Crystal structure of [μ2-3,3-dimethyl-4-(propan-2-yl­idene)thietane-2,2-dithiol­ato-κ4S:S′:S:S′]bis[tricarbonyl­iron(I)](Fe—Fe)

Zhao, P.; Bertke, J.A.; Rauchfuss, T.B.

doi:10.1107/S2056989015018496

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Volume 71| Part 11| November 2015| Pages 1296-1299

https://doi.org/10.1107/S2056989015018496

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Crystal structure of [μ₂-3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-dithiolato-κ⁴S:S′:S:S′]bis[tricarbonyliron(I)](Fe—Fe)

Peihua Zhao,^a Jeffery A. Bertke ^a ^* and Thomas B. Rauchfuss ^a

^aSchool of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
^*Correspondence e-mail: jbertke@illinois.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 16 September 2015; accepted 2 October 2015; online 10 October 2015)

The title complex, [Fe₂(C₈H₁₂S₃)(CO)₆] or [{Fe(CO)₃}₂(μ-L)] [L = 3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-bis(thiolato)], consists of two Fe(CO)₃ moieties double-bridged by a dithiolate ligand. Each of the two Fe^I atoms has a distorted anti-prismatic coordination environment consisting of three carbonyl groups, two S atoms of the dithiolate ligand and the neighboring Fe^I atom [Fe—Fe = 2.4921 (4) Å]. Weak C—H⋯O intermolecular interactions result in the formation of dimers. This is the second crystal structure reported with the 3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-bis(thiolate) ligand and the first in which it bridges two metal atoms.

Keywords: crystal structure; iron(I); thietane; hexacarbonyl.

CCDC reference: 1429290

1. Chemical context

Iron–sulfur complexes have attracted considerable attention over the past decades (Ogino et al., 1998 ). This is mainly because such complexes possess the distinctive iron–sulfur cluster core, which is biologically related to the active site of [FeFe]-hydrogenases (Fontecilla-Camps et al., 2007 ). In particular, [FeFe]-hydrogenases are a class of natural enzymes that can reversibly catalyse the evolution and uptake of hydrogen in several microorganisms (Cammack, 1999 ; Stephenson & Stickland, 1931 ). In view of this, a large number of iron–sulfur cluster complexes have been designed and synthesized as the active site models of [FeFe]-hydrogenases (e.g. Capon et al., 2005 ; Darensbourg et al., 2000 ; Gloaguen & Rauchfuss, 2009 ; Rauchfuss, 2015 ; Tard & Pickett, 2009 ).

Most recently, we investigated the preparation of iron–sulfur complexes via the reaction of 1,3-cyclobutanedithiolate compounds with [Fe₃(CO)₁₂] and have obtained an unexpected iron–sulfur complex, [Fe₂(CO)₆(C₈H₁₂S₃)] or [{Fe(CO)₃}₂(μ-L)] [L = 3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-bis(thiolate), C₈H₁₂S₃], (I).

Fig. 1 shows a possible formation process for the 3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-bis(thiolate) ligand via rearrangement of the dithione starting material and its reaction to form compound (I). Similar rearrangements of dithiones have been reported previously (Elam & Davis, 1967 ). Herein, we report the synthesis conditions and crystal structure of the title complex (I).

Figure 1
Schematic representation of a possible formation process for the 3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-bis(thiolato) ligand from the starting material.

2. Structural commentary

The molecular structure of (I) consists of two six-coordinate iron(I) atoms, each in a distorted trigonal anti-prismatic coordination environment (Fig. 2). The coordination sphere of Fe1 is filled by three carbonyl C atoms [Fe1—C1 = 1.8158 (19), Fe1—C2 = 1.7900 (18), Fe1—C3 = 1.8047 (18) Å), two S atoms of a bridging dithiolate ligand [Fe1—S1 = 2.2675 (5), Fe1—S2 = 2.2636 (5) Å], and the neighboring Fe^I atom [Fe1—Fe2 = 2.4921 (4) Å]. The coordination sphere of Fe2 is similarly filled by three carbonyl C atoms [Fe2—C4 = 1.7986 (19), Fe2—C5 = 1.8013 (19), Fe2—C6 = 1.8054 (19) Å], two S atoms [Fe2—S1 = 2.2624 (5), Fe2—S2 = 2.2601 (5) Å], and the neighboring Fe^I atom.

Figure 2
The molecular structure of (I)

with displacement ellipsoids drawn at the 35% probability level for non-H atoms and spheres of arbitrary size for H atoms.

The C7—S3—C9 bond angle of 77.86 (8)° is significantly smaller than the other angles making up the thietane ring [S3—C7—C8 = 92.82 (10)°; S3—C9—C8 = 96.26 (11)°; C7—C8—C9 = 93.06 (12)°]. The central ring of the anion is nearly planar with a S3—C7—C8—C9 torsion angle of −0.74 (11)°. The plane through S1—C7—S2 is rotated by 89.94 (11)° with respect to the thietane ring. Similarly, the dihedral angle between the thietane ring and the plane through C11—C8—C12 is 89.74 (16)°. The =C(CH₃)₂ group (C13—C10—C14) is only slightly out of the plane of the central ring, making a dihedral angle of 4.63 (18)°.

3. Supramolecular features

There are no significant supramolecular features to discuss with the extended structure of (I). There are weak C—H⋯O intermolecular interactions between one methyl group from the dithiolate ligand and one of the carbonyl oxygen atoms, Table 1. These interactions result in the formation of dimers of (I), Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯O2ⁱ	0.98	2.56	3.334 (2)	136
Symmetry code: (i) -x+2, -y+1, -z+1.

Figure 3
A plot of (a) dimers of (I)

with the C—H⋯O interactions highlighted as blue dashed lines; and (b) an expanded view along the c axis of the packing of (I)

with an overlay of the unit cell. Orange = Fe, yellow = S, red = O, gray = C, green = H.

4. Database survey

Only one other crystal structure with 3,3-dimethyl-4-(propan-2-ylidene)thietane-2,2-bis(thiolate) is reported in the Cambridge Crystallographic Database (Groom & Allen, 2014 ). The compound is a mononuclear square-planar platinum(II) bis(triphenylphosphine) complex (Okuma et al., 2007 ).

A search of the Cambridge Crystallographic Database (Groom & Allen, 2014) returns eighteen hexacarbonyldi-iron(I) complexes in which there is a bridging S—C—S dithiolate moiety. The range of Fe—Fe distances for these compounds is 2.461 Å − 2.501 Å [average 2.482 Å] (Alvarez-Toledano et al., 1999 ; Shi et al., 2011 ). The Fe1—Fe2 distance in (I) of 2.4921 (4) Å falls within this range. The Fe—S distances for the database compounds range from 2.244 Å − 2.296 Å [average 2.271 Å] (Broadhurst et al., 1982 ; Nekhaev et al., 1991 ). All of the Fe—S distances in (I) [average 2.263 Å] fall within this range.

5. Synthesis and crystallization

A mixture of tetramethyl-1,3-cyclobutanedithione (130 mg, 0.76 mmol) and Fe₃(CO)₁₂ (383 mg, 0.76 mmol) was dissolved in 15 ml dry toluene. The reaction mixture was refluxed for 2 h, and the solution color change from a green to a red was observed. After removal of the solvent under vacuum, the resulting residue was chromatographed by silica gel column eluting with hexane–CH₂Cl₂ (10:1, v/v). The main red band was collected to get an orange–red solid (10 mg, 0.02 mmol, 3% yield). Crystals suitable for X-ray diffraction were grown by slow evaporation of hexane of the orange–red solid at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Methyl H atom positions were optimized by rotation about R—C bonds with idealized C—H, R⋯H and H⋯H distances and included as as riding idealized contributors [C—H_methyl = 0.98 Å with U_iso(H) = 1.5U_eq(C)]. The 001 reflection was omitted from the final refinement because it was obscured by the shadow of the beam stop.

Table 2
Experimental details

Crystal data
Chemical formula	[Fe₂(C₈H₁₂S₃)(CO)₆]
M_r	484.12
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.3619 (10), 9.7681 (11), 10.6249 (12)
α, β, γ (°)	88.092 (6), 78.668 (6), 76.559 (6)
V (Å³)	926.51 (18)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.93
Crystal size (mm)	0.27 × 0.13 × 0.05

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Integration (SADABS; Bruker, 2014 )
T_min, T_max	0.752, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	26313, 4095, 3603
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.055, 1.04
No. of reflections	4095
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.26
Computer programs: APEX2, SAINT and XCIF (Bruker, 2014), SHELXTL (Sheldrick, 2008 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), CrystalMaker (CrystalMaker, 1994 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1429290

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018496/wm5218sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018496/wm5218Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015018496/wm5218Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014) and SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008), CrystalMaker (CrystalMaker, 1994); software used to prepare material for publication: XCIF (Bruker, 2014), publCIF (Westrip, 2010).

[µ₂-3,3-Dimethyl-4-(propan-2-ylidene)thietane-2,2-dithiolato-κ⁴S,S':S,S]bis[tricarbonyliron(I)](Fe—Fe) top

Crystal data top

[Fe₂(C₈H₁₂S₃)(CO)₆]	Z = 2
M_r = 484.12	F(000) = 488
Triclinic, P1	D_x = 1.735 Mg m⁻³
a = 9.3619 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7681 (11) Å	Cell parameters from 9920 reflections
c = 10.6249 (12) Å	θ = 2.3–27.1°
α = 88.092 (6)°	µ = 1.93 mm⁻¹
β = 78.668 (6)°	T = 100 K
γ = 76.559 (6)°	Plate, orange
V = 926.51 (18) Å³	0.27 × 0.13 × 0.05 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4095 independent reflections
Radiation source: fine-focus sealed tube	3603 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
profile data from φ and ω scans	θ_max = 27.2°, θ_min = 2.7°
Absorption correction: integration (SADABS; Bruker, 2014)	h = −12→11
T_min = 0.752, T_max = 0.935	k = −12→12
26313 measured reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0274P)² + 0.4094P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4095 reflections	Δρ_max = 0.46 e Å⁻³
230 parameters	Δρ_min = −0.26 e Å⁻³

Special details top

Experimental. One distinct cell was identified using APEX2 (Bruker, 2014). Twelve frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2014) then corrected for absorption by integration using SAINT/SADABS v2014/2 (Bruker, 2014) to sort, merge, and scale the combined data. No decay correction was applied.

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. Structure was phased by direct methods (Sheldrick, 2015). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². The final map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude and resolution.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.76261 (3)	0.69641 (2)	0.81874 (2)	0.01268 (7)
Fe2	0.54756 (3)	0.67026 (2)	0.72314 (2)	0.01297 (7)
S1	0.78928 (4)	0.57564 (4)	0.63376 (4)	0.01365 (9)
S2	0.66378 (4)	0.84946 (4)	0.67671 (4)	0.01170 (9)
S3	0.98623 (4)	0.77978 (5)	0.51958 (4)	0.01510 (9)
O1	1.06505 (15)	0.74224 (16)	0.81135 (13)	0.0298 (3)
O2	0.79552 (19)	0.44486 (15)	0.97850 (14)	0.0394 (4)
O3	0.60206 (15)	0.87309 (13)	1.04475 (12)	0.0228 (3)
O4	0.49994 (16)	0.40404 (14)	0.84072 (15)	0.0342 (4)
O5	0.30956 (14)	0.84235 (14)	0.91503 (13)	0.0236 (3)
O6	0.37887 (15)	0.67444 (16)	0.51589 (13)	0.0289 (3)
C1	0.9483 (2)	0.72664 (19)	0.81121 (16)	0.0194 (4)
C2	0.7844 (2)	0.54209 (19)	0.91537 (17)	0.0229 (4)
C3	0.66473 (19)	0.80602 (18)	0.95676 (17)	0.0158 (3)
C4	0.5173 (2)	0.50717 (19)	0.79429 (18)	0.0217 (4)
C5	0.39957 (19)	0.77459 (18)	0.83967 (17)	0.0176 (4)
C6	0.4451 (2)	0.67316 (19)	0.59538 (17)	0.0193 (4)
C7	0.80188 (18)	0.74138 (17)	0.55009 (16)	0.0126 (3)
C8	0.78750 (18)	0.75972 (17)	0.40463 (15)	0.0133 (3)
C9	0.94031 (18)	0.79590 (17)	0.36484 (16)	0.0145 (3)
C10	1.01847 (19)	0.83374 (17)	0.25666 (16)	0.0152 (3)
C11	0.7806 (2)	0.62209 (19)	0.34363 (17)	0.0189 (4)
H11A	0.6862	0.5968	0.3818	0.028*
H11B	0.8648	0.5469	0.3591	0.028*
H11C	0.7865	0.6344	0.2510	0.028*
C12	0.65819 (19)	0.8813 (2)	0.38437 (17)	0.0200 (4)
H12A	0.6693	0.9681	0.4210	0.030*
H12B	0.5630	0.8603	0.4269	0.030*
H12C	0.6594	0.8933	0.2923	0.030*
C13	0.9618 (2)	0.8528 (2)	0.13289 (17)	0.0205 (4)
H13A	0.8732	0.8135	0.1409	0.031*
H13B	1.0401	0.8039	0.0632	0.031*
H13C	0.9352	0.9533	0.1138	0.031*
C14	1.1685 (2)	0.8657 (2)	0.25251 (18)	0.0218 (4)
H14A	1.1921	0.8566	0.3387	0.033*
H14B	1.1662	0.9620	0.2225	0.033*
H14C	1.2452	0.7994	0.1937	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01333 (12)	0.01381 (12)	0.01084 (12)	−0.00155 (9)	−0.00425 (9)	0.00130 (9)
Fe2	0.01163 (12)	0.01325 (12)	0.01452 (13)	−0.00397 (9)	−0.00246 (9)	0.00064 (9)
S1	0.0144 (2)	0.01203 (18)	0.0139 (2)	−0.00127 (15)	−0.00330 (15)	0.00014 (15)
S2	0.01227 (19)	0.01146 (18)	0.01142 (19)	−0.00226 (15)	−0.00305 (15)	0.00056 (15)
S3	0.01174 (19)	0.0236 (2)	0.01148 (19)	−0.00601 (16)	−0.00357 (15)	0.00040 (16)
O1	0.0193 (7)	0.0544 (9)	0.0193 (7)	−0.0119 (6)	−0.0086 (5)	0.0002 (6)
O2	0.0551 (10)	0.0243 (8)	0.0281 (8)	0.0052 (7)	−0.0018 (7)	0.0122 (6)
O3	0.0259 (7)	0.0243 (7)	0.0171 (7)	−0.0016 (6)	−0.0059 (5)	−0.0038 (5)
O4	0.0307 (8)	0.0213 (7)	0.0478 (9)	−0.0091 (6)	0.0012 (7)	0.0108 (7)
O5	0.0179 (6)	0.0262 (7)	0.0248 (7)	−0.0057 (5)	0.0016 (5)	−0.0053 (6)
O6	0.0243 (7)	0.0419 (8)	0.0265 (7)	−0.0134 (6)	−0.0117 (6)	−0.0014 (6)
C1	0.0213 (9)	0.0254 (9)	0.0107 (8)	−0.0020 (7)	−0.0054 (7)	0.0003 (7)
C2	0.0263 (10)	0.0218 (9)	0.0162 (9)	0.0022 (8)	−0.0030 (7)	−0.0004 (7)
C3	0.0159 (8)	0.0174 (8)	0.0166 (9)	−0.0047 (7)	−0.0087 (7)	0.0058 (7)
C4	0.0173 (9)	0.0211 (9)	0.0255 (10)	−0.0043 (7)	−0.0009 (7)	−0.0017 (8)
C5	0.0172 (9)	0.0181 (8)	0.0211 (9)	−0.0092 (7)	−0.0062 (7)	0.0034 (7)
C6	0.0165 (9)	0.0205 (9)	0.0208 (9)	−0.0067 (7)	0.0000 (7)	−0.0013 (7)
C7	0.0120 (8)	0.0135 (7)	0.0124 (8)	−0.0026 (6)	−0.0030 (6)	0.0009 (6)
C8	0.0127 (8)	0.0173 (8)	0.0096 (8)	−0.0018 (6)	−0.0030 (6)	−0.0007 (6)
C9	0.0146 (8)	0.0168 (8)	0.0129 (8)	−0.0029 (6)	−0.0047 (6)	−0.0008 (6)
C10	0.0154 (8)	0.0142 (8)	0.0149 (8)	−0.0013 (6)	−0.0026 (6)	−0.0016 (6)
C11	0.0202 (9)	0.0245 (9)	0.0145 (8)	−0.0093 (7)	−0.0043 (7)	−0.0025 (7)
C12	0.0166 (9)	0.0281 (10)	0.0135 (8)	0.0000 (7)	−0.0053 (7)	0.0044 (7)
C13	0.0194 (9)	0.0275 (10)	0.0134 (8)	−0.0036 (7)	−0.0028 (7)	0.0033 (7)
C14	0.0185 (9)	0.0269 (10)	0.0213 (9)	−0.0091 (7)	−0.0021 (7)	0.0010 (8)

Geometric parameters (Å, º) top

Fe1—C2	1.7900 (18)	O6—C6	1.140 (2)
Fe1—C3	1.8047 (18)	C7—C8	1.578 (2)
Fe1—C1	1.8158 (19)	C8—C9	1.529 (2)
Fe1—S2	2.2636 (5)	C8—C12	1.529 (2)
Fe1—S1	2.2675 (5)	C8—C11	1.532 (2)
Fe1—Fe2	2.4921 (4)	C9—C10	1.327 (2)
Fe2—C4	1.7986 (19)	C10—C14	1.500 (2)
Fe2—C5	1.8013 (19)	C10—C13	1.502 (2)
Fe2—C6	1.8054 (19)	C11—H11A	0.9800
Fe2—S2	2.2601 (5)	C11—H11B	0.9800
Fe2—S1	2.2624 (5)	C11—H11C	0.9800
S1—C7	1.8376 (17)	C12—H12A	0.9800
S2—C7	1.8365 (17)	C12—H12B	0.9800
S3—C9	1.7725 (17)	C12—H12C	0.9800
S3—C7	1.8159 (17)	C13—H13A	0.9800
O1—C1	1.139 (2)	C13—H13B	0.9800
O2—C2	1.141 (2)	C13—H13C	0.9800
O3—C3	1.138 (2)	C14—H14A	0.9800
O4—C4	1.139 (2)	C14—H14B	0.9800
O5—C5	1.140 (2)	C14—H14C	0.9800

C2—Fe1—C3	91.53 (8)	C8—C7—S3	92.82 (10)
C2—Fe1—C1	97.19 (9)	C8—C7—S2	120.98 (11)
C3—Fe1—C1	98.73 (8)	S3—C7—S2	115.14 (9)
C2—Fe1—S2	156.52 (7)	C8—C7—S1	121.18 (11)
C3—Fe1—S2	94.05 (5)	S3—C7—S1	115.21 (8)
C1—Fe1—S2	104.45 (6)	S2—C7—S1	93.42 (8)
C2—Fe1—S1	94.27 (6)	C9—C8—C12	112.78 (14)
C3—Fe1—S1	156.84 (5)	C9—C8—C11	112.89 (14)
C1—Fe1—S1	102.74 (6)	C12—C8—C11	111.99 (14)
S2—Fe1—S1	72.347 (18)	C9—C8—C7	93.06 (12)
C2—Fe1—Fe2	100.05 (7)	C12—C8—C7	112.71 (13)
C3—Fe1—Fe2	100.38 (5)	C11—C8—C7	112.13 (13)
C1—Fe1—Fe2	153.78 (5)	C10—C9—C8	135.38 (15)
S2—Fe1—Fe2	56.505 (14)	C10—C9—S3	128.31 (14)
S1—Fe1—Fe2	56.527 (14)	C8—C9—S3	96.26 (11)
C4—Fe2—C5	92.90 (8)	C9—C10—C14	121.21 (16)
C4—Fe2—C6	97.79 (8)	C9—C10—C13	123.00 (16)
C5—Fe2—C6	98.27 (8)	C14—C10—C13	115.75 (15)
C4—Fe2—S2	156.52 (6)	C8—C11—H11A	109.5
C5—Fe2—S2	92.61 (6)	C8—C11—H11B	109.5
C6—Fe2—S2	103.96 (6)	H11A—C11—H11B	109.5
C4—Fe2—S1	93.49 (6)	C8—C11—H11C	109.5
C5—Fe2—S1	154.57 (6)	H11A—C11—H11C	109.5
C6—Fe2—S1	105.19 (6)	H11B—C11—H11C	109.5
S2—Fe2—S1	72.505 (18)	C8—C12—H12A	109.5
C4—Fe2—Fe1	99.98 (6)	C8—C12—H12B	109.5
C5—Fe2—Fe1	97.92 (6)	H12A—C12—H12B	109.5
C6—Fe2—Fe1	155.23 (6)	C8—C12—H12C	109.5
S2—Fe2—Fe1	56.639 (13)	H12A—C12—H12C	109.5
S1—Fe2—Fe1	56.720 (15)	H12B—C12—H12C	109.5
C7—S1—Fe2	90.00 (5)	C10—C13—H13A	109.5
C7—S1—Fe1	86.81 (5)	C10—C13—H13B	109.5
Fe2—S1—Fe1	66.753 (15)	H13A—C13—H13B	109.5
C7—S2—Fe2	90.10 (5)	C10—C13—H13C	109.5
C7—S2—Fe1	86.96 (5)	H13A—C13—H13C	109.5
Fe2—S2—Fe1	66.856 (15)	H13B—C13—H13C	109.5
C9—S3—C7	77.86 (8)	C10—C14—H14A	109.5
O1—C1—Fe1	176.96 (16)	C10—C14—H14B	109.5
O2—C2—Fe1	178.63 (18)	H14A—C14—H14B	109.5
O3—C3—Fe1	178.75 (16)	C10—C14—H14C	109.5
O4—C4—Fe2	178.76 (18)	H14A—C14—H14C	109.5
O5—C5—Fe2	177.61 (15)	H14B—C14—H14C	109.5
O6—C6—Fe2	179.05 (16)

C9—S3—C7—C8	0.66 (9)	S3—C7—C8—C12	−117.02 (13)
C9—S3—C7—S2	−125.68 (10)	S2—C7—C8—C12	4.7 (2)
C9—S3—C7—S1	127.24 (10)	S1—C7—C8—C12	121.10 (14)
Fe2—S2—C7—C8	99.53 (12)	S3—C7—C8—C11	115.51 (12)
Fe1—S2—C7—C8	166.35 (13)	S2—C7—C8—C11	−122.78 (14)
Fe2—S2—C7—S3	−150.28 (8)	S1—C7—C8—C11	−6.38 (19)
Fe1—S2—C7—S3	−83.46 (8)	C12—C8—C9—C10	−60.3 (3)
Fe2—S2—C7—S1	−30.32 (6)	C11—C8—C9—C10	67.9 (2)
Fe1—S2—C7—S1	36.49 (5)	C7—C8—C9—C10	−176.5 (2)
Fe2—S1—C7—C8	−99.43 (12)	C12—C8—C9—S3	116.98 (13)
Fe1—S1—C7—C8	−166.14 (12)	C11—C8—C9—S3	−114.84 (13)
Fe2—S1—C7—S3	150.19 (8)	C7—C8—C9—S3	0.77 (11)
Fe1—S1—C7—S3	83.47 (8)	C7—S3—C9—C10	176.85 (18)
Fe2—S1—C7—S2	30.29 (6)	C7—S3—C9—C8	−0.68 (10)
Fe1—S1—C7—S2	−36.43 (5)	C8—C9—C10—C14	178.40 (17)
S3—C7—C8—C9	−0.74 (11)	S3—C9—C10—C14	1.9 (3)
S2—C7—C8—C9	120.97 (13)	C8—C9—C10—C13	0.8 (3)
S1—C7—C8—C9	−122.63 (13)	S3—C9—C10—C13	−175.74 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···O2ⁱ	0.98	2.56	3.334 (2)	136

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

This work was supported by the National Institutes of Health through GM061153.

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