{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,13]],"date-time":"2026-02-13T04:27:10Z","timestamp":1770956830181,"version":"3.50.1"},"reference-count":100,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2018,11,13]],"date-time":"2018-11-13T00:00:00Z","timestamp":1542067200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UID\/QUI\/00100\/2013, RECI\/QEQ-QIN\/0189\/2012, PTDC\/QEQ-EPR\/5841\/2014, SFRH\/BPD\/94291\/2013"],"award-info":[{"award-number":["UID\/QUI\/00100\/2013, RECI\/QEQ-QIN\/0189\/2012, PTDC\/QEQ-EPR\/5841\/2014, SFRH\/BPD\/94291\/2013"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>This paper focuses in the influence of halogen atoms in the design and structural control of the crystal packing of Group VIII halogenated metallocenes. The study is based on the present knowledge on new types of intermolecular contacts such as halogen (X\u22efX, C-X\u22efH, C-X\u22ef\u03c0), \u03c0\u22ef\u03c0, and C-H\u22ef\u03c0 interactions. The presence of novel C-H\u22efM interactions is also discussed. Crystal packings are analysed after database search on this family of compounds. Results are supported by ab initio calculations on electrostatic charge distributions; Hirshfeld analysis is also used to predict the types of contacts to be expected in the molecules. Special attention is given to the competition among hydrogen and halogen interactions, mainly its influence on the nature and geometric orientations of the different supramolecular motifs. Supramolecular arrangements of halogenated metallocenes and Group IV di-halogenated bent metallocenes are also compared and discussed. Analysis supports halogen bonds as the predominant interactions in defining the crystal packing of bromine and iodine 1,1\u2032-halometallocenes.<\/jats:p>","DOI":"10.3390\/molecules23112959","type":"journal-article","created":{"date-parts":[[2018,11,14]],"date-time":"2018-11-14T02:42:41Z","timestamp":1542163361000},"page":"2959","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Halogen and Hydrogen Bonding Interplay in the Crystal Packing of Halometallocenes"],"prefix":"10.3390","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2454-1795","authenticated-orcid":false,"given":"Karina","family":"Shimizu","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, U. Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"given":"Jo\u00e3o","family":"Ferreira da Silva","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, U. Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2018,11,13]]},"reference":[{"key":"ref_1","unstructured":"Jeffrey, G.A. (1997). An Introduction to Hydrogen Bonding, Oxford University Press."},{"key":"ref_2","first-page":"129","article-title":"Van der Waals attractive force","volume":"22","author":"Keesom","year":"1921","journal-title":"Physik. Z."},{"key":"ref_3","first-page":"178","article-title":"Van der Waals\u2019 cohesion forces","volume":"21","author":"Debye","year":"1920","journal-title":"Physik. Z."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"8b","DOI":"10.1039\/tf937330008b","article-title":"The general theory of molecular forces","volume":"33","author":"London","year":"1937","journal-title":"Trans. Faraday Soc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1419","DOI":"10.1021\/ja01452a015","article-title":"Polarity and Ionization from the standpoint of the Lewis Theory of valence","volume":"42","author":"Latimer","year":"1920","journal-title":"J. Am. Chem. Soc."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"601","DOI":"10.1021\/j150223a001","article-title":"Electronic Structures of Atoms","volume":"26","author":"Huggins","year":"1922","journal-title":"J. Phys. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1367","DOI":"10.1021\/ja01355a027","article-title":"The Nature of the chemical bond. II. The one-electron bond and the three-electron bond","volume":"53","author":"Pauling","year":"1931","journal-title":"J. Am. Chem. Soc."},{"key":"ref_8","unstructured":"Pauling, L. (1939). The Nature of the Chemical Bond and the Structure of Molecules and Crystals: An Introduction to Modern Structural Chemistry, Cornell University Press. [3rd ed.]."},{"key":"ref_9","unstructured":"Pimentel, G.C., and McClellan, A.L. (1960). The Hydrogen Bond, W.H. Freeman."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"4540","DOI":"10.1021\/ja00064a016","article-title":"Role of C-H\u22efO hydrogen bonds in the coordination of water molecules. Analysis of neutron diffraction data","volume":"115","author":"Steiner","year":"1993","journal-title":"J. Am. Chem. Soc."},{"key":"ref_11","unstructured":"Desiraju, G.R., and Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, IUCR, Oxford University Press."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1619","DOI":"10.1351\/PAC-REP-10-01-01","article-title":"Defining the hydrogen bond: An account (IUPAC Technical Report)","volume":"83","author":"Arunan","year":"2011","journal-title":"Pure Appl. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1637","DOI":"10.1351\/PAC-REC-10-01-02","article-title":"Definition of the hydrogen bond (IUPAC Recommendations 2011)","volume":"83","author":"Arunan","year":"2011","journal-title":"Pure Appl. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"827","DOI":"10.1039\/b716776h","article-title":"Crucial role of Ru\u22efH interactions in the crystal packing of ruthenocene and its derivatives","volume":"10","author":"Borissova","year":"2008","journal-title":"CrystEngComm"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4281","DOI":"10.1021\/ja01646a008","article-title":"Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta","volume":"76","author":"Wilkinson","year":"1954","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2802","DOI":"10.1039\/C7CE00362E","article-title":"The role of halogen interactions in the crystal structure of biscyclopentadienyl dihalides","volume":"19","author":"Shimizu","year":"2017","journal-title":"CrystEngComm"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"8725","DOI":"10.1021\/ja00205a027","article-title":"The nature of halogen\u22efhalogen interactions: Are short halogen contacts due to specific attractive forces or due to close packing of nonspherical atoms?","volume":"111","author":"Desiraju","year":"1989","journal-title":"J. Am. Chem. Soc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"386","DOI":"10.1021\/ar0400995","article-title":"Halogen Bonding Based Recognition Processes:\u2009 A World Parallel to Hydrogen Bonding","volume":"38","author":"Metrangolo","year":"2005","journal-title":"Acc. Chem. Res."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"3125","DOI":"10.1039\/C2CE26747K","article-title":"Competing hydrogen-bond and halogen-bond donors in crystal engineering","volume":"15","author":"Panikkattu","year":"2013","journal-title":"CrystEngComm"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1002\/chem.19970030115","article-title":"Organic Fluorine Hardly Ever Accepts Hydrogen Bonds","volume":"3","author":"Dunitz","year":"1997","journal-title":"Chem. Eur. J."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"403","DOI":"10.1007\/s12039-011-0091-6","article-title":"The role of weak intermolecular C-H\u22efF interactions in supramolecular assembly: Structural investigations on 3,5-dibenzylidene-piperidin-4-one and database analysis","volume":"123","author":"Rathore","year":"2011","journal-title":"J. Chem. Sci."},{"key":"ref_22","unstructured":"Desiraju, G.R., and Steiner, T. (1999). The Weak Hydrogen Bond: In Structural Chemistry and Biology, IUCR, Oxford University Press."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"354","DOI":"10.1107\/S0365110X63000979","article-title":"A nuclear quadrupole resonance and X-ray study of the crystal structure of 2,5-di-chloroaniline","volume":"16","author":"Sakurai","year":"1963","journal-title":"Acta Crystallogr."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"307","DOI":"10.1007\/BF00745215","article-title":"Characteristic features of various intermolecular contacts x\u22efx in crystals","volume":"22","author":"Zefirov","year":"1981","journal-title":"J. Struct. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"239","DOI":"10.1007\/BF00751732","article-title":"Geometry of halogen-halogen specific interactions in organic crystals","volume":"27","author":"Zefirov","year":"1986","journal-title":"J. Struct. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"3896","DOI":"10.1002\/ange.200805739","article-title":"The Nature of Halogen\u22efHalogen Interactions: A Model Derived from Experimental Charge-Density Analysis","volume":"121","author":"Bui","year":"2009","journal-title":"Angew. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1278","DOI":"10.1021\/cg060117k","article-title":"Using Halogen\u22efHalogen Interactions to Direct Noncentrosymmetric Crystal Packing in Dipolar Organic Molecules","volume":"6","author":"Saha","year":"2006","journal-title":"Cryst. Growth Des."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3242","DOI":"10.1021\/cg400735f","article-title":"Synthon Modularity in Cocrystals of 4-Bromobenzamide with n-Alkanedicarboxylic Acids: Type I and Type II Halogen\u22efHalogen Interactions","volume":"13","author":"Tothadi","year":"2013","journal-title":"Cryst. Growth Des."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"49","DOI":"10.1107\/S2052252513025657","article-title":"Halogen bonds in some dihalogenated phenols: Applications to crystal engineering","volume":"1","author":"Mukherjee","year":"2014","journal-title":"IUCrJ"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1711","DOI":"10.1351\/PAC-REC-12-05-10","article-title":"Definition of the halogen bond (IUPAC Recommendations 2013)","volume":"85","author":"Desiraju","year":"2013","journal-title":"Pure Appl. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1107\/S205225251303491X","article-title":"Type II halogen\u00b7\u00b7\u00b7halogen contacts are halogen bonds","volume":"1","author":"Metrangolo","year":"2014","journal-title":"IUCrJ"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2511","DOI":"10.1002\/1521-3765(20010618)7:12<2511::AID-CHEM25110>3.0.CO;2-T","article-title":"Halogen Bonding: A Paradigm in Supramolecular Chemistry","volume":"7","author":"Metrangolo","year":"2001","journal-title":"Chem. Eur. J."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1007\/s00894-006-0130-2","article-title":"Halogen bonding: The sigma-hole","volume":"13","author":"Clark","year":"2007","journal-title":"J. Mol. Model."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3496","DOI":"10.1039\/c0cs00221f","article-title":"Organic fluorine compounds: A great opportunity for enhanced materials properties","volume":"40","author":"Berger","year":"2011","journal-title":"Chem. Soc. Rev."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"o406","DOI":"10.1107\/S0108270110026405","article-title":"Intermolecular \u03c0-stacking and F\u22efF interactions of fluorine-substituted meso-alkynylporphyrin","volume":"66","author":"Marushima","year":"2010","journal-title":"Acta Crystallogr. Sect. C"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"57","DOI":"10.1002\/qua.560440709","article-title":"Surface electrostatic potentials of halogenated methanes as indicators of directional intermolecular interactions","volume":"44","author":"Brinck","year":"1992","journal-title":"Int. J. Quantum Chem. Quantum Biol. Symp."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1363","DOI":"10.1021\/jm3012068","article-title":"Principles and Applications of Halogen Bonding in Medicinal Chemistry and Chemical Biology","volume":"56","author":"Wilcken","year":"2013","journal-title":"J. Med. Chem."},{"key":"ref_38","first-page":"17","article-title":"Halogen Bonding: Fundamentals and Applications","volume":"126","author":"Metrangolo","year":"2008","journal-title":"Struct. Bond."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2478","DOI":"10.1021\/acs.chemrev.5b00484","article-title":"The Halogen Bond","volume":"116","author":"Cavallo","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3046","DOI":"10.1002\/qua.21352","article-title":"A predicted new type of directional noncovalent interaction","volume":"107","author":"Murray","year":"2007","journal-title":"Int. J. Quantum Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1033","DOI":"10.1007\/s00894-007-0225-4","article-title":"\u03c3-hole bonding: Molecules containing group VI atoms","volume":"13","author":"Murray","year":"2007","journal-title":"J. Mol. Model."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"723","DOI":"10.1007\/s00894-008-0386-9","article-title":"Expansion of the \u03c3-hole concept","volume":"15","author":"Murray","year":"2009","journal-title":"J. Mol. Model."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"6114","DOI":"10.1002\/anie.200800128","article-title":"Halogen bonding in supramolecular chemistry","volume":"47","author":"Metrangolo","year":"2008","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"16789","DOI":"10.1073\/pnas.0407607101","article-title":"Halogen bonds in biological molecules","volume":"101","author":"Auffinger","year":"2004","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_45","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_46","doi-asserted-by":"crossref","first-page":"677","DOI":"10.1016\/j.ccr.2009.09.035","article-title":"Halogen bonding in metal\u2013organic\u2013supramolecular networks","volume":"254","author":"Bertani","year":"2010","journal-title":"Coord. Chem. Rev."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"3057","DOI":"10.1039\/c3ce90042h","article-title":"Halogen bonding: From self-assembly to materials and biomolecules","volume":"15","author":"Pennington","year":"2013","journal-title":"CrystEngComm"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"946","DOI":"10.1039\/b610454a","article-title":"Halogen bonding and other noncovalent interactions involving halogens: A terminology issue","volume":"8","author":"Metrangolo","year":"2006","journal-title":"CrystEngComm"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"12339","DOI":"10.1002\/anie.201502960","article-title":"Halogen Bonding Molecular Capsules","volume":"54","author":"Dumele","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.ccr.2015.09.005","article-title":"Halogen bonding: A. powerful, emerging tool for constructing high-dimensional metal-containing supramolecular networks","volume":"308","author":"Li","year":"2016","journal-title":"Coord. Chem. Rev."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"1189","DOI":"10.1021\/jm061038a","article-title":"Propensities of Polar and Aromatic Amino Acids in Noncanonical Interactions:\u2009 Nonbonded Contacts Analysis of Protein\u2212Ligand Complexes in Crystal Structures","volume":"50","author":"Imai","year":"2007","journal-title":"J. Med. Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2911","DOI":"10.1002\/anie.200806219","article-title":"Evidence for C-Cl\/C-Br\u22ef\u03c0 Interactions as an Important Contribution to Protein\u2013Ligand Binding Affinity","volume":"48","author":"Matter","year":"2009","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"1518","DOI":"10.1039\/b916955e","article-title":"Functionalization of single-wall carbon nanotubes through chloroform adsorption: Theory and experiment","volume":"12","author":"Batista","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"17271","DOI":"10.1021\/acs.jpcc.5b05595","article-title":"Electronic Properties of Halogen-Adsorbed Graphene","volume":"119","author":"Xu","year":"2015","journal-title":"J. Phys. Chem. C"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"232","DOI":"10.1021\/ct700216w","article-title":"Investigations into the Nature of Halogen Bonding Including Symmetry Adapted Perturbation Theory Analyses","volume":"4","author":"Riley","year":"2008","journal-title":"J. Chem. Theory Comput."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"14941","DOI":"10.1039\/c0cp00607f","article-title":"Dispersion dominated halogen\u2013\u03c0 interactions: Energies and locations of m\u00ednima","volume":"12","author":"Wallnoefer","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"4224","DOI":"10.1002\/cphc.201200605","article-title":"Halogen-Bonding Interactions with \u03c0 Systems: CCSD(T), MP2, and DFT Calculations","volume":"13","author":"Forni","year":"2012","journal-title":"ChemPhysChem"},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"386","DOI":"10.1002\/jcc.23507","article-title":"Halogen bonds with benzene: An assessement of DFT functionals","volume":"35","author":"Forni","year":"2014","journal-title":"J. Comput. Chem."},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"9305","DOI":"10.1021\/acs.jpca.6b09395","article-title":"Halogen-\u03c0 Interactions between Benzene and X2\/CX4 (X = Cl, Br): Assessment of Various Density Functionals with Respect to CCSD(T)","volume":"120","author":"Youn","year":"2016","journal-title":"J. Phys. Chem. A"},{"key":"ref_60","doi-asserted-by":"crossref","unstructured":"Kodama, Y., Nishihata, K., Nishio, M., and Nakagawa, N. (1977). Attractive interaction between aliphatic and aromatic systems. Tetrahedron Lett., 2105\u20132108.","DOI":"10.1016\/S0040-4039(01)83692-3"},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"3375","DOI":"10.1021\/ja01133a047","article-title":"Aromatic Compounds as Donor Molecules in Hydrogen Bonding","volume":"74","author":"Tamres","year":"1952","journal-title":"J. Am. Chem. Soc."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"1757","DOI":"10.1039\/b902318f","article-title":"CH\/\u03c0 hydrogen bonds in organic and organometallic chemistry","volume":"11","author":"Nishio","year":"2009","journal-title":"CrystEngComm"},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"2669","DOI":"10.1021\/om971096h","article-title":"X-H\u22ef\u03c0 (X = O, N, C) Hydrogen Bonds in Organometallic Crystals","volume":"17","author":"Braga","year":"1998","journal-title":"Organometallics"},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"659","DOI":"10.1039\/FT9938900659","article-title":"Structures and binding energies of benzene\u2014Methane and benzene\u2014Benzene complexes. An ab initio SCF\/MP2 study","volume":"89","author":"Sakaki","year":"1993","journal-title":"J. Chem. Soc. Faraday Trans."},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"9933","DOI":"10.1016\/j.tet.2007.07.061","article-title":"Inclusion compounds of l,d-dipeptide with small sulfoxides: Flexible sheet structure of (S)-phenylglycyl-(R)-phenylglycine","volume":"63","author":"Akazome","year":"2007","journal-title":"Tetrahedron"},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"2749","DOI":"10.1021\/ol800875k","article-title":"Origin of Enantioselection in Hetero-Diels\u2212Alder Reactions Catalyzed by Naphthyl-TADDOL","volume":"10","author":"Anderson","year":"2008","journal-title":"Org. Lett."},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"10646","DOI":"10.1021\/ja062125v","article-title":"A Single CH\/\u03c0 Weak Hydrogen Bond Governs Stability and the Photocycle of the Photoactive Yellow Protein","volume":"128","author":"Harigai","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"13873","DOI":"10.1039\/c1cp20404a","article-title":"The CH\/\u03c0 hydrogen bond in chemistry. Conformation, supramolecules, optical resolution and interactions involving carbohydrates","volume":"13","author":"Nishio","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"3089","DOI":"10.1039\/C5CE00149H","article-title":"Effect of substituents in the molecular and supramolecular architectures of 1-ferrocenyl-2-(aryl)thioethanones","volume":"17","author":"Harjivan","year":"2015","journal-title":"CrystEngComm"},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"2113","DOI":"10.1039\/b919793a","article-title":"Stacking interaction between homostacks of simple aromatics and the factors influencing these interactions","volume":"12","author":"Choudhury","year":"2010","journal-title":"CrystEngComm"},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"40","DOI":"10.1016\/j.cplett.2004.11.016","article-title":"Interplay between \u03c0-\u03c0 interactions and the H-bonding ability of aromatic nitrogen bases","volume":"401","author":"Mignon","year":"2005","journal-title":"Chem. Phys. Lett."},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"5010","DOI":"10.1021\/ja01503a071","article-title":"Metal\/hydrogen bonding in metallocene conompounds","volume":"82","author":"Trifan","year":"1960","journal-title":"J. Am. Chem. Soc."},{"key":"ref_73","doi-asserted-by":"crossref","unstructured":"Roe, D.M., Bailey, P.M., Mosely, K., and Maitlis, P.M. (1972). Structure of bromobis(triphenylphosphine)-(1,2,3,4-tetrakismethoxycarbonylbuta-1,3-dienyl)palladium and evidence for a C\u2013H\u22efPd interaction. J. Chem. Soc. Chem. Commun., 1273.","DOI":"10.1039\/C39720001273"},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"357","DOI":"10.1016\/S0022-328X(00)98072-0","article-title":"The behaviour of ferrocene and ruthenocene in weakly to strongly protic media. Implications on the mechanism of substitutions involving proton as the electrophile","volume":"127","author":"Cerichelli","year":"1977","journal-title":"J. Organomet. Chem."},{"key":"ref_75","doi-asserted-by":"crossref","first-page":"1254","DOI":"10.1021\/ic50195a016","article-title":"Quantitative data on some oxidative addition reactions and on the Lewis basicity of bis(triphenylphosphine)carbonylchloroiridium(I) Ir(I)[(C6H5)3P]2(CO)Cl","volume":"18","author":"Drago","year":"1979","journal-title":"Inorg. Chem."},{"key":"ref_76","doi-asserted-by":"crossref","unstructured":"Yoshida, T., Tani, K., Yamagata, T., Tatsuno, Y., and Saito, T. (1990). Preparation and structure of [Rh{(\u03b75-C5H4(2-C5H4N))(\u03b75-C5H4PPh2)}(cod)]PF6 and [Ir(H){Fe[\u03b75-C5H3(2-C5H4N)](\u03b75-C5H4PPh2)}(cod)]PF6; a RhI complex having a C\u2013H\u22efRhI interaction and a hydrido IrIII complex (where cod = cyclo-octa-1,5-diene). J. Chem. Soc. Chem. Comm., 292\u2013294.","DOI":"10.1039\/C39900000292"},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"3145","DOI":"10.1039\/b303006g","article-title":"Metals and hydrogen bonds","volume":"16","author":"Brammer","year":"2003","journal-title":"DaltonTrans."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"367","DOI":"10.1016\/0022-2860(92)80114-W","article-title":"Regularities in formation of intramolecular hydrogen bonds with the metal atom Part I. \u03b1-Metallocenylcarbinols of the iron subgroup","volume":"265","author":"Shubina","year":"1992","journal-title":"J. Mol. Struct."},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/0022-2860(93)80225-K","article-title":"Intermolecular hydrogen bonds with d-electrons of transition metal atoms. H-complexes with metallocenes of the iron subgroup","volume":"301","author":"Shubina","year":"1993","journal-title":"J. Mol. Struct."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1016\/0022-2860(94)87052-7","article-title":"Novel types of hydrogen bonds involving transition metal atoms and proton transfer (XH\u22efM, [MH]+\u22efB, [MH]+\u22efA\u2212)","volume":"322","author":"Epstein","year":"1994","journal-title":"J. Mol. Struct."},{"key":"ref_81","doi-asserted-by":"crossref","first-page":"765","DOI":"10.1107\/S010827018900778X","article-title":"Structure of [Pt(C6H5)2(btz-N,N\u2032)].CHCl3, btz = 2,2\u2032-bi-5,6-dihydro-4H-1,3-thiazine","volume":"46","author":"Bruno","year":"1990","journal-title":"Acta Crystallogr. Sect. C"},{"key":"ref_82","doi-asserted-by":"crossref","first-page":"1789","DOI":"10.1039\/DT9910001789","article-title":"The role of transition metal atoms as hydrogen bond acceptors: A neutron diffraction study of [NPrn4]2[PtCl4]\u00b7cis-[PtCl2(NH2Me)2] at 20 K","volume":"7","author":"Brammer","year":"1991","journal-title":"J. Chem. Soc. Dalton Trans."},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"1846","DOI":"10.1021\/om9608364","article-title":"Hydrogen Bonding in Organometallic Crystals. 6. X\u2212H\u22efM Hydrogen Bonds and M\u22ef(H\u2212X) Pseudo-Agostic Bonds","volume":"16","author":"Braga","year":"1997","journal-title":"Organometallics"},{"key":"ref_84","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1107\/S2052520616003954","article-title":"The Cambridge Structural Database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_85","doi-asserted-by":"crossref","first-page":"5461","DOI":"10.1021\/acs.organomet.5b00811","article-title":"The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes","volume":"34","author":"Inkpen","year":"2015","journal-title":"Organometallics"},{"key":"ref_86","doi-asserted-by":"crossref","first-page":"m1806","DOI":"10.1107\/S1600536804028429","article-title":"1,1\u2032-Di-bromo-ferrocene","volume":"60","author":"Hnetinka","year":"2004","journal-title":"Acta Crystallogr. Sect. E"},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"11815","DOI":"10.1039\/C4DT01787K","article-title":"Syntheses and purification of the versatile synthons iodoferrocene and 1,1\u2032-diiodoferrocene","volume":"43","author":"Roemer","year":"2014","journal-title":"Dalton Trans."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"3662","DOI":"10.1021\/ic403169z","article-title":"Novel, Mercury-Free Synthetic Pathway for Trifluoromethylthio-Substituted Metallocenes","volume":"53","author":"Hess","year":"2014","journal-title":"Inorg. Chem."},{"key":"ref_89","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1039\/b206867b","article-title":"Distance criteria for crystal packing analysis of supramolecular motifs","volume":"27","author":"Dance","year":"2003","journal-title":"New J. Chem."},{"key":"ref_90","doi-asserted-by":"crossref","first-page":"372","DOI":"10.1039\/B601467D","article-title":"Multifurcated halogen bonding involving Ph\u2013Cl\u22efH-CPh=N-R\u2032 interactions and its relation to idioteloamphiphile layer architecture","volume":"8","author":"Glaser","year":"2006","journal-title":"CrystEngComm"},{"key":"ref_91","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/S0025-5408(98)00031-2","article-title":"Crystal Engineering: Some Further Strategies","volume":"1","author":"Anthony","year":"1998","journal-title":"Cryst. Eng."},{"key":"ref_92","doi-asserted-by":"crossref","first-page":"466","DOI":"10.1107\/S0021889807067908","article-title":"Mercury CSD 2.0\u2014New features for the visualization and investigation of crystal structures","volume":"41","author":"Macrae","year":"2008","journal-title":"J. Appl. Crystallogr."},{"key":"ref_93","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Vreven, T., Kudin, K.N., and Burant, J.C. (2004). Gaussian 03, Gaussian Inc.. revision C.05."},{"key":"ref_94","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_95","first-page":"79","article-title":"Energy-Adjusted Pseudopotentials for Transition-Metal Elements","volume":"Volume 176","author":"Veillard","year":"1986","journal-title":"Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry"},{"key":"ref_96","doi-asserted-by":"crossref","first-page":"2193","DOI":"10.1063\/1.455064","article-title":"A complete basis set model chemistry. I. The total energies of closed-shell atoms and hydrides of the first-row atoms","volume":"89","author":"Petersson","year":"1988","journal-title":"J. Chem. Phys."},{"key":"ref_97","doi-asserted-by":"crossref","first-page":"6081","DOI":"10.1063\/1.460447","article-title":"A complete basis set model chemistry. II. Open-shell systems and the total energies of the first-row atoms","volume":"94","author":"Petersson","year":"1991","journal-title":"J. Chem. Phys."},{"key":"ref_98","doi-asserted-by":"crossref","first-page":"361","DOI":"10.1002\/jcc.540110311","article-title":"Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis","volume":"11","author":"Breneman","year":"1990","journal-title":"J. Comput. Chem."},{"key":"ref_99","unstructured":"Turner, M.J., McKinnon, J.J., Wolff, S.K., Grimwood, D.J., Spackman, P.R., Jayatilaka, D., and Spackman, M.A. (2017). CrystalExplorer17, University of Western Australia."},{"key":"ref_100","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1039\/B818330A","article-title":"Hirshfeld surface analysis","volume":"11","author":"Spackman","year":"2009","journal-title":"CrystEngComm"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/23\/11\/2959\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T15:29:27Z","timestamp":1760196567000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/23\/11\/2959"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,11,13]]},"references-count":100,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2018,11]]}},"alternative-id":["molecules23112959"],"URL":"https:\/\/doi.org\/10.3390\/molecules23112959","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,11,13]]}}}