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.     

Crystal Structure of the [(C5H4BMe2)2Fe]‐4,4′‐bipyridine Polymer from High Resolution X‐Ray Powder Diffraction

The crystal structure of [(C₅H₄BMe₂)₂Fe]‐4,4′‐bipyridine [ 2 · bipy]_n has been determined by the method of simulated annealing from high resolution X‐ray powder diffraction at room temperature. The compound is of interest, because it proves that highly ordered organometallic macromolecules can be formed in the solid state via the self‐assembly of N–B‐donor‐acceptor bonds. [ 2 · bipy]_n crystallizes in the triclinic space group, P 1, Z = 2, with unit cell parameters of a = 8.3366(2) Å, b = 11.4378(3) Å, c = 12.6740(5) Å, α = 112.065(2)°, β = 108.979(1)°, γ = 90.551(2)°, and V = 1047.06(6) ų. For the structure solution of [ 2 · bipy]_n 11 degrees of freedom (3 translational, 3 orientational, 5 torsion angles) were determined within several hours, demonstrating that the crystal packing and the molecular conformation of medium sized (< 50 non‐hydrogen atoms) coordination compounds can nowadays be solved routinely from high resolution powder diffraction data.     

Theoretical Investigations on 4, 10‐Dinitro‐2, 6,8, 12‐tetraoxa‐4, 10‐diazatetracyclo[5.5.0.05, 903, 11]dodecane

Based on the full optimized molecular geometric structure at B3LYP/cc‐pvtz method, the newly designed compound 4, 10‐dinitro‐2, 6,8, 12‐tetraoxa‐4, 10‐diazatetracyclo[5.5.0.0^{5, 9}0^{3, 11}]dodecane (TEX) was investigated. Additionally, the IR spectrum, the thermal stability, and the detonation performance were predicted. The obtained crystal structure of TEX belongs to Pbca space group and lattice parameters are Z = 8, a = 8.614 Å, b = 12.877 Å, c = 26.065 Å, ρ = 2.015 g · cm^–3. Calculation results show that TEX has better detonation properties than HMX and is a high energy density compound with better stability.     

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 and Crystal Structure of Octahydro‐5H,12H‐4,11‐methano‐1H,7H‐bis[1,2,5]oxadiazolo[3,4‐d:3′,4′‐j][1,7,3,9]dioxadiazacyclododecine

The unusual 12‐membered ring compound, octahydro‐5H,12H‐4,11‐methano‐1H,7H‐bis[1,2,5]oxadiazolo[3,4‐d:3′,4′‐j][1,7,3,9]dioxadiazacyclododecine is obtained from the acid catalyzed reaction of 3‐amino‐4‐hydroxymethylfurazan with formaldehyde instead of the expected methylene‐bridged compound, 4,4′‐methylenebis[4,5‐dihydro‐7H‐[1,2,5]oxadiazolo[3,4‐d][1,3]oxazine]. The compound crystallizes in Tetragonal, P4₃2₁2, a = 6.4141(4) Å, b = 6.4141(4) Å, c = 26.525(3) Å, α = 90°, β = 90°, γ = 90°, V = 1091.27(16) ų, Z = 4, dcalc = 1.614 Mg/m³.     

Structural Investigations and Thermal Behavior of (NH4)[Cr(C2O4)2]·2H2O

Single crystals of ammonium chromium(III) dioxalate dihydrate (or ammonium diaquo bis(μ‐oxalato)chromate(III)) have been obtained from aqueous solution of oxalic acid and ammonium dichromate. A pale violet crystal of good optical quality was used for the structure determination at ?100(2) and 25(2) °C, respectively. The basic crystallographic data for the low temperature data set are as follows: monoclinic, space group C2/m, a = 6.597(2) Å, b = 7.301(2) Å, c = 9.983(3) Å, β = 92.32(2)°, V = 480.5(2) ų. The structure was solved by direct methods and refined (using anisotropic displacement parameters for all non‐hydrogen atoms) to a final residual of R1 = 0.032 for 503 independent observed reflections (I>2σ(I)). The compound is isotypic with the corresponding rubidium salt. The structure is built up from alternating layers parallel to (001) containing (NH₄)⁺ ions or Cr(C₂O₄)₂(H₂O)₂ octahedra, respectively. The corners of the octahedra consist of four O atoms from two oxalate groups and two additional water molecules. The ammonium cations (occupying Wyckoff‐site 2a) are disordered among two possible orientations. They provide linkage between different octahedral layers by hydrogen bridging. The water molecules in turn form hydrogen bridges with adjacent octahedra within the same layer. Further structural characterization included infrared spectroscopy. According to DTA/TG experiments the present compound shows several thermal processes in the range between room temperature and 900 °C.     

Synthesis,Structure, and Properties of a New Calcium(II) Complex of 1,10‐Phenanthroline, 1,2,4,5‐Benzenetetracarboxylic Acid,and a New Precursor to Produce Pure Phase Micro‐crystalline Calcite Particles

The self‐assembly of 1, 0‐phenanthroline (phen) and 1,2,4,5‐benzenetetracarboxylic acid(H₄btc) with Ca(NO₃)₂ gives rise to a two‐dimensional network structure coordination polymer, [Ca(phen)(btc)_0.5(H₂O)] ( 1 ), which was characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. This compound is monoclinic, space group C2/c, with Z = 8 in a unit cell with dimensions a = 21.744(3) Å, b = 10.0151(12) Å, c = 14.7122(17) Å, β = 110.2850(10)°. The structure contains one crystallographic unique Ca^II atom, one phen coordinated molecule and a half of btc^4– anion. The phen molecule acts as a didentate ligand chelating with a Ca^II atom, whereas the btc^4– anion acts as a μ₆‐bridge linking six different Ca^II atoms to form a two‐dimensional network with (4, 4) topological structure. The three dimensional stacking structures are formed by C–H ··· O hydrogen bonding and π–π interaction. The thermal stability and fluorescent properties of 1 were investigated. Calcite particles are produced by calcination of compound 1 at 580 °C. The obtained calcite was characterized by XRD and SEM analyses.     

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.     

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.     

The Structure of Hydrotris(imidazolyl)boratothallium(I) – the First Structurally Authenticated Tris(imidazolyl)borate Metal Complex

The title compound crystallizes in the monoclinic space group P2₁/n with a = 8.706(1), b = 9.192(1), c = 15.261(2) Å, β = 94.740(3)°, V = 1217.0(3) ų, Z = 4, D_calc = 2.278 g cm^–3. The tris(imidazolyl)borate ligand bridges between three thallium atoms. The structure consists of one‐dimensional twisted ladder‐like strands.     

Preparation,Crystal Structure,and Thermal Decomposition of the Intriguing Five‐coordinated Compound [Cu(IMI)4Cl]Cl (IMI = Imidazole)

The intriguing multi‐ligand compound [Cu(IMI)₄Cl]Cl ( 1 ) with the ligand imidazole (IMI) was synthesized and characterized by elemental analysis and FT‐IR spectroscopy. The crystal structure was determined by X‐ray single crystal diffraction and the crystallographic data showed that the compound belongs to the monoclinic P2₁/n space group [α = 8.847(2) Å, b = 13.210(3) Å, c = 13.870(3) Å, and β = 90.164(3)°]. Furthermore, the Cu^II ion is five‐coordinated by four nitrogen atoms from four imidazole ligands and a chlorine atom. The thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetric (TG‐DTG) analysis. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa's method, respectively. The energy of combustion, enthalpy of formation, critical temperature of thermal explosion, entropy of activation (ΔS^≠), enthalpy of activation (ΔH^≠), and free energy of activation (ΔG^≠) were measured and calculated.     

Hydrogen‐Bonding in Cyclic 2‐(3‐Oxo‐3‐phenylpropyl)‐Substituted 1,3‐Diketones: 17O‐NMR Spectra and X‐Ray Structure Determination

Structures of cyclic 2‐(3‐oxo‐3‐phenylpropyl)‐substituted 1,3‐diketones 4a – c were determined by ¹⁷O‐NMR spectroscopy and X‐ray crystallography. In CDCl₃ solution, compounds 4a – c form an eight‐membered‐ring with intramolecular H‐bonding between the enolic OH and the carbonyl O(11)‐atom of the phenylpropyl group, as demonstrated by increased shielding of specifically labeled 4a – c in the ¹⁷O‐NMR spectra (Δδ(¹⁷O(11))=36 ppm). In solid state, intermolecular H‐bonding was observed instead of intramolecular H‐bonding, as evidenced by the X‐ray crystal‐structure analysis of compound 4b . Crystals of compound 4b at 293 K are monoclinic with a=11.7927 (12) Å, b=13.6230 (14) Å, c=9.8900 (10) Å, β=107.192 (2)°, and the space group is P2₁/c with Z=4 (refinement to R=0.0557 on 2154 independent reflections).     

Experimental and theoretical investigation of the molecular and electronic structure of N′‐benzylidene‐N‐[4‐(3‐methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐chloro‐acetic acid hydrazide

The title compound, N′‐benzylidene‐N‐[4‐(3‐methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐chloro‐acetic acid hydrazide, has been synthesized and characterized by elemental analysis, IR, ¹H and ¹³C NMR, and X‐ray single crystal diffraction. The compound crystallizes in the orthorhombic space group P 21 21 21 with a = 5.8671 (3) Å, b = 17.7182 (9) Å, and c = 20.6373 (8) Å. Moreover, the molecular geometry from X‐ray experiment, the molecular geometry, vibrational frequencies, and gauge‐including atomic orbital ¹H and ¹³C chemical shift values of the title compound in the ground state have been calculated by using the Hartree–Fock and density functional methods (B3LYP) with 6‐31G(d) and 6‐31G(d,p) basis sets. The results of the optimized molecular structure are exhibited and compared with the experimental X‐ray diffraction. Besides, molecular electrostatic potential, Frontier molecular orbitals, and thermodynamic properties of the title compound were determined at B3LYP/6‐31G(d) levels of theory. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

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.     

A Nine‐Coordinated ZrIV Complex and a Self‐Assembling System Obtained from a Proton Transfer Compound Containing 2,6‐Pyridinedicarboxylate and 2,6‐Pyridinediammonium; Synthesis and X‐ray Crystal Structure

Starting with a zirconium salt and LH₂ , (pydaH₂)²⁺(pydc)^2?, (pyda=2, 6‐pyridinediamine; pydcH₂=2,6‐pyridinedicarboxylic acid), as a 1:1 proton transfer self‐associated compound, two different compounds were resulted. One of them is a new complex of Zr^IV with a flat pyridine containing ligand and structure of (pydaH)₂[Zr(pydc)₃] · 5H₂O (1) and the other, (pydaH)⁺(NO₃)^? (2) is an ion pair with no zirconium ion. The zirconium(IV) complex (1) is crystallized in triclinic system with space group and Z = 2, the crystallographic parameters are: a = 10.612(5) Å, b = 10.617(5) Å, c = 16.815(8) Å, α = 103.654(9)°, β = 95.821(9)°, γ = 98.891(9)° and R‐value for 16767 collected reflections is 0.0592. The ion pair (2) has crystals of monoclinic system with P2₁ space group and Z = 2. Its crystallographic parameters are: a = 3.6227(11) Å, b = 10.034(4) Å, c = 10.296(4) Å, β = 93.422(9)° and R‐value for 4031 collected reflections is 0.0521. The two compounds were characterized with elemental analysis, ESI/MS, NMR and IR spectroscopy.     

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.     

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 Comprehensive Characterization of Hydrated Alkaline Earth Metal Salts of 5‐Amino‐1H‐tetrazole

Hydrated alkaline earth metal salts of 5‐amino‐1H‐tetrazole ( B ) were synthesized by reaction of B with a suitable metal hydroxide in water. All compounds were fully characterized by analytical (elemental analysis and mass spectrometry) and spectroscopic (IR, Raman, ¹H and ¹³C NMR) methods. Additionally, the crystal structures of the magnesium [ 1· 4H₂O: triclinic, P$\bar {1}$ , a = 5.940(1) Å, b = 7.326(1) Å,c = 7.383(1) Å, α = 106.10(1)°, β = 106.51(1)°, γ = 111.85(1)°, V = 258.0(1) ų], calcium [ 2· 6H₂O: monoclinic, P2₁/m, a = 6.904(1) Å,b = 6.828(1) Å, c = 10.952(2) Å, β = 94.50(2)°, V = 514.6(1) ų], and strontium [ 3· 6H₂O: orthorhombic, Cmcm, a = 6.987(1) Å, b = 28.394(2) Å, c = 7.007(1) Å, V = 1390.3(2) ų] were determined by low temperature X‐ray diffraction. Additionally, the (gas phase) structure of the 5‐amino‐1H‐tetrazole anion ([ B ]^–) was also studied by natural bond orbital (NBO) analysis [B3LYP/6‐31+G(d,p)]. Lastly, standard tests were used to determine the sensitivity towards impact, friction, and electrostatic discharge of the compounds and the thermal stability was assessed by differential scanning calorimetry (DSC) analysis.     

Synthesis,Structure, and Photoluminescence Properties of an Organically‐Templated Uranyl Selenite

The organically‐templated uranyl selenite, (H₂en)[(UO₂)(SeO₃)(HSeO₃)](NO₃) · 0.5H₂O ( 1 ) (en = 1,2‐ethylenediamine) was synthesized and characterized by elemental analyses, IR spectroscopy, TG, and single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 13.170(3) Å, b = 11.055(2) Å, c = 18.009(4) Å, V = 2621.8(9) ų, M = 1316.19, Z = 4, D_cal = 3.334 g · cm^–3, μ(Mo‐K_α) = 17.998 mm^–1, GOF = 1.059, R₁ = 0.0263, wR₂ = 0.0532 [I>2σ(I)]. The X‐ray diffraction analysis reveals that compound 1 has a three‐dimensional (3D) supramolecular structure. It contains negatively charged [UO₂(HSeO₃)(SeO₃)]^– inorganic anion layers and is balanced by [H₂en]²⁺ cations and NO₃^– anions located in the interlayers. Furthermore, the photoluminescence properties of 1 were investigated.     

The Structure of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine in the Solid State and in Solution; Unprecedented Cocrystallization of Four Stereoisomers

The solid and solution structures of a new optically active aminopyridine compound, 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine [(S)‐csaap], 1 , are reported. Crystal data: space group P2₁, a = 8.9729 (5), b = 10.9447 (6), c = 36.693 (2) Å, β = 96.435 (1)°, V = 3580.8 (3) ų, Z = 8, R₁ = 0.0673 and wR₂ = 0.1600 with I > 2σ(I). This chiral compound shows an unprecedented cocrystallization of four stereoisomers, which are characterized by X‐ray crystallography and NMR spectroscopy.