The crystal and molecular structure of the bis(4-N, N1-dimethylaminopyridine) solvate of disalicylicacidatobis(nitrotodioxouranium)(VI)

The structure of the title compound [(C7H4NO8U)(C7H11N2)]2 has been determined by Patterson and Fourier methods from single crystal X-ray diffraction data collected on a four-circle diffractometer. Full-matrix least-squares refinement yielded a final conventional R of 0.041 for 2189 reflections. The complex crystallizes in the space group P with a = 11.004(5), b = 9.981(5), c = 9.928(5) Å, α = 119.6(3), β = 107.7(3), γ = 81.9(3)°, Dm = 2.17, Dc = 2.173g cm−3. The structure is dimeric. The uranium atoms are eight-coordinate and are bridged via centrosymmetrically related carboxylic oxygen atoms. The nitrate group is bidentate and the average U---O (ligand) distance is 2.463 Å. Hydrogen bonding of the type N---HO links two dimethyl-aminopyridine molecules to the dimer

The structure of aliphatic amine adducts of uranyl acetylacetonate. III. Dioxobis(2,4-pentanedionato)mono (2-N-isopropylaminopentan-4-one)uranium(VI)

Introduction: In two earlier structural determinations of compounds of this type we have shown that the conformation of the adduct moiety is dependent on the formation of intramolecular N-H...0 hydrogen bonds (part I: Haigh, Nassimbeni, Pauptit, Rodgers & Sheldrick, 1976; part II: Nassimbeni, Orpen, Pauptit, Rodgers & Haigh, 1977). We have carried out the present analysis to study the conformational effects on the ligand brought about by the steric influence of an isopropyl substituent at N

The structure of aliphatic amine adducts of uranyl acetylacetonate. II. Dioxobis(2,4-pentanedionato)mono (2-N,N-dimethylaminopentan-4-one)uranium(VI)

Introduction: In a previous analysis of a compound of this type, we have established that the adduct molecule is bonded through O and that the geometry about U is pentagonal bipyramidal (Haigh, Nassimbeni, Pauptit, Rodgers & Sheldrick, 1976). We have carried out the present analysis to study the conformational effects on the ligand brought about by substitution at N

The structure of aliphatic amine adducts of uranyl acetylacetonate. IV. Dioxobis(2,4-pentanedionato) mono(2-aminopentan-4-one)uranium(VI)

Introduction: We have shown in three earlier determinations of aliphatic amine adducts of U02(AA)2 (part I: Haigh, Nassimbeni, Pauptit, Rodgers & Sheldrick, 1976; part II: Nassimbeni, Orpen, Pauptit, Rodgers & Haigh, 1977; part III: Rodgers, Nassimbeni & Haigh, 1977) that the conformation of the adduct is dependent on its ability to form hydrogen bonds. The present compound has two H atoms available for hydrogen bonding and may be regarded as the parent of the series

The structure of aliphatic amine adducts of uranyl acetylacetonate. I. Dioxobis(2,4-pentanedionato)mono (2-N-methylaminopentan-4-one)uranium(VI)

Crystals of the title compound are monoclinic with a= 8.314 (5), b= 22.723 (9), c= 12.589 (6) A, /3= 123.0 (2t, Z=4, space group P2dc. The structure was determined by Patterson and Fourier methods and refined by full-matrix least squares to a final R of 0.030 for 2043 independent reflexions. The U atom has pentagonal bipyramidal coordination and the N-methylacetylacetoneamine is bonded to U via O. There are two intramolecular N-H. . .0 hydrogen bonds which govern the geometry of the adduct molecule

The crystal structure of caesium permanganate by x-ray diffraction

The crystal structure of caesium permanganate has been determined. CsMn0₄ crystallises in the orthorhombic space group Pnma. There are four molecules per unit cell with a = 10.0692 Å, b = 5.8080 Å, c = 7.9470 Å. The structure was determined by Fourier syntheses on the (010) and (001) projections and refined by two-dimensional difference syntheses. The structure is similar to that of KMn0₄. The manganese is surrounded by four oxygen atoms at an average distance of 1.629 Å arranged in a slightly distorted tetrahedron. The caesium is surrounded by eight manganese atoms at an average distance of 4.381 Å

Mapping the internal recognition surface of an octanuclear coordination cage using guest libraries

Size and shape criteria for guest binding inside the cavity of an octanuclear cubic coordination cage in water have been established using a new fluorescence displacement assay to quantify guest binding. For aliphatic cyclic ketones of increasing size (from C5 to C11), there is a linear relationship between ΔG for guest binding and the guest’s surface area: the change in ΔG for binding is 0.3 kJ mol–1 Å–2, corresponding to 5 kJ mol–1 for each additional CH2 group in the guest, in good agreement with expectations based on hydrophobic desolvation. The highest association constant is K = 1.2 × 106 M–1 for cycloundecanone, whose volume is approximately 50% of the cavity volume; for larger C12 and C13 cyclic ketones, the association constant progressively decreases as the guests become too large. For a series of C10 aliphatic ketones differing in shape but not size, ΔG for guest binding showed no correlation with surface area. These guests are close to the volume limit of the cavity (cf. Rebek’s 55% rule), so the association constant is sensitive to shape complementarity, with small changes in guest structure resulting in large changes in binding affinity. The most flexible members of this series (linear aliphatic ketones) did not bind, whereas the more preorganized cyclic ketones all have association constants of 104–105 M–1. A crystal structure of the cage·cycloundecanone complex shows that the guest carbonyl oxygen is directed into a binding pocket defined by a convergent set of CH groups, which act as weak hydrogen-bond donors, and also shows close contacts between the exterior surface of the disc-shaped guest and the interior surface of the pseudospherical cage cavity despite the slight mismatch in shape