organic compounds
1-[2,4,6-Trimethyl-3,5-bis(4-oxopiperidin-1-ylmethyl)benzyl]piperidin-4-one
aOrganic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, India, bMaterials Research Centre, Indian Institute of Science, Bengaluru 560 012, India, and cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: edward.tiekink@gmail.com
In the structure of the title compound, C27H39N3O3, each of the (4-oxopiperidin-1-yl)methyl residues adopts a flattened chair conformation (with the N and carbonyl groups being oriented to either side of the central C4 plane) and they occupy positions approximately orthogonal to the central benzene ring [Cbenzene—C—Cmethylene—N torsion angles 103.4 (2), −104.4 (3) and 71.9 (3)°]; further, two of these residues are oriented to one side of the central benzene ring with the third to the other side. In the crystal packing, supramolecular layers in the ab plane are sustained by C—H⋯O interactions.
Related literature
For background to the biological significance of piperidin-4-one and analogous pyran and thiopyran species, see: El-Subbagh et al. (2000); Ganellin et al. (1965); Hagenbach & Gysin (1952); Ileana et al. (1985); Mokio et al. (1989); Pathak et al. (2007). For a related structure, see: Vijayakumar et al. (2010).
Experimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536810016570/hg2682sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016570/hg2682Isup2.hkl
To a suspension of 1.5 equiv. of 4-piperidone hydrochloride monohydrate in benzene (20 ml), 3.0 equiv of K2CO3 was added. After stirring well for 30 min, 2,4,6-tris(bromomethyl)mesitylene (0.5 equiv) in benzene (10 ml) was added, followed by refluxing for 10 h. The completion of reaction was monitored by TLC. The reaction mixture was then allowed to cool to room temperature, filtered to remove the insoluble solids and then the filter cake was washed with dichloromethane. Excess solvents were removed under reduced pressure and the obtained crude product was purified by crystallization using 1:1 ratio of chloroform and methanol; m.pt. 483 K.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.96 to 0.97 Å) and were included in the
in the riding model approximation, with Uiso(H) set to 1.2–1.5Uequiv(C).Piperidin-4-one and their analogous pyran and thiopyran species attract interest owing to their biological properties, viz. anti-viral, anti-tumour (El-Subbagh et al., 2000), central nervous system (Ganellin et al., 1965), local anesthetic (Hagenbach et al., 1952), anti-cancer (Ileana et al., 1985), and anti-microbial (Mokio et al., 1989; Pathak et al., 2007) activities. As a continuation of structural studies of piperidine-4-ones (Vijayakumar et al., 2010), the title compound, (I), was synthesised and characterised by X-ray crystallography.
In compound (I), Fig. 1, the (4-oxopiperidin-1-yl)methyl residues containing the N1 and N2 atoms lie to one side of the central benzene ring and that with the N3 atom to the other. Owing to the presence of methyl substituents on either side of each 4-oxopiperidin-1-yl)methyl residue, the piperidin-4-one rings adopt side-on conformations to minimise steric interactions so that the N atoms occupy positions approximately normal to the plane through the benzene rings. This is quantified by the C2–C1–C7–N1 [103.4 (2) °], C2–C3–C14–N2 [-104.4 (3) °], and C4–C5–C21–N3 [71.9 (3) °] torsion angles. Each of the six-membered piperidin-4-one rings adopts a slightly flattened chair conformation with the N and carbonyl groups lying to either side of the central C4 plane in each case. Only the amine-N3 atom forms a significant intra- or inter-molecular interaction, i.e. an intramolecular C–H···N contact, Table 1. In the crystal packing, molecules are sustained into layers by C–H···O interactions; Table 1. Layers are formed in the ab plane and stack along the c axis, Fig. 2.
For background to the biological interest in piperidin-4-one and analogous pyran and thiopyran species, see: El-Subbagh et al. (2000); Ganellin et al. (1965); Hagenbach et al. (1952); Ileana et al. (1985); Mokio et al. (1989); Pathak et al. (2007). For a related structure, see: Vijayakumar et al. (2010).
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C27H39N3O3 | Z = 2 |
Mr = 453.61 | F(000) = 492 |
Triclinic, P1 | Dx = 1.180 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9315 (16) Å | Cell parameters from 969 reflections |
b = 12.449 (3) Å | θ = 2.9–21.9° |
c = 14.618 (3) Å | µ = 0.08 mm−1 |
α = 67.641 (3)° | T = 293 K |
β = 87.749 (4)° | Block, colourless |
γ = 73.630 (3)° | 0.28 × 0.21 × 0.17 mm |
V = 1277.0 (5) Å3 |
Bruker SMART APEX CCD diffractometer | 4490 independent reflections |
Radiation source: fine-focus sealed tube | 3008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −9→9 |
Tmin = 0.981, Tmax = 0.987 | k = −14→14 |
12284 measured reflections | l = −17→17 |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0929P)2 + 0.3308P] where P = (Fo2 + 2Fc2)/3 |
4490 reflections | (Δ/σ)max = 0.007 |
301 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C27H39N3O3 | γ = 73.630 (3)° |
Mr = 453.61 | V = 1277.0 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9315 (16) Å | Mo Kα radiation |
b = 12.449 (3) Å | µ = 0.08 mm−1 |
c = 14.618 (3) Å | T = 293 K |
α = 67.641 (3)° | 0.28 × 0.21 × 0.17 mm |
β = 87.749 (4)° |
Bruker SMART APEX CCD diffractometer | 4490 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 3008 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.987 | Rint = 0.026 |
12284 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.26 e Å−3 |
4490 reflections | Δρmin = −0.14 e Å−3 |
301 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | −0.1090 (3) | −0.3541 (2) | 0.4155 (2) | 0.1134 (9) | |
O2 | −0.5097 (3) | 0.4895 (2) | 0.2615 (2) | 0.1089 (8) | |
O3 | 1.1430 (3) | 0.1907 (3) | −0.0499 (2) | 0.1334 (11) | |
N1 | 0.2978 (2) | −0.20717 (17) | 0.36948 (14) | 0.0539 (5) | |
N2 | 0.0198 (2) | 0.35113 (19) | 0.26602 (16) | 0.0603 (6) | |
N3 | 0.6691 (2) | 0.18892 (18) | 0.05220 (14) | 0.0558 (5) | |
C1 | 0.4104 (3) | −0.0297 (2) | 0.33087 (17) | 0.0502 (6) | |
C2 | 0.3290 (3) | 0.0681 (2) | 0.35901 (17) | 0.0511 (6) | |
C3 | 0.3003 (3) | 0.1875 (2) | 0.29004 (19) | 0.0532 (6) | |
C4 | 0.3618 (3) | 0.2095 (2) | 0.19514 (18) | 0.0545 (6) | |
C5 | 0.4516 (3) | 0.1122 (2) | 0.16894 (17) | 0.0520 (6) | |
C6 | 0.4721 (3) | −0.0076 (2) | 0.23580 (18) | 0.0511 (6) | |
C7 | 0.4264 (3) | −0.1596 (2) | 0.39930 (19) | 0.0592 (7) | |
H7A | 0.5444 | −0.2101 | 0.3991 | 0.071* | |
H7B | 0.4088 | −0.1636 | 0.4664 | 0.071* | |
C8 | 0.3258 (3) | −0.3350 (2) | 0.4315 (2) | 0.0705 (8) | |
H8A | 0.3095 | −0.3439 | 0.4999 | 0.085* | |
H8B | 0.4462 | −0.3799 | 0.4284 | 0.085* | |
C9 | 0.1999 (4) | −0.3884 (3) | 0.3990 (3) | 0.0792 (9) | |
H9A | 0.2340 | −0.3963 | 0.3369 | 0.095* | |
H9B | 0.2100 | −0.4689 | 0.4483 | 0.095* | |
C10 | 0.0127 (4) | −0.3128 (3) | 0.3857 (2) | 0.0704 (8) | |
C11 | −0.0149 (3) | −0.1805 (2) | 0.3333 (2) | 0.0684 (7) | |
H11A | −0.1333 | −0.1373 | 0.3415 | 0.082* | |
H11B | −0.0036 | −0.1616 | 0.2630 | 0.082* | |
C12 | 0.1175 (3) | −0.1385 (2) | 0.37301 (19) | 0.0580 (6) | |
H12A | 0.1019 | −0.0531 | 0.3340 | 0.070* | |
H12B | 0.0960 | −0.1479 | 0.4410 | 0.070* | |
C13 | 0.2677 (3) | 0.0440 (3) | 0.46323 (19) | 0.0677 (7) | |
H13A | 0.1498 | 0.0375 | 0.4643 | 0.102* | |
H13B | 0.2698 | 0.1097 | 0.4819 | 0.102* | |
H13C | 0.3448 | −0.0303 | 0.5091 | 0.102* | |
C14 | 0.2003 (3) | 0.2953 (2) | 0.3141 (2) | 0.0655 (7) | |
H14A | 0.1946 | 0.2693 | 0.3854 | 0.079* | |
H14B | 0.2641 | 0.3556 | 0.2929 | 0.079* | |
C15 | −0.0916 (3) | 0.2725 (2) | 0.3062 (2) | 0.0587 (6) | |
H15A | −0.1012 | 0.2573 | 0.3761 | 0.070* | |
H15B | −0.0373 | 0.1953 | 0.3004 | 0.070* | |
C16 | −0.2748 (3) | 0.3271 (3) | 0.2531 (2) | 0.0770 (8) | |
H16A | −0.2675 | 0.3275 | 0.1866 | 0.092* | |
H16B | −0.3491 | 0.2767 | 0.2881 | 0.092* | |
C17 | −0.3573 (4) | 0.4534 (3) | 0.2471 (2) | 0.0750 (8) | |
C18 | −0.2391 (4) | 0.5317 (3) | 0.2223 (3) | 0.1045 (12) | |
H18A | −0.2927 | 0.6024 | 0.2380 | 0.125* | |
H18B | −0.2249 | 0.5597 | 0.1516 | 0.125* | |
C19 | −0.0583 (4) | 0.4656 (3) | 0.2789 (3) | 0.0860 (10) | |
H19A | 0.0189 | 0.5170 | 0.2551 | 0.103* | |
H19B | −0.0698 | 0.4493 | 0.3488 | 0.103* | |
C20 | 0.3263 (3) | 0.3379 (3) | 0.1196 (2) | 0.0757 (8) | |
H20A | 0.4242 | 0.3442 | 0.0792 | 0.114* | |
H20B | 0.3107 | 0.3926 | 0.1532 | 0.114* | |
H20C | 0.2214 | 0.3586 | 0.0784 | 0.114* | |
C21 | 0.5171 (3) | 0.1390 (3) | 0.06593 (18) | 0.0628 (7) | |
H21A | 0.5507 | 0.0648 | 0.0536 | 0.075* | |
H21B | 0.4215 | 0.1966 | 0.0174 | 0.075* | |
C22 | 0.6971 (4) | 0.2351 (3) | −0.0532 (2) | 0.0842 (10) | |
H22A | 0.5887 | 0.2925 | −0.0905 | 0.101* | |
H22B | 0.7295 | 0.1686 | −0.0758 | 0.101* | |
C23 | 0.8419 (4) | 0.2969 (4) | −0.0716 (3) | 0.1011 (12) | |
H23A | 0.8620 | 0.3253 | −0.1416 | 0.121* | |
H23B | 0.8064 | 0.3665 | −0.0530 | 0.121* | |
C24 | 1.0056 (4) | 0.2109 (3) | −0.0130 (2) | 0.0797 (9) | |
C25 | 0.9854 (3) | 0.1473 (3) | 0.0935 (2) | 0.0755 (8) | |
H25A | 0.9698 | 0.2031 | 0.1269 | 0.091* | |
H25B | 1.0913 | 0.0811 | 0.1235 | 0.091* | |
C26 | 0.8270 (3) | 0.0975 (2) | 0.1068 (2) | 0.0644 (7) | |
H26A | 0.8527 | 0.0309 | 0.0845 | 0.077* | |
H26B | 0.8071 | 0.0659 | 0.1767 | 0.077* | |
C27 | 0.5526 (3) | −0.1134 (3) | 0.2056 (2) | 0.0691 (8) | |
H27A | 0.4736 | −0.1128 | 0.1572 | 0.104* | |
H27B | 0.5726 | −0.1879 | 0.2628 | 0.104* | |
H27C | 0.6625 | −0.1067 | 0.1777 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0747 (14) | 0.0842 (16) | 0.159 (2) | −0.0394 (13) | 0.0274 (15) | −0.0133 (15) |
O2 | 0.0508 (12) | 0.1078 (18) | 0.160 (2) | −0.0044 (12) | 0.0228 (13) | −0.0575 (16) |
O3 | 0.0656 (14) | 0.245 (3) | 0.131 (2) | −0.0694 (18) | 0.0524 (14) | −0.105 (2) |
N1 | 0.0428 (10) | 0.0519 (12) | 0.0582 (12) | −0.0119 (9) | 0.0099 (9) | −0.0137 (10) |
N2 | 0.0401 (10) | 0.0613 (13) | 0.0751 (14) | −0.0127 (9) | 0.0124 (9) | −0.0238 (11) |
N3 | 0.0351 (10) | 0.0699 (13) | 0.0532 (12) | −0.0180 (9) | 0.0068 (8) | −0.0122 (10) |
C1 | 0.0308 (11) | 0.0641 (15) | 0.0553 (14) | −0.0161 (10) | 0.0028 (10) | −0.0210 (12) |
C2 | 0.0303 (11) | 0.0717 (17) | 0.0548 (14) | −0.0155 (11) | 0.0042 (10) | −0.0276 (13) |
C3 | 0.0307 (11) | 0.0663 (16) | 0.0676 (16) | −0.0172 (11) | 0.0049 (10) | −0.0288 (13) |
C4 | 0.0301 (11) | 0.0641 (16) | 0.0664 (16) | −0.0170 (11) | 0.0025 (10) | −0.0193 (13) |
C5 | 0.0289 (11) | 0.0755 (17) | 0.0561 (14) | −0.0225 (11) | 0.0062 (10) | −0.0251 (13) |
C6 | 0.0305 (11) | 0.0688 (16) | 0.0632 (15) | −0.0209 (11) | 0.0105 (10) | −0.0312 (13) |
C7 | 0.0401 (12) | 0.0672 (17) | 0.0615 (15) | −0.0099 (11) | 0.0024 (11) | −0.0191 (13) |
C8 | 0.0538 (15) | 0.0587 (17) | 0.0804 (19) | −0.0076 (13) | 0.0117 (13) | −0.0137 (14) |
C9 | 0.078 (2) | 0.0552 (17) | 0.100 (2) | −0.0240 (15) | 0.0208 (17) | −0.0225 (16) |
C10 | 0.0621 (17) | 0.0688 (18) | 0.0790 (19) | −0.0278 (14) | 0.0131 (14) | −0.0213 (15) |
C11 | 0.0518 (15) | 0.0663 (17) | 0.0783 (18) | −0.0207 (13) | 0.0024 (13) | −0.0157 (14) |
C12 | 0.0443 (13) | 0.0559 (15) | 0.0659 (16) | −0.0132 (11) | 0.0056 (11) | −0.0161 (12) |
C13 | 0.0547 (15) | 0.0854 (19) | 0.0636 (17) | −0.0163 (14) | 0.0091 (12) | −0.0327 (15) |
C14 | 0.0443 (14) | 0.0750 (18) | 0.0871 (19) | −0.0201 (13) | 0.0092 (13) | −0.0403 (15) |
C15 | 0.0414 (13) | 0.0625 (16) | 0.0712 (16) | −0.0131 (11) | 0.0062 (11) | −0.0262 (13) |
C16 | 0.0466 (15) | 0.087 (2) | 0.098 (2) | −0.0117 (14) | 0.0010 (14) | −0.0419 (18) |
C17 | 0.0468 (15) | 0.080 (2) | 0.085 (2) | −0.0035 (14) | 0.0067 (13) | −0.0281 (16) |
C18 | 0.0654 (19) | 0.064 (2) | 0.153 (3) | −0.0025 (16) | 0.018 (2) | −0.022 (2) |
C19 | 0.0603 (17) | 0.0647 (19) | 0.136 (3) | −0.0224 (15) | 0.0241 (18) | −0.0402 (19) |
C20 | 0.0501 (15) | 0.0744 (19) | 0.086 (2) | −0.0166 (13) | 0.0093 (14) | −0.0149 (16) |
C21 | 0.0425 (13) | 0.0917 (19) | 0.0569 (15) | −0.0282 (13) | 0.0075 (11) | −0.0257 (14) |
C22 | 0.0580 (16) | 0.116 (3) | 0.0561 (17) | −0.0340 (17) | 0.0056 (13) | −0.0031 (16) |
C23 | 0.079 (2) | 0.122 (3) | 0.086 (2) | −0.052 (2) | 0.0246 (18) | −0.008 (2) |
C24 | 0.0575 (17) | 0.123 (3) | 0.092 (2) | −0.0536 (18) | 0.0352 (16) | −0.060 (2) |
C25 | 0.0408 (14) | 0.105 (2) | 0.084 (2) | −0.0235 (14) | 0.0092 (13) | −0.0388 (18) |
C26 | 0.0408 (13) | 0.0757 (18) | 0.0666 (16) | −0.0169 (12) | 0.0054 (11) | −0.0166 (14) |
C27 | 0.0569 (15) | 0.0853 (19) | 0.0825 (19) | −0.0324 (14) | 0.0234 (14) | −0.0440 (16) |
O1—C10 | 1.209 (3) | C13—H13A | 0.9600 |
O2—C17 | 1.205 (3) | C13—H13B | 0.9600 |
O3—C24 | 1.202 (3) | C13—H13C | 0.9600 |
N1—C12 | 1.455 (3) | C14—H14A | 0.9700 |
N1—C8 | 1.457 (3) | C14—H14B | 0.9700 |
N1—C7 | 1.468 (3) | C15—C16 | 1.518 (3) |
N2—C15 | 1.447 (3) | C15—H15A | 0.9700 |
N2—C19 | 1.465 (3) | C15—H15B | 0.9700 |
N2—C14 | 1.474 (3) | C16—C17 | 1.493 (4) |
N3—C26 | 1.444 (3) | C16—H16A | 0.9700 |
N3—C22 | 1.457 (3) | C16—H16B | 0.9700 |
N3—C21 | 1.480 (3) | C17—C18 | 1.477 (4) |
C1—C6 | 1.407 (3) | C18—C19 | 1.526 (4) |
C1—C2 | 1.409 (3) | C18—H18A | 0.9700 |
C1—C7 | 1.515 (3) | C18—H18B | 0.9700 |
C2—C3 | 1.402 (3) | C19—H19A | 0.9700 |
C2—C13 | 1.524 (3) | C19—H19B | 0.9700 |
C3—C4 | 1.404 (3) | C20—H20A | 0.9600 |
C3—C14 | 1.513 (3) | C20—H20B | 0.9600 |
C4—C5 | 1.402 (3) | C20—H20C | 0.9600 |
C4—C20 | 1.511 (4) | C21—H21A | 0.9700 |
C5—C6 | 1.405 (3) | C21—H21B | 0.9700 |
C5—C21 | 1.517 (3) | C22—C23 | 1.516 (4) |
C6—C27 | 1.511 (3) | C22—H22A | 0.9700 |
C7—H7A | 0.9700 | C22—H22B | 0.9700 |
C7—H7B | 0.9700 | C23—C24 | 1.474 (5) |
C8—C9 | 1.522 (4) | C23—H23A | 0.9700 |
C8—H8A | 0.9700 | C23—H23B | 0.9700 |
C8—H8B | 0.9700 | C24—C25 | 1.480 (4) |
C9—C10 | 1.491 (4) | C25—C26 | 1.525 (3) |
C9—H9A | 0.9700 | C25—H25A | 0.9700 |
C9—H9B | 0.9700 | C25—H25B | 0.9700 |
C10—C11 | 1.482 (4) | C26—H26A | 0.9700 |
C11—C12 | 1.517 (3) | C26—H26B | 0.9700 |
C11—H11A | 0.9700 | C27—H27A | 0.9600 |
C11—H11B | 0.9700 | C27—H27B | 0.9600 |
C12—H12A | 0.9700 | C27—H27C | 0.9600 |
C12—H12B | 0.9700 | ||
C12—N1—C8 | 109.97 (18) | N2—C15—C16 | 112.2 (2) |
C12—N1—C7 | 111.77 (19) | N2—C15—H15A | 109.2 |
C8—N1—C7 | 110.82 (19) | C16—C15—H15A | 109.2 |
C15—N2—C19 | 109.09 (19) | N2—C15—H15B | 109.2 |
C15—N2—C14 | 112.1 (2) | C16—C15—H15B | 109.2 |
C19—N2—C14 | 109.6 (2) | H15A—C15—H15B | 107.9 |
C26—N3—C22 | 109.5 (2) | C17—C16—C15 | 112.2 (2) |
C26—N3—C21 | 111.39 (19) | C17—C16—H16A | 109.2 |
C22—N3—C21 | 108.5 (2) | C15—C16—H16A | 109.2 |
C6—C1—C2 | 120.0 (2) | C17—C16—H16B | 109.2 |
C6—C1—C7 | 118.4 (2) | C15—C16—H16B | 109.2 |
C2—C1—C7 | 121.5 (2) | H16A—C16—H16B | 107.9 |
C3—C2—C1 | 119.8 (2) | O2—C17—C18 | 122.0 (3) |
C3—C2—C13 | 120.1 (2) | O2—C17—C16 | 122.6 (3) |
C1—C2—C13 | 120.0 (2) | C18—C17—C16 | 115.4 (2) |
C2—C3—C4 | 120.0 (2) | C17—C18—C19 | 112.1 (3) |
C2—C3—C14 | 121.7 (2) | C17—C18—H18A | 109.2 |
C4—C3—C14 | 118.3 (2) | C19—C18—H18A | 109.2 |
C5—C4—C3 | 120.2 (2) | C17—C18—H18B | 109.2 |
C5—C4—C20 | 119.6 (2) | C19—C18—H18B | 109.2 |
C3—C4—C20 | 120.2 (2) | H18A—C18—H18B | 107.9 |
C4—C5—C6 | 120.0 (2) | N2—C19—C18 | 111.2 (3) |
C4—C5—C21 | 118.9 (2) | N2—C19—H19A | 109.4 |
C6—C5—C21 | 121.0 (2) | C18—C19—H19A | 109.4 |
C5—C6—C1 | 119.8 (2) | N2—C19—H19B | 109.4 |
C5—C6—C27 | 120.9 (2) | C18—C19—H19B | 109.4 |
C1—C6—C27 | 119.2 (2) | H19A—C19—H19B | 108.0 |
N1—C7—C1 | 112.09 (18) | C4—C20—H20A | 109.5 |
N1—C7—H7A | 109.2 | C4—C20—H20B | 109.5 |
C1—C7—H7A | 109.2 | H20A—C20—H20B | 109.5 |
N1—C7—H7B | 109.2 | C4—C20—H20C | 109.5 |
C1—C7—H7B | 109.2 | H20A—C20—H20C | 109.5 |
H7A—C7—H7B | 107.9 | H20B—C20—H20C | 109.5 |
N1—C8—C9 | 112.0 (2) | N3—C21—C5 | 113.1 (2) |
N1—C8—H8A | 109.2 | N3—C21—H21A | 108.9 |
C9—C8—H8A | 109.2 | C5—C21—H21A | 108.9 |
N1—C8—H8B | 109.2 | N3—C21—H21B | 108.9 |
C9—C8—H8B | 109.2 | C5—C21—H21B | 108.9 |
H8A—C8—H8B | 107.9 | H21A—C21—H21B | 107.8 |
C10—C9—C8 | 112.8 (2) | N3—C22—C23 | 110.2 (3) |
C10—C9—H9A | 109.0 | N3—C22—H22A | 109.6 |
C8—C9—H9A | 109.0 | C23—C22—H22A | 109.6 |
C10—C9—H9B | 109.0 | N3—C22—H22B | 109.6 |
C8—C9—H9B | 109.0 | C23—C22—H22B | 109.6 |
H9A—C9—H9B | 107.8 | H22A—C22—H22B | 108.1 |
O1—C10—C11 | 121.5 (3) | C24—C23—C22 | 109.8 (3) |
O1—C10—C9 | 123.7 (3) | C24—C23—H23A | 109.7 |
C11—C10—C9 | 114.8 (2) | C22—C23—H23A | 109.7 |
C10—C11—C12 | 111.3 (2) | C24—C23—H23B | 109.7 |
C10—C11—H11A | 109.4 | C22—C23—H23B | 109.7 |
C12—C11—H11A | 109.4 | H23A—C23—H23B | 108.2 |
C10—C11—H11B | 109.4 | O3—C24—C23 | 122.3 (3) |
C12—C11—H11B | 109.4 | O3—C24—C25 | 122.9 (3) |
H11A—C11—H11B | 108.0 | C23—C24—C25 | 114.8 (2) |
N1—C12—C11 | 111.6 (2) | C24—C25—C26 | 110.8 (2) |
N1—C12—H12A | 109.3 | C24—C25—H25A | 109.5 |
C11—C12—H12A | 109.3 | C26—C25—H25A | 109.5 |
N1—C12—H12B | 109.3 | C24—C25—H25B | 109.5 |
C11—C12—H12B | 109.3 | C26—C25—H25B | 109.5 |
H12A—C12—H12B | 108.0 | H25A—C25—H25B | 108.1 |
C2—C13—H13A | 109.5 | N3—C26—C25 | 112.1 (2) |
C2—C13—H13B | 109.5 | N3—C26—H26A | 109.2 |
H13A—C13—H13B | 109.5 | C25—C26—H26A | 109.2 |
C2—C13—H13C | 109.5 | N3—C26—H26B | 109.2 |
H13A—C13—H13C | 109.5 | C25—C26—H26B | 109.2 |
H13B—C13—H13C | 109.5 | H26A—C26—H26B | 107.9 |
N2—C14—C3 | 112.7 (2) | C6—C27—H27A | 109.5 |
N2—C14—H14A | 109.1 | C6—C27—H27B | 109.5 |
C3—C14—H14A | 109.1 | H27A—C27—H27B | 109.5 |
N2—C14—H14B | 109.1 | C6—C27—H27C | 109.5 |
C3—C14—H14B | 109.1 | H27A—C27—H27C | 109.5 |
H14A—C14—H14B | 107.8 | H27B—C27—H27C | 109.5 |
C6—C1—C2—C3 | 3.8 (3) | O1—C10—C11—C12 | 133.7 (3) |
C7—C1—C2—C3 | −173.44 (19) | C9—C10—C11—C12 | −45.6 (4) |
C6—C1—C2—C13 | −177.93 (19) | C8—N1—C12—C11 | −61.6 (3) |
C7—C1—C2—C13 | 4.8 (3) | C7—N1—C12—C11 | 174.8 (2) |
C1—C2—C3—C4 | −3.7 (3) | C10—C11—C12—N1 | 54.7 (3) |
C13—C2—C3—C4 | 178.0 (2) | C15—N2—C14—C3 | 68.0 (3) |
C1—C2—C3—C14 | 174.9 (2) | C19—N2—C14—C3 | −170.7 (2) |
C13—C2—C3—C14 | −3.3 (3) | C2—C3—C14—N2 | −104.4 (3) |
C2—C3—C4—C5 | 0.1 (3) | C4—C3—C14—N2 | 74.3 (3) |
C14—C3—C4—C5 | −178.57 (19) | C19—N2—C15—C16 | 61.4 (3) |
C2—C3—C4—C20 | 178.1 (2) | C14—N2—C15—C16 | −177.0 (2) |
C14—C3—C4—C20 | −0.6 (3) | N2—C15—C16—C17 | −51.2 (3) |
C3—C4—C5—C6 | 3.4 (3) | C15—C16—C17—O2 | −137.8 (3) |
C20—C4—C5—C6 | −174.6 (2) | C15—C16—C17—C18 | 42.1 (4) |
C3—C4—C5—C21 | −179.76 (19) | O2—C17—C18—C19 | 136.7 (3) |
C20—C4—C5—C21 | 2.2 (3) | C16—C17—C18—C19 | −43.1 (4) |
C4—C5—C6—C1 | −3.3 (3) | C15—N2—C19—C18 | −61.9 (3) |
C21—C5—C6—C1 | 179.92 (19) | C14—N2—C19—C18 | 175.0 (2) |
C4—C5—C6—C27 | 174.0 (2) | C17—C18—C19—N2 | 52.8 (4) |
C21—C5—C6—C27 | −2.8 (3) | C26—N3—C21—C5 | 71.4 (3) |
C2—C1—C6—C5 | −0.3 (3) | C22—N3—C21—C5 | −168.0 (2) |
C7—C1—C6—C5 | 177.04 (19) | C4—C5—C21—N3 | 71.9 (3) |
C2—C1—C6—C27 | −177.6 (2) | C6—C5—C21—N3 | −111.3 (2) |
C7—C1—C6—C27 | −0.3 (3) | C26—N3—C22—C23 | −63.1 (3) |
C12—N1—C7—C1 | −61.7 (3) | C21—N3—C22—C23 | 175.1 (3) |
C8—N1—C7—C1 | 175.3 (2) | N3—C22—C23—C24 | 57.7 (4) |
C6—C1—C7—N1 | −73.9 (2) | C22—C23—C24—O3 | 126.4 (3) |
C2—C1—C7—N1 | 103.4 (2) | C22—C23—C24—C25 | −50.7 (4) |
C12—N1—C8—C9 | 58.7 (3) | O3—C24—C25—C26 | −129.9 (3) |
C7—N1—C8—C9 | −177.2 (2) | C23—C24—C25—C26 | 47.2 (4) |
N1—C8—C9—C10 | −49.5 (3) | C22—N3—C26—C25 | 60.0 (3) |
C8—C9—C10—O1 | −135.9 (3) | C21—N3—C26—C25 | 180.0 (2) |
C8—C9—C10—C11 | 43.5 (4) | C24—C25—C26—N3 | −51.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20a···N3 | 0.96 | 2.46 | 3.184 (4) | 132 |
C9—H9a···O2i | 0.97 | 2.60 | 3.412 (5) | 142 |
C21—H21b···O3ii | 0.97 | 2.48 | 3.252 (4) | 136 |
Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C27H39N3O3 |
Mr | 453.61 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.9315 (16), 12.449 (3), 14.618 (3) |
α, β, γ (°) | 67.641 (3), 87.749 (4), 73.630 (3) |
V (Å3) | 1277.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.28 × 0.21 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.981, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12284, 4490, 3008 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.183, 1.02 |
No. of reflections | 4490 |
No. of parameters | 301 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.14 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20a···N3 | 0.96 | 2.46 | 3.184 (4) | 132 |
C9—H9a···O2i | 0.97 | 2.60 | 3.412 (5) | 142 |
C21—H21b···O3ii | 0.97 | 2.48 | 3.252 (4) | 136 |
Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y, z. |
Footnotes
‡Additional correspondence author, e-mail: kvpsvijayakumar@gmail.com.
Acknowledgements
VV is grateful to DST India for funding through the Young Scientist Scheme (Fast Track Proposal). TN acknowledges the establishment of the CCD facility under the IRHPA-DST programme at the Indian Institute of Science, Bangalore.
References
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El-Subbagh, H. I., Abu-Zaid, S. M., Mahran, M. A., Badria, F. A. & Alofaid, A. M. (2000). J. Med. Chem. 43, 2915–2921. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ganellin, C. R. & Spickett, R. G. (1965). J. Med. Chem. 8, 619–625. CrossRef CAS PubMed Web of Science Google Scholar
Hagenbach, R. E. & Gysin, H. (1952). Experimentia, 8, 184–187. CrossRef CAS Google Scholar
Ileana, B., Dobre, V. & Nicluescu-Duvaz, I. (1985). J. Prakt. Chem. 327, 667–674. Google Scholar
Mokio, I. G., Soldatenkov, A. T., Federov, V. O., Ageev, E. A., Sergeeva, N. D., Lin, S., Stashenku, E. E., Prostakov, N. S. & Andreeva, E. L. (1989). Khim. Farm. Zh. 23, 421–427. Google Scholar
Pathak, C., Karthikeyan, S., More, K. & Vijayakumar, V. (2007). Indian J. Heterocycl. Chem. 16, 295–296. CAS Google Scholar
Sheldrick, G. M. (1998). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vijayakumar, V., Rajesh, K., Suresh, J., Narasimhamurthy, T. & Lakshman, P. L. N. (2010). Acta Cryst. E66, o170. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43. Submitted. Google Scholar
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.
Piperidin-4-one and their analogous pyran and thiopyran species attract interest owing to their biological properties, viz. anti-viral, anti-tumour (El-Subbagh et al., 2000), central nervous system (Ganellin et al., 1965), local anesthetic (Hagenbach et al., 1952), anti-cancer (Ileana et al., 1985), and anti-microbial (Mokio et al., 1989; Pathak et al., 2007) activities. As a continuation of structural studies of piperidine-4-ones (Vijayakumar et al., 2010), the title compound, (I), was synthesised and characterised by X-ray crystallography.
In compound (I), Fig. 1, the (4-oxopiperidin-1-yl)methyl residues containing the N1 and N2 atoms lie to one side of the central benzene ring and that with the N3 atom to the other. Owing to the presence of methyl substituents on either side of each 4-oxopiperidin-1-yl)methyl residue, the piperidin-4-one rings adopt side-on conformations to minimise steric interactions so that the N atoms occupy positions approximately normal to the plane through the benzene rings. This is quantified by the C2–C1–C7–N1 [103.4 (2) °], C2–C3–C14–N2 [-104.4 (3) °], and C4–C5–C21–N3 [71.9 (3) °] torsion angles. Each of the six-membered piperidin-4-one rings adopts a slightly flattened chair conformation with the N and carbonyl groups lying to either side of the central C4 plane in each case. Only the amine-N3 atom forms a significant intra- or inter-molecular interaction, i.e. an intramolecular C–H···N contact, Table 1. In the crystal packing, molecules are sustained into layers by C–H···O interactions; Table 1. Layers are formed in the ab plane and stack along the c axis, Fig. 2.