Unsymmetrically-substituted 2,4,6-trimercaptotriazine: supramolecular self-assembly through C=S center dot center dot center dot H-N hydrogen bonds in the crystal structures of C3N3S3H2Na center dot 3H(2)O and C3N3S3H2Cu(PPh3)(2)

The monosodium salt of trithiocyanuric acid, C3N3S3H2Na, has been isolated as its trihydrate (1) by partial neutralisation of C3N3S3H3 with NaOH. Each sodium in the structure displays a novel cis-S2NaO4 coordination sphere and is hydrogen bonded to the anion, which adopts its thione form. Compound 1 has been used to synthesise other unsymmetrically-metallated trithiocyanuric acid derivatives. typified by [C3N3S3H2Cu(PPh3)(2)] and whose structure has also been determined. The nickel complex [C3N3S3H2NiCl(PPh3)(2)] (.) 0.5CH(2)Cl(2) was also obtained, but only tri-substituted compounds C3N3S3[Au(PPh3)](3) (.) 2CH(2)Cl(2) and C3N3S3(SnMe3)(3) were formed when 1 was reacted with (Ph3P)AuCl and Me3SnCl, respectively. (C) 2002 Elsevier Science B.V. All rights reserved.