Chloridotris(3,5-dimethyl-1H-pyrazole-κN)(formato-κO)copper(II)-dichlorido-bis(3,5-dimethyl-1H-pyrazole-κN)copper(II) (2/1).

The asymmetric unit of the title compound, [Cu(CHO(2))Cl(C(5)H(8)N(2))(3)](2)·[CuCl(2)(C(5)H(8)N(2))(2)] or 2[A]·[B], contains one A mol-ecule and one half-molecule of B, located on a centre of inversion. The Cu(II) environments in A and B are different. In A, the Cu(II) atom is coordinated by three N atoms from three 3,5-dimethyl-1H-pyrazole (L) ligands, one O atom from a formate ligand and a chloride anion in an axial position [Cu-Cl = 2.4275 (7) Å] in a distorted tetra-gonal-pyramidal geometry. The Cu(II) atom in B is coordinated by two N atoms from two L ligands and two chloride anions [Cu-Cl = 2.2524 (6) Å] in a distorted square-planar geometry. In the crystal, inter-molecular N-H⋯O hydrogen bonds link mol-ecules A into centrosymmetric dimers. Inter-molecular N-H⋯Cl hydrogen bonds further link these dimers with the B mol-ecules, forming chains propagating in [101].

Related literature

For metal complexes with pyrazole and its derivatives, see: Trofimenko (1972) ▶; La Monica & Ardizzoia (1997 ▶); Casarin et al. (2005 ▶); Davydenko et al. (2009 ▶). For details of the bio­inorganic chemistry of copper complexes with pyrazole, see: Krämer (1999 ▶); Raptis et al. (1999 ▶). For applications of copper complexes with pyrazole in mol­ecular magnetism and supra­molecular chemistry, see: Krämer et al. (2002 ▶); Seredyuk et al. (2007 ▶).

Experimental

Crystal data

[Cu(CHO2)Cl(C5H8N2)3]2·[CuCl2(C5H8N2)2]

M = 1191.53

Monoclinic,

a = 11.4457 (3) Å

b = 14.4720 (5) Å

c = 17.0313 (5) Å

β = 106.650 (2)°

V = 2702.82 (14) Å3

Z = 2

Mo Kα radiation

μ = 1.42 mm−1

T = 120 K

0.50 × 0.27 × 0.19 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: numerical (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.554, T max = 0.763

36108 measured reflections

5749 independent reflections

4611 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.01

5749 reflections

333 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.72 e Å−3

Δρmin = −0.83 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016461/cv5078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016461/cv5078Isup2.hkl

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

[Cu(CHO2)Cl(C5H8N2)3]2·[CuCl2(C5H8N2)2]	F(000) = 1234
Mr = 1191.53	Dx = 1.464 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 36108 reflections
a = 11.4457 (3) Å	θ = 1.9–26.8°
b = 14.4720 (5) Å	µ = 1.42 mm−1
c = 17.0313 (5) Å	T = 120 K
β = 106.650 (2)°	Block, blue
V = 2702.82 (14) Å3	0.50 × 0.27 × 0.19 mm
Z = 2

Stoe IPDS II diffractometer	5749 independent reflections
Radiation source: fine-focus sealed tube	4611 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω scans	θmax = 26.8°, θmin = 1.9°
Absorption correction: numerical (X-RED32; Stoe & Cie, 2002)	h = −14→14
Tmin = 0.554, Tmax = 0.763	k = −18→18
36108 measured reflections	l = −21→21

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0609P)2] where P = (Fo2 + 2Fc2)/3
5749 reflections	(Δ/σ)max = 0.001
333 parameters	Δρmax = 0.72 e Å−3
0 restraints	Δρmin = −0.83 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.

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.

	x	y	z	Uiso*/Ueq
Cu1	0.73059 (2)	0.426309 (19)	0.646481 (16)	0.03259 (9)
Cu2	1.0000	0.5000	1.0000	0.03732 (11)
Cl1	0.80389 (6)	0.51219 (4)	0.77357 (4)	0.04438 (15)
Cl2	1.02066 (6)	0.36400 (4)	0.94106 (4)	0.04571 (15)
N1	0.87868 (17)	0.34752 (14)	0.66725 (12)	0.0360 (4)
N2	0.97024 (19)	0.34221 (15)	0.73835 (13)	0.0386 (4)
N3	0.78754 (18)	0.50097 (14)	0.56033 (12)	0.0377 (4)
N4	0.7119 (2)	0.50467 (16)	0.48203 (13)	0.0413 (5)
N6	0.62439 (18)	0.31213 (14)	0.65350 (13)	0.0393 (4)
N7	0.5235 (2)	0.29562 (16)	0.58991 (15)	0.0436 (5)
N8	0.83090 (19)	0.46420 (15)	1.00220 (13)	0.0392 (4)
N9	0.7440 (2)	0.44923 (17)	0.93053 (14)	0.0448 (5)
C1	1.0239 (2)	0.25280 (18)	0.65202 (17)	0.0442 (6)
H1	1.0668	0.2121	0.6284	0.080*
C2	0.9111 (2)	0.29314 (16)	0.61396 (15)	0.0372 (5)
C3	1.0590 (2)	0.28477 (17)	0.73078 (16)	0.0407 (5)
C4	0.8330 (3)	0.2839 (2)	0.52783 (17)	0.0491 (6)
H4A	0.7488	0.2820	0.5271	0.080*
H4B	0.8535	0.2279	0.5046	0.080*
H4C	0.8462	0.3358	0.4963	0.080*
C5	1.1709 (3)	0.2667 (2)	0.79957 (19)	0.0563 (7)
H5A	1.2286	0.3156	0.8024	0.080*
H5B	1.2063	0.2090	0.7905	0.080*
H5C	1.1499	0.2638	0.8502	0.080*
C6	0.8677 (3)	0.5884 (2)	0.48219 (18)	0.0547 (7)
H6	0.9216	0.6269	0.4661	0.080*
C7	0.8829 (2)	0.55265 (17)	0.56019 (15)	0.0385 (5)
C8	0.7589 (2)	0.55637 (19)	0.43374 (16)	0.0443 (6)
C9	0.9877 (2)	0.5650 (2)	0.63566 (18)	0.0543 (7)
H9A	0.9576	0.5687	0.6827	0.080*
H9B	1.0305	0.6209	0.6311	0.080*
H9C	1.0421	0.5133	0.6415	0.080*
C11	0.6941 (3)	0.5685 (3)	0.34459 (17)	0.0650 (9)
H11A	0.7164	0.5193	0.3139	0.080*
H11B	0.7169	0.6267	0.3261	0.080*
H11C	0.6076	0.5674	0.3365	0.080*
C12	0.5155 (3)	0.19598 (19)	0.68291 (19)	0.0517 (7)
H12	0.4911	0.1484	0.7114	0.080*
C13	0.6201 (2)	0.25102 (17)	0.71056 (16)	0.0423 (6)
C14	0.4565 (2)	0.22632 (18)	0.60563 (19)	0.0492 (6)
C15	0.7171 (3)	0.2453 (2)	0.79031 (18)	0.0579 (7)
H15A	0.7810	0.2052	0.7847	0.080*
H15B	0.6830	0.2213	0.8315	0.080*
H15C	0.7498	0.3058	0.8061	0.080*
C16	0.3415 (3)	0.1954 (2)	0.5443 (3)	0.0763 (11)
H16A	0.3058	0.2464	0.5097	0.080*
H16B	0.2853	0.1733	0.5724	0.080*
H16C	0.3597	0.1465	0.5115	0.080*
C17	0.6545 (3)	0.4272 (2)	1.02527 (18)	0.0501 (6)
H17	0.5969	0.4145	1.0527	0.080*
C18	0.7763 (2)	0.45062 (17)	1.06020 (16)	0.0406 (5)
C19	0.6368 (2)	0.4267 (2)	0.94247 (18)	0.0491 (6)
C20	0.8437 (3)	0.4582 (2)	1.14949 (17)	0.0557 (7)
H20A	0.9297	0.4616	1.1560	0.080*
H20B	0.8265	0.4050	1.1780	0.080*
H20C	0.8179	0.5130	1.1717	0.080*
C21	0.5268 (3)	0.4061 (3)	0.8719 (2)	0.0783 (11)
H21A	0.5397	0.4290	0.8221	0.080*
H21B	0.4566	0.4357	0.8808	0.080*
H21C	0.5138	0.3406	0.8676	0.080*
C22	0.5712 (2)	0.57910 (18)	0.60437 (17)	0.0472 (6)
H22	0.6418	0.6111	0.6312	0.080*
O1	0.57534 (15)	0.49305 (11)	0.60884 (11)	0.0400 (4)
O2	0.48246 (17)	0.62519 (13)	0.56778 (12)	0.0514 (5)
H2	0.966 (3)	0.371 (3)	0.779 (2)	0.080*
H4	0.650 (4)	0.467 (3)	0.467 (2)	0.080*
H7	0.515 (4)	0.318 (3)	0.551 (2)	0.080*
H9	0.753 (4)	0.459 (3)	0.887 (3)	0.080*

	U11	U22	U33	U12	U13	U23
Cu1	0.02773 (14)	0.03492 (15)	0.03263 (15)	0.00171 (11)	0.00467 (11)	0.00305 (11)
Cu2	0.0337 (2)	0.0406 (2)	0.0404 (2)	−0.00253 (17)	0.01504 (18)	−0.00089 (17)
Cl1	0.0514 (4)	0.0500 (3)	0.0289 (3)	0.0016 (3)	0.0069 (3)	−0.0006 (2)
Cl2	0.0451 (3)	0.0447 (3)	0.0490 (4)	−0.0002 (3)	0.0162 (3)	−0.0035 (3)
N1	0.0305 (10)	0.0389 (10)	0.0353 (10)	0.0008 (8)	0.0043 (8)	0.0000 (8)
N2	0.0339 (10)	0.0426 (11)	0.0360 (11)	0.0053 (8)	0.0048 (9)	0.0021 (9)
N3	0.0307 (10)	0.0482 (11)	0.0299 (10)	−0.0041 (8)	0.0016 (8)	0.0045 (8)
N4	0.0347 (11)	0.0536 (13)	0.0306 (10)	−0.0059 (9)	0.0015 (8)	0.0066 (9)
N6	0.0320 (10)	0.0388 (10)	0.0422 (11)	−0.0006 (8)	0.0028 (8)	0.0047 (9)
N7	0.0330 (11)	0.0440 (12)	0.0471 (13)	−0.0031 (9)	0.0009 (10)	0.0044 (10)
N8	0.0363 (11)	0.0455 (11)	0.0360 (11)	−0.0069 (9)	0.0104 (9)	−0.0047 (9)
N9	0.0426 (12)	0.0569 (13)	0.0358 (11)	−0.0059 (10)	0.0128 (10)	−0.0056 (10)
C1	0.0409 (14)	0.0433 (13)	0.0503 (15)	0.0070 (11)	0.0163 (12)	0.0002 (11)
C2	0.0360 (12)	0.0344 (11)	0.0423 (13)	−0.0010 (9)	0.0129 (10)	−0.0023 (10)
C3	0.0318 (12)	0.0401 (12)	0.0494 (14)	0.0051 (10)	0.0103 (11)	0.0093 (11)
C4	0.0466 (15)	0.0544 (15)	0.0444 (15)	−0.0014 (12)	0.0099 (12)	−0.0135 (12)
C5	0.0424 (15)	0.0629 (18)	0.0571 (18)	0.0138 (13)	0.0037 (13)	0.0100 (14)
C6	0.0412 (15)	0.075 (2)	0.0484 (15)	−0.0128 (14)	0.0142 (12)	0.0134 (14)
C7	0.0308 (12)	0.0460 (13)	0.0384 (12)	−0.0018 (10)	0.0096 (10)	−0.0004 (10)
C8	0.0412 (14)	0.0568 (16)	0.0355 (13)	0.0047 (11)	0.0118 (11)	0.0084 (11)
C9	0.0361 (14)	0.077 (2)	0.0465 (15)	−0.0117 (13)	0.0062 (12)	−0.0054 (14)
C11	0.0569 (19)	0.102 (3)	0.0348 (14)	0.0057 (17)	0.0115 (13)	0.0173 (16)
C12	0.0530 (17)	0.0415 (14)	0.0631 (18)	−0.0055 (12)	0.0205 (14)	0.0070 (13)
C13	0.0449 (14)	0.0368 (12)	0.0453 (14)	0.0025 (10)	0.0131 (11)	0.0039 (10)
C14	0.0389 (14)	0.0405 (13)	0.0656 (18)	−0.0046 (11)	0.0106 (13)	−0.0041 (13)
C15	0.066 (2)	0.0556 (17)	0.0450 (16)	−0.0010 (14)	0.0052 (14)	0.0090 (13)
C16	0.0484 (18)	0.0609 (19)	0.102 (3)	−0.0152 (15)	−0.0063 (18)	−0.0046 (19)
C17	0.0449 (15)	0.0578 (16)	0.0528 (16)	−0.0035 (12)	0.0226 (13)	−0.0044 (13)
C18	0.0435 (14)	0.0404 (12)	0.0403 (13)	−0.0034 (10)	0.0160 (11)	−0.0014 (10)
C19	0.0377 (14)	0.0598 (16)	0.0485 (15)	−0.0013 (12)	0.0103 (12)	−0.0095 (13)
C20	0.0581 (18)	0.0687 (18)	0.0406 (15)	−0.0085 (15)	0.0145 (13)	−0.0011 (13)
C21	0.0467 (18)	0.111 (3)	0.069 (2)	−0.0045 (19)	0.0029 (16)	−0.025 (2)
C22	0.0368 (13)	0.0419 (14)	0.0519 (15)	−0.0009 (11)	−0.0048 (11)	0.0017 (12)
O1	0.0300 (8)	0.0390 (9)	0.0474 (10)	0.0006 (7)	0.0055 (7)	0.0020 (7)
O2	0.0421 (11)	0.0473 (10)	0.0548 (11)	0.0111 (8)	−0.0022 (9)	0.0037 (9)

Cu1—O1	1.9618 (16)	C6—C8	1.363 (4)
Cu1—N1	1.989 (2)	C6—C7	1.389 (4)
Cu1—N3	2.072 (2)	C6—H6	0.9300
Cu1—N6	2.075 (2)	C7—C9	1.496 (4)
Cu1—Cl1	2.4275 (7)	C8—C11	1.497 (4)
Cu2—N8i	2.014 (2)	C9—H9A	0.9600
Cu2—N8	2.014 (2)	C9—H9B	0.9600
Cu2—Cl2	2.2524 (6)	C9—H9C	0.9600
Cu2—Cl2i	2.2524 (6)	C11—H11A	0.9600
N1—C2	1.332 (3)	C11—H11B	0.9600
N1—N2	1.358 (3)	C11—H11C	0.9600
N2—C3	1.347 (3)	C12—C14	1.368 (4)
N2—H2	0.82 (4)	C12—C13	1.403 (4)
N3—C7	1.324 (3)	C12—H12	0.9300
N3—N4	1.367 (3)	C13—C15	1.490 (4)
N4—C8	1.334 (3)	C14—C16	1.495 (4)
N4—H4	0.87 (4)	C15—H15A	0.9600
N6—C13	1.325 (3)	C15—H15B	0.9600
N6—N7	1.359 (3)	C15—H15C	0.9600
N7—C14	1.336 (4)	C16—H16A	0.9600
N7—H7	0.72 (4)	C16—H16B	0.9600
N8—C18	1.326 (3)	C16—H16C	0.9600
N8—N9	1.353 (3)	C17—C19	1.366 (4)
N9—C19	1.340 (4)	C17—C18	1.392 (4)
N9—H9	0.79 (4)	C17—H17	0.9300
C1—C3	1.366 (4)	C18—C20	1.499 (4)
C1—C2	1.395 (4)	C19—C21	1.500 (4)
C1—H1	0.9300	C20—H20A	0.9600
C2—C4	1.489 (4)	C20—H20B	0.9600
C3—C5	1.491 (4)	C20—H20C	0.9600
C4—H4A	0.9600	C21—H21A	0.9600
C4—H4B	0.9600	C21—H21B	0.9600
C4—H4C	0.9600	C21—H21C	0.9600
C5—H5A	0.9600	C22—O2	1.226 (3)
C5—H5B	0.9600	C22—O1	1.248 (3)
C5—H5C	0.9600	C22—H22	0.9300
O1—Cu1—N1	170.57 (8)	N3—C7—C6	109.5 (2)
O1—Cu1—N3	87.20 (8)	N3—C7—C9	121.6 (2)
N1—Cu1—N3	89.99 (8)	C6—C7—C9	128.8 (2)
O1—Cu1—N6	85.42 (7)	N4—C8—C6	106.1 (2)
N1—Cu1—N6	90.96 (8)	N4—C8—C11	121.4 (3)
N3—Cu1—N6	139.85 (8)	C6—C8—C11	132.5 (3)
O1—Cu1—Cl1	95.08 (5)	C7—C9—H9A	109.5
N1—Cu1—Cl1	94.34 (6)	C7—C9—H9B	109.5
N3—Cu1—Cl1	105.43 (6)	H9A—C9—H9B	109.5
N6—Cu1—Cl1	114.51 (6)	C7—C9—H9C	109.5
N8i—Cu2—N8	180.0	H9A—C9—H9C	109.5
N8i—Cu2—Cl2	89.56 (6)	H9B—C9—H9C	109.5
N8—Cu2—Cl2	90.44 (6)	C8—C11—H11A	109.5
N8i—Cu2—Cl2i	90.44 (6)	C8—C11—H11B	109.5
N8—Cu2—Cl2i	89.56 (6)	H11A—C11—H11B	109.5
Cl2—Cu2—Cl2i	180.000 (1)	C8—C11—H11C	109.5
C2—N1—N2	106.2 (2)	H11A—C11—H11C	109.5
C2—N1—Cu1	127.41 (17)	H11B—C11—H11C	109.5
N2—N1—Cu1	126.29 (16)	C14—C12—C13	106.2 (2)
C3—N2—N1	111.1 (2)	C14—C12—H12	126.9
C3—N2—H2	128 (3)	C13—C12—H12	126.9
N1—N2—H2	120 (3)	N6—C13—C12	109.9 (2)
C7—N3—N4	105.55 (19)	N6—C13—C15	122.1 (2)
C7—N3—Cu1	136.28 (17)	C12—C13—C15	128.0 (2)
N4—N3—Cu1	118.13 (15)	N7—C14—C12	106.3 (2)
C8—N4—N3	111.7 (2)	N7—C14—C16	121.8 (3)
C8—N4—H4	127 (3)	C12—C14—C16	132.0 (3)
N3—N4—H4	120 (3)	C13—C15—H15A	109.5
C13—N6—N7	105.4 (2)	C13—C15—H15B	109.5
C13—N6—Cu1	135.97 (18)	H15A—C15—H15B	109.5
N7—N6—Cu1	118.17 (16)	C13—C15—H15C	109.5
C14—N7—N6	112.2 (2)	H15A—C15—H15C	109.5
C14—N7—H7	126 (3)	H15B—C15—H15C	109.5
N6—N7—H7	121 (3)	C14—C16—H16A	109.5
C18—N8—N9	105.5 (2)	C14—C16—H16B	109.5
C18—N8—Cu2	135.42 (18)	H16A—C16—H16B	109.5
N9—N8—Cu2	119.08 (15)	C14—C16—H16C	109.5
C19—N9—N8	111.7 (2)	H16A—C16—H16C	109.5
C19—N9—H9	124 (3)	H16B—C16—H16C	109.5
N8—N9—H9	124 (3)	C19—C17—C18	106.1 (2)
C3—C1—C2	106.7 (2)	C19—C17—H17	127.0
C3—C1—H1	126.7	C18—C17—H17	127.0
C2—C1—H1	126.7	N8—C18—C17	110.2 (2)
N1—C2—C1	109.4 (2)	N8—C18—C20	122.0 (2)
N1—C2—C4	121.2 (2)	C17—C18—C20	127.8 (2)
C1—C2—C4	129.4 (2)	N9—C19—C17	106.5 (2)
N2—C3—C1	106.6 (2)	N9—C19—C21	121.4 (3)
N2—C3—C5	122.3 (2)	C17—C19—C21	132.1 (3)
C1—C3—C5	131.1 (2)	C18—C20—H20A	109.5
C2—C4—H4A	109.5	C18—C20—H20B	109.5
C2—C4—H4B	109.5	H20A—C20—H20B	109.5
H4A—C4—H4B	109.5	C18—C20—H20C	109.5
C2—C4—H4C	109.5	H20A—C20—H20C	109.5
H4A—C4—H4C	109.5	H20B—C20—H20C	109.5
H4B—C4—H4C	109.5	C19—C21—H21A	109.5
C3—C5—H5A	109.5	C19—C21—H21B	109.5
C3—C5—H5B	109.5	H21A—C21—H21B	109.5
H5A—C5—H5B	109.5	C19—C21—H21C	109.5
C3—C5—H5C	109.5	H21A—C21—H21C	109.5
H5A—C5—H5C	109.5	H21B—C21—H21C	109.5
H5B—C5—H5C	109.5	O2—C22—O1	125.9 (2)
C8—C6—C7	107.2 (2)	O2—C22—H22	117.1
C8—C6—H6	126.4	O1—C22—H22	117.1
C7—C6—H6	126.4	C22—O1—Cu1	121.76 (16)
N3—Cu1—N1—C2	−61.4 (2)	C3—C1—C2—C4	178.6 (3)
N6—Cu1—N1—C2	78.5 (2)	N1—N2—C3—C1	0.6 (3)
Cl1—Cu1—N1—C2	−166.9 (2)	N1—N2—C3—C5	179.6 (2)
N3—Cu1—N1—N2	115.12 (19)	C2—C1—C3—N2	−0.4 (3)
N6—Cu1—N1—N2	−105.02 (19)	C2—C1—C3—C5	−179.2 (3)
Cl1—Cu1—N1—N2	9.65 (19)	N4—N3—C7—C6	−0.2 (3)
C2—N1—N2—C3	−0.6 (3)	Cu1—N3—C7—C6	−177.8 (2)
Cu1—N1—N2—C3	−177.71 (17)	N4—N3—C7—C9	−179.3 (2)
O1—Cu1—N3—C7	128.2 (3)	Cu1—N3—C7—C9	3.1 (4)
N1—Cu1—N3—C7	−60.8 (3)	C8—C6—C7—N3	−0.2 (3)
N6—Cu1—N3—C7	−152.3 (2)	C8—C6—C7—C9	178.7 (3)
Cl1—Cu1—N3—C7	33.7 (3)	N3—N4—C8—C6	−0.8 (3)
O1—Cu1—N3—N4	−49.16 (18)	N3—N4—C8—C11	178.3 (3)
N1—Cu1—N3—N4	121.84 (18)	C7—C6—C8—N4	0.6 (3)
N6—Cu1—N3—N4	30.4 (2)	C7—C6—C8—C11	−178.3 (3)
Cl1—Cu1—N3—N4	−143.66 (16)	N7—N6—C13—C12	−0.3 (3)
C7—N3—N4—C8	0.7 (3)	Cu1—N6—C13—C12	171.4 (2)
Cu1—N3—N4—C8	178.75 (18)	N7—N6—C13—C15	178.8 (2)
O1—Cu1—N6—C13	−125.8 (3)	Cu1—N6—C13—C15	−9.4 (4)
N1—Cu1—N6—C13	62.9 (3)	C14—C12—C13—N6	0.4 (3)
N3—Cu1—N6—C13	154.0 (2)	C14—C12—C13—C15	−178.7 (3)
Cl1—Cu1—N6—C13	−32.3 (3)	N6—N7—C14—C12	0.1 (3)
O1—Cu1—N6—N7	45.19 (18)	N6—N7—C14—C16	−179.6 (3)
N1—Cu1—N6—N7	−126.09 (19)	C13—C12—C14—N7	−0.3 (3)
N3—Cu1—N6—N7	−35.0 (2)	C13—C12—C14—C16	179.4 (3)
Cl1—Cu1—N6—N7	138.70 (17)	N9—N8—C18—C17	−0.2 (3)
C13—N6—N7—C14	0.1 (3)	Cu2—N8—C18—C17	179.3 (2)
Cu1—N6—N7—C14	−173.38 (18)	N9—N8—C18—C20	178.3 (2)
Cl2—Cu2—N8—C18	117.9 (3)	Cu2—N8—C18—C20	−2.2 (4)
Cl2i—Cu2—N8—C18	−62.1 (3)	C19—C17—C18—N8	0.2 (3)
Cl2—Cu2—N8—N9	−62.61 (18)	C19—C17—C18—C20	−178.1 (3)
Cl2i—Cu2—N8—N9	117.39 (18)	N8—N9—C19—C17	0.2 (3)
C18—N8—N9—C19	0.0 (3)	N8—N9—C19—C21	−179.5 (3)
Cu2—N8—N9—C19	−179.60 (19)	C18—C17—C19—N9	−0.2 (3)
N2—N1—C2—C1	0.3 (3)	C18—C17—C19—C21	179.4 (4)
Cu1—N1—C2—C1	177.43 (17)	O2—C22—O1—Cu1	165.4 (2)
N2—N1—C2—C4	−178.4 (2)	N3—Cu1—O1—C22	−51.9 (2)
Cu1—N1—C2—C4	−1.3 (3)	N6—Cu1—O1—C22	167.6 (2)
C3—C1—C2—N1	0.0 (3)	Cl1—Cu1—O1—C22	53.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1	0.82 (4)	2.74 (4)	3.270 (2)	124 (3)
N2—H2···Cl2	0.82 (4)	2.66 (4)	3.348 (2)	143 (3)
N9—H9···Cl1	0.79 (4)	2.30 (4)	3.081 (2)	168 (4)
N7—H7···O2ii	0.72 (4)	2.19 (4)	2.903 (3)	170 (4)
N4—H4···O2ii	0.87 (4)	1.98 (4)	2.850 (3)	176 (4)
N4—H4···O1ii	0.87 (4)	2.59 (4)	3.208 (3)	128 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1	0.82 (4)	2.74 (4)	3.270 (2)	124 (3)
N2—H2⋯Cl2	0.82 (4)	2.66 (4)	3.348 (2)	143 (3)
N9—H9⋯Cl1	0.79 (4)	2.30 (4)	3.081 (2)	168 (4)
N7—H7⋯O2i	0.72 (4)	2.19 (4)	2.903 (3)	170 (4)
N4—H4⋯O2i	0.87 (4)	1.98 (4)	2.850 (3)	176 (4)
N4—H4⋯O1i	0.87 (4)	2.59 (4)	3.208 (3)	128 (3)

Symmetry code: (i) .