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The title compound, Na(+) x 3C(2)H(6)NO(2)(+) x 2SiF(6)(2-) x 3C(2)H(5)NO(2), arose from an unexpected reaction of glycine and HF with the glass container. It is an unusual hybrid organic-inorganic network built up from chains of vertex-sharing NaF(4)O(2) and SiF(6) octahedra. A pair of glycinium/glycine molecules bridges the chains into a sheet via a centrosymmetric O...H...O link. The other organic species interact with the network by an extensive N-H...F hydrogen-bond network, including bifurcated and trifurcated bonds. Finally, an extremely short C-H...O interaction (H...O = 2.25 Angstrom) is seen in the crystal structure. The Na atom has site symmetry overline1.

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