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The title compound, C15H11Cl2NO, was synthesized from N-­benzyl­isatin. The compound crystallizes as stacks of mol­ecules running down the c axis. Mol­ecules within each of these stacks inter­act with each other through π–π and C—H...π inter­actions, and inter­act with neighbouring stacks through C—H...O inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107002028/dn3029sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107002028/dn3029Isup2.hkl
Contains datablock I

CCDC reference: 641801

Comment top

Oxindoles occur commonly as subunits of biologically active compounds. For example compound 1 has been found to be a potential inhibitor of the kinase insert domain-containing receptor (KDR), alternatively referred to as VEGFR-2, a receptor for vascular endothelial growth factors (Bouérat et al., 2005). In essence, this compound is believed to function as a key regulator of angiogenesis.

As part of our research programme, we have been interested in the synthesis of substituted heterocycles, such as carbazoles (de Koning et al., 2003; Pelly et al., 2005; Pathak et al., 2006) and fused indole systems (de Koning et al., 2004). During the course of our work on the synthesis of potential kinase inhibitors (Fabbro et al., 2002; Geyer et al., 2005; Noble et al., 2005), we had reason to synthesize the simple oxindole derivative 2 from N-benzyl isatin 3, where the carbonyl at the 3-position of isatin is replaced by two Cl atoms. The structure of the product, (II), was confirmed by single-crystal X-ray crystallography (Fig. 1).

The bond lengths and angles for (II) were found to be typical for compounds of this type. Bond lengths and angles for the nitrogen-containing ring of the indol-2-one system are given in Table 1. A search of the Cambridge Structural Database (CSD; Version 5.27; Allen, 2002) for indol-2-one compounds with dichloro substitution on C2 (or IUPAC position 3; Fig. 1) yielded only two structures, viz. 3,3-dichloro-1H-indol-2(3H)-one, (IV) (CSD refcode KUNMUB; Zukerman-Schpector et al., 1993), and 1,3,3,5-tetrachloro-1,3-dihydroindol-2-one, (V) (QASXEO; Meketa et al., 2005). Comparison of the bond angles around the N-containing five-membered ring indicates that the N—C1 bond length as well as the C8—N—C1 and N—C1—C2 angles are most affected by the atom type bonded to the N atom (Table 3). Comparing geometric parameters around the rest of the five-membered ring for all three structures leads to differences of less than 0.01 Å and 1° for the bond lengths and angles, respectively.

The title compound is capable of rotation around the C9—N and C9—C10 bonds (Fig. 1). The conformation adopted by the molecule is one in which the indol-2-one system is rotated such that it is almost perpendicular [82.03 (3)°] to the phenyl ring (Fig. 2). This conformation allows for a simultaneous C—H···π and ππ interaction between molecules related by the c-glide plane. The C—H···π interaction occurs between the C9/H9B group and the C10–C15 ring (centroid Cg) of a neighbouring molecule (Table 2 and Fig. 2).

The ππ interaction occurs between the ring defined by N, C1, C2, C3 and C8 (the five-membered ring of the indol-2-one system) and the ring defined by C3–C8 (the six-membered ring of the indol-2-one system) of a neighbouring molecule (Fig. 2). In this interaction, the two rings are slipped by 30.2° relative to their ring perpendiculars (the average interplanar distance being 3.484 Å), with the ring centroid to ring centroid distance being 4.0329 (9) Å. Admittedly, the five-membered ring of the indol-2-one system is only partly aromatic, but a significant part of the ring (O, C1 and N) is involved in conjugation with the aromatic six-membered ring as shown by the bond lengths between these atoms (Table 1). The ππ interaction is therefore really between these atoms and those of the neighbouring ring. and if this were taken into account the centroid to centroid distance would be even shorter. A consequence of the C—H···π and ππ interactions is the creation of stacks of molecules running down the c axis (Fig. 3).

Finally, acting between the stacks of molecules just described are C—H···O and C—H···Cl interactions (Table 2 and Fig. 4).

Related literature top

For related literature, see: Allen (2002); Bouérat et al. (2005); Fabbro et al. (2002); Geyer et al. (2005); Koning et al. (2003, 2004); Meketa et al. (2005); Noble et al. (2005); Palazzo (1953); Pathak et al. (2006); Pelly et al. (2005); Zukerman-Schpector, Pinto, da DaC, Silva & Barcellos (1993).

Experimental top

The dione (III) (6.40 g, 27.00 mmol) was dissolved in C6H6 (70 ml) in a round-bottomed flask and cooled to 273 K. PCl5 (12.80 g, 62.10 mmol, 2.3 equivalents) was added and the solution was warmed to 298 K for 24 h. The solvent was removed in vacuo to obtain a yellow–brown residue, which was further purified by column chromatography (5% EtOAc/hexane) to afford (II) as a light-yellow oil. On addition of EtOH, (II) precipitated as a white solid [yield 6.37 g, 81%; m.p. 398–399 K (literature m.p. 399–400 K; Palazzo, 1953)]. 1H NMR (300 MHz, CDCl3, Me4Si): δH 4.94 (2H, s, PhCH2N), 6.72 (1H, d, J = 7.9 Hz, ArH), 7.14 (1H, t, J = 7.6 Hz, ArH), 7.22–7.39 (6H, m, 6 × ArH) and 7.64 (1H, d, J = 7.5 Hz, ArH). 13C NMR (75 MHz, CDCl3): δC 44.5 (PhCH2N), 110.1 (ArCCl2), 124.2 (CH), 124.9 (CH), 127.1 (2 × CH), 128.1 (CH), 129.0 (2 × CH), 129.3 (C), 131.8 (CH), 134.4 (C), 139.8 (C) and 169.2 (CO) (one CH not observed in spectrum).

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H bond lengths of 0.95 (aromatic CH) or 0.99 Å (CH2), and isotropic displacement parameters equal to 1.2 times Ueq of the parent atom.

Computing details top

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: PLATON (Spek, 2003) and SHELXTL (Bruker, 1999b).

Figures top
[Figure 1] Fig. 1. A view of the title molecule showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown with an arbitrary radius.
[Figure 2] Fig. 2. Weak interactions between molecules related by the c-glide plane producing a stack of molecules running down the c axis. Indicated with a star (*) on the diagram are the ππ interactions between the N/C1–C3/C8 and C3–C8 rings. Indicated with a hash (#) are the C—H···π interactions between the C9/H9B group and the C10–C15 ring. Molecules (i), (ii) and (iii) are in the symmetry positions (x, y, z), (x, 1/2 - y, 1/2 + z) and (x, y, 1 + z), respectively.
[Figure 3] Fig. 3. The crystal packing in (II) showing the stacks of molecules running down the c axis.
[Figure 4] Fig. 4. C—H···O interactions between molecules related by the screw symmetry running down the b axis. These interactions act between the stacks shown in Fig 2. Molecules (i), (ii), (iii) and (iv) are in the symmetry positions (x, y, z), (2 - x, 1/2 + y, 1/2 - z), (x, 1 + y, z) and (2 - x, 3/2 + y, 1/2 - z), respectively.
1-Benzyl-3,3-dichloro-1H-indol-2(3H)-one top
Crystal data top
C15H11Cl2NOF(000) = 600
Mr = 292.15Dx = 1.453 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 918 reflections
a = 10.4847 (13) Åθ = 2.5–28.1°
b = 14.4641 (18) ŵ = 0.48 mm1
c = 9.2203 (11) ÅT = 173 K
β = 107.244 (2)°Irregular, colourless
V = 1335.4 (3) Å30.48 × 0.30 × 0.26 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2603 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 28.0°, θmin = 2.0°
ϕ and ω scansh = 1311
8835 measured reflectionsk = 1917
3213 independent reflectionsl = 1112
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0453P)2 + 0.2606P]
where P = (Fo2 + 2Fc2)/3
3213 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C15H11Cl2NOV = 1335.4 (3) Å3
Mr = 292.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.4847 (13) ŵ = 0.48 mm1
b = 14.4641 (18) ÅT = 173 K
c = 9.2203 (11) Å0.48 × 0.30 × 0.26 mm
β = 107.244 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2603 reflections with I > 2σ(I)
8835 measured reflectionsRint = 0.028
3213 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.088H-atom parameters constrained
S = 1.05Δρmax = 0.33 e Å3
3213 reflectionsΔρmin = 0.35 e Å3
172 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
xyzUiso*/Ueq
C10.81611 (13)0.08784 (10)0.34296 (15)0.0290 (3)
C20.70179 (13)0.07206 (9)0.41592 (15)0.0277 (3)
C30.65767 (13)0.16757 (9)0.44019 (15)0.0255 (3)
C40.55791 (14)0.19881 (10)0.49812 (16)0.0317 (3)
H40.50080.15660.52780.038*
C50.54361 (15)0.29423 (11)0.51175 (17)0.0353 (3)
H50.47550.31750.55050.042*
C60.62796 (14)0.35510 (10)0.46923 (16)0.0332 (3)
H60.61710.41960.48060.040*
C70.72862 (14)0.32418 (9)0.41007 (15)0.0287 (3)
H70.78570.36630.38040.034*
C80.74163 (12)0.22953 (9)0.39654 (14)0.0242 (3)
C90.93948 (14)0.22510 (11)0.29027 (16)0.0307 (3)
H9A0.89990.27520.21760.037*
H9B0.97850.17890.23650.037*
C101.04906 (13)0.26494 (9)0.42161 (15)0.0258 (3)
C111.08127 (15)0.35817 (10)0.42543 (18)0.0348 (3)
H111.03330.39790.34580.042*
C121.18380 (16)0.39374 (11)0.5457 (2)0.0432 (4)
H121.20490.45770.54850.052*
C131.25468 (15)0.33616 (12)0.66092 (19)0.0413 (4)
H131.32480.36050.74250.050*
C141.22367 (14)0.24302 (12)0.65765 (17)0.0379 (4)
H141.27280.20340.73660.046*
C151.12072 (14)0.20756 (10)0.53890 (16)0.0305 (3)
H151.09900.14370.53760.037*
N0.83419 (11)0.18114 (8)0.34084 (13)0.0264 (2)
O0.87652 (11)0.02811 (8)0.29883 (14)0.0436 (3)
Cl10.77076 (4)0.01204 (3)0.59136 (4)0.03919 (12)
Cl20.57445 (4)0.00267 (2)0.29337 (4)0.03877 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0271 (7)0.0296 (7)0.0291 (7)0.0042 (5)0.0066 (6)0.0071 (6)
C20.0272 (6)0.0251 (7)0.0283 (7)0.0046 (5)0.0044 (5)0.0006 (5)
C30.0236 (6)0.0261 (6)0.0243 (6)0.0017 (5)0.0032 (5)0.0003 (5)
C40.0261 (7)0.0374 (8)0.0320 (7)0.0016 (6)0.0092 (6)0.0021 (6)
C50.0300 (7)0.0419 (9)0.0344 (8)0.0082 (6)0.0100 (6)0.0003 (6)
C60.0357 (8)0.0290 (7)0.0304 (7)0.0088 (6)0.0031 (6)0.0011 (6)
C70.0323 (7)0.0251 (7)0.0269 (7)0.0017 (5)0.0059 (6)0.0025 (5)
C80.0231 (6)0.0272 (7)0.0205 (6)0.0011 (5)0.0036 (5)0.0009 (5)
C90.0304 (7)0.0376 (8)0.0260 (7)0.0071 (6)0.0115 (6)0.0027 (6)
C100.0244 (6)0.0302 (7)0.0262 (6)0.0035 (5)0.0129 (5)0.0033 (5)
C110.0340 (8)0.0300 (7)0.0414 (8)0.0037 (6)0.0129 (6)0.0027 (6)
C120.0397 (9)0.0343 (8)0.0588 (11)0.0140 (7)0.0197 (8)0.0142 (7)
C130.0266 (7)0.0573 (10)0.0403 (9)0.0072 (7)0.0104 (6)0.0191 (8)
C140.0271 (7)0.0534 (10)0.0333 (8)0.0047 (7)0.0089 (6)0.0007 (7)
C150.0303 (7)0.0283 (7)0.0354 (7)0.0005 (5)0.0138 (6)0.0014 (6)
N0.0251 (6)0.0272 (6)0.0278 (6)0.0052 (4)0.0089 (5)0.0048 (5)
O0.0453 (6)0.0340 (6)0.0566 (7)0.0010 (5)0.0231 (6)0.0132 (5)
Cl10.0488 (2)0.0328 (2)0.0331 (2)0.00729 (15)0.00766 (16)0.00495 (14)
Cl20.0370 (2)0.0331 (2)0.0417 (2)0.01408 (14)0.00464 (16)0.00475 (15)
Geometric parameters (Å, º) top
C1—O1.2107 (17)C8—N1.4109 (17)
C1—N1.3637 (18)C9—N1.4647 (17)
C1—C21.5555 (19)C9—C101.5145 (18)
C2—C31.4945 (19)C9—H9A0.9900
C2—Cl21.7811 (13)C9—H9B0.9900
C2—Cl11.7888 (14)C10—C111.388 (2)
C3—C41.3837 (19)C10—C151.393 (2)
C3—C81.3966 (18)C11—C121.394 (2)
C4—C51.398 (2)C11—H110.9500
C4—H40.9500C12—C131.380 (2)
C5—C61.384 (2)C12—H120.9500
C5—H50.9500C13—C141.384 (2)
C6—C71.397 (2)C13—H130.9500
C6—H60.9500C14—C151.388 (2)
C7—C81.3851 (19)C14—H140.9500
C7—H70.9500C15—H150.9500
O—C1—N127.78 (13)N—C9—C10112.05 (11)
O—C1—C2125.98 (13)N—C9—H9A109.2
N—C1—C2106.23 (11)C10—C9—H9A109.2
C3—C2—C1103.98 (11)N—C9—H9B109.2
C3—C2—Cl2114.13 (10)C10—C9—H9B109.2
C1—C2—Cl2109.70 (9)H9A—C9—H9B107.9
C3—C2—Cl1111.92 (9)C11—C10—C15119.20 (13)
C1—C2—Cl1107.79 (9)C11—C10—C9120.74 (13)
Cl2—C2—Cl1109.04 (7)C15—C10—C9120.05 (13)
C4—C3—C8120.99 (13)C10—C11—C12120.20 (15)
C4—C3—C2131.50 (13)C10—C11—H11119.9
C8—C3—C2107.49 (11)C12—C11—H11119.9
C3—C4—C5118.07 (13)C13—C12—C11120.12 (15)
C3—C4—H4121.0C13—C12—H12119.9
C5—C4—H4121.0C11—C12—H12119.9
C6—C5—C4120.52 (14)C12—C13—C14120.07 (14)
C6—C5—H5119.7C12—C13—H13120.0
C4—C5—H5119.7C14—C13—H13120.0
C5—C6—C7121.79 (14)C13—C14—C15119.97 (15)
C5—C6—H6119.1C13—C14—H14120.0
C7—C6—H6119.1C15—C14—H14120.0
C8—C7—C6117.22 (13)C14—C15—C10120.44 (14)
C8—C7—H7121.4C14—C15—H15119.8
C6—C7—H7121.4C10—C15—H15119.8
C7—C8—C3121.40 (12)C1—N—C8111.85 (11)
C7—C8—N128.30 (12)C1—N—C9123.72 (12)
C3—C8—N110.30 (11)C8—N—C9124.41 (11)
O—C1—C2—C3176.71 (14)C2—C3—C8—N1.99 (14)
N—C1—C2—C33.88 (14)N—C9—C10—C11122.02 (14)
O—C1—C2—Cl254.26 (18)N—C9—C10—C1559.29 (17)
N—C1—C2—Cl2126.33 (10)C15—C10—C11—C120.3 (2)
O—C1—C2—Cl164.35 (17)C9—C10—C11—C12178.97 (13)
N—C1—C2—Cl1115.06 (11)C10—C11—C12—C130.7 (2)
C1—C2—C3—C4178.48 (14)C11—C12—C13—C140.3 (2)
Cl2—C2—C3—C459.00 (18)C12—C13—C14—C150.4 (2)
Cl1—C2—C3—C465.44 (17)C13—C14—C15—C100.8 (2)
C1—C2—C3—C83.51 (14)C11—C10—C15—C140.4 (2)
Cl2—C2—C3—C8122.99 (10)C9—C10—C15—C14178.28 (12)
Cl1—C2—C3—C8112.57 (11)O—C1—N—C8177.71 (14)
C8—C3—C4—C50.0 (2)C2—C1—N—C82.90 (15)
C2—C3—C4—C5177.77 (14)O—C1—N—C93.7 (2)
C3—C4—C5—C60.5 (2)C2—C1—N—C9175.65 (11)
C4—C5—C6—C70.7 (2)C7—C8—N—C1179.33 (13)
C5—C6—C7—C80.5 (2)C3—C8—N—C10.67 (15)
C6—C7—C8—C30.00 (19)C7—C8—N—C92.1 (2)
C6—C7—C8—N180.00 (12)C3—C8—N—C9177.86 (12)
C4—C3—C8—C70.3 (2)C10—C9—N—C1107.55 (15)
C2—C3—C8—C7178.01 (12)C10—C9—N—C870.82 (17)
C4—C3—C8—N179.75 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···Oi0.952.643.325 (2)129
C9—H9B···Cgii0.992.933.660 (2)132
C6—H6···Cl2iii0.952.983.4461 (15)112
C13—H13···Cl1iv0.953.013.4815 (18)112
Symmetry codes: (i) x+2, y+1/2, z+1/2; (ii) x, y1/2, z3/2; (iii) x+1, y+1/2, z+1/2; (iv) x+2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC15H11Cl2NO
Mr292.15
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)10.4847 (13), 14.4641 (18), 9.2203 (11)
β (°) 107.244 (2)
V3)1335.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.48 × 0.30 × 0.26
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8835, 3213, 2603
Rint0.028
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.088, 1.05
No. of reflections3213
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.35

Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SAINT-Plus, SHELXTL (Bruker, 1999), ORTEP-3 (Farrugia, 1997) and SCHAKAL99 (Keller, 1999), PLATON (Spek, 2003) and SHELXTL (Bruker, 1999b).

Selected geometric parameters (Å, º) top
C1—O1.2107 (17)C2—C31.4945 (19)
C1—N1.3637 (18)C3—C81.3966 (18)
C1—C21.5555 (19)C8—N1.4109 (17)
N—C1—C2106.23 (11)C3—C8—N110.30 (11)
C3—C2—C1103.98 (11)C1—N—C8111.85 (11)
C8—C3—C2107.49 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···Oi0.952.643.325 (2)129
C9—H9B···Cgii0.992.933.660 (2)132
C6—H6···Cl2iii0.952.983.4461 (15)112
C13—H13···Cl1iv0.953.013.4815 (18)112
Symmetry codes: (i) x+2, y+1/2, z+1/2; (ii) x, y1/2, z3/2; (iii) x+1, y+1/2, z+1/2; (iv) x+2, y+1/2, z+3/2.
Comparison of selected bond lengths and angles (Å, °) for compound (II), KUNMUB and QASXEO top
Structure/RefcodeN—C1C8—N—C1N—C1—C2
(II)1.364 (2)111.8 (1)106.2 (1)
KUNMUBa1.339 (5)112.8 (3)106.1 (3)
QASXEOb1.37114105
aZukerman-Schpector et al. (1993); bMeketa et al. (2005);
 

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