Ethyl 4′-(4-methoxy­phenyl)-1′,7′′-di­methyl-2,3′′-dioxo-5′′-phenyl-2,3,2′′,3′′,4′′,5′′-tetra­hydro-1H-indole-3-spiro-2′-pyrrolidine-3′-spiro-2′′-(thia­zolo­[3,2-a]­pyrimidine)-6′′-carboxyl­ate

Li, X.-F.; Feng, Y.-Q.; Shi, D.-X..; Chen, H.-L.

doi:10.1107/S1600536803018786

Ethyl 4′-(4-methoxyphenyl)-1′,7′′-dimethyl-2,3′′-dioxo-5′′-phenyl-2,3,2′′,3′′,4′′,5′′-tetrahydro-1H-indole-3-spiro-2′-pyrrolidine-3′-spiro-2′′-(thiazolo[3,2-a]pyrimidine)-6′′-carboxylate

X.-F. Li, Y.-Q. Feng, D.-X. Shi and H.-L. Chen

In the title compound, C₃₄H₃₂N₄O₅S, the two spiro junctions link a planar 2-oxindole ring, a pyrrolidine ring in an envelope conformation and a thiazolo[3,2-a]pyrimidine ring. Two molecules are connected by N—H

N hydrogen bonds, with an N

N distance of 3.027 (2) Å and an N—H

N angle of 140.2°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018786/om6165sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018786/om6165Isup2.hkl Contains datablock I

CCDC reference: 222914

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.053
wR factor = 0.137
Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT165_ALERT_3_C Nr. of Status R Flagged Non-Hydrogen Atoms .....         12
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.03 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.07 Ratio
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         O5
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         C9
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        C11
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....       C12'
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        C7'
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C4     -   C5       =       1.35 Ang.
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H31    ..  H33E     =       1.81 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Spiro-compounds represent an important class of naturally occurring substances, which in many cases exhibit important biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are widely used for the construction of spiro-compounds (Caramella & Grunanger, 1984). In this paper, the structure of the title compound, (I), is reported. The compound was synthesized by the intermolecular [3 + 2]-cycloaddition of azomethine ylide, derived from isatin and sarcosine by a decarboxylative route, and 2-(4-methoxy-benzylidene)-7-methyl-3-oxo-5-phenyl-2,3-dihydro-5H- thiazolo[3,2-a]pyrimidine-6-carboxylic acid ethyl ester (Tozkoparan, 1999).

The molecular structure of (I) is shown in Fig. 1. There exists a dispiro ring in the molecule that consists of a planar 2-oxindole ring, a pyrrolidine ring and a thiazolo[3,2-a]pyrimidine ring. The pyrrolidine ring (N3, C18, C17, C1 and C19) is not planar, and has an envelope conformation. Two molecules are connected by N—H···N hydrogen bonds, with an N···N distance of 3.027 (2) Å and an N—H···N angle 140.2°.

Experimental top

A mixture of 2-(4-methoxy-benzylidene)-7-methyl-3-oxo-5-phenyl- 2,3-dihydro-5H-thiazolo[3,2-a]pyrimidine-6-carboxylic acid ethyl ester (1 mmol), isatin (1 mmol) and sarcosine (1 mmol) was refluxed in methanol (60 ml) until the disappearence of the starting material, as evidenced by thin-layer chromatography. When the reaction was complete, the solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate = 5:1), giving the title compound (I) (m.p. 479–481 K); IR (KBr): 3351.4 (–NH), 1743.4, 1723.1, 1688.2 (C═O) cm⁻¹; ¹H NMR (δ, p.p.m.): 1.03 (m, 3H, –CH₃), 2.17 (s, 3H, –CH₃), 2.23 (s, 3H, N—CH₃), 3.45 (m, 1H,-CH₂), 3.73 (s, 3H, –CH₃), 3.99 (m, 1H, –CH₂), 4.03 (m, 2H, –CH₂), 4.57 (m, 1H, –CH), 5.72 (s, 1H, –CH), 6.69–7.74 (m, 13H, ArH), 7.86 (bs, 1H, –NH). 20 mg of (I) was dissolved in 15 ml dioxane; the solution was kept at room temperature for 15 d and natural evaporation gave colorless single crystals of (I), suitable for X-ray analysis.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids. H atoms have been omitted for clarity.
	Fig. 2. The crystal structure of (I), viewed along the b axis.

Ethyl 4'-(4-methoxyphenyl)-1',7''-dimethyl-2,3''-dioxo-5''-phenyl- 2,3,2'',3'',4'',5''-tetrahydro-1H-indole-3-spiro-2'-pyrrolidine-3'-spiro- 2''-(thiazolo[3,2-a]pyrimidine)-6''-carboxylate top

Crystal data top

C₃₄H₃₂N₄O₅S	D_x = 1.332 Mg m⁻³
M_r = 608.70	Melting point: 481 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.990 (6) Å	Cell parameters from 816 reflections
b = 11.375 (5) Å	θ = 2.3–25.3°
c = 17.815 (8) Å	µ = 0.16 mm⁻¹
β = 92.254 (6)°	T = 293 K
V = 3035 (2) Å³	Block, colorless
Z = 4	0.38 × 0.30 × 0.24 mm
F(000) = 1280

Data collection top

Bruker SMART CCD area-detector diffractometer	6236 independent reflections
Radiation source: fine-focus sealed tube	3567 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −18→12
T_min = 0.905, T_max = 0.960	k = −14→6
14013 measured reflections	l = −21→22

Refinement top

Refinement on F²	278 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.053	w = 1/[σ²(F_o²) + (0.084P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.137	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.34 e Å⁻³
6236 reflections	Δρ_min = −0.40 e Å⁻³
413 parameters

Crystal data top

C₃₄H₃₂N₄O₅S	V = 3035 (2) Å³
M_r = 608.70	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.990 (6) Å	µ = 0.16 mm⁻¹
b = 11.375 (5) Å	T = 293 K
c = 17.815 (8) Å	0.38 × 0.30 × 0.24 mm
β = 92.254 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6236 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	3567 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.960	R_int = 0.042
14013 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	278 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.00	Δρ_max = 0.34 e Å⁻³
6236 reflections	Δρ_min = −0.40 e Å⁻³
413 parameters

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)
S1	−0.11674 (4)	0.75530 (6)	0.22105 (4)	0.03688 (18)
N1	0.02404 (12)	0.74525 (17)	0.30997 (10)	0.0328 (5)
N2	−0.05077 (13)	0.56453 (18)	0.28956 (11)	0.0365 (5)
N3	−0.07997 (15)	1.09805 (18)	0.21885 (13)	0.0474 (6)
N4	−0.27194 (14)	0.98711 (19)	0.28112 (12)	0.0431 (6)
H4	−0.3290	0.9802	0.2758	0.052*
O1	0.07145 (12)	0.93404 (15)	0.32201 (11)	0.0503 (5)
O2	−0.23486 (13)	0.94136 (17)	0.16092 (11)	0.0553 (5)
O3	0.20107 (18)	0.5915 (2)	0.46174 (15)	0.0943 (9)
O4	0.12615 (14)	0.42263 (17)	0.46218 (11)	0.0612 (6)
O5	0.03469 (17)	0.6091 (2)	−0.07219 (14)	0.0942 (7)
C1	−0.05440 (16)	0.8931 (2)	0.23480 (13)	0.0345 (6)
C2	0.01901 (16)	0.8643 (2)	0.29439 (14)	0.0353 (6)
C3	−0.04170 (15)	0.6752 (2)	0.27775 (13)	0.0320 (6)
C4	0.00562 (17)	0.5144 (2)	0.34725 (14)	0.0391 (6)
C5	0.07689 (18)	0.5719 (2)	0.37727 (14)	0.0395 (6)
C6	0.10410 (16)	0.6913 (2)	0.34741 (14)	0.0381 (6)	0.658 (5)
H6A	0.1233	0.7409	0.3900	0.046*	0.658 (5)
C7	0.1797 (2)	0.6886 (4)	0.2903 (2)	0.047 (3)	0.658 (5)
C8	0.1881 (3)	0.5908 (3)	0.2443 (3)	0.0642 (19)	0.658 (5)
H8A	0.1498	0.5272	0.2489	0.077*	0.658 (5)
C9	0.2538 (4)	0.5882 (4)	0.1914 (3)	0.090 (3)	0.658 (5)
H9A	0.2594	0.5227	0.1606	0.108*	0.658 (5)
C10	0.3112 (3)	0.6832 (5)	0.1845 (2)	0.084 (2)	0.658 (5)
H10A	0.3551	0.6815	0.1491	0.101*	0.658 (5)
C11	0.3028 (2)	0.7810 (4)	0.2305 (3)	0.097 (2)	0.658 (5)
H11A	0.3412	0.8446	0.2259	0.117*	0.658 (5)
C12	0.2371 (3)	0.7837 (4)	0.2834 (2)	0.0725 (17)	0.658 (5)
H12A	0.2315	0.8491	0.3142	0.087*	0.658 (5)
C6'	0.10410 (16)	0.6913 (2)	0.34741 (14)	0.0381 (6)	0.342 (5)
H6'A	0.1223	0.7407	0.3904	0.046*	0.342 (5)
C7'	0.1812 (4)	0.6830 (6)	0.2968 (4)	0.041 (5)	0.342 (5)
C8'	0.1718 (4)	0.6392 (6)	0.2240 (5)	0.058 (3)	0.342 (5)
H8'A	0.1160	0.6154	0.2050	0.070*	0.342 (5)
C9'	0.2458 (6)	0.6311 (7)	0.1797 (4)	0.067 (4)	0.342 (5)
H9'A	0.2395	0.6019	0.1310	0.081*	0.342 (5)
C10'	0.3292 (5)	0.6668 (7)	0.2081 (5)	0.093 (3)	0.342 (5)
H10B	0.3787	0.6614	0.1784	0.111*	0.342 (5)
C11'	0.3385 (4)	0.7105 (6)	0.2808 (5)	0.093 (3)	0.342 (5)
H11B	0.3943	0.7344	0.2998	0.111*	0.342 (5)
C12'	0.2645 (5)	0.7186 (6)	0.3252 (4)	0.093 (3)	0.342 (5)
H12B	0.2708	0.7479	0.3738	0.111*	0.342 (5)
C13	−0.0284 (2)	0.3944 (2)	0.36847 (18)	0.0591 (8)
H13A	−0.0106	0.3376	0.3321	0.089*
H13B	−0.0923	0.3962	0.3697	0.089*
H13C	−0.0038	0.3730	0.4171	0.089*
C14	0.1404 (2)	0.5307 (3)	0.43740 (16)	0.0513 (8)
C15	0.1859 (2)	0.3789 (3)	0.52163 (17)	0.0701 (10)
H15A	0.1857	0.4309	0.5648	0.084*
H15B	0.2464	0.3738	0.5044	0.084*
C16	0.1526 (3)	0.2599 (3)	0.54209 (19)	0.0840 (12)
H16A	0.0920	0.2659	0.5571	0.126*
H16B	0.1892	0.2288	0.5828	0.126*
H16C	0.1553	0.2086	0.4995	0.126*
C17	−0.00573 (18)	0.9410 (2)	0.16225 (15)	0.0436 (7)
H17	0.0556	0.9604	0.1788	0.052*
C18	−0.0527 (2)	1.0573 (2)	0.14542 (17)	0.0578 (8)
H18A	−0.0124	1.1131	0.1233	0.069*
H18B	−0.1042	1.0460	0.1114	0.069*
C19	−0.11784 (17)	0.9959 (2)	0.25715 (14)	0.0363 (6)
C20	−0.21457 (18)	0.9697 (2)	0.22538 (15)	0.0392 (6)
C21	−0.22645 (18)	1.0180 (2)	0.34904 (15)	0.0412 (6)
C22	−0.2631 (2)	1.0460 (3)	0.41660 (17)	0.0610 (9)
H22	−0.3245	1.0432	0.4224	0.073*
C23	−0.2051 (2)	1.0782 (3)	0.47544 (18)	0.0732 (10)
H23	−0.2279	1.0959	0.5219	0.088*
C24	−0.1146 (2)	1.0845 (3)	0.46657 (18)	0.0698 (10)
H24	−0.0771	1.1071	0.5069	0.084*
C25	−0.0783 (2)	1.0577 (2)	0.39801 (16)	0.0523 (8)
H25	−0.0172	1.0637	0.3919	0.063*
C26	−0.13495 (17)	1.0217 (2)	0.33891 (14)	0.0373 (6)
C27	0.00084 (18)	0.8565 (2)	0.09764 (15)	0.0442 (7)
C28	0.0820 (2)	0.8029 (3)	0.08501 (17)	0.0561 (8)
H28	0.1314	0.8220	0.1158	0.067*
C29	0.0914 (2)	0.7219 (3)	0.02809 (19)	0.0652 (9)
H29	0.1467	0.6877	0.0205	0.078*
C30	0.0184 (2)	0.6924 (3)	−0.01728 (16)	0.0581 (8)
C31	−0.0630 (2)	0.7450 (3)	−0.00677 (16)	0.0598 (8)
H31	−0.1123	0.7258	−0.0377	0.072*
C32	−0.0709 (2)	0.8272 (3)	0.05051 (15)	0.0560 (8)
H32	−0.1257	0.8632	0.0571	0.067*
C33	−0.0371 (3)	0.5658 (4)	−0.1143 (2)	0.0942 (7)
H33A	−0.0165	0.5093	−0.1498	0.141*	0.658 (5)
H33B	−0.0666	0.6292	−0.1408	0.141*	0.658 (5)
H33C	−0.0781	0.5286	−0.0817	0.141*	0.658 (5)
H33D	−0.0293	0.5828	−0.1664	0.141*	0.342 (5)
H33E	−0.0910	0.6021	−0.0984	0.141*	0.342 (5)
H33F	−0.0408	0.4822	−0.1074	0.141*	0.342 (5)
C34	−0.1376 (2)	1.2022 (2)	0.21455 (18)	0.0631 (9)
H34A	−0.1901	1.1851	0.1838	0.095*
H34B	−0.1058	1.2663	0.1929	0.095*
H34C	−0.1547	1.2235	0.2641	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0340 (4)	0.0352 (3)	0.0407 (4)	−0.0008 (3)	−0.0073 (3)	0.0035 (3)
N1	0.0254 (11)	0.0337 (11)	0.0389 (11)	0.0001 (10)	−0.0039 (9)	−0.0023 (10)
N2	0.0350 (12)	0.0328 (12)	0.0410 (12)	−0.0001 (10)	−0.0068 (10)	0.0021 (10)
N3	0.0530 (15)	0.0327 (12)	0.0572 (15)	0.0043 (11)	0.0101 (12)	0.0077 (11)
N4	0.0292 (12)	0.0477 (14)	0.0519 (14)	0.0019 (10)	−0.0058 (11)	−0.0015 (11)
O1	0.0392 (11)	0.0379 (11)	0.0727 (13)	−0.0061 (9)	−0.0105 (10)	−0.0039 (10)
O2	0.0518 (13)	0.0663 (14)	0.0467 (12)	0.0125 (10)	−0.0128 (10)	−0.0062 (10)
O3	0.100 (2)	0.0732 (17)	0.1042 (19)	−0.0144 (15)	−0.0672 (16)	0.0175 (14)
O4	0.0698 (14)	0.0510 (13)	0.0604 (13)	0.0046 (11)	−0.0274 (11)	0.0133 (10)
O5	0.0910 (17)	0.1129 (18)	0.0796 (15)	−0.0157 (14)	0.0152 (12)	−0.0361 (13)
C1	0.0301 (14)	0.0331 (14)	0.0401 (14)	−0.0037 (11)	−0.0003 (11)	0.0039 (11)
C2	0.0295 (14)	0.0329 (14)	0.0439 (15)	0.0002 (12)	0.0050 (11)	−0.0015 (12)
C3	0.0273 (14)	0.0365 (14)	0.0321 (13)	0.0012 (11)	−0.0007 (10)	−0.0019 (11)
C4	0.0388 (16)	0.0376 (15)	0.0404 (15)	0.0052 (13)	−0.0033 (12)	0.0018 (12)
C5	0.0418 (16)	0.0380 (15)	0.0381 (14)	0.0042 (13)	−0.0072 (12)	−0.0006 (12)
C6	0.0353 (15)	0.0357 (14)	0.0421 (15)	0.0046 (12)	−0.0136 (12)	−0.0065 (12)
C7	0.028 (6)	0.054 (6)	0.058 (5)	0.006 (5)	−0.009 (4)	−0.004 (5)
C8	0.056 (3)	0.072 (4)	0.065 (4)	0.006 (3)	0.010 (3)	−0.009 (3)
C9	0.073 (5)	0.106 (6)	0.092 (5)	0.012 (4)	0.024 (4)	−0.025 (4)
C10	0.042 (4)	0.127 (6)	0.086 (4)	0.009 (4)	0.024 (3)	0.001 (4)
C11	0.059 (4)	0.115 (6)	0.121 (5)	−0.017 (4)	0.038 (4)	−0.005 (4)
C12	0.049 (3)	0.077 (4)	0.094 (4)	−0.013 (3)	0.022 (3)	−0.014 (3)
C6'	0.0353 (15)	0.0357 (14)	0.0421 (15)	0.0046 (12)	−0.0136 (12)	−0.0065 (12)
C7'	0.033 (11)	0.029 (9)	0.060 (9)	0.003 (8)	−0.005 (8)	−0.002 (8)
C8'	0.054 (7)	0.065 (7)	0.056 (6)	−0.029 (6)	0.001 (5)	0.001 (6)
C9'	0.081 (9)	0.059 (7)	0.063 (7)	−0.004 (6)	0.028 (7)	0.002 (5)
C10'	0.040 (4)	0.090 (5)	0.149 (7)	0.011 (4)	0.005 (4)	−0.029 (5)
C11'	0.040 (4)	0.090 (5)	0.149 (7)	0.011 (4)	0.005 (4)	−0.029 (5)
C12'	0.040 (4)	0.090 (5)	0.149 (7)	0.011 (4)	0.005 (4)	−0.029 (5)
C13	0.057 (2)	0.0452 (18)	0.074 (2)	−0.0036 (15)	−0.0166 (16)	0.0173 (16)
C14	0.056 (2)	0.0482 (18)	0.0487 (17)	0.0060 (16)	−0.0149 (15)	−0.0016 (15)
C15	0.082 (2)	0.069 (2)	0.056 (2)	0.0183 (19)	−0.0275 (18)	0.0101 (17)
C16	0.104 (3)	0.075 (3)	0.071 (2)	0.011 (2)	−0.015 (2)	0.023 (2)
C17	0.0422 (16)	0.0406 (15)	0.0486 (16)	−0.0024 (13)	0.0110 (13)	0.0047 (13)
C18	0.070 (2)	0.0462 (18)	0.0581 (19)	0.0055 (16)	0.0193 (16)	0.0151 (15)
C19	0.0353 (15)	0.0341 (14)	0.0392 (14)	0.0014 (11)	−0.0012 (11)	0.0018 (11)
C20	0.0416 (16)	0.0347 (14)	0.0410 (16)	0.0073 (12)	−0.0045 (13)	0.0015 (12)
C21	0.0410 (17)	0.0366 (15)	0.0460 (16)	0.0036 (12)	0.0027 (13)	0.0015 (13)
C22	0.0494 (19)	0.075 (2)	0.059 (2)	0.0085 (17)	0.0105 (16)	−0.0054 (17)
C23	0.078 (3)	0.096 (3)	0.0467 (19)	0.016 (2)	0.0107 (18)	−0.0128 (18)
C24	0.071 (2)	0.084 (3)	0.053 (2)	0.016 (2)	−0.0113 (17)	−0.0245 (18)
C25	0.0449 (18)	0.0538 (18)	0.0577 (19)	0.0055 (14)	−0.0058 (15)	−0.0114 (15)
C26	0.0369 (15)	0.0334 (14)	0.0416 (15)	0.0046 (12)	0.0004 (12)	−0.0007 (12)
C27	0.0431 (17)	0.0491 (17)	0.0409 (15)	−0.0011 (14)	0.0096 (13)	0.0077 (13)
C28	0.0470 (19)	0.0584 (19)	0.063 (2)	0.0026 (16)	0.0045 (15)	−0.0049 (16)
C29	0.052 (2)	0.068 (2)	0.076 (2)	0.0061 (17)	0.0143 (18)	−0.0125 (18)
C30	0.064 (2)	0.064 (2)	0.0473 (18)	−0.0087 (18)	0.0187 (16)	−0.0064 (16)
C31	0.056 (2)	0.085 (2)	0.0382 (16)	−0.0117 (19)	0.0021 (14)	0.0019 (17)
C32	0.0488 (19)	0.076 (2)	0.0437 (17)	0.0032 (16)	0.0098 (14)	0.0017 (16)
C33	0.0910 (17)	0.1129 (18)	0.0796 (15)	−0.0157 (14)	0.0152 (12)	−0.0361 (13)
C34	0.075 (2)	0.0372 (16)	0.077 (2)	0.0126 (16)	0.0083 (18)	0.0093 (16)

Geometric parameters (Å, º) top

S1—C3	1.740 (2)	C11'—C12'	1.3900
S1—C1	1.836 (2)	C11'—H11B	0.9300
N1—C3	1.375 (3)	C12'—H12B	0.9300
N1—C2	1.384 (3)	C13—H13A	0.9600
N1—C6	1.483 (3)	C13—H13B	0.9600
N2—C3	1.284 (3)	C13—H13C	0.9600
N2—C4	1.424 (3)	C15—C16	1.492 (5)
N3—C18	1.461 (3)	C15—H15A	0.9700
N3—C34	1.467 (3)	C15—H15B	0.9700
N3—C19	1.472 (3)	C16—H16A	0.9600
N4—C20	1.354 (3)	C16—H16B	0.9600
N4—C21	1.410 (3)	C16—H16C	0.9600
N4—H4	0.8600	C17—C27	1.505 (4)
O1—C2	1.208 (3)	C17—C18	1.523 (4)
O2—C20	1.220 (3)	C17—H17	0.9800
O3—C14	1.209 (3)	C18—H18A	0.9700
O4—C14	1.327 (3)	C18—H18B	0.9700
O4—C15	1.448 (3)	C19—C26	1.517 (3)
O5—C33	1.378 (4)	C19—C20	1.564 (4)
O5—C30	1.390 (4)	C21—C22	1.380 (4)
C1—C2	1.534 (3)	C21—C26	1.391 (4)
C1—C19	1.569 (3)	C22—C23	1.385 (4)
C1—C17	1.604 (3)	C22—H22	0.9300
C4—C5	1.345 (3)	C23—C24	1.375 (5)
C4—C13	1.510 (4)	C23—H23	0.9300
C5—C14	1.481 (4)	C24—C25	1.390 (4)
C5—C6	1.520 (4)	C24—H24	0.9300
C6—C7	1.554 (4)	C25—C26	1.388 (4)
C6—H6A	0.9800	C25—H25	0.9300
C7—C8	1.3900	C27—C32	1.379 (4)
C7—C12	1.3900	C27—C28	1.387 (4)
C8—C9	1.3900	C28—C29	1.381 (4)
C8—H8A	0.9300	C28—H28	0.9300
C9—C10	1.3900	C29—C30	1.377 (4)
C9—H9A	0.9300	C29—H29	0.9300
C10—C11	1.3900	C30—C31	1.379 (4)
C10—H10A	0.9300	C31—C32	1.392 (4)
C11—C12	1.3900	C31—H31	0.9300
C11—H11A	0.9300	C32—H32	0.9300
C12—H12A	0.9300	C33—H33A	0.9600
C7'—C8'	1.3900	C33—H33B	0.9600
C7'—C12'	1.3900	C33—H33C	0.9600
C8'—C9'	1.3900	C33—H33D	0.9600
C8'—H8'A	0.9300	C33—H33E	0.9600
C9'—C10'	1.3900	C33—H33F	0.9600
C9'—H9'A	0.9300	C34—H34A	0.9600
C10'—C11'	1.3900	C34—H34B	0.9600
C10'—H10B	0.9300	C34—H34C	0.9600

C3—S1—C1	93.18 (11)	H16A—C16—H16B	109.5
C3—N1—C2	116.8 (2)	C15—C16—H16C	109.5
C3—N1—C6	120.1 (2)	H16A—C16—H16C	109.5
C2—N1—C6	122.2 (2)	H16B—C16—H16C	109.5
C3—N2—C4	116.6 (2)	C27—C17—C18	116.6 (2)
C18—N3—C34	113.2 (2)	C27—C17—C1	116.4 (2)
C18—N3—C19	106.9 (2)	C18—C17—C1	103.4 (2)
C34—N3—C19	115.1 (2)	C27—C17—H17	106.6
C20—N4—C21	111.5 (2)	C18—C17—H17	106.6
C20—N4—H4	124.3	C1—C17—H17	106.6
C21—N4—H4	124.3	N3—C18—C17	104.0 (2)
C14—O4—C15	117.3 (2)	N3—C18—H18A	110.9
C33—O5—C30	118.1 (3)	C17—C18—H18A	110.9
C2—C1—C19	114.2 (2)	N3—C18—H18B	110.9
C2—C1—C17	107.1 (2)	C17—C18—H18B	110.9
C19—C1—C17	104.52 (19)	H18A—C18—H18B	109.0
C2—C1—S1	104.91 (16)	N3—C19—C26	112.1 (2)
C19—C1—S1	111.09 (16)	N3—C19—C20	110.6 (2)
C17—C1—S1	115.31 (17)	C26—C19—C20	101.2 (2)
O1—C2—N1	122.1 (2)	N3—C19—C1	102.82 (19)
O1—C2—C1	125.4 (2)	C26—C19—C1	121.0 (2)
N1—C2—C1	112.3 (2)	C20—C19—C1	109.17 (19)
N2—C3—N1	125.3 (2)	O2—C20—N4	126.0 (3)
N2—C3—S1	122.56 (18)	O2—C20—C19	125.8 (2)
N1—C3—S1	112.05 (18)	N4—C20—C19	108.2 (2)
C5—C4—N2	122.1 (2)	C22—C21—C26	122.3 (3)
C5—C4—C13	127.6 (2)	C22—C21—N4	127.6 (3)
N2—C4—C13	110.3 (2)	C26—C21—N4	110.0 (2)
C4—C5—C14	127.7 (3)	C21—C22—C23	117.5 (3)
C4—C5—C6	121.0 (2)	C21—C22—H22	121.3
C14—C5—C6	111.2 (2)	C23—C22—H22	121.3
N1—C6—C5	107.7 (2)	C24—C23—C22	121.4 (3)
N1—C6—C7	108.2 (2)	C24—C23—H23	119.3
C5—C6—C7	115.1 (2)	C22—C23—H23	119.3
N1—C6—H6A	108.6	C23—C24—C25	120.7 (3)
C5—C6—H6A	108.6	C23—C24—H24	119.6
C7—C6—H6A	108.6	C25—C24—H24	119.6
C8—C7—C12	120.0	C26—C25—C24	118.9 (3)
C8—C7—C6	119.1 (3)	C26—C25—H25	120.6
C12—C7—C6	120.8 (3)	C24—C25—H25	120.6
C9—C8—C7	120.0	C25—C26—C21	119.2 (3)
C9—C8—H8A	120.0	C25—C26—C19	131.6 (3)
C7—C8—H8A	120.0	C21—C26—C19	108.9 (2)
C10—C9—C8	120.0	C32—C27—C28	117.6 (3)
C10—C9—H9A	120.0	C32—C27—C17	123.2 (3)
C8—C9—H9A	120.0	C28—C27—C17	119.3 (3)
C9—C10—C11	120.0	C29—C28—C27	121.9 (3)
C9—C10—H10A	120.0	C29—C28—H28	119.0
C11—C10—H10A	120.0	C27—C28—H28	119.0
C10—C11—C12	120.0	C30—C29—C28	119.4 (3)
C10—C11—H11A	120.0	C30—C29—H29	120.3
C12—C11—H11A	120.0	C28—C29—H29	120.3
C11—C12—C7	120.0	C29—C30—C31	120.1 (3)
C11—C12—H12A	120.0	C29—C30—O5	114.9 (3)
C7—C12—H12A	120.0	C31—C30—O5	124.9 (3)
C8'—C7'—C12'	120.0	C30—C31—C32	119.5 (3)
C7'—C8'—C9'	120.0	C30—C31—H31	120.3
C7'—C8'—H8'A	120.0	C32—C31—H31	120.3
C9'—C8'—H8'A	120.0	C27—C32—C31	121.5 (3)
C8'—C9'—C10'	120.0	C27—C32—H32	119.3
C8'—C9'—H9'A	120.0	C31—C32—H32	119.3
C10'—C9'—H9'A	120.0	O5—C33—H33A	109.5
C11'—C10'—C9'	120.0	O5—C33—H33B	109.5
C11'—C10'—H10B	120.0	H33A—C33—H33B	109.5
C9'—C10'—H10B	120.0	O5—C33—H33C	109.5
C10'—C11'—C12'	120.0	H33A—C33—H33C	109.5
C10'—C11'—H11B	120.0	H33B—C33—H33C	109.5
C12'—C11'—H11B	120.0	O5—C33—H33D	109.5
C11'—C12'—C7'	120.0	H33A—C33—H33D	56.3
C11'—C12'—H12B	120.0	H33B—C33—H33D	56.2
C7'—C12'—H12B	120.0	H33C—C33—H33D	141.1
C4—C13—H13A	109.5	O5—C33—H33E	109.5
C4—C13—H13B	109.5	H33A—C33—H33E	141.1
H13A—C13—H13B	109.5	H33B—C33—H33E	56.3
C4—C13—H13C	109.5	H33C—C33—H33E	56.2
H13A—C13—H13C	109.5	H33D—C33—H33E	109.5
H13B—C13—H13C	109.5	O5—C33—H33F	109.5
O3—C14—O4	122.6 (3)	H33A—C33—H33F	56.2
O3—C14—C5	122.1 (3)	H33B—C33—H33F	141.1
O4—C14—C5	115.2 (3)	H33C—C33—H33F	56.3
O4—C15—C16	106.7 (3)	H33D—C33—H33F	109.5
O4—C15—H15A	110.4	H33E—C33—H33F	109.5
C16—C15—H15A	110.4	N3—C34—H34A	109.5
O4—C15—H15B	110.4	N3—C34—H34B	109.5
C16—C15—H15B	110.4	H34A—C34—H34B	109.5
H15A—C15—H15B	108.6	N3—C34—H34C	109.5
C15—C16—H16A	109.5	H34A—C34—H34C	109.5
C15—C16—H16B	109.5	H34B—C34—H34C	109.5

C3—S1—C1—C2	−6.90 (17)	C19—C1—C17—C18	−6.1 (3)
C3—S1—C1—C19	−130.73 (17)	S1—C1—C17—C18	116.1 (2)
C3—S1—C1—C17	110.61 (19)	C34—N3—C18—C17	−172.2 (2)
C3—N1—C2—O1	177.2 (2)	C19—N3—C18—C17	−44.4 (3)
C6—N1—C2—O1	−13.8 (4)	C27—C17—C18—N3	158.5 (2)
C3—N1—C2—C1	−7.3 (3)	C1—C17—C18—N3	29.4 (3)
C6—N1—C2—C1	161.6 (2)	C18—N3—C19—C26	170.7 (2)
C19—C1—C2—O1	−53.8 (3)	C34—N3—C19—C26	−62.6 (3)
C17—C1—C2—O1	61.3 (3)	C18—N3—C19—C20	−77.1 (3)
S1—C1—C2—O1	−175.7 (2)	C34—N3—C19—C20	49.6 (3)
C19—C1—C2—N1	130.9 (2)	C18—N3—C19—C1	39.3 (2)
C17—C1—C2—N1	−114.0 (2)	C34—N3—C19—C1	166.0 (2)
S1—C1—C2—N1	9.0 (2)	C2—C1—C19—N3	97.7 (2)
C4—N2—C3—N1	7.8 (4)	C17—C1—C19—N3	−18.9 (2)
C4—N2—C3—S1	−169.03 (18)	S1—C1—C19—N3	−143.92 (16)
C2—N1—C3—N2	−175.5 (2)	C2—C1—C19—C26	−28.1 (3)
C6—N1—C3—N2	15.3 (4)	C17—C1—C19—C26	−144.8 (2)
C2—N1—C3—S1	1.6 (3)	S1—C1—C19—C26	90.2 (2)
C6—N1—C3—S1	−167.60 (16)	C2—C1—C19—C20	−144.8 (2)
C1—S1—C3—N2	−179.2 (2)	C17—C1—C19—C20	98.5 (2)
C1—S1—C3—N1	3.57 (18)	S1—C1—C19—C20	−26.5 (2)
C3—N2—C4—C5	−13.5 (4)	C21—N4—C20—O2	179.4 (2)
C3—N2—C4—C13	165.1 (2)	C21—N4—C20—C19	−2.3 (3)
N2—C4—C5—C14	179.6 (2)	N3—C19—C20—O2	62.8 (3)
C13—C4—C5—C14	1.3 (5)	C26—C19—C20—O2	−178.3 (2)
N2—C4—C5—C6	−3.8 (4)	C1—C19—C20—O2	−49.6 (3)
C13—C4—C5—C6	177.8 (3)	N3—C19—C20—N4	−115.5 (2)
C3—N1—C6—C5	−28.9 (3)	C26—C19—C20—N4	3.5 (3)
C2—N1—C6—C5	162.6 (2)	C1—C19—C20—N4	132.1 (2)
C3—N1—C6—C7	96.2 (3)	C20—N4—C21—C22	177.6 (3)
C2—N1—C6—C7	−72.4 (3)	C20—N4—C21—C26	0.0 (3)
C4—C5—C6—N1	23.4 (3)	C26—C21—C22—C23	−0.2 (4)
C14—C5—C6—N1	−159.6 (2)	N4—C21—C22—C23	−177.5 (3)
C4—C5—C6—C7	−97.4 (3)	C21—C22—C23—C24	1.3 (5)
C14—C5—C6—C7	79.7 (3)	C22—C23—C24—C25	−0.6 (6)
N1—C6—C7—C8	−90.3 (3)	C23—C24—C25—C26	−1.4 (5)
C5—C6—C7—C8	30.2 (4)	C24—C25—C26—C21	2.5 (4)
N1—C6—C7—C12	87.9 (3)	C24—C25—C26—C19	174.5 (3)
C5—C6—C7—C12	−151.6 (3)	C22—C21—C26—C25	−1.7 (4)
C12—C7—C8—C9	0.0	N4—C21—C26—C25	176.0 (2)
C6—C7—C8—C9	178.2 (3)	C22—C21—C26—C19	−175.4 (3)
C7—C8—C9—C10	0.0	N4—C21—C26—C19	2.4 (3)
C8—C9—C10—C11	0.0	N3—C19—C26—C25	−58.2 (4)
C9—C10—C11—C12	0.0	C20—C19—C26—C25	−176.1 (3)
C10—C11—C12—C7	0.0	C1—C19—C26—C25	63.3 (4)
C8—C7—C12—C11	0.0	N3—C19—C26—C21	114.4 (2)
C6—C7—C12—C11	−178.2 (3)	C20—C19—C26—C21	−3.4 (3)
C12'—C7'—C8'—C9'	0.0	C1—C19—C26—C21	−124.1 (2)
C7'—C8'—C9'—C10'	0.0	C18—C17—C27—C32	−48.3 (4)
C8'—C9'—C10'—C11'	0.0	C1—C17—C27—C32	74.3 (3)
C9'—C10'—C11'—C12'	0.0	C18—C17—C27—C28	133.1 (3)
C10'—C11'—C12'—C7'	0.0	C1—C17—C27—C28	−104.3 (3)
C8'—C7'—C12'—C11'	0.0	C32—C27—C28—C29	−0.7 (4)
C15—O4—C14—O3	1.0 (5)	C17—C27—C28—C29	178.0 (3)
C15—O4—C14—C5	−179.3 (3)	C27—C28—C29—C30	−0.6 (5)
C4—C5—C14—O3	−177.8 (3)	C28—C29—C30—C31	1.3 (5)
C6—C5—C14—O3	5.3 (4)	C28—C29—C30—O5	−179.2 (3)
C4—C5—C14—O4	2.5 (4)	C33—O5—C30—C29	173.1 (3)
C6—C5—C14—O4	−174.4 (2)	C33—O5—C30—C31	−7.4 (5)
C14—O4—C15—C16	176.7 (3)	C29—C30—C31—C32	−0.7 (5)
C2—C1—C17—C27	103.2 (3)	O5—C30—C31—C32	179.8 (3)
C19—C1—C17—C27	−135.4 (2)	C28—C27—C32—C31	1.3 (4)
S1—C1—C17—C27	−13.1 (3)	C17—C27—C32—C31	−177.3 (3)
C2—C1—C17—C18	−127.6 (2)	C30—C31—C32—C27	−0.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2ⁱ	0.86	2.31	3.027 (2)	140

Symmetry code: (i) −x−1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₄H₃₂N₄O₅S
M_r	608.70
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.990 (6), 11.375 (5), 17.815 (8)
β (°)	92.254 (6)
V (Å³)	3035 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.38 × 0.30 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.905, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	14013, 6236, 3567
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.137, 1.00
No. of reflections	6236
No. of parameters	413
No. of restraints	278
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.40

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.