Synthesis and characterization of HN(SPiPr2)(SePPh2) and [Te[N(SPiPr2)(SePPh2)]2

The compound HN(SP(i)Pr(2))(SePPh(2)) has been synthesized from the reaction of Ph(2)P(Se)NH(2) with (i)()Pr(2)P(S)Cl in the presence of NaH in THF. HN(SP(i)Pr(2))(SePPh(2)) crystallizes with eight formula units in space group Pbca of the orthorhombic system in a cell of dimensions at -120 degrees C of a = 9.9560(6) A, b = 17.9053(10) A, c = 22.4156(13) A, and V = 3995.9(4) A(3). The square-planar Te(II) complex [Te[N(SP(i)Pr(2))(SePPh(2))](2)] has been isolated from the reaction of Te(tu)(4)Cl(2) x 2H(2)O (tu = thiourea) with the anion [N(SP(i)Pr(2))(SePPh(2))](-), generated in situ from HN(SP(i)Pr(2))(SePPh(2)) in the presence of KO(t)Bu. [Te[N(SP(i)Pr(2))(SePPh(2))](2)] is dimorphic, crystallizing with one formula unit in space group P1 of the triclinic system in a cell of dimensions at -120 degrees C of a = 9.8476(9) A, b = 10.3296(9) A, c = 11.3429(10) A, alpha = 101.903(1) degrees, beta = 115.471(1) degrees, gamma = 92.281(2) degrees, and V = 1008.4(2) A(3) and also crystallizing with two formula units in space group P2(1)/n of the monoclinic system in a cell of dimensions at -120 degrees C of a = 8.7931(5) A, b = 17.1830(10) A, c = 14,1026(9) A, beta = 104.696(1) degrees, and V = 2061.1(2) A(3). In each instance, the [Te[N(SP(i)Pr(2))(SePPh(2))](2)] molecule possesses a center of symmetry, comprising a Te center liganded in a trans manner by two bidentate N(SP(i)Pr(2))(SePPh(2)) groups. However, the (31)P, (77)Se, and (125)Te NMR spectra of [Te[N(SP(i)Pr(2))(SePPh(2))](2)] show two sets of resonances at 25 degrees C. The (31)P VT NMR spectra show two sets of resonances between -50 and +50 degrees C that coalesce between 80 and 100 degrees C, consistent with the presence of the cis as well as the trans isomer in solution.     

叠氮化氢二聚体的分子间相互作用

通过ａｂ ｉｎｉｔｉｏＨＦ／６－３１Ｇ＊计算求得叠氮化氢二聚体（ＨＮ３）２势能面上四种优化结构型,经ＭＰ４ＳＤＴＱ电子相关校正和基组叠加误差２校正求得这些构型下的分子间相互作用能。结果表明,在四种优化构型中Ｎ３Ｈ．．．ＮＨＮ２最稳定,其分子间相互作用能为－１６．０７ＫＪ．ｍｏｌ＾－１。     

Soluble yttrium chalcogenides: syntheses,structures, and NMR properties of Y[eta 3-N(SPPh2)2]3 and Y[eta 2-N(SePPh2)2]2[eta 3-N(SePPh2)2

The compounds Y[N(QPPh2)2]3 (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe3)2]3 and HN(QPPh2)2 in methylene chloride (CH2Cl2). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh2)2]- ligands bound eta 3 through two S atoms and an N atom. The molecule possesses D3 symmetry, as determined in the solid state by X-ray crystallography and in solution by 89Y and 31P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh2)2]- ligands, but two are bound eta 2 through the two Se atoms and the other ligand is bound eta 3 through the two Se atoms and an N atom. Although a fluxional process is detected in the 31P and 77Se NMR spectra, a triplet is found in the 89Y NMR spectrum of 2 (delta = 436 ppm relative to YCl3 in D2O, 2JY-P = 5 Hz). This implies that on average the conformation of one eta 3- and two eta 2-bound ligands is retained in solution. Crystallographic data for 1: C72H60N3P6S6Y, rhombohedral, R3c, a = 14.927(5) A, c = 56.047(13) A, V = 10815(6) A3, T = 153 K, Z = 6, and R1(F) = 0.042 for the 1451 reflections with I > 2 sigma(I). Crystallographic data for 2: C72H60N3P6Se6Y.Ch2-Cl2, monoclinic, P2(1)n, a = 13.3511(17) A, b = 38.539(7) A, c = 14.108(2) A, beta = 94.085(13) degrees, V = 7241(2) A 3, T = 153 K, Z = 4, and R1(F) = 0.037 for the 8868 reflections with I > 2 sigma(I).     

Infrared spectrum and structure of thorimine (HN=ThH2)

Laser-ablated thorium atoms react with ammonia to form thorimine (NH=ThH(2)), the first actinide imine to be reported. This work underscores the high reactivity of thorium atoms, particularly for N-H bond activation, reveals a new type of multiple bond to actinide atoms, and shows that this bond is strong for thorium as a result of an important contribution from the f orbitals.     

First structural characterization of guanidine, HN=C(NH(2))(2)

Structural information about the free base guanidine in the solid state could be obtained for the first time by determining the crystal structures of the 1:1 as well as the 2:1 co-crystals consisting of neutral guanidine and 2-amino-4,6-dimethyl-1,3,5-triazine using single crystal X-ray diffraction.     

Crystal structure of olanzapine and its solvates. Part 3. Two and three-component solvates with water, ethanol, butan-2-ol and dichloromethane

Crystalline solvates of olanzapine (1), 2-methyl-4-(4-methyl-1-piperazinyl)-10H-thieno[2,3-b][1,5]benzodiazepine, have been characterized by an X-ray analysis and thermal (DSC) data. Crystallization of 1 from ethanol gives a solid containing both water and ethanol molecules; the solvate 1 · H₂O · EtOH (2:2:1) is monoclinic with the space group P2₁/c and the unit-cell volume V = 3752.8(12) Å³. Butan-2-ol forms with 1 solvate which is also a three-component phase, 1 · H₂O · BuOH, but its stoichiometry is different (1:1:1). The space group for this crystal is P2₁/c and the unit-cell volume V = 2216.5(7) Å³. Crystalline olanzapine dichloromethane solvate (2:1), 1 · CH₂Cl₂, is triclinic with the space group .The characteristic feature of all crystal structures is presence of a pair of olanzapine molecules which form dimer stabilized by multiple weak C–Hπ interactions between the N-methylpiperazine fragment and the phenyl / thiophene systems. Theoretical calculations have been performed indicating that the total C–Hπ binding energy is about 8 kcal mol⁻¹. In the crystal structure, the self-assembled olanzapine molecular dimers are arranged into parallel crystal planes. Packing of the layers proceeds in two ways in which structural motives are replicated by (i) perpendicular translation forming columns, and (ii) rotation around the twofold screw axis (parallel to the layer).     

Thermal analyses (TGA and DSC) of some spironolactone solvates

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) studies have been performed on a commercial preparation of spironolactone and on five solvates (acetonitrile, ethyl acetate, ethanol, methanol, and benzene) prepared from it by recrystallization at room temperature. The results of these studies are discussed and compared with those recently reported in the literature for similar preparations. The variable behaviour of these solvates in their release (and partial retention) of solvent before the onset of melting, meant that their stoichiometry had to be measured by elemental microanalyses. Solvent loss from solvate decomposition was followed by thermogravimetric analysis (TGA). Solvate decomposition and spironolactone melting temperatures and enthalpies were determined by differential scanning calorimetry (DSC). The parent substance and two of the solvates (methanol and ethanol) exhibited small exotherms in addition to the expected endotherms.     

Synthesis and Structure of Triphenylscandium-bis(tetrahydrofuran)

Metathesis reaction of ScCl₃(THF)₃ with 3 equiv. of phenyllithium in THF/Et₂O solution affords ScPh₃(THF)₂ ( 1 ) in good yield. The crystallographically determined molecular structure of 1 reveals a trigonal-bipyramidal coordination sphere with the THF molecules in the axial positions and Sc–C bonds of 2.245(4)–2.266(4) Å. The σ-bound phenyl groups are only slightly twisted (0, 8, 18°) with respect to the ScC₃ plane. Ab initio calculations suggest that the THF molecules play some direct role in the moderate coplanarity of the phenyl rings.     

Crystal solvates of carboxy-substituted Zn(II) phthalocyaninates with pyridine

Physicochemical characteristics (composition, energetic and chemical stability) of the molecular complexes of carboxy-substituted Zn(II) phthalocyaninates with pyridine were determined. It was found that the carboxyl substituents in positions 4 and 5 of the complex Zn(4,5-COOH)₈Pc favor the formation of the most stable molecular complexes with pyridine. The carboxyl substituents in the composition of Zn(3-COOH)₄Pc are not solvated with pyridine due to steric hindrances and the formation of the hydrogen bond between the carboxyl H atom and the meso-nitrogen atom; the molecular complexes of a tetrasubstituted Zn(4-COOH)₄Pc with pyridine are unstable.