organic compounds
(3E,5E)-3,5-Bis(2-chlorobenzylidene)-1-propylpiperidin-4-one
aSchool of Pharmacy, Wenzhou Medical College, Wenzhou, Zhejiang Province 325035, People's Republic of China
*Correspondence e-mail: wjzwzmc@126.com
The title compound, C22H21Cl2NO, is a derivative of mono-carbonyl analogues of curcumin (MACs). The molecule has an E conformation for each of the olefinic bonds. The 1-propylpiperidin-4-one ring has a distorted chair conformation with the ring N and the C and O atoms of the carbonyl group deviating from the mean plane of the remaining four ring C atoms by 0.682 (2), −0.134 (3) and −0.340 (4) Å, respectively. The dihedral angle between the benzene rings is 26.5 (1)°. In the crystal, molecules are connected by weak C—H⋯O and C—H⋯π interactions.
Related literature
For related structures, see: Agrawal & Mishra (2010); Liang et al. (2008, 2009); Wu et al. (2010, 2011); Zhao et al. (2010, 2012). For background to and applications of see: Agrawal & Mishra (2010); Wu et al. (2010, 2011); Zhao et al. (2012).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812049252/zq2188sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049252/zq2188Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812049252/zq2188Isup3.cml
The title compound was synthesized by aldol condensation between 1-propylpiperidin-4-one and 2-fluorobenzaldehyde. 1-Propylpiperidin-4-one (1 mmol) and 2-fluorobenzaldehyde (2.1 mmol) were dissolved in absolute ethyl alcohol (20 ml). When the temperature of solution was at 288 K by using ice-water bath, 5 drops of NaOH (40%) were added and the reaction solution became yellow. The reaction was monitored by
After the reaction was over, 20 ml H2O was added and the yellow solid was separated out. Precipitation was filtered and washed with mixture of cold ethanol and water (1:10). The production was purified by silica gel column elution solvent was the mixture of petroleum ether and ethyl acetate (4:1). The yield of production is 76.6%, and the melting point is in the range 397.35 – 401.05 K. The pure product was crystallized in the solution mixture of CH2Cl2 and CH3CH2OH.All H atoms were positioned geometrically and refined using a riding model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for the aromatic H atoms, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for the methylene H atoms, and with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for the methyl H atoms.
Curcumin is a natural drug isolated from turmeric. Curcumin possesses extensive biological activity such as anti-inflammatory, antioxidant, antitumor (Agrawal & Mishra, 2010; Zhao et al., 2012). However, its β-diketone moiety causes instability and poor bioavailability in body. Structural modification to prepare the analogues without the β-diketone moiety leads to mono-carbonyl analogues of curcumin (MACs) which are more stable and possess good pharmacokinetic profiles (Zhao et al., 2012). We synthesized a series of MACs in order to study antitumor and anti-inflammatory activities. In previous researches of our group, we reported the crystal structures of series of 5-carbon-linker mono-carbonyl analogues as following: 1,5-diaryl-1,4-pentadiene-3-ones, 2,6-(diarylidene)cyclohexanone, 2,5-(diarylidene)cyclopentanone (Liang et al., 2008, 2009; Wu et al., 2010, 2011; Zhao et al., 2010, 2012).
In this paper, we present the π interactions (Table 1).
of the title curcumin derivative, C22H21Cl2NO. The molecule has an E conformation for each of the olefinic bonds (Fig. 1). The 1-propylpiperidin-4-one ring has a distorted chair conformation: atoms N1, C1 and O1 deviate from the mean plane (C2-C3-C4-C5) by +0.682 (2), -0.134 (3) and -0.340 (4) Å, respectively. The dihedral angle between the phenyl rings C7-C12 and C14-C19 is 26.5 (1)°. In the crystal, molecules are connected by weak C—H···O and C–H···For related structures, see: Agrawal & Mishra (2010); Liang et al. (2008, 2009); Wu et al. (2010, 2011); Zhao et al. (2010, 2012). For background to and applications of
see: Agrawal & Mishra (2010); Wu et al. (2010, 2011); Zhao et al. (2012).Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SHELXTL (Sheldrick, 2008); 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).C22H21Cl2NO | F(000) = 808 |
Mr = 386.30 | Dx = 1.316 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 4766 reflections |
a = 18.0123 (15) Å | θ = 5.2–54.3° |
b = 7.0128 (6) Å | µ = 0.34 mm−1 |
c = 15.4364 (13) Å | T = 293 K |
V = 1949.9 (3) Å3 | Prismatic, green |
Z = 4 | 0.29 × 0.21 × 0.11 mm |
Bruker SMART CCD area-detector diffractometer | 3807 independent reflections |
Radiation source: fine-focus sealed tube | 3508 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −21→22 |
Tmin = 0.759, Tmax = 1.000 | k = −6→8 |
11133 measured reflections | l = −19→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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.0691P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3807 reflections | Δρmax = 0.22 e Å−3 |
236 parameters | Δρmin = −0.14 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1812 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (5) |
C22H21Cl2NO | V = 1949.9 (3) Å3 |
Mr = 386.30 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 18.0123 (15) Å | µ = 0.34 mm−1 |
b = 7.0128 (6) Å | T = 293 K |
c = 15.4364 (13) Å | 0.29 × 0.21 × 0.11 mm |
Bruker SMART CCD area-detector diffractometer | 3807 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3508 reflections with I > 2σ(I) |
Tmin = 0.759, Tmax = 1.000 | Rint = 0.031 |
11133 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.088 | Δρmax = 0.22 e Å−3 |
S = 1.04 | Δρmin = −0.14 e Å−3 |
3807 reflections | Absolute structure: Flack (1983), 1812 Friedel pairs |
236 parameters | Absolute structure parameter: 0.01 (5) |
1 restraint |
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 | ||
Cl1 | 0.78182 (4) | −0.45470 (9) | 0.63636 (5) | 0.0796 (2) | |
Cl2 | 0.37574 (3) | −0.55096 (7) | 0.88228 (4) | 0.06296 (16) | |
N1 | 0.56671 (8) | 0.1169 (2) | 0.77359 (10) | 0.0401 (3) | |
O1 | 0.63228 (8) | −0.3652 (2) | 0.89850 (10) | 0.0607 (4) | |
C1 | 0.61494 (10) | −0.2139 (3) | 0.86622 (12) | 0.0429 (4) | |
C2 | 0.53972 (9) | −0.1287 (2) | 0.88170 (12) | 0.0403 (4) | |
C3 | 0.52682 (10) | 0.0724 (3) | 0.85301 (11) | 0.0437 (4) | |
H3A | 0.4741 | 0.0920 | 0.8438 | 0.052* | |
H3B | 0.5427 | 0.1588 | 0.8984 | 0.052* | |
C4 | 0.64621 (10) | 0.0972 (3) | 0.78692 (14) | 0.0474 (4) | |
H4A | 0.6619 | 0.1817 | 0.8332 | 0.057* | |
H4B | 0.6722 | 0.1343 | 0.7345 | 0.057* | |
C5 | 0.66643 (9) | −0.1048 (3) | 0.80985 (12) | 0.0423 (4) | |
C6 | 0.72557 (10) | −0.1989 (3) | 0.78005 (13) | 0.0449 (4) | |
H6 | 0.7282 | −0.3274 | 0.7945 | 0.054* | |
C7 | 0.78713 (10) | −0.1247 (3) | 0.72710 (11) | 0.0426 (4) | |
C8 | 0.81962 (12) | 0.0505 (3) | 0.74401 (14) | 0.0541 (5) | |
H8 | 0.7998 | 0.1274 | 0.7873 | 0.065* | |
C9 | 0.88044 (12) | 0.1138 (4) | 0.69847 (16) | 0.0621 (6) | |
H9 | 0.9013 | 0.2317 | 0.7114 | 0.075* | |
C10 | 0.91043 (12) | 0.0031 (4) | 0.63378 (17) | 0.0639 (6) | |
H10 | 0.9516 | 0.0458 | 0.6031 | 0.077* | |
C11 | 0.87924 (12) | −0.1711 (4) | 0.61467 (15) | 0.0585 (5) | |
H11 | 0.8987 | −0.2461 | 0.5705 | 0.070* | |
C12 | 0.81917 (11) | −0.2330 (3) | 0.66148 (12) | 0.0477 (4) | |
C13 | 0.48853 (10) | −0.2435 (3) | 0.91708 (11) | 0.0416 (4) | |
H13 | 0.5036 | −0.3681 | 0.9278 | 0.050* | |
C14 | 0.41197 (10) | −0.1981 (3) | 0.94103 (11) | 0.0407 (4) | |
C15 | 0.39186 (13) | −0.0247 (3) | 0.97859 (13) | 0.0533 (5) | |
H15 | 0.4275 | 0.0699 | 0.9857 | 0.064* | |
C16 | 0.31982 (14) | 0.0090 (4) | 1.00541 (16) | 0.0658 (6) | |
H16 | 0.3074 | 0.1254 | 1.0303 | 0.079* | |
C17 | 0.26585 (13) | −0.1308 (4) | 0.99520 (16) | 0.0650 (6) | |
H17 | 0.2174 | −0.1081 | 1.0134 | 0.078* | |
C18 | 0.28397 (11) | −0.3015 (3) | 0.95846 (14) | 0.0548 (5) | |
H18 | 0.2481 | −0.3956 | 0.9516 | 0.066* | |
C19 | 0.35581 (10) | −0.3336 (3) | 0.93162 (12) | 0.0443 (4) | |
C20 | 0.54687 (11) | 0.3110 (3) | 0.74676 (12) | 0.0460 (4) | |
H20A | 0.5660 | 0.4001 | 0.7893 | 0.055* | |
H20B | 0.4932 | 0.3224 | 0.7465 | 0.055* | |
C21 | 0.57591 (14) | 0.3668 (3) | 0.65862 (15) | 0.0645 (6) | |
H21A | 0.6297 | 0.3709 | 0.6603 | 0.077* | |
H21B | 0.5614 | 0.2709 | 0.6166 | 0.077* | |
C22 | 0.54679 (16) | 0.5583 (3) | 0.63016 (19) | 0.0746 (7) | |
H22A | 0.4937 | 0.5525 | 0.6249 | 0.112* | |
H22B | 0.5681 | 0.5912 | 0.5751 | 0.112* | |
H22C | 0.5600 | 0.6531 | 0.6723 | 0.112* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0878 (4) | 0.0597 (4) | 0.0914 (4) | −0.0037 (3) | 0.0140 (4) | −0.0267 (3) |
Cl2 | 0.0552 (3) | 0.0512 (3) | 0.0825 (4) | −0.0052 (2) | 0.0007 (3) | −0.0101 (3) |
N1 | 0.0345 (7) | 0.0385 (7) | 0.0474 (7) | −0.0002 (6) | 0.0026 (6) | −0.0018 (6) |
O1 | 0.0486 (8) | 0.0557 (8) | 0.0777 (10) | 0.0103 (6) | 0.0083 (7) | 0.0159 (8) |
C1 | 0.0367 (9) | 0.0427 (9) | 0.0494 (10) | 0.0020 (7) | −0.0036 (7) | −0.0021 (8) |
C2 | 0.0364 (8) | 0.0445 (9) | 0.0399 (8) | 0.0012 (7) | 0.0007 (7) | −0.0042 (8) |
C3 | 0.0384 (9) | 0.0438 (9) | 0.0489 (10) | 0.0014 (7) | 0.0073 (7) | −0.0042 (7) |
C4 | 0.0351 (9) | 0.0475 (10) | 0.0596 (11) | −0.0032 (8) | 0.0020 (8) | −0.0013 (9) |
C5 | 0.0311 (9) | 0.0487 (10) | 0.0472 (9) | −0.0006 (7) | −0.0034 (7) | −0.0050 (8) |
C6 | 0.0365 (9) | 0.0485 (10) | 0.0496 (9) | 0.0005 (7) | −0.0017 (8) | −0.0029 (8) |
C7 | 0.0339 (9) | 0.0489 (10) | 0.0451 (9) | 0.0068 (7) | −0.0036 (7) | −0.0020 (8) |
C8 | 0.0389 (11) | 0.0635 (13) | 0.0600 (12) | −0.0005 (9) | −0.0006 (9) | −0.0133 (10) |
C9 | 0.0427 (11) | 0.0660 (13) | 0.0776 (15) | −0.0089 (10) | 0.0006 (10) | 0.0011 (12) |
C10 | 0.0419 (11) | 0.0811 (15) | 0.0688 (13) | −0.0005 (10) | 0.0107 (10) | 0.0121 (12) |
C11 | 0.0520 (12) | 0.0744 (15) | 0.0490 (10) | 0.0166 (10) | 0.0083 (9) | −0.0003 (10) |
C12 | 0.0417 (10) | 0.0518 (11) | 0.0495 (10) | 0.0078 (8) | −0.0044 (8) | −0.0035 (8) |
C13 | 0.0389 (9) | 0.0433 (9) | 0.0425 (9) | 0.0027 (7) | 0.0016 (7) | −0.0009 (7) |
C14 | 0.0400 (9) | 0.0430 (9) | 0.0391 (8) | 0.0054 (7) | 0.0028 (7) | 0.0062 (7) |
C15 | 0.0591 (12) | 0.0473 (11) | 0.0535 (11) | 0.0017 (9) | 0.0146 (10) | 0.0030 (9) |
C16 | 0.0690 (15) | 0.0582 (12) | 0.0703 (14) | 0.0132 (11) | 0.0272 (12) | 0.0026 (11) |
C17 | 0.0487 (12) | 0.0756 (15) | 0.0708 (14) | 0.0113 (11) | 0.0225 (11) | 0.0160 (12) |
C18 | 0.0394 (10) | 0.0651 (13) | 0.0598 (11) | −0.0013 (9) | 0.0070 (8) | 0.0163 (10) |
C19 | 0.0431 (9) | 0.0449 (10) | 0.0450 (9) | 0.0029 (8) | 0.0027 (8) | 0.0097 (8) |
C20 | 0.0436 (10) | 0.0434 (10) | 0.0508 (10) | 0.0028 (8) | 0.0052 (8) | −0.0024 (8) |
C21 | 0.0701 (15) | 0.0563 (13) | 0.0671 (13) | 0.0111 (10) | 0.0247 (12) | 0.0092 (10) |
C22 | 0.0879 (18) | 0.0614 (14) | 0.0746 (15) | 0.0123 (11) | 0.0157 (14) | 0.0184 (12) |
Cl1—C12 | 1.738 (2) | C10—H10 | 0.9300 |
Cl2—C19 | 1.741 (2) | C11—C12 | 1.372 (3) |
N1—C4 | 1.453 (2) | C11—H11 | 0.9300 |
N1—C3 | 1.455 (2) | C13—C14 | 1.463 (2) |
N1—C20 | 1.466 (2) | C13—H13 | 0.9300 |
O1—C1 | 1.213 (2) | C14—C15 | 1.395 (3) |
C1—C5 | 1.484 (3) | C14—C19 | 1.396 (3) |
C1—C2 | 1.500 (2) | C15—C16 | 1.382 (3) |
C2—C13 | 1.340 (2) | C15—H15 | 0.9300 |
C2—C3 | 1.497 (3) | C16—C17 | 1.390 (4) |
C3—H3A | 0.9700 | C16—H16 | 0.9300 |
C3—H3B | 0.9700 | C17—C18 | 1.364 (3) |
C4—C5 | 1.505 (3) | C17—H17 | 0.9300 |
C4—H4A | 0.9700 | C18—C19 | 1.377 (3) |
C4—H4B | 0.9700 | C18—H18 | 0.9300 |
C5—C6 | 1.335 (3) | C20—C21 | 1.509 (3) |
C6—C7 | 1.472 (3) | C20—H20A | 0.9700 |
C6—H6 | 0.9300 | C20—H20B | 0.9700 |
C7—C8 | 1.386 (3) | C21—C22 | 1.507 (3) |
C7—C12 | 1.391 (3) | C21—H21A | 0.9700 |
C8—C9 | 1.375 (3) | C21—H21B | 0.9700 |
C8—H8 | 0.9300 | C22—H22A | 0.9600 |
C9—C10 | 1.376 (4) | C22—H22B | 0.9600 |
C9—H9 | 0.9300 | C22—H22C | 0.9600 |
C10—C11 | 1.377 (3) | ||
C4—N1—C3 | 110.30 (15) | C11—C12—C7 | 122.6 (2) |
C4—N1—C20 | 111.63 (14) | C11—C12—Cl1 | 118.09 (16) |
C3—N1—C20 | 108.46 (14) | C7—C12—Cl1 | 119.35 (16) |
O1—C1—C5 | 122.06 (16) | C2—C13—C14 | 128.35 (17) |
O1—C1—C2 | 121.03 (17) | C2—C13—H13 | 115.8 |
C5—C1—C2 | 116.91 (15) | C14—C13—H13 | 115.8 |
C13—C2—C3 | 125.45 (16) | C15—C14—C19 | 116.66 (17) |
C13—C2—C1 | 116.55 (15) | C15—C14—C13 | 122.67 (18) |
C3—C2—C1 | 117.94 (15) | C19—C14—C13 | 120.57 (17) |
N1—C3—C2 | 112.02 (14) | C16—C15—C14 | 121.1 (2) |
N1—C3—H3A | 109.2 | C16—C15—H15 | 119.4 |
C2—C3—H3A | 109.2 | C14—C15—H15 | 119.4 |
N1—C3—H3B | 109.2 | C15—C16—C17 | 120.2 (2) |
C2—C3—H3B | 109.2 | C15—C16—H16 | 119.9 |
H3A—C3—H3B | 107.9 | C17—C16—H16 | 119.9 |
N1—C4—C5 | 111.19 (15) | C18—C17—C16 | 119.9 (2) |
N1—C4—H4A | 109.4 | C18—C17—H17 | 120.0 |
C5—C4—H4A | 109.4 | C16—C17—H17 | 120.0 |
N1—C4—H4B | 109.4 | C17—C18—C19 | 119.6 (2) |
C5—C4—H4B | 109.4 | C17—C18—H18 | 120.2 |
H4A—C4—H4B | 108.0 | C19—C18—H18 | 120.2 |
C6—C5—C1 | 116.51 (18) | C18—C19—C14 | 122.58 (18) |
C6—C5—C4 | 125.24 (17) | C18—C19—Cl2 | 117.92 (16) |
C1—C5—C4 | 118.16 (15) | C14—C19—Cl2 | 119.49 (14) |
C5—C6—C7 | 128.18 (18) | N1—C20—C21 | 114.26 (16) |
C5—C6—H6 | 115.9 | N1—C20—H20A | 108.7 |
C7—C6—H6 | 115.9 | C21—C20—H20A | 108.7 |
C8—C7—C12 | 116.48 (18) | N1—C20—H20B | 108.7 |
C8—C7—C6 | 121.77 (17) | C21—C20—H20B | 108.7 |
C12—C7—C6 | 121.59 (18) | H20A—C20—H20B | 107.6 |
C9—C8—C7 | 121.8 (2) | C22—C21—C20 | 111.92 (18) |
C9—C8—H8 | 119.1 | C22—C21—H21A | 109.2 |
C7—C8—H8 | 119.1 | C20—C21—H21A | 109.2 |
C8—C9—C10 | 120.1 (2) | C22—C21—H21B | 109.2 |
C8—C9—H9 | 119.9 | C20—C21—H21B | 109.2 |
C10—C9—H9 | 119.9 | H21A—C21—H21B | 107.9 |
C9—C10—C11 | 119.8 (2) | C21—C22—H22A | 109.5 |
C9—C10—H10 | 120.1 | C21—C22—H22B | 109.5 |
C11—C10—H10 | 120.1 | H22A—C22—H22B | 109.5 |
C12—C11—C10 | 119.3 (2) | C21—C22—H22C | 109.5 |
C12—C11—H11 | 120.3 | H22A—C22—H22C | 109.5 |
C10—C11—H11 | 120.3 | H22B—C22—H22C | 109.5 |
O1—C1—C2—C13 | −13.3 (3) | C10—C11—C12—C7 | 1.3 (3) |
C5—C1—C2—C13 | 166.64 (16) | C10—C11—C12—Cl1 | −179.34 (18) |
O1—C1—C2—C3 | 169.50 (17) | C8—C7—C12—C11 | −0.7 (3) |
C5—C1—C2—C3 | −10.6 (2) | C6—C7—C12—C11 | −176.22 (19) |
C4—N1—C3—C2 | −61.51 (19) | C8—C7—C12—Cl1 | 179.91 (15) |
C20—N1—C3—C2 | 175.95 (15) | C6—C7—C12—Cl1 | 4.4 (2) |
C13—C2—C3—N1 | −141.92 (17) | C3—C2—C13—C14 | −4.6 (3) |
C1—C2—C3—N1 | 35.0 (2) | C1—C2—C13—C14 | 178.42 (17) |
C3—N1—C4—C5 | 62.3 (2) | C2—C13—C14—C15 | −39.3 (3) |
C20—N1—C4—C5 | −177.01 (15) | C2—C13—C14—C19 | 144.50 (18) |
O1—C1—C5—C6 | 14.9 (3) | C19—C14—C15—C16 | 0.4 (3) |
C2—C1—C5—C6 | −164.98 (16) | C13—C14—C15—C16 | −175.87 (19) |
O1—C1—C5—C4 | −168.33 (18) | C14—C15—C16—C17 | 0.0 (3) |
C2—C1—C5—C4 | 11.8 (2) | C15—C16—C17—C18 | −0.1 (4) |
N1—C4—C5—C6 | 139.18 (19) | C16—C17—C18—C19 | −0.1 (3) |
N1—C4—C5—C1 | −37.3 (2) | C17—C18—C19—C14 | 0.5 (3) |
C1—C5—C6—C7 | −176.63 (18) | C17—C18—C19—Cl2 | −178.21 (17) |
C4—C5—C6—C7 | 6.9 (3) | C15—C14—C19—C18 | −0.7 (3) |
C5—C6—C7—C8 | 42.7 (3) | C13—C14—C19—C18 | 175.70 (17) |
C5—C6—C7—C12 | −142.0 (2) | C15—C14—C19—Cl2 | 178.04 (14) |
C12—C7—C8—C9 | −0.2 (3) | C13—C14—C19—Cl2 | −5.6 (2) |
C6—C7—C8—C9 | 175.4 (2) | C4—N1—C20—C21 | 66.3 (2) |
C7—C8—C9—C10 | 0.4 (4) | C3—N1—C20—C21 | −171.97 (18) |
C8—C9—C10—C11 | 0.1 (4) | N1—C20—C21—C22 | 173.6 (2) |
C9—C10—C11—C12 | −1.0 (4) |
Cg1 is the centroid of the C14–C19 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20A···O1i | 0.97 | 2.64 | 3.607 (3) | 174 |
C8—H8···Cg1ii | 0.93 | 2.89 | 3.568 | 131 |
C21—H21B···Cg1iii | 0.97 | 3.01 | 3.613 | 121 |
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y, z; (iii) −x+1, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C22H21Cl2NO |
Mr | 386.30 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 293 |
a, b, c (Å) | 18.0123 (15), 7.0128 (6), 15.4364 (13) |
V (Å3) | 1949.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.29 × 0.21 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.759, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11133, 3807, 3508 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.088, 1.04 |
No. of reflections | 3807 |
No. of parameters | 236 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.14 |
Absolute structure | Flack (1983), 1812 Friedel pairs |
Absolute structure parameter | 0.01 (5) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).
Cg1 is the centroid of the C14–C19 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20A···O1i | 0.97 | 2.64 | 3.607 (3) | 173.8 |
C8—H8···Cg1ii | 0.93 | 2.89 | 3.568 | 131 |
C21—H21B···Cg1iii | 0.97 | 3.01 | 3.613 | 121 |
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y, z; (iii) −x+1, −y, z−1/2. |
Acknowledgements
This study was partially supported by the Technology Foundation for Medical Science of Zhejiang Province (grant No. 2012KYA129) and University Students in Zhejiang Science and Technology Innovation Projects (grant No. 2012R413020). The authors are grateful to the associate researcher Sun Jie from Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, for testing and crystal analysis.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Curcumin is a natural drug isolated from turmeric. Curcumin possesses extensive biological activity such as anti-inflammatory, antioxidant, antitumor (Agrawal & Mishra, 2010; Zhao et al., 2012). However, its β-diketone moiety causes instability and poor bioavailability in body. Structural modification to prepare the analogues without the β-diketone moiety leads to mono-carbonyl analogues of curcumin (MACs) which are more stable and possess good pharmacokinetic profiles (Zhao et al., 2012). We synthesized a series of MACs in order to study antitumor and anti-inflammatory activities. In previous researches of our group, we reported the crystal structures of series of 5-carbon-linker mono-carbonyl analogues as following: 1,5-diaryl-1,4-pentadiene-3-ones, 2,6-(diarylidene)cyclohexanone, 2,5-(diarylidene)cyclopentanone (Liang et al., 2008, 2009; Wu et al., 2010, 2011; Zhao et al., 2010, 2012).
In this paper, we present the crystal structure of the title curcumin derivative, C22H21Cl2NO. The molecule has an E conformation for each of the olefinic bonds (Fig. 1). The 1-propylpiperidin-4-one ring has a distorted chair conformation: atoms N1, C1 and O1 deviate from the mean plane (C2-C3-C4-C5) by +0.682 (2), -0.134 (3) and -0.340 (4) Å, respectively. The dihedral angle between the phenyl rings C7-C12 and C14-C19 is 26.5 (1)°. In the crystal, molecules are connected by weak C—H···O and C–H···π interactions (Table 1).