4-Meth­oxy-N-phenyl­aniline

Krzymiński, K.; Wera, M.; Sikorski, A.; Błażejowski, J.

doi:10.1107/S1600536808039457

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o152

doi:10.1107/S1600536808039457

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4-Methoxy-N-phenylaniline

Karol Krzymiński,^a Michał Wera,^a Artur Sikorski ^a and Jerzy Błażejowski ^a ^*

^aFaculty of Chemistry, University of Gdańsk, J. Sobieskiego 18, 80-952 Gdańsk, Poland
^*Correspondence e-mail: bla@chem.univ.gda.pl

(Received 6 November 2008; accepted 24 November 2008; online 17 December 2008)

In the molecule of the title compound, C₁₃H₁₃NO, the two benzene rings are oriented at a dihedral angle of 59.9 (2)°. In the crystal structure, the benzene rings of neighbouring molecules are oriented nearly parallel or perpendicular, making dihedral angles of 2.8 (2) and 79.5 (2)°, respectively. The crystal structure is stabilized by a network of C—H⋯π and N—H⋯π interactions.

Related literature

For general background, see: Acheson (1973 ); Gatto et al. (2006 ); Li et al. (2002 ); Oettmeier & Renger (1980 ); Razavi & McCapra (2000a ,b ); Steiner (2000 ); Takahashi et al. (2001 ); Velusamy et al. (2005 ); Zomer & Jacquemijns (2001 ). For related structures, see: Rodriguez & Bunge (2003 ).

Experimental

Crystal data

C₁₃H₁₃NO
M_r = 199.24
Orthorhombic, P c c n
a = 15.090 (3) Å
b = 18.394 (4) Å
c = 7.596 (2) Å
V = 2108.4 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 (2) K
0.05 × 0.03 × 0.02 mm

Data collection

Kuma KM-4 diffractometer
Absorption correction: none
2443 measured reflections
1851 independent reflections
1005 reflections with I > 2σ(I)
R_int = 0.035
3 standard reflections every 200 reflections intensity decay: 0.5%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.131
S = 0.99
1851 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
C—H⋯π and N—H⋯π interactions (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg2ⁱ	0.93	2.91	3.671 (2)	139
N7—H7⋯Cg1ⁱⁱ	0.86	2.88	3.593 (2)	142
C10—H10⋯Cg1ⁱⁱⁱ	0.93	2.92	3.723 (3)	145
Symmetry codes: (i) x, y, z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1. Cg1 and Cg2 are the centroids of the C1–C6 ring and C8–C13 rings, respectively.

Data collection: KM-4 Software (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). KM-4 Software. Oxford Diffraction, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039457/hk2570sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039457/hk2570Isup2.hkl

checkCIF report

Comment top

Diphenylamines are an important class of aromatic amines widely employed in organic (Acheson, 1973) and organometallic (Li et al., 2002) syntheses. They exhibit interesting biological activities (Oettmeier & Renger, 1980). Some of them are known to be useful antioxidants for modern lubricants (Gatto et al., 2006) or as fragments of molecules with interesting electro-optical properties (Velusamy et al., 2005). Diphenylamines are precursors of acridine-9-carboxylic acids (Acheson, 1973; Zomer & Jacquemijns, 2001), which are starting materials for syntheses of acridinium chemiluminogenic tracers (Razavi & McCapra, 2000a,b; Zomer & Jacquemijns, 2001). The presence of a methoxy group in such tracers enhances their stability in an aquatic environment and brings about a red shifting of the emitted light. The latter feature should increase the potential applicability of acridinium chemiluminogens in immunoassays (Zomer & Jacquemijns, 2001).

In the molecule of the title compound (Fig. 1) the bond lengths and angles are in accordance with the corresponding values in diphenylamine (Rodriguez & Bunge, 2003). Rings A (C1-C6) and B (C8-C13) are planar and oriented at a dihedral angle of 59.9 (2)°.

In the crystal structure, benzene ring systems of neighbouring molecules are oriented nearly parallel or perpendicular. The respective angles between them are 2.8 (2)° and 79.5 (2)°. The crystal structure of the title compound is stabilized by a network of specific C—H···π and N—H···π interactions (Fig. 2 and Table 1) which exhibit an attractive nature (Steiner, 2000; Takahashi et al., 2001), as well as by non-specific dispersive interactions.

Related literature top

For general background, see: Acheson (1973); Li et al. (2002); Oettmeier & Renger (1980); Gatto et al. (2006); Velusamy et al. (2005); Razavi & McCapra (2000a,b); Steiner (2000); Takahashi et al. (2001). For related structres, see: Rodriguez & Bunge (2003); Zomer & Jacquemijns (2001).

Experimental top

The title compound was synthesized by the condensation of 4-methoxy-benzenamine and bromobenzene in the presence of anhydrous potassium carbonate and a catalytic amount of copper iodide (yield; 75%) (Zomer & Jacquemijns, 2001). Elemental analysis (% found/calculated): C 78.16/78.36, H 6.58/6.72, N 7.02/7.03. Colorless crystals (m.p. 379-380 K) suitable for X-ray analysis were grown from absolute ethanol solution.

Computing details top

Data collection: KM-4 Software (Oxford Diffraction, 2003); cell refinement: KM-4 Software (Oxford Diffraction, 2003); data reduction: KM-4 Software (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 25% probability level. Cg1 and Cg2 denote the ring centroids.
	Fig. 2. The arrangement of the molecules in the crystal packing, viewed approximately along the a axis. The C—H···π and N—H···π interactions are represented by dotted lines. H atoms not involved in interactions have been omitted [symmetry codes: (i) x, y, 1 + z; (ii) x, 1/2 - y, -1/2 + z; (iii) 1 - x, 1 - y, 1 - z].

4-Methoxy-N-phenylaniline top

Crystal data top

C₁₃H₁₃NO	F(000) = 848
M_r = 199.24	D_x = 1.255 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 50 reflections
a = 15.090 (3) Å	θ = 2.2–25°
b = 18.394 (4) Å	µ = 0.08 mm⁻¹
c = 7.596 (2) Å	T = 295 K
V = 2108.4 (8) Å³	Block, colorless
Z = 8	0.05 × 0.03 × 0.02 mm

Data collection top

Kuma KM-4 diffractometer	R_int = 0.035
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.2°
Graphite monochromator	h = 0→17
θ/2θ scans	k = −21→0
2443 measured reflections	l = −9→2
1851 independent reflections	3 standard reflections every 200 reflections
1005 reflections with I > 2σ(I)	intensity decay: 0.5%

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.081P)² + 0.0542P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
1851 reflections	Δρ_max = 0.16 e Å⁻³
138 parameters	Δρ_min = −0.15 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: 0.015 (2)

Crystal data top

C₁₃H₁₃NO	V = 2108.4 (8) Å³
M_r = 199.24	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 15.090 (3) Å	µ = 0.08 mm⁻¹
b = 18.394 (4) Å	T = 295 K
c = 7.596 (2) Å	0.05 × 0.03 × 0.02 mm

Data collection top

Kuma KM-4 diffractometer	R_int = 0.035
2443 measured reflections	3 standard reflections every 200 reflections
1851 independent reflections	intensity decay: 0.5%
1005 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 0.99	Δρ_max = 0.16 e Å⁻³
1851 reflections	Δρ_min = −0.15 e Å⁻³
138 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.49051 (14)	0.32843 (9)	0.6655 (3)	0.0526 (6)
C2	0.52660 (14)	0.36650 (10)	0.8048 (3)	0.0533 (5)
H2	0.5861	0.3794	0.8010	0.064*
C3	0.47688 (12)	0.38576 (10)	0.9489 (3)	0.0500 (5)
H3	0.5025	0.4117	1.0409	0.060*
C4	0.38875 (13)	0.36634 (10)	0.9558 (3)	0.0491 (5)
C5	0.35215 (14)	0.32732 (10)	0.8191 (3)	0.0553 (6)
H5	0.2930	0.3133	0.8244	0.066*
C6	0.40192 (15)	0.30921 (10)	0.6763 (3)	0.0577 (6)
H6	0.3760	0.2835	0.5843	0.069*
N7	0.54179 (14)	0.30655 (9)	0.5208 (2)	0.0679 (6)
H7	0.5415	0.2610	0.4954	0.082*
C8	0.59269 (13)	0.35133 (11)	0.4155 (3)	0.0488 (5)
C9	0.59081 (13)	0.42662 (10)	0.4292 (3)	0.0535 (5)
H9	0.5561	0.4486	0.5153	0.064*
C10	0.63953 (16)	0.46850 (13)	0.3170 (3)	0.0701 (7)
H10	0.6377	0.5188	0.3279	0.084*
C11	0.69087 (19)	0.43785 (18)	0.1892 (3)	0.0882 (9)
H11	0.7233	0.4669	0.1124	0.106*
C12	0.69399 (16)	0.36363 (17)	0.1759 (3)	0.0809 (8)
H12	0.7291	0.3422	0.0897	0.097*
C13	0.64619 (14)	0.32079 (13)	0.2877 (3)	0.0633 (6)
H13	0.6497	0.2705	0.2777	0.076*
O14	0.33254 (9)	0.38212 (8)	1.0914 (2)	0.0671 (5)
C15	0.36725 (18)	0.41960 (15)	1.2379 (3)	0.0809 (7)
H15A	0.3220	0.4246	1.3260	0.121*
H15B	0.3871	0.4669	1.2018	0.121*
H15C	0.4162	0.3928	1.2857	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0758 (14)	0.0385 (10)	0.0434 (11)	−0.0006 (9)	0.0030 (11)	0.0020 (9)
C2	0.0537 (11)	0.0521 (11)	0.0542 (13)	−0.0044 (9)	0.0006 (10)	−0.0014 (9)
C3	0.0555 (11)	0.0497 (10)	0.0448 (11)	−0.0027 (9)	−0.0027 (10)	−0.0019 (9)
C4	0.0534 (11)	0.0462 (10)	0.0475 (11)	0.0004 (9)	0.0005 (10)	0.0042 (9)
C5	0.0531 (12)	0.0536 (11)	0.0593 (14)	−0.0081 (9)	−0.0085 (11)	0.0039 (10)
C6	0.0764 (15)	0.0458 (11)	0.0510 (13)	−0.0124 (10)	−0.0146 (11)	0.0016 (10)
N7	0.1075 (14)	0.0417 (8)	0.0546 (11)	−0.0010 (9)	0.0181 (11)	−0.0072 (8)
C8	0.0529 (11)	0.0553 (11)	0.0383 (10)	0.0050 (8)	−0.0078 (9)	−0.0012 (9)
C9	0.0610 (12)	0.0523 (11)	0.0471 (12)	0.0029 (9)	−0.0039 (10)	0.0022 (10)
C10	0.0821 (16)	0.0706 (14)	0.0577 (15)	−0.0181 (12)	−0.0034 (13)	0.0091 (12)
C11	0.0803 (17)	0.125 (2)	0.0595 (17)	−0.0421 (17)	0.0081 (14)	−0.0006 (16)
C12	0.0543 (13)	0.126 (2)	0.0622 (16)	−0.0077 (14)	0.0080 (12)	−0.0266 (15)
C13	0.0589 (13)	0.0755 (14)	0.0556 (13)	0.0104 (11)	−0.0050 (11)	−0.0181 (12)
O14	0.0578 (9)	0.0794 (10)	0.0642 (10)	−0.0026 (7)	0.0064 (7)	−0.0103 (8)
C15	0.0766 (15)	0.1028 (18)	0.0634 (16)	0.0028 (14)	0.0076 (14)	−0.0203 (15)

Geometric parameters (Å, º) top

C1—C2	1.381 (3)	C8—C9	1.389 (3)
C1—C6	1.385 (3)	C9—C10	1.364 (3)
C1—N7	1.403 (3)	C9—H9	0.9300
C2—C3	1.373 (3)	C10—C11	1.364 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.378 (3)	C11—C12	1.370 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—O14	1.365 (2)	C12—C13	1.365 (3)
C4—C5	1.378 (3)	C12—H12	0.9300
C5—C6	1.361 (3)	C13—H13	0.9300
C5—H5	0.9300	O14—C15	1.410 (3)
C6—H6	0.9300	C15—H15A	0.9600
N7—C8	1.381 (3)	C15—H15B	0.9600
N7—H7	0.8600	C15—H15C	0.9600
C8—C13	1.382 (3)

C2—C1—C6	117.68 (19)	C13—C8—C9	118.0 (2)
C2—C1—N7	121.9 (2)	C10—C9—C8	120.4 (2)
C6—C1—N7	120.36 (19)	C10—C9—H9	119.8
C3—C2—C1	121.74 (19)	C8—C9—H9	119.8
C3—C2—H2	119.1	C9—C10—C11	121.1 (2)
C1—C2—H2	119.1	C9—C10—H10	119.4
C2—C3—C4	119.42 (19)	C11—C10—H10	119.4
C2—C3—H3	120.3	C10—C11—C12	119.0 (2)
C4—C3—H3	120.3	C10—C11—H11	120.5
O14—C4—C3	125.00 (18)	C12—C11—H11	120.5
O14—C4—C5	115.48 (17)	C13—C12—C11	120.8 (2)
C3—C4—C5	119.52 (19)	C13—C12—H12	119.6
C6—C5—C4	120.48 (18)	C11—C12—H12	119.6
C6—C5—H5	119.8	C12—C13—C8	120.7 (2)
C4—C5—H5	119.8	C12—C13—H13	119.6
C5—C6—C1	121.15 (19)	C8—C13—H13	119.6
C5—C6—H6	119.4	C4—O14—C15	117.9 (2)
C1—C6—H6	119.4	O14—C15—H15A	109.5
C1—N7—C8	126.1 (2)	O14—C15—H15B	109.5
C8—N7—H7	116.9	H15A—C15—H15B	109.5
C1—N7—H7	116.9	O14—C15—H15C	109.5
N7—C8—C13	119.30 (19)	H15A—C15—H15C	109.5
N7—C8—C9	122.67 (18)	H15B—C15—H15C	109.5

C6—C1—C2—C3	−0.8 (3)	C1—N7—C8—C13	174.0 (2)
N7—C1—C2—C3	−177.82 (17)	C1—N7—C8—C9	−7.8 (3)
C1—C2—C3—C4	0.4 (3)	N7—C8—C9—C10	−177.21 (19)
C2—C3—C4—O14	179.92 (17)	C13—C8—C9—C10	1.1 (3)
C2—C3—C4—C5	0.6 (3)	C8—C9—C10—C11	0.1 (3)
O14—C4—C5—C6	179.34 (17)	C9—C10—C11—C12	−0.9 (4)
C3—C4—C5—C6	−1.3 (3)	C10—C11—C12—C13	0.4 (4)
C4—C5—C6—C1	0.9 (3)	C11—C12—C13—C8	0.8 (4)
C2—C1—C6—C5	0.1 (3)	N7—C8—C13—C12	176.8 (2)
N7—C1—C6—C5	177.18 (18)	C9—C8—C13—C12	−1.5 (3)
C2—C1—N7—C8	−55.5 (3)	C3—C4—O14—C15	−1.6 (3)
C6—C1—N7—C8	127.6 (2)	C5—C4—O14—C15	177.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg2ⁱ	0.93	2.91	3.671 (2)	139
N7—H7···Cg1ⁱⁱ	0.86	2.88	3.593 (2)	142
C10—H10···Cg1ⁱⁱⁱ	0.93	2.92	3.723 (3)	145

Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO
M_r	199.24
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	295
a, b, c (Å)	15.090 (3), 18.394 (4), 7.596 (2)
V (Å³)	2108.4 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.05 × 0.03 × 0.02

Data collection
Diffractometer	Kuma KM-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2443, 1851, 1005
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.131, 0.99
No. of reflections	1851
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.15

Computer programs: KM-4 Software (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 2008), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg2ⁱ	0.93	2.91	3.671 (2)	139
N7—H7···Cg1ⁱⁱ	0.86	2.88	3.593 (2)	142
C10—H10···Cg1ⁱⁱⁱ	0.93	2.92	3.723 (3)	145

Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1.

Acknowledgements

This study was financed by the State Funds for Scientific Research (grant No. N204 123 32/3143, contract No. 3143/H03/2007/32 of the Polish Ministry of Research and Higher Education) for the period 2007–2010.

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