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

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

doi:10.1107/S1600536808011124

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o912

doi:10.1107/S1600536808011124

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

Hapipah M. Ali,^a Kadir Zuraini,^a Basirun Wan Jeffrey,^a Mohd. Razali Rizal ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 March 2008; accepted 20 April 2008; online 26 April 2008)

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

C₁₉H₁₉N₃O₂
M_r = 321.37
Triclinic, $[P \overline 1]$
a = 4.6812 (9) Å
b = 12.419 (3) Å
c = 14.202 (3) Å
α = 109.919 (3)°
β = 91.710 (3)°
γ = 90.751 (3)°
V = 775.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 (2) K
0.40 × 0.13 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
4854 measured reflections
3490 independent reflections
1905 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.196
S = 1.01
3490 reflections
231 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011124/bt2687sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011124/bt2687Isup2.hkl

checkCIF report

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.

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

	Fig. 1. Thermal ellipsoid plot of C₁₉H₁₉N₃O₂; ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radii.
	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

C₁₉H₁₉N₃O₂	Z = 2
M_r = 321.37	F(000) = 340
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART APEXII diffractometer	1905 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 27.5°, θ_min = 1.5°
ω scans	h = −6→3
4854 measured reflections	k = −15→16
3490 independent reflections	l = −17→18

Refinement top

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(F_o²) + (0.0894P)²] where P = (F_o² + 2F_c²)/3
3490 reflections	(Δ/σ)_max = 0.001
231 parameters	Δρ_max = 0.43 e Å⁻³
3 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₉H₁₉N₃O₂	γ = 90.751 (3)°
M_r = 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)°

Data collection top

Bruker SMART APEXII diffractometer	1905 reflections with I > 2σ(I)
4854 measured reflections	R_int = 0.052
3490 independent reflections

Refinement top

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	Δρ_max = 0.43 e Å⁻³
3490 reflections	Δρ_min = −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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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
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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