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The absolute configuration has been determined for the title compound, C21H27NO9S2·C7H8. The compound is a precurser in the synthesis of bicyclic dipeptide isosteres based on mannuronic acid. The seven-membered lactam ring adopts a rigid chair conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680503031X/is6126sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680503031X/is6126Isup2.hkl
Contains datablock I

CCDC reference: 287612

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.027
  • wR factor = 0.049
  • Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.88 Ratio PLAT231_ALERT_4_B Hirshfeld Test (Solvent) C30 - C36 .. 10.00 su
Alert level C PLAT231_ALERT_4_C Hirshfeld Test (Solvent) C30 - C31 .. 6.60 su PLAT231_ALERT_4_C Hirshfeld Test (Solvent) C30 - C35 .. 5.05 su PLAT231_ALERT_4_C Hirshfeld Test (Solvent) C33 - C34 .. 7.03 su
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.97 From the CIF: _reflns_number_total 5724 Count of symmetry unique reflns 3269 Completeness (_total/calc) 175.10% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2455 Fraction of Friedel pairs measured 0.751 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Bicyclic dipeptide mimetics can induce and stabilize hairpin turns in peptide strands (Nagai & Sato, 1985). The originally proposed mechanism has been challenged by recent X-ray and NMR studies (Tremmel & Geyer, 2004). Polyhydroxylated 7,5-fused bicyclic thiazolidinlactams have been inserted into both cyclic and linear oligopeptids (Tremmel & Geyer, 2002). The present ester molecule of the title compound, (I), is a precurser for a class of carbohydrate-based dipeptide derivatives. The mesyl group can be exchanged for an azido group and subsequent reduction forms the amino group of the dipeptide mimetic. After cleavage of the isopropylidene and methylester protecting groups, a hydrophilic bicyclic dipeptide mimetic with an aromatic side chain is obtained. It can serve as a rigid substituent of a D-Phe-Pro dipeptide.

The starting reaction for the synthesis of the mesylated 7,5-fused bicyclic thiazolidinlactam, (I) (Fig. 1), is the condensation of D-γ-mannuronolactone with the methyl ester of L-cysteine. After protection of two hydroxy groups with 2,2-dimethoxypropane, the alcohol in position 9 is selectively activated with mesylchloride. Finally, the benzylation of the remaining free hydroxyl group is performed with benzylbromide and sodium hydride.

In both the crystalline state and in solution the seven-membered lactam ring of (I) populates an inverted chair conformation, compared with the gluco derivatives (Geyer et al., 1999).

Experimental top

The title compound was prepared from (3aS,4S,4aS,7R,9S,9aS)-4-hydroxy-9-methanesulfonyloxy-2,2-dimethyl-8-oxo-octahydro-1,3-dioxa-5-thia-7a-azacyclopenta[f]azulene-7-carboxylic acid methyl ester (1.33 g, 3.25 mmol) by treatment with benzylbromide (1.67 g, 9.75 mmol), sodium hydride (0.12 g, 4.88 mmol) and tetrabutylammonium iodide (20 mg, 0.05 mmol) in dimethylformamide (70 ml) for 3 h at room temperature. Water (200 ml) was added and the reaction mixture was extracted twice with toluene. After removal of the organic solvent, the desired product was purified by flash chromatography. Colourless crystals of (I) were obtained by recrystallization from ethyl acetate (yield: 1.06 g, 2.11 mmol, 65%). Spectroscopic analysis: 1H NMR (500 MHz, DMSO-d6, δ, p.p.m.): 7.38–7.28 (m, 5 H, Ph), 5.30 (s, 1 H, 9a-H), 5.27 (s, 1 H, 6-H), 5.06 (d, 3J3-H,2'-H = 6.80 Hz, 1 H, 3-H), 4.90 (d, 2JBn = 11.21 Hz, 1 H, Ph—CH2), 4.73 (d, 2JBn = 11.21 Hz, 1 H, Ph—CH2), 4.30 (d, 3J9-H,8-H = 2.24 Hz, 1 H, 9-H), 4.26 (dd, 3J8-H,7-H = 9.45 Hz, 3J8-H,9-H = 2.24 Hz, 1 H, 8-H), 4.15 (dd, 3J7-H,8-H = 9.45 Hz, 3J7-H,6-H = 1 Hz, 1 H, 7-H), 3.64 (s, 3 H, OCH3), 3.37 (dd, 2J2'-H,2-H = 11.76 Hz, 3J2'-H,3-H = 7.00 Hz, 1 H, 2'-H), 3.29 (s, 3 H, SCH3), 3.09 (d, 2J2-H,2'-H = 11.76 Hz, 1 H, 2-H), 1.39 (ps, 6 H, CH3). 13C NMR (125 MHz, DMSO-d6, δ, p.p.m.): 169.24, 163.02 (CO), 137.93, 128.30, 127.82, 127.71 (Ph), 108.61 (CqIsopr), 80.51 (9-C), 78.10 (6-C), 76.23 (8-C), 75.11 (CH2—Ph), 70.47 (7-C), 65.63 (3-C), 60.84 (9a-C), 52.43 (OCH3), 38.59 (SCH3), 30.47 (2-C), 26.33, 26.24 (CH3Isopr).

Refinement top

Methyl groups and solvent aromatic H atoms were refined with idealized geometry [for Me H, C—H = 0.98 Å, H—C—H = 109.5° and Uiso(H) = 1.5Ueq(C), with torsion angles from the electron density; for solvent CH, C—H = 0.98 Å, H on the external bisector, Uiso(H) = 1.2Ueq(C)]. All other H atoms were located and refined isotropically. The bond length range is 0.87 (2)–1.07 (2) Å. The absolute structure was determined via the refinement of an inversion twin.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I), with 50% probability displacement ellipsoids.
(3aS,4S,4aS,7R,9S,9aS)-Methyl 4-benzyloxy-9-methanesulfonyloxy-2,2-dimethyl-8-oxo- octahydro-1,3-dioxa-5-thia-7a-aza-cyclopenta[f]azulene-7-carboxylate toluene solvate top
Crystal data top
C21H27NO9S2·C7H8F(000) = 1256
Mr = 593.69Dx = 1.339 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 21120 reflections
a = 10.1251 (6) Åθ = 1.6–26.2°
b = 11.4082 (5) ŵ = 0.23 mm1
c = 25.4972 (15) ÅT = 193 K
V = 2945.2 (3) Å3Plate, colourless
Z = 40.4 × 0.4 × 0.05 mm
Data collection top
Stoe IPDS 2
diffractometer
Rint = 0.037
ω scansθmax = 26.0°, θmin = 1.6°
29561 measured reflectionsh = 1212
5724 independent reflectionsk = 1414
4668 reflections with I > 2σ(I)l = 3131
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0245P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.027(Δ/σ)max = 0.001
wR(F2) = 0.049Δρmax = 0.14 e Å3
S = 0.89Δρmin = 0.18 e Å3
5724 reflectionsAbsolute structure: Flack (1983), with 2479 Friedel pairs
426 parametersAbsolute structure parameter: 0.02 (4)
0 restraints
Crystal data top
C21H27NO9S2·C7H8V = 2945.2 (3) Å3
Mr = 593.69Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.1251 (6) ŵ = 0.23 mm1
b = 11.4082 (5) ÅT = 193 K
c = 25.4972 (15) Å0.4 × 0.4 × 0.05 mm
Data collection top
Stoe IPDS 2
diffractometer
4668 reflections with I > 2σ(I)
29561 measured reflectionsRint = 0.037
5724 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049Δρmax = 0.14 e Å3
S = 0.89Δρmin = 0.18 e Å3
5724 reflectionsAbsolute structure: Flack (1983), with 2479 Friedel pairs
426 parametersAbsolute structure parameter: 0.02 (4)
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
C20.85020 (18)0.77782 (18)0.95213 (7)0.0327 (4)
C30.77303 (18)0.81284 (15)1.00038 (6)0.0284 (4)
C50.66584 (16)0.99122 (15)1.02784 (6)0.0274 (4)
C60.65173 (15)1.12417 (16)1.03027 (6)0.0257 (4)
C70.65328 (16)1.18138 (15)0.97693 (7)0.0258 (4)
C80.78920 (15)1.19366 (14)0.95286 (7)0.0260 (4)
C90.84404 (15)1.08227 (14)0.92964 (6)0.0240 (4)
C9A0.87964 (15)0.99958 (15)0.97450 (7)0.0254 (4)
C100.84174 (16)0.77455 (16)1.05094 (7)0.0309 (4)
C110.9268 (2)0.6090 (2)1.09615 (8)0.0554 (6)
H11A1.0210.62781.09370.083*
H11B0.91520.52371.09610.083*
H11C0.89080.64171.12870.083*
C120.7384 (2)1.07822 (18)1.15471 (7)0.0494 (5)
H12A0.82651.0441.15010.074*
H12B0.67171.02421.14080.074*
H12C0.7221.09171.19210.074*
C130.68236 (15)1.36643 (16)0.94038 (6)0.0310 (4)
C140.59257 (19)1.41538 (19)0.89905 (8)0.0451 (5)
H14A0.64541.45450.8720.068*
H14B0.5321.47210.9150.068*
H14C0.54171.35160.88310.068*
C150.76028 (19)1.45711 (16)0.96994 (8)0.0481 (5)
H15A0.81271.41870.99730.072*
H15B0.69961.51350.98610.072*
H15C0.81931.49830.94570.072*
C160.7629 (2)1.0592 (2)0.84192 (7)0.0407 (5)
C170.67606 (17)0.97882 (16)0.81073 (6)0.0317 (4)
C180.7155 (2)0.86566 (19)0.79949 (7)0.0438 (5)
C190.6336 (2)0.7906 (2)0.77242 (9)0.0529 (6)
C200.5112 (2)0.8287 (2)0.75569 (8)0.0500 (6)
C210.4712 (2)0.9403 (2)0.76620 (8)0.0490 (5)
C220.5527 (2)1.0145 (2)0.79395 (8)0.0420 (5)
C300.89040 (19)0.4904 (2)0.78038 (9)0.0551 (6)
C310.8776 (2)0.3675 (2)0.78532 (10)0.0592 (7)
H310.87730.33250.81910.071*
C320.8657 (2)0.2987 (3)0.74165 (11)0.0697 (7)
H320.85810.21620.74570.084*
C330.8646 (2)0.3454 (3)0.69237 (11)0.0694 (7)
H330.85590.29650.66240.083*
C340.8763 (2)0.4653 (2)0.68713 (10)0.0573 (6)
H340.87530.49870.6530.069*
C350.88932 (19)0.5379 (2)0.72985 (9)0.0522 (6)
H350.89760.62020.7250.063*
C360.9004 (3)0.5663 (3)0.82670 (10)0.0774 (8)
H36A0.96710.62690.82050.116*
H36B0.9260.51920.85720.116*
H36C0.81470.60340.83340.116*
N40.76355 (12)0.94071 (11)0.99905 (5)0.0260 (3)
O10.85730 (13)0.65943 (11)1.05137 (5)0.0436 (3)
O20.87554 (15)0.83954 (12)1.08513 (6)0.0547 (4)
O30.58434 (11)0.93119 (11)1.05154 (5)0.0393 (3)
O40.75838 (11)1.17361 (9)1.06204 (4)0.0297 (3)
O50.83811 (13)1.28422 (13)1.13417 (5)0.0481 (3)
O60.59851 (13)1.25617 (13)1.12440 (5)0.0504 (4)
O70.76835 (11)1.28370 (10)0.91533 (4)0.0297 (2)
O80.60683 (10)1.29935 (11)0.97846 (4)0.0311 (3)
O90.75513 (10)1.02311 (10)0.89575 (4)0.0276 (3)
S10.98560 (4)0.88067 (4)0.951666 (19)0.03503 (11)
S20.72970 (4)1.21124 (4)1.120997 (17)0.03626 (11)
H2A0.7945 (15)0.7885 (15)0.9224 (6)0.029 (4)*
H2B0.8819 (15)0.7044 (16)0.9560 (6)0.025 (4)*
H30.6866 (15)0.7838 (15)1.0003 (6)0.021 (4)*
H60.5732 (15)1.1390 (13)1.0478 (6)0.019 (4)*
H70.5990 (14)1.1384 (14)0.9551 (6)0.018 (4)*
H80.8501 (15)1.2212 (14)0.9781 (6)0.017 (4)*
H90.9279 (15)1.1005 (14)0.9112 (6)0.019 (4)*
H9A0.9303 (14)1.0440 (15)1.0018 (6)0.026 (4)*
H16A0.725 (2)1.146 (2)0.8388 (8)0.069 (7)*
H16B0.8536 (19)1.0503 (17)0.8334 (8)0.044 (6)*
H180.800 (2)0.8411 (18)0.8093 (8)0.053 (6)*
H190.6686 (19)0.715 (2)0.7642 (7)0.052 (6)*
H200.455 (2)0.778 (2)0.7372 (9)0.064 (7)*
H210.385 (2)0.968 (2)0.7547 (9)0.071 (7)*
H220.528 (2)1.086 (2)0.8011 (8)0.057 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0404 (10)0.0255 (11)0.0323 (9)0.0045 (9)0.0041 (8)0.0002 (9)
C30.0296 (8)0.0215 (10)0.0341 (9)0.0030 (8)0.0027 (7)0.0001 (7)
C50.0258 (8)0.0293 (10)0.0272 (9)0.0032 (8)0.0021 (7)0.0003 (8)
C60.0204 (8)0.0283 (10)0.0286 (9)0.0035 (8)0.0015 (7)0.0031 (8)
C70.0246 (8)0.0227 (10)0.0301 (9)0.0004 (7)0.0012 (7)0.0027 (8)
C80.0258 (8)0.0256 (10)0.0266 (8)0.0010 (7)0.0004 (7)0.0017 (8)
C90.0225 (8)0.0224 (9)0.0271 (8)0.0031 (7)0.0016 (7)0.0003 (7)
C9A0.0215 (8)0.0253 (10)0.0294 (9)0.0012 (7)0.0021 (7)0.0021 (8)
C100.0356 (9)0.0247 (10)0.0325 (9)0.0024 (8)0.0010 (8)0.0024 (9)
C110.0754 (15)0.0443 (14)0.0466 (12)0.0169 (12)0.0140 (10)0.0123 (11)
C120.0553 (12)0.0556 (14)0.0374 (11)0.0044 (11)0.0028 (10)0.0076 (9)
C130.0302 (8)0.0251 (10)0.0376 (10)0.0032 (7)0.0075 (7)0.0014 (8)
C140.0425 (11)0.0447 (13)0.0481 (12)0.0128 (9)0.0087 (9)0.0117 (10)
C150.0455 (11)0.0334 (11)0.0655 (13)0.0043 (9)0.0129 (10)0.0141 (10)
C160.0495 (13)0.0443 (13)0.0283 (9)0.0111 (11)0.0000 (9)0.0042 (8)
C170.0410 (10)0.0329 (11)0.0212 (8)0.0040 (8)0.0017 (8)0.0022 (8)
C180.0429 (11)0.0482 (14)0.0402 (11)0.0094 (10)0.0042 (9)0.0076 (10)
C190.0631 (14)0.0418 (14)0.0539 (13)0.0080 (12)0.0017 (11)0.0179 (12)
C200.0483 (13)0.0577 (15)0.0442 (12)0.0108 (12)0.0051 (10)0.0133 (11)
C210.0393 (11)0.0589 (16)0.0487 (13)0.0010 (11)0.0054 (10)0.0015 (11)
C220.0522 (13)0.0354 (13)0.0384 (11)0.0061 (10)0.0041 (9)0.0015 (10)
C300.0312 (10)0.084 (2)0.0502 (14)0.0045 (11)0.0037 (10)0.0075 (13)
C310.0446 (12)0.0732 (19)0.0598 (15)0.0114 (12)0.0050 (10)0.0339 (14)
C320.0611 (15)0.0672 (18)0.0808 (19)0.0167 (14)0.0144 (13)0.0118 (16)
C330.0625 (15)0.079 (2)0.0672 (17)0.0171 (13)0.0114 (12)0.0105 (14)
C340.0505 (13)0.0657 (18)0.0556 (15)0.0074 (11)0.0090 (11)0.0172 (13)
C350.0397 (11)0.0627 (16)0.0541 (14)0.0029 (11)0.0042 (10)0.0218 (12)
C360.0655 (16)0.097 (2)0.0693 (17)0.0131 (16)0.0042 (13)0.0162 (16)
N40.0267 (7)0.0220 (8)0.0292 (7)0.0008 (6)0.0012 (6)0.0021 (6)
O10.0628 (8)0.0268 (7)0.0413 (7)0.0081 (6)0.0141 (7)0.0042 (6)
O20.0842 (11)0.0358 (9)0.0442 (8)0.0022 (7)0.0251 (8)0.0029 (7)
O30.0376 (6)0.0324 (7)0.0480 (8)0.0086 (6)0.0133 (6)0.0015 (6)
O40.0289 (6)0.0320 (6)0.0284 (6)0.0012 (5)0.0007 (5)0.0053 (5)
O50.0570 (8)0.0433 (9)0.0440 (8)0.0089 (7)0.0095 (7)0.0127 (7)
O60.0472 (8)0.0609 (10)0.0431 (8)0.0171 (7)0.0035 (7)0.0149 (7)
O70.0332 (6)0.0215 (6)0.0342 (6)0.0035 (6)0.0054 (5)0.0033 (5)
O80.0295 (6)0.0251 (7)0.0386 (7)0.0039 (5)0.0069 (5)0.0008 (6)
O90.0306 (6)0.0287 (6)0.0236 (5)0.0037 (5)0.0010 (5)0.0005 (5)
S10.0315 (2)0.0287 (2)0.0449 (3)0.0069 (2)0.0058 (2)0.0030 (2)
S20.0406 (2)0.0381 (3)0.0300 (2)0.0029 (2)0.0011 (2)0.0076 (2)
Geometric parameters (Å, º) top
C2—C31.511 (2)C14—H14A0.98
C2—S11.8046 (19)C14—H14B0.98
C2—H2A0.953 (16)C14—H14C0.98
C2—H2B0.902 (18)C15—H15A0.98
C3—N41.462 (2)C15—H15B0.98
C3—C101.529 (2)C15—H15C0.98
C3—H30.936 (16)C16—O91.435 (2)
C5—O31.2309 (19)C16—C171.499 (3)
C5—N41.360 (2)C16—H16A1.07 (2)
C5—C61.525 (2)C16—H16B0.949 (19)
C6—O41.4629 (18)C17—C181.381 (3)
C6—C71.509 (2)C17—C221.382 (3)
C6—H60.928 (15)C18—C191.377 (3)
C7—O81.426 (2)C18—H180.93 (2)
C7—C81.513 (2)C19—C201.381 (3)
C7—H70.923 (16)C19—H190.96 (2)
C8—O71.4195 (19)C20—C211.362 (3)
C8—C91.508 (2)C20—H200.93 (2)
C8—H80.946 (16)C21—C221.378 (3)
C9—O91.4187 (18)C21—H210.98 (2)
C9—C9A1.526 (2)C22—H220.87 (2)
C9—H90.992 (16)C30—C351.398 (3)
C9A—N41.491 (2)C30—C311.413 (3)
C9A—S11.8249 (17)C30—C361.468 (4)
C9A—H9A1.002 (17)C31—C321.368 (4)
C10—O21.194 (2)C31—H310.95
C10—O11.323 (2)C32—C331.365 (3)
C11—O11.459 (2)C32—H320.95
C11—H11A0.98C33—C341.380 (3)
C11—H11B0.98C33—H330.95
C11—H11C0.98C34—C351.375 (3)
C12—S21.746 (2)C34—H340.95
C12—H12A0.98C35—H350.95
C12—H12B0.98C36—H36A0.98
C12—H12C0.98C36—H36B0.98
C13—O71.434 (2)C36—H36C0.98
C13—O81.4537 (19)O4—S21.5902 (11)
C13—C141.500 (2)O5—S21.4180 (14)
C13—C151.504 (2)O6—S21.4265 (13)
C3—C2—S1103.08 (12)H14B—C14—H14C109.5
C3—C2—H2A107.9 (10)C13—C15—H15A109.5
S1—C2—H2A111.2 (10)C13—C15—H15B109.5
C3—C2—H2B109.9 (10)H15A—C15—H15B109.5
S1—C2—H2B109.5 (10)C13—C15—H15C109.5
H2A—C2—H2B114.6 (15)H15A—C15—H15C109.5
N4—C3—C2106.19 (14)H15B—C15—H15C109.5
N4—C3—C10109.55 (14)O9—C16—C17107.45 (15)
C2—C3—C10112.07 (14)O9—C16—H16A108.5 (12)
N4—C3—H3106.9 (10)C17—C16—H16A108.4 (12)
C2—C3—H3112.9 (10)O9—C16—H16B103.9 (12)
C10—C3—H3109.0 (10)C17—C16—H16B112.4 (12)
O3—C5—N4121.13 (15)H16A—C16—H16B115.8 (18)
O3—C5—C6118.07 (15)C18—C17—C22118.20 (18)
N4—C5—C6120.77 (14)C18—C17—C16120.85 (18)
O4—C6—C7108.94 (13)C22—C17—C16120.92 (19)
O4—C6—C5109.68 (13)C19—C18—C17120.7 (2)
C7—C6—C5113.13 (14)C19—C18—H18120.0 (13)
O4—C6—H6107.2 (9)C17—C18—H18119.3 (13)
C7—C6—H6111.4 (9)C18—C19—C20120.0 (2)
C5—C6—H6106.3 (10)C18—C19—H19116.6 (12)
O8—C7—C6112.34 (14)C20—C19—H19123.3 (12)
O8—C7—C8102.92 (13)C21—C20—C19120.0 (2)
C6—C7—C8114.53 (14)C21—C20—H20119.6 (14)
O8—C7—H7108.8 (9)C19—C20—H20120.4 (14)
C6—C7—H7107.9 (10)C20—C21—C22119.9 (2)
C8—C7—H7110.3 (9)C20—C21—H21120.6 (15)
O7—C8—C9113.58 (13)C22—C21—H21119.5 (15)
O7—C8—C7101.84 (12)C21—C22—C17121.2 (2)
C9—C8—C7114.59 (14)C21—C22—H22120.5 (14)
O7—C8—H8108.4 (10)C17—C22—H22118.2 (14)
C9—C8—H8107.9 (10)C35—C30—C31117.8 (2)
C7—C8—H8110.3 (9)C35—C30—C36120.9 (2)
O9—C9—C8113.98 (13)C31—C30—C36121.3 (2)
O9—C9—C9A108.20 (13)C32—C31—C30120.3 (2)
C8—C9—C9A108.29 (13)C32—C31—H31119.8
O9—C9—H9110.8 (9)C30—C31—H31119.8
C8—C9—H9108.9 (10)C33—C32—C31121.8 (3)
C9A—C9—H9106.4 (9)C33—C32—H32119.1
N4—C9A—C9114.01 (12)C31—C32—H32119.1
N4—C9A—S1105.22 (11)C32—C33—C34118.4 (3)
C9—C9A—S1111.06 (11)C32—C33—H33120.8
N4—C9A—H9A109.9 (9)C34—C33—H33120.8
C9—C9A—H9A109.2 (10)C35—C34—C33121.9 (2)
S1—C9A—H9A107.2 (9)C35—C34—H34119
O2—C10—O1125.18 (17)C33—C34—H34119
O2—C10—C3124.65 (16)C34—C35—C30119.8 (2)
O1—C10—C3110.18 (15)C34—C35—H35120.1
O1—C11—H11A109.5C30—C35—H35120.1
O1—C11—H11B109.5C30—C36—H36A109.5
H11A—C11—H11B109.5C30—C36—H36B109.5
O1—C11—H11C109.5H36A—C36—H36B109.5
H11A—C11—H11C109.5C30—C36—H36C109.5
H11B—C11—H11C109.5H36A—C36—H36C109.5
S2—C12—H12A109.5H36B—C36—H36C109.5
S2—C12—H12B109.5C5—N4—C3117.25 (14)
H12A—C12—H12B109.5C5—N4—C9A127.52 (14)
S2—C12—H12C109.5C3—N4—C9A114.03 (13)
H12A—C12—H12C109.5C10—O1—C11117.07 (16)
H12B—C12—H12C109.5C6—O4—S2119.52 (10)
O7—C13—O8105.69 (13)C8—O7—C13105.45 (11)
O7—C13—C14107.47 (14)C7—O8—C13107.76 (12)
O8—C13—C14110.27 (13)C9—O9—C16114.29 (13)
O7—C13—C15110.95 (13)C2—S1—C9A91.98 (8)
O8—C13—C15107.65 (14)O5—S2—O6119.70 (9)
C14—C13—C15114.47 (17)O5—S2—O4103.95 (7)
C13—C14—H14A109.5O6—S2—O4108.94 (7)
C13—C14—H14B109.5O5—S2—C12110.77 (10)
H14A—C14—H14B109.5O6—S2—C12109.23 (10)
C13—C14—H14C109.5O4—S2—C12102.80 (8)
H14A—C14—H14C109.5
S1—C2—C3—N444.96 (15)C32—C33—C34—C350.2 (4)
S1—C2—C3—C1074.62 (16)C33—C34—C35—C300.3 (3)
O3—C5—C6—O4109.63 (16)C31—C30—C35—C340.1 (3)
N4—C5—C6—O472.22 (18)C36—C30—C35—C34178.2 (2)
O3—C5—C6—C7128.53 (16)O3—C5—N4—C34.1 (2)
N4—C5—C6—C749.6 (2)C6—C5—N4—C3177.82 (14)
O4—C6—C7—O872.79 (16)O3—C5—N4—C9A170.73 (15)
C5—C6—C7—O8164.96 (13)C6—C5—N4—C9A11.2 (2)
O4—C6—C7—C844.17 (19)C2—C3—N4—C5159.54 (14)
C5—C6—C7—C878.08 (18)C10—C3—N4—C579.24 (18)
O8—C7—C8—O737.25 (15)C2—C3—N4—C9A32.03 (18)
C6—C7—C8—O7159.49 (14)C10—C3—N4—C9A89.18 (16)
O8—C7—C8—C9160.31 (14)C9—C9A—N4—C567.5 (2)
C6—C7—C8—C977.46 (18)S1—C9A—N4—C5170.54 (13)
O7—C8—C9—O967.30 (17)C9—C9A—N4—C3125.47 (15)
C7—C8—C9—O949.18 (18)S1—C9A—N4—C33.54 (16)
O7—C8—C9—C9A172.24 (13)O2—C10—O1—C113.0 (3)
C7—C8—C9—C9A71.28 (17)C3—C10—O1—C11177.43 (15)
O9—C9—C9A—N447.55 (17)C7—C6—O4—S2134.56 (12)
C8—C9—C9A—N476.45 (17)C5—C6—O4—S2101.13 (13)
O9—C9—C9A—S171.10 (14)C9—C8—O7—C13163.38 (13)
C8—C9—C9A—S1164.90 (11)C7—C8—O7—C1339.64 (15)
N4—C3—C10—O23.7 (2)O8—C13—O7—C827.26 (15)
C2—C3—C10—O2121.3 (2)C14—C13—O7—C8145.01 (14)
N4—C3—C10—O1176.67 (14)C15—C13—O7—C889.15 (16)
C2—C3—C10—O159.08 (19)C6—C7—O8—C13144.76 (13)
O9—C16—C17—C1875.3 (2)C8—C7—O8—C1321.06 (16)
O9—C16—C17—C22102.5 (2)O7—C13—O8—C72.65 (16)
C22—C17—C18—C190.2 (3)C14—C13—O8—C7118.51 (15)
C16—C17—C18—C19177.69 (18)C15—C13—O8—C7115.97 (15)
C17—C18—C19—C200.7 (3)C8—C9—O9—C1689.06 (17)
C18—C19—C20—C210.3 (3)C9A—C9—O9—C16150.42 (15)
C19—C20—C21—C220.6 (3)C17—C16—O9—C9173.04 (15)
C20—C21—C22—C171.2 (3)C3—C2—S1—C9A37.91 (13)
C18—C17—C22—C210.8 (3)N4—C9A—S1—C220.48 (12)
C16—C17—C22—C21178.62 (18)C9—C9A—S1—C2103.33 (12)
C35—C30—C31—C320.5 (3)C6—O4—S2—O5163.57 (12)
C36—C30—C31—C32178.6 (2)C6—O4—S2—O634.90 (14)
C30—C31—C32—C330.6 (3)C6—O4—S2—C1280.89 (13)
C31—C32—C33—C340.2 (4)

Experimental details

Crystal data
Chemical formulaC21H27NO9S2·C7H8
Mr593.69
Crystal system, space groupOrthorhombic, P212121
Temperature (K)193
a, b, c (Å)10.1251 (6), 11.4082 (5), 25.4972 (15)
V3)2945.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.4 × 0.4 × 0.05
Data collection
DiffractometerStoe IPDS 2
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
29561, 5724, 4668
Rint0.037
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.049, 0.89
No. of reflections5724
No. of parameters426
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.18
Absolute structureFlack (1983), with 2479 Friedel pairs
Absolute structure parameter0.02 (4)

Computer programs: X-AREA (Stoe & Cie, 2005), X-AREA, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2004), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
C2—C31.511 (2)C7—C81.513 (2)
C2—S11.8046 (19)C8—O71.4195 (19)
C3—N41.462 (2)C8—C91.508 (2)
C5—N41.360 (2)C9—C9A1.526 (2)
C5—C61.525 (2)C9A—N41.491 (2)
C6—C71.509 (2)C9A—S11.8249 (17)
C7—O81.426 (2)
C3—C2—S1103.08 (12)N4—C9A—C9114.01 (12)
N4—C3—C2106.19 (14)N4—C9A—S1105.22 (11)
N4—C5—C6120.77 (14)C9—C9A—S1111.06 (11)
C7—C6—C5113.13 (14)O7—C13—O8105.69 (13)
O8—C7—C6112.34 (14)C5—N4—C3117.25 (14)
O8—C7—C8102.92 (13)C5—N4—C9A127.52 (14)
C6—C7—C8114.53 (14)C3—N4—C9A114.03 (13)
O7—C8—C9113.58 (13)C8—O7—C13105.45 (11)
O7—C8—C7101.84 (12)C7—O8—C13107.76 (12)
C9—C8—C7114.59 (14)C2—S1—C9A91.98 (8)
C8—C9—C9A108.29 (13)
S1—C2—C3—N444.96 (15)C2—C3—N4—C5159.54 (14)
N4—C5—C6—C749.6 (2)C2—C3—N4—C9A32.03 (18)
C5—C6—C7—O8164.96 (13)C9—C9A—N4—C567.5 (2)
C5—C6—C7—C878.08 (18)S1—C9A—N4—C5170.54 (13)
O8—C7—C8—O737.25 (15)C9—C9A—N4—C3125.47 (15)
C6—C7—C8—O7159.49 (14)S1—C9A—N4—C33.54 (16)
O8—C7—C8—C9160.31 (14)C9—C8—O7—C13163.38 (13)
C6—C7—C8—C977.46 (18)C7—C8—O7—C1339.64 (15)
O7—C8—C9—O967.30 (17)O8—C13—O7—C827.26 (15)
O7—C8—C9—C9A172.24 (13)C6—C7—O8—C13144.76 (13)
C7—C8—C9—C9A71.28 (17)C8—C7—O8—C1321.06 (16)
C8—C9—C9A—N476.45 (17)O7—C13—O8—C72.65 (16)
C8—C9—C9A—S1164.90 (11)C3—C2—S1—C9A37.91 (13)
C6—C5—N4—C3177.82 (14)N4—C9A—S1—C220.48 (12)
C6—C5—N4—C9A11.2 (2)C9—C9A—S1—C2103.33 (12)
 

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