Penta­carbonyl-1κ2C,2κ3C-(ferrocenyl­diphenyl­phosphine-1κP)[μ-2-(4-methyl­phen­yl)-2-aza­propane-1,3-dithiol­ato-1:2κ4S,S′:S,S′]diiron(I)(Fe—Fe)

Tang, Y.-F.; Zhu, J.-L.

doi:10.1107/S1600536808032698

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1423

doi:10.1107/S1600536808032698

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Pentacarbonyl-1κ²C,2κ³C-(ferrocenyldiphenylphosphine-1κP)[μ-2-(4-methylphenyl)-2-azapropane-1,3-dithiolato-1:2κ⁴S,S′:S,S′]diiron(I)(Fe—Fe)

Yan-Feng Tang ^a and Jin-Li Zhu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Nantong University, Natong 226007, People's Republic of China
^*Correspondence e-mail: jinlizhu@ntu.edu.cn

(Received 26 September 2008; accepted 10 October 2008; online 18 October 2008)

The title compound, [Fe₂(C₉H₁₁NS₂){Fe(C₅H₅)(C₁₇H₁₄P)}(CO)₅], was prepared as an azadithiolato–iron model for the iron-only hydrogenase active site. The Fe₂S₂ unit exhibits a butterfly conformation and the ferrocenyldiphenylphosphine ligand is trans to the Fe—Fe bond. The Fe—Fe distance of 2.5160 (8) Å is longer than found in related model structures. Intramolecular C—H⋯S and intermolecular C—H⋯O hydrogen bonds are observed.

Related literature

For general background, see: Cammack (1999 ); Evans & Pickett (2003 ); Nicolet et al. (1999 ); Peters et al. (1998 ). For related structures, see: Hou et al. (2006 ); Lawrence et al. (2001 ); Ott et al. (2004 ).

Experimental

Crystal data

[Fe₃(C₅H₅)(C₉H₁₁NS₂)(C₁₇H₁₄P)(CO)₅]
M_r = 819.25
Monoclinic, P 2₁ /c
a = 13.600 (2) Å
b = 10.8964 (19) Å
c = 23.396 (4) Å
β = 94.741 (3)°
V = 3455.2 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 298 (2) K
0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.760, T_max = 0.868
21457 measured reflections
8202 independent reflections
4258 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.079
S = 0.80
8202 reflections
434 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—C13	1.750 (4)
Fe1—P1	2.2565 (10)
Fe1—S1	2.2762 (11)
Fe1—S2	2.2818 (11)
Fe1—Fe2	2.5160 (8)
Fe2—C11	1.761 (5)
Fe2—C12	1.777 (5)
Fe2—C10	1.813 (5)
Fe2—S2	2.2546 (11)
Fe2—S1	2.2867 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯O2ⁱ	0.98	2.53	3.224 (5)	128
C24—H24⋯S2	0.98	2.72	3.561 (4)	144
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032698/ci2685sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032698/ci2685Isup2.hkl

checkCIF report

Comment top

The iron-only hydrogenases are enzymes that can efficiently catalyze the reversible reaction of hydrogen production (Cammack, 1999; Evans & Pickett, 2003). The active site at which this reaction takes place is composed of a butterfly shaped Fe₂S₂ unit covalently linked to a conventional Fe₄S₄ cluster by a bridged cysteinyl thioether (Peters et al., 1998; Nicolet et al., 1999). We have prepared the title complex as a structural model for the iron-only hydrogenases active site. Herein we report its crystal structure.

The molecular structure of the title complex is shown in Fig.1 and selected bond distances are listed in Table 1. In the Fe₂S₂ unit, the Fe—Fe distance of 2.5160 (8) Å is slightly longer than those observed in related complexes (Lawrence et al., 2001; Ott et al., 2004). The FcPPh₂ (Fc is ferrocenyl and Ph is phenyl) ligand is in apical position (trans to Fe—Fe bond), with an Fe—P distance of 2.2565 (10) Å. The Fe1—C(≡O) distances are ~0.04 Å shorter than those found in a related complex (Hou et al., 2006), consistent with an increase in the charge of Fe1 because one of the CO ligands was replaced by the FcPPh₂ ligand. The ferrocene unit is covalently linked to the Fe₂S₂ unit via the bridged diphenyl P atom, with an Fe1—P1—C23 angle of 118.32 (12)°. The N1 atom is displaced from the C5/C8/C9 plane by 0.168 (3) Å, and the sum of angles around N1 is 355.8°.

Intramolecular C—H···S and intermolecular C—H···O hydrogen bonds are observed.

Related literature top

For general background, see: Cammack (1999); Evans & Pickett (2003); Nicolet et al. (1999); Peters et al. (1998). For related structures, see: Hou et al. (2006); Lawrence et al. (2001); Ott et al. (2004).

Experimental top

The starting material [Fe₂(µ-SCH₂)₂(4-CH₃C₆H₄N)(CO)₆] was obtained in 50% yield according to the literature method (Hou et al., 2006). The solution of Me₃NO (120 mg, 1.06 mmol) was added to a red solution of [Fe₂(µ-SCH₂)₂(4-CH₃C₆H₄N)(CO)₆] (0.50 g, 1.05 mmol) with FcPPh₂ (0.39 g, 1.05 mmol) in CH₃CN (100 ml) via syringe under a nitrogen atmosphere. The reaction mixture was stirred at ambient temperature until the TLC indicated there was no remaining carbonyl complex of starting material. The solvent was removed under vacuum and the resulted dark red residue was purified by column chromatography on silica gel eluting with CH₂Cl₂-hexane (1:5 v/v). A dark red solid was obtained from recrystallization in n-pentane-CH₂Cl₂. Single crystals of the title compound for X-ray analysis were grown from a CH₂Cl₂-hexane (1:5 v/v) solution by slow evaporation at ambient temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 30% probability level.

Pentacarbonyl-1κ²C,2κ³C-(ferrocenyldiphenylphosphine-1κP)[µ-2-(4- methylphenyl)-2-azapropane-1,3-dithiolato- 1:2κ⁴S,S':S,S']diiron(I)(Fe—Fe) top

Crystal data top

[Fe₃(C₅H₅)(C₉H₁₁NS₂)(C₁₇H₁₄P)(CO)₅]	F(000) = 1672
M_r = 819.25	D_x = 1.575 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2549 reflections
a = 13.600 (2) Å	θ = 2.4–22.0°
b = 10.8964 (19) Å	µ = 1.45 mm⁻¹
c = 23.396 (4) Å	T = 298 K
β = 94.741 (3)°	Block, red
V = 3455.2 (11) Å³	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	8202 independent reflections
Radiation source: fine-focus sealed tube	4258 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −17→18
T_min = 0.760, T_max = 0.868	k = −9→14
21457 measured reflections	l = −31→30

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.048	w = 1/[σ²(F_o²) + (0.0157P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max = 0.001
S = 0.80	Δρ_max = 0.66 e Å⁻³
8202 reflections	Δρ_min = −0.39 e Å⁻³
434 parameters

Crystal data top

[Fe₃(C₅H₅)(C₉H₁₁NS₂)(C₁₇H₁₄P)(CO)₅]	V = 3455.2 (11) Å³
M_r = 819.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.600 (2) Å	µ = 1.45 mm⁻¹
b = 10.8964 (19) Å	T = 298 K
c = 23.396 (4) Å	0.20 × 0.20 × 0.10 mm
β = 94.741 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	8202 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	4258 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.868	R_int = 0.070
21457 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 0.80	Δρ_max = 0.66 e Å⁻³
8202 reflections	Δρ_min = −0.39 e Å⁻³
434 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.

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	0.20737 (4)	0.18453 (5)	0.30929 (2)	0.03252 (14)
Fe2	0.20176 (4)	0.09491 (5)	0.40808 (2)	0.03988 (16)
Fe3	0.08083 (4)	0.09519 (5)	0.11522 (2)	0.04244 (16)
S1	0.34466 (7)	0.12772 (9)	0.36528 (4)	0.0387 (2)
S2	0.15575 (7)	−0.00994 (9)	0.32718 (4)	0.0382 (2)
P1	0.26239 (7)	0.19707 (9)	0.22109 (4)	0.0316 (2)
O1	0.2115 (2)	−0.1033 (3)	0.49363 (13)	0.0791 (11)
O2	0.2652 (3)	0.3021 (3)	0.48103 (14)	0.1006 (13)
O3	−0.0037 (2)	0.1481 (3)	0.42412 (14)	0.0962 (12)
O4	0.2502 (2)	0.4345 (2)	0.34576 (12)	0.0634 (9)
O5	0.0021 (2)	0.2479 (3)	0.27912 (12)	0.0661 (9)
N1	0.3407 (2)	−0.1259 (3)	0.34951 (12)	0.0409 (8)
C1	0.4517 (4)	−0.3802 (4)	0.56016 (18)	0.0874 (16)
H1A	0.4496	−0.4671	0.5535	0.131*
H1B	0.4066	−0.3592	0.5881	0.131*
H1C	0.5173	−0.3566	0.5741	0.131*
C2	0.4224 (3)	−0.3132 (4)	0.50438 (17)	0.0536 (11)
C3	0.3533 (3)	−0.3595 (4)	0.46376 (18)	0.0529 (11)
H3	0.3241	−0.4348	0.4706	0.063*
C4	0.3255 (3)	−0.2992 (4)	0.41345 (16)	0.0459 (10)
H4	0.2792	−0.3346	0.3870	0.055*
C5	0.3662 (3)	−0.1853 (4)	0.40172 (16)	0.0394 (9)
C6	0.4364 (3)	−0.1384 (4)	0.44210 (17)	0.0485 (11)
H6	0.4658	−0.0634	0.4353	0.058*
C7	0.4635 (3)	−0.2009 (4)	0.49226 (17)	0.0579 (12)
H7	0.5107	−0.1667	0.5186	0.069*
C8	0.2455 (3)	−0.1362 (3)	0.31877 (16)	0.0479 (11)
H8A	0.2156	−0.2121	0.3304	0.057*
H8B	0.2551	−0.1436	0.2783	0.057*
C9	0.3917 (3)	−0.0175 (3)	0.33541 (15)	0.0448 (10)
H9A	0.3883	−0.0103	0.2940	0.054*
H9B	0.4606	−0.0266	0.3490	0.054*
C10	0.2131 (3)	−0.0291 (4)	0.45986 (18)	0.0539 (12)
C11	0.2391 (3)	0.2194 (4)	0.45270 (18)	0.0651 (14)
C12	0.0758 (3)	0.1262 (4)	0.41723 (17)	0.0561 (12)
C13	0.2339 (3)	0.3362 (4)	0.32971 (15)	0.0385 (10)
C14	0.0838 (3)	0.2218 (3)	0.28947 (16)	0.0431 (10)
C15	0.0207 (4)	0.2515 (5)	0.0789 (2)	0.0749 (15)
H15	0.0568	0.3196	0.0630	0.090*
C16	−0.0165 (4)	0.1463 (5)	0.0488 (2)	0.0738 (15)
H16	−0.0101	0.1287	0.0081	0.089*
C17	−0.0633 (3)	0.0727 (5)	0.0861 (2)	0.0736 (15)
H17	−0.0958	−0.0058	0.0766	0.088*
C18	−0.0557 (3)	0.1293 (5)	0.1406 (2)	0.0686 (14)
H18	−0.0826	0.0979	0.1754	0.082*
C19	−0.0044 (3)	0.2407 (4)	0.1355 (2)	0.0662 (14)
H19	0.0115	0.2999	0.1664	0.079*
C20	0.1400 (3)	−0.0774 (4)	0.12177 (17)	0.0518 (11)
H20	0.1039	−0.1546	0.1152	0.062*
C21	0.1848 (3)	−0.0097 (4)	0.08032 (18)	0.0551 (12)
H21	0.1854	−0.0312	0.0397	0.066*
C22	0.2278 (3)	0.0960 (4)	0.10657 (15)	0.0440 (10)
H22	0.2638	0.1598	0.0874	0.053*
C23	0.2103 (2)	0.0944 (3)	0.16603 (14)	0.0331 (9)
C24	0.1549 (3)	−0.0139 (3)	0.17502 (16)	0.0429 (10)
H24	0.1310	−0.0401	0.2115	0.051*
C25	0.3951 (2)	0.1685 (3)	0.22119 (14)	0.0303 (8)
C26	0.4591 (3)	0.2380 (3)	0.25719 (15)	0.0380 (9)
H26	0.4338	0.2998	0.2791	0.046*
C27	0.5593 (3)	0.2175 (4)	0.26120 (16)	0.0471 (11)
H27	0.6011	0.2650	0.2857	0.056*
C28	0.5975 (3)	0.1257 (4)	0.22858 (17)	0.0483 (11)
H28	0.6650	0.1103	0.2315	0.058*
C29	0.5357 (3)	0.0582 (3)	0.19212 (16)	0.0455 (11)
H29	0.5618	−0.0015	0.1693	0.055*
C30	0.4351 (3)	0.0770 (3)	0.18864 (15)	0.0370 (9)
H30	0.3937	0.0283	0.1645	0.044*
C31	0.2548 (3)	0.3488 (3)	0.18691 (15)	0.0343 (9)
C32	0.3189 (3)	0.3814 (3)	0.14616 (16)	0.0477 (11)
H32	0.3677	0.3266	0.1371	0.057*
C33	0.3115 (3)	0.4942 (4)	0.11883 (17)	0.0577 (12)
H33	0.3544	0.5141	0.0913	0.069*
C34	0.2412 (3)	0.5761 (4)	0.13229 (18)	0.0591 (12)
H34	0.2364	0.6519	0.1140	0.071*
C35	0.1777 (3)	0.5472 (4)	0.17249 (18)	0.0547 (12)
H35	0.1301	0.6034	0.1817	0.066*
C36	0.1843 (3)	0.4339 (3)	0.19954 (15)	0.0427 (10)
H36	0.1405	0.4148	0.2267	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0317 (3)	0.0340 (3)	0.0323 (3)	−0.0013 (3)	0.0052 (2)	−0.0022 (2)
Fe2	0.0415 (4)	0.0483 (4)	0.0305 (3)	−0.0029 (3)	0.0065 (3)	−0.0030 (3)
Fe3	0.0349 (3)	0.0523 (4)	0.0393 (3)	0.0000 (3)	−0.0020 (3)	−0.0046 (3)
S1	0.0357 (6)	0.0427 (6)	0.0374 (6)	−0.0044 (5)	0.0019 (5)	0.0000 (5)
S2	0.0405 (6)	0.0395 (6)	0.0343 (6)	−0.0058 (5)	0.0014 (5)	0.0002 (4)
P1	0.0296 (5)	0.0336 (6)	0.0319 (6)	0.0006 (5)	0.0038 (4)	−0.0019 (4)
O1	0.103 (3)	0.087 (3)	0.051 (2)	0.012 (2)	0.0248 (19)	0.0228 (18)
O2	0.138 (3)	0.099 (3)	0.067 (3)	−0.033 (3)	0.026 (2)	−0.042 (2)
O3	0.055 (2)	0.151 (4)	0.084 (3)	0.020 (2)	0.018 (2)	−0.018 (2)
O4	0.067 (2)	0.046 (2)	0.079 (2)	−0.0107 (16)	0.0131 (17)	−0.0186 (16)
O5	0.0356 (18)	0.080 (2)	0.083 (2)	0.0090 (16)	0.0092 (17)	0.0150 (17)
N1	0.049 (2)	0.038 (2)	0.036 (2)	0.0013 (16)	0.0032 (17)	0.0055 (15)
C1	0.098 (4)	0.094 (4)	0.067 (4)	−0.003 (3)	−0.013 (3)	0.034 (3)
C2	0.056 (3)	0.057 (3)	0.047 (3)	0.001 (2)	0.002 (2)	0.018 (2)
C3	0.055 (3)	0.047 (3)	0.058 (3)	−0.009 (2)	0.010 (2)	0.012 (2)
C4	0.049 (3)	0.044 (3)	0.043 (3)	−0.006 (2)	−0.002 (2)	−0.001 (2)
C5	0.041 (2)	0.040 (3)	0.037 (2)	0.004 (2)	0.0059 (19)	0.0015 (19)
C6	0.042 (3)	0.049 (3)	0.054 (3)	−0.007 (2)	−0.001 (2)	0.014 (2)
C7	0.050 (3)	0.062 (3)	0.059 (3)	−0.004 (2)	−0.011 (2)	0.008 (2)
C8	0.063 (3)	0.035 (3)	0.044 (3)	0.001 (2)	−0.006 (2)	−0.0051 (19)
C9	0.044 (2)	0.046 (3)	0.046 (3)	0.012 (2)	0.014 (2)	0.009 (2)
C10	0.045 (3)	0.080 (4)	0.039 (3)	0.002 (2)	0.016 (2)	−0.006 (2)
C11	0.072 (3)	0.083 (4)	0.043 (3)	−0.010 (3)	0.022 (3)	−0.013 (3)
C12	0.056 (3)	0.074 (3)	0.039 (3)	0.002 (3)	0.005 (2)	−0.006 (2)
C13	0.032 (2)	0.044 (3)	0.040 (2)	0.004 (2)	0.0056 (18)	−0.004 (2)
C14	0.045 (3)	0.037 (3)	0.050 (3)	−0.006 (2)	0.012 (2)	0.0042 (19)
C15	0.073 (4)	0.067 (4)	0.082 (4)	0.013 (3)	−0.011 (3)	0.016 (3)
C16	0.065 (4)	0.094 (5)	0.058 (3)	0.017 (3)	−0.021 (3)	−0.009 (3)
C17	0.038 (3)	0.087 (4)	0.093 (4)	−0.001 (3)	−0.016 (3)	−0.020 (3)
C18	0.035 (3)	0.098 (4)	0.073 (4)	0.004 (3)	0.005 (2)	−0.013 (3)
C19	0.045 (3)	0.071 (4)	0.080 (4)	0.020 (3)	−0.012 (3)	−0.021 (3)
C20	0.055 (3)	0.042 (3)	0.056 (3)	−0.001 (2)	−0.011 (2)	−0.013 (2)
C21	0.047 (3)	0.076 (3)	0.042 (3)	0.003 (2)	0.002 (2)	−0.024 (2)
C22	0.038 (2)	0.058 (3)	0.036 (2)	−0.005 (2)	0.0070 (19)	−0.006 (2)
C23	0.030 (2)	0.037 (2)	0.032 (2)	0.0003 (18)	0.0013 (17)	−0.0005 (18)
C24	0.046 (3)	0.045 (3)	0.036 (2)	−0.002 (2)	−0.001 (2)	−0.0014 (19)
C25	0.030 (2)	0.032 (2)	0.030 (2)	0.0019 (17)	0.0070 (17)	0.0068 (16)
C26	0.037 (2)	0.036 (2)	0.042 (2)	−0.0003 (19)	0.010 (2)	−0.0054 (18)
C27	0.036 (2)	0.052 (3)	0.052 (3)	−0.010 (2)	−0.003 (2)	0.001 (2)
C28	0.025 (2)	0.059 (3)	0.061 (3)	0.006 (2)	0.004 (2)	0.009 (2)
C29	0.039 (3)	0.046 (3)	0.053 (3)	0.012 (2)	0.015 (2)	0.000 (2)
C30	0.037 (2)	0.036 (2)	0.038 (2)	0.0036 (18)	0.0033 (18)	0.0005 (18)
C31	0.032 (2)	0.035 (2)	0.036 (2)	0.0001 (17)	0.0041 (18)	0.0048 (17)
C32	0.042 (3)	0.049 (3)	0.053 (3)	0.013 (2)	0.007 (2)	0.014 (2)
C33	0.053 (3)	0.065 (3)	0.057 (3)	0.006 (3)	0.014 (2)	0.027 (2)
C34	0.060 (3)	0.050 (3)	0.067 (3)	0.008 (2)	−0.001 (3)	0.023 (2)
C35	0.054 (3)	0.045 (3)	0.065 (3)	0.021 (2)	0.004 (2)	0.009 (2)
C36	0.036 (2)	0.050 (3)	0.043 (2)	0.008 (2)	0.0061 (19)	0.001 (2)

Geometric parameters (Å, º) top

Fe1—C13	1.750 (4)	C7—H7	0.93
Fe1—C14	1.754 (4)	C8—H8A	0.97
Fe1—P1	2.2565 (10)	C8—H8B	0.97
Fe1—S1	2.2762 (11)	C9—H9A	0.97
Fe1—S2	2.2818 (11)	C9—H9B	0.97
Fe1—Fe2	2.5160 (8)	C15—C19	1.399 (5)
Fe2—C11	1.761 (5)	C15—C16	1.417 (6)
Fe2—C12	1.777 (5)	C15—H15	0.98
Fe2—C10	1.813 (5)	C16—C17	1.379 (6)
Fe2—S2	2.2546 (11)	C16—H16	0.98
Fe2—S1	2.2867 (11)	C17—C18	1.413 (6)
Fe3—C22	2.025 (4)	C17—H17	0.98
Fe3—C18	2.030 (4)	C18—C19	1.410 (5)
Fe3—C16	2.034 (4)	C18—H18	0.98
Fe3—C17	2.036 (4)	C19—H19	0.98
Fe3—C24	2.038 (4)	C20—C21	1.398 (5)
Fe3—C21	2.040 (4)	C20—C24	1.425 (5)
Fe3—C23	2.041 (3)	C20—H20	0.98
Fe3—C19	2.043 (4)	C21—C22	1.409 (5)
Fe3—C15	2.044 (4)	C21—H21	0.98
Fe3—C20	2.047 (4)	C22—C23	1.431 (4)
S1—C9	1.864 (3)	C22—H22	0.98
S2—C8	1.860 (4)	C23—C24	1.425 (4)
P1—C23	1.806 (3)	C24—H24	0.98
P1—C25	1.832 (3)	C25—C26	1.385 (4)
P1—C31	1.836 (3)	C25—C30	1.392 (4)
O1—C10	1.132 (4)	C26—C27	1.376 (5)
O2—C11	1.157 (4)	C26—H26	0.93
O3—C12	1.132 (4)	C27—C28	1.385 (5)
O4—C13	1.151 (4)	C27—H27	0.93
O5—C14	1.153 (4)	C28—C29	1.363 (5)
N1—C5	1.400 (4)	C28—H28	0.93
N1—C9	1.421 (4)	C29—C30	1.380 (5)
N1—C8	1.433 (4)	C29—H29	0.93
C1—C2	1.519 (5)	C30—H30	0.93
C1—H1A	0.96	C31—C36	1.382 (4)
C1—H1B	0.96	C31—C32	1.391 (4)
C1—H1C	0.96	C32—C33	1.386 (5)
C2—C3	1.376 (5)	C32—H32	0.93
C2—C7	1.385 (5)	C33—C34	1.363 (5)
C3—C4	1.374 (5)	C33—H33	0.93
C3—H3	0.93	C34—C35	1.364 (5)
C4—C5	1.396 (5)	C34—H34	0.93
C4—H4	0.93	C35—C36	1.386 (4)
C5—C6	1.384 (5)	C35—H35	0.93
C6—C7	1.381 (5)	C36—H36	0.93
C6—H6	0.93

C13—Fe1—C14	91.41 (17)	N1—C8—S2	117.6 (2)
C13—Fe1—P1	96.67 (12)	N1—C8—H8A	107.9
C14—Fe1—P1	97.31 (12)	S2—C8—H8A	107.9
C13—Fe1—S1	87.66 (12)	N1—C8—H8B	107.9
C14—Fe1—S1	159.67 (12)	S2—C8—H8B	107.9
P1—Fe1—S1	102.97 (4)	H8A—C8—H8B	107.2
C13—Fe1—S2	152.46 (12)	N1—C9—S1	115.4 (2)
C14—Fe1—S2	87.77 (12)	N1—C9—H9A	108.4
P1—Fe1—S2	110.75 (4)	S1—C9—H9A	108.4
S1—Fe1—S2	83.80 (4)	N1—C9—H9B	108.4
C13—Fe1—Fe2	97.87 (12)	S1—C9—H9B	108.4
C14—Fe1—Fe2	103.39 (12)	H9A—C9—H9B	107.5
P1—Fe1—Fe2	154.30 (4)	O1—C10—Fe2	173.4 (4)
S1—Fe1—Fe2	56.73 (3)	O2—C11—Fe2	178.3 (4)
S2—Fe1—Fe2	55.80 (3)	O3—C12—Fe2	178.3 (4)
C11—Fe2—C12	90.8 (2)	O4—C13—Fe1	176.7 (3)
C11—Fe2—C10	100.0 (2)	O5—C14—Fe1	176.7 (4)
C12—Fe2—C10	95.26 (18)	C19—C15—C16	107.3 (5)
C11—Fe2—S2	159.16 (15)	C19—C15—Fe3	69.9 (3)
C12—Fe2—S2	89.71 (14)	C16—C15—Fe3	69.3 (3)
C10—Fe2—S2	100.70 (14)	C19—C15—H15	126.3
C11—Fe2—S1	85.74 (13)	C16—C15—H15	126.4
C12—Fe2—S1	152.32 (14)	Fe3—C15—H15	126.4
C10—Fe2—S1	112.39 (13)	C17—C16—C15	108.7 (5)
S2—Fe2—S1	84.18 (4)	C17—C16—Fe3	70.3 (3)
C11—Fe2—Fe1	102.51 (14)	C15—C16—Fe3	70.0 (3)
C12—Fe2—Fe1	97.99 (13)	C17—C16—H16	125.6
C10—Fe2—Fe1	153.62 (13)	C15—C16—H16	125.7
S2—Fe2—Fe1	56.83 (3)	Fe3—C16—H16	125.6
S1—Fe2—Fe1	56.34 (3)	C16—C17—C18	108.3 (5)
C22—Fe3—C18	164.24 (18)	C16—C17—Fe3	70.1 (3)
C22—Fe3—C16	120.53 (19)	C18—C17—Fe3	69.5 (2)
C18—Fe3—C16	67.69 (19)	C16—C17—H17	126.0
C22—Fe3—C17	153.86 (18)	C18—C17—H17	125.7
C18—Fe3—C17	40.67 (16)	Fe3—C17—H17	125.8
C16—Fe3—C17	39.61 (17)	C19—C18—C17	107.4 (4)
C22—Fe3—C24	68.59 (15)	C19—C18—Fe3	70.2 (2)
C18—Fe3—C24	108.54 (17)	C17—C18—Fe3	69.9 (2)
C16—Fe3—C24	159.7 (2)	C19—C18—H18	126.3
C17—Fe3—C24	124.54 (19)	C17—C18—H18	126.3
C22—Fe3—C21	40.55 (13)	Fe3—C18—H18	126.3
C18—Fe3—C21	154.22 (19)	C15—C19—C18	108.4 (4)
C16—Fe3—C21	106.06 (18)	C15—C19—Fe3	70.0 (2)
C17—Fe3—C21	118.59 (18)	C18—C19—Fe3	69.3 (2)
C24—Fe3—C21	68.17 (16)	C15—C19—H19	125.9
C22—Fe3—C23	41.20 (12)	C18—C19—H19	125.8
C18—Fe3—C23	126.57 (17)	Fe3—C19—H19	126.0
C16—Fe3—C23	157.2 (2)	C21—C20—C24	108.1 (4)
C17—Fe3—C23	162.63 (19)	C21—C20—Fe3	69.8 (2)
C24—Fe3—C23	40.89 (12)	C24—C20—Fe3	69.3 (2)
C21—Fe3—C23	68.77 (14)	C21—C20—H20	125.8
C22—Fe3—C19	127.14 (18)	C24—C20—H20	126.0
C18—Fe3—C19	40.50 (15)	Fe3—C20—H20	126.1
C16—Fe3—C19	67.59 (18)	C20—C21—C22	108.5 (4)
C17—Fe3—C19	67.78 (18)	C20—C21—Fe3	70.2 (2)
C24—Fe3—C19	123.45 (18)	C22—C21—Fe3	69.1 (2)
C21—Fe3—C19	162.4 (2)	C20—C21—H21	125.9
C23—Fe3—C19	110.29 (16)	C22—C21—H21	125.6
C22—Fe3—C15	108.63 (18)	Fe3—C21—H21	125.7
C18—Fe3—C15	67.97 (19)	C21—C22—C23	108.5 (3)
C16—Fe3—C15	40.67 (16)	C21—C22—Fe3	70.3 (2)
C17—Fe3—C15	67.7 (2)	C23—C22—Fe3	70.00 (19)
C24—Fe3—C15	158.38 (19)	C21—C22—H22	125.9
C21—Fe3—C15	124.6 (2)	C23—C22—H22	125.6
C23—Fe3—C15	122.80 (18)	Fe3—C22—H22	125.7
C19—Fe3—C15	40.03 (16)	C24—C23—C22	106.6 (3)
C22—Fe3—C20	68.06 (16)	C24—C23—P1	126.1 (3)
C18—Fe3—C20	120.63 (19)	C22—C23—P1	126.8 (3)
C16—Fe3—C20	122.40 (18)	C24—C23—Fe3	69.4 (2)
C17—Fe3—C20	106.01 (18)	C22—C23—Fe3	68.8 (2)
C24—Fe3—C20	40.84 (13)	P1—C23—Fe3	132.96 (18)
C21—Fe3—C20	40.00 (14)	C23—C24—C20	108.2 (3)
C23—Fe3—C20	68.76 (14)	C23—C24—Fe3	69.7 (2)
C19—Fe3—C20	157.4 (2)	C20—C24—Fe3	69.9 (2)
C15—Fe3—C20	159.8 (2)	C23—C24—H24	125.9
C9—S1—Fe1	107.79 (13)	C20—C24—H24	125.9
C9—S1—Fe2	111.20 (12)	Fe3—C24—H24	125.9
Fe1—S1—Fe2	66.93 (3)	C26—C25—C30	118.0 (3)
C8—S2—Fe2	108.94 (12)	C26—C25—P1	118.5 (3)
C8—S2—Fe1	116.93 (13)	C30—C25—P1	123.4 (3)
Fe2—S2—Fe1	67.37 (3)	C27—C26—C25	121.5 (3)
C23—P1—C25	102.96 (16)	C27—C26—H26	119.3
C23—P1—C31	104.03 (16)	C25—C26—H26	119.3
C25—P1—C31	100.01 (15)	C26—C27—C28	119.6 (4)
C23—P1—Fe1	118.32 (12)	C26—C27—H27	120.2
C25—P1—Fe1	112.95 (11)	C28—C27—H27	120.2
C31—P1—Fe1	116.22 (12)	C29—C28—C27	119.7 (4)
C5—N1—C9	119.7 (3)	C29—C28—H28	120.2
C5—N1—C8	123.4 (3)	C27—C28—H28	120.2
C9—N1—C8	112.7 (3)	C28—C29—C30	120.9 (4)
C2—C1—H1A	109.5	C28—C29—H29	119.5
C2—C1—H1B	109.5	C30—C29—H29	119.5
H1A—C1—H1B	109.5	C29—C30—C25	120.3 (4)
C2—C1—H1C	109.5	C29—C30—H30	119.9
H1A—C1—H1C	109.5	C25—C30—H30	119.9
H1B—C1—H1C	109.5	C36—C31—C32	117.4 (3)
C3—C2—C7	116.6 (4)	C36—C31—P1	121.7 (3)
C3—C2—C1	122.2 (4)	C32—C31—P1	120.8 (3)
C7—C2—C1	121.2 (4)	C33—C32—C31	121.1 (4)
C4—C3—C2	122.7 (4)	C33—C32—H32	119.4
C4—C3—H3	118.7	C31—C32—H32	119.4
C2—C3—H3	118.7	C34—C33—C32	120.0 (4)
C3—C4—C5	120.6 (4)	C34—C33—H33	120.0
C3—C4—H4	119.7	C32—C33—H33	120.0
C5—C4—H4	119.7	C33—C34—C35	120.3 (4)
C6—C5—C4	117.1 (4)	C33—C34—H34	119.9
C6—C5—N1	122.2 (4)	C35—C34—H34	119.9
C4—C5—N1	120.6 (4)	C34—C35—C36	120.0 (4)
C7—C6—C5	121.3 (4)	C34—C35—H35	120.0
C7—C6—H6	119.4	C36—C35—H35	120.0
C5—C6—H6	119.4	C31—C36—C35	121.3 (4)
C6—C7—C2	121.7 (4)	C31—C36—H36	119.4
C6—C7—H7	119.1	C35—C36—H36	119.4
C2—C7—H7	119.1

C13—Fe1—Fe2—C11	−5.79 (19)	C20—Fe3—C18—C17	−78.6 (3)
C14—Fe1—Fe2—C11	−99.1 (2)	C16—C15—C19—C18	0.7 (5)
P1—Fe1—Fe2—C11	118.10 (17)	Fe3—C15—C19—C18	−58.8 (3)
S1—Fe1—Fe2—C11	76.16 (16)	C16—C15—C19—Fe3	59.5 (3)
S2—Fe1—Fe2—C11	−177.00 (16)	C17—C18—C19—C15	−1.0 (5)
C13—Fe1—Fe2—C12	86.84 (18)	Fe3—C18—C19—C15	59.3 (3)
C14—Fe1—Fe2—C12	−6.51 (19)	C17—C18—C19—Fe3	−60.3 (3)
P1—Fe1—Fe2—C12	−149.28 (16)	C22—Fe3—C19—C15	73.8 (3)
S1—Fe1—Fe2—C12	168.78 (14)	C18—Fe3—C19—C15	−119.7 (4)
S2—Fe1—Fe2—C12	−84.38 (14)	C16—Fe3—C19—C15	−38.3 (3)
C13—Fe1—Fe2—C10	−153.7 (3)	C17—Fe3—C19—C15	−81.3 (3)
C14—Fe1—Fe2—C10	112.9 (3)	C24—Fe3—C19—C15	161.0 (3)
P1—Fe1—Fe2—C10	−29.8 (3)	C21—Fe3—C19—C15	33.6 (7)
S1—Fe1—Fe2—C10	−71.8 (3)	C23—Fe3—C19—C15	117.2 (3)
S2—Fe1—Fe2—C10	35.1 (3)	C20—Fe3—C19—C15	−159.5 (4)
C13—Fe1—Fe2—S2	171.21 (12)	C22—Fe3—C19—C18	−166.5 (3)
C14—Fe1—Fe2—S2	77.86 (13)	C16—Fe3—C19—C18	81.4 (3)
P1—Fe1—Fe2—S2	−64.90 (8)	C17—Fe3—C19—C18	38.4 (3)
S1—Fe1—Fe2—S2	−106.84 (4)	C24—Fe3—C19—C18	−79.2 (3)
C13—Fe1—Fe2—S1	−81.95 (12)	C21—Fe3—C19—C18	153.3 (5)
C14—Fe1—Fe2—S1	−175.30 (13)	C23—Fe3—C19—C18	−123.0 (3)
P1—Fe1—Fe2—S1	41.94 (8)	C15—Fe3—C19—C18	119.7 (4)
S2—Fe1—Fe2—S1	106.84 (4)	C20—Fe3—C19—C18	−39.7 (6)
C13—Fe1—S1—C9	−152.98 (16)	C22—Fe3—C20—C21	−37.4 (2)
C14—Fe1—S1—C9	119.3 (4)	C18—Fe3—C20—C21	157.3 (3)
P1—Fe1—S1—C9	−56.67 (12)	C16—Fe3—C20—C21	75.7 (3)
S2—Fe1—S1—C9	53.25 (12)	C17—Fe3—C20—C21	115.6 (3)
Fe2—Fe1—S1—C9	106.02 (12)	C24—Fe3—C20—C21	−119.6 (3)
C13—Fe1—S1—Fe2	101.00 (11)	C23—Fe3—C20—C21	−81.9 (2)
C14—Fe1—S1—Fe2	13.3 (4)	C19—Fe3—C20—C21	−173.9 (4)
P1—Fe1—S1—Fe2	−162.70 (4)	C15—Fe3—C20—C21	47.0 (6)
S2—Fe1—S1—Fe2	−52.78 (3)	C22—Fe3—C20—C24	82.2 (2)
C11—Fe2—S1—C9	150.9 (2)	C18—Fe3—C20—C24	−83.1 (3)
C12—Fe2—S1—C9	−125.5 (3)	C16—Fe3—C20—C24	−164.7 (3)
C10—Fe2—S1—C9	51.8 (2)	C17—Fe3—C20—C24	−124.8 (3)
S2—Fe2—S1—C9	−47.37 (13)	C21—Fe3—C20—C24	119.6 (3)
Fe1—Fe2—S1—C9	−101.01 (13)	C23—Fe3—C20—C24	37.7 (2)
C11—Fe2—S1—Fe1	−108.09 (16)	C19—Fe3—C20—C24	−54.3 (5)
C12—Fe2—S1—Fe1	−24.5 (3)	C15—Fe3—C20—C24	166.6 (5)
C10—Fe2—S1—Fe1	152.84 (15)	C24—C20—C21—C22	−0.1 (5)
S2—Fe2—S1—Fe1	53.64 (3)	Fe3—C20—C21—C22	58.7 (3)
C11—Fe2—S2—C8	120.3 (4)	C24—C20—C21—Fe3	−58.8 (3)
C12—Fe2—S2—C8	−148.17 (19)	C22—Fe3—C21—C20	119.9 (4)
C10—Fe2—S2—C8	−52.87 (18)	C18—Fe3—C21—C20	−49.8 (5)
S1—Fe2—S2—C8	58.87 (13)	C16—Fe3—C21—C20	−121.6 (3)
Fe1—Fe2—S2—C8	112.07 (13)	C17—Fe3—C21—C20	−80.8 (3)
C11—Fe2—S2—Fe1	8.2 (4)	C24—Fe3—C21—C20	37.8 (2)
C12—Fe2—S2—Fe1	99.76 (14)	C23—Fe3—C21—C20	81.9 (2)
C10—Fe2—S2—Fe1	−164.94 (13)	C19—Fe3—C21—C20	172.2 (5)
S1—Fe2—S2—Fe1	−53.20 (3)	C15—Fe3—C21—C20	−162.2 (3)
C13—Fe1—S2—C8	−119.6 (3)	C18—Fe3—C21—C22	−169.7 (4)
C14—Fe1—S2—C8	151.61 (18)	C16—Fe3—C21—C22	118.5 (3)
P1—Fe1—S2—C8	54.64 (14)	C17—Fe3—C21—C22	159.3 (3)
S1—Fe1—S2—C8	−46.91 (14)	C24—Fe3—C21—C22	−82.1 (3)
Fe2—Fe1—S2—C8	−100.52 (14)	C23—Fe3—C21—C22	−38.0 (2)
C13—Fe1—S2—Fe2	−19.1 (3)	C19—Fe3—C21—C22	52.3 (7)
C14—Fe1—S2—Fe2	−107.87 (12)	C15—Fe3—C21—C22	77.9 (3)
P1—Fe1—S2—Fe2	155.17 (4)	C20—Fe3—C21—C22	−119.9 (4)
S1—Fe1—S2—Fe2	53.61 (3)	C20—C21—C22—C23	0.4 (5)
C13—Fe1—P1—C23	−153.80 (18)	Fe3—C21—C22—C23	59.8 (3)
C14—Fe1—P1—C23	−61.51 (18)	C20—C21—C22—Fe3	−59.4 (3)
S1—Fe1—P1—C23	117.07 (13)	C18—Fe3—C22—C21	163.4 (6)
S2—Fe1—P1—C23	28.86 (14)	C16—Fe3—C22—C21	−78.7 (3)
Fe2—Fe1—P1—C23	82.08 (15)	C17—Fe3—C22—C21	−44.7 (5)
C13—Fe1—P1—C25	85.87 (17)	C24—Fe3—C22—C21	81.0 (3)
C14—Fe1—P1—C25	178.16 (17)	C23—Fe3—C22—C21	119.3 (3)
S1—Fe1—P1—C25	−3.25 (13)	C19—Fe3—C22—C21	−162.5 (3)
S2—Fe1—P1—C25	−91.46 (13)	C15—Fe3—C22—C21	−121.8 (3)
Fe2—Fe1—P1—C25	−38.24 (16)	C20—Fe3—C22—C21	36.9 (2)
C13—Fe1—P1—C31	−28.89 (18)	C18—Fe3—C22—C23	44.1 (7)
C14—Fe1—P1—C31	63.40 (18)	C16—Fe3—C22—C23	162.0 (2)
S1—Fe1—P1—C31	−118.01 (13)	C17—Fe3—C22—C23	−164.0 (4)
S2—Fe1—P1—C31	153.78 (13)	C24—Fe3—C22—C23	−38.3 (2)
Fe2—Fe1—P1—C31	−153.00 (13)	C21—Fe3—C22—C23	−119.3 (3)
C7—C2—C3—C4	0.1 (6)	C19—Fe3—C22—C23	78.2 (3)
C1—C2—C3—C4	179.4 (4)	C15—Fe3—C22—C23	118.9 (3)
C2—C3—C4—C5	−0.9 (6)	C20—Fe3—C22—C23	−82.4 (2)
C3—C4—C5—C6	1.4 (5)	C21—C22—C23—C24	−0.6 (4)
C3—C4—C5—N1	177.6 (3)	Fe3—C22—C23—C24	59.4 (2)
C9—N1—C5—C6	3.7 (5)	C21—C22—C23—P1	171.5 (3)
C8—N1—C5—C6	−151.7 (3)	Fe3—C22—C23—P1	−128.5 (3)
C9—N1—C5—C4	−172.3 (3)	C21—C22—C23—Fe3	−60.0 (3)
C8—N1—C5—C4	32.3 (5)	C25—P1—C23—C24	109.2 (3)
C4—C5—C6—C7	−1.1 (6)	C31—P1—C23—C24	−146.8 (3)
N1—C5—C6—C7	−177.2 (3)	Fe1—P1—C23—C24	−16.1 (4)
C5—C6—C7—C2	0.3 (6)	C25—P1—C23—C22	−61.3 (3)
C3—C2—C7—C6	0.2 (6)	C31—P1—C23—C22	42.6 (4)
C1—C2—C7—C6	−179.0 (4)	Fe1—P1—C23—C22	173.3 (3)
C5—N1—C8—S2	98.7 (4)	C25—P1—C23—Fe3	−155.9 (2)
C9—N1—C8—S2	−58.1 (4)	C31—P1—C23—Fe3	−51.9 (3)
Fe2—S2—C8—N1	−20.0 (3)	Fe1—P1—C23—Fe3	78.7 (3)
Fe1—S2—C8—N1	53.6 (3)	C22—Fe3—C23—C24	−118.2 (3)
C5—N1—C9—S1	−84.2 (4)	C18—Fe3—C23—C24	75.4 (3)
C8—N1—C9—S1	73.6 (3)	C16—Fe3—C23—C24	−161.7 (4)
Fe1—S1—C9—N1	−79.0 (3)	C17—Fe3—C23—C24	37.8 (6)
Fe2—S1—C9—N1	−7.5 (3)	C21—Fe3—C23—C24	−80.8 (2)
C22—Fe3—C15—C19	−126.1 (3)	C19—Fe3—C23—C24	118.1 (2)
C18—Fe3—C15—C19	37.5 (3)	C15—Fe3—C23—C24	161.0 (2)
C16—Fe3—C15—C19	118.4 (4)	C20—Fe3—C23—C24	−37.7 (2)
C17—Fe3—C15—C19	81.6 (3)	C18—Fe3—C23—C22	−166.4 (3)
C24—Fe3—C15—C19	−47.4 (6)	C16—Fe3—C23—C22	−43.4 (5)
C21—Fe3—C15—C19	−168.2 (3)	C17—Fe3—C23—C22	156.0 (5)
C23—Fe3—C15—C19	−82.8 (3)	C24—Fe3—C23—C22	118.2 (3)
C20—Fe3—C15—C19	157.0 (5)	C21—Fe3—C23—C22	37.5 (2)
C22—Fe3—C15—C16	115.5 (3)	C19—Fe3—C23—C22	−123.7 (3)
C18—Fe3—C15—C16	−80.9 (3)	C15—Fe3—C23—C22	−80.8 (3)
C17—Fe3—C15—C16	−36.9 (3)	C20—Fe3—C23—C22	80.5 (2)
C24—Fe3—C15—C16	−165.8 (4)	C22—Fe3—C23—P1	121.1 (4)
C21—Fe3—C15—C16	73.3 (4)	C18—Fe3—C23—P1	−45.3 (4)
C23—Fe3—C15—C16	158.8 (3)	C16—Fe3—C23—P1	77.7 (5)
C19—Fe3—C15—C16	−118.4 (4)	C17—Fe3—C23—P1	−82.9 (6)
C20—Fe3—C15—C16	38.6 (7)	C24—Fe3—C23—P1	−120.7 (3)
C19—C15—C16—C17	−0.1 (5)	C21—Fe3—C23—P1	158.6 (3)
Fe3—C15—C16—C17	59.8 (3)	C19—Fe3—C23—P1	−2.6 (3)
C19—C15—C16—Fe3	−59.9 (3)	C15—Fe3—C23—P1	40.3 (3)
C22—Fe3—C16—C17	157.2 (3)	C20—Fe3—C23—P1	−158.4 (3)
C18—Fe3—C16—C17	−37.8 (3)	C22—C23—C24—C20	0.5 (4)
C24—Fe3—C16—C17	45.4 (6)	P1—C23—C24—C20	−171.6 (3)
C21—Fe3—C16—C17	115.7 (3)	Fe3—C23—C24—C20	59.5 (3)
C23—Fe3—C16—C17	−171.0 (3)	C22—C23—C24—Fe3	−59.0 (2)
C19—Fe3—C16—C17	−81.8 (3)	P1—C23—C24—Fe3	128.9 (3)
C15—Fe3—C16—C17	−119.5 (4)	C21—C20—C24—C23	−0.2 (4)
C20—Fe3—C16—C17	75.3 (4)	Fe3—C20—C24—C23	−59.4 (3)
C22—Fe3—C16—C15	−83.3 (3)	C21—C20—C24—Fe3	59.1 (3)
C18—Fe3—C16—C15	81.7 (3)	C22—Fe3—C24—C23	38.56 (19)
C17—Fe3—C16—C15	119.5 (4)	C18—Fe3—C24—C23	−124.9 (2)
C24—Fe3—C16—C15	164.9 (4)	C16—Fe3—C24—C23	159.4 (5)
C21—Fe3—C16—C15	−124.8 (3)	C17—Fe3—C24—C23	−167.2 (2)
C23—Fe3—C16—C15	−51.5 (6)	C21—Fe3—C24—C23	82.3 (2)
C19—Fe3—C16—C15	37.7 (3)	C19—Fe3—C24—C23	−82.6 (3)
C20—Fe3—C16—C15	−165.2 (3)	C15—Fe3—C24—C23	−48.1 (5)
C15—C16—C17—C18	−0.6 (5)	C20—Fe3—C24—C23	119.3 (3)
Fe3—C16—C17—C18	59.1 (3)	C22—Fe3—C24—C20	−80.8 (2)
C15—C16—C17—Fe3	−59.7 (3)	C18—Fe3—C24—C20	115.7 (3)
C22—Fe3—C17—C16	−49.2 (6)	C16—Fe3—C24—C20	40.1 (6)
C18—Fe3—C17—C16	119.5 (5)	C17—Fe3—C24—C20	73.5 (3)
C24—Fe3—C17—C16	−162.6 (3)	C21—Fe3—C24—C20	−37.0 (2)
C21—Fe3—C17—C16	−80.5 (4)	C23—Fe3—C24—C20	−119.3 (3)
C23—Fe3—C17—C16	168.3 (5)	C19—Fe3—C24—C20	158.0 (3)
C19—Fe3—C17—C16	81.2 (3)	C15—Fe3—C24—C20	−167.4 (5)
C15—Fe3—C17—C16	37.8 (3)	C23—P1—C25—C26	176.8 (3)
C20—Fe3—C17—C16	−121.8 (3)	C31—P1—C25—C26	69.7 (3)
C22—Fe3—C17—C18	−168.7 (4)	Fe1—P1—C25—C26	−54.5 (3)
C16—Fe3—C17—C18	−119.5 (5)	C23—P1—C25—C30	−6.0 (3)
C24—Fe3—C17—C18	77.9 (3)	C31—P1—C25—C30	−113.1 (3)
C21—Fe3—C17—C18	160.0 (3)	Fe1—P1—C25—C30	122.8 (3)
C23—Fe3—C17—C18	48.8 (7)	C30—C25—C26—C27	−0.3 (5)
C19—Fe3—C17—C18	−38.3 (3)	P1—C25—C26—C27	177.1 (3)
C15—Fe3—C17—C18	−81.7 (3)	C25—C26—C27—C28	0.1 (6)
C20—Fe3—C17—C18	118.6 (3)	C26—C27—C28—C29	1.2 (6)
C16—C17—C18—C19	1.0 (5)	C27—C28—C29—C30	−2.2 (6)
Fe3—C17—C18—C19	60.5 (3)	C28—C29—C30—C25	2.1 (6)
C16—C17—C18—Fe3	−59.6 (3)	C26—C25—C30—C29	−0.8 (5)
C22—Fe3—C18—C19	43.4 (8)	P1—C25—C30—C29	−178.0 (3)
C16—Fe3—C18—C19	−81.1 (3)	C23—P1—C31—C36	104.2 (3)
C17—Fe3—C18—C19	−118.0 (4)	C25—P1—C31—C36	−149.6 (3)
C24—Fe3—C18—C19	120.2 (3)	Fe1—P1—C31—C36	−27.7 (3)
C21—Fe3—C18—C19	−161.8 (4)	C23—P1—C31—C32	−74.4 (3)
C23—Fe3—C18—C19	78.3 (3)	C25—P1—C31—C32	31.8 (3)
C15—Fe3—C18—C19	−37.1 (3)	Fe1—P1—C31—C32	153.6 (3)
C20—Fe3—C18—C19	163.4 (3)	C36—C31—C32—C33	−0.8 (6)
C22—Fe3—C18—C17	161.4 (6)	P1—C31—C32—C33	177.8 (3)
C16—Fe3—C18—C17	36.9 (3)	C31—C32—C33—C34	0.9 (6)
C24—Fe3—C18—C17	−121.8 (3)	C32—C33—C34—C35	−0.2 (7)
C21—Fe3—C18—C17	−43.8 (6)	C33—C34—C35—C36	−0.4 (7)
C23—Fe3—C18—C17	−163.8 (3)	C32—C31—C36—C35	0.2 (6)
C19—Fe3—C18—C17	118.0 (4)	P1—C31—C36—C35	−178.5 (3)
C15—Fe3—C18—C17	80.9 (3)	C34—C35—C36—C31	0.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O2ⁱ	0.98	2.53	3.224 (5)	128
C24—H24···S2	0.98	2.72	3.561 (4)	144

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Fe₃(C₅H₅)(C₉H₁₁NS₂)(C₁₇H₁₄P)(CO)₅]
M_r	819.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.600 (2), 10.8964 (19), 23.396 (4)
β (°)	94.741 (3)
V (Å³)	3455.2 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.45
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.760, 0.868
No. of measured, independent and observed [I > 2σ(I)] reflections	21457, 8202, 4258
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.079, 0.80
No. of reflections	8202
No. of parameters	434
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.39

Computer programs: SMART (Bruker, 1997), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Fe1—C13	1.750 (4)	Fe2—C11	1.761 (5)
Fe1—P1	2.2565 (10)	Fe2—C12	1.777 (5)
Fe1—S1	2.2762 (11)	Fe2—C10	1.813 (5)
Fe1—S2	2.2818 (11)	Fe2—S2	2.2546 (11)
Fe1—Fe2	2.5160 (8)	Fe2—S1	2.2867 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O2ⁱ	0.98	2.53	3.224 (5)	128
C24—H24···S2	0.98	2.72	3.561 (4)	144

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors thank the Science Foundation of Nantong Municipality (grant No. K2007011), the Science Foundation of Nantong University (grant Nos. 06Z017 and 06Z022) and the National Natural Science Foundation of China (grant No. 20276009) for financial support.

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