Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103022285/de1224sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103022285/de1224Isup2.hkl |
CCDC reference: 226108
The N-p-methylphenyl-N'-ethoxycarbonylthiourea ligand was synthesized according to the method reported in our previous work (Zhang et al., 2003). To ethanol (30 ml) containing the ligand (2 mmol) was added an ethanol solution of cupric chloride (1 mmol). After stirring the solution at room temperature for 2 h, the mixture was filtered to obtain a white solid, which was then dried in air. Single crystals of (I) were obtained, after one week, by slow evaporation of a chloroform solution. Elemental analysis (C22H28ClCuN4O4S2, 575.59), calculated: C 45.87, H 4.86, N 9.73%; found: C 45.78, H 5.08, N 9.62%.
The structure was solved by direct methods (Sheldrick, 1990) and successive difference Fourier syntheses. The positions of all H atoms were fixed geometrically and C—H and N—H distances were as set by the program, with C—H distances in the range 0.93–0.97 Å and N—H distances of 0.86 Å. Uiso(H) values were fixed at 1.2Ueq(N,C). Please check added text.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[CuCl(C11H14N2O2S)2] | Dx = 1.448 Mg m−3 |
Mr = 575.59 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 998 reflections |
a = 22.826 (7) Å | θ = 3.0–22.6° |
b = 6.971 (2) Å | µ = 1.12 mm−1 |
c = 16.593 (5) Å | T = 293 K |
V = 2640.1 (14) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.20 × 0.16 mm |
F(000) = 1192 |
Make Model CCD area-detector diffractometer | 2943 independent reflections |
Radiation source: fine-focus sealed tube | 1757 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −27→28 |
Tmin = 0.542, Tmax = 0.836 | k = −8→7 |
14770 measured reflections | l = −20→20 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0741P)2 + 0.2626P] where P = (Fo2 + 2Fc2)/3 |
2943 reflections | (Δ/σ)max < 0.001 |
202 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[CuCl(C11H14N2O2S)2] | V = 2640.1 (14) Å3 |
Mr = 575.59 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 22.826 (7) Å | µ = 1.12 mm−1 |
b = 6.971 (2) Å | T = 293 K |
c = 16.593 (5) Å | 0.30 × 0.20 × 0.16 mm |
Make Model CCD area-detector diffractometer | 2943 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1757 reflections with I > 2σ(I) |
Tmin = 0.542, Tmax = 0.836 | Rint = 0.068 |
14770 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.35 e Å−3 |
2943 reflections | Δρmin = −0.32 e Å−3 |
202 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.47544 (3) | 0.7500 | 0.32174 (4) | 0.0580 (3) | |
S1 | 0.45043 (8) | 0.7500 | 0.19262 (9) | 0.0654 (6) | |
S2 | 0.40543 (6) | 0.7500 | 0.41373 (9) | 0.0538 (5) | |
Cl1 | 0.57008 (7) | 0.7500 | 0.35843 (10) | 0.0833 (7) | |
N1 | 0.5099 (2) | 0.7500 | 0.0544 (3) | 0.0569 (15) | |
H1 | 0.5446 | 0.7500 | 0.0343 | 0.068* | |
N2 | 0.5649 (2) | 0.7500 | 0.1683 (3) | 0.0551 (14) | |
H2A | 0.5659 | 0.7500 | 0.2201 | 0.066* | |
N3 | 0.4010 (2) | 0.7500 | 0.5717 (3) | 0.080 (2) | |
H3A | 0.4190 | 0.7500 | 0.6172 | 0.096* | |
N4 | 0.4939 (2) | 0.7500 | 0.5183 (3) | 0.0460 (13) | |
H4 | 0.5154 | 0.7500 | 0.4757 | 0.055* | |
O1 | 0.6249 (2) | 0.7500 | 0.0579 (3) | 0.0832 (16) | |
O2 | 0.66131 (19) | 0.7500 | 0.1832 (3) | 0.0757 (15) | |
O3 | 0.4993 (2) | 0.7500 | 0.6561 (3) | 0.0928 (19) | |
O4 | 0.57942 (16) | 0.7500 | 0.5785 (2) | 0.0540 (11) | |
C1 | 0.4664 (3) | 0.7500 | −0.0052 (4) | 0.0552 (17) | |
C2 | 0.4069 (3) | 0.7500 | 0.0070 (4) | 0.070 (2) | |
H2 | 0.3921 | 0.7500 | 0.0591 | 0.085* | |
C3 | 0.3692 (3) | 0.7500 | −0.0577 (4) | 0.088 (3) | |
H3 | 0.3290 | 0.7500 | −0.0482 | 0.106* | |
C4 | 0.3894 (3) | 0.7500 | −0.1367 (4) | 0.0641 (19) | |
C5 | 0.4478 (3) | 0.7500 | −0.1477 (4) | 0.072 (2) | |
H5 | 0.4628 | 0.7500 | −0.1998 | 0.086* | |
C6 | 0.4857 (3) | 0.7500 | −0.0837 (4) | 0.069 (2) | |
H6 | 0.5257 | 0.7500 | −0.0937 | 0.082* | |
C7 | 0.3486 (4) | 0.7500 | −0.2076 (5) | 0.092 (3) | |
H7A | 0.3452 | 0.8779 | −0.2285 | 0.138* | 0.50 |
H7B | 0.3107 | 0.7053 | −0.1909 | 0.138* | 0.50 |
H7C | 0.3638 | 0.6667 | −0.2487 | 0.138* | 0.50 |
C8 | 0.5105 (2) | 0.7500 | 0.1331 (4) | 0.0509 (16) | |
C9 | 0.6179 (3) | 0.7500 | 0.1292 (4) | 0.0649 (19) | |
C10 | 0.7200 (3) | 0.7500 | 0.1477 (5) | 0.099 (3) | |
H10A | 0.7258 | 0.8631 | 0.1146 | 0.119* | 0.50 |
H10B | 0.7258 | 0.6369 | 0.1146 | 0.119* | 0.50 |
C11 | 0.7608 (3) | 0.7500 | 0.2167 (5) | 0.129 (4) | |
H11A | 0.8004 | 0.7500 | 0.1972 | 0.193* | |
H11B | 0.7542 | 0.6376 | 0.2488 | 0.193* | 0.50 |
H11C | 0.7542 | 0.8624 | 0.2488 | 0.193* | 0.50 |
C12 | 0.3383 (3) | 0.7500 | 0.5751 (4) | 0.061 (2) | |
C13 | 0.3094 (2) | 0.5825 (10) | 0.5800 (3) | 0.0831 (17) | |
H13 | 0.3293 | 0.4668 | 0.5745 | 0.100* | |
C14 | 0.2490 (2) | 0.5846 (11) | 0.5936 (3) | 0.0909 (19) | |
H14 | 0.2289 | 0.4687 | 0.5962 | 0.109* | |
C15 | 0.2190 (3) | 0.7500 | 0.6028 (4) | 0.075 (3) | |
C16 | 0.1543 (3) | 0.7500 | 0.6234 (5) | 0.119 (4) | |
H16A | 0.1477 | 0.8278 | 0.6703 | 0.178* | 0.50 |
H16B | 0.1417 | 0.6211 | 0.6340 | 0.178* | 0.50 |
H16C | 0.1324 | 0.8012 | 0.5789 | 0.178* | 0.50 |
C17 | 0.4342 (2) | 0.7500 | 0.5071 (3) | 0.0454 (15) | |
C18 | 0.5224 (3) | 0.7500 | 0.5916 (4) | 0.0518 (16) | |
C19 | 0.6155 (3) | 0.7500 | 0.6510 (4) | 0.0623 (19) | |
H19A | 0.6075 | 0.6370 | 0.6833 | 0.075* | 0.50 |
H19B | 0.6075 | 0.8630 | 0.6833 | 0.075* | 0.50 |
C20 | 0.6773 (3) | 0.7500 | 0.6239 (5) | 0.093 (3) | |
H20A | 0.6837 | 0.8562 | 0.5881 | 0.139* | 0.50 |
H20B | 0.6855 | 0.6322 | 0.5962 | 0.139* | 0.50 |
H20C | 0.7026 | 0.7616 | 0.6698 | 0.139* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0484 (5) | 0.0897 (7) | 0.0359 (4) | 0.000 | −0.0006 (3) | 0.000 |
S1 | 0.0477 (9) | 0.1125 (16) | 0.0360 (9) | 0.000 | 0.0022 (7) | 0.000 |
S2 | 0.0384 (8) | 0.0879 (13) | 0.0352 (8) | 0.000 | −0.0065 (6) | 0.000 |
Cl1 | 0.0433 (9) | 0.161 (2) | 0.0451 (9) | 0.000 | 0.0001 (7) | 0.000 |
N1 | 0.045 (3) | 0.088 (4) | 0.037 (3) | 0.000 | 0.002 (2) | 0.000 |
N2 | 0.055 (3) | 0.077 (4) | 0.033 (3) | 0.000 | 0.001 (2) | 0.000 |
N3 | 0.037 (3) | 0.176 (7) | 0.028 (3) | 0.000 | −0.001 (2) | 0.000 |
N4 | 0.038 (3) | 0.067 (4) | 0.033 (3) | 0.000 | −0.007 (2) | 0.000 |
O1 | 0.058 (3) | 0.153 (5) | 0.039 (3) | 0.000 | 0.005 (2) | 0.000 |
O2 | 0.044 (2) | 0.131 (5) | 0.052 (3) | 0.000 | 0.007 (2) | 0.000 |
O3 | 0.051 (3) | 0.191 (6) | 0.037 (3) | 0.000 | −0.007 (2) | 0.000 |
O4 | 0.036 (2) | 0.081 (3) | 0.046 (2) | 0.000 | −0.0133 (19) | 0.000 |
C1 | 0.054 (4) | 0.078 (5) | 0.034 (3) | 0.000 | −0.001 (3) | 0.000 |
C2 | 0.059 (4) | 0.115 (6) | 0.038 (4) | 0.000 | 0.007 (3) | 0.000 |
C3 | 0.060 (5) | 0.160 (8) | 0.045 (4) | 0.000 | 0.002 (3) | 0.000 |
C4 | 0.072 (5) | 0.076 (5) | 0.044 (4) | 0.000 | −0.008 (3) | 0.000 |
C5 | 0.063 (5) | 0.115 (7) | 0.038 (4) | 0.000 | 0.006 (3) | 0.000 |
C6 | 0.058 (4) | 0.106 (6) | 0.042 (4) | 0.000 | 0.006 (3) | 0.000 |
C7 | 0.079 (5) | 0.139 (8) | 0.057 (5) | 0.000 | −0.020 (4) | 0.000 |
C8 | 0.044 (4) | 0.067 (5) | 0.042 (3) | 0.000 | 0.003 (3) | 0.000 |
C9 | 0.048 (4) | 0.098 (6) | 0.048 (4) | 0.000 | 0.006 (3) | 0.000 |
C10 | 0.048 (4) | 0.182 (10) | 0.068 (5) | 0.000 | 0.009 (4) | 0.000 |
C11 | 0.053 (5) | 0.249 (14) | 0.084 (6) | 0.000 | 0.009 (4) | 0.000 |
C12 | 0.038 (4) | 0.108 (7) | 0.037 (3) | 0.000 | −0.009 (3) | 0.000 |
C13 | 0.059 (3) | 0.102 (5) | 0.088 (4) | 0.008 (3) | −0.018 (3) | −0.009 (3) |
C14 | 0.056 (3) | 0.126 (6) | 0.090 (4) | −0.026 (4) | −0.011 (3) | 0.016 (4) |
C15 | 0.041 (4) | 0.147 (9) | 0.038 (4) | 0.000 | −0.001 (3) | 0.000 |
C16 | 0.045 (4) | 0.253 (13) | 0.057 (5) | 0.000 | 0.006 (4) | 0.000 |
C17 | 0.034 (3) | 0.058 (4) | 0.044 (3) | 0.000 | −0.010 (3) | 0.000 |
C18 | 0.044 (4) | 0.076 (5) | 0.035 (3) | 0.000 | −0.012 (3) | 0.000 |
C19 | 0.050 (4) | 0.082 (5) | 0.054 (4) | 0.000 | −0.022 (3) | 0.000 |
C20 | 0.046 (4) | 0.127 (8) | 0.105 (7) | 0.000 | −0.025 (4) | 0.000 |
Cu1—S2 | 2.2099 (17) | C4—C7 | 1.500 (9) |
Cu1—S1 | 2.2171 (18) | C5—C6 | 1.369 (9) |
Cu1—Cl1 | 2.2445 (19) | C5—H5 | 0.9300 |
S1—C8 | 1.689 (6) | C6—H6 | 0.9300 |
S2—C17 | 1.683 (6) | C7—H7A | 0.9600 |
N1—C8 | 1.306 (8) | C7—H7B | 0.9600 |
N1—C1 | 1.400 (7) | C7—H7C | 0.9600 |
N1—H1 | 0.8600 | C10—C11 | 1.475 (11) |
N2—C8 | 1.373 (7) | C10—H10A | 0.9700 |
N2—C9 | 1.373 (8) | C10—H10B | 0.9700 |
N2—H2A | 0.8600 | C11—H11A | 0.9600 |
N3—C17 | 1.312 (8) | C11—H11B | 0.9600 |
N3—C12 | 1.434 (8) | C11—H11C | 0.9600 |
N3—H3A | 0.8600 | C12—C13i | 1.343 (7) |
N4—C17 | 1.374 (7) | C12—C13 | 1.343 (7) |
N4—C18 | 1.380 (7) | C13—C14 | 1.397 (7) |
N4—H4 | 0.8600 | C13—H13 | 0.9300 |
O1—C9 | 1.192 (8) | C14—C15 | 1.351 (7) |
O2—C9 | 1.337 (8) | C14—H14 | 0.9300 |
O2—C10 | 1.464 (8) | C15—C14i | 1.351 (7) |
O3—C18 | 1.193 (7) | C15—C16 | 1.515 (9) |
O4—C18 | 1.319 (7) | C16—H16A | 0.9600 |
O4—C19 | 1.458 (7) | C16—H16B | 0.9600 |
C1—C2 | 1.373 (9) | C16—H16C | 0.9600 |
C1—C6 | 1.375 (9) | C19—C20 | 1.480 (9) |
C2—C3 | 1.376 (9) | C19—H19A | 0.9700 |
C2—H2 | 0.9300 | C19—H19B | 0.9700 |
C3—C4 | 1.391 (9) | C20—H20A | 0.9600 |
C3—H3 | 0.9300 | C20—H20B | 0.9600 |
C4—C5 | 1.345 (10) | C20—H20C | 0.9600 |
S2—Cu1—S1 | 118.77 (7) | O2—C10—C11 | 105.4 (6) |
S2—Cu1—Cl1 | 120.58 (7) | O2—C10—H10A | 110.7 |
S1—Cu1—Cl1 | 120.66 (7) | C11—C10—H10A | 110.7 |
C8—S1—Cu1 | 110.9 (2) | O2—C10—H10B | 110.7 |
C17—S2—Cu1 | 110.7 (2) | C11—C10—H10B | 110.7 |
C8—N1—C1 | 135.5 (5) | H10A—C10—H10B | 108.8 |
C8—N1—H1 | 112.2 | C10—C11—H11A | 109.5 |
C1—N1—H1 | 112.2 | C10—C11—H11B | 109.5 |
C8—N2—C9 | 126.6 (5) | H11A—C11—H11B | 109.5 |
C8—N2—H2A | 116.7 | C10—C11—H11C | 109.5 |
C9—N2—H2A | 116.7 | H11A—C11—H11C | 109.5 |
C17—N3—C12 | 127.6 (5) | H11B—C11—H11C | 109.5 |
C17—N3—H3A | 116.2 | C13i—C12—C13 | 120.8 (7) |
C12—N3—H3A | 116.2 | C13i—C12—N3 | 119.5 (3) |
C17—N4—C18 | 125.9 (5) | C13—C12—N3 | 119.5 (3) |
C17—N4—H4 | 117.0 | C12—C13—C14 | 119.0 (6) |
C18—N4—H4 | 117.0 | C12—C13—H13 | 120.5 |
C9—O2—C10 | 114.1 (5) | C14—C13—H13 | 120.5 |
C18—O4—C19 | 114.9 (5) | C15—C14—C13 | 121.9 (6) |
C2—C1—C6 | 117.0 (6) | C15—C14—H14 | 119.0 |
C2—C1—N1 | 126.7 (6) | C13—C14—H14 | 119.0 |
C6—C1—N1 | 116.3 (6) | C14i—C15—C14 | 117.2 (7) |
C1—C2—C3 | 120.4 (6) | C14i—C15—C16 | 121.4 (4) |
C1—C2—H2 | 119.8 | C14—C15—C16 | 121.4 (4) |
C3—C2—H2 | 119.8 | C15—C16—H16A | 109.5 |
C2—C3—C4 | 121.8 (7) | C15—C16—H16B | 109.5 |
C2—C3—H3 | 119.1 | H16A—C16—H16B | 109.5 |
C4—C3—H3 | 119.1 | C15—C16—H16C | 109.5 |
C5—C4—C3 | 117.2 (6) | H16A—C16—H16C | 109.5 |
C5—C4—C7 | 120.6 (7) | H16B—C16—H16C | 109.5 |
C3—C4—C7 | 122.2 (7) | N3—C17—N4 | 117.5 (5) |
C4—C5—C6 | 121.3 (7) | N3—C17—S2 | 121.7 (4) |
C4—C5—H5 | 119.3 | N4—C17—S2 | 120.8 (4) |
C6—C5—H5 | 119.3 | O3—C18—O4 | 125.7 (5) |
C5—C6—C1 | 122.3 (6) | O3—C18—N4 | 125.6 (6) |
C5—C6—H6 | 118.9 | O4—C18—N4 | 108.7 (5) |
C1—C6—H6 | 118.9 | O4—C19—C20 | 106.7 (6) |
C4—C7—H7A | 109.5 | O4—C19—H19A | 110.4 |
C4—C7—H7B | 109.5 | C20—C19—H19A | 110.4 |
H7A—C7—H7B | 109.5 | O4—C19—H19B | 110.4 |
C4—C7—H7C | 109.5 | C20—C19—H19B | 110.4 |
H7A—C7—H7C | 109.5 | H19A—C19—H19B | 108.6 |
H7B—C7—H7C | 109.5 | C19—C20—H20A | 109.5 |
N1—C8—N2 | 115.8 (5) | C19—C20—H20B | 109.5 |
N1—C8—S1 | 125.2 (5) | H20A—C20—H20B | 109.5 |
N2—C8—S1 | 119.0 (4) | C19—C20—H20C | 109.5 |
O1—C9—O2 | 124.5 (6) | H20A—C20—H20C | 109.5 |
O1—C9—N2 | 125.9 (6) | H20B—C20—H20C | 109.5 |
O2—C9—N2 | 109.6 (5) | ||
S2—Cu1—S1—C8 | 180.0 | C10—O2—C9—N2 | 180.0 |
Cl1—Cu1—S1—C8 | 0.0 | C8—N2—C9—O1 | 0.0 |
S1—Cu1—S2—C17 | 180.0 | C8—N2—C9—O2 | 180.0 |
Cl1—Cu1—S2—C17 | 0.0 | C9—O2—C10—C11 | 180.0 |
C8—N1—C1—C2 | 0.0 | C17—N3—C12—C13i | −92.7 (5) |
C8—N1—C1—C6 | 180.0 | C17—N3—C12—C13 | 92.7 (5) |
C6—C1—C2—C3 | 0.0 | C13i—C12—C13—C14 | −2.5 (10) |
N1—C1—C2—C3 | 180.0 | N3—C12—C13—C14 | 172.0 (5) |
C1—C2—C3—C4 | 0.0 | C12—C13—C14—C15 | −0.8 (9) |
C2—C3—C4—C5 | 0.0 | C13—C14—C15—C14i | 4.0 (11) |
C2—C3—C4—C7 | 180.0 | C13—C14—C15—C16 | −175.6 (6) |
C3—C4—C5—C6 | 0.0 | C12—N3—C17—N4 | 180.0 |
C7—C4—C5—C6 | 180.0 | C12—N3—C17—S2 | 0.000 (1) |
C4—C5—C6—C1 | 0.0 | C18—N4—C17—N3 | 0.0 |
C2—C1—C6—C5 | 0.0 | C18—N4—C17—S2 | 180.0 |
N1—C1—C6—C5 | 180.0 | Cu1—S2—C17—N3 | 180.0 |
C1—N1—C8—N2 | 180.0 | Cu1—S2—C17—N4 | 0.0 |
C1—N1—C8—S1 | 0.0 | C19—O4—C18—O3 | 0.000 (1) |
C9—N2—C8—N1 | 0.0 | C19—O4—C18—N4 | 180.0 |
C9—N2—C8—S1 | 180.0 | C17—N4—C18—O3 | 0.000 (1) |
Cu1—S1—C8—N1 | 180.0 | C17—N4—C18—O4 | 180.0 |
Cu1—S1—C8—N2 | 0.0 | C18—O4—C19—C20 | 180.000 (1) |
C10—O2—C9—O1 | 0.0 |
Symmetry code: (i) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.87 | 2.625 | 145 |
N2—H2A···Cl1 | 0.86 | 2.30 | 3.157 | 179 |
N3—H3A···O3 | 0.86 | 1.94 | 2.645 | 138 |
N4—H4···Cl1 | 0.86 | 2.31 | 3.172 | 178 |
Experimental details
Crystal data | |
Chemical formula | [CuCl(C11H14N2O2S)2] |
Mr | 575.59 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 22.826 (7), 6.971 (2), 16.593 (5) |
V (Å3) | 2640.1 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.30 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Make Model CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.542, 0.836 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14770, 2943, 1757 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.161, 1.15 |
No. of reflections | 2943 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.32 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.874 | 2.625 | 145 |
N2—H2A···Cl1 | 0.86 | 2.297 | 3.157 | 179 |
N3—H3A···O3 | 0.86 | 1.943 | 2.645 | 138 |
N4—H4···Cl1 | 0.86 | 2.313 | 3.172 | 178 |
In recent years, many transition metal complexes with thiourea derivatives have been reported (Guillon et al., 1996, 1998) and they have been popularly used in organic syntheses, such as metal-catalyzed asymmetric reduction of carbonyl compounds and carbonylative cyclization of o-hydroxylarylacetylenes etc. (Touchard et al., 1997; Nan et al., 2000). N-substituted-N'-acylthiourea has received greater attention because the existence of acyl and thiocarbonyl groups in the molecule enhances its coordination ability. As a part of our research into thiourea derivatives (Zhang et al., 2001, 2003), we have synthesized the title complex, (I), and the crystal structure is reported herein. \sch
In many cases of the synthesis of copper complexes, irreversible CuII/CuI systems were observed (Guillon et al., 1996, 1998), and much research work has been reported on the reduction of CuII in the presence of thione derivatives (Jeannin et al., 1979; Raper, 1985; Karagiannidis et al., 1990). In our process to synthesize complex (I), the cuprous complex was obtained from the reaction of cupric ions with thiourea. The reducing agent in this reaction is probably carbonylthiourea, according to previous publications (Jeannin et al., 1979). This reaction is similar to that reported by Shen et al. (1997).
In the molecular structure of (I), the two acylthiourea molecules adopt a cis-structure relative to the central CuI ion (Fig. 1). The CuI ion in (I) has trigonal geometry, made up of two S atoms from two ligands and one Cl atom, with Cl1—Cu1—S1 120.66 (7), Cl1—Cu1—S2 120.58 (7) and S1—Cu1—S2 118.77 (7)°. A very interesting phenomenon is that almost all the atoms in the molecule are in the same plane; the mean deviation from the plane is 0 Å, except for one benzene ring which is nearly perpendicular to this plane, at an angle of 92.4°. The molecules of (I) are packed in layers vertical to the b axis, with a distance between these molecular layers of 3.485 Å.
The existence of intramolecular hydrogen bonds in carbonylthiourea evidently influences its coordination properties and promotes the stability of the complexes it forms. In the coordination compound reported by Bourne & Koch (1993), namely cis-bis(N-Benzoyl-N'-propylthiourea)dichloroplatinum(II), the two ligand molecules bind to PtII via the S atoms only, the carbonyl O atoms being locked into position by hydrogen bonds similar to those in the free ligand. The same observation was reported for a CuI complex by Shen et al. (1997). By comparison, in N,N-disubstituted carbonylthiourea complexes, the carbonyl O atom commonly participates in coordination with the central metal ion, e.g. in PtII and CuII complexes (Koch et al., 1994; Richter et al., 1980). This is due to the absence of a thioamide H atom in N,N-disubstituted carbonylthiourea, and thus no hydrogen bonds form. This is also confirmed in complex (I). Here, there are four intramolecular hydrogen bonds in the molecule (Table 1). The acyl atoms O1 and O3 form hydrogen bonds with the H atoms on atoms N1 and N3, and atom Cl1 forms hydrogen bonds with the H atoms on atoms N2 and N4. Since they are locked into the planar six-membered ring formed by these hydrogen bonds, the acyl O atoms in the ligands cannot take part in the coordination with CuI in the same way as the S atoms.