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

Abstract

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.

Related literature  

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

Experimental  

Crystal data  

• C₉H₁₀N₂O₄

• M _r = 210.19

• Orthorhombic,

• a = 4.136 (5) Å

• b = 13.916 (5) Å

• c = 17.194 (5) Å

• V = 989.6 (13) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 293 K

• 0.1 × 0.08 × 0.08 mm

Data collection  

• Oxford Diffraction Xcalibur diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▸) 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: ?

Refinement  

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 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

Data collection: CrysAlis RED (Oxford Diffraction, 2002 ▸); 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 ▸).

Supplementary Material

CCDC reference: 1415489

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C7H7CO1i	0.96	2.60	3.232(4)	124

Symmetry code: (i) .

supplementary crystallographic information

S1. Experimental

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

S2. Refinement

All non-H atoms were refined with anisotropic atomic displacement parameters. All H atoms were localized in a Fourier maps but introduced in calculated positions and treated as riding on their parent C atoms with C_aryl—H_aryl=0.93 Å; C_methyl—H_methyl=0.96 Å and U_iso(H_methyl)=1.5U_eq(C_methyl) or U_iso(H_aryl)=1.2U_eq(C_aryl). The atoms of benzene cycle present parameters of atomic displacements weaker than those of the substituent atoms.

Figures

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].

Crystal data

C9H10N2O4	F(000) = 440
Mr = 210.19	Dx = 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

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

Refinement

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(Fo2) + (0.0312P)2] where P = (Fo2 + 2Fc2)/3
2730 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.12 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.