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The new quaternary niobium thiophosphates ANb(2)P(2)S(12) (A=K, Rb, Cs) have been prepared and characterized. The title compounds were synthesized by reacting Nb metal, A(2)S, P(2)S(5), and S at 600-700 degrees C in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS(6) structure type in the tetragonal space group I$\bar 4$2d with eight formula units per unit cell and lattice constants a=15.923(2) and c=13.238(3) A for CsNb(2)P(2)S(12), a=15.887(3) and c=13.132(3) A for RbNb(2)P(2)S(12), and a=15.850(2) and c=13.119(3) A for KNb(2)P(2)S(12). Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb(2)S(12)] cluster units and [PS(4)] thiophosphate groups. The cavities and tunnels, which are formed by the helical chains, are filled with A(+) ions. Temperature-dependent conductivity studies reveal thermally activated electrical transport behavior. This result is consistent with the observation of a temperature-dependent contribution to the (31)P MAS-NMR shift, suggesting that the delocalized s-electron spin density increases with increasing temperature. These findings are supported by the results of tight-binding band structure calculations which reveal that the unusual electrical transport behavior of ANb(2)P(2)S(12) is a consequence of the structure symmetry. Therefore, CsNb(2)P(2)S(12) may be considered a chalcogenide analogue of metal phosphate bronzes.

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Phosphate Bronzes? -The new title compounds are prepared by reacting Nb metal, A2S (A: K, Rb, Cs), P2S5, and elemental sulfur at 600-700°C for 7 d in evacuated silica tubes. As revealed by single crystal XRD, the ANb 2 P 2 S 12 compounds crystallize isostructurally as variants of the tetragonal TaPS 6 structure type in the tetragonal space group I42d with Z = 8. The structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb2S12] cluster units and [PS4] groups. Temperature-dependent conductivity measurements reveal thermally activated electrical transport behavior. According to the results of tight-binding band structure calculations this unusual electrical transport behavior is a consequence of the structure symmetry. -(GIECK, C.; DERSTROFF, V.; BLOCK, T.; FELSER, C.; REGELSKY, G.; JEPSEN, O.; KSENOFONTOV, V.; GUETLICH, P.; ECKERT*, H.; TREMEL, W.; Chem. Eur.