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The crystal and molecular structures of four compounds of the general formula Hg(S 2 CNR 2 ) 2  are reported. The pale-yellow crystals of [Hg(S 2 CN i Bu 2 ) 2 ] are monoclinic, space group  C 2/ c  with unit cell dimensions  a  = 26.27(2) Å,  b  = 13.654(8) Å,  c  = 13.863(5) Å,  β  = 96.64(4)°,  Z  = 8 and  D  x  = 1.639 Mg m −3 . The yellow crystals of [Hg(S 2 CN( i Pr)Cy) 2 ] are triclinic, space group  P [unk] with unit cell dimensions  a  = 12.291(9) Å,  b  = 11.534(6) Å,  c  = 9.559(4) Å,  α  = 69.82(4)°,  β  = 88.94(4)°,  γ  = 72.00(5)°,  Z  = 2 and  D  x  = 1.747 Mg m −3 . Crystals of yellow [Hg(S 2 CN(Et)Cy) 2 ] are monoclinic, space group  P 2 1 / c  with unit cell dimensions  a  = 8.459(6) Å,  b  = 19.506(9) Å,  c  = 13.955(6) Å,  β  = 92.89(4)°,  Z  = 4 and  D  x  = 1.748 Mg m −3 . The yellow crystals of [Hg(S 2 CN n Bu 2 ) 2 ] are monoclinic, space group  C 2/ c  with unit cell dimensions  a  = 23.210(6) Å,  b  = 16.48(1) Å,  c  = 16.285(6) Å,  β  = 126.81(2)°,  Z  = 8 and  D  x  = 1.623 Mg m −3 . The structures were solved by direct methods and each refined by a full-matrix least-squares procedure to final  R  = 0.037 using 2994 reflections for [Hg(S 2 CN i Bu 2 ) 2 ], to  R  = 0.043 using 3861 reflections for [Hg(S 2 CN( i Pr)Cy) 2 ]; to  R  = 0.041 for 2895 reflections for [Hg(S 2 CN(Et)Cy) 2 ]; and to  R  = 0.065 for 2640 reflections for [Hg(S 2 CN n Bu 2 ) 2 ]. A monomeric motif, featuring distorted tetrahedral geometries, is found for the structures of [Hg(S 2 CN i Bu 2 ) 2 ] and [Hg(S 2 CN( i Pr)Cy) 2 ]. By contrast, dimeric structures, arising from the presence of bridging dithiocarbamate ligands, are found in the structures of [Hg(S 2 CN(Et)Cy) 2 ] and [Hg(S 2 CN n Bu 2 ) 2 ]. A critical examination of crystal structure for these and related systems enables a qualitative explanation for the structural diversity observed in the Hg(S 2 CNR 2 ) 2  compounds. The primary coordination about the mercury centers in Hg(S 2 CNR 2 ) 2  is linear and other associations, be they intra- or intermolecular, give rise to distortions from linearity and result in varied coordination geometries. The nature of the additional interactions is dictated by the need to maximise intermolecular associations.

zeitschrift für kristallographie - crystalline materials

Structural diversity in the mercury(II) bis( N , N -dialkyldithiocarbamate) compounds: an example of the importance of considering crystal structure when rationalising molecular structure