Related literature

Acta Crystallogr Sect E Struct Rep Online

Acta Cryst. E

Acta Crystallographica Section E: Structure Reports Online

1600-5368

International Union of Crystallography

21580170

2979991

ci2973

10.1107/S1600536809051186

ACSEBH

S1600536809051186

Organic Papers

(Z)-3-(4-Methoxyanilino)-1-phenylbut-2-en-1-one

C₁₇H₁₇NO₂

Zhang

Li-Ping

a*Yang

Ming

aFang

Yun

aaSchool of Chemical and Materials Engineering, Jiangnan University, 1800 Lihu Road, Wuxi 214122, Jiangsu, People’s Republic of China

Correspondence e-mail: zlp609@qq.com

0112010

04122009

66Pt 1

e100100

o7o72011200927112009

2010

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

A full version of this article is available from Crystallography Journals Online.

In the title compound, C₁₇H₁₇NO₂, the dihedral angle between the two benzene rings is 6.9 (1)°. The methoxy group is twisted slightly away from the aniline ring [C—O—C—C = 12.2 (3)°]. An intramolecular N—H⋯O hydrogen bond generating an S(6) ring is observed. The crystal packing is stabilized by weak C—H⋯O and C—H⋯π interactions, forming a two-dimensional network.

Related literature

For the biological activity of β-enamino ketones, see: Azzaro et al. (1981 ▶); Dannhardt et al. (1998 ▶); Boger et al. (1989 ▶); Wang et al. (1982 ▶). For the preparation of β-enamino ketones, see: Greenhill (1977 ▶); Elassar & El-Khair (2003 ▶); Zhang et al. (2006 ▶).

Experimental<sec id="sec2.1.1"><title>Crystal data

C₁₇H₁₇NO₂

M _r = 267.32

Monoclinic,

a = 6.435 (2) Å

b = 7.287 (3) Å

c = 30.919 (12) Å

β = 94.954 (6)°

V = 1444.5 (9) Å³

Z = 4

Mo Kα radiation

μ = 0.08 mm⁻¹

T = 294 K

0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.739, T _max = 1.000

7729 measured reflections

2931 independent reflections

1900 reflections with I > 2σ(I)

R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.046

wR(F ²) = 0.135

S = 1.00

2931 reflections

184 parameters

H-atom parameters constrained

Δρ_max = 0.18 e Å⁻³

Δρ_min = −0.17 e Å⁻³

Data collection: <italic>SMART</italic> (Bruker, 1998<xref ref-type="bibr" rid="bb3"> ▶</xref>); cell refinement: <italic>SAINT</italic> (Bruker, 1999<xref ref-type="bibr" rid="bb4"> ▶</xref>); data reduction: <italic>SAINT</italic>; program(s) used to solve structure: <italic>SHELXS97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb9"> ▶</xref>); program(s) used to refine structure: <italic>SHELXL97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb9"> ▶</xref>); molecular graphics: <italic>SHELXTL</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb9"> ▶</xref>); software used to prepare material for publication: <italic>SHELXTL</italic>.</sec></sec><sec sec-type="supplementary-material"><title>Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051186/ci2973sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051186/ci2973Isup2.hkl

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

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2973).

This work was supported financially by Jiangnan University.

supplementary crystallographic information Comment

β-enamino ketones have attracted considerable interest, because they are versatile intermediates for the synthesis of natural therapeutic and biologically active analogues including anticonvulsant (Azzaro et al., 1981), anti-inflammatory (Dannhardt et al., 1998) and antitumor agents (Boger et al., 1989), as well as quinolone antibacterials (Wang et al., 1982). It is therefore not surprising that many synthetic methods have been developed for the preparation of these compounds (Greenhill et al., 1977; Elassar et al., 2003). During the development of new environmental friendly methodologies (Zhang et al., 2006) for the preparation of β-enamino ketones, we synthesized the title compound (Fig.1) and its crystal structure is reported here.

In the title compound, the dihedral angle between the two benzene rings is 6.9 (1)%. The methoxy group is slightly twisted away from the aniline ring, with a C7—O1—C4—C3 torsion angle of 12.2 (3)°. The C10—C11 bond length [1.415 (2) Å] is shorter than the C11—C12 bond length [1.500 (2) Å], and the N1—C9 bond length [1.333 (2) Å] is markedly shorter than the N1—C1 [1.419 (2) Å] bond length, indicating a strong electron delocalization. An intramolecular N1—H1···O2 hydrogen bond observed.

The crystal packing is stabilized by weak C—H···O and C—H···π interactions. Intermolecular C8—H8B···O2 hydrogen bonds link the molecules into a C(6) chain propagating along the a axis (Fig.2). In addition, the crystal packing is stabilized by C—H···π interactions; these interactions link the chains along the b axis, forming a two-dimensional network (Fig.2).

Experimental

A mixture of 1-phenylbutane-1,3-dione (5 mmol), 4-methoxybenzenamine (5 mmol) and InBr₃ (0.05 mmol) was stirred at room temperature for 1 h. After completion of the reaction, the reaction mixture was diluted with H₂O (10 ml) and extracted with EtOAc (210 ml). The combined organic layers were dried, concentrated, purified by column chromatography on SiO₂ with ethyl acetate-cyclohexane (2:8), to obatin a pale yellow solid, with a yield of 78% (m. p. 84–85° C); IR (neat):ν 2979, 2870,1608, 1576, 1504, 1473, 1432,1372, 820, 744 cm^-1; ¹H NMR(CDCl₃, 300 MHz): δ 2.06(s, 3H), 3.80(s, 3H), 5.86(s, 1H), 6.88(d, 2H,Ar—H), 7.09(d, 2H,Ar—H), 7.42–7.45(m, 3H,Ph), 7.89–7.92 (m, 2H, Ph), 12.92 (br s, 1H, NH). ¹³C NMR(CDCl₃, 75 MHz): δ 20.2, 63.7, 93.5, 114.8, 126.5, 127.0, 128.2, 130.7, 131.3, 140.1, 157.2, 163.1, 188.3. ESI-MS: 268(M+1)⁺. Analysis calculated for C₁₇H₁₇NO₂: C 76.38, H 6.41, N 5.24; found: C 76.53, H 6.52, N 5.32. Single crystals suitable for X-ray diffraction study were obtained from ethyl acetate-cyclohexane by slow evaporation at room temperature.

FiguresFig. 1.

The molecular structure of the title compound, showing 30% probability displacement ellipsoids. The dashed line indicates a hydrogen bond.

Fig. 2.

The crystal packing of the title compound, showing C—H···O hydrogen-bonded (dashed lines) chains along the a axis.

Crystal data

C₁₇H₁₇NO₂	F(000) = 568
M_r = 267.32	D_x = 1.229 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2333 reflections
a = 6.435 (2) Å	θ = 2.6–26.3°
b = 7.287 (3) Å	µ = 0.08 mm⁻¹
c = 30.919 (12) Å	T = 294 K
β = 94.954 (6)°	Block, yellow
V = 1444.5 (9) Å³	0.24 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2931 independent reflections
Radiation source: fine-focus sealed tube	1900 reflections with I > 2σ(I)
graphite	R_int = 0.036
φ and ω scans	θ_max = 26.4°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→8
T_min = 0.739, T_max = 1.000	k = −9→7
7729 measured reflections	l = −34→38

Refinement

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0645P)² + 0.2627P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2931 reflections	Δρ_max = 0.18 e Å⁻³
184 parameters	Δρ_min = −0.17 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: 0.035 (3)

Special details

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)

	x	y	z	U_iso*/U_eq
O1	0.0332 (2)	0.1669 (2)	0.45901 (4)	0.0621 (4)
O2	−0.17087 (19)	0.1729 (2)	0.20705 (4)	0.0552 (4)
N1	0.0723 (2)	0.1693 (2)	0.27987 (4)	0.0417 (4)
H1	−0.0489	0.1722	0.2658	0.050*
C1	0.0705 (2)	0.1739 (2)	0.32573 (5)	0.0364 (4)
C2	−0.0759 (3)	0.2824 (3)	0.34338 (5)	0.0412 (4)
H2	−0.1639	0.3558	0.3253	0.049*
C3	−0.0940 (3)	0.2835 (3)	0.38775 (5)	0.0445 (5)
H3	−0.1947	0.3560	0.3992	0.053*
C4	0.0378 (3)	0.1768 (2)	0.41473 (5)	0.0423 (4)
C5	0.1869 (3)	0.0706 (3)	0.39734 (6)	0.0515 (5)
H5	0.2780	0.0005	0.4156	0.062*
C6	0.2022 (3)	0.0673 (3)	0.35319 (6)	0.0480 (5)
H6	0.3015	−0.0069	0.3418	0.058*
C7	−0.1412 (4)	0.2438 (4)	0.47712 (6)	0.0798 (8)
H7A	−0.1385	0.3749	0.4740	0.120*
H7B	−0.1366	0.2126	0.5074	0.120*
H7C	−0.2670	0.1963	0.4623	0.120*
C8	0.4516 (3)	0.1682 (3)	0.27522 (6)	0.0504 (5)
H8A	0.4579	0.2429	0.3009	0.076*
H8B	0.5399	0.2199	0.2549	0.076*
H8C	0.4981	0.0463	0.2828	0.076*
C9	0.2316 (3)	0.1612 (2)	0.25509 (5)	0.0384 (4)
C10	0.1947 (3)	0.1546 (2)	0.21040 (5)	0.0397 (4)
H10	0.3087	0.1449	0.1940	0.048*
C11	−0.0069 (3)	0.1616 (2)	0.18819 (5)	0.0386 (4)
C12	−0.0272 (3)	0.1643 (2)	0.13949 (5)	0.0390 (4)
C13	0.1114 (3)	0.0745 (3)	0.11502 (5)	0.0485 (5)
H13	0.2218	0.0086	0.1288	0.058*
C14	0.0869 (3)	0.0820 (3)	0.07020 (6)	0.0592 (6)
H14	0.1797	0.0195	0.0540	0.071*
C15	−0.0728 (4)	0.1807 (3)	0.04946 (6)	0.0612 (6)
H15	−0.0872	0.1869	0.0193	0.073*
C16	−0.2117 (4)	0.2703 (3)	0.07320 (6)	0.0621 (6)
H16	−0.3203	0.3375	0.0591	0.075*
C17	−0.1908 (3)	0.2612 (3)	0.11809 (6)	0.0525 (5)
H17	−0.2871	0.3205	0.1340	0.063*

Atomic displacement parameters (Å2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0685 (10)	0.0814 (11)	0.0370 (7)	0.0231 (8)	0.0080 (6)	0.0056 (7)
O2	0.0377 (7)	0.0836 (11)	0.0449 (7)	−0.0037 (7)	0.0074 (6)	−0.0087 (7)
N1	0.0333 (8)	0.0548 (10)	0.0370 (8)	−0.0018 (7)	0.0037 (6)	−0.0034 (7)
C1	0.0366 (9)	0.0376 (10)	0.0348 (9)	−0.0016 (7)	0.0027 (7)	−0.0008 (7)
C2	0.0355 (9)	0.0476 (11)	0.0399 (10)	0.0068 (8)	−0.0001 (7)	0.0040 (8)
C3	0.0426 (10)	0.0488 (12)	0.0429 (10)	0.0107 (8)	0.0082 (8)	−0.0013 (8)
C4	0.0476 (10)	0.0462 (11)	0.0329 (9)	0.0030 (8)	0.0031 (8)	0.0010 (8)
C5	0.0565 (12)	0.0516 (12)	0.0463 (11)	0.0195 (10)	0.0038 (9)	0.0093 (9)
C6	0.0557 (11)	0.0438 (11)	0.0456 (11)	0.0178 (9)	0.0100 (8)	0.0023 (9)
C7	0.0960 (18)	0.102 (2)	0.0442 (12)	0.0378 (15)	0.0206 (12)	0.0024 (12)
C8	0.0375 (10)	0.0637 (13)	0.0498 (11)	0.0002 (9)	0.0039 (8)	0.0037 (9)
C9	0.0368 (9)	0.0355 (10)	0.0434 (10)	−0.0023 (7)	0.0066 (7)	0.0012 (8)
C10	0.0372 (9)	0.0442 (11)	0.0388 (9)	−0.0009 (8)	0.0098 (7)	0.0003 (8)
C11	0.0404 (10)	0.0363 (10)	0.0398 (9)	−0.0036 (8)	0.0082 (8)	−0.0024 (8)
C12	0.0424 (10)	0.0361 (10)	0.0384 (9)	−0.0062 (8)	0.0023 (7)	−0.0024 (8)
C13	0.0552 (12)	0.0484 (12)	0.0425 (11)	0.0028 (9)	0.0071 (8)	−0.0012 (9)
C14	0.0729 (14)	0.0622 (14)	0.0439 (11)	−0.0019 (11)	0.0137 (10)	−0.0078 (10)
C15	0.0862 (16)	0.0605 (14)	0.0358 (10)	−0.0136 (12)	−0.0008 (10)	−0.0006 (10)
C16	0.0730 (14)	0.0571 (14)	0.0526 (12)	0.0022 (11)	−0.0148 (10)	0.0031 (10)
C17	0.0555 (12)	0.0505 (12)	0.0505 (12)	0.0040 (10)	−0.0016 (9)	−0.0073 (10)

Geometric parameters (Å, °)

O1—C4	1.374 (2)	C8—C9	1.497 (2)
O1—C7	1.413 (2)	C8—H8A	0.96
O2—C11	1.251 (2)	C8—H8B	0.96
N1—C9	1.333 (2)	C8—H8C	0.96
N1—C1	1.419 (2)	C9—C10	1.383 (2)
N1—H1	0.86	C10—C11	1.415 (2)
C1—C2	1.378 (2)	C10—H10	0.93
C1—C6	1.385 (2)	C11—C12	1.500 (2)
C2—C3	1.387 (2)	C12—C13	1.383 (2)
C2—H2	0.93	C12—C17	1.387 (3)
C3—C4	1.378 (2)	C13—C14	1.382 (2)
C3—H3	0.93	C13—H13	0.93
C4—C5	1.378 (2)	C14—C15	1.368 (3)
C5—C6	1.377 (2)	C14—H14	0.93
C5—H5	0.93	C15—C16	1.370 (3)
C6—H6	0.93	C15—H15	0.93
C7—H7A	0.96	C16—C17	1.385 (3)
C7—H7B	0.96	C16—H16	0.93
C7—H7C	0.96	C17—H17	0.93

C4—O1—C7	117.43 (15)	C9—C8—H8C	109.5
C9—N1—C1	130.43 (15)	H8A—C8—H8C	109.5
C9—N1—H1	114.8	H8B—C8—H8C	109.5
C1—N1—H1	114.8	N1—C9—C10	120.13 (16)
C2—C1—C6	118.82 (15)	N1—C9—C8	120.40 (15)
C2—C1—N1	118.30 (15)	C10—C9—C8	119.40 (15)
C6—C1—N1	122.79 (15)	C9—C10—C11	123.68 (15)
C1—C2—C3	120.92 (16)	C9—C10—H10	118.2
C1—C2—H2	119.5	C11—C10—H10	118.2
C3—C2—H2	119.5	O2—C11—C10	123.41 (16)
C4—C3—C2	119.71 (16)	O2—C11—C12	117.59 (15)
C4—C3—H3	120.1	C10—C11—C12	118.94 (14)
C2—C3—H3	120.1	C13—C12—C17	118.60 (16)
O1—C4—C5	115.81 (15)	C13—C12—C11	122.58 (16)
O1—C4—C3	124.58 (16)	C17—C12—C11	118.82 (16)
C5—C4—C3	119.61 (16)	C14—C13—C12	120.45 (18)
C6—C5—C4	120.56 (17)	C14—C13—H13	119.8
C6—C5—H5	119.7	C12—C13—H13	119.8
C4—C5—H5	119.7	C15—C14—C13	120.44 (19)
C5—C6—C1	120.36 (17)	C15—C14—H14	119.8
C5—C6—H6	119.8	C13—C14—H14	119.8
C1—C6—H6	119.8	C14—C15—C16	119.87 (18)
O1—C7—H7A	109.5	C14—C15—H15	120.1
O1—C7—H7B	109.5	C16—C15—H15	120.1
H7A—C7—H7B	109.5	C15—C16—C17	120.2 (2)
O1—C7—H7C	109.5	C15—C16—H16	119.9
H7A—C7—H7C	109.5	C17—C16—H16	119.9
H7B—C7—H7C	109.5	C16—C17—C12	120.42 (18)
C9—C8—H8A	109.5	C16—C17—H17	119.8
C9—C8—H8B	109.5	C12—C17—H17	119.8
H8A—C8—H8B	109.5

C9—N1—C1—C2	142.48 (19)	N1—C9—C10—C11	2.1 (3)
C9—N1—C1—C6	−40.9 (3)	C8—C9—C10—C11	−175.06 (16)
C6—C1—C2—C3	−0.9 (3)	C9—C10—C11—O2	−0.6 (3)
N1—C1—C2—C3	175.86 (16)	C9—C10—C11—C12	176.46 (16)
C1—C2—C3—C4	0.9 (3)	O2—C11—C12—C13	−149.89 (18)
C7—O1—C4—C5	−167.8 (2)	C10—C11—C12—C13	32.8 (2)
C7—O1—C4—C3	12.2 (3)	O2—C11—C12—C17	30.3 (2)
C2—C3—C4—O1	−179.76 (17)	C10—C11—C12—C17	−146.95 (18)
C2—C3—C4—C5	0.3 (3)	C17—C12—C13—C14	0.2 (3)
O1—C4—C5—C6	178.64 (18)	C11—C12—C13—C14	−179.60 (17)
C3—C4—C5—C6	−1.4 (3)	C12—C13—C14—C15	1.0 (3)
C4—C5—C6—C1	1.4 (3)	C13—C14—C15—C16	−1.1 (3)
C2—C1—C6—C5	−0.2 (3)	C14—C15—C16—C17	0.0 (3)
N1—C1—C6—C5	−176.83 (17)	C15—C16—C17—C12	1.2 (3)
C1—N1—C9—C10	178.77 (16)	C13—C12—C17—C16	−1.3 (3)
C1—N1—C9—C8	−4.1 (3)	C11—C12—C17—C16	178.51 (17)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.91	2.629 (2)	139
C8—H8B···O2ⁱ	0.96	2.49	3.351 (3)	148
C3—H3···Cg2ⁱⁱ	0.93	2.84	3.712 (3)	156
C13—H13···Cg1ⁱⁱⁱ	0.93	2.82	3.619 (3)	145

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

References

Azzaro, M., Geribaldi, S. & Videau, B. (1981). Synthesis, pp. 880–881.

Boger, D. L., Ishizaki, T., Wysocki, J. R. J., Munk, S. A., Kitos, P. A. & Suntornwat, O. (1989). J. Am. Chem. Soc.111, 6461–6463.

Bruker (1998). SMART Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.

Dannhardt, G., Bauer, A. & Nowe, U. (1998). J. Prakt. Chem.340, 256–263.

Elassar, A.-Z. A. & El-Khair, A. A. (2003). Tetrahedron, 59, 8463–8480.

Greenhill, J. V. (1977). Chem. Soc. Rev.6, 277–294.

Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, Y. F., Izawa, T., Kobayashi, S. & Ohno, M. (1982). J. Am. Chem. Soc.104, 6465–6466.

Zhang, Z. H., Yin, L. & Wang, Y. M. (2006). Adv. Synth. Catal.348, 184–190.

Table 1Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.91	2.629 (2)	139
C8—H8B⋯O2ⁱ	0.96	2.49	3.351 (3)	148
C3—H3⋯Cg2ⁱⁱ	0.93	2.84	3.712 (3)	156
C13—H13⋯Cg1ⁱⁱⁱ	0.93	2.82	3.619 (3)	145

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of the C1–C6 and C12–C17 rings, respectively.