[N,N-Bis(2-hydroxy­ethyl)­di­thio­car­bamato-S]­bis­(tri­phenyl­phosphine-P)­copper(I) tri­phenyl­phosphine solvate

In the title compound, [Cu(C₅H₁₀NO₂S₂)(C₁₈H₁₅P)₂]·C₁₈H₁₅P, the Cu atom is in a distorted tetrahedral coordination, with two tri­phenyl­phosphine P atoms and two S atoms from an N,N-bis(2-hydroxy­ethyl)­di­thio­carbamate ligand occupying the vertices. The crystal structure is characterized by alternate layers of complex and tri­phenyl­phosphine mol­ecules.

S1. Comment

Group 12 metals form a wide range of tertiary phosphine (R₃P) complexes of the general stoichiometry L_nMX(L = R₃P, n = 1–4; Attar, Alcock, Frye et al., 1991; Attar, Alcock, Bowmaker et al., 1991; Alyea et al., 1992). The value of n and the net electronic charge on the complex are somewhat dependent upon the coordinating ability of X. Also, the transition metal dithiolates containing MS₄ chromophores show interesting variations in their reactions with Lewis bases (Cordes & Draganjac, 1988; Venkatachalam et al., 1996).

The asymmetric unit of the title structure contains one molecule of [Cu{(C₂H₄OH)₂S₂CN}(PPh₃)₂] together with a molecule of uncoordinated triphenylphosphine. The Cu1 atom is in a distorted tetrahedral environment, with the P atoms of the triphenylphosphine ligands and the S atoms of the bidentate dithiocarbamate ligand occupying the vertices. The angles around Cu1 range between 74.77 (4) (S1—Cu1—S2) and 124.51 (4)° (P1—Cu1—P2). The small S1—Cu1—S2 bond angle is due to the restricted bite angle of the ligand. The P1—Cu1—P2 bond angle is comparable with values reported for other bis(triphenylphosphine)copper(I) compounds (Karaglannidis et al., 1989; Long et al., 1996). The Cu—P distances are comparable to those found in (PPh₃)₂Cu(C₂H₄N₂S₂)Br (Long et al., 1996). The bond lengths of Cu—S1 and S2—C37 are longer than those of Cu—S2 and S1—C37, respectively. One of the S—C bond lengths (S1—C37) is close to the C═S distance of 1.69 Å, while S2—C37 shows a value intermediate between single- and double-bond distances, indicating partial double-bond character. The longer Cu—S bond length (Cu1—S1) lies adjacent to C—S bond which is closer to the C═S bond distance. The same characteristic is found in the structure of [Ni(pipdtc)(PPh₃)₂]ClO₄(PPh₃)·H₂O (pipdtc is piperidinedithiocarbamate; Venkatachalam et al., 1996), but different from the complex of [Au(S₂CPh)(PPh₃)₂] (Lanfredi et al., 1992), where the shorter Au—S bond lies adjacent to the C—S bond length which is closer to the C═S bond distance. The four-membered CuS₂C is nearly planar with normal bond lengths. The bond length of C37—N1 [1.360 (4) Å] has double-bond character, but slightly longer than those observed in a related structure (Jian et al., 1999). All the phenyl rings show normal bond parameters. The P—C bond distances are also normal. The C—P—C angles deviate appreciably from the ideal tetrahedral angle of 109.5°. The crystal structure is characterized by alternate layers of the complexes and the triphenylphosphine ligands which lie parallel to the bc plane. The structure is stabilized by C—H···π and van der Waals interactions (Table 2).

S2. Experimental

Sodium N,N-bis(2-hydroxyethyl)dithiocarbamate, Na[S₂CN(C₂H₄OH)₂], was dissolved in H₂O. CuCl₂ was then added at room temperature with stirring. The brown reaction mixture was filtered and the filtrate was washed with water and dried overnight in vacuo. The dried brown solid was dissolved in EtOH and triphenylphosphine was added at 253–263 K with stirring and refluxed for 4–5 h. Upon cooling, the colourless solution obtained was filtered and left to evaporate. After a few days, colourless solids were separated out and were recrystallized from EtOH/CHCl₃. The single crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature of the EtOH solvent.

S3. Refinement

After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms. The O1 atom in one of the hydroxyethyl groups is disordered and was refined with an occupancy ratio of of 78:22.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

N,N-bis(2-hydroxyethyl)dithiocarbamatobis(triphenylphosphine) Copper(I) Triphenylphosphine

Crystal data

[Cu(C5H10NO2S2)(C18H15P)2]·C18H15P	Z = 2
Mr = 1030.61	F(000) = 1076
Triclinic, P1	Dx = 1.291 Mg m^−3
a = 12.2892 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.1612 (5) Å	Cell parameters from 7234 reflections
c = 19.3696 (7) Å	θ = 1.1–28.3°
α = 95.512 (1)°	µ = 0.62 mm^−1
β = 103.177 (1)°	T = 293 K
γ = 116.801 (1)°	Slab, colourless
V = 2650.47 (16) Å^3	0.40 × 0.30 × 0.14 mm

Data collection

Siemens SMART CCD area-detector diffractometer	11791 independent reflections
Radiation source: fine-focus sealed tube	5663 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Detector resolution: 8.33 pixels mm^-1	θmax = 27.5°, θmin = 1.1°
ω scans	h = −15→14
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −17→17
Tmin = 0.788, Tmax = 0.918	l = −18→25
18118 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0271P)^2] where P = (Fo^2 + 2Fc^2)/3
11791 reflections	(Δ/σ)max < 0.001
624 parameters	Δρmax = 0.44 e Å^−3
2 restraints	Δρmin = −0.76 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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	Occ. (<1)
Cu1	0.80742 (4)	0.72780 (4)	0.17311 (2)	0.03704 (14)
S1	0.66316 (10)	0.56518 (8)	0.21407 (6)	0.0494 (3)
S2	0.90455 (10)	0.77027 (9)	0.30192 (6)	0.0541 (3)
P1	0.89873 (9)	0.64554 (8)	0.11330 (5)	0.0336 (2)
P2	0.75898 (9)	0.86555 (8)	0.13888 (5)	0.0353 (2)
P3	0.34121 (14)	0.21258 (11)	0.40644 (7)	0.0749 (4)
O1A	0.7498 (15)	0.3672 (11)	0.2817 (8)	0.086 (8)	0.225 (12)
H1A	0.8247	0.4165	0.3025	0.129*	0.225 (12)
O1B	0.7558 (12)	0.3435 (8)	0.3739 (6)	0.276 (7)	0.775 (12)
H1B	0.8290	0.3984	0.3858	0.415*	0.775 (12)
O2	0.9872 (8)	0.5264 (7)	0.4329 (3)	0.238 (4)
H2A	0.9325	0.4782	0.3961	0.358*
N1	0.7788 (4)	0.5833 (3)	0.3529 (2)	0.0726 (12)
C1	0.9196 (3)	0.5288 (3)	0.14912 (19)	0.0341 (8)
C2	0.9840 (4)	0.5535 (3)	0.2228 (2)	0.0525 (11)
H2B	1.0138	0.6266	0.2521	0.063*
C3	1.0040 (4)	0.4690 (4)	0.2529 (2)	0.0669 (13)
H3A	1.0489	0.4865	0.3020	0.080*
C4	0.9573 (4)	0.3600 (4)	0.2101 (3)	0.0586 (12)
H4A	0.9698	0.3035	0.2305	0.070*
C5	0.8930 (4)	0.3340 (3)	0.1379 (2)	0.0541 (11)
H5A	0.8620	0.2602	0.1092	0.065*
C6	0.8739 (3)	0.4182 (3)	0.1072 (2)	0.0447 (10)
H6A	0.8300	0.4000	0.0579	0.054*
C7	1.0598 (3)	0.7436 (3)	0.11043 (19)	0.0358 (8)
C8	1.1457 (4)	0.7067 (3)	0.1010 (2)	0.0488 (10)
H8A	1.1213	0.6277	0.0954	0.059*
C9	1.2656 (4)	0.7834 (4)	0.0997 (3)	0.0636 (13)
H9A	1.3216	0.7561	0.0942	0.076*
C10	1.3045 (4)	0.9012 (3)	0.1064 (2)	0.0572 (12)
H10A	1.3854	0.9535	0.1048	0.069*
C11	1.2193 (4)	0.9387 (3)	0.1158 (2)	0.0544 (11)
H11A	1.2437	1.0177	0.1207	0.065*
C12	1.0994 (4)	0.8621 (3)	0.1178 (2)	0.0454 (10)
H12A	1.0441	0.8898	0.1243	0.054*
C13	0.8053 (3)	0.5725 (3)	0.01799 (19)	0.0329 (8)
C14	0.8580 (4)	0.5857 (3)	−0.0391 (2)	0.0404 (9)
H14A	0.9458	0.6322	−0.0295	0.049*
C15	0.7800 (4)	0.5298 (3)	−0.1103 (2)	0.0493 (10)
H15A	0.8161	0.5387	−0.1481	0.059*
C16	0.6511 (4)	0.4619 (3)	−0.1251 (2)	0.0516 (11)
H16A	0.5997	0.4254	−0.1730	0.062*
C17	0.5968 (4)	0.4472 (3)	−0.0698 (2)	0.0512 (11)
H17A	0.5089	0.4001	−0.0801	0.061*
C18	0.6737 (3)	0.5028 (3)	0.0016 (2)	0.0432 (10)
H18A	0.6366	0.4932	0.0390	0.052*
C19	0.9015 (3)	0.9973 (3)	0.1382 (2)	0.0352 (9)
C20	1.0015 (4)	1.0569 (3)	0.2033 (2)	0.0461 (10)
H20A	0.9913	1.0326	0.2460	0.055*
C21	1.1152 (4)	1.1515 (3)	0.2051 (2)	0.0535 (11)
H21A	1.1812	1.1904	0.2488	0.064*
C22	1.1306 (4)	1.1875 (3)	0.1430 (3)	0.0577 (12)
H22A	1.2073	1.2514	0.1446	0.069*
C23	1.0349 (4)	1.1314 (3)	0.0782 (2)	0.0573 (12)
H23A	1.0466	1.1570	0.0360	0.069*
C24	0.9202 (4)	1.0361 (3)	0.0758 (2)	0.0465 (10)
H24A	0.8551	0.9980	0.0317	0.056*
C25	0.6463 (3)	0.8301 (3)	0.0478 (2)	0.0369 (9)
C26	0.6492 (4)	0.7591 (3)	−0.0091 (2)	0.0455 (10)
H26A	0.7087	0.7328	−0.0005	0.055*
C27	0.5646 (4)	0.7273 (3)	−0.0784 (2)	0.0549 (11)
H27A	0.5684	0.6812	−0.1163	0.066*
C28	0.4757 (4)	0.7640 (4)	−0.0907 (3)	0.0603 (12)
H28A	0.4179	0.7413	−0.1370	0.072*
C29	0.4704 (4)	0.8334 (4)	−0.0362 (3)	0.0619 (12)
H29A	0.4099	0.8584	−0.0455	0.074*
C30	0.5555 (4)	0.8669 (3)	0.0334 (2)	0.0520 (11)
H30A	0.5516	0.9143	0.0705	0.062*
C31	0.6961 (3)	0.9253 (3)	0.1992 (2)	0.0376 (9)
C32	0.7103 (4)	1.0365 (3)	0.2033 (2)	0.0513 (11)
H32A	0.7559	1.0846	0.1763	0.062*
C33	0.6565 (4)	1.0765 (4)	0.2477 (3)	0.0639 (13)
H33A	0.6664	1.1512	0.2502	0.077*
C34	0.5897 (5)	1.0071 (4)	0.2875 (3)	0.0730 (14)
H34A	0.5539	1.0342	0.3170	0.088*
C35	0.5751 (4)	0.8956 (4)	0.2838 (3)	0.0745 (14)
H35A	0.5288	0.8475	0.3106	0.089*
C36	0.6289 (4)	0.8563 (4)	0.2407 (2)	0.0554 (11)
H36A	0.6202	0.7822	0.2393	0.066*
C37	0.7816 (4)	0.6345 (3)	0.2950 (2)	0.0474 (10)
C38	0.6678 (6)	0.4721 (4)	0.3495 (3)	0.108 (2)
H38A	0.5920	0.4670	0.3168	0.130*
H38B	0.6568	0.4720	0.3975	0.130*
C39	0.6767 (11)	0.3672 (6)	0.3249 (7)	0.185 (4)
H39A	0.5905	0.3076	0.2990	0.222*	0.225 (12)
H39B	0.7042	0.3425	0.3674	0.222*	0.225 (12)
H39C	0.7025	0.3740	0.2816	0.222*	0.775 (12)
H39D	0.5913	0.3024	0.3114	0.222*	0.775 (12)
C40	0.8777 (6)	0.6438 (5)	0.4234 (3)	0.0982 (19)
H40A	0.8429	0.6102	0.4610	0.118*
H40B	0.8988	0.7252	0.4330	0.118*
C41	1.0001 (8)	0.6379 (7)	0.4292 (3)	0.148 (3)
H41A	1.0278	0.6598	0.3872	0.177*
H41B	1.0665	0.6946	0.4723	0.177*
C42	0.3256 (4)	0.0683 (4)	0.3986 (3)	0.0736 (14)
C43	0.2878 (5)	0.0012 (5)	0.3280 (3)	0.0874 (16)
H43A	0.2738	0.0330	0.2883	0.105*
C44	0.2713 (5)	−0.1090 (5)	0.3162 (4)	0.106 (2)
H44A	0.2440	−0.1518	0.2687	0.127*
C45	0.2939 (6)	−0.1570 (5)	0.3726 (4)	0.107 (2)
H45A	0.2833	−0.2321	0.3641	0.129*
C46	0.3324 (7)	−0.0945 (6)	0.4421 (5)	0.138 (3)
H46A	0.3497	−0.1268	0.4811	0.165*
C47	0.3461 (6)	0.0173 (5)	0.4553 (4)	0.108 (2)
H47A	0.3694	0.0578	0.5029	0.129*
C48	0.4414 (5)	0.2846 (4)	0.5021 (3)	0.0639 (13)
C49	0.5730 (5)	0.3397 (4)	0.5160 (3)	0.0796 (15)
H49A	0.6059	0.3353	0.4778	0.096*
C50	0.6555 (6)	0.4001 (5)	0.5838 (4)	0.0962 (19)
H50A	0.7434	0.4351	0.5916	0.115*
C51	0.6087 (7)	0.4093 (5)	0.6405 (3)	0.098 (2)
H51A	0.6650	0.4522	0.6866	0.117*
C52	0.4801 (6)	0.3557 (5)	0.6295 (3)	0.0929 (18)
H52A	0.4483	0.3605	0.6682	0.111*
C53	0.3960 (5)	0.2930 (5)	0.5594 (3)	0.0818 (15)
H53A	0.3081	0.2568	0.5517	0.098*
C54	0.1838 (5)	0.1845 (4)	0.4070 (2)	0.0649 (13)
C55	0.0865 (6)	0.0806 (5)	0.4143 (3)	0.0857 (16)
H55A	0.1042	0.0205	0.4230	0.103*
C56	−0.0324 (6)	0.0640 (5)	0.4093 (4)	0.105 (2)
H56A	−0.0944	−0.0068	0.4140	0.126*
C57	−0.0614 (7)	0.1493 (7)	0.3975 (3)	0.117 (3)
H57A	−0.1429	0.1376	0.3948	0.140*
C58	0.0276 (9)	0.2520 (7)	0.3896 (3)	0.113 (3)
H58A	0.0073	0.3107	0.3815	0.136*
C59	0.1486 (7)	0.2696 (5)	0.3937 (3)	0.0935 (19)
H59A	0.2084	0.3402	0.3875	0.112*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0467 (3)	0.0355 (3)	0.0384 (3)	0.0244 (2)	0.0180 (2)	0.0143 (2)
S1	0.0560 (7)	0.0412 (6)	0.0466 (6)	0.0163 (5)	0.0227 (5)	0.0121 (5)
S2	0.0656 (7)	0.0457 (6)	0.0415 (6)	0.0274 (6)	0.0022 (5)	0.0025 (5)
P1	0.0376 (5)	0.0313 (5)	0.0387 (6)	0.0200 (4)	0.0154 (5)	0.0114 (4)
P2	0.0426 (6)	0.0328 (5)	0.0390 (6)	0.0221 (5)	0.0173 (5)	0.0133 (4)
P3	0.0951 (11)	0.0748 (9)	0.0525 (8)	0.0418 (8)	0.0192 (8)	0.0115 (7)
O1A	0.124 (15)	0.028 (8)	0.099 (15)	0.025 (8)	0.053 (11)	0.010 (8)
O1B	0.490 (18)	0.204 (8)	0.362 (16)	0.275 (11)	0.263 (14)	0.156 (10)
O2	0.491 (12)	0.355 (8)	0.107 (4)	0.384 (9)	0.107 (6)	0.110 (5)
N1	0.135 (4)	0.067 (3)	0.044 (2)	0.063 (3)	0.040 (2)	0.029 (2)
C1	0.034 (2)	0.034 (2)	0.041 (2)	0.0177 (17)	0.0188 (18)	0.0149 (18)
C2	0.070 (3)	0.052 (2)	0.044 (3)	0.038 (2)	0.014 (2)	0.012 (2)
C3	0.093 (4)	0.079 (3)	0.050 (3)	0.059 (3)	0.016 (3)	0.028 (3)
C4	0.069 (3)	0.058 (3)	0.075 (3)	0.044 (2)	0.030 (3)	0.038 (3)
C5	0.064 (3)	0.035 (2)	0.069 (3)	0.026 (2)	0.025 (3)	0.018 (2)
C6	0.049 (2)	0.038 (2)	0.046 (2)	0.0195 (19)	0.014 (2)	0.0136 (19)
C7	0.040 (2)	0.034 (2)	0.037 (2)	0.0205 (17)	0.0128 (17)	0.0078 (17)
C8	0.046 (2)	0.037 (2)	0.071 (3)	0.021 (2)	0.031 (2)	0.011 (2)
C9	0.043 (3)	0.061 (3)	0.102 (4)	0.031 (2)	0.036 (3)	0.018 (3)
C10	0.037 (2)	0.048 (3)	0.080 (3)	0.012 (2)	0.024 (2)	0.014 (2)
C11	0.047 (3)	0.037 (2)	0.077 (3)	0.015 (2)	0.024 (2)	0.015 (2)
C12	0.041 (2)	0.039 (2)	0.062 (3)	0.0244 (19)	0.016 (2)	0.012 (2)
C13	0.041 (2)	0.0280 (18)	0.040 (2)	0.0227 (17)	0.0167 (18)	0.0127 (17)
C14	0.043 (2)	0.038 (2)	0.045 (2)	0.0203 (18)	0.020 (2)	0.0123 (19)
C15	0.063 (3)	0.054 (3)	0.040 (3)	0.032 (2)	0.024 (2)	0.014 (2)
C16	0.056 (3)	0.046 (2)	0.043 (3)	0.023 (2)	0.004 (2)	0.006 (2)
C17	0.037 (2)	0.045 (2)	0.061 (3)	0.015 (2)	0.008 (2)	0.010 (2)
C18	0.041 (2)	0.034 (2)	0.054 (3)	0.0143 (19)	0.020 (2)	0.016 (2)
C19	0.038 (2)	0.0300 (19)	0.045 (2)	0.0196 (17)	0.0157 (19)	0.0146 (18)
C20	0.051 (3)	0.044 (2)	0.040 (2)	0.020 (2)	0.014 (2)	0.012 (2)
C21	0.047 (3)	0.050 (3)	0.053 (3)	0.020 (2)	0.009 (2)	0.008 (2)
C22	0.049 (3)	0.039 (2)	0.078 (4)	0.014 (2)	0.024 (3)	0.015 (2)
C23	0.062 (3)	0.049 (3)	0.059 (3)	0.019 (2)	0.026 (2)	0.023 (2)
C24	0.053 (3)	0.042 (2)	0.044 (2)	0.022 (2)	0.014 (2)	0.015 (2)
C25	0.037 (2)	0.0310 (19)	0.043 (2)	0.0142 (17)	0.0150 (18)	0.0151 (18)
C26	0.047 (2)	0.043 (2)	0.052 (3)	0.023 (2)	0.018 (2)	0.014 (2)
C27	0.056 (3)	0.054 (3)	0.043 (3)	0.021 (2)	0.011 (2)	0.004 (2)
C28	0.048 (3)	0.065 (3)	0.050 (3)	0.018 (2)	0.003 (2)	0.016 (2)
C29	0.056 (3)	0.073 (3)	0.061 (3)	0.039 (3)	0.007 (2)	0.015 (3)
C30	0.049 (3)	0.052 (2)	0.058 (3)	0.028 (2)	0.014 (2)	0.011 (2)
C31	0.041 (2)	0.036 (2)	0.041 (2)	0.0204 (18)	0.0181 (18)	0.0094 (18)
C32	0.062 (3)	0.045 (2)	0.059 (3)	0.032 (2)	0.025 (2)	0.015 (2)
C33	0.075 (3)	0.055 (3)	0.071 (3)	0.041 (3)	0.025 (3)	0.004 (3)
C34	0.077 (3)	0.080 (4)	0.074 (4)	0.048 (3)	0.032 (3)	−0.002 (3)
C35	0.080 (3)	0.080 (4)	0.087 (4)	0.043 (3)	0.055 (3)	0.027 (3)
C36	0.067 (3)	0.048 (2)	0.064 (3)	0.032 (2)	0.033 (2)	0.015 (2)
C37	0.085 (3)	0.047 (2)	0.035 (2)	0.045 (2)	0.031 (2)	0.0194 (19)
C38	0.214 (7)	0.073 (4)	0.097 (4)	0.086 (4)	0.105 (5)	0.057 (3)
C39	0.331 (14)	0.085 (5)	0.215 (11)	0.129 (7)	0.141 (12)	0.070 (6)
C40	0.175 (6)	0.125 (5)	0.041 (3)	0.111 (5)	0.029 (4)	0.026 (3)
C41	0.246 (9)	0.219 (8)	0.061 (4)	0.189 (8)	0.030 (5)	0.036 (5)
C42	0.065 (3)	0.085 (4)	0.069 (4)	0.041 (3)	0.012 (3)	0.006 (3)
C43	0.085 (4)	0.093 (4)	0.079 (4)	0.047 (3)	0.017 (3)	−0.003 (3)
C44	0.103 (5)	0.092 (5)	0.114 (6)	0.053 (4)	0.022 (4)	−0.018 (4)
C45	0.102 (5)	0.071 (4)	0.143 (7)	0.056 (4)	0.007 (5)	−0.004 (4)
C46	0.161 (7)	0.103 (5)	0.135 (7)	0.084 (5)	−0.013 (6)	0.008 (5)
C47	0.138 (5)	0.081 (4)	0.095 (5)	0.066 (4)	−0.003 (4)	0.006 (4)
C48	0.080 (4)	0.052 (3)	0.056 (3)	0.030 (3)	0.020 (3)	0.011 (2)
C49	0.085 (4)	0.075 (3)	0.073 (4)	0.030 (3)	0.028 (3)	0.025 (3)
C50	0.090 (4)	0.078 (4)	0.085 (5)	0.023 (3)	0.001 (4)	0.020 (4)
C51	0.117 (6)	0.081 (4)	0.069 (4)	0.046 (4)	−0.005 (4)	0.000 (3)
C52	0.119 (5)	0.117 (5)	0.058 (4)	0.074 (4)	0.024 (4)	0.010 (3)
C53	0.090 (4)	0.097 (4)	0.062 (4)	0.052 (3)	0.017 (3)	0.014 (3)
C54	0.091 (4)	0.059 (3)	0.041 (3)	0.040 (3)	0.009 (3)	0.008 (2)
C55	0.090 (4)	0.073 (4)	0.095 (4)	0.048 (3)	0.016 (3)	0.005 (3)
C56	0.079 (4)	0.099 (5)	0.115 (5)	0.039 (4)	0.016 (4)	−0.014 (4)
C57	0.108 (6)	0.167 (7)	0.064 (4)	0.090 (6)	−0.018 (4)	−0.029 (5)
C58	0.189 (8)	0.162 (7)	0.051 (4)	0.146 (7)	0.018 (5)	0.016 (4)
C59	0.165 (6)	0.092 (4)	0.050 (3)	0.087 (4)	0.028 (4)	0.020 (3)

Geometric parameters (Å, º)

Cu1—P2	2.2595 (9)	C24—H24A	0.9300
Cu1—P1	2.2849 (10)	C25—C30	1.389 (5)
Cu1—S2	2.3946 (11)	C25—C26	1.393 (5)
Cu1—S1	2.4287 (10)	C26—C27	1.386 (5)
S1—C37	1.702 (4)	C26—H26A	0.9300
S2—C37	1.710 (4)	C27—C28	1.365 (6)
P1—C13	1.830 (4)	C27—H27A	0.9300
P1—C7	1.830 (4)	C28—C29	1.362 (6)
P1—C1	1.840 (3)	C28—H28A	0.9300
P2—C19	1.831 (4)	C29—C30	1.390 (5)
P2—C31	1.834 (4)	C29—H29A	0.9300
P2—C25	1.841 (4)	C30—H30A	0.9300
P3—C54	1.801 (5)	C31—C36	1.385 (5)
P3—C42	1.808 (5)	C31—C32	1.386 (5)
P3—C48	1.849 (5)	C32—C33	1.393 (6)
O1A—C39	1.360 (10)	C32—H32A	0.9300
O1A—H1A	0.8200	C33—C34	1.359 (6)
O1A—H39C	0.6264	C33—H33A	0.9300
O1B—C39	1.362 (10)	C34—C35	1.389 (6)
O1B—H1B	0.8200	C34—H34A	0.9300
O1B—H39B	0.6113	C35—C36	1.371 (6)
O2—C41	1.414 (8)	C35—H35A	0.9300
O2—H2A	0.8200	C36—H36A	0.9300
N1—C37	1.360 (5)	C38—C39	1.475 (8)
N1—C40	1.463 (6)	C38—H38A	0.9700
N1—C38	1.465 (6)	C38—H38B	0.9700
C1—C6	1.387 (5)	C39—H39A	0.9601
C1—C2	1.391 (5)	C39—H39B	0.9600
C2—C3	1.393 (5)	C39—H39C	0.9600
C2—H2B	0.9300	C39—H39D	0.9600
C3—C4	1.375 (6)	C40—C41	1.520 (8)
C3—H3A	0.9300	C40—H40A	0.9700
C4—C5	1.362 (6)	C40—H40B	0.9700
C4—H4A	0.9300	C41—H41A	0.9700
C5—C6	1.390 (5)	C41—H41B	0.9700
C5—H5A	0.9300	C42—C47	1.374 (7)
C6—H6A	0.9300	C42—C43	1.404 (7)
C7—C8	1.384 (5)	C43—C44	1.358 (7)
C7—C12	1.390 (4)	C43—H43A	0.9300
C8—C9	1.368 (5)	C44—C45	1.350 (8)
C8—H8A	0.9300	C44—H44A	0.9300
C9—C10	1.383 (5)	C45—C46	1.364 (9)
C9—H9A	0.9300	C45—H45A	0.9300
C10—C11	1.381 (5)	C46—C47	1.394 (7)
C10—H10A	0.9300	C46—H46A	0.9300
C11—C12	1.372 (5)	C47—H47A	0.9300
C11—H11A	0.9300	C48—C53	1.368 (7)
C12—H12A	0.9300	C48—C49	1.385 (6)
C13—C18	1.389 (5)	C49—C50	1.359 (7)
C13—C14	1.391 (5)	C49—H49A	0.9300
C14—C15	1.389 (5)	C50—C51	1.370 (8)
C14—H14A	0.9300	C50—H50A	0.9300
C15—C16	1.363 (5)	C51—C52	1.361 (8)
C15—H15A	0.9300	C51—H51A	0.9300
C16—C17	1.370 (6)	C52—C53	1.405 (7)
C16—H16A	0.9300	C52—H52A	0.9300
C17—C18	1.389 (5)	C53—H53A	0.9300
C17—H17A	0.9300	C54—C59	1.396 (6)
C18—H18A	0.9300	C54—C55	1.400 (6)
C19—C24	1.383 (5)	C55—C56	1.355 (7)
C19—C20	1.397 (5)	C55—H55A	0.9300
C20—C21	1.380 (5)	C56—C57	1.346 (8)
C20—H20A	0.9300	C56—H56A	0.9300
C21—C22	1.356 (6)	C57—C58	1.353 (8)
C21—H21A	0.9300	C57—H57A	0.9300
C22—C23	1.368 (6)	C58—C59	1.379 (8)
C22—H22A	0.9300	C58—H58A	0.9300
C23—C24	1.388 (5)	C59—H59A	0.9300
C23—H23A	0.9300
P2—Cu1—P1	124.51 (4)	C30—C29—H29A	120.0
P2—Cu1—S2	112.35 (4)	C25—C30—C29	120.5 (4)
P1—Cu1—S2	109.85 (4)	C25—C30—H30A	119.8
P2—Cu1—S1	122.04 (4)	C29—C30—H30A	119.8
P1—Cu1—S1	102.49 (4)	C36—C31—C32	118.5 (4)
S2—Cu1—S1	74.77 (4)	C36—C31—P2	119.3 (3)
C37—S1—Cu1	82.63 (13)	C32—C31—P2	122.2 (3)
C37—S2—Cu1	83.54 (13)	C31—C32—C33	120.2 (4)
C13—P1—C7	104.59 (16)	C31—C32—H32A	119.9
C13—P1—C1	102.02 (15)	C33—C32—H32A	119.9
C7—P1—C1	101.92 (15)	C34—C33—C32	120.5 (4)
C13—P1—Cu1	113.80 (11)	C34—C33—H33A	119.7
C7—P1—Cu1	116.68 (12)	C32—C33—H33A	119.7
C1—P1—Cu1	115.96 (12)	C33—C34—C35	119.8 (5)
C19—P2—C31	101.80 (16)	C33—C34—H34A	120.1
C19—P2—C25	103.13 (16)	C35—C34—H34A	120.1
C31—P2—C25	103.43 (17)	C36—C35—C34	119.9 (5)
C19—P2—Cu1	111.55 (11)	C36—C35—H35A	120.0
C31—P2—Cu1	116.40 (12)	C34—C35—H35A	120.0
C25—P2—Cu1	118.46 (12)	C35—C36—C31	121.2 (4)
C54—P3—C42	102.2 (2)	C35—C36—H36A	119.4
C54—P3—C48	103.9 (2)	C31—C36—H36A	119.4
C42—P3—C48	102.2 (2)	N1—C37—S1	121.0 (3)
C39—O1A—H1A	109.5	N1—C37—S2	120.7 (3)
C39—O1A—H39C	39.2	S1—C37—S2	118.3 (2)
H1A—O1A—H39C	125.0	N1—C38—C39	114.7 (6)
C39—O1B—H1B	109.5	N1—C38—H38A	108.6
C39—O1B—H39B	38.3	C39—C38—H38A	108.6
H1B—O1B—H39B	131.0	N1—C38—H38B	108.6
C41—O2—H2A	109.5	C39—C38—H38B	108.6
C37—N1—C40	121.4 (4)	H38A—C38—H38B	107.6
C37—N1—C38	120.9 (4)	O1A—C39—O1B	84.7 (11)
C40—N1—C38	117.2 (4)	O1A—C39—C38	122.0 (10)
C6—C1—C2	118.5 (3)	O1B—C39—C38	116.5 (9)
C6—C1—P1	123.9 (3)	O1A—C39—H39A	106.8
C2—C1—P1	117.6 (3)	O1B—C39—H39A	120.8
C1—C2—C3	120.3 (4)	C38—C39—H39A	105.6
C1—C2—H2B	119.9	O1A—C39—H39B	107.1
C3—C2—H2B	119.9	O1B—C39—H39B	23.3
C4—C3—C2	120.0 (4)	C38—C39—H39B	107.7
C4—C3—H3A	120.0	H39A—C39—H39B	106.9
C2—C3—H3A	120.0	O1A—C39—H39C	24.4
C5—C4—C3	120.5 (4)	O1B—C39—H39C	109.1
C5—C4—H4A	119.7	C38—C39—H39C	108.6
C3—C4—H4A	119.7	H39A—C39—H39C	93.4
C4—C5—C6	119.9 (4)	H39B—C39—H39C	131.2
C4—C5—H5A	120.0	O1A—C39—H39D	117.0
C6—C5—H5A	120.0	O1B—C39—H39D	108.8
C1—C6—C5	120.9 (4)	C38—C39—H39D	106.2
C1—C6—H6A	119.6	H39A—C39—H39D	15.3
C5—C6—H6A	119.6	H39B—C39—H39D	92.5
C8—C7—C12	117.4 (3)	H39C—C39—H39D	107.2
C8—C7—P1	123.8 (3)	N1—C40—C41	114.6 (5)
C12—C7—P1	118.8 (3)	N1—C40—H40A	108.6
C9—C8—C7	121.7 (3)	C41—C40—H40A	108.6
C9—C8—H8A	119.1	N1—C40—H40B	108.6
C7—C8—H8A	119.1	C41—C40—H40B	108.6
C8—C9—C10	120.7 (4)	H40A—C40—H40B	107.6
C8—C9—H9A	119.6	O2—C41—C40	113.8 (7)
C10—C9—H9A	119.6	O2—C41—H41A	108.8
C11—C10—C9	117.9 (4)	C40—C41—H41A	108.8
C11—C10—H10A	121.1	O2—C41—H41B	108.8
C9—C10—H10A	121.1	C40—C41—H41B	108.8
C12—C11—C10	121.4 (4)	H41A—C41—H41B	107.7
C12—C11—H11A	119.3	C47—C42—C43	116.6 (5)
C10—C11—H11A	119.3	C47—C42—P3	126.1 (4)
C11—C12—C7	120.8 (4)	C43—C42—P3	117.3 (4)
C11—C12—H12A	119.6	C44—C43—C42	121.9 (6)
C7—C12—H12A	119.6	C44—C43—H43A	119.1
C18—C13—C14	118.3 (3)	C42—C43—H43A	119.1
C18—C13—P1	118.0 (3)	C45—C44—C43	120.7 (6)
C14—C13—P1	123.7 (3)	C45—C44—H44A	119.7
C15—C14—C13	120.2 (4)	C43—C44—H44A	119.7
C15—C14—H14A	119.9	C44—C45—C46	119.6 (6)
C13—C14—H14A	119.9	C44—C45—H45A	120.2
C16—C15—C14	120.5 (4)	C46—C45—H45A	120.2
C16—C15—H15A	119.8	C45—C46—C47	120.5 (7)
C14—C15—H15A	119.8	C45—C46—H46A	119.7
C15—C16—C17	120.4 (4)	C47—C46—H46A	119.7
C15—C16—H16A	119.8	C42—C47—C46	120.7 (6)
C17—C16—H16A	119.8	C42—C47—H47A	119.7
C16—C17—C18	119.7 (4)	C46—C47—H47A	119.7
C16—C17—H17A	120.2	C53—C48—C49	117.5 (5)
C18—C17—H17A	120.2	C53—C48—P3	125.1 (4)
C17—C18—C13	120.9 (4)	C49—C48—P3	117.3 (4)
C17—C18—H18A	119.5	C50—C49—C48	122.1 (6)
C13—C18—H18A	119.5	C50—C49—H49A	118.9
C24—C19—C20	117.9 (3)	C48—C49—H49A	118.9
C24—C19—P2	123.8 (3)	C49—C50—C51	119.7 (6)
C20—C19—P2	118.1 (3)	C49—C50—H50A	120.1
C21—C20—C19	120.8 (4)	C51—C50—H50A	120.1
C21—C20—H20A	119.6	C52—C51—C50	120.2 (6)
C19—C20—H20A	119.6	C52—C51—H51A	119.9
C22—C21—C20	119.8 (4)	C50—C51—H51A	119.9
C22—C21—H21A	120.1	C51—C52—C53	119.5 (6)
C20—C21—H21A	120.1	C51—C52—H52A	120.3
C21—C22—C23	121.0 (4)	C53—C52—H52A	120.3
C21—C22—H22A	119.5	C48—C53—C52	120.9 (5)
C23—C22—H22A	119.5	C48—C53—H53A	119.5
C22—C23—C24	119.6 (4)	C52—C53—H53A	119.5
C22—C23—H23A	120.2	C59—C54—C55	114.7 (5)
C24—C23—H23A	120.2	C59—C54—P3	118.6 (5)
C19—C24—C23	120.8 (4)	C55—C54—P3	126.5 (4)
C19—C24—H24A	119.6	C56—C55—C54	122.7 (5)
C23—C24—H24A	119.6	C56—C55—H55A	118.6
C30—C25—C26	118.2 (4)	C54—C55—H55A	118.6
C30—C25—P2	123.5 (3)	C57—C56—C55	120.5 (7)
C26—C25—P2	118.3 (3)	C57—C56—H56A	119.8
C27—C26—C25	120.8 (4)	C55—C56—H56A	119.8
C27—C26—H26A	119.6	C56—C57—C58	120.2 (7)
C25—C26—H26A	119.6	C56—C57—H57A	119.9
C28—C27—C26	119.6 (4)	C58—C57—H57A	119.9
C28—C27—H27A	120.2	C57—C58—C59	120.0 (7)
C26—C27—H27A	120.2	C57—C58—H58A	120.0
C29—C28—C27	121.0 (4)	C59—C58—H58A	120.0
C29—C28—H28A	119.5	C58—C59—C54	121.9 (6)
C27—C28—H28A	119.5	C58—C59—H59A	119.0
C28—C29—C30	119.9 (4)	C54—C59—H59A	119.0
C28—C29—H29A	120.0
P2—Cu1—S1—C37	−112.58 (13)	C19—P2—C25—C30	−94.1 (3)
P1—Cu1—S1—C37	102.00 (13)	C31—P2—C25—C30	11.7 (3)
S2—Cu1—S1—C37	−5.46 (13)	Cu1—P2—C25—C30	142.2 (3)
P2—Cu1—S2—C37	124.27 (13)	C19—P2—C25—C26	88.3 (3)
P1—Cu1—S2—C37	−92.63 (13)	C31—P2—C25—C26	−166.0 (3)
S1—Cu1—S2—C37	5.43 (13)	Cu1—P2—C25—C26	−35.5 (3)
P2—Cu1—P1—C13	−58.55 (13)	C30—C25—C26—C27	0.7 (5)
S2—Cu1—P1—C13	163.82 (12)	P2—C25—C26—C27	178.5 (3)
S1—Cu1—P1—C13	85.72 (12)	C25—C26—C27—C28	−1.3 (6)
P2—Cu1—P1—C7	63.43 (13)	C26—C27—C28—C29	1.3 (6)
S2—Cu1—P1—C7	−74.19 (13)	C27—C28—C29—C30	−0.7 (6)
S1—Cu1—P1—C7	−152.30 (13)	C26—C25—C30—C29	0.0 (5)
P2—Cu1—P1—C1	−176.45 (13)	P2—C25—C30—C29	−177.7 (3)
S2—Cu1—P1—C1	45.93 (13)	C28—C29—C30—C25	0.0 (6)
S1—Cu1—P1—C1	−32.18 (13)	C19—P2—C31—C36	−149.9 (3)
P1—Cu1—P2—C19	−59.84 (14)	C25—P2—C31—C36	103.3 (3)
S2—Cu1—P2—C19	76.89 (14)	Cu1—P2—C31—C36	−28.4 (3)
S1—Cu1—P2—C19	162.43 (13)	C19—P2—C31—C32	31.9 (3)
P1—Cu1—P2—C31	−176.04 (13)	C25—P2—C31—C32	−74.9 (3)
S2—Cu1—P2—C31	−39.30 (14)	Cu1—P2—C31—C32	153.4 (3)
S1—Cu1—P2—C31	46.23 (14)	C36—C31—C32—C33	−0.7 (6)
P1—Cu1—P2—C25	59.62 (14)	P2—C31—C32—C33	177.5 (3)
S2—Cu1—P2—C25	−163.64 (14)	C31—C32—C33—C34	0.0 (6)
S1—Cu1—P2—C25	−78.11 (14)	C32—C33—C34—C35	0.1 (7)
C13—P1—C1—C6	1.8 (3)	C33—C34—C35—C36	0.5 (8)
C7—P1—C1—C6	−106.2 (3)	C34—C35—C36—C31	−1.3 (7)
Cu1—P1—C1—C6	126.0 (3)	C32—C31—C36—C35	1.4 (6)
C13—P1—C1—C2	−177.6 (3)	P2—C31—C36—C35	−176.9 (4)
C7—P1—C1—C2	74.5 (3)	C40—N1—C37—S1	−177.9 (3)
Cu1—P1—C1—C2	−53.3 (3)	C38—N1—C37—S1	−5.9 (6)
C6—C1—C2—C3	1.4 (6)	C40—N1—C37—S2	2.2 (6)
P1—C1—C2—C3	−179.3 (3)	C38—N1—C37—S2	174.1 (3)
C1—C2—C3—C4	−1.6 (7)	Cu1—S1—C37—N1	−171.6 (3)
C2—C3—C4—C5	1.0 (7)	Cu1—S1—C37—S2	8.4 (2)
C3—C4—C5—C6	−0.2 (7)	Cu1—S2—C37—N1	171.4 (3)
C2—C1—C6—C5	−0.6 (6)	Cu1—S2—C37—S1	−8.5 (2)
P1—C1—C6—C5	−179.9 (3)	C37—N1—C38—C39	92.1 (8)
C4—C5—C6—C1	0.0 (6)	C40—N1—C38—C39	−95.6 (7)
C13—P1—C7—C8	−77.3 (3)	N1—C38—C39—O1A	−25.7 (16)
C1—P1—C7—C8	28.6 (4)	N1—C38—C39—O1B	75.3 (12)
Cu1—P1—C7—C8	156.0 (3)	C37—N1—C40—C41	−81.5 (6)
C13—P1—C7—C12	102.4 (3)	C38—N1—C40—C41	106.2 (6)
C1—P1—C7—C12	−151.6 (3)	N1—C40—C41—O2	−72.0 (6)
Cu1—P1—C7—C12	−24.2 (3)	C54—P3—C42—C47	−88.3 (5)
C12—C7—C8—C9	0.7 (6)	C48—P3—C42—C47	19.1 (6)
P1—C7—C8—C9	−179.5 (3)	C54—P3—C42—C43	91.1 (4)
C7—C8—C9—C10	−1.3 (7)	C48—P3—C42—C43	−161.5 (4)
C8—C9—C10—C11	1.1 (7)	C47—C42—C43—C44	0.6 (8)
C9—C10—C11—C12	−0.4 (7)	P3—C42—C43—C44	−178.9 (4)
C10—C11—C12—C7	−0.1 (6)	C42—C43—C44—C45	−1.7 (10)
C8—C7—C12—C11	0.0 (6)	C43—C44—C45—C46	0.7 (11)
P1—C7—C12—C11	−179.8 (3)	C44—C45—C46—C47	1.2 (12)
C7—P1—C13—C18	−171.9 (3)	C43—C42—C47—C46	1.4 (9)
C1—P1—C13—C18	82.2 (3)	P3—C42—C47—C46	−179.2 (5)
Cu1—P1—C13—C18	−43.4 (3)	C45—C46—C47—C42	−2.3 (12)
C7—P1—C13—C14	6.0 (3)	C54—P3—C48—C53	9.9 (5)
C1—P1—C13—C14	−99.9 (3)	C42—P3—C48—C53	−96.1 (5)
Cu1—P1—C13—C14	134.5 (3)	C54—P3—C48—C49	−166.3 (4)
C18—C13—C14—C15	−0.3 (5)	C42—P3—C48—C49	87.7 (4)
P1—C13—C14—C15	−178.2 (3)	C53—C48—C49—C50	0.2 (8)
C13—C14—C15—C16	0.4 (6)	P3—C48—C49—C50	176.7 (4)
C14—C15—C16—C17	−0.6 (6)	C48—C49—C50—C51	−1.1 (9)
C15—C16—C17—C18	0.7 (6)	C49—C50—C51—C52	1.6 (9)
C16—C17—C18—C13	−0.6 (6)	C50—C51—C52—C53	−1.3 (9)
C14—C13—C18—C17	0.4 (5)	C49—C48—C53—C52	0.1 (8)
P1—C13—C18—C17	178.4 (3)	P3—C48—C53—C52	−176.1 (4)
C31—P2—C19—C24	−120.3 (3)	C51—C52—C53—C48	0.4 (8)
C25—P2—C19—C24	−13.3 (3)	C42—P3—C54—C59	−163.7 (4)
Cu1—P2—C19—C24	114.9 (3)	C48—P3—C54—C59	90.2 (4)
C31—P2—C19—C20	64.9 (3)	C42—P3—C54—C55	11.2 (5)
C25—P2—C19—C20	171.9 (3)	C48—P3—C54—C55	−94.8 (4)
Cu1—P2—C19—C20	−59.9 (3)	C59—C54—C55—C56	−0.3 (8)
C24—C19—C20—C21	−0.1 (5)	P3—C54—C55—C56	−175.5 (5)
P2—C19—C20—C21	175.0 (3)	C54—C55—C56—C57	−0.7 (10)
C19—C20—C21—C22	0.2 (6)	C55—C56—C57—C58	0.9 (10)
C20—C21—C22—C23	−0.1 (7)	C56—C57—C58—C59	−0.1 (10)
C21—C22—C23—C24	0.0 (7)	C57—C58—C59—C54	−1.0 (9)
C20—C19—C24—C23	0.0 (5)	C55—C54—C59—C58	1.1 (7)
P2—C19—C24—C23	−174.8 (3)	P3—C54—C59—C58	176.7 (4)
C22—C23—C24—C19	0.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···Cg1	0.93	2.84	3.633	144
C44—H44A···Cg2^i	0.93	2.97	3.821	153

Symmetry code: (i) x−1, y−1, z.