[Co(ptma)(amp)Cl]2+体系的一反式经式异构体(m3[ZnCl4]·0.5H2O)的晶体结构

在合成[Co(bpma)(tn)Cl]²⁺体系配合物的实验中,得到[Co(ptma)(amp)Cl]²⁺体系的一反式(ptma中仲胺上的氢相对于Cl)经式异构体(m3[ZnCl₄]·0.5H₂O),其中bpma=N,N′-二(2-吡啶基甲基)胺,tn=1,3丙二胺,ptma=N-(2-吡啶基甲基)丙二胺,amp=2-(氨基甲基)吡啶。此配合物异构体构型选择性形成的原因可能主要是其结构中配体间C-H…π相互作用使之更稳定的结果。利用单晶X-射线衍射法测定的晶体学参数:单斜晶系,空间群C2/c,a=1.55978(19)nm,b=1.33324(16)nm,c=2.2077(3)nm,β=94.832(3)°,V=4.5748(10)nm³,D_c=1.696g·cm^-3,Z=8,F₀₀₀=2360,μ(MoKα)=23.72cm^-1,R=0.0475,R_w=0.1204。配合物离子中Co³⁺为六配位。晶胞中含8个配合物阳离子,8个[ZnCl₄]^2-阴离子及4个水分子,对映体的比例为1∶1。     

四（对叔丁基）硫杂杯[4]芳烃选择性包合四氟硼酸分子：晶体结构和理论研究

X－射线晶体衍射测定了4－(对叔丁基)硫杂杯[4]芳烃选择性地包合四氟硼酸分子。晶体学数据为：C₄₀H₄₉O₄S₄BF₄，M_r=808.88， 四方锥， 空间群 P4/nmm，a=1.5887(2), b=1.5887(2), c=0.8428(0) nm, V=2.127(2) nm³, Z=2, D_c=1.263 g·cm^-3, R₁=0.0405, _WR[I>2σ(I)]=0.1218. ¹⁹F NMR谱中，在-151.4 ppm处出现的峰，证实了四氟硼酸的存在。用Bader的分子中的原子理论方法计算了分子结构中的非共价键相互作用。结果显示，在四氟硼酸包合物中，除了F…H－C氢键作用和阳离子－阴离子的静电作用外，F^δ--C^δ+静电作用的存在也对4－(对叔丁基)硫杂杯[4]芳烃憎水空腔包合氟硼酸分子起到了稳定作用。     

两个锰的18-氮杂金属冠醚-6配合物的合成、晶体结构和磁性质研究

以负三价、五啮的N-乙酰水杨酰肼(ashz^3-)作为配体,合成了二个大环六核氮杂金属冠醚[Mn^Ⅲ₆(ashz)₆(MeOH)₆]·6MeOH (1)和[Mn^Ⅲ₆(ashz)₆(DMF)₆]·3DMF (2)。晶体学数据是:配合物1,三方晶系,空间群R3,a=b=24.806(2),c=11.260(1)?,Z=3,μ=1.007mm^-1,R=0.0572,wR=0.1142;配合物2,三方晶系,空间群R3,a=b=26.629(3),c=23.298(4)?,Z=6,μ=0.856mm^-1,R=0.0671,wR=0.1661。这两个配合物属18-氮杂金属冠醚-6结构类型,冠醚分子具有晶体学C_3i对称性。配体ashz^3-通过它的肼基的N-N桥连金属原子,从而形成有中央空穴的六核锰的大环配合物。变温磁化率(4～275K)研究表明,配合物1中金属离子间存在着反铁磁性耦合。     

苄基四甲基环戊二烯基钼羰基化合物的合成及晶体结构

C₅Me₄(benzyl)H reacted with Mo(CO)₆ in refluxing xylene to give the new complex (C₅Me₄benzyl)₂Mo₂(CO)₆. Its molecular structure was characterized by elemental analysis, IR spectra, ¹H NMR and X-ray diffraction. Crystal data for this compound: Triclinic, space group P1, M_r=782.56, a=0.854 43(17) nm, b=0.991 0(2) nm, c=1.035 5(2) nm, α=67.25(3)°, β=87.38(3)°, γ=85.99(3)°, V=0.806 4(3) nm³, Z=1, D_c=1.611 g·cm³, μ(Mo Kα)=0.825 mm^-1, F(000)=398, R=0.032 9, wR=0.083 6 (observed reflections with I>2σ(I)) and R=0.036 2, wR=0.084 3 (all reflections). The X-ray crystal structure of the dimer confirms the structure with terminal CO groups and the Mo-Mo bond distance is 0.326 6 nm. CCDC: 693386.     

含有4,5-二氮芴-9-酮锌(Ⅱ)、钴(Ⅱ)化合物的合成和晶体结构

Two compound crystals of (Hdafo)₂[ZnCl₄]·2H₂O (1) and (Hdafo)₂[CoCl₄]·2H₂O (2) were obtained when we tried synthesizing the mixed ligand compounds of Zinc (Ⅱ) and Cobalt(Ⅱ) with 4,5-diazafluorene-9-one(dafo) and o-phthalic acid, respectively. Their structure was determined by single crystal X-ray diffraction. The crystals all belong to monoclinic system, C2/c space group with crystallographic data:(Hdafo)₂[ZnCl₄]·2H₂O, a=1.6768(5)nm, b=1.2052(3)nm, c=1.3888(4)nm, β=116.793(3), V=2.5053(12)nm³, Z=4, F(000)=1232, M_r=609.57, D_c=1.616g·cm^-3, μ(MoKα)=1.444mm^-1, R₁=0.0373, wR₂=0.0765; (Hdafo)₂[CoCl₄]·2H₂O, a=1.6787(4)nm, b=1.2078(3)nm, c=1.3911(4)nm, β=116.665(3)°, V=2.5204(11)nm³, Z=4, F(000)=1220, M_r=603.13, D_c=1.589g·cm^-3, μ(MoKα)=1.142mm^-1, R₁=0.0257, wR₂=0.0654. The constitutes of the two compounds were proved by elemental, IR Spectra and thermal analyses. CCDC: 1, 198516; 2, 198517.     

一种新颖有机-无机杂化配位聚合物[(C10H16N)2（Pb2I6）·2DMF·H2O]n的自组装合成和晶体结构(英)

A novel coordination polymer [(C₁₀H₁₆N)₂（Pb₂I₆）·2DMF·H₂O]_n (C₁₀H₁₆N=N-butyl-2-Methy-Pyridinium) was synthesized by the reaction of Pb(NO₃)₂ with C₆H₁₀NI at room temperature in DMF solvent and structurally characterized by means of X-ray single diffraction. The title compound crystallizes in triclinic system, space group P1 with a=1.1237(2) nm, b=1.25330(16) nm, c=0.808 00(12) nm, α=102.523(4)°, β=92.475(5)°, γ=95.712(10)°, V=1.102 9(3) nm³, Z=1, D_c=2.470 Mg·m^-3, F(000)=738, chemical formula C₂₆H₄₈N₄O₃Pb₂I₆ and M_r=1 640.46, μ（MoKα）=11.849 mm^-1, the final R=0.057 8 and wR=0.166 5 for 3716 observed reflections with I > 2σ(I). The title compound consists of cations ([(C₁₀H₁₆N)⁺] and anion chain(PbI₃^-),they are combined by static attracting forces in the crystal. DMF and H₂O locate between the organic and inorganic moiety. CCDC: 210812.     

2-[(2-溴苯胺基)甲基]-4-氯苯酚Schiff碱及其铜配合物的合成及晶体结构

以5-氯水杨醛和邻溴苯胺为原料合成了一种新的Schiff碱配体2-[(2-溴苯胺基)甲基]-4-氯苯酚(1)(C₁₃H₉BrClNO,H₂L),继而与过渡金属铜离子配合,得到其配合物2 ([Cu(C₁₃H₈BrClNO)₂],CuL₂)。通过X-射线衍射法对配体及其配合物进行了结构表征。化合物1属正交晶系,Pbca空间群,晶胞参数a=0.710 19(12) nm,b=1.308 2(2) nm,c=2.533 3(5) nm,M_r=310.57,V=2.353 6(7) nm³,D_c=1.753 g·cm^-3,Z=8,μ=3.700 mm^-1,Z=8,F(000)=1 232,R=0.025 0,wR=0.055 5;化合物1依靠分子间的C-H…N,C-H…O,C-H…Cl 氢键及π-π堆积作用进一步联结成二维网状结构。化合物2属单斜晶系,P2₁/c空间群,晶胞参数a=0.956 8(2) nm,b= 1.085 3(3) nm,c=1.204 7(3) nm,β=105.965(7)°,M_r=682.67,V=1.202 8(6) nm³,D_c=1.885 g·cm^-3,Z=2,μ=4.481 mm^-1,F(000)=670,R=0.045 0,wR=0.122 5。2依靠分子间C-H…π作用及卤素…卤素作用进一步联结成三维网状结构。     

一个不常见的Ni(Ⅱ)的戊三酮二水杨酰腙配合物的合成和晶体结构

合成了镍的戊三酮二水杨酰腙配合物Ni(C₁₉H₁₆N₄O₅)的两个同质异晶,测定其晶体结构。该配合物的两个晶体均属单斜晶系,空间群为C2/c,晶体1晶胞参数为:a=1.03076(9)nm,b=1.9105(1)nm,c=0.93305(8)nm,β=101.490(4)°,Z=4,μ=1.119mm^-1,R=0.0370;晶体2晶胞参数为:a=2.1949(3)nm,b=0.9901(2)nm,c=0.8568(1)nm,β=92.799(6)°,Z=4,μ=1.084mm^-1,R=0.0440。两个晶体中镍原子由多啮配体的二个酰氧原子和二个肼氮原子形成平面正方形配位。对配合物的红外光谱进行归属。     

5-溴水杨醛缩乙醇胺Schiff碱Cu(II)配合物的合成和晶体结构

The title complex Cu(L)₂ [HL=N-(5-bromosalicylidene)-2-aminoethanol] was synthesized by the reaction of Cu(CH₃COO)₂·H₂O with N-(5-bromosalicylidene)-2-aminoethanol in the ethanol. It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The crystal of the title complex [Cu(C₉H₉BrNO₂)₂] belongs to monoclinic, space group P2₁/n with a=1.319 1(5) nm, b=0.444 58(16) nm, c=1.656 7(6) nm, β=91.226(5)°, V=0.971 46(6) nm³, Z=2, D_c=1.879 Mg·m^-3, μ=5.264 mm^-1, F(000)=542, and final R₁=0.045 6, wR₂=0.097 0. The complex comprises a four-coordinated copper(II) center, with an N₂O₂ planar coordination environment. The molecules are connected by hydrogen bonds to form two-dimensional layered structure. CCDC: 274180.     

双核Ru配合物(C5Me4iBu)2Ru2(CO)4的合成与晶体结构

The complex (C₅Me₄ⁱBu)₂Ru₂(CO)₄ has been synthesized by the reaction of C₅Me₄ⁱBuH with Ru₃(CO)₁₂ in refluxing xylene and its molecular structure was characterized by elemental analysis, IR spectra, ¹H NMR and X-ray crystal structure determination. Crystal data for this compound: Triclinic, space group P1, M_r=668.78, a=0.865 96(17) nm, b=0.892 90(18) nm, c=0.975 7(2) nm, α=88.39(3)°, β=71.64(3)°, γ=84.99(3)°, V=0.713 3(2) nm³, Z=1, D_c=1.557 g·cm^-3, μ(Mo Kα)=1.091 mm^-1, F(000)=342, R₁=0.025 3, wR₂=0.067 6 (observed reflections with I>2σ(I)) and R₁=0.026 9, wR₂=0.068 2(all reflections). The structure of the dimer confirms the structure with bridging and terminal CO groups, and the Ru-Ru bond distance is 0.275 19(8) nm. CCDC: 693389.     

基于1，2，4-苯三酸与[2，3-f]吡嗪并[1，10]菲咯啉配体的钴(Ⅱ)及镉(Ⅱ)配合物的水热合成与晶体结构

利用水热技术,合成了2个新的配合物{[Co(Hbtc)(Pyphen)(H₂O)]·H₂O}_n (1)和{[Cd₂(btc)(Pyphen)₂Cl]·2H₂O}_n(2) (H₃btc=1,2,4-苯三酸,Pyphen=[2,3-f]吡嗪并[1,10]-菲咯啉),并通过X-射线单晶衍射、元素分析、热重分析和荧光进行了表征。配合物1属三斜晶系,空间群P1,a=0.643 44(13) nm,b=1.202 9(2) nm,c=1.371 6(3) nm,α=95.03(3)°,β=90.46(3)°,γ=103.54(3)°,V=1.027 7(4) nm³,Z=2,CoC₂₃H₁₆N₄O₈,M_r=535.31,D_c=1.730 g·cm^-3,μ(MoKα)=0.900 mm^-1,F(000)=546,GOOF=1.089,R=0.099 2,wR=0.249 0;配合物2属三斜晶系,空间群P1,a=0.968 93(8) nm,b=1.223 82(10) nm,c=1.592 21(14) nm,α=67.486 0(10)°,β=73.158 0(10)°,γ=78.468 0(10)°,V=1.660 9(2) nm³,Z=2,Cd₂C₃₇H₂₃N₈O₈Cl,M_r=967.88,D_c=1.935 g·cm^-3,μ(MoKα)=1.432 mm^-1,F(000)=956,GOOF=1.051,R=0.077 9,wR=0.141 2。结构分析表明：配合物1为无限一维双链结构,配合物2为二维层状结构。此外,氢键和π-π相互作用在加固配合物的结构中起到重要作用。     

含非交换氘的四唑-锌配合物

The solvothermal reaction (D₂O) of 2,6-dideuterium-4-cyanopyridine with ZnCl₂ in the presence of NaN₃ offers a novel complex Zn(OD)(C₆H₂D₂N₄) (1) in which Zn has a distorted tetrahedron composed of two N atoms from one tetrazoyl group and pyridyl group and two O atoms from two deuteratohydroxy OD groups. Crystal data for 1: Pbcn, a=1.456 8(5) nm, b=0.659 2(2) nm, c=1.645 3(5) nm, α=90°, β=90°, γ=90°, V=1.580 0(9) nm³, Z=8, M=231.54, D_c=2.236 Mg·m^-3, μ=3.070 mm^-1, R₁=0.043 4, wR₂=0.120 6, S=1.029. CCDC: 660629.     

2，6-二氯苯甲酸桥联的双核锰配合物的水热合成与晶体结构

A dinuclear manganese(Ⅱ) complex, [Mn₂(L¹)₂(phen)₄]·(ClO₄)₂ (1), has been synthesized and structurally characterized (HL¹=2,6-dichlorobenzoic acid, phen=1,10-phenanthroline). It crystallizes in triclinic system, space group P1 with a=1.112 3(4) nm, b=1.378 2(4) nm, c=2.085 7(3) nm, α=93.768(2)°, β=90.606(10)°, γ=95.606(3)°, V=3.174 8(15) nm³, Z=2, C₆₂H₃₈C₁₆Mn₂N₈O₁₂, M_r=1 409.58, D_c=1.475 g·cm^-3, μ=0.718 mm^-1, F(000)=1 428, R=0.064 3, wR=0.138 3. In the crystal the manganese atom is six-coordinated by two oxygen atoms from two different 2,6-dichlorobenzolate molecules and four nitrogen atoms from two 1,10-phenanthroline molecules, completing an octahedral geometry. CCDC: 692296.     

两种含氨基吡啶衍生物铜(Ⅱ)配合物的合成和晶体结构

Copper(Ⅱ) complexes Cu(C₆H₆N₂)₂(ClO₄)₂ (1) and Cu₂(OAc)₄(C₅H₅ClN₂)₂ (2) with amino-pyridine deriva-tives ligands have been synthesized and characterized by elemental analysis and IR spectrum. Their crystal struc-tures are determined by X-ray diffraction method. Compound 1， C₁₂H₁₆C₁₂CuN₄O₈， M_r=478.73， triclinic， space group ， a=0.7641(1)nm， b=0.7987(1)nm， c=0.7990(1)nm， α=106.78(1)°，β=95.71(1)°， γ=108.85(1)°， V=0.4317(1)nm³， Z=1， D_c=1.841g·cm^-3， μ=1.627mm^-1， F(000) =243，R₁=0.0264， ωR₂=0.0641 (I>2σ(I)). In 1， the center metal ion Cu(Ⅱ) possesses distorted octahedral geometry. Compound 2， C₁₈H₂₂C₁₂Cu₂N₄O₈， M_r=620.38，monoclinic， space group C2/c， a=1.9888(3)， b=0.9158(1)， c=1.4241(2)nm， β=115.89(1)°， V=2.3336(5)nm³， Z=4， D_c=1.766mg·cm^-3， μ=2.104mm^-1， F(000)=1256， R₁=0.0263， wR₂=0.0676 (I>2σ(I)). Compound 2 is dinuclear structure， in which each Cu(Ⅱ) adopts five-coordinated distorted square pyramid geometry. CCDC： 193109; 193110.     

三(邻甲基苄基)氯化锡和二(对甲基苄基)二氯化锡的合成和晶体结构

将邻甲基氯苄和对甲基氯苄在适当的溶剂中与锡粉反应，合成了三(邻甲基苄基)氯化锡1和二(对甲基苄基)二氯化锡2，用X射线衍射方法测定了化合物的晶体结构。化合物(1)的晶体属三方晶系，空间群为R3，晶体学参数：a=1.329 36(8) nm，b=1.329 36(8) nm，c=2.147 0(3) nm，α=β=90°，γ=120°，V=3.285 8(5) nm³，Z=6，D_c=1.424 g·cm^-3，μ(Mo Kα)=12.93 cm^-1，F(000)=1 428，R₁=0.037 1，wR=0.110 2。化合物2的晶体属单斜晶系，空间群为C2/c，晶体学参数：a=2.850 4(3) nm，b=0.491 23(5) nm，c=1.215 32(12) nm，β=112.517(2)°，V=1.571 9(3) nm³，Z=4，D_c=1.690 g·cm^-3，μ(Mo Kα)=19.49 cm^-1，F(000)=792，R₁=0.038 0，wR₂=0.109 4；中心锡原子为畸变四面体配位构型。     

铅离子与镉离子高选择性的大环化合物:对称四甲基六元瓜环与过渡金属及重金属离子的配合作用

利用微分脉冲伏安法研究了对称四甲基六元瓜环(TMeQ[6])与过渡金属的相互作用。结果表明该主体大环化合物对Pb²⁺和Cd²⁺离子具有较好的选择性作用。伏安数据测定表明Pb²⁺及Cd²⁺离子与对称四甲基六元瓜环以n_M²⁺/n_TMeQ[6]=2配位, 其配合平衡常数分别为(K_Pb²⁺=2.12×10⁹ L²·mol^-2, K_Ca²⁺=2.10×10⁹ L²·mol^-2)。Pb²⁺离子与TMeQ[6]的晶体结构进一步证实了上述实验结果。     

含硫、氮Schiff碱配合物—二水二分之一二甲基亚砜醋酸四邻香草醛缩胺基硫脲合镉(Ⅱ)的合成及晶体结构

X射线单晶衍射结果表明,三核镉配合物Cd₃[CH₃O(O)C₆H₃CH=NNHC(S)NH₂]4·[CH₃COO]₂·1/2[CH₃S(O)CH₃]·2H₂O为单斜晶系,空间群为C2/c,a=3.4214(4),b=1.1581(2),c=1.7932(5)nm,β=119.76(1)°,V=6.168nm³,Mr=1427.43,Z=4,D_c=1.54g/cm³,μ=12.48cm^-1,F(000)=2860,最后偏离因子R=0.066.     

3-(水杨酰肼)-丁基-2-酮肟和两个镍的酮肟配合物的合成和晶体结构

合成了3-(水杨酰肼)-丁基-2-酮肟H₂L(1，C₁₁H₁₃N₃O₃)和2个镍的3-(水杨酰肼)-丁基-2-酮肟化合物[Ni(HL)(CH₃COO^-)(C₅H₅N)₂](2)和[Ni(HL)₂]·2C₃H₇NO（3）。化合物1晶体属单斜晶系，空间群为P2₁/n，晶体学参数为：a=0.451 87(2) nm，b=2.086 8(1) nm，c=1.224 48(9) nm，β=94.974(3)°，V=1.150 3(1) nm³，Z=4，D_c=1.358 g·cm^-3，μ=0.101 mm^-1，F(000)=496，R=0.0435，wR=0.142 5。化合物2晶体属单斜晶系，空间群为P2₁/n，晶体学参数为：a=1.362 39(8) nm，b=1.345 37(6) nm，c=1.438 54(7) nm，β=113.138(3)°，V=2.424 6(2) nm³，Z=4，D_c=1.398 g·cm^-3，μ=0.843mm^-1，F(000)=1 064，R=0.042 4，wR=0.116 6。化合物3晶体属单斜晶系，空间群为P2₁/c，晶体学参数为：a=1.104 22(7) nm，b=2.860 1(1) nm，c=1.114 13(7)nm，β=114.589(5)°，V=3.199 5(3) nm³，Z=4，D_c=1.398 g·cm^-3，μ=0.667 mm^-1，F(000)=1 416，R=0.057 6，wR=0.1535。在化合物1晶体中，酮肟分子之间通过分子间氢键形成二维网状结构。在化合物2中，每个镍(Ⅱ)离子由1个3-(水杨酰肼)-丁基-2-酮肟的2个氮原子和1个氧原子，2个吡啶分子中的2个氮原子和1个乙酸根中的1个氧原子形成畸变的NiN₄O₂八面体配位构型，存在分子内氢键O-H(肟)…O(乙酸根)和O-H(酚)…N(酰肼)。在化合物3晶体中，每个镍(Ⅱ)离子由2个3-(水杨酰肼)-丁基-2-酮肟的4个氮原子和2个氧原子配位，形成畸变的NiN₄O₂八面体配位构型。晶体中存在O-H…O和O-H…N两种分子内氢键和O-H…O分子间氢键。     

有机-无机复合物[H2(PW12O40){Zn(C10H8N2)2(H2O)}]·1.5[Zn(C10H8N2)3]·1.75H2O的合成、结构及性能

An organic-inorganic hybrid complex, [H₂(PW₁₂O₄₀){Zn(C₁₀H₈N₂)₂(H₂O)}]·1.5[Zn(C₁₀H₈N₂)₃]·1.75H₂O has been synthesized hydrothermally and structurally characterized by X-ray crystallography. The crystal belongs to monoclinic, space grounp C2/c, with a=4.709 4(2) nm, b=1.431 77(7) nm, c=2.621 07(1) nm, β=90.125(4)°, V=17.673 4(2) nm³, Z=8, D_c=3.087 Mg·m^-3, F(000)=14 884, μ(Mo Kα)=16.327 mm^-1. The structure was refined to R₁=0.068 7 and wR₂=0.158 0 for 20 128 observed reflections with I>2σ(I). Single crystal structure shows that the title compound is constructed from [PW₁₂O₄₀]^3- cluster anion and [Zn(C₁₀H₈N₂)₂(H₂O)]²⁺ metal-organic complex cation, in which metal Zn(Ⅱ) cation are coordinately bonded to the terminal oxygen of Keggin polyanions. The title compound exhibits good catalytic activity for oxidation of benzaldehyde to benzoic acid. CCDC: 624772.     

一个二维锰配位聚合物[Mn2(L)2(1,3-BDC)2]·0.25H2O的合成、结构和表征

The title complex, [Mn₂(L)₂(1,3-BDC)₂]·0.25H₂O 1 (L=2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,3-H₂BDC=1,3-benzenedicarboxylic acid) has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2₁/n with a=1.751 68(6) nm, b=1.160 14(4) nm, c=2.585 30(8) nm, β=104.331(4)°, V=5.090 3(3) nm³, Z=4, C₅₄H_28.50Cl₂F₂Mn₂N₈O_8.25, M_r=1 140.13, D_c=1.488 g·cm^-3, F(000)=2 306, μ(Mo Kα)=0.673 mm^-1, R=0.060 5 and wR=0.161 6. The compound 1 exhibits two-dimensional wavy layer structures, which are further stacked through π-π interactions to form three-dimensional supramolecular architectures. CCDC: 760201.