New isostructural transition metal complexes with a non-innocent di­thiol­ate ligand

Three new complexes with 3,6-di­chloro­benzene-1,2-di­thiol (bdtCl₂), namely methyl­tri­phenyl­phospho­nium bis­(3,6-di­chloro­benzene-1,2-di­thiol­ato-κ²S,S′)cobaltate(1−), (C₁₉H₁₈P)[Co(C₆H₂Cl₂S₂)₂], (I), bis­(methyl­tri­phenyl­phospho­nium) bis­(3,6-di­chloro­benzene-1,2-di­thiol­ato-κ²S,S′)cuprate(2−) di­methyl sulfoxide disolvate, (C₁₉H₁₈P)₂[Cu(C₆H₂Cl₂S₂)₂]·2C₂H₆OS, (II), and methyl­tri­phenyl­phospho­nium bis­(3,6-di­chloro­benzene-1,2-di­thiol­ato-κ²S,S′)cuprate(1−), (C₁₉H₁₈P)[Cu(C₆H₂Cl₂S₂)₂], (III), have been synthesized and characterized by single-crystal X-ray diffraction. The X-ray structure analyses of all three complexes confirm that the four donor S atoms form a slightly distorted square-planar coordination arrangement around the central metal atom. An inter­esting finding for both the Cu^II and Cu^III complexes, i.e. (II) and (III), respectively, is that the coordination polyhedra are principally the same and differ only slightly with respect to the inter­atomic distances.

S1. Introduction

In recent years, di­thiol­ate complexes have attracted considerable inter­est because of their technical applications as superconductors (Zou et al., 1997; Cassoux et al., 1991), pesticides (Szolnai, 1975; Geiger & Minest, 1975; Khajuria et al., 2013), resins and Q-switching dyes for IR spectroscopy (Bigoli et al., 1997; Drexhage & Mueller-Westerhoff, 1972; Yang et al., 2013), compounds with unusual magnetic properties (Coomber et al., 1996; Boudreaux & Mulay, 1976; Cerdeira et al., 2008; Cerdeira et al., 2012) and biocatalysts (Lancaster, 1988; Sellmann et al., 1996). The wide range of technical and biological applications can be attributed to the oxidation–reduction properties of di­thiol­ate ligands. Such ligands are known as non-innocent ligands (Jörgensen, 1966; Stiefel & Karlin, 2004) and are ligands which undergo π-bonding with the metal (e.g. CO, olefins and carbenes). Some of them even have an extended π-delocalized system [e.g. cyclo­penta­dienyl (Cp) derivatives, multi-enes and multi-enyls] and are thus capable of undergoing easy charge and spin delocalization upon oxidation or reduction of the complex. Therefore, they are by definition suspect, as they can be easily oxidized or reduced instead of the metal to which they coordinate (Jörgensen, 1966). Among the consequences of this concept in the field of coordination chemistry is the occurrence of situations in which the assignment of the oxidation state of the central metal atom is difficult, because the ligands can also undergo electron transfer and thus the `ligand oxidation state' changes. Such ligands may occur in several redox forms, e.g. O₂/O₂^.-/O₂^2- or NO⁺/NO^./NO^- or di­thiol­ate and other (e.g. Kaim & Schwederski, 2010).

Recently (Walla et al., 1998; Kameníček et al., 2001, 2002; Kameníček & Mrkvová, 2003; Mrkvová et al., 2004), similar complexes of the general formula R[M(di­thiole)₂], where di­thiole is 1-toluene-3,4-di­thiole (tdt), benzene-1,2-di­thiole (bdt), ethane-1,2-di­thiole (ed) and maleo­nitrile-1,2-di­thiole (mnt), M is Ni, Co and Cu, and R is Me₄N, Et₄N, Pr₄N, Me₃PhN, MePh₃P and Ph₄P, have been studied.

The aim of the present work was to prepare analogous complexes with different transition metals as the central atom. A comparison of the geometrical parameters of two compounds with the same formal oxidation state, i.e. (MePh₃P)[Co^III(bdt)₂], (I), and (MePh₃P)[Cu^III(bdt)₂], (III), and of two compounds with the central Cu atom in different formal oxidation states, i.e. (MePh₃P)₂[Cu^II(bdt)₂].2Me₂SO, (II), and (III), are discussed. The redox properties of these complexes have been discussed recently (Machata et al., 2014) and it was shown that electrochemical reduction takes place predominantly on the central atom and electrochemical oxidation takes place both on the central atom and on the ligand also.

S2. Experimental

S2.1. Materials

The following reagents (Sigma–Aldrich) were used for the syntheses of complexes (I)–(III): CoCl₂·6H₂O ≥ 98%; CuCl₂·2H₂O ≥ 98%; 3,6-di­chloro­benzene-1,2-di­thiole (bdtCl₂) ≥ 95%; methyl­tri­phenyl­phospho­nium bromide (Me₃PhP⁺.Br^-) ≥ 98%. All solvents were obtained from mikroCHEM and were of p.a. grade.

S2.2. Synthesis and crystallization

For the preparation of (MePh₃P)[Co^III(bdt)₂], (I), a solution of Na (0.08 g, 3.3 mmol) in MeOH (10 ml) was added to 3,6-di­chloro­benzene-1,2-di­thiole (bdtCl₂; 0.34 g, 1.6 mmol). To this mixture, a solution of CoCl₂·6H₂O (0.18 g, 0.76 mmol) in MeOH (10 ml) was added. Finally, a solution of methyl­tri­phenyl­phospho­nium bromide (MePh₃P⁺.Br^-; 0.57 g, 1.6 mmol) in MeOH (10 ml) was added. The resulting solution was stirred for 20 min. The complex was precipitated by the slow addition of water accompanied by vigorous stirring. The blue crystalline powder which formed (as crude product) was filtered off, washed with di­ethyl ether and recrystallized from acetone (yield 75%). Crystals of (I) suitable for X-ray diffraction were grown by slow evaporation of a blue solution in an acetone–methanol–toluene solvent mixture (10:1:2 ratio).

The same procedure was used for the preparation of (MePh₃P)₂[Cu^II(bdt)₂].2Me₂SO, (II), and (MePh₃P)[Cu^III(bdt)₂], (III), using CuCl₂·2H₂O (0.13 g, 0.76 mmol) in place of CoCl₂·6H₂O (crude yield is 99%)[what does this relate to?]. The sample of (III) was separated from the crude product with acetone (yield 45%) and crystals suitable for X-ray diffraction were grown by slow evaporation of a green solution in an acetone–methanol–toluene solvent mixture (10:2:1 ratio). The sample of (II) (yellow crystalline powder) was insoluble in acetone (yield 44%) and crystals suitable for X-ray diffraction were grown by slow diffusion between two layers [a yellow di­methyl sulfoxide solution of a sample of (II) and H₂O in a 1:3 ratio]. After crystallization, a single crystal suitable for X-ray analysis was selected.

S2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The positions of all H atoms were optimized geometrically and constrained to ride on their parent atoms, with C—H = 0.95 (aromatic) or 0.98 Å (methyl) and with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

In each of the studied crystal structures, i.e. (I), (II) and (III), the central metal atom is on an inversion centre and is coordinated in a square-planar manner by four di­thiol­ate donor S atoms.

Co^III complex (I) and Cu^III complex (III) are isostructural and crystallize in the centrosymmetric P2₁/c space group (No. 14). Both structures consist of two complex anions (in special positions; the asymmetric part of the unit cell contains two halves of these anions) and one MePh₃P⁺ cation (Figs. 1 and 2). The central metal atom is coordinated by four donor S atoms from two 3,6-di­chloro­benzene-1,2-di­thiol­ate ligands. The X-ray structure analysis of (I) and (III) confirmed a square-planar geometry of the MS₄ chromophore (Table 2). The ratio of complex anion to counter-cation (1:1) results from the found stoichiometry. The expected formal oxidation state of the central metal atom of complexes (I) and (III) is +3.

For Co^III complex (I), the angle between the S2/S1/Co1 and S4/S3/Co2 planes is 83.05 (2)° and the distance between atoms Co1 and Co2 is 10.373 (6) Å. For Cu^III complex (III), the corresponding angle is 83.49 (3)° and the distance between atoms Cu1 and Cu2 is 10.386 (6) Å. The M—S bond lengths for (I) are in the range 2.1570 (6)–2.1641 (6) Å and for (III) are in the range 2.1721 (6)–2.1765 (6) Å.

The values for (I) and (III) are significantly shorter than the usual reported distances for metal complexes in a +2 oxidation state. The range for Co^II is from 2.19 [Cerdeira et al., 2012; Cambridge Structural Database (CSD; Groom & Allen, 2014) refcode LAYMEF] to 2.28 Å (Rao et al., 1986) and the range for Cu^II is from 2.26 (Cerdeira et al., 2012; CSD refcode LAYMAB) to 2.27 Å (Best et al., 1993); this fact also supports the assumption of a +3 oxidation state in these compounds (Table 2).

For comparison, in the CSD, 16 crystal structures with a square-planar arrangement around a central Co^III atom, where the M—S bond lengths range from 2.14 (Ray et al., 2005; CSD refcode MAJYUS) to 2.18 Å (Mrkvová et al., 2004; CSD refcode AWIHIX)), and for Cu^III, where the M—S bond lengths range from 2.16 (Bolligarla & Das, 2011; CSD refcode OYIRUK) to 2.18 Å (Alves et al., 2004; CSD refcode EWAMOE) were found. The structures of complexes (I)/(III) and (II) are stabilized by a system of five and six inter­molecular hydrogen-bond inter­actions, respectively (Table 3, and Figs. 4 and 5; see also Fig. 6 is in Supporting information.

Cu^II complex (II) crystallized in the centrosymmetric P2₁/n space group (No. 14). The asymmetric part of the unit cell consists of half of the centrosymmetric complex anion, one MePh₃P⁺ cation and a di­methyl sulfoxide solvent molecule (Fig. 3). The central metal atom is coordinated in the same way as in complexes (I) and (III) (Table 2), but unlike complexes (I) and (III), the ratio of complex anion to counter-cation is 1:2 for (II). The expected formal oxidation state of the central metal atom of (II) is +2, i.e. Cu^II. This is supported also by the values of the inter­atomic distances Cu1—S1 and Cu1—S2, which are 2.2641 (2) and 2.2671 (2) Å, respectively.

For (II) and (III), the inter­atomic Cu^III—S distance is shorter than the Cu^II—S distance. The `non-innocent' ligands act as a reservoir of electron density and stabilize the oxidation state of the central atom. In the case of compounds (I) and (III), depopulated d-orbitals form stronger coordination bonds with the donor S atoms.

S4. Conclusions

The basic driving force behind this work was to obtain suitable M^III coordination compounds in order to study the electronic structure by charge-density analysis. A chloro-substituted ligand was used to eliminate large anisotropic displacement parameters (ADPs) (Fronc et al., 2009), and also disorder. All the aims of the study, the elimination of disorder and decreasing the thermal motions were successful. Complexes were prepared with Cu in two oxidation states having the formulae (MePh₃P⁺)_n[M(bdtCl₂)₂]^n-, where n = 1 or 2, which could be separated.

Cobalt complexes are very sensitive to oxidation under normal conditions; therefore we were not able to prepare the Co^II analogue. The preparation of complexes with copper in two oxidation states shows the non-innocent character of the di­thiol­ate ligand. The oxidation state of the central metal atom is only the formal number. It is not possible to determine the exact charge of the central atom, but only of the complex anion as a whole. The non-innocet di­thiol­ate ligand is able to stabilize both 2+ and 3+ oxidation states.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2012); cell refinement: CrysAlis CCD (Oxford Diffraction, 2012); data reduction: CrysAlis RED (Oxford Diffraction, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus, 2013), OLEX2 (Dolomanov et al., 2009) and SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1998; Brandenburg & Berndt, 1999); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (*) -x+1, -y+1, -z+2; (**) -x, -y+1, -z+1.]
	Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (*) -x, -y+1, -z+1.]
	Fig. 3. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: -x+1, -y+1, -z+2; (**) -x, -y+1, -z+1.]
	Fig. 4. The crystal packing of compound (I), viewed along the b axis. Red dashed lines indicate hydrogen interactions. [Symmetry codes: (*) -x+1, -y+1, -z+2; (**) -x, -y+1, -z+1.]
	Fig. 5. The crystal packing of compound (II), viewed along the b axis. Red dashed lines indicate hydrogen interactions. [Symmetry code: (*) -x, -y+1, -z+1.]

(I) Methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-κ²S,S')cobaltate(1-)

Crystal data

(C19H18P)[Co(C6H2Cl2S2)2]	F(000) = 1528
Mr = 754.42	Dx = 1.564 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.46050 (18) Å	Cell parameters from 17287 reflections
b = 14.6661 (2) Å	θ = 2.1–28.3°
c = 16.24190 (19) Å	µ = 1.20 mm^−1
β = 91.9170 (11)°	T = 100 K
V = 3204.57 (7) Å^3	Plate, black
Z = 4	0.50 × 0.21 × 0.11 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer	8220 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5470 reflections with I > 2σ(I)
Detector resolution: 10.4340 pixels mm^-1	Rint = 0.034
ω scans	θmax = 29.6°, θmin = 2.1°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)]	h = −18→18
Tmin = 0.746, Tmax = 0.876	k = −20→20
55679 measured reflections	l = −22→22

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0372P)^2 + 1.2776P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
8220 reflections	Δρmax = 0.34 e Å^−3
373 parameters	Δρmin = −0.54 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.37579 (19)	0.32542 (17)	1.02686 (13)	0.0555 (6)
C2	0.3446 (2)	0.23853 (18)	1.04915 (14)	0.0655 (7)
C3	0.2448 (3)	0.2156 (2)	1.04774 (18)	0.0834 (10)
H3A	0.2249	0.1560	1.0632	0.100*
C4	0.1752 (3)	0.2787 (3)	1.02415 (19)	0.0842 (10)
H4A	0.1068	0.2625	1.0218	0.101*
C5	0.2035 (2)	0.3656 (2)	1.00366 (16)	0.0686 (7)
C6	0.30333 (18)	0.39155 (18)	1.00744 (14)	0.0558 (6)
C7	0.00292 (16)	0.61303 (17)	0.66224 (14)	0.0504 (5)
C8	−0.00714 (18)	0.64114 (19)	0.74378 (15)	0.0603 (6)
C9	0.0203 (2)	0.7274 (2)	0.76871 (18)	0.0729 (8)
H9A	0.0111	0.7459	0.8240	0.087*
C10	0.0609 (2)	0.7868 (2)	0.71356 (19)	0.0729 (8)
H10A	0.0793	0.8466	0.7306	0.088*
C11	0.07501 (18)	0.75932 (18)	0.63342 (17)	0.0609 (6)
C12	0.04567 (16)	0.67253 (16)	0.60650 (14)	0.0496 (5)
C13	0.6628 (2)	0.1266 (2)	0.92192 (15)	0.0716 (8)
H13C	0.6411	0.0747	0.9549	0.086*
H13B	0.6355	0.1831	0.9441	0.086*
H13A	0.7356	0.1298	0.9241	0.086*
C14	0.66099 (16)	0.20659 (16)	0.75797 (14)	0.0512 (6)
C15	0.70247 (18)	0.19204 (18)	0.68216 (15)	0.0583 (6)
H15A	0.7090	0.1318	0.6614	0.070*
C16	0.7344 (2)	0.2658 (2)	0.63676 (18)	0.0733 (8)
H16A	0.7627	0.2563	0.5846	0.088*
C17	0.7253 (2)	0.3514 (2)	0.6668 (2)	0.0858 (10)
H17A	0.7483	0.4015	0.6357	0.103*
C18	0.6834 (2)	0.3668 (2)	0.7410 (2)	0.0891 (10)
H18A	0.6766	0.4275	0.7606	0.107*
C19	0.6510 (2)	0.29452 (18)	0.78785 (19)	0.0710 (7)
H19A	0.6224	0.3050	0.8397	0.085*
C20	0.66827 (18)	0.00973 (15)	0.77625 (15)	0.0521 (6)
C21	0.7693 (2)	−0.00720 (19)	0.7868 (2)	0.0739 (8)
H21A	0.8103	0.0341	0.8176	0.089*
C22	0.8100 (2)	−0.0833 (2)	0.7528 (2)	0.0865 (10)
H22A	0.8792	−0.0947	0.7599	0.104*
C23	0.7512 (3)	−0.1430 (2)	0.70863 (19)	0.0777 (8)
H23A	0.7801	−0.1954	0.6847	0.093*
C24	0.6512 (2)	−0.12801 (19)	0.69858 (17)	0.0695 (7)
H24A	0.6107	−0.1706	0.6689	0.083*
C25	0.6092 (2)	−0.05115 (17)	0.73158 (15)	0.0586 (6)
H25A	0.5401	−0.0400	0.7237	0.070*
C26	0.48643 (16)	0.10983 (15)	0.81463 (13)	0.0457 (5)
C27	0.43546 (18)	0.08208 (18)	0.88244 (14)	0.0576 (6)
H27A	0.4709	0.0628	0.9309	0.069*
C28	0.3331 (2)	0.08229 (18)	0.87979 (16)	0.0630 (7)
H28A	0.2981	0.0644	0.9270	0.076*
C29	0.28175 (18)	0.10808 (17)	0.80985 (16)	0.0598 (6)
H29A	0.2111	0.1084	0.8086	0.072*
C30	0.33155 (19)	0.13356 (19)	0.74149 (17)	0.0665 (7)
H30A	0.2955	0.1498	0.6924	0.080*
C31	0.43395 (18)	0.13566 (18)	0.74363 (15)	0.0590 (6)
H31A	0.4684	0.1548	0.6966	0.071*
P1	0.61940 (4)	0.11228 (4)	0.81735 (4)	0.04795 (15)
S1	0.50157 (5)	0.35481 (4)	1.02323 (4)	0.05812 (16)
S2	0.33982 (5)	0.50367 (4)	0.99068 (4)	0.06089 (17)
S3	−0.03600 (5)	0.50483 (4)	0.62858 (4)	0.05421 (15)
S4	0.06212 (4)	0.63607 (4)	0.50499 (4)	0.05287 (15)
Cl1	0.43369 (8)	0.15912 (5)	1.08247 (4)	0.0888 (3)
Cl2	0.11398 (6)	0.44362 (7)	0.97283 (5)	0.0941 (3)
Cl3	−0.05403 (6)	0.56667 (6)	0.81562 (4)	0.0842 (2)
Cl4	0.13127 (6)	0.83333 (5)	0.56651 (5)	0.0821 (2)
Co1	0.5000	0.5000	1.0000	0.04919 (12)
Co2	0.0000	0.5000	0.5000	0.04427 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0670 (16)	0.0583 (15)	0.0415 (12)	−0.0132 (12)	0.0072 (11)	−0.0026 (10)
C2	0.092 (2)	0.0578 (16)	0.0474 (13)	−0.0162 (14)	0.0145 (13)	−0.0061 (11)
C3	0.110 (3)	0.072 (2)	0.0702 (18)	−0.042 (2)	0.0329 (18)	−0.0152 (15)
C4	0.078 (2)	0.099 (3)	0.0778 (19)	−0.036 (2)	0.0262 (16)	−0.0266 (18)
C5	0.0584 (16)	0.088 (2)	0.0604 (15)	−0.0169 (15)	0.0147 (12)	−0.0183 (14)
C6	0.0521 (14)	0.0687 (16)	0.0471 (13)	−0.0130 (12)	0.0087 (10)	−0.0058 (11)
C7	0.0353 (12)	0.0625 (15)	0.0532 (13)	0.0106 (10)	0.0003 (10)	−0.0049 (11)
C8	0.0483 (14)	0.0758 (18)	0.0565 (14)	0.0121 (12)	−0.0001 (11)	−0.0081 (12)
C9	0.0622 (17)	0.090 (2)	0.0664 (17)	0.0132 (16)	−0.0016 (14)	−0.0241 (16)
C10	0.0599 (17)	0.0695 (19)	0.089 (2)	0.0104 (14)	−0.0081 (15)	−0.0289 (16)
C11	0.0458 (14)	0.0577 (16)	0.0791 (17)	0.0072 (11)	−0.0026 (12)	−0.0054 (13)
C12	0.0367 (12)	0.0540 (14)	0.0581 (13)	0.0094 (10)	−0.0008 (10)	−0.0042 (11)
C13	0.0620 (17)	0.093 (2)	0.0590 (15)	−0.0088 (15)	−0.0107 (13)	0.0029 (14)
C14	0.0418 (12)	0.0469 (14)	0.0649 (15)	−0.0072 (10)	0.0003 (11)	0.0056 (11)
C15	0.0559 (15)	0.0585 (15)	0.0605 (15)	−0.0105 (12)	0.0023 (12)	0.0070 (12)
C16	0.0653 (18)	0.076 (2)	0.0791 (18)	−0.0064 (15)	0.0074 (14)	0.0236 (15)
C17	0.0625 (19)	0.069 (2)	0.127 (3)	−0.0043 (15)	0.0117 (18)	0.0366 (19)
C18	0.078 (2)	0.0458 (17)	0.144 (3)	0.0008 (14)	0.014 (2)	0.0090 (18)
C19	0.0641 (17)	0.0555 (17)	0.094 (2)	0.0005 (13)	0.0141 (15)	−0.0024 (14)
C20	0.0483 (14)	0.0480 (14)	0.0602 (14)	−0.0043 (10)	0.0049 (11)	0.0110 (10)
C21	0.0489 (15)	0.0605 (18)	0.112 (2)	−0.0012 (13)	−0.0011 (15)	−0.0042 (15)
C22	0.0587 (18)	0.068 (2)	0.133 (3)	0.0075 (15)	0.0109 (18)	0.0000 (19)
C23	0.091 (2)	0.0570 (17)	0.087 (2)	0.0100 (16)	0.0260 (17)	0.0069 (15)
C24	0.085 (2)	0.0588 (17)	0.0651 (16)	−0.0088 (15)	0.0050 (14)	−0.0014 (13)
C25	0.0584 (15)	0.0595 (16)	0.0577 (14)	−0.0059 (12)	0.0009 (12)	0.0067 (12)
C26	0.0435 (12)	0.0478 (13)	0.0461 (12)	−0.0038 (10)	0.0028 (9)	0.0008 (9)
C27	0.0539 (15)	0.0738 (17)	0.0453 (13)	−0.0073 (12)	0.0027 (11)	0.0037 (11)
C28	0.0593 (16)	0.0719 (17)	0.0589 (15)	−0.0136 (13)	0.0165 (12)	−0.0053 (12)
C29	0.0422 (13)	0.0592 (15)	0.0785 (18)	−0.0017 (11)	0.0081 (12)	−0.0031 (13)
C30	0.0502 (15)	0.0766 (18)	0.0720 (17)	0.0012 (13)	−0.0064 (13)	0.0176 (14)
C31	0.0492 (14)	0.0724 (17)	0.0554 (14)	−0.0017 (12)	0.0035 (11)	0.0176 (12)
P1	0.0422 (3)	0.0521 (4)	0.0495 (3)	−0.0062 (3)	−0.0001 (2)	0.0046 (3)
S1	0.0581 (4)	0.0553 (4)	0.0608 (4)	−0.0020 (3)	−0.0008 (3)	0.0084 (3)
S2	0.0474 (3)	0.0617 (4)	0.0736 (4)	−0.0023 (3)	0.0016 (3)	0.0043 (3)
S3	0.0531 (4)	0.0604 (4)	0.0497 (3)	−0.0021 (3)	0.0095 (3)	0.0008 (3)
S4	0.0505 (3)	0.0519 (3)	0.0566 (3)	−0.0002 (3)	0.0074 (3)	0.0028 (3)
Cl1	0.1438 (8)	0.0578 (4)	0.0650 (4)	−0.0074 (4)	0.0079 (4)	0.0090 (3)
Cl2	0.0500 (4)	0.1302 (8)	0.1024 (6)	−0.0046 (4)	0.0057 (4)	−0.0192 (5)
Cl3	0.0893 (5)	0.1119 (6)	0.0520 (4)	0.0095 (5)	0.0117 (4)	0.0019 (4)
Cl4	0.0833 (5)	0.0558 (4)	0.1072 (6)	−0.0054 (4)	0.0027 (4)	0.0015 (4)
Co1	0.0456 (3)	0.0521 (3)	0.0498 (2)	−0.00371 (19)	0.00065 (19)	0.00547 (19)
Co2	0.0369 (2)	0.0493 (3)	0.0468 (2)	0.00353 (18)	0.00480 (17)	0.00160 (18)

Geometric parameters (Å, º)

C1—C2	1.393 (3)	C17—H17A	0.9500
C1—C6	1.404 (4)	C18—C19	1.384 (4)
C1—S1	1.750 (3)	C18—H18A	0.9500
C2—C3	1.385 (4)	C19—H19A	0.9500
C2—Cl1	1.744 (3)	C20—C25	1.384 (3)
C3—C4	1.362 (5)	C20—C21	1.388 (4)
C3—H3A	0.9500	C20—P1	1.780 (3)
C4—C5	1.375 (4)	C21—C22	1.367 (4)
C4—H4A	0.9500	C21—H21A	0.9500
C5—C6	1.396 (3)	C22—C23	1.367 (4)
C5—Cl2	1.724 (3)	C22—H22A	0.9500
C6—S2	1.740 (3)	C23—C24	1.369 (4)
C7—C12	1.395 (3)	C23—H23A	0.9500
C7—C8	1.398 (3)	C24—C25	1.377 (4)
C7—S3	1.753 (2)	C24—H24A	0.9500
C8—C9	1.374 (4)	C25—H25A	0.9500
C8—Cl3	1.733 (3)	C26—C27	1.378 (3)
C9—C10	1.376 (4)	C26—C31	1.385 (3)
C9—H9A	0.9500	C26—P1	1.789 (2)
C10—C11	1.381 (4)	C27—C28	1.376 (4)
C10—H10A	0.9500	C27—H27A	0.9500
C11—C12	1.398 (3)	C28—C29	1.364 (4)
C11—Cl4	1.729 (3)	C28—H28A	0.9500
C12—S4	1.754 (2)	C29—C30	1.368 (4)
C13—P1	1.790 (2)	C29—H29A	0.9500
C13—H13C	0.9800	C30—C31	1.378 (3)
C13—H13B	0.9800	C30—H30A	0.9500
C13—H13A	0.9800	C31—H31A	0.9500
C14—C15	1.385 (3)	S1—Co1	2.1625 (6)
C14—C19	1.386 (4)	S2—Co1	2.1570 (6)
C14—P1	1.787 (2)	S3—Co2	2.1607 (6)
C15—C16	1.385 (3)	S4—Co2	2.1642 (6)
C15—H15A	0.9500	Co1—S2^i	2.1570 (7)
C16—C17	1.354 (4)	Co1—S1^i	2.1625 (6)
C16—H16A	0.9500	Co2—S3^ii	2.1607 (6)
C17—C18	1.367 (5)	Co2—S4^ii	2.1642 (6)
C2—C1—C6	118.5 (2)	C14—C19—H19A	120.5
C2—C1—S1	122.3 (2)	C25—C20—C21	119.5 (2)
C6—C1—S1	119.21 (18)	C25—C20—P1	121.91 (19)
C3—C2—C1	121.2 (3)	C21—C20—P1	118.5 (2)
C3—C2—Cl1	120.0 (2)	C22—C21—C20	120.0 (3)
C1—C2—Cl1	118.8 (2)	C22—C21—H21A	120.0
C4—C3—C2	119.9 (3)	C20—C21—H21A	120.0
C4—C3—H3A	120.1	C23—C22—C21	120.1 (3)
C2—C3—H3A	120.1	C23—C22—H22A	119.9
C3—C4—C5	120.3 (3)	C21—C22—H22A	119.9
C3—C4—H4A	119.9	C22—C23—C24	120.6 (3)
C5—C4—H4A	119.9	C22—C23—H23A	119.7
C4—C5—C6	121.1 (3)	C24—C23—H23A	119.7
C4—C5—Cl2	119.3 (2)	C23—C24—C25	120.0 (3)
C6—C5—Cl2	119.6 (2)	C23—C24—H24A	120.0
C5—C6—C1	118.8 (2)	C25—C24—H24A	120.0
C5—C6—S2	121.8 (2)	C24—C25—C20	119.7 (3)
C1—C6—S2	119.36 (18)	C24—C25—H25A	120.1
C12—C7—C8	119.0 (2)	C20—C25—H25A	120.1
C12—C7—S3	119.30 (17)	C27—C26—C31	119.5 (2)
C8—C7—S3	121.7 (2)	C27—C26—P1	120.69 (17)
C9—C8—C7	121.1 (3)	C31—C26—P1	119.80 (17)
C9—C8—Cl3	118.8 (2)	C28—C27—C26	119.9 (2)
C7—C8—Cl3	120.1 (2)	C28—C27—H27A	120.0
C8—C9—C10	120.0 (3)	C26—C27—H27A	120.0
C8—C9—H9A	120.0	C29—C28—C27	120.4 (2)
C10—C9—H9A	120.0	C29—C28—H28A	119.8
C9—C10—C11	119.9 (3)	C27—C28—H28A	119.8
C9—C10—H10A	120.0	C28—C29—C30	120.2 (2)
C11—C10—H10A	120.0	C28—C29—H29A	119.9
C10—C11—C12	120.9 (3)	C30—C29—H29A	119.9
C10—C11—Cl4	119.1 (2)	C29—C30—C31	120.2 (2)
C12—C11—Cl4	120.0 (2)	C29—C30—H30A	119.9
C7—C12—C11	119.0 (2)	C31—C30—H30A	119.9
C7—C12—S4	119.13 (18)	C30—C31—C26	119.8 (2)
C11—C12—S4	121.9 (2)	C30—C31—H31A	120.1
P1—C13—H13C	109.5	C26—C31—H31A	120.1
P1—C13—H13B	109.5	C20—P1—C14	108.98 (11)
H13C—C13—H13B	109.5	C20—P1—C26	110.83 (11)
P1—C13—H13A	109.5	C14—P1—C26	109.48 (10)
H13C—C13—H13A	109.5	C20—P1—C13	109.98 (13)
H13B—C13—H13A	109.5	C14—P1—C13	108.86 (13)
C15—C14—C19	120.1 (2)	C26—P1—C13	108.69 (12)
C15—C14—P1	120.22 (19)	C1—S1—Co1	104.15 (9)
C19—C14—P1	119.7 (2)	C6—S2—Co1	104.60 (9)
C14—C15—C16	119.6 (3)	C7—S3—Co2	104.88 (8)
C14—C15—H15A	120.2	C12—S4—Co2	104.80 (8)
C16—C15—H15A	120.2	S2—Co1—S2^i	180.0
C17—C16—C15	119.9 (3)	S2—Co1—S1^i	87.66 (2)
C17—C16—H16A	120.0	S2^i—Co1—S1^i	92.34 (2)
C15—C16—H16A	120.0	S2—Co1—S1	92.34 (2)
C16—C17—C18	121.1 (3)	S2^i—Co1—S1	87.66 (2)
C16—C17—H17A	119.4	S1^i—Co1—S1	180.0
C18—C17—H17A	119.4	S3—Co2—S3^ii	180.0
C17—C18—C19	120.3 (3)	S3—Co2—S4^ii	88.14 (2)
C17—C18—H18A	119.9	S3^ii—Co2—S4^ii	91.86 (2)
C19—C18—H18A	119.9	S3—Co2—S4	91.86 (2)
C18—C19—C14	119.0 (3)	S3^ii—Co2—S4	88.14 (2)
C18—C19—H19A	120.5	S4^ii—Co2—S4	180.0
C6—C1—C2—C3	3.7 (4)	C25—C20—C21—C22	0.3 (4)
S1—C1—C2—C3	−176.85 (19)	P1—C20—C21—C22	−177.1 (2)
C6—C1—C2—Cl1	−174.19 (17)	C20—C21—C22—C23	−0.2 (5)
S1—C1—C2—Cl1	5.2 (3)	C21—C22—C23—C24	−0.7 (5)
C1—C2—C3—C4	0.1 (4)	C22—C23—C24—C25	1.4 (4)
Cl1—C2—C3—C4	178.0 (2)	C23—C24—C25—C20	−1.3 (4)
C2—C3—C4—C5	−1.6 (4)	C21—C20—C25—C24	0.4 (4)
C3—C4—C5—C6	−0.8 (4)	P1—C20—C25—C24	177.73 (19)
C3—C4—C5—Cl2	179.2 (2)	C31—C26—C27—C28	−1.5 (4)
C4—C5—C6—C1	4.6 (4)	P1—C26—C27—C28	178.76 (19)
Cl2—C5—C6—C1	−175.42 (18)	C26—C27—C28—C29	1.3 (4)
C4—C5—C6—S2	−174.2 (2)	C27—C28—C29—C30	0.3 (4)
Cl2—C5—C6—S2	5.8 (3)	C28—C29—C30—C31	−1.8 (4)
C2—C1—C6—C5	−5.9 (3)	C29—C30—C31—C26	1.5 (4)
S1—C1—C6—C5	174.63 (18)	C27—C26—C31—C30	0.1 (4)
C2—C1—C6—S2	172.86 (17)	P1—C26—C31—C30	179.8 (2)
S1—C1—C6—S2	−6.6 (3)	C25—C20—P1—C14	−106.6 (2)
C12—C7—C8—C9	2.9 (4)	C21—C20—P1—C14	70.7 (2)
S3—C7—C8—C9	−177.6 (2)	C25—C20—P1—C26	13.9 (2)
C12—C7—C8—Cl3	−176.68 (17)	C21—C20—P1—C26	−168.7 (2)
S3—C7—C8—Cl3	2.9 (3)	C25—C20—P1—C13	134.1 (2)
C7—C8—C9—C10	−1.8 (4)	C21—C20—P1—C13	−48.5 (2)
Cl3—C8—C9—C10	177.7 (2)	C15—C14—P1—C20	14.3 (2)
C8—C9—C10—C11	−0.6 (4)	C19—C14—P1—C20	−166.2 (2)
C9—C10—C11—C12	2.0 (4)	C15—C14—P1—C26	−107.1 (2)
C9—C10—C11—Cl4	−177.2 (2)	C19—C14—P1—C26	72.5 (2)
C8—C7—C12—C11	−1.5 (3)	C15—C14—P1—C13	134.2 (2)
S3—C7—C12—C11	178.93 (17)	C19—C14—P1—C13	−46.2 (2)
C8—C7—C12—S4	177.92 (17)	C27—C26—P1—C20	94.9 (2)
S3—C7—C12—S4	−1.6 (2)	C31—C26—P1—C20	−84.8 (2)
C10—C11—C12—C7	−0.9 (3)	C27—C26—P1—C14	−144.9 (2)
Cl4—C11—C12—C7	178.24 (17)	C31—C26—P1—C14	35.4 (2)
C10—C11—C12—S4	179.71 (19)	C27—C26—P1—C13	−26.1 (2)
Cl4—C11—C12—S4	−1.2 (3)	C31—C26—P1—C13	154.2 (2)
C19—C14—C15—C16	0.4 (4)	C2—C1—S1—Co1	−173.25 (18)
P1—C14—C15—C16	−179.99 (19)	C6—C1—S1—Co1	6.2 (2)
C14—C15—C16—C17	0.2 (4)	C5—C6—S2—Co1	−177.93 (18)
C15—C16—C17—C18	−1.0 (5)	C1—C6—S2—Co1	3.3 (2)
C16—C17—C18—C19	1.1 (5)	C12—C7—S3—Co2	0.39 (19)
C17—C18—C19—C14	−0.5 (5)	C8—C7—S3—Co2	−179.15 (17)
C15—C14—C19—C18	−0.3 (4)	C7—C12—S4—Co2	1.98 (19)
P1—C14—C19—C18	−179.9 (2)	C11—C12—S4—Co2	−178.60 (17)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27A···Cl1	0.95	2.90	3.441 (2)	118
C4—H4A···S4^iii	0.95	2.95	3.834 (3)	154
C13—H13A···S4^iv	0.98	2.92	3.853 (3)	159
C31—H31A···S1^v	0.95	2.87	3.726 (3)	151
C29—H29A···Cl3^iii	0.95	2.94	3.674 (3)	135

Symmetry codes: (iii) −x, y−1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2; (v) x, −y+1/2, z−1/2.

(II) Bis(methyltriphenylphosphonium) bis(3,6-dichlorobenzene-1,2-dithiolato-κ²S,S')cuprate(2-) dimethyl sulfoxide disolvate

Crystal data

(C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS	F(000) = 1230
Mr = 1192.59	Dx = 1.494 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.94737 (14) Å	Cell parameters from 70625 reflections
b = 11.53304 (11) Å	θ = 3.0–44.9°
c = 16.47990 (17) Å	µ = 0.95 mm^−1
β = 90.6983 (9)°	T = 100 K
V = 2650.69 (5) Å^3	Plate, orange
Z = 2	0.53 × 0.27 × 0.02 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer	28120 independent reflections
Radiation source: Enhance (Mo) X-ray Source	15927 reflections with I > 2σ(I)
Detector resolution: 5.2170 pixels mm^-1	Rint = 0.089
ω scans	θmax = 50.9°, θmin = 2.6°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)]	h = −29→30
Tmin = 0.742, Tmax = 0.981	k = −24→25
369672 measured reflections	l = −35→35

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 0.1295P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
28120 reflections	Δρmax = 1.14 e Å^−3
313 parameters	Δρmin = −0.39 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.27b (release 13-12-2013 CrysAlis171 .NET) (compiled Dec 13 2013,18:28:10) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.20229 (6)	0.61969 (8)	0.52257 (5)	0.01411 (13)
C2	0.29896 (6)	0.64066 (8)	0.54208 (5)	0.01583 (14)
C3	0.33412 (7)	0.74906 (9)	0.56292 (6)	0.01856 (15)
H3	0.4001	0.7593	0.5758	0.022*
C4	0.27154 (7)	0.84246 (9)	0.56470 (6)	0.01890 (16)
H4	0.2942	0.9177	0.5784	0.023*
C5	0.17525 (7)	0.82436 (8)	0.54620 (6)	0.01676 (14)
C6	0.13753 (6)	0.71535 (8)	0.52434 (5)	0.01444 (13)
C7	0.34105 (8)	1.09430 (8)	0.20956 (6)	0.01920 (16)
H7C	0.2987	1.1621	0.2105	0.023*
H7A	0.3369	1.0572	0.1561	0.023*
H7B	0.4073	1.1188	0.2203	0.023*
C14	0.31195 (6)	1.06566 (8)	0.38187 (5)	0.01469 (13)
C19	0.23386 (7)	1.12765 (9)	0.41189 (6)	0.01937 (16)
H19	0.1742	1.1269	0.3835	0.023*
C18	0.24419 (8)	1.19042 (9)	0.48363 (7)	0.02245 (18)
H18	0.1911	1.2317	0.5048	0.027*
C17	0.33186 (8)	1.19275 (9)	0.52417 (6)	0.02125 (17)
H17	0.3386	1.2359	0.5730	0.025*
C16	0.40986 (7)	1.13242 (9)	0.49387 (6)	0.01938 (16)
H16	0.4697	1.1347	0.5220	0.023*
C15	0.40055 (7)	1.06879 (8)	0.42263 (6)	0.01624 (14)
H15	0.4539	1.0277	0.4017	0.019*
C20	0.18635 (6)	0.94138 (8)	0.26401 (5)	0.01459 (13)
C21	0.12351 (7)	0.91080 (8)	0.32564 (6)	0.01723 (15)
H21	0.1410	0.9233	0.3808	0.021*
C22	0.03520 (7)	0.86191 (9)	0.30581 (6)	0.01876 (16)
H22	−0.0084	0.8424	0.3475	0.023*
C23	0.01069 (7)	0.84151 (8)	0.22516 (6)	0.01856 (15)
H23	−0.0499	0.8085	0.2118	0.022*
C24	0.07449 (7)	0.86918 (9)	0.16378 (6)	0.01836 (15)
H24	0.0578	0.8535	0.1088	0.022*
C25	0.16228 (7)	0.91950 (8)	0.18264 (6)	0.01664 (14)
H25	0.2057	0.9389	0.1408	0.020*
C8	0.38173 (6)	0.86877 (7)	0.28620 (5)	0.01370 (13)
C9	0.38465 (7)	0.79763 (8)	0.35489 (6)	0.01706 (15)
H9	0.3493	0.8179	0.4017	0.020*
C10	0.43958 (8)	0.69716 (8)	0.35434 (6)	0.01997 (16)
H10	0.4425	0.6491	0.4011	0.024*
C11	0.49039 (8)	0.66671 (9)	0.28536 (6)	0.02083 (17)
H11	0.5285	0.5985	0.2853	0.025*
C12	0.48535 (8)	0.73606 (9)	0.21662 (6)	0.02147 (17)
H12	0.5190	0.7142	0.1693	0.026*
C13	0.43120 (7)	0.83745 (8)	0.21668 (6)	0.01810 (15)
H13	0.4280	0.8849	0.1696	0.022*
C26	0.20169 (9)	0.36221 (11)	0.69835 (8)	0.0297 (2)
H26A	0.2387	0.3442	0.7477	0.036*
H26B	0.2452	0.3886	0.6559	0.036*
H26C	0.1677	0.2926	0.6798	0.036*
C27	0.20139 (10)	0.58249 (12)	0.74969 (8)	0.0332 (3)
H27A	0.2415	0.5528	0.7943	0.040*
H27B	0.1672	0.6520	0.7677	0.040*
H27C	0.2420	0.6022	0.7036	0.040*
O1	0.06658 (6)	0.43738 (8)	0.79518 (5)	0.02556 (15)
P1	0.30510 (2)	0.99367 (2)	0.28561 (2)	0.01329 (4)
S1	0.16153 (2)	0.48078 (2)	0.49861 (2)	0.01542 (4)
S2	0.01625 (2)	0.69557 (2)	0.50212 (2)	0.01693 (4)
S3	0.11665 (2)	0.47421 (2)	0.71961 (2)	0.02120 (5)
Cl1	0.37970 (2)	0.52434 (2)	0.54206 (2)	0.02084 (4)
Cl2	0.09886 (2)	0.94374 (2)	0.55149 (2)	0.02264 (5)
Cu1	0.0000	0.5000	0.5000	0.01322 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0149 (3)	0.0167 (3)	0.0107 (3)	−0.0008 (3)	0.0004 (2)	−0.0003 (2)
C2	0.0139 (3)	0.0197 (4)	0.0139 (3)	−0.0009 (3)	0.0009 (3)	0.0015 (3)
C3	0.0166 (3)	0.0239 (4)	0.0152 (3)	−0.0052 (3)	−0.0005 (3)	0.0002 (3)
C4	0.0212 (4)	0.0198 (4)	0.0157 (3)	−0.0059 (3)	0.0014 (3)	−0.0016 (3)
C5	0.0196 (4)	0.0156 (3)	0.0151 (3)	−0.0016 (3)	0.0036 (3)	−0.0009 (3)
C6	0.0151 (3)	0.0152 (3)	0.0130 (3)	−0.0003 (3)	0.0019 (3)	0.0003 (2)
C7	0.0229 (4)	0.0169 (4)	0.0177 (4)	−0.0030 (3)	−0.0021 (3)	0.0037 (3)
C14	0.0166 (3)	0.0135 (3)	0.0140 (3)	0.0005 (3)	−0.0014 (3)	−0.0010 (3)
C19	0.0176 (4)	0.0165 (4)	0.0239 (4)	0.0029 (3)	−0.0021 (3)	−0.0034 (3)
C18	0.0235 (4)	0.0176 (4)	0.0264 (5)	0.0025 (3)	0.0043 (4)	−0.0058 (3)
C17	0.0282 (5)	0.0181 (4)	0.0175 (4)	−0.0014 (3)	0.0025 (3)	−0.0054 (3)
C16	0.0217 (4)	0.0204 (4)	0.0159 (4)	−0.0019 (3)	−0.0029 (3)	−0.0027 (3)
C15	0.0165 (3)	0.0174 (3)	0.0148 (3)	0.0005 (3)	−0.0010 (3)	−0.0022 (3)
C20	0.0157 (3)	0.0138 (3)	0.0141 (3)	−0.0001 (3)	−0.0023 (3)	−0.0001 (3)
C21	0.0202 (4)	0.0177 (4)	0.0139 (3)	−0.0010 (3)	−0.0008 (3)	0.0002 (3)
C22	0.0189 (4)	0.0188 (4)	0.0186 (4)	−0.0018 (3)	0.0011 (3)	0.0005 (3)
C23	0.0176 (4)	0.0168 (4)	0.0212 (4)	−0.0016 (3)	−0.0028 (3)	0.0002 (3)
C24	0.0187 (4)	0.0198 (4)	0.0165 (4)	−0.0009 (3)	−0.0034 (3)	−0.0022 (3)
C25	0.0172 (3)	0.0189 (4)	0.0138 (3)	0.0002 (3)	−0.0012 (3)	−0.0006 (3)
C8	0.0152 (3)	0.0132 (3)	0.0127 (3)	−0.0004 (2)	−0.0015 (2)	−0.0007 (2)
C9	0.0216 (4)	0.0160 (3)	0.0136 (3)	0.0013 (3)	0.0005 (3)	0.0008 (3)
C10	0.0259 (4)	0.0154 (3)	0.0186 (4)	0.0018 (3)	−0.0004 (3)	0.0024 (3)
C11	0.0238 (4)	0.0147 (3)	0.0241 (4)	0.0021 (3)	0.0014 (3)	−0.0018 (3)
C12	0.0252 (4)	0.0189 (4)	0.0204 (4)	0.0020 (3)	0.0053 (3)	−0.0024 (3)
C13	0.0221 (4)	0.0175 (4)	0.0147 (3)	0.0005 (3)	0.0025 (3)	−0.0004 (3)
C26	0.0328 (6)	0.0295 (5)	0.0271 (5)	0.0115 (4)	0.0078 (4)	0.0027 (4)
C27	0.0379 (7)	0.0312 (6)	0.0308 (6)	−0.0090 (5)	0.0077 (5)	0.0013 (5)
O1	0.0233 (3)	0.0282 (4)	0.0254 (4)	0.0012 (3)	0.0080 (3)	0.0037 (3)
P1	0.01548 (9)	0.01278 (9)	0.01158 (8)	−0.00015 (7)	−0.00208 (7)	0.00014 (7)
S1	0.01402 (8)	0.01510 (9)	0.01713 (9)	0.00027 (7)	0.00005 (7)	−0.00134 (7)
S2	0.01420 (9)	0.01562 (9)	0.02098 (10)	0.00077 (7)	0.00046 (7)	0.00093 (7)
S3	0.02288 (11)	0.02286 (11)	0.01794 (10)	0.00442 (9)	0.00261 (8)	0.00203 (8)
Cl1	0.01402 (8)	0.02486 (10)	0.02360 (10)	0.00159 (7)	−0.00115 (7)	0.00282 (8)
Cl2	0.02563 (11)	0.01524 (9)	0.02721 (12)	0.00048 (8)	0.00724 (9)	−0.00099 (8)
Cu1	0.01290 (6)	0.01499 (6)	0.01177 (6)	−0.00054 (5)	0.00042 (5)	−0.00054 (5)

Geometric parameters (Å, º)

C1—C2	1.4033 (12)	C22—C23	1.3885 (14)
C1—C6	1.4264 (13)	C22—H22	0.9500
C1—S1	1.7436 (9)	C23—C24	1.3924 (14)
C2—C3	1.3847 (14)	C23—H23	0.9500
C2—Cl1	1.7516 (10)	C24—C25	1.3868 (13)
C3—C4	1.3869 (15)	C24—H24	0.9500
C3—H3	0.9500	C25—H25	0.9500
C4—C5	1.3894 (14)	C8—C13	1.3923 (13)
C4—H4	0.9500	C8—C9	1.3982 (12)
C5—C6	1.4081 (13)	C8—P1	1.7936 (9)
C5—Cl2	1.7437 (10)	C9—C10	1.3891 (13)
C6—S2	1.7413 (9)	C9—H9	0.9500
C7—P1	1.7845 (10)	C10—C11	1.3919 (14)
C7—H7C	0.9800	C10—H10	0.9500
C7—H7A	0.9800	C11—C12	1.3878 (15)
C7—H7B	0.9800	C11—H11	0.9500
C14—C19	1.3983 (13)	C12—C13	1.3921 (14)
C14—C15	1.3998 (13)	C12—H12	0.9500
C14—P1	1.7919 (9)	C13—H13	0.9500
C19—C18	1.3922 (14)	C26—S3	1.7912 (12)
C19—H19	0.9500	C26—H26A	0.9800
C18—C17	1.3865 (16)	C26—H26B	0.9800
C18—H18	0.9500	C26—H26C	0.9800
C17—C16	1.3893 (15)	C27—S3	1.7855 (14)
C17—H17	0.9500	C27—H27A	0.9800
C16—C15	1.3893 (13)	C27—H27B	0.9800
C16—H16	0.9500	C27—H27C	0.9800
C15—H15	0.9500	O1—S3	1.4968 (8)
C20—C21	1.3948 (13)	S1—Cu1	2.2641 (2)
C20—C25	1.4013 (12)	S2—Cu1	2.2671 (2)
C20—P1	1.7943 (9)	Cu1—S1^i	2.2642 (2)
C21—C22	1.3900 (14)	Cu1—S2^i	2.2671 (2)
C21—H21	0.9500
C2—C1—C6	117.96 (8)	C25—C24—C23	120.23 (9)
C2—C1—S1	121.34 (7)	C25—C24—H24	119.9
C6—C1—S1	120.69 (7)	C23—C24—H24	119.9
C3—C2—C1	123.29 (9)	C24—C25—C20	119.36 (9)
C3—C2—Cl1	117.76 (7)	C24—C25—H25	120.3
C1—C2—Cl1	118.94 (7)	C20—C25—H25	120.3
C2—C3—C4	119.04 (9)	C13—C8—C9	120.28 (8)
C2—C3—H3	120.5	C13—C8—P1	120.33 (7)
C4—C3—H3	120.5	C9—C8—P1	119.15 (7)
C3—C4—C5	119.05 (9)	C10—C9—C8	119.66 (9)
C3—C4—H4	120.5	C10—C9—H9	120.2
C5—C4—H4	120.5	C8—C9—H9	120.2
C4—C5—C6	123.19 (9)	C9—C10—C11	120.14 (9)
C4—C5—Cl2	117.39 (7)	C9—C10—H10	119.9
C6—C5—Cl2	119.42 (7)	C11—C10—H10	119.9
C5—C6—C1	117.46 (8)	C12—C11—C10	120.00 (9)
C5—C6—S2	121.98 (7)	C12—C11—H11	120.0
C1—C6—S2	120.54 (7)	C10—C11—H11	120.0
P1—C7—H7C	109.5	C11—C12—C13	120.37 (9)
P1—C7—H7A	109.5	C11—C12—H12	119.8
H7C—C7—H7A	109.5	C13—C12—H12	119.8
P1—C7—H7B	109.5	C12—C13—C8	119.52 (9)
H7C—C7—H7B	109.5	C12—C13—H13	120.2
H7A—C7—H7B	109.5	C8—C13—H13	120.2
C19—C14—C15	120.25 (8)	S3—C26—H26A	109.5
C19—C14—P1	121.12 (7)	S3—C26—H26B	109.5
C15—C14—P1	118.29 (7)	H26A—C26—H26B	109.5
C18—C19—C14	119.57 (9)	S3—C26—H26C	109.5
C18—C19—H19	120.2	H26A—C26—H26C	109.5
C14—C19—H19	120.2	H26B—C26—H26C	109.5
C17—C18—C19	120.04 (9)	S3—C27—H27A	109.5
C17—C18—H18	120.0	S3—C27—H27B	109.5
C19—C18—H18	120.0	H27A—C27—H27B	109.5
C18—C17—C16	120.47 (9)	S3—C27—H27C	109.5
C18—C17—H17	119.8	H27A—C27—H27C	109.5
C16—C17—H17	119.8	H27B—C27—H27C	109.5
C17—C16—C15	120.18 (9)	C7—P1—C14	107.94 (5)
C17—C16—H16	119.9	C7—P1—C8	110.71 (5)
C15—C16—H16	119.9	C14—P1—C8	110.00 (4)
C16—C15—C14	119.48 (9)	C7—P1—C20	110.24 (5)
C16—C15—H15	120.3	C14—P1—C20	111.74 (4)
C14—C15—H15	120.3	C8—P1—C20	106.24 (4)
C21—C20—C25	120.39 (8)	C1—S1—Cu1	103.27 (3)
C21—C20—P1	121.82 (7)	C6—S2—Cu1	103.31 (3)
C25—C20—P1	117.39 (7)	O1—S3—C27	106.34 (6)
C22—C21—C20	119.62 (9)	O1—S3—C26	105.95 (5)
C22—C21—H21	120.2	C27—S3—C26	96.95 (7)
C20—C21—H21	120.2	S1—Cu1—S1^i	179.999 (11)
C23—C22—C21	120.06 (9)	S1—Cu1—S2^i	90.100 (8)
C23—C22—H22	120.0	S1^i—Cu1—S2^i	89.899 (8)
C21—C22—H22	120.0	S1—Cu1—S2	89.899 (8)
C22—C23—C24	120.30 (9)	S1^i—Cu1—S2	90.101 (8)
C22—C23—H23	119.9	S2^i—Cu1—S2	180.0
C24—C23—H23	119.9
C6—C1—C2—C3	0.09 (13)	P1—C20—C25—C24	174.20 (7)
S1—C1—C2—C3	−178.77 (7)	C13—C8—C9—C10	1.95 (14)
C6—C1—C2—Cl1	178.94 (6)	P1—C8—C9—C10	176.41 (8)
S1—C1—C2—Cl1	0.08 (10)	C8—C9—C10—C11	−0.86 (15)
C1—C2—C3—C4	−0.14 (14)	C9—C10—C11—C12	−0.76 (16)
Cl1—C2—C3—C4	−179.00 (7)	C10—C11—C12—C13	1.30 (16)
C2—C3—C4—C5	0.55 (14)	C11—C12—C13—C8	−0.22 (16)
C3—C4—C5—C6	−0.96 (14)	C9—C8—C13—C12	−1.41 (14)
C3—C4—C5—Cl2	178.58 (7)	P1—C8—C13—C12	−175.80 (8)
C4—C5—C6—C1	0.90 (13)	C19—C14—P1—C7	88.84 (9)
Cl2—C5—C6—C1	−178.63 (6)	C15—C14—P1—C7	−84.54 (8)
C4—C5—C6—S2	179.60 (7)	C19—C14—P1—C8	−150.27 (8)
Cl2—C5—C6—S2	0.07 (11)	C15—C14—P1—C8	36.35 (9)
C2—C1—C6—C5	−0.45 (12)	C19—C14—P1—C20	−32.53 (9)
S1—C1—C6—C5	178.43 (7)	C15—C14—P1—C20	154.09 (7)
C2—C1—C6—S2	−179.16 (6)	C13—C8—P1—C7	−24.58 (9)
S1—C1—C6—S2	−0.29 (10)	C9—C8—P1—C7	160.97 (7)
C15—C14—C19—C18	−1.46 (15)	C13—C8—P1—C14	−143.79 (7)
P1—C14—C19—C18	−174.71 (8)	C9—C8—P1—C14	41.76 (9)
C14—C19—C18—C17	1.04 (16)	C13—C8—P1—C20	95.11 (8)
C19—C18—C17—C16	−0.22 (16)	C9—C8—P1—C20	−79.34 (8)
C18—C17—C16—C15	−0.19 (16)	C21—C20—P1—C7	−148.23 (8)
C17—C16—C15—C14	−0.23 (15)	C25—C20—P1—C7	38.93 (9)
C19—C14—C15—C16	1.06 (14)	C21—C20—P1—C14	−28.21 (9)
P1—C14—C15—C16	174.50 (8)	C25—C20—P1—C14	158.96 (7)
C25—C20—C21—C22	−2.16 (14)	C21—C20—P1—C8	91.77 (8)
P1—C20—C21—C22	−174.79 (7)	C25—C20—P1—C8	−81.07 (8)
C20—C21—C22—C23	1.33 (15)	C2—C1—S1—Cu1	168.55 (6)
C21—C22—C23—C24	0.39 (15)	C6—C1—S1—Cu1	−10.28 (7)
C22—C23—C24—C25	−1.29 (15)	C5—C6—S2—Cu1	−167.98 (7)
C23—C24—C25—C20	0.47 (15)	C1—C6—S2—Cu1	10.68 (8)
C21—C20—C25—C24	1.26 (14)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···S1^ii	0.98	2.70	3.6717 (10)	172
C7—H7B···O1^iii	0.98	2.61	3.4511 (14)	144
C15—H15···O1^iii	0.95	2.40	3.1460 (12)	135
C21—H21···Cl2	0.95	2.89	3.7613 (10)	153
C25—H25···S1^ii	0.95	3.01	3.9546 (10)	175
C26—H26B···S1	0.98	3.02	3.6021 (13)	119

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z−1/2.