Ethyl 4,6-O-benzyl­idene-2-de­oxy-N-phthalimido-1-thio-β-d-glucopyran­oside

Hamark, C.; Landström, J.; Eriksson, L.; Widmalm, G.

doi:10.1107/S1600536810047070

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3249

https://doi.org/10.1107/S1600536810047070

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Ethyl 4,6-O-benzylidene-2-deoxy-N-phthalimido-1-thio-β-D-glucopyranoside

Christoffer Hamark,^a Jens Landström,^a Lars Eriksson ^b ^* and Göran Widmalm ^a

^aDepartment of Organic Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden, and ^bDepartment of Environmental and Material Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden
^*Correspondence e-mail: lars.eriksson@mmk.su.se

(Received 10 October 2010; accepted 13 November 2010; online 20 November 2010)

In the title compound, C₂₃H₂₃NO₆S, the plane of the N-phthalimido group makes a dihedral angle of 67.4 (1)° with the least square plane of the sugar ring defined by the C2, C3, C5 and O5 atoms using standard glucose nomenclature. The thioethyl group has the exo-anomeric conformation. In the crystal, intermolecular hydrogen bonds involving the hydroxy groups and the carbonyl O atoms of adjacent N-phthalimido groups form chains parallel to the b axis. The chains are further stabilized by C—H⋯π interactions.

Related literature

For the chemistry and applications of N-acetyl-β-D-glucosamine derivatives, see: Tan et al. (2009 ); Werz et al. (2007 ). For the conformation of related compounds, see: Lemieux & Koto (1974 ); Färnbäck et al. (2007 ). For the synthesis of the title compound, see: Lönn (1985 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₃H₂₃NO₆S
M_r = 441.48
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.6728 (6) Å
b = 9.7583 (10) Å
c = 25.3102 (15) Å
V = 2142.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 293 K
0.30 × 0.12 × 0.05 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) T_min = 0.730, T_max = 0.933
12985 measured reflections
5120 independent reflections
2352 reflections with I > 2σ(I)
R_int = 0.110

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.110
S = 0.83
5120 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 1544 Friedel pairs
Flack parameter: −0.07 (10)

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C23—C28 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O30ⁱ	0.82	2.27	3.014 (3)	150
C14—H14⋯Cgⁱ	0.93	2.98	3.613 (3)	126
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: EXPOSE (Stoe & Cie, 1997); cell refinement: CELL (Stoe & Cie, 1997); data reduction: INTEGRATE (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810047070/rz2504sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047070/rz2504Isup2.hkl

checkCIF report

Comment top

N-acetyl-D-glucosamine (D-GlcNAc) is found in nature in bacteria, crustaceans as well as in mammals. In glycoproteins the β-D-GlcNAc is present in N-linked oligosaccharides and it is of great importance to have access to a large arsenal of different suitably protected synthetic precursors in order to carry out synthesis of a variety of different oligosaccharides (Werz et al. 2007). These can be used as probes in microarray applications or to synthesize N-linked glycoproteins (Tan et al. 2009). In the structure shown in Fig. 1 the least square plane of the N-phthaloyl group makes a dihedral angle of 67.4 (1)° to the sugar ring plane defined by the four atoms (C2,C3,C5,O5).

In glycosides the φ torsion angle (H1—C1—S1—C7) is of particular interest and is for the title compound in agreement with the exo-anomeric effect (Lemieux & Koto, 1974). It is, however sligthly shifted away from a staggered conformation, to 25.4°. The Cremer & Pople (1975) parameters for the different rings are for (O5—C5): Q=0.585 (3) Å, θ=8.4 (3)° and φ=329 (2)°, for (O4,C4,C5,C6,O6,C9): Q=0.575 (3) Å, θ=3.4 (3)° and φ=126 (4)°. These Q-values are similar to total puckering amplitudes for previously described pyranosides (Färnbäck et al., 2007).

Intermolecular hydrogen bonding from the hydroxy group is present (Table 1) where one of the carbonyl O atoms in the N-phthaloyl group act as acceptor, making up chains along the [010] direction shown in Fig. 2. In addition to this conventional hydrogen bond the intermolecular packing is stabilized due to interactions between substituents of the sugar rings. There is a salient C—H···π interaction between the center of gravity (Cg) of the ring C23—C28 of the N-phthaloyl group and the meta position (C14) of the phenyl group (C10—C15). Furthermore there are three more π···π interactions present with d(Cg—Cg) < 4.8 Å with dihedral angles between the interacting π systems in the vicinity of 60° indicating a herringbone packing pattern.

Related literature top

For the chemistry and applications of N-acetyl-β-D-glucosamine derivatives, see: Tan et al. (2009); Werz et al. (2007). For the conformation of related compounds, see: Lemieux & Koto (1974); Färnbäck et al. (2007). For the synthesis of the title compound, see: Lönn (1985). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

The synthesis of the title compound has been described previously (Lönn, 1985). Colourless crystals of the title compound were grown from diethyl ether/pentane (1:1 v/v) at ambient temperature.

Structure description top

For the chemistry and applications of N-acetyl-β-D-glucosamine derivatives, see: Tan et al. (2009); Werz et al. (2007). For the conformation of related compounds, see: Lemieux & Koto (1974); Färnbäck et al. (2007). For the synthesis of the title compound, see: Lönn (1985). For puckering parameters, see: Cremer & Pople (1975).

Computing details top

Data collection: EXPOSE (Stoe & Cie, 1997); cell refinement: CELL (Stoe & Cie, 1997); data reduction: INTEGRATE (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure showing 50% probability displacement ellipsoids.
	Fig. 2. Stereoview showing the intermolecular hydrogen bond intercations between molecules forming a chain along the b-direction.

ethyl 4,6-O-benzylidene-2-deoxy-N-(1,3-dioxo-2,3-dihydro- 1H-isoindol-2-yl)-1-thio-β-D-glucopyranoside top

Crystal data top

C₂₃H₂₃NO₆S	F(000) = 928
M_r = 441.48	D_x = 1.369 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5000 reflections
a = 8.6728 (6) Å	θ = 2.4–23.3°
b = 9.7583 (10) Å	µ = 0.19 mm⁻¹
c = 25.3102 (15) Å	T = 293 K
V = 2142.0 (3) Å³	Prism, colourless
Z = 4	0.30 × 0.12 × 0.05 mm

Data collection top

Stoe IPDS diffractometer	3734 independent reflections
Radiation source: fine-focus sealed tube	2352 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.110
Detector resolution: 6.7 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
φ scan	h = −10→10
Absorption correction: numerical (X-RED; Stoe & Cie, 1997)	k = −11→11
T_min = 0.730, T_max = 0.933	l = −29→29
5120 measured reflections

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0371P)²] where P = (F_o² + 2F_c²)/3
S = 0.83	(Δ/σ)_max < 0.001
5120 reflections	Δρ_max = 0.21 e Å⁻³
281 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1544 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (10)

Crystal data top

C₂₃H₂₃NO₆S	V = 2142.0 (3) Å³
M_r = 441.48	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.6728 (6) Å	µ = 0.19 mm⁻¹
b = 9.7583 (10) Å	T = 293 K
c = 25.3102 (15) Å	0.30 × 0.12 × 0.05 mm

Data collection top

Stoe IPDS diffractometer	3734 independent reflections
Absorption correction: numerical (X-RED; Stoe & Cie, 1997)	2352 reflections with I > 2σ(I)
T_min = 0.730, T_max = 0.933	R_int = 0.110
5120 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.110	Δρ_max = 0.21 e Å⁻³
S = 0.83	Δρ_min = −0.27 e Å⁻³
5120 reflections	Absolute structure: Flack (1983), 1544 Friedel pairs
281 parameters	Absolute structure parameter: −0.07 (10)
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.

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
S1	0.32966 (10)	0.49384 (9)	0.89236 (3)	0.0598 (2)
C7	0.4033 (4)	0.6664 (4)	0.88601 (16)	0.0742 (11)
H7A	0.4218	0.7027	0.9211	0.089*
H7B	0.5018	0.6626	0.8679	0.089*
C8	0.2991 (6)	0.7648 (4)	0.85654 (18)	0.0869 (13)
H8A	0.3469	0.8535	0.8550	0.130*
H8B	0.2021	0.7719	0.8746	0.130*
H8C	0.2822	0.7315	0.8213	0.130*
C1	0.3502 (4)	0.4316 (3)	0.82624 (11)	0.0449 (7)
H1	0.4327	0.4826	0.8085	0.054*
C2	0.3910 (3)	0.2767 (3)	0.82645 (11)	0.0438 (7)
H2	0.3098	0.2297	0.8464	0.053*
C3	0.3922 (3)	0.2146 (3)	0.77071 (11)	0.0440 (7)
H3	0.4823	0.2486	0.7513	0.053*
C4	0.2480 (3)	0.2552 (3)	0.74190 (11)	0.0425 (7)
H4	0.1591	0.2098	0.7582	0.051*
C5	0.2252 (4)	0.4098 (3)	0.74389 (12)	0.0475 (8)
H5	0.3148	0.4557	0.7283	0.057*
O5	0.2082 (2)	0.45149 (19)	0.79800 (8)	0.0495 (5)
O3	0.4053 (3)	0.0694 (2)	0.77736 (10)	0.0681 (7)
H3A	0.3456	0.0306	0.7572	0.102*
O4	0.2607 (2)	0.21320 (19)	0.68835 (8)	0.0463 (5)
C9	0.1286 (4)	0.2511 (3)	0.65856 (12)	0.0504 (8)
H9	0.0378	0.2032	0.6723	0.061*
O6	0.1033 (3)	0.39409 (19)	0.66026 (8)	0.0576 (6)
C6	0.0822 (4)	0.4450 (3)	0.71277 (13)	0.0558 (8)
H6A	−0.0077	0.4030	0.7288	0.067*
H6B	0.0670	0.5435	0.7121	0.067*
C10	0.1571 (4)	0.2085 (3)	0.60276 (12)	0.0470 (7)
C11	0.2464 (4)	0.2843 (3)	0.56915 (14)	0.0632 (10)
H11	0.2842	0.3687	0.5804	0.076*
C12	0.2818 (5)	0.2385 (4)	0.51886 (15)	0.0731 (10)
H12	0.3437	0.2910	0.4967	0.088*
C13	0.2247 (5)	0.1146 (3)	0.50192 (15)	0.0688 (10)
H13	0.2474	0.0830	0.4681	0.083*
C14	0.1343 (5)	0.0382 (3)	0.53503 (15)	0.0699 (10)
H14	0.0957	−0.0458	0.5237	0.084*
C15	0.1001 (4)	0.0850 (3)	0.58515 (14)	0.0594 (9)
H15	0.0379	0.0326	0.6072	0.071*
N2	0.5361 (3)	0.2509 (2)	0.85380 (9)	0.0438 (6)
C21	0.5417 (4)	0.1857 (3)	0.90323 (12)	0.0455 (7)
O22	0.4289 (3)	0.1431 (2)	0.92638 (9)	0.0658 (7)
C23	0.7059 (4)	0.1797 (3)	0.91881 (12)	0.0447 (7)
C24	0.7748 (4)	0.1282 (3)	0.96358 (13)	0.0545 (8)
H24	0.7167	0.0916	0.9911	0.065*
C25	0.9354 (4)	0.1333 (3)	0.96599 (14)	0.0589 (9)
H25	0.9859	0.0994	0.9957	0.071*
C26	1.0203 (4)	0.1878 (4)	0.92502 (15)	0.0598 (9)
H26	1.1273	0.1871	0.9271	0.072*
C27	0.9503 (4)	0.2434 (3)	0.88077 (12)	0.0528 (8)
H27	1.0077	0.2830	0.8537	0.063*
C28	0.7922 (3)	0.2375 (3)	0.87864 (11)	0.0446 (7)
C29	0.6829 (4)	0.2885 (3)	0.83770 (12)	0.0468 (7)
O30	0.7131 (3)	0.3513 (2)	0.79655 (9)	0.0606 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0730 (6)	0.0708 (5)	0.0354 (5)	0.0043 (4)	0.0044 (4)	−0.0071 (4)
C7	0.063 (2)	0.092 (3)	0.068 (3)	−0.021 (2)	0.005 (2)	−0.033 (2)
C8	0.114 (4)	0.069 (2)	0.078 (3)	−0.014 (2)	−0.005 (3)	0.000 (2)
C1	0.0474 (19)	0.0512 (16)	0.0360 (18)	0.0038 (13)	0.0010 (14)	−0.0006 (13)
C2	0.0416 (17)	0.0561 (17)	0.0338 (18)	0.0013 (13)	0.0009 (13)	0.0043 (13)
C3	0.0504 (18)	0.0451 (16)	0.0364 (18)	0.0125 (13)	−0.0011 (13)	0.0021 (12)
C4	0.0486 (17)	0.0449 (15)	0.0340 (18)	0.0057 (13)	0.0002 (12)	0.0043 (13)
C5	0.060 (2)	0.0466 (16)	0.0355 (19)	0.0066 (14)	0.0006 (15)	−0.0020 (12)
O5	0.0534 (13)	0.0574 (12)	0.0377 (13)	0.0118 (9)	−0.0016 (10)	−0.0038 (9)
O3	0.0912 (19)	0.0507 (12)	0.0624 (18)	0.0218 (12)	−0.0265 (13)	−0.0069 (10)
O4	0.0524 (12)	0.0512 (11)	0.0352 (13)	0.0086 (9)	−0.0091 (9)	−0.0031 (8)
C9	0.057 (2)	0.0474 (17)	0.047 (2)	0.0087 (15)	−0.0077 (15)	0.0031 (13)
O6	0.0801 (16)	0.0517 (13)	0.0410 (14)	0.0189 (11)	−0.0137 (11)	−0.0019 (9)
C6	0.063 (2)	0.0601 (19)	0.044 (2)	0.0174 (16)	−0.0084 (16)	0.0004 (14)
C10	0.0546 (18)	0.0479 (16)	0.0385 (19)	0.0018 (14)	−0.0114 (15)	0.0027 (13)
C11	0.089 (3)	0.0551 (19)	0.046 (2)	−0.0067 (18)	−0.0045 (18)	0.0008 (15)
C12	0.096 (3)	0.073 (2)	0.050 (3)	−0.008 (2)	0.001 (2)	0.0095 (18)
C13	0.095 (3)	0.068 (2)	0.043 (2)	0.011 (2)	−0.013 (2)	−0.0061 (17)
C14	0.096 (3)	0.060 (2)	0.054 (3)	−0.0034 (19)	−0.014 (2)	−0.0097 (17)
C15	0.066 (2)	0.0569 (19)	0.055 (2)	−0.0103 (17)	−0.0049 (18)	0.0005 (15)
N2	0.0399 (14)	0.0605 (15)	0.0311 (15)	−0.0018 (12)	−0.0001 (11)	0.0039 (11)
C21	0.0474 (19)	0.0567 (17)	0.0324 (19)	−0.0021 (14)	0.0028 (14)	0.0055 (12)
O22	0.0535 (14)	0.0927 (17)	0.0513 (15)	−0.0082 (12)	0.0001 (12)	0.0279 (12)
C23	0.0504 (19)	0.0476 (15)	0.0361 (18)	0.0017 (14)	−0.0011 (14)	0.0023 (13)
C24	0.059 (2)	0.066 (2)	0.038 (2)	0.0025 (16)	−0.0042 (16)	0.0088 (15)
C25	0.058 (2)	0.072 (2)	0.047 (2)	0.0102 (17)	−0.0126 (18)	0.0021 (16)
C26	0.0464 (19)	0.074 (2)	0.059 (2)	0.0033 (17)	−0.0078 (17)	−0.0069 (18)
C27	0.055 (2)	0.0589 (19)	0.045 (2)	−0.0040 (16)	−0.0001 (15)	−0.0058 (14)
C28	0.0436 (17)	0.0522 (16)	0.0379 (19)	−0.0018 (14)	0.0003 (13)	−0.0043 (13)
C29	0.0509 (19)	0.0556 (18)	0.0339 (19)	−0.0004 (14)	0.0025 (14)	−0.0011 (13)
O30	0.0596 (14)	0.0801 (15)	0.0423 (14)	−0.0080 (11)	0.0040 (11)	0.0159 (11)

Geometric parameters (Å, º) top

S1—C1	1.789 (3)	C6—H6A	0.9700
S1—C7	1.808 (4)	C6—H6B	0.9700
C7—C8	1.515 (6)	C10—C11	1.368 (5)
C7—H7A	0.9700	C10—C15	1.376 (4)
C7—H7B	0.9700	C11—C12	1.384 (5)
C8—H8A	0.9600	C11—H11	0.9300
C8—H8B	0.9600	C12—C13	1.374 (5)
C8—H8C	0.9600	C12—H12	0.9300
C1—O5	1.437 (4)	C13—C14	1.369 (5)
C1—C2	1.553 (4)	C13—H13	0.9300
C1—H1	0.9800	C14—C15	1.381 (5)
C2—N2	1.458 (4)	C14—H14	0.9300
C2—C3	1.535 (4)	C15—H15	0.9300
C2—H2	0.9800	N2—C29	1.387 (4)
C3—O3	1.431 (3)	N2—C21	1.404 (4)
C3—C4	1.501 (4)	C21—O22	1.214 (4)
C3—H3	0.9800	C21—C23	1.479 (4)
C4—O4	1.420 (3)	C23—C24	1.376 (4)
C4—C5	1.523 (4)	C23—C28	1.383 (4)
C4—H4	0.9800	C24—C25	1.395 (5)
C5—O5	1.436 (4)	C24—H24	0.9300
C5—C6	1.509 (4)	C25—C26	1.378 (5)
C5—H5	0.9800	C25—H25	0.9300
O3—H3A	0.8200	C26—C27	1.385 (5)
O4—C9	1.420 (4)	C26—H26	0.9300
C9—O6	1.413 (3)	C27—C28	1.373 (5)
C9—C10	1.493 (4)	C27—H27	0.9300
C9—H9	0.9800	C28—C29	1.490 (4)
O6—C6	1.430 (4)	C29—O30	1.236 (4)

C1—S1—C7	101.41 (16)	C9—O6—C6	113.0 (2)
C8—C7—S1	115.0 (3)	O6—C6—C5	107.5 (3)
C8—C7—H7A	108.5	O6—C6—H6A	110.2
S1—C7—H7A	108.5	C5—C6—H6A	110.2
C8—C7—H7B	108.5	O6—C6—H6B	110.2
S1—C7—H7B	108.5	C5—C6—H6B	110.2
H7A—C7—H7B	107.5	H6A—C6—H6B	108.5
C7—C8—H8A	109.5	C11—C10—C15	118.4 (3)
C7—C8—H8B	109.5	C11—C10—C9	122.1 (3)
H8A—C8—H8B	109.5	C15—C10—C9	119.4 (3)
C7—C8—H8C	109.5	C10—C11—C12	121.5 (3)
H8A—C8—H8C	109.5	C10—C11—H11	119.3
H8B—C8—H8C	109.5	C12—C11—H11	119.3
O5—C1—C2	109.2 (2)	C13—C12—C11	119.4 (4)
O5—C1—S1	109.53 (19)	C13—C12—H12	120.3
C2—C1—S1	110.5 (2)	C11—C12—H12	120.3
O5—C1—H1	109.2	C14—C13—C12	119.6 (4)
C2—C1—H1	109.2	C14—C13—H13	120.2
S1—C1—H1	109.2	C12—C13—H13	120.2
N2—C2—C3	111.2 (2)	C13—C14—C15	120.3 (3)
N2—C2—C1	111.5 (2)	C13—C14—H14	119.8
C3—C2—C1	112.5 (2)	C15—C14—H14	119.8
N2—C2—H2	107.1	C10—C15—C14	120.7 (3)
C3—C2—H2	107.1	C10—C15—H15	119.7
C1—C2—H2	107.1	C14—C15—H15	119.7
O3—C3—C4	112.6 (2)	C29—N2—C21	110.5 (2)
O3—C3—C2	106.5 (2)	C29—N2—C2	127.4 (2)
C4—C3—C2	109.6 (2)	C21—N2—C2	122.1 (2)
O3—C3—H3	109.4	O22—C21—N2	123.9 (3)
C4—C3—H3	109.4	O22—C21—C23	129.3 (3)
C2—C3—H3	109.4	N2—C21—C23	106.8 (2)
O4—C4—C3	108.8 (2)	C24—C23—C28	121.3 (3)
O4—C4—C5	109.1 (2)	C24—C23—C21	130.7 (3)
C3—C4—C5	110.7 (2)	C28—C23—C21	108.0 (3)
O4—C4—H4	109.4	C23—C24—C25	117.2 (3)
C3—C4—H4	109.4	C23—C24—H24	121.4
C5—C4—H4	109.4	C25—C24—H24	121.4
O5—C5—C6	110.4 (3)	C26—C25—C24	120.9 (3)
O5—C5—C4	109.0 (2)	C26—C25—H25	119.5
C6—C5—C4	108.3 (3)	C24—C25—H25	119.5
O5—C5—H5	109.7	C25—C26—C27	121.7 (3)
C6—C5—H5	109.7	C25—C26—H26	119.1
C4—C5—H5	109.7	C27—C26—H26	119.1
C5—O5—C1	110.4 (2)	C28—C27—C26	116.9 (3)
C3—O3—H3A	109.5	C28—C27—H27	121.5
C4—O4—C9	111.6 (2)	C26—C27—H27	121.5
O6—C9—O4	111.5 (2)	C27—C28—C23	121.9 (3)
O6—C9—C10	109.3 (2)	C27—C28—C29	130.4 (3)
O4—C9—C10	107.2 (2)	C23—C28—C29	107.6 (3)
O6—C9—H9	109.6	O30—C29—N2	125.0 (3)
O4—C9—H9	109.6	O30—C29—C28	128.1 (3)
C10—C9—H9	109.6	N2—C29—C28	106.9 (2)

C7—S1—C1—H1	25.4	C9—C10—C11—C12	174.9 (3)
C1—S1—C7—C8	72.3 (3)	C10—C11—C12—C13	0.7 (6)
C7—S1—C1—O5	−94.1 (2)	C11—C12—C13—C14	−0.3 (6)
C7—S1—C1—C2	145.6 (2)	C12—C13—C14—C15	0.2 (6)
O5—C1—C2—N2	178.9 (2)	C11—C10—C15—C14	0.9 (5)
S1—C1—C2—N2	−60.6 (3)	C9—C10—C15—C14	−175.1 (3)
O5—C1—C2—C3	53.1 (3)	C13—C14—C15—C10	−0.5 (6)
S1—C1—C2—C3	173.7 (2)	C3—C2—N2—C29	58.1 (4)
N2—C2—C3—O3	63.6 (3)	C1—C2—N2—C29	−68.4 (4)
C1—C2—C3—O3	−170.5 (2)	C3—C2—N2—C21	−124.5 (3)
N2—C2—C3—C4	−174.3 (2)	C1—C2—N2—C21	109.0 (3)
C1—C2—C3—C4	−48.4 (3)	C29—N2—C21—O22	179.7 (3)
O3—C3—C4—O4	−69.7 (3)	C2—N2—C21—O22	1.9 (5)
C2—C3—C4—O4	172.0 (2)	C29—N2—C21—C23	−1.2 (3)
O3—C3—C4—C5	170.4 (2)	C2—N2—C21—C23	−179.0 (2)
C2—C3—C4—C5	52.1 (3)	O22—C21—C23—C24	−1.8 (6)
O4—C4—C5—O5	178.5 (2)	N2—C21—C23—C24	179.1 (3)
C3—C4—C5—O5	−61.8 (3)	O22—C21—C23—C28	177.8 (3)
O4—C4—C5—C6	58.2 (3)	N2—C21—C23—C28	−1.2 (3)
C3—C4—C5—C6	178.0 (3)	C28—C23—C24—C25	−1.8 (5)
C6—C5—O5—C1	−173.8 (2)	C21—C23—C24—C25	177.8 (3)
C4—C5—O5—C1	67.3 (3)	C23—C24—C25—C26	0.0 (5)
C2—C1—O5—C5	−62.4 (3)	C24—C25—C26—C27	2.1 (5)
S1—C1—O5—C5	176.51 (19)	C25—C26—C27—C28	−2.3 (5)
C3—C4—O4—C9	−178.8 (2)	C26—C27—C28—C23	0.4 (5)
C5—C4—O4—C9	−57.9 (3)	C26—C27—C28—C29	179.1 (3)
C4—O4—C9—O6	57.8 (3)	C24—C23—C28—C27	1.6 (5)
C4—O4—C9—C10	177.3 (2)	C21—C23—C28—C27	−178.1 (3)
O4—C9—O6—C6	−58.9 (3)	C24—C23—C28—C29	−177.3 (3)
C10—C9—O6—C6	−177.2 (3)	C21—C23—C28—C29	3.0 (3)
C9—O6—C6—C5	58.9 (3)	C21—N2—C29—O30	−177.7 (3)
O5—C5—C6—O6	−176.8 (2)	C2—N2—C29—O30	0.0 (5)
C4—C5—C6—O6	−57.5 (3)	C21—N2—C29—C28	3.0 (3)
O6—C9—C10—C11	41.1 (4)	C2—N2—C29—C28	−179.4 (3)
O4—C9—C10—C11	−79.8 (3)	C27—C28—C29—O30	−1.9 (5)
O6—C9—C10—C15	−143.0 (3)	C23—C28—C29—O30	177.0 (3)
O4—C9—C10—C15	96.1 (3)	C27—C28—C29—N2	177.4 (3)
C15—C10—C11—C12	−1.1 (5)	C23—C28—C29—N2	−3.7 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C23—C28 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O30ⁱ	0.82	2.27	3.014 (3)	150
C14—H14···Cgⁱ	0.93	2.98	3.613 (3)	126

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₃NO₆S
M_r	441.48
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.6728 (6), 9.7583 (10), 25.3102 (15)
V (Å³)	2142.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.30 × 0.12 × 0.05

Data collection
Diffractometer	Stoe IPDS
Absorption correction	Numerical (X-RED; Stoe & Cie, 1997)
T_min, T_max	0.730, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	5120, 3734, 2352
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.110, 0.83
No. of reflections	5120
No. of parameters	281
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27
Absolute structure	Flack (1983), 1544 Friedel pairs
Absolute structure parameter	−0.07 (10)

Computer programs: EXPOSE (Stoe & Cie, 1997), CELL (Stoe & Cie, 1997), INTEGRATE (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C23—C28 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O30ⁱ	0.82	2.27	3.014 (3)	150
C14—H14···Cgⁱ	0.93	2.98	3.613 (3)	126

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

This work was supported by a grant from the Swedish Research Council and by the Faculty of Natural Sciences at Stockholm University

References

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