![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
organic compounds
1,2,3-Trimethoxy-4,5,6-trinitrobenzene
aFachrichtung Chemie, Universität des Saarlandes, Postfach 151150, D-66041 Saarbrücken, Germany
*Correspondence e-mail: hegetschweiler@mx.uni-saarland.de
In the title molecule, C9H9N3O9, the three neighbouring nitro groups are tilted with respect to the benzene mean plane by 75.8 (1), 27.7 (1) and 68.1 (1)°. The methyl C atoms of the three neighbouring methoxy groups deviate from this plane by 0.976 (4), −1.425 (4) and 0.632 (4) Å. The crystal packing exhibits weak C—H⋯O interactions.
Related literature
C—H⋯O hydrogen bonding has been reviewed by Castellano (2004). The use of aromatic polynitro compounds for the preparation of aminocyclitols has been reported by Merten et al. (2012
). The crystal structures of related highly substituted polynitro benzene derivatives with three methoxy or hydroxy groups in a 1,2,3-arrangement have been reported by Vicente et al. (2009
) and Neis et al. (2012
), respectively.
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2010); cell SAINT (Bruker, 2010
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: DIAMOND (Brandenburg, 2011
); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812004783/cv5240sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812004783/cv5240Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812004783/cv5240Isup3.cml
The title compound was obtained by nitration of 1,2,3-trimethoxybenzene. Caution: 1,2,3-trimethoxy-4,5,6-trinitrobenzene is a potential explosive. 1H NMR (CDCl3): δ (p.p.m.) = 4.10. 13C NMR (CDCl3): δ (p.p.m.) = 62.2, 63.4, 130.0, 135.4, 148.1, 151.7. Single crystals were grown by slow evaporation of a MeOH solution at room temperature.
In the absence of significant anomalous scatterers, 932 Friedel pairs were merged before the
H atoms were geometrically positioned (C—H 0.98 Å) and refined as riding, with Uiso(H) = 1.5Ueq of the pivot atom.Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008). ![]() | Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. |
C9H9N3O9 | Dx = 1.632 Mg m−3 |
Mr = 303.19 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 2358 reflections |
a = 8.1743 (4) Å | θ = 2.6–22.6° |
b = 16.6121 (9) Å | µ = 0.15 mm−1 |
c = 9.0856 (5) Å | T = 153 K |
V = 1233.75 (11) Å3 | Prism, colourless |
Z = 4 | 0.18 × 0.15 × 0.11 mm |
F(000) = 624 |
Bruker APEXII KappaCCD diffractometer | 1580 independent reflections |
Radiation source: fine-focus sealed tube | 1254 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ϕ and ω scans | θmax = 28.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2010) | h = −10→7 |
Tmin = 0.974, Tmax = 0.984 | k = −17→21 |
10563 measured reflections | l = −12→11 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.1255P] where P = (Fo2 + 2Fc2)/3 |
1580 reflections | (Δ/σ)max < 0.001 |
193 parameters | Δρmax = 0.16 e Å−3 |
1 restraint | Δρmin = −0.23 e Å−3 |
C9H9N3O9 | V = 1233.75 (11) Å3 |
Mr = 303.19 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 8.1743 (4) Å | µ = 0.15 mm−1 |
b = 16.6121 (9) Å | T = 153 K |
c = 9.0856 (5) Å | 0.18 × 0.15 × 0.11 mm |
Bruker APEXII KappaCCD diffractometer | 1580 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2010) | 1254 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.984 | Rint = 0.041 |
10563 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.16 e Å−3 |
1580 reflections | Δρmin = −0.23 e Å−3 |
193 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.7880 (2) | 0.02818 (11) | 0.3568 (2) | 0.0325 (5) | |
O2 | 0.7134 (2) | 0.08500 (12) | 0.0745 (2) | 0.0332 (5) | |
O3 | 0.6929 (3) | 0.25609 (12) | 0.0347 (2) | 0.0355 (5) | |
O4 | 0.8581 (2) | 0.38957 (11) | 0.1784 (3) | 0.0369 (5) | |
O5 | 0.6246 (2) | 0.39213 (12) | 0.2904 (3) | 0.0387 (5) | |
O6 | 0.8947 (3) | 0.36515 (13) | 0.5039 (2) | 0.0442 (6) | |
O7 | 0.8084 (3) | 0.27870 (13) | 0.6640 (2) | 0.0383 (5) | |
O8 | 0.9907 (3) | 0.13621 (13) | 0.6231 (3) | 0.0446 (6) | |
O9 | 0.7445 (3) | 0.08999 (15) | 0.6539 (2) | 0.0485 (6) | |
N1 | 0.7478 (3) | 0.35847 (12) | 0.2482 (3) | 0.0255 (5) | |
N2 | 0.8365 (3) | 0.30026 (14) | 0.5387 (3) | 0.0287 (5) | |
N3 | 0.8482 (3) | 0.12674 (13) | 0.5858 (3) | 0.0315 (5) | |
C1 | 0.7674 (3) | 0.10752 (16) | 0.3301 (3) | 0.0245 (6) | |
C2 | 0.7350 (3) | 0.13658 (16) | 0.1884 (3) | 0.0257 (6) | |
C3 | 0.7256 (3) | 0.22000 (17) | 0.1639 (3) | 0.0261 (5) | |
C4 | 0.7609 (3) | 0.27185 (16) | 0.2797 (3) | 0.0232 (6) | |
C5 | 0.7990 (3) | 0.24349 (16) | 0.4195 (3) | 0.0233 (5) | |
C6 | 0.7997 (3) | 0.16148 (17) | 0.4432 (3) | 0.0248 (6) | |
C7 | 0.6444 (4) | −0.02228 (17) | 0.3407 (4) | 0.0408 (7) | |
H7A | 0.5960 | −0.0136 | 0.2433 | 0.061* | |
H7B | 0.5643 | −0.0084 | 0.4168 | 0.061* | |
H7C | 0.6757 | −0.0789 | 0.3510 | 0.061* | |
C8 | 0.8624 (4) | 0.0513 (2) | 0.0168 (4) | 0.0471 (9) | |
H8A | 0.8364 | 0.0143 | −0.0638 | 0.071* | |
H8B | 0.9197 | 0.0221 | 0.0949 | 0.071* | |
H8C | 0.9324 | 0.0947 | −0.0202 | 0.071* | |
C9 | 0.5854 (4) | 0.21928 (19) | −0.0721 (3) | 0.0344 (7) | |
H9A | 0.5431 | 0.2607 | −0.1388 | 0.052* | |
H9B | 0.4941 | 0.1932 | −0.0211 | 0.052* | |
H9C | 0.6463 | 0.1790 | −0.1288 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0388 (11) | 0.0224 (9) | 0.0362 (12) | 0.0018 (7) | −0.0039 (9) | −0.0010 (9) |
O2 | 0.0433 (11) | 0.0329 (11) | 0.0235 (11) | −0.0015 (8) | −0.0006 (9) | −0.0110 (9) |
O3 | 0.0506 (11) | 0.0346 (11) | 0.0212 (10) | −0.0119 (9) | −0.0101 (10) | 0.0024 (9) |
O4 | 0.0423 (11) | 0.0325 (11) | 0.0360 (12) | −0.0070 (9) | 0.0115 (10) | 0.0034 (9) |
O5 | 0.0322 (10) | 0.0330 (10) | 0.0508 (14) | 0.0058 (8) | 0.0067 (10) | −0.0058 (10) |
O6 | 0.0585 (13) | 0.0411 (12) | 0.0331 (13) | −0.0237 (11) | −0.0018 (11) | −0.0075 (10) |
O7 | 0.0596 (14) | 0.0359 (11) | 0.0195 (11) | 0.0048 (10) | −0.0007 (10) | −0.0029 (9) |
O8 | 0.0416 (12) | 0.0522 (13) | 0.0401 (13) | 0.0123 (10) | −0.0188 (10) | −0.0059 (10) |
O9 | 0.0640 (15) | 0.0502 (13) | 0.0312 (13) | −0.0101 (11) | −0.0018 (11) | 0.0120 (11) |
N1 | 0.0282 (11) | 0.0268 (12) | 0.0216 (11) | −0.0023 (9) | 0.0006 (10) | −0.0046 (11) |
N2 | 0.0285 (11) | 0.0332 (13) | 0.0245 (14) | 0.0013 (9) | −0.0035 (10) | −0.0063 (10) |
N3 | 0.0431 (14) | 0.0274 (12) | 0.0240 (13) | 0.0073 (10) | −0.0068 (11) | −0.0033 (10) |
C1 | 0.0227 (12) | 0.0268 (13) | 0.0240 (15) | 0.0017 (9) | 0.0008 (11) | −0.0022 (11) |
C2 | 0.0274 (14) | 0.0264 (13) | 0.0234 (14) | −0.0009 (10) | 0.0003 (11) | −0.0052 (11) |
C3 | 0.0268 (13) | 0.0326 (13) | 0.0188 (13) | −0.0028 (11) | −0.0012 (11) | −0.0023 (11) |
C4 | 0.0216 (12) | 0.0248 (13) | 0.0232 (14) | −0.0018 (10) | 0.0024 (11) | −0.0009 (11) |
C5 | 0.0204 (11) | 0.0276 (14) | 0.0218 (14) | 0.0013 (10) | 0.0009 (10) | −0.0066 (11) |
C6 | 0.0240 (13) | 0.0306 (13) | 0.0198 (14) | 0.0041 (10) | −0.0027 (11) | 0.0007 (11) |
C7 | 0.0532 (19) | 0.0317 (15) | 0.0376 (17) | −0.0101 (12) | −0.0055 (16) | 0.0010 (15) |
C8 | 0.061 (2) | 0.0464 (19) | 0.0341 (19) | 0.0180 (16) | −0.0004 (15) | −0.0148 (15) |
C9 | 0.0383 (16) | 0.0441 (17) | 0.0209 (14) | −0.0062 (12) | −0.0039 (12) | −0.0013 (13) |
O1—C1 | 1.351 (3) | C1—C6 | 1.389 (4) |
O1—C7 | 1.451 (3) | C1—C2 | 1.400 (4) |
O2—C2 | 1.355 (3) | C2—C3 | 1.406 (4) |
O2—C8 | 1.439 (4) | C3—C4 | 1.390 (4) |
O3—C3 | 1.345 (3) | C4—C5 | 1.390 (4) |
O3—C9 | 1.445 (3) | C5—C6 | 1.379 (4) |
O4—N1 | 1.218 (3) | C7—H7A | 0.9800 |
O5—N1 | 1.214 (3) | C7—H7B | 0.9800 |
O6—N2 | 1.220 (3) | C7—H7C | 0.9800 |
O7—N2 | 1.215 (3) | C8—H8A | 0.9800 |
O8—N3 | 1.224 (3) | C8—H8B | 0.9800 |
O9—N3 | 1.214 (3) | C8—H8C | 0.9800 |
N1—C4 | 1.471 (3) | C9—H9A | 0.9800 |
N2—C5 | 1.469 (3) | C9—H9B | 0.9800 |
N3—C6 | 1.472 (4) | C9—H9C | 0.9800 |
C1—O1—C7 | 116.4 (2) | C6—C5—C4 | 118.6 (2) |
C2—O2—C8 | 114.4 (2) | C6—C5—N2 | 121.2 (2) |
C3—O3—C9 | 121.2 (2) | C4—C5—N2 | 120.2 (2) |
O5—N1—O4 | 125.7 (2) | C5—C6—C1 | 121.4 (2) |
O5—N1—C4 | 116.7 (2) | C5—C6—N3 | 121.7 (2) |
O4—N1—C4 | 117.5 (2) | C1—C6—N3 | 116.7 (2) |
O7—N2—O6 | 125.2 (2) | O1—C7—H7A | 109.5 |
O7—N2—C5 | 117.5 (2) | O1—C7—H7B | 109.5 |
O6—N2—C5 | 117.2 (2) | H7A—C7—H7B | 109.5 |
O9—N3—O8 | 126.0 (3) | O1—C7—H7C | 109.5 |
O9—N3—C6 | 117.2 (2) | H7A—C7—H7C | 109.5 |
O8—N3—C6 | 116.7 (2) | H7B—C7—H7C | 109.5 |
O1—C1—C6 | 118.2 (2) | O2—C8—H8A | 109.5 |
O1—C1—C2 | 121.7 (2) | O2—C8—H8B | 109.5 |
C6—C1—C2 | 119.6 (2) | H8A—C8—H8B | 109.5 |
O2—C2—C1 | 120.6 (2) | O2—C8—H8C | 109.5 |
O2—C2—C3 | 119.7 (2) | H8A—C8—H8C | 109.5 |
C1—C2—C3 | 119.7 (2) | H8B—C8—H8C | 109.5 |
O3—C3—C4 | 115.2 (2) | O3—C9—H9A | 109.5 |
O3—C3—C2 | 126.1 (3) | O3—C9—H9B | 109.5 |
C4—C3—C2 | 118.7 (2) | H9A—C9—H9B | 109.5 |
C3—C4—C5 | 121.9 (2) | O3—C9—H9C | 109.5 |
C3—C4—N1 | 116.4 (2) | H9A—C9—H9C | 109.5 |
C5—C4—N1 | 121.7 (2) | H9B—C9—H9C | 109.5 |
C7—O1—C1—C6 | 119.7 (3) | O4—N1—C4—C5 | 106.2 (3) |
C7—O1—C1—C2 | −68.4 (3) | C3—C4—C5—C6 | −0.7 (4) |
C8—O2—C2—C1 | −77.5 (3) | N1—C4—C5—C6 | 176.2 (2) |
C8—O2—C2—C3 | 102.2 (3) | C3—C4—C5—N2 | 179.7 (2) |
O1—C1—C2—O2 | 4.1 (4) | N1—C4—C5—N2 | −3.5 (4) |
C6—C1—C2—O2 | 175.8 (2) | O7—N2—C5—C6 | −26.9 (4) |
O1—C1—C2—C3 | −175.6 (2) | O6—N2—C5—C6 | 152.5 (3) |
C6—C1—C2—C3 | −3.9 (4) | O7—N2—C5—C4 | 152.7 (2) |
C9—O3—C3—C4 | −151.0 (2) | O6—N2—C5—C4 | −27.9 (3) |
C9—O3—C3—C2 | 32.6 (4) | C4—C5—C6—C1 | 1.6 (4) |
O2—C2—C3—O3 | 1.4 (4) | N2—C5—C6—C1 | −178.7 (2) |
C1—C2—C3—O3 | −178.9 (2) | C4—C5—C6—N3 | 176.3 (2) |
O2—C2—C3—C4 | −175.0 (2) | N2—C5—C6—N3 | −4.0 (4) |
C1—C2—C3—C4 | 4.8 (4) | O1—C1—C6—C5 | 172.7 (2) |
O3—C3—C4—C5 | −179.3 (2) | C2—C1—C6—C5 | 0.7 (4) |
C2—C3—C4—C5 | −2.5 (4) | O1—C1—C6—N3 | −2.3 (3) |
O3—C3—C4—N1 | 3.7 (3) | C2—C1—C6—N3 | −174.3 (2) |
C2—C3—C4—N1 | −179.5 (2) | O9—N3—C6—C5 | 116.1 (3) |
O5—N1—C4—C3 | 101.0 (3) | O8—N3—C6—C5 | −65.4 (3) |
O4—N1—C4—C3 | −76.8 (3) | O9—N3—C6—C1 | −69.0 (3) |
O5—N1—C4—C5 | −76.0 (3) | O8—N3—C6—C1 | 109.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O4i | 0.98 | 2.53 | 3.450 (4) | 156 |
C9—H9C···O9ii | 0.98 | 2.59 | 3.536 (4) | 161 |
C8—H8A···O5iii | 0.98 | 2.44 | 3.352 (4) | 154 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x, y, z−1; (iii) −x+3/2, y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H9N3O9 |
Mr | 303.19 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 153 |
a, b, c (Å) | 8.1743 (4), 16.6121 (9), 9.0856 (5) |
V (Å3) | 1233.75 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.18 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Bruker APEXII KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2010) |
Tmin, Tmax | 0.974, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10563, 1580, 1254 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.081, 1.02 |
No. of reflections | 1580 |
No. of parameters | 193 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.23 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2011).
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O4i | 0.98 | 2.53 | 3.450 (4) | 155.9 |
C9—H9C···O9ii | 0.98 | 2.59 | 3.536 (4) | 161.1 |
C8—H8A···O5iii | 0.98 | 2.44 | 3.352 (4) | 154.0 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x, y, z−1; (iii) −x+3/2, y−1/2, z−1/2. |
Acknowledgements
The authors thank Dr Volker Huch (Universität des Saarlandes) for the collection of the data set.
References
Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Castellano, R. K. (2004). Curr. Org. Chem. 8, 845–865. Web of Science CrossRef CAS Google Scholar
Merten, G. J., Neis, C., Stucky, S., Huch, V., Rentschler, E., Natter, H., Hempelmann, R., Stöwe, K. & Hegetschweiler, K. (2012). Eur. J. Inorg. Chem. pp. 31–35. Web of Science CSD CrossRef Google Scholar
Neis, C., Merten, G. J. & Hegetschweiler, K. (2012). Acta Cryst. E68, o695. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vicente, J., Arcas, A., Galvez-Lopez, M.-D., Jones, P. G. & Bautista, D. (2009). Organometallics, 28, 3501–3517. Web of Science CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Polynitrophenols and their methyl ethers are of interest as possible synthons for the preparation of corresponding aminocyclitols. The crystal structure of the title compound consists of wavy layers which are oriented parallel to the bc plane. In these layers, each molecule is surrounded by six neighbours, and the intermolecular contacts within these layers are mainly based on methoxy groups pointing to neighbouring nitro groups, indicating some weak C—H···O—N hydrogen bonding. Between the layers, some of the contacts such as O5···C1 (2.94 Å) are slightly shorter than the sum of the van der Waals radii. Similar to the structure of 4,6-dinitrobenzene-1,2,3-triol, this observation may indicate some weak donor acceptor interactions. However, it should be noted that the tilting of the nitro groups out of the aromatic plane, which is obviously enforced by the increased steric crowding, disfavours a closer approximation of aromatic moieties which are arranged in neighbouring layers.