Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method
The structural determination of clathrate hydrates, nonstoichiometric crystalline host-guest materials, is challenging because of the dynamical disorder and partial cage occupancies of the guest molecules. The application of direct space methods with Rietveld analysis can determine the powder X-ray...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2018-08-01
|
| Series: | Crystals |
| Subjects: | |
| Online Access: | http://www.mdpi.com/2073-4352/8/8/328 |
| _version_ | 1798039235926687744 |
|---|---|
| author | Yun-Ho Ahn Byeonggwan Lee Kyuchul Shin |
| author_facet | Yun-Ho Ahn Byeonggwan Lee Kyuchul Shin |
| author_sort | Yun-Ho Ahn |
| collection | DOAJ |
| description | The structural determination of clathrate hydrates, nonstoichiometric crystalline host-guest materials, is challenging because of the dynamical disorder and partial cage occupancies of the guest molecules. The application of direct space methods with Rietveld analysis can determine the powder X-ray diffraction (PXRD) patterns of clathrates. Here, we conducted Rietveld analysis with the direct space method for the structural determination of binary tetrahydrofuran (THF) + O2 and 3-hydroxytetrahydrofuran (3-OH THF) + O2 clathrate hydrates in order to identify the hydroxyl substituent effect on interactions between the host framework and the cyclic ether guest molecules. The refined PXRD results reveal that the hydroxyl groups are hydrogen-bonded to host hexagonal rings of water molecules in the 51264 cage, while any evidences of hydrogen bonding between THF guests and the host framework were not observed from PXRD at 100 K. This guest-host hydrogen bonding is thought to induce slightly larger 512 cages in the 3-OH THF hydrate than those in the THF hydrate. Consequently, the disorder dynamics of the secondary guest molecules also can be affected by the hydrogen bonding of larger guest molecules. The structural information of binary clathrate hydrates reported here can improve the understanding of the host-guest interactions occurring in clathrate hydrates and the specialized methodologies for crystal structure determination of clathrate hydrates. |
| first_indexed | 2024-04-11T21:51:06Z |
| format | Article |
| id | doaj.art-36bbadd2655840029f7a2f6d64385532 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-04-11T21:51:06Z |
| publishDate | 2018-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-36bbadd2655840029f7a2f6d643855322022-12-22T04:01:14ZengMDPI AGCrystals2073-43522018-08-018832810.3390/cryst8080328cryst8080328Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space MethodYun-Ho Ahn0Byeonggwan Lee1Kyuchul Shin2School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30318, USADepartment of Applied Chemistry, School of Applied Chemical Engineering, Kyungpook National University, Daegu 41566, KoreaDepartment of Applied Chemistry, School of Applied Chemical Engineering, Kyungpook National University, Daegu 41566, KoreaThe structural determination of clathrate hydrates, nonstoichiometric crystalline host-guest materials, is challenging because of the dynamical disorder and partial cage occupancies of the guest molecules. The application of direct space methods with Rietveld analysis can determine the powder X-ray diffraction (PXRD) patterns of clathrates. Here, we conducted Rietveld analysis with the direct space method for the structural determination of binary tetrahydrofuran (THF) + O2 and 3-hydroxytetrahydrofuran (3-OH THF) + O2 clathrate hydrates in order to identify the hydroxyl substituent effect on interactions between the host framework and the cyclic ether guest molecules. The refined PXRD results reveal that the hydroxyl groups are hydrogen-bonded to host hexagonal rings of water molecules in the 51264 cage, while any evidences of hydrogen bonding between THF guests and the host framework were not observed from PXRD at 100 K. This guest-host hydrogen bonding is thought to induce slightly larger 512 cages in the 3-OH THF hydrate than those in the THF hydrate. Consequently, the disorder dynamics of the secondary guest molecules also can be affected by the hydrogen bonding of larger guest molecules. The structural information of binary clathrate hydrates reported here can improve the understanding of the host-guest interactions occurring in clathrate hydrates and the specialized methodologies for crystal structure determination of clathrate hydrates.http://www.mdpi.com/2073-4352/8/8/328clathrate hydratepowder X-ray diffractionRietveld refinement |
| spellingShingle | Yun-Ho Ahn Byeonggwan Lee Kyuchul Shin Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method Crystals clathrate hydrate powder X-ray diffraction Rietveld refinement |
| title | Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method |
| title_full | Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method |
| title_fullStr | Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method |
| title_full_unstemmed | Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method |
| title_short | Structural Identification of Binary Tetrahydrofuran + O2 and 3-Hydroxytetrahydrofuran + O2 Clathrate Hydrates by Rietveld Analysis with Direct Space Method |
| title_sort | structural identification of binary tetrahydrofuran o2 and 3 hydroxytetrahydrofuran o2 clathrate hydrates by rietveld analysis with direct space method |
| topic | clathrate hydrate powder X-ray diffraction Rietveld refinement |
| url | http://www.mdpi.com/2073-4352/8/8/328 |
| work_keys_str_mv | AT yunhoahn structuralidentificationofbinarytetrahydrofurano2and3hydroxytetrahydrofurano2clathratehydratesbyrietveldanalysiswithdirectspacemethod AT byeonggwanlee structuralidentificationofbinarytetrahydrofurano2and3hydroxytetrahydrofurano2clathratehydratesbyrietveldanalysiswithdirectspacemethod AT kyuchulshin structuralidentificationofbinarytetrahydrofurano2and3hydroxytetrahydrofurano2clathratehydratesbyrietveldanalysiswithdirectspacemethod |