Crystal structure of 1,3,5-trimethyl-2,4-di­nitro­benzene

Brihi, O.; Hamdouni, N.; Boudjada, A.; Meinnel, J.

doi:10.1107/S2056989015014243

organic compounds

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Volume 71| Part 9| September 2015| Pages o670-o671

https://doi.org/10.1107/S2056989015014243

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Crystal structure of 1,3,5-trimethyl-2,4-dinitrobenzene

Ouarda Brihi,^a ^* Noudjoud Hamdouni,^a Ali Boudjada ^a and Jean Meinnel ^b

^aLaboratoire de Cristallographie, Département de Physique, Université Mentouri-Constantine, 25000 Constantine, Algeria, and ^bUMR 6226 CNRS–Université Rennes 1 `Sciences Chimiques de Rennes', Equipe `Matière Condensée et Systèmes Electroactifs', 263 Avenue du Général Leclerc, F-35042 Rennes, France
^*Correspondence e-mail: ouardabrihi@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 July 2015; accepted 28 July 2015; online 22 August 2015)

In the title compound, C₉H₁₀N₂O₄, the planes of the nitro groups subtend dihedral angles of 55.04 (15) and 63.23 (15)° with that of the aromatic ring. These tilts are in opposite senses and the molecule possesses approximate mirror symmetry about a plane normal to the molecule. In the crystal, molecules form stacks in the [100] direction with adjacent molecules related by translation, although the centroid–centroid separation of 4.136 (5) Å is probably too long to regard as a significant aromatic π–π stacking interaction. An extremely weak C—H⋯O interaction is also present.

Keywords: crystal structure; dinitrobenzene; weak C—H⋯O interaction.

CCDC reference: 1415489

1. Related literature

For the structures and properties of related compounds, see: Tazi et al. (1995 ); Hernandez et al. (2003 ).

2. Experimental

2.1. Crystal data

C₉H₁₀N₂O₄
M_r = 210.19
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.136 (5) Å
b = 13.916 (5) Å
c = 17.194 (5) Å
V = 989.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.1 × 0.08 × 0.08 mm

2.2. Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.618, T_max = 1.000
3941 measured reflections
2730 independent reflections
1302 reflections with I > 2σ(I)
R_int = 0.032
Standard reflections: ?

2.3. Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.113
S = 0.93
2730 reflections
139 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7C⋯O1ⁱ	0.96	2.60	3.232 (4)	124
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis RED (Oxford Diffraction, 2002 $[Oxford Diffraction (2002). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED; data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1415489

Crystal structure: contains datablocks ouarda, I. DOI: https://doi.org/10.1107/S2056989015014243/hb7463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014243/hb7463Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015014243/hb7463Isup3.cml

checkCIF report

Related literature top

For the structures and properties of related compounds, see: Tazi et al. (1995); Hernandez et al. (2003).

Experimental top

The commercially available compound (Sigma-Aldrich) Was recrystallized from ethanol solution.

Structure description top

For the structures and properties of related compounds, see: Tazi et al. (1995); Hernandez et al. (2003).

Computing details top

Data collection: CrysAlis RED (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED (Oxford Diffraction, 2002); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of (I) at 293 K, along the b axis.
	Fig. 3. The crystal packing of (I) at 293 K, according to the direction [100].

1,3,5-Trimethyl-2,4-dinitrobenzene top

Crystal data top

C₉H₁₀N₂O₄	F(000) = 440
M_r = 210.19	D_x = 1.411 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1062 reflections
a = 4.136 (5) Å	θ = 3.8–25.0°
b = 13.916 (5) Å	µ = 0.11 mm⁻¹
c = 17.194 (5) Å	T = 293 K
V = 989.6 (13) Å³	Needle, colourless
Z = 4	0.1 × 0.08 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2730 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1302 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
CCD scans	θ_max = 32.2°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −5→3
T_min = 0.618, T_max = 1.000	k = −19→17
3941 measured reflections	l = −25→16

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0312P)²] where P = (F_o² + 2F_c²)/3
2730 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₉H₁₀N₂O₄	V = 989.6 (13) Å³
M_r = 210.19	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.136 (5) Å	µ = 0.11 mm⁻¹
b = 13.916 (5) Å	T = 293 K
c = 17.194 (5) Å	0.1 × 0.08 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2730 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1302 reflections with I > 2σ(I)
T_min = 0.618, T_max = 1.000	R_int = 0.032
3941 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.12 e Å⁻³
2730 reflections	Δρ_min = −0.15 e Å⁻³
139 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.5095 (6)	0.13682 (16)	0.51948 (12)	0.0830 (9)
O2	0.4780 (6)	0.14379 (17)	0.16111 (14)	0.0975 (10)
O11	0.1589 (6)	0.0227 (2)	0.51482 (12)	0.0930 (9)
O22	0.8082 (7)	0.22717 (18)	0.22671 (15)	0.1057 (11)
N1	0.3785 (6)	0.06911 (19)	0.48712 (13)	0.0612 (9)
N2	0.6374 (6)	0.15688 (17)	0.21810 (14)	0.0576 (8)
C1	0.4961 (5)	0.04214 (19)	0.40898 (13)	0.0446 (8)
C2	0.5978 (6)	−0.05263 (18)	0.39734 (15)	0.0482 (8)
C3	0.7215 (6)	−0.07338 (17)	0.32487 (16)	0.0501 (9)
C4	0.7380 (6)	−0.00732 (19)	0.26478 (14)	0.0466 (8)
C5	0.6263 (6)	0.08533 (17)	0.28156 (15)	0.0439 (8)
C6	0.5084 (5)	0.11344 (17)	0.35299 (14)	0.0435 (8)
C7	0.3848 (8)	0.21448 (18)	0.36780 (16)	0.0664 (11)
C8	0.8759 (7)	−0.0350 (2)	0.18697 (15)	0.0632 (10)
C9	0.5834 (7)	−0.1295 (2)	0.45897 (17)	0.0701 (11)
H3	0.79817	−0.13520	0.31580	0.0601*
H7A	0.30028	0.24079	0.32036	0.0995*
H7B	0.55903	0.25404	0.38611	0.0995*
H7C	0.21682	0.21253	0.40631	0.0995*
H8A	1.00516	0.01682	0.16721	0.0947*
H8B	0.70269	−0.04818	0.15135	0.0947*
H8C	1.00773	−0.09134	0.19269	0.0947*
H9A	0.66925	−0.10482	0.50682	0.1050*
H9B	0.70885	−0.18397	0.44265	0.1050*
H9C	0.36286	−0.14884	0.46668	0.1050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1139 (17)	0.0722 (16)	0.0629 (13)	−0.0037 (15)	−0.0125 (13)	−0.0276 (12)
O2	0.130 (2)	0.0873 (18)	0.0751 (14)	−0.0364 (15)	−0.0386 (16)	0.0295 (14)
O11	0.0756 (14)	0.129 (2)	0.0743 (14)	−0.0118 (16)	0.0166 (12)	−0.0084 (15)
O22	0.126 (2)	0.0670 (16)	0.124 (2)	−0.0504 (15)	−0.0339 (17)	0.0323 (15)
N1	0.0600 (14)	0.0690 (18)	0.0547 (14)	0.0088 (14)	−0.0066 (13)	−0.0055 (14)
N2	0.0685 (15)	0.0394 (13)	0.0648 (15)	−0.0027 (12)	−0.0067 (14)	0.0032 (13)
C1	0.0449 (13)	0.0466 (14)	0.0424 (13)	−0.0009 (12)	−0.0070 (12)	−0.0089 (12)
C2	0.0508 (14)	0.0394 (14)	0.0545 (15)	−0.0036 (12)	−0.0098 (13)	−0.0029 (13)
C3	0.0570 (16)	0.0294 (12)	0.0639 (17)	0.0000 (11)	−0.0025 (14)	−0.0069 (13)
C4	0.0507 (14)	0.0362 (14)	0.0529 (14)	−0.0032 (11)	−0.0020 (12)	−0.0082 (13)
C5	0.0477 (13)	0.0327 (12)	0.0513 (15)	−0.0047 (11)	−0.0106 (13)	0.0033 (12)
C6	0.0437 (13)	0.0353 (12)	0.0515 (15)	0.0042 (11)	−0.0110 (12)	−0.0090 (12)
C7	0.083 (2)	0.0434 (16)	0.0727 (19)	0.0206 (15)	−0.0153 (16)	−0.0123 (15)
C8	0.0709 (19)	0.0503 (16)	0.0683 (17)	−0.0045 (15)	0.0121 (15)	−0.0125 (15)
C9	0.082 (2)	0.0544 (19)	0.074 (2)	−0.0040 (18)	−0.0028 (16)	0.0144 (16)

Geometric parameters (Å, º) top

O1—N1	1.221 (3)	C5—C6	1.378 (3)
O2—N2	1.195 (3)	C6—C7	1.518 (4)
O11—N1	1.212 (4)	C3—H3	0.9300
O22—N2	1.216 (4)	C7—H7A	0.9600
N1—C1	1.477 (3)	C7—H7B	0.9600
N2—C5	1.478 (3)	C7—H7C	0.9600
C1—C2	1.399 (4)	C8—H8A	0.9600
C1—C6	1.383 (3)	C8—H8B	0.9600
C2—C3	1.378 (4)	C8—H8C	0.9600
C2—C9	1.507 (4)	C9—H9A	0.9600
C3—C4	1.385 (4)	C9—H9B	0.9600
C4—C5	1.400 (4)	C9—H9C	0.9600
C4—C8	1.505 (4)

O1—N1—O11	124.4 (2)	C5—C6—C7	122.1 (2)
O1—N1—C1	117.7 (2)	C2—C3—H3	118.00
O11—N1—C1	118.0 (2)	C4—C3—H3	118.00
O2—N2—O22	122.9 (3)	C6—C7—H7A	109.00
O2—N2—C5	119.1 (2)	C6—C7—H7B	109.00
O22—N2—C5	118.1 (2)	C6—C7—H7C	109.00
N1—C1—C2	118.0 (2)	H7A—C7—H7B	109.00
N1—C1—C6	117.6 (2)	H7A—C7—H7C	109.00
C2—C1—C6	124.5 (2)	H7B—C7—H7C	109.00
C1—C2—C3	116.0 (2)	C4—C8—H8A	109.00
C1—C2—C9	123.8 (2)	C4—C8—H8B	109.00
C3—C2—C9	120.1 (2)	C4—C8—H8C	109.00
C2—C3—C4	123.7 (2)	H8A—C8—H8B	109.00
C3—C4—C5	116.2 (2)	H8A—C8—H8C	109.00
C3—C4—C8	120.8 (2)	H8B—C8—H8C	109.00
C5—C4—C8	123.0 (2)	C2—C9—H9A	110.00
N2—C5—C4	117.3 (2)	C2—C9—H9B	109.00
N2—C5—C6	118.5 (2)	C2—C9—H9C	109.00
C4—C5—C6	124.2 (2)	H9A—C9—H9B	109.00
C1—C6—C5	115.4 (2)	H9A—C9—H9C	109.00
C1—C6—C7	122.4 (2)	H9B—C9—H9C	109.00

O1—N1—C1—C2	124.4 (3)	C6—C1—C2—C3	1.0 (4)
O11—N1—C1—C2	−55.6 (3)	N1—C1—C6—C5	178.6 (2)
O1—N1—C1—C6	−53.5 (3)	C1—C2—C3—C4	−2.2 (4)
O11—N1—C1—C6	126.6 (3)	C9—C2—C3—C4	178.9 (2)
O2—N2—C5—C6	−116.9 (3)	C2—C3—C4—C5	1.3 (4)
O2—N2—C5—C4	63.2 (3)	C2—C3—C4—C8	−179.9 (2)
O22—N2—C5—C4	−117.2 (3)	C3—C4—C5—C6	0.9 (4)
O22—N2—C5—C6	62.7 (3)	C8—C4—C5—N2	2.0 (4)
N1—C1—C2—C3	−176.7 (2)	C8—C4—C5—C6	−177.9 (2)
N1—C1—C6—C7	−4.4 (3)	C3—C4—C5—N2	−179.2 (2)
C2—C1—C6—C5	1.0 (3)	N2—C5—C6—C1	178.2 (2)
C2—C1—C6—C7	178.0 (2)	N2—C5—C6—C7	1.2 (4)
C6—C1—C2—C9	179.9 (2)	C4—C5—C6—C1	−1.9 (4)
N1—C1—C2—C9	2.2 (4)	C4—C5—C6—C7	−179.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7C···O1ⁱ	0.96	2.60	3.232 (4)	124

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7C···O1ⁱ	0.96	2.60	3.232 (4)	124

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 9| September 2015| Pages o670-o671

https://doi.org/10.1107/S2056989015014243

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