The ground spin-state of [Cu(phpyNO)(2)(H2O)(2)](BF4)(2) was switched between S-total = 1/2 and 3/2 across 175 K. On warming, the space group was changed from P2(1)2(1)2(1) to C222(1) in a single-crystal-to-single-crystal manner, and the transient structure could be monitored by means of the crystallographic analysis. The copper-radical exchange coupling changed from 2J/k(B) = -463(3) to +312(6) K with rather small Cu-O-N-C-2py twisting deformation on one side, while practically no distortion occurred on the other.