π-Stacking among the Anthracenyl Groups of a Copper Complex Resulted in Doubling of Unit Cell Volume To Provide New Polymorphs

[Image: see text] Two polymorphs of the 9-N-(3-imidazolylpropylamino)methylanthracene (Hanthraimmida) containing hydrated copper(II)-2,6-pyridinedicarboxylate complex are reported. The two polymorphs have either lamellar or Herringbone arrangements of π-stacks among the anthracenyl groups of organocation. The difference between the two polymorphs originated from having face-to-face stacking arrangements between the two anthracenyl groups of the symmetry independent cations within the unit cell in one of the polymorphs. The π-stacked anthracenyl groups in consecutive layers of the polymorphs are oriented in one direction in the polymorph designated as P1, whereas the polymorph designated as P2 has such orientations in opposite directions. The unit cell volume of the polymorph P2 (Z = 4) has approximately twice the volume of the polymorph P1 (Z = 2); it happend due to coalescence of two unit cells of P1 in the ab-crystallographic plane. A mixed methanol/water solvate of the copper complex is also reported. It has a channel-like arrangement of the cations; has the anions and the solvents within the cation embraced channel-like enclosures. This complex is unstable, once taken out from the methanol solvent, it transforms in real time to P2 by replacements of the methanol molecules by water molecules.