Di-μ-chlorido-bis­[(2-amino­benzamide-κ2N2,O)chlorido­copper(II)]

Damous, M.; Dénès, G.; Bouacida, S.; Hamlaoui, M.; Merazig, H.; Daran, J.-C.

doi:10.1107/S1600536813021879

metal-organic compounds

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Volume 69| Part 9| September 2013| Page m488

doi:10.1107/S1600536813021879

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Di-μ-chlorido-bis[(2-aminobenzamide-κ²N²,O)chloridocopper(II)]

Maamar Damous,^a George Dénès,^b Sofiane Bouacida,^a,^c ^* Meriem Hamlaoui,^a Hocine Merazig ^a and Jean-Claude Daran ^d

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine 1, 25000 , Algeria, ^bLaboratory of Solid State Chemistry and Mössbauer Spectroscopy, Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, H3G 1M8, Canada, ^cDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi 04000, Algeria, and ^dLaboratoire de Chimie de Coordination, UPR CNRS 8241, 205 route de Narbonne, 31077 Toulouse cedex, France
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 2 August 2013; accepted 5 August 2013; online 10 August 2013)

The title compound, [Cu₂Cl₄(C₇H₈N₂O)₂], crystallizes as discrete [CuLCl₂]₂ (L = 2-aminobenzamide) dimers with inversion symmetry. Each Cu^II ion is five-coordinated and is bound to two bridging chloride ligands, a terminal chloride ligand and a bidentate 2-aminobenzamide ligand. The crystal structure exhibits alternating layers parallel to (010) along the b-axis direction. In the crystal, the components are linked via N—H⋯Cl hydrogen bonds, forming a three-dimensional network. These interactions link the molecules within the layers and also link the layers together and reinforce the cohesion of the structure.

Related literature

For general background to 2-aminobenzamide derivatives, see: Nagaoka et al. (2006 ); Butsch et al. (2011 ); Kapoor et al. (2010 ). For related structures, see: Yang et al. (2012 ); Lah et al. (2006 ). For standard bond lengths, see: Allen (2002 )

Experimental

Crystal data

[Cu₂Cl₄(C₇H₈N₂O)₂]
M_r = 541.21
Monoclinic, P 2₁ /c
a = 8.1888 (5) Å
b = 13.8545 (6) Å
c = 8.1592 (4) Å
β = 98.771 (5)°
V = 914.85 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.93 mm⁻¹
T = 180 K
0.15 × 0.13 × 0.12 mm

Data collection

Agilent Xcalibur (Sapphire1) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.699, T_max = 1
5578 measured reflections
2058 independent reflections
1897 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.058
S = 1.04
2058 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2ⁱ	0.9200	2.4100	3.3113 (16)	166.00
N2—H2A⋯Cl1ⁱⁱ	0.8800	2.7800	3.6439 (16)	169.00
N2—H2B⋯Cl2ⁱⁱⁱ	0.8800	2.5400	3.3493 (17)	153.00
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y, z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813021879/hg5337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021879/hg5337Isup2.hkl

checkCIF report

Comment top

2-aminobenzamide derivatives are well known compounds as anticancer agents (Nagaoka et al., 2006). In addition, it was reported that some 2-aminobenzamide derivatives possessed biological activities, such as Anti-herpes simplex virus activity (Yang et al., 2012). As part of our ongoing studies of complexes based on copper and derivates we report here synthesis and the crystal structure of the title compound, obtained by the reaction of 2-aminobenzamide ligand with copper(II) chloride. The molecular structure of (I), and the atomic numbering used, is illustrated in Fig. 1. The asymmetric unit of (I) consists of one-half of the molecule, with the other half generated by a crystallographic inversion center. All bond distances and angles are within the ranges of accepted values(CSD, Allen, 2002) The complex contain five-coordinate Cu atoms (Fig. 1) with may be described either as square pyramidal with C11 apically bound to a pseudoplanar Cu1—O1—C12—Cl1a—N1 (a:-x, -y,1 - z) fragment or as trigonal bipyramidal with N1 and Cl1a apical (Butsch et al., 2011; Kapoor et al., 2010). The Cu atoms are linked by double Cl atoms bridges, resulting in the formation of dimer. The two Cu atoms, separated by 3.430 (1) Å, are doubly bridged by two chlorido ligands. The bridge is far from symmetrical with Cu—Cl1 and Cu—Cl1a (with a: -x, -y,1 - z) distances of 2.3983 (5) and 2.2990 (6) Å, respectively, and a Cu—Cl1-Cua bridging angle of 93.77 (2)°. The 2-aminobenzamide ligand binds to a single Cu metal ion within the dimer in a chelating manner [Cu—N1: 1.9923 (15) Å and Cu–O1: 2.0988 (13) Å]. The fifth coordination site is occupied by a terminal chlorido ligand at a distance of 2.3043 (6) Å (Lah et al., 2006).

The crystal structure exhibit alternating layers parallel to (010) plane along the b axis (Fig. 2). In the crystal, the components of the structure are linked via intermolecular N—H···Cl hydrogen bonds to form a three-dimensional network (Table1 and Fig.2) These interaction bonds link the molecules within the layers and also link the layers together and reinforcing the cohesion of the structure.

Related literature top

For general background to 2-aminobenzamide derivatives, see: Nagaoka et al. (2006), Butsch et al. (2011); Kapoor et al. (2010). For related structures, see: Yang et al. (2012); Lah et al. (2006). For standard bond lenghs see: Allen, (2002)

Experimental top

An aqueous acidic solution of copper(II) chloride was added to an aqueous solution of the 2-aminobenzamide ligand (L) (1:l mol ratio). The mixture was then stirred for several hours during which time darkish green crystals of [CuLCl₂]₂ were deposited. This crystalline product was collected and washed with ether and was carefully isolated under polarizing microscope for analysis by X-ray diffraction.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. (Farrugia, 2012) The molecule structure of the title dimer with the atomic labelling scheme·Displacement are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radius. Only the contents of the asymmetric unit are numbered.
	Fig. 2. (Brandenburg & Berndt, 2001) A diagram of the layered crystal packing in (I), viewed down the b axis, showing layers parallel to (010) and hydrogen bond connections as dashed line.

Di-µ-chlorido-bis[(2-aminobenzamide-κ²N²,O)chloridocopper(II)] top

Crystal data top

[Cu₂Cl₄(C₇H₈N₂O)₂]	F(000) = 540
M_r = 541.21	D_x = 1.965 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3363 reflections
a = 8.1888 (5) Å	θ = 2.9–28.2°
b = 13.8545 (6) Å	µ = 2.93 mm⁻¹
c = 8.1592 (4) Å	T = 180 K
β = 98.771 (5)°	Cube, green
V = 914.85 (8) Å³	0.15 × 0.13 × 0.12 mm
Z = 2

Data collection top

Agilent Xcalibur (Sapphire1) diffractometer	2058 independent reflections
Radiation source: fine-focus sealed tube	1897 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 8.2632 pixels mm^-1	θ_max = 28.3°, θ_min = 2.9°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −17→18
T_min = 0.699, T_max = 1	l = −10→10
5578 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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0307P)² + 0.3739P] where P = (F_o² + 2F_c²)/3
2058 reflections	(Δ/σ)_max = 0.003
118 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Cu₂Cl₄(C₇H₈N₂O)₂]	V = 914.85 (8) Å³
M_r = 541.21	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1888 (5) Å	µ = 2.93 mm⁻¹
b = 13.8545 (6) Å	T = 180 K
c = 8.1592 (4) Å	0.15 × 0.13 × 0.12 mm
β = 98.771 (5)°

Data collection top

Agilent Xcalibur (Sapphire1) diffractometer	2058 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1897 reflections with I > 2σ(I)
T_min = 0.699, T_max = 1	R_int = 0.022
5578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
2058 reflections	Δρ_min = −0.41 e Å⁻³
118 parameters

Special details top

Experimental. Absorption correction: empirical using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm CrysAlis PRO (Agilent, 2011).

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

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	0.18491 (3)	−0.04957 (2)	0.58700 (3)	0.0126 (1)
Cl1	0.05270 (6)	0.10533 (3)	0.57135 (6)	0.0161 (1)
Cl2	0.36324 (6)	−0.12970 (3)	0.44121 (6)	0.0162 (1)
O1	0.15024 (17)	−0.13480 (9)	0.79155 (16)	0.0156 (4)
N1	0.37924 (19)	−0.00155 (11)	0.74251 (18)	0.0126 (4)
N2	0.1556 (2)	−0.16908 (11)	1.0607 (2)	0.0180 (5)
C1	0.2398 (2)	−0.00937 (12)	0.9884 (2)	0.0107 (5)
C2	0.3341 (2)	0.04226 (12)	0.8882 (2)	0.0111 (5)
C3	0.3819 (2)	0.13689 (13)	0.9288 (2)	0.0147 (5)
C4	0.3337 (3)	0.18053 (13)	1.0665 (2)	0.0181 (5)
C5	0.2408 (3)	0.13070 (13)	1.1664 (2)	0.0171 (5)
C6	0.1958 (2)	0.03556 (13)	1.1275 (2)	0.0140 (5)
C7	0.1801 (2)	−0.10930 (12)	0.9406 (2)	0.0122 (5)
H1A	0.43529	0.04286	0.68835	0.0152*
H1B	0.44964	−0.05231	0.77350	0.0152*
H2A	0.11781	−0.22765	1.03652	0.0216*
H2B	0.17697	−0.15031	1.16476	0.0216*
H3	0.44744	0.17143	0.86209	0.0176*
H4	0.36477	0.24546	1.09246	0.0217*
H5	0.20810	0.16101	1.26070	0.0206*
H6	0.13389	0.00073	1.19728	0.0168*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0105 (1)	0.0152 (1)	0.0119 (1)	0.0003 (1)	0.0005 (1)	−0.0027 (1)
Cl1	0.0141 (2)	0.0125 (2)	0.0198 (2)	0.0006 (2)	−0.0036 (2)	−0.0023 (2)
Cl2	0.0160 (2)	0.0175 (2)	0.0162 (2)	0.0013 (2)	0.0059 (2)	−0.0026 (2)
O1	0.0214 (7)	0.0129 (6)	0.0121 (6)	−0.0036 (5)	0.0016 (5)	−0.0002 (5)
N1	0.0118 (7)	0.0148 (7)	0.0119 (7)	−0.0002 (6)	0.0038 (6)	0.0005 (6)
N2	0.0280 (10)	0.0118 (7)	0.0140 (8)	−0.0036 (7)	0.0026 (7)	−0.0001 (6)
C1	0.0100 (8)	0.0100 (8)	0.0113 (8)	0.0013 (7)	−0.0007 (7)	0.0004 (7)
C2	0.0084 (8)	0.0147 (8)	0.0094 (8)	0.0021 (7)	−0.0011 (7)	0.0005 (7)
C3	0.0141 (9)	0.0149 (8)	0.0146 (9)	−0.0020 (7)	0.0009 (7)	0.0026 (7)
C4	0.0193 (10)	0.0124 (8)	0.0217 (10)	−0.0016 (7)	0.0004 (8)	−0.0032 (7)
C5	0.0177 (10)	0.0176 (9)	0.0162 (9)	0.0016 (8)	0.0030 (8)	−0.0049 (7)
C6	0.0118 (9)	0.0167 (9)	0.0135 (9)	0.0006 (7)	0.0022 (7)	0.0026 (7)
C7	0.0103 (9)	0.0127 (8)	0.0135 (9)	0.0016 (7)	0.0018 (7)	0.0014 (7)

Geometric parameters (Å, º) top

Cu1—Cl1	2.3983 (5)	C1—C2	1.403 (2)
Cu1—Cl2	2.3043 (6)	C1—C6	1.389 (2)
Cu1—O1	2.0988 (13)	C1—C7	1.500 (2)
Cu1—N1	1.9923 (15)	C2—C3	1.394 (2)
Cu1—Cl1ⁱ	2.2990 (6)	C3—C4	1.385 (2)
O1—C7	1.254 (2)	C4—C5	1.382 (3)
N1—C2	1.433 (2)	C5—C6	1.392 (3)
N2—C7	1.322 (2)	C3—H3	0.9500
N1—H1A	0.9200	C4—H4	0.9500
N1—H1B	0.9200	C5—H5	0.9500
N2—H2A	0.8800	C6—H6	0.9500
N2—H2B	0.8800

Cl1—Cu1—Cl2	136.06 (2)	C2—C1—C6	118.81 (15)
Cl1—Cu1—O1	115.54 (4)	C2—C1—C7	120.37 (14)
Cl1—Cu1—N1	92.60 (5)	C6—C1—C7	120.74 (15)
Cl1—Cu1—Cl1ⁱ	86.23 (2)	N1—C2—C1	120.14 (15)
Cl2—Cu1—O1	108.22 (4)	N1—C2—C3	119.81 (15)
Cl2—Cu1—N1	88.98 (5)	C1—C2—C3	120.04 (15)
Cl1ⁱ—Cu1—Cl2	95.55 (2)	C2—C3—C4	119.93 (16)
O1—Cu1—N1	82.72 (6)	C3—C4—C5	120.73 (17)
Cl1ⁱ—Cu1—O1	93.00 (4)	C4—C5—C6	119.28 (16)
Cl1ⁱ—Cu1—N1	174.57 (5)	C1—C6—C5	121.19 (16)
Cu1—Cl1—Cu1ⁱ	93.77 (2)	O1—C7—C1	121.32 (15)
Cu1—O1—C7	125.63 (11)	N2—C7—C1	117.78 (15)
Cu1—N1—C2	112.82 (11)	O1—C7—N2	120.88 (16)
C2—N1—H1A	109.00	C2—C3—H3	120.00
C2—N1—H1B	109.00	C4—C3—H3	120.00
H1A—N1—H1B	108.00	C3—C4—H4	120.00
Cu1—N1—H1A	109.00	C5—C4—H4	120.00
Cu1—N1—H1B	109.00	C4—C5—H5	120.00
H2A—N2—H2B	120.00	C6—C5—H5	120.00
C7—N2—H2A	120.00	C1—C6—H6	119.00
C7—N2—H2B	120.00	C5—C6—H6	119.00

Cl2—Cu1—Cl1—Cu1ⁱ	94.09 (3)	Cu1—N1—C2—C1	55.55 (18)
O1—Cu1—Cl1—Cu1ⁱ	−91.53 (5)	C6—C1—C2—N1	−179.03 (15)
N1—Cu1—Cl1—Cu1ⁱ	−174.69 (5)	C7—C1—C6—C5	−175.43 (17)
Cl1ⁱ—Cu1—Cl1—Cu1ⁱ	0.00 (4)	C2—C1—C7—O1	−29.6 (2)
Cl1—Cu1—Cl1ⁱ—Cu1ⁱ	0.00 (4)	C6—C1—C2—C3	0.0 (2)
Cl2—Cu1—Cl1ⁱ—Cu1ⁱ	−135.94 (2)	C6—C1—C7—O1	147.06 (17)
O1—Cu1—Cl1ⁱ—Cu1ⁱ	115.41 (4)	C6—C1—C7—N2	−31.2 (2)
Cl1—Cu1—O1—C7	−53.92 (15)	C2—C1—C7—N2	152.19 (16)
Cl2—Cu1—O1—C7	121.99 (14)	C2—C1—C6—C5	1.3 (3)
N1—Cu1—O1—C7	35.49 (15)	C7—C1—C2—C3	176.68 (15)
Cl1ⁱ—Cu1—O1—C7	−141.17 (14)	C7—C1—C2—N1	−2.3 (2)
Cl1—Cu1—N1—C2	55.31 (11)	C1—C2—C3—C4	−1.2 (3)
Cl2—Cu1—N1—C2	−168.63 (11)	N1—C2—C3—C4	177.83 (17)
O1—Cu1—N1—C2	−60.11 (11)	C2—C3—C4—C5	1.2 (3)
Cu1—O1—C7—C1	2.6 (2)	C3—C4—C5—C6	0.1 (3)
Cu1—O1—C7—N2	−179.23 (12)	C4—C5—C6—C1	−1.3 (3)
Cu1—N1—C2—C3	−123.45 (14)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱⁱ	0.9200	2.4100	3.3113 (16)	166.00
N2—H2A···Cl1ⁱⁱⁱ	0.8800	2.7800	3.6439 (16)	169.00
N2—H2B···Cl2^iv	0.8800	2.5400	3.3493 (17)	153.00

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x, y−1/2, −z+3/2; (iv) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱ	0.9200	2.4100	3.3113 (16)	166.00
N2—H2A···Cl1ⁱⁱ	0.8800	2.7800	3.6439 (16)	169.00
N2—H2B···Cl2ⁱⁱⁱ	0.8800	2.5400	3.3493 (17)	153.00

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, y−1/2, −z+3/2; (iii) x, y, z+1.

Acknowledgements

This work was supported by the Unité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine1. 25000 Algeria, and the Laboratoire de Chimie de Coordination, 31077 Toulouse cedex, France. Thanks are due to the Ministére de l'Enseignement Supérieur et de la Recherche Scientifique - Algérie (PNR project) for financial support.

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