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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 9| Part 1| January 2024| x231083
https://doi.org/10.1107/S2414314623010830

Bis[1,3-bis­­(2,4,6-tri­methyl­phen­yl)imidazolium] bis­(μ-cis-1,2-di­phenyl­ethene-1,2-di­thiol­ato-κ2S,S′:κS)bis­­[(cis-1,2-di­phenyl­ethene-1,2-di­thiol­ato-κ2S,S′)iron(III)] di­methyl­formamide disolvate

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Jayaraman Selvakumara* and Kuppuswamy Arumugama

aDepartment of Chemistry, Wright State University, 3640 Colonel Glenn Hwy., Dayton, OH 45435, USA
*Correspondence e-mail: selvakumar.jayaraman@wright.edu

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 1 December 2023; accepted 18 December 2023; online 26 December 2023)

The mol­ecular structure of the solvated title salt, (C21H25N2)2[Fe2(C14H10S2)4]·2C3H7NO reveals that the anion is situated on a crystallographic inversion center in the triclinic space group P[\overline{1}]. The title compound crystallizes utilizing a network of weak π-stacking inter­actions of phenyl rings pertaining to the di­thiol­ene unit. Moreover, the acidic imidazolium H atoms [N—C(H)—N] display non-classical hydrogen-bonding inter­actions of the C—H⋯O type to the oxygen atoms of the N,N-dimethyl formamide solvent, and hydrogen atoms on the backbone of imidazolium rings display weak C—H⋯S inter­actions with the di­thiol­ene sulfur atoms.

CCDC reference: 2319850

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[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The iron bis­(di­thiol­ene) dimer, [Fe(S2C2Ph2)2]2 (Schrauzer et al., 1964[Schrauzer, G. N., Mayweg, V., Finck, H. W., Müller-Westerhoff, U. & Heinrich, W. (1964). Angew. Chem. Int. Ed. Engl. 3, 381.]), displays a rich electrochemistry and is generally characterized by two successive ligand-based reduction processes pertaining to the di­thiol­ene units (Patra et al., 2006[Patra, A. K., Bill, E., Bothe, E., Chlopek, K., Neese, F., Weyhermüller, T., Stobie, K., Ward, M. D., McCleverty, J. A. & Wieghardt, K. (2006). Inorg. Chem. 45, 7877-7890.]; Ray et al., 2005[Ray, K., Bill, E., Weyhermüller, T. & Wieghardt, K. (2005). J. Am. Chem. Soc. 127, 5641-5654.]; Yu et al., 2007[Yu, R., Arumugam, K., Manepalli, A., Tran, Y., Schmehl, R., Jacobsen, H. & Donahue, J. P. (2007). Inorg. Chem. 46, 5131-5133.]). Despite their facile redox processes, the solid-state structure of the chemically reduced species [Fe(S2C2Ph2)2]2− have not yet been reported. Recently, we reported several five-coordinate iron bis­(di­thiol­ene) complexes with N-heterocyclic carbene ligands [Fe(S2C2Ph2)2(NHC)] [NHC = 1,3-bis­(2,4,6-tri­methyl­phen­yl)imidazol-2-yl­idene; Selvakumar et al., 2021[Selvakumar, J., Simpson, S. M., Zurek, E. & Arumugam, K. (2021). Inorg. Chem. Front. 8, 59-71.]]. Under electrochemical conditions, these complexes undergo two successive one-electron reductions, with the first reduction being reversible whereas the second reduction is irreversible. This irreversibility is attributed to the cleavage of the coordination of the N-heterocyclic carbene ligand to the respective iron atom (Selvakumar et al., 2021[Selvakumar, J., Simpson, S. M., Zurek, E. & Arumugam, K. (2021). Inorg. Chem. Front. 8, 59-71.]). To isolate and study the solid-state structure of [Fe(S2C2Ph2)2NHC]−, we reduced the neutral complex [Fe(S2C2Ph2)2(NHC)] with a stoichiometric amount of cobaltocene. The reduction process resulted in the decomplexation of NHC and the formation of [Fe(S2C2Ph2)2]22– with two NHC[H] cations serving as counter-ions. Herein, we disclose the mol­ecular structure and solid-state structural characteristics of [Fe(S2C2Ph2)2]2[NHC[H]]2 (Fig. 1[link]).

[Figure 1]
Figure 1
The mol­ecular structure of the cations and the anion in the title compound, with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. The solvent molecule was omitted for clarity. Only one cation was observed in the asymmetric unit and the other was generated by the inversion center at (−x, −y, −z).

Since the reductions of the substrate complex are predom­inantly ligand-based (Patra et al., 2006[Patra, A. K., Bill, E., Bothe, E., Chlopek, K., Neese, F., Weyhermüller, T., Stobie, K., Ward, M. D., McCleverty, J. A. & Wieghardt, K. (2006). Inorg. Chem. 45, 7877-7890.]), the bis­(di­thiol­ene) unit of [(Fe(S2C2Ph2)2(NHC)] undergoes a conversion from thienyl radical monoanions (·S–C=C–S−) to fully reduced 1,2-ene-di­thiol­ate (−S–C=C–S−). The C—S bond lengths in the title compound [C1—S1 = 1.762 (2) Å, C2—S2 = 1.770 (3) Å, C3—S3 = 1.764 (2) Å, C4—S4 = 1.757 (2) Å] are in agreement with pure C—S single-bond lengths. The C1—C2 [1.353 (3) Å] and C3—C4 [1.352 (3) Å] bond lengths are consistent with a double-bond character. Hence, the inter­pretation of the ligands as 1,2-ene-di­thiol­ates is confirmed.

Analysis of the mol­ecular structure revealed no classical hydrogen bonds. However, the presence of non-classical hydrogen-bonding inter­actions involving C—H⋯O and C—H⋯S inter­actions (Fig. 2[link]) is observed. The C—H⋯O and C—H⋯S inter­actions are detailed in Table 1[link]. Moreover, the mol­ecules are also inter­connected by inter­molecular C⋯C inter­actions of the phenyl rings pertaining to the di­thiol­ene units (Fig. 3[link]). All these inter­actions combine to yield a tri-periodic mol­ecular structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C29—H29⋯O1 0.93 (1) 2.22 (1) 3.038 (3) 147 (1)
C30—H30⋯O1 0.93 (1) 2.77 (1) 3.593 (3) 148 (1)
C31—H31⋯S1 0.93 (1) 2.87 (1) 3.763 (3) 162 (1)
C49—H49⋯O1 0.96 (1) 2.59 (1) 3.529 (4) 167 (1)
[Figure 2]
Figure 2
Inter­molecular C—H⋯O and C—H⋯S inter­actions (dotted lines) in the title compound.
[Figure 3]
Figure 3
Inter­molecular C⋯C inter­actions of the phenyl rings (dotted lines) in the title compound.

A CSD structure search for the core [Fe(S2C2Ph2)2]22– revealed no hits. However, structurally similar compounds have been reported in the literature, viz. [Fe(S2C2(C6H4-p-OCH3)2)2]22− (Yu et al., 2007[Yu, R., Arumugam, K., Manepalli, A., Tran, Y., Schmehl, R., Jacobsen, H. & Donahue, J. P. (2007). Inorg. Chem. 46, 5131-5133.]), [Fe(S2C6H4)2]2− (Ray et al., 2005[Ray, K., Bill, E., Weyhermüller, T. & Wieghardt, K. (2005). J. Am. Chem. Soc. 127, 5641-5654.]), and [Fe(S2C6H3(o-CH2CH3))2]2− (Ray et al., 2005[Ray, K., Bill, E., Weyhermüller, T. & Wieghardt, K. (2005). J. Am. Chem. Soc. 127, 5641-5654.]). The Fe—S, C—S, and C—C bond lengths for [Fe(S2C2Ph2)2]2[NHC[H]]2 are in agreement with those in the reported compounds.

Synthesis and crystallization

Cobaltocene (Cp2Co) (3.8 mg, 0.02 mmol) in 1 ml of N,N-dimethyl formamide (DMF) was added dropwise to a stirred solution of [(Fe(S2C2Ph2)2(NHC)] (17 mg, 0.02 mmol; NHC = 1,3-dimesitylimidazol-2-yl­idene) in 2 ml of DMF. This addition induced a colour change of the solution from dark green to brown. After stirring 30 min at 25°C, the reaction mixture was filtered through a celite plug. The filtrate was subjected to vial in a vial for crystallization according to the vapour diffusion method. Brown plate-like shaped crystals of the title compound [(Fe(S2C2Ph2)2)2][NHC(H)]2 were obtained by diffusion of toluene into the brown reaction mixture containing DMF as the solvent (yield: 11 mg, 60%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula (C21H25N2)2[Fe2(C14H10S82)4]·2C3H7NO
Mr 919.12
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 100
a, b, c (Å) 12.4019 (14), 14.8205 (19), 14.9762 (18)
α, β, γ (°) 105.936 (4), 113.662 (3), 94.486 (4)
V (Å3) 2368.2 (5)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.54
Crystal size (mm) 0.57 × 0.28 × 0.2
 
Data collection
Diffractometer Bruker APEXII CCD
No. of measured, independent and observed [I ≥ 2u(I)] reflections 45150, 8282, 6984
Rint 0.054
(sin θ/λ)max (Å−1) 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.090, 1.07
No. of reflections 8282
No. of parameters 558
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.54, −0.40
Computer programs: APEX2 and SAINT (Bruker, 2014[Bruker (2014). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]), OLEX2.solve and OLEX2.refine (Bourhis et al., 2015[Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59-75.]), and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Structural data

CCDC reference: 2319850

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623010830/im4022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623010830/im4022Isup2.hkl

checkCIF report


Computing details top

Bis[1,3-bis(2,4,6-trimethylphenyl)imidazolium] bis(µ-cis-1,2-diphenylethene-1,2-dithiolato-κ2S,S':κS)bis[(cis-1,2-diphenylethene-1,2-dithiolato-κ2S,S')iron(III)] dimethylformamide disolvate top
Crystal data top
(C21H25N2)2[Fe2(C14H10S82)4]·2C3H7NOZ = 2
Mr = 919.12F(000) = 967.9950
Triclinic, P1Dx = 1.289 Mg m−3
a = 12.4019 (14) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.8205 (19) ÅCell parameters from 9889 reflections
c = 14.9762 (18) Åθ = 2.5–24.9°
α = 105.936 (4)°µ = 0.54 mm−1
β = 113.662 (3)°T = 100 K
γ = 94.486 (4)°Prism, black
V = 2368.2 (5) Å30.57 × 0.28 × 0.2 mm
Data collection top
Bruker APEXII CCD
diffractometer		Rint = 0.054
Graphite monochromatorθmax = 25.0°, θmin = 2.8°
φ and ω scansh = −14→14
45150 measured reflectionsk = −17→17
8282 independent reflectionsl = −17→17
6984 reflections with I ≥ 2u(I)
Refinement top
Refinement on F20 restraints
Least-squares matrix: full88 constraints
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0383P)2 + 1.4785P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
8282 reflectionsΔρmax = 0.54 e Å−3
558 parametersΔρmin = −0.40 e Å−3
Special details top

Refinement. Aromatic C–H H atoms were added using the riding-model approximation with C–H bond lengths of 0.95 Å with Uiso (H) = 1.2 Ueq(CarH). Methyl (CH3) H atoms were treated as a rotating group and added using the riding-model approximation to the carbon atom to which they are attached. Methyl H atoms were fixed at a distance of 0.98 Å with Uiso (H) = 1.5 Ueq(CH3). The title compound co-crystallized with one solvent molecule (N, N-dimethyl formamide) per asymmetric unit of the unit cell.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.62110 (3)0.564448 (19)0.55925 (2)0.01723 (9)
N1−0.17750 (16)−0.23003 (12)−0.57291 (14)0.0258 (4)
S20.47668 (4)0.56334 (3)0.40931 (4)0.01803 (12)
S10.70483 (4)0.47741 (3)0.46806 (4)0.01933 (12)
S30.57529 (4)0.69570 (3)0.63988 (4)0.01979 (12)
S40.80666 (5)0.61643 (4)0.68790 (4)0.02292 (12)
O10.89705 (16)0.04702 (13)0.41971 (15)0.0425 (4)
C32−0.12009 (19)−0.28038 (14)−0.63316 (17)0.0250 (5)
C41−0.2576 (2)−0.02146 (15)−0.45253 (18)0.0272 (5)
N30.76879 (17)0.14028 (13)0.35900 (15)0.0304 (4)
C29−0.16751 (19)−0.13524 (15)−0.54035 (17)0.0256 (5)
H29−0.12006 (19)−0.09024 (15)−0.54958 (17)0.0307 (6)*
C31−0.2557 (2)−0.27257 (17)−0.5440 (2)0.0356 (6)
H31−0.2783 (2)−0.33792 (17)−0.5570 (2)0.0428 (7)*
C30−0.2928 (2)−0.20136 (17)−0.4936 (2)0.0381 (6)
H30−0.3458 (2)−0.20830 (17)−0.4650 (2)0.0458 (7)*
C510.7468 (3)0.0959 (2)0.2527 (2)0.0532 (8)
H51a0.7881 (16)0.1389 (6)0.2334 (5)0.0799 (11)*
H51b0.7758 (17)0.0374 (8)0.2456 (4)0.0799 (11)*
H51c0.6618 (3)0.0819 (14)0.2086 (3)0.0799 (11)*
C280.7159 (2)0.83634 (16)0.93701 (17)0.0301 (5)
H280.7528 (2)0.78961 (16)0.96034 (17)0.0362 (6)*
C47−0.4322 (2)−0.0556 (2)−0.6289 (2)0.0439 (6)
H47a−0.5065 (8)−0.0346 (9)−0.6550 (5)0.0658 (10)*
H47b−0.3904 (7)−0.0505 (11)−0.6697 (3)0.0658 (10)*
H47c−0.4488 (14)−0.1212 (3)−0.6326 (3)0.0658 (10)*
C201.1390 (2)0.83725 (18)1.05341 (17)0.0335 (6)
H201.2120 (2)0.86338 (18)1.11234 (17)0.0402 (7)*
C30.70124 (19)0.75091 (14)0.76107 (15)0.0216 (4)
C38−0.2435 (3)−0.2183 (2)−0.7778 (2)0.0441 (7)
H38a−0.3109 (8)−0.2294 (11)−0.7631 (13)0.0662 (10)*
H38b−0.2070 (5)−0.1510 (2)−0.7483 (11)0.0662 (10)*
H38c−0.2706 (13)−0.2388 (10)−0.8514 (3)0.0662 (10)*
C46−0.1792 (2)0.03704 (17)−0.35228 (18)0.0311 (5)
C20.52106 (18)0.50821 (14)0.31254 (15)0.0186 (4)
C60.7759 (2)0.41881 (16)0.28058 (17)0.0270 (5)
H60.8338 (2)0.46730 (16)0.33885 (17)0.0324 (6)*
C120.5064 (2)0.55707 (18)0.16129 (18)0.0341 (5)
H120.5901 (2)0.57460 (18)0.19153 (18)0.0409 (7)*
C42−0.3549 (2)0.00652 (17)−0.51813 (19)0.0307 (5)
C400.0357 (3)−0.43837 (19)−0.8171 (2)0.0436 (7)
H40a0.1087 (9)−0.4529 (12)−0.7738 (2)0.0654 (10)*
H40b−0.0216 (7)−0.4971 (6)−0.8638 (10)0.0654 (10)*
H40c0.0528 (16)−0.4022 (6)−0.8559 (11)0.0654 (10)*
C40.80308 (19)0.71629 (14)0.78183 (15)0.0220 (4)
C48−0.3211 (3)0.2570 (2)−0.3390 (3)0.0611 (9)
H48a−0.2748 (16)0.3033 (3)−0.3510 (16)0.0917 (14)*
H48b−0.4052 (5)0.2563 (5)−0.3746 (13)0.0917 (14)*
H48c−0.2977 (19)0.2740 (7)−0.2661 (4)0.0917 (14)*
C45−0.2011 (2)0.12767 (17)−0.31768 (19)0.0364 (6)
H45−0.1490 (2)0.16899 (17)−0.25154 (19)0.0437 (7)*
C340.0128 (2)−0.38324 (16)−0.65194 (18)0.0294 (5)
H340.0680 (2)−0.41932 (16)−0.62582 (18)0.0353 (6)*
C130.4389 (3)0.5702 (2)0.0680 (2)0.0465 (7)
H130.4776 (3)0.5968 (2)0.0364 (2)0.0559 (8)*
C50.65553 (19)0.40751 (14)0.26261 (15)0.0205 (4)
C10.61786 (18)0.46720 (14)0.33805 (15)0.0190 (4)
C36−0.0978 (2)−0.32501 (17)−0.78864 (18)0.0341 (5)
H36−0.1167 (2)−0.32200 (17)−0.85432 (18)0.0409 (7)*
C39−0.0080 (2)−0.34176 (17)−0.48534 (18)0.0333 (5)
H39a0.0048 (14)−0.2794 (3)−0.4369 (3)0.0499 (8)*
H39b−0.0732 (7)−0.3844 (9)−0.4890 (3)0.0499 (8)*
H39c0.0640 (8)−0.3664 (11)−0.4630 (6)0.0499 (8)*
N2−0.23739 (17)−0.11610 (13)−0.49220 (15)0.0277 (4)
C43−0.3738 (2)0.09706 (17)−0.4782 (2)0.0364 (6)
H43−0.4391 (2)0.11715 (17)−0.5195 (2)0.0437 (7)*
C220.9777 (2)0.70262 (16)0.93387 (17)0.0283 (5)
H220.9432 (2)0.63787 (16)0.91280 (17)0.0339 (6)*
C191.0825 (2)0.89456 (17)0.99812 (18)0.0351 (6)
H191.1177 (2)0.95922 (17)1.01954 (18)0.0421 (7)*
C44−0.2983 (2)0.15838 (17)−0.3789 (2)0.0375 (6)
C160.3247 (2)0.49265 (18)0.16272 (18)0.0330 (5)
H160.2850 (2)0.46698 (18)0.19417 (18)0.0396 (6)*
C100.5705 (2)0.33425 (15)0.17443 (16)0.0270 (5)
H100.4896 (2)0.32567 (15)0.16071 (16)0.0324 (6)*
C211.0869 (2)0.74125 (18)1.02099 (18)0.0337 (5)
H211.1251 (2)0.70247 (18)1.05773 (18)0.0405 (6)*
C260.6386 (2)0.97932 (17)0.97090 (19)0.0375 (6)
H260.6234 (2)1.02789 (17)1.01591 (19)0.0451 (7)*
C170.91867 (19)0.75881 (15)0.87719 (15)0.0233 (5)
C35−0.0160 (2)−0.38001 (16)−0.75048 (18)0.0310 (5)
C250.6059 (2)0.97638 (16)0.87041 (18)0.0336 (6)
H250.5689 (2)1.02335 (16)0.84773 (18)0.0404 (7)*
C90.6060 (2)0.27418 (17)0.10719 (18)0.0355 (6)
H90.5487 (2)0.22552 (17)0.04871 (18)0.0426 (7)*
C230.68333 (18)0.83176 (14)0.83491 (16)0.0226 (5)
C240.62802 (19)0.90339 (15)0.80279 (17)0.0280 (5)
H240.60569 (19)0.90222 (15)0.73525 (17)0.0336 (6)*
C180.9734 (2)0.85541 (16)0.91072 (17)0.0301 (5)
H180.9360 (2)0.89431 (16)0.87377 (17)0.0361 (6)*
C520.7088 (2)0.21868 (18)0.3806 (2)0.0417 (6)
H52a0.7356 (12)0.2458 (9)0.4539 (2)0.0625 (10)*
H52b0.7282 (13)0.2673 (6)0.3550 (13)0.0625 (10)*
H52c0.6232 (2)0.1945 (3)0.3471 (12)0.0625 (10)*
C150.2587 (2)0.5054 (2)0.06950 (19)0.0442 (7)
H150.1751 (2)0.4874 (2)0.03849 (19)0.0531 (8)*
C270.6942 (2)0.90956 (17)1.00431 (19)0.0372 (6)
H270.7172 (2)0.91171 (17)1.07223 (19)0.0446 (7)*
C49−0.0740 (3)0.0049 (2)−0.2849 (2)0.0490 (7)
H49a−0.0160 (9)0.0002 (14)−0.3123 (9)0.0735 (11)*
H49b−0.0375 (11)0.0506 (8)−0.2160 (4)0.0735 (11)*
H49c−0.1014 (4)−0.0568 (7)−0.2832 (12)0.0735 (11)*
C70.8108 (2)0.35869 (18)0.21271 (19)0.0349 (6)
H70.8914 (2)0.36738 (18)0.22544 (19)0.0419 (7)*
C80.7261 (3)0.28626 (18)0.12664 (19)0.0390 (6)
H80.7495 (3)0.24550 (18)0.08161 (19)0.0468 (7)*
C500.8429 (2)0.11203 (16)0.43295 (19)0.0298 (5)
H500.8552 (2)0.14359 (16)0.50027 (19)0.0358 (6)*
C140.3151 (3)0.5444 (2)0.0218 (2)0.0477 (7)
H140.2700 (3)0.5532 (2)−0.0407 (2)0.0572 (8)*
C110.4498 (2)0.51773 (15)0.21005 (16)0.0233 (5)
C33−0.03867 (19)−0.33393 (15)−0.59061 (17)0.0257 (5)
C37−0.1518 (2)−0.27453 (16)−0.73156 (18)0.0295 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.01874 (16)0.01510 (15)0.01784 (15)0.00388 (11)0.01013 (12)0.00228 (11)
N10.0266 (10)0.0184 (9)0.0361 (10)0.0042 (7)0.0188 (9)0.0071 (8)
S20.0202 (3)0.0168 (2)0.0188 (2)0.00595 (19)0.0109 (2)0.00447 (19)
S10.0201 (3)0.0190 (2)0.0193 (2)0.0066 (2)0.0107 (2)0.00334 (19)
S30.0192 (3)0.0172 (2)0.0204 (2)0.0046 (2)0.0095 (2)0.00126 (19)
S40.0200 (3)0.0211 (3)0.0221 (3)0.0055 (2)0.0088 (2)−0.0005 (2)
O10.0375 (10)0.0379 (10)0.0721 (13)0.0193 (8)0.0321 (10)0.0327 (9)
C320.0252 (11)0.0165 (10)0.0333 (12)0.0024 (9)0.0168 (10)0.0030 (9)
C410.0343 (13)0.0220 (11)0.0382 (13)0.0103 (9)0.0264 (11)0.0123 (10)
N30.0292 (10)0.0255 (10)0.0377 (11)0.0095 (8)0.0142 (9)0.0121 (8)
C290.0265 (12)0.0206 (11)0.0348 (12)0.0048 (9)0.0185 (10)0.0093 (9)
C310.0407 (14)0.0218 (12)0.0572 (16)0.0049 (10)0.0332 (13)0.0147 (11)
C300.0466 (15)0.0269 (12)0.0603 (16)0.0087 (11)0.0397 (14)0.0183 (12)
C510.063 (2)0.0543 (18)0.0410 (15)0.0170 (15)0.0214 (15)0.0153 (13)
C280.0368 (13)0.0245 (11)0.0301 (12)0.0055 (10)0.0190 (11)0.0045 (9)
C470.0357 (15)0.0482 (16)0.0436 (15)0.0071 (12)0.0162 (12)0.0117 (13)
C200.0230 (12)0.0403 (14)0.0251 (11)−0.0008 (10)0.0074 (10)0.0003 (10)
C30.0236 (11)0.0184 (10)0.0200 (10)0.0014 (8)0.0104 (9)0.0021 (8)
C380.0530 (17)0.0453 (16)0.0445 (15)0.0284 (14)0.0245 (13)0.0209 (13)
C460.0387 (14)0.0327 (12)0.0341 (12)0.0147 (11)0.0251 (11)0.0133 (10)
C20.0207 (11)0.0162 (10)0.0196 (10)0.0026 (8)0.0118 (8)0.0027 (8)
C60.0289 (12)0.0257 (11)0.0306 (12)0.0055 (9)0.0183 (10)0.0076 (9)
C120.0364 (14)0.0402 (14)0.0336 (13)0.0087 (11)0.0197 (11)0.0174 (11)
C420.0294 (12)0.0303 (12)0.0399 (13)0.0063 (10)0.0208 (11)0.0142 (10)
C400.0511 (17)0.0403 (15)0.0477 (16)0.0212 (13)0.0301 (14)0.0113 (12)
C40.0250 (11)0.0169 (10)0.0222 (10)0.0032 (8)0.0112 (9)0.0031 (8)
C480.060 (2)0.0322 (15)0.093 (3)0.0219 (14)0.0407 (19)0.0109 (15)
C450.0407 (14)0.0328 (13)0.0369 (13)0.0092 (11)0.0227 (12)0.0044 (11)
C340.0239 (12)0.0237 (11)0.0402 (13)0.0070 (9)0.0138 (10)0.0100 (10)
C130.0589 (19)0.0588 (18)0.0403 (15)0.0160 (15)0.0301 (14)0.0301 (13)
C50.0273 (11)0.0190 (10)0.0214 (10)0.0079 (9)0.0152 (9)0.0081 (8)
C10.0231 (11)0.0162 (10)0.0183 (10)0.0020 (8)0.0121 (9)0.0029 (8)
C360.0438 (15)0.0310 (12)0.0313 (12)0.0124 (11)0.0205 (11)0.0090 (10)
C390.0302 (13)0.0319 (13)0.0360 (13)0.0041 (10)0.0134 (11)0.0114 (10)
N20.0329 (11)0.0214 (9)0.0383 (11)0.0080 (8)0.0243 (9)0.0103 (8)
C430.0311 (13)0.0354 (13)0.0552 (16)0.0168 (11)0.0243 (12)0.0229 (12)
C220.0297 (12)0.0213 (11)0.0274 (11)0.0031 (9)0.0109 (10)0.0020 (9)
C190.0301 (13)0.0262 (12)0.0379 (13)−0.0041 (10)0.0130 (11)0.0006 (10)
C440.0416 (15)0.0259 (12)0.0557 (16)0.0133 (11)0.0307 (13)0.0135 (11)
C160.0303 (13)0.0434 (14)0.0302 (12)0.0110 (11)0.0152 (10)0.0157 (11)
C100.0320 (13)0.0243 (11)0.0249 (11)0.0058 (9)0.0151 (10)0.0048 (9)
C210.0316 (13)0.0378 (13)0.0288 (12)0.0089 (11)0.0103 (10)0.0111 (10)
C260.0376 (14)0.0305 (13)0.0391 (14)0.0056 (11)0.0233 (12)−0.0057 (11)
C170.0219 (11)0.0242 (11)0.0216 (10)0.0036 (9)0.0127 (9)−0.0002 (9)
C350.0319 (13)0.0240 (11)0.0375 (13)0.0083 (10)0.0186 (11)0.0055 (10)
C250.0280 (12)0.0238 (12)0.0385 (13)0.0075 (10)0.0119 (11)−0.0016 (10)
C90.0497 (16)0.0278 (12)0.0263 (12)0.0069 (11)0.0201 (11)0.0005 (10)
C230.0188 (11)0.0170 (10)0.0262 (11)−0.0010 (8)0.0112 (9)−0.0021 (8)
C240.0241 (12)0.0237 (11)0.0270 (11)0.0040 (9)0.0085 (10)−0.0002 (9)
C180.0290 (12)0.0244 (12)0.0317 (12)0.0033 (9)0.0113 (10)0.0057 (10)
C520.0362 (14)0.0315 (13)0.0637 (18)0.0177 (11)0.0236 (13)0.0201 (13)
C150.0338 (14)0.0660 (18)0.0303 (13)0.0144 (13)0.0084 (11)0.0200 (13)
C270.0472 (15)0.0333 (13)0.0296 (12)0.0049 (11)0.0224 (12)0.0010 (10)
C490.0555 (18)0.0579 (18)0.0389 (15)0.0297 (15)0.0214 (14)0.0184 (13)
C70.0389 (14)0.0393 (14)0.0459 (14)0.0170 (11)0.0329 (12)0.0187 (12)
C80.0612 (18)0.0340 (13)0.0395 (14)0.0207 (12)0.0386 (13)0.0106 (11)
C500.0238 (12)0.0261 (12)0.0441 (14)0.0026 (10)0.0171 (11)0.0158 (10)
C140.0560 (18)0.0659 (19)0.0278 (13)0.0238 (15)0.0167 (13)0.0256 (13)
C110.0306 (12)0.0212 (10)0.0210 (10)0.0091 (9)0.0146 (9)0.0053 (8)
C330.0231 (11)0.0181 (10)0.0342 (12)0.0012 (9)0.0125 (10)0.0071 (9)
C370.0311 (13)0.0224 (11)0.0366 (13)0.0102 (9)0.0160 (10)0.0093 (10)
Geometric parameters (Å, º) top
Fe1—Fe1i2.9636 (6)C40—C351.510 (3)
Fe1—S2i2.4224 (6)C4—C171.488 (3)
Fe1—S22.2355 (6)C48—H48a0.9600
Fe1—S12.2334 (6)C48—H48b0.9600
Fe1—S32.2357 (6)C48—H48c0.9600
Fe1—S42.2249 (6)C48—C441.515 (3)
N1—C321.452 (3)C45—H450.9300
N1—C291.332 (3)C45—C441.389 (4)
N1—C311.384 (3)C34—H340.9300
S2—C21.7695 (19)C34—C351.388 (3)
S1—C11.762 (2)C34—C331.400 (3)
S3—C31.764 (2)C13—H130.9300
S4—C41.757 (2)C13—C141.376 (4)
O1—C501.234 (3)C5—C11.489 (3)
C32—C331.394 (3)C5—C101.397 (3)
C32—C371.394 (3)C36—H360.9300
C41—C461.390 (3)C36—C351.392 (3)
C41—C421.394 (3)C36—C371.388 (3)
C41—N21.449 (3)C39—H39a0.9600
N3—C511.445 (3)C39—H39b0.9600
N3—C521.459 (3)C39—H39c0.9600
N3—C501.321 (3)C39—C331.507 (3)
C29—H290.9300C43—H430.9300
C29—N21.334 (3)C43—C441.386 (4)
C31—H310.9300C22—H220.9300
C31—C301.347 (3)C22—C211.383 (3)
C30—H300.9300C22—C171.391 (3)
C30—N21.381 (3)C19—H190.9300
C51—H51a0.9600C19—C181.386 (3)
C51—H51b0.9600C16—H160.9300
C51—H51c0.9600C16—C151.381 (3)
C28—H280.9300C16—C111.388 (3)
C28—C231.396 (3)C10—H100.9300
C28—C271.389 (3)C10—C91.387 (3)
C47—H47a0.9600C21—H210.9300
C47—H47b0.9600C26—H260.9300
C47—H47c0.9600C26—C251.379 (4)
C47—C421.505 (3)C26—C271.383 (4)
C20—H200.9300C17—C181.394 (3)
C20—C191.383 (4)C25—H250.9300
C20—C211.380 (3)C25—C241.392 (3)
C3—C41.352 (3)C9—H90.9300
C3—C231.490 (3)C9—C81.385 (4)
C38—H38a0.9600C23—C241.399 (3)
C38—H38b0.9600C24—H240.9300
C38—H38c0.9600C18—H180.9300
C38—C371.517 (3)C52—H52a0.9600
C46—C451.391 (3)C52—H52b0.9600
C46—C491.501 (4)C52—H52c0.9600
C2—C11.353 (3)C15—H150.9300
C2—C111.485 (3)C15—C141.377 (4)
C6—H60.9300C27—H270.9300
C6—C51.394 (3)C49—H49a0.9600
C6—C71.389 (3)C49—H49b0.9600
C12—H120.9300C49—H49c0.9600
C12—C131.389 (3)C7—H70.9300
C12—C111.396 (3)C7—C81.376 (4)
C42—C431.390 (3)C8—H80.9300
C40—H40a0.9600C50—H500.9300
C40—H40b0.9600C14—H140.9300
C40—H40c0.9600
S1—Fe1—S2i98.85 (2)C10—C5—C6118.36 (19)
S1—Fe1—S287.69 (2)C10—C5—C1119.97 (19)
S3—Fe1—S288.78 (2)C2—C1—S1119.93 (15)
S3—Fe1—S2i103.39 (2)C5—C1—S1115.20 (15)
S3—Fe1—S1157.74 (2)C5—C1—C2124.79 (18)
S4—Fe1—S2152.39 (2)C35—C36—H36119.02 (14)
S4—Fe1—S2i106.42 (2)C37—C36—H36119.02 (14)
S4—Fe1—S185.80 (2)C37—C36—C35122.0 (2)
S4—Fe1—S387.22 (2)H39b—C39—H39a109.5
C29—N1—C32125.31 (18)H39c—C39—H39a109.5
C31—N1—C32125.76 (18)H39c—C39—H39b109.5
C31—N1—C29108.87 (18)C33—C39—H39a109.5
C2—S2—Fe1i107.03 (7)C33—C39—H39b109.5
C2—S2—Fe1106.33 (7)C33—C39—H39c109.5
C1—S1—Fe1106.41 (7)C29—N2—C41124.67 (18)
C3—S3—Fe1106.36 (7)C30—N2—C41126.34 (18)
C4—S4—Fe1106.94 (7)C30—N2—C29108.84 (18)
C33—C32—N1118.2 (2)H43—C43—C42118.91 (15)
C37—C32—N1118.17 (19)C44—C43—C42122.2 (2)
C37—C32—C33123.6 (2)C44—C43—H43118.91 (14)
C42—C41—C46123.3 (2)C21—C22—H22119.38 (14)
N2—C41—C46118.9 (2)C17—C22—H22119.38 (12)
N2—C41—C42117.8 (2)C17—C22—C21121.2 (2)
C52—N3—C51117.2 (2)H19—C19—C20120.08 (13)
C50—N3—C51120.7 (2)C18—C19—C20119.8 (2)
C50—N3—C52122.1 (2)C18—C19—H19120.08 (14)
H29—C29—N1125.93 (12)C45—C44—C48121.1 (2)
N2—C29—N1108.13 (18)C43—C44—C48120.4 (2)
N2—C29—H29125.93 (12)C43—C44—C45118.5 (2)
H31—C31—N1126.51 (12)C15—C16—H16119.62 (16)
C30—C31—N1107.0 (2)C11—C16—H16119.62 (13)
C30—C31—H31126.51 (14)C11—C16—C15120.8 (2)
H30—C30—C31126.41 (14)H10—C10—C5119.80 (12)
N2—C30—C31107.2 (2)C9—C10—C5120.4 (2)
N2—C30—H30126.41 (12)C9—C10—H10119.80 (14)
H51a—C51—N3109.5C22—C21—C20120.0 (2)
H51b—C51—N3109.5H21—C21—C20119.98 (14)
H51b—C51—H51a109.5H21—C21—C22119.98 (14)
H51c—C51—N3109.5C25—C26—H26120.21 (14)
H51c—C51—H51a109.5C27—C26—H26120.21 (14)
H51c—C51—H51b109.5C27—C26—C25119.6 (2)
C23—C28—H28119.47 (13)C22—C17—C4121.03 (19)
C27—C28—H28119.47 (15)C18—C17—C4121.1 (2)
C27—C28—C23121.1 (2)C18—C17—C22117.8 (2)
H47b—C47—H47a109.5C34—C35—C40120.8 (2)
H47c—C47—H47a109.5C36—C35—C40120.5 (2)
H47c—C47—H47b109.5C36—C35—C34118.6 (2)
C42—C47—H47a109.5H25—C25—C26119.87 (14)
C42—C47—H47b109.5C24—C25—C26120.3 (2)
C42—C47—H47c109.5C24—C25—H25119.87 (15)
C19—C20—H20120.06 (13)H9—C9—C10119.81 (14)
C21—C20—H20120.06 (14)C8—C9—C10120.4 (2)
C21—C20—C19119.9 (2)C8—C9—H9119.81 (13)
C4—C3—S3119.37 (15)C3—C23—C28121.3 (2)
C23—C3—S3115.50 (15)C24—C23—C28117.72 (19)
C23—C3—C4125.09 (18)C24—C23—C3120.96 (19)
H38b—C38—H38a109.5C23—C24—C25121.0 (2)
H38c—C38—H38a109.5H24—C24—C25119.50 (15)
H38c—C38—H38b109.5H24—C24—C23119.50 (12)
C37—C38—H38a109.5C17—C18—C19121.2 (2)
C37—C38—H38b109.5H18—C18—C19119.40 (14)
C37—C38—H38c109.5H18—C18—C17119.40 (13)
C45—C46—C41117.0 (2)H52a—C52—N3109.5
C49—C46—C41121.6 (2)H52b—C52—N3109.5
C49—C46—C45121.3 (2)H52b—C52—H52a109.5
C1—C2—S2119.10 (15)H52c—C52—N3109.5
C11—C2—S2114.65 (14)H52c—C52—H52a109.5
C11—C2—C1126.13 (18)H52c—C52—H52b109.5
C5—C6—H6119.52 (12)H15—C15—C16119.55 (16)
C7—C6—H6119.52 (14)C14—C15—C16120.9 (3)
C7—C6—C5121.0 (2)C14—C15—H15119.55 (16)
C13—C12—H12119.74 (16)C26—C27—C28120.4 (2)
C11—C12—H12119.74 (14)H27—C27—C28119.81 (15)
C11—C12—C13120.5 (2)H27—C27—C26119.81 (14)
C47—C42—C41121.9 (2)H49a—C49—C46109.5
C43—C42—C41116.9 (2)H49b—C49—C46109.5
C43—C42—C47121.2 (2)H49b—C49—H49a109.5
H40b—C40—H40a109.5H49c—C49—C46109.5
H40c—C40—H40a109.5H49c—C49—H49a109.5
H40c—C40—H40b109.5H49c—C49—H49b109.5
C35—C40—H40a109.5H7—C7—C6120.00 (14)
C35—C40—H40b109.5C8—C7—C6120.0 (2)
C35—C40—H40c109.5C8—C7—H7120.00 (14)
C3—C4—S4119.26 (15)C7—C8—C9119.9 (2)
C17—C4—S4115.04 (15)H8—C8—C9120.05 (13)
C17—C4—C3125.60 (18)H8—C8—C7120.05 (14)
H48b—C48—H48a109.5N3—C50—O1125.1 (2)
H48c—C48—H48a109.5H50—C50—O1117.45 (15)
H48c—C48—H48b109.5H50—C50—N3117.45 (14)
C44—C48—H48a109.5C15—C14—C13119.1 (2)
C44—C48—H48b109.5H14—C14—C13120.43 (15)
C44—C48—H48c109.5H14—C14—C15120.43 (16)
H45—C45—C46118.98 (15)C12—C11—C2120.8 (2)
C44—C45—C46122.0 (2)C16—C11—C2121.00 (19)
C44—C45—H45118.98 (14)C16—C11—C12118.1 (2)
C35—C34—H34118.95 (13)C34—C33—C32116.6 (2)
C33—C34—H34118.95 (13)C39—C33—C32122.9 (2)
C33—C34—C35122.1 (2)C39—C33—C34120.5 (2)
H13—C13—C12119.71 (16)C38—C37—C32122.8 (2)
C14—C13—C12120.6 (2)C36—C37—C32117.1 (2)
C14—C13—H13119.71 (15)C36—C37—C38120.0 (2)
C1—C5—C6121.56 (18)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C29—H29···O10.93 (1)2.22 (1)3.038 (3)147 (1)
C30—H30···O10.93 (1)2.77 (1)3.593 (3)148 (1)
C31—H31···S10.93 (1)2.87 (1)3.763 (3)162 (1)
C49—H49···O10.96 (1)2.59 (1)3.529 (4)167 (1)
 

Acknowledgements

The authors like to acknowledge support by funds from the Chemistry Department, Wright State University, College of Science and Mathematics. The authors would also like to acknowledge Dr Grossie, Wright State University, for help with low-temperature data X-ray diffraction collection.

Funding information

Funding for this research was provided by: American Chemical Society Petroleum Research Fund (grant No. 59893UR7 to Kuppuswamy Arumugam); National Institutes of Health, National Cancer Institute (grant No. CA232765 to Kuppuswamy Arumugam).

References

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