双核配合物[Cu2(TS)(H2O)]·CH3OH的自组装制备和晶体结构

The binuclear complex [Cu₂(TS)(H₂O)]·CH₃OH, where TS denotes the binucleating ligand derived from the schiff base N,N′-bis(3-carboxylsalidene)trimethylenediamine, was obtained from the self-decomposition of mononuclear complex Na₂CuTS·H₂O. It crystallizes in the monoclinic system, space group P2₁/c. The lattice parameters are a=11.935(2)?,b=15.667(3)?,c=11.621(2)?,β=111.60(3)°,V=2020.2(7)?³, Z=4 with R=0.0467. The structure is made of binuclear units, in which two copper atoms are bridged by two phenolic oxygen atoms. The “inside”copper atom is coordinated by two nitrogens, two phenolic oxygens in a planar coordi-nation site, the copper atom deviates from the mean plane by 0.47?. The “outside” copper atom is five coordinated by two phenolic oxygen atoms、two equatorial carboxyl oxygen atoms and one axial water oxygen atom in a distorted tetragonal cone site, the copper atom is pulled out of the equatorial plane by 0.46?.     

2，2-联吡啶-3，3-二羧酸桥联的具有2D网格结构的Mn配位聚合物的合成、晶体结构

A Manganese(Ⅱ) polymer {[Mn(bpdc)(bipy)(H₂O)]·4.5H₂O}_n has been synthesized (bpdc=2,2-bipyridine-3,3-dicarboxylate,bipy=4,4-bipyridine) and characterized by IR, UV, elemental analysis and X-ray crystal structure determination . It crystallizes in Monoclinic system, space group P2/n with a=1.010 13(8) nm, b=1.164 66(9) nm, c=2.147 40(16) nm, β=98.22 20(10)°, V=2.500 4(3) nm³, Z=4, D_c=1.467 g·cm^-3, F(000)=1 144, R₁=0.049 0, wR₂=0.141 2. The crystal structure shows that the Mn²⁺ ions have octahedral coordination geometry with two coordination situations. The Mn²⁺ (1) ion is coordinated with two N atoms of two bipy, and chelated by four O atoms from four carboxylate groups of two bpdc ligands. The neighbor Mn²⁺ (2) ion is coordinated with two oxygen atoms from two water, two N atoms of two 4,4-bipy and two O atoms from two carboxylate groups of two bpdc ligands. Mn(1) and Mn(2) ions are bridged by bpdc and bipy ligands, forming a novel 2D network. CCDC: 651043.     

一维链状铜配位聚合物[Cu(m-BDOA)(bipy)·H2O]n的合成与晶体结构

A novel coordination polymer, [Cu(m-BDOA)(bipy)·H₂O]_n (m-BDOA^2-=benzene-1,3-dioxyacetate), was synthesized and characterized by elemental analysis, IR spectra, X-ray single crystal structure analysis. Crystallographic data are as follows: orthorhombic, space group Pna2₁, a=1.606 9(3) nm, b=1.685 9(3) nm, c=0.699 7(1) nm, V=1.8955(7) nm³, Z=4, D_c=1.619 g·cm^-3, μ=1.200 mm^-1, F(000)=948，R=0.038 1, wR=0.038 6. The copper atom is five-coordinated involving two oxygen atoms of different m-BDOA^2- ligand, two nitrogen atoms of 2,2′-bipy ligand and one coordinated water, there is a distorted square pyramidal environment. Two copper atoms are bridged by m-BDOA^2- ligand, forming a one-dimensional chain along a axis. The adjacent distance of Cu…Cu atoms is 0.877 3nm. The crystal network was formed by the intermolecular hydrogen bond and π-packing interactions.     

过渡金属-碱土金属铜钙四核配合物Cu2Ca2L2(H2O)6·2H2O的合成和晶体结构

The transition metal and alkaline earth metal tetranuclear complex Cu₂Ca₂L₂(H₂O)₆·2H₂O where H₄L represents the Schiff base N-3-carboxylsalicylideneglycylglycine was prepared and its crystal structure was determined by the single-crystal X-ray diffraction method at room temperature. It crystallizes in the monoclinic system, space group C2/c. The lattice parameters are a=2.128 2(2) nm, b=1.231 73(14) nm, c=1.32342(15) nm, β=93.619(2)°, M_r=939.81, D_c=1.803Mg·m^-3, F(000)=1 928, Z=4 with R₁=0.046 6. Each copper atom is coordinated by two nitrogen atoms, one carboxylate oxygen atom and one phenolic oxygen atom, in a square-planner manner. And each calcium atom is coordinated by three water oxygen atoms, three carboxylate oxygen atoms and one phenolic oxygen atom in a distorted pentagonal bipyramid. Two pentagonal bipyramids are connected by two carboxyl groups. CCDC: 239969.     

Cu2(μ-dppb)2(μ-Cl)2的合成、晶体结构及非线性光学性质

The complex Cu₂(μ-dppb)₂(μ-Cl)₂ has been synthesized from the reaction of CuCl， dppb and (n-Bu)₄NCl. The crystal belongs to the triclinic with space group P1. The unit cell parameters are: a=9.939(4)?， b=10.083(6)?， c=14.104(5)?， α=76.46(3)°， β=71.02(2)°， γ=70.87(5)°. The single crystal X-ray diffraction analysis reveals that it has a bi-ring structure with a symmetry center at the middle of two Copper atoms. The outer ring is a 14-membered ring of Cu-dppb-Cu-dppb， and the inner ring is a 4-membered ring composed of two Cl^- and two Cu(Ⅰ). Investigation of third-order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self-defocusing effect with α₂=1.75×10^-13m·W^-1 and n₂=3.19×10^-18m²·W^-1. CCDC: 193113.     

配合物[Cu(o-ABA)2(2，2′-bipy)]·(H2O)的水热合成、晶体结构及电化学性质

The title complex has been synthesized by o-acetamidobenzoic acid and 2,2′-bipyridine(bipy) in the mixture solvent of water and methanol. It crystallizes(C₂₈H₂₆CuN₄O₇, M_r=594.07) in Triclinic space group P1 with a=0.805 3(4) nm, b=0.845 5(4) nm, c=2.001 8(9) nm; α=100.797(8)°, β=93.054(7)°, γ=97.297(7)°, V=1.323 9(10) nm³, D_c=1.490 g·cm^-3, Z=2, F(000)=614. R₁=0.035 9, wR₂=0.080 5. The crystal structure shows that the copper atom is coordinated with four oxygen atoms from two o-acetamidobenzoic acid and two nitrogen atoms from the 2,2′-bipyridine, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 619084.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

配位聚合物[Mn(2，4，6-TMBA)2(H2O)3]n·2nH2O的水热合成和晶体结构

The title compound, [Mn(2,4,6-TMBA)₂(H₂O)₃]_n·2nH₂O(1), where 2,4,6-TMBA=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of monoclinic, space group C2/c with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 04(17) nm, V=2.494 7(9) nm³, Z=4, M=471.40, D_c=1.255 g·cm^-3, μ=0.571 mm^-1, F(000)=996, R_int=0.029 4, R=0.037 6 and wR=0.094 9. The Mn atoms are octahedrally coordinated by two O atoms of two ligands and four O atoms of water. The carboxyl group coordinates to Mn(Ⅱ) in the mode of monodentate, while the O atoms of water molecules coordinates in bridging mode. The complex shows a one-dimensional chain structure bridged by water molecules. CCDC: 297750.     

1,10-邻菲咯啉-铜(Ⅱ)-L-蛋氨酸配合物的合成、表征及其分子结构

The complex [Cu(L-met)(phen)(H₂O)]NO₃·H₂O has been synthesized and investigated by elemental analysis, molar conductivity, spectroscopic and X-ray diffraction methods, where phen=1,10-phenanthroline and L-met=L-methioninate group. The complex crystallized in the monoclinic space group P2₁ with a=12.053(2)?, b=6.886(1)?, c=13.385(3)?, β=113.59(3)°, V=1018.1(3)?³, Z=2,D_c=1.598g·cm^-3, μ=1.223mm^-1, F(000)=506, R₁=0.0306, and wR₂=0.0742. The copper(Ⅱ) atom is ligated in a distorted square-pyramidal geometry by two nitrogen atoms of one phen and the amino nitrogen atom , one carboxylate oxygen atom of L-met in the base plane, and an aqua at the apical position. A one-dimensional chain configuration formed by the hydrogen-bonding and weak Cu-O (the uncoordinated carboxyl oxygen atom) coordination interactions be-tween neighboring [Cu(L-met)(phen)(H₂O)]⁺ cations. CCDC: 183368.     

二维层状铜配位聚合物[Cu2(3-PyOH)2(EDTA)]n的合成与结构研究

A 2D copper coordination polymer of [Cu₂(3-PyOH)₂(EDTA)]_n (EDTA^4-=ethylenediaminetetraacetate quadrivalent anion C₁₀H₁₂N₂O₈, 3-PyOH=3-hydroxypyridine) was synthesized and characterized by the element analysis, IR and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system with space group P2₁/c, a=1.327 5(3) nm, b=0.930 39(19) nm, c=0.948 44(19) nm, β=108.21(3)°, and V=1.112 8(4) nm³, Z=2, R=0.025 2, wR=0.066 1. Each copper(Ⅱ) atom is five-coordinated by three O atoms and one N atom from two different EDTA^4- groups and one N atom from 3-PyOH ligand, forming a distorted square-pyramidal coordination geometry. Two adjacent copper(Ⅱ) atoms are bridged by the bis-tetradentate EDTA^4- groups, constructing a two-dimensional layer structure along bc plane. The adjacent Cu…Cu distances are 0.502 5(3) and 0.611 3(3) nm. CCDC: 618806.     

Dampfdruckmessungen und Protonenresonanzuntersuchung an Hydriden der intermetallischen Phasen Ti2(Ni,Co) und Ti2(Ni,Fe)

NMR and hydrogen equilibrium pressure measurements were performed on hydrides of the intermetallic compounds Ti₂(Ni, Co) and Ti₂(Ni, Fe). The following values of enthalpy H and entropy S for the formation of the hydrides of the intermetallic phases Ti₂Co and Ti₂Ni were found: H(Ti₂CoH _y )=–47.6 kJ/mol H₂, H(Ti₂NiH _y )=–53.7 kJ/mol H₂; S(Ti₂CoH _y )=–119.8 J/(K·mol H₂), S(Ti₂NiH _y )=–127.5 J/(K·mol H₂). By substitution of Ni or Co by Fe, the values of H and S of the corresponding quaternary hydrides become less negative. An interpretation of the experimental results is tried by the model ofShaltiel and coworkers.Proton diffusion was investigated in a series of the intermetallic hydrides Ti₂(Ni, Co)H _x and Ti₂(Ni, Fe)H _x . The diffusion rate is lowered by increased Ni/Fe substitution. Substitution of Ni by Co scarcely effects the hopping process. The activation energies were found to be smaller for the Ti₂Ni-hydrides compared with the Ti₂Co-hydrides.

Herrn Prof. Dr.H. Nowotny zum 70. Geburtstag gewidmet.     

N-substituted amides of 2-cyanopenta-2E,4-dienoic acid

N-Substituted amides of 2-cyanopenta-2E,4-dienoic acid were synthesized by condensation ofN-substituted cyanoacetamides with acrolein in a dioxane-DMSO solution in the presence of Zn(OAc)₂·2H₂O as a condensing agent. X-ray diffraction study of 3-methylanilide of 2-cyanopenta-2E,4-dienoic acid (2d) demonstrated that the crystal structure of this compound is similar to that of 2-cyanopenta-2E,4-dienoic acid studied previously. However, the presence of themeta-tolyl substituent in molecule2d apparently results in the fact that the β-structure, which is typical of 2-cyanopenta-2E,4-dienoic acid, does not exist in the crystalline phase of2d. Henkel Kommanditgesellschaft auf aktien, Deutschland, D-40191 Dusseldorf, Henkelstrasse, 67. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 933–937, May, 1999.     

Reaktivität der Pyrrolpigmente, 2. Mitt.: Deprotonierung von 3-Pyrrolin-2-onen

Deprotonation of 3,4-dimethyl-3-pyrrolin-2-on (1) int-butyl alcohol/potassiumt-butoxide solutions takes place on the N atom, as shown by¹H/²H exchange andpK _a determinations of1 (pK=17.1), 1,3,4-trimethyl-3-pyrrolin-2-one (pK _a =17.6), and 3,4-dimethyl-5-methoxy-2_H-pyrrole (pK _a =16.7). The SCF-MO approximation MINDO/3 indicates, however, that in the gas phase deprotonation of1 should occur at the C atom.

1.Mitt.:Ribó, J. M., Trull, F., Mh. Chem.110, 201 (1979).     

Synthesis ofN-(3-azido-2-nitroxypropyl)-,N-(2,3-diazidopropyl)-, andN-(2-azido-3-methoxypropyl)-N-alkylnitramines

N-(3-Azido-2-nitroxypropyl)-N-alkylnitramines andN-(2,3-diazidopropyl)-N-alkylnitramines were prepared by nitration and azidation ofN-alkyl-N-(2-hydroxy-3-chloropropyl)sulfamates andN-(3-azido-2-hydroxypropyl)-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 206–208, January, 1999.     

sym-Triazine Derivatives. 2. Synthesis, Properties, and Structure of 2-Oxo-1,2-dihydro-sym-triazines

Previously unreported 2-oxo-1,2-dihydro-sym-triazines have been prepared and their alkylation reactions have been studied. It was found that, independently of the structure and nature of the substituent in positions 4 and 6 of the triazine ring or the structure of the alkyl halide used, the reaction occurs regioselectively at the oxygen atom. The stereostructure of the 2-oxo-1,2-dihydro-sym-triazines was investigated by X-ray analysis and it was shown that they exist as dimers in the crystalline state.     

Chinazolinone, 2. Mitt.: Synthese und einige Reaktionen von 2-Azidomethyl-3-aryl-4-chinazolinonen

Starting with the chloromethyl compounds7 the new 2-azidomethyl-3-aryl-4-quinazolinones8 a-h were prepared, some of which have been reduced so far to the corresponding amines9 a, b, e, g by H₂S in good yield. As a first example for the capability of the azides8 to undergo 1,3-dipolar cycloaddition the 2-quinazolinmethyl-1,2,3-triazol-4,5-dicarboxylicacid dimethylesters11 b, e, g were prepared by reacting8 with dimethylacetylenedicarboxylate (10).

1. Mitt.:Domanig R., Arch. Pharm., im Druck.     

Die Photoenolisierung,Autoxidation und Dimerisation von 2-Isobutyliden-1,3-indandion

The title compound,1, slowly decomposes in solution by autodixation, especially in daylight. The chemism of this photoinduced autoxidation has been investigated.Upon irradiation1 passes to the brick red isolable dienol2. The quantum yield is 0.3 at 313 nm in methanol. In solution an equilibrium is set up within several minutes between2 and the colorless deconjugated3. Unpolar or moderately polar solvents shift the equilibrium completely to3, whereas in highly polar solvents2 and3 coexist. In the dark the equilibrium12 (ca. 501 in methanol) is established very slowly.3 upon irradiation reacts further to dimer8. 2 instantaneously reacts with oxygen. With high oxygen concentrations, hydroperoxide9 is formed, with lower ones dehydrodimer10, inter alia.9 and10 may further form12, 14, and15. These reactions, together with ESR spectroscopy, point to a central role of the free radical13 both in the autoxidation and in the reaction1014.Basic catalysis sets up an equilibrium between1 and its dimer,17. The photoreaction12 has been investigated by sensitizing and quenching experiments.

34. Mitteilung:J. Bitter, J. Leitich, H. Partale, O. E. Polansky, W. Riemer, U, Ritter-Thomas, B. Schlamann undB. Stilkerieg, Chem. Ber., im Druck.     

Magnetische Messungen im Nahordnungsbereich vonHeusler-Phasen (Co,T)2 XY

Magnetic measurements onHeusler alloys (Co,T)₂ XY (field and temperature dependence) are performed around theCurie points (temperature range:T _C–50 toT _C+50). A method otherwise used to get rid of ferromagnetic impurities only ( _g versus 1/H plot) is applied to pure ferromagnets and yields completely new _g (extrap.) versusT curves with a maximumT _max> T _C. The method was applied to pure gadolinium first which has aCurie point within the accessible region of the susceptibility measuring device.

     

Fluorosubstituted rhodacarboranes 3,4-(R3P)2-3-H-3,1,2-RhC2B9H11−n F n (n=1, 2, 4): Synthesis, molecular structure, and catalytic properties in hydrosilylation of styrene and phenylacetylene

Hydridorhodacarboranes 3,3-(Ph₂RP)₂-3-H-3,1,2-RhC₂B₉H_11−n F _n (R=Ph, Me;n=1, 2, 4) containing F atoms at the B atoms of the π-carborane ligand were synthesized from (Ph₃P)₃RhCl or (Ph₂MeP)₃RhCl andnido-7,8-C₂B₉H_12−n F _n ⁻ (n=1, 2, 4) salts. Hydridorhodacarboranes 3,3-(Ph₂MeP)₂-3-H-3,1,2-RhC₂B₉H_11−n F _n readily exchange the H atom at the Rh atom for the Cl atom under the action of CH₂Cl₂ to give 3,3-(Ph₂MeP)₂-3-Cl-3,1,2-RhC₂B₉H_11−n F _n . The structures of the 3,3-(Ph₃P)₂-3-H-3,1,2-RhC₂B₉H₇F₄ and 3,3-(Ph₂MeP)₂-3-Cl-3,1,2-RhC₂B₉H₉F₂ complexes were determined by X-ray diffraction analysis. Catalytic properties of the rhodacarbonanes obtained in hydrosilylation of styrene and phenylacetylene by PhMe₂SiH were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 570–578, March, 1997.     

Die Kristallstruktur der isotypen Verbindungen KAg(NO3)2, NH4Ag(NO3)2 und RbAg(NO3)2

KAg(NO₃)₂ crystallizes in space group P2₁/a-C _2h ⁵ ,a=13.953,b=4.955,c=8.220 Å, =97.76°,Z=4. X-ray intensities were collected with a two-circle diffractometer. The structure was solved by means of direct methods andFourier syntheses and was refined by the least squares method toR=0.034 with 1346 observed reflexions. ¹ {Ag₂(NO₃)₄}^2–-chains run parallel toy and are linked by potassium ions. Ag shows a distorted tetrahedral coordination with four relatively close O. K is irregularily surrounded by ten O. The isotypic compounds NH₄Ag(NO₃)₂ and RbAg(NO₃)₂ were refined toR=0.032 and 0.035, respectively. The coordination figures are compareable with those in KAg(NO₃)₂.