TY - JOUR

T1 - Ionic Clathrate Hydrates of Tetra-n-Butylammonium Nitrate (TBANO3) and Mixed TBA(NO3,OH): Novel Superstructures of Tetragonal Structure I

AU - Rodionova, T. V.

AU - Odintsov, D. S.

AU - Manakov, A. Yu

AU - Komarov, V. Yu

PY - 2019/10/1

Y1 - 2019/10/1

N2 - The structures of an ionic clathrate hydrate of tetra-n-butylammonium nitrate TBANO3·26.7H2O and mixed TBA(NO3)1 −x(OH)x·(31.5 − x)H2O hydrate obtained from a mixture of tetra-n-butylammonium nitrate and tetra-n-butylammonium hydroxide are determined by single crystal X-ray diffraction. These structures are new types of superstructures based on classical tetragonal structure I with four- and twofold unit cells volumes for TBANO3·26.7H2O and TBA(NO3)1−x(OH)x·(31.5 − x)H2O respectively. The superstructures form as a result of ordering in the arrangement of multicompartment cavities of the water-anionic framework. A TBA cation is displaced from the center of combined cavities due to the anisotropic environment of the anions, which leads to an additional symmetry reduction. The modes of the nitrate anion incorporation into the water framework of ionic clathrate hydrates are determined for the first time.

AB - The structures of an ionic clathrate hydrate of tetra-n-butylammonium nitrate TBANO3·26.7H2O and mixed TBA(NO3)1 −x(OH)x·(31.5 − x)H2O hydrate obtained from a mixture of tetra-n-butylammonium nitrate and tetra-n-butylammonium hydroxide are determined by single crystal X-ray diffraction. These structures are new types of superstructures based on classical tetragonal structure I with four- and twofold unit cells volumes for TBANO3·26.7H2O and TBA(NO3)1−x(OH)x·(31.5 − x)H2O respectively. The superstructures form as a result of ordering in the arrangement of multicompartment cavities of the water-anionic framework. A TBA cation is displaced from the center of combined cavities due to the anisotropic environment of the anions, which leads to an additional symmetry reduction. The modes of the nitrate anion incorporation into the water framework of ionic clathrate hydrates are determined for the first time.

KW - disordered structures

KW - ionic clathrate hydrates

KW - local ordering

KW - structures

KW - tetra-n-butylammonium hydroxide

KW - tetra-n-butylammonium nitrate

KW - X-ray crystallographic analysis

KW - MIXTURE

KW - TBAB

KW - COLD-STORAGE MATERIAL

KW - HYDROGEN STORAGE

KW - CO2 CAPTURE

KW - BROMIDE

KW - FLUE-GAS

KW - SEPARATION

KW - BUTYL

KW - AMMONIUM-CHLORIDE

UR - http://www.scopus.com/inward/record.url?scp=85074650963&partnerID=8YFLogxK

U2 - 10.1134/S0022476619100123

DO - 10.1134/S0022476619100123

M3 - Article

AN - SCOPUS:85074650963

VL - 60

SP - 1660

EP - 1669

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 10

ER -