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The title compounds, 2-(4-bromo­phenyl)-1,2-di­hydro­pyrimido­[1,2-a]­benzimidazol-4-(3H)-one, C16H12Br­N3O, (IVa), and 4-(4-methylphenyl)-3,4-dihydropyrimido[1,2-a]benzimidazol-2-(1H)-one, C17H15N3O, (Vb), both form R{_2^2}(8) centrosymmetric dimers via N—H...N hydrogen bonds. The N...N distance is 2.943 (3) Å for (IVa) and 2.8481 (16) Å for (Vb), with the corresponding N—H...N angles being 129 and 167°, respectively. However, in other respects, the supra­molecular structures of the two compounds differ. Both compounds contain different C—H...π interactions, in which the C—H...π(centroid) distances are 2.59 and 2.47 Å for (IVa) and (Vb), respectively (the latter being a short distance), with C—H...π(centroid) angles of 158 and 159°, respectively. The supramolecular structures also differ, with a short Br...O distance of 3.117 (2) Å in bromo derivative (IVa), and a C—H...O interaction with a C...O distance of 3.2561 (19) Å and a C—H...O angle of 127° in tolyl system (Vb). The di­hydro­pyrimido part of (Vb) is disordered, with a ratio of the major and minor components of 0.9:0.1. The disorder consists of two non-interchangeable envelope conformers, each with an equatorial tolyl group and an axial methine H atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101021564/gg1087sup1.cif
Contains datablocks global, IVa, Vb

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101021564/gg1087IVasup2.hkl
Contains datablock IVa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101021564/gg1087Vbsup3.hkl
Contains datablock Vb

CCDC references: 182046; 182047

Comment top

Benzimidazoles are associated with antiparasitic (Loewe et al., 1978), central nervous system depressant and anti-inflammatory (Yale & Bristol, 1977; Denzel & Hoehn, 1978a,b) and other pharmacological activities (Berg & Parnell, 1961; Mendzneritskaya et al., 1978; Paget et al., 1969, 1980). Hence, it may be expected that pyrimidobenzimidazoles such as the title compounds, (I) and (II), might display potent biological activity.

In previous research (Quiroga et al., 1999 and references therein) we have shown that the reaction between heterocyclic amines and benzylidene derivatives of compounds with an active methylene group, such Meldrum's acid, dimedone, malonodinitrile or ethyl cyanoacetate, is a good synthetic procedure to produce fused pyridinic and pyrimidinic systems. Here, we describe two regioisomer compounds obtained from the reaction of 2-aminobenzimidazole, (1), the benzaldehydes (2a) and (2 b) and Meldrum's acid, (3). The isomerism in the reaction is due to the two non-equivalent nucleophilic centres in (1), the NH2 group and the endo N. The formation of both products was observed in the two reactions. Related processes with Meldrum's acids are well known (McNab, 1978; Brown et al., 1974). Herein we describe the X-ray crystal structures for the crystalline derivatives with R = Br, (4a), hereinafter (I), and R = CH3, (5 b), hereinafter (II). \sch

Compound (I) (Fig. 1) crystallizes in the monoclinic spacegroup P21/c and (II) (Fig. 2) in the triclinic spacegroup P1. In (II), there is disorder involving the envelope dihydropyrimido part of the molecule, such that the C atom of the envelope lies below and above the mean plane of the other five ring atoms, for the major and minor components, respectively, which are in the ratio 0.9:0.1. This disorder consists of two non-interchangeable conformers, each with an equatorial tolyl group and an axial methine H atom. Thus, two enantiomers are present, since a straightforward `flip' of the envelope would give an axial tolyl and an equatorial H. A view of the two components of the disorder is shown in Fig. 3.

In both compounds, an R22(8) centrosymmetric base-paired dimer (Bernstein et al., 1995) is formed, via the N1—H1···N10(2 - x, 1 - y, -z) hydrogen bond in (I) (Fig. 4) and the corresponding N1—H1···N10(2 - x, 1 - y, 1 - z) hydrogen bond in (II). There is a short Br24.. O4(1 - x, 1/2 + y, 1/2 - z) contact of 3.117 (2) Å in (I). In the case of (II), there is a weak C3—H3A···O2(2 - x, 1 - y, 1 - z)hydrogen bond, with a C···O distance of 3.2561 (19) Å and a C3—H3A···O2 angle of 127 Å. This latter interaction forms an R22(8) ring. These two ring structures link the molecules into a continuous ribbon which runs parallel to the b axis. Alternatively, this ribbon can be regarded as being formed by two antiparallel C22(10) centrosymmetrically related chains (Fig. 5).

The supramolecular structures of the two compounds differ in other respects as well. Both compounds contain different C—H···π(arene) interactions. In (I), there is a C9—H9···CgX(2 - x, 1 - y, -z) contact of 2.59 Å, where CgX is the centroid of ring X, and X is the ring C21—C26. The perpendicular distance C9···CgX is 2.58 Å and the angle at H9 is 158°. This interaction reinforces the strong N—H···O bond described above, since it involves the same two molecules which are thus linked head-to-tail. This interaction can be seen in Figs. 4 and 6. Thus in (I), the main supramolecular structure is the dimer.

In (II), there is a C4A—H4A···CgY(1 - x, 1 - y, 1 - z) contact of 2.47 Å (Y is the ring C5a—C9a). The perpendicular distance C4A···CgY (Please check C4A is correct - C9 given in original CIF) is 2.43 Å and the angle at H4A is 159°. This H···π distance is rather short at ca 2.40 Å, if C—H is given the neutron value of 1.083 Å. This means that it lies within 0.10–0.15 Å of the values found in some alkynyltetraborate structures (Lindeman et al., 1998). Fig. 7 shows that the molecules are linked head-to-tail by this interaction. The minor component of (II) is not involved in any such interaction. Details of all hydrogen bonding are given in Tables 1 and 2.

Only one similar compound which includes H atoms in the analysis was found in the Cambridge Structural Database (CSD, Release?; Allen & Kennard, 1993), namely 2,2-dimethyl-1,2,3,4-tetrahydrobenzimidazo[3,2-a]pyrimid-4-one (VOBLAZ; Bird et al., 1991). In this structure, an identical dimer to that found for (I) and (II) is formed, with an N···N distance of 3.037 (3) Å and an angle at H of 175°. There are C—H···O contacts, but these are too long to be classed as weak hydrogen bonds. In addition, there is a C—H···π(arene) contact involving a methyl H atom of 2.79 Å (perpendicular distance 2.78 Å), with an angle at H of 176°. One noticeable feature of this compound which differs markedly from (I) and (II) is the difference in the angles at the H atoms, which suggests that the interplay between the C—H···π hydrogen bonds, which are very much shorter in (I) and (II) than in VOBLAZ, may have sufficient strength to distort the N—H···N hydrogen bonds in (I) and (II).

Experimental top

A solution of 2-aminobenzimidazole, (1) (2.0 mmoles), and an equimolar amount of 4-bromobenzaldehyde, (2a), or 4-tolualdehyde, (2 b), and Meldrum's acid, (3), in ethanol (20 ml) was refluxed for 1–2 h with thin-layer chromatography control. The solvent was then removed and the resulting precipitate was filtered, washed with ethanol, dried and purified by silica gel chromatography with ethyl acetate as the eluent. The title compounds were eluted in the order (4) then (5) from the column. Colourless crystals suitable for X-ray diffraction were obtained directly from the chromatographic fractions. (I): 20% yield, m.p. 577 K; (II): 69% yield, m.p. 506 K.

Refinement top

All H atoms were treated as riding, with C—H = 0.95 Å (phenyl H) for (I) and 1.00 Å (methine H) for (II). A residual electron density peak of 0.75 e Å-3 was found in the final stages of refinement for (II) at 1.2 Å from C4A, 1.45 Å from C3 and 1.63 Å from N5. This suggested that two envelope forms were present for the dihydropyrimido part of the molecule and it was found that this was the case. Since the next difference map peaks were less than 0.3 e Å-3, the nature of the disorder was not immediately obvious. When atom C4B was put at the position of the difference map peak and atom C4A and the attached tolyl group were refined with a free variable, such that the combined site occupancy factors added up to 1.0, then a minor component consisting of C4B and a staggered tolyl group overlapping the major component tolyl group was found from the resulting difference map (Fig. 6). The minor component was modelled using appropriate DFIX constraints to optimize the position of C4B with respect to C4A, C3, N5 and C41B. ISOR and DELU constraints were applied to the phenyl ring atoms of the minor component (SHELXL97; Sheldrick, 1997). The ratio of major to minor components is ca 0.9:0.1 and consists of two non-interchangeable conformers, each with an axial tolyl group.

Computing details top

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of the major component of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. A view of the major and minor components in the disorder of (II). Only the dihydropyrimido part of the molecule and the tolyl groups are shown and the methyl H atoms have been omitted for clarity.
[Figure 4] Fig. 4. A view of the R22(8) base-paired dimer in (I).
[Figure 5] Fig. 5. A view of the ribbon structure in (II); only the major component is shown. H atoms not involved in the hydrogen bonding have been omitted for clarity. The molecule labelled * is at (2 - x, 1 - y, 1 - z), that labelled # is at (x, y - 1, z) and that labelled $ is at (2 - x, 2 - y, 1 - z).
[Figure 6] Fig. 6. A view of the C—H···π interaction for (I) perpendicular to the ring at C21; atom C9* is in the molecule at (2 - x, 1 - y, -z).
[Figure 7] Fig. 7. A view of the C—H···π interaction for (II) perpendicular to the ring at C5A; atom C4A* is in the molecule at (1 - x, 1 - y, 1 - z).
(IVa) 2-(4-Bromophenyl)-1,2-dihydropyrimido[1,2-a]benzimidazol-4(3H)-one top
Crystal data top
C16H12BrN3OF(000) = 688
Mr = 342.20Dx = 1.638 Mg m3
Monoclinic, P21/cMelting point: 577 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.8807 (2) ÅCell parameters from 3046 reflections
b = 16.2254 (6) Åθ = 3.0–27.4°
c = 13.3379 (5) ŵ = 2.96 mm1
β = 111.280 (2)°T = 120 K
V = 1387.54 (8) Å3Lath, colourless
Z = 40.20 × 0.06 × 0.02 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3046 independent reflections
Radiation source: fine-focus sealed X-ray tube2401 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.078
ϕ scans, and ω scans with κ offsetsθmax = 27.4°, θmin = 3.0°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 88
Tmin = 0.589, Tmax = 0.943k = 2121
8697 measured reflectionsl = 1713
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0658P)2]
where P = (Fo2 + 2Fc2)/3
3046 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.71 e Å3
0 restraintsΔρmin = 1.55 e Å3
Crystal data top
C16H12BrN3OV = 1387.54 (8) Å3
Mr = 342.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.8807 (2) ŵ = 2.96 mm1
b = 16.2254 (6) ÅT = 120 K
c = 13.3379 (5) Å0.20 × 0.06 × 0.02 mm
β = 111.280 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
3046 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
2401 reflections with I > 2σ(I)
Tmin = 0.589, Tmax = 0.943Rint = 0.078
8697 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.01Δρmax = 0.71 e Å3
3046 reflectionsΔρmin = 1.55 e Å3
190 parameters
Special details top

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code-word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the SIZE command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.8909 (4)0.40997 (15)0.06599 (19)0.0202 (5)
C20.8971 (5)0.36859 (17)0.1653 (2)0.0202 (6)
C210.7504 (5)0.41219 (17)0.2108 (2)0.0203 (6)
C220.5453 (5)0.43433 (17)0.1448 (3)0.0234 (7)
C230.4160 (5)0.47768 (19)0.1863 (2)0.0227 (6)
C240.4927 (4)0.49813 (17)0.2952 (2)0.0200 (6)
Br240.31283 (5)0.557959 (18)0.34998 (2)0.02561 (14)
C250.6932 (5)0.47610 (18)0.3619 (2)0.0226 (6)
C260.8204 (5)0.43347 (17)0.3187 (3)0.0232 (7)
C30.8401 (5)0.27790 (18)0.1389 (2)0.0227 (6)
C40.9671 (4)0.23567 (17)0.0811 (2)0.0206 (6)
O40.9921 (4)0.16254 (12)0.07701 (17)0.0271 (5)
N51.0538 (4)0.29104 (14)0.02729 (18)0.0174 (5)
C5A1.1695 (5)0.27315 (18)0.0394 (2)0.0196 (6)
C61.2800 (5)0.20374 (17)0.0502 (2)0.0224 (6)
C71.3886 (5)0.21007 (19)0.1201 (3)0.0256 (7)
C81.3865 (5)0.2825 (2)0.1770 (3)0.0276 (7)
C91.2770 (5)0.35229 (19)0.1643 (2)0.0239 (7)
C9A1.1727 (4)0.34733 (17)0.0929 (2)0.0197 (6)
N101.0655 (4)0.40985 (15)0.05954 (19)0.0190 (5)
C10A0.9990 (5)0.37510 (17)0.0111 (2)0.0181 (6)
H10.81940.45570.04350.024*
H21.04250.37180.21950.024*
H220.49430.41950.07090.028*
H230.27870.49290.14130.027*
H250.74300.49000.43610.027*
H260.95780.41870.36410.028*
H3A0.86080.24790.20670.027*
H3B0.69040.27420.09330.027*
H61.28120.15440.01170.027*
H71.46580.16400.12930.031*
H81.46010.28450.22500.033*
H91.27440.40140.20350.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0244 (14)0.0171 (12)0.0212 (13)0.0060 (11)0.0107 (11)0.0011 (10)
C20.0209 (15)0.0196 (14)0.0209 (15)0.0006 (12)0.0082 (12)0.0019 (12)
C210.0211 (16)0.0143 (13)0.0278 (16)0.0008 (12)0.0116 (13)0.0019 (12)
C220.0274 (17)0.0238 (16)0.0206 (15)0.0036 (13)0.0105 (13)0.0053 (12)
C230.0203 (15)0.0230 (15)0.0238 (15)0.0003 (13)0.0070 (12)0.0019 (13)
C240.0235 (15)0.0162 (13)0.0244 (15)0.0013 (12)0.0135 (12)0.0012 (12)
Br240.0305 (2)0.0222 (2)0.0303 (2)0.00089 (12)0.01833 (16)0.00318 (12)
C250.0265 (16)0.0233 (15)0.0189 (14)0.0017 (14)0.0095 (12)0.0022 (12)
C260.0237 (17)0.0204 (15)0.0260 (16)0.0013 (12)0.0096 (13)0.0052 (12)
C30.0267 (16)0.0170 (14)0.0271 (16)0.0035 (13)0.0132 (13)0.0002 (13)
C40.0235 (16)0.0162 (14)0.0212 (15)0.0006 (12)0.0072 (12)0.0002 (11)
O40.0394 (13)0.0145 (10)0.0329 (12)0.0012 (9)0.0197 (10)0.0022 (9)
N50.0200 (13)0.0127 (11)0.0203 (12)0.0014 (10)0.0084 (10)0.0013 (10)
C5A0.0224 (15)0.0192 (14)0.0177 (14)0.0013 (12)0.0080 (12)0.0012 (12)
C60.0234 (16)0.0146 (13)0.0263 (15)0.0015 (12)0.0056 (13)0.0039 (12)
C70.0239 (16)0.0213 (15)0.0338 (17)0.0026 (14)0.0128 (14)0.0088 (14)
C80.0307 (18)0.0271 (16)0.0294 (17)0.0038 (14)0.0164 (14)0.0084 (14)
C90.0327 (17)0.0187 (15)0.0240 (16)0.0036 (13)0.0149 (13)0.0012 (12)
C9A0.0217 (15)0.0169 (14)0.0197 (14)0.0005 (12)0.0065 (12)0.0040 (11)
N100.0246 (13)0.0144 (11)0.0209 (12)0.0021 (10)0.0120 (11)0.0003 (10)
C10A0.0200 (14)0.0148 (13)0.0192 (14)0.0004 (12)0.0066 (11)0.0023 (11)
Geometric parameters (Å, º) top
N1—C10A1.343 (4)C3—H3A0.9900
N1—C21.472 (4)C3—H3B0.9900
N1—H10.8800C4—O41.203 (3)
C2—C211.527 (4)C4—N51.411 (4)
C2—C31.531 (4)N5—C10A1.411 (3)
C2—H21.0000N5—C5A1.422 (4)
C21—C261.385 (4)C5A—C61.395 (4)
C21—C221.412 (4)C5A—C9A1.404 (4)
C22—C231.396 (4)C6—C71.394 (4)
C22—H220.9500C6—H60.9500
C23—C241.393 (4)C7—C81.395 (5)
C23—H230.9500C7—H70.9500
C24—C251.389 (4)C8—C91.404 (4)
C24—Br241.914 (3)C8—H80.9500
C25—C261.394 (4)C9—C9A1.388 (4)
C25—H250.9500C9—H90.9500
C26—H260.9500C9A—N101.417 (4)
C3—C41.522 (4)N10—C10A1.314 (4)
C10A—N1—C2117.2 (2)C2—C3—H3B108.8
C10A—N1—H1121.4H3A—C3—H3B107.7
C2—N1—H1121.4O4—C4—N5120.7 (3)
N1—C2—C21109.8 (2)O4—C4—C3125.8 (3)
N1—C2—C3108.1 (2)N5—C4—C3113.4 (2)
C21—C2—C3112.7 (2)C4—N5—C10A123.7 (2)
N1—C2—H2108.7C4—N5—C5A128.6 (2)
C21—C2—H2108.7C10A—N5—C5A106.3 (2)
C3—C2—H2108.7C6—C5A—C9A122.0 (3)
C26—C21—C22118.4 (3)C6—C5A—N5132.8 (3)
C26—C21—C2119.8 (3)C9A—C5A—N5105.0 (2)
C22—C21—C2121.7 (3)C7—C6—C5A117.0 (3)
C23—C22—C21121.1 (3)C7—C6—H6121.5
C23—C22—H22119.4C5A—C6—H6121.5
C21—C22—H22119.4C6—C7—C8121.5 (3)
C24—C23—C22118.6 (3)C6—C7—H7119.2
C24—C23—H23120.7C8—C7—H7119.2
C22—C23—H23120.7C7—C8—C9120.9 (3)
C25—C24—C23121.2 (3)C7—C8—H8119.5
C25—C24—Br24121.0 (2)C9—C8—H8119.5
C23—C24—Br24117.8 (2)C9A—C9—C8118.0 (3)
C24—C25—C26119.3 (3)C9A—C9—H9121.0
C24—C25—H25120.3C8—C9—H9121.0
C26—C25—H25120.3C9—C9A—C5A120.4 (3)
C21—C26—C25121.3 (3)C9—C9A—N10129.2 (3)
C21—C26—H26119.4C5A—C9A—N10110.4 (3)
C25—C26—H26119.4C10A—N10—C9A105.9 (2)
C4—C3—C2113.8 (2)N10—C10A—N1128.0 (3)
C4—C3—H3A108.8N10—C10A—N5112.4 (2)
C2—C3—H3A108.8N1—C10A—N5119.6 (3)
C4—C3—H3B108.8
C10A—N1—C2—C21174.8 (2)C10A—N5—C5A—C6173.0 (3)
C10A—N1—C2—C351.5 (3)C4—N5—C5A—C9A165.7 (3)
N1—C2—C21—C26131.3 (3)C10A—N5—C5A—C9A1.2 (3)
C3—C2—C21—C26108.2 (3)C9A—C5A—C6—C72.3 (4)
N1—C2—C21—C2246.5 (4)N5—C5A—C6—C7175.7 (3)
C3—C2—C21—C2274.0 (3)C5A—C6—C7—C80.2 (4)
C26—C21—C22—C230.9 (4)C6—C7—C8—C91.1 (5)
C2—C21—C22—C23176.9 (3)C7—C8—C9—C9A0.6 (5)
C21—C22—C23—C240.7 (4)C8—C9—C9A—C5A3.0 (4)
C22—C23—C24—C250.1 (4)C8—C9—C9A—N10174.7 (3)
C22—C23—C24—Br24179.7 (2)C6—C5A—C9A—C94.0 (4)
C23—C24—C25—C260.6 (4)N5—C5A—C9A—C9179.0 (3)
Br24—C24—C25—C26179.2 (2)C6—C5A—C9A—N10174.1 (3)
C22—C21—C26—C250.3 (4)N5—C5A—C9A—N100.9 (3)
C2—C21—C26—C25177.5 (3)C9—C9A—N10—C10A178.2 (3)
C24—C25—C26—C210.4 (4)C5A—C9A—N10—C10A0.2 (3)
N1—C2—C3—C451.5 (3)C9A—N10—C10A—N1179.3 (3)
C21—C2—C3—C4173.0 (2)C9A—N10—C10A—N50.6 (3)
C2—C3—C4—O4159.2 (3)C2—N1—C10A—N10159.2 (3)
C2—C3—C4—N522.4 (4)C2—N1—C10A—N520.6 (4)
O4—C4—N5—C10A167.4 (3)C4—N5—C10A—N10166.6 (2)
C3—C4—N5—C10A11.1 (4)C5A—N5—C10A—N101.1 (3)
O4—C4—N5—C5A2.5 (5)C4—N5—C10A—N113.6 (4)
C3—C4—N5—C5A175.9 (3)C5A—N5—C10A—N1178.7 (2)
C4—N5—C5A—C620.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N10i0.882.302.943 (3)129
C9—H9···CgXi0.952.593.501 (3)158
Symmetry code: (i) x+2, y+1, z.
(Vb) 4-(4-Methylphenyl)-3,4-dihydropyrimido[1,2-a]benzimidazol-2(1H)-one top
Crystal data top
C17H15N3OZ = 2
Mr = 277.32F(000) = 292
Triclinic, P1Dx = 1.299 Mg m3
Hall symbol: p-1Melting point: 506 K
a = 8.1360 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.8647 (4) ÅCell parameters from 3170 reflections
c = 10.0975 (5) Åθ = 3.0–27.5°
α = 114.8796 (13)°µ = 0.08 mm1
β = 94.9156 (15)°T = 120 K
γ = 100.966 (3)°Block, colourless
V = 709.18 (5) Å30.1 × 0.1 × 0.1 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3170 independent reflections
Radiation source: fine-focus sealed X-ray tube2247 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 1010
Tmin = 0.992, Tmax = 0.992k = 1212
10703 measured reflectionsl = 1313
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0664P)2 + 0.0023P]
where P = (Fo2 + 2Fc2)/3
3170 reflections(Δ/σ)max < 0.001
264 parametersΔρmax = 0.21 e Å3
52 restraintsΔρmin = 0.21 e Å3
Crystal data top
C17H15N3Oγ = 100.966 (3)°
Mr = 277.32V = 709.18 (5) Å3
Triclinic, P1Z = 2
a = 8.1360 (3) ÅMo Kα radiation
b = 9.8647 (4) ŵ = 0.08 mm1
c = 10.0975 (5) ÅT = 120 K
α = 114.8796 (13)°0.1 × 0.1 × 0.1 mm
β = 94.9156 (15)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
3170 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
2247 reflections with I > 2σ(I)
Tmin = 0.992, Tmax = 0.992Rint = 0.056
10703 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04652 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.05Δρmax = 0.21 e Å3
3170 reflectionsΔρmin = 0.21 e Å3
264 parameters
Special details top

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code-word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the SIZE command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.91899 (12)0.67969 (12)0.51394 (12)0.0258 (3)
C20.90560 (16)0.82721 (16)0.55341 (15)0.0266 (3)
O21.01688 (11)0.93793 (11)0.64295 (11)0.0350 (3)
C30.75014 (16)0.84074 (15)0.47112 (16)0.0292 (3)
C4A0.58901 (17)0.71272 (16)0.43032 (16)0.0217 (4)0.907 (4)
C41A0.4544 (3)0.71274 (19)0.3174 (3)0.0205 (4)0.907 (4)
C42A0.4750 (2)0.6777 (2)0.1723 (3)0.0272 (5)0.907 (4)
C43A0.3473 (4)0.6760 (2)0.0706 (2)0.0293 (6)0.907 (4)
C44A0.1950 (4)0.7105 (4)0.1112 (3)0.0263 (7)0.907 (4)
C45A0.1757 (3)0.7467 (3)0.2567 (3)0.0273 (6)0.907 (4)
C46A0.3029 (3)0.7475 (2)0.35847 (19)0.0229 (5)0.907 (4)
C47A0.0573 (3)0.7103 (2)0.0022 (3)0.0411 (5)0.907 (4)
N50.63728 (12)0.56436 (12)0.37319 (12)0.0222 (3)
C5A0.53518 (16)0.41306 (15)0.29563 (14)0.0229 (3)
C60.36396 (16)0.35199 (16)0.23039 (15)0.0305 (4)
C70.30616 (18)0.19275 (16)0.16268 (17)0.0339 (4)
C80.41401 (17)0.09745 (16)0.15937 (15)0.0309 (4)
C90.58416 (17)0.15874 (16)0.22647 (14)0.0263 (3)
C9A0.64417 (15)0.31836 (15)0.29690 (14)0.0217 (3)
N100.80576 (13)0.40885 (13)0.37738 (12)0.0251 (3)
C10A0.79250 (15)0.55081 (15)0.42150 (14)0.0217 (3)
C4B0.6609 (15)0.7020 (14)0.3331 (15)0.025 (4)0.093 (4)
C41B0.492 (2)0.710 (2)0.259 (3)0.019 (4)0.093 (4)
C42B0.377 (4)0.735 (2)0.346 (2)0.017 (4)0.093 (4)
C43B0.215 (3)0.742 (3)0.292 (3)0.020 (4)0.093 (4)
C44B0.172 (3)0.712 (4)0.149 (4)0.013 (4)0.093 (4)
C45B0.280 (4)0.680 (3)0.070 (3)0.019 (4)0.093 (4)
C46B0.442 (3)0.684 (2)0.113 (3)0.022 (4)0.093 (4)
C47B0.001 (3)0.714 (3)0.066 (3)0.058 (7)0.093 (4)
H11.01400.66660.54980.031*
H3A0.77800.84350.37860.035*
H3B0.72540.94060.53310.035*
H4A0.54160.72820.52230.026*0.907 (4)
H42A0.57790.65470.14220.033*0.907 (4)
H43A0.36380.65090.02820.035*0.907 (4)
H45A0.07360.77140.28730.033*0.907 (4)
H46A0.28620.77200.45710.028*0.907 (4)
H47A0.10640.72230.07870.062*0.4535 (18)
H47B0.00560.79600.05260.062*0.4535 (18)
H47C0.03000.61250.03840.062*0.4535 (18)
H47D0.05170.69820.03570.062*0.4535 (18)
H47E0.04900.62450.09560.062*0.4535 (18)
H47F0.08470.80800.00460.062*0.4535 (18)
H60.29010.41630.23210.037*
H70.18960.14700.11710.041*
H80.36990.01140.11020.037*
H90.65740.09380.22440.032*
H4B0.73920.68520.25970.030*0.093 (4)
H42B0.40370.74770.44480.021*0.093 (4)
H43B0.13550.76760.35710.024*0.093 (4)
H45B0.24480.64960.03270.023*0.093 (4)
H46B0.51990.66890.04670.026*0.093 (4)
H47G0.08690.61870.04210.087*0.0465 (18)
H47H0.01770.72100.02550.087*0.0465 (18)
H47I0.03970.80300.13090.087*0.0465 (18)
H47J0.01430.80980.05620.087*0.0465 (18)
H47K0.09030.70740.12380.087*0.0465 (18)
H47L0.03290.62550.03260.087*0.0465 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0172 (6)0.0244 (6)0.0357 (7)0.0054 (5)0.0014 (5)0.0140 (5)
C20.0216 (7)0.0258 (8)0.0345 (8)0.0060 (6)0.0059 (6)0.0151 (7)
O20.0270 (6)0.0259 (6)0.0458 (7)0.0012 (4)0.0021 (5)0.0140 (5)
C30.0257 (7)0.0226 (7)0.0391 (9)0.0068 (6)0.0015 (6)0.0141 (7)
C4A0.0221 (8)0.0201 (8)0.0248 (9)0.0073 (6)0.0050 (6)0.0107 (6)
C41A0.0221 (10)0.0175 (8)0.0245 (10)0.0078 (7)0.0057 (8)0.0105 (8)
C42A0.0298 (10)0.0318 (10)0.0274 (13)0.0160 (8)0.0094 (9)0.0160 (10)
C43A0.0322 (15)0.0361 (11)0.0264 (10)0.0148 (11)0.0094 (11)0.0169 (8)
C44A0.0315 (14)0.0232 (10)0.0266 (16)0.0081 (9)0.0027 (11)0.0131 (12)
C45A0.0187 (11)0.0329 (10)0.0310 (16)0.0087 (8)0.0020 (8)0.0145 (10)
C46A0.0207 (11)0.0252 (9)0.0232 (9)0.0072 (8)0.0042 (8)0.0104 (7)
C47A0.0374 (12)0.0423 (11)0.0421 (13)0.0085 (9)0.0089 (9)0.0210 (10)
N50.0191 (6)0.0210 (6)0.0285 (6)0.0069 (4)0.0021 (4)0.0125 (5)
C5A0.0248 (7)0.0213 (7)0.0245 (7)0.0069 (5)0.0044 (5)0.0116 (6)
C60.0255 (8)0.0278 (8)0.0366 (8)0.0066 (6)0.0026 (6)0.0144 (7)
C70.0285 (8)0.0280 (8)0.0385 (9)0.0025 (6)0.0057 (6)0.0128 (7)
C80.0371 (8)0.0227 (7)0.0282 (8)0.0044 (6)0.0015 (6)0.0090 (6)
C90.0322 (8)0.0245 (7)0.0245 (7)0.0117 (6)0.0056 (6)0.0112 (6)
C9A0.0239 (7)0.0238 (7)0.0206 (7)0.0083 (5)0.0047 (5)0.0117 (6)
N100.0224 (6)0.0241 (6)0.0286 (6)0.0078 (5)0.0026 (5)0.0113 (5)
C10A0.0191 (7)0.0247 (7)0.0251 (7)0.0074 (5)0.0058 (5)0.0134 (6)
C4B0.022 (8)0.023 (8)0.040 (10)0.006 (6)0.013 (6)0.022 (7)
C41B0.016 (5)0.022 (6)0.019 (5)0.006 (4)0.003 (3)0.010 (4)
C42B0.018 (5)0.023 (6)0.016 (5)0.007 (4)0.002 (3)0.012 (4)
C43B0.018 (5)0.029 (6)0.016 (5)0.010 (4)0.005 (4)0.009 (4)
C44B0.014 (5)0.012 (6)0.014 (5)0.006 (4)0.001 (4)0.006 (4)
C45B0.020 (5)0.023 (6)0.016 (5)0.006 (5)0.003 (3)0.009 (4)
C46B0.020 (5)0.029 (6)0.018 (5)0.007 (4)0.005 (4)0.009 (4)
C47B0.036 (12)0.076 (16)0.051 (15)0.022 (10)0.021 (10)0.013 (12)
Geometric parameters (Å, º) top
N1—C21.3668 (17)C5A—C61.3882 (18)
N1—C10A1.3732 (16)C5A—C9A1.4080 (18)
N1—H10.8800C6—C71.384 (2)
C2—O21.2176 (16)C6—H60.9500
C2—C31.5118 (17)C7—C81.395 (2)
C3—C4B1.478 (13)C7—H70.9500
C3—C4A1.5242 (18)C8—C91.3846 (19)
C3—H3A0.9900C8—H80.9500
C3—H3B0.9900C9—C9A1.3889 (19)
C4A—N51.4752 (17)C9—H90.9500
C4A—C41A1.512 (2)C9A—N101.3948 (16)
C4A—H4A1.0000N10—C10A1.3084 (17)
C41A—C42A1.390 (3)C4B—C41B1.541 (18)
C41A—C46A1.391 (3)C4B—H4B1.0000
C42A—C43A1.389 (3)C41B—C42B1.32 (3)
C42A—H42A0.9500C41B—C46B1.39 (3)
C43A—C44A1.396 (3)C42B—C43B1.41 (3)
C43A—H43A0.9500C42B—H42B0.9500
C44A—C45A1.389 (3)C43B—C44B1.35 (3)
C44A—C47A1.501 (3)C43B—H43B0.9500
C45A—C46A1.391 (2)C44B—C45B1.23 (3)
C45A—H45A0.9500C44B—C47B1.58 (4)
C46A—H46A0.9500C45B—C46B1.34 (3)
C47A—H47A0.9800C45B—H45B0.9500
C47A—H47B0.9800C46B—H46B0.9500
C47A—H47C0.9800C47B—H47G0.9800
C47A—H47D0.9800C47B—H47H0.9800
C47A—H47E0.9800C47B—H47I0.9800
C47A—H47F0.9800C47B—H47J0.9800
N5—C10A1.3653 (15)C47B—H47K0.9800
N5—C5A1.4016 (17)C47B—H47L0.9800
N5—C4B1.555 (12)
C2—N1—C10A123.66 (11)C7—C8—H8119.4
C2—N1—H1118.2C8—C9—C9A117.79 (13)
C10A—N1—H1118.2C8—C9—H9121.1
O2—C2—N1121.28 (12)C9A—C9—H9121.1
O2—C2—C3123.55 (12)C9—C9A—N10129.38 (12)
N1—C2—C3115.07 (11)C9—C9A—C5A120.45 (12)
C4B—C3—C2116.0 (5)N10—C9A—C5A110.15 (11)
C4B—C3—C4A45.5 (5)C10A—N10—C9A104.27 (10)
C2—C3—C4A115.86 (11)N10—C10A—N5114.87 (11)
C4B—C3—H3A65.4N10—C10A—N1124.52 (11)
C2—C3—H3A108.3N5—C10A—N1120.56 (11)
C4A—C3—H3A108.3C3—C4B—C41B115.7 (12)
C4B—C3—H3B135.2C3—C4B—N5106.1 (8)
C2—C3—H3B108.3C41B—C4B—N5112.0 (11)
C4A—C3—H3B108.3C3—C4B—H4B107.6
H3A—C3—H3B107.4C41B—C4B—H4B107.6
N5—C4A—C41A110.90 (12)N5—C4B—H4B107.6
N5—C4A—C3107.85 (10)C42B—C41B—C46B117.3 (16)
C41A—C4A—C3112.18 (13)C42B—C41B—C4B114 (2)
N5—C4A—H4A108.6C46B—C41B—C4B129 (2)
C41A—C4A—H4A108.6C41B—C42B—C43B120.2 (17)
C3—C4A—H4A108.6C41B—C42B—H42B119.9
C42A—C41A—C46A118.19 (15)C43B—C42B—H42B119.9
C42A—C41A—C4A122.4 (2)C44B—C43B—C42B120 (2)
C46A—C41A—C4A119.4 (2)C44B—C43B—H43B120.1
C43A—C42A—C41A120.92 (17)C42B—C43B—H43B120.1
C43A—C42A—H42A119.5C45B—C44B—C43B118 (3)
C41A—C42A—H42A119.5C45B—C44B—C47B114 (3)
C42A—C43A—C44A121.10 (19)C43B—C44B—C47B128 (3)
C42A—C43A—H43A119.4C44B—C45B—C46B127 (2)
C44A—C43A—H43A119.4C44B—C45B—H45B116.5
C45A—C44A—C43A117.7 (2)C46B—C45B—H45B116.5
C45A—C44A—C47A121.0 (3)C45B—C46B—C41B118 (2)
C43A—C44A—C47A121.3 (2)C45B—C46B—H46B121.2
C44A—C45A—C46A121.3 (2)C41B—C46B—H46B121.2
C44A—C45A—H45A119.4C44B—C47B—H47G109.5
C46A—C45A—H45A119.4C44B—C47B—H47H109.5
C45A—C46A—C41A120.78 (17)H47G—C47B—H47H109.5
C45A—C46A—H46A119.6C44B—C47B—H47I109.5
C41A—C46A—H46A119.6H47G—C47B—H47I109.5
C10A—N5—C5A105.53 (10)H47H—C47B—H47I109.5
C10A—N5—C4A122.62 (10)C44B—C47B—H47J109.5
C5A—N5—C4A130.07 (10)H47G—C47B—H47J141.1
C10A—N5—C4B109.9 (5)H47H—C47B—H47J56.3
C5A—N5—C4B130.7 (5)H47I—C47B—H47J56.3
C4A—N5—C4B45.0 (5)C44B—C47B—H47K109.5
C6—C5A—N5133.08 (12)H47G—C47B—H47K56.3
C6—C5A—C9A121.84 (12)H47H—C47B—H47K141.1
N5—C5A—C9A105.05 (10)H47I—C47B—H47K56.3
C7—C6—C5A116.74 (13)H47J—C47B—H47K109.5
C7—C6—H6121.6C44B—C47B—H47L109.5
C5A—C6—H6121.6H47G—C47B—H47L56.3
C6—C7—C8121.96 (13)H47H—C47B—H47L56.3
C6—C7—H7119.0H47I—C47B—H47L141.1
C8—C7—H7119.0H47J—C47B—H47L109.5
C9—C8—C7121.16 (13)H47K—C47B—H47L109.5
C9—C8—H8119.4
C10A—N1—C2—O2175.39 (12)C8—C9—C9A—C5A1.7 (2)
C10A—N1—C2—C38.25 (19)C6—C5A—C9A—C92.8 (2)
O2—C2—C3—C4B159.6 (6)N5—C5A—C9A—C9178.90 (11)
N1—C2—C3—C4B16.6 (6)C6—C5A—C9A—N10176.15 (12)
O2—C2—C3—C4A149.42 (14)N5—C5A—C9A—N102.18 (14)
N1—C2—C3—C4A34.31 (17)C9—C9A—N10—C10A178.84 (14)
C4B—C3—C4A—N558.4 (7)C5A—C9A—N10—C10A0.05 (14)
C2—C3—C4A—N543.44 (16)C9A—N10—C10A—N52.30 (15)
C4B—C3—C4A—C41A64.0 (7)C9A—N10—C10A—N1175.22 (12)
C2—C3—C4A—C41A165.86 (15)C5A—N5—C10A—N103.71 (15)
N5—C4A—C41A—C42A53.9 (2)C4A—N5—C10A—N10169.91 (12)
C3—C4A—C41A—C42A66.80 (19)C4B—N5—C10A—N10141.5 (5)
N5—C4A—C41A—C46A125.51 (16)C5A—N5—C10A—N1173.92 (11)
C3—C4A—C41A—C46A113.82 (17)C4A—N5—C10A—N17.72 (19)
C46A—C41A—C42A—C43A0.6 (3)C4B—N5—C10A—N140.9 (6)
C4A—C41A—C42A—C43A178.77 (16)C2—N1—C10A—N10176.90 (13)
C41A—C42A—C43A—C44A0.5 (3)C2—N1—C10A—N55.7 (2)
C42A—C43A—C44A—C45A0.1 (4)C2—C3—C4B—C41B173.3 (12)
C42A—C43A—C44A—C47A179.4 (2)C4A—C3—C4B—C41B71.7 (13)
C43A—C44A—C45A—C46A0.5 (4)C2—C3—C4B—N548.4 (8)
C47A—C44A—C45A—C46A179.8 (2)C4A—C3—C4B—N553.2 (5)
C44A—C45A—C46A—C41A0.4 (3)C10A—N5—C4B—C360.1 (8)
C42A—C41A—C46A—C45A0.2 (3)C5A—N5—C4B—C3166.5 (3)
C4A—C41A—C46A—C45A179.24 (16)C4A—N5—C4B—C356.6 (6)
C41A—C4A—N5—C10A154.46 (15)C10A—N5—C4B—C41B172.7 (12)
C3—C4A—N5—C10A31.26 (17)C5A—N5—C4B—C41B39.3 (15)
C41A—C4A—N5—C5A43.0 (2)C4A—N5—C4B—C41B70.6 (13)
C3—C4A—N5—C5A166.21 (12)C3—C4B—C41B—C42B59 (2)
C41A—C4A—N5—C4B68.4 (7)N5—C4B—C41B—C42B63.2 (19)
C3—C4A—N5—C4B54.8 (7)C3—C4B—C41B—C46B126.4 (19)
C10A—N5—C5A—C6174.71 (15)N5—C4B—C41B—C46B112 (2)
C4A—N5—C5A—C69.9 (2)C46B—C41B—C42B—C43B3 (3)
C4B—N5—C5A—C650.4 (7)C4B—C41B—C42B—C43B178.8 (18)
C10A—N5—C5A—C9A3.35 (13)C41B—C42B—C43B—C44B5 (4)
C4A—N5—C5A—C9A168.14 (12)C42B—C43B—C44B—C45B1 (4)
C4B—N5—C5A—C9A131.5 (6)C42B—C43B—C44B—C47B180 (2)
N5—C5A—C6—C7179.56 (14)C43B—C44B—C45B—C46B6 (5)
C9A—C5A—C6—C71.8 (2)C47B—C44B—C45B—C46B173 (2)
C5A—C6—C7—C80.2 (2)C44B—C45B—C46B—C41B7 (4)
C6—C7—C8—C91.1 (2)C42B—C41B—C46B—C45B2 (3)
C7—C8—C9—C9A0.2 (2)C4B—C41B—C46B—C45B172.5 (19)
C8—C9—C9A—N10176.98 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N10i0.881.982.8481 (16)167
C3—H3A···O2ii0.992.563.2561 (19)127
C4A—H4A···CgYiii1.002.433.419 (16)159
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y+2, z+1; (iii) x+1, y+1, z+1.

Experimental details

(IVa)(Vb)
Crystal data
Chemical formulaC16H12BrN3OC17H15N3O
Mr342.20277.32
Crystal system, space groupMonoclinic, P21/cTriclinic, P1
Temperature (K)120120
a, b, c (Å)6.8807 (2), 16.2254 (6), 13.3379 (5)8.1360 (3), 9.8647 (4), 10.0975 (5)
α, β, γ (°)90, 111.280 (2), 90114.8796 (13), 94.9156 (15), 100.966 (3)
V3)1387.54 (8)709.18 (5)
Z42
Radiation typeMo KαMo Kα
µ (mm1)2.960.08
Crystal size (mm)0.20 × 0.06 × 0.020.1 × 0.1 × 0.1
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.589, 0.9430.992, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
8697, 3046, 2401 10703, 3170, 2247
Rint0.0780.056
(sin θ/λ)max1)0.6480.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.114, 1.01 0.046, 0.120, 1.05
No. of reflections30463170
No. of parameters190264
No. of restraints052
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.71, 1.550.21, 0.21

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2001), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (IVa) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N10i0.882.302.943 (3)129
C9—H9···CgXi0.952.593.501 (3)158
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) for (Vb) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N10i0.881.982.8481 (16)167
C3—H3A···O2ii0.992.563.2561 (19)127
C4A—H4A···CgYiii1.002.433.419 (16)159
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y+2, z+1; (iii) x+1, y+1, z+1.
 

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