Synthesis and crystal structure of N-benzylmethy- lammonium pentachlorothallate (III), [C6H5CH2NH2CH3]2TlCl5

N-Benzylmethylammonium pentachlorothallate (III) salt crystallizes in the monoclinic system P2₁/c with the following unit cell dimensions: a = 10.9540 (8), b = 12.559(1), c = 18.099(2)Å, = 112.1(3)° and Z = 4. The examination of the structure shows an alternate stacking of inorganic layers of pentachlorothallate (III) anions and organic layers of [C₆H₅CH₂NH₂CH₃]⁺ cations parallel to the c axis. The cohesion forces of the packing of N-benzylmethylammonium units in the layer and between two adjacent layers are provided by hydrogen bonds (N—HsCl) and van der Waals contacts.     

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.     

Crystal structure of bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate, [C6H5CH2CHCH2CH2NH2CH2CH2]2HPO4·5H2O

The salt bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate is orthorhombic with the following unit cell dimensions: a = 11.235(2) Å, b = 27.924(6) Å, c = 9.321(4) Å space group Pca2₁ with Z = 4. The structure was solved by the Patterson method and refined to final R value of 0.049 for 1802 independent reflections. The flack parameter is 0.14 with an e.s.d. of 0.23. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O—H,...,O and N—H,...,O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Crystal structure of [Co(o-SC6H4NH2){P(OMe)3}3]PF6

A cobalt-thiolato-phosphite complex [Co(o-SC₆H₄NH₂){P(OMe)₃}₃]PF₆ has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group with a = 10.590(4), b = 11.122(3), c = 13.577(5) Å, = 101.85(1), = 108.50(1), = 101.75(1)°, V = 1420.6(8) ų, and Z = 2. The structure comprises discrete [Co(o-SC₆H₄NH₂){P(OMe)₃}₃]⁺ cations and PF ₆ ^– anions where the metal atom is coordinated in a highly distorted square-pyramidal environment by one chelate o-SC₆H₄NH ₂ ^– (abt) and two P(OMe)₃ ligands in the basal positions, and a third P(OMe)₃ in the axial site with Co–N,, 1.847(5), Co–S, 2.166(2), Co–P, 2.157(2), 2.147(2), and 2.125(2) Å.     

Crystal structure of Zn[Cl2Ti(C5H5)2]2·2C6H6

The structure of crystals of the composition Zn[Cl₂Ti(C₅H₅)₂]₂·2C₆H₆ has been determined from Patterson and Fourier syntheses of two projections, and refined toR = 0·117 by full-matrix three-dimensional least-squares methods. The crystals are orthorhombic:Pbcn,a = 18·45(5),b = 15·40(6),c = 11·35(3) Å,Z= 4. The complex consists of a central distorted ZnCl ₄ ^2– tetrahedron linked along the Cl—Cl edges to two distorted TiCl₂(C₅H₅)₂ ⁺ tetrahedra in such a way that their centres are nearly collinear The two C₆H₆ molecules in the formulae unit may be regarded as benzene of crystallization.     

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.     

Synthesis,characterization and impedance spectroscopy of the new material [(CH3) (C6H5) 3P] 2CoBr4: a member of the A2BX4 family

The crystal structure of bis‐(methyltriphenylphosphonium) tetrabromocobaltate (II), [(C₁₉H₁₈P)₂ CoBr₄] is determined: M_r = 933.203, monoclinic, P2₁, a = 9. 6977 (3) Å, b = 12.5547 (4)Å, c = 16.4503 (6)Å, β = 105.603 (2)°, V = 1929.04 (11)ų, Z = 2, D_x = 1.607 Mg m^‐3, T = 298 K. Differential thermal analysis at high temperatures shows three endothermic peaks characterizing four phases, with onset temperatures at T₁= 313±2 K, T₂ = 320±4 K and T₃= 360±1 K. The structural instability detected via the temperature dependence of permittivity at T₁ is ascribed to order‐disorder transition associated with cation dipole reorientation. Permittivity and ac conductivity studies as a function of temperature (295 K‐375 K) and frequency (0.11 kHz < f <100 kHz) are presented. The results indicate the importance of the cation size and shape on the phase transitions in the system. Bulk conductivity behavior is thermally activated. The associated activation energies are in the range 2.9 to 1.0 eV depending on the temperature regime. Two contributions to the ac conductivity, one dominating at low temperatures and high frequencies which are characterized by superlinear frequency exponent and the second dominates at high temperatures characterized by a sublinear frequency exponent. The behavior is interpreted in terms of the jump relaxation model. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Molecular structure of trans-[Co(NH3)4(NH2CH3)Cl](ClO4)2

The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I>2(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH₃)₄(NH₂CH₃)Cl](ClO₄)₂ molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.     

Crystal structure and phase transition of single crystalline CsNH2SO3

Differential scanning calorimetry (DSC) and X‐ray diffraction measurements have been performed on cesium sulfamate CsNH₂SO₃ single crystal. Two distinct endothermic peaks in the DSC curves are observed at 330 and 436 K. It is pointed out that the peak at 330 K is attributed to the structural phase transition, and the other peak at 436 K is associated with the thermal decomposition of the crystal. The structures in room‐ and high‐temperasture phases are determined, and the space group of the sample crystal is found to change from monoclinic P 2₁/c to orthorhombic Pnma. The structure of the room‐temperature phase consists of two different types of N‐H···O hydrogen bond, but in the high‐temperature phase there is no specific hydrogen bond between the NSO₃ pseudo‐tetrahera. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal structure of [Tb4(H2O)2](C2O4)2(C5H6O4)4

A terbium complex associating two ligands, oxalate and glutarate, was prepared under hydrothermal conditions at 200°C by treating an aqueous suspension of terbium oxalate decahydrate with glutaric acid and guanidinium carbonate. Its structure was solved by X-ray diffraction on a single crystal. It crystallizes in the monoclinic space group P2₁ with lattice constants, a = 9.514(1) Å, b = 9.0681(8) Å, c = 19.702(2) Å, and = 97.90(1)°. The terbium atoms and the oxalate ligands build dense chains which are connected by one side of the carboxylic group of some glutarate ligands, thus forming a sheet at the c level 0 and 1/2. These sheets are bridged by glutarate groups. The terbium atoms are ninefold coordinate with nine oxygen atoms of the ligands or with one water molecule and eight oxygen atoms of the ligands. Each polyhedron of the terbium atoms share one edge and one face of oxygen atoms with the two neighboring ones. The oxalate ligands are bischelating and bismonodentate. The coordination scheme of glutarate differs: either they are bismonodentate from one side and chelating and monodentate from the other side or they are chelating and monodentate from both sides.     

Ether cleavage of [2.2.2]cryptand: synthesis and X-ray crystal structure of [NH(CH2CH2I)3][I5]

Treatment of [2.2.2]cryptand1 in toluene with HI(g) has resulted in the formation of a twophase liquid clathrate solution from which the complex [NH(CH₂CH₂I)₃][I₅]2 has been isolated and crystallographically characterized. Crystal data for2: triclinic, space group $P\bar 1$ ,a=9.301(3) Å,b=10.419(3) Å,c=11.078(3) Å, α=90.20(2)^o, β=103.28(2)^o γ=96.50(2)^o,D _c =3.57g/cm³,Z=2,R _f =0.054,R _w =0.054. The salt is a product of an ether cleavage of the macrobicycle. The crystal structure of2 contains [NH(CH₂CH₂I)₃]⁺ ions and zigzag chains of [I₅]^? ions which self-assemble to form alternating layers, of cations and anions.     

Crystal structure investigation of [Mn(3-CH3C5H4N)2(N3)2(H2O)2]

The crystal structure of the title compound has been determined by single crystal X-ray diffraction methods. [Mn(3-CH₃C₅H₄N)₂(N₃)₂(H₂O)₂] crystallizes in the space group P 1 with a = 7.444(2) Å, b = 7.691(2) Å, c = 8.926(3) Å, α = 99.82(3)°, β = 108.80(2)°, γ = 114.99(2)° and Z = 1. Least squares refinement gave a R value of R_w = 0.046 for 1414 observed reflections. The manganese atom in the title complex is octahedrally coordinated by two oxygen atoms of the water molecules and four nitrogen atoms; two N-atoms are the end atoms of azide groups and the other two nitrogen atoms belong to the 3-methylpyridine molecules. The polyhedra are linked via hydrogen bonds between the water molecules and the azide groups.     

Crystal structure of the orange isomer of [(C6H5)3P]2[C2S2(CF3)2]RuCO

The structure of the title compound has been determined by X-ray analysis. It is monoclinic:a = 10.147,b = 10.081,c = 38.627 Å, β = 102.27 °,Z = 4,P2₁/c. The structure was solved by standard methods and refined by least squares to a (conventional)R-factor of 4.7%. The Ru atom is in square-pyramidal configuration: the Ru-S distances (2.286, 2.336Å) are significantly different, but the Ru-P distances average to 2.389 Å. Comparisons are made with the violet isomer.     

Crystal and molecular structure of the symmetrical bidentate ligand 3,3-di(1-pyrazolyl)pentane, CH3CH2C(C3H3N2)2CH2CH3

The title compound crystallizes in the centrosymmetric space group C2/c with a = 14.4005(23), b = 7.0494(12), c = 11.2462(20) Å, = 101.572(13)° and Z = 4; the molecule lies on a crystallographic C ₂ axis. Hydrogen atoms were both located and refined.     

Crystal and molecular structure of the rutheniumcarbene-tetraborohydrate complex [Ru(BH4)(LAr)(PPh3)2]; (LAr=CN(C6H4Me-4)CH2CH2NC6H3Me-4)

The structure of the title compound has been determined by single crystal X-ray diffraction analysis:P2₁/c,M _r=889.9,a=15.940(1),b=23.357(2),c=18.767(2) Å,=132.62(1)°,V _c=5141.6 ų,Z=4,D _x=1.150 mg m^–3,F(000)=1848; finalR _f=0.074 (R _w=0.085). The BH ₄ ^– ligand in the complex is bidentate. A comparative study indicates that the lengths of the Ru-carbene carbon bond and other bonds to the Ru atom are determined by a combination of several factors, and not just by a purely - or -bonding interaction.     

Molecular structure of AlH3[N(CH2CH2)3CH]2

Reaction of AlH₃[N(CH₂CH₂)₃CH] with hexamethyltrisiloxane, (OSiMe₂)₃, gives rise to the bis-quinuclidine complex AlH₃[N(CH₂CH₂)₃CH]₂, which has been characterized by ¹H and ¹³C NMR spectroscopy and X-ray crystallography. The molecular structure of AlH₃[N(CH₂CH₂)₃CH]₂ consists of a trigonal bipyramidal aluminum with axial coordination of the quinuclidine ligands. Crystal data: orthorhombic, space group Pbcn, a = 10.6895(9), b = 12.266(1), c = 12.3794(9) Å, V = 1623.2(2) ų, and Z = 4.     

Crystal structure and IR spectroscopic study of (CN3H6)2[(UO2)2(C2O4)(CH3COO)4]

Compound (CN₃H₆)₂[(UO₂)₂(C₂O₄)(CH₃COO)₄] is synthesized and characterized by IR spectroscopy and single-crystal X-ray diffraction [a = 8.5264(2) Å, b = 13.8438(4) Å, c = 10.7284(2) Å, β = 103.543(1)°, space group P2₁/n, Z = 2, and R = 0.0258]. The main structural units of the crystals are binuclear [(UO₂)₂C₂O₄(CH₃COO)₄]^2? groups, which belong to the A ₂ K ⁰² B ₄ ⁰¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and B ⁰¹ = CH₃COO^?). The coordination polyhedron of the uranium atom is the UO₈ hexagonal bipyramid with the oxygen atoms of the uranyl ion at the axial positions. Uranium-containing groups and guanidinium cations are connected by electrostatic interactions and by the hydrogen bond system, which involves hydrogen atoms of guanidinium cations and oxygen atoms of oxalate and acetate anions. The results of the spectroscopic study of the compound agree with the X-ray diffraction data.     

Crystal and molecular structure oftrans-ammonium-tetrachlorobis(4-methylpyridine) tungstate(III) tetrahydrate,NH4[WC14(C6H7N)2] ·4H2O

Trans-NH₄[WCl₄(C₆H₇N)₂]·4H₂O crystallizes from a solution oftrans-(C₆H₇NH) [WC1₄(C₆H₇N)₂] in aqueous ammonia. The compound is air sensitive and thermally unstable; space groupI4₁/amd (No. 141),a=18.215(5),c=14.160(3) Å, andZ=8. The structure was solved by the heavy-atom method and refined by least squares toR andR _w of 0.052 and 0.053, respectively. The unit cell contains two almost unrelated parts: the NH ₄ ⁺ and WC1₄(C₆H₇N) ₂ ^– are linked by electrostatic and hydrogen bonds, and the rest of the unit cell is filled with the four isolated (H₂O)₈ clusters ofD _2d symmetry. The O-O distances within the cluster are 2.72(2) and 2.86(2) Å; the anion is located on a symmetry center (C _2h symmetry). The W-C1 and W-N(4-methylpyridine) bonds are 2.427(6), 2.446(6), and 2.168(15) Å.     

Crystal Structure of pyridinium isopolymolybdate (C5H6N)2n[Mo4O13]n

Synthesis and crystal structure are described for pyridinium isopolymolybdate of chemical composition (C₅H₆N)_2n[Mo₄O₁₃]_n. The crystals are triclinic, space group P1, with the following unit‐cell parameters: a =8.2695(11) Å, b =10.544(4) Å, c =11.177(4) Å, α = 71.76(5)°, β = 89.68(3)°, γ = 78.79(3)°, V =906.4(4) ų, Z = 2 (chemical formula (C₅H₆N)₂[Mo₄O₁₃]), D _calcd = 2.755 g·cm^–3. Crystal structure was solved by Patterson methods and refined to a final R value 0.085 for 4045 independent reflections. The studied compound, considered in analogy to triclinic (NH₄)₂Mo₄O₁₃ as pyridinium polyoctamolybdate, is proposed to be better described as pyridinium isopolytetramolybdate (C₅H₆N)_2n[Mo₄O₁₃]_n. It seems that the proper coordination number of molybdenum (VI) ions is five, resulting in pyramidal coordination polyhedra [MoO₅]. Coordination polyhedra joined by common edges form tetramolybdate monomeric unit [Mo₄O₁₃]. The mers are connected by oxygen bridges Mo ‐ O ‐ Mo into infinite ribbon chains. Each two infinite chains are hold together by weaker intermolecular interactions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)