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A novel сalcium trifluoroacetate structure

https://doi.org/10.32362/2410-6593-2021-16-4-352-362

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Abstract

Objectives. The study was devoted to considering the features of the synthesis and crystal structure of calcium trifluoroacetate Ca2(CF3COO)4·8CF3COOH and investigating the products of its thermal behavior.
Methods. The compositions of the proposed structural form were characterized by various physicochemical methods (X-ray diffraction, IR spectroscopy), and the products of thermal decomposition were determined under dynamic vacuum conditions.
Results. The reaction between calcium carbonate and 99% trifluoroacetic acid yielded a new structural type of calcium trifluoroacetate Ca2(CF3COO)4·8CF3COOH (I) in the form of colorless prismatic crystals unstable air. X-ray diffraction results confirmed the composition I: space group P21, with unit cell parameters: a = 10.0193(5) Å, b = 15.2612(7) Å, c = 16.3342(8) Å, β = 106.106(2)°, V = 2399.6(2) Å3, Z = 2. The structure is molecular, constructed from Ca2(CF3COO)4·8CF3COOH dimers. The end molecules of the trifluoroacetic acid were involved in the formation of intramolecular hydrogen bonds with oxygen atoms of the bidentate bridging anions CF3COO. There were strongly pronouncedsymmetric and asymmetric absorption bands of COO and CF3-groups in the IR spectrum of the resulting compound in the range of 1200–1800 cm−1. The definite peak of the oscillation of the OH-group at 3683 cm−1 corresponds to the trifluoroacetic acid molecules present in the structure. The broadpeak of the valence oscillations in the range of 3300–3500 cm−1 is caused by the presence of intramolecular hydrogen bonds. Decomposition began at 250°C and 10−2 mm Hg with calcium fluoride CaF2 as the final decomposition product.
Conclusions. We obtained a previously undescribed calcium–trifluoroacetic acid complex whose composition can be represented by Ca2(CF3COO)4·8CF3COOH. The crystal island structure is a dimeric molecule where the calcium atoms are bound into dimers by four trifluoroacetate groups. The complex was deposited in the Cambridge Structural Data Bank with a deposit number CCDC 2081186. Although the compound has a molecular structure, thermal decomposition leads to the formation of calcium fluoride characterized by a small particle size, which may further determine its applications.

About the Authors

A. A. Vasilyeva
Faculty of Chemistry, Lomonosov Moscow State University
Russian Federation

Alexandra A. Vasilyeva, Student

1-3, Leninskie Gory, GSP-1, Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest.



T. Yu. Glazunova
Faculty of Chemistry, Lomonosov Moscow State University
Russian Federation

Tatyana Yu. Glazunova, Senior Lecturer, Department of Inorganic Chemistry

1-3, Leninskie Gory, GSP-1, Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest.



D. S. Tereshchenko
Faculty of Chemistry, Lomonosov Moscow State University
Russian Federation

Denis S. Tereshchenko, Research Assistant

1-3, Leninskie Gory, GSP-1, Moscow, 119991


Competing Interests:

The authors declare no conflicts of interest.



E. Kh. Lermontova
N.S. Kurnakov Institute of General and Inorganic Chemistry
Russian Federation

Elmira Kh. Lermontova, Researcher

31, Leninskii pr., Moscow, 119071


Competing Interests:

The authors declare no conflicts of interest.



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2. This is to certify that the paper titled A novel сalcium trifluoroacetate structure commissioned to us by Alexandra A. Vasilyeva, Tatyana Yu. Glazunova, Denis S. Tereshchenko, Elmira Kh. Lermontova has been edited for English language and spelling by Enago, an editing brand of Crimson Interactive Inc.
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  • A new molecular structure of calcium trifluoroacetate Ca2(CF3COO)4∙8CF3COOH constructed from dimers was synthesized.
  • The decomposition product of the compound is CaF2 with small particle size.

For citation:


Vasilyeva A.A., Glazunova T.Yu., Tereshchenko D.S., Lermontova E.K. A novel сalcium trifluoroacetate structure. Fine Chemical Technologies. 2021;16(4):352-362. https://doi.org/10.32362/2410-6593-2021-16-4-352-362

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