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
4•
dpma (
2) was obtained by
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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
4•
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–H∙∙∙O 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) Å,
b = 5.66867(14) Å,
c = 17.0106(5) Å,
β = 104.788(3)°, V = 1666.9(1) Å
3, Z = 8, T = 293 K,
R(
F) [I > 2σ(I)] = 0.0391,
wR(
F2) [all] = 0.1113). In
2, besides the N–H∙∙∙O hydrogen bonds, medium strong N–H∙∙∙N hydrogen bonds are present. One
dpmaH cation and the neutral
dpma molecule are connected head to tail by two N–H∙∙∙O hydrogen bonds forming a monocationic cyclic unit. These cyclic units are further connected by N–H∙∙∙O and N–H∙∙∙N hydrogen bonds forming polymeric, polar double-strands along [001]. The perchlorate anions fill the gaps between these strands, and each [ClO
4]
− anion is weakly connected to the NH
2 group by one N–H∙∙∙O hydrogen bond (orthorhombic, non-centrosymmetric space group
Pca2
1 (No. 29),
a = 18.5821(5) Å,
b = 11.4320(3) Å,
c = 6.89400(17) Å, V = 1464.50(6) Å
3, Z = 4, T = 100 K,
R(
F) [I > 2σ(I)] = 0.0234,
wR(
F2) [all] = 0.0575). Both structures are structurally related, and their commonalities are discussed in terms of a graph-set analysis.
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