Differences/similarities of supramolecular motifs are discussed in two new thiophosphoramide structures and their Ni molecular complexes: (C2H5O)2P(S)(NHC(S)NHCH2C6H4X) and [{(C2H5O)2P(S)(NC(S)NHCH2C6H4X)}2Ni] (X = Cl/CH3I/II and III/IV). The structures have equal numbers of donor/acceptor sites contributing to classical hydrogen bonds (PS/CS and 2 × NH in ligands and 2 × PS and 2 × NH in the complexes). However, these donor and acceptor sites contribute to inter/intramolecular hydrogen bonding in ligands and intramolecular hydrogen bonding in complexes. In the supramolecular assemblies of the ligands, the classic hydrogen bonds (N-H⋯S[double bond, length as m-dash]C) are restricted in dimer synthons, and the weaker interactions (formed by Cl/CH3 substituents) compete against each other. In the complexes, despite the lack of classic intermolecular hydrogen bond, numerous weak interactions, e.g., C-H⋯Y (Y = S, O, Ni, N, and π), contribute to the molecular assemblies, which do not include the participation of Cl/CH3. Thus, different packing features of ligands, but similar in complexes are observed. Each ligand and the associated complex show nearly equal supramolecular motifs in the slice of the substituted benzyl groups, related to the formation of C-H⋯Cl/π⋯π for the 4-Cl-C6H4CH2 groups in I/III and C-H⋯π for the 4-CH3-C6H4CH2 groups in II/IV. The repeatabilities of the motifs made by 4-Cl-C6H4CH2/4-CH3-C6H4CH2 were checked by surveying 142/844 structures with 178/1482 segments in the CSD, which show that 17% and 12% of the structures exhibited similarities with the title structures. The methods X-ray crystallography, 2D fingerprint plots, electrostatic potential surfaces, QTAIM, and energy framework calculations were applied to present the discussion.

Department of Chemistry Faculty of Science Ferdowsi University of Mashhad Mashhad Iran

Institute of Physics of the Czech Academy of Sciences Na Slovance 2 Prague 8 182 21 Czech Republic

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Zhu Q. Hattori S. J. Mater. Res. 2023;38:19–36.

Woodley S. M. Catlow R. Nat. Mater. 2008;7:937–946. PubMed

Corpinot M. K. Bučar D.-K. Cryst. Growth Des. 2019;19:1426–1453.

Neumann M. A. van de Streek J. Fabbiani F. P. A. Hidber P. Grassmann O. Nat. Commun. 2015;6:7793. PubMed PMC

Aakeröy C. B. Panikkattu S. Chopade P. D. Desper J. CrystEngComm. 2013;15:3125–3136.

Pourayoubi M. Toghraee M. Zhu J. Dušek M. Bereciartua P. J. Eigner V. CrystEngComm. 2014;16:10870–10887.

Steiner T. Angew. Chem., Int. Ed. 2002;41:48–76.

Desiraju G. R. J. Am. Chem. Soc. 2013;135:9952–9967. PubMed

Lu Y. Lin J. Wang L. Zhang L. Cai C. Chem. Rev. 2020;120:4111–4140. PubMed

Guan W.-L. Chen J.-F. Liu J. Shi B. Yao H. Zhang Y.-M. Wei T.-B. Lin Q. Coord. Chem. Rev. 2024;507:215717.

Bouabdallah I. Harit T. Rahal M. Malek F. Tillard M. Eddike D. Acta Chim. Slov. 2021;68:718–727. PubMed

Kuo C.-H. Huang D.-C. Peng W.-T. Goto K. Chao I. Tao Y.-T. J. Mater. Chem. C. 2014;2:3928–3935.

Cavallo G. Metrangolo P. Milani R. Pilati T. Priimagi A. Resnati G. Terraneo G. Chem. Rev. 2016;116:2478–2601. PubMed PMC

Loveday O. Echeverría J. Nat. Commun. 2021;12:5030. PubMed PMC

Zhuo H.-Y. Jiang L.-X. Li Q.-Z. Li W.-Z. Cheng J.-B. Chem. Phys. Lett. 2014;608:90–94.

Wheeler S. E. Houk K. N. J. Chem. Theory Comput. 2009;5:2301–2312. PubMed PMC

Wheeler S. E. Acc. Chem. Res. 2013;46:1029–1038. PubMed

Wheeler S. E. J. Am. Chem. Soc. 2011;133:10262–10274. PubMed

Kitaigorodsky A., Molecular Crystals and Molecules, Academic Press, New York, 1st edn, 1973

Nangia A. New J. Chem. 2000;24:1049–1055.

Desiraju G. R. Sarma J. A. R. P. J. Chem. Sci. 1986;96:599–605.

Edwards M. R. Jones W. Motherwell W. D. S. Shields G. P. Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A. 2001;356:337–353.

Hosseinpoor S. Pourayoubi M. Abrishami M. Sobati M. Karimi Ahmadabad F. Sabbaghi F. Nečas M. Dušek M. Kučeráková M. Kaur M. CrystEngComm. 2023;25:2557–2569.

Singh A. Ramanan A. Bandyopadhyay D. Cryst. Growth Des. 2011;11:2743–2754.

Romasanta A. K. S. Braga D. Duarte M. T. Grepioni F. CrystEngComm. 2017;19:653–660.

Ranjan S. Devarapalli R. Kundu S. Saha S. Deolka S. Vangala V. R. Reddy C. M. IUCrJ. 2020;7:173–183. PubMed PMC

Tan S. L. Tiekink E. R. T. CrystEngComm. 2021;23:1723–1743.

Edwards M. R. Jones W. Motherwell W. D. S. CrystEngComm. 2006;8:545–551.

Nath N. K. Nangia A. Cryst. Growth Des. 2012;12:5411–5425.

Polito M. D'Oria E. Maini L. Karamertzanis P. G. Grepioni F. Braga D. Price S. L. CrystEngComm. 2008;10:1848–1854.

Safin D. A. Babashkina M. G. Bolte M. Garcia Y. CrystEngComm. 2012;14:774–778.

Safin D. A. Babashkina M. G. Mitoraj M. P. Kubisiak P. Robeyns K. Bolte M. Garcia Y. Inorg. Chem. Front. 2016;3:1419–1431.

Metlushka K. E. Sadkova D. N. Shaimardanova L. N. Nikitina K. A. Ivshin K. A. Islamov D. R. Kataeva O. N. Alfonsov A. V. Kataev V. E. Voloshina A. D. Punegova L. N. Alfonsov V. A. Inorg. Chem. Commun. 2016;66:11–14.

Kataeva O. N. Metlushka K. E. Yamaleeva Z. R. Ivshin K. A. Kiiamov A. G. Lodochnikova O. A. Nikitina K. A. Sadkova D. N. Punegova L. N. Voloshina A. D. Lyubina A. P. Sapunova A. S. Sinyashin O. G. Alfonsov V. A. Cryst. Growth Des. 2019;19:4044–4056.

Luckay R. C. Sheng X. Strasser C. E. Raubenheimer H. G. Safin D. A. Babashkina M. G. Klein A. Dalton Trans. 2009:4646–4652. PubMed

Rojas-Montoya I. D. Santana-Silva A. García-Montalvo V. Muñoz-Hernández M.-Á. Rivera M. New J. Chem. 2014;38:4702–4710.

Flores-Romero V. García-Guzmán O. L. Aguirre-Bautista A. Rojas-Montoya I. D. García-Montalvo V. Rivera M. Jiménez-Sandoval O. Muñoz-Hernández M.-Á. Hernández-Ortega S. New J. Chem. 2020;44:10367–10379.

Mitoraj M. P. Babashkina M. G. Isaev A. Y. Chichigina Y. M. Robeyns K. Garcia Y. Safin D. A. Cryst. Growth Des. 2018;18:5385–5397.

Mitoraj M. P. Sagan F. Babashkina M. G. Isaev A. Y. Chichigina Y. M. Safin D. A. Eur. J. Org. Chem. 2019;2019:493–503.

Khorramaki M. Abad M. Darugar V. Pourayoubi M. Vakili M. Nečas M. Choquesillo-Lazarte D. Andreev P. V. Shchegravina E. S. Polyhedron. 2022;228:116157.

Agilent, CrysAlis PRO, Agil. Technol. Ltd, Yarnton, Oxfordshire, UK, 2014

Sheldrick G. M. Acta Crystallogr., Sect. A: Found. Adv. 2015;71:3–8. PubMed PMC

Petříček V. Palatinus L. Plášil J. Dušek M. Z. Kristallogr. - Cryst. Mater. 2023;238:271–282.

Frisch M. J., et al., Gaussian 09, Revision A.02, Gaussian Inc., Wallingford, CT, 2016

Spackman P. R. Turner M. J. McKinnon J. J. Wolff S. K. Grimwood D. J. Jayatilaka D. Spackman M. A. J. Appl. Crystallogr. 2021;54:1006–1011. PubMed PMC

Turner M. J. Grabowsky S. Jayatilaka D. Spackman M. A. J. Phys. Chem. Lett. 2014;5:4249–4255. PubMed

Spackman M. A. CrystEngComm. 2018;20:5340–5347.

Bader R. F. W., Atoms in Molecules: A Quantum Theory, Oxford University Press, Oxford, 1994

Lu T. Chen F. J. Comput. Chem. 2012;33:580–592. PubMed

Espinosa E. Molins E. Lecomte C. Chem. Phys. Lett. 1998;285:170–173.

Spackman M. A. Cryst. Growth Des. 2015;15:5624–5628.

Bankiewicz B. Matczak P. Palusiak M. J. Phys. Chem. A. 2012;116:452–459. PubMed

Koch U. Popelier P. L. A. J. Phys. Chem. 1995;99:9747–9754.

Babashkina M. G. Safin D. A. Bolte M. Srebro M. Mitoraj M. Uthe A. Klein A. Köckerling M. Dalton Trans. 2011;40:3142–3153. PubMed

Metlushka K. Tufatullin A. Shaimardanova L. Sadkova D. Nikitina K. Lodochnikova O. Kataeva O. Alfonsov V. Heteroat. Chem. 2014;25:636–643.

Etter M. C. MacDonald J. C. Bernstein J. Acta Crystallogr., Sect. B: Struct. Sci. 1990;46:256–262. PubMed

Rozas I. Alkorta I. Elguero J. J. Am. Chem. Soc. 2000;122:11154–11161.

Rajput G. Singh V. Gupta A. N. Yadav M. K. Kumar V. Singh S. K. Prasad A. Drew M. G. B. Singh N. CrystEngComm. 2013;15:4676–4683.

Mitoraj M. P. Babashkina M. G. Robeyns K. Sagan F. Szczepanik D. W. Seredina Y. V. Garcia Y. Safin D. A. Organometallics. 2019;38:1973–1981.

Groom C. R. Bruno I. J. Lightfoot M. P. Ward S. C. Acta Crystallogr., Sect. B: Struct. Sci., Cryst. Eng. Mater. 2016;72:171–179. PubMed PMC