Zhao-Peng Deng

A series of three-dimensional lanthanide metal–organic frameworks with biphenylethene-4,4′-dicarboxylic acid: Hydrothermal syntheses and structures

Biphenylethene-4,4′-dicarboxylic acid (H2bpea) reacts with lanthanide(III) oxide (Ln = Sm, Eu, Gd, Tb, Er) or nitrate salts of lanthanide(III) (Ln = Eu, La, Tb) under hydrothermal conditions to form a series of lanthanide complexes 1–8, which were characterized by elemental analysis, IR, PL TG and single-crystal X-ray diffraction. These eight complexes exhibit four different kinds of 3-D frameworks. The complexes [Ln(bpea)(formate)]n (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Er (5)) were isomorphous and exhibited 3-D pillared layered frameworks. The eight-coordinated lanthanide ions in complexes 1–5 are bridged by the formate anions into 2-D covalent nets, which are further interconnected by the bpea ligands to produce the 3-D framework. While the formate anions are neglected, the new generated 3-D framework shows a four-connected SrAl2 net. The nine-coordinated europium ions in complex [Eu(bpea)(formate)]n (6) are also bridged by the formate anions into similar 2-D covalent nets, which are further interconnected by the bpea ligands to produce a different 3-D framework. Interestingly, complex 6 displays a 2-fold interpenetrating 3-D structure with Pts topology while neglecting the formate anions. The main reason is due primarily to the coordination geometry of the europium ion and the novel μ4:η6-bridging coordination mode of the bpea ligands. Complexes 7 and 8 have the same composition of [Ln(bpea)1.5(H2O)2]n (Ln = La (7) and Tb (8)), but crystallize in the P21/n and P space groups, respectively. In complex 7, the lanthanum centers are bridged by the bpea ligands in a common μ4:η4-bridging coordination mode into 2-D double layer motifs, which are further connected by the other μ4:η4-bridging bpea ligands to produce a 3-D hybrid framework with sixty-membered macro rings. By contrast, the terbium centers in complex 8 are bridged by the bpea ligands in an unprecedented μ4:η5-bridging coordination mode into 2-D layer architectures, which are further connected by the other μ2:η2-bridging bpea ligands to produce a 3-D hybrid framework.

catena-Poly[[aqua­diimidazole­cadmium(II)]-μ-thio­phene-2,5-dicarboxyl­ato]

The CdII atom has distorted pentagonal bipyramidal coordxadination geometry in the coordination polymer [Cd(TDA)(Him)2(H2O)]n [where TDA2− is the thioxadphene-2,5-dicarboxylxadate dianion (C6H2O4S2−) and Him is imidazole (C3H4N2)]. The cadmium ion is bound by four carboxylate O atoms from two independent TDA2− groups, two N atoms from two different imidazole ligands, and one water molxadecule. The carboxylxadate groups bind in bidentate mode to the Cd center, forming a linear chain structure such that the closest Cd⋯Cd distance is 10.577u2005(6)u2005A. The polymeric chains are connected via hydrogen bonds and π–π stacking interxadactions into a three-dimensional network.

(Acetato-κO)[diacetyl monooxime (4-methoxy­benzoyl)hydrazonato-κ3O,N,N′]bis(pyridine-κN)nickel(II)

In the title complex, [Ni(C12H14N3O3)(C2H3O2)(C5H5N)2], the NiII atom is six-coordinated by two N atoms and one O atom from a tridentate hydrazone ligand, two N atoms from two pyridine molecules, and one O atom from an acetate group, leading to a distorted octahedral geometry. The two N atoms of the pyridine molecules occupy the axial sites and the other four coordinated atoms define the equatorial plane. The uncoordinated acetate O atom forms an intramolecular hydrogen bond with the oxime O atom of the hydrazone ligand.

Poly­[strontium(II)-μ2-aqua-μ5-4-carboxyl­ato­phenoxy­acetato]

In the title three-dimensional coordination polymer, [Sr(4-CPOA)(H 2 O)] n (where 4-CPOA 2- is the 4-carboxylatophenoxyacetate dianion, C 9 H 6 O 5 ), each Sr II atom displays a bicapped triangular prismatic configuration, defined by five carboxyl and one ether O atom from five different 4-CPOA 2- ligands, as well as two water molecules. The Sr II atoms are covalently linked by 4-CPOA 2- ligands and water molecules, giving rise to a three-dimensional open framework. In previously studied polymers of this type, the 4-CPOA 2- ligand shows a variety of binding modes to metal ions, from mono- to pentadentate. In the present Sr II complex, a novel hexadentate bridging mode is observed.

The first continuous silver polyhedra framework containing four kinds of coordination spheres

The first continuous silver polyhedra framework containing four kinds of coordination spheres has been successfully prepared by the reaction of silver(I) nitrate and 4(1H)-pyridone-3-sulfonic acid. This polyhedra framework is constructed from four kinds of silver(I) polyhedra by sharing corners, edges and faces.

Tetra­aqua­bis(4-formyl­benzoato-κO)cobalt(II) tetra­hydrate

The CoII atom in the title compound, [Co(C8H5O3)2(H2O)4]·4H2O, which exists in an all-trans octahedral coordination geometry, lies on a center of inversion. The coordinated and uncoordinated water molecules engage in extensive hydrogen-bonding interactions, forming a three-dimensional hydrogen-bonded network.

Di‐μ‐aqua‐bis[aqua(2,2′‐bipyridine‐κ2N,N′)(4‐formylbenzoato‐κO)cobalt(II)] bis(4‐formylbenzoate)

The cation of the title salt, [Co2(C8H5O3)2(C10H8N2)2(H2O)4](C8H5O3)2, or [Co2(4-FBA)2(2,2′-bipy)2(H2O)4]·(4-FBA)2 [where 4-FBA− is the 4-formylxadbenzoate monoanion and 2,2′-bipy is 2,2′-bipyridine], is a dinuclear CoII complex which is located on an inversion centre. The Co atom is six-coordinated by one O atom of a 4-FBA− ligand, one 2,2′-bipy ligand and three water molxadecules in an octaxadhedral geometry. The two Co atoms are bridged by two water molxadecules into a four-membered Co2O2 ring, with a Co⋯Co distance of 3.344u2005(4)u2005A. A linear chain running along the a axis is formed through hydrogen-bonding interxadactions between cations and anions. Two O atoms are disordered equally over two sites.

Aquabis(4‐formylbenzoato)‐κ2O,O′;κO‐(1,10‐phenanthroline‐κ2N,N′)cadmium(II)

The CdII atom in the title complex, [Cd(C8H5O3)2(C12H8N2)(H2O)], is coordinated by three O atoms of two formylxadbenzoate ligands, two N atoms of a 1,10-phenanthroline ligand and one water molxadecule, giving rise to a trigonal–prismatic coordination geometry. Adjacent complex molxadecules are linked into a two-dimensional layer structure via hydrogen-bonding interxadactions.

Tetra­aqua­bis[2-(3-benzoyl­phen­yl)­propanoato-κO]cobalt(II) monohydrate

The title compound, [Co(C16H13O3)2(H2O)4]·H2O, is a transition metal complex of ketoprofen [2-(3-benzoylxadphenxadyl)xadpropanoic acid], a well known nonsteroidal anti-inflammatory drug. The asymmetric unit consists of two half-complexes and one water molxadecule of crystallization. The CoII atoms are located on inversion centers and show an octaxadhedral coordination geometry, defined by two carboxylxadate O atoms from two ketoprofenate ligands and four water molxadecules. The molxadecules are connected via O—H⋯O hydrogen bonds into a three-dimensional network.

Bis(4‐formyl­benzoato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)cadmium(II)–bis­(μ2‐4‐formyl­benzoato‐κ2O:O′)­bis­[(4‐formyl­benzoato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)cadmium(II)] (1/1)

The title compound, [Cd(C8H5O3)2(C12H8N2)][Cd2(C8H5O3)4(C12H8N2)2], having the empirical formulation bisxad(4-formylxadbenzoato)(1,10-phenanthroline)cadmium(II), is a 1/1 cocrystal consisting of mononuclear and dinuclear molxadecules. In the monomeric molxadecule that lies on a special position of site symmetry 2, cadmium is chelated by the N-heterocycle as well as by both carboxylxadate units in a cis-octaxadhedral geometry. The dimeric molxadecule lies on another special position of site symmetry 2 that relates two monomeric units; the octaxadhedral Cd atom is chelated by one carboxylxadate group and the N-heterocycle; the other carboxylxadate group functions as a carboxylxadate bridge between the two metal atoms.