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The title compound, (C5H12NO)2[ZnBr4], was synthesized by hydrothermal reaction of ZnBr2 with 4-methylmorpholine in a HBr/distilled water solution. Each of the two independent cations exhibits a chair conformation; the anion deviates slightly from an tetrahedral configuration. The Zn—Br distances in the anion are in the range of 2.3996 (9)–2.4247 (9) Å. All of the amine H atoms are involved in bifurcated intermolecular N—H...Br hydrogen bonds, building up a trimer.