Synthesis and Crystal Structure of a Zinc(II) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

The title zinc（Ⅱ） complex salt [Zn（H2O）6]（ClO4）2-（PNOS）4, where PNOS is derived from picolinaldehyde N-oxide with semicarbazone, has been prepared and structurally characterized by X-ray single-crystal analysis. It crystallizes in triclinic, space group PI with a = 7.529（3）, b = 10.206（4）, c = 14.678（6）A, a = 86.293（6）, β= 87.686（7）, γ= 81.382（6）°, C28H44Cl2N16O22Zn, Mr = 1093.06, V = 1112.3（8） ,A^3 Z = 1, Dc = 1.632 g/cm^3, S = 1.089, μ（MoKa） = 0.773 mm^-1, F（000） = 564, the final R = 0.0438 and wR = 0.1076 for 3888 independent reflections with Rint = 0.0224. The crystal structure possesses a [Zn（H2O）6]^2＋ cation, two ClO4^- anions and four PNOSs. In the crystal structure, Zn^2＋ cation is located at the symcenter and coordinated by six water molecules. In [Zn（H2O）6]^2＋, an elongate octahedral complex cation, the average Zn-O bond length is 2.087（2） A. There exist a lot of H bonds in the structure, linking the cation [Zn（H2O）6]^2＋, anion ClO4^- and PNOS to form a 3D network.

Synthesis and Crystal Structure of a Complex Bimetallic Salt [Ni(trans_[14]diene)] [Ni (mnt)_2]

The title compound has been synthesized by the reaction of [Ni(trans[14]diene)]I2 with Na[Ni(mnt)2] in water and THF, where [trans[14]diene]= 5, 7,7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca-4, 11-diene and mnt2- = cis-1, 2-dicyano-1,2-ethylenedithiolato. Its crystal structure has been determined by X-raycrystallography analysis with 4827 independent reflections (Fo>4σ(F0). The bimetallic complex salt [Ni (trans [14] diene )] [Ni (mnt )2] (C24 H32N8Ni2S4, Mr = 678. 24 )crystallizes in the triclinic system with space group P1, a = 9. 2911 (9), b= 11. 7075(12), c=15. 799(2) A, α=68. 384(7), β=79. 324(7), γ=67. 581(6)°, V=1474. 9(3) A3, Dc=1. 527 Mg/m3, Z=2, λ=0. 71073 A, μ=1. 589mm-1, F(000) =704,R=0. 0367. The structure consists of slightly distorted Square planar units [Ni(trans[14]diene)]2+ and [Ni(mnt)2]2-.

Synthesis, characterization, spectroscopic and crystallographic investigation of metal complexes of N-benzyl-N-nitrosohydroxylamine

New metal complexes of N-benzyl-N-nitrosohy-droxylamine (BNHA) are isolated and characterized by elemental analysis, IR and UV-VIS spectroscopy. Spectrophotometric titration of aqueous solutions of BNHА by salts of some transition metals allowed to calculate the composition and formation constants of the metal complexes. The crystal structure of Cu (BNHА)2 is studied by X-ray diffraction. The Cu atom is coordinated by four O atoms of two bidentate ligands, which close 5-membered chelate rings. The N-O (1.306 ? - 1.320 ?) and N-N (1.274?? and 1.275? ) bond lengths indicate that π electrons are delocalized over the chelating groups. Complexes form stacks with intermolecular Cu…N contacts equal to 3.118?? and 3.306 ?.

复盐结晶法对除菱锰矿浸出液中镁分配规律研究

电解锰生产系统中Mg^(2+)循环累积已成为该行业的共性技术难题,研发经济实用的除镁方法,符合双碳目标背景下的技术发展方向。研究了一种复盐结晶法来控制电解锰系统中Mg^(2+)浓度。在硫酸锰溶液中加入Al_(2)(SO_(4))_(3)·18H_(2)O生成无定形态氢氧化铝,利用无定形态氢氧化铝的特殊性质,结合传统的复盐结晶技术,将硫酸锰溶液中Mg^(2+)的质量浓度控制在20 g/L以下,并获得有一定附加值的锰镁铝氧化物的前驱体。利用XRD、EDS、ICP-MS等检测手段,通过单因素和正交实验得到以下结论:当以铝镁物质的量比为0.3加入铝盐、反应温度为80℃、反应p H为6、反应时间为1 h时,Mg^(2+)分配系数为0.43、Mn^(2+)损失率为31.51%,溶液中Mg^(2+)质量浓度为17.525 g/L、Al^(3+)质量浓度为0.205×10^(-3)g/L,达到预期目标,可保证电解锰生产系统的健康运行。

络离子浓度对掺铝氧化锌(ZAO)纳米粉体粒径的影响

采用络盐法制备了掺铝氧化锌(ZAO)纳米粉体。通过新复合络盐晶体-(NH4)1.95(Zn0.95Al0.05)(SO4)2.6H2O的合成证实了反应初始溶液中形成了络离子。通过改变(NH4)2SO4的加入量研究了络离子浓度对ZAO粒径的影响。通过XRD、SEM和激光粒度仪对ZAO粉体进行了表征。结果表明:络离子的存在,降低了反应初始溶液中游离金属离子的浓度,使得产物的一次粒径的可调控性增强,有利于纳米级ZAO粉体的制备。

固液相平衡级的通用算法

从热力学原理出发,建立了一种固液相平衡级计算的通用方法,通过自动判别平衡时的相数及析出固相的种类,经过较少的迭代次数就可获得固液相平衡时各相分率和组成,从而满足化工过程模拟计算与实际生产的需要。由于该解法为虚拟的等温蒸发过程,在判别平衡相数的同时给出了过程中晶体的析出顺序与各晶体刚析出时溶液组成,这些中间结果为分离过程的模拟计算提供了理论指导。此算法不仅完全不依赖于相图,而且还可通过对不同进料配比的计算,绘制出全范围内的固液相图。通过实例计算证明该方法可适用于目前文献中尚难以处理的复盐、含结晶水盐以及多离子体系。

一种新络合盐晶体——K_3[InCl_6]的合成

在采用本实验室提出的络盐法制备氧化铟锡(Ind ium-tin-oxide,简称ITO)纳米粉末的试验过程中发现和制备了一种新络合盐晶体———K3[InC l6]。通过XRD、SEM和CCD等测试手段对其物相、形貌、元素成份和结构进行了表征。结果表明:该晶体属单斜晶系,空间群为P21/c,分子式为K3[InC l6],Z=4,其晶胞参数为:a=1.2188nm,b=0.7553nm,c=1.2703nm,α=90.00,°β=108.96°,γ=90.00,°V=110.598nm3。

配合物[1-(4'-bromo-2'-fluorobenzyl)pyridinium]_2[Ni(mnt)_2]和[1-(4'-bromo-2'-fluorobenzyl)pyrazinium]_2[Ni(mnt)_2](mnt^(2-)=maleonitriledithiolate dianion)的合成及晶体结构(英文)

本文报道两个含双(马来二氰基二硫烯)镍?配合物阴离子的离子对化合物。对阳离子为1-(4'-溴-2'-氟苄基)吡啶盐时,生成配合物1。晶体数据:三斜晶系,空间群P1珔,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm3,Z=1。对阳离子为1-(4'-溴-2'-氟苄基)吡嗪盐时,生成配合物2。晶体数据:单斜晶系,空间群P21/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm3,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。

含咪唑盐的三联吡啶铜配合物的合成和分子结构

通过带有不同长度的4-(4-氯烷氧基苯基)-2,2'∶6,2″-三联吡啶和N-甲基咪唑在甲苯中加热反应,制备了3种由烷氧基桥联的新型三联吡啶咪唑配体。研究了配体和过渡金属离子的配位反应。测定了三联吡啶咪唑铜配合物的单晶分子结构,在铜配合物中,Cu(Ⅱ)和两个三联吡啶单元形成扭曲八面体配位方式。Monoclinic,空间群P 21/c;a=1.7229(3)nm,b=1.5924(2)nm,c=2.1590(3)nm,α=90°,β=101.332(2)°,γ=90°,Mr=1298.09,V=5.8078(15)nm^3,Dc=1.485 mg/m3,Z=4,F(000)=2684。

三维网状结构钴配合物的合成与晶体结构表征

以1,5-萘二磺酸钠为原料合成了一种钴的配合物,用X-单晶衍射仪测定其晶体结构。该配合物为单斜晶系,晶胞为P2(1)/c,晶胞参数:a=13.2216(18),b=6.67561(10),c=9.6957(15),β=92.0970(10),°V=855.2(2)3,Z=2,Mr=453.29,Dc=1.760 g/cm3,T=289(2)K,F(000)=466,μ(MoKa)=1.307 mm-1,R=0.0275,wR=0.0686,配合物分子通过分子内和分子间氢键形成三维网状结构。

双(苯并咪唑-2-叶立德)蒽-汞(Ⅱ)配合物的合成和结构

N-丁基苯并咪唑与9,10-二(氯甲基)蒽在加热条件下反应生成氮杂环卡宾盐,接着与六氟磷酸钾进行阴离子交换,形成双(苯并咪唑-2-叶立德)蒽六氟磷酸盐配体1,再将配体1和氧化汞反应生成双(苯并咪唑-2-叶立德)蒽-汞(Ⅱ)配合物2。通过1 H NMR、13 C NMR和单晶衍射确定其分子结构,对配体1和配合物2的紫外和荧光性质进行了研究。

基于8-羟基喹啉衍生物镉配合物制备与晶体结构

以季铵盐配体L与Cd(NO_3)_2·4H_2O反应得到配合物[Cd(L)(NO_3)(H_2O)]·NO_3,并通过X射线衍射、红外光谱、质谱等表征了结构.单晶衍射结果表明中心原子Cd(Ⅱ)与去质子化的L^-的3个O原子和一个N原子,1个单齿配位的硝酸根,1个水的O原子和相邻配体2-吡啶N原子配位,形成一维链状结构.晶体属单斜晶系,Pn空间群,晶胞参数a=0.763 54(6)nm,b=0.912 15(7)nm,c=1.856 50(14)nm,α=90.00,β=91.524 0(10),γ=90.00,V=1.292 53(17)nm^3,Z=2,D_c=1.780 g/cm^3,μ=0.921 mm^(-1),F(000)=696,GOF on F^2=1.023,~aR_1[I>2σ(I)],wR_2=0.037 7,0.090 6,R_1[all data],wR_2=0.043 7,0.094 4.

A Novel Chromium(III) Hybrid Salt, Triethylammonium <i>Trans</i>-Diaquabis(Oxalato-<i>κ</i>²O¹,O²) Chromate(III), (C<SUB>6</SUB>H<SUB>16</SUB>N)[Cr(C<SUB>2</SUB>O<SUB>4</SUB>)<SUB>2</SUB>(H<SUB>2</SUB>O) <SUB>2</SUB>]: Synthesis, Spectroscopic Studies, Thermal Behavior and Crystal Structure

A novel organic-inorganic chromium(III) hybrid salt, triethylammonium trans-diaquabis(oxalato-κ2O1,O2)chromate(III), (C6H16N)[Cr(C2O4)2(H2O)2] (1), has been synthesized in aqueous solution and characterized by elemental and thermal analyses, FTIR and UV-Vis spectroscopies, and by single crystal X-ray structure determination. Compound 1 crystallizes in the orthorhombic system, Pbcn space group with the unit cell parameters a = 11.1776(10), b = 7.6105(10), c = 17.5654(2) Å, α = β = γ = 90°, V = 1494.24(3) Å3, Z = 4 and Z’ = 1/2. The structure of 1 consists of [Cr(C2O4)2(H2O)2]− mononuclear anions and triethylammonium [(C2H5)3NH]+ cations. In the anionic unit, the CrIII ion is six coordinated, in a distorted octahedral geometry, by four equatorial O atoms of two oxalate anions acting as chelating ligands and two O atoms from trans-coordinated water molecules occupying the apical positions with longer metal-oxygen distances. In the solid, O-H … O and N-H … O intra and inter molecular hydrogen bonding interactions connect the components into a 3D network. The triethylammonium cations are disordered among two possible orientations with occupancies rates around 50% for C4, N1, C1a, C1b, C4ii, N1ii, C1aii, C1bii (ii = −x + 1, y, − z + 1/2). The IR spectrum of 1 is consistent with the presence of the various molecular building constituents. The UV-Vis spectrum shows two absorption bands around 564 and 416 nm which are compatible with an anionic chromium (III) complex in an octahedral environment. Thermal studies carried out in air between 25°C and 700°C confirm the anhydrous character of 1 and show that it is stable up to 210°C.

Synthesis, Characterization and Thermal Analysis of an Organic-Inorganic Hybrid Salt Involving <i>Trans</i>-Diaquabis(oxalato-κ²<i>O</i>¹,<i>O</i>²)chromate(III) Complex Anion with Piperidinium as Counter Cation

A new organic-inorganic hybrid salt pipéridinium trans-diaquabis(oxalato)- chromate(III) tetrahydrate, (C5H10NH2)[Cr(C2O4)2(H2O)2]·4H2O (1), has been synthesized in water and characterized by FTIR and UV-Vis spectroscopies, elemental and thermal analyses and by single-crystal X-ray diffraction. 1 crystallizes in the orthorhombic non-centrosymmetric space group Cmc21 with the unit cell parameters a = 7.4329(3), b = 9.9356(5), c = 23.6756(11) &Aring;, α = β = γ = 90°, V = 1748.45(14) &Aring;3 and Z = 4. The structure of 1 consists of [Cr(C2O4)2(H2O)2]- mononuclear anions, piperidinium cations and uncoordinated water molecules. The CrIII ion in the complex [Cr(C2O4)2(H2O)2]- is coordinated in a slightly distorted octahedral environment by four O atoms from two chelating oxalate dianions in the equatorial plane, and two O atoms from trans-coordinated water molecules occupying the apical positions. In the crystal, N-H···O and O-H···O hydrogen bond interactions connect the components into a 3-D framework. The IR spectrum of 1 is consistent with the presence of the various molecular building constituents, namely oxalato and aqua ligands, piperidinium cations and solvent water molecules. The UV-Vis spectrum shows two absorption bands around 564 and 416 nm which are compatible with an anionic chromium(III) complex in an octahedral environment. Thermal analysis shows a three-step decomposition of 1, leading to formation of a metal oxide residue.

两种含有四硫富瓦烯羧酸和1,10-菲咯啉配体的金属配合物的合成、结构及光学性质研究

本文用水溶性的四硫富瓦烯(TTF)羧酸盐PropylTTFK_2(1)合成了两种金属配合物Zn(L^1)(Phen)_2·CH_3OH·2H_2O(配合物3)和Cd(L^1)(Phen)_2·2CH_3OH·H_2O(配合物4)(L^1=PropylTTF^(2-);Phen=1,10-phenanthroline)。经元素分析对配合物的组成进行分析,并通过X射线单晶衍射解析了配合物的晶体结构,表明分子中存在明显的分子间S…S及氢键作用。同时也研究了配合物的紫外、荧光和电化学性质,滴定实验显示两种配合物均是很好的TCNQ电子接受体。