Methyl 1-methyl-3-p-tolyl-1,2,3,3a,4,11c-hexa-hydro-benzo[f]chromeno[4,3-b]pyrrole-3a-carboxyl-ate.

In the title compound, C(25)H(25)NO(3), the dihydro-pyran ring adopts a half-chair conformation, whereas the pyrrolidine ring is in a twist conformation. The tolyl group is oriented at an angle of 82.92 (7)° with respect to the napthalene ring system. In the crystal structure, mol-ecules are linked into centrosymmetric dimers by C-H⋯π inter-actions involving the benzene ring of the tolyl group.

Related literature

For the biological activity of pyrrole derivatives, see: Biava et al. (2005 ▶); Borthwick et al. (2000 ▶); Caine (1993 ▶); Carlson (1993 ▶); Fernandes et al. (2004 ▶); Jiang et al. (2004 ▶); Sokoloff et al. (1990 ▶); Tidey & Miczek (1992 ▶); Wilner (1985 ▶). For a related structure, see: Gunasekaran et al. (2009 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C25H25NO3

M = 387.46

Monoclinic,

a = 12.9899 (6) Å

b = 7.6751 (3) Å

c = 20.5073 (9) Å

β = 96.881 (2)°

V = 2029.83 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa-APEXII area-detector diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.980, T max = 0.984

22975 measured reflections

4790 independent reflections

3176 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.156

S = 1.05

4790 reflections

265 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.19 e Å−3

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 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024738/ci2823sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024738/ci2823Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C25H25NO3	F(000) = 824
Mr = 387.46	Dx = 1.268 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6463 reflections
a = 12.9899 (6) Å	θ = 2.8–25.6°
b = 7.6751 (3) Å	µ = 0.08 mm−1
c = 20.5073 (9) Å	T = 293 K
β = 96.881 (2)°	Prism, colourless
V = 2029.83 (15) Å3	0.25 × 0.20 × 0.20 mm
Z = 4

Bruker Kappa-APEXII area-detector diffractometer	4790 independent reflections
Radiation source: fine-focus sealed tube	3176 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω and φ scans	θmax = 27.8°, θmin = 1.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −17→16
Tmin = 0.980, Tmax = 0.984	k = −8→10
22975 measured reflections	l = −20→26

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.081P)2 + 0.2107P] where P = (Fo2 + 2Fc2)/3
4790 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	−0.09259 (11)	0.31953 (19)	0.17432 (7)	0.0388 (3)
H1	−0.0790	0.2192	0.1471	0.047*
C2	−0.08470 (10)	0.48434 (19)	0.13573 (7)	0.0384 (3)
C3	−0.11550 (11)	0.4919 (2)	0.06634 (7)	0.0446 (4)
C4	−0.15523 (13)	0.3466 (3)	0.02933 (8)	0.0558 (4)
H4	−0.1621	0.2406	0.0503	0.067*
C5	−0.18383 (15)	0.3592 (3)	−0.03703 (9)	0.0697 (6)
H5	−0.2104	0.2622	−0.0605	0.084*
C6	−0.17327 (16)	0.5168 (4)	−0.06962 (10)	0.0765 (6)
H6	−0.1929	0.5245	−0.1147	0.092*
C7	−0.13492 (15)	0.6571 (3)	−0.03608 (9)	0.0681 (6)
H7	−0.1283	0.7612	−0.0584	0.082*
C8	−0.10438 (12)	0.6502 (2)	0.03225 (8)	0.0527 (4)
C9	−0.06138 (14)	0.7959 (2)	0.06742 (9)	0.0569 (5)
H9	−0.0551	0.9007	0.0454	0.068*
C10	−0.02925 (12)	0.7865 (2)	0.13232 (9)	0.0499 (4)
H10	−0.0001	0.8835	0.1546	0.060*
C11	−0.04003 (11)	0.6293 (2)	0.16629 (7)	0.0412 (4)
C12	−0.02357 (12)	0.4915 (2)	0.27124 (7)	0.0421 (4)
H12A	−0.0931	0.5077	0.2830	0.051*
H12B	0.0241	0.4923	0.3115	0.051*
C13	−0.01754 (11)	0.31594 (19)	0.23809 (7)	0.0383 (3)
C14	−0.06451 (12)	0.1678 (2)	0.27941 (8)	0.0460 (4)
H14	−0.0239	0.0616	0.2752	0.055*
C15	−0.17243 (13)	0.1390 (2)	0.24138 (8)	0.0541 (4)
H15A	−0.1732	0.0353	0.2143	0.065*
H15B	−0.2245	0.1268	0.2713	0.065*
C16	−0.06274 (12)	0.2062 (2)	0.35187 (8)	0.0452 (4)
C17	0.02402 (13)	0.1666 (2)	0.39539 (9)	0.0560 (5)
H17	0.0815	0.1176	0.3794	0.067*
C18	0.02723 (15)	0.1980 (3)	0.46167 (10)	0.0649 (5)
H18	0.0867	0.1691	0.4895	0.078*
C19	−0.05580 (15)	0.2713 (2)	0.48788 (8)	0.0584 (5)
C20	−0.14203 (14)	0.3124 (2)	0.44449 (9)	0.0579 (5)
H20	−0.1991	0.3631	0.4604	0.070*
C21	−0.14554 (13)	0.2801 (2)	0.37841 (9)	0.0537 (4)
H21	−0.2052	0.3086	0.3507	0.064*
C22	−0.0533 (2)	0.3059 (3)	0.56044 (9)	0.0838 (7)
H22A	−0.0196	0.4154	0.5711	0.126*
H22B	−0.0157	0.2144	0.5848	0.126*
H22C	−0.1229	0.3100	0.5717	0.126*
C23	−0.28437 (12)	0.2833 (2)	0.15488 (9)	0.0548 (4)
H23A	−0.2814	0.1813	0.1281	0.082*
H23B	−0.2897	0.3850	0.1275	0.082*
H23C	−0.3438	0.2763	0.1784	0.082*
C24	0.09063 (12)	0.2649 (2)	0.22557 (8)	0.0416 (4)
C25	0.26911 (14)	0.2845 (3)	0.26242 (13)	0.0781 (6)
H25A	0.2773	0.1627	0.2723	0.117*
H25B	0.3156	0.3507	0.2929	0.117*
H25C	0.2847	0.3057	0.2185	0.117*
N1	−0.19140 (9)	0.29402 (17)	0.20102 (6)	0.0447 (3)
O1	0.00093 (8)	0.63413 (14)	0.23080 (5)	0.0468 (3)
O2	0.16331 (8)	0.33635 (16)	0.26780 (7)	0.0646 (4)
O3	0.10931 (9)	0.16459 (17)	0.18379 (6)	0.0630 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0344 (7)	0.0380 (8)	0.0430 (8)	−0.0011 (6)	0.0001 (6)	−0.0058 (7)
C2	0.0304 (7)	0.0415 (8)	0.0431 (8)	0.0015 (6)	0.0038 (6)	0.0003 (7)
C3	0.0321 (7)	0.0576 (10)	0.0441 (8)	0.0046 (7)	0.0051 (6)	−0.0006 (8)
C4	0.0458 (9)	0.0734 (12)	0.0471 (9)	−0.0008 (8)	0.0007 (7)	−0.0069 (9)
C5	0.0537 (11)	0.1041 (17)	0.0497 (10)	−0.0019 (10)	−0.0004 (8)	−0.0152 (12)
C6	0.0628 (12)	0.123 (2)	0.0424 (10)	0.0045 (12)	0.0015 (9)	0.0075 (13)
C7	0.0589 (11)	0.0952 (16)	0.0508 (11)	0.0062 (11)	0.0099 (9)	0.0179 (11)
C8	0.0393 (8)	0.0695 (12)	0.0498 (9)	0.0082 (8)	0.0079 (7)	0.0100 (9)
C9	0.0514 (10)	0.0550 (10)	0.0657 (12)	0.0057 (8)	0.0125 (9)	0.0172 (9)
C10	0.0451 (9)	0.0411 (9)	0.0641 (11)	0.0012 (7)	0.0087 (8)	0.0018 (8)
C11	0.0346 (7)	0.0417 (8)	0.0475 (9)	0.0029 (6)	0.0060 (6)	0.0003 (7)
C12	0.0416 (8)	0.0425 (8)	0.0412 (8)	−0.0030 (6)	0.0009 (6)	−0.0026 (7)
C13	0.0356 (7)	0.0374 (8)	0.0405 (8)	−0.0027 (6)	−0.0004 (6)	−0.0008 (7)
C14	0.0456 (9)	0.0403 (8)	0.0514 (9)	−0.0048 (6)	0.0026 (7)	0.0029 (7)
C15	0.0522 (10)	0.0549 (10)	0.0532 (10)	−0.0157 (8)	−0.0020 (8)	0.0042 (8)
C16	0.0408 (8)	0.0444 (9)	0.0492 (9)	−0.0051 (7)	0.0006 (7)	0.0091 (7)
C17	0.0427 (9)	0.0659 (11)	0.0578 (11)	0.0057 (8)	0.0004 (8)	0.0116 (9)
C18	0.0535 (11)	0.0802 (13)	0.0570 (11)	−0.0022 (9)	−0.0100 (8)	0.0153 (10)
C19	0.0630 (11)	0.0621 (11)	0.0489 (10)	−0.0158 (9)	0.0020 (9)	0.0107 (9)
C20	0.0515 (10)	0.0659 (11)	0.0578 (11)	−0.0034 (8)	0.0123 (8)	0.0048 (9)
C21	0.0420 (9)	0.0638 (11)	0.0535 (10)	0.0009 (8)	−0.0013 (7)	0.0090 (9)
C22	0.1037 (18)	0.0954 (17)	0.0512 (11)	−0.0230 (14)	0.0053 (11)	0.0049 (11)
C23	0.0395 (9)	0.0615 (11)	0.0613 (10)	−0.0084 (7)	−0.0022 (8)	−0.0030 (9)
C24	0.0399 (8)	0.0368 (8)	0.0468 (9)	−0.0003 (6)	−0.0005 (7)	0.0044 (7)
C25	0.0356 (10)	0.0670 (13)	0.1270 (19)	0.0046 (8)	−0.0098 (10)	−0.0069 (12)
N1	0.0348 (7)	0.0491 (8)	0.0489 (7)	−0.0082 (5)	−0.0005 (5)	−0.0006 (6)
O1	0.0517 (6)	0.0394 (6)	0.0475 (6)	−0.0069 (5)	−0.0009 (5)	−0.0037 (5)
O2	0.0366 (6)	0.0623 (8)	0.0905 (9)	0.0003 (5)	−0.0102 (6)	−0.0199 (7)
O3	0.0515 (7)	0.0710 (8)	0.0657 (8)	0.0128 (6)	0.0039 (6)	−0.0153 (7)

C1—N1	1.4676 (18)	C14—C15	1.536 (2)
C1—C2	1.502 (2)	C14—H14	0.98
C1—C13	1.5348 (19)	C15—N1	1.454 (2)
C1—H1	0.98	C15—H15A	0.97
C2—C11	1.371 (2)	C15—H15B	0.97
C2—C3	1.432 (2)	C16—C21	1.384 (2)
C3—C4	1.411 (2)	C16—C17	1.385 (2)
C3—C8	1.418 (2)	C17—C18	1.376 (3)
C4—C5	1.370 (2)	C17—H17	0.93
C4—H4	0.93	C18—C19	1.381 (3)
C5—C6	1.397 (3)	C18—H18	0.93
C5—H5	0.93	C19—C20	1.381 (3)
C6—C7	1.341 (3)	C19—C22	1.508 (3)
C6—H6	0.93	C20—C21	1.373 (2)
C7—C8	1.411 (3)	C20—H20	0.93
C7—H7	0.93	C21—H21	0.93
C8—C9	1.409 (3)	C22—H22A	0.96
C9—C10	1.348 (2)	C22—H22B	0.96
C9—H9	0.93	C22—H22C	0.96
C10—C11	1.409 (2)	C23—N1	1.4445 (19)
C10—H10	0.93	C23—H23A	0.96
C11—O1	1.3661 (18)	C23—H23B	0.96
C12—O1	1.4318 (18)	C23—H23C	0.96
C12—C13	1.516 (2)	C24—O3	1.1983 (19)
C12—H12A	0.97	C24—O2	1.3214 (19)
C12—H12B	0.97	C25—O2	1.448 (2)
C13—C24	1.510 (2)	C25—H25A	0.96
C13—C14	1.583 (2)	C25—H25B	0.96
C14—C16	1.512 (2)	C25—H25C	0.96
N1—C1—C2	115.26 (12)	C15—C14—H14	107.7
N1—C1—C13	100.04 (11)	C13—C14—H14	107.7
C2—C1—C13	112.81 (12)	N1—C15—C14	104.68 (12)
N1—C1—H1	109.4	N1—C15—H15A	110.8
C2—C1—H1	109.4	C14—C15—H15A	110.8
C13—C1—H1	109.4	N1—C15—H15B	110.8
C11—C2—C3	118.29 (14)	C14—C15—H15B	110.8
C11—C2—C1	119.61 (13)	H15A—C15—H15B	108.9
C3—C2—C1	121.93 (13)	C21—C16—C17	116.58 (15)
C4—C3—C8	117.66 (15)	C21—C16—C14	123.05 (14)
C4—C3—C2	122.89 (15)	C17—C16—C14	120.37 (15)
C8—C3—C2	119.44 (15)	C18—C17—C16	121.60 (17)
C5—C4—C3	121.10 (19)	C18—C17—H17	119.2
C5—C4—H4	119.5	C16—C17—H17	119.2
C3—C4—H4	119.5	C17—C18—C19	121.54 (17)
C4—C5—C6	120.4 (2)	C17—C18—H18	119.2
C4—C5—H5	119.8	C19—C18—H18	119.2
C6—C5—H5	119.8	C20—C19—C18	116.95 (17)
C7—C6—C5	120.10 (18)	C20—C19—C22	121.04 (19)
C7—C6—H6	119.9	C18—C19—C22	122.01 (19)
C5—C6—H6	119.9	C21—C20—C19	121.54 (17)
C6—C7—C8	121.5 (2)	C21—C20—H20	119.2
C6—C7—H7	119.2	C19—C20—H20	119.2
C8—C7—H7	119.2	C20—C21—C16	121.79 (16)
C9—C8—C7	121.71 (18)	C20—C21—H21	119.1
C9—C8—C3	119.04 (15)	C16—C21—H21	119.1
C7—C8—C3	119.24 (18)	C19—C22—H22A	109.5
C10—C9—C8	121.28 (16)	C19—C22—H22B	109.5
C10—C9—H9	119.4	H22A—C22—H22B	109.5
C8—C9—H9	119.4	C19—C22—H22C	109.5
C9—C10—C11	119.79 (16)	H22A—C22—H22C	109.5
C9—C10—H10	120.1	H22B—C22—H22C	109.5
C11—C10—H10	120.1	N1—C23—H23A	109.5
O1—C11—C2	124.01 (13)	N1—C23—H23B	109.5
O1—C11—C10	113.90 (13)	H23A—C23—H23B	109.5
C2—C11—C10	122.05 (14)	N1—C23—H23C	109.5
O1—C12—C13	113.13 (11)	H23A—C23—H23C	109.5
O1—C12—H12A	109.0	H23B—C23—H23C	109.5
C13—C12—H12A	109.0	O3—C24—O2	123.05 (15)
O1—C12—H12B	109.0	O3—C24—C13	124.09 (14)
C13—C12—H12B	109.0	O2—C24—C13	112.79 (14)
H12A—C12—H12B	107.8	O2—C25—H25A	109.5
C24—C13—C12	113.95 (12)	O2—C25—H25B	109.5
C24—C13—C1	111.64 (12)	H25A—C25—H25B	109.5
C12—C13—C1	107.73 (12)	O2—C25—H25C	109.5
C24—C13—C14	109.32 (12)	H25A—C25—H25C	109.5
C12—C13—C14	110.77 (12)	H25B—C25—H25C	109.5
C1—C13—C14	102.87 (11)	C23—N1—C15	113.43 (13)
C16—C14—C15	115.62 (14)	C23—N1—C1	117.60 (13)
C16—C14—C13	115.10 (12)	C15—N1—C1	103.03 (12)
C15—C14—C13	102.60 (12)	C11—O1—C12	116.89 (11)
C16—C14—H14	107.7	C24—O2—C25	116.50 (15)
N1—C1—C2—C11	94.97 (15)	C12—C13—C14—C16	−24.73 (17)
C13—C1—C2—C11	−19.09 (18)	C1—C13—C14—C16	−139.61 (13)
N1—C1—C2—C3	−89.82 (16)	C24—C13—C14—C15	−131.92 (14)
C13—C1—C2—C3	156.12 (13)	C12—C13—C14—C15	101.71 (14)
C11—C2—C3—C4	175.31 (14)	C1—C13—C14—C15	−13.17 (15)
C1—C2—C3—C4	0.0 (2)	C16—C14—C15—N1	108.16 (15)
C11—C2—C3—C8	−3.5 (2)	C13—C14—C15—N1	−17.95 (16)
C1—C2—C3—C8	−178.76 (13)	C15—C14—C16—C21	−25.5 (2)
C8—C3—C4—C5	−1.2 (2)	C13—C14—C16—C21	93.96 (18)
C2—C3—C4—C5	180.00 (15)	C15—C14—C16—C17	154.05 (15)
C3—C4—C5—C6	0.6 (3)	C13—C14—C16—C17	−86.49 (18)
C4—C5—C6—C7	0.0 (3)	C21—C16—C17—C18	0.5 (3)
C5—C6—C7—C8	0.0 (3)	C14—C16—C17—C18	−179.11 (16)
C6—C7—C8—C9	178.23 (18)	C16—C17—C18—C19	−0.3 (3)
C6—C7—C8—C3	−0.7 (3)	C17—C18—C19—C20	−0.2 (3)
C4—C3—C8—C9	−177.71 (15)	C17—C18—C19—C22	179.83 (19)
C2—C3—C8—C9	1.2 (2)	C18—C19—C20—C21	0.7 (3)
C4—C3—C8—C7	1.2 (2)	C22—C19—C20—C21	−179.40 (18)
C2—C3—C8—C7	−179.93 (14)	C19—C20—C21—C16	−0.5 (3)
C7—C8—C9—C10	−177.77 (16)	C17—C16—C21—C20	0.0 (3)
C3—C8—C9—C10	1.1 (2)	C14—C16—C21—C20	179.53 (16)
C8—C9—C10—C11	−1.0 (2)	C12—C13—C24—O3	−155.81 (15)
C3—C2—C11—O1	−173.98 (12)	C1—C13—C24—O3	−33.5 (2)
C1—C2—C11—O1	1.4 (2)	C14—C13—C24—O3	79.66 (18)
C3—C2—C11—C10	3.7 (2)	C12—C13—C24—O2	27.28 (18)
C1—C2—C11—C10	179.09 (13)	C1—C13—C24—O2	149.60 (13)
C9—C10—C11—O1	176.41 (14)	C14—C13—C24—O2	−97.25 (15)
C9—C10—C11—C2	−1.5 (2)	C14—C15—N1—C23	172.67 (14)
O1—C12—C13—C24	66.46 (16)	C14—C15—N1—C1	44.46 (15)
O1—C12—C13—C1	−57.99 (15)	C2—C1—N1—C23	60.86 (17)
O1—C12—C13—C14	−169.79 (11)	C13—C1—N1—C23	−177.89 (13)
N1—C1—C13—C24	156.25 (12)	C2—C1—N1—C15	−173.59 (12)
C2—C1—C13—C24	−80.75 (15)	C13—C1—N1—C15	−52.33 (13)
N1—C1—C13—C12	−77.92 (13)	C2—C11—O1—C12	−13.3 (2)
C2—C1—C13—C12	45.08 (15)	C10—C11—O1—C12	168.89 (12)
N1—C1—C13—C14	39.14 (14)	C13—C12—O1—C11	42.84 (16)
C2—C1—C13—C14	162.14 (11)	O3—C24—O2—C25	−1.3 (3)
C24—C13—C14—C16	101.64 (15)	C13—C24—O2—C25	175.64 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22A···Cg1i	0.96	2.84	3.788 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22A⋯Cg1i	0.96	2.84	3.788 (2)	169

Symmetry code: (i) . Cg1 is the centroid of the C16–C21 ring.