TY - JOUR

T1 - 2d, or Not 2d: An Almost Perfect Mock of Symmetry

AU - Komarov, Vladislav

AU - Galiev, Ruslan

AU - Artemkina, Sofya

N1 - This research was funded by the Russian Science Foundation (project RSF No. 21-13-00274, https://rscf.ru/project/21-13-00274/, accessed on 19 April 2021). The authors also thank XRD Facility of Nikolaev Institute of Inorganic Chemistry SB RAS for the SC XRD data collection (Ministry of Science and Higher Education of the Russian Federation, N 121031700313-8).

PY - 2023/2

Y1 - 2023/2

N2 - The paper is related to an interesting case of revision of X-ray crystal structure with a lack of experimental data. Complexes V4OSe8I6·X (X = I2 or 3,5-dimethylpyrazole) with O-centered complex molecules [V4O(μ-Se2)4I4(μ-I)2] were synthesized in our group. In the further search for new relative compounds in the V-Se-I-O system, we obtained several crystals with different structures, including “V4OSe6I3”, with incredibly complicated connectivity of {V4O(Se2)4I6} units bridged via both diselenide and iodide ligands. Due to the absence of phase-pure products and the possible instability of some of the phases under ambient conditions, we were mainly guided by the single-crystal X-ray diffraction data. However, seeing a very complex coordination mode in the “V4OSe6I3” structure, we have carefully analyzed the structure from the positions of symmetry and chemical synthesis in this system. The “new structure” was recognized as the complex superposition of the structure of another compound with composition “V4OSe6I10” just found in the same experiment. We outlined the course of observations, reasoning and solutions to the symmetry false estimation problem, which we believe to be of interest to readers dealing with X-ray diffraction analysis.

AB - The paper is related to an interesting case of revision of X-ray crystal structure with a lack of experimental data. Complexes V4OSe8I6·X (X = I2 or 3,5-dimethylpyrazole) with O-centered complex molecules [V4O(μ-Se2)4I4(μ-I)2] were synthesized in our group. In the further search for new relative compounds in the V-Se-I-O system, we obtained several crystals with different structures, including “V4OSe6I3”, with incredibly complicated connectivity of {V4O(Se2)4I6} units bridged via both diselenide and iodide ligands. Due to the absence of phase-pure products and the possible instability of some of the phases under ambient conditions, we were mainly guided by the single-crystal X-ray diffraction data. However, seeing a very complex coordination mode in the “V4OSe6I3” structure, we have carefully analyzed the structure from the positions of symmetry and chemical synthesis in this system. The “new structure” was recognized as the complex superposition of the structure of another compound with composition “V4OSe6I10” just found in the same experiment. We outlined the course of observations, reasoning and solutions to the symmetry false estimation problem, which we believe to be of interest to readers dealing with X-ray diffraction analysis.

KW - Chalcohalide

KW - Crystal structure connectivity

KW - Periodic DFT structure refinement

KW - Polynuclear complex

KW - SC XRD faults

KW - Symmetry false estimation

KW - Vanadium

KW - X-ray single crystal diffraction

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85149238112&origin=inward&txGid=a89eb5fff43212ef8623ede8e031e4a7

UR - https://www.mendeley.com/catalogue/9122adc9-f5d2-3c89-80ac-dfa342d1d639/

U2 - 10.3390/sym15020508

DO - 10.3390/sym15020508

M3 - Article

VL - 15

JO - Symmetry

JF - Symmetry

SN - 2073-8994

IS - 2

M1 - 508

ER -