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Single crystals of the title compound, C39H43N3O11S·2C3H8O, have been obtained from 2-propanol/water solutions. ET-743 belongs to the group of ecteinascidins (ETs), which is a family of novel marine tetra­hydro­iso­quinoline derivatives characterized by a monobridged pentacyclic skeleton. Three large princi­pal planar groups are observed in the three-dimensional structure of the ET-743 mol­ecule, corresponding to three aromatic units which are nearly perpendicular to each other. In the crystal, the methoxy group on the large fused ring system adopts an anti conformation with respect to the S atom, thus presenting the same conformation as that found in solution.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103003676/fa1005sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103003676/fa1005Isup2.hkl
Contains datablock I

CCDC reference: 172159

Comment top

Microbe-derived compounds related to the ecteinascidins (ETs) are saframycines, safracines, naphthydinomycines and quinocarcines. The common structural features of ETs consist of three tetrahydroisoquinoline subunits and an active carbinolamine functional group (Rinehart et al., 1990). ETs are currently obtained by extraction and purification from the marine tunicate Ecteinascidia turbinate, although recently a very efficient synthetic method has been reported (Cuevas et al., 2000). Several compounds of the ET family possess potent antitumor activity. Among them, the natural compound named ET-743 has received considerable attention, as it has been demonstrated to be a potent anticancer agent with proven high efficacy in soft tissue sarcoma and breast cancer (Garcia-Nieto et al., 2000). ET-743 has been accepted for evaluation by EMEA (European Agency for the Evaluation of Medicinal Products) and the Swiss authorities. The structure of the 2-propanol disolvate of ET-743, (I), is presented here.

Selected geometrical features of (I) are shown in Table 1. Although the overall molecular structure of ET-743 is very similar to the N12-oxide derivative (Guan et al., 1993), there is one remarkable difference. The O41—C42 methoxy group, attached to C17 and in a plane perpendicular to the aromatic ring [C16—C17—O41—C42 = 99.2 (3)°], adopts a position anti with respect to the S atom, whereas this conformation was found to be syn in the N12-oxide derivative. This anti conformation is consistent with a previous NMR study (Seaman & Hurley, 1998) and seems to be very important since this part of the molecule is involved in its interaction with DNA (Garcia-Nieto et al., 2000). Molecular simulation studies carried out on the ET-743 molecule (Garcia-Nieto et al., 2000) concluded that the syn conformation is more stable and that the conformation of this methoxy group changes from syn to anti during the solvation process. The present study demonstrates that there is no conformational change, since the ET-743 molecule maintains the same anti conformation in both the solution and solid states.

The crystal packing is mediated mainly by hydrogen bonds between the ET-743 molecule and the two interstitial 2-propanol molecules. The hydrogen-bonding parameters are presented in Table 2.

Experimental top

The sample of ET-743 used for crystallization was either isolated from the Caribbean tunicate Ecteinascidia turbinata by an extraction and purification process (Rinehart et al., 1990) or synthesized (Corey et al., 1996; Cuevas et al., 2000). In both cases, ET-743 was obtained as a lyophilized white-to-pale-yellow amorphous powder. The powder was stored at 253 K in an airtight container. The best and most reproducible crystals, although exhibiting rather bad scattering properties, were obtained from 2-propanol/water (19:1 v/v) by dissolving ET-743 (6–15 mg ml−1) at 303 K and crystallizing it at 277 K. Although no water molecules were detected in the crystal structure of ET-743, the presence of water is important for obtaining single crystals. Hence, it seems that the role of water is only to control the nucleation and crystal-growth rates during the crystallization process.

Refinement top

The space group was deduced from the systematic absences and intensity statistics. All H atoms were found in a difference electron-density map, but they were all placed in calculated positions (C—H = 0.95–1.00 Å), with Uiso values taken as 1.2 times (1.5 for methyl) the Ueq values of the parent atoms. The absolute configuration was assigned to agree with the chirality determined for the N-oxide derivative (Guan et al., 1993). Friedel pairs were not averaged and the refined value of the Flack (1983) parameter was in agreement with this previously established absolute configuration.

Computing details top

Data collection: SMART (Bruker (1997); cell refinement: SMART; data reduction: SAINT (Bruker (1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999b); software used to prepare material for publication: WinGX (Farrugia, 1999a) and PARST (Nardelli, 1995).

Figures top
[Figure 1]
Fig. 1. The molecular formula of ecteinascidin 743 (ET-743).

Fig. 2. ORTEP-3 (Farrugia, 1999b) diagram of the asymmetric unit of the crystal lattice of ET-743, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity.
(I) top
Crystal data top
C39H43N3O11S·2C3H8OF(000) = 1880
Mr = 882.01Dx = 1.284 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 115 reflections
a = 13.0161 (13) Åθ = 10–20°
b = 13.2290 (14) ŵ = 0.14 mm1
c = 26.496 (3) ÅT = 173 K
V = 4562.3 (8) Å3Prism, colourless
Z = 40.3 × 0.25 × 0.2 mm
Data collection top
Bruker SMART CCD 1K
diffractometer
Rint = 0.096
ϕ and ω scansθmax = 26.4°, θmin = 3.5°
14784 measured reflectionsh = 816
7901 independent reflectionsk = 1616
3827 reflections with I > 2σ(I)l = 337
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0345P)2 + 1.7941P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.078(Δ/σ)max < 0.001
wR(F2) = 0.132Δρmax = 0.35 e Å3
S = 1.12Δρmin = 0.27 e Å3
13297 reflectionsAbsolute structure: Flack (1983), 2697 Friedel pairs
575 parametersAbsolute structure parameter: 0.10 (8)
0 restraints
Crystal data top
C39H43N3O11S·2C3H8OV = 4562.3 (8) Å3
Mr = 882.01Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 13.0161 (13) ŵ = 0.14 mm1
b = 13.2290 (14) ÅT = 173 K
c = 26.496 (3) Å0.3 × 0.25 × 0.2 mm
Data collection top
Bruker SMART CCD 1K
diffractometer
3827 reflections with I > 2σ(I)
14784 measured reflectionsRint = 0.096
7901 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.35 e Å3
S = 1.12Δρmin = 0.27 e Å3
13297 reflectionsAbsolute structure: Flack (1983), 2697 Friedel pairs
575 parametersAbsolute structure parameter: 0.10 (8)
0 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.77185 (19)0.92970 (18)0.02651 (9)0.0211 (5)
H10.78280.93040.06390.025*
N20.77276 (14)0.82395 (16)0.00915 (7)0.0187 (4)
C30.87431 (17)0.78826 (18)0.00675 (9)0.0175 (5)
H30.92270.80490.02140.021*
C40.90994 (18)0.85041 (18)0.05287 (9)0.0192 (5)
H40.98170.8280.06030.023*
S440.83586 (5)0.83148 (5)0.11231 (2)0.02398 (13)
C50.98755 (19)1.0248 (2)0.05996 (10)0.0246 (5)
C61.0034 (2)1.1249 (2)0.04472 (11)0.0316 (6)
C70.9420 (2)1.1542 (2)0.00542 (11)0.0338 (6)
C80.8704 (2)1.0921 (2)0.01703 (10)0.0283 (6)
C90.85477 (18)0.99374 (19)0.00204 (9)0.0210 (5)
C100.91737 (18)0.9596 (2)0.03757 (9)0.0204 (5)
C110.88085 (18)0.67259 (19)0.01466 (9)0.0199 (5)
H110.95540.65430.0150.024*
N120.83481 (17)0.62324 (16)0.03006 (8)0.0243 (4)
C130.72496 (19)0.6497 (2)0.03098 (10)0.0240 (5)
H130.69220.60960.05860.029*
C140.6646 (2)0.6281 (2)0.01810 (10)0.0285 (6)
H14A0.61880.68620.02490.034*
H14B0.62060.56810.01250.034*
C150.6867 (2)0.5712 (2)0.10819 (11)0.0304 (6)
H150.61450.56110.10990.036*
C160.7466 (2)0.5473 (2)0.14982 (10)0.0298 (6)
C170.8526 (2)0.5633 (2)0.14654 (10)0.0258 (6)
C180.89576 (19)0.60671 (19)0.10376 (10)0.0232 (5)
C190.83437 (19)0.63046 (18)0.06234 (9)0.0214 (5)
C200.7294 (2)0.60969 (19)0.06405 (10)0.0241 (5)
C210.72411 (19)0.7596 (2)0.04699 (9)0.0237 (5)
H210.6510.78150.05080.028*
C220.65178 (18)0.94065 (18)0.12343 (9)0.0204 (5)
N230.61690 (16)0.85670 (17)0.15530 (8)0.0250 (5)
H230.62920.7950.13510.03*
C240.5048 (2)0.8577 (2)0.16369 (11)0.0325 (6)
H24A0.48340.79450.18070.039*
H24B0.46860.86190.13090.039*
C250.4770 (2)0.9478 (2)0.19607 (11)0.0325 (6)
H25A0.40140.95440.19770.039*
H25B0.50280.9370.23080.039*
C260.4844 (2)1.1379 (2)0.18998 (10)0.0303 (6)
H260.42921.14010.21340.036*
C270.5242 (2)1.2277 (2)0.17198 (11)0.0299 (6)
C280.6053 (2)1.2236 (2)0.13678 (10)0.0282 (6)
C290.64428 (19)1.1320 (2)0.12226 (9)0.0244 (5)
H290.69981.13020.0990.029*
C300.52269 (19)1.0438 (2)0.17486 (10)0.0253 (6)
C310.60430 (19)1.0406 (2)0.14081 (9)0.0223 (5)
O340.93827 (19)1.24878 (17)0.01666 (9)0.0472 (6)
C330.8784 (3)1.2332 (3)0.06117 (14)0.0505 (9)
H33A0.83351.29240.06730.061*
H33B0.9241.22450.09080.061*
O320.81772 (16)1.14489 (15)0.05388 (8)0.0360 (5)
C351.0810 (3)1.1944 (3)0.06874 (14)0.0488 (9)
H35A1.09721.24970.04550.073*
H35B1.14381.15650.07640.073*
H35C1.05261.22220.10.073*
O361.05179 (13)0.98370 (15)0.09741 (7)0.0278 (4)
C371.0327 (2)1.0098 (3)0.14670 (11)0.0354 (7)
C381.1020 (3)0.9530 (4)0.18079 (14)0.0623 (11)
H38A1.1730.96030.16920.093*
H38B1.08290.88130.18060.093*
H38C1.09570.97960.21520.093*
O390.96887 (18)1.07054 (19)0.15839 (8)0.0461 (6)
O400.99822 (13)0.62768 (16)0.10094 (7)0.0284 (4)
H401.02350.62790.13010.043*
O410.91701 (16)0.53831 (16)0.18664 (7)0.0357 (5)
C420.9665 (3)0.4427 (3)0.17908 (15)0.0551 (10)
H42A0.91450.38940.17670.083*
H42B1.01220.42860.20760.083*
H42C1.00660.44480.14780.083*
C430.6994 (3)0.5041 (3)0.19699 (12)0.0448 (8)
H43A0.69830.55590.22340.067*
H43B0.74020.44620.20850.067*
H43C0.62910.4820.18980.067*
C450.77030 (18)0.94827 (19)0.12785 (9)0.0206 (5)
H45A0.78840.96790.16280.025*
H45B0.7951.00230.1050.025*
C460.62339 (19)0.9200 (2)0.06824 (10)0.0215 (5)
O470.57428 (13)0.84945 (15)0.05356 (7)0.0270 (4)
O480.66129 (13)0.99402 (13)0.03862 (6)0.0230 (4)
C490.6670 (2)0.97664 (19)0.01523 (9)0.0230 (5)
H49A0.65931.04120.03370.028*
H49B0.61150.93040.0260.028*
O500.48868 (17)1.32059 (16)0.18514 (9)0.0417 (5)
H500.43811.31420.20460.063*
O510.63919 (18)1.31509 (15)0.11875 (9)0.0447 (6)
C520.7174 (4)1.3119 (3)0.08153 (16)0.0670 (13)
H52A0.77951.28170.0960.1*
H52B0.73261.38070.070.1*
H52C0.69421.27110.05290.1*
O530.77317 (15)0.76637 (15)0.09550 (7)0.0306 (4)
H530.82460.72810.09610.046*
C550.8541 (2)0.5142 (2)0.03232 (11)0.0298 (6)
H55A0.81960.48090.0040.045*
H55B0.92820.50170.03030.045*
H55C0.82740.48720.06420.045*
O800.67443 (17)0.8072 (2)0.25378 (8)0.0452 (6)
H800.67050.82930.22410.068*
C810.7773 (2)0.8176 (3)0.27163 (12)0.0386 (7)
H810.80360.88570.26160.046*
C820.7728 (3)0.8123 (4)0.32837 (13)0.0634 (11)
H82A0.72790.8660.34110.095*
H82B0.8420.82110.34220.095*
H82C0.74560.74640.33870.095*
C830.8452 (4)0.7391 (3)0.24937 (15)0.0655 (11)
H83A0.81990.67190.25880.098*
H83B0.91520.74790.26210.098*
H83C0.84510.74570.21250.098*
O900.1481 (2)0.6500 (3)0.16971 (10)0.0916 (13)
H900.19240.67670.15090.137*
C910.1924 (3)0.6274 (3)0.21686 (13)0.0563 (10)
H910.15150.57150.23240.068*
C920.3010 (4)0.5907 (4)0.2111 (2)0.0973 (18)
H92A0.30360.53820.1850.146*
H92B0.32510.56280.24320.146*
H92C0.34520.64730.20110.146*
C930.1869 (6)0.7165 (4)0.2514 (2)0.116 (2)
H93A0.23680.76760.24060.174*
H93B0.20260.69510.2860.174*
H93C0.11760.74540.25030.174*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0205 (12)0.0243 (13)0.0186 (12)0.0013 (10)0.0017 (10)0.0015 (10)
N20.0151 (9)0.0209 (10)0.0202 (10)0.0004 (8)0.0029 (8)0.0016 (8)
C30.0142 (10)0.0230 (12)0.0154 (11)0.0002 (9)0.0003 (9)0.0021 (9)
C40.0171 (11)0.0223 (13)0.0182 (11)0.0005 (9)0.0001 (9)0.0030 (9)
S440.0273 (3)0.0254 (3)0.0192 (3)0.0064 (3)0.0038 (3)0.0009 (2)
C50.0207 (12)0.0309 (15)0.0222 (13)0.0004 (10)0.0007 (10)0.0062 (10)
C60.0288 (14)0.0312 (15)0.0348 (15)0.0082 (12)0.0002 (12)0.0053 (12)
C70.0389 (16)0.0254 (15)0.0369 (16)0.0074 (12)0.0034 (12)0.0021 (12)
C80.0296 (14)0.0298 (14)0.0256 (14)0.0012 (11)0.0009 (11)0.0018 (11)
C90.0191 (12)0.0249 (13)0.0189 (12)0.0001 (10)0.0029 (9)0.0003 (9)
C100.0163 (11)0.0253 (13)0.0195 (12)0.0016 (9)0.0034 (9)0.0047 (10)
C110.0170 (11)0.0216 (12)0.0213 (12)0.0017 (10)0.0009 (9)0.0014 (10)
N120.0242 (10)0.0245 (11)0.0242 (11)0.0025 (9)0.0031 (9)0.0045 (9)
C130.0211 (12)0.0250 (14)0.0260 (13)0.0029 (10)0.0049 (10)0.0055 (10)
C140.0190 (12)0.0309 (14)0.0356 (15)0.0039 (11)0.0014 (11)0.0030 (11)
C150.0226 (13)0.0326 (15)0.0360 (16)0.0065 (11)0.0078 (11)0.0054 (12)
C160.0319 (15)0.0309 (15)0.0267 (14)0.0055 (12)0.0061 (11)0.0004 (11)
C170.0281 (14)0.0273 (14)0.0219 (13)0.0016 (11)0.0019 (10)0.0009 (10)
C180.0239 (12)0.0191 (12)0.0267 (13)0.0007 (10)0.0018 (10)0.0005 (10)
C190.0213 (11)0.0194 (12)0.0235 (12)0.0005 (10)0.0030 (10)0.0010 (9)
C200.0235 (12)0.0189 (13)0.0300 (14)0.0022 (10)0.0028 (10)0.0042 (10)
C210.0207 (12)0.0273 (14)0.0231 (13)0.0004 (10)0.0060 (10)0.0035 (10)
C220.0158 (11)0.0233 (12)0.0220 (12)0.0001 (9)0.0022 (9)0.0004 (9)
N230.0236 (10)0.0267 (12)0.0245 (11)0.0006 (9)0.0048 (9)0.0004 (9)
C240.0264 (14)0.0380 (17)0.0332 (15)0.0031 (12)0.0061 (11)0.0051 (12)
C250.0284 (14)0.0375 (17)0.0315 (15)0.0022 (12)0.0117 (11)0.0032 (12)
C260.0237 (13)0.0436 (17)0.0236 (13)0.0071 (12)0.0034 (10)0.0054 (12)
C270.0285 (14)0.0336 (16)0.0276 (14)0.0069 (12)0.0003 (11)0.0080 (12)
C280.0307 (15)0.0255 (14)0.0284 (14)0.0012 (11)0.0031 (11)0.0035 (11)
C290.0224 (12)0.0271 (13)0.0236 (13)0.0019 (10)0.0043 (10)0.0035 (10)
C300.0205 (13)0.0331 (15)0.0223 (13)0.0027 (11)0.0011 (10)0.0002 (11)
C310.0212 (12)0.0285 (14)0.0173 (12)0.0022 (10)0.0002 (9)0.0039 (10)
O340.0615 (15)0.0302 (12)0.0498 (14)0.0147 (11)0.0130 (12)0.0102 (10)
C330.057 (2)0.043 (2)0.052 (2)0.0164 (17)0.0091 (17)0.0206 (17)
O320.0420 (12)0.0307 (11)0.0353 (11)0.0059 (9)0.0077 (9)0.0113 (9)
C350.051 (2)0.0386 (19)0.057 (2)0.0203 (16)0.0149 (17)0.0040 (16)
O360.0216 (9)0.0350 (11)0.0267 (10)0.0001 (8)0.0059 (7)0.0061 (8)
C370.0328 (15)0.0443 (19)0.0291 (15)0.0066 (14)0.0043 (12)0.0060 (13)
C380.065 (3)0.085 (3)0.0373 (19)0.010 (2)0.0202 (18)0.0020 (19)
O390.0404 (13)0.0606 (16)0.0374 (12)0.0058 (11)0.0012 (10)0.0198 (11)
O400.0197 (9)0.0415 (11)0.0241 (9)0.0000 (8)0.0015 (7)0.0053 (8)
O410.0388 (11)0.0414 (12)0.0268 (10)0.0030 (10)0.0017 (9)0.0073 (9)
C420.065 (2)0.050 (2)0.050 (2)0.0199 (19)0.0018 (18)0.0130 (18)
C430.0411 (18)0.062 (2)0.0318 (16)0.0165 (16)0.0116 (13)0.0044 (15)
C450.0185 (11)0.0222 (13)0.0212 (12)0.0009 (10)0.0005 (9)0.0029 (10)
C460.0147 (11)0.0257 (13)0.0241 (13)0.0024 (10)0.0015 (9)0.0003 (10)
O470.0204 (9)0.0325 (11)0.0281 (10)0.0043 (8)0.0024 (7)0.0017 (8)
O480.0232 (8)0.0252 (9)0.0204 (9)0.0020 (8)0.0023 (7)0.0009 (7)
C490.0247 (12)0.0282 (13)0.0160 (11)0.0046 (11)0.0017 (10)0.0018 (10)
O500.0409 (12)0.0343 (12)0.0500 (14)0.0069 (10)0.0162 (10)0.0142 (10)
O510.0558 (14)0.0245 (11)0.0538 (14)0.0011 (9)0.0238 (11)0.0056 (10)
C520.094 (3)0.0285 (19)0.079 (3)0.0077 (19)0.055 (3)0.0019 (18)
O530.0364 (11)0.0347 (12)0.0207 (9)0.0042 (9)0.0019 (8)0.0044 (8)
C550.0323 (15)0.0224 (13)0.0345 (15)0.0000 (11)0.0007 (12)0.0074 (11)
O800.0316 (11)0.0730 (17)0.0310 (11)0.0111 (11)0.0005 (9)0.0178 (11)
C810.0345 (16)0.0441 (19)0.0372 (17)0.0072 (14)0.0025 (13)0.0073 (14)
C820.059 (2)0.096 (3)0.0349 (19)0.007 (2)0.0091 (17)0.006 (2)
C830.071 (3)0.067 (3)0.059 (3)0.018 (2)0.005 (2)0.002 (2)
O900.0490 (16)0.187 (4)0.0385 (14)0.055 (2)0.0208 (12)0.0421 (19)
C910.062 (2)0.067 (3)0.039 (2)0.014 (2)0.0104 (17)0.0166 (19)
C920.082 (4)0.091 (4)0.119 (5)0.010 (3)0.024 (3)0.026 (3)
C930.188 (7)0.085 (4)0.075 (4)0.021 (4)0.024 (4)0.008 (3)
Geometric parameters (Å, º) top
C1—N21.473 (3)C28—O511.374 (3)
C1—C91.518 (3)C29—C311.405 (4)
C1—C491.529 (3)C29—H290.95
C1—H11C30—C311.395 (4)
N2—C211.460 (3)O34—C331.429 (4)
N2—C31.466 (3)C33—O321.424 (4)
C3—C41.545 (3)C33—H33A0.99
C3—C111.547 (3)C33—H33B0.99
C3—H31C35—H35A0.98
C4—C101.503 (4)C35—H35B0.98
C4—S441.864 (2)C35—H35C0.98
C4—H41O36—C371.374 (3)
S44—C451.813 (3)C37—O391.197 (4)
C5—C101.390 (3)C37—C381.482 (5)
C5—C61.400 (4)C38—H38A0.98
C5—O361.407 (3)C38—H38B0.98
C6—C71.369 (4)C38—H38C0.98
C6—C351.508 (4)O40—H400.84
C7—C81.377 (4)O41—C421.434 (4)
C7—O341.383 (4)C42—H42A0.98
C8—C91.375 (4)C42—H42B0.98
C8—O321.383 (3)C42—H42C0.98
C9—C101.404 (3)C43—H43A0.98
C11—N121.480 (3)C43—H43B0.98
C11—C191.508 (3)C43—H43C0.98
C11—H111C45—H45A0.99
N12—C551.466 (3)C45—H45B0.99
N12—C131.473 (3)C46—O471.197 (3)
C13—C211.515 (4)C46—O481.348 (3)
C13—C141.546 (4)O48—C491.447 (3)
C13—H131C49—H49A0.99
C14—C201.502 (4)C49—H49B0.99
C14—H14A0.99O50—H500.84
C14—H14B0.99O51—C521.419 (4)
C15—C161.388 (4)C52—H52A0.98
C15—C201.392 (4)C52—H52B0.98
C15—H150.95C52—H52C0.98
C16—C171.399 (4)O53—H530.84
C16—C431.506 (4)C55—H55A0.98
C17—C181.390 (4)C55—H55B0.98
C17—O411.394 (3)C55—H55C0.98
C18—O401.365 (3)O80—C811.427 (4)
C18—C191.394 (4)O80—H800.84
C19—C201.395 (4)C81—C831.486 (5)
C21—O531.438 (3)C81—C821.506 (4)
C21—H211C81—H811
C22—N231.468 (3)C82—H82A0.98
C22—C311.531 (4)C82—H82B0.98
C22—C461.533 (3)C82—H82C0.98
C22—C451.551 (3)C83—H83A0.98
N23—C241.477 (3)C83—H83B0.98
N23—H230.99C83—H83C0.98
C24—C251.513 (4)O90—C911.408 (4)
C24—H24A0.99O90—H900.84
C24—H24B0.99C91—C931.495 (7)
C25—C301.511 (4)C91—C921.503 (7)
C25—H25A0.99C91—H911
C25—H25B0.99C92—H92A0.98
C26—C271.380 (4)C92—H92B0.98
C26—C301.400 (4)C92—H92C0.98
C26—H260.95C93—H93A0.98
C27—O501.359 (3)C93—H93B0.98
C27—C281.410 (4)C93—H93C0.98
C28—C291.370 (4)
N2—C1—C9113.0 (2)C28—C29—H29119.1
N2—C1—C49109.4 (2)C31—C29—H29119.1
C9—C1—C49109.0 (2)C31—C30—C26118.9 (3)
N2—C1—H1108.5C31—C30—C25121.0 (2)
C9—C1—H1108.5C26—C30—C25120.1 (2)
C49—C1—H1108.5C30—C31—C29118.9 (2)
C21—N2—C3113.63 (19)C30—C31—C22121.9 (2)
C21—N2—C1109.66 (19)C29—C31—C22119.2 (2)
C3—N2—C1113.76 (18)C7—O34—C33103.8 (2)
N2—C3—C4109.09 (19)O32—C33—O34108.0 (2)
N2—C3—C11114.03 (19)O32—C33—H33A110.1
C4—C3—C11113.76 (19)O34—C33—H33A110.1
N2—C3—H3106.5O32—C33—H33B110.1
C4—C3—H3106.5O34—C33—H33B110.1
C11—C3—H3106.5H33A—C33—H33B108.4
C10—C4—C3108.50 (19)C8—O32—C33103.6 (2)
C10—C4—S44112.97 (16)C6—C35—H35A109.5
C3—C4—S44116.21 (16)C6—C35—H35B109.5
C10—C4—H4106.1H35A—C35—H35B109.5
C3—C4—H4106.1C6—C35—H35C109.5
S44—C4—H4106.1H35A—C35—H35C109.5
C45—S44—C4108.73 (11)H35B—C35—H35C109.5
C10—C5—C6124.1 (2)C37—O36—C5117.8 (2)
C10—C5—O36116.9 (2)O39—C37—O36122.7 (3)
C6—C5—O36118.8 (2)O39—C37—C38127.3 (3)
C7—C6—C5113.7 (2)O36—C37—C38110.0 (3)
C7—C6—C35122.7 (3)C37—C38—H38A109.5
C5—C6—C35123.7 (3)C37—C38—H38B109.5
C6—C7—C8123.7 (3)H38A—C38—H38B109.5
C6—C7—O34126.8 (3)C37—C38—H38C109.5
C8—C7—O34109.5 (3)H38A—C38—H38C109.5
C9—C8—C7122.7 (3)H38B—C38—H38C109.5
C9—C8—O32127.5 (2)C18—O40—H40109.5
C7—C8—O32109.8 (2)C17—O41—C42111.9 (2)
C8—C9—C10115.8 (2)O41—C42—H42A109.5
C8—C9—C1120.7 (2)O41—C42—H42B109.5
C10—C9—C1123.5 (2)H42A—C42—H42B109.5
C5—C10—C9120.1 (2)O41—C42—H42C109.5
C5—C10—C4121.6 (2)H42A—C42—H42C109.5
C9—C10—C4118.3 (2)H42B—C42—H42C109.5
N12—C11—C19110.2 (2)C16—C43—H43A109.5
N12—C11—C3107.80 (19)C16—C43—H43B109.5
C19—C11—C3117.2 (2)H43A—C43—H43B109.5
N12—C11—H11107.1C16—C43—H43C109.5
C19—C11—H11107.1H43A—C43—H43C109.5
C3—C11—H11107.1H43B—C43—H43C109.5
C55—N12—C13113.6 (2)C22—C45—S44113.34 (17)
C55—N12—C11113.4 (2)C22—C45—H45A108.9
C13—N12—C11107.57 (19)S44—C45—H45A108.9
N12—C13—C21103.9 (2)C22—C45—H45B108.9
N12—C13—C14115.8 (2)S44—C45—H45B108.9
C21—C13—C14114.2 (2)H45A—C45—H45B107.7
N12—C13—H13107.5O47—C46—O48125.0 (2)
C21—C13—H13107.5O47—C46—C22125.3 (2)
C14—C13—H13107.5O48—C46—C22109.7 (2)
C20—C14—C13115.2 (2)C46—O48—C49118.5 (2)
C20—C14—H14A108.5O48—C49—C1107.67 (19)
C13—C14—H14A108.5O48—C49—H49A110.2
C20—C14—H14B108.5C1—C49—H49A110.2
C13—C14—H14B108.5O48—C49—H49B110.2
H14A—C14—H14B107.5C1—C49—H49B110.2
C16—C15—C20121.8 (2)H49A—C49—H49B108.5
C16—C15—H15119.1C27—O50—H50109.5
C20—C15—H15119.1C28—O51—C52116.5 (2)
C15—C16—C17118.1 (2)O51—C52—H52A109.5
C15—C16—C43121.2 (3)O51—C52—H52B109.5
C17—C16—C43120.8 (3)H52A—C52—H52B109.5
C18—C17—O41118.4 (2)O51—C52—H52C109.5
C18—C17—C16120.8 (2)H52A—C52—H52C109.5
O41—C17—C16120.7 (2)H52B—C52—H52C109.5
O40—C18—C17121.6 (2)C21—O53—H53109.5
O40—C18—C19118.1 (2)N12—C55—H55A109.5
C17—C18—C19120.2 (2)N12—C55—H55B109.5
C18—C19—C20119.5 (2)H55A—C55—H55B109.5
C18—C19—C11120.9 (2)N12—C55—H55C109.5
C20—C19—C11119.6 (2)H55A—C55—H55C109.5
C15—C20—C19119.4 (2)H55B—C55—H55C109.5
C15—C20—C14121.1 (2)C81—O80—H80109.5
C19—C20—C14119.5 (2)O80—C81—C83111.0 (3)
O53—C21—N2112.6 (2)O80—C81—C82106.9 (3)
O53—C21—C13107.9 (2)C83—C81—C82112.8 (3)
N2—C21—C13111.4 (2)O80—C81—H81108.7
O53—C21—H21108.3C83—C81—H81108.7
N2—C21—H21108.3C82—C81—H81108.7
C13—C21—H21108.3C81—C82—H82A109.5
N23—C22—C31110.85 (19)C81—C82—H82B109.5
N23—C22—C46109.8 (2)H82A—C82—H82B109.5
C31—C22—C46110.1 (2)C81—C82—H82C109.5
N23—C22—C45108.3 (2)H82A—C82—H82C109.5
C31—C22—C45108.84 (19)H82B—C82—H82C109.5
C46—C22—C45108.88 (19)C81—C83—H83A109.5
C22—N23—C24112.7 (2)C81—C83—H83B109.5
C22—N23—H23105.3H83A—C83—H83B109.5
C24—N23—H23104.4C81—C83—H83C109.5
N23—C24—C25109.2 (2)H83A—C83—H83C109.5
N23—C24—H24A109.8H83B—C83—H83C109.5
C25—C24—H24A109.8C91—O90—H90109.5
N23—C24—H24B109.8O90—C91—C93110.9 (4)
C25—C24—H24B109.8O90—C91—C92111.3 (4)
H24A—C24—H24B108.3C93—C91—C92111.3 (5)
C30—C25—C24111.0 (2)O90—C91—H91107.7
C30—C25—H25A109.4C93—C91—H91107.7
C24—C25—H25A109.4C92—C91—H91107.7
C30—C25—H25B109.4C91—C92—H92A109.5
C24—C25—H25B109.4C91—C92—H92B109.5
H25A—C25—H25B108H92A—C92—H92B109.5
C27—C26—C30122.2 (2)C91—C92—H92C109.5
C27—C26—H26118.9H92A—C92—H92C109.5
C30—C26—H26118.9H92B—C92—H92C109.5
O50—C27—C26124.2 (3)C91—C93—H93A109.5
O50—C27—C28117.3 (3)C91—C93—H93B109.5
C26—C27—C28118.5 (3)H93A—C93—H93B109.5
C29—C28—O51124.2 (2)C91—C93—H93C109.5
C29—C28—C27119.8 (3)H93A—C93—H93C109.5
O51—C28—C27116.0 (2)H93B—C93—H93C109.5
C28—C29—C31121.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O40—H40···O90i0.841.962.687 (3)145
O50—H50···O80ii0.841.842.676 (3)177
O80—H80···N230.841.992.793 (3)161
O90—H90···O53iii0.841.962.783 (4)167
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1/2, z+1/2; (iii) x1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formulaC39H43N3O11S·2C3H8O
Mr882.01
Crystal system, space groupOrthorhombic, P212121
Temperature (K)173
a, b, c (Å)13.0161 (13), 13.2290 (14), 26.496 (3)
V3)4562.3 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.3 × 0.25 × 0.2
Data collection
DiffractometerBruker SMART CCD 1K
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
14784, 7901, 3827
Rint0.096
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.078, 0.132, 1.12
No. of reflections13297
No. of parameters575
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.27
Absolute structureFlack (1983), 2697 Friedel pairs
Absolute structure parameter0.10 (8)

Computer programs: SMART (Bruker (1997), SMART, SAINT (Bruker (1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1999b), WinGX (Farrugia, 1999a) and PARST (Nardelli, 1995).

Selected geometric parameters (Å, º) top
C1—N21.473 (3)C13—C141.546 (4)
N2—C211.460 (3)C17—O411.394 (3)
C3—C111.547 (3)C21—O531.438 (3)
C4—S441.864 (2)C28—O511.374 (3)
S44—C451.813 (3)O34—C331.429 (4)
C7—O341.383 (4)C33—O321.424 (4)
C8—O321.383 (3)C37—O391.197 (4)
C11—N121.480 (3)O41—C421.434 (4)
N12—C131.473 (3)C46—O471.197 (3)
C13—C211.515 (4)O51—C521.419 (4)
N2—C1—C49109.4 (2)N2—C3—C11114.03 (19)
C21—N2—C3113.63 (19)N12—C11—C19110.2 (2)
C21—N2—C1109.66 (19)N12—C11—C3107.80 (19)
C3—N2—C1113.76 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O40—H40···O90i0.841.962.687 (3)145
O50—H50···O80ii0.841.842.676 (3)177
O80—H80···N230.841.992.793 (3)161
O90—H90···O53iii0.841.962.783 (4)167
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1/2, z+1/2; (iii) x1/2, y+3/2, z.
 

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