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The crystal structure of tungsten (II) bromide, W 6 Br 12 , was refined on the basis of X-ray data of a twinned crystal (space group  Bbcm  (No. 64);  a  = 11.799 Å;  b  = 11.813 Å;  c  = 14.790 Å;  Z  = 4). W 6 Br 12  forms the well-known Mo 6 Cl 12  structure, with layers of two-dimensional infinite networks  ∞  2 [(W 6 WBr 8  i )Br 2  a Br 4/2  a−a ]. The cluster bond lengths and bond angles show only small deviations from 4/ mmm  symmetry, which result from internal strain in the 2D network. Mean distances are: [unk](W–W) = 2.633 Å [unk](W–Br i ) = 2.630 Å towards the exo-Br a ; [unk](W–Br i ) = 2.619 Å towards the bridging Br a−a ;  d (W–Br a ) = 2.550 Å;  d (W–Br a−a ) = 2.656 Å. The bond angle at the bridging Br a−a  atom ias about 132°. The structural details of some isotypic compounds are compared and analyzed. It is shown that size effects as well as electronic effects play an important role in the tuning of the metal-to-metal bonds.

The crystal structure of tungsten(II) bromide, W 6 Br 12