Synthesis, Structure and Spectroscopy of Two Structurally Related Hydrogen Bonded Compounds in the dpma/HClO4 System; dpma ≙ (dimethylphosphoryl)methanamine

Crystals

Daniel Buhl¹  Hülya Gün¹  Alexander Jablonka¹ 

[1] Institut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material-und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, Düsseldorf D-40225, Germany;

关键词: phosphine oxide;    X-ray crystal structure;    hydrogen bonding;    graph-set analysis;    tecton;   

DOI  :  10.3390/cryst3020350

来源: mdpi

【 摘 要 】

The new phosphine oxide compound, (dimethylphosphoryl)methanaminium perchlorate, dpmaHClO₄ (1), was synthesized by the reaction of (dimethylphosphoryl) methanamine (dpma) with concentrated perchloric acid. (Dimethylphosphoryl)methanaminium perchlorate (dimethylphosphoryl)methanamine solvate, dpmaHClO₄•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) ų, 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 [ClO₄]⁻ anion is weakly connected to the NH₂ group by one N–H∙∙∙O hydrogen bond (orthorhombic, non-centrosymmetric space group Pca2₁ (No. 29), a = 18.5821(5) Å, b = 11.4320(3) Å, c = 6.89400(17) Å, V = 1464.50(6) ų, 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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