Methyl 3-[(1H-benzimidazol-1-yl)meth­yl]-1-methyl-4-(4-methyl­phen­yl)-2′-oxopyrrolidine-2-spiro-3′-1-benzimidazole-3-carboxyl­ate

Selvanayagam, S.; Sridhar, B.; Ravikumar, K.; Kathiravan, S.; Raghunathan, R.

doi:10.1107/S1600536810035312

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages o2508-o2509

doi:10.1107/S1600536810035312

Open

access

Methyl 3-[(1H-benzimidazol-1-yl)methyl]-1-methyl-4-(4-methylphenyl)-2′-oxopyrrolidine-2-spiro-3′-1-benzimidazole-3-carboxylate

S. Selvanayagam,^a ^* B. Sridhar,^b K. Ravikumar,^b S. Kathiravan ^c and R. Raghunathan ^c

^aDepartment of Physics, Kalasalingam University, Krishnankoil 626 190, India, ^bLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 007, India, and ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: s_selvanayagam@rediffmail.com

(Received 27 August 2010; accepted 1 September 2010; online 4 September 2010)

In the title compound, C₂₉H₂₈N₄O₃, the pyrrolidine ring adopts a twist conformation whereas the oxindole and benzimidazole residues are approximately planar with maximum deviations of 0.159 (1) and 0.011 (1) Å, respectively. The oxindole residue is almost perpendicular to the benzimidazole residue, making a dihedral angle of 89.2 (1)°. The methyl-substituted benzene ring is oriented at angles of 47.7 (1) and 71.0 (1)°, respectively, with respect to the oxindole and benzimidazole residues. An intramolecular C—H⋯O hydrogen bond is observed. In the crystal, molecules associate via N—H⋯N hydrogen bonds, forming R₂²(9) dimers.

Related literature

For general background to pyrrolidine derivatives, see: Obniska et al. (2010 ); Morais et al. (2009 ); Bello et al. (2010 ); Moreno-Clavijo et al. (2009 ); Cheng et al. (2008 ). For related structures, see: Aravindan et al. (2004 ); Selvanayagam et al. (2005 ); Seshadri et al. (2003 ). For ring-puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₉H₂₈N₄O₃
M_r = 480.55
Triclinic, $[P \overline 1]$
a = 9.7605 (5) Å
b = 11.2823 (6) Å
c = 12.2333 (7) Å
α = 79.960 (1)°
β = 69.539 (1)°
γ = 85.358 (1)°
V = 1242.53 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 292 K
0.26 × 0.24 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
14287 measured reflections
5705 independent reflections
5041 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.131
S = 1.04
5705 reflections
328 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N4ⁱ	0.86	2.05	2.888 (2)	165
C16—H16⋯O1	0.93	2.33	3.050 (2)	134
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035312/bt5341sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035312/bt5341Isup2.hkl

checkCIF report

Comment top

Pyrrolidine derivatives possess anticonvulsant (Obniska et al., 2010), anti-angiogenic (Morais et al., 2009) and antitumor (Bello et al., 2010) activities. These derivatives are used as inhibitors of alpha-L-fucosidases (Moreno-Clavijo et al., 2009) and matrix metalloproteinase (Cheng et al., 2008). In view of these importance, we have undertaken the crystal structure determination of the title compound, a pyrrolidine derivative, and the results are presented here.

The molecular structure of (I) is illustrated in Fig. 1. The geometry of the pyrrolidine and oxindole residues of (I) compares well with that reported in other related structures (see, for example, Aravindan et al., 2004; Selvanayagam et al., 2005; Seshadri et al., 2003).

The sum of the angles at N1 of the pyrrolidine ring [334.8°] and N3 of the imidazole ring [359.9°] are in accordance with sp³ and sp² hybridizations. Atom O1 is essentially coplanar with the heterocyclic ring to which it is attached, with a deviation of -0.159 (1) Å. Benzimidazole residue is planar with a maximum deviation of -0.011 (1) Å for atom C22. Atom C29 deviates 0.052 (2) Å from the best plane of the methylphenyl ring.

The dihedral angle between the oxindole and benzimidazole residues is 89.2 (1)°. This indicates that the oxindole residue is almost perpendicular to the benzimidazole residue. The methyl phenyl ring is oriented at an angles of 47.7 (1) and 71.0 (1) ° with respect to the oxindole and benzimidazole residues.

The pyrrolidine ring adopts a twist conformation, with puckering parameters (Cremer & Pople, 1975) q₂ = 0.454 (1) Å and ϕ = 149.9 (2)°.

The molecular structure is influenced by an intramolecular C—H···O hydrogen bonds. Atom O1 acts as a bifurcated acceptor for two intramolecular C—H···O hydrogen bonds. In the molecular packing, N—H···N hydrogen bonds link inversion-related molecules to form R₂²(9) graph-set dimer (Fig.2 and Table 1).

Related literature top

For general background to pyrrolidine derivatives, see: Obniska et al. (2010); Morais et al. (2009); Bello et al. (2010); Moreno-Clavijo et al. (2009); Cheng et al. (2008). For related structures, see: Aravindan et al. (2004); Selvanayagam et al. (2005); Seshadri et al. (2003). For ring-puckering parameters, see: Cremer & Pople (1975).

Experimental top

To a mixture of isatin (1mmol), sarcosine (1mmol) and Baylis-Hillman adduct (1mmol) was added and heated under reflux in methanol (20ml) until the disappearance of the starting materials as evidenced by TLC. The solvent was removed under vacuo. The crude product was subjected to column chromatography using petroleum ether-ethyl acetate as eluent. Single crystals were grown by slow evaporation from methanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); 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, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level
	Fig. 2. Molecular packing of the title compound, viewed down the a axis; H-bonds are shown as dashed lines. For the sake of clarity, H atoms, not involved in hydrogen bonds, have been omitted

Methyl 3-[(1H-benzimidazol-1-yl)methyl]-1-methyl-4-(4-methylphenyl)-2'- oxopyrrolidine-2-spiro-3'-1-benzimidazole-3-carboxylate top

Crystal data top

C₂₉H₂₈N₄O₃	Z = 2
M_r = 480.55	F(000) = 508
Triclinic, P1	D_x = 1.284 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7605 (5) Å	Cell parameters from 8628 reflections
b = 11.2823 (6) Å	θ = 2.0–27.4°
c = 12.2333 (7) Å	µ = 0.09 mm⁻¹
α = 79.960 (1)°	T = 292 K
β = 69.539 (1)°	Block, colourless
γ = 85.358 (1)°	0.26 × 0.24 × 0.22 mm
V = 1242.53 (12) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	5041 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 28.0°, θ_min = 1.8°
ω scans	h = −12→12
14287 measured reflections	k = −14→14
5705 independent reflections	l = −15→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0777P)² + 0.1893P] where P = (F_o² + 2F_c²)/3
5705 reflections	(Δ/σ)_max < 0.001
328 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₉H₂₈N₄O₃	γ = 85.358 (1)°
M_r = 480.55	V = 1242.53 (12) Å³
Triclinic, P1	Z = 2
a = 9.7605 (5) Å	Mo Kα radiation
b = 11.2823 (6) Å	µ = 0.09 mm⁻¹
c = 12.2333 (7) Å	T = 292 K
α = 79.960 (1)°	0.26 × 0.24 × 0.22 mm
β = 69.539 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	5041 reflections with I > 2σ(I)
14287 measured reflections	R_int = 0.017
5705 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
5705 reflections	Δρ_min = −0.26 e Å⁻³
328 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
O1	−0.02562 (10)	0.75938 (10)	0.40536 (9)	0.0564 (2)
O2	0.45463 (10)	0.62452 (9)	0.06224 (9)	0.0556 (2)
O3	0.30370 (10)	0.55640 (7)	0.24567 (8)	0.0475 (2)
N1	0.19339 (11)	0.93029 (8)	0.24498 (9)	0.0415 (2)
N2	0.16540 (13)	0.69375 (10)	0.47180 (9)	0.0498 (3)
H2	0.1161	0.6547	0.5395	0.060*
N3	0.05799 (10)	0.60212 (9)	0.17842 (8)	0.0392 (2)
N4	−0.04307 (15)	0.42908 (11)	0.28856 (10)	0.0592 (3)
C1	0.30089 (16)	0.97153 (11)	0.12846 (10)	0.0467 (3)
H1A	0.3882	0.9989	0.1363	0.056*
H1B	0.2603	1.0371	0.0857	0.056*
C2	0.33690 (12)	0.86094 (10)	0.06345 (9)	0.0371 (2)
H2A	0.4416	0.8431	0.0465	0.045*
C3	0.25260 (11)	0.75294 (9)	0.15982 (9)	0.0337 (2)
C4	0.23182 (12)	0.80336 (10)	0.27776 (9)	0.0363 (2)
C5	0.18078 (18)	1.00891 (12)	0.33182 (12)	0.0546 (3)
H5A	0.2735	1.0115	0.3421	0.082*
H5B	0.1087	0.9780	0.4059	0.082*
H5C	0.1518	1.0886	0.3043	0.082*
C6	0.36486 (13)	0.77598 (10)	0.31879 (10)	0.0383 (2)
C7	0.51257 (14)	0.80220 (12)	0.26535 (11)	0.0468 (3)
H7	0.5466	0.8478	0.1905	0.056*
C8	0.60970 (16)	0.75910 (14)	0.32568 (14)	0.0560 (3)
H8	0.7085	0.7767	0.2906	0.067*
C9	0.55981 (18)	0.69048 (15)	0.43698 (14)	0.0625 (4)
H9	0.6259	0.6620	0.4753	0.075*
C10	0.41285 (18)	0.66350 (14)	0.49225 (13)	0.0592 (4)
H10	0.3794	0.6173	0.5669	0.071*
C11	0.31760 (14)	0.70791 (11)	0.43221 (10)	0.0438 (3)
C12	0.10539 (13)	0.74875 (11)	0.39100 (10)	0.0427 (3)
C13	0.35074 (12)	0.63904 (10)	0.14798 (10)	0.0380 (2)
C14	0.3828 (2)	0.44195 (14)	0.24091 (17)	0.0713 (5)
H14A	0.3969	0.4160	0.1670	0.107*
H14B	0.3277	0.3831	0.3046	0.107*
H14C	0.4762	0.4509	0.2480	0.107*
C15	0.10345 (12)	0.72765 (10)	0.14655 (10)	0.0384 (2)
H15A	0.0272	0.7758	0.1952	0.046*
H15B	0.1105	0.7551	0.0651	0.046*
C16	−0.02908 (15)	0.54492 (13)	0.28527 (11)	0.0517 (3)
H16	−0.0745	0.5843	0.3499	0.062*
C17	0.04075 (15)	0.40654 (11)	0.17515 (12)	0.0481 (3)
C18	0.06481 (18)	0.29959 (12)	0.12571 (15)	0.0613 (4)
H18	0.0230	0.2278	0.1704	0.074*
C19	0.15226 (18)	0.30483 (13)	0.00910 (16)	0.0616 (4)
H19	0.1696	0.2351	−0.0251	0.074*
C20	0.21573 (15)	0.41222 (14)	−0.05946 (14)	0.0554 (3)
H20	0.2742	0.4120	−0.1379	0.066*
C21	0.19363 (13)	0.51890 (12)	−0.01339 (11)	0.0461 (3)
H21	0.2356	0.5903	−0.0590	0.055*
C22	0.10513 (12)	0.51376 (10)	0.10505 (10)	0.0390 (2)
C23	0.31253 (12)	0.88215 (10)	−0.05502 (9)	0.0361 (2)
C24	0.41258 (14)	0.83543 (11)	−0.15145 (11)	0.0440 (3)
H24	0.4914	0.7881	−0.1418	0.053*
C25	0.39601 (17)	0.85871 (13)	−0.26221 (11)	0.0536 (3)
H25	0.4643	0.8269	−0.3252	0.064*
C26	0.27911 (17)	0.92865 (12)	−0.27996 (11)	0.0505 (3)
C27	0.17746 (15)	0.97312 (11)	−0.18349 (11)	0.0475 (3)
H27	0.0969	1.0180	−0.1927	0.057*
C28	0.19461 (13)	0.95146 (11)	−0.07328 (10)	0.0428 (3)
H28	0.1263	0.9837	−0.0106	0.051*
C29	0.2617 (3)	0.95730 (18)	−0.40035 (15)	0.0789 (5)
H29A	0.3561	0.9562	−0.4609	0.118*
H29B	0.2167	1.0357	−0.4086	0.118*
H29C	0.2013	0.8982	−0.4077	0.118*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0441 (5)	0.0703 (6)	0.0480 (5)	−0.0038 (4)	−0.0057 (4)	−0.0113 (4)
O2	0.0484 (5)	0.0570 (5)	0.0528 (5)	0.0094 (4)	−0.0084 (4)	−0.0094 (4)
O3	0.0602 (5)	0.0349 (4)	0.0466 (5)	0.0031 (4)	−0.0212 (4)	0.0000 (3)
N1	0.0536 (6)	0.0351 (5)	0.0368 (5)	0.0028 (4)	−0.0177 (4)	−0.0051 (4)
N2	0.0576 (6)	0.0524 (6)	0.0318 (5)	−0.0095 (5)	−0.0096 (4)	0.0048 (4)
N3	0.0406 (5)	0.0383 (5)	0.0365 (5)	−0.0090 (4)	−0.0115 (4)	0.0004 (4)
N4	0.0737 (8)	0.0534 (6)	0.0456 (6)	−0.0246 (6)	−0.0172 (6)	0.0090 (5)
C1	0.0694 (8)	0.0361 (6)	0.0368 (6)	−0.0109 (5)	−0.0216 (5)	0.0000 (5)
C2	0.0427 (5)	0.0368 (5)	0.0314 (5)	−0.0079 (4)	−0.0135 (4)	0.0008 (4)
C3	0.0368 (5)	0.0332 (5)	0.0298 (5)	−0.0030 (4)	−0.0112 (4)	−0.0009 (4)
C4	0.0406 (5)	0.0359 (5)	0.0307 (5)	−0.0023 (4)	−0.0114 (4)	−0.0018 (4)
C5	0.0766 (9)	0.0460 (7)	0.0448 (7)	0.0063 (6)	−0.0237 (6)	−0.0134 (5)
C6	0.0470 (6)	0.0363 (5)	0.0331 (5)	−0.0020 (4)	−0.0163 (4)	−0.0036 (4)
C7	0.0483 (6)	0.0503 (7)	0.0425 (6)	−0.0057 (5)	−0.0179 (5)	−0.0016 (5)
C8	0.0509 (7)	0.0625 (8)	0.0613 (8)	0.0006 (6)	−0.0275 (6)	−0.0106 (7)
C9	0.0697 (9)	0.0665 (9)	0.0634 (9)	0.0109 (7)	−0.0415 (8)	−0.0080 (7)
C10	0.0788 (10)	0.0575 (8)	0.0446 (7)	0.0028 (7)	−0.0319 (7)	0.0039 (6)
C11	0.0566 (7)	0.0398 (6)	0.0351 (6)	−0.0025 (5)	−0.0175 (5)	−0.0017 (4)
C12	0.0463 (6)	0.0436 (6)	0.0343 (5)	−0.0047 (5)	−0.0075 (5)	−0.0070 (4)
C13	0.0406 (5)	0.0375 (5)	0.0389 (5)	−0.0009 (4)	−0.0177 (4)	−0.0046 (4)
C14	0.0865 (11)	0.0433 (7)	0.0834 (11)	0.0160 (7)	−0.0373 (9)	0.0012 (7)
C15	0.0398 (5)	0.0351 (5)	0.0400 (6)	−0.0048 (4)	−0.0158 (4)	0.0010 (4)
C16	0.0561 (7)	0.0544 (7)	0.0385 (6)	−0.0177 (6)	−0.0094 (5)	0.0022 (5)
C17	0.0555 (7)	0.0417 (6)	0.0492 (7)	−0.0115 (5)	−0.0243 (6)	0.0056 (5)
C18	0.0771 (10)	0.0371 (6)	0.0793 (10)	−0.0093 (6)	−0.0426 (8)	0.0029 (6)
C19	0.0688 (9)	0.0489 (7)	0.0816 (11)	0.0077 (6)	−0.0408 (8)	−0.0205 (7)
C20	0.0486 (7)	0.0646 (8)	0.0584 (8)	0.0025 (6)	−0.0205 (6)	−0.0209 (7)
C21	0.0416 (6)	0.0511 (7)	0.0463 (6)	−0.0083 (5)	−0.0150 (5)	−0.0063 (5)
C22	0.0391 (5)	0.0378 (5)	0.0428 (6)	−0.0057 (4)	−0.0184 (5)	−0.0020 (4)
C23	0.0426 (5)	0.0341 (5)	0.0305 (5)	−0.0078 (4)	−0.0121 (4)	0.0003 (4)
C24	0.0506 (6)	0.0419 (6)	0.0395 (6)	0.0020 (5)	−0.0155 (5)	−0.0075 (5)
C25	0.0706 (9)	0.0530 (7)	0.0369 (6)	0.0040 (6)	−0.0159 (6)	−0.0139 (5)
C26	0.0725 (8)	0.0458 (6)	0.0394 (6)	−0.0056 (6)	−0.0270 (6)	−0.0042 (5)
C27	0.0556 (7)	0.0434 (6)	0.0462 (6)	−0.0016 (5)	−0.0243 (6)	0.0003 (5)
C28	0.0449 (6)	0.0432 (6)	0.0368 (6)	−0.0017 (5)	−0.0115 (5)	−0.0019 (5)
C29	0.1203 (16)	0.0809 (11)	0.0495 (8)	0.0099 (11)	−0.0479 (10)	−0.0122 (8)

Geometric parameters (Å, º) top

O1—C12	1.2271 (16)	C9—C10	1.389 (2)
O2—C13	1.2019 (14)	C9—H9	0.9300
O3—C13	1.3437 (14)	C10—C11	1.3888 (18)
O3—C14	1.4492 (16)	C10—H10	0.9300
N1—C5	1.4662 (16)	C14—H14A	0.9600
N1—C1	1.4668 (16)	C14—H14B	0.9600
N1—C4	1.4732 (14)	C14—H14C	0.9600
N2—C12	1.3555 (16)	C15—H15A	0.9700
N2—C11	1.4055 (17)	C15—H15B	0.9700
N2—H2	0.8600	C16—H16	0.9300
N3—C16	1.3657 (15)	C17—C22	1.4065 (16)
N3—C22	1.4000 (16)	C17—C18	1.409 (2)
N3—C15	1.4639 (14)	C18—C19	1.376 (2)
N4—C16	1.3172 (19)	C18—H18	0.9300
N4—C17	1.3981 (19)	C19—C20	1.400 (2)
C1—C2	1.5467 (16)	C19—H19	0.9300
C1—H1A	0.9700	C20—C21	1.3866 (19)
C1—H1B	0.9700	C20—H20	0.9300
C2—C23	1.5247 (14)	C21—C22	1.3973 (17)
C2—C3	1.5921 (14)	C21—H21	0.9300
C2—H2A	0.9800	C23—C24	1.3968 (16)
C3—C13	1.5357 (15)	C23—C28	1.3998 (16)
C3—C15	1.5735 (15)	C24—C25	1.3976 (18)
C3—C4	1.5840 (15)	C24—H24	0.9300
C4—C6	1.5396 (16)	C25—C26	1.393 (2)
C4—C12	1.5658 (15)	C25—H25	0.9300
C5—H5A	0.9600	C26—C27	1.391 (2)
C5—H5B	0.9600	C26—C29	1.5173 (18)
C5—H5C	0.9600	C27—C28	1.3934 (17)
C6—C7	1.3915 (17)	C27—H27	0.9300
C6—C11	1.4021 (16)	C28—H28	0.9300
C7—C8	1.4033 (18)	C29—H29A	0.9600
C7—H7	0.9300	C29—H29B	0.9600
C8—C9	1.386 (2)	C29—H29C	0.9600
C8—H8	0.9300

C13—O3—C14	115.61 (11)	N2—C12—C4	108.20 (10)
C5—N1—C1	113.09 (10)	O2—C13—O3	124.23 (10)
C5—N1—C4	115.51 (9)	O2—C13—C3	124.75 (10)
C1—N1—C4	106.21 (9)	O3—C13—C3	111.01 (9)
C12—N2—C11	112.18 (10)	O3—C14—H14A	109.5
C12—N2—H2	123.9	O3—C14—H14B	109.5
C11—N2—H2	123.9	H14A—C14—H14B	109.5
C16—N3—C22	105.96 (10)	O3—C14—H14C	109.5
C16—N3—C15	128.19 (11)	H14A—C14—H14C	109.5
C22—N3—C15	125.72 (9)	H14B—C14—H14C	109.5
C16—N4—C17	104.88 (11)	N3—C15—C3	116.04 (9)
N1—C1—C2	105.55 (9)	N3—C15—H15A	108.3
N1—C1—H1A	110.6	C3—C15—H15A	108.3
C2—C1—H1A	110.6	N3—C15—H15B	108.3
N1—C1—H1B	110.6	C3—C15—H15B	108.3
C2—C1—H1B	110.6	H15A—C15—H15B	107.4
H1A—C1—H1B	108.8	N4—C16—N3	114.03 (12)
C23—C2—C1	114.32 (9)	N4—C16—H16	123.0
C23—C2—C3	117.51 (9)	N3—C16—H16	123.0
C1—C2—C3	104.77 (8)	N4—C17—C22	109.58 (11)
C23—C2—H2A	106.5	N4—C17—C18	130.71 (12)
C1—C2—H2A	106.5	C22—C17—C18	119.71 (13)
C3—C2—H2A	106.5	C19—C18—C17	117.84 (13)
C13—C3—C15	109.64 (9)	C19—C18—H18	121.1
C13—C3—C4	112.06 (8)	C17—C18—H18	121.1
C15—C3—C4	113.01 (9)	C18—C19—C20	121.77 (14)
C13—C3—C2	109.12 (9)	C18—C19—H19	119.1
C15—C3—C2	112.02 (8)	C20—C19—H19	119.1
C4—C3—C2	100.71 (8)	C21—C20—C19	121.69 (14)
N1—C4—C6	118.20 (9)	C21—C20—H20	119.2
N1—C4—C12	108.16 (9)	C19—C20—H20	119.2
C6—C4—C12	101.17 (9)	C20—C21—C22	116.65 (12)
N1—C4—C3	100.65 (8)	C20—C21—H21	121.7
C6—C4—C3	112.70 (9)	C22—C21—H21	121.7
C12—C4—C3	116.68 (9)	C21—C22—N3	132.09 (11)
N1—C5—H5A	109.5	C21—C22—C17	122.34 (12)
N1—C5—H5B	109.5	N3—C22—C17	105.55 (10)
H5A—C5—H5B	109.5	C24—C23—C28	117.53 (10)
N1—C5—H5C	109.5	C24—C23—C2	120.08 (10)
H5A—C5—H5C	109.5	C28—C23—C2	122.35 (10)
H5B—C5—H5C	109.5	C23—C24—C25	120.96 (12)
C7—C6—C11	118.67 (11)	C23—C24—H24	119.5
C7—C6—C4	133.14 (10)	C25—C24—H24	119.5
C11—C6—C4	108.15 (10)	C26—C25—C24	121.19 (12)
C6—C7—C8	119.29 (12)	C26—C25—H25	119.4
C6—C7—H7	120.4	C24—C25—H25	119.4
C8—C7—H7	120.4	C27—C26—C25	118.01 (11)
C9—C8—C7	120.61 (13)	C27—C26—C29	120.20 (14)
C9—C8—H8	119.7	C25—C26—C29	121.79 (14)
C7—C8—H8	119.7	C26—C27—C28	120.98 (12)
C8—C9—C10	121.15 (13)	C26—C27—H27	119.5
C8—C9—H9	119.4	C28—C27—H27	119.5
C10—C9—H9	119.4	C27—C28—C23	121.32 (11)
C9—C10—C11	117.67 (13)	C27—C28—H28	119.3
C9—C10—H10	121.2	C23—C28—H28	119.3
C11—C10—H10	121.2	C26—C29—H29A	109.5
C10—C11—C6	122.60 (13)	C26—C29—H29B	109.5
C10—C11—N2	127.34 (12)	H29A—C29—H29B	109.5
C6—C11—N2	110.06 (10)	C26—C29—H29C	109.5
O1—C12—N2	126.27 (11)	H29A—C29—H29C	109.5
O1—C12—C4	125.45 (11)	H29B—C29—H29C	109.5

C5—N1—C1—C2	161.69 (10)	C6—C4—C12—N2	−4.58 (12)
C4—N1—C1—C2	33.99 (12)	C3—C4—C12—N2	118.07 (11)
N1—C1—C2—C23	124.14 (10)	C14—O3—C13—O2	−2.91 (18)
N1—C1—C2—C3	−5.90 (12)	C14—O3—C13—C3	176.04 (12)
C23—C2—C3—C13	92.40 (11)	C15—C3—C13—O2	104.57 (13)
C1—C2—C3—C13	−139.46 (9)	C4—C3—C13—O2	−129.11 (12)
C23—C2—C3—C15	−29.19 (13)	C2—C3—C13—O2	−18.46 (15)
C1—C2—C3—C15	98.95 (10)	C15—C3—C13—O3	−74.38 (11)
C23—C2—C3—C4	−149.56 (10)	C4—C3—C13—O3	51.94 (12)
C1—C2—C3—C4	−21.42 (11)	C2—C3—C13—O3	162.60 (9)
C5—N1—C4—C6	−50.74 (14)	C16—N3—C15—C3	92.19 (15)
C1—N1—C4—C6	75.51 (12)	C22—N3—C15—C3	−83.07 (13)
C5—N1—C4—C12	63.29 (13)	C13—C3—C15—N3	26.13 (13)
C1—N1—C4—C12	−170.47 (9)	C4—C3—C15—N3	−99.65 (11)
C5—N1—C4—C3	−173.86 (10)	C2—C3—C15—N3	147.43 (9)
C1—N1—C4—C3	−47.62 (11)	C17—N4—C16—N3	−0.14 (17)
C13—C3—C4—N1	156.94 (9)	C22—N3—C16—N4	0.01 (16)
C15—C3—C4—N1	−78.59 (10)	C15—N3—C16—N4	−175.99 (12)
C2—C3—C4—N1	41.06 (10)	C16—N4—C17—C22	0.22 (15)
C13—C3—C4—C6	30.07 (12)	C16—N4—C17—C18	−178.59 (15)
C15—C3—C4—C6	154.54 (9)	N4—C17—C18—C19	178.97 (14)
C2—C3—C4—C6	−85.80 (10)	C22—C17—C18—C19	0.3 (2)
C13—C3—C4—C12	−86.36 (12)	C17—C18—C19—C20	−0.2 (2)
C15—C3—C4—C12	38.11 (13)	C18—C19—C20—C21	0.0 (2)
C2—C3—C4—C12	157.77 (9)	C19—C20—C21—C22	0.17 (19)
N1—C4—C6—C7	−59.69 (17)	C20—C21—C22—N3	−178.63 (12)
C12—C4—C6—C7	−177.48 (13)	C20—C21—C22—C17	−0.07 (18)
C3—C4—C6—C7	57.16 (16)	C16—N3—C22—C21	178.86 (13)
N1—C4—C6—C11	122.37 (11)	C15—N3—C22—C21	−5.02 (19)
C12—C4—C6—C11	4.58 (11)	C16—N3—C22—C17	0.13 (13)
C3—C4—C6—C11	−120.78 (10)	C15—N3—C22—C17	176.25 (10)
C11—C6—C7—C8	0.58 (18)	N4—C17—C22—C21	−179.10 (11)
C4—C6—C7—C8	−177.19 (12)	C18—C17—C22—C21	−0.14 (19)
C6—C7—C8—C9	0.4 (2)	N4—C17—C22—N3	−0.21 (14)
C7—C8—C9—C10	−0.6 (2)	C18—C17—C22—N3	178.75 (11)
C8—C9—C10—C11	−0.1 (2)	C1—C2—C23—C24	139.36 (11)
C9—C10—C11—C6	1.2 (2)	C3—C2—C23—C24	−97.22 (12)
C9—C10—C11—N2	−178.74 (13)	C1—C2—C23—C28	−38.27 (14)
C7—C6—C11—C10	−1.40 (19)	C3—C2—C23—C28	85.16 (13)
C4—C6—C11—C10	176.88 (12)	C28—C23—C24—C25	0.84 (18)
C7—C6—C11—N2	178.53 (11)	C2—C23—C24—C25	−176.90 (11)
C4—C6—C11—N2	−3.18 (13)	C23—C24—C25—C26	−0.3 (2)
C12—N2—C11—C10	179.99 (13)	C24—C25—C26—C27	−1.1 (2)
C12—N2—C11—C6	0.05 (15)	C24—C25—C26—C29	178.44 (15)
C11—N2—C12—O1	−173.75 (12)	C25—C26—C27—C28	2.0 (2)
C11—N2—C12—C4	3.05 (14)	C29—C26—C27—C28	−177.59 (14)
N1—C4—C12—O1	47.38 (15)	C26—C27—C28—C23	−1.45 (19)
C6—C4—C12—O1	172.25 (12)	C24—C23—C28—C27	0.02 (17)
C3—C4—C12—O1	−65.10 (16)	C2—C23—C28—C27	177.70 (10)
N1—C4—C12—N2	−129.44 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N4ⁱ	0.86	2.05	2.888 (2)	165
C16—H16···O1	0.93	2.33	3.050 (2)	134

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₉H₂₈N₄O₃
M_r	480.55
Crystal system, space group	Triclinic, P1
Temperature (K)	292
a, b, c (Å)	9.7605 (5), 11.2823 (6), 12.2333 (7)
α, β, γ (°)	79.960 (1), 69.539 (1), 85.358 (1)
V (Å³)	1242.53 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14287, 5705, 5041
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.131, 1.04
No. of reflections	5705
No. of parameters	328
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.26

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), 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···N4ⁱ	0.86	2.05	2.888 (2)	165
C16—H16···O1	0.93	2.33	3.050 (2)	134

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

SS acknowledges the Department of Science and Technology (DST), India, for providing computing facilities under DST-Fast Track Scheme. SS also thanks the Vice Chancellor and management of Kalasalingam University, Krishnankoil, for their support and encouragement.

References

Aravindan, P. G., Selvanayagam, S., Velmurugan, D., Ravikumar, K., Jayashankaran, J. & Raghunathan, R. (2004). Acta Cryst. E60, o2152–o2154. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bello, C., Cea, M., Dal Bello, G., Garuti, A., Rocco, I., Cirmena, G., Moran, E., Nahimana, A., Duchosal, M. A., Fruscione, F., Pronzato, P., Grossi, F., Patrone, F., Ballestrero, A., Dupuis, M., Sordat, B., Nencioni, A. & Vogel, P. (2010). Bioorg. Med. Chem. 18, 3320–3334. Web of Science CrossRef CAS PubMed Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheng, X. C., Wang, Q., Fang, H., Tang, W. & Xu, W. F. (2008). Bioorg. Med. Chem. 16, 7932–7938. Web of Science CrossRef PubMed CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Morais, C., Gobe, G., Johnson, D. W. & Healy, H. (2009). Angiogenesis, 12, 365–379. Web of Science CrossRef PubMed CAS Google Scholar
Moreno-Clavijo, E., Carmona, A. T., Vera-Ayoso, Y., Moreno-Vargas, A. J., Bello, C., Vogel, P. & Robina, I. (2009). Org. Biomol. Chem. 7, 1192–1202. Web of Science CrossRef PubMed CAS Google Scholar
Obniska, J., Kopytko, M., Zagórska, A., Chlebek, I. & Kamiński, K. (2010). Arch. Pharm. (Weinheim), 343, 333–341. Web of Science CrossRef CAS PubMed Google Scholar
Selvanayagam, S., Rathisuganya, P., Shaherin, B., Velmurugan, D., Ravikumar, K. & Poornachandran, M. (2005). Acta Cryst. E61, o3693–o3695. Web of Science CSD CrossRef IUCr Journals Google Scholar
Seshadri, P. R., Selvanayagam, S., Velmurugan, D., Ravikumar, K., Sureshbabu, A. R. & Raghunathan, R. (2003). Acta Cryst. E59, o2025–o2027. Web of Science CSD CrossRef IUCr Journals 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

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 66| Part 10| October 2010| Pages o2508-o2509

doi:10.1107/S1600536810035312

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

Methyl 3-[(1H-benzimidazol-1-yl)meth­yl]-1-methyl-4-(4-methyl­phen­yl)-2′-oxopyrrolidine-2-spiro-3′-1-benzimidazole-3-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Methyl 3-[(1H-benzimidazol-1-yl)methyl]-1-methyl-4-(4-methylphenyl)-2′-oxopyrrolidine-2-spiro-3′-1-benzimidazole-3-carboxylate