Phenyl 2,3-O-isopropyl-idene-1-thio-α-d-rhamnopyran-oside.

In the title compound, C(15)H(20)O(4)S, a dioxolane ring is fused to the pyran ring of the sugar which carries a thio-phenyl substituent on the anomeric C atom. The dioxolane ring adopts an envelope conformation and the pyran ring system a distorted (4)C(1) chair. The structure is stabilized by O-H⋯O hydrogen bonds, forming centrosymmetric dimers that generate an R(2) (2)(10) ring motif. Additional C-H⋯O inter-actions form an extended network. Two C atoms of the phenyl ring are disordered over two positions; the site occupancy factors are ca. 0.7 and 0.3.

Related literature

For the background to angucyline anti­biotics, see: Carreno & Urbano (2005 ▶); Toshima (2003 ▶); Krohn & Rohr (1997 ▶); Rohr & Thiericke (1992 ▶). For previous reports of the title compound, see: Kerekgyarto et al., (1993 ▶); Yu & Wang, (2002 ▶). For related structures, see, for example: Yang et al. (2003 ▶); Wehlan et al. (2004 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C15H20O4S

M = 296.37

Monoclinic,

a = 24.3029 (12) Å

b = 5.3048 (3) Å

c = 12.0795 (7) Å

β = 97.014 (3)°

V = 1545.66 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 295 (2) K

0.37 × 0.30 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.723, T max = 0.983

17181 measured reflections

3318 independent reflections

2560 reflections with I > 2σ(I)

R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.144

S = 1.03

3318 reflections

204 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.37 e Å−3

Absolute structure: Flack (1983 ▶) 1392 Friedel pairs

Flack parameter: 0.03 (10)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97 and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807061004/ng2385sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061004/ng2385Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H20O4S	F000 = 632
Mr = 296.37	Dx = 1.274 Mg m−3
Monoclinic, C2	Mo Kα radiation λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 4464 reflections
a = 24.3029 (12) Å	θ = 5.1–53.9º
b = 5.3048 (3) Å	µ = 0.22 mm−1
c = 12.0795 (7) Å	T = 295 (2) K
β = 97.014 (3)º	Irregular fragment, colourless
V = 1545.66 (15) Å3	0.37 × 0.30 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	3318 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.060
T = 295(2) K	θmax = 27.1º
φ & ω scans	θmin = 1.7º
Absorption correction: multi-scan(SADABS; Bruker, 2004)	h = −30→30
Tmin = 0.723, Tmax = 0.983	k = −6→6
17181 measured reflections	l = −15→15

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.1017P)2 + ] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.144	(Δ/σ)max = 0.002
S = 1.04	Δρmax = 0.33 e Å−3
3318 reflections	Δρmin = −0.37 e Å−3
204 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983) 1392 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.03 (10)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.18083 (7)	0.4599 (4)	0.64558 (13)	0.0532 (4)
C1	0.17180 (10)	0.3676 (5)	0.75001 (19)	0.0463 (6)
H1	0.1818	0.5016	0.8046	0.056*
C2	0.11178 (10)	0.2973 (5)	0.7572 (2)	0.0463 (6)
H2	0.1093	0.1902	0.8225	0.056*
C3	0.08248 (9)	0.1708 (5)	0.6530 (2)	0.0496 (6)
H3	0.0887	−0.0116	0.6565	0.060*
C4	0.09941 (10)	0.2762 (5)	0.5457 (2)	0.0533 (6)
H4	0.0827	0.4433	0.5321	0.064*
O4	0.08181 (8)	0.1174 (5)	0.45401 (18)	0.0823 (8)
H4A	0.0497	0.1512	0.4298	0.123*
C5	0.16240 (11)	0.2999 (7)	0.5535 (2)	0.0642 (8)
H5	0.1796	0.1333	0.5644	0.077*
C6	0.18068 (16)	0.4260 (13)	0.4507 (3)	0.1080 (17)
H6A	0.1657	0.5935	0.4437	0.162*
H6B	0.1674	0.3300	0.3855	0.162*
H6C	0.2204	0.4338	0.4581	0.162*
O2	0.07846 (7)	0.5178 (3)	0.76344 (14)	0.0476 (4)
O3	0.02550 (7)	0.2257 (3)	0.66139 (16)	0.0527 (4)
C7	0.02277 (10)	0.4350 (5)	0.7378 (2)	0.0474 (5)
C8	−0.01126 (11)	0.6449 (5)	0.6803 (2)	0.0570 (7)
H8A	−0.0087	0.7914	0.7273	0.085*
H8B	−0.0493	0.5927	0.6657	0.085*
H8C	0.0025	0.6846	0.6111	0.085*
C9	−0.00051 (14)	0.3396 (9)	0.8398 (3)	0.0822 (10)
H9A	0.0235	0.2116	0.8751	0.123*
H9B	−0.0367	0.2698	0.8185	0.123*
H9C	−0.0031	0.4764	0.8909	0.123*
S1	0.21316 (3)	0.08767 (14)	0.79616 (7)	0.0730 (3)
C10	0.27881 (10)	0.2165 (5)	0.8419 (2)	0.0494 (6)
C11	0.3053 (4)	0.385 (3)	0.7765 (10)	0.077 (3)	0.66 (3)
H11	0.2869	0.4429	0.7094	0.092*	0.66 (3)
C12	0.3583 (4)	0.464 (3)	0.8110 (13)	0.100 (5)	0.66 (3)
H12	0.3765	0.5692	0.7659	0.120*	0.66 (3)
C11A	0.2958 (5)	0.456 (3)	0.8190 (18)	0.058 (4)	0.34 (3)
H11A	0.2721	0.5644	0.7752	0.070*	0.34 (3)
C12A	0.3488 (6)	0.534 (3)	0.8621 (19)	0.073 (4)	0.34 (3)
H12A	0.3587	0.7016	0.8523	0.088*	0.34 (3)
C13	0.38489 (15)	0.3843 (9)	0.9152 (3)	0.0866 (11)
H13	0.4178	0.4591	0.9460	0.104*
C14	0.36232 (13)	0.2024 (11)	0.9680 (3)	0.1015 (17)
H14	0.3821	0.1311	1.0310	0.122*
C15	0.30916 (13)	0.1145 (11)	0.9312 (3)	0.0966 (15)
H15	0.2944	−0.0170	0.9691	0.116*

	U11	U22	U33	U12	U13	U23
O1	0.0429 (9)	0.0662 (11)	0.0483 (10)	−0.0123 (8)	−0.0041 (7)	0.0024 (8)
C1	0.0379 (13)	0.0511 (13)	0.0457 (13)	−0.0075 (10)	−0.0115 (10)	0.0022 (10)
C2	0.0382 (12)	0.0517 (13)	0.0467 (13)	−0.0039 (10)	−0.0041 (10)	0.0062 (10)
C3	0.0297 (10)	0.0385 (11)	0.0767 (18)	−0.0033 (8)	−0.0093 (10)	−0.0065 (10)
C4	0.0415 (13)	0.0636 (15)	0.0507 (15)	0.0054 (12)	−0.0106 (10)	−0.0165 (12)
O4	0.0537 (11)	0.1026 (19)	0.0830 (14)	0.0181 (12)	−0.0224 (10)	−0.0498 (14)
C5	0.0432 (14)	0.091 (2)	0.0564 (16)	0.0000 (14)	−0.0021 (12)	−0.0170 (15)
C6	0.077 (2)	0.192 (5)	0.0571 (19)	−0.017 (3)	0.0178 (17)	−0.007 (3)
O2	0.0397 (9)	0.0506 (10)	0.0503 (9)	−0.0060 (6)	−0.0029 (7)	−0.0082 (7)
O3	0.0337 (8)	0.0411 (9)	0.0796 (12)	−0.0055 (6)	−0.0078 (8)	−0.0083 (8)
C7	0.0386 (12)	0.0497 (12)	0.0528 (14)	−0.0065 (10)	0.0007 (10)	−0.0012 (10)
C8	0.0496 (15)	0.0457 (14)	0.0727 (18)	0.0014 (10)	−0.0040 (12)	−0.0037 (11)
C9	0.0603 (19)	0.111 (3)	0.077 (2)	−0.0063 (18)	0.0179 (16)	0.020 (2)
S1	0.0472 (4)	0.0536 (4)	0.1102 (6)	−0.0067 (3)	−0.0231 (4)	0.0170 (4)
C10	0.0322 (11)	0.0581 (15)	0.0554 (15)	0.0026 (10)	−0.0045 (10)	0.0056 (11)
C11	0.053 (4)	0.113 (7)	0.060 (5)	−0.021 (4)	−0.014 (3)	0.036 (5)
C12	0.050 (4)	0.151 (10)	0.093 (7)	−0.025 (5)	−0.016 (4)	0.063 (7)
C11A	0.031 (4)	0.072 (6)	0.070 (9)	0.014 (4)	0.006 (5)	−0.005 (6)
C12A	0.044 (6)	0.076 (7)	0.102 (11)	−0.020 (4)	0.021 (7)	−0.025 (7)
C13	0.0476 (17)	0.116 (3)	0.090 (2)	−0.0140 (19)	−0.0161 (16)	0.012 (2)
C14	0.0487 (17)	0.180 (5)	0.070 (2)	−0.007 (2)	−0.0170 (15)	0.045 (3)
C15	0.0522 (16)	0.158 (4)	0.075 (2)	−0.017 (2)	−0.0119 (14)	0.057 (3)

O1—C1	1.395 (3)	C8—H8A	0.9600
O1—C5	1.427 (3)	C8—H8B	0.9600
C1—C2	1.518 (3)	C8—H8C	0.9600
C1—S1	1.841 (3)	C9—H9A	0.9600
C1—H1	0.9800	C9—H9B	0.9600
C2—O2	1.429 (3)	C9—H9C	0.9600
C2—C3	1.525 (3)	S1—C10	1.762 (3)
C2—H2	0.9800	C10—C15	1.344 (4)
C3—O3	1.431 (3)	C10—C11	1.400 (8)
C3—C4	1.514 (4)	C10—C11A	1.374 (15)
C3—H3	0.9800	C11—C12	1.369 (10)
C4—O4	1.415 (3)	C11—H11	0.9300
C4—C5	1.527 (4)	C12—C13	1.407 (9)
C4—H4	0.9800	C12—H12	0.9300
O4—H4A	0.8200	C11A—C12A	1.394 (19)
C5—C6	1.524 (5)	C11A—H11A	0.9300
C5—H5	0.9800	C12A—C13	1.295 (18)
C6—H6A	0.9600	C12A—H12A	0.9300
C6—H6B	0.9600	C13—C14	1.313 (6)
C6—H6C	0.9600	C13—H13	0.9300
O2—C7	1.421 (3)	C14—C15	1.394 (5)
O3—C7	1.450 (3)	C14—H14	0.9300
C7—C9	1.506 (4)	C15—H15	0.9300
C7—C8	1.505 (3)
C1—O1—C5	115.3 (2)	O3—C7—C8	109.76 (19)
O1—C1—C2	113.34 (19)	C9—C7—C8	112.7 (3)
O1—C1—S1	114.62 (18)	C7—C8—H8A	109.5
C2—C1—S1	106.12 (17)	C7—C8—H8B	109.5
O1—C1—H1	107.5	H8A—C8—H8B	109.5
C2—C1—H1	107.5	C7—C8—H8C	109.5
S1—C1—H1	107.5	H8A—C8—H8C	109.5
O2—C2—C1	110.9 (2)	H8B—C8—H8C	109.5
O2—C2—C3	101.14 (19)	C7—C9—H9A	109.5
C1—C2—C3	114.6 (2)	C7—C9—H9B	109.5
O2—C2—H2	110.0	H9A—C9—H9B	109.5
C1—C2—H2	110.0	C7—C9—H9C	109.5
C3—C2—H2	110.0	H9A—C9—H9C	109.5
O3—C3—C4	110.6 (2)	H9B—C9—H9C	109.5
O3—C3—C2	102.1 (2)	C10—S1—C1	102.83 (12)
C4—C3—C2	113.3 (2)	C15—C10—C11	117.7 (4)
O3—C3—H3	110.2	C15—C10—C11A	112.7 (8)
C4—C3—H3	110.2	C15—C10—S1	118.9 (3)
C2—C3—H3	110.2	C11—C10—S1	122.1 (3)
O4—C4—C3	111.2 (2)	C11A—C10—S1	125.3 (6)
O4—C4—C5	107.6 (2)	C12—C11—C10	120.2 (6)
C3—C4—C5	110.6 (2)	C12—C11—H11	119.9
O4—C4—H4	109.1	C10—C11—H11	119.9
C3—C4—H4	109.1	C11—C12—C13	119.5 (6)
C5—C4—H4	109.1	C11—C12—H12	120.2
C4—O4—H4A	109.5	C13—C12—H12	120.2
O1—C5—C4	108.3 (2)	C10—C11A—C12A	119.1 (11)
O1—C5—C6	106.2 (3)	C10—C11A—H11A	120.4
C4—C5—C6	112.0 (3)	C12A—C11A—H11A	120.4
O1—C5—H5	110.1	C13—C12A—C11A	122.8 (12)
C4—C5—H5	110.1	C13—C12A—H12A	118.6
C6—C5—H5	110.1	C11A—C12A—H12A	118.6
C5—C6—H6A	109.5	C14—C13—C12A	113.2 (8)
C5—C6—H6B	109.5	C14—C13—C12	118.7 (5)
H6A—C6—H6B	109.5	C14—C13—H13	120.6
C5—C6—H6C	109.5	C12A—C13—H13	115.7
H6A—C6—H6C	109.5	C12—C13—H13	120.6
H6B—C6—H6C	109.5	C13—C14—C15	121.1 (3)
C7—O2—C2	105.45 (18)	C13—C14—H14	119.4
C3—O3—C7	108.72 (17)	C15—C14—H14	119.4
O2—C7—O3	105.01 (18)	C10—C15—C14	121.2 (4)
O2—C7—C9	111.6 (2)	C10—C15—H15	119.4
O3—C7—C9	108.3 (3)	C14—C15—H15	119.4
O2—C7—C8	109.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3i	0.82	2.05	2.861 (2)	169
C8—H8A···O3ii	0.96	2.61	3.224 (3)	122
C14—H14···O2iii	0.93	2.62	3.524 (4)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3i	0.82	2.05	2.861 (2)	169
C8—H8A⋯O3ii	0.96	2.61	3.224 (3)	122
C14—H14⋯O2iii	0.93	2.62	3.524 (4)	164

Symmetry codes: (i) ; (ii) ; (iii) .