A trinuclear Fe–Fe–Ni complex formed by ligand reshuffling

Peleg, A.; Lo, W.; Jiang, J.

doi:10.1107/S1600536811017892

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages m766-m767

doi:10.1107/S1600536811017892

Open

access

A trinuclear Fe–Fe–Ni complex formed by ligand reshuffling

Ariel Peleg,^a Wenfeng Lo ^b and Jianfeng Jiang ^a ^*

^aDepartment of Chemistry, Yeshiva University, 500 West 185th Street, New York, NY 10033, USA, and ^bDepartment of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA
^*Correspondence e-mail: jiang@yu.edu

(Received 13 April 2011; accepted 11 May 2011; online 20 May 2011)

The title complex, dicarbonyl-3κ²C-(μ₃-3,6-dimethyl-3,6-diazaoctane-1,8-dithiolato-1:2:3κ⁷S:S,N,N′,S′:S,S′)(μ₂-3,6-dimethyl-3,6-diazaoctane-1,8-dithiolato-1:2κ⁵S,N,N′,S′:S)-1,2-diiron(II)-3-nickel(0) [Fe₂Ni(C₈H₁₈N₂S₂)₂(CO)₂], is the second example showing M(μ-SR)₂Ni⁰(CO)₂ coordination (M = any metal atom). Both Fe^II ions are five-coordinated in distorted trigonal–bipyramidal geometries by two N atoms and three S atoms. The Ni atom is four-coordinated in a distorted tetrahedral geometry by two S atoms and two carbonyl ligands. One of the 3,6-dimethyl-3,6-diazaoctane-1,8-dithiolate ligands is disordered, the major component having a refined occupancy of 0.873 (2). The Fe⋯Fe distance is 3.0945 (3)Å and the Ni⋯Fe distance is 2.8505 (3) Å.

Related literature

For the structure of [Fe^II(dsdm)Ni⁰(CO)₃]₂ (dsdm = 3,6-dimethyl-3,6-diazaoctane-1,8-dithiolato), see: Bouwman et al. (1999 ). For the structure of [Ni^II(N₂S₂′)Ni⁰(CO)₂] (N₂S₂′ = 4,7-diazadecane-3,8-dione-1,10-dithiolato), see: Linck et al. (2003 ). For the structure of [Fe^II(dsdm)]₂, see: Hu & Lippard (1974 ). The synthesis of the starting materials [Et₄N][Fe^II(CN)₂(CO)₃I] and [Ni^II(dsdm)] has been described by Jiang et al. (2009 ) and Turner et al. (1990 ). For structures of Ni–Fe hydrogenase active sites, see: Fontecilla-Camps et al. (2007 ). Structure checking was performed using PLATON (Spek, 2009 ).

Experimental

Crystal data

[Fe₂Ni(C₈H₁₈N₂S₂)₂(CO)₂]
M_r = 639.16
Triclinic, $[P \overline 1]$
a = 8.4051 (3) Å
b = 12.7146 (5) Å
c = 13.3451 (5) Å
α = 70.475 (1)°
β = 83.208 (1)°
γ = 79.309 (1)°
V = 1318.38 (9) Å³
Z = 2
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 173 K
0.35 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.774, T_max = 0.808
41649 measured reflections
6596 independent reflections
5863 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.056
S = 1.07
6596 reflections
301 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017892/pk2319sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017892/pk2319Isup2.hkl

checkCIF report

Comment top

We studied the reaction between [Ni^II(dsdm)] (Turner et al., 1990) and (Et₄N)[Fe^II(CN)₂(CO)₃I] (Jiang et al., 2009) in methanol solution in an attempt to synthesize a dithiolate bridged Ni-Fe complex [Ni^II(dsdm)Fe^II(CN)₂(CO)₂] to mimic the active site structure of Ni-Fe hydrogenase (Fontecilla-Camps et al., 2007), However, an insoluble material was obtained. Solid state infrared spectroscopy of the material has shown the presence of both CO and CN ligands. This material was then treated with LiHBEt₃ in THF to give a black-colored solution. Surprisingly, [Fe^II(dsdm)]₂Ni⁰(CO)₂] (Fig. 1) was isolated upon diffusion of diethyl ether to the black colored solution.

Reshuffling of ligands on [Ni^II(dsdm)] is not unprecedented. Bouwman has shown that a tetranuclear complex [Fe^II(dsdm)Ni⁰(CO)₃]₂ is isolated by the reaction between [Ni^II(dsdm)] and K[HFe⁰(CO)₄] in refluxing ethanol (Bouwman et al., 1999). Nickel is reduced by the low oxidation iron species in solution. In our system, a similar reshuffling occured, and nickel was reduced by hydride in THF solution.

This molecule crystallizes in the triclinic space group P-1 with one molecule per asymmetric unit. Part of the molecule is disordered. This disorder can be described as an approximate mirror operation about a plane along N4, N3, S4 and Fe2. The ratio between the two components of this disorder was refined freely, and converged at 0.873 (2). Bond lengths and angles between atoms of the major components of the disorders are determined with significantly higher accuracy than for those between the corresponding atoms of the minor components.

Nevertheless, the structure of [Fe^II(dsdm)]₂Ni⁰(CO)₂] shows several interesting features. It is only the second example of a M(µ-SR)₂Ni(CO)₂ coordination other than (Et₄N)₂[Ni^II(S₂N₂')Ni⁰(CO)₂] (S₂N₂' = µ₂-4,7-diazadecane-3,8-dione-1,10-dithiolato-N,N',S,S,S',S') made by Rauchfuss (Linck et al., 2003).

The trinuclear Fe-Fe-Ni complex is not symmetric. The Ni(CO)₂ unit is bridged by two sulfur atoms from one [Fe^II(dsdm)] unit. One such sulfur atom forms an additional bond to the adjacent iron. All four sulfur atoms in this molecule are different in their metal-coordination nature. S3 only coordinates to Fe2; S4 bridges between Fe1 and Fe2; S1 bridges between Fe1 and Ni3; S2 bridges among Fe1, Fe2 and Ni3. Even though both [Fe^II(dsdm)] units are distorted trigonal bipyramidal, their geometries are significantly different. The structure of the non-Ni bridging [Fe(dsdm)] unit is similar to the tetramer, [Fe^II(dsdm)Ni⁰(CO)₃]₂, reported (Bouwman et al., 1999) and the parent [Fe^II(dsdm)]₂ dimer reported by Lippard (Hu and Lippard, 1974). In the non-Ni-bridging [Fe^II(dsdm)] unit, the axial bonds are much longer than the equatorial bonds, i.e., Fe2-N3 (2.381 (2)Å) > Fe2-N4 (2.160 (2)Å), and Fe2-S4 (2.4511 (4)Å) > Fe2-S3 (2.3122 (4)Å) and Fe2-S2 (2.3919 (4)Å). However, the Ni-bridging [Fe(dsdm)] shows more distorted trigonal bipyramidal geometry. Significantly, the difference between the axial Fe1-N1 (2.241 (2)Å) and the equatorial Fe1-N2 (2.204 (2)Å) is not as substantial.

The Fe-Fe distance is 3.0945 (3)Å, which is similar to that in the tetranuclear Fe^II(dsdm)Ni⁰(CO)₃]₂ and shorter than that in the [Fe^II(dsdm)]₂ dimer. The Ni-Fe distance is 2.8505 (3)Å, which is similar to the Ni-Ni distance in (Et₄N)₂[Ni(S₂N₂')Ni(CO)₂].

Related literature top

For the structure of [Fe^II(dsdm)Ni⁰(CO)₃]₂, see: Bouwman et al. (1999). For the structure of [Ni^II(N2S2')Ni⁰(CO)₂], see: Linck et al. (2003). For the structure of [Fe^II(dsdm)]₂, see: Hu & Lippard (1974). The synthesis of the starting materials [Et₄N][Fe^II(CN)₂(CO)₃I] and [Ni^II(dsdm)] has been described by Jiang et al. (2009) and Turner et al. (1990). For structures of Ni-Fe hydrogenase active sites, see: Fontecilla-Camps et al. (2007). Structure checking was performed using PLATON (Spek; 2009).

Experimental top

Anhydrous methanol, THF, diethyl ether and LiHBEt₃ (1M solution in THF) was purchased from Acros. [Ni^II(dsdm)] and (Et₄N)[Fe^II(CN)₂(CO)₃I] were prepared according to published procedure (Turner et al., 1990, Jiang et al., 2009)

To 0.265 g (1.0 mmol) [Ni^II(dsdm)] dissolved in 10 ml methanol, a solution of 0.449 g (1.00 mmol) [Et₄N][Fe^II(CN)₂(CO)₃I] in 5 ml methanol was added. The reaction mixture was kept stirring for 2 h and a brown-colored precipitate formed. The precipitate was collected by filtration, washed with 5 ml methanol 3 times and dried under vacuum to afford 0.300 g light-brown colored powder (IR (ATR): 1983, 2036, 2110 cm^-1). The identity of this brown powder has not been determined. 0.400 ml LiHBEt₃ (1M in THF) was added to 0.086 g of this brown powder suspended in 2 ml THF, and the powders dissolved and the color turned black. The mixture was kept stirring for 2 h, and 6 ml diethyl ether was carefully added. The product, [Fe^II(dsdm)]₂Ni⁰(CO)₂], (0.029 g) was isolated as black needles after 2 days. (IR (THF): 1873, 1906 cm^-1)

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. : Ellipsoid plot of [Fe^II(dsdm)Fe^II(dsdm)Ni⁰(CO)₂] at 50% probability level. The minor disorder component is omitted for the sake of clarity.

dicarbonyl-3κ²C-(µ₃-3,6-dimethyl- 3,6-diazaoctane-1,8-dithiolato- 1:2:3κ⁷S:S,N,N',S':S, S')(µ₂-3,6-dimethyl-3,6-diazaoctane-1,8-dithiolato- 1:2κ⁵S,N,N',S':S)-1,2-diiron(II)- 3-nickel(0) top

Crystal data top

[Fe₂Ni(C₈H₁₈N₂S₂)₂(CO)₂]	Z = 2
M_r = 639.16	F(000) = 664
Triclinic, P1	D_x = 1.610 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4051 (3) Å	Cell parameters from 300 reflections
b = 12.7146 (5) Å	θ = 2.5–28.4°
c = 13.3451 (5) Å	µ = 2.13 mm⁻¹
α = 70.475 (1)°	T = 173 K
β = 83.208 (1)°	Needle, black
γ = 79.309 (1)°	0.35 × 0.10 × 0.10 mm
V = 1318.38 (9) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	6596 independent reflections
Radiation source: fine-focus sealed tube	5863 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→11
T_min = 0.774, T_max = 0.808	k = −16→16
41649 measured reflections	l = −17→17

Refinement top

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0257P)² + 0.7211P] where P = (F_o² + 2F_c²)/3
6596 reflections	(Δ/σ)_max = 0.001
301 parameters	Δρ_max = 0.84 e Å⁻³
2 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Fe₂Ni(C₈H₁₈N₂S₂)₂(CO)₂]	γ = 79.309 (1)°
M_r = 639.16	V = 1318.38 (9) Å³
Triclinic, P1	Z = 2
a = 8.4051 (3) Å	Mo Kα radiation
b = 12.7146 (5) Å	µ = 2.13 mm⁻¹
c = 13.3451 (5) Å	T = 173 K
α = 70.475 (1)°	0.35 × 0.10 × 0.10 mm
β = 83.208 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6596 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	5863 reflections with I > 2σ(I)
T_min = 0.774, T_max = 0.808	R_int = 0.026
41649 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	2 restraints
wR(F²) = 0.056	H-atom parameters constrained
S = 1.07	Δρ_max = 0.84 e Å⁻³
6596 reflections	Δρ_min = −0.31 e Å⁻³
301 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.16309 (2)	0.133392 (18)	0.257975 (16)	0.01240 (5)
Fe2	0.09584 (2)	0.348721 (18)	0.325379 (16)	0.01218 (5)
Ni3	0.28724 (2)	0.242434 (17)	0.047760 (16)	0.01672 (5)
S1	0.43299 (4)	0.11355 (3)	0.18653 (3)	0.01652 (8)
S2	0.10001 (4)	0.33301 (3)	0.15138 (3)	0.01364 (7)
S3	−0.16068 (4)	0.39578 (3)	0.39741 (3)	0.01589 (8)
S4	0.14979 (5)	0.14843 (3)	0.43141 (3)	0.01533 (8)
C1	0.4545 (2)	−0.02863 (14)	0.17643 (14)	0.0227 (3)
H1A	0.5104	−0.0291	0.1087	0.027*
H1B	0.5207	−0.0810	0.2325	0.027*
C2	0.29216 (19)	−0.06906 (14)	0.18532 (13)	0.0200 (3)
H2A	0.2377	−0.0295	0.1199	0.024*
H2B	0.3114	−0.1490	0.1936	0.024*
C3	0.02134 (19)	−0.07559 (13)	0.27173 (13)	0.0176 (3)
H3A	−0.0332	−0.0923	0.3422	0.021*
H3B	0.0314	−0.1417	0.2492	0.021*
C4	−0.07916 (19)	0.02363 (13)	0.19473 (13)	0.0170 (3)
H4A	−0.0334	0.0330	0.1226	0.020*
H4B	−0.1889	0.0082	0.1987	0.020*
C5	−0.14768 (18)	0.22706 (13)	0.12884 (12)	0.0158 (3)
H5A	−0.2637	0.2297	0.1283	0.019*
H5B	−0.0978	0.2168	0.0627	0.019*
C6	−0.11543 (18)	0.33834 (13)	0.13483 (12)	0.0158 (3)
H6A	−0.1801	0.3552	0.1944	0.019*
H6B	−0.1478	0.3985	0.0702	0.019*
C7	0.2542 (2)	−0.12185 (14)	0.37795 (14)	0.0229 (3)
H7A	0.1806	−0.1121	0.4360	0.034*
H7B	0.3559	−0.1004	0.3830	0.034*
H7C	0.2713	−0.1996	0.3810	0.034*
C8	−0.18756 (18)	0.12685 (14)	0.31805 (12)	0.0168 (3)
H8A	−0.2950	0.1178	0.3084	0.025*
H8B	−0.1918	0.1964	0.3326	0.025*
H8C	−0.1433	0.0648	0.3767	0.025*
C9	−0.1930 (2)	0.54613 (14)	0.32196 (14)	0.0213 (3)
H9A	−0.2153	0.5564	0.2493	0.026*
H9B	−0.2860	0.5840	0.3536	0.026*
C10	−0.04347 (19)	0.59781 (13)	0.32169 (13)	0.0193 (3)
H10A	−0.0647	0.6784	0.2848	0.023*
H10B	−0.0214	0.5869	0.3945	0.023*
C15	0.0975 (2)	0.59951 (14)	0.15256 (13)	0.0237 (3)
H15A	0.1044	0.6783	0.1340	0.036*
H15B	−0.0019	0.5911	0.1293	0.036*
H15C	0.1878	0.5634	0.1185	0.036*
C17	0.2083 (2)	0.18224 (14)	−0.03214 (13)	0.0216 (3)
C18	0.4093 (2)	0.34856 (16)	−0.02072 (14)	0.0274 (4)
C11A	0.2515 (4)	0.5652 (2)	0.3033 (3)	0.0152 (6)	0.873 (2)
H11A	0.2306	0.6334	0.3232	0.018*	0.873 (2)
H11B	0.3338	0.5747	0.2449	0.018*	0.873 (2)
C12A	0.3122 (2)	0.46365 (15)	0.39850 (14)	0.0166 (3)	0.873 (2)
H12A	0.4172	0.4723	0.4153	0.020*	0.873 (2)
H12B	0.2376	0.4622	0.4601	0.020*	0.873 (2)
C13A	0.3720 (2)	0.26051 (15)	0.47315 (14)	0.0187 (4)	0.873 (2)
H13A	0.3039	0.2722	0.5336	0.022*	0.873 (2)
H13B	0.4835	0.2593	0.4864	0.022*	0.873 (2)
C14A	0.3555 (3)	0.1464 (4)	0.4646 (2)	0.0190 (7)	0.873 (2)
H14A	0.3792	0.0876	0.5318	0.023*	0.873 (2)
H14B	0.4329	0.1296	0.4100	0.023*	0.873 (2)
C16A	0.4504 (2)	0.35148 (16)	0.28764 (14)	0.0179 (4)	0.873 (2)
H16A	0.4154	0.4095	0.2234	0.027*	0.873 (2)
H16B	0.4629	0.2790	0.2776	0.027*	0.873 (2)
H16C	0.5523	0.3632	0.3045	0.027*	0.873 (2)
C11B	0.258 (3)	0.544 (2)	0.317 (3)	0.0152 (6)	0.127 (2)
H11C	0.2967	0.6154	0.2801	0.018*	0.127 (2)
H11D	0.2327	0.5404	0.3907	0.018*	0.127 (2)
C12B	0.3875 (15)	0.4560 (10)	0.3141 (10)	0.0166 (3)	0.127 (2)
H12C	0.4824	0.4642	0.3440	0.020*	0.127 (2)
H12D	0.4161	0.4556	0.2416	0.020*	0.127 (2)
C13B	0.4403 (15)	0.2509 (10)	0.3774 (10)	0.0187 (4)	0.127 (2)
H13C	0.5410	0.2506	0.4064	0.022*	0.127 (2)
H13D	0.4649	0.2498	0.3049	0.022*	0.127 (2)
C14B	0.368 (2)	0.145 (4)	0.444 (3)	0.0190 (7)	0.127 (2)
H14C	0.3846	0.1305	0.5184	0.023*	0.127 (2)
H14D	0.4285	0.0809	0.4243	0.023*	0.127 (2)
C16B	0.3161 (15)	0.3535 (11)	0.4984 (10)	0.0179 (4)	0.127 (2)
H16D	0.4235	0.3431	0.5213	0.027*	0.127 (2)
H16E	0.2618	0.2923	0.5425	0.027*	0.127 (2)
H16F	0.2565	0.4236	0.5040	0.027*	0.127 (2)
N1	0.18488 (15)	−0.05031 (11)	0.27614 (10)	0.0160 (3)
N2	−0.08327 (15)	0.12932 (11)	0.21968 (10)	0.0137 (2)
N3	0.10106 (16)	0.54665 (11)	0.26911 (10)	0.0163 (3)
N4	0.32667 (15)	0.35576 (11)	0.37691 (10)	0.0146 (2)
O1	0.16438 (17)	0.14540 (12)	−0.08973 (11)	0.0326 (3)
O2	0.4842 (2)	0.41629 (15)	−0.06992 (14)	0.0542 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01141 (10)	0.01167 (10)	0.01369 (10)	−0.00240 (7)	−0.00188 (7)	−0.00282 (8)
Fe2	0.01255 (10)	0.01202 (10)	0.01194 (10)	−0.00203 (8)	−0.00163 (7)	−0.00344 (8)
Ni3	0.01734 (10)	0.01883 (11)	0.01431 (10)	−0.00452 (8)	0.00068 (7)	−0.00536 (8)
S1	0.01209 (16)	0.01827 (18)	0.01966 (18)	−0.00310 (13)	−0.00083 (13)	−0.00635 (15)
S2	0.01514 (17)	0.01348 (17)	0.01239 (16)	−0.00337 (13)	−0.00058 (12)	−0.00372 (13)
S3	0.01420 (17)	0.01595 (18)	0.01823 (18)	−0.00223 (13)	−0.00011 (13)	−0.00679 (14)
S4	0.01799 (17)	0.01352 (17)	0.01314 (16)	−0.00435 (13)	−0.00200 (13)	−0.00111 (13)
C1	0.0172 (8)	0.0192 (8)	0.0312 (9)	0.0001 (6)	0.0009 (6)	−0.0099 (7)
C2	0.0194 (8)	0.0162 (8)	0.0255 (8)	−0.0008 (6)	−0.0006 (6)	−0.0096 (6)
C3	0.0189 (7)	0.0141 (7)	0.0211 (8)	−0.0060 (6)	−0.0020 (6)	−0.0051 (6)
C4	0.0160 (7)	0.0164 (7)	0.0216 (8)	−0.0046 (6)	−0.0034 (6)	−0.0081 (6)
C5	0.0149 (7)	0.0174 (7)	0.0146 (7)	−0.0013 (6)	−0.0042 (5)	−0.0040 (6)
C6	0.0153 (7)	0.0160 (7)	0.0146 (7)	0.0002 (5)	−0.0035 (5)	−0.0034 (6)
C7	0.0265 (8)	0.0152 (8)	0.0243 (8)	−0.0022 (6)	−0.0092 (7)	−0.0009 (6)
C8	0.0144 (7)	0.0192 (8)	0.0160 (7)	−0.0037 (6)	0.0007 (5)	−0.0045 (6)
C9	0.0194 (8)	0.0171 (8)	0.0268 (8)	0.0013 (6)	−0.0065 (6)	−0.0069 (7)
C10	0.0220 (8)	0.0128 (7)	0.0230 (8)	0.0001 (6)	−0.0041 (6)	−0.0059 (6)
C15	0.0357 (10)	0.0173 (8)	0.0159 (7)	−0.0050 (7)	−0.0054 (7)	−0.0006 (6)
C17	0.0215 (8)	0.0216 (8)	0.0208 (8)	0.0032 (6)	−0.0030 (6)	−0.0085 (7)
C18	0.0265 (9)	0.0300 (10)	0.0227 (8)	−0.0067 (7)	0.0054 (7)	−0.0054 (7)
C11A	0.0210 (8)	0.0065 (16)	0.0164 (14)	−0.0054 (9)	−0.0018 (7)	0.0006 (12)
C12A	0.0185 (8)	0.0157 (8)	0.0174 (8)	−0.0044 (6)	−0.0033 (6)	−0.0060 (7)
C13A	0.0210 (9)	0.0168 (9)	0.0174 (8)	−0.0032 (7)	−0.0093 (7)	−0.0012 (7)
C14A	0.0208 (9)	0.0154 (8)	0.0191 (18)	−0.0020 (8)	−0.0099 (9)	−0.0008 (13)
C16A	0.0153 (8)	0.0186 (9)	0.0210 (9)	−0.0038 (7)	0.0010 (6)	−0.0080 (7)
C11B	0.0210 (8)	0.0065 (16)	0.0164 (14)	−0.0054 (9)	−0.0018 (7)	0.0006 (12)
C12B	0.0185 (8)	0.0157 (8)	0.0174 (8)	−0.0044 (6)	−0.0033 (6)	−0.0060 (7)
C13B	0.0210 (9)	0.0168 (9)	0.0174 (8)	−0.0032 (7)	−0.0093 (7)	−0.0012 (7)
C14B	0.0208 (9)	0.0154 (8)	0.0191 (18)	−0.0020 (8)	−0.0099 (9)	−0.0008 (13)
C16B	0.0153 (8)	0.0186 (9)	0.0210 (9)	−0.0038 (7)	0.0010 (6)	−0.0080 (7)
N1	0.0151 (6)	0.0137 (6)	0.0184 (6)	−0.0022 (5)	−0.0025 (5)	−0.0038 (5)
N2	0.0141 (6)	0.0132 (6)	0.0141 (6)	−0.0027 (5)	−0.0017 (5)	−0.0040 (5)
N3	0.0210 (6)	0.0133 (6)	0.0145 (6)	−0.0033 (5)	−0.0028 (5)	−0.0033 (5)
N4	0.0150 (6)	0.0131 (6)	0.0153 (6)	−0.0029 (5)	−0.0017 (5)	−0.0035 (5)
O1	0.0367 (7)	0.0340 (7)	0.0341 (7)	0.0055 (6)	−0.0133 (6)	−0.0223 (6)
O2	0.0591 (11)	0.0505 (10)	0.0465 (10)	−0.0323 (9)	0.0199 (8)	−0.0022 (8)

Geometric parameters (Å, º) top

Fe1—N2	2.2044 (12)	C8—H8C	0.9600
Fe1—N1	2.2408 (13)	C9—C10	1.521 (2)
Fe1—S1	2.3570 (4)	C9—H9A	0.9700
Fe1—S4	2.3734 (4)	C9—H9B	0.9700
Fe1—S2	2.4519 (4)	C10—N3	1.484 (2)
Fe1—Ni3	2.8505 (3)	C10—H10A	0.9700
Fe1—Fe2	3.0945 (3)	C10—H10B	0.9700
Fe2—N4	2.1601 (13)	C15—N3	1.475 (2)
Fe2—S3	2.3122 (4)	C15—H15A	0.9600
Fe2—N3	2.3809 (13)	C15—H15B	0.9600
Fe2—S2	2.3919 (4)	C15—H15C	0.9600
Fe2—S4	2.4511 (4)	C17—O1	1.148 (2)
Ni3—C17	1.7506 (17)	C18—O2	1.138 (2)
Ni3—C18	1.7821 (18)	C11A—N3	1.477 (3)
Ni3—S1	2.3193 (4)	C11A—C12A	1.535 (3)
Ni3—S2	2.3648 (4)	C11A—H11A	0.9700
S1—C1	1.8316 (17)	C11A—H11B	0.9700
S2—C6	1.8361 (15)	C12A—N4	1.474 (2)
S3—C9	1.8240 (17)	C12A—H12A	0.9700
S4—C14A	1.829 (3)	C12A—H12B	0.9700
S4—C14B	1.851 (19)	C13A—N4	1.472 (2)
C1—C2	1.523 (2)	C13A—C14A	1.525 (5)
C1—H1A	0.9700	C13A—H13A	0.9700
C1—H1B	0.9700	C13A—H13B	0.9700
C2—N1	1.481 (2)	C14A—H14A	0.9700
C2—H2A	0.9700	C14A—H14B	0.9700
C2—H2B	0.9700	C16A—N4	1.494 (2)
C3—N1	1.481 (2)	C16A—H16A	0.9600
C3—C4	1.518 (2)	C16A—H16B	0.9600
C3—H3A	0.9700	C16A—H16C	0.9600
C3—H3B	0.9700	C11B—C12B	1.42 (3)
C4—N2	1.4823 (19)	C11B—N3	1.523 (18)
C4—H4A	0.9700	C11B—H11C	0.9700
C4—H4B	0.9700	C11B—H11D	0.9700
C5—N2	1.4851 (19)	C12B—N4	1.420 (12)
C5—C6	1.518 (2)	C12B—H12C	0.9700
C5—H5A	0.9700	C12B—H12D	0.9700
C5—H5B	0.9700	C13B—N4	1.488 (13)
C6—H6A	0.9700	C13B—C14B	1.54 (4)
C6—H6B	0.9700	C13B—H13C	0.9700
C7—N1	1.476 (2)	C13B—H13D	0.9700
C7—H7A	0.9600	C14B—H14C	0.9700
C7—H7B	0.9600	C14B—H14D	0.9700
C7—H7C	0.9600	C16B—N4	1.604 (12)
C8—N2	1.4843 (19)	C16B—H16D	0.9600
C8—H8A	0.9600	C16B—H16E	0.9600
C8—H8B	0.9600	C16B—H16F	0.9600

N2—Fe1—N1	80.24 (5)	H9A—C9—H9B	108.1
N2—Fe1—S1	139.76 (3)	N3—C10—C9	111.84 (13)
N1—Fe1—S1	84.02 (3)	N3—C10—H10A	109.2
N2—Fe1—S4	108.57 (3)	C9—C10—H10A	109.2
N1—Fe1—S4	107.46 (4)	N3—C10—H10B	109.2
S1—Fe1—S4	111.447 (15)	C9—C10—H10B	109.2
N2—Fe1—S2	82.61 (3)	H10A—C10—H10B	107.9
N1—Fe1—S2	150.54 (4)	N3—C15—H15A	109.5
S1—Fe1—S2	94.015 (15)	N3—C15—H15B	109.5
S4—Fe1—S2	100.626 (14)	H15A—C15—H15B	109.5
N2—Fe1—Ni3	98.29 (3)	N3—C15—H15C	109.5
N1—Fe1—Ni3	106.94 (3)	H15A—C15—H15C	109.5
S1—Fe1—Ni3	51.843 (11)	H15B—C15—H15C	109.5
S4—Fe1—Ni3	139.189 (13)	O1—C17—Ni3	175.39 (16)
S2—Fe1—Ni3	52.316 (10)	O2—C18—Ni3	175.96 (19)
N2—Fe1—Fe2	99.68 (3)	N3—C11A—C12A	109.62 (19)
N1—Fe1—Fe2	157.78 (3)	N3—C11A—H11A	109.7
S1—Fe1—Fe2	108.341 (13)	C12A—C11A—H11A	109.7
S4—Fe1—Fe2	51.214 (11)	N3—C11A—H11B	109.7
S2—Fe1—Fe2	49.442 (10)	C12A—C11A—H11B	109.7
Ni3—Fe1—Fe2	95.102 (8)	H11A—C11A—H11B	108.2
N4—Fe2—S3	128.04 (4)	N4—C12A—C11A	112.07 (19)
N4—Fe2—N3	77.79 (5)	N4—C12A—H12A	109.2
S3—Fe2—N3	84.35 (3)	C11A—C12A—H12A	109.2
N4—Fe2—S2	115.98 (4)	N4—C12A—H12B	109.2
S3—Fe2—S2	114.298 (15)	C11A—C12A—H12B	109.2
N3—Fe2—S2	96.66 (3)	H12A—C12A—H12B	107.9
N4—Fe2—S4	84.21 (4)	N4—C13A—C14A	113.18 (18)
S3—Fe2—S4	99.308 (15)	N4—C13A—H13A	108.9
N3—Fe2—S4	159.44 (3)	C14A—C13A—H13A	108.9
S2—Fe2—S4	100.131 (14)	N4—C13A—H13B	108.9
N4—Fe2—Fe1	103.49 (3)	C14A—C13A—H13B	108.9
S3—Fe2—Fe1	117.732 (13)	H13A—C13A—H13B	107.8
N3—Fe2—Fe1	145.50 (3)	C13A—C14A—S4	110.2 (3)
S2—Fe2—Fe1	51.154 (10)	C13A—C14A—H14A	109.6
S4—Fe2—Fe1	49.007 (10)	S4—C14A—H14A	109.6
C17—Ni3—C18	115.76 (8)	C13A—C14A—H14B	109.6
C17—Ni3—S1	114.68 (6)	S4—C14A—H14B	109.6
C18—Ni3—S1	107.23 (6)	H14A—C14A—H14B	108.1
C17—Ni3—S2	117.38 (5)	N4—C16A—H16A	109.5
C18—Ni3—S2	102.18 (6)	N4—C16A—H16B	109.5
S1—Ni3—S2	97.362 (15)	N4—C16A—H16C	109.5
C17—Ni3—Fe1	104.28 (6)	C12B—C11B—N3	118 (2)
C18—Ni3—Fe1	139.94 (6)	C12B—C11B—H11C	107.9
S1—Ni3—Fe1	53.046 (11)	N3—C11B—H11C	107.9
S2—Ni3—Fe1	55.140 (11)	C12B—C11B—H11D	107.9
C1—S1—Ni3	109.86 (6)	N3—C11B—H11D	107.9
C1—S1—Fe1	100.08 (5)	H11C—C11B—H11D	107.2
Ni3—S1—Fe1	75.111 (13)	C11B—C12B—N4	104.5 (15)
C6—S2—Ni3	116.05 (5)	C11B—C12B—H12C	110.9
C6—S2—Fe2	102.65 (5)	N4—C12B—H12C	110.9
Ni3—S2—Fe2	134.701 (17)	C11B—C12B—H12D	110.9
C6—S2—Fe1	98.77 (5)	N4—C12B—H12D	110.9
Ni3—S2—Fe1	72.544 (12)	H12C—C12B—H12D	108.9
Fe2—S2—Fe1	79.404 (13)	N4—C13B—C14B	111.5 (14)
C9—S3—Fe2	98.25 (6)	N4—C13B—H13C	109.3
C14A—S4—C14B	9.0 (10)	C14B—C13B—H13C	109.3
C14A—S4—Fe1	108.34 (8)	N4—C13B—H13D	109.3
C14B—S4—Fe1	99.3 (10)	C14B—C13B—H13D	109.3
C14A—S4—Fe2	97.46 (16)	H13C—C13B—H13D	108.0
C14B—S4—Fe2	96.0 (13)	C13B—C14B—S4	116 (2)
Fe1—S4—Fe2	79.779 (13)	C13B—C14B—H14C	108.2
C2—C1—S1	112.85 (11)	S4—C14B—H14C	108.2
C2—C1—H1A	109.0	C13B—C14B—H14D	108.2
S1—C1—H1A	109.0	S4—C14B—H14D	108.2
C2—C1—H1B	109.0	H14C—C14B—H14D	107.3
S1—C1—H1B	109.0	N4—C16B—H16D	109.5
H1A—C1—H1B	107.8	N4—C16B—H16E	109.5
N1—C2—C1	112.68 (13)	H16D—C16B—H16E	109.5
N1—C2—H2A	109.1	N4—C16B—H16F	109.5
C1—C2—H2A	109.1	H16D—C16B—H16F	109.5
N1—C2—H2B	109.1	H16E—C16B—H16F	109.5
C1—C2—H2B	109.1	C7—N1—C3	109.93 (13)
H2A—C2—H2B	107.8	C7—N1—C2	110.37 (13)
N1—C3—C4	110.94 (12)	C3—N1—C2	110.25 (12)
N1—C3—H3A	109.5	C7—N1—Fe1	111.07 (10)
C4—C3—H3A	109.5	C3—N1—Fe1	108.42 (9)
N1—C3—H3B	109.5	C2—N1—Fe1	106.74 (9)
C4—C3—H3B	109.5	C4—N2—C8	110.02 (12)
H3A—C3—H3B	108.0	C4—N2—C5	109.08 (12)
N2—C4—C3	111.19 (12)	C8—N2—C5	110.03 (12)
N2—C4—H4A	109.4	C4—N2—Fe1	107.80 (9)
C3—C4—H4A	109.4	C8—N2—Fe1	105.61 (9)
N2—C4—H4B	109.4	C5—N2—Fe1	114.21 (9)
C3—C4—H4B	109.4	C15—N3—C11A	108.35 (18)
H4A—C4—H4B	108.0	C15—N3—C10	109.56 (13)
N2—C5—C6	112.18 (12)	C11A—N3—C10	110.6 (2)
N2—C5—H5A	109.2	C15—N3—C11B	115.6 (14)
C6—C5—H5A	109.2	C11A—N3—C11B	10.1 (12)
N2—C5—H5B	109.2	C10—N3—C11B	112.4 (14)
C6—C5—H5B	109.2	C15—N3—Fe2	112.91 (10)
H5A—C5—H5B	107.9	C11A—N3—Fe2	108.45 (12)
C5—C6—S2	111.27 (10)	C10—N3—Fe2	107.01 (9)
C5—C6—H6A	109.4	C11B—N3—Fe2	98.7 (11)
S2—C6—H6A	109.4	C12B—N4—C13A	136.8 (5)
C5—C6—H6B	109.4	C12B—N4—C12A	51.1 (5)
S2—C6—H6B	109.4	C13A—N4—C12A	110.12 (13)
H6A—C6—H6B	108.0	C12B—N4—C13B	113.3 (7)
N1—C7—H7A	109.5	C13A—N4—C13B	55.2 (5)
N1—C7—H7B	109.5	C12A—N4—C13B	143.5 (5)
H7A—C7—H7B	109.5	C12B—N4—C16A	60.8 (5)
N1—C7—H7C	109.5	C13A—N4—C16A	109.72 (13)
H7A—C7—H7C	109.5	C12A—N4—C16A	110.66 (13)
H7B—C7—H7C	109.5	C13B—N4—C16A	57.7 (5)
N2—C8—H8A	109.5	C12B—N4—C16B	106.9 (7)
N2—C8—H8B	109.5	C13A—N4—C16B	50.8 (5)
H8A—C8—H8B	109.5	C12A—N4—C16B	61.5 (5)
N2—C8—H8C	109.5	C13B—N4—C16B	103.5 (7)
H8A—C8—H8C	109.5	C16A—N4—C16B	139.9 (4)
H8B—C8—H8C	109.5	C12B—N4—Fe2	111.3 (5)
C10—C9—S3	110.20 (11)	C13A—N4—Fe2	111.61 (10)
C10—C9—H9A	109.6	C12A—N4—Fe2	107.49 (10)
S3—C9—H9A	109.6	C13B—N4—Fe2	109.0 (5)
C10—C9—H9B	109.6	C16A—N4—Fe2	107.19 (10)
S3—C9—H9B	109.6	C16B—N4—Fe2	112.6 (4)

Experimental details

Crystal data
Chemical formula	[Fe₂Ni(C₈H₁₈N₂S₂)₂(CO)₂]
M_r	639.16
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.4051 (3), 12.7146 (5), 13.3451 (5)
α, β, γ (°)	70.475 (1), 83.208 (1), 79.309 (1)
V (Å³)	1318.38 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.35 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.774, 0.808
No. of measured, independent and observed [I > 2σ(I)] reflections	41649, 6596, 5863
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.056, 1.07
No. of reflections	6596
No. of parameters	301
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.31

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Acknowledgements

This research was supported by Yeshiva University and the Petroleum Research Fund (UNI No. 49424).

References

Bouwman, E., Henderson, R. K., Spek, A. L. & Reedijk, J. (1999). Eur. J. Inorg. Chem. pp. 217–219. CrossRef Google Scholar
Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Fontecilla-Camps, J. C., Volbeda, A., Cavazza, C. & Nicolet, Y. (2007). Chem. Rev. 107, 4273–4303. Web of Science CrossRef PubMed CAS Google Scholar
Hu, W. & Lippard, S. J. (1974). J. Am. Chem. Soc. 96, 2366–2372. CrossRef CAS Google Scholar
Jiang, J., Maruani, M., Solaimanzadeh, J., Lo, W., Koch, S. A. & Millar, M. (2009). Inorg. Chem. 48, 6359–6361. Web of Science CrossRef CAS PubMed Google Scholar
Linck, R. C., Spahn, C. W., Rauchfuss, T. B. & Wilson, S. R. (2003). J. Am. Chem. Soc. 125, 8700–8701. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turner, M. A., Driessen, W. L. & Reedijk, J. (1990). Inorg. Chem. 29, 3331–3335. CSD CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar