Synthesis and Characterization of a Two‐Dimensional Zinc Phosphite,Zn3(tren)(HPO3)3·xH2O (x ≈ 0.5; tren = tris(2‐aminoethyl)amine)

A new zinc phosphite with the formula Zn₃(tren)(HPO₃)₃·xH₂O (x≈0.5) has been synthesized under hydrothermal conditions and characterized by FTIR, elemental analysis, powder X‐ray diffraction, single‐crystal X‐ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the triclinic system, space group (No.2), a = 10.1188(9) Å, b = 10.4194(9) Å, c = 10.5176(9) Å, α = 60.763(2)°, β = 70.6150(10)°, γ = 80.725(2)°, V = 912.77(14) ų, Z = 2. The structure consists of double crankshaft chains, which are linked by Zn‐O‐P bonds to form 8‐ and 12‐membered channels along the [100] direction. The claw‐like Zn‐centered complexes of Zn(N₄C₆H₁₈) as the supported templates, hang into the 12‐MR channels through Zn‐O‐P linkages with framework.     

A New Inorganic‐Organic Hybrid with Zinc Phosphate Layers Pillared by the 4, 4'‐Bipyridine Units

A new inorganic‐organic hybrid zinc phosphate with the formula Zn₂(4, 4'‐bipy)(HPO₄)₂ (4, 4'‐bipy = 4, 4'‐bipyridine) has been synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, FTIR, ICP analysis, elemental analysis, SEM, powder X‐ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the monoclinic system, space group P2₁/c (No.14), a = 10.4479(7), b = 8.1694(5), c = 8.9643(5) Å, β = 97.907(2), V = 757.86(8) ų, Z = 2. The structure consists of ZnO₃N and HPO₄ tetrahedra by corner‐sharing to generate neutral 4.8²‐net sheets, which are pillared through 4, 4'‐bipy ligands to form a 3‐D hybrid framework.     

Solvothermal Synthesis and Structural Characterization of an Organic‐Templated New Aluminogermanate with the GIS Topology

A new organic‐templated aluminogermanate [C₄H₁₂N][AlGe₃O₈] ( 1 ) has been prepared under solvothermal conditions by using 2‐propanol as solvent. The structure of the title compound was characterized by IR spectroscopic, elemental analysis, TG, single‐crystal X‐ray diffraction and powder X‐ray diffraction. Compound 1 crystallizes in the tetragonal space group I4₁/a, a = b = 10.7754(8) Å, c = 9.9116(14) Å, V = 1150.8(2) Å³, Z = 4. The structure of the title compound shows eight‐membered ring channels along a and b axes with a typical GIS topology, and – most importantly – the structure of the inorganic framework is retained when the organic amine is removed by calcination.     

Synthesis,Crystal Structures,and Characterization of Two 3d‐3d Heterometallic Coordination Frameworks: [ZnCo(Hcit)Cl] and [ZnCo(Hcit)Br]

Reactions between CoO, ZnCl₂ (or ZnBr₂), and molten citric acid (Hcit) led to the formation of two 3d‐3d heterometallic coordination frameworks: [ZnCo(Hcit)Cl] ( 1 ) and [ZnCo(Hcit)Br] ( 2 ). X‐ray structure analyses show that both compounds 1 and 2 crystallize in the monoclinic space group P2₁/n [ 1 : a = 5.8699(5) Å, b = 17.7963(13) Å, c = 9.2152(8) Å, β = 106.806(4) °, Z = 4, V = 921.53(13) Å³; 2 : a = 5.909(3) Å, b = 17.798(8) Å, c = 9.302(5) Å, β = 106.374(7) °, Z = 4, V = 938.6(8) Å³]. The structures of the two compounds are almost the same except for the terminal halogen ligand. Both of them are 3D frameworks based on citric acid bridging ligands and a 1D backbone chain built of corner‐shared {CoO₆} and {ZnO₃Cl} polyhedra. Photoluminescence and thermal stabilities of the compounds were studied.     

On the Crystal Structure of a Previously Unknown Anhydrous Zinc Hydroxide Sulfate

Anhydrous zinc hydroxide sulfates are promising precursors for the preparation of pigments and ZnO nanomaterials. The crystal structure of one such compound 5[Zn(OH)₂] · 2[ZnSO₄] was determined from high resolution laboratory X‐ray powder diffraction data by use of a combination of charge flipping, 18 simulated annealing, 26 and difference Fourier analysis. The material crystallizes in the space group P$\bar{1}$ with the lattice parameters of a = 5.4559(2) Å, b = 8.0528(3) Å, c = 8.9275(3) Å, α = 112.697(2)°, β = 85.219(3)°, γ = 95.441(3)°, and a volume of V = 359.76(2) ų. The basic crystal structure consists of brucite type Zn(OH)₂ layers where every sixth octahedral site is vacant. Tetrahedrally coordinated zinc ions are located above and below these vacancies and consecutive layers are bridged by sulfate molecules. The composition of this layered structure can be written as [Zn₅^VI□(OH)₄ · Zn₂^IV(OH)₆ · (SO₄)₂]. Its thermal decomposition was studied by X‐ray powder diffraction and thermal analysis.     

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.     

Synthesis and Structure of a Three‐dimensional Organically Templated Zinc Ethylenediphosphonate, [NH3(CH2)2NH3][Zn3{O3P(CH2)2}4]

A hydrothermal reaction of a mixture of ZnO, HCl, ethylenediphosphonic acid, ethylenediamine, acetic acid in a water, THF mixture gave rise to a new three‐dimensional zinc ethylenediphosphonate, [NH₃(CH₂)₂NH₃][Zn₃{O₃P(CH₂)₂}₄], I . The structure, determined by single crystal X‐ray diffraction, (monoclinic, space group = C2/c, a = 16.9948(14), b = 6.7383(6), c = 16.8886(14)Å, β = 1113.568(1)°, V = 1772.7(3)ų, Z = 4, R₁ = 0.0227, wR₂ = 0.0601), consists of a network of strictly alternating ZnO₄ and PO₃C tetrahedral units linked through their vertices forming the three‐dimensional structure. The amine molecules occupy the middle of the 8‐membered channels and interact with the framework through the hydrogen bonds. Unlike other zinc diphosphonates, I appear to have close similarity to zinc phosphate structures reported in the literature. To our knowledge, this is the first three‐dimensional zinc diphosphonate prepared in the presence of an organic amine molecule.     

Synthesis,Characterization, and Crystal Structure of Na3B20, determined and refined from X‐ray and Neutron Powder Data

At 1050 ?C boron combines with sodium forming a boride of formerly unknown composition and crystal structure. The investigation of the homogeneous, monophasic, and crystalline powder was performed using X‐ray (23 ?C) and neutron (–271.5 ?C) diffraction methods. The structure solution led to an unusual arrangement of boron atoms, characterized by two different types of polyhedra, a distorted pentagonal bipyramid and a distorted octahedron. The Rietveld refinement of the crystal structure was carried out in the orthorhombic space group Cmmm (X‐ray: a = 18.6945(6) Å, b = 5.7009(2) Å, c = 4.1506(1) Å, V = 442.35(1) ų, Z = 2; R_wp = 0.087, R_p = 0.067).     

Syntheses and Crystal Structures of the Novel Ternary Thioborates Na3BS3, K3BS3, and Rb3BS3

The orthothioborates Na₃BS₃, K₃BS₃ and Rb₃BS₃ were prepared from the metal sulfides, amorphous boron and sulfur in solid state reactions at temperatures between 923 and 973 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction experiments. Na₃BS₃ crystallizes in the monoclinic space group C2/c (No. 15) with a = 11.853(14) Å, b = 6.664(10) Å, c = 8.406(10) Å, β = 118.18(2)° and Z = 4. K₃BS₃ and Rb₃BS₃ are monoclinic, space group P2₁/c (No. 14) with a = 10.061(3) Å, b = 6.210(2) Å, c = 12.538(3) Å, β = 112.97(2) and a = 10.215(3) Å, b = 6.407(1) Å, c = 13.069(6) Å, β = 103.64(5)°, Z = 4. The potassium and rubidium compounds are not isotypic. All three compounds contain isolated [BS₃]^3– anions with boron in a trigonal‐planar coordination. The sodium cations in Na₃BS₃ are located between layers of orthothioborate anions, in the case of K₃BS₃ and Rb₃BS₃ stacks of [BS₃]^3– entities are connected via the corresponding cations. X‐ray powder patterns were measured and compared to calculated ones obtained from single crystal X‐ray structure determinations.     

The Crystal and Molecular Structure of γ‐P4S6

The crystal and molecular structure of γ‐P₄S₆ was determined from single‐crystal X‐ray diffraction. It crystallizes monoclinically in the space group P2₁/m (No. 11) with a = 6.627(3) Å, b = 10.504(7) Å, c = 6.878(3) Å, β = 90.18(4)°, V = 478.8(4) ų, and Z = 2. The structure consists of cage‐like P₄S₆ molecules with C_S symmetry arranged with the topology of a cubic close packing.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Synthesis of Organic Chloride Nitrate (C6H8N)2ClNO3, Molecular Structure,and Impact of Anion Disorder on Theoretical Studies

A new organic chloride nitrate compound, (C₆H₈N)₂ClNO₃ ( 1 ) was obtained from reacting Bi(NO₃)₃ · 2H₂O with aniline and HCl. Crystals of X‐ray diffraction quality were grown from aqueous solution. The molecular structure [space group P1 ; unit cell constants: a = 8.4176(14) Å, b = 9.6482(18) Å, c = 10.0363(16) Å, α = 62.993(7)°, β = 86.798(7)°, γ = 72.999(8)°], derived by single‐crystal X‐ray diffraction, comprises of two aniline protonated cations, one chlorine anion, and one disordered nitrate anion. The study of intermolecular interactions using Hirshfeld Surface analysis confirmed that the hydrogen bonds: Cl ··· H, O ··· H/O ··· H, O ··· O and H ··· H contacts play dominant role in the formation of the crystal structure. The analysis of electronic structure and the molecular modelling of four different disorder configurations classify this compound as semiconductors and confirms its good nucleophilic reactivity.     

Synthesis and Crystal Structure of α‐ThTe3

The binary thorium tritelluride, α‐ThTe₃, was synthesized by solid‐state methods at 1223 K. From a single‐crystal X‐ray diffraction study the material crystallizes in the TiS₃ structure type with two formula units in space group C²_2h–P2₁/m of the monoclinic system in a cell with lattice constants a = 6.1730 (4) Å, b = 4.3625(3) Å, c = 10.4161(6) Å, and β = 97.756(3)° (at 100 K). The asymmetric unit of this compound comprises one Th atom and three Te atoms each with site symmetry m. Each Th atom is coordinated to eight Te atoms in a bicapped trigonal‐pyramidal arrangement. Th–Te distances range from 3.1708(4) Å to 3.2496(6) Å. The structure features a Te–Te interaction 2.7631(8) Å in length, which is typical for a Te–Te single bond. Thus α‐ThTe₃ may be charge balanced and formulated as Th⁴⁺Te^2–Te₂^2–.     

Synthesis and Characterization of a New Layered Zinc Phosphite (NH4)[{Zn(H2O)4}0.5Zn2(HPO3)3]

A new layered zinc phosphite with the formula (NH₄)[{Zn(H₂O)₄}_0.5Zn₂(HPO₃)₃] has been synthesized under hydrothermal conditions. Its structure was determined by single‐crystal X‐ray diffraction. The compound crystallizes in the triclinic system, space group (No. 2), a = 7.2507(4), b = 9.7982(6), c = 10.2642(6) Å, α = 63.425(2), β = 87.165(2), γ = 72.999(3)°, V = 620.84(6) ų, Z = 2. The connectivity of ZnO₄ tetrahedra, HPO₃ pseudo pyramids and ZnO₂(H₂O)₄ octahedra results in macroanionic layers with 4.8 net.     

The Synthesis,Structure, and Tunable Emission Spectra of A New Phosphor Sm(IO3)3·2H2O

A new phosphor Sm(IO₃)₃ · 2H₂O was synthesized under mild hydrothermal conditions. The structure was confirmed by single‐crystal X‐ray powder diffraction analysis. It crystallizes in the triclinic system with space group P$\bar{1}$ (No.2), a = 7.1570Å, b = 7.4306Å, c = 10.6367Å, α = 95.205°, β = 104.844°, γ = 109.958°. Some characterizations were performed such as Fourier transform infrared spectroscopy (FTIR), powder X‐ray diffraction (PXRD), thermogravimetric and differential thermal analysis (TG‐DTA), and luminescence spectroscopy. The overall structure of the title compound is two‐dimensional. The adjacent iodate layers are further linked with each other by hydrogen bonds to form a three‐dimensional supramolecular network. The luminescent properties of Sm(IO₃)₃ · 2H₂O were studied, the exhibit tunable emission spectra by means of heating treatment.     

{[Zn2(Bim)3(OH)(H2O)]·(DMF)(H2O)3}∞: A Two Dimensional Coordination Polymer with Layer Silicate‐like Structure

A layer silicate‐like zinc(II) benzimidazolate polymer {[Zn₂(Bim)₃(OH)(H₂O)]·(DMF)(H₂O)₃}_∞ ( 1 ) was synthesized at room temperature and characterized with X‐ray single‐crystallography: Monoclinic, space group C2/m (No.12), a = 10.423(3) Å, b = 17.416(6) Å, c = 16.583(5) Å, β = 92.698(4), V = 3006.8(17) ų.     

A Highly Stable 3D Porous Lanthanum Metal‐organic Framework Constructed From A New Flexible Bis(benzoic acid) Ligand Produced in Situ

By employing diethyl 1,3‐propylidenebis(4‐oxybenzoate) as a precursor, the new three‐dimensional metal‐organic framework [La₂L₂(HL)₂]_n [L = 1,3‐propylidenebis(4‐oxybenzoate)] was prepared and characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The compound crystallizes in the triclinic space group P , with cell parameters: a = 8.299 (2) Å, b = 14.127 (3) Å, c = 14.520 (3) Å, α = 112.43 (3) °, β = 103.10 (3) °, γ = 95.28 (3)°, V = 1502.2 (5) Å³, and Z = 1. Under hydrothermal reaction conditions, two ester groups of the ligand hydrolyzed into carboxylate groups. The carboxylate groups coordinated in situ to metal ions to form the 3D coordination polymer. It exhibits a 10.4 × 10.6 Å rhombic channel along the [011] direction. On the basis of the results of TG analysis, the structure is thermally stable up to ≈? 400 °C.     

The Crystal Structure of Disodium Phosphonate,Na2HPO3

Anhydrous disodium phosphonate, Na₂HPO₃, was prepared by dehydration of its pentahydrate. The crystal structure of Na₂HPO₃ was solved from high resolution X‐ray powder diffraction data (P2₁/n; Z = 4; a = 9.6987(1), b = 6.9795(1), c = 5.0561(1) Å, β = 92.37(1)°; V = 341.97(1) ų). The crystal structure consists of two types of sodium‐oxygen polyhedra, which are connected via common edges and vertices forming layers perpendicular to [100]. These Na(1)‐ and Na(2)‐layers are interlinked via common edges, forming in a 3D‐framework. The resulting topology is providing oxygen arrangements that please the coordinative requirement of phosphorus(III).     

Synthesis,Band and Crystal Structures,and Optical Properties of the Ternary Compound Mg2Te3O8

The new spiroffite Mg₂Te₃O₈ ( 1 ) was prepared by hydrothemal methods and structurally characterized by single‐crystal X‐ray diffraction analysis. Compound 1 crystallizes in the space group C2/c of the monoclinic system with two formula units in a cell: a = 12.6030(7), b = 5.2254(3), c = 11.6331(7) Å, β = 98.6960(10)°, V = 757.30(8) ų. The structure features a 3D open‐framework with spiroffite topology that has large tunnels approximately 3.2 × 5.5 Å. The optical properties and thermal stability of 1 were characterized by UV and IR spectroscopy as well as TG. Calculations of the electronic band structure along with the density of states (DOS) indicate that the present compound is a semiconductor with an indirect band gap, and that the optical absorption is mainly originated from the charge transitions from O‐2p state to Te‐5p and Te‐5s states.     

Synthesis,Spectrothermal and Structural Characterization of Saccharinatobis(tris‐hydroxymethylaminomethane)zinc(II)saccharinate Complex, [Zn(sac)(tham)2](sac)

A novel Zn^II complex of the saccharinate ligand (sac) with tris‐hydroxymethylaminomethane (tham) was synthesized and characterized by elemental analysis, FT‐IR spectroscopy, simultaneous TG and DTA techniques, and X‐ray diffraction. The complex, [Zn(sac)(tham)₂](sac), crystallizes in monoclinic system with space group P2₁/c [a = 7.55954(3) Å, b = 13.0532(6) Å, c = 27.7777(10) Å, β = 100.539(3)°, Z = 4]. The Zn^II ion has a distorted octahedral coordination. The tham ligand has chemically different functions in the structure, acting as both bidentate and tridentate ligands. There are also sac moieties to act as N‐bonded ligand and as a counter anion. The molecular packing of the complex is provided by moderate hydrogen bonds as well as π···π interactions between the sac moieties. The IR spectra and the thermal decomposition of the complex are also discussed.