organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Bis(2,2-di­nitro­prop­yl)formal

aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and bChina Academy of Engineering Physics, Mianyang 621900, People's Republic of China
*Correspondence e-mail: kouxm@scu.edu.cn

(Received 11 March 2009; accepted 23 March 2009; online 28 March 2009)

The complete mol­ecule of the title compound [systematic name: bis(2,2-dinitro­prop­oxy)methane], C7H12N4O10, which was synthesized by the condensation reaction between 2,2-dinitro­propanol and paraformaldehyde in methyl­ene chloride, is generated by crystallographic twofold symmetry with one C atom lying on the rotation axis. In the crystal structure, mol­ecules are linked into chains running parallel to the b axis by inter­molecular C—H⋯O hydrogen-bond inter­actions, generating rings of graph-set motif R22(14).

Related literature

For the applications and chemistry of the title compound, see: Garver et al. (1985[Garver, L. C., Grakauskas, V. & Baum, K. (1985). J. Org. Chem. 50, 1699-1702.]); Hamilton & Wardle (1995[Hamilton, R. S. & Wardle, R. B. (1995). US Patent No. 5 449 835.]); Adolph (1991[Adolph, H. G. (1991). US Patent No. 4 997 499.]); Hamilton & Wardle (1997[Hamilton, R. S. & Wardle, R. B. (1997). US Patent No. 5 648 556.]). For graph-set motifs, see: Bernstein (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C7H12N4O10

  • Mr = 312.21

  • Monoclinic, C 2/c

  • a = 23.330 (3) Å

  • b = 6.207 (3) Å

  • c = 10.009 (6) Å

  • β = 109.60 (3)°

  • V = 1365.6 (11) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.14 mm−1

  • T = 291 K

  • 0.48 × 0.44 × 0.28 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: none

  • 1404 measured reflections

  • 1255 independent reflections

  • 863 reflections with I > 2σ(I)

  • Rint = 0.008

  • 3 standard reflections every 100 reflections intensity decay: 1.5%

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.138

  • S = 1.09

  • 1255 reflections

  • 98 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1A⋯O4i 0.97 2.59 3.509 (3) 158
C1—H1B⋯O4ii 0.97 2.59 3.509 (3) 158
Symmetry codes: (i) [x, -y+1, z+{\script{1\over 2}}]; (ii) -x+1, -y+1, -z.

Data collection: DIFRAC (Gabe & White, 1993[Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association, Pittsburgh meeting. Abstract PA 104.]); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989[Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384-387.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound is an important energetic material used in propellant and explosive formulations (Garver et al. 1985; Hamilton & Wardle, 1995). It was also combined with liquid bis(2,2-dinitropropyl)acetal (BDNPA) to prepare the BDNPF/A energetic plasticizer (Adolph, 1991; Hamilton & Wardle, 1997). Here we report the crystal structure of the title compound.

The molecule of the title compound (Fig. 1), has crystallographically imposed two-fold symmetry. The average of N—O bond length is 1.204 (3) Å. The dihedral angle formed by the planes through the nitro group is 74.3 (2)°. The O(1)—C(2)—C(3)—N(1), O(5)—N(2)—C(3)—C(4) and O(4)—N(2)—C(3)—C(4) torsion angles are 172.59 (17), -176.2 (2) and 5.6 (3) ° respectively. In the crystal structure, the molecules are linked into chains running parallel to the b axis by intermolecular C—H···O hydrogen interactions (Table 1) generating rings of graph set motif R22(14).

Related literature top

For the applications and chemistry of the title compound, see: Garver et al. (1985); Hamilton & Wardle (1995); Adolph (1991); Hamilton & Wardle (1997). For graph-set motifs, see: Bernstein (1995).

Experimental top

The title compound was synthesized by reacting 2,2-dinitropropanol (6.0 g) with paraformaldehyde (0.6 g) in the presence of concentrated sulfuric acid as catalyst in methylene chloride below 5°C. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a diethyl ether/mineral ether (1:6 v/v) solution.

Refinement top

All non-H atoms were refined with anisotropic atomic displacement parameters. All H atoms were positioned geometrically and refined using a riding model, with C—H =0.96–0.97 Å and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Atoms labelled with the suffix 2 are generated by the symmetry operator (1-x, y, 1/2-z).
Bis(2,2-dinitropropoxy)methane top
Crystal data top
C7H12N4O10F(000) = 648
Mr = 312.21Dx = 1.519 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 23 reflections
a = 23.330 (3) Åθ = 5.2–8.7°
b = 6.207 (3) ŵ = 0.14 mm1
c = 10.009 (6) ÅT = 291 K
β = 109.60 (3)°Block, colourless
V = 1365.6 (11) Å30.48 × 0.44 × 0.28 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.008
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 1.9°
Graphite monochromatorh = 2820
ω/2θ scansk = 07
1404 measured reflectionsl = 1212
1255 independent reflections3 standard reflections every 100 reflections
863 reflections with I > 2σ(I) intensity decay: 1.5%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.138 w = 1/[σ2(Fo2) + (0.0654P)2 + 0.7176P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1255 reflectionsΔρmax = 0.18 e Å3
98 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.032 (3)
Crystal data top
C7H12N4O10V = 1365.6 (11) Å3
Mr = 312.21Z = 4
Monoclinic, C2/cMo Kα radiation
a = 23.330 (3) ŵ = 0.14 mm1
b = 6.207 (3) ÅT = 291 K
c = 10.009 (6) Å0.48 × 0.44 × 0.28 mm
β = 109.60 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.008
1404 measured reflections3 standard reflections every 100 reflections
1255 independent reflections intensity decay: 1.5%
863 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.138H-atom parameters constrained
S = 1.09Δρmax = 0.18 e Å3
1255 reflectionsΔρmin = 0.17 e Å3
98 parameters
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
xyzUiso*/UeqOcc. (<1)
O10.54239 (7)0.5416 (3)0.21472 (18)0.0661 (6)
O20.68680 (8)0.8202 (3)0.51558 (17)0.0706 (6)
O30.70016 (9)1.0217 (3)0.3547 (2)0.0854 (7)
O40.60961 (13)0.8225 (4)0.0432 (2)0.1153 (10)
O50.57606 (12)1.0244 (4)0.1735 (3)0.1154 (9)
N10.67637 (8)0.8730 (3)0.3932 (2)0.0538 (5)
N20.60412 (11)0.8729 (4)0.1542 (2)0.0702 (7)
C10.50000.4161 (6)0.25000.0721 (11)
H1A0.52110.32410.32970.087*0.50
H1B0.47890.32410.17030.087*0.50
C20.58346 (10)0.6513 (4)0.3320 (2)0.0619 (7)
H2A0.59910.55500.41240.074*
H2B0.56360.77210.35960.074*
C30.63384 (9)0.7279 (3)0.2821 (2)0.0470 (6)
C40.67114 (13)0.5524 (5)0.2509 (4)0.0887 (10)
H4A0.70000.61350.21220.133*
H4B0.64500.45420.18350.133*
H4C0.69240.47650.33680.133*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0497 (9)0.0705 (11)0.0702 (11)0.0102 (8)0.0098 (8)0.0145 (8)
O20.0670 (11)0.0859 (12)0.0506 (10)0.0086 (9)0.0086 (7)0.0062 (9)
O30.0912 (13)0.0750 (13)0.0901 (14)0.0353 (11)0.0306 (11)0.0070 (10)
O40.179 (3)0.1115 (18)0.0553 (12)0.0540 (17)0.0396 (14)0.0049 (12)
O50.1221 (19)0.0748 (14)0.127 (2)0.0347 (14)0.0122 (15)0.0233 (13)
N10.0481 (10)0.0533 (11)0.0610 (12)0.0045 (9)0.0193 (9)0.0076 (9)
N20.0834 (15)0.0650 (14)0.0552 (13)0.0133 (12)0.0137 (11)0.0046 (11)
C10.0401 (16)0.0499 (18)0.114 (3)0.0000.0094 (17)0.000
C20.0580 (13)0.0718 (15)0.0523 (13)0.0174 (12)0.0138 (10)0.0065 (11)
C30.0464 (11)0.0457 (11)0.0454 (11)0.0006 (9)0.0107 (9)0.0038 (9)
C40.0676 (16)0.0807 (19)0.108 (2)0.0146 (14)0.0159 (15)0.0383 (18)
Geometric parameters (Å, º) top
O1—C11.394 (3)C1—H1A0.9700
O1—C21.416 (3)C1—H1B0.9700
O2—N11.211 (2)C2—C31.500 (3)
O3—N11.205 (2)C2—H2A0.9700
O4—N21.202 (3)C2—H2B0.9700
O5—N21.198 (3)C3—C41.491 (3)
N1—C31.514 (3)C4—H4A0.9600
N2—C31.528 (3)C4—H4B0.9600
C1—O1i1.394 (3)C4—H4C0.9600
C1—O1—C2113.52 (16)O1—C2—H2B110.7
O3—N1—O2124.98 (19)C3—C2—H2B110.7
O3—N1—C3118.63 (19)H2A—C2—H2B108.8
O2—N1—C3116.20 (18)C4—C3—C2114.6 (2)
O5—N2—O4126.0 (3)C4—C3—N1107.70 (18)
O5—N2—C3116.5 (2)C2—C3—N1109.75 (17)
O4—N2—C3117.5 (2)C4—C3—N2112.8 (2)
O1—C1—O1i112.1 (3)C2—C3—N2106.23 (18)
O1—C1—H1A109.2N1—C3—N2105.44 (18)
O1i—C1—H1A109.2C3—C4—H4A109.5
O1—C1—H1B109.2C3—C4—H4B109.5
O1i—C1—H1B109.2H4A—C4—H4B109.5
H1A—C1—H1B107.9C3—C4—H4C109.5
O1—C2—C3105.36 (18)H4A—C4—H4C109.5
O1—C2—H2A110.7H4B—C4—H4C109.5
C3—C2—H2A110.7
C2—O1—C1—O1i70.17 (16)O3—N1—C3—N231.8 (3)
C1—O1—C2—C3165.8 (2)O2—N1—C3—N2152.91 (19)
O1—C2—C3—C466.1 (3)O5—N2—C3—C4176.2 (2)
O1—C2—C3—N1172.59 (17)O4—N2—C3—C45.6 (3)
O1—C2—C3—N259.1 (2)O5—N2—C3—C257.6 (3)
O3—N1—C3—C488.8 (3)O4—N2—C3—C2120.7 (2)
O2—N1—C3—C486.4 (3)O5—N2—C3—N158.9 (3)
O3—N1—C3—C2145.9 (2)O4—N2—C3—N1122.9 (2)
O2—N1—C3—C238.9 (3)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O4ii0.972.593.509 (3)158
C1—H1B···O4iii0.972.593.509 (3)158
Symmetry codes: (ii) x, y+1, z+1/2; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC7H12N4O10
Mr312.21
Crystal system, space groupMonoclinic, C2/c
Temperature (K)291
a, b, c (Å)23.330 (3), 6.207 (3), 10.009 (6)
β (°) 109.60 (3)
V3)1365.6 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.48 × 0.44 × 0.28
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1404, 1255, 863
Rint0.008
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.138, 1.09
No. of reflections1255
No. of parameters98
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.17

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O4i0.972.593.509 (3)158
C1—H1B···O4ii0.972.593.509 (3)158
Symmetry codes: (i) x, y+1, z+1/2; (ii) x+1, y+1, z.
 

Acknowledgements

The authors thank Mr Zhi-Hua Mao of Sichuan University for the X-ray data collection.

References

First citationAdolph, H. G. (1991). US Patent No. 4 997 499.  Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationGabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association, Pittsburgh meeting. Abstract PA 104.  Google Scholar
First citationGarver, L. C., Grakauskas, V. & Baum, K. (1985). J. Org. Chem. 50, 1699-1702.  CrossRef CAS Web of Science Google Scholar
First citationHamilton, R. S. & Wardle, R. B. (1995). US Patent No. 5 449 835.  Google Scholar
First citationHamilton, R. S. & Wardle, R. B. (1997). US Patent No. 5 648 556.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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