A 3 × 3 isomer grid of nine methoxyphenyl-N-pyridinylcarbamates (C₁₃H₁₂N₂O₃) as CxxOMe (x = para-/meta-/ortho-) represents the first phenyl-N-pyridinylcarbamate crystal structures to be reported. Structural relationships have been correlated in all nine crystal structures as derived from ab initio calculations and the solid-state using conformational analysis. N–H···N hydrogen bonds dominate as the primary interaction in all nine isomers. Two isomers (CmmOMe, CmoOMe) form unusual cyclic N–H···N trimer synthons as R³₃(15) with two distinct conformations isolated in the CmoOMe structure, whereas the three CoxOMe isomers form N–H···N hydrogen bonded dimers based on the R²₂(8) motif. For all isomers, C–H···O interactions assist in aggregation, and in most cases the methoxy group augments the hydrogen bonding. The solid state and modeled conformations are mismatched in three isomers where the methoxy groups and meta-methoxyphenyl rings (mOMe) (in the solid state) adopt metastable or unstable conformations compared to their optimized computational models. This is rationalized in terms of preferred solid state conformations and observed interactions as compared to the computational models.