K5.76Ga5.76Si10.24O32·3.4H2O,a gallosilicate with the zeolite gismondine topology

The title compound, K–GaSi–GIS, potassium gallium silicon oxide hydrate, was synthesized hydro­thermally and its crystal structure was determined from data collected on a single crystal of dimensions 10 × 10 × 8 µm at a synchrotron X‐ray source. The compound, which has the aluminosilicate (AlSi) zeolite gismondine (GIS) topology, Ca₄[Al₈Si₈O₃₂]·16H₂O, crystallizes in the tetragonal space group I4₁/a. A disordered distribution of the framework Si/Ga sites leads to higher symmetry of the GIS‐type network compared with the usual monoclinic symmetry in AlSi–GIS. Framework Ga substitution for Al in AlSi–GIS leads to substantial distortion of the crankshaft chains, reducing the effective pore dimensions and suggesting the possibility of pore‐dimension control via partial framework‐cation substitution.     

Zur Koordination des Aluminiums in den Calciumaluminathydraten 2 CaO · Al2O3 · 8 H2O und CaO · Al2O3 · 10 H2O

On the Coordination of Al in the Calcium Aluminate Hydrates 2 CaO · Al₂O₃ · 8 H₂O and CaO · Al₂O₃ · 10 H₂O By investigations with high-resolution ²⁷Al-NMR in solids it is shown that in the compound 2 CaO · Al₂O₃ · 8 H₂O the Al merely exist in octahedral coordination. According to this and considering its structural relationship with 4 CaO · Al₂O₃ · 19 H₂O the dicalcium aluminate hydrate is proposed to be formulated as [Ca₂Al(OH)₆][Al(OH)₃ (H₂O)₃]OH. Likewise for the compound CaO · Al₂O₃ · 10 H₂O the octahedral coordination of the Al is proved by ²⁷Al-NMR. This result corresponds with literature according to which a constitution as cyclohexaaluminate Ca₃[Al₆(OH)₂₄] · 18 H₂O is proposed.     

3Mg(OH)2·MgSO4·8H2O: A Metastable Phase in the System Mg(OH)2‐MgSO4‐H2O

In the course of investigations relating to magnesia oxysulfate cement the basic magnesium salt hydrate 3Mg(OH)₂ · MgSO₄ · 8H₂O (3–1–8 phase) was found as a metastable phase in the system Mg(OH)₂‐MgSO₄‐H₂O at room temperature (the 5–1–2 phase is the stable phase) and was characterized by thermal analysis, Raman spectroscopy, and X‐ray powder diffraction. The complex crystal structure of the 3–1–8 phase was determined from high resolution laboratory X‐ray powder diffraction data [space group C2/c, Z = 4, a = 7.8956(1) Å, b = 9.8302(2) Å, c = 20.1769(2) Å, β = 96.2147(16)°, and V = 1556.84(4) ų]. In the crystal structure of the 3–1–8 phase, parallel double chains of edge‐linked distorted Mg(OH₂)₂(OH)₄ octahedra run along [–110] and [110] direction forming a pattern of crossed rods. Isolated SO₄ tetrahedra and interstitial water molecules separate the stacks of parallel double chains.     

The structures of the α‐alums RbCr(SO4)2·12H2O and CsCr(SeO4)2·12H2O at 293 and 12 K

The crystal structures of the α‐alums rubidium chromium bis(­sulfate) dodecahydrate, RbCr(SO₄)₂·12H₂O, and caesium chromium bis[tetraoxoselenate(VI)] dodecahydrate, CsCr(SeO₄)₂·12H₂O, have been determined by X‐ray diffraction at 293 and 12 K. The metal atoms lie on sites and the anions lie on threefold rotation axes. The accurate and extensive data sets lead to much more precise determinations than are available from earlier work, particularly at 12 K. The changes in the atomic displacement parameters between 293 and 12 K correspond to the respective predominances of intermolecular and intramolecular vibrational effects.     

KCo(H2O)2BP2O8·0.48H2O and K0.17Ca0.42Co(H2O)2BP2O8·H2O: two cobalt borophosphates with helical ribbons and disordered (K,Ca)/H2O schemes

The two title compounds, potassium diaquacobalt(II) borodiphosphate 0.48‐hydrate and potassium–calcium(0.172/0.418) diaquacobalt(II) borodiphosphate monohydrate, were synthesized hydrothermally. They are new members of the borophosphate family characterized by _∞[BP₂O₈]³⁻ helices running along [001] and constructed of boron (Wyckoff position 6b, twofold axis) and phosphorus tetrahedra. The [CoBP₂O₈]⁻ anionic frameworks in the two materials are structurally similar and result from a connection in the ab plane between the CoO₄(H₂O)₂ coordination octahedra (6b position) and the helical ribbons. Nevertheless, the two structures differ in the disorder schemes of the K,Ca and H₂O species. The alkali cations in the structure of the pure potassium compound are disordered over three independent positions, one of them located on a 6b site. Its framework is characterized by double occupation of the tunnels by water molecules located on twofold rotation axes (6b) and a fraction of alkali cations; its cell parameters, compared with those for the mixed K,Ca compound, show abnormal changes, presumably due to the disorder. For the K,Ca compound, the K and Ca cations are on twofold axes (6b) and the channels are occupied only by disordered solvent water molecules. This shows that it is possible, due to the flexibility of the helices, to replace the alkali and alkaline earth cations while retaining the crystal framework.     

Crystal Structure and Luminescence of a Europium Coordination Polymer {[Eu(p-MOBA)_3·2H_2O]·0.5H_2O· 0.5(4,4′-bipy)}_∞

ＩｎｔｒｏｄｕｃｔｉｏｎＭｏｎｏｎｕｃｌｅａｒ ,ｄｉｎｕｃｌｅａｒａｎｄｐｏｌｙｍｅｒｉｃｔｙｐｅｓｏｆｃｒｙｓ ｔａｌｓｔｒｕｃｔｕｒｅｓｆｏｒｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｗｉｔｈｂｅｎｚｏｉｃａｃｉｄａｎｄｉｔｓｄｅｒｉｖａｔｉｖｅｓｈａｖｅｂｅｅｎｏｂｔａｉｎｅｄｂｅｃａｕｓｅｏｆｔｈｅｖａｒｉ ａｔｉｏｎｏｆｂｒｉｄｇｉｎｇｆｏｒｍｓｆｏｒｃａｒｂｏｘｙｌａｔｅｇｒｏｕｐａｎｄｃｏｏｒｄｉｎａ ｔｉｏｎａｂｉｌｉｔｙｏｆｄｉａｍｍｉｎｅｌｉｇａｎｄｓ ,ｓｕｃｈａｓ 1,10 ｐｈｅｎａ…     

RbCrIII(C2O4)2·2H2O,Cs2Mg(C2O4)2·4H2O and Rb2CuII(C2O4)2·2H2O: three new complex oxalate hydrates

Rubidium chromium(III) dioxalate dihydrate [di­aqua­bis(μ‐oxalato)­chromium(III)­rubidium(I)], [RbCr(C₂O₄)₂(H₂O)₂], (I), and dicaesium magnesium dioxalate tetrahydrate [tetra­aqua­bis(μ‐oxalato)­magnesium(II)­dicaesium(I)], [Cs₂Mg(C₂­O₄)₂(H₂O)₄], (II), have layered structures which are new among double‐metal oxalates. In (I), the Rb and Cr atoms lie on sites with imposed 2/m symmetry and the unique water molecule lies on a mirror plane; in (II), the Mg atom lies on a twofold axis. The two non‐equivalent Cr and Mg atoms both show octahedral coordination, with a mean Cr—O distance of 1.966 Å and a mean Mg—O distance of 2.066 Å. Dirubid­ium copper(II) dioxalate dihydrate [di­aqua­bis(μ‐oxalato)­copper(II)­dirubidium(I)], [Rb₂Cu(C₂O₄)₂(H₂O)₂], (III), is also layered and is isotypic with the previously described K₂‐ and (NH₄)₂Cu^II(C₂O₄)₂·2H₂O compounds. The two non‐equivalent Cu atoms lie on inversion centres and are both (4+2)‐coordinated. Hydro­gen bonds are medium‐strong to weak in the three compounds. The oxalate groups are slightly non‐planar only in the Cs–Mg compound, (II), and are more distinctly non‐planar in the K–Cu compound, (III).     

Kristallstrukturen des Sr(BrO3)2 · H2O,Ba(BrO3)2 · H2O,Ba(IO3)2 · H2O,Pb(CIO3)2 · H2O und Pb(BrO3)2 · H2O

Crystal Structure of Sr(BrO₃)₂ · H₂O, Ba(BrO₃)₂ · H₂O, Ba(IO₃)₂ · H₂O, Pb(ClO₃)₂ · H₂O, and Pb(BrO₃)₂ · H₂O The crystall structures of the isostructural halates Sr(BrO₃)₂ · H₂O, Ba(BrO₃)₂ · H₂O, Ba(IO₃)₂ · H₂O, Pb(ClO₃)₂ · H₂O, and Pb(BrO₃)₂ · H₂O were determined using X-ray single crystal data (monoclinic space group C2/c? C, Z = 4), The mean bond lengths and bond angles of the halate ions in the Ba(ClO₃)₂ · 1 H₂O-type compounds, which correspond to those of other halates, are Cl? O, 149.0, Br? O, 165.9, I? O, 180.2 pm, ClO₃^?, 106.4, BrO₃^?, 104.0, and IO₃^?, 99.6°. The structure data obtained are discussed in terms of possible orientational disorder of the water molecules, strengths of the hydrogen bonds, influence of the lead ions on the structure, and site group distortion of the halate ions.     

CoCl_2·6H_2O or LaCl_3·7H_2O Catalyzed Biginelli Reaction. One-Pot Synthesis of 3,4-Dihydropyrimidin-2(1 H)-ones

Ｉｎｔｒｏｄｕｃｔｉｏｎ1,4 Ｄｉｈｙｄｒｏｐｙｒｉｄｉｎｅｓｏｆｔｈｅｎｉｆｅｄｉｐｉｎｅｔｙｐｅ (ｅ .ｇ .Ｉ—ＩＩＩ)ａｒｅｔｈｅｍｏｓｔｓｔｕｄｉｅｄｃｌａｓｓｏｆｏｒｇａｎｉｃｃａｌｃｉｕｍｃｈａｎｎｅｌｍｅｄｉｃｉｎｅ ,ｗｈｉｃｈｈａｖｅｂｅｃｏｍｅａｌｍｏｓｔｉｎｄｉｓｐｅｎｓ ａｂｌｅｆｏｒｔｈｅｔｒｅａｔｍｅｎｔｏｆｃａｒｄｉｏｖａｓｃｕｌａｒｄｉｓｅａｓｅｓｓｕｃｈａｓｈｙｐｅｒｔｅｎｓｉｏｎ ,ｃａｒｄｉａｃａｒｒｈｙｔｈｍｉａｓ ,ｏｒａｎｇｉｎａ .1Ｉｎｔｈｅｐａｓｔｄｅｃａｄｅ…     

{[Eu(ox)(H2O)4]·[CuBr(2‐pzc)2]·4H2O}: Hydrogen Bonding Directed Assembly to Supramolecular Network

A new 3d–4f heterometallic coordination framework, {[Eu(ox)(H₂O)₄] · [CuBr(2‐pzc)₂] · 4H₂O} ( 1 ) [ox = oxalate; 2‐pzc = pyrazine‐2‐carboxylate] was synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis, as well as single‐crystal X‐ray diffraction. Complex 1 represents one 3D supramolecular heterometallic coordination framework that is assembled from rare lanthanide‐ox anionic chains and CuBr(2‐pzc)₂ cationic units through hydrogen bonds.     

A Novel Adipate Bridged Supramolecular Layer: Crystal Structure of the Cobalt(II) Complex [(μ‐C6H8O4)4/2Co(μ‐H2O)2Co(H2O)4] · 4 H2O

The pale‐rose compound [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] · 4 H₂O was prepared from adipic acid and CoCO₃ in aqueous solution. The crystal structure (monoclinic, P2₁/n (no. 14), a = 8.061(1), b = 15.160(2), c = 9.708(2) Å, β = 90.939(7)°, Z = 2, R = 0.0405, wR² = 0.0971) consists of adipate bridged supramolecular [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] layers and hydrogen bonded H₂O molecules. The cobalt atoms Co1 and Co2 are distorted octahedrally coordinated by the O atoms of two bridging trans‐H₂O molecules and four bidentate adipate anions (Co1) and by the O atoms of two bridging trans‐H₂O molecules and four monodentate H₂O molecules (Co2), respectively. Equatorial bonds: d(Co1–O) = 2.048 Å (2 × ), 2.060 Å (2 × ); d(Co2–O) = 2.057 Å (2 × ), 2.072 Å (2 × ). Axial bonds: d(Co1–O) = 2.235 Å (2 × ); d(Co2–O) = 2.156 Å (2 × ).     

Einfach und doppelt deprotonierte Maleinsäure in Praseodym‐hydrogenmaleat‐octahydrat,Pr(C4O4H3)3 · 8 H2O,und Praseodym‐maleatchlorid‐tetrahydrat,Pr(C4O4H2)Cl · 4 H2O

Single and Double Deprotonated Maleic Acid in Praseodymium Hydrogenmaleate Octahydrate, Pr(C₄O₄H₃)₃ · 8 H₂O, and Praseodymiummaleatechloride Tetrahydrate, Pr(C₄O₄H₂)Cl · 4 H₂O Single crystals of Pr(C₄O₄H₃)₃ · 8 H₂O grew by slow evaporation of a solution which had been obtained by dissolving Pr(OH)₃ in aqueous maleic acid. The triclinic compound (P1, Z = 2, a = 728.63(3), b = 1040.23(3), c = 1676.05(8) pm, α = 72.108(2)°, β = 87.774(2)°, γ = 70.851(2)°, R_all = 0.0261) contains Pr³⁺ ions in ninefold coordination of oxygen atoms which belong to two monodentate maleate ions and seven H₂O molecules. There is one further non‐coordinating maleate ion and one crystal water molecule in the unit cell. Thermal treatment of Pr(C₄O₄H₃)₃ · 8 H₂O leads first to the anhydrous compound which then decomposes to the respective oxide in two steps upon further heating. Evaporation of a solution of Pr(C₄O₄H₃)₃ · 8 H₂O which contained additional Cl^– ions yielded single crystals of Pr(C₄O₄H₂)Cl · 4 H₂O. In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 866.0(1), b = 1344.3(1), c = 896.9(1) pm, β = 94.48(2)°, R_all = 0.0227), the Pr³⁺ ions are surrounded by nine oxygen atoms. The latter belong to four H₂O molecules and three maleate ions. Two of the latter act as bidentate ligands.     

K2B4O7-Na2B4O7-Li2B4O7-H2O 四元体系15℃介稳相平衡研究

采用等温蒸发平衡法研究了四元体系K2B4O7-Na2B4O7-Li2B4O7-H2O15℃时的介稳相平衡及平衡液相的物化性质(密度,粘度,电导率,折光率,pH)。根据实验数据绘制了相图,相图中有一个共饱点E,三条单变度曲线E3F,E2F,E1F;三个平衡固相分别为：K2B4O7•4H2O,Na2B4O7•10H2O和Li2B2O4•16H2O;硼酸钾具有最大溶解度,硼酸钠具有最小溶解度。同时,根据试验数据绘制了组成－物化性质关系图,从图可见溶液的密度,粘度和折光率均随着溶液浓度的增大而逐渐增大,在共饱和点F处达到最大值,而溶液的pH值和电导率却随着溶液浓度的增大呈总体下降的趋势。     

New Fluoromanganate(III) Hydrates: Mn3F8 · 12H2O and AgMnF4 · 4H2O

Single crystals of fluoride hydrates Mn₃F₈ · 12 H₂O and AgMnF₄ · 4 H₂O have been prepared and characterized by X-ray methods. Mn₃F₈ · 12 H₂O crystallizes in the space group P1 (a = 623.0(3), b = 896.7(4), c = 931.8(4) pm, α = 110.07(2)°, β = 103.18(2)°, γ = 107.54(2)°, Z = 1); AgMnF₄ · 4 H₂O crystallizes in the space group P2₁/m (a = 700.9(2), b = 726.1(1), c = 749.4(3) pm, β = 107.17(3)°, Z = 2). Both structures contain Jahn-Teller-distorted [Mn(H₂O)₂F₄]^? anions as well as crystal water molecules and exhibit a complex hydrogen bond network between anions and cations, i. e. [Mn(H₂O)₆]²⁺ for the first and a polymeric [Ag(H₂O)₂]^? cation for the second compound.     

Die Kristallstrukturen von K8Ta6O19 · 16H2O und K7NaTa6O19 · 14H2O

The Crystal Structures of K₈Ta₆O₁₉ · 16H₂O and K₇NaTa₆O₁₉ · 14H₂O By alkaline digestion of Ta₂O₅ with p.a. KOH transparent single crystals of the composition K₈Ta₆O₁₉ · 16H₂O are formed. When technical grade KOH is used, the same kind of synthesis yields crystals of the composition K₇NaTa₆O₁₉ · 14H₂O. The latter compound has been given the formula K₈Ta₆O₁₉ · 14H₂O until now. In both cases the isopolyoxoanion [Ta₆O₁₉]⁸ consists of six TaO₆-octahedra connected by edge sharing. This means that the heavy atom partial structure found by Lindquist et al. is confirmed. Additionally the complete structures including the atomic positions of the oxygen atoms of the polyanions as well as those of the cations and crystal water molecules (without hydrogen positions) are determined.     

Synthesis and Crystal Structure of Lithium Tetrametaphosphimate Tetrahydrate Li4(PO2NH)4 · 4 H2O

Single crystals of Li₄(PO₂NH)₄ · 4 H₂O were obtained by dissolving LiOH and H₄(PO₂NH)₄ · 2 H₂O in water and subsequent precipitation with acetone and ethanol followed by slow evaporation of the solvents. The structure of Li₄(PO₂NH)₄ · 4 H₂O was solved by single‐crystal X‐ray methods ( (No. 2), a = 489.2(2), b = 853.2(2), c = 880.5(2) pm, α = 101.71(3), β = 102.39(3), γ = 94.88(3)°, Z = 1). The structure is composed of LiO₄ tetrahedra and (PO₂NH)₄^4? ions. The P₄N₄ rings of the anions exhibit a slightly distorted chair–1 conformation, which is supported by IR data and has been described by torsion angles, displacement asymmetry parameters and puckering parameters. Via Li⁺ ions and hydrogen bonds, the tetrametaphosphimate anions are connected forming a three‐dimensional network.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Oxalato‐ und Quadratato‐Komplexe hochkoordinierter Metallionen: Die Raumnetzstrukturen von La2(C2O4)(C4O4)2(H2O)8 · 2,5 H2O und K[Bi(C2O4)2] · 5 H2O

Oxalato‐ and Squarato‐Bridged Threedimensional Networks: The Crystal Structures of La₂(C₂O₄)(C₄O₄)₂(H₂O)₈ · 2.5 H₂O and K[Bi(C₂O₄)₂] · 5 H₂O The title compounds have been formed by hydrolysis of amino‐ and thioderivatives of squaric acid in the presence of La^III and Bi^III ions. Both compounds are threedimensional coordination polymers in the solid state, as shown by single crystal X‐ray crystallography. In La₂(C₂O₄)(C₄O₄)₂(H₂O)₈ · 2.5 H₂O oxalato‐bridged pairs of LaO₉ polyhedra are connected with identical neighbouring polyhedra by squarate ions. In K[Bi(C₂O₄)₂] · 5 H₂O each Bi atom is fourfold linked to other Bi atoms by the oxalate ions. The resulting 3D network shows a diamond‐like topology with square‐shaped channels. In both structures the channels are partially filled by water molecules.     

[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O,ein gemischtes Halogenid-Hydrat mit anionischen Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2−

[Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2? [Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl₃ and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; V_m = 573.9(4) cm³mol^?1; R = 0.060; R_w = 0.038) is the connection of two anions [Re₃(μ-Cl)₃Br₇(H₂O)₂]^? via a water molecule to dimers, {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2?. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb⁺ cations and crystal water.