1′-Methyl-4′-(4-methyl­phen­yl)dispiro­[1-benzopyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione

Lakshmanan, D.; Murugavel, S.; Kannan, D.; Bakthadoss, M.

doi:10.1107/S1600536811051440

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o11

doi:10.1107/S1600536811051440

Open

access

1′-Methyl-4′-(4-methylphenyl)dispiro[1-benzopyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione

D. Lakshmanan,^a S. Murugavel,^b ^* D. Kannan ^c and M. Bakthadoss ^c ‡

^aDepartment of Physics, C. Abdul Hakeem College of Engineering & Technology, Melvisharam, Vellore 632 509, India, ^bDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India, and ^cDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: smurugavel27@gmail.com

(Received 28 November 2011; accepted 29 November 2011; online 3 December 2011)

In the title compound, C₂₇H₂₄N₂O₃, the pyrroldine ring adopts a twist conformation, while the six-membered pyranone ring of the coumarin ring system is in a sofa conformation. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion R₂²(8) dimers. These dimers are further connected via C—H⋯O hydrogen bonds.

Related literature

For applications of pyrrolidine derivatives, see: Huryn et al. (1991 ); Suzuki et al. (1994 ); Waldmann (1995 ). For ring puckering parameters, see: Cremer & Pople (1975 ) and for asymmetry parameters, see: Duax et al. (1976 ). For closely related pyrrolidine structures, see: Selvanayagam et al. (2011 ); Ali et al. (2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₇H₂₄N₂O₃
M_r = 424.48
Monoclinic, P 2₁ /c
a = 10.4543 (3) Å
b = 14.6018 (4) Å
c = 14.7266 (4) Å
β = 104.043 (2)°
V = 2180.85 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.978, T_max = 0.985
30221 measured reflections
7055 independent reflections
4544 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.153
S = 1.02
7055 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.02	2.874 (1)	174
C5—H5B⋯O3ⁱⁱ	0.96	2.59	3.407 (2)	143
Symmetry codes: (i) -x+2, -y+2, -z; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811051440/bt5735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051440/bt5735Isup2.hkl

checkCIF report

Comment top

Highly functionalized pyrrolidines have gained much interest in the past few years as they constitute the main structural element of many natural and synthetic pharmacologically active compounds (Waldmann, 1995). Optically active pyrrolidines have been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis (Suzuki et al., 1994; Huryn et al., 1991). In view of this importance, the crystal structure of the title compound has been carried out and the results are presented here.

The title compound consists of a pyrrolidine ring connected to a oxindole ring system at C1, a coumarine moiety at C2 and a benzene ring at C3. The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig.1.

The pyrrolidine (N1/C1–C4) ring adopts a twist conformation , with twist about the C4—N1 bond; the puckering parameters (Cremer & Pople, 1975), q₂ = 0.4216 (14) Å and ϕ₂ = 156.9 (2)°, and asymmetry parameters (Duax et al., 1976) ΔC₂[C4—N1] = 5.0 Å. The six membered pyranone ring (O2/C2/C13/C14/C19/C20) of the coumarine moiety adopts screw-boat conformation as indicated from the puckering parameters: Q = 0.5296 (15) Å, θ = 65.9 (2)° and ϕ = 215.9 (2)°. The oxindole unit (N2/C1/C6–C12) is essentially planar [maximum deviation = 0.048 (1) Å for the C1 atom] and is oriented at a dihedral angles of 87.1 (1)° and 28.6 (1)°, respectively, with the pyrrolidine and coumarine rings. The sum of angles at N1 of the pyrrolidine ring (337°) is in accordance with sp³ hybridization, and the sum of angles at N2 of the indole moiety (360°) is in accordance with sp² hybridization. The geometric parameters of the title molecule agrees well with those reported for similar structures (Selvanayagam et al., 2011; Ali et al., 2010).

Ihe molecular structure is stabilized by C3—H3···O3 and C13—H13A···O1 intramolecular hydrogen bonds, forming S(5) and S(6) ring motifs, respectively (Bernstein et al., 1995) (Table 1). The molecular structure is further stabilized by an intramolecular π—π interactions with Cg1—Cg2 seperation of 3.539 (1) Å. (Fig. 2; Cg1 and Cg2 are the centroids of the (N2/C1/C6/C7/C12) indole ring, (C14–C19) benzene ring, respectively). The crystal packing is stabilized by intermolecular N—H···O and C—H···O hydrogen bonds. The molecules at x, y, z and 2-x, 2-y, -z are linked by N2—H2···O1 hydrogen bonds into cyclic centrosymmetric R₂²(8) dimers. This dimers are further connected by C5—H5B···O3 hydrogen bonds forming supramolecular zig zag chains along the c axis (Fig. 3).

Related literature top

For applications of pyrrolidine derivatives, see: Huryn et al. (1991 ); Suzuki et al. (1994); Waldmann (1995). For ring puckering parameters, see: Cremer & Pople (1975) and for asymmetry parameters, see: Duax et al. (1976). For closely related pyrrolidine structures, see: Selvanayagam et al. (2011); Ali et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of E-3-(4-methylbenzylidene)chroman-2-one (0.125 g, 0.5 mmol), isatin (0.08 g, 0.55 mmol) and N- methylglycine (0.025 g, 0.55 mmol) in toluene (5 ml) as solvent was allowed to reflux for 6 hours. After work up, the crude mass was purified by column chromatography to yield the pure product (0.195 g, 92% yield). The compound was recrystallized from ethyl acetate solvent. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a ethylacetate solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); 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 the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small cycles of arbitrary radius.
	Fig. 2. A view of the π···π interactions (dotted lines) in the molecular structure of the title compound. Cg1 and Cg2 are the centroids of the (N2/C1/C6/C7/C12) indole ring and (C14–C19) benzene ring, respectively.
	Fig. 3. View of supramolecular zig zag chain in (I) with N—H···O (blue dashed lines) and C—H···O (red dashed lines) hydrogen bonds along the c axis.[ Colour code: O(red), N(blue), C(black) & H(green).

1'-Methyl-4'-(4-methylphenyl)dispiro[1-benzopyran-3(4H),3'- pyrrolidine-2',3''-indoline]-2,2''-dione top

Crystal data top

C₂₇H₂₄N₂O₃	F(000) = 896
M_r = 424.48	D_x = 1.293 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7063 reflections
a = 10.4543 (3) Å	θ = 2.0–31.2°
b = 14.6018 (4) Å	µ = 0.09 mm⁻¹
c = 14.7266 (4) Å	T = 293 K
β = 104.043 (2)°	Block, colourless
V = 2180.85 (10) Å³	0.26 × 0.23 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7055 independent reflections
Radiation source: fine-focus sealed tube	4544 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 10.0 pixels mm^-1	θ_max = 31.2°, θ_min = 2.0°
ω scans	h = −15→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −21→21
T_min = 0.978, T_max = 0.985	l = −20→21
30221 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0694P)² + 0.398P] where P = (F_o² + 2F_c²)/3
7055 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₇H₂₄N₂O₃	V = 2180.85 (10) Å³
M_r = 424.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4543 (3) Å	µ = 0.09 mm⁻¹
b = 14.6018 (4) Å	T = 293 K
c = 14.7266 (4) Å	0.26 × 0.23 × 0.18 mm
β = 104.043 (2)°

Data collection top

Bruker APEXII CCD diffractometer	7055 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4544 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.985	R_int = 0.031
30221 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.02	Δρ_max = 0.31 e Å⁻³
7055 reflections	Δρ_min = −0.23 e Å⁻³
291 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
C1	0.80511 (12)	0.84780 (8)	0.09959 (8)	0.0326 (2)
C2	0.80733 (12)	0.86879 (8)	0.20643 (8)	0.0335 (2)
C3	0.65980 (12)	0.89026 (9)	0.20385 (9)	0.0367 (3)
H3	0.6207	0.8333	0.2197	0.044*
C4	0.59877 (13)	0.90885 (11)	0.10112 (10)	0.0449 (3)
H4A	0.5042	0.8989	0.0858	0.054*
H4B	0.6166	0.9709	0.0841	0.054*
C5	0.63008 (17)	0.84632 (12)	−0.04637 (10)	0.0548 (4)
H5A	0.5385	0.8313	−0.0695	0.082*
H5B	0.6830	0.8033	−0.0705	0.082*
H5C	0.6459	0.9070	−0.0662	0.082*
C6	0.87724 (13)	0.92422 (9)	0.05686 (9)	0.0383 (3)
C7	0.97873 (13)	0.79028 (9)	0.03856 (9)	0.0382 (3)
C8	1.06331 (16)	0.72827 (11)	0.01407 (11)	0.0528 (4)
H8	1.1311	0.7470	−0.0125	0.063*
C9	1.04343 (19)	0.63686 (12)	0.03057 (13)	0.0626 (5)
H9	1.1002	0.5932	0.0161	0.075*
C10	0.94146 (19)	0.60908 (10)	0.06787 (12)	0.0586 (4)
H10	0.9291	0.5469	0.0767	0.070*
C11	0.85666 (16)	0.67219 (9)	0.09259 (10)	0.0455 (3)
H11	0.7871	0.6532	0.1172	0.055*
C12	0.87840 (13)	0.76409 (8)	0.07963 (8)	0.0348 (3)
C13	0.90158 (13)	0.94596 (10)	0.25105 (10)	0.0450 (3)
H13A	0.8788	1.0018	0.2152	0.054*
H13B	0.8931	0.9573	0.3142	0.054*
C14	1.04058 (14)	0.91967 (12)	0.25330 (11)	0.0520 (4)
C15	1.13597 (18)	0.97997 (16)	0.23772 (14)	0.0717 (6)
H15	1.1152	1.0414	0.2254	0.086*
C16	1.2617 (2)	0.9486 (2)	0.24059 (18)	0.0957 (8)
H16	1.3259	0.9893	0.2313	0.115*
C17	1.2920 (2)	0.8584 (2)	0.2570 (2)	0.1000 (9)
H17	1.3766	0.8380	0.2578	0.120*
C18	1.19962 (18)	0.79673 (18)	0.27257 (14)	0.0791 (6)
H18	1.2205	0.7352	0.2840	0.095*
C19	1.07479 (14)	0.82966 (13)	0.27055 (10)	0.0544 (4)
C20	0.85238 (14)	0.78283 (10)	0.26401 (9)	0.0418 (3)
C21	0.63774 (12)	0.96203 (9)	0.27238 (10)	0.0395 (3)
C22	0.64635 (16)	0.93919 (11)	0.36474 (11)	0.0509 (4)
H22	0.6657	0.8791	0.3843	0.061*
C23	0.62671 (17)	1.00382 (13)	0.42869 (12)	0.0584 (4)
H23	0.6352	0.9864	0.4906	0.070*
C24	0.59504 (15)	1.09288 (12)	0.40314 (13)	0.0560 (4)
C25	0.5856 (2)	1.11562 (12)	0.31114 (15)	0.0677 (5)
H25	0.5637	1.1754	0.2915	0.081*
C26	0.60777 (18)	1.05209 (11)	0.24708 (12)	0.0576 (4)
H26	0.6024	1.0703	0.1858	0.069*
C27	0.5729 (2)	1.16348 (15)	0.47218 (17)	0.0806 (6)
H27A	0.6150	1.2198	0.4624	0.121*
H27B	0.6095	1.1420	0.5347	0.121*
H27C	0.4800	1.1737	0.4635	0.121*
N1	0.66462 (11)	0.84226 (8)	0.05524 (8)	0.0395 (2)
N2	0.97478 (11)	0.88502 (8)	0.02528 (8)	0.0430 (3)
H2	1.0282	0.9148	0.0000	0.052*
O1	0.84748 (11)	1.00547 (6)	0.05046 (8)	0.0525 (3)
O2	0.98473 (10)	0.76670 (8)	0.29036 (7)	0.0546 (3)
O3	0.78215 (12)	0.72821 (8)	0.28723 (8)	0.0607 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0345 (6)	0.0302 (6)	0.0358 (6)	−0.0025 (4)	0.0135 (5)	0.0040 (4)
C2	0.0307 (6)	0.0370 (6)	0.0351 (6)	−0.0028 (5)	0.0122 (5)	0.0013 (5)
C3	0.0304 (6)	0.0405 (6)	0.0426 (7)	−0.0013 (5)	0.0154 (5)	0.0039 (5)
C4	0.0343 (6)	0.0549 (8)	0.0459 (7)	0.0033 (6)	0.0108 (6)	0.0029 (6)
C5	0.0553 (9)	0.0659 (10)	0.0397 (7)	0.0022 (7)	0.0051 (6)	0.0038 (7)
C6	0.0412 (7)	0.0345 (6)	0.0434 (7)	−0.0018 (5)	0.0184 (5)	0.0055 (5)
C7	0.0409 (7)	0.0403 (7)	0.0343 (6)	0.0031 (5)	0.0110 (5)	−0.0006 (5)
C8	0.0489 (8)	0.0610 (10)	0.0504 (8)	0.0121 (7)	0.0157 (7)	−0.0087 (7)
C9	0.0666 (11)	0.0519 (9)	0.0654 (10)	0.0217 (8)	0.0080 (9)	−0.0158 (8)
C10	0.0752 (11)	0.0342 (7)	0.0583 (9)	0.0090 (7)	0.0007 (8)	−0.0044 (6)
C11	0.0564 (8)	0.0341 (6)	0.0432 (7)	−0.0043 (6)	0.0066 (6)	0.0020 (5)
C12	0.0406 (6)	0.0319 (6)	0.0315 (6)	0.0005 (5)	0.0079 (5)	0.0013 (4)
C13	0.0368 (7)	0.0510 (8)	0.0505 (8)	−0.0090 (6)	0.0172 (6)	−0.0151 (6)
C14	0.0345 (7)	0.0732 (10)	0.0499 (8)	−0.0107 (7)	0.0131 (6)	−0.0233 (7)
C15	0.0484 (9)	0.0934 (14)	0.0787 (12)	−0.0280 (9)	0.0260 (9)	−0.0347 (10)
C16	0.0436 (10)	0.144 (2)	0.1069 (18)	−0.0334 (13)	0.0318 (11)	−0.0466 (17)
C17	0.0351 (9)	0.155 (3)	0.1101 (19)	−0.0022 (13)	0.0174 (10)	−0.0376 (18)
C18	0.0427 (9)	0.1165 (17)	0.0735 (12)	0.0177 (10)	0.0055 (8)	−0.0151 (12)
C19	0.0348 (7)	0.0841 (12)	0.0422 (8)	0.0019 (7)	0.0050 (6)	−0.0116 (7)
C20	0.0441 (7)	0.0485 (8)	0.0344 (6)	0.0056 (6)	0.0126 (5)	0.0054 (5)
C21	0.0312 (6)	0.0437 (7)	0.0471 (7)	0.0024 (5)	0.0159 (5)	0.0019 (5)
C22	0.0566 (9)	0.0508 (8)	0.0516 (8)	0.0114 (7)	0.0253 (7)	0.0060 (6)
C23	0.0592 (10)	0.0708 (11)	0.0512 (9)	0.0109 (8)	0.0248 (8)	−0.0019 (8)
C24	0.0411 (8)	0.0614 (10)	0.0685 (10)	0.0054 (7)	0.0190 (7)	−0.0145 (8)
C25	0.0757 (12)	0.0464 (9)	0.0819 (13)	0.0145 (8)	0.0208 (10)	−0.0001 (8)
C26	0.0701 (11)	0.0485 (9)	0.0561 (9)	0.0107 (7)	0.0189 (8)	0.0069 (7)
C27	0.0697 (12)	0.0794 (14)	0.0981 (16)	0.0079 (10)	0.0307 (11)	−0.0328 (11)
N1	0.0348 (5)	0.0465 (6)	0.0364 (5)	−0.0024 (4)	0.0073 (4)	0.0027 (4)
N2	0.0459 (6)	0.0404 (6)	0.0509 (7)	−0.0014 (5)	0.0274 (5)	0.0064 (5)
O1	0.0583 (6)	0.0341 (5)	0.0744 (7)	0.0032 (4)	0.0344 (5)	0.0138 (5)
O2	0.0464 (6)	0.0712 (7)	0.0436 (5)	0.0159 (5)	0.0056 (4)	0.0086 (5)
O3	0.0682 (7)	0.0571 (7)	0.0645 (7)	0.0054 (5)	0.0314 (6)	0.0256 (5)

Geometric parameters (Å, º) top

C1—N1	1.4577 (16)	C13—H13A	0.9700
C1—C12	1.5089 (17)	C13—H13B	0.9700
C1—C6	1.5621 (16)	C14—C19	1.370 (3)
C1—C2	1.5975 (17)	C14—C15	1.391 (2)
C2—C20	1.5240 (18)	C15—C16	1.383 (3)
C2—C13	1.5356 (18)	C15—H15	0.9300
C2—C3	1.5652 (17)	C16—C17	1.363 (4)
C3—C21	1.5110 (18)	C16—H16	0.9300
C3—C4	1.5169 (19)	C17—C18	1.380 (4)
C3—H3	0.9800	C17—H17	0.9300
C4—N1	1.4497 (18)	C18—C19	1.384 (2)
C4—H4A	0.9700	C18—H18	0.9300
C4—H4B	0.9700	C19—O2	1.396 (2)
C5—N1	1.4529 (18)	C20—O3	1.1892 (17)
C5—H5A	0.9600	C20—O2	1.3637 (17)
C5—H5B	0.9600	C21—C26	1.382 (2)
C5—H5C	0.9600	C21—C22	1.382 (2)
C6—O1	1.2243 (16)	C22—C23	1.383 (2)
C6—N2	1.3467 (17)	C22—H22	0.9300
C7—C8	1.3736 (19)	C23—C24	1.372 (2)
C7—C12	1.3857 (18)	C23—H23	0.9300
C7—N2	1.3964 (18)	C24—C25	1.375 (3)
C8—C9	1.381 (2)	C24—C27	1.505 (2)
C8—H8	0.9300	C25—C26	1.382 (2)
C9—C10	1.374 (3)	C25—H25	0.9300
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.387 (2)	C27—H27A	0.9600
C10—H10	0.9300	C27—H27B	0.9600
C11—C12	1.3820 (18)	C27—H27C	0.9600
C11—H11	0.9300	N2—H2	0.8600
C13—C14	1.496 (2)

N1—C1—C12	111.83 (10)	C2—C13—H13B	109.7
N1—C1—C6	113.05 (10)	H13A—C13—H13B	108.2
C12—C1—C6	100.52 (9)	C19—C14—C15	118.22 (16)
N1—C1—C2	102.96 (9)	C19—C14—C13	117.33 (14)
C12—C1—C2	117.43 (10)	C15—C14—C13	124.44 (17)
C6—C1—C2	111.50 (10)	C16—C15—C14	120.0 (2)
C20—C2—C13	106.66 (11)	C16—C15—H15	120.0
C20—C2—C3	110.37 (10)	C14—C15—H15	120.0
C13—C2—C3	112.93 (10)	C17—C16—C15	120.2 (2)
C20—C2—C1	108.58 (10)	C17—C16—H16	119.9
C13—C2—C1	114.63 (10)	C15—C16—H16	119.9
C3—C2—C1	103.64 (9)	C16—C17—C18	121.2 (2)
C21—C3—C4	116.52 (11)	C16—C17—H17	119.4
C21—C3—C2	115.59 (10)	C18—C17—H17	119.4
C4—C3—C2	103.51 (10)	C17—C18—C19	117.7 (2)
C21—C3—H3	106.9	C17—C18—H18	121.2
C4—C3—H3	106.9	C19—C18—H18	121.2
C2—C3—H3	106.9	C14—C19—C18	122.66 (18)
N1—C4—C3	102.26 (11)	C14—C19—O2	120.77 (13)
N1—C4—H4A	111.3	C18—C19—O2	116.53 (18)
C3—C4—H4A	111.3	O3—C20—O2	117.19 (13)
N1—C4—H4B	111.3	O3—C20—C2	125.69 (13)
C3—C4—H4B	111.3	O2—C20—C2	117.12 (12)
H4A—C4—H4B	109.2	C26—C21—C22	116.83 (14)
N1—C5—H5A	109.5	C26—C21—C3	122.78 (13)
N1—C5—H5B	109.5	C22—C21—C3	120.39 (12)
H5A—C5—H5B	109.5	C21—C22—C23	121.36 (15)
N1—C5—H5C	109.5	C21—C22—H22	119.3
H5A—C5—H5C	109.5	C23—C22—H22	119.3
H5B—C5—H5C	109.5	C24—C23—C22	121.72 (16)
O1—C6—N2	125.79 (12)	C24—C23—H23	119.1
O1—C6—C1	125.78 (11)	C22—C23—H23	119.1
N2—C6—C1	108.39 (11)	C23—C24—C25	117.01 (15)
C8—C7—C12	122.44 (13)	C23—C24—C27	122.04 (18)
C8—C7—N2	127.98 (13)	C25—C24—C27	120.95 (18)
C12—C7—N2	109.56 (11)	C24—C25—C26	121.77 (16)
C7—C8—C9	117.18 (16)	C24—C25—H25	119.1
C7—C8—H8	121.4	C26—C25—H25	119.1
C9—C8—H8	121.4	C21—C26—C25	121.29 (16)
C10—C9—C8	121.34 (15)	C21—C26—H26	119.4
C10—C9—H9	119.3	C25—C26—H26	119.4
C8—C9—H9	119.3	C24—C27—H27A	109.5
C9—C10—C11	121.08 (15)	C24—C27—H27B	109.5
C9—C10—H10	119.5	H27A—C27—H27B	109.5
C11—C10—H10	119.5	C24—C27—H27C	109.5
C12—C11—C10	118.15 (15)	H27A—C27—H27C	109.5
C12—C11—H11	120.9	H27B—C27—H27C	109.5
C10—C11—H11	120.9	C4—N1—C5	115.16 (11)
C11—C12—C7	119.70 (12)	C4—N1—C1	107.14 (10)
C11—C12—C1	130.64 (12)	C5—N1—C1	115.52 (11)
C7—C12—C1	109.60 (10)	C6—N2—C7	111.83 (11)
C14—C13—C2	109.89 (12)	C6—N2—H2	124.1
C14—C13—H13A	109.7	C7—N2—H2	124.1
C2—C13—H13A	109.7	C20—O2—C19	121.05 (12)
C14—C13—H13B	109.7

N1—C1—C2—C20	107.25 (11)	C13—C14—C15—C16	−179.46 (17)
C12—C1—C2—C20	−16.07 (14)	C14—C15—C16—C17	1.2 (3)
C6—C1—C2—C20	−131.25 (11)	C15—C16—C17—C18	−1.0 (4)
N1—C1—C2—C13	−133.62 (11)	C16—C17—C18—C19	0.2 (4)
C12—C1—C2—C13	103.06 (13)	C15—C14—C19—C18	−0.3 (2)
C6—C1—C2—C13	−12.12 (15)	C13—C14—C19—C18	178.73 (15)
N1—C1—C2—C3	−10.10 (11)	C15—C14—C19—O2	177.45 (14)
C12—C1—C2—C3	−133.42 (11)	C13—C14—C19—O2	−3.5 (2)
C6—C1—C2—C3	111.40 (11)	C17—C18—C19—C14	0.5 (3)
C20—C2—C3—C21	98.57 (13)	C17—C18—C19—O2	−177.40 (18)
C13—C2—C3—C21	−20.72 (15)	C13—C2—C20—O3	138.05 (15)
C1—C2—C3—C21	−145.34 (11)	C3—C2—C20—O3	15.04 (19)
C20—C2—C3—C4	−132.81 (11)	C1—C2—C20—O3	−97.92 (16)
C13—C2—C3—C4	107.91 (13)	C13—C2—C20—O2	−42.67 (15)
C1—C2—C3—C4	−16.72 (12)	C3—C2—C20—O2	−165.68 (11)
C21—C3—C4—N1	166.01 (10)	C1—C2—C20—O2	81.35 (14)
C2—C3—C4—N1	37.96 (13)	C4—C3—C21—C26	−22.73 (19)
N1—C1—C6—O1	55.83 (18)	C2—C3—C21—C26	99.17 (16)
C12—C1—C6—O1	175.18 (14)	C4—C3—C21—C22	156.91 (13)
C2—C1—C6—O1	−59.61 (18)	C2—C3—C21—C22	−81.19 (16)
N1—C1—C6—N2	−122.03 (12)	C26—C21—C22—C23	−0.4 (2)
C12—C1—C6—N2	−2.69 (13)	C3—C21—C22—C23	179.90 (14)
C2—C1—C6—N2	122.52 (12)	C21—C22—C23—C24	1.4 (3)
C12—C7—C8—C9	1.1 (2)	C22—C23—C24—C25	−1.0 (3)
N2—C7—C8—C9	−176.91 (14)	C22—C23—C24—C27	179.71 (17)
C7—C8—C9—C10	1.5 (2)	C23—C24—C25—C26	−0.4 (3)
C8—C9—C10—C11	−1.7 (3)	C27—C24—C25—C26	178.90 (18)
C9—C10—C11—C12	−0.7 (2)	C22—C21—C26—C25	−1.0 (2)
C10—C11—C12—C7	3.2 (2)	C3—C21—C26—C25	178.70 (15)
C10—C11—C12—C1	−179.77 (13)	C24—C25—C26—C21	1.4 (3)
C8—C7—C12—C11	−3.5 (2)	C3—C4—N1—C5	−177.27 (12)
N2—C7—C12—C11	174.86 (12)	C3—C4—N1—C1	−47.26 (13)
C8—C7—C12—C1	178.92 (13)	C12—C1—N1—C4	162.40 (10)
N2—C7—C12—C1	−2.76 (14)	C6—C1—N1—C4	−85.00 (12)
N1—C1—C12—C11	−53.82 (18)	C2—C1—N1—C4	35.44 (12)
C6—C1—C12—C11	−174.04 (13)	C12—C1—N1—C5	−67.79 (14)
C2—C1—C12—C11	64.87 (18)	C6—C1—N1—C5	44.80 (15)
N1—C1—C12—C7	123.46 (11)	C2—C1—N1—C5	165.25 (11)
C6—C1—C12—C7	3.23 (13)	O1—C6—N2—C7	−176.60 (14)
C2—C1—C12—C7	−117.86 (11)	C1—C6—N2—C7	1.27 (15)
C20—C2—C13—C14	57.15 (15)	C8—C7—N2—C6	179.11 (14)
C3—C2—C13—C14	178.55 (11)	C12—C7—N2—C6	0.90 (16)
C1—C2—C13—C14	−63.05 (16)	O3—C20—O2—C19	−176.49 (13)
C2—C13—C14—C19	−36.75 (18)	C2—C20—O2—C19	4.17 (18)
C2—C13—C14—C15	142.23 (15)	C14—C19—O2—C20	21.8 (2)
C19—C14—C15—C16	−0.5 (3)	C18—C19—O2—C20	−160.33 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.02	2.874 (1)	174
C5—H5B···O3ⁱⁱ	0.96	2.59	3.407 (2)	143

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

Experimental details

Crystal data
Chemical formula	C₂₇H₂₄N₂O₃
M_r	424.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.4543 (3), 14.6018 (4), 14.7266 (4)
β (°)	104.043 (2)
V (Å³)	2180.85 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.23 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.978, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	30221, 7055, 4544
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.728

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.153, 1.02
No. of reflections	7055
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.02	2.874 (1)	174.4
C5—H5B···O3ⁱⁱ	0.96	2.59	3.407 (2)	142.6

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

Footnotes

‡Additional correspondence author, e-mail: bhakthadoss@yahoo.com.

Acknowledgements

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

References

Ali, M. A., Ismail, R., Tan, S. C., Yeap, C. S. & Fun, H.-K. (2010). Acta Cryst. E66, o2533–o2534. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Duax, W. L., Weeks, C. M. & Rohrer, D. C. (1976). Topics in Stereochemistry, Vol. 9, edited by E. L. Eliel & N. L. Allinger, pp. 271–383. New York: John Wiley. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Huryn, D. M., Trost, B. M. & Fleming, I. (1991). Comp. Org. Synth. 1, 64–74. Google Scholar
Selvanayagam, S., Ravikumar, K., Saravanan, P. & Raghunathan, R. (2011). Acta Cryst. E67, o751. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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
Suzuki, H., Aoyagi, S. & Kibayashi, C. (1994). Tetrahedron Lett. 35, 6119–6122. CrossRef CAS Web of Science Google Scholar
Waldmann, H. (1995). Synlett. pp. 133–141. CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o11

doi:10.1107/S1600536811051440

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

1′-Methyl-4′-(4-methyl­phen­yl)di­spiro­[1-benzo­pyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

1′-Methyl-4′-(4-methylphenyl)dispiro[1-benzopyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione