Improved hydrogen release from LiB0.33N0.67H2.67 with noble metal additions

The hydrogen release behavior of the quaternary hydride LiB(0.33)N(0.67)H(2.67) has been successfully improved through the incorporation of small quantities of noble metal. Adding 5 wt % Pd either as Pd metal particles or as PdCl(2) reduced the temperature T(1/2) corresponding to the midpoint of the hydrogen release reaction by DeltaT(1/2) = -43 degrees C and -76 degrees C, respectively. PtCl(2) and Pt nanoparticles supported on a Vulcan carbon substrate proved to be even more effective, with DeltaT(1/2) = -90 degrees C. The amount of NH(3) released during dehydrogenation is reduced compared to that from additive-free material, and, more importantly, at temperatures below 210 degrees C hydrogen is released with no detectable NH(3). In contrast to additive-free LiB(0.33)N(0.67)H(2.67), which melts completely above 190 degrees C and releases hydrogen from the liquid state only above approximately 250 degrees C, hydrogen release from LiB(0.33)N(0.67)H(2.67) + 5 wt % Pt/Vulcan carbon is accompanied by partial melting plus a cascade through a series of solid intermediate phases. Calorimetric measurements indicate that both additive-free and Pt-added LiB(0.33)N(0.67)H(2.67) release hydrogen exothermically, and hence the reverse reaction is thermodynamically unfavorable. By exposing partially dehydrogenated samples to high H(2) pressures at modest temperatures, fractional hydrogen uptake (roughly 15% of the released hydrogen) has been achieved. The mechanism by which noble metals promote hydrogen release is not known, but the behavior is consistent with that expected for a catalyst, including a large effect with small additions and saturation of the effect at low concentration.     

Experimental charge density study of estrogens: 17beta-estradiol.urea

To relate the molecular electrostatic potential to the biological activities of estrogens, a comparative charge density study of different derivatives has been initiated. The second completed charge density analysis of this series for 17beta-estradiol*urea is presented here. This is a large organic system with 52 atoms in a noncentrosymmetric space group, therefore special tools such as an optimal coordinate system and slow, initially constrained refinement have been used to accomplish this study. Our results for the urea molecule reasonably agree with previous experimental and theoretical results. In the 17beta-estradiol molecule, the oxygen atoms appear to be close to sp3 in shape, exhibiting two consistent, distinct lone pairs despite different chemical environments. No significant interaction of the hydroxyl group oxygen with the orbitals of the aromatic ring is observed. Analysis of the electrostatic potential revealed that the negative potential in the lone pair region of the two oxygen atoms is quite different. The topological analysis of the electron density has been performed, and the atomic charges have been estimated.     

Structures of divalent transition metal salts of 4-aminonaphthalene-1-sulfonate: unexpected variations in layering pattern

Salts of 4-aminonaphthalene-1-sulfonate with divalent Mg, Mn, Co, and Ni cations have been crystallized and their structures determined by single crystal X-ray methods. The Mg and Mn salts are isostructural. Crystal data for hexa-aquamagnesium(II) 4-aminonaphthalene-1-sulfonate dihydrate, [Mg(H₂O)₆](H₂NC₁₀H₆SO₃)₂ 2H ₂O: monoclinic, P2₁/c, Z = 2, a = 8.622(3), b = 7.043(3), c = 23.178(3) Å, =93.78(2)°, V = 1404.3(7) ų; hexa-aquamanganese(II) 4-aminonaphthalene-1-sulfonate dihydrate, [Mn(H₂O)₆](H₂NC₁₀H₆SO₃)₂ 2H ₂O: monoclinic, P2₁/c, Z = 2, a = 8.652(3), b = 7.031(4), c = 23.402(2) Å, =93.09(2)°, V = 1421.5(9) ų. The structures are composed of alternating layers of octahedral metal–aqua complexes and sulfonate anions linked by an extensive network of hydrogen bonds. The extra water molecules of crystallization are located in the hexa-aquametal cation layers. The repeat unit along the c axis is a double layer. The Co and Ni compounds are isostructural with each other, but compared to the Mg and Mn compounds, have a strikingly different structure. Crystal data for hexa-aquacobalt(II) 4-aminonaphthalene-1-sulfonate trihydrate, [Co(H₂O)₆](H₂NC₁₀H₆SO₃)₂ 3H ₂O: orthorhombic, Pbca, Z = 8, a = 8.518(1), b = 14.327(2), c = 45.367(6) Å, V = 5536(1) ų; hexa-aquanickel(II) 4-aminonaphthalene-1-sulfonate trihydrate, [Ni(H₂O)₆](H₂NC₁₀H₆SO₃)₂ 3H ₂O: orthorhombic, Pbca, Z = 8, a = 8.4976(6), b = 14.288(1), c = 45.076(3) Å, V = 5472.9(7) ų. These structures also contain layers of octahedral hexa-aquametal complexes and additional water molecules of crystallization sandwiched by layers of sulfonate anions, however the stacking pattern is more complex with a quadruple layer repeat unit and two different types of anion layers.     

Energetic materials: The preparation and structural characterization of melaminium dinitramide and melaminium nitrate

Two energetic salts of the melaminium cation have been prepared and structurally characterized from room temperature X-ray single crystal diffraction data. Melaminium dinitramide (I), triclinic, P1¯, a = 6.6861(11), b = 6.9638(16), c = 10.447(2) Å , = 99.07(3), = 98.30(3), = 108.50(3)°, V = 445.6(2) ų, and Z = 2. Melaminium nitrate (II), monoclinic, P2₁/c, a = 3.5789(7), b = 20.466(4), c = 10.060(2) Å, = 94.01(2)°, V = 735.0(3) ų, and Z = 4. The crystal structures of both salts show distinct monoprotonated melaminium cations and dinitramide- or nitrate anions, respectively. Efficient packing in the solid state is achieved by extensive hydrogen bonding between two-dimensional zigzag ribbons of the melaminium cations and the respective anions resulting in high densities of the solid state structures of 1.74 (I) and 1.71 g/cm³ (II).     

Structure of 1,2,3,4,9,9-hexachloro-6,7-tetrahydro-l,4-methano-naphthalene: a facially differentiated, annulated 1,3-cyclohexadiene

The X-ray crystal structure of the title compound is reported. Crystal data: T = 100 K, monoclinic, P2₁/n, a = 8.2990(17), b = 13.2300(26), c = 12.0350(24) Å, = 93.676(30)°, V = 1318.7 (5) ų, and R = 0.0368. The methylene carbon atoms in the cyclohexadiene ring are disordered over two positions above and below the ring plane. The chlorine substituted endocyclic double bond deviates from planarity with an angle of 8.10(13)° toward the endo-face. The facially differentiated 1,3-cyclohexadiene moiety is only slightly pyramidalized, deviating 1.75(20)° also toward the endo-face of the tricyclic system.     

1,5‐Asymmetric induction during nucleophilic additions to arenetricarbonylchromium complexes: tricarbonyl(η6‐1‐methyl‐4‐{spiro[(1R,2S)‐1,7,7‐trimethylbicyclo[2.2.1]heptane‐3,2′‐1,3‐dioxolan]‐2‐yloxy}benzene)chromium

The tricarbonylchromium unit bound to the arene ring of the chiral title complex, [Cr(C₁₉H₂₆O₃)(CO)₃], is rotated by ca 25° in agreement with the proposed mechanism for 1,5‐asymmetric induction of nucleophilic attack.     

Variable temperature neutron diffraction and X-ray charge density studies of tetraacetylethane

Single crystal neutron diffraction data have been collected on a sample of enolized 3,4-diacetyl-2,5-hexanedione (tetraacetylethane, TAE) at five temperatures between 20 and 298 K to characterize the temperature-dependent behavior of the short, strong, intramolecular hydrogen bond. Upon decreasing the temperature from 298 K to 20 K, the O2-H1 distance decreases from 1.171(11) to 1.081(2) A and the O1...H1 distance increases from 1.327(10) to 1.416(6) A. The convergence of the C-O bond lengths from inequivalent distances at low temperature to identical values (1.285(4) A) at 298 K is consistent with a resonance-assisted hydrogen bond. However, a rigid bond analysis indicates that the structure at 298 K is disordered. The disorder vanishes at lower temperatures. Short intermolecular C-H...O contacts may be responsible for the ordering at low temperature. The intramolecular O...O distance (2.432 +/- 0.006 A) does not change with temperature. X-ray data at 20 K were measured to analyze the charge density and to gain additional insight into the nature of the strong hydrogen bond. Quantum mechanical calculations demonstrate that periodic boundary conditions provide significant enhancement over gas phase models in that superior agreement with the experimental structure is achieved when applying periodicity. One-dimensional potential energy calculations followed by quantum treatment of the proton reproduce the location of the proton nearer to the O2 site reasonably well, although they overestimate the O-H distance at low temperatures. The choice of the single-point energy calculation strategy for the proton potential is justified by the fact that the proton is preferably located nearer to O2 rather than being equally distant to O1 and O2 or evenly distributed (disordered) between them.