(E)-Ethyl 3-(4-fluoroanilino)-2-(4-methoxyphenyl)acrylate

organic compounds Acta Crystallographica Section E Data collection Structure Reports Online Enraf–Nonius CAD-4 diffractometer Absorption correction: scan (North et al., 1968) Tmin = 0.972, Tmax = 0.981 ISSN 1600-5368 (E)-Ethyl 3-(4-fluoroanilino)-2-(4methoxyphenyl)acrylate Da-Gui Zhenga* and Zhu-Ping Xiaob 3073 measured reflections 2943 independent reflections 1807 reflections with I > 2(I) Rint = 0.026 Refinement R[F 2 > 2(F 2)] = 0.050 wR(F 2) = 0.162 S = 1.02 2943 reflections 215 parameters H atoms treated by a mixture of independent and constrained refinement
max = 0.15 e Å3
min = 0.16 e Å3 a Key Laboratory of Applied Organic Chemistry, Higher Institutions of Jiangxi Province, Shangrao Normal College, Shangrao 334001, Jiangxi, People’s Republic of China, and bCollege of Chemistry & Chemical Engineering, Jishou University, Jishou 416000, People’s Republic of China Correspondence e-mail: [email protected] Received 21 October 2008; accepted 21 November 2008 Key indicators: single-crystal X-ray study; T = 293 K; mean (C–C) = 0.004 Å; R factor = 0.050; wR factor = 0.162; data-to-parameter ratio = 13.7. In the title compound, C18H18FNO3, the dihedral angles between the two benzene rings and the plane through the acrylate group and the fluorophenyl ring are 61.58 (8) and 13.33 (9)
, respectively. Molecules are linked into ribbons through C—H  O and N—H  O hydrogen bonds, and further linked by C—H   interactions, forming a threedimensional network. Table 1 Hydrogen-bond geometry (Å,
). D—H  A D—H H  A D  A D—H  A C12—H12  O1i N1—H1  O3ii C16—H16B  Cg1iii C18—H18A  Cg2iv 0.93 0.83 (2) 0.97 0.96 2.49 2.56 (3) 2.99 2.80 3.401 3.229 3.788 3.626 167 138 (2) 141 145 (3) (3) (3) (3) Symmetry codes: (i) x; y þ 1; z; (ii) x þ 1; y þ 1; z; (iii) x; y þ 12; z þ 12; (iv) x þ 1; y; z. Cg1 and Cg2 are the centroids of the C1–C6 and C7–C12 rings, respectively. Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; 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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97. Related literature For related literature regarding the antimicrobial activity of 3arylamino-2-aryl acrylates, see: Shi et al. (2007); Xiao et al. (2007, 2008); Xue et al. (2007). For bond-length data, see: Allen et al. (1987). This research was financially supported by the Education Department of Jiangxi Province, P. R. China (grant No. 2007– 402). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2149). References Experimental Crystal data C18H18FNO3 Mr = 315.33 Monoclinic, P21 =c a = 19.000 (4) Å b = 6.0400 (12) Å c = 15.081 (3) Å = 109.64 (3)
o2456 Zheng and Xiao V = 1630.0 (6) Å3 Z=4 Mo K radiation  = 0.10 mm1 T = 293 (2) K 0.30  0.30  0.20 mm 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. Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351– 359. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Shi, D.-H., You, Z.-L., Xu, C., Zhang, Q. & Zhu, H.-L. (2007). Inorg. Chem. Commun. 10, 404–406. Xiao, Z.-P., Fang, R.-Q., Li, H.-Q., Shi, L., Xue, J.-Y., Zheng, Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. 43, 1828–1836. Xiao, Z.-P., Xue, J.-Y., Tan, S.-H., Li, H.-Q. & Zhu, H.-L. (2007). Bioorg. Med. Chem. 15, 4212–4219. Xue, J.-Y., Xiao, Z.-P., Shi, L., Tan, S.-H., Li, H.-Q. & Zhu, H.-L. (2007). Aust. J. Chem. 60, 957–962. doi:10.1107/S1600536808039184 Acta Cryst. (2008). E64, o2456 supporting information supporting information Acta Cryst. (2008). E64, o2456 [doi:10.1107/S1600536808039184] (E)-Ethyl 3-(4-fluoroanilino)-2-(4-methoxyphenyl)acrylate Da-Gui Zheng and Zhu-Ping Xiao S1. Comment 3-Arylamino-2-aryl acrylates, enamines structurally like Schiff bases, show high antimicrobial activity (Xiao et al., 2007; Xue et al., 2007; Xiao et al., 2008; Shi et al. 2007), especially for bacteria. In a continuation of our work on the structural characterization of enamine derivatives, we report here the crystal structure of the title compound, (I) (Fig. 1). The N1—H group lies approximately in the same planes as the fluorophenyl and acrylate groups (with dihedral angles of 4.7 (2) ° and 8.9 (2) °, respectively), suggesting that one of the p orbitals of N1 is conjugated with the π molecular orbitals of the two moieties, thus shortening both the C1—N1 (1.408 (3) Å) and C13—N1 (1.359 (3) Å) bonds. All other double and single bond lengths fall within normal values (Allen et al., 1987). Molecules are linked into ribbons running along the b-axis via C—H···O and N—H···O hydrogen bonds (Fig. 2 and Table 1). These ribbons are interconnected via weak C16-H16B···π (centroid of C1 to C6) and C18-H18A···π (centroid of C7 to C12) interactions (Table 1 and Fig. 3). S2. Experimental Equimolar quantities (6 mmol) of ethyl 2-(4-methoxyphenyl)-3- oxopropanoate (1.33 g) and 4-fluorobenzenamine (0.67 g) in absolute alcohol (18 ml) were heated at 344–354 K for 2 h. The excess solvent was removed under reduced pressure. The residue was purified by flash chromatography with EtOAc-petrolum ether (1:10) to afford two fractions. The first fraction gave the Z-isomer, and the second fraction, after partial solvent evaporation, furnished colorless blocks of (I) suitable for single-crystal structure determination. S3. Refinement The H atom bonded to N1 was located in a difference Fourier map. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.93, 0.96 and 0.97 Å for the aromatic, CH3 and CH2 type H atoms, respectively. Uiso = 1.2Ueq(parent atoms) were assigned for amino, aromatic and CH2 type Hatoms and 1.5Ueq(parent atoms) for CH3 type H-atoms. Acta Cryst. (2008). E64, o2456 sup-1 supporting information Figure 1 The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Figure 2 A partial packing diagram of the title compound showing the ribbons connected by C—H···O and N—H···O hydrogen bonds (indicated by dashed lines), viewed along the b axis. Acta Cryst. (2008). E64, o2456 sup-2 supporting information Figure 3 The crystal packing of the title compound, showing the linking of the hydrogen bonded ribbons by C—H···π interactions. Dashed lines indicate C—H···O, N—H···O and C-H···π interactions. (E)-Ethyl 3-(4-fluoroanilino)-2-(4-methoxyphenyl)acrylate Crystal data C18H18FNO3 Mr = 315.33 Monoclinic, P21/c a = 19.000 (4) Å b = 6.0400 (12) Å c = 15.081 (3) Å β = 109.64 (3)° V = 1630.0 (6) Å3 Z=4 F(000) = 664 Dx = 1.285 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1632 reflections θ = 1.4–24.7° µ = 0.10 mm−1 T = 293 K Block, colorless 0.30 × 0.30 × 0.20 mm Data collection Enraf–Nonius CAD-4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω/2θ scans Absorption correction: ψ scan (North et al., 1968) Tmin = 0.972, Tmax = 0.981 Acta Cryst. (2008). E64, o2456 3073 measured reflections 2943 independent reflections 1807 reflections with I > 2σ(I) Rint = 0.026 θmax = 25.3°, θmin = 1.1° h = −22→21 k = −7→0 l = 0→18 sup-3 supporting information Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.050 wR(F2) = 0.162 S = 1.02 2943 reflections 215 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0863P)2 + 0.0162P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.15 e Å−3 Δρmin = −0.16 e Å−3 Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.044 (4) 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) C1 C2 H2 C3 H3 C4 C5 H5 C6 H6 C7 C8 H8 C9 H9 C10 C11 H11 C12 H12 C13 H13 C14 x y z Uiso*/Ueq 0.78366 (12) 0.86057 (14) 0.8858 0.90034 (15) 0.9523 0.86292 (16) 0.78687 (17) 0.7620 0.74779 (15) 0.6958 0.64691 (12) 0.59236 (13) 0.6063 0.51803 (13) 0.4825 0.49607 (13) 0.54911 (13) 0.5350 0.62356 (13) 0.6591 0.76733 (13) 0.8176 0.72695 (12) 0.7249 (4) 0.7171 (5) 0.6095 0.8673 (6) 0.8617 1.0237 (5) 1.0339 (5) 1.1403 0.8829 (5) 0.8882 0.3267 (4) 0.1688 (4) 0.0338 0.2090 (5) 0.1013 0.4075 (4) 0.5661 (4) 0.7002 0.5233 (4) 0.6302 0.4059 (4) 0.3699 0.2824 (4) 0.02705 (17) 0.0575 (2) 0.1005 0.0246 (2) 0.0451 −0.0380 (2) −0.0708 (2) −0.1148 −0.0373 (2) −0.0588 0.14607 (16) 0.10497 (18) 0.0862 0.09161 (18) 0.0639 0.11902 (17) 0.16114 (19) 0.1804 0.17434 (19) 0.2032 0.12087 (17) 0.1356 0.16064 (16) 0.0468 (6) 0.0637 (8) 0.076* 0.0733 (9) 0.088* 0.0682 (9) 0.0721 (9) 0.086* 0.0640 (8) 0.077* 0.0431 (6) 0.0494 (7) 0.059* 0.0513 (7) 0.062* 0.0470 (6) 0.0523 (7) 0.063* 0.0510 (7) 0.061* 0.0465 (6) 0.056* 0.0433 (6) Acta Cryst. (2008). E64, o2456 sup-4 supporting information C15 C16 H16A H16B C17 H17A H17B H17C C18 H18A H18B H18C F1 H1 N1 O1 O2 O3 0.76226 (13) 0.87264 (15) 0.8550 0.8630 0.95460 (15) 0.9637 0.9817 0.9709 0.39590 (15) 0.4220 0.3432 0.4057 0.90279 (11) 0.6954 (14) 0.74101 (12) 0.73060 (10) 0.83483 (9) 0.42082 (9) 0.0959 (4) −0.1081 (5) −0.2514 −0.0960 −0.0844 (6) −0.1045 −0.1941 0.0606 0.6241 (5) 0.6374 0.6130 0.7521 1.1721 (4) 0.606 (4) 0.5785 (4) −0.0227 (3) 0.0669 (3) 0.4306 (3) 0.22121 (18) 0.2948 (2) 0.2671 0.3538 0.3113 (3) 0.2530 0.3558 0.3358 0.1368 (2) 0.2032 0.1255 0.1051 −0.07006 (17) 0.0454 (19) 0.06106 (16) 0.26022 (14) 0.23152 (13) 0.10206 (13) 0.0458 (6) 0.0669 (8) 0.080* 0.080* 0.0887 (11) 0.133* 0.133* 0.133* 0.0751 (9) 0.113* 0.113* 0.113* 0.1125 (8) 0.059 (8)* 0.0567 (6) 0.0667 (6) 0.0584 (5) 0.0618 (6) Atomic displacement parameters (Å2) C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 F1 N1 O1 O2 O3 U11 U22 U33 U12 U13 U23 0.0401 (13) 0.0465 (15) 0.0434 (15) 0.0596 (18) 0.074 (2) 0.0450 (15) 0.0403 (13) 0.0456 (14) 0.0412 (13) 0.0361 (12) 0.0490 (15) 0.0449 (14) 0.0364 (12) 0.0410 (13) 0.0441 (13) 0.0616 (17) 0.0565 (18) 0.0521 (16) 0.0896 (13) 0.0359 (12) 0.0589 (11) 0.0439 (10) 0.0399 (10) 0.0536 (15) 0.076 (2) 0.093 (2) 0.073 (2) 0.065 (2) 0.0681 (19) 0.0433 (14) 0.0464 (15) 0.0540 (17) 0.0550 (16) 0.0417 (14) 0.0364 (14) 0.0493 (15) 0.0406 (14) 0.0422 (14) 0.0523 (17) 0.093 (3) 0.091 (2) 0.1078 (17) 0.0658 (15) 0.0540 (12) 0.0583 (12) 0.0733 (13) 0.0482 (14) 0.0642 (17) 0.082 (2) 0.082 (2) 0.085 (2) 0.078 (2) 0.0443 (14) 0.0548 (15) 0.0528 (15) 0.0482 (14) 0.0668 (17) 0.0694 (18) 0.0502 (15) 0.0471 (14) 0.0521 (15) 0.076 (2) 0.104 (3) 0.085 (2) 0.154 (2) 0.0665 (15) 0.0889 (15) 0.0718 (13) 0.0714 (13) −0.0053 (12) −0.0017 (15) −0.0056 (16) −0.0085 (16) 0.0109 (16) 0.0063 (14) −0.0067 (11) −0.0018 (12) −0.0131 (12) −0.0008 (12) −0.0045 (12) −0.0074 (11) −0.0021 (12) −0.0060 (11) −0.0065 (12) 0.0087 (15) 0.0198 (18) 0.0079 (16) −0.0112 (12) 0.0010 (12) −0.0014 (10) 0.0047 (9) 0.0012 (9) 0.0170 (11) 0.0135 (13) 0.0193 (15) 0.0371 (16) 0.0370 (17) 0.0193 (14) 0.0125 (10) 0.0150 (12) 0.0081 (11) 0.0118 (11) 0.0202 (13) 0.0164 (13) 0.0097 (11) 0.0133 (11) 0.0174 (12) 0.0087 (15) 0.0101 (18) 0.0267 (16) 0.0592 (14) 0.0146 (11) 0.0272 (11) 0.0177 (9) 0.0177 (9) 0.0019 (13) 0.0221 (16) 0.026 (2) 0.0172 (18) 0.0304 (18) 0.0157 (17) 0.0005 (12) −0.0075 (13) −0.0127 (13) 0.0038 (13) −0.0085 (13) −0.0033 (13) 0.0004 (13) −0.0046 (12) −0.0088 (13) 0.0069 (16) 0.004 (2) −0.0201 (19) 0.0556 (15) 0.0177 (13) 0.0181 (11) 0.0084 (10) −0.0061 (11) Acta Cryst. (2008). E64, o2456 sup-5 supporting information Geometric parameters (Å, º) C1—C6 C1—C2 C1—N1 C2—C3 C2—H2 C3—C4 C3—H3 C4—C5 C4—F1 C5—C6 C5—H5 C6—H6 C7—C12 C7—C8 C7—C14 C8—C9 C8—H8 C9—C10 C9—H9 C10—O3 C10—C11 1.368 (4) 1.377 (3) 1.408 (3) 1.375 (4) 0.9300 1.355 (4) 0.9300 1.362 (4) 1.363 (3) 1.375 (4) 0.9300 0.9300 1.384 (3) 1.392 (3) 1.486 (3) 1.379 (3) 0.9300 1.378 (4) 0.9300 1.372 (3) 1.381 (3) C11—C12 C11—H11 C12—H12 C13—C14 C13—N1 C13—H13 C14—C15 C15—O1 C15—O2 C16—O2 C16—C17 C16—H16A C16—H16B C17—H17A C17—H17B C17—H17C C18—O3 C18—H18A C18—H18B C18—H18C N1—H1 1.385 (3) 0.9300 0.9300 1.347 (3) 1.359 (3) 0.9300 1.463 (3) 1.208 (3) 1.346 (3) 1.444 (3) 1.499 (4) 0.9700 0.9700 0.9600 0.9600 0.9600 1.425 (3) 0.9600 0.9600 0.9600 0.83 (2) C6—C1—C2 C6—C1—N1 C2—C1—N1 C3—C2—C1 C3—C2—H2 C1—C2—H2 C4—C3—C2 C4—C3—H3 C2—C3—H3 C3—C4—C5 C3—C4—F1 C5—C4—F1 C4—C5—C6 C4—C5—H5 C6—C5—H5 C1—C6—C5 C1—C6—H6 C5—C6—H6 C12—C7—C8 C12—C7—C14 C8—C7—C14 C9—C8—C7 C9—C8—H8 C7—C8—H8 118.7 (2) 119.1 (2) 122.2 (2) 120.5 (3) 119.8 119.8 119.2 (2) 120.4 120.4 121.9 (3) 118.8 (3) 119.3 (3) 118.3 (3) 120.8 120.8 121.4 (2) 119.3 119.3 117.2 (2) 121.8 (2) 120.9 (2) 121.1 (2) 119.4 119.4 C7—C12—H12 C11—C12—H12 C14—C13—N1 C14—C13—H13 N1—C13—H13 C13—C14—C15 C13—C14—C7 C15—C14—C7 O1—C15—O2 O1—C15—C14 O2—C15—C14 O2—C16—C17 O2—C16—H16A C17—C16—H16A O2—C16—H16B C17—C16—H16B H16A—C16—H16B C16—C17—H17A C16—C17—H17B H17A—C17—H17B C16—C17—H17C H17A—C17—H17C H17B—C17—H17C O3—C18—H18A 118.9 118.9 125.6 (2) 117.2 117.2 119.6 (2) 122.8 (2) 117.6 (2) 121.7 (2) 124.2 (2) 114.2 (2) 107.4 (2) 110.2 110.2 110.2 110.2 108.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 Acta Cryst. (2008). E64, o2456 sup-6 supporting information C10—C9—C8 C10—C9—H9 C8—C9—H9 O3—C10—C9 O3—C10—C11 C9—C10—C11 C10—C11—C12 C10—C11—H11 C12—C11—H11 C7—C12—C11 120.5 (2) 119.7 119.7 115.8 (2) 124.6 (2) 119.6 (2) 119.2 (2) 120.4 120.4 122.3 (2) O3—C18—H18B H18A—C18—H18B O3—C18—H18C H18A—C18—H18C H18B—C18—H18C C13—N1—C1 C13—N1—H1 C1—N1—H1 C15—O2—C16 C10—O3—C18 109.5 109.5 109.5 109.5 109.5 126.5 (2) 117.1 (19) 116.3 (19) 115.8 (2) 118.0 (2) C6—C1—C2—C3 N1—C1—C2—C3 C1—C2—C3—C4 C2—C3—C4—C5 C2—C3—C4—F1 C3—C4—C5—C6 F1—C4—C5—C6 C2—C1—C6—C5 N1—C1—C6—C5 C4—C5—C6—C1 C12—C7—C8—C9 C14—C7—C8—C9 C7—C8—C9—C10 C8—C9—C10—O3 C8—C9—C10—C11 O3—C10—C11—C12 C9—C10—C11—C12 C8—C7—C12—C11 C14—C7—C12—C11 0.9 (4) −178.1 (3) 0.1 (5) −1.3 (5) 179.9 (3) 1.4 (5) −179.8 (3) −0.8 (4) 178.2 (3) −0.3 (5) 1.2 (4) 179.8 (2) −0.1 (4) 179.7 (2) −0.7 (4) −179.9 (2) 0.5 (4) −1.3 (4) −180.0 (2) C10—C11—C12—C7 N1—C13—C14—C15 N1—C13—C14—C7 C12—C7—C14—C13 C8—C7—C14—C13 C12—C7—C14—C15 C8—C7—C14—C15 C13—C14—C15—O1 C7—C14—C15—O1 C13—C14—C15—O2 C7—C14—C15—O2 C14—C13—N1—C1 C6—C1—N1—C13 C2—C1—N1—C13 O1—C15—O2—C16 C14—C15—O2—C16 C17—C16—O2—C15 C9—C10—O3—C18 C11—C10—O3—C18 0.5 (4) 177.8 (2) −2.3 (4) −62.1 (3) 119.3 (3) 117.8 (3) −60.8 (3) 179.5 (2) −0.4 (4) 0.3 (3) −179.6 (2) 172.4 (2) 176.2 (3) −4.8 (4) −2.4 (3) 176.8 (2) −169.0 (2) 174.3 (2) −5.2 (4) Hydrogen-bond geometry (Å, º) D—H···A i C12—H12···O1 N1—H1···O3ii C16—H16B···Cg1iii C18—H18A···Cg2iv D—H H···A D···A D—H···A 0.93 0.83 (2) 0.97 0.96 2.49 2.56 (3) 2.99 2.80 3.401 (3) 3.229 (3) 3.788 (3) 3.626 (3) 167 138 (2) 141 145 Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) x, −y+1/2, z+1/2; (iv) −x+1, −y, −z. Acta Cryst. (2008). E64, o2456 sup-7