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The crystal structures of PbBr 2  · SC(NH 2 ) 2  (form I) [ a  = 6.026(2),  b  = 15.369(4),  c  = 4.259(2) Å,  β  = 110.71(5)°,  Z  = 2, space group  P 2 1 ] and of PbBr 2  · 2[SC(NH 2 ) 2 ] (form II) [ a  = 10.583(2),  b  = 12.457(3),  c  = 4.088(2) Å,  β  = 95.61(5)°,  Z  = 2, space group  P 2 1 ] have been determined by single-crystal X-ray diffraction analysis. There is rather similar fivefold primary coordination around Pb 2+  in both complexes, conveniently described as distorted square pyramidal with the most strongly bound bromine at the apex of the pyramid. In PbBr 2  · SC(NH 2 ) 2  (form I) there are 2 sulphurs and 2 bromines in the base of the pyramid and in PbBr 2  · 2[SC(NH 2 ) 2 ] (form II) 4 sulphurs. In PbBr 2  · SC(NH 2 ) 2  (form I) the bases of the pyramids are linked through S – Br edges to form columns along [001], with the coordination around Pb 2+  increased to sevenfold by weaker links to two apex bromines of adjacent pyramids. There is also NH ⋯ Br hydrogen bonding within and between the columns.

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Crystal chemistry of thiourea complexes of lead(II) salts 1: Crystal structures of  mono (thiourea)lead(II) bromide (form I) PbBr 2  · SC(NH 2 ) 2  and of  bis (thiourea)lead(II) bromide (form II) PbBr 2  · 2[SC(NH 2 ) 2 ]