3,5-Bis(4-chloro-benzyl-idene)-1-methyl-piperidin-4-one.

In the title mol-ecule, C(20)H(17)Cl(2)NO, the central heterocyclic ring adopts a flattened boat conformation. The dihedral angles between the planar part of this central heterocyclic ring [maximum deviation = 0.004 (1) Å] and the two almost planar side-chain fragments [maximum deviations = 0.015 (1) and 0.019 (1) Å], that include the aromatic ring and bridging atoms, are 18.1 (1) and 18.0 (1)°. In the crystal, pairs of weak inter-molecular C-H⋯O hydrogen bonds link mol-ecules into inversion dimers that form stacks along the a axis. The structure is further stabilized by weak inter-molecular C-H⋯π inter-actions involving the benzene rings.

Related literature

For non-linear optical organic compounds with two-photon absorption properties and potential biophotonic materials, see: Nesterov et al. (2003 ▶); Nesterov (2004 ▶); Sarkisov et al. (2005 ▶). For the biological importance of 4-piperidone, see: Jia et al. (1988 ▶, 1989 ▶); Dimmock et al. (2001 ▶). For the synthesis of the title compound, see: Dimmock et al. (2001 ▶). For related structures, see: Nesterov (2004 ▶); Nesterov et al. (2003 ▶, 2007a ▶,b ▶,c ▶, 2008 ▶). For weak hydrogen bonds, see: Desiraju & Steiner (1999 ▶). For the van der Waals radius of the H atom, see: Rowland & Taylor (1996 ▶).

Experimental

Crystal data

C20H17Cl2NO

M = 358.25

Monoclinic,

a = 5.4568 (11) Å

b = 13.916 (3) Å

c = 22.289 (4) Å

β = 90.847 (3)°

V = 1692.4 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.39 mm−1

T = 100 K

0.23 × 0.18 × 0.08 mm

Data collection

Bruker SMART APEX II CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.916, T max = 0.970

14890 measured reflections

3461 independent reflections

2830 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.080

S = 1.03

3461 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006994/su2255sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006994/su2255Isup2.hkl

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

C20H17Cl2NO	F(000) = 744
Mr = 358.25	Dx = 1.406 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2327 reflections
a = 5.4568 (11) Å	θ = 2.4–25.2°
b = 13.916 (3) Å	µ = 0.39 mm−1
c = 22.289 (4) Å	T = 100 K
β = 90.847 (3)°	Plate, yellow
V = 1692.4 (6) Å3	0.23 × 0.18 × 0.08 mm
Z = 4

Bruker SMART APEX II CCD diffractometer	3461 independent reflections
Radiation source: fine-focus sealed tube	2830 reflections with I > 2σ(I)
graphite	Rint = 0.042
ω scans	θmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −6→6
Tmin = 0.916, Tmax = 0.970	k = −17→17
14890 measured reflections	l = −27→27

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.030P)2 + 0.850P] where P = (Fo2 + 2Fc2)/3
3461 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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	0.64148 (8)	0.85150 (3)	0.742372 (19)	0.02375 (12)
Cl2	0.64623 (9)	0.87411 (3)	0.01133 (2)	0.02727 (13)
O1	0.1157 (2)	0.92396 (9)	0.37523 (5)	0.0245 (3)
N1	0.5768 (3)	0.71047 (10)	0.37453 (6)	0.0191 (3)
C1	0.7423 (4)	0.62787 (13)	0.37437 (8)	0.0245 (4)
H1A	0.7070	0.5863	0.4087	0.037*
H1B	0.9123	0.6503	0.3773	0.037*
H1C	0.7187	0.5916	0.3370	0.037*
C2	0.6145 (3)	0.76651 (12)	0.42936 (8)	0.0187 (4)
H2A	0.7803	0.7953	0.4295	0.022*
H2B	0.6023	0.7239	0.4648	0.022*
C3	0.4243 (3)	0.84484 (12)	0.43294 (8)	0.0172 (4)
C4	0.3040 (3)	0.87585 (12)	0.37573 (8)	0.0188 (4)
C5	0.4283 (3)	0.84936 (12)	0.31884 (8)	0.0170 (4)
C6	0.6202 (3)	0.77144 (12)	0.32221 (8)	0.0183 (4)
H6A	0.6132	0.7321	0.2852	0.022*
H6B	0.7852	0.8007	0.3255	0.022*
C7	0.3539 (3)	0.89000 (12)	0.48316 (8)	0.0181 (4)
H7A	0.2281	0.9364	0.4772	0.022*
C8	0.4384 (3)	0.87971 (12)	0.54539 (8)	0.0176 (4)
C9	0.2897 (3)	0.91907 (12)	0.59029 (8)	0.0190 (4)
H9A	0.1438	0.9519	0.5788	0.023*
C10	0.3496 (3)	0.91133 (13)	0.65039 (8)	0.0201 (4)
H10A	0.2454	0.9374	0.6800	0.024*
C11	0.5648 (3)	0.86468 (12)	0.66671 (8)	0.0187 (4)
C12	0.7215 (3)	0.82827 (12)	0.62392 (8)	0.0194 (4)
H12A	0.8710	0.7983	0.6358	0.023*
C13	0.6586 (3)	0.83584 (12)	0.56397 (8)	0.0191 (4)
H13A	0.7662	0.8109	0.5347	0.023*
C14	0.3592 (3)	0.89801 (12)	0.26932 (8)	0.0176 (4)
H14A	0.2328	0.9438	0.2755	0.021*
C15	0.4450 (3)	0.89257 (12)	0.20763 (8)	0.0174 (4)
C16	0.2956 (3)	0.93346 (13)	0.16272 (8)	0.0204 (4)
H16A	0.1495	0.9655	0.1739	0.024*
C17	0.3543 (3)	0.92871 (13)	0.10259 (8)	0.0206 (4)
H17A	0.2491	0.9560	0.0728	0.025*
C18	0.5693 (3)	0.88342 (12)	0.08676 (8)	0.0192 (4)
C19	0.7270 (3)	0.84500 (12)	0.12966 (8)	0.0199 (4)
H19A	0.8760	0.8155	0.1181	0.024*
C20	0.6655 (3)	0.84995 (12)	0.18978 (8)	0.0191 (4)
H20A	0.7742	0.8241	0.2193	0.023*

	U11	U22	U33	U12	U13	U23
Cl1	0.0283 (3)	0.0252 (2)	0.0177 (2)	0.00033 (19)	0.00000 (17)	−0.00001 (17)
Cl2	0.0321 (3)	0.0321 (3)	0.0177 (2)	0.0028 (2)	0.00405 (18)	0.00208 (18)
O1	0.0208 (7)	0.0300 (7)	0.0229 (7)	0.0082 (6)	0.0024 (5)	0.0004 (6)
N1	0.0227 (8)	0.0170 (7)	0.0175 (7)	0.0018 (6)	0.0019 (6)	0.0001 (6)
C1	0.0325 (11)	0.0186 (9)	0.0226 (10)	0.0051 (8)	0.0020 (8)	0.0000 (7)
C2	0.0185 (9)	0.0194 (9)	0.0181 (9)	0.0016 (7)	0.0020 (7)	0.0010 (7)
C3	0.0154 (8)	0.0177 (9)	0.0187 (9)	−0.0027 (7)	0.0025 (7)	0.0016 (7)
C4	0.0177 (9)	0.0164 (9)	0.0224 (9)	−0.0014 (7)	0.0021 (7)	−0.0005 (7)
C5	0.0151 (8)	0.0172 (8)	0.0187 (9)	−0.0016 (7)	−0.0007 (7)	−0.0023 (7)
C6	0.0180 (9)	0.0196 (9)	0.0173 (9)	0.0020 (7)	0.0017 (7)	−0.0005 (7)
C7	0.0161 (8)	0.0173 (8)	0.0209 (9)	0.0005 (7)	0.0016 (7)	0.0022 (7)
C8	0.0190 (9)	0.0154 (8)	0.0186 (9)	−0.0025 (7)	0.0028 (7)	0.0002 (7)
C9	0.0158 (9)	0.0175 (9)	0.0237 (9)	0.0014 (7)	0.0015 (7)	−0.0002 (7)
C10	0.0198 (9)	0.0211 (9)	0.0197 (9)	−0.0013 (7)	0.0049 (7)	−0.0030 (7)
C11	0.0214 (9)	0.0175 (9)	0.0172 (9)	−0.0038 (7)	0.0008 (7)	−0.0005 (7)
C12	0.0161 (9)	0.0191 (9)	0.0229 (9)	0.0004 (7)	−0.0001 (7)	0.0009 (7)
C13	0.0185 (9)	0.0198 (9)	0.0193 (9)	0.0005 (7)	0.0056 (7)	−0.0025 (7)
C14	0.0153 (8)	0.0160 (8)	0.0215 (9)	−0.0001 (7)	0.0001 (7)	−0.0021 (7)
C15	0.0181 (9)	0.0154 (8)	0.0188 (9)	−0.0028 (7)	0.0007 (7)	−0.0010 (7)
C16	0.0189 (9)	0.0195 (9)	0.0229 (9)	0.0014 (7)	0.0011 (7)	0.0008 (7)
C17	0.0204 (9)	0.0213 (9)	0.0199 (9)	−0.0006 (7)	−0.0033 (7)	0.0035 (7)
C18	0.0229 (9)	0.0173 (9)	0.0176 (9)	−0.0046 (7)	0.0027 (7)	0.0009 (7)
C19	0.0175 (9)	0.0192 (9)	0.0230 (9)	−0.0017 (7)	0.0019 (7)	−0.0004 (7)
C20	0.0177 (9)	0.0193 (9)	0.0202 (9)	−0.0005 (7)	−0.0015 (7)	0.0013 (7)

Cl1—C11	1.7412 (18)	C8—C9	1.408 (2)
Cl2—C18	1.7437 (18)	C9—C10	1.378 (2)
O1—C4	1.226 (2)	C9—H9A	0.9500
N1—C2	1.462 (2)	C10—C11	1.386 (2)
N1—C1	1.462 (2)	C10—H10A	0.9500
N1—C6	1.464 (2)	C11—C12	1.386 (2)
C1—H1A	0.9800	C12—C13	1.379 (2)
C1—H1B	0.9800	C12—H12A	0.9500
C1—H1C	0.9800	C13—H13A	0.9500
C2—C3	1.508 (2)	C14—C15	1.461 (2)
C2—H2A	0.9900	C14—H14A	0.9500
C2—H2B	0.9900	C15—C16	1.402 (2)
C3—C7	1.345 (2)	C15—C20	1.404 (2)
C3—C4	1.489 (2)	C16—C17	1.384 (2)
C4—C5	1.493 (2)	C16—H16A	0.9500
C5—C14	1.344 (2)	C17—C18	1.382 (2)
C5—C6	1.509 (2)	C17—H17A	0.9500
C6—H6A	0.9900	C18—C19	1.385 (2)
C6—H6B	0.9900	C19—C20	1.388 (2)
C7—C8	1.462 (2)	C19—H19A	0.9500
C7—H7A	0.9500	C20—H20A	0.9500
C8—C13	1.405 (2)
C2—N1—C1	110.01 (14)	C10—C9—C8	121.96 (16)
C2—N1—C6	109.53 (14)	C10—C9—H9A	119.0
C1—N1—C6	110.27 (13)	C8—C9—H9A	119.0
N1—C1—H1A	109.5	C9—C10—C11	118.66 (16)
N1—C1—H1B	109.5	C9—C10—H10A	120.7
H1A—C1—H1B	109.5	C11—C10—H10A	120.7
N1—C1—H1C	109.5	C10—C11—C12	121.30 (16)
H1A—C1—H1C	109.5	C10—C11—Cl1	119.61 (13)
H1B—C1—H1C	109.5	C12—C11—Cl1	119.09 (14)
N1—C2—C3	109.96 (14)	C13—C12—C11	119.45 (16)
N1—C2—H2A	109.7	C13—C12—H12A	120.3
C3—C2—H2A	109.7	C11—C12—H12A	120.3
N1—C2—H2B	109.7	C12—C13—C8	121.23 (16)
C3—C2—H2B	109.7	C12—C13—H13A	119.4
H2A—C2—H2B	108.2	C8—C13—H13A	119.4
C7—C3—C4	116.71 (16)	C5—C14—C15	131.05 (16)
C7—C3—C2	125.96 (16)	C5—C14—H14A	114.5
C4—C3—C2	117.33 (15)	C15—C14—H14A	114.5
O1—C4—C3	121.64 (16)	C16—C15—C20	117.43 (16)
O1—C4—C5	121.21 (16)	C16—C15—C14	117.37 (15)
C3—C4—C5	117.10 (15)	C20—C15—C14	125.19 (16)
C14—C5—C4	116.58 (15)	C17—C16—C15	122.11 (17)
C14—C5—C6	126.10 (16)	C17—C16—H16A	118.9
C4—C5—C6	117.31 (15)	C15—C16—H16A	118.9
N1—C6—C5	109.62 (14)	C18—C17—C16	118.58 (16)
N1—C6—H6A	109.7	C18—C17—H17A	120.7
C5—C6—H6A	109.7	C16—C17—H17A	120.7
N1—C6—H6B	109.7	C17—C18—C19	121.41 (16)
C5—C6—H6B	109.7	C17—C18—Cl2	119.84 (14)
H6A—C6—H6B	108.2	C19—C18—Cl2	118.75 (14)
C3—C7—C8	130.82 (17)	C18—C19—C20	119.40 (16)
C3—C7—H7A	114.6	C18—C19—H19A	120.3
C8—C7—H7A	114.6	C20—C19—H19A	120.3
C13—C8—C9	117.31 (16)	C19—C20—C15	120.99 (16)
C13—C8—C7	125.35 (16)	C19—C20—H20A	119.5
C9—C8—C7	117.31 (16)	C15—C20—H20A	119.5

Cg1 and Cg2 are the centroids of the C15–C20 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1i	0.95	2.47	3.210 (2)	135
C12—H12A···Cg1ii	0.95	2.72	3.439 (2)	133
C19—H19A···Cg2iii	0.95	2.73	3.432 (2)	131

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C15–C20 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O1i	0.95	2.47	3.210 (2)	135
C12—H12A⋯Cg1ii	0.95	2.72	3.439 (2)	133
C19—H19A⋯Cg2iii	0.95	2.73	3.432 (2)	131

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