Copper(II) complexes of novel N-alkylated derivatives of cis,cis-1,3,5-triaminocyclohexane. 1. Preparation and structure

Novel N,N',N' '-trialkylated derivatives of cis,cis-1,3,5-triaminocyclohexane (tach), designated tach-R(3), were prepared through alkylation of N-protected tach with subsequent acid deprotection, to afford N-methyl, N-ethyl, and N-n-propyl derivatives as their trihydrobromide salts. The tach-neopentyl(3) and tach-furan(3) derivatives were prepared by formation of the imine from tach and pivaldehyde or furan-2-carboxaldehyde, respectively, followed by reduction of the imine. Complexes [Cu(tach-R(3))Cl(2)] (R = Me, Et, n-Pr, CH(2)-2-thienyl, and CH(2)-2-furanyl) were prepared from CuCl(2) in MeOH or MeOH-Et(2)O solvent. Crystallographic characterization of [Cu(tach-Et(3))Br(0.8)Cl(1.2)] (Pnma, a = 8.2265(1) A, b = 12.5313(1) A, c = 15.3587(3) A, Z = 4) reveals a square-based pyramidal CuN(3)X(2) coordination sphere in which one nitrogen donor occupies the apical position at a slightly longer distance (Cu-N = 2.218(5) A) than those of the basal nitrogens (Cu-N = 2.053(2) A). The solution-phase (pH 7.4 buffered and methanol) and solid-phase structures of [Cu(tach-R(3))Cl(2)] have been studied extensively by EPR and visible-near-IR spectroscopies. The square-based pyramidal structure is retained in solution, according to correspondence of solution and solid-state data. In aqueous solution, halide is replaced by water, as indicated by the high-energy UV-vis spectral shifts and bonding parameters of [Cu(tach-Et(3))](2+)(aq) derived from EPR data. The proposed aqueous-phase species, in the pH range 7.4 to 10.1, is [Cu(tach-Et(3))(H(2)O)(2)](2+). The complex [Cu(tach-Me(3))](2+)(aq) does not appear to dimerize or form metal-hydroxo species at pH 7.4, in contrast to other Cu(II)-triamine complexes, e.g., [Cu(1,4,7-triazacyclononane)](2+) (aq) and [Cu(tach-H(3))](2+)(aq) (the complex of unalkylated tach). This difference is attributed to the steric effect of the N-alkyl groups in the tach-R(3) series.     

1-(2-Methoxyphenyl)-1,4-Dihydro-5H-Tetrazole-5-Thione and Its Complex with Cd(II): Molecular and Crystal Structures

Russian Journal of Coordination Chemistry - The molecular and crystal structures of 1-(2-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione (L) and its complex with cadmium(II) (II) are studied by...     

Methylation of 5-Amino-3-methylthio-1H-pyrazole Derivatives and Two Related Crystal Structures

5-Amino-3-methylthio-1H-pyrazoles are very important building blocks from which a wide variety of pyrazole derivatives can be prepared. When substituted 5-amino-3-methylthio-1H-pyrazole was treated with CH3I, the methylation occurres at endocyclic two nitrogens at the same time. The ratio of isomers in products was depended upon the nature of 4-position substituent in the pyrazole ring. The products were characterized by X-ray diffraction analysis, and the ratios of isomer were explained by means of the results of ab inito calculation.     

Crystal and Molecular Structure of 2,3,5,6- Bis（ortho-1,10-decylidene）dihydropyrazine

1 INTRODUCTION The 1,4-dihydropyrazine ring system has attrac- ted much interest as a structural unit: 1) the possi- bility of cyclic 8π-electron conjugation gives rise to “antiaromatic” character; 2) these ring systems are thus electron rich and readily lose a single electron (namely single electron transfer reaction, SET) to give stable radical cations which are stabilized by captodative effect and/or other factors. Calculations for planar 1,4-dihydropyrazine have predicted the occup…     

Syntheses and Crystal Structures of Two Coordination Compounds CuLCl（H2O） and Ni（L）2 （HL = 2-Carboxy-1,10-phenanthroline）

Two complexes CuLCl（H2O） 1 and Ni（L）2 2 （HL = 2-carboxy-1,10-phenanthroline） have been synthesized and characterized by single-crystal X-ray crystallography. The structure of 1 has a monoclinic space group P21/n with a = 7.985（2）, b = 16.067（3）, c = 9.694（2） A, β = 98.189（30）°, V= 1231.0（4） A^3, Z = 4, Dc = 1.836 g/cm^3,μ =1.998 mm^-1, F（000） = 684, the final R = 0.0301 and wR = 0.0810. The structure of 2 （C26H14N4NiO10） adopts an orthorhombic system, space group Pbea with a = 9.410（2）, b = 23.2410（5）, c = 23.8680（5） A, V = 5219.9（18） A^3, Z = 8, Mr = 601.12, Dc = 1,530 g/cm^3,μ = 0.809 mm^-1, F（000） = 2448, the final R = 0.0448 and wR = 0.1427. The Cu center of complex 1 exhibits a square pyramidal coordination environment with one oxygen and two nitrogen atoms from deprotonated 2-carboxy-1,10-phenanthroline, one oxygen atom from water and one chloride ion. The Ni center of complex 2 assumes a distorted octahedral coordination geometry consisting of two oxygen atoms and four nitrogen atoms of two deprotonated 2-carboxy-1,10-phenanthroline molecules. Supramolecular assembly has been found via noncovalent bonds, such as hydrogen bonds and π-π stacking interactions.     

Synthesis and Crystal Structure of N-(1'-H-Pyrrol-2'-ylcarbonyl)-5-amino-1,10-phenanthroline

The title compound,N-(1'-H-pyrrol-2'-ylcarbonyl)-5-amino-1,10-phenanthroline,was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine.Determined by X-ray structure analysis,it crystallizes in triclinic system,space group P(1)with the following crystallographic data:C20H21N5O3,Mr=379.42,a=7.8559(4),b=9.1681(6),c =14.6818(9)(A),α=73.254(10),β=88.938(15),γ=68.080(10)°,V=934.66(10)(A)3,Z=2,F(000)=400.Dc=1.348 g/cm3 and μ=0.094 mm-1.The final R=0.0680 and wR=0.1419 for 2142observed reflections with I＞2σ(I),and R=0.1084 and wR=0.1643 for all reflections.Two aromatic ring planes(pyrrole and phenanthroline rings)are connected by the amide plane.Two title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 3-D supramolecule.     

Structure of di-μ-N-Phenylanthranilato-di-1, 5-cyclooctadiene dirhodium(I)

The reaction of [RhCl(COD)]₂ (COD = 1,5-cyclooctadiene) with sodium N-phenylanthranilate leads to the formation of the new crystalline rhodium(I) complex [RhFA(COD)]₂ (FA = N-phenylanthranilate anion). The compound is a dimer with two N-phenylanthranilate ions bridging and COD ligands terminally bonded to rhodium with an Rh … Rh distance equal to 3.424(3) Å. Strong intramolecular hydrogen bonding occurs between the hydrogen of the NH group and the closest carbonyl oxygen in the FA ligands. The crystals are monoclinic, space group P2₁/c, with a = 11.246(8), b = 14.999(9), c = 21.82(2) Å, β = 105.11(6)°. The structure was solved by the heavy-atom method and refined by least squares to R = 0.035 for 4260 diffractometer data.     

Cadmium(II) and Nickel(II) 1-Oxypyridyl-2-Selenolates: Synthesis and Molecular and Crystal Structures

Russian Journal of Coordination Chemistry - Cadmium (C20H16Cd2N4O4Se4) (I) and nickel (C10H8N2NiO2Se2) (II) selenolates are synthesized by the exchange reactions of sodium 1-oxypyridyl-2-selenolate...     

Rearrangement of Derivatives of 1,3-Dithian-5-amineinto Bicyclic 2-Thiazolidines. Crystal Structures of cis- and trans-1-(2-Aryl-1,3-dithain-5-yl)-2-thioureas and cis- and trans-5-Aryl-3-imino-7,7a-dihydro-1H,3H,5H-thiazolo[3,4-c]thiazoles

Under conditions normally applied to transform thioureas into the corresponding carbodiimides, cis- and trans-1-(2-aryl-1,3-dithian-5-yl)-2-thioureas 7 and 8 undergo a rearrangement to 5-aryl-3-imino-7,7a-dihydro-1H, 3H, 5H-thiazolo[3,4-c]thiazoles 9/10 with cis- and trans-fused rings, respectively. The structures of these novel heterocycles were established by X-ray analysis of compounds 9a , 9d , and 10d . The cis-fused compounds 9 are the thermodynamically more stable ones. The stereochemical outcome of the rearrangement depends on the carbenium ion stabilizing capability of the aryl moiety and on the reagent system applied. With Ar = Ph, p-Cl-Ph, p-O₂N-Ph, the reaction can be directed to deliver mainly either the cis-thiazolothiazoles 9 or the trans-thiazolothiazoles 10 . With Ar = 5-methyl-4-imidazolyl or p-Me₂N-Ph, formation of the cis-thiazolothiazoles ( 9a and 9b , resp.) is strongly favored independently of the reaction conditions, In contrast to it 2-aryl analogs, (1,3-dithian-5-yl)-2-thiourea 7g can be transformed into the carbodiimide 11 . Under rigorous conditions, 11 also undergoes rearrangement to the corresponding thiazolothiazole 9g . Mechanisms explaining the above findings are discussed. Reaction of trans-2-phenyl-1,3-dithian-5-amine 6d with phosgene or trichloromethyl chloroformate gives the 5-phenyl-7,7a-dihydro-1H,3H,5H-thiazolo[3,4-c]-thiazol-3-ones 12 and 13 , whereas the amine 5g lacking an aryl substitutent forms the sable isocyanate 14 . Compound 14 is transformed into the corresponding thiazolothiazolone 15 by refluxing in diglyme. Syntheses are described for the 1,3-dithian-5-amines 5 / 6 and the thioureas 7 / 8 derived therefrom. The relative configuration of 7d and 8d was determined by X-ray analysis. NMR data then allowed to assign the configurations of all compounds of types 7 and 8 .     

Crystal Structures of (Z)-1-Phenyl-1-phenylseleno-2-(p-tolylsulfonyl)ethene and (Z)-1,3-Diphenyl-3-phenyl-seleno-2-(p-tolylsulfonyl)-2-propen- 1-ol

1 INTRODUCTION The vinyl sulfones are versatile intermediates in organic chemistry and have been extensively stu- died[1]. The available methodology for vinyl sulfone synthesis mainly consists of Horner-Emmons reac- tions of carbonyl compounds with sulf…     

Comparison of Fungicidal Difference of Two Arylpyrazoles Based on the Crystal Structures,Density Functional Theory Calculation and Molecular Docking

Two arylpyrazoles I and Ⅱ were synthesized and characterized by NMR and single-crystal X-ray diffraction. Compound I displayed 71.4% fungicidal inhibition rate against Rhizoctonia solani at 0.1 ppm, better than the control pyraclostrobin, whereas Ⅱ had little activity. Their fungicidal difference was discussed from theoretic level based on the crystal structure, density functional theory(DFT) calculation and molecular docking. The B3 LYP/6-31 G** level was employed to explore the HOMO-LUMO energy gap and charge distribution. Molecular docking was performed on the probable target protein bc1-enzyme complex. DFT calculation and docking studies supported the in vitro findings.     

Alkoxo Bound Monooxo- and Dioxovanadium(V) Complexes: Synthesis, Characterization, X-ray Crystal Structures, and Solution Reactivity Studies

A large variety of oxovanadium(V) complexes, mononuclear VO(2)(+) and VO(3+) in addition to the dinuclear VO(3+), of the structural type (VOL)(2), (VOHL)(2), VOLHQ, K(VO(2)HL), K(VO(2)H(2)L), or (salampr) (VO(2)L) {where L = Schiff base ligand possessing alkoxo group(s); HQ = 8-hydroxyquinoline; salampr = cation of reduced Schiff base derived from salicylaldehyde and 2-amino-2-methylpropan-1-ol}, bound to alkoxo, phenolate and imine groups have been synthesized in high yields and characterized by several spectral and analytical methods, including single crystal X-ray studies. While the mononuclear VO(2)(+) complexes have been synthesized at alkaline pH, the dinuclear VO(3+) complexes have been synthesized under neutral conditions using alkoxo rich Schiff base ligands. The X-ray structures indicate that the cis-dioxo complexes showed longer V-O(alkoxo) bond lengths compared to the monooxo counterparts. The plot of V-O(phen) bond distances of several VO(3+) complexes vs the lmct showed a near linear correlation with a negative slope. The cyclic voltammograms revealed a reversible V(V)/V(IV) couple with the reduction potentials increasing to more negative ones as the number of alkoxo groups bound to V increases from 1 to 2. Moreover, the cis-dioxo VO(2)(+) complexes are easier to reduce than their monooxo counterparts. The solution stability of these complexes was studied in the presence of added water (1:4, water:solvent), where no decomposition was observed, unlike other Schiff base complexes of V. The conversion of the dioxo complexes to their monooxo counterparts in the presence of catalytic amounts of acid is also demonstrated. The reactivity of alkoxo bound V(V) complexes is also reported. X-ray parameters are as follows. H(4)L(3): monoclinic space group, P2(1)/c; a = 10.480(3), b = 8.719(6), c = 12.954(8) ?; beta = 101.67(4) degrees; V = 1126(1) ?(3); Z = 4; R = 0.060, R(w) = 0.058. Complex 1: monoclinic space group, P2(1)/n; a = 12.988(1), b = 9.306(2), c = 19.730(3) ?; beta = 99.94(1) degrees; V = 2348.9(7) ?(3); Z = 4; R = 0.031, R(w) = 0.027. Complex 2: monoclinic space group, P2(1)/n; a = 12.282(3), b = 11.664(2), c = 12.971(4) ?; beta = 97.89(2) degrees; V = 1840.5(8) ?; Z = 4; R = 0.035, R(w) = 0.038. Complex 5: monoclinic space group, P2(1)/c; a = 17.274(2), b = 6.384(2), c = 16.122(2) ?; beta = 116.67(1) degrees; V = 1588.7(7) ?(3); Z = 4; R = 0.039, R(w) = 0.043. Complex 8: monoclinic space group, P2(1)/c; a = 11.991(1), b = 11.696(4), c = 12.564(3) ?; beta = 110.47(1) degrees; V = 1650.8(8) ?(3); Z = 2; R = 0.045, R(w) = 0.049.     

Syntheses,Crystal Structures and Properties of Two New Compounds from a Flexible Bipodal Acid with Additional Amide Groups

Two novel compounds {[Cu(IBG)(4,4-bipy)(H_2O)_2]_2·11H_2O}_n(1) and {[Co(IBG)-(μ-H_2O)(H_2O)_2]·2H_2O}n(2) based on isophthaloylbisglycine(H_2IBG) have been synthesized and structurally characterized by thermogravimetric analysis, elemental analysis and single-crystal X-ray diffraction. Compound 1 shows a 1D chain sine/cosine chain structure, and compound 2 can be characterized as a 4-connected sql tetragonal planar network with the point symbol of {44·62}. Compound 2 has been characterized by magnetic measurements. In addition, 1 and 2 display an interesting reversible crystal-to-amorphous transformation.