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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3152–o3153.
Published online 2009 November 21. doi:  10.1107/S1600536809048739
PMCID: PMC2972033

N′-[(E)-Benzyl­idene]-1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide

Abstract

In the title compound, C19H18N4O2, the 1,8-naphthyridine ring system is essentially planar [r.m.s. deviation = 0.011 (3) Å]. The dihedral angle between the naphthyridine ring system and the phenyl ring is 28.95 (7)°. The carbohydrazide H atom is involved in an intra­molecular N—H(...)O hydrogen bond, forming a six-membered hydrogen-bonded ring. In the crystal, the mol­ecules arrange themselves into centrosymmetric dimers by means of inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the synthesis of heterocyclic compounds, see: Chen et al. (2001 [triangle]); Zia-ur-Rehman et al. (2006 [triangle], 2009 [triangle]). For their biological activity, see: Ferrarini et al. (2000 [triangle]); Hoock et al. (1999 [triangle]); Nakatani et al. (2001 [triangle]); Roma et al. (2000 [triangle]). For related structures, see: Catalano et al. (2000 [triangle]); Deeba et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3152-scheme1.jpg

Experimental

Crystal data

  • C19H18N4O2
  • M r = 334.37
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3152-efi1.jpg
  • a = 7.1642 (1) Å
  • b = 8.8383 (1) Å
  • c = 14.4560 (2) Å
  • α = 82.624 (6)°
  • β = 85.454 (7)°
  • γ = 68.594 (5)°
  • V = 844.63 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Rigaku R-AXIS RAPID-S diffractometer
  • Absorption correction: multi-scan (Blessing, 1995 [triangle]) T min = 0.983, T max = 0.991
  • 18153 measured reflections
  • 3446 independent reflections
  • 2105 reflections with I > 2σ(I)
  • R int = 0.066

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.175
  • S = 1.03
  • 3446 reflections
  • 236 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048739/is2485sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048739/is2485Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are indebted to the Department of Chemistry and Atatürk University, Turkey, for the use of the X-ray diffractometer purchased under grant No. 2003/219 from the University Research Fund.

supplementary crystallographic information

Comment

1,8-Naphthyridines have been cited in the literature for their medical uses such as antibacterial (Chen et al., 2001), anti-inflammatory (Roma et al., 2000), anti-hypertensive and anti-platelet activities (Ferrarini et al., 2000) agents. Besides few among these have been reported to be excellent fluorescent markers of nucleic acids (Hoock et al., 1999) and probe molecules (Nakatani et al., 2001). In continuation of our work on the synthesis, biological activity and crystal structures of various heterocyclic compounds (Zia-ur-Rehman et al., 2006, 2009), we herein report the synthesis and crystal structure of the title compound (I) (Fig. 1).

The structure of the adjoined pyridine rings comprising of the naphthyridine ring is planar while carbonyl oxygen O1 on C11 is involved in intramolecular hydrogen bonding with N1H, giving rise to a six-membered hydrogen bond ring (Table 1). All bond distances are essentially identical to those found in the literature (Catalano et al., 2000; Deeba et al., 2009). Each molecule forms centrosymmetric dimer through intermolecular C—H···O hydrogen bonds, giving rise the formation of two six-membered hydrogen bond rings per dimer (Fig. 2).

Experimental

A mixture of 1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide (10.0 mmol, 2.46 g), benzaldehyde (11.0 mmol, 1.17 g), ortho phosphoric acid (2 drops) and ethyl alcohol (20.0 ml) was refluxed for a period of two hours. After completion of the reaction as indicated by TLC, three fourth of the solvent was evaporated and the contents were cooled to room temperature. Crystals obtained were washed with cold ethanol and dried; Yield: 89%.

Refinement

H atoms were placed in geometrically idealized positions (C—H = 0.93–0.97 Å) and treated as riding, with Uiso(H) = 1.2Ueq(methine and methylene C) or 1.5Ueq(methyl C). The H atoms attached to atoms N1 and C13 were located in a difference Fourier map and refined freely.

Figures

Fig. 1.
An ORTEP-3 (Farrugia, 1997) drawing of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Perspective view of the three-dimensional crystal packing showing hydrogen-bonded interactions (dashed lines). [Symmetry code: (i) -x + 1, -y - 1, -z.] H atoms not involved in the hydrogen bonds have been omitted for clarity.

Crystal data

C19H18N4O2Z = 2
Mr = 334.37F(000) = 352
Triclinic, P1Dx = 1.315 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1642 (1) ÅCell parameters from 18153 reflections
b = 8.8383 (1) Åθ = 2.5–26.4°
c = 14.4560 (2) ŵ = 0.09 mm1
α = 82.624 (6)°T = 293 K
β = 85.454 (7)°Needles, yellow
γ = 68.594 (5)°0.20 × 0.10 × 0.10 mm
V = 844.63 (4) Å3

Data collection

Rigaku R-AXIS RAPID-S diffractometer3446 independent reflections
Radiation source: fine-focus sealed tube2105 reflections with I > 2σ(I)
graphiteRint = 0.066
ω scansθmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan (Blessing, 1995)h = −8→8
Tmin = 0.983, Tmax = 0.991k = −11→11
18153 measured reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0691P)2 + 0.1621P] where P = (Fo2 + 2Fc2)/3
3446 reflections(Δ/σ)max < 0.001
236 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.17 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/Ueq
C1−0.1188 (4)0.2780 (3)0.28444 (16)0.0632 (7)
H1C−0.10270.18710.33120.095*
H1A−0.25880.33490.27340.095*
H1B−0.06370.35110.30560.095*
C80.3626 (5)−0.3046 (4)0.26006 (19)0.0813 (9)
H8A0.4932−0.34720.23040.122*
H8C0.3494−0.38180.31090.122*
H8B0.3459−0.20340.28340.122*
H130.603 (4)−0.009 (3)−0.3488 (17)0.072 (8)*
H1N0.454 (4)−0.035 (3)−0.2036 (17)0.065 (8)*
C50.1821 (3)0.1032 (3)0.03208 (15)0.0469 (5)
O10.3049 (3)0.1303 (2)−0.12329 (11)0.0627 (5)
N40.0597 (3)0.0569 (2)0.19056 (12)0.0476 (5)
N30.2269 (3)−0.1657 (2)0.10789 (12)0.0466 (5)
N10.4915 (3)−0.1421 (3)−0.20600 (13)0.0546 (5)
C100.3530 (3)−0.1374 (3)−0.04983 (14)0.0468 (5)
C90.3224 (3)−0.2282 (3)0.03032 (15)0.0477 (5)
H90.3716−0.34130.03080.057*
N20.5729 (3)−0.2165 (3)−0.28556 (13)0.0574 (5)
C110.2838 (3)0.0374 (3)−0.05407 (15)0.0480 (5)
C60.1544 (3)0.0025 (3)0.11057 (14)0.0444 (5)
O20.5063 (3)−0.3819 (2)−0.12262 (11)0.0682 (5)
C2−0.0111 (3)0.2171 (3)0.19557 (16)0.0510 (6)
C30.0108 (4)0.3277 (3)0.12111 (17)0.0631 (7)
H3−0.03950.43930.12660.076*
C130.6167 (4)−0.1254 (4)−0.35312 (17)0.0580 (6)
C70.2050 (4)−0.2758 (3)0.19052 (15)0.0564 (7)
H7B0.2152−0.37950.17090.068*
H7A0.0733−0.22810.21990.068*
C140.6940 (4)−0.1896 (3)−0.44275 (15)0.0549 (6)
C40.1069 (4)0.2702 (3)0.04011 (17)0.0594 (7)
H40.12210.3431−0.00970.071*
C120.4574 (4)−0.2336 (3)−0.12865 (15)0.0522 (6)
C150.7825 (4)−0.1063 (3)−0.50867 (17)0.0681 (7)
H150.7952−0.0104−0.49530.082*
C190.6743 (5)−0.3296 (4)−0.46494 (18)0.0778 (9)
H190.6135−0.3863−0.42190.093*
C170.8318 (5)−0.3036 (4)−0.6144 (2)0.0901 (10)
H170.8780−0.3421−0.67200.108*
C160.8518 (5)−0.1637 (4)−0.59383 (19)0.0807 (9)
H160.9123−0.1073−0.63730.097*
C180.7436 (6)−0.3872 (4)−0.5502 (2)0.0992 (12)
H180.7305−0.4826−0.56400.119*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0648 (16)0.0627 (16)0.0549 (15)−0.0110 (13)0.0065 (12)−0.0216 (12)
C80.108 (2)0.0676 (18)0.0590 (16)−0.0244 (17)−0.0082 (16)0.0081 (14)
C50.0490 (13)0.0456 (12)0.0439 (12)−0.0144 (10)0.0011 (10)−0.0061 (10)
O10.0816 (13)0.0578 (10)0.0443 (9)−0.0239 (9)0.0122 (8)−0.0018 (8)
N40.0495 (11)0.0484 (11)0.0412 (10)−0.0126 (9)0.0058 (8)−0.0109 (8)
N30.0524 (11)0.0450 (10)0.0398 (10)−0.0149 (9)0.0093 (8)−0.0096 (8)
N10.0641 (13)0.0592 (13)0.0389 (11)−0.0206 (11)0.0121 (9)−0.0124 (9)
C100.0482 (13)0.0518 (13)0.0381 (11)−0.0155 (10)0.0046 (10)−0.0082 (10)
C90.0492 (13)0.0460 (12)0.0448 (12)−0.0133 (10)0.0070 (10)−0.0111 (10)
N20.0586 (13)0.0661 (13)0.0432 (11)−0.0171 (10)0.0096 (9)−0.0136 (9)
C110.0504 (13)0.0540 (13)0.0392 (11)−0.0192 (11)0.0038 (10)−0.0063 (10)
C60.0421 (12)0.0461 (12)0.0408 (11)−0.0112 (10)0.0033 (9)−0.0070 (9)
O20.0869 (13)0.0542 (11)0.0533 (10)−0.0148 (9)0.0182 (9)−0.0144 (8)
C20.0487 (13)0.0503 (13)0.0493 (13)−0.0099 (11)0.0003 (10)−0.0133 (11)
C30.0777 (18)0.0438 (13)0.0589 (15)−0.0108 (13)0.0029 (13)−0.0105 (11)
C130.0620 (16)0.0665 (17)0.0463 (14)−0.0239 (13)0.0064 (11)−0.0119 (12)
C70.0746 (17)0.0453 (13)0.0436 (12)−0.0187 (12)0.0179 (12)−0.0054 (10)
C140.0554 (15)0.0638 (15)0.0403 (12)−0.0161 (12)0.0055 (10)−0.0076 (11)
C40.0732 (17)0.0480 (14)0.0499 (14)−0.0157 (12)0.0022 (12)−0.0011 (11)
C120.0525 (14)0.0578 (15)0.0435 (13)−0.0162 (12)0.0070 (10)−0.0111 (11)
C150.0797 (19)0.0685 (17)0.0563 (15)−0.0290 (15)0.0143 (13)−0.0099 (13)
C190.110 (2)0.0807 (19)0.0517 (15)−0.0485 (18)0.0251 (15)−0.0146 (14)
C170.125 (3)0.095 (2)0.0570 (17)−0.048 (2)0.0380 (17)−0.0298 (16)
C160.095 (2)0.089 (2)0.0568 (16)−0.0363 (18)0.0282 (15)−0.0125 (15)
C180.154 (3)0.095 (2)0.0663 (19)−0.066 (2)0.038 (2)−0.0343 (17)

Geometric parameters (Å, °)

C1—C21.501 (3)C9—H90.9300
C1—H1C0.9600N2—C131.279 (3)
C1—H1A0.9600O2—C121.220 (3)
C1—H1B0.9600C2—C31.397 (3)
C8—C71.501 (4)C3—C41.369 (3)
C8—H8A0.9600C3—H30.9300
C8—H8C0.9600C13—C141.467 (3)
C8—H8B0.9600C13—H131.01 (3)
C5—C41.391 (3)C7—H7B0.9700
C5—C61.398 (3)C7—H7A0.9700
C5—C111.467 (3)C14—C191.375 (4)
O1—C111.246 (3)C14—C151.384 (3)
N4—C21.328 (3)C4—H40.9300
N4—C61.345 (3)C15—C161.378 (3)
N3—C91.339 (3)C15—H150.9300
N3—C61.388 (3)C19—C181.379 (4)
N3—C71.477 (3)C19—H190.9300
N1—C121.354 (3)C17—C161.367 (4)
N1—N21.379 (3)C17—C181.370 (4)
N1—H1N0.89 (3)C17—H170.9300
C10—C91.373 (3)C16—H160.9300
C10—C111.435 (3)C18—H180.9300
C10—C121.494 (3)
C2—C1—H1C109.5C3—C2—C1120.2 (2)
C2—C1—H1A109.5C4—C3—C2119.4 (2)
H1C—C1—H1A109.5C4—C3—H3120.3
C2—C1—H1B109.5C2—C3—H3120.3
H1C—C1—H1B109.5N2—C13—C14120.2 (2)
H1A—C1—H1B109.5N2—C13—H13123.6 (14)
C7—C8—H8A109.5C14—C13—H13116.3 (14)
C7—C8—H8C109.5N3—C7—C8111.6 (2)
H8A—C8—H8C109.5N3—C7—H7B109.3
C7—C8—H8B109.5C8—C7—H7B109.3
H8A—C8—H8B109.5N3—C7—H7A109.3
H8C—C8—H8B109.5C8—C7—H7A109.3
C4—C5—C6116.1 (2)H7B—C7—H7A108.0
C4—C5—C11121.7 (2)C19—C14—C15118.3 (2)
C6—C5—C11122.2 (2)C19—C14—C13121.3 (2)
C2—N4—C6117.81 (19)C15—C14—C13120.3 (2)
C9—N3—C6119.42 (18)C3—C4—C5120.2 (2)
C9—N3—C7119.91 (18)C3—C4—H4119.9
C6—N3—C7120.65 (17)C5—C4—H4119.9
C12—N1—N2119.2 (2)O2—C12—N1123.7 (2)
C12—N1—H1N117.7 (16)O2—C12—C10122.0 (2)
N2—N1—H1N123.0 (16)N1—C12—C10114.2 (2)
C9—C10—C11120.18 (19)C16—C15—C14120.8 (3)
C9—C10—C12115.2 (2)C16—C15—H15119.6
C11—C10—C12124.6 (2)C14—C15—H15119.6
N3—C9—C10124.7 (2)C14—C19—C18120.9 (3)
N3—C9—H9117.7C14—C19—H19119.5
C10—C9—H9117.7C18—C19—H19119.5
C13—N2—N1115.6 (2)C16—C17—C18120.0 (3)
O1—C11—C10125.0 (2)C16—C17—H17120.0
O1—C11—C5120.8 (2)C18—C17—H17120.0
C10—C11—C5114.23 (19)C17—C16—C15120.0 (3)
N4—C6—N3116.26 (19)C17—C16—H16120.0
N4—C6—C5124.4 (2)C15—C16—H16120.0
N3—C6—C5119.32 (18)C17—C18—C19120.0 (3)
N4—C2—C3122.0 (2)C17—C18—H18120.0
N4—C2—C1117.8 (2)C19—C18—H18120.0
C6—N3—C9—C10−1.1 (3)N4—C2—C3—C40.3 (4)
C7—N3—C9—C10−179.3 (2)C1—C2—C3—C4−179.1 (2)
C11—C10—C9—N31.2 (4)N1—N2—C13—C14−176.7 (2)
C12—C10—C9—N3−178.0 (2)C9—N3—C7—C897.7 (3)
C12—N1—N2—C13−174.3 (2)C6—N3—C7—C8−80.4 (3)
C9—C10—C11—O1179.8 (2)N2—C13—C14—C1916.6 (4)
C12—C10—C11—O1−1.2 (4)N2—C13—C14—C15−165.8 (2)
C9—C10—C11—C5−0.3 (3)C2—C3—C4—C50.0 (4)
C12—C10—C11—C5178.8 (2)C6—C5—C4—C3−0.5 (4)
C4—C5—C11—O1−0.4 (4)C11—C5—C4—C3179.3 (2)
C6—C5—C11—O1179.4 (2)N2—N1—C12—O24.9 (4)
C4—C5—C11—C10179.6 (2)N2—N1—C12—C10−174.99 (19)
C6—C5—C11—C10−0.6 (3)C9—C10—C12—O22.0 (4)
C2—N4—C6—N3179.8 (2)C11—C10—C12—O2−177.1 (2)
C2—N4—C6—C5−0.5 (3)C9—C10—C12—N1−178.1 (2)
C9—N3—C6—N4179.85 (19)C11—C10—C12—N12.8 (3)
C7—N3—C6—N4−2.0 (3)C19—C14—C15—C16−1.0 (4)
C9—N3—C6—C50.1 (3)C13—C14—C15—C16−178.7 (3)
C7—N3—C6—C5178.3 (2)C15—C14—C19—C180.9 (5)
C4—C5—C6—N40.8 (3)C13—C14—C19—C18178.6 (3)
C11—C5—C6—N4−179.0 (2)C18—C17—C16—C15−0.3 (5)
C4—C5—C6—N3−179.5 (2)C14—C15—C16—C170.7 (5)
C11—C5—C6—N30.7 (3)C16—C17—C18—C190.3 (6)
C6—N4—C2—C3−0.1 (3)C14—C19—C18—C17−0.6 (6)
C6—N4—C2—C1179.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O10.89 (3)1.93 (2)2.674 (3)140 (2)
C7—H7B···O2i0.972.453.204 (3)134
C9—H9···O2i0.932.513.340 (3)149

Symmetry codes: (i) −x+1, −y−1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2485).

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