3-[(E)-Benzyl­idene]indolin-2-one

Asiri, A.M.; Zayed, M.E.M.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812024762

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2020

https://doi.org/10.1107/S1600536812024762

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3-[(E)-Benzylidene]indolin-2-one

Abdullah M. Asiri,^a ‡ Mohie E. M. Zayed,^a Seik Weng Ng ^b and Edward R. T. Tiekink ^b ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 25 May 2012; accepted 30 May 2012; online 13 June 2012)

In the title indolin-2-one derivative, C₁₅H₁₁NO, the phenyl ring and the oxoindoline fused-ring system (r.m.s. deviation = 0.011 Å) are aligned at 48.52 (6)°. In the crystal, inversion-related molecules form an N—H⋯O hydrogen-bonded dimer via an eight-membered {⋯HNCO}₂ synthon. The dimeric aggregates are linked into a three-dimensional architecture via C—H⋯O and π–π interactions between the five- and six-membered rings of the fused ring system, with an inter-centroid distance of 3.4538 (8) Å.

Related literature

For the structure of the Z-isomer of the title compound, see: Milanesio et al. (2000 ). For background to related thiazoles, see: Badahdaha et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₁NO
M_r = 221.25
Monoclinic, P 2₁ /n
a = 3.9796 (3) Å
b = 22.2266 (19) Å
c = 12.2484 (10) Å
β = 95.027 (1)°
V = 1079.24 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
6831 measured reflections
2460 independent reflections
2153 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.107
S = 1.03
2460 reflections
158 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.87 (1)	1.98 (1)	2.846 (1)	172 (2)
C13—H13⋯O1ⁱⁱ	0.95	2.57	3.2535 (15)	129
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812024762/mw2072sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024762/mw2072Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812024762/mw2072Isup3.cml

checkCIF report

Comment top

The title compound (I) was isolated as a side-product in the attempted synthesis of thiazole derivatives (Badahdaha et al., 2009) of interest owing to putative biological activity. The indolin-2-onyl fused-ring in (I), Fig. 1, is planar with the r.m.s. deviation being 0.011 Å; the O1 and C9 atoms lie -0.016 (1) and 0.089 (1) Å out of the plane, respectively. The phenyl group is twisted out of this plane, forming a dihedral angle of 48.52 (6)°. The conformation about the C7═C9 bond [1.3439 (16) Å] is E; the structure of the Z-isomer is known (Milanesio et al., 2000).

In the crystal packing, inversion related molecules are connected into a dimer via N—H···O hydrogen bonds, Fig. 2 and Table 1. Molecules are linked into undulating layers in the bc plane via C—H···O interactions, Table 1, and are linked along the a axis via π–π interactions occurring between the five- and six-membered rings of the indolin-2-onyl fused ring system [ring centroid(N1,C1, C6–C7)···centroid(C1–C6)ⁱ = 3.4538 (8) Å, angle of inclination = 1.15 (6)° for i: -1 + x, y, z], Fig. 3.

Related literature top

For the structure of the Z-isomer of the title compound, see: Milanesio et al. (2000). For background to related thiazoles, see: Badahdaha et al. (2009).

Experimental top

The title compound, an unexpected product, was isolated as a side-product from a reaction between 2-(4-nitrobenzylidene)hydrazinecarbothioamide, triethylamine and N-phenyl-2-oxopropanehydrazonoyl chloride in ethanol solution; m.p. 512 K.

Structure description top

For the structure of the Z-isomer of the title compound, see: Milanesio et al. (2000). For background to related thiazoles, see: Badahdaha et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the centrosymmetric dimer in (I) mediated by N—H···O hydrogen bonds shown as blue dashed lines.
	Fig. 3. A view in projection down the a axis of the unit-cell contents of (I), the direction of the stacking of supramolecular layers. The N—H···O, C—H···O and π—π interactions are shown as blue, orange and purple dashed lines, respectively.

3-[(E)-Benzylidene]indolin-2-one top

Crystal data top

C₁₅H₁₁NO	F(000) = 464
M_r = 221.25	D_x = 1.362 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3166 reflections
a = 3.9796 (3) Å	θ = 2.5–28.3°
b = 22.2266 (19) Å	µ = 0.09 mm⁻¹
c = 12.2484 (10) Å	T = 100 K
β = 95.027 (1)°	Prism, orange
V = 1079.24 (15) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2153 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ω scans	h = −3→5
6831 measured reflections	k = −28→28
2460 independent reflections	l = −15→15

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0633P)² + 0.2809P] where P = (F_o² + 2F_c²)/3
2460 reflections	(Δ/σ)_max = 0.001
158 parameters	Δρ_max = 0.27 e Å⁻³
1 restraint	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₅H₁₁NO	V = 1079.24 (15) Å³
M_r = 221.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.9796 (3) Å	µ = 0.09 mm⁻¹
b = 22.2266 (19) Å	T = 100 K
c = 12.2484 (10) Å	0.30 × 0.20 × 0.10 mm
β = 95.027 (1)°

Data collection top

Bruker SMART APEX diffractometer	2153 reflections with I > 2σ(I)
6831 measured reflections	R_int = 0.023
2460 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.27 e Å⁻³
2460 reflections	Δρ_min = −0.26 e Å⁻³
158 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5372 (2)	0.58258 (4)	0.53379 (7)	0.0236 (2)
N1	0.7366 (3)	0.52725 (4)	0.39388 (8)	0.0183 (2)
H1N	0.668 (4)	0.4920 (5)	0.4133 (12)	0.032 (4)*
C1	0.8893 (3)	0.53924 (5)	0.29780 (9)	0.0167 (2)
C2	0.9905 (3)	0.49792 (5)	0.22291 (10)	0.0194 (3)
H2	0.9556	0.4560	0.2321	0.023*
C3	1.1456 (3)	0.52014 (6)	0.13341 (10)	0.0211 (3)
H3	1.2194	0.4929	0.0808	0.025*
C4	1.1938 (3)	0.58149 (6)	0.11990 (10)	0.0207 (3)
H4	1.2987	0.5956	0.0580	0.025*
C5	1.0897 (3)	0.62256 (5)	0.19619 (9)	0.0184 (2)
H5	1.1241	0.6645	0.1866	0.022*
C6	0.9350 (3)	0.60162 (5)	0.28646 (9)	0.0159 (2)
C7	0.8052 (3)	0.62991 (5)	0.38267 (9)	0.0167 (2)
C8	0.6761 (3)	0.57888 (5)	0.44818 (9)	0.0180 (3)
C9	0.7925 (3)	0.68631 (5)	0.42166 (9)	0.0176 (2)
H9	0.7175	0.6901	0.4929	0.021*
C10	0.8793 (3)	0.74284 (5)	0.36866 (9)	0.0167 (2)
C11	0.7759 (3)	0.75418 (5)	0.25856 (9)	0.0179 (2)
H11	0.6540	0.7243	0.2161	0.021*
C12	0.8496 (3)	0.80862 (5)	0.21070 (10)	0.0194 (3)
H12	0.7756	0.8160	0.1360	0.023*
C13	1.0311 (3)	0.85235 (5)	0.27155 (10)	0.0199 (3)
H13	1.0862	0.8892	0.2382	0.024*
C14	1.1317 (3)	0.84202 (5)	0.38124 (10)	0.0203 (3)
H14	1.2557	0.8719	0.4231	0.024*
C15	1.0516 (3)	0.78813 (5)	0.43000 (9)	0.0191 (3)
H15	1.1145	0.7819	0.5058	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0347 (5)	0.0183 (4)	0.0189 (4)	−0.0028 (4)	0.0088 (4)	0.0011 (3)
N1	0.0234 (5)	0.0130 (5)	0.0186 (5)	−0.0015 (4)	0.0024 (4)	0.0020 (4)
C1	0.0150 (5)	0.0178 (6)	0.0167 (5)	0.0001 (4)	−0.0015 (4)	0.0013 (4)
C2	0.0178 (5)	0.0177 (6)	0.0222 (6)	0.0018 (4)	−0.0010 (4)	−0.0010 (4)
C3	0.0191 (5)	0.0246 (6)	0.0193 (6)	0.0039 (5)	0.0001 (4)	−0.0044 (5)
C4	0.0179 (5)	0.0265 (6)	0.0179 (6)	0.0008 (5)	0.0019 (4)	0.0008 (5)
C5	0.0164 (5)	0.0190 (6)	0.0196 (6)	−0.0018 (4)	0.0008 (4)	0.0016 (4)
C6	0.0146 (5)	0.0163 (5)	0.0163 (5)	−0.0004 (4)	−0.0017 (4)	−0.0002 (4)
C7	0.0177 (5)	0.0170 (6)	0.0153 (5)	−0.0017 (4)	0.0004 (4)	0.0025 (4)
C8	0.0209 (6)	0.0157 (6)	0.0171 (5)	−0.0015 (4)	−0.0006 (4)	0.0016 (4)
C9	0.0200 (5)	0.0180 (6)	0.0148 (5)	−0.0005 (4)	0.0020 (4)	0.0006 (4)
C10	0.0172 (5)	0.0146 (5)	0.0188 (5)	0.0008 (4)	0.0046 (4)	−0.0005 (4)
C11	0.0183 (5)	0.0164 (5)	0.0189 (6)	−0.0009 (4)	0.0018 (4)	−0.0009 (4)
C12	0.0200 (6)	0.0202 (6)	0.0181 (5)	0.0015 (4)	0.0032 (4)	0.0022 (4)
C13	0.0196 (6)	0.0151 (5)	0.0255 (6)	−0.0002 (4)	0.0058 (4)	0.0028 (4)
C14	0.0214 (6)	0.0152 (5)	0.0244 (6)	−0.0020 (4)	0.0025 (4)	−0.0038 (4)
C15	0.0224 (6)	0.0182 (6)	0.0167 (5)	0.0015 (4)	0.0018 (4)	−0.0013 (4)

Geometric parameters (Å, º) top

O1—C8	1.2302 (14)	C7—C9	1.3439 (16)
N1—C8	1.3585 (15)	C7—C8	1.5054 (15)
N1—C1	1.3968 (14)	C9—C10	1.4693 (15)
N1—H1N	0.87 (1)	C9—H9	0.9500
C1—C2	1.3825 (16)	C10—C11	1.3978 (16)
C1—C6	1.4068 (16)	C10—C15	1.3993 (16)
C2—C3	1.3946 (17)	C11—C12	1.3871 (16)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.3890 (18)	C12—C13	1.3884 (17)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.3950 (16)	C13—C14	1.3871 (17)
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.3919 (15)	C14—C15	1.3881 (16)
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.4689 (15)	C15—H15	0.9500

C8—N1—C1	111.10 (9)	O1—C8—N1	125.86 (10)
C8—N1—H1N	123.7 (11)	O1—C8—C7	127.13 (10)
C1—N1—H1N	124.9 (11)	N1—C8—C7	106.99 (10)
C2—C1—N1	127.28 (11)	C7—C9—C10	128.54 (10)
C2—C1—C6	122.79 (11)	C7—C9—H9	115.7
N1—C1—C6	109.93 (10)	C10—C9—H9	115.7
C1—C2—C3	117.44 (11)	C11—C10—C15	118.50 (10)
C1—C2—H2	121.3	C11—C10—C9	121.32 (10)
C3—C2—H2	121.3	C15—C10—C9	120.08 (10)
C4—C3—C2	121.10 (11)	C12—C11—C10	120.65 (11)
C4—C3—H3	119.4	C12—C11—H11	119.7
C2—C3—H3	119.4	C10—C11—H11	119.7
C3—C4—C5	120.69 (11)	C13—C12—C11	120.20 (11)
C3—C4—H4	119.7	C13—C12—H12	119.9
C5—C4—H4	119.7	C11—C12—H12	119.9
C4—C5—C6	119.42 (11)	C14—C13—C12	119.78 (11)
C4—C5—H5	120.3	C14—C13—H13	120.1
C6—C5—H5	120.3	C12—C13—H13	120.1
C5—C6—C1	118.55 (10)	C13—C14—C15	120.12 (11)
C5—C6—C7	134.85 (11)	C13—C14—H14	119.9
C1—C6—C7	106.56 (10)	C15—C14—H14	119.9
C9—C7—C6	135.33 (11)	C14—C15—C10	120.67 (11)
C9—C7—C8	119.22 (10)	C14—C15—H15	119.7
C6—C7—C8	105.40 (9)	C10—C15—H15	119.7

C8—N1—C1—C2	179.20 (11)	C1—N1—C8—C7	−0.80 (13)
C8—N1—C1—C6	0.09 (13)	C9—C7—C8—O1	4.54 (18)
N1—C1—C2—C3	−178.59 (11)	C6—C7—C8—O1	−177.79 (11)
C6—C1—C2—C3	0.41 (16)	C9—C7—C8—N1	−176.49 (10)
C1—C2—C3—C4	−0.48 (17)	C6—C7—C8—N1	1.18 (12)
C2—C3—C4—C5	0.40 (17)	C6—C7—C9—C10	8.2 (2)
C3—C4—C5—C6	−0.23 (17)	C8—C7—C9—C10	−175.00 (11)
C4—C5—C6—C1	0.15 (16)	C7—C9—C10—C11	43.93 (18)
C4—C5—C6—C7	177.75 (11)	C7—C9—C10—C15	−139.89 (13)
C2—C1—C6—C5	−0.25 (16)	C15—C10—C11—C12	1.47 (17)
N1—C1—C6—C5	178.91 (10)	C9—C10—C11—C12	177.71 (10)
C2—C1—C6—C7	−178.47 (10)	C10—C11—C12—C13	0.77 (17)
N1—C1—C6—C7	0.68 (12)	C11—C12—C13—C14	−1.57 (17)
C5—C6—C7—C9	−1.8 (2)	C12—C13—C14—C15	0.09 (18)
C1—C6—C7—C9	175.99 (13)	C13—C14—C15—C10	2.20 (18)
C5—C6—C7—C8	−178.91 (12)	C11—C10—C15—C14	−2.95 (17)
C1—C6—C7—C8	−1.11 (11)	C9—C10—C15—C14	−179.24 (10)
C1—N1—C8—O1	178.19 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.87 (1)	1.98 (1)	2.846 (1)	172 (2)
C13—H13···O1ⁱⁱ	0.95	2.57	3.2535 (15)	129

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₁NO
M_r	221.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	3.9796 (3), 22.2266 (19), 12.2484 (10)
β (°)	95.027 (1)
V (Å³)	1079.24 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6831, 2460, 2153
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.107, 1.03
No. of reflections	2460
No. of parameters	158
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.26

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.87 (1)	1.983 (9)	2.846 (1)	172.3 (15)
C13—H13···O1ⁱⁱ	0.95	2.57	3.2535 (15)	129

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z−1/2.

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors are grateful to King Abdulaziz University for providing research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research Scheme (grant No. UM.C/HIR/MOHE/SC/12).

References

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