Dataset Information

Structure, hydrogen bonding and thermal expansion of ammonium carbonate monohydrate.

ABSTRACT: We have determined the crystal structure of ammonium carbonate monohydrate, (NH4)2CO3·H2O, using Laue single-crystal diffraction methods with pulsed neutron radiation. The crystal is orthorhombic, space group Pnma (Z = 4), with unit-cell dimensions a = 12.047?(3), b = 4.453?(1), c = 11.023?(3)?Å and V = 591.3?(3)?Å(3) [?calc = 1281.8?(7)?kg?m(-3)] at 10?K. The single-crystal data collected at 10 and 100?K are complemented by X-ray powder diffraction data measured from 245 to 273?K, Raman spectra measured from 80 to 263?K and an athermal zero-pressure calculation of the electronic structure and phonon spectrum carried out using density functional theory (DFT). We find no evidence of a phase transition between 10 and 273?K; above 273?K, however, the title compound transforms first to ammonium sesquicarbonate monohydrate and subsequently to ammonium bicarbonate. The crystallographic and spectroscopic data and the calculations reveal a quite strongly hydrogen-bonded structure (EHB ? 30-40?kJ?mol(-1)), on the basis of H...O bond lengths and the topology of the electron density at the bond critical points, in which there is no free rotation of the ammonium cation at any temperature. The barrier to free rotation of the ammonium ions is estimated from the observed librational frequency to be ??36?kJ?mol(-1). The c-axis exhibits negative thermal expansion, but the thermal expansion behaviour of the a and b axes is ormal.

SUBMITTER: Fortes AD

PROVIDER: S-EPMC4468514 | biostudies-literature | 2014 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Structure, hydrogen bonding and thermal expansion of ammonium carbonate monohydrate.

Fortes A Dominic AD Wood Ian G IG Alfè Dario D Hernández Eduardo R ER Gutmann Matthias J MJ Sparkes Hazel A HA

Acta crystallographica Section B, Structural science, crystal engineering and materials 20141201 Pt 6

We have determined the crystal structure of ammonium carbonate monohydrate, (NH4)2CO3·H2O, using Laue single-crystal diffraction methods with pulsed neutron radiation. The crystal is orthorhombic, space group Pnma (Z = 4), with unit-cell dimensions a = 12.047 (3), b = 4.453 (1), c = 11.023 (3) Å and V = 591.3 (3) Å(3) [ρcalc = 1281.8 (7) kg m(-3)] at 10 K. The single-crystal data collected at 10 and 100 K are complemented by X-ray powder diffraction data measured from 245 to 273 K, Raman spectra ...[more]

PMID: 25449618

Similar Datasets

Project description:The crystal structure, hydrogen bonding, mechanical properties and Raman spectrum of the lead uranyl silicate monohydrate mineral kasolite, Pb(UO2)(SiO4)·H2O, are investigated by means of first-principles solid-state methods based on density functional theory using plane waves and pseudopotentials. The computed unit cell parameters, bond lengths and angles and X-ray powder pattern of kasolite are found to be in very good agreement with their experimental counterparts. The calculated hydrogen atom positions and associated hydrogen bond structure in the unit cell of kasolite confirmed the hydrogen bond scheme previously determined from X-ray diffraction data. The kasolite crystal structure is formed from uranyl silicate layers having the uranophane sheet anion-topology. The lead ions and water molecules are located in the interlayer space. Water molecules belong to the coordination structure of lead interlayer ions and reinforce the structure by hydrogen bonding between the uranyl silicate sheets. The hydrogen bonding in kasolite is strong and dual, that is, the water molecules are distributed in pairs, held together by two symmetrically related hydrogen bonds, one being directed from the first water molecule to the second one and the other from the second water molecule to the first one. As a result of the full structure determination of kasolite, the determination of its mechanical properties and Raman spectrum becomes possible using theoretical methods. The mechanical properties and mechanical stability of the structure of kasolite are studied using the finite deformation technique. The bulk modulus and its pressure derivatives, the Young and shear moduli, the Poisson ratio and the ductility, hardness and anisotropy indices are reported. Kasolite is a hard and brittle mineral possessing a large bulk modulus of the order of B ∼ 71 GPa. The structure is mechanically stable and very isotropic. The large mechanical isotropy of the structure is unexpected since layered structures are commonly very anisotropic and results from the strong dual hydrogen bonding among the uranyl silicate sheets. The experimental Raman spectrum of kasolite is recorded from a natural mineral sample from the Jánská vein, Příbram base metal ore district, Czech Republic, and determined by using density functional perturbation theory. The agreement is excellent and, therefore, the theoretical calculations are employed to assign the experimental spectrum. Besides, the theoretical results are used to guide the resolution into single components of the bands from the experimental spectrum. A large number of kasolite Raman bands are reassigned. Three bands of the experimental spectrum located at the wavenumbers 1015, 977 and 813 cm-1, are identified as combination bands.

Dataset Information

Structure, hydrogen bonding and thermal expansion of ammonium carbonate monohydrate.

Publications

Structure, hydrogen bonding and thermal expansion of ammonium carbonate monohydrate.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets