organic compounds
Allyl 6-amino-4-(4-chlorophenyl)-5-cyano-2-methyl-4H-pyran-3-carboxylate
aDepartment of Physics, Saranathan College of Engineering, Panjappur, Tiruchirappalli 620 012, Tamilnadu, India, bDepartment of Physics, K. Ramakrishnan College of Engineering, Samayapuram, Tiruchirappalli 621 112, Tamilnadu, India, cDepartment of Chemistry, School of Advanced Sciences, Kalasalingam Academy of Research and Education (Deemed to be University), Krishnankoil 626 126, Tamil Nadu, India, and dDepartment of Physics, Urumu Dhanalakshmi College, Tiruchirappalli, Tamilnadu, India
*Correspondence e-mail: m.velayuthampillai@klu.ac.in
In the title compound, C17H15ClN2O3, the 4H-pyran ring exhibits a shallow-boat conformation and the chlorobenzene ring occupies an axial position. The O-allyl side chain is disordered over two orientations in a 0.585 (14):0.415 (14) ratio. In the crystal, inversion dimers linked by pairs of weak N—H⋯N hydrogen bonds generate R22(12) loops and N—H⋯O hydrogen bonds link the dimers into [001] chains.
Keywords: crystal structure; pyran; hydrogen bonds.
CCDC reference: 1901250
Structure description
Pyran derivatives possess various biological properties such as antimicrobial (Aytemir et al., 2003) and anti-mycobacterial (Kumar et al., 2007) activities. As part of our studies in this area, we now describe the synthesis and structure of the title compound (Fig. 1).
The 4H-pyran ring exhibits a shallow boat conformation with puckering parameters Q = 0.2185 (3) Å, θ = 77.49 (7)° and φ = 170.4 (8)°: atoms O1 and C7 deviate by 0.108 (2) and 0.135 (2) Å, respectively, from the mean plane of the other atoms. The dihedral angle between the phenyl ring and the 4H-pyran ring (all atoms) is 82.43 (14)°.
In the crystal, inversion dimers linked by pairs of weak N2—H2A⋯N1 hydrogen bonds generate (12) loops and N2—H2B⋯O2 hydrogen bonds link the dimers into [001] chains (Table 1, Fig. 2).
Synthesis and crystallization
A mixture of 4-chlorobenzaldehyde (1.0 mmol), malononitrile (1.0 mmol), allyl 3-oxobutanoate (1.0 mmol) and a few drops of piperidine was stirred magnetically in 30 ml of absolute ethanol at 80°C for 90 min. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and the solvent was evaporated. The solid thus appeared was collected and washed with cold water and recrystallized from ethanol solution to result in colourless blocks of the title compound (yield 84%).
Refinement
Crystal data, data collection and structure . The atoms of the allyl group (C15 and C16 and attached H atoms) are disordered over two sets of sites in a 0.585 (14):0.415 (14) ratio.
details are summarized in Table 2Structural data
CCDC reference: 1901250
https://doi.org/10.1107/S2414314619003158/hb4264sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619003158/hb4264Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314619003158/hb4264Isup3.cml
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C17H15ClN2O3 | F(000) = 688 |
Mr = 330.73 | Dx = 1.356 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5292 reflections |
a = 9.3609 (6) Å | θ = 2.6–24.2° |
b = 20.3984 (16) Å | µ = 0.25 mm−1 |
c = 8.5280 (7) Å | T = 296 K |
β = 95.691 (2)° | BLOCK, colourless |
V = 1620.4 (2) Å3 | 0.15 × 0.15 × 0.10 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 2850 independent reflections |
Radiation source: fine-focus sealed tube | 2011 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω and φ scan | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −11→10 |
Tmin = 0.963, Tmax = 0.975 | k = −24→24 |
17502 measured reflections | l = −10→10 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters not defined? |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0544P)2 + 1.3356P] where P = (Fo2 + 2Fc2)/3 |
2850 reflections | (Δ/σ)max = 0.002 |
241 parameters | Δρmax = 0.35 e Å−3 |
38 restraints | Δρmin = −0.32 e Å−3 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All esds are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
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 > 2sigma(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. The hydrogen atoms bound to the C atoms are treated as riding atoms. The H atoms bonded to N were freely refined. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | −0.00313 (10) | 0.32803 (5) | 0.07877 (13) | 0.0874 (4) | |
O1 | 0.46275 (18) | 0.07969 (10) | −0.32817 (19) | 0.0440 (6) | |
O2 | 0.4430 (2) | 0.07085 (12) | 0.2207 (2) | 0.0600 (8) | |
O3 | 0.6401 (2) | 0.11435 (10) | 0.1389 (2) | 0.0516 (7) | |
N1 | −0.0094 (3) | 0.00114 (14) | −0.2957 (3) | 0.0595 (10) | |
N2 | 0.2910 (3) | 0.04447 (15) | −0.5067 (3) | 0.0551 (10) | |
C1 | 0.0785 (3) | 0.25483 (16) | 0.0326 (4) | 0.0542 (11) | |
C2 | 0.0284 (4) | 0.19701 (19) | 0.0833 (4) | 0.0700 (16) | |
C3 | 0.0968 (3) | 0.13891 (16) | 0.0521 (4) | 0.0563 (11) | |
C4 | 0.2143 (3) | 0.13860 (13) | −0.0331 (3) | 0.0357 (8) | |
C5 | 0.2604 (3) | 0.19807 (15) | −0.0864 (4) | 0.0528 (11) | |
C6 | 0.1941 (3) | 0.25649 (15) | −0.0529 (4) | 0.0609 (11) | |
C7 | 0.2883 (3) | 0.07482 (12) | −0.0704 (3) | 0.0344 (8) | |
C8 | 0.2411 (3) | 0.05042 (12) | −0.2353 (3) | 0.0341 (8) | |
C9 | 0.3244 (3) | 0.05766 (13) | −0.3537 (3) | 0.0373 (8) | |
C10 | 0.5275 (3) | 0.08513 (13) | −0.1753 (3) | 0.0381 (8) | |
C11 | 0.4502 (3) | 0.08235 (12) | −0.0517 (3) | 0.0341 (8) | |
C12 | 0.1022 (3) | 0.02369 (13) | −0.2684 (3) | 0.0392 (9) | |
C13 | 0.5096 (3) | 0.08802 (13) | 0.1148 (3) | 0.0385 (8) | |
C14 | 0.6952 (4) | 0.12629 (18) | 0.3027 (4) | 0.0575 (11) | |
C15 | 0.6737 (10) | 0.1954 (4) | 0.3396 (10) | 0.063 (3) | 0.585 (14) |
C16 | 0.6009 (11) | 0.2171 (7) | 0.4480 (10) | 0.088 (4) | 0.585 (14) |
C17 | 0.6848 (3) | 0.09330 (16) | −0.1840 (3) | 0.0519 (10) | |
C15' | 0.6098 (16) | 0.1800 (5) | 0.3735 (17) | 0.075 (4) | 0.415 (14) |
C16' | 0.660 (2) | 0.2373 (7) | 0.391 (3) | 0.127 (8) | 0.415 (14) |
H2B | 0.355 (4) | 0.0512 (16) | −0.574 (4) | 0.062 (10)* | |
H3 | 0.06296 | 0.09957 | 0.08928 | 0.0675* | |
H5 | 0.33816 | 0.19901 | −0.14630 | 0.0633* | |
H6 | 0.22786 | 0.29618 | −0.08817 | 0.0728* | |
H7 | 0.26255 | 0.04150 | 0.00459 | 0.0413* | |
H14A | 0.79655 | 0.11562 | 0.31821 | 0.0690* | 0.585 (14) |
H14B | 0.64492 | 0.09880 | 0.37213 | 0.0690* | 0.585 (14) |
H15 | 0.71649 | 0.22621 | 0.27898 | 0.0751* | 0.585 (14) |
H16A | 0.55631 | 0.18794 | 0.51141 | 0.1052* | 0.585 (14) |
H16B | 0.59278 | 0.26201 | 0.46347 | 0.1052* | 0.585 (14) |
H17A | 0.70457 | 0.09322 | −0.29230 | 0.0778* | |
H17B | 0.73535 | 0.05782 | −0.12929 | 0.0778* | |
H17C | 0.71572 | 0.13413 | −0.13593 | 0.0778* | |
H2 | −0.05207 | 0.19634 | 0.13904 | 0.0840* | |
H2A | 0.207 (3) | 0.0344 (14) | −0.538 (3) | 0.045 (9)* | |
H14C | 0.812 (9) | 0.126 (4) | 0.277 (9) | 0.0690* | 0.415 (14) |
H14D | 0.681 (8) | 0.084 (4) | 0.364 (9) | 0.0690* | 0.415 (14) |
H15' | 0.51942 | 0.17057 | 0.40428 | 0.0903* | 0.415 (14) |
H16C | 0.75006 | 0.24702 | 0.36055 | 0.1522* | 0.415 (14) |
H16D | 0.60634 | 0.26982 | 0.43468 | 0.1522* | 0.415 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0708 (6) | 0.0727 (7) | 0.1122 (8) | 0.0276 (5) | −0.0227 (5) | −0.0415 (6) |
O1 | 0.0404 (10) | 0.0636 (13) | 0.0290 (10) | −0.0127 (9) | 0.0085 (8) | −0.0011 (9) |
O2 | 0.0564 (13) | 0.0928 (17) | 0.0314 (11) | −0.0153 (11) | 0.0075 (9) | 0.0024 (10) |
O3 | 0.0510 (12) | 0.0656 (14) | 0.0369 (11) | −0.0125 (10) | −0.0025 (9) | −0.0035 (9) |
N1 | 0.0499 (15) | 0.0711 (19) | 0.0576 (17) | −0.0178 (14) | 0.0059 (12) | −0.0069 (14) |
N2 | 0.0469 (16) | 0.089 (2) | 0.0302 (13) | −0.0183 (15) | 0.0084 (12) | −0.0110 (13) |
C1 | 0.0465 (18) | 0.055 (2) | 0.058 (2) | 0.0072 (15) | −0.0106 (15) | −0.0197 (16) |
C2 | 0.060 (2) | 0.076 (3) | 0.079 (3) | 0.0079 (19) | 0.0318 (19) | −0.016 (2) |
C3 | 0.0572 (19) | 0.057 (2) | 0.059 (2) | −0.0054 (15) | 0.0276 (15) | −0.0046 (15) |
C4 | 0.0351 (14) | 0.0424 (15) | 0.0298 (13) | −0.0040 (12) | 0.0044 (10) | −0.0037 (11) |
C5 | 0.0490 (17) | 0.0488 (19) | 0.063 (2) | −0.0017 (14) | 0.0174 (15) | 0.0013 (15) |
C6 | 0.061 (2) | 0.0420 (18) | 0.078 (2) | −0.0004 (15) | −0.0014 (18) | −0.0006 (16) |
C7 | 0.0378 (14) | 0.0384 (15) | 0.0277 (13) | −0.0049 (11) | 0.0071 (10) | 0.0009 (11) |
C8 | 0.0348 (14) | 0.0364 (14) | 0.0314 (13) | −0.0050 (11) | 0.0055 (10) | −0.0017 (11) |
C9 | 0.0365 (14) | 0.0428 (16) | 0.0328 (14) | −0.0062 (11) | 0.0050 (11) | −0.0018 (11) |
C10 | 0.0384 (14) | 0.0404 (15) | 0.0356 (14) | −0.0042 (12) | 0.0045 (11) | 0.0006 (12) |
C11 | 0.0374 (14) | 0.0347 (14) | 0.0305 (13) | −0.0029 (11) | 0.0054 (10) | −0.0001 (11) |
C12 | 0.0431 (16) | 0.0411 (16) | 0.0344 (14) | −0.0042 (12) | 0.0085 (12) | −0.0025 (12) |
C13 | 0.0414 (15) | 0.0395 (15) | 0.0345 (14) | 0.0013 (12) | 0.0036 (12) | −0.0008 (12) |
C14 | 0.061 (2) | 0.066 (2) | 0.0419 (17) | −0.0012 (17) | −0.0130 (15) | −0.0092 (15) |
C15 | 0.068 (6) | 0.047 (5) | 0.071 (5) | −0.002 (4) | −0.006 (4) | −0.009 (4) |
C16 | 0.101 (7) | 0.090 (8) | 0.072 (5) | 0.023 (6) | 0.006 (5) | 0.001 (5) |
C17 | 0.0387 (16) | 0.069 (2) | 0.0493 (17) | −0.0069 (14) | 0.0110 (13) | −0.0054 (15) |
C15' | 0.099 (9) | 0.063 (7) | 0.063 (7) | −0.027 (6) | 0.004 (7) | −0.018 (6) |
C16' | 0.154 (14) | 0.074 (10) | 0.159 (15) | 0.028 (9) | 0.049 (11) | 0.019 (10) |
Cl1—C1 | 1.740 (3) | C11—C13 | 1.477 (4) |
O1—C9 | 1.368 (3) | C14—C15 | 1.463 (9) |
O1—C10 | 1.387 (3) | C14—C15' | 1.516 (13) |
O2—C13 | 1.199 (3) | C15—C16 | 1.281 (13) |
O3—C13 | 1.332 (3) | C15'—C16' | 1.263 (19) |
O3—C14 | 1.461 (4) | C2—H2 | 0.9298 |
N1—C12 | 1.144 (4) | C3—H3 | 0.9299 |
N2—C9 | 1.339 (4) | C5—H5 | 0.9300 |
N2—H2A | 0.83 (3) | C6—H6 | 0.9299 |
N2—H2B | 0.88 (4) | C7—H7 | 0.9796 |
C1—C2 | 1.356 (5) | C14—H14A | 0.9696 |
C1—C6 | 1.364 (4) | C14—H14B | 0.9705 |
C2—C3 | 1.385 (5) | C14—H14C | 1.14 (8) |
C3—C4 | 1.377 (4) | C14—H14D | 1.02 (8) |
C4—C5 | 1.380 (4) | C15—H15 | 0.9294 |
C4—C7 | 1.522 (4) | C15'—H15' | 0.9304 |
C5—C6 | 1.386 (4) | C16—H16A | 0.9302 |
C7—C8 | 1.516 (4) | C16—H16B | 0.9297 |
C7—C11 | 1.516 (4) | C16'—H16C | 0.9278 |
C8—C12 | 1.412 (4) | C16'—H16D | 0.9318 |
C8—C9 | 1.344 (4) | C17—H17A | 0.9598 |
C10—C17 | 1.491 (4) | C17—H17B | 0.9600 |
C10—C11 | 1.338 (4) | C17—H17C | 0.9602 |
C9—O1—C10 | 119.7 (2) | C1—C2—H2 | 119.95 |
C13—O3—C14 | 116.5 (2) | C3—C2—H2 | 119.93 |
C9—N2—H2B | 120 (2) | C2—C3—H3 | 119.55 |
H2A—N2—H2B | 121 (3) | C4—C3—H3 | 119.53 |
C9—N2—H2A | 119.0 (18) | C4—C5—H5 | 119.11 |
Cl1—C1—C2 | 120.0 (3) | C6—C5—H5 | 119.09 |
Cl1—C1—C6 | 119.3 (2) | C1—C6—H6 | 120.51 |
C2—C1—C6 | 120.7 (3) | C5—C6—H6 | 120.55 |
C1—C2—C3 | 120.1 (3) | C4—C7—H7 | 108.06 |
C2—C3—C4 | 120.9 (3) | C8—C7—H7 | 108.05 |
C5—C4—C7 | 121.3 (2) | C11—C7—H7 | 108.05 |
C3—C4—C7 | 121.2 (2) | O3—C14—H14A | 109.94 |
C3—C4—C5 | 117.5 (3) | O3—C14—H14B | 109.91 |
C4—C5—C6 | 121.8 (3) | O3—C14—H14C | 94 (4) |
C1—C6—C5 | 118.9 (3) | O3—C14—H14D | 107 (4) |
C4—C7—C8 | 112.2 (2) | C15—C14—H14A | 109.92 |
C4—C7—C11 | 111.2 (2) | C15—C14—H14B | 109.89 |
C8—C7—C11 | 109.1 (2) | H14A—C14—H14B | 108.32 |
C7—C8—C12 | 119.3 (2) | C15'—C14—H14C | 129 (4) |
C7—C8—C9 | 121.6 (2) | C15'—C14—H14D | 108 (4) |
C9—C8—C12 | 118.9 (2) | H14C—C14—H14D | 106 (6) |
O1—C9—N2 | 110.3 (2) | C14—C15—H15 | 117.13 |
O1—C9—C8 | 121.8 (2) | C16—C15—H15 | 117.22 |
N2—C9—C8 | 127.8 (3) | C16'—C15'—H15' | 119.74 |
C11—C10—C17 | 131.2 (2) | C14—C15'—H15' | 119.53 |
O1—C10—C17 | 107.7 (2) | C15—C16—H16B | 119.99 |
O1—C10—C11 | 121.2 (2) | C15—C16—H16A | 120.02 |
C7—C11—C10 | 122.3 (2) | H16A—C16—H16B | 119.99 |
C7—C11—C13 | 112.7 (2) | C15'—C16'—H16C | 120.16 |
C10—C11—C13 | 124.9 (3) | C15'—C16'—H16D | 119.80 |
N1—C12—C8 | 179.0 (3) | H16C—C16'—H16D | 120.04 |
O3—C13—C11 | 115.6 (2) | H17A—C17—H17C | 109.49 |
O2—C13—O3 | 122.6 (2) | H17B—C17—H17C | 109.47 |
O2—C13—C11 | 121.8 (3) | C10—C17—H17A | 109.47 |
O3—C14—C15 | 108.9 (4) | C10—C17—H17B | 109.46 |
O3—C14—C15' | 110.6 (6) | C10—C17—H17C | 109.46 |
C14—C15—C16 | 125.7 (9) | H17A—C17—H17B | 109.49 |
C14—C15'—C16' | 120.7 (14) | ||
C9—O1—C10—C17 | 165.8 (2) | C4—C7—C8—C12 | −72.5 (3) |
C10—O1—C9—N2 | −168.6 (2) | C4—C7—C8—C9 | 102.8 (3) |
C10—O1—C9—C8 | 10.3 (4) | C11—C7—C8—C12 | 163.7 (2) |
C9—O1—C10—C11 | −13.8 (4) | C4—C7—C11—C10 | −106.8 (3) |
C14—O3—C13—C11 | 174.3 (2) | C11—C7—C8—C9 | −20.9 (3) |
C13—O3—C14—C15 | −99.1 (5) | C8—C7—C11—C13 | −164.1 (2) |
C14—O3—C13—O2 | −4.6 (4) | C8—C7—C11—C10 | 17.5 (3) |
Cl1—C1—C6—C5 | 178.7 (3) | C4—C7—C11—C13 | 71.6 (3) |
C2—C1—C6—C5 | −0.4 (5) | C12—C8—C9—O1 | −176.2 (2) |
C6—C1—C2—C3 | 1.7 (5) | C12—C8—C9—N2 | 2.5 (4) |
Cl1—C1—C2—C3 | −177.4 (3) | C7—C8—C9—O1 | 8.4 (4) |
C1—C2—C3—C4 | −1.3 (5) | C7—C8—C9—N2 | −172.9 (3) |
C2—C3—C4—C7 | −178.9 (3) | O1—C10—C11—C7 | −1.5 (4) |
C2—C3—C4—C5 | −0.3 (4) | C17—C10—C11—C13 | 0.8 (5) |
C3—C4—C7—C11 | −138.7 (3) | C17—C10—C11—C7 | 178.9 (3) |
C5—C4—C7—C11 | 42.8 (3) | O1—C10—C11—C13 | −179.7 (2) |
C7—C4—C5—C6 | −179.8 (3) | C10—C11—C13—O3 | 18.1 (4) |
C3—C4—C5—C6 | 1.6 (5) | C7—C11—C13—O2 | 18.7 (4) |
C3—C4—C7—C8 | 98.8 (3) | C10—C11—C13—O2 | −163.0 (3) |
C5—C4—C7—C8 | −79.7 (3) | C7—C11—C13—O3 | −160.2 (2) |
C4—C5—C6—C1 | −1.3 (5) | O3—C14—C15—C16 | 121.1 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.83 (3) | 2.33 (3) | 3.126 (4) | 160 (2) |
N2—H2B···O2ii | 0.88 (4) | 2.05 (3) | 2.894 (3) | 161 (3) |
Symmetry codes: (i) −x, −y, −z−1; (ii) x, y, z−1. |
Acknowledgements
TM thanks Dr D. Srinivasan, Principal of K. Ramakrishnan College of Engineering, Trichy for support.
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