N-(4-Methyl-benz-yl)-3-nitro-aniline.

In the title compound, C(14)H(14)N(2)O(2), the angle between the mean plane of the N-methyl-3-nitro-aniline system (r.m.s. deviation = 0.0185 Å) and the p-tolyl unit is 89.79 (4)°. In the crystal, hydrogen-bonded chains running along [10-1] are generated by the linking of neighbouring mol-ecules via N-H⋯O and C-H⋯O hydrogen bonds involving the 3-nitro-aniline systems and forming R(2) (2)(8) motifs.

Related literature

For related structures, see: Betz et al. (2011 ▶); Stilinović & Portada (2011 ▶); Xing et al. (2006 ▶). For the synthesis, see: Magyarfalvi (2008 ▶). For graph-set theory, see: Etter (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C14H14N2O2

M = 242.27

Monoclinic,

a = 5.1851 (4) Å

b = 21.408 (2) Å

c = 5.6833 (4) Å

β = 98.010 (7)°

V = 624.71 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.57 × 0.50 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire-3 CCD area detector

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.953, T max = 0.958

11868 measured reflections

1856 independent reflections

1373 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.117

S = 1.03

1856 reflections

167 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.11 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024348/fj2555sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024348/fj2555Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H14N2O2	F(000) = 256
Mr = 242.27	Dx = 1.288 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 yb	Cell parameters from 4334 reflections
a = 5.1851 (4) Å	θ = 4.4–32.7°
b = 21.408 (2) Å	µ = 0.09 mm−1
c = 5.6833 (4) Å	T = 296 K
β = 98.010 (7)°	Plate, yellow
V = 624.71 (8) Å3	0.57 × 0.50 × 0.19 mm
Z = 2

Oxford Diffraction Xcalibur diffractometer with a Sapphire-3 CCD area detector	1856 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1373 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 16.3426 pixels mm-1	θmax = 30.0°, θmin = 4.4°
CCD scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −30→30
Tmin = 0.953, Tmax = 0.958	l = −7→7
11868 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0688P)2] where P = (Fo2 + 2Fc2)/3
1856 reflections	(Δ/σ)max < 0.001
167 parameters	Δρmax = 0.16 e Å−3
1 restraint	Δρmin = −0.11 e Å−3

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 on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
O1	0.0400 (4)	0.59135 (11)	0.2460 (4)	0.0814 (8)
O2	0.1836 (4)	0.49767 (11)	0.2911 (3)	0.0688 (7)
N1	0.8389 (4)	0.47827 (11)	−0.2730 (5)	0.0645 (8)
N2	0.1802 (4)	0.54885 (10)	0.1976 (3)	0.0525 (7)
C1	0.6686 (4)	0.52300 (11)	−0.2149 (4)	0.0455 (6)
C2	0.5065 (4)	0.51224 (10)	−0.0402 (4)	0.0417 (6)
C3	0.3489 (4)	0.56021 (10)	0.0150 (4)	0.0434 (6)
C4	0.3374 (5)	0.61797 (11)	−0.0925 (5)	0.0564 (8)
C5	0.4936 (5)	0.62762 (13)	−0.2656 (5)	0.0627 (9)
C6	0.6563 (5)	0.58119 (12)	−0.3245 (4)	0.0558 (8)
C7	0.8676 (5)	0.41780 (13)	−0.1683 (5)	0.0619 (8)
C8	0.6482 (4)	0.37253 (11)	−0.2473 (4)	0.0511 (7)
C9	0.5891 (6)	0.32463 (15)	−0.1024 (5)	0.0703 (10)
C10	0.3929 (7)	0.28214 (14)	−0.1763 (6)	0.0747 (11)
C11	0.2506 (6)	0.28531 (12)	−0.3980 (5)	0.0628 (9)
C12	0.3078 (6)	0.33344 (14)	−0.5412 (5)	0.0669 (9)
C13	0.5021 (6)	0.37587 (13)	−0.4681 (5)	0.0608 (8)
C14	0.0335 (7)	0.23991 (16)	−0.4795 (9)	0.0912 (13)
H1N	0.913 (6)	0.4885 (14)	−0.376 (5)	0.061 (8)*
H2	0.50580	0.47380	0.03580	0.0500*
H4	0.22830	0.64920	−0.04980	0.0680*
H5	0.48930	0.66590	−0.34350	0.0750*
H6	0.76130	0.58890	−0.44120	0.0670*
H7A	0.88320	0.42240	0.00290	0.0740*
H7B	1.02900	0.39970	−0.20470	0.0740*
H9	0.68320	0.32070	0.04860	0.0840*
H10	0.35690	0.25070	−0.07280	0.0890*
H12	0.21290	0.33750	−0.69180	0.0800*
H13	0.53540	0.40770	−0.57100	0.0730*
H14A	−0.04300	0.25020	−0.63840	0.1370*
H14B	−0.09690	0.24240	−0.37530	0.1370*
H14C	0.10230	0.19820	−0.47650	0.1370*

	U11	U22	U33	U12	U13	U23
O1	0.0779 (13)	0.0904 (15)	0.0858 (13)	0.0136 (12)	0.0468 (11)	−0.0109 (11)
O2	0.0736 (12)	0.0795 (13)	0.0590 (10)	−0.0050 (10)	0.0297 (9)	0.0073 (10)
N1	0.0566 (13)	0.0626 (13)	0.0834 (15)	−0.0065 (10)	0.0420 (12)	−0.0110 (11)
N2	0.0432 (10)	0.0693 (14)	0.0474 (10)	−0.0029 (9)	0.0144 (8)	−0.0086 (10)
C1	0.0394 (10)	0.0524 (12)	0.0462 (11)	−0.0081 (9)	0.0108 (8)	−0.0108 (9)
C2	0.0376 (9)	0.0446 (11)	0.0443 (10)	−0.0026 (8)	0.0111 (8)	−0.0001 (8)
C3	0.0394 (10)	0.0537 (12)	0.0387 (9)	−0.0031 (9)	0.0116 (8)	−0.0042 (8)
C4	0.0525 (13)	0.0498 (13)	0.0695 (14)	0.0056 (11)	0.0173 (11)	−0.0005 (12)
C5	0.0689 (16)	0.0546 (14)	0.0668 (15)	0.0009 (12)	0.0177 (13)	0.0136 (12)
C6	0.0534 (13)	0.0654 (15)	0.0530 (13)	−0.0136 (11)	0.0226 (10)	0.0013 (11)
C7	0.0446 (12)	0.0669 (15)	0.0753 (16)	0.0093 (12)	0.0120 (11)	−0.0171 (13)
C8	0.0521 (12)	0.0502 (12)	0.0528 (12)	0.0131 (10)	0.0142 (10)	−0.0040 (10)
C9	0.0801 (19)	0.0749 (17)	0.0551 (14)	0.0082 (16)	0.0069 (13)	0.0144 (14)
C10	0.085 (2)	0.0564 (15)	0.088 (2)	0.0077 (14)	0.0303 (17)	0.0262 (15)
C11	0.0629 (16)	0.0478 (13)	0.0820 (19)	0.0067 (11)	0.0252 (15)	−0.0065 (13)
C12	0.0719 (17)	0.0706 (17)	0.0572 (14)	−0.0026 (14)	0.0057 (12)	−0.0049 (13)
C13	0.0720 (15)	0.0569 (13)	0.0547 (13)	−0.0022 (13)	0.0135 (11)	0.0080 (12)
C14	0.078 (2)	0.0619 (18)	0.137 (3)	−0.0059 (15)	0.027 (2)	−0.021 (2)

O1—N2	1.220 (3)	C11—C14	1.510 (5)
O2—N2	1.217 (3)	C11—C12	1.371 (4)
N1—C1	1.374 (3)	C12—C13	1.377 (4)
N1—C7	1.424 (4)	C2—H2	0.9300
N2—C3	1.468 (3)	C4—H4	0.9300
N1—H1N	0.78 (3)	C5—H5	0.9300
C1—C6	1.390 (3)	C6—H6	0.9300
C1—C2	1.406 (3)	C7—H7A	0.9700
C2—C3	1.376 (3)	C7—H7B	0.9700
C3—C4	1.377 (3)	C9—H9	0.9300
C4—C5	1.374 (4)	C10—H10	0.9300
C5—C6	1.375 (4)	C12—H12	0.9300
C7—C8	1.514 (4)	C13—H13	0.9300
C8—C13	1.374 (4)	C14—H14A	0.9600
C8—C9	1.376 (4)	C14—H14B	0.9600
C9—C10	1.386 (5)	C14—H14C	0.9600
C10—C11	1.370 (4)
O1···C1i	3.362 (3)	C13···H7Bi	3.0900
O1···C6ii	3.364 (3)	H1N···O2vi	2.52 (3)
O2···C7i	3.352 (3)	H1N···H6	2.3000
O2···C13iii	3.282 (4)	H2···O2	2.4200
O1···H14Civ	2.7900	H2···C7	2.6300
O1···H4	2.4000	H2···C8	2.8600
O1···H6ii	2.4400	H2···H7A	2.2800
O2···H1Nii	2.52 (3)	H4···O1	2.4000
O2···H2	2.4200	H5···H14Cviii	2.5700
O2···H7Ai	2.6400	H6···O1vi	2.4400
O2···H13iii	2.6900	H6···H1N	2.3000
N1···C3v	3.398 (3)	H6···H14Cviii	2.5100
N2···C1i	3.333 (3)	H7A···O2v	2.6400
N1···H13	2.6200	H7A···C2	2.7300
C1···O1v	3.362 (3)	H7A···H2	2.2800
C1···N2v	3.333 (3)	H7A···H9	2.4400
C1···C13	3.520 (4)	H7B···C11v	2.9800
C2···C8	3.333 (3)	H7B···C12v	2.9200
C3···N1i	3.398 (3)	H7B···C13v	3.0900
C6···O1vi	3.364 (3)	H9···H7A	2.4400
C7···O2v	3.352 (3)	H9···H14Aix	2.6000
C8···C2	3.333 (3)	H12···H14A	2.3400
C13···C1	3.520 (4)	H13···O2vii	2.6900
C13···O2vii	3.282 (4)	H13···N1	2.6200
C2···H7A	2.7300	H14A···H9x	2.6000
C6···H14Cviii	3.0800	H14A···H12	2.3400
C7···H2	2.6300	H14B···C9i	2.9800
C8···H2	2.8600	H14C···O1xi	2.7900
C9···H14Bv	2.9800	H14C···C6xii	3.0800
C11···H7Bi	2.9800	H14C···H5xii	2.5700
C12···H7Bi	2.9200	H14C···H6xii	2.5100
C1—N1—C7	124.5 (2)	C1—C2—H2	121.00
O1—N2—O2	123.1 (2)	C3—C2—H2	121.00
O1—N2—C3	117.9 (2)	C3—C4—H4	121.00
O2—N2—C3	119.0 (2)	C5—C4—H4	121.00
C7—N1—H1N	123 (2)	C4—C5—H5	120.00
C1—N1—H1N	113 (2)	C6—C5—H5	120.00
N1—C1—C6	120.5 (2)	C1—C6—H6	119.00
C2—C1—C6	117.9 (2)	C5—C6—H6	119.00
N1—C1—C2	121.5 (2)	N1—C7—H7A	108.00
C1—C2—C3	118.1 (2)	N1—C7—H7B	108.00
N2—C3—C4	118.0 (2)	C8—C7—H7A	108.00
N2—C3—C2	117.97 (19)	C8—C7—H7B	108.00
C2—C3—C4	124.0 (2)	H7A—C7—H7B	107.00
C3—C4—C5	117.3 (2)	C8—C9—H9	119.00
C4—C5—C6	120.6 (2)	C10—C9—H9	119.00
C1—C6—C5	122.0 (2)	C9—C10—H10	119.00
N1—C7—C8	115.3 (2)	C11—C10—H10	119.00
C9—C8—C13	116.4 (2)	C11—C12—H12	119.00
C7—C8—C9	121.4 (2)	C13—C12—H12	119.00
C7—C8—C13	122.2 (2)	C8—C13—H13	119.00
C8—C9—C10	121.5 (3)	C12—C13—H13	119.00
C9—C10—C11	121.7 (3)	C11—C14—H14A	109.00
C10—C11—C14	122.2 (3)	C11—C14—H14B	110.00
C10—C11—C12	116.7 (3)	C11—C14—H14C	109.00
C12—C11—C14	121.0 (3)	H14A—C14—H14B	109.00
C11—C12—C13	121.8 (3)	H14A—C14—H14C	109.00
C8—C13—C12	121.9 (3)	H14B—C14—H14C	109.00
C7—N1—C1—C2	0.7 (4)	C3—C4—C5—C6	−0.9 (4)
C7—N1—C1—C6	179.2 (2)	C4—C5—C6—C1	0.6 (4)
C1—N1—C7—C8	73.9 (3)	N1—C7—C8—C9	−152.7 (3)
O1—N2—C3—C2	−179.8 (2)	N1—C7—C8—C13	29.0 (4)
O1—N2—C3—C4	−0.6 (3)	C7—C8—C13—C12	178.1 (3)
O2—N2—C3—C2	−0.8 (3)	C7—C8—C9—C10	−178.3 (3)
O2—N2—C3—C4	178.5 (2)	C13—C8—C9—C10	0.1 (4)
N1—C1—C2—C3	177.4 (2)	C9—C8—C13—C12	−0.3 (4)
C6—C1—C2—C3	−1.1 (3)	C8—C9—C10—C11	0.8 (5)
N1—C1—C6—C5	−178.1 (2)	C9—C10—C11—C12	−1.5 (5)
C2—C1—C6—C5	0.5 (4)	C9—C10—C11—C14	−179.0 (3)
C1—C2—C3—N2	−179.93 (19)	C10—C11—C12—C13	1.3 (5)
C1—C2—C3—C4	0.9 (3)	C14—C11—C12—C13	178.9 (3)
N2—C3—C4—C5	−179.1 (2)	C11—C12—C13—C8	−0.4 (5)
C2—C3—C4—C5	0.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2vi	0.78 (3)	2.52 (3)	3.277 (3)	168 (3)
C6—H6···O1vi	0.93	2.44	3.364 (3)	171
C7—H7A···O2v	0.97	2.64	3.352 (3)	130
C13—H13···O2vii	0.93	2.69	3.282 (4)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2i	0.78 (3)	2.52 (3)	3.277 (3)	168 (3)
C6—H6⋯O1i	0.93	2.44	3.364 (3)	171
C7—H7A⋯O2ii	0.97	2.64	3.352 (3)	130
C13—H13⋯O2iii	0.93	2.69	3.282 (4)	122

Symmetry codes: (i) ; (ii) ; (iii) .