organic compounds
(E)-2-Amino-4-(3,3-dimethyl-2-oxobutylidene)-1-[2-(2-hydroxyethoxy)ethyl]-6-methyl-1,4-dihydropyridine-3-carbonitrile
aSchool of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, Republic of Korea, and bDepartment of Chemistry, Sunchon National University, Sunchon 540-742, Republic of Korea
*Correspondence e-mail: hyungkim@chonnam.ac.kr, chkwak@sunchon.ac.kr
In the title compound, C17H25N3O3, there are intramolecular hydrogen bonds between an amine H atom and the epoxy O atom, and between a dihydropyridine ring H atom and the ketone O atom. In the crystal, molecules are linked into a zigzag chain running parallel to the c axis by hydrogen bonds between the hydroxy group and the ketone O atom. There are also weak C—H⋯O and C—H⋯π interactions which link the molecules into sheets lying in the bc plane.
Related literature
For related structures, see: Ha et al. (2009); Kim et al. (2011). For the synthesis, see: VanAllan & Reynolds (1971).
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 2008); cell RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S160053681203334X/go2062sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681203334X/go2062Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S160053681203334X/go2062Isup3.cml
A mixture of 2-(2-tert-butyl-6-methyl-4H-pyran-4-ylidene)malononitrile (632 mg, 2.94 mmol) and 2-(2-aminoethoxy)ethanol (465 mg, 4.42 mmol) dissolved in n-butanol (7 ml) was heated at 100 °C for 4 h. The mixture was cooled and concentrated under vacuum. The residue was chromatographed on SiO2 eluting with a mixture of EtOAc/MeOH (1:1) solution to afford the title compound (300 mg, 32%) as a yellow solid. Crystals suitable for X-ray analysis were obtained by slow evaporation from a CHCl3/MeOH solution at room temperature. Mp 173 °C.
H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 (CH, sp2), 0.98 (CH, sp3), 0.86 (NH2) and 0.82 Å (OH), respectively and Uiso(H) = 1.2Ueq(C), 1.2Ueq(N) and 1.5Ueq(O), respectively]. The positions of the methyl, amino and hydroxyl H atoms were checked on a final difference map and were found to be satisfactory.
2,6-Disubstituted (1,4-pyridine-4-ylidene)malononitrile derivatives are key intermediates in the synthesis of dihydropyridine-based fluorescent dyes (Ha et al., 2009; Kim et al., 2011), and are readily prepared from the reaction of the corresponding 2,6-disubstituted (4H-pyran-4-ylidene)maolononitrile with a primary amine. We reacted 2-(2-tert-butyl-6-methyl-4H-pyran-4-ylidene)malononitrile with 2-(2-aminoethoxy)ethanol in order to obtain the (1,4-pyridine-4-ylidene)malononitrile substituted with tert-butyl and methyl groups at 2 and 6-positions, respectively. The title compound was however produced as a major product instead of the corresponding malononitrile derivative (VanAllan & Reynolds, 1971). The molecular structure of C17H25N3O3, is shown in (Fig. 1). There are intramolecular hydrogen bonds N3-H3···O1 and C4–H4···O3 (Table 1). An intermolecular hydrogen bond O2-H2···O3(x,1/2-y,-1/2+ z) links the molecules into a zigzag chain which runs along the c axis. These chains are linked to form a sheet by a weak C7–H7A···O21-x,-y,1-z and as C9—H9A···π interaction involving the dihydropyridine ring(1-x,-y,1-z) 1, (Table 1, Fig. 2).
For related structures, see: Ha et al. (2009); Kim et al. (2011). For the synthesis, see: VanAllan & Reynolds (1971).
Data collection: RAPID-AUTO (Rigaku, 2008); cell
RAPID-AUTO (Rigaku, 2008); data reduction: RAPID-AUTO (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C17H25N3O3 | F(000) = 688 |
Mr = 319.40 | Dx = 1.234 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9007 (5) Å | θ = 3.0–27.5° |
b = 13.2890 (7) Å | µ = 0.09 mm−1 |
c = 13.0686 (8) Å | T = 293 K |
β = 91.314 (2)° | Block, brown |
V = 1718.99 (16) Å3 | 0.6 × 0.4 × 0.2 mm |
Z = 4 |
Rigaku R-AXIS RAPID II-S diffractometer | 3912 independent reflections |
Radiation source: fine-focus sealed tube | 3104 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008) | h = −12→12 |
Tmin = 0.960, Tmax = 0.983 | k = −17→17 |
15989 measured reflections | l = −16→16 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0659P)2 + 0.2655P] where P = (Fo2 + 2Fc2)/3 |
3912 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C17H25N3O3 | V = 1718.99 (16) Å3 |
Mr = 319.40 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.9007 (5) Å | µ = 0.09 mm−1 |
b = 13.2890 (7) Å | T = 293 K |
c = 13.0686 (8) Å | 0.6 × 0.4 × 0.2 mm |
β = 91.314 (2)° |
Rigaku R-AXIS RAPID II-S diffractometer | 3912 independent reflections |
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008) | 3104 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.983 | Rint = 0.058 |
15989 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.36 e Å−3 |
3912 reflections | Δρmin = −0.26 e Å−3 |
209 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C10 | 0.88179 (15) | 0.25846 (10) | 0.48356 (11) | 0.0372 (3) | |
O3 | 0.69984 (11) | 0.51832 (9) | 0.73210 (10) | 0.0539 (3) | |
N2 | 0.99132 (14) | 0.23098 (11) | 0.47668 (11) | 0.0514 (4) | |
C11 | 0.33488 (15) | 0.36674 (12) | 0.54335 (13) | 0.0472 (4) | |
H11A | 0.3265 | 0.4021 | 0.6069 | 0.071* | |
H11B | 0.2856 | 0.3046 | 0.5463 | 0.071* | |
H11C | 0.2989 | 0.4074 | 0.4885 | 0.071* | |
N3 | 0.67042 (14) | 0.18281 (10) | 0.35965 (10) | 0.0444 (3) | |
H3A | 0.6055 | 0.1592 | 0.3220 | 0.053* | |
H3B | 0.7520 | 0.1632 | 0.3503 | 0.053* | |
O1 | 0.41901 (10) | 0.06974 (7) | 0.36195 (8) | 0.0411 (3) | |
N1 | 0.51316 (11) | 0.27979 (8) | 0.44545 (9) | 0.0346 (3) | |
O2 | 0.56463 (12) | −0.12848 (9) | 0.36431 (9) | 0.0530 (3) | |
H2 | 0.6107 | −0.0779 | 0.3565 | 0.079* | |
C1 | 0.64429 (14) | 0.25077 (10) | 0.43342 (10) | 0.0338 (3) | |
C2 | 0.74686 (13) | 0.29353 (10) | 0.49497 (10) | 0.0336 (3) | |
C5 | 0.48117 (14) | 0.34495 (10) | 0.52525 (11) | 0.0352 (3) | |
C12 | 0.82613 (14) | 0.41643 (10) | 0.62401 (11) | 0.0355 (3) | |
H12 | 0.9135 | 0.3970 | 0.6085 | 0.043* | |
C4 | 0.57932 (14) | 0.38748 (10) | 0.58437 (11) | 0.0353 (3) | |
H4 | 0.5543 | 0.4309 | 0.6365 | 0.042* | |
C3 | 0.72004 (14) | 0.36870 (10) | 0.57037 (10) | 0.0328 (3) | |
C13 | 0.81221 (14) | 0.49139 (10) | 0.69951 (11) | 0.0355 (3) | |
C14 | 0.93855 (14) | 0.54230 (11) | 0.74837 (11) | 0.0374 (3) | |
C7 | 0.33697 (15) | 0.15161 (11) | 0.39359 (12) | 0.0425 (3) | |
H7A | 0.3218 | 0.1471 | 0.4665 | 0.051* | |
H7B | 0.2500 | 0.1491 | 0.3580 | 0.051* | |
C6 | 0.40756 (16) | 0.24924 (11) | 0.36958 (12) | 0.0417 (3) | |
H6A | 0.4486 | 0.2430 | 0.3032 | 0.050* | |
H6B | 0.3404 | 0.3023 | 0.3645 | 0.050* | |
C8 | 0.36595 (15) | −0.02510 (11) | 0.39327 (12) | 0.0417 (3) | |
H8A | 0.2689 | −0.0262 | 0.3816 | 0.050* | |
H8B | 0.3840 | −0.0349 | 0.4658 | 0.050* | |
C9 | 0.43021 (16) | −0.10829 (11) | 0.33368 (12) | 0.0445 (4) | |
H9A | 0.3772 | −0.1691 | 0.3414 | 0.053* | |
H9B | 0.4280 | −0.0905 | 0.2617 | 0.053* | |
C16 | 0.95355 (17) | 0.50352 (15) | 0.85821 (13) | 0.0536 (4) | |
H16A | 1.0312 | 0.5340 | 0.8908 | 0.080* | |
H16B | 0.9646 | 0.4318 | 0.8574 | 0.080* | |
H16C | 0.8742 | 0.5205 | 0.8954 | 0.080* | |
C17 | 0.91462 (18) | 0.65630 (12) | 0.75167 (14) | 0.0517 (4) | |
H17A | 0.9923 | 0.6888 | 0.7821 | 0.078* | |
H17B | 0.8367 | 0.6703 | 0.7917 | 0.078* | |
H17C | 0.8999 | 0.6811 | 0.6833 | 0.078* | |
C15 | 1.06820 (15) | 0.52174 (14) | 0.69025 (14) | 0.0508 (4) | |
H15A | 1.1427 | 0.5551 | 0.7241 | 0.076* | |
H15B | 1.0582 | 0.5466 | 0.6215 | 0.076* | |
H15C | 1.0850 | 0.4506 | 0.6887 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C10 | 0.0403 (8) | 0.0336 (7) | 0.0380 (7) | −0.0010 (6) | 0.0054 (6) | −0.0014 (5) |
O3 | 0.0340 (6) | 0.0642 (7) | 0.0635 (7) | 0.0013 (5) | 0.0022 (5) | −0.0277 (6) |
N2 | 0.0414 (7) | 0.0528 (8) | 0.0601 (9) | 0.0073 (6) | 0.0055 (6) | −0.0048 (6) |
C11 | 0.0335 (8) | 0.0464 (8) | 0.0617 (10) | 0.0041 (7) | −0.0018 (7) | −0.0061 (7) |
N3 | 0.0469 (7) | 0.0444 (7) | 0.0420 (7) | 0.0025 (6) | 0.0010 (5) | −0.0098 (5) |
O1 | 0.0404 (6) | 0.0358 (5) | 0.0474 (6) | −0.0015 (4) | 0.0056 (4) | 0.0000 (4) |
N1 | 0.0363 (6) | 0.0318 (5) | 0.0353 (6) | 0.0008 (5) | −0.0042 (5) | 0.0015 (4) |
O2 | 0.0527 (7) | 0.0528 (6) | 0.0537 (7) | 0.0076 (5) | 0.0085 (5) | 0.0170 (5) |
C1 | 0.0390 (7) | 0.0301 (6) | 0.0322 (7) | 0.0010 (6) | 0.0029 (5) | 0.0039 (5) |
C2 | 0.0337 (7) | 0.0312 (6) | 0.0360 (7) | 0.0010 (5) | 0.0041 (5) | 0.0018 (5) |
C5 | 0.0341 (7) | 0.0309 (6) | 0.0404 (7) | 0.0030 (5) | −0.0013 (5) | 0.0018 (5) |
C12 | 0.0294 (6) | 0.0374 (7) | 0.0395 (7) | 0.0022 (6) | 0.0008 (5) | −0.0001 (5) |
C4 | 0.0343 (7) | 0.0331 (6) | 0.0385 (7) | 0.0019 (6) | 0.0019 (5) | −0.0025 (5) |
C3 | 0.0349 (7) | 0.0301 (6) | 0.0335 (7) | 0.0013 (5) | 0.0016 (5) | 0.0038 (5) |
C13 | 0.0324 (7) | 0.0383 (7) | 0.0359 (7) | 0.0016 (6) | −0.0004 (5) | 0.0016 (5) |
C14 | 0.0342 (7) | 0.0428 (7) | 0.0349 (7) | −0.0036 (6) | −0.0031 (5) | 0.0029 (6) |
C7 | 0.0359 (7) | 0.0435 (8) | 0.0477 (9) | 0.0030 (6) | −0.0074 (6) | −0.0056 (6) |
C6 | 0.0455 (8) | 0.0386 (7) | 0.0403 (8) | 0.0045 (6) | −0.0127 (6) | 0.0014 (6) |
C8 | 0.0373 (8) | 0.0412 (8) | 0.0465 (9) | −0.0077 (6) | 0.0027 (6) | 0.0021 (6) |
C9 | 0.0488 (9) | 0.0391 (8) | 0.0458 (8) | −0.0069 (7) | 0.0027 (6) | 0.0019 (6) |
C16 | 0.0482 (9) | 0.0698 (11) | 0.0423 (9) | −0.0093 (8) | −0.0081 (7) | 0.0114 (8) |
C17 | 0.0525 (10) | 0.0454 (9) | 0.0570 (10) | −0.0091 (7) | −0.0052 (7) | −0.0010 (7) |
C15 | 0.0340 (8) | 0.0648 (10) | 0.0536 (10) | −0.0091 (7) | 0.0002 (7) | −0.0037 (8) |
C10—N2 | 1.1497 (19) | C4—H4 | 0.9300 |
C10—C2 | 1.4259 (19) | C13—C14 | 1.547 (2) |
O3—C13 | 1.2526 (17) | C14—C16 | 1.529 (2) |
C11—C5 | 1.5011 (19) | C14—C15 | 1.531 (2) |
C11—H11A | 0.9600 | C14—C17 | 1.534 (2) |
C11—H11B | 0.9600 | C7—C6 | 1.510 (2) |
C11—H11C | 0.9600 | C7—H7A | 0.9700 |
N3—C1 | 1.3504 (18) | C7—H7B | 0.9700 |
N3—H3A | 0.8600 | C6—H6A | 0.9700 |
N3—H3B | 0.8600 | C6—H6B | 0.9700 |
O1—C7 | 1.4247 (18) | C8—C9 | 1.502 (2) |
O1—C8 | 1.4289 (17) | C8—H8A | 0.9700 |
N1—C1 | 1.3670 (17) | C8—H8B | 0.9700 |
N1—C5 | 1.3974 (18) | C9—H9A | 0.9700 |
N1—C6 | 1.4811 (18) | C9—H9B | 0.9700 |
O2—C9 | 1.407 (2) | C16—H16A | 0.9600 |
O2—H2 | 0.8200 | C16—H16B | 0.9600 |
C1—C2 | 1.4012 (19) | C16—H16C | 0.9600 |
C2—C3 | 1.4323 (18) | C17—H17A | 0.9600 |
C5—C4 | 1.351 (2) | C17—H17B | 0.9600 |
C12—C3 | 1.401 (2) | C17—H17C | 0.9600 |
C12—C13 | 1.411 (2) | C15—H15A | 0.9600 |
C12—H12 | 0.9300 | C15—H15B | 0.9600 |
C4—C3 | 1.4312 (19) | C15—H15C | 0.9600 |
N2—C10—C2 | 178.37 (16) | O1—C7—C6 | 109.03 (12) |
C5—C11—H11A | 109.5 | O1—C7—H7A | 109.9 |
C5—C11—H11B | 109.5 | C6—C7—H7A | 109.9 |
H11A—C11—H11B | 109.5 | O1—C7—H7B | 109.9 |
C5—C11—H11C | 109.5 | C6—C7—H7B | 109.9 |
H11A—C11—H11C | 109.5 | H7A—C7—H7B | 108.3 |
H11B—C11—H11C | 109.5 | N1—C6—C7 | 114.79 (12) |
C1—N3—H3A | 120.0 | N1—C6—H6A | 108.6 |
C1—N3—H3B | 120.0 | C7—C6—H6A | 108.6 |
H3A—N3—H3B | 120.0 | N1—C6—H6B | 108.6 |
C7—O1—C8 | 112.00 (11) | C7—C6—H6B | 108.6 |
C1—N1—C5 | 119.52 (11) | H6A—C6—H6B | 107.5 |
C1—N1—C6 | 120.22 (11) | O1—C8—C9 | 109.74 (12) |
C5—N1—C6 | 120.06 (11) | O1—C8—H8A | 109.7 |
C9—O2—H2 | 109.5 | C9—C8—H8A | 109.7 |
N3—C1—N1 | 117.96 (13) | O1—C8—H8B | 109.7 |
N3—C1—C2 | 122.20 (13) | C9—C8—H8B | 109.7 |
N1—C1—C2 | 119.82 (12) | H8A—C8—H8B | 108.2 |
C1—C2—C10 | 118.41 (12) | O2—C9—C8 | 113.71 (13) |
C1—C2—C3 | 122.30 (12) | O2—C9—H9A | 108.8 |
C10—C2—C3 | 119.26 (12) | C8—C9—H9A | 108.8 |
C4—C5—N1 | 120.90 (12) | O2—C9—H9B | 108.8 |
C4—C5—C11 | 120.87 (13) | C8—C9—H9B | 108.8 |
N1—C5—C11 | 118.24 (12) | H9A—C9—H9B | 107.7 |
C3—C12—C13 | 125.83 (13) | C14—C16—H16A | 109.5 |
C3—C12—H12 | 117.1 | C14—C16—H16B | 109.5 |
C13—C12—H12 | 117.1 | H16A—C16—H16B | 109.5 |
C5—C4—C3 | 122.91 (13) | C14—C16—H16C | 109.5 |
C5—C4—H4 | 118.5 | H16A—C16—H16C | 109.5 |
C3—C4—H4 | 118.5 | H16B—C16—H16C | 109.5 |
C12—C3—C4 | 125.30 (12) | C14—C17—H17A | 109.5 |
C12—C3—C2 | 120.75 (12) | C14—C17—H17B | 109.5 |
C4—C3—C2 | 113.95 (12) | H17A—C17—H17B | 109.5 |
O3—C13—C12 | 122.76 (13) | C14—C17—H17C | 109.5 |
O3—C13—C14 | 116.80 (12) | H17A—C17—H17C | 109.5 |
C12—C13—C14 | 120.42 (12) | H17B—C17—H17C | 109.5 |
C16—C14—C15 | 109.94 (13) | C14—C15—H15A | 109.5 |
C16—C14—C17 | 108.55 (14) | C14—C15—H15B | 109.5 |
C15—C14—C17 | 108.78 (13) | H15A—C15—H15B | 109.5 |
C16—C14—C13 | 107.47 (12) | C14—C15—H15C | 109.5 |
C15—C14—C13 | 113.36 (12) | H15A—C15—H15C | 109.5 |
C17—C14—C13 | 108.64 (12) | H15B—C15—H15C | 109.5 |
Cg1 is the centroid of the dihydropyridine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.86 | 2.27 | 2.9083 (17) | 131 |
C4—H4···O3 | 0.93 | 2.21 | 2.8405 (17) | 124 |
O2—H2···O3i | 0.82 | 2.03 | 2.650 (2) | 132 |
C7—H7A···O2ii | 0.97 | 2.47 | 3.303 (2) | 144 |
C9—H9A···Cg1ii | 0.97 | 2.81 | 3.5275 (16) | 131 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C17H25N3O3 |
Mr | 319.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.9007 (5), 13.2890 (7), 13.0686 (8) |
β (°) | 91.314 (2) |
V (Å3) | 1718.99 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.6 × 0.4 × 0.2 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID II-S |
Absorption correction | Multi-scan (RAPID-AUTO; Rigaku, 2008) |
Tmin, Tmax | 0.960, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15989, 3912, 3104 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.136, 1.08 |
No. of reflections | 3912 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.26 |
Computer programs: RAPID-AUTO (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
Cg1 is the centroid of the dihydropyridine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.86 | 2.27 | 2.9083 (17) | 131 |
C4—H4···O3 | 0.93 | 2.21 | 2.8405 (17) | 124 |
O2—H2···O3i | 0.82 | 2.03 | 2.650 (2) | 132 |
C7—H7A···O2ii | 0.97 | 2.47 | 3.303 (2) | 144 |
C9—H9A···Cg1ii | 0.97 | 2.81 | 3.5275 (16) | 131 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1. |
Acknowledgements
This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2011–0009193). HJK thanks Cheonnam National University (2011) for financial support.
References
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ha, K., Heo, J. & Kim, H. J. (2009). Acta Cryst. E65, o3131. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kim, Y. H., Kim, H. J., Otgonbaatar, E. & Kwak, C.-H. (2011). Acta Cryst. E67, o670. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2008). RAPIDO-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
VanAllan, J. A. & Reynolds, G. A. (1971). J. Heterocycl. Chem. 8, 367–371. CrossRef CAS Google Scholar
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2,6-Disubstituted (1,4-pyridine-4-ylidene)malononitrile derivatives are key intermediates in the synthesis of dihydropyridine-based fluorescent dyes (Ha et al., 2009; Kim et al., 2011), and are readily prepared from the reaction of the corresponding 2,6-disubstituted (4H-pyran-4-ylidene)maolononitrile with a primary amine. We reacted 2-(2-tert-butyl-6-methyl-4H-pyran-4-ylidene)malononitrile with 2-(2-aminoethoxy)ethanol in order to obtain the (1,4-pyridine-4-ylidene)malononitrile substituted with tert-butyl and methyl groups at 2 and 6-positions, respectively. The title compound was however produced as a major product instead of the corresponding malononitrile derivative (VanAllan & Reynolds, 1971). The molecular structure of C17H25N3O3, is shown in (Fig. 1). There are intramolecular hydrogen bonds N3-H3···O1 and C4–H4···O3 (Table 1). An intermolecular hydrogen bond O2-H2···O3(x,1/2-y,-1/2+ z) links the molecules into a zigzag chain which runs along the c axis. These chains are linked to form a sheet by a weak C7–H7A···O21-x,-y,1-z and as C9—H9A···π interaction involving the dihydropyridine ring(1-x,-y,1-z) 1, (Table 1, Fig. 2).