Bis(hinokitiolato)copper(II): modification (III)

Bis(hinokitiolato)copper(II), Cu(hino)₂, exhibits both anti­bacterial and anti­viral properties, and has been previously shown to exist in two modifications. A third modification has now been confirmed, namely tetra­kis(μ₂-3-isopropyl-7-oxocyclo­hepta-1,3,5-trien-1-olato)bis­(3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato)tricopper(II)–bis­(μ₂-3-isopropyl-7-oxocyclo­hepta-1,3,5-trien-1-olato)bis­[(3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato)copper(II)] (1/1), [Cu(C₁₀H₁₁O₂)₂]₃·[Cu(C₁₀H₁₁O₂)₂]₂, where 3-isopropyl-7-oxocyclo­hepta-1,3,5-trien-1-olate is the systematic name for the hinokitiolate anion. This new modification is composed of discrete [cis-Cu(hino)₂]₂[trans-Cu(hino)₂] trimers and [cis-Cu(hino)₂]₂ dimers. The Cu atoms are bridged by μ₂-O atoms from the hinokitiolate ligands to give distorted square-pyramidal and distorted octa­hedral Cu^II coordination environments. Hence, the Cu^II environments are CuO₅/CuO₆/CuO₅ for the trimer and CuO₅/CuO₅ for the dimer. Each trimer and dimer has crystallographically imposed inversion symmetry. The trimer has never been observed before, the dimer has been seen only once before, and the combination of the two together in the same lattice is unprecedented. The CuO₅ cores exhibit four strong basal Cu—O bonds [1.915 (2)–1.931 (2) Å] and one weak apical Cu—O bond [2.652 (2)–2.658 (2) Å]. The CuO₆ core exhibits four strong equatorial Cu—O bonds [1.922 (2)–1.929 (2) Å] and two very weak axial Cu—O bonds [2.911 (3) Å]. The bite angles for the chelating hinokitiolate ligands range from 83.13 (11) to 83.90 (10)°.

S1. Comment

Hinokitiol (β-thujaplicin) and metal complexes of the hinokitiolate anion have been known for 74 years (Nozoe, 1936). The former is a natural product and of interest for its broad range of biological activities, e.g. antitumor, antibacterial, antifungal and insecticidal properties (Inamori et al., 1993, 2000; Arima et al., 2003; Morita et al., 2003), while the latter metal complexes exhibit antiviral and antimicrobial properties (Miyamoto et al., 1998; Nomiya et al., 2009). Among these compounds, the Cu complex reported by Nozoe in 1936 is arguably the most structurally intriguing. In 2002, initial insights into the `unusual structural chemistry of Cu^II hinokitiol' [also referred to as bis(hinokitiolato)copper(II) or Cu(hino)₂] were provided by Molloy and co-workers, who found that Cu(hino)₂ could be crystallized in two modifications (Barret et al., 2002). Modification (I) turned out to be monomeric trans-Cu(hino)₂, while modification (II) is composed of monomers and dimers, i.e. [cis-Cu(hino)₂]₂.[trans-Cu(hino)₂]₂. trans-Cu(hino)₂. Subsequent studies have further revealed that (I) is polymorphic (Barret et al., 2002; Nomiya et al., 2004; Arvanitis et al., 2004; Ho et al., 2009). A third modification, (III), has been discovered and is reported here. This new modification is composed of dimers and trimers, i.e. [cis-Cu(hino)₂]₂[trans-Cu(hino)₂]. [cis-Cu(hino)₂]₂. Views of the trimer and dimer are given in Figs. 1 and 2, respectively, and selected bond distances and bond valences are summarized in Table 1.

Trimeric Cu^II hinokitiol has never been observed before and therefore constitutes the most notable feature of this study. As shown in Fig. 1, the trimer consists of a single planar trans-Cu(hino)₂ moiety sandwiched between two visibly twisted cis-Cu(hino)₂ moieties. Atom Cu1 is situated at Wyckoff position 1h [space group P1 (No. 2)], requiring that the trimer possess crystallographically imposed inversion symmetry. Atoms Cu1, O1, O2, O1ⁱ and O2ⁱ are also required by symmetry to be exactly coplanar [symmetry code: (i) -x + 1, -y + 1, -z + 1.] In contrast, atoms Cu2, O3, O4, O5 and O6 in the nonplanar cis moieties exhibit displacements of -0.109 (1), 0.168 (1), -0.111 (1), -0.114 (1) and 0.166 (1) Å, respectively, from the least-squares plane defined by those atoms. The end-to-end distances for the Cu(hino)₂ moieties (excluding the isopropyl groups) are 11.358 (7) and 11.274 (6) Å for C4···C4ⁱ and C14···C24, respectively. The shortening of the C14···C24 distance is consistent with the cis moieties being slightly bowed in addition to being twisted. Four of the six hinokitiolate ligands participate in asymmetric µ₂-O bridges to yield the final trimeric structure, with atom Cu1 having a distorted octahedral CuO₆ coordination geometry and atom Cu2 having a distorted CuO₅ square-pyramidal coordination environment. The twisting and bowing of the cis moieties help to facilitate the bridge bonding, and to alleviate steric repulsions between the C21–C27 and C21ⁱ–C27ⁱ cycloheptatriene rings and atoms H8 and H8ⁱ of the central trans moiety, respectively.

The dimeric Cu^II hinokitiol component in (III), while less novel than the cis,trans,cis trimer, is nevertheless also unusual, having been observed only once before, i.e. in modification (II). The cis,cis dimers in (II) and (III) are quite synonymous, but the Cu atoms in both dimers are probably better described as five-coordinate with square-pyramidal environments, rather than `four-coordinate and in a square-planar environment' (Barret et al., 2002). In both (II) and (III), the cis,cis dimers possess crystallographically imposed inversion symmetry. For (III), the dimer is centered on Wyckoff position 1a, i.e. the midpoint between atoms Cu3 and Cu3ⁱⁱ in Fig. 2 [symmetry code: (ii) -x, -y, -z + 2]. Atom Cu3 is 0.105 (1) Å above the least-squares plane defined by atoms O7–O10 and displaced towards atom O9ⁱⁱ. The C34···C44 end-to-end distance is 11.166 (6) Å, indicating that the cis moieties in the dimer are even more bowed than those in the trimer. In contrast, atom Cu1 in (II) is coplanar with atoms O1–O4. The displacements from the least-squares plane defined by these five atoms are -0.103 (1), -0.088 (2), 0.145 (2), 0.141 (2) and -0.095 (2) Å, respectively. The cis moieties in (II) are, however, also bowed, with the C5···C15 end-to-end distance being 11.176 (5) Å. These observations are more consistent with CuO₅ cores and covalent bonding, rather than CuO₄ cores and a fifth axial intermolecular interaction.

A bond-valence analysis (Brown, 2002, 2009) of the CuO_x bonding in the cis,trans,cis trimer and cis,cis dimer is given in Table 1. The CuO₆ values in (III) are compared with those for bis(tropolonato)copper(II) [Cu(trop)₂], which is most often viewed as a square-planar CuO₄ monomer (Robertson, 1951; Macintyre et al., 1966; Berg et al., 1978). The latter view has, however, been challenged by a subsequent claim that Cu(trop)₂ `exists as a sandwich-type dimer' (Hasegawa et al., 1997); a claim reiterated in a recent review article (Vigato et al., 2009). Suffice to say that it is crystallographically impossible for discrete dimers to exist in that 1997 determination. Cu(trop)₂ is either a solid-state monomer or, as entertained below, possibly a solid-state polymer with CuO₆ bonding. Finally, the CuO₅ values for (III) are compared with those for (II). For completeness, the trans,trans dimer values for (II) are also provided.

The CuO₆ equatorial bonds in the trans moiety of the trimer are in the range 1.922 (2)–1.929 (2) Å and are noticably longer than the range of 1.900 (2)–1.918 (2) Å observed in the trans-Cu(hino)₂ monomer, (I). This lengthening of the Cu—O bonds is consistent with oligomerization; the Cu—O bonds in the trans,trans dimer in (II) also experience a similar lengthening [1.915 (2)–1.939 (2) Å]. The CuO₆ axial bonds in (III) are long at 2.911 (3) Å, while those in Cu(trop)₂ are even longer at 3.144 (2) Å. The comparable literature values for CuO₆ equatorial and axial bonds are 1.908 (2)–1.948 (6) and 2.797 (2)–2.948 (2) Å, respectively (Table 2). The CuO₆ average bond valence, bond-valence sum, s/s' and distortion index ΔR are 0.355, 2.128, 0.101–1.462 and 0.191, respectively, for (III), and 0.358, 2.150, 0.053–1.475 and 0.266, respectively, for Cu(trop)₂, while the literature s/s' and ΔR values are 0.07–1.50 and 0.048–0.146, respectively, for Jahn–Teller distorted CuO₆ octahedra (Brown, 2006). All of the numerical values for (III) are in excellent agreement with the presence of a Jahn–Teller elongated CuO₆ octahedron. Cu(trop)₂, on the other hand, is at or beyond the limits of such a description. While axial bonds beyond 3 Å do potentially exist (see Table 2), Cu(trop)₂ is probably better described as a square-planar CuO₄ monomer.

The CuO₅ basal bonds in the cis moieties in both the trimer and dimer in (III) are in the range 1.915 (3)–1.931 (3) Å and are comparable with the range of 1.919 (2)–1.933 (2) Å observed in the cis,cis dimer in (II). The CuO₅ apical bonds in (III) are 2.658 (3) and 2.652 (3) Å for the trimer and dimer, respectively, but only 2.476 (2) Å in the cis,cis dimer in (II). The comparable literature values for CuO₅ basal and apical bonds are 1.898 (3)–1.962 (3) and 2.392 (3)–2.878 (3) Å, respectively (Table 2). The CuO₅ average bond valence, bond-valence sum, s/s' and distortion index ΔR are 0.429, 2.157, 0.167–1.226 and 0.077, respectively, for (III), and 0.431, 2.154, 0.267–1.205 and 0.048, respectively, for (II). All of these values are in excellent agreement with the cis moieties in (III) having distorted CuO₅ square-pyramidal coordination geometries.

The trimers form hydrogen-bonded ribbons in the solid state via the two interactions C5—H5···O5ⁱⁱⁱ [C5—H5 = 0.95, H5···O5ⁱⁱⁱ = 2.40 and C5···O5ⁱⁱⁱ = 3.328 (4) Å, and C5—H5···O5ⁱⁱⁱ = 165.2°; symmetry code: (iii) -x, -y +1, -z + 1] and C6—H6···O3ⁱⁱⁱ [C6—H6 = 0.95, H6···O3ⁱⁱⁱ = 2.43 and C6···O3ⁱⁱⁱ = 3.302 (4) Å, and C6—H6···O3ⁱⁱⁱ = 153.2°]. Chains of dimers are present, but there are no dimer···dimer hydrogen-bonding, π–π stacking or Cu···π interactions involved. The closest dimer···dimer contact is Cu3···C34^iv = 3.399 (4) Å [symmetry code: (iv) -x + 1, -y, -z + 2]. Finally, the ribbons of trimers and chains of dimers are linked via the two interactions C24—H2···O8^v4 [C24—H24 = 0.95, H24···O8^v = 2.52 and C24···O8^v = 3.446 (5) Å, and C24—H24···O8^v = 164.3°; symmetry code: (v) x, y + 1, z] and C45—H45···O3 [C45—H45 = 0.95, H45···O3 = 2.58 and C45···O3 = 3.397 (5) Å, and C45—H45···O3 = 145.0°].

In summary, structural details have been presented for a third modification of the bioactive substance Cu^II hinokitiol. This new modification, (III), is [cis-Cu(hino)₂]₂[trans-Cu(hino)₂]. [cis-Cu(hino)₂]₂, containing a previously undocumented cis,trans,cis trimer. The results from a bond-valence analysis are consistent with the central Cu^II atom having a Jahn–Teller distorted octahedral environment. The `unusual structural chemistry of Cu^II hinokitiol' now encompasses six crystalline forms, i.e. modification (I) with four forms, (II) with one form and (III) with one form. The trans:cis ratios are 1:0, 3:2 and 1:4 for modifications (I)–(III), respectively, making (III) the most cis-enriched modification so far uncovered.

Related literature

For related literature, see: Arima et al. (2003); Arvanitis et al. (2004); Barret et al. (2002); Berg et al. (1978); Brown (2002, 2006, 2009); Hasegawa et al. (1997); Ho et al. (2009); Inamori et al. (1993, 2000); Macintyre et al. (1966); Miyamoto et al. (1998); Morita et al. (2003); Nomiya et al. (2004, 2009); Nozoe (1936); Robertson (1951); Vigato et al. (2009).

S2. Experimental

Modification (III) was isolated from a mixture of assorted crystals of Cu(hino)₂, prepared as described by Arvanitis et al. (2004).

S3. Refinement

All H atoms were allowed to ride on their respective C atoms, with C—H = 0.95, 1.00 and 0.98 Å for the cycloheptatriene, methine and methyl H atoms, respectively, and with U_iso(H) = 1.2U_eq(C) for the cycloheptatriene and methine H atoms, or 1.5U_eq(C) for the methyl H atoms. Bond-valence parameters for Cu and O were taken from bvparm2009.cif and the calculations made with the bond-valence calculator Valence 2.0 distributed by Brown (https://www.ccp14.ac.uk/ccp/web-mirrors/i_d_brown).

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Version 2.02; Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The cis,trans,cis trimer in modification (III). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
	Fig. 2. The cis,cis dimer in modification (III). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (ii) -x, -y, -z + 2.]

tetrakis(µ₂-3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato)-1:2κ³O¹,O⁷:O⁷;1:2κ³O¹:O¹,O⁷;2:3κ³O¹,O⁷:O¹;2:3κ³O⁷:O¹,O⁷-bis(3-isopropyl-7-oxocyclohepta-1,3,5-trienolato)-1κ²O¹,O⁷;3κ²O¹,O⁷-tricopper(II)–bis(µ-3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato)-κ³O¹,O⁷:O⁷;κ³O⁷:O¹,O⁷-bis[(3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato-κ²O,O')copper(II)] (1/1)

Crystal data

[Cu(C10H11O2)2]3·[Cu(C10H11O2)2]2	Z = 1
Mr = 1949.58	F(000) = 1015
Triclinic, P1	Dx = 1.427 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6263 (2) Å	Cell parameters from 10341 reflections
b = 12.8911 (4) Å	θ = 1.1–27.5°
c = 19.4499 (6) Å	µ = 1.22 mm^−1
α = 72.847 (2)°	T = 200 K
β = 79.812 (2)°	Blade, grey-green
γ = 88.897 (2)°	0.30 × 0.15 × 0.03 mm
V = 2268.50 (11) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	10341 independent reflections
Radiation source: fine-focus sealed tube	6392 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
ω scans; 500 1.0° rotations	θmax = 27.5°, θmin = 1.1°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −12→12
Tmin = 0.710, Tmax = 0.970	k = −16→16
34847 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0699P)^2 + 1.131P] where P = (Fo^2 + 2Fc^2)/3
10341 reflections	(Δ/σ)max = 0.001
575 parameters	Δρmax = 1.10 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

Special details

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	0.5000	0.02947 (16)
O1	0.5639 (2)	0.3990 (2)	0.44608 (14)	0.0333 (6)
O2	0.3363 (2)	0.5060 (2)	0.45516 (13)	0.0299 (6)
C1	0.4668 (3)	0.3743 (3)	0.41359 (19)	0.0287 (8)
C2	0.4920 (3)	0.2927 (3)	0.38036 (19)	0.0301 (8)
H2	0.5814	0.2612	0.3843	0.036*
C3	0.4123 (3)	0.2473 (3)	0.3421 (2)	0.0302 (8)
C4	0.2791 (4)	0.2791 (3)	0.3277 (2)	0.0345 (9)
H4	0.2382	0.2403	0.3012	0.041*
C5	0.1976 (4)	0.3597 (3)	0.3465 (2)	0.0344 (9)
H5	0.1097	0.3686	0.3300	0.041*
C6	0.2231 (3)	0.4289 (3)	0.38510 (19)	0.0308 (8)
H6	0.1513	0.4792	0.3901	0.037*
C7	0.3393 (3)	0.4364 (3)	0.41824 (19)	0.0281 (8)
C8	0.4801 (4)	0.1531 (3)	0.3183 (2)	0.0390 (10)
H8	0.5825	0.1738	0.2998	0.047*
C9	0.4727 (5)	0.0519 (4)	0.3841 (3)	0.0562 (12)
H9A	0.5179	0.0682	0.4213	0.084*
H9B	0.5217	−0.0069	0.3685	0.084*
H9C	0.3736	0.0295	0.4047	0.084*
C10	0.4235 (5)	0.1278 (4)	0.2567 (3)	0.0560 (13)
H10A	0.4156	0.1955	0.2182	0.084*
H10B	0.3302	0.0913	0.2757	0.084*
H10C	0.4882	0.0802	0.2364	0.084*
Cu2	0.22722 (4)	0.48975 (4)	0.65615 (2)	0.03157 (14)
O3	0.0913 (2)	0.4638 (2)	0.60138 (14)	0.0322 (6)
O4	0.3175 (2)	0.3681 (2)	0.63143 (14)	0.0345 (6)
O5	0.1353 (2)	0.6115 (2)	0.67941 (14)	0.0340 (6)
O6	0.3252 (3)	0.4905 (2)	0.73454 (15)	0.0379 (6)
C11	0.1100 (3)	0.3752 (3)	0.58307 (19)	0.0275 (8)
C12	0.0092 (3)	0.3390 (3)	0.55120 (19)	0.0286 (8)
H12	−0.0671	0.3865	0.5436	0.034*
C13	−0.0023 (4)	0.2475 (3)	0.52832 (19)	0.0309 (8)
C14	0.0985 (4)	0.1678 (3)	0.5284 (2)	0.0358 (9)
H14	0.0749	0.1100	0.5111	0.043*
C15	0.2275 (4)	0.1625 (3)	0.5504 (2)	0.0367 (9)
H15	0.2820	0.1031	0.5432	0.044*
C16	0.2913 (4)	0.2288 (3)	0.5811 (2)	0.0333 (9)
H16	0.3828	0.2085	0.5910	0.040*
C17	0.2414 (3)	0.3206 (3)	0.59971 (19)	0.0282 (8)
C18	−0.1398 (4)	0.2369 (3)	0.5019 (2)	0.0368 (9)
H18	−0.1555	0.3092	0.4676	0.044*
C19	−0.1406 (4)	0.1529 (4)	0.4602 (3)	0.0507 (12)
H19A	−0.0591	0.1674	0.4201	0.076*
H19B	−0.2279	0.1578	0.4402	0.076*
H19C	−0.1351	0.0798	0.4935	0.076*
C20	−0.2628 (4)	0.2133 (4)	0.5661 (3)	0.0507 (12)
H20A	−0.3507	0.2061	0.5489	0.076*
H20B	−0.2694	0.2731	0.5880	0.076*
H20C	−0.2473	0.1455	0.6028	0.076*
C21	0.1803 (3)	0.6385 (3)	0.7315 (2)	0.0308 (8)
C22	0.1265 (4)	0.7295 (3)	0.7500 (2)	0.0362 (9)
H22	0.0556	0.7636	0.7236	0.043*
C23	0.1570 (4)	0.7805 (3)	0.8004 (2)	0.0384 (9)
C24	0.2505 (4)	0.7446 (4)	0.8484 (2)	0.0459 (11)
H24	0.2589	0.7881	0.8794	0.055*
C25	0.3332 (4)	0.6542 (4)	0.8575 (2)	0.0471 (11)
H25	0.3880	0.6444	0.8949	0.057*
C26	0.3496 (4)	0.5761 (4)	0.8216 (2)	0.0427 (10)
H26	0.4126	0.5206	0.8384	0.051*
C27	0.2870 (4)	0.5664 (3)	0.7638 (2)	0.0326 (9)
C28	0.0827 (5)	0.8858 (4)	0.8015 (2)	0.0514 (12)
H28	0.1250	0.9158	0.8354	0.062*
C29	0.1104 (8)	0.9702 (5)	0.7277 (3)	0.098 (2)
H29A	0.2120	0.9764	0.7082	0.147*
H29B	0.0772	1.0404	0.7326	0.147*
H29C	0.0600	0.9485	0.6942	0.147*
C30	−0.0744 (5)	0.8652 (4)	0.8333 (3)	0.0662 (15)
H30A	−0.0864	0.8122	0.8820	0.099*
H30B	−0.1207	0.8367	0.8013	0.099*
H30C	−0.1170	0.9334	0.8370	0.099*
Cu3	0.17278 (4)	0.02271 (4)	0.96179 (2)	0.03381 (14)
O7	0.2242 (2)	−0.0406 (2)	1.05561 (13)	0.0335 (6)
O8	0.3207 (3)	−0.0632 (2)	0.93001 (14)	0.0373 (6)
O9	0.0403 (2)	0.1228 (2)	0.99115 (13)	0.0345 (6)
O10	0.1364 (3)	0.0970 (2)	0.86581 (14)	0.0372 (6)
C31	0.3330 (3)	−0.0999 (3)	1.0536 (2)	0.0290 (8)
C32	0.3849 (3)	−0.1480 (3)	1.1183 (2)	0.0318 (8)
H32	0.3289	−0.1355	1.1603	0.038*
C33	0.5010 (4)	−0.2099 (3)	1.1334 (2)	0.0324 (8)
C34	0.6006 (4)	−0.2409 (3)	1.0828 (2)	0.0392 (9)
H34	0.6750	−0.2827	1.1019	0.047*
C35	0.6061 (4)	−0.2193 (4)	1.0081 (2)	0.0427 (10)
H35	0.6856	−0.2468	0.9834	0.051*
C36	0.5140 (4)	−0.1639 (4)	0.9638 (2)	0.0406 (10)
H36	0.5384	−0.1622	0.9140	0.049*
C37	0.3914 (4)	−0.1103 (3)	0.9806 (2)	0.0312 (8)
C38	0.5224 (4)	−0.2463 (3)	1.2125 (2)	0.0351 (9)
H38	0.6146	−0.2834	1.2138	0.042*
C39	0.5314 (4)	−0.1503 (4)	1.2427 (2)	0.0442 (10)
H39A	0.5999	−0.0955	1.2087	0.066*
H39B	0.5616	−0.1755	1.2903	0.066*
H39C	0.4384	−0.1184	1.2486	0.066*
C40	0.4074 (4)	−0.3286 (4)	1.2609 (2)	0.0490 (11)
H40A	0.4018	−0.3886	1.2400	0.073*
H40B	0.3165	−0.2931	1.2637	0.073*
H40C	0.4300	−0.3568	1.3101	0.073*
C41	0.0096 (3)	0.1981 (3)	0.9356 (2)	0.0313 (8)
C42	−0.0669 (4)	0.2856 (3)	0.9480 (2)	0.0348 (9)
H42	−0.0895	0.2819	0.9983	0.042*
C43	−0.1172 (4)	0.3774 (3)	0.9021 (2)	0.0371 (9)
C44	−0.1036 (4)	0.4003 (4)	0.8260 (2)	0.0444 (10)
H44	−0.1451	0.4654	0.8022	0.053*
C45	−0.0390 (4)	0.3424 (4)	0.7811 (2)	0.0432 (10)
H45	−0.0461	0.3720	0.7311	0.052*
C46	0.0350 (4)	0.2477 (3)	0.7972 (2)	0.0401 (10)
H46	0.0739	0.2242	0.7562	0.048*
C47	0.0613 (4)	0.1813 (3)	0.8643 (2)	0.0336 (9)
C48	−0.1910 (4)	0.4585 (3)	0.9382 (2)	0.0446 (10)
H48	−0.2007	0.4253	0.9923	0.053*
C49	−0.1021 (6)	0.5623 (5)	0.9176 (4)	0.098 (2)
H49A	−0.1381	0.6050	0.9507	0.147*
H49B	−0.1068	0.6045	0.8672	0.147*
H49C	−0.0038	0.5445	0.9216	0.147*
C50	−0.3371 (5)	0.4816 (6)	0.9216 (4)	0.0860 (19)
H50A	−0.3918	0.4131	0.9343	0.129*
H50B	−0.3310	0.5193	0.8694	0.129*
H50C	−0.3839	0.5276	0.9503	0.129*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0273 (3)	0.0325 (4)	0.0344 (4)	0.0024 (2)	−0.0074 (2)	−0.0177 (3)
O1	0.0275 (12)	0.0393 (16)	0.0420 (16)	0.0054 (11)	−0.0106 (11)	−0.0233 (13)
O2	0.0287 (12)	0.0315 (15)	0.0338 (14)	0.0008 (10)	−0.0077 (10)	−0.0152 (12)
C1	0.0291 (17)	0.028 (2)	0.0279 (19)	−0.0013 (14)	−0.0057 (14)	−0.0068 (17)
C2	0.0265 (17)	0.032 (2)	0.034 (2)	0.0021 (15)	−0.0060 (14)	−0.0132 (18)
C3	0.0317 (18)	0.028 (2)	0.032 (2)	0.0004 (15)	−0.0026 (15)	−0.0127 (17)
C4	0.0332 (18)	0.039 (2)	0.040 (2)	−0.0015 (16)	−0.0091 (16)	−0.0235 (19)
C5	0.0296 (18)	0.039 (2)	0.038 (2)	0.0017 (16)	−0.0124 (15)	−0.0134 (19)
C6	0.0252 (16)	0.035 (2)	0.034 (2)	0.0051 (15)	−0.0065 (14)	−0.0123 (18)
C7	0.0269 (17)	0.031 (2)	0.0266 (19)	0.0006 (14)	−0.0031 (14)	−0.0093 (17)
C8	0.0352 (19)	0.036 (2)	0.051 (3)	−0.0029 (17)	−0.0059 (17)	−0.023 (2)
C9	0.068 (3)	0.035 (3)	0.070 (3)	0.009 (2)	−0.018 (2)	−0.020 (3)
C10	0.060 (3)	0.060 (3)	0.069 (3)	0.009 (2)	−0.015 (2)	−0.048 (3)
Cu2	0.0298 (2)	0.0332 (3)	0.0385 (3)	0.00492 (18)	−0.01134 (18)	−0.0183 (2)
O3	0.0310 (12)	0.0341 (16)	0.0378 (15)	0.0040 (11)	−0.0120 (10)	−0.0169 (13)
O4	0.0311 (12)	0.0371 (16)	0.0425 (16)	0.0066 (11)	−0.0140 (11)	−0.0190 (13)
O5	0.0325 (12)	0.0412 (16)	0.0372 (15)	0.0074 (11)	−0.0128 (11)	−0.0220 (13)
O6	0.0401 (14)	0.0381 (17)	0.0444 (16)	0.0105 (12)	−0.0178 (12)	−0.0202 (14)
C11	0.0269 (16)	0.030 (2)	0.0253 (19)	0.0020 (14)	−0.0027 (14)	−0.0093 (17)
C12	0.0265 (17)	0.028 (2)	0.032 (2)	0.0042 (14)	−0.0049 (14)	−0.0099 (17)
C13	0.0331 (18)	0.032 (2)	0.028 (2)	−0.0010 (15)	−0.0052 (15)	−0.0086 (17)
C14	0.042 (2)	0.029 (2)	0.042 (2)	0.0022 (16)	−0.0129 (17)	−0.0162 (19)
C15	0.045 (2)	0.032 (2)	0.040 (2)	0.0127 (17)	−0.0148 (17)	−0.0164 (19)
C16	0.0309 (18)	0.034 (2)	0.039 (2)	0.0064 (15)	−0.0089 (15)	−0.0160 (19)
C17	0.0288 (17)	0.031 (2)	0.0249 (19)	0.0002 (15)	−0.0055 (14)	−0.0085 (16)
C18	0.039 (2)	0.032 (2)	0.046 (2)	0.0029 (16)	−0.0170 (17)	−0.017 (2)
C19	0.047 (2)	0.053 (3)	0.068 (3)	0.006 (2)	−0.026 (2)	−0.034 (3)
C20	0.035 (2)	0.046 (3)	0.075 (3)	−0.0046 (18)	−0.006 (2)	−0.027 (3)
C21	0.0298 (17)	0.034 (2)	0.030 (2)	−0.0003 (15)	−0.0029 (14)	−0.0138 (18)
C22	0.0347 (19)	0.039 (2)	0.038 (2)	0.0035 (16)	−0.0078 (16)	−0.0156 (19)
C23	0.042 (2)	0.038 (2)	0.037 (2)	−0.0084 (17)	0.0044 (17)	−0.020 (2)
C24	0.048 (2)	0.060 (3)	0.037 (2)	−0.008 (2)	−0.0030 (18)	−0.028 (2)
C25	0.053 (2)	0.056 (3)	0.037 (2)	−0.001 (2)	−0.0152 (19)	−0.017 (2)
C26	0.044 (2)	0.050 (3)	0.039 (2)	0.0015 (19)	−0.0151 (18)	−0.016 (2)
C27	0.0323 (18)	0.035 (2)	0.033 (2)	−0.0024 (16)	−0.0050 (15)	−0.0135 (18)
C28	0.069 (3)	0.046 (3)	0.049 (3)	0.000 (2)	−0.010 (2)	−0.029 (2)
C29	0.166 (6)	0.038 (3)	0.074 (4)	0.015 (4)	0.009 (4)	−0.011 (3)
C30	0.060 (3)	0.058 (3)	0.091 (4)	0.017 (2)	−0.008 (3)	−0.043 (3)
Cu3	0.0364 (2)	0.0356 (3)	0.0318 (3)	0.00532 (19)	−0.01016 (19)	−0.0115 (2)
O7	0.0332 (13)	0.0394 (16)	0.0320 (14)	0.0098 (11)	−0.0093 (10)	−0.0153 (13)
O8	0.0449 (14)	0.0406 (17)	0.0310 (14)	0.0067 (12)	−0.0116 (11)	−0.0154 (13)
O9	0.0394 (14)	0.0362 (16)	0.0272 (14)	0.0047 (11)	−0.0100 (11)	−0.0061 (12)
O10	0.0437 (14)	0.0400 (17)	0.0290 (14)	0.0053 (12)	−0.0083 (11)	−0.0112 (13)
C31	0.0288 (17)	0.025 (2)	0.035 (2)	0.0009 (14)	−0.0080 (15)	−0.0114 (17)
C32	0.0329 (18)	0.037 (2)	0.0269 (19)	0.0026 (16)	−0.0055 (15)	−0.0112 (17)
C33	0.0306 (18)	0.029 (2)	0.040 (2)	−0.0010 (15)	−0.0059 (15)	−0.0138 (18)
C34	0.035 (2)	0.038 (2)	0.046 (3)	0.0081 (17)	−0.0101 (17)	−0.013 (2)
C35	0.0336 (19)	0.055 (3)	0.042 (2)	0.0085 (18)	−0.0007 (17)	−0.022 (2)
C36	0.037 (2)	0.053 (3)	0.036 (2)	0.0055 (18)	−0.0072 (17)	−0.020 (2)
C37	0.0327 (18)	0.032 (2)	0.032 (2)	−0.0041 (15)	−0.0066 (15)	−0.0135 (18)
C38	0.0344 (19)	0.035 (2)	0.036 (2)	0.0102 (16)	−0.0115 (16)	−0.0086 (18)
C39	0.049 (2)	0.048 (3)	0.042 (2)	0.0075 (19)	−0.0164 (19)	−0.018 (2)
C40	0.052 (2)	0.049 (3)	0.041 (2)	0.000 (2)	−0.0111 (19)	−0.005 (2)
C41	0.0298 (17)	0.035 (2)	0.031 (2)	−0.0041 (15)	−0.0064 (15)	−0.0108 (18)
C42	0.0363 (19)	0.035 (2)	0.033 (2)	−0.0027 (16)	−0.0049 (16)	−0.0093 (18)
C43	0.0303 (18)	0.034 (2)	0.044 (2)	−0.0014 (16)	−0.0056 (16)	−0.0063 (19)
C44	0.045 (2)	0.034 (2)	0.049 (3)	−0.0001 (18)	−0.0080 (19)	−0.005 (2)
C45	0.047 (2)	0.050 (3)	0.029 (2)	0.001 (2)	−0.0104 (17)	−0.003 (2)
C46	0.044 (2)	0.043 (3)	0.033 (2)	0.0013 (18)	−0.0064 (17)	−0.011 (2)
C47	0.0324 (18)	0.034 (2)	0.036 (2)	−0.0011 (16)	−0.0102 (15)	−0.0111 (18)
C48	0.043 (2)	0.037 (3)	0.049 (3)	0.0045 (18)	−0.0025 (18)	−0.009 (2)
C49	0.082 (4)	0.069 (4)	0.152 (7)	−0.011 (3)	0.019 (4)	−0.067 (5)
C50	0.052 (3)	0.109 (5)	0.109 (5)	0.028 (3)	−0.015 (3)	−0.052 (4)

Geometric parameters (Å, º)

Cu1—O2^i	1.922 (2)	C25—C26	1.379 (6)
Cu1—O2	1.922 (2)	C25—H25	0.9500
Cu1—O1	1.929 (2)	C26—C27	1.402 (5)
Cu1—O1^i	1.929 (2)	C26—H26	0.9500
O1—C1	1.309 (4)	C28—C29	1.506 (7)
O2—C7	1.301 (4)	C28—C30	1.526 (6)
C1—C2	1.385 (5)	C28—H28	1.0000
C1—C7	1.457 (5)	C29—H29A	0.9800
C2—C3	1.401 (5)	C29—H29B	0.9800
C2—H2	0.9500	C29—H29C	0.9800
C3—C4	1.390 (5)	C30—H30A	0.9800
C3—C8	1.519 (5)	C30—H30B	0.9800
C4—C5	1.386 (5)	C30—H30C	0.9800
C4—H4	0.9500	Cu3—O8	1.915 (3)
C5—C6	1.374 (5)	Cu3—O7	1.915 (2)
C5—H5	0.9500	Cu3—O10	1.921 (3)
C6—C7	1.405 (5)	Cu3—O9	1.931 (3)
C6—H6	0.9500	O7—C31	1.286 (4)
C8—C10	1.520 (5)	O8—C37	1.293 (4)
C8—C9	1.527 (6)	O9—C41	1.297 (4)
C8—H8	1.0000	O10—C47	1.290 (5)
C9—H9A	0.9800	C31—C32	1.402 (5)
C9—H9B	0.9800	C31—C37	1.475 (5)
C9—H9C	0.9800	C32—C33	1.384 (5)
C10—H10A	0.9800	C32—H32	0.9500
C10—H10B	0.9800	C33—C34	1.390 (5)
C10—H10C	0.9800	C33—C38	1.521 (5)
Cu2—O5	1.917 (3)	C34—C35	1.387 (6)
Cu2—O3	1.918 (2)	C34—H34	0.9500
Cu2—O4	1.921 (3)	C35—C36	1.386 (5)
Cu2—O6	1.931 (2)	C35—H35	0.9500
O3—C11	1.294 (4)	C36—C37	1.393 (5)
O4—C17	1.301 (4)	C36—H36	0.9500
O5—C21	1.305 (4)	C38—C40	1.524 (5)
O6—C27	1.287 (4)	C38—C39	1.529 (6)
C11—C12	1.395 (5)	C38—H38	1.0000
C11—C17	1.474 (5)	C39—H39A	0.9800
C12—C13	1.391 (5)	C39—H39B	0.9800
C12—H12	0.9500	C39—H39C	0.9800
C13—C14	1.399 (5)	C40—H40A	0.9800
C13—C18	1.524 (5)	C40—H40B	0.9800
C14—C15	1.377 (5)	C40—H40C	0.9800
C14—H14	0.9500	C41—C42	1.392 (5)
C15—C16	1.385 (5)	C41—C47	1.465 (5)
C15—H15	0.9500	C42—C43	1.393 (5)
C16—C17	1.390 (5)	C42—H42	0.9500
C16—H16	0.9500	C43—C44	1.402 (6)
C18—C20	1.524 (6)	C43—C48	1.524 (6)
C18—C19	1.534 (5)	C44—C45	1.372 (6)
C18—H18	1.0000	C44—H44	0.9500
C19—H19A	0.9800	C45—C46	1.384 (6)
C19—H19B	0.9800	C45—H45	0.9500
C19—H19C	0.9800	C46—C47	1.396 (5)
C20—H20A	0.9800	C46—H46	0.9500
C20—H20B	0.9800	C48—C50	1.504 (6)
C20—H20C	0.9800	C48—C49	1.513 (7)
C21—C22	1.391 (5)	C48—H48	1.0000
C21—C27	1.470 (5)	C49—H49A	0.9800
C22—C23	1.402 (5)	C49—H49B	0.9800
C22—H22	0.9500	C49—H49C	0.9800
C23—C24	1.387 (6)	C50—H50A	0.9800
C23—C28	1.527 (6)	C50—H50B	0.9800
C24—C25	1.383 (6)	C50—H50C	0.9800
C24—H24	0.9500
O2^i—Cu1—O2	180.000 (1)	C25—C26—H26	115.2
O2^i—Cu1—O1	96.10 (10)	C27—C26—H26	115.2
O2—Cu1—O1	83.90 (10)	O6—C27—C26	119.3 (4)
O2^i—Cu1—O1^i	83.90 (10)	O6—C27—C21	115.5 (3)
O2—Cu1—O1^i	96.10 (10)	C26—C27—C21	125.2 (4)
O1—Cu1—O1^i	180.00 (12)	C29—C28—C30	112.8 (5)
C1—O1—Cu1	112.5 (2)	C29—C28—C23	112.0 (4)
C7—O2—Cu1	112.3 (2)	C30—C28—C23	111.7 (4)
O1—C1—C2	118.7 (3)	C29—C28—H28	106.6
O1—C1—C7	114.6 (3)	C30—C28—H28	106.6
C2—C1—C7	126.7 (3)	C23—C28—H28	106.6
C1—C2—C3	133.0 (3)	C28—C29—H29A	109.5
C1—C2—H2	113.5	C28—C29—H29B	109.5
C3—C2—H2	113.5	H29A—C29—H29B	109.5
C4—C3—C2	125.3 (3)	C28—C29—H29C	109.5
C4—C3—C8	119.9 (3)	H29A—C29—H29C	109.5
C2—C3—C8	114.7 (3)	H29B—C29—H29C	109.5
C5—C4—C3	129.0 (3)	C28—C30—H30A	109.5
C5—C4—H4	115.5	C28—C30—H30B	109.5
C3—C4—H4	115.5	H30A—C30—H30B	109.5
C6—C5—C4	130.6 (3)	C28—C30—H30C	109.5
C6—C5—H5	114.7	H30A—C30—H30C	109.5
C4—C5—H5	114.7	H30B—C30—H30C	109.5
C5—C6—C7	129.7 (3)	O8—Cu3—O7	83.64 (10)
C5—C6—H6	115.2	O8—Cu3—O10	95.74 (11)
C7—C6—H6	115.2	O7—Cu3—O10	174.19 (11)
O2—C7—C6	118.3 (3)	O8—Cu3—O9	173.28 (11)
O2—C7—C1	116.1 (3)	O7—Cu3—O9	96.45 (10)
C6—C7—C1	125.6 (3)	O10—Cu3—O9	83.49 (11)
C3—C8—C10	115.2 (3)	C31—O7—Cu3	113.4 (2)
C3—C8—C9	110.3 (3)	C37—O8—Cu3	112.9 (2)
C10—C8—C9	110.8 (4)	C41—O9—Cu3	112.2 (2)
C3—C8—H8	106.7	C47—O10—Cu3	112.9 (2)
C10—C8—H8	106.7	O7—C31—C32	119.2 (3)
C9—C8—H8	106.7	O7—C31—C37	114.7 (3)
C8—C9—H9A	109.5	C32—C31—C37	126.1 (3)
C8—C9—H9B	109.5	C33—C32—C31	133.1 (4)
H9A—C9—H9B	109.5	C33—C32—H32	113.4
C8—C9—H9C	109.5	C31—C32—H32	113.4
H9A—C9—H9C	109.5	C32—C33—C34	126.0 (4)
H9B—C9—H9C	109.5	C32—C33—C38	117.0 (3)
C8—C10—H10A	109.5	C34—C33—C38	117.0 (3)
C8—C10—H10B	109.5	C35—C34—C33	128.8 (4)
H10A—C10—H10B	109.5	C35—C34—H34	115.6
C8—C10—H10C	109.5	C33—C34—H34	115.6
H10A—C10—H10C	109.5	C36—C35—C34	130.3 (4)
H10B—C10—H10C	109.5	C36—C35—H35	114.9
O5—Cu2—O3	95.59 (10)	C34—C35—H35	114.9
O5—Cu2—O4	178.97 (10)	C35—C36—C37	130.4 (4)
O3—Cu2—O4	83.44 (10)	C35—C36—H36	114.8
O5—Cu2—O6	83.13 (11)	C37—C36—H36	114.8
O3—Cu2—O6	163.45 (11)	O8—C37—C36	120.0 (3)
O4—Cu2—O6	97.90 (11)	O8—C37—C31	114.8 (3)
C11—O3—Cu2	113.6 (2)	C36—C37—C31	125.2 (3)
C17—O4—Cu2	112.9 (2)	C33—C38—C40	111.4 (3)
C21—O5—Cu2	114.1 (2)	C33—C38—C39	112.0 (3)
C27—O6—Cu2	113.4 (2)	C40—C38—C39	110.7 (3)
O3—C11—C12	119.8 (3)	C33—C38—H38	107.5
O3—C11—C17	114.2 (3)	C40—C38—H38	107.5
C12—C11—C17	126.0 (3)	C39—C38—H38	107.5
C13—C12—C11	132.9 (3)	C38—C39—H39A	109.5
C13—C12—H12	113.5	C38—C39—H39B	109.5
C11—C12—H12	113.5	H39A—C39—H39B	109.5
C12—C13—C14	126.0 (3)	C38—C39—H39C	109.5
C12—C13—C18	114.5 (3)	H39A—C39—H39C	109.5
C14—C13—C18	119.6 (3)	H39B—C39—H39C	109.5
C15—C14—C13	128.3 (4)	C38—C40—H40A	109.5
C15—C14—H14	115.8	C38—C40—H40B	109.5
C13—C14—H14	115.8	H40A—C40—H40B	109.5
C14—C15—C16	131.0 (4)	C38—C40—H40C	109.5
C14—C15—H15	114.5	H40A—C40—H40C	109.5
C16—C15—H15	114.5	H40B—C40—H40C	109.5
C15—C16—C17	129.6 (3)	O9—C41—C42	118.8 (3)
C15—C16—H16	115.2	O9—C41—C47	114.9 (3)
C17—C16—H16	115.2	C42—C41—C47	126.3 (4)
O4—C17—C16	119.2 (3)	C41—C42—C43	133.3 (4)
O4—C17—C11	115.0 (3)	C41—C42—H42	113.4
C16—C17—C11	125.8 (3)	C43—C42—H42	113.4
C20—C18—C13	109.9 (3)	C42—C43—C44	125.0 (4)
C20—C18—C19	110.2 (3)	C42—C43—C48	116.5 (4)
C13—C18—C19	115.1 (3)	C44—C43—C48	118.4 (4)
C20—C18—H18	107.1	C45—C44—C43	129.4 (4)
C13—C18—H18	107.1	C45—C44—H44	115.3
C19—C18—H18	107.1	C43—C44—H44	115.3
C18—C19—H19A	109.5	C44—C45—C46	130.2 (4)
C18—C19—H19B	109.5	C44—C45—H45	114.9
H19A—C19—H19B	109.5	C46—C45—H45	114.9
C18—C19—H19C	109.5	C45—C46—C47	130.1 (4)
H19A—C19—H19C	109.5	C45—C46—H46	114.9
H19B—C19—H19C	109.5	C47—C46—H46	114.9
C18—C20—H20A	109.5	O10—C47—C46	119.2 (4)
C18—C20—H20B	109.5	O10—C47—C41	115.4 (3)
H20A—C20—H20B	109.5	C46—C47—C41	125.5 (4)
C18—C20—H20C	109.5	C50—C48—C49	111.1 (5)
H20A—C20—H20C	109.5	C50—C48—C43	112.6 (4)
H20B—C20—H20C	109.5	C49—C48—C43	110.8 (3)
O5—C21—C22	118.9 (3)	C50—C48—H48	107.4
O5—C21—C27	113.9 (3)	C49—C48—H48	107.4
C22—C21—C27	127.2 (3)	C43—C48—H48	107.4
C21—C22—C23	132.1 (4)	C48—C49—H49A	109.5
C21—C22—H22	113.9	C48—C49—H49B	109.5
C23—C22—H22	113.9	H49A—C49—H49B	109.5
C24—C23—C22	125.8 (4)	C48—C49—H49C	109.5
C24—C23—C28	117.1 (4)	H49A—C49—H49C	109.5
C22—C23—C28	117.1 (4)	H49B—C49—H49C	109.5
C25—C24—C23	129.0 (4)	C48—C50—H50A	109.5
C25—C24—H24	115.5	C48—C50—H50B	109.5
C23—C24—H24	115.5	H50A—C50—H50B	109.5
C26—C25—C24	131.0 (4)	C48—C50—H50C	109.5
C26—C25—H25	114.5	H50A—C50—H50C	109.5
C24—C25—H25	114.5	H50B—C50—H50C	109.5
C25—C26—C27	129.6 (4)
O2^i—Cu1—O1—C1	173.1 (2)	C23—C24—C25—C26	1.6 (8)
O2—Cu1—O1—C1	−6.9 (2)	C24—C25—C26—C27	0.8 (8)
O1—Cu1—O2—C7	5.9 (2)	Cu2—O6—C27—C26	179.9 (3)
O1^i—Cu1—O2—C7	−174.1 (2)	Cu2—O6—C27—C21	−1.3 (4)
Cu1—O1—C1—C2	−172.2 (3)	C25—C26—C27—O6	175.0 (4)
Cu1—O1—C1—C7	6.5 (4)	C25—C26—C27—C21	−3.7 (7)
O1—C1—C2—C3	179.8 (4)	O5—C21—C27—O6	2.8 (5)
C7—C1—C2—C3	1.3 (7)	C22—C21—C27—O6	−176.5 (3)
C1—C2—C3—C4	0.9 (7)	O5—C21—C27—C26	−178.4 (3)
C1—C2—C3—C8	−176.7 (4)	C22—C21—C27—C26	2.3 (6)
C2—C3—C4—C5	0.2 (7)	C24—C23—C28—C29	122.3 (5)
C8—C3—C4—C5	177.8 (4)	C22—C23—C28—C29	−56.8 (6)
C3—C4—C5—C6	−1.2 (7)	C24—C23—C28—C30	−110.1 (4)
C4—C5—C6—C7	−1.5 (7)	C22—C23—C28—C30	70.8 (5)
Cu1—O2—C7—C6	177.4 (2)	O8—Cu3—O7—C31	5.0 (2)
Cu1—O2—C7—C1	−4.0 (4)	O9—Cu3—O7—C31	−168.2 (2)
C5—C6—C7—O2	−176.7 (4)	O7—Cu3—O8—C37	−7.0 (2)
C5—C6—C7—C1	4.8 (6)	O10—Cu3—O8—C37	167.2 (2)
O1—C1—C7—O2	−1.6 (5)	O7—Cu3—O9—C41	164.3 (2)
C2—C1—C7—O2	176.9 (3)	O10—Cu3—O9—C41	−9.8 (2)
O1—C1—C7—C6	176.8 (3)	O8—Cu3—O10—C47	−165.3 (2)
C2—C1—C7—C6	−4.6 (6)	O9—Cu3—O10—C47	8.0 (2)
C4—C3—C8—C10	22.0 (5)	Cu3—O7—C31—C32	177.8 (3)
C2—C3—C8—C10	−160.3 (4)	Cu3—O7—C31—C37	−2.3 (4)
C4—C3—C8—C9	−104.4 (4)	O7—C31—C32—C33	−176.2 (4)
C2—C3—C8—C9	73.4 (4)	C37—C31—C32—C33	3.9 (7)
O5—Cu2—O3—C11	−172.0 (2)	C31—C32—C33—C34	−0.2 (7)
O4—Cu2—O3—C11	8.3 (2)	C31—C32—C33—C38	179.1 (4)
O6—Cu2—O3—C11	−87.3 (4)	C32—C33—C34—C35	−0.9 (7)
O3—Cu2—O4—C17	−7.6 (2)	C38—C33—C34—C35	179.8 (4)
O6—Cu2—O4—C17	155.8 (2)	C33—C34—C35—C36	−1.7 (8)
O3—Cu2—O5—C21	165.2 (2)	C34—C35—C36—C37	2.6 (8)
O6—Cu2—O5—C21	1.8 (2)	Cu3—O8—C37—C36	−171.5 (3)
O5—Cu2—O6—C27	−0.1 (2)	Cu3—O8—C37—C31	7.5 (4)
O3—Cu2—O6—C27	−86.6 (5)	C35—C36—C37—O8	179.9 (4)
O4—Cu2—O6—C27	179.8 (2)	C35—C36—C37—C31	1.1 (7)
Cu2—O3—C11—C12	172.0 (3)	O7—C31—C37—O8	−3.5 (5)
Cu2—O3—C11—C17	−7.4 (4)	C32—C31—C37—O8	176.4 (3)
O3—C11—C12—C13	−177.7 (4)	O7—C31—C37—C36	175.4 (3)
C17—C11—C12—C13	1.6 (6)	C32—C31—C37—C36	−4.7 (6)
C11—C12—C13—C14	−4.4 (7)	C32—C33—C38—C40	68.0 (4)
C11—C12—C13—C18	175.0 (4)	C34—C33—C38—C40	−112.6 (4)
C12—C13—C14—C15	−0.1 (7)	C32—C33—C38—C39	−56.5 (4)
C18—C13—C14—C15	−179.6 (4)	C34—C33—C38—C39	122.8 (4)
C13—C14—C15—C16	3.5 (8)	Cu3—O9—C41—C42	−170.1 (2)
C14—C15—C16—C17	0.9 (7)	Cu3—O9—C41—C47	9.8 (3)
Cu2—O4—C17—C16	−177.7 (3)	O9—C41—C42—C43	−179.4 (4)
Cu2—O4—C17—C11	5.6 (4)	C47—C41—C42—C43	0.8 (6)
C15—C16—C17—O4	176.9 (4)	C41—C42—C43—C44	2.7 (6)
C15—C16—C17—C11	−6.7 (6)	C41—C42—C43—C48	−176.6 (4)
O3—C11—C17—O4	1.2 (4)	C42—C43—C44—C45	−1.3 (6)
C12—C11—C17—O4	−178.1 (3)	C48—C43—C44—C45	178.0 (4)
O3—C11—C17—C16	−175.3 (3)	C43—C44—C45—C46	−2.6 (7)
C12—C11—C17—C16	5.4 (6)	C44—C45—C46—C47	2.5 (7)
C12—C13—C18—C20	−68.6 (4)	Cu3—O10—C47—C46	175.5 (3)
C14—C13—C18—C20	110.9 (4)	Cu3—O10—C47—C41	−4.9 (4)
C12—C13—C18—C19	166.3 (4)	C45—C46—C47—O10	−178.6 (4)
C14—C13—C18—C19	−14.2 (5)	C45—C46—C47—C41	1.8 (6)
Cu2—O5—C21—C22	176.5 (3)	O9—C41—C47—O10	−3.3 (4)
Cu2—O5—C21—C27	−2.9 (4)	C42—C41—C47—O10	176.5 (3)
O5—C21—C22—C23	−177.2 (4)	O9—C41—C47—C46	176.2 (3)
C27—C21—C22—C23	2.1 (7)	C42—C41—C47—C46	−3.9 (6)
C21—C22—C23—C24	−3.5 (7)	C42—C43—C48—C50	−124.8 (4)
C21—C22—C23—C28	175.5 (4)	C44—C43—C48—C50	55.8 (5)
C22—C23—C24—C25	0.5 (7)	C42—C43—C48—C49	110.1 (5)
C28—C23—C24—C25	−178.4 (4)	C44—C43—C48—C49	−69.3 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.