Novel Vanadium(V) Compounds with a Layer Structure:  Synthesis, Crystal Structures, and Solid State NMR Spectroscopy of [(VO₂)₂(4,4‘-bpy)_0.5(4,4‘-Hbpy)(XO₄)]·H₂O (X = P and As)

Abstract

A novel vanadium(V) phosphate and the arsenate analogue, [(VO(2))(2)(4,4'-bpy)(0.5)(4,4'-Hbpy)(XO(4))].H(2)O (X = P, As; bpy = bipyridine), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. They are the first structurally characterized compounds in the vanadium(V)/4,4'-bpy/phosphate (or arsenate) systems. The two compounds are isostructural and crystallize in the triclinic space group P macro (No. 2) with a = 7.9063(3) A, b = 10.2201(4) A, c = 12.1336(5) A, alpha = 113.4652(7) degrees, beta = 95.7231(7) degrees, gamma = 94.4447(7) degrees, and Z = 2 for the phosphate, and a = 7.8843(6) A, b = 10.3686(7) A, c = 12.2606(9) A, alpha = 113.464(1) degrees, beta = 95.560(1) degrees, gamma = 94.585(1) degrees, and Z = 2 for the arsenate. The structure consists of phosphate-bridged vanadium(V) double chains linked through 4,4'-bpy ligands to form a sheet with the monoprotonated 4,4'-Hbpy(+) ligand being coordinated to the metal atom as a pendent group. The (1)H MAS NMR spectrum exhibits four resonances at 14.2, 9.5, 7.2, and 3.7 ppm with an intensity ratio close to 1:6:6:2, corresponding to three different types of protons in 4,4'-bpy and 4,4'-Hbpy(+) and one type of protons in H(2)O. The peak at 14.2 ppm can be assigned to the proton bonded to the pyridine nitrogen atom, which confirms the presence of 4,4'-Hbpy(+).

Organic template-directed indium phosphite-oxalate hybrid material: Synthesis and characterization of a novel 3D |C6H14N2|[In2(HPO3)3(C2O4)] compound with intersecting channels

“…Wang and co-workers successfully synthesized two organic template-directed indium phosphite compounds |C 2 N 2 H 10 |[In(OH) 3 (HPO 3 )] [10] and |C 4 N 2 H 12 |[In 2 -(HPO 3 ) 3 (H 2 PO 3 ) 2 ] [11]. Subsequently, two indium phosphite compounds were reported by Liu et al [12,13].Recently, the oxalate unit cross-link the inorganic parts and act as a bridge in the phosphate-oxalates giving rise to a new family of inorganic/organic hybrid materials [14][15][16]. Large numbers of template-directed metal phosphate-oxalates have recently been prepared and characterized [17][18][19][20].…”

Hydrothermal synthesis, characterization and magnetic properties of a new 2D arsenic–vanadate layers supported cobalt coordination complex: [Co(en)2(H2O)]{[Co(en)2]2As8V14O42(SO4)}·3H2O

“…With the deep study of polyoxometalate chemistry, various metaloxygen materials have been synthesized, one of which is arsenic-vanadate compounds. Up to date, many arsenicvanadium cluster compounds with various crystal structures and properties have been reported [7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Such as the compounds with a discrete [As 8 V 14 O 42 ] 4À polyoxoanion, including [As 8 V 14 O 42 (X)] nÀ (X = Cl À , n = 5; X ¼ PO 3À 4 , n = 7) [21,22] anion.…”

Hydrothermal synthesis and structure of a novel hybrid germanium vanadate: (2,2 ′ -bpy) 2 (V V O 2 ) 2 (H 2 GeO 4 ) · 6H 2 O

“…Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks containing directly coordinated organonitrogen ligands. In this field, the V/P/O system has been extensively studied [4][5][6][7][8][9], such as {[(1,10-phen)-and [(VO 2 ) 2 (4,4 0 -bpy) 0:5 (4, 4 0 -Hbpy)(PO 4 )] Á H 2 O [7]. The V/As/O system has also been reported, exemplified by the [(VO 2 ) 2 (4,4 0 -bpy) 0:5 (4,4 0 -Hbpy)-(AsO 4 )] Á H 2 O [7] and the mixed valence species [V 4 O 7 -(HAsO 4 ) 2 (o-phen) 2 ] [10].…”

“…Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks containing directly coordinated organonitrogen ligands. In this field, the V/P/O system has been extensively studied [4][5][6][7][8][9], such as {[(1,10-phen)-…”

“…Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks containing directly coordinated organonitrogen ligands. In this field, the V/P/O system has been extensively studied [4][5][6][7][8][9], such as {[(1,10-phen)-V IV [10]. In addition to these, the systems of the V/S/O [11,12], V/Se/O [13][14][15] and V/Te/O [16], such as [V 2 O 2 (OH) 2 (SO 4 )(2,2 0 -bpy) 2 ] [11], [VO(SO 4 )-(2,2 0 -bpy)] 1 [12], (1,10-phen) 2 V 2 SeO 7 , (2,2 0 -bpy)VSeO 4 , (4,4 0 -bpy)V 2 Se 2 O 8 and (4,4 0 -bpy) 2 V 4 Se 3 O 5 Á H 2 O [13], as well as M(phen)V 2 TeO 8 (M ¼ Cu, Ni) [16], have also been well studied.…”