Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

Rb[C6H3(COOH)2(COO–)] · [C6H3(COOH)3] · 2H2O: Synthesis,Crystal Structure,and Properties

The salt Rb[C₆H₃(COO)₂(^–)] · [C₆H₃(COOH)₃] · 2H₂O (I) of trimesic acid was synthesized and its thermal stability and conductivity (10^–11 ohm^–1 cm^–1 at 298 K) were measured. Molecular and crystal structures of I were established by X-ray diffraction analysis. Hydrogen bonding system in complex I was detected by IR and Raman spectroscopies. X-ray diffraction data agree with vibration spectroscopy data.     

Chemical dynamics of the CH(X2Π) + C2H4(X1A1g), CH(X2Π) + C2D4(X1A1g), and CD(X2Π) + C2H4(X1A1g) reactions studied under single collision conditions

The crossed beam reactions of the methylidyne radical with ethylene (CH(X(2)Π) + C(2)H(4)(X(1)A(1g))), methylidyne with D4-ethylene (CH(X(2)Π) + C(2)D(4)(X(1)A(1g))), and D1-methylidyne with ethylene (CD(X(2)Π) + C(2)H(4)(X(1)A(1g))) were conducted at nominal collision energies of 17-18 kJ mol(-1) to untangle the chemical dynamics involved in the formation of distinct C(3)H(4) isomers methylacetylene (CH(3)CCH), allene (H(2)CCCH(2)), and cyclopropene (c-C(3)H(4)) via C(3)H(5) intermediates. By tracing the atomic hydrogen and deuterium loss pathways, our experimental data suggest indirect scattering dynamics and an initial addition of the (D1)-methylidyne radical to the carbon-carbon double bond of the (D4)-ethylene reactant forming a cyclopropyl radical intermediate (c-C(3)H(5)/c-C(3)D(4)H/c-C(3)H(4)D). The latter was found to ring-open to the allyl radical (H(2)CCHCH(2)/D(2)CCHCD(2)/H(2)CCDCH(2)). This intermediate was found to be long lived with life times of at least five times its rotational period and decomposed via atomic hydrogen/deuterium loss from the central carbon atom (C2) to form allene via a rather loose exit transition state in an overall strongly exoergic reaction. Based on the experiments with partially deuterated reactants, no compelling evidence could be provided to support the formation of the cyclopropene and methylacetylene isomers under single collision conditions. Likewise, hydrogen/deuterium shifts in the allyl radical intermediates or an initial insertion of the (D1)-methylidyne radical into the carbon-hydrogen/deuterium bond of the (D4)-ethylene reactant were found to be-if at all-of minor importance. Our experiments propose that in hydrocarbon-rich atmospheres of planets and their moons such as Saturn's satellite Titan, the reaction of methylidyne radicals should lead predominantly to the hitherto elusive allene molecule in these reducing environments.     

Synthesis and structure of a three-dimensional lanthanide complex [Tm2(C5H3N(COO)2)3(H2O)3)]·H2O

A new three-dimensional complex [Tm₂(C₅H₃N(COO)₂)₃(H₂O)₃)]·H₂O (PDC?=?3,5-pyridinedicarboxylate), has been synthesized and its structure determined by x-ray single crystal diffraction methods. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a?=?14.579(4), b?=?11.193(3), c?=?14.839(5)?Å, β?=?94.009(6)°, U?=?2415.5(13)?ų. Two independent PDC ligands bridge Tm^III ions from different orientations to form a network. Thermogravimetric analyses on compound 1 show its high structural stability to 410°C.     

Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2]

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C₉H₇N(C₃H₅)]₂Cu^IICl_2.86Br_1.14 (I), [C₉H₇N(C₃H₅)]Cu^IBr₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^IBr₂ (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P2₁/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) ų, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) ų, Z = 2. The crystals of complex III are monoclinic: space group P2₁/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) ų, Z = 4. The structure of compound I is built of the Cu^IIX ₄ ^2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C₉H₇(C₃H₅)]₂ Cu ₂ ^I Br₄ forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C₉H₇(C₃H₅)]₂Cu ₂ ^I Br₄} _n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.     

[Cu(C8H4F3O2S)2(C12H8N2)]·C3H6O的合成及其晶体结构

标题配合物 [Cu(C8H4 F3O2 S) 2 (C12 H8N2 ) ]·C3H6 O属于三斜晶系 ,空间群为P1,并测得如下晶胞参数a =10 .5 77(3) ,b =15 .72 2 (4) ,c =10 .133(2 ) ,α =94 .5 3(2 ) ,β =10 0 .81(2 ) ,γ =96 .18(2 )° ,V =16 37.0 3 3,Z =2 ,Mr =74 4.18,Dx =1.5 1× 10 6 g·m- 3,F(0 0 0 ) =5 2 6 ,μ =8 2 4cm- 1,最终偏差因子为R =0 .0 83,Rw=0 .0 74。Cu(II)与 2个 4 ,4 ,4 三氟 1 (2 噻吩基 )丁二酮 1,3中的四个氧原子和菲咯啉中的两个氮原子 ,组成了一个畸变的八面体构型。     

配合物3AgNO3·2[C3H7S(CH2)2SC3H7]的晶体结构

本文测定了配合物3AgNO3·2BPrTE的晶体结构, 该晶体属三斜晶系, 空间各为PI,晶胞参数: a=0.8945(1), b=1.2355(2), c=1.3572(5)nm; α=98.69(2)°, β=92.74(2)°, γ=90.45(1)°; V=1.480nm^3; Z=2, 分子中三个Ag原子的配位数均为5, 但它们的配位多面体各不相同, Ag(3)为四方锥体, Ag(2)为三角双锥, Ag(1)则介于两者之间, NO3^-以单齿、不等长双齿和等长双齿两种形式配位于Ag原子。配体BPrTE也具有两种构象, 反式构象具有C1对称性, 并以两种形式和Ag原子配位, 偏转式构象不具有C4对称性, 与Ag原子形成五元螯合环, 分子为三维无限长链结构。     

Thermochemical study of [Sm(C7H5O3)2·(C4H6NO2S)]·2H2O

The product from reaction of samarium chloride hexahydrate with salicylic acid and Thioproline, [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O, was synthesized and characterized by IR, elemental analysis, molar conductance, and thermogravimetric analysis. The standard molar enthalpies of solution of [SmCl₃·6H₂O(s)], [2C₇H₆O₃(s)], [C₄H₇NO₂S(s)] and [Sm(C₇H₅O₃)₂·(C₄H₇NO₂S)·H₂O(s)] in a mixed solvent of absolute ethyl alcohol, dimethyl sulfoxide(DMSO) and 3 mol L^?1 HCl were determined by calorimetry to be Δ_s H _m ^Φ [SmCl₃ δ6H₂O (s), 298.15 K]= ?46.68±0.15 kJ mol^?1 Δ_s H _m ^Φ [2C₇H₆O₃ (s), 298.15 K]= 25.19±0.02 kJ mol^?1, Δ_s H _m ^Φ [C₄H₇NO₂S (s), 298.15 K]=16.20±0.17 kJ mol^?1 and Δ_s H _m ^Φ [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O (s), 298.15 K]= ?81.24±0.67 kJ mol^?1. The enthalpy change of the reaction (1) $$ SmCl_3 \cdot 6H_2 O(s) + 2C_7 H_6 O_3 (s) + C_4 H_7 NO_2 S(s) = Sm(C_7 H_5 O_3 )_2 \cdot (C_4 H_6 NO_2 S) \cdot 2H_2 O(s) + 3HCl(g) + 4H_2 O(1) $$ was determined to be Δ_s H _m ^Φ =123.45±0.71 kJ mol^?1. From date in the literature, through Hess’ law, the standard molar enthalpy of formation of Sm(C₇H₅O₃)₂(C₄H₆NO₂S)δ2H₂O(s) was estimated to be Δ_s H _m ^Φ [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O(s), 298.15 K]= ?2912.03±3.10 kJ mol^?1.     

The solid-state thermal decomposition of Sr3[La(C2O4)3(H2O)2]2·11H2O

Strontium(II)diaquatris(oxalato)lanthanate(III)unidecahydrate, Sr₃[La(C₂O₄)₃(H₂O)₂]₂·11H₂O, has been synthesized and characterized by elemental, IR and electronic spectral studies. Thermal studies (TG, DTG and DTA) in air showed that all the crystal and coordinated water molecules are removed at ca. 225 °C. The final end product at 1,000 °C was shown to be a mixture of mainly SrCO₃, Sr₃La₄O₉ and La₂Sr₂O₅ along with oxides and carbides of both the metal, through the formation of an intermediate mixture of likely SrC₂O₄ and La₂(C₂O₄)_2.8 at 282 °C, and SrCO₃ and La₂O(CO₃)₂ at 540 °C. The multi-step dehydration and decomposition of the compound has been explored from the DSC study in nitrogen up to 670 °C, and the evaluated kinetic parameters are discussed.     

Synthesis and X-ray diffraction study of cs3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)] and Cs5[UO2(CH3COO)3]3[UO2(NCS)4(H2O)] · 2H2O

Cs₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) and Cs₅[UO₂(CH₃COO)₃]₃[UO₂ (NCS)₄(H₂O)] · 2H₂O (II) have been synthesized via the reaction between uranyl acetate and cesium thiocyanate in aqueous solution. According to single-crystal X-ray diffraction data, both compounds crystallize in monoclinic system with the unit cell parameters a = 18.7036(5) Å, b = 16.7787(3) Å, c = 12.9636(3) Å, β = 92.532(1)°, space group C2/c, Z = 4, R = 0.0434 (I); and a = 21.7843(3) Å, b = 24.6436(5) Å, c = 13.1942(2) Å, β = 126.482(1)°, space group Cc, Z = 4, R = 0.0273 (II). Uranium-containing structural units of compound (I) are mononuclear [UO₂(CH₃COO)₃]^? and [UO₂(CH₃COO)(NCS)₂(H₂O)]^? moieties, which correspond to the AB ₃ ⁰¹ and AB⁰¹M ₃ ¹ crystallochemical groups (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?, M¹ = NCS^? and H₂O). The structure of compound II is built of [UO₂(CH₃COO)₃]^? and [UO₂(NCS)₄(H₂O)]^2? complexes, which belong to the AB ₃ ⁰¹ and AM ₅ ¹ crystallochemical groups, respectively. Uranium-containing complexes in both structures are linked into a framework by hydrogen bonds and electrostatic interactions with cesium cations. The IR spectra of compounds I and II agree well with X-ray diffraction data.     

π-Complexes of copper(I) halides with 3-(allylamino)-(C3H5NHC2H4CN, Apn) and 3-(diallylamino)-((C3H5)2NC2H4CN, Dapn)-propanenitrile. syntheses and crystal structures of compounds [CuCl(Apn)], [(H+Apn)Cu2Cl3], [(H+Dapn)CuCl2], and [(H+Dapn)CuBr2]

The ??-complexes [CuCl(C₃H₅NHC₂H₄CN)] (I), [(C₃H₅NH₂C₂H₄CN)Cu₂Cl₃] (II), [((C₃H₅)₂NHC₂H₄CN)CuCl₂] (III), and [((C₃H₅)₂NHC₂H₄CN)CuBr₂] (IV) are obtained as single crystals by the ac electrochemical synthesis on copper wire electrodes from ethanolic solutions of 3-(allylamino)propanenitrile, 3-(diallylamino)propanenitrile, and CuX₂ (X = Cl, Br). Their crystal structures are determined. The crystals of compounds I, III, and IV are monoclinic, space group P2₁/c, Z = 4. The crystals of compound II are triclinic, space group P $\bar 1$ , Z = 2. The unit cell parameters are a = 11.125(4), b = 8.769(4), c = 8.570(4) ?, ?? = 90.94(4)°, V = 835.9(6) ?³ (I); a = 6.2566(4), b = 7.5975(6), c = 11.1251(8) ?, ?? = 90.896(6)°, ?? = 92.827(5)°, ?? = 94.340(5)°, V = 526.57(7) ?³ (II); a = 11.656(4), b = 6.992(4), c = 14.681(5) ?, ?? = 100.89(4)°, V = 1174.9(9) ?³ (III); a =11.845(4), b = 7.282(4), c=14.855(5) ?, ?? = 100.37(4)°, V = 1260.4(9) ?³ (IV). The coordination mode of the Cu(I) atom in complex I includes two halogen atoms, the C=C bond, and the secondary amine N atom. The coordination environment in isostructural crystals of complexes III and IV is formed by the C=C bond and three halogen atoms as in complex II.     

配合物[Sm(C7H5O3)2(C4H6NO2S)]·2H2O的热化学研究

将六水氯化钐,水杨酸与硫代脯氨酸3种物质一起反应,制得了一种新的稀土三元固体配合物[Sm(C7H5O3)2(C4H6NO2S)].2H2O(s)。通过红外光谱、热重差热分析、元素分析等手段确定了其结构与组成。在常压、298.15 K下,分别测定了六水氯化钐、水杨酸、硫代脯氨酸和该配合物在混合溶剂(二甲亚砜∶乙醇∶3 mol.L-1HCl=1∶1∶1)中的溶解焓,并根据热化学原理得出了298.15 K时配合物[Sm(C7H5O3)2(C4H6NO2S)].2H2O(s)的标准摩尔生成焓ΔfHmΘ=(-2913.73±3.10)kJ.mol-1。     

Tantalocene complexes as bidentate métalloligands: (C5Me5)(C5H4X)Ta(H2)(PPh2) (C5Me5) (C5H4X)Ta(CO) (PPh2) (X = PPh2, CH2CH2NMe2)

The synthesis of new bidentate métalloligands derived from tantalocene(C₅Me₅)(C₅H₄X)Ta(H₂)(PPh₂) (X = PPh₂, 2P; X = CH₂CH₂NMe₂2N) and (C₅Me₅)(C₅H₄X)Ta(CO)(PPh₂) 4(P,N) is described. When opposed to chromium unsaturated fragments the phosphino functionalised complexes 2P and 4P act as chelating bidentate ligands affording Ta(V) (C₅Me₅)(C₅H₄PPh₂)Ta(CH₂) (μ-PPh₂)Cr(CO)₄ or Ta(III) (C₅Me₅)(C₅H₄PPh₂)Ta(CO)(μ-PPh₂)Cr(CO)₄ bimetallic complexes. The same reaction carried out starting from 2N gives rise to a μ-phosphido, μ-hydrido dibridged complex Cp*(C₅H₄CH₂CH₂NMe₂)TaH(μ-H)(μ-PPh₂)Cr(CO)₄.     

[Cu2(C2O4)(C12H8N2)2(C3H7NO)2](ClO4)2配合物的合成及其热分解

以邻菲罗啉、2,5二羟基-1,4-二噻烷和Cu(ClO4)2.6H2O为原料,合成了中心对称的双核配合物[Cu2(C2O4)(C12H,N2)2(C3 H7NO)2](ClO4)2(1).通过红外光谱、元素分析等分析测试手段对其进行了表征;借助TG-DTG技术在氮气气氛下研究了配合物的热分解情况,并根据热分析结果确定了...     

OH+ C2H2N←C2H3 + NO→CH3 + NCO反应机理的密度泛函理论研究

应用密度泛函理论研究了反应通道(a)C2H3 NO→CH3 NCO和(b)C2H3 NO→OH C2H2N的反应机理．在B3LYP／6-31G(d)水平上优化了反应物、中间体、过滤态、产物的几何构型，通过频率分析确定了11个中间体和10个过渡态．所有的反应物、中间体、过渡态、产物都在CCSD／6-311 G(d，P)水平上进行了单点能较正．并讨论了反应的异构化过程．计算结果表明10是能量最低的中间体，比反应物的能量低308．479kJ／mol；过渡态1／3，2／5，3／4，4／8比反应物的能量高，其中3／4是能量最高的过渡态，比反应物的能量高91．894kJ／mol．通道(a)和(b)的理论放热值分别为111．059和96．619kJ／mol．     

[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构

氯化钆;甘氨酸;固态配合物;[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构     

X-ray diffraction study of K3[UO2(C2O4)2(NCS)] · 3H2O

The single crystals of K₃[UO₂(C₂O₄)₂(NCS)] · 3H₂O were studied by X-ray diffraction. The compound crystallizes in the monoclinic system, space group P2₁/n, Z = 4, a = 10.673 Å, b = 12.041 Å, c = 13.856 Å, β = 110.18°, R = 0.0290. The basic structural units of the crystals of I are the island complex groups [UO₂(C₂O₄)₂NCS]^3? corresponding to the crystal-chemical group AB⁰¹ ₂M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ^2? , M¹ = NCS^?) of uranyl complexes and connected into a three-dimensional framework through electrostatic interactions and through hydrogen bonds involving potassium ions and water molecules.     

3-(diallylamino)propanenitrile ((C3H5)2NC2H4CN, L) π-complexes with copper(I) ionic salts. Syntheses and crystal structures of compounds [Cu(H+L)ClO4]ClO4 · H2O, [Cu(H+L)BF4]BF4 · H2O, and [Cu(H+L)(H2O)]SiF6 · H2O

Qualitative single crystals of ??-complexes Cu(H⁺L)(ClO₄)]ClO₄ · H₂O (I), Cu(H⁺L)(BF₄)]BF₄ · H₂O (II), and [Cu(H⁺L)(H₂O)]SiF₆ · H₂O (III) are synthesized from solutions of 3-(diallylamino)propanenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5?C5 and from the copper(II) salts (Cu(ClO₄)₂ · 6H₂O, Cu(BF₄)₂ · 6H₂O, and CuSiF₆ · 4H₂O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostructural, space group P2₁/n, Z = 4. For compound III, space group P2₁/c, Z = 8. Unit cell parameters: for I a =7.8153(3), b = 16.7824(7), c = 12.4426(5) ?, ?? = 93.410(2)°, V = 1629.1(1) ?³; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) ?, ?? = 94.354(2)°, V = 1583.2(1); and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) ?, ?? = 91.820(6)°, V = 2843.9(7) ?³. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H⁺L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO ₄ ^? or BF ₄ ^? anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF ₆ ^2? anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F??H (2.05?C2.51 ?).     

Structure of (C3H5NH3)2H2P2O7·H2O

The bis(cyclopropylammonium)dihydrogenodiphosphate monohydrate is a new diphosphate associated with the organic molecule C₃H₅NH₂. We report the chemical preparation and the crystal structure of this organic cation diphosphate. (C₃H₅NH₃)₂H₂P₂O₇.H₂O is orthorhombic (S.G. : P2₁2₁2₁), with Z = 4 and the following unit-cell parameters : a = 4.828(1) Å, b = 11.011(1) Å, c = 25.645(2) Å. The P₂O₇ groups and H₂O water molecules form a succession of bidimensional layers perpendicular to the c axis. The organic cations ensure the three-dimensional cohesion by NH-O hydrogen bonds.