Two new non‐isostructural lanthanide(III) nitride tellurides with the composition M4N2Te3 bearing terbium (Tb4N2Te3) and dysprosium (Dy4N2Te3) could be synthesized by the reaction of terbium (Tb) or dysprosium (Dy) metal with sodium azide (NaN3), tellurium (Te), iodine (I2), and sodium iodide (NaI) as flux in evacuated silica tubes for seven days at 950 °C. Tb4N2Te3 crystallizes orthorhombically in space group Pnna with the lattice parameters a = 727.14(5), b = 1164.37(8), c = 1100.93(7) pm, Vm = 140.33(2) cm3·mol–1 (Z = 4). In contrast, Dy4N2Te3 appears in the monoclinic space group P21/n with the lattice parameters a = 719.56(5), b = 1164.05(8), c = 1097.34(7) pm, β = 91.327(3)°, Vm = 138.34(2) cm3·mol–1 (Z = 4). Corresponding to the lanthanide contraction the cell parameters of Dy4N2Te3 show slightly smaller values compared to Tb4N2Te3, but the change of symmetry leads to a different crystal system. Symmetry operations related to a and c are lost according to P2/n21/n2/a → P121/n1 and the two crystallographically independent M3+ cations in Tb4N2Te3 split into four in Dy4N2Te3. Both Tb3+ cations are coordinated by six anions in first sphere plus one Te2– anion further apart for (Tb1)3+ leading to capped trigonal prisms and distorted octahedra. The four Dy3+ cations with coordination numbers of six plus one and three times six also reside in capped and uncapped distorted octahedral anionic coordination. Both crystal structures have infinite zigzag chains in 1∞{[NM$\rm^{e}_{4/2}$]3+} in common, which are formed by trans‐edge connected [NM4]9+ tetrahedra. They run along [010] and exhibit two crystallographically different N3– anions in both cases. The latter are coordinated on the one hand to two sorts of Tb3+ cations in Tb4N2Te3 and on the other hand to four sorts of Dy3+ cations in Dy4N2Te3 as major structural difference. However, both crystal structures show a clear group‐subgroup relationship.

A new short series of isostructural lanthanoid(III) nitride tellurides with the composition Ln3NTe3 (Ln = Gd–Ho) was synthesized through reactions of the metal (Gd–Ho) with sodium azide (NaN3), tellurium (Te), iodine (I2) and sodium iodide (NaI) as flux in evacuated fused silica tubes for seven days at 950 °C. Black, brick‐shaped single crystals of the Ln3NTe3 represenatives crystallize isotypically with Y3NTe3 in the monoclinic space group P21/c with lattice parameters ranging from a = 815.28(6), b = 1200.92(8), c = 866.07(6) pm and β = 109.092(3)° for Gd3NTe3 to a = 802.37(6), b = 1181.69(8), c = 857.30(6) pm and β = 108.816(3)° for Ho3NTe3 and Z = 4. Three crystallographically independent Ln3+ cations form the basic framework of their crystal structure and are coordinated by six anions each. One trigonal prism and two octahedra with different grades of distortion appear as coordination spheres. Isolated dimers [N2Ln6]12+ (d(N–Ln) = 219–232 pm) as pairs of two edge‐sharing [NLn4]9+ tetrahedra, however, serve as main structural feature. Their three‐dimensional interconnection and charge compensation is achieved by three crystallographically distinct Te2– anions (d(Te–Ln) = 299–337 pm) with contacts to four or five Ln3+ cations each. Finally, this short Ln3NTe3 series closes an information gap between the lanthanoid(III) nitride tellurides and the well‐investigated, but not isotypic nitride sulfides and selenides with the same composition (Ln3NCh3: Ln = La–Nd, Sm, Gd–Dy; Ch = S and Se).

Ln 3NTe3(Ln: Gd-Ho). -Ln3NTe3 (Ln: Gd-Ho) are prepared by solid state reactions of Ln, NaN 3, Te, I2 (as Na trap), and NaI as flux (evacuated silica tubes, 950 C, 7 d). The compounds crystallize isotypically with Y3NTe3 in the monoclinic space group P2 1/c (Z = 4, powder and single crystal XRD). Isolated dimers [N2Ln6] 12+ formed by two edge-sharing [NLn 4] 9+ tetrahedra are the main structural feature. Their 3D interconnection and charge compensation is achieved by three crystallographically distinct Te 2anions in contact to 4 or 5 Ln 3+ cations. -(FOLTIN, M. L.; SCHLEID*, T.; Z. Anorg. Allg. Chem. 641 (2015) 2, 292-297, http://dx.doi.org/10.1002/zaac.201400525 ; Inst. Anorg. Chem., Univ. Stuttgart, D-70569 Stuttgart, Germany; Eng.) -J. Schramke 19-021

Ln 13 N 5 Te 12 (Ln = La-Nd), a quite unusual composition of the lanthanoid(III) nitride tellurides, appears with a new crystal structure and can be obtained by reactions of lanthanoid metal (Ln) with elemental tellurium (Te), sodium azide (NaN 3 ), elemental iodine (I 2 ) and sodium iodide (NaI) as flux in evacuated fused silica tubes for seven days at 900°C. The black, shard-shaped single crystals of the short new series Ln 13 N 5 Te 12 (Ln = La-Nd) crystallize monoclinically in the space group P2 1 /m with lattice parameters ranging from a = 1039.86 (7), b = 1373.29(9), c = 1311.78(9) pm, = 100.103(3)°for La 13 N 5 Te 12 to a = 1016.73 (7), b = 1337.58 (9), c = 1288.92(9) pm, = 100.094(3)°for Nd 13 N 5 Te 12 and Z = 2. Unlike the other ternary [a]

Two new non-isostructural gadolinium(III) oxide nitride chalcogenides with the composition Gd 3 ONCh 2 bearing selenide (Gd 3 ONSe 2 ) and telluride (Gd 3 ONTe 2 ) could be synthesized by the reaction of gadolinium metal (Gd) with gadolinium sesquioxide (Gd 2 O 3 ), sodium azide (NaN 3 ), selenium (Se) or tellurium (Te), iodine (I 2 ) and sodium iodide (NaI) as flux in evacuated silica tubes for seven days at 850 to 950°C. Yellow lath-shaped single crystals of Gd 3 ONSe 2 crystallize isotypically to Tb 3 ONSe 2 in the monoclinic space group C2/m with the lattice parameters a = 1560.12(9), b = 395.24(2), c = 977.35(6) pm, β = 97.321(3)°(Z = 4). In contrast, orthorhombic Gd 3 ONTe 2 forms black rods, appears in the space group Pnma with the lattice parameters a = 1337.87(8), b = 408.47(2), c = 1216.78 (7) pm (Z = 4) and adopts the crystal structure of Nd 3 N 2 SeBr. Three crystallographically independent Gd 3+ cations can be found in both oxide