The Zintl Phase Eu2Si

The Zintl phase Eu₂Si was synthesized from elemental europium and silicon in a sealed tantalum tube in a high‐frequency furnace at 1270 K and subsequent annealing at 970 K. Investigation of the sample by X‐ray powder and single crystal techniques revealed: Co₂Si (anti‐PbCl₂) type, space group Pnma, a = 783.0(1), b = 504.71(9), c = 937.8(1) pm, wR2 = 0.1193, 459 F² values and 20 variables. The structure contains two europium and one silicon site. ¹⁵¹Eu Mössbauer spectroscopic data show a single signal at an isomer shift of −9.63(3) mm/s, compatible with divalent europium. Within the Zintl concept electron counting can be written as (2Eu²⁺)⁴⁺Si⁴⁻, in agreement with the absence of Si‐Si bonding. Each silicon atom has nine europium neighbors in the form of a tri‐capped trigonal prism. The silicon coordinations of the Zintl phases Eu₂Si, Eu₅Si₃, EuSi, and EuSi₂ are compared.     

Investigating the Role of Vacancies on the Thermoelectric Properties of EuCuSb-Eu2ZnSb2 Alloys

AMX compounds with the ZrBeSi structure tolerate a vacancy concentration of up to 50 % on the M-site in the planar MX-layers. Here, we investigate the impact of vacancies on the thermal and electronic properties across the full EuCu_1−xZn_0.5xSb solid solution. The transition from a fully-occupied honeycomb layer (EuCuSb) to one with a quarter of the atoms missing (EuZn_0.5Sb) leads to non-linear bond expansion in the honeycomb layer, increasing atomic displacement parameters on the M and Sb-sites, and significant lattice softening. This, combined with a rapid increase in point defect scattering, causes the lattice thermal conductivity to decrease from 3 to 0.5 W mK⁻¹ at 300 K. The effect of vacancies on the electronic properties is more nuanced; we see a small increase in effective mass, large increase in band gap, and decrease in carrier concentration. Ultimately, the maximum zT increases from 0.09 to 0.7 as we go from EuCuSb to EuZn_0.5Sb.     

K6Pb8Cd: A Zintl Phase with Oligomers of Pb4 Tetrahedra Interconnected by Cd Atoms

Unprecedented (Pb ₄ )Cd(Pb ₄ )Cd(Pb ₄ )Cd(Pb ₄ ) tetramers (see picture) are present in the structure of the title compound, in which they coexist with isolated Pb₄ tetrahedra. Since Cs₆Ge₈Zn has the same stoichiometry as K₆Pb₈Cd but contains exclusively (Ge₄)₂Zn dimers, this can be viewed as a disproportionation reaction of the type (a).     

Zintl Phases: Transitions between Metallic and Ionic Bonding

Experimental studies on compounds of alkali and alkaline earth metals with semi- and metametals have considerably broadened the basis for a discussion of the transition from metallic to ionic bonding. Current interest is focused mainly upon the elucidation of the principles governing the structure of such compounds which are subject to a wide range of variation within this class of materials. A new definition of the term Zintl phase is proposed after consideration of available findings.     

Evidence of a Mixed Magnetic Phase in EuMgGe: A Semi­metallic Zintl Compound with TiNiSi Structure Type

The ternary Zintl phase EuMgGe was synthesized from the elements, and its structure solved by single‐crystal X‐ray diffraction. Chemical bonding is discussed, by means of electronic structure calculations at the DFT level and its physical properties characterized with respect to electronic conductivity, magnetic susceptibility, specific heat capacity, and magnetoresistivity. The compound may be interpreted according to the Zintl‐Klemm concept as (Eu²⁺)(Mg²⁺)(Ge^4–) with isolated germanium anions. Resistivity measurements reveal a semimetallic character, which is consistent with the vanishing energy gap obtained from our calculations. The magnetic susceptibility and the specific heat indicate that two consecutive transitions take place, at 9 and 16 K, and they show evidence of magnetic frustration. A possible physical scenario for this magnetic behavior is discussed based on known models of partially frustrated magnets.     

Homogeneity range of the NaTl-type Zintl phase in the ternary system Li-In-Ag

The remarkably broad homogeneity range of the NaTl-type Zintl phase in the ternary phase diagram Li-In-Ag at room temperature was determined by structure evaluation using X-ray powder diffraction. The colours of the investigated Zintl phases correlate with the valence electron concentration (VEC) as already established for the quasibinary cut Li_0.5(In_xAg_1−x)_0.5 with 0.47?x?1.00, i.e. with decreasing VECs the colour changes from grey over reddish to bright yellow. All compounds in the new quasibinary cut Li_x(In_0.5Ag_0.5)_1−x with 0.47?x?0.60 appear free from vacancies in the Li-sublattice, even for Li-deficient compositions. The partial occupation of Li-sites by excess Ag and In instead is in full agreement with the behaviour of the binary NaTl-type Zintl phases Li_xZn_1−x and Li_xCd_1−x (0.47?x?0.54) with a low VEC about 1.5.     

A10LaCdSb9 (A=Ca,Yb): A Highly Complex Zintl System and the Thermoelectric Properties

Two new Zintl compounds A₁₀LaCdSb₉ (A=Ca, Yb), namely, Ca_9.81(1)La_0.97(1)Cd_1.23(1)Sb₉ and Yb_9.78(1)La_0.97(1)Cd_1.24(1)Sb₉, have been designed and synthesized by applying the Zintl concept. Although both compounds are isoelectronic with their Ca₁₁InSb₉ and Yb₁₁InSb₉ analogues, they crystallize in a new structure type with the orthorhombic space group Ibam (No.72) and feature very complex anion structures, which are composed of unique [Cd₂Sb₆]^12? clusters, dumbbell‐shaped [Sb₂]^4? dimers, and isolated [Sb]^3? anions. For Yb_9.78(1)La_0.97(1)Cd_1.24(1)Sb₉, an extremely low lattice thermal conductivity of 0.29 W m^?1 K^?1 was observed at 875 K, which almost approaches the lowest reported limit of nonglassy or nonionically conducting bulk materials. According to thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses, both compounds show very good thermal stability and no melting or phase transition processes were found below 1173 K. Although related thermoelectric property studies on Yb_9.78(1)La_0.97(1)Cd_1.24(1)Sb₉ only present a maximum ZT of 0.11 at 920 K, owing to its low Seebeck coefficients, these materials are still very promising for their high temperature stability and low thermal conductivity. Furthermore, as mixed cations exist with different charges, it makes this system very flexible in tuning the related electrical properties.     

Orthorhombic Inverse Perovskitic Ba3TtO (Tt = Ge,Si) as Zintl Phases

The isotypic title compounds are obtained in high yield from the reactions of Ba, BaO, and Ge (Si) in welded Ta containers slowly cooled from 1100 °C. The structure of Ba₃GeO was determined by single-crystal X-ray diffraction (orthorhombic symmetry; Pnma (No. 62); a = 7.591(1), b = 10.728(1), c = 7.551(1) Å; Z = 4; R = 0.058, R_w = 0.065 for 780 reflections (I > 3σ(I)) with 2θ_max = 60°)). The structure consists of slightly deformed OBa₆ octahedra that are tilted by £ 14° with respect to their positions in the ideal inverse perovskite structure. These distortions optimize eight of the original twelve equal Ba–Ge distances. The ideal cubic Ca₃SiO (a = 4.699(1) Å) has also been synthesized.     

The Hydrogenation of the Zintl Phase NdGa Studied by in situ Neutron Diffraction

The hydrogenation of the Zintl phase NdGa was studied by in situ neutron powder diffraction. We find a compositional range of 0.1 < x < 0.8 in NdGaH_1+x. Hydrogen atoms are located in two different positions, in HNd₄ tetrahedra, and close to the polyanionic chains. For the latter, the Ga–H distance in NdGaH_1.66 is quite long (ca. 200 pm) with a trigonal bipyramidal Nd₃Ga₂ surrounding of hydrogen atoms. Hydrogen poor NdGaH_<1 phases as known for similar systems were not observed. The changing hydrogen content shows no measureable effect on the unit cell volume, but on lattice parameter ratios. Superstructures occur for 0.53 < x < 0.66 and 0.73 < x < 0.8, leading to a doubling or tripling of the lattice parameter a. They are probably caused by partial hydrogen ordering. The threefold superstructure contains a ¹_∞[(Ga–H–Ga–H–Ga)^6–] moiety with hydrogen bridging two gallium chains.     

The Metallic Zintl Phase Ba3Si4 – Synthesis,Crystal Structure,Chemical Bonding,and Physical Properties

The Zintl phase Ba₃Si₄ has been synthesized from the elements at 1273 K as a single phase. No homogeneity range has been found. The compound decomposes peritectically at 1307(5) K to BaSi₂ and melt. The butterfly‐shaped Si₄⁶⁻ Zintl anion in the crystal structure of Ba₃Si₄ (Pearson symbol tP28, space group P4₂/mnm, a = 8.5233(3) Å, c = 11.8322(6) Å) shows only slightly different Si‐Si bond lengths of d(Si–Si) = 2.4183(6) Å (1×) and 2.4254(3) Å (4×). The compound is diamagnetic with χ ≈ −50 × 10⁻⁶ cm³ mol⁻¹. DC resistivity measurements show a high electrical resistivity (ρ(300 K) ≈ 1.2 × 10⁻³ Ω m) with positive temperature gradient dρ/dT. The temperature dependence of the isotropic signal shift and the spin‐lattice relaxation times in ²⁹Si NMR spectroscopy confirms the metallic behavior. The experimental results are in accordance with the calculated electronic band structure, which indicates a metal with a low density of states at the Fermi level. The electron localization function (ELF) is used for analysis of chemical bonding. The reaction of solid Ba₃Si₄ with gaseous HCl leads to the oxidation of the Si₄⁶⁻ Zintl anion and yields nanoporous silicon.     

Ca3Ag1+xGe3–x (x = 1/3): New Transition Metal Zintl Phase with Intergrowth Structure and Alloying with Aluminum Metal

Abstract. The ternary Zintl phase Ca₃Ag_1+xGe_3–x (x = 1/3) was synthesized by the high‐temperature solid‐state technique and its crystal structure was refined from single‐crystal diffraction data. The compound Ca₃Ag_1.32Ge_2.68(1) adopts the Sc₃NiSi₃ type structure, crystal data: space group C2/m, a = 10.813(1) Å, b = 4.5346(4) Å, c = 14.3391(7) Å, β = 110.05(1)° and V = 660.48(10) ų for Z = 4. Its structure can be interpreted as an intergrowth of fragments cut from the CaGe (CrB‐type) and the CaAg_1+xGe_1–x (TiNiSi‐type) structures, and it therefore represents an alkaline‐earth member of the structure series with the general formula R_2+nT₂X_2+n with n = 4. Unlike the rare‐earth homologues that are fully ordered phases, one seventh of the atomic sites in the unit cell of the title compound are mixed occupied (roughly 2/3Ge and 1/3Ag), and this can be explained by the Zintl concept. The alloying of this phase using aluminum metal yielded the isotypic solid solution Ca₃(Ag/Al)_1+xGe_3–x, in which the aluminum for silver substitution is strictly localized in the TiNiSi substructure, revealing the very different functionality of the two building blocks.     

Ca14Si19 – a Zintl Phase with a Novel Twodimensional Silicon Framework

Ca₁₄Si₁₉ is an overlooked binary phase in the Ca/Si system with a novel type of twodimensional silicon framework (R3 c, a = 867.85(6), c = 6852.8(8) pm, Z = 6). The basic building units are 3,3,3-barrelanes Si₁₁ which are linked by Si₃ bridges to form a twodimensional silicon framework leaving space for interstitial calcium atoms. The thickness of the silicon layers is about 800 pm. The compound is a semiconductor with a band gap of about E_G = 0.1 eV and a diamagnetic moment of χ_mole = ?9 · 10^?4 cm³mol^?1. According to the relatively high linking of silicon atoms the reaction with air and moisture is fairly slow.     

Alkaline Metal Stannide‐Stannates: ‘Double Salts’ with Zintl Sn and Stannate SnO Anions

Using the reduction of tin oxides with the elemental alkaline metals rubidium and cesium, stannide stannates have been synthesized which contain Zintl anions [Sn₄]^4— (i.e. Sn^—I) and isolated oxostannate ions [SnO₃]^4— (i.e. Sn^+II) together with further oxide ions for charge compensation. The crystal structures of the three compounds A_23.6Sn_7.4O_13.2 = A_23.6[Sn₄][SnO₃]_3.4[O]₃ (A = Rb 1a : monoclinic, P2₁/c, a = 2174.2(6), b = 1137.0(6), c = 2373.6(6) pm, β = 116.11(2)°, Z = 4, R1 = 0.056; A = Cs 1b : monoclinic, P2₁/c, a = 2042.6(6), b = 1185.4(3), c = 2481.1(7) pm, β = 97.06(2)°, Z = 4, R1 = 0.075) and Cs₄₈Sn₂₀O₂₁ = Cs₄₈[Sn₄]₄[SnO₃]₄[O]₇[O₂] ( 2 monoclinic, P2/c, a = 1701.8(3), b = 877.4(2), c = 4556.9(7) pm, β= 101.47(1)°, R1 = 0.093) have been determined on the basis of single crystal data. The transparency of the compounds allowed the recording of raman spectra of the anion [Sn₄]^4—. The ¹¹⁹Sn Moessbauer spectrum of the rubidium compound shows a singulet in good agreement with RbSn, overlapping a doublet caused by Sn²⁺ in the asymmetrical environment of the strongly electronegative oxygen ligands of SnO.     

Ein Erdalkalimetallpolyphosphid ungewöhnlicher Zusammensetzung: Die Kristallstruktur von Ba5P9

A Polyphosphide of Unusual Composition: The Crystal Structure of Ba₅P₉ The metallic grey compound Ba₅P₉ can be synthesised from the elements in stoichiometric amounts. It reacts easily with moist air. In the crystal structure (orthorhombic, Fdd2 , a = 1562.6(1) pm, b = 1896.8(2) pm, c = 1027.2(2) pm; Z = 8) anionic P₉ chain fragments are separated by Ba cations. With respect to the stoichiometry a charge of 10‐ results for the polyphosphide anion, but 11 electrons are needed following the (8‐N) rule. According to magnetic measurements the anionic unit is no radical, so a stabilisation by double bonds is discussed.