2-Nitro-1,3-dinitro­oxypropane

Breiner, M.M.; Chavez, D.E.; Parrish, D.A.

doi:10.1107/S1600536813004170

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o384

doi:10.1107/S1600536813004170

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2-Nitro-1,3-dinitrooxypropane

Megan M. Breiner,^a David E. Chavez ^b and Damon A. Parrish ^c ^*

^aMS C920, Los Alamos National Laboratory, Los Alamos, NM 87545, USA, ^bTechnical Staff Member, MS C920, Los Alamos National Laboratory, Los Alamos, NM 87545, USA, and ^cCBMSE, Code 6910, Naval Research Laboratory, Washington, DC 20375, USA
^*Correspondence e-mail: damon.parrish@nrl.navy.mil

(Received 28 January 2013; accepted 11 February 2013; online 16 February 2013)

The title compound, C₃H₅N₃O₈, was synthesized by reacting 2-nitropropane-1,3-diol with acetyl nitrate. The molecule is bisected by a crystallograpic mirror plane. In the crystal, the molecules pack in a ribbon-like fashion along the c axis, with the central nitro groups pointing in the same direction. C—H⋯O contacts apparently provide some additional packing stabilization.

Related literature

Nitrate esters are often studied for their energetic materials properties. For example, we have reported the synthesis and crystal structure of a low melting nitrate ester (Chavez, et al. 2008 )·The title compound was first synthesized by Römer (1955) but no information has been reported on the crystal structure of this material. A smilar structure was reported that differs only in a nitrooxy group at the 2-position (Espenbetov et al. 1984 ).

Experimental

Crystal data

C₃H₅N₃O₈
M_r = 211.10
Orthorhombic, C m c 2₁
a = 14.046 (5) Å
b = 9.607 (5) Å
c = 5.903 (3) Å
V = 796.5 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.38 × 0.02 × 0.01 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.935, T_max = 0.998
3416 measured reflections
841 independent reflections
587 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.083
S = 1.00
841 reflections
70 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯O4ⁱ	0.97	2.56	3.405 (5)	145
Symmetry code: (i) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813004170/ld2094sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004170/ld2094Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004170/ld2094Isup3.cml

checkCIF report

Comment top

In our efforts to synthesize energetic materials with novel properties, we identified the title compound, 2-nitro-1,3-dinitrooxypropane (Fig. 1), as a nitrate ester for which very little information exists in the literature. The compound was synthesized in a one- step process whereby 2-nitropropane-1,3-diol was subjected to nitration conditions using acetyl nitrate as the substrate (Fig. 2). Suitable crystals were grown from carbon tetrachloride and subjected to X-ray analysis for structure confirmation. The molecule lies on a mirror plane, making only half of the molecule crystallographically unique.

Related literature top

Nitrate esters are often studied for their energetic materials properties. For example, we have reported the synthesis and crystal structure of a low melting nitrate ester (Chavez, et al. 2008).The title compound was first synthesized by Römer (1955) but no information has been reported on the crystal structure of this material. A smilar structure was reported that differs only in a nitrooxy group at the 2-position (Espenbetov et al. 1984).

Experimental top

Crystals suitable for X-ray crystallographic analysis were grown from carbon tetrachloride. The crystals were isolated as white needles.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009) and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of 1 showing the labeling of the non-H atoms. Thermal ellipsoids are shown at the 50% probability level.
	Fig. 2. The synthesis of 2-nitro-1,3-dinitrooxypropane.

2-Nitro-1,3-dinitrooxypropane top

Crystal data top

C₃H₅N₃O₈	F(000) = 432
M_r = 211.10	D_x = 1.760 Mg m⁻³
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71073 Å
a = 14.046 (5) Å	µ = 0.18 mm⁻¹
b = 9.607 (5) Å	T = 293 K
c = 5.903 (3) Å	Needle, colourless
V = 796.5 (7) Å³	0.38 × 0.02 × 0.01 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	841 independent reflections
Radiation source: fine focus sealed tube	587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scans	θ_max = 26.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −17→17
T_min = 0.935, T_max = 0.998	k = −11→11
3416 measured reflections	l = −7→7

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) = 0.083	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0389P)²] where P = (F_o² + 2F_c²)/3
841 reflections	(Δ/σ)_max < 0.001
70 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₃H₅N₃O₈	V = 796.5 (7) Å³
M_r = 211.10	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 14.046 (5) Å	µ = 0.18 mm⁻¹
b = 9.607 (5) Å	T = 293 K
c = 5.903 (3) Å	0.38 × 0.02 × 0.01 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	841 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	587 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.998	R_int = 0.052
3416 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.083	H-atom parameters constrained
S = 1.00	Δρ_max = 0.15 e Å⁻³
841 reflections	Δρ_min = −0.18 e Å⁻³
70 parameters

Special details top

Experimental. Acetic acid (6.25 ml) and acetic anhydride (6.25 ml) were added to a 50 ml jacketed flask. The solution was then cooled to 0 degress C and HNO3 (4.25 g, 98%) was added dropwise while maintaining the reaction temperature below 5 degrees C. The reaction was allowed to stir for 20 min. and 2-nitro-1,3-propanediol (1.51 g, 12.5 mmol) was added. After stirring for 2 h at 0 degrees C, the temperature was raised to 20 degrees C over one hour and then stirred at 20 degrees C for an additional hour The reaction mixture was then poured into 25 ml of ice water and stirred. The white solid was filtered and washed with water and air dried to give 2.19 g of crude 1. This material was then recrystallized from carbon tetrachloride to give white needles. The melting point was measured to be 68–69 degrees C. IR analysis (KBr), proton NMR analysis (300 MHz, deuterioacetone), and elemental analysis were also performed for additional characterization.

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
C1	0.5000	0.2314 (4)	0.4290 (7)	0.0314 (8)
H1	0.5000	0.1318	0.3932	0.038*
N2	0.5000	0.2530 (4)	0.6828 (6)	0.0392 (8)
O3	0.5000	0.1504 (4)	0.8026 (5)	0.0743 (10)
O4	0.5000	0.3716 (4)	0.7543 (5)	0.0606 (9)
C5	0.58746 (15)	0.3011 (3)	0.3296 (5)	0.0386 (6)
H5A	0.5877	0.2874	0.1669	0.046*
H5B	0.5839	0.4004	0.3581	0.046*
O6	0.67514 (11)	0.24806 (16)	0.4225 (4)	0.0404 (5)
N7	0.70956 (17)	0.1273 (2)	0.3130 (4)	0.0429 (6)
O8	0.65815 (14)	0.07181 (19)	0.1797 (5)	0.0614 (6)
O9	0.78766 (13)	0.0968 (2)	0.3745 (4)	0.0611 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0337 (18)	0.028 (2)	0.032 (2)	0.000	0.000	−0.0047 (17)
N2	0.0324 (16)	0.045 (2)	0.040 (2)	0.000	0.000	−0.004 (2)
O3	0.105 (3)	0.071 (2)	0.047 (2)	0.000	0.000	0.0159 (19)
O4	0.065 (2)	0.057 (2)	0.060 (2)	0.000	0.000	−0.0235 (17)
C5	0.0322 (14)	0.0359 (14)	0.0477 (17)	0.0026 (11)	0.0018 (13)	0.0015 (14)
O6	0.0318 (9)	0.0415 (11)	0.0480 (11)	0.0025 (8)	−0.0019 (9)	−0.0094 (10)
N7	0.0355 (12)	0.0428 (14)	0.0505 (14)	0.0019 (12)	0.0096 (12)	0.0041 (13)
O8	0.0554 (13)	0.0563 (14)	0.0725 (15)	0.0030 (11)	0.0032 (14)	−0.0254 (15)
O9	0.0359 (11)	0.0679 (15)	0.0796 (17)	0.0153 (9)	0.0032 (11)	0.0177 (12)

Geometric parameters (Å, º) top

C1—N2	1.512 (6)	C5—O6	1.441 (3)
C1—C5	1.517 (3)	C5—H5A	0.9700
C1—C5ⁱ	1.517 (3)	C5—H5B	0.9700
C1—H1	0.9800	O6—N7	1.413 (3)
N2—O3	1.213 (4)	N7—O9	1.192 (3)
N2—O4	1.215 (4)	N7—O8	1.194 (3)

N2—C1—C5	108.8 (2)	O6—C5—H5A	109.0
N2—C1—C5ⁱ	108.8 (2)	C1—C5—H5A	109.0
C5—C1—C5ⁱ	108.2 (3)	O6—C5—H5B	109.0
N2—C1—H1	110.3	C1—C5—H5B	109.0
C5—C1—H1	110.3	H5A—C5—H5B	107.8
C5ⁱ—C1—H1	110.3	N7—O6—C5	114.1 (2)
O3—N2—O4	124.0 (4)	O9—N7—O8	130.4 (2)
O3—N2—C1	117.8 (3)	O9—N7—O6	112.1 (2)
O4—N2—C1	118.2 (3)	O8—N7—O6	117.5 (2)
O6—C5—C1	112.9 (2)

C5—C1—N2—O3	−121.2 (2)	C5ⁱ—C1—C5—O6	176.71 (15)
C5ⁱ—C1—N2—O3	121.2 (2)	C1—C5—O6—N7	85.4 (3)
C5—C1—N2—O4	58.8 (2)	C5—O6—N7—O9	171.0 (2)
C5ⁱ—C1—N2—O4	−58.8 (2)	C5—O6—N7—O8	−9.7 (3)
N2—C1—C5—O6	58.6 (3)

Symmetry code: (i) −x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O4ⁱⁱ	0.97	2.56	3.405 (5)	145

Symmetry code: (ii) −x+1, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₃H₅N₃O₈
M_r	211.10
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	293
a, b, c (Å)	14.046 (5), 9.607 (5), 5.903 (3)
V (Å³)	796.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.38 × 0.02 × 0.01

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.935, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	3416, 841, 587
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.083, 1.00
No. of reflections	841
No. of parameters	70
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009) and XPREP (Bruker, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O4ⁱ	0.97	2.56	3.405 (5)	145

Symmetry code: (i) −x+1, −y+1, z−1/2.

Acknowledgements

The authors would like to thank the DoD/DOE Joint Munitions Technology Development Program. Los Alamos National Laboratory is operated by Los Alamos National Security (LANS, LLC) under contract No. DE—AC52–06 N A25396 for the US Department of Energy. Crystallographic studies were supported in part by the Office of Naval Research (ONR) and the Naval Research Laboratory (NRL).

References

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