Acta Cryst. (2007). E63, m2384 [ doi:10.1107/S160053680704024X ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
S)copper(I) iodideIn the title complex, [Cu(C2H6N2S)4]I, the CuI atom lies on a 
axis. Each CuI centre binds to the S atoms of four N-methylthiourea ligands in a distorted tetrahedral environment. In the crystal structure, intermolecular N-H
S and N-HI hydrogen bonds, together with weak C-HN interactions, link the cations and anions into a three-dimensional network.
To a solution of copper(I) iodide (0.19 g, 1.0 mmol) in acetonitrile (15 ml) was added 2 molar equivalents of N-methylthiourea in acetonitrile (10 ml). The mixture was stirred for half an hour. Then a clear solution was obtained. The solution was concentrated by slow evaporation at room temperature to yield colorless single crystals of the title compound suitable for X-ray stucture determination after a few days.
All H atoms were located from the difference map and refined isotropically The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms.
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
![[Figure 1]](./sj2330fig1thm.gif)
| Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering. |
![[Figure 2]](./sj2330fig2thm.gif)
| Fig. 2. The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines. |
| [Cu(C2H6N2S1)4]I | Z = 4 |
| Mr = 551.08 | F000 = 1096 |
| Tetragonal, I41/a | Dx = 1.739 Mg m−3 |
| Hall symbol: -I 4ad | Mo Kα radiation λ = 0.71073 Å |
| a = 12.5113 (6) Å | Cell parameters from 2767 reflections |
| b = 12.5113 (6) Å | θ = 2.2–37.5º |
| c = 13.4435 (9) Å | µ = 2.91 mm−1 |
| α = 90º | T = 100.0 (1) K |
| β = 90º | Plate, colourless |
| γ = 90º | 0.57 × 0.49 × 0.10 mm |
| V = 2104.4 (2) Å3 |
| Bruker APEXII CCD area-detector diffractometer | 2767 independent reflections |
| Radiation source: fine-focus sealed tube | 2149 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.104 |
| Detector resolution: 8.33 pixels mm-1 | θmax = 37.5º |
| T = 100.0(1) K | θmin = 2.2º |
| ω scans | h = −21→21 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −19→21 |
| Tmin = 0.205, Tmax = 0.748 | l = −22→23 |
| 19549 measured reflections |
| 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)] = 0.034 | All H-atom parameters refined |
| wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0359P)2 + 1.5035P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max = 0.001 |
| 2767 reflections | Δρmax = 1.41 e Å−3 |
| 74 parameters | Δρmin = −0.97 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Cu(C2H6N2S1)4]I | γ = 90º |
| Mr = 551.08 | V = 2104.4 (2) Å3 |
| Tetragonal, I41/a | Z = 4 |
| a = 12.5113 (6) Å | Mo Kα |
| b = 12.5113 (6) Å | µ = 2.91 mm−1 |
| c = 13.4435 (9) Å | T = 100.0 (1) K |
| α = 90º | 0.57 × 0.49 × 0.10 mm |
| β = 90º |
| Bruker APEXII CCD area-detector diffractometer | 2767 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2149 reflections with I > 2σ(I) |
| Tmin = 0.205, Tmax = 0.748 | Rint = 0.104 |
| 19549 measured reflections |
| R[F2 > 2σ(F2)] = 0.034 | Δρmax = 1.41 e Å−3 |
| wR(F2) = 0.085 | Δρmin = −0.97 e Å−3 |
| S = 1.02 | Absolute structure: ? |
| 2767 reflections | Flack parameter: ? |
| 74 parameters | Rogers parameter: ? |
| All H-atom parameters refined |
Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
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 | ||
| I1 | 0.5000 | 0.2500 | 0.8750 | 0.02531 (7) | |
| Cu1 | 0.5000 | 0.2500 | 0.3750 | 0.01643 (8) | |
| S1 | 0.34596 (3) | 0.27148 (3) | 0.47100 (3) | 0.01687 (8) | |
| N1 | 0.43604 (11) | 0.11480 (11) | 0.57710 (11) | 0.0221 (2) | |
| N2 | 0.27169 (11) | 0.17292 (12) | 0.63020 (9) | 0.0191 (2) | |
| C1 | 0.35269 (11) | 0.17989 (11) | 0.56670 (11) | 0.0166 (2) | |
| C2 | 0.26350 (13) | 0.09411 (15) | 0.70884 (13) | 0.0244 (3) | |
| H2A | 0.317 (2) | 0.104 (2) | 0.759 (2) | 0.038 (7)* | |
| H2B | 0.274 (2) | 0.027 (2) | 0.688 (2) | 0.036 (7)* | |
| H2C | 0.196 (2) | 0.0992 (19) | 0.7400 (18) | 0.029 (6)* | |
| H1N1 | 0.487 (2) | 0.1281 (19) | 0.541 (2) | 0.030 (6)* | |
| H2N1 | 0.441 (2) | 0.071 (2) | 0.6272 (16) | 0.020 (6)* | |
| H1N2 | 0.216 (2) | 0.217 (2) | 0.6193 (17) | 0.032 (7)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I1 | 0.01276 (7) | 0.01276 (7) | 0.05041 (15) | 0.000 | 0.000 | 0.000 |
| Cu1 | 0.01618 (10) | 0.01618 (10) | 0.01692 (15) | 0.000 | 0.000 | 0.000 |
| S1 | 0.01308 (14) | 0.01761 (15) | 0.01992 (15) | 0.00135 (10) | −0.00048 (11) | 0.00227 (12) |
| N1 | 0.0165 (5) | 0.0232 (6) | 0.0267 (6) | 0.0041 (4) | 0.0037 (5) | 0.0083 (5) |
| N2 | 0.0127 (5) | 0.0240 (6) | 0.0205 (5) | 0.0013 (4) | 0.0004 (4) | 0.0030 (4) |
| C1 | 0.0133 (5) | 0.0169 (5) | 0.0195 (6) | −0.0002 (4) | −0.0020 (4) | −0.0002 (5) |
| C2 | 0.0187 (6) | 0.0317 (8) | 0.0229 (6) | −0.0009 (5) | 0.0012 (5) | 0.0080 (6) |
| Cu1—S1i | 2.3349 (4) | N1—H2N1 | 0.87 (2) |
| Cu1—S1ii | 2.3350 (4) | N2—C1 | 1.3279 (19) |
| Cu1—S1iii | 2.3350 (4) | N2—C2 | 1.449 (2) |
| Cu1—S1 | 2.3350 (4) | N2—H1N2 | 0.90 (3) |
| S1—C1 | 1.7249 (15) | C2—H2A | 0.96 (3) |
| N1—C1 | 1.3305 (19) | C2—H2B | 0.90 (3) |
| N1—H1N1 | 0.82 (3) | C2—H2C | 0.94 (2) |
| S1i—Cu1—S1ii | 107.789 (9) | C1—N2—H1N2 | 116.7 (16) |
| S1i—Cu1—S1iii | 107.789 (9) | C2—N2—H1N2 | 118.5 (17) |
| S1ii—Cu1—S1iii | 112.894 (18) | N2—C1—N1 | 119.36 (14) |
| S1i—Cu1—S1 | 112.894 (18) | N2—C1—S1 | 119.07 (11) |
| S1ii—Cu1—S1 | 107.786 (9) | N1—C1—S1 | 121.55 (12) |
| S1iii—Cu1—S1 | 107.786 (9) | N2—C2—H2A | 112.0 (16) |
| C1—S1—Cu1 | 107.19 (5) | N2—C2—H2B | 113.5 (18) |
| C1—N1—H1N1 | 115.2 (17) | H2A—C2—H2B | 104 (2) |
| C1—N1—H2N1 | 121.5 (16) | N2—C2—H2C | 110.0 (15) |
| H1N1—N1—H2N1 | 122 (2) | H2A—C2—H2C | 108 (2) |
| C1—N2—C2 | 124.59 (14) | H2B—C2—H2C | 109 (2) |
| S1i—Cu1—S1—C1 | −42.97 (5) | C2—N2—C1—S1 | 174.96 (12) |
| S1ii—Cu1—S1—C1 | 75.96 (5) | Cu1—S1—C1—N2 | −177.32 (10) |
| S1iii—Cu1—S1—C1 | −161.90 (5) | Cu1—S1—C1—N1 | 1.32 (14) |
| C2—N2—C1—N1 | −3.7 (2) |
| Symmetry codes: (i) −x+1, −y+1/2, z; (ii) −y+3/4, x−1/4, −z+3/4; (iii) y+1/4, −x+3/4, −z+3/4. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N1···S1i | 0.82 (3) | 2.61 (2) | 3.3908 (15) | 159 (2) |
| N2—H1N2···I1iv | 0.90 (2) | 2.73 (3) | 3.5340 (14) | 148 (2) |
| N1—H2N1···S1v | 0.87 (2) | 2.64 (2) | 3.4407 (15) | 154 (2) |
| C2—H2A···N2v | 0.96 (3) | 2.62 (3) | 3.374 (2) | 135.4 (19) |
| Symmetry codes: (i) −x+1, −y+1/2, z; (iv) y−1/4, −x+3/4, z−1/4; (v) y+1/4, −x+1/4, z+1/4. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N1···S1i | 0.82 (3) | 2.61 (2) | 3.3908 (15) | 159 (2) |
| N2—H1N2···I1ii | 0.90 (2) | 2.73 (3) | 3.5340 (14) | 148 (2) |
| N1—H2N1···S1iii | 0.87 (2) | 2.64 (2) | 3.4407 (15) | 154 (2) |
| C2—H2A···N2iii | 0.96 (3) | 2.62 (3) | 3.374 (2) | 135.4 (19) |
| Symmetry codes: (i) −x+1, −y+1/2, z; (ii) y−1/4, −x+3/4, z−1/4; (iii) y+1/4, −x+1/4, z+1/4. |
The authors thank Universiti Sains Malaysia for Fundamental Research Grant Scheme (FRGS) grant No. 203/PFIZIK/671064.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bombicz, P., Mutikainen, I., Krunks, M., Leskela, T., Madarasz, J. & Niinisto, L. (2004). Inorg. Chim. Acta, 357, 513–525.
Bruker (2005). APEX2 (Version 1.27), SAINT (Version 7.12A) and SADABS (Version 2004/1). Bruker AXS Inc., Madison, Wisconsin, USA.
Dubler, E. & Bensch, E. (1986). Inorg. Chim. Acta, 125, 37–42.
Eller, P. G., Bradley, D. C., Hursthouse, M. B. & Meek, D. W. (1977). Coord. Chem. Rev. Vol.?, 1–95 [Please give journal volume number]
Kaim, W. & Schwederski, B. (1994). Bioinorganic Chemisty: Inorganic Elements in the Chemistry of Life, p. 367. New York: John Wiley and Sons Inc.
Lobana, T. S., Khanna, S., Butcher, R. J., Hunter, A. D. & Zeller, M. (2006). Polyhedron, 25, 2755–2763.
Sheldrick, G. M. (1998). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
The study of coordination and structural chemistry of copper(I) complexes with sulfur containing ligands has been a matter of interest over the last decades due to their promising biological applications as well as due to their ability to adopt different geometries with variable nuclearities and structural diversity (Eller et al., 1977; Kaim & Schwederski, 1994; Lobana et al., 2006). Consequently, a number of attempts have been made to explore the structures of several copper(I) complexes with thiourea and its derivatives, and these structures have been reported (Bombicz et al., 2004); Dubler & Bensch, 1986; Lobana et al., 2006). Such studies provide models for naturally occurring copper–sulfur containing metalloproteins. As part of our continuing interest in the structural chemistry of metal–sulfur interactions, we report here the crystal structure of the title complex.
In the molecule of the title complex, Cu1 lies on a fourfold roto-inversion axis and the asymmetric unit therefore contain a quarter of the molecule (Fig. 1). The coordination of Cu1 is a distorted tetrahedron, being coordinated by the S atoms of the four N-methylthiourea ligands, with S—Cu—S angles of 107.19 (5) and 112.894 (18)° (Table 1). The Cu—S bond distances [2.3349 (4) and 2.3350 (4) Å] of the title complex lie within the range of those found in the CuI complexes with tetrahedral geometry (Bombicz et al., 2004; Lobana et al., 2006). The orientation of the ligand around Cu1 is indicated by the dihedral angle between the mean planes of Cu1/S1/C1/N1/N2 and C1/C2/N1/N2 [3.86 (9)°]. All other bond lengths and angles are in normal ranges (Allen et al., 1987).
In the crystal packing (Fig. 2), the cations are linked by N1—H1N1···S1(1 − x, 1/2 − y, z) and N1—H2N1···S1(1/4 + y, 1/4 − x, 1/4 + z) hydrogen bonds, and these cations are linked to iodide anions by an N2—H1N2···I1(−1/4 + y, 3/4 − x, −1/4 + z) hydrogen bond to form molecular sheets parallel to the ac plane and these sheets are further connected by weak C2—H2A···N2(1/4 + y, 1/4 − x, 1/4 + z) interactions to form a three-dimensional network.