N-Benzyl-3-nitro­aniline

Stilinović, V.; Portada, T.

doi:10.1107/S1600536811042632

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3013

doi:10.1107/S1600536811042632

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N-Benzyl-3-nitroaniline

Vladimir Stilinović ^a ^* and Tomislav Portada ^b

^aLaboratory of General and Inorganic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102 A, HR-10000 Zagreb, Croatia, and ^bDepartment of Organic Chemistry and Biochemistry, Ruder Bošković Institute, PO Box 180, HR-10002 Zagreb, Croatia
^*Correspondence e-mail: vstilinovic@chem.pmf.hr

(Received 15 September 2011; accepted 14 October 2011; online 22 October 2011)

The molecule of the title compound, C₁₃H₁₂N₂O₂, has a bent conformation with a torsion angle about the central C—N bond of 72.55 (19)°. In the crystal, the molecules are connected via classical N—H⋯O and non-classical C—H⋯O hydrogen bonds into chains along [10 $[\overline{1}]$ ]. The dihedral angle between the ring planes is 86.0 (6)°.

Related literature

For the synthesis of the title compound, see: Magyarfalvi (2008 ). For related structures, see: Betz et al. (2011 ); Iwasaki et al. (1988 ).

Experimental

Crystal data

C₁₃H₁₂N₂O₂
M_r = 228.25
Monoclinic, P 2₁
a = 5.3359 (2) Å
b = 19.2285 (6) Å
c = 5.6017 (2) Å
β = 97.334 (3)°
V = 570.04 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.41 × 0.29 × 0.23 mm

Data collection

Oxford Diffraction Xcalibur CCD diffractometer
7072 measured reflections
1280 independent reflections
1093 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.01
1280 reflections
158 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.84 (2)	2.44 (2)	3.263 (2)	166 (2)
C6—H6⋯O2ⁱ	0.93	2.45	3.364 (2)	169
C13—H13⋯O1ⁱⁱ	0.93	2.67	3.293 (2)	125
C7—H7A⋯O1ⁱⁱⁱ	0.97	2.61	3.318 (2)	130
Symmetry codes: (i) x+1, y, z-1; (ii) x, y, z-1; (iii) x+1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program used to solve structure: SHELXS97 (Sheldrick, 2008 ); program used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ), POV-RAY (Cason et al., 2002 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ), PLATON (Spek, 2009 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811042632/rk2302sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042632/rk2302Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042632/rk2302Isup3.cml

checkCIF report

Comment top

The synthesis of the title compound was a part of Preparatory problems for the 40th International Chemistry Olympiad (Magyarfalvi, 2008). It was prepared and crystalized as a part of the laboratory work with high–school students.

The N–methyl–3–nitroaniline system is almost perfectly planar (the mean plane of the the phenyl ring is at an angle of 1.5 (2)° with the mean plane of the angle nitro group, and 1.4 (2)° with the mean plane of the central C1—N1—C7. The phenyl substituent is at an angle of 86.0 (2)° to the rest of the molecule. The C1—N1—C7—C8 torsion angle is 72.55 (19)°. This conforamtion is similar to thet reported by Betz et al. (2011) for the unsubstituited N–benzylaniline.

The molecules are connected into chains along the [1 0 1] direction by N1—H1···O1ⁱ classical hydrogen bonds of (N1···O1ⁱ = 3.263 (2)Å), which are further fortified by non–classical one C6—H6···O2ⁱ with contact C6···O2ⁱⁱ of 3.364 (2)Å. Interestingly, in a similar compound, N–benzyl–4–nitroaniline (Iwasaki et al., 1988), the N—H···O bonding is entirely absent, which demonstrates the effect of changing the position of the nitro group on tha supramolecular aggregation.

The chains are further interconnected via long non–classical C—H···O (C13—H13···O1ⁱⁱ of 3.293 (2)Å and C7—H7A···O1ⁱⁱⁱ of 3.318 (1)Å) contacts into layers perpendicular to the b axis.

Symmetry codes: (i) x+1, y, z-1; (ii) x, y, z-1; (iii) x+1, y, z.

Related literature top

For the synthesis of the title compound, see: Magyarfalvi (2008). For related structures, see: Betz et al. (2011); Iwasaki et al. (1988).

Experimental top

The title compound was prepared using a slightly modified procedure (Magyarfalvi, 2008) and isolated in a form of yellow crystalline powder. A sample of approximately 100 mg of the compound was dissolved in approximately 10 ml of hot ethanol. The solution was left to cool to room temperature, filtered, and the filtrate was left to crystallize by slow evaporation. The single crystalls suitable for X–ray study were obtained after aproximatelly 4 days.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), POV-RAY (Cason et al., 2002) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of title compound with the atom labeling scheme. Displacement ellipsoids are shown at 30% probability level. Hydrogen atoms are shown as a spheres of arbitrary radius.
	Fig. 2. Chains in the structure of the title compound viewed along the [1 0 1] direction. Hydrogen bonds are indicated by dashed lines.

N-benzyl-3-nitroaniline top

Crystal data top

C₁₃H₁₂N₂O₂	Z = 2
M_r = 228.25	F(000) = 240
Monoclinic, P2₁	D_x = 1.33 Mg m⁻³
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 5.3359 (2) Å	θ = 4.6–54.0°
b = 19.2285 (6) Å	µ = 0.09 mm⁻¹
c = 5.6017 (2) Å	T = 295 K
β = 97.334 (3)°	Plate, yellow
V = 570.04 (3) Å³	0.41 × 0.29 × 0.23 mm

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	1093 reflections with I > 2σ(I)
Radiation source: fine–focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 27.0°, θ_min = 3.8°
ϕ and ω scans	h = −6→6
7072 measured reflections	k = −24→24
1280 independent reflections	l = −7→7

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0615P)²] where P = (F_o² + 2F_c²)/3
1280 reflections	(Δ/σ)_max = 0.003
158 parameters	Δρ_max = 0.14 e Å⁻³
3 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₃H₁₂N₂O₂	V = 570.04 (3) Å³
M_r = 228.25	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.3359 (2) Å	µ = 0.09 mm⁻¹
b = 19.2285 (6) Å	T = 295 K
c = 5.6017 (2) Å	0.41 × 0.29 × 0.23 mm
β = 97.334 (3)°

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	1093 reflections with I > 2σ(I)
7072 measured reflections	R_int = 0.017
1280 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.14 e Å⁻³
1280 reflections	Δρ_min = −0.26 e Å⁻³
158 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
H1	0.844 (5)	0.2074 (13)	0.076 (5)	0.063 (6)*
C3	0.2527 (3)	0.28407 (9)	0.4595 (3)	0.0412 (4)
C2	0.4146 (3)	0.23191 (9)	0.4090 (3)	0.0423 (4)
H2	0.4181	0.1896	0.4896	0.051*
C1	0.5737 (3)	0.24414 (9)	0.2335 (3)	0.0454 (4)
N2	0.0876 (3)	0.27154 (8)	0.6441 (3)	0.0489 (4)
C6	0.5584 (3)	0.30889 (10)	0.1187 (4)	0.0516 (4)
H6	0.6626	0.318	0.0013	0.062*
C4	0.2364 (4)	0.34794 (9)	0.3472 (4)	0.0528 (5)
H4	0.1244	0.382	0.3858	0.063*
N1	0.7446 (4)	0.19560 (9)	0.1759 (4)	0.0663 (5)
O2	−0.0522 (3)	0.31801 (9)	0.6928 (3)	0.0763 (5)
O1	0.0942 (3)	0.21462 (8)	0.7433 (3)	0.0645 (4)
C5	0.3954 (4)	0.35886 (10)	0.1740 (4)	0.0579 (5)
H5	0.3905	0.4013	0.0939	0.069*
C8	0.5655 (3)	0.07735 (9)	0.2164 (3)	0.0496 (4)
C7	0.7768 (4)	0.12849 (11)	0.2881 (5)	0.0616 (5)
H7A	0.7937	0.1347	0.4612	0.074*
H7B	0.9335	0.1085	0.2492	0.074*
C11	0.1852 (4)	−0.01992 (12)	0.0930 (5)	0.0705 (6)
H11	0.0576	−0.0523	0.0518	0.085*
C13	0.4114 (4)	0.08153 (12)	−0.0021 (3)	0.0666 (6)
H13	0.4348	0.1172	−0.1093	0.08*
C10	0.3354 (5)	−0.02457 (12)	0.3060 (5)	0.0739 (6)
H10	0.3118	−0.0606	0.4115	0.089*
C9	0.5222 (4)	0.02354 (12)	0.3673 (4)	0.0651 (5)
H9	0.6224	0.0197	0.5152	0.078*
C12	0.2233 (5)	0.03297 (16)	−0.0607 (4)	0.0764 (6)
H12	0.1207	0.0363	−0.2075	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0386 (7)	0.0460 (9)	0.0405 (8)	−0.0039 (7)	0.0116 (6)	−0.0028 (6)
C2	0.0431 (8)	0.0405 (8)	0.0456 (9)	−0.0033 (7)	0.0142 (7)	0.0021 (7)
C1	0.0417 (8)	0.0458 (9)	0.0515 (10)	−0.0066 (7)	0.0164 (7)	−0.0044 (7)
N2	0.0472 (8)	0.0573 (9)	0.0444 (8)	−0.0030 (7)	0.0150 (6)	−0.0023 (7)
C6	0.0508 (10)	0.0569 (10)	0.0510 (10)	−0.0126 (9)	0.0211 (8)	0.0032 (8)
C4	0.0524 (10)	0.0441 (10)	0.0643 (12)	0.0042 (8)	0.0163 (9)	0.0017 (8)
N1	0.0602 (10)	0.0540 (10)	0.0943 (13)	0.0002 (8)	0.0470 (10)	−0.0012 (9)
O2	0.0773 (10)	0.0795 (11)	0.0811 (11)	0.0173 (9)	0.0447 (9)	−0.0031 (8)
O1	0.0718 (9)	0.0671 (9)	0.0601 (8)	−0.0025 (7)	0.0301 (7)	0.0108 (7)
C5	0.0603 (11)	0.0484 (11)	0.0671 (12)	−0.0028 (9)	0.0164 (10)	0.0147 (8)
C8	0.0481 (9)	0.0457 (10)	0.0577 (10)	0.0089 (8)	0.0171 (8)	−0.0069 (7)
C7	0.0468 (10)	0.0517 (10)	0.0892 (16)	0.0051 (8)	0.0201 (10)	−0.0067 (10)
C11	0.0620 (12)	0.0589 (12)	0.0913 (17)	−0.0032 (10)	0.0128 (12)	−0.0219 (9)
C13	0.0778 (14)	0.0645 (12)	0.0581 (13)	0.0059 (11)	0.0112 (11)	0.0051 (9)
C10	0.0851 (16)	0.0572 (12)	0.0803 (16)	−0.0117 (12)	0.0134 (13)	0.0030 (11)
C9	0.0722 (12)	0.0600 (12)	0.0617 (12)	−0.0029 (11)	0.0030 (10)	0.0041 (10)
C12	0.0778 (14)	0.0816 (14)	0.0653 (13)	0.0054 (13)	−0.0079 (11)	−0.0111 (10)

Geometric parameters (Å, º) top

C3—C2	1.376 (2)	C5—H5	0.93
C3—C4	1.378 (2)	C8—C9	1.374 (3)
C3—N2	1.461 (2)	C8—C13	1.3868 (17)
C2—C1	1.398 (2)	C8—C7	1.511 (3)
C2—H2	0.93	C7—H7A	0.97
C1—N1	1.372 (2)	C7—H7B	0.97
C1—C6	1.399 (3)	C11—C10	1.353 (4)
N2—O2	1.217 (2)	C11—C12	1.364 (4)
N2—O1	1.226 (2)	C11—H11	0.93
C6—C5	1.358 (3)	C13—C12	1.379 (4)
C6—H6	0.93	C13—H13	0.93
C4—C5	1.384 (3)	C10—C9	1.371 (3)
C4—H4	0.93	C10—H10	0.93
N1—C7	1.436 (3)	C9—H9	0.93
N1—H1	0.85 (3)	C12—H12	0.93

C2—C3—C4	124.08 (15)	C9—C8—C13	117.32 (18)
C2—C3—N2	118.44 (14)	C9—C8—C7	120.31 (17)
C4—C3—N2	117.48 (15)	C13—C8—C7	122.36 (19)
C3—C2—C1	118.37 (15)	N1—C7—C8	115.13 (19)
C3—C2—H2	120.8	N1—C7—H7A	108.5
C1—C2—H2	120.8	C8—C7—H7A	108.5
N1—C1—C2	122.14 (17)	N1—C7—H7B	108.5
N1—C1—C6	119.94 (16)	C8—C7—H7B	108.5
C2—C1—C6	117.90 (16)	H7A—C7—H7B	107.5
O2—N2—O1	122.47 (15)	C10—C11—C12	119.1 (2)
O2—N2—C3	118.66 (16)	C10—C11—H11	120.4
O1—N2—C3	118.87 (14)	C12—C11—H11	120.4
C5—C6—C1	121.74 (16)	C12—C13—C8	120.2 (2)
C5—C6—H6	119.1	C12—C13—H13	119.9
C1—C6—H6	119.1	C8—C13—H13	119.9
C3—C4—C5	116.54 (16)	C11—C10—C9	120.4 (2)
C3—C4—H4	121.7	C11—C10—H10	119.8
C5—C4—H4	121.7	C9—C10—H10	119.8
C1—N1—C7	123.70 (18)	C10—C9—C8	121.9 (2)
C1—N1—H1	117.6 (17)	C10—C9—H9	119.1
C7—N1—H1	118.6 (17)	C8—C9—H9	119.1
C6—C5—C4	121.36 (17)	C11—C12—C13	121.1 (2)
C6—C5—H5	119.3	C11—C12—H12	119.4
C4—C5—H5	119.3	C13—C12—H12	119.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.84 (2)	2.44 (2)	3.263 (2)	166 (2)
C6—H6···O2ⁱ	0.93	2.45	3.364 (2)	169
C13—H13···O1ⁱⁱ	0.93	2.67	3.293 (2)	125
C7—H7A···O1ⁱⁱⁱ	0.97	2.61	3.318 (2)	130

Symmetry codes: (i) x+1, y, z−1; (ii) x, y, z−1; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂O₂
M_r	228.25
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	295
a, b, c (Å)	5.3359 (2), 19.2285 (6), 5.6017 (2)
β (°)	97.334 (3)
V (Å³)	570.04 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.41 × 0.29 × 0.23

Data collection
Diffractometer	Oxford Diffraction Xcalibur CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7072, 1280, 1093
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.01
No. of reflections	1280
No. of parameters	158
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.26

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), POV-RAY (Cason et al., 2002) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.84 (2)	2.44 (2)	3.263 (2)	166 (2)
C6—H6···O2ⁱ	0.93	2.446	3.364 (2)	169
C13—H13···O1ⁱⁱ	0.93	2.670	3.293 (2)	125
C7—H7A···O1ⁱⁱⁱ	0.97	2.605	3.318 (2)	130

Symmetry codes: (i) x+1, y, z−1; (ii) x, y, z−1; (iii) x+1, y, z.

Acknowledgements

The authors would like to thank the Ministry of Science, Education and Sport, Republic of Croatia, for financial support of this work through grants 119–1193079–3069, 006–0000000–3216 and 098–0982904–2912.

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