TiFeH2 crystallizes in the orthorhombic Cmmm space group. Ti(1) is bonded to one H(3), two equivalent H(2), and four equivalent H(1) atoms to form distorted TiH7 pentagonal bipyramids that share corners with seven equivalent Ti(1)H7 pentagonal bipyramids, edges with three equivalent Ti(1)H7 pentagonal bipyramids, edges with eight equivalent Fe(1)H5 trigonal bipyramids, and faces with two equivalent Ti(1)H7 pentagonal bipyramids. Fe(1) is bonded to one H(2), two equivalent H(1), and two equivalent H(3) atoms to form FeH5 trigonal bipyramids that share corners with seven equivalent Fe(1)H5 trigonal bipyramids, edges with eight equivalent Ti(1)H7 pentagonal bipyramids, and  an edgeedge with one Fe(1)H5 trigonal bipyramid. There are three inequivalent H sites. In the first H site, H(1) is bonded to four equivalent Ti(1) and two equivalent Fe(1) atoms to form HTi4Fe2 octahedra that share corners with four equivalent H(2)Ti4Fe2 octahedra, corners with six equivalent H(1)Ti4Fe2 octahedra, edges with four equivalent H(3)Ti2Fe4 octahedra, edges with four equivalent H(1)Ti4Fe2 octahedra, and faces with two equivalent H(2)Ti4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 13-58°. In the second H site, H(2) is bonded to four equivalent Ti(1) and two equivalent Fe(1) atoms to form HTi4Fe2 octahedra that share corners with eight equivalent H(3)Ti2Fe4 octahedra, corners with eight equivalent H(1)Ti4Fe2 octahedra, edges with two equivalent H(2)Ti4Fe2 octahedra, and faces with four equivalent H(1)Ti4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. In the third H site, H(3) is bonded to two equivalent Ti(1) and four equivalent Fe(1) atoms to form HTi2Fe4 octahedra that share corners with eight equivalent H(2)Ti4Fe2 octahedra, edges with two equivalent H(3)Ti2Fe4 octahedra, and edges with eight equivalent H(1)Ti4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 42-48°.
TiFeH2 crystallizes in the orthorhombic Cmmm space group. Ti(1) is bonded to one H(3), two equivalent H(2), and four equivalent H(1) atoms to form distorted TiH7 pentagonal bipyramids that share corners with seven equivalent Ti(1)H7 pentagonal bipyramids, edges with three equivalent Ti(1)H7 pentagonal bipyramids, edges with eight equivalent Fe(1)H5 trigonal bipyramids, and faces with two equivalent Ti(1)H7 pentagonal bipyramids. The Ti(1)-H(3) bond length is 1.99 Å. Both Ti(1)-H(2) bond lengths are 2.06 Å. All Ti(1)-H(1) bond lengths are 2.09 Å. Fe(1) is bonded to one H(2), two equivalent H(1), and two equivalent H(3) atoms to form FeH5 trigonal bipyramids that share corners with seven equivalent Fe(1)H5 trigonal bipyramids, edges with eight equivalent Ti(1)H7 pentagonal bipyramids, and  an edgeedge with one Fe(1)H5 trigonal bipyramid. The Fe(1)-H(2) bond length is 1.81 Å. Both Fe(1)-H(1) bond lengths are 1.78 Å. Both Fe(1)-H(3) bond lengths are 1.88 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded to four equivalent Ti(1) and two equivalent Fe(1) atoms to form HTi4Fe2 octahedra that share corners with four equivalent H(2)Ti4Fe2 octahedra, corners with six equivalent H(1)Ti4Fe2 octahedra, edges with four equivalent H(3)Ti2Fe4 octahedra, edges with four equivalent H(1)Ti4Fe2 octahedra, and faces with two equivalent H(2)Ti4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 13-58°. In the second H site, H(2) is bonded to four equivalent Ti(1) and two equivalent Fe(1) atoms to form HTi4Fe2 octahedra that share corners with eight equivalent H(3)Ti2Fe4 octahedra, corners with eight equivalent H(1)Ti4Fe2 octahedra, edges with two equivalent H(2)Ti4Fe2 octahedra, and faces with four equivalent H(1)Ti4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. In the third H site, H(3) is bonded to two equivalent Ti(1) and four equivalent Fe(1) atoms to form HTi2Fe4 octahedra that share corners with eight equivalent H(2)Ti4Fe2 octahedra, edges with two equivalent H(3)Ti2Fe4 octahedra, and edges with eight equivalent H(1)Ti4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 42-48°.