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Acta Cryst. (2007). E63, m2937    [ doi:10.1107/S1600536807055663 ]

[2'-(5-Chloro-2-oxidobenzylidene)benzenesulfonohydrazide-[kappa]2N,O][2'-(2-oxidobenzylidene)benzenesulfonohydrazide-[kappa]2N,O]copper(II)

H. M. Ali, J. Yusnita, M. R. Rizal and S. W. Ng

Abstract top

The CuII atom (site symmetry \overline{1}) in the title compound, [Cu(C13H10ClN2O3S)(C13H11N2O3S)], is N,O-chelated by the monoanionic ligands in a trans-CuN2O2 square-planar geometry. The 2'-(2-oxidobenzylidene)benzenesulfonohydrazide anion is disordered equallywith the chlorine-substituted 2'-(5-chloro-2-oxidobenzylidene)benzenesulfonohydrazide anion. An intermolecular N-H...O hydrogen bond helps to stabilize the crystal structure.

Comment top

The title compound is a mixed-ligand compound in which the C13H11O3N2S anion is disordered with respect to a C13H10O3N2ClS anion. Although the synthesis had used 4-chlorobenzaldehyde as a starting material to prepare the Schiff base, this reagent is probably contaminated with an unknown quantity of benzaldehyde itself.

Related literature top

For the structure of a related ligand, see: Ali et al. (2007).

Experimental top

Benzene sulfonylhydrazide (0.5 g, 0.3 mmol) and 4-chlorobenzaldehyde (0.5 g, 0.3 mmol) were dissolved in ethanol (50 ml). The reactants were heated under reflux for 1 h. The solvent was removed to give the Schiff base, which was purified by recrystallization from ethyl acetate. The organic compound (0.6 g, 2 mmol) dissolved in basified ethanol (50 ml) was heated with copper acetate (0.2 g m, 1 mmol) for 5 h. The solvent was removed and the product recrystallized from DMSO to yield golden blocks of (I).

Refinement top

The refinement initally assumed full occupancy for the chlorine atom but the refinement gave a deep hole in its vicinity. The occupany was allowed to refine; as this refined to nearly 1/2, the occupancy was then set as half. The half-occupancy chlorine atom implies that (I) is a mixed ligand compound having a chlorine substitutent in 50% of the anions but none in the other 50%.

The carbon-bound H atoms were placed at calculated positions (C–H 0.95 Å), and were included in the refinement in the riding model approximation with U(H) set to 1.2Ueq(C). The amino hydrogen atom was located in a difference Fouier map, and was refined with a distance restraint of N–H 0.88±0.01 Å.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as spheres of arbitrary radii. The chlorine atom is statistically disordered with respect to a hydrogen atom and only one possible arrangement of these atoms is shown. The dashed lines denote the intramolecular hydrogen bond. Symmetry code (i) 1 – x, 1 – y, 1 – z.
[2'-(5-Chloro-2-oxidobenzylidene)benzenesulfonohydrazide- κ2N,O][2'-(2-oxidobenzylidene)benzenesulfonohydrazide- κ2N,O)]copper(II) top
Crystal data top
[Cu(C13H10ClN2O3S)(C13H11N2O3S)]Z = 1
Mr = 648.61F(000) = 331
Triclinic, P1Dx = 1.600 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9801 (2) ÅCell parameters from 4328 reflections
b = 9.9993 (2) Åθ = 2.3–31.7°
c = 10.0823 (2) ŵ = 1.12 mm−1
α = 104.393 (1)°T = 106 K
β = 111.091 (1)°Irregular block, gold
γ = 104.635 (1)°0.55 × 0.40 × 0.21 mm
V = 672.96 (3) Å3
Data collection top
Bruker APEX-II
diffractometer		3026 independent reflections
Radiation source: medium-focus sealed tube2769 reflections with I > 2σ(I)
graphiteRint = 0.016
φ and ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.621, Tmax = 0.800k = −12→12
6161 measured reflectionsl = −13→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.20 w = 1/[σ2(Fo2) + (0.0623P)2 + 0.3245P]
where P = (Fo2 + 2Fc2)/3
3026 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.47 e Å−3
1 restraintΔρmin = −0.37 e Å−3
Crystal data top
[Cu(C13H10ClN2O3S)(C13H11N2O3S)]γ = 104.635 (1)°
Mr = 648.61V = 672.96 (3) Å3
Triclinic, P1Z = 1
a = 7.9801 (2) ÅMo Kα radiation
b = 9.9993 (2) ŵ = 1.12 mm−1
c = 10.0823 (2) ÅT = 106 K
α = 104.393 (1)°0.55 × 0.40 × 0.21 mm
β = 111.091 (1)°
Data collection top
Bruker APEX-II
diffractometer		2769 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.016
Tmin = 0.621, Tmax = 0.800θmax = 27.5°
6161 measured reflectionsStandard reflections: 0
3026 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.114Δρmax = 0.47 e Å−3
S = 1.20Δρmin = −0.37 e Å−3
3026 reflectionsAbsolute structure: ?
191 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.50000.50000.50000.02500 (14)
Cl10.1626 (2)−0.10643 (15)−0.20334 (14)0.0409 (3)0.50
S10.45362 (9)0.19783 (6)0.68120 (8)0.03327 (17)
O10.2978 (2)0.41982 (17)0.2953 (2)0.0307 (4)
N10.5095 (3)0.3035 (2)0.4831 (2)0.0280 (4)
N20.6053 (3)0.2800 (2)0.6200 (3)0.0313 (4)
H2N0.691 (4)0.363 (2)0.695 (3)0.042 (8)*
O20.3354 (3)0.05096 (19)0.5676 (3)0.0431 (5)
O30.5800 (3)0.2193 (2)0.8345 (3)0.0469 (5)
C10.2593 (3)0.2975 (3)0.1829 (3)0.0316 (5)
C20.1386 (4)0.2744 (3)0.0309 (3)0.0391 (6)
H20.08050.34400.01180.047*
C30.1027 (5)0.1518 (3)−0.0915 (3)0.0448 (7)
H30.02240.1390−0.19340.054*
C40.1844 (5)0.0473 (3)−0.0649 (4)0.0478 (7)
H40.1626−0.0349−0.14930.057*0.50
C50.2947 (4)0.0620 (3)0.0803 (4)0.0422 (6)
H50.3449−0.01220.09670.051*
C60.3359 (4)0.1868 (2)0.2076 (3)0.0325 (5)
C70.4457 (3)0.1906 (2)0.3564 (3)0.0319 (5)
H70.47400.10510.36350.038*
C80.3039 (3)0.2999 (3)0.6841 (3)0.0313 (5)
C90.1162 (4)0.2416 (3)0.5700 (4)0.0416 (6)
H90.06490.14550.49200.050*
C100.0038 (4)0.3275 (4)0.5720 (4)0.0526 (8)
H10−0.12630.28960.49450.063*
C110.0797 (4)0.4675 (4)0.6855 (4)0.0486 (7)
H110.00150.52520.68480.058*
C120.2683 (4)0.5243 (3)0.8000 (4)0.0412 (6)
H120.31940.62020.87810.049*
C130.3824 (4)0.4401 (3)0.7998 (3)0.0338 (5)
H130.51230.47770.87770.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0256 (2)0.01650 (19)0.0427 (3)0.01142 (15)0.02107 (18)0.01444 (16)
Cl10.0469 (7)0.0369 (6)0.0316 (6)0.0084 (5)0.0199 (5)0.0059 (5)
S10.0386 (3)0.0245 (3)0.0532 (4)0.0176 (2)0.0279 (3)0.0238 (3)
O10.0314 (8)0.0208 (7)0.0440 (10)0.0122 (6)0.0192 (7)0.0128 (7)
N10.0286 (9)0.0212 (9)0.0464 (11)0.0137 (7)0.0237 (9)0.0174 (8)
N20.0302 (10)0.0247 (9)0.0500 (13)0.0148 (8)0.0229 (10)0.0193 (9)
O20.0498 (11)0.0220 (8)0.0711 (13)0.0155 (8)0.0365 (10)0.0228 (9)
O30.0577 (12)0.0452 (11)0.0599 (13)0.0313 (10)0.0304 (11)0.0362 (10)
C10.0313 (11)0.0220 (10)0.0476 (14)0.0073 (9)0.0247 (11)0.0146 (10)
C20.0406 (13)0.0291 (12)0.0486 (15)0.0070 (10)0.0236 (12)0.0172 (11)
C30.0509 (16)0.0360 (14)0.0426 (15)0.0014 (12)0.0267 (13)0.0138 (12)
C40.0613 (18)0.0286 (12)0.0585 (18)0.0068 (12)0.0434 (16)0.0101 (12)
C50.0540 (16)0.0243 (11)0.0586 (18)0.0116 (11)0.0406 (15)0.0122 (12)
C60.0341 (12)0.0198 (10)0.0507 (15)0.0083 (9)0.0282 (11)0.0126 (10)
C70.0330 (12)0.0196 (10)0.0563 (15)0.0135 (9)0.0300 (12)0.0165 (10)
C80.0338 (12)0.0271 (11)0.0507 (14)0.0154 (9)0.0297 (11)0.0225 (11)
C90.0356 (13)0.0345 (13)0.0595 (17)0.0111 (11)0.0297 (13)0.0152 (12)
C100.0296 (13)0.0598 (19)0.074 (2)0.0210 (13)0.0277 (14)0.0238 (17)
C110.0444 (15)0.0522 (17)0.077 (2)0.0316 (14)0.0429 (16)0.0316 (16)
C120.0517 (16)0.0337 (13)0.0593 (17)0.0220 (12)0.0412 (14)0.0201 (12)
C130.0374 (12)0.0312 (12)0.0470 (14)0.0154 (10)0.0280 (11)0.0207 (11)
Geometric parameters (Å, °) top
Cu1—O1i1.9062 (18)C3—H30.9500
Cu1—O11.9062 (18)C4—C51.356 (5)
Cu1—N1i1.9532 (17)C4—H40.9500
Cu1—N11.9532 (17)C5—C61.416 (4)
Cl1—C41.721 (3)C5—H50.9500
S1—O21.430 (2)C6—C71.424 (4)
S1—O31.434 (2)C7—H70.9500
S1—N21.676 (2)C8—C91.375 (4)
S1—C81.760 (2)C8—C131.392 (4)
O1—C11.321 (3)C9—C101.392 (4)
N1—C71.300 (3)C9—H90.9500
N1—N21.427 (3)C10—C111.383 (5)
N2—H2N0.87 (3)C10—H100.9500
C1—C21.406 (4)C11—C121.383 (4)
C1—C61.425 (3)C11—H110.9500
C2—C31.387 (4)C12—C131.387 (3)
C2—H20.9500C12—H120.9500
C3—C41.395 (5)C13—H130.9500
O1i—Cu1—O1180.0C3—C4—Cl1126.0 (3)
O1i—Cu1—N1i91.01 (8)C5—C4—H4119.7
O1—Cu1—N1i88.99 (8)C3—C4—H4119.7
O1i—Cu1—N188.99 (8)C4—C5—C6120.7 (3)
O1—Cu1—N191.01 (8)C4—C5—H5119.6
N1i—Cu1—N1180.0C6—C5—H5119.6
O2—S1—O3120.67 (12)C5—C6—C7117.2 (2)
O2—S1—N2106.95 (12)C5—C6—C1119.6 (3)
O3—S1—N2103.56 (12)C7—C6—C1123.1 (2)
O2—S1—C8108.21 (12)N1—C7—C6124.2 (2)
O3—S1—C8110.29 (12)N1—C7—H7117.9
N2—S1—C8106.12 (10)C6—C7—H7117.9
C1—O1—Cu1126.98 (15)C9—C8—C13122.1 (2)
C7—N1—N2114.94 (18)C9—C8—S1119.4 (2)
C7—N1—Cu1126.16 (17)C13—C8—S1118.46 (19)
N2—N1—Cu1118.78 (15)C8—C9—C10118.1 (3)
N1—N2—S1113.53 (15)C8—C9—H9121.0
N1—N2—H2N112 (2)C10—C9—H9121.0
S1—N2—H2N108 (2)C11—C10—C9120.7 (3)
O1—C1—C2119.2 (2)C11—C10—H10119.7
O1—C1—C6123.1 (2)C9—C10—H10119.7
C2—C1—C6117.7 (2)C12—C11—C10120.6 (3)
C3—C2—C1121.3 (3)C12—C11—H11119.7
C3—C2—H2119.4C10—C11—H11119.7
C1—C2—H2119.4C11—C12—C13119.5 (3)
C4—C3—C2120.0 (3)C11—C12—H12120.2
C4—C3—H3120.0C13—C12—H12120.2
C2—C3—H3120.0C12—C13—C8119.1 (3)
C5—C4—C3120.6 (3)C12—C13—H13120.5
C5—C4—Cl1113.5 (2)C8—C13—H13120.5
N1i—Cu1—O1—C1155.72 (18)O1—C1—C6—C5−177.2 (2)
N1—Cu1—O1—C1−24.28 (18)C2—C1—C6—C52.3 (3)
O1i—Cu1—N1—C7−159.40 (19)O1—C1—C6—C76.2 (3)
O1—Cu1—N1—C720.60 (19)C2—C1—C6—C7−174.3 (2)
O1i—Cu1—N1—N216.33 (15)N2—N1—C7—C6176.1 (2)
O1—Cu1—N1—N2−163.67 (15)Cu1—N1—C7—C6−8.1 (3)
C7—N1—N2—S1−85.6 (2)C5—C6—C7—N1173.5 (2)
Cu1—N1—N2—S198.25 (16)C1—C6—C7—N1−9.8 (4)
O2—S1—N2—N165.37 (18)O2—S1—C8—C9−10.6 (2)
O3—S1—N2—N1−166.16 (16)O3—S1—C8—C9−144.6 (2)
C8—S1—N2—N1−49.98 (19)N2—S1—C8—C9103.9 (2)
Cu1—O1—C1—C2−164.03 (17)O2—S1—C8—C13171.64 (18)
Cu1—O1—C1—C615.5 (3)O3—S1—C8—C1337.7 (2)
O1—C1—C2—C3176.4 (2)N2—S1—C8—C13−73.9 (2)
C6—C1—C2—C3−3.1 (4)C13—C8—C9—C100.2 (4)
C1—C2—C3—C41.1 (4)S1—C8—C9—C10−177.5 (2)
C2—C3—C4—C51.9 (4)C8—C9—C10—C110.2 (5)
C2—C3—C4—Cl1−177.3 (2)C9—C10—C11—C12−0.5 (5)
C3—C4—C5—C6−2.6 (4)C10—C11—C12—C130.5 (4)
Cl1—C4—C5—C6176.62 (19)C11—C12—C13—C8−0.1 (4)
C4—C5—C6—C7177.3 (2)C9—C8—C13—C12−0.3 (4)
C4—C5—C6—C10.5 (4)S1—C8—C13—C12177.43 (18)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O1i0.87 (3)2.13 (3)2.723 (2)125 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.9062 (18)Cu1—N11.9532 (17)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O1i0.87 (3)2.13 (3)2.723 (2)125 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank the University of Canterbury, New Zealand, for the diffraction measurements, and the Science Fund (12–02–03–2031) and the Fundamental Research Grant Scheme (FP064/2006 A) for supporting this study.

references
References top

Ali, H. M., Laila, M., Wan Jeffrey, B. & Ng, S. W. (2007). Acta Cryst. E63, o1821–o1822.

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2005). APEX2 (Version 2.0-2) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.