The crystal structure and thermal decomposition kinetics of cis-hexa­nitro­stilbene

Hexa­nitro­stilbene (HNS) is an energetic material with wide application and excellent comprehensive performance. cis-HNS is successfully prepared using crude HNS with a purity of 95% as the raw material and N-methyl pyrrolidone (NMP) as the solvent. After separation and purification, acetone is used as a solvent to obtain light-yellow crystals at room temperature. The molecular structure of cis-HNS is determined through analysis of Fourier transform infrared, ¹³C NMR and ¹H NMR spectroscopy and single-crystal X-ray diffraction data. The thermal decomposition properties of cis and trans-HNS are studied using differential scanning calorimetry (DSC). When the heating rate is low, cis-HNS will undergo a crystal transformation after melting, from liquid cis-HNS to liquid trans-HNS, and then it will solidify and release heat. According to the results of DSC data, the apparent kinetic parameters of thermal decomposition of cis- and trans-HNS were obtained by Kissinger method [Kissinger (1957). Anal. Chem. 29, 1702–1706] and Ozawa method [Ozawa (1965). Bull. Chem. Soc. Jpn. 38, 1881–1886], respectively. The spontaneous combustion temperature and self-accelerating decomposition temperature of cis and trans-HNS are calculated by the Zhang-Hu-Xie-Li method [Zhang et al. (1994). Thermochim. Acta, 244, 171–176].

Computing details

Cell refinement: SAINT V8.38A (?, 2016); data reduction: SAINT V8.38A (?, 2016); program(s) used to solve structure: ShelXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(cis-HNS)

Crystal data

C14H6N6O12	F(000) = 1824
Mr = 450.25	Dx = 1.815 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.2210 (6) Å	Cell parameters from 6085 reflections
b = 10.3080 (3) Å	θ = 2.2–26.3°
c = 19.4134 (5) Å	µ = 0.16 mm^−1
β = 129.087 (1)°	T = 170 K
V = 3296.17 (16) Å^3	Block, colourless
Z = 8	0.15 × 0.08 × 0.05 mm

Data collection

D8 VENTURE diffractometer	Rint = 0.088
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0842 before and 0.0479 after correction. The Ratio of minimum to maximum transmission is 0.9408. The λ/2 correction factor is Not present.	θmax = 26.5°, θmin = 2.2°
Tmin = 0.701, Tmax = 0.745	h = −26→26
17600 measured reflections	k = −12→12
3373 independent reflections	l = −24→24
2698 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 3.4414P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3373 reflections	Δρmax = 0.29 e Å^−3
298 parameters	Δρmin = −0.28 e Å^−3
301 restraints

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	Occ. (<1)
O6	0.75656 (9)	0.74827 (14)	0.40818 (9)	0.0324 (3)
O4	0.93226 (9)	0.79655 (13)	0.53960 (9)	0.0317 (3)
O7	0.91740 (9)	0.33299 (16)	0.39913 (10)	0.0365 (4)
O11	0.46780 (9)	0.41969 (15)	0.14686 (10)	0.0353 (4)
O10	0.72633 (10)	0.53469 (14)	0.09454 (9)	0.0334 (4)
O12	0.47955 (9)	0.37459 (15)	0.04638 (9)	0.0361 (4)
O8	0.79229 (9)	0.29173 (14)	0.34001 (9)	0.0341 (4)
O9	0.82602 (9)	0.45615 (16)	0.22315 (10)	0.0362 (4)
O1	0.83129 (11)	0.21228 (16)	0.62521 (12)	0.0465 (4)
O2	0.92088 (11)	0.33393 (18)	0.73719 (11)	0.0474 (5)
O5	0.70945 (11)	0.58492 (17)	0.43374 (10)	0.0442 (4)
N4	0.50520 (10)	0.42001 (15)	0.11851 (11)	0.0247 (4)
N6	0.85907 (10)	0.33946 (15)	0.39724 (10)	0.0243 (4)
N5	0.75780 (10)	0.50229 (15)	0.17035 (11)	0.0241 (4)
N2	0.93302 (10)	0.72497 (16)	0.58937 (10)	0.0286 (4)
N3	0.72232 (10)	0.64347 (16)	0.38901 (10)	0.0249 (4)
N1	0.87753 (12)	0.30498 (18)	0.65845 (13)	0.0344 (4)
C11	0.61741 (11)	0.52981 (17)	0.25466 (12)	0.0205 (4)
H11	0.586001	0.532172	0.274032	0.025*
C12	0.58702 (11)	0.47618 (17)	0.17417 (12)	0.0207 (4)
C13	0.63158 (11)	0.47012 (17)	0.14458 (12)	0.0210 (4)
H13	0.609220	0.435334	0.088014	0.025*
C9	0.74601 (11)	0.57442 (16)	0.28371 (11)	0.0180 (4)
O3	0.9443 (2)	0.7628 (4)	0.6570 (2)	0.0451 (9)	0.75
C8	0.82967 (11)	0.62663 (17)	0.33614 (11)	0.0198 (4)
H8	0.840302	0.676894	0.303456	0.024*
C4	0.86181 (11)	0.32986 (19)	0.52342 (12)	0.0241 (4)
H4	0.843144	0.242830	0.507686	0.029*
C1	0.91002 (11)	0.58709 (18)	0.56482 (12)	0.0216 (4)
C7	0.89197 (11)	0.61363 (17)	0.42198 (11)	0.0202 (4)
H7	0.940985	0.656821	0.443962	0.024*
C6	0.89143 (10)	0.53722 (18)	0.48651 (11)	0.0198 (4)
C14	0.70953 (11)	0.51666 (17)	0.20068 (11)	0.0193 (4)
C10	0.69528 (11)	0.58025 (17)	0.30650 (11)	0.0193 (4)
C5	0.87004 (11)	0.40667 (18)	0.47128 (12)	0.0212 (4)
C3	0.88205 (12)	0.38592 (19)	0.59942 (13)	0.0259 (4)
C2	0.90706 (12)	0.51313 (19)	0.62216 (12)	0.0255 (4)
H2	0.921819	0.548945	0.675650	0.031*
O0AA	0.9790 (6)	0.7473 (12)	0.6695 (6)	0.041 (3)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O6	0.0381 (8)	0.0240 (7)	0.0343 (8)	−0.0032 (6)	0.0224 (7)	−0.0083 (6)
O4	0.0421 (9)	0.0257 (7)	0.0292 (7)	−0.0052 (6)	0.0234 (7)	−0.0019 (6)
O7	0.0318 (8)	0.0469 (9)	0.0353 (8)	0.0099 (7)	0.0232 (7)	−0.0007 (7)
O11	0.0278 (8)	0.0429 (9)	0.0433 (9)	−0.0099 (6)	0.0264 (7)	−0.0095 (7)
O10	0.0515 (10)	0.0333 (8)	0.0302 (8)	−0.0017 (7)	0.0328 (8)	0.0008 (6)
O12	0.0286 (8)	0.0453 (9)	0.0297 (8)	−0.0136 (7)	0.0162 (7)	−0.0141 (7)
O8	0.0333 (8)	0.0267 (7)	0.0316 (8)	−0.0083 (6)	0.0154 (7)	−0.0080 (6)
O9	0.0230 (8)	0.0547 (10)	0.0340 (8)	−0.0040 (7)	0.0195 (7)	−0.0104 (7)
O1	0.0479 (10)	0.0393 (9)	0.0728 (12)	0.0085 (8)	0.0478 (10)	0.0213 (8)
O2	0.0672 (12)	0.0524 (10)	0.0434 (10)	0.0200 (9)	0.0447 (10)	0.0196 (8)
O5	0.0562 (11)	0.0589 (11)	0.0342 (8)	−0.0159 (9)	0.0364 (8)	−0.0094 (8)
N4	0.0220 (8)	0.0239 (8)	0.0277 (8)	−0.0021 (7)	0.0154 (7)	−0.0016 (7)
N6	0.0268 (9)	0.0190 (8)	0.0256 (8)	0.0038 (7)	0.0157 (7)	0.0016 (6)
N5	0.0297 (9)	0.0242 (8)	0.0263 (8)	−0.0077 (7)	0.0214 (8)	−0.0076 (7)
N2	0.0310 (9)	0.0304 (9)	0.0194 (8)	−0.0026 (7)	0.0135 (7)	−0.0043 (7)
N3	0.0259 (8)	0.0289 (9)	0.0234 (8)	0.0010 (7)	0.0172 (7)	−0.0032 (7)
N1	0.0398 (10)	0.0353 (10)	0.0472 (11)	0.0182 (9)	0.0365 (10)	0.0184 (9)
C11	0.0224 (9)	0.0194 (9)	0.0243 (9)	0.0017 (7)	0.0168 (8)	0.0019 (7)
C12	0.0192 (9)	0.0189 (9)	0.0216 (9)	−0.0009 (7)	0.0117 (8)	0.0015 (7)
C13	0.0235 (9)	0.0192 (9)	0.0181 (9)	−0.0020 (7)	0.0121 (8)	−0.0001 (7)
C9	0.0205 (9)	0.0157 (8)	0.0183 (8)	0.0003 (7)	0.0124 (7)	0.0028 (7)
O3	0.066 (2)	0.0404 (16)	0.0294 (15)	−0.0062 (19)	0.0304 (18)	−0.0113 (12)
C8	0.0246 (9)	0.0183 (8)	0.0220 (9)	−0.0050 (7)	0.0174 (8)	−0.0021 (7)
C4	0.0193 (9)	0.0217 (9)	0.0317 (10)	0.0042 (7)	0.0163 (8)	0.0049 (8)
C1	0.0195 (9)	0.0233 (9)	0.0203 (9)	0.0004 (7)	0.0118 (8)	0.0002 (7)
C7	0.0210 (9)	0.0209 (9)	0.0215 (9)	−0.0040 (7)	0.0147 (8)	−0.0035 (7)
C6	0.0148 (8)	0.0243 (9)	0.0191 (8)	0.0018 (7)	0.0101 (7)	0.0009 (7)
C14	0.0242 (9)	0.0187 (9)	0.0206 (9)	−0.0014 (7)	0.0168 (8)	0.0002 (7)
C10	0.0231 (9)	0.0170 (8)	0.0172 (8)	0.0018 (7)	0.0124 (8)	0.0011 (7)
C5	0.0182 (9)	0.0240 (9)	0.0210 (9)	0.0029 (7)	0.0122 (7)	0.0002 (7)
C3	0.0254 (10)	0.0301 (10)	0.0312 (10)	0.0100 (8)	0.0222 (9)	0.0115 (8)
C2	0.0241 (10)	0.0321 (10)	0.0213 (9)	0.0072 (8)	0.0148 (8)	0.0039 (8)
O0AA	0.058 (6)	0.036 (5)	0.022 (3)	−0.014 (5)	0.022 (4)	−0.011 (3)

Geometric parameters (Å, º)

O6—N3	1.222 (2)	C11—C12	1.376 (2)
O4—N2	1.208 (2)	C11—C10	1.384 (3)
O7—N6	1.217 (2)	C12—C13	1.383 (3)
O11—N4	1.218 (2)	C13—H13	0.9500
O10—N5	1.218 (2)	C13—C14	1.371 (3)
O12—N4	1.231 (2)	C9—C8	1.483 (2)
O8—N6	1.224 (2)	C9—C14	1.407 (2)
O9—N5	1.225 (2)	C9—C10	1.400 (2)
O1—N1	1.222 (3)	C8—H8	0.9500
O2—N1	1.224 (2)	C8—C7	1.328 (3)
O5—N3	1.221 (2)	C4—H4	0.9500
N4—C12	1.467 (2)	C4—C5	1.380 (3)
N6—C5	1.476 (2)	C4—C3	1.377 (3)
N5—C14	1.476 (2)	C1—C6	1.405 (2)
N2—O3	1.240 (4)	C1—C2	1.383 (3)
N2—C1	1.481 (2)	C7—H7	0.9500
N2—O0AA	1.229 (9)	C7—C6	1.486 (2)
N3—C10	1.470 (2)	C6—C5	1.391 (3)
N1—C3	1.469 (2)	C3—C2	1.379 (3)
C11—H11	0.9500	C2—H2	0.9500
O11—N4—O12	124.49 (16)	C10—C9—C14	113.78 (16)
O11—N4—C12	118.30 (15)	C9—C8—H8	115.2
O12—N4—C12	117.20 (15)	C7—C8—C9	129.67 (16)
O7—N6—O8	125.36 (16)	C7—C8—H8	115.2
O7—N6—C5	117.61 (15)	C5—C4—H4	121.7
O8—N6—C5	117.00 (15)	C3—C4—H4	121.7
O10—N5—O9	125.16 (16)	C3—C4—C5	116.54 (18)
O10—N5—C14	117.68 (16)	C6—C1—N2	120.67 (16)
O9—N5—C14	117.14 (15)	C2—C1—N2	116.30 (16)
O4—N2—O3	123.5 (3)	C2—C1—C6	123.02 (17)
O4—N2—C1	119.57 (15)	C8—C7—H7	117.3
O4—N2—O0AA	119.9 (6)	C8—C7—C6	125.48 (17)
O3—N2—C1	116.6 (3)	C6—C7—H7	117.3
O0AA—N2—C1	115.1 (6)	C1—C6—C7	124.89 (16)
O6—N3—C10	118.21 (15)	C5—C6—C1	114.53 (16)
O5—N3—O6	125.23 (16)	C5—C6—C7	120.57 (16)
O5—N3—C10	116.55 (16)	C13—C14—N5	116.17 (15)
O1—N1—O2	124.80 (18)	C13—C14—C9	125.09 (16)
O1—N1—C3	117.25 (19)	C9—C14—N5	118.73 (16)
O2—N1—C3	117.94 (19)	C11—C10—N3	115.19 (15)
C12—C11—H11	121.1	C11—C10—C9	123.88 (16)
C12—C11—C10	117.81 (16)	C9—C10—N3	120.93 (16)
C10—C11—H11	121.1	C4—C5—N6	115.45 (16)
C11—C12—N4	119.00 (16)	C4—C5—C6	125.06 (17)
C11—C12—C13	122.43 (17)	C6—C5—N6	119.41 (16)
C13—C12—N4	118.54 (16)	C4—C3—N1	117.90 (18)
C12—C13—H13	121.5	C4—C3—C2	122.63 (17)
C14—C13—C12	116.90 (16)	C2—C3—N1	119.46 (18)
C14—C13—H13	121.5	C1—C2—H2	121.0
C14—C9—C8	119.73 (15)	C3—C2—C1	118.05 (17)
C10—C9—C8	126.44 (15)	C3—C2—H2	121.0