Caprolactam (CL) is a high-value chemical and precursor to nylon-6. Industrially, a harsh, liquid acid catalyst transforms C6-oxime to CL but due to the risk and inefficiency of the process, a solid-acid alternative is desirable. Whilst silicoaluminophosphates (SAPOs) have been successful in this domain, their small micropores suffer mass transport limitations. Hierarchically-porous (HP) SAPOs contain an auxiliary mesoporous network generated by soft-templating with surfactant. As well as improved mass transport, the synthesis introduces pendant silanols in the mesopores, with their own catalytic potential. Interestingly, earlier INS studies revealed the loss of oxime and catalyst O-H modes, indicating that the silanols can interact with oxime at low temperature, in a solid-state mixture. Our aim is to clarify the nature of these interactions and to investigate the loss of the O-H bands.