3,3-Dichloro-1-(chloro­meth­yl)indolin-2-one

Wang, Y.; Wan, C.-Q.; Zheng, T.; Cao, S.-L.

doi:10.1107/S1600536810040717

organic compounds

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Volume 66| Part 11| November 2010| Page o2858

https://doi.org/10.1107/S1600536810040717

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3,3-Dichloro-1-(chloromethyl)indolin-2-one

Yao Wang,^a Chong-Qing Wan,^a Tingting Zheng ^a and Sheng-Li Cao ^a ^*

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: sl_cao@sohu.com

(Received 17 September 2010; accepted 11 October 2010; online 20 October 2010)

In the title compound, C₉H₆Cl₃NO, the pyrrole ring is almost coplanar with the benzene ring [dihedral angle = 1.90 (9)°], while the Cl—C—N—C torsion angle is 98.78 (17)°. In the crystal, pairs of molecules are interconnected by pairs of Cl⋯Cl interactions [3.564 (5) Å], forming dimers, which are further peripherally connected through intermolecular C—H⋯O=C and π–π interactions [centroid–centroid distances = 4.134 (7), 4.134 (6) and 4.238 (7) Å], forming a two-dimensional network.

Related literature

For the synthesis of the title compound, see: Höhme & Schwartz, (1974 ). For the synthesis of 1-(chloromethyl) indoline-2,3-dione, see: Höhme & Schwartz, (1973 ). For Cl⋯Cl interactions, see: Reddy et al. (2006 ).

Experimental

Crystal data

C₉H₆Cl₃NO
M_r = 250.50
Monoclinic, P 2₁ /c
a = 8.6102 (1) Å
b = 14.5573 (2) Å
c = 8.2461 (1) Å
β = 93.381 (1)°
V = 1031.78 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
13146 measured reflections
2450 independent reflections
2156 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.06
2450 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1ⁱ	0.93	2.57	3.173 (2)	123
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: APEX2 and SAINT (Bruker, 2007); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810040717/kj2158sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040717/kj2158Isup2.hkl

checkCIF report

Comment top

Höhme and Schwartz reported that the reaction of 1-(hydroxymethyl) indoline-2,3-dione with SOCl₂gave 1-(chloromethyl) indoline-2,3-dione (Höhme & Schwartz, 1973), whereas the reaction in the presence of a small amount of pyridine gave the title compound (Höhme & Schwartz, 1974). However, our experimental results showed that the title compound could also be obtained from the reaction in the absence of pyridine. Here, we report the structure of the title compound.

X-ray crystal analysis shows that the pyrrole ring almost lies within the plane of the benzene ring, while the torsion angle Cl2—C9—N1—C8 equals 98.78 (17)°, as shown in Fig.1. Two molecules arrange in a face to face mode and thus interconnect through intermolecular Cl1···Cl2(-x + 1, -y + 1, -z + 2) interactions (Cl···Cl=3.564 (5) Å) (Reddy et al., 2006), forming a dimer. Each dimeric unit peripherically links to four neihgbouring ones through intermolecular C4—H4···O1=C8 interactions (Table 1), generating a two-dimensional network. π–π interactions (Table 2) between the approximate parallel benzene and/or parrole rings cooperate with those weak interactions to consolidate the supramolecular structure, as shown in Fig. 2.

Related literature top

For the synthesis of the title compound, see: Höhme & Schwartz, (1974). For the synthesis of 1-(chloromethyl) indoline-2,3-dione, see: Höhme & Schwartz, (1973). For Cl···Cl interactions, see: Reddy et al. (2006).

Experimental top

A mixture of indoline-2,3-dione (3.0 g, 0.02 mol) and formalin (5 ml) in 30 ml of water was refluxed for 1 h. After that, the reaction mixture was stirred at room temperature overnight. The resulting precipitate, 1-(hydroxymethyl)indoline-2,3-dione, was separated by filtration and purified by recrystallization from ethanol, which was heated with SOCl₂(25 ml) under reflux for 3.5 h. The reaction mixture was distilled in vacuum to remove excess SOCl₂and the residue was purified by column chromatography on silica gel using dichloromethane/methanol=98:2, v/v, as an eluent (R_f=0.33, dichloromethane/methanol=98:2, v/v; m.p. 141–143°C; yield 50.5% in two steps). The light yellow crystals of the title compound were obtained by slow evaporation from the solution of dichloromethane methanol 98:2 (v/v) at room temperature.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 and PLATON (Spek, 2009).

Figures top

	Fig. 1. The title molecule with the atomic numbering scheme. The displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Cl···Cl and C-H···O=C interactions in the crystalline structure of the title compound. The blue dashed lines indicate Cl···Cl interaction, while the red dashed lines represent C—H···O=C interactions. All the π–π stacking interactions are omitted for clarity. Symmetry codes: iii-x + 1, -y + 1, -z + 2; iv-x + 1, y - 1/2, -z + 3/2.

3,3-Dichloro-1-(chloromethyl)indolin-2-one top

Crystal data top

C₉H₆Cl₃NO	F(000) = 504
M_r = 250.50	D_x = 1.613 Mg m⁻³ D_m = 1.613 Mg m⁻³ D_m measured by not measured
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.6102 (1) Å	Cell parameters from 7007 reflections
b = 14.5573 (2) Å	θ = 2.5–27.8°
c = 8.2461 (1) Å	µ = 0.85 mm⁻¹
β = 93.381 (1)°	T = 296 K
V = 1031.78 (2) Å³	Block, yellow
Z = 4	0.16 × 0.12 × 0.10 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2156 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 27.9°, θ_min = 2.4°
phi and ω scans	h = −11→11
13146 measured reflections	k = −19→19
2450 independent reflections	l = −10→10

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0433P)² + 0.4377P] where P = (F_o² + 2F_c²)/3
2450 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₉H₆Cl₃NO	V = 1031.78 (2) Å³
M_r = 250.50	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6102 (1) Å	µ = 0.85 mm⁻¹
b = 14.5573 (2) Å	T = 296 K
c = 8.2461 (1) Å	0.16 × 0.12 × 0.10 mm
β = 93.381 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2156 reflections with I > 2σ(I)
13146 measured reflections	R_int = 0.016
2450 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
2450 reflections	Δρ_min = −0.49 e Å⁻³
127 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
C9	0.4139 (2)	0.66723 (13)	0.5958 (2)	0.0448 (4)
H9A	0.3747	0.6171	0.5275	0.054*
H9B	0.4404	0.7176	0.5255	0.054*
Cl1	0.72991 (7)	0.48322 (4)	0.99637 (6)	0.06304 (17)
Cl3	0.87749 (7)	0.48989 (4)	0.69017 (7)	0.06607 (17)
Cl2	0.26419 (5)	0.70402 (4)	0.72483 (7)	0.06448 (17)
C1	0.9042 (2)	0.68812 (13)	0.9240 (2)	0.0478 (4)
H1	0.9838	0.6541	0.9762	0.057*
C2	0.9062 (2)	0.78348 (14)	0.9279 (3)	0.0533 (4)
H2	0.9882	0.8138	0.9836	0.064*
C3	0.7883 (2)	0.83366 (12)	0.8503 (2)	0.0497 (4)
H3	0.7922	0.8975	0.8545	0.060*
C4	0.66346 (19)	0.79124 (11)	0.7659 (2)	0.0415 (4)
H4	0.5837	0.8252	0.7139	0.050*
C5	0.66323 (17)	0.69655 (10)	0.76292 (19)	0.0345 (3)
C6	0.78112 (18)	0.64512 (11)	0.84075 (19)	0.0373 (3)
C7	0.74369 (19)	0.54609 (11)	0.8146 (2)	0.0410 (3)
C8	0.58313 (19)	0.54734 (11)	0.7189 (2)	0.0402 (3)
N1	0.54994 (15)	0.63781 (9)	0.68728 (17)	0.0385 (3)
O1	0.50408 (18)	0.48209 (9)	0.68047 (17)	0.0562 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C9	0.0434 (8)	0.0522 (9)	0.0379 (8)	0.0048 (7)	−0.0044 (7)	−0.0021 (7)
Cl1	0.0768 (3)	0.0574 (3)	0.0547 (3)	0.0061 (2)	0.0024 (2)	0.0214 (2)
Cl3	0.0658 (3)	0.0575 (3)	0.0769 (4)	0.0237 (2)	0.0207 (3)	−0.0084 (2)
Cl2	0.0411 (2)	0.0907 (4)	0.0615 (3)	0.0133 (2)	0.0021 (2)	−0.0031 (3)
C1	0.0344 (8)	0.0575 (10)	0.0512 (10)	0.0034 (7)	−0.0008 (7)	0.0031 (8)
C2	0.0421 (9)	0.0578 (11)	0.0595 (11)	−0.0122 (8)	−0.0006 (8)	−0.0053 (9)
C3	0.0509 (10)	0.0381 (8)	0.0609 (11)	−0.0072 (7)	0.0093 (8)	−0.0033 (8)
C4	0.0415 (8)	0.0350 (7)	0.0482 (9)	0.0034 (6)	0.0053 (7)	0.0020 (6)
C5	0.0332 (7)	0.0345 (7)	0.0361 (7)	0.0023 (5)	0.0045 (6)	−0.0008 (6)
C6	0.0358 (7)	0.0380 (8)	0.0386 (8)	0.0064 (6)	0.0062 (6)	0.0018 (6)
C7	0.0452 (8)	0.0369 (8)	0.0416 (8)	0.0106 (6)	0.0072 (7)	0.0039 (6)
C8	0.0473 (8)	0.0355 (7)	0.0383 (8)	0.0015 (6)	0.0075 (7)	−0.0014 (6)
N1	0.0379 (6)	0.0344 (6)	0.0428 (7)	0.0032 (5)	−0.0013 (5)	−0.0021 (5)
O1	0.0701 (9)	0.0399 (6)	0.0583 (8)	−0.0114 (6)	0.0012 (7)	−0.0040 (6)

Geometric parameters (Å, º) top

C9—N1	1.422 (2)	C3—C4	1.390 (2)
C9—Cl2	1.8009 (18)	C3—H3	0.9300
C9—H9A	0.9700	C4—C5	1.379 (2)
C9—H9B	0.9700	C4—H4	0.9300
Cl1—C7	1.7664 (17)	C5—C6	1.388 (2)
Cl3—C7	1.7856 (16)	C5—N1	1.414 (2)
C1—C6	1.378 (2)	C6—C7	1.490 (2)
C1—C2	1.389 (3)	C7—C8	1.551 (2)
C1—H1	0.9300	C8—O1	1.200 (2)
C2—C3	1.378 (3)	C8—N1	1.369 (2)
C2—H2	0.9300

N1—C9—Cl2	111.84 (12)	C4—C5—C6	122.06 (15)
N1—C9—H9A	109.2	C4—C5—N1	127.79 (14)
Cl2—C9—H9A	109.2	C6—C5—N1	110.15 (13)
N1—C9—H9B	109.2	C1—C6—C5	120.33 (15)
Cl2—C9—H9B	109.2	C1—C6—C7	131.67 (15)
H9A—C9—H9B	107.9	C5—C6—C7	107.99 (14)
C6—C1—C2	118.30 (16)	C6—C7—C8	103.95 (12)
C6—C1—H1	120.9	C6—C7—Cl1	113.78 (12)
C2—C1—H1	120.9	C8—C7—Cl1	109.59 (12)
C3—C2—C1	120.73 (17)	C6—C7—Cl3	112.65 (12)
C3—C2—H2	119.6	C8—C7—Cl3	107.40 (11)
C1—C2—H2	119.6	Cl1—C7—Cl3	109.15 (8)
C2—C3—C4	121.61 (16)	O1—C8—N1	127.02 (16)
C2—C3—H3	119.2	O1—C8—C7	126.84 (15)
C4—C3—H3	119.2	N1—C8—C7	106.13 (13)
C5—C4—C3	116.96 (16)	C8—N1—C5	111.52 (13)
C5—C4—H4	121.5	C8—N1—C9	123.16 (14)
C3—C4—H4	121.5	C5—N1—C9	125.26 (13)

C6—C1—C2—C3	−0.1 (3)	C6—C7—C8—O1	−175.08 (17)
C1—C2—C3—C4	0.1 (3)	Cl1—C7—C8—O1	−53.1 (2)
C2—C3—C4—C5	−0.2 (3)	Cl3—C7—C8—O1	65.3 (2)
C3—C4—C5—C6	0.3 (2)	C6—C7—C8—N1	4.91 (17)
C3—C4—C5—N1	179.42 (16)	Cl1—C7—C8—N1	126.87 (12)
C2—C1—C6—C5	0.2 (3)	Cl3—C7—C8—N1	−114.67 (12)
C2—C1—C6—C7	−179.47 (18)	O1—C8—N1—C5	174.89 (17)
C4—C5—C6—C1	−0.3 (2)	C7—C8—N1—C5	−5.10 (18)
N1—C5—C6—C1	−179.56 (15)	O1—C8—N1—C9	−2.4 (3)
C4—C5—C6—C7	179.42 (15)	C7—C8—N1—C9	177.62 (14)
N1—C5—C6—C7	0.16 (18)	C4—C5—N1—C8	−175.89 (16)
C1—C6—C7—C8	176.63 (17)	C6—C5—N1—C8	3.31 (19)
C5—C6—C7—C8	−3.04 (17)	C4—C5—N1—C9	1.3 (3)
C1—C6—C7—Cl1	57.5 (2)	C6—C5—N1—C9	−179.48 (15)
C5—C6—C7—Cl1	−122.18 (13)	Cl2—C9—N1—C8	98.78 (17)
C1—C6—C7—Cl3	−67.4 (2)	Cl2—C9—N1—C5	−78.12 (19)
C5—C6—C7—Cl3	112.91 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.57	3.173 (2)	123
C9—H9A···O1	0.97	2.56	2.879 (2)	100
C9—H9A···O1ⁱⁱ	0.97	2.52	3.256 (2)	133

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

Experimental details

Crystal data
Chemical formula	C₉H₆Cl₃NO
M_r	250.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.6102 (1), 14.5573 (2), 8.2461 (1)
β (°)	93.381 (1)
V (Å³)	1031.78 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13146, 2450, 2156
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.06
No. of reflections	2450
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.49

Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.57	3.173 (2)	123.

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

π–π interactions top

Cg(A)	Cg(B)	Cg(A)···Cg(B) (Å)	sym. code Cg(B)
Cg1	Cg1	4.134 (7)	x, -y +3/2, z-1/2
Cg1	Cg1	4.134 (6)	x, -y +3/2, z+1/2
Cg1	Cg2	4.238 (7)	x, -y +3/2, z-1/2

^* Cg1, Cg2 are the centroids of C1-C2-C3-C4-C5-C6 (benzene) and C5-C6-C7-C8-N1 (pyrrole),respectively.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (project No. 20972099) and the Beijing Municipal Commission of Education (project No. KM200710028008).

References

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