Single-crystal X-ray crystallographic analyses of [NO2][Ga(NO3)(4)] reveal that it undergoes a reversible phase transition without any apparent damage to the crystal during repeated temperature cyclings. The room-temperature, noncentrosymmetric, body-centered tetragonal (I (4) over bar), polymorph 1 (a = 9.2774(3) Angstrom, c = 6.1149(2) Angstrom, Z = 2) consists of well-separated nitronium and tetranitratogallate ions. The [Ga(NO3)(4)](-) units exhibit a slightly squashed tetrahedral geometry in which all of the ligands are monodentate. Below approximately 250 K, distortions fewer the symmetry to the chiral, body-centered monoclinic nonstandard space group I2. Both components (2a: a 9.5857(2) Angstrom, b = 5.9399(1) Angstrom, c = 8.9759(2) Angstrom, beta = 90.409(1)degrees,Z = 2. 2b: a = 9.5898(2) Angstrom, b = 5.9376(1) Angstrom, c = 8.9784(1) Angstrom, beta = 90.420(1)degrees, Z = 2) of the nonmerohedrally twinned structure are independently refined and found to be enantiomeric with nearly identical distance and angle parameters. As in the high-temperature polymorph, the cations and anions are well separated. The most notable change involves two of the nitrate ligands in the [Ga(NO3)(4)](-) ions that have become bidendate, causing the molecular structure to distort toward octahedral geometry.