MgCd4(TcO3)4 crystallizes in the monoclinic Pm space group. Mg(1) is bonded in a 6-coordinate geometry to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms. There are two inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 16-41°. In the second Tc site, Tc(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form distorted corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(2) atoms. In the second Cd site, Cd(2) is bonded in a 6-coordinate geometry to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms. In the third Cd site, Cd(3) is bonded in a distorted rectangular see-saw-like geometry to one O(7), one O(8), two equivalent O(2), and two equivalent O(4) atoms. In the fourth Cd site, Cd(4) is bonded in a 8-coordinate geometry to one O(7), one O(8), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Mg(1), one Tc(1), one Tc(2), one Cd(2), and one Cd(4) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Mg(1), one Tc(1), one Tc(2), one Cd(1), one Cd(2), and one Cd(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Tc(1), one Tc(2), and one Cd(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Tc(1), one Tc(2), one Cd(3), and one Cd(4) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Mg(1), two equivalent Tc(2), one Cd(1), and one Cd(2) atom. In the sixth O site, O(6) is bonded to one Mg(1), two equivalent Tc(1), one Cd(1), and one Cd(2) atom to form corner-sharing OMgCd2Tc2 square pyramids. In the seventh O site, O(7) is bonded to two equivalent Tc(2), one Cd(3), and one Cd(4) atom to form corner-sharing OCd2Tc2 tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Tc(1), one Cd(3), and one Cd(4) atom to form distorted OCd2Tc2 tetrahedra that share corners with two equivalent O(6)MgCd2Tc2 square pyramids and corners with two equivalent O(7)Cd2Tc2 tetrahedra.
MgCd4(TcO3)4 crystallizes in the monoclinic Pm space group. Mg(1) is bonded in a 6-coordinate geometry to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms. The Mg(1)-O(5) bond length is 2.07 Å. The Mg(1)-O(6) bond length is 2.13 Å. Both Mg(1)-O(1) bond lengths are 2.03 Å. Both Mg(1)-O(2) bond lengths are 2.28 Å. There are two inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 16-41°. The Tc(1)-O(1) bond length is 2.07 Å. The Tc(1)-O(2) bond length is 2.13 Å. The Tc(1)-O(3) bond length is 1.99 Å. The Tc(1)-O(4) bond length is 2.03 Å. The Tc(1)-O(6) bond length is 2.14 Å. The Tc(1)-O(8) bond length is 2.00 Å. In the second Tc site, Tc(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form distorted corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. The Tc(2)-O(1) bond length is 2.05 Å. The Tc(2)-O(2) bond length is 2.40 Å. The Tc(2)-O(3) bond length is 2.04 Å. The Tc(2)-O(4) bond length is 2.01 Å. The Tc(2)-O(5) bond length is 2.20 Å. The Tc(2)-O(7) bond length is 2.07 Å. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(2) atoms. The Cd(1)-O(5) bond length is 2.42 Å. The Cd(1)-O(6) bond length is 2.15 Å. Both Cd(1)-O(2) bond lengths are 2.32 Å. In the second Cd site, Cd(2) is bonded in a 6-coordinate geometry to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms. The Cd(2)-O(5) bond length is 2.75 Å. The Cd(2)-O(6) bond length is 2.38 Å. Both Cd(2)-O(1) bond lengths are 2.33 Å. Both Cd(2)-O(2) bond lengths are 2.54 Å. In the third Cd site, Cd(3) is bonded in a distorted rectangular see-saw-like geometry to one O(7), one O(8), two equivalent O(2), and two equivalent O(4) atoms. The Cd(3)-O(7) bond length is 2.28 Å. The Cd(3)-O(8) bond length is 2.28 Å. Both Cd(3)-O(2) bond lengths are 2.76 Å. Both Cd(3)-O(4) bond lengths are 2.28 Å. In the fourth Cd site, Cd(4) is bonded in a 8-coordinate geometry to one O(7), one O(8), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. The Cd(4)-O(7) bond length is 2.28 Å. The Cd(4)-O(8) bond length is 2.43 Å. Both Cd(4)-O(1) bond lengths are 2.76 Å. Both Cd(4)-O(3) bond lengths are 2.32 Å. Both Cd(4)-O(4) bond lengths are 2.70 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Mg(1), one Tc(1), one Tc(2), one Cd(2), and one Cd(4) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Mg(1), one Tc(1), one Tc(2), one Cd(1), one Cd(2), and one Cd(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Tc(1), one Tc(2), and one Cd(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Tc(1), one Tc(2), one Cd(3), and one Cd(4) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Mg(1), two equivalent Tc(2), one Cd(1), and one Cd(2) atom. In the sixth O site, O(6) is bonded to one Mg(1), two equivalent Tc(1), one Cd(1), and one Cd(2) atom to form corner-sharing OMgCd2Tc2 square pyramids. In the seventh O site, O(7) is bonded to two equivalent Tc(2), one Cd(3), and one Cd(4) atom to form corner-sharing OCd2Tc2 tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Tc(1), one Cd(3), and one Cd(4) atom to form distorted OCd2Tc2 tetrahedra that share corners with two equivalent O(6)MgCd2Tc2 square pyramids and corners with two equivalent O(7)Cd2Tc2 tetrahedra.