Alkalimetalltetraethinylozincate und ‐cadmate AI2M(C2H)4 (AI = Na — Cs,M = Zn,Cd): Synthese,Kristallstruktur und spektroskopische Eigenschaften

Alkali Metal Tetraethinylozincates and ‐cadmates A^I₂M(C₂H)₄ (A^I = Na — Cs, M = Zn, Cd): Synthesis, Crystal Structures, and Spectroscopic Properties By reaction of A^IC₂H (A^I = Na — Cs) with divalent zinc and cadmium salts in liquid ammonia the alkali metal tetraethinylozincates and ‐cadmates A^I₂M(C₂H)₄ (M = Zn, Cd) were accessible as polycrystalline powders. While Na₂M(C₂H)₄ is amorphous to X‐rays and the crystal structure of Cs₂Zn(C₂H)₄ could not be solved up to now, the remaining compounds are isotypic to the already known crystal structures of the potassium compounds, as was deduced from powder diffraction with X‐rays and synchrotron radiation. They crystallise in the tetragonal space group I4₁a, contain [M(C₂H)₄]^2— tetrahedra and show structural relationships to the scheelit and anatas structure types. Raman spectroscopic investigations confirm the existence of tetrahedral fragments with C‐C triple bonds in the alkali as well as in the amorphous alkaline earth metal compounds A^IIM(C₂H)₄ (A^II = Mg — Ba, M = Zn, Cd).     

Preparation and Crystal Structure Analyses of Compounds in the Systems HgO/MXO4/H2O (M = Co,Zn, Cd; X = S,Se)

During phase formation experiments under hydrothermal conditions (250 °C, 5d) in the systems HgO/MXO₄/H₂O (M = Co, Zn, Cd; X = S, Se), single crystals of the mercuric compounds (CdSO₄)₂(HgO)₂H₂O (I), (CdSeO₄)₂(HgO)₂H₂O (II), (CdSeO₄)Hg(OH)₂ (III), (CoSO₄)₂(HgO)₂H₂O (IV), (ZnSO₄)₂(HgO)₂H₂O (V), (ZnSeO₄)₂(HgO)₂H₂O (VI), and the mixed‐valent (ZnSe^IVO₃)(ZnSe^VIO₄)Hg^I₂(OH)₂ (VII) were obtained. The crystal structure determinations from X‐ray diffraction data revealed four unique structure types for these compounds. I and II crystallise isotypically in space group P2/n (a ≈ 7.85, b ≈ 6.28, c ≈ 10.5Å, β ≈ 102°), compound III crystallises in space group C2/m (a = 10.540(2), b = 9.0120(8), c = 6.1330(12)Å, β = 100.45(3)°), and the isotypic compounds IV, V and VI crystallise in space group Pbcm (a ≈ 6.15, b ≈ 11.3, c ≈ 13.1Å). Common with these three structure types are distorted octahedral [MO₆] and tetrahedral XO₄ building units which are organised in a layered assembly. Within the layers H bonding of OH groups or H₂O molecules of the [MO₆] octahedra leads to an additional stabilisation. Adjacent layers are separated by mercury atoms which are linearly bonded to two O atoms at short distances, forming either interconnecting [O‐Hg‐O] units which are part of [O‐Hg‐O]_∞ zig‐zag chains, or single [HO‐Hg‐OH] units (realised in compound III). VII is the only compound with mercury in oxidation state +1. It crystallises in space group C2/m (a = 17.342(3), b = 6.1939(10), c = 4.4713(8)Å, β = 90.154(3)°) and is made up of Hg₂²⁺ dumbbells, [ZnO₄(OH)₂] octahedra, and statistically distributed Se^VIO₄ and Se^IVO₃ groups as the main building units.     

Hydrothermal Synthesis and Crystal Structures of Na2Be3(SeO3)4·H2O and Cs2[Mg(H2O)6]3(SeO3)4

The selenites, Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄, were synthesized under hydrothermal conditions. The crystal structures of Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ were determined by single‐crystal X‐ray diffractions. Na₂Be₃(SeO₃)₄ · H₂O crystallizes in the triclinic space group P1 (no. 2) with unit cell parameters a = 4.8493(9), b = 12.013(2), c = 12.077(2) Å, and Z = 2, whereas Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ crystallizes in the monoclinic space group C2/m (no. 12) with lattice cell parameters a = 12.596(6), b = 7.297(4), c = 16.914(8) Å, and Z = 2. Na₂Be₃(SeO₃)₄ · H₂O features a three‐dimensional open framework structure formed by BeO₄ tetrahedra and SeO₃ trigonal pyramids. Na cations and H₂O molecules are located in different tunnels. Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ has a structure composed of isolated [Mg(H₂O)₆] octahedra and SeO₃ trigonal pyramids interacted by hydrogen bonds, and Cs cations are resided in‐between. Both compounds were characterized by thermogravimetric analysis and FT‐IR spectroscopy.     

Crystal Structure of a Cadmium Iodate Monohydrate: Cd(IO3)2·H2O

Single crystals of Cd(IO₃)₂·H₂O are obtained by slow evaporation of aqueous solutions of CdCl₂ and KIO₃. This compound crystallizes in the triclinic space group P1¯ [a = 7.119(2), b = 7.952(2), c = 6.646(2)Å, α = 102.17(2)°, β = 114.13(2)°, γ = 66.78(4)°]. The structure consists in Cd — (μ2‐O)₂ — Cd dimers with a metal — metal distance of 3.74Å. These dimers are connected through two iodate bridges resulting in layers parallel to the (010) plane. The 3D linkage is ensured by I1 — O1 long bonds (2.775Å).     

Das erste Hexaoxoselenat (VI) – Synthese und Charakterisierung von Na12(SeO6)(SeO4)3

The First Hexaoxoselenate(VI) – Synthesis and Characterization of Na₁₂(SeO₆)(SeO₄)₃ Pure Na₁₂(SeO₆)(SeO₄)₃ has been prepared by solid state reaction at 500 °C from a mixture of Na₂O and Na₂SeO₄ in silver crucibles. The crystal structure has been determined from single crystal data (Pnma, a = 1577.2(7), b = 781.7(3), c = 1475.5(7) pm, Z = 4, R1 = 0.030, wR2 = 0.058, 2480 observed reflections [I_o ≥ 2σ(I_o)]). Na₁₂(SeO₆)(SeO₄)₃ contains novel SeO₆^6– anions. There exists an unexpected topological relationship between the SeO₆Naⁱ₈Na^a₂Na^a_4/2 part of the structure and the MoCl₂ structure type (Mo₆Clⁱ₈Cl^a₂Cl^a_4/2). The crystal structure as determined is consistent with spectroscopic data (IR, Raman, ⁷⁷Se‐MAS‐NMR).     

Synthesis and Structure of K[Cd(O2N‐C6H4‐NNN‐C6H4‐NO2)3], an Anionic 1, 3‐Bis(4‐nitrophenyl)triazenido Complex of Cadmium

The reaction of cadmium acetate in methanol with 1, 3‐bis(4‐nitrophenyl)triazene in THF in the presence of KOH yields K[Cd(O₂NC₆H₄NNNC₆H₄NO₂)₃] in form of hexagonal prismatic, red crystals with the trigonal space group R3¯ and a = 12.229(2), c = 48.988(10) Å and Z = 6. In the anionic cadmium complexes, which are located along the threefold axis, the Cd atoms are coordinated in a trigonal prismatic arrangement by the atoms N(1) and N(3) of three triazenido ligands. The potassium cations are coordinated icosahedrally by oxygen atoms of each one nitro group of six neighbouring anionic complexes. The Cd‐N distances are 2.376(4) and 2.350(4) Å, and the K‐O distances are in the range of 2.833(6) to 3.365(6) Å.     

Synthesis and Structure of a New Vanadium(IV)‐Cadmium(II) Compound with the Nitrilotriacetate Ligand: {(NH4)2[(VIVO)2(μ2‐O)(nta)2Cd(H2O)2]·H2O}n

A polymeric V^IV‐Cd compound, {(NH₄)₂[(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]·H₂O}_n (H₃nta = nitrilotriacetic acid), has been prepared and characterized by single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group C2/c with a = 17.3760(2) Å, b = 8.0488(1) Å, c = 17.3380(2) Å, β = 107.9690(10)°, V = 2306.55(5) ų, Z = 4, and R₁ = 0.0303 for 1958 observed reflections. The structure exhibits a heterometallic three‐dimensional network formed by polymeric [(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]^2? anions.     

Synthesis,Crystal Structure,and Characterization of Na7Cu4(AsO4)5

Abstract

Sodium copper (II) arsenate Na₇Cu₄(AsO₄)₅ has been grown by conventional high-temperature, solid-state methods in molten-salt media. It was characterized by single crystal X-ray diffraction (XRD), thermal analysis (DTA–TGA), scanning electron microscopy (SEM), semiquantitative energy dispersive spectroscopy analysis (EDS), and vibrational spectroscopy. Na₇Cu₄(AsO₄)₅ exhibits a three-dimensional framework built up of CuO₅, CuO₄, and AsO₄ polyhedra, with intersecting channels in which the Na⁺ cations are located. The three-dimensional cohesion of the framework results from Cu–O–As bridges. CuO₅ and CuO₄ polyhedra are elongated due to the Jahn–Teller effect, whereas AsO₄ tetrahedra are almost regular. This new structural model is validated by the charge distribution (CD) analysis. The infrared and Raman spectra confirmed the presence of AsO₄ tetrahedra.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional tables and figures.]     

Hydrothermal Synthesis,Crystal Structure Determination,and Magnetic Properties of a New Calcium Iron Iridium Hydrogarnet Ca3(Ir2–xFex)(FeO4)2–x(O4H4)1+x with 0 ≤ x ≤ 1

The new calcium iron iridium hydrogarnet Ca₃(Ir_2–xFe_x)(FeO₄)_2–x(H₄O₄)_1+x (0 ≤ x ≤ 1) was obtained by hydrothermal synthesis under strongly oxidizing alkaline conditions. The compound adopts a garnet‐like crystal structure and crystallizes in the acentric cubic space group I4 3d (no. 220) with a = 12.5396(6) Å determined at T = 100 K for a crystal with a refined composition Ca₃(Ir_1.4Fe_0.6)(FeO₄)_1.4(O₄H₄)_1.6. Iridium and iron statistically occupy the octahedrally coordinated metal position, the two crystallographically independent tetrahedral sites are partially occupied by iron. Hydroxide groups are found to cluster as hydrogarnet defects, i.e. partially substituting oxide anions around the empty tetrahedral metal sites. The presence of hydroxide ions was confirmed by infrared spectroscopy and the hydrogen content was quantified by carrier gas hot extraction; the overall composition was verified by energy dispersive X‐ray spectroscopy. The structure model is supported by ⁵⁷Fe‐Mössbauer spectroscopic data evidencing different Fe sites and a magnetic ordering of the octahedral iron sublattice at room temperature. The thermal decomposition proceeds via three steps of water loss and results in Ca₂Fe₂O₅, Fe₂O₃ and Ir. Mössbauer and magnetization data suggest magnetic order at ambient temperature with complex magnetic interactions.     

新型杂多化合物[(CH3CH2)4N]4H3O· {Na[(HMo2O5)3(HPO4)(H2PO4)3]2}·(H2PO4)2·10H2O的水热合成与晶体结构

杂多化合物在催化、医药、材料及光化学等方面具有广泛的应用前景 [1～ 4 ] ,其中钼磷多金属氧酸盐具有优异的氧化催化性能 [5,6 ] .近年来合成的新奇结构的钼磷多金属氧酸盐中已测定结构的有含帽[7,8] 和非帽[9～ 12 ] 系列 .本文利用水热法合成了未见文献报道的结构新颖的夹心型磷钼多金属氧酸盐[( CH3CH2 ) 4N]4 H3O{Na[( HMo2 O5) 3( HPO4 ) ( H2 PO4 ) 3]2 }· ( H2 PO4 ) 2 · 1 0 H2 O,并测定了其晶体结构 .1　实验与晶体结构分析1 .1　仪器与试剂　元素 Na用美国原子吸收分光光度计测定 ;C,H和 N用 Perkin- Elmer 2 4 0…     

Synthesis,Crystal Structure and Photoluminescence Property of Zinc(II), Cadmium(II), and Lead(II) Complexes with Bidentate Ligand: 1‐(1‐Imidazolyl)‐4‐(imidazol‐1‐ylmethyl)benzene (IIMB)

Assembly of bidentate ligand 1‐(1‐imidazolyl)‐4‐(imidazol‐1‐ylmethyl)benzene (IIMB) with varied metal salts of Zn^II, Cd^II and Pb^II provide three new complexes, [Zn(IIMB)₂](ClO₄)₂·2H₂O ( 1 ), [Cd(IIMB)₂(SCN)₂] ( 2 ) and [Pb(IIMB)₂(SCN)](SCN) ( 3 ). Single crystal X‐ray diffraction studies revealed that complexes 1 and 2 display a similar one‐dimensional double stranded chain structure, while complex 3 is a slight distorted rhombohedral grid network with (4,4) topology. The results indicate that the coordination geometry of the metal ion and the counter anion have great impact on the structure of the complexes. In addition, the photoluminescence properties of ligand IIMB and complexes 1 – 3 were studied in the solid state at room temperature.     

The [Au(CH3SO3)4]– Anion in the Crystal Structures of M[Au(CH3SO3)4] (M = Li,Na, Rb)

The reactions of Au(OH)₃, M₂CO₃ (M = Li, Na, Rb), and methanesulfonic acid at elevated temperatures in sealed glass ampoules lead to single crystals of M[Au(CH₃SO₃)₄] (M = Li, Na, Rb). In the crystal structures of Li[Au(CH₃SO₃)₄] (tetragonal, I$\bar{4}$ , Z = 2,a = 938.64(2) pm, c = 917.01(3) pm, V = 807.93(4) ų) and Rb[Au(CH₃SO₃)₄] (tetragonal, P$\bar{4}$ 2₁c, Z = 2, a = 946.7(1) pm,c = 889.9(1) pm, V = 797.6(2) ų) the complex aurate anions are linked by the M⁺ ions in three dimensions. Contrastingly, in the structure of Na[Au(CH₃SO₃)₄] (triclinic, P$\bar{4}$ , Z = 1, a = 540.04(2) pm,b = 863.75(2) pm, c = 973.29(3) pm, α = 72.694(2)°, β = 75.605(2)°, γ = 77.687(2)°, V = 415.05(2) ų) the complex anions are connected into layers that are further connected by weak hydrogen bonds. The thermal decomposition of Li[Au(CH₃SO₃)₄] was monitored up to 500 °C and leads in a multi‐step process to elemental gold and Li₂SO₄.     

钴、镍-氨基三乙酸配位聚合物Na[M(nta)]·H2O(M=Co,Ni)的水热合成、结构与磁性

由有机配体同金属离子作用构建的配位聚合物具有与无机微孔晶体类似的空旷骨架结构,并在非线性光学材料、磁性材料、超导材料及催化等诸多方面具有潜在的应用前景[1～4].在配位聚合物的合成中,配体的种类不仅直接影响到聚合物的合成,而且还涉及到聚合物的结构维数[5～7].目前,用来构建这些配合物的有机配体大多数都带有相同的可配位基团,较少应用具有两种以上的配位基团的有机配体.本文采用同时含有氮和氧两种配位原子的多齿配体氨基三乙酸[8～12],在水热条件下分别以Co2+和Ni2+作为组装基元,通过自组装合成了具有三维骨架结构的Na[M(nta)]·H2O [M=Co(1),Ni(2)]配位聚合物,并进行了结构与磁性研究.     

Polymorphism of Anhydrous Cadmium Iodate Structure of ε‐Cd(IO3)2

The investigation of CdCl₂‐HIO₃ system, in aqueous and HNO₃ solutions, revealed that anhydrous cadmium iodate presents a marked polymorphism. No less than four new Cd(IO₃)₂polymorphs have been isolated and characterized, two of which showing second harmonic generation activity. Single crystals of ε‐Cd(IO₃)₂ are obtained by slowly evaporating, at 60 °C, a saturated solution of γ‐Cd(IO₃)₂ in 30 % nitric acid. This compound crystallizes in the orthorhombic space group Pca2₁ [a = 17.581(2), b = 5.495(2), c = 11.163(2) Å]. The basic structural unit can be described as the connection of two cadmium polyhedrons with a short metal – metal distance of 3.88Å. These units are further linked through two other iodate bridges resulting in layers parallel to the (100) plane. The 3D linkage is ensured by short bonds of the fourth iodate group.     

A 3D Metal‐organic Framework Containing [Cd(3‐CPOA)]n (3‐CPOA2– = 3‐Carboxyphenoxyacetato Dianion) Expanded by 4,4′‐Bipyridine

The hydrothermal reaction of Cd(NO₃) · 4H₂O with 4,4′‐bipyridine (bipy) and 3‐carboxyphenoxyacetatic acid (3‐H₂CPOA) afforded a 3D metal‐organic framework (MOF) [Cd(3‐CPOA)(bipy)]_n · 3.5nH₂O, which was characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and X‐ray diffraction. The single‐crystal structural analysis revealed that it has a Cds‐type topological network with 1D channels that contain encapsulated water molecular tapes.     

Synthesis and Crystal Structures of Two New Layered Manganese(II) Diphosphonates: Mn2[{(O3PCH2)2NHR}(H2O)F]·H2O

Two manganese phosphonates Mn₂[{(O₃PCH₂)₂NHR}(H₂O)F]·H₂O (R = ?C₆H₁₁ (1) , ?CH₂C₅H₄N (2) ) have been synthesized by hydrothermal reaction and characterized by single–crystal X–ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The two isomorphous compounds feature layered structures in ab plane, in which the tetramers comprised of two MnO₄F₂ and two MnO₅F polyhedra are cross–linked via phosphonate oxygen atoms to form Mn^II phosphonate layers. The organic groups of the ligands are orientated toward the interlayer space.     

Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.     

一种新颖的六帽Keggin型钼钒砷酸盐——(H3O)3[AsMo12O40(VO)6]·6H2O的水热合成和晶体结构

近年来,含有Keggin结构的杂多酸以其优异的结构可修饰性及其在催化、功能材料和医药等方面的潜在应用而引起人们广泛的研究兴趣.在这一领域中,众多过渡金属取代的Keggin型杂多化合物,尤其是含有钒和铝的多金属氧酸盐由于其独特的电磁特性及结构特点而倍受关注.但迄今为止,只有少数带帽Keggin型结构的杂多阴离子被报道.这些Keggin阴离子通常具有低的V/Mo.