Decacarbonyl(μ₄-2-thiodithiobenzoato- κ⁴C,S,S′,S′′)bis(trimethyl phosphite)tetrafer

The title disubstituted tetranuclear cluster, [Fe₄(C₃H₉O₃P)₂(C₇H₄S₃)(CO)₁₀], was obtained by heating the tetranuclear complex TN (Fe₄S₃C₁₉O₁₂H₄) with an excess of trimethyl phosphite in acetone at 328 K. The structure shows that, of the two P(OMe)₃ ligands, one has replaced a carbonyl on an Fe atom in the symmetric part of the tetranuclear cluster, whereas the second one has replaced a carbonyl on an Fe atom in the asymmetric part of the cluster.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.029
• wR factor = 0.076
• Data-to-parameter ratio = 15.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

La chimie organométallique occupe une place importante dans la chimie moderne, due en particulier aux différentes applications qui en découlent: synthèse organique (Alper, 1976–1978), synthèse bioinorganique (Jaouen et al., 1993) et processus catalytiques (Tolman, 1972).

Les réactions de remplacement du monoxyde de carbone catalysés par transfert d'électrons dans des complexes polynucléaires du fer à ligands soufrés ont déjà été étudiées (Darchen et al., 1982). Dans la plupart des cas, la substitution induite à l'électrode conduit aux mêmes résultats que ceux obtenus par voie thermique (Darchen et al., 1983), toutefois pour certains substrats on observe une orientation différente du remplacement des carbonyles suivant le mode d'activation. Ainsi dans le complexe tétranucléaire undecacarbonyl(µ₄-2-thiodithiobenzoato- κ⁴C,S,S',S'')(triphenyl phosphine)tetrafer (Laifa, Benali-Cherif & Berrah, 2003) le ligand PPh₃ occupe une position équatoriale, alors que dans le complexe undecacarbonyl (µ₄-2-thiodithiobenzoato-κ⁴C,S,S',S'')(trimethyl phosphite)tetrafer (Laifa, Benali-Cherif & Merazig, 2003) le ligand P(OMe)₃ occupe une position axiale.

Le complexe TN (Bird et al., 1981) contient deux motifs binucléaires A et B différents et trois sites métalliques non-équivalents qui font de ce complexe un substrat de choix pour l'étude de la régiosélectivité et la stéréosélectivité de la substitution de carbonyles. Partant de ce complexe et en poursuivant nos investigations sur la substitution des carbonyles par des ligands phosphines, nous avons réalisé une réaction de double substitution avec le triméthyl phosphite P(OMe)₃).

Le complexe disubstitué obtenu (Fe₄S₃C₂₃O₁₆P₂H₂₂) contient deux motifs binucléaires A et B différents, liés entre eux par le ligand C₆SCS₂. Le motif A est pseudosymétrique et le squelette Fe₂(CO)₆ est doublement ponté par les deux atomes de soufre S1 et S2 du ligand. Le motif B est asymétrique, seul l'atome S3 du ligand ponte les deux atomes de fer alors que S2 qui ponte le motif A est uniquement lié à l'atome Fe4 du motif B. Cette structure montre que la premiére substitution du carbonyle par la trimethyl phosphite a lieu spécifiquement sur le motif A symétyrique, ponté par S2 en position équatoriale par rapport à la liaison Fe1—Fe2 [Fe1—Fe2—P1 = 113.92 (3)°] et la deuxième substitution sur le motif B asymétrique est aussi en position équatoriale par rapport á la liaison Fe3—Fe4 [Fe3—Fe4—P2 = 94.48 (3)°]. Ce résultat est en accord avec la régle d'une substitution par site métallique dans les complexes polynucléaires (El Kbir et al., 1983).

S2. Experimental

Le complexe tétranucléaire disubstitué (Fe₄S₃C₂₃O₁₆P₂H₂₂) est préparé sous activation thermique du TN, où un carbonyle du motif A symétrique et un carbonyle du motif B asymétrique sont substitués par le ligand trimethyl phosphite, 5,9x10⁻⁴ moles de TN et 1,2 × 10⁻³ moles de P(OMe)₃ sont dissouts dans l'acétone et chauffés à reflux pendant 10 heures sous azote et à l'abri de la lumière. La réaction conduit en premier temps au monosubstitué qui réagit à son tour avec l'éxcès du P(OMe)₃ pour conduire au complexe disubstitué. Le solvant est distillé et le résidu est séparé par chromatographie préparative sur plaque (éluant: éther de pétrole/éther éthylique 8:1). Le complexe disubstitué (Fe₄S₃C₂₃O₁₆PH₁₈) est récupéré aprés lavage du gel de silice à l'acétone puis recristallisé dans l'éther/hexane 1:1), on obtient des cristaux rouges prismatiques.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. Dessin ORTEP-3 (Farrugia, 1997) de la molécule. Les ellipsoides de vibration des atomes ont une probabilité de 50%.

(I)

Crystal data

[Fe4(C3H9O3P)2(C7H4S3)(CO)10]	F(000) = 1880
Mr = 935.96	Dx = 1.764 Mg m^−3
Monoclinic, P21/c	Melting point: 172 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 16.4390 (2) Å	Cell parameters from 25 reflections
b = 8.9990 (3) Å	θ = 10–15°
c = 23.9750 (2) Å	µ = 1.95 mm^−1
β = 96.529 (3)°	T = 293 K
V = 3523.73 (13) Å^3	Prism, red
Z = 4	0.1 × 0.1 × 0.05 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	5439 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.006
Graphite monochromator	θmax = 26.0°, θmin = 2.4°
non–profiled ω scans	h = 0→20
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −11→0
Tmin = 0.818, Tmax = 0.907	l = −29→29
7804 measured reflections	3 standard reflections every 120 min
6840 independent reflections	intensity decay: 3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 2.4041P] where P = (Fo^2 + 2Fc^2)/3
6840 reflections	(Δ/σ)max = 0.001
439 parameters	Δρmax = 0.88 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Fe4	0.76290 (2)	−0.00444 (5)	0.444371 (15)	0.03405 (10)
Fe2	0.80230 (2)	0.07918 (4)	0.283024 (15)	0.03270 (10)
Fe1	0.79409 (2)	0.33984 (4)	0.325608 (16)	0.03439 (10)
Fe3	0.63667 (3)	0.18250 (5)	0.447769 (17)	0.04380 (12)
S2	0.75392 (4)	0.12990 (7)	0.36268 (3)	0.03065 (14)
S1	0.71198 (4)	0.25515 (8)	0.25075 (3)	0.03809 (16)
P2	0.74270 (5)	−0.11885 (10)	0.52125 (3)	0.04369 (19)
P1	0.85180 (5)	0.07617 (9)	0.20256 (3)	0.04316 (19)
O21	0.79639 (15)	−0.2602 (3)	0.53904 (10)	0.0645 (7)
O22	0.65508 (14)	−0.1905 (3)	0.52530 (9)	0.0529 (6)
O19	0.80124 (17)	−0.0090 (3)	0.15257 (10)	0.0695 (7)
O23	0.75084 (16)	−0.0126 (3)	0.57373 (9)	0.0630 (7)
O18	0.87479 (16)	0.2303 (3)	0.17949 (9)	0.0619 (7)
O17	0.91101 (16)	0.1346 (3)	0.49995 (11)	0.0725 (8)
O14	0.76774 (17)	0.3887 (3)	0.48772 (12)	0.0757 (8)
O10	0.68105 (16)	0.5599 (3)	0.36427 (11)	0.0652 (7)
C3	0.61045 (17)	0.2184 (3)	0.26613 (12)	0.0404 (7)
O20	0.93739 (15)	−0.0088 (3)	0.20017 (11)	0.0637 (7)
O11	0.73815 (16)	−0.2213 (3)	0.26874 (11)	0.0686 (7)
O8	0.87576 (16)	0.5267 (3)	0.24892 (11)	0.0691 (7)
O16	0.84553 (16)	−0.2562 (3)	0.39805 (11)	0.0678 (7)
C17	0.8521 (2)	0.0827 (4)	0.47903 (12)	0.0457 (7)
O9	0.93293 (16)	0.3850 (3)	0.41159 (11)	0.0783 (8)
C13	0.6018 (2)	0.1498 (5)	0.51519 (15)	0.0632 (10)
O12	0.96298 (15)	0.0281 (3)	0.34428 (11)	0.0687 (7)
O15	0.51202 (19)	0.4075 (4)	0.41617 (13)	0.0924 (10)
C2	0.58772 (17)	0.1604 (3)	0.31622 (12)	0.0397 (6)
C22	0.6274 (2)	−0.3194 (4)	0.49328 (15)	0.0605 (9)
H22A	0.6616	−0.3349	0.4639	0.091*
H22B	0.5718	−0.3048	0.4771	0.091*
H22C	0.6303	−0.4048	0.5174	0.091*
C4	0.5510 (2)	0.2482 (4)	0.22167 (14)	0.0562 (9)
H4	0.5664	0.2880	0.1886	0.067*
O13	0.5763 (2)	0.1359 (4)	0.55720 (11)	0.0968 (11)
C19	0.7157 (3)	0.0236 (6)	0.13496 (17)	0.0932 (16)
H19A	0.6838	0.0016	0.1651	0.140*
H19B	0.6969	−0.0360	0.1029	0.140*
H19C	0.7099	0.1269	0.1253	0.140*
C5	0.4698 (2)	0.2197 (5)	0.22574 (16)	0.0707 (11)
H5	0.4305	0.2408	0.1957	0.085*
C14	0.7192 (2)	0.3053 (4)	0.47116 (14)	0.0550 (8)
C15	0.5590 (2)	0.3164 (4)	0.42831 (15)	0.0610 (9)
C16	0.81208 (19)	−0.1596 (4)	0.41623 (12)	0.0430 (7)
C6	0.4468 (2)	0.1601 (5)	0.27430 (17)	0.0713 (11)
H6	0.3920	0.1391	0.2770	0.086*
C7	0.50442 (19)	0.1314 (4)	0.31873 (15)	0.0564 (9)
H7	0.4879	0.0917	0.3515	0.068*
C11	0.76216 (18)	−0.1024 (4)	0.27324 (12)	0.0410 (7)
C9	0.8786 (2)	0.3647 (4)	0.37881 (13)	0.0470 (7)
C1	0.64672 (16)	0.1255 (3)	0.36597 (11)	0.0348 (6)
C8	0.8441 (2)	0.4542 (3)	0.27815 (13)	0.0460 (7)
C23	0.7347 (3)	−0.0624 (6)	0.62907 (14)	0.0963 (16)
H23A	0.6780	−0.0889	0.6282	0.144*
H23B	0.7473	0.0162	0.6557	0.144*
H23C	0.7682	−0.1473	0.6399	0.144*
C12	0.9002 (2)	0.0462 (3)	0.31970 (12)	0.0440 (7)
C10	0.72527 (19)	0.4757 (3)	0.34981 (13)	0.0439 (7)
C18	0.9063 (3)	0.2465 (5)	0.12553 (15)	0.0925 (15)
H18A	0.9614	0.2100	0.1283	0.139*
H18B	0.9055	0.3496	0.1151	0.139*
H18C	0.8727	0.1908	0.0976	0.139*
C20	0.9440 (3)	−0.1629 (4)	0.21242 (17)	0.0690 (11)
H20A	0.9350	−0.1795	0.2508	0.103*
H20B	0.9978	−0.1971	0.2067	0.103*
H20C	0.9039	−0.2165	0.1881	0.103*
C21	0.8839 (2)	−0.2621 (6)	0.54557 (19)	0.0947 (16)
H21A	0.9034	−0.2418	0.5101	0.142*
H21B	0.9030	−0.3581	0.5587	0.142*
H21C	0.9042	−0.1877	0.5723	0.142*
S3	0.63088 (4)	−0.03414 (9)	0.40670 (3)	0.04137 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe4	0.0334 (2)	0.0367 (2)	0.03162 (19)	0.00256 (18)	0.00186 (15)	0.00352 (16)
Fe2	0.0350 (2)	0.0303 (2)	0.03301 (19)	−0.00111 (17)	0.00448 (15)	0.00064 (16)
Fe1	0.0343 (2)	0.0295 (2)	0.0388 (2)	−0.00182 (17)	0.00194 (16)	0.00149 (16)
Fe3	0.0405 (2)	0.0494 (3)	0.0430 (2)	0.0093 (2)	0.01113 (18)	0.0037 (2)
S2	0.0296 (3)	0.0313 (3)	0.0305 (3)	0.0008 (3)	0.0015 (2)	0.0019 (3)
S1	0.0411 (4)	0.0371 (4)	0.0348 (3)	−0.0008 (3)	−0.0011 (3)	0.0056 (3)
P2	0.0479 (5)	0.0480 (5)	0.0352 (4)	0.0051 (4)	0.0048 (3)	0.0074 (3)
P1	0.0558 (5)	0.0366 (4)	0.0390 (4)	−0.0051 (4)	0.0136 (3)	−0.0020 (3)
O21	0.0599 (15)	0.0706 (17)	0.0634 (14)	0.0205 (13)	0.0094 (12)	0.0271 (13)
O22	0.0557 (14)	0.0544 (14)	0.0515 (12)	−0.0019 (11)	0.0184 (10)	0.0052 (11)
O19	0.0834 (19)	0.0752 (18)	0.0507 (13)	−0.0152 (15)	0.0108 (13)	−0.0183 (12)
O23	0.0864 (18)	0.0669 (16)	0.0352 (11)	−0.0054 (14)	0.0043 (11)	−0.0010 (11)
O18	0.0953 (19)	0.0472 (14)	0.0467 (12)	−0.0135 (13)	0.0237 (12)	0.0034 (10)
O17	0.0582 (16)	0.090 (2)	0.0650 (15)	−0.0183 (15)	−0.0130 (13)	−0.0078 (14)
O14	0.0707 (18)	0.0669 (18)	0.0872 (19)	−0.0001 (15)	−0.0009 (15)	−0.0274 (15)
O10	0.0655 (16)	0.0542 (15)	0.0772 (17)	0.0216 (13)	0.0141 (13)	−0.0025 (13)
C3	0.0359 (15)	0.0372 (16)	0.0455 (15)	−0.0009 (13)	−0.0062 (12)	0.0067 (13)
O20	0.0665 (16)	0.0559 (15)	0.0741 (16)	0.0022 (13)	0.0316 (13)	0.0045 (12)
O11	0.0654 (16)	0.0463 (15)	0.0929 (19)	−0.0197 (13)	0.0035 (14)	−0.0022 (13)
O8	0.0765 (18)	0.0563 (15)	0.0764 (17)	−0.0147 (14)	0.0165 (14)	0.0217 (13)
O16	0.0768 (18)	0.0514 (15)	0.0761 (16)	0.0156 (14)	0.0131 (14)	−0.0114 (13)
C17	0.0482 (18)	0.0517 (19)	0.0364 (15)	0.0042 (16)	0.0018 (13)	0.0030 (14)
O9	0.0564 (16)	0.094 (2)	0.0778 (17)	−0.0130 (15)	−0.0233 (14)	0.0029 (16)
C13	0.060 (2)	0.075 (3)	0.058 (2)	0.021 (2)	0.0188 (18)	0.0061 (18)
O12	0.0436 (14)	0.0779 (18)	0.0806 (17)	0.0088 (13)	−0.0096 (13)	0.0040 (14)
O15	0.080 (2)	0.094 (2)	0.105 (2)	0.0491 (19)	0.0188 (17)	0.0151 (18)
C2	0.0350 (15)	0.0365 (16)	0.0462 (15)	0.0002 (13)	−0.0017 (12)	0.0043 (13)
C22	0.061 (2)	0.055 (2)	0.066 (2)	−0.0053 (18)	0.0110 (18)	0.0078 (18)
C4	0.052 (2)	0.060 (2)	0.0523 (18)	−0.0045 (17)	−0.0133 (15)	0.0160 (16)
O13	0.106 (2)	0.130 (3)	0.0628 (17)	0.032 (2)	0.0443 (17)	0.0189 (18)
C19	0.087 (3)	0.122 (4)	0.064 (2)	0.013 (3)	−0.022 (2)	−0.030 (3)
C5	0.046 (2)	0.083 (3)	0.076 (2)	−0.005 (2)	−0.0250 (18)	0.023 (2)
C14	0.057 (2)	0.059 (2)	0.0498 (18)	0.0125 (18)	0.0071 (16)	−0.0094 (16)
C15	0.057 (2)	0.067 (2)	0.062 (2)	0.014 (2)	0.0185 (17)	0.0037 (18)
C16	0.0435 (17)	0.0439 (18)	0.0408 (15)	−0.0002 (15)	0.0011 (13)	0.0065 (13)
C6	0.0360 (19)	0.087 (3)	0.086 (3)	−0.0062 (19)	−0.0136 (18)	0.027 (2)
C7	0.0349 (17)	0.066 (2)	0.067 (2)	−0.0038 (16)	−0.0027 (15)	0.0173 (18)
C11	0.0368 (16)	0.0428 (18)	0.0437 (15)	−0.0013 (14)	0.0059 (12)	0.0012 (13)
C9	0.0461 (18)	0.0425 (18)	0.0516 (18)	−0.0035 (15)	0.0027 (15)	0.0030 (14)
C1	0.0279 (14)	0.0387 (15)	0.0378 (14)	−0.0001 (12)	0.0032 (11)	0.0047 (12)
C8	0.0481 (18)	0.0353 (17)	0.0539 (18)	−0.0018 (14)	0.0030 (15)	0.0028 (14)
C23	0.145 (5)	0.110 (4)	0.0361 (18)	−0.001 (3)	0.021 (2)	0.002 (2)
C12	0.0449 (18)	0.0411 (17)	0.0470 (16)	0.0017 (14)	0.0097 (14)	0.0019 (13)
C10	0.0453 (18)	0.0379 (16)	0.0473 (17)	−0.0012 (15)	0.0004 (14)	0.0018 (13)
C18	0.148 (4)	0.082 (3)	0.055 (2)	−0.029 (3)	0.043 (3)	0.010 (2)
C20	0.074 (3)	0.046 (2)	0.092 (3)	0.0116 (19)	0.029 (2)	−0.0016 (19)
C21	0.058 (3)	0.133 (4)	0.090 (3)	0.028 (3)	−0.006 (2)	0.045 (3)
S3	0.0354 (4)	0.0441 (4)	0.0440 (4)	−0.0042 (3)	0.0021 (3)	0.0108 (3)

Geometric parameters (Å, º)

Fe4—C17	1.782 (3)	C3—C4	1.388 (4)
Fe4—C16	1.784 (3)	C3—C2	1.399 (4)
Fe4—P2	2.1695 (8)	O20—C20	1.420 (4)
Fe4—S3	2.2697 (8)	O11—C11	1.141 (4)
Fe4—S2	2.2920 (7)	O8—C8	1.128 (4)
Fe4—Fe3	2.6798 (6)	O16—C16	1.141 (4)
Fe2—C11	1.768 (3)	O9—C9	1.135 (4)
Fe2—C12	1.770 (3)	C13—O13	1.141 (4)
Fe2—P1	2.1776 (8)	O12—C12	1.140 (4)
Fe2—S2	2.1986 (7)	O15—C15	1.141 (4)
Fe2—S1	2.2472 (8)	C2—C7	1.402 (4)
Fe2—Fe1	2.5679 (5)	C2—C1	1.483 (4)
Fe1—C9	1.790 (3)	C22—H22A	0.9600
Fe1—C8	1.800 (3)	C22—H22B	0.9600
Fe1—C10	1.806 (3)	C22—H22C	0.9600
Fe1—S2	2.2201 (8)	C4—C5	1.374 (5)
Fe1—S1	2.2522 (8)	C4—H4	0.9300
Fe3—C15	1.779 (4)	C19—H19A	0.9600
Fe3—C14	1.790 (4)	C19—H19B	0.9600
Fe3—C13	1.800 (4)	C19—H19C	0.9600
Fe3—C1	2.052 (3)	C5—C6	1.373 (5)
Fe3—S3	2.1813 (9)	C5—H5	0.9300
S2—C1	1.773 (3)	C6—C7	1.367 (5)
S1—C3	1.781 (3)	C6—H6	0.9300
P2—O23	1.574 (2)	C7—H7	0.9300
P2—O21	1.579 (2)	C1—S3	1.773 (3)
P2—O22	1.591 (2)	C23—H23A	0.9600
P1—O18	1.556 (2)	C23—H23B	0.9600
P1—O19	1.577 (2)	C23—H23C	0.9600
P1—O20	1.608 (3)	C18—H18A	0.9600
O21—C21	1.430 (4)	C18—H18B	0.9600
O22—C22	1.437 (4)	C18—H18C	0.9600
O19—C19	1.451 (5)	C20—H20A	0.9600
O23—C23	1.453 (4)	C20—H20B	0.9600
O18—C18	1.454 (4)	C20—H20C	0.9600
O17—C17	1.140 (4)	C21—H21A	0.9600
O14—C14	1.134 (4)	C21—H21B	0.9600
O10—C10	1.131 (4)	C21—H21C	0.9600
C17—Fe4—C16	97.86 (14)	O20—P1—Fe2	117.01 (10)
C17—Fe4—P2	90.57 (10)	C21—O21—P2	124.3 (3)
C16—Fe4—P2	93.99 (10)	C22—O22—P2	121.9 (2)
C17—Fe4—S3	159.35 (11)	C19—O19—P1	122.1 (3)
C16—Fe4—S3	102.19 (10)	C23—O23—P2	122.3 (3)
P2—Fe4—S3	92.89 (3)	C18—O18—P1	122.1 (2)
C17—Fe4—S2	97.81 (10)	C4—C3—C2	119.9 (3)
C16—Fe4—S2	94.45 (9)	C4—C3—S1	113.6 (2)
P2—Fe4—S2	167.17 (3)	C2—C3—S1	126.5 (2)
S3—Fe4—S2	75.89 (3)	C20—O20—P1	120.3 (2)
C17—Fe4—Fe3	107.95 (11)	O17—C17—Fe4	177.1 (3)
C16—Fe4—Fe3	152.70 (10)	O13—C13—Fe3	175.8 (3)
P2—Fe4—Fe3	94.49 (3)	C3—C2—C7	117.6 (3)
S3—Fe4—Fe3	51.49 (2)	C3—C2—C1	123.7 (3)
S2—Fe4—Fe3	73.74 (2)	C7—C2—C1	118.6 (3)
C11—Fe2—C12	102.46 (14)	O22—C22—H22A	109.5
C11—Fe2—P1	92.43 (10)	O22—C22—H22B	109.5
C12—Fe2—P1	91.58 (10)	H22A—C22—H22B	109.5
C11—Fe2—S2	98.09 (10)	O22—C22—H22C	109.5
C12—Fe2—S2	90.10 (10)	H22A—C22—H22C	109.5
P1—Fe2—S2	168.73 (3)	H22B—C22—H22C	109.5
C11—Fe2—S1	112.56 (10)	C5—C4—C3	121.0 (3)
C12—Fe2—S1	144.83 (11)	C5—C4—H4	119.5
P1—Fe2—S1	90.15 (3)	C3—C4—H4	119.5
S2—Fe2—S1	82.10 (3)	O19—C19—H19A	109.5
C11—Fe2—Fe1	149.47 (10)	O19—C19—H19B	109.5
C12—Fe2—Fe1	92.38 (10)	H19A—C19—H19B	109.5
P1—Fe2—Fe1	113.92 (3)	O19—C19—H19C	109.5
S2—Fe2—Fe1	54.86 (2)	H19A—C19—H19C	109.5
S1—Fe2—Fe1	55.29 (2)	H19B—C19—H19C	109.5
C9—Fe1—C8	90.32 (14)	C6—C5—C4	119.8 (3)
C9—Fe1—C10	98.63 (14)	C6—C5—H5	120.1
C8—Fe1—C10	99.41 (14)	C4—C5—H5	120.1
C9—Fe1—S2	93.64 (10)	O14—C14—Fe3	175.3 (3)
C8—Fe1—S2	156.54 (10)	O15—C15—Fe3	176.7 (4)
C10—Fe1—S2	102.82 (10)	O16—C16—Fe4	177.9 (3)
C9—Fe1—S1	163.02 (11)	C7—C6—C5	120.1 (3)
C8—Fe1—S1	88.00 (10)	C7—C6—H6	120.0
C10—Fe1—S1	98.31 (10)	C5—C6—H6	120.0
S2—Fe1—S1	81.52 (3)	C6—C7—C2	121.7 (3)
C9—Fe1—Fe2	109.03 (11)	C6—C7—H7	119.2
C8—Fe1—Fe2	102.86 (10)	C2—C7—H7	119.2
C10—Fe1—Fe2	144.05 (10)	O11—C11—Fe2	177.4 (3)
S2—Fe1—Fe2	54.08 (2)	O9—C9—Fe1	177.6 (3)
S1—Fe1—Fe2	55.11 (2)	C2—C1—S3	119.4 (2)
C15—Fe3—C14	99.20 (17)	C2—C1—S2	121.5 (2)
C15—Fe3—C13	93.09 (16)	S3—C1—S2	104.57 (14)
C14—Fe3—C13	97.29 (17)	C2—C1—Fe3	126.8 (2)
C15—Fe3—C1	92.99 (14)	S3—C1—Fe3	69.10 (9)
C14—Fe3—C1	108.25 (13)	S2—C1—Fe3	103.02 (13)
C13—Fe3—C1	152.39 (16)	O8—C8—Fe1	179.2 (3)
C15—Fe3—S3	119.60 (13)	O23—C23—H23A	109.5
C14—Fe3—S3	133.30 (11)	O23—C23—H23B	109.5
C13—Fe3—S3	104.92 (14)	H23A—C23—H23B	109.5
C1—Fe3—S3	49.40 (8)	O23—C23—H23C	109.5
C15—Fe3—Fe4	162.26 (11)	H23A—C23—H23C	109.5
C14—Fe3—Fe4	80.50 (11)	H23B—C23—H23C	109.5
C13—Fe3—Fe4	104.56 (12)	O12—C12—Fe2	178.1 (3)
C1—Fe3—Fe4	70.56 (8)	O10—C10—Fe1	178.7 (3)
S3—Fe3—Fe4	54.51 (2)	O18—C18—H18A	109.5
C1—S2—Fe2	119.56 (9)	O18—C18—H18B	109.5
C1—S2—Fe1	112.28 (10)	H18A—C18—H18B	109.5
Fe2—S2—Fe1	71.06 (2)	O18—C18—H18C	109.5
C1—S2—Fe4	85.30 (9)	H18A—C18—H18C	109.5
Fe2—S2—Fe4	129.66 (3)	H18B—C18—H18C	109.5
Fe1—S2—Fe4	142.92 (3)	O20—C20—H20A	109.5
C3—S1—Fe2	113.33 (10)	O20—C20—H20B	109.5
C3—S1—Fe1	112.88 (10)	H20A—C20—H20B	109.5
Fe2—S1—Fe1	69.60 (2)	O20—C20—H20C	109.5
O23—P2—O21	106.22 (14)	H20A—C20—H20C	109.5
O23—P2—O22	101.11 (13)	H20B—C20—H20C	109.5
O21—P2—O22	98.00 (13)	O21—C21—H21A	109.5
O23—P2—Fe4	112.55 (10)	O21—C21—H21B	109.5
O21—P2—Fe4	118.48 (9)	H21A—C21—H21B	109.5
O22—P2—Fe4	118.12 (9)	O21—C21—H21C	109.5
O18—P1—O19	106.94 (14)	H21A—C21—H21C	109.5
O18—P1—O20	99.33 (14)	H21B—C21—H21C	109.5
O19—P1—O20	97.45 (15)	C1—S3—Fe3	61.50 (9)
O18—P1—Fe2	115.74 (9)	C1—S3—Fe4	85.99 (9)
O19—P1—Fe2	117.48 (10)	Fe3—S3—Fe4	74.01 (3)