{μ-2-[4-(1,3-Benzothia­zol-2-yl)phen­yl]-2-aza­propane-1,3-dithiol­ato-κ4S,S′:S,S′}bis­[tricarbonyl­iron(I)]

Gao, S.; Duan, Q.; Jiang, D.

doi:10.1107/S1600536812003753

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m248

doi:10.1107/S1600536812003753

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{μ-2-[4-(1,3-Benzothiazol-2-yl)phenyl]-2-azapropane-1,3-dithiolato-κ⁴S,S′:S,S′}bis[tricarbonyliron(I)]

Shang Gao,^a ^* Qian Duan ^a and Da-yong Jiang ^a

^aSchool of Materials Science and Engineering, Changchun University of Science and Technology, No. 7989 Weixing Road, Changchun 130022, People's Republic of China
^*Correspondence e-mail: cust_gaoshang@yahoo.cn

(Received 12 January 2012; accepted 28 January 2012; online 4 February 2012)

The title compound, [Fe₂(C₁₅H₁₂N₂S₃)(CO)₆], was prepared as an azadithiolatodiiron model for the active site of [FeFe]-hydrogenase. The Fe₂S₂ core adopts a butterfly shape, with each metal having a pseudo square-pyramidal geometry. The N-substituted azadithiolate is μ₂-κ⁴S,S′:S,S′-coordinated to the Fe(CO)₃ moieties to form two fused six-membered rings with different conformations. The sum of the C—N—C angles around the N atom [356.85 (15)°] indicates a flattening of the trigonal–pyramidal geometry about the N atom and an increase in the degree of sp²-hybridization.

Related literature

For reviews of hydrogenases, see: Cammack (1999 ); Evans & Pickett (2003 ). For the synthesis and structures of models for the active site of Fe-only hydrogenases, see: Lawrence et al. (2001 ); Song et al. (2005 ); Liu & Xiao (2011 ); Yin et al. (2011 ); For structures of Fe-only hydrogenases, see: Nicolet et al. (1999 ); Peters et al. (1998 ).

Experimental

Crystal data

[Fe₂(C₁₅H₁₂N₂S₃)(CO)₆]
M_r = 596.21
Monoclinic, P 2₁ /c
a = 13.8606 (12) Å
b = 7.6900 (7) Å
c = 21.5052 (19) Å
β = 92.447 (1)°
V = 2290.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 273 K
0.45 × 0.22 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.536, T_max = 0.858
12350 measured reflections
4509 independent reflections
4124 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.063
S = 1.04
4509 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2001); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003753/mw2048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003753/mw2048Isup2.hkl

checkCIF report

Comment top

Recently [FeFe]-hydrogenases ([FeFe]Hases) have received more attention than other types of hydrogenases due to their much higher efficiency in hydrogen production (Cammack, 1999; Evans & Pickett, 2003). Crystallographic and IR spectroscopy studies revealed the active site of [FeFe]Hases (so-called H-cluster) to contain a butterfly Fe₂S₂ subunit (Peters et al., 1998) and a variety of transition metal sulfides have been prepared as models of the diiron subunit of the H-cluster (Song et al., 2005; Yin et al., 2011; Liu & Xiao, 2011). We have synthesized the title compound as a structural model for the active site of [FeFe]Hases and report its crystal structure.

In the title compound, the Fe₂S₂ core adopts a butterfly framework with each metal having a pseudo square-pyramidal geometry. The length of the Fe—Fe bond [2.5036 (4) Å] is slightly shorter than those in the structures of natural enzymes (ca 2.6 Å) (Peters et al., 1998; Nicolet et al., 1999). The structure features two fused six-membered rings: Fe1—S1—C7—N1—C8—S2 which adopts a chair conformation and Fe2—S1—C7—N1—C8—S2 which adopts a boat conformation. The sum of the C—N—C angles around N1 atom is 356.85 (15)° implying a noticeable flattening of the trigonal pyramidal geometry about N1 and an increase in the degree of p-π conjugation between the substituted phenyl ring and the p-orbital of the bridging N atom. The distance of N1 from the plane defined by C7, C8 and C9 is 0.146 (2) Å and the dihedral angle between this plane and the mean plane of the adjacent phenyl ring is 2.5 (1)°. The substituted phenyl ring attached to N1 lies in an axial position relative to the metalloheterocycle and slants towards the Fe₂(CO)₃ unit. As a result, the C1—Fe1—Fe2 angle is enlarged by ca 7° compared with the C6—Fe2—Fe1 angle.

The molecular structure of the title compound is shown in Fig.1.

Related literature top

For reviews of hydrogenases, see: Cammack (1999); Evans & Pickett (2003). For the synthesis and structures of models for the active site of Fe-only hydrogenases, see: Lawrence et al. (2001); Song et al. (2005); Liu & Xiao (2011); Yin et al. (2011); For structures of Fe-only hydrogenases, see: Nicolet et al. (1999); Peters et al. (1998).

Experimental top

All reactions and operations related to the title compound were carried out under a dry, prepurified nitrogen atmosphere with standard Schlenk techniques. All solvents were dried and distilled prior to use according to standard methods. The starting material N,N'-bis(chloromethyl)-(4-benzothiazole)-phenylamine was prepared in 50% yield from 4-benzothiazole-phenylamine (Lawrence et al., 2001). A degassed solution of (µ-S₂)Fe₂(CO)₆ (1.38 g, 4.0 mmol) in 30 ml dry THF was cooled to 195 K. LiEt₃BH (1 M solution in THF, 8.0 ml, 8.0 mmol) was dropped into the above solution by syringe over 30 min. N,N'-bis(chloromethyl)-(4-benzothiazole)-phenylamine (2.6 g, 8.0 mmol) was added to the resulting dark green solution causing an immediate change in color to dark red. The mixture was stirred for 2 h at 195 K and another 1 h at room temperature. The solvent was removed on a rotary evaporator and the crude product was purified by column chromatography (silica, 20% dichloromethane in hexane as eluent) to give a red solid (1.37 g, 57%). Recrystallization from a CH₂Cl₂/hexane solution afforded crystals of the title compound suitable for X-ray study.

Computing details top

Data collection: APEX2 (Bruker, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level and H-atoms omitted.

{µ-2-[4-(1,3-Benzothiazol-2-yl)phenyl]-2-azapropane-1,3-dithiolato- κ⁴S,S':S,S'}bis[tricarbonyliron(I)] top

Crystal data top

[Fe₂(C₁₅H₁₂N₂S₃)(CO)₆]	F(000) = 1200
M_r = 596.21	D_x = 1.729 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8061 reflections
a = 13.8606 (12) Å	θ = 2.4–28.9°
b = 7.6900 (7) Å	µ = 1.58 mm⁻¹
c = 21.5052 (19) Å	T = 273 K
β = 92.447 (1)°	Parallelepiped, red
V = 2290.1 (4) Å³	0.45 × 0.22 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	4509 independent reflections
Radiation source: fine-focus sealed tube	4124 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −17→17
T_min = 0.536, T_max = 0.858	k = −9→7
12350 measured reflections	l = −23→26

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0343P)² + 0.6533P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.063	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.28 e Å⁻³
4509 reflections	Δρ_min = −0.23 e Å⁻³
307 parameters

Crystal data top

[Fe₂(C₁₅H₁₂N₂S₃)(CO)₆]	V = 2290.1 (4) Å³
M_r = 596.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.8606 (12) Å	µ = 1.58 mm⁻¹
b = 7.6900 (7) Å	T = 273 K
c = 21.5052 (19) Å	0.45 × 0.22 × 0.10 mm
β = 92.447 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4509 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4124 reflections with I > 2σ(I)
T_min = 0.536, T_max = 0.858	R_int = 0.020
12350 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 1.04	Δρ_max = 0.28 e Å⁻³
4509 reflections	Δρ_min = −0.23 e Å⁻³
307 parameters

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

	x	y	z	U_iso*/U_eq
Fe2	0.110403 (16)	0.28234 (3)	0.149643 (10)	0.03265 (8)
Fe1	0.139110 (16)	0.58723 (3)	0.114026 (11)	0.03417 (8)
S1	0.25452 (3)	0.37829 (6)	0.116610 (19)	0.03648 (10)
S2	0.11928 (3)	0.51324 (5)	0.214607 (19)	0.03527 (10)
S3	0.30972 (4)	−0.29556 (7)	0.43894 (2)	0.04817 (13)
C15	0.37264 (11)	−0.2378 (2)	0.37251 (8)	0.0354 (4)
N1	0.30863 (11)	0.3996 (2)	0.24269 (7)	0.0407 (3)
C9	0.31954 (11)	0.2394 (2)	0.27348 (8)	0.0347 (4)
N2	0.43589 (10)	−0.3512 (2)	0.35595 (7)	0.0392 (3)
C16	0.37529 (13)	−0.4878 (2)	0.44399 (8)	0.0410 (4)
C7	0.34275 (12)	0.4258 (3)	0.18192 (9)	0.0432 (4)
H7A	0.3992	0.3532	0.1772	0.052*
H7B	0.3633	0.5459	0.1785	0.052*
C1	0.21836 (13)	0.7719 (2)	0.11426 (9)	0.0434 (4)
C12	0.35215 (11)	−0.0756 (2)	0.33922 (7)	0.0345 (3)
C20	0.49798 (14)	−0.6393 (3)	0.38954 (9)	0.0463 (4)
H20A	0.5398	−0.6466	0.3570	0.056*
C11	0.28990 (12)	0.0515 (2)	0.36067 (8)	0.0402 (4)
H11A	0.2586	0.0321	0.3974	0.048*
C8	0.23726 (14)	0.5242 (2)	0.25908 (9)	0.0432 (4)
H8A	0.2640	0.6396	0.2538	0.052*
H8B	0.2254	0.5101	0.3029	0.052*
C6	0.13012 (13)	0.0967 (2)	0.20065 (8)	0.0415 (4)
C17	0.37132 (16)	−0.6217 (3)	0.48743 (9)	0.0529 (5)
H17A	0.3293	−0.6159	0.5200	0.063*
C3	0.02675 (14)	0.7039 (3)	0.11762 (9)	0.0476 (4)
C19	0.49426 (15)	−0.7706 (3)	0.43218 (10)	0.0524 (5)
H19A	0.5343	−0.8668	0.4288	0.063*
C10	0.27360 (12)	0.2049 (2)	0.32888 (9)	0.0412 (4)
H10A	0.2315	0.2867	0.3444	0.049*
C18	0.43067 (16)	−0.7617 (3)	0.48100 (10)	0.0555 (5)
H18A	0.4288	−0.8526	0.5095	0.067*
C14	0.38064 (13)	0.1106 (2)	0.25110 (8)	0.0401 (4)
H14A	0.4110	0.1284	0.2139	0.048*
C2	0.12325 (13)	0.5549 (3)	0.03178 (9)	0.0475 (4)
O6	0.13791 (12)	−0.0230 (2)	0.23068 (7)	0.0631 (4)
C21	0.43879 (12)	−0.4948 (2)	0.39519 (8)	0.0370 (4)
O4	0.09231 (14)	0.0933 (2)	0.03168 (8)	0.0794 (5)
C13	0.39634 (12)	−0.0421 (2)	0.28349 (8)	0.0383 (4)
H13A	0.4376	−0.1251	0.2677	0.046*
C4	0.09890 (15)	0.1660 (3)	0.07745 (9)	0.0479 (4)
O2	0.11222 (12)	0.5315 (3)	−0.02042 (7)	0.0755 (5)
O3	−0.04242 (12)	0.7811 (2)	0.12089 (9)	0.0775 (5)
O5	−0.10051 (10)	0.2857 (2)	0.15324 (7)	0.0628 (4)
C5	−0.01899 (13)	0.2869 (2)	0.15329 (8)	0.0417 (4)
O1	0.27005 (11)	0.8864 (2)	0.11324 (9)	0.0698 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe2	0.03394 (13)	0.03136 (14)	0.03265 (13)	−0.00374 (9)	0.00159 (9)	−0.00151 (9)
Fe1	0.03240 (13)	0.03442 (14)	0.03560 (14)	−0.00048 (9)	0.00050 (9)	0.00395 (10)
S1	0.0352 (2)	0.0389 (2)	0.0358 (2)	0.00191 (17)	0.00669 (16)	−0.00009 (17)
S2	0.0368 (2)	0.0348 (2)	0.0344 (2)	0.00106 (17)	0.00365 (16)	−0.00375 (16)
S3	0.0525 (3)	0.0520 (3)	0.0413 (2)	0.0123 (2)	0.0164 (2)	0.0083 (2)
C15	0.0308 (8)	0.0442 (10)	0.0313 (8)	−0.0017 (7)	0.0010 (6)	−0.0003 (7)
N1	0.0400 (8)	0.0405 (8)	0.0412 (8)	0.0023 (6)	−0.0049 (6)	0.0018 (6)
C9	0.0299 (8)	0.0394 (9)	0.0343 (8)	−0.0017 (7)	−0.0050 (6)	−0.0006 (7)
N2	0.0357 (7)	0.0432 (8)	0.0392 (8)	0.0021 (6)	0.0062 (6)	0.0036 (6)
C16	0.0427 (9)	0.0442 (10)	0.0362 (9)	0.0011 (8)	0.0029 (7)	0.0023 (8)
C7	0.0328 (9)	0.0457 (10)	0.0507 (11)	−0.0039 (7)	−0.0031 (7)	0.0118 (8)
C1	0.0371 (9)	0.0390 (10)	0.0544 (11)	0.0054 (8)	0.0040 (8)	0.0045 (8)
C12	0.0309 (8)	0.0393 (9)	0.0332 (8)	−0.0012 (7)	−0.0008 (6)	−0.0012 (7)
C20	0.0431 (10)	0.0481 (11)	0.0482 (11)	0.0048 (8)	0.0056 (8)	0.0013 (9)
C11	0.0360 (9)	0.0483 (10)	0.0367 (9)	0.0004 (8)	0.0079 (7)	0.0013 (8)
C8	0.0514 (10)	0.0359 (9)	0.0413 (9)	0.0009 (8)	−0.0120 (8)	−0.0048 (8)
C6	0.0448 (10)	0.0385 (10)	0.0408 (9)	−0.0051 (8)	−0.0030 (7)	−0.0046 (8)
C17	0.0657 (13)	0.0521 (12)	0.0416 (10)	0.0038 (10)	0.0120 (9)	0.0083 (9)
C3	0.0434 (10)	0.0473 (11)	0.0520 (11)	0.0016 (9)	0.0009 (8)	0.0083 (9)
C19	0.0548 (12)	0.0462 (11)	0.0559 (12)	0.0107 (9)	0.0002 (9)	0.0026 (9)
C10	0.0344 (9)	0.0442 (10)	0.0454 (10)	0.0055 (7)	0.0057 (7)	−0.0019 (8)
C18	0.0711 (14)	0.0467 (12)	0.0484 (12)	0.0032 (10)	0.0003 (10)	0.0122 (9)
C14	0.0429 (9)	0.0455 (10)	0.0323 (8)	0.0001 (8)	0.0061 (7)	−0.0010 (7)
C2	0.0416 (10)	0.0589 (12)	0.0418 (11)	−0.0057 (9)	−0.0003 (8)	0.0099 (9)
O6	0.0816 (11)	0.0460 (8)	0.0606 (9)	−0.0110 (8)	−0.0084 (8)	0.0136 (7)
C21	0.0344 (8)	0.0397 (9)	0.0367 (9)	−0.0017 (7)	−0.0002 (7)	0.0016 (7)
O4	0.1012 (14)	0.0845 (13)	0.0520 (9)	−0.0165 (10)	−0.0026 (9)	−0.0272 (9)
C13	0.0372 (9)	0.0414 (9)	0.0366 (9)	0.0056 (7)	0.0049 (7)	−0.0019 (7)
C4	0.0543 (11)	0.0443 (11)	0.0449 (11)	−0.0076 (9)	−0.0002 (8)	−0.0045 (9)
O2	0.0719 (11)	0.1161 (15)	0.0383 (9)	−0.0164 (10)	−0.0014 (7)	0.0050 (9)
O3	0.0480 (9)	0.0859 (13)	0.0990 (14)	0.0244 (9)	0.0068 (8)	0.0107 (10)
O5	0.0376 (8)	0.0841 (11)	0.0664 (10)	−0.0050 (7)	0.0000 (6)	0.0041 (8)
C5	0.0431 (10)	0.0420 (10)	0.0398 (9)	−0.0055 (8)	−0.0008 (7)	0.0014 (8)
O1	0.0516 (9)	0.0480 (9)	0.1105 (14)	−0.0123 (7)	0.0129 (9)	0.0029 (9)

Geometric parameters (Å, º) top

Fe2—C4	1.793 (2)	C7—H7B	0.9700
Fe2—C5	1.7989 (19)	C1—O1	1.136 (2)
Fe2—C6	1.8140 (19)	C12—C13	1.393 (2)
Fe2—S2	2.2594 (5)	C12—C11	1.395 (2)
Fe2—S1	2.2717 (5)	C20—C19	1.366 (3)
Fe2—Fe1	2.5036 (4)	C20—C21	1.389 (3)
Fe1—C2	1.790 (2)	C20—H20A	0.9300
Fe1—C1	1.7954 (19)	C11—C10	1.377 (3)
Fe1—C3	1.802 (2)	C11—H11A	0.9300
Fe1—S2	2.2647 (5)	C8—H8A	0.9700
Fe1—S1	2.2663 (5)	C8—H8B	0.9700
S1—C7	1.8589 (18)	C6—O6	1.127 (2)
S2—C8	1.8607 (18)	C17—C18	1.366 (3)
S3—C16	1.7360 (19)	C17—H17A	0.9300
S3—C15	1.7622 (17)	C3—O3	1.133 (2)
C15—N2	1.298 (2)	C19—C18	1.401 (3)
C15—C12	1.460 (2)	C19—H19A	0.9300
N1—C9	1.404 (2)	C10—H10A	0.9300
N1—C7	1.423 (2)	C18—H18A	0.9300
N1—C8	1.432 (2)	C14—C13	1.378 (2)
C9—C10	1.400 (2)	C14—H14A	0.9300
C9—C14	1.402 (2)	C2—O2	1.141 (2)
N2—C21	1.389 (2)	O4—C4	1.133 (2)
C16—C17	1.393 (3)	C13—H13A	0.9300
C16—C21	1.399 (2)	O5—C5	1.130 (2)
C7—H7A	0.9700

C4—Fe2—C5	89.75 (9)	C21—C16—S3	109.31 (13)
C4—Fe2—C6	97.84 (9)	N1—C7—S1	115.61 (12)
C5—Fe2—C6	96.54 (8)	N1—C7—H7A	108.4
C4—Fe2—S2	158.12 (7)	S1—C7—H7A	108.4
C5—Fe2—S2	89.18 (6)	N1—C7—H7B	108.4
C6—Fe2—S2	103.99 (6)	S1—C7—H7B	108.4
C4—Fe2—S1	86.46 (6)	H7A—C7—H7B	107.4
C5—Fe2—S1	154.01 (6)	O1—C1—Fe1	178.08 (19)
C6—Fe2—S1	109.45 (6)	C13—C12—C11	117.11 (16)
S2—Fe2—S1	84.991 (17)	C13—C12—C15	119.76 (15)
C4—Fe2—Fe1	102.22 (7)	C11—C12—C15	123.13 (15)
C5—Fe2—Fe1	99.59 (6)	C19—C20—C21	119.52 (18)
C6—Fe2—Fe1	154.19 (6)	C19—C20—H20A	120.2
S2—Fe2—Fe1	56.499 (14)	C21—C20—H20A	120.2
S1—Fe2—Fe1	56.412 (13)	C10—C11—C12	121.78 (16)
C2—Fe1—C1	99.31 (9)	C10—C11—H11A	119.1
C2—Fe1—C3	92.38 (9)	C12—C11—H11A	119.1
C1—Fe1—C3	97.81 (9)	N1—C8—S2	116.38 (12)
C2—Fe1—S2	153.38 (7)	N1—C8—H8A	108.2
C1—Fe1—S2	107.17 (7)	S2—C8—H8A	108.2
C3—Fe1—S2	86.77 (6)	N1—C8—H8B	108.2
C2—Fe1—S1	89.01 (7)	S2—C8—H8B	108.2
C1—Fe1—S1	97.45 (6)	H8A—C8—H8B	107.3
C3—Fe1—S1	164.24 (7)	O6—C6—Fe2	176.05 (17)
S2—Fe1—S1	84.996 (17)	C18—C17—C16	118.27 (19)
C2—Fe1—Fe2	99.09 (7)	C18—C17—H17A	120.9
C1—Fe1—Fe2	147.69 (6)	C16—C17—H17A	120.9
C3—Fe1—Fe2	107.70 (6)	O3—C3—Fe1	177.9 (2)
S2—Fe1—Fe2	56.300 (13)	C20—C19—C18	120.66 (19)
S1—Fe1—Fe2	56.619 (14)	C20—C19—H19A	119.7
C7—S1—Fe1	108.66 (6)	C18—C19—H19A	119.7
C7—S1—Fe2	112.74 (6)	C11—C10—C9	120.92 (16)
Fe1—S1—Fe2	66.969 (15)	C11—C10—H10A	119.5
C8—S2—Fe2	112.15 (6)	C9—C10—H10A	119.5
C8—S2—Fe1	109.86 (7)	C17—C18—C19	121.02 (19)
Fe2—S2—Fe1	67.201 (15)	C17—C18—H18A	119.5
C16—S3—C15	89.40 (8)	C19—C18—H18A	119.5
N2—C15—C12	124.02 (15)	C13—C14—C9	120.90 (16)
N2—C15—S3	114.61 (13)	C13—C14—H14A	119.6
C12—C15—S3	121.36 (12)	C9—C14—H14A	119.6
C9—N1—C7	121.62 (15)	O2—C2—Fe1	178.7 (2)
C9—N1—C8	122.20 (15)	N2—C21—C20	125.75 (16)
C7—N1—C8	113.03 (15)	N2—C21—C16	114.95 (16)
C10—C9—C14	117.48 (16)	C20—C21—C16	119.31 (17)
C10—C9—N1	121.61 (16)	C14—C13—C12	121.78 (16)
C14—C9—N1	120.86 (16)	C14—C13—H13A	119.1
C15—N2—C21	111.73 (15)	C12—C13—H13A	119.1
C17—C16—C21	121.22 (18)	O4—C4—Fe2	179.4 (2)
C17—C16—S3	129.47 (15)	O5—C5—Fe2	176.98 (18)

C4—Fe2—Fe1—C2	5.43 (9)	C3—Fe1—S2—C8	−139.75 (9)
C5—Fe2—Fe1—C2	−86.40 (9)	S1—Fe1—S2—C8	53.70 (6)
C6—Fe2—Fe1—C2	145.66 (15)	Fe2—Fe1—S2—C8	106.44 (6)
S2—Fe2—Fe1—C2	−168.97 (6)	C2—Fe1—S2—Fe2	24.94 (15)
S1—Fe2—Fe1—C2	82.74 (6)	C1—Fe1—S2—Fe2	−149.00 (6)
C4—Fe2—Fe1—C1	−118.59 (14)	C3—Fe1—S2—Fe2	113.81 (7)
C5—Fe2—Fe1—C1	149.58 (13)	S1—Fe1—S2—Fe2	−52.736 (15)
C6—Fe2—Fe1—C1	21.64 (19)	C16—S3—C15—N2	0.16 (14)
S2—Fe2—Fe1—C1	67.01 (12)	C16—S3—C15—C12	179.08 (14)
S1—Fe2—Fe1—C1	−41.28 (12)	C7—N1—C9—C10	−170.21 (16)
C4—Fe2—Fe1—C3	100.90 (10)	C8—N1—C9—C10	−11.7 (2)
C5—Fe2—Fe1—C3	9.07 (9)	C7—N1—C9—C14	12.7 (2)
C6—Fe2—Fe1—C3	−118.87 (16)	C8—N1—C9—C14	171.20 (16)
S2—Fe2—Fe1—C3	−73.50 (7)	C12—C15—N2—C21	−178.63 (15)
S1—Fe2—Fe1—C3	178.20 (7)	S3—C15—N2—C21	0.26 (19)
C4—Fe2—Fe1—S2	174.40 (7)	C15—S3—C16—C17	179.4 (2)
C5—Fe2—Fe1—S2	82.57 (6)	C15—S3—C16—C21	−0.52 (14)
C6—Fe2—Fe1—S2	−45.37 (14)	C9—N1—C7—S1	90.84 (17)
S1—Fe2—Fe1—S2	−108.29 (2)	C8—N1—C7—S1	−69.50 (18)
C4—Fe2—Fe1—S1	−77.30 (7)	Fe1—S1—C7—N1	71.07 (14)
C5—Fe2—Fe1—S1	−169.14 (6)	Fe2—S1—C7—N1	−1.10 (16)
C6—Fe2—Fe1—S1	62.93 (14)	N2—C15—C12—C13	5.1 (2)
S2—Fe2—Fe1—S1	108.29 (2)	S3—C15—C12—C13	−173.67 (13)
C2—Fe1—S1—C7	150.98 (9)	N2—C15—C12—C11	−174.37 (17)
C1—Fe1—S1—C7	51.72 (9)	S3—C15—C12—C11	6.8 (2)
C3—Fe1—S1—C7	−113.8 (3)	C13—C12—C11—C10	−0.9 (3)
S2—Fe1—S1—C7	−54.99 (6)	C15—C12—C11—C10	178.58 (16)
Fe2—Fe1—S1—C7	−107.45 (6)	C9—N1—C8—S2	−93.06 (18)
C2—Fe1—S1—Fe2	−101.57 (6)	C7—N1—C8—S2	67.16 (18)
C1—Fe1—S1—Fe2	159.17 (7)	Fe2—S2—C8—N1	5.80 (16)
C3—Fe1—S1—Fe2	−6.3 (2)	Fe1—S2—C8—N1	−66.87 (15)
S2—Fe1—S1—Fe2	52.460 (15)	C21—C16—C17—C18	−0.5 (3)
C4—Fe2—S1—C7	−151.33 (10)	S3—C16—C17—C18	179.55 (17)
C5—Fe2—S1—C7	126.56 (15)	C21—C20—C19—C18	0.7 (3)
C6—Fe2—S1—C7	−54.26 (9)	C12—C11—C10—C9	−0.2 (3)
S2—Fe2—S1—C7	48.83 (7)	C14—C9—C10—C11	1.4 (3)
Fe1—Fe2—S1—C7	101.47 (7)	N1—C9—C10—C11	−175.78 (16)
C4—Fe2—S1—Fe1	107.20 (7)	C16—C17—C18—C19	0.2 (3)
C5—Fe2—S1—Fe1	25.09 (14)	C20—C19—C18—C17	−0.4 (3)
C6—Fe2—S1—Fe1	−155.72 (6)	C10—C9—C14—C13	−1.6 (3)
S2—Fe2—S1—Fe1	−52.634 (16)	N1—C9—C14—C13	175.70 (16)
C4—Fe2—S2—C8	−117.92 (19)	C15—N2—C21—C20	179.26 (17)
C5—Fe2—S2—C8	154.81 (9)	C15—N2—C21—C16	−0.7 (2)
C6—Fe2—S2—C8	58.28 (9)	C19—C20—C21—N2	179.07 (18)
S1—Fe2—S2—C8	−50.54 (7)	C19—C20—C21—C16	−1.0 (3)
Fe1—Fe2—S2—C8	−103.10 (7)	C17—C16—C21—N2	−179.15 (18)
C4—Fe2—S2—Fe1	−14.81 (18)	S3—C16—C21—N2	0.79 (19)
C5—Fe2—S2—Fe1	−102.08 (6)	C17—C16—C21—C20	0.9 (3)
C6—Fe2—S2—Fe1	161.38 (6)	S3—C16—C21—C20	−179.16 (14)
S1—Fe2—S2—Fe1	52.558 (15)	C9—C14—C13—C12	0.4 (3)
C2—Fe1—S2—C8	131.37 (16)	C11—C12—C13—C14	0.8 (3)
C1—Fe1—S2—C8	−42.57 (9)	C15—C12—C13—C14	−178.70 (16)

Experimental details

Crystal data
Chemical formula	[Fe₂(C₁₅H₁₂N₂S₃)(CO)₆]
M_r	596.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	13.8606 (12), 7.6900 (7), 21.5052 (19)
β (°)	92.447 (1)
V (Å³)	2290.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.45 × 0.22 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.536, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	12350, 4509, 4124
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.063, 1.04
No. of reflections	4509
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.23

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Scientific and Technological Development Project of Jilin Province (grant No. 201101103) and the National Natural Science Foundation of China (grant No. 61106050) for financial support.

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