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The title compound, C18H18N2O5, was synthesized from 2,3-dimethoxy­phenyl­methyl­idenemalononitrile and ethyl aceto­acetate in the presence of triethyl­benzyl­ammonium chloride in an aqueous medium. The pyridone and benzene rings make a dihedral angle of 63.8 (1)°. There are inter­molecular C—H...O and N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028679/ob6584sup1.cif
Contains datablocks wyc16, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028679/ob6584Isup2.hkl
Contains datablock I

CCDC reference: 287684

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.047
  • wR factor = 0.137
  • Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C6 ... 1.43 Ang. PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C10
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

It is known that many pyridine derivatives exhibit a wide spectrum of pharmacological activities and biological activities, such as inhibitory activity (Liu et al., 1980 or 2002?), antimicrobial activity (Aytemir et al., 2003) and anti-inflammatory activity (Ozturk et al., 2002). We report here the crystal structure of the title compound, (I). Its aqueous synthesis (see Experimental) was inspired by the work of Breslow & Rideout (1980), who rediscovered the use of water as a solvent in organic chemistry.

In (I), the C2—C3 bond distance of 1.376 (2) Å is equal to the value of 1.376 (2) Å for C4—C5, indicating double-bond character in both cases, which indicates that the further aromatization took place unexpectedly. The pyridine ring (C1—C5/N1) are essentially planar (Fig. 1), with a maximum deviation of 0.026 (1) Å for C2. This ring forms a dihedral angle of 63.8 (1)° with the benzene ring (C11–C16). Molecules form centrosymmetric dimers by N1—H1A···O1 (1 − x, 3 − y, 1 − z) hydrogen bonds (Table 2), and they are further linked via C16—H16A···O1 (x, y − 1, z) interactions (Fig. 2).

Experimental top

The compound (I) was prepared by the reaction of 2,3-dimethoxylphenylmethylidenemalononitrile (0.42 g, 2 mmol) and ethyl acetoacetate (0.39 g, 3 mmol) in the presence of triethylbenzylammonium chloride (0.1 g) in water at 363 K for 8 h (yield 93%, mp. 513–515 K). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a DMF solution.

1H NMR (CDCl3): 0.89 (t, J = 7.2 Hz, 3H, CH3), 2.68 (s, 3H, CH3), 3.86 (s, 3H, OCH3), 3.92 (s, 3H, OCH3), 4.00 (q, J = 7.2 Hz, 2H, CH2), 6.77 (dd, J = 1.2 Hz, J' = 7.6 Hz, 1H, ArH), 7.04 (dd, J = 1.2 Hz, J' = 8.0 Hz, 1H, ArH), 6.14 (dd, J = 7.6 Hz, J' = 8.0 Hz, 1H, ArH), IR (cm−1): 3052 (ArH), 2852 (C—H), 2224 (CN), 1722, 1661 (C=O), 1592, 1470, 1430 (phenyl ring).

Refinement top

The H atoms were positioned geometrically and refined as riding, with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(parent atom).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure drawing for (I), showing 50% probability of displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The packing diagram of (I) along c. Dashed lines indicate hydrogen bonds.
Ethyl 2-methyl-4-(2,3-dimethoxylphenyl)-5-cyano-6-oxo- pyridin-3-carboxylate top
Crystal data top
C18H18N2O5F(000) = 720
Mr = 342.34Dx = 1.323 Mg m3
Monoclinic, P21/cMelting point = 513–515 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 15.2031 (14) ÅCell parameters from 2339 reflections
b = 7.5946 (7) Åθ = 2.7–25.0°
c = 15.1270 (14) ŵ = 0.10 mm1
β = 100.143 (2)°T = 292 K
V = 1719.3 (3) Å3Block, colorless
Z = 40.2 × 0.1 × 0.1 mm
Data collection top
Bruker SMART CCD area detector
diffractometer
2559 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
Graphite monochromatorθmax = 26.0°, θmin = 2.7°
ϕ and ω scansh = 1818
8803 measured reflectionsk = 89
3379 independent reflectionsl = 1518
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0722P)2 + 0.1609P]
where P = (Fo2 + 2Fc2)/3
3379 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C18H18N2O5V = 1719.3 (3) Å3
Mr = 342.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.2031 (14) ŵ = 0.10 mm1
b = 7.5946 (7) ÅT = 292 K
c = 15.1270 (14) Å0.2 × 0.1 × 0.1 mm
β = 100.143 (2)°
Data collection top
Bruker SMART CCD area detector
diffractometer
2559 reflections with I > 2σ(I)
8803 measured reflectionsRint = 0.026
3379 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.07Δρmax = 0.27 e Å3
3379 reflectionsΔρmin = 0.16 e Å3
226 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.40899 (10)1.3222 (2)0.43955 (11)0.0430 (4)
C20.34531 (10)1.1906 (2)0.40264 (11)0.0412 (4)
C30.32290 (10)1.0534 (2)0.45385 (11)0.0405 (4)
C40.36887 (11)1.0329 (2)0.54334 (11)0.0456 (4)
C50.43235 (11)1.1546 (2)0.57887 (12)0.0464 (4)
C60.30640 (11)1.2085 (2)0.30983 (12)0.0441 (4)
C70.35129 (12)0.8795 (3)0.59942 (12)0.0541 (5)
C80.23996 (17)0.7002 (3)0.64431 (16)0.0776 (7)
H8A0.25710.70820.70910.093*
H8B0.26940.59870.62370.093*
C90.14130 (17)0.6825 (3)0.61880 (18)0.0881 (8)
H9A0.12210.57770.64540.132*
H9B0.12520.67510.55460.132*
H9C0.11290.78320.63990.132*
C100.48522 (13)1.1515 (3)0.67227 (13)0.0631 (5)
H10A0.52481.25090.68070.095*
H10B0.51951.04480.68120.095*
H10C0.44531.15690.71480.095*
C110.25205 (10)0.9258 (2)0.41475 (10)0.0405 (4)
C120.16453 (10)0.9831 (2)0.39121 (10)0.0384 (4)
C130.09645 (11)0.8634 (2)0.35838 (11)0.0444 (4)
C140.11747 (13)0.6886 (2)0.34890 (13)0.0551 (5)
H14A0.07270.60830.32690.066*
C150.20513 (14)0.6326 (3)0.37206 (14)0.0597 (5)
H15A0.21880.51450.36540.072*
C160.27223 (12)0.7487 (2)0.40471 (13)0.0524 (5)
H16A0.33090.70940.42010.063*
C170.11538 (15)1.1994 (3)0.48155 (16)0.0698 (6)
H17A0.10241.32300.48300.105*
H17B0.16181.17020.53110.105*
H17C0.06261.13300.48590.105*
C180.05858 (13)0.8161 (3)0.30424 (15)0.0657 (6)
H18A0.11370.88070.29210.099*
H18B0.06270.72660.34810.099*
H18C0.04750.76220.24980.099*
N10.44813 (9)1.29320 (19)0.52732 (10)0.0477 (4)
H1A0.48621.37020.55190.057*
N20.27760 (11)1.2211 (2)0.23497 (12)0.0656 (5)
O10.42765 (8)1.45469 (16)0.39909 (8)0.0525 (3)
O20.40881 (11)0.7845 (2)0.63687 (13)0.0896 (6)
O30.26547 (9)0.85995 (17)0.60199 (9)0.0570 (4)
O40.14408 (7)1.15804 (14)0.39973 (8)0.0461 (3)
O50.01266 (8)0.93290 (17)0.33772 (9)0.0571 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0337 (8)0.0416 (10)0.0515 (10)0.0016 (7)0.0009 (7)0.0033 (7)
C20.0352 (8)0.0389 (9)0.0471 (9)0.0025 (7)0.0007 (7)0.0018 (7)
C30.0353 (8)0.0369 (9)0.0475 (9)0.0036 (7)0.0023 (7)0.0021 (7)
C40.0407 (8)0.0455 (10)0.0476 (9)0.0006 (8)0.0004 (7)0.0012 (7)
C50.0371 (8)0.0499 (10)0.0497 (10)0.0023 (8)0.0005 (7)0.0015 (8)
C60.0411 (9)0.0394 (9)0.0496 (10)0.0029 (7)0.0022 (7)0.0005 (7)
C70.0530 (10)0.0551 (11)0.0489 (10)0.0004 (9)0.0057 (8)0.0055 (8)
C80.0975 (18)0.0661 (14)0.0700 (14)0.0113 (13)0.0170 (12)0.0216 (11)
C90.1015 (19)0.0786 (18)0.0890 (18)0.0343 (15)0.0305 (15)0.0021 (13)
C100.0518 (11)0.0794 (15)0.0523 (11)0.0077 (10)0.0065 (9)0.0041 (10)
C110.0442 (9)0.0362 (9)0.0390 (8)0.0020 (7)0.0016 (7)0.0003 (6)
C120.0442 (9)0.0322 (8)0.0365 (8)0.0023 (7)0.0006 (7)0.0000 (6)
C130.0448 (9)0.0448 (10)0.0410 (9)0.0053 (8)0.0005 (7)0.0010 (7)
C140.0629 (12)0.0437 (11)0.0563 (11)0.0152 (9)0.0036 (9)0.0104 (8)
C150.0705 (12)0.0350 (10)0.0718 (13)0.0013 (9)0.0080 (10)0.0099 (9)
C160.0518 (10)0.0399 (10)0.0639 (12)0.0060 (8)0.0057 (9)0.0036 (8)
C170.0818 (15)0.0545 (13)0.0757 (14)0.0071 (11)0.0214 (11)0.0120 (10)
C180.0517 (11)0.0715 (15)0.0681 (13)0.0222 (10)0.0058 (9)0.0032 (10)
N10.0385 (7)0.0473 (9)0.0532 (9)0.0067 (6)0.0029 (6)0.0051 (7)
N20.0654 (10)0.0727 (12)0.0546 (10)0.0046 (9)0.0010 (8)0.0033 (8)
O10.0480 (7)0.0434 (7)0.0619 (8)0.0079 (6)0.0017 (6)0.0047 (6)
O20.0730 (10)0.0874 (12)0.0991 (12)0.0109 (9)0.0103 (9)0.0411 (10)
O30.0605 (8)0.0515 (8)0.0581 (8)0.0057 (6)0.0082 (6)0.0114 (6)
O40.0456 (6)0.0347 (7)0.0553 (7)0.0011 (5)0.0016 (5)0.0005 (5)
O50.0409 (6)0.0525 (8)0.0718 (9)0.0097 (6)0.0072 (6)0.0029 (6)
Geometric parameters (Å, º) top
C1—O11.236 (2)C10—H10B0.9600
C1—N11.374 (2)C10—H10C0.9600
C1—C21.435 (2)C11—C121.385 (2)
C2—C31.376 (2)C11—C161.394 (2)
C2—C61.431 (2)C12—O41.3761 (19)
C3—C41.419 (2)C12—C131.401 (2)
C3—C111.492 (2)C13—O51.363 (2)
C4—C51.376 (2)C13—C141.379 (3)
C4—C71.493 (3)C14—C151.384 (3)
C5—N11.356 (2)C14—H14A0.9300
C5—C101.497 (2)C15—C161.373 (3)
C6—N21.144 (2)C15—H15A0.9300
C7—O21.196 (2)C16—H16A0.9300
C7—O31.321 (2)C17—O41.418 (2)
C8—O31.456 (2)C17—H17A0.9600
C8—C91.488 (3)C17—H17B0.9600
C8—H8A0.9700C17—H17C0.9600
C8—H8B0.9700C18—O51.422 (2)
C9—H9A0.9600C18—H18A0.9600
C9—H9B0.9600C18—H18B0.9600
C9—H9C0.9600C18—H18C0.9600
C10—H10A0.9600N1—H1A0.8600
O1—C1—N1120.73 (14)C12—C11—C16119.65 (15)
O1—C1—C2124.92 (15)C12—C11—C3119.47 (14)
N1—C1—C2114.33 (15)C16—C11—C3120.84 (15)
C3—C2—C6121.57 (14)O4—C12—C11120.10 (13)
C3—C2—C1121.70 (15)O4—C12—C13119.65 (14)
C6—C2—C1116.73 (15)C11—C12—C13120.25 (15)
C2—C3—C4119.42 (14)O5—C13—C14124.99 (15)
C2—C3—C11120.11 (14)O5—C13—C12115.60 (15)
C4—C3—C11120.46 (14)C14—C13—C12119.41 (16)
C5—C4—C3119.53 (16)C13—C14—C15120.02 (17)
C5—C4—C7119.07 (15)C13—C14—H14A120.0
C3—C4—C7121.39 (15)C15—C14—H14A120.0
N1—C5—C4118.67 (15)C16—C15—C14121.00 (18)
N1—C5—C10115.76 (15)C16—C15—H15A119.5
C4—C5—C10125.54 (16)C14—C15—H15A119.5
N2—C6—C2178.00 (18)C15—C16—C11119.68 (17)
O2—C7—O3124.17 (19)C15—C16—H16A120.2
O2—C7—C4123.41 (18)C11—C16—H16A120.2
O3—C7—C4112.41 (15)O4—C17—H17A109.5
O3—C8—C9107.19 (19)O4—C17—H17B109.5
O3—C8—H8A110.3H17A—C17—H17B109.5
C9—C8—H8A110.3O4—C17—H17C109.5
O3—C8—H8B110.3H17A—C17—H17C109.5
C9—C8—H8B110.3H17B—C17—H17C109.5
H8A—C8—H8B108.5O5—C18—H18A109.5
C8—C9—H9A109.5O5—C18—H18B109.5
C8—C9—H9B109.5H18A—C18—H18B109.5
H9A—C9—H9B109.5O5—C18—H18C109.5
C8—C9—H9C109.5H18A—C18—H18C109.5
H9A—C9—H9C109.5H18B—C18—H18C109.5
H9B—C9—H9C109.5C5—N1—C1126.15 (14)
C5—C10—H10A109.5C5—N1—H1A116.9
C5—C10—H10B109.5C1—N1—H1A116.9
H10A—C10—H10B109.5C7—O3—C8116.59 (16)
C5—C10—H10C109.5C12—O4—C17113.89 (14)
H10A—C10—H10C109.5C13—O5—C18117.53 (14)
H10B—C10—H10C109.5
O1—C1—C2—C3174.95 (16)C3—C11—C12—O43.2 (2)
N1—C1—C2—C33.4 (2)C16—C11—C12—C130.7 (2)
O1—C1—C2—C65.2 (2)C3—C11—C12—C13176.97 (14)
N1—C1—C2—C6176.37 (14)O4—C12—C13—O50.6 (2)
C6—C2—C3—C4174.61 (15)C11—C12—C13—O5179.60 (14)
C1—C2—C3—C45.2 (2)O4—C12—C13—C14179.18 (15)
C6—C2—C3—C114.2 (2)C11—C12—C13—C140.6 (2)
C1—C2—C3—C11175.96 (14)O5—C13—C14—C15179.99 (17)
C2—C3—C4—C52.8 (2)C12—C13—C14—C150.2 (3)
C11—C3—C4—C5178.31 (15)C13—C14—C15—C160.1 (3)
C2—C3—C4—C7175.82 (16)C14—C15—C16—C110.0 (3)
C11—C3—C4—C73.0 (2)C12—C11—C16—C150.3 (3)
C3—C4—C5—N11.1 (2)C3—C11—C16—C15177.27 (17)
C7—C4—C5—N1179.75 (16)C4—C5—N1—C12.9 (3)
C3—C4—C5—C10179.17 (16)C10—C5—N1—C1178.79 (16)
C7—C4—C5—C102.1 (3)O1—C1—N1—C5179.16 (16)
C5—C4—C7—O251.8 (3)C2—C1—N1—C50.7 (2)
C3—C4—C7—O2126.9 (2)O2—C7—O3—C87.7 (3)
C5—C4—C7—O3128.92 (17)C4—C7—O3—C8171.60 (17)
C3—C4—C7—O352.4 (2)C9—C8—O3—C7165.37 (19)
C2—C3—C11—C1265.9 (2)C11—C12—O4—C1795.16 (18)
C4—C3—C11—C12115.23 (17)C13—C12—O4—C1785.03 (19)
C2—C3—C11—C16116.45 (18)C14—C13—O5—C180.3 (3)
C4—C3—C11—C1662.4 (2)C12—C13—O5—C18179.93 (15)
C16—C11—C12—O4179.13 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···O1i0.932.483.263 (1)141
N1—H1A···O1ii0.861.922.780 (2)177
Symmetry codes: (i) x, y1, z; (ii) x+1, y+3, z+1.

Experimental details

Crystal data
Chemical formulaC18H18N2O5
Mr342.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)292
a, b, c (Å)15.2031 (14), 7.5946 (7), 15.1270 (14)
β (°) 100.143 (2)
V3)1719.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.2 × 0.1 × 0.1
Data collection
DiffractometerBruker SMART CCD area detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8803, 3379, 2559
Rint0.026
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.137, 1.07
No. of reflections3379
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.16

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Selected geometric parameters (Å, º) top
C1—N11.374 (2)C3—C41.419 (2)
C1—C21.435 (2)C4—C51.376 (2)
C2—C31.376 (2)C5—N11.356 (2)
N1—C1—C2114.33 (15)C5—C4—C3119.53 (16)
C3—C2—C1121.70 (15)N1—C5—C4118.67 (15)
C2—C3—C4119.42 (14)C5—N1—C1126.15 (14)
N1—C1—C2—C33.4 (2)C3—C4—C7—O352.4 (2)
C1—C2—C3—C45.2 (2)C2—C3—C11—C1265.9 (2)
C2—C3—C4—C52.8 (2)C4—C5—N1—C12.9 (3)
C3—C4—C5—N11.1 (2)C2—C1—N1—C50.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···O1i0.932.483.263 (1)141
N1—H1A···O1ii0.861.922.780 (2)177
Symmetry codes: (i) x, y1, z; (ii) x+1, y+3, z+1.
 

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