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.     

[Zn3(PO4)2(H2O)0.8(NH3)1.2]

The structure of the title compound, ammineaquadi‐μ₅‐phosphato‐trizinc(II), [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2], consists of two parts: (i) PO₄ and ZnO₄ vertex‐sharing tetrahedra arranged in layers parallel to (100) and (ii) ZnO₂(N/O)₂ tetrahedra located between the layers. Elemental analysis establishes the ammine‐to‐water ratio as 3:2. ZnO₂(N/O)₂ tetrahedra are located at special position 4e (site symmetry 2) in C2/c. The two O atoms of ZnO₂(N/O)₂ are bonded to neighbouring P atoms, forming two Zn—O—P linkages and connecting ZnO₂(N/O)₂ tetrahedra with two adjacent bc plane layers. A noteworthy feature of the structure is the presence of NH₃ and H₂O at the same crystallographic position and, consequently, qualitative changes in the pattern of hydrogen bonding and weaker N/O—H...O electrostatic interactions, as compared to two closely related structures.     

Novel K/Mn phosphate hydrates,K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K₂Mn₃(H₂O)₂[P₂O₇]₂, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H₂O)₂[Al₂(PO₄)₃], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X‐ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A₂M₃(H₂O)₂[P₂O₇]₂, where A = K, NH₄, Rb or Na and M = Mn, Fe, Co or Ni, and AM²⁺(H₂O)₂[M³⁺₂(PO₄)₃], where A = Cs, Rb, K, NH₄ or (H₃O); M²⁺ = Mn, Fe, Co or Ni; and M³⁺ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit‐cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO₂)₂(PO₄)₂]_∞ layers, with a cationic topology similar to the Si/Al‐topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.     

Das erste Vanadium(III)‐Borophosphat: Darstellung und Kristallstruktur von CsV3(H2O)2[B2P4O16(OH)4]

The First Vanadium(III) Borophosphate: Synthesis and Crystal Structure of CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] was prepared under mild hydrothermal conditions (T = 165 °C) from mixtures of CsOH_(aq), VCl₃, H₃BO₃, and H₃PO₄ (molar ratio 1 : 1 : 1 : 2). The crystal structure was determined by X‐ray single crystal methods (monoclinic; space group C2/m, No. 12): a = 958.82(15) pm, b = 1840.8(4) pm, c = 503.49(3) pm; β = 110.675(4)°; Z = 2. The anionic partial structure contains oligomeric units [BP₂O₈(OH)₂]^5–, which are built up by a central BO₂(OH)₂ tetrahedron and two PO₄ tetrahedra sharing common corners. V^III is octahedrally coordinated by oxygen of adjacent phosphate tetrahedra and OH groups of borate tetrahedra as well as oxygen of phosphate tetrahedra and H₂O molecules, respectively (coordination octahedra VO₄(OH)₂ and VO₄(H₂O)₂). The oxidation state +3 for vanadium was confirmed by measurements of the magnetic susceptibility. The trimeric borophosphate groups are connected via vanadium centres to form layers with octahedra‐tetrahedra ring systems, which are likewise linked via V^III‐coordination octahedra. Overall, a three‐dimensional framework constructed from VO₄(OH)₂ and VO₄(H₂O)₂ octahedra as well as BO₂(OH)₂ and PO₄ tetrahedra results. The structure contains channels running along [001], which are occupied by Cs⁺ in a distorted octahedral coordination (CsO₄(H₂O)₂).     

CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure

A novel noncentrosymmetric (NCS) polar fluoride sulfate, CsSbF₂SO₄, was obtained by ionothermal synthesis. A meticulously designed co‐substitution approach was used to successfully replace the [TiO₆]^8? and [PO₄]^3? functional groups in KTiOPO₄ (KTP) with [SbO₄F₂]^7? and [SO₄]^2? units, respectively. The structure of CsSbF₂SO₄ features a pseudo‐3D framework consisting of interconnected 1D [SbF₂O₂SO₄]^5? chains of corner‐sharing [SbO₄F₂]^7? octahedra and [SO₄]^2? tetrahedra. The title compound exhibits a sharply enlarged band gap compared to its parent compound, KTP, benefitting from the introduction of F^? ions and the displacement of Sb³⁺ cations. Second harmonic generation (SHG) measurements manifested that CsSbF₂SO₄ is phase‐matchable and revealed a strong SHG response of about 3.0 KH₂PO₄ (KDP), which is the highest value reported for any metal sulfate reported to date. The reported fluoride sulfate is a promising near ultraviolet (UV) nonlinear optical (NLO) material.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Syntheses and characterization of zero-dimensional molybdoantimonites, A2(Mo4Sb2O18) (A=Y, La, Nd, Sm, Gd and Dy)

Six new isostructural A₂(Mo₄Sb₂O₁₈) (A=Y, La, Nd, Sm, Gd and Dy) compounds have been synthesized by solid-state reactions and characterized by single crystal X-ray diffraction and spectroscopic techniques. They crystallize in C2/c space group with 4 formula units and contain A³⁺ cations and discrete centrosymmetric anionic (Mo₄Sb₂O₁₈)⁶⁻ aggregates, made of tetrahedral MoO₄ and disphenoidal SbO₄ moieties. They exhibit characteristic Sb³⁺ photoluminescence.     

(H3O)Nd(SO4)2

The crystal structure of oxonium neodymium bis(sulfate), (H₃O)Nd(SO₄)₂, shows a two‐dimensional layered framework assembled from SO₄ tetrahedra and NdO₉ tricapped trigonal prisms. One independent sulfate group makes four S—O—Nd linkages, while the other makes five such connections to generate an unprecedented anhydrous anionic [Nd(SO₄)₂]⁻ layer. To achieve charge balance, H₃O⁺ cations are inserted between adjacent layers where they participate in hydrogen‐bonding interactions with the sulfate O atoms of adjacent layers.     

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.     

Tetra­aqua­cobalt(II) bis­[vanadyl(IV) phosphate], [Co(H2O)4][VO(PO4)]2

The structure of [Co(H₂O)₄][VO(PO₄)]₂ is composed of [VO(PO₄)] layers and interlayer tetrahydrated Co²⁺ ions. Alternating VO₅ square pyramids and PO₄ tetrahedra share O‐atom vertices, thus forming the vanadyl phosphate layers. Two vanadyl oxo groups from neighbouring layers are coordinated to each Co atom in a trans fashion, with Co—O distances of 2.157 (4) Å, thus generating a three‐dimensional framework structure.     

Doppelkettenstruktur von (pipzH2)[MnF2(HPO4)(H2O)](H2PO4)

By adding piperazine to a hydrofluoric and phosphoric acid solution of Manganese(III) fluoride, the fluoride phosphate (pipzH₂)[MnF₂(HPO₄)(H₂O)](H₂PO₄) can be crystallized. Its structure is built by piperazinium(2+) cations, (H₂PO₄)^? anions, and an anionic double‐chain of [HPO₄] tetrahedra and [MnO₃F₂(H₂O)] octahedra. The structure is triclinic, space group P , Z = 2, a = 622.97(4), b = 923.46(6), c = 1183.62(7) pm, α = 98.343(6)°, β = 100.747(7)°, γ = 107.642(5)°, R = 0.0289. It is worth noting that a ferrodistortive Jahn‐Teller order is observed with [MnO₃F₂(H₂O)] octahedra strongly elongated along the F–Mn–OH₂ axes perpendicular to the chain plane. The structure is stabilized by very strong hydrogen bonds.     

The rich crystal chemistry of the AMM′(PO4)2 morphotropic series: NaZnAl(PO4)2, the first Na representative with a new structure type

A novel phosphate, sodium zinc aluminium bis(phosphate), NaZnAl(PO₄)₂, was obtained under mild‐temperature hydrothermal conditions at 553 K. The crystal structure has been studied using single‐crystal X‐ray experimental data. The pseudo‐hexagonal phase NaZnAl(PO₄)₂ crystallizes in the monoclinic space group P2₁/c. Its unique crystal structure is based on a three‐dimensional (3D) framework built by Zn‐, Al‐ and P‐centred tetrahedra sharing vertices. Channels parallel to the [101] and [01] directions are limited by six‐ and eight‐membered windows, and incorporate Na atoms. The new compound is discussed as a member of the morphotropic series AMM′PO₄, where A = Na, K, Rb or NH₄, M = Cu, Ni, Co, Fe, Zn or Mg and M′ = Fe, Al or Ga. The title compound is the first Na representative within the series and is characterized by a 3D architecture of tetrahedra populated in an ordered manner by Zn²⁺, Al³⁺ and P⁵⁺ ions.     

Ein neues Lithiumhydrogensulfat,Li2(HSO4)2(H2SO4) – Synthese und Kristallstruktur

A New Lithium Hydrogen Sulfate, Li₂(HSO₄)₂(H₂SO₄) – Synthesis and Crystal Structure The title compound crystallizes in good shaped single crystals from the system lithium sulfate/sulfuric acid in the orthorhombic space group Pccn, unit cell parameters a = 17.645(4), b = 5.378(1), c = 10.667(3) Å. V = 1 012.2 ų, Z = 4, D_x = 2.009 g cm^?3. There are two types of SO₄ tetrahedra, SO₃(OH) and SO₂(OH)₂, connected via hydrogen bonds forming layers parallel to the xy-plane. The layers are linked by Li atoms, which are tetrahedral coordinated by O atoms coming two by two from neighboured layers.     

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.     

Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)]

Two novel isopropylamine‐templated uranyl chromates, [(CH₃)₂CHNH₃]₃[(UO₂)₃(CrO₄)₂O(OH)₃] ( 1 ) and [(CH₃)₂CHNH₃]₂[(UO₂)₂(CrO₄)₃(H₂O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X‐ray diffraction crystal structure analysis [ 1 : trigonal, P31m, a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) ų; 2 : monoclinic, P2₁/c, a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) ų]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO₄ tetrahedra to form [(UO₂)₃(CrO₄)₂O(OH)₃]^3– layers, whereas, in the structure of 2 , UO₇ and UO₆(H₂O) pentagonal bipyramids are linked through CrO₄ tetrahedra into the [(UO₂)₂(CrO₄)₃(H₂O)]^2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.     

Synthese und Kristallstruktur von Te3O3(PO4)2, einer Verbindung mit fünffach koordiniertem Tellur(IV)

Synthesis and Crystal Structure of Te₃O₃(PO₄)₂, a Compound with 5‐fold Coordinate Tellurium(IV) Polycrystalline Te₃O₃(PO₄)₂ is formed during controlled dehydration of (Te₂O₃)(HPO₄) with (Te₈O₁₀)(PO₄)₄ as an intermediate product. Colourless single crystals were prepared by heating stoichiometric amounts of the binary oxides P₂O₅ und TeO₂ in closed silica glass ampoules at 590 °C for 8 hours. The crystal structure (P2₁/c, Z = 4, α = 12.375(2), b = 7.317(1), c = 9.834(1)Å, β = 98.04(1)°, 1939 structure factors, 146 parameters, R[F² > 2σ(F²)] = 0.0187, wR2(F² all) = 0.0367) was determined from four‐circle diffractometer data and consists of [TeO₅] polyhedra und PO₄ tetrahedra as the main building units. The framework structure is made up of cationic zigzag‐chains of composition [Te₂O₃]²⁺ which extend parallel to [001] and anionic [Te(PO₄)₂]^2— units linked laterally to these chains. This leads to the formation of [Te₂O₃][Te(PO₄)₂] layers parallel to the bc plane which are interconnected via weak Te‐O bonds.     

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.     

Synthese und Struktur von Hydrogensulfaten des Typs M(HSO4)(H2SO4) (M = Rb,Cs und NH4)

Synthesis and Structure of Hydrogen Sulfates of the Type M(HSO₄)(H₂SO₄) (M = Rb, Cs and NH₄) From the binary systems M₂SO₄/H₂SO₄ (M = Rb, Cs, NH₄), three new hydrogen sulfates of the type M(HSO₄)(H₂SO₄) could be synthesized and structural characterized. The rubidium and caesium compounds are isotypic whereas NH₄(HSO₄)(H₂SO₄) is topologically very similar to both. All three compounds crystallize with nearly identical cell parameters [Rb: a = 7.382(1), b = 12.440(2), c = 7.861(2), β = 93.03(3); Cs: a = 7.604(1), b = 12.689(2), c = 8.092(2), β = 92.44(3); NH₄: a = 7.521(3), b = 12.541(5), c = 7.749(3), β = 92.74(3)], in the monoclinic space group P2₁/c, There exist two kinds of SO₄-tetrahedra: HSO₄^? anions (S1) and H₂SO₄-molecules (S2). The HSO₄^? anions form hydrogen bridged zigzag chains. In the case of the Rb and Cs compounds, the H₂SO₄ molecules connect these chains forming double layers. The metal atoms are coordinated by 9 O-atoms with M? O-distances of 2.97 – 3.39 Å (Rb) and 3.13 – 3.51 Å (Cs). In the ammonium compound additional hydrogen bonds are formed originating from the NH₄⁺ cation. This finally leads to the formation of S2? NH₄⁺ chains (parallel to the S1 chains) as well as to a three-dimensional connection of both kinds of chains.     

The iron phosphate NaZnFe2(PO4)3

Crystals of sodium zinc diiron(III) triphosphate, NaZnFe₂(PO₄)₃, have been synthesized and structurally characterized by single‐crystal X‐ray diffraction. The compound features a new structural type built up from ZnO₆ octahedra, FeO₆ octahedra and FeO₄ tetrahedra, linked together via the corners and edges of PO₄ tetrahedra to form a three‐dimensional framework, with tunnels running along [100]. Within these tunnels, Na⁺ cations occupy a highly distorted cubic site.     

Hybrid Inorganic‐Organic Frameworks: Synthesis and Crystal Structures of RbFe(SO4)(C2O4)0.5·H2O and CsM(SO4)(C2O4)0.5·H2O (M = Mn,Fe)

Three new alkali metal transition metal sulfate‐oxalates, RbFe(SO₄)(C₂O₄)_0.5 · H₂O and CsM(SO₄)(C₂O₄)_0.5 · H₂O (M = Mn, Fe) were prepared through hydrothermal reactions and characterized by single‐crystal X‐ray diffraction, solid state UV/Vis/NIR diffuse reflectance spectroscopy, infrared spectra, thermogravimetric analysis, and powder X‐ray diffraction. The title compounds all crystallize in the monoclinic space group P2₁/c (no. 14) with lattice parameters: a = 7.9193(5), b = 9.4907(6), c = 8.8090(6) Å, β = 95.180(2)°, Z = 4 for RbFe(SO₄)(C₂O₄)_0.5 · H₂O; a = 8.0654(11), b = 9.6103(13), c = 9.2189(13) Å, β = 94.564(4)°, Z = 4 for CsMn(SO₄)(C₂O₄)_0.5 · H₂O; and a = 7.9377(3), b = 9.5757(4), c = 9.1474(4) Å, β = 96.1040(10)°, Z = 4 for CsFe(SO₄)(C₂O₄)_0.5 · H₂O. All compounds exhibit three‐dimensional frameworks composed of [MO₆] octahedra, [SO₄]^2– tetrahedra, and [C₂O₄]^2– anions. The alkali cations are located in one‐dimensional tunnels.