三维网状冠醚配合物（Bu4N){[K(18-C-6)][Cd4(dmit)2(dmt)3]}的合成与结构

研究了18-冠-6（18-C-6）与KSCN，CdCl2.2.5H2O,(Bu4N2)[Zn(dmit)2] (dmit=4,5-dimercapto-1,3-dithiole-2-thione,C3S5^2-)的反应，生成的标题配 合物（1）通过元素分析，红外光谱，单晶X射线衍射进行了表征，配合物属单斜晶 系，空间群C2/c，晶体学数据：a=3.4780(7)nm,b=1.5170(3)nm,c=2.8440(6)nm,β =105.93(3)°,V=14.427(3)nm^3,Z=8,F(000)=7872,R1=0.0425,wR2=0.0739,配合物 由一个Bu4N^+阳离子和一个{[K(18-C-6)][Cd4(dmit)2(dmt)3]}-(dmt=4,5- dimercapto-1,2-dithiole-3-thione,C3S5^2-)配阴离子组成，{[K(18-C-6)[Cd4 (dmit)2(dmt)3]}-通过K…S，S…S弱相互作用形成三维网状结构。     

一维链状冠醚配合物[K(B18-C-6)]_2[M(SCN)_4](M=Pd,Pt)的合成与结构

合成了苯并18-冠-6（B18-C-6）与K_2[Pd(SCN)_4]生成的配合物[K（B18-C-6 ）]_(12) [Pd(SCN)_4] (1), [K(B18-C-6)]_2[Pt(SCN)_4] (2)和[K(B18-C-6)]_2 [Pt(SCN)_4]·C_2H_4Cl_2 (3),并通过元素分析、红外光谱、单晶X射线衍射进行 了表征。1和2为单斜晶系,空间群P2_l/n,晶体学数据：1, a = 1.00970(17) nm, b = 1.3157(2) nm, c = 1.7303(3) nm, β = 94.841(2)°, V = 2.2852(7) nm~3, Z = 2, F(000) = 1136, R_1 = 0.0257。3为三斜晶系,空间群P1,晶体学 数据：a = 0.95914(18) nm, b = 1.2137(2) nm, c = 2313(2) nm, α = 63.693 (2)°, β = 76.293(2)°, γ-1.2406(4) n~3, Z = 1 F(000)618,R_1 = 0.0366 。在固态,三个配合物相邻的两个[K（B18-C-6）]~+基团通过冠醚氧化原子与钾的 子的相边接而形成一维链状结构。     

一维链状冠醚配合物[k(18-C-6)]~2[M(NO~2)~4](H~2O)(M=Pd,Pt) 的合成与结构

研究了18-C-6分别与k~2[Pd(NO~2~4],k~2[Pt(NO~2)~4])的反应,并通过元素分析、红外光谱、单晶X射线衍射对生成的配合物[k(18-C-6)]~2[Pd(NO~2)~4](H~2O)~0.5(1)和[k(18-C-6)]~2,k~2[Pt(NO~2)~4])(H~2O)(2)进行了表征,两个配合匀匀为单斜晶系,空间P2~1/c.1的晶体学数据：α=1,7104(3),c=1,5763(3)nm,β=93.49(3)°,V=3.9987(14)nm^3,Z=4,D~c=1.507g/cm^3,F(000)=1880,R~1=0.0681,~wR~2=0.1004。2的晶体学数据：a=1.1312(3)nm,b=1.4227(2)nm,c=1.2266(3)nm,β93.141(10)°,V=1.9711(8)nm^3,Z=4,D~c=1.614g/cm^3,F(000)=936,R~1=0.0265,~wR~2=0.0721。在固态,配合物1具有[(18-c-6)]~2[Pd(NO~2)~4](H~2O)(1a)和[(18---c-6)]~2[Pd·(NO~2)~4](1b)两个分子,两者比例这1：1前者相邻的两个分子通过水分是的氧原子相连接形成一维链状结构,后者形面假一维链状结构,在配合物2中相邻的两个分子通过品分子中的氧原子相连接形成一维链状结构。     

二维网状冠醚配合物－苯并15－冠－5、二苯并18－冠－6与Na_2[Pt(SCN)_6]配合物的合成与结构

合成了苯并15-冠-5、二苯并18-冠-6与Na_2[Pt(SCN)_6]的配合物：[Na(B15- C-5)]_2[Pt(SCN)_6] (1),[Na(DB18-C-6)]_2[Pt(SCN)_6] (2),并通过元素分析 、红外光谱、单晶X射线衍射进行了表征。1为单斜晶系,空间群P2_1/c,a = 1. 0974(5) nm,b = 1.5187(7) nm,c = 1.3632(6) nm,β = 96.407(7)°,V = 2. 2568(18) nm~3,Z = 2,D_(calcd) = 1.746 g/cm~3,F(000) = 1184,R_1 = 0. 0357,wR_2 = 0.0868。 2为三斜晶系,空间群 P1-bar,a = 1.2500(3) nm,b = 1.2825(3) nm,c = 1.9342(4) nm,α = 106.82(3)°,β = 102.51(3)°,γ = 103.04(3)°,V = 2.7562 nm~3,Z = 2,D_(calcd) = 1.579 g/cm~3,F(000) = 1316,R_1 = 0.0364,wR_2 = 0.0771。配合物分别由两个[Na(B15-C-5)]~+, [Na(DB18-C-6)]~+配阳离子和一个[Pt(SCN)_6]~(2-)配阴离子组成。配阳离子和配 阴离子通过Na-N键形成二维网状结构。     

对“一维链状冠醚配合物[K(B18-C-6)]2[M(SCN)4](M=Pd,Pt)的合成与结构”一文的更正

我们合成、表征了苯并18-冠-6（B18-C-6）与K_2[Pd-(SCN)_4]，K_2[Pt(SCN) _4]生成的一维链状配合物[K(B18-C-6)]_2[Pd(SCN)_4](1)，[K(B18-C-6)]_2[Pt (SCN)_4](2)和[K(B18-C-6)]_2[Pt(SCN)_4]·C_2H_4Cl_2(3)。其中3为三斜晶系， 空间群P1[化学学报2002，60（8），1465]。厦门大学胡盛志教授认为该化合物的 空间群应为P-1。经将原始数据重新还原、修正，3的空间群的确为P-1，现予以更 正。     

一维链状氰根桥联配合物 [Sm(DMA)~2(H~2O)~4Fe(CN)~6·5H~2O]~n的合成和晶 体结构

以K~3Fe(CN)~6,N,N-二甲基乙酰胺和Sm(NO~3)~3·6H~2O合成了标题配合物[Sm(DMA)~2(H~2O)~4Fe(CN)~6·5H~2O]~n,并通过元素分析,红外光谱进行了表征。利用单晶X射线四圆衍射法测定了晶体结构,结果表明晶体属斜晶系,P2~1/c空间群,晶胞参数a=1.02744(4)nm,b=1.6732(2)nm,c=1.7323(2)nm,β=97.385(3)°,Z=4,R~1=0.0412。     

金属多硫1,2-二硫烯配合物C[Ni(dmid)~2]的研究

首次制得通式为C[Ni(dmid)~2]系列新配位化合物(C为外部阳离子,H~2dmid=4,5-二硫醇-1,3-二硫-2-酮)。当这些配合物用化学法氧化时,得到同一种配合物[Ni(dmid)~2],并确定了这些新配合物的组成,研究了它们的IR,UV,ESR,XPS谱和循环伏安图,测定了室温导电率。XPS谱的研究结果说明,用化学法氧化时电子转移过程主要发生在配体上,配位体的电荷分布发生了变化。     

18-冠-6与Na2[M(mnt)2](M=Cu,Ni)配合物的合成与结构

研究了18-冠-6分别与Na2[M(mnt)2][M=Cu,Ni;mnt=丁二腈烯二硫醇阴离子,C2S2(CN)^2^-~2]的反应,得到的配合物{[Na(18-C-6)][Na(18-C-6)(H2O)]}[Cu(mnt)2](1),[Na(18-C-6)(H2O)]2[Ni(mnt)2].(18-C-6)(2)通过元素分析、红外光谱、X射线单晶衍射进行了表征。两个配合物均为三斜晶系,空间群P1。1的晶体学结构数据：a=1.22697(19)nm,b=1.22780(19)nm,c=1.5665(3)nm,α=95.083(3)°,β=101.534(3)°,Υ=91.007(3)°,V=2.3016(6)nm^3,Z=2,Dcalcd=1.350g/cm^3,F(000)=976,R1=0.0726,wR2=0.1843.2的晶体学结构数据：a=1.11620(17)nm,b=1.22054(18)nm,c=1.27939(18)nm,α=111.647(2)°,β=29.792(3)°,Υ=103.201(2)°,V=2.5461(4)nm^3,Z=1,Dcalcd=1.304g/cm^3,F(000)=642,R1=0.0459,wR2=0.1003.1中的[Cu(mnt)2]^2^-通过mnt的氮原子与[Na(18-C-6)]^+中的钠原子成键,形成了一维链状结构;[Na(18-C-6)(H2O)]^+只起平衡电荷的作用。2中的[Ni(mnt)2]^2^-也通过配体的mnt氮原子与两个[Na(18-C-6)(H2O)]^+中的钠原子成键,形成稳定的中性配合物。     

含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫甲酸)合镍负离子加合物的合成、表征和[Ni(hmtade)][Ni(cdc)2]的晶体结构

合成了七个含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫代甲酸)合镍负离子的加合物[ML][Ni(cdc)2](cdc=N-氰基亚胺基二硫代甲酸根; L=hmtade,hmta, dmtade, tmtate; M=Cu, Ni, Zn), 通过元素分析、红外光谱、电子光谱、磁化率和顺磁共振谱对加合物结构进行了表征。测定了[Ni(hmtade)][Ni(cdc)2]的晶体结构, 其晶体属单斜晶系, C2/c空间群, 晶胞参数: a=1.1883(2), b=1.1753(2),c=2.0482(4)nm, α=90°, β=100.19(1)°, γ=90°,V=2.8154nm^3, Mr=630.19, Dx=1.482g/cm^3, Z=4, 对正负离子间的相互作用进行了讨论。     

混合配合物[Cu~0~.~5Mn~0~.~5(phen)~2Cl]OH.3H~2O的合成与晶 体结构

报道了混合配合物[Cu~0~.~5Mn~0~.~5(phen)~2Cl]OH.3H~2O的合成、表征和晶体结构分析。该晶体属单斜晶系,具有C2/c空间群,a=2.3321(5),b=3.0295(6),c=0.7492(1)nm,β=97.85(3)ⅲ,V=5.244(3)nm^3,Z=8,Dc=1.516g/cm^3,F(000)=1244,R=0.066,Rw=0.068。该化合物含[Cu(phen)~2Cl]^+和[Mn(phen)~2Cl]^+阳离子,它们以金属离子各50%的几率在晶胞中无序排列。晶胞中分两层排布8个这样的阳离子单元;水分子和OH^-离子分布其中。     

Two-dimensional Network Crown Ether Complex. Synthesis and Crystal Structure of 18-Crown-6 Complex: [K(18-C-6)]_2[Cd-(mnt)_2]

ＩｎｔｒｏｄｕｃｔｉｏｎＲｅｃｅｎｔｙｅａｒｓ ,ｃｏｏｒｄｉｎａｔｉｏｎｐｏｌｙｍｅｒｓｈａｖｅｂｅｅｎｒｅ ｃｅｉｖｅｄｍｕｃｈａｔｔｅｎｔｉｏｎｂｅｃａｕｓｅｏｆｔｈｅｉｒｉｎｔｅｒｅｓｔｉｎｇｐｈｙｓｉ ｃａｌｐｒｏｐｅｒｔｉｅｓｓｕｃｈａｓｅｌｅｃｔｒｉｃａｌｃｏｎｄｕｃｔｉｖｉｔｙ ,ｍａｇ ｎｅｔｉｓｍ ,ｎｏｎｌｉｎｅａｒｏｐｔｉｃａｌｐｒｏｐｅｒｔｉｅｓａｎｄｐｏｔｅｎｔｉａｌａｐｐｌｉ ｃａｔｉｏｎｓｉｎｓｅｐａｒａｔｉｏｎａｎｄｃａｔａｌｙｓｔ.1Ｔｈｅｍｏｄｕｌａｒａｐ ｐｒｏａｃｈ…     

苯并18-冠-6与M_2[Pt(SCN)_6](M=Na,K)配合物的合成、结构

合成了苯并 18 冠 6(B18C6)与M2 [Pt(SCN)6 ](M =Na,K)的配合物:｛[Na(B18C6)]6 [Pt(SCN)6 ]｝[Pt(SCN)6 ](SCN)2(1),[K(B18C6)]2 [Pt(SCN)6 ]·4H2 O(2).通过元素分析、红外光谱、单晶X射线衍射进行了表征.1为单斜晶系、空间群R3- ,a =b =1 9933(3)nm,c =2 9760 (6)nm,α =β =90°,γ =12 0°,V =10 2 40 (3)nm3,Z =3,Dcalcd=1 5 64g/cm3,F(0 0 0) =490 8,R1=0 0 5 35,wR2 =0 10 30.2为三斜晶系、空间群P1- ,a =1 1692 (3)nm,b =1 185 3(4)nm,c =1 2 381(5)nm,α =61 419(5)°,β =80 75 7(8)°,γ =89 0 0 3(5)°,V =1 4836(9)nm3,Z =1,Dcalcd=1 476g/cm3,F(0 0 0) =666,R1=0 0 696,wR2 =0 134 6. 1由 ｛[Na(B18C6)]6 [Pt(SCN)6 ]｝4 +配阳离子、[Pt(SCN)6 ]2 -配阴离子和SCN-阴离子组成.相邻｛[Na(B18C6)]6 [Pt(SCN)6 ]｝4 +通过Na—O键形成三维网状结构.[Pt(SCN)6 ]2 -和SCN-仅起平衡电荷的作用.2由两个[K(B18C6)]+配阳离子和一个[Pt(SCN)6 ]2 -配阴离子组成.相邻[K(B18C6)]2 [Pt(SCN)6 ]离子对通过K—O键形成一维链状结构     

苯并15-冠-5与Na_2[M(SCN)_4](M=Pd,Pt)配合物的合成与结构

合成了苯并15-冠-5与Na_2[M(SCN)_4] (M = Pd, Pt)生成的配合物：[Na(B15- C-5)]_2[Pd(SCN)_4] (1), {[Na(B15-C-5)][Na(B15-C-5)(H_2O)]}[Pt(SCN)_4] (2)。1为单斜晶系，空间群P2_1/n，a = 1.0164(6) nm，b = 1.3743(3) nm，c = 1.4987(7) nm，β = 95.248(6)°，V = 2.0847 nm~3，Z = 2，D_(calcd) = 1. 47 g/cm~3，F(000) = 944，R = 0.053，wR = 0.072。2为三斜晶系，空间群P(1- bar)，a = 1.1484(2) nm，b = 1.4210(3) nm，c = 1.5026(3) nm，α = 62.500 (3)°，β = 72.393(3)°，γ = 73.106(4)°，V = 2.0398(7) nm~3，Z = 2， D_(calcd) = 1.674 g/cm~3，F(000) = 1028，R_1 = 0.0327，wR_2 = 0.0885。1 由两个[Na(B15-C-5)]~+配阳离子和一个[Pd(SCN)_4]~(2-)配阴离子组成，两者通 过Na-N键形成中性配合物，[Na(B15-C-5)]~+A相对钯原子呈反式排列。2由[Na (B15-C-5)]~+和[Na(B15-C-5)(H_2O)]~+配阳离子和一个[Pt(SCN)_4]~(2-)配阴离 子组成，它们也通过Na-N键形成中性配合物，配阳离子相对铂原子呈顺式排列。2 的两个分子通过氢键形成二聚结构。     

Synthesis and Crystal Structure of a Sandwiched Trinuclear Complex [Tl_2(18-Crown-6)_2Pt(CN)_4]·2H_2O

1 INTRODUCTION Tetracyanoplatinate ion often forms one-dimen- sional chain compounds, and the Pt–Pt spacings are often only 0.01~0.3 ? longer than those in Pt metal (2.78 ?). The studies of room-temperature electrical conductivities of these complexes indicate that the shorter the Pt–Pt separations in the chains are, the higher the electrical conductivity is[1~3]. Tetracyano- platinate ion may also stack with suitable planar cations into one-dimensional materials such as [Pt- (CNR)4]…     

Two Polymorphs of (Anilinium)(18-Crown-6)[Ni(dmit)2]: Structure and Magnetic Properties

Two polymorphs of monovalent [Ni(dmit)₂]⁻ (dmit²⁻=2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)₂], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)₂]⁻ molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)₂], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ=190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)₂]⁻ dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)₂]⁻ arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K.     

The Novel Benzo-15-Crown-5 with Palladium(II) Complex: [Na(B15CS)]_2,[Pd(SCN)_4]

The extensive pioneering study of Pedersen I has led to a vialal explosion of solutionand solid-state investigation of crown ethers and metal ions which include alkali metal,alkali earth metal, other main-group and transition-metal ions. It is shown that singlecrystal X-ray diffraction analysis is a most powerful technique for the characterization ofthese complexes and numerous solid-state structUral stIJdies have appeared through theyears. The reported B15CS complexes strllcturally charact…     

Synthesis and Characterization of One-dimensional Dicyclohexyl-18-crown-6 Complexes with M2[Cd(mnt)2] (M = Na, K)

Two supramolecular crown ether complexes [Na(DC18C6-A)(H₂O)]{[Na(DC18C6-A)][Cd(mnt)₂]} (1) and [K(DC18C6-A)]₂[Cd(mnt)₂] (2) (DC18C6-A = cis-syn-cis-dicyclohexyl-18-crown-6, isomer A; mnt = maleonitriledithiolate) have been synthesized and characterized by elemental analysis, FT-IR spectroscopy and X-ray single crystal diffraction. Complex 1 is composed of one [Na(DC18C6-A)(H₂O)]⁺ complex cation and one {[Na(DC18C6-A)][Cd(mnt)₂]}⁻ complex anion and displays an infinite chain-like structure through N–Na–N interactions. In complex 2, [K(DC18C6-A)]⁺ complex cation and [Cd(mnt)₂]²⁻ complex anion afford a novel 1D ladder-like structure by N–K–N, N–K–S interactions.     

The Novel Benzo-15-Crown-5 with Palladium(II) Complex:[Na(B15C5)]2[Pd(SCN)4]

A novel Pd(II) Benzo-15-crown-5 complex [Na(B15C5)]2[Pd(SCN)4] has been isolated and characterized by IR and X-ray diffraction analysis.The crystal structure belongs to monoclinic,space group P21/n with cell dimensions,a=1.0164(6),b=1.3743(3),c=1.4987(7) nm,b=95.248(6)o ,V=2.0847nm3,Z=2,F(000)=944,R=0.053,Rw=0.072.The compound consists of two [Na(B15C5)]+ complex cations and a [Pd(SCN)4]2- complex anion.Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)4]2- to form stable neutral complex.