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ISSN: 2056-9890

2-Nitro-1,3-di­nitro­oxypropane

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[Chavez, D. E., Hiskey, M. A., Naud, D. L. & Parrish, D. A. (2008). Angew. Chem. Int. Ed. 23, 8307-8309.])·The title compound was first synthesized by Römer (1955)[Römer, F. (1955). Angew. Chem. 67, 157.] 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[Espenbetov, A. A., Antipin, M. Yu., Struchkov, Yu. T., Philippov, V. A., Tsirel'son, V. G., Ozerov, R. P. & Svetlov, B. S. (1984). Acta Cryst. C40, 2096-2098.]).

[Scheme 1]

Experimental

Crystal data
  • C3H5N3O8

  • Mr = 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[Bruker (2008). SADABS and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.935, Tmax = 0.998

  • 3416 measured reflections

  • 841 independent reflections

  • 587 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT and XPREP (Bruker, 2008[Bruker (2008). SADABS and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

The full-matrix least-squares refinement on F2 included atomic coordinates and anisotropic thermal parameters for all non-H atoms. The H atoms were included using a riding model.

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
[Figure 1] Fig. 1. View of 1 showing the labeling of the non-H atoms. Thermal ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The synthesis of 2-nitro-1,3-dinitrooxypropane.
2-Nitro-1,3-dinitrooxypropane top
Crystal data top
C3H5N3O8F(000) = 432
Mr = 211.10Dx = 1.760 Mg m3
Orthorhombic, Cmc21Mo Kα radiation, λ = 0.71073 Å
a = 14.046 (5) ŵ = 0.18 mm1
b = 9.607 (5) ÅT = 293 K
c = 5.903 (3) ÅNeedle, colourless
V = 796.5 (7) Å30.38 × 0.02 × 0.01 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD
diffractometer
841 independent reflections
Radiation source: fine focus sealed tube587 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scansθmax = 26.3°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1717
Tmin = 0.935, Tmax = 0.998k = 1111
3416 measured reflectionsl = 77
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0389P)2]
where P = (Fo2 + 2Fc2)/3
841 reflections(Δ/σ)max < 0.001
70 parametersΔρmax = 0.15 e Å3
1 restraintΔρmin = 0.18 e Å3
Crystal data top
C3H5N3O8V = 796.5 (7) Å3
Mr = 211.10Z = 4
Orthorhombic, Cmc21Mo Kα radiation
a = 14.046 (5) ŵ = 0.18 mm1
b = 9.607 (5) ÅT = 293 K
c = 5.903 (3) Å0.38 × 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)
Tmin = 0.935, Tmax = 0.998Rint = 0.052
3416 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0381 restraint
wR(F2) = 0.083H-atom parameters constrained
S = 1.00Δρmax = 0.15 e Å3
841 reflectionsΔρmin = 0.18 e Å3
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
xyzUiso*/Ueq
C10.50000.2314 (4)0.4290 (7)0.0314 (8)
H10.50000.13180.39320.038*
N20.50000.2530 (4)0.6828 (6)0.0392 (8)
O30.50000.1504 (4)0.8026 (5)0.0743 (10)
O40.50000.3716 (4)0.7543 (5)0.0606 (9)
C50.58746 (15)0.3011 (3)0.3296 (5)0.0386 (6)
H5A0.58770.28740.16690.046*
H5B0.58390.40040.35810.046*
O60.67514 (11)0.24806 (16)0.4225 (4)0.0404 (5)
N70.70956 (17)0.1273 (2)0.3130 (4)0.0429 (6)
O80.65815 (14)0.07181 (19)0.1797 (5)0.0614 (6)
O90.78766 (13)0.0968 (2)0.3745 (4)0.0611 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0337 (18)0.028 (2)0.032 (2)0.0000.0000.0047 (17)
N20.0324 (16)0.045 (2)0.040 (2)0.0000.0000.004 (2)
O30.105 (3)0.071 (2)0.047 (2)0.0000.0000.0159 (19)
O40.065 (2)0.057 (2)0.060 (2)0.0000.0000.0235 (17)
C50.0322 (14)0.0359 (14)0.0477 (17)0.0026 (11)0.0018 (13)0.0015 (14)
O60.0318 (9)0.0415 (11)0.0480 (11)0.0025 (8)0.0019 (9)0.0094 (10)
N70.0355 (12)0.0428 (14)0.0505 (14)0.0019 (12)0.0096 (12)0.0041 (13)
O80.0554 (13)0.0563 (14)0.0725 (15)0.0030 (11)0.0032 (14)0.0254 (15)
O90.0359 (11)0.0679 (15)0.0796 (17)0.0153 (9)0.0032 (11)0.0177 (12)
Geometric parameters (Å, º) top
C1—N21.512 (6)C5—O61.441 (3)
C1—C51.517 (3)C5—H5A0.9700
C1—C5i1.517 (3)C5—H5B0.9700
C1—H10.9800O6—N71.413 (3)
N2—O31.213 (4)N7—O91.192 (3)
N2—O41.215 (4)N7—O81.194 (3)
N2—C1—C5108.8 (2)O6—C5—H5A109.0
N2—C1—C5i108.8 (2)C1—C5—H5A109.0
C5—C1—C5i108.2 (3)O6—C5—H5B109.0
N2—C1—H1110.3C1—C5—H5B109.0
C5—C1—H1110.3H5A—C5—H5B107.8
C5i—C1—H1110.3N7—O6—C5114.1 (2)
O3—N2—O4124.0 (4)O9—N7—O8130.4 (2)
O3—N2—C1117.8 (3)O9—N7—O6112.1 (2)
O4—N2—C1118.2 (3)O8—N7—O6117.5 (2)
O6—C5—C1112.9 (2)
C5—C1—N2—O3121.2 (2)C5i—C1—C5—O6176.71 (15)
C5i—C1—N2—O3121.2 (2)C1—C5—O6—N785.4 (3)
C5—C1—N2—O458.8 (2)C5—O6—N7—O9171.0 (2)
C5i—C1—N2—O458.8 (2)C5—O6—N7—O89.7 (3)
N2—C1—C5—O658.6 (3)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5B···O4ii0.972.563.405 (5)145
Symmetry code: (ii) x+1, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC3H5N3O8
Mr211.10
Crystal system, space groupOrthorhombic, Cmc21
Temperature (K)293
a, b, c (Å)14.046 (5), 9.607 (5), 5.903 (3)
V3)796.5 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.38 × 0.02 × 0.01
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.935, 0.998
No. of measured, independent and
observed [I > 2σ(I)] reflections
3416, 841, 587
Rint0.052
(sin θ/λ)max1)0.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.083, 1.00
No. of reflections841
No. of parameters70
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C5—H5B···O4i0.972.563.405 (5)145
Symmetry code: (i) x+1, y+1, z1/2.
 

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

First citationBruker (2008). SADABS and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationChavez, D. E., Hiskey, M. A., Naud, D. L. & Parrish, D. A. (2008). Angew. Chem. Int. Ed. 23, 8307–8309.  Web of Science CSD CrossRef
First citationEspenbetov, A. A., Antipin, M. Yu., Struchkov, Yu. T., Philippov, V. A., Tsirel'son, V. G., Ozerov, R. P. & Svetlov, B. S. (1984). Acta Cryst. C40, 2096–2098.  CSD CrossRef CAS Web of Science IUCr Journals
First citationRömer, F. (1955). Angew. Chem. 67, 157.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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COMMUNICATIONS
ISSN: 2056-9890
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