O-Ethyl and O-methyl N-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)thiocarbamate

In both the title structures, O-ethyl N-(2,3,4,6-tetra-O-acetyl-β-D-gluco­pyran­osyl)­thio­carbam­ate, C₁₇H₂₅NO₁₀S, and O-methyl N-(2,3,4,6-tetra-O-acetyl-β-D-gluco­pyran­osyl)­thiocar­bam­ate, C₁₆H₂₃NO₁₀S, the hexo­pyran­osyl ring adopts the ⁴C₁ conformation. All the ring substituents are in equatorial positions. The acetoxy­methyl group is in a gauche–gauche conformation. The S atom is in a synperi­planar conformation, while the C—N—C—O linkage is antiperiplanar. N—H...O intermolecular hydrogen bonds link the mol­ecules into infinite chains and these are connected by C—H...O interactions.

S1. Comment

Many nomadic (define?) sugars have important biological functions (Varki, 1993). They may control various gene expressions to adjust the growth, development, controlled reaction and biochemistry of organs (Garg & Jeanloz, 1985). Query rephrasing. Glycosyl isothiocyanates have been widely used as valuable intermediates in the synthesis of glycosyl thiourea derivatives (Yasuo et al., 1999). Isothiocyanates and glycosyl isothiocyanates have been the focus of synthetic attention in recent years and have potential pharmacological properties (Mukerjee & Ashare, 1991). 1-Deoxynojirimycin, castanospermine and some of their derivatives have also shown anti-HIV activity (Tyms et al., 1990). Many biologically important products have a sugar unit joined through an atom (O, S, N or C) or a group of atoms (Avalos et al., 1990). Here, we report the X-ray structures of O-ethyl N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)carbamothiate, (I), and O-methyl N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)carbamothiate, (II). \sch

The bond lengths and angles in (I) and (II) are normal and agree with those of D-glucopyranose (Ferrier, 1963), N-(β-D-glucopyranosyl)hydroxylamine (Mostad, 1978) and N-(β-D-glucopyranosyl)-S-phenylsulfenamide (Lee et al., 1995). The hexopyranosyl ring in both structures adopts a ⁴C₁ conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.605 (3), q₂ = 0.076 (3) and q₃ = 0.601 (3) Å, and θ = 7.0 (3) and ϕ₂ = 6(2)°, for (I), and Q = 0.590 (5), q₂ = 0.054 (4) and q₃ = 0.587 (5) Å, and θ = 5.3 (4) and ϕ₂ = 2(5)°, for (II). The dihedral angle between the O-acetyl groups and the mean plane through the hexopyranosyl ring is in the range of 74.9 (2) to 89.6 (1)° in (I) and 72.6 (2) to 88.9 (2)° in (II). The anomeric substituent, meanwhile, makes a dihedral angle of 64.7 (1) and 65.2 (2)° in (I) and (II), respectively, with the same ring. All ring substituents are in the equatorial position with respect to the ring in both structures.

In both structures, the acetoxymethyl group is in a gauche-gauche conformation, with O1—C5—C12—O8 and C4—C5—C12—O8 torsion angles of -70.0 (3) and 50.0 (4)°, respectively, for (I), and -71.4 (5) and 49.0 (5)°, respectively, for (II). These values may be compared with those in N-(β-D-glucopyranosyl)-S-phenylsulfenamide (Lee et al., 1995), where the corresponding O5—C5—C6—O6 and C4—C5—C6—O6 torsion angles are 72.4 (3) and -168.2 (3)°, respectively. The S atom is in a syn-periplanar conformation with respect to atom C1, while the C1—N15—C16—O17 linkage is anti-periplanar in both structures.

In the crystals of both (I) and (II), N—H···O intermolecular hydrogen bonds (Table 3) form infinite chains along the a axis. These chains are interconnected by C—H···O interactions (Table 3) to form an elongated spring-like structure along the b axis.

Related literature

For related literature, see: Avalos et al. (1990); Cremer & Pople (1975); Ferrier (1963); Garg & Jeanloz (1985); Lee et al. (1995); Mostad (1978); Mukerjee & Ashare (1991); Tyms et al. (1990); Varki (1993); Yasuo et al. (1999).

S2. Experimental

A solution of 2,3,4,6-tetra-O-acetyl-β-D-glycosyl isothiocyanate (0.3 g) in ethanol (20 ml) and methanol (20 ml) for (I) and (II), respectively, was added dropwise to boiling ethanol (20 ml) for (I) and methanol (20 ml) for (II). The boiling solution was stirred for 2 h while refluxing. After filtration, the clear colourless filtrate was left at room temperature until single crystals suitable for X-ray analysis were obtained.

S3. Refinement

After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their parent atoms. C—H distances? However, the H atom on N15 in both structures, which is involved in intermolecular hydrogen bonding, was located from a difference Fourier map and refined isotropically. The C7, C11 and C13 methyl groups for (I) were refined using rotating-group refinement. Please check - C13 not a methyl carbon. Should it be C14?

Computing details

For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) O-ethyl N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)carbamothiate

Crystal data

C17H25NO10S	F(000) = 460
Mr = 435.44	Dx = 1.264 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.7492 (2) Å	Cell parameters from 4350 reflections
b = 10.4470 (3) Å	θ = 1.4–28.5°
c = 14.3852 (3) Å	µ = 0.19 mm^−1
β = 100.810 (1)°	T = 293 K
V = 1143.90 (5) Å^3	Parallelepiped, colourless
Z = 2	0.44 × 0.34 × 0.30 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5034 independent reflections
Radiation source: fine-focus sealed tube	2780 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 8.33 pixels mm^-1	θmax = 27.9°, θmin = 1.4°
ω scans	h = −8→10
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.921, Tmax = 0.945	l = −18→18
7784 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.0613P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.168	(Δ/σ)max < 0.001
S = 0.88	Δρmax = 0.34 e Å^−3
5034 reflections	Δρmin = −0.31 e Å^−3
267 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.055 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.10 (13)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.54892 (17)	0.41399 (11)	0.68914 (9)	0.0918 (4)
O1	0.4248 (3)	0.7520 (2)	0.67308 (15)	0.0507 (6)
O2	0.4085 (4)	0.6917 (3)	0.92413 (18)	0.0676 (7)
O3	0.5855 (7)	0.8385 (5)	1.0070 (2)	0.148 (2)
O4	0.1738 (3)	0.9040 (3)	0.87532 (16)	0.0582 (6)
O5	−0.0952 (5)	0.8271 (5)	0.8781 (3)	0.1202 (15)
O6	−0.0114 (3)	0.8894 (2)	0.67380 (16)	0.0533 (6)
O7	0.0183 (5)	1.1020 (3)	0.6976 (4)	0.1301 (17)
O8	0.2991 (3)	0.9635 (2)	0.54130 (18)	0.0623 (7)
O9	0.0417 (4)	1.0440 (4)	0.4639 (3)	0.1103 (13)
C1	0.4486 (4)	0.6790 (3)	0.7602 (2)	0.0502 (8)
H1A	0.3712	0.6041	0.7513	0.060*
C2	0.3987 (4)	0.7655 (3)	0.8376 (2)	0.0503 (8)
H2A	0.4778	0.8394	0.8488	0.060*
C3	0.2075 (4)	0.8103 (3)	0.8068 (2)	0.0483 (8)
H3A	0.1282	0.7372	0.8070	0.058*
C4	0.1765 (4)	0.8705 (3)	0.7081 (2)	0.0481 (8)
H4A	0.2381	0.9526	0.7102	0.058*
C5	0.2428 (4)	0.7787 (3)	0.6370 (2)	0.0491 (8)
H5A	0.1763	0.6985	0.6336	0.059*
C6	0.5073 (6)	0.7404 (5)	1.0049 (3)	0.0703 (11)
C7	0.4978 (7)	0.6552 (5)	1.0893 (3)	0.0891 (15)
H7A	0.4821	0.5678	1.0686	0.134*
H7B	0.4005	0.6809	1.1175	0.134*
H7C	0.6048	0.6628	1.1349	0.134*
H7D	0.5103	0.7073	1.1451	0.134*	0.00
H7E	0.5913	0.5936	1.0965	0.134*	0.00
H7F	0.3870	0.6114	1.0800	0.134*	0.00
C8	0.0176 (5)	0.9053 (5)	0.9042 (3)	0.0702 (11)
C9	0.0058 (8)	1.0167 (7)	0.9677 (4)	0.113 (2)
H9A	0.1140	1.0639	0.9770	0.169*
H9B	−0.0149	0.9865	1.0277	0.169*
H9C	−0.0892	1.0714	0.9394	0.169*
C10	−0.0754 (5)	1.0119 (4)	0.6721 (3)	0.0715 (11)
C11	−0.2685 (6)	1.0154 (5)	0.6351 (4)	0.0993 (16)
H11A	−0.2998	0.9483	0.5894	0.149*
H11B	−0.2999	1.0967	0.6055	0.149*
H11C	−0.3302	1.0035	0.6864	0.149*
H11D	−0.3203	1.0840	0.6648	0.149*	0.00
H11E	−0.3198	0.9356	0.6487	0.149*	0.00
H11F	−0.2898	1.0288	0.5679	0.149*	0.00
C12	0.2244 (5)	0.8342 (4)	0.5378 (3)	0.0611 (10)
H12A	0.2846	0.7794	0.4998	0.073*
H12B	0.1012	0.8372	0.5083	0.073*
C13	0.1950 (6)	1.0590 (4)	0.4987 (3)	0.0714 (11)
C14	0.2937 (6)	1.1830 (5)	0.5060 (4)	0.0982 (17)
H14A	0.3959	1.1769	0.5552	0.147*
H14B	0.2194	1.2507	0.5206	0.147*
H14C	0.3290	1.2009	0.4468	0.147*
H14D	0.2336	1.2422	0.4600	0.147*	0.00
H14E	0.4102	1.1685	0.4944	0.147*	0.00
H14F	0.3004	1.2179	0.5683	0.147*	0.00
N15	0.6291 (4)	0.6375 (3)	0.7831 (2)	0.0607 (8)
C16	0.6819 (5)	0.5210 (4)	0.7519 (2)	0.0595 (10)
O17	0.8546 (4)	0.5099 (3)	0.7795 (2)	0.0864 (9)
C18	0.9330 (6)	0.3859 (6)	0.7584 (4)	0.1087 (19)
H18A	0.8999	0.3659	0.6916	0.130*
H18B	0.8925	0.3174	0.7944	0.130*
C19	1.1273 (7)	0.4004 (8)	0.7855 (7)	0.168 (3)
H19A	1.1832	0.3221	0.7725	0.252*
H19B	1.1584	0.4196	0.8517	0.252*
H19C	1.1655	0.4687	0.7496	0.252*
H15A	0.711 (4)	0.695 (3)	0.807 (3)	0.097 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0850 (9)	0.0737 (8)	0.1087 (9)	0.0072 (6)	−0.0027 (7)	−0.0385 (7)
O1	0.0303 (13)	0.0560 (13)	0.0617 (14)	0.0111 (10)	−0.0016 (9)	−0.0068 (11)
O2	0.0764 (19)	0.0550 (15)	0.0611 (16)	−0.0001 (13)	−0.0139 (13)	0.0018 (12)
O3	0.170 (4)	0.181 (5)	0.071 (2)	−0.106 (4)	−0.038 (2)	0.018 (2)
O4	0.0429 (15)	0.0624 (14)	0.0667 (14)	−0.0031 (12)	0.0036 (10)	−0.0150 (13)
O5	0.063 (2)	0.177 (4)	0.128 (3)	−0.050 (2)	0.037 (2)	−0.045 (3)
O6	0.0282 (12)	0.0520 (13)	0.0735 (14)	0.0059 (10)	−0.0062 (10)	−0.0030 (11)
O7	0.060 (2)	0.0587 (19)	0.254 (5)	0.0127 (16)	−0.016 (3)	−0.039 (3)
O8	0.0381 (14)	0.0723 (17)	0.0712 (15)	0.0046 (12)	−0.0032 (10)	0.0120 (13)
O9	0.051 (2)	0.098 (3)	0.162 (3)	0.0101 (17)	−0.0326 (19)	0.026 (2)
C1	0.037 (2)	0.0466 (18)	0.061 (2)	0.0003 (15)	−0.0080 (14)	0.0001 (16)
C2	0.042 (2)	0.0503 (18)	0.0512 (19)	0.0025 (15)	−0.0088 (13)	−0.0019 (15)
C3	0.0349 (19)	0.0472 (17)	0.059 (2)	−0.0026 (14)	0.0001 (13)	−0.0060 (15)
C4	0.0294 (17)	0.0507 (18)	0.0593 (19)	−0.0007 (14)	−0.0041 (13)	−0.0102 (15)
C5	0.0303 (18)	0.0511 (18)	0.060 (2)	0.0040 (14)	−0.0067 (13)	−0.0078 (16)
C6	0.057 (3)	0.087 (3)	0.061 (2)	−0.011 (2)	−0.0037 (17)	−0.006 (2)
C7	0.107 (4)	0.094 (3)	0.061 (3)	0.005 (3)	0.001 (2)	0.000 (2)
C8	0.037 (2)	0.100 (3)	0.072 (2)	−0.007 (2)	0.0088 (17)	−0.008 (2)
C9	0.091 (4)	0.153 (5)	0.101 (4)	0.003 (4)	0.036 (3)	−0.049 (4)
C10	0.047 (2)	0.061 (2)	0.102 (3)	0.018 (2)	0.001 (2)	−0.005 (2)
C11	0.045 (3)	0.093 (4)	0.154 (4)	0.025 (3)	0.003 (3)	0.011 (3)
C12	0.043 (2)	0.072 (2)	0.064 (2)	0.0073 (18)	−0.0034 (16)	−0.0057 (19)
C13	0.053 (3)	0.076 (3)	0.078 (3)	0.016 (2)	−0.0061 (19)	0.018 (2)
C14	0.063 (3)	0.083 (3)	0.141 (5)	−0.002 (3)	0.000 (3)	0.040 (3)
N15	0.0380 (19)	0.0536 (17)	0.081 (2)	0.0081 (14)	−0.0122 (14)	−0.0122 (16)
C16	0.056 (3)	0.055 (2)	0.062 (2)	0.0209 (18)	−0.0045 (16)	−0.0016 (17)
O17	0.0607 (19)	0.0795 (19)	0.107 (2)	0.0341 (16)	−0.0151 (15)	−0.0197 (18)
C18	0.084 (4)	0.112 (4)	0.119 (4)	0.057 (3)	−0.010 (3)	−0.028 (3)
C19	0.088 (5)	0.122 (5)	0.287 (10)	0.020 (5)	0.021 (5)	−0.067 (7)

Geometric parameters (Å, º)

S1—C16	1.667 (4)	C1—N15	1.442 (4)
O1—C5	1.436 (4)	C1—C2	1.538 (5)
O1—C1	1.449 (4)	C2—C3	1.538 (5)
O2—C6	1.365 (5)	C3—C4	1.530 (5)
O2—C2	1.454 (4)	C4—C5	1.558 (4)
O3—C6	1.188 (6)	C5—C12	1.521 (5)
O4—C8	1.352 (4)	C6—C7	1.517 (7)
O4—C3	1.447 (4)	C8—C9	1.493 (7)
O5—C8	1.204 (6)	C10—C11	1.492 (6)
O6—C10	1.371 (5)	C13—C14	1.498 (7)
O6—C4	1.461 (4)	N15—C16	1.385 (5)
O7—C10	1.204 (5)	C16—O17	1.328 (4)
O8—C13	1.355 (5)	O17—C18	1.486 (6)
O8—C12	1.467 (5)	C18—C19	1.490 (8)
O9—C13	1.209 (5)
C5—O1—C1	111.8 (2)	O3—C6—O2	123.0 (4)
C6—O2—C2	117.5 (3)	O3—C6—C7	126.0 (4)
C8—O4—C3	120.1 (3)	O2—C6—C7	111.0 (4)
C10—O6—C4	117.8 (3)	O5—C8—O4	122.5 (4)
C13—O8—C12	117.7 (3)	O5—C8—C9	126.6 (4)
N15—C1—O1	108.4 (3)	O4—C8—C9	110.9 (4)
N15—C1—C2	112.1 (3)	O7—C10—O6	122.0 (4)
O1—C1—C2	108.0 (2)	O7—C10—C11	126.6 (4)
O2—C2—C1	109.2 (3)	O6—C10—C11	111.4 (4)
O2—C2—C3	107.5 (3)	O8—C12—C5	110.6 (3)
C1—C2—C3	109.2 (2)	O9—C13—O8	123.2 (4)
O4—C3—C4	109.7 (3)	O9—C13—C14	126.1 (4)
O4—C3—C2	107.3 (2)	O8—C13—C14	110.6 (4)
C4—C3—C2	111.5 (3)	C16—N15—C1	121.6 (3)
O6—C4—C3	110.0 (3)	O17—C16—N15	108.8 (3)
O6—C4—C5	107.0 (2)	O17—C16—S1	126.1 (3)
C3—C4—C5	110.0 (3)	N15—C16—S1	125.1 (3)
O1—C5—C12	109.0 (3)	C16—O17—C18	116.3 (4)
O1—C5—C4	107.7 (2)	O17—C18—C19	106.9 (5)
C12—C5—C4	113.4 (3)
C5—O1—C1—N15	170.3 (3)	O6—C4—C5—O1	−176.1 (3)
C5—O1—C1—C2	−68.1 (3)	C3—C4—C5—O1	−56.6 (3)
C6—O2—C2—C1	127.3 (3)	O6—C4—C5—C12	63.2 (3)
C6—O2—C2—C3	−114.3 (4)	C3—C4—C5—C12	−177.3 (3)
N15—C1—C2—O2	−64.9 (4)	C2—O2—C6—O3	−0.8 (7)
O1—C1—C2—O2	175.7 (3)	C2—O2—C6—C7	177.6 (4)
N15—C1—C2—C3	177.8 (3)	C3—O4—C8—O5	3.2 (6)
O1—C1—C2—C3	58.4 (3)	C3—O4—C8—C9	−174.8 (4)
C8—O4—C3—C4	98.4 (4)	C4—O6—C10—O7	0.1 (6)
C8—O4—C3—C2	−140.3 (3)	C4—O6—C10—C11	179.8 (3)
O2—C2—C3—O4	69.0 (3)	C13—O8—C12—C5	−125.7 (3)
C1—C2—C3—O4	−172.6 (3)	O1—C5—C12—O8	−70.0 (3)
O2—C2—C3—C4	−170.8 (3)	C4—C5—C12—O8	50.0 (4)
C1—C2—C3—C4	−52.5 (4)	C12—O8—C13—O9	5.0 (6)
C10—O6—C4—C3	106.4 (3)	C12—O8—C13—C14	−177.9 (4)
C10—O6—C4—C5	−134.1 (3)	O1—C1—N15—C16	−91.0 (4)
O4—C3—C4—O6	−72.1 (3)	C2—C1—N15—C16	149.9 (3)
C2—C3—C4—O6	169.2 (2)	C1—N15—C16—O17	177.2 (3)
O4—C3—C4—C5	170.3 (2)	C1—N15—C16—S1	−2.2 (5)
C2—C3—C4—C5	51.6 (3)	N15—C16—O17—C18	175.6 (4)
C1—O1—C5—C12	−170.1 (3)	S1—C16—O17—C18	−5.0 (6)
C1—O1—C5—C4	66.5 (3)	C16—O17—C18—C19	173.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15A···O5^i	0.90 (3)	2.15 (3)	3.046 (5)	178 (3)
C5—H5A···O9^ii	0.98	2.56	3.431 (5)	149

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

(II) O-methyl N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)carbamothiate

Crystal data

C16H23NO10S	F(000) = 444
Mr = 421.41	Dx = 1.347 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.3543 (2) Å	Cell parameters from 3438 reflections
b = 10.2555 (1) Å	θ = 1.4–28.3°
c = 14.0142 (4) Å	µ = 0.21 mm^−1
β = 100.684 (2)°	T = 293 K
V = 1038.66 (4) Å^3	Needle, colourless
Z = 2	0.26 × 0.12 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	4151 independent reflections
Radiation source: fine-focus sealed tube	2094 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 1.5°
ω scans	h = −9→9
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −10→13
Tmin = 0.953, Tmax = 0.985	l = −13→18
7436 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.072	w = 1/[σ^2(Fo^2) + (0.0843P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.184	(Δ/σ)max < 0.001
S = 0.86	Δρmax = 0.28 e Å^−3
4151 reflections	Δρmin = −0.34 e Å^−3
258 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.035 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.17 (17)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.4058 (2)	0.47378 (15)	0.30340 (12)	0.0675 (5)
O1	0.5576 (4)	0.8095 (3)	0.3225 (2)	0.0396 (8)
O2	0.5575 (5)	0.7557 (4)	0.0647 (2)	0.0503 (9)
O3	0.4038 (6)	0.9201 (5)	−0.0190 (3)	0.0806 (14)
O4	0.8071 (4)	0.9680 (4)	0.1122 (2)	0.0427 (8)
O5	1.0902 (6)	0.8938 (6)	0.1109 (4)	0.0936 (18)
O6	1.0039 (4)	0.9559 (3)	0.3143 (2)	0.0434 (8)
O7	0.9609 (6)	1.1694 (4)	0.2877 (4)	0.0901 (16)
O8	0.6980 (4)	1.0214 (4)	0.4549 (3)	0.0511 (10)
O9	0.9684 (5)	1.1029 (5)	0.5307 (3)	0.0795 (14)
O17	0.0900 (5)	0.5878 (4)	0.2208 (3)	0.0601 (10)
C1	0.5251 (6)	0.7396 (5)	0.2322 (3)	0.0387 (11)
H1A	0.6041	0.6619	0.2382	0.046*
C2	0.5748 (6)	0.8280 (5)	0.1541 (3)	0.0385 (11)
H2A	0.4926	0.9040	0.1450	0.046*
C3	0.7743 (6)	0.8717 (5)	0.1825 (3)	0.0362 (10)
H3A	0.8567	0.7969	0.1808	0.043*
C4	0.8099 (6)	0.9309 (4)	0.2829 (3)	0.0331 (10)
H4A	0.7411	1.0129	0.2819	0.040*
C5	0.7482 (6)	0.8377 (5)	0.3552 (3)	0.0380 (11)
H5A	0.8190	0.7565	0.3564	0.046*
C6	0.4684 (7)	0.8124 (6)	−0.0183 (4)	0.0509 (13)
C7	0.4799 (10)	0.7301 (8)	−0.1036 (4)	0.076 (2)
H7A	0.5381	0.6488	−0.0822	0.115*
H7B	0.5514	0.7742	−0.1445	0.115*
H7C	0.3576	0.7140	−0.1394	0.115*
C8	0.9686 (7)	0.9711 (6)	0.0835 (3)	0.0517 (13)
C9	0.9858 (9)	1.0827 (8)	0.0198 (5)	0.086 (2)
H9A	1.1047	1.0804	0.0008	0.129*
H9B	0.9736	1.1624	0.0540	0.129*
H9C	0.8903	1.0782	−0.0370	0.129*
C10	1.0628 (7)	1.0796 (6)	0.3143 (4)	0.0532 (13)
C11	1.2664 (7)	1.0899 (7)	0.3510 (5)	0.0754 (19)
H11A	1.3163	1.0047	0.3677	0.113*
H11B	1.2889	1.1449	0.4074	0.113*
H11C	1.3248	1.1268	0.3014	0.113*
C12	0.7739 (7)	0.8915 (6)	0.4567 (4)	0.0504 (13)
H12A	0.7123	0.8355	0.4966	0.060*
H12B	0.9046	0.8937	0.4851	0.060*
C13	0.8081 (7)	1.1198 (6)	0.4972 (4)	0.0529 (14)
C14	0.7078 (9)	1.2424 (8)	0.4920 (6)	0.085 (2)
H14A	0.5814	1.2283	0.4614	0.127*
H14B	0.7637	1.3041	0.4548	0.127*
H14C	0.7120	1.2757	0.5564	0.127*
N15	0.3383 (6)	0.7011 (4)	0.2131 (3)	0.0436 (10)
C16	0.2752 (7)	0.5893 (5)	0.2442 (3)	0.0438 (12)
C17	−0.0065 (9)	0.4700 (8)	0.2397 (5)	0.085 (2)
H17A	−0.1374	0.4825	0.2195	0.127*
H17B	0.0209	0.4507	0.3078	0.127*
H17C	0.0332	0.3988	0.2040	0.127*
H15A	0.266 (7)	0.751 (7)	0.182 (4)	0.054 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0786 (10)	0.0332 (8)	0.0893 (10)	0.0010 (8)	0.0122 (8)	0.0217 (8)
O1	0.0426 (17)	0.034 (2)	0.0411 (18)	−0.0076 (15)	0.0050 (13)	0.0013 (14)
O2	0.069 (2)	0.032 (2)	0.0442 (19)	−0.0083 (17)	−0.0040 (16)	−0.0023 (15)
O3	0.099 (3)	0.083 (4)	0.055 (2)	0.034 (3)	0.002 (2)	0.008 (2)
O4	0.0471 (18)	0.0334 (19)	0.0484 (18)	−0.0001 (15)	0.0106 (14)	0.0134 (16)
O5	0.073 (3)	0.108 (5)	0.112 (4)	0.038 (3)	0.049 (3)	0.058 (3)
O6	0.0382 (16)	0.028 (2)	0.0606 (19)	−0.0044 (14)	0.0007 (14)	0.0012 (16)
O7	0.077 (3)	0.025 (3)	0.156 (5)	−0.013 (2)	−0.009 (3)	0.018 (3)
O8	0.0448 (19)	0.050 (3)	0.055 (2)	−0.0065 (17)	0.0011 (15)	−0.0137 (17)
O9	0.059 (3)	0.063 (3)	0.104 (3)	−0.010 (2)	−0.019 (2)	−0.020 (3)
O17	0.057 (2)	0.036 (2)	0.082 (3)	−0.0200 (18)	−0.0024 (18)	0.011 (2)
C1	0.043 (2)	0.025 (3)	0.046 (3)	−0.005 (2)	0.005 (2)	0.001 (2)
C2	0.054 (3)	0.024 (3)	0.036 (2)	0.001 (2)	0.004 (2)	0.0009 (19)
C3	0.045 (3)	0.025 (3)	0.037 (2)	−0.004 (2)	0.0046 (19)	0.0097 (19)
C4	0.032 (2)	0.021 (2)	0.044 (2)	−0.0019 (18)	0.0028 (18)	0.0045 (18)
C5	0.038 (2)	0.026 (3)	0.046 (3)	−0.002 (2)	−0.002 (2)	0.001 (2)
C6	0.055 (3)	0.052 (4)	0.043 (3)	−0.007 (3)	0.002 (2)	0.004 (3)
C7	0.113 (5)	0.067 (5)	0.048 (3)	−0.027 (4)	0.009 (3)	−0.007 (3)
C8	0.053 (3)	0.056 (4)	0.048 (3)	0.008 (3)	0.014 (2)	0.016 (3)
C9	0.083 (4)	0.089 (6)	0.095 (5)	0.008 (4)	0.039 (4)	0.053 (5)
C10	0.057 (3)	0.031 (3)	0.070 (3)	−0.013 (3)	0.007 (3)	−0.003 (3)
C11	0.055 (3)	0.057 (5)	0.111 (5)	−0.016 (3)	0.007 (3)	−0.009 (4)
C12	0.051 (3)	0.051 (4)	0.045 (3)	−0.006 (3)	−0.005 (2)	0.003 (2)
C13	0.046 (3)	0.056 (4)	0.055 (3)	−0.011 (3)	0.006 (2)	−0.018 (3)
C14	0.077 (4)	0.066 (5)	0.107 (5)	0.004 (4)	0.008 (4)	−0.030 (4)
N15	0.044 (2)	0.025 (2)	0.055 (3)	−0.0052 (19)	−0.0097 (19)	0.0059 (19)
C16	0.052 (3)	0.024 (3)	0.051 (3)	−0.004 (2)	−0.002 (2)	0.001 (2)
C17	0.081 (4)	0.063 (5)	0.103 (5)	−0.046 (4)	−0.001 (4)	0.020 (4)

Geometric parameters (Å, º)

S1—C16	1.648 (5)	O9—C13	1.198 (6)
O1—C5	1.422 (5)	O17—C16	1.341 (5)
O1—C1	1.436 (5)	O17—C17	1.450 (7)
O2—C6	1.356 (6)	C1—N15	1.407 (6)
O2—C2	1.440 (6)	C1—C2	1.517 (6)
O3—C6	1.203 (7)	C2—C3	1.515 (6)
O4—C8	1.323 (6)	C3—C4	1.510 (6)
O4—C3	1.447 (5)	C4—C5	1.522 (6)
O5—C8	1.203 (7)	C5—C12	1.506 (7)
O6—C10	1.341 (6)	C6—C7	1.477 (9)
O6—C4	1.436 (5)	C8—C9	1.472 (8)
O7—C10	1.202 (7)	C10—C11	1.494 (8)
O8—C13	1.359 (6)	C13—C14	1.453 (10)
O8—C12	1.443 (7)	N15—C16	1.341 (6)
C5—O1—C1	112.2 (3)	O1—C5—C4	108.1 (3)
C6—O2—C2	118.5 (4)	C12—C5—C4	113.5 (4)
C8—O4—C3	119.8 (4)	O3—C6—O2	121.8 (5)
C10—O6—C4	118.1 (4)	O3—C6—C7	126.9 (5)
C13—O8—C12	118.7 (4)	O2—C6—C7	111.0 (6)
C16—O17—C17	118.3 (5)	O5—C8—O4	122.9 (5)
N15—C1—O1	107.7 (4)	O5—C8—C9	124.3 (5)
N15—C1—C2	112.8 (4)	O4—C8—C9	112.7 (5)
O1—C1—C2	108.4 (4)	O7—C10—O6	122.8 (5)
O2—C2—C3	107.8 (3)	O7—C10—C11	125.5 (6)
O2—C2—C1	109.0 (4)	O6—C10—C11	111.7 (5)
C3—C2—C1	109.7 (3)	O8—C12—C5	110.0 (4)
O4—C3—C4	109.7 (4)	O9—C13—O8	121.8 (6)
O4—C3—C2	107.4 (3)	O9—C13—C14	126.7 (6)
C4—C3—C2	110.9 (4)	O8—C13—C14	111.4 (5)
O6—C4—C3	110.4 (3)	C16—N15—C1	124.2 (4)
O6—C4—C5	108.1 (3)	N15—C16—O17	109.1 (4)
C3—C4—C5	110.2 (4)	N15—C16—S1	125.1 (4)
O1—C5—C12	108.8 (3)	O17—C16—S1	125.8 (4)
C5—O1—C1—N15	172.1 (4)	O6—C4—C5—O1	−178.1 (3)
C5—O1—C1—C2	−65.6 (4)	C3—C4—C5—O1	−57.5 (5)
C6—O2—C2—C3	−106.9 (5)	O6—C4—C5—C12	61.1 (5)
C6—O2—C2—C1	134.0 (4)	C3—C4—C5—C12	−178.3 (4)
N15—C1—C2—O2	−65.5 (5)	C2—O2—C6—O3	−0.3 (7)
O1—C1—C2—O2	175.3 (3)	C2—O2—C6—C7	174.4 (4)
N15—C1—C2—C3	176.6 (4)	C3—O4—C8—O5	2.5 (8)
O1—C1—C2—C3	57.5 (5)	C3—O4—C8—C9	−174.1 (5)
C8—O4—C3—C4	96.8 (5)	C4—O6—C10—O7	−1.4 (7)
C8—O4—C3—C2	−142.7 (5)	C4—O6—C10—C11	178.6 (4)
O2—C2—C3—O4	68.5 (5)	C13—O8—C12—C5	−125.7 (4)
C1—C2—C3—O4	−172.9 (4)	O1—C5—C12—O8	−71.4 (5)
O2—C2—C3—C4	−171.6 (4)	C4—C5—C12—O8	49.0 (5)
C1—C2—C3—C4	−53.1 (5)	C12—O8—C13—O9	4.4 (7)
C10—O6—C4—C3	105.3 (5)	C12—O8—C13—C14	−177.8 (5)
C10—O6—C4—C5	−134.2 (4)	O1—C1—N15—C16	−88.5 (6)
O4—C3—C4—O6	−69.3 (4)	C2—C1—N15—C16	151.9 (5)
C2—C3—C4—O6	172.3 (4)	C1—N15—C16—O17	174.7 (4)
O4—C3—C4—C5	171.5 (3)	C1—N15—C16—S1	−4.3 (7)
C2—C3—C4—C5	53.0 (5)	C17—O17—C16—N15	174.3 (5)
C1—O1—C5—C12	−171.2 (4)	C17—O17—C16—S1	−6.7 (7)
C1—O1—C5—C4	65.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15A···O5^i	0.81 (6)	2.08 (6)	2.884 (7)	175 (6)
C5—H5A···O9^ii	0.98	2.55	3.386 (7)	143

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