1-(2,4-Dinitro­phen­yl)-3,3-dinitro­azetidine

Yan, B.; Ma, H.-X.; Hu, Y.; Guan, Y.-L.; Song, J.-R.

doi:10.1107/S1600536809049861

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3215

doi:10.1107/S1600536809049861

Open

access

1-(2,4-Dinitrophenyl)-3,3-dinitroazetidine

Biao Yan,^a,^b Hai-Xia Ma,^b ^* Yin Hu,^b Yu-Lei Guan ^b and Ji-Rong Song ^b

^aSchool of Chemistry and Chemical Engineering, Yulin University, Yulin 719000 Shaanxi, People's Republic of China, and ^bSchool of Chemical Engineering, Northwest University, Xi'an 710069 Shaanxi, People's Republic of China
^*Correspondence e-mail: donghuhai@qq.com

(Received 18 November 2009; accepted 20 November 2009; online 25 November 2009)

In the title compound, C₉H₇N₅O₈, the dihedral angle between the mean plane of the azetidine ring and that of the benzene ring is 26.1 (1)°; the planes of the two nitro groups of the azetidine ring are aligned at 88.7 (1)°.

Related literature

Highly nitrated small-ring heterocycles are good candidates for energetic materials because of the increased performance from the additional energy release upon opening of the strained ring system during decomposition, see: Frumkin et al. (1999 ). Azetidine-based explosives, such as 1,3,3-trinitroazetidine (TNAZ) demonstrate excellent performance, see: Archibald et al., (1990 ); Hiskey & Coburn (1994a ,b ). The title compound is a derivative of 3,3-dinitroazetidine (DNAZ) (Hiskey et al., 1992 , 1993 ), which is a derivative of TNAZ. For the use of DNAZ in the preparation of a variety of solid energetic compounds, see: Ma et al. (2009a ,b ,c ); Gao et al. (2009 ).

Experimental

Crystal data

C₉H₇N₅O₈
M_r = 313.20
Monoclinic, P 2₁ /n
a = 8.113 (2) Å
b = 10.676 (3) Å
c = 14.398 (4) Å
β = 104.681 (4)°
V = 1206.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.31 × 0.26 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
5860 measured reflections
2140 independent reflections
1670 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.118
S = 1.20
2140 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049861/ng2691sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049861/ng2691Isup2.hkl

checkCIF report

Comment top

Highly nitrated small-ring heterocycles are good candidates for energetic materials because of the increased performance from the additional energy release upon opening of the strained ring system during decomposition (Frumkin et al., 1999). Azetidine-based explosives, such as 1,3,3-trinitroazetidine (TNAZ) (Archibald et al., 1990; Hiskey et al., 1994a,b) demonstrate excellent performance partly because of the high strain associated with the four-membered ring. As one of the important derivates of TNAZ, 3,3-dinitroazetidine (DNAZ) (Hiskey et al., 1992; Hiskey et al., 1993) can prepare a variety of solid energetic compounds (Ma et al., 2009a,b,c; Gao et al., 2009). The title compound (I) is a DNAZ derivates. The dihedral angle between the azetidine ring and benzene ring is 26.1° and the planes of two nitryl of azetidine ring is 88.7°. There are no important intermolecular contacts in the crystal structure.

Related literature top

Highly nitrated small-ring heterocycles are good candidates for energetic materials because of the increased performance from the additional energy release upon opening of the strained ring system during decomposition, see: Frumkin et al. (1999). Azetidine-based explosives, such as 1,3,3-trinitroazetidine (TNAZ) (Archibald et al., 1990; Hiskey & Coburn, 1994a,b) demonstrate excellent performance partly because of the high strain associated with the four-membered ring. The title compound is a derivative of 3,3-dinitroazetidine (DNAZ) (Hiskey et al., 1992, 1993), which is a derivative of TNAZ. For the use of DNAZ in the preparation of a variety of solid energetic compounds, see: Ma et al. (2009a,b,c); Gao et al. (2009).

Experimental top

A solution of DNAZ (0.2353 g, 1.6 mmol), 2,4-dinitrochlorobenzene (0.33 ml, 1.6 mmol), and NaHCO₃ (0.28 g, 3.2 mmol) in dichloromethane (30.0 ml) was stirred under reflux for 20 h. The reaction mixture was concentrated in vacuo, water (30 ml) was added, and the unstable mixture was extracted rapidly with dichloromethane (3 * 15 ml). The combined extracts were dried (MgSO₄,), the solvent was concentrated in vacuo, and ethanol (20 ml) was added, and the residue was filtrated to give the yellow compound in 30% yield. Crystals were obtained from dichloromethane, by slow evaporation at room temperature. Elemental analysis calculated for C₉H₇N₅O₈: C 34.61, N 22.36, H 2.253%; found: C 34.61, N 22.22, H 2.249%. IR (KBr, cm^-1): 3100.29, 1585.18, 1526.85, 1335.18, 1304.76, 869.25, 820.72.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELX97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as spheres of arbitrary radius.

1-(2,4-Dinitrophenyl)-3,3-dinitroazetidine top

Crystal data top

C₉H₇N₅O₈	F(000) = 640
M_r = 313.20	D_x = 1.724 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1904 reflections
a = 8.113 (2) Å	θ = 2.4–26.0°
b = 10.676 (3) Å	µ = 0.15 mm⁻¹
c = 14.398 (4) Å	T = 293 K
β = 104.681 (4)°	Block, yellow
V = 1206.3 (6) Å³	0.31 × 0.26 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	1670 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.1°, θ_min = 2.4°
ϕ and ω scans	h = −9→9
5860 measured reflections	k = −11→12
2140 independent reflections	l = −17→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.063P)² + 0.0921P] where P = (F_o² + 2F_c²)/3
2140 reflections	(Δ/σ)_max = 0.028
199 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₇N₅O₈	V = 1206.3 (6) Å³
M_r = 313.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.113 (2) Å	µ = 0.15 mm⁻¹
b = 10.676 (3) Å	T = 293 K
c = 14.398 (4) Å	0.31 × 0.26 × 0.20 mm
β = 104.681 (4)°

Data collection top

Bruker APEXII diffractometer	1670 reflections with I > 2σ(I)
5860 measured reflections	R_int = 0.019
2140 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.20	Δρ_max = 0.21 e Å⁻³
2140 reflections	Δρ_min = −0.21 e Å⁻³
199 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O2	0.56725 (18)	0.14099 (15)	0.95776 (10)	0.0576 (4)
N1	0.06769 (18)	0.16834 (14)	0.89752 (10)	0.0360 (4)
C4	−0.0303 (2)	0.25527 (16)	0.92696 (11)	0.0324 (4)
O8	−0.18514 (19)	0.22095 (15)	0.72839 (10)	0.0566 (4)
N2	0.4618 (2)	0.14859 (15)	0.88135 (11)	0.0419 (4)
C9	−0.1501 (2)	0.33688 (17)	0.86745 (11)	0.0334 (4)
N3	0.3038 (2)	−0.04265 (16)	0.84420 (11)	0.0435 (4)
N5	−0.20374 (19)	0.32296 (17)	0.76316 (11)	0.0429 (4)
C1	0.1375 (2)	0.16202 (18)	0.81278 (12)	0.0376 (4)
H1A	0.1660	0.2430	0.7906	0.045*
H1B	0.0689	0.1131	0.7602	0.045*
C3	0.2168 (2)	0.10713 (18)	0.96128 (12)	0.0384 (4)
H3B	0.1908	0.0288	0.9886	0.046*
H3A	0.2834	0.1618	1.0105	0.046*
N4	−0.2936 (2)	0.53426 (18)	1.04331 (15)	0.0556 (5)
C7	−0.2070 (2)	0.43720 (19)	1.00353 (13)	0.0411 (5)
O3	0.4390 (2)	−0.07976 (16)	0.83333 (12)	0.0679 (5)
C6	−0.0999 (2)	0.35558 (19)	1.06406 (13)	0.0441 (5)
H6	−0.0866	0.3606	1.1300	0.053*
C2	0.2905 (2)	0.09108 (16)	0.87430 (12)	0.0340 (4)
C8	−0.2340 (2)	0.42800 (18)	0.90514 (13)	0.0388 (4)
H8	−0.3082	0.4828	0.8648	0.047*
O1	0.4830 (2)	0.19814 (17)	0.80972 (11)	0.0655 (5)
O7	−0.2721 (2)	0.41195 (17)	0.71504 (11)	0.0671 (5)
O6	−0.3804 (2)	0.61021 (15)	0.98923 (15)	0.0718 (5)
O4	0.1762 (2)	−0.10369 (15)	0.83337 (12)	0.0678 (5)
C5	−0.0131 (2)	0.26685 (19)	1.02664 (12)	0.0407 (5)
H5	0.0596	0.2125	1.0683	0.049*
O5	−0.2740 (3)	0.5369 (2)	1.13090 (13)	0.0877 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0396 (8)	0.0687 (11)	0.0560 (9)	−0.0018 (7)	−0.0034 (7)	0.0035 (7)
N1	0.0336 (8)	0.0430 (9)	0.0315 (7)	0.0082 (7)	0.0083 (6)	0.0019 (6)
C4	0.0289 (9)	0.0349 (10)	0.0344 (9)	−0.0039 (7)	0.0098 (7)	−0.0011 (7)
O8	0.0486 (9)	0.0709 (11)	0.0446 (8)	0.0096 (8)	0.0012 (6)	−0.0167 (7)
N2	0.0366 (9)	0.0427 (9)	0.0457 (9)	0.0007 (7)	0.0092 (7)	0.0018 (7)
C9	0.0295 (9)	0.0389 (10)	0.0311 (8)	−0.0015 (8)	0.0062 (7)	−0.0005 (7)
N3	0.0490 (10)	0.0384 (9)	0.0433 (9)	0.0025 (8)	0.0123 (7)	−0.0007 (7)
N5	0.0306 (8)	0.0574 (11)	0.0387 (9)	0.0037 (8)	0.0050 (7)	0.0027 (8)
C1	0.0342 (10)	0.0451 (11)	0.0338 (9)	0.0067 (8)	0.0089 (7)	0.0017 (8)
C3	0.0375 (10)	0.0404 (11)	0.0364 (9)	0.0059 (8)	0.0075 (7)	0.0039 (8)
N4	0.0443 (10)	0.0497 (12)	0.0779 (13)	−0.0058 (9)	0.0253 (9)	−0.0222 (10)
C7	0.0352 (10)	0.0414 (11)	0.0497 (11)	−0.0052 (8)	0.0164 (8)	−0.0131 (9)
O3	0.0609 (10)	0.0625 (11)	0.0811 (11)	0.0189 (8)	0.0196 (8)	−0.0179 (8)
C6	0.0430 (11)	0.0556 (13)	0.0356 (9)	−0.0058 (9)	0.0135 (8)	−0.0069 (9)
C2	0.0320 (9)	0.0330 (10)	0.0359 (9)	0.0019 (7)	0.0068 (7)	0.0003 (7)
C8	0.0309 (9)	0.0364 (10)	0.0483 (10)	−0.0013 (8)	0.0086 (8)	0.0015 (8)
O1	0.0474 (9)	0.0908 (13)	0.0596 (9)	−0.0145 (8)	0.0159 (7)	0.0171 (8)
O7	0.0700 (11)	0.0777 (12)	0.0478 (8)	0.0224 (9)	0.0043 (7)	0.0165 (8)
O6	0.0689 (11)	0.0460 (10)	0.1116 (14)	0.0094 (9)	0.0432 (10)	−0.0049 (10)
O4	0.0725 (11)	0.0498 (10)	0.0845 (11)	−0.0217 (8)	0.0263 (9)	−0.0118 (8)
C5	0.0397 (10)	0.0480 (12)	0.0339 (10)	0.0030 (9)	0.0083 (8)	0.0032 (8)
O5	0.0877 (13)	0.1094 (16)	0.0693 (11)	0.0103 (11)	0.0260 (10)	−0.0450 (11)

Geometric parameters (Å, º) top

O2—N2	1.2133 (19)	C1—C2	1.530 (2)
N1—C4	1.358 (2)	C1—H1A	0.9700
N1—C1	1.471 (2)	C1—H1B	0.9700
N1—C3	1.473 (2)	C3—C2	1.528 (3)
C4—C5	1.412 (2)	C3—H3B	0.9700
C4—C9	1.420 (2)	C3—H3A	0.9700
O8—N5	1.224 (2)	N4—O6	1.217 (2)
N2—O1	1.209 (2)	N4—O5	1.231 (2)
N2—C2	1.499 (2)	N4—C7	1.449 (3)
C9—C8	1.375 (3)	C7—C6	1.375 (3)
C9—N5	1.461 (2)	C7—C8	1.381 (3)
N3—O4	1.199 (2)	C6—C5	1.370 (3)
N3—O3	1.213 (2)	C6—H6	0.9300
N3—C2	1.504 (2)	C8—H8	0.9300
N5—O7	1.223 (2)	C5—H5	0.9300

C4—N1—C1	132.01 (15)	C2—C3—H3B	113.9
C4—N1—C3	124.20 (14)	N1—C3—H3A	113.9
C1—N1—C3	93.91 (13)	C2—C3—H3A	113.9
N1—C4—C5	117.53 (15)	H3B—C3—H3A	111.1
N1—C4—C9	126.61 (15)	O6—N4—O5	122.96 (19)
C5—C4—C9	115.86 (16)	O6—N4—C7	118.91 (19)
O1—N2—O2	125.62 (17)	O5—N4—C7	118.1 (2)
O1—N2—C2	116.82 (15)	C6—C7—C8	121.05 (18)
O2—N2—C2	117.57 (16)	C6—C7—N4	119.64 (18)
C8—C9—C4	121.83 (16)	C8—C7—N4	119.31 (18)
C8—C9—N5	115.41 (15)	C5—C6—C7	119.63 (17)
C4—C9—N5	122.54 (16)	C5—C6—H6	120.2
O4—N3—O3	125.76 (19)	C7—C6—H6	120.2
O4—N3—C2	115.52 (16)	N2—C2—N3	105.99 (14)
O3—N3—C2	118.72 (17)	N2—C2—C3	116.55 (14)
O7—N5—O8	123.01 (16)	N3—C2—C3	114.47 (15)
O7—N5—C9	118.51 (17)	N2—C2—C1	116.00 (15)
O8—N5—C9	118.39 (15)	N3—C2—C1	114.20 (14)
N1—C1—C2	88.22 (12)	C3—C2—C1	89.46 (13)
N1—C1—H1A	113.9	C9—C8—C7	119.30 (17)
C2—C1—H1A	113.9	C9—C8—H8	120.3
N1—C1—H1B	113.9	C7—C8—H8	120.4
C2—C1—H1B	113.9	C6—C5—C4	122.15 (17)
H1A—C1—H1B	111.1	C6—C5—H5	118.9
N1—C3—C2	88.23 (12)	C4—C5—H5	118.9
N1—C3—H3B	113.9

C1—N1—C4—C5	−151.31 (18)	O1—N2—C2—C3	−140.71 (18)
C3—N1—C4—C5	−15.0 (3)	O2—N2—C2—C3	39.7 (2)
C1—N1—C4—C9	28.7 (3)	O1—N2—C2—C1	−37.3 (2)
C3—N1—C4—C9	165.05 (17)	O2—N2—C2—C1	143.13 (16)
N1—C4—C9—C8	−175.18 (17)	O4—N3—C2—N2	−178.93 (15)
C5—C4—C9—C8	4.9 (3)	O3—N3—C2—N2	1.3 (2)
N1—C4—C9—N5	10.4 (3)	O4—N3—C2—C3	51.2 (2)
C5—C4—C9—N5	−169.55 (16)	O3—N3—C2—C3	−128.56 (18)
C8—C9—N5—O7	23.2 (2)	O4—N3—C2—C1	−50.0 (2)
C4—C9—N5—O7	−162.06 (18)	O3—N3—C2—C1	130.29 (18)
C8—C9—N5—O8	−153.55 (17)	N1—C3—C2—N2	122.10 (16)
C4—C9—N5—O8	21.2 (2)	N1—C3—C2—N3	−113.44 (15)
C4—N1—C1—C2	148.25 (19)	N1—C3—C2—C1	3.06 (14)
C3—N1—C1—C2	3.19 (14)	N1—C1—C2—N2	−122.59 (15)
C4—N1—C3—C2	−152.23 (17)	N1—C1—C2—N3	113.68 (16)
C1—N1—C3—C2	−3.19 (14)	N1—C1—C2—C3	−3.07 (14)
O6—N4—C7—C6	175.89 (19)	C4—C9—C8—C7	−2.9 (3)
O5—N4—C7—C6	−3.2 (3)	N5—C9—C8—C7	171.93 (16)
O6—N4—C7—C8	−4.3 (3)	C6—C7—C8—C9	−1.1 (3)
O5—N4—C7—C8	176.56 (19)	N4—C7—C8—C9	179.16 (17)
C8—C7—C6—C5	2.7 (3)	C7—C6—C5—C4	−0.4 (3)
N4—C7—C6—C5	−177.53 (18)	N1—C4—C5—C6	176.83 (18)
O1—N2—C2—N3	90.61 (19)	C9—C4—C5—C6	−3.2 (3)
O2—N2—C2—N3	−88.97 (19)

Experimental details

Crystal data
Chemical formula	C₉H₇N₅O₈
M_r	313.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.113 (2), 10.676 (3), 14.398 (4)
β (°)	104.681 (4)
V (Å³)	1206.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.31 × 0.26 × 0.20

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5860, 2140, 1670
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.118, 1.20
No. of reflections	2140
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELX97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We thank the National Natural Science Foundation of China (No. 20603026) and the Natural Science Foundation of Shaanxi Province, China (No. 2009JQ2002) for generously supporting this study.

References

Archibald, T. G., Gilardi, R., Baum, K. & George, C. (1990). J. Org. Chem. 55, 2920–2924. CSD CrossRef CAS Web of Science Google Scholar
Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Frumkin, A. E., Churakov, A. M., Strelenko, Y. A., Kachala, V. V. & Tartakkovsky, V. A. (1999). Org. Lett. 1, 721–724. Web of Science CrossRef PubMed CAS Google Scholar
Gao, R., Ma, H. X., Yan, B., Song, J. R. & Wang, Y. H. (2009). Chem. J. Chin. Univ. 30, 577–582. CAS Google Scholar
Hiskey, M. A. & Coburn, M. D. (1994a). US Patent No. 5 336 784. Google Scholar
Hiskey, M. A. & Coburn, M. D. (1994b). Chem. Abstr. 121, 300750s. Google Scholar
Hiskey, M. A., Coburn, M. D., Mitchell, M. A. & Benicewicz, B. C. (1992). J. Heterocycl. Chem. 29, 1855–1856. CrossRef CAS Google Scholar
Hiskey, M. A., Stincipher, M. M. & Brown, J. E. (1993). J. Energ. Mater. 11, 157–165. CrossRef CAS Google Scholar
Ma, H. X., Yan, B., Li, Z. N., Guan, Y. L., Song, J. R., Xu, K. Z. & Hu, R. Z. (2009a). J. Hazard. Mater. 169, 1068–1073. Web of Science CrossRef PubMed CAS Google Scholar
Ma, H. X., Yan, B., Li, Z. N., Song, J. R. & Hu, R. Z. (2009b). J. Therm. Anal. Calorim. 95, 437–444. Web of Science CrossRef CAS Google Scholar
Ma, H. X., Yan, B., Song, J. R., Lü, X. Q. & Wang, L. J. (2009c). Chem. J. Chin. Univ. 30, 371–381. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar