David A. Grachvogel

A New Type of Metal‐Organic Large‐Pore Zeotype

A significant step towards the development of a new family of metal-organic zeolite analogues has been achieved by binding zinc ions to the anion of 4,6-di(1-imidazolyl)-1,3,5-triazine-2-one to produce a novel uncharged large-pore zeotype capable of incorporating a range of guest molecules.

Anion-dependence of the polymeric structures of manganese(II) complexes of N,N′-butylenebis(imidazole)

Abstract The preparations and X-band EPR spectra are reported of a series of manganese(II) complexes with N,N′-butylenebis(imidazole) (=BBI) of the types Mn(BBI)2X2 (X = Cl, Br, NO3, NCS) and [Mn(BBI)3]X2 (X = ClO4, I). An X-ray crystallographic study on Mn(BBI)2Cl2 (1) shows that each Mn atom is coordinated to four imidazole nitrogen atoms and two chloride ions in a trans-octahedral arrangement and that the BBI ligands link the Mn centres into sheets of contiguous 44-membered rings. X-Ray studies on [Mn(BBI)3](ClO4)2, and on analogous compounds containing combinations of ClO4−\PF6− or ClO4−\AsF6− as counter anions, reveal the formation of a family of interpenetrating network structures with anion-dependent cavity sizes.

Ein neuartiger großporiger, metallorganischer Zeotyp

Ein groser Schritt in Richtung einer neuartigen Gruppe von metallorganischen Zeolithanaloga konnte durch die Reaktion von Zinkionen mit 4,6-Di(1-imidazolyl)-1,3,5-triazin-2-on getan werden, wobei ein neuartiger, grosporiger Zeotyp entsteht (siehe Bild), der unterschiedliche Gastmolekule aufnehmen kann.

Diverse polymeric metal complexes formed by the ambidentate ligand 1-(4′-pyridyl)pyridin-4-one

Abstract The preparations are reported of a range of metal complexes of the ‘extended reach’ ambidentate ligand 1-(4′-pyridyl)pyridin-4-one (pypd), four of which have been shown by X-ray studies to have polymeric network structures. The compound [Cu(pypd)2(H2O)4](NO3)2·4H2O (1) forms sheets comprising [Cu(pypd)2(H2O)4] units linked by a complex set of hydrogen bonds. Crystals of stoichiometry Co(pypd)2(NCS)2·MeOH·H2O (2) contain a 1:1 co-crystallisation of [Co(pypd)2(H2O)2(NCS)2] and [Co(pypd)2(MeOH)2(NCS)2] each forming hydrogen bonded chains, which are linked into sheets by further hydrogen bonds. A combination of hydrogen bonding and π–π stacking between pyridyl and pyridone rings in Nd(pypd)2(H2O)2(NO3)3 (3) also generates a sheet structure. The compound [Cd(pypd)3](ClO4)2·3H2O (4) forms a complex 3D network.

Network coordination polymers formed by the ‘star’-shaped ligand hexakis(N-pyridin-4-one-methyl)benzene (HPMB)

Abstract The structures are reported of three coordination polymers formed by the hexadentate O-donor ligand hexakis(N-pyridin-4-one-methyl)benzene (HPMB). The structure of [Cu2(HPMB)(H2O)6](H2·HPMB)(ClO4)6·8H2O comprises chains of 32-membered rings cross-linked by hydrogen bonds to tapes of protonated HPMB ligands. Crystals of [Cu2(HPMB)Cl2(H2O)4]Br2·10H2O form chains of larger, 62-membered, rings with neighbouring chains cross-linked by hydrogen bonds to form sheets. In [Co(HPMB)](BF4)2·8MeOH·3.5H2O all six oxygen atoms of each HPMB ligand coordinate to a cobalt atom resulting in the formation of a contiguous 3-D network emulating the sodium chloride lattice, and containing substantial cavities and channels.

Combination of weak covalent, hydrogen bonding, and Ag⋯π interactions in the formation of a 3D porous network Ag(pypd)2(ClO4)·CH2Cl2 by the ambidentate ligand 1-(4′-pyridyl)pyridin-4-one

An interesting diversity of linkage types — weak covalent, hydrogen bonding, and Ag⋯π interactions — is shown to be involved in the 3D porous network formed by the title compound.

Chain polymeric complexes of some first-series transition-metal ions with N,N,N′,N′-tetra-acetyl-1,4-diaminobutane

The preparations are reported of the compounds [M(TADB)(H 2 O) 2 ](ClO 4 ) 2 (where TADB= N , N , N ′, N ′-tetra-acetyl-1,4-diaminobutane, and M=Mn, Co, Ni and Zn), and also of the analogous tetrafluoroborate salts with M=Mn, Co, Cu and Zn, and the complex Cu(TADB)(ClO 4 ) 2 . Crystals of [Zn(TADB)(H 2 O) 2 ](ClO 4 ) 2 are monoclinic, P 2 1 / n , with a =7.3735(2), b =12.4954(5), c =12.0313(5) A, β =100.581(4)°, and Z =2. Each zinc centre is coordinated to two trans -disposed aqua ligands and two chelating diacetamide units, one from each of two different TADB ligands, which, in turn bridge neighbouring zinc centres so as to generate cationic polymeric chains. X-ray powder diffraction studies show that, except for the copper(II) compounds, the other complexes are isostructural with the zinc complex. X-band EPR spectral results for the manganese(II) complexes and for samples of the other compounds ‘doped’ with small amounts of manganese(II) are also given.

Polymeric lanthanide complexes with extended reach bisamide ligands

Abstract It is shown by X-ray structural studies that the bisamide ligands N,N′-p-xylylenebisacetamide (PXBA, I), N,N′-trans-1,4-cyclohexylaminebisacetamide (1,4-CHBA, II) and N,N′-trans-1,4-cyclohexylaminebis-n-butyramide (1,4-CHBB, III) form polymeric network structures with lanthanide(III) nitrates. In the compound Er2(PXBA)3(NO3)6 (1) the erbium atoms are nine-coordinate and are linked by PXBA bridges to form sheets of contiguous 78-membered metallacyclic rings. In Ce(1,4-CHBA)2(NO3)3 (2) the cerium atoms are ten-coordinate and the 1,4-CHBA ligands bridge adjacent cerium centres to form sheets of contiguous 44-membered rings with (4,4) topology and with a very compact stacking of the adjacent sheets. In Nd(1,4-CHBB)2(NO3)3 (3) the neodymium atoms are eight-coordinate with the 1,4-CHBB ligands also bridging adjacent neodymium centres to form sheets of contiguous 44-membered rings with (4,4) topology, but with a pronounced ‘square-wave’ corrugation and crest-in-trough sheet stacking.