阳离子-π相互作用--[K(DB18C6)]2[M(SCN)4](M=Pd,Pt)的合成与结构研究

合成了二苯并18冠6与Pd,Pt生成的新颖配合物:[K(DB18C6)]2 [Pd(SCN)4] (1), [K(DB18C6)]2 [Pt(SCN)4](2),并通过元素分析、红外光谱、单晶X射线衍射进行了表征.两个配合物均为三斜晶系,空间群P-1.1的晶体学数据:a=0.87375(17)nm,b=1.1900(2)nm,c=1.3180(3)nm,α=73.56(3)°,β=99.90(3)°,γ=82.34(3)°,V=1.298 6(4)nm3,Z=1,F(000)=584,R1=0.075 2,wR2=0.166 0.2的晶体学数据:a=0.855 3(5)nm,b=1.312 7(3)nm,c=1.181 9(3)nm,α=106.21(2)°,β=82.77(3)°,γ=99.72(3)°,V=1.251 6(8)nm3,Z=1,F(000)=818,R1=0.0254,wR2=0.0682.1,2均由两个[K(DB18C6)]+配离子和一个[M(SCN)4]2-配阴离子组成.在固态、配合物两个分子的[K(DB18C6)]+和[M(SCN)4]2-通过K+-π相互作用形成假一维无限链状结构.     

弱相互作用构筑的二维、三维冠醚配合物{[K(18-C-6)2(C2H4Cl2)}[Ni(dmit)2]2和[K(18-C-6)][Ni(dmit)2]的合成与结构

研究了18－冠－6与NiCl·6H2O,K2dmit(dmit=4,5-dimercapto-1,3-dithiole- 2-thione,C3S5^2－）在不同溶剂中反应生成的两个标题配合物{[K(18-C-6)]2 (C2H4Cl2)}[Ni(dmit)2]2（1）和[K(18-C-6)][Ni(dmit)2](2)。通过元素分析、红 外光谱、单晶X射线衍射进行了表征。1和2均属三斜晶系,空间群P1^-.1的晶体学 数据：a=1.0272(2)nm,b=1.2282(3)nm,c=1.4205(3)nm,α=113.473(3)°,β=90. 609(3)°,γ=91.439(3)°,V=1.6430(6)nm^3,Z=2,F（000)=876,R1=0.0503。2的 晶体学数据：a=0.8502(2)nm,b=1.2178(4)nm,c=1.5118(4)nm,α=86.454(5)°,β =77.734(5)°,γ=85.364(5)°,V=1.5228(8)nm^3,Z=2,F(000)=774,R1=0.0565。配 合物1,2分别通过K…S,K…Cl,S…S和K…S,S…S弱相互作用形成二维、三维网状 结构。     

一维链状冠醚配合物[K(B18-C-6)]_2[M(SCN)_4](M=Pd,Pt)的合成与结构

合成了苯并18-冠-6（B18-C-6）与K_2[Pd(SCN)_4]生成的配合物[K（B18-C-6 ）]_(12) [Pd(SCN)_4] (1), [K(B18-C-6)]_2[Pt(SCN)_4] (2)和[K(B18-C-6)]_2 [Pt(SCN)_4]·C_2H_4Cl_2 (3),并通过元素分析、红外光谱、单晶X射线衍射进行 了表征。1和2为单斜晶系,空间群P2_l/n,晶体学数据：1, a = 1.00970(17) nm, b = 1.3157(2) nm, c = 1.7303(3) nm, β = 94.841(2)°, V = 2.2852(7) nm~3, Z = 2, F(000) = 1136, R_1 = 0.0257。3为三斜晶系,空间群P1,晶体学 数据：a = 0.95914(18) nm, b = 1.2137(2) nm, c = 2313(2) nm, α = 63.693 (2)°, β = 76.293(2)°, γ-1.2406(4) n~3, Z = 1 F(000)618,R_1 = 0.0366 。在固态,三个配合物相邻的两个[K（B18-C-6）]~+基团通过冠醚氧化原子与钾的 子的相边接而形成一维链状结构。     

三烃基锡配合物(PhCMe_2CH_2)_3Sn[O_2C(CHRPh)] [R: OH(1), H(2)]的合成、结构、热稳定性、量子化学及毒性研究

甲醇中氧化双[三(2-甲基-2-苯基)丙基锡]分别与DL-扁桃酸、苯乙酸反应,合成了2个三烃基锡配合物(PhCMe2CH2)3Sn[O2CCH(OH)Ph](1)和(PhCMe2CH2)3Sn(O2CCH2Ph)(2)。经IR、1H和13C NMR、元素分析和X-射线单晶衍射表征结构。1和2均属三斜晶系,空间群P1。配合物1晶体学参数:a=0.971 1(2)nm,b=1.176 6(3)nm,c=1.700 8(4)nm,α=96.840(12)°,β=103.235(12)°,γ=110.725(11)°,Z=2,V=1.726 0(7)nm3,Dc=1.288 g·cm-3,μ(Mo Kα)=0.773 mm-1,F(000)=696,R1=0.032 5,wR2=0.087 3。配合物2晶体学参数:a=0.972 85(9)nm,b=1.161 40(11)nm,c=1.689 31(16)nm,α=96.830(5)°,β=101.935(5)°,γ=110.770(4)°,Z=2,V=1.707 1(3)nm3,Dc=1.271 g·cm-3,μ(Mo Kα)=0.778 mm-1,F(000)=680,R1=0.024 8,wR2=0.067 3。1和2的中心锡原子均为畸变四面体构型。通过分子间C-H…O或C-H…π作用,1和2分别形成一维带状或链状结构。热重分析结果表明,1和2具有良好的稳定性。毒性测试的初步结果表明,配合物1、2具有较好的环境相容性,对石螺急性毒性较小。     

18-冠-6与Na2[M(mnt)2](M=Cu,Ni)配合物的合成与结构

研究了18-冠-6分别与Na2[M(mnt)2][M=Cu,Ni;mnt=丁二腈烯二硫醇阴离子,C2S2(CN)^2^-~2]的反应,得到的配合物{[Na(18-C-6)][Na(18-C-6)(H2O)]}[Cu(mnt)2](1),[Na(18-C-6)(H2O)]2[Ni(mnt)2].(18-C-6)(2)通过元素分析、红外光谱、X射线单晶衍射进行了表征。两个配合物均为三斜晶系,空间群P1。1的晶体学结构数据：a=1.22697(19)nm,b=1.22780(19)nm,c=1.5665(3)nm,α=95.083(3)°,β=101.534(3)°,Υ=91.007(3)°,V=2.3016(6)nm^3,Z=2,Dcalcd=1.350g/cm^3,F(000)=976,R1=0.0726,wR2=0.1843.2的晶体学结构数据：a=1.11620(17)nm,b=1.22054(18)nm,c=1.27939(18)nm,α=111.647(2)°,β=29.792(3)°,Υ=103.201(2)°,V=2.5461(4)nm^3,Z=1,Dcalcd=1.304g/cm^3,F(000)=642,R1=0.0459,wR2=0.1003.1中的[Cu(mnt)2]^2^-通过mnt的氮原子与[Na(18-C-6)]^+中的钠原子成键,形成了一维链状结构;[Na(18-C-6)(H2O)]^+只起平衡电荷的作用。2中的[Ni(mnt)2]^2^-也通过配体的mnt氮原子与两个[Na(18-C-6)(H2O)]^+中的钠原子成键,形成稳定的中性配合物。     

Anderson-B-型多金属氧酸盐[Co(2,2''-bipy)3]H-[Al(OH)6(Mo6O18)]·5H2O的合成及晶体结构

以AlCl3·6H2O、Na2MoO4·2H2O、CoCl2·6H2O和2,2'-联吡啶为主要原料合成了Anderson-B-型多金属氧酸盐[Co(2,2'-bipy)3]H[Al(OH)6(Mo6O18)]·5H2O,进行了红外光谱、紫外光谱、差热分析和单晶结构测定.晶体学测定结果表明,化合物属于三斜晶系,Pi空间群,晶胞参数:a=1.216 0(2),b=1.221 5(2),c=1.780 0(4)nm,α=86.83(3)°,β=88.76(3)°,γ=89.82(3)°,V=2.639 4(9)nm3,Z=2,R1=0.079 4,wR2=0.176 6.化合物结构分析表明,在晶体学上,标题化合物分子是由1个[Co(2,2'-bipy)3]2+配阳离子,1个H+离子,2个1/2[Al(OH)6(Mo6O18)]3-多阴离子和5个结晶水分子组成.多阴离子[Al(OH)6(Mo6-O18)]3-借助水分子和金属配离子通过超分子作用形成二维网状结构,网状结构之间又借助超分子作用形成三维无限伸展结构.差热分析表明,标题化合物的失重过程分为2步,多阴离子骨架破坏温度为547.5℃.     

Anderson-B-型多金属氧酸盐[Co(2,2-′bipy)_3]H-[Al(OH)_6(Mo_6O_(18))]·5H_2O的合成及晶体结构

以A lC l3.6H2O、Na2MoO4.2H2O、CoC l2.6H2O和2,2′-联吡啶为主要原料合成了Anderson-B-型多金属氧酸盐[Co(2,2-′b ipy)3]H[A l(OH)6(Mo6O18)].5H2O,进行了红外光谱、紫外光谱、差热分析和单晶结构测定。晶体学测定结果表明,化合物属于三斜晶系,Pī空间群,晶胞参数:a=1.216 0(2),b=1.221 5(2),c=1.780 0(4)nm,α=86.83(3)°,β=88.76(3)°,γ=89.82(3)°,V=2.639 4(9)nm3,Z=2,R1=0.079 4,wR2=0.176 6。化合物结构分析表明,在晶体学上,标题化合物分子是由1个[Co(2,2-′b ipy)3]2 配阳离子,1个H 离子,2个1/2[A l(OH)6(Mo6O18)]3-多阴离子和5个结晶水分子组成。多阴离子[A l(OH)6(Mo6-O18)]3-借助水分子和金属配离子通过超分子作用形成二维网状结构,网状结构之间又借助超分子作用形成三维无限伸展结构。差热分析表明,标题化合物的失重过程分为2步,多阴离子骨架破坏温度为547.5℃。     

新型磷酸钒孔道结构化合物(H3NCH2CH2NH3)3- [ (VO)4(PO4)2 (HPO4)4]的水热 合成及结构表征

以有机分子乙二胺作为模板剂合成了新型磷酸钒孔道化合物(H3NCH2CH2NH3)3^-[(VO)4(PO4)2(HPO4)4,并通过X射线单晶衍射实验进行了结构表征,晶体学数据为：C2/c,a=1.8505(9)nm,b=0.7089(4)nm,c=2.3304(10)nm,β=96.43(3)°,V-3.038(3)nm^3,Z=8,R=0.067,Rw^b=0.1635,该化合物具有非常独特和规整的二维孔道骨架结构,进一步的晶体化学研究表明该化合物为一新的VPO物相。     

一维链状冠醚配合物[k(18-C-6)]~2[M(NO~2)~4](H~2O)(M=Pd,Pt) 的合成与结构

研究了18-C-6分别与k~2[Pd(NO~2~4],k~2[Pt(NO~2)~4])的反应,并通过元素分析、红外光谱、单晶X射线衍射对生成的配合物[k(18-C-6)]~2[Pd(NO~2)~4](H~2O)~0.5(1)和[k(18-C-6)]~2,k~2[Pt(NO~2)~4])(H~2O)(2)进行了表征,两个配合匀匀为单斜晶系,空间P2~1/c.1的晶体学数据：α=1,7104(3),c=1,5763(3)nm,β=93.49(3)°,V=3.9987(14)nm^3,Z=4,D~c=1.507g/cm^3,F(000)=1880,R~1=0.0681,~wR~2=0.1004。2的晶体学数据：a=1.1312(3)nm,b=1.4227(2)nm,c=1.2266(3)nm,β93.141(10)°,V=1.9711(8)nm^3,Z=4,D~c=1.614g/cm^3,F(000)=936,R~1=0.0265,~wR~2=0.0721。在固态,配合物1具有[(18-c-6)]~2[Pd(NO~2)~4](H~2O)(1a)和[(18---c-6)]~2[Pd·(NO~2)~4](1b)两个分子,两者比例这1：1前者相邻的两个分子通过水分是的氧原子相连接形成一维链状结构,后者形面假一维链状结构,在配合物2中相邻的两个分子通过品分子中的氧原子相连接形成一维链状结构。     

阳离子- π相互作用————————[K(DI18C6)]2[M(SCN)4] (M=Pd,Pt)的合成与结构 研究

合成了二苯并18冠6与Pd,Pt生成的新颖配合物：[K(DI18C6)]2[Pd(SCN)4](1),(K(DB18C6)]2[Pt(SCN)4](2),并通过元素分析、红外光谱、单晶X射线衍射进行了表征,两个配合物均为三斜晶系,空间群P-1.1的晶体学数据：a=087375(17)nm,b=1.1990(2)nm,C=1.3180(3)nm,α=73.56(3)°,β=99.90(3)°,γ=82.34(3)°,V=1.2986(4)nm^3,Z=1,F(000)=584,R1=0.0752ωR2=0.1660.2的晶体学数据：a=0.8553(5)nm,b=1.3127(3)nm,c=1.1819(3)nm,α=106.21(2)°,β=82.77(3)°,γ=99.72(3)°V=1.2516(8)nm^3,Z=1,F(000)=818,R1=0.0254,ωR2=0.0682.1,2均由两个[K(DB18C6)^+配离子和一个[M(SCN)4]^2+配阴离子组成。在固态、配合物两个分子的[K(DB18C6)]^+和[M(SCN)4]^2-通过K^+-π相互作用形成假一维无限链状结构。     

具有类白钨矿结构的KGd（MoO4）2的晶体结构和能带结构

以Gd₂O₃、K₂CO₃、MoO₃为原料,采用高温熔盐法,合成了一个含钾的稀土钼酸盐KGd（MoO₄）₂。通过X射线单晶衍射法测定了它在室温下的晶体结构,并测定了它的光学性质。结构分析表明它属于三斜晶系,空间群为P1,a=0.52923（6）nm,b=0.69210（6）nm,c=1.06889（7）nm,α=75.79（8）°,β=76.79（5）°,γ=67.60（4）°,Z=2,R₁（alldata）=0.0258。结构中的K和Gd原子位于各自的晶体学位置,不存在调制结构的现象。此外,我们用得到的晶体学数据,通过密度泛函理论研究了化合物的能带结构、态密度、介电常数,其结果和实验数据相吻合。     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

Structure, thermal stability and properties of Li3Sc(BO3)2

Polycrystalline Li₃Sc(BO₃)₂ was synthesized through the solid-state reaction, which is air-, water- and thermal-stable below about 929 °C. Its crystal structure was resolved and refined on the basis of powder X-ray diffraction data. The metal-borate framework is built up from ScO₆ octahedra connected to each other by sharing common edges, corners and faces of BO₃ units and LiO₄ groups. Coordination surrounding of B-O in this structure, [BO₃]³⁻ group, was confirmed by an infrared absorption spectrum of an Li₃Sc(BO₃)₂. According to the electronic structure calculated by first-principles calculations, an Li₃Sc(BO₃)₂ is an insulator with a wide indirect energy band gap of about 4.4 eV. Considering the facile synthesis, large band gap, and thermal stability and excellent Tb³⁺-doped photoluminescence characteristics of this compound in general, it may be a good candidate as host of phosphors deposited on chip of the light-emitting diodes for white-color conversion.     

金属硫族化合物CsSb2(Se2)0.5Se3的溶剂热合成及其晶体结构分析

以有机溶剂热生长技术(Solvothermal Technique)在180 ℃乙二胺(en)溶液中以SbCl₃与碱金属硒化物Cs₂Se和Se在密闭容器中反应7 d,制备出新的金属硫族化合物CsSb₂(Se₂)_0.5Se₃。以单晶X射线衍射技术测得晶体结构属三斜晶系,空间群为P1,晶胞参数：a=0.653 0(2) nm,b=0.707 1(3) nm,c=0.979 9(4) nm,α=80.37(3)°,β=86.28(3)°,γ=74.61(3)°,V=0.430 0(3) nm³,Z=2。     

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.     

Rh2(μ-SC6H5)2(CO)4的合成和晶体结构

一种路易斯碱，例如膦（PR3）或异氰化物（CNR）加到双核或多核络合物中，会导致低核物种的形成，这就伴随有金属一金属键的断裂[1]．这样的例子很多，如我们曾用F33（CO）12与P（SC6H5）3反应，分离出三个不同的两核铁数合物[2]．现在我们报导另一个例子：用Rh4（CO）12与P（SC6H小反应，同样也得到一个两核物种WhZ（P－SC6H巾（C）4．该化合物首先由B0ltoll＊等人用WhZ（CO）ZC12与苯硫酚C6H。SH反应得到，但有关它的X－rar晶体结构的测定还未见报导·与之相似的化合物Rh。（p－SC。H。F）。门O）。的结构已由ClaverN…     

[Pb2(TNR)(NO3)2(H2O)]的制备和晶体结构研究

[Pb₂(TNR)(NO₃)₂(H₂O)] was prepared by reaction of the aqueous solution of lead nitrate and magnesium styphnate. The crystal structure of Pb₂(TNR)(NO₃)₂(H₂O)was determined by single crystal diffraction analysis. The crystal is triclinic, space group P1 with crystal parameters a=0.7279(2)nm,b=1.0698(2)nm,c=1.0738(2)nm;α=86.82(1)°,β=89.52(2)°,γ=83.50(2)°;V=0.8295(3)nm³,Z=2,D_c=3.201g·cm^-3, F(000)=716. The final R value is 0.0358.In the crystal structure, one lead ion was represented by nine coor-dination geometry; the other was showed as ten coordination geometry.     

Electrical Behavior of New Orthophosphates Na2M3(PO4)3 (M3=GaMn2, GaCd2, InMn2 and FeMnCd) with Alluaudite-Like Structure

New sodium orthophosphates of general formula Na₂M₃(PO₄)₃ belonging to the alluaudite-type structure have been synthesized and characterized by neutron and X-ray powder diffraction. The nature of the M₃ elements (M₃=GaMn₂, GaCd₂, InMn₂ and FeMnCd) was chosen in order to analyze their influence on electrical and magnetic properties. The conductivity of these materials was measured by the complex impedance method and the transport mechanism was studied from complex permittivities and modulus formalism. Electrical results including charge/discharge experiments showed two main behaviors: GaCd₂ and FeMnCd behave as purely ionic conductors whereas GaMn₂ and InMn₂ are mixed ionic-electronic conductors. The magnetic susceptibility data reveal the antiferromagnetic behavior of FeMnCd, InMn₂ and GaMn₂, with a weak ferromagnetic transition at low temperatures.     

Solvothermal Synthesis and Crystal Structure of Zn（en）3 B5O7（OH）3

Introduction Boratecompounds,inwhichboronisboundonly tooxygen,areofconsiderablemineralogicalandindus trialimportance.Thesecompoundscontaininganionic componentscomposedofBO3andBO4groups,which maybelinkedtogetherbysharingoxygenatoms,can formisolatedringsand…     

Synthesis, crystal structure and electrical characterization of two new potassium uranyl molybdates K2(UO2)2(MoO4)O2 and K8(UO2)8(MoO5)3O6

Two new potassium uranyl molybdates K₂(UO₂)₂(MoO₄)O₂ and K₈(UO₂)₈(MoO₅)₃O₆ have been obtained by solid state chemistry . The crystal structures were determined by single crystal X-ray diffraction data, collected with MoKα radiation and a charge coupled device (CCD) detector. Their structures were solved using direct methods and Fourier difference techniques and refined by a least square method on the basis of F² for all unique reflections, with R₁=0.046 for 136 parameters and 1412 reflections with I?2σ(I) for K₂(UO₂)₂(MoO₄)O₂ and R₁=0.055 for 257 parameters and 2585 reflections with I?2σ(I) for K₈(UO₂)₈(MoO₅)₃O₆. The first compound crystallizes in the monoclinic symmetry, space group P2₁/c with a=8.250(1) Å, b=15.337(2) Å, c=8.351(1) Å, β=104.75(1)°, ρ_mes=5.22(2) g/cm³, ρ_cal=5.27(2) g/cm³ and Z=4. The second material adopts a tetragonal unit cell with a=b=23.488(3) Å, c=6.7857(11) Å, ρ_mes=5.44(3) g/cm³, ρ_cal=5.49(2) g/cm³, Z=4 and space group P4/n.In both structures, the uranium atoms adopt a UO₇ pentagonal bipyramid environment, molybdenum atoms are in a MoO₄ tetrahedral environment for K₂(UO₂)₂(MoO₄)O₂ and MoO₅ square pyramid coordination in K₈(UO₂)₈(MoO₅)₃O₆. These compounds are characterized by layered structures. The association of uranyl ions (UO₇) and molybdate oxoanions MoO₄ or MoO₅, give infinite layers [(UO₂)₂(MoO₄)O₂]²⁻ and [(UO₂)₈(MoO₅)₃O₆]⁸⁻ in K₂(UO₂)₂(MoO₄)O₂ and K₈(UO₂)₈(MoO₅)₃O₆, respectively. Conductivity properties of alkali metal within the interlayer spaces have been measured and show an Arrhenius type evolution.