[Ni(CHZ)_3](TNR)·5H_2O的制备、晶体结构和热分解机理

用 2 ,4,6 三硝基间苯二酚 (斯蒂芬酸 ,TNR)镍的水溶液和碳酰肼 (CHZ ,NH2 NHCONHNH2 )水溶液反应 ,制备出配合物 [Ni(CHZ) 3](TNR)·5H2 O ,测定了其晶体结构 ,并用TG DTG ,DSC和IR技术研究了其热分解机理 .该晶体属三斜晶系 ,P1空间群 ,晶胞参数a =1 0 45 40 (1 0 )nm ,b =1 1 6 71 (2 )nm ,c =1 2 2 78(2 )nm ,α=1 0 9 1 90 (1 0 )°,β=1 2 1 1 6 8(1 2 )°,γ =99 70 0 (1 0 )°,V =1 2 6 1 3(3)nm3,Z =2 ,Dc=1 744 g/cm3,μ(Mo ,Kα) =0 873mm-1,F(0 0 0 ) =6 88,R =0 0 41 9,Rw=0 1 0 5 3.在该配合物分子中 ,碳酰肼为双齿配体 ,由羰基O原子和 1位N原子与Ni2 + 离子配位 ,分子中共形成 3个五元平面螯合环 ,中心离子为六配位八面体结构 .该配合物在程序升温条件下 ,分两步脱去所含结晶水 ,第一步失去 4个结晶水 ,第二步失去 1个结晶水 ,在 5 0 0℃时的最终分解产物为Ni2 O3.     

Na2[(VO)12O6B18O39(OH)3]·(11H3O)·4H2O的水热合成和晶体结构

以V2O5, Na2B4O7·0H2O, NaH2PO4·2H2O, 乙二胺和H2O为原料, 按物质的量比0.5∶1∶1∶2.24∶111在180 ℃条件下晶化, 得到棕色晶体Na2[(VO)12O6B18O39(OH)3]·(11H3O)*4H2O. 单晶结构分析结果表明该化合物属单斜晶系, P21/n空间群, 晶胞参数 a=1.389 70(8) nm, b=1.661 59(9) nm, c=1.427 48(8) nm, β=95.691 0(10)°. Z=4, R=0.054 9. 该化合物的结构主要由阴离子簇[(VO)12O6B18O39(OH)3]13-构成. 该阴离子簇由B18O39(OH)3十八元环夹在两个以共边方式交替相连形成的V6O15簇中间, 通过共用氧原子形成三明治式结构新颖的硼-钒-氧阴离子簇, 结构中Na+以离子键方式将阴离子簇相互连接, 形成二维层状结构. 层与层之间通过分子间氢键相互作用. 价态计算结果表明, 结构中n(VⅣ)∶n(VⅤ)=5∶1.     

新型一维链状氰根桥联配合物[Eu(DMF)4(H2O)2Mn(CN)6*H2O]n的合成与晶体结构

以K3Mn(CN) 6,N ,N 二甲基甲酰胺和Eu(NO3) 3·6H2 O为原料合成了新型一维链状氰根桥联配合物[Eu(DMF) 4(H2 O) 2 Mn(CN) 6·H2 O]n,并通过元素分析、红外光谱和紫外光谱进行了表征 .利用单晶X射线四圆衍射测定了配合物的晶体结构 ,结果表明 ,晶体属单斜晶系 ,P2 1/c空间群 ,晶胞参数a =1.2 992 (3)nm ,b =1.2 76 4(3)nm ,c =1.915 4(4 )nm ,β =10 9.42 (3)°,V =2 .995 6 (12 )nm3,Dx=1.5 73Mg/m3,Z =4,R =0 .0 372 ,Rw=0 .0 96 2 ,GOF =1.0 95 .在Eu和Mn原子之间存在两个CN桥 ,配合物呈现一维链状结构 .     

[NEt4][Mn(salophen)(H2O)2]2[Fe(CN)6]· H2O· CH3OH超分子化合物的合成和结构

室温下将 [NEt4 ]3[Fe (CN) 6 ]和 [Mn (salophen) (H2 O) (CH3OH ) ]ClO4 反应 ,得到了超分子化合物[NEt4 ][Mn(salophen) (H2 O) 2 ]2 [Fe(CN) 6 ]·H2 O·CH3OH (salophenH2 =双水杨醛缩邻苯二胺 ) ,并对其进行了晶体结构测定 .结果表明 ,该晶体属三斜晶系 ,空间群P1- ,晶胞参数a =1.2 15 0 ( 4)nm ,b =1.483 4( 6)nm ,c =1.662 5 ( 6)nm ,α =81.896( 7)° ,β =76.980 ( 8)° ,γ =81.12 0 ( 6)°,V =2 .872 ( 2 )nm3,Z =2 ,Dc=1.3 88g·cm-3.晶体的各部分间以氢键连接成网状超分子体系     

[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。     

[La(Phen)2(NO3)2(H2O)2]ClO4·2Phen·H2O的合成与晶体结构

合成了[La(Phen)2(NO3)2(H2O)2]ClO4·2Phen·H2O(1,化学式为C48H38ClN10O13La,Mr=1137.24,Phen=邻菲咯啉),经X-射线单晶衍射测定其晶体结构属于三斜晶系,Pī空间群,a=11.250(4),b=13.364(4),c=16.327(5)(。A),α=103.042(6),β=90.327(6),γ=99.567(6)°,V =2355.8(12)(。A)3,Z = 2,Dc =1.603g·cm-3,F(000)=1148,μ=1.042mm-1,R=0.0569,wR= 0.1064.1由 [La(Phen)2(NO3)2(H2O)2]+ 阳离子,ClO-4阴离子,两个共结晶的Phen分子和1个H2O分子构成.内界的中心金属La(III)离子为十配位的变形的双帽四方反棱柱体,其配位环境分别被6个来自两个双齿配位硝基和两个H2O分子的氧原子和4个来自两个Phen配体的氮原子所包围,形成单核+1价阳离子,外界有1个水分子,1个ClO-4阴离子和两个Phen分子构成.整个分子通过分子间氢键形成3D网络结构.     

[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O的 合成、晶体结构及磁性质

Mn(O2CMe)2·4H2O、咪唑、苯甲酸和N(n-Bu)4MnO4在无水乙醇溶剂中反应,制备得到锰的三核μ3-O桥联配位化合物[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O.该配位化合物的X射线单晶衍射表明,其属于单斜晶系,空间群P21/C,晶胞参数：a=1.52832(19)nm,b=1.9722(2)nm,c=2.1023(3)nm,β=92.597(3)°,Z=4.变温磁化率(5～280K)研究表明,该配位化合物中3个锰离子在低温下存在弱的反铁磁性耦合,交换积分J=-2.34cm^-1。     

新型杂多阴离子[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-的结构及表征

在pH=4.5的水溶液中,Na27[NaAs4W40O140]·60H2O与NiCl2·6H2O, NaVO3·4H2O和NH4Cl反应得到了不同过渡金属离子占据S2位的新型杂多钨酸盐(NH4)21[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]·53H2O,用X射线单晶衍射法和元素分析确定了其结构.晶胞参数为a=2.3305(14) nm, b=2.9467(19) nm, c=1.2671(16) nm, V=8.701(9) nm3, Z=2,空间群Pmmn.在杂多阴离子[{Na2(H2O)3}Ni(H2O)VOAs4W40O140]21-中,配体{As4W40}的1个中心位和4个S2位可以选择性地被不同的金属离子所占据,其中相对的2个S2位被Ni2+和V5+统计性地占据,每种离子占据的概率为50%;{As4W40}中的另2个S2位分别被2个Na+占据,2个Na+间通过一配位水分子桥连.讨论了标题化合物的IR, TG和磁学性质.     

Ge_(10)O_(28)单元构建的两个三维锗酸盐结构:(H_3O)_4Ge_7O_(16)·3H_2O和K_4Ge_9O_(20)

在半水溶剂热条件下 ,采用不同的合成条件合成了两个锗酸盐微孔分子筛 :(H3O) 4Ge7O16 ·3H2 O和K4 Ge9O2 0 .X射线单晶结构解析表明 ,两个晶体结构具有相同的“火箭状”二级结构单元 (SBU) ,SBU的不同的连接方式导致了完全不同的空间结构 .H4 Ge7O16 ·7H2 O的结晶学数据为Mr=894 2 7,P 43m ,a =0 7730 9( 18)nm ,V =0 462 0 5 ( 19)nm3,Z =1,MoKα ,λ =0 0 710 73nm ,R(F) =3 48% ,wR(F2 ) =8 39% .K4 Ge9O2 0 的结晶学数据为 :Mr=112 9 71,I4( 1) /a ,a =1 5 0 0 2 ( 3)nm ,c =0 7383( 2 )nm ,V =1 6618( 7)nm3,Z =4,MoKα ,R(F) =3 92 % ,wR(F2 ) =11 97% .     

[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C10H10N2O4,简作H3L)、1,10-菲啰啉C12H8N2,简作phen)与Eu(NO3)3·4H2O反应,首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O.该晶体属三斜晶系,P1空间群,晶胞参数a=1.378 6(12) nm,b=1.398 8(12) nm,c=1.759 7(16) nm,α=73.977(11)°,β=68.598(12)°,γ=71.224(12)°,V=29.42(4) nm3,Z=2,μ=2.208 mm-1,Dc=1.746 Mg/m3,F(000)=1 556,R=0.037 7,ωR=0.074 4,GOF=0.916.每个配合物晶体中均有两个相似的结构单元,每个结构单元中铕(Ⅲ)配位数为9,分别与两个2-羰基丙酸水杨酰腙和3个水分子配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和CN中的氮与Eu3+配位,形成两个共边的稳定的五元环,另3个配位原子则分别来自3个水分子中的氧原子,该结构单元在空间呈扭曲的单帽四方反棱柱,而在每两个铕的九配位单元周围还有一个游离的1,10-菲啰啉分子和4个水分子.IR,1H NMR及热分解结果佐证了配合物的组成.该配合物具有很好的荧光特性.     

Dielectric characteristics of O2(H2O)i and (O2)2(H2O)i clusters. Computer-aided experiment

Absorption of oxygen molecules by water clusters with sizes of 10 ≤ i ≤ 50 is studied by the molecular dynamics method using the modified TIP4P model. It is revealed that the total dipole moment of the clusters nonmonotonically increases with their sizes. Absorption of O₂ molecules tends to raise the static permittivity of the ultradispersed medium formed by the clusters. The real and imaginary parts of the permittivity of water clusters with absorbed O₂ molecules are aperiodic functions of frequency. The permittivity components turn out to be nonmonotonic functions of cluster sizes. The IR absorption and reflectance spectra are calculated for clusters of pure water and aggregates with absorbed O₂ molecules. After the addition of oxygen molecules, the absorption coefficient of the clusters decreases, while the reflection coefficient increases. It is concluded that the capture of oxygen molecules by atmospheric moisture may reduce the greenhouse effect. Original Russian Text ? A.E. Galashev, V.N. Chukanov, O.A. Galasheva, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 155–160.     

Proton magnetic shielding in H2O and (H2O)2

The proton magnetic shielding constants in the water molecule and its linear perpendicular dimer are computed from SCF-MO-LCGO wave functions by using the uncoupled Hartree-Fock variation-perturbation procedure due to Karplus and Kolker. The convergence of the calculated shielding constants as well as their gauge dependence is studied. The final results for 17-term polynomial variation function indicate that the best choice for the gauge origin corresponds to the molecular electronic centroid.The calculated proton magnetic shielding constant in the water molecule is in remarkable agreement with experimental data and favourably compares with the best coupled Hartree-Fock results. It follows from the calculations for the water dimer that the H-bond NMR-shift amounts in this case —1.0 ppm and qualitatively agrees with the experimental data for the liquid water.     

Diffusivity fractionations of H2(16)O/H2(17)O and H2(16)O/H2(18)O in air and their implications for isotope hydrology

We have determined the isotope effects of (17)O and (18)O substitution of (16)O in H(2)O on molecular diffusivities of water vapor in air by the use of evaporation experiments. The derived diffusion fractionation coefficients (17)alpha(diff) and (18)alpha(diff) are 1.0146 +/- 0.0002 and 1.0283 +/- 0.0003, respectively. We also determined, for the first time, the ratio ln((17)alpha(diff))/ln((18)alpha(diff)) as 0.5185 +/- 0.0002. This ratio, which is in excellent agreement with the theoretical value of 0.5184, is significantly smaller than the ratio in vapor-liquid equilibrium (0.529). We show how this new experimental information gives rise to (17)O excess in meteoric water, and how it can be applied in isotope hydrology.     

Ferromagnetism in malonato-bridged copper(II) complexes. Synthesis,crystal structures,and magnetic properties of [[Cu(H2O)3][Cu(mal)2(H2O)]]n and [[Cu(H2O)4]2[Cu(mal)2(H2O)]][Cu(mal)2(H2O)2][[Cu(H2O)4][Cu(mal)2(H2O)2][(H2mal = malonic acid)

Three malonato-bridged copper(II) complexes of the formulas [[Cu(H2O)3][Cu(C3H2O4)2(H2O)]]n (1), [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]] [Cu(C3H2O4)2(H2O)2][[Cu(H2O)4][Cu(C3H2O4)2(H2O)2]] (2), and [Cu(H2O)4][Cu(C3H2O4)2(H2O)2] (3) (C3H2O4 = malonate dianion) have been prepared, and the structures of the two former have been solved by X-ray diffraction methods. The structure of compound 3 was already known. Complex 1 crystallizes in the orthorhombic space group Pcab, Z = 8, with unit cell parameters of a = 10.339(1) A, b = 13.222(2) A, and c = 17.394(4) A. Complex 2 crystallizes in the monoclinic space group P2/c, Z = 4, with unit cell parameters of a = 21.100(4) A, b = 21.088(4) A, c = 14.007(2) A, and beta = 115.93(2) degrees. Complex 1 is a chain compound with a regular alternation of aquabis(malonato)copper(II) and triaquacopper(II) units developing along the z axis. The aquabis(malonato)copper(II) unit acts as a bridging ligand through two slightly different trans-carboxylato groups exhibiting an anti-syn coordination mode. The four carboxylate oxygens, in the basal plane, and the one water molecule, in the apical position, describe a distorted square pyramid around Cu1, whereas the same metal surroundings are observed around Cu2 but with three water molecules and one carboxylate oxygen building the equatorial plane and a carboxylate oxygen from another malonato filling the apical site. Complex 2 is made up of discrete mono-, di-, and trinuclear copper(II) complexes of the formulas [Cu(C3H2O4)2(H2O)2]2-, [[Cu(H2O)4] [Cu(C3H2O4)2(H2O)2]], and [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]]2+, respectively, which coexist in a single crystal. The copper environment in the mononuclear unit is that of an elongated octahedron with four carboxylate oxygens building the equatorial plane and two water molecules assuming the axial positions. The neutral dinuclear unit contains two types of copper atoms, one that is six-coordinated, as in the mononuclear entity, and another that is distorted square pyramidal with four water molecules building the basal plane and a carboxylate oxygen in the apical position. The overall structure of this dinuclear entity is nearly identical to that of compound 3. Finally, the cationic trimer consists of an aquabis(malonato)copper(II) complex that acts as a bismonodentate ligand through two cis-carboxylato groups (anti-syn coordination mode) toward two tetraaqua-copper(II) terminal units. The environment of the copper atoms is distorted square pyramidal with four carboxylate oxygens (four water molecules) building the basal plane of the central (terminal) copper atom and a water molecule (a carboxylate oxygen) filling the axial position. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-290 K. Overall, ferromagnetic behavior is observed in the three cases: two weak, alternating intrachain ferromagnetic interactions (J = 3.0 cm-1 and alpha J = 1.9 cm-1 with H = -J sigma i[S2i.S2i-1 + alpha S2i.S2i+1]) occur in 1, whereas the magnetic behavior of 2 is the sum of a magnetically isolated spin doublet and ferromagnetically coupled di- (J3 = 1.8 cm-1 from the magnetic study of the model complex 3) and trinuclear (J = 1.2 cm-1 with H = -J (S1.S2 + S1.S3) copper(II) units. The exchange pathway that accounts for the ferromagnetic coupling, through an anti-syn carboxylato bridge, is discussed in the light of the available magneto-structural data.     

Fe2P2O7(H2O)2

The compound diiron diphosphate dihydrate, Fe₂P₂O₇(H₂O)₂, was synthesized hydro­thermally and crystallizes in the monoclinic space group P2₁/n. The compound has a somewhat open framework made up of edge‐sharing iron(II) octahedra that form chains connected by five bridging diphosphates. The remaining octahedral site of each iron is occupied by coordinated water. The H atoms of the water molecules all point into a common channel.     

One‐dimensional Cadmium(II) Coordination Polymers: Syntheses and Crystal Structures of [Cd(H2O)3(C5H6O4)]·2H2O,Cd(H2O)2(C6H8O4), and Cd(H2O)2(C8H12O4)

[Cd(H₂O)₃(C₅H₆O₄)]·2H₂O ( 1 ) and Cd(H₂O)₂(C₆H₈O₄) ( 2 ) were prepared from reactions of fresh CdCO₃ precipitate with aqueous solutions of glutaric acid and adipic acid, respectively, while Cd(H₂O)₂(C₈H₁₂O₄) ( 3 ) crystallized in a filtrate obtained from the hydrothermal reaction of CdCl₂·2.5H₂O, suberic acid and H₂O. Compound 1 consists of hydrogen bonded water molecules and linear {[Cd(H₂O)₃](C₅H₆O₄)_2/2} chains, which result from the pentagonal bipyramidally coordinated Cd atoms bridged by bis‐chelating glutarato ligands. In 2 and 3 , the six‐coordinate Cd atoms are bridged by bis‐chelating adipato and suberato ligands into zigzag chains according to {[Cd(H₂O)₃](C₅H₆O₄)_2/2} and {[Cd(H₂O)₂](C₈H₁₂O₄)_2/2}, respectively. The hydrogen bonds between water and the carboxylate oxygen atoms are responsible for the supramolecular assemblies of the zigzag chains into 3D networks. Crystallographic data: ( 1 ) P1¯ (no. 2), a = 8.012(1), b = 8.160(1), c = 8.939(1) Å, α = 82.29(1)°, β = 76.69(1)°, γ = 81.68(1)°, U = 559.6(1) ų, Z = 2; ( 2 ) C2/c (no. 15), a = 16.495(1), b = 5.578(1), c = 11.073(1) Å, β = 95.48(1)°, U = 1014.2(1) ų, Z = 4; ( 3 ) P2/c (no. 13), a = 9.407(2), b = 5.491(1), c = 11.317(2) Å, β = 95.93(3)°, U = 581.4(2) ų, Z = 2.     

K2[Mo2O4(C2O4)2(H2O)2]·3H2O

The crystal and molecular structure of dipotassium di‐μ‐oxo‐bis[aqua(oxalato‐O¹,O²)oxomolybdenum(III)] trihydrate, K₂­[Mo₂O₄(C₂O₄)₂(H₂O)₂]·3H₂O, has been determined from X‐ray diffraction data. In the dimeric anion, which has approximate twofold symmetry, each Mo atom is in a distorted octahedral coordination, being bonded to one terminal oxo‐O atom, two bridging O atoms, two O atoms from the oxalato ligand and one from the water mol­ecule. Bond lengths trans to the multiple‐bonded terminal oxo ligand are larger than those in the cis position, confirming the trans influence as a generally valid rule.     

Lowest-energy structures of water clusters (H2O)11 and (H2O)13

We employed a four-step searching/screening approach to determine best candidates for the global minima of (H2O)11 and (H2O)13. This approach can be useful when there exist a large number of low-lying and near-isoenergetic isomers, many of which have the same oxygen-skeleton structure. On the two new candidates for the global minimum of (H2O)11, one isomer can be viewed as placing the 11th molecule onto the side of the global minimum of (H2O)10 and the other can be viewed as removing the 12th molecule from the middle layer of the global minimum of (H2O)12. The three leading lowest-energy clusters of (H2O)13 can all be built starting from the global minimum of (H2O)12, with the difference being in the location of the 13th water molecule.