Crystal structures of three [bis(1,3-dithiole-2-thione-4,5-dithiolato)zincate](2-) salts: [Q](2)[Zn(dmit)(2)] (Q=1,4-Me-2-pyridinium or NEt4) and [PPh4](2)[Zn(dmit)(2)] center dot DMSO. Comparison of the dianion packing arrangements in [Q](2)[Zn(dmit)(2)]

W T A Harrison, R A Howie, J L Wardell, S M S V Wardell, N M Comerlato, L A S Costa, A C Silvino, A I de Oliveira, R M Silva

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[Zn(dmit)(2)](2-) dianions in [Q](2)[Zn(dmit)(2)] complexes (2: Q=1,4-Me-2-pyridinium (C7H10N) or NEt4), and [PPh4](2)-[Zn(dmit)(2)] . DMSO ((2: Q = PPh4) . DMSO) have distorted tetrahedral geometries, as a result of the 94.49(3) to 95.27(3)degrees range of the bite angle of the dmit ligands; H-2-dmit= 4,5-dimercapto-1,3-dithiole-2-thione, H2C3S5. The Zn-S bond lengths are in the range from 2.3285(8) to 2.3520(9) Angstrom. In (2: Q = C7H10N) and (2: Q = NEt4),both the cations and the dianions are found in alternating layers, which form columns and sheets. Whereas in (2: Q = C7H10N), there are no S ... S contacts less than the sum of the van der Waals radii, 3.70 Angstrom, S ... S contacts at 3.5792( 13) and 3.6605 (12) Angstrom, within dianion layers, are found in (2: Q = NEt4). In ( (2: Q = PPh4) . DMSO), the steric bulk of the [PPh4] (+) cations is such that the dianions cannot be distributed in well-defined sheets: no S ... S contacts less than 4.0 Angstrom are found in ((2: Q = PPh4) DMSO). The structures are compared with those reported for other [Q](2)[Zn(dmit)(2)] compounds. (C) 2000 Elsevier Science Ltd All rights reserved.

Original languageEnglish
Pages (from-to)821-827
Number of pages7
Publication statusPublished - 2000


  • 1,3-dithiole-2-thione-4,5-dithiolates
  • dmit complexes
  • zinc dmit compounds
  • zincates

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