Crystal structures of four δ-keto esters and a Cambridge Structural Database analysis of cyano–halogen interactions

The revived interest in halogen bonding as a tool in pharmaceutical cocrystals and drug design has indicated that cyano–halogen interactions could play an important role. The crystal structures of four closely related δ-keto esters, which differ only in the substitution at a single C atom (by H, OMe, Cl and Br), are compared, namely ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-en­oate, C₁₉H₂₂N₂O₃, (1), ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperi­din-1-yl)pent-2-enoate, C₂₀H₂₄N₂O₄, (2), ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C₁₉H₂₁ClN₂O₃, (3), and the previously published ethyl 5-(4-bromo­phenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C₁₉H₂₁BrN₂O₃, (4) [Maurya, Vasudev & Gupta (2013). RSC Adv. 3, 12955–12962]. The molecular conformations are very similar, while there are differences in the molecular assemblies. Intermolecular C—H...O hydrogen bonds are found to be the primary interactions in the crystal packing and are present in all four structures. The halogenated derivatives have additional aromatic–aromatic interactions and cyano–halogen interactions, further stabilizing the molecular packing. A database analysis of cyano–halogen interactions using the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662–671] revealed that about 13% of the organic molecular crystals containing both cyano and halogen groups have cyano–halogen interactions in their packing. Three geometric parameters for the C—X...N[triple bond]C interaction (X = F, Cl, Br or I), viz. the N...X distance and the C—X...N and C—N...X angles, were analysed. The results indicate that all the short cyano–halogen contacts in the CSD can be classified as halogen bonds, which are directional noncovalent interactions.

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

Computing details

For all compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

(1) Ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-enoate

Crystal data

C19H22N2O3	Z = 4
Mr = 326.38	F(000) = 696
Monoclinic, P21/n	Dx = 1.243 Mg m^−3
a = 12.4152 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9071 (6) Å	µ = 0.09 mm^−1
c = 16.5072 (12) Å	T = 293 K
β = 107.194 (2)°	Needle, colourless
V = 1743.8 (2) Å^3	0.60 × 0.06 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	Rint = 0.044
Radiation source: fine-focus sealed tube	θmax = 26.4°, θmin = 2.4°
7982 measured reflections	h = −15→10
3550 independent reflections	k = −11→10
2211 reflections with I > 2σ(I)	l = −20→20

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0716P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.010
3550 reflections	Δρmax = 0.22 e Å^−3
217 parameters	Δρmin = −0.26 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.32648 (11)	0.56311 (16)	1.00253 (8)	0.0284 (4)
O2	0.33697 (11)	0.54287 (16)	0.86947 (8)	0.0288 (4)
O3	0.11852 (11)	0.48808 (17)	0.68463 (8)	0.0283 (4)
N1	0.12498 (14)	0.3743 (2)	1.04256 (10)	0.0282 (4)
N2	0.03660 (13)	0.29112 (18)	0.81128 (9)	0.0225 (4)
C1	0.4218 (2)	0.7376 (3)	1.10630 (14)	0.0572 (8)
H1A	0.4796	0.8130	1.1211	0.086*
H1B	0.3507	0.7816	1.1051	0.086*
H1C	0.4397	0.6584	1.1476	0.086*
C2	0.41450 (18)	0.6752 (3)	1.02088 (13)	0.0345 (6)
H2A	0.3963	0.7540	0.9784	0.041*
H2B	0.4858	0.6302	1.0212	0.041*
C3	0.29118 (16)	0.5089 (2)	0.92260 (12)	0.0222 (5)
C4	0.19338 (16)	0.4136 (2)	0.91138 (11)	0.0196 (4)
C5	0.14377 (16)	0.3357 (2)	0.83540 (11)	0.0208 (5)
C6	0.21694 (16)	0.2989 (2)	0.77979 (11)	0.0228 (5)
H6A	0.2020	0.1965	0.7596	0.027*
H6B	0.2955	0.3048	0.8134	0.027*
C7	0.19787 (16)	0.4025 (2)	0.70460 (11)	0.0215 (5)
C8	0.28030 (16)	0.3948 (2)	0.65449 (11)	0.0213 (5)
C9	0.26664 (17)	0.4907 (2)	0.58593 (12)	0.0263 (5)
H9	0.2076	0.5595	0.5726	0.032*
C10	0.33996 (19)	0.4847 (3)	0.53743 (13)	0.0308 (5)
H10	0.3308	0.5500	0.4919	0.037*
C11	0.42705 (18)	0.3818 (2)	0.55653 (13)	0.0321 (5)
H11	0.4760	0.3773	0.5235	0.039*
C12	0.44167 (18)	0.2856 (2)	0.62433 (13)	0.0296 (5)
H12	0.5006	0.2167	0.6371	0.036*
C13	0.36863 (17)	0.2916 (2)	0.67341 (12)	0.0242 (5)
H13	0.3785	0.2266	0.7191	0.029*
C14	−0.01074 (17)	0.1785 (2)	0.74437 (12)	0.0299 (5)
H14A	−0.0367	0.0923	0.7692	0.036*
H14B	0.0480	0.1448	0.7208	0.036*
C15	−0.10796 (18)	0.2415 (3)	0.67380 (12)	0.0348 (6)
H15A	−0.0805	0.3203	0.6445	0.042*
H15B	−0.1399	0.1628	0.6332	0.042*
C16	−0.19830 (17)	0.3042 (3)	0.70906 (13)	0.0340 (6)
H16A	−0.2562	0.3528	0.6641	0.041*
H16B	−0.2331	0.2230	0.7315	0.041*
C17	−0.14767 (17)	0.4158 (2)	0.77833 (12)	0.0282 (5)
H17A	−0.2053	0.4488	0.8032	0.034*
H17B	−0.1221	0.5029	0.7539	0.034*
C18	−0.04958 (16)	0.3512 (2)	0.84731 (11)	0.0251 (5)
H18A	−0.0166	0.4289	0.8883	0.030*
H18B	−0.0764	0.2716	0.8766	0.030*
C19	0.15396 (15)	0.3952 (2)	0.98361 (12)	0.0210 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0253 (8)	0.0295 (9)	0.0276 (7)	−0.0095 (7)	0.0036 (6)	−0.0025 (7)
O2	0.0266 (8)	0.0312 (9)	0.0304 (8)	−0.0010 (7)	0.0113 (7)	0.0051 (7)
O3	0.0267 (9)	0.0271 (9)	0.0317 (7)	0.0064 (7)	0.0094 (6)	0.0051 (7)
N1	0.0267 (10)	0.0335 (11)	0.0248 (9)	−0.0011 (9)	0.0084 (8)	−0.0014 (8)
N2	0.0216 (9)	0.0238 (10)	0.0218 (8)	0.0009 (8)	0.0060 (7)	−0.0038 (8)
C1	0.0667 (19)	0.0504 (18)	0.0425 (14)	−0.0253 (16)	−0.0022 (13)	−0.0074 (14)
C2	0.0247 (12)	0.0276 (13)	0.0462 (13)	−0.0058 (10)	0.0028 (10)	0.0010 (11)
C3	0.0198 (10)	0.0207 (11)	0.0251 (10)	0.0042 (9)	0.0052 (8)	0.0031 (9)
C4	0.0184 (10)	0.0219 (11)	0.0191 (9)	0.0018 (9)	0.0063 (8)	0.0032 (9)
C5	0.0224 (11)	0.0197 (11)	0.0204 (9)	0.0036 (9)	0.0065 (8)	0.0042 (9)
C6	0.0226 (11)	0.0227 (12)	0.0235 (10)	0.0034 (9)	0.0075 (8)	−0.0011 (9)
C7	0.0223 (11)	0.0185 (11)	0.0231 (10)	−0.0024 (9)	0.0059 (8)	−0.0035 (9)
C8	0.0234 (11)	0.0194 (11)	0.0217 (9)	−0.0032 (9)	0.0075 (8)	−0.0048 (9)
C9	0.0306 (12)	0.0212 (12)	0.0277 (10)	−0.0021 (10)	0.0094 (9)	−0.0006 (9)
C10	0.0422 (14)	0.0270 (13)	0.0265 (11)	−0.0055 (11)	0.0152 (10)	0.0014 (10)
C11	0.0392 (13)	0.0282 (13)	0.0367 (11)	−0.0088 (11)	0.0231 (10)	−0.0052 (11)
C12	0.0296 (12)	0.0261 (13)	0.0374 (11)	−0.0008 (10)	0.0163 (10)	−0.0038 (10)
C13	0.0286 (12)	0.0210 (12)	0.0242 (10)	−0.0025 (10)	0.0097 (9)	0.0000 (9)
C14	0.0286 (12)	0.0283 (13)	0.0328 (11)	−0.0016 (10)	0.0090 (9)	−0.0110 (10)
C15	0.0327 (12)	0.0402 (15)	0.0286 (11)	−0.0066 (11)	0.0047 (10)	−0.0131 (11)
C16	0.0258 (12)	0.0397 (15)	0.0312 (11)	0.0003 (11)	0.0002 (9)	−0.0067 (11)
C17	0.0235 (11)	0.0289 (13)	0.0313 (11)	0.0018 (10)	0.0066 (9)	−0.0036 (10)
C18	0.0228 (11)	0.0293 (13)	0.0244 (10)	−0.0004 (10)	0.0089 (9)	−0.0029 (9)
C19	0.0167 (10)	0.0203 (11)	0.0241 (10)	−0.0013 (9)	0.0031 (8)	−0.0021 (9)

Geometric parameters (Å, º)

O1—C3	1.351 (2)	C9—C10	1.380 (3)
O1—C2	1.444 (2)	C9—H9	0.9300
O2—C3	1.216 (2)	C10—C11	1.381 (3)
O3—C7	1.212 (2)	C10—H10	0.9300
N1—C19	1.148 (2)	C11—C12	1.378 (3)
N2—C5	1.332 (2)	C11—H11	0.9300
N2—C18	1.470 (2)	C12—C13	1.384 (3)
N2—C14	1.479 (2)	C12—H12	0.9300
C1—C2	1.494 (3)	C13—H13	0.9300
C1—H1A	0.9600	C14—C15	1.516 (3)
C1—H1B	0.9600	C14—H14A	0.9700
C1—H1C	0.9600	C14—H14B	0.9700
C2—H2A	0.9700	C15—C16	1.515 (3)
C2—H2B	0.9700	C15—H15A	0.9700
C3—C4	1.448 (3)	C15—H15B	0.9700
C4—C5	1.406 (3)	C16—C17	1.505 (3)
C4—C19	1.426 (3)	C16—H16A	0.9700
C5—C6	1.506 (2)	C16—H16B	0.9700
C6—C7	1.508 (3)	C17—C18	1.514 (3)
C6—H6A	0.9700	C17—H17A	0.9700
C6—H6B	0.9700	C17—H17B	0.9700
C7—C8	1.495 (3)	C18—H18A	0.9700
C8—C9	1.388 (3)	C18—H18B	0.9700
C8—C13	1.394 (3)
C3—O1—C2	117.30 (15)	C9—C10—H10	120.0
C5—N2—C18	123.58 (16)	C12—C11—C10	120.3 (2)
C5—N2—C14	124.52 (16)	C12—C11—H11	119.8
C18—N2—C14	111.89 (15)	C10—C11—H11	119.8
C2—C1—H1A	109.5	C11—C12—C13	120.0 (2)
C2—C1—H1B	109.5	C11—C12—H12	120.0
H1A—C1—H1B	109.5	C13—C12—H12	120.0
C2—C1—H1C	109.5	C12—C13—C8	120.17 (18)
H1A—C1—H1C	109.5	C12—C13—H13	119.9
H1B—C1—H1C	109.5	C8—C13—H13	119.9
O1—C2—C1	106.63 (18)	N2—C14—C15	111.93 (17)
O1—C2—H2A	110.4	N2—C14—H14A	109.2
C1—C2—H2A	110.4	C15—C14—H14A	109.2
O1—C2—H2B	110.4	N2—C14—H14B	109.2
C1—C2—H2B	110.4	C15—C14—H14B	109.2
H2A—C2—H2B	108.6	H14A—C14—H14B	107.9
O2—C3—O1	122.00 (18)	C16—C15—C14	110.66 (16)
O2—C3—C4	127.36 (18)	C16—C15—H15A	109.5
O1—C3—C4	110.61 (16)	C14—C15—H15A	109.5
C5—C4—C19	121.38 (17)	C16—C15—H15B	109.5
C5—C4—C3	122.22 (17)	C14—C15—H15B	109.5
C19—C4—C3	116.28 (16)	H15A—C15—H15B	108.1
N2—C5—C4	123.31 (17)	C17—C16—C15	110.18 (17)
N2—C5—C6	118.85 (16)	C17—C16—H16A	109.6
C4—C5—C6	117.83 (17)	C15—C16—H16A	109.6
C5—C6—C7	113.11 (16)	C17—C16—H16B	109.6
C5—C6—H6A	109.0	C15—C16—H16B	109.6
C7—C6—H6A	109.0	H16A—C16—H16B	108.1
C5—C6—H6B	109.0	C16—C17—C18	112.51 (18)
C7—C6—H6B	109.0	C16—C17—H17A	109.1
H6A—C6—H6B	107.8	C18—C17—H17A	109.1
O3—C7—C8	120.84 (17)	C16—C17—H17B	109.1
O3—C7—C6	121.74 (17)	C18—C17—H17B	109.1
C8—C7—C6	117.42 (17)	H17A—C17—H17B	107.8
C9—C8—C13	119.14 (18)	N2—C18—C17	110.73 (15)
C9—C8—C7	118.96 (18)	N2—C18—H18A	109.5
C13—C8—C7	121.87 (17)	C17—C18—H18A	109.5
C10—C9—C8	120.5 (2)	N2—C18—H18B	109.5
C10—C9—H9	119.8	C17—C18—H18B	109.5
C8—C9—H9	119.8	H18A—C18—H18B	108.1
C11—C10—C9	119.96 (19)	N1—C19—C4	176.9 (2)
C11—C10—H10	120.0
C3—O1—C2—C1	169.00 (18)	C6—C7—C8—C9	−178.69 (17)
C2—O1—C3—O2	5.9 (3)	O3—C7—C8—C13	−176.41 (18)
C2—O1—C3—C4	−172.36 (17)	C6—C7—C8—C13	3.0 (3)
O2—C3—C4—C5	5.7 (3)	C13—C8—C9—C10	−0.4 (3)
O1—C3—C4—C5	−176.15 (18)	C7—C8—C9—C10	−178.84 (18)
O2—C3—C4—C19	−178.1 (2)	C8—C9—C10—C11	0.6 (3)
O1—C3—C4—C19	0.0 (2)	C9—C10—C11—C12	−0.5 (3)
C18—N2—C5—C4	17.2 (3)	C10—C11—C12—C13	0.2 (3)
C14—N2—C5—C4	−164.10 (18)	C11—C12—C13—C8	0.0 (3)
C18—N2—C5—C6	−163.92 (17)	C9—C8—C13—C12	0.1 (3)
C14—N2—C5—C6	14.8 (3)	C7—C8—C13—C12	178.50 (17)
C19—C4—C5—N2	28.0 (3)	C5—N2—C14—C15	−122.1 (2)
C3—C4—C5—N2	−156.07 (19)	C18—N2—C14—C15	56.7 (2)
C19—C4—C5—C6	−150.89 (18)	N2—C14—C15—C16	−55.4 (2)
C3—C4—C5—C6	25.1 (3)	C14—C15—C16—C17	53.7 (3)
N2—C5—C6—C7	79.1 (2)	C15—C16—C17—C18	−54.3 (2)
C4—C5—C6—C7	−102.0 (2)	C5—N2—C18—C17	123.2 (2)
C5—C6—C7—O3	−11.8 (3)	C14—N2—C18—C17	−55.6 (2)
C5—C6—C7—C8	168.86 (16)	C16—C17—C18—N2	55.2 (2)
O3—C7—C8—C9	1.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O3^i	0.96	2.48	3.426 (3)	169
C6—H6A···O2^ii	0.97	2.46	3.278 (2)	142
C6—H6B···O2	0.97	2.31	2.798 (3)	110
C14—H14B···O2^ii	0.97	2.52	3.470 (2)	167
C18—H18A···N1	0.97	2.68	3.316 (2)	124
C18—H18A···N1^iii	0.97	2.66	3.341 (3)	127

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x, −y+1, −z+2.

(2) Ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperidin-1-yl)pent-2-enoate

Crystal data

C20H24N2O4	Dx = 1.332 Mg m^−3
Mr = 356.41	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3511 reflections
a = 8.3337 (7) Å	θ = 2.5–27.3°
b = 8.6333 (7) Å	µ = 0.09 mm^−1
c = 24.7075 (19) Å	T = 293 K
V = 1777.6 (2) Å^3	Needle, colourless
Z = 4	0.7 × 0.05 × 0.02 mm
F(000) = 760

Data collection

Bruker APEXII CCD area-detector diffractometer	Rint = 0.079
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.5°
φ and ω scans	h = −9→9
11639 measured reflections	k = −10→10
3129 independent reflections	l = −29→28
2295 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 0.1237P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.110	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.20 e Å^−3
3129 reflections	Δρmin = −0.19 e Å^−3
235 parameters	Absolute structure: Flack x parameter determined using 771 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 1.0 (10)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1452 (3)	−0.0333 (3)	0.83937 (10)	0.0214 (6)
O2	0.2775 (3)	0.0519 (3)	0.76611 (10)	0.0233 (7)
O3	0.6921 (3)	0.0501 (3)	0.77621 (10)	0.0218 (6)
O4	0.6213 (3)	0.1266 (3)	0.52316 (10)	0.0273 (7)
N1	0.2949 (4)	0.0391 (4)	0.95301 (14)	0.0289 (9)
N2	0.5965 (3)	0.2946 (4)	0.87428 (12)	0.0190 (8)
C1	−0.0745 (4)	−0.2096 (5)	0.83533 (16)	0.0253 (10)
H1A	−0.1468	−0.2674	0.8114	0.038*
H1B	−0.0147	−0.2822	0.8582	0.038*
H1C	−0.1375	−0.1397	0.8583	0.038*
C2	0.0408 (5)	−0.1168 (5)	0.80185 (15)	0.0238 (10)
H2A	0.1051	−0.1861	0.7784	0.029*
H2B	−0.0182	−0.0430	0.7785	0.029*
C3	0.2628 (4)	0.0492 (5)	0.81538 (15)	0.0187 (9)
C4	0.3657 (5)	0.1265 (5)	0.85582 (14)	0.0189 (9)
C5	0.4927 (4)	0.2256 (4)	0.84053 (15)	0.0181 (9)
C6	0.5112 (4)	0.2627 (5)	0.78150 (14)	0.0195 (9)
H6A	0.5628	0.3655	0.7778	0.023*
H6B	0.4035	0.2691	0.7647	0.023*
C7	0.6105 (4)	0.1435 (5)	0.75118 (14)	0.0181 (9)
C8	0.6098 (5)	0.1457 (5)	0.69107 (14)	0.0187 (9)
C9	0.7166 (4)	0.0515 (5)	0.66302 (15)	0.0194 (9)
H9	0.7892	−0.0120	0.6827	0.023*
C10	0.7189 (4)	0.0484 (5)	0.60751 (15)	0.0227 (9)
H10	0.7938	−0.0157	0.5891	0.027*
C11	0.6110 (5)	0.1396 (5)	0.57790 (15)	0.0214 (9)
C12	0.5038 (4)	0.2352 (5)	0.60516 (15)	0.0221 (9)
H12	0.4304	0.2978	0.5855	0.026*
C13	0.5045 (4)	0.2386 (4)	0.66112 (15)	0.0187 (9)
H13	0.4321	0.3052	0.6796	0.022*
C14	0.7512 (5)	0.3630 (5)	0.85663 (15)	0.0227 (9)
H14A	0.7654	0.4664	0.8733	0.027*
H14B	0.7518	0.3757	0.8168	0.027*
C15	0.8881 (4)	0.2561 (5)	0.87383 (15)	0.0272 (10)
H15A	0.9918	0.3036	0.8635	0.033*
H15B	0.8784	0.1563	0.8544	0.033*
C16	0.8867 (5)	0.2261 (5)	0.93501 (15)	0.0275 (10)
H16A	0.9669	0.1455	0.9440	0.033*
H16B	0.9168	0.3221	0.9544	0.033*
C17	0.7206 (5)	0.1731 (5)	0.95368 (16)	0.0264 (10)
H17A	0.6976	0.0686	0.9391	0.032*
H17B	0.7176	0.1674	0.9937	0.032*
C18	0.5946 (4)	0.2872 (5)	0.93370 (14)	0.0209 (9)
H18A	0.4871	0.2542	0.9463	0.025*
H18B	0.6167	0.3912	0.9488	0.025*
C19	0.3291 (4)	0.0806 (5)	0.91015 (17)	0.0214 (9)
C20	0.5072 (5)	0.2132 (5)	0.49119 (16)	0.0318 (11)
H20A	0.5271	0.1942	0.4527	0.048*
H20B	0.3981	0.1801	0.5004	0.048*
H20C	0.5191	0.3240	0.4988	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0165 (14)	0.0273 (16)	0.0205 (14)	−0.0047 (12)	−0.0001 (11)	−0.0033 (13)
O2	0.0265 (16)	0.0264 (17)	0.0171 (15)	0.0001 (14)	−0.0004 (11)	−0.0008 (13)
O3	0.0206 (15)	0.0207 (15)	0.0240 (15)	0.0032 (13)	−0.0019 (12)	0.0010 (14)
O4	0.0342 (17)	0.0319 (17)	0.0159 (15)	−0.0002 (15)	0.0019 (13)	0.0002 (13)
N1	0.031 (2)	0.031 (2)	0.025 (2)	−0.0071 (18)	0.0021 (16)	−0.0028 (18)
N2	0.0209 (18)	0.0191 (18)	0.0170 (18)	0.0001 (15)	0.0016 (14)	0.0008 (15)
C1	0.021 (2)	0.026 (2)	0.028 (2)	0.0006 (18)	−0.0038 (18)	−0.002 (2)
C2	0.020 (2)	0.026 (2)	0.025 (2)	0.0024 (19)	−0.0042 (17)	−0.003 (2)
C3	0.017 (2)	0.015 (2)	0.024 (2)	0.0060 (19)	0.0004 (17)	0.0021 (19)
C4	0.021 (2)	0.018 (2)	0.018 (2)	0.0010 (18)	0.0014 (17)	0.0031 (18)
C5	0.019 (2)	0.016 (2)	0.019 (2)	0.0084 (17)	0.0023 (17)	−0.0006 (18)
C6	0.019 (2)	0.019 (2)	0.020 (2)	−0.0001 (17)	−0.0013 (17)	0.0011 (18)
C7	0.015 (2)	0.018 (2)	0.021 (2)	−0.0047 (19)	0.0005 (17)	0.0005 (19)
C8	0.016 (2)	0.020 (2)	0.019 (2)	−0.0042 (19)	−0.0001 (16)	−0.0013 (18)
C9	0.018 (2)	0.018 (2)	0.022 (2)	−0.0023 (18)	0.0014 (17)	0.001 (2)
C10	0.019 (2)	0.023 (2)	0.026 (2)	−0.0002 (19)	0.0046 (17)	−0.002 (2)
C11	0.023 (2)	0.021 (2)	0.019 (2)	−0.007 (2)	0.0007 (17)	−0.0017 (19)
C12	0.023 (2)	0.021 (2)	0.022 (2)	−0.0029 (19)	−0.0026 (17)	0.0009 (18)
C13	0.018 (2)	0.017 (2)	0.022 (2)	−0.0016 (17)	0.0018 (17)	−0.0016 (18)
C14	0.024 (2)	0.023 (2)	0.021 (2)	−0.0046 (19)	0.0028 (18)	−0.0005 (19)
C15	0.017 (2)	0.035 (3)	0.029 (2)	−0.002 (2)	−0.0003 (18)	−0.004 (2)
C16	0.030 (2)	0.028 (2)	0.025 (2)	0.004 (2)	−0.0075 (19)	−0.0006 (19)
C17	0.029 (2)	0.028 (3)	0.023 (2)	−0.0021 (19)	−0.0047 (18)	−0.0022 (19)
C18	0.022 (2)	0.024 (2)	0.017 (2)	−0.004 (2)	−0.0008 (17)	−0.0038 (18)
C19	0.018 (2)	0.020 (2)	0.026 (2)	0.0019 (17)	0.0006 (18)	−0.0050 (19)
C20	0.043 (3)	0.033 (3)	0.020 (2)	0.000 (2)	−0.004 (2)	0.001 (2)

Geometric parameters (Å, º)

O1—C3	1.349 (4)	C5—C6	1.501 (5)
O1—C2	1.462 (4)	C6—C7	1.519 (5)
O2—C3	1.224 (4)	C7—C8	1.485 (5)
O3—C7	1.223 (4)	C8—C9	1.391 (5)
O4—C11	1.360 (4)	C8—C13	1.400 (5)
O4—C20	1.445 (5)	C9—C10	1.372 (5)
N1—C19	1.154 (5)	C10—C11	1.401 (5)
N2—C5	1.341 (5)	C11—C12	1.391 (5)
N2—C18	1.470 (4)	C12—C13	1.383 (5)
N2—C14	1.484 (5)	C14—C15	1.527 (5)
C1—C2	1.499 (5)	C15—C16	1.534 (5)
C3—C4	1.476 (5)	C16—C17	1.530 (5)
C4—C5	1.413 (5)	C17—C18	1.522 (5)
C4—C19	1.433 (5)
C3—O1—C2	114.5 (3)	C8—C7—C6	118.8 (3)
C11—O4—C20	117.4 (3)	C9—C8—C13	118.2 (3)
C5—N2—C18	126.5 (3)	C9—C8—C7	119.2 (4)
C5—N2—C14	123.7 (3)	C13—C8—C7	122.6 (4)
C18—N2—C14	108.7 (3)	C10—C9—C8	121.2 (4)
O1—C2—C1	107.2 (3)	C9—C10—C11	120.2 (4)
O2—C3—O1	121.3 (4)	O4—C11—C12	124.8 (4)
O2—C3—C4	127.4 (4)	O4—C11—C10	115.6 (4)
O1—C3—C4	111.3 (3)	C12—C11—C10	119.5 (3)
C5—C4—C19	125.3 (3)	C13—C12—C11	119.6 (4)
C5—C4—C3	121.9 (3)	C12—C13—C8	121.3 (4)
C19—C4—C3	112.7 (3)	N2—C14—C15	109.1 (3)
N2—C5—C4	125.9 (3)	C14—C15—C16	111.8 (3)
N2—C5—C6	116.3 (3)	C17—C16—C15	110.8 (3)
C4—C5—C6	117.8 (3)	C18—C17—C16	109.5 (3)
C5—C6—C7	113.0 (3)	N2—C18—C17	110.2 (3)
O3—C7—C8	121.1 (3)	N1—C19—C4	177.0 (4)
O3—C7—C6	120.0 (3)
C3—O1—C2—C1	176.2 (3)	C6—C7—C8—C13	−9.2 (5)
C2—O1—C3—O2	0.2 (5)	C13—C8—C9—C10	−0.3 (6)
C2—O1—C3—C4	−178.4 (3)	C7—C8—C9—C10	179.2 (3)
O2—C3—C4—C5	4.6 (6)	C8—C9—C10—C11	−0.9 (6)
O1—C3—C4—C5	−176.9 (3)	C20—O4—C11—C12	−3.1 (6)
O2—C3—C4—C19	−171.2 (4)	C20—O4—C11—C10	177.2 (3)
O1—C3—C4—C19	7.3 (5)	C9—C10—C11—O4	−179.1 (4)
C18—N2—C5—C4	−3.1 (6)	C9—C10—C11—C12	1.2 (6)
C14—N2—C5—C4	163.3 (4)	O4—C11—C12—C13	−180.0 (4)
C18—N2—C5—C6	174.6 (3)	C10—C11—C12—C13	−0.3 (6)
C14—N2—C5—C6	−19.0 (5)	C11—C12—C13—C8	−0.9 (6)
C19—C4—C5—N2	−1.4 (6)	C9—C8—C13—C12	1.2 (6)
C3—C4—C5—N2	−176.7 (3)	C7—C8—C13—C12	−178.3 (3)
C19—C4—C5—C6	−179.1 (3)	C5—N2—C14—C15	−105.1 (4)
C3—C4—C5—C6	5.6 (5)	C18—N2—C14—C15	63.4 (4)
N2—C5—C6—C7	95.8 (4)	N2—C14—C15—C16	−56.5 (4)
C4—C5—C6—C7	−86.3 (4)	C14—C15—C16—C17	51.3 (5)
C5—C6—C7—O3	−14.8 (5)	C15—C16—C17—C18	−52.1 (5)
C5—C6—C7—C8	166.9 (3)	C5—N2—C18—C17	101.8 (4)
O3—C7—C8—C9	−7.0 (6)	C14—N2—C18—C17	−66.3 (4)
C6—C7—C8—C9	171.3 (3)	C16—C17—C18—N2	60.3 (4)
O3—C7—C8—C13	172.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2^i	0.99	2.35	3.274 (5)	154
C2—H2B···O3^ii	0.99	2.54	3.305 (5)	133
C14—H14B···O2^i	0.99	2.56	3.452 (5)	149
C15—H15B···O3	0.99	2.64	3.413 (5)	135
C18—H18A···N1	0.99	2.46	3.325 (5)	146
C20—H20C···N1^i	0.98	2.70	3.541 (6)	145

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, y, z.

(3) Ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate

Crystal data

C19H21ClN2O3	Dx = 1.373 Mg m^−3
Mr = 360.83	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 6432 reflections
a = 4.9520 (3) Å	θ = 2.8–27.6°
b = 13.6151 (7) Å	µ = 0.24 mm^−1
c = 25.8916 (15) Å	T = 293 K
V = 1745.66 (17) Å^3	Rod, colourless
Z = 4	0.34 × 0.12 × 0.10 mm
F(000) = 760

Data collection

Bruker APEXII CCD area-detector diffractometer	Rint = 0.034
Radiation source: fine-focus sealed tube	θmax = 27.7°, θmin = 2.8°
φ and ω scans	h = −6→6
14442 measured reflections	k = −17→15
4047 independent reflections	l = −32→33
3656 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.1249P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.084	(Δ/σ)max = 0.001
S = 1.01	Δρmax = 0.28 e Å^−3
4047 reflections	Δρmin = −0.20 e Å^−3
310 parameters	Absolute structure: Flack x parameter determined using 1382 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.03 (2)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.55221 (14)	0.33608 (4)	0.84527 (2)	0.03002 (16)
O1	−0.0274 (3)	0.73933 (11)	1.10559 (5)	0.0210 (3)
O2	0.1821 (4)	0.63433 (12)	1.05231 (6)	0.0280 (4)
O3	0.1779 (3)	0.40036 (11)	1.09061 (6)	0.0233 (4)
N1	0.0022 (4)	0.69226 (15)	1.22454 (7)	0.0271 (5)
N2	0.5362 (4)	0.50367 (12)	1.18822 (6)	0.0187 (4)
C1	−0.3407 (6)	0.86131 (19)	1.07896 (9)	0.0292 (5)
H1A	−0.491 (6)	0.830 (2)	1.0987 (11)	0.032 (7)*
H1B	−0.237 (6)	0.9116 (19)	1.0997 (10)	0.026 (7)*
H1C	−0.421 (7)	0.891 (2)	1.0485 (12)	0.038 (8)*
C2	−0.1488 (6)	0.78452 (18)	1.06052 (8)	0.0249 (5)
H2A	−0.002 (6)	0.8132 (19)	1.0380 (10)	0.027 (7)*
H2B	−0.232 (5)	0.734 (2)	1.0412 (10)	0.024 (7)*
C3	0.1395 (4)	0.66305 (15)	1.09611 (8)	0.0184 (4)
C4	0.2456 (4)	0.62207 (15)	1.14469 (8)	0.0173 (4)
C5	0.4369 (4)	0.54647 (14)	1.14584 (8)	0.0168 (4)
C6	0.5493 (5)	0.51090 (15)	1.09470 (8)	0.0179 (4)
H6A	0.571 (6)	0.5688 (18)	1.0724 (9)	0.021 (6)*
H6B	0.731 (6)	0.4822 (19)	1.0979 (9)	0.024 (7)*
C7	0.3645 (4)	0.43913 (15)	1.06771 (8)	0.0170 (4)
C8	0.4201 (5)	0.41489 (15)	1.01243 (8)	0.0175 (4)
C9	0.2544 (5)	0.34635 (16)	0.98801 (8)	0.0220 (5)
H9	0.110 (6)	0.317 (2)	1.0070 (11)	0.035 (8)*
C10	0.2952 (5)	0.32180 (17)	0.93666 (9)	0.0250 (5)
H10	0.192 (6)	0.276 (2)	0.9204 (10)	0.030 (7)*
C11	0.5024 (5)	0.36606 (15)	0.90962 (8)	0.0221 (5)
C12	0.6696 (5)	0.43409 (18)	0.93301 (9)	0.0258 (5)
H12	0.809 (7)	0.465 (2)	0.9139 (11)	0.036 (8)*
C13	0.6294 (5)	0.45836 (18)	0.98470 (9)	0.0242 (5)
H13	0.752 (7)	0.502 (2)	1.0017 (11)	0.034 (8)*
C14	0.6662 (5)	0.40587 (16)	1.18793 (8)	0.0216 (5)
H14A	0.686 (5)	0.3820 (18)	1.1536 (10)	0.023 (6)*
H14B	0.863 (6)	0.4121 (18)	1.2002 (10)	0.025 (7)*
C15	0.5062 (6)	0.33622 (18)	1.22216 (9)	0.0276 (5)
H15A	0.323 (7)	0.327 (2)	1.2091 (11)	0.033 (7)*
H15B	0.589 (7)	0.272 (2)	1.2214 (10)	0.037 (8)*
C16	0.4846 (6)	0.37454 (18)	1.27743 (9)	0.0270 (5)
H16A	0.375 (6)	0.332 (2)	1.2988 (10)	0.029 (7)*
H16B	0.660 (7)	0.3732 (19)	1.2917 (11)	0.028 (7)*
C17	0.3655 (5)	0.47757 (19)	1.27722 (9)	0.0258 (5)
H17A	0.159 (6)	0.475 (2)	1.2673 (11)	0.040 (8)*
H17B	0.375 (5)	0.5059 (18)	1.3109 (10)	0.025 (7)*
C18	0.5255 (5)	0.54328 (16)	1.24127 (8)	0.0212 (5)
H18A	0.468 (6)	0.6078 (19)	1.2411 (9)	0.020 (6)*
H18B	0.710 (6)	0.544 (2)	1.2521 (10)	0.026 (7)*
C19	0.1157 (4)	0.66036 (15)	1.18957 (7)	0.0180 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0474 (4)	0.0284 (3)	0.0142 (2)	0.0066 (3)	0.0048 (2)	−0.0023 (2)
O1	0.0276 (8)	0.0211 (7)	0.0144 (7)	0.0060 (7)	−0.0016 (6)	0.0018 (5)
O2	0.0399 (10)	0.0297 (9)	0.0145 (7)	0.0116 (8)	−0.0011 (7)	−0.0007 (6)
O3	0.0248 (8)	0.0243 (8)	0.0208 (7)	−0.0061 (7)	0.0065 (7)	−0.0028 (6)
N1	0.0281 (12)	0.0374 (11)	0.0159 (9)	0.0058 (9)	0.0000 (8)	0.0010 (7)
N2	0.0228 (9)	0.0172 (8)	0.0161 (8)	0.0025 (8)	−0.0020 (7)	−0.0016 (6)
C1	0.0337 (13)	0.0316 (13)	0.0224 (11)	0.0097 (11)	−0.0030 (11)	0.0047 (9)
C2	0.0349 (13)	0.0247 (12)	0.0151 (10)	0.0068 (10)	−0.0034 (10)	0.0038 (8)
C3	0.0221 (10)	0.0165 (10)	0.0168 (9)	−0.0011 (9)	−0.0002 (8)	0.0008 (8)
C4	0.0218 (11)	0.0159 (9)	0.0141 (9)	−0.0018 (8)	−0.0013 (8)	0.0010 (7)
C5	0.0178 (10)	0.0155 (9)	0.0171 (9)	−0.0057 (8)	0.0006 (8)	−0.0011 (7)
C6	0.0189 (10)	0.0200 (10)	0.0148 (9)	−0.0005 (9)	0.0019 (8)	0.0007 (8)
C7	0.0173 (10)	0.0165 (10)	0.0171 (10)	0.0033 (8)	0.0008 (8)	0.0010 (8)
C8	0.0191 (10)	0.0184 (9)	0.0151 (9)	0.0049 (8)	0.0007 (8)	−0.0002 (7)
C9	0.0239 (11)	0.0221 (11)	0.0199 (10)	−0.0018 (10)	0.0014 (8)	−0.0011 (9)
C10	0.0314 (13)	0.0223 (12)	0.0213 (11)	0.0013 (10)	−0.0025 (10)	−0.0048 (9)
C11	0.0301 (13)	0.0239 (11)	0.0122 (9)	0.0111 (9)	0.0011 (8)	−0.0003 (7)
C12	0.0274 (12)	0.0302 (12)	0.0199 (11)	0.0003 (11)	0.0074 (10)	0.0001 (9)
C13	0.0243 (12)	0.0282 (12)	0.0201 (11)	−0.0027 (10)	0.0025 (9)	−0.0031 (9)
C14	0.0255 (12)	0.0219 (11)	0.0175 (10)	0.0075 (9)	−0.0017 (9)	−0.0024 (8)
C15	0.0414 (16)	0.0173 (11)	0.0243 (11)	0.0018 (11)	−0.0057 (10)	−0.0008 (8)
C16	0.0346 (14)	0.0260 (11)	0.0202 (11)	−0.0066 (11)	0.0012 (11)	0.0026 (8)
C17	0.0224 (12)	0.0376 (13)	0.0173 (11)	0.0024 (10)	−0.0006 (9)	−0.0038 (9)
C18	0.0283 (13)	0.0187 (11)	0.0168 (10)	0.0041 (9)	−0.0070 (9)	−0.0036 (8)
C19	0.0195 (11)	0.0199 (10)	0.0146 (9)	−0.0011 (9)	−0.0030 (7)	0.0043 (8)

Geometric parameters (Å, º)

Cl1—C11	1.733 (2)	C8—C13	1.393 (3)
O1—C3	1.350 (3)	C9—C10	1.386 (3)
O1—C2	1.450 (3)	C9—H9	0.96 (3)
O2—C3	1.218 (3)	C10—C11	1.381 (3)
O3—C7	1.218 (3)	C10—H10	0.91 (3)
N1—C19	1.151 (3)	C11—C12	1.382 (4)
N2—C5	1.336 (3)	C12—C13	1.393 (3)
N2—C18	1.477 (2)	C12—H12	0.95 (3)
N2—C14	1.479 (3)	C13—H13	0.96 (3)
C1—C2	1.492 (3)	C14—C15	1.521 (3)
C1—H1A	1.00 (3)	C14—H14A	0.95 (3)
C1—H1B	1.01 (3)	C14—H14B	1.03 (3)
C1—H1C	0.97 (3)	C15—C16	1.527 (3)
C2—H2A	1.01 (3)	C15—H15A	0.97 (3)
C2—H2B	0.95 (3)	C15—H15B	0.97 (3)
C3—C4	1.473 (3)	C16—C17	1.522 (4)
C4—C5	1.399 (3)	C16—H16A	0.97 (3)
C4—C19	1.427 (3)	C16—H16B	0.94 (3)
C5—C6	1.516 (3)	C17—C18	1.515 (3)
C6—C7	1.510 (3)	C17—H17A	1.05 (3)
C6—H6A	0.98 (3)	C17—H17B	0.95 (3)
C6—H6B	0.99 (3)	C18—H18A	0.92 (3)
C7—C8	1.494 (3)	C18—H18B	0.95 (3)
C8—C9	1.394 (3)
C3—O1—C2	115.72 (16)	C9—C10—H10	121.9 (18)
C5—N2—C18	126.25 (18)	C10—C11—C12	121.0 (2)
C5—N2—C14	123.27 (17)	C10—C11—Cl1	119.38 (18)
C18—N2—C14	110.45 (16)	C12—C11—Cl1	119.59 (18)
C2—C1—H1A	110.2 (17)	C11—C12—C13	119.6 (2)
C2—C1—H1B	108.7 (17)	C11—C12—H12	120.4 (17)
H1A—C1—H1B	113 (2)	C13—C12—H12	120.0 (18)
C2—C1—H1C	107.0 (19)	C12—C13—C8	120.1 (2)
H1A—C1—H1C	107 (3)	C12—C13—H13	119.9 (18)
H1B—C1—H1C	111 (2)	C8—C13—H13	119.9 (18)
O1—C2—C1	107.71 (18)	N2—C14—C15	109.4 (2)
O1—C2—H2A	109.3 (16)	N2—C14—H14A	111.0 (15)
C1—C2—H2A	111.9 (15)	C15—C14—H14A	112.6 (16)
O1—C2—H2B	107.2 (16)	N2—C14—H14B	109.7 (15)
C1—C2—H2B	113.9 (17)	C15—C14—H14B	111.4 (15)
H2A—C2—H2B	107 (2)	H14A—C14—H14B	103 (2)
O2—C3—O1	121.50 (19)	C14—C15—C16	111.7 (2)
O2—C3—C4	127.7 (2)	C14—C15—H15A	111.2 (17)
O1—C3—C4	110.76 (17)	C16—C15—H15A	107.8 (17)
C5—C4—C19	123.83 (18)	C14—C15—H15B	109.3 (18)
C5—C4—C3	122.57 (18)	C16—C15—H15B	111.0 (16)
C19—C4—C3	113.34 (18)	H15A—C15—H15B	106 (3)
N2—C5—C4	125.98 (18)	C17—C16—C15	109.80 (19)
N2—C5—C6	116.28 (19)	C17—C16—H16A	109.8 (17)
C4—C5—C6	117.72 (18)	C15—C16—H16A	111.7 (16)
C7—C6—C5	112.84 (18)	C17—C16—H16B	112.1 (17)
C7—C6—H6A	108.4 (15)	C15—C16—H16B	107.3 (17)
C5—C6—H6A	107.3 (14)	H16A—C16—H16B	106 (2)
C7—C6—H6B	109.7 (15)	C18—C17—C16	110.1 (2)
C5—C6—H6B	112.9 (15)	C18—C17—H17A	112.1 (16)
H6A—C6—H6B	105 (2)	C16—C17—H17A	110.3 (17)
O3—C7—C8	120.7 (2)	C18—C17—H17B	107.1 (16)
O3—C7—C6	120.99 (18)	C16—C17—H17B	110.5 (15)
C8—C7—C6	118.32 (18)	H17A—C17—H17B	107 (2)
C9—C8—C13	119.25 (19)	N2—C18—C17	112.00 (18)
C9—C8—C7	118.27 (19)	N2—C18—H18A	110.7 (15)
C13—C8—C7	122.5 (2)	C17—C18—H18A	113.8 (17)
C10—C9—C8	120.7 (2)	N2—C18—H18B	104.0 (16)
C10—C9—H9	120.0 (17)	C17—C18—H18B	108.9 (16)
C8—C9—H9	119.2 (17)	H18A—C18—H18B	107 (2)
C11—C10—C9	119.3 (2)	N1—C19—C4	177.2 (2)
C11—C10—H10	118.7 (18)
C3—O1—C2—C1	175.7 (2)	O3—C7—C8—C13	179.3 (2)
C2—O1—C3—O2	−0.5 (3)	C6—C7—C8—C13	−2.2 (3)
C2—O1—C3—C4	−178.83 (19)	C13—C8—C9—C10	−0.4 (3)
O2—C3—C4—C5	6.0 (4)	C7—C8—C9—C10	179.4 (2)
O1—C3—C4—C5	−175.76 (19)	C8—C9—C10—C11	−0.1 (3)
O2—C3—C4—C19	−168.3 (2)	C9—C10—C11—C12	0.2 (3)
O1—C3—C4—C19	9.9 (3)	C9—C10—C11—Cl1	−179.56 (18)
C18—N2—C5—C4	−18.0 (4)	C10—C11—C12—C13	0.2 (4)
C14—N2—C5—C4	159.7 (2)	Cl1—C11—C12—C13	179.89 (18)
C18—N2—C5—C6	160.3 (2)	C11—C12—C13—C8	−0.6 (4)
C14—N2—C5—C6	−22.0 (3)	C9—C8—C13—C12	0.7 (3)
C19—C4—C5—N2	−4.1 (3)	C7—C8—C13—C12	−179.0 (2)
C3—C4—C5—N2	−177.9 (2)	C5—N2—C14—C15	−118.5 (2)
C19—C4—C5—C6	177.7 (2)	C18—N2—C14—C15	59.5 (2)
C3—C4—C5—C6	3.9 (3)	N2—C14—C15—C16	−57.9 (3)
N2—C5—C6—C7	100.4 (2)	C14—C15—C16—C17	55.1 (3)
C4—C5—C6—C7	−81.2 (2)	C15—C16—C17—C18	−53.4 (3)
C5—C6—C7—O3	−14.4 (3)	C5—N2—C18—C17	117.7 (2)
C5—C6—C7—C8	167.06 (18)	C14—N2—C18—C17	−60.2 (3)
O3—C7—C8—C9	−0.5 (3)	C16—C17—C18—N2	56.8 (2)
C6—C7—C8—C9	178.07 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2	0.98 (3)	2.19 (3)	2.709 (3)	112 (2)
C6—H6B···O3^i	0.99 (3)	2.48 (3)	3.459 (3)	170 (2)
C15—H15A···Cl1^ii	0.97 (3)	2.95 (3)	3.688 (2)	133 (2)
C15—H15B···N1^iii	0.97 (3)	2.69 (3)	3.417 (3)	132 (2)
C18—H18A···N1	0.92 (3)	2.61 (3)	3.319 (3)	134 (2)
C18—H18B···N1^i	0.95 (3)	2.59 (3)	3.142 (3)	117 (2)

Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+1/2, −z+2; (iii) −x+1, y−1/2, −z+5/2.