Jian-Hua Qin

MnII Coordination Polymers Based on Bi-, Tri-, and Tetranuclear and Polymeric Chain Building Units: Crystal Structures and Magnetic Properties

Five new Mn(II) coordination polymers, namely [Mn(2)(tbip)(2)(bix)] (1), [Mn(3)(tbip)(3)(bix)(2)] (2), [Mn(3)(tbip)(2)(Htbip)(2)(bib)(2)]·4H(2)O (3), [Mn(4)(tbip)(4)(bbp)(2)(H(2)O)(2)] (4), and [Mn(4)(tbip)(4)(bip)]·2H(2)O (5), were prepared by hydrothermal reactions of Mn(II) acetate with H(2)tbip (5-tert-butyl isophthalic acid) in the presence of different di-imidazolyl coligands (bix =1,4-bis(imidazol-1-ylmethyl)benzene, bib =1,4-bis(imidazol) butane, bbp =1,3-bis(benzimidazol)propane, bip =1,3-bis(imidazol)propane). All complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal X-ray crystallography, and powder X-ray diffraction. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric, trimeric, and tetrameric motifs to polymeric chains depending upon the coligands used. Complex 1 has a 3D 6-connected polycatenane network with dinuclear [Mn(2)O(2)] secondary building units. Complex 2 possesses a 3D 8-connected structure with trinuclear [Mn(3)(COO)(6)] units. Complex 3 shows a 3D pcu net based on trinuclear [Mn(3)(COO)(6)] clusters as nodes. Complex 4 features a 3D 8-connected structure constructed from the distorted square-grid tetranuclear [Mn(4)(μ(2)-COO)(8)(μ(2)-H(2)O)] units. Complex 5 shows a 3D (4,5,6)-connected net containing 1D μ-O/μ-COO alternately bridged chains. Magnetic susceptibility measurements indicate that complexes 1 and 3-5 show weak antiferromagnetic interactions between the adjacent Mn(II) ions, whereas 2 is a three-spin center homometallic ferromagnetic system.

Syntheses, structures and photoluminescence of five zinc(II) coordination polymers based on 5-methoxyisophthalate and flexible N-donor ancillary ligands

A series of zinc(II) coordination polymers with 5-methoxyisophthalate (CH3O–H2ip) and five related flexible N-donor ancillary ligands, [Zn(CH3O-ip)(bime)0.5] (1), [Zn(CH3O-ip)(btx)]2·H2O (2), [Zn(CH3O-ip)(bix)]2 (3), Zn(CH3O-ip)(bib) (4), [Zn2(CH3O-ip)2(bbim)]2 (5) [bime = 1,2-bis(imidazol-1′-yl)ethane, btx = 1,4-bis(triazol-1-ylmethyl)benzene), bix = 1,4-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(2-methyl-imidazol-1-yl)butane, bbim = 1,1′-(1,4-butanediyl)bis(benzimidazole)], have been synthesized under hydrothermal conditions. Complexes 1–5 were structurally characterized by elemental analysis, infrared spectra and X-ray single-crystal diffraction. These complexes display different types of entanglements. Complex 1 features an extended 3D polythreaded network based on 2D coordination frameworks with a (3,4)-connected (42.6)(42.63.8) topology. Complex 2 shows a rare example of entangled coordination polymer containing both interpenetrating and polythreading features. Complex 3 manifests a highly corrugated 2D (4,4) layer. The layers are penetrated by each other to give rise to 3D polycatenations. While 4 and 5 exhibit three-fold interpenetrated 3D 4-connected (65.8) and (3,4)-connected (42.6)(42.6.102.12) topologies, respectively. These results suggest that both 5-methoxyisophthalate and N-donor ancillary ligands influence on the final resulting structures. Furthermore, luminescent properties and thermogravimetric properties of these complexes were investigated.

Exploring the structural diversities and magnetic properties of copper(II) and manganese(II) complexes based on 5-methoxyisophthalate and flexible bis(imidazole) ligands

Six copper(II) and manganese(II) coordination polymers with 5-methoxyisophthalate (CH3O-ip) and three related flexible N-donor ancillary ligands, {[Cu3(CH3O-ip)2(bie)(OH)2]}n (1), {[Cu2(CH3O-ip)2(bib)2]·H2O}n (2), {[Cu(CH3O-ip)(bbb)(H2O)]·H2O}n (3), {[Mn3(CH3O-ip)4(H2O)2]·(H2-bie)·4H2O}n (4), {[Mn(CH3O-ip)(bib)]}n (5) and {[Mn(CH3O-ip)(bbb)]}n (6) [bie = 1,2-bis(imidazol-1′-yl)ethane; bib = 1,4-bis(imidazol-1-ylmethyl)benzene; bbb = 1,1′-(1,4-butanediyl)bis(benzimidazole)], have been synthesized under hydrothermal conditions. Complexes 1–6 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 exhibits a three-dimensional (3D) framework with a (3,4)-connected (5·8·9)(5·112)(5·83·112) topology. Complex 2 shows a two-dimensional (2D) layered structure with a (3,5)-connected (42·6)(42·67·8) topology and further stacks via hydrogen-bonding interactions to give a 3D supramolecular architecture. Complex 3 possesses a 1D chain and further stacks into a 2D supramolecular architecture via hydrogen-bonding interactions. Complex 4 is a 2D layered structure with a (4,4) topology and further stacks via hydrogen-bonding interactions to generate a 3D supramolecular architecture. Similar to 2, complex 5 displays a 2D layered structure with a (3,5)-connected (42·6)(42·67·8) topology. Complex 6 features a 3D structure with a (3,5)-connected (4·6·8)(4·64·85) topology. Thermogravimetric properties and magnetic properties of 1–6 were also investigated.

Two unique (4,5,6)-connected 2D CdII coordination polymers based on the 5-nitro-1,2,3-benzenetricarboxylate ligand

Two new 2D coordination polymers, [Cd3(nbta)2(H2O)4] (1) and [Cd3(nbta)2(bbi)2H2O)2] (2) (H3nbta = 5-nitro-1,2,3-benzenetricarboxylate, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) have been synthesized and structurally characterized by single X-ray structure analysis. The versatile conformations and binding modes of the nbta ligand as well as the coordination environment of the CdII atoms result in two unique (4,5,6)-connected 2D CdII-coordination polymers, both of which show enthralling helical structures.

catena-Poly[[[bis-[2,2'-(propane-1,3-diyl-dithio)bis-(1,3,4-thia-diazole)-κN]copper(II)]-bis-[μ-2,2'-(propane-1,3-diyldithio)bis-(1,3,4-thia-diazole)-κN:N]] bis-(perchlorate)].

In the title compound, {[Cu(C7H8N4S4)4](ClO4)2}n, the CuII atom, occupying a crystallographic inversion centre, is six-coordinated by six N atoms of three symmetry-related 2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole) (L) ligands in a slightly distorted octahedral geometry. The ligand L adopts two kinds of coordination modes in the crystal structure; one is a monodentate coordination mode and serves to complete the octahedral coordination of the Cu atom and the other is an N:N′-bidentate bridging mode in a trans configuration, bridging Cu atoms via translation symmetry along the b axis into a chain structure. The perchlorate ions serve as acceptors for intermolecular C—H⋯O hydrogen bonds, which link the chains into a three-dimensional network.

Synthesis and Crystal Structure of a Porous Framework Obtained by In Situ Ligand Formation From 4,4′-Dipyridyldisulfide

A new complex, [Ni2(H2O)(5-Br-ip)2(dps)2]n (1) (5-Br-H2ip = 5-bromoisophthalate, dps = 4,4′-dipyridylsulfide) has been hydrothermally synthesized by in situ generation of 4,4′-dipyridylsulfide ligand from a 4,4′-dipyridyldisulfide (dpds) precursor and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray analysis. Complex 1 belongs to the orthorhombic system, Fdd2 space group, a = 28.789(16) Å, b = 13.903(8) Å, c = 27.693(15) Å, F (000) = 3984, R1 = 0.0799, wR2 = 0.1957. Complex 1 contains [Ni2(H2O)]4+ dimers bridged by pairs of ligands into a single 3D diamond network with alternately left-handed and right-handed helical channels. Moreover, the thermal stabilities of 1 were also discussed. Supplemental materials are available for this article. Go to the publishers online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.

Synthesis, Structure, and Magnetic Property of a New Co(II) Complex Based on 5-Methylisophthalic Acid and 1,6-Bis(triazol)hexane

A new complex, {[Co2(mip)2(bth)2](H2O)0.5}n (1), [H2mip = 5-methylisophthalic acid; bth = 1,6-bis(triazol)hexane], has been synthesized by hydrothermal reaction of Co(II) salt, H2mip and bth ligands. The X-ray single-crystal structure shows that the complex belongs to the triclinic system, P-1 space group, a = 10.0919(16) Å, b = 14.222(2) Å, c = 15.322(2) Å, and α = 101.276(2)º, β = 102.717(2)º, γ = 94.896(2)º. The dinuclear Co(II) units are bridged by mip2− to form a 1D double polymeric chain, which is further connected by bth to generate a 3D network. Moreover, the IR spectroscopy, elemental analysis and magnetic property of 1 were also characterized.

Two Mn(II)/Co(II) Coordination Polymers Involving 4,4′-dipyridyltrisulfide/4,4′-dipyridylsulfide Obtained by In Situ Ligand Formation From 4,4′-dipyridyldisulfide

Two coordination polymers, [Mn(dpts)(5-Br-ip)]n (1) and [Co2(dps)2(5-Br-Hip)4]n (2) (dpts = 4,4′-dipyridyltrisulfide, dps = 4,4′-dipyridylsulfide, 5-Br-H2ip = 5-Bromoisophthalate), have been hydrothermally synthesized by in situ generation of dps and dpts ligands from a 4,4′-dipyridyldisulfide (dpds) precursor in the presence of Mn(II) and Co(II) ions, respectively. Complex 1 belongs to the triclinic system, P–1 space group, a = 8.925(4) Å, b = 10.236(5) Å, c = 12.184(6) Å, α = 69.539°, β = 84.699°, γ = 77.991°. Complex 2 belongs to the hexagonal system, P6522 space group, a = 16.6696(12) Å, b = 16.6696(12) Å, c = 36.999(5) Å, γ = 120°. Complex 1 presents a one-dimensional structure based on binuclear Mn(II) clusters. However, complex 2 displays a two-dimensional network containing the double helical chains.

Crystal structure of ethanolatopenta{2,2′-[1,2-propanedithiobis( 1,3,4-thiadiazole)]}dicopper(II) tetrakisperchlorate, [Cu2(C2H5OH)(C7H8N4S4)5][ClO4]4

C37H46Cl4Cu2N20O17S20, triclinic, P1 (no. 2), a = 10.7533(9) Å, b = 17.752(1) Å, c = 20.349(2) Å, + = 96.841(1)°, * = 101.606(1)°, ( = 103.362(1)°, V = 3645.8 Å, Z = 2, Rgt(F) = 0.063, wRref(F) = 0.180, T = 291 K. Source of material The reaction of 1,2-[propanebis(thio)]bis[1,3,4-thiadiazole] (0.25 mmol) with Cu(ClO4)2 (0.1 mmol) in MeOH (10 mL) for a few minutes afforded a light blue solid, which was filtered, washed with acetone, and dried in air. The single crystals suitable for X-ray diffraction analysis were obtained by slow diffusion of Et2O into the acetonitrile solution of the solid. Experimental details The high residual values are due to the poor quality of the crystal. PLATON treatment was performed and none solvent molecule was suggested. Discussion In recent years, the rational design of coordination polymers based on multi-dentate or flexible bridging ligands as linkers and metal centers as connectors represents one of the most rapidly deZ. Kristallogr. NCS 225 (2010) 339-342 / DOI 10.1524/ncrs.2010.0148 339

Bis(1,3,4-thia­diazol-2-yl) disulfide

The title compound, C4H2N4S4, lies about a twofold rotation axis situated at the mid-point of the central S—S bond. Each of two thiadiazole rings is essentially planar, with an rms deviation for the unique thiadiazole ring plane of 0.0019 (7) Å. C—H⋯N hydrogen bonds link adjacent molecules, forming zigzag chains along the c axis. In addition, these chains are connected by intermolecular S⋯S interactions [S⋯S = 3.5153 (11) Å] , forming corrugated sheets, and further fabricate a three-dimensional supramolecular structure by intermolecular N⋯S contacts [S⋯N = 3.1941 (17) Å].