supplementary materials
Methyl 2-methyl-3,5-dinitrobenzoate
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.
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).
In the absence of significant anomalous scattering effects, Friedal pairs were
merged.
The H-atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined
as riding with Uiso(H) = xUeq(C), where x = 1.2 for
aryl and 1.5 for methyl H atoms.
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).
Methyl 2-methyl-3,5-dinitrobenzoate
top
Crystal data top
| C9H8N2O6 | F(000) = 496 |
| Mr = 240.17 | Dx = 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 | Rint = 0.034 |
| Detector resolution: 7.40 pixels mm-1 | θmax = 28.3°, θmin = 2.4° |
| ω scans | h = −5→9 |
Absorption correction: multi-scan
(SADABS; Bruker, 2005) | k = −11→9 |
| Tmin = 0.985, Tmax = 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(Fo2) + (0.0444P)2 + 0.0609P]
where P = (Fo2 + 2Fc2)/3 |
| 1510 reflections | (Δ/σ)max < 0.001 |
| 156 parameters | Δρmax = 0.16 e Å−3 |
| 0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
| C9H8N2O6 | V = 1043.30 (16) Å3 |
| Mr = 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) |
| Tmin = 0.985, Tmax = 0.987 | Rint = 0.034 |
| 6284 measured reflections | θmax = 28.3° |
Refinement top
| R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
| wR(F2) = 0.097 | Δρmax = 0.16 e Å−3 |
| S = 1.02 | Δρmin = −0.16 e Å−3 |
| 1510 reflections | Absolute structure: ? |
| 156 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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, °) 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 codes: (i) x−1/2, −y+1/2, −z. |
Table 1
Hydrogen-bond geometry (Å, °) 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 codes: (i) x−1/2, −y+1/2, −z. |
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.
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Tahir, M. N., Raza, A. R., Saddiqa, A., Danish, M. & Saleem, I. (2009). Acta Cryst. E65, o2819.
![[Figure 1]](./hb5296fig1thm.gif)
![[Figure 2]](./hb5296fig2thm.gif)
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.