Research output: Contribution to journal › Article › peer-review
[CuEn 3]MoO4 : Synthesis, Structure, Jahn-Teller Effect, Transformations in the Range 100–1263 K. / Khranenko, S. P.; Sukhikh, A. S.; Nikolaev, R. E. et al.
In: Journal of Structural Chemistry, Vol. 61, No. 2, 01.02.2020, p. 267-273.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - [CuEn 3]MoO4
T2 - Synthesis, Structure, Jahn-Teller Effect, Transformations in the Range 100–1263 K
AU - Khranenko, S. P.
AU - Sukhikh, A. S.
AU - Nikolaev, R. E.
AU - Gromilov, S. A.
PY - 2020/2/1
Y1 - 2020/2/1
N2 - 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 P3 ¯ , 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 P3 ¯ 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, P3 ¯ 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.
AB - 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 P3 ¯ , 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 P3 ¯ 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, P3 ¯ 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.
KW - complex salt
KW - copper tris-ethylenediamine
KW - crystal chemistry
KW - Jahn-Teller effect
KW - molybdate anion
KW - X-ray diffraction analysis
KW - CRYSTAL-STRUCTURES
KW - TRIS(ETHYLENEDIAMINE)ZINC(II) SULFATE
KW - PROGRAM
UR - http://www.scopus.com/inward/record.url?scp=85087982733&partnerID=8YFLogxK
U2 - 10.1134/S0022476620020110
DO - 10.1134/S0022476620020110
M3 - Article
AN - SCOPUS:85087982733
VL - 61
SP - 267
EP - 273
JO - Journal of Structural Chemistry
JF - Journal of Structural Chemistry
SN - 0022-4766
IS - 2
ER -
ID: 24753283