Проведен сравнительный кристаллохимический анализ о-[Pd(NH3)4]3Мо7O24·6H2O (а = 17.3472(3), b = 28.9064(4), с = 30.2463(4) Å, пр. гр. Ibca, V = 15166.9 Å3, Z = 16) и m-[Pd(NH3)4]3Мо7O24·3H2O (а = 10.6617(2), b = 20.5248(5), с = 16.4676(3) Å, b = 103.0792(10), пр. гр. P21/n, V = 3510.11(13) Å3, Z = 4). Изучены продукты термического разложения o-[Pd(NH3)4]3Мо7O24·6H2O. В атмосфере Н2 при 900°С образуется смесь разнометальных твердых растворов на основе ОЦК-решетки Мо и ГЦК-решетки Pd, а в атмосфере 90%Не/10%Н2 при 910°С - смесь твердого раствора на основе ОЦК-решетки Мо и Pd2Mo3N.

A comparative crystal chemical analysis of о-[Pd(NH3)4]3Мо7O24·6H2O (а = 17.3472(3) Å, b = 28.9064(4) Å, с = 30.2463(4) Å, space group Ibca, V = 15166.9 Å3, Z = 16) and m-[Pd(NH3)4]3Мо7O24·3H2O (а = 10.6617(2) Å, b = 20.5248(5) Å, с = 16.4676(3) Å, β = 103.0792(10)°, space group P21/n, V = 3510.11(13) Å3, Z = 4) is performed. Thermal decomposition products of o-[Pd(NH3)4]3Мо7O24·6H2O are studied. In the Н2 atmosphere at 900 °C, a mixture of mixed-metal solid solutions based on the Мо bcc lattice and the Pd fcc lattice is formed while in the 90

An Erratum to this paper has been published: https://doi.org/10.1134/S0022476622040205

[Pd(NH3)4]2Mo8O26 (I) and Na2[Pd(NH3)4]2Mo8O27·5H2O (II) are synthesized and their crystal structures are determined. In the structure of I, isolated octamolybdate anions have a β-configuration; Mo atoms are bonded to 14 (6×2 + 2×1) terminal O atoms, the distances to which are in a range of 1.693-1.733 Å. The Mo–O distances with bridging O atoms connecting two Mo atoms range within 1.755-2.228 Å; with those connecting three Mo atoms it is 1.927-2.390 Å; and with those connecting five Mo atoms, it is 2.143-2.501 Å. The mutual arrangement of octamolybdate anions can be described in terms of a three-layer close packing: aT ≈ 9.5 Å, αT ≈ 69.8°. In the structure of II, octamolybdate anions form infinite chains ([Mo8O27]6–)∞. The Mo atoms are bonded to 16 (4×2 + 2×1 + 2×2.5) terminal O atoms, the distances to which are in a range of 1.705-1.901 Å. Some terminal O atoms are involved in the additional coordination of Na+ cations, as a result of which, a complex 3D structure forms. The Mo–O distances with bridging O atoms connecting two Mo atoms range within 1.755-2.367 Å; with those connecting three Mo atoms it is 1.868-2.218 Å; with those connecting four Mo atoms it is 1.957-2.365 Å. The anions form pseudohexagonal layers (a ≈ c ≈ 9.2 Å, ∠β ≈ 120°) perpendicular to the Y axis.

[Pd(NH 3 ) 4 ] 2 Mo 8 O 26 ( I ) and Na 2 [Pd(NH 3 ) 4 ] 2 Mo 8 O 27 ·5H 2 O ( II ) are synthesized and their crystal structures are determined. In the structure of I , isolated octamolybdate anions have a β-configuration; Mo atoms are bonded to 14 (6×2 + 2×1) terminal O atoms, the distances to which are in a range of 1.693-1.733 Å. The Mo–O distances with bridging O atoms connecting two Mo atoms range within 1.755-2.228 Å; with those connecting three Mo atoms it is 1.927-2.390 Å; and with those connecting five Mo atoms, it is 2.143-2.501 Å. The mutual arrangement of octamolybdate anions can be described in terms of a three-layer close packing: a T ≈ 9.5 Å, α T ≈ 69.8°. In the structure of II , octamolybdate anions form infinite chains ([Mo 8 O 27 ] 6– ) ∞ . The Mo atoms are bonded to 16 (4×2 + 2×1 + 2×2.5) terminal O atoms, the distances to which are in a range of 1.705-1.901 Å. Some terminal O atoms are involved in the additional coordination of Na + cations, as a result of which, a complex 3D structure forms. The Mo–O distances with bridging O atoms connecting two Mo atoms range within 1.755-2.367 Å; with those connecting three Mo atoms it is 1.868-2.218 Å; with those connecting four Mo atoms it is 1.957-2.365 Å. The anions form pseudohexagonal layers ( a ≈ c ≈ 9.2 Å, ∠β ≈ 120°) perpendicular to the Y axis.

[Pd(NH3)4]3(Мо7 – хWxO24)⋅6H2O crystals with different Mo/W ratios have been formed as a result of the crystallization of a mixture of Na6W7O24, Na6Мо7O24, and [Pd(NH3)4](NO3)2 aqueous solutions. Ten crystals with 0.8 ≤ x ≤ 3.4 have been studied. In the polyanion, Mo and W atoms occupy preferred sites rather than are distributed statistically. The crystallographic characteristics of [Pd(NH3)4]3(Мо3.6W3.4O24)⋅6H2O are found to be as follows: a = 17.4294(2) Å, b = 28.9215(4) Å, c = 30.4435(4) Å, sp. gr. Ibca, V = 15346.1(3) Å3, and Z = 16. The anion packing in the structure has been analyzed. It is shown that anions are arranged into a pseudohexagonal motif. The products of thermal decomposition in H2 atmosphere have been studied. It is shown that a mixture of solid substitutional solutions based on Pd and Mo(W) lattices is formed at 800°C.

— [Pd(NH 3 ) 4 ] 3 (Мо 7 – х W x O 24 )⋅6H 2 O crystals with different Mo/W ratios have been formed as a result of the crystallization of a mixture of Na 6 W 7 O 24 , Na 6 Мо 7 O 24 , and [Pd(NH 3 ) 4 ](NO 3 ) 2 aqueous solutions. Ten crystals with 0.8 ≤ x ≤ 3.4 have been studied. In the polyanion, Mo and W atoms occupy preferred sites rather than are distributed statistically. The crystallographic characteristics of [Pd(NH 3 ) 4 ] 3 (Мо 3.6 W 3.4 O 24 )⋅6H 2 O are found to be as follows: a = 17.4294(2) Å, b = 28.9215(4) Å, c = 30.4435(4) Å, sp. gr. Ibca , V = 15346.1(3) Å 3 , and Z = 16. The anion packing in the structure has been analyzed. It is shown that anions are arranged into a pseudohexagonal motif. The products of thermal decomposition in H 2 atmosphere have been studied. It is shown that a mixture of solid substitutional solutions based on Pd and Mo(W) lattices is formed at 800°C.

Проведен синтез и определены кристаллические структуры [Pd(NH3)4]2Мо8O26 (I) и Na2[Pd(NH3)4]2Мо8O27·5H2O (II). В структуре I у изолированных октамолибдат-анионов β-конфигурация, атомы Мо связаны с 14 (6×2 + 2×1) терминальными атомами О, расстояния до которых лежат в интервале 1.693—1.733 Å. Интервал расстояний Мо—O с участием мостиковых атомов О, связывающих два атома Мо — 1.755—2.228 Å, три — 1.927—2.390 Å, пять — 2.143—2.501 Å. Взаимное расположение октамолибдат-анионов можно описать в терминах плотнейшей трехслойной упаковки: aT ≈ 9.5 Å, aT ≈ 69.8°. В структуре II октамолибдат-анионы образуют бесконечные цепочки ([Мо8O27]6–)∞. Атомы Мо связаны с 16 (4×2 + 2×1 + 2×2.5) терминальными атомами О, расстояния до которых лежат в интервале 1.705—1.901 Å. Часть терминальных атомов О участвует в дополнительной координации катионов Na+, в результате чего формируется сложная 3D структура. Интервал расстояний Мо—O с участием мостиковых атомов О, связывающих два атома Мо — 1.755—2.367 Å, три — 1.868—2.218 Å, четыре — 1.957—2.365 Å. Анионы образуют псевдогексагональные слои (a ≈ c ≈ 9.2 Å, ∠β ≈ 120°), которые располагаются перпендикулярно оси Y.

The crystal structure of [CuEn3]MoO4 (En is ethylenediamine) is studied in a range 100–390 K. The crystallographic data at 100 K are as follows: a = 27.5808(9) Å, c = 9.9043(4) Å, space group $$P\overline 3 $$, V = 6524.8(4) Å3, Z = 18. The coordination of copper atoms is a distorted square bipyramid. In three crystallographically independent cations. four short Cu-N distances are 2.041(2)–2.093(2) Å, two long ones in a trans position are 2.397(2)–2.496(2) Å (at 200 K these intervals are 2.039(4)–2.148(4) Å and 2.332(2)–2.461(4) Å respectively). In a range from 200 K to 298 K, the transition occurs to the space group $$P\overline 3 $$c1 (a = 15.9992(6) Å, c = 9.9385(4) Å, V = 2203.17(19) Å3, Z = 6) and the Cu-N distances are aligned: 2.086(6) Å, 2.162(7) Å, 2.273(8) Å. At 390 K the Jahn-Teller effect disappears and the Cu-N distances are 2.153(4) Å (a = 9.2785(14) Å, c = 10.0035(18) Å, $$P\overline 3 $$ 1c, V = 745.8(3) Å3, Z = 2). It is shown that with increasing temperature from 100 K to 320 K the average Mo-O distances decrease from 1.766 Å to 1.699 Å. The ex situ powder X-ray diffraction study of the formation process of metal and carbide phases is performed during [CuEn3]MoO4 thermal decomposition in the He atmosphere in the presence of LiH. Starting from 973 K, a mixture of Mo2C and the fcc phase based on the Cu structure (a ≈ 3.65 Å) forms.

Two complex salts with heptatungstate anions and [Pd(NH3)4]2+ and Na+ cations are synthesized. In the structure of Na2[Pd(NH3)]5(W7O24)2·16H2O (a = 11.5703(3) Å, b = 12.4653(4) Å, c = 14.8201(5) Å, α = 69.733(1)°, β = 97.231(1)°, γ = 75.816(1)°, space group P-1, V = 1937.8(1) Å3, Z = 1), the Na+ cations link heptatungstate anions into dimers; the Na…O distances are 2.321–2.446 Å. In the structure of Na[Pd(NH3)4]2(HW7O24)·7H2O (a = 11.1113(8) Å, b = 17.9869(12) Å, c = 17.8140(13) Å, β = 96.974(2)°, space group P21/n, V = 3533.9(4) Å3, Z = 4), the bridging Na+ cations link hydroheptatungstate anions into zigzag chains; the Na…O distances are 2.291–2.724 Å.

Two crystal structures containing [Pd(NH 3 ) 4 ] 2+ cations and WO_4^2- and W_7O_24^6- anions are studied. For the [Pd(NH 3 ) 4 ]WO 4 structure at 150 K the following crystallographic data are obtained: a = 7.4626(3) Å, c = 15.5718(8) Å, space group I 4 1 /amd, V = 867.20 Å 3 , 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 Å 3 . 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(NH 3 ) 4 ] 3 W 7 O 24 ·4.4H 2 O 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 P 2 1 /m, V = 1896.41 Å 3 , 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(NH 3 ) 4 ] 3 W 7 O 24 ·4.4H 2 O 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.

Two crystal structures containing [Pd(NH3)4]2+ cations and $$\text{WO}_4^{2-}$$ and $$\text{W}_7\text{O}_{24}^{6-}$$ 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.

Кристаллическая структура [CuEn3]MoO4 (En — этилендиамин) изучена в интервале 100—390 K. Кристаллографические данные при 100 K: а = 27.5808(9), с = 9.9043(4) Å, пр. гр. Р-3, V = 6524.8(4) Å3, Z = 18. Координация атомов меди — искаженная квадратная бипирамида, в трех кристаллографически независимых катионах четыре коротких расстояния Cu—N лежат в интервале 2.041(2)—2.093(2) Å, два длинных в транс-положении — 2.397(2)—2.496(2) Å (при 200 K эти интервалы 2.039(4)—2.148(4) и 2.332(2)—2.461(4) Å соответственно). В интервале от 200 K до 298 K происходит переход к пространственной группе P-3c1 (а = 15.9992(6), с = 9.9385(4) Å, V = 2203.17(19) Å3, Z = 6), расстояния Cu—N сближаются: 2.086(6), 2.162(7), 2.273(8) Å. При 390 K эффект Яна—Теллера исчезает, расстояния Cu—N 2.153(4) Å (а = 9.2785(14), с = 10.0035(18) Å, P-31c, V = 745.8(3) Å3, Z = 2). Показано, что при повышении температуры от 100 K до 320 K средние расстояния Mo—О уменьшаются от 1.766 Å до 1.699 Å. Проведено ex situ рентгенографическое исследование процесса образования металлических и карбидных фаз при термическом разложении [CuEn3]MoO4 в атмосфере Не в присутствии LiH: начиная с 973 K образуется смесь Mo2C и ГЦК-фазы на основе структуры Cu (а ≈ 3.65 Å).

Проведен синтез двух комплексных солей с участием гептавольфрамат-анионов и катионов [Pd(NH3)4]2+ и Na+. В структуре Na2[Pd(NH3)4]5(W7O24)2×16H2O (а = 11.5703(3) Å, b = 12.4653(4) Å, с = 14.8201(5) Å, α = 69.733(1)°, β = 97.231(1)°, γ = 75.816(1)°, пр. гр. P-1, V = 1937.8(1) Å3, Z = 1) катионы Na+ связывают гептавольфрамат-анионы в димеры, расстояния Na…О 2.321—2.446 Å. В структуре Na[Pd(NH3)4]2(HW7O24)×7H2O (а = 11.1113(8) Å, b = 17.9869(12) Å, с = 17.8140(13) Å, β = 96.974(2)°, пр. гр. P21/n, V = 3533.9(4) Å3, Z = 4) мостиковые катионы Na+ связывают гидрогептавольфрамат-анионы в зигзагообразные цепочки расстояния Na…О 2.291—2.724 Å.

Изучены две кристаллические структуры с участием катионов [Pd(NH3)4]2+ и анионов WO42– и W7O246–. Для структуры [Pd(NH3)4]WO4 при 150 K получены кристаллографические данные: а = 7.4626(3) Å, с = 15.5718(8) Å, пр. гр. I41/amd, V = 867.20 Å3, Z = 4. При повышении температуры до 400 K параметры элементарной ячейки изменяются разнонаправлено: а увеличивается на 0.032 Å, с уменьшается на 0.036 Å. Общее увеличение объема ячейки составляет 5 Å3. В интервале от 150 K до 400 K наблюдаемые расстояния W—О уменьшаются на 0.019 Å — от 1.778(18) Å до 1.759(3) Å. Для структуры [Pd(NH3)4]3W7O24·4.4H2O при 298 K кристаллографические данные следующие: а = 8.3409(2) Å, b = 22.2654(6) Å, с = 10.5450(3) Å, β = 104.449(1)°, пр. гр. P21/m, V = 1896.41 Å3, Z = 2. В гептавольфрамат-анионе наиболее короткие — расстояния W—O c участием концевых атомов О 1.731—1.745 Å. Расстояния до мостиковых атомов О, связывающих два атома W — 1.930—2.406 Å, три — 1.882—2.234 Å, четыре — 2.192—2.220 Å. Показано, что структура [Pd(NH3)4]3W7O24·4.4H2O имеет псевдогексагональный мотив в направлении а. Проведено термическое разложение солей в присутствии LiH в атмосфере Не при 1273 K, ex situ рентгенографическое исследование показало образование сплавов Pd—W.

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) angstrom, c = 15.5718(8) angstrom, space group I4(1)/amd, V = 867.20 angstrom(3), Z = 4. With increasing temperature to 400 K, the unit cell parameters change in different directions: a increases by 0.032 angstrom, c decreases by 0.036 angstrom. The total increase in the unit cell volume is 5 angstrom(3). In a range of 150 K to 400 K, the observed W-O distances decrease by 0.019 angstrom from 1.778(18) angstrom to 1.759(3) angstrom. For the [Pd(NH3)(4)](3)W7O24.4.4H(2)O structure at 298 K the crystallographic data are as follows: a = 8.3409(2) angstrom, b = 22.2654(6) angstrom, c = 10.5450(3) angstrom, beta = 104.449(1)degrees, space group P2(1)/m, V = 1896.41 angstrom(3), Z = 2. In the heptatungstate anion the shortest are the W-O distances with the terminal O atoms (1.7311.745 angstrom). The distances to the bridging O atoms connecting two W atoms are 1.9302.406 angstrom; those connecting three W atoms are 1.8822.234 angstrom, and those connecting four W atoms are 2.1922.220 angstrom. It is shown that the [Pd(NH3)(4)](3)W7O24.4.4H(2)O 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 PdW alloys.