Received 8 February 2007
In the zigzag polymeric title compound, [Zn(S2P(OEt)2)2(NC5H4CH)2CH2C5H4N)]n or [Zn(C4H10O2PS2)2(C12H12N2)]n, the Zn atom adopts a distorted tetrahedral ZnN2S2 geometry; the bridging di-4-pyridylethane molecules are each disposed about a centre of inversion.
Previous work on structures related to the title compound, [Zn(S2P(OR)2)2(NC5H4CH2CH2C5H4N)]n, (I), has shown that when R = iPr and Cy (Lai et al., 2004a), zigzag polymeric chains are found. By contrast, increasing the bulk of R to iBu, results in the formation of a straight chain (Lai et al., 2004b).
The asymmetric unit in (I) comprises Zn[S2P(OEt)2]2 and half each of two 1,2-di-4-pyridylethane ligands, as each of these is disposed about an inversion centre. The coordination geometry (Fig. 1) is distorted tetrahedral, with both dithiophosphate ligands coordinating in the monodentate mode. This is substantiated by the relatively narrow range of tetrahedral angles and the disparity in the P-S bond distances (Table 1). In keeping with expectation (Chen et al., 2006), the topology of the polymeric chain formed in (I) is zigzag (Fig. 2). Chains are linked via C-HS interactions (details in Table 2).
| || Figure 1 |
The asymmetric unit of (I), showing the atom-labelling scheme. Only the major component of the disorder is shown. Displacement ellipsoids are drawn at the 35% probability level (arbitrary spheres for the H atoms).
| || Figure 2 |
View of the linear polymer in (I). Colour code: Zn brown, S yellow, P pink, O red, N blue, C grey and H green.
The title compound was prepared by refluxing the parent zinc dithiophosphate with 1,2-di-4-pyridylethane according to a literature procedure (Lai et al., 2004a). Colourless crystals of (I) were isolated by the slow evaporation of an acetonitrile/CHCl3 (1:3) solution (m.p. 389-391 K).
H atoms were positioned geometrically (C-H = 0.95-0.99 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). Disorder was modelled for the O4 ethyl group in that two positions were resolved for the atoms O4 and C7 [occupancy of the major component = 0.662 (9)] but not for the other atoms of this group. The atoms of the minor component were refined isotropically. The maximum and minimum residual electron-density peaks are located 0.96 and 0.78 Å, respectively, from atoms C14 and S4.
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006) and ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
This work was supported by the departmental research grant AX-0026 from The Robert A. Welch Foundation. Cheminova is thanked for the gift of the dithiophosphate ligand used in this study. The authors also thank the EPSRC X-ray Crystallographic Service, University of Southampton for the data collection.
Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., Garcia-Granda, S., Gould, R. O., Smits, J. M. M. & Smykalla, C. (1992). The DIRDIF Program System. Technical Report. Crystallography Laboratory, University of Nijmegen, The Netherlands.
Brandenburg, K. (2006). DIAMOND. Release 3.1. Crystal Impact GbR, Bonn, Germany.
Chen, D., Lai, C. S. & Tiekink, E. R. T. (2006). CrystEngComm, 8, 51-58.
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Lai, C. S., Liu, S. & Tiekink, E. R. T. (2004a). CrystEngComm, 6, 221-226.
Lai, C. S., Liu, S. & Tiekink, E. R. T. (2004b). Acta Cryst. E60, m1005-m1007.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.