The New Carbodiimide Li2Gd2Sr(CN2)5 Having a Crystal Structure Related to That of Gd2(CN2)3

The new carbodiimide compounds Li₂RE₂Sr(CN₂)₅ (RE = Sm, Gd, Eu, Tb) were prepared by a straight forward solid state metathesis reaction of REF₃, SrF₂, and Li₂(CN₂) at around 600 °C. The crystal structure of Li₂Gd₂Sr(CN₂)₅ was solved based on X‐ray single‐crystal diffraction data. Corresponding Li₂RE₂Sr(CN₂)₅ compounds were analyzed by isotypic indexing of their powder patterns. The crystal structure of Li₂Gd₂Sr(CN₂)₅ can be well related to that of Gd₂(CN₂)₃, because both structures are based on layered structures composed of close packed layers of [N=C=N]^2– sticks, alternating with layers of metal ions. The crystal structure of Li₂Gd₂Sr(CN₂)₅ can be considered to contain an ABC layer sequence of [N = C=N]^2– layers with the interlayer voids being occupied by (three) distinct types of cations.     

Rare Earth Carbodiimide Silicates: RE2(CN2)(SiO4)

Rare earth carbodiimide silicates RE₂(CN₂)(SiO₄) with RE = Y, La, and Pr were synthesised by solid state metathesis reactions of RECl₃, Li₂(CN₂), and SiO₂ or Li₂SiO₄, respectively, in silica tubes at 550 °C. All three compounds crystallise with different structures, although all of them represent distorted derivatives of the sodium chloride type structure. The structure of Y₂(CN₂)(SiO₄) was refined monoclinically (C2/m, Z = 2, a = 1301.382(5) pm, b = 377.630(1) pm, c = 527.656(2) pm, β = 93.9816(2) °) from X‐ray powder data. The crystal structure of La₂(CN₂)(SiO₄) was refined in a different monoclinic space group (P2₁/c, Z = 4, a = 660.3(1) pm, b = 1282.0(2) pm, c = 656.2(1) pm, β = 105.23(2) °), and the structure of Pr₂(CN₂)(SiO₄) was refined triclinically (P\bar{1} , Z = 2, a = 646.7(2) pm, b = 669.2(2) pm, c = 671.8(2) pm, α = 86.18(3) °, β = 73.22(3) °, γ = 74.08(3) °) from X‐ray single crystal data.     

3-硝基-1,2,4-三唑-5-酮镱配合物的制备及其晶体结构

３硝基１，２，４三唑５酮（ＮＴＯ）的锂盐水溶液与Ｙｂ２Ｏ３的稀硝酸溶液反应，制备了标题配合物，其化学式为Ｙｂ（ＮＴＯ）３·１０Ｈ２Ｏ。用Ｘ射线衍射法测定配合物的晶体结构，其分子式为［Ｙｂ（ＮＴＯ）３（Ｈ２Ｏ）４］·６Ｈ２Ｏ。属单斜晶系，空间群为Ｃ２／ｃ。晶胞参数如下：ａ＝３６９３１（５）ｎｍ，ｂ＝０６６８３（１０）ｎｍ，ｃ＝２５６５６（３）ｎｍ，β＝１３０９７４（５）°，Ｖ＝４７８１１（１１）ｎｍ３，Ｚ＝８，Ｄｃ＝２０１３ｇ·ｃｍ－３，μ＝４０１７ｍｍ－１，Ｆ（０００）＝２８５０。镱离子的配位数为７，其配位多面体为五角双锥。     

镧系四元混合阴离子配合物[Ln(CCl3COO)2(CH3COO)(Phen)(H2O)]2的合成与晶体结构

在水乙醇溶液中合成了３ 种四元混合阴离子配合物， 用元素分析、ＩＲ、ＵＶ 及单晶Ｘ射线衍射进行了表征。［Ｌａ（ＣＣｌ３ＣＯＯ）２（ＣＨ３ＣＯＯ）（Ｐｈｅｎ）（Ｈ２Ｏ）］２·２ＤＭＦ 晶体属三斜晶系， Ｐ１ 空间群， 晶胞参数：ａ＝ １－２５１０（４） ｎｍ ， ｂ＝ １－３４６０（５） ｎｍ ， ｃ ＝ １－０３４３（３） ｎｍ ， α＝ １０２－４７（３）°， β＝ １０２－３４（２）°， γ＝ １１３－８２（２）°， μ（ＭｏＫα） ＝ ２０．４７ ｃｍ －１ ， Ｚ＝ １， Ｄｃ＝ １－８００ ｇ·ｃｍ － ３ ， Ｆ（０００） ＝ ７８０－００。稀土配合物中醋酸根以桥联方式配位， 三氯醋酸根则有２ 种配位方式， 在二者共同参与配位的体系中呈现出丰富的配位模式。     

Eu(BA)3phen的晶体结构和荧光光谱

标题配合物晶体属三斜晶系，Ｐ１空间群，晶胞参数ａ＝１０７９２（２）ｎｍ，ｂ＝１１８９６（２）ｎｍ，ｃ＝１２４４６ｎｍ，α＝１０５１２（３）°，β＝９３７６（３）°，γ＝１１３１９（３）°，Ｖ＝１３９２（１）ｎｍ－３，Ｚ＝２，Ｄｘ＝１６５９ｇ·ｃｍ－３。配合物晶体由双核分子组成，两个中心Ｅｕ３＋通过羧基桥联，它们的化学环境相同。Ｅｕ３＋的配位数为８，其配位多面体为一畸变的四方反棱柱体。在７７Ｋ配合物的荧光光谱说明配合物中仅存在一种Ｅｕ３＋格位。     

二(四氢糠基茚)稀土氯化物的合成及晶体结构

将四氢糠基茚锂分别与无水三氯化钇和无水三氯化钆以摩尔比2;1反应,除去不溶物和溶剂后,将产物在甲苯/THF中冷冻得到晶体(C₄H₇OCH₂C₉H₆)₂LnCl[Ln=Y(1);Ln=Gd(2)].这两种配合物都是单分子无溶剂化合物,在空气中稳定.配合物1和2的晶体结构都属于正交晶系,P2₁2₁2₁空间群,晶胞参数分别为a=1.04252(9)nm,b=1.47455(12)nm,c=1.49799(13)nm,Z=4,Dc=1.508g/cm³;a=1.03701(10)nm,b=1.47233(12)nm,c=1.51354(14)nm,Z=4,Dc=1.699g/cm³.它们的结构相似,但空间构象不同.稀土中心离子分别与两个茚中的五元环和两个氧原子及氯原子成键,形成九配位结构.     

钇与丙氨酸配合物[Y（Ala）（H2O）6]Cl3的合成,表征及晶体结构

合成了钇人氨酸配合物的单晶，用Ｘ射线衍射法了配合物单晶的结构，化学式为「Ｙ（Ａｌａ）（Ｈ２Ｏ）６」Ｃｌ３。的晶体属单斜晶系，Ｐ２１／ｃ空间群，晶胞参数：ｄ＝０．８４４３（２）ｎｍ，ｂ＝１．５６５８（３）ｎｍ，ｃ＝１．１３５９（２）ｎｍ，β＝１０２．０９（２），Ｖ＝１．４６８４（５）ｎｍ＾３，Ｚ＝４，ＤＣ＝１．７７５ｇ／ｃｍ＾３，Ｙ＾３＋的配位数为８，其配位多面丛为三角十二面体。通过元素分析、红外光     

Crystal Structures and Thermal Behaviour of Lanthanide(III) Hexanoate 1, 10‐Phenanthroline Complexes, [M(C5H11CO2)3(phen)] and [Tm(C5H11CO2)2(NO3)(phen)]

Lanthanide(III) hexanoate 1, 10‐phenanthroline complexes crystallise in the space group P2₁/n. The compounds consist of dimers, whereby two lanthanide ions are held together by two bidentate bridging and two tridentate bridging carboxylate groups. The first coordination sphere of the lanthanide ions is completed by one bidentate chelating carboxylate group and by one bidentate 1, 10‐phenanthroline molecule, resulting in the coordination number 9. The dimers have a spherical form, which has important consequences for the thermal properties of complexes. The basic idea behind the preparation of this type of compounds is the stabilisation of the ionic lanthanide layer, so that the smaller lanthanide ions (from which the normal alkanoates do not show mesomorphism because they are too small) show liquid crystallinity. The stabilisation of the ionic layer was successful, expressed by the high melting temperatures, but mesomorphism is not observed. The absence of mesomorphism is related to the isotropic structure of the compounds. A lower symmetry is obtained when a hexanoate group is replaced by a nitrate group. Thulium(III) dihexanoate nitrate 1, 10‐phenanthroline crystallises in the space group P1¯. However, this compound also shows a spherical dimeric structure, but no mesomorphism.     

镧系邻菲罗啉四元混合阴离子配合物的合成和晶体结构

从水／乙醇溶剂和酸性溶液中合成一系列包含ｐｈｅｎ（ｐｈｅｎ：邻菲罗啉）的镧系四元混合阴离子配合物。采用元素分析、红外光谱、紫外光谱、热分析和单晶Ｘ射线衍射对其组成和结构进行了表征。结果表明，［Ｃｅ（ＣＨ３ＣＯＯ）２（ＮＯ３）（ｐｈｅｎ）２］属单斜晶系，空间群Ｃ２／ｍ，ａ＝１５４４４（６）ｎｍ，ｂ＝１２２７３（５）ｎｍ，ｃ＝１２７７６（５）ｎｍ，β＝１３１８９（２）°，Ｖ＝１８０２（１）ｎｍ３，Ｚ＝２，Ｒ＝００２４，Ｒｗ＝００３２。     

CeAgAs2 — a New Derivative of the HfCuSi2 Type of Structure: Synthesis,Crystal Structure and Magnetic Properties

Single crystals of CeAgAs₂ have been obtained by chemical transport reactions starting from a pre‐reacted powder sample. The crystal structure was solved using X‐ray diffraction (space group Pmca, No. 57, a = 5.7586(4) Å, b = 5.7852(4) Å, c = 21.066(3) Å, Z = 8) and refined to a residual of R(F) = 0.029 for 46 refined parameters and 1020 reflections. The structure of CeAgAs₂ represents a new distorted and ordered variant of the HfCuSi₂ type. The characteristic feature of this structure are infinite cis‐trans chains of As atoms with As—As distances of 2.563(1) Å and 2.601(1) Å. CeAgAs₂ is paramagnetic (μ_eff = 2.37 μ_B, θ = —10.5(2) K), with antiferromagnetic ordering at 5.5(2) K and exhibits a metamagnetic transition starting at 4.6 kOe and T = 1.8 K.     

（TAGH）2（TNR）的合成、晶体结构及热分析

合成了三氨基胍三硝基间苯二酚盐(TAGH)2(TNR)(TAG)三氨基胍;TNR:2,4,6-三硝基间苯二酚),并对其进行了元素分析及红外光谱表征.利用X射线单晶衍射分析测定了其晶体结构.该晶体属于单斜晶系,空间群为C2/c,晶体学数据为,a=2.2892(6)nm,b=1.2802(3)nm,c=1.3661(4)nm,β=111.174(5)°,V=3.7333(16)nm3,Z=8.该化合物是由二个C(N2H3)3+与一个(C6HN3O8)2相结合而成的离子型化合物.用差示扫描量热法、热重法和微商热重法研究了该化合物的热分解过程,研究结果表明,在10 K·min-1的升温速率下,该化合物只有一个剧烈的放热分解过程,该过程发生在450.1-477.7K之间,且分解产物主要是气体产物.     

O-半乳吡喃糖基N,N-二(2-氯乙基)磷酰二胺酯的合成及其晶体结构

为探讨糖基磷酰胺酯类化合物的抗肿瘤活性,用三氯氧磷作磷酰化试剂,合成了标题化合物.通过重结晶,分离出标题化合物的一个纯异构体.经X射线衍射单晶结构分析,该晶体属单斜晶系,空间群P2₁,a=1.3474(5)nm,b=1.0624(4)nm,c=1.6916(5)nm,β=110.55(3)°,z=4,D_x=1.35g/cm³.收集到独立衍射点4379个,其中2159个为可观测点.最终一致性因子R=0.079.结构分析结果表明,反应中形成的手性磷原子为R构型.     

Synthesis and Crystal Structure of 5-N-i-Propyl-2-(2′-nitrobenzenesulfonyl)-glutamine

The title compound, 5-N-I-propyl-2-(2′-nitrobenzenesulfonyl)-glutamine, was synthesized and its structure was confirmed by IR, MS, 1H NMR, and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The crystal belongs to Monoclinic, space group P2(1), with α=0.69281(11) nm,b=0.76508(12),c=1.5843(3) nm,α=90°,β=90.941(3)°,γ=90°,V=0.8397(2) nm3,Z=2,Dc=1.477 g/cm3,μ=0.236 mm-1 , F(000)=392, R=0.0297, and wR=0.0664.     

Crystal Structure of the RE2PbS4 (RE = Y,Dy, Ho,Er, and Tm) Compounds and a Comparison with the Crystal Structures of other Rare Earth Lead Chalcogenides

The crystal structure of the RE₂PbS₄ (RE = Y, Dy, Ho, Er and Tm) compounds (space group Cmc2₁, Pearson symbol oC112, a = 0.79301(3) nm, b = 2.86966(9) nm, c = 1.20511(5) nm, R_Bragg = 0.0979 for Y₂PbS₄; a = 0.79484(8) nm, b = 2.8721(3) nm, c = 1.2039(1) nm, for Dy₂PbS₄; a = 0.79081(2) nm, b = 2.86222(7) nm, c = 1.20220(4) nm, R_Bragg = 0.0859 for Ho₂PbS₄; a = 0.7863(2) nm, b = 2.8525(5) nm, c = 1.1995(2) nm, R1 = 0.0482 for Er₂PbS₄ and a = 0.78419(3) nm, b = 2.84184(9) nm, c = 1.19655(4) nm, R_Bragg = 0.0893 for Tm₂PbS₄) was investigated by means of X‐ray single crystal and powder diffraction. Each RE atoms is octahedrally coordinated by six S atoms. Each Pb atoms is surrounded by seven S atoms to form a mono‐capped trigonal prism.     

[Eu2(TCM)2(DMSO)6]·2DMSO双核笼状稀土配合物的合成与结构

报道一个H3TCM配体在较小尺寸的溶剂DMSO中与稀土离子Eu3+通过自组装形成的双核笼状结构, 从中可进一步看出溶剂分子的尺寸对该双核结构的影响.     

Missing Carbodiimide and Oxide Carbodiimide of Scandium: Sc2(CN2)3 and Sc2O2(CN2)

The new scandium(III) carbodiimides Sc₂(CN₂)₃ and Sc₂O₂(CN₂) were prepared by solid-state metathesis reactions between Li₂(CN₂) and ScCl₃ and, regarding Sc₂O₂(CN₂), Sc₂O₃ was added. The X-ray powder diffraction pattern refinements lead to a trigonal-rhombohedral (R3 c) crystal system for Sc₂(CN₂)₃ and to an orthorhombic (Immm) crystal system for Sc₂O₂(CN₂). The structure of Sc₂(CN₂)₃ is isotypic to the well-known rare earth carbodiimides RE₂(CN₂)₃ with the smaller cations RE = Tm, Yb, and Lu, whereas Sc₂O₂(CN₂) is not isotypic to the known RE₂O₂(CN₂) (RE = Y, La, Ce–Gd, except Pm) compounds. Both crystal structures are represented by layered arrangements of scandium, respectively scandium and oxide, alternating with carbodiimide layers.     

Synthesis and Crystal Structure of Cs(VO2)3(TeO3)2, a New Layered Cesium Vanadium(V) Tellurite

Synthetic Cs(VO₂)₃(TeO₃)₂ is built up from infinite sheets of distorted octahedral V^VO₆ groups, sharing vertices. These octahedral layers are “capped” by Te atoms (as parts of pyramidal [Te^IVO₃]^2– groups) on both faces of each V/O sheet, with inter‐layer, 12‐coordinate, Cs⁺ cations providing charge compensation. Cs(VO₂)₃(TeO₃)₂ is isostructural with M(VO₂)₃(SeO₃)₂ (M = NH₄, K). Crystal data: Cs(VO₂)₃(TeO₃)₂, M_r = 732.93, hexagonal, space group P6₃ (No. 173), a = 7.2351(9) Å, c = 11.584(2) Å, V = 525.1(2) ų, Z = 2, R(F) = 0.030, wR(F ²) = 0.063.     

Crystal and electronic structures of CaAl2Si2-type rare-earth copper zinc phosphides RECuZnP2 (RE=Pr, Nd, Gd-Tm, Lu)

The quaternary rare-earth phosphides RECuZnP₂ (RE=Pr, Nd, Gd-Tm, Lu) have been prepared by reaction of the elements at 900 °C, completing this versatile series which forms for nearly all RE metals. They adopt the trigonal CaAl₂Si₂-type structure (Pearson symbol hP5, space group P3?m1, Z=1), as confirmed by single-crystal X-ray diffraction analysis on ErCuZnP₂ and powder X-ray diffraction analysis on the remaining members. The Cu and Zn atoms are assumed to be disordered over the single transition-metal site. Band structure calculations on a hypothetically ordered YCuZnP₂ model suggest a semimetal, with a zero band gap between the valence and conduction bands. This electronic structure is supported by XPS valence band spectra for RECuZnP₂ (RE=Gd-Er), in which the intensity drops off smoothly at the Fermi edge. The absence of a band gap permits the electron count to deviate from the precise value of 16 e⁻ per formula unit, as demonstrated by the formation of a solid solution in GdCu_xZn_2−xP₂ (1.0≤x≤1.3), while still retaining the CaAl₂Si₂-type structure. Because the Cu 2p XPS spectra indicate that the Cu atoms are always monovalent, the substitution of Cu for Zn leads to a decrease in electron count and a lowering of the Fermi level in the valence band. The magnetic susceptibility of RECuZnP₂ (RE=Gd-Er), which obeys the Curie-Weiss law, confirms the presence of trivalent RE atoms.     

镧系四元混配化合物[Ln(BA)2(NO3)(phen)]2的合成、晶体结构和波谱研究

在酸性介质、含水溶剂中合成了四元混配化合物[Ln(BA)₂(NO₃)(phen)]₂(BA=苯甲酸根;Ln=La,Ce,Pr,Nd,Sm,Eu,Dy,Gd,Tb,Er),用元素分析、IR、DTA-TG等方法对配合物进行了表征.研究了配合物的顺磁性能和荧光性能.镨配合物的单晶衍射结果表明,配合物属三斜晶系,双核,Pr³⁺的配位数为9,4个BA呈二种配位方式,丰富了四元配合物的结构表现形式.