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Crystal structures of ammonium citrates

Published online by Cambridge University Press:  11 December 2018

Austin M. Wheatley  and
James A. Kaduk Open the ORCID record for James A. Kaduk [Opens in a new window]
Austin M. Wheatley
Affiliation:
North Central College, 131 S. Loomis St., Naperville IL 60540, USA
James A. Kaduk*
Affiliation:
North Central College, 131 S. Loomis St., Naperville IL 60540, USA Illinois Institute of Technology, 3101 S. Dearborn St., Chicago IL 60616, USA
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]
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Abstract

The crystal structures of (NH4)H2C6H5O7 and (NH4)3C6H5O7 have been determined using a combination of powder and single crystal techniques. The structure of (NH4)2HC6H5O7 has been determined previously by single crystal diffraction. All three structures were optimized using density functional techniques. The crystal structures are dominated by N-H⋅⋅⋅O hydrogen bonds, though O-H⋅⋅⋅O hydrogen bonds are also important. In (NH4)H2C6H5O7 very strong centrosymmetric charge-assisted O-H-O hydrogen bonds link one end of the citrate into chains along the b-axis. A more-normal O-H⋅⋅⋅O hydrogen bond links the other end of the citrate to the central ionized carboxyl group. In (NH4)2HC6H5O7, the very strong centrosymmetric O-H-O hydrogen bonds link the citrates into zig-zag chains along the b-axis. The citrates occupy layers parallel to the bc plane, and the ammonium ions link the layers through N-H⋅⋅⋅O hydrogen bonds. In (NH4)3C6H5O7, the hydroxyl group forms a hydrogen bond to a terminal carboxylate, and there is an extensive array of N-H⋅⋅⋅O hydrogen bonds. The energies of the density functional theory-optimized structures lead to a correlation between the energy of an N-H⋅⋅⋅O hydrogen bond and the Mulliken overlap population: E(N-H⋅⋅⋅O) (kcal/mole) = 23.1(overlap)½. Powder patterns of (NH4)H2C6H5O7 and (NH4)3C6H5O7 have been submitted to International Centre for Diffraction Data for inclusion in the powder diffraction file.

Keywords

ammoniumcitratepowder diffractionRietveld refinementdensity functional theory
Type
Technical Article
Information
Powder Diffraction , Volume 34 , Issue 1 , March 2019 , pp. 35 - 43
Copyright
Copyright © International Centre for Diffraction Data 2018 

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