The self-adaptation of manganese-chloride arrangement with the tripodal ligand 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (Me 3-TBzIm) afforded a rare 3D metal-organic framework, [Mn 5Cl 10(Me 3-TBzIm) 4] n (1) showing a high spin ground state with S = 15/ 2. ? 2012 The Royal Society of Chemistry.