(Z)-Ethyl 3-(2,6-diisopropyl-anilino)but-2-enoate.

The title compound, C(18)H(27)NO(2), crystallizes as the enamine form with Z geometry. The β-enamino-ester fragment forms a dihedral angle of 87.5 (1)° with the isopropyl-phenyl frame. The structure exhibits an intra-molecular N-H⋯O hydrogen bond. In addition, in the crystal, mol-ecules are linked by a centrosymmetric inter-molecular N-H⋯O hydrogen bond.

Related literature

For methods used in the preparation of β-enamino­ketones and β-enamino­esters, see: Zhang & Yang (2009 ▶); Bartoli et al. (2004 ▶); Braibante et al. (2006 ▶). These compounds are used the preparation of key inter­mediates of pharmaceutical products (Michael et al., 1999 ▶), amino­acids (Palmieri & Cimmerelli, 1996 ▶), peptides and alkaloids (David et al., 1999 ▶). For our work on the synthesis of enamino­esters, see: Amézquita-Valencia et al. (2009 ▶).

Experimental

Crystal data

C18H27NO2

M = 289.41

Triclinic,

a = 8.4750 (17) Å

b = 8.8995 (18) Å

c = 11.956 (2) Å

α = 94.901 (3)°

β = 91.801 (3)°

γ = 101.255 (4)°

V = 880.1 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 298 K

0.29 × 0.21 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

7319 measured reflections

3233 independent reflections

1574 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.085

S = 0.84

3233 reflections

199 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.11 e Å−3

Δρmin = −0.10 e Å−3

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003260/gw2075sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003260/gw2075Isup2.hkl

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

C18H27NO2	Z = 2
Mr = 289.41	F(000) = 316
Triclinic, P1	Dx = 1.092 Mg m−3
Hall symbol: -P 1	Melting point: 326.3(2) K
a = 8.4750 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8995 (18) Å	Cell parameters from 1942 reflections
c = 11.956 (2) Å	θ = 2.5–24.1°
α = 94.901 (3)°	µ = 0.07 mm−1
β = 91.801 (3)°	T = 298 K
γ = 101.255 (4)°	Prism, colorless
V = 880.1 (3) Å3	0.29 × 0.21 × 0.05 mm

Bruker SMART APEX CCD area-detector diffractometer	1574 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
graphite	θmax = 25.4°, θmin = 1.7°
Detector resolution: 0.83 pixels mm-1	h = −10→10
ω scans	k = −10→10
7319 measured reflections	l = −14→14
3233 independent 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3
3233 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.11 e Å−3
1 restraint	Δρmin = −0.10 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
O1	0.40766 (16)	0.15127 (14)	0.48653 (10)	0.0730 (4)
O2	0.30098 (15)	0.36079 (13)	0.46776 (9)	0.0683 (4)
N1	0.49463 (18)	0.01679 (16)	0.28928 (11)	0.0554 (4)
H1	0.4882 (18)	0.0192 (18)	0.3638 (8)	0.066*
C1	0.3661 (2)	0.2415 (2)	0.42624 (15)	0.0556 (5)
C2	0.3774 (2)	0.23743 (19)	0.30792 (14)	0.0574 (5)
H2	0.3404	0.3129	0.2713	0.069*
C3	0.4383 (2)	0.1311 (2)	0.24509 (14)	0.0521 (5)
C4	0.4449 (2)	0.1348 (2)	0.12035 (14)	0.0821 (7)
H4A	0.5552	0.1526	0.0999	0.123*
H4B	0.3952	0.2161	0.0974	0.123*
H4C	0.3885	0.0382	0.0838	0.123*
C5	0.5595 (2)	−0.1002 (2)	0.22757 (13)	0.0508 (5)
C6	0.7234 (2)	−0.0729 (2)	0.20876 (14)	0.0579 (5)
C7	0.7848 (2)	−0.1914 (3)	0.15333 (15)	0.0697 (6)
H7	0.8937	−0.1763	0.1392	0.084*
C8	0.6859 (3)	−0.3301 (3)	0.11939 (15)	0.0710 (6)
H8	0.7291	−0.4091	0.0842	0.085*
C9	0.5242 (3)	−0.3537 (2)	0.13675 (14)	0.0638 (5)
H9	0.4591	−0.4480	0.1118	0.077*
C10	0.4557 (2)	−0.2397 (2)	0.19079 (13)	0.0529 (5)
C11	0.8341 (2)	0.0779 (2)	0.24878 (18)	0.0793 (6)
H11	0.7657	0.1534	0.2650	0.095*
C12	0.9507 (3)	0.1411 (3)	0.1612 (2)	0.1274 (9)
H12A	1.0269	0.0753	0.1486	0.191*
H12B	1.0068	0.2428	0.1879	0.191*
H12C	0.8915	0.1448	0.0920	0.191*
C13	0.9264 (3)	0.0662 (3)	0.35821 (18)	0.1140 (8)
H13A	0.8516	0.0412	0.4157	0.171*
H13B	0.9972	0.1628	0.3807	0.171*
H13C	0.9884	−0.0129	0.3471	0.171*
C14	0.2780 (2)	−0.2639 (2)	0.21149 (15)	0.0665 (5)
H14	0.2455	−0.1650	0.2053	0.080*
C15	0.2454 (2)	−0.3071 (2)	0.33083 (17)	0.0971 (7)
H15A	0.2766	−0.4035	0.3403	0.146*
H15B	0.1326	−0.3164	0.3431	0.146*
H15C	0.3064	−0.2286	0.3840	0.146*
C16	0.1727 (2)	−0.3808 (2)	0.12593 (19)	0.1022 (8)
H16A	0.1915	−0.3503	0.0516	0.153*
H16B	0.0614	−0.3855	0.1412	0.153*
H16C	0.1988	−0.4803	0.1311	0.153*
C17	0.2874 (3)	0.3794 (2)	0.58714 (14)	0.0862 (7)
H17A	0.3930	0.3940	0.6249	0.103*
H17B	0.2202	0.2884	0.6120	0.103*
C18	0.2146 (2)	0.5158 (2)	0.61480 (15)	0.0817 (6)
H18A	0.2811	0.6051	0.5891	0.123*
H18B	0.2064	0.5312	0.6947	0.123*
H18C	0.1092	0.4994	0.5785	0.123*

	U11	U22	U33	U12	U13	U23
O1	0.1105 (11)	0.0678 (9)	0.0517 (8)	0.0418 (8)	0.0065 (7)	0.0118 (7)
O2	0.1025 (11)	0.0614 (8)	0.0497 (8)	0.0382 (8)	0.0095 (7)	0.0023 (6)
N1	0.0797 (11)	0.0503 (9)	0.0418 (8)	0.0262 (8)	0.0075 (8)	0.0038 (8)
C1	0.0659 (14)	0.0490 (12)	0.0539 (12)	0.0173 (11)	0.0035 (10)	0.0014 (10)
C2	0.0800 (14)	0.0495 (11)	0.0487 (11)	0.0265 (10)	0.0032 (10)	0.0070 (9)
C3	0.0637 (13)	0.0487 (11)	0.0461 (11)	0.0158 (10)	0.0014 (9)	0.0067 (9)
C4	0.1282 (19)	0.0817 (15)	0.0491 (11)	0.0482 (14)	0.0115 (11)	0.0131 (11)
C5	0.0670 (14)	0.0497 (12)	0.0405 (10)	0.0222 (11)	0.0045 (10)	0.0052 (9)
C6	0.0666 (15)	0.0558 (13)	0.0546 (11)	0.0179 (12)	0.0060 (10)	0.0089 (10)
C7	0.0696 (15)	0.0803 (15)	0.0657 (13)	0.0283 (14)	0.0127 (11)	0.0091 (12)
C8	0.0917 (18)	0.0764 (16)	0.0537 (12)	0.0419 (14)	0.0057 (12)	−0.0036 (11)
C9	0.0837 (16)	0.0548 (12)	0.0541 (12)	0.0210 (12)	−0.0033 (11)	−0.0027 (10)
C10	0.0703 (15)	0.0498 (12)	0.0429 (10)	0.0222 (11)	0.0012 (10)	0.0050 (9)
C11	0.0711 (15)	0.0695 (15)	0.0960 (17)	0.0116 (13)	0.0051 (13)	0.0055 (13)
C12	0.112 (2)	0.124 (2)	0.139 (2)	−0.0138 (17)	0.0189 (18)	0.0496 (18)
C13	0.117 (2)	0.1073 (19)	0.0989 (18)	−0.0166 (16)	−0.0228 (16)	0.0004 (15)
C14	0.0711 (15)	0.0559 (13)	0.0741 (14)	0.0173 (11)	0.0021 (11)	0.0060 (11)
C15	0.0893 (18)	0.1064 (18)	0.0986 (17)	0.0148 (14)	0.0304 (14)	0.0286 (15)
C16	0.0800 (17)	0.0877 (17)	0.132 (2)	0.0130 (14)	−0.0184 (15)	−0.0127 (15)
C17	0.137 (2)	0.0852 (15)	0.0495 (12)	0.0540 (15)	0.0167 (12)	0.0017 (11)
C18	0.1002 (17)	0.0771 (15)	0.0726 (14)	0.0309 (13)	0.0199 (12)	−0.0032 (11)

O1—C1	1.2173 (18)	C11—C13	1.525 (3)
O2—C1	1.3543 (18)	C11—C12	1.529 (2)
O2—C17	1.4337 (18)	C11—H11	0.9800
N1—C3	1.3439 (19)	C12—H12A	0.9600
N1—C5	1.4310 (19)	C12—H12B	0.9600
N1—H1	0.894 (8)	C12—H12C	0.9600
C1—C2	1.419 (2)	C13—H13A	0.9600
C2—C3	1.350 (2)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.497 (2)	C14—C16	1.525 (2)
C4—H4A	0.9600	C14—C15	1.529 (2)
C4—H4B	0.9600	C14—H14	0.9800
C4—H4C	0.9600	C15—H15A	0.9600
C5—C6	1.392 (2)	C15—H15B	0.9600
C5—C10	1.402 (2)	C15—H15C	0.9600
C6—C7	1.392 (2)	C16—H16A	0.9600
C6—C11	1.510 (2)	C16—H16B	0.9600
C7—C8	1.371 (3)	C16—H16C	0.9600
C7—H7	0.9300	C17—C18	1.483 (2)
C8—C9	1.370 (2)	C17—H17A	0.9700
C8—H8	0.9300	C17—H17B	0.9700
C9—C10	1.388 (2)	C18—H18A	0.9600
C9—H9	0.9300	C18—H18B	0.9600
C10—C14	1.510 (2)	C18—H18C	0.9600
C1—O2—C17	116.95 (14)	C11—C12—H12A	109.5
C3—N1—C5	125.68 (14)	C11—C12—H12B	109.5
C3—N1—H1	113.3 (10)	H12A—C12—H12B	109.5
C5—N1—H1	121.1 (10)	C11—C12—H12C	109.5
O1—C1—O2	121.97 (16)	H12A—C12—H12C	109.5
O1—C1—C2	126.24 (17)	H12B—C12—H12C	109.5
O2—C1—C2	111.79 (16)	C11—C13—H13A	109.5
C3—C2—C1	124.19 (16)	C11—C13—H13B	109.5
C3—C2—H2	117.9	H13A—C13—H13B	109.5
C1—C2—H2	117.9	C11—C13—H13C	109.5
N1—C3—C2	122.83 (15)	H13A—C13—H13C	109.5
N1—C3—C4	116.49 (15)	H13B—C13—H13C	109.5
C2—C3—C4	120.68 (15)	C10—C14—C16	113.93 (16)
C3—C4—H4A	109.5	C10—C14—C15	111.14 (15)
C3—C4—H4B	109.5	C16—C14—C15	110.36 (17)
H4A—C4—H4B	109.5	C10—C14—H14	107.0
C3—C4—H4C	109.5	C16—C14—H14	107.0
H4A—C4—H4C	109.5	C15—C14—H14	107.0
H4B—C4—H4C	109.5	C14—C15—H15A	109.5
C6—C5—C10	122.50 (16)	C14—C15—H15B	109.5
C6—C5—N1	118.98 (17)	H15A—C15—H15B	109.5
C10—C5—N1	118.49 (17)	C14—C15—H15C	109.5
C7—C6—C5	117.78 (18)	H15A—C15—H15C	109.5
C7—C6—C11	120.22 (19)	H15B—C15—H15C	109.5
C5—C6—C11	121.99 (17)	C14—C16—H16A	109.5
C8—C7—C6	120.58 (19)	C14—C16—H16B	109.5
C8—C7—H7	119.7	H16A—C16—H16B	109.5
C6—C7—H7	119.7	C14—C16—H16C	109.5
C9—C8—C7	120.76 (18)	H16A—C16—H16C	109.5
C9—C8—H8	119.6	H16B—C16—H16C	109.5
C7—C8—H8	119.6	O2—C17—C18	108.30 (15)
C8—C9—C10	121.37 (19)	O2—C17—H17A	110.0
C8—C9—H9	119.3	C18—C17—H17A	110.0
C10—C9—H9	119.3	O2—C17—H17B	110.0
C9—C10—C5	116.97 (17)	C18—C17—H17B	110.0
C9—C10—C14	122.14 (18)	H17A—C17—H17B	108.4
C5—C10—C14	120.88 (16)	C17—C18—H18A	109.5
C6—C11—C13	111.31 (17)	C17—C18—H18B	109.5
C6—C11—C12	113.78 (18)	H18A—C18—H18B	109.5
C13—C11—C12	110.29 (19)	C17—C18—H18C	109.5
C6—C11—H11	107.0	H18A—C18—H18C	109.5
C13—C11—H11	107.0	H18B—C18—H18C	109.5
C12—C11—H11	107.0
C17—O2—C1—O1	1.9 (2)	C7—C8—C9—C10	−1.2 (3)
C17—O2—C1—C2	−178.36 (16)	C8—C9—C10—C5	−0.6 (2)
O1—C1—C2—C3	−0.6 (3)	C8—C9—C10—C14	−179.51 (16)
O2—C1—C2—C3	179.68 (17)	C6—C5—C10—C9	1.9 (2)
C5—N1—C3—C2	179.47 (17)	N1—C5—C10—C9	−176.47 (13)
C5—N1—C3—C4	0.0 (3)	C6—C5—C10—C14	−179.16 (14)
C1—C2—C3—N1	0.2 (3)	N1—C5—C10—C14	2.5 (2)
C1—C2—C3—C4	179.67 (17)	C7—C6—C11—C13	−79.3 (2)
C3—N1—C5—C6	88.8 (2)	C5—C6—C11—C13	99.3 (2)
C3—N1—C5—C10	−92.8 (2)	C7—C6—C11—C12	46.0 (2)
C10—C5—C6—C7	−1.4 (2)	C5—C6—C11—C12	−135.40 (19)
N1—C5—C6—C7	176.92 (14)	C9—C10—C14—C16	−27.7 (2)
C10—C5—C6—C11	179.97 (15)	C5—C10—C14—C16	153.41 (16)
N1—C5—C6—C11	−1.7 (2)	C9—C10—C14—C15	97.75 (19)
C5—C6—C7—C8	−0.4 (2)	C5—C10—C14—C15	−81.16 (19)
C11—C6—C7—C8	178.25 (17)	C1—O2—C17—C18	179.70 (16)
C6—C7—C8—C9	1.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.89 (1)	2.02 (1)	2.7402 (18)	137 (1)
N1—H1···O1i	0.89 (1)	2.68 (1)	3.3371 (18)	132 (1)

Table 1

Selected Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.89 (1)	2.02 (1)	2.7402 (18)	137 (1)
N1—H1⋯O1i	0.89 (1)	2.68 (1)	3.3371 (18)	132 (1)

Symmetry code: (i) .