Methyl 3-(4-methoxy-phen-yl)-1-methyl-1,2,3,3a,4,11b-hexa-hydro-benzo[f]chromeno[4,3-b]pyrrole-3a-carboxyl-ate.

In the title compound, C(25)H(25)NO(4), the pyrrolidine ring exhibits an envelope conformation and the tetra-hydro-pyran ring exhibits a half-chair conformation. The crystal structure is stabilized by inter-molecular C-H⋯π inter-actions.

Related literature

For general background to the applications and biological activity of chromenopyrrole compounds, see: Caine (1993 ▶); Carlson (1993 ▶); Sokoloff et al. (1990 ▶); Wilner (1985 ▶); Biava et al. (2005 ▶); Fernandes et al. (2004 ▶); Borthwick et al. (2000 ▶); Jiang et al. (2004 ▶). For a related structure, see: Nirmala et al. (2009 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C25H25NO4

M = 403.46

Triclinic,

a = 7.9287 (5) Å

b = 10.8707 (6) Å

c = 11.6884 (7) Å

α = 95.662 (3)°

β = 92.332 (4)°

γ = 91.797 (4)°

V = 1001.05 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.981, T max = 0.985

21741 measured reflections

4776 independent reflections

3836 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.164

S = 1.05

4776 reflections

274 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.34 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010056/bt5203sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010056/bt5203Isup2.hkl

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

C25H25NO4	Z = 2
Mr = 403.46	F(000) = 428
Triclinic, P1	Dx = 1.339 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9287 (5) Å	Cell parameters from 4776 reflections
b = 10.8707 (6) Å	θ = 1.8–28°
c = 11.6884 (7) Å	µ = 0.09 mm−1
α = 95.662 (3)°	T = 293 K
β = 92.332 (4)°	Block, colourless
γ = 91.797 (4)°	0.25 × 0.22 × 0.19 mm
V = 1001.05 (10) Å3

Bruker APEXII CCD area-detector diffractometer	4776 independent reflections
Radiation source: fine-focus sealed tube	3836 reflections with I > 2σ(I)
graphite	Rint = 0.050
ω and φ scans	θmax = 28.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.981, Tmax = 0.985	k = −14→14
21741 measured reflections	l = −15→15

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) = 0.164	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.099P)2 + 0.1502P] where P = (Fo2 + 2Fc2)/3
4776 reflections	(Δ/σ)max < 0.001
274 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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 > 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	0.28588 (16)	0.64583 (12)	0.75782 (11)	0.0302 (3)
C2	0.3939 (2)	0.54431 (14)	0.75627 (13)	0.0390 (3)
H2	0.4605	0.5336	0.8216	0.047*
C3	0.4023 (2)	0.46191 (16)	0.66078 (15)	0.0517 (4)
H3	0.4730	0.3954	0.6628	0.062*
C4	0.3065 (3)	0.47564 (17)	0.56016 (15)	0.0549 (5)
H4	0.3152	0.4200	0.4951	0.066*
C5	0.2008 (2)	0.57083 (16)	0.55850 (14)	0.0467 (4)
H5	0.1366	0.5797	0.4917	0.056*
C6	0.18576 (18)	0.65693 (13)	0.65573 (12)	0.0356 (3)
C7	0.0693 (2)	0.75203 (15)	0.65447 (13)	0.0411 (4)
H7	0.0030	0.7590	0.5881	0.049*
C8	0.05266 (19)	0.83293 (15)	0.74783 (13)	0.0407 (3)
H8	−0.0254	0.8948	0.7458	0.049*
C9	0.15365 (17)	0.82395 (13)	0.84889 (12)	0.0322 (3)
C10	0.27031 (16)	0.73371 (12)	0.85626 (11)	0.0281 (3)
C11	0.36725 (15)	0.72609 (11)	0.96946 (11)	0.0269 (3)
H11	0.3837	0.6393	0.9817	0.032*
C12	0.57832 (17)	0.81208 (16)	1.10401 (12)	0.0403 (4)
H12A	0.6351	0.8921	1.1238	0.048*
H12B	0.6540	0.7484	1.1240	0.048*
C13	0.41479 (16)	0.80366 (13)	1.16870 (11)	0.0311 (3)
H13	0.4151	0.7246	1.2024	0.037*
C14	0.27455 (15)	0.79025 (12)	1.07047 (11)	0.0280 (3)
C15	0.22197 (17)	0.91646 (12)	1.03958 (12)	0.0331 (3)
H15A	0.1609	0.9565	1.1023	0.040*
H15B	0.3224	0.9673	1.0304	0.040*
C16	0.12443 (17)	0.71790 (14)	1.10765 (12)	0.0349 (3)
C17	0.0270 (3)	0.52672 (19)	1.1624 (2)	0.0776 (7)
H17A	0.0029	0.5627	1.2381	0.116*
H17B	0.0641	0.4440	1.1666	0.116*
H17C	−0.0732	0.5248	1.1132	0.116*
C18	0.66502 (17)	0.73843 (15)	0.91570 (13)	0.0394 (3)
H18A	0.7666	0.7891	0.9293	0.059*
H18B	0.6331	0.7310	0.8351	0.059*
H18C	0.6842	0.6578	0.9396	0.059*
C19	0.38660 (16)	0.90191 (13)	1.26574 (11)	0.0304 (3)
C20	0.43808 (19)	1.02529 (14)	1.26490 (12)	0.0375 (3)
H20	0.4962	1.0494	1.2028	0.045*
C21	0.4050 (2)	1.11255 (14)	1.35383 (13)	0.0410 (3)
H21	0.4418	1.1943	1.3516	0.049*
C22	0.31722 (18)	1.07914 (14)	1.44666 (12)	0.0367 (3)
C23	0.26739 (18)	0.95725 (15)	1.45086 (12)	0.0393 (3)
H23	0.2102	0.9334	1.5135	0.047*
C24	0.30326 (18)	0.87017 (14)	1.36077 (12)	0.0365 (3)
H24	0.2701	0.7879	1.3645	0.044*
C25	0.1930 (2)	1.1439 (2)	1.62332 (14)	0.0566 (5)
H25A	0.0839	1.1100	1.5958	0.085*
H25B	0.1796	1.2175	1.6741	0.085*
H25C	0.2513	1.0843	1.6641	0.085*
N1	0.53080 (13)	0.79497 (11)	0.98078 (9)	0.0307 (3)
O1	0.11812 (13)	0.90921 (10)	0.93631 (9)	0.0414 (3)
O2	−0.00673 (14)	0.76045 (13)	1.13242 (13)	0.0625 (4)
O3	0.15812 (16)	0.59997 (11)	1.11635 (13)	0.0602 (4)
O4	0.28770 (16)	1.17310 (11)	1.52900 (10)	0.0519 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0296 (6)	0.0321 (6)	0.0298 (6)	−0.0027 (5)	0.0054 (5)	0.0073 (5)
C2	0.0454 (8)	0.0389 (7)	0.0336 (7)	0.0070 (6)	0.0048 (6)	0.0056 (6)
C3	0.0669 (11)	0.0452 (9)	0.0437 (9)	0.0145 (8)	0.0089 (8)	0.0019 (7)
C4	0.0749 (12)	0.0513 (10)	0.0367 (9)	0.0022 (9)	0.0062 (8)	−0.0065 (7)
C5	0.0546 (10)	0.0527 (9)	0.0317 (8)	−0.0054 (8)	−0.0013 (7)	0.0024 (6)
C6	0.0364 (7)	0.0404 (7)	0.0304 (7)	−0.0057 (6)	0.0025 (5)	0.0073 (6)
C7	0.0394 (8)	0.0520 (9)	0.0325 (7)	0.0001 (7)	−0.0067 (6)	0.0113 (6)
C8	0.0359 (7)	0.0474 (8)	0.0404 (8)	0.0099 (6)	−0.0026 (6)	0.0120 (6)
C9	0.0300 (6)	0.0353 (7)	0.0320 (7)	0.0030 (5)	0.0010 (5)	0.0068 (5)
C10	0.0252 (6)	0.0313 (6)	0.0288 (6)	0.0005 (5)	0.0028 (5)	0.0072 (5)
C11	0.0239 (6)	0.0301 (6)	0.0279 (6)	0.0043 (5)	0.0040 (5)	0.0070 (5)
C12	0.0250 (6)	0.0628 (10)	0.0322 (7)	0.0038 (6)	0.0005 (5)	0.0003 (6)
C13	0.0277 (6)	0.0376 (7)	0.0288 (6)	0.0042 (5)	0.0018 (5)	0.0061 (5)
C14	0.0239 (6)	0.0327 (6)	0.0280 (6)	0.0034 (5)	0.0032 (5)	0.0034 (5)
C15	0.0308 (6)	0.0344 (7)	0.0339 (7)	0.0069 (5)	−0.0009 (5)	0.0008 (5)
C16	0.0291 (7)	0.0443 (8)	0.0309 (7)	−0.0018 (6)	0.0049 (5)	0.0012 (6)
C17	0.0787 (15)	0.0543 (11)	0.1033 (18)	−0.0161 (10)	0.0519 (13)	0.0120 (11)
C18	0.0269 (7)	0.0548 (9)	0.0378 (7)	0.0067 (6)	0.0085 (6)	0.0064 (6)
C19	0.0251 (6)	0.0402 (7)	0.0262 (6)	0.0019 (5)	0.0001 (5)	0.0052 (5)
C20	0.0391 (7)	0.0441 (8)	0.0302 (7)	−0.0039 (6)	0.0053 (6)	0.0085 (6)
C21	0.0476 (8)	0.0380 (7)	0.0371 (8)	−0.0034 (6)	−0.0010 (6)	0.0052 (6)
C22	0.0341 (7)	0.0460 (8)	0.0287 (7)	0.0051 (6)	−0.0044 (5)	−0.0010 (6)
C23	0.0360 (7)	0.0540 (9)	0.0280 (7)	−0.0030 (6)	0.0058 (6)	0.0050 (6)
C24	0.0384 (7)	0.0408 (7)	0.0305 (7)	−0.0043 (6)	0.0024 (6)	0.0066 (6)
C25	0.0484 (9)	0.0837 (13)	0.0347 (8)	0.0121 (9)	0.0016 (7)	−0.0109 (8)
N1	0.0221 (5)	0.0412 (6)	0.0296 (6)	0.0029 (4)	0.0037 (4)	0.0051 (4)
O1	0.0434 (6)	0.0443 (6)	0.0364 (6)	0.0202 (5)	−0.0060 (4)	0.0007 (4)
O2	0.0303 (6)	0.0720 (9)	0.0899 (10)	0.0074 (5)	0.0210 (6)	0.0215 (7)
O3	0.0556 (7)	0.0393 (6)	0.0896 (10)	−0.0023 (5)	0.0395 (7)	0.0125 (6)
O4	0.0600 (7)	0.0559 (7)	0.0375 (6)	0.0077 (6)	0.0027 (5)	−0.0085 (5)

C1—C2	1.4171 (19)	C14—C15	1.5193 (18)
C1—C6	1.4234 (19)	C15—O1	1.4274 (16)
C1—C10	1.4331 (18)	C15—H15A	0.9700
C2—C3	1.366 (2)	C15—H15B	0.9700
C2—H2	0.9300	C16—O2	1.1864 (17)
C3—C4	1.397 (3)	C16—O3	1.3304 (19)
C3—H3	0.9300	C17—O3	1.444 (2)
C4—C5	1.353 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.411 (2)	C17—H17C	0.9600
C5—H5	0.9300	C18—N1	1.4503 (16)
C6—C7	1.408 (2)	C18—H18A	0.9600
C7—C8	1.346 (2)	C18—H18B	0.9600
C7—H7	0.9300	C18—H18C	0.9600
C8—C9	1.413 (2)	C19—C24	1.3823 (19)
C8—H8	0.9300	C19—C20	1.391 (2)
C9—O1	1.3547 (17)	C20—C21	1.376 (2)
C9—C10	1.3757 (18)	C20—H20	0.9300
C10—C11	1.5137 (17)	C21—C22	1.385 (2)
C11—N1	1.4715 (17)	C21—H21	0.9300
C11—C14	1.5365 (17)	C22—O4	1.3652 (17)
C11—H11	0.9800	C22—C23	1.377 (2)
C12—N1	1.4661 (18)	C23—C24	1.389 (2)
C12—C13	1.5321 (19)	C23—H23	0.9300
C12—H12A	0.9700	C24—H24	0.9300
C12—H12B	0.9700	C25—O4	1.415 (2)
C13—C19	1.5078 (18)	C25—H25A	0.9600
C13—C14	1.5584 (18)	C25—H25B	0.9600
C13—H13	0.9800	C25—H25C	0.9600
C14—C16	1.5083 (19)
C2—C1—C6	116.85 (13)	C11—C14—C13	102.15 (9)
C2—C1—C10	123.60 (12)	O1—C15—C14	112.60 (11)
C6—C1—C10	119.53 (12)	O1—C15—H15A	109.1
C3—C2—C1	121.38 (14)	C14—C15—H15A	109.1
C3—C2—H2	119.3	O1—C15—H15B	109.1
C1—C2—H2	119.3	C14—C15—H15B	109.1
C2—C3—C4	121.19 (16)	H15A—C15—H15B	107.8
C2—C3—H3	119.4	O2—C16—O3	122.75 (14)
C4—C3—H3	119.4	O2—C16—C14	125.01 (14)
C5—C4—C3	119.19 (15)	O3—C16—C14	112.14 (11)
C5—C4—H4	120.4	O3—C17—H17A	109.5
C3—C4—H4	120.4	O3—C17—H17B	109.5
C4—C5—C6	121.58 (15)	H17A—C17—H17B	109.5
C4—C5—H5	119.2	O3—C17—H17C	109.5
C6—C5—H5	119.2	H17A—C17—H17C	109.5
C7—C6—C5	120.90 (14)	H17B—C17—H17C	109.5
C7—C6—C1	119.31 (13)	N1—C18—H18A	109.5
C5—C6—C1	119.77 (14)	N1—C18—H18B	109.5
C8—C7—C6	120.99 (13)	H18A—C18—H18B	109.5
C8—C7—H7	119.5	N1—C18—H18C	109.5
C6—C7—H7	119.5	H18A—C18—H18C	109.5
C7—C8—C9	120.09 (13)	H18B—C18—H18C	109.5
C7—C8—H8	120.0	C24—C19—C20	117.15 (13)
C9—C8—H8	120.0	C24—C19—C13	119.33 (12)
O1—C9—C10	124.81 (12)	C20—C19—C13	123.51 (12)
O1—C9—C8	113.03 (12)	C21—C20—C19	121.51 (13)
C10—C9—C8	122.12 (13)	C21—C20—H20	119.2
C9—C10—C1	117.93 (12)	C19—C20—H20	119.2
C9—C10—C11	118.97 (12)	C20—C21—C22	120.28 (14)
C1—C10—C11	122.96 (11)	C20—C21—H21	119.9
N1—C11—C10	114.52 (10)	C22—C21—H21	119.9
N1—C11—C14	101.23 (10)	O4—C22—C23	124.85 (14)
C10—C11—C14	111.22 (10)	O4—C22—C21	115.66 (14)
N1—C11—H11	109.9	C23—C22—C21	119.49 (13)
C10—C11—H11	109.9	C22—C23—C24	119.42 (13)
C14—C11—H11	109.9	C22—C23—H23	120.3
N1—C12—C13	106.97 (11)	C24—C23—H23	120.3
N1—C12—H12A	110.3	C19—C24—C23	122.11 (14)
C13—C12—H12A	110.3	C19—C24—H24	118.9
N1—C12—H12B	110.3	C23—C24—H24	118.9
C13—C12—H12B	110.3	O4—C25—H25A	109.5
H12A—C12—H12B	108.6	O4—C25—H25B	109.5
C19—C13—C12	118.15 (12)	H25A—C25—H25B	109.5
C19—C13—C14	115.05 (10)	O4—C25—H25C	109.5
C12—C13—C14	103.36 (10)	H25A—C25—H25C	109.5
C19—C13—H13	106.5	H25B—C25—H25C	109.5
C12—C13—H13	106.5	C18—N1—C12	110.87 (11)
C14—C13—H13	106.5	C18—N1—C11	115.47 (11)
C16—C14—C15	110.32 (11)	C12—N1—C11	106.57 (10)
C16—C14—C11	114.99 (11)	C9—O1—C15	118.16 (10)
C15—C14—C11	108.79 (10)	C16—O3—C17	115.85 (14)
C16—C14—C13	109.58 (11)	C22—O4—C25	117.54 (14)
C15—C14—C13	110.74 (11)
C6—C1—C2—C3	0.6 (2)	C12—C13—C14—C15	−87.13 (13)
C10—C1—C2—C3	178.95 (14)	C19—C13—C14—C11	158.84 (11)
C1—C2—C3—C4	1.0 (3)	C12—C13—C14—C11	28.58 (13)
C2—C3—C4—C5	−1.5 (3)	C16—C14—C15—O1	−69.67 (14)
C3—C4—C5—C6	0.4 (3)	C11—C14—C15—O1	57.34 (14)
C4—C5—C6—C7	−176.93 (16)	C13—C14—C15—O1	168.84 (10)
C4—C5—C6—C1	1.3 (2)	C15—C14—C16—O2	−14.5 (2)
C2—C1—C6—C7	176.53 (13)	C11—C14—C16—O2	−137.97 (16)
C10—C1—C6—C7	−1.9 (2)	C13—C14—C16—O2	107.68 (17)
C2—C1—C6—C5	−1.7 (2)	C15—C14—C16—O3	169.18 (12)
C10—C1—C6—C5	179.87 (13)	C11—C14—C16—O3	45.69 (16)
C5—C6—C7—C8	178.81 (15)	C13—C14—C16—O3	−68.65 (15)
C1—C6—C7—C8	0.6 (2)	C12—C13—C19—C24	−145.25 (14)
C6—C7—C8—C9	0.5 (2)	C14—C13—C19—C24	92.10 (15)
C7—C8—C9—O1	−177.94 (14)	C12—C13—C19—C20	35.71 (18)
C7—C8—C9—C10	−0.3 (2)	C14—C13—C19—C20	−86.94 (16)
O1—C9—C10—C1	176.35 (12)	C24—C19—C20—C21	−1.1 (2)
C8—C9—C10—C1	−1.0 (2)	C13—C19—C20—C21	177.95 (13)
O1—C9—C10—C11	0.5 (2)	C19—C20—C21—C22	−0.7 (2)
C8—C9—C10—C11	−176.85 (12)	C20—C21—C22—O4	−178.57 (13)
C2—C1—C10—C9	−176.25 (13)	C20—C21—C22—C23	1.8 (2)
C6—C1—C10—C9	2.07 (19)	O4—C22—C23—C24	179.22 (13)
C2—C1—C10—C11	−0.6 (2)	C21—C22—C23—C24	−1.2 (2)
C6—C1—C10—C11	177.76 (11)	C20—C19—C24—C23	1.7 (2)
C9—C10—C11—N1	−93.00 (14)	C13—C19—C24—C23	−177.37 (12)
C1—C10—C11—N1	91.35 (14)	C22—C23—C24—C19	−0.6 (2)
C9—C10—C11—C14	21.00 (17)	C13—C12—N1—C18	−150.22 (12)
C1—C10—C11—C14	−154.65 (12)	C13—C12—N1—C11	−23.81 (14)
N1—C12—C13—C19	−132.33 (12)	C10—C11—N1—C18	−74.85 (14)
N1—C12—C13—C14	−3.96 (15)	C14—C11—N1—C18	165.40 (11)
N1—C11—C14—C16	−161.46 (11)	C10—C11—N1—C12	161.56 (11)
C10—C11—C14—C16	76.47 (14)	C14—C11—N1—C12	41.81 (12)
N1—C11—C14—C15	74.25 (12)	C10—C9—O1—C15	7.9 (2)
C10—C11—C14—C15	−47.82 (14)	C8—C9—O1—C15	−174.55 (12)
N1—C11—C14—C13	−42.87 (12)	C14—C15—O1—C9	−37.70 (17)
C10—C11—C14—C13	−164.94 (10)	O2—C16—O3—C17	−2.3 (3)
C19—C13—C14—C16	−78.79 (14)	C14—C16—O3—C17	174.09 (16)
C12—C13—C14—C16	150.94 (11)	C23—C22—O4—C25	−2.7 (2)
C19—C13—C14—C15	43.13 (15)	C21—C22—O4—C25	177.75 (14)

Cg4 is the centroid of the C1/C6–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O3	0.98	2.48	2.8514 (18)	102
C13—H13···O3	0.98	2.53	2.9610 (18)	107
C17—H17B···Cg4i	0.97	2.94	3.502 (2)	119

Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C1/C6–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17B⋯Cg4i	0.97	2.94	3.502 (2)	119

Symmetry code: (i) .