Z. Kristallogr.

NCS 220 (2005) 519-520 519

© by Oldenbourg Wissenschaftsverlag, München

Crystal structure of dibarium mononitride, Ba2N,

an alkaline earth metal subnitride

O. Reckeweg* and F. J. DiSalvo

Cornell University, Department of Chemistry and Chemical Biology, Baker Laboratory, Ithaca, NY 14853-1301, USA

Received August 28, 2005, accepted and available on-line December 3, 2005; CSD no. 409851

off the resulting metallic regulus and show a very strong affinity
towards oxygen and water.

Discussion
As the other subnitrides of the alkaline earth metal triade [1-7],
Ba2N crystallizes in the rhombohedral anti CdCl2 structure type.
In most AE2NX compounds (AE = Ca, Sr or Ba; X = H, F, Cl or Br)
[4] the space between the [AE6/3N] slabs is occupied by an anion
that holds them together. Comparing these structures to the struc-
ture of the AE2N compounds and referring to the ionic formula-
tion (AE2+)2(N3– )(e– ) [2,4,8], it has been suggested that the excess
electron [2] is located in the space between the ionic AE-N-AE
slabs. The ionicity in the title compound is indicated by an Ba—N
distance of 276.75(6) pm typical for ionic nitrides. The structural
data reported so far for Ba2N [9-14] corroborate in principle the
present results. However, only the a lattice parameters found so
far (399 pm – 405 pm) agree in the range of the accuracy of the re-
spective measurements, while the c lattice parameters vary for yet
undetermined reasons in the range from 2208 pm – 2270 pm.

Table 1. Data collection and handling.

Abstract
Ba2N, trigonal, R3m (no. 166), a = 4.0290(6) Å,
c = 22.425(4) Å, V = 315.3 Å3, Z = 3, Rgt(F) = 0.026, Crystal: black hexagonal plate,
size 0.02 × 0.12 × 0.12 mm
wRref(F2) = 0.063, T = 293 K. Wavelength: Mo K radiation (0.71073 Å)
: 183.85 cm−1
Source of material Diffractometer, scan mode: Bruker SMART CCD, /
Black single crystals of Ba2N with a bluish lustre were obtained 2 max: 49.42°
from the reaction of Ba, NaN3 and Na (molar ratio 6:2:20) taking N(hkl)measured, N(hkl)unique: 709, 93
Criterion for Iobs, N(hkl)gt: Iobs > 2 (Iobs), 93
place in an arc-welded Ta ampoule at 1300 K for 2 h and subse- N(param)refined: 7
quent annealing for 7 d at 800 K. The reaction was kept perma- Programs: SHELXTL [15], CrystalMaker [16]
nently under dynamic vacuum. Crystals of Ba2N could be chipped

Table 2. Atomic coordinates and displacement parameters (in Å2).

Atom Site x y z U11 U22 U33 U12 U13 U23

Ba 6c 0 0 0.26647(5) 0.0196(6) U11 0.060(1) ½U11 0 0

N 3a 0 0 0 0.015(5) U11 0.035(9) ½U11 0 0

Acknowledgment. We wish to thank Prof. Dr. mult. A. Simon for advice and
inspiring discussions.

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_____________
* Correspondence author (e-mail: or22@cornell.edu)
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