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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1569–o1570.
Published online 2010 June 5. doi:  10.1107/S1600536810018957
PMCID: PMC3006689

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

Abstract

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 (An external file that holds a picture, illustration, etc.
Object name is e-66-o1569-efi2.jpg12). 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 [triangle]); Norman (1996 [triangle]); Rajopadhye & Popp (1988 [triangle]). For details of the synthesis, see: Hyatt et al. (2007 [triangle]). For the melting point, see: Schmidt et al. (2008 [triangle])·For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1569-scheme1.jpg

Experimental

Crystal data

  • C18H12N2O4
  • M r = 320.30
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1569-efi3.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.102
  • S = 1.05
  • 1714 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: APEX2 and SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)
Table 2
C=O(...)π inter­actions (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810018957/fb2183sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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).

supplementary crystallographic information

Comment

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 Rval<0.05. The corresponding extremal distances from this search equalled to 1.531 and 1.578 Å for JOBDEG and NAQRAY, respectively.

Experimental

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 (Rf = 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 (Rf = 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).

Refinement

All the H atoms were discernible in the difference electron density maps. Nevertheless, the hydrogen atoms were placed into the idealized positions and allowed to ride on the carrier atoms, with C—H = 0.93 and 0.97 Å for aryl and methylene hydrogens, respectively. Uiso(H) = 1.2Ueq(C)aryl/methylene.

Figures

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 ...

Crystal data

C18H12N2O4F(000) = 332
Mr = 320.30Dx = 1.472 Mg m3
Monoclinic, P21/cMelting point = 569–570 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 12.2572 (3) ÅCell parameters from 243 reflections
b = 5.2314 (1) Åθ = 1.8–27.2°
c = 12.5122 (3) ŵ = 0.11 mm1
β = 115.747 (1)°T = 296 K
V = 722.66 (3) Å3Block, orange
Z = 20.45 × 0.32 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer1714 independent reflections
Radiation source: fine-focus sealed tube1496 reflections with I > 2σ(I)
graphiteRint = 0.028
ω scansθmax = 27.9°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −16→16
Tmin = 0.723, Tmax = 0.893k = −6→6
13976 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.102w = 1/[σ2(Fo2) + (0.0422P)2 + 0.1818P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1714 reflectionsΔρmax = 0.19 e Å3
110 parametersΔρmin = −0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
24 constraintsExtinction coefficient: 0.060 (5)
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/Ueq
C10.22945 (10)−0.0885 (2)0.68434 (10)0.0390 (3)
C20.26127 (11)−0.2721 (3)0.62433 (12)0.0474 (3)
H50.2193−0.29050.54250.057*
C30.35869 (12)−0.4288 (3)0.69112 (14)0.0539 (4)
H40.3818−0.55500.65270.065*
C40.42235 (12)−0.4035 (3)0.81260 (14)0.0566 (4)
H30.4875−0.51100.85450.068*
C50.38964 (12)−0.2189 (3)0.87211 (12)0.0526 (3)
H20.4318−0.20100.95400.063*
C60.29262 (11)−0.0609 (2)0.80716 (11)0.0429 (3)
C70.23681 (12)0.1498 (3)0.84203 (12)0.0478 (3)
C80.13013 (12)0.2405 (2)0.72484 (12)0.0488 (3)
C90.04837 (11)0.1014 (3)0.51355 (11)0.0484 (3)
H9A0.09000.07460.46390.058*
H9B0.01080.26890.49550.058*
N10.13504 (9)0.0917 (2)0.63726 (9)0.0448 (3)
O20.05930 (10)0.4097 (2)0.71384 (11)0.0696 (4)
O10.26316 (11)0.2447 (2)0.93787 (9)0.0691 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0363 (5)0.0370 (6)0.0449 (6)−0.0013 (5)0.0187 (5)0.0035 (5)
C20.0446 (6)0.0499 (8)0.0498 (7)−0.0001 (5)0.0223 (5)−0.0031 (6)
C30.0506 (7)0.0464 (8)0.0736 (9)0.0055 (6)0.0352 (7)0.0004 (7)
C40.0436 (7)0.0509 (8)0.0731 (9)0.0099 (6)0.0232 (7)0.0159 (7)
C50.0471 (7)0.0550 (8)0.0488 (7)−0.0009 (6)0.0145 (6)0.0106 (6)
C60.0442 (6)0.0403 (6)0.0449 (6)−0.0024 (5)0.0200 (5)0.0030 (5)
C70.0573 (7)0.0441 (7)0.0500 (7)−0.0051 (6)0.0306 (6)−0.0006 (6)
C80.0546 (7)0.0393 (7)0.0623 (8)0.0022 (6)0.0344 (6)0.0042 (6)
C90.0438 (6)0.0483 (7)0.0494 (7)0.0030 (6)0.0169 (6)0.0149 (6)
N10.0425 (5)0.0424 (6)0.0477 (6)0.0057 (4)0.0179 (5)0.0044 (5)
O20.0796 (7)0.0511 (6)0.0934 (9)0.0219 (5)0.0518 (7)0.0109 (6)
O10.0868 (8)0.0726 (8)0.0564 (6)−0.0037 (6)0.0390 (6)−0.0127 (5)

Geometric parameters (Å, °)

C1—C21.3757 (17)C5—H20.9300
C1—C61.3958 (17)C6—C71.4605 (18)
C1—N11.4081 (15)C7—O11.2051 (16)
C2—C31.3892 (19)C7—C81.5554 (19)
C2—H50.9300C8—O21.2053 (16)
C3—C41.381 (2)C8—N11.3665 (17)
C3—H40.9300C9—N11.4486 (16)
C4—C51.381 (2)C9—C9i1.515 (3)
C4—H30.9300C9—H9A0.9700
C5—C61.3847 (18)C9—H9B0.9700
C2—C1—C6121.32 (11)C1—C6—C7107.40 (11)
C2—C1—N1127.98 (11)O1—C7—C6130.57 (14)
C6—C1—N1110.70 (11)O1—C7—C8124.38 (13)
C1—C2—C3117.20 (12)C6—C7—C8105.05 (10)
C1—C2—H5121.4O2—C8—N1127.39 (14)
C3—C2—H5121.4O2—C8—C7126.91 (13)
C4—C3—C2122.18 (13)N1—C8—C7105.69 (11)
C4—C3—H4118.9N1—C9—C9i110.73 (13)
C2—C3—H4118.9N1—C9—H9A109.5
C3—C4—C5120.21 (13)C9i—C9—H9A109.5
C3—C4—H3119.9N1—C9—H9B109.5
C5—C4—H3119.9C9i—C9—H9B109.5
C4—C5—C6118.51 (13)H9A—C9—H9B108.1
C4—C5—H2120.7C8—N1—C1111.12 (10)
C6—C5—H2120.7C8—N1—C9124.73 (11)
C5—C6—C1120.58 (12)C1—N1—C9123.94 (11)
C5—C6—C7132.02 (12)
C6—C1—C2—C30.09 (18)O1—C7—C8—O2−1.6 (2)
N1—C1—C2—C3−179.95 (12)C6—C7—C8—O2179.12 (13)
C1—C2—C3—C4−0.3 (2)O1—C7—C8—N1177.33 (13)
C2—C3—C4—C50.4 (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—C10.07 (19)C7—C8—N1—C11.81 (13)
C4—C5—C6—C7−179.40 (13)O2—C8—N1—C9−4.4 (2)
C2—C1—C6—C50.03 (18)C7—C8—N1—C9176.68 (11)
N1—C1—C6—C5−179.94 (11)C2—C1—N1—C8179.03 (12)
C2—C1—C6—C7179.61 (11)C6—C1—N1—C8−1.01 (14)
N1—C1—C6—C7−0.36 (13)C2—C1—N1—C94.11 (19)
C5—C6—C7—O11.7 (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—C178.73 (17)
C1—C6—C7—C81.38 (13)

Symmetry codes: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9A···O1ii0.972.473.262 (2)139

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

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···CgO···CgC···CgC═O···Cg
C8—O2···Cg13.8207 (12)4.4046 (12)111.34 (10)
C8—O2···Cg13.6269 (15)4.6449 (17)142.86 (10)
C8—O2···Cg23.5874 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2183).

References

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