A two-dimensional Zn(II) coordination polymer with a three-dimensional supramolecular architecture comprising 5-dimethylamino-isophthalic acid and 1,3-bis(4-pyridyl)propane

A new zinc coordination polymer, [Zn(L)(bpp)·H₂O]_n, was synthesized using 5-dimethylamino-isophthalic acid (H₂L) and 1,3-bis(4-pyridyl)propane (bpp) as organic linkers. In the complex, adjacent Zn²⁺ ions are linked by L^2? anions to form a one-dimensional (1D) [ZnL]_n chain. Then bpp ligands expand the 1D chains into a corrugated two-dimensional (2D) layer network by linking neighboring Zn²⁺ ions. These adjacent layers are further stacked together by direct C?H···π supramolecular interactions, generating a three-dimensional (3D) supramolecular structure. From the viewpoint of topology, the 2D network can be rationalized to a uninodal four-connected non-interpenetrated sql/Shubnikov tetragonal plane net with {4⁴.6²} topology. Moreover, the solid state properties such as thermogravimetric analysis and luminescence were also investigated.     

Synthesis and crystal structure of a copper coordination polymer [(Cu(btapo)2BrCH3OH)+Br−]n (btapo=1,3-bis(benzotriazol-1-yl) propan-2-ol)

A new coordination polymer [(Cu(btapo)₂BrCH₃OH)⁺Br⁻]_n (btapo = 1,3-bis(benzotria- zol-1-yl) propan-2-ol) was synthesized by the reaction of CuBr₂ and btapo, a new ligand synthesized in our laboratory, in THF. Its structure was determined by single-crystal X-ray crystallography. It crystallizes in tetragonal I4(1)/a space group with the crystal cell parameters of a=11.987(9) ?, c=54.24(4) ?, V=7794(10) ?³, and Z=8. The crystal X-ray analysis shows that each copper atom is five-coordinated with a bromine atom and four nitrogen atoms from four ligands to form a slightly distorted square pyramid. Each ligand bridges two copper atoms to form a two-strand helical chain. The chains are further extended to a three-dimensional network by the hydrogen bonds between the hydroxyl groups and the bromine anions. Supplementary material Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC 600471. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax;(+44) 1223–336-033; e-mail: deposit@ccdc.cam.ac.uk).     

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne and imidazole with Cu(II) generates a discrete complex not a coordination polymer: crystal structure of [μ-4,4′-(1,2-ethynediyl)-bis(pyridine-2,6-dicarboxylato)-N,O, O′-μ-N′, O′′, O′′′]-diaqua-bis(imidazole)-dicopper(II)

Reaction of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne and imidazole with Cu(II) produces crystals containing a discrete complex of [μ-4,4′-(1,2-ethynediyl)-bis(pyridine-2,6-dicarboxylato)-N, O, O′-μ-N′, O′′, O′′′]-diaqua-bis(imidazole)-dicopper(II) complex (1), [(C₁₆H₄N₂O₈)(C₃H₄N₂)₂(H₂O)₂Cu₂] instead of a linear coordination polymer. The complex crystallizes in the monoclinic space group P2₁/n with a = 5.3763(8) ?, b = 18.522(3) ?, c = 11.4827(7) ?, β = 93.705(3) ° and Z = 2. The complex sits on a center of symmetry such that the two halves of the molecule are related by inversion symmetry. The molecules pack in layers in which the molecules are joined by intermolecular N–H⋯O hydrogen bonds between imidazole and carboxylate groups and O–H⋯O hydrogen bonds between carboxylate groups and water.     

Self-assembly of a Cd(II) coordination polymer with the 3,5L2 topology: Synthesis,structure, and properties

A new cadmium(II) coordination polymer, [Cd(ntdc)(dps)·H₂O]_n, was synthesized using 3-nitro-thiophene-2,5-dicarboxylic acid (H₂ntdc) and 4,4´-dipyridylsulfide (dps) as organic linkers. In the complex, adjacent Cd²⁺ ions are linked by ntdc^2? anions adopting a new coordination mode to form a one-dimensional (1D) [Cd(ntdc)]_n chain. Then dps ligands further expand the 1D chain into a corrugated two-dimensional (2D) layer network by linking neighboring Cd²⁺ ions. Topologically, the 2D network can be rationalized to a 3,5-connected 3,5L2 topology. Moreover, solid state properties such as thermogravimetric analysis and photoluminescent property were also investigated.     

The synthesis and structure of a novel alternating 1-D cobalt coordination polymer [Co(2,5-PDC)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>Co(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>]·4H<Subscript>2</Subscript>O

A novel cobalt complex [Co(2,5-PDC)₂(H₂O)₂Co(H₂O)₄]·4H₂O (2,5-PDCH₂ = 2,5-pyridinedicarboxylic acid) was synthesized and its crystal structure has been determined by X-ray diffraction. The crystallographic data are: triclinic P−1, a = 7.112(2) ?, b = 8.939(3) ?, c = 9.719(3) ?, α = 91.153(5)°, β = 101.136(5)°, γ = 108.001(4)°, V = 574.4(3) ?³, Z = 1. The compound [Co(2,5-PDC)₂(H₂O)₂Co(H₂O)₄]·4H₂O exhibits a novel one-dimensional network constructed from the interconnection of Co(2,5-PDC)₂(H₂O)₂ and Co(H₂O)₄, in which two kinds of six-coordinated Co(II) atoms have both octahedral coordination environments. Each 2,5-PDC anion connects two different coordinated cobalt ions alternately in an one-dimensional chain. The zigzag 1D alternating chains are linked by extensive hydrogen bonds to form a three-dimensional (3D) supramolecular structure, in which uncoordinated solvate molecules act as space filling particles. Supplementary data CCDC-264249 contains the supplementary crystallographic data for this paper. Copies of this information may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: t44–1223–336033; e-mail: deposit@ccdc.cam.ac.uk or ) or also available from the author Xiaoqing Wang.     

Synthesis and structural properties of a 1-D copper(I) coordination polymer

A coordination polymer catena-chloro(4-pyridinecarboxylic acid)copper(I): [Cu(C₆H₅ O₂N)Cl]_n (1) has been prepared directly by reacting Cu^IICl₂ 2H₂O and 4-cyanopyridine in the presence of disodium maleate under hydrothermal conditions at 140°C. Crystal data for 1 are as follows: monoclinic, P2₁/n, a = 16.4623(9) Å, b = 3.7795(2) Å, c = 24.7612(11) Å, = 101.534(1)°, V = 1509.5(1) ų, Z = 4, D _calc. = 1.955 g cm^–3, R1 = 0.0511, wR2 = 0.1060 for all 2666 reflections. In this 1-D stair-polymer, two [Cu–Cl–Cu]_n zigzag chains are held together by weak interchain Cu–Cl bonds. The 4-pyridinecarboxylic acid ligands derived from the 4-CNpy molecules coordinate to the approximately tetrahedral Cu(I) centers through pyridyl-N atoms. The carboxyl ends of 4-pyridinecarboxylic acid participate in interchain hydrogen-bonding interactions to form a 2-D supramolecular network.     

Synthesis and structural characterization of a novel polymeric gadolinium(III)–copper(II) complex of iminodiacetic acid

A novel polymeric Gd₂Cu₃ complex of iminodiacetic acid (H₂L¹=NH{CH₂COOH}₂), namely, Gd₂Cu₃(L¹)₆, 1, has been synthesized and structurally characterized. In the title complex, the Gd³⁺ ion is nine-coordinated by six O atoms from three bidentate chelating carboxylate groups and three O atoms from three anti-anti bridging carboxylic groups of six L¹ ligands; the Cu²⁺ ion is six-coordinated by four O and two N atoms from two chelating L¹ ligands. Each pair of Gd(III) atoms is bridged by three L¹ ligands, each of which also chelates with one copper(II) ion, thus forming a Gd₂Cu₃ cluster unit. Such cluster units are cross-linked by flexible L¹ ligands into a three-dimensional coordination framework. The title complex crystallizes in the trigonal space group P-3c1 (No. 165) with a = b = 13.433(4), c = 14.770(6) Å; V = 2308(1) ų; D_calca = 1.859 g cm^–3; Z = 2.     

Synthesis and crystal structure of an infinite double- stranded chain manganese(II) coordination polymer bridged through 1,2-bis(imidazol-1-yl)ethane ligand

The manganese complex [Mn(bim)₂(NCO)₂]_n (1) (bim = 1,2-bis(imidazol-1-yl)ethane) has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in the monoclinic space group C2/c, a = 9.896(3) Å, b = 15.383(4) Å, c = 13.949(4) Å, β = 98.966(5)^∘, V = 2097.5(9) ų, Z = 4. The coordination geometry of Mn(II) atom is distorted octahedral; it is coordinated equatorially by four nitrogen atoms from the imidazole rings of four symmetry-related bim ligands, and axially by two nitrogen atoms from two symmetry-related cyanate anions. The structure is polymeric, with 18-membered spiro-fused rings and each 18-membered ring involving two inversion-related bim molecules.     

Synthesis and crystallographic characterization of a six coordinate Cu(II) complex based on hexamethylenetetramine ligand

The title compound, Cu(H₂O)₆]Cl₂.2{(CH₂)₆N₄}.4H₂O ( 1 ), has been prepared under mild hydrothermal conditions. Each Cu^II atom, located on a centre of symmetry, is coordinated by six water molecules in distorted octahedral coordination geometry. The hexamethylenetetramine molecule does not coordinate to the Cu atom but links with the Cu complex via three O—H…N hydrogen bonds. The remaining N atom of the hexamethylenetetramine is hydrogen‐bonded to the solvent water molecule. In the crystal structure, intermolecular O—H…O, O—H…N and O—H…Cl hydrogen bonds link the components into a three‐dimensional network. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of counter-anion on the coordination geometry of manganese(II) complexes with methyl-2-pyrazinecarboximidate ligand

Two new complexes of [Mn(2-MPyzCI)₂Cl₂].H²O (1) and [Mn(2-MPyzCI)₂(H₂O)₂](NO₃)₂ (2) were synthesized from the reaction of MnX₂.4H₂O (X=Cl^? and NO₃^?) with 2-cyanopyrazine in methanolic solution. The chelating methyl pyrazine-2-carboximidate (2-MPyzCI) ligand is formed via the methanolysis of 2-cyanopyrazine. Although coordination environment around manganes(II) ions is similar, but these complexes are different in geometrical position of 2-MPyzCI ligands. As both compounds are synthesized under the same reaction conditions, the only difference between these two complexes are counter ions and changing of geometrical position of ligands can be considered as a result of influence of the counter-anions on the molecular structures.     

Crystal structure of N,N-bis(2,5-dioxopyrrolidin-1-ylmethyl)glycine

The preparation and molecular and crystal structures of the title compound are reported. The compound crystallizes in the triclinic space group (No. 2) with unit cell dimensions of a = 7.2493(3) Å, b = 8.9287(4) Å, c = 10.6594(4) Å, = 90.419(3)°, = 91.287(3)°, = 103.153(3)°, V = 671.62(5) ų, and Z = 2. The molecular structure of the title compound consists of three sections, the glycine chain and the two 2,5-dioxopyrrolidin-1-ylmethyl groups. Every molecule is linked with three adjacent molecules through three hydrogen-bonding patterns which are 8-membered or 20-membered rings. The chain of rings appears periodically, which makes the molecule form a layer structure in the crystal.     

Synthesis and structural characterization of a novel polymeric praseodymium(III) complex with a new flexible double betaine

A novel polymeric Pr(III) complex with a new double betaine, namely [{Pr(L¹)_1.5(H₂O)₂} _n ][ClOli4]3 _n ·nH₂O (1) (L¹ = 1,4-diazoniobicyclo[2,2,2]octane-1,4-dipropionate), has been synthesized and characterized by X-ray analysis. In the title complex, the Pr(III) atom is nine-coordinated by seven oxygen atoms from five L¹ ligands and two aqua ligands. Each pair of adjacent praseodymium(III) atoms is linked by a pair of ³ chelating and bridging carboxylate groups, thus forming an infinite metal···metal chain running parallel to the a direction, and such chains are cross-linked by flexible backbones of L¹ ligands into a three-dimensional network with the perchlorate anions and lattice water molecules accommodated in the interstitial space. The title complex crystallizes in the monoclinic space group P2₁/n with a = 8.085(2), b = 14.316(3), c = 29.775(6) Å, = 103.04(3)° and Z = 4.     

Preparation and characterization of a bidentate carboxylate-bridged dinuclear cadmium(II) complex with bis(2-pyridylmethyl)amino-3-propionic acid

The carboxylate-bridged dinuclear complex [Cd(-pmpa)(H₂O)](ClO₄)·H₂O (1) (Hpmpa = bis(2-pyridylmethyl)amino-3-propionic acid) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the monoclinic system P2 ₁/n with a = 7.9678(6) Å, b = 17.5103(9) Å, c = 14.3147(9) Å, = 94.1030(10)°, V = 1992.0(2) ų, Z = 4. The carboxylate group of the pmpa ligand adopts a bidentate bridging coordination mode, and the ligand acts as -bridge linking two cadmium(II) ions to form a dinuclear complex. Each cadmium atom is seven-coordinate, with a distorted pentagonal bipyramidal geometry. The cyclic voltammogram of 1 undergoes irreversible one-electron oxidation to the Cd(III) and reversible one-electron reduction to the Cd(I).     

Growth and properties of an organometallic nonlinear optical crystal: bis(isothiocyanato)‐bis(4‐methylpyridine)zinc(II) (Zn(SCN)2(C6H7N)2)

Bis(isothiocyanato)‐bis(4‐methylpyridine)zinc(II)(Zn(SCN)₂(C₆H₇N)₂), (abbreviated as ZBNC) single crystals of optical quality have been grown from acetone solution by the slow temperature‐lowering method. Its solubilities at different temperatures in acetone were measured. The X‐ray powder diffraction (XRPD) spectroscopy of ZBNC crystal was performed at room temperature. The second harmonic generation (SHG) efficiency was determined by powder technique of Kurtz and Perry using Nd:YAG laser, which is equivalent to KDP crystal. The thermal decomposition process was characterized by thermal gravity and differential thermal analysis (TG\DTA). The specific heat of the crystal is 1440.67 J/mol·K at 325 K. The IR spectrum was recorded in the 500∼3500 cm^–1 region, using KBr pellets on a Nicolet 170sx FT‐IR spectrometer. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of copper(II) tetraaza macrocyclic complex with 2- benzimidazolepropionate ligand

A mononuclear complex [Cu(L)(bip)₂] (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0^1.18, 0^7.12]docosane; bip = 2-benzimidazolepropionate) has been synthesized and structurally characterized by X-ray crystal structure analysis. The crystals are monoclinic P2 ₁/n with a = 10.2990(2), b = 15.9400(3), c = 11.991(14) Å, = 101.92(7)°, V = 1926(2) ų, Z = 2. The copper(II) coordination geometry exhibits an axially elongated octahedron with four nitrogen atoms from the macrocycle and two oxygen atoms from the bip ligands. The cyclic voltammogram of 1gives 2 one-electron waves corresponding to Cu^II/Cu^III and Cu^II/Cu^I processes.     

Hydrothermal synthesis and structure of a novel terbium coordination polymer with packing cavities, {[Tb(TCB)1/2(H2TCB)1/2(H2O)](H2O)2}n (H2TCB = 1, 2, 4, 5‐benzenetetracarboxylic acid)

A novel terbium coordination polymer {[Tb(TCB)_1/2(H₂TCB)_1/2(H₂O)](H₂O)₂}_n (H₂TCB = 1, 2, 4, 5‐benzenetetracarboxylic acid) ( 1 ) has been hydrothermally synthesized and determined by single crystal X‐ray diffraction method, which features a very interesting three‐dimensional framework with large packing cavities. It crystallizes in the monoclinic space group P2₁/n with a = 1.0723(4) nm, b = 0.7168(3) nm, c = 1.7155(6) nm, β = 97.079(4)°, V = 1.3086(8) nm³, Z = 4, and final R₁ = 0.0203, wR₂ = 0.0404. In 1, the protonated carboxylate groups are free, the other carboxylate groups are bonded to Tb³⁺ ion in three modes: the chelating bidentate, the bridging bidentate and bridging tridentate. Moreover each Tb³⁺ ion is coordinated by nine oxygen atoms from six carboxylate groups and one water molecule respectively to complete a deformed tricapped trigonal prismatic geometry. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Syntheses,crystal structures and properties of Cd(II) and Ag(I) complexes based on 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole

Abstract

Complexes of [CdL₂(NO₃)₂]·1.5H₂O and [Ag₂(μ-L)₂(NO₃)₂] were synthesized by the reactions of 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole (L) with Cd(NO₃)₂·4H₂O and AgNO₃, respectively. Their structures were determined by single crystal X-ray diffraction. The photophysical property and thermal stability were characterized by FT???IR, UV???Vis absorption, fluorescence, and thermogravimetric analysis (TGA). Both complexes belong to the triclinic system with space group p???1. The central metal of [CdL₂(NO₃)₂]·1.5H₂O has a distorted octahedral geometry [CdN₄O₂], while two central Ag(I) atoms of [Ag₂(μ-L)₂(NO₃)₂] exhibit distorted tetrahedral geometries [AgN₃O].     

Synthesis,characterization and crystal structure of a novel Ni(II) coordination polymer with dipyrido[3,2‐a:2′,3′‐c]phenazine and 4,4′‐oxy(bisbenzoate)

A novel coordination polymer, [Ni(dppz)(oba)(H₂O)]·0.5H₂O (dppz = dipyrido[3,2‐a:2′,3′‐c]phenazine and oba = 4,4′‐oxy(bisbenzoate)) has been synthesized through hydrothermal method and characterized by IR, and single‐crystal X‐ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 23.163(5), b = 18.211(4), c = 14.460(3) Å, α = γ = 90°, β = 100.45(3)°, V = 5998(2) ų, Z = 2. The structure was solved by direct methods and refined to R = 0.0866 (wR₂ = 0.1836). The compound exhibits interesting one‐dimensional chain structures, which are further stacked through π‐π interactions to form supramolecular double chains. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

pH‐Controlled topologies of two Co(II) complexes based on 5‐Nitro‐1,2,3‐benzenetricarboxylic acid and 1,6‐Bis(1,2,4‐triazole‐1‐yl)hexane

Two new Co(II) coordination polymers, [Co(Hnbta)(bth)]_n ( 1 ) and {[Co₃(nbta)₂(bth)₃(H₂O)]·H₂O}_n ( 2 ), (H₃nbta = 5‐nitro‐1,2,3‐benzenetricarboxylic acid and bth = 1,6‐bis(1,2,4‐triazole‐1‐yl)hexane), have been synthesized under different pH values through hydrothermal reactions. Both complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis (TGA), and single‐crystal X‐ray crystallography. Complex 1 exhibits a 3D polythreaded network based on 4‐connected sql 2D layer. Complex 2 has a (4,4,5)‐connected trinodal 3D pillar‐layered network with a (4²·6⁴)₂(4²·6⁷·8)₂(6⁴·8²) topology. Magnetic susceptibility measurements indicate that complexes 1 and 2 show weak antiferromagnetic interactions between the adjacent Co(II) ions.