1-Chloro-acetyl-2,6-bis-(2-chloro-phen-yl)-3,5-dimethyl-piperidin-4-one oxime.

In the title compound, C(21)H(21)Cl(3)N(2)O(2), the piperidine ring adopts a distorted boat conformation. One of the chloro-phenyl rings is almost perpendicular to the best plane through piperidine ring, making a dihedral angle of 88.7 (1)°, whereas the other ring is twisted by 71.8 (1)°. The crystal packing is stabilized by inter-molecular C-H⋯O, C-H⋯Cl and O-H⋯O inter-actions.

Related literature

For general background to piperidine derivatives, see: Perumal et al. (2001 ▶); Dimmock et al. (2001 ▶); Ravindran et al. (1991 ▶); Senthilkumar et al. (1992 ▶). For the synthesis of the title compound, see: Aridoss et al. (2007 ▶). For asymmetry parameters, see: Nardelli (1983 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C21H21Cl3N2O2

M = 439.75

Monoclinic,

a = 9.8147 (6) Å

b = 15.5929 (11) Å

c = 13.9498 (9) Å

β = 93.529 (4)°

V = 2130.8 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.45 mm−1

T = 293 K

0.23 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.903, T max = 0.927

10047 measured reflections

4689 independent reflections

4181 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.076

S = 1.03

4689 reflections

255 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), 2045 Friedel pairs

Flack parameter: 0.04 (4)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018489/bt5245sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018489/bt5245Isup2.hkl

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

C21H21Cl3N2O2	F(000) = 912
Mr = 439.75	Dx = 1.371 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1231 reflections
a = 9.8147 (6) Å	θ = 2.5–28.3°
b = 15.5929 (11) Å	µ = 0.45 mm−1
c = 13.9498 (9) Å	T = 293 K
β = 93.529 (4)°	Block, colorless
V = 2130.8 (2) Å3	0.23 × 0.19 × 0.17 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	4689 independent reflections
Radiation source: fine-focus sealed tube	4181 reflections with I > 2σ(I)
graphite	Rint = 0.019
ω and φ scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
Tmin = 0.903, Tmax = 0.927	k = −20→20
10047 measured reflections	l = −18→18

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)] = 0.031	H-atom parameters constrained
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0346P)2 + 0.6047P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4689 reflections	Δρmax = 0.20 e Å−3
255 parameters	Δρmin = −0.18 e Å−3
2 restraints	Absolute structure: Flack (1983), 2045 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.04 (4)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.88541 (8)	0.18026 (6)	0.71303 (5)	0.0929 (3)
Cl2	0.40087 (5)	0.06564 (4)	0.47110 (4)	0.05560 (15)
Cl3	1.07034 (7)	−0.00744 (6)	0.60948 (5)	0.0826 (2)
O1	0.57421 (15)	0.18007 (9)	0.60868 (9)	0.0470 (3)
O2	0.91903 (18)	0.31451 (10)	0.26625 (12)	0.0605 (4)
H2A	0.9746	0.3323	0.2295	0.091*
N1	0.71338 (13)	0.12798 (9)	0.49843 (9)	0.0296 (3)
C2	0.64401 (17)	0.18068 (11)	0.42143 (12)	0.0328 (3)
H2	0.5740	0.2141	0.4519	0.039*
C3	0.74830 (19)	0.24562 (13)	0.38710 (13)	0.0400 (4)
H3	0.7049	0.2779	0.3332	0.048*
C4	0.87049 (17)	0.19941 (13)	0.35168 (12)	0.0372 (4)
C5	0.89159 (17)	0.10640 (13)	0.37891 (12)	0.0365 (4)
H5	0.8338	0.0725	0.3334	0.044*
C6	0.84595 (16)	0.08546 (12)	0.48021 (11)	0.0326 (4)
H6	0.9157	0.1072	0.5274	0.039*
C7	0.67616 (17)	0.13972 (11)	0.58982 (12)	0.0334 (4)
C8	0.7634 (2)	0.10242 (15)	0.67283 (13)	0.0480 (5)
H8A	0.8093	0.0511	0.6523	0.058*
H8B	0.7066	0.0870	0.7247	0.058*
C9	0.56989 (17)	0.12926 (12)	0.34100 (11)	0.0343 (4)
C10	0.45857 (18)	0.07723 (13)	0.35647 (13)	0.0403 (4)
C11	0.3877 (2)	0.03212 (19)	0.28473 (16)	0.0584 (6)
H11	0.3146	−0.0027	0.2987	0.070*
C12	0.4266 (2)	0.0394 (2)	0.19198 (18)	0.0749 (8)
H12	0.3798	0.0094	0.1427	0.090*
C13	0.5331 (2)	0.0905 (2)	0.17247 (14)	0.0668 (7)
H13	0.5585	0.0956	0.1096	0.080*
C14	0.6050 (2)	0.13518 (15)	0.24530 (13)	0.0467 (5)
H14	0.6779	0.1698	0.2303	0.056*
C15	0.7918 (3)	0.30940 (15)	0.46641 (19)	0.0625 (6)
H15A	0.8360	0.2792	0.5196	0.094*
H15B	0.7127	0.3386	0.4873	0.094*
H15C	0.8539	0.3504	0.4421	0.094*
N16	0.95359 (17)	0.23024 (11)	0.29455 (11)	0.0465 (4)
C17	1.0382 (2)	0.07602 (18)	0.36986 (17)	0.0626 (7)
H17A	1.0663	0.0894	0.3069	0.094*
H17B	1.0430	0.0152	0.3799	0.094*
H17C	1.0974	0.1044	0.4172	0.094*
C18	0.83630 (18)	−0.01119 (13)	0.49265 (12)	0.0383 (4)
C19	0.9322 (2)	−0.05775 (16)	0.54924 (15)	0.0545 (6)
C20	0.9212 (3)	−0.14576 (19)	0.5596 (2)	0.0722 (8)
H20	0.9846	−0.1754	0.5993	0.087*
C21	0.8168 (3)	−0.18886 (17)	0.5115 (2)	0.0773 (9)
H21	0.8093	−0.2479	0.5186	0.093*
C22	0.7226 (3)	−0.14545 (15)	0.4525 (2)	0.0633 (6)
H22	0.6528	−0.1751	0.4187	0.076*
C23	0.7326 (2)	−0.05725 (13)	0.44401 (14)	0.0442 (4)
H23	0.6682	−0.0281	0.4047	0.053*

	U11	U22	U33	U12	U13	U23
Cl1	0.0956 (5)	0.1161 (7)	0.0641 (4)	−0.0307 (5)	−0.0182 (3)	−0.0161 (4)
Cl2	0.0480 (2)	0.0744 (4)	0.0455 (2)	−0.0132 (3)	0.01178 (18)	0.0075 (3)
Cl3	0.0570 (3)	0.1203 (6)	0.0682 (4)	0.0274 (4)	−0.0150 (3)	0.0165 (4)
O1	0.0603 (8)	0.0469 (8)	0.0361 (6)	0.0160 (7)	0.0201 (6)	−0.0008 (6)
O2	0.0812 (10)	0.0457 (9)	0.0588 (9)	−0.0093 (8)	0.0375 (8)	0.0098 (7)
N1	0.0321 (6)	0.0311 (7)	0.0265 (6)	0.0048 (6)	0.0077 (5)	0.0017 (6)
C2	0.0351 (7)	0.0332 (9)	0.0312 (7)	0.0075 (7)	0.0108 (6)	0.0053 (8)
C3	0.0492 (9)	0.0333 (9)	0.0389 (8)	0.0022 (8)	0.0157 (7)	0.0065 (8)
C4	0.0406 (9)	0.0426 (10)	0.0291 (7)	−0.0039 (8)	0.0081 (6)	−0.0013 (8)
C5	0.0358 (8)	0.0445 (11)	0.0302 (7)	0.0046 (8)	0.0108 (6)	0.0025 (8)
C6	0.0299 (7)	0.0418 (10)	0.0267 (7)	0.0050 (7)	0.0059 (6)	0.0018 (7)
C7	0.0424 (9)	0.0309 (9)	0.0280 (7)	−0.0008 (8)	0.0104 (6)	−0.0002 (7)
C8	0.0569 (11)	0.0593 (14)	0.0278 (8)	0.0018 (10)	0.0043 (7)	0.0017 (9)
C9	0.0350 (8)	0.0384 (10)	0.0297 (7)	0.0113 (8)	0.0043 (6)	0.0045 (8)
C10	0.0354 (8)	0.0479 (12)	0.0376 (8)	0.0073 (8)	0.0037 (7)	0.0014 (9)
C11	0.0411 (10)	0.0771 (17)	0.0569 (12)	−0.0041 (11)	0.0015 (9)	−0.0111 (12)
C12	0.0513 (12)	0.121 (2)	0.0518 (12)	0.0018 (15)	−0.0036 (10)	−0.0304 (15)
C13	0.0527 (12)	0.113 (2)	0.0341 (10)	0.0121 (14)	0.0031 (9)	−0.0081 (12)
C14	0.0440 (9)	0.0632 (14)	0.0332 (9)	0.0088 (9)	0.0047 (7)	0.0068 (9)
C15	0.0833 (16)	0.0416 (12)	0.0662 (14)	−0.0151 (12)	0.0334 (12)	−0.0112 (11)
N16	0.0512 (9)	0.0489 (10)	0.0408 (8)	−0.0070 (8)	0.0159 (7)	0.0031 (8)
C17	0.0455 (11)	0.0840 (18)	0.0611 (12)	0.0212 (12)	0.0255 (10)	0.0193 (13)
C18	0.0403 (8)	0.0427 (10)	0.0332 (8)	0.0137 (9)	0.0121 (7)	0.0077 (8)
C19	0.0533 (11)	0.0663 (15)	0.0452 (10)	0.0238 (11)	0.0137 (9)	0.0159 (11)
C20	0.0852 (19)	0.0641 (17)	0.0700 (16)	0.0433 (16)	0.0252 (14)	0.0256 (14)
C21	0.100 (2)	0.0420 (14)	0.095 (2)	0.0247 (15)	0.0457 (18)	0.0173 (15)
C22	0.0753 (15)	0.0421 (13)	0.0755 (15)	0.0036 (12)	0.0277 (13)	−0.0037 (12)
C23	0.0492 (10)	0.0376 (11)	0.0473 (10)	0.0089 (9)	0.0137 (8)	0.0043 (9)

Cl1—C8	1.772 (2)	C9—C14	1.402 (2)
Cl2—C10	1.7383 (18)	C10—C11	1.377 (3)
Cl3—C19	1.738 (3)	C11—C12	1.376 (3)
O1—C7	1.224 (2)	C11—H11	0.9300
O2—N16	1.408 (2)	C12—C13	1.355 (4)
O2—H2A	0.8200	C12—H12	0.9300
N1—C7	1.360 (2)	C13—C14	1.388 (3)
N1—C2	1.484 (2)	C13—H13	0.9300
N1—C6	1.496 (2)	C14—H14	0.9300
C2—C9	1.527 (3)	C15—H15A	0.9600
C2—C3	1.537 (2)	C15—H15B	0.9600
C2—H2	0.9800	C15—H15C	0.9600
C3—C4	1.508 (2)	C17—H17A	0.9600
C3—C15	1.529 (3)	C17—H17B	0.9600
C3—H3	0.9800	C17—H17C	0.9600
C4—N16	1.269 (2)	C18—C23	1.388 (3)
C4—C5	1.510 (3)	C18—C19	1.394 (3)
C5—C17	1.527 (3)	C19—C20	1.385 (4)
C5—C6	1.543 (2)	C20—C21	1.367 (4)
C5—H5	0.9800	C20—H20	0.9300
C6—C18	1.521 (3)	C21—C22	1.377 (4)
C6—H6	0.9800	C21—H21	0.9300
C7—C8	1.513 (3)	C22—C23	1.384 (3)
C8—H8A	0.9700	C22—H22	0.9300
C8—H8B	0.9700	C23—H23	0.9300
C9—C10	1.388 (3)
N16—O2—H2A	109.5	C9—C10—Cl2	120.52 (14)
C7—N1—C2	117.79 (13)	C12—C11—C10	118.9 (2)
C7—N1—C6	120.37 (13)	C12—C11—H11	120.5
C2—N1—C6	119.18 (12)	C10—C11—H11	120.5
N1—C2—C9	114.70 (14)	C13—C12—C11	120.0 (2)
N1—C2—C3	107.79 (14)	C13—C12—H12	120.0
C9—C2—C3	114.42 (14)	C11—C12—H12	120.0
N1—C2—H2	106.4	C12—C13—C14	120.8 (2)
C9—C2—H2	106.4	C12—C13—H13	119.6
C3—C2—H2	106.4	C14—C13—H13	119.6
C4—C3—C15	110.84 (17)	C13—C14—C9	121.3 (2)
C4—C3—C2	110.21 (15)	C13—C14—H14	119.3
C15—C3—C2	111.38 (15)	C9—C14—H14	119.3
C4—C3—H3	108.1	C3—C15—H15A	109.5
C15—C3—H3	108.1	C3—C15—H15B	109.5
C2—C3—H3	108.1	H15A—C15—H15B	109.5
N16—C4—C3	125.40 (18)	C3—C15—H15C	109.5
N16—C4—C5	115.98 (16)	H15A—C15—H15C	109.5
C3—C4—C5	118.42 (14)	H15B—C15—H15C	109.5
C4—C5—C17	113.10 (16)	C4—N16—O2	112.12 (16)
C4—C5—C6	112.98 (14)	C5—C17—H17A	109.5
C17—C5—C6	109.75 (15)	C5—C17—H17B	109.5
C4—C5—H5	106.9	H17A—C17—H17B	109.5
C17—C5—H5	106.9	C5—C17—H17C	109.5
C6—C5—H5	106.9	H17A—C17—H17C	109.5
N1—C6—C18	111.03 (13)	H17B—C17—H17C	109.5
N1—C6—C5	111.49 (13)	C23—C18—C19	117.14 (19)
C18—C6—C5	109.74 (14)	C23—C18—C6	120.39 (16)
N1—C6—H6	108.2	C19—C18—C6	122.42 (19)
C18—C6—H6	108.2	C20—C19—C18	121.4 (2)
C5—C6—H6	108.2	C20—C19—Cl3	117.39 (19)
O1—C7—N1	122.74 (16)	C18—C19—Cl3	121.19 (18)
O1—C7—C8	117.68 (15)	C21—C20—C19	119.8 (2)
N1—C7—C8	119.57 (15)	C21—C20—H20	120.1
C7—C8—Cl1	108.57 (15)	C19—C20—H20	120.1
C7—C8—H8A	110.0	C20—C21—C22	120.5 (2)
Cl1—C8—H8A	110.0	C20—C21—H21	119.8
C7—C8—H8B	110.0	C22—C21—H21	119.8
Cl1—C8—H8B	110.0	C21—C22—C23	119.4 (3)
H8A—C8—H8B	108.4	C21—C22—H22	120.3
C10—C9—C14	115.36 (17)	C23—C22—H22	120.3
C10—C9—C2	122.45 (14)	C22—C23—C18	121.7 (2)
C14—C9—C2	122.10 (17)	C22—C23—H23	119.1
C11—C10—C9	123.57 (17)	C18—C23—H23	119.1
C11—C10—Cl2	115.90 (15)
C7—N1—C2—C9	−121.63 (16)	C3—C2—C9—C10	−170.16 (16)
C6—N1—C2—C9	76.79 (18)	N1—C2—C9—C14	−119.16 (18)
C7—N1—C2—C3	109.65 (16)	C3—C2—C9—C14	6.2 (2)
C6—N1—C2—C3	−51.92 (19)	C14—C9—C10—C11	1.6 (3)
N1—C2—C3—C4	58.14 (18)	C2—C9—C10—C11	178.1 (2)
C9—C2—C3—C4	−70.73 (19)	C14—C9—C10—Cl2	−178.56 (15)
N1—C2—C3—C15	−65.3 (2)	C2—C9—C10—Cl2	−2.0 (2)
C9—C2—C3—C15	165.81 (17)	C9—C10—C11—C12	−1.1 (4)
C15—C3—C4—N16	−77.9 (2)	Cl2—C10—C11—C12	179.0 (2)
C2—C3—C4—N16	158.32 (18)	C10—C11—C12—C13	0.0 (4)
C15—C3—C4—C5	107.4 (2)	C11—C12—C13—C14	0.6 (4)
C2—C3—C4—C5	−16.4 (2)	C12—C13—C14—C9	−0.1 (4)
N16—C4—C5—C17	24.7 (2)	C10—C9—C14—C13	−1.0 (3)
C3—C4—C5—C17	−160.10 (18)	C2—C9—C14—C13	−177.52 (19)
N16—C4—C5—C6	150.15 (16)	C3—C4—N16—O2	−0.2 (3)
C3—C4—C5—C6	−34.6 (2)	C5—C4—N16—O2	174.59 (16)
C7—N1—C6—C18	77.29 (19)	N1—C6—C18—C23	52.7 (2)
C2—N1—C6—C18	−121.62 (16)	C5—C6—C18—C23	−71.05 (19)
C7—N1—C6—C5	−160.01 (15)	N1—C6—C18—C19	−129.93 (16)
C2—N1—C6—C5	1.1 (2)	C5—C6—C18—C19	106.36 (18)
C4—C5—C6—N1	42.4 (2)	C23—C18—C19—C20	−2.6 (3)
C17—C5—C6—N1	169.59 (18)	C6—C18—C19—C20	179.90 (18)
C4—C5—C6—C18	165.79 (15)	C23—C18—C19—Cl3	177.34 (14)
C17—C5—C6—C18	−67.0 (2)	C6—C18—C19—Cl3	−0.2 (2)
C2—N1—C7—O1	12.7 (2)	C18—C19—C20—C21	1.9 (3)
C6—N1—C7—O1	174.07 (17)	Cl3—C19—C20—C21	−178.02 (19)
C2—N1—C7—C8	−166.86 (16)	C19—C20—C21—C22	0.2 (4)
C6—N1—C7—C8	−5.5 (2)	C20—C21—C22—C23	−1.5 (4)
O1—C7—C8—Cl1	−88.46 (18)	C21—C22—C23—C18	0.7 (3)
N1—C7—C8—Cl1	91.14 (18)	C19—C18—C23—C22	1.3 (3)
N1—C2—C9—C10	64.5 (2)	C6—C18—C23—C22	178.83 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1i	0.82	2.01	2.7515 (18)	150
C12—H12···Cl2ii	0.93	2.68	3.485 (3)	145
C20—H20···O1iii	0.93	2.42	3.158 (3)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1i	0.82	2.01	2.7515 (18)	150
C12—H12⋯Cl2ii	0.93	2.68	3.485 (3)	145
C20—H20⋯O1iii	0.93	2.42	3.158 (3)	136

Symmetry codes: (i) ; (ii) ; (iii) .