Acta Cryst. (2009). E65, o739 [ doi:10.1107/S1600536809007430 ]
The title compound, C17H16ClNO, was synthesized using a solvent-free method by reaction of 4-(dimethylamino)benzaldehyde with 4-chloroacetophenone and NaOH. The chlorophenyl ring makes a dihedral angle of 18.1 (3)° with the central propenone unit, while the (dimethylamino)phenyl group is disordered over two orientations of equal occupancies, which make dihedral angles with the central propenone unit of 32.9 (3) and 57.4 (3)°, respectively.
4-(Dimethylamino)benzaldehyde (0.5 mmol) and 4-chloroacetophenone (0.5 mmol), NaOH (0.5 mmol) were mixed in 50 ml flask under solvent-free conditions After stirring for 6 min at 373 K, the mixture was slowly solidified to give the title compound. Recrystallization from ethanol gave a yellow crystalline solid. Elemental analysis calculated: C 71.45, H 5.64, N 4.90%; found: C 71.53, H 5.56, N 4.95%.
All H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.96 Å and Uiso(H) = 1.2 or 1.5Ueq(C). The five-membered ring was treated as disordered between two orientations with site occupancy factors refined to 0.500 (5). The bonds N1—C16, N1—C16', N1—C17 and N1—C17' were restrained to be 1.47 (1)Å.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2339fig1thm.gif)
| Fig. 1. The molecular structure showing 30% probability displacement ellipsoids for non-H atoms. |
| C17H16ClNO | F(000) = 600 |
| Mr = 285.76 | Dx = 1.283 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 987 reflections |
| a = 16.792 (2) Å | θ = 2.5–19.9° |
| b = 14.5602 (16) Å | µ = 0.25 mm−1 |
| c = 6.1160 (8) Å | T = 298 K |
| β = 98.333 (2)° | Needle, yellow |
| V = 1479.5 (3) Å3 | 0.42 × 0.20 × 0.13 mm |
| Z = 4 |
| Bruker SMART CCD diffractometer | 2605 independent reflections |
| Radiation source: fine-focus sealed tube | 1066 reflections with I > 2˘I) |
| graphite | Rint = 0.068 |
| φ and ω scans | θmax = 25.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −19→19 |
| Tmin = 0.901, Tmax = 0.968 | k = −17→12 |
| 7357 measured reflections | l = −7→7 |
| 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.170 | H-atom parameters constrained |
| S = 0.90 | w = 1/[σ2(Fo2) + (0.0749P)2] where P = (Fo2 + 2Fc2)/3 |
| 2605 reflections | (Δ/σ)max < 0.001 |
| 237 parameters | Δρmax = 0.16 e Å−3 |
| 4 restraints | Δρmin = −0.12 e Å−3 |
| C17H16ClNO | V = 1479.5 (3) Å3 |
| Mr = 285.76 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 16.792 (2) Å | µ = 0.25 mm−1 |
| b = 14.5602 (16) Å | T = 298 K |
| c = 6.1160 (8) Å | 0.42 × 0.20 × 0.13 mm |
| β = 98.333 (2)° |
| Bruker SMART CCD diffractometer | 2605 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1066 reflections with I > 2˘I) |
| Tmin = 0.901, Tmax = 0.968 | Rint = 0.068 |
| 7357 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
| wR(F2) = 0.170 | Δρmax = 0.16 e Å−3 |
| S = 0.90 | Δρmin = −0.12 e Å−3 |
| 2605 reflections | Absolute structure: ? |
| 237 parameters | Flack parameter: ? |
| 4 restraints | Rogers parameter: ? |
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) | |
| Cl1 | 1.12683 (6) | 0.14642 (9) | 1.2060 (3) | 0.1285 (7) | |
| N1 | 0.34724 (18) | 0.1225 (2) | 0.8419 (7) | 0.0891 (11) | |
| O1 | 0.80650 (17) | 0.1009 (2) | 0.4377 (6) | 0.1225 (12) | |
| C1 | 0.8071 (2) | 0.1135 (2) | 0.6344 (8) | 0.0739 (11) | |
| C2 | 0.8853 (2) | 0.1192 (2) | 0.7831 (7) | 0.0683 (10) | |
| C3 | 0.8921 (2) | 0.1538 (2) | 0.9959 (7) | 0.0742 (11) | |
| H3 | 0.8460 | 0.1712 | 1.0530 | 0.089* | |
| C4 | 0.9663 (2) | 0.1627 (2) | 1.1247 (7) | 0.0801 (11) | |
| H4 | 0.9701 | 0.1868 | 1.2666 | 0.096* | |
| C5 | 1.0345 (2) | 0.1356 (3) | 1.0416 (9) | 0.0831 (12) | |
| C6 | 1.0292 (3) | 0.0990 (3) | 0.8348 (9) | 0.0889 (13) | |
| H6 | 1.0755 | 0.0792 | 0.7816 | 0.107* | |
| C7 | 0.9552 (2) | 0.0914 (2) | 0.7048 (7) | 0.0792 (11) | |
| H7 | 0.9520 | 0.0673 | 0.5629 | 0.095* | |
| C8 | 0.7314 (2) | 0.1221 (2) | 0.7236 (7) | 0.0754 (11) | |
| H8 | 0.7343 | 0.1272 | 0.8762 | 0.090* | |
| C9 | 0.6615 (2) | 0.1233 (3) | 0.6088 (7) | 0.0872 (12) | |
| H9 | 0.6617 | 0.1225 | 0.4568 | 0.105* | |
| C10 | 0.5811 (2) | 0.1255 (3) | 0.6741 (6) | 0.0639 (9) | |
| C11 | 0.5655 (5) | 0.0979 (6) | 0.8724 (14) | 0.055 (2) | 0.500 (5) |
| H11 | 0.6076 | 0.0821 | 0.9821 | 0.065* | 0.500 (5) |
| C12 | 0.4860 (5) | 0.0928 (6) | 0.9147 (13) | 0.059 (2) | 0.500 (5) |
| H12 | 0.4773 | 0.0651 | 1.0463 | 0.070* | 0.500 (5) |
| C13 | 0.4234 (2) | 0.1232 (2) | 0.7863 (7) | 0.0639 (10) | |
| C14 | 0.4419 (4) | 0.1658 (5) | 0.5679 (11) | 0.057 (2) | 0.500 (5) |
| H14 | 0.4007 | 0.1885 | 0.4641 | 0.068* | 0.500 (5) |
| C15 | 0.5208 (4) | 0.1695 (5) | 0.5295 (12) | 0.059 (2) | 0.500 (5) |
| H15 | 0.5339 | 0.2012 | 0.4075 | 0.070* | 0.500 (5) |
| C16 | 0.2783 (5) | 0.0794 (8) | 0.7432 (18) | 0.103 (4) | 0.500 (5) |
| H16A | 0.2583 | 0.1102 | 0.6074 | 0.154* | 0.510 (7) |
| H16B | 0.2383 | 0.0815 | 0.8404 | 0.154* | 0.510 (7) |
| H16C | 0.2902 | 0.0166 | 0.7128 | 0.154* | 0.510 (7) |
| C17 | 0.3364 (5) | 0.1683 (7) | 1.0661 (13) | 0.106 (4) | 0.500 (5) |
| H17A | 0.3811 | 0.1526 | 1.1758 | 0.158* | 0.510 (7) |
| H17B | 0.2874 | 0.1466 | 1.1123 | 0.158* | 0.510 (7) |
| H17C | 0.3338 | 0.2337 | 1.0483 | 0.158* | 0.510 (7) |
| C11' | 0.5658 (5) | 0.1596 (6) | 0.8637 (16) | 0.060 (2) | 0.500 (5) |
| H11' | 0.6089 | 0.1842 | 0.9581 | 0.073* | 0.500 (5) |
| C12' | 0.4923 (4) | 0.1618 (6) | 0.9327 (12) | 0.060 (2) | 0.500 (5) |
| H12' | 0.4859 | 0.1870 | 1.0688 | 0.072* | 0.500 (5) |
| C14' | 0.4368 (4) | 0.0774 (5) | 0.6145 (12) | 0.059 (2) | 0.500 (5) |
| H14' | 0.3949 | 0.0445 | 0.5344 | 0.070* | 0.500 (5) |
| C15' | 0.5112 (4) | 0.0760 (5) | 0.5472 (12) | 0.064 (2) | 0.500 (5) |
| H15' | 0.5184 | 0.0436 | 0.4203 | 0.076* | 0.500 (5) |
| C16' | 0.2804 (4) | 0.1498 (7) | 0.6472 (14) | 0.090 (3) | 0.500 (5) |
| H16D | 0.2919 | 0.2095 | 0.5931 | 0.135* | 0.490 (7) |
| H16E | 0.2290 | 0.1509 | 0.6988 | 0.135* | 0.490 (7) |
| H16F | 0.2791 | 0.1056 | 0.5302 | 0.135* | 0.490 (7) |
| C17' | 0.3231 (5) | 0.0619 (6) | 0.9866 (13) | 0.079 (3) | 0.500 (5) |
| H17D | 0.3431 | 0.0019 | 0.9590 | 0.119* | 0.490 (7) |
| H17E | 0.2654 | 0.0604 | 0.9688 | 0.119* | 0.490 (7) |
| H17F | 0.3437 | 0.0804 | 1.1347 | 0.119* | 0.490 (7) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0640 (8) | 0.1472 (12) | 0.1697 (14) | −0.0010 (6) | 0.0012 (8) | −0.0022 (9) |
| N1 | 0.053 (2) | 0.084 (2) | 0.132 (3) | 0.0039 (18) | 0.021 (2) | −0.008 (3) |
| O1 | 0.085 (2) | 0.211 (4) | 0.078 (2) | 0.001 (2) | 0.0324 (18) | 0.006 (2) |
| C1 | 0.069 (3) | 0.072 (3) | 0.087 (3) | −0.0025 (19) | 0.033 (2) | 0.000 (2) |
| C2 | 0.061 (2) | 0.061 (2) | 0.089 (3) | −0.0045 (18) | 0.032 (2) | 0.003 (2) |
| C3 | 0.059 (3) | 0.080 (3) | 0.087 (3) | 0.0014 (18) | 0.024 (2) | −0.003 (2) |
| C4 | 0.074 (3) | 0.075 (3) | 0.094 (3) | −0.001 (2) | 0.022 (2) | −0.003 (2) |
| C5 | 0.060 (3) | 0.074 (3) | 0.118 (4) | 0.003 (2) | 0.023 (3) | 0.007 (3) |
| C6 | 0.071 (3) | 0.084 (3) | 0.120 (4) | 0.003 (2) | 0.043 (3) | −0.005 (3) |
| C7 | 0.074 (3) | 0.074 (3) | 0.097 (3) | 0.001 (2) | 0.037 (3) | −0.007 (2) |
| C8 | 0.062 (2) | 0.090 (3) | 0.077 (3) | −0.010 (2) | 0.021 (2) | −0.015 (2) |
| C9 | 0.071 (3) | 0.130 (3) | 0.063 (3) | 0.021 (2) | 0.018 (2) | 0.019 (2) |
| C10 | 0.058 (2) | 0.075 (2) | 0.059 (3) | 0.007 (2) | 0.0076 (19) | 0.001 (2) |
| C11 | 0.050 (5) | 0.057 (5) | 0.056 (6) | 0.007 (4) | 0.003 (4) | 0.004 (5) |
| C12 | 0.069 (6) | 0.057 (5) | 0.052 (5) | −0.006 (5) | 0.013 (4) | 0.000 (4) |
| C13 | 0.050 (2) | 0.054 (2) | 0.087 (3) | 0.0039 (19) | 0.005 (2) | −0.008 (2) |
| C14 | 0.057 (5) | 0.051 (5) | 0.058 (5) | 0.002 (3) | 0.000 (3) | 0.008 (3) |
| C15 | 0.066 (5) | 0.053 (5) | 0.058 (5) | −0.007 (4) | 0.012 (4) | 0.003 (3) |
| C16 | 0.076 (6) | 0.114 (8) | 0.118 (10) | −0.024 (6) | 0.015 (6) | −0.030 (7) |
| C17 | 0.071 (6) | 0.151 (9) | 0.098 (8) | −0.002 (5) | 0.025 (5) | −0.002 (6) |
| C11' | 0.053 (5) | 0.058 (6) | 0.067 (6) | −0.005 (5) | −0.001 (4) | −0.012 (5) |
| C12' | 0.058 (5) | 0.072 (6) | 0.051 (5) | −0.008 (5) | 0.011 (4) | −0.008 (4) |
| C14' | 0.047 (4) | 0.060 (6) | 0.067 (5) | −0.005 (3) | 0.000 (4) | −0.011 (4) |
| C15' | 0.067 (5) | 0.064 (6) | 0.060 (5) | 0.005 (4) | 0.008 (4) | −0.006 (4) |
| C16' | 0.049 (5) | 0.111 (8) | 0.105 (8) | −0.001 (5) | −0.001 (5) | 0.014 (6) |
| C17' | 0.076 (5) | 0.094 (7) | 0.071 (7) | 0.011 (5) | 0.023 (5) | 0.011 (5) |
| Cl1—C5 | 1.729 (4) | C11—H11 | 0.930 |
| N1—C17' | 1.353 (7) | C12—C13 | 1.296 (8) |
| N1—C13 | 1.370 (4) | C12—H12 | 0.930 |
| N1—C16 | 1.377 (7) | C13—C14' | 1.292 (7) |
| N1—C17 | 1.559 (7) | C13—C12' | 1.468 (8) |
| N1—C16' | 1.565 (7) | C13—C14 | 1.545 (8) |
| O1—C1 | 1.215 (4) | C14—C15 | 1.379 (8) |
| C1—C8 | 1.460 (5) | C14—H14 | 0.930 |
| C1—C2 | 1.486 (5) | C15—H15 | 0.930 |
| C2—C3 | 1.385 (5) | C16—H16A | 0.960 |
| C2—C7 | 1.391 (4) | C16—H16B | 0.960 |
| C3—C4 | 1.379 (5) | C16—H16C | 0.960 |
| C3—H3 | 0.930 | C17—H17A | 0.960 |
| C4—C5 | 1.376 (5) | C17—H17B | 0.960 |
| C4—H4 | 0.930 | C17—H17C | 0.960 |
| C5—C6 | 1.364 (5) | C11'—C12' | 1.362 (10) |
| C6—C7 | 1.380 (5) | C11'—H11' | 0.930 |
| C6—H6 | 0.930 | C12'—H12' | 0.930 |
| C7—H7 | 0.930 | C14'—C15' | 1.372 (9) |
| C8—C9 | 1.278 (5) | C14'—H14' | 0.930 |
| C8—H8 | 0.930 | C15'—H15' | 0.930 |
| C9—C10 | 1.463 (5) | C16'—H16D | 0.960 |
| C9—H9 | 0.930 | C16'—H16E | 0.960 |
| C10—C11' | 1.320 (9) | C16'—H16F | 0.960 |
| C10—C11 | 1.339 (9) | C17'—H17D | 0.960 |
| C10—C15 | 1.399 (8) | C17'—H17E | 0.960 |
| C10—C15' | 1.495 (8) | C17'—H17F | 0.960 |
| C11—C12 | 1.398 (10) | ||
| C17'—N1—C13 | 123.1 (5) | N1—C13—C12' | 122.2 (5) |
| C13—N1—C16 | 130.6 (5) | C12—C13—C14 | 114.4 (5) |
| C13—N1—C17 | 116.6 (4) | N1—C13—C14 | 122.0 (4) |
| C16—N1—C17 | 112.5 (5) | C15—C14—C13 | 118.8 (6) |
| C17'—N1—C16' | 114.4 (6) | C15—C14—H14 | 120.6 |
| C13—N1—C16' | 113.7 (5) | C13—C14—H14 | 120.6 |
| O1—C1—C8 | 120.0 (4) | C14—C15—C10 | 119.9 (6) |
| O1—C1—C2 | 119.6 (3) | C14—C15—H15 | 120.0 |
| C8—C1—C2 | 120.4 (4) | C10—C15—H15 | 120.0 |
| C3—C2—C7 | 118.0 (4) | N1—C16—H16A | 109.5 |
| C3—C2—C1 | 122.8 (3) | N1—C16—H16B | 109.5 |
| C7—C2—C1 | 119.2 (4) | H16A—C16—H16B | 109.5 |
| C4—C3—C2 | 121.1 (4) | N1—C16—H16C | 109.5 |
| C4—C3—H3 | 119.5 | H16A—C16—H16C | 109.5 |
| C2—C3—H3 | 119.5 | H16B—C16—H16C | 109.5 |
| C5—C4—C3 | 119.5 (4) | N1—C17—H17A | 109.5 |
| C5—C4—H4 | 120.2 | N1—C17—H17B | 109.5 |
| C3—C4—H4 | 120.2 | H17A—C17—H17B | 109.5 |
| C6—C5—C4 | 120.6 (4) | N1—C17—H17C | 109.5 |
| C6—C5—Cl1 | 120.5 (3) | H17A—C17—H17C | 109.5 |
| C4—C5—Cl1 | 118.9 (4) | H17B—C17—H17C | 109.5 |
| C5—C6—C7 | 119.8 (4) | C10—C11'—C12' | 125.5 (7) |
| C5—C6—H6 | 120.1 | C10—C11'—H11' | 117.2 |
| C7—C6—H6 | 120.1 | C12'—C11'—H11' | 117.2 |
| C6—C7—C2 | 120.9 (4) | C11'—C12'—C13 | 118.2 (7) |
| C6—C7—H7 | 119.6 | C11'—C12'—H12' | 120.9 |
| C2—C7—H7 | 119.6 | C13—C12'—H12' | 120.9 |
| C9—C8—C1 | 125.2 (4) | C13—C14'—C15' | 121.8 (6) |
| C9—C8—H8 | 117.4 | C13—C14'—H14' | 119.1 |
| C1—C8—H8 | 117.4 | C15'—C14'—H14' | 119.1 |
| C8—C9—C10 | 131.4 (4) | C14'—C15'—C10 | 121.1 (6) |
| C8—C9—H9 | 114.3 | C14'—C15'—H15' | 119.4 |
| C10—C9—H9 | 114.3 | C10—C15'—H15' | 119.4 |
| C11—C10—C15 | 119.4 (5) | N1—C16'—H16D | 109.5 |
| C11—C10—C9 | 123.4 (4) | N1—C16'—H16E | 109.5 |
| C15—C10—C9 | 116.7 (4) | H16D—C16'—H16E | 109.5 |
| C9—C10—C15' | 122.2 (4) | N1—C16'—H16F | 109.5 |
| C10—C11—C12 | 120.1 (6) | H16D—C16'—H16F | 109.5 |
| C10—C11—H11 | 120.0 | H16E—C16'—H16F | 109.5 |
| C12—C11—H11 | 120.0 | N1—C17'—H17D | 109.5 |
| C13—C12—C11 | 125.6 (7) | N1—C17'—H17E | 109.5 |
| C13—C12—H12 | 117.2 | H17D—C17'—H17E | 109.5 |
| C11—C12—H12 | 117.2 | N1—C17'—H17F | 109.5 |
| C14'—C13—N1 | 118.5 (4) | H17D—C17'—H17F | 109.5 |
| C12—C13—N1 | 123.5 (5) | H17E—C17'—H17F | 109.5 |
| C14'—C13—C12' | 118.6 (5) |
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This paper discloses a user-friendly, solvent-free protocol for the synthesis of chalcones, starting from the fragrant aldehydes and fragrant ketones in the presence of NaOH. The method can be considered to be a general route for chalcone synthesis, and the title compound was prepared in this way.
The bond lengths and angles of the molecule (Fig. 1) are normal and comparable to those observed in the related compound (Li et al., 1992). The (dimethylamino)phenyl group exhibits rotational disorder, with one orientation including atoms C10, C11, C12, C13, C14 and C15, and another orientation including C10, C11', C12', C13, C14' and C15'. The refined site occupancy factors for the two orientations is 0.500 (5).