%0 Journal Article
%T Synthesis, Structure and Spectroscopy of Two Structurally Related Hydrogen Bonded Compounds in the dpma/HClO4 System; dpma (dimethylphosphoryl)methanamine
%A Daniel Buhl
%A H邦lya G邦n
%A Alexander Jablonka
%A Guido J. Reiss
%J Crystals
%D 2013
%I MDPI AG
%R 10.3390/cryst3020350
%X The new phosphine oxide compound, (dimethylphosphoryl)methanaminium perchlorate, dpmaHClO 4 ( 1), was synthesized by the reaction of (dimethylphosphoryl) methanamine ( dpma) with concentrated perchloric acid. (Dimethylphosphoryl)methanaminium perchlorate (dimethylphosphoryl)methanamine solvate, dpmaHClO 4ˋ dpma ( 2) was obtained by the slow evaporation of an equimolar methanolic solution of 1 and dpma at room temperature. For both compounds, single-crystal X-ray structures, IR and Raman spectra are reported. The assignment of the spectroscopic data were supported by quantum chemical calculations at the B3LYP/6-311G(2d,p) level of theory. In 1, the dpmaH cations form polymeric, polar double-strands along [010] by head to tail connections via N每HˋˋˋO hydrogen bonds. The perchlorate anions are located between these strands attached by one medium strong and two weaker un-bifurcated hydrogen bonds (monoclinic, centrosymmetric space group C2/ c, a = 17.8796(5) ˋ, b = 5.66867(14) ˋ, c = 17.0106(5) ˋ, 汕 = 104.788(3)∼, V = 1666.9(1) ˋ 3, Z = 8, T = 293 K, R( F) [I > 2考(I)] = 0.0391, wR( F 2) [all] = 0.1113). In 2, besides the N每HˋˋˋO hydrogen bonds, medium strong N每HˋˋˋN hydrogen bonds are present. One dpmaH cation and the neutral dpma molecule are connected head to tail by two N每HˋˋˋO hydrogen bonds forming a monocationic cyclic unit. These cyclic units are further connected by N每HˋˋˋO and N每HˋˋˋN hydrogen bonds forming polymeric, polar double-strands along [001]. The perchlorate anions fill the gaps between these strands, and each [ClO 4] ˋ anion is weakly connected to the NH 2 group by one N每HˋˋˋO hydrogen bond (orthorhombic, non-centrosymmetric space group Pca2 1 (No. 29), a = 18.5821(5) ˋ, b = 11.4320(3) ˋ, c = 6.89400(17) ˋ, V = 1464.50(6) ˋ 3, Z = 4, T = 100 K, R( F) [I > 2考(I)] = 0.0234, wR( F 2) [all] = 0.0575). Both structures are structurally related, and their commonalities are discussed in terms of a graph-set analysis.
%K phosphine oxide
%K X-ray crystal structure
%K hydrogen bonding
%K graph-set analysis
%K tecton
%U http://www.mdpi.com/2073-4352/3/2/350