Crystal structure of methyl 1-methyl-2-oxo­spiro­[indoline-3,2′-oxirane]-3′-carboxyl­ate

Savithri, M.P.; Yuvaraj, P.S.; Reddy, B.S.R.; Raja, R.; SubbiahPandi, A.

doi:10.1107/S2056989015006398

organic compounds

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Volume 71| Part 5| May 2015| Pages o274-o275

https://doi.org/10.1107/S2056989015006398

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Crystal structure of methyl 1-methyl-2-oxospiro[indoline-3,2′-oxirane]-3′-carboxylate

M. P. Savithri,^a P. S. Yuvaraj,^b B. S. R. Reddy,^b R. Raja ^c and A. SubbiahPandi ^c ^*

^aDepartment of Physics, Queen Mary's College (Autonomous), Chennai 600 004, India, ^bUniversity of Madras, Industrial Chemistry Laboratory, Central Leather Research Institute, Adyar, Chennai 600 020, India, and ^cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 February 2015; accepted 29 March 2015; online 2 April 2015)

In the title compound, C₁₂H₁₁NO₄, the dihedral angle between the indole ring system (r.m.s. deviation = 0.019 Å) and the oxirane ring is 88.8 (2)°. The oxirane O atom and the bridging ester O atom are in an approximate syn conformation [O—C—C—O = −25.4 (3)°] In the crystal, inversion dimers linked by pair of C—H⋯O hydrogen bonds generate R₂²(8) loops, where the C—H donor group forms part of the oxirane ring. A second C—H⋯O interaction arising from one of the C—H groups of the benzene ring links the dimers into [001] double chains.

Keywords: crystal structure; ester; spiro compound; indoline; oxirane; hydrogen bonding.

CCDC reference: 1056692

1. Related literature

For the bioactivity of indole derivatives, see: Di Fabio et al. (2007 ); Sharma & Tepe (2004 ). For a related structure, see: Savithri et al. (2015 ).

2. Experimental

2.1. Crystal data

C₁₂H₁₁NO₄
M_r = 233.22
Triclinic, $[P \overline 1]$
a = 7.1401 (4) Å
b = 8.7787 (4) Å
c = 9.0678 (4) Å
α = 91.517 (3)°
β = 104.227 (3)°
γ = 94.714 (3)°
V = 548.44 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.30 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.963, T_max = 0.969
11311 measured reflections
1927 independent reflections
1480 reflections with I > 2σ(I)
R_int = 0.037

2.3. Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.173
S = 1.06
1927 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.95 (3)	2.52 (3)	3.414 (3)	157 (2)
C9—H9⋯O1ⁱⁱ	0.93	2.43	3.335 (4)	163
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y, z+1.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1056692

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015006398/hb7369sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006398/hb7369Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015006398/hb7369Isup3.cml

checkCIF report

Related literature top

For the bioactivity of indole derivatives, see: Di Fabio et al. (2007); Sharma & Tepe (2004). For a related structure, see: Savithri et al. (2015).

Experimental top

To a solution of the catalyst of diphenyl[(R)-2-pyrrolidinyl]methanol (0.15mmol) and trans-α-ylideneoxindoles 1 (0.5 mmol) in nHexane for HPLC grade (2.7ml) was added TBHP (5.5M in decane solution, 0.6mol) at room temperature (25°C). The resultant heterogeneous mixture was maintained under stirring until the reaction completion (TLC nHexane/EtOAc). After wards, the crude reaction mixture was purified by flash chromatography on silica gel (nHexane/EtOAc) to furnish the epoxy oxindoles trans-2 and cis-3. Colourless blocks were obtained by slow evaporation of a solution of the title compound in ethyl acetate at room temperature.

Structure description top

For the bioactivity of indole derivatives, see: Di Fabio et al. (2007); Sharma & Tepe (2004). For a related structure, see: Savithri et al. (2015).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The molecular packing as viewed along the a axis. Dashed lines shows the C—H···O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. A partial view of the hydrogen-bond interactions C9—H9···O1 and C3—H3···O3 along a axis.

Methyl 1-methyl-2-oxospiro[indoline-3,2'-oxirane]-3'-carboxylate top

Crystal data top

C₁₂H₁₁NO₄	Z = 2
M_r = 233.22	F(000) = 244
Triclinic, P1	D_x = 1.412 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1401 (4) Å	Cell parameters from 1927 reflections
b = 8.7787 (4) Å	θ = 2.3–25.0°
c = 9.0678 (4) Å	µ = 0.11 mm⁻¹
α = 91.517 (3)°	T = 293 K
β = 104.227 (3)°	Block, colourless
γ = 94.714 (3)°	0.35 × 0.30 × 0.30 mm
V = 548.44 (5) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	1927 independent reflections
Radiation source: fine-focus sealed tube	1480 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω and φ scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
T_min = 0.963, T_max = 0.969	k = −10→10
11311 measured 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.102P)² + 0.172P] where P = (F_o² + 2F_c²)/3
1927 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₁₁NO₄	γ = 94.714 (3)°
M_r = 233.22	V = 548.44 (5) Å³
Triclinic, P1	Z = 2
a = 7.1401 (4) Å	Mo Kα radiation
b = 8.7787 (4) Å	µ = 0.11 mm⁻¹
c = 9.0678 (4) Å	T = 293 K
α = 91.517 (3)°	0.35 × 0.30 × 0.30 mm
β = 104.227 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1927 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1480 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.969	R_int = 0.037
11311 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.30 e Å⁻³
1927 reflections	Δρ_min = −0.27 e Å⁻³
158 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 > 2sigma(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
O2	0.0254 (2)	0.10821 (18)	0.36778 (18)	0.0462 (5)
O4	0.1745 (3)	−0.03538 (19)	0.15149 (19)	0.0536 (5)
O3	0.4764 (3)	0.0432 (2)	0.2809 (2)	0.0632 (6)
O1	0.1739 (3)	0.3246 (2)	0.1663 (2)	0.0643 (6)
N1	0.2372 (3)	0.4866 (2)	0.3794 (3)	0.0504 (6)
C7	0.2040 (3)	0.3195 (3)	0.5623 (3)	0.0425 (6)
C2	0.3047 (4)	0.0282 (2)	0.2698 (3)	0.0429 (6)
C4	0.1736 (3)	0.2320 (2)	0.4166 (2)	0.0379 (5)
C3	0.2223 (4)	0.0750 (3)	0.3974 (3)	0.0428 (6)
C6	0.2456 (3)	0.4711 (3)	0.5343 (3)	0.0486 (6)
C5	0.1928 (3)	0.3492 (3)	0.3012 (3)	0.0438 (6)
C8	0.2075 (4)	0.2738 (4)	0.7065 (3)	0.0566 (7)
H8	0.1811	0.1715	0.7247	0.068*
C11	0.2901 (4)	0.5825 (4)	0.6509 (4)	0.0717 (10)
H11	0.3174	0.6849	0.6334	0.086*
C1	0.2456 (5)	−0.0803 (4)	0.0221 (3)	0.0692 (9)
H1A	0.1393	−0.1255	−0.0577	0.104*
H1B	0.3391	−0.1534	0.0521	0.104*
H1C	0.3056	0.0081	−0.0141	0.104*
C12	0.2681 (5)	0.6277 (3)	0.3066 (5)	0.0774 (10)
H12A	0.2979	0.7114	0.3813	0.116*
H12B	0.1528	0.6440	0.2303	0.116*
H12C	0.3742	0.6214	0.2597	0.116*
C10	0.2921 (5)	0.5344 (5)	0.7951 (4)	0.0845 (12)
H10	0.3223	0.6068	0.8761	0.101*
C9	0.2516 (5)	0.3848 (5)	0.8237 (4)	0.0796 (11)
H9	0.2537	0.3576	0.9225	0.096*
H3	0.273 (4)	0.024 (3)	0.488 (3)	0.052 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0454 (10)	0.0440 (9)	0.0450 (9)	−0.0086 (7)	0.0076 (7)	0.0005 (7)
O4	0.0565 (11)	0.0523 (11)	0.0456 (10)	0.0033 (8)	0.0026 (8)	−0.0115 (8)
O3	0.0524 (13)	0.0730 (13)	0.0597 (12)	0.0065 (9)	0.0068 (9)	−0.0112 (9)
O1	0.0859 (15)	0.0673 (12)	0.0455 (11)	0.0096 (10)	0.0247 (10)	0.0167 (9)
N1	0.0464 (12)	0.0339 (11)	0.0738 (15)	0.0021 (8)	0.0206 (10)	0.0087 (9)
C7	0.0352 (12)	0.0495 (14)	0.0418 (13)	0.0004 (10)	0.0099 (9)	−0.0061 (10)
C2	0.0477 (15)	0.0335 (12)	0.0425 (13)	0.0041 (10)	0.0020 (10)	0.0010 (9)
C4	0.0380 (12)	0.0387 (12)	0.0351 (11)	−0.0034 (9)	0.0078 (9)	0.0011 (9)
C3	0.0477 (14)	0.0373 (12)	0.0382 (13)	−0.0010 (10)	0.0024 (10)	0.0032 (10)
C6	0.0333 (13)	0.0470 (14)	0.0650 (17)	0.0033 (10)	0.0125 (11)	−0.0104 (11)
C5	0.0425 (13)	0.0441 (13)	0.0476 (14)	0.0047 (10)	0.0154 (10)	0.0087 (10)
C8	0.0495 (15)	0.0805 (19)	0.0392 (14)	−0.0009 (13)	0.0128 (11)	−0.0032 (12)
C11	0.0491 (17)	0.0595 (18)	0.100 (3)	0.0038 (13)	0.0116 (16)	−0.0328 (17)
C1	0.077 (2)	0.082 (2)	0.0455 (15)	0.0188 (16)	0.0083 (13)	−0.0170 (14)
C12	0.0574 (18)	0.0453 (16)	0.137 (3)	0.0067 (13)	0.0348 (18)	0.0312 (17)
C10	0.061 (2)	0.110 (3)	0.074 (2)	0.0127 (19)	0.0073 (16)	−0.052 (2)
C9	0.062 (2)	0.128 (3)	0.0476 (17)	0.0067 (19)	0.0138 (14)	−0.0251 (18)

Geometric parameters (Å, º) top

O2—C3	1.421 (3)	C3—H3	0.95 (3)
O2—C4	1.433 (3)	C6—C11	1.380 (4)
O4—C2	1.311 (3)	C8—C9	1.382 (4)
O4—C1	1.446 (3)	C8—H8	0.9300
O3—C2	1.201 (3)	C11—C10	1.382 (5)
O1—C5	1.209 (3)	C11—H11	0.9300
N1—C5	1.356 (3)	C1—H1A	0.9600
N1—C6	1.402 (3)	C1—H1B	0.9600
N1—C12	1.446 (3)	C1—H1C	0.9600
C7—C8	1.373 (3)	C12—H12A	0.9600
C7—C6	1.384 (4)	C12—H12B	0.9600
C7—C4	1.470 (3)	C12—H12C	0.9600
C2—C3	1.484 (4)	C10—C9	1.367 (5)
C4—C3	1.466 (3)	C10—H10	0.9300
C4—C5	1.509 (3)	C9—H9	0.9300

C3—O2—C4	61.80 (14)	O1—C5—C4	126.6 (2)
C2—O4—C1	116.2 (2)	N1—C5—C4	106.3 (2)
C5—N1—C6	111.2 (2)	C7—C8—C9	117.8 (3)
C5—N1—C12	122.4 (3)	C7—C8—H8	121.1
C6—N1—C12	126.4 (2)	C9—C8—H8	121.1
C8—C7—C6	121.6 (2)	C6—C11—C10	116.7 (3)
C8—C7—C4	131.6 (2)	C6—C11—H11	121.7
C6—C7—C4	106.7 (2)	C10—C11—H11	121.7
O3—C2—O4	125.0 (2)	O4—C1—H1A	109.5
O3—C2—C3	121.3 (2)	O4—C1—H1B	109.5
O4—C2—C3	113.7 (2)	H1A—C1—H1B	109.5
O2—C4—C3	58.71 (14)	O4—C1—H1C	109.5
O2—C4—C7	123.07 (19)	H1A—C1—H1C	109.5
C3—C4—C7	125.9 (2)	H1B—C1—H1C	109.5
O2—C4—C5	116.78 (18)	N1—C12—H12A	109.5
C3—C4—C5	121.0 (2)	N1—C12—H12B	109.5
C7—C4—C5	105.51 (19)	H12A—C12—H12B	109.5
O2—C3—C4	59.48 (14)	N1—C12—H12C	109.5
O2—C3—C2	119.95 (19)	H12A—C12—H12C	109.5
C4—C3—C2	121.3 (2)	H12B—C12—H12C	109.5
O2—C3—H3	117.1 (15)	C9—C10—C11	122.8 (3)
C4—C3—H3	116.4 (16)	C9—C10—H10	118.6
C2—C3—H3	112.8 (15)	C11—C10—H10	118.6
C11—C6—C7	120.9 (3)	C10—C9—C8	120.3 (3)
C11—C6—N1	128.8 (3)	C10—C9—H9	119.9
C7—C6—N1	110.3 (2)	C8—C9—H9	119.9
O1—C5—N1	127.2 (2)

C1—O4—C2—O3	−4.4 (4)	C4—C7—C6—N1	2.0 (3)
C1—O4—C2—C3	178.6 (2)	C5—N1—C6—C11	178.4 (2)
C3—O2—C4—C7	−115.0 (2)	C12—N1—C6—C11	−2.3 (4)
C3—O2—C4—C5	111.7 (2)	C5—N1—C6—C7	−0.6 (3)
C8—C7—C4—O2	44.0 (4)	C12—N1—C6—C7	178.7 (2)
C6—C7—C4—O2	−140.1 (2)	C6—N1—C5—O1	179.6 (2)
C8—C7—C4—C3	−28.9 (4)	C12—N1—C5—O1	0.2 (4)
C6—C7—C4—C3	147.0 (2)	C6—N1—C5—C4	−1.0 (3)
C8—C7—C4—C5	−178.4 (2)	C12—N1—C5—C4	179.7 (2)
C6—C7—C4—C5	−2.5 (2)	O2—C4—C5—O1	−37.7 (3)
C4—O2—C3—C2	−110.9 (2)	C3—C4—C5—O1	30.3 (4)
C7—C4—C3—O2	110.4 (2)	C7—C4—C5—O1	−178.4 (2)
C5—C4—C3—O2	−104.4 (2)	O2—C4—C5—N1	142.9 (2)
O2—C4—C3—C2	108.6 (2)	C3—C4—C5—N1	−149.1 (2)
C7—C4—C3—C2	−141.0 (2)	C7—C4—C5—N1	2.2 (2)
C5—C4—C3—C2	4.2 (3)	C6—C7—C8—C9	0.9 (4)
O3—C2—C3—O2	157.5 (2)	C4—C7—C8—C9	176.2 (3)
O4—C2—C3—O2	−25.4 (3)	C7—C6—C11—C10	0.5 (4)
O3—C2—C3—C4	87.1 (3)	N1—C6—C11—C10	−178.5 (2)
O4—C2—C3—C4	−95.8 (2)	C6—C11—C10—C9	−0.3 (5)
C8—C7—C6—C11	−0.8 (4)	C11—C10—C9—C8	0.5 (5)
C4—C7—C6—C11	−177.1 (2)	C7—C8—C9—C10	−0.7 (4)
C8—C7—C6—N1	178.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.95 (3)	2.52 (3)	3.414 (3)	157 (2)
C9—H9···O1ⁱⁱ	0.93	2.43	3.335 (4)	163

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.95 (3)	2.52 (3)	3.414 (3)	157 (2)
C9—H9···O1ⁱⁱ	0.93	2.43	3.335 (4)	163

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

Acknowledgements

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for the data collection.

References

Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Di Fabio, R., Micheli, F., Alvaro, G., Cavanni, P., Donati, D., Gagliardi, T., Fontana, G., Giovannini, R., Maffeis, M., Mingardi, A., Tranquillini, M. E. & Vitulli, G. (2007). Bioorg. Med. Chem. Lett. 17, 2254–2259. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Savithri, M. P., Yuvaraj, P. S., Reddy, B. S. R., Raja, R. & SubbiahPandi, A. (2015). Acta Cryst. E71, o188–o189. CSD CrossRef IUCr Journals Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 5| May 2015| Pages o274-o275

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of methyl 1-methyl-2-oxo­spiro­[indoline-3,2′-oxirane]-3′-carboxyl­ate

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of methyl 1-methyl-2-oxospiro[indoline-3,2′-oxirane]-3′-carboxylate