organic compounds
1-(2-Hydroxy-5-methylphenyl)ethanone [(1H-indol-3-yl)acetyl]hydrazone
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
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.
Related literature
For a related compound that co-crystallizes with 3-indolylacetylhydrazine, see: Ali et al. (2007).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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).
Supporting information
10.1107/S1600536808011124/bt2687sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011124/bt2687Isup2.hkl
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.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.99 to 0.99 Å) and were included in the
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.
Data collection: APEX2 (Bruker, 2007); cell
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).C19H19N3O2 | Z = 2 |
Mr = 321.37 | F(000) = 340 |
Triclinic, P1 | Dx = 1.376 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.6812 (9) Å | Cell parameters from 985 reflections |
b = 12.419 (3) Å | θ = 3.0–28.3° |
c = 14.202 (3) Å | µ = 0.09 mm−1 |
α = 109.919 (3)° | T = 100 K |
β = 91.710 (3)° | Plate, pale yellow |
γ = 90.751 (3)° | 0.40 × 0.13 × 0.05 mm |
V = 775.7 (3) Å3 |
Bruker SMART APEXII diffractometer | 1905 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 27.5°, θmin = 1.5° |
ω scans | h = −6→3 |
4854 measured reflections | k = −15→16 |
3490 independent reflections | l = −17→18 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.196 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0894P)2] where P = (Fo2 + 2Fc2)/3 |
3490 reflections | (Δ/σ)max = 0.001 |
231 parameters | Δρmax = 0.43 e Å−3 |
3 restraints | Δρmin = −0.46 e Å−3 |
C19H19N3O2 | γ = 90.751 (3)° |
Mr = 321.37 | V = 775.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.6812 (9) Å | Mo Kα radiation |
b = 12.419 (3) Å | µ = 0.09 mm−1 |
c = 14.202 (3) Å | T = 100 K |
α = 109.919 (3)° | 0.40 × 0.13 × 0.05 mm |
β = 91.710 (3)° |
Bruker SMART APEXII diffractometer | 1905 reflections with I > 2σ(I) |
4854 measured reflections | Rint = 0.052 |
3490 independent reflections |
R[F2 > 2σ(F2)] = 0.060 | 3 restraints |
wR(F2) = 0.196 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.43 e Å−3 |
3490 reflections | Δρmin = −0.46 e Å−3 |
231 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. |
x | y | z | Uiso*/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)* | |
O2 | 0.5909 (4) | 0.08863 (17) | 0.43759 (15) | 0.0259 (5) | |
N1 | 0.0800 (5) | 0.21073 (19) | 0.61339 (17) | 0.0198 (5) | |
N2 | 0.2703 (5) | 0.1345 (2) | 0.55630 (18) | 0.0205 (6) | |
H2N | 0.287 (9) | 0.0706 (17) | 0.565 (3) | 0.055 (12)* | |
N3 | 0.8788 (6) | 0.3894 (2) | 0.33999 (18) | 0.0224 (6) | |
H3N | 0.989 (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 | −0.5215 | 0.5206 | 0.7676 | 0.029* | |
C3 | −0.6195 (6) | 0.4327 (3) | 0.8597 (2) | 0.0251 (7) | |
H3 | −0.7480 | 0.4874 | 0.8985 | 0.030* | |
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 | −0.3487 | 0.1879 | 0.8377 | 0.027* | |
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 | −0.5727 | 0.2956 | 1.0119 | 0.045* | |
H7B | −0.8452 | 0.2434 | 0.9390 | 0.045* | |
H7C | −0.8269 | 0.3772 | 1.0037 | 0.045* | |
C8 | −0.0378 (6) | 0.1881 (2) | 0.6856 (2) | 0.0196 (6) | |
C9 | 0.0212 (7) | 0.0829 (2) | 0.7102 (2) | 0.0282 (7) | |
H9A | 0.2248 | 0.0659 | 0.7027 | 0.042* | |
H9B | −0.0926 | 0.0183 | 0.6646 | 0.042* | |
H9C | −0.0299 | 0.0952 | 0.7794 | 0.042* | |
C10 | 0.4156 (6) | 0.1572 (2) | 0.4841 (2) | 0.0199 (6) | |
C11 | 0.3479 (6) | 0.2641 (2) | 0.4612 (2) | 0.0216 (6) | |
H11A | 0.1536 | 0.2549 | 0.4296 | 0.026* | |
H11B | 0.3454 | 0.3294 | 0.5251 | 0.026* | |
C12 | 0.5528 (6) | 0.2925 (2) | 0.3940 (2) | 0.0201 (6) | |
C13 | 0.7169 (6) | 0.3905 (2) | 0.4185 (2) | 0.0216 (6) | |
H13 | 0.7181 | 0.4508 | 0.4813 | 0.026* | |
C14 | 0.6163 (6) | 0.2267 (2) | 0.2925 (2) | 0.0207 (6) | |
C15 | 0.5219 (7) | 0.1205 (3) | 0.2253 (2) | 0.0255 (7) | |
H15 | 0.3838 | 0.0759 | 0.2444 | 0.031* | |
C16 | 0.6313 (7) | 0.0813 (3) | 0.1311 (2) | 0.0306 (8) | |
H16 | 0.5677 | 0.0090 | 0.0851 | 0.037* | |
C17 | 0.8355 (7) | 0.1464 (3) | 0.1020 (2) | 0.0302 (8) | |
H17 | 0.9079 | 0.1174 | 0.0365 | 0.036* | |
C18 | 0.9324 (7) | 0.2513 (3) | 0.1664 (2) | 0.0274 (7) | |
H18 | 1.0698 | 0.2956 | 0.1467 | 0.033* | |
C19 | 0.8215 (6) | 0.2900 (3) | 0.2617 (2) | 0.0231 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0203 (11) | 0.0229 (11) | 0.0256 (11) | 0.0048 (9) | 0.0064 (9) | 0.0065 (9) |
O2 | 0.0220 (12) | 0.0258 (11) | 0.0294 (11) | 0.0088 (9) | 0.0113 (9) | 0.0077 (9) |
N1 | 0.0119 (12) | 0.0211 (12) | 0.0228 (12) | 0.0040 (10) | 0.0046 (10) | 0.0024 (10) |
N2 | 0.0178 (13) | 0.0187 (12) | 0.0235 (12) | 0.0040 (11) | 0.0058 (10) | 0.0048 (11) |
N3 | 0.0184 (14) | 0.0229 (13) | 0.0264 (13) | 0.0008 (11) | 0.0045 (11) | 0.0087 (11) |
C1 | 0.0122 (14) | 0.0250 (15) | 0.0211 (14) | 0.0001 (12) | −0.0006 (12) | 0.0056 (12) |
C2 | 0.0172 (16) | 0.0236 (15) | 0.0281 (16) | 0.0032 (13) | −0.0008 (13) | 0.0043 (13) |
C3 | 0.0157 (15) | 0.0297 (16) | 0.0248 (16) | 0.0078 (13) | 0.0046 (13) | 0.0022 (13) |
C4 | 0.0135 (15) | 0.0329 (17) | 0.0237 (15) | 0.0019 (13) | 0.0026 (12) | 0.0060 (13) |
C5 | 0.0149 (15) | 0.0263 (15) | 0.0250 (15) | 0.0020 (12) | 0.0009 (12) | 0.0064 (13) |
C6 | 0.0118 (14) | 0.0206 (14) | 0.0202 (14) | 0.0012 (12) | −0.0005 (11) | 0.0036 (12) |
C7 | 0.0214 (17) | 0.0393 (19) | 0.0274 (16) | 0.0050 (15) | 0.0085 (14) | 0.0076 (14) |
C8 | 0.0136 (15) | 0.0210 (14) | 0.0213 (14) | 0.0005 (12) | 0.0014 (12) | 0.0032 (12) |
C9 | 0.0292 (18) | 0.0226 (15) | 0.0329 (17) | 0.0065 (14) | 0.0135 (14) | 0.0085 (14) |
C10 | 0.0151 (14) | 0.0196 (14) | 0.0215 (14) | 0.0026 (12) | 0.0002 (12) | 0.0023 (12) |
C11 | 0.0171 (15) | 0.0228 (14) | 0.0244 (15) | 0.0069 (12) | 0.0046 (12) | 0.0068 (12) |
C12 | 0.0127 (14) | 0.0238 (15) | 0.0248 (15) | 0.0078 (12) | 0.0039 (12) | 0.0091 (12) |
C13 | 0.0173 (15) | 0.0225 (15) | 0.0252 (15) | 0.0074 (12) | 0.0045 (12) | 0.0079 (12) |
C14 | 0.0122 (14) | 0.0263 (15) | 0.0247 (15) | 0.0061 (12) | 0.0023 (12) | 0.0098 (12) |
C15 | 0.0224 (16) | 0.0256 (15) | 0.0267 (16) | 0.0013 (13) | 0.0012 (13) | 0.0065 (13) |
C16 | 0.0322 (19) | 0.0290 (17) | 0.0283 (17) | 0.0021 (15) | −0.0023 (15) | 0.0069 (14) |
C17 | 0.0321 (19) | 0.0381 (18) | 0.0192 (15) | 0.0105 (15) | 0.0048 (14) | 0.0074 (14) |
C18 | 0.0219 (17) | 0.0321 (17) | 0.0300 (16) | 0.0034 (14) | 0.0078 (14) | 0.0123 (14) |
C19 | 0.0159 (15) | 0.0263 (15) | 0.0275 (16) | 0.0064 (12) | 0.0021 (13) | 0.0096 (13) |
O1—C1 | 1.364 (3) | C7—H7C | 0.9800 |
O1—H1O | 0.85 (3) | C8—C9 | 1.491 (4) |
O2—C10 | 1.226 (3) | C9—H9A | 0.9800 |
N1—C8 | 1.288 (3) | C9—H9B | 0.9800 |
N1—N2 | 1.375 (3) | C9—H9C | 0.9800 |
N2—C10 | 1.352 (4) | C10—C11 | 1.505 (4) |
N2—H2N | 0.85 (3) | C11—C12 | 1.494 (4) |
N3—C13 | 1.363 (4) | C11—H11A | 0.9900 |
N3—C19 | 1.367 (4) | C11—H11B | 0.9900 |
N3—H3N | 0.85 (3) | C12—C13 | 1.365 (4) |
C1—C2 | 1.381 (4) | C12—C14 | 1.436 (4) |
C1—C6 | 1.406 (4) | C13—H13 | 0.9500 |
C2—C3 | 1.379 (4) | C14—C15 | 1.396 (4) |
C2—H2 | 0.9500 | C14—C19 | 1.404 (4) |
C3—C4 | 1.389 (4) | C15—C16 | 1.376 (4) |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.386 (4) | C16—C17 | 1.404 (5) |
C4—C7 | 1.508 (4) | C16—H16 | 0.9500 |
C5—C6 | 1.394 (4) | C17—C18 | 1.374 (4) |
C5—H5 | 0.9500 | C17—H17 | 0.9500 |
C6—C8 | 1.475 (4) | C18—C19 | 1.392 (4) |
C7—H7A | 0.9800 | C18—H18 | 0.9500 |
C7—H7B | 0.9800 | ||
C1—O1—H1O | 101 (3) | H9A—C9—H9B | 109.5 |
C8—N1—N2 | 118.6 (2) | C8—C9—H9C | 109.5 |
C10—N2—N1 | 121.3 (2) | H9A—C9—H9C | 109.5 |
C10—N2—H2N | 121 (3) | H9B—C9—H9C | 109.5 |
N1—N2—H2N | 118 (3) | O2—C10—N2 | 119.0 (3) |
C13—N3—C19 | 109.0 (2) | O2—C10—C11 | 122.4 (3) |
C13—N3—H3N | 125 (2) | N2—C10—C11 | 118.6 (2) |
C19—N3—H3N | 126 (2) | C12—C11—C10 | 114.4 (2) |
O1—C1—C2 | 117.0 (3) | C12—C11—H11A | 108.7 |
O1—C1—C6 | 122.2 (2) | C10—C11—H11A | 108.7 |
C2—C1—C6 | 120.8 (3) | C12—C11—H11B | 108.7 |
C3—C2—C1 | 120.4 (3) | C10—C11—H11B | 108.7 |
C3—C2—H2 | 119.8 | H11A—C11—H11B | 107.6 |
C1—C2—H2 | 119.8 | C13—C12—C14 | 106.0 (3) |
C2—C3—C4 | 121.0 (3) | C13—C12—C11 | 125.4 (3) |
C2—C3—H3 | 119.5 | C14—C12—C11 | 128.6 (3) |
C4—C3—H3 | 119.5 | N3—C13—C12 | 110.4 (3) |
C5—C4—C3 | 117.7 (3) | N3—C13—H13 | 124.8 |
C5—C4—C7 | 120.6 (3) | C12—C13—H13 | 124.8 |
C3—C4—C7 | 121.8 (3) | C15—C14—C19 | 118.7 (3) |
C4—C5—C6 | 123.4 (3) | C15—C14—C12 | 134.3 (3) |
C4—C5—H5 | 118.3 | C19—C14—C12 | 107.0 (3) |
C6—C5—H5 | 118.3 | C16—C15—C14 | 119.2 (3) |
C5—C6—C1 | 116.8 (3) | C16—C15—H15 | 120.4 |
C5—C6—C8 | 121.1 (3) | C14—C15—H15 | 120.4 |
C1—C6—C8 | 122.1 (3) | C15—C16—C17 | 121.0 (3) |
C4—C7—H7A | 109.5 | C15—C16—H16 | 119.5 |
C4—C7—H7B | 109.5 | C17—C16—H16 | 119.5 |
H7A—C7—H7B | 109.5 | C18—C17—C16 | 121.2 (3) |
C4—C7—H7C | 109.5 | C18—C17—H17 | 119.4 |
H7A—C7—H7C | 109.5 | C16—C17—H17 | 119.4 |
H7B—C7—H7C | 109.5 | C17—C18—C19 | 117.5 (3) |
N1—C8—C6 | 116.3 (3) | C17—C18—H18 | 121.3 |
N1—C8—C9 | 123.2 (3) | C19—C18—H18 | 121.3 |
C6—C8—C9 | 120.5 (2) | N3—C19—C18 | 129.9 (3) |
C8—C9—H9A | 109.5 | N3—C19—C14 | 107.6 (2) |
C8—C9—H9B | 109.5 | C18—C19—C14 | 122.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1o···N1 | 0.85 (3) | 1.75 (2) | 2.540 (3) | 153 (4) |
N2—H2n···O2i | 0.85 (3) | 2.05 (3) | 2.884 (3) | 166 (4) |
N3—H3n···O1ii | 0.85 (3) | 2.08 (3) | 2.913 (3) | 166 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H19N3O2 |
Mr | 321.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 4.6812 (9), 12.419 (3), 14.202 (3) |
α, β, γ (°) | 109.919 (3), 91.710 (3), 90.751 (3) |
V (Å3) | 775.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.13 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEXII diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4854, 3490, 1905 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.196, 1.01 |
No. of reflections | 3490 |
No. of parameters | 231 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.46 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1o···N1 | 0.85 (3) | 1.75 (2) | 2.540 (3) | 153 (4) |
N2—H2n···O2i | 0.85 (3) | 2.05 (3) | 2.884 (3) | 166 (4) |
N3—H3n···O1ii | 0.85 (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
We thank the Science Fund (12–02-03–2031) for supporting this study, and the University of Malaya for the purchase of the diffractometer.
References
Ali, H. M., Zuraini, K., Wan Jefrey, B. & Ng, S. W. (2007). Acta Cryst. E63, o1729–o1730. Web of Science CSD CrossRef IUCr Journals Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
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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.