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Title: Molecular and crystal structures of some novel derivatives of 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles

Abstract

The stereochemical aspects of the interaction of 2,6-bis(arylidene)-cyclohexanone and 2,6-bis(arylidene)-3-methylcyclohexanone with arylhydrazine (aryl is phenyl or 4-nitrophenyl) and methylhydrazine are investigated using X-ray diffraction analysis. The molecular structure of the 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles synthesized is determined by X-ray diffraction analysis for the first time. It is established that the stereochemistry of the products of the interaction between the cyclohexanone derivatives and arylhydrazines depends on the electronic nature of the substituent in the aryl group. Two regioisomeric products with different positions of the methyl group in the cyclohexane ring with respect to the arylidene fragment are synthesized by the reaction of 2,6-bis(4-methoxybenzylidene)-3-methylcyclohexanone with methylhydrazine. The influence of the substituents at the nitrogen atom of the pyrazoline ring on the intramolecular electronic interactions and the geometry of the heterocycle in the compounds under investigation is discussed.

Authors:
; ; ; ; ; ;  [1]
  1. National Academy of Sciences of Ukraine, Scientific and Technological Corporation 'Institute for Single Crystals' (Ukraine)
Publication Date:
OSTI Identifier:
21090947
Resource Type:
Journal Article
Resource Relation:
Journal Name: Crystallography Reports; Journal Volume: 52; Journal Issue: 2; Other Information: DOI: 10.1134/S1063774507020149; Copyright (c) 2007 Nauka/Interperiodica; Article Copyright (c) 2007 Pleiades Publishing, Inc; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; CRYSTAL STRUCTURE; CYCLOHEXANONE; INDAZOLES; INTERACTIONS; MOLECULAR STRUCTURE; PYRAZOLINES; X-RAY DIFFRACTION

Citation Formats

Abakumov, V. V., Shishkina, S. V., Zubatyuk, R. I., Gella, I. M., Pivnenko, N. S., Kutulya, L. A., E-mail: kutulya@isc.kharkov.com, and Shishkin, O. V. Molecular and crystal structures of some novel derivatives of 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles. United States: N. p., 2007. Web. doi:10.1134/S1063774507020149.
Abakumov, V. V., Shishkina, S. V., Zubatyuk, R. I., Gella, I. M., Pivnenko, N. S., Kutulya, L. A., E-mail: kutulya@isc.kharkov.com, & Shishkin, O. V. Molecular and crystal structures of some novel derivatives of 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles. United States. doi:10.1134/S1063774507020149.
Abakumov, V. V., Shishkina, S. V., Zubatyuk, R. I., Gella, I. M., Pivnenko, N. S., Kutulya, L. A., E-mail: kutulya@isc.kharkov.com, and Shishkin, O. V. Thu . "Molecular and crystal structures of some novel derivatives of 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles". United States. doi:10.1134/S1063774507020149.
@article{osti_21090947,
title = {Molecular and crystal structures of some novel derivatives of 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles},
author = {Abakumov, V. V. and Shishkina, S. V. and Zubatyuk, R. I. and Gella, I. M. and Pivnenko, N. S. and Kutulya, L. A., E-mail: kutulya@isc.kharkov.com and Shishkin, O. V.},
abstractNote = {The stereochemical aspects of the interaction of 2,6-bis(arylidene)-cyclohexanone and 2,6-bis(arylidene)-3-methylcyclohexanone with arylhydrazine (aryl is phenyl or 4-nitrophenyl) and methylhydrazine are investigated using X-ray diffraction analysis. The molecular structure of the 3-aryl-7-arylidene-3,3a,4,5,6,7-hexahydroindazoles synthesized is determined by X-ray diffraction analysis for the first time. It is established that the stereochemistry of the products of the interaction between the cyclohexanone derivatives and arylhydrazines depends on the electronic nature of the substituent in the aryl group. Two regioisomeric products with different positions of the methyl group in the cyclohexane ring with respect to the arylidene fragment are synthesized by the reaction of 2,6-bis(4-methoxybenzylidene)-3-methylcyclohexanone with methylhydrazine. The influence of the substituents at the nitrogen atom of the pyrazoline ring on the intramolecular electronic interactions and the geometry of the heterocycle in the compounds under investigation is discussed.},
doi = {10.1134/S1063774507020149},
journal = {Crystallography Reports},
number = 2,
volume = 52,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}
  • Two new cationic polyhydrido cluster complexes of iridium have been synthesized and characterized by single-crystal x-ray diffraction and by ir and /sup 1/H and /sup 31/P NMR spectroscopy (Ir/sup 3/(dppp)/sub 3/(H)/sub 7/(CO))/sup 2+ (2) and (Ir3/(PN)/sub 3/(H)/sub 7)2+/ (5), where dppp = 1,3-bis(diphenylphosphino)propane and PN = 1-(2-pyridyl)-2-(diphenylphosphino)ethane, were synthesized by the reaction of CO with (Ir/sub 3/(dppp)/sub 3/(H)/sub 7/)/sup 2+/ (1) in CH/sub 2/Cl/sub 2/ solution and H/sub 2/ with (Ir(PN)(COD))/sup +/ (4) in CH/sub 3/OH solution, respectively. Crystal structures for both compounds is reported. The hydride positions were not located in the crystal structure analyses but were deduced frommore » structural and /sup 1/H NMR data. The molecular structure of 2 consists of a bilateral triangle of three iridium atoms with a carbonyl at the vertex and a chelating dppp ligand on each iridium atom. /sup 1/H NMR data with use of acetone-d/sub 6/ as solvent showed that 2 possesses four doubly bridging hydrides and three terminal hydrides, yielding C/sub 1/ symmetry. The molecular structure of 5 consists of an approximately equilateral triangle of three iridium atoms (average Ir-Ir distance 2.746 (1) /angstrom/) with one PN ligand chelated to each iridium atom. /sup 1/H NMR analysis, with use of CD/sub 2/Cl/sub 2/ as solvent, showed that 5 has one triply bridging hydride and six terminal hydrides, giving C/sub 3/ symmetry. (Ir/sub 3/(dppp)/sub 3/(H)/sub 7/(CH/sub 3/C/sub 6/H/sub 4/NC))/sup 2+/ (3) a complex structurally analogous to 2, was synthesized from 1 and p-tolyl isocyanide in CH/sub 2/Cl/sub 2/ solution and characterized by ir and /sup 1/H and /sup 31/P NMR spectroscopy. 44 refs., 3 figs., 3 tabs.« less
  • Trifluoromethyl derivatives of C{sub 86} were obtained by the reaction of a mixture of higher fullerenes with trifluoromethyl iodide, followed by the HPLC separation of the products. The crystal and molecular structures of C{sub 86}(CF{sub 3}){sub 16} (two isomers) and C{sub 86}(CF{sub 3}){sub 18} were determined by single-crystal X-ray diffraction using synchrotron radiation. All compounds studied are derivatives of the cage isomer of C{sub 86} no. 17 (C{sub 2}).
  • Trifluoromethyl derivatives of C{sub 82} have been obtained by the reaction between a higher fullerene mixture and trifluoromethyliodide, with subsequent isolation by high-performance liquid chromatography. The crystal and molecular structures of C{sub 82}(CF{sub 3}){sub 12} and C{sub 82}(CF{sub 3}){sub 18} have been determined by single crystal X-ray diffraction using synchrotron radiation. Both molecules are derivatives of C{sub 2}-C{sub 82} fullerene (isomer 3).
  • Several series of complexes of the types (MeHg(SR)) and (Hg(SR){sub 2}) have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed {sup 1}H, {sup 13}C, and {sup 199}Hg NMR studies revealed several general trends. The {sup 199}Hg chemical shifts moved upfield in the order (MeHg(SR)) < (Hg(SCR{prime}R{double prime}R{prime}{double prime}){sub 2}) < (Hg(S-aryl){sub 2}) < (Hg(S-pyridyl){sub 2}). For the (MeHg(SR)) series of complexes, {sup 1}J(Hg-C) correlates with {delta}({sup 13}C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limitedmore » correlation of {delta}({sup 199}Hg) with steric cone angles for a subset of the complexes. Crystal data for the complexes are reported. 86 refs., 7 figs., 11 tabs.« less
  • Ruthenium methoxide dimer (Cp*Ru({mu}-OMe)){sub 2} (1, Cp* = {eta}{sup 5}-C{sub 5}Me{sub 5}) is produced by reaction of (Cp*RuCl{sub 2}){sub 2} or Cp*RuCl{sub 2}(pyr) with NaOMe in methanol or by reaction of CP* (PCy{sub 3})RuCl with LiOMe in methanol. Compound 1 is best prepared in pure form (in 84% yield) by reaction of the tetranuclear cluster (Cp*RuCl){sub 4} with 4 equiv of LiOMe in methanol. An X-ray crystallography study revealed that 1 has a dimeric structure with bridging methoxy ligands. The dimer is folded along the O{hor ellipsis}O axis, with a fold angle of 124.3{degree}. Complex 1 crystallizes in the monoclinicmore » space group C2/c with a = 15.821 (8) {angstrom}, b = 6.659 (3) {angstrom}, c = 21.51 (1) {angstrom}, {beta} = 103.32 (3){degree}, Z = 8, V = 2,205 (2) {angstrom}{sup 3}, and R{sub F} = 2.17%. Ethoxide dimer (Cp*Ru({mu}-OEt)){sub 2} (2), prepared from (Cp*RuCl){sub 4} and LiOEt in ethanol, combines with carbon monoxide to form the adduct (Cp*(CO)Ru({mu}-OEt)){sub 2} (3). Compound 3 crystallizes in tetragonal space group P{anti 4}2{sub 1}C with a = 26.22 (2) {angstrom}, c = 8.709 (5) {angstrom}, Z = 8, V = 5,986 (6) {angstrom}{sup 3}, and R{sub F} = 5.68%. An analogous adduct of 1, (Cp*(CO)Ru({mu}-OMe)){sub 2} (4), is observed by {sup 1}H NMR but is unstable in solution, eventually decomposing to (Cp*Ru(CO)({mu}-CO)){sub 2}. Reaction of LiO-2,6-{sup t}bu{sub 2}c{sub 6}H{sub 3} with (Cp*RuCl){sub 4} in toluene gives the {eta}{sup 5}-oxocyclohexadienyl complex Cp*Ru({eta}{sup 5}-2,6-{sup t}Bu{sub 2}C{sub 6}H{sub 3}O) (5), which was crystallographically characterized. Compound 5 crystallizes in space group P2{sub 1}/n with a = 12.203 (3) {angstrom}, b = 10.028 (3) {angstrom}, c = 18.414 (4) {angstrom}, {beta} = 99.11 (2){degree}, Z = 4, V = 2,225 (1) {angstrom}{sup 3}, and R{sub F} = 3.03%.« less