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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, C
19H
22N
2O
3, (1), ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C
20H
24N
2O
4, (2), ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C
19H
21ClN
2O
3, (3), and the previously published ethyl 5-(4-bromophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C
19H
21BrN
2O
3, (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—
XN
C interaction (
X = F, Cl, Br or I),
viz. the N
X distance and the C—
XN 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.
Supporting information
CCDC references: 1424077; 1424078; 1424079; 1424080
Crystal data, data collection and structure refinement details are summarized
in Table 1.
S2. Results and discussion
top
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).
(1) Ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-enoate
top
Crystal data top
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) Å3 | 0.60 × 0.06 × 0.02 mm |
Data collection top
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 top
Refinement on F2 | 3 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0716P)2] where P = (Fo2 + 2Fc2)/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 |
Crystal data top
C19H22N2O3 | V = 1743.8 (2) Å3 |
Mr = 326.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.4152 (10) Å | µ = 0.09 mm−1 |
b = 8.9071 (6) Å | T = 293 K |
c = 16.5072 (12) Å | 0.60 × 0.06 × 0.02 mm |
β = 107.194 (2)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2211 reflections with I > 2σ(I) |
7982 measured reflections | Rint = 0.044 |
3550 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 3 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
3550 reflections | Δρmin = −0.26 e Å−3 |
217 parameters | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O3i | 0.96 | 2.48 | 3.426 (3) | 169 |
C6—H6A···O2ii | 0.97 | 2.46 | 3.278 (2) | 142 |
C6—H6B···O2 | 0.97 | 2.31 | 2.798 (3) | 110 |
C14—H14B···O2ii | 0.97 | 2.52 | 3.470 (2) | 167 |
C18—H18A···N1 | 0.97 | 2.68 | 3.316 (2) | 124 |
C18—H18A···N1iii | 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
top
Crystal data top
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) Å3 | Needle, colourless |
Z = 4 | 0.7 × 0.05 × 0.02 mm |
F(000) = 760 | |
Data collection top
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 top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0497P)2 + 0.1237P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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) |
Crystal data top
C20H24N2O4 | V = 1777.6 (2) Å3 |
Mr = 356.41 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.3337 (7) Å | µ = 0.09 mm−1 |
b = 8.6333 (7) Å | T = 293 K |
c = 24.7075 (19) Å | 0.7 × 0.05 × 0.02 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2295 reflections with I > 2σ(I) |
11639 measured reflections | Rint = 0.079 |
3129 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.110 | Δρmax = 0.20 e Å−3 |
S = 1.01 | Δρmin = −0.19 e Å−3 |
3129 reflections | Absolute structure: Flack x parameter determined using 771 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
235 parameters | Absolute structure parameter: 1.0 (10) |
0 restraints | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O2i | 0.99 | 2.35 | 3.274 (5) | 154 |
C2—H2B···O3ii | 0.99 | 2.54 | 3.305 (5) | 133 |
C14—H14B···O2i | 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···N1i | 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
top
Crystal data top
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) Å3 | Rod, colourless |
Z = 4 | 0.34 × 0.12 × 0.10 mm |
F(000) = 760 | |
Data collection top
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 top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.1249P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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) |
Crystal data top
C19H21ClN2O3 | V = 1745.66 (17) Å3 |
Mr = 360.83 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.9520 (3) Å | µ = 0.24 mm−1 |
b = 13.6151 (7) Å | T = 293 K |
c = 25.8916 (15) Å | 0.34 × 0.12 × 0.10 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 3656 reflections with I > 2σ(I) |
14442 measured reflections | Rint = 0.034 |
4047 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | All H-atom parameters refined |
wR(F2) = 0.084 | Δρmax = 0.28 e Å−3 |
S = 1.01 | Δρmin = −0.20 e Å−3 |
4047 reflections | Absolute structure: Flack x parameter determined using 1382 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
310 parameters | Absolute structure parameter: 0.03 (2) |
0 restraints | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O3i | 0.99 (3) | 2.48 (3) | 3.459 (3) | 170 (2) |
C15—H15A···Cl1ii | 0.97 (3) | 2.95 (3) | 3.688 (2) | 133 (2) |
C15—H15B···N1iii | 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···N1i | 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. |
Experimental details
| (1) | (2) | (3) |
Crystal data |
Chemical formula | C19H22N2O3 | C20H24N2O4 | C19H21ClN2O3 |
Mr | 326.38 | 356.41 | 360.83 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 12.4152 (10), 8.9071 (6), 16.5072 (12) | 8.3337 (7), 8.6333 (7), 24.7075 (19) | 4.9520 (3), 13.6151 (7), 25.8916 (15) |
α, β, γ (°) | 90, 107.194 (2), 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 1743.8 (2) | 1777.6 (2) | 1745.66 (17) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.24 |
Crystal size (mm) | 0.60 × 0.06 × 0.02 | 0.7 × 0.05 × 0.02 | 0.34 × 0.12 × 0.10 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector | Bruker APEXII CCD area-detector | Bruker APEXII CCD area-detector |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7982, 3550, 2211 | 11639, 3129, 2295 | 14442, 4047, 3656 |
Rint | 0.044 | 0.079 | 0.034 |
(sin θ/λ)max (Å−1) | 0.625 | 0.595 | 0.653 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.140, 1.02 | 0.047, 0.110, 1.01 | 0.034, 0.084, 1.01 |
No. of reflections | 3550 | 3129 | 4047 |
No. of parameters | 217 | 235 | 310 |
No. of restraints | 3 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.22, −0.26 | 0.20, −0.19 | 0.28, −0.20 |
Absolute structure | ? | Flack x parameter determined using 771 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) | Flack x parameter determined using 1382 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Absolute structure parameter | ? | 1.0 (10) | 0.03 (2) |
Hydrogen-bond geometry (Å, º) for (1) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O3i | 0.96 | 2.48 | 3.426 (3) | 169.1 |
C6—H6A···O2ii | 0.97 | 2.46 | 3.278 (2) | 142.2 |
C6—H6B···O2 | 0.97 | 2.31 | 2.798 (3) | 110.2 |
C14—H14B···O2ii | 0.97 | 2.52 | 3.470 (2) | 166.8 |
C18—H18A···N1 | 0.97 | 2.68 | 3.316 (2) | 123.9 |
C18—H18A···N1iii | 0.97 | 2.66 | 3.341 (3) | 127.3 |
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. |
Hydrogen-bond geometry (Å, º) for (2) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O2i | 0.99 | 2.35 | 3.274 (5) | 154.3 |
C2—H2B···O3ii | 0.99 | 2.54 | 3.305 (5) | 133.4 |
C14—H14B···O2i | 0.99 | 2.56 | 3.452 (5) | 149.2 |
C15—H15B···O3 | 0.99 | 2.64 | 3.413 (5) | 134.8 |
C18—H18A···N1 | 0.99 | 2.46 | 3.325 (5) | 145.9 |
C20—H20C···N1i | 0.98 | 2.70 | 3.541 (6) | 144.6 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (3) top
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···O3i | 0.99 (3) | 2.48 (3) | 3.459 (3) | 170 (2) |
C15—H15A···Cl1ii | 0.97 (3) | 2.95 (3) | 3.688 (2) | 133 (2) |
C15—H15B···N1iii | 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···N1i | 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. |
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