Crystal engineering in copper/halide/N-organobase system may generate diverse structures with tunable properties because varied stereochemistry of copper atoms and the different redox potential between Cu(Ⅱ) and Cu(Ⅰ).The d9 configuration of Cu(lⅡ) ion is subject to dynamic Jahn-Teller distortion on all its stereochemistry, which can offer unique characteristics in the formation of metal centers (i.e., normal bond, weak bond, coordination flexibility, polarity and Lewis acid).