Acta Cryst. (2008). E64, m796 [ doi:10.1107/S1600536808013068 ]
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N)bis(thiosemicarbazide-S)copper(I)In the title complex, [Cu(CH5N3S)2(NCS)], the non-H part of the molecule is strictly planar, lying on the mirror plane at y = 0.25. The Cu atom lies at the centre of a triangle formed by the coordination of three monodentate groups, viz. two thiosemicarbazide ligands and one NCS- anion. Weak intermolecular N-H
S interactions generate a two-dimensional network.
Copper chloride dihydrate (0.3 mmol 51.2 mg) was dissolved in absolute methanol (10 ml), and was added dropwise to a solution of an equate ligand thiosemicarbazide in MeOH (10 ml). The solution was stirred for 10 minutes, then NaSCN was added. The solution became bottle-green. The mother liquid was placed at room temperature, and single crystals were obtained on standing. Elemental analysis for C3H10Cu N7S3 calculated: C 36.03, H 10.08, N %; found: C 36.12, H 10.26, N 98.05%.
All H atoms were placed geometrically and treated as riding on their parent atoms with N—H 0.86 Å (thiosemicarbazide) [Uiso(H) = 1.2Ueq(N)].
The copper atom presents an abnormally elongated displacement ellipsoid perpendicular to the mirror plane, suggeesting some kind of disorder around its (average) symmetric position.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bg2183fig1thm.gif)
| Fig. 1. The crystal structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. N-bound H atoms have been omitted for clarity. |
| [Cu(CH5N3S)2(NCS)] | F(000) = 616 |
| Mr = 303.90 | Dx = 1.815 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 3130 reflections |
| a = 11.488 (2) Å | θ = 2.3–28.2° |
| b = 6.6085 (12) Å | µ = 2.50 mm−1 |
| c = 14.650 (3) Å | T = 298 K |
| V = 1112.2 (4) Å3 | Block, black |
| Z = 4 | 0.38 × 0.27 × 0.24 mm |
| Bruker SMART CCD area-detector diffractometer | 1077 independent reflections |
| Radiation source: fine-focus sealed tube | 947 reflections with I > 2σ(I) |
| graphite | Rint = 0.021 |
| φ and ω scans | θmax = 25.0°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
| Tmin = 0.44, Tmax = 0.55 | k = −7→7 |
| 5593 measured reflections | l = −17→10 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0469P)2 + 0.712P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 1077 reflections | Δρmax = 0.67 e Å−3 |
| 86 parameters | Δρmin = −0.54 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0072 (9) |
| [Cu(CH5N3S)2(NCS)] | V = 1112.2 (4) Å3 |
| Mr = 303.90 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 11.488 (2) Å | µ = 2.50 mm−1 |
| b = 6.6085 (12) Å | T = 298 K |
| c = 14.650 (3) Å | 0.38 × 0.27 × 0.24 mm |
| Bruker SMART CCD area-detector diffractometer | 1077 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 947 reflections with I > 2σ(I) |
| Tmin = 0.44, Tmax = 0.55 | Rint = 0.021 |
| 5593 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.080 | Δρmax = 0.67 e Å−3 |
| S = 1.05 | Δρmin = −0.54 e Å−3 |
| 1077 reflections | Absolute structure: ? |
| 86 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.28439 (4) | 0.2500 | 0.53244 (3) | 0.0689 (3) | |
| N1 | 0.1200 (2) | 0.2500 | 0.25507 (19) | 0.0338 (6) | |
| H1A | 0.1489 | 0.2500 | 0.2009 | 0.041* | |
| H1B | 0.0458 | 0.2500 | 0.2625 | 0.041* | |
| N2 | 0.3047 (2) | 0.2500 | 0.31376 (19) | 0.0361 (7) | |
| H2 | 0.3483 | 0.2500 | 0.3615 | 0.043* | |
| N3 | 0.3600 (2) | 0.2500 | 0.22780 (18) | 0.0348 (6) | |
| H3A | 0.3244 | 0.1616 | 0.1914 | 0.052* | 0.50 |
| H3B | 0.3555 | 0.3732 | 0.2035 | 0.052* | 0.50 |
| N4 | 0.4655 (2) | 0.2500 | 0.7081 (2) | 0.0457 (8) | |
| H4A | 0.5262 | 0.2500 | 0.7423 | 0.055* | |
| H4B | 0.4729 | 0.2500 | 0.6496 | 0.055* | |
| N5 | 0.3516 (2) | 0.2500 | 0.83438 (18) | 0.0349 (7) | |
| H5 | 0.2839 | 0.2500 | 0.8594 | 0.042* | |
| N6 | 0.4526 (2) | 0.2500 | 0.88959 (19) | 0.0414 (7) | |
| H6A | 0.4426 | 0.1645 | 0.9359 | 0.062* | 0.50 |
| H6B | 0.4647 | 0.3741 | 0.9112 | 0.062* | 0.50 |
| N7 | 0.4475 (3) | 0.2500 | 0.4928 (2) | 0.0415 (7) | |
| S1 | 0.13368 (7) | 0.2500 | 0.43541 (6) | 0.0335 (2) | |
| S2 | 0.23512 (7) | 0.2500 | 0.68064 (5) | 0.0318 (2) | |
| S3 | 0.68866 (8) | 0.2500 | 0.47665 (7) | 0.0528 (3) | |
| C1 | 0.1893 (3) | 0.2500 | 0.3264 (2) | 0.0283 (7) | |
| C2 | 0.3611 (3) | 0.2500 | 0.7450 (2) | 0.0286 (7) | |
| C3 | 0.5450 (3) | 0.2500 | 0.4851 (2) | 0.0278 (7) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0292 (3) | 0.1520 (7) | 0.0256 (3) | 0.000 | −0.00124 (17) | 0.000 |
| N1 | 0.0205 (13) | 0.0557 (17) | 0.0252 (13) | 0.000 | −0.0003 (10) | 0.000 |
| N2 | 0.0214 (13) | 0.0632 (18) | 0.0237 (14) | 0.000 | −0.0002 (11) | 0.000 |
| N3 | 0.0254 (13) | 0.0517 (17) | 0.0274 (15) | 0.000 | 0.0048 (11) | 0.000 |
| N4 | 0.0261 (15) | 0.088 (2) | 0.0236 (14) | 0.000 | −0.0024 (11) | 0.000 |
| N5 | 0.0260 (13) | 0.0529 (17) | 0.0259 (15) | 0.000 | −0.0030 (11) | 0.000 |
| N6 | 0.0339 (15) | 0.0617 (19) | 0.0285 (15) | 0.000 | −0.0088 (12) | 0.000 |
| N7 | 0.0338 (18) | 0.0549 (19) | 0.0357 (16) | 0.000 | 0.0011 (13) | 0.000 |
| S1 | 0.0242 (4) | 0.0521 (5) | 0.0242 (4) | 0.000 | 0.0021 (3) | 0.000 |
| S2 | 0.0232 (4) | 0.0477 (5) | 0.0243 (4) | 0.000 | −0.0017 (3) | 0.000 |
| S3 | 0.0279 (5) | 0.0971 (8) | 0.0333 (5) | 0.000 | −0.0009 (4) | 0.000 |
| C1 | 0.0242 (15) | 0.0345 (16) | 0.0263 (16) | 0.000 | −0.0003 (12) | 0.000 |
| C2 | 0.0256 (15) | 0.0335 (16) | 0.0265 (16) | 0.000 | −0.0038 (12) | 0.000 |
| C3 | 0.0286 (18) | 0.0395 (18) | 0.0152 (14) | 0.000 | 0.0017 (12) | 0.000 |
| Cu1—N7 | 1.962 (3) | N4—H4A | 0.8600 |
| Cu1—S1 | 2.2401 (10) | N4—H4B | 0.8600 |
| Cu1—S2 | 2.2437 (10) | N5—C2 | 1.314 (4) |
| N1—C1 | 1.313 (4) | N5—N6 | 1.414 (4) |
| N1—H1A | 0.8600 | N5—H5 | 0.8600 |
| N1—H1B | 0.8600 | N6—H6A | 0.8900 |
| N2—C1 | 1.339 (4) | N6—H6B | 0.8900 |
| N2—N3 | 1.410 (4) | N7—C3 | 1.126 (4) |
| N2—H2 | 0.8600 | S1—C1 | 1.721 (3) |
| N3—H3A | 0.8900 | S2—C2 | 1.727 (3) |
| N3—H3B | 0.8900 | S3—C3 | 1.655 (3) |
| N4—C2 | 1.315 (4) | ||
| N7—Cu1—S1 | 123.38 (10) | C2—N5—H5 | 119.9 |
| N7—Cu1—S2 | 121.85 (10) | N6—N5—H5 | 119.9 |
| S1—Cu1—S2 | 114.77 (4) | N5—N6—H6A | 109.3 |
| C1—N1—H1A | 120.0 | N5—N6—H6B | 109.4 |
| C1—N1—H1B | 120.0 | H6A—N6—H6B | 109.5 |
| H1A—N1—H1B | 120.0 | C3—N7—Cu1 | 168.5 (3) |
| C1—N2—N3 | 124.7 (3) | C1—S1—Cu1 | 107.58 (11) |
| C1—N2—H2 | 117.7 | C2—S2—Cu1 | 108.46 (11) |
| N3—N2—H2 | 117.7 | N1—C1—N2 | 119.4 (3) |
| N2—N3—H3A | 109.2 | N1—C1—S1 | 120.9 (2) |
| N2—N3—H3B | 109.4 | N2—C1—S1 | 119.7 (2) |
| H3A—N3—H3B | 109.5 | N5—C2—N4 | 119.0 (3) |
| C2—N4—H4A | 120.0 | N5—C2—S2 | 118.3 (2) |
| C2—N4—H4B | 120.0 | N4—C2—S2 | 122.7 (3) |
| H4A—N4—H4B | 120.0 | N7—C3—S3 | 178.6 (3) |
| C2—N5—N6 | 120.1 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···S3i | 0.86 | 2.64 | 3.485 (3) | 167. |
| N1—H1B···N3i | 0.86 | 2.14 | 2.998 (4) | 177. |
| N2—H2···N7 | 0.86 | 2.24 | 3.093 (4) | 175. |
| N3—H3A···S2ii | 0.89 | 2.81 | 3.5481 (11) | 141. |
| N3—H3B···S2iii | 0.89 | 2.72 | 3.5481 (11) | 155. |
| N4—H4A···S2iv | 0.86 | 2.65 | 3.501 (3) | 170. |
| N4—H4B···N7 | 0.86 | 2.32 | 3.161 (4) | 167. |
| N5—H5···S3v | 0.86 | 2.64 | 3.342 (3) | 140. |
| N6—H6A···S1vi | 0.89 | 2.88 | 3.5144 (12) | 130. |
| N6—H6B···S1vii | 0.89 | 2.75 | 3.5144 (11) | 144. |
| Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+1/2, −y, z−1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) x+1/2, y, −z+3/2; (v) x−1/2, y, −z+3/2; (vi) −x+1/2, −y, z+1/2; (vii) −x+1/2, −y+1, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···S3i | 0.86 | 2.64 | 3.485 (3) | 167. |
| N1—H1B···N3i | 0.86 | 2.14 | 2.998 (4) | 177. |
| N2—H2···N7 | 0.86 | 2.24 | 3.093 (4) | 175. |
| N3—H3A···S2ii | 0.89 | 2.81 | 3.5481 (11) | 141. |
| N3—H3B···S2iii | 0.89 | 2.72 | 3.5481 (11) | 155. |
| N4—H4A···S2iv | 0.86 | 2.65 | 3.501 (3) | 170. |
| N4—H4B···N7 | 0.86 | 2.32 | 3.161 (4) | 167. |
| N5—H5···S3v | 0.86 | 2.64 | 3.342 (3) | 140. |
| N6—H6A···S1vi | 0.89 | 2.88 | 3.5144 (12) | 130. |
| N6—H6B···S1vii | 0.89 | 2.75 | 3.5144 (11) | 144. |
| Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+1/2, −y, z−1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) x+1/2, y, −z+3/2; (v) x−1/2, y, −z+3/2; (vi) −x+1/2, −y, z+1/2; (vii) −x+1/2, −y+1, z+1/2. |
We acknowledge the Natural Science Foundation of Liaocheng University (X051002) for support.
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Capacchi, L. C., Gaspsrri, G. F., Ferrari, M. & Nardelli, M. (1968). Chem. Commun. pp. 910–911.
Chattopadhyay, D., Majumdar, S. K., Lowe, P., Schwalbe, C. H., Chattopadhyay, S. K. & Ghosh, S. (1991). Dalton Trans. pp. 2121–2124.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Thiosemicarbazide can behave as a chelating agent(Chattopadhyay et al.,1991) or as a monodentate ligand(Capacchi et al., 1968). Among the different N,S donors studies,thiosemicarbazides and thiosemicarbazines are of special interest as both of these free ligands and their copper complexes exhibit a variety of biological activities including antitumour activity(Chattopadhyay et al.,1991). In this paper, Cu(CH5N3S)2(NCS) was synthesized by the reaction of CuCl2.6H2O, thiosemicarbazide and NaSCN at room temperature and the structure of the resulting complex is presented herein. The non-H part of the molecule is strictly planar, lying on the mirror plane at y=0.25. The Cu atom lies at the centre of a planar triangle formed by coordination of three monodentate groups, two thiosemicarbazide ligands and one NCS anion (Fig. 1). The Cu—S bond length (2.2415 (13) Å) is comparable to those in [Cu(SC(NH2)NHNH2)Cl2] (2.266 (1) Å,Chattopadhyay et al., 1991), while the Cu—N bond is shorter than the corresponding value therein (2.002 (4)Å).
In the crystal structure, weak intermolecular C—H···S interactions determine a two-dimensional network.