2-{(E)-4-[4-(Trifluoro-meth-yl)phen-oxy]but-2-en-yloxy}phenyl N-methyl-carbamate.

In the title compound, C19H18F3NO4, which was designed and synthesized as a dual-site inhibitor of insect AChE (acetyl-cholinesterase), the dihedral angle between the methyl-carbamate group and the benzene ring is 72.47 (6)°. In the crystal, inversion dimers are linked by pairs of N-H⋯O hydrogen bonds.

Related literature

For background to multivalent ligand-receptor inter­actions and their pharmaceutical applications, see: Carlier et al. (1999 ▶); Hu et al. (2002 ▶); Kitov et al. (2000 ▶); Kopytek et al. (2000 ▶); Kryger et al. (1999 ▶); Lee & Lee (1995 ▶); Luedtke et al. (2003 ▶); Mammen et al. (1998 ▶); Pang et al. (1996 ▶). For agrochemical applications of the cluster effect, see: Ma et al. (2010 ▶); Zhao et al. (2008 ▶, 2009 ▶). For the structure of AChE from Torpedo californica (TcAChe), see: Sussman et al. (1991 ▶); Harel et al. (1993 ▶).

Experimental

Crystal data

C19H18F3NO4

M = 381.34

Monoclinic,

a = 12.413 (3) Å

b = 9.3936 (19) Å

c = 16.202 (3) Å

β = 111.65 (3)°

V = 1755.9 (6) Å3

Z = 4

Cu Kα radiation

μ = 1.05 mm−1

T = 173 K

0.47 × 0.30 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.639, T max = 0.780

11613 measured reflections

3163 independent reflections

2615 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.107

S = 1.07

3163 reflections

274 parameters

60 restraints

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.22 e Å−3

Data collection: RAPID-AUTO (Rigaku 2001 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813001347/mw2102sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813001347/mw2102Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813001347/mw2102Isup3.cml

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

C19H18F3NO4	F(000) = 792
Mr = 381.34	Dx = 1.443 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 468 reflections
a = 12.413 (3) Å	θ = 2.2–68.3°
b = 9.3936 (19) Å	µ = 1.05 mm−1
c = 16.202 (3) Å	T = 173 K
β = 111.65 (3)°	Block, colorless
V = 1755.9 (6) Å3	0.47 × 0.30 × 0.25 mm
Z = 4

Rigaku R-AXIS RAPID IP area-detector diffractometer	3163 independent reflections
Radiation source: rotating anode	2615 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans at fixed χ = 45°	θmax = 68.2°, θmin = 3.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
Tmin = 0.639, Tmax = 0.780	k = −11→10
11613 measured reflections	l = −18→19

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) = 0.107	w = 1/[σ2(Fo2) + (0.0381P)2 + 0.8611P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
3163 reflections	Δρmax = 0.29 e Å−3
274 parameters	Δρmin = −0.22 e Å−3
60 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: 0.0033 (3)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.4769 (4)	−0.2372 (3)	0.2853 (4)	0.0698 (14)	0.710 (12)
F2	0.4529 (5)	−0.0522 (5)	0.2121 (3)	0.0731 (13)	0.710 (12)
F3	0.5816 (4)	−0.0554 (8)	0.3412 (5)	0.090 (2)	0.710 (12)
F1'	0.5251 (13)	−0.2132 (15)	0.3448 (14)	0.109 (5)	0.290 (12)
F2'	0.4491 (9)	−0.111 (2)	0.2122 (6)	0.111 (5)	0.290 (12)
F3'	0.5655 (11)	−0.0074 (18)	0.3219 (13)	0.092 (5)	0.290 (12)
O1	0.13692 (11)	0.11336 (15)	0.41856 (9)	0.0376 (4)
O2	−0.17712 (11)	0.32576 (15)	0.48990 (9)	0.0348 (3)
O3	0.02201 (12)	0.28785 (14)	0.67050 (9)	0.0367 (4)
O4	−0.03869 (11)	0.50607 (14)	0.60863 (9)	0.0313 (3)
N1	0.12414 (13)	0.41620 (18)	0.60530 (11)	0.0336 (4)
H1	0.1242	0.4945	0.5755	0.040*
C1	0.47480 (19)	−0.0960 (2)	0.29620 (17)	0.0477 (6)
C2	0.38579 (17)	−0.0443 (2)	0.32947 (14)	0.0360 (5)
C3	0.27526 (17)	−0.1023 (2)	0.29649 (13)	0.0360 (5)
H3	0.2584	−0.1773	0.2543	0.043*
C4	0.18957 (17)	−0.0526 (2)	0.32412 (13)	0.0332 (5)
H4	0.1141	−0.0930	0.3009	0.040*
C5	0.21432 (16)	0.0570 (2)	0.38617 (13)	0.0318 (4)
C6	0.32588 (18)	0.1133 (2)	0.42067 (15)	0.0422 (5)
H6	0.3437	0.1868	0.4640	0.051*
C7	0.41034 (18)	0.0630 (2)	0.39219 (15)	0.0439 (5)
H7	0.4862	0.1022	0.4158	0.053*
C8	0.01688 (16)	0.0769 (2)	0.37353 (13)	0.0354 (5)
H8A	0.0055	−0.0264	0.3792	0.043*
H8B	−0.0081	0.1005	0.3096	0.043*
C9	−0.05238 (17)	0.1595 (2)	0.41472 (13)	0.0329 (5)
H9	−0.0182	0.2416	0.4485	0.039*
C10	−0.15720 (18)	0.1256 (2)	0.40707 (14)	0.0381 (5)
H10	−0.1877	0.0412	0.3745	0.046*
C11	−0.23549 (17)	0.2024 (2)	0.44281 (13)	0.0337 (5)
H11A	−0.3074	0.2308	0.3935	0.040*
H11B	−0.2569	0.1392	0.4832	0.040*
C12	−0.22437 (16)	0.3914 (2)	0.54436 (12)	0.0300 (4)
C13	−0.33741 (17)	0.3764 (2)	0.53971 (13)	0.0354 (5)
H13	−0.3893	0.3149	0.4967	0.042*
C14	−0.37483 (18)	0.4512 (2)	0.59798 (14)	0.0394 (5)
H14	−0.4523	0.4402	0.5948	0.047*
C15	−0.30069 (18)	0.5415 (2)	0.66040 (14)	0.0392 (5)
H15	−0.3271	0.5922	0.7001	0.047*
C16	−0.18725 (17)	0.5581 (2)	0.66513 (13)	0.0347 (5)
H16	−0.1360	0.6209	0.7076	0.042*
C17	−0.14992 (16)	0.4832 (2)	0.60820 (12)	0.0296 (4)
C18	0.03597 (16)	0.3915 (2)	0.63119 (12)	0.0290 (4)
C19	0.22029 (18)	0.3175 (2)	0.62487 (16)	0.0446 (6)
H19A	0.2818	0.3611	0.6091	0.067*
H19B	0.1936	0.2300	0.5904	0.067*
H19C	0.2504	0.2947	0.6884	0.067*

	U11	U22	U33	U12	U13	U23
F1	0.082 (2)	0.0421 (13)	0.117 (3)	0.0125 (13)	0.073 (2)	0.0034 (16)
F2	0.084 (3)	0.083 (2)	0.077 (2)	0.0261 (19)	0.059 (2)	0.019 (2)
F3	0.0276 (13)	0.136 (5)	0.100 (3)	−0.001 (2)	0.0170 (15)	−0.051 (3)
F1'	0.099 (7)	0.091 (7)	0.172 (12)	0.058 (6)	0.092 (8)	0.046 (7)
F2'	0.038 (4)	0.192 (13)	0.093 (7)	−0.003 (6)	0.011 (4)	−0.102 (8)
F3'	0.065 (7)	0.090 (7)	0.159 (11)	−0.039 (6)	0.087 (8)	−0.045 (7)
O1	0.0312 (7)	0.0435 (8)	0.0390 (8)	−0.0012 (6)	0.0141 (6)	−0.0093 (7)
O2	0.0333 (7)	0.0358 (8)	0.0412 (8)	−0.0074 (6)	0.0207 (6)	−0.0109 (6)
O3	0.0369 (8)	0.0314 (8)	0.0423 (8)	0.0002 (6)	0.0151 (6)	0.0082 (6)
O4	0.0279 (7)	0.0274 (7)	0.0399 (7)	0.0004 (6)	0.0139 (6)	0.0013 (6)
N1	0.0307 (8)	0.0351 (9)	0.0369 (9)	0.0017 (7)	0.0148 (7)	0.0039 (8)
C1	0.0362 (12)	0.0442 (13)	0.0672 (16)	0.0019 (11)	0.0243 (11)	0.0044 (13)
C2	0.0302 (10)	0.0354 (11)	0.0437 (11)	0.0024 (9)	0.0151 (9)	0.0051 (9)
C3	0.0347 (10)	0.0354 (11)	0.0385 (11)	−0.0001 (9)	0.0141 (9)	−0.0032 (9)
C4	0.0300 (10)	0.0346 (11)	0.0344 (10)	−0.0010 (8)	0.0111 (8)	−0.0010 (9)
C5	0.0302 (10)	0.0330 (10)	0.0327 (10)	0.0027 (8)	0.0121 (8)	0.0035 (8)
C6	0.0342 (11)	0.0405 (12)	0.0489 (12)	−0.0047 (10)	0.0118 (9)	−0.0112 (10)
C7	0.0285 (10)	0.0434 (12)	0.0573 (14)	−0.0043 (9)	0.0130 (10)	−0.0055 (11)
C8	0.0313 (10)	0.0384 (11)	0.0380 (11)	−0.0031 (9)	0.0145 (9)	−0.0050 (9)
C9	0.0347 (10)	0.0314 (10)	0.0335 (10)	−0.0015 (9)	0.0137 (8)	−0.0049 (8)
C10	0.0408 (11)	0.0331 (11)	0.0439 (12)	−0.0048 (9)	0.0200 (9)	−0.0095 (9)
C11	0.0334 (10)	0.0322 (10)	0.0367 (11)	−0.0048 (8)	0.0142 (8)	−0.0041 (8)
C12	0.0303 (10)	0.0313 (10)	0.0315 (10)	0.0019 (8)	0.0147 (8)	0.0007 (8)
C13	0.0297 (10)	0.0400 (12)	0.0382 (11)	−0.0026 (9)	0.0145 (9)	−0.0030 (9)
C14	0.0315 (10)	0.0457 (13)	0.0463 (12)	0.0046 (9)	0.0205 (9)	0.0035 (10)
C15	0.0408 (12)	0.0441 (12)	0.0378 (11)	0.0078 (10)	0.0206 (10)	0.0003 (10)
C16	0.0379 (11)	0.0333 (11)	0.0325 (10)	0.0025 (9)	0.0125 (9)	−0.0001 (9)
C17	0.0279 (9)	0.0291 (10)	0.0331 (10)	0.0013 (8)	0.0129 (8)	0.0029 (8)
C18	0.0271 (9)	0.0294 (10)	0.0284 (9)	−0.0008 (8)	0.0077 (8)	−0.0031 (8)
C19	0.0319 (11)	0.0475 (13)	0.0549 (13)	0.0068 (10)	0.0168 (10)	0.0000 (11)

F1—C1	1.339 (3)	C6—H6	0.9500
F2—C1	1.351 (4)	C7—H7	0.9500
F3—C1	1.312 (5)	C8—C9	1.487 (3)
F1'—C1	1.363 (7)	C8—H8A	0.9900
F2'—C1	1.287 (8)	C8—H8B	0.9900
F3'—C1	1.337 (9)	C9—C10	1.300 (3)
O1—C5	1.361 (2)	C9—H9	0.9500
O1—C8	1.438 (2)	C10—C11	1.488 (3)
O2—C12	1.373 (2)	C10—H10	0.9500
O2—C11	1.429 (2)	C11—H11A	0.9900
O3—C18	1.210 (2)	C11—H11B	0.9900
O4—C18	1.379 (2)	C12—C13	1.384 (3)
O4—C17	1.395 (2)	C12—C17	1.401 (3)
N1—C18	1.329 (2)	C13—C14	1.387 (3)
N1—C19	1.451 (3)	C13—H13	0.9500
N1—H1	0.8800	C14—C15	1.379 (3)
C1—C2	1.479 (3)	C14—H14	0.9500
C2—C7	1.383 (3)	C15—C16	1.390 (3)
C2—C3	1.387 (3)	C15—H15	0.9500
C3—C4	1.379 (3)	C16—C17	1.369 (3)
C3—H3	0.9500	C16—H16	0.9500
C4—C5	1.392 (3)	C19—H19A	0.9800
C4—H4	0.9500	C19—H19B	0.9800
C5—C6	1.393 (3)	C19—H19C	0.9800
C6—C7	1.376 (3)
C5—O1—C8	117.30 (15)	H8A—C8—H8B	108.4
C12—O2—C11	117.06 (15)	C10—C9—C8	123.63 (19)
C18—O4—C17	116.65 (14)	C10—C9—H9	118.2
C18—N1—C19	121.73 (18)	C8—C9—H9	118.2
C18—N1—H1	119.1	C9—C10—C11	128.22 (19)
C19—N1—H1	119.1	C9—C10—H10	115.9
F2'—C1—F3'	104.5 (10)	C11—C10—H10	115.9
F3—C1—F1	107.3 (4)	O2—C11—C10	108.98 (16)
F3—C1—F2	104.9 (4)	O2—C11—H11A	109.9
F1—C1—F2	100.1 (3)	C10—C11—H11A	109.9
F2'—C1—F1'	113.7 (8)	O2—C11—H11B	109.9
F3'—C1—F1'	99.7 (8)	C10—C11—H11B	109.9
F2'—C1—C2	119.7 (6)	H11A—C11—H11B	108.3
F3—C1—C2	116.1 (4)	O2—C12—C13	125.72 (17)
F3'—C1—C2	109.8 (7)	O2—C12—C17	115.42 (16)
F1—C1—C2	115.2 (2)	C13—C12—C17	118.84 (18)
F2—C1—C2	111.6 (3)	C12—C13—C14	119.89 (19)
F1'—C1—C2	107.4 (5)	C12—C13—H13	120.1
C7—C2—C3	119.2 (2)	C14—C13—H13	120.1
C7—C2—C1	121.03 (19)	C15—C14—C13	120.68 (19)
C3—C2—C1	119.8 (2)	C15—C14—H14	119.7
C4—C3—C2	120.9 (2)	C13—C14—H14	119.7
C4—C3—H3	119.5	C14—C15—C16	119.8 (2)
C2—C3—H3	119.5	C14—C15—H15	120.1
C3—C4—C5	119.58 (19)	C16—C15—H15	120.1
C3—C4—H4	120.2	C17—C16—C15	119.53 (19)
C5—C4—H4	120.2	C17—C16—H16	120.2
O1—C5—C4	124.58 (18)	C15—C16—H16	120.2
O1—C5—C6	115.86 (18)	C16—C17—O4	119.88 (17)
C4—C5—C6	119.54 (19)	C16—C17—C12	121.22 (18)
C7—C6—C5	120.2 (2)	O4—C17—C12	118.71 (17)
C7—C6—H6	119.9	O3—C18—N1	126.96 (18)
C5—C6—H6	119.9	O3—C18—O4	123.69 (17)
C6—C7—C2	120.6 (2)	N1—C18—O4	109.33 (16)
C6—C7—H7	119.7	N1—C19—H19A	109.5
C2—C7—H7	119.7	N1—C19—H19B	109.5
O1—C8—C9	108.10 (16)	H19A—C19—H19B	109.5
O1—C8—H8A	110.1	N1—C19—H19C	109.5
C9—C8—H8A	110.1	H19A—C19—H19C	109.5
O1—C8—H8B	110.1	H19B—C19—H19C	109.5
C9—C8—H8B	110.1
F2'—C1—C2—C7	−132.8 (10)	C5—O1—C8—C9	−175.09 (16)
F3—C1—C2—C7	12.8 (5)	O1—C8—C9—C10	−160.9 (2)
F3'—C1—C2—C7	−11.9 (10)	C8—C9—C10—C11	−177.9 (2)
F1—C1—C2—C7	139.4 (4)	C12—O2—C11—C10	−165.39 (16)
F2—C1—C2—C7	−107.3 (3)	C9—C10—C11—O2	−0.2 (3)
F1'—C1—C2—C7	95.6 (11)	C11—O2—C12—C13	−19.5 (3)
F2'—C1—C2—C3	46.2 (10)	C11—O2—C12—C17	161.91 (17)
F3—C1—C2—C3	−168.2 (4)	O2—C12—C13—C14	−178.79 (18)
F3'—C1—C2—C3	167.0 (10)	C17—C12—C13—C14	−0.2 (3)
F1—C1—C2—C3	−41.6 (4)	C12—C13—C14—C15	0.4 (3)
F2—C1—C2—C3	71.7 (3)	C13—C14—C15—C16	0.1 (3)
F1'—C1—C2—C3	−85.4 (11)	C14—C15—C16—C17	−0.7 (3)
C7—C2—C3—C4	1.2 (3)	C15—C16—C17—O4	175.88 (17)
C1—C2—C3—C4	−177.75 (19)	C15—C16—C17—C12	0.8 (3)
C2—C3—C4—C5	−0.2 (3)	C18—O4—C17—C16	117.69 (19)
C8—O1—C5—C4	−12.6 (3)	C18—O4—C17—C12	−67.1 (2)
C8—O1—C5—C6	169.01 (18)	O2—C12—C17—C16	178.33 (17)
C3—C4—C5—O1	−179.48 (18)	C13—C12—C17—C16	−0.4 (3)
C3—C4—C5—C6	−1.1 (3)	O2—C12—C17—O4	3.2 (3)
O1—C5—C6—C7	179.85 (19)	C13—C12—C17—O4	−175.48 (17)
C4—C5—C6—C7	1.3 (3)	C19—N1—C18—O3	−1.9 (3)
C5—C6—C7—C2	−0.3 (3)	C19—N1—C18—O4	176.30 (17)
C3—C2—C7—C6	−1.0 (3)	C17—O4—C18—O3	−18.9 (3)
C1—C2—C7—C6	178.0 (2)	C17—O4—C18—N1	162.82 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.88	2.22	3.072 (2)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.88	2.22	3.072 (2)	163

Symmetry code: (i) .