1,2,3-Trimeth­oxy-4,5,6-trinitro­benzene

Merten, G.J.; Neis, C.; Hegetschweiler, K.

doi:10.1107/S1600536812004783

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o694

doi:10.1107/S1600536812004783

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1,2,3-Trimethoxy-4,5,6-trinitrobenzene

Günter J. Merten,^a Christian Neis ^a and Kaspar Hegetschweiler ^a ^*

^aFachrichtung Chemie, Universität des Saarlandes, Postfach 151150, D-66041 Saarbrücken, Germany
^*Correspondence e-mail: hegetschweiler@mx.uni-saarland.de

(Received 25 January 2012; accepted 3 February 2012; online 17 February 2012)

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

C₉H₉N₃O₉
M_r = 303.19
Orthorhombic, P n a 2₁
a = 8.1743 (4) Å
b = 16.6121 (9) Å
c = 9.0856 (5) Å
V = 1233.75 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 153 K
0.18 × 0.15 × 0.11 mm

Data collection

Bruker APEXII KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.974, T_max = 0.984
10563 measured reflections
1580 independent reflections
1254 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.02
1580 reflections
193 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) x, y, z-1; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812004783/cv5240sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004783/cv5240Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004783/cv5240Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: 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).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

1,2,3-Trimethoxy-4,5,6-trinitrobenzene top

Crystal data top

C₉H₉N₃O₉	D_x = 1.632 Mg m⁻³
M_r = 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

Data collection top

Bruker APEXII KappaCCD diffractometer	1580 independent reflections
Radiation source: fine-focus sealed tube	1254 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 28.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −10→7
T_min = 0.974, T_max = 0.984	k = −17→21
10563 measured reflections	l = −12→11

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0427P)² + 0.1255P] where P = (F_o² + 2F_c²)/3
1580 reflections	(Δ/σ)_max < 0.001
193 parameters	Δρ_max = 0.16 e Å⁻³
1 restraint	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₉N₃O₉	V = 1233.75 (11) Å³
M_r = 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

Data collection top

Bruker APEXII KappaCCD diffractometer	1580 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	1254 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.984	R_int = 0.041
10563 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.081	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
1580 reflections	Δρ_min = −0.23 e Å⁻³
193 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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.974, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	10563, 1580, 1254
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.23

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2011).

Hydrogen-bond geometry (Å, º) top

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

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