3,3-Dinitro­azetidinium chloride

Abstract

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,

• a = 6.6807 (17) Å

• b = 10.4409 (17) Å

• c = 9.9707 (19) Å

• V = 695.5 (2) ų

• 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[F ² > 2σ(F ²)] = 0.021

• wR(F ²) = 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)

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were placed at calculated idealized positions and refined using a riding model, with C—H = 0.97 Å and N—H = 0.90 Å [and U_iso(H) = 1.2U_eq(C,N)].

Figures

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.

Crystal data

C3H6N3O4+·Cl−	Z = 4
Mr = 183.56	F(000) = 376
Orthorhombic, Cmc21	Dx = 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

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

Refinement

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(Fo2) + (0.0313P)2 + 0.199P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.055	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.18 e Å−3
708 reflections	Δρmin = −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	Flack parameter: 0.09 (7)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.