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Acta Cryst. (2008). E64, m1423    [ doi:10.1107/S1600536808032698 ]

Pentacarbonyl-1[kappa]2C,2[kappa]3C-(ferrocenyldiphenylphosphine-1[kappa]P)[[mu]-2-(4-methylphenyl)-2-azapropane-1,3-dithiolato-1:2[kappa]4S,S':S,S']diiron(I)(Fe-Fe)

Y.-F. Tang and J.-L. Zhu

Abstract top

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.

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.

Refinement top

H atoms were placed in geometrically calculated positions (C—H = 0.93–0.98 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(Cmethyl)

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
[Figure 1] 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
Mr = 819.25Dx = 1.575 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2549 reflections
a = 13.600 (2) Åθ = 2.4–22.0°
b = 10.8964 (19) ŵ = 1.45 mm−1
c = 23.396 (4) ÅT = 298 K
β = 94.741 (3)°Block, red
V = 3455.2 (11) Å30.20 × 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 tube4258 reflections with I > 2σ(I)
graphiteRint = 0.070
φ and ω scansθmax = 28.4°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −17→18
Tmin = 0.760, Tmax = 0.868k = −9→14
21457 measured reflectionsl = −31→30
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.048 w = 1/[σ2(Fo2) + (0.0157P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.079(Δ/σ)max = 0.001
S = 0.80Δρmax = 0.66 e Å−3
8202 reflectionsΔρmin = −0.38 e Å−3
434 parameters
Crystal data top
[Fe3(C5H5)(C9H11NS2)(C17H14P)(CO)5]V = 3455.2 (11) Å3
Mr = 819.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.600 (2) ŵ = 1.45 mm−1
b = 10.8964 (19) ÅT = 298 K
c = 23.396 (4) Å0.20 × 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)
Tmin = 0.760, Tmax = 0.868Rint = 0.070
21457 measured reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.079Δρmax = 0.66 e Å−3
S = 0.80Δρmin = −0.38 e Å−3
8202 reflectionsAbsolute structure: ?
434 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Fe10.20737 (4)0.18453 (5)0.30929 (2)0.03252 (14)
Fe20.20176 (4)0.09491 (5)0.40808 (2)0.03988 (16)
Fe30.08083 (4)0.09519 (5)0.11522 (2)0.04244 (16)
S10.34466 (7)0.12772 (9)0.36528 (4)0.0387 (2)
S20.15575 (7)−0.00994 (9)0.32718 (4)0.0382 (2)
P10.26239 (7)0.19707 (9)0.22109 (4)0.0316 (2)
O10.2115 (2)−0.1033 (3)0.49363 (13)0.0791 (11)
O20.2652 (3)0.3021 (3)0.48103 (14)0.1006 (13)
O3−0.0037 (2)0.1481 (3)0.42412 (14)0.0962 (12)
O40.2502 (2)0.4345 (2)0.34576 (12)0.0634 (9)
O50.0021 (2)0.2479 (3)0.27912 (12)0.0661 (9)
N10.3407 (2)−0.1259 (3)0.34951 (12)0.0409 (8)
C10.4517 (4)−0.3802 (4)0.56016 (18)0.0874 (16)
H1A0.4496−0.46710.55350.131*
H1B0.4066−0.35920.58810.131*
H1C0.5173−0.35660.57410.131*
C20.4224 (3)−0.3132 (4)0.50438 (17)0.0536 (11)
C30.3533 (3)−0.3595 (4)0.46376 (18)0.0529 (11)
H30.3241−0.43480.47060.063*
C40.3255 (3)−0.2992 (4)0.41345 (16)0.0459 (10)
H40.2792−0.33460.38700.055*
C50.3662 (3)−0.1853 (4)0.40172 (16)0.0394 (9)
C60.4364 (3)−0.1384 (4)0.44210 (17)0.0485 (11)
H60.4658−0.06340.43530.058*
C70.4635 (3)−0.2009 (4)0.49226 (17)0.0579 (12)
H70.5107−0.16670.51860.069*
C80.2455 (3)−0.1362 (3)0.31877 (16)0.0479 (11)
H8A0.2156−0.21210.33040.057*
H8B0.2551−0.14360.27830.057*
C90.3917 (3)−0.0175 (3)0.33541 (15)0.0448 (10)
H9A0.3883−0.01030.29400.054*
H9B0.4606−0.02660.34900.054*
C100.2131 (3)−0.0291 (4)0.45986 (18)0.0539 (12)
C110.2391 (3)0.2194 (4)0.45270 (18)0.0651 (14)
C120.0758 (3)0.1262 (4)0.41723 (17)0.0561 (12)
C130.2339 (3)0.3362 (4)0.32971 (15)0.0385 (10)
C140.0838 (3)0.2218 (3)0.28947 (16)0.0431 (10)
C150.0207 (4)0.2515 (5)0.0789 (2)0.0749 (15)
H150.05680.31960.06300.090*
C16−0.0165 (4)0.1463 (5)0.0488 (2)0.0738 (15)
H16−0.01010.12870.00810.089*
C17−0.0633 (3)0.0727 (5)0.0861 (2)0.0736 (15)
H17−0.0958−0.00580.07660.088*
C18−0.0557 (3)0.1293 (5)0.1406 (2)0.0686 (14)
H18−0.08260.09790.17540.082*
C19−0.0044 (3)0.2407 (4)0.1355 (2)0.0662 (14)
H190.01150.29990.16640.079*
C200.1400 (3)−0.0774 (4)0.12177 (17)0.0518 (11)
H200.1039−0.15460.11520.062*
C210.1848 (3)−0.0097 (4)0.08032 (18)0.0551 (12)
H210.1854−0.03120.03970.066*
C220.2278 (3)0.0960 (4)0.10657 (15)0.0440 (10)
H220.26380.15980.08740.053*
C230.2103 (2)0.0944 (3)0.16603 (14)0.0331 (9)
C240.1549 (3)−0.0139 (3)0.17502 (16)0.0429 (10)
H240.1310−0.04010.21150.051*
C250.3951 (2)0.1685 (3)0.22119 (14)0.0303 (8)
C260.4591 (3)0.2380 (3)0.25719 (15)0.0380 (9)
H260.43380.29980.27910.046*
C270.5593 (3)0.2175 (4)0.26120 (16)0.0471 (11)
H270.60110.26500.28570.056*
C280.5975 (3)0.1257 (4)0.22858 (17)0.0483 (11)
H280.66500.11030.23150.058*
C290.5357 (3)0.0582 (3)0.19212 (16)0.0455 (11)
H290.5618−0.00150.16930.055*
C300.4351 (3)0.0770 (3)0.18864 (15)0.0370 (9)
H300.39370.02830.16450.044*
C310.2548 (3)0.3488 (3)0.18691 (15)0.0343 (9)
C320.3189 (3)0.3814 (3)0.14616 (16)0.0477 (11)
H320.36770.32660.13710.057*
C330.3115 (3)0.4942 (4)0.11883 (17)0.0577 (12)
H330.35440.51410.09130.069*
C340.2412 (3)0.5761 (4)0.13229 (18)0.0591 (12)
H340.23640.65190.11400.071*
C350.1777 (3)0.5472 (4)0.17249 (18)0.0547 (12)
H350.13010.60340.18170.066*
C360.1843 (3)0.4339 (3)0.19954 (15)0.0427 (10)
H360.14050.41480.22670.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0317 (3)0.0340 (3)0.0323 (3)−0.0013 (3)0.0052 (2)−0.0022 (2)
Fe20.0415 (4)0.0483 (4)0.0305 (3)−0.0029 (3)0.0065 (3)−0.0030 (3)
Fe30.0349 (3)0.0523 (4)0.0393 (3)0.0000 (3)−0.0020 (3)−0.0046 (3)
S10.0357 (6)0.0427 (6)0.0374 (6)−0.0044 (5)0.0019 (5)0.0000 (5)
S20.0405 (6)0.0395 (6)0.0343 (6)−0.0058 (5)0.0014 (5)0.0002 (4)
P10.0296 (5)0.0336 (6)0.0319 (6)0.0006 (5)0.0038 (4)−0.0019 (4)
O10.103 (3)0.087 (3)0.051 (2)0.012 (2)0.0248 (19)0.0228 (18)
O20.138 (3)0.099 (3)0.067 (3)−0.033 (3)0.026 (2)−0.042 (2)
O30.055 (2)0.151 (4)0.084 (3)0.020 (2)0.018 (2)−0.018 (2)
O40.067 (2)0.046 (2)0.079 (2)−0.0107 (16)0.0131 (17)−0.0186 (16)
O50.0356 (18)0.080 (2)0.083 (2)0.0090 (16)0.0092 (17)0.0150 (17)
N10.049 (2)0.038 (2)0.036 (2)0.0013 (16)0.0032 (17)0.0055 (15)
C10.098 (4)0.094 (4)0.067 (4)−0.003 (3)−0.013 (3)0.034 (3)
C20.056 (3)0.057 (3)0.047 (3)0.001 (2)0.002 (2)0.018 (2)
C30.055 (3)0.047 (3)0.058 (3)−0.009 (2)0.010 (2)0.012 (2)
C40.049 (3)0.044 (3)0.043 (3)−0.006 (2)−0.002 (2)−0.001 (2)
C50.041 (2)0.040 (3)0.037 (2)0.004 (2)0.0059 (19)0.0015 (19)
C60.042 (3)0.049 (3)0.054 (3)−0.007 (2)−0.001 (2)0.014 (2)
C70.050 (3)0.062 (3)0.059 (3)−0.004 (2)−0.011 (2)0.008 (2)
C80.063 (3)0.035 (3)0.044 (3)0.001 (2)−0.006 (2)−0.0051 (19)
C90.044 (2)0.046 (3)0.046 (3)0.012 (2)0.014 (2)0.009 (2)
C100.045 (3)0.080 (4)0.039 (3)0.002 (2)0.016 (2)−0.006 (2)
C110.072 (3)0.083 (4)0.043 (3)−0.010 (3)0.022 (3)−0.013 (3)
C120.056 (3)0.074 (3)0.039 (3)0.002 (3)0.005 (2)−0.006 (2)
C130.032 (2)0.044 (3)0.040 (2)0.004 (2)0.0056 (18)−0.004 (2)
C140.045 (3)0.037 (3)0.050 (3)−0.006 (2)0.012 (2)0.0042 (19)
C150.073 (4)0.067 (4)0.082 (4)0.013 (3)−0.011 (3)0.016 (3)
C160.065 (4)0.094 (5)0.058 (3)0.017 (3)−0.021 (3)−0.009 (3)
C170.038 (3)0.087 (4)0.093 (4)−0.001 (3)−0.016 (3)−0.020 (3)
C180.035 (3)0.098 (4)0.073 (4)0.004 (3)0.005 (2)−0.013 (3)
C190.045 (3)0.071 (4)0.080 (4)0.020 (3)−0.012 (3)−0.021 (3)
C200.055 (3)0.042 (3)0.056 (3)−0.001 (2)−0.011 (2)−0.013 (2)
C210.047 (3)0.076 (3)0.042 (3)0.003 (2)0.002 (2)−0.024 (2)
C220.038 (2)0.058 (3)0.036 (2)−0.005 (2)0.0070 (19)−0.006 (2)
C230.030 (2)0.037 (2)0.032 (2)0.0003 (18)0.0013 (17)−0.0005 (18)
C240.046 (3)0.045 (3)0.036 (2)−0.002 (2)−0.001 (2)−0.0014 (19)
C250.030 (2)0.032 (2)0.030 (2)0.0019 (17)0.0070 (17)0.0068 (16)
C260.037 (2)0.036 (2)0.042 (2)−0.0003 (19)0.010 (2)−0.0054 (18)
C270.036 (2)0.052 (3)0.052 (3)−0.010 (2)−0.003 (2)0.001 (2)
C280.025 (2)0.059 (3)0.061 (3)0.006 (2)0.004 (2)0.009 (2)
C290.039 (3)0.046 (3)0.053 (3)0.012 (2)0.015 (2)0.000 (2)
C300.037 (2)0.036 (2)0.038 (2)0.0036 (18)0.0033 (18)0.0005 (18)
C310.032 (2)0.035 (2)0.036 (2)0.0001 (17)0.0041 (18)0.0048 (17)
C320.042 (3)0.049 (3)0.053 (3)0.013 (2)0.007 (2)0.014 (2)
C330.053 (3)0.065 (3)0.057 (3)0.006 (3)0.014 (2)0.027 (2)
C340.060 (3)0.050 (3)0.067 (3)0.008 (2)−0.001 (3)0.023 (2)
C350.054 (3)0.045 (3)0.065 (3)0.021 (2)0.004 (2)0.009 (2)
C360.036 (2)0.050 (3)0.043 (2)0.008 (2)0.0061 (19)0.001 (2)
Geometric parameters (Å, °) top
Fe1—C131.750 (4)C7—H70.93
Fe1—C141.754 (4)C8—H8A0.97
Fe1—P12.2565 (10)C8—H8B0.97
Fe1—S12.2762 (11)C9—H9A0.97
Fe1—S22.2818 (11)C9—H9B0.97
Fe1—Fe22.5160 (8)C15—C191.399 (5)
Fe2—C111.761 (5)C15—C161.417 (6)
Fe2—C121.777 (5)C15—H150.98
Fe2—C101.813 (5)C16—C171.379 (6)
Fe2—S22.2546 (11)C16—H160.98
Fe2—S12.2867 (11)C17—C181.413 (6)
Fe3—C222.025 (4)C17—H170.98
Fe3—C182.030 (4)C18—C191.410 (5)
Fe3—C162.034 (4)C18—H180.98
Fe3—C172.036 (4)C19—H190.98
Fe3—C242.038 (4)C20—C211.398 (5)
Fe3—C212.040 (4)C20—C241.425 (5)
Fe3—C232.041 (3)C20—H200.98
Fe3—C192.043 (4)C21—C221.409 (5)
Fe3—C152.044 (4)C21—H210.98
Fe3—C202.047 (4)C22—C231.431 (4)
S1—C91.864 (3)C22—H220.98
S2—C81.860 (4)C23—C241.425 (4)
P1—C231.806 (3)C24—H240.98
P1—C251.832 (3)C25—C261.385 (4)
P1—C311.836 (3)C25—C301.392 (4)
O1—C101.132 (4)C26—C271.376 (5)
O2—C111.157 (4)C26—H260.93
O3—C121.132 (4)C27—C281.385 (5)
O4—C131.151 (4)C27—H270.93
O5—C141.153 (4)C28—C291.363 (5)
N1—C51.400 (4)C28—H280.93
N1—C91.421 (4)C29—C301.380 (5)
N1—C81.433 (4)C29—H290.93
C1—C21.519 (5)C30—H300.93
C1—H1A0.96C31—C361.382 (4)
C1—H1B0.96C31—C321.391 (4)
C1—H1C0.96C32—C331.386 (5)
C2—C31.376 (5)C32—H320.93
C2—C71.385 (5)C33—C341.363 (5)
C3—C41.374 (5)C33—H330.93
C3—H30.93C34—C351.364 (5)
C4—C51.396 (5)C34—H340.93
C4—H40.93C35—C361.386 (4)
C5—C61.384 (5)C35—H350.93
C6—C71.381 (5)C36—H360.93
C6—H60.93
C13—Fe1—C1491.41 (17)N1—C8—S2117.6 (2)
C13—Fe1—P196.67 (12)N1—C8—H8A107.9
C14—Fe1—P197.31 (12)S2—C8—H8A107.9
C13—Fe1—S187.66 (12)N1—C8—H8B107.9
C14—Fe1—S1159.67 (12)S2—C8—H8B107.9
P1—Fe1—S1102.97 (4)H8A—C8—H8B107.2
C13—Fe1—S2152.46 (12)N1—C9—S1115.4 (2)
C14—Fe1—S287.77 (12)N1—C9—H9A108.4
P1—Fe1—S2110.75 (4)S1—C9—H9A108.4
S1—Fe1—S283.80 (4)N1—C9—H9B108.4
C13—Fe1—Fe297.87 (12)S1—C9—H9B108.4
C14—Fe1—Fe2103.39 (12)H9A—C9—H9B107.5
P1—Fe1—Fe2154.30 (4)O1—C10—Fe2173.4 (4)
S1—Fe1—Fe256.73 (3)O2—C11—Fe2178.3 (4)
S2—Fe1—Fe255.80 (3)O3—C12—Fe2178.3 (4)
C11—Fe2—C1290.8 (2)O4—C13—Fe1176.7 (3)
C11—Fe2—C10100.0 (2)O5—C14—Fe1176.7 (4)
C12—Fe2—C1095.26 (18)C19—C15—C16107.3 (5)
C11—Fe2—S2159.16 (15)C19—C15—Fe369.9 (3)
C12—Fe2—S289.71 (14)C16—C15—Fe369.3 (3)
C10—Fe2—S2100.70 (14)C19—C15—H15126.3
C11—Fe2—S185.74 (13)C16—C15—H15126.4
C12—Fe2—S1152.32 (14)Fe3—C15—H15126.4
C10—Fe2—S1112.39 (13)C17—C16—C15108.7 (5)
S2—Fe2—S184.18 (4)C17—C16—Fe370.3 (3)
C11—Fe2—Fe1102.51 (14)C15—C16—Fe370.0 (3)
C12—Fe2—Fe197.99 (13)C17—C16—H16125.6
C10—Fe2—Fe1153.62 (13)C15—C16—H16125.7
S2—Fe2—Fe156.83 (3)Fe3—C16—H16125.6
S1—Fe2—Fe156.34 (3)C16—C17—C18108.3 (5)
C22—Fe3—C18164.24 (18)C16—C17—Fe370.1 (3)
C22—Fe3—C16120.53 (19)C18—C17—Fe369.5 (2)
C18—Fe3—C1667.69 (19)C16—C17—H17126.0
C22—Fe3—C17153.86 (18)C18—C17—H17125.7
C18—Fe3—C1740.67 (16)Fe3—C17—H17125.8
C16—Fe3—C1739.61 (17)C19—C18—C17107.4 (4)
C22—Fe3—C2468.59 (15)C19—C18—Fe370.2 (2)
C18—Fe3—C24108.54 (17)C17—C18—Fe369.9 (2)
C16—Fe3—C24159.7 (2)C19—C18—H18126.3
C17—Fe3—C24124.54 (19)C17—C18—H18126.3
C22—Fe3—C2140.55 (13)Fe3—C18—H18126.3
C18—Fe3—C21154.22 (19)C15—C19—C18108.4 (4)
C16—Fe3—C21106.06 (18)C15—C19—Fe370.0 (2)
C17—Fe3—C21118.59 (18)C18—C19—Fe369.3 (2)
C24—Fe3—C2168.17 (16)C15—C19—H19125.9
C22—Fe3—C2341.20 (12)C18—C19—H19125.8
C18—Fe3—C23126.57 (17)Fe3—C19—H19126.0
C16—Fe3—C23157.2 (2)C21—C20—C24108.1 (4)
C17—Fe3—C23162.63 (19)C21—C20—Fe369.8 (2)
C24—Fe3—C2340.89 (12)C24—C20—Fe369.3 (2)
C21—Fe3—C2368.77 (14)C21—C20—H20125.8
C22—Fe3—C19127.14 (18)C24—C20—H20126.0
C18—Fe3—C1940.50 (15)Fe3—C20—H20126.1
C16—Fe3—C1967.59 (18)C20—C21—C22108.5 (4)
C17—Fe3—C1967.78 (18)C20—C21—Fe370.2 (2)
C24—Fe3—C19123.45 (18)C22—C21—Fe369.1 (2)
C21—Fe3—C19162.4 (2)C20—C21—H21125.9
C23—Fe3—C19110.29 (16)C22—C21—H21125.6
C22—Fe3—C15108.63 (18)Fe3—C21—H21125.7
C18—Fe3—C1567.97 (19)C21—C22—C23108.5 (3)
C16—Fe3—C1540.67 (16)C21—C22—Fe370.3 (2)
C17—Fe3—C1567.7 (2)C23—C22—Fe370.00 (19)
C24—Fe3—C15158.38 (19)C21—C22—H22125.9
C21—Fe3—C15124.6 (2)C23—C22—H22125.6
C23—Fe3—C15122.80 (18)Fe3—C22—H22125.7
C19—Fe3—C1540.03 (16)C24—C23—C22106.6 (3)
C22—Fe3—C2068.06 (16)C24—C23—P1126.1 (3)
C18—Fe3—C20120.63 (19)C22—C23—P1126.8 (3)
C16—Fe3—C20122.40 (18)C24—C23—Fe369.4 (2)
C17—Fe3—C20106.01 (18)C22—C23—Fe368.8 (2)
C24—Fe3—C2040.84 (13)P1—C23—Fe3132.96 (18)
C21—Fe3—C2040.00 (14)C23—C24—C20108.2 (3)
C23—Fe3—C2068.76 (14)C23—C24—Fe369.7 (2)
C19—Fe3—C20157.4 (2)C20—C24—Fe369.9 (2)
C15—Fe3—C20159.8 (2)C23—C24—H24125.9
C9—S1—Fe1107.79 (13)C20—C24—H24125.9
C9—S1—Fe2111.20 (12)Fe3—C24—H24125.9
Fe1—S1—Fe266.93 (3)C26—C25—C30118.0 (3)
C8—S2—Fe2108.94 (12)C26—C25—P1118.5 (3)
C8—S2—Fe1116.93 (13)C30—C25—P1123.4 (3)
Fe2—S2—Fe167.37 (3)C27—C26—C25121.5 (3)
C23—P1—C25102.96 (16)C27—C26—H26119.3
C23—P1—C31104.03 (16)C25—C26—H26119.3
C25—P1—C31100.01 (15)C26—C27—C28119.6 (4)
C23—P1—Fe1118.32 (12)C26—C27—H27120.2
C25—P1—Fe1112.95 (11)C28—C27—H27120.2
C31—P1—Fe1116.22 (12)C29—C28—C27119.7 (4)
C5—N1—C9119.7 (3)C29—C28—H28120.2
C5—N1—C8123.4 (3)C27—C28—H28120.2
C9—N1—C8112.7 (3)C28—C29—C30120.9 (4)
C2—C1—H1A109.5C28—C29—H29119.5
C2—C1—H1B109.5C30—C29—H29119.5
H1A—C1—H1B109.5C29—C30—C25120.3 (4)
C2—C1—H1C109.5C29—C30—H30119.9
H1A—C1—H1C109.5C25—C30—H30119.9
H1B—C1—H1C109.5C36—C31—C32117.4 (3)
C3—C2—C7116.6 (4)C36—C31—P1121.7 (3)
C3—C2—C1122.2 (4)C32—C31—P1120.8 (3)
C7—C2—C1121.2 (4)C33—C32—C31121.1 (4)
C4—C3—C2122.7 (4)C33—C32—H32119.4
C4—C3—H3118.7C31—C32—H32119.4
C2—C3—H3118.7C34—C33—C32120.0 (4)
C3—C4—C5120.6 (4)C34—C33—H33120.0
C3—C4—H4119.7C32—C33—H33120.0
C5—C4—H4119.7C33—C34—C35120.3 (4)
C6—C5—C4117.1 (4)C33—C34—H34119.9
C6—C5—N1122.2 (4)C35—C34—H34119.9
C4—C5—N1120.6 (4)C34—C35—C36120.0 (4)
C7—C6—C5121.3 (4)C34—C35—H35120.0
C7—C6—H6119.4C36—C35—H35120.0
C5—C6—H6119.4C31—C36—C35121.3 (4)
C6—C7—C2121.7 (4)C31—C36—H36119.4
C6—C7—H7119.1C35—C36—H36119.4
C2—C7—H7119.1
C13—Fe1—Fe2—C11−5.79 (19)C20—Fe3—C18—C17−78.6 (3)
C14—Fe1—Fe2—C11−99.1 (2)C16—C15—C19—C180.7 (5)
P1—Fe1—Fe2—C11118.10 (17)Fe3—C15—C19—C18−58.8 (3)
S1—Fe1—Fe2—C1176.16 (16)C16—C15—C19—Fe359.5 (3)
S2—Fe1—Fe2—C11−177.00 (16)C17—C18—C19—C15−1.0 (5)
C13—Fe1—Fe2—C1286.84 (18)Fe3—C18—C19—C1559.3 (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—C1573.8 (3)
S1—Fe1—Fe2—C12168.78 (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—C10112.9 (3)C24—Fe3—C19—C15161.0 (3)
P1—Fe1—Fe2—C10−29.8 (3)C21—Fe3—C19—C1533.6 (7)
S1—Fe1—Fe2—C10−71.8 (3)C23—Fe3—C19—C15117.2 (3)
S2—Fe1—Fe2—C1035.1 (3)C20—Fe3—C19—C15−159.5 (4)
C13—Fe1—Fe2—S2171.21 (12)C22—Fe3—C19—C18−166.5 (3)
C14—Fe1—Fe2—S277.86 (13)C16—Fe3—C19—C1881.4 (3)
P1—Fe1—Fe2—S2−64.90 (8)C17—Fe3—C19—C1838.4 (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—C18153.3 (5)
C14—Fe1—Fe2—S1−175.30 (13)C23—Fe3—C19—C18−123.0 (3)
P1—Fe1—Fe2—S141.94 (8)C15—Fe3—C19—C18119.7 (4)
S2—Fe1—Fe2—S1106.84 (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—C9119.3 (4)C18—Fe3—C20—C21157.3 (3)
P1—Fe1—S1—C9−56.67 (12)C16—Fe3—C20—C2175.7 (3)
S2—Fe1—S1—C953.25 (12)C17—Fe3—C20—C21115.6 (3)
Fe2—Fe1—S1—C9106.02 (12)C24—Fe3—C20—C21−119.6 (3)
C13—Fe1—S1—Fe2101.00 (11)C23—Fe3—C20—C21−81.9 (2)
C14—Fe1—S1—Fe213.3 (4)C19—Fe3—C20—C21−173.9 (4)
P1—Fe1—S1—Fe2−162.70 (4)C15—Fe3—C20—C2147.0 (6)
S2—Fe1—S1—Fe2−52.78 (3)C22—Fe3—C20—C2482.2 (2)
C11—Fe2—S1—C9150.9 (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—C951.8 (2)C17—Fe3—C20—C24−124.8 (3)
S2—Fe2—S1—C9−47.37 (13)C21—Fe3—C20—C24119.6 (3)
Fe1—Fe2—S1—C9−101.01 (13)C23—Fe3—C20—C2437.7 (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—C24166.6 (5)
C10—Fe2—S1—Fe1152.84 (15)C24—C20—C21—C22−0.1 (5)
S2—Fe2—S1—Fe153.64 (3)Fe3—C20—C21—C2258.7 (3)
C11—Fe2—S2—C8120.3 (4)C24—C20—C21—Fe3−58.8 (3)
C12—Fe2—S2—C8−148.17 (19)C22—Fe3—C21—C20119.9 (4)
C10—Fe2—S2—C8−52.87 (18)C18—Fe3—C21—C20−49.8 (5)
S1—Fe2—S2—C858.87 (13)C16—Fe3—C21—C20−121.6 (3)
Fe1—Fe2—S2—C8112.07 (13)C17—Fe3—C21—C20−80.8 (3)
C11—Fe2—S2—Fe18.2 (4)C24—Fe3—C21—C2037.8 (2)
C12—Fe2—S2—Fe199.76 (14)C23—Fe3—C21—C2081.9 (2)
C10—Fe2—S2—Fe1−164.94 (13)C19—Fe3—C21—C20172.2 (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—C8151.61 (18)C16—Fe3—C21—C22118.5 (3)
P1—Fe1—S2—C854.64 (14)C17—Fe3—C21—C22159.3 (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—C2252.3 (7)
C14—Fe1—S2—Fe2−107.87 (12)C15—Fe3—C21—C2277.9 (3)
P1—Fe1—S2—Fe2155.17 (4)C20—Fe3—C21—C22−119.9 (4)
S1—Fe1—S2—Fe253.61 (3)C20—C21—C22—C230.4 (5)
C13—Fe1—P1—C23−153.80 (18)Fe3—C21—C22—C2359.8 (3)
C14—Fe1—P1—C23−61.51 (18)C20—C21—C22—Fe3−59.4 (3)
S1—Fe1—P1—C23117.07 (13)C18—Fe3—C22—C21163.4 (6)
S2—Fe1—P1—C2328.86 (14)C16—Fe3—C22—C21−78.7 (3)
Fe2—Fe1—P1—C2382.08 (15)C17—Fe3—C22—C21−44.7 (5)
C13—Fe1—P1—C2585.87 (17)C24—Fe3—C22—C2181.0 (3)
C14—Fe1—P1—C25178.16 (17)C23—Fe3—C22—C21119.3 (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—C2136.9 (2)
C13—Fe1—P1—C31−28.89 (18)C18—Fe3—C22—C2344.1 (7)
C14—Fe1—P1—C3163.40 (18)C16—Fe3—C22—C23162.0 (2)
S1—Fe1—P1—C31−118.01 (13)C17—Fe3—C22—C23−164.0 (4)
S2—Fe1—P1—C31153.78 (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—C40.1 (6)C19—Fe3—C22—C2378.2 (3)
C1—C2—C3—C4179.4 (4)C15—Fe3—C22—C23118.9 (3)
C2—C3—C4—C5−0.9 (6)C20—Fe3—C22—C23−82.4 (2)
C3—C4—C5—C61.4 (5)C21—C22—C23—C24−0.6 (4)
C3—C4—C5—N1177.6 (3)Fe3—C22—C23—C2459.4 (2)
C9—N1—C5—C63.7 (5)C21—C22—C23—P1171.5 (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—C432.3 (5)C25—P1—C23—C24109.2 (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—C20.3 (6)C25—P1—C23—C22−61.3 (3)
C3—C2—C7—C60.2 (6)C31—P1—C23—C2242.6 (4)
C1—C2—C7—C6−179.0 (4)Fe1—P1—C23—C22173.3 (3)
C5—N1—C8—S298.7 (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—Fe378.7 (3)
Fe1—S2—C8—N153.6 (3)C22—Fe3—C23—C24−118.2 (3)
C5—N1—C9—S1−84.2 (4)C18—Fe3—C23—C2475.4 (3)
C8—N1—C9—S173.6 (3)C16—Fe3—C23—C24−161.7 (4)
Fe1—S1—C9—N1−79.0 (3)C17—Fe3—C23—C2437.8 (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—C24118.1 (2)
C18—Fe3—C15—C1937.5 (3)C15—Fe3—C23—C24161.0 (2)
C16—Fe3—C15—C19118.4 (4)C20—Fe3—C23—C24−37.7 (2)
C17—Fe3—C15—C1981.6 (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—C22156.0 (5)
C23—Fe3—C15—C19−82.8 (3)C24—Fe3—C23—C22118.2 (3)
C20—Fe3—C15—C19157.0 (5)C21—Fe3—C23—C2237.5 (2)
C22—Fe3—C15—C16115.5 (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—C2280.5 (2)
C24—Fe3—C15—C16−165.8 (4)C22—Fe3—C23—P1121.1 (4)
C21—Fe3—C15—C1673.3 (4)C18—Fe3—C23—P1−45.3 (4)
C23—Fe3—C15—C16158.8 (3)C16—Fe3—C23—P177.7 (5)
C19—Fe3—C15—C16−118.4 (4)C17—Fe3—C23—P1−82.9 (6)
C20—Fe3—C15—C1638.6 (7)C24—Fe3—C23—P1−120.7 (3)
C19—C15—C16—C17−0.1 (5)C21—Fe3—C23—P1158.6 (3)
Fe3—C15—C16—C1759.8 (3)C19—Fe3—C23—P1−2.6 (3)
C19—C15—C16—Fe3−59.9 (3)C15—Fe3—C23—P140.3 (3)
C22—Fe3—C16—C17157.2 (3)C20—Fe3—C23—P1−158.4 (3)
C18—Fe3—C16—C17−37.8 (3)C22—C23—C24—C200.5 (4)
C24—Fe3—C16—C1745.4 (6)P1—C23—C24—C20−171.6 (3)
C21—Fe3—C16—C17115.7 (3)Fe3—C23—C24—C2059.5 (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—Fe3128.9 (3)
C15—Fe3—C16—C17−119.5 (4)C21—C20—C24—C23−0.2 (4)
C20—Fe3—C16—C1775.3 (4)Fe3—C20—C24—C23−59.4 (3)
C22—Fe3—C16—C15−83.3 (3)C21—C20—C24—Fe359.1 (3)
C18—Fe3—C16—C1581.7 (3)C22—Fe3—C24—C2338.56 (19)
C17—Fe3—C16—C15119.5 (4)C18—Fe3—C24—C23−124.9 (2)
C24—Fe3—C16—C15164.9 (4)C16—Fe3—C24—C23159.4 (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—C2382.3 (2)
C19—Fe3—C16—C1537.7 (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—C23119.3 (3)
Fe3—C16—C17—C1859.1 (3)C22—Fe3—C24—C20−80.8 (2)
C15—C16—C17—Fe3−59.7 (3)C18—Fe3—C24—C20115.7 (3)
C22—Fe3—C17—C16−49.2 (6)C16—Fe3—C24—C2040.1 (6)
C18—Fe3—C17—C16119.5 (5)C17—Fe3—C24—C2073.5 (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—C16168.3 (5)C19—Fe3—C24—C20158.0 (3)
C19—Fe3—C17—C1681.2 (3)C15—Fe3—C24—C20−167.4 (5)
C15—Fe3—C17—C1637.8 (3)C23—P1—C25—C26176.8 (3)
C20—Fe3—C17—C16−121.8 (3)C31—P1—C25—C2669.7 (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—C1877.9 (3)C31—P1—C25—C30−113.1 (3)
C21—Fe3—C17—C18160.0 (3)Fe1—P1—C25—C30122.8 (3)
C23—Fe3—C17—C1848.8 (7)C30—C25—C26—C27−0.3 (5)
C19—Fe3—C17—C18−38.3 (3)P1—C25—C26—C27177.1 (3)
C15—Fe3—C17—C18−81.7 (3)C25—C26—C27—C280.1 (6)
C20—Fe3—C17—C18118.6 (3)C26—C27—C28—C291.2 (6)
C16—C17—C18—C191.0 (5)C27—C28—C29—C30−2.2 (6)
Fe3—C17—C18—C1960.5 (3)C28—C29—C30—C252.1 (6)
C16—C17—C18—Fe3−59.6 (3)C26—C25—C30—C29−0.8 (5)
C22—Fe3—C18—C1943.4 (8)P1—C25—C30—C29−178.0 (3)
C16—Fe3—C18—C19−81.1 (3)C23—P1—C31—C36104.2 (3)
C17—Fe3—C18—C19−118.0 (4)C25—P1—C31—C36−149.6 (3)
C24—Fe3—C18—C19120.2 (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—C1978.3 (3)C25—P1—C31—C3231.8 (3)
C15—Fe3—C18—C19−37.1 (3)Fe1—P1—C31—C32153.6 (3)
C20—Fe3—C18—C19163.4 (3)C36—C31—C32—C33−0.8 (6)
C22—Fe3—C18—C17161.4 (6)P1—C31—C32—C33177.8 (3)
C16—Fe3—C18—C1736.9 (3)C31—C32—C33—C340.9 (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—C350.2 (6)
C19—Fe3—C18—C17118.0 (4)P1—C31—C36—C35−178.5 (3)
C15—Fe3—C18—C1780.9 (3)C34—C35—C36—C310.4 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C22—H22···O2i0.982.533.224 (5)128
C24—H24···S20.982.723.561 (4)144
Symmetry codes: (i) x, −y+1/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Fe1—C131.750 (4)Fe2—C111.761 (5)
Fe1—P12.2565 (10)Fe2—C121.777 (5)
Fe1—S12.2762 (11)Fe2—C101.813 (5)
Fe1—S22.2818 (11)Fe2—S22.2546 (11)
Fe1—Fe22.5160 (8)Fe2—S12.2867 (11)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C22—H22···O2i0.982.533.224 (5)128
C24—H24···S20.982.723.561 (4)144
Symmetry codes: (i) x, −y+1/2, z−1/2.
Acknowledgements top

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.

references
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