Supporting Information

Prediction of Novel Tin Nitrides SnxNy Phases

Under Pressure

Busheng Wang†, Rabii Larhlimi†, Hubert Valencia‡, Frédéric Guégan†

and Gilles Frapper*,†

†Applied Quantum Chemistry Group, E4 Team, IC2MP UMR 7285, Université de Poitiers - CNRS, 4 rue
Michel Brunet TSA 51106, 86073 Poitiers Cedex 9, France
‡Institute of Materials and Systems for Sustainability Furo-cho, Chikusa, Nagoya 464-8603, Japan

*Email: gilles.frapper@univ-poitiers.fr

S1
 Contents

S1. Methodology details ................................................................................................... s3

S1.1 Evolutionary algorithm (USPEX) ....................................................................... s3
S1.2 DFT calculations (VASP)..................................................................................... s3
S1.3 Phonon calculations .......................................................................................... s4
S1.4 Detonation properties: computational details ................................................ s5
S2. Thermodynamic stability ............................................................................................ s6
S3. Structural parameters ................................................................................................. s8
S4. Energies...................................................................................................................... s13
S5. Phonon dispersion curves of the SnxNy compounds ................................................ s16
S6. Electronic properties ................................................................................................. s19
S7. Comparison of predicted phases with literatures .................................................... s27
S8. Metastable compositions.......................................................................................... s37
S9. Dynamically unstable Sn(N5)2 pentazolate ............................................................... s48
S10. AIMD calculations.................................................................................................... s49
S11. References ...............................................................................................................S54

S2
S1. Methodology details

S1.1 Evolutionary algorithm (USPEX)

USPEX (Universal Structure Predictor: Evolutionary Xtallography)1-3 is a global

evolutionary algorithm (EA) for the prediction of crystal structures developed by the A.R.
Oganov laboratory since 2004 (see http://uspex-team.org/en/uspex/overview ). In this
work, this EA code is interfaced with VASP (Vienna Ab initio Simulation Package)4 for
density functional theory (DFT) structure relaxations (shape, volume, and atomic positions
are optimized by VASP). The EA development allows prediction of the stable and
metastable structures knowing only their chemical composition. Simultaneous search for
compositions and structures are also possible. This variable-composition technique is used
to investigate stable compounds in the Sn-N binary phase diagram at 0 GPa, 20 GPa, 50
GPa, 100 GPa, and 200 GPa, at zero Kelvin. For the resulting SnxNy (where x and y are
positive integers) minimum a fixed composition is then employed to locate the most stable
structure. The latter EA search is performed at least twice to ensure convergence to a global
minimum.
A large number (100) of randomly created structures is chosen in the first generation
of the EA. In the next generations, 80 structures are generated. What is the generation
process? For each parent structure from a previous generation, the fitness is computed as
the free enthalpy derived from an ab initio total energy calculations (here VASP). All
structures are then tested against three constraints: interatomic distances, cell angles and
cell lengths. 80% of the best (i.e. lowest enthalpy) optimized structures are selected to
participate in producing the next generation. A new candidate structure is produced from
parent structures using one of four operators defined in Refs 1-3: (i) heredity, (ii)
permutation, (iii) lattice mutations, and (iv) atomic mutation, which account for 50, 10, 10,
and 10% of the structures in the new generation. The remaining 20% are randomly
generated (similarly to those of the first generation). A fixed composition EA search is
considered achieved when the same global structure minimum is found during 10
consecutive generations. Typically, such search requires between 15 and 30 generations.
For searching the novel pentazolate-based compounds, e.g. Sn(N5)2 and Sn(N5)4,
molecular crystal searches3 were carried out. The cyclo-N5 and Sn are considered as a

S3
molecular unit and an atom, in Mol_1 and Mol_2, respectively. The cyclo-N5 pentazolate
was treated as an integral unit in the molecular crystal (building blocks, instead of isolated
N and Sn atoms). Up to 44 atoms per primitive cell was considered. Meanwhile, fixed-
composition searches for SnN10 and SnN20 were also carried out, to confirm the nature of
the lowest energy structures.

S1.2 DFT calculations (VASP)

First-principles calculations are performed using the projected-augmented-wave

(PAW)5 method as implemented in VASP (version 5.4.4). Exchange-correlation energy is
treated using Perdew-Burke-Ernzerhof (PBE)6 within the generalized gradient
approximation (GGA)7. A kinetic cutoff energy of 600 eV is used for the wavefunction
expansion with a Monkhorst-Pack k mesh grid with a spacing of 2π × 0.03 Å−1. This ensure
−5
that enthalpy converges to a criterion lower than 1 × 10 eV per cell. In USPEX
calculation, 5 successive steps of increasing convergence accuracy are usually required (ie.
5 INCAR files). An illustration of this local optimization procedure is given in the PhD
manuscript of B. Huang, “Computational materials discovery: prediction of carbon dioxide
and nitrogen-based compounds under pressure using density functional theory and
evolutionary algorithm”, supervised by Pr. G. Frapper, IC2MP, Poitiers University
(France), Dec. 2017 http://theses.univ-poitiers.fr/notice/view/59262 ). The parameters and
criterion associated with VASP calculations then correspond to the last (5th) step of the
highest accuracy.

Ab initio molecular dynamics (AIMD) simulations based on DFT are also carried out
using VASP code to examine the thermal stability of (meta)stable candidate phases. AIMD
calculations were performed up to 900 K. The timestep was 1 fs, and the total simulation
time was as long as 10 ps. In such AIMD simulations, the Brillouin zone integration is
restricted to the Γ point of the supercell, due to a high calculation cost.

S1.3 Phonon calculations

In this work, first principles phonon calculations using the finite displacements method
at a quasi-harmonic level are done using the open source package PHONOPY8
S4
(https://atztogo.github.io/phonopy/). Supercell structures with or without displacements
are created from a reference Sn-N unit cell considering all possible crystal symmetry
operations. In general, a 2x2x2 supercell is sufficient, but larger ones can be required to
avoid unphysical imaginary frequencies. Force constants are calculated using the optimized
structure (VASP). In addition, the effect of zero-point energy (ZPE) on the stability of Sn-
N is studied. We find that the inclusion of ZPE only moderately shift the stability figures,
but doesn’t change the phase stability order. Thus, the energies presented in this manuscript
are not ZPE corrected.

S1.4 Detonation properties: computational details

Velocity of detonation (VOD) and detonation pressure are two important performance
parameters for energetic materials. To estimate the values of detonation velocity (D)
and detonation pressure (P) for SnN2, SnN3, SnN4, and SnN5 at 1 atm, the empirical
Kamlet-Jacobs equations9 are used. They consist in the following equations:

𝐷 = 1.01 (√𝑁(𝑀𝑄)1⁄2 ) (1 + 1.30𝜌)

𝑃 = 15.58𝜌2 𝑁√𝑀𝑄

where D is the detonation velocity (mm/μs = 10-6 km/10-6 s); P is the detonation pressure; N
is the quantity of matter of the gaseous detonation products (here N2), per gram of explosive
(mol/g); M is the average molecular weights of the gaseous products (g/mol); Q is the
chemical energy of detonation (J/g) defined as the difference between the enthalpies of
formation of the products (Sn3N4(s) and N2(g)) and the explosive reactant, and ρ is the
density of the explosive (g/cm3). High energy-density materials typically detonate at a rate
between 5.5-9.5 km/s (velocity of detonation, VOD).

S5
S2. Thermodynamic stability
The widespread exchange-correlation approximations (local-density approximation
(LDA) and GGA) are typically very efficient and accurate for periodic solids.
Unfortunately, they often fail to produce accurate formation energies for molecular species
(e.g. O2, H2, N2, F2, and Cl2 molecules), leading to a discrepancy with the experimental
values of up to 10 to 20%.10 Indeed, a correction for the N2 molecule have to be taken into
account for the enthalpies of formation at 0 GPa. The enthalpy of formation Δr 𝐻𝑓 of SnxNy
compounds is defined as

𝑦
Δr 𝐻𝑓 (Sn𝑥 𝑁𝑦 ) = 𝐻(Sn𝑥 𝑁𝑦 )– 𝑥𝐻(Sn)– (𝐻(𝑁2 ) + 𝐻𝑐 (𝑁2 ))
2
where Hc(N2) is the correction enthalpy, 0.447 eV/atom11, which is obtained by fitting a set
of data [𝛥𝑟 𝐻𝑓𝐸𝑥𝑝𝑡. vs. 𝛥𝑟 𝐻𝑓𝐷𝐹𝑇 for AlN, Be3N2, Ca3N2, Ge3N4, Li3N, Mg3N2, and Si3N4].
With correction to their enthalpy of formation, the Fd-3m Sn3N4 (Δr 𝐻𝑓 = -0.067 eV/atom)
and Im-3 SnN8 (Δr 𝐻𝑓 = -0.068 eV/atom) phases are now located on the convex hull at 0
GPa, as shown in Figure S1. The table S1 presents the enthalpy and formation enthalpy of
Fd-3m Sn3N4 with different pseudopotentials and correction energy schemes.
Note that our conclusions do not change whether or not a correction is applied.

Table S1. The enthalpy and formation enthalpy of Fd-3m Sn3N4 phases by using different
pseudopotentials and correction energies. MP refers to Materials Project; Grindy refers to
author Grindy of Ref. 10; Sn_d refers to 4d states of Sn are treated as valence states.

Formation enthalpy (eV/atom)

Pseudopotentials Enthalpy
VASP PAW (eV/atom) MP17 Grindy10
No correction
correction correction
Fd-3m N & Sn_d -6.262 0.140 0.000 -0.038
Sn3N4 N & Sn (this work) -6.214 0.188 -0.026 -0.067

S6
 Figure S1. Convex-hull diagrams for the Sn-N system at selected pressures. Enthalpy
correction for N2 is taken at atmospheric pressure. Solid symbols denote stable structures,
empty ones represent metastable structures. The space group is indicated for each novel
stable structure. At 1 atm (top diagram), half-filled stars denote quenchable phases, and
an empty pentagon indicates the lowest pentazolate P-1 SnN20 at this pressure. Their
space group and formation enthalpies are indicated.

S7
S3. Structural parameters
S3.1. Crystal structures
Table S2. Structural parameters of the predicted SnxNy compounds at selected pressures
(distances in Å, angles in °, pressure in GPa).
Space
Phase P Z Lattice Parameters Atomic coordinates (fractional)
Group

Stable

a=8.856, b=8.856, c=8.856 Sn (0.000, 0.000, 0.000), (0.375, 0.375,

Sn3N4 20 8 Fd-3m
α=90.0, β=90.0, γ=90.0 0.375); N (-0.242, -0.242, -0.242)
Sn (0.220, 0.348, -0.468), (0.000, 0.000,
a=3.017, b=9.750, c=6.660
Sn3N4 50 2 P21/c 0.500); N (-0.313, -0.313, 0.189), (0.061,
α=90.0, β=48.5, γ=90.0
0.052, -0.215)
a=9.279, b=9.279, c=5.282 Sn (-0.326, 0.148, 0.263); N (0.000, 0.000,
Sn3N4 80 6 R3c
α=90.0, β=90.0, γ=120.0 0.200), (-0.220, -0.325, 0.088)
a=6.291, b=6.291, c=6.291 Sn (0.375, 0.000, 0.250); N (0.063, 0.063,
Sn3N4 100 4 I-43d
α=90.0, β=90.0, γ=90.0 0.063)

a=4.999, b=4.999, c=4.999 Sn (0.500, 0.500, 0.500); N (-0.084, -

SnN2 20 4 Pa-3
α=90.0, β=90.0, γ=90.0 0.084, -0.084)
a=4.094, b=4.094, c=4.987 Sn (-0.353, 0.000, 0.333); N (0.365, 0.205,
SnN2 100 3 P3121
α=90.0, β=90.0, γ=120.0 -0.425)
Sn (0.094, 0.244, -0.212); N (-0.363, -
a=3.766, b=4.669, c=4.274 0.347, -0.302), (-0.283, 0.191, 0.030), (-
SnN4 100 2 P-1
α=85.4, β=110.4, γ=84.3 0.284, 0.353, 0.276), (-0.343, -0.083, -
0.442)
Sn (-0.252, 0.097, -0.210); N (-0.081, -
a=4.333, b=3.753, c=6.261 0.327, 0.472), (-0.316, -0.356, 0.369),
SnN5 50 2 P-1 (II)
α=96.9, β=80.2, γ=70.8 (0.293, -0.289, -0.304), (0.046, 0.332, -
0.026), (0.494, -0.289, -0.165)
a=4.177, b=4.307, c=8.742 Sn (0.000, 0.000, 0.250); N (-0.393, 0.110,
SnN6 200 4 Ibam
α=90.0, β=90.0, γ=90.0 0.125), (0.372, -0.269, 0.000)
Sn (0.000, 0.000, 0.000); N (-0.255, 0.440,
a=5.047, b=4.246, c=3.638
SnN8 50 1 P-1 (I) 0.479), (0.264, -0.443, 0.161), (-0.282, -
α= 114.3, β=100.0, γ=71.2
0.236, 0.128), (0.274, 0.241, -0.490)
Sn (0.000, 0.000, 0.000); N 0.243, 0.002,
a=6.713, b=6.713, c=7.135 0.357), (0.126, 0.123, 0.262), (0.157,
SnN20 50 2 I-4
α=90.0, β=90.0, γ=90.0 0.306, 0.306), (0.291, 0.294, 0.432),
(0.350, 0.111, 0.465)

S8
Continued

Metastable

a=4.407, b=3.235, c=7.103 Sn (-0.248, 0.250, -0.102), (-0.286, 0.250,

Sn2N 20 2 P21/m
α=90.0, β=97.4, γ=90.0 0.386); N (-0.005, 0.250, -0.338)
Sn (0.000, 0.000, 0.000), (0.000, 0.000,
a=3.022, b=3.022, c=31.384
Sn2N 50 6 R-3m 0.500), (0.000, 0.000, 0.257); N (0.000,
α=90.0, β=90.0, γ=120.0
0.000, -0.127)
a=5.502, b=3.133, c=9.472 Sn (0.000, 0.000, 0.000), (0.300, 0.000,
Sn3N2 20 1 C2/m
α=90.0, β=107.7, γ=90.0 0.350); N (-0.233, 0.000, -0.124)
a= 2.997, b= 2.997, c= 8.229 Sn (0.333, 0.667, -0.151), (0.000, 0.000,
Sn3N2 50 2 P-3m1
α=90.0, β=90.0, γ=120.0 0.500); N (0.333, 0.667, 0.351)
Sn (0.000, 0.000, -0.371), (0.000, 0.000,
a= 3.606, b= 3.606, c= 35.242
SnN 0 4 R-3m 0.127); N (0.000, 0.000, -0.194), (0.000,
α=90.0, β=90.0, γ=120.0
0.000, 0.067),
a=3.149, b=3.149, c=10.424 Sn (0.000, 0.000, -0.369); N (0.000, 0.000,
SnN 20 4 I4/mmm
α=90.0, β=90.0, γ=90.0 -0.162)
Sn (0.000, -0.170, 0.000), (0.500, 0.000,
a=3.000, b=14.715, c=3.037
SnN 100 6 Cmmm 0.500); N (0.000, 0.363, 0.500), (0.000,
α=90.0, β=90.0, γ=90.0
0.000, 0.000)
a=5.091, b=3.156, c=5.021 Sn (0.000, 0.500, 0.021); N (-0.282, 0.000,
SnN3 20 2 Imm2
α=90.0, β=90.0, γ=90.0 -0.077), (0.000, 0.500, -0.431)
a=4.137, b=4.285, c= 6.824 Sn (-0.294, 0.000, -0.177); N (-0.112,
SnN3 100 4 C2/m
α=90.0, β= 98.2, γ=90.0 0.241, -0.443), (-0.219, 0.000, 0.129)
a=5.033, b=5.033, c=7.465 Sn (0.000, 0.000, 0.250); N (-0.321, 0.179,
SnN4 20 4 I4/mcm
α=90.0, β=90.0, γ=90.0 0.082)
a=7.843, b=7.843, c=7.997 Sn (0.000, 0.000, 0.000); N (0.195, 0.000,
SnN6 20 6 R-3c
α=90.0, β=90.0, γ=120.0 0.250), (0.341, 0.000, 0.250)
Sn (0.500, 0.000, 0.500); N (0.167, -0.211,
a= 3.149, b= 3.902, c= 4.444
SnN8 200 1 P-1 (II) -0.197), (-0.369, 0.222, -0.110), (0.163, -
α= 72.3, β= 102.9, γ=76.4
0.407, 0.326), (0.206, 0.429, -0.144)
Sn (0.500, 0.000, 0.000), (0.000, 0.500,
0.500); N (-0.421, 0.162, 0.136), (-0.342,
0.120, 0.278), (-0.319, 0.256, 0.320), (-
0.384, 0.380, 0.204), (-0.447, 0.322,
0.090), (-0.201, 0.264, -0.205), (-0.099,
0.122, -0.294), (-0.028, 0.174, -0.399), (-
0.087, 0.347, -0.375), (-0.194, 0.404, -
a=9.347, b=8.513, c=8.254
SnN20 0 2 P-1 0.254), (0.100, 0.296, 0.300), (0.015,
α=91.7, β=91.2, γ=63.3
0.277, 0.173), (0.118, 0.173, 0.069),
(0.265, 0.131, 0.132), (0.255, 0.206,
0.275), (0.242, 0.292, -0.221), (0.233,
0.361, -0.363), (0.380, 0.312, -0.424),
(0.482, 0.210, -0.320), (0.396, 0.198, -
0.195)

S9
 Sn (0.000, 0.000, 0.000),(0.500, 0.500,
0.500); N(0.083, 0.166, 0.149), (0.176,
0.122, 0.290), (0.193, 0.269, 0.336),
(0.112, 0.402, 0.223), (0.044, 0.338,
0.108), (0.294, 0.239, -0.180), (0.393,
0.099, -0.280), (0.466, 0.160, -0.388),
a=8.772, b=8.009, c=7.873 (0.413, 0.338, -0.356), (0.306, 0.388, -
SnN20a 0 2 P-1
α=91.0, β=90.6, γ=66.3 0.226), (-0.414, 0.297, 0.293), (0.497,
0.286, 0.155), (-0.396, 0.180, 0.048), (-
0.245, 0.129, 0.121), (-0.256, 0.201,
0.272), (-0.248, 0.296, -0.224), (-0.257,
0.362, -0.376), (-0.106, 0.305, -0.447), (-
0.002, 0.202, -0.339), (-0.090, 0.199, -
0.201)
Sn(-0.049, 0.125, -0.007); N(-0.470, 0.359,
0.287), (-0.356, 0.101, 0.194), (0.482, -
0.004, 0.066), (0.270, 0.195, 0.092),
(0.294, 0.420, 0.223), (0.201, -0.138, -
0.343), (0.422, -0.217, -0.429), (0.397, -
0.207, 0.299), (0.159, -0.128, 0.221),
a=5.892, b=5.852, c=4.646
SnN20 100 1 P1 II (0.035, -0.075, 0.446), (-0.470, 0.118, -
α=112.6, β=102.1, γ=65.2
0.356), (0.299, 0.253, -0.382), (0.267, -
0.494, -0.253), (0.477, -0.473, -0.154), (-
0.368, 0.287, -0.208), (-0.128, -0.356, -
0.095), (-0.093, 0.410, -0.285), (-0.114,
0.420, 0.431), (-0.152, -0.345, 0.445), (-
0.156, -0.211, -0.260)
a
SnN20 crystallographic structures are optimized by SCAN-rVV10 Functional.

S10
Continued
Quenchable
a=4.910, b=3.398, c=7.758 Sn (0.223, 0.250, 0.122), (0.262, 0.250, -
Sn2N 0 2 P21/m
α=90.0, β=96.7, γ=90.0 0.396); N (0.000, 0.250, 0.346)
a=3.271, b=3.271, c=10.891 Sn (0.000, 0.000, 0.366); N (0.000, 0.000,
SnN 0 4 I4/mmm
α=90.0, β=90.0, γ=90.0 0.165)
a=9.141, b=9.141, c=9.141 Sn (0.000, 0.000, 0.000), (0.375, 0.375,
Sn3N4 0 8 Fd-3m
α=90.0, β=90.0, γ=90.0 0.375); N (0.241, 0.241, 0.241)
a=5.145, b=5.145, c=5.145 Sn (0.500, 0.500, 0.500); N (-0.083, -
SnN2b 0 4 Pa-3 α=90.0, β=90.0, γ=90.0 0.083, -0.083)

a=3.387, b=5.212, c=5.352 Sn (0.000, 0.500, -0.474); N (0.000, -

SnN3 0 2 Imm2
α=90.0, β=90.0, γ=90.0 0.285, -0.074), (0.000, 0.500, 0.058)
Sn (0.153, 0.237, -0.182); N (-0.435, -
a=4.394, b=5.343, c=4.775 0.307, -0.307), (-0.243, 0.191, 0.049), (-
SnN4 0 2 P-1
α=83.8, β=107.6, γ=89.2 0.254, 0.324, 0.274), (-0.385, -0.086, -
0.455)
b
Experimental and theoretical SnN2 crystallographic structures are discussed in S7.2.

S11
Table S3. Structural parameters of tin and nitrogen phases at selected pressures (distances
in Å, angles in °, pressure in GPa).

Phase P Space Group Lattice Parameters Atomic coordinates (fractional)

Sn 0 Fd-3m a=6.655, b=6.655, c=6.655 Sn (0.125, 0.125, 0.125)

α=90.0, β=90.0, γ=90.0
Sn 5 I41amd a=5.804, b=5.804, c=3.101 Sn (0.000, 0.750, 0.125)
α=90.0, β=90.0, γ=90.0
Sn 20 I4/mmm a=3.417, b=3.417, c=3.745 Sn (0.000, 0.000, 0.000)
α=90.0, β=90.0, γ=90.0
a=3.335, b=3.335, c=3.335
Sn 50 Im-3m Sn (0.000, 0.000, 0.000)
α=90.0, β=90.0, γ=90.0

N 0 Pa-3a a=5.856, b=5.856, c=5.856 N (0.055, 0.055, 0.055)

α=90.0, β=90.0, γ=90.0
N 20 P41212b a=3.099, b=3.099, c=8.760 N (0.317, 0.447, 0.272)
α=90.0, β=90.0, γ=90.0
N 20 P21/c a=3.106, b=3.092, c=5.865 N (-0.064, 0.118, 0.456)
α=90.0, β=48.2, γ=90.0
N 20 Pbcn a=3.094, b=4.936, c=5.496 N (-0.382, -0.146, 0.326)
α=90.0, β=90.0, γ=90.0
N 50 P41212 a=2.836, b=2.836, c=8.048 N (0.296, 0.452, 0.274)
α=90.0, β=90.0, γ=90.0
N 50 P21/c a=2.854, b=2.819, c=5.487 N (-0.070, 0.127, 0.453)
α=90.0, β=47.2, γ=90.0
N 50 Pbcn a=2.822, b=4.490, c=5.118 N (-0.372, -0.141, 0.332)
α=90.0, β=90.0, γ=90.0
N 80 I213 a=3.554, b=3.554, c=3.554 N (0.174, 0.174, 0.174)
α=90.0, β=90.0, γ=90.0
N 100 I213c a=3.513, b=3.513, c=3.513 N (0.176, 0.176, 0.176)
α=90.0, β=90.0, γ=90.0
N (0.212, 0.278, -0.339), (-0.281,
N 200 Pba2 a=4.238, b=4.228, c=4.051
0.279, 0.344), (0.482, 0.164, 0.183),
α=90.0, β=90.0, γ=90.0
(-0.337, 0.485, -0.180)
a,b c
Molecular crystal (N-N=1.11 Å in triple bonded N2). 3D covalent net (N-N= 1.34 Å, 3-coordinated N,
10-rings).

S12
S3.2 Volume change of Sn3N4, Sn and N2 upon compression.

The evolution of volumes for Sn3N4 compounds under pressure is presented on Figure
S2 and Table S4, as well as for constitutive 3Sn + 2N2 elements. Volume per formula unit
decreases faster between 0 and 200 GPa for the separate elements than that for Sn3N4
compounds. This suggests that Sn3N4 compounds are stabilized at high pressure because
of the PV contribution in enthalpy (H = U+PV).

Figure S2. Plot of theoretical volume (at PBE level of theory) upon compression for Fd-
3m, P21/c, R3c, and I-43d phases of Sn3N4, the sum of 3 times the volume of Sn and 2
times the volume of N2 equivalent phases at a given pressure is also indicated with
hexagonal symbols for comparison. The line for the latter trace is just a guide for the eye.

Table S4. Evolution of volumes for Sn3N4 compounds and constitutive Sn+N elements
under pressure.
Phase Pressure range
10~30 (GPa) 30~70 (GPa) 70~90 (GPa) 90~200 (GPa)

volume (Å3/GPa) Sn3N4 -0.34 -0.20 -0.13 -0.08

3Sn+2N2 -1.35 -0.60 -0.18 -0.11

S13
S4. Energies
Table S5. Calculated enthalpies of the predicted SnxNy compounds at different pressure.
Space Pressure Enthalpy ZPE Formation Enthalpy
Structure
Group (GPa) (eV/atom) (eV/atom) (eV/atom)
Stable
Sn3N4 Fd-3m 20 -4.595 0.075 -0.481
Sn3N4 P21/c 50 -2.480 0.079 -0.934
Sn3N4 R3c 80 -0.613 0.085 -1.164
Sn3N4 I-43d 100 0.524 0.089 -1.288
SnN2 Pa-3 20 -5.057 0.088 -0.384
SnN2 P3121 100 -0.394 0.106 -1.122
SnN4 P-1 100 -1.570 0.130 -0.782
SnN5 P-1 (II) 50 -4.081 0.119 -0.483
SnN6 Ibam 200 1.756 0.159 -0.801
SnN8 P-1 (I) 50 -4.370 0.135 -0.331
SnN20 I-4 50 -4.710 0.143 -0.165
Metastable
Sn2N P21/m 20 -2.863 0.050 -0.142
Sn2N R-3m 50 -0.120 0.046 -0.445
Sn3N2 C2/m 20 -3.349 0.054 -0.227
Sn3N2 P-3m1 50 -0.752 0.057 -0.559
SnN R-3m 0 -5.851 0.055 0.229
SnN I4/mmm 20 -4.005 0.052 -0.308
SnN Cmmm 100 1.661 0.071 -0.971
SnN3 Imm2 20 -5.298 0.100 -0.130
SnN3 C2/m 100 -1.022 0.111 -0.805
SnN4 I4/mcm 20 -5.539 0.082 -0.083
SnN6 R-3c 20 -5.809 0.106 -0.016
SnN8 P-1 (II) 200 1.453 0.161 -0.552
SnN20 P-1 0 -7.524 0.121 0.592
Quenchable
Sn2N P21/m 0 -5.171 0.038 0.160
SnN I4/mmm 0 -5.708 0.040 0.372
Sn3N4 Fd-3m 0 -6.214 0.066 0.188
SnN2 Pa-3 0 -6.414 0.080 0.417
SnN3 Imm2 0 -6.644 0.081 0.562
SnN4 P-1 0 -6.565 0.088 0.866
Structures are ordered by compositions (from Sn-rich to N-rich), pressure (low to high), and separated in

S14
three groups: thermodynamically stable, metastable, and quenchable (metastable phases that retain their
structure after pressure relaxation).

Table S6. Calculated enthalpies of tin and nitrogen phases at different pressure.

P Enthalpy ZPE
Phase Space Group
(GPa) (eV/atom) (eV/atom)
Sn 0 Fd-3m -3.831 0.013
Sn 5 I41amd -2.948 0.011
Sn 20 I4/mmm -0.764 0.009
Sn 50 Im-3m 2.983 0.013
N 0 Pa-3 -8.320 0.080
N 20 P41212 0.108
N 20 P21/c -6.632 0.108
N 20 Pbcn 0.110
N 50 P41212 0.120
N 50 P21/c -4.921 0.120
N 50 Pbcn 0.124
N 80 I213 -3.757 0.170
N 100 I213 -3.067 0.174
N 200 Pba2 0.075 0.189

S15
S5. Phonon dispersion curves of the SnxNy compounds
Figure S3. Phonon dispersion curves of the SnxNy compounds at selected pressures. No
imaginary phonon modes are found in the whole Brillouin zone, which confirms their
dynamical stability.

a. Ground stable phases

S16
b. Metastable phases

S17
c. Quenchable phases

S18
S6. Electronic properties
Figure S4. Density of states (DOS) at PAW-GGA-PBE level
a. Ground stable phases

S19
b. Metastable phases

S20
c. Quenchable phases

S21
Figure S5. DOS at HSE06 level

S22
Figure S6. (a) eHT band structure for an infinite armchair –[N42-]x– chain in P-1 SnN8.
Energy gap is indicated. (b) Crystal structure of the infinite N4 chain.

S23
Figure S7. Electron Localization Function

S24
Figure S8. DDEC6 bond order

The bond orders were computed by the Chargemol program using Manz’ bond order
equation with DDEC6 partitioning. See the references in the manuscript.

S25
S26
S27
S7. Comparison of predicted phases with the literature
S7.1. Sn3N4

At ambient and high pressures, several Sn3N4 polymorphs have been proposed as
ground-state structures or metastable structures in the recent years.13 We present our results
together with those of Kearney et al13 in Table S8. Kearney et al proposed a Fd-3m phase
for Sn3N4 for low pressure, in agreement with our calculations. A notable exception, though,
is the ground state phase predicted between 69 and 88 GPa (our results) or 87 and 97 GPa
in Ref. 13. Kearney et al predict a R-3c phase (Figure S9 b) while we found a R3c phase
(Figure S9a) for the corresponding stability areas. In their work, the authors didn’t report
any phono dispersion results. In order to compare the relative stability of R3c and R-3c, we
performed such analysis, see the phonon dispersions for R3c and R-3c in Figure S10. We
found, at our level of theory, that this structure would be dynamically unstable and should
distort to our energetically favorable structure (R3c). However, at PBE and SCAN levels
of theory, R-3c lies above our USPEX phase R3c with only +2 meV/atom and +1 meV/atom,
respectively. Note this such a small energy difference is not conclusive. Moreover, the
effect of temperature on crystal stability may lead to a stabilization of R3c over R-3c.
The structural difference between R-3c and R3c is illustrated by the local NSn6
polyhedra. In stable R3c, slightly distorted octahedral NSn6 units are observed while
regular Oh NSn6 octahedrons are present in dynamically unstable R-3c structure.

Figure S9. The crystal structures of (a) R3c and (b) R-3c Sn3N4 phases. The structural
difference between R-3c and R3c is illustrated by the local NSn6 polyhedra.

S28
 Figure S10. (a)(c) Phonon dispersion of R3c Sn3N4 by PBE (red, top) and SCAN (blue,
bottom) functionals. (b)(d) Phonon dispersion curve of R-3c phase by PBE and SCAN
functionals.

Table S7. Computing parameters of Sn3N4 phases

This work Kearney et al results13

Functional PBE SCAN PBE0 hybrid
Exchange-correlation GGA Meta-GGA GGA
Pseudo-potentials PAW PAW PAW
Cut-off energy 600 eV 600 eV 950 eV
-1 -1
k-points 2π × 0.03 Å 2π × 0.03 Å 4×4×4

Procedure to calculate an
ISIF=3 ISIF=3 N/A
H(P) curve
DFT code VASP VASP VASP

S29
Table S8. Experimental crystal structures of Sn3N4 phases (distances in Å, angles in °,
pressure in GPa).

Space
Phase P Z Lattice Parameters Atomic coordinates (fractional)
Group
a=9.037, b=9.037, c=9.037 Sn (0.000, 0.000, 0.000), (0.375, 0.375,
Sn3N413 0 8 Fd-3m
α=90.0, β=90.0, γ=90.0 0.375); N (0.241, 0.241, 0.241)
a=9.141, b=9.141, c=9.141 Sn (0.000, 0.000, 0.000), (0.375, 0.375,
Sn3N4 0 8 Fd-3m
α=90.0, β=90.0, γ=90.0 0.375); N (0.241, 0.241, 0.241)
Sn (0.221, 0.348, -0.469), (0.000, 0.000,
a=2.976, b=9.711, c=6.599
Sn3N413 56 2 P21/c 0.500); N (-0.315, -0.313, 0.189), (0.061,
α=90.0, β=49.1, γ=90.0
0.052, -0.215)
Sn (0.220, 0.348, -0.468), (0.000, 0.000,
a=3.002, b=9.6970, c=6.635
Sn3N4 56 2 P21/c 0.500); N (-0.311, -0.312, 0.188), (0.061,
α=90.0, β=48.5, γ=90.0
0.052, -0.215)

S30
Figure S11. Band structures and DOS of Sn3N4 phases at PBE level. (a) Fd-3m at 0 GPa.
(b) P21/c at 50 GPa. (c) R3c at 80 GPa. (d) I-43d at 100 GPa. The colored bands indicate
the atomic contributions to the band structure, from red (high Sn contributions) to green
(high nitrogen contribution). Right panel shows the total DOS of the bands shaded in
grey. The partial DOS for Sn and N associated with different orbitals are shown by
colored lines.

S31
 Figure S12. Evolution of the - energy gap (Eg in eV) for each Sn3N4 phases at PBE
and HSE06 theory.

Table S9. The evolution of the energy gap and Sn-N distances in Sn3N4 phases at PBE and
HSE06//PBE levels (distances in Å, pressure in GPa, optical band gap Eg in eV).

Sn coord. Egb
N coord.
Phases P [Sn-Sn
[Sn-N distance]
distance]a PBE//PBE HSE06//PBE
4 [3.96]
Fd-3m 0 4 [2.12-2.20] 0.23 1.31
6 [3.23]
4 [2.06-2.18]
P21/c 50 6 [3.02] 1.77 3.03
5 [2.06-2.18]
5 [2.02-2.36]
R3c 80 7 [2.92] 2.12 3.18
6 [2.13-2.26]
I-43d 100 8 [2.92] 6 [2.05-2.32] 3.36 4.72
a
Shortest Sn-Sn interatomic separation and Sn-N bond lengths (weighted values). b Level of theory:
PBE//PBE means PBE energy on PBE optimized structure; HSE06//PBE means HSE06 energy on PBE
optimized structure.

S32
 Figure S13. The calculated enthalpy differences as a function of pressure for various
Sn3N4 structures with (a) PBE and (b) SCAN functional. The insets show the enthalpies
of R3c, R-3c, I-43d and P21/c. Obviously, in both of PBE and SCAN functional, our
structure R3c is lower than R-3c, that the one proposed by reference13.

Table S10. Relative enthalpies of R3c and R-3c Sn3N4 with different functionals.
Relative enthalpies ΔE (meV/f.u.)
Pressure
PBE SCAN PBE0
(GPa)
R3c R-3c R3c R-3c R3c R-3c
80 0 14 0 8 0 4
90 0 18 0 13 0 6

S33
 Figure S14. Evolution of Bader charges upon compression in Sn3N4 phases (PBE level).

Table S11. The integration of the crystal orbital Hamiltonian population (-ICOHP) at the
Fermi level enthalpies of four phases Sn3N4 at increasing pressure.
Space group Pressure (GPa) Interaction -ICOHP Average (eV/pair)
Fd-3m 0 Sn-N 4.733
(SG 227) 20 Sn-N 5.150
P21/c 50 Sn-N 4.359
(SG 14) 70 Sn-N 4.529
R3c 80 Sn-N 3.800
(SG 161) 100 Sn-N 3.902
I-43d 100 Sn-N 3.412
(SG 220) 200 Sn-N 3.726

S34
S7.2. SnN2
Recently, pyrite-type SnN2 was synthesized successfully by using a laser-heated
diamond-anvil cell under pressure14. The structure information of the SnN2 quenched at
ambient pressure is presented in Table S12 with our theoretical results, showing a good
agreement.

Table S12. Comparison with experimental SnN2 phases (distances in Å, angles in °,
pressure in GPa).

Space
Phase P Z Lattice Parameters Atomic coordinates (fractional)
Group
a=5.069, b=5.069, c=5.069 Sn (0.500, 0.500, 0.500); N (-0.086, -
SnN214 0 4 Pa-3
α=90.0, β=90.0, γ=90.0 0.086, -0.086)
USPEX a=5.145, b=5.145, c=5.145 Sn (0.500, 0.500, 0.500); N (-0.083, -
0 4 Pa-3
SnN2 α=90.0, β=90.0, γ=90.0 0.083, -0.083)

S35
S8. Metastable composition
In this section, we discuss the structural and electronic properties of novel metastable
phases located by our UPEX EA searches. All stationary structures are located at
0≤HHull≤150 meV on the potential energy surface, for a given pressure (see Figure 1 in
the article).

S8.1. SnN3

We find that SnN3 stoichiometry does not yield any stable structure at any pressure we
studied. The best ground-state structures candidates, Imm2 (SG 44) [0-58 GPa] and C2/m
(SG 12) [above 58 GPa], are shown in Figure S15. The orthorhombic Imm2 phase lies at
+130 meV/atom above the convex hull at 50 GPa. Its structure presents well separated (3.3
Å) bent triatomic N3 units encapsulated in a four channel of tin (Figure S15a). N-N bond
lengths of 1.33 Å and a valence angle of 113.0° are computed in N3 at 20 GPa. The
electropositive Sn atoms can provide four electrons to a N3 unit, if one considers a full
electron transfer. An open-shell 19 valence electrons species N34- should then be considered,
which is isoelectronic to molecular open-shell O-Cl-O. On the other hand, if one considers
a formal transfer of 3 electrons to the N3 unit, a closed shell N33- with 18 valence electrons
is expected. It would possess a single/ double bond character in agreement with the
calculated distance of 1.33 Å (a AX2E1 VSEPR type structure (bent), indicated in Figure
S15c). In such case, the remaining electron must be located in the valence s/p tin states.
The calculated electronic DOS corroborates our findings (Figure S15d): the Fermi level
crosses a region mainly based on nitrogen π antibonding states that would be the πx* of a
molecule-like N34-. Since half of the πx* band appear filled, SnN3 is expected to be metallic.

The triatomic bent N3 network is maintained when pressure is released to ambient

conditions, therefore Imm2 should be quenchable and lies at 559 meV/atom (corrected
energy: 304 meV/atom) above the convex hull. Moreover, AIMD simulations show that
SnN3 is thermally stable, at least up to 900 K (see Figure S31).

S36
 Figure S15. Crystal structures of SnN3 (a) Imm2 at 20 GPa and (b) C2/m at 100 GPa;
(c) Lewis structure of N33-; (d) and (e) Projected DOS and COHP of bent N3 in Imm2
SnN3 at 20 GPa, and zig-zag N-chain in C2/m SnN3 at 100 GPa, respectively.

Above 58 GPa, a C/2m SnN3 phase becomes more stable than Imm2. Its structure is
based on Sn2N2 slab alternating with an all-trans zigzag infinite chain of poly-N2 (Figure
S15 b). If one considers nitrides in Sn2N2 slabs, formally (2Sn4+,2N3-), one electron remain
that can be transfer to the N2 repeating unit of polynitrogen. In the latter, regular N-N
distances of 1.29 Å are observed, intermediate between a single (1.34 Å) and a double (1.22
Å) bond at 100 GPa. The DOS of C2/m SnN3 are shown in Figure S15e. This phase is

S37
calculated to be metallic. The bands crossing the Fermi level are π-based, i.e. (π1, π2*)
bands of poly-N2 with some lone pair characteristics. Note that a Peierls distortion should
occur in the -(N2-)x- chain as the Fermi level crosses π bands. The strong ionic interactions
between Sn4+ cations and -(N22-)x- chains should however prevent substantial Peierls
distortion of the polymeric chain. As a result, the difference among successive N-N bonds
is small, less than 0.001 Å. High-pressure C2/m phase does not present a dynamically stable
structure at 1 atm, C2/m SnN3 should therefore not be quenchable.

S8.2. SnN4

As shown in Figure 11 in article, SnN4 has three metastable phases with a sequence of
P4/mbm (SG 127) [0-11 GPa] → I4/mcm (SG 140) [11-55 GPa] → P-1 (SG 2) [55-75 GPa].
At pressure above 75 GPa P-1 becomes thermodynamically stable. Tetragonal I4/mcm lies
at 142 meV/atm above the convex hull at 20 GPa. The I4/mcm structure displays square
anti-prism Sn(N2)8 clusters with Sn-N bond lengths of 2.24 Å at 20 GPa (Figure S16a). The
N-N distance is 1.22 Å, indicating N-N double bond character. According to the Zintl-
Klemm concept, SnN4 can be described as (Sn4+, 2N22-). Diazenide N22- would then have
12 valence electrons and its electronic ground-state configuration would be
1σg22σu*21πu42σg21πg*2. The N22- dumbbell possesses a bond order of 2 and is a solid-state
equivalent of the O2 molecular. As shown in the calculated DOS (Figure S16b), the Fermi
level crosses a high density of states corresponding to the degenerated 1πg* levels. I4/mcm
SnN4 is then expected to be a metal at 20 GPa.

S38
 Figure S16. (a) Crystal structures of SnN4 I4/mcm at 20 GPa and (b) calculated DOS.

Figure S17. Schematic molecular orbital diagram of N24- (adapted from our published
MO diagram in reference). The solid and dashed lines indicate the primary and secondary
parentage of the molecular orbitals (MO), respectively (2s-2pz mixing). Only the valence
orbitals are shown. LUMO, lowest unoccupied MO; HOMO, highest occupied MO.
S39
S8.3. SnN6

The stable high-pressure phase of SnN6, Ibam, transforms into metastable R-3c phase
below 50 GPa. R-3c SnN6 displays Sn(N2)12 clusters where each N2 is linked to four tin
atoms (See Figure S18). Long Sn-N bonds are calculated, 2.52-2.67 Å, a value within the
range of weak dative bonds. N2 units are observed with a N-N separation of 1.15 Å at 20
GPa (1.12 Å in triple bonded N2). The computed formation enthalpy of R-3c SnN6 is only
-0.016 ev/atm at 20 GPa.

Figure S18. (a) Crystal structures of SnN6 R-3c at 20 GPa.

(b) Local structural environment of tin.

S40
S8.4. SnN

SnN structures are found metastable over the whole studied pressure range. The phase
sequence is R-3m (SG 166) [0 - 14 GPa] → I4/mmm (SG 139) [14 - 55 GPa] → Cmmm
(SG 65) [55 - 181 GPa] → P63/mmc (SG 194) [above 181 GPa]. At atmospheric pressure,
the lowest energy crystalline phase of SnN is R-3m, which is lower than all the phases
reported by Caskey et al15. They proposed a C2/m (SG 12) SnN as the lowest energy phase
at atmospheric pressure. Meanwhile, a distorted CuFeO2-type P-1 (SG 2) was reported by
the same authors as a metastable phase, which matches the experimental XRD pattern.
However, in our methodology, both of the reported phases lie above our USPEX one R-3m
(SG 166) with a difference of 14 and 111 meV/atom, respectively. The crystal structure of
our new phase R-3m SnN is shown in Figure S19a. The calculated enthalpy differences as
function of pressure for our SnN structures and four others published SnN phases15 is also
reported in Figure S19b. The hexagonal R-3m structure is based on nitrides Sn4N4 layers
stacked along the (001) direction with an interlayer spacing of 2.71 Å (Sn-Sn=3.41 Å) at 0
GPa (see Figure S19a). Each nitrogen seats in a tetrahedral site with Sn-N distances ranging
from 2.13 Å to 2.35 Å. 4-coordinated tin atoms are located in the top and bottom of the
tetrahedral sites, while 5-coordinated tin atoms lie within the Sn4N4 layers. This localized
bonding scheme leads to a mixed-valence Sn(II)-/Sn(IV) compound. Meanwhile, the R-3m
SnN is quenchable, as shown in Figure S5. Furthermore, AIMD simulations show that R-
3m SnN is thermally stable, at least up to 900 K (see Figure S34). A HSE06 gap of 0.3 eV
is computed for R-3m SnN (Figure S5), indicating a possible semiconductor.

S41
 Figure S19. (a) Crystal structure of R-3m SnN at atmospheric pressure. (b) The H-P of
various SnN structures with four other SnN phases from reference.

Isoelectronic SiC and GeN phases have been proposed within the Pbca (SG 61)
geometry16, we also predicted that phase with our EA search, but it lies above our proposed
structure R-3m (SG 166). The formation enthalpy difference is +78 meV/atom at
atmospheric pressure. In Materials Project database17, a metallic SnN phase is proposed
with Cm structure (SG 8) with 4-coordinated Sn and N atoms. It is, in our methodology,
far above our proposed structure the corresponding enthalpy difference being 224
meV/atom at atmospheric pressure.

The tetragonal I4/mmm structure is based on nitrides Sn2N2 bilayers opposed along the
(100) direction (see Figure S20a). Each nitrogen seats in a square pyramidal site with Sn-
N distances of 2.16 Å (apical) and 2.25 Å (basal) at 20 GPa. Tin has an octahedral
environment, Sn(N)5Sn with a Sn-Sn single bond (2.73 Å in SnN vs 2.88 Å in elemental
diamond Fd-3m Sn). This localized bonding scheme leads to Sn(III) or a mixed-valence
Sn(II)-/Sn(IV) compound (calculated Bader charges at PBE level, Sn:+1.47e; N:-1.47e)).
A HSE06 gap of 0.8 eV is computed (see Figure S20b), I4/mmm SnN is therefore expected
to be semiconducting.

S42
 Figure S20. (a)Crystal structures and (b) DOS (PBE and HSE06) of SnN I4/mmm at 20
GPa.
When pressure increases, a Cmmm phase appears as the lowest phase above 55 GPa.
Sn3N3 slabs are observed with 5- and 6-coordinated N3- anions (see Figure S21a). Note that
there are electrons delocalized over the interlayer spacing. The Fermi level crosses a low
density of states, mainly of tin character (see Figure S4).

Figure S21. Crystal structure of SnN Cmmm at 100 GPa (Sn-Sn bonds are not drawn). (a)
Isosurface of ELF with a value of 0.8. (b) ELF contours in the (001) plane.

S43
S8.5. SnN8
S8.5.1 Im-3 SnN8 at atmospheric pressure
At atmospheric pressure, the lowest crystalline phase of SnN8 is Im-3. This cubic
structure presents an unusual coordination mode of tin: four N2 dimers are surrounding
each tin center, forming a square planar ML4 fragment with 2.94 Å for Sn-N distance (See
Figure S22). In the second coordination sphere, four others N2 dimers are located above
and below each ML4 fragment at a longer distance of 3.01 Å. Figure S22c enlightens the
M(N2)8 fragments found in solid-sate SnN8 compound. Note that the resulting packing
leads the structure to exhibit vacancies (radius of 3.23A). In Im-3 SnN8, each N2 is linked
to two metal centers with bent Sn-N-N angles (~130°). A slightly elongated N-N bond
length of 1.13 Å is calculated, compared to 1.10 Å in free N2. Sn-Sn contacts are larger
than 4.9 Å, a signature of the presence of isolated Sn4+ cations. We propose an ionic picture
in which one electron is attributed per N2 unit (Sn4+, 4N2-). Here, each radical N2- ligand
acts as a three-electron donor ligand to two Sn centers (see Lewis structure in Figure S22d).
A two electrons - two centers (2e-2c) bond is associated with the short Sn-N distance of
2.94 Å, while a two electrons - three centers (2e-3c) bond is associated with the long Sn-N
contact of 3.01Å. This bonding mode explains the relative stability of this nitrogen-rich tin
compound. However, Im-3 SnN8 is found thermally unstable even at 300 K, as shown in
Figure S33.

Figure S22. Crystal structure of Im-3 SnN8 phase at 1 atm. In (a), the shortest Sn-N
separations are displayed, while in (b) short and long separations are drawn. (c) local
structural environment of tin complex. Distance are in angstroms (d) a Lewis structure of
tin complex.

S44
S8.5.2 P-1-II SnN8 at high pressure

High-pressure P-1-II SnN8 phase presents one-dimensional compressed polynitrogen

chains running in tin channels (see Figure S23). This one-dimensional nitrogen ribbon is
especially interesting with respect to its topology: two types of rings are present, an 8- and
a 6-membered ones. Thus, the repeating unit of poly-N8 is based on non-planar eight
membered ring with four pyramidal three-coordinated nitrogen atoms and four bent two-
coordinated ones. The covalent N-N separations are 1.30-1.39 Å at 200 GPa, within the
range of a single bond. These local geometries are expected in N84- building units from
VSEPR considerations, in which tin gives its four valence electrons (See a Lewis structure
in Figure S23c). As SnN8 abides the octet rule, one may expect that this solid-state
compound possesses a substantial energy gap between its valence and conduction bands.
This what we observed in its DOS: SnN8 is an insulator at 200 GPa (PBE and HSE06 gaps
of 1.7 and 3.1 eV, respectively, see Figure S5).

Figure 23. (a) Crystal structure of P-1-II SnN8 at 200 GPa (view along the (001)
direction). (b) view of its nitrogen chain with fused 8- and 6-rings. (c) Lewis structure of
its N8- repeating unit.

S45
S8.6. Sn2N and Sn3N2

S8.6.1. Sn2N

Sn2N phases are shown in the Figure S24. This 1:2 stoichiometry presents three phases
from 0 to 200 GPa, with a transition phase sequence of P21/m (SG 11) [0 - 20 GPa] → R-
3m (SG 166) [20 - 168 GPa] → C2/m (SG 12) [above 168 GPa]. In these Sn2N phases,
isolated nitrogen atoms are found, which may be described as isolated N3- anions (to reach
the octet count). This requires the two tin atoms from the formula unit to transfer 3 electrons,
yielding a 5 valence electrons per Sn2 network. These valence electrons remain within the
tin framework. All the tin-rich phases are metallic, thus electrons are expected to be
strongly delocalized over the all atoms. The attribution of a unique formal oxidation
number for tin is therefore not adapted here.

The P21/m phase has a formation enthalpy of +0.160 eV/atom at 1 atm, and is found
dynamically stable. Its structure consists in a distorted network of hexagonal close packed
Sn layers, with N atoms within the fourfold channels. The Fermi level crosses a high
density of states mainly of Sn character. Sn2N is therefore expected to be a metal.

Figure S24. Crystal structures of Sn2N phases. (a) P21/m at 1 atm, (b) R-3m at 50 GPa,
and (c) C2/m at 200 GPa.

S46
S8.6.2. Sn3N2

The 3:2 composition has been theoretically proposed for group 14 – nitrides compounds
in the metastable Pm-3m A3N2 structure with A=C, Si and Ge17. The latter phase exhibits a
cage structure with 4- and 3-coordinated A and N, respectively (see Figure S25a for Sn3N2).
A formal oxidation state of +2 is assigned per A atom. However, at 1 atm, the lowest
ground-state Sn3N2 compound found by our EA searches has the C2/m structure (SG 12).
Its formation energy is 0.206 eV/atom lower than that of the Pm-3m structure. C2/m Sn3N2
structure may be seen as a packing compact hexagonal Sn layers along the c direction with
an interlayer spacing of 2.64 Å and 3.18 Å (Sn-Sn=3.13-3.16 Å) at 20 GPa. The N3- anions
occupy half of the tetrahedral sites in every two Sn-slabs. Thus Sn4+ cations are surrounded
by six N3- anions in octahedral sites (see Figure S25b). Moreover, we may also consider
Sn3N2 structure as interacting Sn3N2 slabs through Sn-Sn delocalized bonds (Sn-Sn=3.03-
3.45 Å at 20 GPa). Formally a [2Sn2+, 1Sn4+, 2N3-]2+ slab may be considered, where only
2 electrons per formula unit assure the delocalized bonding between the Sn3N2 sheets. The
analysis of its projected DOS (Figure S4) shows that the Fermi level crosses a density of
states with a tin character. Sn3N2 is expected to be a metal which is confirmed in both of
PBE and HSE06 level, see Figure S25d.

Figure S25. Crystal structure of metastable Sn3N2 phases at 1 atm. (a) Si3N2-like Pm-3m.
(b) C2/m Sn3N2. (c) Isosurface of ELF with a value of 0.8 for C2/m Sn3N2. (d) the DOS
of C2/m by PBE and HSE06.

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S9. Dynamically unstable Sn(N5)2 pentazolate

Table S13. Structural information and phonon dispersion of pentazolate Sn(N5)2 phases
(distances in Å, angles in °, pressure in GPa).

space
group, Pressure Structural information Phonon dispersion
Z

a=7.978, b=9.038, c=5.802,

α=90.0, β=90.0, γ=90.0;
Sn (0.000, 0.500, 0.261);
P21212, N (-0.210, -0.185, 0.330),
0
Z=2 (-0.187, -0.283, 0.160),
(-0.269, -0.240, -0.025),
(-0.343, -0.114, 0.032),
(-0.306, -0.079, 0.250).

a=6.694, b=6.694, c=7.875,

α=90.0, β=90.0, γ=90.0;
I4/m, Sn (0.000, 0.000, -0.258);
50
Z=4 N (-0.205, 0.477, 0.000),
(-0.171, -0.415, 0.134),
(-0.113, -0.242, 0.082).

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S10. AIMD calculations
AIMD simulations with canonical ensemble using the Nosé heat bath scheme were
performed to evaluate the thermal stability of specific phases up to 900 K for 10 ps, see
Figure S27-S34. Radial distribution functions (RDF) of specific phases are presented in
Figure S26, which reveals if the contact between atoms is preserved at high
temperature. The interval of RDF analysis is set as 0.02 Å.

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Figure S26. Radial distribution functions (RDF) for the N-N and Sn-N separations
observed during AIMD simulations at ambient pressure and T up to 900 K. For
Sn(N5)4 P-1, the black arrows indicate the average N−N distance in cyclo-N5-.

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Figure S27. Snapshots of the Sn2N P21/m 2 × 2 × 2 supercell at ambient pressure at the
end of 10ps.

Figure S28. Snapshots of the SnN I4/mmm 2 × 2 × 2 supercell at ambient pressure at the
end of 10ps.

Figure S29. Snapshots of the Sn3N4 Fd-3m 1 × 1 × 1 supercell at ambient pressure at the
end of 10ps.

Figure S30. Snapshots of the SnN2 Pa-3 2 × 2 × 2 supercell at ambient pressure at the
end of 10ps.

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Figure S31. Snapshots of the SnN3 Imm2 2 × 2 × 2 supercell at ambient pressure at the end
of 10ps.

Figure S32. Snapshots of the SnN4 P-1 3 × 3 × 3 supercell at ambient pressure at the end
of 10ps.

Figure S33. Snapshots of the SnN8 Im-3 1 × 1 × 1 supercell at ambient pressure at the
end of 10ps.

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 900 K
Figure S34. Snapshots of the SnN R-3m 1 × 1 × 1 supercell at ambient pressure at the
end of 10ps.

Figure S35. Snapshots of the SnN20 P-1 1 × 2 × 2 supercell at ambient pressure at the
end of 10ps.

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Formation enthalpy of Fd-3m Sn3N4 in MaterialProject:

https://materialsproject.org/materials/mp-16031/#corrections-eqn;

Cm SnN: https://materialsproject.org/materials/mvc-13927/;

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Pm-3m A3N2 with A = C, Si and Ge in MaterialProject:

C3N2: https://materialsproject.org/materials/mp-1105655/;

Si3N2: https://materialsproject.org/materials/mp-971682/;

Ge3N2: https://materialsproject.org/materials/mp-971694/.

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