Crystal structure, thermal properties and detonation characterization of bis­(5-amino-1,2,4-triazol-4-ium-3-yl)methane dichloride

Bis(5-amino-1,2,4-triazol-4-ium-3-yl)methane dichloride (BATZM·Cl₂ or C₅H₁₀N₈²⁺·2Cl⁻) was synthesized and crystallized, and the crystal structure was characterized by single-crystal X-ray diffraction; it belongs to the space group C2/c (monoclinic) with Z = 4. The structure of BATZM·Cl₂ can be described as a V-shaped mol­ecule with reasonable chemical geometry and no disorder, and its one-dimensional structure can be described as a rhombic helix. The specific molar heat capacity (C_p,m) of BATZM·Cl₂ was determined using the continuous C_p mode of a microcalorimeter and theoretical calculations, and the C_p,m value is 276.18 J K⁻¹ mol⁻¹ at 298.15 K. The relative deviations between the theoretical and experimental values of C_p,m, H_T – H_298.15K and S_T – S_298.15K of BATZM·Cl₂ are almost equivalent at each temperature. The detonation velocity (D) and detonation pressure (P) of BATZM·Cl₂ were estimated using the nitro­gen equivalent equation according to the experimental density; BATZM·Cl₂ has a higher detonation velocity (7143.60 ± 3.66 m s⁻¹) and detonation pressure (21.49 ± 0.03 GPa) than TNT. The above results for BATZM·Cl₂ are com­pared with those of bis­(5-amino-1,2,4-triazol-3-yl)methane (BATZM) and the effect of salt formation on them is discussed.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Bis(5-amino-1,2,4-triazol-4-ium-3-yl)methane dichloride

Crystal data

C5H10N8^2+·2Cl^−	F(000) = 520
Mr = 253.11	Dx = 1.608 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.962 (2) Å	Cell parameters from 2030 reflections
b = 5.9225 (7) Å	θ = 3.5–27.2°
c = 11.6649 (15) Å	µ = 0.60 mm^−1
β = 127.027 (1)°	T = 296 K
V = 1045.8 (2) Å^3	Rodlike, colourless
Z = 4	0.37 × 0.31 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer	1075 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.027
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 27.2°, θmin = 3.5°
Tmin = 0.810, Tmax = 0.882	h = −24→23
2863 measured reflections	k = −6→7
1140 independent reflections	l = −14→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	All H-atom parameters refined
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 0.6221P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
1140 reflections	Δρmax = 0.30 e Å^−3
90 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.10191 (2)	0.20091 (6)	0.02328 (4)	0.03403 (17)
N2	0.34191 (7)	−0.17966 (18)	0.10735 (13)	0.0292 (3)
N1	0.29098 (7)	−0.0173 (2)	0.10993 (12)	0.0293 (3)
C1	0.34034 (8)	0.1360 (2)	0.21100 (14)	0.0278 (3)
N3	0.42443 (7)	0.07293 (19)	0.27632 (12)	0.0265 (3)
C2	0.42214 (8)	−0.1206 (2)	0.20957 (13)	0.0263 (3)
N4	0.31125 (10)	0.3135 (2)	0.23856 (18)	0.0440 (4)
C3	0.500000	−0.2549 (4)	0.250000	0.0361 (5)
H1	0.2360 (12)	−0.023 (3)	0.0545 (18)	0.031 (4)*
H3	0.4699 (13)	0.136 (3)	0.344 (2)	0.040 (5)*
H4B	0.3441 (14)	0.399 (4)	0.300 (2)	0.049 (5)*
H4A	0.2563 (16)	0.332 (4)	0.188 (2)	0.054 (6)*
H3A	0.4805 (13)	−0.348 (3)	0.171 (2)	0.046 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0248 (2)	0.0361 (2)	0.0306 (2)	0.00612 (12)	0.01106 (17)	0.00698 (12)
N2	0.0190 (5)	0.0294 (6)	0.0311 (6)	−0.0025 (4)	0.0108 (5)	−0.0058 (4)
N1	0.0158 (5)	0.0348 (6)	0.0294 (6)	−0.0034 (4)	0.0095 (5)	−0.0085 (5)
C1	0.0221 (6)	0.0326 (7)	0.0270 (6)	−0.0062 (5)	0.0140 (5)	−0.0048 (5)
N3	0.0181 (5)	0.0301 (6)	0.0228 (5)	−0.0069 (4)	0.0077 (5)	−0.0037 (4)
C2	0.0192 (6)	0.0267 (6)	0.0264 (6)	−0.0035 (5)	0.0102 (5)	0.0005 (5)
N4	0.0287 (7)	0.0466 (8)	0.0484 (9)	−0.0061 (6)	0.0188 (7)	−0.0232 (6)
C3	0.0203 (9)	0.0277 (9)	0.0430 (12)	0.000	0.0100 (9)	0.000

Geometric parameters (Å, º)

N2—C2	1.2938 (17)	N3—H3	0.827 (19)
N2—N1	1.3759 (16)	C2—C3	1.4819 (17)
N1—C1	1.3271 (17)	N4—H4B	0.79 (2)
N1—H1	0.834 (18)	N4—H4A	0.84 (2)
C1—N4	1.314 (2)	C3—H3A	0.934 (19)
C1—N3	1.3412 (17)	C3—H3A^i	0.933 (19)
N3—C2	1.3717 (17)
C2—N2—N1	104.02 (11)	N2—C2—C3	122.78 (12)
C1—N1—N2	111.63 (10)	N3—C2—C3	125.66 (11)
C1—N1—H1	126.9 (11)	C1—N4—H4B	121.3 (15)
N2—N1—H1	121.4 (11)	C1—N4—H4A	117.2 (15)
N4—C1—N1	126.11 (13)	H4B—N4—H4A	121 (2)
N4—C1—N3	127.90 (13)	C2^i—C3—C2	115.07 (17)
N1—C1—N3	105.99 (11)	C2^i—C3—H3A	110.9 (12)
C1—N3—C2	106.85 (10)	C2—C3—H3A	105.9 (12)
C1—N3—H3	128.1 (13)	C2^i—C3—H3A^i	105.9 (12)
C2—N3—H3	125.1 (13)	C2—C3—H3A^i	110.9 (12)
N2—C2—N3	111.51 (12)	H3A—C3—H3A^i	108 (2)
C2—N2—N1—C1	0.59 (15)	N1—N2—C2—C3	177.35 (11)
N2—N1—C1—N4	178.84 (15)	C1—N3—C2—N2	0.10 (15)
N2—N1—C1—N3	−0.54 (15)	C1—N3—C2—C3	−177.58 (12)
N4—C1—N3—C2	−179.10 (15)	N2—C2—C3—C2^i	142.26 (15)
N1—C1—N3—C2	0.27 (14)	N3—C2—C3—C2^i	−40.31 (10)
N1—N2—C2—N3	−0.41 (15)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Cl	0.84 (2)	2.47 (2)	3.2408 (16)	153.4 (19)
N4—H4B···Cl^ii	0.79 (2)	2.44 (2)	3.1911 (15)	159.9 (19)
N3—H3···Cl^iii	0.827 (19)	2.30 (2)	3.1213 (11)	175.3 (18)
N1—H1···N2^iv	0.834 (18)	2.342 (16)	2.8815 (16)	122.9 (14)
N1—H1···Cl	0.834 (18)	2.691 (17)	3.3438 (12)	136.3 (14)

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1/2, −y−1/2, −z.