(Z)-3-(4-Hydroxy­phenethyl­amino)-2-methyl-1-phenyl­prop-2-en-1-one

The title compound, C₁₈H₁₉NO₂, was synthesized by the substituted one-carbon unit transfer reaction of 4-(2-amino­ethyl)phenol with an imidazolidine derivative. In the crystal structure, the mol­ecules are packed together by inter­molecular O—H...O and N—H...O hydrogen bonds into layers. The different layers are stacked together by π–π inter­actions with a centroid-to-centroid distance of 5.836 Å between 4-hydroxy­phene groups in adjacent layers.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.074
• wR factor = 0.157
• Data-to-parameter ratio = 13.8

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S1. Comment

Secondary enamines have attracted a great deal of attention in recent years because of their range of applications (Duthaler, 2003; Stanovnik & Svete, 2004; Elassar & Ei-Khair, 2003). Moreover, functionalize secondary enamine derives may enable chemical and biological studies on these derivatives, which will be used in pharmaceutical reseach. Here we carried out the synthesis of secondary enamine derivative according to early papers (Fan et al., 2005; Li et al., 2004).

The molecular geometry of compound (I) including C=N is an E configuration (Fig. 1). The bond distance of C10—C12 and C12—C13 are shorter than normal case. These bond distances suggest delocalization of π electrons, and there is a great interaction between π bond of the C9—C10 and N lone-pair electrons.

The O—H···O and N—H···O hydrogen bonds were responsible for packing of molecules (see Fig. 2). two parallel benzen groups attached to carbonyl located in one unit which was formed by the intermolecular hydrogen bonds O1- H1— O2. The units are linked together by intermolecular hydrogen bonds N1- H1A—O2.

In the crystal sructure,the molecules are linked together into layers by a combination of O1- H1— O2 and N1- H1A—O2 hydrogen bonds. The different layers were stacked together by π -π interactions between 4-hydroxyphene groups in adjacent layers (see Fig.3).

Related literature

For related literature, see: Duthaler (2003); Elassar & Ei-Khair (2003); Fan et al. (2005); Flack & Bernardinelli (1999); Li et al. (2004); Stanovnik & Svete (2004).

S2. Experimental

Into a 50 ml 3-necked roundbottom flask, was placed a solution of 2-(3,4-dimethyl-1-tosylimidazolidin-2-yl)-1-phenylpropan-1-one (0.387 g, 1 mmol) in anhydrous acetonitrile (10 ml). To this was added 4-(2-aminoethyl)phenol (0.137 g, 1 mmol). The resulting solution was allowed to react, with stirring, for 2 h while the temperature was maintained at reflux in a bath of oil. The reaction progress was monitored by TLC (EtOAc/PE = 1:1). The residue was purified by eluting through a column with a 1:10 EA/PE solvent system This resulted in 0.253 g (90%) of (Z)-3-(4-hydroxyphenethylamino)-2-methyl-1-phenylprop-2-en-1-one as a white solid. Crystals of the compound were obtained by slow evaporation of an ethanol solution. m.p.=189–190oC.1H-NMR (300 MHz, ? p.p.m., DMSO-d6): 1.68 (s, 3H), 2.68 (t, 2H), 3.22 (m, 2H), 6.59–6.71 (m, 4H), 6.93–7.05 (m, 3H), 7.30–7.35 (m, 3H), 9.24 (br, 1H),10.86 (br, 1H).

S3. Refinement

H atoms bonded to C atoms were treated as riding atoms, with C–H = 0.93–0.97 Å, their U_iso values were set at 1.2 U_eq (C atom); The amine H atom were refined freely in isotropic approximation; The H atom bonded to N3 was permitted to ride at the distance deduced from difference maps (0.88 A Ê), with U_iso(H) = 1.2Ueq(N).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1999).

Figures

	Fig. 1. The structure of the compound (I) with the atom-numbering scheme, showing 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitary radii
	Fig. 2. Packing diagram of (I), showing the hydrogen bond interactions (dashed lines) and hydrogen bonds are indicated by dashed lines
	Fig. 3. A view along the b axis showing the stacking of the layers. with small black spheres representing H atoms.

(Z)-3-(4-Hydroxyphenethylamino)-2-methyl-1-phenylprop-2-en-1-one

Crystal data

C18H19NO2	F(000) = 604
Mr = 282.35	Dx = 1.248 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2yn	Cell parameters from 1527 reflections
a = 9.8035 (17) Å	θ = 2.5–21.9°
b = 9.4636 (16) Å	µ = 0.08 mm^−1
c = 16.457 (3) Å	T = 294 K
β = 100.064 (2)°	Block, colorless
V = 1503.3 (4) Å^3	0.30 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker SMART CCD area detector diffractometer	2085 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
φ and ω scans	h = −11→11
7096 measured reflections	k = −11→9
2657 independent reflections	l = −11→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 1.2494P] where P = (Fo^2 + 2Fc^2)/3
2657 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−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 (Ų)

	x	y	z	Uiso*/Ueq
N1	1.0477 (2)	−0.0208 (3)	0.30663 (14)	0.0409 (6)
H1A	1.1270	−0.0581	0.3253	0.061*
O1	0.6077 (2)	−0.1801 (3)	−0.01827 (14)	0.0591 (7)
H1	0.6602	−0.2100	−0.0480	0.089*
O2	1.2241 (2)	0.2788 (2)	0.12128 (13)	0.0486 (6)
C1	0.6726 (3)	−0.1854 (3)	0.06243 (19)	0.0431 (8)
C2	0.8010 (3)	−0.2461 (3)	0.0859 (2)	0.0440 (8)
H2	0.8478	−0.2840	0.0464	0.053*
C3	0.8598 (3)	−0.2502 (3)	0.1681 (2)	0.0436 (8)
H3	0.9459	−0.2931	0.1832	0.052*
C4	0.7964 (3)	−0.1934 (3)	0.22892 (19)	0.0388 (7)
C5	0.6678 (3)	−0.1302 (3)	0.2033 (2)	0.0481 (8)
H5	0.6217	−0.0903	0.2425	0.058*
C6	0.6073 (3)	−0.1253 (4)	0.1214 (2)	0.0498 (9)
H6	0.5220	−0.0813	0.1058	0.060*
C7	0.8627 (3)	−0.1961 (3)	0.31844 (19)	0.0447 (8)
H7A	0.9313	−0.2709	0.3271	0.054*
H7B	0.7925	−0.2175	0.3515	0.054*
C8	0.9321 (3)	−0.0567 (3)	0.34762 (18)	0.0425 (8)
H8A	0.8637	0.0183	0.3379	0.051*
H8B	0.9653	−0.0621	0.4066	0.051*
C9	1.0387 (3)	0.0649 (3)	0.24285 (17)	0.0366 (7)
H9	0.9512	0.0994	0.2209	0.044*
C10	1.1465 (3)	0.1080 (3)	0.20575 (18)	0.0396 (7)
C11	1.2915 (3)	0.0590 (4)	0.2396 (2)	0.0673 (11)
H11A	1.3160	0.0869	0.2963	0.101*
H11B	1.3550	0.1008	0.2083	0.101*
H11C	1.2960	−0.0421	0.2356	0.101*
C12	1.1256 (3)	0.2083 (3)	0.14051 (18)	0.0382 (7)
C13	0.9861 (3)	0.2319 (3)	0.08866 (18)	0.0345 (7)
C14	0.9037 (3)	0.1187 (3)	0.05629 (19)	0.0449 (8)
H14	0.9292	0.0272	0.0730	0.054*
C15	0.7844 (3)	0.1412 (3)	−0.0005 (2)	0.0544 (9)
H15	0.7305	0.0646	−0.0221	0.065*
C16	0.7448 (4)	0.2756 (4)	−0.0251 (2)	0.0555 (9)
H16	0.6647	0.2901	−0.0637	0.067*
C17	0.8237 (3)	0.3888 (3)	0.0073 (2)	0.0524 (9)
H17	0.7963	0.4803	−0.0085	0.063*
C18	0.9440 (3)	0.3665 (3)	0.0634 (2)	0.0452 (8)
H18	0.9976	0.4435	0.0846	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0348 (14)	0.0486 (15)	0.0379 (15)	0.0017 (11)	0.0024 (11)	0.0086 (12)
O1	0.0525 (14)	0.0759 (17)	0.0436 (14)	−0.0026 (12)	−0.0062 (11)	−0.0095 (13)
O2	0.0433 (13)	0.0539 (13)	0.0481 (13)	−0.0179 (10)	0.0070 (10)	−0.0008 (11)
C1	0.0408 (18)	0.0431 (18)	0.0423 (19)	−0.0109 (14)	−0.0013 (15)	−0.0055 (15)
C2	0.0480 (19)	0.0398 (17)	0.0452 (19)	−0.0014 (14)	0.0115 (16)	−0.0058 (15)
C3	0.0382 (17)	0.0417 (18)	0.050 (2)	0.0064 (13)	0.0050 (15)	0.0069 (15)
C4	0.0362 (17)	0.0376 (16)	0.0436 (18)	−0.0046 (13)	0.0091 (14)	0.0001 (14)
C5	0.0380 (18)	0.058 (2)	0.050 (2)	−0.0032 (15)	0.0128 (15)	−0.0105 (17)
C6	0.0320 (17)	0.059 (2)	0.055 (2)	0.0067 (15)	−0.0010 (15)	−0.0119 (18)
C7	0.0425 (18)	0.0486 (19)	0.0440 (19)	−0.0009 (14)	0.0106 (15)	0.0131 (15)
C8	0.0435 (18)	0.0498 (18)	0.0344 (17)	−0.0014 (14)	0.0074 (14)	0.0032 (15)
C9	0.0357 (16)	0.0376 (16)	0.0328 (16)	−0.0007 (13)	−0.0041 (13)	−0.0014 (14)
C10	0.0321 (16)	0.0445 (18)	0.0413 (18)	−0.0070 (13)	0.0042 (14)	0.0008 (15)
C11	0.0360 (19)	0.089 (3)	0.075 (3)	−0.0027 (18)	0.0047 (18)	0.028 (2)
C12	0.0409 (17)	0.0366 (16)	0.0378 (17)	−0.0068 (14)	0.0089 (14)	−0.0049 (14)
C13	0.0398 (16)	0.0320 (15)	0.0327 (16)	−0.0077 (12)	0.0089 (13)	0.0007 (13)
C14	0.0534 (19)	0.0307 (16)	0.0477 (19)	−0.0045 (14)	0.0009 (16)	0.0049 (14)
C15	0.053 (2)	0.0450 (19)	0.057 (2)	−0.0135 (16)	−0.0116 (17)	0.0025 (17)
C16	0.053 (2)	0.054 (2)	0.054 (2)	−0.0042 (16)	−0.0061 (17)	0.0120 (17)
C17	0.055 (2)	0.0383 (18)	0.061 (2)	0.0016 (15)	0.0029 (18)	0.0160 (16)
C18	0.0485 (19)	0.0331 (16)	0.053 (2)	−0.0068 (14)	0.0044 (16)	0.0008 (15)

Geometric parameters (Å, º)

N1—C9	1.317 (3)	C8—H8B	0.9700
N1—C8	1.456 (4)	C9—C10	1.371 (4)
N1—H1A	0.8600	C9—H9	0.9300
O1—C1	1.370 (4)	C10—C12	1.421 (4)
O1—H1	0.8200	C10—C11	1.507 (4)
O2—C12	1.259 (3)	C11—H11A	0.9600
C1—C6	1.375 (4)	C11—H11B	0.9600
C1—C2	1.376 (4)	C11—H11C	0.9600
C2—C3	1.376 (4)	C12—C13	1.497 (4)
C2—H2	0.9300	C13—C18	1.380 (4)
C3—C4	1.376 (4)	C13—C14	1.390 (4)
C3—H3	0.9300	C14—C15	1.380 (4)
C4—C5	1.393 (4)	C14—H14	0.9300
C4—C7	1.503 (4)	C15—C16	1.370 (4)
C5—C6	1.375 (4)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.374 (4)
C6—H6	0.9300	C16—H16	0.9300
C7—C8	1.523 (4)	C17—C18	1.381 (4)
C7—H7A	0.9700	C17—H17	0.9300
C7—H7B	0.9700	C18—H18	0.9300
C8—H8A	0.9700
C9—N1—C8	124.3 (2)	N1—C9—C10	126.1 (3)
C9—N1—H1A	117.8	N1—C9—H9	117.0
C8—N1—H1A	117.8	C10—C9—H9	117.0
C1—O1—H1	109.5	C9—C10—C12	121.0 (3)
O1—C1—C6	118.3 (3)	C9—C10—C11	119.7 (3)
O1—C1—C2	122.3 (3)	C12—C10—C11	119.1 (3)
C6—C1—C2	119.4 (3)	C10—C11—H11A	109.5
C3—C2—C1	119.6 (3)	C10—C11—H11B	109.5
C3—C2—H2	120.2	H11A—C11—H11B	109.5
C1—C2—H2	120.2	C10—C11—H11C	109.5
C2—C3—C4	122.6 (3)	H11A—C11—H11C	109.5
C2—C3—H3	118.7	H11B—C11—H11C	109.5
C4—C3—H3	118.7	O2—C12—C10	121.9 (3)
C3—C4—C5	116.6 (3)	O2—C12—C13	116.2 (3)
C3—C4—C7	122.2 (3)	C10—C12—C13	121.8 (3)
C5—C4—C7	121.2 (3)	C18—C13—C14	118.2 (3)
C6—C5—C4	121.6 (3)	C18—C13—C12	120.3 (3)
C6—C5—H5	119.2	C14—C13—C12	121.0 (3)
C4—C5—H5	119.2	C15—C14—C13	120.5 (3)
C5—C6—C1	120.2 (3)	C15—C14—H14	119.7
C5—C6—H6	119.9	C13—C14—H14	119.7
C1—C6—H6	119.9	C16—C15—C14	120.4 (3)
C4—C7—C8	112.8 (2)	C16—C15—H15	119.8
C4—C7—H7A	109.0	C14—C15—H15	119.8
C8—C7—H7A	109.0	C15—C16—C17	119.9 (3)
C4—C7—H7B	109.0	C15—C16—H16	120.1
C8—C7—H7B	109.0	C17—C16—H16	120.1
H7A—C7—H7B	107.8	C16—C17—C18	119.8 (3)
N1—C8—C7	113.4 (3)	C16—C17—H17	120.1
N1—C8—H8A	108.9	C18—C17—H17	120.1
C7—C8—H8A	108.9	C13—C18—C17	121.2 (3)
N1—C8—H8B	108.9	C13—C18—H18	119.4
C7—C8—H8B	108.9	C17—C18—H18	119.4
H8A—C8—H8B	107.7
O1—C1—C2—C3	−178.9 (3)	C9—C10—C12—O2	159.6 (3)
C6—C1—C2—C3	2.3 (4)	C11—C10—C12—O2	−14.8 (5)
C1—C2—C3—C4	−1.2 (5)	C9—C10—C12—C13	−22.9 (4)
C2—C3—C4—C5	−0.1 (4)	C11—C10—C12—C13	162.8 (3)
C2—C3—C4—C7	−178.8 (3)	O2—C12—C13—C18	−40.9 (4)
C3—C4—C5—C6	0.2 (5)	C10—C12—C13—C18	141.4 (3)
C7—C4—C5—C6	179.0 (3)	O2—C12—C13—C14	131.0 (3)
C4—C5—C6—C1	0.9 (5)	C10—C12—C13—C14	−46.7 (4)
O1—C1—C6—C5	179.0 (3)	C18—C13—C14—C15	1.0 (5)
C2—C1—C6—C5	−2.2 (5)	C12—C13—C14—C15	−171.0 (3)
C3—C4—C7—C8	99.4 (3)	C13—C14—C15—C16	−0.6 (5)
C5—C4—C7—C8	−79.3 (4)	C14—C15—C16—C17	−0.5 (6)
C9—N1—C8—C7	97.2 (3)	C15—C16—C17—C18	1.2 (5)
C4—C7—C8—N1	−63.8 (3)	C14—C13—C18—C17	−0.3 (5)
C8—N1—C9—C10	175.8 (3)	C12—C13—C18—C17	171.8 (3)
N1—C9—C10—C12	−175.9 (3)	C16—C17—C18—C13	−0.8 (5)
N1—C9—C10—C11	−1.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.91	2.728 (3)	178
N1—H1A···O2^ii	0.86	2.20	3.014 (3)	158

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+5/2, y−1/2, −z+1/2.