(Z)-3-Hydrazinyl­idene-1-phenyl­indolin-2-one

Abdel-Aziz, H.A.; Bari, A.; Aboul-Fadl, T.; Ng, S.W.

doi:10.1107/S1600536810043916

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3014

https://doi.org/10.1107/S1600536810043916

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(Z)-3-Hydrazinylidene-1-phenylindolin-2-one

Hatem A. Abdel-Aziz,^a Ahmed Bari,^a T. Aboul-Fadl ^a and Seik Weng Ng ^b ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 26 October 2010; accepted 27 October 2010; online 31 October 2010)

The indoline fused-ring system of the title Schiff base, C₁₄H₁₁N₃O, is planar (r.m.s. deviation = 0.005 Å); the phenyl substituent is aligned at 66.5 (1)° with respect to the ring system. The amino –NH₂ unit forms an intramolecular hydrogen bond with the carbonyl O atom. Molecules are connected by an intermolecular N—H⋯N hydrogen bond, generating a zigzag chain that runs along the short c axis of the unit cell.

Related literature

For the synthesis of the title compound, see: de Diesbach & Heppner (1949 ).

Experimental

Crystal data

C₁₄H₁₁N₃O
M_r = 237.26
Orthorhombic, F d d 2
a = 19.328 (3) Å
b = 41.612 (5) Å
c = 5.6288 (7) Å
V = 4527 (1) Å³
Z = 16
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.35 × 0.04 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
10569 measured reflections
1430 independent reflections
1188 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.092
S = 1.03
1430 reflections
171 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: 1138 Friedel pairs were merged

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯O1	0.88 (1)	2.06 (2)	2.772 (3)	137 (3)
N3—H2⋯N2ⁱ	0.89 (1)	2.22 (1)	3.102 (3)	177 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ .

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810043916/bt5393sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043916/bt5393Isup2.hkl

checkCIF report

Comment top

Isatin derivatives such as phenylisatin have been studied in the context of its biological properties. We have synthesized the condensation product of phenylisatin with hydrazine for evaluation as a chemotherapeutic agent. The title hydrazone (Scheme I) is only mentioned once in the chemical literature (de Diesbach & Heppner, 1949). The indolinyl fused-ring is twisted with respect to the phenyl substituent by 66.5 (1)° (Fig. 1). The amino –NH2 unit forms an intramolecular hydrogen bond with the carbonyl O atom; the unit uses its other H atom for intermolecular hydrogen bonding to the two-coordinate N atom (Fig. 2). The intramolecular N—H···N interaction generates a zigzag chain that runs along the short c axis of the unit cell.

Related literature top

For the synthesis of the title compound, see: de Diesbach & Heppner (1949).

Experimental top

1-Phenylindoline-2,3-dione (0.220 g, 1 mmol) and hydrazine hydrate (0.055 g, 1.1 mmol) were dissolved in methanol (25 ml) and the solution heated for 1 h. The solvent was evaporated and the product recrystallized from ethanol to give yellow prismatic crystals; yield 70%.

Structure description top

For the synthesis of the title compound, see: de Diesbach & Heppner (1949).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₄H₁₁N₃O at the 70% probability level; H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded chain structure.

(Z)-3-Hydrazinylidene-1-phenylindolin-2-one top

Crystal data top

C₁₄H₁₁N₃O	F(000) = 1984
M_r = 237.26	D_x = 1.392 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1516 reflections
a = 19.328 (3) Å	θ = 2.3–27.8°
b = 41.612 (5) Å	µ = 0.09 mm⁻¹
c = 5.6288 (7) Å	T = 100 K
V = 4527 (1) Å³	Prism, yellow
Z = 16	0.35 × 0.04 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	1188 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.079
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −24→24
10569 measured reflections	k = −54→54
1430 independent reflections	l = −7→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.054P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1430 reflections	Δρ_max = 0.27 e Å⁻³
171 parameters	Δρ_min = −0.22 e Å⁻³
3 restraints	Absolute structure: 1138 Friedel pairs were merged
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₄H₁₁N₃O	V = 4527 (1) Å³
M_r = 237.26	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 19.328 (3) Å	µ = 0.09 mm⁻¹
b = 41.612 (5) Å	T = 100 K
c = 5.6288 (7) Å	0.35 × 0.04 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	1188 reflections with I > 2σ(I)
10569 measured reflections	R_int = 0.079
1430 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	3 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.27 e Å⁻³
1430 reflections	Δρ_min = −0.22 e Å⁻³
171 parameters	Absolute structure: 1138 Friedel pairs were merged

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

	x	y	z	U_iso*/U_eq
O1	0.27334 (9)	0.09714 (4)	0.4984 (3)	0.0193 (4)
N1	0.34809 (10)	0.10293 (4)	0.1772 (4)	0.0161 (5)
N2	0.28770 (10)	0.02682 (5)	0.3752 (4)	0.0177 (5)
N3	0.24626 (11)	0.03226 (5)	0.5601 (4)	0.0201 (5)
C1	0.37995 (12)	0.08200 (6)	0.0120 (5)	0.0158 (6)
C2	0.42392 (12)	0.08987 (6)	−0.1705 (5)	0.0179 (6)
H2A	0.4368	0.1115	−0.2002	0.022*
C3	0.44890 (12)	0.06483 (6)	−0.3103 (5)	0.0206 (6)
H3	0.4788	0.0695	−0.4396	0.025*
C4	0.43087 (13)	0.03306 (6)	−0.2640 (5)	0.0213 (6)
H4	0.4485	0.0164	−0.3621	0.026*
C5	0.38720 (12)	0.02553 (6)	−0.0752 (5)	0.0192 (6)
H5	0.3753	0.0038	−0.0428	0.023*
C6	0.36135 (12)	0.05005 (6)	0.0645 (5)	0.0160 (5)
C7	0.31593 (12)	0.05137 (6)	0.2694 (4)	0.0158 (6)
C8	0.30841 (12)	0.08581 (6)	0.3372 (5)	0.0162 (5)
C9	0.35079 (12)	0.13736 (5)	0.1607 (5)	0.0158 (5)
C10	0.32204 (13)	0.15233 (6)	−0.0360 (5)	0.0181 (5)
H10	0.3004	0.1400	−0.1570	0.022*
C11	0.32528 (13)	0.18547 (6)	−0.0538 (5)	0.0207 (6)
H11	0.3055	0.1960	−0.1872	0.025*
C12	0.35737 (13)	0.20340 (6)	0.1227 (5)	0.0210 (6)
H12	0.3597	0.2261	0.1097	0.025*
C13	0.38601 (14)	0.18805 (6)	0.3177 (5)	0.0217 (6)
H13	0.4078	0.2004	0.4386	0.026*
C14	0.38314 (13)	0.15489 (6)	0.3378 (5)	0.0198 (6)
H14	0.4031	0.1444	0.4710	0.024*
H1	0.2435 (15)	0.0522 (4)	0.612 (6)	0.031 (8)*
H2	0.2355 (14)	0.0151 (5)	0.646 (5)	0.036 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0229 (9)	0.0166 (8)	0.0185 (11)	0.0001 (7)	0.0040 (9)	−0.0017 (8)
N1	0.0184 (10)	0.0129 (9)	0.0170 (12)	−0.0001 (8)	0.0014 (9)	−0.0021 (9)
N2	0.0164 (10)	0.0159 (10)	0.0207 (13)	−0.0012 (8)	−0.0024 (10)	−0.0009 (9)
N3	0.0242 (11)	0.0158 (11)	0.0203 (13)	−0.0006 (9)	0.0045 (11)	−0.0002 (10)
C1	0.0153 (11)	0.0148 (11)	0.0173 (15)	0.0024 (9)	−0.0039 (11)	−0.0006 (10)
C2	0.0176 (12)	0.0160 (11)	0.0202 (14)	0.0004 (9)	−0.0008 (12)	0.0017 (11)
C3	0.0150 (11)	0.0274 (13)	0.0194 (14)	0.0013 (10)	−0.0011 (12)	0.0005 (12)
C4	0.0183 (12)	0.0227 (12)	0.0229 (16)	0.0056 (10)	−0.0027 (12)	−0.0055 (11)
C5	0.0206 (12)	0.0138 (11)	0.0232 (15)	−0.0005 (9)	−0.0026 (13)	−0.0018 (11)
C6	0.0137 (11)	0.0163 (11)	0.0179 (14)	0.0000 (9)	−0.0036 (11)	0.0000 (11)
C7	0.0145 (12)	0.0154 (12)	0.0175 (15)	0.0002 (9)	−0.0020 (11)	−0.0014 (10)
C8	0.0147 (11)	0.0155 (11)	0.0183 (14)	−0.0006 (9)	−0.0028 (11)	0.0025 (11)
C9	0.0157 (12)	0.0125 (11)	0.0192 (14)	0.0003 (9)	0.0033 (10)	0.0003 (11)
C10	0.0211 (12)	0.0175 (12)	0.0159 (14)	−0.0013 (10)	0.0003 (11)	−0.0013 (11)
C11	0.0246 (13)	0.0204 (12)	0.0172 (14)	0.0034 (10)	0.0039 (12)	0.0011 (11)
C12	0.0246 (13)	0.0115 (10)	0.0268 (16)	−0.0012 (10)	0.0058 (13)	−0.0023 (11)
C13	0.0213 (13)	0.0216 (12)	0.0222 (15)	−0.0037 (10)	0.0025 (12)	−0.0066 (12)
C14	0.0202 (12)	0.0212 (12)	0.0181 (14)	0.0001 (10)	−0.0020 (12)	−0.0016 (11)

Geometric parameters (Å, º) top

O1—C8	1.227 (3)	C5—C6	1.381 (4)
N1—C8	1.381 (3)	C5—H5	0.9500
N1—C1	1.415 (3)	C6—C7	1.451 (3)
N1—C9	1.436 (3)	C7—C8	1.491 (3)
N2—C7	1.302 (3)	C9—C14	1.385 (4)
N2—N3	1.332 (3)	C9—C10	1.387 (4)
N3—H1	0.883 (10)	C10—C11	1.384 (3)
N3—H2	0.888 (10)	C10—H10	0.9500
C1—C2	1.373 (4)	C11—C12	1.388 (4)
C1—C6	1.408 (3)	C11—H11	0.9500
C2—C3	1.392 (4)	C12—C13	1.386 (4)
C2—H2A	0.9500	C12—H12	0.9500
C3—C4	1.392 (4)	C13—C14	1.385 (3)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.393 (4)	C14—H14	0.9500
C4—H4	0.9500

C8—N1—C1	110.66 (19)	N2—C7—C6	126.0 (2)
C8—N1—C9	125.2 (2)	N2—C7—C8	126.6 (2)
C1—N1—C9	123.8 (2)	C6—C7—C8	107.4 (2)
C7—N2—N3	118.4 (2)	O1—C8—N1	126.3 (2)
N2—N3—H1	117 (2)	O1—C8—C7	127.8 (2)
N2—N3—H2	115 (2)	N1—C8—C7	105.9 (2)
H1—N3—H2	124 (3)	C14—C9—C10	121.3 (2)
C2—C1—C6	122.7 (2)	C14—C9—N1	119.7 (2)
C2—C1—N1	127.9 (2)	C10—C9—N1	119.0 (2)
C6—C1—N1	109.4 (2)	C11—C10—C9	119.2 (2)
C1—C2—C3	117.3 (2)	C11—C10—H10	120.4
C1—C2—H2A	121.3	C9—C10—H10	120.4
C3—C2—H2A	121.3	C10—C11—C12	120.3 (3)
C4—C3—C2	121.2 (3)	C10—C11—H11	119.9
C4—C3—H3	119.4	C12—C11—H11	119.9
C2—C3—H3	119.4	C11—C12—C13	119.8 (2)
C5—C4—C3	120.5 (2)	C11—C12—H12	120.1
C5—C4—H4	119.7	C13—C12—H12	120.1
C3—C4—H4	119.7	C14—C13—C12	120.5 (3)
C6—C5—C4	119.2 (2)	C14—C13—H13	119.7
C6—C5—H5	120.4	C12—C13—H13	119.7
C4—C5—H5	120.4	C9—C14—C13	119.0 (3)
C5—C6—C1	119.0 (2)	C9—C14—H14	120.5
C5—C6—C7	134.4 (2)	C13—C14—H14	120.5
C1—C6—C7	106.6 (2)

C8—N1—C1—C2	−178.8 (2)	C1—N1—C8—O1	−178.4 (2)
C9—N1—C1—C2	7.9 (4)	C9—N1—C8—O1	−5.2 (4)
C8—N1—C1—C6	−0.4 (3)	C1—N1—C8—C7	0.3 (3)
C9—N1—C1—C6	−173.7 (2)	C9—N1—C8—C7	173.5 (2)
C6—C1—C2—C3	1.7 (4)	N2—C7—C8—O1	−2.1 (4)
N1—C1—C2—C3	179.9 (2)	C6—C7—C8—O1	178.5 (2)
C1—C2—C3—C4	−1.1 (4)	N2—C7—C8—N1	179.2 (2)
C2—C3—C4—C5	−0.1 (4)	C6—C7—C8—N1	−0.1 (2)
C3—C4—C5—C6	0.7 (4)	C8—N1—C9—C14	70.8 (3)
C4—C5—C6—C1	0.0 (4)	C1—N1—C9—C14	−116.8 (3)
C4—C5—C6—C7	179.9 (2)	C8—N1—C9—C10	−110.5 (3)
C2—C1—C6—C5	−1.2 (4)	C1—N1—C9—C10	61.8 (3)
N1—C1—C6—C5	−179.7 (2)	C14—C9—C10—C11	−0.6 (4)
C2—C1—C6—C7	178.8 (2)	N1—C9—C10—C11	−179.2 (2)
N1—C1—C6—C7	0.3 (3)	C9—C10—C11—C12	0.4 (4)
N3—N2—C7—C6	−179.1 (2)	C10—C11—C12—C13	−0.3 (4)
N3—N2—C7—C8	1.8 (4)	C11—C12—C13—C14	0.3 (4)
C5—C6—C7—N2	0.6 (4)	C10—C9—C14—C13	0.6 (4)
C1—C6—C7—N2	−179.4 (2)	N1—C9—C14—C13	179.2 (2)
C5—C6—C7—C8	179.9 (3)	C12—C13—C14—C9	−0.4 (4)
C1—C6—C7—C8	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1	0.88 (1)	2.06 (2)	2.772 (3)	137 (3)
N3—H2···N2ⁱ	0.89 (1)	2.22 (1)	3.102 (3)	177 (3)

Symmetry code: (i) −x+1/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃O
M_r	237.26
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	100
a, b, c (Å)	19.328 (3), 41.612 (5), 5.6288 (7)
V (Å³)	4527 (1)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.04 × 0.02

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10569, 1430, 1188
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.092, 1.03
No. of reflections	1430
No. of parameters	171
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)	0.27, −0.22
Absolute structure	1138 Friedel pairs were merged

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1	0.88 (1)	2.06 (2)	2.772 (3)	137 (3)
N3—H2···N2ⁱ	0.89 (1)	2.22 (1)	3.102 (3)	177 (3)

Symmetry code: (i) −x+1/2, −y, z+1/2.

Acknowledgements

The authors thank King Saud University and the University of Malaya for supporting this study.

References

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