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Acta Cryst. (2010). E66, o291    [ doi:10.1107/S1600536810000371 ]

(E)-N'-[(E)-3-(4-Hydroxy-3-methoxyphenyl)allylidene]isonicotinohydrazide

H. S. Naveenkumar, A. Sadikun, P. Ibrahim, C. K. Quah and H.-K. Fun

Abstract top

In the title compound, C16H15N3O3, the dihedral angle between the pyridine and benzene rings is 7.66 (5)°. The crystal packing is consolidated by intermolecular C-H...O and O-H...N interactions, which link the molecules into zigzag chains propagating along [010]. The chains are further linked into a three-dimensional network by N-H...O, C-H...N, C-H...O and C-H...[pi] interactions.

Comment top

In the search of new compounds, isoniazid derivatives have been found to possess potential tuberculostatic activities (e.g. Janin, 2007). As a part of a current work of synthesis of (E)-N'-substituted isonicotinohydrazide derivatives, we present the crystal structure of the title compound, (I), (Fig. 1).

The pyridine ring (N1/C1–C5) in (I) forms dihedral angle of 7.66 (5)° with the benzene ring (C10–C15), indicating that they are almost co-planar to each other. Bond lengths and angles are within normal ranges, and comparable to closely related structures (Naveenkumar et al., 2009a,b,c; Shi, 2005).

The crystal packing is consolidated by intermolecular C2—H2A···O3 and O2—H1O2···N1 interactions (Fig. 2) which link the independent molecules into zig-zag chains along the [0 1 0] direction. The crystal structure is further linked via N2—H1N2···O1, C4—H4A···N3 and C7—H7A···O1 interactions, into three-dimensional network. The structure is also stabilized by C—H···π interactions (Table 1).

Related literature top

For the synthesis, see: Lourenco et al. (2008). For the tuberculostatic activities of isoniazid derivatives, see: Janin (2007). For related structures, see: Naveenkumar et al. (2009a,b,c); Shi (2005). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

The isoniazid derivative was prepared following the procedure by Lourenco et al. (2008). (E)-N'-[(E)-3-(4-hydroxy-3-methoxyphenyl) allylidene]isonicotinohydrazide was prepared by reaction between the 4-hydroxy-3-methoxy cinnamaldehyde (1.0 eq) with isoniazid (1.0 eq) in ethanol/water. After stirring for 1-3 h at room temperature, the resulting mixture was concentrated under reduced pressure. The residue, purified by washing with cold ethanol and ethyl ether, afforded the pure derivative. Yellow needles of (I) were obtained by recrystallization from methanol.

Refinement top

Atoms H1N2 and H1O2 were located in a difference Fourier map and refined freely. The remaining H atoms were positioned geometrically and refined using a riding model, with C-H = 0.93–0.96 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating-group model was applied for the methyl groups.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) showing 50% displacement ellipsoids.
[Figure 2] Fig. 2. The crystal packing of (I), viewed down the a axis. H atoms not involving in hydrogen bonds (dashed lines) have been omitted for clarity.
(E)-N'-[(E)-3-(4-Hydroxy-3- methoxyphenyl)allylidene]isonicotinohydrazide top
Crystal data top
C16H15N3O3F(000) = 624
Mr = 297.31Dx = 1.402 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9970 reflections
a = 5.0470 (1) Åθ = 2.2–30.1°
b = 28.9314 (6) ŵ = 0.10 mm−1
c = 9.6446 (2) ÅT = 100 K
β = 90.010 (1)°Needle, yellow
V = 1408.27 (5) Å30.53 × 0.20 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD
diffractometer		4144 independent reflections
Radiation source: fine-focus sealed tube3534 reflections with I > 2σ(I)
graphiteRint = 0.030
φ and ω scansθmax = 30.2°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		h = −7→7
Tmin = 0.950, Tmax = 0.992k = −40→40
33857 measured reflectionsl = −13→13
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0505P)2 + 0.5887P]
where P = (Fo2 + 2Fc2)/3
4144 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
C16H15N3O3V = 1408.27 (5) Å3
Mr = 297.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.0470 (1) ŵ = 0.10 mm−1
b = 28.9314 (6) ÅT = 100 K
c = 9.6446 (2) Å0.53 × 0.20 × 0.08 mm
β = 90.010 (1)°
Data collection top
Bruker SMART APEXII CCD
diffractometer		4144 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		3534 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.992Rint = 0.030
33857 measured reflectionsθmax = 30.2°
Refinement top
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110Δρmax = 0.43 e Å−3
S = 1.05Δρmin = −0.22 e Å−3
4144 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.08233 (15)0.46282 (3)0.88942 (9)0.01916 (18)
O20.21767 (17)0.74390 (3)0.22611 (9)0.01855 (18)
O30.60188 (15)0.73516 (3)0.41721 (8)0.01721 (17)
N10.7016 (2)0.32923 (3)1.14947 (11)0.0203 (2)
N20.64104 (19)0.47193 (3)0.84655 (10)0.01645 (19)
N30.68169 (19)0.51003 (3)0.76213 (10)0.0175 (2)
C10.5730 (2)0.38057 (4)0.96577 (15)0.0242 (3)
H1A0.45550.38730.89430.029*
C20.5420 (2)0.34088 (4)1.04462 (15)0.0260 (3)
H2A0.40200.32121.02330.031*
C30.8987 (3)0.35853 (4)1.17893 (13)0.0235 (3)
H3A1.00930.35151.25310.028*
C40.9479 (2)0.39885 (4)1.10550 (12)0.0213 (2)
H4A1.08870.41801.12940.026*
C50.7823 (2)0.41004 (4)0.99545 (11)0.0149 (2)
C60.8505 (2)0.45104 (4)0.90682 (11)0.0144 (2)
C70.4745 (2)0.52317 (4)0.69452 (12)0.0179 (2)
H7A0.31810.50630.70020.021*
C80.4869 (2)0.56419 (4)0.61002 (12)0.0184 (2)
H8A0.64250.58140.60960.022*
C90.2819 (2)0.57851 (4)0.53159 (12)0.0181 (2)
H9A0.13490.55920.52730.022*
C100.2689 (2)0.62152 (4)0.45276 (11)0.0158 (2)
C110.4478 (2)0.65790 (4)0.47779 (11)0.0158 (2)
H11A0.57620.65460.54630.019*
C120.4357 (2)0.69838 (4)0.40220 (11)0.0141 (2)
C130.2379 (2)0.70419 (4)0.29982 (11)0.0144 (2)
C140.0603 (2)0.66845 (4)0.27564 (12)0.0173 (2)
H14A−0.06950.67190.20800.021*
C150.0737 (2)0.62759 (4)0.35120 (12)0.0173 (2)
H15A−0.04780.60410.33420.021*
C160.7875 (2)0.73391 (4)0.52991 (12)0.0176 (2)
H16A0.90590.75980.52290.026*
H16B0.88730.70570.52590.026*
H16C0.69340.73540.61630.026*
H1N20.476 (3)0.4640 (5)0.8667 (16)0.025 (4)*
H1O20.284 (4)0.7669 (7)0.272 (2)0.048 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0127 (4)0.0203 (4)0.0245 (4)−0.0018 (3)0.0008 (3)0.0028 (3)
O20.0221 (4)0.0158 (4)0.0178 (4)−0.0010 (3)−0.0061 (3)0.0024 (3)
O30.0162 (4)0.0151 (4)0.0203 (4)−0.0022 (3)−0.0061 (3)0.0015 (3)
N10.0241 (5)0.0162 (5)0.0204 (5)−0.0010 (4)0.0014 (4)0.0014 (4)
N20.0127 (4)0.0140 (4)0.0226 (5)−0.0011 (3)0.0009 (3)0.0045 (4)
N30.0172 (4)0.0131 (4)0.0221 (5)−0.0014 (3)0.0008 (3)0.0035 (4)
C10.0188 (5)0.0180 (6)0.0358 (7)−0.0030 (4)−0.0089 (5)0.0068 (5)
C20.0201 (6)0.0178 (6)0.0400 (7)−0.0052 (4)−0.0061 (5)0.0068 (5)
C30.0312 (6)0.0218 (6)0.0175 (5)−0.0057 (5)−0.0059 (4)0.0030 (5)
C40.0249 (6)0.0206 (6)0.0183 (5)−0.0066 (4)−0.0042 (4)0.0012 (4)
C50.0139 (5)0.0130 (5)0.0178 (5)0.0010 (4)0.0029 (4)−0.0013 (4)
C60.0139 (5)0.0128 (5)0.0163 (5)−0.0004 (4)0.0009 (4)−0.0009 (4)
C70.0162 (5)0.0154 (5)0.0220 (5)−0.0018 (4)0.0009 (4)0.0018 (4)
C80.0169 (5)0.0154 (5)0.0228 (6)−0.0009 (4)0.0011 (4)0.0025 (4)
C90.0170 (5)0.0153 (5)0.0221 (6)−0.0014 (4)0.0006 (4)0.0018 (4)
C100.0154 (5)0.0155 (5)0.0166 (5)0.0012 (4)0.0008 (4)0.0006 (4)
C110.0136 (5)0.0168 (5)0.0171 (5)0.0015 (4)−0.0021 (4)0.0010 (4)
C120.0124 (4)0.0149 (5)0.0149 (5)0.0004 (4)0.0003 (3)−0.0018 (4)
C130.0157 (5)0.0152 (5)0.0122 (5)0.0018 (4)−0.0003 (3)−0.0003 (4)
C140.0178 (5)0.0186 (5)0.0155 (5)−0.0005 (4)−0.0042 (4)−0.0015 (4)
C150.0166 (5)0.0164 (5)0.0190 (5)−0.0018 (4)−0.0013 (4)−0.0022 (4)
C160.0154 (5)0.0197 (5)0.0178 (5)−0.0003 (4)−0.0045 (4)−0.0015 (4)
Geometric parameters (Å, °) top
O1—C61.2301 (13)C5—C61.5021 (15)
O2—C131.3550 (13)C7—C81.4410 (16)
O2—H1O20.87 (2)C7—H7A0.9300
O3—C121.3626 (13)C8—C91.3470 (16)
O3—C161.4352 (13)C8—H8A0.9300
N1—C21.3360 (16)C9—C101.4598 (15)
N1—C31.3373 (16)C9—H9A0.9300
N2—C61.3494 (14)C10—C151.4000 (15)
N2—N31.3856 (13)C10—C111.4075 (15)
N2—H1N20.884 (17)C11—C121.3808 (15)
N3—C71.2895 (15)C11—H11A0.9300
C1—C21.3862 (17)C12—C131.4142 (15)
C1—C51.3875 (16)C13—C141.3881 (15)
C1—H1A0.9300C14—C151.3904 (16)
C2—H2A0.9300C14—H14A0.9300
C3—C41.3871 (17)C15—H15A0.9300
C3—H3A0.9300C16—H16A0.9600
C4—C51.3889 (16)C16—H16B0.9600
C4—H4A0.9300C16—H16C0.9600
C13—O2—H1O2110.8 (13)C9—C8—H8A118.7
C12—O3—C16117.55 (9)C7—C8—H8A118.7
C2—N1—C3116.70 (10)C8—C9—C10126.10 (10)
C6—N2—N3119.56 (9)C8—C9—H9A117.0
C6—N2—H1N2121.8 (10)C10—C9—H9A117.0
N3—N2—H1N2118.3 (10)C15—C10—C11118.52 (10)
C7—N3—N2114.31 (9)C15—C10—C9120.18 (10)
C2—C1—C5118.81 (11)C11—C10—C9121.29 (10)
C2—C1—H1A120.6C12—C11—C10121.02 (10)
C5—C1—H1A120.6C12—C11—H11A119.5
N1—C2—C1123.79 (11)C10—C11—H11A119.5
N1—C2—H2A118.1O3—C12—C11125.39 (10)
C1—C2—H2A118.1O3—C12—C13114.57 (9)
N1—C3—C4123.91 (11)C11—C12—C13120.04 (10)
N1—C3—H3A118.0O2—C13—C14119.67 (10)
C4—C3—H3A118.0O2—C13—C12121.34 (10)
C3—C4—C5118.58 (11)C14—C13—C12118.99 (10)
C3—C4—H4A120.7C13—C14—C15120.91 (10)
C5—C4—H4A120.7C13—C14—H14A119.5
C1—C5—C4118.19 (11)C15—C14—H14A119.5
C1—C5—C6122.84 (10)C14—C15—C10120.51 (10)
C4—C5—C6118.76 (10)C14—C15—H15A119.7
O1—C6—N2124.21 (10)C10—C15—H15A119.7
O1—C6—C5120.96 (10)O3—C16—H16A109.5
N2—C6—C5114.79 (9)O3—C16—H16B109.5
N3—C7—C8119.57 (10)H16A—C16—H16B109.5
N3—C7—H7A120.2O3—C16—H16C109.5
C8—C7—H7A120.2H16A—C16—H16C109.5
C9—C8—C7122.51 (10)H16B—C16—H16C109.5
C6—N2—N3—C7170.58 (10)C8—C9—C10—C15165.29 (12)
C3—N1—C2—C11.0 (2)C8—C9—C10—C11−15.62 (18)
C5—C1—C2—N10.6 (2)C15—C10—C11—C12−1.36 (16)
C2—N1—C3—C4−1.61 (19)C9—C10—C11—C12179.53 (10)
N1—C3—C4—C50.7 (2)C16—O3—C12—C11−6.79 (15)
C2—C1—C5—C4−1.55 (18)C16—O3—C12—C13172.87 (9)
C2—C1—C5—C6173.17 (11)C10—C11—C12—O3−178.97 (10)
C3—C4—C5—C10.97 (18)C10—C11—C12—C131.38 (16)
C3—C4—C5—C6−173.96 (11)O3—C12—C13—O2−1.11 (15)
N3—N2—C6—O1−1.93 (17)C11—C12—C13—O2178.58 (10)
N3—N2—C6—C5−179.76 (9)O3—C12—C13—C14179.36 (10)
C1—C5—C6—O1−144.63 (12)C11—C12—C13—C14−0.95 (16)
C4—C5—C6—O130.05 (16)O2—C13—C14—C15−179.00 (10)
C1—C5—C6—N233.28 (15)C12—C13—C14—C150.54 (16)
C4—C5—C6—N2−152.04 (11)C13—C14—C15—C10−0.54 (17)
N2—N3—C7—C8176.04 (10)C11—C10—C15—C140.93 (16)
N3—C7—C8—C9176.67 (11)C9—C10—C15—C14−179.95 (10)
C7—C8—C9—C10174.30 (11)
Hydrogen-bond geometry (Å, °) top
Cg1 is the centroid of the C10–C15 benzene ring.
D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1i0.886 (15)1.999 (15)2.8622 (12)164.4 (14)
O2—H1O2···N1ii0.87 (2)1.96 (2)2.7750 (13)156.9 (19)
C2—H2A···O3iii0.932.553.1651 (14)124
C4—H4A···N3iv0.932.603.4747 (14)156
C7—H7A···O1i0.932.523.2405 (14)135
C16—H16B···Cg1v0.962.653.4556 (12)142
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+2; (v) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
Cg1 is the centroid of the C10–C15 benzene ring.
D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1i0.886 (15)1.999 (15)2.8622 (12)164.4 (14)
O2—H1O2···N1ii0.87 (2)1.96 (2)2.7750 (13)156.9 (19)
C2—H2A···O3iii0.932.553.1651 (14)124
C4—H4A···N3iv0.932.603.4747 (14)156
C7—H7A···O1i0.932.523.2405 (14)135
C16—H16B···Cg1v0.962.653.4556 (12)142
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+2; (v) x+1, y, z.
Acknowledgements top

This research was supported by Universiti Sains Malaysia (USM) under the University Research Grant (No. 1001/PFARMASI/815005). HKF and CKQ thank USM for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). HSNK and CKQ are grateful financial assistance through a USM fellowship.

references
References top

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