配位聚合物{[Cd(pda)(4,4'-bipy)(H2O)]·H2O}n的合成、晶体结构与荧光性质

在水热条件下利用间苯二乙酸,4,4'-二联吡啶和硝酸镉反应生成配位聚合物{[Cd(pda)(4,4'-bipy)(H2O)]·H2O｝n(1)(1,3-H2pda=间苯二乙酸、4,4'-bipy=4,4'-二联吡啶).其晶体结构采用红外光谱、热重分析及单晶X射线衍射等手段进行了表征.结构分析表明该配位聚合物属三斜晶系,空间群为Pī;晶体学参数:a=0.7991(4)nm,b=1.1514(5) nm,c=1.2075(5) nm;α=107.352(6)°,β=97.505(6)°,γ=108.925(6)°,V=970.8(8) nm3.其基本结构单元由两个Cd(Ⅱ)离子、两个间苯二乙酸根、四个4,4'-二联吡啶、两个水分子组成.有趣的是所有的闭合环[Cd2(pda)2]通过两线状4,4 '-二联吡啶支撑连接形成一维管状配位聚合物.同时对该配位聚合物的荧光性质进行研究,发现在366 nm处呈现较强的荧光发射(λex=300 nm).     

二2-(2'-吡啶基)苯并咪唑一水合锌(Ⅱ)配合物的合成和结构表征

采用水热法合成了新配合物二2-(2'-吡啶基)苯并咪唑一水合锌(Ⅱ)配位聚合物{[Zn(L)2·H2O]}n(1),[L=2-(2'-吡啶基)苯并咪唑],用元素分析、红外光谱和X射线单晶结构等进行了表征,结果表明该配位聚合物属于单斜晶系,P21/c空间群.晶胞参数为:a=1.25188(19) nm,b =1.30095(19) nm,c=1.3300(2) nm,β =102.676(3)°,F(000) =968,Dc=1.483 g · cm-3,V=2.1133(5) nm3,Mr=471.81,Z=4,μ=1.192 mm-1,R1=0.0539,wR2=0.0819.该配位聚合物晶体是由配位水与苯并咪唑上的氮原子形成氢键以及配体2-(2'-吡啶基)苯并咪唑之间的π-π堆积作用连接而成的无限延伸的一维链状结构.     

锰(Ⅱ)与5-[(蒽-9-亚甲基)-氨基]-间苯二甲酸的超分子配位聚合物的合成、表征及性能研究

以桥联配体5-[(蒽-9-亚甲基)-氨基]-间苯二甲酸和Mn(CH3COO)2·4H2O 为原料,通过溶剂热法成功合成了一个新型三维超分子结构的配位聚合物{[Mn2(H2O)4(CH3OH)(C2H5OH)(L)2]·(CH3OH)2·H2O}n(H2L=5-[(蒽-9-亚甲基)-氨基]-间苯二甲酸),并通过红外光谱、元素分析、X射线粉末衍射、单晶 X 射线衍射和热重分析,对配位聚合物的单晶结构进行了表征.该配位聚合物属于三斜晶系,空间群P-1,晶胞参数:a=9.6850(19) nm,b=14.278(3) nm,c=17.666(4) nm,α=87.15(3)°,β=89.99(3)°,γ=83.96(3)°,V=2426.3(8) nm3,Z=2.该晶体结构为一维配位链,通过链与链之间的π…π相互作用和氢键形成了三维超分子结构.此外,在室温条件下,固态荧光测试表明配体及其配位聚合物分别在456 nm (λex=417 nm)和506 nm (λex=402 nm)具有较强的荧光.     

三维配位聚合物[Co(pda)(SCN)(H2O)]n [pda=3-(3-吡啶基)丙烯酸]的合成和晶体结构

以CoCl2、3-(3-吡啶基)丙烯酸(pda)和KSCN为原料,在水热反应条件下,合成了一种三维配位聚合物[Co(pda)(SCN)(H2O)]n晶体,对其进行了元素分析、红外光谱表征、X射线单晶衍射测定和热重分析.该配位聚合物属三斜晶系,P-1空间群,晶胞参数为a=0.7309(5)nm,b=0.8799(6)nm,c=0.9634(6)nm,α=68.128(10)°,β=73.241(11)°,γ=71.218(12)°,V=0.5343(6)nm3,Z=2,dc=1.760g/cm3,μ=1.792mm-1,F(000)＝268,R1=0.0450, wR2= 0.1035.X射线单晶衍射显示形成一个三维的网络结构.     

新型三维配位聚合物[La(C5H4NCOO)3(H2O)2]n的水热合成和晶体结构

在水热反应条件下,设计合成了一种新型三维配位聚合物[La(C5H4NCOO)3(H2O)2]n的单晶体,对其进行了元素分析、热重分析、红外光谱表征、X射线单晶衍射测定.该配位聚合物属单斜晶系,P2(1)/c空间群,晶胞参数为a=0.9747(4)nm,b=1.9904(7)nm,c=1.1613(4)nm,α=90°,β=111.761(6)°,γ=90°,V=2.0925(13)nm3,Z=4,dc=1.718g/cm3,μ=2.090mm-1,F(000)＝1064,R1=0.0374, wR2=0.0683.X射线衍射结果显示La3+离子之间以4-氰基吡啶的羧基为桥形成一维链状结构,通过4-氰基吡啶的吡啶基与配位的水分子之间的氢键形成三维的网络结构.热重分析表明该配位聚合物在230℃下稳定.     

2D配位聚合物{[Eu(pdc)(ox)0.5(H2O)4]·2H2O}n的结构和荧光性质

用氯化铕和2,4-吡啶二甲酸在水热条件下反应合成了一个二维铕稀土配位聚合物{[Eu (pdc) (ox)05(H2O)4]·2H2O}n(1)(H2pdc=2,4-吡啶二甲酸;ox=草酸根阴离子),草酸根离子由部分2,4-吡啶二甲酸分解产生.X-射线单晶衍射分析表明,该配位聚合物属单斜晶系,P121/c1 (No.14)空间群,晶胞参数为a=1.53047(15) nm,b=1.10973(9) nm,c =0.85494(15) nm,β=102.81(1)°,α=y =90°.Eu3+为九配位,除了与一个pdc阴离子配体和一个ox阴离子配体螫合配位外,还与四个水分子配位.pdc阴离子通过2-位羧基以μ2-桥联方式连接两个Eu3+,吡啶环上的氮原子与其中一个Eu3+配位,4-位羧基没有参与配位.草酸根阴离子以螯合方式连接两个Eu3+.配体pdc和ox与Eu3+通过配位键连接形成了少见的2D之字形平面,该配合物在紫外光的激发下显示鲜艳的红色荧光,表明该配位聚合物具有良好的荧光性质,热重分析表明该配位聚合物具有较好的热稳定性.     

之字链配合物Cu(phth)2(H2O)2的合成、表征及晶体结构

用Cu(NO3)2·3H2O和phth(邻苯二甲酸)混合反应得到了配合物Cu(phth)2(H2O)2(1).通过元素分析、红外光谱对配合物进行了表征,用X射线单晶衍射仪测定了配合物的晶体结构.配合物为单斜晶系,P2(1)/c空间群.晶胞参数a=0.83895(17)nm,b=1.4441(3)nm,c=0.70992(14)nm,β=112.14(3)°,V=0.7967(3)nm3,Z=2,Dc=1.792 g/cm3,F(000)=438.0,S=1.100,R1=0.0376,wR2=0.0998.铜原子为四配位,呈畸变正方形构型,通过邻苯二甲酸根的π-π堆积作用形成了一维之字型链,相邻的链之间靠氢键和π-π堆积作用形成三维分子结构.     

新型配位聚合物[Ni(C6H4NO2)2(H2O)4]n的水热合成和晶体结构

以NiCl2·6H2O和4-氰基吡啶为原料,在中温水热反应条件下,合成了一种新型配位聚合物[Ni(C6H4NO2)2(H2O)4]n单晶体,并对其进行了元素分析、红外光谱表征和X射线单晶衍射测定.该配位聚合物属三斜晶系,P-1空间群,a=0.6298(4)nm,b=0.6907(4)nm,c=0.9243(5)nm,α=96.437(8)°,β=105.184(9)°,γ=113.314(9)°,V=0.3456(3)nm3,Z=2,dc=1.802 g/cm3,μ=1.452mm-1,F(000)=194,R1=0.0309,R2=0.0753.该晶体通过配位键的连接和分子间氢键相互作用形成三维的网状结构.     

二维锰(Ⅱ)配位聚合物[Mn2(bppc)4(H2O)]n·2nH2O的合成、晶体结构及热稳定性研究

以2,6-双(2-吡嗪基)吡啶-4-对苯甲酸和MnCl2为原料,在水热条件下合成了二维锰(Ⅱ)配位聚合物[Mn2(bppc)4(H2O)]n·2nH2O,并用元素分析、红外光谱、X射线单晶衍射对此配位聚合物进行了表征,测定结果表明,晶体属于单斜晶系,P2(1)/c空间群,晶胞参数为:a=10.3918(9) nm, b=24.519(2) nm ,c=7.0140(6) nm,α=90°,β=105.0890(10)°,γ=90°.此配位聚合物中MnII之间通过配体中吡嗪环上的氮和羧基氧的桥连形成一维链状结构,一维链再通过羧基基团上的氧的进一步桥连形成二维结构.另外,热重分析表明,此配位聚合物具有较好的热力学稳定性.     

一维镉(Ⅱ)配合物[Cd(H2ASA)2(H2O)2]n的合成、晶体结构及光致变色性质

以5-偶氮四唑水杨酸(H3ASA)和CdCl2·2.5H2O为原料,通过常规溶液法合成了一个镉配合物[Cd(H2ASA)2(H2O)2]n(1).通过X-射线单晶衍射、X-射线粉末衍射、元素分析、红外光谱、热重分析、紫外光谱进行结构解析和性质表征.结果 表明配合物1属于三斜晶系,Pi空间群,晶胞参数为a =0.702 39(5) nm,b=0.735 15(6) nm,c=1.229 41(7)nm,α =82.557(5)°,β=75.453(6)°,γ =61.882(8)°,V=0.541 90(8) nm3,Z=1,μ=1.083 mm-1,Dc=1.884g/cm3.配合物1中具有H2ASA-,作为μ2-桥联配体连接两个不同的Cd(Ⅱ)离子形成无限一维链结构,相邻直链通过O…O、O…N氢键和π-π堆积作用形成三维超分子框架.紫外光谱测试表明配合物1在365 nm紫外光照射下具有光致异构性质.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.     

Synthesis and crystal structure of di(2-aminopyrimidinium) trichlorodimethyl(2-aminopyrimidine)stannate(IV) chloride (H-2APY)2[SnMe2Cl3(2APY)]Cl

The synthesis and molecular structure of di(2-aminopyrimidinium) trichlorodimethyl(2-aminopyrimidine)stannate(IV) chloride (H-2APY)₂[SnMe₂Cl₃(2APY)]Cl is reported. The compound crystallized in the orthorhombic space group Pnma with a = 20.524(1) Å, b = 10.822(1) Å, c = 10.472(1) Å and V = 2325.9(3) ų, Z = 4. The structure consists of three fragments: the hexacoordinated organotin anionic complex [SnMe₂Cl₃(2APY)]⁻, which exhibits distorted octahedral geometry; two protonated 2-aminopyrimidinium cations (H-2APY)⁺, and one chloride anion.

     

Molecular structures of (tBu)Ga(S2CNnPr2)2 and (iPrO)Ga(S2CNEt2)2: An example of an unusual ligand pseudorotation

The molecular structures of (^tBu)Ga(S₂CNⁿPr₂)₂ (1) and (ⁱPrO)Ga(S₂CNEt₂)₂ (2) have been determined. The variation in the geometries observed for bis-dithiocarbamate compounds of gallium, (X)Ga(S₂CNMe₂)₂ (X=Cl, ⁱPrO, ^tBu) do not lie along the Berry pseudorotation pathway for the square-based pyramid to trigonal bipyramid geometrical transition. Instead, the structures appear to lie on an unusual ligand two-step, Texas, pseudorotation mechanism which results in a highly distorted trigonal bipyramidal geometry. Crystal data: (1) monoclinic, P2₁,/c, a = 9.786(1), b = 29.218(3), c = 9.452(1) Å, = 108.379(9)°, V = 2564.7(5) ų, and Z = 4. (2) Monoclinic, P2₁ /c, a = 10.980(3), b = 15.673(4), c = 12.461(3) Å, = 97.47(2)°, V = 2126.2(9) ų and Z = 4.     

A Unique Example of a Co-crystal of [Co(AMTTO)2(H2O)2](NO3)2 and [Co(AMTTO)2(CH3CN)2](NO3)2 (AMTTO = 4-amino-5-methyl-1,2,4-triazol-3(2H)-thione)

A co-crystal of cobalt(II) complexes, Co(AMTTO)₂(CH₃CN)₂]²⁺(NO₃)₂. [Co(AMTTO)₂(H₂O)₂]²⁺(NO₃)₂, compound (1) was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P2₁/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R₁?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)₂(CH₃CN)₂]²⁺ and [Co(AMTTO)₂(H₂O)₂]²⁺ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.

Graphic Abstract

A co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.

     

Crystal structures of mixed compounds Cu(2)Gly(D-Ser)(L-Ser)2 and Cu(2)Gly 3(L-Ser)

-The crystal structures of mixed coordination compounds, Cu(2)Gly(D-Ser)(L-Ser)₂(I) and Cu(2)Gly ₃(L-Ser)(II), which contain the amino acid residues of glycine (Gly) and serine (Ser) in the 1: 3 and 3: 1 ratio, respectively, are studied by electron diffraction. Crystals I and II are triclinic, Z = 1, and space group P1. For I, a = 8.96(2) Å, b = 9.66(2) Å, c = 5.07(2) Å, α = β = 90°, and γ = 92.8(3)°. For II, a = 8.37(2) Å, b = 9.65(2) Å, c = 5.06(2) Å, α = β = 90°, and γ = 92.8(3)°. Compounds I and II have layered structures that are based on the CuGly(L-Ser) fragment. Structures I and II differ mainly in their interlayer spacing and configuration of the interlayer space.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

Crystal and molecular structures of 1-(2-carboxypropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (1) (C17H21NO4) and 1-(2-carbamoyl propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C17H22N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol containing 2-methylalanine fragment are described in this paper. The space groups and unit-cell parameters are: compound1 (C₁₇H₂₁NO₄): monoclinic, space groupP2₁/n,a=5.787(1),b=18.703(4),c=23.526(5)Å,=96.49(2)°; compound2 (C₁₇H₂₂N₂O₃): triclinic, space groupP¯1,a=8.321(1),b=10.121(1),c=10.368(1)Å,=109.49(1)°,=90.49(1)°, =103.48(1)°. The structures were solved by direct methods and refined with full matrix least-squares techniques toR indices of 0.055 and 0.049, respectively. The molecules of compound1 exist in the crystal as dual ions. The molecules of compound2 are compact and their external chain is twisted in a characteristic way (similar to that found in peptides).     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).     

(TMTSF)2(2,5-Tcnqbr2): Structure and Physical Properties

The 2:1 charge-transfer salt (TMTSF)₂(2,5-TCNQBr2) has been prepared and its physical properties investigated. Its crystal structure consists of segregated stacks of TMTSF donors (ring-over-bond overlap pattern; mean interplanar spacing of 3.6A) and chains of edge-on and disordered 2,5-TCNQBr2 acceptors. Infrared data are suggestive of unit charge on the 2,5-TCNQBr2 molecule and, therefore, half charge on the TMTSF donor. Resistivity data are successfully interpreted on the basis of a percolation construction. Magnetic data are also presented.