Darstellung, Ramanspektren und Kristallstrukturen von V₂O₃(SO₄)₂, K[VO(SO₄)₂] und NH₄[VO(SO₄)₂]

Abstract

Die Oxo‐sulfato‐vanadate(V)V2O3(SO4)4, K[VO(SO4)2] und NH4[VO(SO4)2] wurden dargestellt und ihre Strukturen röntgenographisch ermittelt. Die Struktur von V2O3(SO4)2 besteht aus einem dreidimensionalen Netzwerk von SO4‐Tetraedern und Paaren eckenverknüpfter VO6‐Oktaeder. Die Sauerstoffatome der Sulfationen sind an vier verschiedene Vanadinatome koordiniert. K[VO(SO4)2] und NH4[VO(SO4)2] sind isostrukturell. VO6‐Oktaeder, mit einem endständigen Sauerstoffatom, und Paare von SO4‐Tetraedern sind über Ecken zu Ketten verknüpft. Diese bilden über weitere gemeinsame Ecken Schichten. Die Sulfationen sind in Richtung planarer SO3‐ Moleküle und eines Sauerstoffatoms, das an Vanadium gebunden ist, verzerrt. Dies gibt eine Erklärung für den Mechanismus der bei 400°C reversiblen Reaktion K[VO(SO4)2] ⇄ K[VO2(SO4)] + SO3. Die Ramanspektren der genannten Verbindungen wurden gemessen und zugeordnet. Kristalldaten: V2O3(SO4)2, monoklin, Raumgruppe P21/a, a = 947,2(4), b = 891,3(3), c = 989,1(4)pm, β = 104,56(3)°, Z = 4, 878 unabhängige Reflexe, R(Rw) = 0,039(0,033); K[VO(SO4)2], orthorhombisch, Raumgruppe P212121, a = 495,3(2), b = 869,6(9), c = 1627(1) pm, Z = 4, 642 unabhängige Reflexe, R(RW) = 0,11(0,10); NH4[VO(SO4)2], orthorhombisch, Raumgruppe P212121, a = 495,3(1), b = 870,0(2), c = 1676,7(4) pm, Z = 4, 768 unabhängige Reflexe, R(Rw) = 0, 088(0,083).

Methanesulfonates of High‐Valent Metals: Syntheses and Structural Features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and Their Thermal Decomposition under N2 and O2 Atmosphere

“…The asymmetric unit contains one vanadium atom, which is in distorted octahedral coordination of one terminal oxide ligand, one bridging oxide ion, and four monodentate methanesulfonate anions ( Figure 5 . [17] The coordination sphere of vanadium is completed by four methanesulfonate ligands, so finally each [V 2 O 3 ] moiety is surrounded by two chelating and four monodentate methanesulfonate ions, a coordination pattern which has already been reported for V 2…”

Lithiation of V2O3(SO4)2 – a flexible insertion host

“…was synthesised by modifying a method reported by Richter et al 23 V 2 O 5 (Sigma Aldrich, $99.6%, 3.64 g) was stirred with an excess of concentrated sulfuric acid (Fischer, >95%, 30 mL) at 140 C for 48 h according to eqn (1).…”

Tetrakis(tetramethylammonium) di-μ-sulfato-bis[oxosulfatovanadate(V)]

“…ammonium, potassium and others) are known to form a variety of frameworks and clusters. Thus, in monoclinic K 3 (VO) 2 (SO 4 ) 4 (Eriksen et al, 1996) and orthorhombic (NH 4 )VO(SO 4 ) 2 (Richter & Mattes, 1992), V square pyramids are linked into chains by sharing corners with a pair of SO 4 groups. However, in both these structures there is weak bond between the V atom of one chain and an O atom from another, which yields a layered structure and distorted octahedra ± a typical V polyhedron.…”

“…However, in both these structures there is weak bond between the V atom of one chain and an O atom from another, which yields a layered structure and distorted octahedra ± a typical V polyhedron. In the potassium vanadyl sulfate salt K 4 (VO) 3 (SO 4 ) 5 (Fehrmann et al, 1989), and in vanadyl oxide sulfate, V 2 O 3 (SO 4 ) 2 (Richter & Mattes, 1992), the V atom also has distorted octahedral coordination and, by sharing corners with the sulfate group, forms a three-dimensional framework with zeolite-like tunnels, which are ®lled with K in the former but are empty in the latter compound. The dimeric vanadyl sulfate cluster was found only in Cs 4 V 2 O 3 (SO 4 ) 4 (Nielsen et al, 1993), where two V square pyramids share a corner with each other and, in addition, each of them shares a corner and an edge with sulfate groups.…”