supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m1959-m1960    [ doi:10.1107/S1600536807029431 ]

Pentacarbonyl-1[kappa]2C,2[kappa]3C-(diphenylphosphine-1[kappa]P)([mu]-2-propyl-2-azapropane-1,3-dithiolato-1[kappa]2S,S':2[kappa]2S,S')diiron(Fe-Fe)

Z. Wang, J.-H. Liu and L.-C. Sun

Abstract top

The title compound, [Fe2(C5H11NS2)(C12H11P)(CO)5], has been prepared and characterized as a model compound of the iron hydrogenase active site through controlled CO ligand displacement of ([mu]-SCH2)2N(CH2CH2CH3)[Fe2(CO)6] with diphenylphosphine. The central Fe2S2 structure is in a butterfly conformation, and each Fe atom displays pseudo-square-pyramidal geometry. The phosphine group occupies an apical position. The propyl group on the bridging N atom is in an equatorial position and takes a zigzag form. In the crystal packing, adjacent pairs of molecules are associated by S...S (3.625 Å) intermolecular nonbonded weak interactions.

Comment top

Iron hydrogenases (Fe—H2ase) are highly efficient enzymes that catalyze the reversible reduction of protons to molecular hydrogen. Crystallographic study revealed that the active site of Fe—H2ase is comprised of one unusual low-valent diiron disulfide that is linked by a cysteine-ligand to a [Fe4S4] cluster, with one bridging carbonyl and an additional terminal carbonyl, cyanide and aqua ligands and the non-proteic dithiolate (Nicolet et al., 2000; Frey, 2002). The molecule of the title compound, (I), (Fig. 1), exhibits some resemblance to the active site of Fe-hydrogenases.

The central 2Fe2S structure in compound I is in the butterfly conformation, with a dihedral angle of 108.4 (2)° between the two Fe2S planes, and each iron atom displays pseudo-square-pyramidal geometry. The Fe—Fe distance in (I) (2.5143 (6) Å) agrees well with those found in other similar complexes [2.49–2.51 Å; Lawrence et al., 2001; Liu et al., 2004; Wang et al., 2005, Gao et al., 2007]. The phosphine group occupies an apical position. The propyl group on the bridged nitrogen atom is in an equatorial position and the propyl chain takes the zigzag form.

As shown in the packing diagram (Fig. 2), adjacent pairs of molecules are associated by S···S(3.625 Å) intermolecular non-bonded weak interactions. The distance is close to the sum of the van der Waals radii for two sulfur atoms (3.6 Å).

Related literature top

For literature on 2Fe2S complexes, where the two Fe atoms are bridged by a dithiolate ligand and each of the Fe atoms coordinated by carbonyl groups or tertiary phosphine ligands, see Lawrence et al. (2001); Liu et al. (2004); Wang et al. (2005); Gao et al. (2007).

For related literature, see: Frey (2002); Milway et al. (2006); Nicolet et al. (2000).

Experimental top

(µ-SCH2)2NCH2CH2CH3[Fe2(CO)6] (0.10 g, 0.23 mmol) was dissolved in dry acetonitrile (15 ml) and Me3NO.2H2O (51 mg, 0.46 mmol) was added under an argon atmosphere. When the color of the solution turned dark red Diphenylphosphine (46 mg, 0.25 mmol) was added and the solution was stirred at 293 K for 1.5 h and the color turned to red. After the solvent was removed in vacuum, the crude product was purified by column chromatography on silica gel with CH2Cl2/hexane (1:1) as eluent to give I as red solid (109 mg, 81%). Single crystals of (I) for X-ray analysis were grown by slow diffusion of hexane into a solution of the complex in CH2Cl2 at 275 K.

Refinement top

H atoms bonded to P atoms were located geometrically and allowed to ride on its parent atoms with distance restraints of P—H = 1.32 (2) Å, and with Uiso(H) = 1.2Ueq(P). Other H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis, showing S···S intermolecular weak interactions (dashed lines). H atoms have been omitted.
Pentacarbonyl-1κ2C,2κ3C-(diphenylphosphine-1κP)(µ-2-propyl-2- azapropane-1,3-dithiolato-1κ2S,S':2κ2S,S')diiron(Fe—Fe) top
Crystal data top
[Fe2(C5H11NS2)(C12H11P)(CO)5]F(000) = 1200
Mr = 587.20Dx = 1.487 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.4627 (15) ÅCell parameters from 3783 reflections
b = 12.1985 (15) Åθ = 2.4–23.4°
c = 17.2573 (2) ŵ = 1.36 mm−1
β = 90.162 (2)°T = 273 K
V = 2623.6 (6) Å3Block, red
Z = 40.30 × 0.20 × 0.08 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		4885 independent reflections
Radiation source: fine-focus sealed tube3350 reflections with I > 2σ(I)
graphiteRint = 0.041
φ and ω scansθmax = 25.5°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→8
Tmin = 0.686, Tmax = 0.899k = −13→14
13194 measured reflectionsl = −20→20
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.037 w = 1/[σ2(Fo2) + (0.0429P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.087(Δ/σ)max < 0.001
S = 0.92Δρmax = 0.44 e Å−3
4885 reflectionsΔρmin = −0.38 e Å−3
302 parameters
Crystal data top
[Fe2(C5H11NS2)(C12H11P)(CO)5]V = 2623.6 (6) Å3
Mr = 587.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.4627 (15) ŵ = 1.36 mm−1
b = 12.1985 (15) ÅT = 273 K
c = 17.2573 (2) Å0.30 × 0.20 × 0.08 mm
β = 90.162 (2)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		4885 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3350 reflections with I > 2σ(I)
Tmin = 0.686, Tmax = 0.899Rint = 0.041
13194 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087Δρmax = 0.44 e Å−3
S = 0.92Δρmin = −0.38 e Å−3
4885 reflectionsAbsolute structure: ?
302 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 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
xyzUiso*/Ueq
Fe10.30424 (3)0.45814 (4)0.12088 (2)0.05683 (14)
Fe20.23171 (3)0.36249 (4)0.00279 (2)0.06549 (15)
P0.34731 (6)0.61660 (7)0.17360 (4)0.0584 (2)
S20.13569 (6)0.48156 (7)0.07511 (4)0.0643 (2)
S10.35457 (6)0.49763 (7)−0.00134 (4)0.0620 (2)
O50.51096 (19)0.3537 (2)0.14933 (14)0.0892 (7)
C110.2452 (2)0.7071 (3)0.21361 (15)0.0594 (7)
C170.4470 (2)0.6044 (2)0.25035 (16)0.0623 (8)
C50.4302 (3)0.3951 (3)0.13735 (16)0.0657 (8)
O40.2164 (2)0.3518 (2)0.25765 (14)0.1033 (8)
C70.2972 (2)0.6299 (2)−0.03031 (17)0.0698 (8)
H7A0.35530.6816−0.03810.084*
H7B0.26060.6207−0.07960.084*
C220.4207 (3)0.5575 (3)0.32002 (18)0.0893 (11)
H22A0.35020.53680.32940.107*
O10.1227 (2)0.3756 (2)−0.14763 (15)0.1042 (9)
N10.22289 (19)0.6757 (2)0.02462 (13)0.0661 (7)
C40.2501 (2)0.3940 (3)0.20373 (19)0.0713 (9)
O30.4083 (2)0.2168 (2)−0.04003 (16)0.1197 (10)
C120.1424 (2)0.6704 (3)0.22953 (17)0.0747 (9)
H12A0.12490.59730.22060.090*
C180.5521 (3)0.6346 (3)0.23811 (19)0.0735 (9)
H18A0.57160.66660.19130.088*
C10.1643 (3)0.3708 (3)−0.0897 (2)0.0764 (9)
C190.6285 (3)0.6179 (3)0.2949 (2)0.0903 (11)
H19A0.69910.63910.28590.108*
C140.0908 (3)0.8476 (4)0.2707 (2)0.0965 (12)
H14A0.03880.89520.28970.116*
C90.1694 (4)0.8407 (4)−0.0525 (2)0.1237 (15)
H9A0.09870.8103−0.06210.148*
H9B0.21570.8199−0.09510.148*
O20.1204 (2)0.1872 (2)0.08541 (18)0.1176 (10)
C30.3380 (3)0.2727 (3)−0.02344 (18)0.0809 (10)
C200.6026 (4)0.5713 (3)0.3630 (3)0.1004 (12)
H20A0.65500.55990.40060.120*
C160.2692 (3)0.8157 (3)0.22726 (17)0.0743 (9)
H16A0.33800.84170.21740.089*
C20.1618 (3)0.2550 (3)0.0515 (2)0.0834 (10)
C130.0657 (3)0.7404 (4)0.25838 (19)0.0878 (11)
H13A−0.00280.71470.26940.105*
C60.1233 (2)0.6155 (3)0.02812 (18)0.0723 (9)
H6A0.09640.6050−0.02420.087*
H6B0.07090.65890.05610.087*
C100.1619 (5)0.9682 (4)−0.0479 (3)0.153 (2)
H10A0.13340.9962−0.09570.229*
H10B0.23220.9982−0.03920.229*
H10C0.11560.9887−0.00600.229*
C210.4982 (4)0.5408 (4)0.3766 (2)0.1135 (14)
H21A0.47960.50890.42370.136*
H10.3993 (18)0.6872 (19)0.1294 (13)0.061 (7)*
C150.1918 (3)0.8861 (3)0.2554 (2)0.0918 (11)
H15A0.20830.95950.26400.110*
C80.2117 (3)0.7970 (3)0.0188 (2)0.0990 (12)
H8A0.16570.82120.06070.119*
H8B0.28180.82920.02750.119*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0436 (2)0.0801 (3)0.0468 (2)−0.00482 (19)0.00266 (17)−0.0036 (2)
Fe20.0520 (3)0.0888 (4)0.0557 (3)−0.0045 (2)0.0037 (2)−0.0147 (2)
P0.0474 (4)0.0806 (6)0.0472 (4)−0.0090 (4)0.0007 (3)−0.0009 (4)
S20.0407 (4)0.0926 (6)0.0597 (4)−0.0059 (4)0.0050 (3)−0.0133 (4)
S10.0424 (4)0.0942 (6)0.0496 (4)0.0001 (4)0.0043 (3)−0.0024 (4)
O50.0612 (15)0.118 (2)0.0883 (16)0.0159 (13)0.0021 (13)0.0201 (13)
C110.0552 (19)0.079 (2)0.0445 (15)−0.0028 (15)−0.0037 (13)−0.0057 (14)
C170.0560 (18)0.075 (2)0.0556 (17)−0.0081 (15)−0.0063 (14)−0.0049 (15)
C50.060 (2)0.085 (2)0.0525 (16)−0.0046 (17)0.0073 (15)0.0067 (16)
O40.108 (2)0.122 (2)0.0805 (16)−0.0190 (15)0.0295 (15)0.0187 (14)
C70.0607 (19)0.092 (2)0.0566 (17)0.0015 (16)0.0021 (15)0.0050 (16)
C220.076 (2)0.132 (3)0.060 (2)−0.023 (2)−0.0126 (18)0.005 (2)
O10.101 (2)0.140 (2)0.0720 (16)−0.0120 (15)−0.0218 (15)−0.0162 (15)
N10.0534 (15)0.0848 (19)0.0602 (15)0.0054 (13)0.0046 (12)−0.0012 (13)
C40.061 (2)0.087 (2)0.066 (2)−0.0055 (17)0.0042 (17)−0.0049 (18)
O30.114 (2)0.118 (2)0.128 (2)0.0364 (18)0.0429 (19)0.0009 (18)
C120.064 (2)0.098 (3)0.0629 (19)−0.0093 (18)0.0071 (16)−0.0216 (17)
C180.057 (2)0.089 (2)0.074 (2)−0.0034 (16)−0.0104 (17)−0.0060 (17)
C10.060 (2)0.097 (3)0.073 (2)−0.0115 (17)0.0076 (18)−0.0206 (19)
C190.064 (2)0.096 (3)0.111 (3)0.0000 (19)−0.021 (2)−0.017 (2)
C140.083 (3)0.132 (4)0.075 (2)0.026 (3)−0.002 (2)−0.027 (2)
C90.137 (4)0.148 (5)0.087 (3)0.016 (3)−0.010 (3)−0.003 (3)
O20.118 (2)0.103 (2)0.131 (2)−0.0263 (18)0.0403 (19)−0.0058 (18)
C30.081 (3)0.093 (3)0.069 (2)−0.001 (2)0.0114 (19)−0.0051 (18)
C200.098 (3)0.105 (3)0.098 (3)0.005 (3)−0.046 (3)−0.008 (2)
C160.070 (2)0.086 (3)0.067 (2)−0.0087 (19)−0.0003 (17)−0.0069 (18)
C20.069 (2)0.099 (3)0.082 (2)−0.002 (2)0.0084 (19)−0.025 (2)
C130.059 (2)0.126 (3)0.078 (2)−0.001 (2)0.0031 (17)−0.034 (2)
C60.0519 (19)0.095 (2)0.070 (2)0.0088 (17)−0.0029 (15)−0.0055 (17)
C100.226 (6)0.091 (4)0.141 (4)0.044 (3)0.021 (4)0.007 (3)
C210.138 (4)0.133 (4)0.070 (2)−0.024 (3)−0.032 (3)0.018 (2)
C150.105 (3)0.084 (3)0.086 (3)0.004 (2)0.005 (2)−0.013 (2)
C80.102 (3)0.111 (3)0.084 (3)0.024 (2)0.003 (2)0.004 (2)
Geometric parameters (Å, °) top
Fe1—C41.766 (3)O3—C31.148 (4)
Fe1—C51.770 (3)C12—C131.376 (4)
Fe1—P2.2021 (9)C12—H12A0.9300
Fe1—S12.2543 (8)C18—C191.380 (4)
Fe1—S22.2603 (9)C18—H18A0.9300
Fe1—Fe22.5143 (6)C19—C201.345 (5)
Fe2—C31.778 (4)C19—H19A0.9300
Fe2—C21.786 (4)C14—C131.361 (5)
Fe2—C11.805 (4)C14—C151.370 (5)
Fe2—S12.2512 (9)C14—H14A0.9300
Fe2—S22.2602 (9)C9—C81.439 (5)
P—C171.820 (3)C9—C101.561 (5)
P—C111.821 (3)C9—H9A0.9700
P—H11.32 (2)C9—H9B0.9700
S2—C61.831 (3)O2—C21.138 (4)
S1—C71.833 (3)C20—C211.374 (5)
O5—C51.145 (3)C20—H20A0.9300
C11—C161.378 (4)C16—C151.381 (4)
C11—C121.386 (4)C16—H16A0.9300
C17—C221.372 (4)C13—H13A0.9300
C17—C181.377 (4)C6—H6A0.9700
O4—C41.144 (3)C6—H6B0.9700
C7—N11.440 (3)C10—H10A0.9600
C7—H7A0.9700C10—H10B0.9600
C7—H7B0.9700C10—H10C0.9600
C22—C211.387 (5)C21—H21A0.9300
C22—H22A0.9300C15—H15A0.9300
O1—C11.126 (4)C8—H8A0.9700
N1—C61.444 (4)C8—H8B0.9700
N1—C81.490 (4)
C4—Fe1—C591.03 (13)C7—N1—C6112.7 (2)
C4—Fe1—P98.50 (11)C7—N1—C8113.7 (2)
C5—Fe1—P95.76 (11)C6—N1—C8115.3 (3)
C4—Fe1—S1163.81 (11)O4—C4—Fe1179.0 (3)
C5—Fe1—S189.67 (9)C13—C12—C11121.0 (3)
P—Fe1—S197.52 (3)C13—C12—H12A119.5
C4—Fe1—S288.97 (10)C11—C12—H12A119.5
C5—Fe1—S2159.03 (11)C17—C18—C19120.4 (3)
P—Fe1—S2104.99 (3)C17—C18—H18A119.8
S1—Fe1—S284.65 (3)C19—C18—H18A119.8
C4—Fe1—Fe2108.26 (10)O1—C1—Fe2179.5 (3)
C5—Fe1—Fe2104.18 (10)C20—C19—C18121.1 (4)
P—Fe1—Fe2145.99 (3)C20—C19—H19A119.5
S1—Fe1—Fe256.02 (2)C18—C19—H19A119.5
S2—Fe1—Fe256.20 (2)C13—C14—C15120.7 (3)
C3—Fe2—C291.87 (16)C13—C14—H14A119.7
C3—Fe2—C198.92 (15)C15—C14—H14A119.7
C2—Fe2—C1103.33 (15)C8—C9—C10110.4 (4)
C3—Fe2—S186.31 (12)C8—C9—H9A109.6
C2—Fe2—S1152.32 (11)C10—C9—H9A109.6
C1—Fe2—S1104.24 (11)C8—C9—H9B109.6
C3—Fe2—S2158.79 (11)C10—C9—H9B109.6
C2—Fe2—S287.26 (11)H9A—C9—H9B108.1
C1—Fe2—S2101.90 (11)O3—C3—Fe2178.4 (4)
S1—Fe2—S284.73 (3)C19—C20—C21119.5 (4)
C3—Fe2—Fe1103.04 (11)C19—C20—H20A120.2
C2—Fe2—Fe197.72 (11)C21—C20—H20A120.2
C1—Fe2—Fe1148.90 (11)C11—C16—C15120.5 (3)
S1—Fe2—Fe156.14 (2)C11—C16—H16A119.8
S2—Fe2—Fe156.21 (2)C15—C16—H16A119.8
C17—P—C11104.48 (13)O2—C2—Fe2176.7 (4)
C17—P—Fe1113.19 (10)C14—C13—C12119.6 (3)
C11—P—Fe1121.25 (10)C14—C13—H13A120.2
C17—P—H198.0 (10)C12—C13—H13A120.2
C11—P—H199.6 (10)N1—C6—S2113.6 (2)
Fe1—P—H1117.0 (10)N1—C6—H6A108.8
C6—S2—Fe2111.91 (10)S2—C6—H6A108.8
C6—S2—Fe1110.18 (10)N1—C6—H6B108.8
Fe2—S2—Fe167.59 (3)S2—C6—H6B108.8
C7—S1—Fe2112.84 (10)H6A—C6—H6B107.7
C7—S1—Fe1109.50 (10)C9—C10—H10A109.5
Fe2—S1—Fe167.84 (3)C9—C10—H10B109.5
C16—C11—C12118.5 (3)H10A—C10—H10B109.5
C16—C11—P119.7 (2)C9—C10—H10C109.5
C12—C11—P121.8 (2)H10A—C10—H10C109.5
C22—C17—C18118.4 (3)H10B—C10—H10C109.5
C22—C17—P120.5 (2)C20—C21—C22119.8 (4)
C18—C17—P120.9 (2)C20—C21—H21A120.1
O5—C5—Fe1178.7 (3)C22—C21—H21A120.1
N1—C7—S1114.4 (2)C14—C15—C16119.8 (4)
N1—C7—H7A108.7C14—C15—H15A120.1
S1—C7—H7A108.7C16—C15—H15A120.1
N1—C7—H7B108.7C9—C8—N1117.4 (3)
S1—C7—H7B108.7C9—C8—H8A108.0
H7A—C7—H7B107.6N1—C8—H8A108.0
C17—C22—C21120.8 (3)C9—C8—H8B108.0
C17—C22—H22A119.6N1—C8—H8B108.0
C21—C22—H22A119.6H8A—C8—H8B107.2
C4—Fe1—Fe2—C3−99.28 (16)C4—Fe1—S1—Fe214.9 (4)
C5—Fe1—Fe2—C3−3.37 (15)C5—Fe1—S1—Fe2107.42 (10)
P—Fe1—Fe2—C3120.64 (12)P—Fe1—S1—Fe2−156.82 (3)
S1—Fe1—Fe2—C376.41 (12)S2—Fe1—S1—Fe2−52.37 (3)
S2—Fe1—Fe2—C3−175.18 (12)C17—P—C11—C1667.9 (3)
C4—Fe1—Fe2—C2−5.54 (16)Fe1—P—C11—C16−162.90 (19)
C5—Fe1—Fe2—C290.36 (15)C17—P—C11—C12−113.5 (3)
P—Fe1—Fe2—C2−145.63 (12)Fe1—P—C11—C1215.8 (3)
S1—Fe1—Fe2—C2170.14 (12)C11—P—C17—C2263.2 (3)
S2—Fe1—Fe2—C2−81.44 (12)Fe1—P—C17—C22−70.7 (3)
C4—Fe1—Fe2—C1126.9 (2)C11—P—C17—C18−121.4 (3)
C5—Fe1—Fe2—C1−137.2 (2)Fe1—P—C17—C18104.7 (2)
P—Fe1—Fe2—C1−13.2 (2)C4—Fe1—C5—O5−11 (15)
S1—Fe1—Fe2—C1−57.39 (19)P—Fe1—C5—O587 (15)
S2—Fe1—Fe2—C151.03 (19)S1—Fe1—C5—O5−175 (100)
C4—Fe1—Fe2—S1−175.68 (11)S2—Fe1—C5—O5−101 (15)
C5—Fe1—Fe2—S1−79.78 (10)Fe2—Fe1—C5—O5−120 (15)
P—Fe1—Fe2—S144.23 (5)Fe2—S1—C7—N166.4 (2)
S2—Fe1—Fe2—S1108.41 (4)Fe1—S1—C7—N1−7.0 (2)
C4—Fe1—Fe2—S275.90 (11)C18—C17—C22—C21−0.2 (5)
C5—Fe1—Fe2—S2171.81 (10)P—C17—C22—C21175.3 (3)
P—Fe1—Fe2—S2−64.18 (5)S1—C7—N1—C6−70.3 (3)
S1—Fe1—Fe2—S2−108.41 (4)S1—C7—N1—C8156.2 (2)
C4—Fe1—P—C1762.32 (15)C5—Fe1—C4—O44(20)
C5—Fe1—P—C17−29.59 (14)P—Fe1—C4—O4−92 (20)
S1—Fe1—P—C17−120.01 (11)S1—Fe1—C4—O497 (20)
S2—Fe1—P—C17153.54 (11)S2—Fe1—C4—O4163 (20)
Fe2—Fe1—P—C17−155.71 (11)Fe2—Fe1—C4—O4110 (20)
C4—Fe1—P—C11−62.99 (15)C16—C11—C12—C13−0.1 (5)
C5—Fe1—P—C11−154.90 (14)P—C11—C12—C13−178.8 (2)
S1—Fe1—P—C11114.67 (11)C22—C17—C18—C190.0 (5)
S2—Fe1—P—C1128.22 (11)P—C17—C18—C19−175.5 (2)
Fe2—Fe1—P—C1178.98 (12)C3—Fe2—C1—O1−5(51)
C3—Fe2—S2—C6116.7 (3)C2—Fe2—C1—O1−99 (51)
C2—Fe2—S2—C6−155.14 (16)S1—Fe2—C1—O184 (51)
C1—Fe2—S2—C6−52.10 (15)S2—Fe2—C1—O1171 (100)
S1—Fe2—S2—C651.37 (11)Fe1—Fe2—C1—O1130 (51)
Fe1—Fe2—S2—C6103.67 (11)C17—C18—C19—C200.4 (5)
C3—Fe2—S2—Fe113.1 (3)C2—Fe2—C3—O3−141 (12)
C2—Fe2—S2—Fe1101.18 (12)C1—Fe2—C3—O3115 (12)
C1—Fe2—S2—Fe1−155.77 (11)S1—Fe2—C3—O311 (12)
S1—Fe2—S2—Fe1−52.30 (3)S2—Fe2—C3—O3−54 (12)
C4—Fe1—S2—C6140.93 (15)Fe1—Fe2—C3—O3−43 (12)
C5—Fe1—S2—C6−128.9 (3)C18—C19—C20—C21−0.5 (6)
P—Fe1—S2—C642.41 (11)C12—C11—C16—C15−0.6 (4)
S1—Fe1—S2—C6−53.97 (11)P—C11—C16—C15178.1 (2)
Fe2—Fe1—S2—C6−106.17 (11)C3—Fe2—C2—O280 (6)
C4—Fe1—S2—Fe2−112.90 (11)C1—Fe2—C2—O2179 (100)
C5—Fe1—S2—Fe2−22.7 (3)S1—Fe2—C2—O2−6(6)
P—Fe1—S2—Fe2148.58 (3)S2—Fe2—C2—O2−79 (6)
S1—Fe1—S2—Fe252.21 (3)Fe1—Fe2—C2—O2−24 (6)
C3—Fe2—S1—C7148.92 (15)C15—C14—C13—C12−0.7 (6)
C2—Fe2—S1—C7−124.1 (3)C11—C12—C13—C140.7 (5)
C1—Fe2—S1—C750.64 (15)C7—N1—C6—S271.9 (3)
S2—Fe2—S1—C7−50.33 (10)C8—N1—C6—S2−155.4 (2)
Fe1—Fe2—S1—C7−102.69 (11)Fe2—S2—C6—N1−69.1 (2)
C3—Fe2—S1—Fe1−108.40 (11)Fe1—S2—C6—N14.0 (2)
C2—Fe2—S1—Fe1−21.4 (2)C19—C20—C21—C220.3 (7)
C1—Fe2—S1—Fe1153.33 (11)C17—C22—C21—C200.1 (6)
S2—Fe2—S1—Fe152.36 (3)C13—C14—C15—C160.0 (6)
C4—Fe1—S1—C7122.3 (4)C11—C16—C15—C140.7 (5)
C5—Fe1—S1—C7−145.10 (15)C10—C9—C8—N1179.3 (3)
P—Fe1—S1—C7−49.34 (11)C7—N1—C8—C963.0 (4)
S2—Fe1—S1—C755.12 (11)C6—N1—C8—C9−69.2 (4)
Fe2—Fe1—S1—C7107.48 (11)
Table 1
Selected geometric parameters (Å, °) top
Fe1—P2.2021 (9)P—H11.32 (2)
Fe1—Fe22.5143 (6)
P—Fe1—Fe2145.99 (3)C7—N1—C8113.7 (2)
C7—N1—C6112.7 (2)C6—N1—C8115.3 (3)
Acknowledgements top

The authors are grateful to the Ministry of Science and Technology of China and the Chinese National Natural Science Foundation (grant Nos. 20471013, 20633020 and 20672017), the Swedish Energy Agency, the K & A Wallenberg Foundation, the Program of Introducing Talents of Discipline to Universities, and the Swedish Research Council for financial support of this work.

references
References top

Bruker (2001). SMART (Version ?), SAINT (Version ?) and SHELXTL (Version 6.14). Bruker AXS Inc., Madison, Wisconsin, USA.

Frey, M. (2002). ChemBioChem, 3, 153–160.

Gao, W., Ekström, J., Liu, J., Chen, C., Eriksson, L., Weng, L., Åkermark, B. & Sun, L. (2007). Inorg. Chem. 46, 1981–1991.

Lawrence, J. D., Li, H., Rauchfuss, T. B., Tnard, M. B. & Rohmer, M. (2001). Angew. Chem. Int. Ed. 40, 1768–1771.

Liu, T., Wang, M., Shi, Z., Cui, H., Dong, W., Chen, J., Åkermark, B. & Sun, L. (2004). Chem. Eur. J. 10, 4474–4479.

Milway, V. A., Tareque Abedin, S. M., Thompson, L. K. & Miller, D. O. (2006). Inorg. Chim. Acta, 359, 2700–2711.

Nicolet, Y., Lemon, B. J., Fontecilla-Camps, J. C. & Peters, J. W. (2000). Trends Biochem. Sci. 25, 138–143.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wang, F., Wang, M., Liu, X., Jin, K., Dong, W., Li, G., Åkermark, B. & Sun, L. (2005). Chem. Commun. 25, 3221–3223.