Methyl 4-(4-chloro-phen-yl)-3,3a,4,4a,5,12c-hexa-hydro-2-thia-naphtho-[1',2':3,2]furo[5,4-b]pyrrolizine-4a-carboxyl-ate.

In the title compound, C(25)H(22)ClNO(3)S, both the pyrrolidinyl and thia-zolyl rings adopt envelope conformations whereas the dihydro-pyran ring adopts a half-chair conformation. The chloro-phenyl and naphthalenyl ring systems are oriented at a dihedral angle of 59.7 (1)°. The crystal packing is stabilized by an intra-molecular C-H⋯N hydrogen bond and weak inter-molecular C-H⋯π inter-actions.

Related literature

For related structures, see: Nirmala et al. (2009 ▶); Selvanayagam et al. (2010 ▶). For the superposition of related structures, see: Gans & Shalloway (2001 ▶). For ring-puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C25H22ClNO3S

M = 451.95

Orthorhombic,

a = 8.0740 (6) Å

b = 12.1109 (8) Å

c = 22.1813 (15) Å

V = 2169.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 292 K

0.23 × 0.21 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

25236 measured reflections

5157 independent reflections

4559 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.110

S = 1.04

5157 reflections

281 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.15 e Å−3

Absolute structure: Flack (1983 ▶), 2186 Friedel pairs

Flack parameter: 0.01 (6)

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028746/ng5001sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028746/ng5001Isup2.hkl

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

C25H22ClNO3S	F(000) = 944
Mr = 451.95	Dx = 1.384 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 16148 reflections
a = 8.0740 (6) Å	θ = 2.1–27.6°
b = 12.1109 (8) Å	µ = 0.30 mm−1
c = 22.1813 (15) Å	T = 292 K
V = 2169.0 (3) Å3	Block, colourless
Z = 4	0.23 × 0.21 × 0.19 mm

Bruker SMART APEX CCD area-detector diffractometer	4559 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
graphite	θmax = 28.1°, θmin = 1.8°
ω scans	h = −10→10
25236 measured reflections	k = −15→16
5157 independent reflections	l = −29→29

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0624P)2 + 0.2403P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
5157 reflections	Δρmax = 0.28 e Å−3
281 parameters	Δρmin = −0.15 e Å−3
0 restraints	Absolute structure: Flack (1983), 2186 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (6)

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
Cl1	−0.39547 (9)	0.77136 (7)	0.50917 (3)	0.0888 (2)
S1	−0.28910 (8)	1.01078 (6)	0.12895 (3)	0.07732 (19)
O1	0.2032 (2)	0.67004 (11)	0.21872 (8)	0.0728 (5)
O2	0.2227 (2)	0.98332 (12)	0.25861 (7)	0.0698 (4)
O3	0.21864 (19)	0.84359 (14)	0.32261 (7)	0.0693 (4)
N1	−0.13547 (18)	0.82523 (13)	0.15571 (7)	0.0510 (4)
C1	0.03210 (19)	0.86266 (14)	0.17424 (8)	0.0409 (3)
H1	0.0406	0.9429	0.1697	0.049*
C2	0.1710 (2)	0.80726 (14)	0.14034 (9)	0.0479 (4)
C3	0.2357 (2)	0.85149 (16)	0.08546 (9)	0.0514 (4)
C4	0.1812 (3)	0.95119 (18)	0.05993 (8)	0.0586 (5)
H4	0.1006	0.9921	0.0799	0.070*
C5	0.2432 (3)	0.9901 (3)	0.00649 (10)	0.0750 (6)
H5	0.2045	1.0563	−0.0094	0.090*
C6	0.3656 (3)	0.9295 (3)	−0.02419 (11)	0.0887 (9)
H6	0.4055	0.9545	−0.0611	0.106*
C7	0.4251 (3)	0.8353 (3)	−0.00020 (12)	0.0814 (8)
H7	0.5082	0.7971	−0.0204	0.098*
C8	0.3646 (3)	0.79322 (19)	0.05482 (11)	0.0647 (6)
C9	0.4312 (3)	0.6989 (2)	0.08106 (14)	0.0822 (8)
H9	0.5146	0.6606	0.0611	0.099*
C10	0.3768 (3)	0.66178 (18)	0.13531 (15)	0.0802 (7)
H10	0.4270	0.6010	0.1532	0.096*
C11	0.2438 (2)	0.71561 (15)	0.16450 (11)	0.0596 (5)
C12	0.0538 (3)	0.70803 (15)	0.24674 (11)	0.0570 (5)
H12A	0.0551	0.6882	0.2891	0.068*
H12B	−0.0405	0.6720	0.2281	0.068*
C13	0.0355 (2)	0.83233 (13)	0.24070 (8)	0.0401 (3)
C14	−0.1375 (2)	0.87464 (13)	0.26073 (8)	0.0416 (3)
H14	−0.1306	0.9554	0.2608	0.050*
C15	−0.2488 (2)	0.84365 (17)	0.20738 (8)	0.0511 (4)
H15	−0.3079	0.7750	0.2166	0.061*
C16	−0.3753 (2)	0.9351 (2)	0.19154 (10)	0.0695 (6)
H16A	−0.3922	0.9837	0.2258	0.083*
H16B	−0.4809	0.9028	0.1804	0.083*
C17	−0.2033 (3)	0.8788 (2)	0.10353 (9)	0.0636 (5)
H17A	−0.2894	0.8336	0.0856	0.076*
H17B	−0.1175	0.8910	0.0736	0.076*
C18	−0.1970 (2)	0.84189 (14)	0.32279 (8)	0.0447 (4)
C19	−0.2712 (3)	0.74099 (17)	0.33593 (10)	0.0611 (5)
H19	−0.2815	0.6881	0.3058	0.073*
C20	−0.3297 (3)	0.71840 (19)	0.39317 (11)	0.0664 (6)
H20	−0.3805	0.6512	0.4014	0.080*
C21	−0.3120 (3)	0.79610 (19)	0.43776 (9)	0.0585 (5)
C22	−0.2352 (3)	0.89380 (18)	0.42702 (9)	0.0594 (5)
H22	−0.2210	0.9450	0.4579	0.071*
C23	−0.1785 (2)	0.91603 (15)	0.36953 (9)	0.0507 (4)
H23	−0.1262	0.9831	0.3621	0.061*
C24	0.1702 (2)	0.89594 (14)	0.27369 (8)	0.0441 (4)
C25	0.3441 (3)	0.8996 (3)	0.35799 (12)	0.0927 (9)
H25A	0.4469	0.8997	0.3363	0.139*
H25B	0.3584	0.8619	0.3957	0.139*
H25C	0.3099	0.9743	0.3654	0.139*

	U11	U22	U33	U12	U13	U23
Cl1	0.0877 (4)	0.1109 (5)	0.0676 (3)	0.0124 (4)	0.0262 (3)	0.0256 (3)
S1	0.0624 (3)	0.0981 (4)	0.0715 (3)	0.0219 (3)	−0.0083 (3)	0.0120 (3)
O1	0.0696 (9)	0.0436 (7)	0.1053 (12)	0.0169 (7)	0.0198 (9)	0.0080 (7)
O2	0.0752 (10)	0.0577 (8)	0.0764 (9)	−0.0241 (8)	−0.0210 (8)	0.0036 (7)
O3	0.0568 (8)	0.0881 (10)	0.0630 (9)	−0.0065 (8)	−0.0181 (7)	0.0179 (8)
N1	0.0377 (7)	0.0616 (9)	0.0536 (8)	−0.0053 (7)	−0.0014 (6)	−0.0136 (7)
C1	0.0361 (7)	0.0378 (8)	0.0490 (9)	−0.0001 (6)	−0.0001 (7)	−0.0084 (6)
C2	0.0380 (8)	0.0436 (8)	0.0622 (10)	−0.0047 (7)	0.0031 (8)	−0.0183 (8)
C3	0.0396 (9)	0.0584 (10)	0.0560 (10)	−0.0130 (8)	0.0042 (7)	−0.0246 (8)
C4	0.0552 (11)	0.0717 (12)	0.0488 (10)	−0.0096 (10)	0.0044 (8)	−0.0121 (9)
C5	0.0699 (13)	0.1004 (16)	0.0549 (11)	−0.0197 (13)	0.0044 (10)	−0.0034 (12)
C6	0.0671 (15)	0.140 (3)	0.0586 (14)	−0.0266 (18)	0.0179 (12)	−0.0136 (15)
C7	0.0525 (12)	0.117 (2)	0.0743 (15)	−0.0184 (14)	0.0228 (11)	−0.0421 (16)
C8	0.0415 (9)	0.0743 (13)	0.0783 (14)	−0.0148 (10)	0.0118 (9)	−0.0323 (11)
C9	0.0540 (12)	0.0672 (14)	0.125 (2)	−0.0026 (11)	0.0293 (14)	−0.0387 (15)
C10	0.0567 (12)	0.0478 (11)	0.136 (2)	0.0087 (10)	0.0226 (15)	−0.0153 (13)
C11	0.0502 (10)	0.0388 (9)	0.0899 (15)	−0.0004 (8)	0.0112 (10)	−0.0130 (9)
C12	0.0566 (11)	0.0405 (9)	0.0739 (13)	0.0020 (8)	0.0084 (10)	0.0057 (8)
C13	0.0345 (7)	0.0346 (7)	0.0510 (9)	0.0001 (6)	0.0008 (7)	−0.0017 (6)
C14	0.0337 (7)	0.0401 (8)	0.0511 (9)	−0.0012 (6)	0.0019 (7)	−0.0004 (7)
C15	0.0374 (8)	0.0641 (10)	0.0518 (10)	−0.0081 (7)	0.0012 (7)	−0.0060 (8)
C16	0.0389 (10)	0.1115 (17)	0.0580 (11)	0.0141 (11)	−0.0023 (8)	−0.0057 (12)
C17	0.0440 (9)	0.0976 (16)	0.0491 (10)	−0.0024 (11)	−0.0040 (9)	−0.0129 (10)
C18	0.0350 (8)	0.0460 (8)	0.0530 (9)	−0.0001 (7)	0.0004 (7)	0.0019 (7)
C19	0.0650 (12)	0.0503 (10)	0.0680 (12)	−0.0094 (9)	0.0068 (10)	−0.0009 (9)
C20	0.0659 (13)	0.0591 (11)	0.0742 (13)	−0.0068 (10)	0.0101 (11)	0.0146 (10)
C21	0.0465 (10)	0.0742 (12)	0.0547 (10)	0.0105 (10)	0.0059 (8)	0.0164 (9)
C22	0.0547 (11)	0.0701 (12)	0.0535 (10)	0.0023 (10)	−0.0019 (9)	−0.0027 (9)
C23	0.0442 (9)	0.0528 (9)	0.0553 (10)	−0.0042 (7)	−0.0006 (8)	−0.0006 (8)
C24	0.0336 (8)	0.0499 (9)	0.0489 (9)	0.0028 (7)	0.0009 (7)	−0.0022 (7)
C25	0.0586 (14)	0.150 (3)	0.0690 (15)	−0.0026 (16)	−0.0224 (12)	−0.0050 (16)

Cl1—C21	1.7473 (19)	C10—C11	1.413 (3)
S1—C16	1.803 (2)	C10—H10	0.9300
S1—C17	1.831 (2)	C12—C13	1.519 (2)
O1—C11	1.363 (3)	C12—H12A	0.9700
O1—C12	1.433 (3)	C12—H12B	0.9700
O2—C24	1.188 (2)	C13—C24	1.520 (2)
O3—C24	1.316 (2)	C13—C14	1.553 (2)
O3—C25	1.450 (3)	C14—C18	1.511 (2)
N1—C17	1.435 (3)	C14—C15	1.533 (2)
N1—C15	1.484 (2)	C14—H14	0.9800
N1—C1	1.485 (2)	C15—C16	1.547 (3)
C1—C2	1.507 (2)	C15—H15	0.9800
C1—C13	1.519 (2)	C16—H16A	0.9700
C1—H1	0.9800	C16—H16B	0.9700
C2—C11	1.366 (3)	C17—H17A	0.9700
C2—C3	1.429 (3)	C17—H17B	0.9700
C3—C4	1.404 (3)	C18—C23	1.380 (3)
C3—C8	1.429 (3)	C18—C19	1.392 (3)
C4—C5	1.370 (3)	C19—C20	1.382 (3)
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.406 (4)	C20—C21	1.373 (3)
C5—H5	0.9300	C20—H20	0.9300
C6—C7	1.348 (4)	C21—C22	1.357 (3)
C6—H6	0.9300	C22—C23	1.381 (3)
C7—C8	1.410 (4)	C22—H22	0.9300
C7—H7	0.9300	C23—H23	0.9300
C8—C9	1.390 (4)	C25—H25A	0.9600
C9—C10	1.358 (4)	C25—H25B	0.9600
C9—H9	0.9300	C25—H25C	0.9600
C16—S1—C17	86.54 (11)	C24—C13—C14	109.79 (13)
C11—O1—C12	117.08 (16)	C18—C14—C15	116.91 (14)
C24—O3—C25	115.36 (19)	C18—C14—C13	117.39 (14)
C17—N1—C15	108.65 (15)	C15—C14—C13	103.06 (14)
C17—N1—C1	115.64 (16)	C18—C14—H14	106.2
C15—N1—C1	107.59 (13)	C15—C14—H14	106.2
N1—C1—C2	113.81 (13)	C13—C14—H14	106.2
N1—C1—C13	102.20 (14)	N1—C15—C14	105.76 (13)
C2—C1—C13	111.28 (14)	N1—C15—C16	109.84 (16)
N1—C1—H1	109.8	C14—C15—C16	112.78 (16)
C2—C1—H1	109.8	N1—C15—H15	109.5
C13—C1—H1	109.8	C14—C15—H15	109.5
C11—C2—C3	118.79 (17)	C16—C15—H15	109.5
C11—C2—C1	119.09 (17)	C15—C16—S1	106.49 (13)
C3—C2—C1	122.02 (16)	C15—C16—H16A	110.4
C4—C3—C2	123.46 (17)	S1—C16—H16A	110.4
C4—C3—C8	117.4 (2)	C15—C16—H16B	110.4
C2—C3—C8	119.1 (2)	S1—C16—H16B	110.4
C5—C4—C3	122.0 (2)	H16A—C16—H16B	108.6
C5—C4—H4	119.0	N1—C17—S1	106.90 (13)
C3—C4—H4	119.0	N1—C17—H17A	110.3
C4—C5—C6	119.7 (3)	S1—C17—H17A	110.3
C4—C5—H5	120.1	N1—C17—H17B	110.3
C6—C5—H5	120.1	S1—C17—H17B	110.3
C7—C6—C5	120.1 (2)	H17A—C17—H17B	108.6
C7—C6—H6	120.0	C23—C18—C19	117.43 (17)
C5—C6—H6	120.0	C23—C18—C14	118.64 (15)
C6—C7—C8	121.6 (2)	C19—C18—C14	123.92 (16)
C6—C7—H7	119.2	C20—C19—C18	120.9 (2)
C8—C7—H7	119.2	C20—C19—H19	119.6
C9—C8—C7	121.7 (2)	C18—C19—H19	119.6
C9—C8—C3	119.2 (2)	C21—C20—C19	119.39 (19)
C7—C8—C3	119.0 (2)	C21—C20—H20	120.3
C10—C9—C8	121.2 (2)	C19—C20—H20	120.3
C10—C9—H9	119.4	C22—C21—C20	121.25 (18)
C8—C9—H9	119.4	C22—C21—Cl1	119.01 (18)
C9—C10—C11	119.9 (2)	C20—C21—Cl1	119.70 (17)
C9—C10—H10	120.0	C21—C22—C23	118.9 (2)
C11—C10—H10	120.0	C21—C22—H22	120.5
O1—C11—C2	124.87 (17)	C23—C22—H22	120.5
O1—C11—C10	113.6 (2)	C18—C23—C22	122.07 (18)
C2—C11—C10	121.5 (2)	C18—C23—H23	119.0
O1—C12—C13	111.22 (16)	C22—C23—H23	119.0
O1—C12—H12A	109.4	O2—C24—O3	123.72 (17)
C13—C12—H12A	109.4	O2—C24—C13	124.82 (16)
O1—C12—H12B	109.4	O3—C24—C13	111.43 (15)
C13—C12—H12B	109.4	O3—C25—H25A	109.5
H12A—C12—H12B	108.0	O3—C25—H25B	109.5
C12—C13—C1	109.08 (15)	H25A—C25—H25B	109.5
C12—C13—C24	112.97 (15)	O3—C25—H25C	109.5
C1—C13—C24	110.94 (14)	H25A—C25—H25C	109.5
C12—C13—C14	112.92 (14)	H25B—C25—H25C	109.5
C1—C13—C14	100.46 (13)
C17—N1—C1—C2	−83.59 (19)	C2—C1—C13—C14	−166.96 (12)
C15—N1—C1—C2	154.79 (16)	C12—C13—C14—C18	53.3 (2)
C17—N1—C1—C13	156.33 (15)	C1—C13—C14—C18	169.33 (14)
C15—N1—C1—C13	34.71 (17)	C24—C13—C14—C18	−73.75 (18)
N1—C1—C2—C11	−94.1 (2)	C12—C13—C14—C15	−76.75 (19)
C13—C1—C2—C11	20.8 (2)	C1—C13—C14—C15	39.28 (16)
N1—C1—C2—C3	89.84 (19)	C24—C13—C14—C15	156.20 (14)
C13—C1—C2—C3	−155.34 (15)	C17—N1—C15—C14	−135.34 (16)
C11—C2—C3—C4	−173.48 (17)	C1—N1—C15—C14	−9.46 (19)
C1—C2—C3—C4	2.6 (3)	C17—N1—C15—C16	−13.4 (2)
C11—C2—C3—C8	5.5 (2)	C1—N1—C15—C16	112.51 (17)
C1—C2—C3—C8	−178.41 (15)	C18—C14—C15—N1	−149.27 (15)
C2—C3—C4—C5	−178.47 (18)	C13—C14—C15—N1	−18.92 (18)
C8—C3—C4—C5	2.6 (3)	C18—C14—C15—C16	90.68 (19)
C3—C4—C5—C6	−0.2 (3)	C13—C14—C15—C16	−138.98 (16)
C4—C5—C6—C7	−2.0 (4)	N1—C15—C16—S1	−18.99 (19)
C5—C6—C7—C8	1.7 (4)	C14—C15—C16—S1	98.69 (16)
C6—C7—C8—C9	−176.9 (2)	C17—S1—C16—C15	34.61 (15)
C6—C7—C8—C3	0.7 (3)	C15—N1—C17—S1	39.89 (18)
C4—C3—C8—C9	174.88 (19)	C1—N1—C17—S1	−81.16 (16)
C2—C3—C8—C9	−4.1 (3)	C16—S1—C17—N1	−44.10 (15)
C4—C3—C8—C7	−2.8 (3)	C15—C14—C18—C23	−138.51 (17)
C2—C3—C8—C7	178.22 (17)	C13—C14—C18—C23	98.24 (19)
C7—C8—C9—C10	177.1 (2)	C15—C14—C18—C19	41.0 (2)
C3—C8—C9—C10	−0.4 (3)	C13—C14—C18—C19	−82.2 (2)
C8—C9—C10—C11	3.6 (4)	C23—C18—C19—C20	2.5 (3)
C12—O1—C11—C2	12.4 (3)	C14—C18—C19—C20	−176.99 (19)
C12—O1—C11—C10	−170.33 (19)	C18—C19—C20—C21	−1.0 (3)
C3—C2—C11—O1	174.65 (18)	C19—C20—C21—C22	−1.3 (3)
C1—C2—C11—O1	−1.6 (3)	C19—C20—C21—Cl1	176.54 (18)
C3—C2—C11—C10	−2.4 (3)	C20—C21—C22—C23	1.9 (3)
C1—C2—C11—C10	−178.61 (18)	Cl1—C21—C22—C23	−175.99 (16)
C9—C10—C11—O1	−179.5 (2)	C19—C18—C23—C22	−2.0 (3)
C9—C10—C11—C2	−2.2 (3)	C14—C18—C23—C22	177.58 (17)
C11—O1—C12—C13	−41.6 (3)	C21—C22—C23—C18	−0.2 (3)
O1—C12—C13—C1	59.6 (2)	C25—O3—C24—O2	−0.4 (3)
O1—C12—C13—C24	−64.3 (2)	C25—O3—C24—C13	−178.41 (17)
O1—C12—C13—C14	170.33 (16)	C12—C13—C24—O2	149.37 (19)
N1—C1—C13—C12	73.74 (17)	C1—C13—C24—O2	26.5 (2)
C2—C1—C13—C12	−48.09 (18)	C14—C13—C24—O2	−83.6 (2)
N1—C1—C13—C24	−161.19 (13)	C12—C13—C24—O3	−32.6 (2)
C2—C1—C13—C24	76.98 (16)	C1—C13—C24—O3	−155.50 (15)
N1—C1—C13—C14	−45.13 (15)	C14—C13—C24—O3	94.37 (17)

Cg is the centroid of the chlorophenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···N1	0.97	2.57	2.903 (3)	100
C25—H25A···Cgi	0.96	2.79	3.431 (3)	125

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the chloro­phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯N1	0.97	2.57	2.903 (3)	100
C25—H25A⋯Cgi	0.96	2.79	3.431 (3)	125

Symmetry code: (i) .