5,8,11-Trioxa-2,14-di­thia­bi­cyclo­[13.4.1]­icosa-1(19),15,17-trien-20-one

The title compound, C₁₅H₂₀O₄S₂, crystallizes in a chiral space group although it contains mirror symmetry. The tropone ring is inclined at an angle of 50.3 (1)° to the crown ether ring. The planarity of the tropone ring system itself is diminished by as much as 20.8 (4)°.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

C15H20O4S2	Dx = 1.346 Mg m^−3
Mr = 328.43	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 9.682 (5) Å	θ = 10.6–18.3°
b = 18.654 (5) Å	µ = 0.34 mm^−1
c = 8.977 (5) Å	T = 296 K
V = 1621.3 (13) Å^3	Prism, yellow
Z = 4	0.40 × 0.30 × 0.30 mm
F(000) = 696

Data collection

Enraf-Nonius FR590 diffractometer	1420 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 27.0°, θmin = 3.0°
ω–2θ scans	h = −12→0
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968)	k = 0→23
Tmin = 0.879, Tmax = 0.903	l = 0→11
2032 measured reflections	3 standard reflections every 120 min
2032 independent reflections	intensity decay: 1.3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 0.4494P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2032 reflections	Δρmax = 0.32 e Å^−3
190 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (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	0.75578 (12)	0.16943 (6)	0.60467 (12)	0.0591 (3)
S2	0.95524 (10)	0.09292 (5)	0.10713 (12)	0.0540 (3)
O1	0.9491 (3)	0.13814 (13)	0.3976 (3)	0.0542 (6)
O2	0.4435 (4)	0.14195 (19)	0.5079 (3)	0.0756 (9)
O3	0.4211 (4)	0.0656 (2)	0.2297 (4)	0.0883 (11)
O4	0.6484 (3)	0.06549 (15)	−0.0091 (4)	0.0651 (8)
C1	0.8522 (4)	0.16703 (18)	0.3311 (4)	0.0439 (8)
C2	0.8465 (4)	0.16256 (19)	0.1680 (4)	0.0453 (9)
C3	0.7810 (4)	0.2084 (2)	0.0728 (4)	0.0552 (11)
H3	0.8035	0.2025	−0.0271	0.066*
C4	0.6852 (4)	0.2629 (2)	0.1020 (6)	0.0638 (12)
H4	0.6599	0.2913	0.0212	0.077*
C5	0.6254 (5)	0.2791 (2)	0.2333 (5)	0.0627 (12)
H5	0.5614	0.3162	0.2298	0.075*
C6	0.6449 (4)	0.2487 (2)	0.3737 (5)	0.0576 (10)
H6	0.5836	0.2638	0.4470	0.069*
C7	0.7418 (4)	0.19962 (18)	0.4185 (4)	0.0485 (9)
C8	0.5926 (5)	0.1886 (3)	0.6934 (5)	0.0699 (13)
H8A	0.6065	0.1893	0.8004	0.084*
H8B	0.5630	0.2362	0.6635	0.084*
C9	0.4805 (5)	0.1370 (3)	0.6584 (5)	0.0765 (15)
H9A	0.5114	0.0886	0.6802	0.092*
H9B	0.4007	0.1471	0.7202	0.092*
C10	0.3329 (5)	0.0971 (3)	0.4689 (6)	0.0782 (14)
H10A	0.2501	0.1115	0.5219	0.094*
H10B	0.3539	0.0479	0.4956	0.094*
C11	0.3104 (5)	0.1028 (3)	0.3059 (6)	0.0874 (17)
H11A	0.2222	0.0815	0.2796	0.105*
H11B	0.3091	0.1528	0.2764	0.105*
C12	0.4169 (6)	0.0725 (3)	0.0787 (7)	0.0918 (17)
H12A	0.4318	0.1222	0.0514	0.110*
H12B	0.3269	0.0581	0.0421	0.110*
C13	0.5264 (5)	0.0266 (3)	0.0098 (6)	0.0753 (14)
H13A	0.5439	−0.0146	0.0731	0.090*
H13B	0.4947	0.0092	−0.0861	0.090*
C14	0.7572 (5)	0.0237 (2)	−0.0672 (5)	0.0638 (11)
H14A	0.7333	0.0072	−0.1664	0.077*
H14B	0.7716	−0.0180	−0.0046	0.077*
C15	0.8873 (4)	0.0674 (2)	−0.0737 (4)	0.0554 (10)
H15A	0.8693	0.1105	−0.1308	0.066*
H15B	0.9573	0.0401	−0.1264	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0616 (6)	0.0642 (6)	0.0515 (5)	0.0118 (6)	−0.0143 (6)	0.0011 (6)
S2	0.0479 (5)	0.0586 (5)	0.0555 (5)	0.0060 (5)	−0.0054 (5)	0.0073 (6)
O1	0.0480 (14)	0.0583 (14)	0.0563 (15)	0.0093 (13)	−0.0171 (16)	0.0036 (15)
O2	0.067 (2)	0.102 (2)	0.0584 (17)	−0.005 (2)	−0.0026 (18)	0.0070 (18)
O3	0.095 (3)	0.107 (3)	0.063 (2)	0.040 (2)	−0.010 (2)	−0.0088 (19)
O4	0.0577 (17)	0.0521 (16)	0.085 (2)	−0.0055 (15)	−0.0012 (18)	−0.0075 (16)
C1	0.0410 (19)	0.0362 (17)	0.054 (2)	−0.0059 (17)	−0.0140 (18)	0.0061 (17)
C2	0.0435 (19)	0.0393 (18)	0.053 (2)	−0.0056 (17)	−0.0086 (18)	0.0060 (17)
C3	0.065 (3)	0.049 (2)	0.051 (2)	0.0000 (19)	−0.014 (2)	0.0096 (19)
C4	0.073 (3)	0.050 (2)	0.068 (3)	0.007 (2)	−0.026 (3)	0.017 (2)
C5	0.061 (3)	0.048 (2)	0.079 (3)	0.014 (2)	−0.016 (3)	0.011 (2)
C6	0.055 (2)	0.053 (2)	0.065 (3)	0.009 (2)	−0.009 (2)	−0.001 (2)
C7	0.051 (2)	0.0424 (18)	0.052 (2)	−0.0023 (18)	−0.013 (2)	0.0018 (18)
C8	0.080 (3)	0.082 (3)	0.048 (2)	0.021 (3)	−0.008 (2)	−0.013 (2)
C9	0.069 (3)	0.111 (4)	0.050 (2)	0.020 (3)	0.006 (2)	0.010 (3)
C10	0.054 (3)	0.099 (4)	0.082 (3)	0.002 (3)	0.007 (3)	−0.018 (3)
C11	0.061 (3)	0.111 (4)	0.090 (4)	0.025 (3)	−0.016 (3)	−0.022 (4)
C12	0.088 (4)	0.078 (3)	0.110 (5)	−0.002 (3)	0.007 (4)	0.007 (4)
C13	0.076 (3)	0.067 (3)	0.083 (3)	−0.012 (3)	0.008 (3)	−0.004 (3)
C14	0.072 (3)	0.057 (2)	0.063 (3)	−0.005 (3)	−0.008 (3)	−0.005 (2)
C15	0.059 (2)	0.063 (2)	0.044 (2)	0.002 (2)	0.002 (2)	0.0044 (19)

Geometric parameters (Å, º)

S1—C7	1.769 (4)	C1—C7	1.459 (5)
S1—C8	1.805 (5)	C1—C2	1.467 (5)
S2—C2	1.760 (4)	C2—C3	1.365 (5)
S2—C15	1.815 (4)	C3—C4	1.401 (5)
O1—C1	1.236 (4)	C4—C5	1.348 (6)
O2—C9	1.401 (5)	C5—C6	1.394 (6)
O2—C10	1.404 (6)	C6—C7	1.371 (5)
O3—C12	1.362 (6)	C8—C9	1.485 (6)
O3—C11	1.448 (6)	C10—C11	1.483 (7)
O4—C13	1.396 (5)	C12—C13	1.497 (7)
O4—C14	1.411 (5)	C14—C15	1.502 (6)
C7—S1—C8	106.6 (2)	C4—C5—C6	129.9 (4)
C2—S2—C15	104.76 (19)	C7—C6—C5	129.0 (4)
C9—O2—C10	113.3 (4)	C6—C7—C1	128.4 (4)
C12—O3—C11	113.8 (4)	C6—C7—S1	122.9 (3)
C13—O4—C14	112.9 (3)	C1—C7—S1	108.6 (3)
O1—C1—C7	118.5 (3)	C9—C8—S1	114.7 (3)
O1—C1—C2	119.1 (4)	O2—C9—C8	110.4 (4)
C7—C1—C2	122.2 (3)	O2—C10—C11	108.4 (5)
C3—C2—C1	127.3 (4)	O3—C11—C10	108.8 (4)
C3—C2—S2	123.1 (3)	O3—C12—C13	109.7 (5)
C1—C2—S2	109.2 (3)	O4—C13—C12	110.6 (4)
C2—C3—C4	130.2 (4)	O4—C14—C15	109.9 (3)
C5—C4—C3	127.6 (4)	C14—C15—S2	114.3 (3)
O1—C1—C2—C3	−155.7 (4)	C2—C1—C7—S1	160.8 (3)
C7—C1—C2—C3	29.2 (6)	C8—S1—C7—C6	19.8 (4)
O1—C1—C2—S2	17.7 (4)	C8—S1—C7—C1	−163.4 (3)
C7—C1—C2—S2	−157.4 (3)	C7—S1—C8—C9	78.8 (4)
C15—S2—C2—C3	−29.8 (4)	C10—O2—C9—C8	−176.9 (4)
C15—S2—C2—C1	156.5 (3)	S1—C8—C9—O2	−66.9 (5)
C1—C2—C3—C4	−12.1 (7)	C9—O2—C10—C11	−175.7 (4)
S2—C2—C3—C4	175.3 (3)	C12—O3—C11—C10	−174.8 (5)
C2—C3—C4—C5	−6.2 (8)	O2—C10—C11—O3	73.0 (6)
C3—C4—C5—C6	2.3 (8)	C11—O3—C12—C13	−174.4 (4)
C4—C5—C6—C7	8.3 (8)	C14—O4—C13—C12	177.1 (4)
C5—C6—C7—C1	1.1 (7)	O3—C12—C13—O4	−91.7 (6)
C5—C6—C7—S1	177.3 (4)	C13—O4—C14—C15	−175.8 (4)
O1—C1—C7—C6	162.2 (4)	O4—C14—C15—S2	66.2 (4)
C2—C1—C7—C6	−22.6 (6)	C2—S2—C15—C14	−75.7 (3)
O1—C1—C7—S1	−14.4 (4)