Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O3PH)(4,4′-bpy)(H2O), Zn(O3PH)(4,4′-bpy)0.5 and Mn[O2PH(C6H5)]2(4,4′-bpy) (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine)

Four novel coordination polymers: Ag(dpa) I, Co(O₃PH)(4,4′-bpy)(H₂O) II, Zn(O₃PH)(4,4′-bpy)_0.5 III and Mn[O₂PH(C₆H₅)]₂(4,4′-bpy) IV (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine), were synthesized by microwave heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21/n with a=11.576(2) Å, b=5.585(2) Å, c=15.243(4) Å, β=109.00(2)°, V=931.8(3) ų. II crystallizes in monoclinic Cc space group with a=22.477(7) Å, b=5.280(1) Å, c=10.404(4) Å, β=96.08(3)°, V=1227.8(7) ų. III crystallizes in monoclinic P21/c space group with a=9.758(2) Å, b=7.449(3) Å, c=10.277(2) Å, β=100.02(2)°, V=735.6(4) ų. IV crystallizes in monoclinic space group P2/c with a=10.174(1) Å, b=11.817(3) Å, c=18.784(4) Å, β=102.14(1)°, V=2207.8(8) ų. I consists of linear metal–metal chains wrapped by dpa ligands. II and III consist of two-dimensional M^II(O₃PH) inorganic sheets cross-linked by 4,4′-bpy ligands, while IV is formed by Mn[O₂PH(C₆H₅)]₂ sheets cross-linked by 4,4′-bpy ligands. I exhibits two-step thermal decomposition at ~200 and ~250°C, resulting in the reduction of Ag⁺ to Ag metal. II loses its coordination water at ~100°C, leaving vacant coordination sites at Co²⁺ ions, while the original framework remains intact. The removal of 4,4′-bpy in II–IV occurs at elevated temperatures above 250, 200 and 400°C respectively.     

Crystal growth and characterization of a new co-ordination complex—barium tetrakis(maleate) dihydrate

Crystals of barium tetrakis(maleate) dihydrate [Ba₄(C₄H₂O₄)₄]^?2H₂O are grown in gelated hydrosilica matrix. Single crystal X-ray diffraction studies show that the crystal system is monoclinic with space group P2₁/c. The unit cell dimensions are a=9.3721(2)  Å, b=20.5880(7)  Å, c=14.0744(4) Å, α=γ=90°, β=90.289(2)°. Powder XRD studies confirmed the single phase nature of the grown crystals. The FTIR data is in conformity with the XRD results. The TG–DTA curves of the material indicate a three-step thermal decomposition. The response of the dielectric properties in the temperature range 30 °C to 500 °C is correlated with the TG–DTA results.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

A new molecular C60 complex with bis(methylenedithio)tetrathiafulvalene (BMDT-TTF): Synthesis, crystal structure, and properties

A new molecular C₆₀ complex of the composition (BMDT-TTF) · C₆₀ · 2CS₂ (I) with the bis(methylenedithio)tetrathiafulvalene (BMDT-TTF) organic donor is synthesized. The molecular and crystal structures of this complex are determined by x-ray diffraction. The (BMDT-TTF) · C₆₀ · 2CS₂ (I) compound crystallizes in a monoclinic crystal system. The main crystal data are as follows: a=13.550(5) Å, b=9.964(7) Å, c=17.125(8) Å, β=99.52(4)°, V=2280(2) ų, M=1229.45, and space group P2₁/m. Crystals of I have a layered structure: layers consisting of C₆₀ molecules alternate with layers composed of BMDT-TTF and CS₂ molecules. It is found that, in complex I, the donor and C₆₀ molecules are linked through the shortest contacts, which leads to a change in the molecular geometry of BMDT-TTF. The donor molecules in a crystal layer are characterized by the shortest S...S contacts. The IR data indicate the electroneutrality of the fullerene molecule. The electrical conductivity of (BMDT-TTF) · C₆₀ · 2CS₂ single crystals is measured using the four-point probe method at room temperature: σ_RT=2×10^?5 Ω^?1 cm^?1.     

X-ray structure refinement and ionic conductivity of Na6.69Ca3.355(SO4)6Cl0.77F0.63

The structure of Na_6.69Ca_3.355(SO₄)₆Cl_0.77F_0.63, isostructural with fluorapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed a space group P6₃/m with lattice parameters of a?=?9.477 (2) Å, c?=?6.865 (5) Å. Final refinement led to R _F?=?1.83 % and R _B?=?7.64 %. The location of Na⁺ ions in the M (2) sites surrounding the channels was related particularly to the high polarizability of the Ca²⁺. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at σ _500 °C?=?1.03?×?10^?5?S?cm^?1 and E_a?=?0.70 eV.     

The Mössbauer spectrum of synthetic hureaulite: Fe5 2+(H2O)4(PO4H)2(PO4)2

The crystal structure of synthetic ferrous hureaulite, Fe₅ ²⁺ (H₂O)₄(PO₄H)₂(PO₄)₂, was refined from single-crystal X-ray data. It is monoclinic, space group C2/c, with a=17.487(4), b=9.017(2), c=9.338(2) Å, β=96.27(3)°, V=1463.6(6) Å³, Z=4 and D _calc=3.327 g/cm³. This end member of the hureaulite series was crystallized under distinctly acidic conditions, by a method that gives perfect crystals, large enough for X-ray single crystal studies. The main feature of the hureaulite structure is that it has an equal number of normal (PO₄)³⁺ and acid (PO₄H)²⁺ tetradentate groups. These are centered on Fe²⁺ atoms and share corners with edge-linked octahedra, forming pentamer units. The five Fe²⁺ atoms are distributed on three distinct sites in these units. This can be directly observed in the Mössbauer spectrum at 295 K, which contains three doublets whose relative intensities correspond to the 1:2:2 distributions of crystallographic sites.     

Crystal chemistry and physical properties of the ternary compounds RE5B4C5 (RE=Ce,Pr, Nd)

The ternary rare-earth metal boride carbides RE₅B₄C₅ (RE=Ce, Pr, Nd) were prepared by arc melting the mixtures of the pure elements and subsequent annealing at 1270 K. Their crystal structures were determined from single crystal X-ray diffraction data. They crystallize in the Ce₅B₄C₅ type of structure (space group Pna2₁, Z=8). Two new compounds were found, Pr₅B₄C₅: a=24.592(2) Å, b=8.4563(5) Å, c=8.4918(5) Å, R₁=0.043 (wR₂=0.076) for 2871 reflections with I_o?2σ(I_o)); for Nd₅B₄C₅: a=24.301(1) Å, b=8.3126(5) Å, c=8.3545(4) Å, R₁=0.035 (wR₂=0.069) for 3707 reflections with I_o?2σ(I_o)). Its structural arrangement consists of a three-dimensional framework of rare-earth atoms resulting from the stacking of slightly corrugated two-dimensional square nets, leading to voids filled with B₄C₄, B₃C₃, BC₂ finite chains and isolated carbon atoms. Ce₅B₄C₅ is an antiferromagnet at 5 K followed by a metamagnetic transition in elevated external fields. Pr₅B₄C₅ and Nd₅B₄C₅ are ferromagnets below T_C=12 and 15 K, respectively.     

Synthesis of a new magnetic Y2Mn2/3Re4/3O7 with pyrochlore-like structure

A complex oxide of the Y₂Mn_2/3Re_4/3O₇ composition with pyrochlore-like structure and parameters of hexagonal unit cell _a=14.91(1) Å _c=17.53(1) Å was synthesized. The magnetic susceptibility and magnetization measurements showed that below 190 K this oxide possesses spontaneous magnetic moment. In the paramegnetic region, the magnetic susceptibility obeys the Curie-Weiss law χ=C/(T?Θ), with C=2.07 cm³ K mol^?1 and Θ=?160 K, and the effective magnetic moment corresponding to the cationic combination Mn²⁺-Re⁵⁺. The data obtained allow one to assume that the compound has a noncollinear antiferromagnetic structure.     

Crystal structure of and evidence of a lattice distortion in (Me2ø2P)(TCNQ)2

(Dimethyldiphenylphosphonium)⁺(7,7,8,8-tetracyanoquinodimethanide)^?₂ is monoclinic, space group C_c, with a = 32.01(2), b = 6.56(1), $\text{c = 15.72(2)}\text{A}\text{?}$, β = 107.4(8)°. The TCNQ's stack plane-to-plane in columns parallel to b with (i) a mean interplanar spacing of 3.28 Å along the conducting chains and (ii) an exocyclic bond to quinonoid ring overlap of adjacent molecules. The conductivity along b, the needle axis, varies as $\text{σ = σ}{}_0\text{exp}\text{(}\text{?E}{}_{\mathrm{a}}\text{kT}\text{)}$ where σ_{300 K} = 0.05 S cm^?1 and E_a = 0.20 eV (Diethyldiphenylphosphonium)⁺(7,7,8,8-tetracyanoquinodimethanide)^?₂ is similarly monoclinic, space group C_c, with a = 31.48(2), b = 6.51(1), $\text{c = 15.48(2)}\text{A}\text{?}$, β = 104.2(8)°. The conductivity at 300 K and activation energy, both determined along b, are 1–10 S cm^?1 and 0.05 eV respectively. There is evidence of a lattice distortion in the dimethyl analogue only.     

AgTh2(PO4)3 — A new case of the non-hydrogen bonded phosphate ferroelectric

The basic crystallographic data of AgTh₂(PO₄)₃ single crystals have been determined for the first time by means of X-ray diffraction methods. The crystals are monoclinic, space group isCc with four formula units per unit cell. The dimensions of the unit cell are:a=17·385 Å,b=6·815 Å,c=8·148 Å,β=101·10°. Using the Sawyer and Tower method it has been proved that the crystals possess ferroelectric properties. Performing the measurements at room temperature the values of spontaneous polarization and coercive field in the direction normal to (100) face have been determined.     

TSC study of electric dipole relaxations in chlorapatite

Electric dipole relaxations in chlorapatite, Ca₅(PO₄)₃Cl, have been studied with the fractional polarization mode of the thermally stimulated currents (TSC) method. Fifty-one of the fifty-seven sets of data obtained in the range 10–443°K fell naturally into four groups yielding compensation temperatures T_C of T_C1, = 202°C, T_C2: = 202°C, T_C3 = 420°C and T_C4= 644°C, with estimated error < 10°C, and characteristic relaxation times τ_C of τ_C1 = 1.3 × 10^?7s, τ_C2 = 3.2 × 10^?6s, τ_C3 = 8.8 × 10^?5s and τ_C4 = 2.3 × 10^?4s. Atomic-scale physical models involving Cl^? ion motion are offered for the 202°C compensation at the temperature of the reported monoclinic-to-hexagonal phase transition and for the 420°C compensation, at which temperature the Cl^? ions individually are thought to have enough thermal energy to maintain the hexagonal form dynamically.     

Synthesis of BaSO4 nanoparticles by precipitation method using sodium hexa metaphosphate as a stabilizer

We describe the synthesis and structure of Barium sulfate nanoparticles by precipitation method in the presence of water soluble inorganic stabilizing agent, sodium hexametaphosphate, (NaPO₃)₆. The structural parameters were refined by the Rietveld refinement method using powder X-ray diffraction data. Barium sulfate nanoparticles were crystallized in the orthorhombic structure with space group Pbnm (No. 62) having the lattice parameters a=7.215(1) (Å), b=8.949(1) (Å) and c=5.501(1) (Å) respectively. Transmission electron microscopy study reveals that the nanoparticles are size range, 30–50 nm. Fourier transform infrared spectra showed distinct absorption due to the SO₄^2? moiety at 1115 and 1084 cm^?1 indicating formation of barium sulfate nanoparticles free from the phosphate group from the stabilizer used in the synthesis.     

Ferromagnetic ordering in the MMnF6 series (M = Ni,Cu, Zn,Pd)

Neutron diffraction experiments performed on MMnF₆ compounds (M = Ni, Cu, Zn, Pd) have shown that both NiMnF₆ and ZnMnF₆ crystallize in the rhombohedral R$\text{3}$ space group with a cationic ordering, whereas PdMnF₆ shows cationic disordering (R$\text{3}$c, a = 5.46 Å, α = 54.45°). CuMnF₆ has a monoclinic distortion derived from the MnF₃ structural type (a = 8.57 Å, b = 4.85 Å, c = 13.46 Å, β = 92.12°). The magnetic properties can be correlated with the structure: the R$\text{3}$ ordered compounds show a ferromagnetic behavior (T_C(NiMnF₆) = 39 K; T_C(ZnMnF₆) = 9.5 K; T_C(CdMnF₆) = 8 K), while the other two have an antiferromagnetic ordering.     

Synthesis,Crystal Structure,Hirshfeld Surface Analysis,and Physicochemical Study of an Anhydrous Organic Acidic Cyclohexaphosphate

The new organic–inorganic hybrid [5-Cl-2-(CH₃)C₆H₃NH₃]₄H₂P₆O₁₈ has been synthesized by the slow evaporation method. X-ray diffraction on a single crystal shows that this acidic cyclohexaphosphate crystallized in the monoclinic space group C _2/c with a?=?33.89(11) Å, b?=?9.16(16) Å, c?=?13.68(3) Å, β?=?91.35(2)°, V?=?4244.9(19) ų and Z?=?4. ³¹P MAS-NMR and ¹³C CP/MAS-NMR results are in accordance with X-ray findings. Fluorescent study shows the blue photoluminescence. Furthermore, FT-IR analysis was studied and the complete vibrational assignments were done. Intermolecular interactions were analyzed using Hirshfeld surface analysis and the associated 2D fingerprint plots.     

Studies in molecular structure,symmetry and conformation—Part XIV. Crystal and molecular structure of L-isoleucine hydrochloride monohydrate form II

The crystal structure of a new form of L-isoleucine hydrochloride monohydrate C₆H₁₃O₂NHClH₂O (termed form II) has been determined using three-dimensional photographic data. This differs conformationally from the hydrochloride derivative (termed form I, Trommel and Bijvoet 1954) reported earlier. The crystal belongs to the orthorhombic space group P2₁2₁2₁ with cell dimensions,a=5.87±0.01,b=24.77±0.02 andc=6.85±0.01 ? and four molecules per cell,ρ _obs=1.240 g/cm³,ρ _cal=1.238 g/cm³,μ for CuKa=32.6 cm⁻¹. Contribution No. 420 from the Department of Crystallography and Biophysics, University of Madras, Madras 600025.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Conformational and Structural Analysis of 6‐(4‐Methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one

Abstract

The cis stereochemistry of 6‐(4‐methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one was studied by use of a PM3 semi‐empirical quantum mechanical model, and x‐ray crystallographic analysis. It crystallizes in the monoclinic space group P2 ₁ /n with a = 10.812(1) Å, b = 16.464(2) Å, c = 13.379(1) Å, α = 90.00°, β = 98.39(1)°, γ = 90.00°, V = 2356.07(4) Å³, Z = 4, D _calc = 1.3067 g cm^?3, F(0 0 0) = 976.41, and μ = 0.086 mm^?1. The structure was solved by direct methods and refined to R = 0.066 for 1257 independent reflections [I > 4σ (I)]. The results from x‐ray diffraction were seen to be generally consistent with the results from previously reported spectroscopic investigations, beside theoretical calculations, except for conformations of five‐membered fused heterocycles. Two inter‐ and intramolecular weak interactions in addition to carbon atoms (C1 and C3) with different chiralities were found in the structure. The conformational study was performed by randomly scanning the potential energy surface belonging to the title compound with respect to selected torsion angles.     

DFT(B3LYP/LanL2DZ), non-linear optical and electrical studies of a new hybrid compound: [C6H10(NH3)2]CoCl4·H2O

A new organic-inorganic material [C₆H₁₀(NH₃)₂]CoCl₄·H₂O was reported. The title compound was synthesized at room temperature by slow evaporation and then characterized by a single X-ray diffraction, spectroscopic measurements, thermal analysis and dielectric technique. It crystallizes in the non-centrosymmetric space group Pna2₁ with the following unit cell parameters: a=12.5328(1) Å, b=9.0908(1) Å, c=11.7440(1) and α=β=γ=90°. The structure can be described by the alternation of two different cationic-anionic layers. It consists of isolated H₂O, isolated [CoCl₄]²⁻ tetrahedral anions and diammoniumcyclohexane [C₆H₁₀(NH₃)₂]²⁺ cations, which are connected via N–H…Cl, N–H…O and O–H…N hydrogen bonds. The Hirshfeld surface analysis was conducted to investigate intermolecular interactions and associated 2D fingerprint plots, revealing the relative contribution of these interactions in the crystal structure quantitatively. Theoretical calculations were performed using DFT/B3LYP/LanL2DZ method for studying the molecular structure and vibrational spectra and especially to examine the non-linear optical behavior of the compound. Solid state ¹³C NMR spectrum shows three signals correspond to three different carbon environments. Thermal analysis discloses a phase transition at the temperature 315 K and the evaporation of water molecule at 327 K. A detailed dielectric study was reported and shows a good agreement with thermal measurements.     

Crystal Structures of Tetrakis‐(4‐chlorophenylthio)‐butatriene and Tetrakis‐(tert‐butylthio)‐butatriene

Tetrakis‐(4‐chlorophenylthio)‐butatriene (3a) and tetrakis‐(tert‐butylthio)‐butatriene (3b) were synthesized, and their crystal structures were determined. The compound 3a is monoclinic, space group P2₁/c, a=6.9785(8), b=8.6803(9), c=22.884(2) Å, β=93.887(6)^o, V=1383.0(3) ų, Z=2. The compound 3b is monoclinic, space group P2₁/n, a=11.0615(6), b=10.8507(4), c=11.2717(6) Å, β =116.427(2)^o, V=1211.5(1) ų, Z=4. The title compounds 3a and 3b reside on an inversion center so that only half of the molecule is crystallographically unique. Both compounds are not planar. The crystal structures of 3a and 3b have cumulated double bonds. The C7–C8–C8ⁱ and C5–C6–C6ⁱ angles that show the linearity in both structures, respectively, are 176.4(3)° in 3a and 175.6(2)° in 3b.     

The crystal structures of the ion conductors (NH+4)Zr2(PO4)3and (H3O+)Zr2(PO4)3

The crystal structures of (NH⁺₄)Zr₂(PO₄)₃ and (H₃O⁺)Zr₂(PO₄)₃ have been determined from neutron time-of-flight powder diffraction data obtained at 15 K. Both compounds are rhombohedral, $\text{R}\text{3}\text{c}$, with cell parameters a=8.7088(1) and c=24.2197(4) Å for the ammonium compound and a=8.7528(2), c=23.6833(11) Å for the hydronium compound. In both cases the ions are completely localized in the type I cavities and hydrogen bonded to lattice oxygens. The measured unit cell parameters are relatively large for this class of compounds but the entrance ways into the cavities are still too small to allow for unrestricted movement of the ions. Thus the low conductivity of the hydronium ion is related to this and other structural features.