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Acta Cryst. (2008). E64, o912    [ doi:10.1107/S1600536808011124 ]

1-(2-Hydroxy-5-methylphenyl)ethanone [(1H-indol-3-yl)acetyl]hydrazone

H. M. Ali, K. Zuraini, B. Wan Jeffrey, M. R. Rizal and S. W. Ng

Abstract top

The indolyl -NH group of the title Schiff base, C19H19N3O2, forms a hydrogen bond to the -OH group of an inversion-related molecule, resulting in a hydrogen-bonded dimer; adjacent dimers are further linked through an interdimer N-H...O hydrogen bond involving the -C(=O)-NH-N=fragment to form a linear ribbon that runs along the a axis.

Comment top

The Schiff base that is derived by condensing 2,4-dihydroxyacetophenone with indole-3-acetylhydrazine crystallizes as a co-crystal with unchanged indole-3-acetylhydrazine (Ali et al., 2007). The reason for the formation of the co-crystal appears to be related to the ease of hydrogen bond formation as the parent ketone itself has two possible donor sites.

In the similar synthesis but with 2-hydroxy-5-methylacetophenone, only the pure Schiff base is obtained (Scheme I, Fig. 1). The indolyl –NH unit forms a hydrogen bond to the –OH unit of an inversion-related molecule to furnish a hydrogen-bonded dimer; adjacent dimers are further linked through an inter-dimer N–H···O hydrogen involving the –C(=O)–NH–N= fragment to form a linear ribbon chain that runs along the shortest axis of the triclinic unit cell (Fig. 2). The hydroxy group itself engages in intramolecular hydrogen bonding.

Related literature top

For a related compound that co-crystallizes with 3-indolylacetylhydrazine, see: Ali et al. (2007).

Experimental top

Indole-3-acetylhydrazine (0.55 g, 4 mmol) and 2-hydroxy-5-methylacetophenone (0.52 g, 4 mmol) were dissolved in ethanol (100 ml). The reactants were heated under reflux for 1 h. The solvent was removed to give the tSchiff base, which was purified by recrystallization from ethanol.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.99 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The amino and hydroxy H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H/O–H 0.85±0.01 Å; their displacement parameters were freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of C19H19N3O2; ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radii.
[Figure 2] Fig. 2. Hydrogen-bonded chain structure. Dashed lines denote H atoms.
1-(2-Hydroxy-5-methylphenyl)ethanone [(1H-indol-3-yl)acetyl]hydrazone top
Crystal data top
C19H19N3O2Z = 2
Mr = 321.37F000 = 340
Triclinic, P1Dx = 1.376 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 4.6812 (9) ÅCell parameters from 985 reflections
b = 12.419 (3) Åθ = 3.0–28.3º
c = 14.202 (3) ŵ = 0.09 mm−1
α = 109.919 (3)ºT = 100 (2) K
β = 91.710 (3)ºPlate, pale yellow
γ = 90.751 (3)º0.40 × 0.13 × 0.05 mm
V = 775.7 (3) Å3
Data collection top
Bruker SMART APEXII
diffractometer		1905 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.052
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 1.5º
ω scansh = −6→3
Absorption correction: nonek = −15→16
4854 measured reflectionsl = −17→18
3490 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.196  w = 1/[σ2(Fo2) + (0.0894P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
3490 reflectionsΔρmax = 0.43 e Å−3
231 parametersΔρmin = −0.46 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C19H19N3O2γ = 90.751 (3)º
Mr = 321.37V = 775.7 (3) Å3
Triclinic, P1Z = 2
a = 4.6812 (9) ÅMo Kα
b = 12.419 (3) ŵ = 0.09 mm−1
c = 14.202 (3) ÅT = 100 (2) K
α = 109.919 (3)º0.40 × 0.13 × 0.05 mm
β = 91.710 (3)º
Data collection top
Bruker SMART APEXII
diffractometer		3490 independent reflections
Absorption correction: none1905 reflections with I > 2σ(I)
4854 measured reflectionsRint = 0.052
Refinement top
R[F2 > 2σ(F2)] = 0.0603 restraints
wR(F2) = 0.196H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.43 e Å−3
3490 reflectionsΔρmin = −0.46 e Å−3
231 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1−0.1765 (5)0.39859 (17)0.64793 (15)0.0232 (5)
H1O−0.097 (9)0.335 (2)0.617 (3)0.072 (15)*
O20.5909 (4)0.08863 (17)0.43759 (15)0.0259 (5)
N10.0800 (5)0.21073 (19)0.61339 (17)0.0198 (5)
N20.2703 (5)0.1345 (2)0.55630 (18)0.0205 (6)
H2N0.287 (9)0.0706 (17)0.565 (3)0.055 (12)*
N30.8788 (6)0.3894 (2)0.33999 (18)0.0224 (6)
H3N0.989 (6)0.4440 (19)0.339 (2)0.021 (8)*
C1−0.2982 (6)0.3739 (2)0.7244 (2)0.0201 (6)
C2−0.4852 (6)0.4525 (3)0.7818 (2)0.0241 (7)
H2−0.52150.52060.76760.029*
C3−0.6195 (6)0.4327 (3)0.8597 (2)0.0251 (7)
H3−0.74800.48740.89850.030*
C4−0.5699 (6)0.3340 (3)0.8822 (2)0.0243 (7)
C5−0.3819 (6)0.2562 (3)0.8235 (2)0.0226 (7)
H5−0.34870.18790.83770.027*
C6−0.2391 (6)0.2731 (2)0.7447 (2)0.0184 (6)
C7−0.7165 (7)0.3105 (3)0.9666 (2)0.0302 (8)
H7A−0.57270.29561.01190.045*
H7B−0.84520.24340.93900.045*
H7C−0.82690.37721.00370.045*
C8−0.0378 (6)0.1881 (2)0.6856 (2)0.0196 (6)
C90.0212 (7)0.0829 (2)0.7102 (2)0.0282 (7)
H9A0.22480.06590.70270.042*
H9B−0.09260.01830.66460.042*
H9C−0.02990.09520.77940.042*
C100.4156 (6)0.1572 (2)0.4841 (2)0.0199 (6)
C110.3479 (6)0.2641 (2)0.4612 (2)0.0216 (6)
H11A0.15360.25490.42960.026*
H11B0.34540.32940.52510.026*
C120.5528 (6)0.2925 (2)0.3940 (2)0.0201 (6)
C130.7169 (6)0.3905 (2)0.4185 (2)0.0216 (6)
H130.71810.45080.48130.026*
C140.6163 (6)0.2267 (2)0.2925 (2)0.0207 (6)
C150.5219 (7)0.1205 (3)0.2253 (2)0.0255 (7)
H150.38380.07590.24440.031*
C160.6313 (7)0.0813 (3)0.1311 (2)0.0306 (8)
H160.56770.00900.08510.037*
C170.8355 (7)0.1464 (3)0.1020 (2)0.0302 (8)
H170.90790.11740.03650.036*
C180.9324 (7)0.2513 (3)0.1664 (2)0.0274 (7)
H181.06980.29560.14670.033*
C190.8215 (6)0.2900 (3)0.2617 (2)0.0231 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0203 (11)0.0229 (11)0.0256 (11)0.0048 (9)0.0064 (9)0.0065 (9)
O20.0220 (12)0.0258 (11)0.0294 (11)0.0088 (9)0.0113 (9)0.0077 (9)
N10.0119 (12)0.0211 (12)0.0228 (12)0.0040 (10)0.0046 (10)0.0024 (10)
N20.0178 (13)0.0187 (12)0.0235 (12)0.0040 (11)0.0058 (10)0.0048 (11)
N30.0184 (14)0.0229 (13)0.0264 (13)0.0008 (11)0.0045 (11)0.0087 (11)
C10.0122 (14)0.0250 (15)0.0211 (14)0.0001 (12)−0.0006 (12)0.0056 (12)
C20.0172 (16)0.0236 (15)0.0281 (16)0.0032 (13)−0.0008 (13)0.0043 (13)
C30.0157 (15)0.0297 (16)0.0248 (16)0.0078 (13)0.0046 (13)0.0022 (13)
C40.0135 (15)0.0329 (17)0.0237 (15)0.0019 (13)0.0026 (12)0.0060 (13)
C50.0149 (15)0.0263 (15)0.0250 (15)0.0020 (12)0.0009 (12)0.0064 (13)
C60.0118 (14)0.0206 (14)0.0202 (14)0.0012 (12)−0.0005 (11)0.0036 (12)
C70.0214 (17)0.0393 (19)0.0274 (16)0.0050 (15)0.0085 (14)0.0076 (14)
C80.0136 (15)0.0210 (14)0.0213 (14)0.0005 (12)0.0014 (12)0.0032 (12)
C90.0292 (18)0.0226 (15)0.0329 (17)0.0065 (14)0.0135 (14)0.0085 (14)
C100.0151 (14)0.0196 (14)0.0215 (14)0.0026 (12)0.0002 (12)0.0023 (12)
C110.0171 (15)0.0228 (14)0.0244 (15)0.0069 (12)0.0046 (12)0.0068 (12)
C120.0127 (14)0.0238 (15)0.0248 (15)0.0078 (12)0.0039 (12)0.0091 (12)
C130.0173 (15)0.0225 (15)0.0252 (15)0.0074 (12)0.0045 (12)0.0079 (12)
C140.0122 (14)0.0263 (15)0.0247 (15)0.0061 (12)0.0023 (12)0.0098 (12)
C150.0224 (16)0.0256 (15)0.0267 (16)0.0013 (13)0.0012 (13)0.0065 (13)
C160.0322 (19)0.0290 (17)0.0283 (17)0.0021 (15)−0.0023 (15)0.0069 (14)
C170.0321 (19)0.0381 (18)0.0192 (15)0.0105 (15)0.0048 (14)0.0074 (14)
C180.0219 (17)0.0321 (17)0.0300 (16)0.0034 (14)0.0078 (14)0.0123 (14)
C190.0159 (15)0.0263 (15)0.0275 (16)0.0064 (12)0.0021 (13)0.0096 (13)
Geometric parameters (Å, °) top
O1—C11.364 (3)C7—H7C0.9800
O1—H1O0.85 (3)C8—C91.491 (4)
O2—C101.226 (3)C9—H9A0.9800
N1—C81.288 (3)C9—H9B0.9800
N1—N21.375 (3)C9—H9C0.9800
N2—C101.352 (4)C10—C111.505 (4)
N2—H2N0.85 (3)C11—C121.494 (4)
N3—C131.363 (4)C11—H11A0.9900
N3—C191.367 (4)C11—H11B0.9900
N3—H3N0.85 (3)C12—C131.365 (4)
C1—C21.381 (4)C12—C141.436 (4)
C1—C61.406 (4)C13—H130.9500
C2—C31.379 (4)C14—C151.396 (4)
C2—H20.9500C14—C191.404 (4)
C3—C41.389 (4)C15—C161.376 (4)
C3—H30.9500C15—H150.9500
C4—C51.386 (4)C16—C171.404 (5)
C4—C71.508 (4)C16—H160.9500
C5—C61.394 (4)C17—C181.374 (4)
C5—H50.9500C17—H170.9500
C6—C81.475 (4)C18—C191.392 (4)
C7—H7A0.9800C18—H180.9500
C7—H7B0.9800
C1—O1—H1O101 (3)H9A—C9—H9B109.5
C8—N1—N2118.6 (2)C8—C9—H9C109.5
C10—N2—N1121.3 (2)H9A—C9—H9C109.5
C10—N2—H2N121 (3)H9B—C9—H9C109.5
N1—N2—H2N118 (3)O2—C10—N2119.0 (3)
C13—N3—C19109.0 (2)O2—C10—C11122.4 (3)
C13—N3—H3N125 (2)N2—C10—C11118.6 (2)
C19—N3—H3N126 (2)C12—C11—C10114.4 (2)
O1—C1—C2117.0 (3)C12—C11—H11A108.7
O1—C1—C6122.2 (2)C10—C11—H11A108.7
C2—C1—C6120.8 (3)C12—C11—H11B108.7
C3—C2—C1120.4 (3)C10—C11—H11B108.7
C3—C2—H2119.8H11A—C11—H11B107.6
C1—C2—H2119.8C13—C12—C14106.0 (3)
C2—C3—C4121.0 (3)C13—C12—C11125.4 (3)
C2—C3—H3119.5C14—C12—C11128.6 (3)
C4—C3—H3119.5N3—C13—C12110.4 (3)
C5—C4—C3117.7 (3)N3—C13—H13124.8
C5—C4—C7120.6 (3)C12—C13—H13124.8
C3—C4—C7121.8 (3)C15—C14—C19118.7 (3)
C4—C5—C6123.4 (3)C15—C14—C12134.3 (3)
C4—C5—H5118.3C19—C14—C12107.0 (3)
C6—C5—H5118.3C16—C15—C14119.2 (3)
C5—C6—C1116.8 (3)C16—C15—H15120.4
C5—C6—C8121.1 (3)C14—C15—H15120.4
C1—C6—C8122.1 (3)C15—C16—C17121.0 (3)
C4—C7—H7A109.5C15—C16—H16119.5
C4—C7—H7B109.5C17—C16—H16119.5
H7A—C7—H7B109.5C18—C17—C16121.2 (3)
C4—C7—H7C109.5C18—C17—H17119.4
H7A—C7—H7C109.5C16—C17—H17119.4
H7B—C7—H7C109.5C17—C18—C19117.5 (3)
N1—C8—C6116.3 (3)C17—C18—H18121.3
N1—C8—C9123.2 (3)C19—C18—H18121.3
C6—C8—C9120.5 (2)N3—C19—C18129.9 (3)
C8—C9—H9A109.5N3—C19—C14107.6 (2)
C8—C9—H9B109.5C18—C19—C14122.4 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N10.85 (3)1.75 (2)2.540 (3)153 (4)
N2—H2n···O2i0.85 (3)2.05 (3)2.884 (3)166 (4)
N3—H3n···O1ii0.85 (3)2.08 (3)2.913 (3)166 (3)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N10.85 (3)1.75 (2)2.540 (3)153 (4)
N2—H2n···O2i0.85 (3)2.05 (3)2.884 (3)166 (4)
N3—H3n···O1ii0.85 (3)2.08 (3)2.913 (3)166 (3)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.
Acknowledgements top

We thank the ScienceFund (12–02-03–2031) for supporting this study, and the for University of Malaya for the purchase of the diffractometer.

references
References top

Ali, H. M., Zuraini, K., Wan Jefrey, B. & Ng, S. W. (2007). Acta Cryst. E63, o1729–o1730.

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2008). publCIF. In preparation.