Methyl 2-(4-ferrocenylbenzamido)thiophene-3-carboxylate and ethyl 2-(4-ferrocenylbenzamido)-1,3-thiazole-4-acetate, a unique ferrocene derivative containing a thiazole moiety

Alley, S.; Gallagher, J.F.; Hooper, V.M.; Kenny, P.T.M.; Lough, A.J.

doi:10.1107/S010827010501783X

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 7| July 2005| Pages m365-m369

doi:10.1107/S010827010501783X

Methyl 2-(4-ferrocenylbenzamido)thiophene-3-carboxylate and ethyl 2-(4-ferrocenylbenzamido)-1,3-thiazole-4-acetate, a unique ferrocene derivative containing a thiazole moiety

Steven Alley,^a John F. Gallagher,^a ^* Vincent M. Hooper,^b Peter T. M. Kenny ^a ^* and Alan J. Lough ^c

^aSchool of Chemical Sciences, National Institute for Cellular Biotechnology, Dublin City University, Dublin 9, Ireland, ^bSchool of Chemical Sciences, Dublin City University, Dublin 9, Ireland, and ^cDepartment of Chemistry, 80 St George Street, University of Toronto, Ontario, Canada M5S 3H6
^*Correspondence e-mail: john.gallagher@dcu.ie, peter.kenny@dcu.ie

(Received 5 May 2005; accepted 6 June 2005; online 30 June 2005)

The conformations and hydrogen bonding in the thiophene and thiazole title compounds, [Fe(C₅H₅)(C₂₀H₁₄NO₃S)], (I), and [Fe(C₅H₅)(C₁₉H₁₇N₂O₃S)], (II), are discussed. The sequence (C₅H₄)–(C₆H₄)–(CONH)–(C₄H₂S)–(CO₂Me) of rings and moieties in (I) is close to being planar; all consecutive interplanar angles are less than 10°. An intramolecular N—H⋯O=C_ester hydrogen bond [graph set S(6), N⋯O = 2.768 (2) Å and N—H⋯O = 134 (2)°] effects the molecular planarity, and aggregation occurs via hydrogen-bonded chains formed from intermolecular C_ar—H⋯O=C_ester/amide interactions along [010], with C⋯O distances ranging from 3.401 (3) to 3.577 (2) Å. The thiazole system in (II) crystallizes with two molecules in the asymmetric unit; these differ in the conformation along their long molecular axes; for example, the interplanar angle between the phenylene (C₆H₄) and thiazole (C₃NS) rings is 8.1 (2)° in one molecule and 27.66 (14)° in the other. Intermolecular N—H⋯O=C_ester hydrogen bonds [N⋯O = 2.972 (4) and 2.971 (3) Å], each augmented by a C_phenylene—H⋯O=C_ester interaction [3.184 (5) and 3.395 (4) Å], form motifs with graph set $[R_{2}^{1}]$ (7) and generate chains along [100]. The amide C=O groups do not participate in hydrogen bonding. Compound (II) is the first reported ferrocenyl-containing thiazole structure.

Comment

Ferrocene (Fc) and its derivatives continue to attract much attention in coordination chemistry, with important roles encompassing both structural and electronic capabilities (Adams, 1999 ). Integration of ferrocene into new hybrid systems has expanded the potential of organometallic materials with a range of feasible applications (Togni & Halterman, 1998 ; Togni & Hayashi, 1995 ; Hudson et al., 2001 ). We report here the structures of two 4-ferrocenylbenzamide systems with terminal thiophenecarboxylate, (I), and thiazoleacetate groups, (II).

A view of (I) with the atomic numbering scheme is shown in Fig. 1. Bond lengths and angles are in accord with anticipated values (Allen, 2002 ). In (I), the Fe—C bond lengths for the substituted η⁵-C₅H₄ ring are in the range 2.038 (2)–2.054 (2) Å and are similar to those in the η⁵-C₅H₅ ring [2.037 (2)–2.054 (2) Å]; the Fe⋯Cg1 and Fe⋯Cg2 distances are 1.6462 (10) and 1.6525 (10) Å, respectively, the Cg1⋯Fe1⋯Cg2 angle is 177.20 (5)°, and the C₅/C₅ interplanar angle is 3.81 (15)° [Cg1 and Cg2 are the η⁵-C₅H₄ and η⁵(C₅H₅) ring centroids, respectively]. The η⁵C₅ rings are slightly staggered from eclipsed geometry, with the five C1n⋯Cg1⋯Cg2⋯C2n pseudo-torsion angles in the range 12.24 (16)–12.79 (15)° (n = 1–5).

The related 4-FcC₆H₄CO₂R carboxylates [R = Me (Savage et al., 2002 ), Et and ⁱPr (Anderson et al., 2003 )] have conformations that can be defined by the interplanar angles between the η⁵-C₅H₄ and C₆H₄ rings, and between the C₆H₄ ring and carboxylate CO₂R group. These are, respectively, 9.35 (13) and 8.5 (2)° for Me, 6.88 (12) and 2.59 (17)° for Et, and 10.5 (2) and 19.5 (5)° for ⁱPr. In (I), the (C₅H₄)–(C₆H₄)–(CONH)–(C₄H₂S)–(CO₂Me) system has interplanar angles between successive C₅H₄, C₆H₄, CONH, C₄H₂S and CO₂Me moieties of 9.36 (11), 8.79 (17), 1.97 (14) and 6.33 (11)°, respectively. Apart from slight twisting, no ring bending occurs along the long molecular axis as a result of steric effects; this situation is in contrast to that found in 2-(ferrocenyl)thiophene-3-carboxylic acid (Gallagher et al., 2001 ), where significant bending from linearity occurs in the thienyl ring relative to the η⁵-C₅H₄ ring to which it is bonded.

Methyl 2-[(ferrocenylcarbonyl)amino]thiophene-3-carboxylate, (C₅H₅)Fe(C₅H₄)–(CONH)–(C₄H₂S)–(CO₂Me), (III) (Alley et al., 2005 ), differs from (I) in that it does not have the 1,4-phenylene C₆H₄ ring between the C₅H₄ and CONH groups. Geometric data are comparable in the two structures, with maximum differences within 0.01 Å and 2° for the amidothiophenecarboxylate residues. The C—S—C and S—C—N(H) angles are 90.98 (10) and 123.58 (15)° in (I), and 90.93 (11) and 123.54 (16)° in (III); the Cambridge Structural Database (CSD; Version 5.26 of February 2005; Allen, 2002) average for thiophene C—S—C angles is 92.0° (range 88.7–97.9°). For S—C=C_carboxy angles, the average is 111.4° (range 105.5–113.9°); the equivalent S1—C2=C3 angles in (I) and (III) are 111.89 (15) and 111.94 (15)°, respectively (Allen, 2002). CSD analysis shows that both (I) and (III) have regular amidothiophenecarboxylate moieties.

An intramolecular N—H⋯O=C_ester hydrogen bond (Table 1) forms a ring in (I), with graph set S(6) (Bernstein et al., 1995 ), thus enforcing planarity along the molecular axis; the N⋯O distance is 2.768 (2) Å, slightly longer than the corresponding value [2.727 (2) Å] in (III). Molecules of (I) assemble as one-dimensional chains along the b-axis direction through C—H⋯O=C interactions, as shown in Fig. 2 with details in Table 1. These generate $[R_{2}^{1}]$ (7) and R₃²(15) motifs that, in combination with the S(6) ring, produce a larger R₂²(20) ring. Overall, the crystal structure comprises one-dimensional chains, aggregating via weak C7—H7C⋯π(thienyl)ⁱⁱⁱ contacts (H7C⋯Cg3ⁱⁱⁱ = 2.83 Å; symmetry code as in Table 1), which link pairs of screw-axis-related chains to form a ladder extending along [010]; there are normal van der Waals separations between pairs of ladders. Examination of (I) with PLATON (Spek, 2002 ) reveals no solvent-accessible voids in the crystal structure and a packing index of 72.6.

Compound (II) is the first structurally characterized ferrocene derivative containing a thiazole moiety to be reported, and this compound crystallizes with two molecules (A and B) in the asymmetric unit of space group P $[\overline{1}]$ , as shown in Figs. 3(a) and 3(b). The conformations of these molecules differ slightly along their long molecular axes with respect to the orientations of the amidothiazoleacetate groups, and there is some minor ethoxy disorder [0.915 (7):0.085 (7)] in molecule A. Bond lengths and angles are unexceptional and are comparable to data available from corresponding fragments available in the CSD.

In (II), the Fe—C bond lengths for the η⁵-C₅H₄ ring in A are in the range 2.031 (4)–2.048 (3) Å and are similar to those [2.033 (3)–2.040 (4) Å] for the η⁵-C₅H₅ ring. Molecule B has similar values [2.032 (4)–2.047 (3) Å] for the substituted ring but two contrasting Fe⋯η⁵-C₅H₅ bond lengths [i.e. Fe1—C23B/C24B = 2.005 (4)/2.023 (5) Å]. These Fe—C C atoms have the largest U_eq values, cf. 0.0785 (17) and 0.0733 (15) Å² versus an average U_eq of 0.043 Å² for all 48 C atoms present (Spek, 2002); however, no disorder is present and the bond-length contraction must be a result of a small measure of librational motion and ring slippage (0.06 Å). The Fe⋯Cg1/Cg2 distances are 1.6407 (17) and 1.6450 (18) Å in A, and 1.6400 (17) and 1.644 (2) Å in B, the Cg1⋯Fe1⋯Cg2 angles are 178.76 (9) and 178.96 (10)°, and both C₅/C₅ interplanar angles are 1.6 (3)° [Cg1 and Cg2 are defined as for (I) above]. The η⁵C₅ rings deviate from eclipsed geometry, with five C1n⋯Cg1⋯Cg2⋯C2n (n = 1–5) pseudo-torsion angles ranging from 13.5 (3) to 14.5 (3)° in A and from 5.7 (3) to 7.3 (3)° in B, in the same sense as in A.

A minor conformational difference between molecules A and B is in the orientation of the Fc—C₆H₄– moiety with respect to the CONH–(thiazolyl)–CO₂Et fragment, resulting in the O1A—C1A—C34A—C33A [171.9 (3)°] and O1B—C1B—C34B—C33B [161.3 (3)°] torsion angles being significantly different. The amidothiazole groups adopt similar conformations in the two molecules, with N—H cis to N and C=O cis to S. A search of the CSD for this fragment gave 11 hits all with this same orientation, indicating that this is a preferred solid-state conformation. The cis-oriented pairs of N⋯N and O⋯S distances are 2.333 (4) and 2.342 (4) Å, and 2.669 (2) and 2.660 (3) Å, respectively, and are oriented in a suitable fashion for bidentate coordination to metal systems. As found for (I), molecule A contains consecutive ring and moiety planes that are essentially coplanar along the long molecular axis; however, in molecule B, the interplanar twists are larger; for example, the C₆H₄ and amide O=C—N(H) group planes are inclined at an angle of 17.2 (3)° (Figs. 3a and 3b). In tandem, slight bending occurs along the long molecular axis in molecule A, as evidenced by the C11n—C31n⋯C34n angle [176.4 (2)°; n = A or B], in contrast to the near linear value [178.46 (19)°] in B.

In (II), intermolecular N_amide—H⋯O=C_ester hydrogen bonds link the molecules, forming chains extending along [100], as shown in Fig. 4 with details in Table 2. This interaction, in combination with C—H⋯O=C_ester interactions, results in hydrogen-bonded rings with graph set $[R_{2}^{1}]$ (7), augmented by weaker secondary contacts C7B*⋯N2A and C7A⋯N2B (involving thiazole N atoms). Combination with the N—H⋯O=C hydrogen bonds produces rings with graph sets R₂²(9) and, overall for the pairs of rings, R₂²(12). The chains are linked into a ladder structure extending along [100] by C5A—H5A⋯π(thiaz-B)# interactions [symmetry code: (#) −x, −y, 1 − z; C5A⋯π(thiaz-centroid) = 3.511 (4) Å]. No comparable C5B⋯π(thiaz-A) interaction is present; the thiazole S atoms and amide C=O groups are not involved in hydrogen bonding. The packing index is 68.9 based on the major conformation of molecule A.

Of interest for comparison with (II) are the high-precision structural data for the molecular structure of thiazole (IV) from a combined analysis of gas-phase electron diffraction data, rotational constants and ab initio calculations (Bone et al., 1999 ). The corresponding mean values for (II) are S—C(C) = 1.713 (2) Å, S—C(N) = 1.730 (6) Å, C—N = 1.391 (2) Å and C=N = 1.299 (2) Å, demonstrating that the thiazole groups are relatively unperturbed through molecular or crystal packing forces in (II) and are comparable to the gas-phase structure data for (IV).

A search for amidothienyl and amidothiazolyl fragments in crystal structures in the CSD reveals seven and 21 systems (with coordinates), respectively. A search for structures incorporating the ferrocenyl moiety (as C₅FeC₅) and a thiophene-type heteroaromatic ring yielded 30 structures; when the thiophene-type ring was replaced with a thiazole heteroaromatic ring, there were no hits. This lack of structural data is somewhat unusual given the vast output of structural ferrocene research to date (Adams, 1999; Allen 2002). For comparison, a CSD search with ferrocene and pyridinyl (as C₅N) gives a total of 335 structures, revealing the wealth of structural data available for N-heteroaromatic groups, such as pyridine donor ligands, in ferrocene chemistry when compared with S-heteroaromatic systems, such as thiazole (Allen, 2002). Studies are in progress to extend the synthetic, structural and electrochemistry of these new systems in coordination chemistry.

Figure 1
A view of (I)

, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A view of the hydrogen-bond interactions (dashed lines) in the crystal structure of (I)

. [Symmetry codes: (*) x, 1 + y, z; (#) x, −1 + y, z.]

Figure 3
(a) A view of the major conformer of molecule A in (II)

and (b) a view of molecule B in (II)

, with the atomic numbering schemes. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4
The hydrogen-bonding pattern involving molecules A and B in (II)

. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (*) 1 − x, 1 − y, 1 − z; ($) −x, 1 − y, 1 − z.]

Experimental

Compounds (I) and (II) were synthesized according to standard coupling procedures using 4-ferrocenylbenzoic acid as its acid chloride and methyl 2-aminothiophene-3-carboxylate or ethyl 2-amino-4-thiazoleacetate in yields of ca 30 and 26%, respectively. Recrystallization, in both cases, was undertaken from petroleum spirits/Et₂O to produce red plates, (I) (m.p. 487–489 K), and an orange crystalline solid, (II) (421–423 K). Crystals suitable for X-ray diffraction studies were grown by diffusion of pentane vapour into a CH₂Cl₂ solution of the appropriate compound. Although the syntheses are uncomplicated, problems arose during the purification of (I) as it decomposes on both silica and alumina to give the starting materials plus a third compound, identified by ¹H and ¹³C NMR as methyl 4-ferrocenylbenzoate. Isolation of modest quantities of (I) was achieved by repeated recrystallization of column fractions, though the eventual overall yield was poor.

Compound (I)

Crystal data

[Fe(C₅H₅)(C₂₀H₁₄NO₃S)]
M_r = 445.30
Monoclinic, P 2₁ /n
a = 10.1428 (3) Å
b = 8.0965 (2) Å
c = 23.0557 (7) Å
β = 95.4912 (14)°
V = 1884.67 (9) Å³
Z = 4
D_x = 1.569 Mg m⁻³
Mo Kα radiation
Cell parameters from 6335 reflections
θ = 2.6–27.5°
μ = 0.94 mm⁻¹
T = 150 (1) K
Plate, red
0.22 × 0.16 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
φ scan and ω scans with κ offsets
Absorption correction: multi-scan(DENZO–SMN; Otwinowski & Minor, 1997 )T_min = 0.820, T_max = 0.912
6335 measured reflections
4313 independent reflections
3441 reflections with I > 2σ(I)
R_int = 0.049
θ_max = 27.5°
h = −13 → 13
k = −10 → 10
l = −25 → 29

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.088
S = 1.06
4313 reflections
268 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.033P)² + 1.226P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.63 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0024 (6)

Table 1
Hydrogen-bond geometry (Å, °) for (I)

Cg3 is the centroid of the thiophene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.81 (2)	2.14 (2)	2.768 (2)	134 (2)
C5—H5⋯O2ⁱ	0.95	2.56	3.411 (3)	150
C15—H15⋯O1ⁱⁱ	0.95	2.56	3.401 (3)	147
C32—H32⋯O1ⁱⁱ	0.95	2.65	3.577 (2)	165
C7—H7C⋯Cg3ⁱⁱⁱ	0.98	2.83	3.604 (2)	136
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Compound (II)

Crystal data

[Fe(C₅H₅)(C₁₉H₁₇NO₃S)]
M_r = 474.36
Triclinic, $[P \overline 1]$
a = 12.7466 (4) Å
b = 12.8752 (8) Å
c = 13.5661 (7) Å
α = 91.811 (3)°
β = 106.096 (3)°
γ = 92.735 (3)°
V = 2134.35 (18) Å³
Z = 4
D_x = 1.476 Mg m⁻³
Mo Kα radiation
Cell parameters from 12087 reflections
θ = 2.6–27.5°
μ = 0.83 mm⁻¹
T = 150 (1) K
Needle, red
0.20 × 0.07 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
φ scan and ω scans with κ offsets
Absorption correction: multi-scan(DENZO–SMN; Otwinowski & Minor, 1997)T_min = 0.851, T_max = 0.967
15129 measured reflections
9714 independent reflections
5617 reflections with I > 2σ(I)
R_int = 0.069
θ_max = 27.5°
h = −16 → 16
k = −16 → 16
l = −16 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.127
S = 1.00
9714 reflections
573 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0472P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0015 (4)

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O2B^iv	0.88	2.12	2.972 (4)	162
N1B—H1B⋯O2A^v	0.88	2.18	2.971 (3)	149
C33A—H33A⋯O2B^iv	0.95	2.24	3.184 (5)	173
C33B—H33B⋯O2A^v	0.95	2.46	3.395 (4)	167
C7A—H72⋯N2B^v	0.99	2.68	3.654 (6)	168
C7B—H75⋯N2A^iv	0.99	2.56	3.536 (5)	169
Symmetry codes: (iv) -x, -y+1, -z+1; (v) -x+1, -y+1, -z+1.

Compound (I) crystallized in the monoclinic system; space group P2₁/n was assigned from the systematic absences and confirmed by the analysis. Compound (II) crystallized in the triclinic system; space group P $[\overline{1}]$ was assumed and confirmed by the analysis, and the asymmetric unit was chosen so as to show clearly the overall similarity of the two independent molecules A and B. It became obvious during the refinement of (II) that there was some slight disorder at the terminal O3A—C7A—C8A moiety and this was allowed for. In the final refinement cycles, the bond lengths of the disordered ester group of molecule A were restrained via soft DFIX restraints to be the same as in the ordered molecule B; a common isotropic displacement parameter of 0.035 Å² was assigned to the minor-occupancy atoms. The final refined occupancies for the major and minor conformers were 0.915 (7) and 0.085 (7). In (I) and (II) [except for atom H1 bonded to N1 in (I)], all H atoms bound to C and N atoms were treated as riding, with U_iso(H) values of 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C,N) for the remainder (methyl C—H = 0.98 Å, methylene C—H = 0.99 Å, aromatic C—H = 0.95 Å and amide N—H = 0.88 Å). The N1—H1 distance in (I) refined to 0.81 (2) Å.

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; structure solution: SHELXS97 (Sheldrick, 1997 ); structure refinement: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002) and ORTEX (McArdle, 1995 ); publication software: SHELXL97, NRCVAX (Gabe et al., 1989 ) and PREP8 (Ferguson, 1998 ).

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S010827010501783X/fg1846sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S010827010501783X/fg1846Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S010827010501783X/fg1846IIsup3.hkl

Comment top

Ferrocene and its derivatives continue to attract much attention in coordination chemistry with important roles encompassing both structural and electronic capabilities (Adams, 1999). Integration of ferrocene into new hybrid systems has expanded the potential of organometallic materials with a range of feasible applications (Togni & Halterman, 1998; Togni & Hayashi, 1995; Hudson et al., 2001). We report here the structures of two 4-ferrocenylbenzoylamide systems with terminal thienyl methyl carboxylate, (I), and thiazolyl acetate groups, (II).

A view of (I) with the atomic numbering scheme is shown in Fig. 1. Bond lengths and angles are in accord with anticipated values (Allen, 2002). In (I), the Fe—C bond lengths for the substituted η⁵(C₅H₄) ring are in the range 2.038 (2)–2.054 (2) Å and are similar to those in the η⁵(C₅H₅) ring [2.037 (2)–2.054 (2) Å]; the Fe···Cg1 and Fe···Cg2 distances are 1.6462 (10) and 1.6525 (10) Å, respectively, the Cg1···Fe1···Cg2 angle is 177.20 (5)°, and the C₅/C₅ interplanar angle is 3.81 (15)° [Cg1 and Cg2 are the η⁵(C₅H₄) and η⁵(C₅H₅) ring centroids, respectively]. The η⁵-C₅ rings are slightly staggered from eclipsed geometry, with the five C1n···Cg1···Cg2···C2n torsion angles in the range 12.24 (16)–12.79 (15)° (n = 1–5).

The related 4-FcC₆H₄CO₂R carboxylates [R = Me (Savage et al., 2002), Et and ⁱPr (Anderson et al., 2003)] have conformations that can be defined by the interplanar angles between the η⁵(C₅H₄) and (C₆H₄) rings and between the (C₆H₄) ring and carboxylate (CO₂R) groups. These are, respectively, 9.35 (13) and 8.5 (2)° (Me), 6.88 (12) and 2.59 (17)° (Et), and 10.5 (2) and 19.5 (5)° (ⁱPr). In (I), the (C₅H₄)–C₆H₄–CONH–(C₄H₂S)–CO₂Me system has interplanar angles between successive (C₅H₄), (C₆H₄), (CONH), (C₄H₂S) and (CO₂Me) moieties of 9.36 (11), 8.79 (17), 1.97 (14) and 6.33 (11)°, respectively. Apart from small twisting, no ring bending occurs along the long molecular axis as a result of steric effects; this situation is in contrast to that found (Gallagher et al., 2001) in 2-(ferrocenyl)thiophene-3-carboxylic acid, where significant bending from linearity occurs in the thienyl ring relative to the η⁵(C₅H₄) ring to which it is bonded.

Methyl 2-{2-[(ferrocenylcarbonyl)amino]-1-thienyl}-3-carboxylate, (C₅H₅)Fe(C₅H₄)–CONH-(C₄H₂S)–CO₂Me, (III) (Alley et al., 2005), differs from (I) in that it does not have the 1,4-phenylene (C₆H₄) ring between the (C₅H₄) and CONH groups. Geometric data are comparable in the two structures, with maximum differences within 0.01 Å and 2° for the amidothienyl carboxylate residues. Angles involving S, for example C—S—C and S—C—N(H), are 90.98 (10) and 123.58 (15)° in (I), and 90.93 (11) and 123.54 (16)° in (III); the Cambridge Structural Database (CSD; Version 5.26 of February 2005; Allen, 2002) average for thienyl C—S—C angles is 92.0° (range 88.7–97.9°). For S—C═C_carboxy angles, the average is 111.4° (range 105.5–113.9°); the equivalent S1—C2═C3 angles in (I) and (III) are 111.89 (15) and 111.94 (15)° (Allen, 2002). CSD analysis shows that both (I) and (III) have regular amidothienyl carboxylate moieties.

An intramolecular N—H···O═C_ester hydrogen bond (Table 1) forms a ring in (I), graph set S(6), (Bernstein et al., 1995) thus enforcing planarity along the molecular axis; the N···O distance is 2.768 (2) Å, slightly longer than the corresponding value [2.727 (2) Å] in (III). Molecules of (I) assemble as one-dimensional chains along the b-axis direction through C—H···O═C interactions, as shown in Fig. 2 with details in Table 1. These generate R¹₂(7) and R²₃(15) motifs that in combination with the S(6) ring produce a larger R²₂(20) ring. Overall, the crystal structure comprises one-dimensional chains, aggregating via weak C7—H7C···π(thienyl)ⁱⁱⁱ contacts (H7C···Cg3ⁱⁱⁱ = 2.83 Å; symmetry code as in Table 1), which link pairs of screw-axis related chains to form a ladder extending along [010]; there are normal van der Waals separations between pairs of ladders. Examination of (I) with PLATON (Spek, 2002) reveals no solvent accessible voids in the crystal structure and a packing index of 72.6.

Compound (II) is the first structurally characterized ferrocene derivative containing a thiazole moiety to be reported and this compound crystallizes with two molecules (A and B) in the asymmetric unit of space group P1, as shown in Figs. 3(a) and 3(b). Their conformations differ slightly along their long molecular axes with respect to the orientations of the amidothiazolylcarboxylate groups and there is some minor ethoxy disorder [0.915 (7):0.085 (7)] in molecule A. Bond lengths and angles are unexceptional and are comparable to data available from corresponding fragments available in the CSD.

In (II), the Fe—C bond lengths for the η⁵(C₅H₄) ring in A are 2.031 (4)–2.048 (3) Å and are similar to those [2.033 (3)–2.040 (4) Å] for the η⁵(C₅H₅) ring. Molecule B has similar values [2.032 (4)–2.047 (3) Å] for the substituted ring, but two contrasting Fe···η⁵(C₅H₅) bond lengths [i.e. Fe1—C23B/C24B = 2.005 (4)/2.023 (5) Å]. This Fe—C pair have the largest U_eq values, of 0.0785 (17) and 0.0733 (15) Å², compared with an average U_eq of 0.043 Å² for all 48 C atoms present (Spek, 2002); however, no disorder is present and the bond-length contraction must be due to a small measure of librational motion and ring slippage (0.06 Å). The Fe···Cg1/Cg2 distances are 1.6407 (17) and 1.6450 (18) Å (in A), and 1.6400 (17) and 1.644 (2) Å (in B), the Cg1···Fe1···Cg2 angles are 178.76 (9) and 178.96 (10)°, and both C₅/C₅ interplanar angles are 1.6 (3)° [Cg1 and Cg2 are defined as for (I) above]. The η⁵-C₅ rings deviate from eclipsed geometry, with five C1n···Cg1···Cg2···C2n (n = 1–5) torsion angles from 13.5 (3) to 14.5 (3)° in A and 5.7 (3) to 7.3 (3)° in B, in the same sense as in A.

A minor conformational difference between molecules A and B is in the orientation of the Fc—C₆H₄– moiety with respect to the CONH–(thiazolyl)–CO₂Et fragment, resulting in the O1A—C1A—C34A—C33A [171.9 (3)°] and O1B—C1B—C34B—C33B [161.3 (3)°] torsion angles being significantly different. The amido(thiazolyl) groups adopt similar conformations in both molecules with N—H cis to N and C═O cis to S. A search of the CSD for this fragment gave 11 hits all with this same orientation, indicating that this is a preferred solid-state conformation. The cis-oriented pairs of N···N and O···S distances are 2.333 (4) and 2.342 (4) Å, and 2.669 (2) and 2.660 (3) Å, respectively, and are oriented in a suitable fashion for bidentate coordination to metal systems. As found for (I), molecule A contains consecutive ring and moiety planes that are essentially coplanar along the long molecular axis; however, in B, the interplanar twists are larger; for example, the C₆H₄ and amide O═C—N(H) group planes are inclined at 17.2 (3)° (Figs. 3a and 3b). In tandem, slight bending occurs along the long molecular axis in A, as evidenced by the C11n—C31n···C34n angle [176.4 (2)°; n = A or B], in contrast to the near linear value [178.46 (19)°] in B.

In (II), intermolecular _amideN—H···O═C_ester hydrogen bonds link the molecules, forming chains extending along [100], as shown in Fig. 4 with details in Table 2. This interaction, in combination with C—H···O═ C_ester interactions, results in hydrogen-bonded rings with graph set R¹₂(7), augmented by weaker secondary contacts C7B*···N2A and C7A···N2B (involving thiazolyl N atoms). Combination with the N—H···O═C hydrogen bonds produces rings with graph sets R²₂(9) and, overall for the pairs of rings, R²₂(12). The chains are linked into a ladder structure extending along [100] by C5A—H5A···π(thiaz-B)# interactions [symmetry code: (#) = −x,-y,1 − z; C5A···π(thiaz-centroid) = 3.511 (4) Å]. No comparable C5B···π(thiaz-A) interaction is present; the thiazolyl S atoms and amide C═O groups are not involved in hydrogen bonding. The packing index is 68.9 and based on the major conformation of molecule A.

Of interest for comparison with (II) are the high-precision structural data for the molecular structure of thiazole (IV) from a combined analysis of gas-phase electron diffraction data, rotational constants and ab-initio calculations (Bone et al., 1999). The corresponding mean values from (II) are S—C(C) = 1.713 (2) Å, S—C(N) = 1.730 (6) Å, C—N = 1.391 (2) Å and C═N = 1.299 (2) Å, demonstrating that the thiazole groups are relatively unperturbed through molecular or crystal packing forces in (II) and are comparable to the gas-phase structure data for (IV).

A search for amidothienyl and amidothiazolyl fragments in crystal structures in the CSD reveals seven and 21 systems (with coordinates), respectively. A search for structures incorporating the ferrocenyl moiety (as C₅FeC₅) and a thiophene-type heteroaromatic ring yielded 30 structures; when the thiophene-type ring was replaced with a thiazole heteroaromatic ring, there were no hits. This lack of structural data is somewhat unusual given the vast output of structural ferrocene research to date (Adams, 1999; Allen 2002). For comparison, a CSD search with ferrocene and pyridinyl (as C₅N) gives a total of 335 structures, revealing the wealth of structural data available for N-heteroaromatic groups, such as pyridine donor ligands in ferrocene chemistry, when compared with S-heteroaromatic systems, such as thiazole (Allen, 2002). Studies are in progress to extend the synthetic, structural and electrochemistry of these new systems in coordination chemistry.

Experimental top

Compounds (I) and (II) were synthesized by standard coupling procedures using 4-(ferrocenyl)benzoic acid as its acid chloride, with methyl 2-aminothiophene-3-carboxylate or ethyl 2-amino-4-thiazoleacetate in yields of ca 30 and 26%, respectively. Recrystallizations for both compounds were undertaken from petroleum spirits/Et₂O to produce red plates (I) (m.p. 487–489 K) and an orange crystalline solid (II) (421–423 K). Crystals suitable for X-ray diffraction studies were grown by diffusion of pentane vapour into a CH₂Cl₂ solution of the appropriate compound. Although the syntheses are uncomplicated, problems arose during the purification of (I), as it decomposes on both silica and alumina to give the starting materials plus a third compound, identified by ¹H and ¹³C NMR as methyl para-ferrocenyl benzoate. Isolation of modest quantities of (I) was achieved by repeated recrystallizations of column fractions though the eventual overall yield was poor.

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: PLATON (Spek, 2002) and ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97, NRCVAX (Gabe et al., 1989) and PREP8 (Ferguson, 1998).

Figures top

	Fig. 1. A view of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the hydrogen-bond interactions (dashed lines) in the crystal structure of (I). [Symmetry codes: (*) x, 1 + y, z; (#) x, −1 + y, z.]
	Fig. 3. (a) A view of the major conformer of molecule A in (II) and (b) a view of molecule B in (II), with the atomic numbering schemes. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. The hydrogen-bonding pattern involving molecules A and B in (II). Hyddrogen bonds are shown as dashed lines. [Symmetry codes: (*) 1 − x, 1 − y, 1 − z; ($) −x, 1 − y, 1 − z.]

(I) Methyl 2-[(4-ferrocenylbenzoyl)amino]-3-thiophenecarboxylate top

Crystal data top

C₂₃H₁₉FeNO₃S	F(000) = 920
M_r = 445.30	D_x = 1.569 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 488 K
Hall symbol: -p 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.1428 (3) Å	Cell parameters from 6335 reflections
b = 8.0965 (2) Å	θ = 2.6–27.5°
c = 23.0557 (7) Å	µ = 0.94 mm⁻¹
β = 95.4912 (14)°	T = 150 K
V = 1884.67 (9) Å³	Plate, red
Z = 4	0.22 × 0.16 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	4313 independent reflections
Radiation source: fine-focus sealed X-ray tube	3441 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ scan and ω scans with κ offsets	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −13→13
T_min = 0.820, T_max = 0.912	k = −10→10
6335 measured reflections	l = −25→29

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.033P)² + 1.226P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4313 reflections	Δρ_max = 0.35 e Å⁻³
268 parameters	Δρ_min = −0.63 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (6)

Crystal data top

C₂₃H₁₉FeNO₃S	V = 1884.67 (9) Å³
M_r = 445.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1428 (3) Å	µ = 0.94 mm⁻¹
b = 8.0965 (2) Å	T = 150 K
c = 23.0557 (7) Å	0.22 × 0.16 × 0.10 mm
β = 95.4912 (14)°

Data collection top

Nonius KappaCCD diffractometer	4313 independent reflections
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	3441 reflections with I > 2σ(I)
T_min = 0.820, T_max = 0.912	R_int = 0.049
6335 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.35 e Å⁻³
4313 reflections	Δρ_min = −0.63 e Å⁻³
268 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Planes data (I) ###############

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.3764(0.0065)x + 1.0490(0.0092)y + 10.7730(0.0232)z = 0.4034(0.0035)

* 0.0000(0.0014) C21 * −0.0003(0.0014) C22 * 0.0005(0.0014) C23 * −0.0005(0.0014) C24 * 0.0003(0.0014) C25 1.6524(0.0010) Fe1 2.6428(0.0084) C1 2.9039(0.0091) O1 2.2242(0.0092) N1 2.3050(0.0117) S1

Rms deviation of fitted atoms = 0.0004

8.4960(0.0058)x + 1.4976(0.0083)y + 9.9470(0.0215)z = 3.5060(0.0033)

Angle to previous plane (with approximate e.s.d.) = 3.81(0.15)

* 0.0010(0.0013) C11 * −0.0006(0.0013) C12 * 0.0000(0.0013) C13 * 0.0007(0.0013) C14 * −0.0011(0.0013) C15 − 1.6460(0.0010) Fe1 − 0.1921(0.0075) C1 0.1180(0.0081) O1 − 0.5751(0.0082) N1 − 0.3236(0.0104) S1

Rms deviation of fitted atoms = 0.0008

9.2707(0.0036)x + 0.8962(0.0070)y + 6.9405(0.0191)z = 3.3457(0.0013)

Angle to previous plane (with approximate e.s.d.) = 9.36(0.11)

* 0.0057(0.0015) C31 * −0.0046(0.0015) C32 * −0.0013(0.0014) C33 * 0.0063(0.0014) C34 * −0.0052(0.0015) C35 * −0.0008(0.0015) C36 0.0340(0.0033) C1 0.2008(0.0037) O1 − 0.1415(0.0037) N1 0.0170(0.0033) C11

Rms deviation of fitted atoms = 0.0045

9.7991(0.0022)x + 0.1600(0.0080)y + 3.7750(0.0191)z = 3.3261(0.0074)

Angle to previous plane (with approximate e.s.d.) = 9.71(0.07)

* 0.0032(0.0012) C2 * −0.0030(0.0013) C3 * 0.0010(0.0014) C4 * 0.0009(0.0013) C5 * −0.0021(0.0010) S1 − 1.8223(0.0107) Fe1 − 0.0218(0.0040) C1 − 0.0182(0.0034) O1 0.0168(0.0033) N1

Rms deviation of fitted atoms = 0.0023

9.7142(0.0070)x + 0.0456(0.0241)y + 4.4864(0.0555)z = 3.2045(0.0161)

Angle to previous plane (with approximate e.s.d.) = 1.97(0.14)

* 0.0000(0.0000) C1 * 0.0000(0.0000) O1 * 0.0000(0.0000) N1 0.0029(0.0177) C31 0.1743(0.0154) C32 − 0.0057(0.0076) C34

Rms deviation of fitted atoms = 0.0000

9.7142 (0.0070)x + 0.0456(0.0241)y + 4.4864(0.0555)z = 3.2045(0.0161)

Angle to previous plane (with approximate e.s.d.) = 0.00(0.19)

* 0.0000(0.0000) C1 * 0.0000(0.0000) O1 * 0.0000(0.0000) N1 − 0.0580(0.0063) C2 − 0.1401(0.0138) C4 − 0.1312(0.0150) C5 − 0.0762(0.0098) S1

Rms deviation of fitted atoms = 0.0000

9.2707(0.0036)x + 0.8962(0.0070)y + 6.9405(0.0191)z = 3.3457(0.0013)

Angle to previous plane (with approximate e.s.d.) = 8.79(0.17)

Rms deviation of fitted atoms = 0.0045

9.7991(0.0022)x + 0.1600(0.0080)y + 3.7750(0.0191)z = 3.3261(0.0074)

Angle to previous plane (with approximate e.s.d.) = 9.71(0.07)

* 0.0032(0.0012) C2 * −0.0030(0.0013) C3 * 0.0010(0.0014) C4 * 0.0009(0.0013) C5 * −0.0021(0.0010) S1 − 1.8223(0.0107) Fe1 − 0.0218(0.0040) C1 − 0.0182(0.0034) O1 0.0168(0.0033) N1

Rms deviation of fitted atoms = 0.0023

9.5253(0.0054)x − 0.3900(0.0276)y + 5.7354(0.0435)z = 2.5870(0.0068)

Angle to previous plane (with approximate e.s.d.) = 6.33(0.11)

* 0.0000(0.0000) O2 * 0.0000(0.0000) O3 * 0.0000(0.0000) C6 0.0262(0.0067) C7 − 0.1572(0.0105) C4 0.6556(0.0094) C31 0.6559(0.0069) C33 0.4292(0.0108) C34

Rms deviation of fitted atoms = 0.0000

Distances and angles in (I) ###########################

Distance M.·O 7.8520 (0.0015) Fe1 - O1 8.6858 (0.0015) Fe1 - O2 10.9332 (0.0015) Fe1 - O3

Distance M.·S 10.1770 (0.0006) Fe1 - S1

Angle MCC 124.38 (0.07) Fe1 - C11 - C1

Angle CCC 179.40 (0.15) C11 - C31 - C34 177.94 (0.13) C11 - C31 - C1 175.38 (0.13) C11 - C34 - C1

Dihedral angle MCCC −80.61 (0.23) Fe1 - C11 - C31 - C32 99.11 (0.21) Fe1 - C11 - C31 - C36

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.10728 (3)	−0.22659 (3)	0.129472 (12)	0.01830 (10)
S1	0.36891 (5)	0.75731 (6)	−0.10918 (2)	0.02415 (14)
O1	0.33126 (17)	0.60101 (18)	−0.00909 (7)	0.0302 (4)
O2	0.38773 (15)	0.22531 (17)	−0.17757 (6)	0.0244 (3)
O3	0.44198 (15)	0.35213 (18)	−0.25904 (6)	0.0265 (3)
N1	0.36581 (17)	0.4273 (2)	−0.08213 (7)	0.0199 (4)
C1	0.3398 (2)	0.4583 (2)	−0.02603 (9)	0.0211 (4)
C2	0.37838 (19)	0.5489 (2)	−0.12352 (9)	0.0193 (4)
C3	0.4003 (2)	0.5189 (2)	−0.18075 (9)	0.0207 (4)
C4	0.4106 (2)	0.6685 (3)	−0.21286 (10)	0.0252 (5)
C5	0.3958 (2)	0.8042 (3)	−0.18006 (10)	0.0285 (5)
C6	0.4087 (2)	0.3515 (3)	−0.20382 (9)	0.0210 (4)
C7	0.4538 (2)	0.1914 (3)	−0.28508 (10)	0.0321 (5)
C11	0.2705 (2)	−0.0775 (2)	0.13321 (8)	0.0186 (4)
C12	0.2063 (2)	−0.0661 (2)	0.18613 (9)	0.0205 (4)
C13	0.2050 (2)	−0.2262 (3)	0.21145 (9)	0.0221 (4)
C14	0.2673 (2)	−0.3375 (3)	0.17507 (9)	0.0226 (4)
C15	0.3074 (2)	−0.2470 (2)	0.12701 (9)	0.0201 (4)
C21	−0.0227 (2)	−0.1230 (3)	0.06705 (10)	0.0326 (5)
C22	−0.0858 (2)	−0.1486 (3)	0.11858 (10)	0.0269 (5)
C23	−0.0804 (2)	−0.3205 (3)	0.13123 (10)	0.0271 (5)
C24	−0.0143 (2)	−0.4002 (3)	0.08752 (11)	0.0324 (5)
C25	0.0216 (2)	−0.2782 (3)	0.04774 (10)	0.0344 (6)
C31	0.28777 (19)	0.0561 (2)	0.09125 (9)	0.0196 (4)
C32	0.3309 (2)	0.0234 (2)	0.03631 (9)	0.0206 (4)
C33	0.3480 (2)	0.1500 (3)	−0.00238 (9)	0.0214 (4)
C34	0.3223 (2)	0.3137 (2)	0.01192 (9)	0.0197 (4)
C35	0.2775 (2)	0.3456 (3)	0.06595 (9)	0.0248 (5)
C36	0.2608 (2)	0.2202 (3)	0.10520 (9)	0.0235 (4)
H1	0.362 (2)	0.334 (3)	−0.0948 (10)	0.022 (6)*
H4	0.4262	0.6721	−0.2528	0.030*
H5	0.3997	0.9138	−0.1945	0.034*
H7A	0.5255	0.1298	−0.2633	0.048*
H7B	0.4736	0.2043	−0.3256	0.048*
H7C	0.3704	0.1310	−0.2840	0.048*
H12	0.1710	0.0315	0.2015	0.025*
H13	0.1686	−0.2540	0.2467	0.027*
H14	0.2799	−0.4524	0.1817	0.027*
H15	0.3513	−0.2914	0.0959	0.024*
H21	−0.0119	−0.0197	0.0486	0.039*
H22	−0.1246	−0.0658	0.1407	0.032*
H23	−0.1151	−0.3728	0.1634	0.032*
H24	0.0028	−0.5153	0.0853	0.039*
H25	0.0672	−0.2970	0.0142	0.041*
H32	0.3486	−0.0871	0.0256	0.025*
H33	0.3777	0.1254	−0.0393	0.026*
H35	0.2581	0.4561	0.0761	0.030*
H36	0.2306	0.2455	0.1419	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01750 (16)	0.02174 (17)	0.01567 (16)	−0.00155 (11)	0.00158 (11)	0.00031 (11)
S1	0.0305 (3)	0.0196 (3)	0.0228 (3)	−0.0015 (2)	0.0047 (2)	−0.0005 (2)
O1	0.0476 (10)	0.0200 (8)	0.0246 (8)	−0.0027 (7)	0.0112 (7)	−0.0018 (6)
O2	0.0288 (8)	0.0211 (7)	0.0240 (8)	−0.0011 (6)	0.0067 (6)	0.0002 (6)
O3	0.0333 (9)	0.0269 (8)	0.0201 (8)	−0.0032 (7)	0.0076 (6)	−0.0039 (6)
N1	0.0247 (9)	0.0178 (9)	0.0173 (9)	−0.0012 (7)	0.0031 (7)	0.0000 (7)
C1	0.0190 (10)	0.0232 (11)	0.0212 (11)	−0.0027 (8)	0.0025 (8)	−0.0015 (8)
C2	0.0189 (10)	0.0188 (10)	0.0199 (11)	−0.0009 (8)	0.0004 (8)	0.0005 (8)
C3	0.0195 (10)	0.0211 (10)	0.0214 (11)	−0.0006 (8)	0.0021 (8)	0.0005 (8)
C4	0.0285 (12)	0.0257 (11)	0.0221 (11)	−0.0034 (9)	0.0049 (9)	0.0045 (8)
C5	0.0339 (13)	0.0243 (11)	0.0276 (12)	−0.0046 (9)	0.0044 (10)	0.0059 (9)
C6	0.0189 (10)	0.0256 (11)	0.0188 (10)	−0.0007 (8)	0.0027 (8)	−0.0011 (8)
C7	0.0337 (13)	0.0337 (13)	0.0299 (13)	−0.0033 (10)	0.0080 (10)	−0.0121 (10)
C11	0.0187 (10)	0.0210 (10)	0.0161 (10)	−0.0024 (8)	0.0017 (8)	−0.0021 (7)
C12	0.0210 (10)	0.0233 (10)	0.0168 (10)	−0.0013 (8)	0.0000 (8)	−0.0031 (8)
C13	0.0222 (10)	0.0290 (11)	0.0146 (10)	−0.0006 (8)	−0.0002 (8)	0.0025 (8)
C14	0.0230 (11)	0.0228 (10)	0.0215 (11)	0.0010 (8)	−0.0005 (8)	0.0030 (8)
C15	0.0162 (10)	0.0236 (11)	0.0205 (10)	0.0007 (8)	0.0022 (8)	−0.0002 (8)
C21	0.0283 (12)	0.0415 (14)	0.0265 (12)	−0.0038 (10)	−0.0050 (10)	0.0109 (10)
C22	0.0195 (11)	0.0338 (12)	0.0267 (12)	0.0017 (9)	−0.0007 (9)	0.0003 (9)
C23	0.0197 (11)	0.0342 (12)	0.0271 (12)	−0.0064 (9)	0.0010 (9)	0.0019 (9)
C24	0.0258 (12)	0.0318 (12)	0.0382 (14)	−0.0064 (10)	−0.0036 (10)	−0.0106 (10)
C25	0.0263 (12)	0.0579 (16)	0.0182 (11)	−0.0042 (11)	−0.0019 (9)	−0.0073 (10)
C31	0.0167 (10)	0.0202 (10)	0.0220 (11)	−0.0028 (8)	0.0027 (8)	−0.0008 (8)
C32	0.0237 (11)	0.0186 (10)	0.0196 (11)	0.0006 (8)	0.0036 (8)	−0.0022 (8)
C33	0.0225 (11)	0.0237 (10)	0.0188 (10)	−0.0005 (8)	0.0053 (8)	−0.0015 (8)
C34	0.0191 (10)	0.0208 (10)	0.0191 (10)	−0.0010 (8)	0.0008 (8)	−0.0007 (8)
C35	0.0302 (12)	0.0193 (10)	0.0258 (12)	0.0003 (9)	0.0078 (9)	−0.0031 (8)
C36	0.0285 (11)	0.0234 (10)	0.0196 (11)	−0.0001 (9)	0.0076 (9)	−0.0031 (8)

Geometric parameters (Å, º) top

Fe1—C11	2.044 (2)	C3—C4	1.429 (3)
Fe1—C12	2.038 (2)	C3—C6	1.462 (3)
Fe1—C13	2.048 (2)	C4—C5	1.350 (3)
Fe1—C14	2.054 (2)	C11—C12	1.440 (3)
Fe1—C15	2.042 (2)	C11—C15	1.433 (3)
Fe1—C21	2.037 (2)	C12—C13	1.422 (3)
Fe1—C22	2.050 (2)	C13—C14	1.420 (3)
Fe1—C23	2.054 (2)	C14—C15	1.420 (3)
Fe1—C24	2.051 (2)	C21—C22	1.418 (3)
Fe1—C25	2.041 (2)	C21—C25	1.420 (4)
S1—C2	1.724 (2)	C22—C23	1.422 (3)
S1—C5	1.724 (2)	C23—C24	1.418 (3)
O1—C1	1.225 (2)	C24—C25	1.419 (3)
O2—C6	1.216 (2)	C31—C32	1.404 (3)
O3—C6	1.348 (2)	C31—C36	1.401 (3)
O3—C7	1.443 (3)	C32—C33	1.380 (3)
N1—C1	1.368 (3)	C33—C34	1.396 (3)
N1—C2	1.385 (3)	C34—C35	1.390 (3)
C1—C34	1.482 (3)	C35—C36	1.381 (3)
C11—C31	1.473 (3)	N1—H1	0.81 (2)
C2—C3	1.381 (3)

C2—S1—C5	90.98 (10)	C24—Fe1—C14	110.61 (9)
C6—O3—C7	115.33 (17)	C21—Fe1—C23	68.15 (9)
C1—N1—C2	124.05 (18)	C12—Fe1—C23	128.64 (9)
C1—N1—H1	120.4 (17)	C25—Fe1—C23	68.23 (9)
C2—N1—H1	114.8 (17)	C15—Fe1—C23	153.64 (9)
O1—C1—N1	119.99 (19)	C11—Fe1—C23	165.07 (9)
O1—C1—C34	122.73 (19)	C13—Fe1—C23	110.48 (9)
N1—C1—C34	117.27 (17)	C22—Fe1—C23	40.54 (9)
S1—C2—N1	123.58 (15)	C24—Fe1—C23	40.42 (9)
S1—C2—C3	111.89 (15)	C14—Fe1—C23	121.11 (9)
N1—C2—C3	124.53 (18)	C15—C11—C12	106.82 (17)
C2—C3—C4	111.85 (18)	C15—C11—C31	126.11 (18)
C2—C3—C6	122.12 (18)	C12—C11—C31	126.97 (18)
C4—C3—C6	126.02 (19)	C15—C11—Fe1	69.42 (11)
C3—C4—C5	112.5 (2)	C12—C11—Fe1	69.12 (11)
S1—C5—C4	112.82 (17)	C31—C11—Fe1	123.56 (14)
O2—C6—O3	123.01 (18)	C13—C12—C11	108.20 (18)
O2—C6—C3	125.35 (19)	C13—C12—Fe1	70.03 (11)
O3—C6—C3	111.63 (17)	C11—C12—Fe1	69.57 (11)
C21—Fe1—C12	115.89 (9)	C14—C13—C12	108.25 (18)
C21—Fe1—C25	40.75 (10)	C14—C13—Fe1	69.95 (12)
C12—Fe1—C25	149.59 (9)	C12—C13—Fe1	69.23 (11)
C21—Fe1—C15	126.25 (9)	C13—C14—C15	108.12 (18)
C12—Fe1—C15	68.85 (8)	C13—C14—Fe1	69.55 (12)
C25—Fe1—C15	107.10 (9)	C15—C14—Fe1	69.30 (12)
C21—Fe1—C11	104.69 (9)	C14—C15—C11	108.60 (18)
C12—Fe1—C11	41.31 (8)	C14—C15—Fe1	70.14 (12)
C25—Fe1—C11	115.55 (9)	C11—C15—Fe1	69.52 (11)
C15—Fe1—C11	41.06 (8)	C22—C21—C25	108.4 (2)
C21—Fe1—C13	151.00 (9)	C22—C21—Fe1	70.21 (13)
C12—Fe1—C13	40.74 (8)	C25—C21—Fe1	69.79 (13)
C25—Fe1—C13	167.86 (9)	C21—C22—C23	107.6 (2)
C15—Fe1—C13	68.38 (8)	C21—C22—Fe1	69.20 (13)
C11—Fe1—C13	69.02 (8)	C23—C22—Fe1	69.88 (12)
C21—Fe1—C22	40.59 (9)	C24—C23—C22	108.1 (2)
C12—Fe1—C22	106.78 (9)	C24—C23—Fe1	69.67 (12)
C25—Fe1—C22	68.46 (9)	C22—C23—Fe1	69.58 (12)
C15—Fe1—C22	164.07 (9)	C23—C24—C25	108.1 (2)
C11—Fe1—C22	125.70 (9)	C23—C24—Fe1	69.91 (12)
C13—Fe1—C22	118.99 (9)	C25—C24—Fe1	69.34 (13)
C21—Fe1—C24	68.25 (10)	C24—C25—C21	107.7 (2)
C12—Fe1—C24	167.65 (9)	C24—C25—Fe1	70.07 (13)
C25—Fe1—C24	40.59 (10)	C21—C25—Fe1	69.45 (13)
C15—Fe1—C24	119.07 (9)	C36—C31—C32	118.07 (18)
C11—Fe1—C24	150.81 (9)	C36—C31—C11	120.53 (18)
C13—Fe1—C24	130.71 (9)	C32—C31—C11	121.40 (18)
C22—Fe1—C24	68.22 (9)	C33—C32—C31	120.82 (18)
C21—Fe1—C14	165.43 (9)	C32—C33—C34	120.95 (19)
C12—Fe1—C14	68.50 (8)	C35—C34—C33	118.19 (18)
C25—Fe1—C14	128.95 (9)	C35—C34—C1	116.73 (18)
C15—Fe1—C14	40.56 (8)	C33—C34—C1	125.09 (18)
C11—Fe1—C14	68.86 (8)	C36—C35—C34	121.46 (19)
C13—Fe1—C14	40.49 (8)	C35—C36—C31	120.51 (19)
C22—Fe1—C14	153.65 (9)

C2—N1—C1—O1	−2.9 (3)	C31—C11—C15—C14	−176.65 (19)
C2—N1—C1—C34	176.86 (18)	C25—C21—C22—C23	0.0 (2)
C1—N1—C2—C3	−177.7 (2)	C21—C22—C23—C24	−0.1 (2)
C1—N1—C2—S1	2.5 (3)	C22—C23—C24—C25	0.1 (2)
C5—S1—C2—C3	−0.46 (17)	C23—C24—C25—C21	−0.1 (3)
C5—S1—C2—N1	179.34 (18)	C22—C21—C25—C24	0.0 (3)
N1—C2—C3—C4	−179.22 (19)	C15—C11—C31—C36	−173.1 (2)
S1—C2—C3—C4	0.6 (2)	C12—C11—C31—C36	11.2 (3)
N1—C2—C3—C6	1.8 (3)	Fe1—C11—C31—C36	99.1 (2)
S1—C2—C3—C6	−178.42 (16)	C15—C11—C31—C32	7.2 (3)
C2—C3—C4—C5	−0.4 (3)	C12—C11—C31—C32	−168.55 (19)
C6—C3—C4—C5	178.5 (2)	Fe1—C11—C31—C32	−80.6 (2)
C3—C4—C5—S1	0.1 (3)	C36—C31—C32—C33	0.9 (3)
C2—S1—C5—C4	0.21 (19)	C11—C31—C32—C33	−179.33 (19)
C7—O3—C6—O2	−1.2 (3)	C31—C32—C33—C34	−0.3 (3)
C7—O3—C6—C3	179.41 (17)	C32—C33—C34—C35	−0.7 (3)
C2—C3—C6—O2	6.0 (3)	C32—C33—C34—C1	178.9 (2)
C4—C3—C6—O2	−172.9 (2)	O1—C1—C34—C35	8.6 (3)
C2—C3—C6—O3	−174.58 (18)	N1—C1—C34—C35	−171.15 (19)
C4—C3—C6—O3	6.6 (3)	O1—C1—C34—C33	−171.0 (2)
C15—C11—C12—C13	0.2 (2)	N1—C1—C34—C33	9.2 (3)
C31—C11—C12—C13	176.56 (19)	C33—C34—C35—C36	1.1 (3)
C11—C12—C13—C14	−0.1 (2)	C1—C34—C35—C36	−178.5 (2)
C12—C13—C14—C15	−0.1 (2)	C34—C35—C36—C31	−0.5 (3)
C13—C14—C15—C11	0.2 (2)	C32—C31—C36—C35	−0.6 (3)
C12—C11—C15—C14	−0.2 (2)	C11—C31—C36—C35	179.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.81 (2)	2.14 (2)	2.768 (2)	134 (2)
C5—H5···O2ⁱ	0.95	2.56	3.411 (3)	150
C15—H15···O1ⁱⁱ	0.95	2.56	3.401 (3)	147
C32—H32···O1ⁱⁱ	0.95	2.65	3.577 (2)	165
C7—H7C···Cg3ⁱⁱⁱ	0.98	2.83	3.604 (2)	136

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1/2, y−1/2, −z−1/2.

(II) Ethyl 2-[(4-ferrocenylbenzoyl)amino]-4-(1,3-thiazole)acetate top

Crystal data top

C₂₄H₂₂FeN₂O₃S	Z = 4
M_r = 474.36	F(000) = 984
Triclinic, P1	D_x = 1.476 Mg m⁻³
Hall symbol: -P 1	Melting point: 422 K
a = 12.7466 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.8752 (8) Å	Cell parameters from 12087 reflections
c = 13.5661 (7) Å	θ = 2.6–27.5°
α = 91.811 (3)°	µ = 0.83 mm⁻¹
β = 106.096 (3)°	T = 150 K
γ = 92.735 (3)°	Needle, red
V = 2134.35 (18) Å³	0.20 × 0.07 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	9714 independent reflections
Radiation source: fine-focus sealed X-ray tube	5617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ϕ scan and ω scans with κ offsets	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −16→16
T_min = 0.851, T_max = 0.967	k = −16→16
15129 measured reflections	l = −16→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0472P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
9714 reflections	Δρ_max = 0.35 e Å⁻³
573 parameters	Δρ_min = −0.47 e Å⁻³
6 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0015 (4)

Crystal data top

C₂₄H₂₂FeN₂O₃S	γ = 92.735 (3)°
M_r = 474.36	V = 2134.35 (18) Å³
Triclinic, P1	Z = 4
a = 12.7466 (4) Å	Mo Kα radiation
b = 12.8752 (8) Å	µ = 0.83 mm⁻¹
c = 13.5661 (7) Å	T = 150 K
α = 91.811 (3)°	0.20 × 0.07 × 0.04 mm
β = 106.096 (3)°

Data collection top

Nonius KappaCCD diffractometer	9714 independent reflections
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	5617 reflections with I > 2σ(I)
T_min = 0.851, T_max = 0.967	R_int = 0.069
15129 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	6 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	Δρ_max = 0.35 e Å⁻³
9714 reflections	Δρ_min = −0.47 e Å⁻³
573 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.10206 (4)	0.65069 (4)	0.89920 (4)	0.03399 (14)
S1A	0.72421 (6)	0.54294 (7)	0.60277 (7)	0.0378 (2)
O1A	0.56479 (17)	0.48700 (19)	0.68635 (17)	0.0388 (6)
O2A	0.96302 (18)	0.7918 (2)	0.50731 (18)	0.0442 (6)
N1A	0.51968 (19)	0.6159 (2)	0.57640 (19)	0.0320 (6)
H1A	0.4684	0.6568	0.5456	0.038*
N2A	0.63768 (19)	0.6924 (2)	0.4917 (2)	0.0327 (6)
C1A	0.4973 (2)	0.5486 (3)	0.6456 (2)	0.0317 (8)
C2A	0.6182 (2)	0.6227 (3)	0.5527 (2)	0.0298 (7)
C3A	0.7421 (2)	0.6839 (3)	0.4806 (2)	0.0309 (7)
C4A	0.7989 (2)	0.6089 (3)	0.5347 (2)	0.0362 (8)
H4A	0.8714	0.5943	0.5351	0.043*
C5A	0.7758 (2)	0.7565 (3)	0.4093 (3)	0.0372 (8)
H51	0.7408	0.7303	0.3377	0.045*
H52	0.7478	0.8256	0.4181	0.045*
C6A	0.8968 (3)	0.7697 (3)	0.4249 (2)	0.0383 (8)
O3A	0.92290 (18)	0.7616 (3)	0.33630 (19)	0.0426 (10)	0.915 (7)
C7A	1.0400 (3)	0.7803 (4)	0.3411 (4)	0.0507 (13)	0.915 (7)
H71	1.0471	0.8030	0.2741	0.061*	0.915 (7)
H72	1.0745	0.8355	0.3942	0.061*	0.915 (7)
C8A	1.0942 (4)	0.6815 (5)	0.3669 (4)	0.0626 (16)	0.915 (7)
H81	1.1705	0.6903	0.3653	0.094*	0.915 (7)
H82	1.0561	0.6262	0.3166	0.094*	0.915 (7)
H83	1.0919	0.6627	0.4357	0.094*	0.915 (7)
C11A	0.0997 (2)	0.5680 (3)	0.7683 (2)	0.0334 (8)
C12A	0.0684 (3)	0.5021 (3)	0.8399 (3)	0.0366 (8)
H12A	0.1045	0.4426	0.8685	0.044*
C13A	−0.0255 (3)	0.5413 (3)	0.8604 (3)	0.0386 (8)
H13A	−0.0634	0.5124	0.9053	0.046*
C14A	−0.0535 (3)	0.6309 (3)	0.8030 (3)	0.0420 (9)
H14A	−0.1132	0.6725	0.8027	0.050*
C15A	0.0233 (2)	0.6474 (3)	0.7463 (2)	0.0364 (8)
H15A	0.0239	0.7022	0.7012	0.044*
C21A	0.2610 (3)	0.6949 (3)	0.9703 (3)	0.0500 (10)
H21A	0.3229	0.6718	0.9516	0.060*
C22A	0.2129 (3)	0.6474 (3)	1.0400 (3)	0.0467 (10)
H22A	0.2360	0.5869	1.0765	0.056*
C23A	0.1237 (3)	0.7062 (3)	1.0458 (3)	0.0513 (10)
H23A	0.0759	0.6922	1.0872	0.062*
C24A	0.1180 (3)	0.7893 (3)	0.9795 (3)	0.0563 (11)
H24A	0.0659	0.8411	0.9683	0.068*
C25A	0.2035 (3)	0.7817 (3)	0.9327 (3)	0.0526 (11)
H25A	0.2191	0.8274	0.8843	0.063*
C31A	0.1972 (2)	0.5610 (3)	0.7307 (2)	0.0314 (7)
C32A	0.2219 (3)	0.6345 (3)	0.6658 (3)	0.0394 (9)
H32A	0.1729	0.6874	0.6420	0.047*
C33A	0.3170 (3)	0.6313 (3)	0.6357 (3)	0.0405 (9)
H33A	0.3323	0.6817	0.5912	0.049*
C34A	0.3906 (2)	0.5548 (3)	0.6702 (2)	0.0305 (7)
C35A	0.3651 (3)	0.4808 (3)	0.7328 (3)	0.0419 (9)
H35A	0.4137	0.4272	0.7558	0.050*
C36A	0.2703 (3)	0.4835 (3)	0.7623 (3)	0.0425 (9)
H36A	0.2543	0.4316	0.8051	0.051*
O3C	0.9272 (19)	0.699 (2)	0.366 (2)	0.035*	0.085 (7)
C7C	1.032 (2)	0.734 (4)	0.349 (4)	0.035*	0.085 (7)
H73	1.0568	0.8052	0.3793	0.042*	0.085 (7)
H74	1.0284	0.7323	0.2751	0.042*	0.085 (7)
C8C	1.105 (5)	0.655 (4)	0.404 (4)	0.035*	0.085 (7)
H84	1.1804	0.6850	0.4262	0.052*	0.085 (7)
H85	1.1003	0.5942	0.3579	0.052*	0.085 (7)
H86	1.0818	0.6351	0.4641	0.052*	0.085 (7)
Fe2	0.37355 (3)	0.23279 (4)	0.07428 (4)	0.03324 (14)
S1B	−0.30369 (7)	−0.00479 (8)	0.25740 (7)	0.0422 (2)
O1B	−0.14071 (18)	−0.0188 (2)	0.17146 (18)	0.0463 (7)
O2B	−0.3855 (2)	0.2100 (2)	0.5140 (2)	0.0561 (7)
O3B	−0.3776 (2)	0.1416 (2)	0.66424 (18)	0.0487 (7)
N1B	−0.0847 (2)	0.0488 (2)	0.3338 (2)	0.0368 (7)
H1B	−0.0300	0.0777	0.3831	0.044*
N2B	−0.1961 (2)	0.0458 (2)	0.4451 (2)	0.0380 (7)
C1B	−0.0669 (3)	0.0227 (3)	0.2415 (3)	0.0355 (8)
C2B	−0.1859 (2)	0.0317 (3)	0.3530 (3)	0.0348 (8)
C3B	−0.3053 (3)	0.0267 (3)	0.4423 (3)	0.0359 (8)
C4B	−0.3734 (3)	0.0010 (3)	0.3484 (3)	0.0448 (9)
H4B	−0.4502	−0.0122	0.3346	0.054*
C5B	−0.3346 (3)	0.0336 (3)	0.5422 (3)	0.0419 (9)
H53	−0.2710	0.0146	0.5980	0.050*
H54	−0.3956	−0.0183	0.5388	0.050*
C6B	−0.3677 (2)	0.1390 (3)	0.5694 (3)	0.0348 (8)
C7B	−0.4060 (3)	0.2413 (4)	0.7034 (3)	0.0587 (12)
H75	−0.4678	0.2698	0.6519	0.070*
H76	−0.3426	0.2926	0.7183	0.070*
C8B	−0.4369 (3)	0.2198 (4)	0.7985 (3)	0.0707 (15)
H87	−0.5078	0.1803	0.7809	0.106*
H88	−0.4422	0.2857	0.8345	0.106*
H89	−0.3813	0.1791	0.8430	0.106*
C11B	0.3496 (2)	0.1131 (3)	0.1621 (2)	0.0318 (7)
C12B	0.3789 (3)	0.0753 (3)	0.0738 (3)	0.0367 (8)
H12B	0.3361	0.0270	0.0222	0.044*
C13B	0.4829 (3)	0.1221 (3)	0.0762 (3)	0.0405 (9)
H13B	0.5213	0.1109	0.0263	0.049*
C14B	0.5192 (3)	0.1880 (3)	0.1658 (3)	0.0396 (9)
H14B	0.5866	0.2284	0.1870	0.048*
C15B	0.4376 (2)	0.1834 (3)	0.2183 (2)	0.0344 (8)
H15B	0.4408	0.2208	0.2806	0.041*
C21B	0.2282 (3)	0.3007 (3)	0.0225 (3)	0.0483 (10)
H21B	0.1605	0.2788	0.0340	0.058*
C22B	0.2649 (3)	0.2662 (4)	−0.0599 (3)	0.0557 (11)
H22B	0.2278	0.2173	−0.1136	0.067*
C23B	0.3684 (4)	0.3183 (5)	−0.0478 (4)	0.0785 (17)
H23B	0.4142	0.3107	−0.0919	0.094*
C24B	0.3910 (4)	0.3841 (4)	0.0428 (4)	0.0733 (15)
H24B	0.4545	0.4291	0.0698	0.088*
C25B	0.3040 (3)	0.3709 (3)	0.0844 (3)	0.0587 (11)
H25B	0.2979	0.4048	0.1456	0.070*
C31B	0.2456 (2)	0.0904 (3)	0.1871 (2)	0.0314 (7)
C32B	0.2212 (2)	0.1389 (3)	0.2701 (2)	0.0318 (8)
H32B	0.2735	0.1878	0.3133	0.038*
C33B	0.1223 (2)	0.1177 (3)	0.2919 (2)	0.0318 (8)
H33B	0.1077	0.1515	0.3495	0.038*
C34B	0.0448 (2)	0.0467 (3)	0.2290 (2)	0.0323 (8)
C35B	0.0693 (3)	−0.0022 (3)	0.1463 (3)	0.0468 (10)
H35B	0.0172	−0.0510	0.1029	0.056*
C36B	0.1676 (3)	0.0189 (3)	0.1262 (3)	0.0477 (10)
H36B	0.1827	−0.0162	0.0695	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0359 (3)	0.0337 (3)	0.0330 (3)	0.0011 (2)	0.0111 (2)	−0.0004 (2)
S1A	0.0320 (4)	0.0398 (6)	0.0421 (5)	0.0052 (4)	0.0098 (4)	0.0083 (4)
O1A	0.0388 (12)	0.0366 (16)	0.0425 (14)	0.0057 (11)	0.0128 (11)	0.0094 (11)
O2A	0.0441 (13)	0.0513 (18)	0.0396 (14)	−0.0107 (12)	0.0189 (11)	−0.0104 (12)
O3A	0.0380 (14)	0.058 (3)	0.0358 (15)	0.0060 (13)	0.0157 (12)	0.0045 (15)
N1A	0.0302 (13)	0.0336 (18)	0.0334 (15)	0.0028 (11)	0.0107 (12)	0.0036 (13)
N2A	0.0318 (14)	0.0322 (18)	0.0336 (15)	0.0015 (12)	0.0085 (12)	−0.0001 (13)
C1A	0.0315 (16)	0.032 (2)	0.0306 (17)	−0.0017 (14)	0.0079 (14)	−0.0061 (15)
C2A	0.0279 (16)	0.032 (2)	0.0288 (16)	0.0020 (13)	0.0067 (13)	−0.0031 (15)
C3A	0.0286 (16)	0.033 (2)	0.0311 (17)	−0.0023 (13)	0.0091 (14)	−0.0034 (15)
C4A	0.0297 (16)	0.040 (2)	0.041 (2)	0.0014 (15)	0.0133 (15)	0.0044 (17)
C5A	0.0359 (17)	0.039 (2)	0.0411 (19)	0.0025 (15)	0.0186 (15)	0.0009 (17)
C6A	0.0448 (19)	0.036 (2)	0.039 (2)	−0.0005 (16)	0.0216 (17)	−0.0022 (17)
C7A	0.049 (2)	0.057 (4)	0.053 (3)	−0.004 (2)	0.026 (2)	0.003 (3)
C8A	0.053 (3)	0.075 (5)	0.055 (4)	0.012 (3)	0.005 (3)	−0.002 (3)
C11A	0.0362 (17)	0.032 (2)	0.0316 (18)	0.0002 (14)	0.0099 (14)	0.0008 (15)
C12A	0.0371 (18)	0.037 (2)	0.0357 (19)	−0.0021 (15)	0.0109 (15)	0.0003 (16)
C13A	0.0359 (18)	0.042 (2)	0.0404 (19)	−0.0047 (15)	0.0162 (15)	0.0024 (17)
C14A	0.0301 (17)	0.056 (3)	0.041 (2)	0.0048 (16)	0.0114 (15)	0.0024 (18)
C15A	0.0354 (17)	0.041 (2)	0.0335 (18)	0.0057 (15)	0.0094 (15)	0.0078 (16)
C21A	0.043 (2)	0.058 (3)	0.044 (2)	−0.0107 (19)	0.0064 (17)	−0.005 (2)
C22A	0.049 (2)	0.047 (3)	0.039 (2)	−0.0056 (18)	0.0046 (17)	0.0006 (18)
C23A	0.062 (2)	0.054 (3)	0.040 (2)	−0.009 (2)	0.0217 (19)	−0.014 (2)
C24A	0.074 (3)	0.035 (3)	0.056 (3)	0.002 (2)	0.015 (2)	−0.012 (2)
C25A	0.062 (2)	0.048 (3)	0.044 (2)	−0.018 (2)	0.0126 (19)	−0.002 (2)
C31A	0.0367 (17)	0.029 (2)	0.0285 (16)	−0.0013 (14)	0.0101 (14)	−0.0013 (15)
C32A	0.0394 (18)	0.041 (2)	0.043 (2)	0.0138 (16)	0.0169 (16)	0.0126 (17)
C33A	0.0449 (19)	0.039 (2)	0.043 (2)	0.0039 (16)	0.0195 (16)	0.0131 (17)
C34A	0.0357 (17)	0.029 (2)	0.0265 (16)	0.0003 (14)	0.0088 (14)	−0.0024 (14)
C35A	0.0454 (19)	0.038 (2)	0.051 (2)	0.0126 (16)	0.0244 (17)	0.0152 (18)
C36A	0.047 (2)	0.036 (2)	0.053 (2)	0.0091 (16)	0.0255 (17)	0.0175 (18)
Fe2	0.0322 (2)	0.0350 (3)	0.0354 (3)	0.0050 (2)	0.0132 (2)	0.0056 (2)
S1B	0.0348 (4)	0.0496 (6)	0.0448 (5)	0.0034 (4)	0.0152 (4)	0.0034 (4)
O1B	0.0416 (13)	0.0576 (19)	0.0410 (14)	−0.0107 (12)	0.0173 (11)	−0.0112 (13)
O2B	0.0802 (19)	0.0459 (18)	0.0618 (17)	0.0311 (15)	0.0456 (15)	0.0245 (15)
O3B	0.0612 (16)	0.0533 (19)	0.0373 (14)	0.0206 (13)	0.0198 (12)	0.0068 (13)
N1B	0.0349 (15)	0.042 (2)	0.0371 (16)	−0.0043 (13)	0.0178 (12)	−0.0043 (14)
N2B	0.0427 (16)	0.0363 (19)	0.0418 (17)	−0.0002 (13)	0.0235 (13)	0.0009 (14)
C1B	0.0403 (18)	0.033 (2)	0.0385 (19)	0.0003 (15)	0.0200 (16)	−0.0003 (16)
C2B	0.0366 (17)	0.030 (2)	0.043 (2)	−0.0014 (14)	0.0203 (15)	0.0023 (16)
C3B	0.0389 (18)	0.028 (2)	0.050 (2)	0.0081 (14)	0.0260 (16)	0.0061 (16)
C4B	0.0351 (18)	0.049 (3)	0.058 (2)	0.0105 (16)	0.0240 (18)	0.009 (2)
C5B	0.0461 (19)	0.036 (2)	0.057 (2)	0.0086 (16)	0.0335 (18)	0.0153 (18)
C6B	0.0297 (16)	0.038 (2)	0.043 (2)	0.0092 (14)	0.0169 (15)	0.0091 (17)
C7B	0.061 (2)	0.067 (3)	0.051 (2)	0.021 (2)	0.018 (2)	−0.007 (2)
C8B	0.055 (2)	0.098 (4)	0.059 (3)	−0.011 (2)	0.020 (2)	−0.030 (3)
C11B	0.0329 (16)	0.029 (2)	0.0358 (18)	0.0049 (14)	0.0129 (14)	0.0023 (15)
C12B	0.0399 (18)	0.033 (2)	0.044 (2)	0.0046 (15)	0.0221 (16)	−0.0020 (16)
C13B	0.0397 (18)	0.043 (2)	0.047 (2)	0.0074 (16)	0.0256 (16)	0.0036 (18)
C14B	0.0323 (17)	0.044 (2)	0.044 (2)	0.0035 (15)	0.0124 (15)	0.0075 (18)
C15B	0.0352 (17)	0.037 (2)	0.0311 (17)	0.0080 (14)	0.0087 (14)	0.0004 (15)
C21B	0.043 (2)	0.055 (3)	0.048 (2)	0.0124 (18)	0.0117 (18)	0.013 (2)
C22B	0.066 (3)	0.058 (3)	0.040 (2)	0.021 (2)	0.0048 (19)	0.007 (2)
C23B	0.075 (3)	0.109 (5)	0.078 (3)	0.046 (3)	0.052 (3)	0.066 (3)
C24B	0.056 (3)	0.051 (3)	0.101 (4)	0.000 (2)	0.001 (3)	0.038 (3)
C25B	0.065 (3)	0.047 (3)	0.060 (3)	0.022 (2)	0.007 (2)	0.007 (2)
C31B	0.0332 (16)	0.028 (2)	0.0353 (18)	0.0033 (13)	0.0136 (14)	0.0052 (15)
C32B	0.0324 (16)	0.035 (2)	0.0294 (17)	0.0051 (14)	0.0103 (14)	−0.0002 (15)
C33B	0.0343 (17)	0.036 (2)	0.0278 (16)	0.0072 (14)	0.0125 (14)	−0.0001 (15)
C34B	0.0346 (17)	0.032 (2)	0.0334 (18)	0.0006 (14)	0.0148 (14)	0.0043 (15)
C35B	0.051 (2)	0.047 (3)	0.048 (2)	−0.0161 (18)	0.0287 (18)	−0.0203 (19)
C36B	0.054 (2)	0.049 (3)	0.048 (2)	−0.0103 (18)	0.0324 (18)	−0.0149 (19)

Geometric parameters (Å, º) top

Fe1—C11A	2.034 (3)	C33A—H33A	0.9500
Fe1—C12A	2.031 (4)	C35A—H35A	0.9500
Fe1—C13A	2.040 (3)	C36A—H36A	0.9500
Fe1—C14A	2.048 (3)	Fe2—C11B	2.040 (3)
Fe1—C15A	2.036 (3)	Fe2—C12B	2.032 (4)
Fe1—C21A	2.033 (3)	Fe2—C13B	2.037 (3)
Fe1—C22A	2.040 (4)	Fe2—C14B	2.047 (3)
Fe1—C23A	2.033 (4)	Fe2—C15B	2.033 (3)
Fe1—C24A	2.033 (4)	Fe2—C21B	2.041 (4)
Fe1—C25A	2.035 (4)	Fe2—C23B	2.005 (4)
S1A—C2A	1.735 (3)	Fe2—C22B	2.031 (4)
S1A—C4A	1.716 (3)	Fe2—C24B	2.023 (5)
O1A—C1A	1.226 (4)	Fe2—C25B	2.042 (4)
O2A—C6A	1.215 (4)	S1B—C2B	1.724 (3)
O3A—C6A	1.335 (3)	S1B—C4B	1.711 (4)
O3A—C7A	1.483 (3)	O1B—C1B	1.224 (4)
N1A—C1A	1.374 (4)	O2B—C6B	1.192 (4)
N1A—C2A	1.379 (4)	O3B—C6B	1.327 (4)
N2A—C2A	1.300 (4)	O3B—C7B	1.472 (5)
N2A—C3A	1.390 (4)	N1B—C1B	1.367 (4)
C1A—C34A	1.493 (4)	N1B—C2B	1.394 (4)
C3A—C4A	1.346 (5)	N2B—C2B	1.299 (4)
C3A—C5A	1.498 (5)	N2B—C3B	1.393 (4)
C5A—C6A	1.498 (4)	C1B—C34B	1.498 (4)
C7A—C8A	1.482 (5)	C3B—C4B	1.348 (5)
C11A—C12A	1.435 (5)	C3B—C5B	1.504 (5)
C11A—C15A	1.426 (5)	C5B—C6B	1.505 (5)
C11A—C31A	1.473 (4)	C7B—C8B	1.480 (6)
C12A—C13A	1.414 (5)	C11B—C12B	1.428 (4)
C13A—C14A	1.416 (5)	C11B—C15B	1.430 (4)
C14A—C15A	1.416 (5)	C11B—C31B	1.475 (4)
C21A—C22A	1.403 (5)	C12B—C13B	1.421 (4)
C21A—C25A	1.398 (6)	C13B—C14B	1.414 (5)
C22A—C23A	1.415 (5)	C14B—C15B	1.413 (4)
C23A—C24A	1.412 (6)	C21B—C25B	1.369 (6)
C24A—C25A	1.411 (6)	C21B—C22B	1.395 (5)
C31A—C32A	1.395 (5)	C22B—C23B	1.417 (6)
C31A—C36A	1.394 (5)	C23B—C24B	1.423 (7)
C32A—C33A	1.384 (4)	C24B—C25B	1.382 (6)
C33A—C34A	1.394 (5)	C31B—C32B	1.387 (4)
C34A—C35A	1.382 (5)	C31B—C36B	1.388 (5)
C35A—C36A	1.376 (4)	C32B—C33B	1.389 (4)
O3C—C7C	1.474 (5)	C33B—C34B	1.392 (4)
C7C—C8C	1.480 (6)	C34B—C35B	1.385 (4)
N1A—H1A	0.8800	C35B—C36B	1.372 (5)
C4A—H4A	0.9500	N1B—H1B	0.8800
C5A—H51	0.9900	C4B—H4B	0.9500
C5A—H52	0.9900	C5B—H53	0.9900
C7A—H71	0.9900	C5B—H54	0.9900
C7A—H72	0.9900	C7B—H75	0.9900
C8A—H81	0.9800	C7B—H76	0.9900
C8A—H82	0.9800	C8B—H87	0.9800
C8A—H83	0.9800	C8B—H88	0.9800
C7C—H73	0.9900	C8B—H89	0.9800
C7C—H74	0.9900	C12B—H12B	0.9500
C8C—H84	0.9800	C13B—H13B	0.9500
C8C—H85	0.9800	C14B—H14B	0.9500
C8C—H86	0.9800	C15B—H15B	0.9500
C12A—H12A	0.9500	C21B—H21B	0.9500
C13A—H13A	0.9500	C22B—H22B	0.9500
C14A—H14A	0.9500	C23B—H23B	0.9500
C15A—H15A	0.9500	C24B—H24B	0.9500
C21A—H21A	0.9500	C25B—H25B	0.9500
C22A—H22A	0.9500	C32B—H32B	0.9500
C23A—H23A	0.9500	C33B—H33B	0.9500
C24A—H24A	0.9500	C35B—H35B	0.9500
C25A—H25A	0.9500	C36B—H36B	0.9500
C32A—H32A	0.9500

C12A—Fe1—C23A	129.21 (16)	C7C—C8C—H86	109.5
C12A—Fe1—C24A	167.90 (16)	H84—C8C—H86	109.5
C23A—Fe1—C24A	40.64 (16)	H85—C8C—H86	109.5
C12A—Fe1—C21A	117.36 (16)	C23B—Fe2—C24B	41.4 (2)
C23A—Fe1—C21A	67.86 (16)	C23B—Fe2—C22B	41.09 (19)
C24A—Fe1—C21A	67.83 (17)	C24B—Fe2—C22B	68.62 (19)
C12A—Fe1—C11A	41.34 (13)	C23B—Fe2—C12B	124.5 (2)
C23A—Fe1—C11A	167.01 (16)	C24B—Fe2—C12B	163.3 (2)
C24A—Fe1—C11A	150.01 (17)	C22B—Fe2—C12B	106.53 (16)
C21A—Fe1—C11A	106.95 (14)	C23B—Fe2—C15B	156.0 (2)
C12A—Fe1—C25A	150.07 (16)	C24B—Fe2—C15B	120.95 (18)
C23A—Fe1—C25A	68.22 (17)	C22B—Fe2—C15B	161.75 (16)
C24A—Fe1—C25A	40.58 (16)	C12B—Fe2—C15B	68.65 (14)
C21A—Fe1—C25A	40.21 (16)	C23B—Fe2—C13B	107.31 (17)
C11A—Fe1—C25A	116.12 (15)	C24B—Fe2—C13B	126.50 (18)
C12A—Fe1—C15A	68.87 (14)	C22B—Fe2—C13B	120.21 (16)
C23A—Fe1—C15A	151.46 (16)	C12B—Fe2—C13B	40.88 (13)
C24A—Fe1—C15A	117.54 (16)	C15B—Fe2—C13B	68.44 (14)
C21A—Fe1—C15A	128.10 (15)	C23B—Fe2—C11B	161.5 (2)
C11A—Fe1—C15A	41.03 (13)	C24B—Fe2—C11B	155.0 (2)
C25A—Fe1—C15A	107.50 (16)	C22B—Fe2—C11B	123.82 (16)
C12A—Fe1—C22A	107.94 (16)	C12B—Fe2—C11B	41.07 (13)
C23A—Fe1—C22A	40.67 (15)	C15B—Fe2—C11B	41.11 (13)
C24A—Fe1—C22A	68.34 (17)	C13B—Fe2—C11B	69.12 (13)
C21A—Fe1—C22A	40.29 (14)	C23B—Fe2—C21B	67.67 (17)
C11A—Fe1—C22A	127.82 (15)	C24B—Fe2—C21B	66.66 (17)
C25A—Fe1—C22A	68.12 (16)	C22B—Fe2—C21B	40.06 (15)
C15A—Fe1—C22A	166.15 (14)	C12B—Fe2—C21B	120.64 (15)
C12A—Fe1—C13A	40.66 (13)	C15B—Fe2—C21B	126.02 (14)
C23A—Fe1—C13A	109.56 (15)	C13B—Fe2—C21B	155.43 (15)
C24A—Fe1—C13A	129.98 (16)	C11B—Fe2—C21B	107.60 (14)
C21A—Fe1—C13A	151.38 (17)	C23B—Fe2—C25B	68.1 (2)
C11A—Fe1—C13A	68.89 (13)	C24B—Fe2—C25B	39.76 (19)
C25A—Fe1—C13A	167.69 (16)	C22B—Fe2—C25B	67.55 (17)
C15A—Fe1—C13A	68.29 (14)	C12B—Fe2—C25B	154.80 (16)
C22A—Fe1—C13A	118.70 (15)	C15B—Fe2—C25B	108.87 (16)
C12A—Fe1—C14A	68.61 (15)	C13B—Fe2—C25B	163.52 (16)
C23A—Fe1—C14A	118.91 (15)	C11B—Fe2—C25B	120.32 (16)
C24A—Fe1—C14A	108.94 (17)	C21B—Fe2—C25B	39.19 (16)
C21A—Fe1—C14A	166.50 (16)	C23B—Fe2—C14B	120.93 (17)
C11A—Fe1—C14A	68.89 (13)	C24B—Fe2—C14B	109.01 (16)
C25A—Fe1—C14A	128.93 (17)	C22B—Fe2—C14B	155.79 (15)
C15A—Fe1—C14A	40.57 (13)	C12B—Fe2—C14B	68.44 (14)
C22A—Fe1—C14A	152.17 (15)	C15B—Fe2—C14B	40.54 (13)
C13A—Fe1—C14A	40.53 (14)	C13B—Fe2—C14B	40.52 (14)
C2A—S1A—C4A	88.04 (16)	C11B—Fe2—C14B	68.89 (13)
C6A—O3A—C7A	116.9 (3)	C21B—Fe2—C14B	162.92 (15)
C1A—N1A—C2A	123.5 (3)	C25B—Fe2—C14B	126.99 (16)
C1A—N1A—H1A	118.2	C4B—S1B—C2B	88.03 (17)
C2A—N1A—H1A	118.2	C6B—O3B—C7B	116.6 (3)
C2A—N2A—C3A	110.1 (3)	C1B—N1B—C2B	122.9 (3)
O1A—C1A—N1A	120.1 (3)	C1B—N1B—H1B	118.6
O1A—C1A—C34A	121.9 (3)	C2B—N1B—H1B	118.6
N1A—C1A—C34A	118.0 (3)	C2B—N2B—C3B	109.0 (3)
N2A—C2A—N1A	121.0 (3)	O1B—C1B—N1B	120.4 (3)
N2A—C2A—S1A	115.6 (2)	O1B—C1B—C34B	121.4 (3)
N1A—C2A—S1A	123.3 (3)	N1B—C1B—C34B	118.2 (3)
C4A—C3A—N2A	114.7 (3)	N2B—C2B—N1B	120.8 (3)
C4A—C3A—C5A	128.6 (3)	N2B—C2B—S1B	116.6 (2)
N2A—C3A—C5A	116.7 (3)	N1B—C2B—S1B	122.6 (2)
C3A—C4A—S1A	111.6 (2)	C4B—C3B—N2B	115.0 (3)
C3A—C4A—H4A	124.2	C4B—C3B—C5B	127.1 (3)
S1A—C4A—H4A	124.2	N2B—C3B—C5B	117.9 (3)
C6A—C5A—C3A	114.6 (3)	C3B—C4B—S1B	111.3 (2)
C6A—C5A—H51	108.6	C3B—C4B—H4B	124.4
C3A—C5A—H51	108.6	S1B—C4B—H4B	124.4
C6A—C5A—H52	108.6	C3B—C5B—C6B	114.6 (3)
C3A—C5A—H52	108.6	C3B—C5B—H53	108.6
H51—C5A—H52	107.6	C6B—C5B—H53	108.6
O2A—C6A—O3A	123.7 (3)	C3B—C5B—H54	108.6
O2A—C6A—C5A	124.2 (3)	C6B—C5B—H54	108.6
O3A—C6A—C5A	111.9 (3)	H53—C5B—H54	107.6
C8A—C7A—O3A	107.9 (4)	O2B—C6B—O3B	124.0 (3)
C8A—C7A—H71	110.1	O2B—C6B—C5B	125.8 (3)
O3A—C7A—H71	110.1	O3B—C6B—C5B	110.2 (3)
C8A—C7A—H72	110.1	O3B—C7B—C8B	106.8 (4)
O3A—C7A—H72	110.1	O3B—C7B—H75	110.4
H71—C7A—H72	108.4	C8B—C7B—H75	110.4
C15A—C11A—C12A	107.0 (3)	O3B—C7B—H76	110.4
C15A—C11A—C31A	126.0 (3)	C8B—C7B—H76	110.4
C12A—C11A—C31A	126.8 (3)	H75—C7B—H76	108.6
C15A—C11A—Fe1	69.58 (19)	C7B—C8B—H87	109.5
C12A—C11A—Fe1	69.21 (19)	C7B—C8B—H88	109.5
C31A—C11A—Fe1	122.6 (2)	H87—C8B—H88	109.5
C13A—C12A—C11A	108.0 (3)	C7B—C8B—H89	109.5
C13A—C12A—Fe1	70.0 (2)	H87—C8B—H89	109.5
C11A—C12A—Fe1	69.5 (2)	H88—C8B—H89	109.5
C13A—C12A—H12A	126.0	C12B—C11B—C15B	106.6 (3)
C11A—C12A—H12A	126.0	C12B—C11B—C31B	126.9 (3)
Fe1—C12A—H12A	126.1	C15B—C11B—C31B	126.3 (3)
C12A—C13A—C14A	108.6 (3)	C12B—C11B—Fe2	69.2 (2)
C12A—C13A—Fe1	69.31 (19)	C15B—C11B—Fe2	69.18 (19)
C14A—C13A—Fe1	70.0 (2)	C31B—C11B—Fe2	123.3 (2)
C12A—C13A—H13A	125.7	C13B—C12B—C11B	108.5 (3)
C14A—C13A—H13A	125.7	C13B—C12B—Fe2	69.7 (2)
Fe1—C13A—H13A	126.5	C11B—C12B—Fe2	69.8 (2)
C13A—C14A—C15A	107.8 (3)	C13B—C12B—H12B	125.8
C13A—C14A—Fe1	69.42 (19)	C11B—C12B—H12B	125.8
C15A—C14A—Fe1	69.25 (18)	Fe2—C12B—H12B	126.3
C13A—C14A—H14A	126.1	C14B—C13B—C12B	108.0 (3)
C15A—C14A—H14A	126.1	C14B—C13B—Fe2	70.1 (2)
Fe1—C14A—H14A	126.8	C12B—C13B—Fe2	69.38 (19)
C14A—C15A—C11A	108.7 (3)	C14B—C13B—H13B	126.0
C14A—C15A—Fe1	70.18 (19)	C12B—C13B—H13B	126.0
C11A—C15A—Fe1	69.40 (18)	Fe2—C13B—H13B	126.1
C14A—C15A—H15A	125.7	C15B—C14B—C13B	108.1 (3)
C11A—C15A—H15A	125.7	C15B—C14B—Fe2	69.20 (18)
Fe1—C15A—H15A	126.3	C13B—C14B—Fe2	69.36 (19)
C25A—C21A—C22A	109.1 (4)	C15B—C14B—H14B	126.0
C25A—C21A—Fe1	70.0 (2)	C13B—C14B—H14B	126.0
C22A—C21A—Fe1	70.1 (2)	Fe2—C14B—H14B	127.0
C25A—C21A—H21A	125.4	C14B—C15B—C11B	108.8 (3)
C22A—C21A—H21A	125.4	C14B—C15B—Fe2	70.26 (19)
Fe1—C21A—H21A	126.0	C11B—C15B—Fe2	69.72 (18)
C21A—C22A—C23A	107.3 (4)	C14B—C15B—H15B	125.6
C21A—C22A—Fe1	69.6 (2)	C11B—C15B—H15B	125.6
C23A—C22A—Fe1	69.4 (2)	Fe2—C15B—H15B	126.0
C21A—C22A—H22A	126.4	C25B—C21B—C22B	110.0 (4)
C23A—C22A—H22A	126.4	C25B—C21B—Fe2	70.5 (2)
Fe1—C22A—H22A	126.2	C22B—C21B—Fe2	69.6 (2)
C24A—C23A—C22A	108.0 (4)	C25B—C21B—H21B	125.0
C24A—C23A—Fe1	69.7 (2)	C22B—C21B—H21B	125.0
C22A—C23A—Fe1	69.9 (2)	Fe2—C21B—H21B	126.5
C24A—C23A—H23A	126.0	C21B—C22B—C23B	106.5 (4)
C22A—C23A—H23A	126.0	C21B—C22B—Fe2	70.3 (2)
Fe1—C23A—H23A	126.0	C23B—C22B—Fe2	68.5 (2)
C25A—C24A—C23A	107.9 (4)	C21B—C22B—H22B	126.7
C25A—C24A—Fe1	69.8 (2)	C23B—C22B—H22B	126.7
C23A—C24A—Fe1	69.7 (2)	Fe2—C22B—H22B	126.0
C25A—C24A—H24A	126.1	C22B—C23B—C24B	107.1 (4)
C23A—C24A—H24A	126.1	C22B—C23B—Fe2	70.4 (2)
Fe1—C24A—H24A	126.0	C24B—C23B—Fe2	70.0 (3)
C21A—C25A—C24A	107.7 (4)	C22B—C23B—H23B	126.4
C21A—C25A—Fe1	69.8 (2)	C24B—C23B—H23B	126.4
C24A—C25A—Fe1	69.6 (2)	Fe2—C23B—H23B	124.8
C21A—C25A—H25A	126.1	C25B—C24B—C23B	107.8 (4)
C24A—C25A—H25A	126.1	C25B—C24B—Fe2	70.9 (3)
Fe1—C25A—H25A	126.0	C23B—C24B—Fe2	68.7 (3)
C36A—C31A—C32A	117.7 (3)	C25B—C24B—H24B	126.1
C36A—C31A—C11A	121.1 (3)	C23B—C24B—H24B	126.1
C32A—C31A—C11A	121.1 (3)	Fe2—C24B—H24B	126.0
C33A—C32A—C31A	120.9 (3)	C21B—C25B—C24B	108.5 (4)
C33A—C32A—H32A	119.5	C21B—C25B—Fe2	70.4 (2)
C31A—C32A—H32A	119.5	C24B—C25B—Fe2	69.4 (3)
C32A—C33A—C34A	120.6 (3)	C21B—C25B—H25B	125.8
C32A—C33A—H33A	119.7	C24B—C25B—H25B	125.8
C34A—C33A—H33A	119.7	Fe2—C25B—H25B	126.1
C35A—C34A—C33A	118.5 (3)	C32B—C31B—C36B	117.6 (3)
C35A—C34A—C1A	117.4 (3)	C32B—C31B—C11B	122.3 (3)
C33A—C34A—C1A	124.1 (3)	C36B—C31B—C11B	120.1 (3)
C36A—C35A—C34A	120.9 (3)	C31B—C32B—C33B	121.7 (3)
C36A—C35A—H35A	119.6	C31B—C32B—H32B	119.2
C34A—C35A—H35A	119.6	C33B—C32B—H32B	119.2
C35A—C36A—C31A	121.3 (3)	C32B—C33B—C34B	119.8 (3)
C35A—C36A—H36A	119.3	C32B—C33B—H33B	120.1
C31A—C36A—H36A	119.3	C34B—C33B—H33B	120.1
O3C—C7C—C8C	101 (3)	C35B—C34B—C33B	118.6 (3)
O3C—C7C—H73	111.5	C35B—C34B—C1B	117.0 (3)
C8C—C7C—H73	111.5	C33B—C34B—C1B	124.3 (3)
O3C—C7C—H74	111.5	C36B—C35B—C34B	120.9 (3)
C8C—C7C—H74	111.5	C36B—C35B—H35B	119.5
H73—C7C—H74	109.3	C34B—C35B—H35B	119.5
C7C—C8C—H84	109.5	C35B—C36B—C31B	121.4 (3)
C7C—C8C—H85	109.5	C35B—C36B—H36B	119.3
H84—C8C—H85	109.5	C31B—C36B—H36B	119.3

C2A—N1A—C1A—O1A	−3.4 (5)	C6A—O3A—O3C—C7C	−122 (3)
C2A—N1A—C1A—C34A	175.3 (3)	C7A—O3A—O3C—C7C	−6 (3)
C3A—N2A—C2A—N1A	179.6 (3)	O3A—O3C—C7C—C8C	172 (4)
C3A—N2A—C2A—S1A	0.9 (3)	C2B—N1B—C1B—O1B	−0.9 (5)
C1A—N1A—C2A—N2A	−175.5 (3)	C2B—N1B—C1B—C34B	178.9 (3)
C1A—N1A—C2A—S1A	3.1 (4)	C3B—N2B—C2B—N1B	178.0 (3)
C4A—S1A—C2A—N2A	−0.5 (3)	C3B—N2B—C2B—S1B	0.0 (4)
C4A—S1A—C2A—N1A	−179.2 (3)	C1B—N1B—C2B—N2B	171.5 (3)
C2A—N2A—C3A—C4A	−0.8 (4)	C1B—N1B—C2B—S1B	−10.6 (5)
C2A—N2A—C3A—C5A	177.8 (3)	C4B—S1B—C2B—N2B	0.8 (3)
N2A—C3A—C4A—S1A	0.4 (4)	C4B—S1B—C2B—N1B	−177.2 (3)
C5A—C3A—C4A—S1A	−178.0 (3)	C2B—N2B—C3B—C4B	−1.2 (5)
C2A—S1A—C4A—C3A	0.0 (3)	C2B—N2B—C3B—C5B	177.1 (3)
C4A—C3A—C5A—C6A	−20.6 (5)	N2B—C3B—C4B—S1B	1.8 (4)
N2A—C3A—C5A—C6A	161.0 (3)	C5B—C3B—C4B—S1B	−176.3 (3)
O3C—O3A—C6A—O2A	89.9 (17)	C2B—S1B—C4B—C3B	−1.4 (3)
C7A—O3A—C6A—O2A	0.4 (6)	C4B—C3B—C5B—C6B	−89.9 (5)
O3C—O3A—C6A—C5A	−94.5 (17)	N2B—C3B—C5B—C6B	92.0 (4)
C7A—O3A—C6A—C5A	176.0 (3)	C7B—O3B—C6B—O2B	−3.9 (5)
C3A—C5A—C6A—O2A	−51.5 (5)	C7B—O3B—C6B—C5B	178.0 (3)
C3A—C5A—C6A—O3A	132.9 (3)	C3B—C5B—C6B—O2B	10.3 (5)
O3C—O3A—C7A—C8A	12.9 (12)	C3B—C5B—C6B—O3B	−171.6 (3)
C6A—O3A—C7A—C8A	84.6 (5)	C6B—O3B—C7B—C8B	167.5 (3)
C12A—Fe1—C11A—C15A	118.4 (3)	C23B—Fe2—C11B—C12B	44.7 (5)
C23A—Fe1—C11A—C15A	166.4 (6)	C24B—Fe2—C11B—C12B	−170.9 (3)
C24A—Fe1—C11A—C15A	−54.4 (4)	C22B—Fe2—C11B—C12B	75.7 (2)
C21A—Fe1—C11A—C15A	−129.2 (2)	C15B—Fe2—C11B—C12B	−118.2 (3)
C25A—Fe1—C11A—C15A	−86.9 (2)	C13B—Fe2—C11B—C12B	−37.45 (18)
C22A—Fe1—C11A—C15A	−168.6 (2)	C21B—Fe2—C11B—C12B	116.7 (2)
C13A—Fe1—C11A—C15A	80.8 (2)	C25B—Fe2—C11B—C12B	157.6 (2)
C14A—Fe1—C11A—C15A	37.2 (2)	C14B—Fe2—C11B—C12B	−81.0 (2)
C23A—Fe1—C11A—C12A	48.0 (7)	C23B—Fe2—C11B—C15B	162.9 (5)
C24A—Fe1—C11A—C12A	−172.7 (3)	C24B—Fe2—C11B—C15B	−52.7 (4)
C21A—Fe1—C11A—C12A	112.4 (2)	C22B—Fe2—C11B—C15B	−166.2 (2)
C25A—Fe1—C11A—C12A	154.7 (2)	C12B—Fe2—C11B—C15B	118.2 (3)
C15A—Fe1—C11A—C12A	−118.4 (3)	C13B—Fe2—C11B—C15B	80.7 (2)
C22A—Fe1—C11A—C12A	73.0 (2)	C21B—Fe2—C11B—C15B	−125.1 (2)
C13A—Fe1—C11A—C12A	−37.60 (19)	C25B—Fe2—C11B—C15B	−84.2 (2)
C14A—Fe1—C11A—C12A	−81.2 (2)	C14B—Fe2—C11B—C15B	37.19 (19)
C12A—Fe1—C11A—C31A	−121.2 (4)	C23B—Fe2—C11B—C31B	−76.6 (6)
C23A—Fe1—C11A—C31A	−73.2 (7)	C24B—Fe2—C11B—C31B	67.8 (5)
C24A—Fe1—C11A—C31A	66.0 (4)	C22B—Fe2—C11B—C31B	−45.6 (3)
C21A—Fe1—C11A—C31A	−8.8 (3)	C12B—Fe2—C11B—C31B	−121.3 (3)
C25A—Fe1—C11A—C31A	33.4 (3)	C15B—Fe2—C11B—C31B	120.5 (3)
C15A—Fe1—C11A—C31A	120.4 (4)	C13B—Fe2—C11B—C31B	−158.7 (3)
C22A—Fe1—C11A—C31A	−48.2 (4)	C21B—Fe2—C11B—C31B	−4.6 (3)
C13A—Fe1—C11A—C31A	−158.8 (3)	C25B—Fe2—C11B—C31B	36.3 (3)
C14A—Fe1—C11A—C31A	157.6 (3)	C14B—Fe2—C11B—C31B	157.7 (3)
C15A—C11A—C12A—C13A	0.1 (4)	C15B—C11B—C12B—C13B	−0.1 (4)
C31A—C11A—C12A—C13A	175.5 (3)	C31B—C11B—C12B—C13B	175.8 (3)
Fe1—C11A—C12A—C13A	59.7 (2)	Fe2—C11B—C12B—C13B	59.2 (3)
C15A—C11A—C12A—Fe1	−59.6 (2)	C15B—C11B—C12B—Fe2	−59.3 (2)
C31A—C11A—C12A—Fe1	115.8 (3)	C31B—C11B—C12B—Fe2	116.6 (3)
C23A—Fe1—C12A—C13A	73.3 (3)	C23B—Fe2—C12B—C13B	75.9 (3)
C24A—Fe1—C12A—C13A	43.4 (8)	C24B—Fe2—C12B—C13B	46.8 (6)
C21A—Fe1—C12A—C13A	156.1 (2)	C22B—Fe2—C12B—C13B	117.3 (2)
C11A—Fe1—C12A—C13A	−119.1 (3)	C15B—Fe2—C12B—C13B	−81.3 (2)
C25A—Fe1—C12A—C13A	−169.4 (3)	C11B—Fe2—C12B—C13B	−119.8 (3)
C15A—Fe1—C12A—C13A	−80.9 (2)	C21B—Fe2—C12B—C13B	158.5 (2)
C22A—Fe1—C12A—C13A	113.4 (2)	C25B—Fe2—C12B—C13B	−170.4 (3)
C14A—Fe1—C12A—C13A	−37.2 (2)	C14B—Fe2—C12B—C13B	−37.6 (2)
C23A—Fe1—C12A—C11A	−167.5 (2)	C23B—Fe2—C12B—C11B	−164.3 (2)
C24A—Fe1—C12A—C11A	162.5 (7)	C24B—Fe2—C12B—C11B	166.6 (5)
C21A—Fe1—C12A—C11A	−84.8 (2)	C22B—Fe2—C12B—C11B	−122.9 (2)
C25A—Fe1—C12A—C11A	−50.3 (4)	C15B—Fe2—C12B—C11B	38.48 (17)
C15A—Fe1—C12A—C11A	38.26 (18)	C13B—Fe2—C12B—C11B	119.8 (3)
C22A—Fe1—C12A—C11A	−127.4 (2)	C21B—Fe2—C12B—C11B	−81.7 (2)
C13A—Fe1—C12A—C11A	119.1 (3)	C25B—Fe2—C12B—C11B	−50.6 (4)
C14A—Fe1—C12A—C11A	81.9 (2)	C14B—Fe2—C12B—C11B	82.19 (19)
C11A—C12A—C13A—C14A	−0.1 (4)	C11B—C12B—C13B—C14B	0.5 (4)
Fe1—C12A—C13A—C14A	59.2 (2)	Fe2—C12B—C13B—C14B	59.7 (3)
C11A—C12A—C13A—Fe1	−59.3 (2)	C11B—C12B—C13B—Fe2	−59.2 (2)
C23A—Fe1—C13A—C12A	−128.0 (2)	C23B—Fe2—C13B—C14B	117.6 (3)
C24A—Fe1—C13A—C12A	−169.2 (2)	C24B—Fe2—C13B—C14B	76.0 (3)
C21A—Fe1—C13A—C12A	−48.6 (4)	C22B—Fe2—C13B—C14B	160.6 (2)
C11A—Fe1—C13A—C12A	38.2 (2)	C12B—Fe2—C13B—C14B	−119.2 (3)
C25A—Fe1—C13A—C12A	154.6 (7)	C15B—Fe2—C13B—C14B	−37.3 (2)
C15A—Fe1—C13A—C12A	82.4 (2)	C11B—Fe2—C13B—C14B	−81.6 (2)
C22A—Fe1—C13A—C12A	−84.3 (2)	C21B—Fe2—C13B—C14B	−168.3 (3)
C14A—Fe1—C13A—C12A	120.0 (3)	C25B—Fe2—C13B—C14B	46.4 (6)
C12A—Fe1—C13A—C14A	−120.0 (3)	C23B—Fe2—C13B—C12B	−123.2 (3)
C23A—Fe1—C13A—C14A	112.0 (2)	C24B—Fe2—C13B—C12B	−164.9 (3)
C24A—Fe1—C13A—C14A	70.8 (3)	C22B—Fe2—C13B—C12B	−80.2 (3)
C21A—Fe1—C13A—C14A	−168.6 (3)	C15B—Fe2—C13B—C12B	81.9 (2)
C11A—Fe1—C13A—C14A	−81.8 (2)	C11B—Fe2—C13B—C12B	37.6 (2)
C25A—Fe1—C13A—C14A	34.6 (8)	C21B—Fe2—C13B—C12B	−49.2 (4)
C15A—Fe1—C13A—C14A	−37.6 (2)	C25B—Fe2—C13B—C12B	165.5 (5)
C22A—Fe1—C13A—C14A	155.6 (2)	C14B—Fe2—C13B—C12B	119.2 (3)
C12A—C13A—C14A—C15A	0.1 (4)	C12B—C13B—C14B—C15B	−0.7 (4)
Fe1—C13A—C14A—C15A	58.8 (2)	Fe2—C13B—C14B—C15B	58.5 (2)
C12A—C13A—C14A—Fe1	−58.7 (2)	C12B—C13B—C14B—Fe2	−59.2 (2)
C12A—Fe1—C14A—C13A	37.3 (2)	C23B—Fe2—C14B—C15B	159.8 (3)
C23A—Fe1—C14A—C13A	−86.7 (3)	C24B—Fe2—C14B—C15B	115.7 (3)
C24A—Fe1—C14A—C13A	−130.1 (2)	C22B—Fe2—C14B—C15B	−164.3 (4)
C21A—Fe1—C14A—C13A	156.2 (6)	C12B—Fe2—C14B—C15B	−81.9 (2)
C11A—Fe1—C14A—C13A	81.8 (2)	C13B—Fe2—C14B—C15B	−119.8 (3)
C25A—Fe1—C14A—C13A	−171.1 (2)	C11B—Fe2—C14B—C15B	−37.7 (2)
C15A—Fe1—C14A—C13A	119.4 (3)	C21B—Fe2—C14B—C15B	43.5 (6)
C22A—Fe1—C14A—C13A	−50.8 (4)	C25B—Fe2—C14B—C15B	75.1 (3)
C12A—Fe1—C14A—C15A	−82.1 (2)	C23B—Fe2—C14B—C13B	−80.4 (3)
C23A—Fe1—C14A—C15A	153.9 (2)	C24B—Fe2—C14B—C13B	−124.4 (3)
C24A—Fe1—C14A—C15A	110.5 (2)	C22B—Fe2—C14B—C13B	−44.5 (5)
C21A—Fe1—C14A—C15A	36.8 (8)	C12B—Fe2—C14B—C13B	37.9 (2)
C11A—Fe1—C14A—C15A	−37.6 (2)	C15B—Fe2—C14B—C13B	119.8 (3)
C25A—Fe1—C14A—C15A	69.6 (3)	C11B—Fe2—C14B—C13B	82.2 (2)
C22A—Fe1—C14A—C15A	−170.2 (3)	C21B—Fe2—C14B—C13B	163.4 (5)
C13A—Fe1—C14A—C15A	−119.4 (3)	C25B—Fe2—C14B—C13B	−165.1 (2)
C13A—C14A—C15A—C11A	0.0 (4)	C13B—C14B—C15B—C11B	0.6 (4)
Fe1—C14A—C15A—C11A	58.9 (2)	Fe2—C14B—C15B—C11B	59.3 (2)
C13A—C14A—C15A—Fe1	−58.9 (2)	C13B—C14B—C15B—Fe2	−58.6 (3)
C12A—C11A—C15A—C14A	0.0 (4)	C12B—C11B—C15B—C14B	−0.3 (4)
C31A—C11A—C15A—C14A	−175.5 (3)	C31B—C11B—C15B—C14B	−176.3 (3)
Fe1—C11A—C15A—C14A	−59.4 (2)	Fe2—C11B—C15B—C14B	−59.6 (2)
C12A—C11A—C15A—Fe1	59.3 (2)	C12B—C11B—C15B—Fe2	59.3 (2)
C31A—C11A—C15A—Fe1	−116.1 (3)	C31B—C11B—C15B—Fe2	−116.7 (3)
C12A—Fe1—C15A—C14A	81.4 (2)	C23B—Fe2—C15B—C14B	−46.9 (5)
C23A—Fe1—C15A—C14A	−53.7 (4)	C24B—Fe2—C15B—C14B	−83.3 (3)
C24A—Fe1—C15A—C14A	−87.4 (3)	C22B—Fe2—C15B—C14B	159.3 (5)
C21A—Fe1—C15A—C14A	−169.8 (2)	C12B—Fe2—C15B—C14B	81.4 (2)
C11A—Fe1—C15A—C14A	119.9 (3)	C13B—Fe2—C15B—C14B	37.3 (2)
C25A—Fe1—C15A—C14A	−130.2 (2)	C11B—Fe2—C15B—C14B	119.8 (3)
C22A—Fe1—C15A—C14A	160.5 (6)	C21B—Fe2—C15B—C14B	−165.5 (2)
C13A—Fe1—C15A—C14A	37.6 (2)	C25B—Fe2—C15B—C14B	−125.4 (2)
C12A—Fe1—C15A—C11A	−38.54 (19)	C23B—Fe2—C15B—C11B	−166.7 (4)
C23A—Fe1—C15A—C11A	−173.6 (3)	C24B—Fe2—C15B—C11B	156.9 (2)
C24A—Fe1—C15A—C11A	152.7 (2)	C22B—Fe2—C15B—C11B	39.4 (6)
C21A—Fe1—C15A—C11A	70.3 (3)	C12B—Fe2—C15B—C11B	−38.44 (18)
C25A—Fe1—C15A—C11A	109.9 (2)	C13B—Fe2—C15B—C11B	−82.5 (2)
C22A—Fe1—C15A—C11A	40.6 (7)	C21B—Fe2—C15B—C11B	74.7 (2)
C13A—Fe1—C15A—C11A	−82.4 (2)	C25B—Fe2—C15B—C11B	114.8 (2)
C14A—Fe1—C15A—C11A	−119.9 (3)	C14B—Fe2—C15B—C11B	−119.8 (3)
C12A—Fe1—C21A—C25A	154.1 (2)	C23B—Fe2—C21B—C25B	−82.3 (3)
C23A—Fe1—C21A—C25A	−82.0 (3)	C24B—Fe2—C21B—C25B	−37.3 (3)
C24A—Fe1—C21A—C25A	−38.0 (2)	C22B—Fe2—C21B—C25B	−121.3 (4)
C11A—Fe1—C21A—C25A	110.6 (2)	C12B—Fe2—C21B—C25B	159.7 (3)
C15A—Fe1—C21A—C25A	70.4 (3)	C15B—Fe2—C21B—C25B	75.0 (3)
C22A—Fe1—C21A—C25A	−120.2 (4)	C13B—Fe2—C21B—C25B	−165.2 (3)
C13A—Fe1—C21A—C25A	−172.5 (3)	C11B—Fe2—C21B—C25B	116.7 (3)
C14A—Fe1—C21A—C25A	40.7 (8)	C14B—Fe2—C21B—C25B	41.4 (6)
C12A—Fe1—C21A—C22A	−85.7 (3)	C23B—Fe2—C21B—C22B	39.0 (3)
C23A—Fe1—C21A—C22A	38.2 (2)	C24B—Fe2—C21B—C22B	84.0 (3)
C24A—Fe1—C21A—C22A	82.2 (3)	C12B—Fe2—C21B—C22B	−79.0 (3)
C11A—Fe1—C21A—C22A	−129.2 (2)	C15B—Fe2—C21B—C22B	−163.7 (3)
C25A—Fe1—C21A—C22A	120.2 (4)	C13B—Fe2—C21B—C22B	−43.9 (5)
C15A—Fe1—C21A—C22A	−169.4 (2)	C11B—Fe2—C21B—C22B	−122.0 (3)
C13A—Fe1—C21A—C22A	−52.3 (4)	C25B—Fe2—C21B—C22B	121.3 (4)
C14A—Fe1—C21A—C22A	160.9 (6)	C14B—Fe2—C21B—C22B	162.7 (5)
C25A—C21A—C22A—C23A	−0.1 (4)	C25B—C21B—C22B—C23B	−0.2 (5)
Fe1—C21A—C22A—C23A	−59.4 (2)	Fe2—C21B—C22B—C23B	−59.2 (3)
C25A—C21A—C22A—Fe1	59.3 (3)	C25B—C21B—C22B—Fe2	59.0 (3)
C12A—Fe1—C22A—C21A	111.4 (3)	C23B—Fe2—C22B—C21B	−117.7 (4)
C23A—Fe1—C22A—C21A	−118.6 (4)	C24B—Fe2—C22B—C21B	−78.7 (3)
C24A—Fe1—C22A—C21A	−80.8 (3)	C12B—Fe2—C22B—C21B	118.2 (3)
C11A—Fe1—C22A—C21A	69.8 (3)	C15B—Fe2—C22B—C21B	46.5 (6)
C25A—Fe1—C22A—C21A	−37.0 (2)	C13B—Fe2—C22B—C21B	160.5 (2)
C15A—Fe1—C22A—C21A	37.1 (8)	C11B—Fe2—C22B—C21B	76.6 (3)
C13A—Fe1—C22A—C21A	154.4 (2)	C25B—Fe2—C22B—C21B	−35.7 (3)
C14A—Fe1—C22A—C21A	−170.6 (3)	C14B—Fe2—C22B—C21B	−167.7 (3)
C12A—Fe1—C22A—C23A	−130.0 (2)	C24B—Fe2—C22B—C23B	39.0 (3)
C24A—Fe1—C22A—C23A	37.8 (2)	C12B—Fe2—C22B—C23B	−124.0 (3)
C21A—Fe1—C22A—C23A	118.6 (4)	C15B—Fe2—C22B—C23B	164.2 (5)
C11A—Fe1—C22A—C23A	−171.6 (2)	C13B—Fe2—C22B—C23B	−81.7 (3)
C25A—Fe1—C22A—C23A	81.6 (3)	C11B—Fe2—C22B—C23B	−165.6 (3)
C15A—Fe1—C22A—C23A	155.6 (6)	C21B—Fe2—C22B—C23B	117.7 (4)
C13A—Fe1—C22A—C23A	−87.1 (3)	C25B—Fe2—C22B—C23B	82.0 (3)
C14A—Fe1—C22A—C23A	−52.0 (4)	C14B—Fe2—C22B—C23B	−50.0 (5)
C21A—C22A—C23A—C24A	0.0 (4)	C21B—C22B—C23B—C24B	−0.3 (5)
Fe1—C22A—C23A—C24A	−59.5 (3)	Fe2—C22B—C23B—C24B	−60.7 (3)
C21A—C22A—C23A—Fe1	59.5 (2)	C21B—C22B—C23B—Fe2	60.4 (3)
C12A—Fe1—C23A—C24A	−170.8 (2)	C24B—Fe2—C23B—C22B	−117.5 (4)
C21A—Fe1—C23A—C24A	81.3 (3)	C12B—Fe2—C23B—C22B	74.7 (3)
C11A—Fe1—C23A—C24A	149.9 (6)	C15B—Fe2—C23B—C22B	−167.9 (3)
C25A—Fe1—C23A—C24A	37.8 (2)	C13B—Fe2—C23B—C22B	116.4 (3)
C15A—Fe1—C23A—C24A	−49.0 (4)	C11B—Fe2—C23B—C22B	40.6 (6)
C22A—Fe1—C23A—C24A	119.1 (3)	C21B—Fe2—C23B—C22B	−38.0 (3)
C13A—Fe1—C23A—C24A	−129.3 (2)	C25B—Fe2—C23B—C22B	−80.4 (3)
C14A—Fe1—C23A—C24A	−85.8 (3)	C14B—Fe2—C23B—C22B	158.5 (2)
C12A—Fe1—C23A—C22A	70.1 (3)	C22B—Fe2—C23B—C24B	117.5 (4)
C24A—Fe1—C23A—C22A	−119.1 (3)	C12B—Fe2—C23B—C24B	−167.8 (2)
C21A—Fe1—C23A—C22A	−37.8 (2)	C15B—Fe2—C23B—C24B	−50.3 (5)
C11A—Fe1—C23A—C22A	30.8 (8)	C13B—Fe2—C23B—C24B	−126.1 (3)
C25A—Fe1—C23A—C22A	−81.3 (3)	C11B—Fe2—C23B—C24B	158.1 (4)
C15A—Fe1—C23A—C22A	−168.1 (3)	C21B—Fe2—C23B—C24B	79.5 (3)
C13A—Fe1—C23A—C22A	111.6 (2)	C25B—Fe2—C23B—C24B	37.1 (3)
C14A—Fe1—C23A—C22A	155.1 (2)	C14B—Fe2—C23B—C24B	−83.9 (3)
C22A—C23A—C24A—C25A	0.1 (4)	C22B—C23B—C24B—C25B	0.7 (5)
Fe1—C23A—C24A—C25A	−59.6 (3)	Fe2—C23B—C24B—C25B	−60.3 (3)
C22A—C23A—C24A—Fe1	59.7 (3)	C22B—C23B—C24B—Fe2	61.0 (3)
C12A—Fe1—C24A—C25A	155.5 (7)	C23B—Fe2—C24B—C25B	118.9 (4)
C23A—Fe1—C24A—C25A	119.0 (4)	C22B—Fe2—C24B—C25B	80.2 (3)
C21A—Fe1—C24A—C25A	37.6 (2)	C12B—Fe2—C24B—C25B	156.3 (5)
C11A—Fe1—C24A—C25A	−48.0 (4)	C15B—Fe2—C24B—C25B	−82.5 (3)
C15A—Fe1—C24A—C25A	−85.0 (3)	C13B—Fe2—C24B—C25B	−167.3 (2)
C22A—Fe1—C24A—C25A	81.2 (3)	C11B—Fe2—C24B—C25B	−44.9 (5)
C13A—Fe1—C24A—C25A	−168.8 (2)	C21B—Fe2—C24B—C25B	36.7 (2)
C14A—Fe1—C24A—C25A	−128.4 (3)	C14B—Fe2—C24B—C25B	−125.5 (3)
C12A—Fe1—C24A—C23A	36.5 (9)	C22B—Fe2—C24B—C23B	−38.7 (2)
C21A—Fe1—C24A—C23A	−81.4 (3)	C12B—Fe2—C24B—C23B	37.3 (7)
C11A—Fe1—C24A—C23A	−167.0 (3)	C15B—Fe2—C24B—C23B	158.6 (2)
C25A—Fe1—C24A—C23A	−119.0 (4)	C13B—Fe2—C24B—C23B	73.7 (3)
C15A—Fe1—C24A—C23A	156.0 (2)	C11B—Fe2—C24B—C23B	−163.8 (3)
C22A—Fe1—C24A—C23A	−37.8 (2)	C21B—Fe2—C24B—C23B	−82.2 (3)
C13A—Fe1—C24A—C23A	72.2 (3)	C25B—Fe2—C24B—C23B	−118.9 (4)
C14A—Fe1—C24A—C23A	112.6 (2)	C14B—Fe2—C24B—C23B	115.6 (3)
C22A—C21A—C25A—C24A	0.1 (4)	C22B—C21B—C25B—C24B	0.6 (5)
Fe1—C21A—C25A—C24A	59.5 (3)	Fe2—C21B—C25B—C24B	59.1 (3)
C22A—C21A—C25A—Fe1	−59.4 (2)	C22B—C21B—C25B—Fe2	−58.5 (3)
C23A—C24A—C25A—C21A	−0.1 (4)	C23B—C24B—C25B—C21B	−0.8 (5)
Fe1—C24A—C25A—C21A	−59.6 (3)	Fe2—C24B—C25B—C21B	−59.7 (3)
C23A—C24A—C25A—Fe1	59.5 (3)	C23B—C24B—C25B—Fe2	58.9 (3)
C12A—Fe1—C25A—C21A	−51.1 (4)	C23B—Fe2—C25B—C21B	81.0 (3)
C23A—Fe1—C25A—C21A	81.0 (3)	C24B—Fe2—C25B—C21B	119.6 (4)
C24A—Fe1—C25A—C21A	118.9 (4)	C22B—Fe2—C25B—C21B	36.5 (2)
C11A—Fe1—C25A—C21A	−85.6 (3)	C12B—Fe2—C25B—C21B	−44.6 (5)
C15A—Fe1—C25A—C21A	−129.0 (2)	C15B—Fe2—C25B—C21B	−124.4 (2)
C22A—Fe1—C25A—C21A	37.0 (2)	C13B—Fe2—C25B—C21B	158.0 (5)
C13A—Fe1—C25A—C21A	163.0 (6)	C11B—Fe2—C25B—C21B	−80.6 (3)
C14A—Fe1—C25A—C21A	−168.7 (2)	C14B—Fe2—C25B—C21B	−165.9 (2)
C12A—Fe1—C25A—C24A	−170.0 (3)	C23B—Fe2—C25B—C24B	−38.6 (3)
C23A—Fe1—C25A—C24A	−37.8 (2)	C22B—Fe2—C25B—C24B	−83.1 (3)
C21A—Fe1—C25A—C24A	−118.9 (4)	C12B—Fe2—C25B—C24B	−164.2 (4)
C11A—Fe1—C25A—C24A	155.6 (2)	C15B—Fe2—C25B—C24B	116.0 (3)
C15A—Fe1—C25A—C24A	112.2 (3)	C13B—Fe2—C25B—C24B	38.4 (7)
C22A—Fe1—C25A—C24A	−81.8 (3)	C11B—Fe2—C25B—C24B	159.8 (3)
C13A—Fe1—C25A—C24A	44.1 (8)	C21B—Fe2—C25B—C24B	−119.6 (4)
C14A—Fe1—C25A—C24A	72.4 (3)	C14B—Fe2—C25B—C24B	74.5 (3)
C15A—C11A—C31A—C36A	175.8 (3)	C12B—C11B—C31B—C32B	−173.8 (3)
C12A—C11A—C31A—C36A	1.3 (5)	C15B—C11B—C31B—C32B	1.3 (5)
Fe1—C11A—C31A—C36A	88.6 (4)	Fe2—C11B—C31B—C32B	−86.1 (4)
C15A—C11A—C31A—C32A	−1.3 (5)	C12B—C11B—C31B—C36B	5.8 (5)
C12A—C11A—C31A—C32A	−175.8 (3)	C15B—C11B—C31B—C36B	−179.1 (3)
Fe1—C11A—C31A—C32A	−88.5 (4)	Fe2—C11B—C31B—C36B	93.5 (4)
C36A—C31A—C32A—C33A	−1.2 (5)	C36B—C31B—C32B—C33B	−0.4 (5)
C11A—C31A—C32A—C33A	176.0 (3)	C11B—C31B—C32B—C33B	179.2 (3)
C31A—C32A—C33A—C34A	−0.4 (5)	C31B—C32B—C33B—C34B	−0.4 (5)
C32A—C33A—C34A—C35A	1.7 (5)	C32B—C33B—C34B—C35B	0.7 (5)
C32A—C33A—C34A—C1A	−177.1 (3)	C32B—C33B—C34B—C1B	−176.2 (3)
O1A—C1A—C34A—C35A	−6.8 (5)	O1B—C1B—C34B—C35B	−15.6 (5)
N1A—C1A—C34A—C35A	174.4 (3)	N1B—C1B—C34B—C35B	164.6 (3)
O1A—C1A—C34A—C33A	171.9 (3)	O1B—C1B—C34B—C33B	161.3 (3)
N1A—C1A—C34A—C33A	−6.8 (5)	N1B—C1B—C34B—C33B	−18.5 (5)
C33A—C34A—C35A—C36A	−1.3 (5)	C33B—C34B—C35B—C36B	−0.2 (6)
C1A—C34A—C35A—C36A	177.5 (3)	C1B—C34B—C35B—C36B	176.9 (4)
C34A—C35A—C36A—C31A	−0.3 (6)	C34B—C35B—C36B—C31B	−0.7 (6)
C32A—C31A—C36A—C35A	1.6 (5)	C32B—C31B—C36B—C35B	1.0 (6)
C11A—C31A—C36A—C35A	−175.7 (3)	C11B—C31B—C36B—C35B	−178.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2Bⁱ	0.88	2.12	2.972 (4)	162
N1B—H1B···O2Aⁱⁱ	0.88	2.18	2.971 (3)	149
C33A—H33A···O2Bⁱ	0.95	2.24	3.184 (5)	173
C33B—H33B···O2Aⁱⁱ	0.95	2.46	3.395 (4)	167
C7A—H72···N2Bⁱⁱ	0.99	2.68	3.654 (6)	168
C7B—H75···N2Aⁱ	0.99	2.56	3.536 (5)	169

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₂₃H₁₉FeNO₃S	C₂₄H₂₂FeN₂O₃S
M_r	445.30	474.36
Crystal system, space group	Monoclinic, P2₁/n	Triclinic, P1
Temperature (K)	150	150
a, b, c (Å)	10.1428 (3), 8.0965 (2), 23.0557 (7)	12.7466 (4), 12.8752 (8), 13.5661 (7)
α, β, γ (°)	90, 95.4912 (14), 90	91.811 (3), 106.096 (3), 92.735 (3)
V (Å³)	1884.67 (9)	2134.35 (18)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.94	0.83
Crystal size (mm)	0.22 × 0.16 × 0.10	0.20 × 0.07 × 0.04

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)
T_min, T_max	0.820, 0.912	0.851, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	6335, 4313, 3441	15129, 9714, 5617
R_int	0.049	0.069
(sin θ/λ)_max (Å⁻¹)	0.650	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.088, 1.06	0.050, 0.127, 1.00
No. of reflections	4313	9714
No. of parameters	268	573
No. of restraints	0	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.63	0.35, −0.47

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002) and ORTEX (McArdle, 1995), SHELXL97, NRCVAX (Gabe et al., 1989) and PREP8 (Ferguson, 1998).

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.81 (2)	2.14 (2)	2.768 (2)	134 (2)
C5—H5···O2ⁱ	0.95	2.56	3.411 (3)	150
C15—H15···O1ⁱⁱ	0.95	2.56	3.401 (3)	147
C32—H32···O1ⁱⁱ	0.95	2.65	3.577 (2)	165
C7—H7C···Cg3ⁱⁱⁱ	0.98	2.83	3.604 (2)	136

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1/2, y−1/2, −z−1/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2Bⁱ	0.88	2.12	2.972 (4)	162
N1B—H1B···O2Aⁱⁱ	0.88	2.18	2.971 (3)	149
C33A—H33A···O2Bⁱ	0.95	2.24	3.184 (5)	173
C33B—H33B···O2Aⁱⁱ	0.95	2.46	3.395 (4)	167
C7A—H72···N2Bⁱⁱ	0.99	2.68	3.654 (6)	168
C7B—H75···N2Aⁱ	0.99	2.56	3.536 (5)	169

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

Acknowledgements

SA, JFG and PTMK thank Dublin City University and the Department of Education, Ireland, for funding the National Institute for Cellular Biotechnology (PRTLI programme, round #3, 2001–2008).

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ISSN: 2053-2296

Volume 61| Part 7| July 2005| Pages m365-m369

doi:10.1107/S010827010501783X

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Methyl 2-(4-ferrocenylbenzamido)thiophene-3-carboxylate and ethyl 2-(4-ferrocenylbenzamido)-1,3-thiazole-4-acetate, a unique ferrocene derivative containing a thiazole moiety

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds