Pamela J. Zapf

New solids from old clusters: syntheses and structures of [Cu(en)2]2[Mo8O26], [Cu(enMe)2]3[V15O36Cl]·2.5H2O and Cs0.5[Ni(en)2]3[V18O42Cl]·2en·6H2O

Abstract One-dimensional and two-dimensional solids consisting of polyoxoanions bridged by (M(LL)2)2+ groups have been synthesized by hydrothermal methods and structurally characterized by X-ray crystallography.

Organic/inorganic composite materials: the roles of organoamine ligands in the design of inorganic solids

Abstract The influence of organic components on the microstructure of inorganic solids has been extensively documented in recent years and has been shown to provide an efficacious method for the design of new materials. The synergism between the various chemical constituents at the organic/inorganic interface may result in imprinting of structural information from the organic molecules onto the inorganic framework. In this paper, the structural consequences of introducing organic components into several families of materials, including oxometalphosphates, transition metal oxides and transition metal halides and pseudohalides are briefly reviewed.

DIPYRIDYLAMINE-LIGATED OCTAMOLYBDATE CLUSTERS AGGREGATED INTO EXTENDED RIBBONS AND LAYERS VIA HYDROGEN BONDING

The hydrothermal reaction of MoO 3 with 4,4′-dipyridylamine yields [Mo 8 O 26 (4,4′-dpa) 2 ][4,4′-dpaH 2 ] 2 . The structure consists of octamolybdate clusters linked via H-bonding to the (dpaH 2 ) 2+ cations into one-dimensional ribbons which are in turn connected through H-bonding into two-dimensional sheets.

Ag (I)–organodiimine coordination complex polymers: structural influences of ligand geometries and charge-compensating oxoanions

Abstract Hydrothermal synthesis has been exploited in the preparation of two new materials of the Ag(I)-organodiimine class of materials. By exploiting variations in ligand geometry and tether length and the structural influence of different oxoanions, the inorganic oxides [Ag(dpe)(NO3)](dpe=1,2-bias(4-pyridyl)ethane) and [Ag2(2,4′-bpy)2(SO4)(H2O)]·5H2O(2·5H2O) were isolated. Compound 1 was prepared in the reaction of Ag(NO3), dpe, and H2O in the mole ratio 1:1:500 at 120°C for 24 h, while compound 2 was prepared from Ag2SO4, 2,4′-bpy, and H2O under similar conditions. The structure of 1 is constructed from {Ag(dpe)}nn+ chains linked through η2, μ2–NO3− groups into a two-dimensional network. The structure of 2·5H2O consists of one-dimensional sinusoidal chains. The Ag(I) sites exhibit two distinct geometries: one is ‘T’-shaped through bonding to two nitrogen donors from two 2,4′-bpy groups and a sulfate oxygen; the second site is also ‘T’-shaped through bonding to two pyridyl nitrogen atoms and an aqua ligand.

Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes

Abstract Two new vanadium oxide compounds, which contain interlamellar transition metal complexes bound to vanadium oxide sheets, were synthesized hydrothermally. The crystal structure of each reveals unusual coordination geometries and interlayer bonding. [Ni(2,2′-bipyridine)]2[V12O32] (1) was prepared from the reaction of V2O5, NiO, H2O and 2,2′-bipyridyl in the molar ratio 4:8:3312:0.5. The isomorphous compounds [M(2,2′-bipy)]2[V12O32] (where M is Co (1a) and Cu (1b)) were prepared in a similar fashion. The Ni coordination compound 1 crystallizes as amber needles, and the structure was solved in the space group C2/m (#12) with unit cell parameters a =24.344(3) A , b =6.897(3) A , c =12.028(2) A , β=93.60(2)° (R(Rw)=0.039(0.038)). This compound is composed of vanadium(V) oxide layers with nickel atoms coordinated within a single layer via four Ni–O–V linkages. Bidentate bipyridine (bpy) ligands complete the coordination sphere of the nickel atoms and interdigitate via π–π stacking with bpy ligands from the adjacent layer. Cu(en)2[V6O14] (2) crystallizes as black plates in the space group P21/n (#14) with unit cell parameters a =8.934(2) A , b =6.558(1) A , c =15.694(2) A , β=99.93(2)° (R(Rw)=0.039(0.035)), from the reaction of CuCl2·2H2O, V2O5, H2O and ethylenediamine in the ratio 1:1:447:4. This structure consists of mixed-valent vanadium(IV,V) oxide sheets forming weak O–Cu bonds to intercalated copper bis(ethylenediamine) complexes.

Crystal engineering of inorganic/organic composite solids: thestructure-directing role of aromatic ammonium cations in the synthesis ofthe ‘step’-layered molybdenum oxide phase[4,4′-H2bpy][Mo7O22]·H2O

The hydrothermal reaction of MoO 3 , Mo metal, NiCl 2 and 4,4′-bipyridine yields a step-layered molybdenum oxide [4,4′-H 2 bpy)][Mo 7 O 22 ]·H 2 O, a material structurally related to layered MoO 3 .

One- and two-dimensional organic-inorganic composite solids constructed from molybdenum oxide clusters and chains linked through {M(2,2′-bpy)}2+ fragments (M = Co, Ni, Cu)

Hydrothermal reactions of Na 2 MoO 4 ·2H 2 O and MoO 3 with MCl 2 ·xH 2 O (M = Co, Ni, Cu) and 2,2′-bipyridine yield one- and two-dimensional solids, characterized by molybdenum oxide monomers, clusters and chains linked by {M(2,2′-bpy)} 2+ groups and represented by the formulae [M(bpy) x - (H 2 O) y Mo n O 3n +1 ] (n = 2, M = Cu, x= 1, y = 0; n = 3, M = Co, x = 1, y = 0; n = 4, M = Ni, x = 2, y = 0).

A two-dimensional network constructed from hexamolybdate, octamolybdate and [Cu3(4,7-phen)3]3+ clusters: [{Cu3(4,7-phen)3}2{Mo14O45}]

The hydrothermal reaction of Cu(SO4)·H2O, MoO3, 4,7-phenanthroline and water yields [{Cu3(4,7-phen)3}2{Mo14O45}], a material exhibiting a two-dimensional network constructed from (Mo6O19)2– and (Mo8O26)4– clusters linked through planar cyclic {Cu3(4,7-phen)33}+ clusters.