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Z. Naturforsch. 54 b, 389-393 (1999); received October 23, 1998 18-Crown-6, Caesium Macrocyclic Complexes, Dicyanamide, Crystal Structure The new macrocyclic complex of composition Cs(18-crown-6)N(CN)2-H20 has been pre­ pared and characterized by X-ray crystallography (monoclinic, space group P21 In, with a = 11.218(3), b = 8.563(7), c = 21.704(2) Ä; ß = 92.66(1)°, V = 2083(2) Ä3, Z = 4; final R = 0.034 and Rw = 0.038 for 2529 independent reflections with I > 3cr(I)). The complex adopts a molecular dimeric array [Cs(18c6)(^r-H20){N(CN)2}]2(2:2 anion-paired encapsulate). The dimerization of Cs(18c6)+ moieties takes place surprisingly not via the nitrilic nitrogen atoms, but via the water molecules (Cs-0 3.139(5), 3.334(5) A), which is an unprecedented example in the chemistry of M(18c6)+ complexes. The caesium atom adopts nine-fold coordination (Cs-0 (ether) 3.099(5) 3.280(5) A). One cyano group of the counter anion completes the coordina­ tion environment of the caesium atom (Cs-N 3.420(8) A), while the second one is involved in hydrogen bonding.

Structure of a Cs(18-crown-6)N(CN) 2 · H 2 O Complex: Assembly of the Dimeric 2:2 Anion Paired Encapsulate by Means of μ 2 -Bridging Water Molecules