4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates: Synthesis and crystal structures

Two complex salts, i.e., 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates, [H2(Crypt-222)][MnCl4] · 1.5H2O (I) and [H2(Crypt-222)][ZnCl4] · 2H2O (II) were synthesized and their crystal structures were studied by X-ray diffraction. Crystals I and II are trigonal (space group R $$\bar 3$$ c, Z = 12); I: a = 11.033, c = 77.775 Å; II: a = 11.046, c = 77.555 Å (the structures were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.056 (I) and 0.065 (II) for all 2634 (I) and 2636 (II) independent reflections; CAD-4 automated diffractometer, λMoK α). The [MnCl4]2− or [ZnCl4]2− anion in structures I or II and the 2.2.2-cryptand dication (with two protonated N atoms) lie on crystal axis 3. The dication contains trifurcate hydrogen bonds N+-H(…O)3. The bond lengths and bond angles in tetrahedral anions [MnCl4]2− or [ZnCl4]2− are disproportional, probably, due to the Jahn-Teller effect. The molecules of water of crystallization in crystals I, II are disordered over two positions.