3,3-Dinitro­azetidinium chloride

Yan, B.; Li, H.-Y.; Zhao, N.-N.; Li, J.; Ma, H.-X.

doi:10.1107/S1600536812046302

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3376

doi:10.1107/S1600536812046302

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3,3-Dinitroazetidinium chloride

Biao Yan,^a,^b Hong-Ya Li,^a,^b Ning-Ning Zhao,^b Jie Li ^b and Hai-Xia Ma ^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 29 October 2012; accepted 9 November 2012; online 17 November 2012)

In the title gem-dinitroazetidinium chloride salt, C₃H₆N₃O₄⁺·Cl⁻, the cations and anions lie on a mirror plane. The azetidine ring is virtually planar, with a mean deviation from the plane of 0.0569 Å. The dihedral angle between the two nitro groups is 90.00 (5)°. In the crystal, the ions are linked by N—H⋯Cl interactions, forming a chain along the c-axis direction, and C—H⋯O interactions, forming a layer parallel to (010).

Related literature

For 1,3,3-trinitroazetidine and compounds prepared from its derivative 3,3-dinitroazetidine, see: Archibald et al. (1990 ); Hiskey et al. (1992 ); Ma et al. (2009a ,b , 2011 ); Yan et al. (2009 , 2010 ); Gao et al. (2009 ). For related structures, see: Gao et al. (2010 ); Ma et al. (2010 ). For the synthesis, see: Li et al. (2004 ).

Experimental

Crystal data

C₃H₆N₃O₄⁺·Cl⁻
M_r = 183.56
Orthorhombic, C m c 2₁
a = 6.6807 (17) Å
b = 10.4409 (17) Å
c = 9.9707 (19) Å
V = 695.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 293 K
0.35 × 0.34 × 0.30 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.839, T_max = 0.860
1968 measured reflections
708 independent reflections
696 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.055
S = 1.10
708 reflections
62 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 252 Friedel pairs
Flack parameter: 0.09 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl	0.90	2.35	3.087 (2)	139
N1—H1D⋯Clⁱ	0.90	2.19	3.0575 (19)	163
C1—H1B⋯O4ⁱⁱ	0.97	2.58	3.543 (2)	172
Symmetry codes: (i) $[-x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (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/S1600536812046302/zq2187sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046302/zq2187Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046302/zq2187Isup3.cml

checkCIF report

Comment top

Dinitro- and trinitro-derivatives of azetidine are of interest because they contain strained ring systems. This makes them good candidates for energetic materials (propellants or explosives). Azetidine-based explosives, such as 1,3,3-trinitroazetidine (TNAZ) (Archibald et al., 1990) 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) can prepare a variety of solid energetic materials with high oxygen-balance (Ma et al., 2009a; Ma et al., 2009b; Yan et al., 2009; Gao et al., 2009; Yan et al., 2010; Ma et al., 2010; Gao et al., 2010; Ma et al., 2011). This paper reports the crystal structure of the title DNAZ salt, C₃H₆N₃O₄⁺.Cl^-.

In the title dinitroazetidinium chloride salt, cations and anions lie on a mirror plane. The azetidine ring is virtually planar, with a mean deviation from the plane of 0.0569 Å. The dihedral angle between the two nitro groups is 90.00 (5)°. In the crystal, the ions are linked by N–H···Cl and C–H···O interactions.

Related literature top

For 1,3,3-trinitroazetidine and compounds prepared from its derivative 3,3-dinitroazetidine, see: Archibald et al. (1990); Hiskey et al. (1992); Ma et al. (2009a,b, 2011); Yan et al. (2009, 2010); Gao et al. (2009). For related structures, see: Gao et al. (2010); Ma et al. (2010). For the synthesis, see: Li et al. (2004).

Experimental top

The title compound was synthesized and purified by a reported method (Li et al., 2004). The compound was then dissolved in water and colorless crystals were isolated after 1 d.

Elemental analysis calculated for C₃H₆N₃O₄Cl: C 19.63, N 22.89, H 3.29%; found: C 19.74, N 23.10, H 3.19%.

IR (KBr, cm^-1): 3057, 2623, 1588, 1406, 1333, 850, 808.

Computing details top

Data collection: APEX2 (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.

3,3-Dinitroazetidinium chloride top

Crystal data top

C₃H₆N₃O₄⁺·Cl⁻	Z = 4
M_r = 183.56	F(000) = 376
Orthorhombic, Cmc2₁	D_x = 1.753 Mg m⁻³
Hall symbol: C 2c -2	Mo Kα radiation, λ = 0.71073 Å
a = 6.6807 (17) Å	µ = 0.52 mm⁻¹
b = 10.4409 (17) Å	T = 293 K
c = 9.9707 (19) Å	Block, colourless
V = 695.5 (2) Å³	0.35 × 0.34 × 0.30 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	708 independent reflections
Radiation source: fine-focus sealed tube	696 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 27.9°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −8→8
T_min = 0.839, T_max = 0.860	k = −13→12
1968 measured reflections	l = −11→13

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.021	w = 1/[σ²(F_o²) + (0.0313P)² + 0.199P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.055	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.18 e Å⁻³
708 reflections	Δρ_min = −0.16 e Å⁻³
62 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.227 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 252 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.09 (7)

Crystal data top

C₃H₆N₃O₄⁺·Cl⁻	V = 695.5 (2) Å³
M_r = 183.56	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 6.6807 (17) Å	µ = 0.52 mm⁻¹
b = 10.4409 (17) Å	T = 293 K
c = 9.9707 (19) Å	0.35 × 0.34 × 0.30 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	708 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	696 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.860	R_int = 0.019
1968 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.055	Δρ_max = 0.18 e Å⁻³
S = 1.10	Δρ_min = −0.16 e Å⁻³
708 reflections	Absolute structure: Flack (1983), 252 Friedel pairs
62 parameters	Absolute structure parameter: 0.09 (7)
1 restraint

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
Cl	0.0000	0.34257 (4)	0.24339 (6)	0.03211 (19)
N2	0.0000	0.14030 (15)	0.5026 (2)	0.0277 (4)
O3	0.0000	0.07128 (19)	0.7449 (3)	0.0571 (6)
C1	0.1613 (2)	0.35120 (12)	0.57848 (17)	0.0255 (3)
H1A	0.2305	0.3773	0.6596	0.031*
H1B	0.2557	0.3293	0.5081	0.031*
N3	0.0000	0.1881 (2)	0.7388 (3)	0.0354 (4)
N1	0.0000	0.44299 (15)	0.5346 (2)	0.0269 (4)
H1C	0.0000	0.4581	0.4457	0.032*
H1D	0.0000	0.5170	0.5808	0.032*
O4	0.0000	0.2614 (3)	0.8318 (2)	0.0536 (6)
O1	0.16253 (18)	0.10036 (10)	0.46749 (16)	0.0425 (4)
C2	0.0000	0.24966 (18)	0.6017 (2)	0.0217 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0359 (3)	0.0347 (3)	0.0258 (3)	0.000	0.000	0.0048 (3)
N2	0.0314 (9)	0.0207 (8)	0.0309 (11)	0.000	0.000	0.0002 (7)
O3	0.0562 (12)	0.0522 (10)	0.0629 (14)	0.000	0.000	0.0373 (12)
C1	0.0226 (7)	0.0236 (7)	0.0304 (8)	−0.0015 (5)	0.0008 (6)	−0.0013 (5)
N3	0.0232 (8)	0.0556 (11)	0.0273 (9)	0.000	0.000	0.0133 (13)
N1	0.0323 (10)	0.0202 (7)	0.0283 (9)	0.000	0.000	−0.0012 (7)
O4	0.0463 (12)	0.0904 (16)	0.0240 (9)	0.000	0.000	−0.0017 (9)
O1	0.0365 (7)	0.0362 (6)	0.0549 (9)	0.0117 (4)	−0.0002 (7)	−0.0136 (6)
C2	0.0218 (9)	0.0215 (9)	0.0217 (11)	0.000	0.000	0.0007 (7)

Geometric parameters (Å, º) top

N2—O1ⁱ	1.2147 (14)	C1—H1B	0.9700
N2—O1	1.2147 (14)	N3—O4	1.203 (4)
N2—C2	1.510 (3)	N3—C2	1.511 (3)
O3—N3	1.221 (3)	N1—C1ⁱ	1.5073 (19)
C1—N1	1.5073 (18)	N1—H1C	0.9000
C1—C2	1.5294 (19)	N1—H1D	0.9000
C1—H1A	0.9700	C2—C1ⁱ	1.5294 (19)

O1ⁱ—N2—O1	126.74 (19)	O4—N3—C2	115.2 (2)
O1ⁱ—N2—C2	116.63 (9)	O3—N3—C2	118.0 (3)
O1—N2—C2	116.63 (9)	C1—N1—C1ⁱ	91.30 (15)
N1—C1—C2	88.89 (11)	C1—N1—H1C	113.4
N1—C1—H1A	113.8	C1—N1—H1D	113.4
C2—C1—H1A	113.8	H1C—N1—H1D	110.7
N1—C1—H1B	113.8	N2—C2—N3	105.67 (17)
C2—C1—H1B	113.8	N2—C2—C1	115.17 (13)
H1A—C1—H1B	111.1	N3—C2—C1	115.58 (13)
O4—N3—O3	126.7 (3)	C1—C2—C1ⁱ	89.62 (15)

C2—C1—N1—C1ⁱ	8.66 (17)	O3—N3—C2—N2	0.0
O1ⁱ—N2—C2—N3	89.58 (16)	O4—N3—C2—C1	51.39 (11)
O1—N2—C2—N3	−89.58 (16)	O3—N3—C2—C1	−128.61 (11)
O1ⁱ—N2—C2—C1	−141.56 (16)	O4—N3—C2—C1ⁱ	−51.39 (11)
O1—N2—C2—C1	39.3 (2)	O3—N3—C2—C1ⁱ	128.61 (11)
O1ⁱ—N2—C2—C1ⁱ	−39.3 (2)	N1—C1—C2—N2	109.30 (15)
O1—N2—C2—C1ⁱ	141.56 (16)	N1—C1—C2—N3	−126.93 (15)
O4—N3—C2—N2	180.0	N1—C1—C2—C1ⁱ	−8.53 (17)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl	0.90	2.35	3.087 (2)	139
N1—H1D···Clⁱⁱ	0.90	2.19	3.0575 (19)	163
C1—H1B···O1	0.97	2.50	2.8432 (19)	100
C1—H1B···O4ⁱⁱⁱ	0.97	2.58	3.543 (2)	172

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

Experimental details

Crystal data
Chemical formula	C₃H₆N₃O₄⁺·Cl⁻
M_r	183.56
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	293
a, b, c (Å)	6.6807 (17), 10.4409 (17), 9.9707 (19)
V (Å³)	695.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.35 × 0.34 × 0.30

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.839, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	1968, 708, 696
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.10
No. of reflections	708
No. of parameters	62
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16
Absolute structure	Flack (1983), 252 Friedel pairs
Absolute structure parameter	0.09 (7)

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl	0.90	2.35	3.087 (2)	139
N1—H1D···Clⁱ	0.90	2.19	3.0575 (19)	163
C1—H1B···O4ⁱⁱ	0.97	2.58	3.543 (2)	172

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

Acknowledgements

We thank the National Natural Science Foundation of China (grant No. 21073141), the Education Committee Foundation of Shaanxi Province (grant Nos. 11 JK0564 and 11J K0582) and the Project sponsored by SRF for AT, YLU (No. 09GK019) for generously supporting this study.

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