Shi-Yao Yang

Substituent effect on the assembly of coordination polymers containing isophthalic acid and its derivatives

Four coordination polymers [Zn4(H2O)(ip)4(py)6]n1, {[Zn2(hip)2(py)4]2·(py)}n2, [Zn(tbip)(py)2]n3 and [Mn(tbip)(py)2]n4 (H2ip = isophthalic acid, H2hip = 5-hydroxyisophthalic acid, H2tbip = 5-tert-butylisophthalic acid, py = pyridine), have been hydrothermally synthesized and characterized. The photoluminescent properties of 1–3 have also been investigated. For 1–3, as substituents change from H, OH to tert-butyl, the coordination numbers of Zn2+ ions decrease, and the dimensionalities of the structures of 1–3 decrease from 2D (4,4) net, 1D double stranded chain to 1D chain. For 3 and 4, as Mn2+ tends to have a higher coordination number as compared to Zn2+, the structure of 4 is a 2D (4,4) net while the structure of 3 is a 1D chain. The substituents on isophthalic acid influence the coordination environments of metal ions and the coordination modes of the carboxyls, and thus determine the structures of the coordination polymers. The coordination behavior of metal ions also affects the formation of the structures.

Control of the topologies and packing modes of three 2D coordination polymers through variation of the solvent ratio of a binary solvent mixture

By tuning the ratio of solvents in a binary solvent mixture, the coordination geometries of the metal centers were controlled and three 2D coordination polymers, [Zn(bdc)(dma)]n1, [Zn3(bdc)3(dma)2]n2 and {[Zn(bdc)(H2O)]·(DMA)}n3, were synthesized from zinc(II) nitrate and H2bdc in water/DMA solvents (H2bdc = benzene-1,4-dicarboxylic acid, DMA = N,N-dimethylacetamide). As the ratio of water/DMA increases, the number of DMA ancillary ligands coordinated to the zinc ion decreases, until all the DMA are substituted by water. The change in the ratio of solvents (which also act as ancillary ligands) affords a means to adjust the local coordination environment of the zinc ion, leading to three types of SBUs, which further determine the topologies and the packing modes of the coordination polymers.

Effect of ionic radius on the assemblies of first row transition metal–5-tert-butylisophthalates–(2,2′-bipyridine or phenanthroline) coordination compounds

18 coordination compounds of Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+, with mixed organic ligands 5-tert-butylisophthalic acid, 2,2′-bipyridine or phenanthroline, have been hydrothermally synthesized and characterized. Structure analysis shows that the ionic radius of a metal ion determines the form of the metal centre and the structure of the product. Large metal ions tend to have higher coordination numbers, connect to more bridging ligands and form multinuclear metal centres. On the contrary, small metal ions tend to connect to fewer bridging ligands, and act as mononuclear metal centres for discrete coordination compounds or low dimensional coordination polymers. The influences of other factors such as molar ratio of reactants, pH and temperature, have also been discussed. The magnetic properties of the temperature dependent cobalt compounds have been investigated.

Synthesis, crystal structure and properties of a one-dimensional polymeric copper(II) complex of tetrachlorophthalate

The coordination polymer [Cu2L2(H2O)6 · 2(H2O)]n (L = μ-tetrachlorophthalate dianion) has been synthesized and characterized by X-ray crystallography, i.r. spectroscopy, electronic spectroscopy and cyclic voltammetry. The structure of the complex is a one-dimensional zigzag chain. The i.r. spectra reveal that the tetrachlorophthalate groups are bismonodentate ligands, and this is confirmed by the crystal structure determination. Cyclic voltammetry reveals two steps of a quasi-reversible oxidation–reduction processes for the complex.

catena-Poly­[[[tetra­aqua­cobalt(II)]-μ-pyrazine] phthalate]

The Co atom, the pyrazine heterocycle and the phthalate dianion are in special positions in the crystal structure of the title compound, [Co(C4H4N2)(H2O)4](C8H4O4); the Co atom and the N-heterocycle are located on sites of mmm symmetry, whereas the dianion is disordered over a 2mm site. The four water ligands constitute a square plane surrounding the Co atom, and the other two coordination sites are occupied by the N atoms of two different N-heterocycles. The cationic entity propagates as a linear μ-pyrazine-bridged chain that runs along the a axis of the orthorhombic unit cell. The dianion interacts with the Co atom through hydrogen bonds.

CRYSTAL STRUCTURE OF A 3D COORDINATION POLYMER: SODIUM ZINC TEREPHTHALATE HYDRATE Ν,Ν-DIMETHYLFORMAMIDE SOLVATE

Figure 1. ORTEP plot of a portion of the title complex (50% probability ellipsoids, hydrogen atoms have been omitted for clarity). Selected bond distances and angles: Znl-02 1.932(2), Znl-03a 1.953(3), Znl-06 1.955(2), Znl-Olw 1.991(3), Znl-04a 2.756(3), Nal-05 2.310(3), Nal-Olb 2.371(3), Nal-04c 2.373(3), Nal-07 2.427(3), Nal-Ol 2.472(3), Nal-Olw 2.505(3), Ol-Nalb 2.371(3) A, 02-Znl-03a 99.09(11), 02Znl-06 109.48(12), 03a-Znl-06 119.09(12), 02-Znl-01w 108.89(11), O3a-Znl-Olw 113.09(12), 06Znl-Olw 106.70(11), 05-Nal-07 100.24(11), 05-Nal-01 89.01(10), 07-Nal-0 1 89.80(10), 05-NalOlw 90.60(10), 07-Nal-01 w 162.57(11), Ol-Nal-Olw 76.68(10)°, Symmetry operations: a = l+x, M2-y, 1 /2+z, b = -x,\ -y, 1 -z,c = -χ, 1 /2+y, 1 /2-z.

Crystal structure of a 3D coordination polymer: Zinc terephthalate hydrate

Figure 1. ORTEP plot of a portion of the ID zigzag chain formed in zinc terephthalate hydrate. The diagram was drawn at the 50% probability level and hydrogen atoms have been omitted for clarity. Selected bond distances and angles: Znl-Ol 1.9446(17), Zn l -03 1.978(3), Zn l -026 2.1829(17) Ä; O l -Zn l -O la 138.68(12), 01 -Zn l -03 110.66(6), 01-Znl -026 88.43(7), 03-Znl -02b 87.14(5), 01-Znl -02c 93.58(7), 02A-Zn 1 -02c 174.28(9)°. Symmetry transformation: a = x, y, z+5/2, b = x, -y+1, z+1/2, c = x, y+1, -z+2.

CRYSTAL STRUCTURE OF MONO AQUA 5-NITRO-1,3- BENZENEDICARBOXYLATOZINC· PYRIDINE MONOHYDRATE

Figure 1. ORTEP plot of the title complex at the 35% probability level. Selected bond distances and angles: Z n l O l = 1.977(2), Z n l 0 4 A = 1.973(2), Z n l O l w = 1.971(2), Z n l N 2 = 2.014(2) 0 1 W 0 2 W = 2.616(3), 0 1 W 0 2 B = 2.692(3), 0 2 W 0 3 B = 2.708(3), 0 2 W 0 6 C = 2.851(4) Ä; 0 1 Z n l N 2 = 106.9(1), 0 1 Z n l 0 4 A = 101.4(1), O l Z n l O l w = 115.1(1), N 2 Z n l 0 1 w = 106.8(1), N 2 Z n l 0 4 A = 126.3(1) Symmetry transformation: A = x,y,z + \ \ B = -x + \,-y + ζ + \ \C =-x\-y+ 2\-ζ + \ .

Crystal structure of poly[(N,N-di-methyl-acetamide-κO)(μ4-5-methyl-isophthalato-κ(5) O:O,O':O'':O''')manganese(II)].

The title compound, poly[(N,N-dimethylacetamide-κO)(μ4-5-methylisophthalato-κ5 O,O′:O′,O′′:O′′)manganese(II)], [Mn(C9H6O4)(C3H7NO)]n, was obtained from a mixture containing MnCl2·4H2O and 5-methylisophthalic acid in N,N-dimethylacetamide solution. The Mn2+ ion is coordinated by five O atoms from four bridging 5-methylisophthalate ligands and one O atom from one N,N-dimethylacetamide ligand, defining a considerably distorted coordination polyhedron with one very long Mn—O bond of 2.623 (2) Å. The Mn2+ ions are joined by carboxylate groups, forming rod-shaped secondary building units along the a axis. The rods are further connected by 5-methylisophthalate ligands to form the pcu (primitive cubic net) structure.

2-(3-Oxo-3,4-dihydro-2H-1,4-benzothia­zin-4-yl)acetohydrazide

In the title compound, C10H11N3O2S, the thiazine ring exists in a conformation intermediate between twist-boat and half-chair. The dihedral angle between the mean plane of the thiazine ring and the hydrazide group is 89.45 (13)°. In the crystal, N—H⋯O hydrogen bonds link the molecules into (100) sheets and weak C—H⋯O interactions further consolidate the packing.