Abstract: | Hydrogen Bonds in the Monoammoniates of Potassium and Cesium Amide X‐ray structure determination was carried out on the monoammoniates of potassium and cesium amide. Crystals of KNH2 · NH3 were grown from liquid NH3 at 50 °C > T > 20 °C. They crystallize in the cold part of a pressure resistant glass apparatus. Single crystals of CsNH2 · NH3 were obtained by zone‐melting at —30 °C in x‐ray capillaries. The following data characterize the crystal chemistry of the compounds: KNH2 · NH3 Cmc21, Z = 4 21 °C a = 3, 938(1) Å, b = 10, 983(3) Å, c = 5, 847(1) Å CsNH2 · NH3 Pnma, Z = 4 30 °C a = 7, 103(1) Å, b = 5, 390(1) Å, c = 10, 106(2) Å For CsNH2 · NH3 all hydrogen atom positions were successfully refined. The structure of both ammoniates may be described by a distorted hexagonal close packed arrangement of cations with the NH3 molecules in the octahedral and the NH2— anions in the trigonal bipyramidal interstices. The three H atoms of the NH3 molecules are involved in hydrogen bridge bonds to two amide ions with d(N(NH3)···N(NH2—)) = 2.60Å for the K and 3.19Å for the Cs compound and to a further NH3 molecule with d(N(NH3)···N(NH3)) = 2.98Å for the K and 3.56Å for the Cs compound. Structural relationship of the ammoniates to the monohydrates of KOH and RbOH is discussed. |