Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides
The crystal structures, interactions, and contacts analyses of four <i>N</i>-(ferrocenylalkyl)benzene-carboxamide derivatives are described as the <i>N</i>-(ferrocenylmethyl)benzenecarboxamide <b>4a</b>, <i>N</i>-(ferrocenylmethyl)-2,6-difluorobenzenec...
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2025-03-01
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| author | John F. Gallagher Christian Jelsch Peter T. M. Kenny Alan J. Lough |
| author_facet | John F. Gallagher Christian Jelsch Peter T. M. Kenny Alan J. Lough |
| author_sort | John F. Gallagher |
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| description | The crystal structures, interactions, and contacts analyses of four <i>N</i>-(ferrocenylalkyl)benzene-carboxamide derivatives are described as the <i>N</i>-(ferrocenylmethyl)benzenecarboxamide <b>4a</b>, <i>N</i>-(ferrocenylmethyl)-2,6-difluorobenzenecarboxamide <b>4e</b>, <i>N</i>-(ferrocenylmethyl)pentafluorobenzenecarboxamide <b>4f</b> and <i>N</i>-(ferrocenylethyl)-4-fluorobenzenecarboxamide <b>5</b>. Intermolecular amide⋯amide hydrogen-bonding interactions as 1D intermolecular chains are present in all four crystal structures, with N⋯O distances ranging from 2.819 (2) to 2.924 (3) Å. Three of the crystal structures have one molecule per asymmetric unit, except the phenyl <b>4a</b>, which has <i>Z</i>’=2. In the structure of <b>4a</b>, Fc(C-H)⋯(phenyl) and <sub>phenyl</sub>C-H⋯π(C<sub>5</sub>H<sub>4</sub>) ring interactions dominate the interaction landscape, together with (1:1) face-to-face (phenyl)⋯(phenyl) and (C<sub>5</sub>H<sub>5</sub>)⋯(C<sub>5</sub>H<sub>5</sub>) ring stacked pairs (Fc = ferrocenyl moiety). In <b>4e</b>, interlocking ferrocenyls, short C-H⋯(C-F) and C-H⋯O hydrogen bonds are the only additional notable intermolecular interactions. In the pentafluorophenyl derivative <b>4f</b>, a remarkable selection of interactions is present with interwoven 1D ferrocenyl⋯(C<sub>6</sub>F<sub>5</sub>) stacking and C-H⋯F interactions; molecules aggregate forming impressive 1D columns comprising intertwined (Fc⋯C<sub>6</sub>F<sub>5</sub>⋯)<sub>n</sub> ring stacking. In the ethyl bridged system <b>5</b>, C-H⋯F and C-H⋯π (arene) contacts with (4-fluorobenzene) ring⋯ring pairs combine and stack about inversion centres. The reported <i>para</i>-F substituted structure <b>REYWOU</b> (<b>4d</b>) is used for comparisons with the <b>4a</b>, <b>4e</b>, <b>4f</b>, and <b>5</b> crystal structures. In view of the rich interaction chemistry, contacts enrichment analyses of the Hirshfeld surface highlights several interesting features in all five ferrocenylalkylcarboxamide structures. |
| format | Article |
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| spelling | doaj-art-b4c7ae31deb04ebd933dfab78fcf08e02025-08-20T02:28:33ZengMDPI AGCrystals2073-43522025-03-0115429910.3390/cryst15040299Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)BenzenecarboxamidesJohn F. Gallagher0Christian Jelsch1Peter T. M. Kenny2Alan J. Lough3School of Chemical Sciences, Dublin City University, D09 V209 Dublin, IrelandCRM2, CNRS UMR 7036, Faculté des Sciences et Technologies, Université de Lorraine, 54000 Nancy, FranceSchool of Chemical Sciences, Dublin City University, D09 V209 Dublin, IrelandDepartment of Chemistry, University of Toronto, Toronto, ON M5S 3H6, CanadaThe crystal structures, interactions, and contacts analyses of four <i>N</i>-(ferrocenylalkyl)benzene-carboxamide derivatives are described as the <i>N</i>-(ferrocenylmethyl)benzenecarboxamide <b>4a</b>, <i>N</i>-(ferrocenylmethyl)-2,6-difluorobenzenecarboxamide <b>4e</b>, <i>N</i>-(ferrocenylmethyl)pentafluorobenzenecarboxamide <b>4f</b> and <i>N</i>-(ferrocenylethyl)-4-fluorobenzenecarboxamide <b>5</b>. Intermolecular amide⋯amide hydrogen-bonding interactions as 1D intermolecular chains are present in all four crystal structures, with N⋯O distances ranging from 2.819 (2) to 2.924 (3) Å. Three of the crystal structures have one molecule per asymmetric unit, except the phenyl <b>4a</b>, which has <i>Z</i>’=2. In the structure of <b>4a</b>, Fc(C-H)⋯(phenyl) and <sub>phenyl</sub>C-H⋯π(C<sub>5</sub>H<sub>4</sub>) ring interactions dominate the interaction landscape, together with (1:1) face-to-face (phenyl)⋯(phenyl) and (C<sub>5</sub>H<sub>5</sub>)⋯(C<sub>5</sub>H<sub>5</sub>) ring stacked pairs (Fc = ferrocenyl moiety). In <b>4e</b>, interlocking ferrocenyls, short C-H⋯(C-F) and C-H⋯O hydrogen bonds are the only additional notable intermolecular interactions. In the pentafluorophenyl derivative <b>4f</b>, a remarkable selection of interactions is present with interwoven 1D ferrocenyl⋯(C<sub>6</sub>F<sub>5</sub>) stacking and C-H⋯F interactions; molecules aggregate forming impressive 1D columns comprising intertwined (Fc⋯C<sub>6</sub>F<sub>5</sub>⋯)<sub>n</sub> ring stacking. In the ethyl bridged system <b>5</b>, C-H⋯F and C-H⋯π (arene) contacts with (4-fluorobenzene) ring⋯ring pairs combine and stack about inversion centres. The reported <i>para</i>-F substituted structure <b>REYWOU</b> (<b>4d</b>) is used for comparisons with the <b>4a</b>, <b>4e</b>, <b>4f</b>, and <b>5</b> crystal structures. In view of the rich interaction chemistry, contacts enrichment analyses of the Hirshfeld surface highlights several interesting features in all five ferrocenylalkylcarboxamide structures.https://www.mdpi.com/2073-4352/15/4/299aggregationaromatic ring stackingcolumnarcontact enrichment analysiscrystal structureferrocene |
| spellingShingle | John F. Gallagher Christian Jelsch Peter T. M. Kenny Alan J. Lough Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides Crystals aggregation aromatic ring stacking columnar contact enrichment analysis crystal structure ferrocene |
| title | Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides |
| title_full | Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides |
| title_fullStr | Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides |
| title_full_unstemmed | Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides |
| title_short | Impressive 1D (Ferrocenyl⋯C<sub>6</sub>F<sub>5</sub><i>R</i>⋯)<sub>n</sub> Stacking Due to Cooperative Interactions in <i>N</i>-(Ferrocenylmethyl)Pentafluorobenzenecarboxamide: Four Crystal Structures and Contacts Analyses in <i>N</i>-(Ferrocenylalkyl)Benzenecarboxamides |
| title_sort | impressive 1d ferrocenyl⋯c sub 6 sub f sub 5 sub i r i ⋯ sub n sub stacking due to cooperative interactions in i n i ferrocenylmethyl pentafluorobenzenecarboxamide four crystal structures and contacts analyses in i n i ferrocenylalkyl benzenecarboxamides |
| topic | aggregation aromatic ring stacking columnar contact enrichment analysis crystal structure ferrocene |
| url | https://www.mdpi.com/2073-4352/15/4/299 |
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