[2′-(5-Chloro-2-oxidobenzyl­idene)benzene­sulfonohydrazide-κ²N,O][2′-(2-oxidobenzyl­idene)benzene­sulfonohydrazide-κ²N,O]copper(II)

The Cu^II atom (site symmetry ) 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.

Key indicators

• Single-crystal X-ray study
• T = 106 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.031
• wR factor = 0.114
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         20 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.08
PLAT301_ALERT_3_C Main Residue  Disorder .........................       2.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C3     -   C4     ...       1.39 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C4     -   C5     ...       1.36 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  Cl1    ..  C9      ..       3.24 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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).

S3. Refinement

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 1.2U_eq(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

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

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)

Crystal data

[Cu(C13H10ClN2O3S)(C13H11N2O3S)]	Z = 1
Mr = 648.61	F(000) = 331
Triclinic, P1	Dx = 1.600 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9801 (2) Å	Cell parameters from 4328 reflections
b = 9.9993 (2) Å	θ = 2.3–31.7°
c = 10.0823 (2) Å	µ = 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) Å^3

Data collection

Bruker APEX-II diffractometer	3026 independent reflections
Radiation source: medium-focus sealed tube	2769 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ϕ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.621, Tmax = 0.800	k = −12→12
6161 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0623P)^2 + 0.3245P] where P = (Fo^2 + 2Fc^2)/3
3026 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.47 e Å^−3
1 restraint	Δρmin = −0.37 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.5000	0.5000	0.02500 (14)
Cl1	0.1626 (2)	−0.10643 (15)	−0.20334 (14)	0.0409 (3)	0.50
S1	0.45362 (9)	0.19783 (6)	0.68120 (8)	0.03327 (17)
O1	0.2978 (2)	0.41982 (17)	0.2953 (2)	0.0307 (4)
N1	0.5095 (3)	0.3035 (2)	0.4831 (2)	0.0280 (4)
N2	0.6053 (3)	0.2800 (2)	0.6200 (3)	0.0313 (4)
H2N	0.691 (4)	0.363 (2)	0.695 (3)	0.042 (8)*
O2	0.3354 (3)	0.05096 (19)	0.5676 (3)	0.0431 (5)
O3	0.5800 (3)	0.2193 (2)	0.8345 (3)	0.0469 (5)
C1	0.2593 (3)	0.2975 (3)	0.1829 (3)	0.0316 (5)
C2	0.1386 (4)	0.2744 (3)	0.0309 (3)	0.0391 (6)
H2	0.0805	0.3440	0.0118	0.047*
C3	0.1027 (5)	0.1518 (3)	−0.0915 (3)	0.0448 (7)
H3	0.0224	0.1390	−0.1934	0.054*
C4	0.1844 (5)	0.0473 (3)	−0.0649 (4)	0.0478 (7)
H4	0.1626	−0.0349	−0.1493	0.057*	0.50
C5	0.2947 (4)	0.0620 (3)	0.0803 (4)	0.0422 (6)
H5	0.3449	−0.0122	0.0967	0.051*
C6	0.3359 (4)	0.1868 (2)	0.2076 (3)	0.0325 (5)
C7	0.4457 (3)	0.1906 (2)	0.3564 (3)	0.0319 (5)
H7	0.4740	0.1051	0.3635	0.038*
C8	0.3039 (3)	0.2999 (3)	0.6841 (3)	0.0313 (5)
C9	0.1162 (4)	0.2416 (3)	0.5700 (4)	0.0416 (6)
H9	0.0649	0.1455	0.4920	0.050*
C10	0.0038 (4)	0.3275 (4)	0.5720 (4)	0.0526 (8)
H10	−0.1263	0.2896	0.4945	0.063*
C11	0.0797 (4)	0.4675 (4)	0.6855 (4)	0.0486 (7)
H11	0.0015	0.5252	0.6848	0.058*
C12	0.2683 (4)	0.5243 (3)	0.8000 (4)	0.0412 (6)
H12	0.3194	0.6202	0.8781	0.049*
C13	0.3824 (4)	0.4401 (3)	0.7998 (3)	0.0338 (5)
H13	0.5123	0.4777	0.8777	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0256 (2)	0.01650 (19)	0.0427 (3)	0.01142 (15)	0.02107 (18)	0.01444 (16)
Cl1	0.0469 (7)	0.0369 (6)	0.0316 (6)	0.0084 (5)	0.0199 (5)	0.0059 (5)
S1	0.0386 (3)	0.0245 (3)	0.0532 (4)	0.0176 (2)	0.0279 (3)	0.0238 (3)
O1	0.0314 (8)	0.0208 (7)	0.0440 (10)	0.0122 (6)	0.0192 (7)	0.0128 (7)
N1	0.0286 (9)	0.0212 (9)	0.0464 (11)	0.0137 (7)	0.0237 (9)	0.0174 (8)
N2	0.0302 (10)	0.0247 (9)	0.0500 (13)	0.0148 (8)	0.0229 (10)	0.0193 (9)
O2	0.0498 (11)	0.0220 (8)	0.0711 (13)	0.0155 (8)	0.0365 (10)	0.0228 (9)
O3	0.0577 (12)	0.0452 (11)	0.0599 (13)	0.0313 (10)	0.0304 (11)	0.0362 (10)
C1	0.0313 (11)	0.0220 (10)	0.0476 (14)	0.0073 (9)	0.0247 (11)	0.0146 (10)
C2	0.0406 (13)	0.0291 (12)	0.0486 (15)	0.0070 (10)	0.0236 (12)	0.0172 (11)
C3	0.0509 (16)	0.0360 (14)	0.0426 (15)	0.0014 (12)	0.0267 (13)	0.0138 (12)
C4	0.0613 (18)	0.0286 (12)	0.0585 (18)	0.0068 (12)	0.0434 (16)	0.0101 (12)
C5	0.0540 (16)	0.0243 (11)	0.0586 (18)	0.0116 (11)	0.0406 (15)	0.0122 (12)
C6	0.0341 (12)	0.0198 (10)	0.0507 (15)	0.0083 (9)	0.0282 (11)	0.0126 (10)
C7	0.0330 (12)	0.0196 (10)	0.0563 (15)	0.0135 (9)	0.0300 (12)	0.0165 (10)
C8	0.0338 (12)	0.0271 (11)	0.0507 (14)	0.0154 (9)	0.0297 (11)	0.0225 (11)
C9	0.0356 (13)	0.0345 (13)	0.0595 (17)	0.0111 (11)	0.0297 (13)	0.0152 (12)
C10	0.0296 (13)	0.0598 (19)	0.074 (2)	0.0210 (13)	0.0277 (14)	0.0238 (17)
C11	0.0444 (15)	0.0522 (17)	0.077 (2)	0.0316 (14)	0.0429 (16)	0.0316 (16)
C12	0.0517 (16)	0.0337 (13)	0.0593 (17)	0.0220 (12)	0.0412 (14)	0.0201 (12)
C13	0.0374 (12)	0.0312 (12)	0.0470 (14)	0.0154 (10)	0.0280 (11)	0.0207 (11)

Geometric parameters (Å, º)

Cu1—O1^i	1.9062 (18)	C3—H3	0.9500
Cu1—O1	1.9062 (18)	C4—C5	1.356 (5)
Cu1—N1^i	1.9532 (17)	C4—H4	0.9500
Cu1—N1	1.9532 (17)	C5—C6	1.416 (4)
Cl1—C4	1.721 (3)	C5—H5	0.9500
S1—O2	1.430 (2)	C6—C7	1.424 (4)
S1—O3	1.434 (2)	C7—H7	0.9500
S1—N2	1.676 (2)	C8—C9	1.375 (4)
S1—C8	1.760 (2)	C8—C13	1.392 (4)
O1—C1	1.321 (3)	C9—C10	1.392 (4)
N1—C7	1.300 (3)	C9—H9	0.9500
N1—N2	1.427 (3)	C10—C11	1.383 (5)
N2—H2N	0.87 (3)	C10—H10	0.9500
C1—C2	1.406 (4)	C11—C12	1.383 (4)
C1—C6	1.425 (3)	C11—H11	0.9500
C2—C3	1.387 (4)	C12—C13	1.387 (3)
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.395 (5)	C13—H13	0.9500
O1^i—Cu1—O1	180.0	C3—C4—Cl1	126.0 (3)
O1^i—Cu1—N1^i	91.01 (8)	C5—C4—H4	119.7
O1—Cu1—N1^i	88.99 (8)	C3—C4—H4	119.7
O1^i—Cu1—N1	88.99 (8)	C4—C5—C6	120.7 (3)
O1—Cu1—N1	91.01 (8)	C4—C5—H5	119.6
N1^i—Cu1—N1	180.0	C6—C5—H5	119.6
O2—S1—O3	120.67 (12)	C5—C6—C7	117.2 (2)
O2—S1—N2	106.95 (12)	C5—C6—C1	119.6 (3)
O3—S1—N2	103.56 (12)	C7—C6—C1	123.1 (2)
O2—S1—C8	108.21 (12)	N1—C7—C6	124.2 (2)
O3—S1—C8	110.29 (12)	N1—C7—H7	117.9
N2—S1—C8	106.12 (10)	C6—C7—H7	117.9
C1—O1—Cu1	126.98 (15)	C9—C8—C13	122.1 (2)
C7—N1—N2	114.94 (18)	C9—C8—S1	119.4 (2)
C7—N1—Cu1	126.16 (17)	C13—C8—S1	118.46 (19)
N2—N1—Cu1	118.78 (15)	C8—C9—C10	118.1 (3)
N1—N2—S1	113.53 (15)	C8—C9—H9	121.0
N1—N2—H2N	112 (2)	C10—C9—H9	121.0
S1—N2—H2N	108 (2)	C11—C10—C9	120.7 (3)
O1—C1—C2	119.2 (2)	C11—C10—H10	119.7
O1—C1—C6	123.1 (2)	C9—C10—H10	119.7
C2—C1—C6	117.7 (2)	C12—C11—C10	120.6 (3)
C3—C2—C1	121.3 (3)	C12—C11—H11	119.7
C3—C2—H2	119.4	C10—C11—H11	119.7
C1—C2—H2	119.4	C11—C12—C13	119.5 (3)
C4—C3—C2	120.0 (3)	C11—C12—H12	120.2
C4—C3—H3	120.0	C13—C12—H12	120.2
C2—C3—H3	120.0	C12—C13—C8	119.1 (3)
C5—C4—C3	120.6 (3)	C12—C13—H13	120.5
C5—C4—Cl1	113.5 (2)	C8—C13—H13	120.5
N1^i—Cu1—O1—C1	155.72 (18)	O1—C1—C6—C5	−177.2 (2)
N1—Cu1—O1—C1	−24.28 (18)	C2—C1—C6—C5	2.3 (3)
O1^i—Cu1—N1—C7	−159.40 (19)	O1—C1—C6—C7	6.2 (3)
O1—Cu1—N1—C7	20.60 (19)	C2—C1—C6—C7	−174.3 (2)
O1^i—Cu1—N1—N2	16.33 (15)	N2—N1—C7—C6	176.1 (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—N1	173.5 (2)
Cu1—N1—N2—S1	98.25 (16)	C1—C6—C7—N1	−9.8 (4)
O2—S1—N2—N1	65.37 (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—C9	103.9 (2)
Cu1—O1—C1—C2	−164.03 (17)	O2—S1—C8—C13	171.64 (18)
Cu1—O1—C1—C6	15.5 (3)	O3—S1—C8—C13	37.7 (2)
O1—C1—C2—C3	176.4 (2)	N2—S1—C8—C13	−73.9 (2)
C6—C1—C2—C3	−3.1 (4)	C13—C8—C9—C10	0.2 (4)
C1—C2—C3—C4	1.1 (4)	S1—C8—C9—C10	−177.5 (2)
C2—C3—C4—C5	1.9 (4)	C8—C9—C10—C11	0.2 (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—C13	0.5 (4)
Cl1—C4—C5—C6	176.62 (19)	C11—C12—C13—C8	−0.1 (4)
C4—C5—C6—C7	177.3 (2)	C9—C8—C13—C12	−0.3 (4)
C4—C5—C6—C1	0.5 (4)	S1—C8—C13—C12	177.43 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1^i	0.87 (3)	2.13 (3)	2.723 (2)	125 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.