The crystal structure of perdeuterated methanol monoammoniate, CD3OD·ND3, has been solved from neutron powder diffraction data collected at 4.2 and 180 K. The crystal structure is orthorhombic, space groupPbca(Z= 8), with unit-cell dimensionsa= 11.02320 (7),b= 7.66074 (6),c= 7.59129 (6) Å,V= 641.053 (5) Å3[ρcalc= 1162.782 (9) kg m−3] at 4.2 K, anda= 11.21169 (5),b= 7.74663 (4),c= 7.68077 (5) Å,V= 667.097 (4) Å3[ρcalc= 1117.386 (7) kg m−3] at 180 K. The crystal structure was determined byab initiomethods from the powder data; atomic coordinates and anisotropic displacement parameters were subsequently refined by the Rietveld method toRp< 3% at both temperatures. The crystal comprises a sheet-like structure in thebccrystallographic plane, consisting of strongly hydrogen bonded elements; these sheets are stacked along theaaxis, and adjacent sheets are linked by what may be comparatively weak C—D...O hydrogen bonds. Within the strongly bonded sheet structure, ND3molecules are tetrahedrally coordinated by the hydroxy moieties of the methanol molecule, accepting one hydrogen bond (O—D...N) of length ∼1.75 Å, and donating three hydrogen bonds (N—D...O) of length 2.15–2.25 Å. Two of the methyl deuterons appear to participate in weak interlayer hydrogen bonds (C—D...O) of length 2.7–2.8 Å. The hydrogen bonds are ordered at both 4.2 and 180 K. The relative volume change on warming from 4.2 to 180 K, ΔV/V, is +4.06%, which is comparable to, but more nearly isotropic (as determined from the relative change in axial lengths,e.g.Δa/a) than, that observed in deuterated methanol monohydrate.