Hexa-μ-chloro-μ₄-oxo-tetrakis{[5-(2,4,6-trimethylphenyl)pyrazole-κN²]copper(II)}

The title compound, [Cu₄Cl₆O(C₁₂H₁₄N₂)₄], is a new example of the well known [Cu₄(μ₄-O)(μ-X)₆L₄] class of complex (X⁻ is Cl⁻, Br⁻ or I⁻, and L is a monodentate ligand). The molecule has crystallographic C₂ symmetry, with two Cl⁻ ions on each edge of a Cu₄ tetrahedron. Two of these, on opposite edges of the tetrahedron, accept intramolecular hydrogen bonds from two of the pyrazole N—H donors.

S1. Comment

The [Cu₄(µ₄-O)(µ-X)₆L₄]^n- structural type is well known, where X⁻ can be Cl⁻, Br⁻ or I⁻ and L is a mondentate ligand. The terminal ligand L can be a halide (giving n = 4), or a variety of neutral monodentate N or O donors (giving n = 0), such as imidazoles (Atria et al., 1999; Clegg et al., 1988), thiazolines (Bolos & Christidis, 2002), pyridines (Gill & Sterns, 1970; Händler, 1990; Kilbourn & Dunitz, 1967), pyrazines (Näther & Jeß, 2002), amines (Pavlenko et al., 1993), sulfimides (Kelly et al., 1999), phosphine oxides (Jorík et al., 1996) or sulfoxides (Guy et al., 1988) (not a complete list). Only one previous example containing a pyrazole terminal ligand has been structurally characterized, namely [Cu₄(µ₄-O)(µ-Cl)₆(L¹)₄] (L¹ is 3,4-dimethyl-5-phenylpyrazole; Keij et al., 1991). As part of our studies of the reactions of substituted pyrazoles with Cu^II salts (Liu et al., 2001; Liu, McAllister et al., 2002; Liu, McLaughlin et al., 2002), we have now isolated the title compound, (I), as a second example with a similar formulation, namely [Cu₄(µ₄-O)(µ-Cl)₆(L²)₄] [L² is 5-(2,4,6-trimethylphenyl)pyrazole]. \sch

The approximately tetrahedral cluster core in (I) has crystallographic C₂ symmetry, with the C₂ axis at (1/2, y, 1/4) passing through atoms Cl34, O3 and Cl35. The two unique Cu centres have very similar distorted trigonal-bipyramidal stereochemistries, with τ values of 0.7198 (14) (Cu1) and 0.7560 (12) (Cu2), which are closer to the ideal value of 1 for a trigonal bipyramid than the value of 0 expected for an ideal square pyramid (Addison et al., 1984). The Cu—N, Cu—O and Cu—Cl distances in the molecule lie within the usual ranges, but show small differences between the two Cu centres.

Interestingly, the Cu—Cl bonds to the two ligands that accept N—H···Cl hydrogen bonds (see below) are not notably longer than the other Cu—Cl bonds in the molecule, showing that the small Cu—Cl bond-length variations cannot be attributed to this feature of the structure. The Cu—O—Cu angles in the molecule also show small distortions from the tetrahedral angle. These small deviations from ideal tetrahedral molecular symmetry are common in [Cu₄(µ₄-O)(µ-X)₆L₄] complexes, and have a significant effect on their magnetic properties (Blake et al., 1997, and references therein). The four unique Cu···Cu distances in the structure range from 3.0570 (4)–3.1689 (5) Å.

The four L² ligands in the molecule form two pairs of intramolecular hydrogen bonds, with N19—H19 and N19ⁱ—H19ⁱ [symmetry code: (i) 1 − x, y, 1/2 − z] interacting with atom Cl34, and N5—H5 and N5ⁱ—H5ⁱ with atom Cl35. This is the same pattern of intramolecular hydrogen bonding shown by [Cu₄(µ₄-O)(µ-Cl)₆(L¹)₄] (Keij et al., 1991).

The molecules in the crystal associate through two unique π–π interactions. One is between the aryl groups C23—C28 and C9ⁱⁱ—C14ⁱⁱ [symmetry code: (ii) 1 − x, y + 1, 1/2 − z]. The least-squares planes of these two groups have a dihedral angle between them of 5.89 (11)°, and are separated by an average of 3.72 Å. The centroids of the two interacting aryl rings are offset by 1.69 Å. The second π–π interaction is between the opposite face of C23—C28 and C23ⁱⁱⁱ—C28ⁱⁱⁱ [symmetry code: (iii) 1 − x, 2 − y, 1 − z]. These two rings are coplanar by symmetry and separated by 3.70 Å, with centroids offset by 2.59 Å. The effect of these interactions is to associate the molecules into discrete π–π-stacked tetrads, which zigzag along the crystallographic [110] direction. There are no other significant intermolecular interactions in the lattice. Request from coeditor - please insert references to Figs. 1 and 2 at appropriate places.

S2. Experimental

A solution of CuCl₂ (0.13 g, 1.0 mmol) in MeOH (10 ml) was added to a solution of 3-mesitylpyrazole (0.37 g, 2.0 mmol) and NaOH (0.040 g, 1.0 mol) in MeOH (20 ml), yielding an immediate green precipitate. The mixture was stirred overnight and then filtered. Slow concentration of the filtrate by evaporation yielded dark-blue crystals of (I), contaminated by a smaller amount of paler blue [CuCl₂L₄]. Elemental analysis of (I), found: C 46.9, H 4.9, N 9.1%; calculated for C₄₈H₅₆Cl₆Cu₄N₈O: C 47.0, H 4.6, N 9.1%.

S3. Refinement

The slightly high displacement parameters on atoms C26, C27 and C30 may be indicative of a small degree of librational disorder involving these atoms. However, attempts to refine a static disorder model for the C23—C31 mesityl group to take account of this were unsuccessful and the original model has been retained. All H atoms were placed in calculated positions and refined using a riding model, with the methyl group torsion angles being allowed to refine freely. The fixed C—H distances were: C—H(aryl) = 0.95, C—H(methyl) = 0.98 and N—H = 0.88 Å. The H-atom U_iso parameters were fixed at 1.2U_eq(C) for the C—H(aryl) and N—H groups, and at 1.5U_eq(C) for C—H(methyl).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.

Figures

	Fig. 1. The molecular structure of (I), with 50% probability displacement ellipsoids and the atom-numbering scheme [symmetry code: (i) 1 − x, y, 1/2 − z]. All carbon-bound H atoms have been omitted for clarity.
	Fig. 2. A partial packing diagram for (I), highlighting the association via the mesityl substituents to give discrete π–π-stacked tetrads. All atoms are plotted with arbitrary radii.

Hexa-µ-chloro-µ₄-oxo-tetrakis{[5-(2,4,6-trimethylphenyl)pyrazole- κN²]copper(II)}

Crystal data

[Cu4Cl6O(C12H14N2)4]	F(000) = 2504
Mr = 1227.87	Dx = 1.543 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 45511 reflections
a = 21.6279 (2) Å	θ = 2.6–27.5°
b = 11.8266 (1) Å	µ = 1.93 mm^−1
c = 20.8023 (3) Å	T = 150 K
β = 96.4448 (5)°	Lath, dark blue
V = 5287.28 (10) Å^3	0.30 × 0.24 × 0.14 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	6034 independent reflections
Radiation source: fine-focus sealed tube	5044 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
please specify type of scans	h = −27→28
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −15→15
Tmin = 0.595, Tmax = 0.774	l = −26→26
45511 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 4.466P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
6034 reflections	Δρmax = 0.49 e Å^−3
311 parameters	Δρmin = −0.81 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00148 (15)

Special details

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi = 0 degree settings 1 degree omega exposures for chi = 90 degree settings

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. All non-H atoms were refined anisotropically, and no restraints were applied. All H atoms were placed in calculated positions and refined using a riding model.

The asymmetric unit contains half a complex molecule lying on the crystallographic C₂ axis at (-x + 1, y, −z + 0.5).

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

	x	y	z	Uiso*/Ueq
Cu1	0.426319 (12)	0.36039 (2)	0.238778 (15)	0.04162 (11)
Cu2	0.496150 (13)	0.54027 (2)	0.323955 (15)	0.04324 (11)
O3	0.5000	0.44886 (17)	0.2500	0.0384 (5)
N4	0.35552 (9)	0.25795 (16)	0.22768 (10)	0.0425 (4)
N5	0.36226 (9)	0.15433 (16)	0.20167 (10)	0.0428 (4)
H5	0.3974	0.1293	0.1893	0.051*
C6	0.30923 (10)	0.09383 (19)	0.19679 (11)	0.0393 (5)
C7	0.26532 (11)	0.1628 (2)	0.21986 (13)	0.0483 (6)
H7	0.2228	0.1454	0.2224	0.058*
C8	0.29589 (11)	0.2633 (2)	0.23875 (13)	0.0486 (6)
H8	0.2770	0.3266	0.2569	0.058*
C9	0.30819 (10)	−0.02384 (19)	0.17203 (11)	0.0379 (5)
C10	0.34290 (10)	−0.1081 (2)	0.20700 (11)	0.0392 (5)
C11	0.34189 (10)	−0.2179 (2)	0.18222 (12)	0.0426 (5)
H11	0.3651	−0.2755	0.2059	0.051*
C12	0.30778 (11)	−0.2444 (2)	0.12395 (13)	0.0476 (6)
C13	0.27367 (12)	−0.1601 (2)	0.09014 (13)	0.0473 (6)
H13	0.2501	−0.1781	0.0501	0.057*
C14	0.27291 (11)	−0.0497 (2)	0.11313 (12)	0.0411 (5)
C15	0.38043 (13)	−0.0833 (2)	0.27164 (13)	0.0537 (6)
H15A	0.3882	−0.1540	0.2958	0.081*
H15B	0.3571	−0.0312	0.2965	0.081*
H15C	0.4202	−0.0487	0.2643	0.081*
C16	0.30785 (15)	−0.3645 (2)	0.09786 (18)	0.0683 (9)
H16A	0.2670	−0.3817	0.0746	0.103*
H16B	0.3167	−0.4176	0.1339	0.103*
H16C	0.3399	−0.3717	0.0683	0.103*
C17	0.23448 (13)	0.0389 (2)	0.07473 (13)	0.0504 (6)
H17A	0.2235	0.0119	0.0304	0.076*
H17B	0.2586	0.1090	0.0740	0.076*
H17C	0.1964	0.0532	0.0949	0.076*
N18	0.49638 (10)	0.63686 (16)	0.39910 (11)	0.0490 (5)
N19	0.53308 (9)	0.72953 (16)	0.40653 (10)	0.0427 (4)
H19	0.5535	0.7575	0.3759	0.051*
C20	0.53478 (12)	0.7744 (2)	0.46656 (12)	0.0450 (5)
C21	0.49727 (15)	0.7054 (2)	0.49919 (15)	0.0595 (7)
H21	0.4888	0.7133	0.5428	0.071*
C22	0.47435 (15)	0.6224 (2)	0.45565 (15)	0.0620 (7)
H22	0.4468	0.5635	0.4650	0.074*
C23	0.57056 (11)	0.8778 (2)	0.48577 (12)	0.0447 (5)
C24	0.56339 (12)	0.9751 (2)	0.44704 (13)	0.0472 (6)
C25	0.59777 (14)	1.0717 (3)	0.46630 (15)	0.0599 (7)
H25	0.5933	1.1369	0.4396	0.072*
C26	0.63744 (15)	1.0760 (3)	0.52183 (17)	0.0698 (9)
C27	0.64407 (14)	0.9790 (4)	0.55972 (16)	0.0765 (11)
H27	0.6723	0.9806	0.5982	0.092*
C28	0.61102 (14)	0.8788 (3)	0.54381 (14)	0.0595 (7)
C29	0.51840 (13)	0.9808 (2)	0.38650 (13)	0.0531 (6)
H29A	0.5096	1.0601	0.3752	0.080*
H29B	0.4796	0.9425	0.3938	0.080*
H29C	0.5367	0.9436	0.3510	0.080*
C30	0.6721 (2)	1.1830 (4)	0.5435 (2)	0.1104 (18)
H30A	0.6777	1.2296	0.5056	0.166*
H30B	0.7129	1.1633	0.5661	0.166*
H30C	0.6481	1.2253	0.5727	0.166*
C31	0.61846 (18)	0.7784 (4)	0.58792 (16)	0.0851 (11)
H31A	0.6564	0.7869	0.6180	0.128*
H31B	0.6214	0.7095	0.5622	0.128*
H31C	0.5824	0.7730	0.6124	0.128*
Cl32	0.38760 (3)	0.47698 (5)	0.31567 (4)	0.05574 (19)
Cl33	0.42428 (3)	0.41732 (5)	0.12669 (3)	0.05115 (16)
Cl34	0.5000	0.69909 (6)	0.2500	0.04494 (19)
Cl35	0.5000	0.19798 (6)	0.2500	0.0531 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03262 (16)	0.03060 (16)	0.0631 (2)	−0.00468 (10)	0.01176 (13)	−0.00346 (11)
Cu2	0.03790 (17)	0.02994 (16)	0.0631 (2)	−0.00101 (10)	0.01120 (13)	−0.00571 (12)
O3	0.0316 (10)	0.0258 (10)	0.0588 (13)	0.000	0.0098 (9)	0.000
N4	0.0346 (9)	0.0328 (9)	0.0616 (12)	−0.0020 (8)	0.0113 (8)	−0.0060 (8)
N5	0.0320 (9)	0.0355 (10)	0.0628 (12)	−0.0042 (7)	0.0141 (9)	−0.0084 (9)
C6	0.0322 (10)	0.0361 (11)	0.0505 (12)	−0.0041 (9)	0.0083 (9)	−0.0026 (9)
C7	0.0311 (11)	0.0441 (13)	0.0712 (16)	−0.0052 (10)	0.0130 (11)	−0.0124 (12)
C8	0.0347 (11)	0.0401 (13)	0.0727 (16)	−0.0015 (10)	0.0130 (11)	−0.0112 (11)
C9	0.0303 (10)	0.0353 (11)	0.0493 (12)	−0.0046 (8)	0.0100 (9)	−0.0022 (9)
C10	0.0297 (10)	0.0402 (11)	0.0487 (12)	−0.0026 (9)	0.0086 (9)	−0.0020 (9)
C11	0.0302 (10)	0.0394 (12)	0.0588 (14)	0.0002 (9)	0.0078 (9)	−0.0004 (10)
C12	0.0380 (11)	0.0377 (12)	0.0670 (15)	−0.0012 (10)	0.0059 (11)	−0.0099 (11)
C13	0.0401 (12)	0.0449 (13)	0.0553 (14)	−0.0003 (10)	−0.0012 (10)	−0.0090 (11)
C14	0.0341 (11)	0.0395 (12)	0.0504 (12)	−0.0021 (9)	0.0069 (9)	−0.0009 (10)
C15	0.0532 (15)	0.0548 (16)	0.0521 (14)	0.0084 (12)	0.0012 (12)	−0.0060 (12)
C16	0.0565 (17)	0.0456 (16)	0.099 (2)	0.0041 (13)	−0.0105 (16)	−0.0240 (15)
C17	0.0492 (14)	0.0453 (14)	0.0559 (14)	0.0025 (11)	0.0029 (11)	0.0033 (11)
N18	0.0482 (12)	0.0350 (10)	0.0664 (13)	−0.0045 (8)	0.0179 (10)	−0.0061 (9)
N19	0.0445 (10)	0.0349 (10)	0.0508 (11)	−0.0027 (8)	0.0143 (9)	−0.0027 (8)
C20	0.0478 (13)	0.0398 (12)	0.0492 (13)	0.0070 (10)	0.0133 (10)	−0.0018 (10)
C21	0.0735 (19)	0.0498 (15)	0.0608 (16)	−0.0014 (14)	0.0312 (14)	−0.0021 (12)
C22	0.0665 (18)	0.0467 (15)	0.0784 (19)	−0.0042 (13)	0.0334 (16)	0.0013 (13)
C23	0.0403 (12)	0.0496 (13)	0.0459 (12)	0.0026 (10)	0.0119 (10)	−0.0106 (10)
C24	0.0461 (13)	0.0439 (13)	0.0545 (13)	−0.0025 (10)	0.0183 (11)	−0.0111 (11)
C25	0.0598 (17)	0.0511 (15)	0.0738 (18)	−0.0111 (13)	0.0293 (15)	−0.0183 (13)
C26	0.0575 (17)	0.076 (2)	0.079 (2)	−0.0158 (16)	0.0241 (16)	−0.0375 (18)
C27	0.0471 (15)	0.120 (3)	0.0615 (18)	0.0032 (18)	0.0022 (14)	−0.046 (2)
C28	0.0519 (15)	0.076 (2)	0.0516 (14)	0.0118 (14)	0.0095 (12)	−0.0148 (14)
C29	0.0562 (15)	0.0448 (14)	0.0595 (15)	0.0054 (12)	0.0114 (12)	0.0014 (11)
C30	0.084 (3)	0.115 (3)	0.139 (4)	−0.047 (2)	0.043 (3)	−0.083 (3)
C31	0.078 (2)	0.119 (3)	0.0559 (17)	0.034 (2)	−0.0013 (16)	0.0053 (19)
Cl32	0.0379 (3)	0.0439 (3)	0.0893 (5)	−0.0063 (2)	0.0241 (3)	−0.0210 (3)
Cl33	0.0481 (3)	0.0464 (3)	0.0598 (4)	−0.0054 (3)	0.0097 (3)	−0.0010 (3)
Cl34	0.0443 (4)	0.0266 (3)	0.0626 (5)	0.000	0.0000 (4)	0.000
Cl35	0.0325 (4)	0.0269 (4)	0.0988 (7)	0.000	0.0023 (4)	0.000

Geometric parameters (Å, º)

Cu1—O3	1.8987 (11)	C15—H15C	0.9800
Cu1—N4	1.9460 (19)	C16—H16A	0.9800
Cu1—Cl32	2.3370 (7)	C16—H16B	0.9800
Cu1—Cl33	2.4226 (7)	C16—H16C	0.9800
Cu1—Cl35	2.4900 (7)	C17—H17A	0.9800
Cu2—O3	1.8897 (12)	C17—H17B	0.9800
Cu2—N18	1.936 (2)	C17—H17C	0.9800
Cu2—Cl32	2.4517 (7)	N18—C22	1.329 (4)
Cu2—Cl33^i	2.3944 (7)	N18—N19	1.352 (3)
Cu2—Cl34	2.4353 (6)	N19—C20	1.353 (3)
Cu1—Cu2	3.0570 (4)	N19—H19	0.8800
Cu1—Cu2^i	3.0873 (4)	C20—C21	1.381 (4)
Cu1—Cu1^i	3.1689 (5)	C20—C23	1.478 (4)
Cu2—Cu2^i	3.1000 (6)	C21—C22	1.389 (4)
N4—C8	1.337 (3)	C21—H21	0.9500
N4—N5	1.354 (3)	C22—H22	0.9500
N5—C6	1.346 (3)	C23—C24	1.404 (4)
N5—H5	0.8800	C23—C28	1.409 (4)
C6—C7	1.378 (3)	C24—C25	1.397 (4)
C6—C9	1.483 (3)	C24—C29	1.504 (4)
C7—C8	1.396 (3)	C25—C26	1.360 (5)
C7—H7	0.9500	C25—H25	0.9500
C8—H8	0.9500	C26—C27	1.390 (5)
C9—C10	1.401 (3)	C26—C30	1.512 (4)
C9—C14	1.403 (3)	C27—C28	1.405 (5)
C10—C11	1.397 (3)	C27—H27	0.9500
C10—C15	1.519 (3)	C28—C31	1.499 (5)
C11—C12	1.382 (3)	C29—H29A	0.9800
C11—H11	0.9500	C29—H29B	0.9800
C12—C13	1.384 (4)	C29—H29C	0.9800
C12—C16	1.521 (3)	C30—H30A	0.9800
C13—C14	1.391 (3)	C30—H30B	0.9800
C13—H13	0.9500	C30—H30C	0.9800
C14—C17	1.509 (3)	C31—H31A	0.9800
C15—H15A	0.9800	C31—H31B	0.9800
C15—H15B	0.9800	C31—H31C	0.9800
O3—Cu1—N4	174.93 (8)	H16A—C16—H16B	109.5
O3—Cu1—Cl32	87.19 (4)	C12—C16—H16C	109.5
N4—Cu1—Cl32	96.36 (6)	H16A—C16—H16C	109.5
O3—Cu1—Cl33	83.66 (2)	H16B—C16—H16C	109.5
N4—Cu1—Cl33	97.46 (6)	C14—C17—H17A	109.5
Cl32—Cu1—Cl33	121.70 (3)	C14—C17—H17B	109.5
O3—Cu1—Cl35	83.92 (5)	H17A—C17—H17B	109.5
N4—Cu1—Cl35	91.01 (6)	C14—C17—H17C	109.5
Cl32—Cu1—Cl35	131.74 (2)	H17A—C17—H17C	109.5
Cl33—Cu1—Cl35	104.297 (19)	H17B—C17—H17C	109.5
O3—Cu2—N18	177.07 (7)	C22—N18—N19	105.5 (2)
O3—Cu2—Cl33^i	84.63 (4)	C22—N18—Cu2	132.08 (19)
N18—Cu2—Cl33^i	94.33 (7)	N19—N18—Cu2	121.26 (16)
O3—Cu2—Cl34	85.37 (5)	N18—N19—C20	112.2 (2)
N18—Cu2—Cl34	93.31 (6)	N18—N19—H19	123.9
Cl33^i—Cu2—Cl34	131.71 (2)	C20—N19—H19	123.9
O3—Cu2—Cl32	84.12 (2)	N19—C20—C21	105.4 (2)
N18—Cu2—Cl32	98.77 (7)	N19—C20—C23	122.2 (2)
Cl33^i—Cu2—Cl32	118.77 (3)	C21—C20—C23	132.4 (2)
Cl34—Cu2—Cl32	106.94 (2)	C20—C21—C22	106.5 (2)
Cu2—O3—Cu2^i	110.21 (10)	C20—C21—H21	126.8
Cu2—O3—Cu1	107.593 (12)	C22—C21—H21	126.8
Cu2—O3—Cu1^i	109.161 (13)	N18—C22—C21	110.4 (3)
Cu1—O3—Cu1^i	113.12 (10)	N18—C22—H22	124.8
C8—N4—N5	105.14 (18)	C21—C22—H22	124.8
C8—N4—Cu1	135.35 (16)	C24—C23—C28	120.2 (3)
N5—N4—Cu1	119.49 (14)	C24—C23—C20	120.2 (2)
C6—N5—N4	112.46 (19)	C28—C23—C20	119.7 (3)
C6—N5—H5	123.8	C25—C24—C23	119.0 (3)
N4—N5—H5	123.8	C25—C24—C29	118.5 (3)
N5—C6—C7	105.9 (2)	C23—C24—C29	122.5 (2)
N5—C6—C9	120.3 (2)	C26—C25—C24	122.6 (3)
C7—C6—C9	133.8 (2)	C26—C25—H25	118.7
C6—C7—C8	106.2 (2)	C24—C25—H25	118.7
C6—C7—H7	126.9	C25—C26—C27	117.7 (3)
C8—C7—H7	126.9	C25—C26—C30	121.9 (4)
N4—C8—C7	110.3 (2)	C27—C26—C30	120.3 (4)
N4—C8—H8	124.9	C26—C27—C28	123.1 (3)
C7—C8—H8	124.9	C26—C27—H27	118.5
C10—C9—C14	120.4 (2)	C28—C27—H27	118.5
C10—C9—C6	120.0 (2)	C27—C28—C23	117.4 (3)
C14—C9—C6	119.6 (2)	C27—C28—C31	120.5 (3)
C11—C10—C9	119.0 (2)	C23—C28—C31	122.1 (3)
C11—C10—C15	119.4 (2)	C24—C29—H29A	109.5
C9—C10—C15	121.6 (2)	C24—C29—H29B	109.5
C12—C11—C10	121.3 (2)	H29A—C29—H29B	109.5
C12—C11—H11	119.4	C24—C29—H29C	109.5
C10—C11—H11	119.4	H29A—C29—H29C	109.5
C11—C12—C13	118.9 (2)	H29B—C29—H29C	109.5
C11—C12—C16	120.2 (2)	C26—C30—H30A	109.5
C13—C12—C16	120.9 (2)	C26—C30—H30B	109.5
C12—C13—C14	121.8 (2)	H30A—C30—H30B	109.5
C12—C13—H13	119.1	C26—C30—H30C	109.5
C14—C13—H13	119.1	H30A—C30—H30C	109.5
C13—C14—C9	118.6 (2)	H30B—C30—H30C	109.5
C13—C14—C17	119.8 (2)	C28—C31—H31A	109.5
C9—C14—C17	121.6 (2)	C28—C31—H31B	109.5
C10—C15—H15A	109.5	H31A—C31—H31B	109.5
C10—C15—H15B	109.5	C28—C31—H31C	109.5
H15A—C15—H15B	109.5	H31A—C31—H31C	109.5
C10—C15—H15C	109.5	H31B—C31—H31C	109.5
H15A—C15—H15C	109.5	Cu1—Cl32—Cu2	79.30 (2)
H15B—C15—H15C	109.5	Cu2^i—Cl33—Cu1	79.72 (2)
C12—C16—H16A	109.5	Cu2^i—Cl34—Cu2	79.06 (3)
C12—C16—H16B	109.5	Cu1^i—Cl35—Cu1	79.04 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···Cl35	0.88	2.56	3.079 (2)	119
N19—H19···Cl34	0.88	2.83	3.274 (2)	113