Geometrical variations of two manganese(II) complexes with closely related quinoline-based tripodal ligands

Abstract

Structural analyses of the compounds di-μ-acetato-κ4 O:O′-bis{[2-methoxy-N,N-bis(quinolin-2-ylmethyl)ethanamine-κ4 N,N′,N′′,O]manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn2(C23O2)2(C23H23N3O)2](C24H20B)·1.45CH2Cl2 or [Mn(DQMEA)(μ-OAc)2Mn(DQMEA)](BPh4)2·1.45CH2Cl2 or [1](BPh4)2·1.45CH2Cl2, and (acetato-κO)[2-hydroxy-N,N-bis(quinolin-2-ylmethyl)ethanamine-κ4 N,N′,N′′,O](methanol-κO)manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH3COO)(C22H21N3O)(CH3OH)](C24H20B)·CH3OH or [Mn(DQEA)(OAc)(CH3OH)]BPh4·CH3OH or [2]BPh4·CH3OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to MnII ions. In the asymmetric unit, compound [1](BPh4)2·(CH2Cl2)1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitrogen, the nitrogen atom of each quinoline group, and the methoxy-oxygen of the tetradentate DQMEA ligand, and two bridging-acetate oxygen atoms. The symmetric MnII centers have a distorted, octahedral geometry in which the quinoline nitrogen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each MnII center, a coordinated acetate oxygen participates in C—H...O hydrogen-bonding interactions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak π–π stacking interactions and intermolecular cation–anion interactions stabilize the crystal packing. In the asymmetric unit, compound [2]BPh4·CH3OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitrogen, the nitrogen atom of each quinoline group, and the alcohol oxygen of the tetradentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the MnII center in [2]BPh4·CH3OH is also a distorted octahedron, but the quinoline nitrogen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O—H...O) and quinolyl (C—H...O and N—H...O) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of intermolecular O3—H3...O2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and intermolecular cation–anion interactions contribute to the crystal packing.

Foreword to the special virtual issue in tribute to Jerry P. Jasinski

“…We were especially pleased to see that four of the articles had direct contributions from Jerry himself, as well as some of his former students and postdocs from Keene State College. The topical coverage of the articles spans the full spectrum of non-biological crystallography, including organic and main-group compounds (Thiruvalluvar et al, 2021;Mahesha et al, 2021;Allah et al, 2021;Malla et al, 2022;Rajegowda et al, 2021;Purdy et al, 2021), complexes of transition metals and lanthanides (Addison et al, 2022;Frey et al, 2021;Ullery et al, 2021;Sghyar et al, 2021;Tinapple et al, 2021;Mikhalyova et al, 2022;Pavlischuk et al, 2021), transition metal and actinide clusters (Park et al, 2022;Patel et al, 2022;Kelley et al, 2021), and coordination polymers (Lobana et al, 2022). It also includes two articles (Foxman, 2021;Zheng & Campbell, 2021) first published as part of the 'Modern approaches and tools for teaching crystallography' special issue in Acta E that describe the tutorial for teaching space groups and crystallographic symmetry that Jerry developed with Bruce Foxman.…”