(3E,5E)-1-Acryloyl-3,5-bis-(2,4-dichloro-benzyl-idene)piperidin-4-one hemihydrate.

The asymmetric unit of the title compound, C(22)H(15)Cl(4)NO(2)·0.5H(2)O, consists of a (3E,5E)-1-acryloyl-3,5-bis-(2,4-dichloro-benzyl-idene)piperidin-4-one mol-ecule and a half-mol-ecule of water (the O atom of the water mol-ecule lies on a twofold axis). The piperidin-4-one ring adopts an envelope conformation. The dihedral angle between the two terminal benzene rings is 8.84 (11)°. In the crystal, mol-ecules are connected by C-H⋯O hydrogen bonds forming supra-molecular chains along the c axis. Furthermore, adjacent chains are inter-connected by the water mol-ecules via O-H⋯O hydrogen bonds.

Related literature

For details and applications of α,β-unsaturated carbonyl compounds, see: Oh et al. (2006 ▶); El-Subbagh et al. (2000 ▶); Husain et al. (2006 ▶); Favier et al. (2005 ▶). For details of the preparation, see: Dimmock et al. (2000 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

2C22H15Cl4NO2·H2O

M = 952.32

Monoclinic,

a = 27.0296 (12) Å

b = 11.3031 (5) Å

c = 18.9580 (14) Å

β = 133.807 (2)°

V = 4180.0 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.59 mm−1

T = 296 K

0.41 × 0.22 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.794, T max = 0.947

22264 measured reflections

6084 independent reflections

3314 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.140

S = 1.04

6084 reflections

273 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016023/sj5130sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016023/sj5130Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811016023/sj5130Isup3.cml

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

2C22H15Cl4NO2·H2O	F(000) = 1944
Mr = 952.32	Dx = 1.513 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4558 reflections
a = 27.0296 (12) Å	θ = 3.0–23.7°
b = 11.3031 (5) Å	µ = 0.59 mm−1
c = 18.9580 (14) Å	T = 296 K
β = 133.807 (2)°	Plate, yellow
V = 4180.0 (4) Å3	0.41 × 0.22 × 0.09 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	6084 independent reflections
Radiation source: fine-focus sealed tube	3314 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 30.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −37→37
Tmin = 0.794, Tmax = 0.947	k = −15→15
22264 measured reflections	l = −26→26

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0565P)2 + 1.3835P] where P = (Fo2 + 2Fc2)/3
6084 reflections	(Δ/σ)max < 0.001
273 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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
Cl1	0.19792 (3)	0.76399 (7)	0.69001 (5)	0.0713 (2)
Cl2	0.42591 (5)	0.54693 (7)	0.82870 (7)	0.0917 (3)
Cl3	0.03129 (4)	0.56068 (7)	1.19385 (5)	0.0758 (2)
Cl4	−0.03353 (4)	0.74207 (6)	0.87822 (6)	0.0793 (2)
O1	0.18932 (9)	0.28214 (16)	0.88038 (12)	0.0674 (5)
O1W	0.0000	0.0870 (4)	0.2500	0.1570 (17)
H1W1	−0.0368	0.1548	0.2124	0.235*
O2	0.13682 (9)	0.76238 (14)	0.86903 (13)	0.0622 (5)
C1	0.33740 (12)	0.57044 (19)	0.92958 (17)	0.0525 (6)
H1A	0.3468	0.5447	0.9845	0.063*
C2	0.38244 (13)	0.5423 (2)	0.92100 (19)	0.0599 (6)
H2A	0.4215	0.4978	0.9691	0.072*
C3	0.36913 (13)	0.5808 (2)	0.84014 (19)	0.0553 (6)
C4	0.31230 (12)	0.64792 (19)	0.76899 (17)	0.0520 (6)
H4A	0.3040	0.6748	0.7152	0.062*
C5	0.26793 (11)	0.67438 (18)	0.77940 (15)	0.0463 (5)
C6	0.27789 (11)	0.63624 (18)	0.85892 (15)	0.0432 (5)
C7	0.23003 (11)	0.66960 (19)	0.86785 (15)	0.0450 (5)
H7A	0.2063	0.7399	0.8371	0.054*
C8	0.21566 (11)	0.61329 (18)	0.91388 (14)	0.0428 (5)
C9	0.16516 (11)	0.66934 (18)	0.91293 (15)	0.0450 (5)
C10	0.15150 (11)	0.61138 (17)	0.96889 (14)	0.0415 (5)
C11	0.18741 (13)	0.49604 (19)	1.02007 (17)	0.0514 (6)
H11A	0.2303	0.5116	1.0866	0.062*
H11B	0.1589	0.4479	1.0226	0.062*
N12	0.20085 (11)	0.43276 (15)	0.96822 (15)	0.0519 (5)
C13	0.24670 (13)	0.4960 (2)	0.96662 (18)	0.0544 (6)
H13A	0.2556	0.4483	0.9339	0.065*
H13B	0.2900	0.5100	1.0331	0.065*
C14	0.10773 (11)	0.66486 (18)	0.96949 (15)	0.0435 (5)
H14A	0.0858	0.7311	0.9294	0.052*
C15	0.08921 (11)	0.63488 (17)	1.02373 (15)	0.0412 (5)
C16	0.02599 (12)	0.66960 (18)	0.98959 (16)	0.0485 (5)
C17	0.00789 (12)	0.64771 (19)	1.04118 (18)	0.0525 (6)
H17A	−0.0346	0.6715	1.0165	0.063*
C18	0.05393 (12)	0.5901 (2)	1.12973 (17)	0.0505 (6)
C19	0.11714 (12)	0.5554 (2)	1.16688 (16)	0.0513 (6)
H19A	0.1481	0.5171	1.2269	0.062*
C20	0.13390 (11)	0.57787 (19)	1.11453 (15)	0.0462 (5)
H20A	0.1767	0.5543	1.1404	0.055*
C21	0.17589 (12)	0.3248 (2)	0.92493 (16)	0.0501 (6)
C22	0.13274 (16)	0.2603 (2)	0.9335 (2)	0.0657 (7)
H22A	0.1364	0.2797	0.9847	0.079*
C23	0.09076 (18)	0.1794 (3)	0.8743 (2)	0.0836 (9)
H23A	0.0609 (16)	0.130 (3)	0.877 (2)	0.100*
H23B	0.0891 (17)	0.161 (3)	0.826 (2)	0.100*

	U11	U22	U33	U12	U13	U23
Cl1	0.0626 (4)	0.0989 (5)	0.0619 (4)	0.0183 (3)	0.0467 (3)	0.0281 (3)
Cl2	0.1113 (7)	0.0861 (5)	0.1412 (7)	0.0305 (4)	0.1113 (6)	0.0297 (5)
Cl3	0.0849 (5)	0.1020 (6)	0.0794 (4)	−0.0122 (4)	0.0715 (4)	−0.0143 (4)
Cl4	0.0618 (4)	0.0870 (5)	0.0905 (5)	0.0289 (4)	0.0533 (4)	0.0392 (4)
O1	0.0783 (13)	0.0780 (12)	0.0699 (11)	0.0054 (9)	0.0603 (11)	−0.0090 (9)
O1W	0.191 (5)	0.105 (3)	0.240 (5)	0.000	0.174 (4)	0.000
O2	0.0806 (12)	0.0583 (10)	0.0728 (11)	0.0209 (8)	0.0626 (10)	0.0227 (8)
C1	0.0539 (14)	0.0573 (13)	0.0553 (13)	−0.0014 (11)	0.0412 (12)	0.0075 (11)
C2	0.0550 (15)	0.0579 (14)	0.0759 (16)	0.0061 (11)	0.0487 (14)	0.0129 (12)
C3	0.0637 (16)	0.0483 (12)	0.0806 (16)	−0.0016 (11)	0.0600 (14)	0.0012 (11)
C4	0.0634 (15)	0.0525 (13)	0.0579 (13)	−0.0086 (11)	0.0486 (13)	−0.0030 (10)
C5	0.0488 (13)	0.0467 (12)	0.0504 (12)	−0.0060 (10)	0.0371 (11)	−0.0010 (9)
C6	0.0466 (12)	0.0445 (11)	0.0462 (11)	−0.0090 (9)	0.0350 (10)	−0.0035 (9)
C7	0.0480 (13)	0.0474 (12)	0.0449 (11)	−0.0027 (9)	0.0342 (10)	−0.0013 (9)
C8	0.0459 (12)	0.0464 (11)	0.0419 (10)	−0.0002 (9)	0.0325 (10)	−0.0002 (9)
C9	0.0515 (13)	0.0463 (12)	0.0438 (11)	0.0006 (10)	0.0355 (11)	−0.0005 (9)
C10	0.0484 (12)	0.0411 (10)	0.0425 (10)	0.0012 (9)	0.0344 (10)	−0.0005 (8)
C11	0.0719 (16)	0.0474 (12)	0.0601 (13)	0.0108 (11)	0.0551 (13)	0.0074 (10)
N12	0.0748 (13)	0.0409 (9)	0.0746 (12)	0.0072 (9)	0.0647 (12)	0.0057 (9)
C13	0.0651 (15)	0.0558 (13)	0.0671 (14)	0.0107 (11)	0.0551 (13)	0.0123 (11)
C14	0.0479 (12)	0.0405 (11)	0.0455 (11)	−0.0005 (9)	0.0336 (10)	−0.0002 (8)
C15	0.0440 (12)	0.0374 (10)	0.0497 (11)	−0.0017 (9)	0.0352 (10)	−0.0052 (9)
C16	0.0528 (14)	0.0399 (11)	0.0594 (13)	0.0044 (10)	0.0413 (12)	0.0018 (9)
C17	0.0520 (14)	0.0522 (13)	0.0685 (15)	−0.0018 (11)	0.0474 (13)	−0.0081 (11)
C18	0.0591 (15)	0.0528 (12)	0.0588 (13)	−0.0081 (11)	0.0480 (12)	−0.0135 (11)
C19	0.0584 (15)	0.0586 (14)	0.0477 (12)	0.0013 (11)	0.0407 (12)	−0.0025 (10)
C20	0.0441 (12)	0.0536 (12)	0.0473 (11)	0.0023 (10)	0.0340 (10)	−0.0051 (9)
C21	0.0583 (14)	0.0524 (13)	0.0517 (12)	0.0147 (11)	0.0427 (12)	0.0103 (10)
C22	0.088 (2)	0.0556 (14)	0.0835 (18)	−0.0039 (14)	0.0704 (17)	−0.0055 (13)
C23	0.083 (2)	0.086 (2)	0.083 (2)	−0.0061 (18)	0.058 (2)	0.0030 (18)

Cl1—C5	1.743 (2)	C11—N12	1.451 (3)
Cl2—C3	1.735 (3)	C11—H11A	0.9700
Cl3—C18	1.730 (2)	C11—H11B	0.9700
Cl4—C16	1.736 (2)	N12—C21	1.360 (3)
O1—C21	1.226 (3)	N12—C13	1.449 (3)
O1W—H1W1	1.0501	C13—H13A	0.9700
O2—C9	1.226 (2)	C13—H13B	0.9700
C1—C2	1.373 (3)	C14—C15	1.461 (3)
C1—C6	1.397 (3)	C14—H14A	0.9300
C1—H1A	0.9300	C15—C20	1.400 (3)
C2—C3	1.380 (3)	C15—C16	1.401 (3)
C2—H2A	0.9300	C16—C17	1.385 (3)
C3—C4	1.373 (3)	C17—C18	1.378 (3)
C4—C5	1.376 (3)	C17—H17A	0.9300
C4—H4A	0.9300	C18—C19	1.380 (3)
C5—C6	1.403 (3)	C19—C20	1.370 (3)
C6—C7	1.466 (3)	C19—H19A	0.9300
C7—C8	1.337 (3)	C20—H20A	0.9300
C7—H7A	0.9300	C21—C22	1.477 (4)
C8—C9	1.494 (3)	C22—C23	1.273 (4)
C8—C13	1.516 (3)	C22—H22A	0.9300
C9—C10	1.494 (3)	C23—H23A	1.01 (3)
C10—C14	1.336 (3)	C23—H23B	0.90 (3)
C10—C11	1.510 (3)
C2—C1—C6	122.4 (2)	C13—N12—C11	112.94 (19)
C2—C1—H1A	118.8	N12—C13—C8	110.76 (19)
C6—C1—H1A	118.8	N12—C13—H13A	109.5
C1—C2—C3	119.2 (2)	C8—C13—H13A	109.5
C1—C2—H2A	120.4	N12—C13—H13B	109.5
C3—C2—H2A	120.4	C8—C13—H13B	109.5
C4—C3—C2	121.3 (2)	H13A—C13—H13B	108.1
C4—C3—Cl2	118.93 (19)	C10—C14—C15	129.64 (19)
C2—C3—Cl2	119.8 (2)	C10—C14—H14A	115.2
C3—C4—C5	118.2 (2)	C15—C14—H14A	115.2
C3—C4—H4A	120.9	C20—C15—C16	115.8 (2)
C5—C4—H4A	120.9	C20—C15—C14	123.2 (2)
C4—C5—C6	123.3 (2)	C16—C15—C14	120.84 (19)
C4—C5—Cl1	117.01 (17)	C17—C16—C15	122.5 (2)
C6—C5—Cl1	119.65 (17)	C17—C16—Cl4	117.38 (18)
C1—C6—C5	115.5 (2)	C15—C16—Cl4	120.08 (17)
C1—C6—C7	123.27 (19)	C18—C17—C16	118.8 (2)
C5—C6—C7	121.13 (19)	C18—C17—H17A	120.6
C8—C7—C6	129.2 (2)	C16—C17—H17A	120.6
C8—C7—H7A	115.4	C17—C18—C19	120.7 (2)
C6—C7—H7A	115.4	C17—C18—Cl3	119.11 (19)
C7—C8—C9	117.79 (19)	C19—C18—Cl3	120.14 (18)
C7—C8—C13	124.7 (2)	C20—C19—C18	119.4 (2)
C9—C8—C13	117.56 (18)	C20—C19—H19A	120.3
O2—C9—C8	120.56 (19)	C18—C19—H19A	120.3
O2—C9—C10	120.8 (2)	C19—C20—C15	122.6 (2)
C8—C9—C10	118.57 (18)	C19—C20—H20A	118.7
C14—C10—C9	117.60 (18)	C15—C20—H20A	118.7
C14—C10—C11	124.36 (19)	O1—C21—N12	120.6 (2)
C9—C10—C11	118.04 (19)	O1—C21—C22	121.0 (2)
N12—C11—C10	109.96 (17)	N12—C21—C22	118.4 (2)
N12—C11—H11A	109.7	C23—C22—C21	123.1 (3)
C10—C11—H11A	109.7	C23—C22—H22A	118.4
N12—C11—H11B	109.7	C21—C22—H22A	118.4
C10—C11—H11B	109.7	C22—C23—H23A	127.5 (18)
H11A—C11—H11B	108.2	C22—C23—H23B	117 (2)
C21—N12—C13	120.28 (19)	H23A—C23—H23B	116 (3)
C21—N12—C11	126.8 (2)
C6—C1—C2—C3	0.5 (4)	C10—C11—N12—C13	62.9 (2)
C1—C2—C3—C4	0.9 (4)	C21—N12—C13—C8	118.9 (2)
C1—C2—C3—Cl2	179.49 (18)	C11—N12—C13—C8	−61.9 (2)
C2—C3—C4—C5	−1.2 (3)	C7—C8—C13—N12	−153.1 (2)
Cl2—C3—C4—C5	−179.73 (17)	C9—C8—C13—N12	26.5 (3)
C3—C4—C5—C6	0.0 (3)	C9—C10—C14—C15	−174.22 (19)
C3—C4—C5—Cl1	177.85 (17)	C11—C10—C14—C15	6.4 (4)
C2—C1—C6—C5	−1.5 (3)	C10—C14—C15—C20	29.1 (3)
C2—C1—C6—C7	−178.5 (2)	C10—C14—C15—C16	−155.2 (2)
C4—C5—C6—C1	1.3 (3)	C20—C15—C16—C17	−0.9 (3)
Cl1—C5—C6—C1	−176.51 (16)	C14—C15—C16—C17	−176.90 (19)
C4—C5—C6—C7	178.3 (2)	C20—C15—C16—Cl4	179.54 (15)
Cl1—C5—C6—C7	0.5 (3)	C14—C15—C16—Cl4	3.6 (3)
C1—C6—C7—C8	−29.5 (3)	C15—C16—C17—C18	0.3 (3)
C5—C6—C7—C8	153.7 (2)	Cl4—C16—C17—C18	179.86 (16)
C6—C7—C8—C9	178.76 (19)	C16—C17—C18—C19	0.4 (3)
C6—C7—C8—C13	−1.6 (4)	C16—C17—C18—Cl3	−179.14 (16)
C7—C8—C9—O2	1.8 (3)	C17—C18—C19—C20	−0.5 (3)
C13—C8—C9—O2	−177.8 (2)	Cl3—C18—C19—C20	179.05 (17)
C7—C8—C9—C10	−176.47 (19)	C18—C19—C20—C15	−0.2 (3)
C13—C8—C9—C10	3.9 (3)	C16—C15—C20—C19	0.9 (3)
O2—C9—C10—C14	−0.3 (3)	C14—C15—C20—C19	176.7 (2)
C8—C9—C10—C14	178.02 (19)	C13—N12—C21—O1	−3.3 (3)
O2—C9—C10—C11	179.2 (2)	C11—N12—C21—O1	177.6 (2)
C8—C9—C10—C11	−2.5 (3)	C13—N12—C21—C22	176.3 (2)
C14—C10—C11—N12	150.5 (2)	C11—N12—C21—C22	−2.8 (3)
C9—C10—C11—N12	−28.9 (3)	O1—C21—C22—C23	−22.3 (4)
C10—C11—N12—C21	−117.9 (2)	N12—C21—C22—C23	158.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2i	1.05	2.19	3.180 (3)	157
C4—H4A···O1ii	0.93	2.29	3.186 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O2i	1.05	2.19	3.180 (3)	157
C4—H4A⋯O1ii	0.93	2.29	3.186 (3)	162

Symmetry codes: (i) ; (ii) .