Three oxo complexes with a tetra­nuclear [Cu₄(μ₂-Cl)₆(μ₄-O)] unit

The three title compounds, namely 4-phenyl-1H-imidazolium hexa-μ₂-chloro-chloro-μ₄-oxo-tris­(4-phenyl-1H-imidazole-κN¹)­tetra­copper(II) monohydrate, (C₉H₉N₂)[Cu₄Cl₇O(C₉H₈N₂)₃]·H₂O, hexa-μ₂-chloro-μ₄-oxo-tetra­kis­(pyridine N-oxide-κO)tetra­copper(II), [Cu₄Cl₆O(C₅H₅NO)₄], and hexa-μ₂-chloro-tetra­kis(2-methyl-1H-imidazole-κN¹)-μ₄-oxo-tetra­copper(II) methanol trisolvate, [Cu₄Cl₆O(C₄H₆N₂)₄]·3CH₄O, exhibit the same Cu₄OCl₆ framework, where the O atom at the centre of an almost regular tetra­hedron bridges four copper cations at the corners. This group is in turn surrounded by a Cl₆ octa­hedron, leading to a rather globular species. This special arrangement of the Cu^II cations results in a diversity of magnetic behaviours.

S1. Comment

Polynuclear Cu^II complexes with various bridges between the metal centres have attracted much attention in the past decade, from both an experimental and a theoretical point of view, and a significant amount of research has been devoted to analyzing their structural and magnetic properties.

We have for some time focused our interest on a subset of these systems, namely the [Cu₄OCl₆L₄] complexes, where L denotes any Lewis ligand base. They contain both a µ₄-bridging O atom and µ₂-halogen atoms in their structures, and are usually characterized by an interesting magnetic behaviour, not always easy to model. In this context, our group has presented some years ago a detailed study of one such complex, viz. Cu₄OCl₆L₄, L = imidazole (Atria et al., 1999), where the magnetic properties exhibited by the compound were successfully modelled in a rather simple and elegant fashion.

The structural complexity of these [Cu₄OCl₆L₄] systems as well as their challenging magnetic properties promoted sustained structural work on the subject, as disclosed by a search of the Cambridge Structural Database (CSD; November 2005 version and updates; Allen, 2002) which yielded 52 hits of related structures, ranging from the pioneering works performed some forty years ago (Bertrand, 1967; Kilbourn & Dunitz, 1967) to the most recent ones (viz. Lyakhov et al., 2004; Sun et al., 2004; Skorda et al., 2005).

Following our interest in this family, we describe here the crystal and molecular structures of another three copper complexes sharing the same highly symmetric Cu₄OCl₆ framework and formulated as (Cu₄OCl₆)Cl(PhIm)₃·(HPhIm)·H₂O, (I), (Cu₄OCl₆)(PyNO)₄, (II), and (Cu₄OCl₆)(MeIm)₄·3CH₃OH, (III) (PhIm: is phenylimydazole, PyNO is pyridine N-oxide and MeIm is 2-methylimidazole. The present work should be considered as the introductory structural part of a comprehensive magneto-structural study, and it will be followed by the magnetic studies and associated modelling, to be reported elsewhere.

Figs. 1 to 3 show individual ellipsoid plots of the three compounds, while Tables 1, 3 and 4 provide selected bond distances and angles of the central cores. Tables 2 and 5 present some hydrogen-bonding interactions for (I) and (III). In all three structures, the four Cu atoms bound to O1 define an almost perfect tetrahedron with the O atom at its centre, while each chloride anion coordinates to two different Cu_i,Cu_j cations and lies at the bisector of the corresponding Cu_i—O1—Cu_j angles. The Cl₆ array defines a nearly perfect octahedron, centred at, though beyond bonding distance to, atom O1 and interpenetrating the copper tetrahedron. The major differences found in the complexes are due to the external ligands attached to copper, viz. three PhIm groups and one chloride ion in (I), four PyNO groups in (II), and four MeIm groups in (III). This situation makes (I) unique in the sense that, since the fourth ligand is an anion, the complete globular core becomes and anion itself, requiring of a charged HPhIm⁺ cation as a counter-ion to achieve charge balance. The other two cores, instead, are neutral.

Each metal centre is five-coordinate, with τ parameters (Addison et al., 1984) showing coordination geometries biased towards an irregular trigonal bipyramid (ideal τ = 1) rather than to a square pyramid (ideal τ = 0). The observed τ ranges are 0.74–0.87 for (I), 0.62–0.84 for (II) and 0.64–0.82% for (III).

In all three cases, the trigonal base is defined by three chloride ions [mean Cu—Cl values 2.41 (6), 2.41 (8), 2.42 (11) and 2.42 (4) for (I), (II), (II') and (III), respectively], the O atom occupying one of the apical positions [mean Cu—O = 1.909 (9), 1.90 (3), 1.90 (2) and 1.913 (5) Å]. The remaining one is in turn filled either by an aromatic N atom [from PhIm in (I), except for Cu4, where the site is occupied by Cl7, or from MeIm in (III)], or by an O atom [from PyNO in the case of (II)] [mean Cu—N = 1.921 (7) and1.947 (11) Å for (I) and (III); mean Cu—O = 1.910 (19) and 1.904 (16) Å for (II) and (II').

The cage structure is such that all Cu^II cations are at similar distances to each other, viz. the shortest diagonal of the six rhomboidal Cu—O—Cu—Cl loops in the (Cu₄OCl₆) cage. Intermetallic distances span the ranges 3.0658 (10)–3.1563 (10) Å, [3.0778 (15)–3.1316 (14) Å, 3.0358 (16)–3.1673 (17) Å and 3.0945 (9)–3.1436 (9) Å. These differences are among the largest reported in similar structures [the maximum being 3.061–3.197 Å for the 7-azaindole-N analogue to the compounds reported here (Poitras & Beauchamp, 1992)].

Table 6 compares the mean values of the Cu—O and Cu—Cl core bond distances in all reported cases in the CSD with those in the structures presented here. The similarity is apparent, confirming the rigidity of the [Cu₄OCl₆] nucleus.

The external ligands do not exhibit any non-standard feature worth mentioning.

The crystal structures of (I) and (III) are stabilized by different solvates/counter-ions, viz. a HPhIm⁺ and a (disordered) water molecule in (I) and three methanol molecules (one of them disordered) in (III). Owing to their different capabilities for hydrogen bonding and π contacts, they interact with neighbouring molecules in quite a diverse way, leading to different non-bonding interaction schemes. Structure (I) contains a number of medium strength N—H···X bonds (X = Cl and O) (Table 2), which organize the molecules into broad two-dimensional structures parallel to (−110). A similar state of affairs is found in compound (III), with the difference that here the strongest N—H···X bonds (Table 5) determine by themselves the three-dimensional structure. Finally, in structure (II), there are no significant intermolecular interactions.

In spite of the fact that measurement of the magnetic susceptibility as a function of temperature showed that all three compounds follow the Curie–Weiss law, they have dissimilar magnetic properties. Evaluation of these behaviours, as well as a search for adequate fitting models, is in progress.

S2. Experimental

All chemicals and reagents are commercially available and were used as received without further purification. The three copper(II) complexes were synthesized by a method previously reported (Atria et al., 1999). A methanol solution of the organic ligand (1 mmol) was added with constant stirring to a solution containing copper chloride (1 mmol) in the same solvent. The resulting solution was refluxed for 45 min. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the complex in methanol. C,H and N microanalyses were carried out with a Fison Carlo Erba EA 1108 equipment. Calc.(%)/Found(%) values are as follows:

Complex 1: C, 38.95; H, 2.82; N,10.09 / C, 38.70; H, 2.78; N, 9.89.

Complex 2; C, 27.71; H, 2.37; N,6.46 / C, 27.69, H, 2.11; N, 6.25.

Complex 3; C, 25.15; H, 4.00; N,12.34 / C, 24.99; H, 3.87; N, 12.07.

S3. Refinement

H atoms attached to C and N atoms were placed at calculated positions (N—H = 0.86 Å, C—H_aromatic = 0.93 Å and C—H_methyl = 0.96 Å) and allowed to ride. Even though located in a rather shallow electron density plateau, H atoms from the methyl groups were also included (AFIX 137 in SHELXL97; Sheldrick, 1997) because of their incidence in the refinement. The alcohol OH groups were treated by use of the AFIX 147 instruction in SHELXL97, subject to orientational restraint. H atoms bound to the disordered water molecule in (I) were not included in the model. All H atoms were assigned a U_iso(H) value of xU_eq(carrier), with x = 1.2 for aromatic H atoms, and x = 1.5 for methyl and hydroxy H atoms. In spite of the heavy atoms present, the crystals used for data collection were poorly diffracting, and only with measurement times of 20, 20 and 15 s per frame, respectively, was it possible to account for an observed/unique ratio of reflections of ca 0.5. A residual effect of this was the uncertainty with which some solvent molecules could be determined; thus, in (I), a full hydration water molecule appeared split into three partially occupied sites, and was refined with an overall isotropic displacement parameter and occupations restrained to sum to 1, and in (III), one of the three methanol solvent molecules appeared to have its O atom split over two sites, refined with occupation factors adding up to 1. In addition, a PLATON (Spek, 2003) run detected in this latter structure (void) solvent accessible regions of 35 ų, in which the electron density was hardly differentiable from background. A PLATON SQUEEZE refinement, however, would not significantly improve the refinement. The rather high R indices obtained are probably the result of poor data quality. However, the large number of parameters (518, 708 and 393, respectively) might have played also a non-negligible role [see Krebs (2000) for a detailed analysis].

Computing details

For all compounds, data collection: SMART-NT (Bruker, 2001). Cell refinement: SAINT-NT (Bruker 2000) for (I); SAINT-NT (Bruker, 2000) for (II), (III). For all compounds, data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. : A displacement ellipsoid plot of (I) (30% probability level).
	Fig. 2. : A displacement ellipsoid plot of one of the (very similar) independent moieties in (II), as representative of both (30% probability level).
	Fig. 3. : A displacement ellipsoid plot of (III) (30% probability level).

(I) 4-phenyl-1H-imidazolium hexa-µ₂-chloro-chloro-µ₄-oxo-tris(4-phenyl-1H-imidazole- κN¹)tetracopper(II) monohydrate

Crystal data

(C9H9N2)[Cu4Cl7O(C9H8N2)3]·H2O	Z = 2
Mr = 1114.03	F(000) = 1116
Triclinic, P1	Dx = 1.701 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.394 (3) Å	Cell parameters from 5240 reflections
b = 14.823 (3) Å	θ = 2.3–27.8°
c = 14.924 (3) Å	µ = 2.40 mm^−1
α = 97.707 (6)°	T = 297 K
β = 113.562 (5)°	Block, blue
γ = 112.860 (5)°	0.25 × 0.19 × 0.17 mm
V = 2175.6 (8) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	9092 independent reflections
Radiation source: fine-focus sealed tube	5466 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ϕ and ω scans	θmax = 28.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −15→14
Tmin = 0.57, Tmax = 0.66	k = −19→19
22917 measured reflections	l = −17→18

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0156P)^2] where P = (Fo^2 + 2Fc^2)/3
7542 reflections	(Δ/σ)max = 0.001
517 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. C,H and N microanalyses were carried out with a Fison Carlo Erba EA 1108 equipment.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.77808 (6)	0.90319 (4)	0.79700 (4)	0.03643 (17)
Cu2	0.98017 (6)	0.96676 (4)	0.71767 (4)	0.03664 (17)
Cu3	0.81222 (6)	0.73106 (4)	0.68913 (4)	0.03595 (17)
Cu4	0.67256 (6)	0.84118 (4)	0.55749 (4)	0.03766 (17)
Cl1	0.58992 (16)	0.90048 (13)	0.65430 (11)	0.0764 (5)
Cl2	0.85700 (13)	0.95999 (10)	0.54164 (9)	0.0464 (3)
Cl3	0.64755 (13)	0.66407 (9)	0.50742 (9)	0.0410 (3)
Cl4	0.98832 (13)	1.05698 (9)	0.86311 (10)	0.0481 (4)
Cl5	0.79907 (16)	0.76009 (10)	0.84133 (10)	0.0595 (4)
Cl6	1.04420 (12)	0.82723 (9)	0.71443 (9)	0.0393 (3)
Cl7	0.50716 (13)	0.81194 (10)	0.40215 (9)	0.0469 (3)
O1	0.8112 (3)	0.8590 (2)	0.6882 (2)	0.0251 (7)
N11	0.7364 (4)	0.9408 (3)	0.9023 (3)	0.0420 (11)
N12	1.1471 (4)	1.0781 (3)	0.7437 (3)	0.0374 (11)
N13	0.8085 (4)	0.6003 (3)	0.6925 (3)	0.0364 (11)
N21	0.7563 (4)	1.0244 (3)	1.0461 (3)	0.0417 (11)
H21	0.7880	1.0732	1.1027	0.050*
N22	1.3150 (4)	1.1707 (3)	0.7228 (3)	0.0456 (12)
H22	1.3748	1.1845	0.7037	0.055*
N23	0.7313 (4)	0.4356 (3)	0.6762 (3)	0.0486 (12)
H23	0.6761	0.3699	0.6524	0.058*
C11	0.8110 (5)	1.0258 (4)	0.9852 (4)	0.0382 (13)
H11	0.8924	1.0803	0.9995	0.046*
C12	1.2216 (6)	1.0759 (4)	0.7061 (4)	0.0518 (15)
H12	1.2122	1.0145	0.6704	0.062*
C13	0.7053 (6)	0.5058 (5)	0.6414 (4)	0.0546 (16)
H13	0.6228	0.4901	0.5866	0.066*
C21	0.6404 (6)	0.9312 (4)	1.0020 (4)	0.0437 (14)
C22	1.2981 (5)	1.2404 (4)	0.7751 (4)	0.0460 (14)
C23	0.8615 (5)	0.4852 (4)	0.7569 (4)	0.0393 (13)
C31	0.6291 (5)	0.8805 (4)	0.9124 (4)	0.0447 (14)
H31	0.5590	0.8149	0.8656	0.054*
C32	1.1961 (6)	1.1845 (4)	0.7890 (4)	0.0518 (15)
H32	1.1624	1.2121	0.8239	0.062*
C33	0.9061 (5)	0.5843 (4)	0.7638 (4)	0.0444 (14)
H33	0.9934	0.6371	0.8113	0.053*
C41	0.5540 (5)	0.9029 (4)	1.0484 (4)	0.0468 (14)
C42	1.3837 (7)	1.3558 (4)	0.8077 (4)	0.0629 (18)
C43	0.9209 (6)	0.4286 (5)	0.8126 (5)	0.0604 (17)
C51	0.5640 (6)	0.9745 (5)	1.1245 (4)	0.0532 (16)
H51	0.6267	1.0445	1.1470	0.064*
C52	1.4891 (7)	1.4013 (5)	0.7923 (5)	0.079 (2)
H52	1.5136	1.3603	0.7608	0.095*
C53	0.8643 (6)	0.3233 (5)	0.7823 (5)	0.081 (2)
H53	0.7797	0.2819	0.7236	0.097*
C61	0.4831 (8)	0.9438 (6)	1.1669 (5)	0.081 (2)
H61	0.4972	0.9928	1.2222	0.097*
C62	1.5603 (6)	1.5075 (5)	0.8228 (5)	0.081 (2)
H62	1.6331	1.5373	0.8117	0.097*
C63	0.9311 (8)	0.2780 (5)	0.8377 (7)	0.096 (3)
H63	0.8931	0.2058	0.8133	0.115*
C71	0.3838 (8)	0.8460 (8)	1.1322 (6)	0.100 (3)
H71	0.3262	0.8279	1.1596	0.120*
C72	1.5288 (8)	1.5698 (5)	0.8678 (6)	0.102 (3)
H72	1.5807	1.6419	0.8904	0.123*
C73	1.0518 (8)	0.3346 (7)	0.9278 (6)	0.096 (3)
H73	1.0918	0.3025	0.9688	0.115*
C81	0.3692 (7)	0.7719 (6)	1.0540 (6)	0.104 (3)
H81	0.3012	0.7033	1.0289	0.125*
C82	1.4201 (9)	1.5259 (5)	0.8798 (6)	0.116 (3)
H82	1.3922	1.5674	0.9062	0.140*
C83	1.1108 (8)	0.4399 (6)	0.9548 (5)	0.119 (3)
H83	1.1955	0.4818	1.0132	0.143*
C91	0.4543 (7)	0.7994 (5)	1.0136 (5)	0.081 (2)
H91	0.4455	0.7489	0.9628	0.098*
C92	1.3505 (7)	1.4193 (5)	0.8528 (5)	0.103 (3)
H92	1.2792	1.3900	0.8656	0.124*
C93	1.0447 (8)	0.4841 (5)	0.8954 (6)	0.120 (3)
H93	1.0881	0.5562	0.9135	0.144*
N14	1.0640 (6)	0.7829 (4)	0.4427 (4)	0.0848 (18)
H14	1.1342	0.8346	0.4502	0.102*
N24	0.8811 (5)	0.6936 (4)	0.4373 (3)	0.0575 (13)
H24	0.8084	0.6782	0.4401	0.069*
C14	0.9707 (7)	0.7878 (5)	0.4565 (4)	0.0607 (17)
H14A	0.9674	0.8484	0.4767	0.073*
C24	0.9175 (8)	0.6243 (6)	0.4127 (5)	0.072 (2)
C34	1.0316 (8)	0.6797 (6)	0.4139 (5)	0.089 (2)
H34	1.0813	0.6535	0.3979	0.107*
C44	0.8391 (8)	0.5102 (5)	0.3875 (4)	0.072 (2)
C54	0.7303 (7)	0.4692 (6)	0.3999 (6)	0.096 (3)
H54	0.7015	0.5120	0.4231	0.115*
C64	0.6609 (8)	0.3612 (6)	0.3774 (5)	0.100 (3)
H64	0.5874	0.3318	0.3876	0.120*
C74	0.7024 (9)	0.3001 (6)	0.3405 (7)	0.111 (3)
H74	0.6533	0.2283	0.3228	0.134*
C84	0.8063 (9)	0.3374 (6)	0.3293 (6)	0.108 (3)
H84	0.8347	0.2938	0.3073	0.129*
C94	0.8759 (7)	0.4439 (6)	0.3503 (5)	0.096 (2)
H94	0.9488	0.4708	0.3389	0.116*
O1WA	1.3172 (9)	0.9019 (6)	0.4661 (8)	0.064 (2)*	0.50
O1WB	1.3318 (11)	0.9224 (8)	0.5302 (9)	0.065 (4)*	0.34
O1WC	1.274 (3)	0.8854 (19)	0.401 (2)	0.077 (9)*	0.16

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0476 (4)	0.0379 (4)	0.0331 (4)	0.0229 (3)	0.0264 (4)	0.0111 (3)
Cu2	0.0334 (4)	0.0319 (4)	0.0401 (4)	0.0095 (3)	0.0213 (3)	0.0093 (3)
Cu3	0.0444 (4)	0.0299 (4)	0.0394 (4)	0.0218 (3)	0.0212 (4)	0.0146 (3)
Cu4	0.0363 (4)	0.0439 (4)	0.0364 (4)	0.0221 (3)	0.0180 (3)	0.0156 (3)
Cl1	0.0773 (13)	0.1352 (15)	0.0539 (10)	0.0804 (12)	0.0375 (10)	0.0303 (10)
Cl2	0.0423 (9)	0.0550 (9)	0.0415 (8)	0.0171 (7)	0.0223 (7)	0.0305 (7)
Cl3	0.0416 (9)	0.0346 (8)	0.0384 (8)	0.0203 (7)	0.0123 (7)	0.0076 (6)
Cl4	0.0565 (10)	0.0288 (8)	0.0505 (9)	0.0089 (7)	0.0340 (8)	0.0022 (6)
Cl5	0.1042 (13)	0.0453 (9)	0.0554 (9)	0.0405 (9)	0.0548 (10)	0.0282 (7)
Cl6	0.0388 (8)	0.0367 (8)	0.0461 (8)	0.0202 (6)	0.0241 (7)	0.0083 (6)
Cl7	0.0420 (9)	0.0569 (9)	0.0414 (8)	0.0258 (7)	0.0166 (7)	0.0228 (7)
O1	0.0268 (19)	0.0267 (18)	0.0219 (17)	0.0126 (15)	0.0129 (15)	0.0073 (14)
N11	0.043 (3)	0.055 (3)	0.032 (3)	0.023 (2)	0.024 (2)	0.011 (2)
N12	0.033 (3)	0.051 (3)	0.045 (3)	0.023 (2)	0.030 (2)	0.023 (2)
N13	0.050 (3)	0.015 (2)	0.038 (3)	0.018 (2)	0.013 (2)	0.011 (2)
N21	0.043 (3)	0.046 (3)	0.029 (3)	0.020 (2)	0.016 (2)	0.004 (2)
N22	0.053 (3)	0.062 (3)	0.050 (3)	0.033 (3)	0.042 (3)	0.028 (3)
N23	0.046 (3)	0.023 (3)	0.068 (3)	0.013 (2)	0.024 (3)	0.017 (2)
C11	0.027 (3)	0.037 (3)	0.037 (3)	0.009 (3)	0.013 (3)	0.002 (3)
C12	0.068 (5)	0.050 (4)	0.033 (3)	0.028 (4)	0.023 (3)	0.012 (3)
C13	0.059 (5)	0.064 (4)	0.066 (4)	0.041 (4)	0.039 (4)	0.034 (4)
C21	0.061 (4)	0.062 (4)	0.032 (3)	0.036 (3)	0.035 (3)	0.021 (3)
C22	0.043 (4)	0.052 (4)	0.041 (3)	0.016 (3)	0.024 (3)	0.021 (3)
C23	0.027 (3)	0.031 (3)	0.048 (3)	0.015 (3)	0.007 (3)	0.013 (3)
C31	0.049 (4)	0.046 (4)	0.052 (4)	0.026 (3)	0.032 (3)	0.019 (3)
C32	0.072 (5)	0.041 (4)	0.068 (4)	0.030 (3)	0.053 (4)	0.022 (3)
C33	0.037 (4)	0.034 (3)	0.057 (4)	0.022 (3)	0.017 (3)	0.008 (3)
C41	0.042 (4)	0.051 (4)	0.038 (3)	0.019 (3)	0.013 (3)	0.023 (3)
C42	0.089 (5)	0.037 (4)	0.067 (4)	0.019 (4)	0.050 (4)	0.030 (3)
C43	0.058 (5)	0.078 (5)	0.061 (4)	0.051 (4)	0.020 (4)	0.042 (4)
C51	0.079 (5)	0.085 (4)	0.045 (4)	0.056 (4)	0.054 (4)	0.034 (3)
C52	0.077 (5)	0.054 (5)	0.096 (5)	0.009 (4)	0.055 (5)	0.024 (4)
C53	0.038 (4)	0.056 (4)	0.162 (7)	0.032 (4)	0.042 (4)	0.069 (5)
C61	0.093 (7)	0.141 (8)	0.068 (5)	0.088 (6)	0.056 (5)	0.053 (5)
C62	0.066 (5)	0.065 (5)	0.101 (6)	0.007 (4)	0.058 (5)	0.027 (4)
C63	0.090 (6)	0.075 (5)	0.183 (9)	0.069 (5)	0.083 (7)	0.079 (6)
C71	0.069 (6)	0.202 (11)	0.100 (7)	0.090 (7)	0.062 (6)	0.107 (8)
C72	0.110 (7)	0.055 (5)	0.156 (8)	0.022 (5)	0.094 (7)	0.042 (5)
C73	0.092 (7)	0.136 (8)	0.124 (7)	0.086 (7)	0.062 (6)	0.100 (7)
C81	0.078 (6)	0.095 (6)	0.133 (8)	0.017 (5)	0.070 (6)	0.039 (6)
C82	0.137 (8)	0.045 (5)	0.154 (8)	0.030 (5)	0.082 (7)	0.010 (5)
C83	0.113 (7)	0.094 (6)	0.087 (6)	0.067 (6)	−0.017 (5)	0.017 (5)
C91	0.083 (6)	0.064 (5)	0.107 (6)	0.022 (4)	0.070 (5)	0.025 (4)
C92	0.125 (7)	0.041 (5)	0.148 (7)	0.028 (5)	0.090 (6)	0.013 (5)
C93	0.103 (7)	0.068 (5)	0.125 (7)	0.055 (5)	−0.010 (6)	0.025 (5)
N14	0.083 (5)	0.075 (5)	0.102 (5)	0.031 (4)	0.060 (4)	0.025 (4)
N24	0.060 (4)	0.054 (3)	0.057 (3)	0.024 (3)	0.034 (3)	0.014 (3)
C14	0.059 (5)	0.056 (5)	0.052 (4)	0.021 (4)	0.023 (4)	0.013 (3)
C24	0.086 (6)	0.091 (6)	0.058 (4)	0.064 (5)	0.036 (4)	0.011 (4)
C34	0.089 (6)	0.094 (6)	0.116 (6)	0.056 (5)	0.073 (6)	0.016 (5)
C44	0.090 (6)	0.067 (5)	0.052 (4)	0.043 (5)	0.033 (4)	−0.007 (3)
C54	0.085 (6)	0.078 (6)	0.146 (7)	0.053 (5)	0.069 (6)	0.018 (5)
C64	0.115 (7)	0.085 (6)	0.121 (7)	0.040 (6)	0.084 (6)	0.032 (5)
C74	0.098 (8)	0.077 (6)	0.151 (8)	0.049 (6)	0.057 (7)	0.011 (5)
C84	0.093 (7)	0.065 (6)	0.140 (7)	0.053 (5)	0.034 (6)	−0.006 (5)
C94	0.092 (6)	0.096 (6)	0.122 (7)	0.043 (5)	0.079 (6)	0.015 (5)

Geometric parameters (Å, º)

Cu1—O1	1.921 (3)	C41—C91	1.397 (7)
Cu2—O1	1.899 (3)	C42—C52	1.345 (7)
Cu3—O1	1.903 (3)	C42—C92	1.364 (7)
Cu4—O1	1.913 (3)	C43—C93	1.338 (8)
Cu1—Cu2	3.0658 (10)	C43—C53	1.356 (7)
Cu1—Cu3	3.0923 (9)	C51—C61	1.357 (7)
Cu1—Cu4	3.1272 (10)	C51—H51	0.9300
Cu2—Cu3	3.1563 (10)	C52—C62	1.368 (7)
Cu2—Cu4	3.1179 (11)	C52—H52	0.9300
Cu3—Cu4	3.1394 (9)	C53—C63	1.361 (7)
Cu1—N11	1.920 (4)	C53—H53	0.9300
Cu2—N12	1.921 (4)	C61—C71	1.337 (9)
Cu3—N13	1.929 (3)	C61—H61	0.9300
Cu1—Cl5	2.3816 (14)	C62—C72	1.334 (7)
Cu1—Cl4	2.3846 (15)	C62—H62	0.9300
Cu1—Cl1	2.4310 (16)	C63—C73	1.365 (9)
Cu2—Cl4	2.3347 (13)	C63—H63	0.9300
Cu2—Cl2	2.4179 (14)	C71—C81	1.390 (9)
Cu2—Cl6	2.4878 (13)	C71—H71	0.9300
Cu3—Cl5	2.3366 (14)	C72—C82	1.346 (9)
Cu3—Cl3	2.4049 (14)	C72—H72	0.9300
Cu3—Cl6	2.4988 (15)	C73—C83	1.357 (8)
Cu4—Cl7	2.2373 (14)	C73—H73	0.9300
Cu4—Cl1	2.3347 (14)	C81—C91	1.372 (8)
Cu4—Cl2	2.4081 (14)	C81—H81	0.9300
Cu4—Cl3	2.4906 (13)	C82—C92	1.376 (8)
N11—C11	1.316 (5)	C82—H82	0.9300
N11—C31	1.365 (6)	C83—C93	1.370 (7)
N12—C12	1.265 (6)	C83—H83	0.9300
N12—C32	1.397 (5)	C91—H91	0.9300
N13—C13	1.313 (6)	C92—H92	0.9300
N13—C33	1.384 (5)	C93—H93	0.9300
N21—C11	1.332 (5)	N14—C14	1.279 (6)
N21—C21	1.366 (6)	N14—C34	1.376 (7)
N21—H21	0.8600	N14—H14	0.8600
N22—C12	1.338 (6)	N24—C14	1.304 (6)
N22—C22	1.343 (5)	N24—C24	1.336 (6)
N22—H22	0.8600	N24—H24	0.8600
N23—C13	1.314 (5)	C14—H14A	0.9300
N23—C23	1.371 (6)	C24—C34	1.323 (8)
N23—H23	0.8600	C24—C44	1.484 (8)
C11—H11	0.9300	C34—H34	0.9300
C12—H12	0.9300	C44—C54	1.347 (8)
C13—H13	0.9300	C44—C94	1.374 (7)
C21—C31	1.367 (6)	C54—C64	1.404 (8)
C21—C41	1.457 (6)	C54—H54	0.9300
C22—C32	1.330 (6)	C64—C74	1.356 (8)
C22—C42	1.497 (7)	C64—H64	0.9300
C23—C33	1.325 (5)	C74—C84	1.280 (9)
C23—C43	1.455 (6)	C74—H74	0.9300
C31—H31	0.9300	C84—C94	1.387 (8)
C32—H32	0.9300	C84—H84	0.9300
C33—H33	0.9300	C94—H94	0.9300
C41—C51	1.376 (6)
N11—Cu1—O1	177.06 (16)	C22—C32—H32	124.9
N11—Cu1—Cl5	94.89 (12)	N12—C32—H32	124.9
O1—Cu1—Cl5	83.92 (8)	C23—C33—N13	112.5 (5)
N11—Cu1—Cl4	97.77 (14)	C23—C33—H33	123.8
O1—Cu1—Cl4	85.17 (9)	N13—C33—H33	123.8
Cl5—Cu1—Cl4	113.91 (6)	C51—C41—C91	117.7 (5)
N11—Cu1—Cl1	95.82 (13)	C51—C41—C21	122.8 (5)
O1—Cu1—Cl1	82.87 (9)	C91—C41—C21	119.5 (5)
Cl5—Cu1—Cl1	128.60 (6)	C52—C42—C92	117.5 (6)
Cl4—Cu1—Cl1	114.12 (6)	C52—C42—C22	124.2 (6)
O1—Cu2—N12	177.61 (14)	C92—C42—C22	118.2 (6)
O1—Cu2—Cl4	87.07 (8)	C93—C43—C53	117.3 (5)
N12—Cu2—Cl4	93.09 (13)	C93—C43—C23	117.7 (6)
O1—Cu2—Cl2	84.42 (9)	C53—C43—C23	124.8 (6)
N12—Cu2—Cl2	93.56 (12)	C61—C51—C41	120.6 (6)
Cl4—Cu2—Cl2	125.31 (5)	C61—C51—H51	119.7
O1—Cu2—Cl6	84.65 (8)	C41—C51—H51	119.7
N12—Cu2—Cl6	97.24 (12)	C42—C52—C62	120.4 (6)
Cl4—Cu2—Cl6	123.41 (5)	C42—C52—H52	119.8
Cl2—Cu2—Cl6	109.40 (5)	C62—C52—H52	119.8
O1—Cu3—N13	177.67 (14)	C43—C53—C63	120.1 (7)
O1—Cu3—Cl5	85.58 (8)	C43—C53—H53	119.9
N13—Cu3—Cl5	92.48 (11)	C63—C53—H53	119.9
O1—Cu3—Cl3	85.73 (9)	C71—C61—C51	122.6 (7)
N13—Cu3—Cl3	94.69 (12)	C71—C61—H61	118.7
Cl5—Cu3—Cl3	133.12 (6)	C51—C61—H61	118.7
O1—Cu3—Cl6	84.27 (9)	C72—C62—C52	122.2 (7)
N13—Cu3—Cl6	97.72 (13)	C72—C62—H62	118.9
Cl5—Cu3—Cl6	114.59 (5)	C52—C62—H62	118.9
Cl3—Cu3—Cl6	110.20 (5)	C53—C63—C73	122.4 (7)
O1—Cu4—Cl7	177.16 (9)	C53—C63—H63	118.8
O1—Cu4—Cl1	85.71 (9)	C73—C63—H63	118.8
Cl7—Cu4—Cl1	95.61 (6)	C61—C71—C81	118.2 (7)
O1—Cu4—Cl2	84.42 (9)	C61—C71—H71	120.9
Cl7—Cu4—Cl2	96.98 (5)	C81—C71—H71	120.9
Cl1—Cu4—Cl2	121.59 (6)	C62—C72—C82	118.5 (7)
O1—Cu4—Cl3	83.13 (8)	C62—C72—H72	120.8
Cl7—Cu4—Cl3	94.08 (5)	C82—C72—H72	120.8
Cl1—Cu4—Cl3	127.48 (6)	C83—C73—C63	116.9 (6)
Cl2—Cu4—Cl3	108.12 (5)	C83—C73—H73	121.5
Cu4—Cl1—Cu1	81.99 (5)	C63—C73—H73	121.5
Cu4—Cl2—Cu2	80.49 (4)	C91—C81—C71	120.5 (7)
Cu3—Cl3—Cu4	79.76 (4)	C91—C81—H81	119.8
Cu2—Cl4—Cu1	81.02 (4)	C71—C81—H81	119.8
Cu3—Cl5—Cu1	81.89 (4)	C72—C82—C92	119.8 (7)
Cu2—Cl6—Cu3	78.54 (4)	C72—C82—H82	120.1
Cu2—O1—Cu3	112.23 (13)	C92—C82—H82	120.1
Cu2—O1—Cu4	109.75 (13)	C73—C83—C93	119.6 (7)
Cu3—O1—Cu4	110.75 (13)	C73—C83—H83	120.2
Cu2—O1—Cu1	106.73 (13)	C93—C83—H83	120.2
Cu3—O1—Cu1	107.94 (12)	C81—C91—C41	120.3 (6)
Cu4—O1—Cu1	109.32 (13)	C81—C91—H91	119.9
C11—N11—C31	105.3 (4)	C41—C91—H91	119.9
C11—N11—Cu1	127.4 (4)	C42—C92—C82	121.5 (7)
C31—N11—Cu1	127.0 (4)	C42—C92—H92	119.3
C12—N12—C32	103.7 (4)	C82—C92—H92	119.3
C12—N12—Cu2	128.7 (4)	C43—C93—C83	123.2 (7)
C32—N12—Cu2	126.1 (3)	C43—C93—H93	118.4
C13—N13—C33	102.6 (4)	C83—C93—H93	118.4
C13—N13—Cu3	128.4 (4)	C14—N14—C34	107.6 (6)
C33—N13—Cu3	127.9 (4)	C14—N14—H14	126.2
C11—N21—C21	107.2 (4)	C34—N14—H14	126.2
C11—N21—H21	126.4	C14—N24—C24	110.9 (6)
C21—N21—H21	126.4	C14—N24—H24	124.5
C12—N22—C22	107.2 (5)	C24—N24—H24	124.5
C12—N22—H22	126.4	N14—C14—N24	108.4 (6)
C22—N22—H22	126.4	N14—C14—H14A	125.8
C13—N23—C23	108.4 (4)	N24—C14—H14A	125.8
C13—N23—H23	125.8	C34—C24—N24	104.9 (7)
C23—N23—H23	125.8	C34—C24—C44	130.1 (7)
N11—C11—N21	112.1 (4)	N24—C24—C44	125.0 (7)
N11—C11—H11	123.9	C24—C34—N14	108.1 (6)
N21—C11—H11	123.9	C24—C34—H34	125.9
N12—C12—N22	113.3 (5)	N14—C34—H34	125.9
N12—C12—H12	123.4	C54—C44—C94	118.4 (7)
N22—C12—H12	123.4	C54—C44—C24	121.1 (6)
N13—C13—N23	112.6 (5)	C94—C44—C24	120.5 (7)
N13—C13—H13	123.7	C44—C54—C64	119.2 (6)
N23—C13—H13	123.7	C44—C54—H54	120.4
N21—C21—C31	105.8 (4)	C64—C54—H54	120.4
N21—C21—C41	122.2 (5)	C74—C64—C54	119.3 (7)
C31—C21—C41	132.1 (5)	C74—C64—H64	120.4
C32—C22—N22	105.6 (5)	C54—C64—H64	120.4
C32—C22—C42	131.2 (5)	C84—C74—C64	122.6 (8)
N22—C22—C42	123.2 (5)	C84—C74—H74	118.7
C33—C23—N23	103.9 (4)	C64—C74—H74	118.7
C33—C23—C43	134.3 (5)	C74—C84—C94	119.2 (7)
N23—C23—C43	121.8 (5)	C74—C84—H84	120.4
N11—C31—C21	109.6 (5)	C94—C84—H84	120.4
N11—C31—H31	125.2	C44—C94—C84	121.3 (7)
C21—C31—H31	125.2	C44—C94—H94	119.4
C22—C32—N12	110.2 (4)	C84—C94—H94	119.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···Cl6^i	0.86	2.44	3.213 (4)	150
N22—H22···Cl7^ii	0.86	2.54	3.373 (4)	164
N23—H23···Cl7^iii	0.86	2.50	3.351 (4)	169
N14—H14···O1WA	0.86	1.99	2.782 (10)	154
N14—H14···O1WB	0.86	1.97	2.734 (13)	147
N14—H14···O1WC	0.86	2.06	2.82 (3)	146
N24—H24···Cl3	0.86	2.52	3.351 (5)	162

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.

(II) hexa-µ₂-chloro-chloro-µ₄-oxo-tetrakis(pyridine N-oxide- κO)tetracopper(II) 0.2-hydrate

Crystal data

[Cu4Cl6O(C5H5NO)4]·0.2H2O	Z = 4
Mr = 863.30	F(000) = 1704
Triclinic, P1	Dx = 1.908 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.638 (3) Å	Cell parameters from 4677 reflections
b = 16.237 (4) Å	θ = 2.2–25.0°
c = 17.139 (4) Å	µ = 3.36 mm^−1
α = 106.249 (5)°	T = 297 K
β = 102.401 (6)°	Block, blue
γ = 94.255 (5)°	0.15 × 0.05 × 0.03 mm
V = 3005.7 (13) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	10510 independent reflections
Radiation source: fine-focus sealed tube	5765 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ϕ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −13→13
Tmin = 0.64, Tmax = 0.91	k = −19→18
24860 measured reflections	l = −20→20

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0142P)^2 + 7.7343P] where P = (Fo^2 + 2Fc^2)/3
10510 reflections	(Δ/σ)max = 0.001
703 parameters	Δρmax = 0.85 e Å^−3
619 restraints	Δρmin = −0.61 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.37270 (8)	0.84751 (6)	0.73746 (6)	0.0484 (3)
Cu2	0.63193 (8)	0.81493 (6)	0.78544 (6)	0.0490 (3)
Cu3	0.42643 (7)	0.67239 (6)	0.76692 (6)	0.0450 (3)
Cu4	0.47611 (8)	0.71397 (6)	0.60968 (5)	0.0494 (3)
Cl1	0.32708 (17)	0.81897 (13)	0.59102 (12)	0.0552 (6)
Cl2	0.68179 (18)	0.76224 (16)	0.65196 (13)	0.0740 (7)
Cl3	0.36771 (17)	0.58603 (12)	0.61073 (12)	0.0540 (5)
Cl4	0.54685 (18)	0.93899 (13)	0.82990 (14)	0.0744 (7)
Cl5	0.26911 (19)	0.74902 (14)	0.79287 (15)	0.0729 (7)
Cl6	0.62450 (17)	0.69134 (14)	0.83991 (14)	0.0624 (6)
O1	0.4760 (3)	0.7604 (3)	0.7215 (3)	0.0318 (9)
O11	0.2809 (5)	0.9419 (3)	0.7640 (3)	0.0634 (16)
O12	0.7926 (4)	0.8637 (3)	0.8460 (3)	0.0600 (15)
O13	0.3713 (4)	0.5844 (3)	0.8099 (3)	0.0522 (13)
O14	0.4912 (4)	0.6756 (3)	0.4981 (3)	0.0595 (14)
N11	0.1762 (7)	0.9340 (5)	0.7170 (5)	0.069 (2)
N12	0.8080 (5)	0.9344 (4)	0.9100 (4)	0.0467 (17)
N13	0.4355 (5)	0.5170 (4)	0.8067 (4)	0.0478 (16)
N14	0.4035 (5)	0.6238 (4)	0.4362 (4)	0.0420 (15)
C11	0.0831 (9)	0.8896 (7)	0.7211 (7)	0.094 (3)
H11	0.0904	0.8577	0.7588	0.113*
C12	0.7706 (6)	0.9305 (5)	0.9798 (5)	0.050 (2)
H12	0.7399	0.8776	0.9835	0.061*
C13	0.5223 (7)	0.5177 (5)	0.8722 (5)	0.058 (2)
H13	0.5419	0.5651	0.9205	0.069*
C14	0.3084 (7)	0.6573 (5)	0.4085 (5)	0.060 (2)
H14	0.3050	0.7154	0.4345	0.072*
C21	−0.0274 (9)	0.8878 (7)	0.6713 (8)	0.111 (4)
H21	−0.0939	0.8550	0.6749	0.133*
C22	0.7788 (7)	1.0057 (6)	1.0445 (4)	0.066 (3)
H22	0.7445	1.0046	1.0886	0.079*
C23	0.5818 (8)	0.4478 (6)	0.8671 (6)	0.075 (3)
H23	0.6401	0.4451	0.9125	0.090*
C24	0.2146 (7)	0.6109 (6)	0.3437 (5)	0.069 (3)
H24	0.1502	0.6362	0.3235	0.083*
C31	−0.0374 (10)	0.9370 (9)	0.6144 (8)	0.120 (4)
H31	−0.1109	0.9381	0.5803	0.144*
C32	0.8373 (8)	1.0814 (6)	1.0439 (5)	0.073 (3)
H32	0.8462	1.1324	1.0876	0.088*
C33	0.5543 (10)	0.3840 (7)	0.7956 (7)	0.096 (3)
H33	0.6000	0.3390	0.7904	0.115*
C34	0.2220 (8)	0.5249 (7)	0.3105 (5)	0.076 (3)
H34	0.1575	0.4892	0.2702	0.092*
C41	0.0619 (11)	0.9821 (8)	0.6107 (7)	0.127 (4)
H41	0.0580	1.0137	0.5728	0.153*
C42	0.8811 (7)	1.0786 (6)	0.9772 (5)	0.065 (2)
H42	0.9238	1.1288	0.9761	0.079*
C43	0.4677 (9)	0.3800 (5)	0.7320 (5)	0.067 (3)
H43	0.4466	0.3320	0.6843	0.081*
C44	0.3216 (8)	0.4905 (6)	0.3352 (6)	0.084 (3)
H44	0.3326	0.4351	0.3063	0.101*
C51	0.1754 (8)	0.9815 (7)	0.6662 (5)	0.083 (3)
H51	0.2448	1.0136	0.6657	0.100*
C52	0.8660 (6)	1.0066 (6)	0.9119 (5)	0.057 (2)
H52	0.8979	1.0085	0.8670	0.069*
C53	0.4090 (7)	0.4512 (6)	0.7398 (5)	0.059 (2)
H53	0.3480	0.4520	0.6951	0.071*
C54	0.4058 (7)	0.5422 (5)	0.4057 (5)	0.047 (2)
H54	0.4658	0.5170	0.4318	0.057*
Cu1'	0.77732 (8)	0.77483 (7)	0.16179 (6)	0.0565 (3)
Cu2'	0.90001 (8)	0.61293 (7)	0.15525 (6)	0.0530 (3)
Cu3'	1.04378 (9)	0.80233 (8)	0.23597 (7)	0.0814 (4)
Cu4'	0.87531 (8)	0.72920 (7)	0.32565 (6)	0.0531 (3)
Cl1'	0.71490 (18)	0.80582 (14)	0.29258 (13)	0.0631 (6)
Cl2'	0.90027 (17)	0.58335 (13)	0.29260 (12)	0.0551 (5)
Cl3'	1.08343 (18)	0.82214 (14)	0.37812 (12)	0.0630 (6)
Cl4'	0.71090 (17)	0.62569 (14)	0.07852 (13)	0.0629 (6)
Cl5'	0.9296 (2)	0.86490 (18)	0.14377 (16)	0.0972 (9)
Cl6'	1.09750 (18)	0.65445 (17)	0.15285 (14)	0.0765 (7)
O1'	0.9017 (3)	0.7272 (3)	0.2213 (3)	0.0396 (10)
O11'	0.6695 (5)	0.8308 (4)	0.1018 (3)	0.0687 (16)
O12'	0.8777 (4)	0.4967 (4)	0.0828 (3)	0.0687 (16)
O13'	1.1754 (6)	0.8839 (5)	0.2399 (4)	0.107 (2)
O14'	0.8427 (5)	0.7390 (4)	0.4335 (3)	0.0648 (15)
N11'	0.5524 (7)	0.8032 (5)	0.0853 (5)	0.0669 (19)
N12'	0.9461 (6)	0.4377 (4)	0.1012 (4)	0.0523 (17)
N13'	1.2760 (6)	0.9049 (6)	0.2979 (5)	0.076 (2)
N14'	0.8974 (5)	0.6912 (4)	0.4809 (3)	0.0446 (15)
C11'	0.4961 (8)	0.7364 (6)	0.0206 (5)	0.076 (3)
H11'	0.5396	0.7051	−0.0140	0.091*
C12'	0.9174 (6)	0.3929 (5)	0.1502 (5)	0.051 (2)
H12'	0.8523	0.4032	0.1731	0.061*
C13'	1.3316 (9)	0.9924 (7)	0.3294 (6)	0.083 (3)
H13'	1.2983	1.0386	0.3163	0.100*
C14'	0.8249 (8)	0.6317 (6)	0.4926 (6)	0.084 (3)
H14'	0.7435	0.6206	0.4686	0.101*
C21'	0.3772 (8)	0.7121 (7)	0.0028 (6)	0.087 (3)
H21'	0.3410	0.6658	−0.0445	0.105*
C22'	0.9857 (8)	0.3312 (6)	0.1663 (5)	0.067 (2)
H22'	0.9684	0.3022	0.2031	0.081*
C23'	1.4460 (8)	0.9996 (7)	0.3840 (6)	0.091 (3)
H23'	1.4848	1.0558	0.4117	0.109*
C24'	0.8827 (8)	0.5872 (6)	0.5445 (5)	0.080 (3)
H24'	0.8367	0.5474	0.5592	0.096*
C31'	0.3107 (8)	0.7530 (7)	0.0517 (6)	0.083 (3)
H31'	0.2295	0.7364	0.0423	0.100*
C32'	1.0788 (8)	0.3106 (6)	0.1299 (6)	0.079 (3)
H32'	1.1191	0.2648	0.1370	0.095*
C33'	1.5009 (11)	0.9402 (8)	0.3993 (8)	0.110 (4)
H33'	1.5790	0.9519	0.4313	0.132*
C34'	1.0026 (9)	0.5989 (6)	0.5749 (5)	0.072 (3)
H34'	1.0376	0.5635	0.6046	0.087*
C41'	0.3743 (10)	0.8221 (7)	0.1173 (6)	0.097 (3)
H41'	0.3316	0.8525	0.1532	0.116*
C42'	1.1092 (7)	0.3598 (6)	0.0831 (5)	0.064 (2)
H42'	1.1741	0.3495	0.0600	0.077*
C43'	1.4397 (9)	0.8548 (8)	0.3664 (7)	0.111 (4)
H43'	1.4748	0.8100	0.3813	0.133*
C44'	1.0669 (8)	0.6588 (7)	0.5624 (6)	0.079 (3)
H44'	1.1483	0.6710	0.5865	0.095*
C51'	0.4932 (9)	0.8515 (7)	0.1359 (6)	0.086 (3)
H51'	0.5299	0.9008	0.1799	0.104*
C52'	1.0448 (7)	0.4257 (6)	0.0691 (5)	0.074 (3)
H52'	1.0679	0.4606	0.0388	0.088*
C53'	1.3240 (9)	0.8364 (8)	0.3100 (6)	0.091 (3)
H53'	1.2850	0.7801	0.2837	0.109*
C54'	1.0134 (7)	0.7039 (5)	0.5135 (5)	0.062 (2)
H54'	1.0602	0.7458	0.5021	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0473 (6)	0.0445 (6)	0.0492 (6)	0.0129 (5)	0.0102 (5)	0.0075 (5)
Cu2	0.0460 (6)	0.0427 (6)	0.0489 (6)	0.0028 (5)	0.0024 (5)	0.0070 (5)
Cu3	0.0392 (5)	0.0388 (6)	0.0556 (6)	0.0064 (4)	0.0114 (5)	0.0121 (5)
Cu4	0.0438 (6)	0.0578 (7)	0.0375 (6)	−0.0002 (5)	0.0064 (4)	0.0048 (5)
Cl1	0.0586 (13)	0.0489 (14)	0.0470 (12)	0.0094 (10)	0.0008 (10)	0.0055 (10)
Cl2	0.0519 (13)	0.106 (2)	0.0487 (13)	−0.0107 (13)	0.0143 (10)	0.0027 (13)
Cl3	0.0526 (12)	0.0407 (12)	0.0581 (13)	−0.0026 (10)	0.0026 (10)	0.0088 (10)
Cl4	0.0640 (14)	0.0489 (14)	0.0795 (16)	0.0228 (11)	−0.0178 (12)	−0.0063 (12)
Cl5	0.0690 (14)	0.0704 (16)	0.1076 (19)	0.0326 (12)	0.0534 (14)	0.0419 (15)
Cl6	0.0463 (12)	0.0649 (15)	0.0834 (16)	0.0043 (10)	0.0083 (11)	0.0410 (13)
O1	0.034 (2)	0.025 (2)	0.040 (2)	0.0040 (17)	0.0114 (18)	0.0138 (19)
O11	0.069 (3)	0.053 (3)	0.052 (3)	0.039 (3)	−0.015 (3)	0.005 (3)
O12	0.039 (3)	0.057 (4)	0.053 (3)	0.008 (2)	−0.013 (2)	−0.013 (3)
O13	0.054 (3)	0.051 (3)	0.072 (4)	0.017 (3)	0.043 (3)	0.028 (3)
O14	0.058 (3)	0.069 (4)	0.041 (3)	−0.010 (3)	0.013 (2)	0.004 (3)
N11	0.077 (5)	0.056 (5)	0.072 (5)	0.004 (4)	0.004 (4)	0.026 (4)
N12	0.027 (3)	0.053 (4)	0.037 (4)	−0.004 (3)	0.006 (3)	−0.018 (3)
N13	0.032 (3)	0.047 (4)	0.059 (4)	−0.003 (3)	0.020 (3)	0.003 (3)
N14	0.053 (4)	0.040 (4)	0.036 (4)	−0.011 (3)	0.008 (3)	0.023 (3)
C11	0.064 (5)	0.088 (8)	0.127 (9)	0.020 (5)	0.011 (6)	0.034 (6)
C12	0.027 (4)	0.058 (5)	0.058 (5)	0.008 (4)	0.008 (4)	0.007 (4)
C13	0.054 (5)	0.049 (5)	0.056 (5)	−0.019 (4)	−0.005 (4)	0.015 (4)
C14	0.086 (6)	0.058 (5)	0.035 (5)	0.022 (4)	−0.003 (4)	0.022 (4)
C21	0.064 (6)	0.094 (9)	0.168 (12)	0.027 (6)	0.031 (6)	0.024 (7)
C22	0.089 (7)	0.085 (6)	0.011 (4)	0.002 (5)	0.014 (4)	−0.004 (4)
C23	0.087 (7)	0.067 (7)	0.065 (6)	0.011 (5)	−0.021 (5)	0.042 (5)
C24	0.061 (5)	0.080 (6)	0.054 (6)	0.012 (5)	−0.008 (4)	0.018 (5)
C31	0.064 (6)	0.150 (12)	0.127 (10)	0.053 (7)	−0.011 (7)	0.028 (7)
C32	0.082 (7)	0.072 (6)	0.048 (5)	−0.004 (5)	0.008 (5)	0.000 (5)
C33	0.123 (9)	0.068 (7)	0.102 (8)	0.012 (6)	0.025 (6)	0.036 (6)
C34	0.062 (5)	0.091 (7)	0.059 (6)	−0.022 (5)	0.007 (5)	0.011 (5)
C41	0.114 (8)	0.165 (12)	0.120 (9)	0.042 (8)	0.009 (8)	0.081 (8)
C42	0.067 (6)	0.055 (5)	0.062 (6)	−0.007 (5)	0.010 (5)	0.006 (4)
C43	0.116 (8)	0.034 (5)	0.046 (5)	−0.011 (5)	0.034 (5)	−0.003 (4)
C44	0.068 (6)	0.061 (6)	0.094 (7)	0.009 (5)	0.032 (5)	−0.031 (5)
C51	0.079 (6)	0.110 (8)	0.066 (6)	0.040 (6)	0.004 (5)	0.039 (6)
C52	0.035 (5)	0.069 (6)	0.049 (5)	−0.016 (4)	0.002 (4)	0.000 (4)
C53	0.049 (5)	0.071 (6)	0.044 (5)	−0.009 (4)	0.013 (4)	0.002 (4)
C54	0.063 (5)	0.028 (4)	0.050 (5)	0.008 (4)	0.009 (4)	0.014 (4)
Cu1'	0.0553 (6)	0.0590 (7)	0.0567 (7)	0.0058 (5)	0.0094 (5)	0.0239 (6)
Cu2'	0.0427 (6)	0.0682 (7)	0.0452 (6)	0.0143 (5)	0.0095 (5)	0.0120 (5)
Cu3'	0.0584 (7)	0.1193 (11)	0.0602 (7)	−0.0279 (7)	0.0095 (6)	0.0315 (7)
Cu4'	0.0503 (6)	0.0695 (8)	0.0440 (6)	0.0109 (5)	0.0139 (5)	0.0218 (5)
Cl1'	0.0571 (13)	0.0727 (16)	0.0703 (15)	0.0219 (11)	0.0220 (11)	0.0306 (13)
Cl2'	0.0523 (12)	0.0587 (14)	0.0601 (13)	0.0126 (10)	0.0192 (10)	0.0220 (11)
Cl3'	0.0579 (13)	0.0730 (16)	0.0515 (13)	−0.0012 (11)	0.0064 (10)	0.0166 (12)
Cl4'	0.0472 (12)	0.0622 (15)	0.0655 (14)	0.0108 (10)	−0.0061 (10)	0.0118 (12)
Cl5'	0.0834 (17)	0.119 (2)	0.105 (2)	−0.0225 (15)	0.0115 (15)	0.0765 (18)
Cl6'	0.0519 (13)	0.120 (2)	0.0642 (15)	0.0150 (13)	0.0205 (11)	0.0338 (14)
O1'	0.029 (2)	0.058 (3)	0.030 (2)	−0.0072 (19)	0.0142 (18)	0.009 (2)
O11'	0.066 (3)	0.070 (4)	0.083 (4)	0.013 (3)	0.014 (3)	0.046 (3)
O12'	0.058 (3)	0.071 (3)	0.055 (3)	0.022 (3)	−0.012 (3)	0.000 (3)
O13'	0.081 (4)	0.150 (5)	0.083 (5)	−0.046 (4)	−0.003 (3)	0.054 (4)
O14'	0.078 (4)	0.082 (4)	0.059 (3)	0.037 (3)	0.042 (3)	0.035 (3)
N11'	0.078 (4)	0.063 (5)	0.065 (5)	0.009 (4)	0.012 (4)	0.032 (4)
N12'	0.047 (4)	0.051 (4)	0.036 (4)	0.003 (3)	−0.012 (3)	−0.004 (3)
N13'	0.043 (4)	0.107 (6)	0.074 (5)	−0.014 (4)	0.024 (4)	0.019 (5)
N14'	0.048 (4)	0.056 (4)	0.032 (4)	0.020 (3)	0.010 (3)	0.014 (3)
C11'	0.058 (5)	0.098 (8)	0.059 (6)	0.017 (5)	0.022 (5)	−0.004 (5)
C12'	0.026 (4)	0.062 (6)	0.056 (5)	−0.001 (4)	0.032 (4)	−0.010 (4)
C13'	0.088 (6)	0.095 (6)	0.069 (7)	0.012 (5)	0.038 (5)	0.014 (6)
C14'	0.050 (5)	0.114 (8)	0.093 (7)	−0.031 (5)	0.019 (5)	0.049 (6)
C21'	0.073 (6)	0.100 (8)	0.078 (7)	0.029 (5)	0.005 (5)	0.017 (5)
C22'	0.087 (7)	0.067 (6)	0.043 (5)	0.002 (5)	0.019 (5)	0.009 (5)
C23'	0.054 (6)	0.086 (7)	0.094 (8)	−0.032 (5)	0.013 (5)	−0.016 (7)
C24'	0.071 (5)	0.115 (8)	0.054 (6)	−0.031 (6)	0.014 (5)	0.036 (5)
C31'	0.039 (5)	0.116 (9)	0.096 (8)	0.036 (5)	0.007 (4)	0.036 (6)
C32'	0.074 (6)	0.097 (8)	0.081 (7)	0.030 (5)	0.033 (5)	0.032 (6)
C33'	0.098 (8)	0.090 (8)	0.129 (10)	0.030 (5)	0.047 (7)	−0.004 (7)
C34'	0.082 (6)	0.068 (7)	0.054 (6)	0.008 (5)	0.006 (5)	0.008 (5)
C41'	0.107 (7)	0.129 (9)	0.062 (7)	0.021 (7)	0.044 (6)	0.024 (5)
C42'	0.043 (5)	0.086 (7)	0.065 (6)	0.030 (5)	0.016 (4)	0.021 (5)
C43'	0.073 (7)	0.108 (7)	0.119 (9)	0.011 (6)	0.014 (6)	−0.008 (7)
C44'	0.048 (5)	0.116 (9)	0.068 (6)	0.010 (5)	−0.006 (5)	0.036 (6)
C51'	0.083 (6)	0.098 (8)	0.062 (6)	0.016 (6)	0.006 (5)	0.006 (5)
C52'	0.062 (6)	0.105 (8)	0.066 (6)	0.020 (5)	0.024 (5)	0.037 (6)
C53'	0.097 (7)	0.107 (7)	0.080 (7)	0.040 (6)	0.042 (5)	0.026 (6)
C54'	0.044 (4)	0.073 (6)	0.072 (6)	0.001 (4)	0.015 (4)	0.027 (5)

Geometric parameters (Å, º)

Cu1—O1	1.923 (4)	Cu1'—O1'	1.926 (5)
Cu2—O1	1.909 (4)	Cu2'—O1'	1.879 (5)
Cu3—O1	1.917 (4)	Cu3'—O1'	1.907 (4)
Cu4—O1	1.853 (4)	Cu4'—O1'	1.871 (4)
Cu1—Cu2	3.0778 (15)	Cu1'—Cu2'	3.0697 (15)
Cu1—Cu3	3.1085 (15)	Cu1'—Cu3'	3.0358 (16)
Cu1—Cu4	3.1316 (14)	Cu1'—Cu4'	3.1067 (15)
Cu2—Cu3	3.1014 (14)	Cu2'—Cu3'	3.1673 (17)
Cu2—Cu4	3.0820 (14)	Cu2'—Cu4'	3.0873 (14)
Cu3—Cu4	3.1117 (15)	Cu3'—Cu4'	3.0962 (15)
Cu1—O11	1.939 (5)	Cu1'—O11'	1.896 (5)
Cu2—O12	1.920 (4)	Cu2'—O12'	1.910 (5)
Cu3—O13	1.911 (5)	Cu3'—Cl3'	2.304 (2)
Cu4—O14	1.890 (5)	Cu4'—O14'	1.931 (5)
Cu1—Cl1	2.353 (2)	Cu1'—Cl5'	2.341 (2)
Cu1—Cl4	2.384 (2)	Cu1'—Cl4'	2.411 (2)
Cu1—Cl5	2.443 (2)	Cu1'—Cl1'	2.435 (2)
Cu2—Cl4	2.320 (2)	Cu2'—Cl6'	2.359 (2)
Cu2—Cl2	2.419 (2)	Cu2'—Cl4'	2.365 (2)
Cu2—Cl6	2.442 (2)	Cu2'—Cl2'	2.530 (2)
Cu3—Cl6	2.327 (2)	Cu3'—O13'	1.926 (6)
Cu3—Cl5	2.340 (2)	Cu3'—Cl5'	2.344 (3)
Cu3—Cl3	2.563 (2)	Cu3'—Cl6'	2.622 (3)
Cu4—Cl2	2.351 (2)	Cu4'—Cl2'	2.331 (2)
Cu4—Cl3	2.356 (2)	Cu4'—Cl1'	2.375 (2)
Cu4—Cl1	2.554 (2)	Cu4'—Cl3'	2.591 (2)
O11—N11	1.284 (8)	O11'—N11'	1.346 (8)
O12—N12	1.317 (6)	O12'—N12'	1.349 (7)
O13—N13	1.366 (7)	O13'—N13'	1.315 (8)
O14—N14	1.336 (7)	O14'—N14'	1.368 (7)
N11—C11	1.283 (11)	N11'—C11'	1.321 (10)
N11—C51	1.314 (10)	N11'—C51'	1.341 (10)
N12—C52	1.297 (9)	N12'—C12'	1.331 (9)
N12—C12	1.373 (9)	N12'—C52'	1.380 (10)
N13—C53	1.290 (9)	N13'—C53'	1.328 (11)
N13—C13	1.335 (9)	N13'—C13'	1.418 (11)
N14—C54	1.285 (8)	N14'—C54'	1.321 (9)
N14—C14	1.325 (9)	N14'—C14'	1.322 (9)
C11—C21	1.375 (12)	C11'—C21'	1.354 (11)
C11—H11	0.9300	C11'—H11'	0.9300
C12—C22	1.381 (9)	C12'—C22'	1.376 (10)
C12—H12	0.9300	C12'—H12'	0.9300
C13—C23	1.366 (10)	C13'—C23'	1.429 (12)
C13—H13	0.9300	C13'—H13'	0.9300
C14—C24	1.372 (10)	C14'—C24'	1.392 (12)
C14—H14	0.9300	C14'—H14'	0.9300
C21—C31	1.416 (15)	C21'—C31'	1.337 (11)
C21—H21	0.9300	C21'—H21'	0.9300
C22—C32	1.365 (11)	C22'—C32'	1.380 (11)
C22—H22	0.9300	C22'—H22'	0.9300
C23—C33	1.323 (12)	C23'—C33'	1.253 (13)
C23—H23	0.9300	C23'—H23'	0.9300
C24—C34	1.369 (11)	C24'—C34'	1.360 (11)
C24—H24	0.9300	C24'—H24'	0.9300
C31—C41	1.344 (15)	C31'—C41'	1.372 (12)
C31—H31	0.9300	C31'—H31'	0.9300
C32—C42	1.338 (11)	C32'—C42'	1.359 (11)
C32—H32	0.9300	C32'—H32'	0.9300
C33—C43	1.298 (12)	C33'—C43'	1.411 (13)
C33—H33	0.9300	C33'—H33'	0.9300
C34—C44	1.361 (11)	C34'—C44'	1.276 (11)
C34—H34	0.9300	C34'—H34'	0.9300
C41—C51	1.455 (12)	C41'—C51'	1.369 (12)
C41—H41	0.9300	C41'—H41'	0.9300
C42—C52	1.344 (10)	C42'—C52'	1.396 (11)
C42—H42	0.9300	C42'—H42'	0.9300
C43—C53	1.375 (11)	C43'—C53'	1.434 (12)
C43—H43	0.9300	C43'—H43'	0.9300
C44—C54	1.389 (10)	C44'—C54'	1.347 (11)
C44—H44	0.9300	C44'—H44'	0.9300
C51—H51	0.9300	C51'—H51'	0.9300
C52—H52	0.9300	C52'—H52'	0.9300
C53—H53	0.9300	C53'—H53'	0.9300
C54—H54	0.9300	C54'—H54'	0.9300
O1—Cu1—O11	174.1 (2)	O11'—Cu1'—O1'	173.2 (2)
O1—Cu1—Cl1	86.48 (14)	O11'—Cu1'—Cl5'	86.82 (19)
O11—Cu1—Cl1	98.17 (16)	O1'—Cu1'—Cl5'	86.34 (14)
O1—Cu1—Cl4	84.58 (13)	O11'—Cu1'—Cl4'	100.42 (18)
O11—Cu1—Cl4	89.79 (17)	O1'—Cu1'—Cl4'	83.68 (14)
Cl1—Cu1—Cl4	123.45 (9)	Cl5'—Cu1'—Cl4'	124.57 (10)
O1—Cu1—Cl5	83.81 (14)	O11'—Cu1'—Cl1'	100.24 (18)
O11—Cu1—Cl5	97.17 (19)	O1'—Cu1'—Cl1'	83.24 (13)
Cl1—Cu1—Cl5	117.44 (9)	Cl5'—Cu1'—Cl1'	121.84 (10)
Cl4—Cu1—Cl5	116.85 (9)	Cl4'—Cu1'—Cl1'	110.84 (8)
O1—Cu2—O12	176.5 (2)	O1'—Cu2'—O12'	172.9 (2)
O1—Cu2—Cl4	86.69 (14)	O1'—Cu2'—Cl6'	87.64 (14)
O12—Cu2—Cl4	96.78 (16)	O12'—Cu2'—Cl6'	98.42 (18)
O1—Cu2—Cl2	83.16 (14)	O1'—Cu2'—Cl4'	85.97 (14)
O12—Cu2—Cl2	94.19 (17)	O12'—Cu2'—Cl4'	87.15 (16)
Cl4—Cu2—Cl2	126.03 (10)	Cl6'—Cu2'—Cl4'	134.49 (9)
O1—Cu2—Cl6	82.68 (14)	O1'—Cu2'—Cl2'	81.62 (14)
O12—Cu2—Cl6	95.83 (17)	O12'—Cu2'—Cl2'	99.72 (18)
Cl4—Cu2—Cl6	125.21 (9)	Cl6'—Cu2'—Cl2'	109.00 (8)
Cl2—Cu2—Cl6	105.80 (9)	Cl4'—Cu2'—Cl2'	114.48 (8)
O13—Cu3—O1	177.9 (2)	O1'—Cu3'—O13'	172.5 (2)
O13—Cu3—Cl6	96.39 (16)	O1'—Cu3'—Cl3'	89.26 (14)
O1—Cu3—Cl6	85.70 (13)	O13'—Cu3'—Cl3'	96.5 (2)
O13—Cu3—Cl5	91.75 (16)	O1'—Cu3'—Cl5'	86.69 (15)
O1—Cu3—Cl5	86.82 (14)	O13'—Cu3'—Cl5'	85.9 (2)
Cl6—Cu3—Cl5	132.15 (9)	Cl3'—Cu3'—Cl5'	135.30 (11)
O13—Cu3—Cl3	98.35 (16)	O1'—Cu3'—Cl6'	79.74 (15)
O1—Cu3—Cl3	80.62 (14)	O13'—Cu3'—Cl6'	102.3 (2)
Cl6—Cu3—Cl3	118.76 (8)	Cl3'—Cu3'—Cl6'	112.46 (9)
Cl5—Cu3—Cl3	106.39 (8)	Cl5'—Cu3'—Cl6'	110.52 (10)
O1—Cu4—O14	173.7 (2)	O1'—Cu4'—O14'	175.8 (2)
O1—Cu4—Cl2	86.27 (14)	O1'—Cu4'—Cl2'	87.45 (15)
O14—Cu4—Cl2	88.07 (16)	O14'—Cu4'—Cl2'	96.57 (17)
O1—Cu4—Cl3	87.77 (14)	O1'—Cu4'—Cl1'	86.09 (15)
O14—Cu4—Cl3	98.02 (17)	O14'—Cu4'—Cl1'	90.10 (17)
Cl2—Cu4—Cl3	130.38 (9)	Cl2'—Cu4'—Cl1'	134.67 (8)
O1—Cu4—Cl1	82.24 (14)	O1'—Cu4'—Cl3'	81.79 (13)
O14—Cu4—Cl1	98.36 (17)	O14'—Cu4'—Cl3'	98.17 (17)
Cl2—Cu4—Cl1	120.98 (9)	Cl2'—Cu4'—Cl3'	108.46 (8)
Cl3—Cu4—Cl1	106.83 (8)	Cl1'—Cu4'—Cl3'	114.86 (8)
Cu1—Cl1—Cu4	79.20 (6)	Cu4'—Cl1'—Cu1'	80.46 (7)
Cu4—Cl2—Cu2	80.49 (7)	Cu4'—Cl2'—Cu2'	78.73 (7)
Cu4—Cl3—Cu3	78.35 (6)	Cu3'—Cl3'—Cu4'	78.22 (7)
Cu2—Cl4—Cu1	81.74 (7)	Cu2'—Cl4'—Cu1'	79.99 (7)
Cu3—Cl5—Cu1	81.03 (7)	Cu1'—Cl5'—Cu3'	80.80 (8)
Cu3—Cl6—Cu2	81.10 (7)	Cu2'—Cl6'—Cu3'	78.77 (7)
Cu4—O1—Cu2	110.0 (2)	Cu4'—O1'—Cu2'	110.8 (2)
Cu4—O1—Cu3	111.3 (2)	Cu4'—O1'—Cu3'	110.1 (2)
Cu2—O1—Cu3	108.3 (2)	Cu2'—O1'—Cu3'	113.6 (2)
Cu4—O1—Cu1	112.1 (2)	Cu4'—O1'—Cu1'	109.8 (2)
Cu2—O1—Cu1	106.9 (2)	Cu2'—O1'—Cu1'	107.6 (2)
Cu3—O1—Cu1	108.1 (2)	Cu3'—O1'—Cu1'	104.8 (2)
N11—O11—Cu1	117.9 (5)	N11'—O11'—Cu1'	118.2 (4)
N12—O12—Cu2	117.2 (4)	N12'—O12'—Cu2'	122.0 (4)
N13—O13—Cu3	116.1 (4)	N13'—O13'—Cu3'	124.7 (6)
N14—O14—Cu4	121.6 (4)	N14'—O14'—Cu4'	119.1 (4)
C11—N11—O11	125.3 (9)	C11'—N11'—C51'	121.1 (9)
C11—N11—C51	123.9 (9)	C11'—N11'—O11'	123.2 (8)
O11—N11—C51	110.7 (8)	C51'—N11'—O11'	115.6 (8)
C52—N12—O12	121.8 (7)	C12'—N12'—O12'	119.4 (7)
C52—N12—C12	118.5 (7)	C12'—N12'—C52'	121.4 (7)
O12—N12—C12	119.5 (7)	O12'—N12'—C52'	119.2 (7)
C53—N13—C13	120.3 (8)	O13'—N13'—C53'	112.9 (9)
C53—N13—O13	118.8 (7)	O13'—N13'—C13'	119.5 (9)
C13—N13—O13	120.9 (7)	C53'—N13'—C13'	126.5 (9)
C54—N14—C14	119.3 (7)	C54'—N14'—C14'	122.3 (8)
C54—N14—O14	122.3 (7)	C54'—N14'—O14'	123.0 (7)
C14—N14—O14	118.3 (7)	C14'—N14'—O14'	114.7 (7)
N11—C11—C21	121.9 (11)	N11'—C11'—C21'	122.3 (9)
N11—C11—H11	119.0	N11'—C11'—H11'	118.9
C21—C11—H11	119.0	C21'—C11'—H11'	118.9
N12—C12—C22	119.7 (8)	N12'—C12'—C22'	118.9 (7)
N12—C12—H12	120.2	N12'—C12'—H12'	120.6
C22—C12—H12	120.2	C22'—C12'—H12'	120.6
N13—C13—C23	118.9 (8)	N13'—C13'—C23'	110.6 (9)
N13—C13—H13	120.6	N13'—C13'—H13'	124.7
C23—C13—H13	120.6	C23'—C13'—H13'	124.7
N14—C14—C24	123.3 (8)	N14'—C14'—C24'	113.2 (8)
N14—C14—H14	118.3	N14'—C14'—H14'	123.4
C24—C14—H14	118.3	C24'—C14'—H14'	123.4
C11—C21—C31	118.4 (11)	C31'—C21'—C11'	121.5 (10)
C11—C21—H21	120.8	C31'—C21'—H21'	119.3
C31—C21—H21	120.8	C11'—C21'—H21'	119.3
C32—C22—C12	120.0 (8)	C12'—C22'—C32'	122.4 (9)
C32—C22—H22	120.0	C12'—C22'—H22'	118.8
C12—C22—H22	120.0	C32'—C22'—H22'	118.8
C33—C23—C13	118.0 (9)	C33'—C23'—C13'	128.4 (11)
C33—C23—H23	121.0	C33'—C23'—H23'	115.8
C13—C23—H23	121.0	C13'—C23'—H23'	115.8
C34—C24—C14	115.7 (8)	C34'—C24'—C14'	123.5 (9)
C34—C24—H24	122.1	C34'—C24'—H24'	118.2
C14—C24—H24	122.1	C14'—C24'—H24'	118.2
C41—C31—C21	118.4 (11)	C21'—C31'—C41'	113.3 (9)
C41—C31—H31	120.8	C21'—C31'—H31'	123.4
C21—C31—H31	120.8	C41'—C31'—H31'	123.4
C42—C32—C22	116.7 (9)	C42'—C32'—C22'	117.3 (9)
C42—C32—H32	121.6	C42'—C32'—H32'	121.3
C22—C32—H32	121.6	C22'—C32'—H32'	121.3
C43—C33—C23	124.3 (11)	C23'—C33'—C43'	117.5 (13)
C43—C33—H33	117.8	C23'—C33'—H33'	121.2
C23—C33—H33	117.8	C43'—C33'—H33'	121.2
C44—C34—C24	121.5 (9)	C44'—C34'—C24'	119.6 (10)
C44—C34—H34	119.2	C44'—C34'—H34'	120.2
C24—C34—H34	119.2	C24'—C34'—H34'	120.2
C31—C41—C51	119.9 (12)	C51'—C41'—C31'	127.5 (10)
C31—C41—H41	120.0	C51'—C41'—H41'	116.3
C51—C41—H41	120.0	C31'—C41'—H41'	116.3
C32—C42—C52	122.9 (9)	C32'—C42'—C52'	121.1 (8)
C32—C42—H42	118.5	C32'—C42'—H42'	119.4
C52—C42—H42	118.5	C52'—C42'—H42'	119.4
C33—C43—C53	115.8 (9)	C33'—C43'—C53'	120.7 (12)
C33—C43—H43	122.1	C33'—C43'—H43'	119.7
C53—C43—H43	122.1	C53'—C43'—H43'	119.7
C34—C44—C54	116.6 (8)	C34'—C44'—C54'	118.0 (9)
C34—C44—H44	121.7	C34'—C44'—H44'	121.0
C54—C44—H44	121.7	C54'—C44'—H44'	121.0
N11—C51—C41	117.5 (10)	N11'—C51'—C41'	114.2 (10)
N11—C51—H51	121.3	N11'—C51'—H51'	122.9
C41—C51—H51	121.3	C41'—C51'—H51'	122.9
N12—C52—C42	121.5 (8)	N12'—C52'—C42'	118.5 (8)
N12—C52—H52	119.3	N12'—C52'—H52'	120.8
C42—C52—H52	119.3	C42'—C52'—H52'	120.8
N13—C53—C43	122.5 (8)	N13'—C53'—C43'	115.7 (11)
N13—C53—H53	118.8	N13'—C53'—H53'	122.2
C43—C53—H53	118.8	C43'—C53'—H53'	122.2
N14—C54—C44	122.1 (8)	N14'—C54'—C44'	123.1 (8)
N14—C54—H54	118.9	N14'—C54'—H54'	118.5
C44—C54—H54	118.9	C44'—C54'—H54'	118.5

(III) hexa-µ₂-chloro-chlorotetrakis(2-methyl-1H-imidazole- κN¹)-µ₄-oxo-tetracopper(II) methanol tetrasolvate, [Cu₄Cl₆O(C₄H₆N₂)₄]·3CH₄O

Crystal data

[Cu4Cl6O(C4H6N2)4]·3CH4O	F(000) = 1824
Mr = 907.42	Dx = 1.694 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4230 reflections
a = 10.2454 (13) Å	θ = 2.5–26.7°
b = 17.826 (2) Å	µ = 2.85 mm^−1
c = 19.557 (2) Å	T = 297 K
β = 94.877 (2)°	Block, blue
V = 3558.9 (7) Å^3	0.23 × 0.19 × 0.05 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	7783 independent reflections
Radiation source: fine-focus sealed tube	5314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ϕ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −13→13
Tmin = 0.56, Tmax = 0.87	k = −23→23
17557 measured reflections	l = −24→25

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0443P)^2 + 0.1035P] where P = (Fo^2 + 2Fc^2)/3
6277 reflections	(Δ/σ)max = 0.026
390 parameters	Δρmax = 0.78 e Å^−3
30 restraints	Δρmin = −0.92 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.80123 (6)	0.28053 (3)	0.19659 (3)	0.04329 (18)
Cu2	0.96175 (6)	0.41386 (3)	0.26350 (3)	0.04332 (18)
Cu3	0.75126 (6)	0.33541 (3)	0.34455 (3)	0.04207 (17)
Cu4	1.01405 (6)	0.25310 (3)	0.31893 (3)	0.04303 (18)
Cl1	0.96798 (14)	0.18571 (8)	0.20874 (7)	0.0563 (4)
Cl2	1.16410 (14)	0.35293 (9)	0.30633 (10)	0.0787 (5)
Cl3	0.85745 (13)	0.22571 (7)	0.40202 (7)	0.0527 (4)
Cl4	0.89523 (16)	0.39304 (8)	0.14668 (7)	0.0618 (4)
Cl5	0.59902 (12)	0.29892 (8)	0.25119 (7)	0.0518 (3)
Cl6	0.85849 (16)	0.45132 (8)	0.36794 (8)	0.0696 (5)
O1	0.8811 (3)	0.32015 (16)	0.28096 (15)	0.0356 (7)
N11	0.7087 (4)	0.2400 (2)	0.1144 (2)	0.0481 (11)
N12	1.0334 (4)	0.5131 (2)	0.2502 (2)	0.0458 (11)
N13	0.6177 (4)	0.3505 (2)	0.4085 (2)	0.0490 (11)
N14	1.1462 (4)	0.1871 (2)	0.3654 (2)	0.0508 (11)
N21	0.5701 (5)	0.2249 (3)	0.0245 (2)	0.0677 (14)
H21	0.5108	0.2349	−0.0080	0.081*
N22	1.0450 (5)	0.6338 (3)	0.2396 (2)	0.0667 (14)
H22	1.0219	0.6799	0.2334	0.080*
N23	0.4530 (5)	0.3943 (3)	0.4584 (3)	0.0730 (15)
H23	0.3875	0.4220	0.4668	0.088*
N24	1.2449 (6)	0.0929 (3)	0.4165 (3)	0.0821 (18)
H24	1.2607	0.0479	0.4307	0.099*
C11	0.6213 (6)	0.2749 (3)	0.0711 (3)	0.0549 (15)
C12	0.9642 (6)	0.5749 (3)	0.2382 (3)	0.0539 (14)
C13	0.5248 (6)	0.4020 (3)	0.4057 (3)	0.0565 (15)
C14	1.1394 (6)	0.1146 (3)	0.3775 (3)	0.0602 (16)
C21	0.6255 (6)	0.1569 (4)	0.0364 (3)	0.0704 (18)
H21A	0.6091	0.1131	0.0112	0.084*
C22	1.1686 (7)	0.6090 (4)	0.2525 (3)	0.0730 (19)
H22A	1.2443	0.6380	0.2560	0.088*
C23	0.4999 (7)	0.3355 (4)	0.4970 (3)	0.0739 (19)
H23A	0.4675	0.3176	0.5369	0.089*
C24	1.3235 (7)	0.1530 (4)	0.4303 (4)	0.085 (2)
H24A	1.4038	0.1536	0.4564	0.102*
C31	0.7105 (6)	0.1661 (3)	0.0934 (3)	0.0599 (16)
H31	0.7619	0.1285	0.1147	0.072*
C32	1.1619 (6)	0.5343 (3)	0.2592 (3)	0.0599 (16)
H32	1.2328	0.5022	0.2685	0.072*
C33	0.6014 (6)	0.3084 (3)	0.4667 (3)	0.0612 (16)
H33	0.6530	0.2678	0.4821	0.073*
C34	1.2623 (6)	0.2112 (3)	0.3991 (3)	0.0633 (17)
H34	1.2931	0.2603	0.3998	0.076*
C41	0.5822 (6)	0.3541 (4)	0.0717 (3)	0.079 (2)
H41A	0.5433	0.3649	0.1135	0.119*
H41B	0.5199	0.3639	0.0332	0.119*
H41C	0.6579	0.3852	0.0686	0.119*
C42	0.8196 (6)	0.5787 (3)	0.2239 (3)	0.0773 (19)
H42A	0.7978	0.6154	0.1888	0.116*
H42B	0.7807	0.5928	0.2650	0.116*
H42C	0.7868	0.5306	0.2088	0.116*
C43	0.5028 (7)	0.4594 (4)	0.3511 (4)	0.088 (2)
H43A	0.5820	0.4874	0.3476	0.132*
H43B	0.4343	0.4928	0.3623	0.132*
H43C	0.4778	0.4352	0.3081	0.132*
C44	1.0318 (6)	0.0622 (3)	0.3529 (4)	0.080 (2)
H44A	0.9563	0.0716	0.3775	0.120*
H44B	1.0602	0.0114	0.3606	0.120*
H44C	1.0096	0.0699	0.3047	0.120*
O1B	1.2786 (8)	−0.0511 (3)	0.4615 (3)	0.149 (3)
H1B	1.2322	−0.0871	0.4496	0.223*
O1C	0.6708 (8)	0.1777 (4)	0.6027 (4)	0.168 (3)
H1C	0.6192	0.1654	0.6305	0.252*
C1B	1.3277 (10)	−0.0603 (5)	0.5287 (4)	0.143 (4)
H1B1	1.4088	−0.0334	0.5365	0.215*
H1B2	1.3426	−0.1126	0.5379	0.215*
H1B3	1.2660	−0.0412	0.5586	0.215*
C1C	0.7647 (9)	0.2258 (6)	0.6340 (5)	0.146 (4)
H1C1	0.7224	0.2637	0.6590	0.219*
H1C2	0.8127	0.2490	0.5996	0.219*
H1C3	0.8238	0.1977	0.6650	0.219*
C1A	0.1699 (17)	0.5334 (8)	0.4479 (9)	0.090 (4)	0.50
H1E1	0.0919	0.5034	0.4472	0.134*	0.50
H1E2	0.1991	0.5354	0.4026	0.134*	0.50
H1E3	0.1514	0.5832	0.4629	0.134*	0.50
O1A	0.2678 (9)	0.5014 (6)	0.4930 (5)	0.0829 (19)	0.50
H1A	0.2413	0.4975	0.5312	0.124*	0.50
C2A	0.1990 (18)	0.5588 (6)	0.4426 (11)	0.090 (4)	0.50
H2F1	0.2327	0.5734	0.4880	0.134*	0.50
H2F2	0.1085	0.5729	0.4353	0.134*	0.50
H2F3	0.2480	0.5834	0.4094	0.134*	0.50
O2A	0.2103 (9)	0.4815 (5)	0.4356 (5)	0.0829 (19)	0.50
H2A	0.1707	0.4682	0.3994	0.124*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0435 (4)	0.0486 (4)	0.0366 (3)	−0.0009 (3)	−0.0040 (3)	−0.0038 (3)
Cu2	0.0401 (4)	0.0428 (4)	0.0465 (4)	−0.0033 (3)	0.0007 (3)	0.0015 (3)
Cu3	0.0384 (4)	0.0487 (4)	0.0394 (3)	0.0017 (3)	0.0044 (3)	−0.0024 (3)
Cu4	0.0389 (4)	0.0450 (4)	0.0441 (4)	0.0064 (3)	−0.0030 (3)	0.0013 (3)
Cl1	0.0518 (8)	0.0600 (8)	0.0557 (8)	0.0139 (7)	−0.0039 (7)	−0.0147 (7)
Cl2	0.0398 (8)	0.0644 (10)	0.1277 (15)	−0.0067 (7)	−0.0170 (9)	0.0274 (10)
Cl3	0.0490 (8)	0.0613 (8)	0.0474 (8)	0.0082 (7)	0.0023 (7)	0.0136 (7)
Cl4	0.0806 (11)	0.0608 (9)	0.0425 (8)	−0.0173 (8)	−0.0033 (8)	0.0081 (7)
Cl5	0.0379 (7)	0.0677 (9)	0.0485 (8)	−0.0001 (6)	−0.0028 (6)	−0.0084 (7)
Cl6	0.0832 (11)	0.0622 (9)	0.0671 (10)	−0.0253 (8)	0.0289 (9)	−0.0250 (8)
O1	0.0319 (18)	0.0428 (18)	0.0320 (17)	0.0009 (14)	0.0020 (14)	−0.0005 (14)
N11	0.047 (3)	0.056 (3)	0.040 (2)	−0.001 (2)	−0.005 (2)	−0.010 (2)
N12	0.047 (3)	0.038 (2)	0.053 (3)	−0.002 (2)	0.004 (2)	0.000 (2)
N13	0.046 (3)	0.057 (3)	0.046 (3)	0.000 (2)	0.013 (2)	−0.008 (2)
N14	0.043 (3)	0.047 (3)	0.061 (3)	0.012 (2)	0.002 (2)	0.001 (2)
N21	0.060 (3)	0.097 (4)	0.045 (3)	−0.016 (3)	−0.007 (3)	−0.013 (3)
N22	0.081 (4)	0.042 (3)	0.078 (4)	−0.002 (3)	0.011 (3)	0.014 (3)
N23	0.058 (3)	0.082 (4)	0.082 (4)	0.012 (3)	0.029 (3)	−0.014 (3)
N24	0.083 (4)	0.066 (4)	0.094 (4)	0.030 (3)	−0.007 (4)	0.026 (3)
C11	0.051 (4)	0.073 (4)	0.039 (3)	−0.012 (3)	0.000 (3)	0.000 (3)
C12	0.058 (4)	0.052 (3)	0.052 (3)	0.001 (3)	0.007 (3)	0.000 (3)
C13	0.052 (4)	0.056 (4)	0.062 (4)	0.004 (3)	0.012 (3)	−0.005 (3)
C14	0.058 (4)	0.058 (4)	0.064 (4)	0.019 (3)	0.001 (3)	0.005 (3)
C21	0.068 (4)	0.085 (5)	0.058 (4)	−0.015 (4)	0.003 (4)	−0.028 (4)
C22	0.065 (5)	0.076 (5)	0.080 (5)	−0.021 (4)	0.014 (4)	−0.001 (4)
C23	0.073 (5)	0.090 (5)	0.063 (4)	−0.002 (4)	0.032 (4)	−0.002 (4)
C24	0.057 (4)	0.090 (5)	0.101 (6)	0.017 (4)	−0.029 (4)	0.000 (5)
C31	0.056 (4)	0.065 (4)	0.059 (4)	−0.005 (3)	0.007 (3)	−0.013 (3)
C32	0.053 (4)	0.054 (4)	0.073 (4)	−0.012 (3)	0.008 (3)	−0.003 (3)
C33	0.061 (4)	0.065 (4)	0.059 (4)	0.003 (3)	0.012 (3)	0.003 (3)
C34	0.051 (4)	0.068 (4)	0.068 (4)	0.009 (3)	−0.014 (3)	0.007 (3)
C41	0.080 (5)	0.079 (5)	0.074 (5)	−0.004 (4)	−0.026 (4)	0.015 (4)
C42	0.075 (5)	0.068 (4)	0.089 (5)	0.022 (4)	0.004 (4)	0.002 (4)
C43	0.065 (5)	0.091 (5)	0.108 (6)	0.027 (4)	0.015 (4)	0.014 (5)
C44	0.078 (5)	0.054 (4)	0.105 (5)	0.003 (3)	−0.007 (4)	0.016 (4)
O1B	0.227 (8)	0.072 (4)	0.140 (5)	0.033 (4)	−0.023 (6)	0.013 (4)
O1C	0.191 (8)	0.159 (6)	0.168 (7)	−0.047 (5)	0.106 (6)	−0.034 (5)
C1B	0.201 (12)	0.104 (7)	0.118 (8)	−0.002 (7)	−0.023 (8)	0.013 (6)
C1C	0.133 (9)	0.166 (10)	0.140 (9)	−0.023 (8)	0.022 (7)	−0.043 (7)
C1A	0.111 (7)	0.069 (7)	0.092 (5)	−0.013 (6)	0.026 (5)	−0.022 (6)
O1A	0.073 (5)	0.090 (5)	0.085 (5)	0.011 (4)	0.006 (4)	−0.012 (4)
C2A	0.111 (7)	0.069 (7)	0.092 (5)	−0.013 (6)	0.026 (5)	−0.022 (6)
O2A	0.073 (5)	0.090 (5)	0.085 (5)	0.011 (4)	0.006 (4)	−0.012 (4)

Geometric parameters (Å, º)

Cu1—O1	1.913 (3)	C12—C42	1.486 (8)
Cu2—O1	1.907 (3)	C13—C43	1.483 (8)
Cu3—O1	1.916 (3)	C14—C44	1.493 (8)
Cu4—O1	1.914 (3)	C21—C31	1.365 (7)
Cu1—Cu2	3.1144 (9)	C21—H21A	0.9300
Cu1—Cu3	3.1375 (9)	C22—C32	1.340 (7)
Cu1—Cu4	3.1354 (9)	C22—H22A	0.9300
Cu2—Cu3	3.1146 (9)	C23—C33	1.331 (8)
Cu2—Cu4	3.0945 (9)	C23—H23A	0.9300
Cu3—Cu4	3.1436 (9)	C24—C34	1.334 (8)
Cu1—N11	1.935 (4)	C24—H24A	0.9300
Cu1—Cl1	2.4005 (14)	C31—H31	0.9300
Cu1—Cl5	2.4322 (15)	C32—H32	0.9300
Cu1—Cl4	2.4624 (15)	C33—H33	0.9300
Cu2—N12	1.942 (4)	C34—H34	0.9300
Cu2—Cl4	2.3573 (15)	C41—H41A	0.9600
Cu2—Cl2	2.4257 (16)	C41—H41B	0.9600
Cu2—Cl6	2.4708 (16)	C41—H41C	0.9600
Cu3—N13	1.949 (4)	C42—H42A	0.9600
Cu3—Cl6	2.3665 (15)	C42—H42B	0.9600
Cu3—Cl5	2.3887 (14)	C42—H42C	0.9600
Cu3—Cl3	2.4623 (14)	C43—H43A	0.9600
Cu4—N14	1.958 (4)	C43—H43B	0.9600
Cu4—Cl2	2.3781 (16)	C43—H43C	0.9600
Cu4—Cl3	2.4283 (15)	C44—H44A	0.9600
Cu4—Cl1	2.4773 (14)	C44—H44B	0.9600
N11—C11	1.334 (6)	C44—H44C	0.9600
N11—C31	1.380 (6)	O1B—C1B	1.377 (9)
N12—C12	1.320 (6)	O1B—H1B	0.8200
N12—C32	1.366 (7)	O1C—C1C	1.390 (9)
N13—C13	1.320 (7)	O1C—H1C	0.8219
N13—C33	1.385 (7)	C1B—H1B1	0.9600
N14—C14	1.318 (7)	C1B—H1B2	0.9600
N14—C34	1.378 (7)	C1B—H1B3	0.9600
N21—C11	1.348 (6)	C1C—H1C1	0.9600
N21—C21	1.351 (7)	C1C—H1C2	0.9600
N21—H21	0.8600	C1C—H1C3	0.9600
N22—C12	1.337 (7)	C1A—O1A	1.400 (9)
N22—C22	1.345 (7)	C1A—H1E1	0.9600
N22—H22	0.8600	C1A—H1E2	0.9600
N23—C13	1.323 (7)	C1A—H1E3	0.9600
N23—C23	1.356 (7)	O1A—H1A	0.8200
N23—H23	0.8600	C2A—O2A	1.389 (8)
N24—C14	1.326 (7)	C2A—H2F1	0.9600
N24—C24	1.354 (8)	C2A—H2F2	0.9600
N24—H24	0.8600	C2A—H2F3	0.9600
C11—C41	1.467 (8)	O2A—H2A	0.8200
O1—Cu1—N11	175.85 (16)	Cu2—Cl4—Cu1	80.48 (5)
O1—Cu1—Cl1	85.75 (9)	Cu3—Cl5—Cu1	81.20 (4)
N11—Cu1—Cl1	96.52 (13)	Cu3—Cl6—Cu2	80.13 (5)
O1—Cu1—Cl5	83.67 (10)	Cu2—O1—Cu1	109.21 (14)
N11—Cu1—Cl5	92.25 (13)	Cu2—O1—Cu4	108.16 (14)
Cl1—Cu1—Cl5	132.62 (6)	Cu1—O1—Cu4	110.01 (14)
O1—Cu1—Cl4	83.57 (10)	Cu2—O1—Cu3	109.09 (14)
N11—Cu1—Cl4	98.96 (14)	Cu1—O1—Cu3	110.01 (15)
Cl1—Cu1—Cl4	108.28 (6)	Cu4—O1—Cu3	110.32 (14)
Cl5—Cu1—Cl4	116.15 (6)	C11—N11—C31	106.4 (5)
O1—Cu1—Cu2	35.33 (9)	C11—N11—Cu1	127.5 (4)
N11—Cu1—Cu2	146.92 (13)	C31—N11—Cu1	125.9 (4)
Cl1—Cu1—Cu2	98.61 (4)	C12—N12—C32	106.9 (4)
Cl5—Cu1—Cu2	98.73 (4)	C12—N12—Cu2	125.5 (4)
Cl4—Cu1—Cu2	48.28 (4)	C32—N12—Cu2	127.3 (4)
O1—Cu1—Cu4	35.00 (9)	C13—N13—C33	105.9 (5)
N11—Cu1—Cu4	146.65 (13)	C13—N13—Cu3	127.8 (4)
Cl1—Cu1—Cu4	51.08 (3)	C33—N13—Cu3	126.3 (4)
Cl5—Cu1—Cu4	104.43 (4)	C14—N14—C34	106.1 (5)
Cl4—Cu1—Cu4	99.18 (4)	C14—N14—Cu4	128.9 (4)
Cu2—Cu1—Cu4	59.355 (19)	C34—N14—Cu4	124.7 (4)
O1—Cu1—Cu3	35.02 (9)	C11—N21—C21	110.1 (5)
N11—Cu1—Cu3	140.84 (13)	C11—N21—H21	125.0
Cl1—Cu1—Cu3	107.39 (4)	C21—N21—H21	125.0
Cl5—Cu1—Cu3	48.80 (3)	C12—N22—C22	108.5 (5)
Cl4—Cu1—Cu3	102.22 (4)	C12—N22—H22	125.8
Cu2—Cu1—Cu3	59.76 (2)	C22—N22—H22	125.8
Cu4—Cu1—Cu3	60.15 (2)	C13—N23—C23	108.6 (5)
O1—Cu2—N12	175.27 (16)	C13—N23—H23	125.7
O1—Cu2—Cl4	86.66 (9)	C23—N23—H23	125.7
N12—Cu2—Cl4	95.48 (13)	C14—N24—C24	109.1 (5)
O1—Cu2—Cl2	85.21 (10)	C14—N24—H24	125.5
N12—Cu2—Cl2	97.61 (13)	C24—N24—H24	125.4
Cl4—Cu2—Cl2	115.62 (7)	N11—C11—N21	108.8 (5)
O1—Cu2—Cl6	82.32 (10)	N11—C11—C41	127.8 (5)
N12—Cu2—Cl6	93.28 (13)	N21—C11—C41	123.4 (5)
Cl4—Cu2—Cl6	137.30 (6)	N12—C12—N22	109.2 (5)
Cl2—Cu2—Cl6	104.42 (7)	N12—C12—C42	125.8 (5)
O1—Cu2—Cu4	35.99 (9)	N22—C12—C42	125.0 (5)
N12—Cu2—Cu4	146.57 (13)	N13—C13—N23	110.1 (5)
Cl4—Cu2—Cu4	102.77 (4)	N13—C13—C43	125.1 (6)
Cl2—Cu2—Cu4	49.23 (4)	N23—C13—C43	124.9 (6)
Cl6—Cu2—Cu4	91.96 (4)	N14—C14—N24	109.6 (6)
O1—Cu2—Cu3	35.55 (9)	N14—C14—C44	127.3 (5)
N12—Cu2—Cu3	139.74 (13)	N24—C14—C44	123.1 (6)
Cl4—Cu2—Cu3	105.48 (4)	N21—C21—C31	105.2 (5)
Cl2—Cu2—Cu3	103.39 (5)	N21—C21—H21A	127.4
Cl6—Cu2—Cu3	48.47 (4)	C31—C21—H21A	127.4
Cu4—Cu2—Cu3	60.83 (2)	C32—C22—N22	106.9 (6)
O1—Cu2—Cu1	35.46 (9)	C32—C22—H22A	126.6
N12—Cu2—Cu1	146.26 (13)	N22—C22—H22A	126.6
Cl4—Cu2—Cu1	51.24 (4)	C33—C23—N23	106.7 (6)
Cl2—Cu2—Cu1	102.05 (4)	C33—C23—H23A	126.7
Cl6—Cu2—Cu1	107.80 (4)	N23—C23—H23A	126.7
Cu4—Cu2—Cu1	60.66 (2)	C34—C24—N24	106.0 (5)
Cu3—Cu2—Cu1	60.49 (2)	C34—C24—H24A	127.0
O1—Cu3—N13	179.36 (16)	N24—C24—H24A	127.0
O1—Cu3—Cl6	85.00 (10)	C21—C31—N11	109.6 (6)
N13—Cu3—Cl6	95.48 (13)	C21—C31—H31	125.2
O1—Cu3—Cl5	84.81 (9)	N11—C31—H31	125.2
N13—Cu3—Cl5	94.55 (13)	C22—C32—N12	108.6 (6)
Cl6—Cu3—Cl5	130.37 (6)	C22—C32—H32	125.7
O1—Cu3—Cl3	83.07 (9)	N12—C32—H32	125.7
N13—Cu3—Cl3	97.10 (14)	C23—C33—N13	108.8 (6)
Cl6—Cu3—Cl3	115.17 (6)	C23—C33—H33	125.6
Cl5—Cu3—Cl3	111.54 (5)	N13—C33—H33	125.6
O1—Cu3—Cu2	35.35 (9)	C24—C34—N14	109.2 (6)
N13—Cu3—Cu2	144.99 (13)	C24—C34—H34	125.4
Cl6—Cu3—Cu2	51.40 (4)	N14—C34—H34	125.4
Cl5—Cu3—Cu2	99.71 (4)	C11—C41—H41A	109.5
Cl3—Cu3—Cu2	106.90 (4)	C11—C41—H41B	109.5
O1—Cu3—Cu1	34.96 (9)	H41A—C41—H41B	109.5
N13—Cu3—Cu1	144.39 (12)	C11—C41—H41C	109.5
Cl6—Cu3—Cu1	109.94 (4)	H41A—C41—H41C	109.5
Cl5—Cu3—Cu1	50.00 (4)	H41B—C41—H41C	109.5
Cl3—Cu3—Cu1	94.18 (4)	C12—C42—H42A	109.5
Cu2—Cu3—Cu1	59.75 (2)	C12—C42—H42B	109.5
O1—Cu3—Cu4	34.82 (9)	H42A—C42—H42B	109.5
N13—Cu3—Cu4	145.49 (13)	C12—C42—H42C	109.5
Cl6—Cu3—Cu4	92.78 (5)	H42A—C42—H42C	109.5
Cl5—Cu3—Cu4	105.28 (4)	H42B—C42—H42C	109.5
Cl3—Cu3—Cu4	49.53 (4)	C13—C43—H43A	109.5
Cu2—Cu3—Cu4	59.27 (2)	C13—C43—H43B	109.5
Cu1—Cu3—Cu4	59.891 (19)	H43A—C43—H43B	109.5
O1—Cu4—N14	175.20 (16)	C13—C43—H43C	109.5
O1—Cu4—Cl2	86.41 (10)	H43A—C43—H43C	109.5
N14—Cu4—Cl2	94.01 (14)	H43B—C43—H43C	109.5
O1—Cu4—Cl3	84.05 (10)	C14—C44—H44A	109.5
N14—Cu4—Cl3	92.23 (14)	C14—C44—H44B	109.5
Cl2—Cu4—Cl3	133.59 (6)	H44A—C44—H44B	109.5
O1—Cu4—Cl1	83.60 (9)	C14—C44—H44C	109.5
N14—Cu4—Cl1	100.70 (13)	H44A—C44—H44C	109.5
Cl2—Cu4—Cl1	110.47 (7)	H44B—C44—H44C	109.5
Cl3—Cu4—Cl1	113.38 (5)	C1B—O1B—H1B	109.5
O1—Cu4—Cu2	35.84 (9)	C1C—O1C—H1C	109.7
N14—Cu4—Cu2	144.21 (13)	O1B—C1B—H1B1	109.4
Cl2—Cu4—Cu2	50.57 (4)	O1B—C1B—H1B2	109.5
Cl3—Cu4—Cu2	108.43 (4)	H1B1—C1B—H1B2	109.5
Cl1—Cu4—Cu2	97.46 (4)	O1B—C1B—H1B3	109.5
O1—Cu4—Cu1	34.99 (9)	H1B1—C1B—H1B3	109.5
N14—Cu4—Cu1	148.93 (13)	H1B2—C1B—H1B3	109.5
Cl2—Cu4—Cu1	102.59 (4)	O1C—C1C—H1C1	109.8
Cl3—Cu4—Cu1	94.92 (4)	O1C—C1C—H1C2	109.5
Cl1—Cu4—Cu1	48.93 (3)	H1C1—C1C—H1C2	109.5
Cu2—Cu4—Cu1	59.986 (19)	O1C—C1C—H1C3	109.2
O1—Cu4—Cu3	34.87 (9)	H1C1—C1C—H1C3	109.5
N14—Cu4—Cu3	140.74 (13)	H1C2—C1C—H1C3	109.5
Cl2—Cu4—Cu3	103.72 (5)	O2A—C2A—H2F1	109.5
Cl3—Cu4—Cu3	50.48 (3)	O2A—C2A—H2F2	109.5
Cl1—Cu4—Cu3	105.22 (4)	H2F1—C2A—H2F2	109.5
Cu2—Cu4—Cu3	59.90 (2)	O2A—C2A—H2F3	109.5
Cu1—Cu4—Cu3	59.96 (2)	H2F1—C2A—H2F3	109.5
Cu1—Cl1—Cu4	79.98 (4)	H2F2—C2A—H2F3	109.5
Cu4—Cl2—Cu2	80.20 (5)	C2A—O2A—H2A	109.5
Cu4—Cl3—Cu3	80.00 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···Cl3^i	0.86	2.36	3.220 (5)	174
N22—H22···Cl5^ii	0.86	2.49	3.304 (5)	159
N23—H23···O1A	0.86	1.97	2.813 (10)	167
N23—H23···O2A	0.86	2.15	2.935 (10)	152
N24—H24···O1B	0.86	1.87	2.727 (7)	175
O1B—H1B···O1C^iii	0.82	2.19	2.655 (9)	116
O1C—H1C···Cl4^iv	0.82	2.56	3.274 (7)	146
O1A—H1A···Cl6^v	0.82	2.47	3.223 (9)	153
O2A—H2A···Cl2^vi	0.82	2.74	3.416 (9)	141

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+2, −y, −z+1; (iv) x−1/2, −y+1/2, z+1/2; (v) −x+1, −y+1, −z+1; (vi) x−1, y, z.