organic compounds
5-Chloro-1-(prop-2-ynyl)indoline-2,3-dione
aResearch Department of Physics, S.D.N.B. Vaishnav College for Women, Chromepet, Chennai 600 044, India, and bOrganic Chemistry Division, CSIR Central Leather Research Institute, Chennai 600 020, India
*Correspondence e-mail: lakssdnbvc@gmail.com
In the title isatin derivative, C11H6ClNO2, the indoline ring is planar (r.m.s. deviation = 0.009 Å), with the two ketone O atoms lying in the plane and the chlorine atom displaced by 0.036 (1) Å. The dihedral angle between the mean plane of the indoline ring system with that of the propynyl chain is 73 (8)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains propagating along the b-axis direction. The chains are linked via weak π–π interactions [inter-centroid distance = 3.728 (1) Å], forming slabs parallel to the bc plane.
Keywords: crystal structure; isatin; terminal alkynes; C—H⋯O hydrogen bonds; π–π interactions.
CCDC reference: 1444744
Structure description
Isatins (indole-2,3-diones) are used in the synthesis of a large variety of heterocylic compounds (da Silva et al., 2001). Isatin and its derivatives have been reported to show pharmacological actions such as antimicrobial, anticancer, antiviral, anticonvulsant, anti-inflammatory and analgesic (Bhrigu et al., 2010). Biological properties of isatin include a range of actions in the brain and offer protection against certain types of infections (Pandeya et al., 2005). They have been evaluated for antibacterial and antifungal activities (Ramachandran, 2011), and have been reported to possess anti-MES activity (Smitha et al., 2008).
In the title compound, Fig. 1, the indoline ring is planar (r.m.s. deviation = 0.009 Å). Atom Cl1 is displaced from this mean plane by 0.036 (1) Å, while the O atoms, O1 and O2, lie in the plane of the ring system. The indoline ring is nearly perpendicular to the mean plane passing through the 1-propynyl chain as indicated by the C8—N1—C9—C10 torsion angle of 91.0 (2)°.
In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming chains along the b-axis direction (Table 1 and Fig. 2). The chains are linked by slipped parallel π–π interactions, forming slabs lying parallel to the bc plane [Cg1⋯Cg2i = 3.728 (1) Å, inter-planar distance = 3.327 (1) Å, slippage = 1.71 Å, Cg1 and Cg2 are the centroids of the N1/C1/C6–C8 and C1–C6 rings, respectively; symmetry code: (i) −x + , −y + , −z + 1].
Synthesis and crystallization
To a solution of 5-chloroindoline-2,3-dione (0.82 g, 5 mmol) in DMF (20 ml) potassium carbonate (1.04 g, 7.5 mmol) was added and the solution was stirred at room temperature. Propargyl bromide (0.7 ml, 7.5 mmol) was added dropwise and the resulting mixture was stirred overnight. After completion of the reaction (monitored by TLC), the mixture was partitioned between CH2Cl2 and water, and the CH2Cl2 layer was collected. The aqueous layer was extracted three times with CH2Cl2. The combined organic extracts were dried over anhydrous Na2SO4, and concentrated under vacuum to obtain the desired product. Colourless block-like crystals were obtained by slow evaporation of a solution in chloroform.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1444744
10.1107/S2414314616003977/su4018sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616003977/su4018Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616003977/su4018Isup3.cml
To a solution of 5-chloroindoline-2,3-dione (0.82 g, 5 mmol) in DMF (20 ml) potassium carbonate (1.04 g, 7.5 mmol) was added and the solution was stirred at room temperature. Propargyl bromide (0.7 ml, 7.5 mmol) was added dropwise and the resulting mixture was stirred overnight. After completion of the reaction (monitored by TLC), the mixture was partitioned between CH2Cl2 and water, and the CH2Cl2 layer was collected. The aqueous layer was extracted three times with CH2Cl2. The combined organic extracts were dried over anhydrous Na2SO4, and concentrated under vacuum to obtain the desired product. Colourless block-like crystals were obtained by slow evaporation of a solution in chloroform.
Isatins (indole-2,3-diones) are used in the synthesis of a large variety of heterocylic compounds (da Silva et al., 2001). Isatin and its derivatives have been reported to show pharmacological actions such as antimicrobial, anticancer, antiviral, anticonvulsant, anti-inflammatory and analgesic (Bhrigu et al., 2010). Biological properties of isatin include a range of actions in the brain and offer protection against certain types of infections (Pandeya et al., 2005). They have been evaluated for antibacterial and antifungal activities (Ramachandran, 2011), and have been reported to possess anti-MES activity (Smitha et al., 2008).
In the title compound, Fig. 1, the indoline ring is planar (r.m.s. deviation = 0.009 Å). Atom Cl1 is displaced from this mean plane by 0.036 (1) Å, while the O atoms, O1 and O2, lie in the plane of the ring system. The indoline ring is nearly perpendicular to the mean plane passing through the 1-propynyl chain as indicated by the C8—N1—C9—C10 torsion angle of 91.0 (2) °.
In the crystal, molecules are linked by C—H···O hydrogen bonds, forming chains along the b-axis direction (Table 1 and Fig. 2). The chains are linked by slipped parallel π–π interactions, forming slabs lying parallel to the bc plane [Cg1···Cg2i = 3.728 (1) Å, inter-planar distance = 3.327 (1) Å, slippage = 1.71 Å, Cg1 and Cg2 are the centroids of the N1/C1/C6–C8 and C1–C6 rings, respectively; symmetry code: (i) −x + 3/2, −y + 1/2, −z + 1].
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Crystal packing of the title compound, viewed along the a axis. The C—H···O hydrogen bonds are shown as dotted lines (see Table 1). |
C11H6ClNO2 | F(000) = 896 |
Mr = 219.62 | Dx = 1.485 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.0004 (4) Å | Cell parameters from 1429 reflections |
b = 7.9035 (3) Å | θ = 2.5–25.0° |
c = 16.8880 (6) Å | µ = 0.36 mm−1 |
β = 101.057 (1)° | T = 296 K |
V = 1965.00 (12) Å3 | Block, colourless |
Z = 8 | 0.30 × 0.25 × 0.25 mm |
Bruker Kappa APEXII CCD diffractometer | 1429 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
ω and φ scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −17→12 |
Tmin = 0.897, Tmax = 0.913 | k = −9→7 |
5667 measured reflections | l = −20→20 |
1723 independent reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0391P)2 + 1.521P] where P = (Fo2 + 2Fc2)/3 |
1723 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C11H6ClNO2 | V = 1965.00 (12) Å3 |
Mr = 219.62 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.0004 (4) Å | µ = 0.36 mm−1 |
b = 7.9035 (3) Å | T = 296 K |
c = 16.8880 (6) Å | 0.30 × 0.25 × 0.25 mm |
β = 101.057 (1)° |
Bruker Kappa APEXII CCD diffractometer | 1723 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 1429 reflections with I > 2σ(I) |
Tmin = 0.897, Tmax = 0.913 | Rint = 0.020 |
5667 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.18 e Å−3 |
1723 reflections | Δρmin = −0.25 e Å−3 |
136 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.62704 (12) | 0.4097 (2) | 0.47196 (10) | 0.0358 (4) | |
C2 | 0.54523 (12) | 0.3261 (3) | 0.46003 (12) | 0.0459 (5) | |
H2 | 0.5035 | 0.3370 | 0.4119 | 0.055* | |
C3 | 0.52684 (13) | 0.2247 (3) | 0.52229 (13) | 0.0483 (5) | |
H3 | 0.4717 | 0.1676 | 0.5160 | 0.058* | |
C4 | 0.58942 (12) | 0.2078 (2) | 0.59317 (12) | 0.0435 (5) | |
C5 | 0.67249 (12) | 0.2900 (2) | 0.60527 (11) | 0.0390 (4) | |
H5 | 0.7146 | 0.2776 | 0.6531 | 0.047* | |
C6 | 0.69011 (11) | 0.3908 (2) | 0.54372 (10) | 0.0342 (4) | |
C7 | 0.76974 (12) | 0.4937 (2) | 0.53727 (11) | 0.0378 (4) | |
C8 | 0.74633 (13) | 0.5761 (2) | 0.45251 (11) | 0.0409 (4) | |
C9 | 0.61323 (16) | 0.5719 (3) | 0.33937 (11) | 0.0528 (5) | |
H9A | 0.6327 | 0.6845 | 0.3275 | 0.063* | |
H9B | 0.5486 | 0.5763 | 0.3391 | 0.063* | |
C10 | 0.62976 (14) | 0.4554 (3) | 0.27659 (11) | 0.0505 (5) | |
C11 | 0.64529 (17) | 0.3631 (4) | 0.22730 (13) | 0.0708 (7) | |
H11 | 0.6577 | 0.2894 | 0.1879 | 0.085* | |
Cl1 | 0.56412 (4) | 0.08187 (8) | 0.67021 (4) | 0.0692 (2) | |
N1 | 0.66111 (11) | 0.5215 (2) | 0.41938 (8) | 0.0420 (4) | |
O1 | 0.79434 (10) | 0.67110 (19) | 0.42323 (8) | 0.0563 (4) | |
O2 | 0.84013 (9) | 0.51612 (19) | 0.58385 (8) | 0.0544 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0398 (9) | 0.0333 (10) | 0.0348 (9) | 0.0067 (8) | 0.0081 (7) | −0.0063 (7) |
C2 | 0.0385 (10) | 0.0474 (12) | 0.0479 (11) | 0.0040 (9) | −0.0014 (8) | −0.0099 (9) |
C3 | 0.0369 (10) | 0.0430 (12) | 0.0663 (13) | −0.0032 (9) | 0.0135 (9) | −0.0109 (10) |
C4 | 0.0454 (10) | 0.0377 (11) | 0.0530 (11) | 0.0018 (8) | 0.0238 (9) | −0.0007 (9) |
C5 | 0.0403 (10) | 0.0408 (11) | 0.0367 (9) | 0.0064 (8) | 0.0096 (8) | −0.0012 (8) |
C6 | 0.0341 (9) | 0.0337 (10) | 0.0358 (9) | 0.0026 (7) | 0.0090 (7) | −0.0049 (8) |
C7 | 0.0381 (10) | 0.0354 (10) | 0.0408 (10) | 0.0027 (8) | 0.0094 (8) | −0.0056 (8) |
C8 | 0.0504 (11) | 0.0339 (10) | 0.0424 (10) | 0.0053 (9) | 0.0186 (9) | −0.0031 (8) |
C9 | 0.0693 (13) | 0.0506 (13) | 0.0364 (10) | 0.0156 (11) | 0.0051 (9) | 0.0035 (9) |
C10 | 0.0578 (12) | 0.0583 (14) | 0.0336 (10) | 0.0107 (10) | 0.0038 (9) | 0.0031 (10) |
C11 | 0.0820 (17) | 0.0843 (18) | 0.0424 (12) | 0.0237 (14) | 0.0027 (11) | −0.0117 (12) |
Cl1 | 0.0749 (4) | 0.0646 (4) | 0.0789 (4) | −0.0021 (3) | 0.0422 (3) | 0.0151 (3) |
N1 | 0.0526 (9) | 0.0411 (9) | 0.0317 (8) | 0.0054 (8) | 0.0067 (7) | 0.0000 (7) |
O1 | 0.0687 (9) | 0.0482 (9) | 0.0598 (9) | −0.0010 (7) | 0.0316 (7) | 0.0062 (7) |
O2 | 0.0406 (8) | 0.0610 (10) | 0.0586 (9) | −0.0075 (7) | 0.0016 (7) | −0.0006 (7) |
C1—C2 | 1.374 (3) | C6—C7 | 1.466 (2) |
C1—C6 | 1.395 (2) | C7—O2 | 1.203 (2) |
C1—N1 | 1.416 (2) | C7—C8 | 1.550 (3) |
C2—C3 | 1.391 (3) | C8—O1 | 1.210 (2) |
C2—H2 | 0.9300 | C8—N1 | 1.363 (2) |
C3—C4 | 1.379 (3) | C9—N1 | 1.459 (2) |
C3—H3 | 0.9300 | C9—C10 | 1.461 (3) |
C4—C5 | 1.385 (3) | C9—H9A | 0.9700 |
C4—Cl1 | 1.7367 (19) | C9—H9B | 0.9700 |
C5—C6 | 1.375 (2) | C10—C11 | 1.163 (3) |
C5—H5 | 0.9300 | C11—H11 | 0.9300 |
C2—C1—C6 | 120.91 (17) | O2—C7—C6 | 131.19 (18) |
C2—C1—N1 | 128.89 (17) | O2—C7—C8 | 123.86 (17) |
C6—C1—N1 | 110.20 (15) | C6—C7—C8 | 104.95 (15) |
C1—C2—C3 | 117.85 (17) | O1—C8—N1 | 127.83 (18) |
C1—C2—H2 | 121.1 | O1—C8—C7 | 126.21 (18) |
C3—C2—H2 | 121.1 | N1—C8—C7 | 105.95 (15) |
C4—C3—C2 | 120.75 (18) | N1—C9—C10 | 112.24 (16) |
C4—C3—H3 | 119.6 | N1—C9—H9A | 109.2 |
C2—C3—H3 | 119.6 | C10—C9—H9A | 109.2 |
C3—C4—C5 | 121.73 (18) | N1—C9—H9B | 109.2 |
C3—C4—Cl1 | 119.72 (15) | C10—C9—H9B | 109.2 |
C5—C4—Cl1 | 118.55 (15) | H9A—C9—H9B | 107.9 |
C6—C5—C4 | 117.27 (17) | C11—C10—C9 | 178.3 (2) |
C6—C5—H5 | 121.4 | C10—C11—H11 | 180.0 |
C4—C5—H5 | 121.4 | C8—N1—C1 | 111.27 (15) |
C5—C6—C1 | 121.47 (16) | C8—N1—C9 | 123.39 (17) |
C5—C6—C7 | 130.92 (16) | C1—N1—C9 | 125.34 (17) |
C1—C6—C7 | 107.61 (15) | ||
C6—C1—C2—C3 | 1.1 (3) | C1—C6—C7—C8 | −0.14 (18) |
N1—C1—C2—C3 | −178.77 (17) | O2—C7—C8—O1 | −0.2 (3) |
C1—C2—C3—C4 | −0.7 (3) | C6—C7—C8—O1 | 180.00 (17) |
C2—C3—C4—C5 | −0.1 (3) | O2—C7—C8—N1 | −179.26 (17) |
C2—C3—C4—Cl1 | 179.38 (14) | C6—C7—C8—N1 | 0.98 (18) |
C3—C4—C5—C6 | 0.4 (3) | O1—C8—N1—C1 | 179.53 (18) |
Cl1—C4—C5—C6 | −179.05 (13) | C7—C8—N1—C1 | −1.47 (19) |
C4—C5—C6—C1 | 0.0 (3) | O1—C8—N1—C9 | 0.4 (3) |
C4—C5—C6—C7 | 179.80 (17) | C7—C8—N1—C9 | 179.41 (15) |
C2—C1—C6—C5 | −0.8 (3) | C2—C1—N1—C8 | −178.69 (18) |
N1—C1—C6—C5 | 179.11 (15) | C6—C1—N1—C8 | 1.5 (2) |
C2—C1—C6—C7 | 179.39 (16) | C2—C1—N1—C9 | 0.4 (3) |
N1—C1—C6—C7 | −0.73 (19) | C6—C1—N1—C9 | −179.44 (16) |
C5—C6—C7—O2 | 0.3 (3) | C10—C9—N1—C8 | 90.9 (2) |
C1—C6—C7—O2 | −179.88 (19) | C10—C9—N1—C1 | −88.1 (2) |
C5—C6—C7—C8 | −179.97 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.33 | 3.236 (3) | 164 |
Symmetry code: (i) −x+3/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.33 | 3.236 (3) | 164 |
Symmetry code: (i) −x+3/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H6ClNO2 |
Mr | 219.62 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 15.0004 (4), 7.9035 (3), 16.8880 (6) |
β (°) | 101.057 (1) |
V (Å3) | 1965.00 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.30 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.897, 0.913 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5667, 1723, 1429 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.092, 1.06 |
No. of reflections | 1723 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.25 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS2014 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Acknowledgements
The authors thank The Department of Chemistry, IIT, Chennai, for the data collection.
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