NMR crystallography is an emerging method for atomic-resolution structural analysis of ubiquitous vanadium(V) sites in inorganic and bioinorganic complexes as well as vanadium-containing proteins. NMR crystallography allows for characterization of vanadium(V) containing solids, based on the simultaneous measurement of (VN)-V-51-N-15 internuclear distances and anisotropic spin interactions, described by C-13, N-15, and V-51 chemical shift anisotropy and V-51 electric field gradient tensors. We show that the experimental V-51, C-13, and N-15 NMR parameters are essential for inferring correct coordination numbers and deriving correct geometries in density functional theory (DFT) calculations, particularly in the absence of single-crystal X-ray structures. We first validate this approach on a structurally known vanadium(V) complex, (N-15-salicylideneglycinate)-(benzhydroxamate)oxovanadium(V), VO(15)NGlySalbz. We then apply this approach to derive the three-dimensional structure of (methoxo)(N-15-salicylidene-glycinato)oxovanadium(V) with solvated methanol, [VO((15)NGlySal)(OCH3)].(CH3OH). This is a representative complex with potentially variable coordination geometry depending on the solvation level of the solid. The solid material containing molecules of CH3OH, formally expressed as [VO((15)NGlySal)(OCH3)].(CH3OH), is found to have one molecule of CH3OH weakly coordinated to the vanadium. The material is therefore best described as [VO((15)NGlySal)(OCH3)(CH3OH)] as deduced by the combination of multinuclear solid-state NMR experiments and DFT calculations. The approach reported here can be used for structural analysis of systems that are not amenable to single-crystal X-ray diffraction characterization and which can contain weakly associated solvents.