Undeca-carbonyl-μ(2)-methane-thiol-ato-μ(2)-[(pyridin-2-yl)methane-thiol-ato]-μ(4)-sulfido-tetra-iron(II)(2 Fe-Fe).

The title compound, [Fe(4)(C(6)H(6)NS)(CH(3)S)S(CO)(11)], com-prises two butterfly-shaped sub-cluster cores, Fe(2)S(2)N and Fe(2)S(2), joined together by a spiro-type μ(4)-S atom. The (pyridin-2-yl)methane-thiol-ate ligand is attached to the Fe(2)(CO)(5) unit in a μ-κN:κ(2)S mode, and the methane-thiol-ate ligand is coordinated to the Fe(2)(CO)(6) unit in a μ-κ(2)S fashion.

Related literature

For general background to iron–carbonyl clusters, see: Capon et al. (2009 ▶); Tard & Pickett (2009 ▶); Gloaguen & Rauchfuss (2009 ▶); DuBois & DuBois (2009 ▶). For the syntheses of μ4-S atom-containing Fe2(CO)6 butterfly-shaped complexes, see: Song (2005 ▶); Wang et al. (2000 ▶). For related structures, see: Song et al. (2000 ▶, 2002 ▶).

Experimental

Crystal data

[Fe4(C6H6NS)(CH3S)S(CO)11]

M = 734.87

Monoclinic,

a = 9.1253 (3) Å

b = 28.9515 (15) Å

c = 10.0376 (11) Å

β = 98.3238 (12)°

V = 2623.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.46 mm−1

T = 296 K

0.19 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.628, T max = 0.684

22650 measured reflections

6151 independent reflections

4914 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.093

S = 1.19

6151 reflections

335 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047751/tk5011sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047751/tk5011Isup2.hkl

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

[Fe4(C6H6NS)(CH3S)S(CO)11]	F(000) = 1456
Mr = 734.87	Dx = 1.860 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4914 reflections
a = 9.1253 (3) Å	θ = 2.2–27.9°
b = 28.9515 (15) Å	µ = 2.46 mm−1
c = 10.0376 (11) Å	T = 296 K
β = 98.3238 (12)°	Block, red
V = 2623.9 (3) Å3	0.19 × 0.16 × 0.15 mm
Z = 4

Bruker SMART APEX CCD diffractometer	6151 independent reflections
Radiation source: fine-focus sealed tube	4914 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω and φ scans	θmax = 27.8°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→11
Tmin = 0.628, Tmax = 0.684	k = −36→37
22650 measured reflections	l = −12→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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H-atom parameters constrained
S = 1.19	w = 1/[σ2(Fo2) + (0.P)2 + 7.4281P] where P = (Fo2 + 2Fc2)/3
6151 reflections	(Δ/σ)max < 0.001
335 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.50 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
C1	0.3087 (6)	0.1314 (2)	−0.0125 (5)	0.0612 (15)
C2	0.1355 (7)	0.1881 (2)	0.1127 (5)	0.0654 (16)
C3	0.1362 (6)	0.0911 (2)	0.1218 (5)	0.0624 (15)
C4	0.6043 (5)	0.09347 (17)	0.4471 (5)	0.0459 (11)
C5	0.3874 (5)	0.04298 (17)	0.3159 (5)	0.0454 (11)
C6	0.2725 (5)	0.23874 (17)	0.4290 (5)	0.0473 (11)
C7	0.4244 (6)	0.17741 (18)	0.6064 (5)	0.0492 (12)
C8	0.1887 (6)	0.20957 (17)	0.6739 (5)	0.0522 (12)
C9	0.0277 (5)	0.1125 (2)	0.6643 (5)	0.0543 (13)
C10	0.2578 (6)	0.07232 (18)	0.5986 (5)	0.0492 (12)
C11	−0.0013 (6)	0.06344 (19)	0.4274 (6)	0.0553 (13)
C12	−0.1349 (6)	0.1994 (2)	0.5184 (6)	0.0664 (16)
H12A	−0.2317	0.1881	0.4837	0.100*
H12B	−0.1330	0.2324	0.5089	0.100*
H12C	−0.1116	0.1914	0.6119	0.100*
C13	0.6172 (6)	0.16550 (17)	0.1184 (6)	0.0591 (15)
H13A	0.5847	0.1828	0.0368	0.071*
H13B	0.7106	0.1785	0.1601	0.071*
C14	0.6407 (5)	0.11606 (17)	0.0822 (5)	0.0463 (11)
C15	0.7145 (6)	0.1058 (2)	−0.0263 (5)	0.0627 (15)
H15	0.7458	0.1294	−0.0782	0.075*
C16	0.7408 (6)	0.0605 (2)	−0.0560 (6)	0.0666 (16)
H16	0.7893	0.0530	−0.1284	0.080*
C17	0.6937 (6)	0.0267 (2)	0.0236 (6)	0.0659 (16)
H17	0.7109	−0.0043	0.0062	0.079*
C18	0.6214 (5)	0.03872 (17)	0.1287 (5)	0.0510 (12)
H18	0.5920	0.0153	0.1823	0.061*
Fe1	0.25779 (7)	0.13887 (2)	0.14905 (6)	0.04061 (16)
Fe2	0.46539 (6)	0.09889 (2)	0.30222 (6)	0.03290 (14)
Fe3	0.24023 (7)	0.18660 (2)	0.52126 (6)	0.03460 (15)
Fe4	0.11363 (7)	0.10806 (2)	0.51490 (6)	0.03607 (15)
N1	0.5907 (4)	0.08240 (13)	0.1587 (4)	0.0406 (9)
O1	0.3419 (5)	0.1255 (2)	−0.1178 (4)	0.1053 (19)
O2	0.0599 (6)	0.21896 (19)	0.0902 (5)	0.114 (2)
O3	0.0630 (6)	0.05878 (19)	0.1038 (5)	0.1026 (17)
O4	0.6892 (4)	0.08923 (15)	0.5427 (4)	0.0741 (12)
O5	0.3306 (5)	0.00851 (13)	0.3287 (5)	0.0763 (12)
O6	0.2891 (5)	0.27134 (13)	0.3701 (4)	0.0717 (12)
O7	0.5400 (4)	0.17148 (16)	0.6638 (4)	0.0743 (12)
O8	0.1601 (5)	0.22297 (15)	0.7736 (4)	0.0820 (13)
O9	−0.0211 (5)	0.11492 (18)	0.7626 (4)	0.0858 (14)
O10	0.3524 (5)	0.05028 (16)	0.6518 (4)	0.0795 (13)
O11	−0.0745 (5)	0.03477 (16)	0.3740 (5)	0.0909 (15)
S1	0.48087 (14)	0.17202 (4)	0.23270 (12)	0.0434 (3)
S2	0.26921 (11)	0.13019 (3)	0.37332 (9)	0.0301 (2)
S3	0.00216 (12)	0.17347 (4)	0.42431 (12)	0.0420 (3)

	U11	U22	U33	U12	U13	U23
C1	0.048 (3)	0.090 (4)	0.045 (3)	0.015 (3)	0.005 (2)	0.003 (3)
C2	0.072 (4)	0.078 (4)	0.046 (3)	0.029 (3)	0.011 (3)	0.010 (3)
C3	0.056 (3)	0.082 (4)	0.046 (3)	0.003 (3)	−0.002 (2)	−0.012 (3)
C4	0.038 (2)	0.048 (3)	0.054 (3)	0.002 (2)	0.014 (2)	0.006 (2)
C5	0.046 (3)	0.042 (3)	0.052 (3)	0.006 (2)	0.017 (2)	−0.002 (2)
C6	0.051 (3)	0.044 (3)	0.049 (3)	0.000 (2)	0.015 (2)	−0.005 (2)
C7	0.046 (3)	0.055 (3)	0.047 (3)	−0.008 (2)	0.009 (2)	−0.010 (2)
C8	0.066 (3)	0.043 (3)	0.047 (3)	0.009 (2)	0.007 (2)	−0.004 (2)
C9	0.043 (3)	0.071 (4)	0.051 (3)	0.004 (3)	0.016 (2)	0.008 (3)
C10	0.051 (3)	0.051 (3)	0.049 (3)	0.000 (2)	0.019 (2)	0.011 (2)
C11	0.049 (3)	0.057 (3)	0.060 (3)	−0.005 (3)	0.009 (2)	0.007 (3)
C12	0.046 (3)	0.077 (4)	0.082 (4)	0.021 (3)	0.026 (3)	0.002 (3)
C13	0.070 (4)	0.046 (3)	0.073 (4)	0.000 (3)	0.048 (3)	0.009 (3)
C14	0.041 (2)	0.052 (3)	0.050 (3)	−0.002 (2)	0.020 (2)	0.001 (2)
C15	0.068 (4)	0.072 (4)	0.057 (3)	−0.010 (3)	0.040 (3)	−0.002 (3)
C16	0.064 (4)	0.084 (4)	0.060 (3)	−0.011 (3)	0.035 (3)	−0.017 (3)
C17	0.060 (3)	0.061 (4)	0.084 (4)	0.002 (3)	0.035 (3)	−0.023 (3)
C18	0.050 (3)	0.045 (3)	0.062 (3)	0.012 (2)	0.020 (2)	0.002 (2)
Fe1	0.0455 (4)	0.0488 (4)	0.0281 (3)	0.0108 (3)	0.0070 (3)	0.0025 (3)
Fe2	0.0319 (3)	0.0332 (3)	0.0354 (3)	0.0025 (3)	0.0108 (2)	0.0028 (2)
Fe3	0.0368 (3)	0.0362 (3)	0.0321 (3)	0.0000 (3)	0.0092 (2)	−0.0026 (3)
Fe4	0.0322 (3)	0.0404 (4)	0.0369 (3)	−0.0024 (3)	0.0095 (2)	0.0050 (3)
N1	0.0370 (19)	0.044 (2)	0.043 (2)	0.0056 (17)	0.0139 (16)	0.0025 (17)
O1	0.092 (3)	0.195 (6)	0.031 (2)	0.030 (4)	0.017 (2)	−0.013 (3)
O2	0.141 (5)	0.116 (4)	0.082 (3)	0.084 (4)	0.005 (3)	0.023 (3)
O3	0.099 (4)	0.106 (4)	0.097 (4)	−0.039 (3)	−0.005 (3)	−0.024 (3)
O4	0.050 (2)	0.095 (3)	0.071 (3)	0.008 (2)	−0.015 (2)	0.015 (2)
O5	0.089 (3)	0.041 (2)	0.106 (3)	−0.012 (2)	0.038 (3)	−0.003 (2)
O6	0.100 (3)	0.048 (2)	0.072 (3)	−0.001 (2)	0.027 (2)	0.014 (2)
O7	0.043 (2)	0.100 (3)	0.074 (3)	−0.002 (2)	−0.0098 (19)	−0.012 (2)
O8	0.118 (4)	0.085 (3)	0.046 (2)	0.024 (3)	0.024 (2)	−0.017 (2)
O9	0.075 (3)	0.133 (4)	0.058 (2)	−0.004 (3)	0.038 (2)	0.008 (3)
O10	0.067 (3)	0.093 (3)	0.077 (3)	0.027 (2)	0.009 (2)	0.041 (2)
O11	0.086 (3)	0.078 (3)	0.103 (4)	−0.035 (3)	−0.005 (3)	−0.014 (3)
S1	0.0511 (7)	0.0349 (6)	0.0489 (7)	−0.0006 (5)	0.0225 (5)	0.0025 (5)
S2	0.0304 (5)	0.0326 (5)	0.0282 (5)	0.0010 (4)	0.0069 (4)	0.0013 (4)
S3	0.0349 (6)	0.0500 (7)	0.0420 (6)	0.0060 (5)	0.0083 (5)	0.0020 (5)

C1—O1	1.153 (6)	C13—C14	1.500 (7)
C1—Fe1	1.764 (5)	C13—S1	1.820 (5)
C2—O2	1.132 (6)	C13—H13A	0.9700
C2—Fe1	1.814 (6)	C13—H13B	0.9700
C3—O3	1.150 (7)	C14—N1	1.360 (6)
C3—Fe1	1.768 (6)	C14—C15	1.393 (6)
C4—O4	1.150 (6)	C15—C16	1.372 (8)
C4—Fe2	1.792 (5)	C15—H15	0.9300
C5—O5	1.140 (6)	C16—C17	1.372 (8)
C5—Fe2	1.781 (5)	C16—H16	0.9300
C6—O6	1.135 (6)	C17—C18	1.368 (7)
C6—Fe3	1.817 (5)	C17—H17	0.9300
C7—O7	1.140 (6)	C18—N1	1.339 (6)
C7—Fe3	1.791 (5)	C18—H18	0.9300
C8—O8	1.138 (6)	Fe1—Fe2	2.5394 (9)
C8—Fe3	1.795 (5)	Fe1—S1	2.2968 (14)
C9—O9	1.142 (6)	Fe1—S2	2.2525 (11)
C9—Fe4	1.794 (5)	Fe2—S1	2.2401 (13)
C10—O10	1.142 (6)	Fe2—N1	2.022 (3)
C10—Fe4	1.785 (5)	Fe2—S2	2.2148 (11)
C11—O11	1.148 (6)	Fe3—Fe4	2.5473 (9)
C11—Fe4	1.809 (6)	Fe3—S2	2.2485 (12)
C12—S3	1.834 (5)	Fe3—S3	2.2801 (13)
C12—H12A	0.9600	Fe4—S2	2.2428 (11)
C12—H12B	0.9600	Fe4—S3	2.2761 (13)
C12—H12C	0.9600
O1—C1—Fe1	178.5 (6)	C4—Fe2—S2	106.51 (15)
O2—C2—Fe1	179.6 (7)	N1—Fe2—S2	153.28 (11)
O3—C3—Fe1	176.7 (6)	C5—Fe2—S1	157.93 (16)
O4—C4—Fe2	177.3 (5)	C4—Fe2—S1	105.45 (16)
O5—C5—Fe2	175.5 (4)	N1—Fe2—S1	86.20 (11)
O6—C6—Fe3	178.3 (5)	S2—Fe2—S1	78.70 (4)
O7—C7—Fe3	178.1 (5)	C5—Fe2—Fe1	100.93 (16)
O8—C8—Fe3	177.2 (5)	C4—Fe2—Fe1	155.39 (16)
O9—C9—Fe4	177.0 (5)	N1—Fe2—Fe1	97.22 (11)
O10—C10—Fe4	178.4 (5)	S2—Fe2—Fe1	56.06 (3)
O11—C11—Fe4	178.7 (5)	S1—Fe2—Fe1	57.03 (4)
S3—C12—H12A	109.5	C7—Fe3—C8	89.5 (2)
S3—C12—H12B	109.5	C7—Fe3—C6	99.0 (2)
H12A—C12—H12B	109.5	C8—Fe3—C6	102.1 (2)
S3—C12—H12C	109.5	C7—Fe3—S2	90.87 (16)
H12A—C12—H12C	109.5	C8—Fe3—S2	154.62 (17)
H12B—C12—H12C	109.5	C6—Fe3—S2	102.91 (15)
C14—C13—S1	112.8 (3)	C7—Fe3—S3	161.59 (17)
C14—C13—H13A	109.0	C8—Fe3—S3	94.30 (18)
S1—C13—H13A	109.0	C6—Fe3—S3	97.79 (16)
C14—C13—H13B	109.0	S2—Fe3—S3	78.05 (4)
S1—C13—H13B	109.0	C7—Fe3—Fe4	105.66 (17)
H13A—C13—H13B	107.8	C8—Fe3—Fe4	100.27 (17)
N1—C14—C15	121.9 (5)	C6—Fe3—Fe4	146.63 (16)
N1—C14—C13	118.4 (4)	S2—Fe3—Fe4	55.34 (3)
C15—C14—C13	119.7 (4)	S3—Fe3—Fe4	55.93 (4)
C16—C15—C14	119.6 (5)	C10—Fe4—C9	91.7 (2)
C16—C15—H15	120.2	C10—Fe4—C11	98.7 (2)
C14—C15—H15	120.2	C9—Fe4—C11	99.4 (2)
C15—C16—C17	118.4 (5)	C10—Fe4—S2	88.43 (15)
C15—C16—H16	120.8	C9—Fe4—S2	154.46 (19)
C17—C16—H16	120.8	C11—Fe4—S2	105.78 (17)
C18—C17—C16	119.5 (5)	C10—Fe4—S3	157.89 (17)
C18—C17—H17	120.2	C9—Fe4—S3	92.88 (18)
C16—C17—H17	120.2	C11—Fe4—S3	101.88 (17)
N1—C18—C17	123.7 (5)	S2—Fe4—S3	78.25 (4)
N1—C18—H18	118.2	C10—Fe4—Fe3	101.82 (17)
C17—C18—H18	118.2	C9—Fe4—Fe3	99.59 (18)
C1—Fe1—C3	90.3 (3)	C11—Fe4—Fe3	151.45 (17)
C1—Fe1—C2	98.5 (2)	S2—Fe4—Fe3	55.55 (3)
C3—Fe1—C2	103.2 (3)	S3—Fe4—Fe3	56.08 (4)
C1—Fe1—S2	157.68 (18)	C18—N1—C14	116.8 (4)
C3—Fe1—S2	90.26 (18)	C18—N1—Fe2	122.8 (3)
C2—Fe1—S2	103.12 (17)	C14—N1—Fe2	120.3 (3)
C1—Fe1—S1	92.86 (19)	C13—S1—Fe2	100.25 (17)
C3—Fe1—S1	152.38 (19)	C13—S1—Fe1	112.1 (2)
C2—Fe1—S1	103.4 (2)	Fe2—S1—Fe1	68.06 (4)
S2—Fe1—S1	76.76 (4)	Fe2—S2—Fe4	134.64 (5)
C1—Fe1—Fe2	103.19 (17)	Fe2—S2—Fe3	133.46 (5)
C3—Fe1—Fe2	97.69 (19)	Fe2—S2—Fe1	69.28 (4)
C2—Fe1—Fe2	149.67 (19)	Fe4—S2—Fe3	69.11 (4)
S2—Fe1—Fe2	54.66 (3)	Fe4—S2—Fe1	136.32 (5)
S1—Fe1—Fe2	54.91 (4)	Fe3—S2—Fe1	125.89 (5)
C5—Fe2—C4	95.8 (2)	C12—S3—Fe4	115.7 (2)
C5—Fe2—N1	96.52 (18)	C12—S3—Fe3	113.0 (2)
C4—Fe2—N1	98.67 (18)	Fe4—S3—Fe3	67.98 (4)
C5—Fe2—S2	89.81 (15)

Table 1

Selected bond lengths (Å)

Fe1—Fe2	2.5394 (9)
Fe1—S1	2.2968 (14)
Fe1—S2	2.2525 (11)
Fe2—S1	2.2401 (13)
Fe2—N1	2.022 (3)
Fe2—S2	2.2148 (11)
Fe3—Fe4	2.5473 (9)
Fe3—S2	2.2485 (12)
Fe3—S3	2.2801 (13)
Fe4—S2	2.2428 (11)
Fe4—S3	2.2761 (13)