Metal-rich phosphides RE5Ir19P12 with Sc5Co19P12 type structure

Pfannenschmidt, Ulrike; Rodewald, Ute Ch.; Hoffmann, Rolf‐Dieter; Pöttgen, Rainer

doi:10.1016/j.jssc.2011.07.045

Cited by 10 publications

(10 citation statements)

References 34 publications

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“…The cerium atoms (site symmetry 4mm) have coordination number 16 with eight phosphorus and eight iridium atoms in their first coordination sphere. Similar to the structures of Ce 4 Ir 13.55 P 9 22 and Ce 5 Ir 18.0 P 12 44 the cerium atoms in CeIr 2 P 2 have eight phosphorus neighbors as closest contacts. The shortest Ce-Ce distances correspond to the lattice parameter a (415 pm).…”

Section: Crystal Chemistrymentioning

confidence: 59%

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CaBe2Ge2 type phosphides REIr2P2 (RE = La–Nd, Sm) and arsenides REIr2As2 (RE = La–Nd): synthesis, structure, and solid state NMR spectroscopy

et al. 2012

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The phosphides REIr(2)P(2) (RE = La-Nd, Sm) and arsenides REIr(2)As(2) (RE = La-Nd) were synthesized by a ceramic route via precursor compounds REIr(2) with phosphorus and arsenic, respectively. Well-shaped single crystals were obtained from lead and bismuth fluxes, respectively. The nine pnictides crystallize with the tetragonal CaBe(2)Ge(2) type structure, space group P4/nmm. The structures of CeIr(2)P(2), SmIr(2)P(2), LaIr(2)As(2) and CeIr(2)As(2) were refined from single crystal X-ray diffractometer data. The structures are composed of three-dimensional [Ir(2)P(2)] and [Ir(2)As(2)] networks in which the rare earth atoms fill cavities of coordination number 16 (8 P + 8 Ir). The phosphorus and arsenic atoms have tetrahedral and square pyramidal iridium coordination. Temperature dependent magnetic susceptibility measurements show intermediate cerium valence for CeIr(2)P(2). The rare-earth and phosphorus local environments in LaIr(2)P(2) are characterized further by (139)La and (31)P single and double resonance solid state nuclear magnetic resonance (NMR) spectroscopy. Strong (31)P Knight shifts and extremely short spin-lattice relaxation times indicate that the bonding character of the phosphide species is strongly metallic. The two crystallographically distinct phosphorus sites are well-resolved in the (31)P magic-angle spinning (MAS) spectrum and also differ significantly with respect to their effective magnetic shielding anisotropies. Unambiguous site assignments are accomplished on the basis of homonuclear (31)P-(31)P magnetic dipole-dipole interactions, which can be measured in a site-resolved fashion in this compound using static (31)P spin echo decay spectroscopy. The highly symmetric La environment in LaIr(2)P(2) is characterized by a sharp (139)La MAS-NMR spectrum, revealing rather weak nuclear electric quadrupole coupling. Furthermore, a second local environment is detected, which is characterized by stronger quadrupolar coupling and similar dipolar coupling strength with (31)P as the regular site, according to (139)La{(31)P} rotational echo double resonance (REDOR) NMR results. On the basis of these data we attribute this site to a La species next to a phosphorus vacancy. From the signal area of this resonance we deduce a composition LaIr(2)P(1.90).

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Section: Crystal Chemistrymentioning

confidence: 59%

“…6. 44 Fig. 8a shows the effect of systematic incrementation of the dipolar evolution time t 1 upon the lineshape obtained by Fourier transforming the echo.…”

Section: Solid State Nmr Results On Lair 2 Pmentioning

confidence: 99%

CaBe2Ge2 type phosphides REIr2P2 (RE = La–Nd, Sm) and arsenides REIr2As2 (RE = La–Nd): synthesis, structure, and solid state NMR spectroscopy

et al. 2012

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“…Synthesis : Samples for the investigations have been prepared by a double sintering procedure of pressed pellets obtained from the mixtures of the starting materials (powders of thulium or lutetium, palladium and red phosphorus, all with a stated purity better than 99.99 wt.%, Alfa‐Aesar, Johnson Matthey Company). Starting compositions of the prepared samples were Tm 14 Pd 53 P 33 , Tm 24 Pd 43 P 33 , and Lu 14 Pd 53 P 33 (all given in molar percentage), and were chosen using reported data of earlier known ternary rare earth metal and palladium phosphides [1–19] . The total mass of every sample was 0.5 g. The pressed pellets were sealed in vacuumed silica tubes, and then sintered in a muffle furnace by gradually heating (200 degrees per day) from the ambient temperature to the 1070 K and holding at this temperature for 3 days.…”

Section: Methodsmentioning

confidence: 99%

“…[18] Compounds of the ternary rare earth and iridium phosphides RE 5 Ir 19 P 12 (RE = Sc, Y, LaÀ Nd, SmÀ Lu) with Sc 5 Co 19 P 12 -type structure have recently been reported. [19] However, ternary phosphides with the Zr 2 Fe 12 P 7 -type structure [20] are very common among the compounds of the RE-M-P systems, where M = Fe, Co, and Ni, and have not yet been obtained earlier with Pd. Only the ternary phosphide Yb 2 + 3x Pd 12-3 + x P 7 (x = 0.4) with the crystal structure closely related to the hexagonal Zr 2 Fe 12 P 7 -type was reported.…”

Section: Introductionmentioning

confidence: 99%

New ternary phosphides RE₅Pd₉P₇ (RE=Tm, Lu): synthesis, crystal and electronic structure

Zhak

Köhler

Karychort

et al. 2022

Zeitschrift anorg allge chemie

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The crystal structure of the new ternary phosphideTm5Pd9P7 was determined from powder X‐ray diffraction data: space group P6‾ , a=9.9971(2), c=3.94371(8) Å, RI=0.0518, Rp=0.0667, Rp=0.0667, wRp=0.1065. The crystal structure of the phosphide Tm5Pd9P7 is closely related with the Zr2Fe12P7‐type, and is formed by combination of two types of structural units with the compositions [TmPd6P3] and [TmTm3Pd3P3] mutually displaced by 1/2 along the c axis. Connection of the last units forms the trigonal prisms [Tm6] around P3 atoms in the crystallographic position 1a (0 0 0). The isotypic ternary phosphide Lu5Pd9P7 was synthesized (a=9.9934(7), c=3.9207(4) Å). The electronic and bonding properties of Tm5Pd9P7 are obtained from tight binding linear muffin‐tin orbital (TB‐LMTO) calculations and a crystal orbital Hamiltonian population (COHP) bonding analysis. These analyses show strong covalent bonding within (Pd9P7)15− nanotubes which are ionically bound via the Tm atoms to three dimensional network.

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“…Due to the low reactivity, only few ternary iridium phosphides had been synthesized by heating mixtures of the elements in corundum crucibles [10,11] [7], AIrP (A = Sr, Ba, La -Nd, Eu) [8,9], AIr 2 P 2 (A = K, Rb, Cs, Ca, Sr, Ba, Eu) [8 -12], Ca 4 Ir 8 P 7 [13], Lu 3 Ir 7 P 5 [14], Sm 15 Ir 33 P 26 [15], Ce 4 Ir 13.55 P 9 [16], Ce 13 Ir 34.4 P 24 [17], ScIrP [18], and the three series RE 7 Ir 17 P 12 (RE = Y, Gd, Tb, Dy, Ho) [19], RE 5 Ir 19 P 12 [20] and REIr 2 P 2 (RE = La -Nd, Sm) [21,22].…”

Section: Introductionmentioning

confidence: 99%

Lead-flux Growth of Eu₄Ir₈As₇ Crystals

Pfannenschmidt¹,

Pöttgen²

2013

Zeitschrift Für Naturforschung B

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Single crystals of the new arsenide Eu 4 Ir 8 As 7 were grown from a lead flux. The structure was refined on the basis of single-crystal X-ray diffractometer data: Ca 4 Ir 8 P 7 type, P2 1 /m, a = 1311.3(1), b = 408.4(1), c = 1360.3(1) pm, β = 98.45(1) • , wR2 = 0.0640, 1985 F 2 values, 95 variables. The iridium and arsenic atoms in the Eu 4 Ir 8 As 7 structure build up a complex three-dimensional, covalently bonded [Ir 8 As 7 ] network with Ir-As distances ranging from 239 to 260 pm. Each iridium atom has three or four arsenic neighbors in slightly distorted trigonal-planar or tetrahedral coordination. The four crystallographically independent europium atoms fill cavities of coordination numbers 12, 13, and 15 (2 ×) within the [Ir 8 As 7 ] network. Parts of the Eu 4 Ir 8 As 7 structure resemble known simpler structure types, and one can describe the Eu 4 Ir 8 As 7 structure as an intergrowth variant of CaBe 2 Ge 2 -, TiNiSi-and AlB 2 -related slabs.

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Metal-rich phosphides RE5Ir19P12 with Sc5Co19P12 type structure

Cited by 10 publications

References 34 publications

CaBe2Ge2 type phosphides REIr2P2 (RE = La–Nd, Sm) and arsenides REIr2As2 (RE = La–Nd): synthesis, structure, and solid state NMR spectroscopy

CaBe2Ge2 type phosphides REIr2P2 (RE = La–Nd, Sm) and arsenides REIr2As2 (RE = La–Nd): synthesis, structure, and solid state NMR spectroscopy

New ternary phosphides RE₅Pd₉P₇ (RE=Tm, Lu): synthesis, crystal and electronic structure

Lead-flux Growth of Eu₄Ir₈As₇ Crystals

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Metal-rich phosphides RE5Ir19P12 with Sc5Co19P12 type structure

Cited by 10 publications

References 34 publications

CaBe2Ge2 type phosphides REIr2P2 (RE = La–Nd, Sm) and arsenides REIr2As2 (RE = La–Nd): synthesis, structure, and solid state NMR spectroscopy

CaBe2Ge2 type phosphides REIr2P2 (RE = La–Nd, Sm) and arsenides REIr2As2 (RE = La–Nd): synthesis, structure, and solid state NMR spectroscopy

New ternary phosphides RE5Pd9P7 (RE=Tm, Lu): synthesis, crystal and electronic structure

Lead-flux Growth of Eu4Ir8As7 Crystals

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New ternary phosphides RE₅Pd₉P₇ (RE=Tm, Lu): synthesis, crystal and electronic structure

Lead-flux Growth of Eu₄Ir₈As₇ Crystals