4-Methyl-3-nitro­benzaldehyde

Guo, Z.-R.; Li, H.-B.; Li, F.

doi:10.1107/S1600536810033635

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2420

https://doi.org/10.1107/S1600536810033635

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4-Methyl-3-nitrobenzaldehyde

Ze-Rong Guo,^a ^* Hua-Bo Li ^a and Fang Li ^a

^aState Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, People's Republic of China
^*Correspondence e-mail: guozr531408@sohu.com

(Received 11 August 2010; accepted 20 August 2010; online 28 August 2010)

In the crystal structure of the title compound, C₈H₇NO₃, molecules are linked through weak intermolecular C—H⋯O hydrogen bonding.

Related literature

For the preparation, see: Johnson et al. (1991 ). For general background to supramolecular electron-transfer materials, see: Yagi et al. (2003 ); Ezoe et al. (2006 ); Normand-Bayle et al. (2005 ); Ward et al. (2005 ). For a related structure, see: Zhang et al. (2009 ).

Experimental

Crystal data

C₈H₇NO₃
M_r = 165.15
Monoclinic, P 2₁ /c
a = 3.9052 (6) Å
b = 17.841 (3) Å
c = 11.0663 (15) Å
β = 97.647 (2)°
V = 764.14 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.32 × 0.20 × 0.12 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.745, T_max = 1.000
4088 measured reflections
1353 independent reflections
1012 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.114
S = 1.05
1353 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.13 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
C4—H4⋯O3ⁱ	0.93	2.47	3.319 (2)	152
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810033635/lx2167sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810033635/lx2167Isup2.hkl

checkCIF report

Comment top

The title compound is an important intermediate for preparing supramolecular electron transfer materials (Yagi et al., 2003; Ezoe et al., 2006) and it has been utilized to synthesize medicinal compounds with biological activities. Herein we report the crystal structure of the title compound (Fig. 1).

The title compound crystallizes in the monoclinic space group P2₁/c, the unit cell is consists of four molecules. In the title compound, the bond distances and bond angles are similar to those of the reported compound (Zhang et al., 2009). The crystal packing (Fig. 2) is stabilized by a weak intermolecular C—H···O hydrogen bond between the benzene H atom and the oxygen of the aldehyde group(Table 1).

Related literature top

For the preparation, see: Johnson et al. (1991). For general background to supramolecular electron-transfer materials, see: Yagi et al. (2003); Ezoe et al. (2006); Normand-Bayle et al. (2005); Ward et al. (2005). For a related structure, see: Zhang et al. (2009).

Experimental top

The title compound was obtained according to the literature method (Johnson et al., 1991). Single crystals suitable for X–ray diffraction were prepared by slow evaporation of a solution of the title compound in diethyl ether at room temperature.

Structure description top

For the preparation, see: Johnson et al. (1991). For general background to supramolecular electron-transfer materials, see: Yagi et al. (2003); Ezoe et al. (2006); Normand-Bayle et al. (2005); Ward et al. (2005). For a related structure, see: Zhang et al. (2009).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. C—H···O interaction (dotted lines) in the crystal structure of the title compound.

4-Methyl-3-nitrobenzaldehyde top

Crystal data top

C₈H₇NO₃	F(000) = 344
M_r = 165.15	D_x = 1.435 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1083 reflections
a = 3.9052 (6) Å	θ = 2.2–23.9°
b = 17.841 (3) Å	µ = 0.11 mm⁻¹
c = 11.0663 (15) Å	T = 293 K
β = 97.647 (2)°	Block, colorless
V = 764.14 (19) Å³	0.32 × 0.20 × 0.12 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	1353 independent reflections
Radiation source: fine-focus sealed tube	1012 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −4→4
T_min = 0.745, T_max = 1.000	k = −21→18
4088 measured reflections	l = −13→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0555P)² + 0.1376P] where P = (F_o² + 2F_c²)/3
1353 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₈H₇NO₃	V = 764.14 (19) Å³
M_r = 165.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9052 (6) Å	µ = 0.11 mm⁻¹
b = 17.841 (3) Å	T = 293 K
c = 11.0663 (15) Å	0.32 × 0.20 × 0.12 mm
β = 97.647 (2)°

Data collection top

Bruker APEX CCD area-detector diffractometer	1353 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1012 reflections with I > 2σ(I)
T_min = 0.745, T_max = 1.000	R_int = 0.018
4088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.05	Δρ_max = 0.13 e Å⁻³
1353 reflections	Δρ_min = −0.16 e Å⁻³
110 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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	1.3758 (4)	0.60008 (9)	1.06104 (12)	0.0824 (5)
O2	1.0886 (5)	0.70092 (9)	1.05565 (14)	0.0976 (6)
O3	0.8183 (5)	0.42460 (9)	0.60139 (14)	0.0937 (6)
N1	1.1695 (4)	0.64374 (9)	1.00814 (13)	0.0537 (4)
C1	0.7588 (6)	0.75833 (11)	0.8424 (2)	0.0680 (6)
H1A	0.6294	0.7831	0.7740	0.102*
H1B	0.9756	0.7835	0.8638	0.102*
H1C	0.6300	0.7594	0.9105	0.102*
C2	0.8234 (4)	0.67836 (9)	0.80931 (16)	0.0479 (4)
C3	0.6869 (5)	0.65315 (10)	0.69353 (16)	0.0549 (5)
H3	0.5619	0.6866	0.6403	0.066*
C4	0.7290 (5)	0.58141 (10)	0.65495 (15)	0.0546 (5)
H4	0.6312	0.5669	0.5772	0.065*
C5	0.9177 (4)	0.52988 (10)	0.73139 (14)	0.0483 (4)
C6	0.9618 (5)	0.45197 (11)	0.69313 (17)	0.0640 (5)
H6	1.1124	0.4217	0.7440	0.077*
C7	1.0625 (4)	0.55297 (9)	0.84592 (14)	0.0458 (4)
H7	1.1943	0.5197	0.8975	0.055*
C8	1.0119 (4)	0.62533 (9)	0.88392 (14)	0.0440 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0988 (12)	0.0828 (11)	0.0565 (9)	0.0162 (9)	−0.0233 (8)	−0.0012 (7)
O2	0.1323 (15)	0.0757 (11)	0.0757 (11)	0.0201 (10)	−0.0198 (10)	−0.0281 (9)
O3	0.1213 (14)	0.0757 (11)	0.0727 (10)	0.0141 (9)	−0.0293 (9)	−0.0225 (8)
N1	0.0589 (9)	0.0527 (9)	0.0476 (8)	−0.0074 (7)	0.0000 (7)	−0.0003 (7)
C1	0.0713 (13)	0.0501 (11)	0.0811 (14)	0.0055 (9)	0.0046 (11)	0.0069 (10)
C2	0.0438 (9)	0.0461 (10)	0.0540 (10)	−0.0021 (7)	0.0074 (8)	0.0087 (7)
C3	0.0530 (10)	0.0593 (12)	0.0504 (10)	0.0036 (8)	−0.0001 (8)	0.0172 (8)
C4	0.0554 (11)	0.0646 (12)	0.0412 (9)	−0.0009 (9)	−0.0028 (8)	0.0046 (8)
C5	0.0472 (10)	0.0536 (10)	0.0429 (9)	−0.0010 (7)	0.0011 (7)	0.0010 (7)
C6	0.0730 (13)	0.0625 (13)	0.0527 (11)	0.0082 (10)	−0.0063 (9)	−0.0047 (9)
C7	0.0439 (9)	0.0480 (10)	0.0438 (9)	0.0007 (7)	0.0000 (7)	0.0072 (7)
C8	0.0427 (9)	0.0488 (10)	0.0396 (9)	−0.0064 (7)	0.0028 (7)	0.0046 (7)

Geometric parameters (Å, º) top

O1—N1	1.2135 (19)	C3—C4	1.366 (3)
O2—N1	1.209 (2)	C3—H3	0.9300
O3—C6	1.197 (2)	C4—C5	1.392 (2)
N1—C8	1.467 (2)	C4—H4	0.9300
C1—C2	1.503 (2)	C5—C7	1.380 (2)
C1—H1A	0.9600	C5—C6	1.470 (3)
C1—H1B	0.9600	C6—H6	0.9300
C1—H1C	0.9600	C7—C8	1.380 (2)
C2—C3	1.395 (2)	C7—H7	0.9300
C2—C8	1.399 (2)

O2—N1—O1	121.80 (16)	C3—C4—C5	120.32 (16)
O2—N1—C8	119.68 (16)	C3—C4—H4	119.8
O1—N1—C8	118.51 (15)	C5—C4—H4	119.8
C2—C1—H1A	109.5	C7—C5—C4	118.69 (17)
C2—C1—H1B	109.5	C7—C5—C6	119.82 (16)
H1A—C1—H1B	109.5	C4—C5—C6	121.49 (16)
C2—C1—H1C	109.5	O3—C6—C5	124.79 (18)
H1A—C1—H1C	109.5	O3—C6—H6	117.6
H1B—C1—H1C	109.5	C5—C6—H6	117.6
C3—C2—C8	115.51 (16)	C5—C7—C8	120.08 (15)
C3—C2—C1	118.29 (16)	C5—C7—H7	120.0
C8—C2—C1	126.21 (16)	C8—C7—H7	120.0
C4—C3—C2	122.81 (16)	C7—C8—C2	122.57 (15)
C4—C3—H3	118.6	C7—C8—N1	115.84 (14)
C2—C3—H3	118.6	C2—C8—N1	121.59 (15)

C8—C2—C3—C4	0.8 (3)	C5—C7—C8—N1	178.59 (14)
C1—C2—C3—C4	−179.54 (18)	C3—C2—C8—C7	0.4 (2)
C2—C3—C4—C5	−0.7 (3)	C1—C2—C8—C7	−179.27 (16)
C3—C4—C5—C7	−0.5 (3)	C3—C2—C8—N1	−179.79 (14)
C3—C4—C5—C6	178.88 (17)	C1—C2—C8—N1	0.5 (3)
C7—C5—C6—O3	172.0 (2)	O2—N1—C8—C7	−167.19 (17)
C4—C5—C6—O3	−7.4 (3)	O1—N1—C8—C7	11.8 (2)
C4—C5—C7—C8	1.6 (2)	O2—N1—C8—C2	13.0 (3)
C6—C5—C7—C8	−177.77 (16)	O1—N1—C8—C2	−167.98 (17)
C5—C7—C8—C2	−1.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.93	2.47	3.319 (2)	152

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₇NO₃
M_r	165.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	3.9052 (6), 17.841 (3), 11.0663 (15)
β (°)	97.647 (2)
V (Å³)	764.14 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.20 × 0.12

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.745, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4088, 1353, 1012
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.114, 1.05
No. of reflections	1353
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.16

Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.9300	2.4700	3.319 (2)	152.00

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the State Key Laboratory of Explosion Science and Technology Foundation (YBKT09–10, SKLEST–ZZ–09–10), Beijing Institute of Technology.

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