(C4N3H15)[(BO2)2(GeO2)4]: the first organically templated 3D borogermanate showing 1D 12-rings, large channels, and a novel zeolite-type framework topology constructed from Ge8O24 and B2O7 cluster units

The first organically templated 3D borogermanate with a novel zeolite-type topology, (C4N3H15)[(BO2)2(GeO2)4] FJ-17, has been solvothermally synthesized and characterized by IR spectroscopy, powder X-ray diffraction (PXRD), TGA, and single-crystal X-ray diffraction. The compound crystallized in the monoclinic space group P2(1)/c with a = 6.967(1) A, b = 10.500(1) A, c = 20.501(1) A, beta = 90.500(3) degrees , V = 1499.68(8) A3, and Z = 4. The framework topology of this compound is the previously unknown topology with the vertex symbols 3.4.3.9.3.8(2) (vertex 1), 3.8.3.4.6(2).9(2) (vertex 2), 3.8(2).4.6(2).6(2).8 (vertex 3), 4.8.4.8.8(3).12 (vertex 4), 4.8.4.8.8(2).12 (vertex 5), and 3.8.4.6(2).6.8(2) (vertex 6). The structure is constructed from Ge8O24 and B2O7 clusters. The Ge8O24 cluster contains eight GeO4 tetrahedra that share vertices; the B2O7 unit is composed of two BO4 tetrahedra sharing a vertex. The cyclic Ge8O24 clusters connect to each other through vertices to form a 2D layer with 8,12-nets. The adjacent layers are further linked by the dimeric B2O7 cluster units, resulting in a 3D framework with 12- and 8-ring channels along the a and b axes, respectively. In addition, there is a unique B2GeO9 3-ring in the structure.     

Synthesis and crystal structure of a novel germanate: (NH4)4[(GeO2)3(GeO1.5F3)2].0.67H2O

The novel microporous germanate (NH4)4[(GeO2)3(GeO1.5F3)2].0.67H2O was prepared from an aqueous solution containing germanium dioxide, pyridine, hydrofluoric acid, and 2,6-diaminopyridine as a template. The solution was kept at 165 degrees C in a Teflon-lined autoclave for 4 days. Large crystals were produced and studied by X-ray powder diffraction, FTIR, thermal analysis, and elemental analysis. The structure was determined by single-crystal X-ray diffraction. The crystal is orthorhombic, space group Pbcn, with a = 7.0065(4) A, b = 11.7976(6) A, c = 19.5200(14) A, and Z = 4. The structure is a layered framework built up from GeO4 tetrahedral and GeO3F3 octahedral units. The polyhedral units are connected in such a way that they form a zeolite-like porous structure with three- and nine-membered rings. Half of the ammonium ions are located inside the nine-membered rings. The other half are above and below the three-membered rings. The connectivity of the germanium polyhedral units is interrupted along the c axis by ammonium ions and water molecules inserted between the layers.     

A three‐dimensional open‐framework zinc arsenate, (C4H12N2)2[Zn7(AsO4)6­(H2O)2]

The title compound, dipiperazinium heptazinc hexakis(arsen­ate) dihydrate, is built from vertex‐sharing AsO₄ tetrahedra, ZnO₄ tetrahedra and ZnO₅ trigonal bipyramids. The connectivity between these polyhedra give rise to an open framework with eight‐ring channels along the crystallographic [001] and [011] directions. The piperazinium cations are located within these channels.     

NC12H8(NH)2[Gd(N3C12H8)4] und [Gd(N3C12H8)3(N3C12H9)]·PhCN: Ein Beitrag zur Reaktivität und Kristallchemie homoleptischer Selten‐Erd‐Pyridylbenzimidazolate

NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] and [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN: A Contribution to the Reactivity and Crystal Chemistry of Homoleptic Pyridylbenzimidazolates of the Rare Earth Elements Transparent colourless crystals of the compound NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] were obtained by solvent‐free reaction of gadolinium metal with molten 2‐(2‐Pyridyl)‐benzimidazole. Transparent yellow crystals of the compound [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN were obtained by further reacting NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] with benzonitrile thermally. Both compounds exhibit homoleptic pure nitrogen coordinations of gadolinium, the PhCN ligand is not coordinating. Whilst NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] is salt like and consists of (NC₁₂H₈(NH)₂)⁺ and [Gd(N₃C₁₂H₈)₄]^— ions, [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN has a molecular structure of uncharged [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)] units.     

Replacement of Trimethylamine in Trimethylamine‐trispentafluoroethyl‐borane. Structures of [(C2F5)3BNMe3], [NMe4][(C2F5)3BOH], and K[(C2F5)3BCH2(CO)C6H5]

Trimethylamine‐tris(pentafluoroethyl)borane [(C₂F₅)₃BNMe₃] ( 1 ) reacts at 190 °C with water under displacement of the trimethylamine ligand to yield the hydroxy‐tris(pentafluoroethyl)borate [(C₂F₅)₃BOH]^? ( 2 ). In tributylamine 1 reacts with alkynes HC≡CR to form novel ethynyl‐tris(pentafluoroethyl)borate anions [(C₂F₅)₃BC≡CR]^? – R = C₆H₅ ( 3 ), C₆H₄CH₃ ( 4 ), Si(CH(CH₃)₂)₃ ( 5 ) – in moderate yields. Compound 3 adds water across the triple bond to form the novel anion [(C₂F₅)₃BCH₂(CO)C₆H₅]^? ( 6 ). The structures of [(C₂F₅)₃BNMe₃], [NMe₄][(C₂F₅)₃BOH] and K[(C₂F₅)₃BCH₂(CO)C₆H₅] have been determined by x‐ray crystallography.     

(C5H14N2)[Zn3(HPO4)4], a New 3D Open‐framework Zincophosphate Synthesized by Hydrothermal Reversible Transformation of (C5H14N2)[Zn2(HPO4)3]·H2O

In the system ZnO/H₃PO₄/H₂O/1,4‐diazacycloheptane (C₅H₁₂N₂), a new zincophosphate (ZnPO), (C₅H₁₄N₂)[Zn₃(HPO₄)₄] ( I ), was prepared by hydrothermal transformation (180 °C) of the known ZnPO hydrate (C₅H₁₄N₂)[Zn₂(HPO₄)₃]·H₂O ( II ). The thermally‐induced transformation is reversible; upon keeping the heterogeneous mixture of I and mother liquor at 80 °C recrystallization of II was observed. Single‐crystal X‐ray crystallography revealed that I possesses a unique three‐dimensional (3D) open‐framework structure built from corner‐linked ZnO₄ and HPO₄ tetrahedra. The (3,4)‐connected framework of I differs considerably from the 3D open‐framework ZnPO structure of II . Crystal data for I : Monoclinic system, space group Cc (No. 9) , Z = 4, a = 9.1389(6), b = 23.627(2), c = 9.3073(6) Å, β = 109.463(7)°, T = 298 K.     

New Mixed Ligand Organotellurium(IV) Compounds Containing Dithiocarbamates and the More Flexible Imidotetraphenyldithiodiphosphinates. The Crystal Structures of C8H8Te(S2CNEt2)[(SPPh2)2N] · H2O,C8H8Te(S2CNC5H10)[(SPPh2)2N], and C8H8Te(S2CNC4H8S)[(SPPh2)2N]

The synthesis of the following mixed ligand organotellurium(IV) compounds C₈H₈Te(S₂CNEt₂)[(SPPh₂)₂N] · H₂O ( 1 ), C₈H₈Te(S₂CNC₅H₁₀)[(SPPh₂)₂N] ( 2 ), C₈H₈Te(S₂CNC₄H₈O)[(SPPh₂)₂N] ( 3 ) and C₈H₈Te(S₂CNC₄H₈S)[(SPPh₂)₂N] ( 4 ) was achieved. They were characterized by IR, ¹H, ¹³C, ³¹P and ¹²⁵Te NMR, mass spectroscopy, and elemental analyses. The X‐ray crystal structures of 1 , 2 and 4 were determined. The both types of ligands display an asymmetrical chelating coordination mode on interaction with the tellurium atom. When these aniso‐bonded donor atoms are included in the coordination sphere, the tellurium atom exhibit an effective co‐ordination number of seven. The arrangement may be described as 1 : 2 : 2 : 2 coordination with a presumably stereoactive lone‐pair of electrons.     

Proton‐stabilized three‐dimensional anionic framework in H[Zn6O2(BO3)3]

A three‐dimensional anionic framework built up from [ZnO₄] tetra­hedra and planar [BO₃] groups, stabilized by H atoms, has been found for hydrogen zinc oxide borate, H[Zn₆O₂(BO₃)₃]. Boron and one of the borate O atoms are on 18e (2) positions. Triple units of [ZnO₄] tetra­hedra sharing a common oxygen vertex on a 12c (3) site and strong asymmetrical linear hydrogen bonds with the H atom [on a 12c (3) position] disordered over a twofold axis are specific structural features of this zincoborate. There is evidence that the reported Zn₄O(BO₃)₂ [Harrison, Gier & Stuky (1993). Angew. Chem. Int. Ed. Engl. 32 , 724–726] corresponds to this structure.     

C3N6H6(H3BO3)2的合成及晶体结构

以三聚氰胺和硼酸为原料在水溶液中反应合成出了一种新的BCN化合物先驱体C3N6H6(H3BO3)2。XRD表征结果表明三聚氰胺和硼酸的最佳配比为1∶3(物质的量比)。用单晶X-射线衍射分析法测定了该化合物的晶体结构。该化合物属单斜晶系,空间群为P21/C,晶胞参数为a=0.3597(7)nm,b=2.0105(4)nm,c=1.4112(3)nm,α=90,°β=92.07(3),°γ=90,°V=1.0199(3)nm3,Z=4,D c=1.627g.cm-3,μ(MoKα)=0.144mm-1,F(000)=520。晶体结构经全矩阵最小二乘法修正,最终可靠因子R1=0.0519,wR2=0.1361。该化合物是由C3N6H6分子和H3BO3分子通过氢键加合组装形成的三维超分子结构化合物。     

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.     

(Me2NH2)[(Ph3Sn)3(MoO4)2], ein Triorganozinnmolybdat mit Schichtstruktur

(Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂], a Triorganotin Molybdate with Layer Structure The reaction of [(Ph₃Sn)₂MoO₄] with (Me₂NH₂)Cl in an acetonitrile/water mixture leads to the formation of (Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂] ( 1 ). ( 1 ) crystallizes in the space group Pca2₁ with a = 1967.0(4), b = 1353.1(2) and c = 2176.6(5) pm. In the crystal structure of 1 Ph₃SnO₂ bipyramides and MoO₄ tetrahedra are linked by corner sharing to give a layer structure. Additionally the layers are connected by O···H···N hydrogen bridges between MoO₄ groups and [Me₂NH₂]⁺ ions to give a 3D network structure.     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

[C4N2H12]1.5[Zn2(PO4)(HPO4)2]·H2O晶体的合成与表征

由于在电学、磁学、光学、吸附、离子交换和催化等领域具有潜在的应用价值,具有开放骨架结构的金属磷酸盐的合成一直受到人们的广泛关注。在这些磷酸盐微孔化合物中,磷酸锌晶体是拓扑结构最为丰富的一种犤1犦。自从Stucky等犤2犦报道具有SOD、Li-ABW、FAU等已知结构磷酸锌的合成以来,已经有近百种具有0-D犤3,4犦,1-D犤5,6犦,2-D犤7～9犦,3-D犤10～13犦结构的磷酸锌被成功地合成出来。其中令人瞩目的是具有螺旋孔道的手性磷酸锌犤14犦以及具有二十四元环孔道的两种微孔磷酸锌化合物犤15,16犦的合成。这些化合物大多是采用水热技术以有…     

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2‐Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O,and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L₂Pd(N₃)₂ (L = PPh₃ ( 1 ), AsPh₃ ( 2 ), and 2‐chloropyridine ( 3 )), the dimeric [(AsPh₄)₂][Pd₂(N₃)₄Cl₂] ( 4 ), the homoleptic azido palladate [(PNP)₂][Pd(N₃)₄] ( 5 ) and the homoleptic azido platinates [(AsPh₄)₂][Pt(N₃)₄] · 2 H₂O ( 6 ) and [(AsPh₄)₂][Pt(N₃)₆] ( 7 ) were determined by X‐ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1 , 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd₂(N₃)₄Cl₂]^2– anions show end‐on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C_4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N₃)₆]^2– anions in 7 are centrosymmetric (idealized S₆ symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers.     

Strukturen von planaren und tetraedrischen TetrafulminatoMetallkomplexen: [N(C3H7)4]2 [Ni(CNO)4], [N(C3H7)4]2 [Pt(CNO)4] und [N(C3H7)4]2 [Zn(CNO)4]

Pseudohalogeno Metal Compounds. LXXVIII. Structures of Planar and Tetrahedral Tetrafulminato Metal Complexes: [N(C₃H₇)₄]₂ [Ni(CNO)₄], [N(C₃H₇)₄]₂ [Pt(CNO)₄], and [N(C₃H₇)₄]₂ [Zn(CNO)₄] The crystals contain the tetrafulminatometallates of an ideal square planar structure ([Ni(CNO)₄]^2–, [Pt(CNO)₄]^2–) with D_4h symmetry at the nickel and platinum atom and a tetrahedron ([Zn(CNO)₄]^2–) with perfect T_d symmetry at the zinc atom and with linear C≡N–O ligands. The metal carbon bonds (Ni–C: 187 pm, Pt–C: 200 pm, Zn–C: 201 pm) of the metal fulminates are very close to those of the corresponding cyano complexes. In the crystals the anions ([Ni(CNO)₄]^2–, [Pt(CNO)₄]^2–, [Zn(CNO)₄]^2–) are separated by the cations ([N(C₃H₇)₄]⁺) which explains the thermal stability of these compounds.     

Two new groups of homoleptic rare earth pyridylbenzimidazolates: (NC12H8(NH)2)[Ln(N3C12H8)4] with Ln = Y,Tb, Yb,and [Ln(N3C12H8)2(N3C12H9)2][Ln(N3C12H8)4](N3C12H9)2 with Ln = La,Sm, Eu

The compounds (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y, Tb, Yb, and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), with Ln = La, Sm, Eu, were obtained by reactions of the group 3 metals yttrium and lanthanum as well as the lanthanides europium, samarium, terbium, and ytterbium with 2-(2-pyridyl)-benzimidazole. The reactions were carried out in melts of the amine without any solvent and led to two new groups of homoleptic rare earth pyridylbenzimidazolates. The trivalent rare earth atoms have an eightfold nitrogen coordination of four chelating pyridylbenzimidazolates giving an ionic structure with either pyridylbenzimidazolium or [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)](+) counterions. With Y, Eu, Sm, and Yb, single crystals were obtained whereas the La- and Tb-containing compounds were identified by powder methods. The products were investigated by X-ray single crystal or powder diffraction and MIR and far-IR spectroscopy, and with DTA/TG regarding their thermal behavior. They are another good proof of the value of solid-state reaction methods for the formation of homoleptic pnicogenides of the lanthanides. Despite their difference in the chemical formula, both types (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y (1), Tb (2), Yb (3), and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), Ln = La (4), Sm (5), Eu (6), crystallize isotypic in the tetragonal space group I4(1). Crystal data for (1): T = 170(2) K, a = 1684.9(1) pm, c = 3735.0(3) pm, V = 10603.5(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.053, wR2 = 0.113. Crystal data for (3): T = 170(2) K, a = 1683.03(7) pm, c = 3724.3(2) pm, V = 10549.4(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.047, wR2 = 0.129. Crystal data for (5): T = 103(2) K, a = 1690.1(2) pm, c = 3759.5(4) pm, V = 10739(2) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.050, wR2 = 0.117. Crystal data for (6): T = 170(2) K, a = 1685.89(9) pm, c = 3760.0(3) pm, V = 10686.9(11) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.060, wR2 = 0.144.