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The structures are reported of nine closely related tetra­hydro-1,4-ep­oxy-1-benzazepines carrying pendant heterocyclic sub­stituents, namely: 2-exo-(5-nitro­furan-2-yl)-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C14H12N2O4, (I), 7-fluoro-2-exo-(1-methyl-1H-pyrrol-2-yl)-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C15H15FN2O, (II), 7-fluoro-2-exo-(5-methyl­furan-2-yl)-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C15H14FNO2, (III), 7-fluoro-2-exo-(3-methylthio­phen-2-yl)-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C15H14FNOS, (IV), 7-fluoro-2-exo-(5-methyl­thio­phen-2-yl)-2,3,4,5-tetra­hy­dro-1,4-ep­oxy-1H-1-benzazepine, C15H14FNOS, (V), 7-chloro-2-exo-(5-methyl­furan-2-yl)-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C15H14ClNO2, (VI), 2-exo-(5-methyl­furan-2-yl)-7-trifluoro­meth­oxy-2,3,4,5-tetrahydro-1,4-ep­oxy-1H-1-benzazepine, C16H14F3NO3, (VII), 2-exo-(3-methyl­thio­phen-2-yl)-7-trifluoro­meth­oxy-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C16H14F3NO2S, (VIII), and 2-exo-(5-nitro­furan-2-yl)-7-trifluoro­meth­oxy-2,3,4,5-tetra­hydro-1,4-ep­oxy-1H-1-benzazepine, C15H11F3N2O5, (IX). All nine compounds crystallize in centrosymmetric space groups as racemic mixtures with configuration (2RS,4SR). There are no direction-specific inter­actions between the mol­ecules in (V). The mol­ecules in (III), (IV), (VI) and (VII) are linked into simple chains, by means of a single C-H...O hydrogen bond in each of (III), (VI) and (VII), and by means of a single C-H...[pi](arene) hydrogen bond in (IV), while the mol­ecules in (VIII) are linked into a chain of rings. In each of (I) and (II), a combination of one C-H...O hydrogen bond and one C-H...[pi](arene) hydrogen bond links the mol­ecules into sheets, albeit of completely different construction in the two compounds. In (IX), the sheet structure is built from a combination of four independent C-H...O hydrogen bonds and one C-H...[pi](arene) hydrogen bond. Comparisons are made with some related compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011200707X/sk3430sup1.cif
Contains datablocks global, I, II, III, IV, V, VI, VII, VIII, IX

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IIsup3.hkl
Contains datablock II

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IIIsup4.hkl
Contains datablock III

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IVsup5.hkl
Contains datablock IV

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430Vsup6.hkl
Contains datablock V

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430VIsup7.hkl
Contains datablock VI

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430VIIsup8.hkl
Contains datablock VII

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430VIIIsup9.hkl
Contains datablock VIII

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Structure factor file (CIF format) https://doi.org/10.1107/S010827011200707X/sk3430IXsup10.hkl
Contains datablock IX

CCDC references: 873897; 873898; 873899; 873900; 873901; 873902; 873903; 873904; 873905

Comment top

We report here the molecular and supramolecular structures of nine closely related tetrahydro-1,4-epoxy-1-benzazepines carrying pendant heterocyclic substituents, compounds (I)–(IX) (Fig. 1 and Scheme 1), and we compare these with some related compounds whose structures were reported recently, (X)–(XII) (Blanco et al., 2008) and (XIII)–(XV) (Blanco et al., 2009) (Scheme 2). The work reported here continues our structural study of this class of epoxybenzazepines (Acosta et al., 2008; Blanco et al., 2008, 2009; Gómez et al., 2008, 2009), which is itself associated with a synthetic programme to identify structurally novel antiparasitic agents having new modes of action against both Trypanosoma cruzi and Leishmania chagasi (Gómez et al., 2008; Yépez et al., 2006; Gómez-Ayala et al., 2010). Compounds (I)–(IX) were all prepared by appropriate modification of the procedure previously reported by Acosta et al. (2008).

The molecular constitutions of (I)–(XV) differ in just two respects: the identity of the simple substituent at position 7 (cf. Fig. 1) and the nature of the heterocyclic substituent at position 2. Of the compounds newly reported here, (II)–(V), along with the previously reported (X) and (XI) (Blanco et al., 2008), all carry a fluoro substituent at position 7, and (VI), along with (XIII) and (XV) (Blanco et al., 2009), has a chloro substituent at this position, while (VII)–(IX), and (XII) (Blanco et al., 2008) all have a trifluoromethoxy substituent at position 7. The substituents at position 2 comprise a variety of simply substituted furan units in (I), (III), (VI), (VII), (IX) and (X), or thienyl units, in (IV), (V), (VIII) and (XI)–(XV), with a substituted pyrrole unit in (II). Compounds (I)–(IX) all crystallize in centrosymmetric space groups, with Z' = 1. The molecules contain two stereogenic centres, at atoms C2 and C4, and the reference molecules in (I)–(IX) were all selected to have the R configuration at atom C2 and, on this basis, the configuration at atom C4 is always S in the reference molecules. The space groups for (I)–(IX) indicate that these compounds all crystallize as true racemates with configurations (2RS,4SR). By contrast, (X) crystallizes with Z' = 2 in the centrosymmetric space group P21/c, while (XII) crystallizes in the Sohnke space group P21 with Z' = 1 as a single enantiomorph, having configuration (2S,4R) in the crystal selected for data collection (Blanco et al., 2008).

The shapes of the heterobicyclic ring systems in (I)–(VIII) [(VII)?] and (IX) are all very similar, as indicated by the ring-puckering parameters (Cremer & Pople, 1975), although (VIII) differs somewhat (Table 1). In each of (I)–(VII) and (IX), the five-membered ring adopts a half-chair conformation, for which the idealized value of the puckering angle ϕ is (36k + 18)°, where k represents an integer. On the other hand, this ring in (VIII) adopts a conformation close to an envelope form, folded across the line N1···C4, where the ideal value of ϕ is (36k)°. The six-membered rings all adopt conformations intermediate between a half-chair form, where the idealized values of the puckering angles are θ = 129.2° and ϕ = (60k + 30)°, and an envelope form, where the idealized values are θ = 125.3° and ϕ = (60k)°, where k represents an integer in each case.

The supramolecular assembly in (I)–(IX) is dominated by C—H···O and C—H···π(arene) hydrogen bonds, although a C—H···π(thienyl) interaction is present in the structure of (VIII) (Table 2). The criteria for acceptance of such intermolecular interactions as structurally significant may be simply stated: (i) C—H···O contacts have been discounted if the C—H···O angle is significantly less than 140° (cf. Wood et al., 2009); (ii) C—H···π contacts have been discounted if the H···(ring centroid) distance exceeds 2.90 Å; (iii) all contacts involving methyl C—H bonds have been discounted; and (iv) C—H···F contacts have all been discounted (Howard et al., 1996; Brammer et al., 2001; Thallypally & Nangia, 2001). In addition, we may note here that none of the structures of (I)–(IX) exhibits any aromatic ππ stacking interactions.

Subject to the criteria enumerated above, it is then convenient to discuss the supramolecular assembly of (I)–(IX) in order of increasing complexity, and then briefly to compare these supramolecular structures with those of the related compounds, (X)–(XII) (Blanco et al., 2008).

There are no direction-specific intermolecular interactions of any kind in the structure of (IV), so that this structure may be regarded as zero-dimensional, built from essentially isolated molecules. In each of (III) and (VII), which carry the same heterocyclic substituent but different substituents at position 7 (see Scheme 1), a single rather long but almost linear C—H···O hydrogen bond links molecules related by translation into C(4) (Bernstein et al., 1995) chains running parallel to the [100] direction (Figs. 2 and 3). Two such chains, related to one another by inversion, pass through each unit cell in (VII), but there are four chains passing through each unit cell in (III) (Fig. 4).

In the structure of (VI), the molecules are again linked into a chain by a single C—H···O hydrogen bond (Table 2), but now the chain is of C(3) type running parallel to the [010] direction, and the component molecules are related by a 21 screw axis (Fig. 5). The chains in (IV) are built from a single C—H···π(arene) hydrogen bond linking molecules related by an n-glide plane, such that the chain is parallel to the [101] direction (Fig. 6). In the structure of (VIII), molecules related by translation along [010] are linked into C(4) chains by a C—H···O hydrogen bond (Fig. 7), exactly analogous to the chain formation in (III) and (VII). However, the action of the C—H···O hydrogen bond in (VIII) is modestly augmented by a C—H···π(thienyl) contact, so that the hydrogen-bonded assembly here should more properly be regarded as a chain of rings. Thus, for each of (III), (IV), (VI), (VII) and (VIII), the supramolecular assembly takes the form of a one-dimensional hydrogen-bonded structure, with simple chains in the first four of these compounds and a chain of rings in (VIII).

The hydrogen-bonded supramolecular assembly in each of (I) and (II) is two-dimensional and, in each case, the sheet structure is built from a combination of one C—H···O hydrogen bond and one C—H···.π(arene) hydrogen bond. However, except for the π(arene) acceptor, the donors and acceptors all differ (Table 2), so that the construction of the sheet is also different in the two compounds.

The formation of the sheet structure in (II) is readily analysed in terms of two one-dimensional substructures, each in the form of a simple chain involving just one type of hydrogen bond. Molecules of (II) related by translation are linked by a C—H···O hydrogen bond to form a C(4) chain running parallel to the [010] direction, analogous to the C(4) chains in (III) and (VII). In addition, molecules of (II) related by a c-glide plane are linked by a C—H···π(arene) hydrogen bond into a chain running parallel to the [001] direction. The combination of these two simple chain motifs generates a sheet lying parallel to (100) and containing just one type of ring (Fig. 8).

In the structure of (I), by contrast, a C—H···O hydrogen bond links pairs of molecules which are related by inversion to form a cyclic centrosymmetric dimeric unit characterized by an R22(10) motif. This dimeric unit is centred across (0, 1/2, 0) and it may conveniently be regarded as the basic building block in the formation of the sheet structure of (I). The dimer centred across (0, 1/2, 0) is directly linked by a C—H···π(arene) hydrogen bond to four further such dimers, centred respectively across (0, 0, 1/2), (0, 0, -1/2), (0, 1, 1/2) and (0, 1, -1/2), so forming a sheet lying parallel to (100) and containing two types of ring, both of them centrosymmetric (Fig. 9).

The sheet structure of (IX) is considerably more complex than those in (I) and (II) as five independent hydrogen bonds are involved, four of C—H···O type and one of C—H···π(arene) type (Table 2). However, the essential features of the sheet formation can be conveniently, although not uniquely, analysed in terms of just three of the C—H···O hydrogen bonds. Just as for (I), so too for (IX), a cyclic centrosymmetric dimer unit can be regarded as the basic building block for the sheet structure, but in the structure of (IX) the dimer motif is of R22(16) type (Fig. 10), as opposed to the R22(10) motif in (I). This reference dimer is centred across (1/2, 1, 1/2) and the C—H···O hydrogen bond which involves atom H3B (Table 2) links this dimer directly to the four similar dimer units centred across (1/2, 1/2, 1), (1/2, 1/2, 0), (1/2, 3/2, 1) and (1/2, 3/2, 0) (Fig. 11). In addition, the same reference dimer across (1/2, 1, 1/2) is linked by the C—H···O hydrogen bond involving atom H8 to four further dimeric units, centred across (1/2, -1/2, 1), (1/2, -1/2, 0), (1/2, 5/2, 1) and (1/2, 5/2, 0) (Fig. 12). These interactions in combination give rise to a complex sheet lying parallel to (100). The remaining two hydrogen bonds both lie within the sheet, so that they serve to augment its strength and increase its complexity, but they do not influence the overall dimensionality of the hydrogen-bonded assembly.

We briefly compare here the structures of (X)–(XV) (Blanco et al., 2008, 2009) with those of (I)–(IX). In the structure of (X), which crystallizes with Z' = 2, a combination of one C—H···N hydrogen bond and three C—H···O hydrogen bonds links the molecules into a chain of edge-fused R43(20) rings, anti-parallel pairs of which are weakly linked by two rather long C—H···π(arene) hydrogen bonds. It is noteworthy that (X) is the only example amongst (I)–(XII) where the Z' value is other than 1 and the only example where the structure contains a C—H···N hydrogen bond.

As with the closely related (V), there are no hydrogen bonds of any kind in the structure of (XI), although the molecules of (XI) are weakly linked into centrosymmetric dimers by a single aromatic ππ stacking interaction involving the fluoro-substituted ring. Compounds (V) and (XI) both crystallize in space group P21/c with Z' = 1, and with somewhat similar unit-cell dimensions. Comparison of the two sets of atomic coordinates shows that these also are somewhat similar, but with sufficient differences in detail that (V) and (XI) could, at best, be described as only approximately isostructural. In particular, the ππ stacking interaction present in the structure of (XI) is absent from the structure of (V).

Compound (XII) is the only example in the series (I)–(XV) which crystallizes as a single enantiomorph. The molecules of (XII) are linked by two C—H···O hydrogen bonds, both having the fused-ring O atom as the acceptor, to form a sheet containing a single type of R43(20) ring.

Although (XIII) and (XIV) both crystallize with Z' = 1 in space group Pbca, the unit-cell dimensions for these two compounds are very different, as are their modes of supramolecular assembly. Paired C—H···π(thienyl) hydrogen bonds link molecules of (XIII) into centrosymmetric dimers, while a combination of C—H···O and C—H···π(thienyl) hydrogen bonds links the molecules of (XIV) into a chain of rings. A more complex chain of rings is formed in (XV) built from four independent hydrogen bonds, two of C—H···O type and one each of C—H···π(thienyl) and C—H···π(arene) types.

Accordingly, despite the rather small differences in molecular composition and molecular constitution amongst the members of the series (I)–(XV), no two of the compounds display the same pattern of supramolecular assembly.

Related literature top

For related literature, see: Acosta et al. (2008); Bernstein et al. (1995); Blanco et al. (2008, 2009); Brammer et al. (2001); Cremer & Pople (1975); Gómez et al. (2008, 2009); Gómez-Ayala, Castrillón, Palma, Leal, Escobar & Bahsas (2010); Howard et al. (1996); Thallypally & Nangia (2001); Wood et al. (2009); Yépez et al. (2006).

Experimental top

For the synthesis of (I)–(IX), sodium tungstate dihydrate (10% mol), followed by 30% aqueous hydrogen peroxide solution (12 mmol), were added to a stirred and cooled (ice-bath) solution of the appropriately substituted 2-allyl-N-(heteroarylmethyl)aniline (4 mmol) in methanol (30 ml). The resulting mixtures were stirred at 273 K for 2–8 h and then at ambient temperature for an additional 12–20 h. Each mixture was filtered and then extracted with ethyl acetate (2 × 50 ml) and, for each, the combined extracts were dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and toluene (30 ml) was added to the resulting solid residue. These mixtures were heated under reflux for 6–8 h and, after cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was subject to column chromatographic resolution over silica gel using heptane–ethyl acetate (compositions ranged from 50:1 to 10:1 v/v) as eluent. Crystallization from heptane or heptane–ethyl acetate gave crystals suitable for single-crystal X-ray diffraction. Compound (I), pale yellow, yield 64%, m.p. 411 K; MS (70 eV) m/z (%) 272 (M+, 30), 255 (3), 242 (3), 130 (10), 104 (100), 105 (67). Compound (II), colourless, yield 21%, m.p. 427 K; MS (70 eV) m/z (%) 258 (M+, 30), 241 (18), 228 (1), 148 (9), 123 (9), 122 (15), 107 (100). Compound (III), colourless, yield 60%, m.p. 375 K; MS (70 eV) m/z (%) 259 (M+, 33), 242 (18), 229 (6), 148 (9), 123 (27), 122 (52), 108 (100). Compound (IV), colourless, yield 66%, m.p. 399 K; MS (70 eV) m/z (%) 275 (M+, 52), 258 (30), 245 (9), 148 (15), 124 (79), 123 (91), 122 (100). Compound (V), colourless, yield 64%, m.p. 376 K; MS (70 eV) m/z (%) 275 (M+, 52), 258 (36), 245 (12), 148 (12), 124 (100), 123 (82), 122 (79). Compound (VI), colourless, yield 67%, m.p. 386 K; MS (70 eV) m/z (%) 275 (M+, 35Cl, 18), 258 (12), 245 (3), 164 (6), 139 (27), 138 (33), 108 (100). Compound (VII), colourless, yield 57%, m.p. 366 K; MS (70 eV) m/z (%) 325 (M+, 18), 308 (12), 295 (3), 214 (6), 189 (27), 188 (45), 108 (100). Compound (VIII), colourless, yield 69%, m.p. 351 K; MS (70 eV) m/z (%) 341 (M+, 30), 324 (21), 311 (6), 214 (9), 189 (67), 188 (100), 124 (70). Compound (IX), pale yellow, yield 56%, m.p. 438 K; MS (70 eV) m/z (%) 356 (M+, 9), 339 (1), 326 (1), 214 (12), 189 (70), 188 (100).

Refinement top

All H atoms were located in difference maps and then treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic and heteroaromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. Crystals of (IX) diffracted very weakly at high θ and consquently reflections with θ > 25.5° were omitted from the final refinements. Despite this, fewer than 60% (1631 out of 2749) of the reflections out to θ = 25.5° were labelled as observed.

Computing details top

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structures of (I)–(IX), showing the atom-labelling schemes. (a) Compound (I), (b) (II), (c) (III), (d) (IV), (e) (V), (f) (VI), (g) (VII), (h) (VIII) and (i) (IX). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (III), showing the formation of a hydrogen-bonded C(4) chain running parallel to [100]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (x + 1, y, z) and (-x + 1, y, z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (VII), showing the formation of a hydrogen-bonded C(4) chain running parallel to [100]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (x + 1, y, z) and (-x + 1, y, z), respectively.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (III), viewed approximately along [100], showing the arrangement of the four chains passing through each unit cell. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 5] Fig. 5. Part of the crystal structure of (VI), showing the formation of a hydrogen-bonded C(3) chain running parallel to [010]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-x + 1/2, y - 1/2, -z + 1/2), (-x + 1/2, y + 1/2, -z + 1/2), (x, y - 1, z) and (x, y + 1, z), respectively.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (IV), showing the formation of a hydrogen-bonded chain running parallel to [101]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted.
[Figure 7] Fig. 7. Part of the crystal structure of (VIII), showing the formation of a hydrogen-bonded C(4) chain running parallel to [010]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (x, y + 1, z) and (x, y - 1, z), respectively.
[Figure 8] Fig. 8. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (100) and containing only a single type of ring. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
[Figure 9] Fig. 9. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (100) and containing two types of ring. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
[Figure 10] Fig. 10. Part of the crystal structure of (IX), showing the formation of a cyclic centrosymmetric R22(16) motif. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (-x + 1, -y + 2, -z + 1).
[Figure 11] Fig. 11. A stereoview of part of the crystal structure of (IX), showing the action of the hydrogen bond involving atom H3B in the linking of the R22(16) dimers. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
[Figure 12] Fig. 12. A stereoview of part of the crystal structure of (IX), showing the action of the hydrogen bond involving atom H8 in the linking of the R22(16) dimers. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
(I) 2-exo-(5-nitrofuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy- 1H-1-benzazepine top
Crystal data top
C14H12N2O4F(000) = 568
Mr = 272.26Dx = 1.464 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2835 reflections
a = 7.2248 (5) Åθ = 2.8–27.5°
b = 18.1447 (19) ŵ = 0.11 mm1
c = 9.4504 (8) ÅT = 120 K
β = 94.279 (6)°Block, pale yellow
V = 1235.42 (19) Å30.38 × 0.27 × 0.22 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2835 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1868 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2323
Tmin = 0.960, Tmax = 0.976l = 1212
18226 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0626P)2 + 0.5339P]
where P = (Fo2 + 2Fc2)/3
2835 reflections(Δ/σ)max = 0.001
181 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C14H12N2O4V = 1235.42 (19) Å3
Mr = 272.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.2248 (5) ŵ = 0.11 mm1
b = 18.1447 (19) ÅT = 120 K
c = 9.4504 (8) Å0.38 × 0.27 × 0.22 mm
β = 94.279 (6)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2835 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1868 reflections with I > 2σ(I)
Tmin = 0.960, Tmax = 0.976Rint = 0.047
18226 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.139H-atom parameters constrained
S = 1.05Δρmax = 0.28 e Å3
2835 reflectionsΔρmin = 0.29 e Å3
181 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O140.74199 (18)0.72903 (7)0.26127 (14)0.0311 (3)
O210.51992 (18)0.53677 (7)0.20618 (14)0.0302 (3)
O510.0841 (2)0.45586 (9)0.18575 (17)0.0450 (4)
O520.3362 (2)0.42819 (9)0.31571 (17)0.0484 (4)
N10.7940 (2)0.65364 (8)0.29746 (16)0.0269 (4)
N250.2495 (2)0.46536 (9)0.22568 (19)0.0360 (4)
C20.7725 (3)0.61739 (11)0.15524 (19)0.0290 (4)
H20.85690.57370.15400.035*
C30.8342 (3)0.67659 (11)0.0504 (2)0.0342 (5)
H3A0.95540.66380.01450.041*
H3B0.74100.68250.03100.041*
C40.8491 (3)0.74663 (11)0.1412 (2)0.0322 (5)
H40.79360.78970.08720.039*
C51.0452 (3)0.76363 (11)0.1985 (2)0.0337 (5)
H5A1.04840.81190.24730.040*
H5B1.12700.76650.11920.040*
C5a1.1144 (3)0.70423 (11)0.3014 (2)0.0296 (4)
C61.2998 (3)0.69754 (11)0.3510 (2)0.0325 (5)
H61.38770.73170.32000.039*
C71.3589 (3)0.64225 (12)0.4445 (2)0.0350 (5)
H71.48640.63850.47640.042*
C81.2311 (3)0.59195 (11)0.4918 (2)0.0334 (5)
H81.27110.55420.55660.040*
C91.0461 (3)0.59730 (11)0.4442 (2)0.0297 (4)
H90.95860.56320.47630.036*
C9a0.9884 (3)0.65272 (10)0.34914 (19)0.0266 (4)
C220.5770 (3)0.59338 (11)0.1235 (2)0.0301 (4)
C230.4365 (3)0.61302 (12)0.0268 (2)0.0364 (5)
H230.44090.65050.04300.044*
C240.2833 (3)0.56748 (11)0.0493 (2)0.0351 (5)
H240.16470.56770.00130.042*
C250.3422 (3)0.52358 (11)0.1583 (2)0.0304 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0267 (9)0.0266 (8)0.0273 (8)0.0008 (6)0.0013 (6)0.0001 (7)
C20.0302 (10)0.0286 (10)0.0281 (10)0.0027 (8)0.0018 (8)0.0027 (8)
C30.0366 (12)0.0378 (12)0.0287 (10)0.0049 (9)0.0043 (8)0.0014 (9)
C40.0345 (11)0.0303 (10)0.0327 (11)0.0052 (8)0.0080 (8)0.0071 (8)
C50.0365 (12)0.0282 (11)0.0375 (11)0.0002 (8)0.0106 (9)0.0027 (9)
C5a0.0298 (11)0.0293 (10)0.0301 (10)0.0002 (8)0.0056 (8)0.0036 (8)
C60.0270 (11)0.0329 (11)0.0382 (11)0.0047 (8)0.0066 (8)0.0067 (9)
C70.0285 (11)0.0381 (12)0.0379 (11)0.0019 (9)0.0003 (8)0.0081 (9)
C80.0372 (12)0.0291 (10)0.0329 (11)0.0046 (8)0.0045 (9)0.0023 (8)
C90.0324 (11)0.0262 (10)0.0303 (10)0.0027 (8)0.0017 (8)0.0014 (8)
C9a0.0264 (10)0.0264 (10)0.0273 (9)0.0001 (7)0.0033 (7)0.0038 (8)
O140.0329 (8)0.0273 (7)0.0338 (8)0.0059 (6)0.0066 (6)0.0005 (6)
O210.0277 (7)0.0307 (7)0.0314 (7)0.0006 (6)0.0039 (5)0.0019 (6)
C220.0329 (11)0.0280 (10)0.0293 (10)0.0040 (8)0.0011 (8)0.0044 (8)
C230.0410 (12)0.0336 (11)0.0337 (11)0.0086 (9)0.0037 (9)0.0011 (9)
C240.0318 (11)0.0353 (11)0.0365 (11)0.0043 (9)0.0092 (9)0.0052 (9)
C250.0268 (10)0.0302 (10)0.0332 (10)0.0024 (8)0.0036 (8)0.0075 (8)
N250.0320 (10)0.0340 (10)0.0411 (10)0.0012 (7)0.0033 (8)0.0073 (8)
O510.0310 (9)0.0456 (10)0.0565 (10)0.0064 (7)0.0091 (7)0.0078 (8)
O520.0413 (9)0.0458 (10)0.0562 (10)0.0029 (7)0.0094 (8)0.0144 (8)
Geometric parameters (Å, º) top
N1—C9a1.452 (2)C6—H60.9500
N1—O141.453 (2)C7—C81.396 (3)
N1—C21.494 (2)C7—H70.9500
C2—C221.487 (3)C8—C91.381 (3)
C2—C31.550 (3)C8—H80.9500
C2—H21.0000C9—C9a1.391 (3)
C3—C41.533 (3)C9—H90.9500
C3—H3A0.9900O21—C251.351 (2)
C3—H3B0.9900O21—C221.373 (2)
C4—O141.455 (2)C22—C231.362 (3)
C4—C51.511 (3)C23—C241.410 (3)
C4—H41.0000C23—H230.9500
C5—C5a1.511 (3)C24—C251.346 (3)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—N251.426 (3)
C5a—C61.391 (3)N25—O521.221 (2)
C5a—C9a1.403 (3)N25—O511.238 (2)
C6—C71.383 (3)
C9a—N1—O14108.47 (13)C7—C6—H6119.2
C9a—N1—C2109.31 (14)C5a—C6—H6119.2
O14—N1—C2101.25 (13)C6—C7—C8119.91 (19)
C22—C2—N1110.14 (15)C6—C7—H7120.0
C22—C2—C3112.87 (16)C8—C7—H7120.0
N1—C2—C3104.74 (15)C9—C8—C7119.81 (19)
C22—C2—H2109.7C9—C8—H8120.1
N1—C2—H2109.7C7—C8—H8120.1
C3—C2—H2109.7C8—C9—C9a119.80 (18)
C4—C3—C2103.18 (15)C8—C9—H9120.1
C4—C3—H3A111.1C9a—C9—H9120.1
C2—C3—H3A111.1C9—C9a—C5a121.28 (18)
C4—C3—H3B111.1C9—C9a—N1117.45 (16)
C2—C3—H3B111.1C5a—C9a—N1121.24 (17)
H3A—C3—H3B109.1N1—O14—C4104.30 (13)
O14—C4—C5107.72 (15)C25—O21—C22105.11 (14)
O14—C4—C3103.62 (15)C23—C22—O21109.69 (17)
C5—C4—C3113.24 (16)C23—C22—C2135.1 (2)
O14—C4—H4110.7O21—C22—C2115.19 (16)
C5—C4—H4110.7C22—C23—C24107.45 (19)
C3—C4—H4110.7C22—C23—H23126.3
C4—C5—C5a109.96 (16)C24—C23—H23126.3
C4—C5—H5A109.7C25—C24—C23104.81 (18)
C5a—C5—H5A109.7C25—C24—H24127.6
C4—C5—H5B109.7C23—C24—H24127.6
C5a—C5—H5B109.7C24—C25—O21112.93 (18)
H5A—C5—H5B108.2C24—C25—N25130.42 (18)
C6—C5a—C9a117.70 (18)O21—C25—N25116.62 (16)
C6—C5a—C5122.90 (18)O52—N25—O51124.64 (18)
C9a—C5a—C5119.39 (18)O52—N25—C25119.15 (17)
C7—C6—C5a121.50 (19)O51—N25—C25116.20 (17)
C9a—N1—C2—C22159.65 (15)C2—N1—C9a—C997.98 (19)
O14—N1—C2—C2286.02 (17)O14—N1—C9a—C5a29.6 (2)
C9a—N1—C2—C378.72 (18)C2—N1—C9a—C5a79.9 (2)
O14—N1—C2—C335.61 (17)C9a—N1—O14—C466.22 (16)
C22—C2—C3—C4109.06 (17)C2—N1—O14—C448.73 (16)
N1—C2—C3—C410.76 (19)C5—C4—O14—N178.34 (17)
C2—C3—C4—O1418.09 (19)C3—C4—O14—N141.90 (17)
C2—C3—C4—C598.33 (18)C25—O21—C22—C230.7 (2)
O14—C4—C5—C5a48.6 (2)C25—O21—C22—C2179.16 (16)
C3—C4—C5—C5a65.4 (2)N1—C2—C22—C23113.7 (2)
C4—C5—C5a—C6167.85 (18)C3—C2—C22—C232.9 (3)
C4—C5—C5a—C9a11.6 (2)N1—C2—C22—O2168.3 (2)
C9a—C5a—C6—C70.1 (3)C3—C2—C22—O21175.00 (15)
C5—C5a—C6—C7179.59 (19)O21—C22—C23—C240.4 (2)
C5a—C6—C7—C80.5 (3)C2—C22—C23—C24178.4 (2)
C6—C7—C8—C90.5 (3)C22—C23—C24—C250.1 (2)
C7—C8—C9—C9a0.1 (3)C23—C24—C25—O210.6 (2)
C8—C9—C9a—C5a0.7 (3)C23—C24—C25—N25178.3 (2)
C8—C9—C9a—N1177.17 (17)C22—O21—C25—C240.8 (2)
C6—C5a—C9a—C90.7 (3)C22—O21—C25—N25178.89 (16)
C5—C5a—C9a—C9179.77 (17)C24—C25—N25—O52173.6 (2)
C6—C5a—C9a—N1177.09 (16)O21—C25—N25—O524.1 (3)
C5—C5a—C9a—N12.4 (3)C24—C25—N25—O515.6 (3)
O14—N1—C9a—C9152.45 (15)O21—C25—N25—O51176.76 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C24—H24···O51i0.952.453.359 (3)161
C5—H5B···Cg1ii0.992.663.458 (2)138
Symmetry codes: (i) x, y+1, z; (ii) x, y+3/2, z1/2.
(II) 7-fluoro-2-exo-(1-methyl-1H-pyrrol-2-yl)-2,3,4,5-tetrahydro- 1,4-epoxy-1H-1-benzazepine top
Crystal data top
C15H15FN2OF(000) = 1088
Mr = 258.29Dx = 1.390 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2824 reflections
a = 27.141 (4) Åθ = 2.6–27.5°
b = 5.4082 (7) ŵ = 0.10 mm1
c = 17.2849 (18) ÅT = 120 K
β = 103.275 (9)°Plate, colourless
V = 2469.3 (6) Å30.41 × 0.27 × 0.10 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2824 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1511 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.6°
ϕ and ω scansh = 3434
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 76
Tmin = 0.961, Tmax = 0.990l = 2222
21463 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0685P)2 + 0.4858P]
where P = (Fo2 + 2Fc2)/3
2824 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C15H15FN2OV = 2469.3 (6) Å3
Mr = 258.29Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.141 (4) ŵ = 0.10 mm1
b = 5.4082 (7) ÅT = 120 K
c = 17.2849 (18) Å0.41 × 0.27 × 0.10 mm
β = 103.275 (9)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2824 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1511 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.990Rint = 0.092
21463 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.148H-atom parameters constrained
S = 1.05Δρmax = 0.28 e Å3
2824 reflectionsΔρmin = 0.23 e Å3
173 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F70.01915 (5)0.3742 (3)0.66891 (8)0.0505 (5)
O140.19103 (6)0.7729 (3)0.52314 (8)0.0286 (4)
N10.13816 (7)0.7982 (3)0.48250 (10)0.0257 (5)
N210.12186 (6)0.9895 (3)0.30722 (10)0.0257 (5)
C20.13640 (8)0.6477 (4)0.40853 (12)0.0248 (5)
H20.10120.58560.38700.030*
C30.17219 (9)0.4283 (4)0.43747 (12)0.0297 (6)
H3A0.15280.27420.43960.036*
H3B0.19580.40210.40230.036*
C40.20074 (9)0.5081 (4)0.52100 (13)0.0278 (5)
H40.23780.47480.52900.033*
C50.17983 (8)0.3871 (4)0.58606 (13)0.0278 (5)
H5A0.17930.20530.57930.033*
H5B0.20180.42680.63870.033*
C5a0.12698 (8)0.4803 (4)0.58172 (12)0.0239 (5)
C60.09639 (9)0.3784 (4)0.62816 (13)0.0284 (5)
H60.10800.24330.66260.034*
C70.04905 (9)0.4769 (5)0.62322 (14)0.0340 (6)
C80.03026 (10)0.6729 (5)0.57556 (15)0.0418 (7)
H80.00270.73570.57380.050*
C90.06068 (9)0.7776 (5)0.52991 (14)0.0357 (6)
H90.04880.91560.49690.043*
C9a0.10843 (8)0.6807 (4)0.53242 (12)0.0248 (5)
C220.15270 (8)0.8044 (4)0.34745 (12)0.0244 (5)
C230.19743 (9)0.8140 (4)0.32281 (13)0.0298 (6)
H230.22570.70810.34040.036*
C240.19421 (9)1.0070 (5)0.26726 (13)0.0326 (6)
H240.21961.05470.24050.039*
C250.14742 (9)1.1130 (4)0.25908 (13)0.0306 (6)
H250.13481.24910.22570.037*
C2110.07125 (9)1.0523 (5)0.31534 (14)0.0358 (6)
H21A0.04930.90690.30310.054*
H21B0.05771.18640.27840.054*
H21C0.07271.10600.37000.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0247 (10)0.0276 (11)0.0263 (10)0.0001 (8)0.0088 (8)0.0006 (9)
C20.0269 (13)0.0244 (12)0.0241 (12)0.0015 (10)0.0078 (9)0.0018 (10)
C30.0354 (14)0.0279 (13)0.0273 (12)0.0015 (11)0.0102 (10)0.0011 (11)
C40.0254 (12)0.0254 (13)0.0324 (12)0.0023 (10)0.0063 (10)0.0004 (11)
C50.0270 (13)0.0293 (13)0.0265 (12)0.0006 (10)0.0050 (9)0.0015 (10)
C5a0.0276 (12)0.0210 (12)0.0226 (11)0.0032 (10)0.0049 (9)0.0037 (10)
C60.0331 (14)0.0276 (13)0.0243 (12)0.0042 (10)0.0059 (10)0.0005 (11)
C70.0322 (14)0.0412 (15)0.0322 (13)0.0072 (12)0.0151 (11)0.0042 (12)
F70.0423 (9)0.0647 (11)0.0513 (9)0.0034 (8)0.0248 (7)0.0190 (8)
C80.0345 (15)0.0536 (18)0.0427 (15)0.0122 (13)0.0199 (12)0.0132 (14)
C90.0367 (15)0.0371 (15)0.0372 (14)0.0114 (12)0.0165 (11)0.0112 (12)
C9a0.0276 (12)0.0253 (13)0.0233 (11)0.0006 (10)0.0096 (10)0.0021 (10)
O140.0282 (9)0.0260 (9)0.0317 (9)0.0039 (7)0.0069 (7)0.0026 (7)
N210.0225 (10)0.0296 (11)0.0247 (9)0.0002 (8)0.0048 (8)0.0013 (9)
C220.0258 (12)0.0245 (12)0.0235 (11)0.0007 (10)0.0071 (9)0.0034 (10)
C230.0273 (13)0.0348 (14)0.0288 (12)0.0014 (11)0.0097 (10)0.0021 (11)
C240.0356 (14)0.0393 (15)0.0248 (12)0.0085 (12)0.0109 (10)0.0034 (11)
C250.0370 (15)0.0319 (14)0.0224 (12)0.0095 (11)0.0058 (10)0.0006 (11)
C2110.0262 (13)0.0393 (15)0.0407 (14)0.0026 (11)0.0049 (11)0.0013 (13)
Geometric parameters (Å, º) top
N1—O141.452 (2)C7—C81.368 (3)
N1—C9a1.456 (3)C7—F71.373 (3)
N1—C21.507 (3)C8—C91.387 (3)
C2—C221.498 (3)C8—H80.9500
C2—C31.542 (3)C9—C9a1.389 (3)
C2—H21.0000C9—H90.9500
C3—C41.536 (3)N21—C251.373 (3)
C3—H3A0.9900N21—C221.385 (3)
C3—H3B0.9900N21—C2111.453 (3)
C4—O141.458 (3)C22—C231.377 (3)
C4—C51.519 (3)C23—C241.407 (3)
C4—H41.0000C23—H230.9500
C5—C5a1.506 (3)C24—C251.371 (3)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—H250.9500
C5a—C61.394 (3)C211—H21A0.9800
C5a—C9a1.399 (3)C211—H21B0.9800
C6—C71.375 (3)C211—H21C0.9800
C6—H60.9500
O14—N1—C9a107.02 (15)C8—C7—C6123.5 (2)
O14—N1—C2101.24 (15)F7—C7—C6118.3 (2)
C9a—N1—C2110.68 (16)C7—C8—C9118.1 (2)
C22—C2—N1109.60 (17)C7—C8—H8121.0
C22—C2—C3113.46 (18)C9—C8—H8121.0
N1—C2—C3104.21 (16)C8—C9—C9a120.1 (2)
C22—C2—H2109.8C8—C9—H9120.0
N1—C2—H2109.8C9a—C9—H9120.0
C3—C2—H2109.8C9—C9a—C5a120.9 (2)
C4—C3—C2103.48 (18)C9—C9a—N1117.2 (2)
C4—C3—H3A111.1C5a—C9a—N1121.88 (19)
C2—C3—H3A111.1N1—O14—C4104.16 (14)
C4—C3—H3B111.1C25—N21—C22108.94 (19)
C2—C3—H3B111.1C25—N21—C211124.4 (2)
H3A—C3—H3B109.0C22—N21—C211126.59 (18)
O14—C4—C5107.69 (17)C23—C22—N21106.96 (19)
O14—C4—C3104.16 (17)C23—C22—C2131.6 (2)
C5—C4—C3112.42 (19)N21—C22—C2121.37 (19)
O14—C4—H4110.8C22—C23—C24108.5 (2)
C5—C4—H4110.8C22—C23—H23125.7
C3—C4—H4110.8C24—C23—H23125.7
C5a—C5—C4109.42 (19)C25—C24—C23106.9 (2)
C5a—C5—H5A109.8C25—C24—H24126.5
C4—C5—H5A109.8C23—C24—H24126.5
C5a—C5—H5B109.8C24—C25—N21108.6 (2)
C4—C5—H5B109.8C24—C25—H25125.7
H5A—C5—H5B108.2N21—C25—H25125.7
C6—C5a—C9a118.6 (2)N21—C211—H21A109.5
C6—C5a—C5121.7 (2)N21—C211—H21B109.5
C9a—C5a—C5119.68 (19)H21A—C211—H21B109.5
C7—C6—C5a118.9 (2)N21—C211—H21C109.5
C7—C6—H6120.6H21A—C211—H21C109.5
C5a—C6—H6120.6H21B—C211—H21C109.5
C8—C7—F7118.2 (2)
O14—N1—C2—C2284.41 (19)C5—C5a—C9a—N12.2 (3)
C9a—N1—C2—C22162.38 (17)O14—N1—C9a—C9148.88 (19)
O14—N1—C2—C337.33 (19)C2—N1—C9a—C9101.6 (2)
C9a—N1—C2—C375.9 (2)O14—N1—C9a—C5a30.5 (2)
C22—C2—C3—C4105.9 (2)C2—N1—C9a—C5a79.0 (2)
N1—C2—C3—C413.3 (2)C9a—N1—O14—C467.33 (18)
C2—C3—C4—O1415.5 (2)C2—N1—O14—C448.60 (17)
C2—C3—C4—C5100.8 (2)C5—C4—O14—N179.32 (18)
O14—C4—C5—C5a47.7 (2)C3—C4—O14—N140.24 (19)
C3—C4—C5—C5a66.4 (2)C25—N21—C22—C230.6 (2)
C4—C5—C5a—C6172.14 (19)C211—N21—C22—C23178.7 (2)
C4—C5—C5a—C9a10.5 (3)C25—N21—C22—C2176.10 (18)
C9a—C5a—C6—C70.6 (3)C211—N21—C22—C22.1 (3)
C5—C5a—C6—C7178.0 (2)N1—C2—C22—C23103.2 (3)
C5a—C6—C7—C80.8 (4)C3—C2—C22—C2312.8 (3)
C5a—C6—C7—F7179.67 (19)N1—C2—C22—N2172.5 (2)
F7—C7—C8—C9179.5 (2)C3—C2—C22—N21171.44 (18)
C6—C7—C8—C90.0 (4)N21—C22—C23—C240.2 (2)
C7—C8—C9—C9a1.0 (4)C2—C22—C23—C24176.0 (2)
C8—C9—C9a—C5a1.2 (4)C22—C23—C24—C250.2 (2)
C8—C9—C9a—N1179.5 (2)C23—C24—C25—N210.6 (3)
C6—C5a—C9a—C90.3 (3)C22—N21—C25—C240.7 (2)
C5—C5a—C9a—C9177.1 (2)C211—N21—C25—C24178.92 (19)
C6—C5a—C9a—N1179.65 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O14i0.992.583.530 (3)161
C25—H25···Cg1ii0.952.813.654 (2)149
Symmetry codes: (i) x, y1, z; (ii) x, y+2, z1/2.
(III) 7-fluoro-2-exo-(5-methylfuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy- 1H-1-benzazepine top
Crystal data top
C15H14FNO2F(000) = 544
Mr = 259.27Dx = 1.409 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2807 reflections
a = 5.5265 (5) Åθ = 3.5–27.5°
b = 10.6652 (19) ŵ = 0.10 mm1
c = 20.905 (4) ÅT = 120 K
β = 97.166 (11)°Block, colourless
V = 1222.6 (3) Å30.26 × 0.25 × 0.14 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2807 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1657 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.5°
ϕ and ω scansh = 77
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.974, Tmax = 0.986l = 2727
17136 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0926P)2 + 0.2769P]
where P = (Fo2 + 2Fc2)/3
2807 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
C15H14FNO2V = 1222.6 (3) Å3
Mr = 259.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.5265 (5) ŵ = 0.10 mm1
b = 10.6652 (19) ÅT = 120 K
c = 20.905 (4) Å0.26 × 0.25 × 0.14 mm
β = 97.166 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2807 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1657 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.986Rint = 0.061
17136 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.175H-atom parameters constrained
S = 1.06Δρmax = 0.29 e Å3
2807 reflectionsΔρmin = 0.40 e Å3
173 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F70.8894 (3)0.36913 (15)0.20663 (7)0.0470 (5)
O140.4759 (3)0.09418 (15)0.43212 (8)0.0300 (4)
O210.2993 (3)0.38189 (14)0.53473 (7)0.0270 (4)
N10.4498 (3)0.22775 (17)0.42032 (9)0.0260 (5)
C20.6064 (4)0.2809 (2)0.47792 (11)0.0271 (5)
H20.66390.36660.46750.033*
C30.8259 (4)0.1900 (2)0.48794 (11)0.0307 (6)
H3A0.97210.22780.47270.037*
H3B0.86480.16700.53400.037*
C40.7383 (4)0.0755 (2)0.44708 (11)0.0287 (6)
H40.77480.00400.47180.034*
C50.8431 (4)0.0719 (2)0.38330 (11)0.0310 (6)
H5A1.02350.07290.39110.037*
H5B0.79120.00590.35960.037*
C5a0.7525 (4)0.1848 (2)0.34396 (11)0.0278 (5)
C60.8592 (4)0.2229 (2)0.28997 (11)0.0312 (6)
H60.98810.17570.27570.037*
C70.7748 (4)0.3299 (3)0.25767 (11)0.0338 (6)
C80.5828 (4)0.4001 (2)0.27423 (11)0.0345 (6)
H80.52660.47220.25010.041*
C90.4744 (4)0.3618 (2)0.32747 (11)0.0288 (6)
H90.34120.40790.34020.035*
C9a0.5601 (4)0.2563 (2)0.36215 (11)0.0263 (5)
C220.4728 (4)0.2873 (2)0.53541 (11)0.0261 (5)
C230.4824 (4)0.2226 (2)0.59076 (11)0.0309 (6)
H230.58530.15310.60310.037*
C240.3087 (4)0.2776 (2)0.62774 (11)0.0308 (6)
H240.27580.25240.66940.037*
C250.2004 (4)0.3727 (2)0.59183 (11)0.0271 (5)
C2510.0046 (4)0.4629 (2)0.60230 (11)0.0321 (6)
H25A0.07120.43750.64020.048*
H25B0.11880.46380.56430.048*
H25C0.07460.54700.60930.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0255 (10)0.0251 (11)0.0275 (10)0.0005 (8)0.0036 (8)0.0008 (8)
C20.0270 (12)0.0273 (13)0.0267 (12)0.0033 (10)0.0019 (9)0.0018 (10)
C30.0271 (12)0.0340 (14)0.0306 (13)0.0011 (10)0.0024 (10)0.0035 (10)
C40.0186 (11)0.0314 (13)0.0354 (13)0.0027 (10)0.0008 (9)0.0007 (10)
C50.0268 (12)0.0284 (14)0.0375 (14)0.0003 (10)0.0028 (10)0.0040 (10)
C5a0.0200 (11)0.0311 (13)0.0320 (13)0.0016 (10)0.0020 (9)0.0063 (10)
C60.0250 (12)0.0409 (15)0.0283 (12)0.0003 (11)0.0049 (10)0.0042 (11)
C70.0303 (13)0.0498 (17)0.0221 (12)0.0087 (12)0.0065 (10)0.0003 (11)
F70.0449 (9)0.0661 (12)0.0318 (8)0.0035 (8)0.0123 (7)0.0072 (7)
C80.0356 (14)0.0383 (15)0.0285 (13)0.0014 (11)0.0005 (10)0.0021 (11)
C90.0251 (12)0.0354 (14)0.0257 (12)0.0033 (10)0.0023 (9)0.0030 (10)
C9a0.0219 (11)0.0299 (13)0.0272 (12)0.0048 (9)0.0033 (9)0.0040 (9)
O140.0250 (8)0.0280 (9)0.0375 (9)0.0011 (7)0.0053 (7)0.0004 (7)
O210.0274 (8)0.0267 (9)0.0273 (9)0.0016 (7)0.0057 (6)0.0001 (7)
C220.0258 (12)0.0227 (12)0.0295 (12)0.0005 (9)0.0023 (9)0.0024 (9)
C230.0311 (13)0.0284 (13)0.0327 (13)0.0003 (10)0.0014 (10)0.0015 (10)
C240.0375 (13)0.0305 (13)0.0256 (12)0.0012 (11)0.0091 (10)0.0002 (10)
C250.0294 (12)0.0276 (13)0.0250 (12)0.0050 (10)0.0060 (9)0.0046 (9)
C2510.0319 (13)0.0318 (14)0.0328 (13)0.0004 (11)0.0056 (10)0.0028 (10)
Geometric parameters (Å, º) top
N1—O141.450 (2)C6—H60.9500
N1—C9a1.459 (3)C7—F71.372 (3)
N1—C21.503 (3)C7—C81.378 (3)
C2—C221.489 (3)C8—C91.390 (3)
C2—C31.546 (3)C8—H80.9500
C2—H21.0000C9—C9a1.389 (3)
C3—C41.534 (3)C9—H90.9500
C3—H3A0.9900O21—C251.377 (3)
C3—H3B0.9900O21—C221.391 (3)
C4—O141.459 (2)C22—C231.343 (3)
C4—C51.519 (3)C23—C241.431 (3)
C4—H41.0000C23—H230.9500
C5—C5a1.508 (3)C24—C251.356 (3)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—C2511.484 (3)
C5a—C61.398 (3)C251—H25A0.9800
C5a—C9a1.399 (3)C251—H25B0.9800
C6—C71.377 (3)C251—H25C0.9800
O14—N1—C9a107.71 (16)F7—C7—C6118.2 (2)
O14—N1—C2101.49 (15)F7—C7—C8118.3 (2)
C9a—N1—C2109.29 (17)C6—C7—C8123.5 (2)
C22—C2—N1111.71 (18)C7—C8—C9117.7 (2)
C22—C2—C3112.27 (19)C7—C8—H8121.2
N1—C2—C3103.63 (17)C9—C8—H8121.2
C22—C2—H2109.7C9a—C9—C8120.2 (2)
N1—C2—H2109.7C9a—C9—H9119.9
C3—C2—H2109.7C8—C9—H9119.9
C4—C3—C2103.64 (17)C9—C9a—C5a121.4 (2)
C4—C3—H3A111.0C9—C9a—N1116.97 (19)
C2—C3—H3A111.0C5a—C9a—N1121.5 (2)
C4—C3—H3B111.0N1—O14—C4104.22 (15)
C2—C3—H3B111.0C25—O21—C22106.69 (17)
H3A—C3—H3B109.0C23—C22—O21109.6 (2)
O14—C4—C5107.04 (17)C23—C22—C2134.6 (2)
O14—C4—C3104.30 (17)O21—C22—C2115.82 (19)
C5—C4—C3112.34 (19)C22—C23—C24107.3 (2)
O14—C4—H4111.0C22—C23—H23126.3
C5—C4—H4111.0C24—C23—H23126.3
C3—C4—H4111.0C25—C24—C23106.7 (2)
C5a—C5—C4108.78 (18)C25—C24—H24126.7
C5a—C5—H5A109.9C23—C24—H24126.7
C4—C5—H5A109.9C24—C25—O21109.7 (2)
C5a—C5—H5B109.9C24—C25—C251133.1 (2)
C4—C5—H5B109.9O21—C25—C251117.2 (2)
H5A—C5—H5B108.3C25—C251—H25A109.5
C6—C5a—C9a118.2 (2)C25—C251—H25B109.5
C6—C5a—C5121.9 (2)H25A—C251—H25B109.5
C9a—C5a—C5119.9 (2)C25—C251—H25C109.5
C7—C6—C5a119.0 (2)H25A—C251—H25C109.5
C7—C6—H6120.5H25B—C251—H25C109.5
C5a—C6—H6120.5
O14—N1—C2—C2282.6 (2)C6—C5a—C9a—N1175.8 (2)
C9a—N1—C2—C22163.83 (18)C5—C5a—C9a—N12.7 (3)
O14—N1—C2—C338.5 (2)O14—N1—C9a—C9154.56 (18)
C9a—N1—C2—C375.1 (2)C2—N1—C9a—C996.0 (2)
C22—C2—C3—C4105.7 (2)O14—N1—C9a—C5a28.8 (3)
N1—C2—C3—C415.0 (2)C2—N1—C9a—C5a80.7 (2)
C2—C3—C4—O1413.7 (2)C9a—N1—O14—C466.04 (19)
C2—C3—C4—C5101.9 (2)C2—N1—O14—C448.72 (19)
O14—C4—C5—C5a50.6 (2)C5—C4—O14—N180.3 (2)
C3—C4—C5—C5a63.3 (2)C3—C4—O14—N138.9 (2)
C4—C5—C5a—C6165.2 (2)C25—O21—C22—C230.4 (2)
C4—C5—C5a—C9a13.3 (3)C25—O21—C22—C2179.20 (17)
C9a—C5a—C6—C71.2 (3)N1—C2—C22—C23107.0 (3)
C5—C5a—C6—C7177.3 (2)C3—C2—C22—C238.9 (4)
C5a—C6—C7—F7177.0 (2)N1—C2—C22—O2174.5 (2)
C5a—C6—C7—C82.5 (4)C3—C2—C22—O21169.54 (18)
F7—C7—C8—C9177.68 (19)O21—C22—C23—C240.2 (3)
C6—C7—C8—C91.8 (4)C2—C22—C23—C24178.3 (2)
C7—C8—C9—C9a0.2 (3)C22—C23—C24—C250.8 (3)
C8—C9—C9a—C5a1.3 (3)C23—C24—C25—O211.0 (3)
C8—C9—C9a—N1175.29 (19)C23—C24—C25—C251178.6 (2)
C6—C5a—C9a—C90.6 (3)C22—O21—C25—C240.9 (2)
C5—C5a—C9a—C9179.1 (2)C22—O21—C25—C251178.77 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O14i0.992.553.527 (3)169
Symmetry code: (i) x+1, y, z.
(IV) 7-fluoro-2-exo-(3-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy- 1H-1-benzazepine top
Crystal data top
C15H14FNOSF(000) = 576
Mr = 275.34Dx = 1.420 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2944 reflections
a = 9.272 (2) Åθ = 2.9–27.5°
b = 10.9142 (13) ŵ = 0.25 mm1
c = 12.963 (2) ÅT = 120 K
β = 101.023 (11)°Needle, colourless
V = 1287.6 (4) Å30.36 × 0.19 × 0.14 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2944 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2049 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1314
Tmin = 0.914, Tmax = 0.965l = 1616
20089 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0574P)2 + 1.162P]
where P = (Fo2 + 2Fc2)/3
2944 reflections(Δ/σ)max = 0.002
173 parametersΔρmax = 0.65 e Å3
0 restraintsΔρmin = 0.50 e Å3
Crystal data top
C15H14FNOSV = 1287.6 (4) Å3
Mr = 275.34Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.272 (2) ŵ = 0.25 mm1
b = 10.9142 (13) ÅT = 120 K
c = 12.963 (2) Å0.36 × 0.19 × 0.14 mm
β = 101.023 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2944 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2049 reflections with I > 2σ(I)
Tmin = 0.914, Tmax = 0.965Rint = 0.059
20089 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.03Δρmax = 0.65 e Å3
2944 reflectionsΔρmin = 0.50 e Å3
173 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S210.73323 (7)0.36360 (7)0.54429 (5)0.0367 (2)
F70.67363 (18)0.48049 (16)0.15000 (12)0.0426 (4)
O140.87502 (16)0.34916 (15)0.31779 (13)0.0268 (4)
N10.7208 (2)0.34258 (18)0.26739 (15)0.0227 (4)
C20.6530 (2)0.4340 (2)0.33016 (18)0.0230 (5)
H20.56220.46780.28490.028*
C30.7692 (3)0.5373 (2)0.3529 (2)0.0295 (6)
H3A0.73720.61070.30970.035*
H3B0.78770.56070.42810.035*
C40.9063 (3)0.4801 (2)0.3228 (2)0.0290 (6)
H40.99540.49790.37770.035*
C50.9300 (3)0.5206 (2)0.2149 (2)0.0304 (6)
H5A0.92990.61120.21080.036*
H5B1.02620.49050.20290.036*
C5a0.8081 (3)0.4693 (2)0.13190 (19)0.0250 (5)
C60.7939 (3)0.5023 (2)0.0261 (2)0.0297 (6)
H60.85890.56020.00480.036*
C70.6837 (3)0.4489 (2)0.04656 (19)0.0304 (6)
C80.5844 (3)0.3665 (2)0.02092 (19)0.0287 (5)
H80.50910.33270.07330.034*
C90.5977 (2)0.3339 (2)0.08428 (19)0.0249 (5)
H90.53060.27740.10490.030*
C9a0.7097 (2)0.3845 (2)0.15926 (18)0.0224 (5)
C220.6115 (2)0.3756 (2)0.42537 (17)0.0219 (5)
C230.4768 (2)0.3294 (2)0.43404 (18)0.0227 (5)
C240.4746 (3)0.2853 (2)0.53732 (18)0.0253 (5)
H240.39000.25010.55690.030*
C250.6039 (3)0.2983 (2)0.6045 (2)0.0324 (6)
H250.62090.27410.67620.039*
C2310.3468 (3)0.3223 (3)0.3454 (2)0.0369 (6)
H23A0.34330.24110.31280.055*
H23B0.35560.38520.29300.055*
H23C0.25650.33600.37270.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0188 (9)0.0245 (11)0.0243 (10)0.0001 (8)0.0030 (8)0.0004 (8)
C20.0211 (11)0.0250 (12)0.0237 (12)0.0018 (9)0.0064 (9)0.0012 (10)
C30.0311 (13)0.0265 (13)0.0326 (13)0.0057 (11)0.0105 (11)0.0025 (11)
C40.0241 (12)0.0314 (13)0.0310 (13)0.0073 (10)0.0035 (10)0.0033 (11)
C50.0241 (12)0.0330 (14)0.0361 (14)0.0068 (10)0.0112 (10)0.0012 (11)
C5a0.0245 (12)0.0209 (12)0.0311 (13)0.0016 (9)0.0092 (10)0.0005 (10)
C60.0303 (13)0.0267 (13)0.0359 (14)0.0038 (10)0.0155 (11)0.0054 (11)
C70.0337 (13)0.0335 (14)0.0259 (13)0.0125 (11)0.0103 (10)0.0084 (11)
F70.0466 (10)0.0546 (11)0.0279 (8)0.0111 (8)0.0102 (7)0.0145 (7)
C80.0256 (12)0.0330 (14)0.0270 (12)0.0076 (11)0.0038 (10)0.0025 (11)
C90.0208 (11)0.0251 (12)0.0300 (13)0.0016 (9)0.0077 (9)0.0001 (10)
C9a0.0240 (11)0.0200 (12)0.0241 (11)0.0046 (9)0.0071 (9)0.0007 (9)
O140.0184 (8)0.0292 (9)0.0318 (9)0.0019 (7)0.0028 (7)0.0024 (7)
S210.0264 (3)0.0503 (5)0.0299 (3)0.0075 (3)0.0035 (2)0.0081 (3)
C220.0203 (10)0.0225 (12)0.0218 (11)0.0004 (9)0.0014 (9)0.0005 (9)
C230.0230 (11)0.0234 (12)0.0222 (11)0.0001 (9)0.0050 (9)0.0021 (9)
C240.0266 (12)0.0253 (13)0.0257 (12)0.0004 (10)0.0098 (10)0.0014 (10)
C250.0394 (14)0.0345 (14)0.0229 (12)0.0013 (12)0.0050 (11)0.0048 (11)
C2310.0271 (13)0.0483 (17)0.0337 (14)0.0077 (12)0.0018 (11)0.0093 (12)
Geometric parameters (Å, º) top
N1—O141.456 (2)C6—H60.9500
N1—C9a1.459 (3)C7—F71.370 (3)
N1—C21.499 (3)C7—C81.373 (4)
C2—C221.503 (3)C8—C91.392 (3)
C2—C31.549 (3)C8—H80.9500
C2—H21.0000C9—C9a1.393 (3)
C3—C41.533 (3)C9—H90.9500
C3—H3A0.9900S21—C251.707 (3)
C3—H3B0.9900S21—C221.733 (2)
C4—O141.457 (3)C22—C231.371 (3)
C4—C51.523 (4)C23—C241.427 (3)
C4—H41.0000C23—C2311.499 (3)
C5—C5a1.510 (3)C24—C251.348 (3)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—H250.9500
C5a—C9a1.392 (3)C231—H23A0.9800
C5a—C61.399 (3)C231—H23B0.9800
C6—C71.379 (4)C231—H23C0.9800
O14—N1—C9a107.34 (16)F7—C7—C8118.6 (2)
O14—N1—C2101.62 (16)F7—C7—C6117.7 (2)
C9a—N1—C2110.66 (17)C8—C7—C6123.7 (2)
N1—C2—C22111.31 (19)C7—C8—C9117.8 (2)
N1—C2—C3103.85 (18)C7—C8—H8121.1
C22—C2—C3115.5 (2)C9—C8—H8121.1
N1—C2—H2108.7C8—C9—C9a119.8 (2)
C22—C2—H2108.7C8—C9—H9120.1
C3—C2—H2108.7C9a—C9—H9120.1
C4—C3—C2103.61 (19)C5a—C9a—C9121.5 (2)
C4—C3—H3A111.0C5a—C9a—N1121.6 (2)
C2—C3—H3A111.0C9—C9a—N1116.9 (2)
C4—C3—H3B111.0N1—O14—C4103.81 (16)
C2—C3—H3B111.0C25—S21—C2292.48 (12)
H3A—C3—H3B109.0C23—C22—C2127.1 (2)
O14—C4—C5107.8 (2)C23—C22—S21110.36 (17)
O14—C4—C3104.08 (18)C2—C22—S21122.49 (16)
C5—C4—C3112.8 (2)C22—C23—C24112.2 (2)
O14—C4—H4110.6C22—C23—C231124.6 (2)
C5—C4—H4110.6C24—C23—C231123.2 (2)
C3—C4—H4110.6C25—C24—C23113.6 (2)
C5a—C5—C4109.1 (2)C25—C24—H24123.2
C5a—C5—H5A109.9C23—C24—H24123.2
C4—C5—H5A109.9C24—C25—S21111.36 (19)
C5a—C5—H5B109.9C24—C25—H25124.3
C4—C5—H5B109.9S21—C25—H25124.3
H5A—C5—H5B108.3C23—C231—H23A109.5
C9a—C5a—C6118.5 (2)C23—C231—H23B109.5
C9a—C5a—C5120.1 (2)H23A—C231—H23B109.5
C6—C5a—C5121.3 (2)C23—C231—H23C109.5
C7—C6—C5a118.6 (2)H23A—C231—H23C109.5
C7—C6—H6120.7H23B—C231—H23C109.5
C5a—C6—H6120.7
O14—N1—C2—C2287.67 (19)C8—C9—C9a—N1177.6 (2)
C9a—N1—C2—C22158.58 (18)O14—N1—C9a—C5a29.2 (3)
O14—N1—C2—C337.2 (2)C2—N1—C9a—C5a80.9 (3)
C9a—N1—C2—C376.6 (2)O14—N1—C9a—C9149.65 (19)
N1—C2—C3—C412.8 (2)C2—N1—C9a—C9100.3 (2)
C22—C2—C3—C4109.3 (2)C9a—N1—O14—C467.2 (2)
C2—C3—C4—O1416.2 (2)C2—N1—O14—C449.0 (2)
C2—C3—C4—C5100.4 (2)C5—C4—O14—N179.4 (2)
O14—C4—C5—C5a47.2 (3)C3—C4—O14—N140.6 (2)
C3—C4—C5—C5a67.1 (3)N1—C2—C22—C2394.9 (3)
C4—C5—C5a—C9a8.6 (3)C3—C2—C22—C23147.0 (2)
C4—C5—C5a—C6173.4 (2)N1—C2—C22—S2187.6 (2)
C9a—C5a—C6—C70.3 (4)C3—C2—C22—S2130.4 (3)
C5—C5a—C6—C7177.6 (2)C25—S21—C22—C230.3 (2)
C5a—C6—C7—F7178.7 (2)C25—S21—C22—C2177.5 (2)
C5a—C6—C7—C81.3 (4)C2—C22—C23—C24177.6 (2)
F7—C7—C8—C9179.0 (2)S21—C22—C23—C240.2 (3)
C6—C7—C8—C91.0 (4)C2—C22—C23—C2314.0 (4)
C7—C8—C9—C9a0.3 (3)S21—C22—C23—C231178.3 (2)
C6—C5a—C9a—C90.9 (3)C22—C23—C24—C250.2 (3)
C5—C5a—C9a—C9178.9 (2)C231—C23—C24—C25178.7 (2)
C6—C5a—C9a—N1177.9 (2)C23—C24—C25—S210.5 (3)
C5—C5a—C9a—N10.1 (3)C22—S21—C25—C240.5 (2)
C8—C9—C9a—C5a1.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C24—H24···Cg1i0.952.563.443 (3)154
Symmetry code: (i) x1/2, y+1/2, z+1/2.
(V) 7-fluoro-2-exo-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy- 1H-1-benzazepine top
Crystal data top
C15H14FNOSF(000) = 576
Mr = 275.34Dx = 1.411 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2975 reflections
a = 9.2106 (16) Åθ = 3.0–27.5°
b = 10.906 (2) ŵ = 0.25 mm1
c = 13.4259 (13) ÅT = 120 K
β = 106.086 (12)°Plate, colourless
V = 1295.8 (4) Å30.39 × 0.24 × 0.10 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2975 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1888 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1414
Tmin = 0.908, Tmax = 0.975l = 1717
20023 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0367P)2 + 0.733P]
where P = (Fo2 + 2Fc2)/3
2975 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C15H14FNOSV = 1295.8 (4) Å3
Mr = 275.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.2106 (16) ŵ = 0.25 mm1
b = 10.906 (2) ÅT = 120 K
c = 13.4259 (13) Å0.39 × 0.24 × 0.10 mm
β = 106.086 (12)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2975 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1888 reflections with I > 2σ(I)
Tmin = 0.908, Tmax = 0.975Rint = 0.082
20023 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.03Δρmax = 0.25 e Å3
2975 reflectionsΔρmin = 0.31 e Å3
173 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S210.77817 (7)0.65565 (6)0.49078 (5)0.02927 (17)
F70.13536 (16)0.52473 (13)0.12616 (10)0.0381 (4)
O140.45370 (18)0.63367 (14)0.33326 (12)0.0283 (4)
N10.5321 (2)0.64634 (16)0.25375 (14)0.0231 (4)
C20.6567 (2)0.5554 (2)0.28974 (18)0.0247 (5)
H20.69100.52770.22900.030*
C30.5796 (3)0.4466 (2)0.32923 (19)0.0295 (6)
H3A0.56040.37780.27910.035*
H3B0.64250.41680.39710.035*
C40.4311 (3)0.5017 (2)0.33886 (19)0.0306 (6)
H40.41360.47900.40680.037*
C50.2958 (3)0.4674 (2)0.24979 (18)0.0293 (6)
H5A0.28900.37720.24240.035*
H5B0.20190.49740.26370.035*
C5a0.3132 (2)0.52449 (19)0.15110 (18)0.0237 (5)
C60.2145 (3)0.4968 (2)0.05498 (19)0.0284 (5)
H60.13320.44140.04980.034*
C70.2359 (3)0.5505 (2)0.03230 (18)0.0280 (5)
C80.3531 (3)0.6300 (2)0.03024 (18)0.0279 (5)
H80.36630.66400.09230.034*
C90.4509 (3)0.6584 (2)0.06547 (17)0.0256 (5)
H90.53320.71260.06970.031*
C9a0.4292 (2)0.60785 (19)0.15560 (17)0.0227 (5)
C220.7885 (2)0.60794 (19)0.36990 (17)0.0234 (5)
C230.9329 (3)0.6163 (2)0.36471 (18)0.0280 (5)
H230.96260.59450.30470.034*
C241.0358 (3)0.6605 (2)0.45681 (18)0.0275 (5)
H241.14050.67190.46410.033*
C250.9704 (3)0.6848 (2)0.53327 (18)0.0275 (5)
C2511.0413 (3)0.7310 (2)0.64117 (19)0.0372 (6)
H25A1.15130.73440.65390.056*
H25B1.01600.67560.69140.056*
H25C1.00280.81330.64860.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0211 (10)0.0214 (9)0.0285 (10)0.0013 (8)0.0096 (9)0.0006 (8)
C20.0232 (12)0.0218 (11)0.0298 (13)0.0026 (9)0.0084 (11)0.0000 (10)
C30.0283 (13)0.0219 (12)0.0338 (14)0.0032 (10)0.0013 (11)0.0033 (10)
C40.0362 (14)0.0278 (12)0.0289 (13)0.0056 (11)0.0109 (12)0.0052 (10)
C50.0245 (13)0.0324 (14)0.0328 (14)0.0038 (10)0.0107 (11)0.0005 (11)
C5a0.0209 (12)0.0206 (11)0.0300 (13)0.0032 (9)0.0079 (11)0.0000 (10)
C60.0221 (12)0.0272 (12)0.0369 (15)0.0002 (10)0.0101 (11)0.0042 (11)
C70.0243 (13)0.0299 (12)0.0275 (13)0.0030 (10)0.0032 (11)0.0061 (11)
F70.0353 (9)0.0497 (9)0.0275 (8)0.0043 (7)0.0055 (7)0.0069 (7)
C80.0295 (13)0.0270 (12)0.0290 (13)0.0044 (10)0.0110 (11)0.0010 (10)
C90.0247 (12)0.0212 (11)0.0330 (14)0.0013 (10)0.0114 (11)0.0013 (10)
C9a0.0203 (12)0.0190 (10)0.0291 (13)0.0024 (9)0.0071 (10)0.0020 (10)
O140.0296 (9)0.0288 (9)0.0295 (9)0.0004 (7)0.0133 (8)0.0044 (7)
S210.0251 (3)0.0307 (3)0.0336 (3)0.0029 (3)0.0110 (3)0.0053 (3)
C220.0225 (12)0.0198 (11)0.0276 (13)0.0010 (9)0.0066 (11)0.0011 (9)
C230.0276 (13)0.0279 (12)0.0299 (13)0.0005 (10)0.0103 (11)0.0021 (10)
C240.0202 (12)0.0279 (12)0.0338 (13)0.0027 (10)0.0062 (11)0.0044 (11)
C250.0248 (13)0.0230 (12)0.0328 (13)0.0032 (10)0.0046 (11)0.0020 (10)
C2510.0368 (15)0.0356 (14)0.0369 (15)0.0039 (12)0.0063 (13)0.0052 (12)
Geometric parameters (Å, º) top
N1—O141.452 (2)C6—H60.9500
N1—C9a1.456 (3)C7—F71.370 (3)
N1—C21.492 (3)C7—C81.378 (3)
C2—C221.496 (3)C8—C91.385 (3)
C2—C31.550 (3)C8—H80.9500
C2—H21.0000C9—C9a1.394 (3)
C3—C41.532 (3)C9—H90.9500
C3—H3A0.9900S21—C221.732 (2)
C3—H3B0.9900S21—C251.732 (2)
C4—O141.459 (3)C22—C231.354 (3)
C4—C51.516 (3)C23—C241.418 (3)
C4—H41.0000C23—H230.9500
C5—C5a1.512 (3)C24—C251.353 (3)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—C2511.502 (3)
C5a—C61.390 (3)C251—H25A0.9800
C5a—C9a1.391 (3)C251—H25B0.9800
C6—C71.372 (3)C251—H25C0.9800
O14—N1—C9a107.82 (16)F7—C7—C6118.5 (2)
O14—N1—C2101.14 (15)F7—C7—C8118.2 (2)
C9a—N1—C2110.56 (16)C6—C7—C8123.2 (2)
N1—C2—C22112.13 (18)C7—C8—C9117.6 (2)
N1—C2—C3103.65 (17)C7—C8—H8121.2
C22—C2—C3113.87 (19)C9—C8—H8121.2
N1—C2—H2109.0C8—C9—C9a120.3 (2)
C22—C2—H2109.0C8—C9—H9119.9
C3—C2—H2109.0C9a—C9—H9119.9
C4—C3—C2103.41 (18)C5a—C9a—C9120.9 (2)
C4—C3—H3A111.1C5a—C9a—N1121.8 (2)
C2—C3—H3A111.1C9—C9a—N1117.22 (19)
C4—C3—H3B111.1N1—O14—C4103.82 (15)
C2—C3—H3B111.1C22—S21—C2592.71 (11)
H3A—C3—H3B109.0C23—C22—C2127.0 (2)
O14—C4—C5107.48 (19)C23—C22—S21109.74 (18)
O14—C4—C3103.88 (18)C2—C22—S21123.02 (16)
C5—C4—C3113.2 (2)C22—C23—C24114.0 (2)
O14—C4—H4110.7C22—C23—H23123.0
C5—C4—H4110.7C24—C23—H23123.0
C3—C4—H4110.7C25—C24—C23113.4 (2)
C5a—C5—C4109.05 (19)C25—C24—H24123.3
C5a—C5—H5A109.9C23—C24—H24123.3
C4—C5—H5A109.9C24—C25—C251129.2 (2)
C5a—C5—H5B109.9C24—C25—S21110.10 (18)
C4—C5—H5B109.9C251—C25—S21120.72 (18)
H5A—C5—H5B108.3C25—C251—H25A109.5
C6—C5a—C9a118.6 (2)C25—C251—H25B109.5
C6—C5a—C5121.6 (2)H25A—C251—H25B109.5
C9a—C5a—C5119.8 (2)C25—C251—H25C109.5
C7—C6—C5a119.2 (2)H25A—C251—H25C109.5
C7—C6—H6120.4H25B—C251—H25C109.5
C5a—C6—H6120.4
O14—N1—C2—C2283.99 (19)C8—C9—C9a—C5a2.6 (3)
C9a—N1—C2—C22162.00 (18)C8—C9—C9a—N1177.18 (19)
O14—N1—C2—C339.26 (19)O14—N1—C9a—C5a26.4 (3)
C9a—N1—C2—C374.8 (2)C2—N1—C9a—C5a83.3 (2)
N1—C2—C3—C415.1 (2)O14—N1—C9a—C9153.33 (18)
C22—C2—C3—C4107.0 (2)C2—N1—C9a—C997.0 (2)
C2—C3—C4—O1414.5 (2)C9a—N1—O14—C465.9 (2)
C2—C3—C4—C5101.7 (2)C2—N1—O14—C450.13 (19)
O14—C4—C5—C5a48.2 (2)C5—C4—O14—N180.0 (2)
C3—C4—C5—C5a65.9 (2)C3—C4—O14—N140.2 (2)
C4—C5—C5a—C6172.4 (2)N1—C2—C22—C23121.8 (2)
C4—C5—C5a—C9a8.3 (3)C3—C2—C22—C23120.9 (2)
C9a—C5a—C6—C71.2 (3)N1—C2—C22—S2164.2 (2)
C5—C5a—C6—C7179.6 (2)C3—C2—C22—S2153.1 (2)
C5a—C6—C7—F7178.34 (19)C25—S21—C22—C230.61 (18)
C5a—C6—C7—C81.2 (3)C25—S21—C22—C2174.32 (19)
F7—C7—C8—C9177.89 (19)C2—C22—C23—C24174.6 (2)
C6—C7—C8—C91.6 (3)S21—C22—C23—C240.1 (3)
C7—C8—C9—C9a0.3 (3)C22—C23—C24—C250.7 (3)
C6—C5a—C9a—C93.0 (3)C23—C24—C25—C251179.3 (2)
C5—C5a—C9a—C9177.7 (2)C23—C24—C25—S211.1 (3)
C6—C5a—C9a—N1176.74 (19)C22—S21—C25—C241.00 (18)
C5—C5a—C9a—N12.5 (3)C22—S21—C25—C251179.4 (2)
(VI) 7-chloro-2-exo-(5-methylfuran-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy- 1H-1-benzazepine top
Crystal data top
C15H14ClNO2F(000) = 576
Mr = 275.72Dx = 1.396 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3017 reflections
a = 10.2835 (13) Åθ = 3.1–27.5°
b = 5.4829 (3) ŵ = 0.29 mm1
c = 23.428 (2) ÅT = 120 K
β = 96.665 (9)°Needle, colourless
V = 1312.0 (2) Å30.42 × 0.18 × 0.14 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3017 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1902 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 67
Tmin = 0.889, Tmax = 0.961l = 3030
20222 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0623P)2 + 0.6498P]
where P = (Fo2 + 2Fc2)/3
3017 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
C15H14ClNO2V = 1312.0 (2) Å3
Mr = 275.72Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.2835 (13) ŵ = 0.29 mm1
b = 5.4829 (3) ÅT = 120 K
c = 23.428 (2) Å0.42 × 0.18 × 0.14 mm
β = 96.665 (9)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3017 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1902 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.961Rint = 0.073
20222 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.07Δρmax = 0.33 e Å3
3017 reflectionsΔρmin = 0.44 e Å3
173 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O140.34374 (16)0.4489 (3)0.30724 (7)0.0291 (4)
O210.34664 (15)0.6791 (3)0.46890 (6)0.0289 (4)
N10.44200 (19)0.4982 (4)0.35536 (8)0.0275 (5)
C20.3899 (2)0.3569 (4)0.40257 (10)0.0273 (6)
H20.46400.30970.43190.033*
C30.3302 (2)0.1242 (5)0.37220 (10)0.0298 (6)
H3A0.38540.02050.38270.036*
H3B0.24080.09340.38230.036*
C40.3276 (2)0.1848 (4)0.30807 (10)0.0295 (6)
H40.24210.13600.28630.035*
C50.4406 (2)0.0723 (4)0.28161 (10)0.0287 (6)
H5A0.42990.10210.23960.034*
H5B0.44190.10610.28810.034*
C5a0.5680 (2)0.1835 (4)0.30853 (9)0.0250 (5)
C60.6901 (2)0.0847 (4)0.30085 (10)0.0264 (5)
H60.69540.05650.27770.032*
C70.8034 (2)0.1929 (4)0.32700 (10)0.0290 (6)
Cl70.95437 (6)0.06118 (13)0.31858 (3)0.0402 (2)
C80.7997 (2)0.4044 (5)0.35946 (11)0.0309 (6)
H80.87830.47960.37610.037*
C90.6792 (2)0.5027 (4)0.36694 (10)0.0292 (6)
H90.67490.64720.38900.035*
C9a0.5643 (2)0.3926 (4)0.34255 (10)0.0253 (5)
C220.2939 (2)0.5053 (4)0.43032 (10)0.0299 (6)
C230.1629 (3)0.5149 (6)0.42683 (12)0.0457 (8)
H230.10280.41470.40360.055*
C240.1308 (3)0.7045 (6)0.46471 (13)0.0471 (8)
H240.04530.75390.47140.056*
C250.2439 (2)0.7993 (5)0.48904 (10)0.0323 (6)
C2510.2788 (3)1.0005 (5)0.53044 (11)0.0387 (7)
H25A0.19891.08300.53910.058*
H25B0.33541.11770.51360.058*
H25C0.32520.93380.56590.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0276 (11)0.0286 (11)0.0247 (10)0.0009 (9)0.0035 (8)0.0002 (9)
C20.0315 (13)0.0259 (13)0.0238 (12)0.0039 (10)0.0002 (10)0.0022 (10)
C30.0317 (14)0.0269 (13)0.0311 (13)0.0003 (10)0.0047 (10)0.0003 (11)
C40.0310 (13)0.0253 (13)0.0306 (13)0.0029 (11)0.0029 (10)0.0021 (11)
C50.0337 (14)0.0249 (13)0.0266 (12)0.0031 (11)0.0004 (10)0.0021 (10)
C5a0.0309 (13)0.0244 (13)0.0198 (11)0.0010 (10)0.0026 (9)0.0035 (10)
C60.0346 (14)0.0230 (12)0.0220 (11)0.0008 (10)0.0044 (10)0.0016 (10)
C70.0294 (13)0.0318 (14)0.0265 (12)0.0025 (11)0.0066 (10)0.0030 (11)
Cl70.0313 (4)0.0456 (4)0.0446 (4)0.0025 (3)0.0081 (3)0.0080 (3)
C80.0287 (13)0.0311 (14)0.0322 (13)0.0039 (11)0.0010 (10)0.0024 (11)
C90.0327 (14)0.0242 (13)0.0302 (13)0.0008 (10)0.0012 (11)0.0041 (10)
C9a0.0284 (13)0.0247 (13)0.0226 (11)0.0009 (10)0.0020 (9)0.0017 (10)
O140.0315 (9)0.0273 (9)0.0259 (9)0.0008 (7)0.0079 (7)0.0016 (7)
O210.0309 (9)0.0309 (9)0.0248 (8)0.0034 (7)0.0019 (7)0.0008 (7)
C220.0314 (13)0.0335 (14)0.0235 (12)0.0019 (11)0.0022 (10)0.0024 (11)
C230.0291 (15)0.0559 (18)0.0498 (17)0.0059 (13)0.0047 (13)0.0183 (15)
C240.0344 (15)0.0543 (19)0.0521 (17)0.0119 (14)0.0031 (13)0.0159 (15)
C250.0360 (14)0.0355 (15)0.0256 (12)0.0105 (12)0.0050 (10)0.0011 (11)
C2510.0495 (17)0.0385 (16)0.0286 (13)0.0101 (13)0.0063 (12)0.0020 (12)
Geometric parameters (Å, º) top
N1—C9a1.447 (3)C6—H60.9500
N1—O141.449 (2)C7—C81.389 (3)
N1—C21.499 (3)C7—Cl71.744 (2)
C2—C221.486 (3)C8—C91.381 (4)
C2—C31.552 (3)C8—H80.9500
C2—H21.0000C9—C9a1.390 (3)
C3—C41.536 (3)C9—H90.9500
C3—H3A0.9900O21—C251.375 (3)
C3—H3B0.9900O21—C221.380 (3)
C4—O141.458 (3)C22—C231.341 (4)
C4—C51.510 (3)C23—C241.430 (4)
C4—H41.0000C23—H230.9500
C5—C5a1.515 (3)C24—C251.339 (4)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—C2511.485 (3)
C5a—C61.399 (3)C251—H25A0.9800
C5a—C9a1.399 (3)C251—H25B0.9800
C6—C71.385 (3)C251—H25C0.9800
C9a—N1—O14107.95 (17)C6—C7—C8121.6 (2)
C9a—N1—C2109.85 (18)C6—C7—Cl7119.11 (19)
O14—N1—C2101.58 (16)C8—C7—Cl7119.26 (19)
C22—C2—N1110.6 (2)C9—C8—C7118.5 (2)
C22—C2—C3113.8 (2)C9—C8—H8120.7
N1—C2—C3104.07 (18)C7—C8—H8120.7
C22—C2—H2109.4C8—C9—C9a120.7 (2)
N1—C2—H2109.4C8—C9—H9119.6
C3—C2—H2109.4C9a—C9—H9119.6
C4—C3—C2103.37 (19)C9—C9a—C5a120.8 (2)
C4—C3—H3A111.1C9—C9a—N1117.3 (2)
C2—C3—H3A111.1C5a—C9a—N1121.9 (2)
C4—C3—H3B111.1N1—O14—C4104.19 (16)
C2—C3—H3B111.1C25—O21—C22107.26 (19)
H3A—C3—H3B109.1C23—C22—O21109.2 (2)
O14—C4—C5107.8 (2)C23—C22—C2135.1 (2)
O14—C4—C3103.82 (18)O21—C22—C2115.7 (2)
C5—C4—C3112.7 (2)C22—C23—C24107.1 (2)
O14—C4—H4110.7C22—C23—H23126.5
C5—C4—H4110.7C24—C23—H23126.5
C3—C4—H4110.7C25—C24—C23107.1 (2)
C4—C5—C5a109.52 (19)C25—C24—H24126.4
C4—C5—H5A109.8C23—C24—H24126.4
C5a—C5—H5A109.8C24—C25—O21109.4 (2)
C4—C5—H5B109.8C24—C25—C251134.3 (2)
C5a—C5—H5B109.8O21—C25—C251116.3 (2)
H5A—C5—H5B108.2C25—C251—H25A109.5
C6—C5a—C9a118.4 (2)C25—C251—H25B109.5
C6—C5a—C5122.5 (2)H25A—C251—H25B109.5
C9a—C5a—C5119.2 (2)C25—C251—H25C109.5
C7—C6—C5a119.9 (2)H25A—C251—H25C109.5
C7—C6—H6120.0H25B—C251—H25C109.5
C5a—C6—H6120.0
C9a—N1—C2—C22160.05 (19)C6—C5a—C9a—N1176.4 (2)
O14—N1—C2—C2285.8 (2)C5—C5a—C9a—N13.4 (3)
C9a—N1—C2—C377.4 (2)O14—N1—C9a—C9151.4 (2)
O14—N1—C2—C336.7 (2)C2—N1—C9a—C998.6 (2)
C22—C2—C3—C4108.3 (2)O14—N1—C9a—C5a30.6 (3)
N1—C2—C3—C412.2 (2)C2—N1—C9a—C5a79.4 (2)
C2—C3—C4—O1416.7 (2)C9a—N1—O14—C466.5 (2)
C2—C3—C4—C599.8 (2)C2—N1—O14—C449.0 (2)
O14—C4—C5—C5a48.8 (2)C5—C4—O14—N178.8 (2)
C3—C4—C5—C5a65.2 (3)C3—C4—O14—N141.0 (2)
C4—C5—C5a—C6167.6 (2)C25—O21—C22—C230.5 (3)
C4—C5—C5a—C9a12.2 (3)C25—O21—C22—C2178.9 (2)
C9a—C5a—C6—C70.5 (3)N1—C2—C22—C23101.1 (4)
C5—C5a—C6—C7179.4 (2)C3—C2—C22—C2315.6 (4)
C5a—C6—C7—C82.3 (4)N1—C2—C22—O2178.1 (2)
C5a—C6—C7—Cl7178.08 (17)C3—C2—C22—O21165.18 (19)
C6—C7—C8—C92.1 (4)O21—C22—C23—C240.3 (3)
Cl7—C7—C8—C9178.33 (19)C2—C22—C23—C24179.0 (3)
C7—C8—C9—C9a0.0 (4)C22—C23—C24—C250.0 (3)
C8—C9—C9a—C5a1.8 (4)C23—C24—C25—O210.3 (3)
C8—C9—C9a—N1176.2 (2)C23—C24—C25—C251178.4 (3)
C6—C5a—C9a—C91.5 (3)C22—O21—C25—C240.5 (3)
C5—C5a—C9a—C9178.6 (2)C22—O21—C25—C251178.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O14i1.002.493.312 (3)140
Symmetry code: (i) x+1/2, y1/2, z+1/2.
(VII) 2-exo-(5-methylfuran-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro- 1,4-epoxy-1H-1-benzazepine top
Crystal data top
C16H14F3NO3Z = 2
Mr = 325.28F(000) = 336
Triclinic, P1Dx = 1.501 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.5088 (6) ÅCell parameters from 3299 reflections
b = 10.7619 (17) Åθ = 3.1–27.5°
c = 13.1398 (19) ŵ = 0.13 mm1
α = 110.011 (10)°T = 120 K
β = 98.797 (10)°Needle, colourless
γ = 92.271 (12)°0.41 × 0.19 × 0.08 mm
V = 719.80 (18) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3299 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1690 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.111
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 67
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.949, Tmax = 0.990l = 1717
21281 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0626P)2 + 0.2269P]
where P = (Fo2 + 2Fc2)/3
3299 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C16H14F3NO3γ = 92.271 (12)°
Mr = 325.28V = 719.80 (18) Å3
Triclinic, P1Z = 2
a = 5.5088 (6) ÅMo Kα radiation
b = 10.7619 (17) ŵ = 0.13 mm1
c = 13.1398 (19) ÅT = 120 K
α = 110.011 (10)°0.41 × 0.19 × 0.08 mm
β = 98.797 (10)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3299 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1690 reflections with I > 2σ(I)
Tmin = 0.949, Tmax = 0.990Rint = 0.111
21281 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.147H-atom parameters constrained
S = 1.01Δρmax = 0.26 e Å3
3299 reflectionsΔρmin = 0.31 e Å3
209 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F10.9339 (3)0.22573 (19)0.11911 (14)0.0515 (5)
F20.9163 (4)0.35443 (18)0.04447 (15)0.0609 (6)
F30.5900 (4)0.2905 (3)0.07717 (17)0.0731 (7)
O140.4590 (3)0.04233 (17)0.39016 (14)0.0258 (4)
O210.3182 (3)0.40634 (16)0.56232 (13)0.0243 (4)
O710.7675 (4)0.14349 (19)0.01534 (15)0.0365 (5)
N10.4265 (4)0.1666 (2)0.37127 (17)0.0239 (5)
C20.6028 (5)0.2625 (3)0.4668 (2)0.0247 (6)
H20.66060.33860.44640.030*
C30.8230 (5)0.1821 (3)0.4833 (2)0.0294 (6)
H3A0.96900.21240.45930.035*
H3B0.86830.19040.56140.035*
C40.7259 (4)0.0393 (3)0.4108 (2)0.0261 (6)
H40.77170.02340.45030.031*
C50.8106 (5)0.0038 (3)0.3005 (2)0.0271 (6)
H5A0.99290.00970.31200.033*
H5B0.75880.09960.26020.033*
C5a0.6997 (4)0.0761 (2)0.2337 (2)0.0238 (6)
C60.7803 (5)0.0758 (3)0.1387 (2)0.0267 (6)
H60.90780.02320.11290.032*
C70.6738 (5)0.1528 (3)0.0817 (2)0.0286 (6)
C80.4829 (5)0.2280 (3)0.1143 (2)0.0296 (6)
H80.40770.27740.07250.036*
C90.4049 (5)0.2288 (3)0.2099 (2)0.0288 (6)
H90.27560.28070.23470.035*
C9a0.5117 (4)0.1556 (2)0.2697 (2)0.0235 (6)
C220.4840 (5)0.3140 (2)0.5655 (2)0.0234 (6)
C230.4977 (5)0.2925 (3)0.6616 (2)0.0288 (6)
H230.59910.23440.68500.035*
C240.3308 (5)0.3735 (3)0.7216 (2)0.0295 (6)
H240.29970.37940.79220.035*
C250.2260 (5)0.4400 (2)0.6588 (2)0.0234 (6)
C710.7994 (6)0.2516 (3)0.0398 (2)0.0367 (7)
C2510.0376 (5)0.5375 (3)0.6731 (2)0.0283 (6)
H25A0.12000.62750.69510.042*
H25B0.05350.53210.73020.042*
H25C0.07740.51710.60350.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0231 (12)0.0208 (12)0.0271 (12)0.0019 (9)0.0046 (9)0.0075 (10)
C20.0252 (14)0.0217 (14)0.0250 (14)0.0005 (11)0.0059 (11)0.0051 (11)
C30.0244 (14)0.0311 (16)0.0296 (15)0.0031 (12)0.0059 (12)0.0063 (13)
C40.0196 (14)0.0286 (15)0.0310 (15)0.0052 (11)0.0050 (11)0.0114 (13)
C50.0241 (14)0.0256 (15)0.0325 (16)0.0060 (11)0.0088 (12)0.0094 (13)
C5a0.0190 (13)0.0206 (14)0.0285 (15)0.0005 (11)0.0027 (11)0.0054 (12)
C60.0243 (14)0.0255 (15)0.0288 (15)0.0028 (11)0.0086 (12)0.0063 (12)
C70.0326 (16)0.0321 (16)0.0198 (14)0.0020 (12)0.0089 (12)0.0059 (12)
C80.0315 (16)0.0334 (16)0.0249 (15)0.0067 (12)0.0038 (12)0.0115 (13)
C90.0250 (14)0.0299 (16)0.0290 (15)0.0068 (12)0.0047 (12)0.0069 (13)
C9a0.0230 (14)0.0215 (14)0.0247 (14)0.0016 (11)0.0059 (11)0.0058 (11)
O140.0243 (10)0.0224 (10)0.0323 (11)0.0020 (8)0.0067 (8)0.0109 (8)
O710.0485 (13)0.0350 (12)0.0302 (11)0.0095 (10)0.0179 (9)0.0117 (10)
C710.0435 (19)0.044 (2)0.0279 (16)0.0147 (15)0.0131 (14)0.0157 (15)
F10.0661 (13)0.0627 (13)0.0422 (11)0.0236 (10)0.0312 (10)0.0282 (10)
F20.0877 (15)0.0456 (12)0.0470 (12)0.0127 (11)0.0259 (11)0.0095 (10)
F30.0667 (14)0.127 (2)0.0631 (14)0.0527 (13)0.0282 (11)0.0691 (14)
O210.0288 (10)0.0222 (10)0.0216 (10)0.0041 (8)0.0061 (8)0.0067 (8)
C220.0234 (14)0.0193 (14)0.0282 (15)0.0037 (11)0.0052 (11)0.0087 (12)
C230.0357 (16)0.0247 (15)0.0273 (15)0.0049 (12)0.0050 (12)0.0106 (12)
C240.0369 (16)0.0306 (16)0.0229 (14)0.0065 (12)0.0090 (12)0.0100 (12)
C250.0273 (14)0.0198 (14)0.0210 (13)0.0006 (11)0.0078 (11)0.0033 (11)
C2510.0302 (15)0.0261 (15)0.0277 (15)0.0043 (12)0.0070 (12)0.0075 (12)
Geometric parameters (Å, º) top
N1—C9a1.450 (3)C7—O711.421 (3)
N1—O141.454 (3)C8—C91.386 (4)
N1—C21.499 (3)C8—H80.9500
C2—C221.487 (3)C9—C9a1.380 (4)
C2—C31.549 (4)C9—H90.9500
C2—H21.0000O71—C711.321 (3)
C3—C41.527 (4)C71—F31.323 (3)
C3—H3A0.9900C71—F21.324 (3)
C3—H3B0.9900C71—F11.329 (3)
C4—O141.457 (3)O21—C251.376 (3)
C4—C51.517 (4)O21—C221.383 (3)
C4—H41.0000C22—C231.352 (4)
C5—C5a1.508 (4)C23—C241.429 (4)
C5—H5A0.9900C23—H230.9500
C5—H5B0.9900C24—C251.348 (4)
C5a—C61.387 (4)C24—H240.9500
C5a—C9a1.405 (3)C25—C2511.491 (3)
C6—C71.386 (4)C251—H25A0.9800
C6—H60.9500C251—H25B0.9800
C7—C81.382 (4)C251—H25C0.9800
C9a—N1—O14107.84 (18)C7—C8—C9117.7 (2)
C9a—N1—C2109.50 (19)C7—C8—H8121.1
O14—N1—C2101.50 (18)C9—C8—H8121.1
C22—C2—N1111.2 (2)C9a—C9—C8121.2 (2)
C22—C2—C3113.5 (2)C9a—C9—H9119.4
N1—C2—C3104.3 (2)C8—C9—H9119.4
C22—C2—H2109.3C9—C9a—C5a120.5 (2)
N1—C2—H2109.3C9—C9a—N1117.6 (2)
C3—C2—H2109.3C5a—C9a—N1121.8 (2)
C4—C3—C2103.6 (2)N1—O14—C4104.10 (17)
C4—C3—H3A111.0C71—O71—C7119.2 (2)
C2—C3—H3A111.0O71—C71—F3113.3 (3)
C4—C3—H3B111.0O71—C71—F2113.2 (2)
C2—C3—H3B111.0F3—C71—F2107.1 (3)
H3A—C3—H3B109.0O71—C71—F1108.5 (2)
O14—C4—C5107.6 (2)F3—C71—F1106.9 (2)
O14—C4—C3103.99 (19)F2—C71—F1107.6 (3)
C5—C4—C3112.8 (2)C25—O21—C22106.90 (19)
O14—C4—H4110.7C23—C22—O21109.3 (2)
C5—C4—H4110.7C23—C22—C2135.2 (2)
C3—C4—H4110.7O21—C22—C2115.5 (2)
C5a—C5—C4109.8 (2)C22—C23—C24107.1 (2)
C5a—C5—H5A109.7C22—C23—H23126.5
C4—C5—H5A109.7C24—C23—H23126.5
C5a—C5—H5B109.7C25—C24—C23106.9 (2)
C4—C5—H5B109.7C25—C24—H24126.6
H5A—C5—H5B108.2C23—C24—H24126.6
C6—C5a—C9a118.6 (2)C24—C25—O21109.9 (2)
C6—C5a—C5122.2 (2)C24—C25—C251133.5 (2)
C9a—C5a—C5119.2 (2)O21—C25—C251116.6 (2)
C7—C6—C5a119.6 (2)C25—C251—H25A109.5
C7—C6—H6120.2C25—C251—H25B109.5
C5a—C6—H6120.2H25A—C251—H25B109.5
C8—C7—C6122.3 (2)C25—C251—H25C109.5
C8—C7—O71122.7 (2)H25A—C251—H25C109.5
C6—C7—O71114.9 (2)H25B—C251—H25C109.5
C9a—N1—C2—C22159.6 (2)C2—N1—C9a—C998.8 (3)
O14—N1—C2—C2286.6 (2)O14—N1—C9a—C5a29.8 (3)
C9a—N1—C2—C377.8 (2)C2—N1—C9a—C5a79.9 (3)
O14—N1—C2—C336.0 (2)C9a—N1—O14—C466.7 (2)
C22—C2—C3—C4109.6 (2)C2—N1—O14—C448.4 (2)
N1—C2—C3—C411.6 (3)C5—C4—O14—N178.9 (2)
C2—C3—C4—O1417.1 (3)C3—C4—O14—N141.0 (2)
C2—C3—C4—C599.2 (2)C8—C7—O71—C7141.8 (4)
O14—C4—C5—C5a48.5 (3)C6—C7—O71—C71141.1 (3)
C3—C4—C5—C5a65.7 (3)C7—O71—C71—F374.3 (3)
C4—C5—C5a—C6167.7 (2)C7—O71—C71—F247.8 (3)
C4—C5—C5a—C9a11.1 (3)C7—O71—C71—F1167.2 (2)
C9a—C5a—C6—C70.3 (4)C25—O21—C22—C231.0 (3)
C5—C5a—C6—C7179.1 (2)C25—O21—C22—C2179.1 (2)
C5a—C6—C7—C81.9 (4)N1—C2—C22—C23105.6 (3)
C5a—C6—C7—O71179.0 (2)C3—C2—C22—C2311.6 (4)
C6—C7—C8—C92.5 (4)N1—C2—C22—O2174.4 (3)
O71—C7—C8—C9179.4 (2)C3—C2—C22—O21168.4 (2)
C7—C8—C9—C9a0.9 (4)O21—C22—C23—C240.7 (3)
C8—C9—C9a—C5a1.3 (4)C2—C22—C23—C24179.3 (3)
C8—C9—C9a—N1177.4 (2)C22—C23—C24—C250.2 (3)
C6—C5a—C9a—C91.9 (4)C23—C24—C25—O210.4 (3)
C5—C5a—C9a—C9179.3 (2)C23—C24—C25—C251179.2 (3)
C6—C5a—C9a—N1176.7 (2)C22—O21—C25—C240.8 (3)
C5—C5a—C9a—N12.1 (4)C22—O21—C25—C251178.8 (2)
O14—N1—C9a—C9151.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O14i0.992.583.545 (3)165
Symmetry code: (i) x+1, y, z.
(VIII) 2-exo-(3-methylthiophen-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro- 1,4-epoxy-1H-1-benzazepine top
Crystal data top
C16H14F3NO2SF(000) = 704
Mr = 341.35Dx = 1.555 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3348 reflections
a = 16.234 (3) Åθ = 2.6–27.5°
b = 5.6113 (5) ŵ = 0.26 mm1
c = 16.665 (3) ÅT = 120 K
β = 106.143 (14)°Block, colourless
V = 1458.2 (4) Å30.38 × 0.32 × 0.24 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3348 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2493 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.6°
ϕ and ω scansh = 2121
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 77
Tmin = 0.906, Tmax = 0.939l = 2121
21849 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0464P)2 + 1.2783P]
where P = (Fo2 + 2Fc2)/3
3348 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
C16H14F3NO2SV = 1458.2 (4) Å3
Mr = 341.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.234 (3) ŵ = 0.26 mm1
b = 5.6113 (5) ÅT = 120 K
c = 16.665 (3) Å0.38 × 0.32 × 0.24 mm
β = 106.143 (14)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3348 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2493 reflections with I > 2σ(I)
Tmin = 0.906, Tmax = 0.939Rint = 0.070
21849 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.11Δρmax = 0.30 e Å3
3348 reflectionsΔρmin = 0.42 e Å3
209 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S210.41310 (4)0.35094 (11)0.92562 (4)0.03043 (17)
F10.01593 (9)1.1704 (3)0.33237 (10)0.0460 (4)
F20.00757 (11)0.8241 (3)0.37535 (11)0.0636 (6)
F30.10805 (11)0.8884 (3)0.34085 (10)0.0501 (4)
O140.39200 (9)0.4578 (3)0.67877 (9)0.0233 (3)
O710.09158 (10)1.0632 (3)0.45501 (10)0.0324 (4)
N10.30547 (11)0.4484 (3)0.68755 (11)0.0218 (4)
C20.31597 (14)0.5535 (4)0.77282 (13)0.0237 (4)
H20.26310.64670.77150.028*
C30.39199 (14)0.7315 (4)0.78423 (14)0.0269 (5)
H3A0.37290.89750.78840.032*
H3B0.43880.69320.83490.032*
C40.42139 (14)0.6969 (4)0.70506 (13)0.0234 (4)
H40.48530.70610.71870.028*
C50.38013 (13)0.8682 (4)0.63472 (14)0.0233 (4)
H5A0.38671.03370.65620.028*
H5B0.40940.85590.59010.028*
C5a0.28585 (13)0.8114 (4)0.59901 (13)0.0226 (4)
C60.23136 (13)0.9575 (4)0.53963 (13)0.0240 (4)
H60.25301.09570.51940.029*
C70.14545 (14)0.8985 (4)0.51059 (14)0.0267 (5)
C80.11120 (15)0.6989 (4)0.53724 (15)0.0308 (5)
H80.05170.66490.51730.037*
C90.16605 (14)0.5487 (4)0.59399 (14)0.0283 (5)
H90.14450.40660.61170.034*
C9a0.25238 (13)0.6061 (4)0.62495 (13)0.0223 (4)
C220.32612 (13)0.3607 (4)0.83779 (13)0.0231 (4)
C230.26886 (14)0.1832 (4)0.84007 (14)0.0255 (5)
C240.29619 (16)0.0410 (4)0.91387 (14)0.0306 (5)
H240.26390.08870.92580.037*
C250.37292 (16)0.1100 (5)0.96509 (15)0.0327 (5)
H250.40080.03421.01640.039*
C710.05325 (16)0.9854 (5)0.37774 (16)0.0360 (6)
C2310.18665 (15)0.1382 (4)0.77280 (15)0.0317 (5)
H23A0.19960.06250.72470.048*
H23B0.15720.28990.75540.048*
H23C0.14970.03300.79450.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0215 (9)0.0197 (9)0.0234 (9)0.0004 (7)0.0050 (7)0.0004 (7)
C20.0259 (11)0.0211 (10)0.0237 (11)0.0005 (9)0.0062 (9)0.0023 (9)
C30.0306 (11)0.0242 (11)0.0259 (11)0.0048 (9)0.0078 (9)0.0050 (9)
C40.0227 (10)0.0187 (10)0.0275 (11)0.0027 (8)0.0050 (8)0.0010 (8)
C50.0229 (10)0.0182 (10)0.0285 (11)0.0023 (8)0.0064 (9)0.0010 (9)
C5a0.0236 (10)0.0200 (10)0.0237 (10)0.0005 (8)0.0059 (8)0.0028 (8)
C60.0250 (10)0.0196 (10)0.0273 (11)0.0008 (9)0.0072 (9)0.0003 (9)
C70.0275 (11)0.0261 (11)0.0240 (11)0.0042 (9)0.0029 (9)0.0023 (9)
C80.0247 (11)0.0321 (13)0.0315 (12)0.0042 (10)0.0011 (9)0.0008 (10)
C90.0282 (11)0.0264 (11)0.0274 (11)0.0067 (9)0.0027 (9)0.0018 (9)
C9a0.0248 (10)0.0195 (10)0.0206 (10)0.0002 (8)0.0031 (8)0.0015 (8)
O140.0233 (7)0.0184 (7)0.0277 (8)0.0006 (6)0.0061 (6)0.0031 (6)
O710.0294 (8)0.0315 (9)0.0316 (9)0.0057 (7)0.0005 (7)0.0047 (7)
C710.0326 (13)0.0377 (14)0.0333 (13)0.0030 (11)0.0018 (10)0.0092 (11)
F10.0378 (8)0.0546 (10)0.0398 (9)0.0105 (7)0.0013 (7)0.0198 (7)
F20.0493 (10)0.0755 (13)0.0484 (10)0.0325 (9)0.0158 (8)0.0236 (9)
F30.0643 (11)0.0499 (10)0.0364 (8)0.0133 (8)0.0143 (8)0.0053 (7)
S210.0280 (3)0.0382 (3)0.0228 (3)0.0005 (3)0.0032 (2)0.0009 (2)
C220.0236 (10)0.0229 (10)0.0225 (10)0.0019 (9)0.0060 (8)0.0010 (9)
C230.0269 (11)0.0241 (11)0.0270 (11)0.0023 (9)0.0097 (9)0.0003 (9)
C240.0383 (13)0.0286 (12)0.0280 (12)0.0034 (10)0.0145 (10)0.0034 (10)
C250.0376 (13)0.0358 (13)0.0249 (11)0.0082 (11)0.0091 (10)0.0041 (10)
C2310.0300 (12)0.0293 (12)0.0345 (13)0.0052 (10)0.0070 (10)0.0022 (10)
Geometric parameters (Å, º) top
N1—O141.453 (2)C7—O711.424 (3)
N1—C9a1.454 (3)C8—C91.389 (3)
N1—C21.504 (3)C8—H80.9500
C2—C221.507 (3)C9—C9a1.390 (3)
C2—C31.558 (3)C9—H90.9500
C2—H21.0000O71—C711.338 (3)
C3—C41.535 (3)C71—F11.327 (3)
C3—H3A0.9900C71—F31.330 (3)
C3—H3B0.9900C71—F21.332 (3)
C4—O141.450 (2)S21—C251.710 (3)
C4—C51.520 (3)S21—C221.729 (2)
C4—H41.0000C22—C231.370 (3)
C5—C5a1.514 (3)C23—C241.429 (3)
C5—H5A0.9900C23—C2311.507 (3)
C5—H5B0.9900C24—C251.356 (3)
C5a—C9a1.393 (3)C24—H240.9500
C5a—C61.396 (3)C25—H250.9500
C6—C71.383 (3)C231—H23A0.9800
C6—H60.9500C231—H23B0.9800
C7—C81.378 (3)C231—H23C0.9800
O14—N1—C9a107.61 (15)C7—C8—C9118.2 (2)
O14—N1—C2102.84 (14)C7—C8—H8120.9
C9a—N1—C2109.17 (16)C9—C8—H8120.9
N1—C2—C22111.01 (17)C8—C9—C9a120.1 (2)
N1—C2—C3104.15 (16)C8—C9—H9120.0
C22—C2—C3116.62 (18)C9a—C9—H9120.0
N1—C2—H2108.2C9—C9a—C5a121.1 (2)
C22—C2—H2108.2C9—C9a—N1117.45 (19)
C3—C2—H2108.2C5a—C9a—N1121.42 (18)
C4—C3—C2103.83 (17)C4—O14—N1104.42 (14)
C4—C3—H3A111.0C71—O71—C7116.85 (19)
C2—C3—H3A111.0F1—C71—F3108.4 (2)
C4—C3—H3B111.0F1—C71—F2107.3 (2)
C2—C3—H3B111.0F3—C71—F2107.1 (2)
H3A—C3—H3B109.0F1—C71—O71108.0 (2)
O14—C4—C5108.33 (17)F3—C71—O71112.7 (2)
O14—C4—C3102.82 (17)F2—C71—O71113.1 (2)
C5—C4—C3114.04 (18)C25—S21—C2292.38 (11)
O14—C4—H4110.5C23—C22—C2127.0 (2)
C5—C4—H4110.5C23—C22—S21110.75 (17)
C3—C4—H4110.5C2—C22—S21122.09 (16)
C5a—C5—C4110.53 (17)C22—C23—C24112.3 (2)
C5a—C5—H5A109.5C22—C23—C231124.7 (2)
C4—C5—H5A109.5C24—C23—C231123.1 (2)
C5a—C5—H5B109.5C25—C24—C23113.2 (2)
C4—C5—H5B109.5C25—C24—H24123.4
H5A—C5—H5B108.1C23—C24—H24123.4
C9a—C5a—C6118.75 (19)C24—C25—S21111.44 (18)
C9a—C5a—C5119.43 (19)C24—C25—H25124.3
C6—C5a—C5121.82 (19)S21—C25—H25124.3
C7—C6—C5a119.1 (2)C23—C231—H23A109.5
C7—C6—H6120.5C23—C231—H23B109.5
C5a—C6—H6120.5H23A—C231—H23B109.5
C8—C7—C6122.7 (2)C23—C231—H23C109.5
C8—C7—O71120.5 (2)H23A—C231—H23C109.5
C6—C7—O71116.7 (2)H23B—C231—H23C109.5
O14—N1—C2—C2296.50 (18)C2—N1—C9a—C998.8 (2)
C9a—N1—C2—C22149.43 (17)O14—N1—C9a—C5a31.9 (2)
O14—N1—C2—C329.79 (19)C2—N1—C9a—C5a79.0 (2)
C9a—N1—C2—C384.3 (2)C5—C4—O14—N176.87 (19)
N1—C2—C3—C43.6 (2)C3—C4—O14—N144.16 (19)
C22—C2—C3—C4119.1 (2)C9a—N1—O14—C468.27 (18)
C2—C3—C4—O1423.8 (2)C2—N1—O14—C446.93 (18)
C2—C3—C4—C593.2 (2)C8—C7—O71—C7166.6 (3)
O14—C4—C5—C5a44.4 (2)C6—C7—O71—C71117.3 (2)
C3—C4—C5—C5a69.4 (2)C7—O71—C71—F1171.56 (18)
C4—C5—C5a—C9a7.7 (3)C7—O71—C71—F351.9 (3)
C4—C5—C5a—C6173.21 (19)C7—O71—C71—F269.8 (3)
C9a—C5a—C6—C72.2 (3)N1—C2—C22—C2359.9 (3)
C5—C5a—C6—C7178.7 (2)C3—C2—C22—C23178.9 (2)
C5a—C6—C7—C80.7 (3)N1—C2—C22—S21124.53 (17)
C5a—C6—C7—O71175.31 (19)C3—C2—C22—S215.5 (3)
C6—C7—C8—C91.7 (4)C25—S21—C22—C230.06 (18)
O71—C7—C8—C9177.5 (2)C25—S21—C22—C2176.31 (18)
C7—C8—C9—C9a2.5 (4)C2—C22—C23—C24175.7 (2)
C8—C9—C9a—C5a1.1 (3)S21—C22—C23—C240.3 (2)
C8—C9—C9a—N1176.7 (2)C2—C22—C23—C2314.9 (4)
C6—C5a—C9a—C91.3 (3)S21—C22—C23—C231179.03 (18)
C5—C5a—C9a—C9179.6 (2)C22—C23—C24—C250.7 (3)
C6—C5a—C9a—N1179.03 (19)C231—C23—C24—C25178.7 (2)
C5—C5a—C9a—N11.9 (3)C23—C24—C25—S210.7 (3)
O14—N1—C9a—C9150.29 (19)C22—S21—C25—C240.44 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O14i0.992.413.383 (3)168
C3—H3A···Cg2i0.992.703.533 (3)142
Symmetry code: (i) x, y+1, z.
(IX) 2-exo-(5-nitrofuran-2-yl)-7-trifluoromethoxy-2,3,4,5-tetrahydro-1,4- epoxy-1H-1-benzazepine top
Crystal data top
C15H11F3N2O5F(000) = 728
Mr = 356.26Dx = 1.610 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3380 reflections
a = 20.4120 (15) Åθ = 3.0–27.5°
b = 7.3690 (18) ŵ = 0.15 mm1
c = 10.035 (3) ÅT = 120 K
β = 103.091 (15)°Block, pale yellow
V = 1470.2 (6) Å30.26 × 0.25 × 0.14 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2743 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1634 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.081
Detector resolution: 9.091 pixels mm-1θmax = 25.5°, θmin = 3.0°
ϕ and ω scansh = 2424
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 88
Tmin = 0.963, Tmax = 0.980l = 1212
18612 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0863P)2 + 1.0699P]
where P = (Fo2 + 2Fc2)/3
2743 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C15H11F3N2O5V = 1470.2 (6) Å3
Mr = 356.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 20.4120 (15) ŵ = 0.15 mm1
b = 7.3690 (18) ÅT = 120 K
c = 10.035 (3) Å0.26 × 0.25 × 0.14 mm
β = 103.091 (15)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2743 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1634 reflections with I > 2σ(I)
Tmin = 0.963, Tmax = 0.980Rint = 0.081
18612 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0620 restraints
wR(F2) = 0.183H-atom parameters constrained
S = 1.07Δρmax = 0.31 e Å3
2743 reflectionsΔρmin = 0.32 e Å3
226 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F10.01000 (12)0.1560 (3)0.7817 (2)0.0611 (7)
F20.07503 (12)0.0187 (3)0.6750 (3)0.0639 (8)
F30.00887 (12)0.2265 (4)0.5746 (3)0.0690 (8)
O140.24772 (12)0.6455 (3)0.3307 (2)0.0353 (6)
O210.44541 (11)0.7397 (3)0.5260 (2)0.0336 (6)
O510.59492 (13)0.8004 (3)0.4230 (3)0.0439 (7)
O520.56407 (12)0.8959 (3)0.6051 (3)0.0416 (7)
O710.09501 (12)0.3048 (3)0.7434 (2)0.0377 (6)
N10.27937 (14)0.5196 (4)0.4377 (3)0.0326 (7)
N250.55395 (15)0.8132 (4)0.4958 (3)0.0356 (8)
C20.33194 (17)0.6361 (5)0.5242 (3)0.0325 (8)
H20.34510.58750.61960.039*
C30.29723 (17)0.8236 (5)0.5223 (4)0.0327 (8)
H3A0.28500.84830.61050.039*
H3B0.32680.92220.50330.039*
C40.23388 (18)0.8055 (5)0.4051 (4)0.0345 (9)
H40.22810.91510.34490.041*
C50.16989 (17)0.7652 (5)0.4518 (4)0.0349 (9)
H5A0.13100.76650.37220.042*
H5B0.16250.85960.51710.042*
C5a0.17550 (17)0.5794 (5)0.5206 (3)0.0308 (8)
C60.12920 (17)0.5190 (5)0.5933 (3)0.0313 (8)
H60.09080.59010.59680.038*
C70.13973 (17)0.3538 (5)0.6606 (3)0.0334 (8)
C80.19444 (18)0.2448 (5)0.6571 (4)0.0358 (9)
H80.20100.13310.70550.043*
C90.23916 (17)0.3016 (5)0.5820 (4)0.0341 (9)
H90.27650.22740.57660.041*
C9a0.22985 (17)0.4677 (5)0.5137 (3)0.0312 (8)
C220.39078 (17)0.6375 (5)0.4589 (3)0.0324 (8)
C230.40413 (17)0.5620 (5)0.3450 (4)0.0341 (9)
H230.37480.48580.28200.041*
C240.46951 (17)0.6165 (5)0.3362 (4)0.0347 (9)
H240.49270.58600.26730.042*
C250.49149 (17)0.7212 (5)0.4473 (4)0.0323 (8)
C710.04820 (19)0.1791 (6)0.6939 (4)0.0414 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0381 (16)0.0219 (17)0.0384 (16)0.0004 (13)0.0101 (14)0.0005 (14)
C20.040 (2)0.023 (2)0.0355 (19)0.0009 (16)0.0104 (16)0.0024 (16)
C30.0363 (19)0.023 (2)0.043 (2)0.0019 (15)0.0164 (16)0.0064 (16)
C40.044 (2)0.019 (2)0.041 (2)0.0012 (16)0.0127 (17)0.0002 (16)
C50.038 (2)0.023 (2)0.043 (2)0.0021 (15)0.0065 (17)0.0008 (16)
C5a0.0381 (19)0.020 (2)0.0328 (19)0.0003 (15)0.0050 (16)0.0033 (15)
C60.0323 (18)0.025 (2)0.0359 (19)0.0025 (15)0.0072 (16)0.0003 (16)
C70.0366 (19)0.029 (2)0.0374 (19)0.0047 (16)0.0134 (16)0.0017 (16)
C80.042 (2)0.020 (2)0.046 (2)0.0010 (16)0.0100 (18)0.0036 (16)
C90.0337 (19)0.021 (2)0.048 (2)0.0006 (16)0.0102 (17)0.0006 (17)
C9a0.0338 (19)0.024 (2)0.038 (2)0.0030 (15)0.0123 (16)0.0020 (16)
O140.0436 (14)0.0282 (14)0.0350 (13)0.0004 (11)0.0109 (11)0.0015 (11)
O710.0417 (14)0.0325 (16)0.0417 (14)0.0073 (12)0.0154 (12)0.0029 (12)
C710.037 (2)0.039 (3)0.051 (2)0.0023 (18)0.014 (2)0.0023 (19)
F10.0588 (15)0.0574 (17)0.0775 (17)0.0142 (12)0.0373 (14)0.0040 (13)
F20.0583 (15)0.0304 (15)0.111 (2)0.0096 (12)0.0353 (15)0.0079 (13)
F30.0505 (15)0.080 (2)0.0691 (17)0.0183 (13)0.0029 (13)0.0198 (15)
O210.0356 (14)0.0246 (14)0.0420 (14)0.0027 (11)0.0119 (12)0.0017 (11)
C220.0335 (19)0.022 (2)0.040 (2)0.0015 (15)0.0054 (16)0.0046 (16)
C230.038 (2)0.028 (2)0.038 (2)0.0045 (16)0.0110 (17)0.0038 (16)
C240.039 (2)0.029 (2)0.039 (2)0.0055 (17)0.0154 (17)0.0045 (17)
C250.0326 (19)0.024 (2)0.043 (2)0.0018 (16)0.0144 (17)0.0054 (17)
N250.0407 (18)0.0216 (18)0.0469 (19)0.0005 (14)0.0150 (16)0.0052 (15)
O510.0439 (15)0.0365 (16)0.0590 (17)0.0006 (12)0.0277 (14)0.0052 (13)
O520.0485 (16)0.0276 (15)0.0506 (16)0.0044 (12)0.0153 (13)0.0031 (13)
Geometric parameters (Å, º) top
N1—C9a1.449 (4)C7—O711.414 (4)
N1—O141.455 (4)C8—C91.374 (5)
N1—C21.490 (4)C8—H80.9500
C2—C221.493 (5)C9—C9a1.395 (5)
C2—C31.551 (5)C9—H90.9500
C2—H21.0000O71—C711.342 (4)
C3—C41.544 (5)C71—F11.313 (4)
C3—H3A0.9900C71—F31.329 (4)
C3—H3B0.9900C71—F21.334 (4)
C4—O141.457 (4)O21—C251.365 (4)
C4—C51.514 (5)O21—C221.387 (4)
C4—H41.0000C22—C231.353 (5)
C5—C5a1.526 (5)C23—C241.415 (5)
C5—H5A0.9900C23—H230.9500
C5—H5B0.9900C24—C251.346 (5)
C5a—C61.392 (5)C24—H240.9500
C5a—C9a1.396 (5)C25—N251.429 (5)
C6—C71.385 (5)N25—O521.231 (4)
C6—H60.9500N25—O511.232 (4)
C7—C81.383 (5)
C9a—N1—O14108.1 (2)C6—C7—O71117.5 (3)
C9a—N1—C2110.0 (2)C9—C8—C7118.6 (3)
O14—N1—C2101.7 (2)C9—C8—H8120.7
N1—C2—C22107.1 (3)C7—C8—H8120.7
N1—C2—C3103.9 (3)C8—C9—C9a120.2 (3)
C22—C2—C3113.5 (3)C8—C9—H9119.9
N1—C2—H2110.7C9a—C9—H9119.9
C22—C2—H2110.7C9—C9a—C5a121.0 (3)
C3—C2—H2110.7C9—C9a—N1117.2 (3)
C4—C3—C2103.5 (3)C5a—C9a—N1121.8 (3)
C4—C3—H3A111.1N1—O14—C4104.1 (2)
C2—C3—H3A111.1C71—O71—C7117.3 (3)
C4—C3—H3B111.1F1—C71—F3108.0 (3)
C2—C3—H3B111.1F1—C71—F2107.8 (3)
H3A—C3—H3B109.0F3—C71—F2106.7 (3)
O14—C4—C5106.3 (3)F1—C71—O71108.8 (3)
O14—C4—C3103.5 (3)F3—C71—O71112.7 (3)
C5—C4—C3114.5 (3)F2—C71—O71112.5 (3)
O14—C4—H4110.7C25—O21—C22104.4 (3)
C5—C4—H4110.7C23—C22—O21109.9 (3)
C3—C4—H4110.7C23—C22—C2134.7 (3)
C4—C5—C5a109.5 (3)O21—C22—C2115.4 (3)
C4—C5—H5A109.8C22—C23—C24108.0 (3)
C5a—C5—H5A109.8C22—C23—H23126.0
C4—C5—H5B109.8C24—C23—H23126.0
C5a—C5—H5B109.8C25—C24—C23104.7 (3)
H5A—C5—H5B108.2C25—C24—H24127.7
C6—C5a—C9a118.6 (3)C23—C24—H24127.7
C6—C5a—C5122.3 (3)C24—C25—O21113.1 (3)
C9a—C5a—C5119.1 (3)C24—C25—N25131.2 (3)
C7—C6—C5a119.2 (3)O21—C25—N25115.7 (3)
C7—C6—H6120.4O52—N25—O51124.5 (3)
C5a—C6—H6120.4O52—N25—C25119.7 (3)
C8—C7—C6122.4 (3)O51—N25—C25115.8 (3)
C8—C7—O71120.0 (3)
C9a—N1—C2—C22163.0 (3)C2—N1—C9a—C5a84.7 (4)
O14—N1—C2—C2282.6 (3)C9a—N1—O14—C466.3 (3)
C9a—N1—C2—C376.6 (3)C2—N1—O14—C449.5 (3)
O14—N1—C2—C337.8 (3)C5—C4—O14—N180.6 (3)
N1—C2—C3—C413.5 (3)C3—C4—O14—N140.3 (3)
C22—C2—C3—C4102.4 (3)C8—C7—O71—C7180.4 (4)
C2—C3—C4—O1415.6 (3)C6—C7—O71—C71104.3 (4)
C2—C3—C4—C599.7 (3)C7—O71—C71—F1177.7 (3)
O14—C4—C5—C5a49.2 (4)C7—O71—C71—F357.9 (4)
C3—C4—C5—C5a64.5 (4)C7—O71—C71—F262.9 (4)
C4—C5—C5a—C6169.2 (3)C25—O21—C22—C230.1 (4)
C4—C5—C5a—C9a9.1 (4)C25—O21—C22—C2179.5 (3)
C9a—C5a—C6—C72.4 (5)N1—C2—C22—C231.1 (5)
C5—C5a—C6—C7175.9 (3)C3—C2—C22—C23112.9 (4)
C5a—C6—C7—C80.8 (5)N1—C2—C22—O21179.8 (3)
C5a—C6—C7—O71174.4 (3)C3—C2—C22—O2166.2 (4)
C6—C7—C8—C91.2 (5)O21—C22—C23—C240.2 (4)
O71—C7—C8—C9176.2 (3)C2—C22—C23—C24178.9 (4)
C7—C8—C9—C9a1.4 (5)C22—C23—C24—C250.5 (4)
C8—C9—C9a—C5a0.3 (5)C23—C24—C25—O210.6 (4)
C8—C9—C9a—N1179.4 (3)C23—C24—C25—N25179.0 (3)
C6—C5a—C9a—C92.2 (5)C22—O21—C25—C240.4 (4)
C5—C5a—C9a—C9176.1 (3)C22—O21—C25—N25179.2 (3)
C6—C5a—C9a—N1178.7 (3)C24—C25—N25—O52176.7 (4)
C5—C5a—C9a—N12.9 (5)O21—C25—N25—O522.8 (5)
O14—N1—C9a—C9155.4 (3)C24—C25—N25—O512.2 (5)
C2—N1—C9a—C994.3 (4)O21—C25—N25—O51178.2 (3)
O14—N1—C9a—C5a25.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O14i0.992.503.474 (4)170
C3—H3B···O51ii0.992.603.504 (5)152
C8—H8···O14iii0.952.483.411 (4)166
C24—H24···O52iv0.952.423.338 (5)162
C4—H4···Cg1iii1.002.843.749 (4)152
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+2, z+1; (iii) x, y+1/2, z+1/2; (iv) x, y+3/2, z1/2.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC14H12N2O4C15H15FN2OC15H14FNO2C15H14FNOS
Mr272.26258.29259.27275.34
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/cMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)120120120120
a, b, c (Å)7.2248 (5), 18.1447 (19), 9.4504 (8)27.141 (4), 5.4082 (7), 17.2849 (18)5.5265 (5), 10.6652 (19), 20.905 (4)9.272 (2), 10.9142 (13), 12.963 (2)
α, β, γ (°)90, 94.279 (6), 9090, 103.275 (9), 9090, 97.166 (11), 9090, 101.023 (11), 90
V3)1235.42 (19)2469.3 (6)1222.6 (3)1287.6 (4)
Z4844
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.110.100.100.25
Crystal size (mm)0.38 × 0.27 × 0.220.41 × 0.27 × 0.100.26 × 0.25 × 0.140.36 × 0.19 × 0.14
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.960, 0.9760.961, 0.9900.974, 0.9860.914, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
18226, 2835, 1868 21463, 2824, 1511 17136, 2807, 1657 20089, 2944, 2049
Rint0.0470.0920.0610.059
(sin θ/λ)max1)0.6500.6500.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.139, 1.05 0.053, 0.148, 1.05 0.058, 0.175, 1.06 0.050, 0.135, 1.03
No. of reflections2835282428072944
No. of parameters181173173173
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.290.28, 0.230.29, 0.400.65, 0.50


(V)(VI)(VII)(VIII)
Crystal data
Chemical formulaC15H14FNOSC15H14ClNO2C16H14F3NO3C16H14F3NO2S
Mr275.34275.72325.28341.35
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/nTriclinic, P1Monoclinic, P21/c
Temperature (K)120120120120
a, b, c (Å)9.2106 (16), 10.906 (2), 13.4259 (13)10.2835 (13), 5.4829 (3), 23.428 (2)5.5088 (6), 10.7619 (17), 13.1398 (19)16.234 (3), 5.6113 (5), 16.665 (3)
α, β, γ (°)90, 106.086 (12), 9090, 96.665 (9), 90110.011 (10), 98.797 (10), 92.271 (12)90, 106.143 (14), 90
V3)1295.8 (4)1312.0 (2)719.80 (18)1458.2 (4)
Z4424
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.250.290.130.26
Crystal size (mm)0.39 × 0.24 × 0.100.42 × 0.18 × 0.140.41 × 0.19 × 0.080.38 × 0.32 × 0.24
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.908, 0.9750.889, 0.9610.949, 0.9900.906, 0.939
No. of measured, independent and
observed [I > 2σ(I)] reflections
20023, 2975, 1888 20222, 3017, 1902 21281, 3299, 1690 21849, 3348, 2493
Rint0.0820.0730.1110.070
(sin θ/λ)max1)0.6500.6500.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.106, 1.03 0.052, 0.143, 1.07 0.056, 0.147, 1.01 0.048, 0.128, 1.11
No. of reflections2975301732993348
No. of parameters173173209209
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.310.33, 0.440.26, 0.310.30, 0.42


(IX)
Crystal data
Chemical formulaC15H11F3N2O5
Mr356.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)20.4120 (15), 7.3690 (18), 10.035 (3)
α, β, γ (°)90, 103.091 (15), 90
V3)1470.2 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.26 × 0.25 × 0.14
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.963, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
18612, 2743, 1634
Rint0.081
(sin θ/λ)max1)0.607
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.183, 1.07
No. of reflections2743
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.32

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Ring-puckering parameters (Å, °) for (I)–(IX) top
(a)Five-membered rings
CompoundQ2ϕ2
(I)0.444 (2)13.3 (3)
(II)0.445 (2)16.9 (3)
(III)0.444 (2)19.5 (3)
(IV)0.447 (2)16.2 (3)
(V)0.457 (2)18.8 (3)
(VI)0.446 (2)15.4 (3)
(VII)0.443 (3)14.7 (4)
(VIII)0.434 (2)4.5 (3)
(IX)0.448 (2)17.0 (3)
(b)Six-membered rings
CompoundQθϕ
(I)0.607 (2)130.0 (2)164.7 (2)
(II)0.616 (2)129.7 (2)166.3 (3)
(III)0.617 (2)130.5 (2)162.3 (3)
(IV)0.621 (2)128.2 (2)166.3 (3)
(V)0.625 (2)127.0 (2)163.9 (2)
(VI)0.609 (2)130.6 (2)165.0 (3)
(VII)0.613 (2)129.6 (2)165.2 (3)
(VIII)0.606 (2)128.8 (2)170.1 (3)
(IX)0.627 (4)126.8 (4)162.5 (5)
(c)Seven-membered rings
CompoundQϕ2ϕ3
(I)1.126 (2)16.62 (11)300.6 (4)
(II)1.123 (2)16.61 (12)297.8 (4)
(III)1.143 (2)14.76 (12)297.8 (4)
(IV)1.111 (2)16.39 (13)298.8 (4)
(V)1.108 (2)14.36 (13)297.6 (4)
(VI)1.132 (2)16.55 (12)298.8 (4)
(VII)1.125 (2)16.77 (15)300.2 (5)
(VIII)1.109 (2)21.02 (13)306.8 (4)
(IX)1.117 (4)14.4 (2)299.0 (7)
Ring-puckering angles in the five-membered rings refer to the atom sequence O14—N1—C2—C3—C4. Ring-puckering angles in the six-membered rings refer to the atom sequence O14—N1—C9a—C5a—C5—C4. Ring-puckering angles in the seven-membered rings refer to the atom sequence N1—C2—C3—C4—C5—C5a—C9a.
Hydrogen-bond parameters (Å, °) for (I)–(IV) and (VI)–(IX) top
D—H···AD—HH···AD···AD—H···A
(I)
C24—H24···O51i0.952.453.359 (3)161
C5—H5B···Cg1a,ii0.992.663.458 (2)138
(II)
C5—H5A···O14iii0.992.583.530 (3)161
C25—H25···Cg1a,iv0.952.813.654 (2)149
(III)
C5—H5A···O14v0.992.553.527 (3)169
(IV)
C24—H24···Cg1a,vi0.952.563.443 (3)154
(VI)
C4—H4···O14vii1.002.493.312 (3)140
(VII)
C5—H5A···O14v0.992.583.545 (3)165
(VIII)
C5—H5A···O14viii0.992.413.383 (3)168
C3—H3A···Cg2b,viii0.992.703.533 (3)142
(IX)
C3—H3A···O51ix0.992.593.502 (5)153
C3—H3B···O14x0.992.503.475 (5)170
C8—H8···O14xi0.952.483.412 (6)165
C24—H24···O52ii0.952.423.340 (6)162
C4—H4···Cg1a,ii1.002.843.751 (5)152
Notes: (a) Cg1 represents the centroid of the C5a/C6–C9/C9a ring; (b) Cg2 represents the centroid of the S21/C22–C25 ring. Symmetry codes: (i) -x, -y + 1, -z; (ii) x, -y + 3/2, z - 1/2; (iii) x, y - 1, z; (iv) x, -y + 2, z - 1/2; (v) x + 1, y, z; (vi) x - 1/2, -y + 1/2, z + 1/2; (vii) -x + 1/2, y - 1/2, -z + 1/2; (viii) x, y + 1, z; (ix) -x + 1, -y + 2, -z + 1; (x) x, -y + 3/2, z + 1/2; (xi) x, -y + 1/2, z + 1/2.
 

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