Interpenetration of a three-dimensional Cu(I) coordination framework controlled by adjusting the symmetry of its secondary building unit

[Display omitted] •Complex 1 and 2 are distinct structural characteristic: twofold interpenetrating diamondlike framework for 1 and a noncatenated structure based on infinite[Cu(SCN)]n chains for 2.•The symmetry matching of their secondary building unit (SBU) are of particular importance to control their degree of interpenetration.•Tetrakis(3-pyridyloxymethylene) methane (L) can be served as a good candidate for the construction of MOFs due to its specific tetrahedral configuration and flexible conformation. Two new coordination polymers based on CuX (X=SCN, I) and L have been successfully prepared by solvothermal reactions: [Cu4I4L] (1) and [Cu4(SCN)4L] (2) (L=tetrakis(3-pyridyloxymethylene)methane), exhibiting a doubly-fold interpenetrating diamondlike framework for 1 and a noncatenated structure with infinite[Cu(SCN)]n chains for 2. Their structural analysis shows the symmetry matching of their secondary building unit (SBU) can effectively control their degree of interpenetration.