Crystal Structure of 1,10-Diazonia-18-crown-6 Bis(hydrogen oxalate) and 1,10-Diazonia-18-crown-6 Oxalate Dihydrate

Abstract

An X-ray diffraction study has been performed to study the crystal structure of 1,10-diazonia-18-crown-6 bis(hydrogen oxalate) [H₂DA18C6]²⁺·2C₂HO ^-₄ (I) and 1,10-diazonia-18-crown-6 oxalate dihydrate [H₂DA18C6]²⁺·2C₂O ^-₄ ·2H₂O (II). Crystals I are triclinic: space group $P\bar 1$, a = 7.825, b = 7.861, c = 9.349 Å, α = 97.28, β = 110.22, γ = 99.12°, Z = 1. Crystals II are monoclinic: space group P2 ₁ /n, a = 8.783, b = 10.640, c = 10.225 Å, β = 97.04°, Z = 2. The structures of I and II were solved by direct methods and refined by the full-matrix least-squares procedure anisotropically to R = 0.036 (I) and 0.042 (II) for all 2206 (I) and 1990 (II) unique reflections measured (CAD-4 automatic diffractometer, λCuK _α). In the crystal structures, the ionic complexes (salts) I and II are not individual “guest–host” complex molecules but are parts of complex (infinite in two directions) three-dimensional layers of H-bonded molecular anions and DA18C6 dications (and water molecules in II). In structures I and II, the centrosymmetric DA18C6 dications have different conformations: two-angle in I and four-angle in II. The unusual four-angle conformation of the DA18C6 dication was found for the first time.