The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

A urea complex of copper(II) hypophosphite at 293, 100 and 15 K

The crystal structure of poly­[copper(II)‐di‐μ‐hypophosphito‐μ‐urea], [Cu(H₂PO₂)₂(CH₄N₂O)]_n, has been determined at 293, 100 and 15 K. The geometry of the hypophosphite anion is very close to ideal, with point symmetry mm2. Each Cu atom lies on an inversion centre and is coordinated to six O atoms from four hypophosphite anions and two urea mol­ecules, forming a tetragonal bipyramid. The unique urea molecule lies on a twofold axis. Each hypophosphite anion in the structure is coordinated to two Cu atoms. The hypophosphite anions, urea mol­ecules and Cu^II cations form polymeric ribbons. The Cu^II cations in the ribbon are linked together by two hypophos­phite anions and a urea mol­ecule, which is coordinated to Cu via an O atom. The ribbons are linked to each other by N—­H?O hydrogen bonds and form polymeric layers.     

The bivalent metal hypophosphites Sr(H2PO2)2, Pb(H2PO2)2 and Ba(H2PO2)2

The structures of isomorphous monoclinic strontium and lead bis­(di­hydrogenphosphate), Sr(H₂PO₂)₂ and Pb(H₂PO₂)₂, and orthorhombic barium bis­(di­hydrogen­phos­phate), Ba(H₂PO₂)₂, consist of layers of hypophosphite anions and metal cations exhibiting square antiprismatic coordination by O atoms. The Sr and Pb atoms are located on sites with point symmetry 2, and the Ba atoms are on sites with point symmetry 222. Within the layers, each anion bridges four metal cations.     

Synthesis and Crystal Structure of Two Modifications of Hexaaquamagnesium(II) Hypophosphite

Two modifications of hexaaquamagnesium(II) hypophosphite [Mg(H₂O)₆](H₂PO₂)₂ have been synthesized and structurally characterized. Literature data are available for one of these forms. The geometrical characteristics of hexaaqua cations, hypophosphite anions, and nets of hydrogen bonds between the hypophosphite anions and the coordinated water molecules are analyzed. The packing motif of the structure-forming fragments was found to be the same for the two structures, except that modification of the inner structure of the complex cation leads to different nets of hydrogen-bonded cations and anions.     

Hexa­aqua­nickel(II) bis­(hypophosphite)

The structure of hexa­aqua­nickel(II) bis­(hypophosphite), [Ni(H₂O)₆](H₂PO₂)₂, has been determined. The crystals are prismatic. The packing of the Ni and P atoms (not the entire hypophosphite anions) is the same as in the structures of [Co(H₂O)₆](H₂PO₂)₂ and [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂. The Ni^II cations have a pseudo‐face‐centered cubic cell, with cell parameter a 10.216 Å and tetrahedral cavities occupied by P atoms. The Ni^II cation has crystallographically imposed twofold symmetry and has an octahedral coordination sphere consisting of six water O atoms, two of which also lie on the twofold axis. The planes of oppositely coordinated water mol­ecules are in a cross conformation. The geometry of the hypophosphite anion is close to point symmetry mm2. The hypophosphite anions are hydrogen bonded to the coordinated water molecules.     

Iron(III) dihydrogenphosphate(I)

The structure of rhombohedral (R) iron(III) tris­[di­hydrogen­phosphate(I)] or iron(III) hypophosphite, Fe(H₂PO₂)₃, has been determined by single‐crystal X‐ray diffraction. The structure consists of [001] chains of Fe³⁺ cations in octa­hedral sites with symmetry bridged by bidentate hypophosphite anions.     

Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

Lithium and beryllium hypophosphites

The structures of monoclinic (C2/m) lithium di­hydrogenphosphate, LiH₂PO₂, and tetragonal (P4₁2₁2) beryllium bis(di­hydrogenphosphate), Be(H₂PO₂)₂, have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of hypophosphite anions and metal cations in tetrahedral coordination by O atoms. Within the layers, the anions bridge four Li⁺ and two Be²⁺ cations, respectively. In LiH₂PO₂, the Li atom lies on a twofold axis and the H₂PO₂⁻ anion has the PO₂ atoms on a mirror plane. In Be(H₂PO₂)₂, the Be atom lies on a twofold axis and the H₂PO₂⁻ anion is in a general position.     

Synthesis and crystal structures of anhydrous lithium and ammonium hypophosphites

Conditions of synthesis (temperature, precursors) have been selected to grow crystals of anhydrous lithium and ammonium hypophosphites. The crystal structure of LiH₂PO₂ has been determined. Cell parameters and atomic positions in (NH₄)H₂PO₂ at room temperature and at 100 K have been refined. By their oxygen atoms the hypophosphite anions serve to bridge the four cations. Each oxygen atom is bonded to two cations, creating puckered layers parallel to the (001) planes. The structures show much similarity in the general arrangement, but differ in the type of the tetrahedral cation-anion bonds. In LiH₂PO₂, the Li-O bond is ionic (1.933(4) Å); in (NH₄)H₂PO₂, N-H...O is a hydrogen bond (2.846(1) Å).Original Russian Text Copyright © 2004 by M. I. Naumova, N. V. Kuratieva, D. Yu. Naumov, and N. V. PodberezskayaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 491–496, May–June 2004.     

The first three‐dimensional vanadium hypophosphite

The title synthesized hypophosphite has the formula V(H₂PO₂)₃. Its structure is based on VO₆ octahedra and (H₂PO₂)⁻ pseudo‐tetrahedra. The asymmetric unit contains two crystallographically distinct V atoms and six independent (H₂PO₂)⁻ groups. The connection of the polyhedra generates [VPO₆H₂]⁶⁻ chains extended along a, b and c, leading to the first three‐dimensional network of an anhydrous transition metal hypophosphite.     

Synthesis and Structure of New BiMn2MO6 Compounds Where M=P, As, or V

The new compounds BiMn₂PO₆, BiMn₂AsO₆, and BiMn₂ VO₆ have been prepared and shown to be structurally related to several other BiA₂MO₆ compounds. The structure of BiMn₂PO₆ was refined from neutron powder diffraction data in space group Pnma with a=12.04 Å, b=5.37 Å, c=8.13 Å, and Z=4. It contains (BiO₂)¹⁻ chains and (PO₄)³⁻ tetrahedra. The observed fivefold coordination for the Mn²⁺ cations is unusual for Mn in this oxidation state.     

Copper(II) hypophosphite: the α‐ and β‐forms at 270 and 100 K,and the γ‐form at 270 K

Copper(II) hypophosphite has been shown to exist as several polymorphs. The crystal structures of monoclinic α‐, ortho­rhombic β‐ and ortho­rhombic γ‐Cu(H₂PO₂)₂ have been determined at different temperatures. The geometry of the hypophosphite anion in all three polymorphs is very close to the idealized one, with point symmetry mm2. Despite having different space groups, the structures of the α‐ and β‐polymorphs are very similar. The polymeric layers formed by the Cu atoms and the hypophosphite ions, which are identical in the α‐ and β‐polymorphs, stack in the third dimension in different ways. Each hypophosphite anion is coordinated to three Cu atoms. On cooling, a minimum amount of contraction was observed in the direction normal to the layers. The structure of the polymeric layers in the γ‐­polymorph is quite different. There are two symmetry‐independent hypophosphite anions; the first is coordinated to two Cu atoms, while the second is coordinated to four Cu atoms. In all three polymorphs, the Cu atoms are coordinated by six O atoms of six hypophosphite anions, forming tetragonal bipyramids; in the α‐ and β‐polymorphs, there are four short and two long Cu—O distances, while in the γ‐polymorph, there are four long and two short Cu—O distances.     

Verbindungen des Typs MII3MIII(PO4)3 mit Eulytinstruktur (MII = Pb,Sr, Ba; MIII = La,Lanthanide, Y,Sc, Bi,In, TI)1

A number of new phosphates of the formula M^II₃M^III(PO₄)₃ has been prepared. They have the cubic structure of eulytite (Bi₄(SiO₄)₃). Obviously all combinations of the cations being specified in the title for M^II and M^III seem to be possible; moreover, Ca₃Bi(PO₄)₃ does exist. The ions M^II and M^III are distributed on the positions of Bi in a statistical manner. The peculiar dependence of the lattive constants of the lanthanide compounds Pb₃Ln(PO₄)₃ (including La) on the (Atomic number of the lanthanide ions suggests the conclusion that the small trivalent cations (r < 1 Å) do not have a close contact with the surrounding oxygen ions forming a distorted octahedron.     

Two molybdenum (VI) monophosphates with a tunnel structure: AMoO2PO4 (A=Cs, Tl) and structural relationships in the series

Two new molybdenum (VI) monophosphates CsMoO₂PO₄ and TlMoO₂PO₄ have been synthesized by solid state chemistry. Their structure were determined from single crystal X-ray diffraction studies. The frameworks MoO₂PO₄ delimit tunnels in which are located the univalent cations. Structural relationships between the different monophosphates of the AMoO₂PO₄ series with A = Ag, Na, K, Tl, Cs, are presented in which two kinds of frameworks appear owing to the size of the univalent cations.     

Cation Distribution Studies in Double Orthophosphates with Whitlockite Structure

Abstract

The structure of β-Ca₃ (PO₄)₂ is known to be similar to that of whitlockite (R3c, Z =21). The cations are distributed in five different positions, the position Ca(4) being only half occupied. The whitlockite network is stable while the filling of the Ca(4) position changes from 0 to 1. The presence of vacancies allows to provide heterovalent substitutions 3Ca²⁺ = 2M³⁺ + and Ca²⁺ + 0 = 2Me⁺ with limits of compositions Ca₉M (PO₄)₇ and Ca_loMe(PO₄)₇ respectively. The possible cation size can be changed from 0.55 Å (Fe³⁺) to 1.51 Å (K⁺). In order to check these suggestions we have synthesized Ca₉M(PO₄)₇ (M = rare earth element, Y, Bi, Fe, Al, In, Sc) compounds, The double phosphates were studied by luminescence, infrared spectroscopy and X-ray diffraction. All these compounds are isostructural to β-Ca₃(PO₄)₂. The cell parameters gradually decrease for M = La-Ho, Y and remain constant for M = Er-Lu. This divergence can be attributed to the change of the coordination number of the rare earth element. A considerable decrease of parameters is observed for the compounds of small-size trivalent elements, their IR spectra show more bands. By luminescence it was found that rare earth elements and Y, Bi occupy Ca(1), Ca(2), Ca(3) positions. The study of Ca_9.18 Fe_0.88 (PO₄)₇ structure shows that Fe³⁺ occupies octa-hedral Ca(5) site. The considerable decrease of lattice parameters and changes in IR spectra of compounds with M = Fe, Al, In, Sc result from the occupation of Ca(5) Site with trivalent cations and from redistribution of charges in the cation sublattice of the β-Ca₃(PO₄)₂ type structure.     

Phase formation, crystal structure, and electrical conductivity of triple phosphates of alkali metals and titanium

For triple phosphates of composition A′_0.5A_0.5 Ti₂(PO₄)₃ (A?A′=Li?Na, Na?K, K?Rb), phase formation is studied, the crystal structure is refined, and the electrical conductivity is measured. The compounds are classified with the NaZr₂(PO₄)₃ structure type (NZP, space group R $\bar 3$ c). The phosphate frameworks are built of TiO₆ octahedra and PO₄ tetrahedra. Extraframework positions M1 are fully occupied by randomly distributed alkali cations. Positions M2 are vacant. Correlations are found between the structural distortion and electrical conductivity of the phosphates, on one hand, and the alkali cation size, on the other.     

NH4Ag3(PO3F)2, a layered monofluorophosphate(V) with seven different Ag sites

Single crystals of ammonium trisilver bis[fluorophosphate(V)], NH₄Ag₃(PO₃F)₂, were obtained from an aqueous solution and the structure was refined from a racemically twinned crystal. The asymmetric unit contains seven crystallographically distinct Ag atoms (two of which are located on twofold axes), four PO₃F tetrahedra and two ammonium cations. The layered structure is composed of silver–monofluorophosphate sheets, [Ag₃(PO₃F)₂]⁻, that extend parallel to (100). The F atoms of the PO₃F tetrahedra point towards the ammonium cations, which are located in the interlayer space and stabilize the structure via moderate N—H...O and N—H...F hydrogen bonds.     

The chemistry of the phosphates of barium and tetravalent cations in the 1:1 stoichiometry

The chemistry of phosphates of barium and tetravalent cations [BaM^IV(PO₄)₂] is reviewed. Such phosphates crystallise in the C2/m space group for M^IV=Ti, Zr, Hf, Ge, Sn, and Mo, and in the P2₁/n space group for BaTh(PO₄)₂. The existence of BaM^IV(PO₄)₂ in which M^IV=Pb, Ce, and U is further evaluated. Several aspects, such as phase transitions in the compounds with yavapaiite structure, solid solutions of BaM^IV(PO₄)₂ compounds and practical applications are briefly discussed.     

Precipitation phenomena in FeCl3-NaH2PO2 aqueous solutions at 245°C

Precipitation phenomena in aqueous solutions containing FeCl₃ and NaH₂PO₂ in varying concentrations have been studied at 245 °C. The composition and the morphology of the resulting particles depended strongly on the concentration ratios of the reacting ions. In the presence of small amounts of NaH₂PO₂ only hematite formed of different particle shapes. An increased addition of hypophosphite ions had two effects: first, anions of phosphorus were incorporated in the solids and, second, ferric ions were reduced to ferrous ions giving a variety of products.Supported by the Electric Power Research Institute, Contract RP-966-2.On leave from Yokohama City University, Japan.     

Dirubidium fluoro­trioxophosphate,Rb2PO3F,at 290 and 130 K,and dicaesium fluoro­trioxophosphate,Cs2PO3F,at 240 and 100 K

The structure of Rb₂PO₃F was determined at 290 and 130 K, while that of Cs₂PO₃F was determined at 240 and 100 K. Both compounds belong to the β‐K₂SO₄ family. The structure analysis did not reveal signs of a phase transition in either compound. Crystal chemical considerations do not favour the presence of a phase transition in either Rb₂PO₃F or Cs₂PO₃F. However, glass‐like phase transitions were observed by differential scanning calorimetry in slightly humid samples at 175 and 177 K for Rb₂PO₃F and Cs₂PO₃F, respectively, but were not observed in well dried samples. The bond distances are normal and Cs₂PO₃F is twinned.