CrO2 crystallizes in the trigonal R3m space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2) and three equivalent O(1) atoms to form corner-sharing CrO4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-59°. In the second Cr site, Cr(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Cr(1)O4 tetrahedra and edges with four equivalent Cr(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cr(1) and two equivalent Cr(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Cr(1) and three equivalent Cr(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent Cr(2) atoms. In the fourth O site, O(4) is bonded in a water-like geometry to two equivalent Cr(2) atoms.
CrO2 crystallizes in the trigonal R3m space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2) and three equivalent O(1) atoms to form corner-sharing CrO4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-59°. The Cr(1)-O(2) bond length is 1.88 Å. All Cr(1)-O(1) bond lengths are 1.82 Å. In the second Cr site, Cr(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Cr(1)O4 tetrahedra and edges with four equivalent Cr(2)O6 octahedra. The Cr(2)-O(2) bond length is 2.09 Å. The Cr(2)-O(3) bond length is 1.93 Å. Both Cr(2)-O(1) bond lengths are 2.05 Å. Both Cr(2)-O(4) bond lengths are 1.84 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cr(1) and two equivalent Cr(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Cr(1) and three equivalent Cr(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent Cr(2) atoms. In the fourth O site, O(4) is bonded in a water-like geometry to two equivalent Cr(2) atoms.