1-Benzoyl-3,3-dinitro­azetidine

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

doi:10.1107/S1600536809051290

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o57

doi:10.1107/S1600536809051290

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1-Benzoyl-3,3-dinitroazetidine

Biao Yan,^a,^b Hai-Xia Ma,^b ^* Jun-Feng Li,^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 19 November 2009; accepted 28 November 2009; online 4 December 2009)

In the title gem-dinitroazetidine derivative, C₁₀H₉N₃O₅, the azetidine ring is almost planar, the maximum value of the endocyclic torsion angle being 0.92 (14)°. The gem-dinitro groups are mutually perpendicular and the dihedral angle between the azetidine and benzene rings is 46.70 (10)°

Related literature

For energetic materials based on 3,3-dinitroazetidine, see: Archibald et al. (1990 ); Gao et al. (2009 ); Hiskey & Coburn (1994a ,b ); Ma, Yan, Li, Guan et al. (2009 ); Ma, Yan, Li, Song & Hu (2009 ); Ma, Yan, Song et al. (2009 ).

Experimental

Crystal data

C₁₀H₉N₃O₅
M_r = 251.20
Monoclinic, P 2₁ /c
a = 13.176 (4) Å
b = 6.2344 (19) Å
c = 13.522 (4) Å
β = 92.612 (6)°
V = 1109.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.39 × 0.27 × 0.15 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.954, T_max = 0.981
5306 measured reflections
1975 independent reflections
1210 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 0.98
1975 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.16 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/S1600536809051290/gk2242sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051290/gk2242Isup2.hkl

checkCIF report

Comment top

Dinitro- and trinitro-derivatives of azetidine are of interest because they contain strained ring system. This makes them good candidates for energetic materials (propellants or explosives). Initial reports on the synthesis of 1,3,3-trinitroazetidine (TNAZ) included the synthesis of 3,3-dinitroazetidine (DNAZ) in the synthesis pathway (Archibald et al., 1990). However, later on less expensive synthesis of DNAZ was reported (Hiskey et al., 1994a,b). Starting from DNAZ as a substrate a variety of solid energetic compounds can be prepared (Gao et al., 2009; Ma, Yan, Li, Guan et al., 2009; Ma, Yan, Li, Song & Hu, 2009; Ma, Yan, Song et al., 2009). This paper reports synthesis and crystal structure of the title DNAZ derivate.

Related literature top

For energetic materials based on 3,3-dinitroazetidine, see: Archibald et al. (1990); Gao et al. (2009); Hiskey & Coburn (1994a,b); Ma, Yan, Li, Guan et al. (2009); Ma, Yan, Li, Song & Hu (2009); Ma, Yan, Song et al. (2009).

Experimental top

A solution of DNAZ (0.40 g, 2.72 mmol), benzoyl chloride (0.35 ml, 2.99 mmol) and NaHCO₃ (0.23 g, 2.72 mmol) in dichloromethane (20.0 ml) was stirred under reflux for 16 h. The reaction mixture was concentrated in vacuo, acetone (30.0 ml) was added, and the mixture was stirred for 30 min, standing, filtered. The solid product was washed with ethanol and purified by recrystallization from dichloromethane to give the pure colorless compound in 81.7% yield. The title compound (52 mg,0.2 mmol) was dissolved in chloroform (10 ml). Colorless crystals were isolated after several days. Elemental analysis calculated for C₁₀H₉N₃O₅: C 47.81, N 16.73, H 3.61%; found: C 47.29, N 16.88, H 3.63%. IR (KBr, cm^-1): 3057, 2961, 1640, 1578, 1526, 1335, 1304, 706. ¹H NMR (CDCl₃): (δdelta/p.p.m.) 7.649 (2H), 7.581 (4H), 7.489 (2H), 5.025 (4H).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound 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-benzoyl-3,3-dinitroazetidine top

Crystal data top

C₁₀H₉N₃O₅	F(000) = 520
M_r = 251.20	D_x = 1.504 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 862 reflections
a = 13.176 (4) Å	θ = 3.0–21.2°
b = 6.2344 (19) Å	µ = 0.12 mm⁻¹
c = 13.522 (4) Å	T = 296 K
β = 92.612 (6)°	Block, colorless
V = 1109.6 (6) Å³	0.39 × 0.27 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	1975 independent reflections
Radiation source: fine-focus sealed tube	1210 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 25.1°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −15→15
T_min = 0.954, T_max = 0.981	k = −7→7
5306 measured reflections	l = −15→11

Refinement top

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0493P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.001
1975 reflections	Δρ_max = 0.15 e Å⁻³
164 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

Crystal data top

C₁₀H₉N₃O₅	V = 1109.6 (6) Å³
M_r = 251.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.176 (4) Å	µ = 0.12 mm⁻¹
b = 6.2344 (19) Å	T = 296 K
c = 13.522 (4) Å	0.39 × 0.27 × 0.15 mm
β = 92.612 (6)°

Data collection top

Bruker SMART APEXII diffractometer	1975 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	1210 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.981	R_int = 0.028
5306 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 0.98	Δρ_max = 0.15 e Å⁻³
1975 reflections	Δρ_min = −0.16 e Å⁻³
164 parameters

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.

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
N3	0.68948 (11)	0.3359 (2)	0.80874 (11)	0.0468 (4)
O5	0.75063 (10)	0.01052 (19)	0.84162 (10)	0.0599 (4)
O1	0.75527 (11)	0.6527 (2)	0.99733 (12)	0.0775 (5)
O2	0.61765 (11)	0.8369 (2)	1.01338 (11)	0.0705 (5)
O3	0.44932 (11)	0.6147 (2)	0.89476 (11)	0.0713 (5)
O4	0.52323 (10)	0.8514 (2)	0.80573 (12)	0.0702 (5)
C6	0.91631 (15)	0.0829 (3)	0.71825 (16)	0.0579 (6)
H6	0.9293	−0.0078	0.7719	0.070*
C7	0.98541 (16)	0.0983 (3)	0.64582 (19)	0.0692 (6)
H7	1.0451	0.0188	0.6510	0.083*
C8	0.96726 (16)	0.2296 (3)	0.56602 (18)	0.0654 (6)
H8	1.0145	0.2398	0.5172	0.078*
C9	0.87872 (16)	0.3464 (3)	0.55826 (16)	0.0601 (6)
H9	0.8658	0.4351	0.5038	0.072*
C10	0.80912 (15)	0.3321 (3)	0.63113 (14)	0.0509 (5)
H10	0.7494	0.4115	0.6255	0.061*
C5	0.82730 (13)	0.2012 (3)	0.71215 (14)	0.0439 (5)
C4	0.75447 (13)	0.1743 (3)	0.79194 (14)	0.0444 (5)
C3	0.69359 (15)	0.5702 (3)	0.79507 (14)	0.0498 (5)
H3A	0.6629	0.6195	0.7326	0.060*
H3B	0.7607	0.6314	0.8072	0.060*
C1	0.62456 (13)	0.5904 (3)	0.88225 (13)	0.0419 (5)
C2	0.62480 (14)	0.3459 (3)	0.89365 (14)	0.0489 (5)
H2B	0.6575	0.2956	0.9551	0.059*
H2A	0.5586	0.2801	0.8821	0.059*
N1	0.66923 (14)	0.7057 (3)	0.97243 (13)	0.0541 (5)
N2	0.52333 (12)	0.6935 (3)	0.85921 (13)	0.0513 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0634 (10)	0.0315 (8)	0.0468 (10)	0.0014 (7)	0.0156 (8)	0.0040 (7)
O5	0.0819 (10)	0.0343 (7)	0.0641 (9)	0.0015 (6)	0.0103 (8)	0.0088 (7)
O1	0.0730 (10)	0.0680 (10)	0.0889 (13)	−0.0016 (8)	−0.0258 (9)	0.0058 (8)
O2	0.0914 (11)	0.0603 (9)	0.0607 (10)	−0.0037 (8)	0.0135 (9)	−0.0178 (8)
O3	0.0565 (9)	0.0876 (12)	0.0710 (11)	0.0034 (8)	0.0172 (8)	0.0072 (9)
O4	0.0717 (10)	0.0584 (9)	0.0800 (11)	0.0119 (7)	−0.0017 (8)	0.0189 (8)
C6	0.0657 (13)	0.0471 (12)	0.0611 (14)	0.0105 (10)	0.0041 (12)	0.0029 (10)
C7	0.0581 (13)	0.0652 (14)	0.0848 (18)	0.0108 (11)	0.0108 (13)	−0.0071 (13)
C8	0.0668 (14)	0.0598 (13)	0.0712 (17)	−0.0057 (11)	0.0222 (12)	−0.0085 (12)
C9	0.0764 (14)	0.0533 (13)	0.0513 (13)	0.0010 (11)	0.0115 (11)	0.0033 (10)
C10	0.0579 (11)	0.0497 (12)	0.0453 (12)	0.0058 (9)	0.0050 (10)	−0.0012 (10)
C5	0.0536 (11)	0.0324 (10)	0.0454 (12)	−0.0006 (8)	0.0004 (9)	−0.0043 (9)
C4	0.0553 (11)	0.0320 (10)	0.0454 (11)	−0.0013 (9)	−0.0008 (9)	−0.0019 (9)
C3	0.0641 (12)	0.0355 (10)	0.0511 (12)	0.0046 (8)	0.0147 (10)	0.0054 (9)
C1	0.0495 (11)	0.0356 (9)	0.0407 (11)	0.0024 (8)	0.0038 (9)	0.0001 (8)
C2	0.0604 (11)	0.0393 (10)	0.0477 (12)	−0.0017 (9)	0.0101 (9)	0.0022 (9)
N1	0.0679 (12)	0.0413 (10)	0.0528 (11)	−0.0070 (9)	0.0002 (10)	0.0038 (8)
N2	0.0565 (11)	0.0492 (10)	0.0482 (10)	0.0039 (9)	0.0035 (8)	−0.0039 (8)

Geometric parameters (Å, º) top

N3—C4	1.348 (2)	C8—H8	0.9300
N3—C2	1.462 (2)	C9—C10	1.379 (3)
N3—C3	1.474 (2)	C9—H9	0.9300
O5—C4	1.224 (2)	C10—C5	1.378 (3)
O1—N1	1.2134 (19)	C10—H10	0.9300
O2—N1	1.2133 (18)	C5—C4	1.486 (2)
O3—N2	1.2109 (19)	C3—C1	1.527 (2)
O4—N2	1.2212 (19)	C3—H3A	0.9700
C6—C7	1.371 (3)	C3—H3B	0.9700
C6—C5	1.385 (2)	C1—N2	1.500 (2)
C6—H6	0.9300	C1—N1	1.511 (2)
C7—C8	1.367 (3)	C1—C2	1.532 (2)
C7—H7	0.9300	C2—H2B	0.9700
C8—C9	1.375 (3)	C2—H2A	0.9700

C4—N3—C2	124.17 (15)	N3—C3—C1	87.62 (12)
C4—N3—C3	133.82 (14)	N3—C3—H3A	114.0
C2—N3—C3	94.70 (12)	C1—C3—H3A	114.0
C7—C6—C5	120.6 (2)	N3—C3—H3B	114.0
C7—C6—H6	119.7	C1—C3—H3B	114.0
C5—C6—H6	119.7	H3A—C3—H3B	111.2
C8—C7—C6	120.5 (2)	N2—C1—N1	105.88 (14)
C8—C7—H7	119.7	N2—C1—C3	115.48 (15)
C6—C7—H7	119.7	N1—C1—C3	116.01 (15)
C7—C8—C9	119.7 (2)	N2—C1—C2	116.42 (14)
C7—C8—H8	120.2	N1—C1—C2	113.13 (15)
C9—C8—H8	120.2	C3—C1—C2	89.82 (12)
C8—C9—C10	120.0 (2)	N3—C2—C1	87.84 (12)
C8—C9—H9	120.0	N3—C2—H2B	114.0
C10—C9—H9	120.0	C1—C2—H2B	114.0
C5—C10—C9	120.60 (18)	N3—C2—H2A	114.0
C5—C10—H10	119.7	C1—C2—H2A	114.0
C9—C10—H10	119.7	H2B—C2—H2A	111.2
C10—C5—C6	118.61 (18)	O2—N1—O1	126.33 (18)
C10—C5—C4	123.34 (16)	O2—N1—C1	118.88 (17)
C6—C5—C4	118.01 (18)	O1—N1—C1	114.78 (17)
O5—C4—N3	119.23 (17)	O3—N2—O4	125.66 (17)
O5—C4—C5	122.48 (16)	O3—N2—C1	117.90 (16)
N3—C4—C5	118.29 (15)	O4—N2—C1	116.44 (16)

C5—C6—C7—C8	−0.5 (3)	N3—C3—C1—N1	116.69 (15)
C6—C7—C8—C9	−0.3 (3)	N3—C3—C1—C2	0.88 (14)
C7—C8—C9—C10	0.5 (3)	C4—N3—C2—C1	154.51 (16)
C8—C9—C10—C5	0.0 (3)	C3—N3—C2—C1	0.92 (14)
C9—C10—C5—C6	−0.7 (3)	N2—C1—C2—N3	117.73 (15)
C9—C10—C5—C4	−178.42 (16)	N1—C1—C2—N3	−119.27 (16)
C7—C6—C5—C10	0.9 (3)	C3—C1—C2—N3	−0.88 (14)
C7—C6—C5—C4	178.79 (17)	N2—C1—N1—O2	6.0 (2)
C2—N3—C4—O5	10.7 (3)	C3—C1—N1—O2	135.59 (16)
C3—N3—C4—O5	152.76 (19)	C2—C1—N1—O2	−122.61 (16)
C2—N3—C4—C5	−170.27 (16)	N2—C1—N1—O1	−174.84 (15)
C3—N3—C4—C5	−28.2 (3)	C3—C1—N1—O1	−45.3 (2)
C10—C5—C4—O5	152.40 (18)	C2—C1—N1—O1	56.5 (2)
C6—C5—C4—O5	−25.3 (3)	N1—C1—N2—O3	−92.40 (18)
C10—C5—C4—N3	−26.6 (2)	C3—C1—N2—O3	137.76 (16)
C6—C5—C4—N3	155.63 (16)	C2—C1—N2—O3	34.3 (2)
C4—N3—C3—C1	−150.25 (19)	N1—C1—N2—O4	87.52 (18)
C2—N3—C3—C1	−0.92 (14)	C3—C1—N2—O4	−42.3 (2)
N3—C3—C1—N2	−118.56 (15)	C2—C1—N2—O4	−145.79 (16)

Experimental details

Crystal data
Chemical formula	C₁₀H₉N₃O₅
M_r	251.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.176 (4), 6.2344 (19), 13.522 (4)
β (°)	92.612 (6)
V (Å³)	1109.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.39 × 0.27 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.954, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	5306, 1975, 1210
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 0.98
No. of reflections	1975
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (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

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