Decacarbon­yl[μ4-(ethane-1,2-diyl­dinitrilo)­tetra­kis­(methane­thiol­ato)]bis(triphenyl­phosphane)tetra­iron(2 Fe—Fe)

Gao, W.-M.; Li, J.-M.

doi:10.1107/S160053681105584X

Decacarbonyl[μ₄-(ethane-1,2-diyldinitrilo)tetrakis(methanethiolato)]bis(triphenylphosphane)tetrairon(2 Fe—Fe)

In the title compound, [Fe₄(C₆H₁₂N₂S₄)(C₁₈H₁₅P)₂(CO)₁₀], the unit cell contains one molecule, which exhibits a crystallographically imposed center of symmetry. The independent Fe₂S₂ fragment [Fe—Fe = 2.527 (1) Å] is in a butterfly conformation, and each Fe atom displays a pseudo-square-pyramidal coordination geometry. The phosphane group occupies an apical position [Fe—P = 2.2670 (14) Å]. In the crystal, weak intermolecular C—H

O hydrogen bonds link the molecules into chains along [110].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681105584X/cv5221sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053681105584X/cv5221Isup2.hkl Contains datablock I

CCDC reference: 611477

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.008 Å
R factor = 0.055
wR factor = 0.090
Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.968
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     --  C6      ..        5.7 su
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0080 Ang
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600        105
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         68

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00300 Deg.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Macrocyclic complexes containing butterfly [Fe₂S₂] clusters have aroused considerable attention due to their unique structures and interesting phyical and chemical properties (Gloaguen & Rauchfuss, 2009; Yin et al., 2011; Zhao et al., 2009). In recent years, Liu and co-workers reported a series of macrocyclic complexes (Liu, Xiao et al., 2011; Liu & Yin, 2011) with the structure of active site of [FeFe]-hydrogenases. Following the above consideration and ongoing our works in this field (Gao et al., 2011), we report here a dimer structure of the title compound (I) - a new structure model of Fe₂S₂ cluster.

The title molecule (Fig. 1) lies across a crystallographic inversion centre which is situated at the midpoint of the C8–C8A (1.552 (8) Å, symmetry code: (A) 1-x, 1-y, 1-z) bond. The independent Fe₂S₂ fragment [Fe—Fe 2.527 (1) Å] is in a butterfly conformation, and each Fe atom displays pseudo square-pyramidal coordination geometry. The phosphane group occupies an apical position [Fe—P 2.2670 (14) Å], while the (thiomethyl)ethane-1,2-diamine group on the bridging N atom is in an equatorial position and takes a zigzag form. Complex (I) contains two fused six-membered rings, in which one six-membered ring (N1C7S2Fe2S1C6) has a chair conformation and the other six-membered ring (N1C7S2Fe1S1C6) has a boat conformation. The substituent attached to the bridgehead N1 lies in an equatorial position and the unpaired electrons of nitrogen lie in an axial position which is consistent with corresponding diiron azadithiolate complexes (Gao et al., 2011). The sum of the C–N–C angles around nitrogen is 342.9 °, which means there is no π–π conjugation between the substituent group and the p-orbital of nitrogen.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into infinite chains along the [110] direction (Fig. 2).

Related literature top

For background to macrocyclic complexes containing butterfly [Fe₂S₂] clusters, see: Gloaguen & Rauchfuss (2009); Yin et al. (2011); Zhao et al. (2009). For related structures containing butterfly [Fe₂S₂] clusters, see: Liu et al. (2011); Liu & Yin (2011); Song et al. (2011); Gao et al. (2011). For details of the synthesis, see: Gao et al. (2011).

Experimental top

A solution of [{Fe₂(CO)₅µ-(SCH₂)₂NCH₂CH₂Nµ-(SCH₂)₂Fe₂(CO)₅}(PPh₃)₂] (0.4 g, 0.5 mmol) and Me₃NO.2H₂O (0.111 g, 1 mmol) dissolved in MeCN (40 mL) was stirred for 5 to 10 min at room temperature. Then, a solution of PPh₃ (0.524 g, 1 mmol), dissolved in CH₂Cl₂ (2 mL) was added. After 1 h, the solvent was evaporated, and the crude product was purified by chromatography on silica gel with CH₂Cl₂/hexane (1/2 v/v) as the eluent to give the crystals suitable for X-ray diffraction study. Elemental analysis (%) calcd for C₅₂H₄₂Fe₄N₂O₁₀P₂S₄: C, 49.24; H, 3.34; N, 2.21. Found: C, 49.25; H, 3.39; N, 2.19.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 at the 30% probability level [symmetry code: (A) 1-x, 1-y, 1-z]. H atoms have been omitted for clarity.
	Fig. 2. Part of the zigzag infinite chain linked via hydrogen bonds (dashed lines) in [110] direction. H atoms have been omitted for clarity, except for those involved in hydrogen-bonded interactions.

Decacarbonyl[µ₄-(ethane-1,2-diyldinitrilo)tetrakis(methanethiolato)] bis(triphenylphosphane)tetrairon(2 Fe—Fe) top

Crystal data top

[Fe₄(C₆H₁₂N₂S₄)(C₁₈H₁₅P)₂(CO)₁₀]	Z = 1
M_r = 1268.46	F(000) = 646
Triclinic, P1	D_x = 1.579 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.854 (2) Å	Cell parameters from 1603 reflections
b = 11.995 (2) Å	θ = 2.4–22.1°
c = 12.202 (3) Å	µ = 1.34 mm⁻¹
α = 63.257 (3)°	T = 296 K
β = 71.881 (3)°	Block, red
γ = 74.736 (3)°	0.30 × 0.20 × 0.15 mm
V = 1334.0 (5) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	5124 independent reflections
Radiation source: fine-focus sealed tube	3098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
phi and ω scans	θ_max = 26.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→11
T_min = 0.732, T_max = 0.818	k = −14→13
7640 measured reflections	l = −14→15

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.005P)²] where P = (F_o² + 2F_c²)/3
5124 reflections	(Δ/σ)_max < 0.001
334 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[Fe₄(C₆H₁₂N₂S₄)(C₁₈H₁₅P)₂(CO)₁₀]	γ = 74.736 (3)°
M_r = 1268.46	V = 1334.0 (5) Å³
Triclinic, P1	Z = 1
a = 10.854 (2) Å	Mo Kα radiation
b = 11.995 (2) Å	µ = 1.34 mm⁻¹
c = 12.202 (3) Å	T = 296 K
α = 63.257 (3)°	0.30 × 0.20 × 0.15 mm
β = 71.881 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5124 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3098 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.818	R_int = 0.072
7640 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.01	Δρ_max = 0.56 e Å⁻³
5124 reflections	Δρ_min = −0.61 e Å⁻³
334 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 > 2sigma(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
Fe1	0.15320 (7)	0.23740 (6)	0.47610 (6)	0.0398 (2)
Fe2	0.30658 (7)	0.34428 (7)	0.26923 (6)	0.0454 (2)
P1	0.08582 (12)	0.15121 (11)	0.68873 (11)	0.0381 (3)
S2	0.37365 (12)	0.20598 (11)	0.44901 (11)	0.0431 (3)
S1	0.17511 (12)	0.44442 (11)	0.39346 (11)	0.0456 (3)
C26	0.1553 (4)	0.2004 (5)	0.7753 (4)	0.0370 (12)
C25	−0.0910 (4)	0.1748 (4)	0.7554 (4)	0.0385 (12)
N1	0.4172 (4)	0.4284 (4)	0.4331 (3)	0.0444 (11)
C24	0.0359 (5)	−0.1018 (5)	0.8356 (4)	0.0471 (13)
H24A	−0.0485	−0.0687	0.8661	0.057*
C23	0.1836 (5)	0.3697 (5)	0.8167 (4)	0.0488 (14)
H23A	0.1648	0.4544	0.8036	0.059*
O4	−0.0977 (4)	0.3248 (4)	0.4041 (3)	0.0736 (12)
O2	0.5107 (4)	0.5091 (4)	0.1278 (3)	0.0767 (13)
C22	0.2369 (5)	0.1175 (5)	0.8561 (4)	0.0501 (14)
H22A	0.2553	0.0326	0.8701	0.060*
C8	0.5101 (5)	0.4944 (5)	0.4367 (4)	0.0556 (15)
H8A	0.5050	0.5787	0.3706	0.067*
H8B	0.5978	0.4510	0.4177	0.067*
C21	0.1301 (4)	0.3260 (5)	0.7571 (4)	0.0445 (13)
H21A	0.0757	0.3823	0.7035	0.053*
C7	0.4326 (5)	0.2940 (5)	0.5059 (4)	0.0510 (14)
H7A	0.3858	0.2775	0.5924	0.061*
H7B	0.5247	0.2633	0.5058	0.061*
C5	0.1659 (5)	0.0983 (5)	0.4589 (4)	0.0543 (15)
C20	−0.1759 (5)	0.1481 (4)	0.7106 (4)	0.0519 (14)
H20A	−0.1429	0.1233	0.6436	0.062*
O3	0.4167 (4)	0.1517 (4)	0.1686 (4)	0.0926 (14)
C6	0.2828 (5)	0.4894 (5)	0.4487 (4)	0.0541 (15)
H6A	0.2823	0.5799	0.4046	0.065*
H6B	0.2473	0.4714	0.5374	0.065*
C19	−0.1426 (5)	0.2119 (4)	0.8561 (4)	0.0475 (13)
H19A	−0.0870	0.2290	0.8894	0.057*
C18	0.1256 (5)	−0.0211 (4)	0.7533 (4)	0.0408 (12)
C3	0.3731 (5)	0.2276 (5)	0.2085 (5)	0.0573 (15)
C17	−0.3569 (5)	0.1958 (5)	0.8585 (5)	0.0648 (16)
H17A	−0.4467	0.2036	0.8924	0.078*
C16	0.2516 (5)	−0.0765 (5)	0.7143 (4)	0.0537 (15)
H16A	0.3153	−0.0254	0.6604	0.064*
C2	0.4311 (5)	0.4440 (5)	0.1847 (4)	0.0544 (15)
C4	0.0004 (6)	0.2890 (5)	0.4372 (5)	0.0513 (14)
C15	0.2905 (5)	0.1613 (5)	0.9155 (4)	0.0548 (15)
H15A	0.3445	0.1054	0.9697	0.066*
C14	0.1934 (6)	−0.2823 (5)	0.8335 (5)	0.0593 (16)
H14A	0.2159	−0.3694	0.8606	0.071*
C13	0.0692 (6)	−0.2307 (5)	0.8735 (5)	0.0600 (16)
H13A	0.0064	−0.2830	0.9270	0.072*
C12	0.2649 (5)	0.2874 (6)	0.8954 (5)	0.0560 (16)
H12A	0.3025	0.3164	0.9348	0.067*
C11	−0.2760 (5)	0.2232 (5)	0.9060 (5)	0.0609 (16)
H11A	−0.3105	0.2494	0.9720	0.073*
C10	−0.3078 (5)	0.1569 (5)	0.7613 (5)	0.0584 (15)
H10A	−0.3634	0.1367	0.7304	0.070*
C1	0.1951 (5)	0.4157 (6)	0.1694 (5)	0.0597 (16)
C9	0.2834 (5)	−0.2050 (5)	0.7537 (5)	0.0616 (16)
H9A	0.3680	−0.2394	0.7253	0.074*
O1	0.1203 (4)	0.4602 (4)	0.1054 (3)	0.0830 (13)
O5	0.1750 (4)	0.0079 (4)	0.4432 (4)	0.0970 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0444 (5)	0.0435 (5)	0.0331 (4)	−0.0135 (4)	−0.0038 (4)	−0.0161 (4)
Fe2	0.0527 (5)	0.0477 (5)	0.0316 (4)	−0.0118 (4)	−0.0030 (4)	−0.0141 (4)
P1	0.0382 (8)	0.0400 (8)	0.0348 (7)	−0.0102 (6)	−0.0030 (6)	−0.0147 (6)
S2	0.0446 (8)	0.0442 (8)	0.0371 (7)	−0.0105 (6)	−0.0037 (6)	−0.0147 (6)
S1	0.0502 (9)	0.0410 (8)	0.0427 (8)	−0.0092 (6)	−0.0071 (7)	−0.0149 (6)
C26	0.035 (3)	0.043 (3)	0.027 (3)	−0.016 (2)	0.002 (2)	−0.010 (2)
C25	0.035 (3)	0.038 (3)	0.037 (3)	−0.009 (2)	−0.002 (2)	−0.012 (2)
N1	0.042 (3)	0.045 (3)	0.045 (3)	−0.020 (2)	0.000 (2)	−0.017 (2)
C24	0.042 (3)	0.045 (3)	0.044 (3)	−0.013 (3)	0.004 (3)	−0.014 (3)
C23	0.048 (3)	0.058 (4)	0.045 (3)	−0.017 (3)	−0.001 (3)	−0.026 (3)
O4	0.062 (3)	0.091 (3)	0.068 (3)	−0.011 (2)	−0.024 (2)	−0.027 (2)
O2	0.074 (3)	0.077 (3)	0.062 (3)	−0.037 (2)	0.006 (2)	−0.013 (2)
C22	0.048 (3)	0.047 (3)	0.046 (3)	−0.012 (3)	−0.009 (3)	−0.008 (3)
C8	0.065 (4)	0.071 (4)	0.036 (3)	−0.041 (3)	0.005 (3)	−0.020 (3)
C21	0.040 (3)	0.053 (3)	0.038 (3)	−0.014 (3)	−0.001 (2)	−0.017 (3)
C7	0.047 (3)	0.062 (4)	0.038 (3)	−0.016 (3)	0.000 (3)	−0.016 (3)
C5	0.055 (4)	0.068 (4)	0.049 (3)	−0.022 (3)	−0.003 (3)	−0.030 (3)
C20	0.055 (4)	0.058 (4)	0.050 (3)	−0.022 (3)	−0.009 (3)	−0.022 (3)
O3	0.120 (4)	0.095 (3)	0.076 (3)	−0.006 (3)	−0.013 (3)	−0.056 (3)
C6	0.071 (4)	0.044 (3)	0.048 (3)	−0.021 (3)	−0.001 (3)	−0.021 (3)
C19	0.045 (3)	0.055 (3)	0.039 (3)	−0.012 (3)	−0.002 (3)	−0.018 (3)
C18	0.043 (3)	0.045 (3)	0.032 (3)	−0.013 (3)	0.000 (2)	−0.016 (2)
C3	0.072 (4)	0.060 (4)	0.039 (3)	−0.015 (3)	−0.005 (3)	−0.021 (3)
C17	0.034 (3)	0.068 (4)	0.068 (4)	−0.012 (3)	0.001 (3)	−0.013 (3)
C16	0.049 (4)	0.044 (3)	0.051 (3)	−0.014 (3)	0.006 (3)	−0.012 (3)
C2	0.064 (4)	0.054 (4)	0.042 (3)	−0.005 (3)	−0.017 (3)	−0.015 (3)
C4	0.063 (4)	0.053 (4)	0.042 (3)	−0.023 (3)	−0.008 (3)	−0.018 (3)
C15	0.050 (4)	0.065 (4)	0.046 (3)	−0.016 (3)	−0.021 (3)	−0.008 (3)
C14	0.076 (5)	0.036 (3)	0.056 (4)	−0.014 (3)	−0.003 (3)	−0.015 (3)
C13	0.065 (4)	0.049 (4)	0.053 (4)	−0.029 (3)	0.004 (3)	−0.009 (3)
C12	0.047 (4)	0.086 (5)	0.051 (3)	−0.032 (3)	−0.002 (3)	−0.035 (3)
C11	0.046 (4)	0.070 (4)	0.053 (4)	−0.007 (3)	0.010 (3)	−0.027 (3)
C10	0.052 (4)	0.067 (4)	0.060 (4)	−0.023 (3)	−0.015 (3)	−0.020 (3)
C1	0.063 (4)	0.078 (4)	0.033 (3)	−0.019 (3)	−0.005 (3)	−0.017 (3)
C9	0.053 (4)	0.053 (4)	0.058 (4)	−0.003 (3)	0.005 (3)	−0.018 (3)
O1	0.089 (3)	0.098 (3)	0.058 (3)	−0.009 (3)	−0.030 (2)	−0.022 (2)
O5	0.137 (4)	0.082 (3)	0.101 (3)	−0.030 (3)	−0.019 (3)	−0.059 (3)

Geometric parameters (Å, º) top

Fe1—C5	1.739 (6)	C8—C8ⁱ	1.552 (8)
Fe1—C4	1.745 (7)	C8—H8A	0.9700
Fe1—S2	2.2624 (14)	C8—H8B	0.9700
Fe1—P1	2.2670 (14)	C21—H21A	0.9300
Fe1—S1	2.2694 (13)	C7—H7A	0.9700
Fe2—C1	1.765 (6)	C7—H7B	0.9700
Fe2—C3	1.760 (6)	C5—O5	1.152 (5)
Fe2—C2	1.788 (6)	C20—C10	1.368 (8)
Fe2—S1	2.2723 (14)	C20—H20A	0.9300
Fe2—S2	2.2743 (14)	O3—C3	1.142 (5)
P1—C26	1.823 (5)	C6—H6A	0.9700
P1—C18	1.835 (4)	C6—H6B	0.9700
P1—C25	1.839 (4)	C19—C11	1.381 (6)
S2—C7	1.816 (6)	C19—H19A	0.9300
S1—C6	1.812 (4)	C18—C16	1.393 (6)
C26—C21	1.385 (6)	C17—C11	1.360 (7)
C26—C22	1.391 (6)	C17—C10	1.373 (7)
C25—C20	1.370 (7)	C17—H17A	0.9300
C25—C19	1.398 (6)	C16—C9	1.370 (6)
N1—C7	1.441 (5)	C16—H16A	0.9300
N1—C6	1.443 (5)	C15—C12	1.385 (6)
N1—C8	1.461 (5)	C15—H15A	0.9300
C24—C13	1.377 (6)	C14—C9	1.360 (6)
C24—C18	1.387 (5)	C14—C13	1.368 (6)
C24—H24A	0.9300	C14—H14A	0.9300
C23—C12	1.376 (6)	C13—H13A	0.9300
C23—C21	1.380 (6)	C12—H12A	0.9300
C23—H23A	0.9300	C11—H11A	0.9300
O4—C4	1.156 (5)	C10—H10A	0.9300
O2—C2	1.154 (7)	C1—O1	1.157 (6)
C22—C15	1.377 (6)	C9—H9A	0.9300
C22—H22A	0.9300

C5—Fe1—C4	90.6 (2)	C23—C21—C26	121.6 (5)
C5—Fe1—S2	88.79 (16)	C23—C21—H21A	119.5
C4—Fe1—S2	158.94 (18)	C26—C21—H21A	119.5
C5—Fe1—P1	94.85 (16)	N1—C7—S2	114.2 (3)
C4—Fe1—P1	99.09 (16)	N1—C7—H7A	108.8
S2—Fe1—P1	102.17 (5)	S2—C7—H7A	108.8
C5—Fe1—S1	150.83 (16)	N1—C7—H7B	108.8
C4—Fe1—S1	86.21 (15)	S2—C7—H7B	108.8
S2—Fe1—S1	84.04 (4)	H7A—C7—H7B	107.7
P1—Fe1—S1	114.29 (5)	O5—C5—Fe1	177.9 (5)
C1—Fe2—C3	91.5 (2)	C10—C20—C25	121.5 (5)
C1—Fe2—C2	100.9 (2)	C10—C20—H20A	119.3
C3—Fe2—C2	99.1 (2)	C25—C20—H20A	119.3
C1—Fe2—S1	88.47 (17)	N1—C6—S1	115.5 (3)
C3—Fe2—S1	160.45 (16)	N1—C6—H6A	108.4
C2—Fe2—S1	100.14 (16)	S1—C6—H6A	108.4
C1—Fe2—S2	154.73 (16)	N1—C6—H6B	108.4
C3—Fe2—S2	88.13 (17)	S1—C6—H6B	108.4
C2—Fe2—S2	104.11 (16)	H6A—C6—H6B	107.5
S1—Fe2—S2	83.70 (5)	C11—C19—C25	120.0 (4)
C26—P1—C18	104.7 (2)	C11—C19—H19A	120.0
C26—P1—C25	103.0 (2)	C25—C19—H19A	120.0
C18—P1—C25	102.3 (2)	C24—C18—C16	117.2 (4)
C26—P1—Fe1	116.21 (13)	C24—C18—P1	123.6 (4)
C18—P1—Fe1	111.65 (14)	C16—C18—P1	119.2 (3)
C25—P1—Fe1	117.26 (15)	O3—C3—Fe2	179.8 (6)
C7—S2—Fe1	114.11 (16)	C11—C17—C10	120.5 (5)
C7—S2—Fe2	108.06 (16)	C11—C17—H17A	119.8
Fe1—S2—Fe2	67.70 (4)	C10—C17—H17A	119.8
C6—S1—Fe1	118.03 (16)	C9—C16—C18	121.1 (4)
C6—S1—Fe2	106.23 (17)	C9—C16—H16A	119.4
Fe1—S1—Fe2	67.62 (4)	C18—C16—H16A	119.4
C21—C26—C22	118.8 (4)	O2—C2—Fe2	178.3 (4)
C21—C26—P1	118.9 (4)	O4—C4—Fe1	176.3 (4)
C22—C26—P1	122.7 (4)	C22—C15—C12	120.7 (5)
C20—C25—C19	118.3 (4)	C22—C15—H15A	119.6
C20—C25—P1	119.3 (4)	C12—C15—H15A	119.6
C19—C25—P1	122.8 (3)	C9—C14—C13	119.4 (5)
C7—N1—C6	113.8 (4)	C9—C14—H14A	120.3
C7—N1—C8	115.0 (4)	C13—C14—H14A	120.3
C6—N1—C8	114.1 (4)	C14—C13—C24	120.5 (4)
C13—C24—C18	121.0 (4)	C14—C13—H13A	119.8
C13—C24—H24A	119.5	C24—C13—H13A	119.8
C18—C24—H24A	119.5	C23—C12—C15	119.5 (4)
C12—C23—C21	120.0 (5)	C23—C12—H12A	120.3
C12—C23—H23A	120.0	C15—C12—H12A	120.3
C21—C23—H23A	120.0	C17—C11—C19	119.9 (5)
C15—C22—C26	120.0 (4)	C17—C11—H11A	119.7
C15—C22—H22A	120.0	C19—C11—H11A	119.7
C26—C22—H22A	120.0	C17—C10—C20	119.2 (5)
N1—C8—C8ⁱ	115.5 (4)	C17—C10—H10A	120.4
N1—C8—H8A	108.4	C20—C10—H10A	120.4
C8ⁱ—C8—H8A	108.4	O1—C1—Fe2	178.3 (5)
N1—C8—H8B	108.4	C14—C9—C16	120.7 (5)
C8ⁱ—C8—H8B	108.4	C14—C9—H9A	119.6
H8A—C8—H8B	107.5	C16—C9—H9A	119.6

C5—Fe1—P1—C26	139.2 (2)	C25—P1—C26—C22	115.3 (4)
C4—Fe1—P1—C26	−129.4 (2)	Fe1—P1—C26—C22	−115.0 (3)
S2—Fe1—P1—C26	49.39 (18)	C26—P1—C25—C20	179.4 (4)
S1—Fe1—P1—C26	−39.52 (18)	C18—P1—C25—C20	−72.2 (4)
C5—Fe1—P1—C18	19.2 (2)	Fe1—P1—C25—C20	50.5 (4)
C4—Fe1—P1—C18	110.6 (2)	C26—P1—C25—C19	−4.5 (4)
S2—Fe1—P1—C18	−70.61 (16)	C18—P1—C25—C19	104.0 (4)
S1—Fe1—P1—C18	−159.52 (15)	Fe1—P1—C25—C19	−133.4 (3)
C5—Fe1—P1—C25	−98.6 (2)	C21—C26—C22—C15	−0.2 (6)
C4—Fe1—P1—C25	−7.2 (2)	P1—C26—C22—C15	177.6 (3)
S2—Fe1—P1—C25	171.60 (16)	C7—N1—C8—C8ⁱ	−71.4 (6)
S1—Fe1—P1—C25	82.94 (19)	C6—N1—C8—C8ⁱ	63.5 (7)
C5—Fe1—S2—C7	−160.8 (2)	C12—C23—C21—C26	0.4 (7)
C4—Fe1—S2—C7	110.8 (5)	C22—C26—C21—C23	0.0 (6)
P1—Fe1—S2—C7	−66.07 (17)	P1—C26—C21—C23	−177.8 (3)
S1—Fe1—S2—C7	47.55 (17)	C6—N1—C7—S2	71.8 (4)
C5—Fe1—S2—Fe2	98.66 (16)	C8—N1—C7—S2	−153.9 (3)
C4—Fe1—S2—Fe2	10.2 (4)	Fe1—S2—C7—N1	−69.5 (3)
P1—Fe1—S2—Fe2	−166.64 (4)	Fe2—S2—C7—N1	3.5 (4)
S1—Fe1—S2—Fe2	−53.08 (5)	C19—C25—C20—C10	0.1 (7)
C1—Fe2—S2—C7	−129.1 (4)	P1—C25—C20—C10	176.4 (4)
C3—Fe2—S2—C7	141.5 (2)	C7—N1—C6—S1	−64.6 (4)
C2—Fe2—S2—C7	42.6 (2)	C8—N1—C6—S1	160.1 (3)
S1—Fe2—S2—C7	−56.34 (16)	Fe1—S1—C6—N1	57.8 (4)
C1—Fe2—S2—Fe1	−19.8 (4)	Fe2—S1—C6—N1	−15.1 (4)
C3—Fe2—S2—Fe1	−109.24 (16)	C20—C25—C19—C11	−1.2 (7)
C2—Fe2—S2—Fe1	151.89 (16)	P1—C25—C19—C11	−177.4 (4)
S1—Fe2—S2—Fe1	52.97 (4)	C13—C24—C18—C16	−2.1 (7)
C5—Fe1—S1—C6	−120.6 (4)	C13—C24—C18—P1	175.2 (4)
C4—Fe1—S1—C6	155.0 (2)	C26—P1—C18—C24	104.2 (4)
S2—Fe1—S1—C6	−43.94 (19)	C25—P1—C18—C24	−2.7 (4)
P1—Fe1—S1—C6	56.75 (19)	Fe1—P1—C18—C24	−129.2 (3)
C5—Fe1—S1—Fe2	−23.5 (3)	C26—P1—C18—C16	−78.5 (4)
C4—Fe1—S1—Fe2	−107.90 (15)	C25—P1—C18—C16	174.6 (4)
S2—Fe1—S1—Fe2	53.14 (4)	Fe1—P1—C18—C16	48.0 (4)
P1—Fe1—S1—Fe2	153.83 (5)	C24—C18—C16—C9	1.6 (7)
C1—Fe2—S1—C6	−142.7 (2)	P1—C18—C16—C9	−175.8 (4)
C3—Fe2—S1—C6	127.2 (5)	C26—C22—C15—C12	−0.2 (7)
C2—Fe2—S1—C6	−41.9 (2)	C9—C14—C13—C24	−1.0 (8)
S2—Fe2—S1—C6	61.38 (16)	C18—C24—C13—C14	1.9 (8)
C1—Fe2—S1—Fe1	103.14 (16)	C21—C23—C12—C15	−0.8 (7)
C3—Fe2—S1—Fe1	13.1 (5)	C22—C15—C12—C23	0.7 (7)
C2—Fe2—S1—Fe1	−156.05 (16)	C10—C17—C11—C19	0.2 (8)
S2—Fe2—S1—Fe1	−52.84 (5)	C25—C19—C11—C17	1.1 (7)
C18—P1—C26—C21	−173.5 (3)	C11—C17—C10—C20	−1.3 (8)
C25—P1—C26—C21	−66.9 (4)	C25—C20—C10—C17	1.2 (7)
Fe1—P1—C26—C21	62.8 (4)	C13—C14—C9—C16	0.4 (8)
C18—P1—C26—C22	8.7 (4)	C18—C16—C9—C14	−0.8 (8)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20A···O5ⁱⁱ	0.93	2.39	3.182 (7)	143

Symmetry code: (ii) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Fe₄(C₆H₁₂N₂S₄)(C₁₈H₁₅P)₂(CO)₁₀]
M_r	1268.46
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	10.854 (2), 11.995 (2), 12.202 (3)
α, β, γ (°)	63.257 (3), 71.881 (3), 74.736 (3)
V (Å³)	1334.0 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.732, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	7640, 5124, 3098
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.090, 1.01
No. of reflections	5124
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.61

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).