7-Methyl-1H-indole-2,3-dione

Lyncee, M.-T.A.; Desikan, V.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314617003789

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170378

https://doi.org/10.1107/S2414314617003789

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7-Methyl-1H-indole-2,3-dione

Myrria-Tahisha A. Lyncee,^a Vasumathi Desikan,^a James A. Golen ^b and David R. Manke ^b ^*

^aDepartment of Science & Math, Massasoit Community College, 1 Massasoit Boulevard, Brockton, MA 02302, USA, and ^bDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 8 March 2017; accepted 8 March 2017; online 9 January 2017)

The title compound, C₉H₇NO₂, has a single molecule in the asymmetric unit, with the non-H atoms possessing a mean deviation from planarity of 0.034 Å. In the crystal, the molecules dimerize through pairs of N—H⋯O hydrogen bonds. The nine-membered rings of the isatins stack along the b axis, through parallel slipped π–π interactions [intercentroid distance = 3.8832 (4) Å, interplanar distance = 3.4038 (7) Å and slippage = 1.8690 (12) Å].

Keywords: crystal structure; isatins; hydrogen bonding; π–π interactions.

CCDC reference: 1536802

Structure description

As part of our continuing study of the intermolecular interactions of substituted isatins, we report the crystal structure of 7-methyl-1H-indole-2,3-dione (Fig. 1). The molecule is nearly planar, with the non-H atoms in the structure demonstrating a mean deviation from planarity of 0.034 Å. The bond lengths and angles are consistent with those observed in the reported N-substituted derivative of 7-methyl-1H-indole-2,3-dione (Mironova et al., 2015 ).

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

In the crystal, the molecules dimerize through pairs of N1—H1⋯O1ⁱ hydrogen bonds (Table 1). This dimerization is observed in other 7-substituted isatin compounds (Garden et al., 2006 ; Golen & Manke, 2016a ,b ; Mohamed et al., 2008 ). The one reported exception is 7-chloroisatin, which forms a tetrameric assembly though its N—H⋯O hydrogen bonds (Sun & Cai, 2010 ). The nine-membered rings of the 7-methylisatin units stack along [010] with parallel slipped π–π interactions [intercentroid distance = 3.8832 (4) Å, interplanar distance = 3.4038 (7) Å and slippage = 1.8690 (12) Å]. The packing of the title compound, including hydrogen bonding, is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88 (1)	2.03 (1)	2.8907 (17)	170 (2)
Symmetry code: (i) -x+1, -y, -z+1.

Figure 2
The molecular packing of the title compound along the b axis, with hydrogen bonds shown as dashed lines.

Synthesis and crystallization

A commercial sample (AK Scientific) of 7-methylisatin was recrystallized by the slow evaporation of an acetonitrile solution to yield orange plates suitable for single-crystal diffraction analysis.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₇NO₂
M_r	161.16
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	7.8114 (10), 3.8832 (4), 24.362 (3)
β (°)	99.055 (5)
V (Å³)	729.76 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.19 × 0.18 × 0.04

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.701, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	18978, 1342, 1147
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.089, 1.09
No. of reflections	1342
No. of parameters	114
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)	0.20, −0.17
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1536802

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003789/sj4097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003789/sj4097Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617003789/sj4097Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

7-Methyl-1H-indole-2,3-dione top

Crystal data top

C₉H₇NO₂	F(000) = 336
M_r = 161.16	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.8114 (10) Å	Cell parameters from 7064 reflections
b = 3.8832 (4) Å	θ = 2.9–25.2°
c = 24.362 (3) Å	µ = 0.11 mm⁻¹
β = 99.055 (5)°	T = 200 K
V = 729.76 (15) Å³	Plate, orange
Z = 4	0.19 × 0.18 × 0.04 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	1147 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.050
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 25.5°, θ_min = 3.4°
T_min = 0.701, T_max = 0.745	h = −9→9
18978 measured reflections	k = −4→4
1342 independent reflections	l = −29→29

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.036P)² + 0.3841P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.20 e Å⁻³
1342 reflections	Δρ_min = −0.17 e Å⁻³
114 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.035 (5)

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.

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

	x	y	z	U_iso*/U_eq
O1	0.71863 (14)	−0.0390 (3)	0.54254 (4)	0.0339 (3)
O2	0.86187 (14)	0.1882 (3)	0.65601 (5)	0.0368 (3)
N1	0.47768 (16)	0.2518 (4)	0.56258 (5)	0.0245 (3)
H1	0.4086 (18)	0.206 (5)	0.5316 (5)	0.029*
C1	0.64162 (19)	0.1320 (4)	0.57297 (6)	0.0247 (4)
C2	0.71578 (19)	0.2489 (4)	0.63341 (6)	0.0249 (4)
C3	0.57186 (19)	0.4265 (4)	0.65299 (6)	0.0227 (4)
C4	0.5546 (2)	0.5703 (4)	0.70413 (6)	0.0273 (4)
H4	0.6491	0.5730	0.7339	0.033*
C5	0.3958 (2)	0.7094 (4)	0.71040 (7)	0.0303 (4)
H5	0.3804	0.8089	0.7449	0.036*
C6	0.2585 (2)	0.7045 (4)	0.66648 (7)	0.0286 (4)
H6	0.1515	0.8049	0.6719	0.034*
C7	0.27078 (19)	0.5583 (4)	0.61465 (6)	0.0245 (4)
C8	0.43097 (19)	0.4204 (4)	0.60971 (6)	0.0217 (4)
C9	0.1214 (2)	0.5477 (5)	0.56768 (7)	0.0332 (4)
H9A	0.0248	0.6828	0.5776	0.050*
H9B	0.0843	0.3085	0.5606	0.050*
H9C	0.1575	0.6447	0.5342	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0267 (6)	0.0463 (8)	0.0293 (6)	0.0072 (5)	0.0062 (5)	−0.0098 (5)
O2	0.0240 (6)	0.0523 (8)	0.0326 (6)	0.0067 (6)	−0.0001 (5)	−0.0013 (6)
N1	0.0217 (7)	0.0307 (7)	0.0208 (7)	0.0019 (6)	0.0023 (5)	−0.0027 (6)
C1	0.0209 (7)	0.0282 (8)	0.0258 (8)	0.0013 (7)	0.0061 (6)	0.0003 (7)
C2	0.0233 (8)	0.0273 (8)	0.0243 (8)	0.0005 (7)	0.0045 (6)	0.0022 (6)
C3	0.0235 (8)	0.0226 (8)	0.0226 (8)	−0.0008 (6)	0.0051 (6)	0.0013 (6)
C4	0.0302 (9)	0.0282 (8)	0.0233 (8)	−0.0022 (7)	0.0036 (6)	−0.0007 (7)
C5	0.0393 (10)	0.0280 (9)	0.0263 (8)	0.0002 (7)	0.0133 (7)	−0.0033 (7)
C6	0.0290 (8)	0.0243 (8)	0.0356 (9)	0.0034 (7)	0.0146 (7)	0.0013 (7)
C7	0.0237 (8)	0.0212 (8)	0.0294 (8)	0.0010 (6)	0.0070 (6)	0.0047 (6)
C8	0.0248 (8)	0.0198 (8)	0.0218 (7)	−0.0007 (6)	0.0077 (6)	0.0025 (6)
C9	0.0243 (8)	0.0364 (10)	0.0389 (10)	0.0063 (7)	0.0044 (7)	0.0018 (8)

Geometric parameters (Å, º) top

O1—C1	1.2219 (18)	C4—C5	1.383 (2)
O2—C2	1.2096 (18)	C5—H5	0.9500
N1—H1	0.875 (9)	C5—C6	1.391 (2)
N1—C1	1.348 (2)	C6—H6	0.9500
N1—C8	1.4184 (19)	C6—C7	1.401 (2)
C1—C2	1.562 (2)	C7—C8	1.384 (2)
C2—C3	1.461 (2)	C7—C9	1.501 (2)
C3—C4	1.391 (2)	C9—H9A	0.9800
C3—C8	1.399 (2)	C9—H9B	0.9800
C4—H4	0.9500	C9—H9C	0.9800

C1—N1—H1	122.1 (11)	C6—C5—H5	119.8
C1—N1—C8	111.40 (12)	C5—C6—H6	118.5
C8—N1—H1	126.2 (11)	C5—C6—C7	123.01 (15)
O1—C1—N1	128.12 (14)	C7—C6—H6	118.5
O1—C1—C2	125.78 (13)	C6—C7—C9	122.86 (14)
N1—C1—C2	106.09 (12)	C8—C7—C6	115.23 (14)
O2—C2—C1	123.77 (14)	C8—C7—C9	121.90 (14)
O2—C2—C3	131.48 (15)	C3—C8—N1	110.23 (13)
C3—C2—C1	104.74 (12)	C7—C8—N1	126.90 (14)
C4—C3—C2	132.06 (14)	C7—C8—C3	122.87 (14)
C4—C3—C8	120.39 (14)	C7—C9—H9A	109.5
C8—C3—C2	107.47 (13)	C7—C9—H9B	109.5
C3—C4—H4	121.0	C7—C9—H9C	109.5
C5—C4—C3	118.09 (14)	H9A—C9—H9B	109.5
C5—C4—H4	121.0	H9A—C9—H9C	109.5
C4—C5—H5	119.8	H9B—C9—H9C	109.5
C4—C5—C6	120.40 (15)

O1—C1—C2—O2	2.2 (3)	C3—C4—C5—C6	−0.1 (2)
O1—C1—C2—C3	−176.68 (16)	C4—C3—C8—N1	−178.04 (14)
O2—C2—C3—C4	−2.8 (3)	C4—C3—C8—C7	1.0 (2)
O2—C2—C3—C8	−179.42 (17)	C4—C5—C6—C7	0.9 (3)
N1—C1—C2—O2	−179.03 (16)	C5—C6—C7—C8	−0.7 (2)
N1—C1—C2—C3	2.08 (16)	C5—C6—C7—C9	178.84 (15)
C1—N1—C8—C3	2.46 (18)	C6—C7—C8—N1	178.62 (14)
C1—N1—C8—C7	−176.57 (15)	C6—C7—C8—C3	−0.3 (2)
C1—C2—C3—C4	175.98 (16)	C8—N1—C1—O1	175.98 (16)
C1—C2—C3—C8	−0.66 (16)	C8—N1—C1—C2	−2.74 (17)
C2—C3—C4—C5	−177.07 (16)	C8—C3—C4—C5	−0.8 (2)
C2—C3—C8—N1	−0.94 (17)	C9—C7—C8—N1	−0.9 (2)
C2—C3—C8—C7	178.13 (14)	C9—C7—C8—C3	−179.79 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (1)	2.03 (1)	2.8907 (17)	170 (2)

Symmetry code: (i) −x+1, −y, −z+1.

References

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IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170378

https://doi.org/10.1107/S2414314617003789

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

7-Methyl-1H-indole-2,3-dione

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds