The reactions of AIMe(2)Y (Y = Me or Cl) with new ligands 2-(1,3,5-dithiazinan-5-yl)ethanol (1), 2-(1,3,5-dithiazinan-5-yl)-1 -methylethanol (2), and 2-(1,3,5-dithiazinan-5-yl)-1 -phenylethanol (3) are described. The ligands are coordinated to aluminum atoms by nitrogen and oxygen atoms, with a nitrogen based spiranic structure. Equimolar reactions gave dimeric structures bearing pentacoordinated aluminum atoms a(AIMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates (4-7) as well as monometallic compounds with tetracoordinated aluminum atoms a(AIMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates (8-9). Reactions with 2 equiv of the aluminum reagents afforded tetracoordinated dialuminum complexes O-(AIMeY)-O-(AIMe(2)y)-2-(1,3,5-dithiazinan-5-yl)ethanolate (10-18). The structures of the new compounds were determined by NMR (H-1,C-13, and Al-27) and complemented by X-ray diffraction of compounds 4, 10, and 16-18. Relevant intermolecular interactions C-(HS)-S-..., C-(HCl)-Cl-..., and C-H(...)pi found in the crystalline network are reported.