LiHSO4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with four equivalent S(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. H(1) is bonded in a distorted single-bond geometry to one O(2) and one O(4) atom. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one H(1), and one S(1) atom. In the third O site, O(3) is bonded in a linear geometry to one Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one H(1) and one S(1) atom.
LiHSO4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with four equivalent S(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.92 Å. Both Li(1)-O(1) bond lengths are 2.02 Å. H(1) is bonded in a distorted single-bond geometry to one O(2) and one O(4) atom. The H(1)-O(2) bond length is 1.67 Å. The H(1)-O(4) bond length is 1.01 Å. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.48 Å. The S(1)-O(3) bond length is 1.45 Å. The S(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one H(1), and one S(1) atom. In the third O site, O(3) is bonded in a linear geometry to one Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one H(1) and one S(1) atom.