［La(CH2ClCOO)2(NO3)(phen)(H2O)］n的合成和晶体结构

合成了混合阴离子配合物［La(CH₂ClCOO)₂(NO₃)(phen)(H₂O)］_n。配合物经元素分析、IR、DTA-TG和UV等表征。用X射线单晶结构分析解析了标题配合物的晶体结构，三斜，空间群P1，晶胞参数为a=10.533(2)?，b=13.136(3)?，c=7.776(1)?，α=96.59(1)°，β=95.76(1)°，γ=108.42(2)°，V=1003.3(3)?³，Z=2,Dc=1.940 g/cm³, F(000)=572, μ(Mo Kα)=24.36 cm^-1。     

［Ln(EO2)3］(ClO4)3·3H2O的晶体结构研究

合成了希土高氯酸盐开环冠醚二缩乙二醇(EO2)晶体，(Ln=Nd, Ho)，测定了结构，文内以Nd-L的数据为主要研究对象(方括号内是Ho-L的数据)。晶体属单斜晶系，P2₁/n空间群，化学式［Ln(EO2)₃］(ClO₄)₃·3H₂O，晶胞参数为：a=14.124(1)［14.087］, b=13.990(1)［14.039］, c=15.265(1)［15.014］?; β=95.78(1)［95.64］°; V=3001.1(6)［2955］?³; Mr=815.01［835.70］; Z=4; Dc=1.804［1.865］g/cm³；石墨单色器，μ(MoKα)=2.09［3.07］ mm^-1，最终偏离因子R=0.055［0.074］, R_W=0.071［0.109］。研究结果表明晶体具有相同的结构，配位多面体为九配位三帽三棱柱。发现EO2醚链有绕C-C键呈STT分布的规律。弱配体高氯酸根不参加配位。     

簇合物Co3(CO)7(μ3-S)[μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH]和Co3(CO)7(μ3-S)[μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)]的合成与晶体结构

用Co₂(CO)₈分别与两个杂环配体C(S)NHP(S)(C₆H₄OCH₃)OC(Ph)CH (L₁)和C(S)NHC(CH₃)₂P(S)(Cl)N(Ph) (L₂)反应,合成两个新的三核钴羰基硫簇合物Co₃(CO)₇(μ₃-S)[μ,η²-CNP(S)(C₆H₄OCH₃)OC(Ph)CH](Ⅰ)和Co₃(CO)₇(μ₃-S)[μ,η²-SCNC(CH₃)₂P(S)(Cl)N(Ph)](Ⅱ)。用元素分析,IR, ¹H NMR, ³¹P NMR及MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,空间群P1,Ⅰ的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.601(3)°,γ=88.535(2)°,V=1.4318(5)nm³,Z=2,D_c=1.641g·cm^-3,F(000)=716,μ=1.893mm^-1,R=0.0602,R_w=0.1515。Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm³,Z=2,D_c=1.841g·cm^-3,F(000)=690,μ=2.419mm^-1,R=0.0423,R_w=0.1075。Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有CO作为端基配体与三个Co原子成键。Ⅰ中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件。     

(μ-FcC≡CH)Co2(CO)6簇合物羰基取代衍生物的合成和分子结构

The substituted reactions of (μ-FcC≡CH)Co₂(CO)₆ with PPh₃, AsPh₃ and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, ¹H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co₂(CO)_6-nL[n=1, L=PPh₃（2）, AsPh₃（3）; n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P2₁/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm³, Z=4, F(000)=1 480, D_c=1.515 g·cm^-3, μ=15.62 cm^-1; final R indices [I > 2σ(I)]: R₁=0.040 9, ωR₂=0.076 9; S=1.007, Δρ_max=463e·nm^-3, Δρ_min=-395 e·nm^-3. The cluster 3 crystallizes in monoclinic, space group P2₁/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm³, Z=4, F(000)=1 552, D_c=1.574 g·cm^-3, μ=24.87 cm^-1; final R indices[I> 2σ（I）]：R₁=0.0437, ωR₂=0.078 2; S=0.995, Δρ_max=530 e·nm^-3, Δρ_min=-444 e·nm^-3. CCDC: 221860, 2; 221863, 3.     

镧系四元混合阴离子配合物［Pr(CH3CH2COO)2(NO3)(phen)2］合成和晶体结构

在含水溶剂、酸性环境中合成了镧系四元混合阴离子配合物［Pr(CH₃CH₂COO)₂(NO₃)(phen)］₂并解析了其晶体结构,三斜,空间群P1,a=0.9650(2) nm, b=1.2949(4) nm,c=0.8994(2)nm, α=95.37(3)°,β=111.05(2)°,γ=102.87(2)°,V=1.0037(5) nm^{3, Dc=1.758 g·cm-3, Z=1, F(000)=528, μ(MoKα)=24.64 cm-1, R=0.024, R_W=0.034。四个丙酸根呈二种配位方式,Pr3+为九配位。}     

含硫杂核原子簇Cp*WFeCo(CO)8(μ3-S)和(Cp*W)2Fe(CO)7(μ3-S)的合成及结构研究

本文利用过渡金属的亲硫性，通过Cp^*-W(CO)₃Cl(Cp^*=C₅H₅, C₅H₄CH₃)与HFe₂Co(CO)₉(μ₃-S)反应，得到四种含硫异核金属羰基原子簇化合物Cp^*WFeCo(CO)₈(μ相似文献   

乙烯基混金属羰基簇取代衍生物的合成和分子结构

The mono- and di- substituted derivatives of the parent cluster {μ₃-H(Ph)C=C}FeCo₂(CO)₉ (1) have been synthesized by facile substitution reactions. The compound {μ₃-H(Ph)C=C}FeCo₂(CO)₇(dppe) (2)， {μ₃-H(Ph)C=C}FeCo₂(CO)₈(PPh₃) (3) and {μ₃-H(Ph)C=C}FeCo₂(CO)₈(AsPh₃) (4) were characterized by elemental analysis， IR， ¹H ，³¹P NMR， MS and X-ray crystallography. The new cluster 2 crystallizes in monoclinic space group P2₁/n， with a=0. 8614(5)nm， b=1.6404(8)nm， c=2.6574(14)nm， β=96.3222(12)°， V=3.732(3)nm³， Z=4， S=0.886， Δρ_max=0.335e·nm^-3， Δρ_min=-0.379e·nm^-3. Final R indices [I >2σ(I)]： R₁=0.0432， wR₂=0.0695. CCDC： 164600.     

一维链状配位聚合物[Ca(L)2·(CH3OH)2]n的合成、结构及热稳定性

The coordination polymer [Ca(L)₂·(CH₃OH)₂]_n (HL=N-phenylanthranilic acid) (1) was synthesized by the reaction of calcium perchlorate with N-phenylanthranilic acid in the CH₃OH/H₂O. It was characterized by elemental analysis, IR, thermal analysis and X-ray single crystal structure analysis. The crystal of the title complex [Ca(L)₂·(CH₃OH)₂]_n belongs to triclinic, space group P1 with a=0.751 5(3) nm, b=1.079 6(4) nm, c=1.629 5(6) nm, α=83.547(5)°, β=89.001(6)°, γ=72.257(5)°, V=1.251 0(8) nm³, Z=2, D_c=1.403 Mg·m^-3, F(000)=556, and final R₁=0.066 8, wR₂=0.140 4. The complex comprises a seven-coordinated calcium(Ⅱ) center, with a O₇ distorted pengonal bipyramidal coordination environment. Adjacent Ca(Ⅱ) ions are bridged by N-phenylanthranilicate groups, resulting in a 1D chain structure. The adjacent Ca…Ca distances are 0.382 8 nm and 0.384 6 nm. Furthermore, the molecules are connected by hydrogen bonds to form two dimensional layered structure. CCDC: 652445.     

一维链状冠醚配合物:[{Na(18-C-6)}2(H2O)]n[M(SCN)4]n(M=Pd、Pt)的合成与结构

The reactions of 18-crown-6 with Na₂[M(SCN)₄] (M= Pd,Pt) were studied and the complex 1 [{Na(18-C-6)}₂(H₂O)]_n[Pd(SCN)₄]_n and complex 2 [{Na(18-C-6)}₂(H₂O)]_n[Pt(SCN)₄]_n were characterized by ele-mental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P2₁/n with cell dimensions, 1:a=1.05734(7),b=1.42250(10),c=1.47762(10) nm,β=107.5330(10)°,V=2.1192(2)nm³,Z=2,D_calcd=1.460g·cm^-3,F(000)=964,R₁=0.0406,wR₂=0.1264 and 2:a=1.05985(19),b=1.4237(3),c=1.4744(3) nm,β=107. 096(3)°, V=2.1264(7)nm³,Z=2,D_calcd=1.690g·cm^-3,F(000)=1028,R₁=0.0292,wR₂=0.0859. In the solid state, the complexes 1 and 2 show an one-dimensional chain of [{Na(18-C-6)}₂(H₂O)]²⁺ complex cations and [M(SCN)₄]^2- (M=Pd,Pt) complex anions bridged by Na-N in-teractions.     

四元混配配合物[Ce(CH2=C(CH3)-COO)2(NO3)(phen)]2的合成、表征及晶体结构

A new complex with mixed-quadriligand [Ce(CH₂=C(CH₃)-COO)₂(NO₃)(phen)]₂ has been synthesized in aqueous solution of slight acidity and characterized by elementary analysis, IR and TGA. The crystal structure determination shows that the complex belongs to triclinic, space group P1, a=9.614?, b=10.047?, c=11.821?, Z=2, α=100.88(3)°, β=106.29(3)°, γ=97.93(2)°, V=1054(5)?³, D_c=1.741g·cm^-3, F(000)=546.00, μ(MoKα)=22.06cm^-1. And the crystal is consisted of a binuclear molecule. The coordina-tion of Ce³⁺ is nine.     

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.     

镧系四元混合阴离子配合物［Ce(p-MBA)2(NO3)(phen)］2的合成和晶体结构

We synthesized new mixed anion complex of lanthanide ［Ce(p-MBA)₂(NO₃)(phen)］₂ in slightly acidic solution of ethanol and determined the single crystal structure. The title complex is triclinic, space group P1, a=1.1027(4) nm, b=1.2511(5) nm, c=1.0633(3) nm, α=106.90(3)°, β=96.73(3)°, γ=86.85(3)°, V=1.3937(9) nm³, D_C=1.555 g·cm^-3, Z=1, F(000)=650.00 and μ(MoKα)=16.82 cm^-1. The four p-MBA ligands have two kinds of coordination modes and the coordination number of the Ce³⁺ is nine. There is some aromatic-stacking interaction in the benzene rings of two p-MBA ligands.     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.     

一维链状配位聚合物[Cu3(TFSSB)2·(H2O)4·4H2O]n的合成和晶体结构

The title complex [Cu₃(TFSSB)₂·(H₂O)₄·4H₂O]_n (TFSSB=taurine 3-formylsalicylic schiff base) was synthesized by TFSSB and copper(Ⅱ) acetate monohydrate in ethanol solution and the crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic system, space group P2₁ / n，with cell parameters: a=0.927 9(6) nm, b=1.173 0(2) nm, c=1.471(2) nm, β=106.96(2)°, and V=1.531(2) nm³, Z=2, D_c=1.890 g·cm^-3, μ=2.291 mm^-1, F(000)=882, R₁=0.025 9, wR₂=0.065 9. The Cu1 is five-coordinate, the Cu2 is four-coordinate. CCDC: 253298.     

(NH2CH2CH2NH3)4[WⅤO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O的合成、晶体结构、EPR以及与同构物的比较

Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH₂CH₂CH₂NH₃)₄[W^ⅤO₂(OC₆H₄O)₂]₂(NH₃CH₂CH₂NH₃)·H₂O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH₃OH, CH₃CN and NH₂CH₂CH₂NH₂. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm³, Z=2, R₁=0.062 8, wR₂=0.183 7. Compared the complex with its analogous complexes (NH₂CH₂CH₂NH₃)₃[Mo^ⅤO₂(OC₆H₄O)₂], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.     

三缺位杂多阴离子α-A-PW9O349-的甲基硅衍生物(TBA)3[α-A-PW9O34(CH3SiO)3(CH3Si)]的合成和晶体结构

Reaction of the trivacant heteropolyanions α-A-PW₉O₃₄^9- with CH₃SiCl₃ leads to the formation of the organosilyl derivative (TBA)₃[α-A-PW₉O₃₄(CH₃SiO)₃(CH₃Si)]. The crystal X-ray diffraction analysis shows that the crystal belongs to orthorhombic with space group Pca2₁, M=3177.09 and the unit cell parameters: a=25.761(5)?,b=14.519(3)?,c=24.396(5)?.V=9124(3)?³,Z=4,D_c=2.225g·cm^-3,μ(MoKα)=11.438mm^-1,F(000)=5464,R=0.0561,R_w=0.0866. The anion consists of one α-A-PW₉O₃₄^9- anion linked by three CH₃SiO⁺ groups, which attached to the fourth CH₃Si through three Si-O-Si bridges.     

一维链状铜配位聚合物[Cu(bpb)0.5(CH3COO)2]n的合成与晶体结构

A coordination complex of [Cu(bpb)_0.5(CH₃COO)₂]_n (bpb=1,4-bis(pyridine-3-aminomethyl)benzene) has been synthesized and characterized by elemental analysis, IR spectra, TG and X-ray single crystal diffraction. The title complex crystallizes in triclinic with space group P1, a=0.771 98(15) nm, b=0.827 62(17) nm, c=1.116 0(2) nm, α=96.71(3)°, β=90.03(3)°, γ=105.39(3)°, and V=0.682 4(3) nm³, Z=2, R=0.042 4, wR=0.091 1. The title complex is composed of dicopper tetracarboxylate units. Copper(Ⅱ) atom asumes a square-pyramidal coordination geometry formed with one pyridyl N atom from bpb and four O atoms from four bridging acetate anions. Two adjacent dicopper tetracarboxylate units are linked into a 1D chain by the bpb ligands, which were further connected by inter-chain hydrogen bonds to form a 2D network structure. CCDC: 667605.     

L-丙氨酸桥联配位聚合物[Cu2(L-ala)2(phen)2]n·2nClO4·2nH2O的合成及其结构

The complex, [Cu₂(L-ala)₂(phen)₂]_n·2nClO₄·2nH₂O(L-ala=L-alaninate, phen=1,10-phenanthroline) has been synthesized and investigated by elemental analysis, IR spectroscopy, and X-ray diffraction methods. The complex crystallizes in the monoclinic space group P2₁ with a=1.161 1(4) nm, b=0.717 2(2) nm, c=2.074 1(7) nm, β=101.028(6)°, V=1.695 4(9) nm³, D_c=1.760 g·cm^-3, Z=4, μ=1.493 mm^-1, F(000)=916, R=0.052 2, wR=0.127 9 for 7 131 unique reflections. The cations of [Cu₂(L-ala)₂(phen)₂]_n²ⁿ⁺ have an one-dimensional polymeric structure, due to the bridging of two Cu(phen)²⁺ units by a carboxylate group of L-alaninate, and each Cu(Ⅱ) ion is in a slightly distorted square-pyramidal coordination geometry, with the phen (N,N′) and the L-ala(N,O) acting as bidentate ligands in the equatorial plane and another carboxylate oxygen atom from a symmetry-related neighboring L-alaninate ion in the apical position. CCDC: 277541.     

配合物[Ce(CH2=C(CH3)COO)2(NO3)(Bipy)]的合成及晶体结构

The new complex [Ce(CH₂=C(CH₃)COO)₂(NO₃)(Phen)]₂ was prepared in ethanol-aqueous solution with 8-hydroxyquinoline as the acidity regulator. Its crystal structure was determined by X-ray diffraction analysis. The title complex is triclinic, space group P1, a=1.00832(3)nm, b=1.02858(8)nm, c=1.12350(8)nm, α=113.9250(10)°, β=103.8210(10)°, γ=81.4650(10)°, V=1.03252(14)nm³, Z=1, D_c=1.700g·cm^-3, F(000)=522. The coordination number of Ce³⁺ is nine. CCDC: 211278.     

一维链状锰配位聚合物[Mn(3,5-Me2PhCO2)2(phen)]n的合成与晶体结构

A manganese coordination polymer [Mn(3,5-Me₂PhCO₂)₂(phen)]_n(phen=1,10-phenanthroline) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.770 3(4) nm, b=1.145 2(6) nm, c=1.537 0(9) nm, α=78.182(9)°, β=77.170(9)°, γ=89.784(9)°, V=1.292 8(12) nm³, Z=2, M_r=533.47, D_c=1.370 g·cm^-3, μ=0.549 mm^-1, F(000)=554, R_int=0.043 4, R=0.060 8 ,wR=0.148 4. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from phen and four oxygen atoms from four 3,5-dimethylbenzolate molecules, completing an octahedral geometry. And the title complex forms one-dimensional chain structure through bridging 3,5-dimethylbenzolate molecules. CCDC: 642920.