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Bipodal NЈ,NЈ,NٞNٞ-tetraalkyl-N,NЉ-phenylenedicarbonylbis(thiourea) readily 'self-assemble into' Pt 2 L 2 and Pt 3 L 3 metallamacrocyclic complexes depending on whether the S,O chelating moieties are meta or para relative to each other in the ligand. Thus treatment of PtCl 4 2with one equivalent of 3,3,3Ј,3Ј-tetra(n-butyl)-1,1Ј-terephthaloylbis(thiourea), {H 2 L 1 } 2 , leads to the exclusive formation of the cis-[Pt(L 1 -S,O)] 3 complex, while 3,3,3Ј,3Ј-tetraethyl-1,1Ј-isophthaloylbis(thiourea), {H 2 L 2 } 2 , yields only the cis-[Pt(L 2 -S,O)] 2 complex. The cis-[Pt(L 1 -S,O)] 3 complex forms extremely friable crystals, necessitating X-ray data collection in mother-liquor, the lattice of which was found to contain chloroform, water and ethanol molecules as 'guests'. By contrast, the sparingly soluble diethyl-substituted Pt 2 L 2 complex does not include solvent molecules in the crystal lattice.

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Abstract.5-(4-Methoxyphenyl)-4-phenyl-2-phenylamino-1,3,4-thiadiazolium chloride, C21HI8N3 -

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