(3Z)-5-Chloro-3-(hy­droxy­imino)­indolin-2-one

Martins, B.B.; Gervini, V.C.; Pires, F.C.; Bortoluzzi, A.J.; Oliveira, A.B. de

doi:10.1107/S2414314616015066

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161506

https://doi.org/10.1107/S2414314616015066

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(3Z)-5-Chloro-3-(hydroxyimino)indolin-2-one

Bianca Barreto Martins,^a Vanessa Carratu Gervini,^a ^* Fabricio Carvalho Pires,^a Adailton João Bortoluzzi ^b and Adriano Bof de Oliveira ^c

^aEscola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900 Rio Grande-RS, Brazil, ^bDepartamento de Química, Universidade Federal de Santa Catarina, Campus Universitário Trindade, 88040-900 Florianópolis-SC, Brazil, and ^cDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão-SE, Brazil
^*Correspondence e-mail: vanessa.gervini@gmail.com

Edited by I. Brito, University of Antofagasta, Chile (Received 18 September 2016; accepted 22 September 2016; online 7 October 2016)

In the title compound, C₈H₅ClN₂O₂ (common name: 5-chloroisatin 3-oxime), the molecular structure deviates slightly from the ideal planarity, with a maximum deviation of 0.0478 (8) Å for the non-H atoms. In the crystal, molecules are linked by N—H⋯O interactions, building centrosymmetric dimers with graph-set motif R₂²(8). Additionally, the molecules are connected by pairs of O—H⋯O interactions into chains along [100] with a C(6) motif. The hydrogen-bonded dimers and chains build a two-dimensional network parallel to (100). The packing also features π–π stacking interactions between benzene rings [centroid–centroid distance = 3.748 (2) Å].

Keywords: crystal structure; chloroisatin derivative; two-dimensional hydrogen-bonded network; oxime derivative.

CCDC reference: 1505940

Structure description

As part of our study on the structural chemistry of isatin derivatives we report herein the crystal structure of 5-chloroisatin-3-oxime (for the asymmetric unit, see Fig. 1). The title compound is almost planar with an r.m.s. maximum deviation for the non-H atoms of 0.0478 (8) Å for O2. In the solid state, the molecules are connected into dimers via pairs of N1—H1⋯O1 interactions and a graph-set motif $[R_{2}^{2}]$ (8) is observed. In addition, the molecules are connected into chains with a C(6) graph-set motif by O2—H5⋯O1 hydrogen bonds (Fig. 2 and Table 1). The O—H⋯O interactions connect the centrosymmetric dimers building a two-dimensional network, a tape structure, parallel to (100). As the outstanding feature, the ketone oxygen atom, O1, accepts two hydrogen bonds. As the difference between the two H⋯O distances is less than 0.2 Å, the hydrogen bonds presumably have roughly equal strength and the arrangement may be described as symmetric. The packing also features π–π stacking interactions between benzene rings [centroid–centroid distance = 3.748 (2) A °].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	2.00	2.8476 (13)	162
O2—H5⋯O1ⁱⁱ	0.84	1.94	2.7235 (12)	155
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with labeling and displacement ellipsoids drawn at the 40% probability level.

Figure 2
Partial view of the crystal structure of the title compound. Hydrogen bonds are shown as dashed lines; see Table 2

for details.

Synthesis and crystallization

The glacial acetic acid catalyzed reaction of 5-chloroisatin (3 mmol) and hydroxylamine hydrochloride (3 mmol) in ethanol (50 ml) was stirred and refluxed for 6 h. After cooling and filtering, single crystals suitable for X-ray diffraction were obtained from the ethanolic solution by solvent evaporation. For an alternative synthesis of 5-chloroisatin-3-oxime, see: Kearney et al., 1992 .

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₅ClN₂O₂
M_r	196.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	7.4296 (3), 7.5187 (3), 14.3206 (7)
β (°)	94.184 (1)
V (Å³)	797.83 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.44
Crystal size (mm)	0.24 × 0.20 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.902, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	10472, 2451, 2182
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.095, 1.05
No. of reflections	2451
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.28
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), DIAMOND (Brandenburg, 2006 ), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Structural data

CCDC reference: 1505940

Crystal structure: contains datablock . DOI: https://doi.org/10.1107/S2414314616015066/bx4003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616015066/bx4003Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015066/bx4003Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

(3Z)-5-Chloro-3-(hydroxyimino)indolin-2-one top

Crystal data top

C₈H₅ClN₂O₂	F(000) = 400
M_r = 196.59	D_x = 1.637 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4296 (3) Å	Cell parameters from 5902 reflections
b = 7.5187 (3) Å	θ = 2.8–30.6°
c = 14.3206 (7) Å	µ = 0.44 mm⁻¹
β = 94.184 (1)°	T = 200 K
V = 797.83 (6) Å³	Prism, orange
Z = 4	0.24 × 0.20 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	2451 independent reflections
Radiation source: fine-focus sealed tube, Bruker APEX2	2182 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
φ and ω scans	θ_max = 30.6°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→10
T_min = 0.902, T_max = 0.933	k = −10→10
10472 measured reflections	l = −19→20

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0537P)² + 0.2884P] where P = (F_o² + 2F_c²)/3
2451 reflections	(Δ/σ)_max = 0.001
119 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.58311 (15)	0.21274 (15)	0.43029 (7)	0.0205 (2)
C2	0.64041 (15)	0.39353 (14)	0.39942 (7)	0.0192 (2)
C3	0.72801 (14)	0.48058 (14)	0.48207 (7)	0.0182 (2)
C4	0.80538 (14)	0.64698 (15)	0.49770 (7)	0.0202 (2)
H2	0.8097	0.7320	0.4488	0.024*
C5	0.87646 (15)	0.68356 (15)	0.58850 (7)	0.0215 (2)
C6	0.87171 (16)	0.56117 (17)	0.66104 (8)	0.0246 (2)
H3	0.9214	0.5918	0.7219	0.030*
C7	0.79446 (16)	0.39372 (16)	0.64513 (8)	0.0237 (2)
H4	0.7913	0.3086	0.6940	0.028*
C8	0.72266 (14)	0.35647 (14)	0.55542 (7)	0.0193 (2)
Cl1	0.97441 (4)	0.89044 (4)	0.61183 (2)	0.03057 (11)
N1	0.63574 (13)	0.20035 (13)	0.52268 (6)	0.02202 (19)
H1	0.6178	0.1066	0.5576	0.026*
N2	0.59837 (14)	0.43956 (13)	0.31406 (6)	0.0231 (2)
O1	0.50045 (13)	0.09832 (11)	0.38255 (6)	0.02689 (19)
O2	0.64795 (14)	0.61138 (12)	0.29692 (6)	0.0291 (2)
H5	0.6115	0.6396	0.2420	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0238 (5)	0.0208 (5)	0.0166 (4)	0.0020 (4)	−0.0008 (4)	0.0000 (4)
C2	0.0217 (5)	0.0208 (5)	0.0147 (4)	0.0018 (4)	−0.0004 (3)	−0.0002 (3)
C3	0.0192 (4)	0.0223 (5)	0.0130 (4)	0.0027 (4)	−0.0005 (3)	0.0006 (3)
C4	0.0217 (5)	0.0233 (5)	0.0153 (4)	0.0008 (4)	−0.0002 (4)	0.0012 (4)
C5	0.0220 (5)	0.0238 (5)	0.0183 (5)	−0.0009 (4)	−0.0021 (4)	−0.0014 (4)
C6	0.0273 (5)	0.0299 (6)	0.0157 (4)	−0.0004 (4)	−0.0049 (4)	0.0002 (4)
C7	0.0282 (5)	0.0269 (5)	0.0154 (5)	0.0000 (4)	−0.0033 (4)	0.0040 (4)
C8	0.0204 (4)	0.0212 (5)	0.0160 (4)	0.0017 (4)	−0.0010 (3)	0.0014 (4)
Cl1	0.03654 (18)	0.02817 (16)	0.02608 (16)	−0.00784 (11)	−0.00398 (12)	−0.00205 (10)
N1	0.0285 (5)	0.0207 (4)	0.0162 (4)	−0.0008 (3)	−0.0029 (3)	0.0021 (3)
N2	0.0282 (5)	0.0244 (4)	0.0166 (4)	0.0011 (4)	−0.0003 (3)	0.0010 (3)
O1	0.0375 (5)	0.0234 (4)	0.0190 (4)	−0.0039 (3)	−0.0029 (3)	−0.0013 (3)
O2	0.0416 (5)	0.0271 (4)	0.0176 (4)	−0.0048 (4)	−0.0044 (3)	0.0054 (3)

Geometric parameters (Å, º) top

C1—O1	1.2343 (13)	C5—Cl1	1.7393 (11)
C1—N1	1.3551 (13)	C6—C7	1.3955 (16)
C1—C2	1.5006 (15)	C6—H3	0.9500
C2—N2	1.2869 (13)	C7—C8	1.3833 (14)
C2—C3	1.4629 (14)	C7—H4	0.9500
C3—C4	1.3882 (15)	C8—N1	1.4038 (14)
C3—C8	1.4078 (14)	N1—H1	0.8800
C4—C5	1.3947 (14)	N2—O2	1.3704 (13)
C4—H2	0.9500	O2—H5	0.8400
C5—C6	1.3902 (16)

O1—C1—N1	126.11 (10)	C5—C6—C7	120.52 (10)
O1—C1—C2	127.48 (10)	C5—C6—H3	119.7
N1—C1—C2	106.38 (9)	C7—C6—H3	119.7
N2—C2—C3	135.31 (10)	C8—C7—C6	117.41 (10)
N2—C2—C1	117.97 (10)	C8—C7—H4	121.3
C3—C2—C1	106.62 (9)	C6—C7—H4	121.3
C4—C3—C8	120.73 (9)	C7—C8—N1	128.05 (10)
C4—C3—C2	133.49 (9)	C7—C8—C3	121.93 (10)
C8—C3—C2	105.78 (9)	N1—C8—C3	110.02 (9)
C3—C4—C5	116.89 (10)	C1—N1—C8	111.19 (9)
C3—C4—H2	121.6	C1—N1—H1	124.4
C5—C4—H2	121.6	C8—N1—H1	124.4
C6—C5—C4	122.52 (10)	C2—N2—O2	111.96 (9)
C6—C5—Cl1	118.78 (8)	N2—O2—H5	109.5
C4—C5—Cl1	118.69 (9)

O1—C1—C2—N2	1.07 (18)	C5—C6—C7—C8	−0.52 (18)
N1—C1—C2—N2	−177.28 (10)	C6—C7—C8—N1	−178.76 (11)
O1—C1—C2—C3	178.05 (11)	C6—C7—C8—C3	0.66 (17)
N1—C1—C2—C3	−0.30 (12)	C4—C3—C8—C7	−0.45 (16)
N2—C2—C3—C4	−2.8 (2)	C2—C3—C8—C7	179.89 (10)
C1—C2—C3—C4	−179.06 (11)	C4—C3—C8—N1	179.07 (10)
N2—C2—C3—C8	176.75 (13)	C2—C3—C8—N1	−0.59 (12)
C1—C2—C3—C8	0.54 (11)	O1—C1—N1—C8	−178.44 (11)
C8—C3—C4—C5	0.08 (15)	C2—C1—N1—C8	−0.07 (12)
C2—C3—C4—C5	179.63 (11)	C7—C8—N1—C1	179.91 (11)
C3—C4—C5—C6	0.05 (17)	C3—C8—N1—C1	0.43 (13)
C3—C4—C5—Cl1	−179.83 (8)	C3—C2—N2—O2	0.03 (19)
C4—C5—C6—C7	0.18 (18)	C1—C2—N2—O2	175.92 (9)
Cl1—C5—C6—C7	−179.94 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.00	2.8476 (13)	162
O2—H5···O1ⁱⁱ	0.84	1.94	2.7235 (12)	155

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

Acknowledgements

ABO is an associate researcher in the project `Dinitrosyl complexes containing thiol and/or thiosemicarbazone: synthesis, characterization and treatment against cancer', funded by FAPESP, Proc. 2015/12098–0, and acknowledges Professor José Clayston Melo Pereira (UNESP, Brazil) for his support in this work. The authors acknowledge the Laboratory of Crystallography at the Federal University of Santa Catarina (UFSC, Brazil) and the financial support from FINEP (Brazil).

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