A methodology has been developed for the semi-automatic assignment and chec
king of formal oxidation states for metal atoms in the majority of metallo-
organic complexes stored in the Cambridge Structural Database (CSD). The me
thod uses both chemical connectivity and bond-length data, via ligand donor
group templates and bond-valence sums, respectively. In order to use bond-
length data, the CSD program QUEST has been modified to allow the coordinat
ion sphere of metal atoms to be recalculated using user-defined criteria at
search time. The new methodology has been used successfully to validate th
e +1, +2 and +3 oxidation states in 743 four-coordinate copper complexes in
the CSD for which atomic coordinates are available in ca 99% of structures
using one or other method, and both succeed for >86% of structures.