The title compound, (C(16)H(36)N)(2)[W(6)Cl(14)], undergoes a reversible phase transition at 268 (1) K. The structure at 150 and 200 K has monoclinic (P2(1)/c) symmetry. Both crystallographically independent tungsten chloride cluster anions sit on crystallographic inversion centers [symmetry codes: (-x, -y + 1, -z) and (-x + 1, -y + 2, -z)]. Two previous studies at room temperature describe the structure in the space group P2(1)/n with a unit-cell volume approximately half the size of the low-temperature unit cell [Zietlow, Schaefer et al. (1986). Inorg. Chem. 25, 2195-2198; Venkataraman et al. (1999). Inorg. Chem. 38, 828-830]. The unit cells of the room- and low-temperature polymorphs are closely related. The hydrocarbon chain of one of the tetrabutylammonium cations is disordered at both 150 and 200 K.

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