Difluorotetrakis(2‐oxypyridine)dirhenium(III) – Preparation,Crystallographic Structure,and Electrochemical Properties

The solid‐state‐melt reaction of (NH₄)₂[Re₂F₈] · 2H₂O with 2‐hydroxypyridine (2‐HOpy) produced dark‐red Re₂(2‐Opy)₄F₂ ( 1 ). This air‐stable compound was obtained in crystalline form as 1· CHCl₃. It was characterized in the solid state by single‐crystal X‐ray diffraction and in solution by UV/Vis spectroscopy and cyclic voltammetry. 1· CHCl₃ forms triclinic crystals with α = 8.3254(5) Å, b = 8.5563(5) Å, c = 11.6784(8) Å, α = 82.723(3)°, β = 75.769(3) °, γ = 64.407(2) °. The Re–Re and Re–F distances were 2.2091(7) and 2.115(6) Å, respectively. The molecule is isostructural with the corresponding chloro derivative.     

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.     

Synthesis,Crystal Structure,and Properties of the Sodium Molybdate Fluoride Na3MoO4F

The compound Na₃MoO₄F was synthesized by high temperature solution methods. Single‐crystal X‐ray diffraction analysis reveals that Na₃MoO₄F crystallizes in the orthorhombic space group Pnma (No. 62) with lattice constants a = 5.588(2) Å, b = 7.515(3) Å, c = 12.876(5) Å, and Z = 4. The crystal structure consists of isolated MoO₄ groups and [FNa₃]_∞ chains, which are connected by Na–O bonds to form a three‐dimensional framework. A detailed structure comparison between Na₃MoO₄F and NaMoO₃F was carried out. IR spectroscopy and bond valence sum analysis of Na₃MoO₄F indicate that the structure is reasonable. In addition, the electronic structure was investigated by the first‐principles method.     

Synthesis,Crystal Structure,and Variable‐Temperature‐Luminescent Property of the Organically Templated Pentaborate [C10N2H9][B5O6(OH)4]·H3BO3·H2O

The organically templated pentaborate [C₁₀N₂H₉][B₅O₆(OH)₄] · H₃BO₃ · H₂O ( 1a ) was synthesized by boric acid and 4, 4′‐bipyridine in aqueous solution and characterized by single‐crystal X‐ray diffraction, elemental analysis, FTIR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and photoluminescence spectroscopy. The compound crystallizes in the triclinic system with space group P$\bar{1}$ (a = 9.196(3) Å, b = 9.822(3) Å, c = 12.113(3) Å, α = 66.243(3)°, β = 76.998(3)°, γ = 75.067(3)°, V = 958.4(5) ų, and Z = 2). The polyanions form a novel 3D supramolecular network with three kinds of channels by extensive hydrogen bonds. The title compound shows a UV photoluminescence with an emission maximum at 372 nm upon excitation at 248 nm, and the photoluminescence can be modified from UV to blue by means of a simple heat‐treatment process. The pentaborate could be a promising blue component for possible application in the white LED.     

The Sodium (Iso)Cyanurates Nax[H3–xC3N3O3]·yH2O (x = 1–3, y = 0, 1): A Key‐Series for Understanding the Crystal Chemistry of Metal (Iso)Cyanurates

The (iso)cyanurates Na[H₂C₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃], and Na₃[C₃N₃O₃] were synthesized phase pure from Na₂CO₃ · 10H₂O, NaOH, and cyanuric acid, respectively, in aqueous solution by carefully adjusting the crystallization conditions. The crystal structures of all compounds were determined by single‐crystal X‐ray diffraction {Na₂[HC₃N₃O₃] · H₂O: P1 , a = 3.51660(10) Å, b = 7.8300(3) Å, c = 11.3966(4) Å, α = 86.4400(10)°, β = 85.5350(10)°, γ = 85.0720(10)°, Z = 2, R₁ = 0.030, wR₂ = 0.078; Na₂[HC₃N₃O₃]: Pnma, a = 6.3409(6) Å, b = 12.2382(13) Å, c = 6.5919(7) Å, Z = 4, R₁ = 0.045, wR₂ = 0.079; Na₃[C₃N₃O₃]: R3 c, a = 11.7459(3) Å, c = 6.5286(3) Å, Z = 3, R₁ = 0.039, wR₂ = 0.066}. The structures show ribbons (Na[H₂C₃N₃O₃] · H₂O), dimers (Na₂[HC₃N₃O₃] · H₂O), chains (Na₂[HC₃N₃O₃]), or columns (Na₃[C₃N₃O₃]) of hydrogen‐bonded and parallel stacked (iso)cyanurate anions. These motifs are shown to be characteristic for certain degrees of protonation and hydration, and all (iso)cyanurate crystal structures found so far were classified accordingly. X‐ray powder patterns, thermogravimetry curves, IR and UV/Vis spectra were measured for all compounds.     

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.     

Three Ternary Rare Earth(III) Complexes Based on 3‐[(4,6‐Dimethyl‐2‐pyrimidinyl)thio]‐propanoic Acid and 1,10‐Phenanthroline: Synthesis,Crystal Structure and Antioxidant Activity

Three ternary rare earth [Nd^III ( 1 ), Sm^III ( 2 ) and Y^III ( 3 )] complexes based on 3‐[(4,6‐dimethyl‐2‐pyrimidinyl)thio]‐propanoic acid (HL) and 1,10‐phenanthroline (Phen) were synthesized and characterized by IR and UV/Vis spectroscopy, TGA, and single‐crystal X‐ray diffraction. The crystal structures showed that complexes 1 – 3 contain dinuclear rare earth units bridged by four propionate groups and are of general formula [REL₃(Phen)]₂ · nH₂O (for 1 and 2 : n = 2; for 3 : n = 0). All rare earth ions are nine‐coordinate with distorted mono‐capped square antiprismatic coordination polyhedra. Complex 1 crystallizes in the monoclinic system, space group P2₁/c with a = 16.241(7) Å, b = 16.095(7) Å, c = 19.169(6) Å, β = 121.48(2)°. Complex 2 crystallizes in the monoclinic system, space group P2₁/c with a = 16.187(5) Å, b = 16.045(4) Å, c = 19.001(4) Å, β = 120.956(18)°. Complex 3 crystallizes in the triclinic system, space group P1 with a = 11.390(6) Å, b = 13.636(6) Å, c = 15.958(7) Å, α = 72.310(17)°, β = 77.548(15)°, γ = 78.288(16)°. The antioxidant activity test shows that all complexes own higher antioxidant activity than free ligands.     

Synthesis,Crystal Structure,and Characterization of three New Letrozole Complexes

Three new letrozole complexes {[Cu(Le)₄Cl₂] · (H₂O)} ( 1 ), {[Ni(Le)₄Cl₂] · (H₂O)}( 2 ) and {[Co(Le)₄Cl₂] · (H₂O)} ( 3 ) (Le = letrozole = 1‐[bis(4‐cyanophenyl)methyl]‐1, 2, 4‐triazole) were obtained from self‐assembly of CuCl₂, NiCl₂ · 6H₂O, and CoCl₂ · 6H₂O with medicine letrozole. All compounds were characterized by IR spectroscopy, elemental, single‐crystal as well as powder X‐ray diffraction, and thermogravimetric analyses. The analyses of the structures indicate that all crystals belong to monoclinic system, space group C2/c, for complex 1 with crystal data a = 34.501(18) Å, b = 12.724(7) Å, c = 16.116(9) Å, β = 114.958(7) °, V = 6414(6) Å ³, Z = 4, F(000) = 2660, R₁ = 0.0668, wR₂ = 0.1574; for complex 2 , a = 34.769(6) Å, b = 12.7267(18) Å, c = 16.046(2) Å, β = 115.281(3) °, V = 6420.1(16) Å ³, Z = 4, F(000) = 2656, R₁ = 0.0510, wR₂ = 0.0896; for complex 3 , a = 35.063(8) Å,b = 12.658(3) Å, c = 16.056(4) Å, β = 115.387(3) °, V = 6438(2) ų, Z = 4, F(000) = 2652, R₁ = 0.0528, wR₂ = 0.1205. The local arrangements around central metal atoms (Cu^II, Ni^II, and Co^II) can be best described as distorted octahedra which are constructed by two chlorine atoms and four monodentate nitrogen atoms from different letrozole ligands. XRD results of 1 – 3 show that all peaks displayed in the measured patterns at room temperature closely match those in the simulated patterns generated from single‐crystal diffraction data, indicating single phases of 1 – 3 were formed.     

New Borate‐citrate: Synthesis,Structure, and Properties of Sr[B(C6H5O7)2](H2O)4·3H2O

Single crystals of Sr[B(C₆H₅O₇)₂](H₂O)₄ · 3H₂O, a new borate‐citrate material, were grown with sizes up to 8 × 6 × 2 mm by slow evaporation of water at room temperature. The structure of Sr[B(C₆H₅O₇)₂](H₂O)₄ · 3H₂O was determined by single‐crystal X‐ray diffraction. It crystallizes in the monoclinic space group P2₁/c, with a = 11.363(3) Å, b = 18.829(4) Å, c = 11.976(3) Å, β = 110.736(3)°, and Z = 4. The SrO₈ dodecahedra, BO₄ tetrahedra and citrate groups are linked together to form chains. The compound was characterized by IR and UV/Vis/NIR transmittance spectroscopy as well as thermal analysis.     

Hetero‐metallic Lanthanide CPs Involving Sodium: Synthesis,Crystal Structure,and Luminescence Properties

[TbNa(4‐msal)₄(phen)₂]_n ( 1 ) (4‐msal = 4‐methyl salicylic acid), a new hetero‐metallic lanthanide coordination polymer (CP) involving sodium was synthesized. It crystallizes in the monoclinic space group P2₁/n, with a = 20.4809(9) Å, b = 9.8183(2) Å, c = 26.1987(11) Å, α = 90.00°, β = 112.922(5)°, γ = 90.00°, V = 4852.2(3) ų, and Z = 4. The complex was characterized by single crystal and powder X‐ray diffraction, elemental analysis (EA), and Fourier transform infrared (FT‐IR) and luminescence spectroscopy. The luminescence properties of a powder sample of 1 were studied at room temperature and the luminescence lifetime and total quantum yield (QY) were determined.     

Synthesis,Crystal Structure,Theoretical Study,and Luminescence Spectroscopy of A W/Cu/S Cluster with 1, 10‐Phenanthroline

The reaction of [NH₄]₂WOS₃ with Cu(CH₃CN)₄ClO₄ and 1, 10‐phenanthroline(phen) in CH₂Cl₂ afforded the butterfly‐shaped cluster {[WOS₃Cu₂(phen)₂] · CH₂Cl₂} ( 1 ), which was characterized by elemental analysis, single‐crystal X‐ray diffraction as well as IR and fluorescence spectroscopy. The complex crystallizes in the triclinic system with space group P$\bar{1}$ [a = 8.3976(17) Å, b = 9.6771(19) Å, c = 18.460(4) Å, α = 89.94(3)°, β = 80.33(3)°, γ = 70.38(3)°, V = 1390.5(5) ų, and Z = 2]. Single crystal X‐ray diffraction analysis reveals that complex 1 displays pairwise π–π stacking. Density functional theory and time‐dependent density functional theory calculations at the B3LYP/LanL2DZf+6‐31G* level were performed on complex 1 to rationalize its experimental absorption spectra. Fluorescence spectroscopy reveals that complex 1 exhibits luminescence in EtOH solution at room temperature.     

Sodium tris(glycinium) bis(hexafluorosilicate) glycine trisolvate

The title compound, Na⁺·3C₂H₆NO₂⁺·2SiF₆²⁻·3C₂H₅NO₂, arose from an unexpected reaction of glycine and HF with the glass container. It is an unusual hybrid organic–inorganic network built up from chains of vertex‐sharing NaF₄O₂ and SiF₆ octahedra. A pair of glycinium/glycine molecules bridges the chains into a sheet via a centrosymmetric O...H...O link. The other organic species interact with the network by an extensive N—H...F hydrogen‐bond network, including bifurcated and trifurcated bonds. Finally, an extremely short C—H...O interaction (H...O = 2.25 Å) is seen in the crystal structure. The Na atom has site symmetry .     

Synthesis,Structure Characterization,and Optical Properties of the Aluminosilicate Li2Na3AlSi2O8

The aluminosilicate Li₂Na₃AlSi₂O₈ was crystallized from the Li₂CO₃–H₃BO₃ flux system. It crystallizes in the orthorhombic space group Cmca, with cell dimensions a = 14.1045 (19) Å, b = 14.7054 (19) Å, c = 7.0635 (9) Å, and Z = 8. The crystal structure consists of a two‐dimensional infinite layer, which is composed of [Al₂Si₂O₁₂] groups and [SiO₄] tetrahedra. The lithium and sodium atoms filling in the interlayer and intralayer link the layers together and balance the charge. IR spectroscopy and BVS calculations were used to verify the validity of the structure. The calculated band structures and the density of states of Li₂Na₃AlSi₂O₈ suggest that its direct gap is 4.28 eV.     

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.     

A new 3s–3d heterometallic polymer containing N‐methyliminodiacetic acid: synthesis,structure and characterization

A new complex {[Na₂(H₂O)₃(µ‐L)₂Cu]₄}_∞ (L = N‐methyliminodiacetic acid) has been synthesized and structurally characterized. The complex crystallizes in the monoclinic, space group C2/c, with the unit cell parameters a = 16.556(3) Å, b = 8.0622(13) Å, c = 12.671(2) Å, α = 90°, β = 95.849(2)°, γ = 90°. The central metal Cu (II) ion is coordinated with two nitrogen atoms and four oxygen atoms belonging to two ligands. Simultaneously, the sodium is six‐coordinated with oxygen atoms coming from the ligand and water molecule; the sodium atoms related are bridged by oxygen atoms, forming a sodium chain. The structure consists of CuL₂ moieties linked by sodium chain via the exo oxygen atoms of two ligands, forming a novel three‐dimensional structure. Moreover, elemental analysis, IR, UV‐vis, ESR spectroscopy and thermal stability were determined. Copyright © 2007 John Wiley & Sons, Ltd.     

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 and Characterization of an Inorganic‐Organic Hybrid Layered Zinc Phosphite [(C2H3N3)Zn(HPO3)]

A inorganic‐organic hybrid zinc phosphite (C₂H₃N₃)Zn(HPO₃) ( 1 ) has been prepared under solvothermal conditions in the presence of 1,2,4‐triazole (trz) ligand.Its structure was determined by single‐crystal X‐ray diffraction, and further characterized by powder X‐ray diffraction (XRD), FTIR spectroscopy, elemental analysis, ICP analysis, thermogravimetric analysis and fluorescent spectrum. It crystallizes in the monoclinic system, space group P2₁/n, a = 7.5515(6) Å, b = 9.1813(8) Å, c = 10.0125(8) Å, β = 111.267(1)°, V = 646.92(9) ų, Z = 4. The structure consists of left‐handed and right‐handed helical chains that are connected through bridging oxygen atoms to form a two‐dimensional layer structure with 4.8‐net. The compound exhibits intense photoluminescence upon photo‐excitation at 326 nm.     

Synthesis and Crystal Structures of Axially Substituted Titaniumphthalocyanines and Preparation of PcTi@SBA‐15 and PcTi&TiOx@SBA‐15 Materials

Four axially substituted titanium(IV)phthalocyanines of formula trans‐[PcTi(OSiPh₃)₂], [PcTi{(NH)₂C₆H₄}], [PcTi(η²‐S₂)], and [PcTi=S] were prepared starting from the reactive species N,N′‐di‐4‐tolylureato(phthalocyaninato)titanium(IV). The prepared compounds were characterized by using UV/Vis‐spectroscopy, FT‐IR and raman spectroscopy, TGA, elementalanalysis and MALDI‐TOF measurements. The compound trans‐[PcTi(OSiPh₃)₂] crystallizes from chlorobenzene in the triclinic space group P with a = 10.4160(8) Å, b = 11.2160(8) Å, c = 13.1495(9) Å, α = 114.124(5)°, β = 99.452(6)°, γ = 96.174(6)°, and Z = 1. [PcTiS₂] crystallizes from chlorobenzene in the monoclinic space group P2₁/n with a = 13.114(3) Å, b = 9.752(2) Å, c = 20.975(5) Å, β = 100.46(2), and Z = 4. The crystal structures of both compounds are discussed. The reactive ureato complex could also successfully be anchored onto SBA‐15 and TiO_x@SBA‐15 materials using the apical ureato ligand as a good leaving group for the reaction with the silanol groups of the host material.     

LixNayBa14LiN6: New Representatives of the Subnitride Family

Three new metal‐rich phases, Li₄Na₁₁Ba₁₄LiN₆, Li₅Na₁₀Ba₁₄LiN₆ and Na₁₄Ba₁₄LiN₆ have been prepared and their crystal structure determined. According to single crystal and powder X‐ray diffraction data, all compounds crystallize with cubic unit cells (Li₄Na₁₁Ba₁₄LiN₆: , a = 17.874(2) Å, Z = 4, V = 5710(1) ų; Li₅Na₁₀Ba₁₄LiN₆: , a = 17.799(1) Å, Z = 4, V = 5638.7(6) ų; Na₁₄Ba₁₄LiN₆: , a = 17.7955(5) Å, Z = 4, V = 5635.6(2) Å). The last mentioned compound crystallizes in the Na₁₄Ba₁₄CaN₆ type, and both Li₄Na₁₁Ba₁₄LiN₆ and Li₅Na₁₀Ba₁₄LiN₆ have related structures. These compounds open a series of metal‐rich Ba nitrides, containing the new Ba₁₄LiN₆ cluster.     

Reinvestigation and Characterization of the Magnesium Borate Fluoride Mg5(BO3)F

The magnesium borate fluoride Mg₅(BO₃)₃F was grown by spontaneous crystallization with molten flux based on the MgF₂‐LiF‐Na₂CO₃‐H₃BO₃ solvent. Structure solution from single‐crystal X‐ray diffraction shows that the title compound crystallizes in the orthorhombic space group Pnma (No. 62) with cell dimensions of a = 10.068(5) Å, b = 14.858(7) Å, c = 4.540(2) Å and Z = 4. Its structure features a three‐dimensional (3D) Mg‐O‐F framework composed of MgO₅F and MgO₆ polyhedra and isolated BO₃ groups. The detailed structure comparison referred to Mg₅(BO₃)₃F, Mg₃BO₃F₃ and β‐Mg₂BO₃F was carried out. The infrared spectrum (IR) and the bond valence sum (BVS) calculations of Mg₅(BO₃)₃F verify the validity of the structure. The calculated band structure and the density of states of Mg₅(BO₃)₃F suggest that its indirect bandgap is 5.27 eV. The compound was additionally investigated by UV/Vis‐NIR diffuse reflectance spectroscopy and thermal analysis.