Tetra-kis{2-[2-(2,6-dichloro-anilino)phen-yl]ethano-ato-κ(2)O:O'}bis-[(dimethyl sulfoxide-κO)copper(II)](Cu-Cu): a binuclear Cu(II) complex with the non-steroidal anti-inflammatory drug diclofenac.

The title compound, [Cu(2)(C(14)H(10)Cl(2)NO(2))(4)(C(2)H(6)OS)(2)], comprises a Cu(II) (2) core that is quadruply bridged by four carboxyl-ate ligands with the dimethyl sulfoxide ligands binding along the Cu⋯Cu axis. The four carboxyl-ate ligands bind in a bidentate syn-syn bridging mode. Mol-ecules reside on crystallographic inversion centres bis-ecting the mid-point of the Cu⋯Cu axis. There are no inter-molecular inter-actions of note.

Related literature

CuII complexes of non-steroidal anti-inflammatory drugs (NSAIDs) show enhanced anti-inflammatory activity and reduced gastrointestinal toxicity compared with their uncomplexed parent drug, see: Weder et al. (2002 ▶). The structure of the Cu–NSAID is likely to be an important factor for its biological activity. For example, the anti-tumor activity of the monomeric CuII complex of aspirin ([Cu(Asp)2(py)2]) is reportedly more effective than the dimeric [Cu2(Asp)4] complex, see: Oberley & Buettner (1979 ▶). It has been shown that dinuclear Cu–NSAID complexes exhibit similar bio­logical activity to mononuclear complexes, but with higher stability (Dimiza et al., 2011 ▶), making them relevant compounds in the treatment of tumor cell lines (Theodorou et al., 1999 ▶). For mono- and binuclear CuII complexes of diclofenac, see: Sayen et al. (2012 ▶) for [Cu(diclofenac)2(H2O)2]·2H2O and Kovala-Demertzi et al. (1997 ▶) for [Cu2(diclofenac)4(DMF)2].

Experimental

Crystal data

[Cu2(C14H10Cl2NO2)4(C2H6OS)2]

M = 1463.90

Triclinic,

a = 10.357 (5) Å

b = 12.787 (5) Å

c = 12.925 (5) Å

α = 81.605 (5)°

β = 75.561 (5)°

γ = 68.489 (5)°

V = 1539.4 (11) Å3

Z = 1

Mo Kα radiation

μ = 1.17 mm−1

T = 100 K

0.30 × 0.21 × 0.18 mm

Data collection

Oxford Diffraction SuperNova Atlas diffractometer

Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010 ▶) T min = 0.867, T max = 1.000

42084 measured reflections

10796 independent reflections

9113 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 0.99

10796 reflections

396 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201152X/gg2076sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201152X/gg2076Isup2.hkl

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

[Cu2(C14H10Cl2NO2)4(C2H6OS)2]	Z = 1
Mr = 1463.90	F(000) = 746
Triclinic, P1	Dx = 1.579 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.357 (5) Å	Cell parameters from 19895 reflections
b = 12.787 (5) Å	θ = 3.0–33.3°
c = 12.925 (5) Å	µ = 1.17 mm−1
α = 81.605 (5)°	T = 100 K
β = 75.561 (5)°	Prismatic, green
γ = 68.489 (5)°	0.30 × 0.21 × 0.18 mm
V = 1539.4 (11) Å3

Oxford Diffraction SuperNova Atlas diffractometer	10796 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	9113 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 10.4508 pixels mm-1	θmax = 33.4°, θmin = 3.0°
CCD scans	h = −15→15
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010)	k = −18→19
Tmin = 0.867, Tmax = 1.000	l = −19→19
42084 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.0335P)2 + 0.9652P] where P = (Fo2 + 2Fc2)/3
10796 reflections	(Δ/σ)max = 0.012
396 parameters	Δρmax = 0.71 e Å−3
1 restraint	Δρmin = −0.51 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cu1	0.120933 (16)	0.021416 (13)	0.473791 (12)	0.01201 (4)
Cl3	−0.08018 (4)	0.53916 (3)	0.12807 (3)	0.02570 (8)
Cl2	−0.24985 (4)	0.22114 (3)	1.09549 (3)	0.02408 (7)
S1D	0.46463 (3)	−0.01303 (3)	0.37338 (3)	0.01652 (7)
Cl4	0.36720 (4)	0.26927 (3)	0.29584 (3)	0.02399 (8)
Cl1	−0.13597 (4)	−0.16032 (3)	0.90149 (3)	0.02907 (9)
O2	0.02500 (10)	0.14887 (8)	0.38286 (8)	0.01807 (19)
O1D	0.31958 (10)	0.04789 (8)	0.43929 (8)	0.01638 (18)
O1	0.03591 (10)	0.12257 (9)	0.59225 (8)	0.0190 (2)
O1'	0.16521 (11)	−0.08291 (9)	0.36053 (8)	0.0197 (2)
O2'	0.17899 (11)	−0.11273 (9)	0.57158 (9)	0.0205 (2)
N012	0.05900 (13)	0.35894 (10)	0.27795 (10)	0.0178 (2)
H012	0.097 (2)	0.2948 (17)	0.2976 (15)	0.021*
C14	−0.21991 (14)	0.07801 (12)	1.10092 (11)	0.0177 (2)
C28	−0.06437 (14)	0.42098 (11)	0.35062 (11)	0.0169 (2)
C8	−0.31758 (14)	0.17788 (12)	0.88170 (10)	0.0159 (2)
N1	−0.19748 (13)	0.08795 (11)	0.90651 (10)	0.0205 (2)
H1	−0.153 (2)	0.0471 (17)	0.8576 (16)	0.025*
C31	0.17566 (15)	0.56327 (12)	0.07734 (12)	0.0199 (3)
H31	0.1352	0.6248	0.0308	0.024*
C13	−0.21504 (15)	0.01805 (13)	1.19914 (11)	0.0199 (3)
H13	−0.2323	0.0557	1.2620	0.024*
C27	−0.07237 (16)	0.51895 (12)	0.39113 (12)	0.0205 (3)
H27	0.0052	0.5456	0.3691	0.025*
C2	−0.15089 (14)	0.23216 (12)	0.72217 (11)	0.0162 (2)
H2A	−0.0860	0.2187	0.7713	0.019*
H2B	−0.1537	0.3038	0.6800	0.019*
C9	−0.19799 (14)	0.02709 (12)	1.00581 (11)	0.0176 (3)
C1	−0.08847 (14)	0.13770 (11)	0.64569 (10)	0.0136 (2)
C30	0.09412 (15)	0.50313 (12)	0.14053 (11)	0.0187 (3)
C1D	0.44047 (16)	−0.01951 (14)	0.24247 (11)	0.0219 (3)
H02A	0.3665	−0.0520	0.2481	0.033*
H02B	0.5298	−0.0667	0.1995	0.033*
H02C	0.4118	0.0566	0.2080	0.033*
C5	−0.55113 (15)	0.35002 (13)	0.82325 (12)	0.0232 (3)
H5	−0.6306	0.4077	0.8023	0.028*
C12	−0.18466 (15)	−0.09755 (14)	1.20482 (12)	0.0221 (3)
H12	−0.1810	−0.1394	1.2718	0.026*
C11	−0.15969 (15)	−0.15203 (13)	1.11267 (13)	0.0223 (3)
H11	−0.1375	−0.2313	1.1161	0.027*
C7	−0.45321 (15)	0.19793 (13)	0.94636 (11)	0.0190 (3)
H7	−0.4663	0.1523	1.0103	0.023*
C6	−0.56910 (15)	0.28436 (13)	0.91755 (12)	0.0216 (3)
H6	−0.6609	0.2986	0.9625	0.026*
C2D	0.50562 (18)	−0.15937 (13)	0.41473 (14)	0.0281 (3)
H03A	0.5213	−0.1717	0.4879	0.042*
H03B	0.5917	−0.2037	0.3665	0.042*
H03C	0.4263	−0.1828	0.4124	0.042*
C4	−0.41565 (15)	0.33051 (12)	0.75986 (12)	0.0198 (3)
H4	−0.4034	0.3757	0.6955	0.024*
C26	−0.19259 (16)	0.57789 (13)	0.46336 (12)	0.0227 (3)
H26	−0.1974	0.6449	0.4900	0.027*
C22	−0.17896 (14)	0.28408 (11)	0.32842 (11)	0.0162 (2)
H22A	−0.1299	0.2857	0.2522	0.019*
H22B	−0.2780	0.2907	0.3311	0.019*
C32	0.31703 (15)	0.53252 (12)	0.08282 (12)	0.0205 (3)
H32	0.3734	0.5742	0.0412	0.025*
C10	−0.16740 (15)	−0.09000 (13)	1.01577 (11)	0.0196 (3)
C21	−0.10505 (14)	0.17246 (11)	0.38384 (10)	0.0142 (2)
C23	−0.17988 (14)	0.38320 (11)	0.37996 (11)	0.0159 (2)
C3	−0.29740 (14)	0.24632 (11)	0.78848 (10)	0.0151 (2)
C24	−0.29898 (15)	0.44231 (12)	0.45452 (12)	0.0201 (3)
H24	−0.3769	0.4160	0.4769	0.024*
C25	−0.30575 (16)	0.53873 (13)	0.49652 (13)	0.0243 (3)
H25	−0.3872	0.5775	0.5475	0.029*
C33	0.37580 (15)	0.44104 (12)	0.14897 (12)	0.0196 (3)
H33	0.4735	0.4179	0.1507	0.024*
C34	0.29167 (14)	0.38323 (11)	0.21269 (11)	0.0167 (2)
C29	0.14713 (14)	0.41375 (11)	0.21268 (11)	0.0163 (2)

	U11	U22	U33	U12	U13	U23
Cu1	0.01134 (7)	0.01206 (8)	0.01214 (7)	−0.00424 (6)	−0.00065 (5)	−0.00190 (5)
Cl3	0.01649 (15)	0.03093 (19)	0.02816 (18)	−0.00870 (14)	−0.00621 (13)	0.00686 (14)
Cl2	0.02819 (18)	0.02315 (17)	0.02436 (16)	−0.01136 (14)	−0.00732 (14)	−0.00237 (13)
S1D	0.01188 (14)	0.01976 (16)	0.01874 (15)	−0.00561 (12)	−0.00296 (11)	−0.00384 (12)
Cl4	0.02377 (17)	0.01794 (16)	0.02430 (16)	−0.00113 (13)	−0.00500 (13)	0.00066 (12)
Cl1	0.02692 (18)	0.02932 (19)	0.02732 (18)	−0.00156 (15)	−0.00549 (14)	−0.01270 (15)
O2	0.0154 (4)	0.0174 (5)	0.0202 (5)	−0.0061 (4)	−0.0037 (4)	0.0033 (4)
O1D	0.0130 (4)	0.0179 (5)	0.0176 (4)	−0.0055 (4)	−0.0002 (3)	−0.0039 (4)
O1	0.0154 (4)	0.0255 (5)	0.0171 (4)	−0.0091 (4)	0.0031 (4)	−0.0097 (4)
O1'	0.0168 (5)	0.0198 (5)	0.0232 (5)	−0.0089 (4)	0.0040 (4)	−0.0112 (4)
O2'	0.0176 (5)	0.0186 (5)	0.0256 (5)	−0.0086 (4)	−0.0057 (4)	0.0057 (4)
N012	0.0174 (5)	0.0128 (5)	0.0200 (5)	−0.0058 (4)	0.0018 (4)	0.0003 (4)
C14	0.0140 (6)	0.0215 (7)	0.0176 (6)	−0.0060 (5)	−0.0030 (5)	−0.0018 (5)
C28	0.0164 (6)	0.0154 (6)	0.0163 (6)	−0.0046 (5)	−0.0010 (5)	−0.0003 (5)
C8	0.0138 (6)	0.0196 (6)	0.0139 (5)	−0.0041 (5)	−0.0031 (4)	−0.0048 (5)
N1	0.0152 (5)	0.0249 (6)	0.0139 (5)	−0.0001 (5)	0.0005 (4)	−0.0023 (4)
C31	0.0186 (6)	0.0176 (6)	0.0207 (6)	−0.0060 (5)	−0.0012 (5)	0.0019 (5)
C13	0.0152 (6)	0.0294 (7)	0.0163 (6)	−0.0087 (5)	−0.0040 (5)	−0.0014 (5)
C27	0.0205 (6)	0.0192 (7)	0.0220 (6)	−0.0080 (5)	−0.0023 (5)	−0.0026 (5)
C2	0.0149 (6)	0.0175 (6)	0.0167 (6)	−0.0064 (5)	−0.0002 (5)	−0.0062 (5)
C9	0.0116 (5)	0.0231 (7)	0.0159 (6)	−0.0038 (5)	−0.0016 (5)	−0.0019 (5)
C1	0.0139 (5)	0.0135 (6)	0.0123 (5)	−0.0031 (4)	−0.0028 (4)	−0.0013 (4)
C30	0.0150 (6)	0.0198 (6)	0.0206 (6)	−0.0070 (5)	−0.0021 (5)	0.0000 (5)
C1D	0.0190 (6)	0.0308 (8)	0.0181 (6)	−0.0108 (6)	−0.0015 (5)	−0.0066 (5)
C5	0.0145 (6)	0.0254 (7)	0.0257 (7)	−0.0015 (5)	−0.0044 (5)	−0.0035 (6)
C12	0.0150 (6)	0.0296 (8)	0.0202 (6)	−0.0072 (5)	−0.0059 (5)	0.0051 (6)
C11	0.0152 (6)	0.0213 (7)	0.0279 (7)	−0.0035 (5)	−0.0062 (5)	0.0012 (6)
C7	0.0157 (6)	0.0244 (7)	0.0157 (6)	−0.0066 (5)	−0.0005 (5)	−0.0033 (5)
C6	0.0124 (6)	0.0288 (8)	0.0220 (6)	−0.0053 (5)	−0.0005 (5)	−0.0074 (6)
C2D	0.0259 (8)	0.0193 (7)	0.0342 (8)	−0.0007 (6)	−0.0085 (6)	−0.0017 (6)
C4	0.0181 (6)	0.0197 (6)	0.0196 (6)	−0.0043 (5)	−0.0032 (5)	−0.0025 (5)
C26	0.0226 (7)	0.0181 (7)	0.0260 (7)	−0.0040 (5)	−0.0040 (6)	−0.0069 (5)
C22	0.0162 (6)	0.0161 (6)	0.0163 (6)	−0.0055 (5)	−0.0050 (5)	0.0013 (5)
C32	0.0190 (6)	0.0197 (7)	0.0217 (6)	−0.0091 (5)	0.0017 (5)	−0.0015 (5)
C10	0.0141 (6)	0.0226 (7)	0.0196 (6)	−0.0023 (5)	−0.0032 (5)	−0.0052 (5)
C21	0.0156 (6)	0.0143 (6)	0.0116 (5)	−0.0044 (5)	−0.0015 (4)	−0.0024 (4)
C23	0.0157 (6)	0.0142 (6)	0.0168 (6)	−0.0041 (5)	−0.0037 (5)	0.0002 (4)
C3	0.0132 (5)	0.0170 (6)	0.0153 (5)	−0.0049 (5)	−0.0006 (4)	−0.0068 (4)
C24	0.0148 (6)	0.0210 (7)	0.0220 (6)	−0.0043 (5)	−0.0015 (5)	−0.0022 (5)
C25	0.0183 (7)	0.0240 (7)	0.0259 (7)	−0.0025 (5)	0.0000 (5)	−0.0084 (6)
C33	0.0147 (6)	0.0199 (7)	0.0233 (6)	−0.0056 (5)	−0.0004 (5)	−0.0056 (5)
C34	0.0168 (6)	0.0135 (6)	0.0177 (6)	−0.0033 (5)	−0.0025 (5)	−0.0020 (5)
C29	0.0164 (6)	0.0140 (6)	0.0175 (6)	−0.0062 (5)	0.0005 (5)	−0.0024 (5)

Cu1—O2	1.9647 (11)	C2—H2B	0.9900
Cu1—O1	1.9655 (11)	C9—C10	1.405 (2)
Cu1—O2'	1.9725 (11)	C1—O1'i	1.2592 (17)
Cu1—O1'	1.9799 (11)	C30—C29	1.400 (2)
Cu1—O1D	2.1344 (14)	C1D—H02A	0.9800
Cu1—Cu1i	2.6619 (12)	C1D—H02B	0.9800
Cl3—C30	1.7350 (17)	C1D—H02C	0.9800
Cl2—C14	1.7344 (17)	C5—C6	1.389 (2)
S1D—O1D	1.5122 (11)	C5—C4	1.390 (2)
S1D—C1D	1.7889 (16)	C5—H5	0.9500
S1D—C2D	1.7905 (18)	C12—C11	1.388 (2)
Cl4—C34	1.7368 (15)	C12—H12	0.9500
Cl1—C10	1.7406 (16)	C11—C10	1.385 (2)
O2—C21	1.2649 (17)	C11—H11	0.9500
O1—C1	1.2595 (16)	C7—C6	1.389 (2)
O1'—C1i	1.2592 (17)	C7—H7	0.9500
O2'—C21i	1.2578 (16)	C6—H6	0.9500
N012—C29	1.3959 (18)	C2D—H03A	0.9800
N012—C28	1.4212 (18)	C2D—H03B	0.9800
N012—H012	0.80 (2)	C2D—H03C	0.9800
C14—C13	1.386 (2)	C4—C3	1.392 (2)
C14—C9	1.405 (2)	C4—H4	0.9500
C28—C27	1.394 (2)	C26—C25	1.388 (2)
C28—C23	1.397 (2)	C26—H26	0.9500
C8—C7	1.3966 (19)	C22—C23	1.511 (2)
C8—C3	1.401 (2)	C22—C21	1.5198 (19)
C8—N1	1.4193 (18)	C22—H22A	0.9900
N1—C9	1.4003 (19)	C22—H22B	0.9900
N1—H1	0.81 (2)	C32—C33	1.384 (2)
C31—C30	1.386 (2)	C32—H32	0.9500
C31—C32	1.387 (2)	C21—O2'i	1.2579 (16)
C31—H31	0.9500	C23—C24	1.3992 (19)
C13—C12	1.389 (2)	C24—C25	1.390 (2)
C13—H13	0.9500	C24—H24	0.9500
C27—C26	1.388 (2)	C25—H25	0.9500
C27—H27	0.9500	C33—C34	1.386 (2)
C2—C3	1.5050 (19)	C33—H33	0.9500
C2—C1	1.5203 (19)	C34—C29	1.402 (2)
C2—H2A	0.9900
O2—Cu1—O1	86.92 (5)	H02A—C1D—H02C	109.5
O2—Cu1—O2'	167.83 (4)	H02B—C1D—H02C	109.5
O1—Cu1—O2'	92.47 (6)	C6—C5—C4	119.31 (14)
O2—Cu1—O1'	90.59 (5)	C6—C5—H5	120.3
O1—Cu1—O1'	167.60 (4)	C4—C5—H5	120.3
O2'—Cu1—O1'	87.41 (6)	C11—C12—C13	120.00 (14)
O2—Cu1—O1D	97.11 (5)	C11—C12—H12	120.0
O1—Cu1—O1D	94.31 (4)	C13—C12—H12	120.0
O2'—Cu1—O1D	95.06 (4)	C10—C11—C12	119.50 (15)
O1'—Cu1—O1D	98.06 (4)	C10—C11—H11	120.3
O2—Cu1—Cu1i	86.45 (4)	C12—C11—H11	120.3
O1—Cu1—Cu1i	85.35 (3)	C6—C7—C8	120.25 (13)
O2'—Cu1—Cu1i	81.39 (4)	C6—C7—H7	119.9
O1'—Cu1—Cu1i	82.36 (3)	C8—C7—H7	119.9
O1D—Cu1—Cu1i	176.41 (3)	C5—C6—C7	120.16 (13)
O1D—S1D—C1D	106.71 (7)	C5—C6—H6	119.9
O1D—S1D—C2D	106.52 (7)	C7—C6—H6	119.9
C1D—S1D—C2D	98.13 (8)	S1D—C2D—H03A	109.5
C21—O2—Cu1	120.01 (9)	S1D—C2D—H03B	109.5
S1D—O1D—Cu1	133.22 (6)	H03A—C2D—H03B	109.5
C1—O1—Cu1	121.65 (9)	S1D—C2D—H03C	109.5
C1i—O1'—Cu1	124.30 (9)	H03A—C2D—H03C	109.5
C21i—O2'—Cu1	125.79 (9)	H03B—C2D—H03C	109.5
C29—N012—C28	119.75 (12)	C5—C4—C3	121.55 (14)
C29—N012—H012	116.5 (14)	C5—C4—H4	119.2
C28—N012—H012	115.4 (14)	C3—C4—H4	119.2
C13—C14—C9	122.73 (14)	C25—C26—C27	119.88 (14)
C13—C14—Cl2	118.27 (11)	C25—C26—H26	120.1
C9—C14—Cl2	118.98 (11)	C27—C26—H26	120.1
C27—C28—C23	120.00 (13)	C23—C22—C21	111.97 (11)
C27—C28—N012	121.21 (13)	C23—C22—H22A	109.2
C23—C28—N012	118.79 (13)	C21—C22—H22A	109.2
C7—C8—C3	120.06 (13)	C23—C22—H22B	109.2
C7—C8—N1	121.86 (13)	C21—C22—H22B	109.2
C3—C8—N1	118.07 (12)	H22A—C22—H22B	107.9
C9—N1—C8	123.36 (12)	C33—C32—C31	119.92 (13)
C9—N1—H1	111.4 (14)	C33—C32—H32	120.0
C8—N1—H1	113.6 (14)	C31—C32—H32	120.0
C30—C31—C32	119.23 (13)	C11—C10—C9	122.69 (14)
C30—C31—H31	120.4	C11—C10—Cl1	118.58 (12)
C32—C31—H31	120.4	C9—C10—Cl1	118.73 (11)
C14—C13—C12	119.40 (14)	O2'i—C21—O2	125.72 (13)
C14—C13—H13	120.3	O2'i—C21—C22	117.28 (12)
C12—C13—H13	120.3	O2—C21—C22	116.98 (12)
C26—C27—C28	120.68 (14)	C28—C23—C24	118.49 (13)
C26—C27—H27	119.7	C28—C23—C22	120.72 (12)
C28—C27—H27	119.7	C24—C23—C22	120.72 (13)
C3—C2—C1	115.83 (11)	C4—C3—C8	118.60 (12)
C3—C2—H2A	108.3	C4—C3—C2	120.36 (13)
C1—C2—H2A	108.3	C8—C3—C2	121.01 (12)
C3—C2—H2B	108.3	C25—C24—C23	121.42 (14)
C1—C2—H2B	108.3	C25—C24—H24	119.3
H2A—C2—H2B	107.4	C23—C24—H24	119.3
N1—C9—C14	122.05 (14)	C26—C25—C24	119.44 (14)
N1—C9—C10	122.15 (13)	C26—C25—H25	120.3
C14—C9—C10	115.66 (13)	C24—C25—H25	120.3
O1'i—C1—O1	125.60 (12)	C32—C33—C34	119.82 (13)
O1'i—C1—C2	117.90 (12)	C32—C33—H33	120.1
O1—C1—C2	116.48 (12)	C34—C33—H33	120.1
C31—C30—C29	122.77 (13)	C33—C34—C29	122.24 (13)
C31—C30—Cl3	118.42 (11)	C33—C34—Cl4	119.09 (11)
C29—C30—Cl3	118.81 (10)	C29—C34—Cl4	118.66 (10)
S1D—C1D—H02A	109.5	N012—C29—C30	120.60 (13)
S1D—C1D—H02B	109.5	N012—C29—C34	123.50 (13)
H02A—C1D—H02B	109.5	C30—C29—C34	115.89 (12)
S1D—C1D—H02C	109.5
O1—Cu1—O2—C21	−80.75 (10)	C3—C8—C7—C6	1.2 (2)
O2'—Cu1—O2—C21	6.7 (3)	N1—C8—C7—C6	−177.75 (13)
O1'—Cu1—O2—C21	87.09 (10)	C4—C5—C6—C7	−1.9 (2)
O1D—Cu1—O2—C21	−174.72 (10)	C8—C7—C6—C5	1.2 (2)
Cu1i—Cu1—O2—C21	4.78 (10)	C6—C5—C4—C3	0.2 (2)
C1D—S1D—O1D—Cu1	54.37 (10)	C28—C27—C26—C25	0.5 (2)
C2D—S1D—O1D—Cu1	−49.71 (10)	C30—C31—C32—C33	1.5 (2)
O2—Cu1—O1D—S1D	−106.94 (9)	C12—C11—C10—C9	0.8 (2)
O1—Cu1—O1D—S1D	165.63 (8)	C12—C11—C10—Cl1	−179.88 (11)
O2'—Cu1—O1D—S1D	72.77 (9)	N1—C9—C10—C11	176.25 (13)
O1'—Cu1—O1D—S1D	−15.32 (9)	C14—C9—C10—C11	0.3 (2)
O2—Cu1—O1—C1	84.24 (11)	N1—C9—C10—Cl1	−3.02 (18)
O2'—Cu1—O1—C1	−83.59 (11)	C14—C9—C10—Cl1	−179.00 (10)
O1'—Cu1—O1—C1	5.6 (3)	Cu1—O2—C21—O2'i	−9.74 (19)
O1D—Cu1—O1—C1	−178.85 (10)	Cu1—O2—C21—C22	168.74 (9)
Cu1i—Cu1—O1—C1	−2.44 (10)	C23—C22—C21—O2'i	116.54 (13)
O2—Cu1—O1'—C1i	−93.06 (12)	C23—C22—C21—O2	−62.08 (16)
O1—Cu1—O1'—C1i	−14.8 (3)	C27—C28—C23—C24	−3.4 (2)
O2'—Cu1—O1'—C1i	74.93 (11)	N012—C28—C23—C24	177.69 (13)
O1D—Cu1—O1'—C1i	169.68 (11)	C27—C28—C23—C22	173.79 (13)
Cu1i—Cu1—O1'—C1i	−6.72 (11)	N012—C28—C23—C22	−5.15 (19)
O2—Cu1—O2'—C21i	2.2 (3)	C21—C22—C23—C28	85.23 (16)
O1—Cu1—O2'—C21i	89.04 (12)	C21—C22—C23—C24	−97.69 (15)
O1'—Cu1—O2'—C21i	−78.54 (11)	C5—C4—C3—C8	2.1 (2)
O1D—Cu1—O2'—C21i	−176.41 (11)	C5—C4—C3—C2	−175.91 (13)
Cu1i—Cu1—O2'—C21i	4.12 (11)	C7—C8—C3—C4	−2.8 (2)
C29—N012—C28—C27	−26.4 (2)	N1—C8—C3—C4	176.17 (12)
C29—N012—C28—C23	152.56 (13)	C7—C8—C3—C2	175.18 (12)
C7—C8—N1—C9	−13.2 (2)	N1—C8—C3—C2	−5.80 (19)
C3—C8—N1—C9	167.83 (13)	C1—C2—C3—C4	−100.88 (15)
C9—C14—C13—C12	1.3 (2)	C1—C2—C3—C8	81.12 (16)
Cl2—C14—C13—C12	−177.01 (11)	C28—C23—C24—C25	2.1 (2)
C23—C28—C27—C26	2.1 (2)	C22—C23—C24—C25	−175.05 (13)
N012—C28—C27—C26	−178.99 (14)	C27—C26—C25—C24	−1.8 (2)
C8—N1—C9—C14	−63.1 (2)	C23—C24—C25—C26	0.5 (2)
C8—N1—C9—C10	121.19 (16)	C31—C32—C33—C34	−2.6 (2)
C13—C14—C9—N1	−177.33 (13)	C32—C33—C34—C29	0.3 (2)
Cl2—C14—C9—N1	0.95 (18)	C32—C33—C34—Cl4	−179.55 (11)
C13—C14—C9—C10	−1.3 (2)	C28—N012—C29—C30	−59.39 (19)
Cl2—C14—C9—C10	176.94 (10)	C28—N012—C29—C34	121.85 (15)
Cu1—O1—C1—O1'i	8.65 (19)	C31—C30—C29—N012	177.19 (14)
Cu1—O1—C1—C2	−169.98 (9)	Cl3—C30—C29—N012	−3.74 (19)
C3—C2—C1—O1'i	3.49 (18)	C31—C30—C29—C34	−4.0 (2)
C3—C2—C1—O1	−177.76 (12)	Cl3—C30—C29—C34	175.12 (10)
C32—C31—C30—C29	1.9 (2)	C33—C34—C29—N012	−178.30 (13)
C32—C31—C30—Cl3	−177.23 (11)	Cl4—C34—C29—N012	1.52 (19)
C14—C13—C12—C11	−0.1 (2)	C33—C34—C29—C30	2.9 (2)
C13—C12—C11—C10	−0.9 (2)	Cl4—C34—C29—C30	−177.30 (10)

Cu1—O2	1.9647 (11)
Cu1—O1	1.9655 (11)
Cu1—O2′	1.9725 (11)
Cu1—O1′	1.9799 (11)
Cu1—O1D	2.1344 (14)
Cu1—Cu1i	2.6619 (12)

O2—Cu1—O1	86.92 (5)
O2—Cu1—O2′	167.83 (4)
O1—Cu1—O2′	92.47 (6)
O2—Cu1—O1′	90.59 (5)
O1—Cu1—O1′	167.60 (4)
O2′—Cu1—O1′	87.41 (6)
O2—Cu1—O1D	97.11 (5)
O1—Cu1—O1D	94.31 (4)
O2′—Cu1—O1D	95.06 (4)
O1′—Cu1—O1D	98.06 (4)
O2—Cu1—Cu1i	86.45 (4)
O1—Cu1—Cu1i	85.35 (3)
O2′—Cu1—Cu1i	81.39 (4)
O1′—Cu1—Cu1i	82.36 (3)
O1D—Cu1—Cu1i	176.41 (3)

Symmetry code: (i) .