Characterization of tetra-n-butylphosphonium bromide semiclathrate hydrate by crystal structure analysis

Sanehiro Muromachi, Satoshi Takeya, Yoshitaka Yamamoto, Ryo Ohmura

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

We report the crystal structure analysis of the semiclathrate hydrate of tetra-n-butylphosphonium bromide (TBPB), which is a candidate material for refrigeration and gas-capture technologies. Refinement of the single crystal X-ray diffraction measurements revealed that the found structure of the TBPB hydrate has an orthorhombic structure, with the space group Pmma, and unit cell parameters a = 21.065(5), b = 12.657(3) and c = 11.992(3) Å. The chemical formula is TBPB·38H2O. The TBP ion is accommodated in a combined cage that consists of two tetrakaidecahedra and two pentakaidecahedra. The structure features three dodecahedral cages for each TBPB molecule that may accommodate small gas molecules (e.g., CH4, CO2 and N 2). The structure determined in this work is compared in detail with that of a similar hydrate, tetra-n-butylammonium bromide (TBAB) hydrate. In contrast to the TBAB hydrates, the most stable structure of the TBPB hydrate is not tetragonal but orthorhombic. Since C-P has a longer bond length than C-N, the TBP ion was packed tightly by the combined cage, having complex disorder. The relative comparison of the atom positions showed that the difference in the bond lengths of the two cations is counteracted by the displacement of water molecules in the TBPB hydrate lattice.

Original languageEnglish
Pages (from-to)2056-2060
Number of pages5
JournalCrystEngComm
Volume16
Issue number10
DOIs
Publication statusPublished - 2014 Mar 14

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Hydrates
Bromides
hydrates
bromides
Crystal structure
crystal structure
Bond length
Molecules
Gases
Ions
molecules
Refrigeration
gases
Cations
ions
Positive ions
Single crystals
disorders
cations
X ray diffraction

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Characterization of tetra-n-butylphosphonium bromide semiclathrate hydrate by crystal structure analysis. / Muromachi, Sanehiro; Takeya, Satoshi; Yamamoto, Yoshitaka; Ohmura, Ryo.

In: CrystEngComm, Vol. 16, No. 10, 14.03.2014, p. 2056-2060.

Research output: Contribution to journalArticle

Muromachi, Sanehiro ; Takeya, Satoshi ; Yamamoto, Yoshitaka ; Ohmura, Ryo. / Characterization of tetra-n-butylphosphonium bromide semiclathrate hydrate by crystal structure analysis. In: CrystEngComm. 2014 ; Vol. 16, No. 10. pp. 2056-2060.
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