Strong hydrogen bonded supramolecular architecture in a crystal of the {3-[2-(1,3-benzodioxol-5-yl)-7-methoxy-1-benzofuran-5-yl] propyl} diethylamine cation with the hydrogen bonded chloride hydrate anion (halides) assembly: X-ray structure, DFT calculations, Hirshfeld surface analysis

Abstract

The crystal structure of {3-[2-(1,3-benzodioxol-5-yl)-7-methoxy-1-benzofuran-5-yl] propyl} diethylamine hydrohloride hydrate [C₂₃H₂₈NO₄]⁺•[H₂OCl]^– is determined. The molecular geometrical parameters, frontier molecular orbital energies (HOMO, LUMO), their energy gap (ΔE), molecular electrostatic potential analysis of the compound are calculated by DFT/B3LYP at the 6-311G(d,p) level. The benzofuran and benzodioxo ring systems, except the diethylamine group, are essentially planar and a dihedral angle between the ring systems is 7.38(14)°. The compound crystallizes in the monoclinic space group P21/c, with a = 15.230(4) Å, b = 11.418(2) Å, c = 12.880(3) Å, β = 94.56(3)°, V = 2232.8(9) ų, D_calc = 1.297g/cm³, Z = 4. The hydrogen bonded Cl and H₂O are self-assembled to form a supramolecular array of strong N–H…Cl and O–H…Cl bifurcated hydrogen bonds making tetramers which consist of a fused four-membered ring with a graph-set descriptor and a pseudo cyclic centrosymmetric R₂²(8) ring motif. The hybrid dihalide-dihydrate clusters of [Cl₂(H₂O)₂]^2– are observed, too. The supramolecular crystal packing is consolidated by these bifurcated hydrogen bonds and the stacking of the sheet through strong π…π interactions. Moreover, the intra chain hydrogen bonds form intermolecular and intramolecular C–H…O hydrogen bonds, and the 1D supramolecular array is organized by C–H…π interactions. The contacts in the crystal structure are analyzed using the Hirshfeld surfaces computational method. The calculated geometrical parameters are in good agreement with the single crystal XRD data.