Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055663/hb2629sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055663/hb2629Isup2.hkl |
CCDC reference: 672610
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).
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.
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).
[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) Å3 |
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 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) = 0.114 | H 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 parameters | Δρmax = 0.47 e Å−3 |
1 restraint | Δρmin = −0.37 e Å−3 |
[Cu(C13H10ClN2O3S)(C13H11N2O3S)] | γ = 104.635 (1)° |
Mr = 648.61 | V = 672.96 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.9801 (2) Å | Mo Kα radiation |
b = 9.9993 (2) Å | µ = 1.12 mm−1 |
c = 10.0823 (2) Å | T = 106 K |
α = 104.393 (1)° | 0.55 × 0.40 × 0.21 mm |
β = 111.091 (1)° |
Bruker APEX-II diffractometer | 3026 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2769 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 0.800 | Rint = 0.016 |
6161 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 1 restraint |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | Δρmax = 0.47 e Å−3 |
3026 reflections | Δρmin = −0.37 e Å−3 |
191 parameters |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Cu1—O1i | 1.9062 (18) | C3—H3 | 0.9500 |
Cu1—O1 | 1.9062 (18) | C4—C5 | 1.356 (5) |
Cu1—N1i | 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 |
O1i—Cu1—O1 | 180.0 | C3—C4—Cl1 | 126.0 (3) |
O1i—Cu1—N1i | 91.01 (8) | C5—C4—H4 | 119.7 |
O1—Cu1—N1i | 88.99 (8) | C3—C4—H4 | 119.7 |
O1i—Cu1—N1 | 88.99 (8) | C4—C5—C6 | 120.7 (3) |
O1—Cu1—N1 | 91.01 (8) | C4—C5—H5 | 119.6 |
N1i—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 |
N1i—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) |
O1i—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) |
O1i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.87 (3) | 2.13 (3) | 2.723 (2) | 125 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C13H10ClN2O3S)(C13H11N2O3S)] |
Mr | 648.61 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 106 |
a, b, c (Å) | 7.9801 (2), 9.9993 (2), 10.0823 (2) |
α, β, γ (°) | 104.393 (1), 111.091 (1), 104.635 (1) |
V (Å3) | 672.96 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.55 × 0.40 × 0.21 |
Data collection | |
Diffractometer | Bruker APEX-II diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.621, 0.800 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6161, 3026, 2769 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.114, 1.20 |
No. of reflections | 3026 |
No. of parameters | 191 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.37 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.87 (3) | 2.13 (3) | 2.723 (2) | 125 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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.