Polynitrides

Polynitrides are solid chemical compounds with a large amount of nitrogen, beyond what would be expected from valencies. Some with N2 ions are termed pernitrides. Azides are not considered polynitrides, although pentazolates are.

They are formed at high pressures and mostly at high temperature. Many are stable under high pressure, but some are metastable when decompressed to standard conditions. They are high energy density materials, capable of exploding with high power. Some are very hard, almost as strong as diamond.

Nitrogen anions can take the form of diazenide [N2−2], pentazolate [N−5], 1-dimensional chains [N2−4], hexazine dianion [N2−6], pernitride N4−2 and even include dinitrogen molecules.

List

Formula Crystallography Properties References
Empirical Structural Notes Crystal Space
group		 Unit cell (Å)
Formula units (Z)
 Volume
(Å3)		 Density
(g·cm−3)
At pressure
(GPa)
Bulk modulus
at zero pressure
(K0) (GPa)
Lowest observed
pressure (GPa)
 Comments
LiN [Li+]2[N2−2] diazenide orthorhombic Immm a=3.1181 b=4.4372 c=10.7912 8 149.30 0 0 black, metallic luster
orthorhombic Cmcm a=3.819 b=6.471 c=3.446 8 85.16 73.6 112(19) 19.0
LiN2 Li+N−2 N−2 dimers hexagonal P63/mmc a=2.631 c=7.615 2 45.64 21.2 63(4) 4.6 white
LiN5 Li+N−5 pentazolate monoclinic P2 a=3.808 b=3.838 c=2.410

β=99.84°

 1 34.70 73.6 0
73.6 (XRD)
tr-BeN4 Be2+[poly-N2−4] 1D chains, N4 torsion angle = 17.1° triclinic

(2D layers)

 P1 a=3.275 b=4.212 c=3.704

α=103.43º β=105.61º γ=111.86º

 1 42.4 0 0
triclinic P1 a=2.4062 b=3.5119 c=3.506

α=104.29° β=111.39° γ=96.71°

 1 26.02 83.5
m-BeN4 2D infinite sheets of fused N10 rings monoclinic P21/c a=3.283 b=3.2765 c=4.8185

β=99.67°

 2 51.10 96.8 96.8
Amm2-CN6 2D Amm2
Amm2-CN10 2D Amm2
NaN2 Na+N−2 N−2 dimers tetragonal P4/mmm a=3.001 c=4.101 1 36.93 4.0 2.8 black, metallic luster
Na3N8 [Na+]3[N23/4−]4 N20.75- dimers tetragonal I41/amd a=4.9597 c=16.29 4 400.7 27.6 7.7 black, metallic luster
Na2N5 [Na+]2[N2−5] pentazolate-derived dianion monoclinic Pm a=4.781 b=2.5873 c=4.934

β=119.6°

 1 53.1 50.0 18 (Raman)
NaN5 Na+N−5 pentazolate orthorhombic Pmn21 a=5.455 b=2.836 c=5.662 2 87.6 52.9 12 (Raman)

25 (XRD)
NaN7 Na+N−5·N2 pentazolate

nitrogen-inclusion

 monoclinic P21/n a=10.321 b=8.672 c=11.0409

β=91.70°

 16 987.8 52.9 40
α-Mg2N4 [Mg2+]2[a'-N4−4][b'-N4−4] cis-tetranitrogen tetraanion monoclinic P21/n a=7.5182 b=6.5426 c=13.4431

β=130.080°

 2 505.95 0 0
β-Mg2N4 [Mg2+]2[a-N4−4][b-N4−4] cis-tetranitrogen tetraanion monoclinic P21/n a=7.114 b=5.824 c=8.804

β=104.04°

 2 354.0 58.5 2.3
MgN4 Mg2+[poly-N2−4] 1D chains, N4 torsion angle = 0°
isoelectronic to polythiazyl
cis-polyacetylene geometry		 orthorhombic Ibam a=3.5860 b=7.526 c=5.1098 1 137.90 58.5 0.9 (Raman)
58.5 (XRD)		 : Figure S3 
SiN2 Si4+N4−2 pernitride cubic Pa3 a=4.1205 4 69.96 5.327 140 140
K3N8 [K+]3[N23/4−]4
tetragonal I41/amd a=5.331 c=17.552 4 498.8 27 27 reflective
K2N6 [K+]2[N2−6] planar hexazine dianion hexagonal P6/mmm a=5.281 c=2.661 1 64.27 50
  • 20 (Raman)
  • 21 (XRD)
 reflective
K9N56 [K+]18[N4−6][N−5]14·18N2
orthorhombic Ibam a=5.2380 b=34.560 c=23.205 8 4200.7 61 32
Sc2N6 triclinic P1 a=2.9170 b=4.328 c=4.812 α=99.36 β=104.29 γ=99.52 1 56.73 5.093 78 metallic
Sc2N8 monoclinic P21/c a=3.3278 b=5.6802 c=7.3964 β=98.905° 2 138.13 4.857 metallic
ScN5 monoclinic P21/m a=3.3225 b=6.440 c=3.7067 β=104.34 2 76.84 4.971 indirect semiconductor
Sc4N3 cubic Fm3m a= 4.2492 4 233.9 6.301 125
TiN2 Ti4+N4−2 pernitride tetragonal I4/mcm a=4.334 c=5.294 4 99.44 0 385(7) 0
VN2 V4+N4−2 pernitride tetragonal I4/mcm a=4.3015 c=4.9827 4 92.195 5.6883 73.3 347 0
MnN4 chains triclinic P1 a=3.58 b=3.70 c=5.01

α=94.2° β=111.2° γ=71.6°

 58.7 108 GPa
FeN2 orthorhombic Pnnm a=4.431 b=3.722 c=2.421 2 39.93 58.5
FeN4 Fe2+[poly-N2−4] 1D chains, N4 torsion angle = 36°
polytetrazene geometry		 triclinic a=2.5089 b=3.524 c=3.5409

105.08 110.26 92.03

 1 28.09 106 : Figure S3 
CoN2 orthorhombic Pnnm 31 GPa 216
CoN3 orthorhombic Pnma a=2.555 b=3.463 c=10.655 90-120 GPa
CoN5 monoclinic C2/c a=4.951 b=6.910 c=8.062 β=95.77 90-120 GPa
NiN2 pernitride orthorhombic Pnnm 36 GPa
NiN2 diazenide tetragonal P4/mbm
ZnN4 1D chain orthorhombic Ibam 14-130 GPa
YN6 N189+ rings 100 GPa
Y(N5)3·N2 Y3+[N−5]3·N2 pentazolate

nitrogen-inclusion

 monoclinic P21/c a=9.617 b=6.932 c=6.609

β=95.13°

 4 438.8 5.092 125 GPa
Y2N11 N-double helix 100 GPa
Y5N14 tetragonal P4/mbm a=8.451 c=4.7316 2 337.93 6.296 50
Nb2N3 orthorhombic Pnma a=7.897 b=2.857 c=7.660 4 8.755 56 GPa
NbN2 tetragonal I4mm a=2.8365 c=11.444 4 8.723 80 GPa
NbN4 monoclinic P21/n a=4.4827 b=5.4543 c=5.439

β=101.47

 4 7.59 105:100-120 GPa
NbN5 orthorhombic Fdd2 a=11.833 b=13.870 c=3.6001 16 7.323 100-120 GPa
RuN2 Ru4+N4−2 pernitride orthorhombic Pnnm 0
RhN2 Rh4+N4−2 pernitride orthorhombic Pnnm 235 0
RhN2 pernitride monoclinic P21/c
PdN2 Pd4+N4−2 pernitride Pa3 13
AgN7 N5 ring + N2 P1 15 GPa 5 black
AgN5 P21/c 15 GPa
AgN4 P1 26.3 GPa 12
SbN4 Sb25+N810- N8 chains monoclinic P21/n 100-120 GPa
CsN5 Cs+N−5 pentazolate Pbca
CsN5 triclinic P1
LaN8 N18 rings trigonal R3
LaN8 N8 cage tetragonal P4/n high energy density
Ce2N6 N4 zigzags C2/m a=5.717 b=4.661 c=6.548

β=93.270

 174.20 ambient
CeN4 chains I41/a a=6.711 c=2.879 0
CeN6 hexazine R3m a=5.890 c=4.108
CeN14 sheet hexagonal P6mm a=5.748 c=2.447
CeN17 sheet hexagonal P6mm a=6.111 c=2.842
Hf2N11 N double helix hexagonal P6422
TaN4 N4 chains monoclinic P21/n 100
TaN5 branched infinite chains orthorhombic Fdd2 100
WN8·N2 1 D chain, N2 molecules orthorhombic Immm
WN6 N66- hexaazacyclohexane derivative rhombohedral R3m
ReN2 [Re5+]2[N4−2][N3−]2 pernitride

nitride

 monoclinic P21/c a=3.625 b=6.407 c=4.948

β=111.48°

 0 330 0 very hard
ReN2 Re4+N24- pernitride tetragonal P4/mbm 175
ReN8·N2 1 D chain, N2 molecules orthorhombic Immm 105-130 GPa
OsN2 Os4+N4−2 pernitride orthorhombic Pnnm 358 0
Os5N28·3N2 1D chain, N2 molecules orthorhombic Pnnm
IrN2 Ir4+N4−2 pernitride monoclinic P21/c 428 0
PtN2 Pt4+N4−2 pernitride Pa3 372 0
PbN2 Pb2+N2−2 diazenide

(provisional, N2x- dimers)

 tetragonal I4/mcm 65 15

Notes

  1. ↑ Based on empirical formula
  2. 1 2 Zero denotes ambient pressure (1 bar = 0.0001 GPa)
  3. 1 2 Extrapolated to zero pressure using the third-order Birch–Murnaghan equation of state
  4. 1 2 3 4 5 Unknown polymorph
  5. 1 2 predicted structure
  6. ↑ Modeled using the third-order Birch–Murnaghan equation of state
  7. ↑ Extrapolated to zero pressure using the second-order Birch–Murnaghan equation of state

References

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