Syntheses and Characterizations of Four Organically Templated One-Dimensional Molybdenum Compounds including the First Inorganic−Organic Mixed-Anion Structures in the Mo/X/O (X = As, P) System

Four new organically templated molybdenum compounds, (C 4 H 12 N 2 )[MoO 2 (H 2 AsO 4 ) (AsO 4 )] ( 1 ), (C 4 H 12 N 2 )[MoO 2 (H 2 PO 4 )(PO 4 )]·H 2 O ( 2 ), (C 4 H 12 N 2 )[MoO 2 (C 2 O 4 )(HAsO 4 )] ( 3 ), and (C 6 H 14 N 2 ) 3 [(MoO 2 ) 4 (C 2 O 4 ) 4 (H 2 PO 4 ) 2 ]·8.5H 2 O ( 4 ), have been prepared under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction and thermogravimetric (TG) analysis. All four structures are one-dimensional and contain diprotonated amine cations. The first three compounds are the first organically templated chain structures in the Mo VI /X/O (X = As, P) lattices; 3 and 4 are the first inorganic−organic mixed anion materials in the molybdenum arsenate and phosphate systems, respectively. Crystal data: 1, monoclinic, P 2 1 / n, a =13.4544(8) Å, b = 6.5648(4) Å, c = 14.6312(8) Å, β = 107.522(1)°, Z = 4; 2, triclinic, P -1, a = 6.4249(3) Å, b = 8.6860(4) Å, c = 12.4506(6) Å, α = 80.539(1)°, β = 75.140(1)°, γ = 70.161(1)°, Z = 2; 3, monoclinic, P 2 1 / n, a = 6.4577(2) Å, b = 13.0135(3) Å, c = 15.3606(2) Å, β = 93.199(1)°, Z = 4; 4, triclinic, P -1, a = 8.6384(1) Å, b = 17.7583(3) Å, c = 18.1172(3) Å, α = 97.979(1)°, β = 102.441(1)°, γ = 98.830(1)°, Z = 2. Both crystals of 1 and 2 contain the double [Mo 2 X 2 O 12 (H 2 XO 4 )]∞ ribbon, which can be derived from that of VO(HPO 4 )·4H 2 O. Introduction of oxalate anions into the reaction results in 3 and 4, which contain unusual [MoAsO 6 (C 2 O 4 )]∞ and [Mo 2 PO 8 (C 2 O 4 ) 2 ]∞ chains, respectively. According to the results of TG and DT analyses, the structural motifs of 1, 3, and 4 are thermally stable up to ∼250 °C.