Two metastable high hydrates of energetic material 3,3′,5,5′-tetra­nitro-4,4′-bi­pyrazole

Domasevitch, K.V.; Krautscheid, H.

doi:10.1107/S2053229624003346

Two metastable high hydrates of energetic material 3,3′,5,5′-tetranitro-4,4′-bipyrazole

Poly-stoichiometry of hydrated phases is relatively uncommon for organic materials and extended libraries of such species adopting different aqua-to-substrate ratios are still rare. The kinetically controlled higher hydrates could be particularly interesting for their structural relationships, which presumably may imprint some features of the substrate/substrate and aqua/substrate bonding in solutions, and provide insights into the nucleation stage. Two metastable high hydrates are prepared by crash crystallization. The crystal structures of 3,3′,5,5′-tetranitro-4,4′-bipyrazole tetrahydrate, C₆H₂N₈O₈·4H₂O, (1), and 3,3′,5,5′-tetranitro-4,4′-bipyrazole pentahydrate, C₆H₂N₈O₈·5H₂O, (2), are intrinsically related to the previously reported anhydrate and monohydrate, while displaying natural evolution of the patterns upon progressive watering. The accumulation of the water molecules causes their clustering, with the generation of one-dimensional tapes and two-dimensional layers in the genuine channel hydrates (1) and (2), respectively, versus the pocket hydrate structure of C₆H₂N₈O₈·H₂O. The hydration primarily affects the pyrazole sites. It conditions the emergence of N—H

O and O—H

N hydrogen bonds, which is a destructive factor for pyrazole/pyrazole N—H

N hydrogen bonding. At the same time, extensive noncovalent interactions of the organic molecules, namely, lone pair–π-hole O

N interactions of the NO₂/NO₂ and NO₂/pyrazole types, are more competitive to the hydrogen bonding and the motifs of mutual organic/organic stacks remain intact with the increase in hydration. These trends agree with the results of Hirshfeld surface analysis. The contributions of the contacts involving H atoms are increased in line with the growing number of water molecules, while the fraction of O

N/N

O (NO₂) contacts is nearly invariant. One may postulate the significance of the lone pair–π-hole interactions to the aggregation of nitro species in solutions and their relevance for the sebsequent development of the solid-state patterns through nucleation.

Keywords: molecular hydrate; hydrogen bonding; N-heterocyclic aromatic compound; nitro compounds; lone pair–π-hole interaction; crystal structure; Ostwald rule.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229624003346/vp3035sup1.cif Contains datablocks global, 1, 2
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229624003346/vp30351sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229624003346/vp30352sup3.hkl Contains datablock 2

CCDC references: 2348676; 2348675

Computing details top

3,3',5,5'-Tetranitro-4,4'-bipyrazole tetrahydrate (1) top

Crystal data top

C₆H₂N₈O₈·4H₂O	D_x = 1.764 Mg m⁻³
M_r = 386.22	Cu Kα radiation, λ = 1.54186 Å
Orthorhombic, Pbca	Cell parameters from 14295 reflections
a = 21.4196 (8) Å	θ = 4.0–79.7°
b = 6.1927 (2) Å	µ = 1.53 mm⁻¹
c = 21.9265 (8) Å	T = 183 K
V = 2908.44 (18) Å³	Needle, colorless
Z = 8	0.10 × 0.07 × 0.05 mm
F(000) = 1584

Data collection top

STOE STADIVARI diffractometer	3101 independent reflections
Radiation source: GeniX 3D HF Cu	2195 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.038
Detector resolution: 5.81 pixels mm^-1	θ_max = 79.8°, θ_min = 4.0°
rotation method, ω scans	h = −26→27
Absorption correction: multi-scan (LANA; Koziskova et al., 2016)	k = −7→2
T_min = 0.771, T_max = 0.927	l = −27→25
20365 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	All H-atom parameters refined
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0519P)²] where P = (F_o² + 2F_c²)/3
S = 0.90	(Δ/σ)_max < 0.001
3101 reflections	Δρ_max = 0.20 e Å⁻³
276 parameters	Δρ_min = −0.23 e Å⁻³
32 restraints	Extinction correction: SHELXL2019 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00205 (15)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.14098 (7)	0.6584 (2)	0.57023 (6)	0.0348 (3)
O2	0.06762 (7)	0.4647 (2)	0.52816 (6)	0.0344 (3)
O3	0.25768 (7)	0.5011 (3)	0.29894 (7)	0.0392 (3)
O4	0.16120 (7)	0.4025 (3)	0.28851 (6)	0.0382 (3)
O5	−0.00180 (7)	0.7610 (3)	0.28928 (7)	0.0383 (3)
O6	0.09120 (7)	0.8045 (2)	0.32791 (6)	0.0336 (3)
O7	0.02799 (7)	−0.1219 (2)	0.44849 (6)	0.0360 (3)
O8	0.11324 (7)	0.0525 (2)	0.47155 (7)	0.0390 (3)
N1	0.21495 (8)	0.6041 (3)	0.47257 (7)	0.0268 (3)
N2	0.24037 (7)	0.5836 (3)	0.41701 (7)	0.0266 (3)
N3	0.11831 (8)	0.5552 (3)	0.52746 (7)	0.0266 (3)
N4	0.20511 (8)	0.4678 (3)	0.31930 (7)	0.0285 (3)
N5	−0.01516 (7)	0.3807 (3)	0.34525 (7)	0.0270 (3)
N6	−0.01111 (7)	0.1998 (2)	0.37827 (7)	0.0267 (3)
N7	0.04235 (8)	0.7030 (3)	0.32128 (7)	0.0283 (3)
N8	0.06291 (8)	0.0349 (3)	0.44517 (7)	0.0280 (3)
C1	0.15489 (8)	0.5422 (3)	0.47268 (8)	0.0243 (3)
C2	0.13753 (8)	0.4775 (3)	0.41480 (7)	0.0234 (3)
C3	0.19343 (8)	0.5102 (3)	0.38276 (7)	0.0243 (3)
C4	0.03595 (8)	0.5028 (3)	0.35335 (7)	0.0240 (3)
C5	0.07673 (8)	0.4020 (3)	0.39341 (7)	0.0234 (3)
C6	0.04372 (8)	0.2129 (3)	0.40688 (7)	0.0235 (3)
O1W	0.28405 (7)	0.7280 (2)	0.56554 (6)	0.0330 (3)
O2W	0.37886 (7)	0.5771 (3)	0.64017 (7)	0.0385 (3)
O3W	0.21480 (8)	0.7967 (3)	0.67571 (7)	0.0364 (3)
O4W	0.12499 (8)	0.4908 (3)	0.70570 (7)	0.0361 (3)
H1N	0.2402 (13)	0.644 (5)	0.5067 (10)	0.060 (9)*
H2N	−0.0520 (12)	0.431 (5)	0.3242 (13)	0.071 (10)*
H1	0.2626 (13)	0.751 (5)	0.5985 (10)	0.065 (10)*
H2	0.3174 (11)	0.661 (5)	0.5777 (13)	0.055 (9)*
H3	0.4142 (12)	0.517 (5)	0.6312 (15)	0.074 (11)*
H4	0.3835 (17)	0.697 (5)	0.6616 (15)	0.097 (13)*
H5	0.2375 (17)	0.851 (7)	0.7040 (14)	0.102 (14)*
H6	0.1853 (12)	0.892 (4)	0.6691 (13)	0.067 (10)*
H7	0.1577 (13)	0.570 (5)	0.6966 (16)	0.084 (12)*
H8	0.127 (2)	0.474 (7)	0.7456 (11)	0.130 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0352 (8)	0.0409 (9)	0.0284 (6)	0.0001 (6)	−0.0029 (5)	−0.0098 (5)
O2	0.0297 (8)	0.0396 (9)	0.0340 (7)	−0.0074 (6)	0.0051 (6)	−0.0027 (5)
O3	0.0309 (8)	0.0486 (10)	0.0383 (7)	−0.0059 (6)	0.0113 (6)	−0.0026 (6)
O4	0.0352 (9)	0.0482 (10)	0.0312 (7)	−0.0031 (6)	−0.0007 (6)	−0.0073 (5)
O5	0.0353 (8)	0.0393 (9)	0.0402 (8)	0.0038 (6)	−0.0093 (6)	0.0113 (6)
O6	0.0324 (8)	0.0314 (8)	0.0370 (7)	−0.0056 (5)	0.0016 (6)	0.0063 (5)
O7	0.0411 (9)	0.0247 (8)	0.0421 (7)	−0.0071 (6)	0.0053 (6)	0.0024 (5)
O8	0.0345 (8)	0.0344 (9)	0.0481 (8)	0.0002 (6)	−0.0106 (6)	0.0082 (6)
N1	0.0266 (8)	0.0261 (8)	0.0278 (7)	−0.0022 (6)	−0.0003 (6)	−0.0002 (5)
N2	0.0240 (8)	0.0267 (9)	0.0292 (7)	−0.0024 (6)	0.0008 (6)	0.0019 (5)
N3	0.0283 (8)	0.0256 (9)	0.0259 (7)	0.0016 (6)	−0.0011 (6)	0.0000 (5)
N4	0.0272 (8)	0.0292 (9)	0.0289 (7)	0.0003 (6)	0.0034 (6)	−0.0003 (5)
N5	0.0253 (8)	0.0265 (9)	0.0291 (7)	0.0000 (6)	−0.0001 (6)	−0.0001 (5)
N6	0.0251 (8)	0.0228 (8)	0.0321 (7)	−0.0006 (5)	−0.0007 (6)	−0.0003 (5)
N7	0.0290 (8)	0.0289 (9)	0.0270 (7)	0.0016 (6)	0.0016 (6)	0.0023 (5)
N8	0.0296 (8)	0.0246 (9)	0.0299 (7)	−0.0004 (6)	0.0026 (6)	0.0001 (5)
C1	0.0238 (9)	0.0229 (9)	0.0263 (8)	−0.0003 (6)	0.0016 (6)	0.0010 (6)
C2	0.0251 (9)	0.0203 (9)	0.0248 (7)	−0.0007 (6)	0.0011 (6)	0.0017 (5)
C3	0.0238 (9)	0.0237 (9)	0.0254 (8)	−0.0004 (6)	0.0010 (6)	−0.0001 (6)
C4	0.0257 (9)	0.0224 (10)	0.0238 (7)	−0.0005 (6)	0.0007 (6)	0.0008 (5)
C5	0.0227 (9)	0.0237 (9)	0.0239 (7)	0.0014 (6)	0.0003 (6)	−0.0003 (5)
C6	0.0234 (8)	0.0212 (9)	0.0261 (8)	0.0000 (6)	−0.0003 (6)	0.0003 (5)
O1W	0.0296 (8)	0.0383 (9)	0.0312 (7)	−0.0018 (6)	−0.0023 (5)	−0.0008 (5)
O2W	0.0308 (8)	0.0362 (9)	0.0484 (8)	0.0016 (6)	−0.0038 (6)	−0.0076 (6)
O3W	0.0344 (8)	0.0396 (9)	0.0353 (7)	−0.0019 (6)	−0.0040 (6)	−0.0034 (5)
O4W	0.0351 (8)	0.0388 (9)	0.0344 (7)	−0.0054 (6)	−0.0034 (6)	0.0024 (6)

Geometric parameters (Å, º) top

O1—N3	1.2343 (19)	N6—C6	1.334 (2)
O2—N3	1.222 (2)	N7—C4	1.432 (2)
O3—N4	1.229 (2)	N8—C6	1.445 (2)
O4—N4	1.226 (2)	C1—C2	1.382 (2)
O5—N7	1.231 (2)	C2—C3	1.403 (2)
O6—N7	1.229 (2)	C2—C5	1.461 (2)
O7—N8	1.228 (2)	C4—C5	1.387 (2)
O8—N8	1.228 (2)	C5—C6	1.399 (2)
N1—N2	1.340 (2)	O1W—H1	0.87 (2)
N1—C1	1.342 (2)	O1W—H2	0.87 (2)
N1—H1N	0.96 (2)	O2W—H3	0.87 (2)
N2—C3	1.335 (2)	O2W—H4	0.88 (2)
N3—C1	1.436 (2)	O3W—H5	0.86 (2)
N4—C3	1.438 (2)	O3W—H6	0.88 (2)
N5—N6	1.337 (2)	O4W—H7	0.88 (2)
N5—C4	1.342 (2)	O4W—H8	0.88 (2)
N5—H2N	0.97 (2)

N2—N1—C1	111.34 (14)	N1—C1—N3	120.54 (15)
N2—N1—H1N	120.4 (17)	C2—C1—N3	129.62 (16)
C1—N1—H1N	127.9 (17)	C1—C2—C3	100.85 (15)
C3—N2—N1	103.74 (14)	C1—C2—C5	128.86 (16)
O2—N3—O1	125.27 (16)	C3—C2—C5	130.27 (15)
O2—N3—C1	118.00 (15)	N2—C3—C2	114.24 (15)
O1—N3—C1	116.74 (15)	N2—C3—N4	118.40 (16)
O4—N4—O3	123.93 (16)	C2—C3—N4	127.34 (16)
O4—N4—C3	117.35 (16)	N5—C4—C5	110.10 (16)
O3—N4—C3	118.71 (16)	N5—C4—N7	120.07 (16)
N6—N5—C4	110.35 (15)	C5—C4—N7	129.82 (17)
N6—N5—H2N	125.7 (19)	C4—C5—C6	101.07 (15)
C4—N5—H2N	123 (2)	C4—C5—C2	128.37 (16)
C6—N6—N5	105.11 (15)	C6—C5—C2	130.56 (16)
O6—N7—O5	124.88 (17)	N6—C6—C5	113.37 (15)
O6—N7—C4	117.78 (16)	N6—C6—N8	118.48 (16)
O5—N7—C4	117.33 (16)	C5—C6—N8	128.11 (16)
O7—N8—O8	125.24 (17)	H1—O1W—H2	105 (3)
O7—N8—C6	117.68 (16)	H3—O2W—H4	112 (3)
O8—N8—C6	117.09 (16)	H5—O3W—H6	105 (4)
N1—C1—C2	109.82 (15)	H7—O4W—H8	105 (3)

C1—N1—N2—C3	1.0 (2)	N6—N5—C4—N7	178.71 (14)
C4—N5—N6—C6	−0.10 (19)	O6—N7—C4—N5	−176.65 (16)
N2—N1—C1—C2	−0.5 (2)	O5—N7—C4—N5	3.7 (2)
N2—N1—C1—N3	−178.74 (15)	O6—N7—C4—C5	1.7 (3)
O2—N3—C1—N1	−168.07 (16)	O5—N7—C4—C5	−177.98 (18)
O1—N3—C1—N1	12.1 (2)	N5—C4—C5—C6	−0.02 (19)
O2—N3—C1—C2	14.1 (3)	N7—C4—C5—C6	−178.48 (17)
O1—N3—C1—C2	−165.77 (18)	N5—C4—C5—C2	179.92 (16)
N1—C1—C2—C3	−0.23 (19)	N7—C4—C5—C2	1.5 (3)
N3—C1—C2—C3	177.82 (18)	C1—C2—C5—C4	112.2 (2)
N1—C1—C2—C5	−178.66 (17)	C3—C2—C5—C4	−65.7 (3)
N3—C1—C2—C5	−0.6 (3)	C1—C2—C5—C6	−67.8 (3)
N1—N2—C3—C2	−1.2 (2)	C3—C2—C5—C6	114.2 (2)
N1—N2—C3—N4	−179.43 (16)	N5—N6—C6—C5	0.1 (2)
C1—C2—C3—N2	0.9 (2)	N5—N6—C6—N8	−177.89 (14)
C5—C2—C3—N2	179.30 (18)	C4—C5—C6—N6	−0.04 (19)
C1—C2—C3—N4	178.95 (18)	C2—C5—C6—N6	−179.98 (17)
C5—C2—C3—N4	−2.7 (3)	C4—C5—C6—N8	177.70 (17)
O4—N4—C3—N2	−179.33 (17)	C2—C5—C6—N8	−2.2 (3)
O3—N4—C3—N2	−0.2 (3)	O7—N8—C6—N6	1.3 (2)
O4—N4—C3—C2	2.7 (3)	O8—N8—C6—N6	−179.11 (16)
O3—N4—C3—C2	−178.14 (18)	O7—N8—C6—C5	−176.33 (17)
N6—N5—C4—C5	0.1 (2)	O8—N8—C6—C5	3.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1W	0.96 (2)	1.68 (2)	2.634 (2)	177 (3)
N5—H2N···O4Wⁱ	0.97 (2)	1.76 (2)	2.723 (2)	172 (3)
O1W—H1···O3W	0.87 (2)	2.00 (2)	2.866 (2)	178 (3)
O1W—H2···O2W	0.87 (2)	1.97 (2)	2.771 (2)	153 (3)
O2W—H3···N6ⁱⁱ	0.87 (2)	2.10 (2)	2.942 (2)	164 (3)
O2W—H4···O4Wⁱⁱⁱ	0.88 (2)	2.07 (2)	2.939 (2)	168 (3)
O3W—H5···O3^iv	0.86 (2)	2.31 (3)	3.116 (2)	156 (4)
O3W—H6···O2Wⁱⁱⁱ	0.88 (2)	1.90 (2)	2.766 (2)	170 (3)
O4W—H7···O3W	0.88 (2)	1.92 (2)	2.779 (2)	166 (3)
O4W—H8···O4^v	0.88 (2)	2.62 (4)	3.136 (2)	118 (3)
O4W—H8···O6^iv	0.88 (2)	2.39 (4)	3.051 (2)	132 (4)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x+1/2, y+1/2, z; (iv) x, −y+3/2, z+1/2; (v) x, −y+1/2, z+1/2.

3,3',5,5'-Tetranitro-4,4'-bipyrazole pentahydrate (2) top

Crystal data top

C₆H₂N₈O₈·5H₂O	F(000) = 832
M_r = 404.24	D_x = 1.726 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54186 Å
a = 11.2164 (5) Å	Cell parameters from 14313 reflections
b = 20.8114 (6) Å	θ = 3.9–80.1°
c = 6.6646 (3) Å	µ = 1.51 mm⁻¹
β = 90.435 (4)°	T = 183 K
V = 1555.67 (11) Å³	Needle, colorless
Z = 4	0.09 × 0.07 × 0.03 mm

Data collection top

STOE STADIVARI diffractometer	3321 independent reflections
Radiation source: GeniX 3D HF Cu	2619 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.041
Detector resolution: 5.81 pixels mm^-1	θ_max = 79.5°, θ_min = 3.9°
rotation method, ω scans	h = −13→14
Absorption correction: multi-scan (LANA; Koziskova et al., 2016)	k = −9→25
T_min = 0.787, T_max = 0.963	l = −8→8
14058 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: difference Fourier map
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0939P)²] where P = (F_o² + 2F_c²)/3
3321 reflections	(Δ/σ)_max < 0.001
296 parameters	Δρ_max = 0.42 e Å⁻³
53 restraints	Δρ_min = −0.32 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.28035 (12)	−0.04718 (6)	0.3996 (2)	0.0386 (3)
O2	0.13306 (12)	−0.01590 (6)	0.5861 (2)	0.0392 (3)
O3	0.37077 (12)	0.25979 (6)	0.3829 (2)	0.0403 (3)
O4	0.19788 (12)	0.25621 (6)	0.5233 (2)	0.0387 (3)
O5	−0.13642 (12)	0.21076 (8)	0.3560 (2)	0.0467 (4)
O6	0.03913 (12)	0.18784 (7)	0.2445 (2)	0.0399 (3)
O7	0.07786 (14)	0.04766 (7)	1.1095 (2)	0.0438 (4)
O8	0.23648 (12)	0.07031 (7)	0.9392 (2)	0.0405 (3)
N1	0.36281 (13)	0.07172 (7)	0.3696 (2)	0.0280 (3)
N2	0.38173 (13)	0.13466 (7)	0.3548 (2)	0.0283 (3)
N3	0.22147 (13)	−0.00586 (7)	0.4864 (2)	0.0304 (3)
N4	0.28528 (13)	0.23088 (7)	0.4509 (2)	0.0296 (3)
N5	−0.09369 (13)	0.15151 (7)	0.7006 (2)	0.0286 (3)
N6	−0.05416 (14)	0.11939 (7)	0.8599 (2)	0.0308 (3)
N7	−0.03690 (13)	0.18720 (7)	0.3731 (2)	0.0307 (3)
N8	0.12899 (14)	0.07156 (7)	0.9660 (2)	0.0318 (3)
C1	0.26111 (14)	0.05963 (7)	0.4645 (2)	0.0265 (3)
C2	0.20628 (15)	0.11677 (7)	0.5198 (2)	0.0259 (3)
C3	0.28840 (14)	0.16143 (8)	0.4436 (2)	0.0263 (3)
C4	−0.00963 (14)	0.15605 (8)	0.5601 (3)	0.0267 (3)
C5	0.09402 (15)	0.12615 (7)	0.6253 (2)	0.0257 (3)
C6	0.05760 (15)	0.10474 (8)	0.8161 (2)	0.0278 (3)
O1W	0.54652 (12)	0.00552 (6)	0.2491 (2)	0.0359 (3)
O3W	0.61658 (12)	0.18711 (6)	0.2917 (2)	0.0379 (3)
O2W	0.71826 (17)	0.08688 (8)	0.0706 (3)	0.0375 (4)	0.86
O2WA	0.7582 (16)	0.0942 (9)	0.123 (3)	0.059 (4)*	0.14
H3A	0.787930	0.070453	0.214496	0.089*	0.14
H4A	0.812770	0.103103	0.039756	0.089*	0.14
O4W	0.67352 (12)	0.31146 (6)	0.1914 (2)	0.0356 (3)
O5W	0.49162 (15)	0.38334 (7)	0.3636 (3)	0.0486 (4)
H3	0.7943 (17)	0.0863 (18)	0.042 (5)	0.058 (10)*	0.86
H4	0.685 (3)	0.088 (2)	−0.041 (4)	0.098 (15)*	0.86
H1	0.603 (2)	0.0235 (11)	0.179 (4)	0.046 (7)*
H2	0.540 (3)	−0.0326 (10)	0.202 (4)	0.071 (10)*
H5	0.5436 (16)	0.1760 (12)	0.283 (4)	0.044 (7)*
H6	0.6573 (19)	0.1615 (11)	0.226 (4)	0.043 (6)*
H7	0.661 (2)	0.3132 (13)	0.062 (3)	0.053 (8)*
H8	0.658 (3)	0.2735 (10)	0.228 (4)	0.063 (8)*
H9	0.5443 (19)	0.3606 (13)	0.306 (4)	0.070 (9)*
H10	0.434 (2)	0.3591 (14)	0.402 (5)	0.074 (10)*
H1N	0.423 (2)	0.0455 (13)	0.328 (4)	0.048 (7)*
H2N	−0.1678 (19)	0.1639 (11)	0.697 (3)	0.034 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0394 (7)	0.0202 (6)	0.0562 (8)	0.0021 (5)	0.0040 (6)	−0.0097 (5)
O2	0.0367 (7)	0.0237 (7)	0.0575 (8)	−0.0042 (5)	0.0111 (6)	0.0005 (5)
O3	0.0370 (7)	0.0225 (7)	0.0616 (9)	−0.0065 (5)	0.0125 (6)	−0.0006 (5)
O4	0.0366 (7)	0.0219 (6)	0.0577 (8)	0.0029 (5)	0.0114 (6)	−0.0038 (5)
O5	0.0273 (7)	0.0508 (9)	0.0620 (9)	0.0069 (6)	0.0011 (6)	0.0231 (7)
O6	0.0334 (7)	0.0463 (8)	0.0401 (7)	0.0019 (6)	0.0057 (5)	0.0096 (6)
O7	0.0470 (8)	0.0434 (8)	0.0409 (7)	−0.0028 (6)	0.0021 (6)	0.0133 (6)
O8	0.0334 (7)	0.0438 (8)	0.0445 (7)	0.0067 (6)	−0.0006 (5)	0.0055 (6)
N1	0.0267 (7)	0.0191 (7)	0.0382 (7)	0.0014 (5)	0.0022 (5)	−0.0027 (5)
N2	0.0290 (7)	0.0189 (7)	0.0369 (7)	−0.0001 (5)	0.0010 (6)	−0.0005 (5)
N3	0.0303 (7)	0.0190 (7)	0.0419 (8)	0.0003 (5)	−0.0008 (6)	−0.0020 (5)
N4	0.0308 (7)	0.0190 (7)	0.0390 (7)	−0.0001 (5)	0.0021 (6)	−0.0012 (5)
N5	0.0252 (7)	0.0198 (7)	0.0408 (7)	0.0010 (5)	0.0049 (5)	0.0007 (5)
N6	0.0321 (8)	0.0232 (7)	0.0372 (7)	0.0000 (5)	0.0035 (6)	0.0012 (5)
N7	0.0249 (7)	0.0246 (7)	0.0425 (8)	−0.0025 (5)	0.0000 (6)	0.0055 (6)
N8	0.0365 (8)	0.0233 (7)	0.0358 (7)	0.0018 (6)	−0.0004 (6)	0.0002 (5)
C1	0.0270 (8)	0.0179 (8)	0.0346 (8)	−0.0003 (6)	0.0006 (6)	−0.0011 (6)
C2	0.0269 (8)	0.0187 (7)	0.0319 (7)	0.0011 (6)	−0.0009 (6)	−0.0010 (5)
C3	0.0269 (8)	0.0176 (8)	0.0343 (8)	0.0000 (6)	0.0011 (6)	−0.0016 (6)
C4	0.0257 (8)	0.0181 (8)	0.0364 (8)	−0.0008 (5)	0.0020 (6)	0.0009 (6)
C5	0.0258 (8)	0.0166 (7)	0.0347 (8)	−0.0012 (5)	0.0020 (6)	−0.0013 (5)
C6	0.0317 (8)	0.0190 (7)	0.0327 (8)	−0.0001 (6)	0.0012 (6)	0.0007 (6)
O1W	0.0340 (7)	0.0238 (7)	0.0500 (7)	0.0026 (5)	0.0070 (6)	−0.0027 (5)
O3W	0.0277 (7)	0.0249 (7)	0.0611 (9)	−0.0023 (5)	0.0034 (6)	−0.0020 (5)
O2W	0.0347 (9)	0.0337 (9)	0.0442 (10)	−0.0025 (7)	0.0040 (8)	0.0027 (7)
O4W	0.0305 (7)	0.0222 (7)	0.0542 (8)	−0.0005 (5)	0.0048 (5)	0.0046 (5)
O5W	0.0492 (9)	0.0228 (7)	0.0741 (11)	−0.0007 (6)	0.0115 (8)	0.0004 (6)

Geometric parameters (Å, º) top

O1—N3	1.2313 (19)	N8—C6	1.451 (2)
O2—N3	1.216 (2)	C1—C2	1.390 (2)
O3—N4	1.2221 (19)	C2—C3	1.406 (2)
O4—N4	1.2161 (19)	C2—C5	1.460 (2)
O5—N7	1.2236 (19)	C4—C5	1.386 (2)
O6—N7	1.2134 (19)	C5—C6	1.411 (2)
O7—N8	1.224 (2)	O1W—H1	0.872 (18)
O8—N8	1.220 (2)	O1W—H2	0.855 (19)
N1—N2	1.331 (2)	O3W—H5	0.852 (17)
N1—C1	1.332 (2)	O3W—H6	0.828 (17)
N1—H1N	0.92 (3)	O2W—H3	0.875 (19)
N2—C3	1.329 (2)	O2W—H4	0.83 (2)
N3—C1	1.441 (2)	O2WA—H3A	0.8500
N4—C3	1.447 (2)	O2WA—H4A	0.8500
N5—N6	1.328 (2)	O4W—H7	0.875 (17)
N5—C4	1.337 (2)	O4W—H8	0.845 (19)
N5—H2N	0.87 (2)	O5W—H9	0.851 (19)
N6—C6	1.325 (2)	O5W—H10	0.861 (19)
N7—C4	1.436 (2)

N2—N1—C1	111.01 (13)	C5—C4—N7	130.37 (15)
N2—N1—H1N	116.4 (17)	C4—C5—C6	100.17 (14)
C1—N1—H1N	132.1 (17)	C4—C5—C2	129.33 (15)
C3—N2—N1	104.66 (14)	C6—C5—C2	130.42 (15)
O2—N3—O1	125.39 (15)	N6—C6—C5	114.03 (15)
O2—N3—C1	118.13 (14)	N6—C6—N8	118.41 (15)
O1—N3—C1	116.48 (15)	C5—C6—N8	127.53 (15)
O4—N4—O3	124.81 (15)	H1—O1W—H2	105 (2)
O4—N4—C3	117.78 (14)	H5—O3W—H6	109 (2)
O3—N4—C3	117.40 (14)	O2WA—O2W—H3A	33.1
N6—N5—C4	111.26 (14)	O2WA—O2W—H4A	47.1
N6—N5—H2N	119.0 (15)	H3A—O2W—H4A	69.4
C4—N5—H2N	129.6 (14)	O2WA—O2W—H3	53 (2)
C6—N6—N5	104.48 (14)	H3A—O2W—H3	64.5
O6—N7—O5	125.14 (16)	H4A—O2W—H3	18.2
O6—N7—C4	118.13 (14)	O2WA—O2W—H4	149 (3)
O5—N7—C4	116.72 (15)	H3A—O2W—H4	161.5
O8—N8—O7	125.10 (16)	H4A—O2W—H4	103.8
O8—N8—C6	116.73 (15)	H3—O2W—H4	104 (3)
O7—N8—C6	118.17 (15)	O2W—O2WA—H3A	124.8
N1—C1—C2	110.28 (14)	O2W—O2WA—H4A	102.5
N1—C1—N3	119.50 (14)	H3A—O2WA—H4A	108.4
C2—C1—N3	130.14 (15)	O2W—O2WA—H3	86 (3)
C1—C2—C3	100.21 (14)	H3A—O2WA—H3	101.1
C1—C2—C5	128.84 (15)	H4A—O2WA—H3	28.3
C3—C2—C5	130.94 (14)	O2W—O2WA—H4	18 (2)
N2—C3—C2	113.84 (14)	H3A—O2WA—H4	138.6
N2—C3—N4	116.95 (14)	H4A—O2WA—H4	85.7
C2—C3—N4	129.21 (15)	H3—O2WA—H4	73 (3)
N5—C4—C5	110.06 (15)	H7—O4W—H8	107 (2)
N5—C4—N7	119.54 (15)	H9—O5W—H10	110 (2)

C1—N1—N2—C3	−0.03 (18)	N6—N5—C4—N7	177.78 (14)
C4—N5—N6—C6	0.81 (18)	O6—N7—C4—N5	−176.42 (15)
N2—N1—C1—C2	−0.29 (19)	O5—N7—C4—N5	3.1 (2)
N2—N1—C1—N3	176.78 (14)	O6—N7—C4—C5	1.5 (3)
O2—N3—C1—N1	174.75 (15)	O5—N7—C4—C5	−178.95 (17)
O1—N3—C1—N1	−6.0 (2)	N5—C4—C5—C6	0.08 (18)
O2—N3—C1—C2	−8.8 (3)	N7—C4—C5—C6	−178.03 (17)
O1—N3—C1—C2	170.46 (17)	N5—C4—C5—C2	177.08 (15)
N1—C1—C2—C3	0.46 (17)	N7—C4—C5—C2	−1.0 (3)
N3—C1—C2—C3	−176.22 (17)	C1—C2—C5—C4	−117.2 (2)
N1—C1—C2—C5	179.77 (16)	C3—C2—C5—C4	61.9 (3)
N3—C1—C2—C5	3.1 (3)	C1—C2—C5—C6	58.9 (3)
N1—N2—C3—C2	0.35 (19)	C3—C2—C5—C6	−122.0 (2)
N1—N2—C3—N4	179.72 (14)	N5—N6—C6—C5	−0.78 (19)
C1—C2—C3—N2	−0.50 (18)	N5—N6—C6—N8	177.12 (14)
C5—C2—C3—N2	−179.79 (16)	C4—C5—C6—N6	0.44 (19)
C1—C2—C3—N4	−179.78 (16)	C2—C5—C6—N6	−176.50 (15)
C5—C2—C3—N4	0.9 (3)	C4—C5—C6—N8	−177.23 (16)
O4—N4—C3—N2	176.67 (15)	C2—C5—C6—N8	5.8 (3)
O3—N4—C3—N2	−3.1 (2)	O8—N8—C6—N6	−165.51 (15)
O4—N4—C3—C2	−4.1 (3)	O7—N8—C6—N6	13.8 (2)
O3—N4—C3—C2	176.20 (17)	O8—N8—C6—C5	12.1 (3)
N6—N5—C4—C5	−0.57 (19)	O7—N8—C6—C5	−168.60 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1W	0.92 (3)	1.70 (3)	2.610 (2)	173 (3)
N5—H2N···O4Wⁱ	0.87 (2)	1.85 (2)	2.723 (2)	179 (2)
O1W—H1···O2W	0.87 (2)	1.99 (2)	2.833 (2)	163 (2)
O1W—H2···O5Wⁱⁱ	0.86 (2)	1.84 (2)	2.685 (2)	170 (3)
O2W—H3···N6ⁱⁱⁱ	0.88 (2)	2.21 (3)	3.000 (2)	151 (3)
O2W—H4···O5W^iv	0.83 (2)	2.33 (3)	2.949 (3)	131 (3)
O2W—H4···O1^v	0.83 (2)	2.57 (3)	3.241 (3)	139 (3)
O3W—H5···N2	0.85 (2)	2.07 (2)	2.885 (2)	160 (2)
O3W—H6···O2W	0.83 (2)	1.99 (2)	2.802 (2)	166 (2)
O4W—H7···O3W^iv	0.88 (2)	1.87 (2)	2.735 (2)	173 (2)
O4W—H8···O3W	0.85 (2)	1.91 (2)	2.749 (2)	176 (3)
O5W—H9···O4W	0.85 (2)	1.94 (2)	2.784 (2)	175 (3)
O5W—H10···O3	0.86 (2)	2.19 (3)	2.910 (2)	141 (3)
O5W—H10···O8^iv	0.86 (2)	2.67 (3)	3.065 (2)	109 (2)

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

Geometry of lone pair–π-hole interactions (Å, °) for (1) and (2) top

Compound	O-atom donor	Group	O···N	O···plane	φ
O···N (nitro)
(1)	O3	(C3/N4/O3/O4)ⁱⁱⁱ	3.031 (2)	2.8316 (16)	69.10 (3)
	O6	(C6/N8/O7/O8)^vii	3.002 (2)	2.8835 (18)	73.85 (3)
	O7	(C4/N7/O5/O6)^ix	3.008 (2)	2.8201 (19)	69.64 (4)
	O7	(C1/N3/O1/O2)^ix	3.277 (2)	3.098 (2)	70.98 (5)
	O7	(C6/N8/O7/O8)^viii	3.085 (2)	2.951 (2)	73.05 (5)
	O1w	(C1/N3/O1/O2)ⁱⁱⁱ	3.029 (2)	2.8845 (19)	72.23 (4)
(2)	O3	(C3/N4/O3/O4)^iv	3.034 (2)	2.9979 (16)	81.16 (2)
	O4	(C3/N4/O3/O4)^vii	3.019 (2)	2.9866 (16)	81.65 (2)
	O6	(C6/N8/O7/O8)^viii	3.217 (2)	2.911 (2)	64.81 (4)
	O7	(C1/N3/O1/O2)^ix	3.175 (2)	3.0653 (18)	74.89 (3)
	O1w	(C1/N3/O1/O2)^vi	3.132 (2)	2.9153 (19)	68.56 (4)

O···N(H) (ring)
(1)	O2	(N5/N6/C4/C5/C6)ⁱ	3.144 (2)	3.0726 (16)	77.77 (3)
	O5	(N5/N6/C4/C5/C6)^xiii	3.063 (2)	2.770 (3)	64.73 (5)
(2)	O1	(N5/N6/C4/C5/C6)^iv	3.087 (2)	2.738 (3)	62.49 (5)
	O5	(N5/N6/C4/C5/C6)^x	3.0857 (19)	2.781 (2)	64.32 (5)
	O8	(N1/N2/C1/C2/C3)^ix	3.190 (2)	3.1830 (19)	86.20 (4)

Notes: O···plane is a distance of the O-atom donor to the mean plane of the nitro (pyrazole) group and φ is an angle of the O···N axis to the plane of the nitro (pyrazole) group. [Symmetry codes for (1): (iii) -x+1/2, y+1/2, z; (vii) x, y+1, z; (viii) -x, -y, -z+1; (ix) x, y-1, z, (xiii) -x, y+1/2, -z+1/2. Symmetry codes for (2): (iv) x, -y+1/2, z?1/2; (vi) -x+1, -y, -z+1; (vii) x, -y+1/2, z+1/2; (viii) x, y, z-1; (ix) x, y, z+1; (x) -x, -y, -z+1.]

Number of the identified interactions per single H₂Tnbpz molecule adopted for different hydrate environments in the structures of anhydrate PITGEH, monohydrate PITGIL and high hydrates (1) and (2) top

Bond type	PITGEH	PITGIL	(1)	(2)
NH···N/N···HN	2	2	-	-
NH···O/O···HN	4	-	-	-
NH···Ow	-	1	2	2
N···HOw	-	1	2	2
O···HOw	-	2	3	4
N···O/O···N (NO₂)	8	4	7	6
N···O/O···N (ring)	10	10	4	6
O₂N···Ow	-	1	1	1
π···Ow	-	-	-	1
O(N)···π/π···O(N)	2	2	4	-
N···NO₂/O₂N···N	2	-	-	-
O···O (NO₂)^a	4	4	6	3

Note: (a) number of O···O contacts below 3.05 Å adopted by nitro groups.

Contributions of the different kinds of the contacts (%) to the Hirshfeld surfaces of individual organic molecules in anhydrate PITGEH, monohydrate PITGIL and high hydrates (1) and (2). top

Contacts	PITGEH	PITGIL	(1)	(2)
All···O,N	80.7	69.3	56.7	54.5
All···H	14.1	26.7	38.5	40.8

O···H/H···O	20.3	27.0	37.9	35.3
N···H/H···N	5.2	8.7	5.0	8.8
C···H/H···C	0.0	0.3	0.4	1.2
N···O/O···N	27.8	21.9	21.2	19.3
C···O/O···C	11.0	8.1	8.5	10.3
C···N/N···C	0.0	0.3	2.3	0.1
O···O	32.9	29.7	17.9	21.1
N···N	2.7	3.1	3.6	0.5
H···H	0.0	0.8	3.2	3.4

For the 2D plots for the principal contact, see Fig. 9.

Calculated interaction energies (kJ mol^-1). top

Path	Type^a	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
(1)
Org···Org^ix	A	6.19	-16.8	-3.2	-29.2	18.9	-33.9
Org···Orgⁱ	B	6.29	-16.8	-3.1	-27.0	16.8	-33.3
Org···Org^viii	C	8.30	-2.9	-1.2	-14.1	8.6	-10.9
Org···Org^x	D	6.86	1.3	-4.1	-28.1	19.2	-14.3
Org···Org^xi	E	8.71	-7.4	-1.6	-8.8	4.2	-14.1
Org···(O1w)	NH···OH₂	5.54	-82.2	-20.1	-7.9	85.0	-56.1
Org···(O4w)ⁱ	NH···OH₂	5.59	-62.8	-16.1	-6.9	56.8	-49.3
Org···(O2w)^vi	OH···N	5.90	-28.2	-4.7	-5.9	33.4	-17.8
Org···(O4w)^xii	OH···O	5.69	-12.0	-1.6	-5.9	11.1	-12.1
Org···(O3w)^xii	OH···O	5.09	0.4	-0.8	-4.1	3.0	-1.8
Org···(O1w)^x	H₂O···NO₂	4.50	-19.1	-4.1	-10.3	10.7	-25.5

(2)
Org···Org^iv	A	6.66	-17.1	-2.7	-23.2	14.3	-31.5
Org···Org^x	B	6.10	-18.8	-3.4	-25.6	12.5	-37.0
Org···Org^viii	C	6.33	-14.7	-2.9	-29.6	22.3	-29.8
Org···Org^xi	D	8.35	-2.8	-1.3	-12.0	5.1	-11.2
Org···(O1w)	NH···OH₂	5.56	-83.7	-20.6	-6.7	87.3	-55.7
Org···(O4w)ⁱ	NH···OH₂	5.61	-68.5	-17.5	-8.1	64.1	-52.9
Org···(O3w)	OH···N	5.72	-22.3	-5.0	-7.2	41.8	-7.8
Org···(O2w)^xii	OH···N	5.88	-11.9	-4.3	-6.5	24.1	-6.6
Org···(O4w)^xiii	OH···O	7.10	1.1	-0.4	-2.3	1.6	-0.1
Org···(O5w)	OH···O	6.77	-14.9	-2.1	-3.5	16.7	-10.0
Org···(O2w)^v	OH···O	6.21	-4.6	-0.8	-3.6	3.7	-6.3
Org···(O1w)^vi	H₂O···NO₂	4.43	-19.2	-3.6	-11.7	10.8	-26.4
Org···(O5w)^vii	H₂O···π	4.29	-4.2	-1.3	-7.2	3.2	-9.6

Interaction energies were calculated employing the CE-B3LYP/6-31G(d,p) functional/basis set combination. The scale factors used to determine E_tot: k_ele = 1.057, k_pol = 0.740, k_dis = 0.871, and k_rep = 0.618 (Mackenzie et al., 2017). (a) For details of the interaction modes in (1), see Fig. 10 and for details of the interaction modes in (2), see Fig. 11; R is a distance between centroids of the interacting molecules. Symmetry codes for (1): (i) -x, -y+1, -z+1; (vi) x-1/2, -y+1/2, -z+1; (viii) -x, -y, -z+1; (ix) x, y-1, z; (x) -x+1/2, y-1/2, z; (xi) -x, y-1/2, -z+1/2; (xii) x, -y+3/2, z-1/2; Symmetry codes for (2): (i) x-1, -y+1/2, z+1/2; (iv) x, -y+1/2, z-1/2; (v) -x+1, -y, -z; (vi) -x+1, -y, -z+1; (vii) x, -y+1/2, z+1/2; (viii) x, y, z-1; (x) -x, -y, -z+1; (xi) -x, -y, -z+2; (xii) x-1, y, z+1; (xiii) x-1, y, z.

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Two metastable high hydrates of energetic material 3,3′,5,5′-tetra­nitro-4,4′-bi­pyrazole

Supporting information

Two metastable high hydrates of energetic material 3,3′,5,5′-tetranitro-4,4′-bipyrazole