A 1:1 cocrystal of di-μ-chloro-bis{[N-(1-hydroxy­but-2-yl)­salicyl­idene­iminato-N,O,O′]copper(II)} monohydrate and its methanol solvate

The structure consists of two crystallographically independent and differently solvated binuclear complexes, {[Cu₂Cl₂(C₁₁H₁₄NO₂)₂]·CH₄O}·{[Cu₂Cl₂(C₁₁H₁₄NO₂)₂]·H₂O}. The water and methanol solvate mol­ecules are similarly connected with the complex mol­ecules by two hydrogen bonds. The asymmetrical system of hydrogen bonds breaks up the potential centrosymmetricity of both chelate mol­ecules. All copper(II) centres are in a square-pyramidal environment, with four short bonds in the basal plane formed by two trans O atoms and one N atom of the tridentate ligand, and a bridge chloride ion. The fifth axial long bond is formed by a chloride ligand which lies in the basal plane of the neighbouring copper(II) ion.

S1. Comment

The stereochemistry of bis(µ-halide) bridged copper(II) dimers has attracted our attention in recent years (Bukowska-Strzyżewska et al., 1997). The present study on the title compound, (I), forms part of our work on the structure of dimeric copper(II) complexes with Schiff bases obtained from aromatic aldehyde and aliphatic amino-alcohols. We have previously reported several such compounds and studied their structural features (Bukowska-Strzyżewska et al., 1992; Maniukiewicz et al., 1994, 1995, 1996). It seems interesting to compare the influence of the solvation or hydration on the shape of dimeric molecules. \sch

The view of the two crystallographically independent binuclear complexes (molecules A and B) with the atom-labelling scheme is shown in Fig. 1a and 1 b. Each copper(II) ion is five-coordinated with approximate square-pyramidal geometry. Apart from small changes in the chemically equivalent bond lengths and angles of the molecules A and B, the largest dissimilarities exist in the geometry of Cu₂Cl₂ cores. The individual Cu–Cl–Cu bridges formed by one short Cu–Cl and one long Cu–Cl bonds have distinctly differentiated bond lengths. The short Cu–Cl bonds vary from 2.2550 (11) to 2.2645 (11) Å and the long Cu–Cl bonds from 2.6662 (12) to 2.9112 (13) Å. The Cu···Cu nonbonding distances are 3.450 (1) and 3.422 (1) Å for Cu1···Cu2 and Cu1'···Cu2', respectively. The central CuCl₂Cu rings are not planar. The dihedral angles change from 21.9 (1) to 23.1 (1)° for Cu1'–Cl1'–Cl2'–Cu2' and Cu1–Cl1–Cl2–Cu2, respectively.

The asymmetrical system of hydrogen bonds of molecules A and B is shown in Fig. 1a and 1 b. It spoils the potential centrosymmetricity of the binuclear molecules and induces the deformation of the core CuCl₂Cu rings and of Cu^II polyhedra. As we can see from Table 2 all three hydrogen bonds formed by methanol solvated complex B are distinctly shorter than the bonds formed by molecule A. The observed deformation of Cu^II coordination polyhedra from idealized square-pyramidal geometry toward the trigonal-bipyramidal is also on average greater in molecule B, than A. The deformation parameter τ computed on the basis of the two maximal valency angles of Cu atom as (α₁ - α₂)/60 (Adison et al., 1985) is 21.9 and 12.6% for Cu^II centres in A and 20.9 and 17.3% in B.

S2. Experimental

The title compound was prepared by modification of a previously described procedure (Samus et al., 1987). The complex was prepared by addition of CuCl₂·2H₂O (0.001 mol) to a warm solution containing the ligand (0.001 mol) in methanol (50 ml). The resulting solution was filtered and allowed to cool. Slow evaporation deposited dark green crystals analysed as [Cu₂Cl₂(C₁₁H₁₄NO₂)₂]·H₂O·CH₃OH. Analysis found: C 43.55, N 4.56, H 5.46%; calculated C 43.64, N 4.43, H 5.37%.

S3. Refinement

The structure of the title compound was solved by direct methods. Refinement was based on full-matrix least-squares calculations, with anisotropic displacement parameters for all non-H atoms and isotropic displacement parameters for H atoms. H atoms attached to O atoms were located directly from the difference map. The remaining H atoms were placed at their calculated position and refined using a riding model.

Computing details

Data collection: P3 Software (Siemens, 1990); cell refinement: P3 Software; data reduction: SHELXTL/PC XDISK (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1993); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1a. View of the hydrated A molecule with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Fig. 1 b. A perspective drawing of the B molecule solvated by CH3OH with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Di-µ-chlorobis[N-2-hydroxybuthyl)salicylideneiminato-N,O,O'copper(II)] methanol hydrate (1/1/1).

Crystal data

[Cu2Cl2(C11H14NO2)2].CH4O·[Cu2Cl2(C11H14NO2)2].H2O	Z = 2
Mr = 1214.94	F(000) = 1248
Triclinic, P1	Dx = 1.535 Mg m^−3 Dm = 1.55 (3) Mg m^−3 Dm measured by flotation in CH3I/CCl4
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.877 (1) Å	Cell parameters from 15 reflections
b = 15.079 (2) Å	θ = 10–20°
c = 16.212 (3) Å	µ = 1.86 mm^−1
α = 65.10 (2)°	T = 295 K
β = 71.71 (2)°	Prism, dark green
γ = 69.93 (2)°	0.40 × 0.35 × 0.30 mm
V = 2628.4 (6) Å^3

Data collection

Siemens P3 diffractometer	7583 reflections with I > 2σ(I)
Radiation source: FK60-10 Siemens Mo tube	Rint = 0.018
Graphite monochromator	θmax = 25.1°, θmin = 2.0°
ω–2θ scans	h = 0→15
Absorption correction: ψ scan North et al., 1968	k = −16→17
Tmin = 0.495, Tmax = 0.573	l = −18→19
9070 measured reflections	2 standard reflections every 100 reflections
8666 independent reflections	intensity decay: none

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.10	Calculated w = 1/[σ^2(Fo^2) + (0.0604P)^2 + 2.9616P] where P = (Fo^2 + 2Fc^2)/3
8666 reflections	(Δ/σ)max = 0.022
604 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
Cu1	0.25470 (3)	0.65369 (3)	0.15637 (3)	0.04031 (10)
Cu2	0.31012 (4)	0.44825 (3)	0.35362 (3)	0.04856 (12)
Cl1	0.41110 (8)	0.52512 (7)	0.15756 (7)	0.0523 (2)
Cl2	0.19709 (9)	0.60363 (7)	0.34025 (6)	0.0543 (2)
O1	0.3318 (2)	0.74790 (18)	0.14353 (17)	0.0468 (6)
O3	0.2043 (2)	0.40909 (18)	0.32345 (19)	0.0510 (7)
O2	0.1627 (2)	0.56135 (17)	0.16697 (17)	0.0477 (6)
H1	0.1819	0.5196	0.2180	0.057*
O4	0.4317 (2)	0.4786 (2)	0.3817 (2)	0.0615 (7)
H2	0.4459	0.5333	0.3403	0.074*
N1	0.1196 (2)	0.7565 (2)	0.1231 (2)	0.0426 (7)
N2	0.4028 (3)	0.3112 (2)	0.3942 (2)	0.0526 (8)
C1	0.1714 (3)	0.8907 (3)	0.1324 (2)	0.0432 (8)
C2	0.2818 (3)	0.8389 (3)	0.1475 (2)	0.0434 (8)
C3	0.3413 (3)	0.8884 (3)	0.1661 (3)	0.0541 (10)
H3	0.4167	0.8546	0.1765	0.065*
C4	0.2958 (4)	0.9833 (3)	0.1698 (3)	0.0632 (11)
H4	0.3389	1.0157	0.1820	0.076*
C5	0.1876 (4)	1.0339 (3)	0.1546 (3)	0.0634 (12)
H5	0.1547	1.0998	0.1588	0.076*
C6	0.1265 (4)	0.9892 (3)	0.1354 (3)	0.0567 (11)
H6	0.0521	1.0248	0.1233	0.068*
C7	0.0983 (3)	0.8481 (3)	0.1166 (2)	0.0459 (9)
H7	0.0281	0.8920	0.0998	0.055*
C8	0.0351 (3)	0.7194 (3)	0.1107 (3)	0.0510 (10)
H8	−0.0386	0.7604	0.1256	0.061*
C9	0.0455 (3)	0.6123 (3)	0.1804 (3)	0.0524 (10)
H9A	0.0193	0.6134	0.2424	0.063*
H9B	0.0016	0.5784	0.1710	0.063*
C10	0.0578 (4)	0.7260 (3)	0.0114 (3)	0.0616 (11)
H10A	0.1310	0.6840	−0.0033	0.074*
H10B	0.0579	0.7944	−0.0287	0.074*
C12	0.2095 (3)	0.3181 (3)	0.3282 (2)	0.0458 (9)
C11	0.2952 (3)	0.2318 (3)	0.3607 (2)	0.0475 (9)
C13	0.1268 (4)	0.3059 (3)	0.2977 (3)	0.0590 (11)
H13	0.0681	0.3639	0.2752	0.071*
C14	0.1276 (4)	0.2142 (3)	0.2992 (3)	0.0659 (12)
H14	0.0688	0.2078	0.2791	0.079*
C15	0.2124 (4)	0.1303 (3)	0.3295 (3)	0.0652 (12)
H15	0.2139	0.0664	0.3291	0.078*
C16	0.2938 (4)	0.1386 (3)	0.3605 (3)	0.0592 (11)
H16	0.3518	0.0798	0.3831	0.071*
C17	0.3865 (3)	0.2329 (3)	0.3933 (3)	0.0528 (10)
H17	0.4387	0.1697	0.4169	0.063*
C18	0.5000 (4)	0.3001 (3)	0.4307 (3)	0.0625 (11)
H18	0.5610	0.2465	0.4175	0.075*
C19	0.5338 (4)	0.3988 (3)	0.3798 (3)	0.0666 (12)
H19A	0.5840	0.4027	0.4104	0.080*
H19B	0.5717	0.4045	0.3171	0.080*
C20	0.4678 (4)	0.2740 (4)	0.5328 (3)	0.0831 (15)
H20A	0.4278	0.2219	0.5588	0.100*
H20B	0.4178	0.3327	0.5456	0.100*
C21	−0.0296 (5)	0.6970 (5)	−0.0100 (4)	0.0925 (16)
H21A	−0.0134	0.7025	−0.0737	0.111*
H21B	−0.0290	0.6283	0.0295	0.111*
H21C	−0.1027	0.7396	0.0039	0.111*
C22	0.5675 (6)	0.2395 (8)	0.5796 (5)	0.162 (4)
H22A	0.5435	0.2239	0.6455	0.194*
H22B	0.6170	0.1804	0.5672	0.194*
H22C	0.6068	0.2920	0.5538	0.194*
Cu1'	−0.17619 (4)	0.91260 (3)	0.27670 (3)	0.04102 (10)
Cu2'	−0.38935 (3)	1.12610 (3)	0.22481 (3)	0.03957 (10)
Cl1'	−0.19207 (7)	1.02871 (7)	0.13373 (6)	0.0461 (2)
Cl2'	−0.39781 (8)	0.98836 (7)	0.35473 (6)	0.0509 (2)
O1'	−0.2123 (2)	0.81429 (18)	0.25407 (17)	0.0480 (6)
O2'	−0.1389 (2)	1.00978 (18)	0.31181 (18)	0.0500 (6)
H1'	−0.2056	1.0681	0.3138	0.060*
O3'	−0.3043 (2)	1.17189 (18)	0.26968 (18)	0.0479 (6)
O4'	−0.4767 (2)	1.08607 (17)	0.16933 (16)	0.0438 (6)
H2'	−0.4394	1.0160	0.1736	0.053*
N1'	−0.1159 (3)	0.8157 (2)	0.3858 (2)	0.0464 (7)
N2'	−0.4227 (2)	1.2538 (2)	0.12435 (19)	0.0403 (7)
C1'	−0.1527 (3)	0.6696 (3)	0.3851 (2)	0.0449 (9)
C2'	−0.2034 (3)	0.7177 (3)	0.3062 (2)	0.0449 (9)
C3'	−0.2441 (4)	0.6593 (3)	0.2818 (3)	0.0569 (10)
H3'	−0.2796	0.6914	0.2290	0.068*
C4'	−0.2352 (4)	0.5586 (3)	0.3317 (3)	0.0694 (12)
H4'	−0.2647	0.5207	0.3134	0.083*
C5'	−0.1846 (4)	0.5112 (3)	0.4082 (3)	0.0724 (13)
H5'	−0.1789	0.4407	0.4430	0.087*
C6'	−0.1431 (4)	0.5660 (3)	0.4340 (3)	0.0592 (11)
H6'	−0.1057	0.5335	0.4857	0.071*
C7'	−0.1118 (3)	0.7216 (3)	0.4197 (3)	0.0508 (10)
H7'	−0.0749	0.6815	0.4714	0.061*
C8'	−0.0729 (3)	0.8592 (3)	0.4314 (3)	0.0543 (10)
H8'	−0.0856	0.8234	0.4971	0.065*
C9'	−0.1406 (4)	0.9674 (3)	0.4100 (3)	0.0587 (10)
H9C	−0.2165	0.9689	0.4446	0.070*
H9D	−0.1088	1.0049	0.4270	0.070*
C10'	0.0514 (4)	0.8474 (4)	0.3967 (3)	0.0687 (12)
H10C	0.0643	0.8920	0.3334	0.082*
H10D	0.0870	0.7795	0.3983	0.082*
C11'	−0.3139 (3)	1.3385 (3)	0.1512 (3)	0.0447 (9)
C12'	−0.2750 (3)	1.2587 (3)	0.2299 (3)	0.0456 (9)
C13'	−0.2019 (3)	1.2750 (3)	0.2683 (3)	0.0620 (11)
H13'	−0.1751	1.2226	0.3219	0.074*
C14'	−0.1705 (4)	1.3642 (3)	0.2319 (4)	0.0768 (13)
H14'	−0.1211	1.3735	0.2598	0.092*
C15'	−0.2107 (4)	1.4420 (3)	0.1565 (4)	0.0774 (14)
H15'	−0.1869	1.5037	0.1303	0.093*
C16'	−0.2806 (4)	1.4278 (3)	0.1169 (3)	0.0615 (11)
H16'	−0.3103	1.4818	0.0653	0.074*
C17'	−0.3858 (3)	1.3309 (3)	0.1033 (2)	0.0431 (8)
H17'	−0.4088	1.3887	0.0511	0.052*
C18'	−0.4950 (3)	1.2566 (3)	0.0678 (2)	0.0450 (9)
H18'	−0.4747	1.2996	0.0049	0.054*
C19'	−0.4678 (3)	1.1488 (3)	0.0720 (2)	0.0495 (9)
H19C	−0.5204	1.1411	0.0461	0.059*
H19D	−0.3930	1.1306	0.0378	0.059*
C20'	−0.6165 (3)	1.2983 (3)	0.1048 (3)	0.0535 (10)
H20C	−0.6252	1.3647	0.1035	0.064*
H20D	−0.6359	1.2564	0.1684	0.064*
C21'	0.1063 (5)	0.8711 (5)	0.4510 (5)	0.114 (2)
H21D	0.1859	0.8638	0.4268	0.137*
H21E	0.0712	0.9393	0.4486	0.137*
H21F	0.0941	0.8259	0.5141	0.137*
C22'	−0.6976 (4)	1.3038 (3)	0.0509 (3)	0.0681 (12)
H22D	−0.7737	1.3305	0.0777	0.082*
H22E	−0.6794	1.3467	−0.0124	0.082*
H22F	−0.6902	1.2373	0.0530	0.082*
O5	0.4994 (4)	0.6383 (3)	0.2490 (3)	0.1205 (14)
H1W	0.4318	0.6726	0.2215	0.145*
H2W	0.5465	0.6341	0.2018	0.145*
O5'	−0.3945 (2)	0.90100 (19)	0.17167 (18)	0.0538 (7)
H5M	−0.3360	0.8861	0.1931	0.065*
C23'	−0.3491 (4)	0.8973 (4)	0.0817 (3)	0.0774 (14)
H23A	−0.4098	0.9133	0.0515	0.093*
H23B	−0.3034	0.8308	0.0856	0.093*
H23C	−0.3037	0.9453	0.0468	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0400 (2)	0.0346 (2)	0.0420 (2)	−0.00693 (17)	−0.00721 (17)	−0.01197 (17)
Cu2	0.0501 (2)	0.0399 (2)	0.0501 (2)	−0.00588 (19)	−0.0141 (2)	−0.01177 (19)
Cl1	0.0454 (5)	0.0436 (4)	0.0601 (5)	−0.0018 (4)	−0.0061 (4)	−0.0212 (4)
Cl2	0.0653 (6)	0.0427 (5)	0.0427 (5)	−0.0022 (4)	−0.0072 (4)	−0.0150 (4)
O1	0.0416 (12)	0.0410 (12)	0.0548 (14)	−0.0107 (10)	−0.0073 (11)	−0.0153 (11)
O3	0.0476 (13)	0.0375 (13)	0.0636 (16)	−0.0069 (11)	−0.0180 (12)	−0.0116 (11)
O2	0.0529 (14)	0.0368 (12)	0.0511 (14)	−0.0102 (11)	−0.0166 (11)	−0.0094 (11)
O4	0.0636 (16)	0.0553 (15)	0.0681 (17)	−0.0134 (13)	−0.0227 (14)	−0.0180 (13)
N1	0.0448 (15)	0.0367 (15)	0.0427 (15)	−0.0074 (12)	−0.0127 (12)	−0.0099 (12)
N2	0.0520 (17)	0.0463 (17)	0.0519 (18)	−0.0055 (14)	−0.0158 (14)	−0.0114 (14)
C1	0.053 (2)	0.0367 (17)	0.0351 (17)	−0.0122 (15)	−0.0029 (15)	−0.0109 (14)
C2	0.0518 (19)	0.0405 (18)	0.0335 (17)	−0.0158 (16)	−0.0012 (15)	−0.0106 (14)
C3	0.059 (2)	0.052 (2)	0.051 (2)	−0.0188 (18)	−0.0102 (18)	−0.0140 (17)
C4	0.084 (3)	0.060 (2)	0.060 (2)	−0.035 (2)	−0.011 (2)	−0.0234 (19)
C5	0.087 (3)	0.043 (2)	0.063 (2)	−0.023 (2)	−0.002 (2)	−0.0241 (18)
C6	0.062 (2)	0.043 (2)	0.056 (2)	−0.0095 (18)	−0.0063 (19)	−0.0147 (18)
C7	0.0461 (19)	0.0401 (18)	0.0423 (19)	−0.0027 (15)	−0.0086 (15)	−0.0122 (15)
C8	0.0447 (19)	0.049 (2)	0.054 (2)	−0.0067 (16)	−0.0149 (17)	−0.0126 (17)
C9	0.0481 (19)	0.055 (2)	0.054 (2)	−0.0205 (17)	−0.0134 (17)	−0.0096 (17)
C10	0.064 (2)	0.064 (2)	0.055 (2)	−0.015 (2)	−0.0149 (19)	−0.0168 (19)
C12	0.0490 (19)	0.0420 (19)	0.0387 (18)	−0.0149 (16)	−0.0018 (15)	−0.0089 (15)
C11	0.053 (2)	0.0398 (18)	0.0384 (18)	−0.0100 (16)	−0.0025 (16)	−0.0089 (15)
C13	0.060 (2)	0.053 (2)	0.060 (2)	−0.0164 (19)	−0.013 (2)	−0.0134 (19)
C14	0.069 (3)	0.075 (3)	0.064 (3)	−0.030 (2)	−0.008 (2)	−0.028 (2)
C15	0.084 (3)	0.056 (2)	0.062 (2)	−0.027 (2)	−0.002 (2)	−0.0271 (19)
C16	0.068 (3)	0.045 (2)	0.053 (2)	−0.0095 (19)	−0.001 (2)	−0.0183 (18)
C17	0.051 (2)	0.0390 (19)	0.051 (2)	−0.0019 (17)	−0.0080 (17)	−0.0080 (17)
C18	0.054 (2)	0.059 (2)	0.068 (3)	−0.0055 (19)	−0.023 (2)	−0.015 (2)
C19	0.060 (2)	0.057 (2)	0.076 (3)	−0.012 (2)	−0.025 (2)	−0.011 (2)
C20	0.077 (3)	0.099 (4)	0.068 (3)	−0.019 (3)	−0.020 (2)	−0.023 (3)
C21	0.100 (3)	0.116 (4)	0.086 (3)	−0.030 (3)	−0.039 (3)	−0.040 (3)
C22	0.117 (5)	0.253 (10)	0.093 (5)	−0.045 (6)	−0.057 (4)	−0.015 (6)
Cu1'	0.0460 (2)	0.0383 (2)	0.0388 (2)	−0.00768 (18)	−0.01387 (17)	−0.01171 (17)
Cu2'	0.0432 (2)	0.0373 (2)	0.0402 (2)	−0.00941 (17)	−0.01204 (17)	−0.01313 (17)
Cl1'	0.0462 (4)	0.0479 (5)	0.0373 (4)	−0.0111 (4)	−0.0074 (3)	−0.0096 (4)
Cl2'	0.0520 (5)	0.0488 (5)	0.0418 (5)	−0.0127 (4)	−0.0052 (4)	−0.0092 (4)
O1'	0.0613 (14)	0.0381 (12)	0.0461 (13)	−0.0068 (11)	−0.0200 (11)	−0.0139 (10)
O2'	0.0573 (14)	0.0425 (13)	0.0572 (14)	−0.0079 (11)	−0.0268 (12)	−0.0164 (11)
O3'	0.0570 (14)	0.0398 (12)	0.0562 (14)	−0.0088 (11)	−0.0236 (11)	−0.0191 (11)
O4'	0.0501 (13)	0.0403 (12)	0.0444 (12)	−0.0112 (10)	−0.0149 (10)	−0.0142 (10)
N1'	0.0510 (16)	0.0443 (16)	0.0450 (16)	−0.0067 (13)	−0.0170 (13)	−0.0155 (13)
N2'	0.0431 (15)	0.0391 (14)	0.0403 (14)	−0.0072 (12)	−0.0106 (12)	−0.0160 (12)
C1'	0.0471 (19)	0.0404 (18)	0.0400 (18)	−0.0093 (15)	−0.0024 (15)	−0.0131 (15)
C2'	0.0455 (19)	0.0415 (18)	0.0420 (18)	−0.0089 (15)	−0.0036 (15)	−0.0144 (15)
C3'	0.070 (2)	0.050 (2)	0.055 (2)	−0.0190 (19)	−0.0105 (19)	−0.0208 (18)
C4'	0.092 (3)	0.054 (2)	0.070 (3)	−0.030 (2)	−0.011 (2)	−0.024 (2)
C5'	0.101 (3)	0.045 (2)	0.066 (3)	−0.031 (2)	−0.009 (3)	−0.010 (2)
C6'	0.070 (3)	0.046 (2)	0.047 (2)	−0.0120 (19)	−0.0093 (19)	−0.0054 (17)
C7'	0.050 (2)	0.050 (2)	0.044 (2)	−0.0055 (17)	−0.0141 (16)	−0.0101 (17)
C8'	0.061 (2)	0.059 (2)	0.047 (2)	−0.0149 (19)	−0.0215 (17)	−0.0146 (17)
C9'	0.068 (2)	0.061 (2)	0.057 (2)	−0.006 (2)	−0.0288 (19)	−0.0267 (18)
C10'	0.062 (3)	0.067 (3)	0.076 (3)	−0.009 (2)	−0.018 (2)	−0.028 (2)
C11'	0.0414 (18)	0.0388 (17)	0.055 (2)	−0.0082 (15)	−0.0041 (16)	−0.0232 (15)
C12'	0.0403 (18)	0.0426 (18)	0.060 (2)	−0.0023 (15)	−0.0106 (16)	−0.0291 (16)
C13'	0.053 (2)	0.056 (2)	0.093 (3)	−0.0002 (18)	−0.034 (2)	−0.039 (2)
C14'	0.055 (2)	0.072 (3)	0.132 (4)	−0.012 (2)	−0.035 (2)	−0.053 (3)
C15'	0.067 (3)	0.056 (2)	0.122 (4)	−0.027 (2)	−0.023 (3)	−0.032 (3)
C16'	0.060 (2)	0.045 (2)	0.080 (3)	−0.0154 (19)	−0.015 (2)	−0.021 (2)
C17'	0.0463 (19)	0.0385 (17)	0.0423 (18)	−0.0077 (15)	−0.0073 (15)	−0.0155 (15)
C18'	0.054 (2)	0.0440 (18)	0.0350 (17)	−0.0116 (16)	−0.0139 (15)	−0.0088 (14)
C19'	0.063 (2)	0.0496 (19)	0.0424 (18)	−0.0122 (17)	−0.0196 (17)	−0.0169 (16)
C20'	0.052 (2)	0.052 (2)	0.055 (2)	−0.0133 (17)	−0.0153 (18)	−0.0152 (18)
C21'	0.085 (3)	0.149 (5)	0.150 (5)	−0.036 (4)	−0.039 (4)	−0.074 (4)
C22'	0.065 (2)	0.059 (2)	0.089 (3)	−0.011 (2)	−0.037 (2)	−0.021 (2)
O5	0.146 (3)	0.074 (2)	0.158 (3)	−0.042 (2)	−0.107 (3)	0.009 (2)
O5'	0.0639 (15)	0.0490 (14)	0.0564 (15)	−0.0117 (12)	−0.0224 (12)	−0.0203 (12)
C23'	0.098 (3)	0.077 (3)	0.069 (3)	−0.011 (3)	−0.028 (3)	−0.036 (2)

Geometric parameters (Å, º)

Cu1—O1	1.907 (3)	Cu1'—Cl2'	2.7862 (12)
Cu1—N1	1.937 (3)	Cu2'—O3'	1.910 (3)
Cu1—O2	2.043 (3)	Cu2'—N2'	1.943 (3)
Cu1—Cl1	2.2646 (11)	Cu2'—O4'	1.999 (3)
Cu1—Cl2	2.6662 (12)	Cu2'—Cl2'	2.2560 (12)
Cu2—O3	1.912 (3)	Cu2'—Cl1'	2.7752 (12)
Cu2—N2	1.945 (3)	O1'—C2'	1.326 (4)
Cu2—O4	1.996 (3)	O2'—C9'	1.440 (5)
Cu2—Cl2	2.2550 (11)	O2'—H1'	0.9999
Cu2—Cl1	2.9112 (13)	O3'—C12'	1.322 (4)
O1—C2	1.320 (4)	O4'—C19'	1.450 (4)
O3—C12	1.321 (4)	O4'—H2'	0.9805
O2—C9	1.433 (4)	N1'—C7'	1.277 (5)
O2—H1	0.8511	N1'—C8'	1.482 (5)
O4—C19	1.447 (5)	N2'—C17'	1.278 (5)
O4—H2	0.8500	N2'—C18'	1.479 (5)
N1—C7	1.276 (5)	C1'—C6'	1.403 (5)
N1—C8	1.479 (5)	C1'—C2'	1.415 (5)
N2—C17	1.275 (5)	C1'—C7'	1.431 (6)
N2—C18	1.477 (5)	C2'—C3'	1.396 (6)
C1—C2	1.410 (5)	C3'—C4'	1.370 (6)
C1—C6	1.413 (5)	C3'—H3'	0.9601
C1—C7	1.439 (6)	C4'—C5'	1.384 (7)
C2—C3	1.400 (6)	C4'—H4'	0.9602
C3—C4	1.368 (6)	C5'—C6'	1.369 (7)
C3—H3	0.9601	C5'—H5'	0.9600
C4—C5	1.382 (6)	C6'—H6'	0.9600
C4—H4	0.9600	C7'—H7'	0.9600
C5—C6	1.365 (6)	C8'—C10'	1.495 (6)
C5—H5	0.9600	C8'—C9'	1.510 (6)
C6—H6	0.9600	C8'—H8'	0.9601
C7—H7	0.9600	C9'—H9C	0.9600
C8—C10	1.509 (6)	C9'—H9D	0.9600
C8—C9	1.522 (5)	C10'—C21'	1.494 (8)
C8—H8	0.9600	C10'—H10C	0.9600
C9—H9A	0.9600	C10'—H10D	0.9599
C9—H9B	0.9600	C11'—C16'	1.387 (5)
C10—C21	1.514 (7)	C11'—C12'	1.422 (5)
C10—H10A	0.9600	C11'—C17'	1.440 (5)
C10—H10B	0.9600	C12'—C13'	1.410 (6)
C12—C11	1.410 (5)	C13'—C14'	1.371 (6)
C12—C13	1.398 (6)	C13'—H13'	0.9601
C11—C16	1.413 (6)	C14'—C15'	1.382 (7)
C11—C17	1.440 (6)	C14'—H14'	0.9599
C13—C14	1.368 (6)	C15'—C16'	1.371 (7)
C13—H13	0.9600	C15'—H15'	0.9600
C14—C15	1.379 (6)	C16'—H16'	0.9599
C14—H14	0.9599	C17'—H17'	0.9600
C15—C16	1.357 (7)	C18'—C20'	1.502 (5)
C15—H15	0.9600	C18'—C19'	1.516 (5)
C16—H16	0.9600	C18'—H18'	0.9600
C17—H17	0.9600	C19'—H19C	0.9599
C18—C20	1.483 (7)	C19'—H19D	0.9600
C18—C19	1.507 (6)	C20'—C22'	1.521 (6)
C18—H18	0.9600	C20'—H20C	0.9599
C19—H19A	0.9601	C20'—H20D	0.9599
C19—H19B	0.9600	C21'—H21D	0.9600
C20—C22	1.523 (8)	C21'—H21E	0.9597
C20—H20A	0.9599	C21'—H21F	0.9599
C20—H20B	0.9600	C22'—H22D	0.9600
C21—H21A	0.9600	C22'—H22E	0.9600
C21—H21B	0.9599	C22'—H22F	0.9600
C21—H21C	0.9600	O5—H1W	0.9829
C22—H22A	0.9600	O5—H2W	0.8249
C22—H22B	0.9600	O5'—C23'	1.408 (5)
C22—H22C	0.9600	O5'—H5M	0.8500
Cu1'—O1'	1.894 (3)	C23'—H23A	0.9599
Cu1'—N1'	1.943 (3)	C23'—H23B	0.9600
Cu1'—O2'	2.015 (3)	C23'—H23C	0.9601
Cu1'—Cl1'	2.2615 (11)
O1—Cu1—N1	93.79 (11)	N1'—Cu1'—Cl1'	162.78 (10)
O1—Cu1—O2	175.87 (10)	O2'—Cu1'—Cl1'	90.79 (8)
N1—Cu1—O2	82.08 (11)	O1'—Cu1'—Cl2'	94.15 (8)
O1—Cu1—Cl1	95.08 (8)	N1'—Cu1'—Cl2'	101.89 (9)
N1—Cu1—Cl1	162.71 (10)	O2'—Cu1'—Cl2'	84.78 (8)
O2—Cu1—Cl1	88.86 (7)	Cl1'—Cu1'—Cl2'	93.01 (4)
O1—Cu1—Cl2	92.50 (8)	O3'—Cu2'—N2'	93.77 (12)
N1—Cu1—Cl2	99.08 (9)	O3'—Cu2'—O4'	175.97 (10)
O2—Cu1—Cl2	88.39 (8)	N2'—Cu2'—O4'	82.44 (11)
Cl1—Cu1—Cl2	95.33 (4)	O3'—Cu2'—Cl2'	92.03 (8)
O3—Cu2—N2	93.16 (13)	N2'—Cu2'—Cl2'	165.58 (9)
O3—Cu2—O4	174.57 (11)	O4'—Cu2'—Cl2'	91.98 (7)
N2—Cu2—O4	82.25 (13)	O3'—Cu2'—Cl1'	90.68 (8)
O3—Cu2—Cl2	92.76 (8)	N2'—Cu2'—Cl1'	99.70 (9)
N2—Cu2—Cl2	167.03 (11)	O4'—Cu2'—Cl1'	88.62 (7)
O4—Cu2—Cl2	92.32 (9)	Cl2'—Cu2'—Cl1'	93.42 (4)
O3—Cu2—Cl1	89.95 (9)	Cu1'—Cl1'—Cu2'	84.95 (4)
N2—Cu2—Cl1	102.41 (10)	Cu2'—Cl2'—Cu1'	84.79 (4)
O4—Cu2—Cl1	88.21 (9)	C2'—O1'—Cu1'	127.5 (2)
Cl2—Cu2—Cl1	89.12 (4)	C9'—O2'—Cu1'	108.3 (2)
Cu1—Cl1—Cu2	82.60 (4)	C9'—O2'—H1'	96.3
Cu2—Cl2—Cu1	88.62 (4)	Cu1'—O2'—H1'	110.0
C2—O1—Cu1	124.7 (2)	C12'—O3'—Cu2'	126.7 (2)
C12—O3—Cu2	127.3 (2)	C19'—O4'—Cu2'	108.1 (2)
C9—O2—Cu1	108.5 (2)	C19'—O4'—H2'	108.2
C9—O2—H1	111.7	Cu2'—O4'—H2'	106.8
Cu1—O2—H1	91.2	C7'—N1'—C8'	119.7 (3)
C19—O4—Cu2	110.0 (3)	C7'—N1'—Cu1'	125.7 (3)
C19—O4—H2	108.2	C8'—N1'—Cu1'	114.6 (2)
Cu2—O4—H2	109.0	C17'—N2'—C18'	119.7 (3)
C7—N1—C8	120.4 (3)	C17'—N2'—Cu2'	126.1 (3)
C7—N1—Cu1	125.2 (3)	C18'—N2'—Cu2'	114.2 (2)
C8—N1—Cu1	114.3 (2)	C6'—C1'—C2'	119.5 (4)
C17—N2—C18	118.8 (3)	C6'—C1'—C7'	117.2 (4)
C17—N2—Cu2	126.7 (3)	C2'—C1'—C7'	123.3 (3)
C18—N2—Cu2	114.5 (3)	O1'—C2'—C3'	118.8 (3)
C2—C1—C6	119.4 (4)	O1'—C2'—C1'	123.5 (4)
C2—C1—C7	123.8 (3)	C3'—C2'—C1'	117.7 (3)
C6—C1—C7	116.8 (3)	C4'—C3'—C2'	121.6 (4)
O1—C2—C3	119.0 (3)	C4'—C3'—H3'	120.0
O1—C2—C1	123.6 (3)	C2'—C3'—H3'	118.4
C3—C2—C1	117.4 (3)	C3'—C4'—C5'	120.7 (5)
C4—C3—C2	122.3 (4)	C3'—C4'—H4'	119.5
C4—C3—H3	118.8	C5'—C4'—H4'	119.8
C2—C3—H3	118.9	C6'—C5'—C4'	119.3 (4)
C3—C4—C5	120.0 (4)	C6'—C5'—H5'	120.4
C3—C4—H4	120.4	C4'—C5'—H5'	120.3
C5—C4—H4	119.6	C5'—C6'—C1'	121.2 (4)
C6—C5—C4	120.0 (4)	C5'—C6'—H6'	120.1
C6—C5—H5	119.8	C1'—C6'—H6'	118.7
C4—C5—H5	120.2	N1'—C7'—C1'	126.0 (4)
C5—C6—C1	120.9 (4)	N1'—C7'—H7'	116.9
C5—C6—H6	120.1	C1'—C7'—H7'	117.0
C1—C6—H6	118.9	N1'—C8'—C10'	109.6 (3)
N1—C7—C1	125.1 (3)	N1'—C8'—C9'	105.4 (3)
N1—C7—H7	117.5	C10'—C8'—C9'	114.1 (4)
C1—C7—H7	117.4	N1'—C8'—H8'	109.6
N1—C8—C10	109.9 (3)	C10'—C8'—H8'	107.8
N1—C8—C9	105.0 (3)	C9'—C8'—H8'	110.2
C10—C8—C9	113.6 (4)	O2'—C9'—C8'	107.1 (3)
N1—C8—H8	108.8	O2'—C9'—H9C	110.6
C10—C8—H8	109.5	C8'—C9'—H9C	109.1
C9—C8—H8	109.8	O2'—C9'—H9D	110.4
O2—C9—C8	106.9 (3)	C8'—C9'—H9D	110.9
O2—C9—H9A	110.0	H9C—C9'—H9D	108.7
C8—C9—H9A	109.9	C8'—C10'—C21'	113.6 (4)
O2—C9—H9B	110.4	C8'—C10'—H10C	108.5
C8—C9—H9B	110.9	C21'—C10'—H10C	108.3
H9A—C9—H9B	108.7	C8'—C10'—H10D	109.7
C8—C10—C21	113.8 (4)	C21'—C10'—H10D	108.5
C8—C10—H10A	109.6	H10C—C10'—H10D	108.2
C21—C10—H10A	109.3	C16'—C11'—C12'	119.5 (4)
C8—C10—H10B	108.8	C16'—C11'—C17'	117.5 (4)
C21—C10—H10B	107.1	C12'—C11'—C17'	123.0 (3)
H10A—C10—H10B	108.0	O3'—C12'—C13'	118.5 (3)
O3—C12—C11	124.0 (4)	O3'—C12'—C11'	124.3 (3)
O3—C12—C13	118.6 (3)	C13'—C12'—C11'	117.2 (3)
C11—C12—C13	117.4 (4)	C14'—C13'—C12'	121.5 (4)
C12—C11—C16	119.1 (4)	C14'—C13'—H13'	119.6
C12—C11—C17	123.7 (4)	C12'—C13'—H13'	118.9
C16—C11—C17	117.2 (4)	C13'—C14'—C15'	120.8 (4)
C14—C13—C12	122.0 (4)	C13'—C14'—H14'	119.7
C14—C13—H13	119.6	C15'—C14'—H14'	119.4
C12—C13—H13	118.4	C14'—C15'—C16'	119.0 (4)
C13—C14—C15	120.6 (5)	C14'—C15'—H15'	120.4
C13—C14—H14	120.1	C16'—C15'—H15'	120.5
C15—C14—H14	119.3	C15'—C16'—C11'	122.0 (4)
C16—C15—C14	119.3 (4)	C15'—C16'—H16'	119.7
C16—C15—H15	120.1	C11'—C16'—H16'	118.2
C14—C15—H15	120.6	N2'—C17'—C11'	125.7 (3)
C15—C16—C11	121.6 (4)	N2'—C17'—H17'	116.9
C15—C16—H16	119.4	C11'—C17'—H17'	117.4
C11—C16—H16	119.0	N2'—C18'—C20'	109.8 (3)
N2—C17—C11	125.1 (3)	N2'—C18'—C19'	104.9 (3)
N2—C17—H17	117.4	C20'—C18'—C19'	114.5 (3)
C11—C17—H17	117.6	N2'—C18'—H18'	109.3
C20—C18—N2	109.8 (4)	C20'—C18'—H18'	108.6
C20—C18—C19	113.6 (5)	C19'—C18'—H18'	109.7
N2—C18—C19	105.9 (3)	O4'—C19'—C18'	106.3 (3)
C20—C18—H18	108.2	O4'—C19'—H19C	110.2
N2—C18—H18	109.6	C18'—C19'—H19C	110.5
C19—C18—H18	109.8	O4'—C19'—H19D	110.6
O4—C19—C18	107.3 (3)	C18'—C19'—H19D	110.4
O4—C19—H19A	109.8	H19C—C19'—H19D	108.7
C18—C19—H19A	109.8	C18'—C20'—C22'	113.5 (4)
O4—C19—H19B	110.9	C18'—C20'—H20C	108.9
C18—C19—H19B	110.6	C22'—C20'—H20C	109.0
H19A—C19—H19B	108.4	C18'—C20'—H20D	108.4
C18—C20—C22	113.8 (5)	C22'—C20'—H20D	108.9
C18—C20—H20A	109.0	H20C—C20'—H20D	107.9
C22—C20—H20A	109.3	C10'—C21'—H21D	111.9
C18—C20—H20B	108.1	C10'—C21'—H21E	108.3
C22—C20—H20B	108.2	H21D—C21'—H21E	109.5
H20A—C20—H20B	108.2	C10'—C21'—H21F	108.1
C10—C21—H21A	111.9	H21D—C21'—H21F	109.5
C10—C21—H21B	107.1	H21E—C21'—H21F	109.5
H21A—C21—H21B	109.5	C20'—C22'—H22D	110.0
C10—C21—H21C	109.3	C20'—C22'—H22E	109.1
H21A—C21—H21C	109.5	H22D—C22'—H22E	109.5
H21B—C21—H21C	109.5	C20'—C22'—H22F	109.3
C20—C22—H22A	111.5	H22D—C22'—H22F	109.5
C20—C22—H22B	108.0	H22E—C22'—H22F	109.5
H22A—C22—H22B	109.5	H1W—O5—H2W	98.7
C20—C22—H22C	109.0	C23'—O5'—H5M	102.8
H22A—C22—H22C	109.5	O5'—C23'—H23A	108.9
H22B—C22—H22C	109.5	O5'—C23'—H23B	109.6
O1'—Cu1'—N1'	93.65 (12)	H23A—C23'—H23B	109.5
O1'—Cu1'—O2'	175.30 (10)	O5'—C23'—H23C	109.9
N1'—Cu1'—O2'	82.11 (12)	H23A—C23'—H23C	109.5
O1'—Cu1'—Cl1'	93.85 (8)	H23B—C23'—H23C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O3	0.85	1.84	2.664 (4)	165
O2′—H1′···O3′	1.00	1.69	2.629 (4)	156
O4—H2···O5	0.85	1.82	2.662 (5)	171
O4′—H2′···O5′	0.98	1.64	2.611 (4)	170
O5—H1W···O1	0.98	1.83	2.793 (5)	165
O5′—H5M···O1′	0.85	1.89	2.718 (4)	163