[μ-3-(Methyl-sulfan-yl)benzene-1,2-di-thiol-ato-1:2κ(4) S,S':S,S']bis-[tri-carbonyl-iron(I)].

The title compound, [Fe2(C7H6S3)(CO)6], was prepared as a biomimic for the active site of [FeFe]-hydrogenases. The central Fe2S2 core is in a butterfly conformation and each Fe(I) atom has a pseudo-square-pyramidal coordination by three O atoms and two S atoms. The Fe-Fe distance is 2.471 (2) Å and the dihedral angle between the two Fe-S-Fe planes is 78.96 (7)°. The least-squares plane through the -S(C7H6S)S- bridge nearly bis-ects the mol-ecular structure: except for the two Fe(CO)3 units, all atoms are in this plane with an average deviation from the plane of 0.028 (3) Å. In the crystal, the mol-ecules are linked into chains along [001] by C-H⋯π(arene) inter-actions.

Related literature

For general background to [FeFe]-hydrogenases, see: Capon et al. (2009 ▶); Tard & Pickett (2009 ▶). For the crystal structure of the natural enzyme, see: Peters et al. (1998 ▶); Nicolet et al. (1999 ▶). For related structures and the synthesis, see: Maiolo et al. (1981 ▶); Wang et al. (2005 ▶); Dong et al. (2006 ▶).

Experimental

Crystal data

[Fe2(C7H6S3)(CO)6]

M = 466.06

Monoclinic,

a = 16.531 (17) Å

b = 7.975 (8) Å

c = 13.047 (13) Å

β = 92.055 (13)°

V = 1719 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.08 mm−1

T = 295 K

0.39 × 0.24 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.555, T max = 0.847

8260 measured reflections

3024 independent reflections

2098 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.084

S = 0.97

3024 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); 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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009860/vn2067sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009860/vn2067Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Fe2(C7H6S3)(CO)6]	F(000) = 928
Mr = 466.06	Dx = 1.801 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2629 reflections
a = 16.531 (17) Å	θ = 2.5–27.1°
b = 7.975 (8) Å	µ = 2.08 mm−1
c = 13.047 (13) Å	T = 295 K
β = 92.055 (13)°	Block, red
V = 1719 (3) Å3	0.39 × 0.24 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	3024 independent reflections
Radiation source: fine-focus sealed tube	2098 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
φ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −19→18
Tmin = 0.555, Tmax = 0.847	k = −9→9
8260 measured reflections	l = −15→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 0.97	w = 1/[σ2(Fo2) + (0.0341P)2] where P = (Fo2 + 2Fc2)/3
3024 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
Fe1	0.17590 (2)	0.29795 (7)	0.64150 (4)	0.04642 (17)
Fe2	0.18906 (3)	0.54555 (7)	0.52941 (4)	0.04814 (18)
S3	0.46296 (5)	0.53167 (12)	0.73543 (7)	0.0462 (2)
S2	0.22860 (5)	0.28468 (12)	0.48479 (7)	0.0475 (2)
S1	0.27674 (5)	0.48911 (12)	0.66349 (7)	0.0446 (2)
C8	0.35707 (16)	0.3899 (4)	0.5983 (2)	0.0354 (7)
C10	0.3893 (2)	0.2051 (4)	0.4606 (3)	0.0481 (9)
H10A	0.3730	0.1375	0.4055	0.058*
C2	0.0831 (2)	0.2118 (5)	0.5909 (3)	0.0560 (10)
C9	0.33421 (18)	0.2915 (4)	0.5159 (3)	0.0401 (8)
C5	0.1075 (2)	0.5260 (5)	0.4373 (4)	0.0605 (11)
C1	0.21760 (19)	0.1120 (6)	0.6991 (3)	0.0564 (10)
C7	0.43793 (17)	0.4062 (4)	0.6280 (3)	0.0377 (8)
C11	0.4698 (2)	0.2221 (5)	0.4897 (3)	0.0514 (9)
H11A	0.5086	0.1648	0.4535	0.062*
C12	0.49397 (19)	0.3216 (4)	0.5709 (3)	0.0449 (9)
H12A	0.5488	0.3324	0.5879	0.054*
O2	0.02428 (15)	0.1593 (4)	0.5570 (3)	0.0859 (10)
O1	0.24308 (17)	−0.0076 (4)	0.7338 (3)	0.0867 (11)
C4	0.2506 (2)	0.6882 (6)	0.4606 (4)	0.0700 (12)
O5	0.05695 (18)	0.5075 (4)	0.3771 (3)	0.0918 (11)
O6	0.09707 (19)	0.7802 (4)	0.6518 (3)	0.0961 (12)
O4	0.2905 (2)	0.7821 (5)	0.4201 (3)	0.1088 (13)
O3	0.09360 (19)	0.4359 (5)	0.8164 (3)	0.0994 (12)
C6	0.1338 (2)	0.6903 (5)	0.6042 (4)	0.0643 (12)
C3	0.1254 (2)	0.3805 (6)	0.7494 (4)	0.0631 (11)
C13	0.57037 (19)	0.5072 (4)	0.7506 (3)	0.0543 (10)
H13A	0.5900	0.5721	0.8082	0.082*
H13B	0.5956	0.5454	0.6897	0.082*
H13C	0.5831	0.3911	0.7619	0.082*

	U11	U22	U33	U12	U13	U23
Fe1	0.0379 (3)	0.0561 (4)	0.0452 (3)	−0.0011 (2)	0.0000 (2)	0.0002 (3)
Fe2	0.0429 (3)	0.0491 (4)	0.0522 (4)	0.0050 (2)	−0.0029 (2)	−0.0011 (3)
S3	0.0421 (4)	0.0487 (6)	0.0479 (6)	−0.0040 (4)	0.0011 (4)	−0.0067 (5)
S2	0.0480 (4)	0.0519 (6)	0.0422 (6)	−0.0004 (4)	−0.0046 (4)	−0.0077 (5)
S1	0.0379 (4)	0.0538 (6)	0.0423 (6)	0.0033 (4)	0.0016 (4)	−0.0123 (4)
C8	0.0392 (15)	0.036 (2)	0.0313 (19)	0.0026 (15)	0.0060 (13)	−0.0023 (16)
C10	0.061 (2)	0.046 (2)	0.038 (2)	0.0035 (18)	0.0044 (17)	−0.0051 (18)
C2	0.052 (2)	0.058 (3)	0.057 (3)	0.0055 (19)	−0.0012 (18)	0.002 (2)
C9	0.0433 (16)	0.040 (2)	0.037 (2)	0.0048 (15)	0.0035 (14)	0.0003 (17)
C5	0.052 (2)	0.061 (3)	0.068 (3)	0.0124 (19)	−0.001 (2)	−0.002 (2)
C1	0.0372 (17)	0.070 (3)	0.061 (3)	−0.0023 (19)	−0.0012 (17)	−0.001 (2)
C7	0.0405 (16)	0.0300 (19)	0.043 (2)	−0.0003 (14)	0.0051 (14)	0.0067 (16)
C11	0.056 (2)	0.050 (2)	0.050 (3)	0.0106 (18)	0.0194 (17)	0.003 (2)
C12	0.0416 (17)	0.046 (2)	0.048 (2)	0.0045 (16)	0.0079 (15)	0.0058 (19)
O2	0.0549 (15)	0.087 (2)	0.115 (3)	−0.0205 (15)	−0.0156 (17)	−0.004 (2)
O1	0.0665 (18)	0.085 (2)	0.108 (3)	0.0094 (17)	−0.0127 (18)	0.028 (2)
C4	0.062 (2)	0.069 (3)	0.079 (3)	0.006 (2)	−0.005 (2)	0.006 (3)
O5	0.0720 (19)	0.109 (3)	0.092 (3)	0.0123 (17)	−0.034 (2)	−0.008 (2)
O6	0.083 (2)	0.088 (3)	0.117 (3)	0.0311 (18)	−0.0015 (19)	−0.043 (2)
O4	0.101 (2)	0.096 (3)	0.130 (4)	−0.025 (2)	0.021 (2)	0.030 (3)
O3	0.087 (2)	0.145 (3)	0.068 (3)	0.028 (2)	0.0250 (19)	−0.007 (2)
C6	0.048 (2)	0.064 (3)	0.080 (3)	0.004 (2)	−0.011 (2)	−0.005 (3)
C3	0.0422 (19)	0.087 (3)	0.060 (3)	0.005 (2)	0.0038 (19)	0.007 (3)
C13	0.0432 (18)	0.055 (3)	0.064 (3)	−0.0049 (16)	−0.0044 (17)	−0.001 (2)

Fe1—C1	1.789 (5)	C8—C9	1.373 (4)
Fe1—C2	1.786 (4)	C10—C9	1.368 (5)
Fe1—C3	1.788 (5)	C10—C11	1.378 (5)
Fe1—Fe2	2.471 (2)	C10—H10A	0.9300
Fe1—S1	2.2695 (19)	C11—C12	1.372 (5)
Fe1—S2	2.253 (2)	C11—H11A	0.9300
Fe2—C4	1.789 (5)	C12—H12A	0.9300
Fe2—C5	1.781 (4)	C13—H13A	0.9600
Fe2—C6	1.784 (5)	C13—H13B	0.9600
Fe2—S1	2.2763 (19)	C13—H13C	0.9600
Fe2—S2	2.263 (2)	O3—C3	1.127 (5)
C1—O1	1.131 (4)	O6—C6	1.139 (5)
C2—O2	1.133 (4)	S1—C8	1.787 (3)
C4—O4	1.140 (5)	S2—C9	1.779 (3)
C5—O5	1.135 (5)	S3—C7	1.759 (4)
C7—C12	1.385 (5)	S3—C13	1.790 (4)
C8—C7	1.385 (4)
C2—Fe1—C3	90.77 (19)	C8—S1—Fe1	101.39 (13)
C2—Fe1—C1	98.59 (17)	C8—S1—Fe2	100.67 (13)
C3—Fe1—C1	99.1 (2)	Fe1—S1—Fe2	65.86 (5)
C2—Fe1—S2	90.09 (15)	C9—C8—C7	120.6 (3)
C3—Fe1—S2	159.76 (15)	C9—C8—S1	115.9 (2)
C1—Fe1—S2	100.74 (14)	C7—C8—S1	123.4 (2)
C2—Fe1—S1	157.30 (13)	C9—C10—C11	117.3 (3)
C3—Fe1—S1	90.84 (14)	C9—C10—H10A	121.3
C1—Fe1—S1	103.50 (13)	C11—C10—H10A	121.3
S2—Fe1—S1	80.80 (5)	O2—C2—Fe1	178.5 (4)
C2—Fe1—Fe2	100.45 (13)	C10—C9—C8	122.1 (3)
C3—Fe1—Fe2	103.00 (16)	C10—C9—S2	122.0 (3)
C1—Fe1—Fe2	150.44 (12)	C8—C9—S2	115.9 (2)
S2—Fe1—Fe2	57.01 (5)	O5—C5—Fe2	177.1 (4)
S1—Fe1—Fe2	57.20 (5)	O1—C1—Fe1	178.4 (4)
C5—Fe2—C6	92.06 (19)	C8—C7—C12	117.4 (3)
C5—Fe2—C4	98.5 (2)	C8—C7—S3	118.3 (2)
C6—Fe2—C4	100.1 (2)	C12—C7—S3	124.3 (2)
C5—Fe2—S2	87.98 (13)	C12—C11—C10	121.5 (3)
C6—Fe2—S2	153.34 (15)	C12—C11—H11A	119.3
C4—Fe2—S2	106.31 (16)	C10—C11—H11A	119.3
C5—Fe2—S1	161.32 (14)	C11—C12—C7	121.0 (3)
C6—Fe2—S1	91.81 (15)	C11—C12—H12A	119.5
C4—Fe2—S1	98.82 (15)	C7—C12—H12A	119.5
S2—Fe2—S1	80.45 (5)	O4—C4—Fe2	177.5 (5)
C5—Fe2—Fe1	104.41 (14)	O6—C6—Fe2	178.4 (4)
C6—Fe2—Fe1	97.78 (16)	O3—C3—Fe1	178.5 (5)
C4—Fe2—Fe1	150.30 (13)	S3—C13—H13A	109.5
S2—Fe2—Fe1	56.64 (3)	S3—C13—H13B	109.5
S1—Fe2—Fe1	56.94 (5)	H13A—C13—H13B	109.5
C7—S3—C13	103.30 (16)	S3—C13—H13C	109.5
C9—S2—Fe1	101.52 (13)	H13A—C13—H13C	109.5
C9—S2—Fe2	101.73 (12)	H13B—C13—H13C	109.5
Fe1—S2—Fe2	66.35 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Cg1i	0.96	2.69	3.590 (5)	157

Table 1

Selected bond lengths (Å)

Fe1—C1	1.789 (5)
Fe1—C2	1.786 (4)
Fe1—C3	1.788 (5)
Fe1—S1	2.2695 (19)
Fe1—S2	2.253 (2)
Fe2—C4	1.789 (5)
Fe2—C5	1.781 (4)
Fe2—C6	1.784 (5)
Fe2—S1	2.2763 (19)
Fe2—S2	2.263 (2)

Table 2

C—H⋯π(arene) inter­action geometry (Å, °)

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯Cg1i	0.96	2.69	3.590 (5)	157

Symmetry code: (i) .