N-Isopropyl-3-methyl-2-nitro­benzamide

Chen, Y.; Guo, L.; Song, W.; Zhang, J.; Tian, D.

doi:10.1107/S1600536809031997

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2278

doi:10.1107/S1600536809031997

Open

access

N-Isopropyl-3-methyl-2-nitrobenzamide

Yu Chen,^a Li-hua Guo,^a Wei Song,^a Jing Zhang ^a and Dan-bi Tian ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: tiandanbi@126.com

(Received 3 July 2009; accepted 12 August 2009; online 29 August 2009)

In the title compound, C₁₁H₁₄N₂O₃, the bond lengths and angles are within normal ranges. Weak intermolecular N—H⋯O interactions link the molecules into chains along the a axis. A non-classical intramolecular C—H⋯O interaction (nitro O atom and a H atom of the nearest methyl group) is found, forming a six-membered ring with a twisted conformation. This six-membered ring has a twisted conformation.

Related literature

For bond–length data, see: Allen et al. (1987 ). For general background, see: Lahm et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₃
M_r = 222.24
Orthorhombic, P b c a
a = 9.4230 (19) Å
b = 13.250 (3) Å
c = 20.041 (4) Å
V = 2502.2 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.974, T_max = 0.991
2260 measured reflections
2260 independent reflections
1135 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.174
S = 1.00
2260 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.00	2.855 (3)	173
C11—H11A⋯O3	0.96	2.37	3.021 (5)	124
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031997/rk2153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031997/rk2153Isup2.hkl

checkCIF report

Comment top

The title compound contains nitro– and acetylamino–groups, which can react with different groups to prepare various functional organic compounds as a fine organic intermediate (Lahm et al., 2005). We herein report the crystal structure.

In the title molecule (I), (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). Intramolecular C—H···O interaction (Table 1) results in the formation of a six–membered ring (O3/N2/C10/C9/C11/H11A), having twisted conformation.

In the crystal structure, weak intermolecular N—H···O interactions (Table 1) link the molecules into chains along the a axis (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For bond–length data, see: Allen et al. (1987). For general background, see: Lahm et al. (2005).

Experimental top

N–isopropyl–3–methyl–2–nitrobenzamide were dissolved in DMF (50 mL). The solution was then poured to ice water. The crystalline product was isolated by filtration, washed with water (600 ml), dried and gave the product 1.8 g. The single crystals were obtained by evaporating the acetone slowly at room temperature for about 14 d.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title molecular structure, with the atom–labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. A packing diagram for (I).

N-Isopropyl-3-methyl-2-nitrobenzamide top

Crystal data top

C₁₁H₁₄N₂O₃	F(000) = 944
M_r = 222.24	D_x = 1.180 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 9.4230 (19) Å	θ = 10–13°
b = 13.250 (3) Å	µ = 0.09 mm⁻¹
c = 20.041 (4) Å	T = 298 K
V = 2502.2 (9) Å³	Needle, colourless
Z = 8	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1135 reflections with I > 2σ(I)
Radiation source: fine–focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 2.0°
ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.974, T_max = 0.991	l = 0→24
2260 measured reflections	3 standard reflections every 200 reflections
2260 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.174	w = 1/[σ²(F_o²) + (0.06P)² + 0.9P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2260 reflections	Δρ_max = 0.22 e Å⁻³
146 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0059 (11)

Crystal data top

C₁₁H₁₄N₂O₃	V = 2502.2 (9) Å³
M_r = 222.24	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.4230 (19) Å	µ = 0.09 mm⁻¹
b = 13.250 (3) Å	T = 298 K
c = 20.041 (4) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1135 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.974, T_max = 0.991	3 standard reflections every 200 reflections
2260 measured reflections	intensity decay: 1%
2260 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
2260 reflections	Δρ_min = −0.16 e Å⁻³
146 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.1002 (2)	0.4262 (2)	0.21752 (13)	0.0801 (9)
N1	−0.0987 (3)	0.4490 (2)	0.27836 (16)	0.0642 (9)
H1A	−0.1881	0.4367	0.2809	0.077*
C1	0.0066 (6)	0.4504 (4)	0.3892 (3)	0.1265 (19)
H1B	0.0699	0.3974	0.3756	0.190*
H1C	−0.0769	0.4215	0.4089	0.190*
H1D	0.0533	0.4928	0.4212	0.190*
O2	−0.0336 (3)	0.51283 (19)	0.09602 (15)	0.0890 (10)
N2	0.0028 (3)	0.4269 (2)	0.08678 (16)	0.0635 (8)
C2	−0.1321 (5)	0.5952 (3)	0.3487 (2)	0.1034 (16)
H2A	−0.1543	0.6345	0.3099	0.155*
H2B	−0.0871	0.6374	0.3814	0.155*
H2C	−0.2178	0.5675	0.3670	0.155*
O3	0.1088 (3)	0.4024 (2)	0.05598 (16)	0.1007 (11)
C3	−0.0342 (4)	0.5115 (3)	0.32994 (19)	0.0676 (11)
H3A	0.0523	0.5415	0.3114	0.081*
C4	−0.0271 (3)	0.4105 (2)	0.22794 (18)	0.0540 (9)
C5	−0.1076 (3)	0.3415 (2)	0.18197 (18)	0.0519 (9)
C6	−0.1956 (4)	0.2662 (3)	0.2058 (2)	0.0698 (11)
H6A	−0.2102	0.2600	0.2516	0.084*
C7	−0.2619 (4)	0.2004 (3)	0.1630 (2)	0.0793 (12)
H7A	−0.3206	0.1500	0.1798	0.095*
C8	−0.2420 (4)	0.2086 (3)	0.0961 (2)	0.0736 (11)
H8A	−0.2884	0.1636	0.0679	0.088*
C9	−0.1545 (4)	0.2819 (3)	0.0684 (2)	0.0642 (10)
C10	−0.0889 (3)	0.3463 (2)	0.11363 (19)	0.0540 (9)
C11	−0.1371 (5)	0.2899 (3)	−0.0058 (2)	0.0973 (15)
H11A	−0.0743	0.3448	−0.0160	0.146*
H11B	−0.2279	0.3020	−0.0260	0.146*
H11C	−0.0981	0.2282	−0.0228	0.146*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0298 (12)	0.130 (2)	0.0802 (19)	−0.0125 (14)	0.0014 (13)	−0.0014 (17)
N1	0.0309 (14)	0.083 (2)	0.079 (2)	−0.0139 (15)	0.0058 (16)	−0.0135 (18)
C1	0.146 (5)	0.126 (4)	0.107 (4)	0.021 (4)	−0.047 (4)	0.009 (4)
O2	0.096 (2)	0.0519 (16)	0.119 (3)	−0.0036 (16)	0.0068 (18)	0.0099 (17)
N2	0.0583 (19)	0.064 (2)	0.068 (2)	−0.0068 (18)	−0.0004 (17)	−0.0036 (17)
C2	0.106 (4)	0.079 (3)	0.125 (4)	0.010 (3)	−0.028 (3)	−0.028 (3)
O3	0.078 (2)	0.114 (2)	0.111 (2)	−0.0197 (18)	0.0431 (19)	−0.0240 (19)
C3	0.053 (2)	0.084 (3)	0.066 (3)	−0.019 (2)	0.001 (2)	−0.005 (2)
C4	0.0306 (17)	0.064 (2)	0.068 (2)	−0.0026 (17)	−0.0016 (18)	0.009 (2)
C5	0.0355 (17)	0.049 (2)	0.071 (2)	−0.0031 (16)	0.0008 (17)	0.0032 (19)
C6	0.058 (2)	0.074 (3)	0.077 (3)	−0.011 (2)	0.002 (2)	0.005 (2)
C7	0.076 (3)	0.065 (3)	0.096 (3)	−0.025 (2)	−0.003 (3)	0.005 (3)
C8	0.070 (3)	0.060 (2)	0.091 (3)	−0.011 (2)	−0.014 (3)	−0.004 (2)
C9	0.061 (2)	0.054 (2)	0.078 (3)	0.0006 (19)	−0.003 (2)	0.000 (2)
C10	0.0430 (19)	0.046 (2)	0.073 (3)	0.0032 (17)	0.0025 (18)	0.0047 (19)
C11	0.115 (4)	0.097 (3)	0.080 (3)	−0.018 (3)	−0.006 (3)	−0.010 (3)

Geometric parameters (Å, º) top

O1—C4	1.235 (3)	C3—H3A	0.9800
N1—C4	1.318 (4)	C4—C5	1.503 (4)
N1—C3	1.457 (4)	C5—C6	1.382 (4)
N1—H1A	0.8600	C5—C10	1.383 (5)
C1—C3	1.488 (6)	C6—C7	1.375 (5)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C7—C8	1.357 (5)
C1—H1D	0.9600	C7—H7A	0.9300
O2—N2	1.203 (3)	C8—C9	1.391 (5)
N2—O3	1.218 (3)	C8—H8A	0.9300
N2—C10	1.475 (4)	C9—C10	1.391 (5)
C2—C3	1.491 (5)	C9—C11	1.499 (5)
C2—H2A	0.9600	C11—H11A	0.9600
C2—H2B	0.9600	C11—H11B	0.9600
C2—H2C	0.9600	C11—H11C	0.9600

C4—N1—C3	123.4 (3)	N1—C4—C5	116.6 (3)
C4—N1—H1A	118.3	C6—C5—C10	116.9 (3)
C3—N1—H1A	118.3	C6—C5—C4	122.0 (3)
C3—C1—H1B	109.5	C10—C5—C4	120.9 (3)
C3—C1—H1C	109.5	C7—C6—C5	120.9 (4)
H1B—C1—H1C	109.5	C7—C6—H6A	119.5
C3—C1—H1D	109.5	C5—C6—H6A	119.5
H1B—C1—H1D	109.5	C8—C7—C6	120.2 (4)
H1C—C1—H1D	109.5	C8—C7—H7A	119.9
O2—N2—O3	124.3 (3)	C6—C7—H7A	119.9
O2—N2—C10	117.5 (3)	C7—C8—C9	122.2 (4)
O3—N2—C10	118.2 (3)	C7—C8—H8A	118.9
C3—C2—H2A	109.5	C9—C8—H8A	118.9
C3—C2—H2B	109.5	C10—C9—C8	115.6 (4)
H2A—C2—H2B	109.5	C10—C9—C11	123.7 (4)
C3—C2—H2C	109.5	C8—C9—C11	120.7 (4)
H2A—C2—H2C	109.5	C5—C10—C9	124.1 (3)
H2B—C2—H2C	109.5	C5—C10—N2	118.0 (3)
N1—C3—C1	111.4 (3)	C9—C10—N2	117.8 (3)
N1—C3—C2	110.1 (3)	C9—C11—H11A	109.5
C1—C3—C2	111.3 (4)	C9—C11—H11B	109.5
N1—C3—H3A	108.0	H11A—C11—H11B	109.5
C1—C3—H3A	108.0	C9—C11—H11C	109.5
C2—C3—H3A	108.0	H11A—C11—H11C	109.5
O1—C4—N1	124.1 (3)	H11B—C11—H11C	109.5
O1—C4—C5	119.3 (3)

C4—N1—C3—C1	−95.0 (4)	C7—C8—C9—C11	−178.9 (4)
C4—N1—C3—C2	141.1 (4)	C6—C5—C10—C9	1.1 (5)
C3—N1—C4—O1	−3.0 (6)	C4—C5—C10—C9	176.8 (3)
C3—N1—C4—C5	175.6 (3)	C6—C5—C10—N2	179.1 (3)
O1—C4—C5—C6	132.9 (4)	C4—C5—C10—N2	−5.2 (5)
N1—C4—C5—C6	−45.8 (4)	C8—C9—C10—C5	−0.8 (5)
O1—C4—C5—C10	−42.6 (5)	C11—C9—C10—C5	178.0 (4)
N1—C4—C5—C10	138.7 (3)	C8—C9—C10—N2	−178.8 (3)
C10—C5—C6—C7	−0.6 (5)	C11—C9—C10—N2	0.0 (5)
C4—C5—C6—C7	−176.3 (3)	O2—N2—C10—C5	−62.5 (4)
C5—C6—C7—C8	−0.2 (6)	O3—N2—C10—C5	118.6 (4)
C6—C7—C8—C9	0.5 (6)	O2—N2—C10—C9	115.6 (4)
C7—C8—C9—C10	0.0 (6)	O3—N2—C10—C9	−63.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.00	2.855 (3)	173
C11—H11A···O3	0.96	2.37	3.021 (5)	124

Symmetry code: (i) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₃
M_r	222.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	9.4230 (19), 13.250 (3), 20.041 (4)
V (Å³)	2502.2 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.974, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2260, 2260, 1135
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.174, 1.00
No. of reflections	2260
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.16

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.00	2.855 (3)	173.00
C11—H11A···O3	0.96	2.37	3.021 (5)	124.00

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Lahm, G. P., Selby, T. P., Freudenberger, J. H., Stevenson, T. M., Myers, B. J., Seburyamo, G., Smith, B. K., Flexner, L., Clark, C. E. & Cordova, D. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar