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New indides Ce3Ge0.66In4.34 and Ce11Ge4.74In5.26 were synthesized from the elements by arc‐melting and subsequent annealing at 870 K. Single crystals were grown through special annealing procedures in sealed tantalum tubes in a high‐frequency furnace. Both compounds were investigated on the basis of X‐ray powder and single crystal data: I4/mcm, La3GeIn4 type, a = 848.8(1), c = 1192.0(2) pm, Z = 4, wR2 = 0.0453, 499 F2 values, 17 variables for Ce3Ge0.66In4.34 and I4/mmm, Sm11Ge4In6 type (ordered version of the Ho11Ge10 type), a = 1199.3(2), c = 1662.0(3) pm, wR2 = 0.0507, 1217 F2 values, 41 variables for Ce11Ge4.74In5.26. The Ce3Ge0.66In4.34 structure shows a mixed Ge/In occupancy on the 4c Wyckoff position. This site is octahedrally coordinated by cerium atoms. These octahedra share all edges, leading to a three‐dimensional network. The latter is penetrated by a two‐dimensional indium substructure which consists of flattened tetrahedra at In–In distances of 291 and 300 pm. The Ce11Ge4.74In5.26 structure contains three crystallographically independent germanium sites. The latter are coordinated by eight or nine cerium neighbors. These CN8 and CN9 polyhedra are condensed to a complex network which is penetrated by a three‐dimensional indium network with In–In distances of 301–314 pm. The 16m site shows a mixed In/Ge occupancy. Chemical bonding in both compounds is dominated by the p elements. Both ternaries studied exhibit localized magnetism due to the presence of Ce3+ ions. The compound Ce3GeIn4 remains paramagnetic down to 1.72 K, whereas Ce11Ge4In6 orders ferromagnetically at TC = 7.5 K.

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CeNiIn1.0-0.7Ge0-0.3 (ZrNiAl-type structure): a = 0.7530-0.75078(4), c = 0.3974-0.39883(2) nm; CeNiGe1.0-0.7In0-0.3 (TiNiSi-type structure): a = 0.7242-0.72864(4), b = 0.4308-0.43363(2), c = 0.7241-0.72776(3) nm;The substitution of the Indium by Germanium was confirmed from the investigated crystal structure of the CeNiIn0.95Ge0.05 compound by X-ray single crystal method (ZrNiAl-type structure; space group P-62m; a = 0.74877(11), c = 0.40085(8) nm; R1 = 0.0284; 312 F 2 values; 15 variables). In the structure of title compound the mixture of (0,95In + 0,05Ge) occupies the 3g (x 0 1/2) site.The formation of solid solutions and the character of the unit cell parameters variation in the studied and related systems briefly discussed.