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X-ray powder diffraction data for tetrazene nitrate monohydrate, C2H9N11O4

Published online by Cambridge University Press:  02 November 2021

J. Maixner Open the ORCID record for J. Maixner [Opens in a new window]  and
J. Ryšavý
J. Maixner*
Affiliation:
Central Laboratories, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic
J. Ryšavý
Affiliation:
Faculty of Chemical Technology, Institute of Energetic Materials, University of Pardubice, Studentská 95, 532 10Pardubice, Czech Republic
*
a)Author to whom correspondence should be addressed. Electronic mail: jaroslav.maixner@vscht.cz
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Abstract

X-ray powder diffraction data, unit-cell parameters, and space group for tetrazene nitrate monohydrate, C2H9N11O4, are reported [a = 5.205(1) Å, b = 13.932(3) Å, c = 14.196(4) Å, β = 97.826(3)°, unit-cell volume V = 1019.8(4) Å3, Z = 4, and space group P21/c]. All measured lines were indexed and are consistent with the P21/c space group. No detectable impurities were observed.

Keywords

X-ray powder diffractiontetrazenehydrateexplosivemunitions industry
Type
New Diffraction Data
Information
Powder Diffraction , Volume 36 , Issue 4 , December 2021 , pp. 270 - 272
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Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of International Centre for Diffraction Data

I. INTRODUCTION

Tetrazene, first prepared in 1892 by Thiele (Reference Thiele1892), is a primary explosive mainly used in the munitions industry as an energetic sensitizer particularly in percussion and stab priming compositions (Hagel and Redecker, Reference Hagel and Redecker1986; Matyáš and Pachman, Reference Matyáš and Pachman2013). It was first studied in 1910 by Hofmann and Roth (Reference Hofmann and Roth1910) who also prepared several anionic and cationic salts of tetrazene. This ability is attributed to the zwitterion nature of tetrazene, which was discovered after several revisions of the molecule structure in 1971 by Duke (Reference Duke1971). These salts, aside of few minor mentions (McNutt, Reference McNutt1933; Straka and Vachovec, Reference Straka and Vachovec1944; Conduit, Reference Conduit1955; Patinkin et al., Reference Patinkin, Horwitz and Lieber1955; Špičák and Šimeček, Reference Špičák and Šimeček1957; Багал, Reference Багал1975), were never truly studied.

We have not found this compound in the CSD database (Groom et al., Reference Groom, Bruno, Lightfoot and Ward2016) or in the PDF4+ database (Gates-Rector and Blanton, Reference Gates-Rector and Blanton2019). Therefore, we have decided to characterize this compound by an X-ray powder diffraction (XRD) technique. In our study, we present powder data for tetrazene nitrate monohydrate (C2H9N11O4; Figure 1).

Figure 1. Structural formula of tetrazene nitrate monohydrate.

II. EXPERIMENTAL

A. Synthesis

The synthesis of tetrazene nitrate was inspired by the first preparation of this compound type by Hofmann and Roth (Reference Hofmann and Roth1910): Tetrazene (1.5 g; 7.97 mmol) was dissolved in 65% nitric acid (20 ml; 292 mmol) and diethylether (80 ml) was added dropwise. First, a layer of heavy white liquid separates in the mixture, which with further diethylether starts to coagulate to form lumps that eventually within a matter of minutes fall apart into course heavy white powder. The solid was filtered off and washed with ether.

B. Specimen preparation

Tetrazene nitrate monohydrate is a primary explosive and therefore must be handled very carefully. The synthesized powder is very well crystallized with crystallite size suitable for powder XRD, and therefore, no grinding is necessary. The sample could be front-loaded into the specimen holder and limited force was used to make the sample surface flat.

C. Diffraction data collection and reduction

The diffraction pattern for the title compound was collected at room temperature with an X'Pert3 Powder θ–θ powder diffractometer with parafocusing Bragg–Brentano geometry using CuKα radiation (λ = 1.5418 Å, Ni filter, generator setting: 40 kV, 30 mA). An ultrafast PIXCEL detector with 255 channels was employed to collect XRD data over the angular range from 5 to 80° 2θ with a step size of 0.026° 2θ and a counting time of 0.618 s per step.

The software package HighScore Plus V 4.8(PANalytical, Almelo, Netherlands) was used to smooth the data, to fit the background, to eliminate the Kα 2 component and the top of the smoothed peaks were used to determine the peak positions and intensities of the diffraction peaks (Table I). The d-values were calculated using CuKα 1 radiation (λ = 1.5406 Å).

TABLE I. Indexed X-ray powder diffraction data for C2H9N11O4.

Only the peaks with I rel of 1 or greater are presented [a = 5.205(1) Å, b = 13.932(3) Å, c = 14.196(4) Å, β = 97.826(3)°, unit-cell volume V = 1019.8(4) Å3, Z = 4, and space group P21/c]. All lines were indexed and are consistent with the P21/c space group. The d-values were calculated using CuKα 1 radiation (λ = 1.5406 Å).

III. RESULTS AND DISCUSSION

The automatic indexing of results was obtained using Dicvol (Boultif and Louër, Reference Boultif and Louër2004). The experimental powder diffraction pattern is shown in Figure 2. Tetrazene nitrate monohydrate, C2H9N11O4, is monoclinic with the space group P21/c and unit-cell parameters: a = 5.205(1) Å, b = 13.932(3) Å, c = 14.196(4) Å, β = 97.826(3)°, unit-cell volume V = 1019.8(4) Å3, and Z = 4. The figures of merits are F 20 = 16.3(0.0205, 60) and M 20 = 8.8 (de Wolff, Reference de Wolff1968; Smith and Snyder, Reference Smith and Snyder1979). All measured lines (Table I) were indexed and are consistent with the P21/c space group.

Figure 2. X-ray powder diffraction pattern of tetrazene nitrate monohydrate using CuKα radiation (λ = 1.5418 Å).

Funding

Part of this work was supported by the University of Pardubice, Czech Republic, under the project no. SGS_2021_004.

References

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Figure 0

Figure 1. Structural formula of tetrazene nitrate monohydrate.

Figure 1

TABLE I. Indexed X-ray powder diffraction data for C2H9N11O4.

Figure 2

Figure 2. X-ray powder diffraction pattern of tetrazene nitrate monohydrate using CuKα radiation (λ = 1.5418 Å).