From Cs[C2N3] to Cs3[C6N9] – a thermal and structural investigation
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Olaf Reckeweg
,
Francis J. DiSalvo
Abstract
Cesium dicyanamide Cs[C2N3] (≡ Cs[N(CN)2] or Cs[dca]) was obtained by a metathesis reaction in form of transparent colorless platelets. The results of single-crystal X-ray structure measurements and refinements (C2/c, Z = 8) with the monoclinic cell parameters a = 932.31(8), b = 1274.67(9), c = 824.94(7) pm, β = 110.803(3)° at −70 °C and a = 939.59(7), b = 1281.58(8), c = 827.57(6) pm, β = 110.610(3)° at 20 °C corroborate earlier results for this compound. The Raman and IR spectra of Cs[C2N3] are presented for the first time and the result compares well with those of NaCs2[C2N3]3. The heat-driven cyclotrimerization process of Cs[C2N3] was studied by thermal analyses (DSC) and temperature-dependent X-ray powder diffraction methods. At 370 °C, its trimerization product Cs3[C6N9] is formed, crystallizing in the orthorhombic space group Pbam with the cell parameters a = 3043.0(3), b = 1052.4(1) and c = 415.21(4) pm for Z = 4. The IR spectrum of this cesium tricyanomelaminate (Cs3[C6N9] or Cs3[TCM]) is presented, but a well-resolved Raman spectrum could not be acquired owing to fluorescence phenomena. An overview about the cyclotrimerization reactions of all pseudo-binary alkali-metal dicyanamides (A[C2N3]) to their corresponding tricyanomelaminates (A 3[C6N9]) with A = Li–Cs gives a basis for a discussion of the different thermal and structural characteristics.
Dedicated to Professor Thomas Bredow of the University of Bonn on the occasion of his 60th birthday.
Acknowledgments
Thanks are due for acquiring the Raman spectrum of Cs[C2N3] to Armin Schulz (MPI-FKF Stuttgart, Germany); for measuring the single-crystal intensity data Cs[C2N3] (room temperature) we are indebted to Dr. Falk Lissner (IAC, Universität Stuttgart, Germany).
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Research ethics: Not applicable.
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Author contributions: The authors have accepted responsibility for the entire content of this submitted manuscript and approved its submission.
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Competing interests: The authors state no conflict of interest.
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Research funding: None declared.
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Data availability: Crystallographic data can be obtained as indicated in the manuscript.
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Articles in the same Issue
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Articles in the same Issue
- Frontmatter
- In this issue
- Editorial
- Thomas Bredow zum 60. Geburtstag gewidmet
- Research Articles
- Ni2Mo3N: crystal structure, thermal properties, and catalytic activity for ammonia decomposition
- Ionic conductivity of nanocrystalline γ-AgI prepared by high-energy ball milling
- Ba3Mg4Au4 – a ternary auride composed of BaAu2- and BaMg2Au-related slabs
- Solvothermal synthesis and selected properties of {[Ni(dien)2]3[V6As8O26]}2+·2 Cl– featuring the small [V6IVAs8IIIO26]4– cluster anion
- Ab initio calculations of the chemisorption of atomic H and O on Pt and Ir metal and on bimetallic Pt x Ir y surfaces
- mcGFN-FF: an accurate force field for optimization and energetic screening of molecular crystals
- A molecular mechanics implementation of the cyclic cluster model
- A computational characterization of N-heterocyclic carbenes for catalytic and nonlinear optical applications
- Oxygen diffusion in β-Ga2O3 single crystals under different oxygen partial pressures at 1375 °C
- Origin of extended visible light absorption in nitrogen-doped CuTa2O6 perovskites: the role of copper defects
- High-temperature all-solid-state batteries with LiBH4 as electrolyte – a case study exploring the performance of TiO2 nanorods, Li4Ti5O12 and graphite as active materials
- Cu2Mg5Sn5Se16 – the first selenospinel of the A2B5C5X16 type
- Crystal structures and crystallographic classification of titanium silicophosphates – with a note on structure and composition of silicophosphates “M3P5SiO19”
- From Cs[C2N3] to Cs3[C6N9] – a thermal and structural investigation
- A Hybrid Monte Carlo study of argon solidification
