catena-Poly[[bis­(5-chloro-2-nitro­benzoato)copper(II)]-bis­(μ-5-chloro-2-nitro­benzoato)]

Lim, E.K.; Teoh, S.G.; Razak, I.A.; Fun, H.-K.

doi:10.1107/S1600536809001895

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages m211-m212

doi:10.1107/S1600536809001895

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catena-Poly[[bis(5-chloro-2-nitrobenzoato)copper(II)]-bis(μ-5-chloro-2-nitrobenzoato)]

Eng Khoon Lim,^a Siang Guan Teoh,^a Ibrahim Abdul Razak ^b ‡ and Hoong-Kun Fun ^b ^*

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 17 December 2008; accepted 15 January 2009; online 23 January 2009)

In the title compound, [Cu₂(C₇H₃ClNO₄)₄]_n, the coordination geometry around each Cu^II ion is distorted square-pyramidal. The CuO₅ coordination is formed by five O atoms from the carboxylate groups of five 5-chloro-2-nitrobenzoate ligands. This coordination leads to the formation of centrosymmetric binuclear units which are edge-shared, forming a linear chain along the a axis, with the Cu^II ions alternately separated by 2.5891 (4) and 3.1763 (4) Å. The chains are interconnected into a three-dimensional network by C—H⋯O interactions.

Related literature

For general background, see: Balaraman et al. (2006 ); Tomoya et al. (2005 ). For bond-length data, see: Allen et al. (1987 ). For related structures, see: Kabbani et al. (2004 ); Stachová et al. (2004 ).

Experimental

Crystal data

[Cu₂(C₇H₃ClNO₄)₄]
M_r = 929.30
Triclinic, $[P \overline 1]$
a = 5.0353 (1) Å
b = 11.8001 (3) Å
c = 13.8595 (3) Å
α = 84.539 (2)°
β = 85.553 (1)°
γ = 85.610 (2)°
V = 815.30 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 100.0 (1) K
0.47 × 0.21 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.498, T_max = 0.875
11613 measured reflections
4656 independent reflections
3994 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.116
S = 1.10
4656 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O5	1.942 (2)
Cu1—O6ⁱ	1.946 (2)
Cu1—O2ⁱⁱ	1.950 (2)
Cu1—O1ⁱⁱⁱ	2.008 (2)
Cu1—O1	2.165 (2)
Symmetry codes: (i) -x, -y, -z+1; (ii) x-1, y, z; (iii) -x+1, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O4^iv	0.93	2.44	3.254 (3)	146
C11—H11A⋯O8^v	0.93	2.46	3.384 (3)	172
C14—H14A⋯O4ⁱ	0.93	2.54	3.417 (3)	156
Symmetry codes: (i) -x, -y, -z+1; (iv) -x, -y+1, -z+1; (v) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001895/ci2748sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001895/ci2748Isup2.hkl

checkCIF report

Comment top

The ability to induce DNA cleavage in the presence of H₂O₂ and reductants by phenanthroline-based copper complexes such as [Cu(imda)(5,6-dmp)] (where 5,6-dmp is 5,6-dimethyl-1,10-phenanthroline) and [Cu(N,N'-dialkyl-1,10-phenanthroline -2,9-dimethanamine)] (Balaraman et al., 2006; Tomoya et al., 2005) have driven us to investigate the DNA cleavage ability of benzoic acid-based copper complexes. Several benzoic acid-based copper complexes have been prepared in our laboratory and their DNA cleavage abilities are further investigated. In this paper, we report the crystal structure of the title compound.

In the title compound, the coordination geometry around each Cu^II ion can be described as square-pyramidal, formed by five O atoms from the carboxylate groups of five 5-chloro-2-nitrobenzoate ligands. The basal plane positions are occupied by atoms O5, O6A, O2B and O1C with an average Cu—O bond length of 1.962 (2) Å. The apical position is occupied by atom O1 (Fig.1). The Cu1 atom is displaced away from the basal plane by 0.1689 (3) Å and the Cu—Cu(-x,-y,1 - z) separation is 2.5891 (4) Å. Similar CuO₅ coordination were observed in related structures reported by Kabbani et al. (2004) and Stachová et al. (2004). The CuO₅ square pyramids are edge-shared to form a linear polymeric chain along the a axis. In the chain, the Cu^II ions are alternately separated by 2.5891 (4) and 3.1763 (4) Å.

Bond lengths of the ligands have normal values (Allen et al., 1987). The dihedral angle between nitro groups and the benzene rings are: C1–C6/N1/O3/O4 = 12.0 (3)° and C9–C14/N2/O7/O8 = 65.1 (3)°.

The polymeric chains are interconnected through C—H···O intramolecular interactions, forming a three-dimensional network (Table 2 and Fig. 2).

Related literature top

For general background, see: Balaraman et al. (2006); Tomoya et al. (2005). For bond-length data, see: Allen et al. (1987). For related structures, see: Kabbani et al. (2004); Stachová et al. (2004).

Experimental top

An ethanol solution (50 ml) of 5-chloro-2-nitrobenzoic acid (4.84 g, 0.024 mol) was added to a solution of copper(II) sulfate pentahydrate (3.00 g, 0.012 mol) in ethanol (50 ml) and the mixture was stirred and refluxed for 2 h. The resulting solution was filtered and left to cool down to room temperature. After a few days of slow evaporation, blue crystals suitable for X-ray analysis were collected.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. Part of the polymeric chain of the title compound, showing the coordination environment of the Cu atom and with displacement ellipsoids drawn at the 50% probability level. H-atoms are omitted for clarity. Symmetry codes: (A) -x, -y, 1-z; (B) x-1, y, z; (C) 1-x, -y, 1-z.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

catena-Poly[[bis(5-chloro-2-nitrobenzoato)copper(II)]-bis(µ-5-chloro- 2-nitrobenzoato)] top

Crystal data top

[Cu₂(C₇H₃ClNO₄)₄]	Z = 1
M_r = 929.30	F(000) = 462
Triclinic, P1	D_x = 1.893 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0353 (1) Å	Cell parameters from 4198 reflections
b = 11.8001 (3) Å	θ = 2.4–33.5°
c = 13.8595 (3) Å	µ = 1.72 mm⁻¹
α = 84.539 (2)°	T = 100 K
β = 85.553 (1)°	Plate, blue
γ = 85.610 (2)°	0.47 × 0.21 × 0.08 mm
V = 815.30 (3) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4656 independent reflections
Radiation source: fine-focus sealed tube	3994 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
T_min = 0.498, T_max = 0.875	k = −16→16
11613 measured reflections	l = −19→19

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0656P)² + 0.3146P] where P = (F_o² + 2F_c²)/3
4656 reflections	(Δ/σ)_max = 0.001
244 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

[Cu₂(C₇H₃ClNO₄)₄]	γ = 85.610 (2)°
M_r = 929.30	V = 815.30 (3) Å³
Triclinic, P1	Z = 1
a = 5.0353 (1) Å	Mo Kα radiation
b = 11.8001 (3) Å	µ = 1.72 mm⁻¹
c = 13.8595 (3) Å	T = 100 K
α = 84.539 (2)°	0.47 × 0.21 × 0.08 mm
β = 85.553 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4656 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3994 reflections with I > 2σ(I)
T_min = 0.498, T_max = 0.875	R_int = 0.034
11613 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.10	Δρ_max = 0.72 e Å⁻³
4656 reflections	Δρ_min = −1.04 e Å⁻³
244 parameters

Special details top

Experimental. The data was collected with the Oxford Cryosystem Cobra low-temperature attachment

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	0.21339 (5)	0.05196 (2)	0.471444 (19)	0.01008 (9)
Cl1	0.39928 (16)	0.36470 (6)	0.09685 (5)	0.02730 (16)
Cl2	−0.29870 (15)	−0.38843 (6)	0.13820 (5)	0.02494 (16)
O1	0.6289 (3)	0.09053 (14)	0.45747 (12)	0.0112 (3)
O2	1.0009 (3)	0.17993 (14)	0.40983 (12)	0.0130 (3)
O3	0.6319 (4)	0.29482 (16)	0.56079 (13)	0.0190 (4)
O4	0.2829 (4)	0.41394 (17)	0.56834 (15)	0.0242 (4)
O5	0.2124 (3)	−0.02541 (15)	0.35393 (12)	0.0138 (3)
O6	−0.1564 (3)	−0.11767 (15)	0.40442 (12)	0.0141 (3)
O7	0.1420 (4)	0.10970 (17)	0.17610 (15)	0.0247 (4)
O8	0.5268 (4)	0.0237 (2)	0.13998 (16)	0.0283 (5)
N1	0.4497 (4)	0.35283 (18)	0.52330 (16)	0.0162 (4)
N2	0.2865 (4)	0.02437 (19)	0.16027 (15)	0.0172 (4)
C1	0.4307 (5)	0.3520 (2)	0.41832 (17)	0.0138 (4)
C2	0.2609 (5)	0.4338 (2)	0.3721 (2)	0.0191 (5)
H2A	0.1571	0.4864	0.4073	0.023*
C3	0.2481 (5)	0.4361 (2)	0.2728 (2)	0.0215 (5)
H3A	0.1339	0.4899	0.2403	0.026*
C4	0.4063 (5)	0.3577 (2)	0.22185 (19)	0.0191 (5)
C5	0.5750 (5)	0.2744 (2)	0.26839 (18)	0.0150 (4)
H5A	0.6780	0.2219	0.2329	0.018*
C6	0.5877 (4)	0.2705 (2)	0.36849 (18)	0.0128 (4)
C7	0.7537 (4)	0.1749 (2)	0.41697 (16)	0.0116 (4)
C8	0.0272 (4)	−0.0881 (2)	0.34205 (17)	0.0125 (4)
C9	0.0247 (5)	−0.1317 (2)	0.24379 (17)	0.0131 (4)
C10	0.1569 (5)	−0.0832 (2)	0.16019 (18)	0.0156 (5)
C11	0.1618 (5)	−0.1279 (2)	0.07137 (19)	0.0209 (5)
H11A	0.2577	−0.0948	0.0173	0.025*
C12	0.0212 (5)	−0.2231 (2)	0.06434 (19)	0.0217 (5)
H12A	0.0200	−0.2545	0.0053	0.026*
C13	−0.1169 (5)	−0.2706 (2)	0.14635 (19)	0.0187 (5)
C14	−0.1152 (5)	−0.2281 (2)	0.23593 (18)	0.0168 (5)
H14A	−0.2060	−0.2632	0.2903	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00866 (14)	0.01013 (15)	0.01168 (15)	−0.00058 (9)	−0.00121 (9)	−0.00174 (10)
Cl1	0.0418 (4)	0.0235 (3)	0.0178 (3)	−0.0067 (3)	−0.0126 (3)	0.0037 (2)
Cl2	0.0375 (4)	0.0189 (3)	0.0210 (3)	−0.0106 (3)	−0.0089 (3)	−0.0029 (2)
O1	0.0094 (7)	0.0094 (8)	0.0142 (7)	0.0000 (6)	−0.0016 (6)	0.0014 (6)
O2	0.0087 (7)	0.0118 (8)	0.0181 (8)	0.0005 (6)	−0.0013 (6)	0.0012 (6)
O3	0.0224 (9)	0.0174 (9)	0.0175 (9)	0.0029 (7)	−0.0051 (7)	−0.0030 (7)
O4	0.0250 (10)	0.0228 (10)	0.0237 (10)	0.0053 (8)	0.0051 (8)	−0.0068 (8)
O5	0.0148 (8)	0.0154 (8)	0.0120 (7)	−0.0021 (6)	−0.0019 (6)	−0.0032 (6)
O6	0.0135 (7)	0.0151 (8)	0.0144 (8)	−0.0012 (6)	−0.0007 (6)	−0.0049 (6)
O7	0.0288 (10)	0.0179 (10)	0.0275 (10)	−0.0044 (8)	−0.0037 (8)	−0.0001 (8)
O8	0.0184 (9)	0.0366 (12)	0.0305 (11)	−0.0099 (8)	0.0025 (8)	−0.0026 (9)
N1	0.0169 (9)	0.0138 (10)	0.0181 (10)	−0.0024 (7)	0.0002 (8)	−0.0021 (8)
N2	0.0204 (10)	0.0178 (11)	0.0137 (9)	−0.0049 (8)	−0.0012 (8)	−0.0004 (8)
C1	0.0140 (10)	0.0113 (11)	0.0164 (11)	−0.0027 (8)	−0.0004 (8)	−0.0023 (8)
C2	0.0167 (11)	0.0139 (12)	0.0264 (13)	−0.0007 (9)	−0.0003 (9)	−0.0013 (10)
C3	0.0182 (11)	0.0162 (12)	0.0299 (14)	0.0012 (9)	−0.0099 (10)	0.0040 (10)
C4	0.0229 (12)	0.0191 (13)	0.0164 (11)	−0.0073 (10)	−0.0057 (9)	0.0014 (9)
C5	0.0178 (11)	0.0127 (11)	0.0149 (11)	−0.0032 (8)	−0.0024 (8)	−0.0005 (8)
C6	0.0100 (9)	0.0100 (10)	0.0185 (11)	−0.0021 (8)	−0.0015 (8)	0.0002 (8)
C7	0.0136 (10)	0.0113 (10)	0.0104 (9)	−0.0026 (8)	−0.0001 (8)	−0.0033 (8)
C8	0.0126 (10)	0.0114 (11)	0.0138 (10)	0.0001 (8)	−0.0018 (8)	−0.0022 (8)
C9	0.0132 (10)	0.0134 (11)	0.0132 (10)	−0.0001 (8)	−0.0025 (8)	−0.0032 (8)
C10	0.0149 (10)	0.0146 (11)	0.0176 (11)	−0.0027 (8)	−0.0012 (8)	−0.0010 (9)
C11	0.0232 (12)	0.0250 (14)	0.0145 (11)	−0.0040 (10)	−0.0002 (9)	−0.0012 (10)
C12	0.0273 (13)	0.0242 (14)	0.0151 (11)	−0.0021 (10)	−0.0033 (10)	−0.0078 (10)
C13	0.0222 (12)	0.0157 (12)	0.0197 (12)	−0.0031 (9)	−0.0063 (9)	−0.0033 (9)
C14	0.0196 (11)	0.0153 (12)	0.0155 (11)	−0.0029 (9)	−0.0016 (9)	0.0000 (9)

Geometric parameters (Å, º) top

Cu1—O5	1.942 (2)	C1—C2	1.384 (4)
Cu1—O6ⁱ	1.946 (2)	C1—C6	1.397 (3)
Cu1—O2ⁱⁱ	1.950 (2)	C2—C3	1.381 (4)
Cu1—O1ⁱⁱⁱ	2.008 (2)	C2—H2A	0.93
Cu1—O1	2.165 (2)	C3—C4	1.383 (4)
Cu1—Cu1ⁱ	2.5891 (5)	C3—H3A	0.93
Cl1—C4	1.729 (3)	C4—C5	1.393 (4)
Cl2—C13	1.739 (3)	C5—C6	1.390 (3)
O1—C7	1.279 (3)	C5—H5A	0.93
O1—Cu1ⁱⁱⁱ	2.0075 (17)	C6—C7	1.490 (3)
O2—C7	1.246 (3)	C8—C9	1.502 (3)
O2—Cu1^iv	1.9501 (17)	C9—C10	1.388 (3)
O3—N1	1.221 (3)	C9—C14	1.400 (3)
O4—N1	1.236 (3)	C10—C11	1.382 (3)
O5—C8	1.263 (3)	C11—C12	1.388 (4)
O6—C8	1.262 (3)	C11—H11A	0.93
O6—Cu1ⁱ	1.9459 (16)	C12—C13	1.380 (4)
O7—N2	1.223 (3)	C12—H12A	0.93
O8—N2	1.220 (3)	C13—C14	1.383 (3)
N1—C1	1.466 (3)	C14—H14A	0.93
N2—C10	1.472 (3)

O5—Cu1—O6ⁱ	170.11 (7)	C4—C3—H3A	120.3
O5—Cu1—O2ⁱⁱ	88.98 (7)	C3—C4—C5	121.7 (2)
O6ⁱ—Cu1—O2ⁱⁱ	90.41 (7)	C3—C4—Cl1	119.2 (2)
O5—Cu1—O1ⁱⁱⁱ	90.80 (7)	C5—C4—Cl1	119.1 (2)
O6ⁱ—Cu1—O1ⁱⁱⁱ	88.11 (7)	C6—C5—C4	119.3 (2)
O2ⁱⁱ—Cu1—O1ⁱⁱⁱ	170.10 (6)	C6—C5—H5A	120.3
O5—Cu1—O1	97.86 (7)	C4—C5—H5A	120.3
O6ⁱ—Cu1—O1	91.67 (6)	C5—C6—C1	118.1 (2)
O2ⁱⁱ—Cu1—O1	108.91 (7)	C5—C6—C7	117.9 (2)
O1ⁱⁱⁱ—Cu1—O1	80.92 (7)	C1—C6—C7	123.9 (2)
O5—Cu1—Cu1ⁱ	85.61 (5)	O2—C7—O1	125.4 (2)
O6ⁱ—Cu1—Cu1ⁱ	84.53 (5)	O2—C7—C6	118.2 (2)
O2ⁱⁱ—Cu1—Cu1ⁱ	90.98 (5)	O1—C7—C6	116.31 (19)
O1ⁱⁱⁱ—Cu1—Cu1ⁱ	79.14 (5)	O6—C8—O5	126.5 (2)
O1—Cu1—Cu1ⁱ	159.80 (5)	O6—C8—C9	116.6 (2)
C7—O1—Cu1ⁱⁱⁱ	127.17 (15)	O5—C8—C9	116.8 (2)
C7—O1—Cu1	133.75 (15)	C10—C9—C14	117.8 (2)
Cu1ⁱⁱⁱ—O1—Cu1	99.07 (7)	C10—C9—C8	123.8 (2)
C7—O2—Cu1^iv	117.23 (15)	C14—C9—C8	118.4 (2)
C8—O5—Cu1	120.91 (15)	C11—C10—C9	122.9 (2)
C8—O6—Cu1ⁱ	121.94 (15)	C11—C10—N2	115.9 (2)
O3—N1—O4	123.8 (2)	C9—C10—N2	121.1 (2)
O3—N1—C1	118.2 (2)	C10—C11—C12	118.8 (2)
O4—N1—C1	118.0 (2)	C10—C11—H11A	120.6
O8—N2—O7	124.6 (2)	C12—C11—H11A	120.6
O8—N2—C10	118.2 (2)	C13—C12—C11	119.0 (2)
O7—N2—C10	117.1 (2)	C13—C12—H12A	120.5
C2—C1—C6	122.5 (2)	C11—C12—H12A	120.5
C2—C1—N1	118.5 (2)	C12—C13—C14	122.2 (2)
C6—C1—N1	119.0 (2)	C12—C13—Cl2	119.5 (2)
C3—C2—C1	118.9 (2)	C14—C13—Cl2	118.3 (2)
C3—C2—H2A	120.6	C13—C14—C9	119.3 (2)
C1—C2—H2A	120.6	C13—C14—H14A	120.4
C2—C3—C4	119.5 (3)	C9—C14—H14A	120.4
C2—C3—H3A	120.3

O5—Cu1—O1—C7	89.7 (2)	Cu1ⁱⁱⁱ—O1—C7—O2	4.5 (3)
O6ⁱ—Cu1—O1—C7	−92.9 (2)	Cu1—O1—C7—O2	−174.59 (15)
O2ⁱⁱ—Cu1—O1—C7	−1.9 (2)	Cu1ⁱⁱⁱ—O1—C7—C6	179.81 (14)
O1ⁱⁱⁱ—Cu1—O1—C7	179.3 (2)	Cu1—O1—C7—C6	0.7 (3)
Cu1ⁱ—Cu1—O1—C7	−171.52 (14)	C5—C6—C7—O2	76.9 (3)
O5—Cu1—O1—Cu1ⁱⁱⁱ	−89.55 (8)	C1—C6—C7—O2	−107.4 (3)
O6ⁱ—Cu1—O1—Cu1ⁱⁱⁱ	87.82 (8)	C5—C6—C7—O1	−98.7 (2)
O2ⁱⁱ—Cu1—O1—Cu1ⁱⁱⁱ	178.83 (6)	C1—C6—C7—O1	77.0 (3)
O1ⁱⁱⁱ—Cu1—O1—Cu1ⁱⁱⁱ	0.000 (2)	Cu1ⁱ—O6—C8—O5	8.8 (3)
Cu1ⁱ—Cu1—O1—Cu1ⁱⁱⁱ	9.18 (17)	Cu1ⁱ—O6—C8—C9	−171.10 (15)
O2ⁱⁱ—Cu1—O5—C8	−88.27 (18)	Cu1—O5—C8—O6	−7.7 (3)
O1ⁱⁱⁱ—Cu1—O5—C8	81.83 (18)	Cu1—O5—C8—C9	172.23 (15)
O1—Cu1—O5—C8	162.78 (18)	O6—C8—C9—C10	160.5 (2)
Cu1ⁱ—Cu1—O5—C8	2.79 (17)	O5—C8—C9—C10	−19.5 (4)
O3—N1—C1—C2	−167.1 (2)	O6—C8—C9—C14	−20.7 (3)
O4—N1—C1—C2	11.5 (3)	O5—C8—C9—C14	159.4 (2)
O3—N1—C1—C6	11.7 (3)	C14—C9—C10—C11	−1.9 (4)
O4—N1—C1—C6	−169.6 (2)	C8—C9—C10—C11	177.0 (2)
C6—C1—C2—C3	−0.8 (4)	C14—C9—C10—N2	174.1 (2)
N1—C1—C2—C3	177.9 (2)	C8—C9—C10—N2	−7.1 (4)
C1—C2—C3—C4	−0.6 (4)	O8—N2—C10—C11	−64.3 (3)
C2—C3—C4—C5	1.5 (4)	O7—N2—C10—C11	112.1 (3)
C2—C3—C4—Cl1	−177.4 (2)	O8—N2—C10—C9	119.4 (3)
C3—C4—C5—C6	−0.8 (4)	O7—N2—C10—C9	−64.1 (3)
Cl1—C4—C5—C6	178.02 (18)	C9—C10—C11—C12	2.3 (4)
C4—C5—C6—C1	−0.6 (3)	N2—C10—C11—C12	−173.9 (2)
C4—C5—C6—C7	175.3 (2)	C10—C11—C12—C13	−0.6 (4)
C2—C1—C6—C5	1.5 (3)	C11—C12—C13—C14	−1.5 (4)
N1—C1—C6—C5	−177.3 (2)	C11—C12—C13—Cl2	178.9 (2)
C2—C1—C6—C7	−174.2 (2)	C12—C13—C14—C9	1.8 (4)
N1—C1—C6—C7	7.0 (3)	Cl2—C13—C14—C9	−178.53 (19)
Cu1^iv—O2—C7—O1	−3.4 (3)	C10—C9—C14—C13	−0.2 (4)
Cu1^iv—O2—C7—C6	−178.60 (15)	C8—C9—C14—C13	−179.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O4^v	0.93	2.44	3.254 (3)	146
C11—H11A···O8^vi	0.93	2.46	3.384 (3)	172
C14—H14A···O4ⁱ	0.93	2.54	3.417 (3)	156

Symmetry codes: (i) −x, −y, −z+1; (v) −x, −y+1, −z+1; (vi) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₇H₃ClNO₄)₄]
M_r	929.30
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.0353 (1), 11.8001 (3), 13.8595 (3)
α, β, γ (°)	84.539 (2), 85.553 (1), 85.610 (2)
V (Å³)	815.30 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.72
Crystal size (mm)	0.47 × 0.21 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.498, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	11613, 4656, 3994
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.116, 1.10
No. of reflections	4656
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −1.04

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Selected bond lengths (Å) top

Cu1—O5	1.942 (2)	Cu1—O1ⁱⁱⁱ	2.008 (2)
Cu1—O6ⁱ	1.946 (2)	Cu1—O1	2.165 (2)
Cu1—O2ⁱⁱ	1.950 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O4^iv	0.93	2.44	3.254 (3)	146
C11—H11A···O8^v	0.93	2.46	3.384 (3)	172
C14—H14A···O4ⁱ	0.93	2.54	3.417 (3)	156

Symmetry codes: (i) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z.

Footnotes

‡On sabbatical leave at Universiti Sains Malaysia.

Acknowledgements

HKF thanks the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312.

References

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