Competition between hydrogen bonds and halogen bonds: a structural studyElectronic supplementary information (ESI) available. CCDC 1820020-1820028. TGA, DSC, and crystallographic data. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8nj00537k

The competition and balance between intermolecular hydrogen bonds (HBs) and halogen bonds (XBs) were explored by co-crystallizing tetra-functionalized (2 × HB (-OH) and 2 × XB (-C&z.tbd;C-I)) molecules, trans -1,4-bis(iodoethynyl)cyclohexane-1,4-diol ( D1 ) and cis -1,4-bis(iodoethynyl)cyclohexane-1,4-diol ( D2 ), with six ditopic nitrogen based acceptor molecules. The crystal structures of both D1 and D2 showed non-covalent interactions between HB/XB donors and available acceptor sites (oxygen/triple bond/negative region of iodine). In three co-crystals of D1 the HB and XB donors act in similar ways as both activated iodine and hydroxyl hydrogen bind to the nitrogen acceptors in the solid state. In contrast, in a co-crystal of D2 , a geometric isomer of D1 , there were only hydrogen bonds to the co-former and the halogen-bond donor interacted with the hydroxyl oxygen atoms of D2 . A stronger tendency for linear XB interactions (as well as greater van der Waals radii reduction) was observed with nitrogen atoms as acceptors (average reduction = 21%) compared to those involving an oxygen atom as an acceptor (average reduction = 16%). A control molecule, trans -1,4-diethynylcyclohexane-1,4-diol ( D3 ), which has only HB donors (-OH and -C&z.tbd;C-H) was also examined to get a better understanding of the balance between XB and HB intercations. The ethynyl hydrogen atom did not form hydrogen bonds to the nitrogen atoms in acceptors, and only O-H N and -C&z.tbd;C-H O hydrogen bonds were observed in these structures. O-H hydrogen-bond donors and R-C&z.tbd;C-I halogen-bond donors are close competitors for suitable acceptor sites in solid-state assembly.