Rb(GaPO4)2(OH)(H2O)·H2O: a hydrated rubidium gallium phosphate analogue of GaPO4·2H2O and leucophosphite

Crystals of the title hydrated rubidium gallium phosphate, rubidium aqua‐μ₃‐hydroxo‐di‐μ‐phosphato‐digallium hydrate, were synthesized hydro­thermally at 453 K under autogenous pressure. The solid crystallizes in the monoclinic system and its structure was determined from single‐crystal X‐ray diffraction analysis. It is similar to dihydrated gallium phosphate, GaPO₄·2H₂O, which is isostructural with the mineral leucophosphite. The structure is built up from a three‐dimensional anionic framework composed of corner‐linked octameric Ga₄(PO₄)₄(OH)₂(H₂O)₂ units. The Ga atom is in an octahedral coordination. Connection of the Ga₄P₄ species generates eight‐ring channels, in which are encapsulated the Rb⁺ cations and water mol­ecules.     

(NH4)2ZrGe3O9: a new microporous zirconogermanate

A new microporous zirconogermanate, di­ammonium zirconium trigermanate, (NH₄)₂ZrGe₃O₉ (FDZG‐2), analogous to wadeite (K₂ZrSi₃O₉), was hydro­thermally synthesized using ZrO(NO₃)₂·2H₂O as the source of zirconium and 1,4‐di­amino­butane as a structure‐directing agent. Single‐crystal X‐ray diffraction analysis reveals that the framework structure is built up of cyclic trigermanate units crosslinked by ZrO₆ octahedra. The Zr atom lies at a site with symmetry and the unique N atom of the ammonium ion lies at a site with threefold symmetry. Large cages are observed, with two NH₄⁺ cations in each. The structure contains intersecting six‐ and three‐membered ring (6MR and 3MR) channels, but only the 6MR channels can accommodate the NH₄⁺ ions.     

CsTiP2O7

From single‐crystal X‐ray data, cesium titanium pyrophos­phate, CsTiP₂O₇, is found to crystallize in the KAlP₂O₇ structure type. It possesses a three‐dimensional tunnel structure built by the corner‐sharing of distorted TiO₆ octahedra and P₂O₇ pyrophosphate groups. The Cs⁺ cations are in the tunnels.     

Penkvilksite‐2O: Na2TiSi4O11·2H2O

The crystal structure of synthetic penkvilksite‐2O, disodium titanium tetrasilicate dihydrate, Na₂TiSi₄O₁₁·2H₂O, a microporous titanosilicate, confirms the major features of a previous model that had been obtained by order–disorder (OD) theory from the known structure of penkvilksite‐1M. An important difference from the previous model involves the hydrogen bonding of the water molecule which, on the basis of a Raman spectrum and the finding of only one of the two H atoms, is proposed to be disordered about a fixed O–H direction. The structure of penkvilksite‐2O is based on (100) silicate layers linked by isolated TiO₆ octahedra to form a heteropolyhedral framework. The layer is strongly corrugated, based on interlaced spiral chains, and is crossed by two different channels that have an effective channel width of about 3 Å.     

A non‐twinned polymorph of CaTe2O5 from a hydrothermally grown crystal

In contrast with the multiple twinning and/or domain formation found in the mica‐like polymorphs of CaTe₂O₅, calcium pentaoxidoditellurate(IV), that have been prepared by solid‐state reactions and for which complete structure determinations have not been successful up to now, the crystal structure of a hydrothermally grown phase was fully determined from a non‐twinned crystal. The structure is made up of alternating layers of Ca²⁺ cations and of ²_∞[Te₂O₅]²⁻ anions stacked along [100]. The lone‐pair electrons E of the Te^IV atoms are stereochemically active and protrude into channels within the anionic layer. In comparison with analogous M^IITe₂O₅ structures (M = Mg, Mn, Ni or Cu) with ditellurate(IV) anions that are exclusively made up of corner‐sharing TeO_x (x = 3–5) polyhedra resulting in flat ²_∞[Te₂O₅]²⁻ layers, the anionic layers in CaTe₂O₅ are undulating and are built of corner‐ and edge‐sharing [TeO₄] polyhedra.     

Synthesis and Crystal Structure of KSc(HPO4)2

KSc(HPO₄)₂ was obtained by hydrothermal synthesis. The crystal structure was determined from single‐crystal X‐ray data: orthorhombic, space group Pnma (No. 62), a = 14.5095(10), b = 5.4260(4), c = 8.4882(5) Å, V = 668.26(8) ų and Z = 4. The crystal structure of KSc(HPO₄)₂ represents a new structure type containing twelve‐ and four‐membered rings forming channels along [010] built of alternating ScO₆ octahedra and HPO₄^2? groups. Potassium ions reside within the twelve membered ring channels.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

(K4Li4)Al8Ge8O32·8H2O: an Li+‐exchanged potassium aluminogermanate with the zeolite gismondine (GIS) topology

The title compound, lithium potassium dialuminium di­ger­man­ium octaoxide dihydrate, (K,Li)‐(Al,Ge)‐GIS (GIS is gismondine), is the result of a 50% Li⁺ exchange into the K‐(Al,Ge)‐GIS structure. The (K,Li)‐(Al,Ge)‐GIS structure was determined from a 4 × 4 × 2 µm octahedral single crystal at the ESRF synchrotron X‐ray source. The ion exchange results in a symmetry transformation from I2/a for K‐(Al,Ge)‐GIS to C2/c for (K,Li)‐(Al,Ge)‐GIS. The structural change is due to disordering of K⁺ ions with Li⁺ ions along the [001] channel and ordering of water molecules in the [101] channels. The distance between sites partially occupied by K⁺ ions increases from 2.19 (3) Å in K‐(Al,Ge)‐GIS to 2.94 (3) Å in (K,Li)‐(Al,Ge)‐GIS. The Li⁺ ions occupy positions along the twofold axis at the intersection of the eight‐membered‐ring channels in a twofold coordination with water mol­ecules. For the four closest framework O²⁻ anions, the Li⃛O distances are 3.87 (4) Å.     

Synthesis,Crystal Structure and Characterization of a new Protonated Magnesium Borophosphate: (H3O)Mg(H2O)2[BP2O8]·H2O

A new protonated borophosphate (H₃O)Mg(H₂O)₂[BP₂O₈]·H₂O ( 1 ) was synthesized under mild hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, FTIR spectroscopy and TG‐DTA. The compound crystallizes in the hexagonal system, space group P6(1)22 (No 178), a = 9.4462(7) Å, c = 15.759(2) Å, V = 1217.8(2) Å³, and Z = 6. There exist infinite helical $^1_\infty$ {[BP₂O₈]^3–} ribbons built up from corner‐sharing PO₄ and BO₄ tetrahedra, which are connected by MgO₄(H₂O)₂ leading to an infinite three‐dimensional open‐framework. The H₃O⁺ ions are located at the free thread of the helical ribbons, whereas crystallized water occupy the channels of the helical ribbons. The dehydration of the compound occurs at a higher temperature which is presumably due to the anisotropic hydrogen bonds in the crystal structure. The luminescent properties of the compound were studied.     

Preparation,Crystal Structure and Vibrational Spectra of Ca2P2O6·2H2O and [Ca(H2O)3(H2P2O6)]·0.5(C12H24O6)·H2O

The calcium salts Ca₂P₂O₆ · 2H₂O ( 1 ) and [Ca(H₂O)₃(H₂P₂O₆)] · 0.5(C₁₂H₂₄O₆) · H₂O ( 2 ) were prepared and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic space group Pbca and compound 2 in the monoclinic space group P2₁/n. The crystal structure of compound 1 consists of chains of edge‐sharing [CaO₇] polyhedra linked by hypodiphosphate(IV) anions to form a three‐dimensional network. The crystal structure of compound 2 consists of alternated layers of crown ether and water molecules and respective ionic units. Within the layers of ionic units the Ca²⁺ cations are octahedrally coordinated by three monodentate dihydrogenhypodiphosphate(IV) anions and three water molecules. The IR/Raman spectra of the title compounds were recorded and interpreted, especially with respect to the [P₂O₆]^4– and [H₂P₂O₆]^2– groups. The phase purity of 2 was verified by powder diffraction measurements.     

Strong Attraction of Caffeine to the Mercurous Dumbbell in the Salt [Hg2(Caf)2](ClO4)2(H2O)2

Colourless single crystals of the caffeine adduct of mercurous perchlorate dihydrate, [Hg₂(Caf)₂](ClO₄)₂(H₂O)₂, were grown from aqueous solutions of mercurous perchlorate and caffeine by isothermal evaporation at ambient temperature. The crystal structure (monoclinic, P2₁/n, Z = 4, a = 1628.0(2), b = 780.4(1), c = 2229.6(3) pm, β = 99.84(1)°, R₁(all data) = 0.0894) contains [trans‐Caf‐Hg‐Hg‐Caf]²⁺ cations with a Hg‐Hg distance of 250.88(6) pm, Hg‐N (bond) distances of 214.4(6) and 215.1(6) pm and Hg‐Hg‐N angles of 176.9(2) and 165.1(2)°, respectively. These cations are attached via weak Hg‐O contacts to dimers which are further arranged to leave large channels into which one crystal water molecule is included. The second water molecule and the two perchlorate anions are weakly attracted to one Hg atom.     

Sm2As4O9: Ein ungewöhnliches Samarium(III)‐Oxoarsenat(III) gemäß Sm4[As2O5]2[As4O8]

Sm₂As₄O₉: An Unusual Samarium(III) Oxoarsenate(III) According to Sm₄[As₂O₅]₂[As₄O₈] Pale yellow single crystals of the new samarium(III) oxoarsenate(III) with the composition Sm₄As₈O₁₈ were obtained by a typical solid‐state reaction between Sm₂O₃ and As₂O₃ using CsCl and SmCl₃ as fluxing agents. The compound crystallizes in the triclinic crystal system with the space group (No. 2, Z = 2; a = 681.12(5), b = 757.59(6), c = 953.97(8) pm, α = 96.623(7), β = 103.751(7), γ = 104.400(7)°). The crystal structure of samarium(III) oxoarsenate(III) with the formula type Sm₄[As₂O₅]₂[As₄O₈] (≡ 2 × Sm₂As₄O₉) contains two crystallographically different Sm³⁺ cations, where (Sm1)³⁺ is coordinated by eight, but (Sm2)³⁺ by nine oxygen atoms. Two different discrete oxoarsenate(III) anions are present in the crystal structure, namely [As₂O₅]^4? and [As₄O₈]^4?. The [As₂O₅]^4? anion is built up of two Ψ¹‐tetrahedra [AsO₃]^3? with a common corner, whereas the [As₄O₈]^4? anion consists of four Ψ¹‐tetrahedra with ring‐shaped vertex‐connected [AsO₃]^3? pyramids. Thus at all four crystallographically different As³⁺ cations stereochemically active non‐binding electron pairs (“lone pairs”) are observed. These “lone pairs” direct towards the center of empty channels running parallel to [010] in the overall structure, where these “empty channels” being formed by the linkage of layers with the ecliptically conformed [As₂O₅]^4? anions and the stair‐like shaped [As₄O₈]^4? rings via common oxygen atoms (O1 – O6, O8 and O9). The oxygen‐atom type O7, however, belongs only to the cyclo‐[As₄O₈]^4? unit as one of the two different corner‐sharing oxygen atoms.     

Cu3V10O28·24H2O and CuNa4V10O28·23H2O

The crystal structures of tricopper decavanadate tetracosa­hydrate, (I), and copper tetra­sodium decavanadate tricosa­hydrate, (II), have been determined by single‐crystal X‐ray diffraction. Both compounds exhibit a catenary structure consisting of [V₁₀O₂₈]⁶⁻ anions linked by Cu²⁺ cations in (I) or by Na⁺ cations in (II). Compound (II) also contains a polymeric linear array of edge‐sharing [Na(OH₂)₆]⁺ and [Cu(OH₂)₆]²⁺ octahedra. In both compounds, the [V₁₀O₂₈]⁶⁻ ions lie about inversion centres and the Cu²⁺ ions in (I) also lie about inversion centers.     

K2[Mo2O4(C2O4)2(H2O)2]·3H2O

The crystal and molecular structure of dipotassium di‐μ‐oxo‐bis[aqua(oxalato‐O¹,O²)oxomolybdenum(III)] trihydrate, K₂­[Mo₂O₄(C₂O₄)₂(H₂O)₂]·3H₂O, has been determined from X‐ray diffraction data. In the dimeric anion, which has approximate twofold symmetry, each Mo atom is in a distorted octahedral coordination, being bonded to one terminal oxo‐O atom, two bridging O atoms, two O atoms from the oxalato ligand and one from the water mol­ecule. Bond lengths trans to the multiple‐bonded terminal oxo ligand are larger than those in the cis position, confirming the trans influence as a generally valid rule.     

Lithium carnallite,LiCl·MgCl2·7H2O

The title compound, lithium magnesium chloride heptahydrate, LiCl·MgCl₂·7H₂O, was analyzed in 1988 by powder X‐ray diffraction [Emons, Brand, Pohl & Köhnke (1988). Z. Anorg. Allg. Chem. 563 , 180–184] and a monoclinic crystal lattice was determined. In the present work, the structure was solved from single‐crystal diffraction data. A trigonal structure was found, exhibiting a network structure of Mg(H₂O)₆ octahedra and Li(H₂O)Cl₃ tetrahedra connected by H...Cl hydrogen bonds. The [Li(H₂O)]⁺ unit is coordinated by distorted edge‐connected Cl⁻ octahedra.     

Li2AlB5O10

A new compound, dilithium aluminium pentaborate, Li₂Al­B₅O₁₀, has been synthesized by solid‐state reaction and its structure determined by single‐crystal X‐ray diffraction. This compound is composed of [B₅O₁₀]^5? groups linked by AlO₄ tetrahedra. The [B₅O₁₀]^5? group consists of two hexagonal B–­O rings perpendicular to each other connected by tetracoordinated boron. All the B–O rings in this structure can be divided into two groups, with one group approximately parallel and the other perpendicular to the c axis.     

Further Example of Diphosphates: Synthesis and Characterization of K2Li2P2O7

By the application of cation substitution, a new mixed‐alkali metal diphosphate, K₂Li₂P₂O₇, was successfully synthesized through high temperature solution method for the first time. The single‐crystal X‐ray structural analysis shows that it crystallizes in the monoclinic space group C2/c (no. 15), with lattice constants a = 9.814(3) Å, b = 5.5163(15) Å, c = 13.538(4) Å, Z = 4, and β = 110.47(2)°. Its open cage‐like _∞³[Li₂(P₂O₇)]^2– framework is built up from alternating arrangement of Li₂O₆ and P₂O₇ dimers that form eight and twelve‐membered‐ring channels along the [010] direction, and the K atoms are entrapped in the larger twelve‐membered‐ring channels. Detailed structure comparisons in the N₄P₂O₇ (N = mixed alkali metals) family are discussed. In addition, the structural validity was verified through the IR spectrum. Thermal analyses and UV/Vis/NIR diffuse reflectance spectrum are also performed on the reported compound.     

A cyanide‐bridged bimetallic complex, [CrPr(CN)6(C3H7NO)4(H2O)3]·H2O

The crystal structure of the bimetallic cyanide‐bridged title complex, tri­aqua‐1κ³O‐μ‐cyano‐1:2κ²N:C‐penta­cyano‐2κ⁵C‐tetrakis(N,N‐di­methyl­form­amide)‐1κ⁴O‐chromium(III)­prase­odymium(III) monohydrate, was obtained by single‐crystal X‐ray diffraction. The central praseodymium(III) ion is eight‐coordinate, arranged in a square antiprism, while the chromium(III) ion is six‐coordinate, oriented octahedrally. Molecules in the crystal lattice are held together by a network of hydrogen bonds.     

Synthesis and Structure of the New Compound La2O(CN2)2 Possessing an Interchanged Anion Proportion Compared to the Parent La2O2(CN2). Synthese und Kristallstruktur der neuen Verbindung La2O(CN2)2 mit einem vertauschten Anionenverhältnis gegenüber der Bezugsverbindung La2O2(CN2)

La₂O(CN₂)₂ was synthesized from a 1:1:2 molar reaction mixture of LaCl₃, LaOCl, and Li₂(CN₂) at 650 °C. Well developed single crystals were grown from a LiCl‐KCl flux. The crystal structure was refined as monoclinic (space group C2/c, Z = 2, a = 13.530(2) Å, b = 6.250(1) Å, c = 6.1017(9) Å, β = 104.81(2)°) from single crystal X‐ray diffraction data. The La³⁺ and (CN₂)^2— ions in the crystal structure of La₂O(CN₂)₂ can be compared to Fe³⁺ and S₂^2— ions in the cubic pyrite structure, being arranged like in a distorted NaCl type structure with their centers of gravity. In addition, the O^2— ions in La₂O(CN₂)₂ are occupying 1/4 of the tetrahedral voids formed by the arrangement of metal ions.     

An Organically Templated Copper Pentaborate with Infinite Metallo-chains:[Cu(C3N2H4)4][Cu(CH3COO)2(C3N2H4)2(H2O)2][B5O6(OH)4]2

A novel organically templated copper pentaborate, [Cu(C₃N₂H₄)₄][Cu(CH₃COO)₂(C₃N₂H₄)₂(H₂O)₂]‐ [B₅O₆(OH)₄]₂, was synthesized by hydrothermal reaction and characterized by elemental analysis, single‐crystal X‐ray diffraction, FT‐IR spectroscopy, Raman spectroscopy and TGA. The crystal structure of this compound consists of two copper‐centered polyhedra and two discrete [B₅O₆(OH)₄]^? pentaborate anions, which are linked together through intensive hydrogen bonding interactions, forming a 3D framework with large channels along c axis. The discrete pentaborate anions form infinite layers by hydrogen bonds. Moreover, the two crystallographically different octahedral coppers are connected by common oxygen atom to form an infinite chain.