Structure of a binuclear silver(I) complex [Ph3PAg(O2CCH2Ph)]2

The reaction of [Ph₃PAgI]₄ with sodium phenylacetate in MeOH and CH₂Cl₂ at room temperature gave rise to a binuclear silver complex with triphenylphosphine and phenylacetate mixed ligands, [Ph₃PAg(O₂CCH₂Ph)]₂. The crystal and molecular structure of the complex has been determined by single crystal X-ray diffraction analysis. The space group is witha=9.198(2),b=9.516(2),c=13.842(3) Å, =102.00(3), =108.34(3), =93.58(3)°,Z=1, andDc=1.506 g cm^–3. The silver atoms are each coordinated by one phosphorus atom from triphenylphosphine and two oxygen atoms from the carboxylate groups in a T-shape. The complex is further characterized by its IR,¹H, and³¹P NMR spectra.     

Crystal structure of NH3(CH2)2NH3(BiI4)2·4H2O

The ethylenediammonium bis tetraiodobismuthate(III) tetrahydrate salt is monoclinic with the following unit cell dimensions:a=7.476(3)Å,b=13.194(3)Å,c=13.916(9)Å, β=95.22(6)°, space groupP2₁ lc withZ=2. The structure consists of disordered ethylenediammonium cations, water molecules and polynuclear anions in which slightly distored [BiI₆]^3? octahedra sharingcis edges are interconnected into chains. The [BiI₄]^? anions are connected through O(W2)?H...I hydrogen bonds, so that infinite two dimensional chains parallel to thea axis with anionic period [BiI₄(H₂O)]^? are formed in the structure. These chains are themselves interconnected by means of the O?H...I and N...O(I) bonds originating respectively from the water molecules and the ethylenediammonium entities, forming a three-dimensional network.     

X-ray crystal and molecular structure of dichlorobis [2(1H)-pyridinethione-S]iron(II)

Attempts to prepare the mixed ligand complex, FeCl₂(pyS)(Ph₃P)₂ from the reaction of iron(III) chloride with 2(1H)-pyridinethione-S(HpyS) and triphenylphosphine(Ph₃P) in ethanol instead formed FeCl₂(HPyS)₂ characterized by X-ray crystallography. The structure was determined by the heavy atom method, using MoK diffractometer data, and refined by full-matrix least squares toR=0.049 for 1123 observed reflections. The molecule possesses twofold symmetry with a distorted tetrahedral geometry about the iron(II) center with S-Fe-S and Cl-Fe-Cl bond angles of 98.76(5)° and 115.79(5)° and Fe-S and Fe-Cl bond distances 2.345(1) Å and 2.288(1) Å, respectively. Hydrogen bonding between NH and chlorine atoms leads to a polymeric type structure of linked molecules running approximately parallel to thea axis.     

(Aroxymethyl)triphenyltin compounds: Crystal and molecular structure of triphenyl(p-toloxymethyl)tin

Compounds, Ph₃SnCH₂OAr, are available from Ph₃SnCH₂I and NaOAr in EtOH. The crystal and molecular structure of Ph₃SnCH₂OC₆H₄Me-p (II) has been determined by X-ray crystallography. The molecule in the crystal contains a slightly distorted tetrahedral tin atom [C-Sn-C valency angles varying from 106.9(5) to 114.1(6)°] with an intramolecular Sn---O distance of 2.900(11) Å. NMR spectral data for (II) and for Ph₃SnCH₂OC₆H₃Br₂-2,4 are reported.     

X-ray and neutron diffraction studies of the hydridotriruthenium cluster complex (μ-H)Ru3(CO)7(μ-As(C6H5)CH2As(C6H5)2) ((C6H5 2AsCH2As(C6H5)·CH2Cl2: an example of dibridged metal-metal bond M(μ-H)(μ-X)M,involving a heavy bridgehead atom

The title compound is (μ-H)Ru₃(CO)₇(μ-As(C₆H₅)CH₂As(C₆H₅)₂)((C₆H₅)₂ AsCH₂As(C₆H₅)₂)·CH₂C1₂. Crystal data: monoclinic,P2₁/n, cell parameters (X-ray)a=12.82(2) Å,b=22.91(2) Å,c=17.83(2) Å, β=99.1(3)°; (neutron)a=12.94(1) Å, β=22.95(2)Å,c=17.93(3)Å,β=99.55(5)°. The structure was solved from X-ray data. FinalR indices areR(F)=0.051,R _w (F)=0.049 (X-ray);R(F)=0.064,R _w (F)=0.048,R(F ²)=0.072,R _w (F²)=0.088 (neutron). The complex is derived from Ru₃(CO)₈(dpam)₂ through reaction with hydrogen. The structure consists of a triangular array of metal atoms involving three metal-metal bonds[Ru(1)?Ru(2)=2.912(7)Å;Ru(1)?Ru(3)=2.829(3) A; Ru(2)?Ru(3)=2.845(6) Å]. The metal-metal edge Ru(1)?Ru(2) is supported by a bridging bis(diphenylarsino)methane ligand which lies in the equatorial plane. Activation of the second dpam ligand has generated the new face-bridging ligand unit μ-As(C₆H₅)CH₂As(C₆H₅)₂. In this unit, the bridgehead As atom spans over the Ru(1)?Ru(2) bond, while the second As atom is only bonded to Ru(3). The metal environment is achieved by CO ligands. The hydride ligand is bridging the Ru(1)?Ru(2) vector [Ru(1)?H=1.791(10) Å; Ru(2)?H=1.818(8) Å]. Geometric features of the dibridged Ru(μ-H)(μ-As)Ru bond are discussed.     

Crystallographic investigations of 1,4-benzothiazin-2(1H)one and 3-methyl-1,4-benzothiazin-2(1H)one

The crystal structures of 1,4-benzothiazin-2(1H)one (C₈H₇SNO) (I) and 3-methyl-1,4-benzothiazin-2(1H)one (C₉H₉SNO) (II) have been determined by X-ray diffraction methods. I crystallizes in the monoclinic system with space group P2₁/n, while II crystallizes in triclinic with space group P $\bar 1$ . The molecular features in both the structures are almost similar; however, there exists an intermolecular interaction in (II) that could be due to the methyl group.     

Preparation and studies of new crystals in the K3H(SO4)2-(NH4)3H(SO4)2-H2O system

To elucidate the effect of isomorphic substitution on the kinetics of phase transitions, single crystals of (K _x (NH₄)_1?x ) _m H _n (SO₄)_{(m + n)/2} · yH₂O solid solutions are grown from the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O system, whose end members are known to undergo superprotonic phase transitions of fundamentally different kinetics. The chemical composition of the single crystals grown is determined by energy dispersive X-ray microanalysis. The thermal and optical behavior of (K,NH₄)₉H₇(SO₄)₈ · H₂O single crystals is studied in the temperature range 295–420 K and the crystal structure at 295 K is determined. A comparison of the results of the studies with data for crystal K₉H₇(SO₄)₈ · H₂O published earlier shows that the substitution of ammonium for potassium atoms lowers the temperature of the structural phase transition by 8 K.     

Crystal structure of (Z)-1-(sec-butyl)-3-(4-dimethylaminophenyl)-2-(1H-1,2,4-triazol-1-yl)propen-2-one

The crystal structure of the title compound is determined by X-ray diffraction studies. The structure is solved by the direct method. The experimental data are obtained on a DAR-UMB diffractometer by the θ-θ/2θ scan technique using MoK _α radiation. The crystal is monoclinic, a = 17.913(3) Å, b = 17.239(3) Å, c = 5.501(5) Å, γ = 74.4(3)°, space group P2₁/a, Z = 4 for C₁₇H₂₂N₄O, and ρ_calcd = 1.211 g/cm³. The molecule consists of the phenyl and triazole rings and the dimethylamino, carbonyl, and isopropyl groups attached to the rings. The dihedral angle between the rings is 67.4°. The carbonyl oxygen atom and the triazole ring are in the trans position relative to each other. The N-C-C-O torsion angle is 172.8°. The molecule is in the Z isomeric form.     

Crystal and molecular structure of di-μ-bromobromopentakis(benzimidazole)dicopper(II) monobromide tetrahydrate [Cu2Br3(C7H6N2)5]Br·4H2O

A new complex compound. [Cu₂Br₃(C₇H₆N₂)₅]Br·4H₂O, has been synthesized and its crystal structure investigated by single-crystal X-ray methods. The crystals are isostructural with those of the [Cu₂Cl₃(C₇H₆N₂)₅]Cl·4H₂O salt. They are orthorombic, space group Pnma with 4 formula units in a cell of dimensions:a+19.923(1),b+17.555(2),c+12.0523(4)Å. The structure was refined by full-matrix least-squares to giveR+0.047 andR _w+0.053 for 3569 intensities above 3σ(I). As in the chloride compound, the complex cation consists of pairs of distorted trigonal bipyramidal Cu(II) centers which share an edge by two equatorial bromide ions. The Cu...Cu nonbonding distance in the complex in 3.4894(7)Å. The two Cu?Br?Cu bridges are not equivalent and their geometry is slightly different from that in the chloride complex. Comparison of the investigated structure to other binulear bis(μ-halide) bridged copper(II) complexes of similar structure has been made.     

The disordered structure of (p-tolythiomethyl)triphenylgermanium

The disordered crystal structure of Ph₃GeCH₂SC₆H₄Me has been determined in space groupC2/c with cell dimensionsa=16.916(8),b=11.110(8),c=24.217(16)Å, and -98.86(2)°. The structure can be represented by two overlapping images which are only partially resolved. The germanium atom is in a distorted tetrahedral environment and refinement converged atR=0.049. The crystal structure of a similar organogermanium compound, Ph₃GeCH₂SO₂C₆H₅, which crystallizes in space group Cmca witha=11.037(2),b=17.077(3), andc=23.016(6)Å, is also shown to be highly disordered.     

Crystal structure of [N-(2-carbamoylethyl)iminodiacetato]-aqua(1,10-phenanthroline)cobalt(III) chloride 3.5 hydrate

The crystal structure of [N-(2-carbamoylethyl)iminodiacetato]-aqua(1,10-phenanthroline) cobalt(III) chloride 3.5 hydrate [Co(Ceida)(H₂O)(Phen)Cl · 3.5H₂O (I) has been determined by ¹H NMR technique and X-ray diffraction analysis. The crystals are triclinic, a = 10.352(2) Å, b = 12.534(3) Å, c = 20.665(4) Å, α = 107.02(3)°, β = 92.22(3)°, γ = 111.63(3)°, Z = 4, space group $P\bar 1$ , andR = 0.0438. The unit cell involves two crystallographically nonequivalent but virtually identical cationic complexes [Co(Ceida)(H₂O)(Phen)]⁺. The tridentate chelate ligand Ceida ^2? (N + 2O) occupies the face in the coordination octahedron of the Co atom, and the propionamide group remains free. The mean bond lengths are as follows: Co-O_Ceida, 1.876 Å; Co-N_Ceida, 1.981 Å; Co-N_Phen, 1.945 Å; and Co-O_w, 1.915 Å. In the structure, the arrangement of cationic complexes and certain water molecules exhibits a pseudosymmetry (the 2₁ axis). The cations and water molecules are located in the layers, and the anions are arranged between the layers. The structural elements are linked by hydrogen bonds and van der Waals interactions.     

Alkali-metal hydrogen selenate-phosphates M 2 H 3(SeO4)(PO4) (M = Rb or K) and M 4H5(SeO4)3(PO4)(M = K or Na)

Crystalline hydrogen selenate-phosphates M ₂H₃(SeO₄)(PO₄) [M = Rb (I) or K (II)] and M ₄H₅(SeO₄)₃(PO₄) [M = K (III) or Na (IV)] were obtained by reactions of Rb, K, and Na carbonates with mixtures of selenic and phosphoric acid solutions. The X-ray structure study of single crystals revealed that I and II are isostructural (sp. gr. Pn). In these structures, SeO₄ and H₃PO₄ tetrahedra are linked by hydrogen bonds to form corrugated layers. Structures III and IV (sp. gr. $P\bar 1$ ) have similar arrangements of non-hydrogen atoms but different hydrogen-bond systems. In III = K₄(HSeO₄)₂{H[H(Se,P)O₄]₂}, the HSeO₄ groups branch from the infinite anionic {H[H(Se,P)O₄]₂} chains. In IV = Na₄[H(SeO₄)₂]{H[H_1.5(Se, P)O₄]₂}, the anionic {H[H_1.5(Se,P)O₄]₂} chains are crosslinked by hydrogen bonds formed by the [H(SeO₄)₂] dimers.     

Crystal structures of two modifications of sodium pentahydrogendiphosphate NaH5(PO4)2

Two crystalline modifications of NaH₅(PO₄)₂ are obtained by the reaction of Na₂CO₃ with an excess of orthophosphoric acid. The crystal structures of α-and β-NaH₅(PO₄)₂ are determined by X-ray diffraction analysis. The crystal data are a = 8.484(4) Å, b = 7.842(3) Å, c = 10.353(4) Å, β = 90.50(3)°, V = 689.3(3) ų, space group P2₁/c, Z = 4, and R ₁ = 0.0250 for the α modification and a = 7.127(2) Å, b = 13.346(4) Å, c = 7.177(2) Å, β = 95.5(2)°, V = 679.5(3) ų, space group P2₁/c, Z = 4, and R ₁ = 0.0232 for the β modification. Based of the hydrogen-bond system, the formulas of the α and β modifications can be represented as Na(H₂PO₄)(H₃PO₄) and Na[H(H₂PO₄)₂], respectively. They correspond to the stable and metastable forms of the compound.     

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO₂(n-C₃H₇COO)₂(H₂O)₂ (I) and Mg(H₂O)₆[UO₂(n-C₃H₇COO)₃]₂ (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P2₁/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group $Pa\bar 3$ , Z = 4, and R = 0.0173. The main structural units of I and II are [UO₂(C₃H₇COO)₂(H₂O)₂] molecules and [UO₂(C₃H₇COO)₃]^? anionic complexes, respectively, which belong to AB ₂ ⁰¹ M ₂ ¹ (I) and AB ₃ ⁰¹ (II) crystal chemical groups of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₇COO^?, and M ¹ = H₂O). A crystal chemical analysis of UO₂ L ₂ · nH₂O compounds, where L is a carboxylate ion, is performed.     

Synthesis and crystal structure of new carbonate NaPb2(CO3)2(OH)

Crystals of a new lead carbonate, NaPb₂(CO₃)₂(OH), sp. gr. P31c, were prepared by hydrothermal synthesis. The crystal structure was established by the heavy-atom method without knowing the exact chemical formula of the compound. The polar structure of the carbonate and the distortion of the pseudosymmetry described by the supergroup P $\bar 3$ 1c are caused by the acentric arrangement of the oxygen atoms providing the satisfactory coordination of Pb and Na atoms. The bonds between a hydroxyl group and two crystallographically independent Pb atoms are directed along the c-axis and have different lengths. The study of the carbonate by the second harmonic generation method in a temperature range of 20–250°C revealed the nonlinear optical properties comparable with the similar properties of quartz. The comparison of the structure of the new carbonate with a number of carbonates demonstrated that the new compound is structurally similar to ewaldite BaCa(CO₃)₂, diorthosilicate NaBa₃[Si₂O₇](OH), and Ba[AlSiO₄]₂ containing a double silicon—oxygen layer.     

Crystal of catena-(μ2-terephthalato)-bis (N-methylimidazole)-copper(II)

A new one-dimensional chain complex [Cu(ta) (N-MeIm)₂]n (where ta = terephthalic acid dianion,N-MeIm =N-methylimidazole) has been synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the Monoclinic space groupP2₁/c with the parameters:a = 5.2930(11)Å,b = 14.679(3)Å,c = 11.007(3)Å, β = 104.84(3)^°,V = 826.7(3)ų, withZ = 4 formula units. In the structure, each Cu atom is coordinated by a pair ofN-methylimidazole ligands and a pair of monodentate carboxylate groups, affording a square planar N₂O₂ geometry. Both carboxylate groups of the terephthalate dianion coordinate in a monodentate mode bridging two Cu(II) ions with formation of 1D zigzag chain along thec axis. This supramolecular compound exhibits a three-dimensional solid state structure constituted by hydrogen bonds and C–H–π stacking interactions.     

Structures of Tris(2-hydroxyethyl)ammonium Salts of Succinic Acid

Succinic acid salts-tris(2-hydroxyethyl)ammonium succinate (C₆H₁₆NO₃) ₂ ⁺ C₄H₄O ₄ ^2? (monoclinic crystals, sp. gr. P2₁/c, Z = 4) and tris(2-hydroxyethyl)ammonium hydrogen succinate (C₆H₁₆NO₃)⁺C₄H₅O ₄ ^? (monoclinic crystals, sp. gr. P2₁/c, Z = 4)—were synthesized and structurally characterized. The specific features of the three-dimensional structures of tris(2-hydroxyethyl)ammonium salts of succinic acid are considered. The role of interionic electrostatic interactions in the structure stabilization and the formation of products of composition 1: 1 and 1: 2 derived from succinic acid is discussed.     

Crystal structure of pentakis ethylenediammonium bis undecachlorodiantimonate(III) tetrahydrate, (NH3(CH2)2NH3)5(Sb2Cl11)2·4H2O

The pentakis ethylenediammonium bis undecachlorodiantimonate(III) tetrahydrate salt is monoclinic with the following unit cell dimensions:a=16.271(5) Å,b=13.004(4) Å,c=13.932(4) Å, β=111.72(2)°, space groupP2₁/c withZ=2. The structure was solved by Patterson methods and refined to a finalR value of 0.023 for 4435 reflections withF ₀>4σ(F ₀). The structure shows a layer arrangement perpendicular to thea axis: planes of the [Sb₂Cl₁₁]⁵⁻ bioctahedra alternate with planes of [NH₃(CH₂)₂NH₃]²⁺ dications. The [Sb₂Cl₁₁]⁵⁻ bioctahedra are connected through O−H...Cl hydrogen bonds, such that infinite chains of composition [Sb₂Cl₁₁(H₂O]_n ⁵ⁿ⁻ are formed in the structure, parallel to the twofold axis. These chains are themselves interconnected by means of N−H...Cl and O−H...Cl bonds originating from the [NH₃(CH₂)₂NH₃]²⁺ entities and the water molecules, respectively, and form a threedimensional network.     

Crystal structure of [Rb0.24(H2O)0.76]VO(H2O)(PO4), a new monoclinic variety in the series of layered vanadyl phosphates

The crystal structure of a new monoclinic variety of hydrous rubidium vanadyl phosphate [Rb_0.24(H₂O)_0.76]VO(H₂O)(PO₄) doped with Al³⁺ ions is studied by X-ray (R = 0.054) diffraction: a = 6.2655(4) Å, b = 6.2712(3) Å, c = 6.8569(5) Å, β = 107.805(7)°, space group P2₁/m, Z = 2, and D _x = 2.792 g/cm³. The new phase obtained by the hydrothermal synthesis in the V₂O₅-Rb₂CO₃-AlPO₄-H₂O system has a layer-type structure in which Rb atoms and water molecules are located between layers of vertexsharing [VO₅(H₂O)] octahedra and [PO₄] tetrahedra. Rb intercalates based on VOPO₄ · 2H₂O are described by general formula [Rb _x (H₂O)_{1 ? x} ]V _1?x ^V V _x ^IV O(H₂O)(PO₄), where x ≤ 0.5, and the amount of reduced vanadium and interlayer water molecules is determined by the amount of introduced rubidium atoms.     

Hydrothermal synthesis and the crystal structure of borate cancrinite (Na,Ca)2[Na6(AlSiO4)6](BO3) · 2H2O

Transparent prismatic single crystals of borate cancrinite (Na,Ca)₂[Na₆(AlSiO₄)₆](BO₃) · 2H₂O are prepared through hydrothermal crystallization. The parameters of the hexagonal unit cell and intensities of 10806 reflections are measured on an Enraf—Nonius CAD4 automated diffractometer. The compound crystallizes in the hexagonal crystal system with the unit cell parameters a = 12.745(4) Å, c = 5.180(2) Å, V = 728.6(4) ų, and space group P6₃. The structure is determined by direct methods and refined using the full-matrix least-squares procedure in the anisotropic approximation for the non-hydrogen atoms. The refinement of the structure is performed to the final discrepancy factor R ₁ = 0.027 for 2889 unique reflections with I > 2 σ (I). In the structure of the borate cancrinite, the AlO₄ and SiO₄ tetrahedra form a zeolite-like framework in which twelve-membered hexagonal channels are occupied by sodium atoms and BO₃ groups, whereas six-membered channels are filled with sodium and calcium atoms and water molecules. The mean interatomic distances are found to be as follows: (Si-O)_mean = 1.614 Å and (Al-O)_mean = 1.741 Å in the AlO₄ and SiO₄ tetrahedra, (Na-O)_mean = 2.542 Å in the seven-vertex sodium polyhedra, and [(Na,Ca)-O]_mean = 2.589 Å in the ditrigonal bipyramids.