Single crystals of the phosphides Sm 6 Rh 30 P 19 and Lu 6 Rh 30 P 19 were synthesized from the elements with the bismuth flux technique. Polycrystalline Eu 6 Rh 30 Sb 19 was obtained from the elements by arc-melting and subsequent annealing. The structures of the phosphides were refined from single-crystal X-ray diffractometer data: P 6 3 / m , a = 1,555.07(9), c = 383.38(2) pm, wR 2 = 0.0500, 1044 F 2 values, 58 variables for Sm 6 Rh 30 P 19 and a = 1,551.99(15), c = 376.32(3) pm, wR 2 = 0.0725, 1022 F 2 values, 58 variables for Lu 6 Rh 30 P 19 . Sm 6 Rh 30 P 19 and Lu 6 Rh 30 P 19 crystallize with the Sm 6 Rh 30 Si 19 -type structure, which is closely related to the Yb 6 Co 30 P 19 type. The rhodium and phosphorus atoms build up three-dimensional [Rh 30 P 19 ] networks (225–255 pm Rh–P and 276–288 pm Rh–Rh in Sm 6 Rh 30 P 19 ) which leave hexagonal prismatic cavities for the rare earth atoms. The phosporus atoms on the c axis have distorted octahedral rhodium coordination and show disorder on the c axis (refinement with a split position). Temperature dependent magnetic susceptibility data of Eu 6 Rh 30 Sb 19 show Curie-Weiss behavior with an experimental magnetic moment of 7.78(1) µ B Eu atom −1 and θ P = −9.6(1) K, compatible with divalent europium. The europium atoms in Eu 6 Rh 30 Sb 19 are ordered antiferromagnetically at T N = 3.9(4) K which is corroborated by specific heat data. The divalent ground state of europium is manifested in the 151 Eu Mössbauer spectrum with an isomer shift value of −10.44(1) mm s −1 at 78 K. The 121 Sb Mössbauer spectrum with an isomer shift of −7.12(2) mm s −1 (envelope signal of the four crystallographically independent antimony sites) underpins the antimonide character.

The metal-rich antimonide Gd5Rh19Sb12 was synthesized by induction-melting of the elements in a sealed tantalum ampoule. The Gd5Rh19Sb12 structure was refined from single crystal X-ray diffractometer data of a twinned crystal: P31m, a = 1,349.3(3), c = 417.99(12) pm, wR2 = 0.0682, 1545 F 2 values and 67 variables. Gd5Rh19Sb12 is closely related to the Sc5Co19P12-type. A split position of Rh5 is avoided by a translationengleiche symmetry reduction of index 2 from P 6 & oline; $\overline{6}$ 2m to P31m, leading to a fully ordered model. The crucial difference between Sc5Co19P12 and Gd5Rh19Sb12 concerns the position of the transition metal atoms on the c axis. The Co4 atoms show a split position around the origin in Sc5Co19P12 (Co4@Sc6 trigonal prisms) while the Rh5 atoms in Gd5Rh19Sb12 are shifted by c/2 and then form Rh5@Sb6 trigonal prisms. The remaining substructures of Sc5Co19P12 and Gd5Rh19Sb12 are comparable. The Rh-Sb and Rh-Rh distances within the [Rh19Sb12] substructure range from 255-290 and 292-336 pm, respectively.

X-ray pure samples of EuMgSi were synthesized by reactions of the elements in sealed niobium tubes using a high frequency and subsequently a resistance furnace.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Polycrystalline samples of the ZrCuSiAs type antimonide oxides REZnSbO and REMnSbO (RE = Ce, Pr) were prepared from RESb precursors and MnO, respectively ZnO via a ceramic route. X-ray photoelectron spectroscopy (XPS) studies are used to investigate the charge assignments. For comparison the CeO2 and Pr6O11 reference standards were also investigated. Detailed component analysis of Sb 3d, O 1s, C 1s, Mn 2p, Zn 2p, Pr 3d and Ce 3d core-level spectra determined the types of valence states and their proportions on the samples' surfaces. The results show that praseodymium is in a +3 oxidation state, whereas cerium exists in both +3 and +4 states. The formations of three manganese states in REMnSbO and one dominating Zn(II) state in REZnSbO have also been noticed. (C) 2012 Elsevier Masson SAS. All rights reserved.

The crystal structures of the mixed borates Sr3Er2(BO3)(4) [Pnma, no. 62, Z = 4, a = 738.08(2), b = 1588.94(4), c = 867.81(2) pm, 683 reflections, 70 parameters, R1 = 0.037, wR2 = 0.077] and Sr3Ho2(BO3)(4) [Pnma, no. 62, Z = 4, a = 738.45(7), b = 1591.55(12), c = 871.03(9) pm, 691 reflections, 59 parameters, R1 = 0.069, wR2 = 0.098] and europium oxonitridoborate Eu-5(BO2.51(7)N0.49(7))(4) [Pnma, no. 62, Z = 12, a = 2232.2(5), b = 1603.1(3), c = 879.59(18) pm, 2880 reflections, 313 parameters, R1 = 0.027, wR2 = 0.059] were solved from single-crystal X-ray diffraction data. Eu-5(BO2.51(7)N0.49(7))(4) adopts a threefold superstructure of the structure of Sr(3)Ln(2)(BO3)(4) (Ln = Ho, Er). In both structure types, the different cations are situated on common sites with a pronounced preferential occupation but no complete ordering. These conclusions are based on the crystal structure refinement, Eu-151 Mossbauer spectroscopy and MAPLE (Madelung part of lattice energy) calculations. The proposed Eu-5(BO3)(4) contains nitrogen and has a formula Eu-5(BO2.51(7)N0.49(7))(4) as confirmed by Eu-151 Mossbauer spectroscopy. The optical reflectance spectrum of Eu-5(BO2.51(7)N0.49(7))(4) is in accordance with the yellow colour of the compound.

The ternary antimonides RE 4 T 7 Sb 6 (RE=Gd-Lu; T =Ru, Rh) have been synthesized from the elements by arc-melting and subsequent annealing in an induction furnace. The samples have been characterized by powder X-ray diffraction. Four structures were refined on the basis of single-crystal X-ray diffractometer data: U 4 Re 7 Si 6 type, space group Im3m with a=862.9(2) pm, wR2=0.0296, 163 F 2 values for Er 4 Ru 7 Sb 6 ; a=864.1(1) pm, wR2=0.1423, 153 F 2 values for Yb 4 Ru 7 Sb 6 ; a=872.0(2) pm, wR2=0.0427, 172 F 2 values for Tb 4 Rh 7 Sb 6 ; and a=868.0(2) pm, wR2=0.0529, 154 F 2 values for Er 4 Rh 7 Sb 6 , with 10 variables per refinement. The structures have T1@Sb 6 octahedra and slightly distorted RE@T2 6 Sb 6 cuboctahedra as building units. The distorted cuboctahedra are condensed via all trapezoidal faces, and this network leaves octahedral voids for the T1 atoms. The ruthenium-based series of compounds was studied by temperature-dependent magnetic susceptibility measurements. Lu 4 Ru 7 Sb 6 is Pauli-paramagnetic. The antimonides RE 4 Ru 7 Sb 6 with RE=Dy, Ho, Er, and Tm show Curie-Weiss paramagnetism. Antiferromagnetic ordering occurs at 10.0(5), 5.1(5) and 4.0(5) K for Dy 4 Ru 7 Sb 6 , Ho 4 Ru 7 Sb 6 and Er 4 Ru 7 Sb 6 , respectively, while Tm 4 Ru 7 Sb 6 remains paramagnetic. Yb 4 Ru 7 Sb 6 is an intermediate-valent compound with a reduced magnetic moment of 3.71(1) μ B per Yb as compared to 4.54 μ B for a free Yb 3+ ion

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

AbstractX‐ray photoelectron spectroscopy reveals that the praseodymium species in the title compounds are in a pure +3 oxidation state, whereas cerium exists in both +3 and +4 states.

Four N,N'-disubstituted 1,2-diaminobenzes (1a: R = t-Bu, 1b: R = adamantyl, 1c: R = Ph, 1d: R = Dipp) have been prepared and reacted with E[N(SiMe3)2]2 (E = Ge, Sn) to give the benzannulated N-heterocyclic germylenes 2a-d and stannylenes 3a-d. Germylene 2d and stannylenes 3a, 3c and 3d have been characterized by X-ray diffraction showing different types of intermolecular interactions in the solid state. Deprotonation of 1b with n-BuLi yields the lithium stannyl anion Li[4] with an n-Bu group bound to the tin(II) center.

The Zintl phases Eu3Mg5Si5 and Eu3Mg5Ge5 were synthesized by high-frequency melting of the elements in sealed tantalum tubes. Both of their structures have been refined from X-ray single crystal diffractometer data: Sr12Mg17.8Li2.2Si20 type, Pnma, a = 1424.3(1), b = 450.5(2), c = 1821.4(2) pm, wR2 = 0.0544, 1995 F2 values, 80 variables for Eu3Mg5Si5 and a = 1445.8(2), b = 452.9(1), c = 1845.0(2) pm, wR2 = 0.0375, 2053 F2 values, 80 variables for Eu3Mg5Ge5. The electron precise Zintl phases [Eu2+]3[Mg2+]5[Si4]2[Si38] and [Eu2+]3[Mg2+]5[Ge4]2[Ge38] contain isolated tetrelide ions and bent Si3 (d(SiSi): 239241 pm) and Ge3 units (d(GeGe): 251256 pm) units respectively which have single bond character and are isoelectronic to Cl2O, Cl2S, and [P35]. The formal chemical bonding is confirmed by ab-initio calculations. The ecliptic stacking of the anions along b causes a strong dispersion of the dedicated bands. Eu3Mg5Si5 is predicted to be a semi-metal; i.e., a semi-conductor with zero energy gap between bands derived from anti-bonding silicon states. Eu3Mg5Ge5, however, appears to be a metal, due to the participation of germanium-d orbitals to states at the Fermi level. The divalent europium has been manifested through magnetic susceptibility measurements. At high temperatures, Eu3Mg5Si5 and Eu3Mg5Ge5 are CurieWeiss paramagnets with experimental magnetic moments of 7.96(1) and 7.94(1) mu B/Eu atoms, respectively. Magnetic ordering, hinting at frustrated interactions, is observed at 19.1 (Eu3Mg5Si5) and 14.2 (Eu3Mg5Ge5) K. Temperature dependent 151Eu Mossbauer spectra are indicative of purely divalent europium and complex magnetic hyperfine field splitting at low temperatures.

AbstractThe title compounds are synthesized by high‐frequency melting of the elements followed by annealing at 1600 K for 30 min and 900 K for 90 min.

The stannides YPdSn and YPd2Sn were synthesized by high-frequency melting of the elements in sealed tantalum tubes. Both structures were refined on the basis of single crystal X-ray diffractometer data: TiNiSi type, Pnma, a=715.4(1), b=458.8(1), c=789.1(1)pm, wR2=0.0461, 510F2 values, 20 variables for YPdSn and MnCu2Al type, Fm3¯m, a=671.44(8), wR2=0.0740, 55 F2 values, 5 parameters for YPd2Sn. The yttrium atoms in the new stannide YPdSn are coordinated by two tilted Pd3Sn3 hexagons (ordered AlB2 superstructure). In the Heusler phase YPd2Sn each yttrium atom has octahedral tin coordination and additionally eight palladium neighbors. The cubic site symmetry of yttrium is reflected in the 119Sn Mössbauer spectrum which shows no quadrupole splitting. In contrast, YPdSn shows a single signal at δ=1.82(1)mm/s subjected to quadrupole splitting of ΔEQ=0.93(1)mm/s. Both compounds have been characterized by high-resolution 89Y solid state NMR spectroscopy, which indicates the presence of strong Knight shifts. The spectrum of YPd2Sn is characterized by an unusually large linewidth, suggesting the presence of a Knight shift distribution reflecting local disordering effects. The range of 89Y Knight shifts of several binary and ternary intermetallic yttrium compounds is briefly discussed.

AbstractThe first metastable iron‐based superconductor of mean composition Na0.9Fe1.7As2 is prepared by topochemical deintercalation of Na+ ions from solid NaFeAs with iodine in THF at room temperature for 40 h.

Two K([2.2.2]crypt) salts of lanthanide-doped semimetal clusters were prepared, both of which contain at the same time two types of ternary intermetalloid anions, [Ln@Sn7Bi7](4-) and [Ln@Sn4Bi9](4-), in 0.70:0.30 (Ln = La) or 0.39:0.61 (Ln = Ce) ratios. The cluster shells represent nondeltahedral, fullerane-type arrangements of 14 or 13 main group metal atoms that embed the Ln(3+) cations. The assignment of formal +III oxidation states for the Ln sites was confirmed by means of magnetic measurements that reveal a diamagnetic La(III) compound and a paramagnetic Ce(III) analogue. Whereas the cluster anions with a 14-atomic main-group metal cage represent the second examples in addition to a related Eu(II) cluster published just recently, the 13-atomic cages exhibit a yet unprecedented enneahedral topology. In contrast to the larger cages, which accord to the Zintl-Klemm-Busmann electron number-structure correlation, the smaller clusters require a more profound interpretation of the bonding situation. Quantum chemical investigations served to shed light on these unusual complexes and showed significant narrowing of the HOMO-LUMO gap upon incorporation of Ce3+ within the semimetal cages.

The stannides YPdSn and YPd{sub 2}Sn were synthesized by high-frequency melting of the elements in sealed tantalum tubes. Both structures were refined on the basis of single crystal X-ray diffractometer data: TiNiSi type, Pnma, a=715.4(1), b=458.8(1), c=789.1(1) pm, wR2=0.0461, 510 F{sup 2} values, 20 variables for YPdSn and MnCu{sub 2}Al type, Fm3 Macron m, a=671.44(8), wR2=0.0740, 55 F{sup 2} values, 5 parameters for YPd{sub 2}Sn. The yttrium atoms in the new stannide YPdSn are coordinated by two tilted Pd{sub 3}Sn{sub 3} hexagons (ordered AlB{sub 2} superstructure). In the Heusler phase YPd{sub 2}Sn each yttrium atom has octahedral tin coordination and additionally eight palladium neighbors. The cubic site symmetry of yttrium is reflected in the {sup 119}Sn Moessbauer spectrum which shows no quadrupole splitting. In contrast, YPdSn shows a single signal at {delta}=1.82(1) mm/s subjected to quadrupole splitting of {Delta}E{sub Q}=0.93(1) mm/s. Both compounds have been characterized by high-resolution {sup 89}Y solid state NMR spectroscopy, which indicates the presence of strong Knight shifts. The spectrum of YPd{sub 2}Sn is characterized by an unusually large linewidth, suggesting the presence of a Knight shift distribution reflecting local disordering effects. The range of {sup 89}Y Knight shifts of several binary and ternary intermetallic yttrium more » compounds is briefly discussed. - Graphical abstract: YPdSn and YPd{sub 2}Sn: Structure, {sup 89}Y solid state NMR and {sup 119}Sn Moessbauer spectroscopy. Highlights: Black-Right-Pointing-Pointer Synthesis and structure of ternary stannides YPdSn and YPd{sub 2}Sn. Black-Right-Pointing-Pointer {sup 119}Sn Moessbauer spectroscopic investigation of YPdSn and YPd{sub 2}Sn. Black-Right-Pointing-Pointer {sup 89}Y solid state NMR of intermetallics. « less

The CaBe2Ge2-type antimonide EuPd2Sb2 (P4/nmm, a = 462.43(7), c = 1056.1(2) pm) was synthesized by induction melting of the elements in a sealed tantalum tube. Temperature-dependent magnetic susceptibility measurements have revealed Curie-Weiss behavior with an experimental magnetic moment of 7.93(1) μB/Eu atom, indicating stable divalent europium. EuPd2Sb2 orders antiferromagnetically at TN = 4.5(2) K as is also evident from almost full hyperfine field splitting (Bh = 19.5 T) in the 151Eu Mössbauer spectrum at 4.2 K