Di­chloro­tetrakis(3-phenyl­pyrazole-κN²)copper(II)

In the title compound, [CuCl₂(C₉H₈N₂)₄], there are two independent mol­ecules in the asymmetric unit. The Cu²⁺ ions lie on inversion centres and are octahedrally coordinated by two Cl atoms and four pyrazole N atoms. All pyrazole N—H groups form intramolecular hydrogen bonds, giving rise to five-membered hydrogen-bonded rings incorporating the Cu atoms.

S1. Comment

This paper is a continuation of our X-ray crystal structure studies on copper(II) chloride complexes incorporating phenylpyrazoles (Małecka et al., 1998, 2001). This group of complexes is considered because of their expected biological activities as fungicides and herbicides (Nasiadek, 1985). Previous studies on copper(II) complexes with different substituted pyrazoles were undertaken with regard to their protolitic properties and the influence of the nature and position of substituents on metal complexation (Kostka & Strawiak, 1982; Goslar et al., 1987, 1988). On the other hand, we are investigating nitrogen-containing heterocyclic ligands and their complexes because of the expected pharmacological activity, by analogy to cis-platinum complexes (Hollis, 1989; Reedijk, 1996).

The X-ray structure analysis of the title complex, (I), was carried out in order to elucidate the geometry around the Cu²⁺ ion and the packing arrangement in the crystal, which is often related to the coordination ability towards transition metal ions (Ochocki et al., 1998)

The compound crystallizes with two crystallographically independent centrosymmetric molecules, A and B, in the asymmetric unit, with the two Cu²⁺ ions located on the centres of symmetry at (0, 0, 0) and (1/2, 0, 1/2), respectively.

The metal coordination polyhedron is an elongated octahedral bipyramid with two Cl⁻ ions in trans-apical positions and four pyrazole N atoms in the equatorial plane. The Cl—Cu—Cl lines deviates by 2.19 (6) and 2.58 (7)° from being orthogonal to these equatorial planes for molecules A and B, respectively.

In the two independent molecules, some differences are observed with regard to the rotation of the phenyl and pyrazole rings about the Cn5—Cn51 bond joining them, as shown by the Nn1—Cn5—Cn51—Cn52 (n = 1–4) torsion angles (see Table 1).

The orientation of the pyrazole ligands around the metal ions is not the same in the two independent molecules, as indicated by the Cl—Cu—N—N torsion angles. The different distortions of the ligands in molecules A and B can be explained by the different packing interactions in each molecule. These interactions are of the C—H···Cl and C—H···Cg types (Cg are the centroids of pyrazole rings Nn1/Nn2/Cn3/Cn4/Cn5, where n = 2, 3). The geometry for these weak interactions is given in Table 2.

Two intramolecular hydrogen bonds are observed in each molecule, producing four five-membered hydrogen-bonded rings incorporating the Cu atoms (see Fig. 1) which adopt the following conformations: H11-envelope in ring I, twisted in rings II and IV, and N31-half-chair in ring III. The puckering parameters (Cremer & Pople, 1975) corresponding to the Cu—Nn2—Nn1—Hn1—Cl (n = 1–4) atom sequences are q₂ = 0.11 (1) Å and ϕ₂ = 65 (2)°, q₂ = 0.18 (1) Å and ϕ₂ = −142 (1)°, q₂ = 0.28 (1) Å and ϕ₂ = 19 (1)°, and q₂ = 0.19 (1) Å and ϕ₂ = −144 (1)° for rings I, II, III and IV, respectively.

The bond distances and angles in both molecules are in a good agreement with expected values (Allen et al., 1987).

S2. Experimental

The title compound was obtained by mixing hot ethanol solutions of CuCl₂·2H₂O and 5-phenylpyrazole in a 1:4 molar ratio. On cooling to room temperature, a crystalline material began to separate. This material was filtered off and washed three times with cold solvent and dried in vacuo over phosphorus pentaoxide, giving single-crystal of the title compound suitable for X-ray analysis.

S3. Refinement

All H atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93 Å) and refined with a riding model. For the H atoms of the phenyl and pyrazole rings (except for the H atoms of the N—H groups), U_iso values were constrained to be 1.2U_eq of the carrier atom. The H atoms of the N—H groups were placed in calculated positions and their U_iso values were refined.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: PARST97 (Nardelli, 1996).

Figures

Fig. 1. Views of molecules A (top) and B (bottom), with the atom-numbering schemes and the intramolecular hydrogen bonds (dashed lines) which give rise to five-membered hydrogen-bonded rings I, II, III and IV. All H atoms, except for H11, H21, H31 and H41 (shown as spheres), have been omitted for clarity. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Dichlorotetrakis(3-phenylpyrazole-κN²)copper(II)

Crystal data

[CuCl2(C9H8N2)4]	Z = 2
Mr = 711.14	F(000) = 734
Triclinic, P1	Dx = 1.359 Mg m^−3 Dm = 1.356 Mg m^−3 Dm measured by flotation in tetralin and iodomethane
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 11.587 (4) Å	Cell parameters from 22 reflections
b = 12.676 (3) Å	θ = 23.0–31.9°
c = 13.352 (3) Å	µ = 2.60 mm^−1
α = 81.54 (2)°	T = 293 K
β = 72.71 (2)°	Prism, blue
γ = 68.29 (2)°	0.6 × 0.5 × 0.25 mm
V = 1738.1 (9) Å^3

Data collection

Rigaku AFC-5S diffractometer	4962 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 67.5°, θmin = 3.5°
ω scans	h = −13→13
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = −15→11
Tmin = 0.296, Tmax = 0.569	l = −15→15
6374 measured reflections	3 standard reflections every 150 reflections
6079 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0958P)^2 + 0.0725P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.152	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 0.41 e Å^−3
6079 reflections	Δρmin = −0.65 e Å^−3
432 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0275 (12)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	0.0000	0.0569 (2)
Cl1	0.12897 (7)	0.15564 (6)	−0.08589 (6)	0.0643 (2)
N11	−0.0889 (2)	0.20318 (18)	0.11819 (19)	0.0552 (5)
H11	−0.0242	0.2198	0.0779	0.088 (12)*
N12	−0.1076 (2)	0.10393 (18)	0.11776 (18)	0.0553 (6)
C13	−0.2162 (3)	0.1107 (2)	0.1906 (2)	0.0563 (7)
H13	−0.2530	0.0542	0.2077	0.068*
C14	−0.2672 (3)	0.2151 (2)	0.2380 (2)	0.0552 (6)
H14	−0.3424	0.2408	0.2916	0.066*
C15	−0.1843 (3)	0.2723 (2)	0.1897 (2)	0.0512 (6)
C151	−0.1851 (3)	0.3846 (2)	0.2075 (2)	0.0564 (7)
C152	−0.0879 (4)	0.4248 (3)	0.1528 (3)	0.0702 (8)
H152	−0.0188	0.3803	0.1028	0.084*
C153	−0.0917 (4)	0.5306 (3)	0.1713 (3)	0.0863 (11)
H153	−0.0259	0.5573	0.1331	0.104*
C154	−0.1932 (5)	0.5968 (3)	0.2464 (3)	0.0894 (12)
H154	−0.1959	0.6680	0.2593	0.107*
C155	−0.2875 (5)	0.5575 (3)	0.3005 (3)	0.0895 (12)
H155	−0.3554	0.6019	0.3515	0.107*
C156	−0.2864 (4)	0.4515 (3)	0.2822 (3)	0.0745 (9)
H156	−0.3534	0.4261	0.3200	0.089*
N22	−0.1327 (2)	0.08868 (19)	−0.07984 (19)	0.0574 (6)
N21	−0.1145 (2)	0.17437 (19)	−0.14692 (18)	0.0573 (6)
H21	−0.0447	0.1900	−0.1641	0.070 (10)*
C23	−0.2490 (3)	0.0912 (3)	−0.0754 (3)	0.0760 (9)
H23	−0.2879	0.0409	−0.0352	0.091*
C24	−0.3057 (3)	0.1814 (3)	−0.1406 (3)	0.0823 (10)
H24	−0.3869	0.2015	−0.1514	0.099*
C25	−0.2172 (3)	0.2333 (2)	−0.1845 (2)	0.0615 (7)
C251	−0.2181 (3)	0.3309 (3)	−0.2590 (3)	0.0680 (8)
C252	−0.1243 (4)	0.3780 (3)	−0.2821 (3)	0.0856 (11)
H252	−0.0574	0.3475	−0.2497	0.103*
C253	−0.1259 (5)	0.4698 (3)	−0.3523 (4)	0.1040 (14)
H253	−0.0606	0.5000	−0.3665	0.125*
C254	−0.2218 (5)	0.5159 (4)	−0.4006 (4)	0.1125 (16)
H254	−0.2226	0.5779	−0.4477	0.135*
C255	−0.3166 (5)	0.4715 (4)	−0.3799 (4)	0.1172 (17)
H255	−0.3827	0.5034	−0.4130	0.141*
C256	−0.3164 (4)	0.3772 (4)	−0.3085 (3)	0.0981 (13)
H256	−0.3815	0.3467	−0.2951	0.118*
Cu2	0.5000	0.0000	0.5000	0.0555 (2)
Cl2	0.46849 (7)	0.23252 (5)	0.49205 (6)	0.0597 (2)
N32	0.5021 (2)	0.0188 (2)	0.34623 (18)	0.0557 (5)
N31	0.4599 (2)	0.1238 (2)	0.30059 (17)	0.0534 (5)
H31	0.4367	0.1861	0.3315	0.066 (10)*
C33	0.5283 (3)	−0.0536 (3)	0.2727 (2)	0.0655 (8)
H33	0.5596	−0.1324	0.2814	0.079*
C34	0.5023 (3)	0.0053 (3)	0.1820 (2)	0.0679 (8)
H34	0.5125	−0.0259	0.1197	0.081*
C35	0.4588 (3)	0.1183 (3)	0.2009 (2)	0.0556 (7)
C351	0.4166 (3)	0.2198 (3)	0.1343 (2)	0.0615 (7)
C352	0.3572 (3)	0.2166 (3)	0.0588 (3)	0.0791 (10)
H352	0.3447	0.1501	0.0515	0.095*
C353	0.3170 (5)	0.3102 (5)	−0.0048 (3)	0.1081 (15)
H353	0.2785	0.3067	−0.0556	0.130*
C354	0.3334 (5)	0.4088 (5)	0.0065 (4)	0.1149 (16)
H354	0.3064	0.4721	−0.0370	0.138*
C355	0.3896 (5)	0.4150 (4)	0.0816 (4)	0.1044 (14)
H355	0.3991	0.4827	0.0897	0.125*
C356	0.4322 (4)	0.3201 (3)	0.1456 (3)	0.0810 (10)
H356	0.4711	0.3240	0.1959	0.097*
N42	0.6902 (2)	−0.03688 (19)	0.46034 (18)	0.0535 (5)
N41	0.7378 (2)	0.04696 (19)	0.45446 (17)	0.0518 (5)
H41	0.6913	0.1154	0.4726	0.097 (13)*
C43	0.7908 (3)	−0.1288 (2)	0.4277 (2)	0.0583 (7)
H43	0.7869	−0.2000	0.4239	0.070*
C44	0.9040 (3)	−0.1031 (2)	0.3998 (2)	0.0589 (7)
H44	0.9876	−0.1529	0.3748	0.071*
C45	0.8670 (2)	0.0107 (2)	0.4168 (2)	0.0500 (6)
C451	0.9410 (3)	0.0860 (2)	0.3962 (2)	0.0549 (6)
C452	0.8884 (3)	0.1964 (3)	0.4325 (3)	0.0688 (8)
H452	0.8043	0.2224	0.4745	0.083*
C453	0.9603 (4)	0.2670 (3)	0.4064 (3)	0.0826 (10)
H453	0.9245	0.3406	0.4301	0.099*
C454	1.0853 (4)	0.2279 (4)	0.3451 (3)	0.0877 (11)
H454	1.1338	0.2755	0.3272	0.105*
C455	1.1386 (4)	0.1197 (4)	0.3103 (3)	0.0870 (11)
H455	1.2235	0.0937	0.2697	0.104*
C456	1.0678 (3)	0.0499 (3)	0.3350 (3)	0.0700 (8)
H456	1.1050	−0.0234	0.3105	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0662 (4)	0.0404 (3)	0.0560 (4)	−0.0078 (3)	−0.0171 (3)	−0.0041 (2)
Cl1	0.0614 (4)	0.0592 (4)	0.0724 (5)	−0.0277 (3)	−0.0089 (3)	−0.0029 (3)
N11	0.0567 (13)	0.0444 (11)	0.0620 (13)	−0.0187 (10)	−0.0091 (11)	−0.0053 (10)
N12	0.0592 (14)	0.0450 (11)	0.0594 (13)	−0.0185 (10)	−0.0102 (11)	−0.0050 (10)
C13	0.0589 (16)	0.0527 (15)	0.0601 (16)	−0.0229 (13)	−0.0161 (14)	−0.0003 (12)
C14	0.0528 (15)	0.0527 (15)	0.0554 (15)	−0.0145 (12)	−0.0103 (12)	−0.0060 (12)
C15	0.0554 (15)	0.0415 (13)	0.0528 (14)	−0.0089 (11)	−0.0168 (12)	−0.0055 (11)
C151	0.0680 (17)	0.0428 (13)	0.0584 (16)	−0.0133 (12)	−0.0254 (14)	0.0002 (12)
C152	0.085 (2)	0.0537 (16)	0.075 (2)	−0.0251 (16)	−0.0231 (17)	−0.0044 (15)
C153	0.118 (3)	0.063 (2)	0.098 (3)	−0.046 (2)	−0.042 (2)	0.0046 (19)
C154	0.132 (4)	0.0485 (18)	0.102 (3)	−0.026 (2)	−0.056 (3)	−0.0042 (18)
C155	0.110 (3)	0.0516 (18)	0.095 (3)	−0.0044 (19)	−0.030 (2)	−0.0229 (18)
C156	0.079 (2)	0.0552 (17)	0.078 (2)	−0.0103 (16)	−0.0143 (18)	−0.0172 (15)
N22	0.0616 (14)	0.0477 (12)	0.0610 (14)	−0.0174 (11)	−0.0169 (11)	0.0010 (10)
N21	0.0549 (14)	0.0502 (12)	0.0646 (14)	−0.0160 (11)	−0.0184 (11)	0.0034 (11)
C23	0.068 (2)	0.074 (2)	0.088 (2)	−0.0327 (17)	−0.0187 (18)	0.0078 (18)
C24	0.064 (2)	0.078 (2)	0.106 (3)	−0.0229 (17)	−0.0333 (19)	0.012 (2)
C25	0.0563 (16)	0.0525 (15)	0.0684 (18)	−0.0056 (13)	−0.0218 (14)	−0.0045 (13)
C251	0.0645 (18)	0.0511 (16)	0.074 (2)	−0.0015 (14)	−0.0214 (16)	−0.0010 (14)
C252	0.105 (3)	0.0572 (19)	0.100 (3)	−0.0242 (19)	−0.045 (2)	0.0115 (18)
C253	0.125 (4)	0.059 (2)	0.123 (4)	−0.028 (2)	−0.040 (3)	0.020 (2)
C254	0.118 (4)	0.072 (3)	0.110 (3)	−0.003 (3)	−0.028 (3)	0.026 (2)
C255	0.097 (3)	0.109 (4)	0.113 (4)	0.003 (3)	−0.047 (3)	0.031 (3)
C256	0.075 (2)	0.096 (3)	0.105 (3)	−0.009 (2)	−0.035 (2)	0.018 (2)
Cu2	0.0436 (3)	0.0676 (4)	0.0534 (3)	−0.0190 (3)	−0.0153 (2)	0.0079 (3)
Cl2	0.0575 (4)	0.0448 (3)	0.0690 (4)	−0.0081 (3)	−0.0160 (3)	−0.0062 (3)
N32	0.0526 (13)	0.0544 (13)	0.0563 (13)	−0.0147 (10)	−0.0158 (11)	0.0024 (10)
N31	0.0541 (13)	0.0545 (13)	0.0507 (12)	−0.0175 (10)	−0.0161 (10)	0.0016 (10)
C33	0.0671 (19)	0.0562 (16)	0.0672 (18)	−0.0165 (14)	−0.0143 (15)	−0.0045 (14)
C34	0.072 (2)	0.072 (2)	0.0582 (17)	−0.0201 (16)	−0.0171 (15)	−0.0115 (15)
C35	0.0483 (14)	0.0686 (17)	0.0495 (15)	−0.0204 (13)	−0.0138 (12)	0.0015 (13)
C351	0.0549 (16)	0.0710 (19)	0.0571 (16)	−0.0202 (14)	−0.0186 (13)	0.0058 (14)
C352	0.082 (2)	0.097 (3)	0.066 (2)	−0.035 (2)	−0.0309 (18)	0.0104 (18)
C353	0.107 (3)	0.142 (4)	0.085 (3)	−0.043 (3)	−0.055 (3)	0.029 (3)
C354	0.115 (4)	0.117 (4)	0.101 (3)	−0.025 (3)	−0.056 (3)	0.047 (3)
C355	0.119 (3)	0.076 (3)	0.112 (3)	−0.029 (2)	−0.041 (3)	0.022 (2)
C356	0.082 (2)	0.084 (2)	0.081 (2)	−0.0271 (19)	−0.038 (2)	0.0158 (19)
N42	0.0484 (12)	0.0546 (12)	0.0565 (13)	−0.0183 (10)	−0.0141 (10)	0.0022 (10)
N41	0.0428 (11)	0.0502 (12)	0.0582 (13)	−0.0122 (10)	−0.0125 (10)	−0.0012 (10)
C43	0.0512 (15)	0.0495 (14)	0.0710 (18)	−0.0134 (12)	−0.0161 (14)	−0.0032 (13)
C44	0.0452 (14)	0.0563 (15)	0.0678 (17)	−0.0091 (12)	−0.0131 (13)	−0.0067 (13)
C45	0.0420 (13)	0.0541 (14)	0.0519 (14)	−0.0135 (11)	−0.0154 (11)	0.0015 (11)
C451	0.0483 (14)	0.0598 (16)	0.0597 (16)	−0.0188 (12)	−0.0222 (13)	0.0052 (13)
C452	0.0554 (17)	0.0635 (18)	0.087 (2)	−0.0145 (14)	−0.0258 (16)	−0.0048 (16)
C453	0.095 (3)	0.0615 (19)	0.111 (3)	−0.0320 (19)	−0.053 (2)	0.0073 (19)
C454	0.087 (3)	0.096 (3)	0.103 (3)	−0.055 (2)	−0.038 (2)	0.019 (2)
C455	0.070 (2)	0.103 (3)	0.096 (3)	−0.049 (2)	−0.010 (2)	−0.002 (2)
C456	0.0585 (18)	0.078 (2)	0.075 (2)	−0.0278 (16)	−0.0119 (15)	−0.0069 (17)

Geometric parameters (Å, º)

Cu1—N12	1.998 (2)	Cu2—N42	1.993 (2)
Cu1—N12^i	1.998 (2)	Cu2—N42^ii	1.993 (2)
Cu1—N22	2.027 (2)	Cu2—N32^ii	2.026 (2)
Cu1—N22^i	2.027 (2)	Cu2—N32	2.026 (2)
Cu1—Cl1	2.8174 (10)	Cu2—Cl2	2.8226 (10)
N11—C15	1.343 (3)	N32—C33	1.335 (4)
N11—N12	1.355 (3)	N32—N31	1.356 (3)
N11—H11	0.8600	N31—C35	1.347 (3)
N12—C13	1.324 (4)	N31—H31	0.8600
C13—C14	1.396 (4)	C33—C34	1.379 (4)
C13—H13	0.9300	C33—H33	0.9300
C14—C15	1.369 (4)	C34—C35	1.365 (4)
C14—H14	0.9300	C34—H34	0.9300
C15—C151	1.474 (4)	C35—C351	1.464 (4)
C151—C152	1.374 (4)	C351—C356	1.383 (5)
C151—C156	1.381 (4)	C351—C352	1.391 (4)
C152—C153	1.381 (4)	C352—C353	1.370 (5)
C152—H152	0.9300	C352—H352	0.9300
C153—C154	1.382 (6)	C353—C354	1.367 (7)
C153—H153	0.9300	C353—H353	0.9300
C154—C155	1.339 (6)	C354—C355	1.372 (7)
C154—H154	0.9300	C354—H354	0.9300
C155—C156	1.395 (5)	C355—C356	1.389 (5)
C155—H155	0.9300	C355—H355	0.9300
C156—H156	0.9300	C356—H356	0.9300
N22—C23	1.320 (4)	N42—C43	1.322 (4)
N22—N21	1.341 (3)	N42—N41	1.350 (3)
N21—C25	1.347 (4)	N41—C45	1.347 (3)
N21—H21	0.8600	N41—H41	0.8600
C23—C24	1.410 (5)	C43—C44	1.398 (4)
C23—H23	0.9300	C43—H43	0.9300
C24—C25	1.361 (5)	C44—C45	1.377 (4)
C24—H24	0.9300	C44—H44	0.9300
C25—C251	1.468 (4)	C45—C451	1.453 (4)
C251—C252	1.364 (5)	C451—C456	1.391 (4)
C251—C256	1.385 (5)	C451—C452	1.399 (4)
C252—C253	1.381 (5)	C452—C453	1.379 (5)
C252—H252	0.9300	C452—H452	0.9300
C253—C254	1.351 (6)	C453—C454	1.378 (6)
C253—H253	0.9300	C453—H453	0.9300
C254—C255	1.354 (7)	C454—C455	1.367 (6)
C254—H254	0.9300	C454—H454	0.9300
C255—C256	1.414 (6)	C455—C456	1.362 (5)
C255—H255	0.9300	C455—H455	0.9300
C256—H256	0.9300	C456—H456	0.9300
N12—Cu1—N12^i	180.0 (2)	N42—Cu2—N42^ii	180.00 (13)
N12—Cu1—N22	87.39 (10)	N42—Cu2—N32^ii	89.90 (9)
N12^i—Cu1—N22	92.61 (10)	N42^ii—Cu2—N32^ii	90.10 (9)
N12—Cu1—N22^i	92.61 (10)	N42—Cu2—N32	90.10 (9)
N12^i—Cu1—N22^i	87.39 (10)	N42^ii—Cu2—N32	89.90 (9)
N22—Cu1—N22^i	180.00 (13)	N32^ii—Cu2—N32	180.000 (1)
N12—Cu1—Cl1	88.90 (7)	N42—Cu2—Cl2	88.92 (7)
N12^i—Cu1—Cl1	91.10 (7)	N42^ii—Cu2—Cl2	91.08 (7)
N22—Cu1—Cl1	88.1 (2)	N32^ii—Cu2—Cl2	92.35 (7)
N22^i—Cu1—Cl1	91.94 (7)	N32—Cu2—Cl2	87.65 (7)
C15—N11—N12	111.3 (2)	C33—N32—N31	105.3 (2)
C15—N11—H11	124.4	C33—N32—Cu2	133.9 (2)
N12—N11—H11	124.4	N31—N32—Cu2	120.57 (18)
C13—N12—N11	106.1 (2)	C35—N31—N32	111.6 (2)
C13—N12—Cu1	133.42 (19)	C35—N31—H31	124.2
N11—N12—Cu1	119.00 (18)	N32—N31—H31	124.2
N12—C13—C14	109.8 (2)	N32—C33—C34	110.1 (3)
N12—C13—H13	125.1	N32—C33—H33	124.9
C14—C13—H13	125.1	C34—C33—H33	124.9
C15—C14—C13	106.2 (3)	C35—C34—C33	106.9 (3)
C15—C14—H14	126.9	C35—C34—H34	126.5
C13—C14—H14	126.9	C33—C34—H34	126.5
N11—C15—C14	106.6 (2)	N31—C35—C34	106.0 (3)
N11—C15—C151	122.0 (3)	N31—C35—C351	122.5 (3)
C14—C15—C151	131.3 (3)	C34—C35—C351	131.4 (3)
C152—C151—C156	118.8 (3)	C356—C351—C352	118.8 (3)
C152—C151—C15	122.2 (3)	C356—C351—C35	121.7 (3)
C156—C151—C15	119.0 (3)	C352—C351—C35	119.5 (3)
C151—C152—C153	120.8 (4)	C353—C352—C351	120.8 (4)
C151—C152—H152	119.6	C353—C352—H352	119.6
C153—C152—H152	119.6	C351—C352—H352	119.6
C152—C153—C154	120.1 (4)	C354—C353—C352	119.9 (4)
C152—C153—H153	120.0	C354—C353—H353	120.0
C154—C153—H153	120.0	C352—C353—H353	120.0
C155—C154—C153	119.3 (3)	C353—C354—C355	120.5 (4)
C155—C154—H154	120.3	C353—C354—H354	119.7
C153—C154—H154	120.3	C355—C354—H354	119.7
C154—C155—C156	121.6 (4)	C354—C355—C356	120.0 (5)
C154—C155—H155	119.2	C354—C355—H355	120.0
C156—C155—H155	119.2	C356—C355—H355	120.0
C151—C156—C155	119.5 (4)	C351—C356—C355	120.0 (4)
C151—C156—H156	120.3	C351—C356—H356	120.0
C155—C156—H156	120.3	C355—C356—H356	120.0
C23—N22—N21	105.6 (3)	C43—N42—N41	106.0 (2)
C23—N22—Cu1	134.4 (2)	C43—N42—Cu2	134.4 (2)
N21—N22—Cu1	119.66 (18)	N41—N42—Cu2	119.28 (17)
N22—N21—C25	112.6 (3)	C45—N41—N42	112.0 (2)
N22—N21—H21	123.7	C45—N41—H41	124.0
C25—N21—H21	123.7	N42—N41—H41	124.0
N22—C23—C24	109.9 (3)	N42—C43—C44	110.0 (3)
N22—C23—H23	125.0	N42—C43—H43	125.0
C24—C23—H23	125.0	C44—C43—H43	125.0
C25—C24—C23	106.0 (3)	C45—C44—C43	106.2 (2)
C25—C24—H24	127.0	C45—C44—H44	126.9
C23—C24—H24	127.0	C43—C44—H44	126.9
N21—C25—C24	105.8 (3)	N41—C45—C44	105.8 (2)
N21—C25—C251	121.7 (3)	N41—C45—C451	122.9 (2)
C24—C25—C251	132.4 (3)	C44—C45—C451	131.3 (3)
C252—C251—C256	118.2 (3)	C456—C451—C452	117.9 (3)
C252—C251—C25	122.2 (3)	C456—C451—C45	119.5 (3)
C256—C251—C25	119.6 (4)	C452—C451—C45	122.6 (3)
C251—C252—C253	121.7 (4)	C453—C452—C451	120.6 (3)
C251—C252—H252	119.1	C453—C452—H452	119.7
C253—C252—H252	119.1	C451—C452—H452	119.7
C254—C253—C252	120.5 (5)	C454—C453—C452	119.6 (4)
C254—C253—H253	119.8	C454—C453—H453	120.2
C252—C253—H253	119.8	C452—C453—H453	120.2
C253—C254—C255	119.6 (4)	C455—C454—C453	120.5 (3)
C253—C254—H254	120.2	C455—C454—H454	119.8
C255—C254—H254	120.2	C453—C454—H454	119.8
C254—C255—C256	120.8 (4)	C456—C455—C454	120.2 (4)
C254—C255—H255	119.6	C456—C455—H455	119.9
C256—C255—H255	119.6	C454—C455—H455	119.9
C251—C256—C255	119.2 (5)	C455—C456—C451	121.3 (3)
C251—C256—H256	120.4	C455—C456—H456	119.4
C255—C256—H256	120.4	C451—C456—H456	119.4
C15—N11—N12—C13	−0.4 (3)	N42—Cu2—N32—C33	81.9 (3)
C15—N11—N12—Cu1	167.67 (18)	N42^ii—Cu2—N32—C33	−98.1 (3)
N22—Cu1—N12—C13	77.0 (3)	Cl2—Cu2—N32—C33	170.9 (3)
N22^i—Cu1—N12—C13	−103.0 (3)	N42—Cu2—N32—N31	−104.7 (2)
Cl1—Cu1—N12—C13	165.1 (3)	N42^ii—Cu2—N32—N31	75.3 (2)
N22—Cu1—N12—N11	−87.1 (2)	Cl2—Cu2—N32—N31	−15.8 (2)
N22^i—Cu1—N12—N11	92.9 (2)	C33—N32—N31—C35	0.2 (3)
Cl1—Cu1—N12—N11	1.0 (2)	Cu2—N32—N31—C35	−174.82 (17)
N11—N12—C13—C14	0.0 (3)	N31—N32—C33—C34	−0.2 (3)
Cu1—N12—C13—C14	−165.6 (2)	Cu2—N32—C33—C34	173.9 (2)
N12—C13—C14—C15	0.4 (3)	N32—C33—C34—C35	0.2 (4)
N12—N11—C15—C14	0.6 (3)	N32—N31—C35—C34	−0.1 (3)
N12—N11—C15—C151	178.5 (2)	N32—N31—C35—C351	179.7 (2)
C13—C14—C15—N11	−0.6 (3)	C33—C34—C35—N31	0.0 (3)
C13—C14—C15—C151	−178.2 (3)	C33—C34—C35—C351	−179.8 (3)
N11—C15—C151—C152	−0.6 (4)	N31—C35—C351—C356	30.6 (5)
C14—C15—C151—C152	176.8 (3)	C34—C35—C351—C356	−149.6 (4)
N11—C15—C151—C156	179.9 (3)	N31—C35—C351—C352	−148.2 (3)
C14—C15—C151—C156	−2.8 (5)	C34—C35—C351—C352	31.6 (5)
C156—C151—C152—C153	−0.6 (5)	C356—C351—C352—C353	1.3 (6)
C15—C151—C152—C153	179.9 (3)	C35—C351—C352—C353	−179.9 (4)
C151—C152—C153—C154	0.8 (6)	C351—C352—C353—C354	−0.9 (7)
C152—C153—C154—C155	−0.3 (6)	C352—C353—C354—C355	−0.3 (8)
C153—C154—C155—C156	−0.5 (6)	C353—C354—C355—C356	1.1 (8)
C152—C151—C156—C155	−0.2 (5)	C352—C351—C356—C355	−0.5 (6)
C15—C151—C156—C155	179.4 (3)	C35—C351—C356—C355	−179.3 (4)
C154—C155—C156—C151	0.8 (6)	C354—C355—C356—C351	−0.7 (7)
N12—Cu1—N22—C23	−76.9 (3)	N32^ii—Cu2—N42—C43	100.9 (3)
N12^i—Cu1—N22—C23	103.1 (3)	N32—Cu2—N42—C43	−79.1 (3)
Cl1—Cu1—N22—C23	−165.8 (3)	Cl2—Cu2—N42—C43	−166.7 (3)
N12—Cu1—N22—N21	94.7 (2)	N32^ii—Cu2—N42—N41	−85.86 (19)
N12^i—Cu1—N22—N21	−85.3 (2)	N32—Cu2—N42—N41	94.14 (19)
Cl1—Cu1—N22—N21	5.7 (2)	Cl2—Cu2—N42—N41	6.5 (2)
C23—N22—N21—C25	1.0 (3)	C43—N42—N41—C45	1.1 (3)
Cu1—N22—N21—C25	−172.72 (19)	Cu2—N42—N41—C45	−173.84 (17)
N21—N22—C23—C24	−0.6 (4)	N41—N42—C43—C44	−0.5 (3)
Cu1—N22—C23—C24	171.9 (2)	Cu2—N42—C43—C44	173.3 (2)
N22—C23—C24—C25	−0.1 (5)	N42—C43—C44—C45	−0.3 (3)
N22—N21—C25—C24	−1.1 (4)	N42—N41—C45—C44	−1.3 (3)
N22—N21—C25—C251	179.9 (3)	N42—N41—C45—C451	175.8 (2)
C23—C24—C25—N21	0.7 (4)	C43—C44—C45—N41	0.9 (3)
C23—C24—C25—C251	179.6 (4)	C43—C44—C45—C451	−175.8 (3)
N21—C25—C251—C252	−10.1 (5)	N41—C45—C451—C456	−164.8 (3)
C24—C25—C251—C252	171.1 (4)	C44—C45—C451—C456	11.4 (5)
N21—C25—C251—C256	169.5 (3)	N41—C45—C451—C452	12.9 (4)
C24—C25—C251—C256	−9.3 (6)	C44—C45—C451—C452	−170.9 (3)
C256—C251—C252—C253	0.4 (6)	C456—C451—C452—C453	1.1 (5)
C25—C251—C252—C253	180.0 (4)	C45—C451—C452—C453	−176.6 (3)
C251—C252—C253—C254	0.0 (7)	C451—C452—C453—C454	−0.7 (5)
C252—C253—C254—C255	−0.1 (8)	C452—C453—C454—C455	−0.3 (6)
C253—C254—C255—C256	−0.1 (8)	C453—C454—C455—C456	0.8 (6)
C252—C251—C256—C255	−0.6 (6)	C454—C455—C456—C451	−0.4 (6)
C25—C251—C256—C255	179.8 (4)	C452—C451—C456—C455	−0.5 (5)
C254—C255—C256—C251	0.5 (8)	C45—C451—C456—C455	177.3 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···Cl1	0.86	2.40	3.071 (2)	135
N21—H21···Cl1	0.86	2.41	3.081 (3)	135
N31—H31···Cl2	0.86	2.47	3.120 (3)	133
N41—H41···Cl2	0.86	2.41	3.084 (2)	135
C14—H14···Cl2^iii	0.93	2.93	3.805 (3)	158
C155—H155···Cl2^iv	0.93	2.85	3.707 (4)	154
C13—H13···Cg3^iii	0.93	2.90	3.638 (5)	137
C455—H455···Cg3^v	0.93	2.88	3.693 (6)	146
C456—H456···Cg2^vi	0.93	2.87	3.670 (5)	144

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