title: 3-Picoline mediated self-assembly of M(II)-malonate complexes (M = Ni/Co/Mn/Mg/Zn/Cu) assisted by various weak forces involving lone pair-π, π-π, and anion···π-hole interactions.
abstract: Five M(II)-malonate complexes having a common formula (C(6)H(9)N(2))(4)[M(II)(C(3)H(2)O(4))(2)(H(2)O)(2)](PF(6))(2).(H(2)O)(2) (1-5) [where C(6)H(9)N(2) = protonated 3-picoline, M(II) = Ni/Co/Mn/Mg/Zn, C(3)H(4)O(4) = malonic acid, and PF(6)(-) = hexafluorophospahte], have been synthesized and their crystal structures have been determined. Complexes 1-5 were found to be isostructural and protonated 3-picoline has primarily mediated the self-assembly process. Role of a discrete water dimer in complexes 1-5 was also studied. Weaker π-interactions have also played crucial role in stabilizing 1D chain constructed by discrete [M(II)(C(3)H(2)O(4))(2)(H(2)O)(2)] units. An additional copper complex namely, (C(6)H(9)N(2))(4)[Cu(C(3)H(2)O(4))(2)](PF(6))(2) (6) has been synthesized from the same reagents and was found to have a completely different structure from the others. Structures of all the complexes are fully described and compared here. Moreover, the lone pair-π and π-π noncovalent interactions have been analyzed by means of DFT calculations, mainly focusing our attention to the influence of the coordinating metal on the strength of the interactions and the interplay between hydrogen bonding and π-interactions. We also present here Hirshfeld surface analysis to investigate the close intermolecular contacts.
authors.affiliation: Department of Chemistry, Jadavpur University , Kolkata 700 032, India.
authors.forename: Monojit
authors.initials: M
authors.lastname: Mitra
authors.forename: Prankrishna
authors.initials: P
authors.lastname: Manna
authors.forename: Antonio
authors.initials: A
authors.lastname: Bauzá
authors.forename: Pablo
authors.initials: P
authors.lastname: Ballester
authors.forename: Saikat Kumar
authors.initials: SK
authors.lastname: Seth
authors.forename: Somnath
authors.initials: S
authors.lastname: Ray Choudhury
authors.forename: Antonio
authors.initials: A
authors.lastname: Frontera
authors.forename: Subrata
authors.initials: S
authors.lastname: Mukhopadhyay