Hydrothermal synthesis of three-dimensional open-framework beryllium phosphites with 3,4-connected networks

Two new beryllium phosphites, H₂en·Be₃(HPO₃)₄ (1) and H₂pda·Be₃(HPO₃)₄ (2), have been synthesized under hydrothermal conditions. Single-crystal structural analyses reveal that both compounds have three-dimensional inorganic frameworks constructed from strictly alternating BeO₄ tetrahedra and HPO₃ pseudo pyramids. The structure of compound 1 can be described as a pillared layered structure with 12-ring channels. The structure of compound 2 has an interesting sqp topology if Be₃(HPO₃)₄ clusters are regarded as 5-connected nodes in the network.     

Solvent-free synthesis of new metal phosphites with double-layered,pillared-layered,and framework structures

Three new metal phosphites, formulated as (H₃O)₂·Mn₂(HPO₃)₃ (1), Co(bpy) (H₂O) (HPO₃) (2), and H₂tmpda·Zn₃(HPO₃)₄ (3), have been synthesized under solvent-free conditions, where bpy = 4,4′-bipyridine, and tmpda = N,N,N′,N′-tetramethyl-1,3-propanediamine. Compound 1 has a double-layered structure with a thickness of 5.68 Å. Compound 2 has an inorganic-organic hybrid framework with cobalt phosphite layers pillared by bpy ligands. Compound 3 has a three-dimensional open-framework structure containing 8-ring channels. The temperature dependence of the magnetic susceptibility of compounds 1 and 2 were also investigated.     

Hydrothermal Syntheses, Crystal Structure and Thermal Behavior of [(CH_3)_2NH_2]_2[B_5O_6(OH)_4]_2·[HCON(CH_3)_2] and [NH_3CH_2CH_2NH_3]_2·[B_(14)O_(20)(OH)_6]

Two novel organic base templated nonmetal borates [(CH₃)₂NH₂]₂[B₅O₆(OH)₄]₂·[HCON(CH₃)₂] ( ? ) and [NH₃CH₂CH₂NH₃]₂[B₁₄O₂₀(OH)₆] ( II ) have been synthesized under hydrothermal conditions, and characterized by elemental analyses, FT‐IR spectroscopy, X‐ray diffraction, and TG‐DTA. Their crystal structures were determined from single crystal X‐ray diffraction. The crystal structure of compound I is characterized by forming a 3D supramolecular structure with large channels along axes b and c through O? H···O hydrogen‐bonding among the [B₅O₆(OH)₄]^? anions. The crystal structure of compound II is characterized by forming a 3D supramolecular structure with large channels along axis a and direction [111] through O? H···O hydrogen‐bonding among the [B₁₄O₂₀(OH)₆]^4? anions. The templating organic amine cations in I and II are both obtained through in situ hydrothermal reactions, and are both located in the channels of the 3D supramolecular structure, respectively. Their thermal behavior has been also investigated.     

IR spectra and thermal decomposition/dehydration of double complex salts of lanthanum(III) sulphate complex anions with several cobalt(III) ammine complex cations

Double complex salts of lanthanum(III) sulphate complex anions with several cobalt(III) ammine complex cations, [Co(NH₃)₆][La(SO₄)₃]·H₂O (1), (NH₄)₃[Co(NH₃)₅ H₂O]-[La(SO₄)₃]₂·2H₂O (2), and (NH₄)₃[Co(NH₃)₄(H₂O)₂][La(SO₄)₃]₂·2H₂O (3), were prepared by the addition of hexaamminecobalt(III), pentaammineaquacobalt(III), and cis- tetra-amminediaquacobalt(III) complexes to the solution containing lanthanum(III) ion and excess ammonium sulphate. The IR spectra of sulphate groups of these double complex salts were much more complicated than those of the almost free sulphate groups such as (NH₄)₂SO₄ and [Co(NH₃)₆]₂(SO₄)₃·5H₂O. Furthermore, values of activation energy in the dehydration process of 1, 2 and 3 were estimated using modified Doyle's and Wiedemann's method. They were 95.6 ± 4.3, 157.1 ± 15.5 and 163.2 ± 20.8 kJ mol^?1, respectively. Here, one molecule water is released per molecule of 1, 2 and 3.     

(C5H6N)4[Be6(HPO3)8]·H2O: A low-density open-framework beryllium phosphite with multidirectional 12-ring channels

Employing the common pyridine (=py) solvent as the source of structure-directing agents (SDAs), a novel three-dimensional open-framework beryllium phosphite (Hpy)₄[Be₆(HPO₃)₈]·H₂O (1), has been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. It crystallizes in the orthorhombic system, space group Pbca (No. 61), a = 20.0034(4) Å, b = 20.2188(4) Å, c = 20.9731(3) Å, V = 8482.5(3) Å³, and Z = 8. The alternating connection of BeO₄ tetrahedra and HPO₃ pseudopyramids give rise to a (3, 4)-connected network with multidirectional intersecting 12-ring channels. The compound possesses a low density and a new {4.8.10}{4².6.8.10.12}{4².6}₃{4².8.10².12}{4³.6².8} topology.     

A novel chain-like molybdenum phosphate: hydrothermal synthesis,crystal structure and characterization of [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]-Na5[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O

A novel organic/inorganic hybrid molybdenum phosphate, [NH₃(CH₂CH₂)₂NH₃]₃[NH₃(CH₂CH₂)₂NH₂]Na₅-[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂·4H₂O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃] units bonded together with NaO₆ octahedra, forming dimers. Further, these dimers connect with each other through four Na⁺ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.     

Darstellung,Kristallstruktur, thermischer Abbau und Schwingungsspektren von [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O

Preparation, Crystal Structure, Thermal Decomposition, and Vibrational Spectra of [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O is a suitable compound for the quantitative determination of beryllium. It can be obtained by reaction of aqueous solutions of carbonatoberyllate with [Co(NH₃)₆]Cl₃. The crystal structure (trigonal‐rhombohedral, R3c (Nr. 161), a = 1071,6(1) pm, c = 5549,4(9) pm, V_EZ = 5519(1) · 10⁶ pm³, Z = 6, R1(I ≥ 2σ(I)) = 0,037, wR2(I ≥ 2σ(I)) = 0,094) contains [Co(NH₃)₆]³⁺‐ and [Be₄O(CO₃)₆]^6–‐ions, which are directly hydrogen bonded as well as with water molecules. The complex cations and anions occupy the positions of a distorted anti‐CaF₂‐type. The thermal decomposition, IR and Raman spectra are presented and discussed.     

Self-assembly of reduced molybdophosphate-based supramolecular architectures and the study of their magnetic properties

Reduced molybdophosphate-based supramolecular compounds, such as (4,4′-H₂bipy)[Co(H₂O)₂]₂[Co(H₂PO₄)₂(HPO₄)₄(PO₄)₂(MoO₂)₁₂(OH)₆] · 17H₂O (1), [Co(2,2′-bipy)₂(H₂O)]₄[Co(H₂O)₂][Co(HPO₄)₆(PO₄)₂(MoO₂)₁₂(OH)₆] · 2H₂O (2), and [Co(2,2′-bipy)₂(H₂O)]₄[Co(H₂PO₄)(H₂O)₂]₂[Co(HPO₄)₆(PO₄)₂(MoO₂)₁₂(OH)₆] · 8H₂O (3) (4,4′-bipy=4,4′-bipyridine, 2,2′-bipy=2,2′-bipyridine), have been synthesized under hydrothermal conditions and characterized. Compound 1 exhibits a three-dimensional supramolecular twofold interpenetrating architecture built up of one-dimensional [P₄Mo₆]-based infinite covalent chains and free 4,4′-bipy molecules. Compound 2 also shows a three-dimensional supramolecular network constructed from one-dimensional covalent [P₄Mo₆]-based chains. Unlike compounds 1 and 2, compound 3 exhibits an interesting three-dimensional ‘honeycomb-like’ supramolecular network constructed by the stacking of [Co(2,2′-bipy)₂(H₂O)] units with one-dimensional channels, in which the [P₄Mo₆]-based polyoxometalate chains are located. The magnetic properties of compounds 2 and 3 are reported. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Structural and spectroscopic characterization of the dirhenium acetamidate products resulting from the hydrolysis of acetonitrile

Unsaturated molecules such as nitriles are activated upon coordination to a dirhenium core. Acetonitrile is hydrolyzed in the presence of water to produce coordinated bridging acetamidate ligands as demonstrated by the reaction of [N(C₄H₉)₄]₂[Re₂Cl₈] with CH₃CN and water in ethanol to form the acetamidate complexes, [N(C₄H₉)₄][Re₂Cl₅(μ-CH₃C(O)NH)(μ-CH₃C(OH)N)]·3CH₂Cl₂ [I] and Re₂Cl₄(μ-CH₃C(O)NH)(μ-dppm)₂·4 CH₂Cl₂/0.833 EtOH [II]. Compound II is formed when I is reduced upon coordination of bis(diphenylphosphino)methane (dppm). Compounds I and II were characterized using X-ray crystallography and a variety of other spectroscopic methods.     

具有三维交叉孔道的新型亚磷酸锌的合成与结构

本文报道了一种新型三维亚磷酸锌[HO(CH₂)₂NH₃]₂•[Zn₃(HPO₃)₄]的合成和晶体结构。在它的结构中，ZnO₄和HPO₃严格按照顶点连接的方式交替相连。骨架结构存在两个沿着不同方向无限延伸的由ZnO₄和HPO₃组成的四元环链，在[0 1 0]、[0 4 15]和[0 -4 15]三个方向形成了三个交叉8元环孔道，有机胺阳离子起着平衡电荷和稳定骨架的结构。它的晶体数据为：[HO(CH₂)₂NH₃]₂•[Zn₃(HPO₃)₄],M=640.21, 正交晶系, Fdd2空间群, a=2.8528, b=0.8426, c=1.6159nm, Z=8, V=3.884nm³, R₁=0.0219, wR₂=0.0544。     

[Ni(C6N2H14)2][Zn4(H2O)(HPO3)5]: A new open-framework zinc phosphite with intersecting 8-, 12- and 16-ring channels

A new three-dimensional (3-D) zinc phosphite with Zn/P ratio of 4/5, [Ni(C₆N₂H₁₄)₂][Zn₄(H₂O)(HPO₃)₅] (1), has been prepared by using self-assembled nickel complexes as the structure-directing agents. Its structure is built up from strict alternation of ZnO₄ tetrahedra and HPO₃ pseudo-pyramids, resulting in an open framework with multi-directional intersecting 8-, 12- and 16-ring channels. The unique nickel complexes Ni(DACH)₂ (DACH=1,2-diaminocyclohexane) only involving the cis-DACH acting as ligands are self-assembled under hydrothermal conditions, and act as the structure-directing agents (SDAs) to direct the formation of compound 1. Nickel complexes reside in the channels in a manner that the hydrophobic ends of the cis-DACH molecules exclusively protrude into the 16-ring pores and the amino groups closely interact with the charged inorganic framework through weak H-bonds. The interesting arrangements of nickel complexes imply a feasible approach to the design and synthesis of extra-large pore materials.     

Supramolecular compounds of indium sulfates with nitrogen-containing cations

Compounds with a general formula [Cat][In(H₂O) _n (SO₄)₂] _x · mH₂O (where Cat = C(NH₂)₃, H(2,2′-Bipy), H₂(4,4′-Bipy), H₂[Py(CH₂)₃Py], and H₃N(CH₂)₆NH₃) were synthesized and identified from the elemental analysis, IR, and thermogravimetric analysis data. X-ray diffraction analysis of crystalline [C(NH₂)₃][In(H₂O)₂(SO₄)₂] complex showed that the polymer chains of In aquasulfate form ensembles with guanidinium ions. The structure of [H₂(4,4′-Bipy)][In₂(H₂O)₆(SO₄)₄] · 2H₂O consists of the dimeric anions of indium sulfate. The coordination sphere of In includes three O atoms of three SO₄ groups and three O atoms of water molecules. The dimers are united into framework by diprotonated Bipy cations.     

Supramolecularly assembled water layers stabilized by sebacic anions in complexes of Zn(II) and Co(II)

Two three-dimensional supramolecular water architectures, [Zn(phen)₃]₂·[Zn(C₁₀H₁₆O₄)·(H₂O)₃]·(C₁₀H₁₆O₄)₂·20H₂O (1) and [Co(phen)₃]₂·[Co(H₂O)₆]·(C₁₀H₁₆O₄)₃·30H₂O (2) [phen = 1,10-Phenanthroline, C₁₀H₁₆O₄ = sebacic dianion], have been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffractions. The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions. The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.     

A series of new organic–inorganic compounds templated by the [SiW12O40]4− polyanion

Two couples of new compounds templated by the polyanion [SiW₁₂O₄₀]^4?,[Hbix][Cu^I(bix)]₃[SiW₁₂O₄₀]·4H₂O (1) and [Cu^II(H₂O)(Hbix)₂(bix)]₂[Cu^II(H₂O)₂(Hbix)₂(bix)][SiW₁₂O₄₀]₃·4H₂O (2) (bix = 1,4-Bis(imidazol-1-ylmethyl)benzene), [Cu^I(bbi)]₄[SiW₁₂O₄₀]·2H₂O (3) and [Cu^II(bbi₂)]₂[SiW₁₂O₄₀] (4) (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) were hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses and single X-ray diffraction. Compounds 1 and 2 were synthesized from the same reactants but exhibited distinct structures which could be ascribed to the different ratios of the reactant bix to Cu^II. In compound 1, the higher ratio of bix results in the transformation of the Cu^II to Cu^I, the [SiW₁₂O₄₀]^4? templates direct the Cu^I–bix coordination polymers to form a 3D supramolecular framework with grid-like channels along two directions. The [SiW₁₂O₄₀]^4? templates in compound 2 locate in the voids of the 3D supramolecular network constructed by Cu^II–bix coordination polymers, which exhibits the interdigitation fashion in both the formation of the 2D layer and the 3D framework. Compounds 3 and 4 were synthesized similar to 1 and 2, except for the change of bix to bbi. In compound 3, the Cu^I–bbi polymers form a supramolecular metal–organic host framework with rhombic channels in which the SiW₁₂ templates reside. Compound 4 shows a framework with hexagonal channels constructed by Cu^II–bbi coordination polymers which accommodated the SiW₁₂ templates.     

Cyano-bridged complexes based on re tetrahedral cluster anions, Ni2+ cations, and polydentate amines

Interaction of the tetrahedral chalcocyanide cluster anionic complexes of Re, K₄[Re₄Q₄(CN)₁₂] (Q=S, Se, Te), with Ni²⁺ cationic complexes with polydentate amines, such as ethylenediamine (En), diethylenetriamine (Dien), or triethylenetetraamine (Trien) was used to synthesize six novel complexes: [Ni(NH₃)₄(En)][{Ni(NH₃)(En)₂}Re₄Te₄(CN)₁₂] · 2H₂O, [{Ni(En)₂}₂Re₄Se₄(CN)₁₂] · 3.5H₂O, [Ni(NH₃)₃(Dien)]₂[Re₄Se₄(CN)₁₂] · 5.5H₂O, [{Ni(NH₃)₂(Dien)}₂Re₄Te₄(CN)₁₂] · 2.5H₂O. [Ni(NH₃)₂(Trien)][{Ni(NH₃)(Trien)}Re₄Se₄(CN)₁₂] · 2.5H₂O, [{Ni(Trien)}₂Re₄S₄(CN)₁₂] · 3H₂O. The complexes were studied by single-crystal X-ray diffraction analysis.     

Novel inorganic ionic compounds based on Re6 chalcocyanide cluster complexes: synthesis and crystal structures of [CuNH3(trien)]2[Re6S8(CN)6] · 7H2O, [CuNH3(trien)]2[Re6Se8(CN)6] and [CuNH3(trien)]2[Re6Te8(CN)6] · H2O

Three new octahedral rhenium chalcocyanide cluster compounds [CuNH₃(trien)]₂[Re₆S₈(CN)₆] · 7H₂O (1), [CuNH₃(trien)]₂[Re₆Se₈(CN)₆] (2) and [CuNH₃(trien)]₂[Re₆Te₈(CN)₆] · H₂O (3) exhibiting ionic structures have been obtained by the diffusion of an ammonia solution of KCs₃[Re₆S₈(CN)₆] (for 1), K₄[Re₆Se₈(CN)₆] · 3.5H₂O (for 2) or Cs₄[Re₆Te₈(CN)₆] · 2H₂O (for 3) into a glycerol solution of CuCl₂ · 2H₂O in the presence of trien (trien=triethylenetetramine). The compounds have been characterized by single-crystal X-ray diffraction. All three compounds contain a cationic complex [CuNH₃(trien)]²⁺ which was not described previously.     

Structure and spectral characteristics of (NH4)2[Re2(HPO4)4 · 2H2O]

The compound (NH₄)₂[Re₂(HPO₄)₄ · 2H₂O] has been synthesized and characterized by electronic and vibrational spectroscopy. The molecular structure has been determined by X-ray diffraction (MoK _α radiation, λ = 0.71073 Å). The (NH₄)₂[Re₂(HPO₄)₄ · 2H₂O] coordination units form centrosymmetrical binuclear ordering with each metal atom being coordinated in a distorted octahedron incorporating one rhenium atom, one oxygen atom of the water molecule, and four phosphate oxygen atoms in the equatorial plane. The rhenium-rhenium bond length (2.2207 Å) corresponds to a quadruple bond between the atoms. The [Re₂(HPO₄)₄ · 2H₂O]^2- complex anions in the crystal are associated through strong hydrogen bonds formed by the phosphate O-H···O groups. The stability of dirhenium(III) tetra-μ-phosphates in aqueous solutions is considered.     

Synthesis and characterization of two new inorganic–organic hybrid cobalt molybdenum(V) phosphates

Two new inorganic–organic hybrid cobalt phosphomolybdates (Hdien)₂[Co(dien)]₂[Co(dien)(H₂O)]₂[CoMo₁₂O₂₄(HPO₄)₂(H₂PO₄)₂(PO₄)₄(OH)₆]?···?5H₂O (1) and (H₂dien)₂[Co(dien)]₂[Co(H₂O)₂]₂[CoMo₁₂O₂₄(HPO₄)₄(PO₄)₄(OH)₆]?···?7H₂O (2) (dien?=?diethylenetriamine), involving molybdenum in the V oxidation state and covalently bonded transition metal complexes, have been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) chain framework, in which dien molecules adopt two kinds of coordination modes. Compound 2 shows a two-dimensional (2D) layer framework with three types of unusual tunnels. To the best of our knowledge, it is the first time [Co(dien)] units are directly incorporated into 1D and 2D skeletons of reduced molybdenum phosphates. The electrochemical properties of the two compounds were studied via the method of bulk-modified carbon paste electrodes. Furthermore, the magnetic properties of compound 2 are reported.     

Assembly of 3‐D Network Structures Containing Oxydiacetate and CeIII or CeIV

Reaction of CeCl₃·7H₂O with Na₂(oda) (oda = O(CH₂CO₂)₂^2— oxydiacetate) in a 2:3 ratio gives the neutral cerium(III) complex [Ce₂(oda)₃(H₂O)₃]·9H₂O ( 1 ). Treatment of a 1:3 mixture of CeCl₃·7H₂O and H₂oda in water with 4 molar equivalents of NaOH also gives 1 but, with a larger excess of NaOH, the tri‐sodium salt Na₃[Ce(oda)₃]·9H₂O ( 2 ) is isolated. Formation of a tri‐ammonium analogue of 2 can be achieved by neutralisation of an aqueous solution of CeCl₃·7H₂O and H₂(oda) in a 1:3 ratio by NH₄OH, giving (NH₄)₃[Ce(oda)₃]·7H₂O ( 3 ). Use of the cerium(IV) reagent (NH₄)₂[Ce(NO₃)₆] with Na₂(oda) results in reduction to cerium(III) under ambient conditions and isolation of 1 . However, in the absence of light this reaction yields crystals of the novel cerium(IV) heterobimetallic [Ce(oda)₃Na₄(NO₃)₂] ( 4 ). Each of these complexes exhibit a 3‐D network structure having a common nine‐coordinate [Ce(oda)₃]^n— (n = 2 or 3) subunit, irrespective of the oxidation state of cerium. In 1 , six [Ce(oda)₃]^3— anions are connected, through bridging bidentate carboxylates, to a second Ce³⁺ site further coordinated by three water molecules. In contrast, the ammonium salt 2 , displays isolated [Ce(oda)₃]^3— anions, devoid of further carboxylate bonding, but enmeshed within a network of hydrogen‐bonded NH₄⁺ cations and water molecules. The remarkable structure of 4 consists of infinite 2‐D sheets of [Na₂(NO₃)]⁺ pillared by [Ce(oda)₃]^2— units, the connectivity arising by multidentate nitrate and carboxylate bridging.     

Hydrothermal synthesis and structural determination of a three-dimensional microporous iron(III)phosphate: [H3N(CH2)4NH3]3[Fe8(HPO4)12(PO4)2(H2O)6]

A new microporous iron (III) phosphate, [H₃N(CH₂)₄NH₃]₃[Fe₈(HPO₄)₁₂(PO₄)₂(H₂O)₆], has been prepared using low temperature hydrothermal methods and characterized by single-crystal X-ray diffraction, EDAX, infrared spectroscopy, thermogravimetric analysis and bond valence sums. The title compound crystallizes as light pink hexagonal-shaped tabs in the centrosymmetric hexagonal space group 3¯ (No.147) with a = b = 13.495(2) Å, c = 9.396(2) Å, V = 1481.9(4) ų and Z = 4 with R/R_w = 0.044/0.048. The compound exhibits a complicated three-dimensional microporous structure with quaternary ammonium ions acting as a template for the framework. It is similar to previously reported [HN(CH₂CH₂)₃NH]₃[Fe₈(HPO₄)₁₂(PO₄)₂(H₂O)₆].