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The reaction between BiC1, and 3 equivalents of LiCNHR] (R = 2,6-Me,C6H,) afforded the trinuclear bismuth imidoamide species [Bi,(p-NR),(NHR)] whilst BiPh, and 3 equivalents of the alcohol HOR' (R' = 2,6-Cl,C,H3) gave the hexanuclear oxoalkoxide compound [Bi6(p3-O),-(p-OR),(OR),] both of which have been characterised by X-ray crystallography.

The crystal structure of the title compound, (C4H12N)[BiCl2(C6H5)2], contains a [BiCl2Ph2]− anion with an equatorially vacant trigonal‐bipyramidal geometry.

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