Benzenepropanenitrile (BPN) and its hydrate clusters are studied by R2PI and IR-UV ion-depletion spectroscopy in the CH/OH stretch regions, aided by theoretical calculations. A single water molecule binds to the terminal nitrile 'lone-pair' of the anti-BPN host, but there is also evidence for a side-type structure with OH donating to the nitrile pi-electrons. In the gauche-BPN cluster, water is located at an intermediate angle that facilitates O center dot center dot center dot HC(ortho) interaction. A wide range of attachment angles is possible, as the intrinsic preference for linear hydrogen bonding is mediated by additional CH center dot center dot center dot O interactions that depend on molecular geometry near the nitrile group. (C) 2016 Elsevier B.V. All rights reserved.