NaCeAgTe4 crystallizes in the tetragonal P4/nmm space group. Na(1) is bonded to four equivalent Ag(1), four equivalent Te(1), and four equivalent Te(3) atoms to form distorted NaAg4Te8 cuboctahedra that share corners with four equivalent Na(1)Ag4Te8 cuboctahedra, edges with four equivalent Na(1)Ag4Te8 cuboctahedra, edges with eight equivalent Ag(1)Na4Ag4Te4 cuboctahedra, faces with four equivalent Na(1)Ag4Te8 cuboctahedra, and faces with four equivalent Ag(1)Na4Ag4Te4 cuboctahedra. Ce(1) is bonded in a 9-coordinate geometry to four equivalent Te(1) and five equivalent Te(2) atoms. Ag(1) is bonded to four equivalent Na(1), four equivalent Ag(1), and four equivalent Te(3) atoms to form distorted AgNa4Ag4Te4 cuboctahedra that share corners with four equivalent Ag(1)Na4Ag4Te4 cuboctahedra, edges with eight equivalent Na(1)Ag4Te8 cuboctahedra, faces with four equivalent Na(1)Ag4Te8 cuboctahedra, and faces with eight equivalent Ag(1)Na4Ag4Te4 cuboctahedra. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Ce(1), and four equivalent Te(1) atoms. In the second Te site, Te(2) is bonded to five equivalent Ce(1) atoms to form a mixture of distorted corner and edge-sharing TeCe5 trigonal bipyramids. In the third Te site, Te(3) is bonded in a 8-coordinate geometry to four equivalent Na(1) and four equivalent Ag(1) atoms.
NaCeAgTe4 crystallizes in the tetragonal P4/nmm space group. Na(1) is bonded to four equivalent Ag(1), four equivalent Te(1), and four equivalent Te(3) atoms to form distorted NaAg4Te8 cuboctahedra that share corners with four equivalent Na(1)Ag4Te8 cuboctahedra, edges with four equivalent Na(1)Ag4Te8 cuboctahedra, edges with eight equivalent Ag(1)Na4Ag4Te4 cuboctahedra, faces with four equivalent Na(1)Ag4Te8 cuboctahedra, and faces with four equivalent Ag(1)Na4Ag4Te4 cuboctahedra. All Na(1)-Ag(1) bond lengths are 3.58 Å. All Na(1)-Te(1) bond lengths are 3.63 Å. All Na(1)-Te(3) bond lengths are 3.29 Å. Ce(1) is bonded in a 9-coordinate geometry to four equivalent Te(1) and five equivalent Te(2) atoms. All Ce(1)-Te(1) bond lengths are 3.29 Å. There are four shorter (3.29 Å) and one longer (3.32 Å) Ce(1)-Te(2) bond length. Ag(1) is bonded to four equivalent Na(1), four equivalent Ag(1), and four equivalent Te(3) atoms to form distorted AgNa4Ag4Te4 cuboctahedra that share corners with four equivalent Ag(1)Na4Ag4Te4 cuboctahedra, edges with eight equivalent Na(1)Ag4Te8 cuboctahedra, faces with four equivalent Na(1)Ag4Te8 cuboctahedra, and faces with eight equivalent Ag(1)Na4Ag4Te4 cuboctahedra. All Ag(1)-Ag(1) bond lengths are 3.15 Å. All Ag(1)-Te(3) bond lengths are 2.90 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Ce(1), and four equivalent Te(1) atoms. All Te(1)-Te(1) bond lengths are 3.15 Å. In the second Te site, Te(2) is bonded to five equivalent Ce(1) atoms to form a mixture of distorted corner and edge-sharing TeCe5 trigonal bipyramids. In the third Te site, Te(3) is bonded in a 8-coordinate geometry to four equivalent Na(1) and four equivalent Ag(1) atoms.