Tetra­kis{2-[2-(2,6-dichloro­anilino)phen­yl]ethano­ato-κ2O:O′}bis­[(dimethyl sulfoxide-κO)copper(II)](Cu—Cu): a binuclear CuII complex with the non-steroidal anti-inflammatory drug diclofenac

Sayen, S.; Guillon, E.

doi:10.1107/S160053681201152X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m474-m475

doi:10.1107/S160053681201152X

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Tetrakis{2-[2-(2,6-dichloroanilino)phenyl]ethanoato-κ²O:O′}bis[(dimethyl sulfoxide-κO)copper(II)](Cu—Cu): a binuclear Cu^II complex with the non-steroidal anti-inflammatory drug diclofenac

Stéphanie Sayen ^a and Emmanuel Guillon ^a ^*

^aInstitut de Chimie Moléculaire de Reims, ICMR, UMR CNRS 7312, Université de Reims Champagne Ardenne, Moulin de la Housse, BP 1039, 51687 Reims cedex 2, France
^*Correspondence e-mail: emmanuel.guillon@univ-reims.fr

(Received 10 February 2012; accepted 16 March 2012; online 24 March 2012)

The title compound, [Cu₂(C₁₄H₁₀Cl₂NO₂)₄(C₂H₆OS)₂], comprises a Cu^II₂ core that is quadruply bridged by four carboxylate ligands with the dimethyl sulfoxide ligands binding along the Cu⋯Cu axis. The four carboxylate ligands bind in a bidentate syn–syn bridging mode. Molecules reside on crystallographic inversion centres bisecting the mid-point of the Cu⋯Cu axis. There are no intermolecular interactions of note.

Related literature

Cu^II 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 Cu^II 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 Cu^II 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_r = 1463.90
Triclinic, $[P \overline 1]$
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 $[Oxford Diffraction (2010). CrysAlis PRO and ABSPACK. Oxford Diffraction, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 0.99
10796 reflections
396 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

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) -x, -y, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and ABSPACK. Oxford Diffraction, Yarnton, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681201152X/gg2076sup1.cif

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

checkCIF report

Comment top

The proposed curative properties of Cu-based non-steroidal anti-inflammatory drugs (NSAIDs) have led to the development of numerous Cu(II) complexes of NSAIDs with enhanced anti-inflammatory activity and reduced gastrointestinal toxicity compared with their uncomplexed parent drug (Weder et al., 2002). Furthermore, little is known of their pharmacokinetic and biodistribution profile in both humans and animals, stabilty in biological media, or of the relative potency/efficacy of the Cu^II monomeric versus Cu^II dimeric complexes. 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 Cu^II complex of aspirin ([Cu(Asp)₂(py)₂]) is reportedly more effective than the dimeric [Cu₂(Asp)₄] complex (Oberley & Buettner, 1979). Thus, it appears to be essential to obtain structural information on Cu^(II) complexes of NSAIDs in order to fully understand their biological activity. Being able to act as a ligand through its carboxylate function of the aromatic ring, different diclofenac complexes (Cu-NSAID complex) were described in the literature. It gives rise to a mononuclear [Cu(diclofenac)₂(H₂O)₂].2H₂O complex (Sayen et al., 2012) and a binuclear [Cu₂(diclofenac)₄(DMF)₂] complex without a metal-metal bond (Kovala-Demertzi et al., 1997). The former resulted in a distorted octahedral geometry, whereas the latter resulted in a binuclear copper complex where each metal centre is described as a perfect square bipyramid with a DMF oxygen occupying apical position. In order to favour the metal···metal bond, which stabilizes the complex and thus impact the biological activity, we have tried various coordinating solvents during the recrystallization.

The structure of the binuclear [bis(2-[2-(2,6-dichlorophenyl)aminophenyl]ethanoate)bis(DMSO)copper(II)] complex (I) has been obtained. It consists of a quadruply bridged neutral molecule lying on a crystallographic centre of inversion (Fig. 1). Indeed, the four carboxylato moieties act as bridging ligands exhibiting a centre of symmetry midway between the two Cu atoms. The solvent used in the synthesis binds in the position trans to the Cu—Cu axis. The dimeric structure has a Cu—Cu distance of 2.6619 (12) Å, with an octahedral stereochemistry tetragonally elongated along the Cu—Cu-O_solvent axis due to the Jahn-Teller effect (Table 1).

In the binuclear unit, the carboxylic acids are fully deprotonated to balance the charge from the Cu^II ions. The stability of the structure is ensured via a network of /p···/p interactions involving the phenyl acetate rings of the diclofenac molecules. On the other hand, no intermolecular H-bonding is observed (Fig. 2).

The use of DMSO solvent allowed the formation of a binuclear complex with a Cu₂ metal core, which stabilizes the complex in biological media. It was shown that binuclear Cu-NSAID complexes exhibit similar biological activity as the mononuclear complex, but with a higher stability (Dimiza et al., 2011), making them relevant compounds in the treatment of tumor cell lines (Theodorou et al., 1999).

Related literature top

Cu(II) complexes ofnon-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 Cu^II 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 binuclear 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 Cu 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 top

The [bis(2-[2-(2,6-dichlorophenyl)aminophenyl]ethanoate)bis(DMSO)copper(II)] was prepared from a mixture of copper sulfate and diclofenac sodium salt in the molar ratio 1:2 in deionized water. After stirring for 2 hrs at room temperature, the reaction mixture was filtered and the green precipitate was washed with water and dried in air. Crystals suitable for X-ray diffraction measurements were obtained by slow evaporation of a DMSO solution of the complex.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. : A representation of the title compound (I) with displacement ellipsoids at the 30% probability level.
	Fig. 2. : The π···π stacking interactions in the [Cu₂(diclofenac)₄(DMSO)₂] complex (H atoms are omitted for clarity).

Tetrakis{2-[2-(2,6-dichloroanilino)phenyl]ethanoato- κ²O:O'}bis[(dimethyl sulfoxide-κO)copper(II)](Cu—Cu) top

Crystal data top

[Cu₂(C₁₄H₁₀Cl₂NO₂)₄(C₂H₆OS)₂]	Z = 1
M_r = 1463.90	F(000) = 746
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0335P)² + 0.9652P] where P = (F_o² + 2F_c²)/3
10796 reflections	(Δ/σ)_max = 0.012
396 parameters	Δρ_max = 0.71 e Å⁻³
1 restraint	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Cu₂(C₁₄H₁₀Cl₂NO₂)₄(C₂H₆OS)₂]	γ = 68.489 (5)°
M_r = 1463.90	V = 1539.4 (11) Å³
Triclinic, P1	Z = 1
a = 10.357 (5) Å	Mo Kα radiation
b = 12.787 (5) Å	µ = 1.17 mm⁻¹
c = 12.925 (5) Å	T = 100 K
α = 81.605 (5)°	0.30 × 0.21 × 0.18 mm
β = 75.561 (5)°

Data collection top

Oxford Diffraction SuperNova Atlas diffractometer	10796 independent reflections
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010)	9113 reflections with I > 2σ(I)
T_min = 0.867, T_max = 1.000	R_int = 0.030
42084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.71 e Å⁻³
10796 reflections	Δρ_min = −0.51 e Å⁻³
396 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₄H₁₀Cl₂NO₂)₄(C₂H₆OS)₂]
M_r	1463.90
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.357 (5), 12.787 (5), 12.925 (5)
α, β, γ (°)	81.605 (5), 75.561 (5), 68.489 (5)
V (Å³)	1539.4 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.30 × 0.21 × 0.18

Data collection
Diffractometer	Oxford Diffraction SuperNova Atlas
Absorption correction	Multi-scan (ABSPACK; Oxford Diffraction, 2010)
T_min, T_max	0.867, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	42084, 10796, 9113
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.774

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 0.99
No. of reflections	10796
No. of parameters	396
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.51

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

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

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

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

Dr S. Chevreux and Professor E. Wenger are gratefully acknowledged for the crystal structure determination.

References

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