Dimensional reductions from 2-D Nb4P2S21 to 1-D ANb2PS10 (A=Na, K, Rb, Cs, Tl) and to 0-D Tl5[Nb2S4Cl8]Cl using halide molten salts

We found new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a 0-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 °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 ANb2PS10 (A=Na, K, Rb, Cs, Tl). 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 Tl5[Nb2S4Cl8]Cl. Crystal data for TlNb2PS10: monoclinic, Pn, a=6.9452(11) Å, b=7.3761(12) Å, 12.873(2) Å, β=104.472(3)°, and Z=2. Crystal data for Tl5[Nb2S4Cl8]Cl: orthorhombic, Immm, a=7.001(5) Å, b=9.509(7) Å, c=15.546(11) Å, and Z=2.