Synthesis and Crystal Structure of a Novel Manganese Coordination Polymer Constructed by 3,5-Dimethylbenzoic Acid with 4,4'-Bipyridine

A novel manganese coordination polymer [Mn（L）2（bipy）]n （HL = 3,5-dimethylbenzoic acid, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized by a hydrothermal method. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group C2/c with a = 2.0996（8）, b = 1,1835（5）, c = 0.9958（4） nm, β = 110.161（5）°, V = 2,3229（16） nm^3, Z = 4, C28H26MnN2O4, Mr = 509.45, Dc= 1.457 g/cm^3,μ = 0.607 mm^-1, F（000） = 1060, Rim = 0.0566, R = 0.0334 and wR = 0.1078. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 4,4＇-bipy and four oxygen atoms from 3,5-dimethylbenzolate molecules, completing an octahedral geometry. The 4,4＇-bipy molecules bridge the infinite chain [Mn（L）2（bipy）]n to form a two-dimensional layer.

Syntheses,Crystal Structures,and Magnetic Properties of Two Manganese(Ⅱ) Coordination Polymers Based on Bifunctional Pyridine-benzene Carboxylic Acids

Two manganese（II） coordination polymers, namely, {[Mn（PIP）（BIBP）]·（BIBP）0.5}n（1） and {[Mn（PTA）（BIMBP）（H2O）]·H2O（0.69）}n（2）（H2PIP = 5-（4-pyridyl）-isophthalic acid, H2 PTA =6-（4-pyridyl）-terephthalic acid, BIBP = 4,4？-bis（imidazol-1-yl）biphenyl, and BIMBP =4,4？-bis（imidazol-1-ylmethyl）biphenyl）, have been synthesized by using the bifunctional pyrinde-benzene carboxylic acids and bis（imidazole） linkers as mixed ligands to react with Mn SO4,and further characterized by elemental analysis, IR, and PXRD. Compound 1 is in the triclicnic system, space group P1 with a = 10.1089（8）, b = 13.1927（12）, c = 14.0638（12）A, α = 69.437（2）, β= 73.2890（10）, γ = 78.5320（10）o, V = 1671.9（2） A^3, Z = 2, Dc = 1.449 g/cm^3, F（000） = 705,μ（MoK α） = 0.453 mm^-1, S = 1.053, R = 0.0491 and wR = 0.1367 for 5837 unique reflections（Rint =0.0208） with I 〉 2σ（I）. Compound 2 belongs to the monoclicnic system, space group C2/c with a =15.199（3）, b = 19.731（3）, c = 21.537（5） ？, β = 105.228（3）o, V = 6232（2） A^3, Z = 8, Dc = 1.363g/cm^3, F（000） = 2648, μ（MoK α） = 0.475 mm^-1, S = 1.048, R = 0.0489 and wR = 0.1151 for 7414 unique reflections（Rint = 0.0425） with I 〉 2σ（I）. Structural analyses reveal that complex 1 is a4-connected（44.62）-sql bilayer structure with binuclear [Mn2（COO）2] SBU, while complex 2 is a normally（3,5）-connected（42.67.8）（42.6）-3,5L2 monolayer. And the sheets interacted with the adjacent sheets through weak interactions, finally giving a stable three-dimensional（3D）supramolecule. Besides, the variable-temperature magnetic susceptibility measurement of complex1 was investigated.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(NAA)_2(4,4’-bipy)(H_2O)_4]_n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain-like coordination polymer [Mn（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized from 2,4,6-trimethylbenzoic acid, 1,10-phenanthroline and anhydrous manganese（Ⅱ ） sulfate and then characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.05643（16）, b = 2.05643（16）, c = 1.3939（2） nm, V = 5.8946（11） nm^3, Mr = 579.54, Z = 8, Dc = 1.306 g/cm^3, μ（MoKα） = 0.490 mm^-1, F（000） = 2424, S = 0.985, the final R = 0.0411 and wR = 0.0950. The Flack factor is -0.01（2）. The crystal structure shows that two neighboring man- ganese（Ⅱ ） ions are linked together by one bridge-chelating 2,4,6-trimethylbenzoic group, forming a one-dimensional chain structure. The manganese（Ⅱ ） ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline, three oxygen atoms from three 2,4,6-trimethylbenzoic acids and one water oxygen atom, giving a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex was also investigated.

Preparation, Crystal Structure and Thermal Behaviour of a One-dimensional Coordination Polymer [Mn(m-CPOAH)_2(H_2O)_2]_n

The coordination polymer of [Mn(m-CPOAH)2(H2O)2]n (m-CPOAH– = 3-carboxyl- phenoxyacetate) has been synthesized and characterized by elemental analyses, IR, TG and single- crystal X-ray diffraction. The title complex crystallizes in the triclinic system, space group P1 with a = 4.7013(9), b = 5.6822(11), c = 17.758(4) ?, α = 87.39(3), β = 85.39(3), γ = 85.76(3)o, V = 471.18(17) ?3, Z = 1, Mr = 481.26, Dc = 1.696 g/cm3, μ = 0.770 mm-1, F(000) = 247, R = 0.0385 and wR = 0.1015. The Mn(II) atom assumes a distorted octahedral geometry, involving four carboxyl oxygen atoms from different m-CPOAH– ligands and two coordinated water molecules. The Mn(II) atoms are linked by the m-CPOAH– ligand to form a one-dimensional chain structure along the a axis. The shortest Mn…Mn separation within the polymer is 7.401(4) ?. A three- dimensional supramolecular network is constructed by O–H…O hydrogen bonding interactions.