Hexacarbonyl-2κ(3) C,3κ(3) C-di-μ3-sulfido-tetra-kis-(tetra-hydro-furan-1κO)calcium-diiron(II)(Fe-Fe).

Reaction between [Fe2(μ-S2)(CO)6] and [Ca(thf)4(dpp-BIAN)] [dpp-BIAN = 1,2-bis-(2,6-diisopropyl-phenyl-imino)-acenaphthene and thf = tetra-hydro-furan] proceeds as a redox process via a two-electron reduction of [Fe2(μ-S2)(CO)6] and a two-electron oxidation of (dpp-BIAN)(2-), resulting in the formation of the title heterometallic trinuclear cluster, [CaFe2(μ3-S)2(C4H8O)4(CO)6], and neutral dpp-BIAN. In the cluster, the Ca(II) atom is connected to two S atoms of an Fe2S2 core [Ca-S = 2.7463 (8) and 2.7523 (8) Å]. No Fe-Ca bonds are formed [Fe⋯Ca = 3.6708 (6) and 3.5802 (6) Å]. There are five close C-H⋯O-C contacts in the crystal structure.

Related literature

For the synthesis and structure of [Fe2(CO)6(μ-S2)], see: Hieber & Beck (1958 ▶); Seyferth et al. (1982 ▶), and of [Ca(thf)4(dpp-BIAN)], see: Fedushkin et al. (2003 ▶). For the synthesis and structures of related heterometallic clusters with an Fe2S2 core, see: Konchenko et al. (2010 ▶); Cowie et al. (1989 ▶); Veith et al. (2005 ▶); Eremenko et al. (1994 ▶); Pasynskii et al. (1993 ▶). For FeS-clusters as model compounds for active sites of hydrogenases, see: Gloaguen & Rauchfuss (2009 ▶).

Experimental

Crystal data

[CaFe2S2(C4H8O)4(CO)6]

M = 672.38

Orthorhombic,

a = 10.9189 (4) Å

b = 12.4167 (5) Å

c = 21.4545 (9) Å

V = 2908.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 1.37 mm−1

T = 150 K

0.25 × 0.11 × 0.08 mm

Data collection

Bruker–Nonius X8 APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.726, T max = 0.899

21313 measured reflections

5951 independent reflections

5319 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.057

S = 1.01

5951 reflections

334 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983) ▶, 2601 Friedel pairs

Flack parameter: 0.006 (11)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812048039/zl2517sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048039/zl2517Isup2.hkl

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

[CaFe2S2(C4H8O)4(CO)6]	F(000) = 1392
Mr = 672.38	Dx = 1.535 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7648 reflections
a = 10.9189 (4) Å	θ = 2.5–26.2°
b = 12.4167 (5) Å	µ = 1.37 mm−1
c = 21.4545 (9) Å	T = 150 K
V = 2908.7 (2) Å3	Prism, black
Z = 4	0.25 × 0.11 × 0.08 mm

Bruker–Nonius X8 APEX CCD area-detector diffractometer	5951 independent reflections
Radiation source: fine-focus sealed tube	5319 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 25 pixels mm-1	θmax = 26.4°, θmin = 1.9°
φ scans	h = −13→11
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→15
Tmin = 0.726, Tmax = 0.899	l = −26→26
21313 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H-atom parameters constrained
wR(F2) = 0.057	w = 1/[σ2(Fo2) + (0.029P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.002
5951 reflections	Δρmax = 0.36 e Å−3
334 parameters	Δρmin = −0.32 e Å−3
0 restraints	Absolute structure: Flack (1983), 2601 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.006 (11)

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	0.79820 (3)	0.40586 (3)	0.674330 (16)	0.02253 (8)
Fe2	0.82499 (3)	0.59531 (3)	0.635135 (17)	0.02489 (9)
Ca1	0.51290 (4)	0.49436 (4)	0.60998 (2)	0.01931 (10)
S1	0.67335 (5)	0.54573 (5)	0.70434 (3)	0.02536 (14)
S2	0.75029 (6)	0.45765 (5)	0.57341 (3)	0.02487 (14)
O1	1.02452 (18)	0.32234 (16)	0.61922 (10)	0.0441 (5)
O2	0.88333 (18)	0.40811 (19)	0.80361 (9)	0.0479 (5)
O3	0.64995 (17)	0.21109 (14)	0.69010 (9)	0.0348 (5)
O4	1.04619 (17)	0.58348 (18)	0.55847 (9)	0.0467 (5)
O5	0.9470 (2)	0.68878 (18)	0.74443 (11)	0.0561 (6)
O6	0.71495 (19)	0.78658 (16)	0.57777 (10)	0.0459 (5)
O11	0.35797 (14)	0.48969 (14)	0.68605 (8)	0.0259 (4)
O21	0.44972 (16)	0.30895 (12)	0.59998 (8)	0.0287 (4)
O31	0.43354 (16)	0.49442 (14)	0.50679 (8)	0.0284 (4)
O41	0.44134 (17)	0.67554 (12)	0.60327 (8)	0.0278 (4)
C1	0.9361 (3)	0.3532 (2)	0.64150 (13)	0.0301 (6)
C2	0.8518 (2)	0.4082 (2)	0.75288 (12)	0.0302 (6)
C3	0.7062 (2)	0.2881 (2)	0.68292 (11)	0.0254 (5)
C4	0.9604 (2)	0.5880 (2)	0.58892 (13)	0.0325 (6)
C5	0.8992 (3)	0.6536 (2)	0.70162 (15)	0.0353 (7)
C6	0.7565 (2)	0.7112 (2)	0.60022 (13)	0.0317 (6)
C12	0.3812 (3)	0.4509 (2)	0.74846 (13)	0.0350 (7)
H12A	0.4171	0.5084	0.7747	0.042*
H12B	0.4378	0.3887	0.7478	0.042*
C13	0.2579 (3)	0.4183 (3)	0.77249 (15)	0.0525 (9)
H13A	0.2547	0.4221	0.8186	0.063*
H13B	0.2365	0.3444	0.7590	0.063*
C14	0.1737 (3)	0.5006 (3)	0.74314 (15)	0.0529 (9)
H14A	0.0893	0.4724	0.7394	0.063*
H14B	0.1722	0.5681	0.7677	0.063*
C15	0.2301 (2)	0.5187 (2)	0.67990 (14)	0.0345 (6)
H15A	0.1895	0.4731	0.6482	0.041*
H15B	0.2218	0.5951	0.6673	0.041*
C22	0.3577 (3)	0.2470 (2)	0.63353 (15)	0.0365 (7)
H22A	0.2800	0.2878	0.6367	0.044*
H22B	0.3865	0.2293	0.6761	0.044*
C23	0.3400 (3)	0.1453 (2)	0.59526 (15)	0.0431 (8)
H23A	0.3138	0.0842	0.6218	0.052*
H23B	0.2790	0.1563	0.5617	0.052*
C24	0.4666 (3)	0.1266 (2)	0.56874 (14)	0.0385 (7)
H24A	0.4635	0.0811	0.5309	0.046*
H24B	0.5214	0.0926	0.5998	0.046*
C25	0.5076 (3)	0.2404 (2)	0.55347 (13)	0.0347 (7)
H25A	0.5979	0.2463	0.5559	0.042*
H25B	0.4811	0.2609	0.5110	0.042*
C32	0.3135 (2)	0.4568 (2)	0.48866 (12)	0.0314 (6)
H32A	0.2548	0.5175	0.4869	0.038*
H32B	0.2828	0.4027	0.5187	0.038*
C33	0.3296 (3)	0.4070 (3)	0.42478 (13)	0.0442 (7)
H33A	0.3264	0.3275	0.4272	0.053*
H33B	0.2651	0.4323	0.3958	0.053*
C34	0.4545 (4)	0.4447 (4)	0.40367 (16)	0.0787 (14)
H34A	0.5097	0.3822	0.3978	0.094*
H34B	0.4478	0.4837	0.3636	0.094*
C35	0.5017 (3)	0.5140 (3)	0.45056 (13)	0.0566 (10)
H35A	0.4928	0.5902	0.4377	0.068*
H35B	0.5898	0.4991	0.4575	0.068*
C42	0.3891 (3)	0.7332 (2)	0.55093 (13)	0.0458 (9)
H42A	0.3244	0.6896	0.5307	0.055*
H42B	0.4530	0.7500	0.5197	0.055*
C43	0.3355 (3)	0.8361 (2)	0.57789 (14)	0.0410 (7)
H43A	0.3371	0.8954	0.5471	0.049*
H43B	0.2504	0.8250	0.5924	0.049*
C44	0.4212 (3)	0.8579 (2)	0.63176 (13)	0.0336 (6)
H44A	0.3818	0.9041	0.6636	0.040*
H44B	0.4977	0.8927	0.6174	0.040*
C45	0.4458 (3)	0.7462 (2)	0.65700 (12)	0.0323 (7)
H45A	0.5272	0.7430	0.6772	0.039*
H45B	0.3826	0.7256	0.6879	0.039*

	U11	U22	U33	U12	U13	U23
Fe1	0.02134 (17)	0.02364 (17)	0.02262 (17)	−0.00130 (15)	−0.00090 (15)	−0.00073 (16)
Fe2	0.02297 (18)	0.02352 (18)	0.02818 (19)	−0.00199 (15)	0.00003 (16)	−0.00004 (16)
Ca1	0.0206 (2)	0.0174 (2)	0.0200 (2)	−0.00045 (19)	−0.0008 (2)	−0.0010 (2)
S1	0.0212 (3)	0.0320 (3)	0.0229 (3)	0.0001 (3)	−0.0003 (3)	−0.0069 (3)
S2	0.0221 (3)	0.0320 (3)	0.0205 (3)	0.0010 (3)	0.0008 (3)	−0.0038 (3)
O1	0.0291 (11)	0.0478 (12)	0.0555 (14)	0.0062 (9)	0.0066 (10)	−0.0083 (11)
O2	0.0443 (12)	0.0709 (14)	0.0286 (11)	−0.0113 (11)	−0.0107 (9)	0.0019 (11)
O3	0.0381 (11)	0.0308 (10)	0.0355 (11)	−0.0085 (9)	0.0007 (9)	0.0050 (9)
O4	0.0287 (11)	0.0664 (15)	0.0450 (13)	0.0017 (10)	0.0092 (10)	0.0121 (11)
O5	0.0552 (15)	0.0513 (14)	0.0618 (15)	−0.0080 (12)	−0.0199 (13)	−0.0194 (12)
O6	0.0474 (13)	0.0367 (12)	0.0536 (13)	0.0089 (10)	0.0131 (11)	0.0177 (11)
O11	0.0215 (9)	0.0311 (9)	0.0251 (9)	0.0010 (7)	0.0008 (7)	0.0064 (8)
O21	0.0337 (10)	0.0173 (8)	0.0351 (11)	−0.0034 (8)	0.0009 (8)	−0.0027 (8)
O31	0.0287 (9)	0.0347 (9)	0.0216 (9)	−0.0068 (8)	−0.0037 (7)	−0.0046 (8)
O41	0.0457 (11)	0.0165 (8)	0.0211 (9)	0.0027 (8)	−0.0039 (8)	−0.0005 (7)
C1	0.0288 (15)	0.0287 (14)	0.0327 (15)	−0.0034 (11)	−0.0052 (13)	0.0009 (12)
C2	0.0258 (14)	0.0332 (14)	0.0317 (15)	−0.0054 (12)	0.0007 (11)	0.0002 (13)
C3	0.0259 (13)	0.0301 (14)	0.0201 (13)	0.0042 (11)	−0.0003 (11)	0.0015 (11)
C4	0.0297 (15)	0.0330 (15)	0.0348 (16)	−0.0065 (13)	−0.0056 (13)	0.0094 (13)
C5	0.0298 (15)	0.0282 (14)	0.0481 (18)	−0.0011 (12)	−0.0051 (14)	−0.0031 (14)
C6	0.0301 (14)	0.0309 (15)	0.0343 (16)	−0.0048 (12)	0.0097 (13)	0.0020 (13)
C12	0.0436 (17)	0.0327 (15)	0.0286 (15)	0.0051 (13)	−0.0018 (12)	0.0076 (12)
C13	0.070 (2)	0.0479 (19)	0.0393 (18)	−0.0196 (18)	0.0223 (17)	0.0036 (15)
C14	0.0278 (16)	0.074 (2)	0.057 (2)	−0.0113 (17)	0.0132 (15)	−0.0199 (18)
C15	0.0214 (14)	0.0376 (16)	0.0444 (16)	−0.0007 (11)	−0.0016 (12)	0.0003 (14)
C22	0.0353 (16)	0.0262 (14)	0.0481 (18)	−0.0054 (11)	0.0045 (14)	−0.0005 (14)
C23	0.0445 (18)	0.0223 (14)	0.062 (2)	−0.0072 (13)	−0.0101 (16)	−0.0049 (14)
C24	0.0493 (19)	0.0211 (14)	0.0452 (18)	0.0025 (12)	−0.0067 (15)	−0.0104 (12)
C25	0.0444 (18)	0.0262 (14)	0.0336 (16)	0.0033 (12)	−0.0011 (14)	−0.0063 (12)
C32	0.0251 (13)	0.0353 (14)	0.0337 (14)	0.0005 (12)	−0.0032 (12)	0.0006 (12)
C33	0.0467 (18)	0.0561 (19)	0.0298 (15)	−0.0167 (17)	−0.0119 (14)	−0.0038 (15)
C34	0.083 (3)	0.117 (3)	0.037 (2)	−0.055 (3)	0.0211 (19)	−0.026 (2)
C35	0.0482 (19)	0.093 (3)	0.0284 (16)	−0.0292 (19)	0.0058 (14)	−0.0035 (17)
C42	0.085 (3)	0.0277 (16)	0.0253 (16)	0.0141 (15)	−0.0124 (16)	0.0010 (12)
C43	0.056 (2)	0.0279 (15)	0.0388 (17)	0.0138 (14)	−0.0080 (15)	0.0006 (13)
C44	0.0411 (16)	0.0207 (13)	0.0388 (16)	0.0087 (11)	−0.0040 (14)	−0.0054 (12)
C45	0.0480 (18)	0.0257 (14)	0.0232 (15)	0.0006 (12)	−0.0011 (12)	−0.0066 (11)

Fe1—C3	1.784 (3)	C14—C15	1.507 (4)
Fe1—C2	1.784 (3)	C14—H14A	0.9900
Fe1—C1	1.786 (3)	C14—H14B	0.9900
Fe1—Fe2	2.5152 (5)	C15—H15A	0.9900
Fe1—S1	2.2999 (7)	C15—H15B	0.9900
Fe1—S2	2.3185 (7)	C22—C23	1.519 (4)
Fe2—S1	2.3077 (7)	C22—H22A	0.9900
Fe2—S2	2.3110 (7)	C22—H22B	0.9900
Ca1—S1	2.7523 (8)	C23—C24	1.513 (4)
Ca1—S2	2.7463 (8)	C23—H23A	0.9900
Ca1—Fe1	3.5802 (6)	C23—H23B	0.9900
Ca1—Fe2	3.6708 (6)	C24—C25	1.517 (4)
Fe2—C4	1.783 (3)	C24—H24A	0.9900
Fe2—C6	1.787 (3)	C24—H24B	0.9900
Fe2—C5	1.793 (3)	C25—H25A	0.9900
Ca1—O11	2.3513 (17)	C25—H25B	0.9900
Ca1—O31	2.3773 (17)	C32—C33	1.514 (4)
Ca1—O41	2.3858 (16)	C32—H32A	0.9900
Ca1—O21	2.4128 (16)	C32—H32B	0.9900
O1—C1	1.144 (3)	C33—C34	1.511 (4)
O2—C2	1.142 (3)	C33—H33A	0.9900
O3—C3	1.147 (3)	C33—H33B	0.9900
O4—C4	1.143 (3)	C34—C35	1.421 (4)
O5—C5	1.143 (3)	C34—H34A	0.9900
O6—C6	1.146 (3)	C34—H34B	0.9900
O11—C12	1.445 (3)	C35—H35A	0.9900
O11—C15	1.448 (3)	C35—H35B	0.9900
O21—C22	1.456 (3)	C42—C43	1.519 (4)
O21—C25	1.456 (3)	C42—H42A	0.9900
O31—C35	1.438 (3)	C42—H42B	0.9900
O31—C32	1.445 (3)	C43—C44	1.511 (4)
O41—C42	1.449 (3)	C43—H43A	0.9900
O41—C45	1.450 (3)	C43—H43B	0.9900
C12—C13	1.498 (4)	C44—C45	1.513 (3)
C12—H12A	0.9900	C44—H44A	0.9900
C12—H12B	0.9900	C44—H44B	0.9900
C13—C14	1.512 (5)	C45—H45A	0.9900
C13—H13A	0.9900	C45—H45B	0.9900
C13—H13B	0.9900
C3—Fe1—C2	95.79 (12)	O11—C12—H12A	110.8
C3—Fe1—C1	102.44 (11)	C13—C12—H12A	110.8
C2—Fe1—C1	95.85 (12)	O11—C12—H12B	110.8
C3—Fe1—S1	104.86 (8)	C13—C12—H12B	110.8
C2—Fe1—S1	85.27 (9)	H12A—C12—H12B	108.9
C1—Fe1—S1	152.42 (9)	C12—C13—C14	102.7 (2)
C3—Fe1—S2	101.35 (8)	C12—C13—H13A	111.2
C2—Fe1—S2	162.08 (9)	C14—C13—H13A	111.2
C1—Fe1—S2	85.60 (9)	C12—C13—H13B	111.2
S1—Fe1—S2	85.31 (2)	C14—C13—H13B	111.2
C3—Fe1—Fe2	150.09 (8)	H13A—C13—H13B	109.1
C2—Fe1—Fe2	105.19 (9)	C15—C14—C13	103.2 (2)
C1—Fe1—Fe2	96.45 (9)	C15—C14—H14A	111.1
S1—Fe1—Fe2	57.06 (2)	C13—C14—H14A	111.1
S2—Fe1—Fe2	56.95 (2)	C15—C14—H14B	111.1
C3—Fe1—Ca1	78.55 (8)	C13—C14—H14B	111.1
C2—Fe1—Ca1	130.14 (9)	H14A—C14—H14B	109.1
C1—Fe1—Ca1	133.92 (9)	O11—C15—C14	105.9 (2)
S1—Fe1—Ca1	50.242 (18)	O11—C15—H15A	110.6
S2—Fe1—Ca1	50.091 (18)	C14—C15—H15A	110.6
Fe2—Fe1—Ca1	71.653 (13)	O11—C15—H15B	110.6
C4—Fe2—C6	98.93 (12)	C14—C15—H15B	110.6
C4—Fe2—C5	95.07 (13)	H15A—C15—H15B	108.7
C6—Fe2—C5	101.39 (12)	O21—C22—C23	105.1 (2)
C4—Fe2—S1	159.96 (9)	O21—C22—H22A	110.7
C6—Fe2—S1	100.61 (9)	C23—C22—H22A	110.7
C5—Fe2—S1	85.40 (10)	O21—C22—H22B	110.7
C4—Fe2—S2	86.35 (9)	C23—C22—H22B	110.7
C6—Fe2—S2	101.99 (9)	H22A—C22—H22B	108.8
C5—Fe2—S2	156.06 (9)	C24—C23—C22	102.4 (2)
S1—Fe2—S2	85.31 (2)	C24—C23—H23A	111.3
C4—Fe2—Fe1	103.58 (9)	C22—C23—H23A	111.3
C6—Fe2—Fe1	147.66 (9)	C24—C23—H23B	111.3
C5—Fe2—Fe1	99.45 (9)	C22—C23—H23B	111.3
S1—Fe2—Fe1	56.767 (19)	H23A—C23—H23B	109.2
S2—Fe2—Fe1	57.24 (2)	C23—C24—C25	102.0 (2)
C4—Fe2—Ca1	132.13 (9)	C23—C24—H24A	111.4
C6—Fe2—Ca1	79.91 (9)	C25—C24—H24A	111.4
C5—Fe2—Ca1	132.39 (10)	C23—C24—H24B	111.4
S1—Fe2—Ca1	48.504 (18)	C25—C24—H24B	111.4
S2—Fe2—Ca1	48.359 (18)	H24A—C24—H24B	109.2
Fe1—Fe2—Ca1	67.779 (13)	O21—C25—C24	105.6 (2)
O11—Ca1—O31	112.59 (6)	O21—C25—H25A	110.6
O11—Ca1—O41	80.18 (6)	C24—C25—H25A	110.6
O31—Ca1—O41	79.87 (6)	O21—C25—H25B	110.6
O11—Ca1—O21	80.36 (6)	C24—C25—H25B	110.6
O31—Ca1—O21	79.24 (6)	H25A—C25—H25B	108.8
O41—Ca1—O21	143.19 (6)	O31—C32—C33	105.7 (2)
O11—Ca1—S2	150.84 (5)	O31—C32—H32A	110.6
O31—Ca1—S2	94.48 (5)	C33—C32—H32A	110.6
O41—Ca1—S2	116.64 (5)	O31—C32—H32B	110.6
O21—Ca1—S2	94.94 (5)	C33—C32—H32B	110.6
O11—Ca1—S1	87.31 (5)	H32A—C32—H32B	108.7
O31—Ca1—S1	156.48 (5)	C34—C33—C32	104.5 (2)
O41—Ca1—S1	91.96 (5)	C34—C33—H33A	110.9
O21—Ca1—S1	117.94 (5)	C32—C33—H33A	110.9
S2—Ca1—S1	69.38 (2)	C34—C33—H33B	110.9
O11—Ca1—Fe1	110.53 (4)	C32—C33—H33B	110.9
O31—Ca1—Fe1	132.56 (5)	H33A—C33—H33B	108.9
O41—Ca1—Fe1	126.70 (5)	C35—C34—C33	107.6 (3)
O21—Ca1—Fe1	89.44 (4)	C35—C34—H34A	110.2
S2—Ca1—Fe1	40.358 (15)	C33—C34—H34A	110.2
S1—Ca1—Fe1	39.970 (15)	C35—C34—H34B	110.2
O11—Ca1—Fe2	125.05 (5)	C33—C34—H34B	110.2
O31—Ca1—Fe2	118.37 (4)	H34A—C34—H34B	108.5
O41—Ca1—Fe2	89.48 (5)	C34—C35—O31	107.7 (3)
O21—Ca1—Fe2	127.18 (4)	C34—C35—H35A	110.2
S2—Ca1—Fe2	38.966 (16)	O31—C35—H35A	110.2
S1—Ca1—Fe2	38.903 (15)	C34—C35—H35B	110.2
Fe1—Ca1—Fe2	40.568 (10)	O31—C35—H35B	110.2
Fe1—S1—Fe2	66.17 (2)	H35A—C35—H35B	108.5
Fe1—S1—Ca1	89.79 (2)	O41—C42—C43	105.8 (2)
Fe2—S1—Ca1	92.59 (2)	O41—C42—H42A	110.6
Fe2—S2—Fe1	65.82 (2)	C43—C42—H42A	110.6
Fe2—S2—Ca1	92.67 (2)	O41—C42—H42B	110.6
Fe1—S2—Ca1	89.55 (2)	C43—C42—H42B	110.6
C12—O11—C15	109.66 (19)	H42A—C42—H42B	108.7
C12—O11—Ca1	121.67 (15)	C44—C43—C42	101.7 (2)
C15—O11—Ca1	128.63 (16)	C44—C43—H43A	111.4
C22—O21—C25	109.24 (18)	C42—C43—H43A	111.4
C22—O21—Ca1	131.11 (15)	C44—C43—H43B	111.4
C25—O21—Ca1	119.65 (15)	C42—C43—H43B	111.4
C35—O31—C32	107.36 (19)	H43A—C43—H43B	109.3
C35—O31—Ca1	126.33 (16)	C43—C44—C45	102.7 (2)
C32—O31—Ca1	125.54 (14)	C43—C44—H44A	111.2
C42—O41—C45	109.29 (18)	C45—C44—H44A	111.2
C42—O41—Ca1	129.91 (15)	C43—C44—H44B	111.2
C45—O41—Ca1	120.79 (14)	C45—C44—H44B	111.2
O1—C1—Fe1	177.8 (3)	H44A—C44—H44B	109.1
O2—C2—Fe1	178.1 (2)	O41—C45—C44	105.3 (2)
O3—C3—Fe1	177.5 (2)	O41—C45—H45A	110.7
O4—C4—Fe2	178.9 (2)	C44—C45—H45A	110.7
O5—C5—Fe2	178.7 (3)	O41—C45—H45B	110.7
O6—C6—Fe2	178.5 (2)	C44—C45—H45B	110.7
O11—C12—C13	104.6 (2)	H45A—C45—H45B	108.8

D—H···A	D—H	H···A	D···A	D—H···A
C34—H34A···O1i	0.99	2.57	3.437 (5)	146
C34—H34B···O2ii	0.99	2.62	3.329 (4)	129
C42—H42A···O6iii	0.99	2.63	3.362 (4)	131
C45—H45B···O3iv	0.99	2.65	3.470 (3)	141
C15—H15A···O1v	0.99	2.67	3.561 (3)	150

Table 1

Selected bond lengths (Å)

Fe1—Fe2	2.5152 (5)
Fe1—S1	2.2999 (7)
Fe1—S2	2.3185 (7)
Fe2—S1	2.3077 (7)
Fe2—S2	2.3110 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C34—H34A⋯O1i	0.99	2.57	3.437 (5)	146
C34—H34B⋯O2ii	0.99	2.62	3.329 (4)	129
C42—H42A⋯O6iii	0.99	2.63	3.362 (4)	131
C45—H45B⋯O3iv	0.99	2.65	3.470 (3)	141
C15—H15A⋯O1v	0.99	2.67	3.561 (3)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .