Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113012547/fn3135sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113012547/fn3135Isup2.hkl |
CCDC reference: 950432
For related literature, see: Angelusiu et al. (2009); Babb et al. (2003); Belicchi-Ferrari, Bisceglie, Pelosi, Pinelli & Tarasconi (2007); Belicchi-Ferrari, Fava, Pelosi & Tarasconi (2000); Bera et al. (2004); Hassanien et al. (2008); Ke et al. (2007); Latheef et al. (2006); Leovac et al. (2009); Lin et al. (2001); Moon et al. (2006); Palaska et al. (2002); Pradeep & Leroy (2007); Simonov et al. (2002); Wang et al. (2000, 2010); Wei et al. (2012).
The 2-hydroxy-N'-(2-oxo-2-phenylethanethioyl)benzohydrazide ligand was prepared according to the literature method of Wang et al. (2000). The ligand (0.0315 g, 0.1 mmol) and copper(II) chloride dihydrate (0.0341 g, 0.2 mmol) were dissolved in a mixed solvent of methanol and dimethylformamide (12 ml, 5:1 v/v). Diaminodiphenylmethane (0.0102 g 0.05 mmol) was added and the solution was stirred for 3 h at room temperature. The resulting dark-green mixture was filtered and the filtrate was allowed to evaporate in air at room temperature. Black crystals of (I) were separated from the filtrate after 5 d.
All C- and N-bound H atoms were located in idealized positions using the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cu8(C15H10N3O3S)4Cl4(C3H7NO)2]·2C3H7NO | F(000) = 2208 |
Mr = 2191.78 | Dx = 1.762 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 31053 reflections |
a = 9.5672 (19) Å | θ = 4.8–37.0° |
b = 19.153 (4) Å | µ = 2.32 mm−1 |
c = 23.006 (5) Å | T = 298 K |
β = 101.53 (3)° | Plate, black |
V = 4130.6 (14) Å3 | 0.48 × 0.46 × 0.08 mm |
Z = 2 |
Bruker APEXII area-detector diffractometer | 7277 independent reflections |
Radiation source: fine-focus sealed tube | 3279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.102 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −11→11 |
Tmin = 0.324, Tmax = 0.852 | k = −22→22 |
24190 measured reflections | l = −23→27 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0107P)2] where P = (Fo2 + 2Fc2)/3 |
7277 reflections | (Δ/σ)max < 0.001 |
545 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[Cu8(C15H10N3O3S)4Cl4(C3H7NO)2]·2C3H7NO | V = 4130.6 (14) Å3 |
Mr = 2191.78 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5672 (19) Å | µ = 2.32 mm−1 |
b = 19.153 (4) Å | T = 298 K |
c = 23.006 (5) Å | 0.48 × 0.46 × 0.08 mm |
β = 101.53 (3)° |
Bruker APEXII area-detector diffractometer | 7277 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 3279 reflections with I > 2σ(I) |
Tmin = 0.324, Tmax = 0.852 | Rint = 0.102 |
24190 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.43 e Å−3 |
7277 reflections | Δρmin = −0.39 e Å−3 |
545 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 | ||
Cu3 | 0.39336 (7) | 0.34243 (3) | 0.05179 (3) | 0.0466 (2) | |
Cu2 | 0.41792 (7) | 0.18888 (3) | 0.02684 (3) | 0.0484 (2) | |
Cu1 | 0.17175 (7) | −0.01066 (3) | 0.05228 (3) | 0.0534 (2) | |
C24 | 0.2240 (6) | 0.4713 (2) | 0.0437 (2) | 0.0417 (15) | |
Cu4 | 0.27845 (7) | 0.54031 (3) | −0.06425 (3) | 0.0487 (2) | |
S2 | 0.24764 (15) | 0.40676 (7) | 0.09695 (6) | 0.0487 (4) | |
S1 | 0.44019 (16) | 0.11889 (6) | −0.04867 (7) | 0.0562 (5) | |
Cl1 | 0.01911 (17) | −0.07536 (7) | 0.08654 (8) | 0.0805 (6) | |
O4 | 0.4752 (4) | 0.27899 (14) | 0.00178 (16) | 0.0463 (10) | |
O3 | 0.3824 (4) | 0.24981 (15) | 0.08936 (16) | 0.0472 (10) | |
O1 | 0.1750 (4) | −0.07137 (17) | −0.01473 (18) | 0.0612 (12) | |
O2 | 0.2019 (4) | 0.05524 (17) | 0.11715 (16) | 0.0568 (11) | |
N2 | 0.2962 (4) | 0.0518 (2) | 0.0232 (2) | 0.0430 (12) | |
N3 | 0.3299 (4) | 0.11163 (19) | 0.0584 (2) | 0.0458 (13) | |
N1 | 0.3175 (4) | −0.0055 (2) | −0.06389 (19) | 0.0503 (13) | |
H1 | 0.3568 | −0.0049 | −0.0944 | 0.060* | |
C9 | 0.3434 (6) | 0.0524 (3) | −0.0253 (3) | 0.0463 (16) | |
C1 | 0.2345 (6) | −0.0633 (3) | −0.0573 (3) | 0.0523 (18) | |
C3 | 0.3122 (6) | −0.1253 (3) | −0.1422 (3) | 0.0603 (18) | |
H3 | 0.3923 | −0.0970 | −0.1387 | 0.072* | |
C17 | 0.5376 (6) | 0.2969 (3) | −0.0433 (3) | 0.0414 (15) | |
C11 | 0.3081 (5) | 0.1630 (3) | 0.1524 (3) | 0.0424 (15) | |
C15 | 0.3899 (6) | 0.2765 (3) | 0.1900 (3) | 0.0536 (17) | |
H15 | 0.4223 | 0.3212 | 0.1838 | 0.064* | |
C2 | 0.2186 (6) | −0.1166 (3) | −0.1047 (3) | 0.0468 (16) | |
C10 | 0.2760 (6) | 0.1073 (3) | 0.1076 (3) | 0.0426 (15) | |
C16 | 0.3599 (6) | 0.2303 (3) | 0.1431 (3) | 0.0442 (15) | |
C12 | 0.2871 (6) | 0.1464 (3) | 0.2093 (3) | 0.0567 (17) | |
H12 | 0.2491 | 0.1031 | 0.2157 | 0.068* | |
C13 | 0.3207 (6) | 0.1918 (3) | 0.2553 (3) | 0.0612 (18) | |
H13 | 0.3090 | 0.1790 | 0.2931 | 0.073* | |
C7 | 0.0969 (6) | −0.1573 (3) | −0.1111 (3) | 0.077 (2) | |
H7 | 0.0319 | −0.1503 | −0.0865 | 0.092* | |
C4 | 0.2859 (7) | −0.1770 (3) | −0.1856 (3) | 0.0667 (19) | |
H4 | 0.3504 | −0.1844 | −0.2103 | 0.080* | |
C5 | 0.1645 (8) | −0.2173 (3) | −0.1920 (3) | 0.080 (2) | |
H5 | 0.1450 | −0.2507 | −0.2219 | 0.096* | |
C6 | 0.0730 (7) | −0.2079 (3) | −0.1541 (4) | 0.092 (3) | |
H6 | −0.0071 | −0.2363 | −0.1576 | 0.110* | |
C21 | 0.5800 (5) | 0.3756 (3) | −0.1198 (2) | 0.0453 (15) | |
H21 | 0.5641 | 0.4182 | −0.1395 | 0.054* | |
C20 | 0.6698 (6) | 0.3280 (3) | −0.1381 (2) | 0.0547 (17) | |
H20 | 0.7100 | 0.3378 | −0.1708 | 0.066* | |
C18 | 0.6363 (6) | 0.2520 (2) | −0.0613 (3) | 0.0505 (17) | |
H18 | 0.6593 | 0.2107 | −0.0403 | 0.061* | |
C22 | 0.5117 (5) | 0.3620 (3) | −0.0726 (2) | 0.0406 (15) | |
C19 | 0.7004 (6) | 0.2656 (3) | −0.1078 (3) | 0.0540 (17) | |
H19 | 0.7633 | 0.2336 | −0.1190 | 0.065* | |
C14 | 0.3728 (6) | 0.2576 (3) | 0.2455 (3) | 0.0605 (18) | |
H14 | 0.3962 | 0.2889 | 0.2768 | 0.073* | |
O5 | 0.3919 (4) | 0.46983 (16) | −0.09307 (15) | 0.0527 (11) | |
N5 | 0.2816 (4) | 0.47185 (19) | −0.00202 (19) | 0.0395 (12) | |
N6 | 0.1331 (4) | 0.5261 (2) | 0.05204 (18) | 0.0449 (12) | |
H6A | 0.0861 | 0.5207 | 0.0799 | 0.054* | |
N4 | 0.3697 (4) | 0.41427 (19) | −0.00783 (18) | 0.0368 (11) | |
C23 | 0.4184 (5) | 0.4177 (3) | −0.0580 (3) | 0.0390 (15) | |
Cl2 | 0.34465 (14) | 0.62983 (6) | −0.11493 (6) | 0.0529 (4) | |
O7 | 0.0657 (4) | 0.51708 (18) | −0.13635 (18) | 0.0640 (12) | |
O6 | 0.1610 (4) | 0.59854 (16) | −0.02370 (17) | 0.0555 (12) | |
C26 | 0.0201 (6) | 0.6418 (3) | 0.0416 (3) | 0.0455 (15) | |
C25 | 0.1106 (6) | 0.5871 (3) | 0.0209 (3) | 0.0456 (16) | |
N7 | −0.0444 (5) | 0.5541 (3) | −0.2273 (3) | 0.0625 (15) | |
C31 | −0.0011 (6) | 0.7014 (3) | 0.0087 (3) | 0.0570 (17) | |
H31 | 0.0326 | 0.7050 | −0.0264 | 0.068* | |
C30 | −0.0744 (7) | 0.7573 (3) | 0.0284 (3) | 0.071 (2) | |
H30 | −0.0892 | 0.7983 | 0.0063 | 0.086* | |
C29 | −0.1230 (6) | 0.7516 (3) | 0.0788 (3) | 0.072 (2) | |
H29 | −0.1710 | 0.7890 | 0.0917 | 0.086* | |
C32 | 0.0193 (6) | 0.5629 (3) | −0.1722 (3) | 0.0552 (18) | |
H32 | 0.0307 | 0.6087 | −0.1586 | 0.066* | |
C27 | −0.0303 (6) | 0.6356 (3) | 0.0923 (3) | 0.070 (2) | |
H27 | −0.0167 | 0.5944 | 0.1141 | 0.084* | |
C28 | −0.1030 (6) | 0.6918 (3) | 0.1116 (3) | 0.078 (2) | |
H28 | −0.1375 | 0.6883 | 0.1465 | 0.093* | |
C33 | −0.0661 (8) | 0.4853 (3) | −0.2527 (3) | 0.147 (4) | |
H33A | 0.0081 | 0.4548 | −0.2331 | 0.221* | |
H33B | −0.0641 | 0.4875 | −0.2942 | 0.221* | |
H33C | −0.1570 | 0.4678 | −0.2477 | 0.221* | |
C34 | −0.1024 (6) | 0.6121 (3) | −0.2669 (3) | 0.089 (2) | |
H34A | −0.0885 | 0.6552 | −0.2453 | 0.134* | |
H34B | −0.2024 | 0.6048 | −0.2816 | 0.134* | |
H34C | −0.0539 | 0.6141 | −0.2996 | 0.134* | |
N8 | 0.4154 (6) | −0.0589 (3) | 0.2213 (2) | 0.0628 (15) | |
C35 | 0.4662 (7) | −0.0543 (3) | 0.1726 (3) | 0.068 (2) | |
H35 | 0.4215 | −0.0810 | 0.1405 | 0.081* | |
O8 | 0.5672 (5) | −0.0181 (2) | 0.16552 (18) | 0.0770 (14) | |
C37 | 0.4734 (7) | −0.0171 (3) | 0.2717 (3) | 0.093 (2) | |
H37A | 0.5610 | −0.0375 | 0.2924 | 0.139* | |
H37B | 0.4066 | −0.0148 | 0.2978 | 0.139* | |
H37C | 0.4916 | 0.0292 | 0.2590 | 0.139* | |
C36 | 0.2939 (7) | −0.1033 (3) | 0.2249 (3) | 0.107 (3) | |
H36A | 0.2199 | −0.0756 | 0.2361 | 0.160* | |
H36B | 0.3230 | −0.1391 | 0.2539 | 0.160* | |
H36C | 0.2588 | −0.1244 | 0.1869 | 0.160* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu3 | 0.0628 (5) | 0.0336 (4) | 0.0459 (5) | −0.0005 (4) | 0.0171 (4) | 0.0020 (4) |
Cu2 | 0.0647 (5) | 0.0325 (4) | 0.0509 (5) | −0.0049 (4) | 0.0185 (4) | 0.0005 (4) |
Cu1 | 0.0576 (5) | 0.0413 (4) | 0.0616 (6) | −0.0075 (4) | 0.0130 (4) | 0.0029 (4) |
C24 | 0.044 (4) | 0.036 (4) | 0.044 (4) | −0.015 (3) | 0.005 (3) | −0.004 (3) |
Cu4 | 0.0575 (5) | 0.0409 (4) | 0.0492 (5) | 0.0015 (4) | 0.0142 (4) | 0.0059 (4) |
S2 | 0.0588 (11) | 0.0424 (9) | 0.0480 (11) | 0.0026 (8) | 0.0179 (9) | 0.0049 (8) |
S1 | 0.0813 (13) | 0.0352 (8) | 0.0597 (12) | −0.0083 (8) | 0.0325 (10) | −0.0032 (8) |
Cl1 | 0.0832 (13) | 0.0662 (11) | 0.1000 (15) | −0.0327 (9) | 0.0376 (11) | −0.0103 (10) |
O4 | 0.066 (3) | 0.025 (2) | 0.054 (3) | −0.0012 (18) | 0.026 (2) | 0.0009 (19) |
O3 | 0.075 (3) | 0.029 (2) | 0.040 (3) | −0.0038 (18) | 0.018 (2) | −0.0018 (19) |
O1 | 0.087 (3) | 0.044 (2) | 0.056 (3) | −0.017 (2) | 0.024 (3) | −0.005 (2) |
O2 | 0.074 (3) | 0.042 (2) | 0.058 (3) | −0.019 (2) | 0.020 (2) | −0.003 (2) |
N2 | 0.059 (3) | 0.032 (3) | 0.040 (3) | −0.006 (2) | 0.014 (3) | 0.001 (2) |
N3 | 0.065 (3) | 0.024 (3) | 0.049 (4) | −0.007 (2) | 0.014 (3) | 0.004 (2) |
N1 | 0.063 (3) | 0.038 (3) | 0.053 (4) | −0.003 (3) | 0.017 (3) | 0.004 (3) |
C9 | 0.055 (4) | 0.031 (3) | 0.056 (5) | 0.005 (3) | 0.018 (4) | 0.007 (3) |
C1 | 0.070 (5) | 0.029 (4) | 0.053 (5) | 0.002 (3) | −0.001 (4) | 0.000 (4) |
C3 | 0.059 (5) | 0.044 (4) | 0.073 (5) | −0.007 (3) | 0.002 (4) | −0.007 (4) |
C17 | 0.041 (4) | 0.032 (3) | 0.051 (5) | −0.012 (3) | 0.011 (3) | −0.012 (3) |
C11 | 0.044 (4) | 0.043 (4) | 0.039 (4) | −0.009 (3) | 0.005 (3) | −0.003 (3) |
C15 | 0.071 (5) | 0.039 (4) | 0.048 (5) | 0.006 (3) | 0.007 (4) | 0.003 (4) |
C2 | 0.050 (4) | 0.036 (4) | 0.052 (5) | 0.004 (3) | 0.008 (4) | −0.002 (3) |
C10 | 0.048 (4) | 0.039 (4) | 0.040 (4) | 0.009 (3) | 0.006 (3) | 0.012 (3) |
C16 | 0.052 (4) | 0.041 (4) | 0.040 (5) | 0.007 (3) | 0.010 (3) | 0.008 (3) |
C12 | 0.067 (5) | 0.052 (4) | 0.054 (5) | −0.004 (3) | 0.016 (4) | 0.002 (4) |
C13 | 0.078 (5) | 0.066 (4) | 0.048 (5) | 0.002 (4) | 0.032 (4) | 0.004 (4) |
C7 | 0.062 (5) | 0.050 (4) | 0.124 (7) | −0.013 (4) | 0.032 (5) | −0.035 (4) |
C4 | 0.079 (6) | 0.062 (4) | 0.062 (5) | 0.016 (4) | 0.019 (4) | −0.016 (4) |
C5 | 0.079 (6) | 0.066 (5) | 0.085 (6) | −0.003 (4) | −0.009 (5) | −0.025 (4) |
C6 | 0.076 (6) | 0.074 (5) | 0.132 (8) | −0.015 (4) | 0.039 (5) | −0.039 (5) |
C21 | 0.054 (4) | 0.045 (4) | 0.037 (4) | −0.011 (3) | 0.009 (3) | 0.003 (3) |
C20 | 0.053 (4) | 0.069 (4) | 0.047 (4) | 0.000 (3) | 0.022 (4) | −0.005 (4) |
C18 | 0.063 (5) | 0.034 (4) | 0.056 (5) | −0.012 (3) | 0.016 (4) | 0.002 (3) |
C22 | 0.039 (4) | 0.044 (4) | 0.038 (4) | −0.010 (3) | 0.007 (3) | 0.002 (3) |
C19 | 0.050 (4) | 0.043 (4) | 0.070 (5) | −0.005 (3) | 0.015 (4) | −0.008 (4) |
C14 | 0.073 (5) | 0.050 (4) | 0.054 (5) | 0.007 (3) | 0.003 (4) | −0.007 (4) |
O5 | 0.069 (3) | 0.043 (2) | 0.052 (3) | 0.012 (2) | 0.026 (2) | 0.009 (2) |
N5 | 0.051 (3) | 0.033 (3) | 0.037 (3) | 0.000 (2) | 0.014 (3) | 0.003 (2) |
N6 | 0.051 (3) | 0.035 (3) | 0.053 (3) | 0.001 (2) | 0.021 (3) | −0.002 (3) |
N4 | 0.049 (3) | 0.030 (3) | 0.032 (3) | −0.001 (2) | 0.009 (3) | −0.004 (2) |
C23 | 0.042 (4) | 0.038 (4) | 0.038 (4) | 0.001 (3) | 0.009 (3) | −0.006 (3) |
Cl2 | 0.0584 (10) | 0.0466 (9) | 0.0541 (10) | −0.0054 (7) | 0.0122 (8) | 0.0105 (8) |
O7 | 0.079 (3) | 0.050 (3) | 0.058 (3) | −0.006 (2) | 0.002 (3) | 0.005 (2) |
O6 | 0.073 (3) | 0.042 (2) | 0.059 (3) | 0.011 (2) | 0.029 (2) | 0.013 (2) |
C26 | 0.052 (4) | 0.031 (4) | 0.052 (5) | −0.003 (3) | 0.006 (4) | −0.008 (3) |
C25 | 0.046 (4) | 0.035 (4) | 0.052 (5) | −0.012 (3) | 0.000 (4) | −0.006 (3) |
N7 | 0.064 (4) | 0.068 (4) | 0.052 (4) | 0.003 (3) | 0.004 (3) | −0.001 (4) |
C31 | 0.066 (5) | 0.048 (4) | 0.053 (5) | 0.005 (4) | 0.000 (4) | −0.002 (4) |
C30 | 0.087 (6) | 0.046 (4) | 0.075 (6) | 0.014 (4) | 0.000 (5) | −0.004 (4) |
C29 | 0.065 (5) | 0.050 (5) | 0.100 (7) | 0.007 (4) | 0.013 (5) | −0.022 (5) |
C32 | 0.050 (5) | 0.070 (5) | 0.049 (5) | −0.002 (4) | 0.017 (4) | −0.007 (4) |
C27 | 0.092 (5) | 0.033 (4) | 0.098 (6) | −0.003 (4) | 0.049 (5) | −0.001 (4) |
C28 | 0.077 (5) | 0.061 (5) | 0.107 (6) | 0.002 (4) | 0.046 (5) | −0.001 (5) |
C33 | 0.209 (10) | 0.091 (6) | 0.110 (7) | −0.011 (6) | −0.047 (6) | −0.046 (5) |
C34 | 0.076 (5) | 0.112 (6) | 0.074 (5) | 0.026 (4) | 0.001 (4) | 0.031 (5) |
N8 | 0.077 (4) | 0.071 (4) | 0.040 (4) | 0.001 (3) | 0.010 (3) | 0.003 (3) |
C35 | 0.081 (6) | 0.065 (5) | 0.054 (5) | 0.010 (4) | 0.008 (5) | −0.002 (4) |
O8 | 0.105 (4) | 0.069 (3) | 0.066 (3) | −0.020 (3) | 0.038 (3) | −0.008 (2) |
C37 | 0.161 (7) | 0.071 (5) | 0.049 (5) | −0.005 (5) | 0.027 (5) | −0.012 (4) |
C36 | 0.086 (6) | 0.157 (7) | 0.078 (6) | −0.044 (5) | 0.020 (5) | −0.008 (5) |
Cu3—N4 | 1.924 (4) | C5—C6 | 1.364 (7) |
Cu3—O4 | 1.942 (3) | C5—H5 | 0.9300 |
Cu3—O3 | 1.985 (3) | C6—H6 | 0.9300 |
Cu3—S2 | 2.2629 (15) | C21—C20 | 1.375 (6) |
Cu3—Cl2i | 2.6869 (17) | C21—C22 | 1.400 (6) |
Cu3—Cu2 | 3.0146 (10) | C21—H21 | 0.9300 |
Cu2—N3 | 1.916 (4) | C20—C19 | 1.387 (6) |
Cu2—O4 | 1.933 (3) | C20—H20 | 0.9300 |
Cu2—O3 | 1.934 (3) | C18—C19 | 1.360 (6) |
Cu2—S1 | 2.2378 (15) | C18—H18 | 0.9300 |
Cu1—N2 | 1.901 (4) | C22—C23 | 1.473 (6) |
Cu1—O2 | 1.932 (3) | C19—H19 | 0.9300 |
Cu1—O1 | 1.936 (4) | C14—H14 | 0.9300 |
Cu1—Cl1 | 2.1793 (16) | O5—C23 | 1.278 (5) |
C24—N5 | 1.282 (6) | N5—N4 | 1.410 (5) |
C24—N6 | 1.401 (5) | N6—C25 | 1.365 (6) |
C24—S2 | 1.723 (5) | N6—H6A | 0.8600 |
Cu4—O5 | 1.931 (3) | N4—C23 | 1.329 (6) |
Cu4—N5 | 1.937 (4) | Cl2—Cu3i | 2.6869 (17) |
Cu4—O6 | 1.948 (4) | O7—C32 | 1.225 (6) |
Cu4—Cl2 | 2.2349 (14) | O6—C25 | 1.237 (6) |
Cu4—O7 | 2.396 (4) | C26—C27 | 1.353 (7) |
S1—C9 | 1.723 (5) | C26—C31 | 1.363 (6) |
O4—C17 | 1.341 (5) | C26—C25 | 1.495 (7) |
O3—C16 | 1.349 (6) | N7—C32 | 1.305 (6) |
O1—C1 | 1.238 (6) | N7—C33 | 1.438 (6) |
O2—C10 | 1.267 (5) | N7—C34 | 1.473 (6) |
N2—C9 | 1.285 (6) | C31—C30 | 1.404 (7) |
N2—N3 | 1.403 (5) | C31—H31 | 0.9300 |
N3—C10 | 1.337 (6) | C30—C29 | 1.338 (7) |
N1—C1 | 1.388 (6) | C30—H30 | 0.9300 |
N1—C9 | 1.410 (6) | C29—C28 | 1.364 (7) |
N1—H1 | 0.8600 | C29—H29 | 0.9300 |
C1—C2 | 1.480 (7) | C32—H32 | 0.9300 |
C3—C2 | 1.372 (6) | C27—C28 | 1.401 (7) |
C3—C4 | 1.393 (6) | C27—H27 | 0.9300 |
C3—H3 | 0.9300 | C28—H28 | 0.9300 |
C17—C18 | 1.400 (6) | C33—H33A | 0.9600 |
C17—C22 | 1.415 (6) | C33—H33B | 0.9600 |
C11—C12 | 1.401 (6) | C33—H33C | 0.9600 |
C11—C16 | 1.412 (6) | C34—H34A | 0.9600 |
C11—C10 | 1.472 (6) | C34—H34B | 0.9600 |
C15—C14 | 1.367 (6) | C34—H34C | 0.9600 |
C15—C16 | 1.381 (6) | N8—C35 | 1.310 (7) |
C15—H15 | 0.9300 | N8—C37 | 1.427 (6) |
C2—C7 | 1.384 (7) | N8—C36 | 1.455 (6) |
C12—C13 | 1.358 (6) | C35—O8 | 1.227 (6) |
C12—H12 | 0.9300 | C35—H35 | 0.9300 |
C13—C14 | 1.391 (6) | C37—H37A | 0.9600 |
C13—H13 | 0.9300 | C37—H37B | 0.9600 |
C7—C6 | 1.372 (7) | C37—H37C | 0.9600 |
C7—H7 | 0.9300 | C36—H36A | 0.9600 |
C4—C5 | 1.378 (7) | C36—H36B | 0.9600 |
C4—H4 | 0.9300 | C36—H36C | 0.9600 |
N4—Cu3—O4 | 91.67 (16) | C5—C4—H4 | 119.9 |
N4—Cu3—O3 | 160.14 (15) | C3—C4—H4 | 119.9 |
O4—Cu3—O3 | 76.21 (13) | C6—C5—C4 | 119.5 (7) |
N4—Cu3—S2 | 86.69 (13) | C6—C5—H5 | 120.3 |
O4—Cu3—S2 | 166.13 (11) | C4—C5—H5 | 120.3 |
O3—Cu3—S2 | 101.28 (11) | C5—C6—C7 | 121.3 (6) |
N4—Cu3—Cl2i | 102.02 (12) | C5—C6—H6 | 119.4 |
O4—Cu3—Cl2i | 90.06 (11) | C7—C6—H6 | 119.4 |
O3—Cu3—Cl2i | 93.79 (10) | C20—C21—C22 | 122.0 (5) |
S2—Cu3—Cl2i | 103.76 (5) | C20—C21—H21 | 119.0 |
N4—Cu3—Cu2 | 124.37 (12) | C22—C21—H21 | 119.0 |
O4—Cu3—Cu2 | 38.83 (9) | C21—C20—C19 | 120.0 (5) |
O3—Cu3—Cu2 | 39.11 (10) | C21—C20—H20 | 120.0 |
S2—Cu3—Cu2 | 134.21 (4) | C19—C20—H20 | 120.0 |
Cl2i—Cu3—Cu2 | 101.31 (4) | C19—C18—C17 | 123.4 (5) |
N3—Cu2—O4 | 167.09 (16) | C19—C18—H18 | 118.3 |
N3—Cu2—O3 | 91.61 (17) | C17—C18—H18 | 118.3 |
O4—Cu2—O3 | 77.62 (14) | C21—C22—C17 | 118.1 (5) |
N3—Cu2—S1 | 87.08 (14) | C21—C22—C23 | 116.2 (5) |
O4—Cu2—S1 | 103.10 (11) | C17—C22—C23 | 125.8 (5) |
O3—Cu2—S1 | 175.38 (11) | C18—C19—C20 | 118.6 (5) |
N3—Cu2—Cu3 | 128.62 (14) | C18—C19—H19 | 120.7 |
O4—Cu2—Cu3 | 39.05 (10) | C20—C19—H19 | 120.7 |
O3—Cu2—Cu3 | 40.35 (10) | C15—C14—C13 | 120.5 (6) |
S1—Cu2—Cu3 | 139.05 (4) | C15—C14—H14 | 119.8 |
N2—Cu1—O2 | 81.56 (17) | C13—C14—H14 | 119.8 |
N2—Cu1—O1 | 89.25 (17) | C23—O5—Cu4 | 112.6 (3) |
O2—Cu1—O1 | 169.68 (16) | C24—N5—N4 | 115.7 (4) |
N2—Cu1—Cl1 | 175.61 (13) | C24—N5—Cu4 | 131.8 (4) |
O2—Cu1—Cl1 | 95.72 (12) | N4—N5—Cu4 | 112.4 (3) |
O1—Cu1—Cl1 | 93.73 (12) | C25—N6—C24 | 127.4 (5) |
N5—C24—N6 | 119.1 (5) | C25—N6—H6A | 116.3 |
N5—C24—S2 | 125.0 (4) | C24—N6—H6A | 116.3 |
N6—C24—S2 | 115.9 (4) | C23—N4—N5 | 111.3 (4) |
O5—Cu4—N5 | 81.59 (16) | C23—N4—Cu3 | 129.9 (4) |
O5—Cu4—O6 | 169.20 (15) | N5—N4—Cu3 | 118.6 (3) |
N5—Cu4—O6 | 87.64 (16) | O5—C23—N4 | 121.8 (5) |
O5—Cu4—Cl2 | 96.88 (11) | O5—C23—C22 | 118.3 (5) |
N5—Cu4—Cl2 | 160.15 (13) | N4—C23—C22 | 119.8 (5) |
O6—Cu4—Cl2 | 93.52 (11) | Cu4—Cl2—Cu3i | 101.58 (6) |
O5—Cu4—O7 | 95.19 (14) | C32—O7—Cu4 | 118.4 (4) |
N5—Cu4—O7 | 105.76 (15) | C25—O6—Cu4 | 130.8 (4) |
O6—Cu4—O7 | 86.93 (14) | C27—C26—C31 | 120.8 (5) |
Cl2—Cu4—O7 | 94.09 (10) | C27—C26—C25 | 122.8 (6) |
C24—S2—Cu3 | 94.0 (2) | C31—C26—C25 | 116.2 (6) |
C9—S1—Cu2 | 93.5 (2) | O6—C25—N6 | 122.7 (5) |
C17—O4—Cu2 | 131.0 (3) | O6—C25—C26 | 119.1 (5) |
C17—O4—Cu3 | 126.3 (3) | N6—C25—C26 | 118.2 (5) |
Cu2—O4—Cu3 | 102.12 (16) | C32—N7—C33 | 121.0 (6) |
C16—O3—Cu2 | 126.7 (3) | C32—N7—C34 | 123.2 (6) |
C16—O3—Cu3 | 132.7 (3) | C33—N7—C34 | 115.7 (5) |
Cu2—O3—Cu3 | 100.54 (16) | C26—C31—C30 | 119.2 (6) |
C1—O1—Cu1 | 129.7 (4) | C26—C31—H31 | 120.4 |
C10—O2—Cu1 | 112.5 (4) | C30—C31—H31 | 120.4 |
C9—N2—N3 | 114.5 (4) | C29—C30—C31 | 120.0 (6) |
C9—N2—Cu1 | 131.6 (4) | C29—C30—H30 | 120.0 |
N3—N2—Cu1 | 113.5 (3) | C31—C30—H30 | 120.0 |
C10—N3—N2 | 110.8 (4) | C30—C29—C28 | 120.9 (7) |
C10—N3—Cu2 | 129.9 (4) | C30—C29—H29 | 119.6 |
N2—N3—Cu2 | 118.6 (3) | C28—C29—H29 | 119.6 |
C1—N1—C9 | 126.2 (5) | O7—C32—N7 | 126.7 (6) |
C1—N1—H1 | 116.9 | O7—C32—H32 | 116.7 |
C9—N1—H1 | 116.9 | N7—C32—H32 | 116.7 |
N2—C9—N1 | 119.5 (5) | C26—C27—C28 | 119.4 (6) |
N2—C9—S1 | 125.5 (4) | C26—C27—H27 | 120.3 |
N1—C9—S1 | 115.0 (4) | C28—C27—H27 | 120.3 |
O1—C1—N1 | 123.3 (5) | C29—C28—C27 | 119.6 (6) |
O1—C1—C2 | 120.1 (6) | C29—C28—H28 | 120.2 |
N1—C1—C2 | 116.6 (6) | C27—C28—H28 | 120.2 |
C2—C3—C4 | 119.3 (6) | N7—C33—H33A | 109.5 |
C2—C3—H3 | 120.3 | N7—C33—H33B | 109.5 |
C4—C3—H3 | 120.3 | H33A—C33—H33B | 109.5 |
O4—C17—C18 | 120.1 (5) | N7—C33—H33C | 109.5 |
O4—C17—C22 | 122.1 (5) | H33A—C33—H33C | 109.5 |
C18—C17—C22 | 117.7 (5) | H33B—C33—H33C | 109.5 |
C12—C11—C16 | 118.0 (5) | N7—C34—H34A | 109.5 |
C12—C11—C10 | 116.1 (5) | N7—C34—H34B | 109.5 |
C16—C11—C10 | 125.9 (5) | H34A—C34—H34B | 109.5 |
C14—C15—C16 | 120.9 (6) | N7—C34—H34C | 109.5 |
C14—C15—H15 | 119.5 | H34A—C34—H34C | 109.5 |
C16—C15—H15 | 119.5 | H34B—C34—H34C | 109.5 |
C3—C2—C7 | 120.4 (6) | C35—N8—C37 | 120.5 (6) |
C3—C2—C1 | 124.2 (6) | C35—N8—C36 | 121.6 (6) |
C7—C2—C1 | 115.3 (6) | C37—N8—C36 | 117.8 (5) |
O2—C10—N3 | 121.2 (5) | O8—C35—N8 | 126.0 (7) |
O2—C10—C11 | 119.7 (5) | O8—C35—H35 | 117.0 |
N3—C10—C11 | 119.0 (5) | N8—C35—H35 | 117.0 |
O3—C16—C15 | 119.5 (5) | N8—C37—H37A | 109.5 |
O3—C16—C11 | 121.1 (5) | N8—C37—H37B | 109.5 |
C15—C16—C11 | 119.4 (6) | H37A—C37—H37B | 109.5 |
C13—C12—C11 | 121.9 (5) | N8—C37—H37C | 109.5 |
C13—C12—H12 | 119.1 | H37A—C37—H37C | 109.5 |
C11—C12—H12 | 119.1 | H37B—C37—H37C | 109.5 |
C12—C13—C14 | 119.3 (6) | N8—C36—H36A | 109.5 |
C12—C13—H13 | 120.4 | N8—C36—H36B | 109.5 |
C14—C13—H13 | 120.4 | H36A—C36—H36B | 109.5 |
C6—C7—C2 | 119.3 (6) | N8—C36—H36C | 109.5 |
C6—C7—H7 | 120.4 | H36A—C36—H36C | 109.5 |
C2—C7—H7 | 120.4 | H36B—C36—H36C | 109.5 |
C5—C4—C3 | 120.2 (6) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O8ii | 0.86 | 1.97 | 2.814 (6) | 167 |
N6—H6A···O7iii | 0.86 | 2.25 | 3.089 (6) | 164 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu8(C15H10N3O3S)4Cl4(C3H7NO)2]·2C3H7NO |
Mr | 2191.78 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.5672 (19), 19.153 (4), 23.006 (5) |
β (°) | 101.53 (3) |
V (Å3) | 4130.6 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.32 |
Crystal size (mm) | 0.48 × 0.46 × 0.08 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.324, 0.852 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24190, 7277, 3279 |
Rint | 0.102 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.067, 0.97 |
No. of reflections | 7277 |
No. of parameters | 545 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.39 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cu3—N4 | 1.924 (4) | Cu1—N2 | 1.901 (4) |
Cu3—O4 | 1.942 (3) | Cu1—O2 | 1.932 (3) |
Cu3—O3 | 1.985 (3) | Cu1—O1 | 1.936 (4) |
Cu3—S2 | 2.2629 (15) | Cu1—Cl1 | 2.1793 (16) |
Cu3—Cl2i | 2.6869 (17) | Cu4—O5 | 1.931 (3) |
Cu2—N3 | 1.916 (4) | Cu4—N5 | 1.937 (4) |
Cu2—O4 | 1.933 (3) | Cu4—O6 | 1.948 (4) |
Cu2—O3 | 1.934 (3) | Cu4—Cl2 | 2.2349 (14) |
Cu2—S1 | 2.2378 (15) | Cu4—O7 | 2.396 (4) |
N4—Cu3—O4 | 91.67 (16) | N2—Cu1—O2 | 81.56 (17) |
O4—Cu3—O3 | 76.21 (13) | N2—Cu1—O1 | 89.25 (17) |
N4—Cu3—S2 | 86.69 (13) | O2—Cu1—Cl1 | 95.72 (12) |
O4—Cu3—S2 | 166.13 (11) | O1—Cu1—Cl1 | 93.73 (12) |
O3—Cu3—Cl2i | 93.79 (10) | O5—Cu4—N5 | 81.59 (16) |
N3—Cu2—O3 | 91.61 (17) | N5—Cu4—O6 | 87.64 (16) |
O4—Cu2—O3 | 77.62 (14) | O5—Cu4—Cl2 | 96.88 (11) |
N3—Cu2—S1 | 87.08 (14) | O6—Cu4—Cl2 | 93.52 (11) |
O4—Cu2—S1 | 103.10 (11) | O5—Cu4—O7 | 95.19 (14) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O8ii | 0.86 | 1.97 | 2.814 (6) | 167.4 |
N6—H6A···O7iii | 0.86 | 2.25 | 3.089 (6) | 164.2 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) −x, −y+1, −z. |
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Thiosemicarbazides and their derivatives have attracted considerable interest, not only because of their potentially beneficial biological properties, such as antibacterial, antitumour and antiviral activities (Angelusiu et al., 2009; Belicchi-Ferrari et al., 2007; Palaska et al., 2002), but also because of their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Many metal complexes derived from thiosemicarbazone have been structurally characterized and they possess a wide variety of biological activities (Leovac et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003; Simonov et al., 2002; Belicchi-Ferrari et al., 2000). Acylthiosemicarbazide ligands contain O, S and N as potential donor atoms, and can support mono- and multinuclear structural complexes. However, only two complexes have so far been reported by our group based on 1,4-diacylthiosemicarbazone ligands (Wang et al., 2010; Ke et al., 2007), and they refer to an extended structure or a mononuclear complex, respectively.
Recently, much attention has been paid to multinuclear complexes, because of their magnetic properties and theoretical significance (Wei et al., 2012; Pradeep & Leroy, 2007; Moon et al., 2006; Lin et al., 2001). Thiosemicarbazide derivatives contain an N—N segment which can bridge two metal atoms, enabling them to form multinuclear complexes. However, there is no previous report of a multinuclear complex with a 1,4-diacylthiosemicarbazide ligand. In order to obtain such a multinuclear complex, we modified the side group by replacing one of the phenyl groups with a phenol to yield the title copper complex, (I), which represents the first example of a multinuclear complex involving 1-(2-oxidobenzoyl)-2-(2-oxo-2-phenylethanethioyl)hydrazine-1,2-diide (L) ligands.
Compound (I) crystallizes with the octanuclear molecule located on an inversion centre. The asymmetric unit contains four CuII cations, two crystallographically independent L ligands, two chloride ligands and two dimethylformamide (DMF) solvent molecules (Fig. 1). The trianionic L ligand chelates two CuII cations via three O atoms, two hydrazinide N atoms and one S atom, and bridges to a third CuII cation via phenolate atom O3 or O4. Atom Cu1 is four-coordinated in a square-planar geometry by two carbonyl O atoms, one hydrazinide N atom from the L ligand and one chloride ligand. Atom Cu2 has a similar four-coordination and is triply chelated by one phenolate O atom, one hydrazinide N atom and one S atom, with the fourth position occupied by a phenolate O atom from another L ligand. Atom Cu3 has a square-pyramidal coordination environment, having a base similar to Cu2 (triple-chelated by one phenolate O atom, one hydrazinide N atom and one S atom, with the fourth position occupied by a phenolate O atom from another L ligand), with the axial position occupied by atom Cl2i [symmetry code: (i) -x + 1, -y + 1, -z] which bridges to a CuII cation in the symmetry-related moiety. Chelated by two phenolate O atoms and one hydrazinide N atom, atom Cu4 adopts a square-pyramidal coordination environment, with one µ2-bridging Cl atom, one hydrazinide N atom and two carbonyl O atoms forming the base, and with an O atom from a coordinated DMF molecule in the apical position. The asymmetric unit presents a saddle-shaped tetranuclear substructure and two asymmetric units further condense into an X-shaped octanuclear molecule by sharing two chloride anions (Fig. 2).
Interestingly, there is a distinct difference between the conformations of the two crystallographically independent L ligands. One ligand (containing atoms N4–N6 and denoted L1), located at the interior of the X-shaped octanuclear molecule, exhibits coplanar characteristics, the maximum deviation from the least-squares plane being 0.2795 (3) Å [For which atom?]. The other ligand (containing atoms N1–N3 and denoted L2) is contorted and is located at the fringe of the X-shaped octanuclear molecule; the maximum deviation of atom O3 from the least-squares plane is 0.6560 (3) Å, and the dihedral angle between the two rings is 43.38 (2)°. This significant difference between the ligands is because of intermolecular π–π interactions. The dihedral angle between L1 (Cu4/O5/N4–N6/O6 plane) and L2 (Cu1/O1/N1–N3/O2 plane) is 54.98 (9)°. The molecule is buckled at the two µ2-bridging phenol O atoms [Atom numbers?]. The Cu—Cl bond lengths for the bridging Cl atom are 2.2349 (14) and 2.6869 (17) Å, while the bond length for the terminal Cl atom is 2.1793 (16) Å. As expected [Why?], the Cu4—O7 distance [2.396 (4) Å] is notably longer than the common Cu—O distance ([Reference value?]; Bera et al., 2004). Neighbouring Cu···Cu interatomic separations are Cu1···Cu2 = 4.5876 (11), Cu2···Cu3 = 3.0146 (10) and Cu3···Cu4 = 4.6396 (12) Å, with the separation between the CuII cations double-bridged by phenolate O atoms being much shorter than the others.
Details of the hydrogen-bond geometry are given in Table 2. Molecules are connected to free DMF solvent molecules via an N1—H1···O8ii hydrogen bond and are further connected to each other via an N6—H6A···O7iii hydrogen bond (Fig. 3; see Table 2 for symmetry codes). In addition, there is also a C—H···π stacking interaction, with a C4—H4···Cg(-x + 1, -y, -z) separation of 2.959 Å between the molecules, which contributes to the stability of (I).
In a previously reported cobalt complex (Ke et al., 2007), the tridentate thiosemicarbazone ligands coordinate to the CoII cation through one N atom and two carbonyl O atoms in a chelating mode, and the complex has a mononuclear structure. In the previously reported cadmium complex (Wang et al., 2010), the ligands coordinate to the CdII cations via N and S atoms in a bridging motif, and the structure is characterized by a two-dimensional architecture. In the present copper octanuclear complex, (I), each ligand chelates two CuII cations and then, through the O atom of the phenolic hydroxyl group, bridges a third CuII cation, which unites the two dinuclear components and forms the saddle-shaped tetranuclear structure. Compared with the previously reported ligands, one phenol hydroxy group has been added to the phenyl group, resulting in the difference in coordination mode, and this difference shows that the L ligands have various coordination motifs.