(3Z)-3-Hydrazinylideneindolin-2-one

Ara Jamal, R.; Ashiq, U.; Yousuf, S.

doi:10.1107/S1600536811035367

organic compounds

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Volume 67| Part 10| October 2011| Page o2576

https://doi.org/10.1107/S1600536811035367

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(3Z)-3-Hydrazinylideneindolin-2-one

Rifat Ara Jamal,^a ^* Uzma Ashiq ^a and Sammer Yousuf ^b

^aDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, and ^bH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: rifat_jamal@yahoo.com

(Received 27 August 2011; accepted 30 August 2011; online 14 September 2011)

The title molecule, C₈H₇N₃O, is almost planar, with a maximum deviation of 0.0232 (2) Å from the least-squares plane. The Z conformation of the C=N double bond is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, adjacent molecules are linked by intermolecular N—H⋯N and N—H⋯O hydrogen bonds, forming zigzag sheets parallel to the c axis; the sheets are further stabilized by π–π interactions [centroid–centroid distance = 3.7390 (10) Å].

Related literature

For the biological activity of related compounds, see: Sarangapani et al. (1994 ). For related structures, see: Ali et al. (2005a ,b ); Pelosi et al. (2005 ).

Experimental

Crystal data

C₈H₇N₃O
M_r = 161.17
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.7211 (5) Å
b = 11.4263 (13) Å
c = 13.3693 (15) Å
V = 721.20 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 K
0.50 × 0.10 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.950, T_max = 0.991
4234 measured reflections
811 independent reflections
776 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.079
S = 1.08
811 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯O1	0.88 (2)	2.09 (2)	2.784 (2)	135 (2)
N3—H1N3⋯N2ⁱ	0.91 (2)	2.20 (3)	3.098 (2)	169 (2)
N1—H1N1⋯O1ⁱⁱ	0.90 (2)	1.98 (2)	2.866 (2)	168 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811035367/ng5222sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035367/ng5222Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035367/ng5222Isup3.cml

checkCIF report

Comment top

Isatins are very important compounds due to their antifungal properties (Sarangapani & Reddy, 1994). In view of this biological significance, the crystal structure of the title compound has been determined (Fig. 1). The title compound I was found to be antifungal and phytotoxic (U. Ashiq & R.A. Jamal, unpublished results).

The title structure consists of a hydrazine group and indole ring linked by C=N bond exist in Z conformation. The molecule is essentially planar with a maximum deviation of 0.0232 (2) Å from the least-square plane. The Z conformation of the olefinic bond is get stablized by N3—H2N3···O1 intramolecular hydrogen bond (Fig. 1). The bond lengths and angles all are in normal range as in other structurally related compounds (Ali et al., 2005a,2005b; Pelosi et al., 2005)]. In the crystal structure, the molecules are linked by N3—H1N3···N2 and N1—H1N1···O1 intermolecular hydrogen bonds to form zig zag sheets running parallel to c axis. (symmetry codes as in Table 1, Fig. 2). The intermolecular interactions network is further strengthened by significant π–π interactions between pyrrole (Cg(1)= N1/C5–C8) and phenyl (Cg(2)= C1–C5/C8) rings; (Cg(1)to Cg(2) distance = 3.7390 (10) Å; -1+X,Y,Z).

Related literature top

For the biological activity of related compounds, see: Sarangapani et al. (1994). For related structures, see: Ali et al. (2005a,b); Pelosi et al. (2005).

Experimental top

To a solution of 2,3-Indolinedione (25 mmol, 3.67 g) in 30 ml of ethanol with few drops of glacial acetic acid, hydrazine hydrate (12.5 ml, 250 mmol), was added. The mixture was refluxed for 2 h and a solid was obtained upon removal of the solvent by rotary evaporation. Crystal of the title compound suitable for X-ray crystallographic study were grown from a solution of ethanol by slow evaporation at room temperature.

Structure description top

For the biological activity of related compounds, see: Sarangapani et al. (1994). For related structures, see: Ali et al. (2005a,b); Pelosi et al. (2005).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 50% probability level. The dashed lines indicates the intramolecular hydrogen bonds.
	Fig. 2. The crystal packing of the title compound I. Only hydrogen atoms involved in hydrogen bonding are shown.

(3Z)-3-Hydrazinylideneindolin-2-one top

Crystal data top

C₈H₇N₃O	D_x = 1.484 Mg m⁻³
M_r = 161.17	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 2104 reflections
a = 4.7211 (5) Å	θ = 3.1–27.5°
b = 11.4263 (13) Å	µ = 0.10 mm⁻¹
c = 13.3693 (15) Å	T = 273 K
V = 721.20 (14) Å³	Plate, colorles
Z = 4	0.50 × 0.10 × 0.09 mm
F(000) = 336

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	811 independent reflections
Radiation source: fine-focus sealed tube	776 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→5
T_min = 0.950, T_max = 0.991	k = −13→13
4234 measured reflections	l = −16→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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0512P)² + 0.0832P] where P = (F_o² + 2F_c²)/3
811 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₈H₇N₃O	V = 721.20 (14) Å³
M_r = 161.17	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.7211 (5) Å	µ = 0.10 mm⁻¹
b = 11.4263 (13) Å	T = 273 K
c = 13.3693 (15) Å	0.50 × 0.10 × 0.09 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	811 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	776 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.991	R_int = 0.021
4234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.12 e Å⁻³
811 reflections	Δρ_min = −0.16 e Å⁻³
121 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.1159 (3)	0.11147 (11)	0.46693 (10)	0.0443 (4)
N2	0.2067 (3)	−0.13322 (13)	0.54465 (10)	0.0345 (4)
N3	0.0172 (4)	−0.12868 (16)	0.47156 (13)	0.0429 (4)
C8	0.5392 (4)	−0.02667 (15)	0.65275 (13)	0.0331 (4)
C6	0.2809 (4)	0.08289 (15)	0.53444 (14)	0.0343 (4)
C7	0.3271 (4)	−0.03705 (14)	0.57432 (13)	0.0317 (4)
N1	0.4577 (4)	0.15444 (13)	0.58597 (13)	0.0405 (4)
C1	0.6635 (5)	−0.10479 (17)	0.71866 (14)	0.0408 (5)
H1A	0.6159	−0.1837	0.7167	0.049*
C4	0.8090 (5)	0.13277 (19)	0.72546 (15)	0.0460 (5)
H4A	0.8570	0.2117	0.7277	0.055*
C2	0.8591 (5)	−0.06419 (19)	0.78751 (15)	0.0469 (5)
H2B	0.9425	−0.1160	0.8323	0.056*
C5	0.6139 (4)	0.09186 (16)	0.65757 (14)	0.0357 (5)
C3	0.9315 (5)	0.0535 (2)	0.79003 (16)	0.0491 (6)
H3A	1.0651	0.0794	0.8361	0.059*
H2N3	−0.028 (5)	−0.060 (2)	0.4466 (16)	0.048 (6)*
H1N3	−0.064 (6)	−0.199 (2)	0.4587 (17)	0.066 (8)*
H1N1	0.481 (6)	0.231 (2)	0.5712 (16)	0.060 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0552 (9)	0.0305 (7)	0.0471 (7)	0.0065 (6)	−0.0067 (7)	0.0062 (6)
N2	0.0372 (8)	0.0285 (8)	0.0379 (8)	−0.0002 (7)	0.0034 (7)	0.0003 (6)
N3	0.0488 (10)	0.0313 (9)	0.0485 (9)	−0.0036 (8)	−0.0060 (9)	0.0006 (8)
C8	0.0338 (10)	0.0300 (9)	0.0356 (9)	0.0003 (9)	0.0061 (8)	0.0005 (7)
C6	0.0382 (10)	0.0273 (9)	0.0374 (9)	0.0020 (8)	0.0044 (9)	0.0014 (7)
C7	0.0342 (9)	0.0237 (8)	0.0371 (8)	0.0007 (8)	0.0047 (8)	0.0004 (7)
N1	0.0488 (10)	0.0234 (8)	0.0494 (9)	−0.0043 (7)	0.0025 (9)	0.0039 (7)
C1	0.0448 (11)	0.0346 (10)	0.0430 (10)	0.0047 (10)	0.0000 (10)	0.0022 (8)
C4	0.0437 (12)	0.0425 (11)	0.0517 (11)	−0.0096 (11)	0.0048 (10)	−0.0088 (9)
C2	0.0454 (12)	0.0545 (12)	0.0407 (10)	0.0126 (11)	−0.0036 (10)	−0.0016 (9)
C5	0.0365 (11)	0.0313 (9)	0.0393 (9)	−0.0031 (8)	0.0062 (8)	−0.0005 (7)
C3	0.0402 (12)	0.0627 (14)	0.0443 (10)	0.0001 (11)	−0.0030 (10)	−0.0113 (10)

Geometric parameters (Å, º) top

O1—C6	1.236 (2)	N1—C5	1.404 (3)
N2—C7	1.299 (2)	N1—H1N1	0.90 (2)
N2—N3	1.326 (2)	C1—C2	1.384 (3)
N3—H2N3	0.88 (2)	C1—H1A	0.9300
N3—H1N3	0.91 (3)	C4—C5	1.375 (3)
C8—C1	1.385 (3)	C4—C3	1.378 (3)
C8—C5	1.401 (3)	C4—H4A	0.9300
C8—C7	1.455 (3)	C2—C3	1.388 (3)
C6—N1	1.356 (3)	C2—H2B	0.9300
C6—C7	1.487 (2)	C3—H3A	0.9300

C7—N2—N3	119.15 (15)	C2—C1—C8	119.33 (19)
N2—N3—H2N3	118.5 (15)	C2—C1—H1A	120.3
N2—N3—H1N3	112.9 (15)	C8—C1—H1A	120.3
H2N3—N3—H1N3	128 (2)	C5—C4—C3	118.1 (2)
C1—C8—C5	119.17 (19)	C5—C4—H4A	120.9
C1—C8—C7	134.24 (18)	C3—C4—H4A	120.9
C5—C8—C7	106.57 (15)	C1—C2—C3	120.3 (2)
O1—C6—N1	126.82 (17)	C1—C2—H2B	119.8
O1—C6—C7	126.73 (17)	C3—C2—H2B	119.8
N1—C6—C7	106.45 (16)	C4—C5—C8	121.84 (18)
N2—C7—C8	126.17 (16)	C4—C5—N1	128.95 (18)
N2—C7—C6	127.29 (17)	C8—C5—N1	109.21 (17)
C8—C7—C6	106.52 (15)	C4—C3—C2	121.2 (2)
C6—N1—C5	111.25 (15)	C4—C3—H3A	119.4
C6—N1—H1N1	123.2 (16)	C2—C3—H3A	119.4
C5—N1—H1N1	125.3 (17)

N3—N2—C7—C8	−179.67 (18)	C7—C8—C1—C2	−178.4 (2)
N3—N2—C7—C6	−0.8 (3)	C8—C1—C2—C3	−0.4 (3)
C1—C8—C7—N2	−3.2 (4)	C3—C4—C5—C8	−0.2 (3)
C5—C8—C7—N2	178.52 (18)	C3—C4—C5—N1	178.8 (2)
C1—C8—C7—C6	177.8 (2)	C1—C8—C5—C4	0.6 (3)
C5—C8—C7—C6	−0.5 (2)	C7—C8—C5—C4	179.15 (17)
O1—C6—C7—N2	1.1 (3)	C1—C8—C5—N1	−178.57 (17)
N1—C6—C7—N2	−178.18 (18)	C7—C8—C5—N1	0.0 (2)
O1—C6—C7—C8	−179.83 (17)	C6—N1—C5—C4	−178.5 (2)
N1—C6—C7—C8	0.8 (2)	C6—N1—C5—C8	0.6 (2)
O1—C6—N1—C5	179.82 (17)	C5—C4—C3—C2	−0.5 (3)
C7—C6—N1—C5	−0.9 (2)	C1—C2—C3—C4	0.8 (3)
C5—C8—C1—C2	−0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···O1	0.88 (2)	2.09 (2)	2.784 (2)	135 (2)
N3—H1N3···N2ⁱ	0.91 (2)	2.20 (3)	3.098 (2)	169 (2)
N1—H1N1···O1ⁱⁱ	0.90 (2)	1.98 (2)	2.866 (2)	168 (3)

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

Experimental details

Crystal data
Chemical formula	C₈H₇N₃O
M_r	161.17
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	273
a, b, c (Å)	4.7211 (5), 11.4263 (13), 13.3693 (15)
V (Å³)	721.20 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.10 × 0.09

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.950, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	4234, 811, 776
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.08
No. of reflections	811
No. of parameters	121
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···O1	0.88 (2)	2.09 (2)	2.784 (2)	135 (2)
N3—H1N3···N2ⁱ	0.91 (2)	2.20 (3)	3.098 (2)	169 (2)
N1—H1N1···O1ⁱⁱ	0.90 (2)	1.98 (2)	2.866 (2)	168 (3)

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

Acknowledgements

The authors are thankful to the Higher Education Commission (HEC) of Pakistan for financial support under the National Research Grants Program for Universities (grant No. 1862/R&D/10).

References

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