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The caesium hydrogen benzoylcyanoximate (L - ) complex with 18-crown-6 of composition Cs(18-crown-6){H(L) 2 } has been prepared and studied by means of X-ray diffraction [monoclinic, space group P2 1 /n, with a = 9.906(1), b = 18.387(3), c = 18.855(3)Å, β = 90.13(1)°, V = 3434.3(9) Å, Z = 4; final R1 = 0.043 for the 6431 independent reflections used. The lattice consists of Cs(18-crown-6) +  cations and complex hydrogen oximate anions {H(L) 2 } - , formed via strong hydrogen bonding between the oxygen atoms of nitroso-groups [O - - - O ca. 2.456(5)Å]. The caesium atom deviates by 1.492(3) Å from the mean plane of the oxygen atoms of the macrocyclic ether (dominant orientation of disordered ligand, 60%) and adopts a typical “sunrise coordination” [Cs-O (ether) 3.040(9)-3.312(7) Å]. The hydrogen oximate groups are bonded to the metal center only on one side of the crown ether plane via the oxygen atoms of nitroso-groups and the nitrogen atoms of cyano groups (Cs-O ca. 3.040(9), 3.312(7) Å; Cs-N ca. 3.469(5), 3.679(6) Å). The coordination polyhedron of Cs +  can be described as a distorted bicapped tetragonal prism.

Synthesis and Crystal Structure of a Caesium Hydrogen Benzoylcyanoximate Complex with 18-Crown-6: Cs(18-Crown-6){H(L) 2 }