The average Mo-N and Mo-X (X = Cl, Br) distances observed in the single crystals of mer-1, mer-2 and cisfac- [3] 3+ match those obtained by extended X-ray absorption fine structure spectroscopy at the Mo K-edge of the powders (EXAFS, Figure -Figure , Table -Table ) and are well reproduced by a structural model derived from DFT calculations (B3LYP/D3BJ/ZORA/TZVP/CPCM(MeCN), Table , Table ).