A chiral heterometallic complex, obtained from the solvothermal reaction of [Zn(4-pytpy)2](BF4)2 [4-pytpy=4'-(4-pyridyl)-2,2':6',2''-terpyridine] and CuCN, exhibits a rare self-catenated network formed by two 3D cationic and one 3D anionic frameworks.