{"title":"六种聚(芳基亚磺酰基)和聚(芳基硫酰基)二茂铁的分子和晶体结构。","authors":"Tobias Blockhaus, Karlheinz Sünkel","doi":"10.1107/S2053229624009318","DOIUrl":null,"url":null,"abstract":"<p><p>Starting from (p-tolylsulfinyl)ferrocene (1), a mixture of the complete series [CpFe{C<sub>5</sub>H<sub>5-n</sub>(SOTol-p)<sub>n</sub>}] (n = 2-4) (2-4) in all regioisomers was obtained. After chromatographic separation, crystals of 1,2-bis[(4-methylbenzene)sulfinyl]ferrocene, 2a, and 1,3-bis[(4-methylbenzene)sulfinyl]ferrocene, 2b, both [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>19</sub>H<sub>17</sub>O<sub>2</sub>S<sub>2</sub>)], as well as of 1,2,3-tris[(4-methylbenzene)sulfinyl]ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>26</sub>H<sub>23</sub>O<sub>3</sub>S<sub>3</sub>)], 3a, and 1,2,3,4-tetrakis[(4-methylbenzene)sulfinyl]ferrocene ethyl acetate 0.75-solvate, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>33</sub>H<sub>29</sub>O<sub>4</sub>S<sub>4</sub>)]·0.75C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>, 4, could be isolated. Their molecular and crystal structures are compared with each other and also with the so far unreported structures of related 1,2-bis(phenylsulfanyl)ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>17</sub>H<sub>13</sub>S<sub>2</sub>)], 5, and 1,2,3,4-tetrakis(phenylsulfanyl)ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>29</sub>H<sub>21</sub>S<sub>4</sub>)], 6. In all the sulfinyl structures, the O atoms of the S=O groups are in equatorial positions, except for that in tetrasubstituted 4. All the arene rings of these compounds (except for one ring in 4) are in axial positions directed away from the Fe atom, mostly in a near perpendicular orientation with respect to the plane of the cyclopentadienyl ring. The main intermolecular interactions in the crystals are C-H...H-C, C-H...π and C-H...O, while C-H...S interactions are much less important, except for tetrasulfanyl compound 6. π-π interactions (intramolecular) are only important in compound 3a. Hirshfeld analysis shows that dispersion terms are dominant for the interaction energies of all six compounds. In general, the calculated total interaction energies increase with increasing number of substituents and are higher for the sulfinyl than for the sulfanyl groups.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"716-727"},"PeriodicalIF":0.7000,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11535883/pdf/","citationCount":"0","resultStr":"{\"title\":\"Molecular and crystal structures of six poly(arylsulfinyl)- and poly(arylsulfanyl)ferrocenes.\",\"authors\":\"Tobias Blockhaus, Karlheinz Sünkel\",\"doi\":\"10.1107/S2053229624009318\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Starting from (p-tolylsulfinyl)ferrocene (1), a mixture of the complete series [CpFe{C<sub>5</sub>H<sub>5-n</sub>(SOTol-p)<sub>n</sub>}] (n = 2-4) (2-4) in all regioisomers was obtained. After chromatographic separation, crystals of 1,2-bis[(4-methylbenzene)sulfinyl]ferrocene, 2a, and 1,3-bis[(4-methylbenzene)sulfinyl]ferrocene, 2b, both [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>19</sub>H<sub>17</sub>O<sub>2</sub>S<sub>2</sub>)], as well as of 1,2,3-tris[(4-methylbenzene)sulfinyl]ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>26</sub>H<sub>23</sub>O<sub>3</sub>S<sub>3</sub>)], 3a, and 1,2,3,4-tetrakis[(4-methylbenzene)sulfinyl]ferrocene ethyl acetate 0.75-solvate, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>33</sub>H<sub>29</sub>O<sub>4</sub>S<sub>4</sub>)]·0.75C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>, 4, could be isolated. Their molecular and crystal structures are compared with each other and also with the so far unreported structures of related 1,2-bis(phenylsulfanyl)ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>17</sub>H<sub>13</sub>S<sub>2</sub>)], 5, and 1,2,3,4-tetrakis(phenylsulfanyl)ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>29</sub>H<sub>21</sub>S<sub>4</sub>)], 6. In all the sulfinyl structures, the O atoms of the S=O groups are in equatorial positions, except for that in tetrasubstituted 4. All the arene rings of these compounds (except for one ring in 4) are in axial positions directed away from the Fe atom, mostly in a near perpendicular orientation with respect to the plane of the cyclopentadienyl ring. The main intermolecular interactions in the crystals are C-H...H-C, C-H...π and C-H...O, while C-H...S interactions are much less important, except for tetrasulfanyl compound 6. π-π interactions (intramolecular) are only important in compound 3a. Hirshfeld analysis shows that dispersion terms are dominant for the interaction energies of all six compounds. In general, the calculated total interaction energies increase with increasing number of substituents and are higher for the sulfinyl than for the sulfanyl groups.</p>\",\"PeriodicalId\":7115,\"journal\":{\"name\":\"Acta Crystallographica Section C Structural Chemistry\",\"volume\":\" \",\"pages\":\"716-727\"},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2024-11-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11535883/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta Crystallographica Section C Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2053229624009318\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/10/4 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section C Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2053229624009318","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/4 0:00:00","PubModel":"Epub","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Molecular and crystal structures of six poly(arylsulfinyl)- and poly(arylsulfanyl)ferrocenes.
Starting from (p-tolylsulfinyl)ferrocene (1), a mixture of the complete series [CpFe{C5H5-n(SOTol-p)n}] (n = 2-4) (2-4) in all regioisomers was obtained. After chromatographic separation, crystals of 1,2-bis[(4-methylbenzene)sulfinyl]ferrocene, 2a, and 1,3-bis[(4-methylbenzene)sulfinyl]ferrocene, 2b, both [Fe(C5H5)(C19H17O2S2)], as well as of 1,2,3-tris[(4-methylbenzene)sulfinyl]ferrocene, [Fe(C5H5)(C26H23O3S3)], 3a, and 1,2,3,4-tetrakis[(4-methylbenzene)sulfinyl]ferrocene ethyl acetate 0.75-solvate, [Fe(C5H5)(C33H29O4S4)]·0.75C4H8O2, 4, could be isolated. Their molecular and crystal structures are compared with each other and also with the so far unreported structures of related 1,2-bis(phenylsulfanyl)ferrocene, [Fe(C5H5)(C17H13S2)], 5, and 1,2,3,4-tetrakis(phenylsulfanyl)ferrocene, [Fe(C5H5)(C29H21S4)], 6. In all the sulfinyl structures, the O atoms of the S=O groups are in equatorial positions, except for that in tetrasubstituted 4. All the arene rings of these compounds (except for one ring in 4) are in axial positions directed away from the Fe atom, mostly in a near perpendicular orientation with respect to the plane of the cyclopentadienyl ring. The main intermolecular interactions in the crystals are C-H...H-C, C-H...π and C-H...O, while C-H...S interactions are much less important, except for tetrasulfanyl compound 6. π-π interactions (intramolecular) are only important in compound 3a. Hirshfeld analysis shows that dispersion terms are dominant for the interaction energies of all six compounds. In general, the calculated total interaction energies increase with increasing number of substituents and are higher for the sulfinyl than for the sulfanyl groups.
期刊介绍:
Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.