[Co(dmg)2Cl2]3·[Co(dmg)2Cl(OH)]·[Co(dmg)(phen)]·(H2O)4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

晶态配合物荧光材料[Ni(3,5-(SO3)2 CatH2)(phen)2(H2O)]·4H2O的合成、结构及性质

利用缓慢蒸发溶剂法合成了单核镍(Ⅱ)配合物[Ni(3,5-(So3)2CatH2)(phen)2(H2O)]·4H2O(CatH2=1,2-二羟基苯,phen=1,10-邻菲罗啉).利用X-射线单晶衍射、元素分析、红外光谱、热重分析和荧光光谱等对其进行了表征.结果表明,该配合物属于三斜晶系,P1空间群.镍离子与一个1,2-二羟基苯-3,5-二磺酸根离子、两个1, 1O-邻菲罗啉配体和一个水分子配位,形成[Ni(3,5-(SO3)2CatH2)(phen)2(H2 O)]结构.在结构单元中,还有四个未配位的水分子.未配位的水分子和[Ni(3,5-(SO3)2CatH2)(phen)2(H2 O)]结构通过O-H…O氢键相连,形成三维网状结构.与配体相比,配合物的荧光发射谱发生红移,发射峰在645 nm.荧光寿命为1.07 ns.     

基于四核混合价态[Co2ⅡCo2Ⅲ(SO4)6]2-分子簇构为筑的三维网络结构

在水热条件下,利用H2biim(H2biim=2,2'-联咪唑)与金属离子Co“组装,得到一个结构新颖的混合价态CoⅡ/Ⅲ四核簇状配合物[Co4(H2biim)4(Hbiim)2(SO4)3]·3H2O (1),并对其进行元素分析、红外光谱、热重分析、拓扑分析、X-射线单晶衍射等测定.标题配合物属单斜晶系P21/c空间群,晶胞参数:a=1.23477 (6) nm,b=2.19524(13) nm,c =2.22162(9) nm,β=121.735(2)°,Z=4,V=5.1216 (4) nm3,Dc =1.779 g·cm-3,μ=1.486mm-1.X-射线单晶衍射分析表明四核簇状配合物1中H2biim配体分别以中性的H2biim配体和负一价的Hbiim-配体与钴离子配位,SO42-分别以单齿、三齿和四齿与钴离子配位,构成四核[Co4(SO4)6]2-簇,四核Co簇再进一步以[Co(H2biim) (Hbiim)2]+结构单元链接形成具有一维通道的三维孔洞结构.     

钴（II）三元配合物[Co（pht）2（MeOH）2（H2O）2]的合成与晶体结构

利用溶剂热法合成了一个新的钴（II）配合物[Co（pht）2（MeOH）2（H2O）2]（Hpht：苯妥英,即5,5-二苯基-2,2眯唑烷酮）,通过元素分析、红外光谱、热重差热分析、X射线单晶衍射等技术对其结构进行了表征。单晶结构分析表明,该晶体属单斜晶系,P21／C空间群,晶胞参数：a=1．2124（2）nm,b=1．09996（19）nm,c=1．1574（2）nm,β=92．555（2）°,V=1．5419（5）nm^3,Dc=1．425mg／m^3,Z=2,F（000）=690,μ=0．615mm^-1,R1=0．0467,wR2=0．1116[I〉2σ（I）],GOF=1．026。Co（II）离子位于八面体的中心,与六个配位原子配位（4O＋2N）。     

配位聚合物{[Co3(TCOPM)2(H2O)2]·17H2O}n的合成和结构

采用三(对-苯甲酸)甲烷(H3TCOPM)为配体,以Co为中心离子采用自组装的方法合成了配位聚合物{[Co3(TCOPM)2(H2O)2]·17H2O}n,利用单晶衍射仪,红外光谱,TG和元素分析对其进行了晶体结构的解析和表征.它属于单斜晶系,C2/c空间群,晶胞参数分别为a=2.9675(13) nm,b =1.3548(5) nm,c=1.8659 (5) nm,α=90.00°,β=124.61(2)°,γ=90.00°,V=6.174(4) nm3,Mr=959.47,Z=4,Dc=1.187 g/cm3,μ =0.860 mm-1,F(000)=2268.0.结果表明,配位聚合物中H3TCOPM的三个羧酸全部和Co配位,形成三维结构,展现了一个具有tfd连接拓扑网络结构,其孔隙率为47.6;.     

配合物[Co(SCN)2(HSCN)2(dabco)2]的合成、晶体结构与表征

以SCN-和三乙撑二胺(dabco)为配体,以钴为中心离子采用自组装的方法合成了配合物[Co(SCN)2(HSCN)2(dabco)2],采用单晶X射线衍射、红外光谱、热重分析和元素分析等方法对其进行了晶体结构的解析和表征.它属于单斜晶系,P21/n空间群,晶胞参数分别为a＝0.71964(11)nm,b＝1.12716(17)nm,c＝1.4454(2)nm,β＝96.629(2)°,V＝1.1646(3)nm3,Dc＝1.470 g/cm3,Z＝2,F(000)＝534,μ＝1.115mm-1.热重分析表明,该配合物在530 K以下稳定.     

二聚体配合物[Mn(1,6-nds)(phen)_2(H_2O)]_2·(CH_3OH)_3·(H_2O)_2的合成、晶体结构及荧光性质

采用水热法合成了二聚体Mn(Ⅱ)配合物[Mn(1,6-nds)(phen)2(H2O)]2·(CH3OH)3·(H2O)2,(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。采用X射线单晶衍射、红外光谱、热重分析和紫外可见光谱等方法对配合物进行了表征。X射线单晶衍射表征结果表明,该配合物晶体属于三斜晶系,空间群为P-1。锰离子与两个1,10-邻菲罗啉分子、一个水分子和1,6-萘二磺酸根离子配位,形成[Mn(1,6-nds)(phen)2(H2O)]结构单元。这种结构单元、未配位的甲醇和水分子通过两种类型的氢键O-H…O和O-H…S相连,形成三维网状结构。与配体相比,配合物的荧光光谱发生红移,其最大发射峰在439 nm。     

钴(Ⅱ)三元配合物[Co(pht)2(MeOH)2(H2O)2]的合成与晶体结构

利用溶剂热法合成了一个新的钴(Ⅱ)配合物[Co(pht)2(MeOH)2(H2O)2](Hpht:苯妥英,即5,5-二苯基-2,2咪唑烷酮),通过元素分析、红外光谱、热重差热分析、X射线单晶衍射等技术对其结构进行了表征.单晶结构分析表明,该晶体属单斜晶系,P21/C空间群,晶胞参数:a=1.2124(2)nm,b=1.09996(19)nm,c=1.1574(2)nm,β=92.555(2)°,V=1.5419(5)nm3,Dc=1.425 mg/m3,Z=2,F(000)=690,μ=0.615 nm-1,R1=0.0467,wR2=0.1116[I>2σ(I)],GOF=1.026.Co(Ⅱ)离子位于八面体的中心,与六个配位原子配位(40+2N).     

双核钆混配配合物[Gd(Ts-p-aba)3(phen)]2·2DMF·4.4H2O的合成与晶体结构

采用溶剂热合成法合成了双核钆混配配合物[Gd(Ts-p-aba)3(phen)]2·2DMF·4.4H2O(Ts-p-aba-=N-对甲苯磺酰对氨基苯甲酸根离子,phen=1,10-邻菲罗啉,DMF=N,N-二甲基甲酰胺),并利用红外光谱(FT-IR)、热重分析(TG-DSC)和X-射线单晶衍射等实验手段研究了配合物的组成、结构和性质.X-射线单晶衍射结果表明:该配合物晶体属三斜晶系,P1空间群,晶胞参数是:a=1.10505(12) nm,b=1.74570(18) nm,c=1.78163(19) nm,α=70.321(2)°,β=85.357(2)°,γ=82.600(2)°,V=3.2066(6) nm3,Mr=2633.99,Dc=1.364 g/cm3,Z=1,μ=1.197mm-.6个氧原子和2个氮原子在钆离子周围形成一个变形的反四方棱柱体配位环境.配合物存在着丰富的氢键,将配合物连接成二维层状超分子结构.     

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.     

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 structure of trans-[Co(NH3)4(NH2CH3)Cl](ClO4)2

The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I>2(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH₃)₄(NH₂CH₃)Cl](ClO₄)₂ molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Synthesis and crystal structure of [CrCl3(dmpe)]2(μ-dmpe)·2(CH2Cl2): A diphosphine ligand bridging two isolated Cr(III) centers

Reaction of dmpe (bis(1,2-dimethylphosphino)ethane) with CrCl₃(THF)₃ gives deep red crystalline Cr₂(dmpe)₃(Cl)₆·2CH₂Cl₂ in 85% yield. The X-ray crystal structure of the title compound shows a bridgingtrans dmpe ligand between two isolated Cr(III) centers. Each Cr(III) atom bears a chelating dmpe group and three Cl atoms in a roughly octahedral geometry. Crystal data: C₂₀H₄₈Cl₁₀Cr₂P₆,M=933.0, monoclinic,P2₁/n,a=9.221(3),b=10.587(2),c=21.868(2) Å,=98.962(3)°,D _calc=1.47 g cm^–3,Z=2. FinalR=0.054,R _w =0.063 from 1964 observed reflections (I>3(I)), 3489 measured.     

Synthesis and crystal structures of nitratocobaltates Na2[Co(NO3)4], K2[Co(NO3)4], and Ag[Co(NO3)3] and potassium nitratonickelate K2[Ni(NO3)4]

The cobalt(II) and nickel(II) nitrate complexes with an island structure (Na₂[Co(NO₃)₄] (I) and K₂[Co(NO₃)₄] (II)] and a chain structure [Ag[Co(NO₃)₃] (III) and K₂[Ni(NO₃)₄] (IV)] are synthesized and investigated using X-ray diffraction. In the anionic complex [Co(NO₃)₄]^2? of the crystal structure of compound I, the Co coordination polyhedron is a twisted tetragonal prism formed by the O atoms of four asymmetric bidentate nitrate groups. In the anion [Co(NO₃)₄]^2? of the crystal structure of compound II, one of the four NO₃ groups is monodentate and the other NO₃ groups are bidentate (the coordination number of the cobalt atom is equal to seven, and the cobalt coordination polyhedron is a monocapped trigonal prism). The crystal structures of compounds III and IV contain infinite chains of the compositions [Co(NO₃)₂(NO₃)_2/2]^? and [Ni(NO₃)₃(NO₃)_2/2]^2?, respectively. In the crystal structure of compound III, seven oxygen atoms of one monodentate and three bidentate nitrate groups form a dodecahedron with an unoccupied vertex of the A type around the Co atom. In the crystal structure of compound IV, the octahedral polyhedron of the Ni atom is formed by five nitrate groups, one of which is terminal bidentate. The data on the structure of Co(II) coordination polyhedra in the known nitratocobaltates are generalized.