Hydrothermal Synthesis and Crystal Structure of a Coordinated Polymer： [Ni（pda）（H2O）3]n （pda = Pyridine-2,3-dicarboxylate）

1 INTRODUCTIONThe design and synthesis of metal-organic coor- dinated polymer have attracted considerable atten- tion in recent years. The infinite networks construc- ted from transition metal complexes have intere- sting structures as well as potential applications as smart electronic, magnetic porous materials, cataly- sis, host-guest chemistry, and so on[1～4]. In the as- sembly and synthesis of polymer structures, the me- tal ions, bi- or multi-dentate ligand, solvent and the ratio of …     

Crystal structures and magnetic properties of new cyano-bridged two-dimensional grid-like bimetallic assemblies [Ni(tn)2]2[Cr(CN)5((NO)]OH*H2O and [NI(tn)2]2[Co(CN)6]NO3*2H2O (tn=1,3-propanediamine)

Two bimetallic assemblies, [Ni(tn)(2)](2)[Cr(CN)(5)(NO)]OH.H(2)O (1) and [Ni(tn)(2)](2)[Co(CN)(6)]NO(3).2H(2)O (2) (tn = 1,3-diaminopropane), have been prepared and structurally and magnetically characterized. Crystal data for 1 (2): space group P1 (P1), a = 8.698(3) (8.937(2)) A, b = 10.001(2) (9.863(1)) A, c = 10.158(2) (10.064(1)) A, alpha = 87.40(2) (86.064(10)) degrees, beta = 65.10(2) (65.489(10)) degrees, gamma = 81.63(2) (81.572(12)) degrees and Z = 1 (1). Both structures consist of two-dimensional grid-like polycations containing Ni-N triple bond C-M linkages (M = Cr or Co) and counteranions (OH, NO(3)). Magnetic studies of 1 showed that the complex displays a metamagnetic behavior originating from intralayer ferromagnetic and interlayer antiferromagnetic interactions. Long-range antiferromagnetic ordering was observed at T(N) = 3.3 K. Complex 2 exhibits intramolecular ferromagnetic interactions through the diamagnetic N triple bond C-Co-N triple bond C bridges, owing to superexchange involving the empty d(sigma) orbital of the diamagnetic Co(III) ion.     

A new bimetallic intercalated 3-D assembly magnet [{(323)Ni}3{FeIII(CN)6}2]n x 12nH2O (323 = N,N'-bis(3-aminopropyl) ethylenediamine): an unprecedented concomitant presence of meridional and facial arrangment of ferricyanide anion

A novel molecular based magnet of three-dimensional (3-D) cyanide-bridged bimetallic assembly, [{(323)Ni}3{FeIII(CN)6}2]n x 2nH2O where 323 = N,N'-bis(3-aminopropyl) ethylenediamine, was synthesized and structurally characterized. The compound crystallizes in the orthorhombic space group Pbca with a = 15.6560 A, b = 15.2910 A, c = 50.9120 A, and Z = 8. The assembly has two intercalated 3-D networks created by FeIII-CN-NiII-NC-FeIII linkages. The ferricyanide anion adopts both facial and meridional arrangements through the linkage. Interesting magnetic properties including 3-dimensional magnetic ordering were revealed. The assembly displays 3-dimensional magnetic ordering below 5.2 +/- 0.1 K and field-induced magnetic behavior below 5.1 +/- 0.1 K and above 1.15 +/-0.05 kOe.     

Hydro(solvo)thermal Construction of a Copper Coordination Polymer Involving in Situ Ligand Synthesis: Preparation and Structure of [Cu_3(bdcO)_2(H_2O)_2]_n

1 INTRODUCTION Increasing attention has been paid to the coppercoordination polymer frameworks not only due totheir intriguing structure diversity but also theirpotential applications in the areas of molecular ad-sorption, catalysis, electromagnetism and photo-chemistry[1～4]. Incorporation of both organic and in-organic components in these compounds has createda new direction in searching for functional materialswith desired structures and properties. Over the lastdecades, the majority o…     

Syntheses and Crystal Structures of Two Novel 1-D Metal Complexes with Dicyanamide： [Zn（pheen）（dca）2]n and [Cu（quin）2（dca）2]n

1 INTRODUCTION Polymeric transition metal complexes with di-cyanamide have attracted considerable attention because of their interesting coordination and phy-sical properties in recent years[1]. The dicyanamide is a versatile ligand coordinated to metal…     

A new type of single-helix coordination polymer with mixed ligands [M2(phen)2(e,a-cis-1,4-chdc)2(H2O)2]n (M=Co and Ni; phen=1,10-phenanthroline; chdc=cyclohexanedicarboxylate)

A new family of single-stranded helices coordination polymers with mixed ligands, [M2(phen)2(e,a-cis-1,4-chdc)2(H2O)2]n (1, M=Co; 2, M=Ni; chdc=cyclohexanedicarboxylic acid; phen=1,10-phenanthroline), were prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, TG analysis, and single-crystal X-ray diffraction analysis. X-ray crystal structural analyses reveal that 1 and 2 are isomorphic and belong to the monoclinic system. C40H36Co2N4O10, P2(1)/c, a=10.0566(5) A, b=8.8843(5) A, c=20.2912(14) A, beta=100.052(3) degrees, Z=2 for 1; and C40H36Ni2N4O10, P2(1)/c, a=9.8921(6) A, b=9.0151(4) A, c=20.1628(17) A, beta=100.31(2) degrees, Z=2 for 2. In the structures of 1 and 2, the 1,4-chdc ligand possesses only one kind of e,a-cis-conformation although there are both cis- and trans-conformations in the raw material. Two oxygen atoms of one carboxyl in 1,4-chdc ligand and another oxygen atom of contraposition carboxyl link adjacent Co or Ni atoms into an infinite 1-D zigzag chain. The most attractive structural feature of 1 and 2 is that they both exhibit an infinite chiral chainlike structure with 2(1) helices along the b axis. In addition, the right-handed and the left-handed chains are alternate. Meanwhile, the adjacent chains of 1 and 2 are linked via hydrogen bonds into 2-D network structures, which further form 3-D frameworks via pi-pi interactions of 1,10-phen.     

Cyano-bridged homometallic 1-D and bimetallic 2-D assemblies: synthesis,structures, and magnetic properties of [Ni(baepn)(CN)]n(ClO4)n and [Ni(baepn)]2n[Fe(CN)(6)]n(H2O)8n

Cyano-bridged homometallic complex [Ni(baepn)(CN)](n)(ClO(4))(n)(1) and bimetallic complex [Ni(baepn)](2)(n)[Fe(CN)(6)](n)(H(2)O)(8)(n)(2) [baepn = N,N'-bis(2-aminoethyl)-1,3-propanediamine] were synthesized and characterized. 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.560(3) A, b = 10.700(3) A, c = 14.138(9) A, beta = 90.18(6) degrees, and Z = 4; 2 crystallizes in the monoclinic space group P2(1)/c with a = 8.951(2) A, b = 13.672(3) A, c = 14.392(3) A, beta = 98.906(4) degrees, and Z = 4. The complex 1 has one-dimensional structure whose chain vector runs along the b axis with baepn ligands and perchlorate anions alternately arranged up and down in the c direction. The antiferromagnetic nature of 1 was explained in terms of the infinite chain model and Haldane gap, giving g = 2.33, J = -29.4 cm(-1), and the magnitude of Haldane gap E(g) = 5.22 K. The complex 2 that constitutes the first example of 2-D bimetallic assembly of Ni(II) ion and ferrocyanide anion is composed of the neutral layers based on the [Ni(4)Fe(4)] square grid spanning in the bc plane. For 2, the analysis with the Curie-Weiss law in 2-300 K range results in THETA = 0.200 K and the magnetism was explained in terms of the ability of ferrocyanide in the -Ni-NC-Fe-CN-Ni unit to promote ferromagnetic Ni-Ni interaction.     

New members in the Ni(n+1)(QO3)nX2 family: unusual 3D network based on Ni4ClO3 cubane-like clusters in Ni7(TeO3)6Cl2

Three new members in the family of nickel(II) tellurium(IV)/selenium(IV) oxyhalides generally formulated as Ni(n+1)(QO3)nX2 (Q = Te, X = Cl, n = 6, 10; Q = Se, X = Br, n = 4) have been synthesized by solid-state reactions of NiX2, QO2, and NiO (or Ni2O3) at high temperature. The structure of Ni7(TeO3)6Cl2 features a novel 3D network based on Ni4ClO3 cubane-like clusters with Te atoms located at the cavities of the network. Ni4ClO3 clusters are interconnected into a hexagonal layer through additional O...O edges. The neighboring two layers are further interconnected, via sharing of common Ni(II) atoms, into a novel 3D network. The 3D open framework of Ni5(SeO3)4Br2 is built from 2D nickel(II) oxybromide layers bridged by Se and additional Ni atoms. The structure of Ni11(TeO3)10Cl2 features a condensed 3D network based on NiO5Cl, NiO6, and NiO5 polyhedra interconnected via corner and edge sharing, as well as O-Te-O bridges. The results of magnetic property measurements indicate that all three compounds display antiferromagnetic interactions between nickel(II) centers.     

Preparation,Characterization and Crystal Structure Determination of a Nickel Complex [Ni（ftsc）2NOa]NO3 （Hftsc = Furan-2-carbaldehyde Thiosemicarbazone）

A new Ni（II） complex, [Ni（ftsc）2NO3]NO3 （Hftsc = furan-2-carbaldehyde thiosemicarbazone）, has been synthesized and characterized by IR, UV spectra and single-crystal X-ray diffraction analysis. It crystalfizes in a monoclinic system, space group P2 1/n, with a = 10.5203（13）, b = 9.2094（11）, c = 20.829（3）A,β = 91.518（2）°, V= 2 017.3（5）A^3, Z = 4, F（000） = 1064, Dc = 1.716 g/cm^3, and wR = 0.0800. The complex contains a six-coordinated nickel（II） center which is bound to two imine nitrogen atoms and two thiolato sulfur atoms of two ligands as well as two oxygen atoms from a nitrate anion to assume a distorted octahedral coordination geometry. In addition, intermolecular N-H…O and C-H…O hydrogen bonds between adjacent molecules link the molecules together to form a three-dimensional structure.     

Synthesis and Crystal Structure of a One-dimensional Azido-bridged Manganese (II) Compound [Mn(N_3)_2(H_2O)_3·C_6H_(12)N_4]_n

1 INTRODUCTION The azide anion is a good bridging ligand for di- valent metal ions to form discrete, one-dimensional, two-dimensional or three-dimensional complexes. In recent years, these complexes have drawn consider- able attentions for their interesting magnetic charace- ristics which attribute to the efficient magnetic coup- ling ability of the azido bridges[1]. When the azide anion acts as a bridging ligand, two typical modes are adopted: end-to-end (EE, μ1, 3) or end-on (EO, μ1…     

Synthesis, crystal structure, and spectroscopic characterization of trans-bis[(mu-1,3-bis(4-pyridyl)propane)(mu-(3-thiopheneacetate-O))(3-thiopheneacetate-O)]dicopper(II), [[Cu2(O2CCH2C4H3S)4mu-(BPP)2]]n: from a dinuclear paddle-wheel copper(II) unit to a 2-D coordination polymer involving monatomic carboxylate bridges

From the reaction between a dinuclear paddle-wheel carboxylate, namely [Cu2mu-(O2CCH2C4H3S)4] (1), and the flexible ligand 1,3-bis(4-pyridyl)propane (BPP) a neutral 2-D coordination polymer [[Cu2(O2CCH2C4H3S)4mu-(BPP)2]]n (2) was obtained. Compounds 1 and 2 were characterized by means of elemental analysis, thermal analysis (TG/DSC), vibrational spectroscopy, and electron paramagnetic resonance (EPR). The crystal structure of 2 reveals that each Cu(II) is coordinated by two nitrogen atoms from different BPP ligands and two 3-thiopheneacetate groups within a distorted square planar geometry in a trans-[N, N, O, O] arrangement. The BPP ligand adopts a TG conformation bridging two copper centers giving rise to a 1-D sinusoidal polymeric chain along the crystallographic c axis. Adjacent 1-D chains are extended into a 2-D coordination network through pairs of monatomic carboxylate bridges in direction of the b axis. This bridging mode affords centrosymmetric dimeric units Cu2O2, and therefore, the copper ions are involved in a CuN2O2O' chromophore displaying a (4 + 1) square pyramidal coordination in the resultant 2-D polymeric network. The polycrystalline X-band EPR spectrum of 2 at room temperature is characteristic of a triplet state with nonnegligible zero-field splitting in agreement with the crystal structure. Crystal data for 2: monoclinic, space group P2(1)/c, a = 9.4253(10) A, b = 10.9373(10) A, c = 23.6378(10) A, beta = 98.733(4) degrees, Z = 2.     

Magneto-structural correlations in Cu(tn)Cl2 (tn = 1,3-diaminopropane): two-dimensional spatially anisotropic triangular magnet formed by hydrogen bonds

A novel polymeric one-dimensional compound Cu(tn)Cl2 (tn = 1,3-diaminopropane) was prepared and structurally characterized, and its spectral, magnetic, thermodynamic, and thermal properties were studied. The unique structure shows ladderlike chains composed of Cu(II) atoms and chloro bridging ligands [Cu(-mu(3)-Cl-)Cu2] running along the crystallographic c axis. The coordination geometry about copper (4 + 2) approximates that of a strongly elongated octahedron. The equatorial plane of the coordination octahedron is formed by a chelate N-bonded tn ligand and two chloro ligands. One of the chloro ligands is terminal, and the other one, mu3-Cl-, forms two additional longer bonds to the neighboring copper atoms and thus occupies the axial octahedral positions. The electronic ground state of the Cu(II) ion is of d(z)2 symmetry and suggests the activation of intraladder and interladder Cl...H-N hydrogen bonds as exchange paths that form a two-dimensional pattern of a triangular symmetry. The interaction due to the hydrogen bonds seems to play an important role in molecular packing and magnetic coupling. The studies of magneto-structural correlations including electron paramagnetic resonance measurements and thermodynamic and magnetic properties revealed a two-dimensional character of magnetic correlations with the effective intralayer exchange coupling J/k(B) approximately -3 K. No phase transition to the ordered state has been observed down to 60 mK. Cu(tn)Cl2 with the interlayer coupling J' approximately 10(-3)J and moderate intralayer interaction represents an excellent example of a two-dimensional magnetic system.     

THE SYNTHESIS AND STRUCTURE OF THE IMIDAZOLATE-BRIDGED HETEROTRINUCLEAR COMPLEX (en)_2Ni[(Im)Co-(NH_3)_5]_2(CIO_4)_6·5H_2O

<正> (H2NC2H4NH2)2Ni [(C3H3N2) Co (NH3)5]2 (CIO4)6 · 5H2O,NiCo2Cl6O29N18C10H62, Mr = 1288. 00, monoclinic, C2/c, a = 31. 832(4), b = 9. 691 (1), c=15. 425(4)(?),β=90. 71(2)°, Z = 4, V = 4758. 0(?)3, Dc=1. 798g/cm3, μ (MoKa) = 15. 22cm-1, F(000)=2656. The three metal nuclei, one Ni( Ⅱ ) and two Co( Ⅲ ), bridged by two imidazolyl anions (Im = C3H3N2), form an isosceles triangle. The Ni( Ⅱ ) atom is situated on the two-fold axis and coordinated by six nitrogen atoms to form a distorted octahedron with two nitrogen atoms from two Im in cis-positions. The two Co( Ⅲ ) atoms are related by C2 symmetry and each Co( Ⅲ ) is coordinated by six nitrogen atoms to form an octahedral configuration.     

Synthesis and Crystal Structure of [La（BTC）（H2O）6]n

1 INTRODUCTION desired topologies owing to their rich coordination modes[8~12] and we have been exploring the chemi- The assembly of metal-organic infinite frame- stry of coordination polymers constructed by tran- works via coordination of metal ions with multifunc- sition metals and benzoic multicarboxylic acids[13~16]. tional organic ligands is a field of increasing inte- In addition, lanthanide ions have high affinity for rest[1~4]. A rational designed and predictable coor- hard donor a…     

配位聚合物[Mn(2，4，6-TMBA)2(H2O)3]n·2nH2O的水热合成和晶体结构

The title compound, [Mn(2,4,6-TMBA)₂(H₂O)₃]_n·2nH₂O(1), where 2,4,6-TMBA=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of monoclinic, space group C2/c with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 04(17) nm, V=2.494 7(9) nm³, Z=4, M=471.40, D_c=1.255 g·cm^-3, μ=0.571 mm^-1, F(000)=996, R_int=0.029 4, R=0.037 6 and wR=0.094 9. The Mn atoms are octahedrally coordinated by two O atoms of two ligands and four O atoms of water. The carboxyl group coordinates to Mn(Ⅱ) in the mode of monodentate, while the O atoms of water molecules coordinates in bridging mode. The complex shows a one-dimensional chain structure bridged by water molecules. CCDC: 297750.     

配合物[Ni(Pht)(Medpq)(H2O)3]n的水热合成、表征及自然键轨道(NBO)分析

采用水热法合成了一种新型金属配合物[Ni(Pht)(Medpq)(H2O)3]n(1)(Pht=phthalic acid,Medpq=2-methyldipyrido[3,2-f∶2′,3′-h]quinoxaline),并对其进行了元素分析、红外光谱、热重表征、X射线单晶衍射测定和理论计算。在晶体中,Ni(Ⅱ)与来自于Medpq分子上的2个氮原子,邻苯二甲酸上的1个氧原子及来自于3个不同的配位水分子上的3个氧原子配位,形成畸变的八面体构型。整个晶体由Pht-Ni-Medpq单元组成零维结构。应用Guassian03W程序,在HF/LANL2DZ水平上对标题化合物的自然键轨道(NBO)进行了分析,结果表明Ni(Ⅱ)与配位原子间的价键类型都属于共价键范畴。     

Cyclic polyvanadates incorporating template transition metal cationic species: synthesis and structures of hexavanadate [PdV6O18]4-, octavanadate [Cu2V8O24]4-, and decavanadate [Ni4V10O30(OH)2(H2O)6]4-

Three types of heteropolyvanadates, [(C2H5)4N]4[PdV6O18] (1), [(C2H5)4N]4[Cu2V8O24] (2), and [(C6H5)4P]4[Ni4V10O30(OH)2(H2O)6] (3), were synthesized through the reaction between the [VO3]- anion and metal template cations of Pd(II), Cu(II), and Ni(II). The X-ray crystal structures of 1 (a = 29.952(4) A, b = 12.911(2) A, and c = 13.678(2) A, orthorhombic, space group Pca2(1) with Z = 4), 2 (a = 13.740(1) A, b = 22.488(2) A, c = 18.505(2) A, and beta= 94.058(2) degrees , monoclinic, space group P2(1)/n with Z = 4), and 3 (a = 12.333(2) A, b = 16.208(4) A, c = 16.516(3) A, alpha = 112.438(3) degrees , beta = 94.735(3) degrees , and gamma = 104.749(3) degrees , triclinic, space group P with Z = 1) demonstrate that the metal cationic species induced cyclic [VO3](n-)n (n = 6, 8, 10) ring formation and the cations are incorporated in the rings themselves. In the metal inclusion products, the cyclic vanadates act as macrocyclic ligands, in which the metal cationic species act as the templates. The cyclic vanadate is composed of tetrahedral VO4 units that share corners and incorporates a metal cationic species in the center of the molecules. The bowl-shaped complex 1 includes a Pd2+ cation that is coordinated by the oxygen donors of a boatlike hexavanadate ring. The diamagnetic complex 1 was characterized via 51V and 17O NMR spectroscopy. Complex 2 involves an octavanadate ring and two Cu2+, which are located on both sides of the mean plane as defined by the eight oxygen atoms that bridge the vanadium atoms. In the case of complex 3, the di-mu-hydroxo-bridged Ni2+ dimer with capped Ni2+ aqua ions is formed by hydrolysis to form the decavanadate ring, in which two of the tetrahedral vanadate units are not bonded to the Ni2+ core but supported by hydrogen bonds through the aqua-ligand in the capped Ni2+ cation. Complexes 1-3 in solution were clearly identified by their characteristic isotope patterns using ESI-MS studies.     

Preparation,Characterization and Crystal Structure Determination of a Nickel Complex [Ni(ftsc)_2NO_3]NO_3(Hftsc=Furan-2-carbaldehyde Thiosemicarbazone)

A new Ni(II) complex, [Ni(ftsc)2NO3]NO3 (Hftsc=furan-2-carbaldehyde thiosemicarba-zone), has been synthesized and characterized by IR, UV spectra and single-crystal X-ray diffraction analysis. It crystallizes in a monoclinic system, space group P21/n, with a=10.5203(13), b=9.2094(11), c=20.829(3), β=91.518(2)°, V=2 017.3(5)3, Z=4, F(000)=1064, Dc=1.716 g/cm3, and wR= 0.0800. The complex contains a six-coordinated nickel(II) center which is bound to two imine nitrogen atoms and two thiolato sulfur atoms of two ligands as well as two oxygen atoms from a nitrate anion to assume a distorted octahedral coordination geometry. In addition, intermolecular N-H···O and C-H···O hydrogen bonds between adjacent molecules link the molecules together to form a three-dimensional structure.     

SYNTHESIS AND STRUCTURE OF (Ph_4P)_2[Ni_3(μ-SC_3H_6S)_4]·2CH_3CN

<正> (Ph4P)2[Ni3(u-SC3H6S)4].2CH3CN was obtained from the reaction of NiCl2.6H2O,Na2(1,2-pdt)(pdtH2=CH3CH(SH)CH2SH) and Ph4PBr.Mr=1361. 80, P21/c,a=10.802(2),b=30.111 (7),c=9. 907(3) A ,B=93. 60(3) ;V= 3216. 0 A3;Z=2,Dc=1. 41g/cm3. The three Ni atoms of the anion are linearly arranged and bridged by four sulfur atoms from the four 1 ,2-propyldithiolato ligands.     

Synthesis and Characterization of a One-dimensional Chain Polymer {[Cu(4-CPOA)(3-PyOH)2(H2O)2](H2O}n

A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]·H2O}n (4-CPOA2- = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The complex C19H22N2O10Cu crystallizes in triclinic system, space group P-1with a = 7.672(2), b = 18.490(4), c = 13.271(3) (A), α = 72.81(3), β ＝ 84.64(3), γ = 87.28(3)°, V = 1026.3(4) (A)3, Z = 2, Mr = 501.94, Dc = 1.624 g/cm3, μ = 1.126 mm-1, F(000) = 518, the final R = 0.0580 and wR = 0.1310 for 3364 observed reflections with I > 2σ(I). Each Cu(II) ion is coordinated with two different carboxyl O atoms from two 4-carboxyphenoxyacetate groups, two N atoms from two 3-PyOH ligands and two water molecules, residing in a distorted octahedral environment. Adjacent Cu(II) atoms are linked by bi-monodentate 4-CPOA2- groups into an one-dimensional chain along the b axis. A three-dimensional supramolecular network is constructed by O-H…O hydrogen bonds.