By using 1,3-cyclohexane-bis(methylamine) (CHBMA) as the template, a novel zinc phosphatophosphite (TJPU-3) with extra-large 20-ring channels was synthesized. Cobalt doping produced a bimetallic phosphite (TJPU-6) with 12-ring apertures. While the templates sit in the cis configuration in TJPU-3, they are in the trans configuration in TJPU-6. This result has the potential for separation and recognition of CHBMA isomers.