Hydrogen Bonds, Halogen Bonds, and Other Non-Covalent Interactions in a Series of Iodocymantrenes [Mn(C5InH5-n)(CO)2L], L = CO, PPh3, and n=1-5

In this study, the molecular and crystal structures of iodocymantrenes [Mn(C5InH5-n)(CO)2(PPh3)] (1b n = 1; 2, n = 2; 3, n = 3) are reported and compared with the known structures of [Mn(C5InH5-n)(CO)3] (1a, n = 1; 5, n = 5) and [Mn(C5I4H)(CO)2(PPh3)] (4). In the crystals, many weak interactions like H bonds (H & mldr;O, H & mldr;I, H & mldr;pi), halogen bonds (I & mldr;I, I & mldr;O, I & mldr;C, I & mldr;pi), and pi-pi contacts are found. Hirshfeld analyses show that H bonding is far more important when the PPh3 ligand is present, and this is mainly based on dispersive interactions. However, without the PPh3 ligand, H & mldr;I and other I & mldr;X contacts are the most frequently observed intermolecular interactions.