A new type of mixed anionic framework in microporous rubidium copper vanadyl(V) phosphate,Rb2Cu(VO2)2(PO4)2

In dirubidium copper bis[vanadyl(V)] bis(phosphate), Rb₂Cu(VO₂)₂(PO₄)₂, three different oxo complexes form an anionic framework. VO₅ polyhedra in a trigonal bipyramidal configuration and PO₄ tetrahedra share vertices to form eight‐membered rings, which lie in layers perpendicular to the a axis of the monoclinic unit cell. Cu atoms at centres of symmetry have square‐planar coordination and link these layers along [100] to form a three‐dimensional anionic framework, viz. [Cu(VO₂)₂(PO₄)₂]_∞²⁻. Intersecting channels in the [100], [001] and [011] directions contain Rb⁺ cations. Topological relations between this new structure type and the crystal structures of A(VO₂)(PO₄) (A = Ba, Sr or Pb) and BaCrF₂LiF₄ are discussed.     

Co0.50VOPO4·2H2O

The crystal structure of cobalt vanadophosphate dihydrate {systematic name: poly[diaqua‐μ‐oxido‐μ‐phosphato‐hemicobalt(II)vanadium(II)]}, Co_0.50VOPO₄·2H₂O, shows a three‐dimensional framework assembled from VO₅ square pyramids, PO₄ tetrahedra and Co[O₂(H₂O)₄] octahedra. The Co^II ions have local 4/m symmetry, with the equatorial water molecules in the mirror plane, while the V and apical O atom of the vanadyl group are located on the fourfold rotation axis and the P atoms reside on sites. The PO₄ tetrahedra connect the VO₅ polyhedra to form a planar P–V–O layer. The [Co(H₂O)₄]²⁺ cations link adjacent P–V–O layers via vanadyl O atoms to generate an unprecedented three‐dimensional open framework. Powder diffraction measurements reveal that the framework collapses on removal of the water molecules.     

catena‐Poly[bis(ethane‐1,2‐diammonium) [manganese(II)‐di‐μ‐phosphato‐κ4O:O′]]: a one‐dimensional manganese phosphate

The title compound, {(C₂H₁₀N₂)₂[Mn(PO₄)₂]}_n, contains anionic square‐twisted chains of formula [Mn(PO₄)₂]⁴⁻ constructed from corner‐sharing four‐membered rings of alternating MnO₄ and PO₄ units. The Mn and P atoms have distorted tetrahedral coordination and the Mn atom lies on a twofold axis. The linear manganese–phosphate chains are held together by hydrogen‐bonding interactions involving the framework O atoms and the H atoms of the ethane‐1,2‐diammonium cations, which lie in the interchain spaces.     

The triple pyrophosphate Cs3CaFe(P2O7)2

The complex phosphate tricaesium calcium iron bis(diphosphate), Cs₃CaFe(P₂O₇)₂, has been prepared by the flux method. Isolated [FeO₅] and [CaO₆] polyhedra are linked by two types of P₂O₇ groups into a three‐dimensional framework. The latter is penetrated by hexagonal channels along the a axis where three Cs atoms are located. Calculations of caesium Voronoi–Dirichlet polyhedra give coordination schemes for the three Cs atoms as [8 + 3], [9 + 1] and [9 + 4]. The structure includes features of both two‐ and three‐dimensional frameworks of caesium double pyrophosphates.     

Hexagonal ammonium zinc ­phosphate, (NH4)ZnPO4, at 10 K

The title compound, (NH₄)ZnPO₄–HEX, is built up from a three‐dimensional network of ZnO₄ and PO₄ tetrahedra [d_av(Zn—O) = 1.9400 (7) Å and d_av(P—O) = 1.5396 (7) Å], fused together via Zn—O—P links [θ_av = 133.47 (4)°]. An undisordered linear Zn—O—P bond occurs (all three atoms lie on a threefold axis). Extra‐framework NH₄⁺ cations, which interact with the [ZnPO₄]^? framework by hydrogen bonds, complete the crystal structure.     

The solid solution (Fe0.81Al0.19)(H2PO4)3 with a strong hydrogen bond

Single crystals of the solid solution iron aluminium tris(dihydrogenphosphate), (Fe_0.81Al_0.19)(H₂PO₄)₃, have been prepared under hydrothermal conditions. The compound is a new monoclinic variety (γ‐form) of iron aluminium phosphate (Fe,Al)(H₂PO₄)₃. The structure is based on a two‐dimensional framework of distorted corner‐sharing MO₆ (M = Fe, Al) polyhedra sharing corners with PO₄ tetrahedra. Strong hydrogen bonds between the OH groups of the H₂PO₄ tetrahedra and the O atoms help to consolidate the crystal structure.     

Poly­[di­aqua‐μ4‐oxalato‐di‐μ6‐phos­phato‐tetrazinc]

The structure of the title compound, [Zn₄(C₂O₄)(PO₄)₂(H₂O)₂]_n, which was synthesized under hydro­thermal conditions, consists of zinc phosphate layers joined by bridging oxalate ligands to generate a three‐dimensional framework. An extended zinc phosphate layer lies parallel to the ab plane and within this layer there are helical chains, composed of ZnO₆ octahedra and ZnO₅ square pyramids, that run parallel to the b axis and coincide with the 2₁ screw element. The oxalate groups sit on crystallographic inversion centers.     

A novel In3O16 fragment in Cs3In3(PO4)4

The double phosphate Cs₃In₃(PO₄)₄, prepared by a flux technique, features a fragment of composition In₃O₁₆ formed by three corner‐sharing InO₆ polyhedra. The central In atom resides on a twofold rotation axis, while the other two In atoms are on general positions. The O atoms in this fragment also belong to PO₄ tetrahedra, which link the structure into an overall three‐dimensional anionic In–O–P network that is penetrated by tunnels running along c. Two independent Cs⁺ cations reside inside the tunnels, one of which sits on a centre of inversion. In general, the organization of the framework is similar to that of K₃In₃(PO₄)₄, which also contains an In₃O₁₆ fragment. However, in the latter case the unit consists of one InO₇ polyhedron and one InO₆ polyhedron sharing an edge, with a third InO₆ octahedron connected via a shared corner. Calculations of the Voronoi–Dirichlet polyhedra of the alkali metals give coordination schemes for Cs of [9+2] and [8+4] ( symmetry), and for K of [8+1], [7+2] and [7+2]. This structural analysis shows that the coordination requirements of the alkali metals residing inside the tunnels cause the difference in the In₃O₁₆ geometry.     

Crystallographic report: A two‐dimensional zinc phosphate framework: [H3N(CH2)3NH3]0.5[Zn2(PO4)(HPO4)]

The two‐dimensional zinc phosphate [H₃N(CH₂)₃NH₃]_0.5[Zn₂(PO₄)(HPO₄)], has been synthesized hydrothermally using 1,3‐diaminopropane as the template. Its structure contains an inorganic framework with three‐, four‐, or six‐membered rings, built from PO₄, PO₃(OH) and ZnO₄ tetrahedral moieties sharing vertexes. The protonated 1,3‐diaminopropane molecules interact with the framework through hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.     

K3Ga2(PO4)3 and Na3Ga(PO4)2

The structures of tripotassium digallium tris(phosphate), K₃Ga₂(PO₄)₃, and trisodium gallium bis(phosphate), Na₃Ga(PO₄)₂, have different irregular one‐dimensional alkali ion‐containing channels along the a axis of the orthorhombic and triclinic unit cells, respectively. The anionic subsystems consist of vortex‐linked PO₄ tetrahedra and GaO₄ tetrahedra or GaO₅ trigonal bipyramids in the first and second structure, respectively.     

Dy2(SO3)2(SO4)(H2O)2: the first lanthanide mixed sulfate–sulfite inorganic compound

The first lanthanide mixed sulfate–sulfite inorganic coordination polymer, poly[diaqua‐μ₄‐sulfato‐di‐μ₄‐sulfito‐didysprosium(III)], [Dy₂(SO₃)₂(SO₄)(H₂O)₂]_n, has been obtained, in which both sulfate and sulfite groups originate from the disproportionation of S₂O₃²⁻ under hydrothermal and weakly acidic conditions. The crystal structure of the title compound exhibits a three‐dimensional framework. The Dy^III ion is surrounded by eight O atoms from one water molecule and two sulfate and five sulfite groups. These DyO₈ polyhedra have two shared edges and form an infinite zigzag Dy—O chain. In the bc plane, neighbouring chains are integrated through SO₃ trigonal pyramids, forming a two‐dimensional sheet. Along the a‐axial direction, the sulfate group, with the central S atom lying on a twofold axis, links adjacent two‐dimensional sheets via two S—O—Dy connections, thus generating the three‐dimensional framework.     

Mercury(II) polyphosphate,Hg(PO3)2

Single crystals of mercury(II) polyphosphate, Hg(PO₃)₂, were prepared from HgO in an acidic polyphosphate melt. The structure is isotypic with α‐Cd(PO₃)₂ and comprises infinite polyphosphate chains with a period of four phosphate units. Chains of the form ¹_∞[PO₃^?] are linked by Hg²⁺ to form a three‐dimensional network. The Hg atom is located at the centre of a distorted octahedron of O atoms with distances 2.173 (5) < (Hg—O)_mean < 2.503 (6) Å. The [HgO₆] polyhedra form zigzag‐like chains of the form ¹_∞[HgO₂O_4/2] parallel to the c axis.     

Mg7(AsO4)2(HAsO4)4: a new magnesium arsenate with a very strong hydrogen bond

A new compound, heptamagnesium bis­(arsenate) tetrakis(hydrogenarsenate), Mg₇(AsO₄)₂(HAsO₄)₄, was synthesized by a hydro­thermal method. The structure is based on a three‐dimensional framework of edge‐ and corner‐sharing MgO₆, MgO₄(OH)₂, MgO₅, AsO₃(OH) and AsO₄ polyhedra. Average Mg—O and As—O bond lengths are in the ranges 2.056–2.154 and 1.680–1.688 Å, respectively. Each of the two non‐equivalent OH groups is bonded to both an Mg and an As atom. One OH group is involved in a very short hydrogen bond [O⋯O = 2.468 (3) Å]. The formula unit is centrosymmetric, with all atoms in general positions except for one Mg atom, which has site symmetry . The compound is isotypic with Mn₇(AsO₄)₂(HAsO₄)₄ and M₇(PO₄)₂(HPO₄)₄, where M is Fe, Co or Mn.     

A layered fluorinated gallium phosphate organically templated by propane‐1,3‐diaminium,an analog of the aluminophosphate MIL‐12: Ga2(PO4)F5·C3H12N2

Crystals of the oxyfluorinated gallium phosphate MIL‐12 (digallium phosphate penta­fluoride propane‐1,3‐diaminium), (C₃H₁₂N₂)[Ga₂(PO₄)F₅], were synthesized hydro­thermally at 453 K under autogenous pressure using propane‐1,3‐diamine as the structure‐directing agent. The title compound is isomorphous with the aluminium phosphate having the MIL‐12 structural type. The structure is built up from a two‐dimensional anionic network inter­calated by the diamine species. The inorganic layer is composed of corner‐linked GaO₂F₄ octa­hedra and PO₄ tetra­hedra. The diprotonated diamine group is located on a mirror plane, between the inorganic sheets, and inter­acts preferentially via hydrogen bonding through the ammonium groups and the terminal F and bridging O atoms of the inorganic layer. One of the Ga atoms lies on an inversion centre and the other lies on a mirror plane, as does the P atom, two of the phosphate O atoms and one of the F atoms.     

Ba5Cl4(H2O)8(VPO5)8: a novel three‐dimensional framework solid

The novel hydrothermally synthesized title compound, pentabarium tetrachloride octahydrate octakis(oxovanadium phosphate), Ba₅Cl₄(H₂O)₈(VPO₅)₈, crystallizes in the orthorhombic space group Cmca with a unit cell containing four formula units. Two Ba²⁺ cations, two Cl⁻ anions and the O atoms of four water molecules are situated on the (100) mirror plane, while the third independent Ba²⁺ cation is on the intersection of the (100) plane and the twofold axis parallel to a. Two phosphate P atoms are on twofold axes, while the remaining independent P atom and both V atoms are in general positions. The structure is characterized by two kinds of layers, namely anionic oxovanadium phosphate (VPO₅), composed of corner‐sharing VO₅ square pyramids and PO₄ tetrahedra, and cationic barium chloride hydrate clusters, Ba₅Cl₄(H₂O)₈, composed of three Ba²⁺ cations linked by bridging chloride anions. The layers are connected by Ba—O bonds to generate a three‐dimensional structure.     

A first Mn member in the struvite morphotropic series,CsMn(H2O)6(PO4): hydrothermal synthesis,crystal structure and interconnections within the family of related phosphates

Caesium manganese hexahydrate phosphate, CsMn(H₂O)₆(PO₄), was synthesized under hydrothermal conditions. Its crystal structure was determined from single‐crystal X‐ray diffraction data. The novel phase crystallizes in the hexagonal space group P6₃mc and represents the first manganese member in the struvite morphotropic series, AM(H₂O)₆(TO₄). Its crystal structure is built from Mn(H₂O)₆ octahedra and PO₄ tetrahedra linked into a framework via hydrogen bonding. The large Cs atoms are encapsulated in the framework cuboctahedral cavities. It is shown that the size of the A⁺ ionic radius within the morphotropic series AM(H₂O)₆(XO₄) results is certain types of crystal structures and affects the values of the unit‐cell parameters. Structural relationships with Na(H₂O)Mg(H₂O)₆(PO₄) and the mineral hazenite, KNa(H₂O)₂Mg₂(H₂O)₁₂(PO₄)₂, are discussed.     

[H3N(CH2)2NH3]0.5[BePO4], a ­beryllophosphate analogue of ­aluminosilicate zeolite gismondine

Hydro­thermally prepared ethyl­enedi­ammonium beryl­lo­phosphate, (C₂H₁₀N₂)_0.5[BePO₄], is an analogue of aluminosilicate zeolite gismondine. A three‐dimensional network of vertex‐sharing BeO₄ and PO₄ tetrahedra [d_av(Be—O) = 1.618 (3) Å, d_av(P—O) = 1.5246 (14) Å and θ_av(Be—O—P) = 139.8°] encapsulates the disordered ethyl­enedi­ammonium cations in an eight‐ring channel system.     

Syntheses and Crystal Structures of Two New Open‐Framework Tin(II) Phosphates: Sn5O2(PO4)2 and Sn4O(PO4)2

Two new three‐dimensional neutral open‐framework tin(II) phosphates, Sn₅O₂(PO₄)₂ and Sn₄O(PO₄)₂, were synthesized under hydrothermal conditions with different ratio of tin(II) oxalate, phosphoric acid and 4,4′‐diaminodiphenylmethane. Their crystal structures have been solved by single‐crystal X‐ray diffraction methods. Sn₅O₂(PO₄)₂ crystallizes in the space group and contains six‐membered ring and twelve‐membered ring channels running parallel to the b axis. Sn₄O(PO₄)₂ crystallizes in the space group P2₁/n and contains intersecting eight‐membered ring channels. These two compounds have rare trigonal‐planar Sn₃O.     

Poly[bis[aquaneodymium(III)]‐μ2‐oxalato‐di‐μ4‐succinato]

In the title compound, [Nd₂(C₄H₄O₄)₂(C₂O₄)(H₂O)₂]_n, the flexible succinate anion assumes the gauche conformation and bridges the nine‐coordinate Nd atoms to generate two‐dimensional layers parallel to (010). The coordination polymer layers are linked into a three‐dimensional framework by the rigid oxalate ligands. The oxalate ions are located on a center of inversion.     

Three new acid M+ arsenates and phosphates with multiply protonated As/PO4 groups

The crystal structures of caesium dihydrogen arsenate(V) bis[trihydrogen arsenate(V)], Cs(H₂AsO₄)(H₃AsO₄)₂, ammonium dihydrogen arsenate(V) trihydrogen arsenate(V), NH₄(H₂AsO₄)(H₃AsO₄), and dilithium bis(dihydrogen phosphate), Li₂(H₂PO₄)₂, were solved from single‐crystal X‐ray diffraction data. NH₄(H₂AsO₄)(H₃AsO₄), which was hydrothermally synthesized (T = 493 K), is homeotypic with Rb(H₂AsO₄)(H₃AsO₄), while Cs(H₂AsO₄)(H₃AsO₄)₂ crystallizes in a novel structure type and Li₂(H₂PO₄)₂ represents a new polymorph of this composition. The Cs and Li compounds grew at room temperature from highly acidic aqueous solutions. Li₂(H₂PO₄)₂ forms a three‐dimensional (3D) framework of PO₄ tetrahedra sharing corners with Li₂O₆ dimers built of edge‐sharing LiO₄ groups, which is reinforced by hydrogen bonds. The two arsenate compounds are characterized by a 3D network of AsO₄ groups that are connected solely via multiple strong hydrogen bonds. A statistical evaluation of the As—O bond lengths in singly, doubly and triply protonated AsO₄ groups gave average values of 1.70 (2) Å for 199 As—OH bonds, 1.728 (19) Å for As—OH bonds in HAsO₄ groups, 1.714 (12) Å for As—OH bonds in H₂AsO₄ groups and 1.694 (16) Å for As—OH bonds in H₃AsO₄ groups, and a grand mean value of 1.667 (18) Å for As—O bonds to nonprotonated O atoms.