An Unusual 3D Zinc-Organic Framework Constructed from Paddle-Wheel-Based Carboxylate Sheets Bridged by Acetate Ions

A zinc‐2,6‐naphthalenedicarboxylate metal‐organic framework, (H2NEt2)[Zn2(AcO)(NDC)2]·nDEF (1) (DEF = N,N‐diethylformamide, AcO = acetate), was solvothermally synthesized in the presence of small amounts of acetic acid and characterized by single‐crystal and powder X‐ray diffraction and thermogravimetric analysis. Compound 1 is an anionic 3D paddle‐wheel MOF, in which the zinc‐naphthalenedicarboxylate sheets are linked together by bridging acetate ions. Compound 1 exhibits large square channels (13 × 13 Å), which contain DEF molecules and, alternatively, charge‐balancing diethylammonium cations in situ generated by the hydrolysis of DEF under the solvothermal conditions used. The anionic host framework of 1 is unstable upon removal of guest DEF molecules suggesting that host‐guest hydrogen bond interactions are crucial for maintaining the structural integrity of this compound.