Amine-Templated Unidimensional Phosphate−Diphosphates of Gallium and Vanadium, [NH₃CH₂CH₂NH₃][M(H₂PO₄)(P₂O₇)] (M = Ga, V)

Abstract

A new one-dimensional gallium phosphate−diphosphate, [C2H10N2][Ga(H2PO4)(P2O7)], has been synthesized under solvothermal conditions at 433 K in the presence of ethylenediamine, and the structure was determined using room-temperature single-crystal X-ray diffraction data (M r = 402.76, monoclinic, space group Cc, a = 8.6139(4), b = 14.929(1), and c = 9.3109(4) Å, and β = 106.541(4)°; V = 1147.8 Å3, Z = 4, R = 4.39%, and R w = 5.03% for 2049 observed data (I > 3(σ(I))). The structure consists of anionic chains of formula [Ga(H2PO4)(P2O7)]2- containing GaO6 octahedra linked by PO2(OH)2 and P2O7 units, which are charge-balanced by ethylenediamine dications. The chains are held together by a network of hydrogen bonds involving both interchain and chain−diamine interactions. Polycrystalline samples of the isostructural vanadium and mixed vanadium−gallium analogues, [C2H10N2][V(H2PO4)(P2O7)] and [C2H10N2][[V x Ga1 - x (H2PO4)(P2O7)] (x ∼ 0.65), have also been prepared. The former has an effective magnetic moment of 2.70(1) μB per vanadium cation consistent with the presence of V3+ ions in an octahedral environment.

Hydrothermal synthesis and characterization of a new 3D vanadium(III) phosphite (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O

“…Up to date only Al, In, Ga, and Fe are known to exhibit pure +3 oxidation state in 3D [38]. It is noteworthy that the title compound is a new example of a 3D open-framework vanadium phosphite, in which the vanadium atoms are at the +3 oxidation state exclusively.…”

New open-framework phosphate and phosphite compounds of gallium

“…In fact, gallium is known to adopt 4-, 5-and 6-coordinations in many of the gallophosphate structures [5]. Persistent research over the years has yielded many gallophosphates that exhibit monomeric [6], one- [7,8], two- [9,10] and three-dimensional [11][12][13][14] structures with variations in the Ga:P ratios.…”

“…During the present study aimed at probing the reactivity of gallium and to prepare open-framework compounds of gallium in the presence of organic amines, four new phosphate and one phosphite compounds of gallium have been synthesized. The compounds, [ 7 ], V, were synthesized by employing hydrothermal methods. All the compounds possess three-dimensionally extended structures.…”

New Gallium Phosphate Frameworks Containing 1,4-Diaminobutane and 1,5-Diaminopentane: [NH3(CH2)xNH3][Ga4(PO4)4(HPO4)] and [NH3(CH2)xNH3][Ga(PO4)(HPO4)] (x=4 and 5)

“…(II) and (IV) contain GaPO chains of the same connectivity which consist of a gallium-phosphate backbone with 'pendant' PO 3 5 N octahedra that incorporate the structure-directing amine. The present chains have, however, been observed in a number of other phosphate systems including those of Al (32,33), Co (26) and Zn (34,35).…”