Synthesis and X-ray crystal structures of six [TeL4][MF6] salts, where L is ethylene- or trimethylene-thiourea, and M is Si, Ge or Sn. Five Te(II) complexes with a novel type of structure linked together by unusual N–HF hydrogen bonds

The complexes [Te(etu)₄][SiF₆] (1), [Te(etu)₄][SiF₆] · H₂O (2), [Te(trtu)₄][SiF₆] (3), [Te(etu)₄][GeF₆] · H₂O (4), [Te(trtu)₄][GeF₆] (5) and [Te(etu)₄][SnF₆] (6) (etu = ethylenethiourea, trtu = trimethylenethiourea) have been prepared and their crystal structures determined by X-ray crystallographic methods. The crystals of 1, 3 and 5 are tetragonal; space groups P4cc (No. 103) with Z = 4 for 1, P4nc (No. 104) with Z = 2 for 3, and I4 (No. 79) with Z = 2 for 5. The crystals of 2, 4 and 6 are orthorhombic, space group Pccn (No. 56) with Z = 8 for 2 and 4 and Z = 4 for 6; those of 2 and 4 being isomorphous. The cations contain square planar or slightly distorted square planar TeS₄ coordination groups. In 1, 3 and 5 the Te atoms are located on fourfold rotation axes; the cations have fourfold rotational symmetry and the four thiourea ligands extend to the same side of the TeS₄ plane. These are the first examples of [TeL₄]²⁺ conformers of this type. In 2 and 4 the Te atoms lie on general positions; the cations are distorted versions of those in 1, and also in these the four ligands extend to the same side of the TeS₄ plane. In 6 the Te atoms are located on twofold rotation axes, the conformation of the cations corresponds to the point group C₂ with two neighbouring ligands extending to one side of the coordination plane and the remaining two to the opposite side. In 1–5 each of the four ligands forms a N–HF bond to the same F atom in the counter ion. The crystals of 1–5 are red, and those of 6 are yellow. The red colour is attributed to interactions of Te and S lone electron pairs caused by ligand TeS₄/TeSC tilt angles markedly different from 90°.     

Synthesis of ansa -zirconocenes based on 2-(phenylethynyl)-1 H -indene. The crystal and molecular structure of the complex [μ-CH2CH2(η5-2-PhC≡CInd)2]ZrCl2 (Ind is inden-1-yl)

Alkynyl-substituted indene was first used as a ligand for the synthesis of transition metal complexes. ansa-Zirconocenes containing ethylene and dimethylsilylene bridges were synthesized starting from 2-(phenylethynyl)-1H-indene. The structure of the former compound was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 68–73, January, 2007.     

晶性3，4－聚异戊二烯的结构研究

采用ＷＡＸＤ、ＳＡＸＳ和Ｘ－射线平板照相法研究了不同聚合条件和拉伸倍数下的晶性３，４－聚异戊二烯的结构．结果发现，降低催化体系反应速度有利于产物结晶；不同的含氮类给电子试剂对聚合物的结晶结构影响较大．取向样品随着拉伸倍数的增加结晶度和长周期增大，微晶尺寸变小．ＳＡＸＳ的散射强度计算表明，该聚合物属多分散非均一粒子体系，微孔半径在３．５－１６．４ｎｍ间．     

Synthesis,alkylation, and molecular and crystal structure ofN-methylmorpholinium 6-amino-3,5-dicyano-1,4-dihydropyridine-4-spirocyclohexane-2-thiolate

The reaction of cyano(cyclohexylidene)thioacetamide with cyanothioacetamide or malononitrile andN-methylmorpholine yieldsN-methylmorpholinium 6-amino-3,5-dicyano-1,4-dihydropyridine-4-spirocyclohexane-2-thiolate. Its structure was established based on the results of alkylation and X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2535–2540, October, 1996.     

Synthesis,molecular and crystal structures,and characteristic features of electronic structures of salicylamide-based B,Si-containing chelates

The reaction of 4-(2-hydroxybenzoyl)-2,2,6,6-tetramethyl-2,6-disilamorpholine with BF₃Et₂O afforded (O-B)-chelate 4-[2-(difluoroboroxy)benzoyl]-2,2,6,6-tetramethyl-2,6-disilamorpholine. Treatment of the latter with BF₃Et₂O or SOCl₂ gave rise to products of the disilamorpholine ring opening, viz., (O-B) chelate 2-(difluoroboroxy)-N,N-bis(dimethylfluorosilylmethyl)benzamide or 2-(difluoroboroxy)-N, N-bis(dimethylchlorosilylmethyl)benzamide, respectively. The structures of the compounds synthesized were confirmed by X-ray diffraction analysis and ¹H, ¹³C, and ²⁹Si NMR spectroscopy. High-precision X-ray diffraction study and quantum-chemical calculations demonstrated that the coordination OSi bond is absent in the two last-mentioned compounds.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1846–1853, September, 2004.     

Interconnection between the Structures and Sorption Characteristics of Mesophase Materials of MCM-41 Type Containing Alkylpyridines

Under the conditions studied for the synthesis of mesophase materials with alkylpyridinium halides an increase in the density of packing of these molecules in the encapsulated micelles was observed with an increase in the length of the alkyl radicals. The difference in the density of packing of these surface active reagents (SAR) depended to a considerable extent on the perfection of the hexagonal structure and the characteristic absorption properties of the mesophase materials of MCM-41 type.     

Crystallization of chiral compounds. 1. Spectroscopic,thermochemical, and crystallographic investigation of homochiral and racemic glycidyl p-toluenesulfonate

Crystalline specimens of homochiral and racemic glycidyl p-toluenesulfonate were studied by IR spectroscopy, differential scanning calorimetry, and X-ray diffraction analysis. The melting phase diagram of glycidyl p-toluenesulfonate was constructed. The stacking effect in the crystals of the racemic sulfonate is responsible for a more dense molecular packing, with the result that a heterochiral type of crystallization becomes more favorable.     

Synthesis and structure of novel derivatives of thieno[2,3-b]thiocine. An unusual product of intramolecular cycloaddition of 2-homomethallylthio-5-methyl-3-thiophenecarbonitrile oxide

9-Methyl-3,3a,4,5-tetrahydro-6H-thieno[2,3-b]thiocino[4,5-c]isoxazole and 9-hydroxyimino-2-methyl-7-methylene-6, 7,8,9-tetrahydro-5H-thieno[2,3-b]thiocine have been prepared for the first time by the oxidation of 2--alkenylthio-3-thiophenecarbaldoximes with NaOCl. X-ray structural investigations of thieno[2,3-b]thiocine and 2-homomethallylthio-5-methyl-3-thiophenecarbaldoxime have been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1262–1266, July, 1993.     

The preparation and X-ray structural study of complexes that catalyze isocyanate cyclotrimerization

A 11-complex of trinitrophenol with benzyldimethylamine (1) and a 111-complex, the product of the interaction of benzyldimethylamine, glycidyl phenyl ether, and phenol (2), have been synthesized and characterized by means of X-ray analysis. Complex1 is a precursor for the catalysts of selective isocyanate cyclotrimerization, while complex2 is one of those catalysts. In the crystal structure complex1 forms H-bonded cationic-anionic aggregates with proton transfer from phenol to the N-atom of the tertiary amine. Complex2 crystallizes as a monohydrate (2a) with a strong H-bond between the quaternary ammonium and phenolic components, and exists in crystals in the form of globular H-bonded dimeric hydrates. Possible pathways of dissociation of complex2a are discussed. The data obtained may be used as a basis for further interpretation of the regularities of cyclotrimerization of isocyanates catalyzed by complexes of this type.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 92–97, January, 1993.     

Synthesis and Inclusion Properties of the Host Compound 1,3-Dihydro-1,1,3,3-tetraphenylisobenzofuran. X-Ray Crystal Structures of the Free Host and of an Inclusion Compound with 1,4-Dioxane

A novel host molecule, 1, suitable for crystalline lattice-type inclusion, has been synthesized, and its cocrystal formation ability has been investigated. Host 1 proved to be of potential use for organic solvent separation and retrieval, and a promising auxiliary for solidification of certain odorous substances. The crystal structures of the solvent-free host 1, and its complex with 1,4-dioxane (1 : 1), have been determined by single crystal X-ray diffraction. The structure of 1 (guest-free) is triclinic, P , with a = 9.452(2), b = 10.359(3), c = 13.116(3) Å, = 101.80(2), = 106.53(1) and = 104.32(1)°. The spacious, propeller-like molecules are held together by weak van der Waals' forces. The dioxane inclusion compound is monoclinic, P21/a, with a = 15.050(1), b = 8.641(1) and c = 20.658(1) Å, and = 94.56(1)°, and contains two crystallographically independent guest molecules, both located around symmetry centres. The molecular packing seems to be governed by C—H···O type bonds (C···O = 3.31 and 3.48 Å) from the host to the dioxane oxygens.