具有类白钨矿结构的KGd(MoO_4)_2的晶体结构和能带结构(英文)

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=0.529 23(6)nm,b=0.692 10(6)nm,c=1.068 89(7)nm,α=75.79(8)°,β=76.79(5)°,γ=67.60(4)°,Z=2,R1(all data)=0.025 8。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。     

新型混合价态双核钴化合物Co(Ⅰ)Co(Ⅱ)(μ-Ph_2Ppy)_2(μ-CO)_2Cl_3的合成和分子结构

本文合成了新型混合价态双核钴化合物Co(Ⅰ)Co(Ⅱ)(μ-Ph_2Ppy)_2(μ-CO)_2Cl_3[Ph_2Ppy为2-(二苯基膦基)吡啶],并对其分子结构进行了测定,收集到了三维独立的衍射点3569个,晶体空间群为P2_1nb。晶胞参数a=13.32(1),b=14.31(1),c=18.94(2),Z=4。用直接法解出结构,用全矩阵最小二乘法进行结构精修,最终的R值为0.072。结构特征是:不考虑Co—Co键的情况下,一个钻原子是五配位变形三角双锥构型,形式氧化态为+1。另一个钻原子是六配位变形八面体构型,形式氧化态为+2。Co—Co键距为2.685(1)。该分子属C-(2v)点群。该分子进一步还原可得到具有w-框架结构的新混合价态化合物Co(0)Co(Ⅰ)(μ-Ph_2Ppy)_2(μ-CO)(CO)Cl。     

三核铁簇硫酸盐K_2(H_3O)_3[Fe_3(H_2O)_3O(SO_4)_6]·6H_2O的合成与晶体结构

在室温条件下合成了含三核铁簇的硫酸盐配合物K2(H3O)3[Fe3(H2O)3O(SO4)6].6 H2O,借助IR光谱、紫外-可见吸收光谱、X射线光电子能谱(XPS)和X射线单晶衍射等测试手段对其结构进行了表征.结果表明,标题化合物属于六方晶系,P6(3)/m空间群,晶胞参数为:a=b=0.963 7(2)nm,c=1.885 1(9)nm,V=1.516 3(9)nm3,Z=2,Dc=2.316 g/cm3,GOOF=1.089,R1=0.062 8,wR2=0.165 1.其分子由1个三核铁簇阴离子[Fe3(H2O)3O(SO4)6]5-、2个K+离子、3个水合质子H3O+和6个结晶水分子组成.     

一个新颖氰根桥联化合物SmFe(CN)_6(DMSO)_2·H_2O的合成与结构

稀土氯化物SmCl3(6H2O与K3Fe(CN)6在水/乙醇/DMSO混合溶剂中反应合成了标题化合物: SmFe(CN)6(DMSO)2(H2O(C10H14N6O3S2FeSm, Mr = 536.59),晶体属单斜晶系,空间群 P2/n,a = 7.759(1), b = 10.673(1),c = 11.014（2）?,β= 97.106（2）(,V = 905.0（2）? 3, Z = 2 , Dc = 1.969 g/cm3, F（000）= 520,R = 0.0474 , wR = 0.0925。该化合物为氰基桥联稀土-过渡金属化合物,稀土离子(Sm3+)为7配位的五角双锥构型。化合物的结构可描述为由方砖铺砌成的楼梯状二维层结构,层之间由氢键连接沿b轴方向堆积而成三维网状结构。     

混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3的合成晶体结构及性能

[Mn3O(O2CCH2Cl)6(C5H5N)2(H2O)]· CH2ClCOO· H2O在 pH=4.5的 HOAc NaOAc的缓冲水溶液中和 2,2′联吡啶 (bipy)反应,制得了混合价双核锰配合物 [(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3· 1.5H2O。该配位化合物的 X射线单晶衍射表明,该晶体属单斜晶系,空间群 P21/c,晶胞参数： a=1.3854(3), b=1.3943(3), c=2.4225(5)nm,β =103.30°, V=4.554(2)nm3, Z=4, Dc=1.448g· cm－ 3。其紫外可见光谱在 640nm处有一个峰,可指派为桥配体 O2－到 Mn?的电荷迁移光谱 .循环伏安实验说明,此配合物在半波电位 E1/2为 1.25V处,有一个可逆的氧化还原峰,这相应于 (Ⅲ, Ⅳ )态氧化为 (Ⅳ,Ⅳ )态 ,另外在 0.37V处有一阴极峰,相应于 (Ⅲ,Ⅳ )态还原为 (Ⅲ,Ⅲ )态,在 0.81V处有一氧化峰,相应于 (Ⅲ,Ⅲ )态氧化为 (Ⅲ,Ⅳ )态,这两个峰是不可逆的。     

新型三维开放骨架稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4(Ln=Gd,Eu)的合成、结构及荧光性质

以哌嗪为模板剂,在水-乙醇混合溶剂体系中溶剂热合成了两个具有三维开放骨架结构的稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4（Ln = Gd,化合物1和Eu,化合物2）,并对其进行了结构表征、热重以及荧光光谱分析. 单晶结构解析表明,化合物1和2属于同构异质,均结晶于单斜晶系,P21/c空间群,化合物1,a = 19.691(3) ?,b = 19.249(3) ?,c = 13.186(2) ?,β = 92.33(0)o,V = 4993.5(1) ?3, Z =4. 化合物2,a = 19.7233(8) ?,b = 19.2791(8) ?,c = 13.2095(5) ?,β = 92.329(1)o,V = 5018.7(3) ?3, Z =4. 两个化合物在ab平面上由SO4,GdO8和GdO9多面体共边或共角交错连接形成含有八元环和十六元环的二维层状结构,该二维层沿c方向平行排列,相邻层通过SO4四面体相连形成具有孔道的三维开放骨架结构,其孔道之中包含平衡骨架负电荷的质子化哌嗪分子. 化合物2的固体荧光光谱分析显示其在397nm激发波长下,表现出典型的Eu3+发光性质.       

异双核化合物PdMo(μ-Ph~2Ppy)~2(μ-CO)(CO)~2I~2.0.5CH~2Cl~2的合成和晶体结构

本文合成了新的异双核化合物PdMo(μ-Ph~2Ppy)~2(μ-CO)(CO)~2I~2.0.5CH~2Cl~2, 对它进行了表征, 并测定其晶体和分子结构。该化合物属PI空间群, a=0.9500(2), b=1.1302(2), c=1.993(1)nm, α=102.82(3),β=101.21(3), γ=94.57(2)°, D~x=1.82g/cm^3, Z=2, R=0.064。晶体结构测定表明, 该化合物具有Pd-Mo键, 键长为0.28596(9)nm。如将Pd-Mo键考虑在内, Pd原子为d^9五配位构型, Mo原子为d^5七配位构型。两者的形式氧化态均为+1。     

[(C6H5 NO2)Pr(H2O)4](CrMo6O24H6)·(C6H5NO2)·2.5H2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[(C6H5NO2)2Pr(H2O)4](CrMo6O24H6)·2.5H2O,通过红外光谱和X射线单晶衍射对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.a=2.3442(9)nm,b=1.3291(5)nm,c=2.458(1)nm,β=103.08(1)°,V=7.460(5)nm3,R1=0.0727,wR2=0.1903.结构分析表明,[CrMo6O24H6]3-阴离子通过端氧担载一个配位的Pr3+离子形成中性的(C6H5NO2)Pr(H2O)4(CrMo6O24H6)基团,相邻的中性基团在Ot—Pr—Ot桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构.     

两个具stp三维拓扑构型的稀土配位聚合物{[Ln_2(pda)_3(H_2O)_2]·2H_2O}_n(Ln=Nd,La)

本文利用水热合成方法,将稀土氧化物与邻苯二乙酸(H2pda)反应得到了2个新颖的稀土配位聚合物{[Ln2(pda)3(H2O)2]·2H2O}n(Ln=Nd(1),La(2))。测定了它们的晶体结构,并进行了X-射线单晶衍射、红外光谱、荧光光谱和热重分析等性质的表征。晶体结构测定表明这2个化合物为异质同晶化合物。属单斜晶系,C2/c空间群。晶体学参数分别为配合物1:a=2.629 06(18)nm,b=1.611 72(11)nm,c=0.783 27(5)nm,β=93.173(5)°,V=3.313 9(4)nm3,Z=4,F(000)=1 840,μ=3.173 mm-1,Dc=1.878 g·cm-3,R1=0.022 6,wR2=0.060 9;配合物2:a=2.627 1(14)nm,b=1.614 9(8)nm,c=0.796 6(4)nm,β=92.850(9)°,V=3.375(3)nm3,Z=4,F(000)=1 816,μ=2.570 mm-1,Dc=1.823 g·cm-3,R1=0.0466,wR2=0.1416。化合物中邻苯二乙酸配体连接相邻的稀土金属离子,形成复杂的具有stp拓朴构型的三维网络结构。     

双核铜配合物[Cu(μ-C6H5COO)2(C4H8O)]2的合成及表征

采用氧化-加成法,合成了配合物[Cu(μ-C6H5COO)2(C4H8O)]2,通过单晶X射线衍射,FT-IR、ESR光谱等手段对标题配合物的结构和性质进行了测试和表征.其晶胞参数为:单斜晶系,空间群为P21/c,晶胞参数为:a=0.920 1(1)nm,b=1.769 0(4)nm,c=1.094 9(4)nm,β=108.97(1)°,V=1.685 4(3)nm3,Dc=1.46g/cm3,Z=2;它是由四个桥联苯甲酸和两个四氢呋喃组成的二聚体.     

新型混价稀土氟化物KEuLaF~6: 结构设计和碱金属还原法相结合的新产品

用钾还原Eu~0.5La~0.5F~3合成了KEuLaF~6。新化合物属于UCl~3的填隙结构,gagarinite和NaNdF~4的相关型。空间群P3, 三方晶系, 点阵参数: a=646.8(6),c=373.9(4)pm, c/a=0.578, V=135.47·10^6(12)pm^3, D~p~y~c=5.37,D~x=5.44g·cm^-^3, Z=1。新化合物在空气中稳定, 不溶于水。还报道新化合物的荧光图谱和红外     

Synthesen und Kristallstrukturen von neuen Alkalimetall‐Selten‐Erd‐Telluriden der Zusammensetzungen KLnTe2 (Ln = La,Pr, Nd,Gd), RbLnTe2 (Ln = Ce,Nd) und CsLnTe2 (Ln = Nd)

Syntheses and Crystal Structures of New Alkali Metal Rare‐Earth Tellurides of the Compositions KLnTe₂ (Ln = La, Pr, Nd, Gd), RbLnTe₂ (Ln = Ce, Nd) and CsLnTe₂ (Ln = Nd) Of the compounds ALnQ₂ (A = Na, K, Rb, Cs; Ln = rare earth‐metal; Q = S, Se, Te) the crystal structures of the new tellurides KLaTe₂, KPrTe₂, KNdTe₂, KGdTe₂, RbCeTe₂, RbNdTe₂, and CsNdTe₂ were determined by single‐crystal X‐ray analyses. They all crystallize in the α‐NaFeO₂ type with space group R3¯m and three formula units in the unit cell. The lattice parameters are: KLaTe₂: a = 466.63(3) pm, c = 2441.1(3) pm; KPrTe₂: a = 459.73(2) pm, c = 2439.8(1) pm; KNdTe₂: a = 457.83(3) pm, c = 2443.9(2) pm; KGdTe₂: a = 449.71(2) pm, c = 2443.3(1) pm; RbCeTe₂: a = 465.18(2) pm, c = 2533.6(2) pm; RbNdTe₂: a = 459.80(3) pm, c = 2536.5(2) pm, and CsNdTe₂: a = 461.42(3) pm, c = 2553.9(3) pm. Characteristics of the α‐NaFeO₂ structure type as an ordered substitutional variant of the rock‐salt (NaCl) type are layers of corner‐sharing [(A⁺/Ln³⁺)(Te^2—)₆] octahedra with a layerwise alternating occupation by the cations A⁺ and Ln³⁺.     

Kristallstruktur von Tl4Fe(CN)6

Crystal Structure of Tl₄Fe(CN)₆ Single crystals of Tl₄Fe(CN)₆ have been prepared for the first time and its crystal structure was determined. The pale yellow compound crystallizes in the triclinic space group P1 (No. 2) with the lattice parameters a = 726.6(1) pm, b = 797.4(8) pm, c = 1 336.0(1) pm, α = 104.7(9)°, β = 90.0(8)°, γ = 97.6(7)°, Z = 2 in a new structure type.     

钇磷钨三元杂多配合物的合成及其稀土多元渗与导电性的研究

合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、~(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm~3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10~(-2)S·cm~(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。     

Single Crystals of NaPrTe2 with LiTiO2‐Type Structure

During attempts to synthesize rare‐earth nitride tellurides black and bead‐shaped single crystals of the title compound sodium praseodymium(III) ditelluride (NaPrTe₂) were obtained as a by‐product by reacting a mixture of praseodymium, sodium azide (NaN₃) and tellurium at 900 °C for seven days in evacuated torch‐sealed silica vessels. NaPrTe₂ crystallizes cubic (space group: Fd3¯m, Z = 16; a = 1285.51(9) pm, V_m = 79.96(1) cm³/mol, R₁ = 0.028 for 146 unique reflections) and exhibits the Na⁺ and Pr³⁺ cations in slightly distorted octahedra of six telluride anions (d(Na—Te) = 325 pm, d(Pr—Te) = 317 pm) each. The main characteristics of this new structure type for alkali‐metal rare‐earth(III) dichalcogenides can be derived from the rock‐salt type structure (NaCl, cubic closest‐packed Te^2— arrangement, all octahedral voids occupied with Na⁺ and Pr³⁺) with alternating layers consisting of Na⁺ and Pr³⁺ cations in a ratio of 3:1 and 1:3, respectively, piled along the [111] direction.     

Ternäre Halogenide vom Typ A3MX6. III [1, 2]. Synthese,Strukturen und Ionenleitfähigkeit der Halogenide Na3MX6 (X = Cl,Br)

Ternary Halides of the A₃MX₆ Type. III [1, 2]. Synthesis, Structures, and Ionic Conductivity of the Halides Na₃MX₆ (X = Cl, Br) The bromides Na₃MBr₆ crystallize with the stuffed LiSbF₆-type structure (type I; M = Sm? Gd) or with the structure of the mineral cryolite (type II; M = Gd? Lu). The structure types were refined from single crystal X-ray data (Na₃SmBr₆: trigonal, space group R3 , a = 740.8(2) pm, c = 1 998.9(8) pm, Z = 3; Na₃YBr₆: monoclinic, space group P2₁/n, a = 721.3(4) pm, b = 769.9(2) pm, c = 1 074.8(4) pm, β = 90.60(4)°, Z = 2). Reversible phase transitions from one structure to the other occur. The phase transition temperatures were determined for the bromides as well as for the chlorides Na₃MCl₆ (M = Eu? Lu). The refinement of both structures for one compound was possible for Na₃GdBr₆ (I: trigonal, space group R3 , a = 737.1(5) pm, c = 1 887(2) pm, Z = 3; II: monoclinic, space group P2₁/n, a = 725.2(1) pm, b = 774.1(3) pm, c = 1 080.1(3) pm, β = 90.76(3)°, Z = 2). All compounds exhibit ionic conductivity of the sodium ions which decreases with the change from type I to type II. The conductivity of the bromides is always higher when compared with the respective chlorides.     

Synthesis and Crystal Structure of Er_2Si_2O_7

1INTRODUCTIONThecompoundwithcompositionIRE,O,:ZSiO,(RE~rareEarth)exhibitsex-tensivepolymorphismthatarecharacterizedbyboundariesateuropiumandholmiumalongtheseriesoftrivalentrareearths.Asfarasthestructureisconcerned,typeCisofspecialstabilitybecauseitsrangecanbeextendedbeyondthesmallestrareearthLug toScs tl'z}.Notlongago,wereportedstructureofNd,Si,O,withstructureformAt33.SynthesisandstructureofErZSiZO7withstructureformCarehereinre-ported.2EXPERIMENTAL'ThestartingmaterialsEr,O,…     

Synthese und Kristallstrukturbestimmung von Dimethyldi-(N-Methylimidazolium)siliciumbromid

Synthesis and Crystal Structure Determination of Dimethyldi-(N-Methylimidazolium)silicon Bromide The reaction of dibromodimethylsilane with n-methylimidazole (NMI) leads to a 1:2 compound stable at room temperature. The reaction was carried out at room temperature and colorless, moisture sensitive crystals were obtained by sublimation. The addition compound crystallizes in the orthorhombic space group Pcam (No. 57) with lattice constants a = 1 110 96(8) pm, b = 1 142.3(2) pm and c = 1 238.9(3) pm. For 1 317 independent reflections, measured at 21°C, the structure could be refined to R = 0.040 and R_w = 0.041.     

Darstellung und Kristallstruktur von Cs4SnO3

Preparation and Crystal Structure of Cs₄SnO₃ Crystals of Cs₄SnO₃ were synthesized by reaction of SnO with elemental Cs. The compound crystallizes with the triclinic spacegroup P1 with lattice constants a = 737.61(9) pm, b = 1171.3(1) pm, c = 1199.2(1) pm, α = 66.08(3)°, β = 80.88(2)°, γ = 82.28(3)° and Z = 4. The crystal structure exhibits isolated stannate(II) ions [Sn^IIO₃]^4– of ψ-tetrahedral form. Whereas a new structure type is present, there is a close relationship with the structures of the Cs stanntates and plumbates(IV).