{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T02:35:13Z","timestamp":1760150113096,"version":"build-2065373602"},"reference-count":22,"publisher":"MDPI AG","issue":"10","license":[{"start":{"date-parts":[[2023,10,14]],"date-time":"2023-10-14T00:00:00Z","timestamp":1697241600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"FCT\u2014Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UI\/BD\/152244\/2021"],"award-info":[{"award-number":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UI\/BD\/152244\/2021"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Institute of Molecular Sciences","award":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UI\/BD\/152244\/2021"],"award-info":[{"award-number":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UI\/BD\/152244\/2021"]}]},{"DOI":"10.13039\/501100001871","name":"FCT\u2014Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UI\/BD\/152244\/2021"],"award-info":[{"award-number":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UI\/BD\/152244\/2021"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Crystals"],"abstract":"<jats:p>DFT-D3 calculations based on structural X-ray diffraction data obtained for 3-oxo-camphorsulfonyl imine (1), camphorsulfonyl chloride (2) and seven camphor sulfonimines (O2SNC10H13NR, L1\u2212L7), from which L2 (R=4-OHC6H4), L4 (R=4-ClC6H4) and L6 (R=3,5-(CH3)2C6H3) are synthesized and characterized in this work, provide information into the intra- and inter-molecular interactions with concomitant elucidation of the supramolecular arrangement of the compounds. The DFT-D3 calculations performed in small clusters of two or three molecular units reproduce the interactions observed via X-ray analyses, showing that, as a general trend, the structural arrangement of the molecules is driven by electronic rather than by packing parameters. In all compounds, the self-assembly of 3D structures involves the sulfonyl imine group (-NSO2) either to establish hydrogen bonds through oxygen atoms or non-classic oxygen\u2013aliphatic hydrogen or non-bonding interactions (NBIs), which also involve sulfonyl oxygen atoms. Interestingly, the camphor sulfonimine compounds (L2, L3), having protic groups (R=C6H4X:X=OH, L2 or X=NH2, L3) at the aromatic imine substituents (=NR), present an extra \u03c0-\u03c0 stacking, which is absent in the other compounds\u2019 aromatic derivatives. The X-ray analysis shows that all the reported camphor sulfonimine compounds display the E configuration with respect to the imine substituent (R). The study of the redox behavior of the compounds by cyclic voltammetry enables insight into the solution properties of the compounds and the rationalization of the molecular interactions that stand in the solid and solution states. Camphor sulfonimine compounds (L) display appropriate binding atoms to coordinate transition metals. The results herein show that monodentate coordination through the nitrogen atom of the sulfonimine five-membered ring to the {Ag(NO3)} metal center is favored. When this imine nitrogen atom is not itself involved in the organic framework, DFT-D3 calculations show that the complexation does not affect the non-covalent interactions that are reproduced in the MOF structure.<\/jats:p>","DOI":"10.3390\/cryst13101499","type":"journal-article","created":{"date-parts":[[2023,10,14]],"date-time":"2023-10-14T14:38:42Z","timestamp":1697294322000},"page":"1499","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0672-1146","authenticated-orcid":false,"given":"Joana Pais","family":"da Costa","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences and Departamento de Engenharia Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Avenida Ant\u00f3nio Jos\u00e9 de Almeida, n. 12, 1000-043 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6825-1696","authenticated-orcid":false,"given":"Maria Fernanda Nascimento Neves","family":"de Carvalho","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences and Departamento de Engenharia Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Avenida Ant\u00f3nio Jos\u00e9 de Almeida, n. 12, 1000-043 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4740-0613","authenticated-orcid":false,"given":"Adelino Moura","family":"Galv\u00e3o","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences and Departamento de Engenharia Qu\u00edmica, Instituto Superior T\u00e9cnico, Campus Taguspark, Universidade de Lisboa, Avenida Professor Doutor Cavaco Silva, 2744-016 Porto Salvo, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2023,10,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5160","DOI":"10.1021\/ic00075a036","article-title":"Transition metal complexes of (1S,2S,3S)-3-hidroxy-camphorsultam","volume":"32","author":"Carvalho","year":"1993","journal-title":"Inorg. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"6270","DOI":"10.1021\/ic00104a042","article-title":"Synthesis, structure and electrochemistry of palladium complexes with camphor-derived chiral ligands","volume":"33","author":"Carvalho","year":"1994","journal-title":"Inorg. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"55","DOI":"10.1016\/j.jinorgbio.2016.11.003","article-title":"Synthesis and assessment of the cytotoxic and DNA binding properties of Ag(I) camphor sulphonylimine complexes","volume":"166","author":"Cardoso","year":"2017","journal-title":"J. Inorg. Biochem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2174","DOI":"10.1002\/asia.201800496","article-title":"Non-Bonding Interactions Enable the Selective Formation of Branched Products in Palladium-Catalyzed Allylic Substitution Reactions","volume":"13","author":"Wang","year":"2018","journal-title":"Chem. Asian J."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"3417","DOI":"10.1016\/j.bmcl.2005.05.025","article-title":"Potential new antitumor agents from an innovative combination of camphorato, a ramification of traditional Chinese medicine, with a platinum moiety","volume":"15","author":"Wang","year":"2005","journal-title":"Bioorg. Med. Chem. Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"4600","DOI":"10.1021\/acs.jpcb.7b01377","article-title":"Thermal Conductance in Cross-linked Polymers: Effects of Non-Bonding Interactions","volume":"121","author":"Rashidi","year":"2017","journal-title":"J. Phys. Chem. B"},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Carvalho, M.F.N.N., Leite, S., Costa, J.P., Galv\u00e3o, A.M., and Leit\u00e3o, J.H. (2019). Ag(I) camphor complexes: Antimicrobial activity by design. J. Inorg. Biochem., 199.","DOI":"10.1016\/j.jinorgbio.2019.110791"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1016\/j.poly.2014.11.020","article-title":"Insight into the cytotoxic activity of polynuclear Cu(I) camphor complexes","volume":"87","author":"Fernandes","year":"2015","journal-title":"Polyhedron"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"186","DOI":"10.1016\/j.jorganchem.2013.10.040","article-title":"Synthesis, characterization and study of properties of Zn(II) camphor derived complexes","volume":"760","author":"Fernandes","year":"2014","journal-title":"J. Organometal. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Goerigk, L. (2017). A comprehensive overview of the DFT-D3 London-dispersion correction. Non-Covalent Interact. Quantum Chem. Phys., 195\u2013219.","DOI":"10.1016\/B978-0-12-809835-6.00007-4"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Leit\u00e3o, J.H., Sousa, S.A., Leite, S.A., and Carvalho, M.F.N.N. (2018). Silver camphorimine complexes: Novel antibacterial compounds from old medicines. Antibiotics, 7.","DOI":"10.3390\/antibiotics7030065"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1441","DOI":"10.1039\/CT9028101441","article-title":"Studies of the terpenes and allied compounds. The sulphonation of camphor. I. Camphorsulphonic acid (reychler): The formation of anhydramides","volume":"81","author":"Armstrong","year":"1902","journal-title":"J. Chem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"10484","DOI":"10.1039\/C8NJ00536B","article-title":"Cooperative intermolecular S\u2013Cl\u22efO and F\u22efF associations in the crystal packing of \u03b1,\u03c9-di(sulfonyl chloride) perfluoroalkanes, ClSO2(CF2)nSO2Cl, where n = 4, 6","volume":"42","author":"Liu","year":"2018","journal-title":"New J. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2514","DOI":"10.1021\/ar5001555","article-title":"Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different","volume":"47","author":"Mukherjee","year":"2014","journal-title":"Acc. Chem. Res."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"165","DOI":"10.1021\/cr00002a004","article-title":"A Survey of Hammett Substituent Constants and Resonance and Field Parameters","volume":"97","author":"Hansch","year":"1991","journal-title":"Chem. Rev."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Costa, J.P., Sousa, S.A., Galv\u00e3o, A.M., Mata, J.M., Leit\u00e3o, J.H., and Carvalho, M.F.N.N. (2021). Key Parameters on the Antibacterial Activity of Silver Camphor Complexes. Antibiotics, 10.","DOI":"10.3390\/antibiotics10020135"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1347","DOI":"10.1002\/jcc.540141112","article-title":"General atomic and molecular electronic structure system","volume":"14","author":"Schmidt","year":"1993","journal-title":"J. Comput. Chem."},{"key":"ref_18","first-page":"154104","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"Chem. Phys."},{"key":"ref_19","unstructured":"Sheldrick, G.M. (1998). SHELX-97- Programs for Crystal Structure Analysis (Release 97-2), Instit\u00fct f\u00fcr Anorganische Chemie der Universit\u00e4t. Tammanstrasse 4, D-3400."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"837","DOI":"10.1107\/S0021889899006020","article-title":"WINGX","volume":"32","author":"Farrugia","year":"1999","journal-title":"J. Appl. Crystallogr."},{"key":"ref_21","unstructured":"(2023, September 01). Chemcraft-Graphical Software for Visualization of Quantum Chemistry Computations. Available online: https:\/\/www.chemcraftprog.com."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"226","DOI":"10.1107\/S1600576719014092","article-title":"Mercury 4.0: From visualization to analysis, design and prediction","volume":"53","author":"Macrae","year":"2020","journal-title":"Wood J. Appl. Cryst."}],"container-title":["Crystals"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4352\/13\/10\/1499\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T21:06:53Z","timestamp":1760130413000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4352\/13\/10\/1499"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,10,14]]},"references-count":22,"journal-issue":{"issue":"10","published-online":{"date-parts":[[2023,10]]}},"alternative-id":["cryst13101499"],"URL":"https:\/\/doi.org\/10.3390\/cryst13101499","relation":{},"ISSN":["2073-4352"],"issn-type":[{"type":"electronic","value":"2073-4352"}],"subject":[],"published":{"date-parts":[[2023,10,14]]}}}