Benita Barton*, Cedric W McCleland*, Mino R Caira*, Muhammad-Ameen Adam and Eric C Hosten,
{"title":"顺式和反式-1,4-双(二苯基羟甲基)环己烷非对映异构体混合物在吡啶和甲基吡啶溶液中的主-客络合:显著的包合选择性和不常见的宿主构象","authors":"Benita Barton*, Cedric W McCleland*, Mino R Caira*, Muhammad-Ameen Adam and Eric C Hosten, ","doi":"10.1021/acs.cgd.4c0104110.1021/acs.cgd.4c01041","DOIUrl":null,"url":null,"abstract":"<p >A 0.85:0.15 <i>cis</i>:<i>trans</i> diastereoisomeric mixture of 1,4-bis(diphenylhydroxymethyl)cyclohexane has been shown to form host–guest inclusion compounds with pyridine (<b>PYR</b>) and the three isomeric methylpyridines (<b>2MP</b>, <b>3MP</b>, <b>4MP</b>). Diastereoisomeric mixtures of the host compound were found in the crystalline products, but with the <i>trans</i> isomer dominating, ranging from 69% for <b>PYR</b> to 97% for <b>4MP</b>. Crystals selected from these mixtures for SCXRD analysis were found to comprise the <i>cis</i> host species (<b>H1</b>) for <b>PYR</b> and <b>3MP</b> and the <i>trans</i> isomer (<b>H2</b>) in the case of <b>2MP</b> and <b>4MP</b>. Thermal experiments established that the most stable inclusion complex is obtained with <b>PYR</b> because its release occurs at a higher temperature compared with the three <b>MPs</b> in their respective complexes. In mixed solvent crystallization experiments, the host was usually selective toward <b>PYR</b>, unsurprising given that the <b>PYR</b> complex is the most stable of the four. We therefore suggest that this host compound has potential to separate binary mixtures of the guest solutions considered here. SCXRD analysis also established that the (guest)N···H–O(<b>H1</b>) hydrogen bond is shorter for <b>PYR</b> than the <b>MPs</b>, which is consistent with the higher selectivity of the host species observed for <b>PYR</b>. Hirshfeld surface analyses revealed more extensive C···H/H···C and H···N/N···H interactions between <b>PYR</b> and the host compared compared to the host–guest complexes of the <b>MPs</b>. The crystal structure determination on <b>H1</b>·2(<b>PYR</b>) furthermore revealed that the cyclohexyl ring adopts the unexpected boat conformation. Conformational analysis of <b>H1</b>·2(<b>PYR</b>) as well as the individual host compounds was performed through molecular modeling at the molecular mechanics (MMFF) and DFT (ωB97X-D/6-31G*) levels. This established that when the diastereoisomeric host mixture is crystallized from <b>PYR</b>, a comparatively high-energy host–guest complex is preferred, with a high-energy boat conformer of <i>cis</i>-1,4-bis(diphenylhydroxymethyl)cyclohexane being selected.</p><p >The cyclohexyl moiety of the host compound 1,4-bis(diphenylhydroxymethyl)cyclohexane adopted a higher energy boat conformation in its complex with its preferred guest species, pyridine.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01041","citationCount":"0","resultStr":"{\"title\":\"Host–Guest Complexations of a Diastereoisomeric Mixture of cis- and trans-1,4-Bis(diphenylhydroxymethyl)cyclohexane in Pyridine and Methylpyridine Solutions: Significant Inclusion Selectivities and an Uncommon Host Conformation\",\"authors\":\"Benita Barton*, Cedric W McCleland*, Mino R Caira*, Muhammad-Ameen Adam and Eric C Hosten, \",\"doi\":\"10.1021/acs.cgd.4c0104110.1021/acs.cgd.4c01041\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A 0.85:0.15 <i>cis</i>:<i>trans</i> diastereoisomeric mixture of 1,4-bis(diphenylhydroxymethyl)cyclohexane has been shown to form host–guest inclusion compounds with pyridine (<b>PYR</b>) and the three isomeric methylpyridines (<b>2MP</b>, <b>3MP</b>, <b>4MP</b>). Diastereoisomeric mixtures of the host compound were found in the crystalline products, but with the <i>trans</i> isomer dominating, ranging from 69% for <b>PYR</b> to 97% for <b>4MP</b>. Crystals selected from these mixtures for SCXRD analysis were found to comprise the <i>cis</i> host species (<b>H1</b>) for <b>PYR</b> and <b>3MP</b> and the <i>trans</i> isomer (<b>H2</b>) in the case of <b>2MP</b> and <b>4MP</b>. Thermal experiments established that the most stable inclusion complex is obtained with <b>PYR</b> because its release occurs at a higher temperature compared with the three <b>MPs</b> in their respective complexes. In mixed solvent crystallization experiments, the host was usually selective toward <b>PYR</b>, unsurprising given that the <b>PYR</b> complex is the most stable of the four. We therefore suggest that this host compound has potential to separate binary mixtures of the guest solutions considered here. SCXRD analysis also established that the (guest)N···H–O(<b>H1</b>) hydrogen bond is shorter for <b>PYR</b> than the <b>MPs</b>, which is consistent with the higher selectivity of the host species observed for <b>PYR</b>. Hirshfeld surface analyses revealed more extensive C···H/H···C and H···N/N···H interactions between <b>PYR</b> and the host compared compared to the host–guest complexes of the <b>MPs</b>. The crystal structure determination on <b>H1</b>·2(<b>PYR</b>) furthermore revealed that the cyclohexyl ring adopts the unexpected boat conformation. Conformational analysis of <b>H1</b>·2(<b>PYR</b>) as well as the individual host compounds was performed through molecular modeling at the molecular mechanics (MMFF) and DFT (ωB97X-D/6-31G*) levels. This established that when the diastereoisomeric host mixture is crystallized from <b>PYR</b>, a comparatively high-energy host–guest complex is preferred, with a high-energy boat conformer of <i>cis</i>-1,4-bis(diphenylhydroxymethyl)cyclohexane being selected.</p><p >The cyclohexyl moiety of the host compound 1,4-bis(diphenylhydroxymethyl)cyclohexane adopted a higher energy boat conformation in its complex with its preferred guest species, pyridine.</p>\",\"PeriodicalId\":34,\"journal\":{\"name\":\"Crystal Growth & Design\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-10-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01041\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Crystal Growth & Design\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.cgd.4c01041\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.cgd.4c01041","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Host–Guest Complexations of a Diastereoisomeric Mixture of cis- and trans-1,4-Bis(diphenylhydroxymethyl)cyclohexane in Pyridine and Methylpyridine Solutions: Significant Inclusion Selectivities and an Uncommon Host Conformation
A 0.85:0.15 cis:trans diastereoisomeric mixture of 1,4-bis(diphenylhydroxymethyl)cyclohexane has been shown to form host–guest inclusion compounds with pyridine (PYR) and the three isomeric methylpyridines (2MP, 3MP, 4MP). Diastereoisomeric mixtures of the host compound were found in the crystalline products, but with the trans isomer dominating, ranging from 69% for PYR to 97% for 4MP. Crystals selected from these mixtures for SCXRD analysis were found to comprise the cis host species (H1) for PYR and 3MP and the trans isomer (H2) in the case of 2MP and 4MP. Thermal experiments established that the most stable inclusion complex is obtained with PYR because its release occurs at a higher temperature compared with the three MPs in their respective complexes. In mixed solvent crystallization experiments, the host was usually selective toward PYR, unsurprising given that the PYR complex is the most stable of the four. We therefore suggest that this host compound has potential to separate binary mixtures of the guest solutions considered here. SCXRD analysis also established that the (guest)N···H–O(H1) hydrogen bond is shorter for PYR than the MPs, which is consistent with the higher selectivity of the host species observed for PYR. Hirshfeld surface analyses revealed more extensive C···H/H···C and H···N/N···H interactions between PYR and the host compared compared to the host–guest complexes of the MPs. The crystal structure determination on H1·2(PYR) furthermore revealed that the cyclohexyl ring adopts the unexpected boat conformation. Conformational analysis of H1·2(PYR) as well as the individual host compounds was performed through molecular modeling at the molecular mechanics (MMFF) and DFT (ωB97X-D/6-31G*) levels. This established that when the diastereoisomeric host mixture is crystallized from PYR, a comparatively high-energy host–guest complex is preferred, with a high-energy boat conformer of cis-1,4-bis(diphenylhydroxymethyl)cyclohexane being selected.
The cyclohexyl moiety of the host compound 1,4-bis(diphenylhydroxymethyl)cyclohexane adopted a higher energy boat conformation in its complex with its preferred guest species, pyridine.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.