Sr4CaCo2(SO3)2 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent Sr sites. In the first Sr site, Sr(1) is bonded in a 8-coordinate geometry to four equivalent S(1), two equivalent O(1), and two equivalent O(2) atoms. In the second Sr site, Sr(2) is bonded in a 9-coordinate geometry to two equivalent O(1), two equivalent O(2), and five equivalent O(3) atoms. Ca(1) is bonded to four equivalent S(1) atoms to form distorted corner-sharing CaS4 tetrahedra. Co(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form corner-sharing CoO5 square pyramids. S(1) is bonded to four equivalent Sr(1) and two equivalent Ca(1) atoms to form distorted SSr4Ca2 pentagonal pyramids that share corners with four equivalent O(1)Sr4Co2 octahedra, corners with four equivalent O(2)Sr4Co2 octahedra, corners with eight equivalent S(1)Sr4Ca2 pentagonal pyramids, edges with two equivalent O(1)Sr4Co2 octahedra, edges with two equivalent O(2)Sr4Co2 octahedra, edges with two equivalent S(1)Sr4Ca2 pentagonal pyramids, and faces with two equivalent S(1)Sr4Ca2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 38°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Sr(1), two equivalent Sr(2), and two equivalent Co(1) atoms to form distorted OSr4Co2 octahedra that share corners with two equivalent O(1)Sr4Co2 octahedra, corners with six equivalent O(3)Sr5Co octahedra, corners with four equivalent S(1)Sr4Ca2 pentagonal pyramids, edges with two equivalent O(1)Sr4Co2 octahedra, edges with two equivalent S(1)Sr4Ca2 pentagonal pyramids, faces with two equivalent O(3)Sr5Co octahedra, and faces with four equivalent O(2)Sr4Co2 octahedra. The corner-sharing octahedral tilt angles range from 18-55°. In the second O site, O(2) is bonded to two equivalent Sr(1), two equivalent Sr(2), and two equivalent Co(1) atoms to form distorted OSr4Co2 octahedra that share corners with two equivalent O(2)Sr4Co2 octahedra, corners with six equivalent O(3)Sr5Co octahedra, corners with four equivalent S(1)Sr4Ca2 pentagonal pyramids, edges with two equivalent O(2)Sr4Co2 octahedra, edges with two equivalent S(1)Sr4Ca2 pentagonal pyramids, faces with two equivalent O(3)Sr5Co octahedra, and faces with four equivalent O(1)Sr4Co2 octahedra. The corner-sharing octahedral tilt angles range from 19-56°. In the third O site, O(3) is bonded to five equivalent Sr(2) and one Co(1) atom to form distorted OSr5Co octahedra that share corners with four equivalent O(3)Sr5Co octahedra, corners with six equivalent O(1)Sr4Co2 octahedra, corners with six equivalent O(2)Sr4Co2 octahedra, edges with eight equivalent O(3)Sr5Co octahedra, faces with two equivalent O(1)Sr4Co2 octahedra, and faces with two equivalent O(2)Sr4Co2 octahedra. The corner-sharing octahedral tilt angles range from 12-56°.
Sr4CaCo2(SO3)2 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent Sr sites. In the first Sr site, Sr(1) is bonded in a 8-coordinate geometry to four equivalent S(1), two equivalent O(1), and two equivalent O(2) atoms. All Sr(1)-S(1) bond lengths are 3.17 Å. Both Sr(1)-O(1) bond lengths are 2.56 Å. Both Sr(1)-O(2) bond lengths are 2.55 Å. In the second Sr site, Sr(2) is bonded in a 9-coordinate geometry to two equivalent O(1), two equivalent O(2), and five equivalent O(3) atoms. Both Sr(2)-O(1) bond lengths are 2.77 Å. Both Sr(2)-O(2) bond lengths are 2.78 Å. There is one shorter (2.47 Å) and four longer (2.78 Å) Sr(2)-O(3) bond lengths. Ca(1) is bonded to four equivalent S(1) atoms to form distorted corner-sharing CaS4 tetrahedra. All Ca(1)-S(1) bond lengths are 2.72 Å. Co(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form corner-sharing CoO5 square pyramids. The Co(1)-O(3) bond length is 1.93 Å. Both Co(1)-O(1) bond lengths are 1.98 Å. Both Co(1)-O(2) bond lengths are 1.98 Å. S(1) is bonded to four equivalent Sr(1) and two equivalent Ca(1) atoms to form distorted SSr4Ca2 pentagonal pyramids that share corners with four equivalent O(1)Sr4Co2 octahedra, corners with four equivalent O(2)Sr4Co2 octahedra, corners with eight equivalent S(1)Sr4Ca2 pentagonal pyramids, edges with two equivalent O(1)Sr4Co2 octahedra, edges with two equivalent O(2)Sr4Co2 octahedra, edges with two equivalent S(1)Sr4Ca2 pentagonal pyramids, and faces with two equivalent S(1)Sr4Ca2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 38°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Sr(1), two equivalent Sr(2), and two equivalent Co(1) atoms to form distorted OSr4Co2 octahedra that share corners with two equivalent O(1)Sr4Co2 octahedra, corners with six equivalent O(3)Sr5Co octahedra, corners with four equivalent S(1)Sr4Ca2 pentagonal pyramids, edges with two equivalent O(1)Sr4Co2 octahedra, edges with two equivalent S(1)Sr4Ca2 pentagonal pyramids, faces with two equivalent O(3)Sr5Co octahedra, and faces with four equivalent O(2)Sr4Co2 octahedra. The corner-sharing octahedral tilt angles range from 18-55°. In the second O site, O(2) is bonded to two equivalent Sr(1), two equivalent Sr(2), and two equivalent Co(1) atoms to form distorted OSr4Co2 octahedra that share corners with two equivalent O(2)Sr4Co2 octahedra, corners with six equivalent O(3)Sr5Co octahedra, corners with four equivalent S(1)Sr4Ca2 pentagonal pyramids, edges with two equivalent O(2)Sr4Co2 octahedra, edges with two equivalent S(1)Sr4Ca2 pentagonal pyramids, faces with two equivalent O(3)Sr5Co octahedra, and faces with four equivalent O(1)Sr4Co2 octahedra. The corner-sharing octahedral tilt angles range from 19-56°. In the third O site, O(3) is bonded to five equivalent Sr(2) and one Co(1) atom to form distorted OSr5Co octahedra that share corners with four equivalent O(3)Sr5Co octahedra, corners with six equivalent O(1)Sr4Co2 octahedra, corners with six equivalent O(2)Sr4Co2 octahedra, edges with eight equivalent O(3)Sr5Co octahedra, faces with two equivalent O(1)Sr4Co2 octahedra, and faces with two equivalent O(2)Sr4Co2 octahedra. The corner-sharing octahedral tilt angles range from 12-56°.