Abstract

AbstractThe ureates of the alkali metals Na – Cs were synthesized from urea and the metals in liquid ammonia at temperatures below 50 °C. The crystal structures were determined using single‐crystal X‐ray diffraction. NaCN2H3O crystallizes in the monoclinic system [P21/c, Z = 16, a = 17.529(1) Å, b = 6.4784(5) Å, c = 10.8211(9) Å, β = 96.938(1)°]. All other ureates are orthorhombic, with KCN2H3O and RbCN2H3O being isotypic [Pbca, Z = 8, KCN2H3O: a = 7.102(4) Å, b = 7.221(4) Å, c = 13.533(8) Å; RbCN2H3O: a = 7.1973(8) Å, b = 7.3531(8) Å, c = 13.921(2) Å]. CsCN2H3O adopts a smaller unit cell [P212121, Z = 4, a = 6.3520(3) Å, b = 7.1645(4) Å, c = 9.0911(5) Å]. The ureates of K, Rb, and Cs contain hydrogen‐bond networks, the imino nitrogen atom acting as the hydrogen‐bond acceptor in CsCN2H3O. In KCN2H3O and RbCN2H3O, however, the carbonyl oxygen atom accepts the hydrogen bonds.

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