4-Methyl-3-[4-(3-pyrid­yl)pyrimidin-2-yl­oxy]aniline

Tang, S.-G.; Yang, C.-L.; Chen, J.-H.; Bi, S.; Guo, C.

doi:10.1107/S1600536809023770

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1707

doi:10.1107/S1600536809023770

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4-Methyl-3-[4-(3-pyridyl)pyrimidin-2-yloxy]aniline

Shi-Gui Tang,^a Cheng-Long Yang,^b Jun-Hua Chen,^c Sheng Bi ^d and Cheng Guo ^c ^*

^aCollege of Biology and Pharmacy Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, ^bCollege of Kang ni, Nanjing College of Engineering, Hongjing Road No. 1 Jiangning District, Nanjing, Nanjing 211167, People's Republic of China, ^cCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^dGuangdong Petroleum College of Technology, Chisha Road No. 23 Nanhai District, Fushan, Fushan 528222, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 3 June 2009; accepted 21 June 2009; online 27 June 2009)

In the title compound, C₁₆H₁₄N₄O, there are intermolecular N—H⋯N hydrogen bonds which may be effective in stabilizing the crystal. The title compound is an important medicament and is used in the synthesis of antitumour drugs.

Related literature

For bond-length data, see: Allen et al. (1987 )

Experimental

Crystal data

C₁₆H₁₄N₄O
M_r = 278.31
Monoclinic, P 2₁ /c
a = 8.5800 (17) Å
b = 20.360 (4) Å
c = 8.0780 (16) Å
β = 98.29 (3)°
V = 1396.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.983, T_max = 0.991
2698 measured reflections
2526 independent reflections
1587 reflections with I > 2σ(I)
R_int = 0.018
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.170
S = 1.01
2526 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N4ⁱ	0.86	2.47	3.214 (4)	145
N1—H1B⋯N2ⁱⁱ	0.86	2.43	3.166 (4)	144
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x, -y+1, -z+2.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); 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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023770/pv2165sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023770/pv2165Isup2.hkl

checkCIF report

Comment top

Some derivatives of benzenamine are important medical materials. We report here the crystal structure of the title compound, (I), which was synthesized by the reaction of tert-butyl-4-methyl-3-(4-(3-pyridinyl)pyrimidin-2 -yloxy)phenylcarbamate and dichloromethane with trifluoroacetic acid. The molecular structure of (I) is shown in Fig. 1. The bond lengths and angles in (I) are within normal ranges (Allen et al. 1987). The structure is stabilized by N—H···N type hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For bond-length data, see: Allen et al. (1987)

Experimental top

In a three neck bottom flask containing dichloromethane (65 ml) and trifluoroacetic acid (20 ml) was added tert-butyl-4-methyl-3- (4-(3-pyridinyl)pyrimidin-2-yloxy)phenylcarbamate (7.5 g) at 273 K. After the addition of all chemicals, the flask was taken off the ice-water bath and the reaction was allowed to take place for 6 h at room temperature. Neutralized with sodium bicarbonate and separated the dichloromethane and aqueous layers. On evaporation of dichloromethane a solid product was obtained. Crystals of (I) suitable for X-ray diffraction were obstained by slow evaporation of a cyclohexane solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); 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: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A packing diagram of (I). The intermolecular hydrogen bonds are shown as dashed lines.

4-Methyl-3-[4-(3-pyridyl)pyrimidin-2-yloxy]aniline top

Crystal data top

C₁₆H₁₄N₄O	F(000) = 584
M_r = 278.31	D_x = 1.324 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.5800 (17) Å	θ = 9–13°
b = 20.360 (4) Å	µ = 0.09 mm⁻¹
c = 8.0780 (16) Å	T = 293 K
β = 98.29 (3)°	Block, colorless
V = 1396.4 (5) Å³	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1587 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 25.3°, θ_min = 2.0°
ω/2θ scans	h = −10→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→24
T_min = 0.983, T_max = 0.991	l = −9→9
2698 measured reflections	3 standard reflections every 200 reflections
2526 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)] = 0.061	H-atom parameters constrained
wR(F²) = 0.170	w = 1/[σ²(F_o²) + (0.06P)² + 1.4P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2526 reflections	Δρ_max = 0.28 e Å⁻³
190 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (4)

Crystal data top

C₁₆H₁₄N₄O	V = 1396.4 (5) Å³
M_r = 278.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5800 (17) Å	µ = 0.09 mm⁻¹
b = 20.360 (4) Å	T = 293 K
c = 8.0780 (16) Å	0.20 × 0.20 × 0.10 mm
β = 98.29 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1587 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.018
T_min = 0.983, T_max = 0.991	3 standard reflections every 200 reflections
2698 measured reflections	intensity decay: 1%
2526 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.01	Δρ_max = 0.28 e Å⁻³
2526 reflections	Δρ_min = −0.30 e Å⁻³
190 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
O	0.1194 (2)	0.51325 (11)	0.7760 (3)	0.0508 (6)
N1	−0.2002 (3)	0.66654 (13)	1.0241 (4)	0.0543 (8)
H1A	−0.2537	0.7024	1.0186	0.065*
H1B	−0.1955	0.6419	1.1111	0.065*
C1	0.1120 (5)	0.5926 (2)	0.4732 (5)	0.0680 (11)
H1C	0.1658	0.5515	0.4963	0.102*
H1D	0.1862	0.6258	0.4525	0.102*
H1E	0.0335	0.5879	0.3765	0.102*
N2	0.3246 (3)	0.44734 (12)	0.7623 (3)	0.0416 (7)
C2	0.0341 (4)	0.61219 (17)	0.6213 (4)	0.0460 (8)
N3	0.3632 (3)	0.56324 (13)	0.7919 (4)	0.0497 (7)
C3	−0.0526 (4)	0.66983 (17)	0.6214 (4)	0.0498 (9)
H3B	−0.0593	0.6973	0.5285	0.060*
C4	−0.1290 (4)	0.68813 (16)	0.7523 (4)	0.0480 (9)
H4A	−0.1857	0.7272	0.7468	0.058*
N4	0.4792 (4)	0.26228 (15)	0.6373 (4)	0.0649 (9)
C5	−0.1216 (3)	0.64847 (14)	0.8928 (4)	0.0405 (8)
C6	−0.0318 (3)	0.59152 (14)	0.8984 (4)	0.0395 (8)
H6A	−0.0230	0.5645	0.9921	0.047*
C7	0.0441 (3)	0.57516 (15)	0.7653 (4)	0.0403 (8)
C8	0.2772 (4)	0.50942 (15)	0.7753 (4)	0.0412 (8)
C9	0.4799 (4)	0.43896 (15)	0.7646 (4)	0.0406 (8)
C10	0.5823 (4)	0.49200 (17)	0.7776 (5)	0.0522 (9)
H10A	0.6898	0.4863	0.7773	0.063*
C11	0.5179 (4)	0.55349 (17)	0.7909 (5)	0.0556 (10)
H11A	0.5845	0.5898	0.7995	0.067*
C12	0.5341 (4)	0.37050 (15)	0.7517 (4)	0.0411 (8)
C13	0.4408 (4)	0.32551 (17)	0.6553 (5)	0.0526 (9)
H13A	0.3447	0.3400	0.5990	0.063*
C14	0.6177 (5)	0.24293 (19)	0.7200 (5)	0.0630 (11)
H14A	0.6476	0.1993	0.7104	0.076*
C15	0.7182 (5)	0.28438 (19)	0.8184 (5)	0.0619 (10)
H15A	0.8136	0.2687	0.8737	0.074*
C16	0.6774 (4)	0.34860 (18)	0.8347 (5)	0.0531 (9)
H16A	0.7445	0.3772	0.9004	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0398 (13)	0.0379 (12)	0.0783 (18)	−0.0001 (10)	0.0208 (11)	−0.0024 (11)
N1	0.066 (2)	0.0395 (16)	0.0609 (19)	0.0056 (14)	0.0227 (16)	−0.0018 (14)
C1	0.069 (3)	0.083 (3)	0.055 (2)	−0.006 (2)	0.019 (2)	0.000 (2)
N2	0.0410 (16)	0.0358 (14)	0.0497 (17)	−0.0021 (12)	0.0123 (12)	−0.0049 (12)
C2	0.0391 (18)	0.053 (2)	0.046 (2)	−0.0059 (16)	0.0087 (15)	0.0002 (16)
N3	0.0463 (17)	0.0412 (16)	0.0619 (19)	−0.0045 (13)	0.0084 (14)	−0.0053 (14)
C3	0.0455 (19)	0.052 (2)	0.051 (2)	−0.0074 (17)	0.0033 (16)	0.0154 (17)
C4	0.0435 (19)	0.0358 (18)	0.065 (2)	0.0023 (15)	0.0084 (17)	0.0086 (16)
N4	0.062 (2)	0.0462 (18)	0.090 (3)	−0.0014 (16)	0.0242 (18)	−0.0145 (17)
C5	0.0369 (17)	0.0353 (17)	0.050 (2)	−0.0061 (14)	0.0070 (14)	−0.0037 (15)
C6	0.0381 (17)	0.0328 (17)	0.048 (2)	−0.0047 (14)	0.0077 (15)	0.0052 (14)
C7	0.0340 (17)	0.0313 (16)	0.057 (2)	−0.0029 (13)	0.0106 (15)	−0.0013 (15)
C8	0.0406 (18)	0.0393 (18)	0.0453 (19)	−0.0014 (15)	0.0116 (14)	−0.0034 (15)
C9	0.0393 (18)	0.0424 (18)	0.0414 (18)	−0.0007 (14)	0.0101 (14)	−0.0043 (14)
C10	0.0387 (18)	0.048 (2)	0.071 (3)	−0.0050 (16)	0.0125 (17)	−0.0057 (18)
C11	0.045 (2)	0.045 (2)	0.076 (3)	−0.0100 (16)	0.0074 (18)	−0.0075 (18)
C12	0.0387 (18)	0.0407 (18)	0.0462 (19)	−0.0019 (14)	0.0143 (15)	−0.0032 (15)
C13	0.0426 (19)	0.047 (2)	0.070 (2)	−0.0003 (16)	0.0138 (17)	−0.0118 (18)
C14	0.070 (3)	0.044 (2)	0.081 (3)	0.010 (2)	0.033 (2)	0.000 (2)
C15	0.058 (2)	0.057 (2)	0.072 (3)	0.018 (2)	0.012 (2)	0.006 (2)
C16	0.050 (2)	0.054 (2)	0.056 (2)	0.0034 (17)	0.0087 (17)	−0.0060 (17)

Geometric parameters (Å, º) top

O—C8	1.357 (4)	N4—C14	1.336 (5)
O—C7	1.413 (4)	N4—C13	1.342 (4)
N1—C5	1.387 (4)	C5—C6	1.389 (4)
N1—H1A	0.8600	C6—C7	1.376 (4)
N1—H1B	0.8600	C6—H6A	0.9300
C1—C2	1.506 (5)	C9—C10	1.387 (4)
C1—H1C	0.9600	C9—C12	1.478 (4)
C1—H1D	0.9600	C10—C11	1.379 (5)
C1—H1E	0.9600	C10—H10A	0.9300
N2—C8	1.337 (4)	C11—H11A	0.9300
N2—C9	1.340 (4)	C12—C13	1.381 (5)
C2—C7	1.379 (5)	C12—C16	1.386 (5)
C2—C3	1.389 (5)	C13—H13A	0.9300
N3—C8	1.317 (4)	C14—C15	1.375 (5)
N3—C11	1.344 (4)	C14—H14A	0.9300
C3—C4	1.374 (5)	C15—C16	1.365 (5)
C3—H3B	0.9300	C15—H15A	0.9300
C4—C5	1.387 (4)	C16—H16A	0.9300
C4—H4A	0.9300

C8—O—C7	119.9 (2)	C6—C7—O	115.6 (3)
C5—N1—H1A	120.0	C2—C7—O	120.8 (3)
C5—N1—H1B	120.0	N3—C8—N2	128.5 (3)
H1A—N1—H1B	120.0	N3—C8—O	119.8 (3)
C2—C1—H1C	109.5	N2—C8—O	111.7 (3)
C2—C1—H1D	109.5	N2—C9—C10	121.3 (3)
H1C—C1—H1D	109.5	N2—C9—C12	116.2 (3)
C2—C1—H1E	109.5	C10—C9—C12	122.5 (3)
H1C—C1—H1E	109.5	C11—C10—C9	117.1 (3)
H1D—C1—H1E	109.5	C11—C10—H10A	121.4
C8—N2—C9	115.6 (3)	C9—C10—H10A	121.4
C7—C2—C3	115.5 (3)	N3—C11—C10	122.8 (3)
C7—C2—C1	123.0 (3)	N3—C11—H11A	118.6
C3—C2—C1	121.5 (3)	C10—C11—H11A	118.6
C8—N3—C11	114.6 (3)	C13—C12—C16	117.5 (3)
C4—C3—C2	123.0 (3)	C13—C12—C9	120.1 (3)
C4—C3—H3B	118.5	C16—C12—C9	122.4 (3)
C2—C3—H3B	118.5	N4—C13—C12	124.5 (3)
C3—C4—C5	120.1 (3)	N4—C13—H13A	117.8
C3—C4—H4A	120.0	C12—C13—H13A	117.8
C5—C4—H4A	120.0	N4—C14—C15	123.1 (3)
C14—N4—C13	116.3 (3)	N4—C14—H14A	118.4
C4—C5—N1	120.1 (3)	C15—C14—H14A	118.4
C4—C5—C6	118.2 (3)	C16—C15—C14	119.7 (4)
N1—C5—C6	121.7 (3)	C16—C15—H15A	120.2
C7—C6—C5	119.9 (3)	C14—C15—H15A	120.2
C7—C6—H6A	120.0	C15—C16—C12	118.9 (4)
C5—C6—H6A	120.0	C15—C16—H16A	120.5
C6—C7—C2	123.2 (3)	C12—C16—H16A	120.5

C7—C2—C3—C4	−2.5 (5)	C7—O—C8—N2	−171.2 (3)
C1—C2—C3—C4	178.0 (3)	C8—N2—C9—C10	−0.8 (5)
C2—C3—C4—C5	0.0 (5)	C8—N2—C9—C12	179.5 (3)
C3—C4—C5—N1	−179.2 (3)	N2—C9—C10—C11	1.1 (5)
C3—C4—C5—C6	1.9 (5)	C12—C9—C10—C11	−179.2 (3)
C4—C5—C6—C7	−1.3 (4)	C8—N3—C11—C10	−1.5 (5)
N1—C5—C6—C7	179.8 (3)	C9—C10—C11—N3	0.1 (6)
C5—C6—C7—C2	−1.2 (5)	N2—C9—C12—C13	34.5 (4)
C5—C6—C7—O	−174.0 (3)	C10—C9—C12—C13	−145.2 (3)
C3—C2—C7—C6	3.1 (5)	N2—C9—C12—C16	−145.1 (3)
C1—C2—C7—C6	−177.4 (3)	C10—C9—C12—C16	35.2 (5)
C3—C2—C7—O	175.4 (3)	C14—N4—C13—C12	0.1 (5)
C1—C2—C7—O	−5.0 (5)	C16—C12—C13—N4	0.2 (5)
C8—O—C7—C6	−119.7 (3)	C9—C12—C13—N4	−179.3 (3)
C8—O—C7—C2	67.4 (4)	C13—N4—C14—C15	−0.3 (6)
C11—N3—C8—N2	1.9 (5)	N4—C14—C15—C16	0.0 (6)
C11—N3—C8—O	179.5 (3)	C14—C15—C16—C12	0.4 (6)
C9—N2—C8—N3	−0.8 (5)	C13—C12—C16—C15	−0.5 (5)
C9—N2—C8—O	−178.5 (3)	C9—C12—C16—C15	179.1 (3)
C7—O—C8—N3	10.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.86	2.47	3.214 (4)	145
N1—H1B···N2ⁱⁱ	0.86	2.43	3.166 (4)	144

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₄O
M_r	278.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.5800 (17), 20.360 (4), 8.0780 (16)
β (°)	98.29 (3)
V (Å³)	1396.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.983, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2698, 2526, 1587
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.170, 1.01
No. of reflections	2526
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.30

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.8600	2.4700	3.214 (4)	145.00
N1—H1B···N2ⁱⁱ	0.8600	2.4300	3.166 (4)	144.00

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, −y+1, −z+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 (1989). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
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