Elsevier

Polyhedron

Volume 21, Issue 21, 15 September 2002, Pages 2107-2116
Polyhedron

Bis(1,3-dithiole-2-one-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(dmio)2]. Structural comparisons of [Q][Sb(dmio)2] and bis(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(dmit)2]

https://doi.org/10.1016/S0277-5387(02)01156-7Get rights and content

Abstract

Bis(1,3-dithiole-2-one-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(C3OS4)2], [Q][Sb(dmio)2] (3: Q=NEt4, 1,4-dimethylpyridinium (DMP), PPh4 or ferrocenyl-CH2NMe3) and bis(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(C3S5)2], [Q][Sb(dmit)2] (1: Q=AsPh4 or NBu4) have been obtained from SbBr3–NaSCN and [Q]2[Zn(dmio)2]or [Q]2[Zn(dmit)2]. The crystal structures of (1: Q=AsPh4 or NBu4) and (3: Q=NEt4 and DMP) have been determined. In all cases, the Sb centres are 6-coordinated and, with the inclusion of the lone pair, are considered to have pseudo pentagonal bipyramidal structures. The interanion interactions in these and related complexes are compared.

Interanion interactions in [Q][Sb(dmio)2] and [Q][Sb(dmit)2] complexes have been determined and compared.

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Introduction

The 1,3-dithiole-2-thione-4,5-dithiolate dianion, [C3S5]2−, (dmit), Fig. 1, has been extensively studied as a ligand with both transition and main group metal complexes [1], [1](a), [1](b) and binds to metal centres primarily through the thiolato sulfur atoms forming, in the majority of cases, chelate complexes. Intermolecular or interanionic secondary metal–sulfur interactions can also occur to link the neutral or ionic complexes into aggregated species. Such is the case with bis(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1-) [Q][Sb(dmit)2], (1) [2], [3], and also bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate(1-) complexes, [Q][Bi(dmit)2], (2) [4], [5], [6] (Q=quaternary ammonium, arsonium cation, etc). The secondary metal–sulfur bonding in [1: Q=NEt4, 1,4-dimethylpyridinium (DMP), or PPh4] involves the thione sulfur atoms, which connect the bis chelated anions into arrays, varying in form with the cation [Q]+. Metal-thione intermolecular interactions also arise in [NBu4][Bi(dmit)2] (2: Q=NBu4) [4], but in (2: Q=NEt4) [5], [(2: Q=NEt4)·1/2Et2O] [5] and [(2: Q=AsPh4)·1/2DMSO] [4], it is the thiolato sulfur atoms which take part in the secondary bonding. In addition to these metal–sulfur interactions there can be weak intermolecular S⋯S contacts at distances less than the sum of the van der Waals radii of 3.60 Å, which further interconnect the anionic assemblies. In contrast, there are no interanion interactions in the benzene-1,2-dithiolato complex [NEt4][Sb(1,2-S2C6H4)2] (CSD reference code: HEGCUR) in which the benzene-1,2-dithiolato ligand is merely chelating [7].

Related to the dmit ligand is the 1,3-dithiole-2-one-4,5-dithiolate dianion, [C3OS4]2− (termed dmio in this paper, but also known as dmid) [1], [1](a), [1](b), [8], [8](a), [8](b). The structures of few dmio complexes have been reported [1b]. As expected, only small structural differences are found between dmit and dmio complexes when these 1,2-dithiolato ligands merely act as chelates, as in [Q][R2SnX(dmit)] and [Q][R2SnX(dmio)] [9], [10], [10](a), [10](b), [Q]2[Sn(dmit)3] and [Q]2[Sn(dmio)3] [11], as well as [Q][Zn(dmit)2] and [Q][Zn(dmio)2] [12]. However, when the chalcogen atoms are involved in secondary bonding, structural differences are realised as is the case with the pair, Me2Sn(dmit) and Me2Sn(dmio) [9], [13].

A series of bis(1,3-dithiole-2-one-4,5-dithiolato)antimonate(1-) complexes, [Q][Sb(dmio)2] (3) have been prepared and the structures of two complexes, (3: Q=NEt4 and DMP), have been determined and are now reported. These are compared with the structures of the previously reported (1: Q=NEt4, DMP and PPh4) as well as with those of the new compounds, (1: Q=NBu4 and AsPh4).

Section snippets

General

NMR spectra were run on Bruker 250 and 300 MHz instruments, IR spectra on Nicolet Magna 760 FTIR, Philips Analytical PU9800 and Nicolet Fourier-transform spectrometers and UV–Vis spectra on a Varian–Cary 1E UV–Vis instrument. Melting points (m.p.) were measured on a Melt–TempII instrument and a Kofler hotstage and are uncorrected. Elemental analyses were obtained using a Perkin–Elmer 2400 Instrument or from Butterworth Laboratories Ltd, Middlesex. The compounds,

General

The dmit complexes, (1: Q=NBu4 and AsPh4), were prepared from [Q]2[Zn(dmit)2] and SbBr3–NaSCN in acetone, using a previously reported procedure [2]. A related procedure was used to obtain (3: Q=NEt4, DMP, PPh4 or FcCH2NMe3) from [Q]2[Zn(dmio)2] and SbBr3–NaSCN. The complexes have little solubility in non-coordinating solvents: the NMR spectra were run in DMSO-d6 for this reason. The values of ν(CC) for 1 and 3 are generally found in the regions 1430–1443 and 1455–1470 cm−1, respectively, while

Supplementary material

Crystallographic data for the structural analyses have been deposited with the Cambridge Crystallographic Data Centre, CCDC numbers 174409–174412. Copies of this information may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: [email protected] or www: http://www.ccdc.cam.ac.uk).

Acknowledgements

We acknowledge the use of the Chemical Database Service of the EPSRC at Daresbury, UK and the National Data Collection Service of the EPSRC, now at the University of Southampton, previously at the University of Wales, Cardiff, and the expert assistance of the staff there. The financial support of CNPq, FAPERJ and FUJB, Brazil is gratefully acknowledged.

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