New Series of Layered Vanadyl Phosphates with Varied Polyamine Templates

Four two-dimensional vanadyl phosphates, (H3dien)[(VOPO4)2(OH)]·H2O (dien = diethylenetriamine) (1), (H2dach)1.5[(VOPO4)2(OH)]·2H2O (dach = 1,4-diaminocyclohexane) (2), (H2tmdpp)[V3O4(OH)(PO4)2]·3H2O (tmdpp = 4,4‘-trimethylenedipiperidine) (3), and (H2tmdpp)(H1.5tmdpp)K0.5[V5O7(H2O)2(PO4)4]·H2O (4), with clearly distinct but orderly increasing layer separations from 7.75 to 18.07 Å, have been prepared via hydrothermal routes and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility or ion-exchange studies. The series possesses three unique layer topologies, but all contain VIVO5 square pyramid, PO4 tetrahedron, discrete dimers of V−O polyhedra, and 3-, 4-, 5-, and 8-membered rings. Structures 1 and 2 are VIV species, having the same layer topology but different amine cations. Compounds 3 and 4 are VIV/VV mixed valent, holding the same amine templates in varied inclined angles. Being similar to 1 and 2, the layer of 3 contains extra vanadate groups. In contrast, the layers in 4 are distinct and contain VVO6 and VIVO6 octahedra besides VIVO5 square pyramid. It exhibits an interlayer d-spacing of 18.07 Å, the largest propped up by noncovalent intermediates between VPO layers. With an extremely low density of 1.71 g·cm-3, compound 4 also demonstrates the lightest layered material ever prepared in the V/P/O system. Structural relationship, template effect, factors controlling layer gaps, ion exchange, thermal stability, and magnetic properties are discussed

New Series of Layered Vanadyl Phosphates with Varied Polyamine Templates

Four two-dimensional vanadyl phosphates, (H3dien)[(VOPO4)2(OH)]·H2O (dien = diethylenetriamine) (1), (H2dach)1.5[(VOPO4)2(OH)]·2H2O (dach = 1,4-diaminocyclohexane) (2), (H2tmdpp)[V3O4(OH)(PO4)2]·3H2O (tmdpp = 4,4‘-trimethylenedipiperidine) (3), and (H2tmdpp)(H1.5tmdpp)K0.5[V5O7(H2O)2(PO4)4]·H2O (4), with clearly distinct but orderly increasing layer separations from 7.75 to 18.07 Å, have been prepared via hydrothermal routes and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility or ion-exchange studies. The series possesses three unique layer topologies, but all contain VIVO5 square pyramid, PO4 tetrahedron, discrete dimers of V−O polyhedra, and 3-, 4-, 5-, and 8-membered rings. Structures 1 and 2 are VIV species, having the same layer topology but different amine cations. Compounds 3 and 4 are VIV/VV mixed valent, holding the same amine templates in varied inclined angles. Being similar to 1 and 2, the layer of 3 contains extra vanadate groups. In contrast, the layers in 4 are distinct and contain VVO6 and VIVO6 octahedra besides VIVO5 square pyramid. It exhibits an interlayer d-spacing of 18.07 Å, the largest propped up by noncovalent intermediates between VPO layers. With an extremely low density of 1.71 g·cm-3, compound 4 also demonstrates the lightest layered material ever prepared in the V/P/O system. Structural relationship, template effect, factors controlling layer gaps, ion exchange, thermal stability, and magnetic properties are discussed

New Series of Layered Vanadyl Phosphates with Varied Polyamine Templates

Four two-dimensional vanadyl phosphates, (H3dien)[(VOPO4)2(OH)]·H2O (dien = diethylenetriamine) (1), (H2dach)1.5[(VOPO4)2(OH)]·2H2O (dach = 1,4-diaminocyclohexane) (2), (H2tmdpp)[V3O4(OH)(PO4)2]·3H2O (tmdpp = 4,4‘-trimethylenedipiperidine) (3), and (H2tmdpp)(H1.5tmdpp)K0.5[V5O7(H2O)2(PO4)4]·H2O (4), with clearly distinct but orderly increasing layer separations from 7.75 to 18.07 Å, have been prepared via hydrothermal routes and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility or ion-exchange studies. The series possesses three unique layer topologies, but all contain VIVO5 square pyramid, PO4 tetrahedron, discrete dimers of V−O polyhedra, and 3-, 4-, 5-, and 8-membered rings. Structures 1 and 2 are VIV species, having the same layer topology but different amine cations. Compounds 3 and 4 are VIV/VV mixed valent, holding the same amine templates in varied inclined angles. Being similar to 1 and 2, the layer of 3 contains extra vanadate groups. In contrast, the layers in 4 are distinct and contain VVO6 and VIVO6 octahedra besides VIVO5 square pyramid. It exhibits an interlayer d-spacing of 18.07 Å, the largest propped up by noncovalent intermediates between VPO layers. With an extremely low density of 1.71 g·cm-3, compound 4 also demonstrates the lightest layered material ever prepared in the V/P/O system. Structural relationship, template effect, factors controlling layer gaps, ion exchange, thermal stability, and magnetic properties are discussed

New Series of Layered Vanadyl Phosphates with Varied Polyamine Templates

Four two-dimensional vanadyl phosphates, (H3dien)[(VOPO4)2(OH)]·H2O (dien = diethylenetriamine) (1), (H2dach)1.5[(VOPO4)2(OH)]·2H2O (dach = 1,4-diaminocyclohexane) (2), (H2tmdpp)[V3O4(OH)(PO4)2]·3H2O (tmdpp = 4,4‘-trimethylenedipiperidine) (3), and (H2tmdpp)(H1.5tmdpp)K0.5[V5O7(H2O)2(PO4)4]·H2O (4), with clearly distinct but orderly increasing layer separations from 7.75 to 18.07 Å, have been prepared via hydrothermal routes and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility or ion-exchange studies. The series possesses three unique layer topologies, but all contain VIVO5 square pyramid, PO4 tetrahedron, discrete dimers of V−O polyhedra, and 3-, 4-, 5-, and 8-membered rings. Structures 1 and 2 are VIV species, having the same layer topology but different amine cations. Compounds 3 and 4 are VIV/VV mixed valent, holding the same amine templates in varied inclined angles. Being similar to 1 and 2, the layer of 3 contains extra vanadate groups. In contrast, the layers in 4 are distinct and contain VVO6 and VIVO6 octahedra besides VIVO5 square pyramid. It exhibits an interlayer d-spacing of 18.07 Å, the largest propped up by noncovalent intermediates between VPO layers. With an extremely low density of 1.71 g·cm-3, compound 4 also demonstrates the lightest layered material ever prepared in the V/P/O system. Structural relationship, template effect, factors controlling layer gaps, ion exchange, thermal stability, and magnetic properties are discussed

New Series of Layered Vanadyl Phosphates with Varied Polyamine Templates

Four two-dimensional vanadyl phosphates, (H3dien)[(VOPO4)2(OH)]·H2O (dien = diethylenetriamine) (1), (H2dach)1.5[(VOPO4)2(OH)]·2H2O (dach = 1,4-diaminocyclohexane) (2), (H2tmdpp)[V3O4(OH)(PO4)2]·3H2O (tmdpp = 4,4‘-trimethylenedipiperidine) (3), and (H2tmdpp)(H1.5tmdpp)K0.5[V5O7(H2O)2(PO4)4]·H2O (4), with clearly distinct but orderly increasing layer separations from 7.75 to 18.07 Å, have been prepared via hydrothermal routes and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility or ion-exchange studies. The series possesses three unique layer topologies, but all contain VIVO5 square pyramid, PO4 tetrahedron, discrete dimers of V−O polyhedra, and 3-, 4-, 5-, and 8-membered rings. Structures 1 and 2 are VIV species, having the same layer topology but different amine cations. Compounds 3 and 4 are VIV/VV mixed valent, holding the same amine templates in varied inclined angles. Being similar to 1 and 2, the layer of 3 contains extra vanadate groups. In contrast, the layers in 4 are distinct and contain VVO6 and VIVO6 octahedra besides VIVO5 square pyramid. It exhibits an interlayer d-spacing of 18.07 Å, the largest propped up by noncovalent intermediates between VPO layers. With an extremely low density of 1.71 g·cm-3, compound 4 also demonstrates the lightest layered material ever prepared in the V/P/O system. Structural relationship, template effect, factors controlling layer gaps, ion exchange, thermal stability, and magnetic properties are discussed

Rb₆(InCo)₂(Si₉O₂₆): A Mixed-Metal Silicate Containing 20-Membered-Ring Silicate Single Layers with a Very Low Si:O Ratio

A new cobalt−indium silicate, Rb6(InCo)2(Si9O26), has been synthesized via a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. It crystallizes in the noncentrosymmetric orthorhombic space group Aba2 (No. 41) with a = 20.779(1) Å, b = 12.0944(6) Å, c = 10.7761(5) Å, V = 2708.1(2) Å3, and Z = 4. The structure consists of 20-membered-ring silicate single layers of corner-sharing SiO4 tetrahedra interconnected by dimers of edge-sharing CoO4 tetrahedra and InO6 octahedra into a 3D framework. The Si:O ratio for the title compound is the lowest among the known single-layer silicates. Magnetic susceptibility confirms the divalent state of the cobalt ion. The powder sample has a second-harmonic-generation signal, confirming the absence of a center of symmetry in the structure

Rb₆(InCo)₂(Si₉O₂₆): A Mixed-Metal Silicate Containing 20-Membered-Ring Silicate Single Layers with a Very Low Si:O Ratio

A new cobalt−indium silicate, Rb6(InCo)2(Si9O26), has been synthesized via a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. It crystallizes in the noncentrosymmetric orthorhombic space group Aba2 (No. 41) with a = 20.779(1) Å, b = 12.0944(6) Å, c = 10.7761(5) Å, V = 2708.1(2) Å3, and Z = 4. The structure consists of 20-membered-ring silicate single layers of corner-sharing SiO4 tetrahedra interconnected by dimers of edge-sharing CoO4 tetrahedra and InO6 octahedra into a 3D framework. The Si:O ratio for the title compound is the lowest among the known single-layer silicates. Magnetic susceptibility confirms the divalent state of the cobalt ion. The powder sample has a second-harmonic-generation signal, confirming the absence of a center of symmetry in the structure

Synthesis, Crystal Structure, and Solid State NMR Spectroscopy of NH₄[(V₂O₃)₂(4,4‘-bpy)₂(H₂PO₄)(PO₄)₂]·0.5H₂O, a Mixed-Valence Vanadium(IV,V) Phosphate with a Pillared Layer Structure

A mixed-valence vanadium phosphate, NH4[(V2O3)2(4,4‘-bpy)2(H2PO4)(PO4)2]·0.5H2O, has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.6354(8) Å, b = 9.9786(6) Å, c = 23.369(1) Å, β = 92.713(1)°, and Z = 4 with R1 = 0.0389. The structure consists of dimers of edge-sharing vanadium(IV,V) octahedra that are connected by corner-sharing phosphate tetrahedra to form layers in the ab-plane, which are further linked through 4,4‘-bipyridine pillars to generate a 3-D framework. Magnetic susceptibility confirms the valence of the vanadium atoms. The 31P MAS NMR spectrum shows a resonance centered at 80 ppm with a shoulder at ca. 83 ppm in an intensity ratio close to 1:2, which correspond to two distinct P sites. The observed large downfield 31P NMR shifts can be ascribed to magnetic exchange coupling involving phosphorus atoms. The unpaired electron spin density at the phosphorus nucleus was determined from variable-temperature 31P NMR spectra. The 1H MAS NMR spectrum was fitted to six components in accordance with the structure as determined from X-ray diffraction

Flux Synthesis, Crystal Structures, and Solid-State NMR Spectroscopy of Two Indium Silicates Containing Varied In−O Coordination Geometries

Two novel indium silicates, K5In3Si7O21 (1) and K4In2Si8O21 (2), have been synthesized by a flux-growth method and characterized by single-crystal X-ray diffraction. The structure of 1 consists of siebener single chains of corner-sharing SiO4 tetrahedra running along the b axis linked via corner-sharing by In2O9 face-sharing octahedral dimers and InO5 trigonal bipyramids to form a 3D framework. The structure of 2 consists of a 3D silicate framework containing 6- and 14-ring channels. InO5 square pyramids are located within the 14-ring channels sharing corners with the silicate framework. The solid-state 29Si MAS NMR spectrum of compound 1 was recorded; it shows the influence of the indium atoms in the second coordination sphere of the silicon on the chemical shift. Crystal data:  1, orthorhombic, Pna21 (No. 33), a = 12.4914(3) Å, b = 16.8849(3) Å, c = 10.2275(2) Å, V = 2157.1(1) Å3 and Z = 4; 2, monoclinic, P21/n (No. 14), a = 8.4041(3) Å, b = 11.4919(4) Å, c = 10.4841(3) Å, β = 90.478(2)°, V = 1012.5(1) Å3 and Z = 2

Hydrothermal Synthesis, Crystal Structure, and Solid-State NMR Spectroscopy of a New Indium Silicate: K₂In(OH)(Si₄O₁₀)

A new indium(III) silicate, K2In(OH)(Si4O10), has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the monoclinic space group P21/m (No. 11) with a = 11.410(1) Å, b = 8.373(1) Å, c = 11.611(1) Å, β = 112.201(2)°, and Z = 4. The structure, which is analogous to that of K2CuSi4O10, consists of unbranched vierer 4-fold chains of corner-sharing SiO4 tetrahedra running along the b axis linked together via corner sharing by chains of trans-corner-sharing InO4(OH)2 octahedra to form a 3-D framework which delimits 8-ring and 6-ring channels to accommodate K+ cations. The presence of hydroxyl groups is confirmed by IR spectroscopy. The 29Si MAS NMR exhibits four resonances at −88.6, −90.1, −97.4, and −98.2 ppm corresponding to four distinct crystallographic Si sites. A 1H → 29Si CP/MAS NMR experiment was performed to assign the four resonances