Symplectically asystatic actions of compact Lie groups

In this paper we introduce the notion of symplectically asystatic Hamiltonian action on a Kahler manifold. In the algebraic setting we prove that if a complex linear group G acts on a Kahler manifold in a symplectically asystatic fashion, then the G-orbits are spherical. Finally, we give the complete classification of symplectically asystatic irreducible representations.     

Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

Does Hydrogen Bonding Matter in Crystal Engineering? Crystal Structures of Salts of Isomeric Ions

The preparation and structure determinations of the crystalline salts [3,3'-H(2)bipy][PtCl(4)] (2), [2,2'-H(2)bipy][PtCl(4)] (3) and [1,4'-Hbipy][PtCl(4)] (4) and [3,3'-H(2)bipy][SbCl(5)] (6) and [1,4'-Hbipy][SbCl(5)] (8) are reported. In addition a redetermination of the structure of the metastable salt [4,4'-H(2)bipy][SbCl(5)] (5 b) in the corrected space group Pbcm is described. These structures are compared to those of the known salt [4,4'-H(2)bipy][PtCl(4)] (1), the stable triclinic form of [4,4'-H(2)bipy][SbCl(5)] (5 a) and [2,2'-H(2)bipy][SbCl(5)] (7). In the case of the salts of the rigid [PtCl(4)](2-) ion, structures 2, 3 and 4 are essentially isostructural despite the differing hydrogen-bonding capability of the cations. Similarly, among the salts of [SbCl(5)](2-) ions, structures 7 and 8 are essentially isostructural. Structure 6 differs from these in having a differing pattern of aggregation of the [SbCl(5)](2-) ions to form polymeric rather than tetrameric units. It is evident that local hydrogen-bonding interactions, although significant, are not the only or even the decisive influence on the crystal structures formed by these salts. These observations are not in good accord with the heuristic "sticky tecton" or supramolecular synthon models for synthetic crystallography or crystal engineering.     

Cation and anion diversity in [M(dithiooxalate)2]2- salts: structure robustness in crystal synthesis

A series of crystalline salts based on the [M(dto)2]2- (dto = 1,2-dithiooxalate, M = Ni, Pt, Cu) dianion with hydrogen-bond donor cations have been synthesised following a molecular tectonics approach. The chelating M(dto)[dot dot dot]HN supramolecular synthon has been exploited in a systematic study of its robustness. The effects of competition between hydrogen-bond acceptors, of the shape and functionality of the cations and of varying the metal in the anion are discussed. The preparation and structural characterisation of the new crystalline phases [4,4'-H(2)bipy][Pt(dto)2] (2), [HNC5H4CO2H-4]2[Pt(dto)2] (5), [HNC5H4CO2H-3]2[Pt(dto)2] (6), [HNC5H4CH2CO2H-4]2[Ni(dto)2] (7), [HNC(5)H(4)CH(2)CO(2)H-3]2[Ni(dto)2] (8), [HNC5H4CONH2-4]2[Ni(dto)2] (9), [HNC5H4CHNOH-4]2[Ni(dto)2] (10), [HNC5H4CHNOH-3]2[Ni(dto)2] (11), [4,4'-H2bipip][Ni(dto)2] (12), [H2NC5H9CO2H-4]2[Pt(dto)2] (12), [H2NC5H9CO2H-4]2[Cu(dto)2] (14), [H2NC5H9CO2H-3]2[Ni(dto)2][H2O]2 (15), [H2NC5H9CO2H-3]2[Pt(dto)2][H2O]2 (16), [H2NC5H9CO2H-3]2[Cu(dto)2][H2O]2 (17), [H(Me)NC5H9CO2H-4]2[Ni(dto)2][H2O]2 (18) is reported. The charge-assisted NH[dot dot dot]dto synthon is formed in each of compounds 1-20, and is apparently much more robust than the conventional synthons used (such as the carboxylic acid dimer), which have a much lower rate of occurrence. The NH[dot dot dot]dto synthon may be generalised to 3- and 4-pyridinium species and 3- and 4-piperidinium derivatives. In the latter cases branching of the hydrogen-bond networks through the NH2 groups arises. The robustness of the NH...dto synthon allows structures of the form [NH cation]2[M(dto)2] to be regarded as being formed by the packing of neutral supermolecules. Cases of isomorphism (as in 16-18) and latent polymorphism (e.g. in 4 and 6) are noted.     

Synthesis and structural studies of 1,1'-bis-amino-functionalized ferrocenes, ferrocene salts, and ferrocenium salts

Having isolated and characterized a series of sodium cyclopentadienide salts, we have synthesized a number of 1,1'-bis-amino-functionalized ferrocenes, 1,1'-bis-amino-functionalized ferrocene salts, and 1,1'-bis-amino-functionalized ferrocenium salts. Among these are the first crystallographically characterized examples of cyclopentadienyl units containing (piperidin-N-ylethyl)- and (pyrid-2-ylmethyl)cyclopentadienyl side chains. In the cases of some of the ferrocenes, ferrocene salts, and ferrocenium salts, there are some interesting structural features in the solid state. These include C-H...N and C-H...pi cloud interactions as well as N-H...O and N-H...F hydrogen bonds.     

Thermal solid state synthesis of coordination complexes from hydrogen bonded precursors

Thermal dehydrochlorination of crystalline 4-picolinium salts of [PtCl4]2- and [PdCl4]2- leads to formation of trans-[MCl2(4-picoline)2](M = Pt, Pd).     

N-monofunctionalized 1,4,7-triazacyclononane macrocycles as building blocks in inorganic crystal engineering

The syntheses of N-(3-prop-1-ene)-1,4,7-triazacyclononane molybdenum tricarbonyl (2), N-(4-but-1-ene)-1,4,7-triazacyclononane molybdenum tricarbonyl (3), N-(3-prop-1-ene)-1,4,7-triazacyclononane molybdenum trioxide (5), N-(4-but-1-ene)-1,4,7-triazacyclononane molybdenum trioxide (6), N-(hydroxyethyl)-1,4,7-triazacyclononane molybdenum trioxide (7), and N-(2-methylpyridyl)-1,4,7-triazacyclononane molybdenum trioxide (8) have been achieved. The objective of this work is to systematically vary the functionality of the pendant group in order to create different crystal packing in the solid state. This is evidenced in comparing the structures of 1,4,7-triazacyclononane molybdenum trioxide (4) and 5-8, which were determined using X-ray crystallography. The synthesis and characterization of the new ligand N-(2-methylpyridyl)-1,4,7-triazacyclononane (L5) is reported.