OXOMOLYBDENUM(V) POLYANION CLUSTERS - HYDROTHERMAL SYNTHESES AND STRUCTURES OF (NH4)(5)NA-4(NA[MO6O12(OH)(3)(O3PC6H5)(4))](2))CENTER-DOT-6H(2)O AND (C(6)H(5)CH(2)NME(3))(4)K-4(K-2[MO6O12(OH)(3)(O3PC6H5)(4)](2))CENTER-DOT-1 0H(2)O AND THEIR RELATIONSH

摘要

The hydrothermal syntheses of the binuclear Mo(V) species (Et(4)N)[Mo2O4Cl3(H2O)(3)]. 0.5H(2)O (3 . 0.5H(2)O) and of the hexanuclear (NH4)(5)Na-4{Na[Mo6O 12(OH)(3)(O3PC6H5)(4)](2)}. 6H(2)O (1 . 6H(2)O) and (C(6)H(5)CH(2)NMe(3))(4)K-4{K-2[Mo6O12(OH)(3)(O3PC6H5)(4)](2)}. 10H(2)O (2 . 10H(2)O) are described. X-ray crystallography revealed that both 1 . 6H(2)O and 2 . 10H(2)O contain the cyclic Mo(V) anion [Mo6O12(OH)(3)(O3PC6H5)(4)](5-) as the fundamental structural motif. This hexanuclear core may be considered as a trimer constructed from {Mo(2)O10} units consisting of edge-sharing octahedra with alternating short-long Mo(V)-Mo(V) distances. The structure of 3 . 0.5H(2)O provides a structural prototype for this binuclear unit. Crystal data: 1 . 6H(2)O, C48H78N5O60Na5P8Mo12, monoclinic C2/c, a = 31.254(7), b = 30.441(6), c = 13.455(3) Angstrom, beta = 112.87(2)degrees, V = 11795(2) Angstrom(3), Z = 4, D-cacl = 1.80 g cm(-3), 2162 reflections, R = 0.069; 2 . 10H(2)O, C88H130N4O64P8K6Mo12, monoclinic P2/c, a = 19.203(4), b = 17.221(4), c = 20.949(5) Angstrom, beta = 98.91(3)degrees, V = 6844(1) Angstrom(3), Z = 2, D-calc = 1.86 g cm(-3), 4181 reflections, R = 0.065; 3 . 0.5H(2)O, C8H27NO75Cl3Mo2, monoclinic P2(1), a = 7.923(2), b = 12.255(3), c = 20.511(3) Angstrom, beta = 100.83(2)degrees, V = 1956.2(6) Angstrom(3), Z = 4, D-calc = 1.89 g cm(-3), 2161 reflections, R = 0.060. [References: 45]