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BY-NC-ND 3.0 license Open Access Published by De Gruyter (O) April 12, 2016

Crystal structure of pentacalcium tetranitridovanadate(V) mononitride based on a powder diffraction study, Ca5[VN4]N

Alexander Ovchinnikov and Peter Höhn


Ca5N5V, orthorhombic, Pbcm (no. 57), a = 6.0371(3) Å, b = 16.6146(7) Å, c = 6.7815(3) Å, V = 680.21(5) Å3, Z = 4, R(P) = 0.0100, RF(all) = 0.0348, T = 293 K.

CCDC no.:: 431041

Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Sample, setting:Yellow powder, transmission geomety
Wavelength, μ:Cu Kα radiation (1.54056 Å), 450.05 cm−1
Diffractometer, scan mode:Huber Guinier G670, step scan (0.005°)
2θ range / data points:8.0-100.3°, 18461
Background funtion:26 Legendre polynoms
Profile function:Pseudo-Voigt
N(hkl), N(param.):334, 61
Programs:JANA2006 [6], Diamond [7]

Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).


Source of material

Calcium nitride, Ca3N2, was prepared from calcium lumps and nitrogen gas at 1023 K. The resulting red single phase material was mixed with vanadium powder in the ratio Ca:V = 5:1. The mixture was pelletized and annealed under nitrogen stream at 1000 K for 60 h and then at 1323 K for 48 h. The yellow microcrystalline product was identified as a new phase according to PXRD.


Although isolated [VN4]7− units were found in different crystal modifications of Li7VN4 [1], only crystal structures with one-dimensional anions represented by infinite chains of corner sharing 1(VN2/2N24−) tetrahedra have been reported so far for nitridovanadates(V) of alkaline earth metals [2, 3]. Inspection of the PXRD pattern and further Rietveld refinement revealed that the title phase is isotypic with another group V element ternary nitride, Sr5NbN5 [4], and belongs to the Na5OAsO4 structure type [5]. The structure can be described as consisting of isolated [VN4]7− tetrahedra and zigzag chains of corner-sharing 1(NCa4Ca2/27+) octahedra running along the c direction as shown in the figure. A distortion of the tetrahedra lowers the local symmetry down to Cs. Refined V—N distances lie in the range 1.85(2) Å – 1.91(3) Å, which is close to the values observed for other nitrides bearing tetrahedrally coordinated V(V) [13]. Band-structure calculations revealed an insulating ground state in accordance with the crystal structure.


Dr. Horst Borrmann and Mr. Steffen Hückmann are acknowledged for collecting PXRD data.


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Received: 2015-11-25
Accepted: 2016-3-18
Published Online: 2016-4-12
Published in Print: 2016-9-1

©2016 Alexander Ovchinnikov et al., published by De Gruyter.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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