Synthesis and crystal structure of langbeinite related mixed‐metal phosphates K1.822Nd0.822Zr1.178(PO4)3 and K2LuZr(PO4)3

Two potassium lanthanide zirconium orthophosphates with general composition K_1.822Nd_0.822Zr_1.178(PO₄)₃ (KNdZrP) and K₂LuZr(PO₄)₃ (KLuZrP) were prepared using the flux technique. Original synthetic procedure has been examined for the flux growth of the complex phosphates containing zirconium and lanthanide. Both compounds have been synthesized in the complex melts containing at the same time potassium phosphates and transition metal fluorides. The structures were solved from the single crystal (KNdZrP) and powder (KLuZrP) X‐ray diffraction data. Both compounds are isotypic to langbeinite mineral and crystallize in cubic system (sp. gr. P2₁3) with the cell parameters a = 10.3228(2) and a = 10.29668(5) Å respectively. The rigid framework is built up from the isolated [MO₆] octahedra and [PO₄] tetrahedra interlinked via vertices. The potassium cations are located in the large closed cavities of the framework. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal structure of new phosphate NaFe 4 2+ Fe 3 3+ [PO4]6

New sodium iron orthophosphate NaFe ₄ ²⁺ Fe ₃ ³⁺ [PO₄]₆ was synthesized by the hydrothermal method. The crystal structure (sp. gr. $P\bar 1$ ) was established by the heavy-atom method, with the exact chemical formula of the compound being unknown; R _hkl = 0.0492, R _whkl = 0.0544, S = 0.52. The new compound is analogous to iron phosphate Fe ₃ ²⁺ Fe ₄ ³⁺ [PO₄]₆ studied earlier. However, these two compounds differ in the Fe²⁺ and Fe³⁺ contents, because Na⁺ ions in the new compound are located at the centers of symmetry not occupied earlier.     

Synthesis and crystal structure characterization of (E)-2,2,2-Trifluoro-N-[2-(2-nitrovinyl)phenyl]acetamide

The title compound, (E)-2,2,2-trifluoro-N-[2-(2-nitrovinyl)phenyl]acetamide, was synthesized and characterized by ¹H and ¹³C NMR and HRMS spectroscopy. Its molecular configuration was investigated by X-ray crystallography. The crystal structure analysis revealed that the structure exhibits intermolecular hydrogen bonds of the type N–H…O and intermolecular hydrogen bonds of the type N–H…F, and molecules are linked by weak C–H…O contacts. Furthermore, the two oxygen atoms of nitro group are disordered over two positions, respectively, with site occupancy factors of 0.8:0.2 and 0.6:0.4. Three fluorine atoms are also disordered over two positions, respectively, one fluorine atom with site occupancy factors of 0.6:0.4 and the other two fluorine atoms with site occupancy factors of 0.5:0.5.     

Synthesis and structure of iron zirconium phosphate Fe1/3[Zr2(PO4)3]

Iron zirconium phosphate Fe_1/3 [Zr₂(PO₄)₃] is synthesized by heat treatment of gels with the stoichiometric composition of components. The compound prepared is characterized using electron probe microanalysis, X-ray diffraction, and IR spectroscopy. The crystal structure of the Fe_1/3[Zr₂(PO₄)₃] phosphate is refined in space group P2₁/n by the Rietveld method in the isotropic approximation for atomic displacements of all elements.     

New phosphate Fe0.5Nb1.5(PO4)3 with an electrically neutral framework. Synthesis and crystal structure

A new iron-niobium phosphate, Fe_0.5Nb_1.5(PO₄)₃, has been prepared and studied by X-ray diffraction, electron microprobe analysis, IR spectroscopy, and neutron powder diffraction. On the basis of X-ray powder data, it was found that the synthesized phosphate crystallizes into the sp. gr. R $\bar 3$ c and corresponds to the structural type of sodium-zirconium phosphate NaZr₂(PO₄)₃. The structure was refined by the Rietveld method based on a powder neutron diffraction experiment. The obtained phosphate belongs to complex niobium orthophosphates and has a framework structure with a zero framework charge.     

Synthesis and crystal structure of novel complex phosphate Li5Cu2Al(PO4)4

A new complex phosphate Li₅Cu₂Al(PO₄)₄ has been obtained by the flux method in the Cs-Li-Cu-V-P-O system. Its crystal structure has been determined by X-ray diffraction (R ₁ = 2.74%) to be as follows: sp. gr. $P\bar 1$ , a = 4.860(5) Å, b = 7.788(5) Å, c = 8.324(5) Å, α = 69.542(5)°, β = 90.016(5)°, γ = 75.318(5)°, Z = 1, and V = 284.2(4) ų. The compound under study has a dense structure and a three-dimensional framework build up of [LiO₅], [AlO₆], [Cu/LiO₅], and [CuO₄] polyhedra and [PO₄] tetrahedra. A comparative crystal-chemical analysis of two isotypic compounds with a general formula Li₅Cu₂ M(PO₄)₄ (M = Fe, Al) has been performed. Topological relations between the Na₂Mg₅(PO₄)₄ and Li₅Cu₂ M(PO₄)₄ crystal structures, which are characterized by different cationic compositions, are revealed.     

Studies on a new Rb3H9(PO4)4 crystal

A new type of trirubidium nonahydrogen tetraphosphate, Rb₃H₉(PO₄)₄, crystal has been crystallized. Differential scanning calorimetry (DSC) and X‐ray diffraction measurements have been performed on the title compound. The crystal does not undergo any structural phase transition in the temperature range from 120 to 440 K except a melting transition at 399 K. The compound belongs to a monoclinic system with space group C2/c at room temperature. The structure is built on a framework of PO₄ tetrahedra linked by five types of OH‐O hydrogen bonds in the length range from 2.472(4) to 2.679(4) Å. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mixed tetrahedral anionic framework in the K3Ga2(PO4)3 crystal structure

The crystal structure of a new synthetic potassium gallophosphate K₃Ga₂(PO₄)₃ grown from a solution in the melt of a mixture of GaPO₄ and K₂MoO₄ is determined using X-ray diffraction (Bruker Smart diffractometer, 2θ_max= 56.6°, R = 0.044 for 2931 reflections, T = 100 K). The main crystal data are as follows: a = 8.661(2) Å, b = 17.002(4) Å, c = 8.386(2) Å, space group Pna2₁, Z= 4, and ρ_calcd = 2.91 g/cm³. The synthesized crystals represent the third phase in the structure type previously established for the K₃Al₂[(As,P)O₄]₃ compound. It is shown that the structure consists of a three-dimensional anionic microporous tetrahedral framework of the mixed type, which is formed by PO₄ and GaO₄ tetrahedra shared by vertices. Large-sized cations K⁺ occupy channels of the zeolite-like framework. The crystal chemical features of the formation of structure types of compounds with mixed frameworks described by the general formula A ₃ ⁺ M ₂ ³⁺ (TO₄)₃ (where A = K, Rb, (NH₄), Tl; M = Al, Ga, Fe, Sc, Yb; T = P, As) are analyzed.     

Synthesis,characterization, crystal structure and NLO properties of a new mixed crystal potassium sodium ammonium dihydrogenphosphate K0.23Na0.23(NH4)0.54H2PO4

Potassium sodium ammonium dihydrogenphosphate K_0.23Na_0.23(NH₄)_0.54H₂PO₄ (KSADP), a new mixed crystal has been grown in aqueous medium by the slow evaporation of equimolar mixture of ammonium dihydrogenphosphate (ADP), potassium dihydrogenphosphate (KDP) and sodium dihydrogenphosphate (SDP). Crystal composition as determined by single crystal X-ray diffraction analysis reveals that it belongs to the tetragonal system with noncentrosymmetric space group I-42d and it is structurally similar to ADP with cell parameter values, a=7.4794(4) Å; b=7.4794(4) Å; c=7.2974(11) Å; υ=408.23(7) Å³; z=4. The presence of sodium and potassium in ADP matrix was confirmed by inductively coupled plasma emission spectrometry and energy dispersive X-ray spectroscopy. The partial cationic substitution results in defect centers influencing the physical properties. Slight shifts in vibrational patterns could be attributed to strains in the lattice. Refinement of structure by single crystal XRD analysis reveals that potassium, sodium and ammonium coexist in the mixed crystal. The surface morphology of the as-grown specimen, which is changed as a result of cationic incorporation, was studied by scanning electron microscopy. The relative second harmonic generation (SHG) efficiency measurements revealed that the mixed crystal has a superior NLO activity than ADP.     

Synthesis and crystal structure of 2-anilino-6<Emphasis Type="Italic">H</Emphasis>-5-(1-phenyl-3-methyl-5-pyrazolone-4-ylene)-1,3,4-thiadiazine

A novel pyrazolone derivative 2-anilino-6H-5-(1-phenyl-3-methyl-5-pyrazolone-4-ylene)-1,3,4-thiadiazine (PMCP-PTSC) containing NNS hexa-atomic heterocycle has been obtained and characterized by means of single crystal X-ray diffraction, IR and ¹H NMR spectroscopies. It is interesting that when grown from two different solvents, two different crystalline structures are formed. The monoclinic crystal A belongs to a P2₁/c space group. The unit cell parameters are a = 16.414(4) Å, b = 12.530(3) Å, c = 8.432(1) Å, = 91.75(2) Å, and Z = 4. The triclinic crystal B belongs to a P space group. The unit cell parameters are a = 11.386(2) Å, b = 12.326(2) Å, c = 12.411(3) Å, = 83.07(1)°, = 87.76(2)°, = 86.52(2)°, and Z = 4. The structure analyses show the title compound is the keto-form. Dimers in crystal packing of A and supramolecular one-dimensional (B) concatenate structures were assembled by the intermolecular hydrogen bonds.     

Synthesis and crystal structure of new double indium phosphates M 3 I In(PO4)2 (M I = K and Rb)

Double potassium indium and rubidium indium phosphates K₃In(PO₄)₂ (I) and Rb₃In(PO₄)₂ (II) are synthesized by solid-phase sintering at T = 900°C. The compounds prepared are characterized by X-ray powder diffraction (I and II), X-ray single-crystal diffraction (II), and laser-radiation second harmonic generation. Structure I is solved using the Patterson function and refined by the Rietveld method. Both compounds crystallize in the monoclinic crystal system. For crystals I, the unit cell parameters are as follows: a = 15.6411(1) Å, b = 11.1909(1) Å, c = 9.6981(1) Å, β = 90.119(1)°, space group C2/c, R _p = 4.02%, and R _wp = 5.25%. For crystals II, the unit cell parameters are as follows: a = 9.965(2) Å, b = 11.612(2) Å, c = 15.902(3) Å, β = 90.30(3)°, space group P2₁/n, R ₁ = 4.43%, and wR ₂ = 10.76%. Structures I and II exhibit a similar topology of the networks which are built up of { In[PO₄]₂} (I) and { In₂[PO₄]₄} (II) structural units.     

Synthesis, crystal structure, and molecular modeling (AM1) of Methyl 6-chloro-4-(2-chlorophenyl)-5-formyl-2-methyl-1, 4-dihydropyridine-3-carboxylate

The synthesis and structural characterization of Methyl 6-chloro-4-(2-chlorophenyl)-5-formyl-2-methyl-1,4-dihydropyridine-3-carboxylate is described. The structure was refined to R₁ = 0.0470 for 2665 reflections (with I > 2(I)). Crystal data: C₁₅H₁₃C₁₂NO₃, monoclinic,space group P2₁/c, a = 11.163(9), b = 14.484(8), c = 9.422(7) Å, V = 1512.9(19) ų, Z = 4. The results of crystallographic and molecular modeling (AM1) were compared. The Cl atom attached to the phenyl group has two possible orientations, having 75% (sp) and 25% (ap) occupancy, respectively. The molecules in the crystal are held together by means of intermolecular hydrogen bonds of the type N=H...O and by C=H...O interactions.     

Phase transitions in Cs5(HSO4)2(H2PO4)3 crystal

The symmetry (sp. gr.I $\bar 4$ 3d) and lattice parameters have been determined for the first time for Cs₅(H₂SO₄)₂(H₂PO₄)₃ crystals in the temperature range from 172 to 390 K. The thermal and optical properties of crystals, as well as their conductivity, have been investigated at elevated temperatures. It is shown that a crystal heated to T = 365 K undergoes a phase transition with symmetry lowering to the tetragonal phase (with the parameters a = 4.965(1) Å and c = 5.016(1) Å), while at T ≈ 390 K a phase transition to the cubic phase is presumably observed. With a decrease in temperature, a phase transition without a change in symmetry occurs at T = 240 K.     

Synthesis and crystal structures of lithium polyphosphates, LiPO3, Li4H(PO3)5, and LiMn(PO3)3

Polyphosphates of the compositions LiPO₃, Li₄H(PO₃)₅, and LiMn(PO₃)₃ were prepared by the reactions of Li₂CO₃ and MnO₂ with melts of polyphosphoric acids at 240–350°C, and their crystal structures were established. The unit-cell parameters are a = 13.074 Å, b = 5.4068 Å, c = 16.452 Å, β = 99.00°, sp. gr. P2/n; a = 6.6434 Å, b = 7.253 Å, c = 11.399 Å, α = 72.60°, β = 83.36°, γ = 85.32°, sp. gr.; $P\bar 1$ ; a = 8.364 Å, b = 8.561 Å, c = 8.6600 Å, sp. gr. P2₁2₁2₁, respectively. The influence of cations on the structures of the compounds is discussed.     

Synthesis and crystal structure elucidation of 1-(4-fluorobenzyl)-2-(4-cyanophenyl)-1H- benzimidazole-5-carbonitrile

The synthesis and spectral identification of 1-(4-fluorobenzyl)-2-(4-cyanophenyl)-1H-benzimidazole-5-carbonitrile (1) have been reported. IR, ¹H NMR, and EI mass spectral analysis were used for its spectral identification. The structure of 1 was confirmed by X-ray crystallographic studies. Intramolecular hydrogen bond occurs between the imidazole nitrogen and one of hydrogen of the florobenzene. The crystal packing is governed by C–HN intermolecular hydrogen bonds. The molecular structure observed in crystal and the optimised geometries at the HF level by doing semi-empirical and ab initio calculations were compared.     

Diaquabis(5-methoxyindole-2-carboxylato)bis(3-picoline)nickel(II) Complex: Synthesis,Characterization, XRD,TGA, DFT and HSA

A new complex of diaquabis(5-methoxyindole-2-carboxylato)bis(3-picoline)nickel(II) (Ni(5-MeOI2CA)₂(3-pic)₂(H₂O)₂), was synthesized for the first time and characterized by elemental analysis, FT-IR and electronic spectroscopy (UV-Vis) and single-crystal X-ray diffraction (XRD) techniques. The thermal degradation of the Ni(II) complex was investigated using thermogravimetric and differential thermal analyses techniques in oxygen atmosphere. The molecular structure of the complex was determined by single crystal X-ray diffraction technique. Hirshfeld surface analysis (HSA) investigated the packing modes and intermolecular interactions in molecular crystals, as they provide a visual picture of intermolecular interactions. In addition, all computational studies at B3LYP/6-311++G(d,p) were carried out for theoretical characterization of Ni(II) complex. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP/6-311++G(d,p) was a successful choice for title compound. After a successful optimization, FMOs, chemical activity, non-linear optical properties (NLO), molecular electrostatic potential (MEP), Mulliken population (MPA), natural population analyses (NPA), Fukui function analysis (FFA) and natural bond orbital analysis (NBO), which could not obtained by experimental ways, were calculated and investigated. The computed of net charges and chemical activity studies which helped to identifying the electrophilic/nucleophilic nature.     

Synthesis, characterization, and crystal structure of 1-(4-chloro-benzoyl)-3-naphthalen-1-yl-thiourea

1-(4-Chloro-benzoyl)-3-naphthalen-1-yl-thiourea has been synthesized and characterized by elemental analysis, IR spectroscopy, and mass spectrometry. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1, with a = 6.962(1) Å, b = 10.770(3) Å, c = 11.738(2) Å, = 65.76(2)°, = 80.03(1)°, = 84.86(2)°, and D _calc= 1.432 g cm^–1 for Z = 2. The thermal behavior of the compound has been studied by DTA and TG. The antibacterial activities of the title compound were investigated for three Gram (+) and two Gram (–) bacteria by employing broth microdilution method and subsequently, inhibitory activity against yeast-like fungi was also determined.     

Synthesis and crystal structures of nitratocobaltates Na2[Co(NO3)4], K2[Co(NO3)4], and Ag[Co(NO3)3] and potassium nitratonickelate K2[Ni(NO3)4]

The cobalt(II) and nickel(II) nitrate complexes with an island structure (Na₂[Co(NO₃)₄] (I) and K₂[Co(NO₃)₄] (II)] and a chain structure [Ag[Co(NO₃)₃] (III) and K₂[Ni(NO₃)₄] (IV)] are synthesized and investigated using X-ray diffraction. In the anionic complex [Co(NO₃)₄]^2? of the crystal structure of compound I, the Co coordination polyhedron is a twisted tetragonal prism formed by the O atoms of four asymmetric bidentate nitrate groups. In the anion [Co(NO₃)₄]^2? of the crystal structure of compound II, one of the four NO₃ groups is monodentate and the other NO₃ groups are bidentate (the coordination number of the cobalt atom is equal to seven, and the cobalt coordination polyhedron is a monocapped trigonal prism). The crystal structures of compounds III and IV contain infinite chains of the compositions [Co(NO₃)₂(NO₃)_2/2]^? and [Ni(NO₃)₃(NO₃)_2/2]^2?, respectively. In the crystal structure of compound III, seven oxygen atoms of one monodentate and three bidentate nitrate groups form a dodecahedron with an unoccupied vertex of the A type around the Co atom. In the crystal structure of compound IV, the octahedral polyhedron of the Ni atom is formed by five nitrate groups, one of which is terminal bidentate. The data on the structure of Co(II) coordination polyhedra in the known nitratocobaltates are generalized.     

Synthesis and crystal structure of (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate

The reaction between 1-phenylsulphenyl-2-phenylethyne and p-toluenesulfonic acid in methylene chloride gives (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate (1) in good yields. This reaction is both a regio- and a stereospecific cis addition, confirmed by X-ray crystal structure analysis of the title compound. 1 crystallizes in the monoclinic space group P2₁/n with the lattice parameters a = 10.556(3), b = 9.730(3), c = 19.687(3) Å, = 105.05(2)°, V = 1952.7(8) ų, and Z = 4. The results of elemental analysis, IR and NMR spectroscopy are included.     

Hole defects in the crystal structure of synthetic lipscombite (Fe 4.7 3+ Fe 2.3 2+ )[PO4]4O2.7(OH)1.3 and genetic crystal chemistry of minerals of the lipscombite-barbosalite series

The crystal structure of a synthetic analog of the mineral lipscombite (Fe _2.3 ²⁺ Fe _4.7 ³⁺ )[PO₄]₄O_2.7(OH)_1.3 obtained under hydrothermal conditions in the LiF-Fe₂O₃-(NH₄)₂HPO₄-H₂O system is resolved (R = 0.040) by X-ray diffraction analysis (Bruker Smart diffractometer with a highly sensitive CCD detector, MoK _α radiation): a = 14.776(3) Å, b = 14.959(3) Å, c = 7.394(1) Å, β = 119.188(4)°, sp. gr. C2/c, Z = 4, ρ_exp = 3.8 g/cm³, ρ_calcd = 3.9 g/cm³. Fe²⁺ and Fe³⁺ cations are statistically distributed in each of four crystallographically independent positions, while occupying the corresponding octahedra with probabilities of 60, 90, 100, and 91%. The ratio Fe²⁺/Fe³⁺ in the composition of the crystals was established by Mössbauer spectroscopy. Lipscombite is interpreted as a mineral of variable composition described by the formula (Fe _x ²⁺ Fe _n?x ³⁺ )[PO₄]₄O_y(OH)_4?y . The field of stability is determined as a function of the iron content and the ratio Fe²⁺/Fe³⁺. It is shown that at n = 6 iron cations are ordered in octahedra and barbosalite structure is formed. An interpretation of genetically and structurally related members of the lipscombite family within a unified polysomatic series is proposed.