3,4-Dinitro-1H-pyrazole benzene 0.25-solvate.

The asymmetric unit of the title compound, 4C(3)H(2)N(2)O(4)·C(6)H(6), contains two independent dinitro-pyrazole mol-ecules and half a benzene solvent mol-ecule, which lies on a crystallographic inversion centre. Each pyrazole ring is essentially planar (mean deviations of 0.009 and 0.002 Å), with the two nitro groups rotated out of the plane [dihedral angles = 11.7 (2)/31.1 (1) and 21.8 (2)/25.0 (1)° for the two mol-ecules].

Related literature

For the biological properties of polynitro­pyrazoles, see: Alejandre-Durán et al. (1986 ▶); Grigor’ev et al. (1998) ▶; Xuan et al. (1999 ▶). For their detonation properties, see: Keshavarz et al. (2007 ▶); Zaitsev et al. (2009) ▶. For the synthesis, see: Katritzky et al. (2005 ▶).

Experimental

Crystal data

2C3H2N4O4·0.5C6H6

M = 355.23

Monoclinic,

a = 7.4579 (15) Å

b = 9.787 (2) Å

c = 19.534 (4) Å

β = 94.87 (3)°

V = 1420.7 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 123 K

0.30 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.957, T max = 0.971

3454 measured reflections

3256 independent reflections

1267 reflections with I > 2σ(I)

R int = 0.084

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.105

S = 0.92

3256 reflections

235 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.33 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2000 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku, 2000 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015996/zs2110sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015996/zs2110Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811015996/zs2110Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C3H2N4O4·0.5C6H6	F(000) = 724
Mr = 355.23	Dx = 1.661 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3256 reflections
a = 7.4579 (15) Å	θ = 2.1–27.5°
b = 9.787 (2) Å	µ = 0.15 mm−1
c = 19.534 (4) Å	T = 123 K
β = 94.87 (3)°	Block, colorless
V = 1420.7 (5) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	3256 independent reflections
Radiation source: fine-focus sealed tube	1267 reflections with I > 2σ(I)
graphite	Rint = 0.084
Detector resolution: 10.00 pixels mm-1	θmax = 27.5°, θmin = 2.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.957, Tmax = 0.971	l = −25→25
3256 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
S = 0.92	(Δ/σ)max < 0.001
3256 reflections	Δρmax = 0.27 e Å−3
235 parameters	Δρmin = −0.33 e Å−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (6)

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.9887 (4)	0.1907 (3)	0.19586 (16)	0.0327 (8)
C2	1.1357 (4)	0.1088 (4)	0.19047 (17)	0.0420 (9)
H2	1.2585	0.1359	0.1953	0.050*
C3	0.8410 (4)	0.1014 (3)	0.18468 (16)	0.0289 (8)
C4	0.5086 (4)	0.5510 (3)	0.09984 (17)	0.0387 (9)
C5	0.3685 (4)	0.6383 (3)	0.11466 (16)	0.0344 (8)
C6	0.6606 (4)	0.6268 (4)	0.10959 (18)	0.0538 (11)
H6	0.7801	0.5975	0.1045	0.065*
C7	1.1648 (8)	0.0615 (7)	0.0108 (2)	0.0902 (16)
H7	1.2790	0.1045	0.0180	0.108*
C8	1.0067 (11)	0.1372 (5)	0.0150 (2)	0.0921 (19)
H8	1.0132	0.2318	0.0258	0.111*
C9	0.8469 (8)	0.0760 (7)	0.0040 (2)	0.0880 (17)
H9	0.7399	0.1279	0.0063	0.106*
N1	0.9970 (4)	0.3361 (3)	0.20565 (14)	0.0409 (7)
N2	0.6477 (3)	0.1259 (3)	0.18791 (15)	0.0431 (8)
N3	1.0721 (3)	−0.0172 (3)	0.17704 (15)	0.0415 (8)
N4	0.8896 (3)	−0.0246 (3)	0.17325 (13)	0.0364 (7)
N5	0.5049 (4)	0.4072 (3)	0.08235 (17)	0.0540 (9)
N6	0.1748 (3)	0.6197 (3)	0.10954 (15)	0.0422 (7)
N7	0.6079 (4)	0.7520 (4)	0.12796 (17)	0.0533 (9)
N8	0.4295 (3)	0.7621 (3)	0.13217 (14)	0.0455 (8)
O1	1.1467 (3)	0.3853 (3)	0.22096 (13)	0.0593 (8)
O2	0.8580 (3)	0.4027 (3)	0.19682 (14)	0.0638 (8)
O3	0.6020 (3)	0.2140 (3)	0.22658 (13)	0.0616 (8)
O4	0.5471 (3)	0.0518 (3)	0.15166 (14)	0.0585 (8)
O5	0.6340 (4)	0.3642 (3)	0.05424 (15)	0.0840 (10)
O6	0.3762 (4)	0.3390 (3)	0.09674 (17)	0.0864 (10)
O7	0.1130 (3)	0.5307 (3)	0.07052 (13)	0.0636 (8)
O8	0.0861 (3)	0.6953 (3)	0.14284 (14)	0.0631 (8)
H7A	0.684 (5)	0.820 (4)	0.127 (3)	0.17 (2)*
H3	1.138 (3)	−0.091 (2)	0.1735 (17)	0.052 (11)*

	U11	U22	U33	U12	U13	U23
C1	0.0275 (18)	0.0321 (19)	0.038 (2)	−0.0016 (15)	0.0019 (15)	0.0026 (17)
C2	0.0259 (18)	0.042 (2)	0.057 (2)	0.0014 (17)	−0.0032 (16)	−0.004 (2)
C3	0.0226 (16)	0.0290 (18)	0.0343 (18)	0.0030 (14)	−0.0015 (14)	0.0029 (16)
C4	0.0326 (19)	0.039 (2)	0.044 (2)	0.0008 (17)	−0.0042 (15)	−0.001 (2)
C5	0.0306 (18)	0.034 (2)	0.038 (2)	−0.0019 (16)	−0.0017 (14)	−0.0027 (18)
C6	0.0279 (19)	0.070 (3)	0.063 (3)	−0.001 (2)	−0.0027 (18)	0.013 (3)
C7	0.112 (5)	0.101 (5)	0.056 (3)	−0.015 (4)	−0.007 (3)	0.007 (3)
C8	0.177 (6)	0.047 (3)	0.047 (3)	−0.006 (4)	−0.019 (4)	−0.001 (3)
C9	0.127 (5)	0.089 (5)	0.046 (3)	0.043 (4)	−0.004 (3)	−0.002 (3)
N1	0.0403 (18)	0.0392 (19)	0.0422 (18)	−0.0050 (15)	−0.0027 (14)	−0.0002 (16)
N2	0.0299 (16)	0.0406 (19)	0.058 (2)	−0.0009 (15)	−0.0004 (15)	0.0044 (18)
N3	0.0257 (15)	0.042 (2)	0.056 (2)	0.0115 (15)	−0.0010 (13)	−0.0006 (17)
N4	0.0232 (14)	0.0343 (17)	0.0511 (18)	0.0016 (12)	0.0007 (12)	0.0042 (15)
N5	0.051 (2)	0.048 (2)	0.061 (2)	0.0108 (18)	−0.0078 (17)	−0.0066 (19)
N6	0.0311 (16)	0.0382 (18)	0.056 (2)	−0.0012 (15)	−0.0003 (14)	0.0049 (18)
N7	0.045 (2)	0.049 (2)	0.063 (2)	−0.0178 (18)	−0.0099 (16)	0.0041 (19)
N8	0.0431 (18)	0.0332 (18)	0.059 (2)	−0.0049 (15)	−0.0009 (15)	−0.0002 (17)
O1	0.0446 (15)	0.0533 (17)	0.0775 (19)	−0.0211 (14)	−0.0100 (13)	−0.0038 (16)
O2	0.0497 (15)	0.0403 (16)	0.099 (2)	0.0119 (13)	−0.0072 (15)	0.0013 (16)
O3	0.0338 (14)	0.0637 (19)	0.089 (2)	0.0096 (14)	0.0136 (13)	−0.0253 (18)
O4	0.0272 (13)	0.0502 (17)	0.096 (2)	−0.0024 (12)	−0.0094 (12)	−0.0134 (17)
O5	0.071 (2)	0.078 (2)	0.105 (2)	0.0246 (17)	0.0199 (17)	−0.030 (2)
O6	0.082 (2)	0.0369 (18)	0.141 (3)	−0.0096 (16)	0.015 (2)	−0.0024 (19)
O7	0.0371 (14)	0.066 (2)	0.085 (2)	−0.0130 (14)	−0.0100 (13)	−0.0203 (18)
O8	0.0405 (15)	0.0539 (18)	0.098 (2)	0.0059 (14)	0.0231 (14)	−0.0095 (18)

C1—C2	1.370 (4)	C8—C9	1.335 (7)
C1—C3	1.409 (4)	C8—H8	0.9500
C1—N1	1.436 (4)	C9—C7i	1.377 (7)
C2—N3	1.339 (4)	C9—H9	0.9500
C2—H2	0.9500	N1—O2	1.224 (3)
C3—N4	1.310 (4)	N1—O1	1.229 (3)
C3—N2	1.468 (3)	N2—O3	1.214 (3)
C4—C6	1.355 (4)	N2—O4	1.225 (3)
C4—C5	1.398 (4)	N3—N4	1.359 (3)
C4—N5	1.448 (4)	N3—H3	0.876 (10)
C5—N8	1.328 (4)	N5—O6	1.221 (4)
C5—N6	1.451 (4)	N5—O5	1.223 (4)
C6—N7	1.344 (4)	N6—O8	1.217 (3)
C6—H6	0.9500	N6—O7	1.222 (3)
C7—C9i	1.377 (7)	N7—N8	1.344 (4)
C7—C8	1.401 (7)	N7—H7A	0.878 (10)
C7—H7	0.9500
C2—C1—C3	104.2 (3)	C8—C9—C7i	120.8 (5)
C2—C1—N1	124.3 (3)	C8—C9—H9	119.6
C3—C1—N1	131.3 (3)	C7i—C9—H9	119.6
N3—C2—C1	106.3 (3)	O2—N1—O1	124.5 (3)
N3—C2—H2	126.8	O2—N1—C1	118.8 (3)
C1—C2—H2	126.8	O1—N1—C1	116.6 (3)
N4—C3—C1	112.7 (3)	O3—N2—O4	126.1 (3)
N4—C3—N2	116.7 (3)	O3—N2—C3	118.1 (3)
C1—C3—N2	130.5 (3)	O4—N2—C3	115.7 (3)
C6—C4—C5	105.5 (3)	C2—N3—N4	113.3 (3)
C6—C4—N5	124.4 (3)	C2—N3—H3	125 (2)
C5—C4—N5	130.0 (3)	N4—N3—H3	121 (2)
N8—C5—C4	111.4 (3)	C3—N4—N3	103.4 (3)
N8—C5—N6	116.7 (3)	O6—N5—O5	125.4 (3)
C4—C5—N6	131.7 (3)	O6—N5—C4	118.5 (3)
N7—C6—C4	106.1 (3)	O5—N5—C4	116.1 (3)
N7—C6—H6	127.0	O8—N6—O7	125.0 (3)
C4—C6—H6	127.0	O8—N6—C5	118.0 (3)
C9i—C7—C8	119.4 (5)	O7—N6—C5	117.0 (3)
C9i—C7—H7	120.3	N8—N7—C6	113.4 (3)
C8—C7—H7	120.3	N8—N7—H7A	126 (3)
C9—C8—C7	119.8 (5)	C6—N7—H7A	119 (3)
C9—C8—H8	120.1	C5—N8—N7	103.7 (3)
C7—C8—H8	120.1
C3—C1—C2—N3	0.1 (4)	C1—C3—N2—O3	−29.0 (5)
N1—C1—C2—N3	−175.8 (3)	N4—C3—N2—O4	−31.6 (4)
C2—C1—C3—N4	−0.1 (4)	C1—C3—N2—O4	152.5 (3)
N1—C1—C3—N4	175.4 (3)	C1—C2—N3—N4	−0.1 (4)
C2—C1—C3—N2	175.9 (3)	C1—C3—N4—N3	0.0 (4)
N1—C1—C3—N2	−8.6 (6)	N2—C3—N4—N3	−176.6 (3)
C6—C4—C5—N8	0.5 (4)	C2—N3—N4—C3	0.1 (4)
N5—C4—C5—N8	176.4 (4)	C6—C4—N5—O6	155.9 (4)
C6—C4—C5—N6	175.6 (3)	C5—C4—N5—O6	−19.3 (6)
N5—C4—C5—N6	−8.5 (6)	C6—C4—N5—O5	−23.7 (5)
C5—C4—C6—N7	−1.0 (4)	C5—C4—N5—O5	161.0 (3)
N5—C4—C6—N7	−177.2 (3)	N8—C5—N6—O8	−25.2 (4)
C9i—C7—C8—C9	−0.8 (8)	C4—C5—N6—O8	159.9 (3)
C7—C8—C9—C7i	0.8 (9)	N8—C5—N6—O7	153.1 (3)
C2—C1—N1—O2	166.3 (3)	C4—C5—N6—O7	−21.8 (5)
C3—C1—N1—O2	−8.5 (6)	C4—C6—N7—N8	1.2 (4)
C2—C1—N1—O1	−12.0 (5)	C4—C5—N8—N7	0.3 (4)
C3—C1—N1—O1	173.2 (3)	N6—C5—N8—N7	−175.7 (3)
N4—C3—N2—O3	146.8 (3)	C6—N7—N8—C5	−0.9 (4)