Novel Layered Hybrid Fluoroaluminate in the Composition Space Diagram of the Al(OH)3-HguaCl-HFaq-EtOH System

A composition space diagram is used to establish the stability regions of hybrid fluoroaluminates synthesized by solvothermal reactions in the Al(OH)(3)-HguaCl-HFaq-EtOH system. The syntheses are conducted using microwave heating at 190 degrees C for 1 h. The structures of two new guanidinium fluoroaluminates, (H3O)(2)center dot[Hgua](16)center dot (Al4F18)(3)center dot H2O and [Hgua](2)center dot(Al5F17), are reported. (H3O)(2)center dot[Hgua](16)center dot(Al4F18)(3)center dot H2O, determined from single-crystal X-ray data, consists of discrete (Al4F18)(6-) polyanions, while [Hgua](2)center dot(Al5F17), solved from powder X-ray diffraction data in direct space, contains unprecedented Al5F17 layers constructed from the intergrowth of HTB and perovskite columns. A disorder of H2O and H3O+ is evidenced in (H3O)(2)center dot[Hgua](16)center dot(Al4F18)(3)center dot H2O together with a disorder of guanidinium cations in the interlayer space of [Hgua](2)center dot(Al5F17).