The three-dimensional metal-organic framework poly[bis(dimethylammonium) [hexa-mu(2)-formato-kappa(12)O:O'-aluminium(III)sodium(I)]], {(C(6)H(8)N)(2)[AlNa(HCOO)(6)]}(n), was obtained serendipitously and has been characterized by X-ray diffraction. The product has arisen as a result of a hydrolysis reaction of dimethylformamide (DMF) and contains dimethylammonium (DMA) cations included in structural voids formed by a three-dimensional [AlNa(HCOO)(6)](-) network. This study provides evidence that, in the presence of traces of aluminium, DMF stored in a glass bottle can be hydrolysed to formate and dimethylamine with simultaneous extraction of Na(+) cations from the glass. It also demonstrates that care must be taken regarding the metal and water content when DMF is not freshly distilled, since the hydrolysis of amide can occur.
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