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Structural analyses of the compounds di-μ-acetato-κ 4 O : O ′-bis{[2-methoxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ]manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn 2 (C 23 O 2 ) 2 (C 23 H 23 N 3 O) 2 ](C 24 H 20 B)·1.45CH 2 Cl 2 or [Mn(DQMEA)(μ-OAc) 2 Mn(DQMEA)](BPh 4 ) 2 ·1.45CH 2 Cl 2 or [1] (BPh 4 ) 2 ·1.45CH 2 Cl 2 , and (acetato-κ O )[2-hydroxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ](methanol-κ O )manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH 3 COO)(C 22 H 21 N 3 O)(CH 3 OH)](C 24 H 20 B)·CH 3 OH or [Mn(DQEA)(OAc)(CH 3 OH)]BPh 4 ·CH 3 OH or [2] BPh 4 ·CH 3 OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to Mn II ions. In the asymmetric unit, compound [1] (BPh 4 ) 2 ·(CH 2 Cl 2 ) 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 Mn II 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 Mn II 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] BPh 4 ·CH 3 OH 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 Mn II center in [2] BPh 4 ·CH 3 OH 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.