1,1′-(Ethane-1,2-di­yl)bis­(indoline-2,3-dione)

Wang, Y.; Cao, S.-L.; Wan, C.-Q.; Yuan, J.-L.

doi:10.1107/S1600536810018957

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages o1569-o1570

doi:10.1107/S1600536810018957

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1,1′-(Ethane-1,2-diyl)bis(indoline-2,3-dione)

Yao Wang,^a Sheng-Li Cao,^a ^* Chong-Qing Wan ^a and Jing-Li Yuan ^a

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

(Received 6 February 2010; accepted 20 May 2010; online 5 June 2010)

The molecule of the title compound, C₁₈H₁₂N₂O₄, is situated on a crystallographic centre of symmetry. The molecule has a zigzag structure, with two parallel symmetry-related indoline-2,3-dione fragments linked by an ethylene group at each N atom. In the crystal, the molecules stack in columns along the b axis. There are two such columns in the structure. The molecules within each column are parallel; however, the molecules in the two columns differ in the respective orientation of the indoline-2,3-dione fragments. In one column, they are approximately parallel to (112), while in the other they are approximately parallel to ( $[\overline{1}]$ 12). The interplanar angle between the indoline-2,3-dione fragments in the two columns is 80.83 (3)°. The molecules within each column are related by mutual displacement of their centres of symmetry, that is (0, ±1/2, ±1/2). The packing between the molecules is provided by weak interactions only, viz. C—H⋯O hydrogen bonds and π–π [centroid–centroid distance = 3.8745 (8) Å] and C=O⋯π interactions.

Related literature

For the biological and pharmacological activity of 1,2-bis[(indolin-2,3-dion)-1-yl]ethane and its analogues, see: Breinholt et al. (1996 ); Norman (1996 ); Rajopadhye & Popp (1988 ). For details of the synthesis, see: Hyatt et al. (2007 ). For the melting point, see: Schmidt et al. (2008 )·For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₈H₁₂N₂O₄
M_r = 320.30
Monoclinic, P 2₁ /c
a = 12.2572 (3) Å
b = 5.2314 (1) Å
c = 12.5122 (3) Å
β = 115.747 (1)°
V = 722.66 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.45 × 0.32 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.723, T_max = 0.893
13976 measured reflections
1714 independent reflections
1496 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.102
S = 1.05
1714 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.19 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
C9—H9A⋯O1ⁱ	0.97	2.47	3.262 (2)	139
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
C=O⋯π interactions (Å, °)

Cg1 and Cg2 are the centroids of the N1,C1,C6–C8 pyrrole and C1—C6 benzene rings, respectively.

C=O⋯Cg	O⋯Cg	C⋯Cg	C=O⋯Cg
C8—O2⋯Cg1	3.8207 (12)	4.4046 (12)	111.34 (10)
C8—O2⋯Cg1	3.6269 (15)	4.6449 (17)	142.86 (10)
C8—O2⋯Cg2	3.5874 (14)	3.5278 (14)	77.47 (9)
Symmetry codes: (i) x, 1+y, z; (ii) $[-x, {1\over 2} + y, {3\over 2} - z]$ ; (iii) x, 1+y, z.

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: 10.1107/S1600536810018957/fb2183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810018957/fb2183Isup2.hkl

checkCIF report

Comment top

Isatins present a wide range of important biological and pharmacological activities. Fungicide (Breinholt et al., 1996), antianxiety (Norman, 1996; Breinholt et al., 1996) and anticonvulsant ones (Rajopadhye & Popp, 1988) are among them. In particular, the title compound, 1,2-bis[(indolin-2,3-dion)-1-yl]ethane, and related 1,1-bis{4-[(2,3-dioxoindolin-1-yl)methyl]phenyl}methane and 1-(3,4-dichlorobenzyl)indoline-2,3-dione (Hyatt et al., 2007) have been considered as potent and selective carboxylesterase inhibitors (Hyatt et al., 2007). Herein, we report the structure of the title compound.

The centrosymmetric molecule takes a zigzag fashion, with two symmetric parallel indoline-2,3-dione fragments being linked by the ethylene group to the N atoms (Fig. 1). There are only weak intermolecular interactions in the structure: a π-electron—π-electron ring interaction between N1\C1\C6\C7\C8 (pyrrole) and C1\C2\C3\C4\C5\C6 (benzene) rings (symmetry code: x, y+1, z) with the distance between the respective centroids equal to 3.8745 (8) Å. A C-H···O bond is given in Tab. 1 while C═O···π-electron ring interactions are listed in Tab. 2.

The distance C7-C8 (1.5554 (19) Å) corresponds well to the pertinent distances previously observed in well determined structures with the indoline-2,3-dione fragment. The search in the Cambridge Structural Database (Allen, 2002; Cambridge Structural Database, version 5.31 and addenda up to 26 February 2010) yielded 12 hits with structures determined with R_val<0.05. The corresponding extremal distances from this search equalled to 1.531 and 1.578 Å for JOBDEG and NAQRAY, respectively.

Related literature top

For the biological and pharmacological activity of 1,2-bis((indolin-2,3-dion)-1-yl)ethane and its analogues, see: Breinholt et al. (1996); Norman (1996); Rajopadhye & Popp (1988). For details of the synthesis, see: Hyatt et al. (2007). For the melting point, see: Schmidt et al. (2008).For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

A mixture of indoline-2,3-dione (1.47 g, 10 mmol), 1,2-dibromoethane (5.64 g, 30 mmol) and K₂CO₃ (2 g, 14.5 mmol) in N,N-dimethylformamide (20 ml) was heated at 100-120 °C for 3 h. After cooling to room temperature, the reaction mixture was poured into 0°C water (100 ml). The resulting precipitate was separated by filtration, dried in air and then it was purified by column chromatography on a silica gel with dichloromethane/methanol = 95:5, v/v, as an eluent. The precipitate included the prevailing product 1-(2-bromoethyl)indoline-2,3-dione (R_f = 0.77, m.p. 131-132°C; yield 60.9%) as well as the the title product 1,2-bis[(indolin-2,3-dion)-1-yl]ethane (R_f = 0.64, m.p. 296-297°C; yield 13.1%). The prevailing product, 1-(2-bromoethyl)indoline-2,3-dione, has been determined by a mass spectrometric analysis while its melting point (131-132°C) corresponded to 131°C reported by Schmidt et al. (2008). The orange crystals of the title compound that measured 0.40 × 0.30 × 0.20 mm on average were obtained by slow evaporation from the solution of dichloromethane N,N-dimethylformamide 50:50 (v/v).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007) 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. Symmetry code: (i): -x, -y, -z+1.
	Fig. 2. The column motifs of the molecules of the title compound. The π-electron ring···π-electron ring interactions are shown as a red dashed lines. Cg1, Cg2 are the centroids of the N1-C1-C6-C7-C8 (pyrrole) and C1-C2-C3-C4-C5-C6 (benzene) rings, respectively. Symmetry codes: (i): x, 1+y, z; (ii): -x, 1/2+y, 3/2-z.

1,1'-(Ethane-1,2-diyl)bis(indoline-2,3-dione) top

Crystal data top

C₁₈H₁₂N₂O₄	F(000) = 332
M_r = 320.30	D_x = 1.472 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 569–570 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.2572 (3) Å	Cell parameters from 243 reflections
b = 5.2314 (1) Å	θ = 1.8–27.2°
c = 12.5122 (3) Å	µ = 0.11 mm⁻¹
β = 115.747 (1)°	T = 296 K
V = 722.66 (3) Å³	Block, orange
Z = 2	0.45 × 0.32 × 0.25 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1714 independent reflections
Radiation source: fine-focus sealed tube	1496 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.9°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −16→16
T_min = 0.723, T_max = 0.893	k = −6→6
13976 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0422P)² + 0.1818P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1714 reflections	Δρ_max = 0.19 e Å⁻³
110 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
24 constraints	Extinction coefficient: 0.060 (5)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₈H₁₂N₂O₄	V = 722.66 (3) Å³
M_r = 320.30	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2572 (3) Å	µ = 0.11 mm⁻¹
b = 5.2314 (1) Å	T = 296 K
c = 12.5122 (3) Å	0.45 × 0.32 × 0.25 mm
β = 115.747 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1714 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1496 reflections with I > 2σ(I)
T_min = 0.723, T_max = 0.893	R_int = 0.028
13976 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
1714 reflections	Δρ_min = −0.16 e Å⁻³
110 parameters

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 > 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
C1	0.22945 (10)	−0.0885 (2)	0.68434 (10)	0.0390 (3)
C2	0.26127 (11)	−0.2721 (3)	0.62433 (12)	0.0474 (3)
H5	0.2193	−0.2905	0.5425	0.057*
C3	0.35869 (12)	−0.4288 (3)	0.69112 (14)	0.0539 (4)
H4	0.3818	−0.5550	0.6527	0.065*
C4	0.42235 (12)	−0.4035 (3)	0.81260 (14)	0.0566 (4)
H3	0.4875	−0.5110	0.8545	0.068*
C5	0.38964 (12)	−0.2189 (3)	0.87211 (12)	0.0526 (3)
H2	0.4318	−0.2010	0.9540	0.063*
C6	0.29262 (11)	−0.0609 (2)	0.80716 (11)	0.0429 (3)
C7	0.23681 (12)	0.1498 (3)	0.84203 (12)	0.0478 (3)
C8	0.13013 (12)	0.2405 (2)	0.72484 (12)	0.0488 (3)
C9	0.04837 (11)	0.1014 (3)	0.51355 (11)	0.0484 (3)
H9A	0.0900	0.0746	0.4639	0.058*
H9B	0.0108	0.2689	0.4955	0.058*
N1	0.13504 (9)	0.0917 (2)	0.63726 (9)	0.0448 (3)
O2	0.05930 (10)	0.4097 (2)	0.71384 (11)	0.0696 (4)
O1	0.26316 (11)	0.2447 (2)	0.93787 (9)	0.0691 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0363 (5)	0.0370 (6)	0.0449 (6)	−0.0013 (5)	0.0187 (5)	0.0035 (5)
C2	0.0446 (6)	0.0499 (8)	0.0498 (7)	−0.0001 (5)	0.0223 (5)	−0.0031 (6)
C3	0.0506 (7)	0.0464 (8)	0.0736 (9)	0.0055 (6)	0.0352 (7)	0.0004 (7)
C4	0.0436 (7)	0.0509 (8)	0.0731 (9)	0.0099 (6)	0.0232 (7)	0.0159 (7)
C5	0.0471 (7)	0.0550 (8)	0.0488 (7)	−0.0009 (6)	0.0145 (6)	0.0106 (6)
C6	0.0442 (6)	0.0403 (6)	0.0449 (6)	−0.0024 (5)	0.0200 (5)	0.0030 (5)
C7	0.0573 (7)	0.0441 (7)	0.0500 (7)	−0.0051 (6)	0.0306 (6)	−0.0006 (6)
C8	0.0546 (7)	0.0393 (7)	0.0623 (8)	0.0022 (6)	0.0344 (6)	0.0042 (6)
C9	0.0438 (6)	0.0483 (7)	0.0494 (7)	0.0030 (6)	0.0169 (6)	0.0149 (6)
N1	0.0425 (5)	0.0424 (6)	0.0477 (6)	0.0057 (4)	0.0179 (5)	0.0044 (5)
O2	0.0796 (7)	0.0511 (6)	0.0934 (9)	0.0219 (5)	0.0518 (7)	0.0109 (6)
O1	0.0868 (8)	0.0726 (8)	0.0564 (6)	−0.0037 (6)	0.0390 (6)	−0.0127 (5)

Geometric parameters (Å, º) top

C1—C2	1.3757 (17)	C5—H2	0.9300
C1—C6	1.3958 (17)	C6—C7	1.4605 (18)
C1—N1	1.4081 (15)	C7—O1	1.2051 (16)
C2—C3	1.3892 (19)	C7—C8	1.5554 (19)
C2—H5	0.9300	C8—O2	1.2053 (16)
C3—C4	1.381 (2)	C8—N1	1.3665 (17)
C3—H4	0.9300	C9—N1	1.4486 (16)
C4—C5	1.381 (2)	C9—C9ⁱ	1.515 (3)
C4—H3	0.9300	C9—H9A	0.9700
C5—C6	1.3847 (18)	C9—H9B	0.9700

C2—C1—C6	121.32 (11)	C1—C6—C7	107.40 (11)
C2—C1—N1	127.98 (11)	O1—C7—C6	130.57 (14)
C6—C1—N1	110.70 (11)	O1—C7—C8	124.38 (13)
C1—C2—C3	117.20 (12)	C6—C7—C8	105.05 (10)
C1—C2—H5	121.4	O2—C8—N1	127.39 (14)
C3—C2—H5	121.4	O2—C8—C7	126.91 (13)
C4—C3—C2	122.18 (13)	N1—C8—C7	105.69 (11)
C4—C3—H4	118.9	N1—C9—C9ⁱ	110.73 (13)
C2—C3—H4	118.9	N1—C9—H9A	109.5
C3—C4—C5	120.21 (13)	C9ⁱ—C9—H9A	109.5
C3—C4—H3	119.9	N1—C9—H9B	109.5
C5—C4—H3	119.9	C9ⁱ—C9—H9B	109.5
C4—C5—C6	118.51 (13)	H9A—C9—H9B	108.1
C4—C5—H2	120.7	C8—N1—C1	111.12 (10)
C6—C5—H2	120.7	C8—N1—C9	124.73 (11)
C5—C6—C1	120.58 (12)	C1—N1—C9	123.94 (11)
C5—C6—C7	132.02 (12)

C6—C1—C2—C3	0.09 (18)	O1—C7—C8—O2	−1.6 (2)
N1—C1—C2—C3	−179.95 (12)	C6—C7—C8—O2	179.12 (13)
C1—C2—C3—C4	−0.3 (2)	O1—C7—C8—N1	177.33 (13)
C2—C3—C4—C5	0.4 (2)	C6—C7—C8—N1	−1.95 (13)
C3—C4—C5—C6	−0.3 (2)	O2—C8—N1—C1	−179.26 (13)
C4—C5—C6—C1	0.07 (19)	C7—C8—N1—C1	1.81 (13)
C4—C5—C6—C7	−179.40 (13)	O2—C8—N1—C9	−4.4 (2)
C2—C1—C6—C5	0.03 (18)	C7—C8—N1—C9	176.68 (11)
N1—C1—C6—C5	−179.94 (11)	C2—C1—N1—C8	179.03 (12)
C2—C1—C6—C7	179.61 (11)	C6—C1—N1—C8	−1.01 (14)
N1—C1—C6—C7	−0.36 (13)	C2—C1—N1—C9	4.11 (19)
C5—C6—C7—O1	1.7 (2)	C6—C1—N1—C9	−175.93 (11)
C1—C6—C7—O1	−177.84 (14)	C9ⁱ—C9—N1—C8	−95.50 (17)
C5—C6—C7—C8	−179.10 (13)	C9ⁱ—C9—N1—C1	78.73 (17)
C1—C6—C7—C8	1.38 (13)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1ⁱⁱ	0.97	2.47	3.262 (2)	139

Symmetry code: (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₂N₂O₄
M_r	320.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.2572 (3), 5.2314 (1), 12.5122 (3)
β (°)	115.747 (1)
V (Å³)	722.66 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.45 × 0.32 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.723, 0.893
No. of measured, independent and observed [I > 2σ(I)] reflections	13976, 1714, 1496
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.102, 1.05
No. of reflections	1714
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: APEX2 (Bruker, 2007), APEX2 (Bruker, 2007) 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
C9—H9A···O1ⁱ	0.97	2.47	3.262 (2)	139

Symmetry code: (i) x, −y+1/2, z−1/2.

C═O···π interactions (Å, °) top

Cg1 and Cg2 are the centroids of the N1,C1,C6–C8 pyrrole and C1—C6 benzene rings, respectively.

C═O···Cg	O···Cg	C···Cg	C═O···Cg
C8—O2···Cg1	3.8207 (12)	4.4046 (12)	111.34 (10)
C8—O2···Cg1	3.6269 (15)	4.6449 (17)	142.86 (10)
C8—O2···Cg2	3.5874 (14)	3.5278 (14)	77.47 (9)

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

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

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Breinholt, J., Demuth, H., Heide, M., Jensen, G. W., Moller, I. L., Nielson, R. I., Olsen, C. E. & Rosendahl, C. N. (1996). Acta Chem. Scand. 50, 443–445. CrossRef CAS Web of Science Google Scholar
Bruker (2007). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hyatt, J. L., Moak, T., Hatfield, M. J., Tsurkan, L., Edwards, C. C., Wierdl, M., Danks, M. K., Wadkins, R. M. & Potter, P. M. (2007). J. Med. Chem. 50, 1876–1885. Web of Science CrossRef PubMed CAS Google Scholar
Norman, T. R. (1996). Med. Sci. Res. 24, 153–154. CAS Google Scholar
Rajopadhye, M. & Popp, F. D. (1988). J. Med. Chem. 31, 1001–1005. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Schmidt, M. S., Reverdito, A. M., Kremenchuzky, L., Perillo, I. A. & Blanco, M. M. (2008). Molecules, 13, 831–840. Web of Science PubMed Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar