Synthesis and Crystal Structure of Manganese‐tris(1,2‐ethanediamine)tetratelluride [Mn(en)3]Te4 Exhibiting Intermolecular Interactions between the Tetratelluride Anions

Air‐sensitive black crystals of the new compound [Mn(en)₃]Te₄ were synthesized by reacting MnCl₂ · 4 H₂O, K₂Te₃ and elemental Te in 1,2‐ethanediamine (en) under solvothermal conditions at 433 K. The compound crystallizes in the monoclinic space group P2₁/n with lattice parameters a = 839.51(7) pm, b = 1551.3(1) pm, c = 1432.6(1) pm, and β = 90.28(2)°. Isolated [Mn(en)₃]²⁺ cations and Te₄^2– anions are arranged in an alternating fashion parallel to the crystallographic b‐axis. One terminal Te atom of the Te₄^2– anions exhibits a short intermolecular contact to a neighboured anion thus forming Te₈^4– anions. A slightly longer interionic Te…Te separation is observed between two of the inner Te atoms of neighboured Te₈^4– anions. Taking these longer separations into account infinite Te‐chains are formed running parallel to [001]. The intermolecular Te…Te interactions affect the Te–Te bond lengths within the Te₄^2– anion leading to a lengthening of the average Te–Te distance. Short N–H…Te distances indicate hydrogen bonding between the cations and anions. DTA‐TG measurements show that at 441 K the material decomposes in one step. The resulting crystalline material consists of MnTe₂ and Te.     

Beiträge zur Kristallchemie der Urantelluride. II. Die Kristallstruktur des Diuranpentatellurids U2Te5

Contributions to the Crystal Chemistry of Uranium Tellurides. II. The Crystal Structure of Diuranium Pentatelluride U₂Te₅ Via chemical transport reactions with TeBr₄ as transporting agent single crystals of the title compound up to a size of 5 mm were available from the elements. The analysis by atomic emission spectrometry gave UTe_2.52(4). By X-ray single crystal structure analysis we found that U₂Te₅ crystallizes monoclinic (space group C2/m, Z = 4) with a = 3443.3(5) pm, b = 418.65(3) pm, c = 607.97(6) pm and β = 95.35(1)º in a new structure type. The layer structure is built up by bicapped trigonal prisms, one half as isolated building units, the other connected via faces as fourfold capped biprisms. A structural relationship of diuranium pentatelluride to the adjacent phases in the phase diagram U? Te can be expressed by the formulation as UTe₂ · UTe₃.     

Rheniumselenidtelluride Re2SexTe5–x: Die Struktur von Re6Se8Te7

Rhenium Selenidetellurides Re₂Se_xTe_5–x: The Structure of Re₆Se₈Te₇ Well-crystallized rhenium selenidetellurides of the Re₂Te₅-type structure were prepared from the elements in evacuated sealed quartz glas tubes at 1 130 K within 14 d. The orthorhombic lattice parameters of the phases shrink with increasing selenium content from a = 1 304.9(1) ? 1 255.8(2) pm, b = 1 297.5(1) ? 1 260.0(2) pm, and c = 1 425.1(1) ? 1 408.2(1) pm. The phase width ends at composition Re₂Se_2.7Te_2.3. An X-ray structure analysis of a crystal of composition Re₆Se₈Te₇ was performed. Selenium and tellurium atoms differ structurally completely: Whereas the selenium atoms are separated within distorted octahedral [Re₆Se₈] clusters, the tellurium atoms form homonuclear bonded bicyclic [Te(Te₃)₂] units. They also link the clusters which are arranged according to the motif of a cubic closest packing.     

Die KristallStrukturen von K6[Ge2Te6] und K6[Sn2Te6] und ihre kristall-chemische Beziehung zum K6[Si2Te6]-Typ

Crystal Structures of K₆[Ge₂Te₆] and K₆[Sn₂Te₆] and their Relations to the K₆[Si₂Te₆] Type K₆[Ge₂Te₆] and K₆[Sn₂Te₆], the first members of the families of telluro-digermanates and telluro-distannates have been prepared and their structures determined. The space group is C 2/c with cell constants a = 16.010(8), b = 13.619(8), c = 9.713(5) Å, β = 95.19(5)° and Z = 4 for the Ge compound. The Sn compound has space group P 2₁/c, a = 9.590(5), b = 13.654(8), c = 9.606(5) Å, β = 116.84(5) and Z = 2. The structures were established by direct methods, using four-circle diffractometer data. The final R value for 828 (1677) independent reflexions is 0.068 (0.047) for the Ge (Sn) compound. Both structures have discrete X₂Te₆ groups (X = Ge, Sn) in staggered conformation connected by K atoms in distorted octahedral or trigonal prismatic environments and bear direct subgroup relationships to that of K₆[Si₂Te₆]. The average X? Te distance is 2.579 (2.724) Å and the X? X distance 2.492 (2.814) Å.     

Sr13□NbAs11 and Eu13□NbAs11 – Defect Variants of the Ca14AlSb11 Structure with asymmetric [As3]7− anions

The novel compounds Sr₁₃NbAs₁₁ and Eu₁₃NbAs₁₁ have been synthesized from SrAs, Eu₅As₄, Sr, Nb and As in niobium ampoules at 1173–1273 K. The tetragonal tI 200 phases are defect variants of the Ca₁₄AlSb₁₁ structure (space group I4₁/acd (no. 142); Sr₁₃□NbAs₁₁: a = 1649.8(2) and c = 2214.1(3); Eu₁₃□NbAs₁₁: a = 1632.9(8) and c = 2197.3(8) pm; Z = 8). The structures are built from the cations Sr²⁺, and Eu²⁺, respectively, and from the anions [NbAs₄]^7?, As^3?, and the linear polyanion [As₃]^7?. This polyanion (isosteric to I₃^?) is asymmetric with d(As? As) = 273.0 and 346.0 pm (Sr) and 274.7 and 335.6 pm (Eu), respectively. The bond lengths in the tetrahedral anions are d(Nb? As) = 250.8 and 251.1 pm. The complete structural arrangement is related to that of Cu₂O by forming two interpenetrating networks. The oxygen atoms are substituted by niobium centered As₄ tetrahedra, and the Cu atoms are substituted by As₆ octahedra (centered by Sr, Eu). The central As atoms of the polyanions connect the nets. Both As networks are enveloped by the remaining cations forming cubes, tetragonal antiprisms and capped trigonal prisms.     

Über Oxidtelluride (M2O2Te) der leichten Lanthanide (M = La–Nd,Sm–Ho) im A-Typ mit anti-ThCr2Si2-Struktur

On Oxytellurides (M₂O₂Te) of the Early Lanthanides (M = La–Nd, Sm–Ho) with A- or anti -ThCr₂Si₂-Type Crystal Structure By reacting elementary lanthanide metal (M = La–Nd, Sm–Ho) with tellurium dioxide (TeO₂) in a 2 : 1 molar ratio, it is possible to obtain pure and single-phase oxytellurides of the composition M₂O₂Te at 750 °C in evacuated silica tubes within a few days. When larger quantities of cesium chloride (CsCl) are added as flux, plate-like single crystals with square cross-section are formed which are not sensitive to hydrolysis and very suitable for crystal structure refinements from X-ray data. In the anti-ThCr₂Si₂ analogous crystal structure (tetragonal, I4/mmm, Z = 2; La₂O₂Te: a = 412.31(4), c = 1309.6(1) pm; Ce₂O₂Te: a = 408.17(4), c = 1294.7(1) pm; Pr₂O₂Te: a = 405.62(4), c = 1285.8(1) pm; Nd₂O₂Te: a = 403.08(4), c = 1277.1(1) pm; Sm₂O₂Te: a = 399.83(4), c = 1265.5(1) pm; Eu₂O₂Te: a = 397.56(4), c = 1257.9(1) pm; Gd₂O₂Te: a = 396.20(4), c = 1253.2(1) pm; Tb₂O₂Te: a = 393.89(4), c = 1245.4(1) pm; Dy₂O₂Te: a = 392.34(4), c = 1240.3(1) pm; Ho₂O₂Te: a = 390.57(6), c = 1239.0(3) pm) the M³⁺ cations are surrounded by nine anions (4 O^2– und 4 + 1 Te^2–) in the shape of a capped square antiprism. The anions show coordination numbers of four (O^2–: tetrahedra) and eight plus two (Te^2–: bicapped cubes) with respect to the cations. PbO-analogous square {[OM_4/4]₂}²⁺ triple layer slabs are present parallel (001), which originate through two-dimensional infinite linking of [OM₄]¹⁰⁺ tetrahedra via two trans-orientated pairs of edges (i. e. four edges altogether). These cationic layers are piled alternatingly along [001] with likewise quadratic single layers of Te^2– anions, which take care of the three-dimensional coherence as well as of the charge balance.     

The Crystal Structure of Tl2Te3 – a Reinvestigation

Crystals of the title compound were obtained by annealing a powder of Tl₂Te₃ in a vertical temperature gradient (230 °C–240 °C, 4 weeks). Tl₂Te₃ crystallizes in space group C2/c with lattice parameters of a = 13.275(1) Å, b = 6.562(1) Å, c = 7.918(1) Å, and β = 107.14°(2). The tellurium atoms form chains [Te₃^2–], consisting of interconnected linear triatomic · Te–^Te–Te · groups which are isosteric with XeF₂. The Te–Te distances of the XeF₂-like units are 3.02 Å, the connecting ones 2.83 Å.     

Polymere,bandförmige Tellurkationen in den Strukturen des Chloroberyllats Te7[Be2Cl6] und des Chlorobismutats (Te4)(Te10)[Bi4Cl16]

Polymeric, Band Shaped Tellurium Cations in the Structures of the Chloroberyllate Te₇[Be₂Cl₆] and the Chlorobismutate (Te₄)(Te₁₀)[Bi₄Cl₁₆] Te₇[Be₂Cl₆] is obtained at 250 °C in an eutectic Na₂[BeCl₄] / BeCl₂ melt from Te, TeCl₄ und BeCl₂ in form of black crystals, which are sensitive towards hydrolysis in moist air. (Te₄) (Te₁₀)[Bi₄Cl₁₆] is prepared from Te, TeCl₄ und BiCl₃ by chemical vapour transport in sealed evacuated glass ampoules in a temperature gradient 150 ° → 90 °Cin form of needle shaped crystals with a silver lustre. The structures of both compounds were determined based on single crystal X‐ray diffraction data (Te₇[Be₂Cl₆]: orthorhombic, Pnnm, Z = 2, a = 541.60(3), b = 974.79(6), c = 1664.4(1) pm; (Te₄)(Te₁₀)[Bi₄Cl₁₆]: triclinic, P1¯, Z = 2, a = 547.2(3), b = 1321.1(7), c = 1490(1) pm, α = 102.09(5)°, β = 95.05(5)°, γ = 96.69(4)°). The structure of Te₇[Be₂Cl₆] consists of one‐dimensional polymeric cations (Te₇²⁺)_n which form folded bands and of discrete [Be₂Cl₆]^2— anions which form double tetrahedraconnected by a common edge. By a different way of folding compared with the cations present in the structures of Te₇[MOX₄]X (M = Nb, W; X = Cl, Br) the (Te₇²⁺)_n cation in Te₇[Be₂Cl₆]represents a new, isomeric form. The structure of (Te₄)(Te₁₀)[Bi₄Cl₁₆] contains two different polymeric cations. (Te₁₀²⁺)_n consists of planar Te₁₀ groups in the form of three corner‐sharing Te₄ rings connected to folded bands. (Te₄²⁺)_n forms in contrast to the so far notoriously observed discrete, square‐planar E₄²⁺ ions a chain of rectangular planar Te₄ rings (Te—Te 274 and 281 pm) connected by Te‐Te bonds of 297 pm. [Bi₄Cl₁₆]^4— has a complex one‐dimensional structure of edge‐ and corner‐sharing BiCl₇ units.     

The Sodium Antimony Telluridogermanate(III) Na9Sb[Ge2Te6]2

Systematic studies in the quaternary system Na/Ge/Sb/Te yielded the new compound Na₉Sb[Ge₂Te₆]₂. Its crystal structure is isotypic to Na₉Sb[Ge₂Se₆]₂ (space group C2/c with a = 9.541(2), b = 26.253(7), c = 7.5820(18) Å and β = 122.233(15)°, Z = 2). The structure is characterized by Ge–Ge dumbbells that are octahedrally coordinated by Te, forming ethane‐like [Ge₂Te₆]^6– anions. Cation sites are occupied by Na⁺ as well as shared by Na⁺ and Sb³⁺. Na₉Sb[Ge₂Te₆]₂ is formally obtained from the reaction of one equivalent Na₈[Ge₄Te₁₀] and one equivalent NaSbTe₂. In contrast to members of the metastable solid solution series (NaSbTe₂)_1–x(GeTe)_x, Na₉Sb[Ge₂Te₆]₂ is a thermodynamically stable compound. It is a semiconductor with a bandgap of 1.51 eV.     

Tellur-Polykationen stabilisiert durch Nioboxidhalogenide: Synthese und Kristallstrukturen von Te7NbOBr5 und Te7NbOCl5

Tellurium Cations stabilized by Niobium Oxytrihalides: Synthesis and Crystal Structure of Te₇NbOBr₅ and Te₇NbOCl₅ The reaction of Te₂Br with NbOBr₃ in a sealed evacuated glass ampoule at 225°C yields Te₇NbOBr₅ in form of bright black needles. Te₇NbOCl₅ is obtained from tellurium, TeCl₄ and NbOCl₃ at 220°C. Both compounds crystallize orthorhombic in the space group Pcca (Te₇NbOBr₅: a = 2 651,9(4) pm, b = 836.6(1) pm, c = 794.6(1) pm; Te₇NbOCl₅: a = 2 597.7(5) pm, b = 805.1(1) pm, c = 791.2(1) pm). The crystal structure determinations show that Te₇NbOBr₅ and Te₇NbOCl₅ are built of one-dimensional polymeric tellurium cations, one-dimensional associated pyramidal NbOX₄ groups (X = Cl, Br) and isolated halide anions. Magnetic properties of Te₇NbOX₅ were determined and confirm the expected diamagnetism. Te₇NbOX₅ can thus be formulated as [Te₇²⁺] [NbOX₄^?] (X^?). The charge distribution in the structure type Te₇MOX₅ (M = W, Nb; X = Cl, Br) became clear by synthesis and characterisation of the two niobium containing compounds.     

Synthesis and Crystal Structure of Te6[MCl6] (M = Zr,Hf), Containing a Polymeric Chalcogen Cation (Te62+)n

The reaction of tellurium, tellurium tetrachloride, and ZrCl₄ or HfCl₄, respectively, under the conditions of chemical vapour transport in a temperature gradient 220 → 200 °C yields black crystals of Te₆[ZrCl₆] and Te₆[HfCl₆]. While Te₆[ZrCl₆] is formed almost quantitatively, Te₆[HfCl₆] is always accompanied by neighbored phases such as Te₄[HfCl₆] and Te₈[HfCl₆]. The crystal structures of Te₆[ZrCl₆] (orthorhombic, Pbcm, a = 1095.4(1), b = 1085.2(1), c = 1324.5(1) pm) and Te₆[HfCl₆] (a = 1094.8(2), b = 1086.3(2), c = 1325.0(2) pm) are isotypic and consist of one‐dimensional polymeric (Te₆²⁺)_n cations and of discrete, only slightly distorted octahedral [MCl₆]^2‐ anions (M = Zr, Hf). The cations are build of five membered rings which are connected via single Te atoms to a polymer ‐Te‐Te₅‐Te‐Te₅‐. Out of the six Te atoms of the asymmetric unit of the chain four atoms exhibit two bonds and two atoms exhibit three bonds. The connecting, threefold coordinated Te atoms of the five membered rings carry formally the positive charges. In consistence with the assumption of the presence of throughout localized bonds eH band structure calculations for Te₆[ZrCl₆] show semiconducting behaviour with a band gap of 1.8 eV.     

Ba2Ge2Te5, ein neues Kettentelluridogermanat(III)

On Ba₂Ge₂Te₅, a New Telluridogermanate(III) with Chain Structure The new compound Ba₂Ge₂Te₅ crystallizes in the orthorhombic system (space group: Pna2₁ (No. 33)) with lattice constants s. “Inhaltsübersicht”. In the structure distorted Ge₂Te₆- trigonal prisms are connected by common corners to infinite chains.     

Das prismatische Te62+-Ion in der Struktur von Te6(NbOCl4)2

The Prismatic Te₆²⁺ Ion in the Structure of Te₆(NbOCl₄)₂ Te₆(NbOCl₄)₂ is obtained from Te, TeCl₄ and NbOCl₃ at 200°C. It crystallizes triclinic, space group P1 (a = 915,5(4) pm, b = 1655,3(6) pm, c = 3134,4(9) pm, α = 42,62(2)°, β = 117,12(6)°, γ = 138,24(8)°). The crystal structure analysis shows, that the structure is built of one-dimensional polymeric [NbOCl₄^?] chains in which the monomers are linked via linear O? Nb? O-bridges and from discrete Te₆²⁺ polycations that are also arranged in strands, but without significant interactions. The structure is closley related but not isotypic to the previously reported tungsten containing analogue Te₆(WOCl₄)₂ (monoclinic, P2₁/c). A comparison of the two structures shows that rotations of the cationic strands relative to the anionic strands lead to different cation-anion interactions.     

[Ge4O6Te4]4—, an Adamantanoid Oxotellurido Germanate(IV) with a Central Ge4O6 Core

[Mn(en)₃]₂[Ge₄O₆Te₄]·1.5en ( 1 ) and (enH)₃[Mn(en)₃]₃[Ge₄O₆Te₄]₂I·4.7en ( 2 ) may be prepared at 150 °C by solvothermal reaction of elemental Ge and Te with Mn(OOCCH₃)₂ ·4H₂O in the presence of [CH₃)₄N]I as a mineralizer in respectively superheated ethylenediamine (en) or an en/CH₃OH (3:2) mixture. Both contain the novel [Ge₄O₆Te₄]^4— anion with a central adamantanoid Ge₄O₆ core and four terminal Te atoms and represent the first examples of such a mixed [M₄E₆E₄′]^4— anion (M = Si‐Sn; E = O‐Te). As a result of their increased polarity, the Ge‐Te bonds of 2 are markedly shorter (2.438 — 2.462Å) than those previously reported for telluridogermanates(IV).     

Nb2Y2X6, a Novel Type of NbIV Compounds with Cross-linked Nb2 and Y2 Dumbbells (Y = Se,Te; X = Br,I)

The compounds Nb₂Se₂Br₆, Nb₂Te₂Br₆, and Nb₂Te₂I₆ were prepared from the elements in sealed quartz ampoulès at 1073 K. The crystalline solids, exhibiting a metallic lustre, are insensitive against moisture and oxygen. All compounds undergo several reversible thermal transitions with temperature (DTA). Beside binary halides only NbYX₃ is present in the gas phase. The structures consist of one-dimensional infinite chains of halogen bridged Nb₂(Y₂)X₄ units containing single side-on bonded Nb₂ and Y₂ dumbbells forming a quasi tetrahedral Nb₂Y₂ cluster (Nb? Nb ? 283.2; 287.5; 293.2 pm; Se? Se ? 230.5 pm; Te? Te ? 267.0; 268.5 pm). The structural and magnetic properties clearly prove the formal oxidation states Nb⁴⁺ and Y^1?, unexpected from stoichiometry. (Structural data: all P2/a (No. 13); Nb₂Se₂Br₆: a = 1254.0(12); b = 689.7(10); c = 662.4(10) pm; β = 98.9(1)°; Z = 2; 1274 hkl; R = 0.066. Nb₂Te₂Br₆: a = 1259.7(13); b = 713.5(9); c = 667.0(9) pm; β = 97.6(1)°; 1557 hkl; R = 0.043. Nb₂Te₂I₆: a = 1347.3(3); b = 742.9(2); c = 714.1(2) pm; β = 98.52(2)°; 1540 hkl; R = 0.026).     

Über polygermane: XI. Funktionalisierung von hexaphenyldigerman

The optimum conditions for selectively cleaving off two phenyl groups in Ge₂Ph₆ by trichloroacetic acid have been determined. Neither trihaloacetic acids nor HCl/AlCl₃ nor reactive tetrahalides MCl₄ are suitable reagents for cleaving one phenyl group alone. The ¹³C NMR chemical shifts of functional phenyl-mono- and -digermanes are given. The crystal structure of 1,2-bis(trichloroacetate)tetraphenyldigermane has been determined and refined to R = 0.048. The digermane bond is bridged by both acetates (distances GeGe 239.3(2), GeO 207.3(3) and 231.4(3) pm). The Ge atoms have trigonal bipyramidal coordination.     

Unexpected Ge–Ge Contacts in the Two‐Dimensional Ge4Se3Te Phase and Analysis of Their Chemical Cause with the Density of Energy (DOE) Function

A hexagonal phase in the ternary Ge–Se–Te system with an approximate composition of GeSe_0.75Te_0.25 has been known since the 1960s but its structure has remained unknown. We have succeeded in growing single crystals by chemical transport as a prerequisite to solve and refine the Ge₄Se₃Te structure. It consists of layers that are held together by van der Waals type weak chalcogenide–chalcogenide interactions but also display unexpected Ge–Ge contacts, as confirmed by electron microscopy analysis. The nature of the electronic structure of Ge₄Se₃Te was characterized by chemical bonding analysis, in particular by the newly introduced density of energy (DOE) function. The Ge–Ge bonding interactions serve to hold electrons that would otherwise go into antibonding Ge–Te contacts.     

[K(15-Krone-5)2]2Te8 — ein bicyclisches Polytellurid

[K(15-Crown-5)₂]₂Te₈ – a Bicyclic Polytelluride The octatelluride [K(15-crown-5)₂]₂Te₈ has been synthesized by the oxydation of a potassium tritelluride solution in dimethylformamide by iron(III) chloride in the presence of 15-crown-5, forming black crystals, which were characterized by an X-ray structure determination. Space group Pca2₁, Z = 4, 4 548 observed unique reflections, R = 0.048. Lattice dimensions at –70°C: a = 1 881(1), b = 2 211(2), c = 1 530(1) pm. The structure consists of cations [K(15-crown-5)₂]⁺, in which the potassium ions are sandwichlike coordinated by the oxygen atoms of the two disordered crown ether molecules, and of bicyclic Te₈^2? ions. In these anions a Te²⁺ ion is chelated in a planar fashion by a Te₃^2? and a Te₄^2? unit.     

The Crystal Structures of Eu5Ge3 and EuIrGe2

Eu₅Ge₃ and EuIrGe₂ were prepared from the elements in tantalum tubes, and their crystal structures were determined from single crystal X-ray data. Eu₅Ge₃ adopts the structure of Cr₅B₃: I4/mcm, a = 799.0(1)pm, c = 1 536.7(1)pm, Z = 4, wR2 = 0.0421 for 669 F² values and 16 variables. The structure of Eu₅Ge₃ contains isolated germanium atoms and germanium atom pairs with a Ge? Ge distance of 256.0 pm. Eu₅Ge₃ may be described as a Zintl phase with the formulation [5 Eu²⁺]¹⁰⁺[Ge]^4?[Ge₂]^6?. Magnetic investigations of Eu₅Ge₃ show Curie-Weiss behaviour above 50 K with a magnetic moment of μ_exp = 7.6(1) μ_B which is close to the free ion value of μ_eff = 7.94 μ_B for Eu²⁺. EuIrGe₂ is isotypic with CeNiSi₂: Cmcm, a = 445.5(2) pm, b = 1 737.4(4) pm, c = 426.6(1) pm, Z = 4, wR2 = 0.0507 for 295 F² values and 18 variables. The structure of EuIrGe₂ is an intergrowth of ThCr₂Si₂-like slabs with composition EuIr₂Ge₂ and AlB₂-like slabs with composition EuGe₂ in an AB stacking sequence. Both slabs are distorted when compared to the symmetry of the prototypes. The Ge? Ge distance of 256.6 pm in the AlB₂-like fragment is comparable to that in Eu₅Ge₃.     

Quaternary Germanides RE3TRh4Ge4 (RE = Ce,Pr, Nd; T = Nb,Ta) – A New Coloring Variant of the Aristotype AlB2

The quaternary germanides RE₃TRh₄Ge₄ (RE = Ce, Pr, Nd; T = Nb, Ta) were synthesized from the elements by arc‐melting and subsequent annealing in a muffle furnace. The structure of Ce₃TaRh₄Ge₄ was refined from single‐crystal X‐ray diffractometer data: new type, Pbam, a = 719.9(2), b = 1495.0(3), c = 431.61(8), wR₂ = 0.0678, 1004 F² values, and 40 variables. Isotypy of the remaining phases was evident from X‐ray powder patterns. Ce₃TaRh₄Ge₄ is a new superstructure variant of the aristotype AlB₂ with an ordering of cerium and tantalum on the aluminum site, whereas the honey‐comb network is built up by a 1:1 ordering of rhodium and germanium. This crystal‐chemical relationship is discussed based on a group‐subgroup scheme. The distinctly different size of tantalum and cerium leads to a pronounced puckering of the [Rh₄Ge₄] network, which shows the shortest interatomic distances (253–271 pm Rh–Ge) within the Ce₃TaRh₄Ge₄ structure. Another remarkable structural feature concerns the tantalum coordination with six shorter Ta–Rh bonds (265–266 pm) and six longer Ta–Ge bonds (294–295 pm). The [Rh₄Ge₄] network fully separates the tantalum and cerium atoms (Ce–Ce > 387 pm, Ta–Ta > 431 pm, and Ce–Ta > 359 pm). The electronic density of states DOS from DFT calculations show metallic behavior with large contributions of localized Ce 4f as well as itinerant ones from all constituents at the Fermi level but no significant magnetic polarization on Ce could be identified. The bonding characteristics described based on overlap populations illustrate further the crystal chemistry observations of the different coordination of Ce1 and Ce2 in Ce₃TaRh₄Ge₄. The Rh–Ge interactions within the network are highlighted as dominant. The bonding magnitudes follow the interatomic distances and identify differences of Ta bonding vs. Ce1/Ce2 bonding with the Rh and Ge substructures.