TY - JOUR

T1 - Complex Salts Containing [Pd(NH3)4]2+ Cations and WO42− and W7O246− Anions

T2 - The Precursors of Pd–W Metal Alloys

AU - Khranenko, S. P.

AU - Sukhikh, A. S.

AU - Komarov, V. Yu

AU - Gromilov, S. A.

PY - 2020/3/1

Y1 - 2020/3/1

N2 - Two crystal structures containing [Pd(NH3)4]2+ cations and WO42− and W7O246− anions are studied. For the [Pd(NH3)4]WO4 structure at 150 K the following crystallographic data are obtained: a = 7.4626(3) Å, c = 15.5718(8) Å, space group I41/amd, V = 867.20 Å3, Z = 4. With increasing temperature to 400 K, the unit cell parameters change in different directions: a increases by 0.032 Å, c decreases by 0.036 Å. The total increase in the unit cell volume is 5 Å3. In a range of 150 K to 400 K, the observed W-O distances decrease by 0.019 Å from 1.778(18) Å to 1.759(3) Å. For the [Pd(NH3)4]3W7O24·4.4H2O structure at 298 K the crystallographic data are as follows: a = 8.3409(2) Å, b = 22.2654(6) Å, c = 10.5450(3) Å, β = 104.449(1)°, space group P21/m, V = 1896.41 Å3, Z = 2. In the heptatungstate anion the shortest are the W—O distances with the terminal O atoms (1.731–1.745 Å). The distances to the bridging O atoms connecting two W atoms are 1.930–2.406 Å; those connecting three W atoms are 1.882–2.234 Å, and those connecting four W atoms are 2.192–2.220 Å. It is shown that the [Pd(NH3)4]3W7O24·4.4H2O structure has a pseudohexagonal motif in the a direction. The thermal decomposition of the salts is performed in the presence of LiH in the He atmosphere at 1273 K. The ex situ powder X-ray diffraction study reveals the formation of Pd–W alloys.

AB - Two crystal structures containing [Pd(NH3)4]2+ cations and WO42− and W7O246− anions are studied. For the [Pd(NH3)4]WO4 structure at 150 K the following crystallographic data are obtained: a = 7.4626(3) Å, c = 15.5718(8) Å, space group I41/amd, V = 867.20 Å3, Z = 4. With increasing temperature to 400 K, the unit cell parameters change in different directions: a increases by 0.032 Å, c decreases by 0.036 Å. The total increase in the unit cell volume is 5 Å3. In a range of 150 K to 400 K, the observed W-O distances decrease by 0.019 Å from 1.778(18) Å to 1.759(3) Å. For the [Pd(NH3)4]3W7O24·4.4H2O structure at 298 K the crystallographic data are as follows: a = 8.3409(2) Å, b = 22.2654(6) Å, c = 10.5450(3) Å, β = 104.449(1)°, space group P21/m, V = 1896.41 Å3, Z = 2. In the heptatungstate anion the shortest are the W—O distances with the terminal O atoms (1.731–1.745 Å). The distances to the bridging O atoms connecting two W atoms are 1.930–2.406 Å; those connecting three W atoms are 1.882–2.234 Å, and those connecting four W atoms are 2.192–2.220 Å. It is shown that the [Pd(NH3)4]3W7O24·4.4H2O structure has a pseudohexagonal motif in the a direction. The thermal decomposition of the salts is performed in the presence of LiH in the He atmosphere at 1273 K. The ex situ powder X-ray diffraction study reveals the formation of Pd–W alloys.

KW - crystal chemistry

KW - heptatungstate anion

KW - palladium tetrammine

KW - single crystal X-ray diffraction analysis

KW - thermal decomposition

KW - tungstate anion

KW - CRYSTAL-STRUCTURES

UR - http://www.scopus.com/inward/record.url?scp=85088665808&partnerID=8YFLogxK

U2 - 10.1134/S0022476620030117

DO - 10.1134/S0022476620030117

M3 - Article

AN - SCOPUS:85088665808

VL - 61

SP - 449

EP - 455

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 3

ER -