Dimensional reductions from 2-D Nb4P2S21 to 1-D ANb2PS10 (A = Na, K, Rb, Cs, Tl) and to O-D Tl5[Nb2S4C18]Cl using halide molten salts

We found new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a O-D molecular complex containing a Nb2S4 core from a 2-D ternary thiophosphate, Nb4P2S21. When Nb4P2S21 was reacted with alkali metal halides (ACl; A = Na, K, Rb, CS) or TlCl at 500-700 degrees C, the -S-S-S- bridges in 2-D Nb2PS10-S-S10PNb2 were excised to form a 1-D chain, and cations were inserted between the chains to form ANb(2)PS(10) (A = Na, K, Rb, Cs, TI). We also found that thallium chloride (TlCl) is an excellent reagent for further excision, and it substitutes chloride ligands for the sulfur ligands of 2-D Nb4P2S21 to form the molecular complex Tl-5[Nb2S4Cl8]Cl. Crystal data for TlNb2PS10: monoclinic, P-n, a=6.9452(H)angstrom, b=7.3761(12)angstrom, 12.873(2)angstrom, beta =104.472(3)degrees, and Z=2. Crystal data for Tl-5[Nb2S4Cl8]Cl: orthorhombic, lmmm, a=7.001(5)angstrom, b=9.509(7)angstrom, c= 15.546(11)angstrom, and Z=2. (C) 2008 Elsevier Inc. All rights reserved.