CaCd4(TcO3)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(4), one O(5), one O(6), one O(8), and two equivalent O(9) atoms. There are four inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one O(1), one O(10), one O(12), one O(4), one O(5), and one O(8) atom to form TcO6 octahedra that share corners with four equivalent Tc(4)O6 octahedra and  a cornercorner with one Tc(3)O5 square pyramid. The corner-sharing octahedral tilt angles range from 12-30°. In the second Tc site, Tc(2) is bonded to one O(11), one O(2), one O(3), one O(6), and one O(7) atom to form TcO5 square pyramids that share  a cornercorner with one Tc(4)O6 octahedra and corners with four equivalent Tc(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 32°. In the third Tc site, Tc(3) is bonded to one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form distorted TcO5 square pyramids that share  a cornercorner with one Tc(1)O6 octahedra and corners with four equivalent Tc(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 32°. In the fourth Tc site, Tc(4) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form TcO6 octahedra that share corners with four equivalent Tc(1)O6 octahedra and  a cornercorner with one Tc(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 12-30°. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 3-coordinate geometry to one O(10), one O(6), and one O(9) atom. In the second Cd site, Cd(2) is bonded in a distorted water-like geometry to one O(10) and one O(9) atom. In the third Cd site, Cd(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(3), one O(5), and one O(8) atom. In the fourth Cd site, Cd(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(2), one O(3), one O(5), and one O(8) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Ca(1), one Tc(1), one Tc(4), and one Cd(3) atom. In the second O site, O(2) is bonded to one Tc(2), one Tc(3), one Cd(3), and one Cd(4) atom to form OCd2Tc2 tetrahedra that share corners with two equivalent O(5)CaCd2Tc2 square pyramids, corners with two equivalent O(6)CaCdTc2 tetrahedra, corners with three equivalent O(11)Cd2Tc2 tetrahedra, and corners with three equivalent O(12)Cd2Tc2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Tc(2), one Tc(3), one Cd(3), and one Cd(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one Tc(1), and one Tc(4) atom. In the fifth O site, O(5) is bonded to one Ca(1), one Tc(1), one Tc(4), one Cd(3), and one Cd(4) atom to form distorted OCaCd2Tc2 square pyramids that share  a cornercorner with one O(6)CaCdTc2 tetrahedra,  a cornercorner with one O(11)Cd2Tc2 tetrahedra,  a cornercorner with one O(12)Cd2Tc2 tetrahedra, corners with two equivalent O(2)Cd2Tc2 tetrahedra,  an edgeedge with one O(11)Cd2Tc2 tetrahedra,  an edgeedge with one O(12)Cd2Tc2 tetrahedra, and  an edgeedge with one O(10)CaCd2Tc trigonal pyramid. In the sixth O site, O(6) is bonded to one Ca(1), one Tc(2), one Tc(3), and one Cd(1) atom to form distorted OCaCdTc2 tetrahedra that share  a cornercorner with one O(5)CaCd2Tc2 square pyramid,  a cornercorner with one O(11)Cd2Tc2 tetrahedra,  a cornercorner with one O(12)Cd2Tc2 tetrahedra, corners with two equivalent O(2)Cd2Tc2 tetrahedra, and corners with two equivalent O(10)CaCd2Tc trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted linear geometry to one Tc(2) and one Tc(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(1), one Tc(1), one Tc(4), one Cd(3), and one Cd(4) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to two equivalent Ca(1), one Tc(4), one Cd(1), and one Cd(2) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Tc(1), one Cd(1), and one Cd(2) atom to form distorted OCaCd2Tc trigonal pyramids that share  a cornercorner with one O(12)Cd2Tc2 tetrahedra, corners with two equivalent O(6)CaCdTc2 tetrahedra, and  an edgeedge with one O(5)CaCd2Tc2 square pyramid. In the eleventh O site, O(11) is bonded to one Tc(2), one Tc(4), one Cd(3), and one Cd(4) atom to form distorted OCd2Tc2 tetrahedra that share  a cornercorner with one O(5)CaCd2Tc2 square pyramid,  a cornercorner with one O(6)CaCdTc2 tetrahedra, corners with three equivalent O(2)Cd2Tc2 tetrahedra,  an edgeedge with one O(5)CaCd2Tc2 square pyramid, and  an edgeedge with one O(12)Cd2Tc2 tetrahedra. In the twelfth O site, O(12) is bonded to one Tc(1), one Tc(3), one Cd(3), and one Cd(4) atom to form distorted OCd2Tc2 tetrahedra that share  a cornercorner with one O(5)CaCd2Tc2 square pyramid,  a cornercorner with one O(6)CaCdTc2 tetrahedra, corners with three equivalent O(2)Cd2Tc2 tetrahedra,  a cornercorner with one O(10)CaCd2Tc trigonal pyramid,  an edgeedge with one O(5)CaCd2Tc2 square pyramid, and  an edgeedge with one O(11)Cd2Tc2 tetrahedra.
CaCd4(TcO3)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(4), one O(5), one O(6), one O(8), and two equivalent O(9) atoms. The Ca(1)-O(1) bond length is 2.62 Å. The Ca(1)-O(10) bond length is 2.28 Å. The Ca(1)-O(4) bond length is 2.34 Å. The Ca(1)-O(5) bond length is 2.82 Å. The Ca(1)-O(6) bond length is 2.41 Å. The Ca(1)-O(8) bond length is 2.49 Å. There is one shorter (2.58 Å) and one longer (2.92 Å) Ca(1)-O(9) bond length. There are four inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one O(1), one O(10), one O(12), one O(4), one O(5), and one O(8) atom to form TcO6 octahedra that share corners with four equivalent Tc(4)O6 octahedra and  a cornercorner with one Tc(3)O5 square pyramid. The corner-sharing octahedral tilt angles range from 12-30°. The Tc(1)-O(1) bond length is 1.88 Å. The Tc(1)-O(10) bond length is 2.07 Å. The Tc(1)-O(12) bond length is 2.07 Å. The Tc(1)-O(4) bond length is 1.93 Å. The Tc(1)-O(5) bond length is 2.11 Å. The Tc(1)-O(8) bond length is 1.93 Å. In the second Tc site, Tc(2) is bonded to one O(11), one O(2), one O(3), one O(6), and one O(7) atom to form TcO5 square pyramids that share  a cornercorner with one Tc(4)O6 octahedra and corners with four equivalent Tc(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 32°. The Tc(2)-O(11) bond length is 2.02 Å. The Tc(2)-O(2) bond length is 2.08 Å. The Tc(2)-O(3) bond length is 2.04 Å. The Tc(2)-O(6) bond length is 2.15 Å. The Tc(2)-O(7) bond length is 1.90 Å. In the third Tc site, Tc(3) is bonded to one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form distorted TcO5 square pyramids that share  a cornercorner with one Tc(1)O6 octahedra and corners with four equivalent Tc(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 32°. The Tc(3)-O(12) bond length is 2.02 Å. The Tc(3)-O(2) bond length is 2.09 Å. The Tc(3)-O(3) bond length is 2.06 Å. The Tc(3)-O(6) bond length is 2.12 Å. The Tc(3)-O(7) bond length is 1.89 Å. In the fourth Tc site, Tc(4) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form TcO6 octahedra that share corners with four equivalent Tc(1)O6 octahedra and  a cornercorner with one Tc(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 12-30°. The Tc(4)-O(1) bond length is 1.89 Å. The Tc(4)-O(11) bond length is 2.10 Å. The Tc(4)-O(4) bond length is 1.93 Å. The Tc(4)-O(5) bond length is 2.07 Å. The Tc(4)-O(8) bond length is 1.93 Å. The Tc(4)-O(9) bond length is 2.01 Å. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 3-coordinate geometry to one O(10), one O(6), and one O(9) atom. The Cd(1)-O(10) bond length is 2.39 Å. The Cd(1)-O(6) bond length is 2.36 Å. The Cd(1)-O(9) bond length is 2.50 Å. In the second Cd site, Cd(2) is bonded in a distorted water-like geometry to one O(10) and one O(9) atom. The Cd(2)-O(10) bond length is 2.22 Å. The Cd(2)-O(9) bond length is 2.25 Å. In the third Cd site, Cd(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(3), one O(5), and one O(8) atom. The Cd(3)-O(1) bond length is 2.79 Å. The Cd(3)-O(11) bond length is 2.24 Å. The Cd(3)-O(12) bond length is 2.54 Å. The Cd(3)-O(2) bond length is 2.25 Å. The Cd(3)-O(3) bond length is 2.59 Å. The Cd(3)-O(5) bond length is 2.29 Å. The Cd(3)-O(8) bond length is 2.77 Å. In the fourth Cd site, Cd(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(2), one O(3), one O(5), and one O(8) atom. The Cd(4)-O(11) bond length is 2.51 Å. The Cd(4)-O(12) bond length is 2.26 Å. The Cd(4)-O(2) bond length is 2.33 Å. The Cd(4)-O(3) bond length is 2.42 Å. The Cd(4)-O(5) bond length is 2.44 Å. The Cd(4)-O(8) bond length is 2.47 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Ca(1), one Tc(1), one Tc(4), and one Cd(3) atom. In the second O site, O(2) is bonded to one Tc(2), one Tc(3), one Cd(3), and one Cd(4) atom to form OCd2Tc2 tetrahedra that share corners with two equivalent O(5)CaCd2Tc2 square pyramids, corners with two equivalent O(6)CaCdTc2 tetrahedra, corners with three equivalent O(11)Cd2Tc2 tetrahedra, and corners with three equivalent O(12)Cd2Tc2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Tc(2), one Tc(3), one Cd(3), and one Cd(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one Tc(1), and one Tc(4) atom. In the fifth O site, O(5) is bonded to one Ca(1), one Tc(1), one Tc(4), one Cd(3), and one Cd(4) atom to form distorted OCaCd2Tc2 square pyramids that share  a cornercorner with one O(6)CaCdTc2 tetrahedra,  a cornercorner with one O(11)Cd2Tc2 tetrahedra,  a cornercorner with one O(12)Cd2Tc2 tetrahedra, corners with two equivalent O(2)Cd2Tc2 tetrahedra,  an edgeedge with one O(11)Cd2Tc2 tetrahedra,  an edgeedge with one O(12)Cd2Tc2 tetrahedra, and  an edgeedge with one O(10)CaCd2Tc trigonal pyramid. In the sixth O site, O(6) is bonded to one Ca(1), one Tc(2), one Tc(3), and one Cd(1) atom to form distorted OCaCdTc2 tetrahedra that share  a cornercorner with one O(5)CaCd2Tc2 square pyramid,  a cornercorner with one O(11)Cd2Tc2 tetrahedra,  a cornercorner with one O(12)Cd2Tc2 tetrahedra, corners with two equivalent O(2)Cd2Tc2 tetrahedra, and corners with two equivalent O(10)CaCd2Tc trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted linear geometry to one Tc(2) and one Tc(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(1), one Tc(1), one Tc(4), one Cd(3), and one Cd(4) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to two equivalent Ca(1), one Tc(4), one Cd(1), and one Cd(2) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Tc(1), one Cd(1), and one Cd(2) atom to form distorted OCaCd2Tc trigonal pyramids that share  a cornercorner with one O(12)Cd2Tc2 tetrahedra, corners with two equivalent O(6)CaCdTc2 tetrahedra, and  an edgeedge with one O(5)CaCd2Tc2 square pyramid. In the eleventh O site, O(11) is bonded to one Tc(2), one Tc(4), one Cd(3), and one Cd(4) atom to form distorted OCd2Tc2 tetrahedra that share  a cornercorner with one O(5)CaCd2Tc2 square pyramid,  a cornercorner with one O(6)CaCdTc2 tetrahedra, corners with three equivalent O(2)Cd2Tc2 tetrahedra,  an edgeedge with one O(5)CaCd2Tc2 square pyramid, and  an edgeedge with one O(12)Cd2Tc2 tetrahedra. In the twelfth O site, O(12) is bonded to one Tc(1), one Tc(3), one Cd(3), and one Cd(4) atom to form distorted OCd2Tc2 tetrahedra that share  a cornercorner with one O(5)CaCd2Tc2 square pyramid,  a cornercorner with one O(6)CaCdTc2 tetrahedra, corners with three equivalent O(2)Cd2Tc2 tetrahedra,  a cornercorner with one O(10)CaCd2Tc trigonal pyramid,  an edgeedge with one O(5)CaCd2Tc2 square pyramid, and  an edgeedge with one O(11)Cd2Tc2 tetrahedra.