A hydrothermal reaction of copper acetate with ammonium molybdate, 4,4-bpy (4,4-bipyridine) and 1,10-phen (1,10-phenanthroline) led to the formation of brown crystals of [Cu2(1,10-phen)2(4,4-bpy)]2 [Mo8O26]4H2O 1. Single-crystal X-ray analysis has revealed that 1 (C68H56N12O30Cu4Mo8) crystallizes in the triclinic system, space group P with a = 11.270(3), b = 13.113(6), c = 13.906(3) ? = 103.33(4), b = 98.54(2), g = 101.29(2)? V = 1920.1(1) ?3, Mr = 2542.93, Z = 1, Dc = 2.199 g/cm3, m = 2.435 mm-1, F(000) = 1240, the final R = 0.0445, wR = 0.1082 and S = 1.021 for 5052 observed reflections with I >2s(I). It consists of copper (Ⅰ) tetramer units and -[Mo8O26]4- anions, which are further attached into a three-dimensional framework through hydrogen bonding and - stacking interactions.
The title compound (Himi)4[Mo8O26(imi)2]4H2O (imi = imidazole) 1 was synthe- sized by the reaction of H2MoO4 and imidazole in aqueous solution. Single-crystal X-ray analysis reveals that compound 1 is crystallized in the triclinic system, space group P with a = 10.6219(8), b = 10.7260(8), c = 11.3220(9) , a = 92.842(2), b =117.364(1), g = 101.655(1), C18H36Mo8N12- O30, Mr = 1668.11, V = 1106.8(2) 3, Z = 1, Dc = 2.503 g/cm3, F(000) = 804, m = 2.298 mm-1, the final R = 0.0714 and wR = 0.1651 for 3121 observed reflections with I > 2s(I). The X-ray crystal structure analysis suggests that compound 1 is built up by two imidazole ligands coordinated by the centrosymmetric octamolybdate anions, protonated imidazole cations and crystallization water molecules.
The hydrothermal reaction of Na2MoO4?2H2O, SmCl3 in acidified H2O/CH3CN solution gives rise to the title compound as colorless needle crystals, which was characterized by elemental analysis, IR and X-ray single-crystal diffraction techniques. Crystallographic data: Orthorhombic, Pnma, H3Mo3NaO11, Mr = 489.83, a = 8.411（2）, b = 7.566（2）, c = 14.359（3） ?, V = 913.8（3） ? 3, Z = 4, Dc = 3.560 g·cm-3, ( = 4.148 mm-1, F（000） = 912, the final R = 0.0649 and wR = 0.1569 for 1885 observed reflections with I ≥ 2σ（I）. The title compound consists of infinite chains built up by distorted {MoO6} octahedra via edge sharing, which are further connected into a three-dimensional framework by sodium ions and protoned water molecules.
The hydrothermal reaction of Na2MoO4·2H2O, V2O5 and en in water gave rise to a graphite-shaped vanadate [H3O]2V3O8 1, which is doped with molybdenum. Compound 1 crystallizes in tetragonal system, space group P4bm, H6O10V2.9Mo0.1, Mr = 323.37, a = 8.904(1), c =5.573(1) , V = 441.8(1) 3, Z = 2, Dc = 2.431 gcm—3, m = 3.137 mm—1, F(000) = 314, the final R = 0.0477, wR = 0.0993 for 260 observed reflections. Its two-dimensional framework is built up by corner-shared {VVO4} tetrahedra and {VIVO5} square pyramids with all of the terminal oxygen atoms toward the same orientation and further connected inta three-dimensional framework through hydrogen bonding between the protoned water molecules.
Sodium molybdate was reduced to produce ring-like compounds in the presence of carboxylic acids. Compound 1: Na8(H2O)28(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(CH3C- OO)2]}11H2O (C8H103O102Na9S2Mo18, Mr = 3829.85), where the {Mo18} ring is built up by two acetic acids connecting two {Mo9} building blocks and the 1-D chain of 1 is formed through the coordinated sodium cations. Crystal data: triclinic, space group P, a = 11.3228(2), b = 15.4170(2), c = 16.7209(3) ? a = 113.006(1), b = 108.455(1), g = 92.430(1), V = 2501.98(7) 3, Z = 1, Dc = 2.542 g/cm3, F(000) = 1854, (MoKa) = 2.381 mm-1, T = 293(2) K, final R = 0.0532 and wR = 0.1203 for 7291 observed reflections with I > 2(I) from 8775 independent reflections. Compound 2: Na8(H2O)22(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(C2H5COO)2]}10H2O (C10H93O94Na9- S2Mo18, Mr = 3715.79). Crystal data: monoclinic, space group C2/m, a = 18.044(1), b = 25.944(2), c = 10.4087(6) ? b = 106.613(2), V = 4669.3(5) 3, Z = 2, Dc = 2.643 g/cm3, F(000) = 3584, (MoKa) = 2.542 mm-1, T = 293(2) K, final R = 0.0536 and wR = 0.1621 for 4617 observed reflections with I > 2(I) from 5398 independent reflections. Similar to 1, the {Mo18} ring is built up by two {Mo9} building blocks that are connected up by two propanoic acids and these {Mo18} rings are further linked into a two-dimensional layer through the coordinated sodium cations.
The title compound, [C3H5N2]4[(C6H5NO2)2(Mo8O26)] 1, was synthesized by the reaction of H2MoO4, nicotinic acid and imidazole in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C24H30Mo8N10O30) crystallizes in the monoclinic system, space group P21/n, Mr = 1706.10, a = 12.529(1), b = 12.796(1), c = 14.038(1) , b = 100.2(1), V = 2215.3(2) 3, Z = 2, Dc = 2.558 g/cm3, F(000) = 1640, = 2.299 mm-1, the final R = 0.0527 and wR = 0.0964 for 3064 observed reflections with I > 2s(I). X-ray crystal structure analysis suggests that compound 1 consists of centrosymmetric dinicotinatooctamolybdate anion and four protonated imidazole cations, which are linked into a three-dimensional framework through hydrogen bonding.
A novel compound [（NH4）6][Gd2Mo36O112（H2O）20]·52H2O （1） was obtained from the reaction of （NH4）6Mo7O24·4H2O with GdCl3 at pH = 1.32. The X-ray structural analysis reveals that 1 crystallizes in monoclinic system, space group C2/c, Mr = 6937.77, a = 42.313（1）, b=12.924（1）, c=26.404（1） ?, β= 127.07（1）o, V=15086.2（6） ? 3, Z = 4, Dc = 2.976g·cm－3, ( = 3.316 mm－1, F（000） = 12963, the final R = 0.0585 and wR = 0.1490 for 5431 observed reflections. It contains a usual structural unit {Mo36}, which is linked to two eight-coordinated Gd3+ cations with the Gd-O distances from 2.31（5） to 2.46（5）
