Cargando…

Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior

Moolooite, Cu(C(2)O(4))·nH(2)O, is a typical biomineral which forms due to Cu-bearing minerals coming into contact with oxalic acid sources such as bird guano deposits or lichens, and no single crystals of moolooite of either natural or synthetic origin have been found yet. This paper reports, for t...

Descripción completa

Detalles Bibliográficos
Autores principales: Kornyakov, Ilya V., Gurzhiy, Vladislav V., Kuz’mina, Mariya A., Krzhizhanovskaya, Maria G., Chukanov, Nikita V., Chislov, Mikhail V., Korneev, Anatolii V., Izatulina, Alina R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10094873/
https://www.ncbi.nlm.nih.gov/pubmed/37047759
http://dx.doi.org/10.3390/ijms24076786
_version_ 1785023945780494336
author Kornyakov, Ilya V.
Gurzhiy, Vladislav V.
Kuz’mina, Mariya A.
Krzhizhanovskaya, Maria G.
Chukanov, Nikita V.
Chislov, Mikhail V.
Korneev, Anatolii V.
Izatulina, Alina R.
author_facet Kornyakov, Ilya V.
Gurzhiy, Vladislav V.
Kuz’mina, Mariya A.
Krzhizhanovskaya, Maria G.
Chukanov, Nikita V.
Chislov, Mikhail V.
Korneev, Anatolii V.
Izatulina, Alina R.
author_sort Kornyakov, Ilya V.
collection PubMed
description Moolooite, Cu(C(2)O(4))·nH(2)O, is a typical biomineral which forms due to Cu-bearing minerals coming into contact with oxalic acid sources such as bird guano deposits or lichens, and no single crystals of moolooite of either natural or synthetic origin have been found yet. This paper reports, for the first time, on the preparation of single crystals of a synthetic analog of the copper-oxalate biomineral moolooite, and on the refinement of its crystal structure from the single-crystal X-ray diffraction (SCXRD) data. Along with the structural model, the SCXRD experiment showed the significant contribution of diffuse scattering to the overall diffraction data, which comes from the nanostructural disorder caused by stacking faults of Cu oxalate chains as they lengthen. This type of disorder should result in the chains breaking, at which point the H(2)O molecules may be arranged. The amount of water in the studied samples did not exceed 0.15 H(2)O molecules per formula unit. Apparently, the mechanism of incorporation of H(2)O molecules governs the absence of good-quality single crystals in nature and a lack of them in synthetic experiments: the more H(2)O content in the structure, the stronger the disorder will be. A description of the crystal structure indicates that the ideal structure of the Cu oxalate biomineral moolooite should not contain H(2)O molecules and should be described by the Cu(C(2)O(4)) formula. However, it was shown that natural and synthetic moolooite crystals contain a significant portion of “structural” water, which cannot be ignored. Considering the substantially variable amount of water, which can be incorporated into the crystal structure, the formula Cu(C(2)O(4))·nH(2)O for moolooite is justified.
format Online
Article
Text
id pubmed-10094873
institution National Center for Biotechnology Information
language English
publishDate 2023
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-100948732023-04-13 Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior Kornyakov, Ilya V. Gurzhiy, Vladislav V. Kuz’mina, Mariya A. Krzhizhanovskaya, Maria G. Chukanov, Nikita V. Chislov, Mikhail V. Korneev, Anatolii V. Izatulina, Alina R. Int J Mol Sci Article Moolooite, Cu(C(2)O(4))·nH(2)O, is a typical biomineral which forms due to Cu-bearing minerals coming into contact with oxalic acid sources such as bird guano deposits or lichens, and no single crystals of moolooite of either natural or synthetic origin have been found yet. This paper reports, for the first time, on the preparation of single crystals of a synthetic analog of the copper-oxalate biomineral moolooite, and on the refinement of its crystal structure from the single-crystal X-ray diffraction (SCXRD) data. Along with the structural model, the SCXRD experiment showed the significant contribution of diffuse scattering to the overall diffraction data, which comes from the nanostructural disorder caused by stacking faults of Cu oxalate chains as they lengthen. This type of disorder should result in the chains breaking, at which point the H(2)O molecules may be arranged. The amount of water in the studied samples did not exceed 0.15 H(2)O molecules per formula unit. Apparently, the mechanism of incorporation of H(2)O molecules governs the absence of good-quality single crystals in nature and a lack of them in synthetic experiments: the more H(2)O content in the structure, the stronger the disorder will be. A description of the crystal structure indicates that the ideal structure of the Cu oxalate biomineral moolooite should not contain H(2)O molecules and should be described by the Cu(C(2)O(4)) formula. However, it was shown that natural and synthetic moolooite crystals contain a significant portion of “structural” water, which cannot be ignored. Considering the substantially variable amount of water, which can be incorporated into the crystal structure, the formula Cu(C(2)O(4))·nH(2)O for moolooite is justified. MDPI 2023-04-05 /pmc/articles/PMC10094873/ /pubmed/37047759 http://dx.doi.org/10.3390/ijms24076786 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Kornyakov, Ilya V.
Gurzhiy, Vladislav V.
Kuz’mina, Mariya A.
Krzhizhanovskaya, Maria G.
Chukanov, Nikita V.
Chislov, Mikhail V.
Korneev, Anatolii V.
Izatulina, Alina R.
Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior
title Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior
title_full Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior
title_fullStr Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior
title_full_unstemmed Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior
title_short Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior
title_sort crystal chemistry of the copper oxalate biomineral moolooite: the first single-crystal x-ray diffraction studies and thermal behavior
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10094873/
https://www.ncbi.nlm.nih.gov/pubmed/37047759
http://dx.doi.org/10.3390/ijms24076786
work_keys_str_mv AT kornyakovilyav crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT gurzhiyvladislavv crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT kuzminamariyaa crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT krzhizhanovskayamariag crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT chukanovnikitav crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT chislovmikhailv crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT korneevanatoliiv crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior
AT izatulinaalinar crystalchemistryofthecopperoxalatebiomineralmoolooitethefirstsinglecrystalxraydiffractionstudiesandthermalbehavior