Ethyl 7′-(6-benz­yloxy-2,2-dimethyl­tetra­hydro­furo[3,2-d][1,3]dioxol-5-yl)-2-oxo-5′,6′,7′,7a'-tetra­hydro-1′H,2H-spiro­[acenaphthyl­ene-1,5′-pyrrolo­[1,2-c][1,3]thia­zole]-6′-carboxyl­ate

Jagadeesan, G.; Sethusankar, K.; Prasanna, R.; Raghunathan, R.

doi:10.1107/S1600536812032291

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2505-o2506

https://doi.org/10.1107/S1600536812032291

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Ethyl 7′-(6-benzyloxy-2,2-dimethyltetrahydrofuro[3,2-d][1,3]dioxol-5-yl)-2-oxo-5′,6′,7′,7a'-tetrahydro-1′H,2H-spiro[acenaphthylene-1,5′-pyrrolo[1,2-c][1,3]thiazole]-6′-carboxylate

G. Jagadeesan,^a K. Sethusankar,^b ^* R. Prasanna ^c and R. Raghunathan ^c

^aDepartment of Physics, Dr MGR Educational and Research Institute, Dr MGR University, Chennai 600 095, India, ^bDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^cDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 2 July 2012; accepted 16 July 2012; online 21 July 2012)

In the title compound, C₃₄H₃₅NO₇S, the acenaphthylene unit is essentially planar (r.m.s. deviation = 0.0335 Å). The pyrrolothiazole ring system is folded about the bridging N—C bond; the thiazolidine and pyrrolidine rings adopt S- and C-envelope conformations, respectively, with a `butterfly' angle between the mean planes of 51.38 (10)°. The dioxolane and tetrahydrofuran rings adopt O- and a C-envelope conformations, respectively, with a `butterfly' angle between the mean planes of 57.12 (10)°. Two C atoms are each disordered over two positions with site-occupancy factors of 0.450 (7) and 0.550 (7). The crystal packing is stabilized by C—H⋯O interactions, generating an R₂²(14) graph-set ring motif.

Related literature

For the biological properties of spiroheterocycles, see: Kilonda et al. (1995 ); Ferguson et al. (2005 ). For a related structure, see: Jagadeesan et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₃₄H₃₅NO₇S
M_r = 601.69
Monoclinic, P 2₁
a = 8.588 (5) Å
b = 20.446 (5) Å
c = 8.851 (5) Å
β = 93.282 (5)°
V = 1551.6 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.955, T_max = 0.970
13521 measured reflections
5470 independent reflections
4678 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.083
S = 1.03
5470 reflections
400 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 2630 Friedel pairs
Flack parameter: 0.04 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3ⁱ	0.93	2.51	3.375 (4)	155
C17—H17A⋯O7ⁱⁱ	0.97	2.44	3.309 (3)	148
C23—H23F⋯O4ⁱⁱⁱ	0.96	2.57	3.497 (9)	163
C31—H31⋯O5^iv	0.93	2.47	3.393 (4)	173
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (ii) x+1, y, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (iv) x, y, z-1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812032291/pv2565sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032291/pv2565Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032291/pv2565Isup3.cml

checkCIF report

Comment top

The design and novel synthesis of glycospiroheterocycles are interesting because of the synthetic challenge they present and their biological profile against viruses, bacteria, and cancer cells (Ferguson et al., 2005). Pyrrolidines and pyrroles are common structural motifs in drugs and drug candidates owing to their ability to act as selective glycosidase inhibitors, which are used in the treatment of diabetes, cancer, malaria and viral infections, including AIDS (Kilonda et al., 1995).

In the title molecule (Fig. 1), the acenaphthylene moiety (C19/C24–C34) is essentially planar (rmsd = 0.0335 Å) with O3 deviating from the acenaphthylene moiety by 0.209 (3) Å. The pyrrolothiazole ring (C15–C20/N1/S1) system is folded about the bridging N1–C16 bond, as observed in another structurally similar compound (Jagadeesan et al., 2012). The thiazolidine ring (C16–C18/N1/S1) adopts an S1-envelope conformation with S1 deviating from the mean plane of the remaining ring atoms by 0.815 (3) Å while the pyrrolidine ring (C15/C16/C19/C20/N1) adopt adopts a C20-envelope conformation with C20 deviating from the mean plane of the remaining ring atoms by 0.538 (3) Å; the "butter-fly" angle between the mean planes C16-C18/N1 and C15/C16/C19/N1 being 51.38 (10) °. The dioxolane ring (C9–C11/O6/O7) adopts an O7-envelope conformation with the atom O7 deviating from the mean plane of the remaining ring atoms by 0.299 (4) Å. The tetrahydrofuran ring (O5/C8/C9/C11/C12) adopts a C12-envelope conformation with C12 deviating from the mean plane of the remaining ring atoms by 0.607 (3) Å; the "butter-fly" angle between the mean planes O5/C8/C9/C11 and O6/C9–C11 is 57.12 (10) °.

The crystal packing is stabilized by C—H···O intermolecular interactions; C5—H5···O3 and C23—H23F···O4 hydrogen bonds generate R²₂(14) graphset ring motif (Bernstein, et al., 1995) (Table 1 and Fig. 2).

Related literature top

For the biological properties of spiroheterocycles, see: Kilonda et al. (1995); Ferguson et al. (2005). For a related structure, see: Jagadeesan et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of α-D-xylo-hept-5-enofuranuronic acid, 5,6-dideoxy-1,2-O-(1-methylethylidene)-3-O- (phenylmethyl)-, ethyl ester (0.300 g, 0.86 mmol), acenaphthenequinone (0.156 g, 0.86 mmol) and 4-thiazolidinecarboxyli cacid (0.137 g, 1.0 mmol) was refluxed in toluene for about 5 h under Dean stark reaction condition to yield the title compound. After the completion of reaction as indicated by TLC, solvent was evaporated under reduced pressure. The crude product was purified by column chromatography using hexane: EtOAc (4:1) as eluent. The block shaped single crystals of the title compound suitable for X-ray diffraction were obtained from solution of hexane: EtOAc (4:1) by slow evaportion at room temperature.

Structure description top

For the biological properties of spiroheterocycles, see: Kilonda et al. (1995); Ferguson et al. (2005). For a related structure, see: Jagadeesan et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 30% probability level. H–atoms are present as small spheres of arbitary radius. The minor fractions of the disordered carbon atoms have been represented by broken bonds.
	Fig. 2. The crystal packing of the title compound viewed down c axis, showing the hydrogen bonds resulting in R²₂(14) graph-set ring motif. H–atoms not involved in hydrogen bonds have been excluded for clarity.

Ethyl 7'-(6-benzyloxy-2,2-dimethyltetrahydrofuro[3,2-d][1,3]dioxol- 5-yl)-2-oxo-5',6',7',7a'-tetrahydro-1'H,2H-spiro[acenaphthylene- 1,5'-pyrrolo[1,2-c][1,3]thiazole]-6'-carboxylate top

Crystal data top

C₃₄H₃₅NO₇S	F(000) = 636
M_r = 601.69	D_x = 1.288 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5470 reflections
a = 8.588 (5) Å	θ = 2.3–25.0°
b = 20.446 (5) Å	µ = 0.15 mm⁻¹
c = 8.851 (5) Å	T = 293 K
β = 93.282 (5)°	Block, colourless
V = 1551.6 (13) Å³	0.30 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	5470 independent reflections
Radiation source: fine-focus sealed tube	4678 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.955, T_max = 0.970	k = −24→24
13521 measured reflections	l = −10→10

Refinement top

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0365P)² + 0.1903P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
5470 reflections	Δρ_max = 0.17 e Å⁻³
400 parameters	Δρ_min = −0.16 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 2630 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (7)

Crystal data top

C₃₄H₃₅NO₇S	V = 1551.6 (13) Å³
M_r = 601.69	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.588 (5) Å	µ = 0.15 mm⁻¹
b = 20.446 (5) Å	T = 293 K
c = 8.851 (5) Å	0.30 × 0.20 × 0.20 mm
β = 93.282 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	5470 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4678 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.970	R_int = 0.031
13521 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.17 e Å⁻³
S = 1.03	Δρ_min = −0.16 e Å⁻³
5470 reflections	Absolute structure: Flack (1983), 2630 Friedel pairs
400 parameters	Absolute structure parameter: 0.04 (7)
5 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6985 (4)	1.0180 (2)	−0.1860 (4)	0.0964 (12)
H1	0.7439	0.9791	−0.1517	0.116*
C2	0.7881 (4)	1.0639 (3)	−0.2530 (5)	0.1233 (17)
H2	0.8946	1.0569	−0.2592	0.148*
C3	0.7226 (6)	1.1190 (2)	−0.3098 (5)	0.1204 (15)
H3	0.7837	1.1503	−0.3544	0.145*
C4	0.5673 (7)	1.12883 (19)	−0.3019 (5)	0.1210 (16)
H4	0.5213	1.1662	−0.3442	0.145*
C5	0.4768 (4)	1.08343 (17)	−0.2310 (4)	0.0861 (10)
H5	0.3703	1.0906	−0.2259	0.103*
C6	0.5424 (3)	1.02855 (15)	−0.1686 (3)	0.0598 (7)
C7	0.4478 (3)	0.97918 (18)	−0.0920 (3)	0.0767 (9)
H7A	0.3442	0.9965	−0.0788	0.092*
H7B	0.4373	0.9401	−0.1540	0.092*
C8	0.4389 (2)	0.91510 (11)	0.1311 (2)	0.0385 (5)
H8	0.3568	0.8941	0.0667	0.046*
C9	0.3749 (2)	0.94455 (12)	0.2722 (2)	0.0444 (5)
H9	0.3382	0.9896	0.2576	0.053*
C10	0.2888 (3)	0.89133 (16)	0.4821 (2)	0.0579 (7)
C11	0.5109 (2)	0.93842 (12)	0.3919 (2)	0.0448 (5)
H11	0.5512	0.9815	0.4227	0.054*
C12	0.5534 (2)	0.86545 (11)	0.2003 (2)	0.0371 (5)
H12	0.4946	0.8287	0.2394	0.045*
C13	0.1895 (4)	0.9367 (2)	0.5694 (3)	0.0944 (12)
H13A	0.2072	0.9285	0.6758	0.142*
H13B	0.0816	0.9295	0.5401	0.142*
H13C	0.2165	0.9812	0.5481	0.142*
C14	0.2592 (5)	0.8205 (2)	0.5147 (5)	0.1105 (13)
H14A	0.3315	0.7940	0.4630	0.166*
H14B	0.1546	0.8094	0.4802	0.166*
H14C	0.2727	0.8129	0.6217	0.166*
C15	0.6747 (2)	0.83868 (11)	0.0969 (2)	0.0348 (5)
H15	0.6642	0.8626	0.0009	0.042*
C16	0.8441 (2)	0.84394 (11)	0.1576 (2)	0.0358 (5)
H16	0.8497	0.8358	0.2669	0.043*
C17	0.9220 (2)	0.90903 (12)	0.1268 (3)	0.0475 (6)
H17A	0.9987	0.9196	0.2078	0.057*
H17B	0.8451	0.9438	0.1190	0.057*
C18	1.0597 (3)	0.81554 (12)	0.0079 (3)	0.0522 (6)
H18A	1.0795	0.7891	−0.0799	0.063*
H18B	1.1515	0.8145	0.0770	0.063*
C19	0.8148 (2)	0.74831 (11)	−0.0048 (2)	0.0346 (5)
C20	0.6583 (2)	0.76627 (10)	0.0622 (2)	0.0361 (5)
H20	0.6520	0.7429	0.1583	0.043*
C21	0.5169 (3)	0.74830 (13)	−0.0381 (3)	0.0469 (6)
C24	0.8642 (2)	0.67578 (11)	0.0284 (2)	0.0402 (5)
C25	0.9027 (3)	0.64571 (11)	−0.1152 (3)	0.0447 (5)
C26	0.9563 (3)	0.58507 (13)	−0.1508 (3)	0.0633 (7)
H26	0.9807	0.5543	−0.0758	0.076*
C27	0.9734 (4)	0.57065 (14)	−0.3031 (3)	0.0784 (9)
H27	1.0113	0.5297	−0.3286	0.094*
C28	0.9366 (4)	0.61442 (15)	−0.4160 (3)	0.0701 (8)
H28	0.9489	0.6026	−0.5160	0.084*
C29	0.8805 (3)	0.67706 (13)	−0.3835 (3)	0.0501 (6)
C30	0.8345 (3)	0.72664 (15)	−0.4870 (3)	0.0603 (7)
H30	0.8428	0.7201	−0.5902	0.072*
C31	0.7775 (3)	0.78419 (14)	−0.4354 (3)	0.0606 (7)
H31	0.7448	0.8160	−0.5054	0.073*
C32	0.7663 (3)	0.79738 (13)	−0.2803 (2)	0.0505 (6)
H32	0.7273	0.8373	−0.2490	0.061*
C33	0.8127 (2)	0.75142 (11)	−0.1771 (2)	0.0371 (5)
C34	0.8683 (2)	0.69111 (11)	−0.2306 (2)	0.0411 (5)
N1	0.92549 (18)	0.79087 (9)	0.08164 (18)	0.0381 (4)
O1	0.4185 (2)	0.78642 (10)	−0.0821 (2)	0.0725 (6)
O3	0.8674 (2)	0.65153 (8)	0.15251 (18)	0.0547 (4)
O4	0.52013 (16)	0.96312 (8)	0.05080 (16)	0.0437 (4)
O5	0.62621 (14)	0.90082 (8)	0.32626 (14)	0.0443 (4)
O6	0.44787 (17)	0.90588 (11)	0.51319 (16)	0.0641 (5)
O7	0.26019 (15)	0.90235 (10)	0.32494 (15)	0.0540 (4)
S1	1.01420 (7)	0.89962 (4)	−0.04894 (7)	0.05884 (19)
O2	0.5175 (2)	0.68557 (9)	−0.0717 (2)	0.0714 (5)
C22'	0.3864 (13)	0.6486 (8)	−0.1444 (12)	0.086 (3)	0.450 (7)
H22A	0.2876	0.6703	−0.1319	0.103*	0.450 (7)
H22B	0.3818	0.6044	−0.1052	0.103*	0.450 (7)
C23'	0.4283 (13)	0.6493 (6)	−0.3035 (11)	0.1009 (19)	0.450 (7)
H23A	0.4392	0.6937	−0.3366	0.151*	0.450 (7)
H23B	0.3478	0.6281	−0.3653	0.151*	0.450 (7)
H23C	0.5251	0.6265	−0.3124	0.151*	0.450 (7)
C22	0.3883 (11)	0.6700 (5)	−0.1829 (12)	0.086 (3)	0.550 (7)
H22C	0.2916	0.6651	−0.1326	0.103*	0.550 (7)
H22D	0.3754	0.7047	−0.2572	0.103*	0.550 (7)
C23	0.4290 (11)	0.6083 (4)	−0.2567 (10)	0.1009 (19)	0.550 (7)
H23D	0.5275	0.6131	−0.3016	0.151*	0.550 (7)
H23E	0.3499	0.5977	−0.3338	0.151*	0.550 (7)
H23F	0.4362	0.5739	−0.1828	0.151*	0.550 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0573 (19)	0.134 (3)	0.098 (2)	0.0049 (18)	0.0028 (16)	0.065 (2)
C2	0.079 (2)	0.175 (5)	0.117 (3)	−0.009 (3)	0.015 (2)	0.080 (3)
C3	0.129 (4)	0.115 (4)	0.122 (3)	−0.018 (3)	0.051 (3)	0.036 (3)
C4	0.175 (5)	0.071 (2)	0.125 (3)	0.031 (3)	0.077 (3)	0.037 (2)
C5	0.092 (2)	0.084 (2)	0.087 (2)	0.0304 (19)	0.0397 (19)	0.0205 (19)
C6	0.0566 (15)	0.079 (2)	0.0437 (14)	0.0024 (14)	0.0009 (11)	0.0184 (14)
C7	0.0585 (17)	0.111 (3)	0.0592 (17)	−0.0106 (17)	−0.0081 (13)	0.0336 (17)
C8	0.0280 (9)	0.0504 (15)	0.0372 (11)	−0.0020 (9)	0.0039 (8)	0.0018 (10)
C9	0.0380 (12)	0.0514 (14)	0.0445 (13)	0.0096 (10)	0.0072 (10)	0.0016 (11)
C10	0.0417 (12)	0.090 (2)	0.0424 (12)	0.0033 (14)	0.0073 (10)	0.0081 (14)
C11	0.0417 (12)	0.0520 (14)	0.0411 (12)	0.0047 (10)	0.0071 (10)	−0.0068 (11)
C12	0.0296 (10)	0.0476 (14)	0.0345 (11)	−0.0010 (9)	0.0036 (9)	−0.0028 (9)
C13	0.0661 (18)	0.170 (4)	0.0487 (16)	0.029 (2)	0.0149 (14)	−0.0141 (19)
C14	0.119 (3)	0.109 (3)	0.105 (3)	−0.024 (2)	0.013 (2)	0.036 (2)
C15	0.0286 (10)	0.0455 (13)	0.0305 (10)	0.0004 (9)	0.0021 (8)	0.0014 (9)
C16	0.0313 (10)	0.0418 (12)	0.0345 (11)	−0.0003 (9)	0.0028 (9)	−0.0012 (9)
C17	0.0340 (10)	0.0476 (15)	0.0608 (14)	−0.0032 (11)	0.0013 (9)	−0.0043 (12)
C18	0.0345 (12)	0.0582 (16)	0.0648 (15)	−0.0015 (11)	0.0107 (10)	−0.0054 (13)
C19	0.0321 (10)	0.0377 (11)	0.0346 (11)	0.0023 (9)	0.0052 (8)	0.0009 (9)
C20	0.0321 (10)	0.0452 (13)	0.0317 (11)	−0.0022 (9)	0.0065 (8)	−0.0009 (9)
C21	0.0345 (12)	0.0538 (15)	0.0527 (14)	−0.0048 (11)	0.0055 (10)	−0.0127 (12)
C24	0.0371 (11)	0.0436 (13)	0.0401 (12)	0.0022 (10)	0.0035 (9)	0.0069 (10)
C25	0.0463 (13)	0.0412 (13)	0.0468 (13)	0.0013 (10)	0.0054 (10)	0.0007 (10)
C26	0.089 (2)	0.0420 (15)	0.0600 (17)	0.0096 (14)	0.0137 (14)	0.0007 (12)
C27	0.117 (2)	0.0443 (16)	0.076 (2)	0.0183 (17)	0.0216 (18)	−0.0119 (15)
C28	0.094 (2)	0.0634 (19)	0.0549 (16)	0.0003 (16)	0.0226 (15)	−0.0207 (15)
C29	0.0542 (14)	0.0567 (16)	0.0404 (13)	−0.0010 (12)	0.0104 (10)	−0.0077 (12)
C30	0.0706 (17)	0.078 (2)	0.0330 (13)	0.0014 (15)	0.0098 (12)	−0.0029 (13)
C31	0.0716 (17)	0.0724 (19)	0.0383 (13)	0.0173 (15)	0.0068 (11)	0.0142 (13)
C32	0.0549 (14)	0.0560 (16)	0.0416 (13)	0.0129 (12)	0.0100 (10)	0.0027 (12)
C33	0.0342 (11)	0.0409 (12)	0.0367 (11)	0.0032 (9)	0.0061 (8)	0.0009 (10)
C34	0.0391 (11)	0.0434 (14)	0.0414 (12)	−0.0023 (10)	0.0073 (9)	−0.0011 (10)
N1	0.0274 (8)	0.0453 (11)	0.0420 (10)	0.0013 (8)	0.0058 (7)	−0.0026 (9)
O1	0.0433 (10)	0.0815 (14)	0.0902 (14)	0.0097 (10)	−0.0177 (9)	−0.0275 (12)
O3	0.0681 (11)	0.0518 (10)	0.0443 (10)	0.0055 (8)	0.0057 (8)	0.0112 (8)
O4	0.0403 (8)	0.0511 (10)	0.0394 (8)	−0.0005 (7)	0.0001 (6)	0.0072 (7)
O5	0.0342 (7)	0.0624 (10)	0.0358 (7)	0.0096 (8)	−0.0017 (6)	−0.0075 (8)
O6	0.0459 (9)	0.1101 (15)	0.0364 (8)	0.0056 (10)	0.0033 (6)	0.0089 (10)
O7	0.0340 (7)	0.0880 (12)	0.0405 (8)	−0.0025 (9)	0.0080 (6)	0.0014 (9)
S1	0.0471 (3)	0.0637 (4)	0.0672 (4)	−0.0115 (3)	0.0167 (3)	0.0101 (4)
O2	0.0556 (11)	0.0612 (13)	0.0963 (14)	−0.0141 (9)	−0.0061 (10)	−0.0252 (11)
C22'	0.079 (2)	0.057 (7)	0.119 (5)	−0.017 (3)	−0.024 (3)	−0.027 (5)
C23'	0.121 (4)	0.081 (5)	0.096 (4)	0.002 (5)	−0.032 (4)	−0.024 (4)
C22	0.079 (2)	0.057 (7)	0.119 (5)	−0.017 (3)	−0.024 (3)	−0.027 (5)
C23	0.121 (4)	0.081 (5)	0.096 (4)	0.002 (5)	−0.032 (4)	−0.024 (4)

Geometric parameters (Å, º) top

C1—C2	1.370 (5)	C17—H17B	0.9700
C1—C6	1.375 (4)	C18—N1	1.447 (3)
C1—H1	0.9300	C18—S1	1.827 (3)
C2—C3	1.344 (6)	C18—H18A	0.9700
C2—H2	0.9300	C18—H18B	0.9700
C3—C4	1.354 (6)	C19—N1	1.471 (3)
C3—H3	0.9300	C19—C33	1.525 (3)
C4—C5	1.384 (5)	C19—C20	1.544 (3)
C4—H4	0.9300	C19—C24	1.566 (3)
C5—C6	1.359 (4)	C20—C21	1.508 (3)
C5—H5	0.9300	C20—H20	0.9800
C6—C7	1.484 (4)	C21—O1	1.198 (3)
C7—O4	1.415 (3)	C21—O2	1.317 (3)
C7—H7A	0.9700	C24—O3	1.204 (3)
C7—H7B	0.9700	C24—C25	1.466 (3)
C8—O4	1.419 (3)	C25—C26	1.366 (3)
C8—C9	1.517 (3)	C25—C34	1.399 (3)
C8—C12	1.518 (3)	C26—C27	1.396 (4)
C8—H8	0.9800	C26—H26	0.9300
C9—O7	1.409 (3)	C27—C28	1.365 (4)
C9—C11	1.537 (3)	C27—H27	0.9300
C9—H9	0.9800	C28—C29	1.404 (4)
C10—O6	1.410 (3)	C28—H28	0.9300
C10—O7	1.417 (3)	C29—C34	1.393 (3)
C10—C14	1.501 (4)	C29—C30	1.408 (4)
C10—C13	1.503 (4)	C30—C31	1.363 (4)
C11—O6	1.398 (3)	C30—H30	0.9300
C11—O5	1.406 (3)	C31—C32	1.408 (3)
C11—H11	0.9800	C31—H31	0.9300
C12—O5	1.441 (2)	C32—C33	1.355 (3)
C12—C15	1.526 (3)	C32—H32	0.9300
C12—H12	0.9800	C33—C34	1.414 (3)
C13—H13A	0.9600	O2—C22'	1.473 (7)
C13—H13B	0.9600	O2—C22	1.475 (6)
C13—H13C	0.9600	C22'—C23'	1.474 (10)
C14—H14A	0.9600	C22'—H22A	0.9700
C14—H14B	0.9600	C22'—H22B	0.9700
C14—H14C	0.9600	C23'—H23A	0.9600
C15—C20	1.517 (3)	C23'—H23B	0.9600
C15—C16	1.526 (3)	C23'—H23C	0.9600
C15—H15	0.9800	C22—C23	1.471 (9)
C16—N1	1.474 (3)	C22—H22C	0.9700
C16—C17	1.521 (3)	C22—H22D	0.9700
C16—H16	0.9800	C23—H23D	0.9600
C17—S1	1.795 (2)	C23—H23E	0.9600
C17—H17A	0.9700	C23—H23F	0.9600

C2—C1—C6	121.1 (4)	H17A—C17—H17B	108.6
C2—C1—H1	119.4	N1—C18—S1	106.80 (15)
C6—C1—H1	119.4	N1—C18—H18A	110.4
C3—C2—C1	120.1 (4)	S1—C18—H18A	110.4
C3—C2—H2	119.9	N1—C18—H18B	110.4
C1—C2—H2	119.9	S1—C18—H18B	110.4
C2—C3—C4	119.9 (4)	H18A—C18—H18B	108.6
C2—C3—H3	120.1	N1—C19—C33	117.75 (17)
C4—C3—H3	120.1	N1—C19—C20	102.15 (16)
C3—C4—C5	120.3 (4)	C33—C19—C20	114.44 (16)
C3—C4—H4	119.9	N1—C19—C24	107.62 (16)
C5—C4—H4	119.9	C33—C19—C24	102.38 (16)
C6—C5—C4	120.5 (3)	C20—C19—C24	112.68 (17)
C6—C5—H5	119.8	C21—C20—C15	114.78 (18)
C4—C5—H5	119.8	C21—C20—C19	113.89 (17)
C5—C6—C1	117.9 (3)	C15—C20—C19	103.72 (16)
C5—C6—C7	121.5 (3)	C21—C20—H20	108.0
C1—C6—C7	120.5 (3)	C15—C20—H20	108.0
O4—C7—C6	110.0 (2)	C19—C20—H20	108.0
O4—C7—H7A	109.7	O1—C21—O2	124.9 (2)
C6—C7—H7A	109.7	O1—C21—C20	124.2 (2)
O4—C7—H7B	109.7	O2—C21—C20	110.9 (2)
C6—C7—H7B	109.7	O3—C24—C25	128.6 (2)
H7A—C7—H7B	108.2	O3—C24—C19	123.6 (2)
O4—C8—C9	110.44 (18)	C25—C24—C19	107.87 (18)
O4—C8—C12	109.82 (16)	C26—C25—C34	119.6 (2)
C9—C8—C12	100.97 (16)	C26—C25—C24	132.6 (2)
O4—C8—H8	111.7	C34—C25—C24	107.80 (19)
C9—C8—H8	111.7	C25—C26—C27	118.0 (3)
C12—C8—H8	111.7	C25—C26—H26	121.0
O7—C9—C8	108.83 (19)	C27—C26—H26	121.0
O7—C9—C11	103.87 (17)	C28—C27—C26	122.4 (3)
C8—C9—C11	103.81 (17)	C28—C27—H27	118.8
O7—C9—H9	113.2	C26—C27—H27	118.8
C8—C9—H9	113.2	C27—C28—C29	121.1 (2)
C11—C9—H9	113.2	C27—C28—H28	119.5
O6—C10—O7	105.64 (17)	C29—C28—H28	119.5
O6—C10—C14	109.8 (3)	C34—C29—C28	115.6 (2)
O7—C10—C14	108.7 (3)	C34—C29—C30	116.7 (2)
O6—C10—C13	110.0 (2)	C28—C29—C30	127.6 (2)
O7—C10—C13	109.6 (2)	C31—C30—C29	119.8 (2)
C14—C10—C13	112.9 (3)	C31—C30—H30	120.1
O6—C11—O5	111.7 (2)	C29—C30—H30	120.1
O6—C11—C9	104.83 (17)	C30—C31—C32	122.5 (2)
O5—C11—C9	106.55 (16)	C30—C31—H31	118.7
O6—C11—H11	111.2	C32—C31—H31	118.7
O5—C11—H11	111.2	C33—C32—C31	119.4 (2)
C9—C11—H11	111.2	C33—C32—H32	120.3
O5—C12—C8	102.65 (17)	C31—C32—H32	120.3
O5—C12—C15	111.29 (15)	C32—C33—C34	118.1 (2)
C8—C12—C15	116.53 (17)	C32—C33—C19	133.6 (2)
O5—C12—H12	108.7	C34—C33—C19	108.30 (18)
C8—C12—H12	108.7	C29—C34—C25	123.2 (2)
C15—C12—H12	108.7	C29—C34—C33	123.4 (2)
C10—C13—H13A	109.5	C25—C34—C33	113.27 (19)
C10—C13—H13B	109.5	C18—N1—C19	118.65 (18)
H13A—C13—H13B	109.5	C18—N1—C16	111.09 (18)
C10—C13—H13C	109.5	C19—N1—C16	111.32 (15)
H13A—C13—H13C	109.5	C7—O4—C8	113.87 (18)
H13B—C13—H13C	109.5	C11—O5—C12	108.05 (15)
C10—C14—H14A	109.5	C11—O6—C10	111.37 (16)
C10—C14—H14B	109.5	C9—O7—C10	109.72 (17)
H14A—C14—H14B	109.5	C17—S1—C18	87.71 (11)
C10—C14—H14C	109.5	C21—O2—C22'	125.8 (7)
H14A—C14—H14C	109.5	C21—O2—C22	110.4 (4)
H14B—C14—H14C	109.5	O2—C22'—C23'	101.0 (8)
C20—C15—C16	102.45 (16)	O2—C22'—H22A	111.6
C20—C15—C12	114.38 (17)	C23'—C22'—H22A	111.6
C16—C15—C12	115.66 (16)	O2—C22'—H22B	111.6
C20—C15—H15	108.0	C23'—C22'—H22B	111.6
C16—C15—H15	108.0	H22A—C22'—H22B	109.4
C12—C15—H15	108.0	C23—C22—O2	107.0 (7)
N1—C16—C17	109.70 (16)	C23—C22—H22C	110.3
N1—C16—C15	104.77 (16)	O2—C22—H22C	110.3
C17—C16—C15	114.75 (18)	C23—C22—H22D	110.3
N1—C16—H16	109.1	O2—C22—H22D	110.3
C17—C16—H16	109.1	H22C—C22—H22D	108.6
C15—C16—H16	109.1	C22—C23—H23D	109.5
C16—C17—S1	106.38 (15)	C22—C23—H23E	109.5
C16—C17—H17A	110.5	H23D—C23—H23E	109.5
S1—C17—H17A	110.5	C22—C23—H23F	109.5
C16—C17—H17B	110.5	H23D—C23—H23F	109.5
S1—C17—H17B	110.5	H23E—C23—H23F	109.5

C6—C1—C2—C3	−3.2 (7)	C28—C29—C30—C31	177.8 (3)
C1—C2—C3—C4	−0.6 (8)	C29—C30—C31—C32	1.8 (4)
C2—C3—C4—C5	2.2 (8)	C30—C31—C32—C33	−0.3 (4)
C3—C4—C5—C6	0.0 (7)	C31—C32—C33—C34	−1.2 (3)
C4—C5—C6—C1	−3.6 (5)	C31—C32—C33—C19	−178.8 (2)
C4—C5—C6—C7	180.0 (4)	N1—C19—C33—C32	−69.6 (3)
C2—C1—C6—C5	5.3 (6)	C20—C19—C33—C32	50.4 (3)
C2—C1—C6—C7	−178.3 (4)	C24—C19—C33—C32	172.7 (2)
C5—C6—C7—O4	−131.1 (3)	N1—C19—C33—C34	112.6 (2)
C1—C6—C7—O4	52.6 (4)	C20—C19—C33—C34	−127.35 (19)
O4—C8—C9—O7	163.47 (15)	C24—C19—C33—C34	−5.1 (2)
C12—C8—C9—O7	−80.38 (19)	C28—C29—C34—C25	−2.6 (3)
O4—C8—C9—C11	−86.4 (2)	C30—C29—C34—C25	176.9 (2)
C12—C8—C9—C11	29.8 (2)	C28—C29—C34—C33	−179.3 (2)
O7—C9—C11—O6	−12.6 (2)	C30—C29—C34—C33	0.1 (3)
C8—C9—C11—O6	−126.3 (2)	C26—C25—C34—C29	2.4 (4)
O7—C9—C11—O5	105.99 (19)	C24—C25—C34—C29	−175.3 (2)
C8—C9—C11—O5	−7.8 (2)	C26—C25—C34—C33	179.4 (2)
O4—C8—C12—O5	74.99 (18)	C24—C25—C34—C33	1.7 (3)
C9—C8—C12—O5	−41.62 (19)	C32—C33—C34—C29	1.3 (3)
O4—C8—C12—C15	−46.9 (2)	C19—C33—C34—C29	179.4 (2)
C9—C8—C12—C15	−163.49 (18)	C32—C33—C34—C25	−175.8 (2)
O5—C12—C15—C20	128.42 (18)	C19—C33—C34—C25	2.4 (3)
C8—C12—C15—C20	−114.4 (2)	S1—C18—N1—C19	100.49 (19)
O5—C12—C15—C16	9.7 (3)	S1—C18—N1—C16	−30.4 (2)
C8—C12—C15—C16	126.9 (2)	C33—C19—N1—C18	−21.1 (3)
C20—C15—C16—N1	29.11 (19)	C20—C19—N1—C18	−147.37 (18)
C12—C15—C16—N1	154.21 (17)	C24—C19—N1—C18	93.8 (2)
C20—C15—C16—C17	149.47 (18)	C33—C19—N1—C16	109.69 (19)
C12—C15—C16—C17	−85.4 (2)	C20—C19—N1—C16	−16.6 (2)
N1—C16—C17—S1	25.76 (19)	C24—C19—N1—C16	−135.40 (17)
C15—C16—C17—S1	−91.84 (18)	C17—C16—N1—C18	3.3 (2)
C16—C15—C20—C21	−164.34 (17)	C15—C16—N1—C18	126.92 (18)
C12—C15—C20—C21	69.7 (2)	C17—C16—N1—C19	−131.35 (17)
C16—C15—C20—C19	−39.46 (19)	C15—C16—N1—C19	−7.7 (2)
C12—C15—C20—C19	−165.40 (15)	C6—C7—O4—C8	−178.8 (2)
N1—C19—C20—C21	160.00 (19)	C9—C8—O4—C7	−113.4 (2)
C33—C19—C20—C21	31.6 (3)	C12—C8—O4—C7	136.1 (2)
C24—C19—C20—C21	−84.8 (2)	O6—C11—O5—C12	94.59 (19)
N1—C19—C20—C15	34.54 (19)	C9—C11—O5—C12	−19.3 (2)
C33—C19—C20—C15	−93.84 (19)	C8—C12—O5—C11	38.9 (2)
C24—C19—C20—C15	149.72 (17)	C15—C12—O5—C11	164.21 (18)
C15—C20—C21—O1	−4.0 (3)	O5—C11—O6—C10	−115.1 (2)
C19—C20—C21—O1	−123.3 (3)	C9—C11—O6—C10	−0.1 (3)
C15—C20—C21—O2	175.35 (19)	O7—C10—O6—C11	12.7 (3)
C19—C20—C21—O2	56.0 (3)	C14—C10—O6—C11	129.8 (3)
N1—C19—C24—O3	61.5 (3)	C13—C10—O6—C11	−105.4 (3)
C33—C19—C24—O3	−173.8 (2)	C8—C9—O7—C10	131.1 (2)
C20—C19—C24—O3	−50.3 (3)	C11—C9—O7—C10	21.0 (2)
N1—C19—C24—C25	−118.61 (18)	O6—C10—O7—C9	−21.5 (3)
C33—C19—C24—C25	6.1 (2)	C14—C10—O7—C9	−139.2 (2)
C20—C19—C24—C25	129.55 (18)	C13—C10—O7—C9	97.0 (3)
O3—C24—C25—C26	−2.4 (4)	C16—C17—S1—C18	−36.36 (15)
C19—C24—C25—C26	177.7 (3)	N1—C18—S1—C17	38.98 (17)
O3—C24—C25—C34	174.8 (2)	O1—C21—O2—C22'	−11.9 (7)
C19—C24—C25—C34	−5.0 (2)	C20—C21—O2—C22'	168.8 (6)
C34—C25—C26—C27	−0.5 (4)	O1—C21—O2—C22	5.5 (6)
C24—C25—C26—C27	176.5 (3)	C20—C21—O2—C22	−173.8 (6)
C25—C26—C27—C28	−0.9 (5)	C21—O2—C22'—C23'	97.2 (11)
C26—C27—C28—C29	0.7 (5)	C22—O2—C22'—C23'	47.9 (17)
C27—C28—C29—C34	1.1 (4)	C21—O2—C22—C23	159.1 (8)
C27—C28—C29—C30	−178.4 (3)	C22'—O2—C22—C23	−62 (2)
C34—C29—C30—C31	−1.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3ⁱ	0.93	2.51	3.375 (4)	155
C17—H17A···O7ⁱⁱ	0.97	2.44	3.309 (3)	148
C23—H23F···O4ⁱⁱⁱ	0.96	2.57	3.497 (9)	163
C31—H31···O5^iv	0.93	2.47	3.393 (4)	173

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

Experimental details

Crystal data
Chemical formula	C₃₄H₃₅NO₇S
M_r	601.69
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	8.588 (5), 20.446 (5), 8.851 (5)
β (°)	93.282 (5)
V (Å³)	1551.6 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.955, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	13521, 5470, 4678
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.083, 1.03
No. of reflections	5470
No. of parameters	400
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16
Absolute structure	Flack (1983), 2630 Friedel pairs
Absolute structure parameter	0.04 (7)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), 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
C5—H5···O3ⁱ	0.93	2.51	3.375 (4)	155
C17—H17A···O7ⁱⁱ	0.97	2.44	3.309 (3)	148
C23—H23F···O4ⁱⁱⁱ	0.96	2.57	3.497 (9)	163
C31—H31···O5^iv	0.93	2.47	3.393 (4)	173

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

Acknowledgements

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

References

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Volume 68| Part 8| August 2012| Pages o2505-o2506

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

Ethyl 7′-(6-benz­yl­oxy-2,2-di­methyl­tetra­hydro­furo[3,2-d][1,3]dioxol-5-yl)-2-oxo-5′,6′,7′,7a'-tetra­hydro-1′H,2H-spiro­[ace­naphthyl­ene-1,5′-pyrrolo­[1,2-c][1,3]thia­zole]-6′-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl 7′-(6-benzyloxy-2,2-dimethyltetrahydrofuro[3,2-d][1,3]dioxol-5-yl)-2-oxo-5′,6′,7′,7a'-tetrahydro-1′H,2H-spiro[acenaphthylene-1,5′-pyrrolo[1,2-c][1,3]thiazole]-6′-carboxylate