Crystal structure of 2-[4(E)-2,6-bis-(4-chloro-phen-yl)-3-ethyl-piperidin-4-yl-idene]acetamide.

In the title piperidine derivative, C21H22Cl2N2O, the piperidine ring adopts a chair conformation. The chloro-phenyl rings are oriented at an angle of 45.59 (14)° with respect to each other. In the crystal, mol-ecules are linked via N-H⋯O hydrogen bonds, forming C(4) chains along [100]. The chains are linked by C-H⋯O hydrogen bonds, forming sheets parallel to the ab plane. Within the sheets, there are N-H⋯π inter-actions present. The crystal studied was refined as an inversion twin.

Related literature

For background to piperidienes, their properties and syntheses, see: Deopura et al. (2008 ▸); Greenberg et al. (2000 ▸); Johnsson (2004 ▸); Katritzky et al. (1989 ▸); Kornblum & Singaram (1979 ▸); Moorthy & Singhal (2005 ▸); Prostakov & Gaivoronskaya (1978 ▸); Yu et al. (2002 ▸); Zabicky (1970 ▸).

Experimental

Crystal data

C21H22Cl2N2O

M = 389.30

Orthorhombic,

a = 8.3293 (2) Å

b = 12.2924 (3) Å

c = 19.3226 (4) Å

V = 1978.39 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.34 mm−1

T = 296 K

0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

31733 measured reflections

4427 independent reflections

4220 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.097

S = 1.04

4427 reflections

248 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.30 e Å−3

Absolute structure: Refined as an inversion twin

Absolute structure parameter: 0.37 (7)

Data collection: SMART (Bruker, 2001 ▸); cell refinement: SAINT (Bruker, 2001 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL2014/7 and PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015018666/su5218sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018666/su5218Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015018666/su5218fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015018666/su5218fig2.tif

Crystal packing of the title compound, viewed along the c axis. The N—H⋯O and C-H⋯O hydrogen bonds are shown as dashed lines (see Table 1). For clarity H atoms not involved in these hydrogen bonds have been omitted.

Click here for additional data file.

. DOI: 10.1107/S2056989015018666/su5218fig3.tif

Crystal packing of the title compound, showing the N—H⋯π inter­actions as dashed lines (see Table 1). For clarity H atoms not involved in these inter­actions have been omitted.

CCDC reference: 1064003

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H22Cl2N2O	Dx = 1.307 Mg m−3
Mr = 389.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 24148 reflections
a = 8.3293 (2) Å	θ = 2.2–27.4°
b = 12.2924 (3) Å	µ = 0.34 mm−1
c = 19.3226 (4) Å	T = 296 K
V = 1978.39 (8) Å3	Block, colourless
Z = 4	0.22 × 0.20 × 0.18 mm
F(000) = 816

Bruker SMART APEX CCD area-detector diffractometer	Rint = 0.022
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 2.0°
ω scans	h = −10→10
31733 measured reflections	k = −15→15
4427 independent reflections	l = −25→23
4220 reflections with I > 2σ(I)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0559P)2 + 0.4463P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
4427 reflections	Δρmax = 0.40 e Å−3
248 parameters	Δρmin = −0.29 e Å−3
4 restraints	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.37 (7)

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. Refined as a 2-component inversion twin

	x	y	z	Uiso*/Ueq
Cl1	0.04419 (14)	0.50344 (7)	0.45059 (5)	0.0738 (3)
Cl2	0.93853 (17)	0.89463 (11)	−0.00442 (7)	0.1046 (5)
O1	−0.1377 (2)	1.14174 (17)	0.30563 (13)	0.0563 (5)
N1	0.3564 (2)	0.88167 (15)	0.23773 (11)	0.0350 (4)
N2	0.0334 (3)	1.2760 (2)	0.33460 (15)	0.0547 (6)
C1	0.1001 (3)	0.6176 (2)	0.40293 (14)	0.0424 (6)
C2	0.0568 (4)	0.7187 (2)	0.42740 (14)	0.0464 (6)
H2	−0.0033	0.7254	0.4677	0.056*
C3	0.1046 (3)	0.8104 (2)	0.39085 (14)	0.0432 (5)
H3	0.0799	0.8791	0.4080	0.052*
C4	0.1888 (3)	0.80111 (17)	0.32911 (12)	0.0323 (4)
C5	0.2270 (3)	0.69817 (19)	0.30503 (13)	0.0358 (5)
H5	0.2818	0.6907	0.2634	0.043*
C6	0.1841 (3)	0.60526 (19)	0.34250 (14)	0.0402 (5)
H6	0.2122	0.5364	0.3267	0.048*
C7	0.2364 (3)	0.90357 (17)	0.29068 (12)	0.0332 (5)
H7	0.2824	0.9549	0.3241	0.040*
C8	0.0906 (3)	0.95793 (18)	0.25622 (14)	0.0361 (5)
H8A	0.0433	0.9093	0.2224	0.043*
H8B	0.0099	0.9751	0.2907	0.043*
C9	0.1484 (2)	1.06071 (18)	0.22138 (13)	0.0336 (5)
C10	0.2759 (2)	1.03897 (18)	0.16737 (12)	0.0328 (4)
H10	0.2308	0.9871	0.1341	0.039*
C11	0.4174 (2)	0.98078 (18)	0.20494 (13)	0.0326 (4)
H11	0.4597	1.0292	0.2409	0.039*
C12	0.5523 (2)	0.95166 (19)	0.15563 (13)	0.0346 (5)
C13	0.6907 (3)	1.0149 (2)	0.15428 (18)	0.0477 (6)
H13	0.7032	1.0707	0.1864	0.057*
C14	0.8102 (3)	0.9962 (3)	0.1058 (2)	0.0583 (8)
H14	0.9014	1.0398	0.1047	0.070*
C15	0.7925 (4)	0.9128 (3)	0.05980 (18)	0.0587 (8)
C16	0.6613 (4)	0.8458 (3)	0.06195 (18)	0.0600 (8)
H16	0.6530	0.7874	0.0315	0.072*
C17	0.5407 (3)	0.8655 (2)	0.10996 (16)	0.0470 (6)
H17	0.4512	0.8204	0.1114	0.056*
C18	0.3314 (3)	1.1388 (2)	0.12639 (14)	0.0401 (5)
H18A	0.3625	1.1955	0.1586	0.048*
H18B	0.4255	1.1194	0.0995	0.048*
C19	0.2027 (4)	1.1833 (2)	0.07772 (17)	0.0519 (7)
H19A	0.2440	1.2455	0.0535	0.078*
H19B	0.1731	1.1282	0.0449	0.078*
H19C	0.1100	1.2043	0.1041	0.078*
C20	0.1091 (3)	1.16038 (19)	0.24254 (13)	0.0368 (5)
H20	0.1610	1.2180	0.2208	0.044*
C21	−0.0092 (3)	1.18930 (19)	0.29731 (14)	0.0393 (5)
H1N	0.430 (3)	0.850 (3)	0.2575 (17)	0.050 (9)*
H2NA	−0.032 (3)	1.298 (3)	0.3633 (15)	0.047 (9)*
H2NB	0.125 (2)	1.301 (3)	0.334 (2)	0.066 (11)*

	U11	U22	U33	U12	U13	U23
Cl1	0.1153 (8)	0.0524 (4)	0.0536 (4)	−0.0239 (4)	0.0060 (5)	0.0144 (3)
Cl2	0.1058 (8)	0.1019 (8)	0.1062 (9)	0.0398 (7)	0.0651 (8)	0.0203 (7)
O1	0.0416 (10)	0.0438 (10)	0.0835 (16)	0.0000 (8)	0.0188 (10)	−0.0017 (10)
N1	0.0271 (9)	0.0326 (9)	0.0453 (11)	0.0044 (7)	−0.0004 (8)	0.0075 (8)
N2	0.0546 (14)	0.0479 (13)	0.0615 (16)	−0.0027 (11)	0.0157 (13)	−0.0105 (12)
C1	0.0502 (14)	0.0401 (12)	0.0370 (13)	−0.0066 (10)	−0.0053 (11)	0.0088 (10)
C2	0.0533 (14)	0.0520 (15)	0.0339 (12)	0.0017 (12)	0.0073 (11)	0.0025 (10)
C3	0.0492 (14)	0.0391 (12)	0.0413 (13)	0.0082 (10)	0.0035 (11)	−0.0012 (10)
C4	0.0303 (9)	0.0321 (10)	0.0345 (11)	0.0019 (8)	−0.0046 (9)	0.0032 (8)
C5	0.0326 (10)	0.0372 (11)	0.0375 (12)	−0.0005 (9)	0.0011 (9)	−0.0016 (9)
C6	0.0454 (13)	0.0317 (11)	0.0436 (13)	−0.0005 (9)	−0.0047 (11)	−0.0017 (9)
C7	0.0315 (10)	0.0293 (10)	0.0387 (12)	−0.0006 (8)	−0.0021 (9)	0.0009 (8)
C8	0.0265 (9)	0.0305 (10)	0.0514 (14)	0.0017 (8)	0.0029 (9)	0.0078 (9)
C9	0.0247 (9)	0.0319 (10)	0.0443 (12)	0.0013 (8)	−0.0018 (9)	0.0068 (9)
C10	0.0271 (9)	0.0308 (9)	0.0406 (12)	0.0001 (8)	−0.0003 (8)	0.0019 (9)
C11	0.0254 (9)	0.0326 (10)	0.0399 (12)	−0.0016 (8)	−0.0016 (8)	−0.0008 (9)
C12	0.0280 (9)	0.0342 (10)	0.0416 (12)	0.0036 (8)	−0.0007 (9)	0.0041 (9)
C13	0.0318 (11)	0.0512 (14)	0.0602 (16)	−0.0026 (10)	0.0024 (12)	−0.0017 (13)
C14	0.0344 (13)	0.0653 (19)	0.075 (2)	0.0031 (12)	0.0135 (13)	0.0118 (16)
C15	0.0528 (16)	0.0614 (18)	0.0619 (18)	0.0242 (14)	0.0213 (14)	0.0157 (14)
C16	0.079 (2)	0.0479 (15)	0.0534 (17)	0.0151 (15)	0.0114 (16)	−0.0061 (12)
C17	0.0484 (14)	0.0404 (12)	0.0522 (16)	0.0003 (11)	0.0026 (12)	−0.0026 (11)
C18	0.0355 (11)	0.0383 (11)	0.0465 (14)	0.0017 (9)	0.0071 (10)	0.0073 (10)
C19	0.0494 (15)	0.0527 (15)	0.0537 (16)	0.0108 (12)	0.0062 (13)	0.0176 (13)
C20	0.0338 (10)	0.0308 (10)	0.0457 (13)	0.0001 (8)	0.0032 (10)	0.0057 (9)
C21	0.0387 (12)	0.0299 (11)	0.0494 (14)	0.0060 (9)	0.0053 (10)	0.0065 (9)

Cl1—C1	1.742 (3)	C9—C20	1.332 (3)
Cl2—C15	1.752 (3)	C9—C10	1.513 (3)
O1—C21	1.230 (3)	C10—C18	1.531 (3)
N1—C7	1.455 (3)	C10—C11	1.558 (3)
N1—C11	1.464 (3)	C10—H10	0.9800
N1—H1N	0.821 (14)	C11—C12	1.516 (3)
N2—C21	1.334 (4)	C11—H11	0.9800
N2—H2NA	0.824 (14)	C12—C17	1.381 (4)
N2—H2NB	0.824 (14)	C12—C13	1.390 (3)
C1—C6	1.370 (4)	C13—C14	1.386 (4)
C1—C2	1.378 (4)	C13—H13	0.9300
C2—C3	1.389 (4)	C14—C15	1.365 (5)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.388 (4)	C15—C16	1.370 (5)
C3—H3	0.9300	C16—C17	1.389 (4)
C4—C5	1.385 (3)	C16—H16	0.9300
C4—C7	1.515 (3)	C17—H17	0.9300
C5—C6	1.399 (3)	C18—C19	1.528 (4)
C5—H5	0.9300	C18—H18A	0.9700
C6—H6	0.9300	C18—H18B	0.9700
C7—C8	1.538 (3)	C19—H19A	0.9600
C7—H7	0.9800	C19—H19B	0.9600
C8—C9	1.510 (3)	C19—H19C	0.9600
C8—H8A	0.9700	C20—C21	1.489 (4)
C8—H8B	0.9700	C20—H20	0.9300
C7—N1—C11	112.88 (17)	C11—C10—H10	107.3
C7—N1—H1N	106 (3)	N1—C11—C12	109.44 (18)
C11—N1—H1N	110 (2)	N1—C11—C10	108.71 (17)
C21—N2—H2NA	117 (2)	C12—C11—C10	112.1 (2)
C21—N2—H2NB	123 (3)	N1—C11—H11	108.8
H2NA—N2—H2NB	120 (4)	C12—C11—H11	108.8
C6—C1—C2	121.7 (2)	C10—C11—H11	108.8
C6—C1—Cl1	119.9 (2)	C17—C12—C13	118.3 (2)
C2—C1—Cl1	118.4 (2)	C17—C12—C11	122.1 (2)
C1—C2—C3	118.9 (2)	C13—C12—C11	119.6 (2)
C1—C2—H2	120.6	C14—C13—C12	121.0 (3)
C3—C2—H2	120.6	C14—C13—H13	119.5
C4—C3—C2	121.0 (2)	C12—C13—H13	119.5
C4—C3—H3	119.5	C15—C14—C13	119.1 (3)
C2—C3—H3	119.5	C15—C14—H14	120.4
C5—C4—C3	118.7 (2)	C13—C14—H14	120.4
C5—C4—C7	122.3 (2)	C14—C15—C16	121.2 (3)
C3—C4—C7	119.0 (2)	C14—C15—Cl2	118.8 (3)
C4—C5—C6	120.9 (2)	C16—C15—Cl2	119.9 (3)
C4—C5—H5	119.6	C15—C16—C17	119.5 (3)
C6—C5—H5	119.6	C15—C16—H16	120.3
C1—C6—C5	118.8 (2)	C17—C16—H16	120.3
C1—C6—H6	120.6	C12—C17—C16	120.7 (3)
C5—C6—H6	120.6	C12—C17—H17	119.7
N1—C7—C4	111.75 (18)	C16—C17—H17	119.7
N1—C7—C8	108.56 (19)	C19—C18—C10	113.2 (2)
C4—C7—C8	111.50 (18)	C19—C18—H18A	108.9
N1—C7—H7	108.3	C10—C18—H18A	108.9
C4—C7—H7	108.3	C19—C18—H18B	108.9
C8—C7—H7	108.3	C10—C18—H18B	108.9
C9—C8—C7	107.72 (18)	H18A—C18—H18B	107.8
C9—C8—H8A	110.2	C18—C19—H19A	109.5
C7—C8—H8A	110.2	C18—C19—H19B	109.5
C9—C8—H8B	110.2	H19A—C19—H19B	109.5
C7—C8—H8B	110.2	C18—C19—H19C	109.5
H8A—C8—H8B	108.5	H19A—C19—H19C	109.5
C20—C9—C8	123.6 (2)	H19B—C19—H19C	109.5
C20—C9—C10	123.1 (2)	C9—C20—C21	126.9 (2)
C8—C9—C10	112.56 (19)	C9—C20—H20	116.6
C9—C10—C18	115.28 (18)	C21—C20—H20	116.6
C9—C10—C11	106.90 (18)	O1—C21—N2	122.7 (3)
C18—C10—C11	112.36 (18)	O1—C21—C20	123.7 (2)
C9—C10—H10	107.3	N2—C21—C20	113.5 (2)
C18—C10—H10	107.3
C6—C1—C2—C3	−2.2 (4)	C7—N1—C11—C10	−62.6 (2)
Cl1—C1—C2—C3	178.2 (2)	C9—C10—C11—N1	57.4 (2)
C1—C2—C3—C4	2.7 (4)	C18—C10—C11—N1	−175.2 (2)
C2—C3—C4—C5	−1.1 (4)	C9—C10—C11—C12	178.48 (18)
C2—C3—C4—C7	179.2 (2)	C18—C10—C11—C12	−54.1 (3)
C3—C4—C5—C6	−1.0 (3)	N1—C11—C12—C17	45.3 (3)
C7—C4—C5—C6	178.6 (2)	C10—C11—C12—C17	−75.4 (3)
C2—C1—C6—C5	0.1 (4)	N1—C11—C12—C13	−136.7 (2)
Cl1—C1—C6—C5	179.7 (2)	C10—C11—C12—C13	102.6 (3)
C4—C5—C6—C1	1.5 (4)	C17—C12—C13—C14	3.6 (4)
C11—N1—C7—C4	−173.73 (18)	C11—C12—C13—C14	−174.5 (3)
C11—N1—C7—C8	62.9 (2)	C12—C13—C14—C15	−1.3 (5)
C5—C4—C7—N1	−14.2 (3)	C13—C14—C15—C16	−1.9 (5)
C3—C4—C7—N1	165.5 (2)	C13—C14—C15—Cl2	176.3 (2)
C5—C4—C7—C8	107.5 (3)	C14—C15—C16—C17	2.7 (5)
C3—C4—C7—C8	−72.8 (3)	Cl2—C15—C16—C17	−175.5 (2)
N1—C7—C8—C9	−58.3 (2)	C13—C12—C17—C16	−2.8 (4)
C4—C7—C8—C9	178.2 (2)	C11—C12—C17—C16	175.2 (3)
C7—C8—C9—C20	−111.6 (2)	C15—C16—C17—C12	−0.3 (5)
C7—C8—C9—C10	59.3 (3)	C9—C10—C18—C19	−68.9 (3)
C20—C9—C10—C18	−13.2 (3)	C11—C10—C18—C19	168.3 (2)
C8—C9—C10—C18	175.8 (2)	C8—C9—C20—C21	−7.2 (4)
C20—C9—C10—C11	112.5 (2)	C10—C9—C20—C21	−177.2 (2)
C8—C9—C10—C11	−58.5 (2)	C9—C20—C21—O1	−39.1 (4)
C7—N1—C11—C12	174.66 (19)	C9—C20—C21—N2	144.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NB···O1i	0.82 (1)	2.17 (2)	2.973 (3)	165 (4)
C6—H6···O1ii	0.93	2.55	3.454 (3)	163
N1—H1N···Cgii	0.82 (1)	2.85 (4)	3.626 (2)	157 (3)

Table 1

Hydrogen-bond geometry (, )

Cg is the centroid of the C1C6 ring.

DHA	DH	HA	D A	DHA
N2H2NBO1i	0.82(1)	2.17(2)	2.973(3)	165(4)
C6H6O1ii	0.93	2.55	3.454(3)	163
N1H1N Cg ii	0.82(1)	2.85(4)	3.626(2)	157(3)

Symmetry codes: (i) ; (ii) .