Methyl 2-methyl-3,5-dinitro­benzoate

Raza, A.R.; Saddiqa, A.; Tahir, M.N.; Danish, M.; Iqbal, M.S.

doi:10.1107/S1600536809055494

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o288

https://doi.org/10.1107/S1600536809055494

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Methyl 2-methyl-3,5-dinitrobenzoate

Abdul Rauf Raza,^a Aisha Saddiqa,^a M. Nawaz Tahir,^b ^* Muhammad Danish ^a and Mohammad Saeed Iqbal ^c

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 26 December 2009; accepted 27 December 2009; online 9 January 2010)

In the title compound, C₉H₈N₂O₆, the methyl ester group is almost planar (r.m.s. deviation = 0.002 Å) and is oriented at a dihedral angle of 24.27 (16)° with respect to the benzene ring. The nitro groups make dihedral angles of 4.2 (5)° and 60.21 (11)° with the benzene ring. In the crystal, molecules are linked by C—H⋯O interactions, resulting in zigzag chains.

Related literature

For a related structure, see: Tahir et al. (2009 ).

Experimental

Crystal data

C₉H₈N₂O₆
M_r = 240.17
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.7948 (5) Å
b = 8.8478 (8) Å
c = 17.3539 (17) Å
V = 1043.30 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.30 × 0.10 × 0.09 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.985, T_max = 0.987
6284 measured reflections
1510 independent reflections
1001 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.097
S = 1.02
1510 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9C⋯O2ⁱ	0.96	2.56	3.353 (4)	140
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809055494/hb5296sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055494/hb5296Isup2.hkl

checkCIF report

Comment top

Our work is aimed at the synthesis of various isocoumarins and the title compound (I, Fig. 1) is an intermediate for their preparation.

We have reported crystal structures of 2-Methyl-3,5-dinitrobenzoic acid (Tahir et al., 2009) and the title compound is its methyl ester.

In the title compound benzene ring A (C1–C6) is of course planar. The methyl ester B (O2/C7/O1/C8) is also planar with a maximum r. m. s. deviation of 0.0014 Å from the mean square plane. The dihedral angle between A/B is 24.27 (16)°. Two nitro groups C (O3/N1/O4) and D (O5/N2/O6) are oriented at dihedral angles of 60.21 (11)° and 4.22 (51)° respectively, with the benzene ring. The dihedral angle between C/D is 63.24 (25)°. The molecules are stabilized due to intra as well inter-molecular and C–H···O interactions (Table 1, Fig. 2) in the form of zigzag polymeric chains.

Related literature top

For a related structure, see: Tahir et al. (2009).

Experimental top

H₂SO₄ (5 ml) was added as a catalyst to a stirred solution of 2-methyl-3,5-dinitrobenzoic acid (1 g, 4.4 mmol) (Tahir et al., 2009) in MeOH (20 ml) and refluxed for 5 h. The progress of reaction was monitored by TLC. The crystals were immediately obtained upon gradual cooling followed by pouring reaction mixture to beaker. The crude product was filtered and consecutive washing with MeOH and H₂O afforded impure crystals of (I). The recrystalization from CHCl₃ afforded (69.3%) colourless needles of the title compound (I).

Structure description top

Our work is aimed at the synthesis of various isocoumarins and the title compound (I, Fig. 1) is an intermediate for their preparation.

We have reported crystal structures of 2-Methyl-3,5-dinitrobenzoic acid (Tahir et al., 2009) and the title compound is its methyl ester.

For a related structure, see: Tahir et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Partial packing diagram of (I).

Methyl 2-methyl-3,5-dinitrobenzoate top

Crystal data top

C₉H₈N₂O₆	F(000) = 496
M_r = 240.17	D_x = 1.529 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1510 reflections
a = 6.7948 (5) Å	θ = 2.4–28.3°
b = 8.8478 (8) Å	µ = 0.13 mm⁻¹
c = 17.3539 (17) Å	T = 296 K
V = 1043.30 (16) Å³	Needle, colourless
Z = 4	0.30 × 0.10 × 0.09 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1510 independent reflections
Radiation source: fine-focus sealed tube	1001 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 2.4°
ω scans	h = −5→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −11→9
T_min = 0.985, T_max = 0.987	l = −23→21
6284 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0444P)² + 0.0609P] where P = (F_o² + 2F_c²)/3
1510 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₉H₈N₂O₆	V = 1043.30 (16) Å³
M_r = 240.17	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.7948 (5) Å	µ = 0.13 mm⁻¹
b = 8.8478 (8) Å	T = 296 K
c = 17.3539 (17) Å	0.30 × 0.10 × 0.09 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1510 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1001 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.987	R_int = 0.034
6284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
1510 reflections	Δρ_min = −0.17 e Å⁻³
156 parameters

Special details top

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	0.7519 (3)	0.6592 (2)	0.08307 (14)	0.0613 (8)
O2	0.9455 (3)	0.4581 (2)	0.07824 (14)	0.0640 (8)
O3	0.4935 (4)	−0.0440 (3)	0.14759 (15)	0.0822 (10)
O4	0.2279 (3)	0.0187 (2)	0.08784 (14)	0.0704 (9)
O5	0.0268 (4)	0.4613 (3)	0.26197 (17)	0.0929 (10)
O6	0.1892 (3)	0.6626 (3)	0.23914 (14)	0.0731 (9)
N1	0.3765 (4)	0.0489 (3)	0.12346 (13)	0.0495 (8)
N2	0.1635 (3)	0.5275 (3)	0.23353 (14)	0.0552 (10)
C1	0.6122 (3)	0.4298 (3)	0.11981 (14)	0.0356 (8)
C2	0.5898 (3)	0.2738 (3)	0.10750 (14)	0.0348 (8)
C3	0.4175 (4)	0.2112 (3)	0.13733 (14)	0.0388 (8)
C4	0.2759 (4)	0.2888 (3)	0.17786 (15)	0.0417 (9)
C5	0.3090 (4)	0.4397 (3)	0.18916 (15)	0.0393 (8)
C6	0.4714 (4)	0.5114 (3)	0.16018 (15)	0.0414 (9)
C7	0.7890 (4)	0.5130 (3)	0.09141 (16)	0.0403 (9)
C8	0.9151 (5)	0.7524 (3)	0.0570 (3)	0.0850 (16)
C9	0.7325 (4)	0.1820 (3)	0.06173 (17)	0.0491 (10)
H4	0.16360	0.24127	0.19659	0.0500*
H6	0.48749	0.61477	0.16753	0.0497*
H8A	1.02426	0.74060	0.09162	0.1274*
H8B	0.87514	0.85644	0.05607	0.1274*
H8C	0.95366	0.72162	0.00616	0.1274*
H9A	0.83335	0.14382	0.09519	0.0737*
H9B	0.79104	0.24423	0.02263	0.0737*
H9C	0.66471	0.09904	0.03793	0.0737*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0486 (11)	0.0371 (11)	0.0983 (17)	−0.0068 (9)	0.0159 (12)	0.0010 (11)
O2	0.0356 (10)	0.0614 (13)	0.0950 (17)	0.0043 (10)	0.0103 (11)	0.0042 (13)
O3	0.104 (2)	0.0439 (13)	0.0988 (19)	0.0038 (14)	−0.0224 (16)	0.0074 (12)
O4	0.0598 (13)	0.0670 (14)	0.0843 (17)	−0.0270 (11)	−0.0044 (13)	−0.0147 (13)
O5	0.0706 (16)	0.0951 (18)	0.113 (2)	−0.0172 (15)	0.0572 (16)	−0.0307 (16)
O6	0.0693 (15)	0.0584 (15)	0.0916 (19)	0.0121 (12)	0.0221 (14)	−0.0147 (13)
N1	0.0574 (15)	0.0460 (15)	0.0450 (14)	−0.0120 (13)	0.0060 (12)	−0.0029 (11)
N2	0.0467 (14)	0.0669 (19)	0.0520 (16)	0.0031 (13)	0.0099 (12)	−0.0151 (14)
C1	0.0305 (12)	0.0395 (16)	0.0367 (14)	−0.0004 (11)	−0.0031 (11)	−0.0010 (11)
C2	0.0325 (13)	0.0404 (15)	0.0315 (13)	0.0011 (12)	−0.0033 (11)	0.0000 (11)
C3	0.0438 (15)	0.0372 (15)	0.0355 (14)	−0.0059 (13)	−0.0059 (12)	0.0005 (11)
C4	0.0354 (14)	0.0507 (17)	0.0389 (16)	−0.0069 (13)	0.0014 (12)	0.0003 (13)
C5	0.0311 (13)	0.0474 (16)	0.0395 (15)	0.0006 (12)	0.0022 (10)	−0.0071 (12)
C6	0.0380 (14)	0.0405 (15)	0.0457 (16)	−0.0013 (12)	−0.0032 (12)	−0.0018 (12)
C7	0.0357 (14)	0.0414 (16)	0.0437 (16)	−0.0032 (12)	−0.0005 (12)	−0.0011 (12)
C8	0.066 (2)	0.049 (2)	0.140 (4)	−0.0214 (17)	0.028 (2)	0.010 (2)
C9	0.0468 (15)	0.0458 (16)	0.0547 (19)	0.0022 (13)	0.0062 (15)	−0.0038 (13)

Geometric parameters (Å, º) top

O1—C7	1.326 (3)	C2—C9	1.494 (4)
O1—C8	1.454 (4)	C3—C4	1.375 (4)
O2—C7	1.191 (3)	C4—C5	1.368 (4)
O3—N1	1.218 (4)	C5—C6	1.369 (4)
O4—N1	1.214 (3)	C4—H4	0.9300
O5—N2	1.204 (4)	C6—H6	0.9300
O6—N2	1.212 (4)	C8—H8A	0.9600
N1—C3	1.482 (4)	C8—H8B	0.9600
N2—C5	1.474 (4)	C8—H8C	0.9600
C1—C2	1.405 (4)	C9—H9A	0.9600
C1—C6	1.388 (4)	C9—H9B	0.9600
C1—C7	1.493 (4)	C9—H9C	0.9600
C2—C3	1.395 (3)

C7—O1—C8	116.3 (2)	C1—C6—C5	120.0 (2)
O3—N1—O4	124.7 (3)	O1—C7—O2	123.1 (3)
O3—N1—C3	118.4 (3)	O1—C7—C1	111.4 (2)
O4—N1—C3	116.9 (2)	O2—C7—C1	125.5 (2)
O5—N2—O6	123.9 (3)	C3—C4—H4	122.00
O5—N2—C5	118.4 (3)	C5—C4—H4	122.00
O6—N2—C5	117.7 (2)	C1—C6—H6	120.00
C2—C1—C6	120.9 (2)	C5—C6—H6	120.00
C2—C1—C7	121.4 (2)	O1—C8—H8A	109.00
C6—C1—C7	117.7 (2)	O1—C8—H8B	109.00
C1—C2—C3	115.1 (2)	O1—C8—H8C	109.00
C1—C2—C9	123.0 (2)	H8A—C8—H8B	109.00
C3—C2—C9	121.8 (2)	H8A—C8—H8C	109.00
N1—C3—C2	118.8 (2)	H8B—C8—H8C	110.00
N1—C3—C4	115.8 (2)	C2—C9—H9A	109.00
C2—C3—C4	125.4 (2)	C2—C9—H9B	109.00
C3—C4—C5	116.5 (2)	C2—C9—H9C	109.00
N2—C5—C4	118.6 (2)	H9A—C9—H9B	109.00
N2—C5—C6	119.2 (2)	H9A—C9—H9C	110.00
C4—C5—C6	122.2 (3)	H9B—C9—H9C	109.00

C8—O1—C7—O2	−0.4 (5)	C7—C1—C6—C5	−178.3 (2)
C8—O1—C7—C1	178.9 (3)	C2—C1—C7—O1	157.0 (2)
O3—N1—C3—C2	60.3 (3)	C2—C1—C7—O2	−23.7 (4)
O3—N1—C3—C4	−121.3 (3)	C6—C1—C7—O1	−24.1 (3)
O4—N1—C3—C2	−119.0 (3)	C6—C1—C7—O2	155.2 (3)
O4—N1—C3—C4	59.4 (3)	C1—C2—C3—N1	176.8 (2)
O5—N2—C5—C4	4.3 (4)	C1—C2—C3—C4	−1.4 (4)
O5—N2—C5—C6	−176.2 (3)	C9—C2—C3—N1	0.4 (4)
O6—N2—C5—C4	−175.8 (3)	C9—C2—C3—C4	−177.8 (3)
O6—N2—C5—C6	3.7 (4)	N1—C3—C4—C5	−178.2 (2)
C6—C1—C2—C3	1.1 (3)	C2—C3—C4—C5	0.1 (4)
C6—C1—C2—C9	177.4 (2)	C3—C4—C5—N2	−178.9 (2)
C7—C1—C2—C3	179.9 (2)	C3—C4—C5—C6	1.7 (4)
C7—C1—C2—C9	−3.8 (4)	N2—C5—C6—C1	178.5 (2)
C2—C1—C6—C5	0.6 (4)	C4—C5—C6—C1	−2.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9C···O2ⁱ	0.96	2.56	3.353 (4)	140

Symmetry code: (i) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₉H₈N₂O₆
M_r	240.17
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.7948 (5), 8.8478 (8), 17.3539 (17)
V (Å³)	1043.30 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.10 × 0.09

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.985, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	6284, 1510, 1001
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.097, 1.02
No. of reflections	1510
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9C···O2ⁱ	0.96	2.56	3.353 (4)	140

Symmetry code: (i) x−1/2, −y+1/2, −z.

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore and for technical support, respectively.

References

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