(anti-Chlorido-thio-semicabazide-κS)bis-(tri-phenyl-phosphane-κP)copper(I) 0.48-hydrate.

In the mononuclear title complex, [CuCl(CH5N3S)(C18H15P)2]·0.48H2O, the Cu(I) ion is in a slightly distorted tetra-hedral coordination geometry formed by two P atoms from two tri-phenyl-phosphane ligands, one S atom from a thio-semicarbazide ligand and one chloride anion. An intra-molecular N-H⋯N hydrogen bond [graph-set motif S(5)] stabilizes the thio-semicarbazide ligand in its anti conformation, and an intra-molecular N-H⋯Cl hydrogen bond between the hydrazine N-H group and the chloride anion influences the arrangement and orientation of the ligands around the metal center. A weak intra-molecular C-H⋯Cl hydrogen bond is also present. In the crystal, complex mol-ecules are connected through N-H⋯Cl hydrogen bonds originating from the amide -NH2 group, and through O-H⋯S and O-H⋯Cl hydrogen bonds involving the solvent water mol-ecule. Both the direct N-H⋯Cl hydrogen bonds as well as the bridging hydrogen bonds mediated by the water mol-ecule connect the complex mol-ecules into zigzag chains that propagate along [010]. The solvent water mol-ecule is partially occupied, with a refined occupancy of 0.479 (7).

Related literature

For the coordination of thio­semicarbazide and thio­semicarbazones with metal complexes, see: Andreetti et al. (1970 ▶); Chattopadhyay et al. (1991 ▶); Jia et al. (2008a ▶,b ▶); Villa et al. (1972a ▶,b ▶); Qirong et al. (1987 ▶). For potential applications of related complexes, see: Alagarsamy & Parthiban (2011 ▶); Kowol et al. (2007 ▶); Pelosi (2010 ▶); Yu et al. (2009 ▶); Wattanakanjana et al. (2012 ▶). For n class="Chemical">hydrogen-bond graph-set motifs, see: Bernstein, et al. (1995 ▶). For a description of the Cambridge Structural Database (CSD), see: Allen (2002 ▶).

Experimental

Crystal data

[CuCl(CH5N3S)(C18H15P)2]·0.48H2O

M = 723.29

Monoclinic,

a = 14.8723 (7) Å

b = 12.4829 (6) Å

c = 19.2103 (9) Å

β = 96.126 (1)°

V = 3546.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.87 mm−1

T = 293 K

0.34 × 0.11 × 0.07 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003) ▶ T min = 0.880, T max = 1

48021 measured reflections

8591 independent reflections

6691 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.110

S = 1.06

8591 reflections

428 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶) and SHELXLE Rev609 (Hübschle et al., 2011 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813008556/lh5600sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008556/lh5600Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CuCl(CH5N3S)(C18H15P)2]·0.48H2O	F(000) = 1499.2
Mr = 723.29	Dx = 1.355 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.8723 (7) Å	Cell parameters from 7520 reflections
b = 12.4829 (6) Å	θ = 2.3–23.0°
c = 19.2103 (9) Å	µ = 0.87 mm−1
β = 96.126 (1)°	T = 293 K
V = 3546.0 (3) Å3	Block, colorless
Z = 4	0.34 × 0.11 × 0.07 mm

Bruker SMART APEX CCD diffractometer	8591 independent reflections
Radiation source: sealed tube	6691 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
φ and ω scans	θmax = 28.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −19→19
Tmin = 0.880, Tmax = 1	k = −16→16
48021 measured reflections	l = −25→25

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	Hydrogen site location: mixed
wR(F2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.050P)2 + 1.0259P] where P = (Fo2 + 2Fc2)/3
8591 reflections	(Δ/σ)max = 0.001
428 parameters	Δρmax = 0.42 e Å−3
4 restraints	Δρmin = −0.19 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.87688 (2)	0.69145 (2)	0.14512 (2)	0.03859 (9)
O1	0.6525 (4)	0.3863 (6)	0.1104 (3)	0.106 (3)	0.479 (7)
H1C	0.701 (4)	0.417 (8)	0.120 (6)	0.159*	0.479 (7)
H1D	0.631 (7)	0.336 (6)	0.130 (5)	0.159*	0.479 (7)
Cl1	0.84280 (4)	0.50261 (5)	0.14456 (3)	0.04861 (15)
S1	0.80953 (5)	0.77828 (5)	0.23718 (4)	0.05356 (18)
P1	1.02443 (4)	0.69509 (5)	0.19010 (3)	0.03600 (13)
P2	0.80809 (4)	0.77112 (5)	0.04621 (3)	0.03623 (14)
N1	0.64208 (18)	0.7719 (2)	0.27084 (16)	0.0810 (8)
H1A	0.5922	0.7396	0.2761	0.097*
H1B	0.6491	0.8380	0.2829	0.097*
N2	0.69393 (15)	0.61907 (19)	0.22675 (13)	0.0648 (7)
H2	0.7356	0.5829	0.2096	0.078*
N3	0.6107 (2)	0.5707 (3)	0.2361 (2)	0.1044 (13)
H3A	0.583 (3)	0.566 (4)	0.1932 (13)	0.125*
H3B	0.618 (3)	0.5052 (19)	0.248 (3)	0.125*
C1	0.70773 (18)	0.7203 (2)	0.24444 (13)	0.0514 (6)
C11	1.11233 (14)	0.66548 (18)	0.13309 (11)	0.0365 (5)
C12	1.09407 (17)	0.58379 (19)	0.08457 (13)	0.0469 (6)
H12	1.0388	0.5483	0.0817	0.056*
C13	1.1577 (2)	0.5551 (2)	0.04057 (14)	0.0567 (7)
H13	1.1452	0.5004	0.0081	0.068*
C14	1.2390 (2)	0.6069 (2)	0.04457 (15)	0.0585 (7)
H14	1.2815	0.5874	0.0147	0.070*
C15	1.25819 (18)	0.6875 (2)	0.09241 (16)	0.0583 (7)
H15	1.3138	0.7222	0.0950	0.070*
C16	1.19517 (16)	0.7173 (2)	0.13669 (13)	0.0477 (6)
H16	1.2083	0.7722	0.1689	0.057*
C21	1.05730 (15)	0.82700 (19)	0.22479 (13)	0.0418 (5)
C22	1.0509 (2)	0.9125 (2)	0.17833 (15)	0.0582 (7)
H22	1.0288	0.9006	0.1318	0.070*
C23	1.0763 (2)	1.0143 (2)	0.1993 (2)	0.0718 (9)
H23	1.0726	1.0702	0.1671	0.086*
C24	1.1072 (2)	1.0327 (3)	0.2678 (2)	0.0782 (10)
H24	1.1258	1.1011	0.2822	0.094*
C25	1.1109 (2)	0.9510 (3)	0.3150 (2)	0.0877 (12)
H25	1.1304	0.9644	0.3618	0.105*
C26	1.0856 (2)	0.8474 (3)	0.29384 (16)	0.0646 (8)
H26	1.0879	0.7923	0.3265	0.077*
C31	1.05437 (16)	0.60214 (19)	0.26296 (12)	0.0419 (5)
C32	1.14238 (18)	0.5696 (2)	0.28240 (14)	0.0559 (7)
H32	1.1889	0.5962	0.2586	0.067*
C33	1.1621 (2)	0.4978 (3)	0.33684 (16)	0.0677 (8)
H33	1.2217	0.4774	0.3498	0.081*
C34	1.0941 (2)	0.4567 (3)	0.37161 (16)	0.0727 (9)
H34	1.1074	0.4085	0.4082	0.087*
C35	1.0072 (2)	0.4869 (3)	0.35232 (16)	0.0747 (9)
H35	0.9611	0.4581	0.3755	0.090*
C36	0.98627 (19)	0.5600 (2)	0.29870 (14)	0.0573 (7)
H36	0.9266	0.5807	0.2867	0.069*
C41	0.68669 (15)	0.7430 (2)	0.02893 (12)	0.0422 (5)
C42	0.65597 (19)	0.6448 (3)	0.04902 (16)	0.0626 (7)
H42	0.6965	0.5956	0.0710	0.075*
C43	0.5651 (2)	0.6188 (3)	0.0366 (2)	0.0890 (11)
H43	0.5449	0.5524	0.0503	0.107*
C44	0.5049 (2)	0.6905 (4)	0.0044 (2)	0.0912 (12)
H44	0.4439	0.6731	−0.0035	0.109*
C45	0.5344 (2)	0.7876 (3)	−0.01622 (19)	0.0780 (10)
H45	0.4935	0.8360	−0.0386	0.094*
C46	0.62496 (18)	0.8145 (3)	−0.00402 (16)	0.0610 (7)
H46	0.6445	0.8812	−0.0180	0.073*
C51	0.85129 (15)	0.73927 (18)	−0.03696 (12)	0.0389 (5)
C52	0.79750 (19)	0.7307 (3)	−0.10006 (14)	0.0580 (7)
H52	0.7360	0.7458	−0.1022	0.070*
C53	0.8345 (2)	0.6999 (3)	−0.16006 (15)	0.0660 (8)
H53	0.7975	0.6944	−0.2021	0.079*
C54	0.9242 (2)	0.6776 (2)	−0.15837 (15)	0.0587 (7)
H54	0.9482	0.6560	−0.1989	0.070*
C55	0.97882 (19)	0.6872 (2)	−0.09687 (15)	0.0576 (7)
H55	1.0404	0.6735	−0.0956	0.069*
C56	0.94248 (17)	0.7172 (2)	−0.03655 (14)	0.0486 (6)
H56	0.9801	0.7226	0.0052	0.058*
C61	0.80914 (16)	0.91750 (19)	0.04859 (12)	0.0429 (5)
C62	0.7576 (2)	0.9697 (2)	0.09473 (15)	0.0605 (7)
H62	0.7245	0.9294	0.1238	0.073*
C63	0.7549 (3)	1.0802 (2)	0.09799 (17)	0.0766 (9)
H63	0.7194	1.1138	0.1286	0.092*
C64	0.8040 (3)	1.1398 (3)	0.05644 (19)	0.0857 (11)
H64	0.8020	1.2142	0.0584	0.103*
C65	0.8562 (3)	1.0901 (3)	0.01195 (19)	0.0883 (11)
H65	0.8905	1.1310	−0.0158	0.106*
C66	0.8586 (2)	0.9793 (2)	0.00755 (15)	0.0623 (7)
H66	0.8941	0.9467	−0.0234	0.075*

	U11	U22	U33	U12	U13	U23
Cu1	0.03296 (15)	0.04514 (17)	0.03791 (16)	−0.00235 (12)	0.00491 (11)	0.00367 (12)
O1	0.104 (5)	0.132 (6)	0.074 (4)	−0.054 (4)	−0.025 (3)	0.031 (3)
Cl1	0.0553 (4)	0.0380 (3)	0.0546 (4)	−0.0016 (3)	0.0157 (3)	−0.0045 (3)
S1	0.0600 (4)	0.0470 (4)	0.0581 (4)	−0.0062 (3)	0.0267 (3)	−0.0090 (3)
P1	0.0326 (3)	0.0408 (3)	0.0345 (3)	−0.0015 (2)	0.0031 (2)	0.0009 (2)
P2	0.0323 (3)	0.0405 (3)	0.0359 (3)	−0.0013 (2)	0.0036 (2)	0.0022 (2)
N1	0.0616 (16)	0.0768 (18)	0.111 (2)	0.0057 (14)	0.0397 (16)	−0.0275 (16)
N2	0.0507 (13)	0.0628 (15)	0.0868 (17)	−0.0123 (11)	0.0347 (12)	−0.0253 (13)
N3	0.068 (2)	0.099 (2)	0.156 (3)	−0.0340 (19)	0.055 (2)	−0.046 (3)
C1	0.0513 (15)	0.0576 (16)	0.0480 (14)	0.0054 (12)	0.0178 (12)	−0.0065 (12)
C11	0.0350 (11)	0.0408 (12)	0.0339 (11)	0.0038 (9)	0.0047 (9)	0.0038 (9)
C12	0.0510 (14)	0.0423 (13)	0.0475 (14)	−0.0025 (11)	0.0055 (11)	−0.0006 (11)
C13	0.0751 (19)	0.0470 (15)	0.0499 (15)	0.0075 (14)	0.0155 (13)	−0.0055 (12)
C14	0.0648 (18)	0.0579 (17)	0.0574 (16)	0.0172 (14)	0.0276 (14)	0.0085 (13)
C15	0.0424 (14)	0.0652 (18)	0.0700 (18)	−0.0009 (12)	0.0180 (13)	0.0062 (15)
C16	0.0407 (13)	0.0538 (15)	0.0491 (14)	−0.0042 (11)	0.0061 (11)	−0.0041 (11)
C21	0.0315 (11)	0.0457 (13)	0.0484 (13)	−0.0006 (9)	0.0057 (10)	−0.0063 (10)
C22	0.0693 (18)	0.0483 (15)	0.0594 (17)	−0.0014 (13)	0.0173 (14)	−0.0006 (13)
C23	0.074 (2)	0.0436 (16)	0.102 (3)	−0.0007 (14)	0.0286 (19)	−0.0052 (16)
C24	0.0532 (18)	0.0538 (18)	0.126 (3)	−0.0037 (14)	0.0035 (19)	−0.031 (2)
C25	0.086 (2)	0.080 (2)	0.088 (3)	0.009 (2)	−0.030 (2)	−0.039 (2)
C26	0.0679 (19)	0.0608 (17)	0.0601 (17)	0.0080 (15)	−0.0159 (14)	−0.0101 (14)
C31	0.0436 (13)	0.0444 (13)	0.0368 (12)	0.0000 (10)	0.0006 (10)	0.0007 (10)
C32	0.0508 (15)	0.0623 (17)	0.0540 (15)	0.0066 (13)	0.0028 (12)	0.0120 (13)
C33	0.0650 (19)	0.072 (2)	0.0642 (18)	0.0212 (16)	−0.0008 (15)	0.0146 (15)
C34	0.096 (3)	0.0641 (19)	0.0569 (18)	0.0155 (18)	0.0017 (17)	0.0196 (15)
C35	0.081 (2)	0.085 (2)	0.0607 (19)	−0.0052 (18)	0.0165 (16)	0.0279 (17)
C36	0.0543 (16)	0.0706 (18)	0.0470 (15)	−0.0003 (14)	0.0062 (12)	0.0146 (13)
C41	0.0337 (11)	0.0549 (15)	0.0376 (12)	−0.0034 (10)	0.0021 (9)	−0.0042 (10)
C42	0.0473 (15)	0.0670 (18)	0.0710 (19)	−0.0138 (13)	−0.0052 (13)	0.0002 (15)
C43	0.062 (2)	0.096 (3)	0.106 (3)	−0.037 (2)	−0.0070 (19)	0.006 (2)
C44	0.0389 (17)	0.141 (4)	0.092 (3)	−0.019 (2)	−0.0038 (16)	−0.006 (2)
C45	0.0416 (16)	0.110 (3)	0.080 (2)	0.0091 (17)	−0.0061 (15)	0.003 (2)
C46	0.0427 (15)	0.0740 (19)	0.0654 (18)	0.0024 (13)	0.0007 (13)	0.0113 (15)
C51	0.0401 (12)	0.0391 (12)	0.0381 (12)	−0.0010 (10)	0.0075 (9)	0.0010 (9)
C52	0.0441 (14)	0.086 (2)	0.0431 (14)	0.0032 (14)	0.0008 (11)	−0.0040 (14)
C53	0.0654 (19)	0.093 (2)	0.0395 (14)	−0.0050 (16)	0.0033 (13)	−0.0071 (14)
C54	0.0719 (19)	0.0564 (17)	0.0520 (16)	−0.0060 (14)	0.0265 (14)	−0.0076 (12)
C55	0.0478 (15)	0.0610 (17)	0.0672 (18)	0.0020 (13)	0.0206 (13)	−0.0021 (14)
C56	0.0417 (13)	0.0567 (16)	0.0477 (14)	0.0002 (11)	0.0063 (11)	−0.0009 (11)
C61	0.0479 (13)	0.0395 (12)	0.0401 (12)	−0.0013 (10)	−0.0011 (10)	0.0033 (10)
C62	0.077 (2)	0.0506 (16)	0.0557 (16)	0.0073 (14)	0.0170 (14)	0.0043 (13)
C63	0.111 (3)	0.0526 (18)	0.067 (2)	0.0171 (18)	0.0143 (19)	−0.0046 (15)
C64	0.140 (3)	0.0417 (17)	0.073 (2)	−0.002 (2)	0.003 (2)	−0.0008 (16)
C65	0.136 (3)	0.0539 (19)	0.079 (2)	−0.027 (2)	0.030 (2)	0.0082 (17)
C66	0.079 (2)	0.0498 (16)	0.0603 (17)	−0.0128 (14)	0.0192 (15)	0.0005 (13)

Cu1—P1	2.2714 (6)	C31—C36	1.387 (3)
Cu1—P2	2.2872 (6)	C32—C33	1.385 (4)
Cu1—S1	2.3841 (7)	C32—H32	0.9300
Cu1—Cl1	2.4110 (7)	C33—C34	1.369 (5)
O1—H1C	0.82 (2)	C33—H33	0.9300
O1—H1D	0.82 (2)	C34—C35	1.359 (5)
S1—C1	1.697 (3)	C34—H34	0.9300
P1—C21	1.823 (2)	C35—C36	1.386 (4)
P1—C11	1.831 (2)	C35—H35	0.9300
P1—C31	1.836 (2)	C36—H36	0.9300
P2—C61	1.828 (2)	C41—C42	1.377 (4)
P2—C51	1.828 (2)	C41—C46	1.385 (4)
P2—C41	1.834 (2)	C42—C43	1.386 (4)
N1—C1	1.316 (3)	C42—H42	0.9300
N1—H1A	0.8600	C43—C44	1.366 (5)
N1—H1B	0.8600	C43—H43	0.9300
N2—C1	1.319 (3)	C44—C45	1.362 (5)
N2—N3	1.406 (4)	C44—H44	0.9300
N2—H2	0.8600	C45—C46	1.383 (4)
N3—H3A	0.879 (19)	C45—H45	0.9300
N3—H3B	0.851 (19)	C46—H46	0.9300
C11—C16	1.387 (3)	C51—C56	1.383 (3)
C11—C12	1.389 (3)	C51—C52	1.383 (3)
C12—C13	1.382 (4)	C52—C53	1.384 (4)
C12—H12	0.9300	C52—H52	0.9300
C13—C14	1.365 (4)	C53—C54	1.359 (4)
C13—H13	0.9300	C53—H53	0.9300
C14—C15	1.373 (4)	C54—C55	1.366 (4)
C14—H14	0.9300	C54—H54	0.9300
C15—C16	1.382 (4)	C55—C56	1.382 (4)
C15—H15	0.9300	C55—H55	0.9300
C16—H16	0.9300	C56—H56	0.9300
C21—C26	1.372 (4)	C61—C66	1.372 (4)
C21—C22	1.388 (4)	C61—C62	1.394 (4)
C22—C23	1.373 (4)	C62—C63	1.382 (4)
C22—H22	0.9300	C62—H62	0.9300
C23—C24	1.367 (5)	C63—C64	1.360 (5)
C23—H23	0.9300	C63—H63	0.9300
C24—C25	1.362 (5)	C64—C65	1.364 (5)
C24—H24	0.9300	C64—H64	0.9300
C25—C26	1.395 (5)	C65—C66	1.386 (4)
C25—H25	0.9300	C65—H65	0.9300
C26—H26	0.9300	C66—H66	0.9300
C31—C32	1.383 (3)
P1—Cu1—P2	129.47 (2)	C36—C31—P1	119.14 (18)
P1—Cu1—S1	100.02 (3)	C31—C32—C33	120.8 (3)
P2—Cu1—S1	103.44 (3)	C31—C32—H32	119.6
P1—Cu1—Cl1	102.44 (2)	C33—C32—H32	119.6
P2—Cu1—Cl1	110.26 (2)	C34—C33—C32	120.2 (3)
S1—Cu1—Cl1	110.06 (2)	C34—C33—H33	119.9
H1C—O1—H1D	129 (10)	C32—C33—H33	119.9
C1—S1—Cu1	108.44 (9)	C35—C34—C33	119.6 (3)
C21—P1—C11	102.72 (10)	C35—C34—H34	120.2
C21—P1—C31	104.98 (11)	C33—C34—H34	120.2
C11—P1—C31	101.42 (10)	C34—C35—C36	121.1 (3)
C21—P1—Cu1	111.56 (8)	C34—C35—H35	119.4
C11—P1—Cu1	119.40 (7)	C36—C35—H35	119.4
C31—P1—Cu1	115.04 (8)	C35—C36—C31	120.0 (3)
C61—P2—C51	103.67 (11)	C35—C36—H36	120.0
C61—P2—C41	101.63 (11)	C31—C36—H36	120.0
C51—P2—C41	103.36 (10)	C42—C41—C46	118.6 (2)
C61—P2—Cu1	114.33 (8)	C42—C41—P2	118.0 (2)
C51—P2—Cu1	117.63 (8)	C46—C41—P2	123.4 (2)
C41—P2—Cu1	114.30 (8)	C41—C42—C43	120.4 (3)
C1—N1—H1A	120.0	C41—C42—H42	119.8
C1—N1—H1B	120.0	C43—C42—H42	119.8
H1A—N1—H1B	120.0	C44—C43—C42	120.3 (3)
C1—N2—N3	119.6 (2)	C44—C43—H43	119.9
C1—N2—H2	120.2	C42—C43—H43	119.9
N3—N2—H2	120.2	C45—C44—C43	119.9 (3)
N2—N3—H3A	104 (3)	C45—C44—H44	120.0
N2—N3—H3B	111 (3)	C43—C44—H44	120.0
H3A—N3—H3B	102 (4)	C44—C45—C46	120.3 (3)
N1—C1—N2	117.8 (3)	C44—C45—H45	119.8
N1—C1—S1	121.9 (2)	C46—C45—H45	119.8
N2—C1—S1	120.19 (19)	C45—C46—C41	120.4 (3)
C16—C11—C12	119.0 (2)	C45—C46—H46	119.8
C16—C11—P1	124.28 (18)	C41—C46—H46	119.8
C12—C11—P1	116.67 (17)	C56—C51—C52	117.7 (2)
C13—C12—C11	120.2 (2)	C56—C51—P2	118.30 (18)
C13—C12—H12	119.9	C52—C51—P2	123.93 (19)
C11—C12—H12	119.9	C51—C52—C53	120.5 (3)
C14—C13—C12	120.2 (3)	C51—C52—H52	119.8
C14—C13—H13	119.9	C53—C52—H52	119.8
C12—C13—H13	119.9	C54—C53—C52	120.9 (3)
C13—C14—C15	120.3 (2)	C54—C53—H53	119.6
C13—C14—H14	119.8	C52—C53—H53	119.6
C15—C14—H14	119.8	C53—C54—C55	119.6 (3)
C14—C15—C16	120.2 (3)	C53—C54—H54	120.2
C14—C15—H15	119.9	C55—C54—H54	120.2
C16—C15—H15	119.9	C54—C55—C56	119.9 (3)
C15—C16—C11	120.1 (2)	C54—C55—H55	120.0
C15—C16—H16	120.0	C56—C55—H55	120.0
C11—C16—H16	120.0	C55—C56—C51	121.4 (2)
C26—C21—C22	118.1 (2)	C55—C56—H56	119.3
C26—C21—P1	124.3 (2)	C51—C56—H56	119.3
C22—C21—P1	117.53 (19)	C66—C61—C62	117.9 (2)
C23—C22—C21	121.6 (3)	C66—C61—P2	123.5 (2)
C23—C22—H22	119.2	C62—C61—P2	118.63 (19)
C21—C22—H22	119.2	C63—C62—C61	121.1 (3)
C24—C23—C22	119.5 (3)	C63—C62—H62	119.5
C24—C23—H23	120.2	C61—C62—H62	119.5
C22—C23—H23	120.2	C64—C63—C62	120.0 (3)
C25—C24—C23	120.0 (3)	C64—C63—H63	120.0
C25—C24—H24	120.0	C62—C63—H63	120.0
C23—C24—H24	120.0	C63—C64—C65	119.7 (3)
C24—C25—C26	120.7 (3)	C63—C64—H64	120.1
C24—C25—H25	119.7	C65—C64—H64	120.1
C26—C25—H25	119.7	C64—C65—C66	120.9 (3)
C21—C26—C25	119.9 (3)	C64—C65—H65	119.6
C21—C26—H26	120.0	C66—C65—H65	119.6
C25—C26—H26	120.0	C61—C66—C65	120.4 (3)
C32—C31—C36	118.3 (2)	C61—C66—H66	119.8
C32—C31—P1	122.49 (19)	C65—C66—H66	119.8
N3—N2—C1—N1	0.5 (5)	C32—C31—C36—C35	−0.1 (4)
N3—N2—C1—S1	177.1 (3)	P1—C31—C36—C35	177.8 (2)
Cu1—S1—C1—N1	−154.9 (2)	C61—P2—C41—C42	−156.0 (2)
Cu1—S1—C1—N2	28.6 (3)	C51—P2—C41—C42	96.8 (2)
C21—P1—C11—C16	18.2 (2)	Cu1—P2—C41—C42	−32.3 (2)
C31—P1—C11—C16	−90.2 (2)	C61—P2—C41—C46	25.0 (3)
Cu1—P1—C11—C16	142.20 (18)	C51—P2—C41—C46	−82.3 (2)
C21—P1—C11—C12	−163.36 (18)	Cu1—P2—C41—C46	148.6 (2)
C31—P1—C11—C12	88.22 (19)	C46—C41—C42—C43	−0.3 (4)
Cu1—P1—C11—C12	−39.3 (2)	P2—C41—C42—C43	−179.4 (3)
C16—C11—C12—C13	−0.1 (4)	C41—C42—C43—C44	0.0 (6)
P1—C11—C12—C13	−178.7 (2)	C42—C43—C44—C45	0.5 (6)
C11—C12—C13—C14	0.0 (4)	C43—C44—C45—C46	−0.6 (6)
C12—C13—C14—C15	0.2 (4)	C44—C45—C46—C41	0.3 (5)
C13—C14—C15—C16	−0.3 (4)	C42—C41—C46—C45	0.1 (4)
C14—C15—C16—C11	0.2 (4)	P2—C41—C46—C45	179.2 (2)
C12—C11—C16—C15	0.0 (4)	C61—P2—C51—C56	95.5 (2)
P1—C11—C16—C15	178.4 (2)	C41—P2—C51—C56	−158.8 (2)
C11—P1—C21—C26	−114.0 (2)	Cu1—P2—C51—C56	−31.8 (2)
C31—P1—C21—C26	−8.3 (3)	C61—P2—C51—C52	−87.8 (2)
Cu1—P1—C21—C26	117.0 (2)	C41—P2—C51—C52	17.9 (3)
C11—P1—C21—C22	67.8 (2)	Cu1—P2—C51—C52	144.9 (2)
C31—P1—C21—C22	173.51 (19)	C56—C51—C52—C53	0.7 (4)
Cu1—P1—C21—C22	−61.3 (2)	P2—C51—C52—C53	−176.0 (2)
C26—C21—C22—C23	3.4 (4)	C51—C52—C53—C54	−0.1 (5)
P1—C21—C22—C23	−178.3 (2)	C52—C53—C54—C55	−0.9 (5)
C21—C22—C23—C24	−1.3 (5)	C53—C54—C55—C56	1.4 (4)
C22—C23—C24—C25	−1.3 (5)	C54—C55—C56—C51	−0.8 (4)
C23—C24—C25—C26	1.7 (5)	C52—C51—C56—C55	−0.3 (4)
C22—C21—C26—C25	−2.9 (4)	P2—C51—C56—C55	176.6 (2)
P1—C21—C26—C25	178.8 (2)	C51—P2—C61—C66	−18.1 (3)
C24—C25—C26—C21	0.5 (5)	C41—P2—C61—C66	−125.2 (2)
C21—P1—C31—C32	−77.2 (2)	Cu1—P2—C61—C66	111.2 (2)
C11—P1—C31—C32	29.5 (2)	C51—P2—C61—C62	162.3 (2)
Cu1—P1—C31—C32	159.82 (19)	C41—P2—C61—C62	55.3 (2)
C21—P1—C31—C36	104.9 (2)	Cu1—P2—C61—C62	−68.4 (2)
C11—P1—C31—C36	−148.4 (2)	C66—C61—C62—C63	1.4 (4)
Cu1—P1—C31—C36	−18.1 (2)	P2—C61—C62—C63	−179.1 (2)
C36—C31—C32—C33	−0.9 (4)	C61—C62—C63—C64	−0.9 (5)
P1—C31—C32—C33	−178.8 (2)	C62—C63—C64—C65	−0.3 (6)
C31—C32—C33—C34	1.0 (5)	C63—C64—C65—C66	1.2 (6)
C32—C33—C34—C35	0.0 (5)	C62—C61—C66—C65	−0.6 (4)
C33—C34—C35—C36	−1.1 (5)	P2—C61—C66—C65	179.9 (3)
C34—C35—C36—C31	1.1 (5)	C64—C65—C66—C61	−0.7 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···Cl1	0.82 (2)	2.37 (2)	3.186 (5)	179 (12)
O1—H1D···S1i	0.82 (2)	2.70 (10)	3.218 (5)	123 (9)
N1—H1B···Cl1ii	0.86	2.48	3.302 (3)	161
N1—H1A···N3	0.86	2.27	2.628 (5)	105
N2—H2···Cl1	0.86	2.35	3.202 (2)	170
C42—H42···Cl1	0.93	2.72	3.626 (3)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1C⋯Cl1	0.82 (2)	2.37 (2)	3.186 (5)	179 (12)
O1—H1D⋯S1i	0.82 (2)	2.70 (10)	3.218 (5)	123 (9)
N1—H1B⋯Cl1ii	0.86	2.48	3.302 (3)	161
N1—H1A⋯N3	0.86	2.27	2.628 (5)	105
N2—H2⋯Cl1	0.86	2.35	3.202 (2)	170
C42—H42⋯Cl1	0.93	2.72	3.626 (3)	164

Symmetry codes: (i) ; (ii) .