The crystal structure of perdeuterated methanol hemiammoniate (CD3OD0.5ND3) determined from neutron powder diffraction data at 4.2 and 180 K

摘要

The crystal structure of perdeuterated methanol hemiammoniate, CD3OD-0.5ND3, has been solved from neutron powder diffraction data collected at 4.2 and 180 K. The structure is orthorhombic, space group Pn21a (Z = 4), with unitcelldimensions a = 12.70615 (16), b = 8.84589 (9), c = 4.73876 (4) A ° , V = 532.623 (8) A ° 3 [calc = 1149.57 (2) kg m3] at 4.2 K, and a = 12.90413 (16), b =8.96975 (8), c = 4.79198 (4) A ° , V = 554.656 (7) A ° 3 [calc = 1103.90 (1) kg m3] at 180 K. The crystal structure was determined by ab initio methods from the powder data; atomic coordinates and isotropic displacement parameters were subsequently refined by the Rietveld method to Rp ’ 2% at both temperatures.The crystal structure comprises a three-dimensionally hydrogen-bonded network in which the ND3 molecules are tetrahedrally coordinated by the hydroxy moieties of the methanol molecule. This connectivity leads to the formation of zigzag chains of ammonia–hydroxy groups extending along the c axis, formed via N—DO hydrogen bonds; these chains are cross-linked along the a axis through the hydroxy moiety of the second methanol molecule via N — DO and O—DO hydrogen bonds. This ‘bridging’ hydroxy group in turn donates an O—DN hydrogen bond to ammonia in adjacent chains stacked along the b axis. The methyl deuterons in methanol hemiammoniate, unlike those in methanol monoammoniate, do not participate in hydrogen bonding and reveal evidence of orientational disorder at 180 K. The relative volume change on warming from 4.2 to 180 K, V/V, is + 4.14%, which is comparable to, but more nearly isotropic (as determined from the relative change in axial lengths,e.g. a/a) than, that observed in deuterated methanol monohydrate, and very similar to what is observed in methanol monoammoniate.