基于邻苯二甲酰-L-丙氨酸配体的两例Cu（Ⅱ）纯手性同质多晶配合物:合成与结构

合成了2例Cu（Ⅱ）的纯手性同质多晶[CuL₂（Phen）]（HL=邻苯二甲酰-L-丙氨酸,Phen=1,10-菲咯啉）,并对其进行了表征。X射线单晶衍射测定表明,邻苯二甲酰-L-丙氨酸在2例配合物中采取了相同的配位方式,Cu（Ⅱ）原子具有变形的八面体配位环境,分别和2个邻苯二甲酰-L-丙氨酸离子上的2个羧基氧原子,1个1,10-菲咯啉的2个氮原子配位。不同的是这2例同质多晶显示出不同的颜色,并且配合物1属于单斜晶系,C2空间群,配合物2属于正交晶系,P2₁2₁2₁空间群。配合物1通过π…π堆积作用形成一维链状结构,配合物2是简单小分子结构。此外,DFT理论研究表明,配合物1具有较低的能量,稳定性更高。     

间规聚苯乙烯的同质多晶现象

间规聚苯乙烯具有复杂的同质多晶现象，有α，β，γ，δ四种晶型和两种介晶型。本文综述了间规聚苯乙烯的晶体结构、晶型转变以及其结晶和熔融行为等方面的研究进展。     

基于邻苯二甲酰-L-丙氨酸配体的两例Cu(Ⅱ)纯手性同质多晶配合物:合成与结构（英文）

合成了2例Cu(Ⅱ)的纯手性同质多晶[CuL_2(Phen)](HL=邻苯二甲酰-L-丙氨酸,Phen=1,10-菲咯啉),并对其进行了表征。X射线单晶衍射测定表明,邻苯二甲酰-L-丙氨酸在2例配合物中采取了相同的配位方式,Cu(Ⅱ)原子具有变形的八面体配位环境,分别和2个邻苯二甲酰-L-丙氨酸离子上的2个羧基氧原子,1个1,10-菲咯啉的2个氮原子配位。不同的是这2例同质多晶显示出不同的颜色,并且配合物1属于单斜晶系,C2空间群,配合物2属于正交晶系,P2_12_12_1空间群。配合物1通过π…π堆积作用形成一维链状结构,配合物2是简单小分子结构。此外,DFT理论研究表明,配合物1具有较低的能量,稳定性更高。     

3-氨基-1,4,5,6-四氢吡咯[3,4-c]吡唑构筑的钴(Ⅱ)、铜(Ⅱ)配合物的晶体结构

以3-氨基-1,4,5,6-四氢吡咯[3,4-c]吡唑（Athpp）为配体合成了2个金属配合物即CoCl₄（Athpp）₂·2H₂O（1）和CuCl₄（Athpp）₂（2）。用红外、元素分析和X-射线单晶衍射等手段表征了晶体结构。配合物1结晶在P1空间群而配合物2结晶在P2₁/n空间群。金属中心均采取扭曲八面体构型。此外,还研究了配合物的固体荧光性质     

以Eu^3＋为荧光探针研究（LaO）3BO3的结构

利用多晶Ｘ射线衍射法研究了（ＬａＯ）３ＢＯ３合成的工艺条件和结构。以少量Ｌｉ２ＣＯ３作助熔可在较低温度和较短反应时间内制备出（ＬａＯ３）ＢＯ３纯物相。（ＬａＯ）３ＢＯ３属单斜晶系，空间群为Ｐ２１／ｍ或Ｐ２１。根据Ｅｕ＾３＋荧光光谱以５Ｄ０→７Ｆ２电偶极跃迁为主及５Ｄ０→７ＦＪ（Ｊ＝０、１、２、３、４）跃迁的谱峰数并结合空间群中各个等效点的对称性，推断Ｌａ＾３＋在（ＬａＯ）３ＢＯ３中所处格位的点对称     

基于咪唑离子液体的锰（Ⅱ）配合物的合成、晶体结构及发光性能

室温下,通过改变卤化咪唑类离子液体的种类,合成了2个结构和光学性能不同的低维锰(Ⅱ)配合物(C_4H_7N_2)[MnCl_3(H_2O)](1)和(C_4H_7N_2)_2[MnBr_4](2)。采用单晶X射线衍射、光致发光光谱、X射线激发发射光谱、衰减曲线、热重分析等手段对配合物进行了详细的表征。X射线单晶衍射结果表明:配合物1属单斜晶系,P2_1/n空间群,中心离子Mn(Ⅱ)为八面体构型;配合物2属三斜晶系,空间群为■,中心离子Mn(Ⅱ)为四面体构型。在370 nm紫外光的激发下,固体配合物1和2分别发射深红色光和绿色光,其荧光寿命分别为200.11和37.23μs,量子产率分别为23.52%和5.54%,并且在X射线激发下,表现出优良的X射线荧光性能。     

（Y，Gd）Al3（BO3）4：Ce，Tb的光谱特性及稀土离子间的能量传递

采用高温固相反应合成了(Y，Gd)Al3(BO3)4中掺杂Ce^3 和Tb^3 的样品，并研究了其结构特性、光谱特性和发光过程中稀土离子问的能量传递。(Y，Gd)Al3(BO3)4属于三角晶系，具有R32的空间群，掺入Ce^3 ，Tb^3 杂质后晶格结构没有变化。(Y，Gd)Al3(BO3)4：Ce，Tb的激发光谱由3个宽谱带组成，这3个谱带分别对应于Ce^3 的4f-5d跃迁吸收。在该体系中存在Ce^3 →Tb^3 ，Gd^3→Tb^3 和Gd^3 →Ce^3 的能量传递，其中Ce^3 起敏化剂和中间体的双重作用。     

[NiCl（Ph2PCH2CH2OH）2Cl·H2O]^＋Cl^-和[Ni（Ph2P（O）CH2CH2OH）4]^2＋[NiCl4]^2-的合成及晶体结构

通过NiCl2.6H2O与双齿配体2-（二苯基膦）乙醇（Ph2PCH2CH2OH）或其氧化物2-（二苯基氧膦）乙醇[Ph2P（O）CH2CH2OH]的反应,制得两种结构新颖的阳离子型镍配合物[NiCl（Ph2PCH2CH2OH）2（H2O）]^＋Cl^-（1）和[Ni（Ph2P（O）CH2CH2OH）4]^2＋[NiCl4]^2-（2）.通过元素分析、31P核磁共振及X射线单晶衍射对配合物1和2的结构进行了表征.配合物1的晶体属单斜晶系,C2/c空间群,中心金属Ni具有六配位八面体几何构型.配合物2属四方晶系,I4（1）/a空间群,中心原子Ni与P＝＝O基团中的O配位形成平面四边形构型.     

一种不对称Salamo-型螯合配体及其钴（Ⅱ）配合物：合成、表征与晶体结构

合成了一种不对称Salamo-型螯合配体4-氯-6’-甲氧基-2,2’-[乙二氧双（氮次甲基）]二酚（H₂L）及其钴（Ⅱ）配合物[Co（L）（H₂O）],并通过元素分析、红外光谱、紫外-可见吸收光谱及X-射线单晶衍射方法对配体H₂L及其配合物进行了表征。结果表明：配体属单斜晶系,P2₁/n空间群,配合物属正交晶系,Iba2空间群。配合物为单核结构,由1个Co（Ⅱ）离子和1个四齿的L^2-配体单元和1个配位水分子组成,中心Co（Ⅱ）原子的配位数是5,且具有稍微扭曲的三角双锥几何结构,而配合物分子通过分子间C8-H8…Cl1氢键组装成1D链状的超分子结构。     

1(R),2(R)-二(2-苯并咪唑)乙二醇四核铜(Ⅱ) 配合物的合成与晶体结构

合成了一种新配合物1（R）,2（R）－二（2－苯并咪唑）乙二醇四核铜（Ⅱ[Cu4(bbmed)4Cl2L2].Cl2(CH3OH)5(H2O)2(L=MeOH或H2O,Hbbmed=1(R),2(R)-二（2－苯并咪唑）乙二醇,bbmed表示去质子后的配体）简称Cu( Ⅱ）-bbmed)。该晶体经X－射线衍射确定为正交晶系,空间群C221（20）,晶胞参数a=1.7424(5),b=2.4942(7),c=3.8887(11)nm,V=16.900(8)nm^3,Z=4,Dc=1.427g.cm^-3,F(000)=7472,并对它进行了元素分析、IR、^1H NMR及ESR表征。     

Solid-state polymerization of diacetylene: 1,11,13,23-tetracosatetrayne

The solid-state polymerization of a diacetylene, 1,11,13,23-tetracosatetrayne, was studied using x-ray powder diffraction and electron diffraction. It is shown that the material exhibits polymorphism. Thermochromic transitions, which are generally observed for diacetylenes, are related to the particular crystalline phase using x-ray powder diffraction. The unit cell dimensions and space group of one polymorph were determined by electron diffraction analysis: a = 20.83 Å, b = 4.84 Å, c = 10.08 Å, β = 92.4°, space group: P2₁/n. © 1995 John Wiley & Sons, Inc.     

Polymorphism in homochiral zinc phosphonates

This paper reports four homochiral zinc phosphonates, alpha-(S)-[Zn 2(pemp)(pempH)Cl] (1), alpha-(R)-[Zn 2(pemp)(pempH)Cl] (2), beta-(S)-[Zn 2(pemp)(pempH)Cl] (3), and beta-(R)-[Zn 2(pemp)(pempH)Cl] (4) [pempH 2 = (1-phenylethyl)amino]methylphosphonic acid]. Both 1 and 2 are enantiomers, crystallizing in an orthorhombic P2(1)2(1)2(1) space group, while 3 and 4 are polymorphic phases of 1 and 2, respectively, crystallizing in a monoclinic P2(1) space group. The polymorphism is induced by temperature or additional organic molecules.     

Kristall- und Molekülstruktur von Bis(1,1-diethyl-3-thiobenzoyl-thioureato)nickel(II)

Crystal and Molecular Structure of Bis(1,1-diethyl-3-thiobenzoyl-thioureato)nickel(II). Bis(1, 1-diethyl-3-thiobenzoyl-thioureato)nickel(II) forms two modifications, whose structures have been determined by X-ray structure analysis. The monoclinic modification crystallizes in the space group P2₁/n with a = 13.709, b = 8.571, c = 12.803 Å, β = 68.10° and Z = 2. The triclinic modification crystallizes in the space group I1 with a = 14.406, b = 7.761, c = 11.734 Å, α = 86.10, β = 97.39, γ = 90.18° and Z = 2. The molecular structures of both modifications are nearly identical (packing polymorphism). The coordination is exactly planar, the ligands are arranged in trans position. The average Ni? S bond length is 2.153 Å in the monoclinic form and 2.163 Å in the triclinic form. The chelate rings deviate from planarity.     

γ‐Sodium gallate: a Rietveld refinement using X‐ray powder diffraction

Tetrahedrally coordinated oxides usually present polymorphism, but for NaGaO₂, only the β polymorph has been reported. In this work, the synthesis and structural characterization of γ‐sodium gallate, γ‐NaGaO₂, are presented. The crystal structure belongs to the orthorhombic system, space group Pbca (No. 61), and has been characterized by a Rietveld refinement of the X‐ray powder diffraction pattern. The structure is similar to those exhibited by the γ phases of many tetrahedral oxides.     

Polymorphism of 2,5‐[(diphenylphosphanyl)methyl]‐1,1,2,4,4,5‐hexaphenyl‐1,4‐diphospha‐2,5‐diboracyclohexane

2,5‐[(Diphenylphosphanyl)methyl]‐1,1,2,4,4,5‐hexaphenyl‐1,4‐diphospha‐2,5‐diboracyclohexane shows polymorphism as two tetrahydrofuran (THF) disolvates [C₆₄H₅₈B₂P₄·2C₄H₈O, (Ia) and (Ib)] and pseudo‐polymorphism as its toluene monosolvate [C₆₄H₅₈B₂P₄·C₇H₈, (Ic)]. In each of polymorphs (Ia) and (Ib), the diphosphadiboracyclohexane molecule is located on a centre of inversion. The THF molecule of (Ib) is disordered over two sites, with a site‐occupation factor of 0.612 (8) for the major‐occupied site. Both structures crystallize in the same space group (P2₁/n), but they display a different crystal packing. For pseudo‐polymorph (Ic), although the space group is P2₁/c, which is just a different setting of the P2₁/n space group of (Ia) and (Ib), the crystal packing is completely different. Although the crystal packing in these three structures is significantly different, their molecular conformations are surprisingly the same.     

A new conformer of indium germanate InGe3O7.5(en): conformational polymorphism in germanate family

A new conformer of indium germanate InGe(3)O(7.5)(en) (denoted as δ-type), constructed with the flexible unit of In(2)Ge(6)O(15)N(2) was successfully prepared through a solvothermal method. The crystal data for the δ-type InGe(3)O(7.5)(en) are listed as follows: triclinic, space group P-1 (No.2), a = 7.826(4) ?, b = 8.287(3) ?, c = 9.224(4) ?, α = 71.887(17)°, β = 85.343(18)°, γ = 63.734(12)°, V = 508.64 ?(3), Z = 2. Four relevant conformers of indium germanate are compared with each other. The conformational polymorphism in the germanate family is reported for the first time.     

SOM assembly of hydroxynaphthoquinone and its oxime: polymorphic X-ray structures and EPR studies

Investigation on solvent-induced polymorphism in X-ray structures of 2-hydroxy-1,4-naphthoquinone (Lawsone) 1, is carried out. In protic methanol, 1 crystallizes in monoclinic space group P2(1)/c (1a) comprising of 2D hydrogen bonded network via cyclic dimers. In aprotic solvent such as acetone on the other hand, 1 exhibits orthorhombic space group Pna 2(1) (1b) and emerges with 1D catemeric chain. Solvent-induced topological isomerism of cyclic dimers and helical catemeric chains arising from (i) bifurcated intra- and inter molecular hydrogen bondings viz. O-H...O=C interactions between C(2) hydroxyl and C(1), C(4) carbonyls, (ii) C-H...O interactions viz. C(3)-H...O(1)C(1) have been discussed. A signal for radical in 1 at g = 2.0058 is signatured by EPR spectrum and it's oxime derivative viz. 2-hydroxy-4-naphthoquinone-1-oxime 2, in solid state shows biradical and monoradical formation with aggregation of dimer and monomer due to non-covalent hydrogen bonds. Zero field split parameters for 2 are estimated to be D = 215 G, Ex = 13 G, Ey = 47 G at 298 K. A half field signal at 77 K indicates triplet ground state. Frozen glass EPR of 2 resolves as regioregular dimeric-monomeric species showing hyperfine interactions with 1-oximino nitrogen in dimer A (14N) = 15.5 G].     

2‐[4‐Phenyl‐5‐(2‐pyridyl)‐4H‐1,2,4‐triazol‐3‐yl]nicotinic acid: a case of solvent‐dependent polymorphism

The title compound, C₁₉H₁₃N₅O₂, crystallizes in two monoclinic forms depending on the solvent used. From methanol or acetone, a yellow form [(Ia), m.p. 533 K] in the space group P2₁ is obtained, while with ethanol as the solvent, an orange form [(Ib), m.p. 541 K] in the space group Cc results. The conformers observed in the two polymorphs differ primarily in the relative orientation of pyridine/phenyl and triazole rings. Molecules of both polymorphs form chains through carboxyl O—H...N hydrogen bonding; however, in each crystal structure, a different group acts as acceptor, viz. a triazole and a pyridyl N atom for (Ia) and (Ib), respectively. This is the first case of polymorphism observed for crystals of a 3,4,5‐trisubstituted 1,2,4‐triazole derivative.     

Two new polymorphs of di­phenyl(4‐pyridyl)­methyl methacryl­ate

The title compound (D4PyMA), C₂₂H₁₉NO₂, exhibits polymorphism after crystallization by slow evaporation from a binary mixture of chloro­form and hexane. Long needle‐like crystals have an orthorhombic structure (space group Fdd2), with one mol­ecule in the asymmetric unit, while small tablet‐like crystals exhibit a monoclinic crystal structure (space group P2₁/n), in which two independent but chemically identical mol­ecules comprise the asymmetric unit. The bond lengths and angles are normal, while the torsion angles around the –C—O– bond linking the di­phenyl(4‐pyridyl)methyl and methacryl­ate groups show the flexibility of the mol­ecule by way of packing effects. The two polymorphs both contain weak C—H⋯π and C—H⋯O/N contacts but have different conformations.     

Fuzzy space periodic symmetries for polyynes and their cyano-compounds

In our previous papers on the molecular fuzzy symmetry, we analyzed the basic characterization in connection with the fuzzy point group symmetry. In this paper, polyynes and their cyano-derivatives are chosen as a prototype of linear molecules to probe the one-dimensional fuzzy space group of parallel translation. It is notable that the space group is an infinite group whereas the point group is a finite group. For the fuzzy point group, we focus on considering the fuzzy characterization introduced due to the difference of atomic types in the monomer through point symmetry transformation in the beginning; and then we consider the difference between the infinity of space group and the finite size of real molecules. The difference between the point group and the space group lies in the translation symmetry transformation. This is the theme of this work. Starting with a simple case, we will only analyze the one-dimensional translation transformation and space fuzzy inversion symmetry transformation in this paper. The theory of the space group is often used in solid state physics; and some of its conclusions will be referred to. More complicated fuzzy space groups will be discussed in our future papers.