Synthesis and Crystal Structure of (PzCH<Subscript>2</Subscript>CHOHCH<Subscript>2</Subscript>PzH)·(Ph<Subscript>2</Subscript>SnCl<Subscript>3</Subscript>) (Pz = 3,5-dimethylpyrazol-1-yl)

Abstract  

Reaction of Ph₂SnCl₂ with 1,3-bis(3,5-dimethylpyrazol-1-yl)-2-propanol (L) in a 1:1 ratio yields L(SnPh₂Cl₂)₂ adduct, which partly hydrolyzes to the title complex (C₂₅H₃₁Cl₃N₄OSn, Mr = 628.58) during crystal growing in the air. The title complex is of monoclinic, space group P2₁/n with a = 9.0338(9), b = 17.890(1), c = 17.340(1) ?, β = 95.533(1)^o, V = 2798.9(5) ?³, Z = 4, Dc = 1.492 Mg/m³, λ(MoKα) = 0.71073 ?, μ = 1.224 mm⁻¹, F(000) = 1272, R = 0.023, wR = 0.054 for 4212 observed reflections with I ≥ 2σ(I). The crystal structure indicates that there is no direct interaction between the pyrazolyl ligand and the tin atom, but this complex forms a supramolecular structure through weak intermolecular C–H⋯Cl and O–H⋯Cl hydrogen bonds.     

Structural Studies of the Isomorphous MCl<Subscript>2</Subscript>(PMe<Subscript>3</Subscript>)<Subscript>4</Subscript> (M = Mo,W) Complexes

Abstract  

The structure of WCl₂(PMe₃)₄ has been determined in order to allow for a comparison with its molybdenum analogue. The complexes are isomorphous, and exhibit trans-pseudooctahedral coordination, with crystallographically imposed [`4]2m\overline{4}2m (D<sub>2d</sub>) symmetry. A significant distortion occurs involving the PMe<sub>3</sub> ligands, through which one opposing pair tilts upward toward one axial chloride ligand, while the other pair tilts in an opposite manner, by 9.33°. The complex crystallizes in the tetragonal space group I[`4]2mI\overline{4}2m, with a = b = 9.4987(4) ?, c = 12.1058(5) ?, V = 1092.25(8) ?³, D _calc = 1.700 at 150(1) K. For a better comparison, the structure of the molybdenum complex was redetermined, at a low temperature. Its space group is also I[`4]2mI\overline{4}2m with a = b = 9.5193(3) ?, c = 12.1083(5) ?, V = 1097.22 ?³, D _calc = 1.426 at 150(1) K. In accord with the larger cell volume, the molybdenum complex possesses slightly longer M–Cl and M–P bonds.     

Synthesis and structure of [(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>CSSC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>[OsBr<Subscript>6</Subscript>]Br<Subscript>2</Subscript> · 3H<Subscript>2</Subscript>O

The complex [(NH₂)₂CSSC(NH₂)₂]₂[OsBr₆]Br₂ · 3H₂O is synthesized by the reaction of K₂OsBr₆ with thiocarbamide in concentrated HBr and characterized using electronic absorption and IR absorption spectroscopy. Its crystal structure is determined by X-ray diffraction. The crystals are orthorhombic, a = 11.730(2) Å, b = 14.052(3) Å, c = 16.994(3) Å, space group Cmcm, and Z = 4. The [OsBr₆]^2? anionic complex has an octahedral structure. The Os-Br distances fall in the range 2.483–2.490 Å. The α,α′-dithiobisformamidinium cation is a product of the oxidation of thiocarbamide. The S-S and C-S distances are 2.016 and 1.784 Å, respectively. The H₂O molecules, Br^?ions, and NH₂ groups of the cation are linked by hydrogen bonds.     

Synthesis and Crystal Structure of a Novel Double-Chain Coordination Polymer [Zn<Subscript>2</Subscript>(bipy)<Subscript>2</Subscript>(btec)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>n</Subscript> (bipy = 2,2′-bipyridine; btec = 1,2,4,5-benzenetetracarboxylate)

Abstract  A novel aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. Compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.7449(6) ?, b = 8.9286(8) ?, c = 10.7422(8) ?, α = 80.95(1)°, β = 70.21(1)°, γ = 78.14(1)°, V = 680.93(10) ?³, Z = 2. The coordination geometry of Zn(II) atom is distorted trigonal bipyramidal with two nitrogen atoms of one 2,2′-bipy group, two oxygen atoms from two different btec ligands, and one water. The 16-membered rings are alternately arranged forming an infinite 1-D double-chain structure. A 3-D network was constructed by interlayer C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state. Graphical Abstract  A 1-D double-chain aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. A 3-D network was constructed by intermolecular C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state.      

Synthesis and Crystal Structure of [Na(H<Subscript>2</Subscript>O)<Subscript>1.5</Subscript>][Na(H<Subscript>2</Subscript>O)<Subscript>3.5</Subscript>] X<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O (X = 4′-Methoxy-7-Hydroxyisoflavone-3′-Sulfonate)

Abstract  

Water-soluble derivative of formononetin, [Na(H₂O)_1.5][Na(H₂O)_3.5] X₂·2H₂O(X = 4′-methoxy-7-hydroxyisoflavone-3′-sulfonate) was synthesized by sulfonation reaction. It was characterized by IR, ¹H NMR and single-crystal X-ray diffraction analysis. Single-crystal X-ray diffraction analysis showed that the title compound crystallized in a triclinic space group P-1 with cell parameters a = 6.9642(15) ?, b = 13.343(3) ?, c = 20.634(5) ?, α = 107.115(3)˚, β = 93.121(4)˚, γ = 91.911(3)˚, V = 1827.3(7) ?⁻³, D _c  = 1.575 Mg m ⁻³, Z = 2. There are two conformers of 4′-methoxy-7-hydroxyisoflavone-3′-sulfonate anions, two kinds of sodium cations, five coordinated water molecules and two lattice water molecules in the crystal structure. The sodium atoms coordinated with the oxygen atoms from water molecules, hydroxyl groups and sulfo-groups to form a Na–O coordinated network. Aromatic π···π stacking interactions and hydrogen bonding existed in the crystal structure of title compound, which together with coordinated interactions and electrostatic interactions between sodium cations and anions sulfonates C₁₆H₁₀O₄SO₃ ⁻ lead to the moieties into a three-dimensional network.     

Crystal Structure and Characterization of [Ni(RPOEt)<Subscript>2</Subscript>(C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH)<Subscript>2</Subscript>](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript> [RPOEt = bis{(diphenylphosphinyl)methyl}ethyl phosphinate]

Abstract  

The compound [Ni(RPOEt)₂(C₂H₅OH)₂](ClO₄)₂ (1) [RPOEt = bis{(diphenylphosphinyl)methyl}ethyl phosphinate] has been prepared in the form of single crystals and characterized by elemental and thermal analyses, IR spectroscopy and by a single crystal X-ray diffraction study. The complex crystallizes in the triclinic P[`1] P\bar{1} space group with a = 9.8773(5), b = 13.741(1), c = 14.287(1) ?, α = 64.313(9), β = 70.280(5), γ = 89.973(7)o, V = 1620.5(2) ?³, and Z = 1. The nickel(II) atom in 1, situated at the centre of symmetry, is coordinated by four oxygen atoms from two RPOEt ligands and two oxygen atoms from two ethanol molecules in a slightly distorted octahedral environment. The third phosphoryl-oxygen atom from the phosphinate ligand is hydrogen bonded to the oxygen atom of the ethanol molecule coordinated to nickel(II). The complex [Ni(RPOEt)₂(C₂H₅OH)₂]²⁺ cations are linked by the C–H···O hydrogen bonds into one-dimensional chains and by the composite π···π and C–H···π phenyl interactions into a final three-dimensional structure.     

Crystal and molecular structure of phenanthrolinium peroxodisulfate dihydrate (C<Subscript>12</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>8</Subscript> · 2H<Subscript>2</Subscript>O

The crystal structure of (HPhen)₂S₂O₈ · 2H₂O is studied using X-ray diffraction. The crystals are monoclinic, a = 23.716(5) Å, b = 10.220(2) Å, c = 13.103(3) Å, β = 128.03(2)°, V = 2501.6(9) ų, Z = 4, space group C2/c, and R = 0.0745 for 1579 reflections with I > 2σ(I). The crystal is built of S₂O ₈ ^2? centrosymmetric anions, HPhen ⁺ cations, and molecules of crystallization water. Hydrogen bonds link the structural units into chains. Within a chain, stacking interactions are observed between the phenanthroline rings (the interplanar spacing between the rings is 3.8 Å, and the dihedral angle between their planes is 8°). The data of IR spectroscopy confirm the formation of the N(Phen)-H bond.     

The Crystal Structures of Bis(2-amino-5-methylpyridinium) Tetrabromometallate(II): Intermolecular Interactions in (C<Subscript>6</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>[MBr<Subscript>4</Subscript>]; M = Cd and Co

Abstract The crystallization and structures of a triclinic (henceforth T) (C₆H₉N₂)₂[CdBr₄] and a monoclinic (henceforth M) of (C₆H₉N₂)₂[CoBr₄] are reported. The crystal packing of both solids is analyzed and compared: both contain parallel chains of cations and stacks of anions. In both T and M, each [MBr₄]²⁻ is hydrogen bonded non-symmetrically to surrounding cations in a ladder chains that run along b axis, with planar cations in both structures falling in parallel to the planes to anions. In T the cation chains are further involved in classical π···π stacking, while in M the cation chains show less significant stacking, with longer repeat distance. Index Abstract Extensive N–H···Br hydrogen bonds link both anions and cations into chains of the ladder type parallel to the crystallographic b axis. The crystal structures of bis(2-amino-5-methylpyridinium) tetrabromometallate(II): Intermolecular interactions in (C6H9N2)2[MBr4]; M = Cd and Co Rawhi Al-Far and Basem Fares Ali      

Anisotropy of microhardness and fracture of (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>Ni(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O (ANSH) crystals

The Vickers hardness of the (010) and (001) planes in (NH₄)₂Ni(SO₄)₂ · 6H₂O (ANSH) crystals has been measured. Anisotropy hardness of the first kind is revealed for the (010) plane in ANSH. The hardness anisotropy coefficient k ₂ was determined to be 1.5. The temperature dependence of the microhardness of the (001) face of ANSH crystals was investigated in the temperature range from 20 to 80°C. The character of fracture of the (100), (010), and (001) planes during indentation with a spherical indenter has been qualitatively determined.     

X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(CrO<Subscript>4</Subscript>)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 4H<Subscript>2</Subscript>O

The compound Rb₂[(UO₂)₂(CrO₄)₃(H₂O)₂] · 4H₂O was studied by X-ray diffraction. The crystals are monoclinic, a = 10.695(2) Å, b = 14.684(3) Å, c = 14.125(3) Å, β = 108.396(4)°, sp. gr. P2₁/c, Z = 4, V = 2104.9(7) ų, and R = 0.0491. The main structural units are layers consisting of [(UO₂)₂(CrO₄)₃(H₂O)₂]^2? anions belonging to the crystal-chemical group A ₂ T ₂ ³ B ²M ₂ ¹ (A = UL ₂ ²⁺ , T ³ and B ² are CrO ₄ ^2? , and M ¹ is H₂O) of uranyl complexes. The uranium-containing layered groups are held together by electrostatic interactions with rubidium cations, as well as by hydrogen bonds with the participation of inner- and outer-sphere water molecules.     

AErP<Subscript>2</Subscript>O<Subscript>7</Subscript> (A = Rb,Cs) and HEuP<Subscript>2</Subscript>O<Subscript>7</Subscript>·3H<Subscript>2</Subscript>O: Crystal Structures,Vibrational Studies and Thermal Behaviours

Abstract  

New diphosphates AErP₂O₇, A = Rb (1), Cs (2), and HEuP₂O₇·3H₂O (3) have been prepared via soft chemistry route from evaporation of aqueous solution. Their crystal structures have been solved by single crystal diffraction data. The compounds (1) and (2) crystallize in the monoclinic space group P2₁/c with the following unit cell dimensions: (1) a = 7.7248(4) ?, b = 10.9342(6) ?, c = 8.6716(3) ?, β = 105.434(4)° and Z = 4; (2) a = 7.9192(4) ?, b = 10.8606(4) ?, c = 8.7684(5) ?, β = 104.317(5)° and Z = 4. Compound (3) crystallises in the triclinic space group P − 1, with the unit cell parameters: a = 6.4036(5) ?, b = 6.8753(6) ?, c = 9.7964(8) ?, α = 81.706(7)°, β = 80.218(7)°, γ = 88.381(7)°. Crystal structure of (1) and (2) consists of 3D open framework built from [ErO₆] octahedra sharing corners with [P₂O₇] units, leading to the formation of channels running along c direction in which A⁺ [A = Rb(1), Cs(2)] ions are located. The compound (3), on the other hand, exhibits a lamellar structure, in which edge-sharing polyhedra of eightfold coordinated europium form chains along [010]. These chains are joined in turn to each others using diphosphates bridges. A network of O–H···O hydrogen bonds reinforces the cohesion of the structure of (3). The diphosphate groups in (1), (2) and (3) adopts an eclipsed configuration. IR and Raman spectra of the three new phosphates show usual signals related to the P₂O₇ diphosphate group and the water molecule. TG and DTA studies were carried out on crystals of (3). The data are correlated to the crystal structures ones.     

Pseudosymmetry in Cr(urea)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>·3NO<Subscript>3</Subscript>

Abstract  

The low temperature crystal structure of the complex, Cr(urea)₄(H₂O)₂·3NO₃ (1), displays intriguing pseudosymmetry that complicates the structure determination. 1 crystallises in the centrosymmetric monoclinic space group P2₁/c with Z = 8 and Z′ = 2; a = 18.3338(4) ?, b = 16.5472(4) ?, c = 13.9252(3) ? and β = 106.3260(10)°, V = 4054.19(16) ?³. The two symmetry independent [Cr(urea)₄(H₂O)₂]³⁺ ions in the asymmetric unit both feature coordinated urea (O=C(NH₂)₂) and lie on general positions. A further six independent nitrate anions complete the structure. The unit cell is primitive but the two Cr³⁺ ions are related by a pseudo translation of ?, ?, 0. The deviation from a truly C-centred cell is clear from an examination of geometry of the urea ligands and the hydrogen bonds which they form. The identification of the space group in this case is described and methods for quantifying the degree of deviation from a C-centred cell discussed.     

Crystal structure of byelorussite-(Ce) NaMnBa<Subscript>2</Subscript>Ce<Subscript>2</Subscript>(TiO)<Subscript>2</Subscript>[Si<Subscript>4</Subscript>O<Subscript>12</Subscript>]<Subscript>2</Subscript>(F,OH) · H<Subscript>2</Subscript>O

The crystal structure of the mineral byelorussite-(Ce) NaMnBa₂Ce₂Ti₂Si₈O₂₆(F,OH) · H₂O belonging to the joaquinite group was solved and refined to R = 0.033 based on 4813 reflections with I > σ2(I). The parameters of the orthorhombic unit cell are a = 22.301(4) Å, b = 10.514(2) Å, c = 9.669(2) Å, V = 2267.1(8) ų, sp. gr. Ama2, and Z = 4. The structure is composed of three-layer sheets, which consist of dimers of edge-sharing Ti octahedra located between isolated four-membered [Si₄O₂] rings. The sheets are linked to each other by Mn 5-vertex polyhedra to form a heteropolyhedral framework. Large cavities in the framework are occupied by Na 6-vertex polyhedra, Ba 11-vertex polyhedra, and REE 9-vertex polyhedra.     

Synthesis,Crystal Structure and NLO Properties of a Mixed Crystal K<Subscript>1−x</Subscript>(NH<Subscript>4</Subscript>)<Subscript>x</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> (x = 0.5)

Abstract  

A new mixed crystal K_1−x(NH₄)_xH₂PO₄ (KADP) of ammonium dihydrogen phosphate (ADP) of ADP–KCl system has been synthesized with x = 0.5 by slow evaporation of the mixture of equimolar aqueous solution at room temperature. Crystal composition 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 crystals with the following parameters: a = 7.418(3) ?; c = 7.2284(6) ?; v = 404.63(4) ?³; z = 4. The substitution results in defect centers which influence the physical properties. Mixed crystal has a superior NLO activity, twice that of KH₂PO₄ (KDP), a well known NLO material and the enhanced NLO activity is rationalized. The structural analysis of KADP and the influence of partial cationic substitution in ADP by K⁺ ions on the NLO properties are reported.     

Synthesis and X-ray diffraction study of [UO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2C<Subscript>12</Subscript>H<Subscript>18</Subscript>O

The compound [UO₂(NO₃)₂(H₂O)₂] · 2C₁₂H₁₈O was synthesized and studied by IR spectroscopy and X-ray diffraction. The structure consists of the neutral island groups [UO₂(NO₃)₂(H₂O)₂], which belong to the crystal-chemical group AB ⁰¹ ₂ M ¹ ₂ (A = UO₂ ²⁺, B ⁰¹ = NO₃⁻, M ¹ = H₂O) of uranyl complexes, and 1-adamantyl methyl ketone molecules. The characteristic features of the association of the complexes [UO₂(NO₃)₂(H₂O)₂] and 1-adamantyl methyl ketone molecules in the crystal structure via hydrogen bonds are considered with the use of Voronoi-Dirichlet polyhedra.     

Crystal structure of the solid solution NH<Subscript>4</Subscript>Al<Subscript>0.62</Subscript>Cr<Subscript>0.38</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 12H<Subscript>2</Subscript>O

The solid solution NH₄Al_0.62Cr_0.38(SO₄)₂ · 12H₂O was studied by X-ray diffraction. The crystal structure was determined in a series of the maximal subgroups Pa3? > R3? > P1? > P1. Reflections forbidden in sp. gr. Pa3? are indicative of symmetry lower than cubic. In the centrosymmetric models under consideration, all sulfate groups are oppositely oriented with respect to each other. In non-centrosymmetric sp. gr. P1, four of the eight sulfate groups have the same orientation, whereas the other four groups are oriented in an opposite direction.     

Synthesis and crystal structure of Na<Subscript>3</Subscript>(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>· H<Subscript>2</Subscript>O

Single crystals of the compound Na₃(H₃O)[UO₂(SeO₃)₂]₂ · H₂O (I) have been synthesized, and their structure has been investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 9.543(6)Å, b = 9.602(7)Å, c = 11.742(8)Å, α = 66.693(16)°, β = 84.10(2)°, γ = 63.686(14)°, space group P \(\bar 1\), Z = 2, and R = 0.0734. The uranium-containing structural units of the crystals are [UO₂(SeO₃)₂]^2? chains, which belong to the crystal-chemical group AB ² B ¹¹ (A = UO ₂ ²⁺ , B ² = SeO ₃ ^2? , B ¹¹ = SeO ₃ ^2? ) of the uranyl complexes. The structures of the compounds containing the [UO₂(SeO₃)₂]^2? anionic complexes are compared.     

Crystal growth and properties of Rb<Subscript>2</Subscript>Ni(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O (RNSH)

Large single crystals of rubidium nickel hexahydrate Rb₂Ni(SO₄)₂ · 6H₂O (RNSH) of optical quality were grown for the first time. The atomic structure of RNSH crystals was refined. A comparative analysis of the crystal structures of (M ¹⁺)₂Ni(SO₄)₂ · 6H₂O, where M ¹⁺ is K, Rb, or Cs, was performed. The solubility curve of RNSH in water was measured. The optical and thermogravimetric properties of RNSH were investigated. The internal defect structure of RNSH crystals was studied by X-ray topography.     

Crystal structure and properties of K<Subscript>2</Subscript>[OsO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O

The synthesis and X-ray diffraction study of the compound K₂[OsO₂(C₂O₄)₂] · 2H₂O are performed. The compound crystallizes in the triclinic crystal system, space group P \(\bar 1\), a = 6.545(1) Å, b = 6.835(2) Å, c = 7.595(2) Å, α = 85.76(2)°, β = 65.33(2)°, γ = 71.14(2)°, and Z = 1. The osmium atom is located at the center of symmetry and has a distorted octahedral coordination formed by oxygen atoms: two oxygen atoms of the osmyl group occupy the apical positions [Os-O, 1.730(2) Å], and four oxygen atoms of the oxalate ions lie in the equatorial plane. The K⁺ cation is surrounded by ten oxygen atoms located at different K-O distances in the range from 2.787(2) to 3.158(2) Å. The assignment of the absorption bands in the IR spectrum of K₂[OsO₂(C₂O₄)₂] · 2H₂O is performed. The electronic absorption spectra of the compound are recorded in different solvents, and the thermal behavior in air is studied.     

Aqua{pentahydrogennitrilotris(methylenephosphonato)}lithium hydrate [Li(H<Subscript>2</Subscript>O){N(CH<Subscript>2</Subscript>PO<Subscript>3</Subscript>)<Subscript>3</Subscript>H<Subscript>5</Subscript>}] • H<Subscript>2</Subscript>O: Synthesis and structure

Aqua{pentahydrogennitrilotris(methylenephosphonato)}lithium hydrate is a linear coordination polymer. Its crystal structure is described in space group P^–1, Z = 2; a = 5.5732(2), b = 7.0106(2), and c = 16.9010(5) Å; α = 97.515(2)°, β = 94.551(2)°, and γ = 95.123(2)°. The tetrahedral coordination of the Li atom includes two oxygen atoms of a phosphonate ligand, one oxygen atom of another phosphonate ligand, and a water molecule. Complex formation is accompanied by closing of the eight-membered Li–O–P–C–N–C–P–O chelate ring. Polymeric chains run along the [100] direction. The chains are connected by hydrogen bonds.