Johnson orthoester Claisen rearrangement products of some (1-oxa-4-thiaspiro[4.5]dec-6-en-6-yl)alkanols

The crystal structures of two 1-oxa-4-thia­spiro­[4.5]­decane derivatives, ethyl 6-benzyl­idene-1-oxa-4-thia­spiro­[4.5]­decane-7-acetate, C₁₉H₂₄O₃S, and (6-ethyl­idene-1-oxa-4-thia­spiro­[4.5]­decan-7-yl)­ethyl 4-bromo­benzoate, C₁₉H₂₃BrO₃S, obtained under Johnson orthoester Claisen rearrangement conditions, exhibit different olefin geometry. Both structures are composed of independent mol­ecules separated by normal van der Waals distances. The S-Csp³ bond distances are significantly different from each other, as has been observed in similar structures; the remaining molecular dimensions are as expected.

S1. Comment

In studies of 1,3-diastereoface selection under Johnson orthoester Claisen rearrangement conditions, we have reacted (1-oxa-4-thiaspiro[4.5]dec-6-en-6-yl)(phenyl)methanol, (I) and (1-oxa-4-thiaspiro[4.5]dec-6-en-6-yl)(methyl)methanol, (II) with triethyl orthoacetate. Whereas (I) furnished a single product identified as ethyl 6-benzylidene-1-oxa-4-thiaspiro[4.5]decane-7-acetate, (III), (II) furnished a mixture of two products which were inseparable by routine chromatographic techniques. However, the corresponding alcohols, obtained on LiAlH₄ reduction in Et₂O, separated well by radial chromatography. The more polar alcohol was identified, from its 4-bromobenzoate ester derivative, as 2-(6-ethylidene-1-oxa-4-thiaspiro[4.5]decan-7-yl)ethanol, (IV). Since (IV) is a consequence of rearrangement anti to the acetal sulfur, the less polar alcohol must, therefore, be a product of rearrangement syn to the acetal sulfur and possess the stereostructure shown for (V). Compound (III) is also a consequence of rearrangement syn to the acetal sulfur. The difference in the olefin geometry of (IV) from that of (III) and (V) must be noted. In this paper, we describe the crystal structures of (III) and of the 4-bromobenzoate ester of (IV), (VI). \sch

The structures of (III) and (VI) are presented in Figs. 1 and 2, respectively, and are composed of independent molecules separated by normal van der Waals distances. One C atom of the heterocyclic ring in (III) is disordered over two sites, C1 and C1*, with nonequivalent site occupancy factors of 0.58 (2) and 0.42 (2), respectively, indicating the presence of two conformations of the five-membered ring. It is interesting to note that in (III), as a result of the disorder, the rings S1/C1/C2/O1/C3 and S1/C1*/C2/O1/C3 adopt C2- and S1-envelope conformations, with atoms S1 and C2 0.773 (19) and 0.554 (11) Å, respectively, out of the planes of the remaining ring atoms [maximum deviations 0.009 (5) and 0.014 (4) Å, respectively]. The corresponding heterocyclic ring in (VI) adopts a C2-envelope conformation, with C2 0.542 (9) Å out of the plane formed by the remaining ring atoms [maximium deviation 0.030 (3) Å for C3]. In both structures the six-membered ring C3—C8 adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.539 (6) and 0.590 (6) Å, and θ = 171.0 (6) and 5.1 (6) and ϕ = 69 (4) and 83 (6)°, in (III) and (VI), respectively. The phenyl rings in both the structures are essentially planar.

The bond distances and angles in the two structures are normal and agree well with the corresponding values reported for similar compounds in the Cambridge Structural Database (Allen & Kennard, 1993). The S—C_sp3 bond distances, although significantly different from each other in (III) [1.880 (5) Å for S—C3, and a mean of 1.811 (5) Å for S—C1 and S—C1*], are in excellent agreement with the corresponding bond distances in (VI) [1.878 (5) and 1.798 (6) Å]. Similar nonequivalent S—C bond distances have been reported in the crystal structures of cyclohexanespiro-2'-(1',3'-oxathiolan-5'-one 3'-oxide) (Frechina et al., 1992), (+)-(3S,4R)-6-phenyl-1-oxa-4-thiaspiro[4.5]decan-8-one (Sonoda et al., 1992), two derivatives of an oxa-thia-spiro-decene (Parvez et al., 1997) and 2-(7-ethylidene-6-methyl-1-oxa-4-thiaspiro[4.5]dec-7-yl)ethanol (Parvez et al., 1998).

S2. Experimental

Compound (III) was prepared by the Johnson orthoester Claisen rearrangement of (I) on treatment with triethylorthoacetate in toluene at reflux under nitrogen. A similar reaction using (II) furnished an ester which was reduced with lithium aluminium hydride in diethyl ether at 253–273 K to generate the alcohol (IV). Alcohol (IV) was then esterified with 4-bromobenzoyl chloride following standard methods to obtain (VI).

S3. Refinement

One C atom of the heterocyclic ring in (III) was disordered over two sites, C1 and C1*, with nonequivalent site occupancy factors of 0.58 (2) and 0.42 (2), respectively. For both compounds (III) and (VI) most of the H atoms were located from difference Fourier syntheses but these were included in the refinements at geometrically idealized positions with C—H 0.93–1.00 Å, utilizing a riding model and isotropic displacement parameters. Although the starting material for (III) was a racemic mixture of diastereomers, the final product of (III) crystallized in a non-centrosymmetric space group. However, its absolute structure could not be determined because the equivalent reflections were not collected. The Flack parameter (Flack, 1983) for the inverted structure was 0.12 (18).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (III); CAD-4 Software (Enraf-Nonius, 1989) for (VI). Cell refinement: MSC/AFC Diffractometer Control Software for (III); CAD-4 Software for (VI). For both compounds, data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The ORTEPII (Johnson, 1976) drawing of (III) with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. ORTEPII (Johnson, 1976) drawing of (VI) with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii.

(III) ethyl 6-benzylidene-1-oxa-4-thiaspiro[4.5]decane-7-acetate

Crystal data

C19H24O3S	F(000) = 712
Mr = 332.44	Dx = 1.269 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 10.369 (2) Å	θ = 10–15°
b = 20.791 (3) Å	µ = 0.20 mm^−1
c = 8.071 (3) Å	T = 170 K
V = 1740.0 (8) Å^3	Plate, colourless
Z = 4	0.52 × 0.48 × 0.14 mm

Data collection

Rigaku AFC-6S diffractometer	1147 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.00
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
ω/2θ scans	h = 0→13
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968)	k = 0→27
Tmin = 0.90, Tmax = 0.97	l = 0→10
2150 measured reflections	3 standard reflections every 200 reflections
2150 independent reflections	intensity decay: <0.1%

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.82P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.01
2150 reflections	Δρmax = 0.33 e Å^−3
219 parameters	Δρmin = −0.28 e Å^−3
1 restraint	Absolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (18)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.93535 (13)	0.19996 (7)	0.76797 (19)	0.0381 (3)
O1	0.9410 (3)	0.09980 (18)	0.9678 (4)	0.0359 (9)
O2	1.4073 (3)	0.1698 (2)	0.4511 (5)	0.0416 (10)
O3	1.2621 (4)	0.2080 (2)	0.2721 (7)	0.0625 (13)
C1	0.8669 (12)	0.2086 (6)	0.9739 (14)	0.048 (4)	0.58 (2)
H1A	0.8865	0.2514	1.0210	0.058*	0.58 (2)
H1B	0.7723	0.2023	0.9720	0.058*	0.58 (2)
C1*	0.9642 (19)	0.2133 (7)	0.9860 (18)	0.043 (5)	0.42 (2)
H1*1	1.0561	0.2240	1.0050	0.051*	0.42 (2)
H1*2	0.9107	0.2494	1.0265	0.051*	0.42 (2)
C2	0.9318 (6)	0.1565 (3)	1.0699 (7)	0.0497 (16)
H2A	1.0191	0.1707	1.1037	0.060*
H2B	0.8816	0.1468	1.1712	0.060*
C3	0.9849 (5)	0.1142 (2)	0.8052 (6)	0.0253 (12)
C4	1.1324 (4)	0.1093 (2)	0.7915 (6)	0.0242 (11)
C5	1.1871 (5)	0.1132 (3)	0.6168 (6)	0.0270 (12)
H5	1.2770	0.0958	0.6216	0.032*
C6	1.1108 (5)	0.0698 (3)	0.4980 (7)	0.0320 (12)
H6A	1.1405	0.0778	0.3832	0.038*
H6B	1.1292	0.0243	0.5248	0.038*
C7	0.9653 (5)	0.0810 (3)	0.5070 (7)	0.0382 (14)
H7A	0.9206	0.0509	0.4312	0.046*
H7B	0.9451	0.1255	0.4716	0.046*
C8	0.9177 (5)	0.0703 (3)	0.6857 (7)	0.0351 (13)
H8A	0.8236	0.0781	0.6908	0.042*
H8B	0.9335	0.0251	0.7181	0.042*
C9	1.2005 (5)	0.0950 (2)	0.9241 (7)	0.0301 (13)
H9	1.1525	0.0905	1.0237	0.036*
C10	1.3436 (5)	0.0846 (2)	0.9401 (7)	0.0297 (11)
C11	1.3869 (5)	0.0379 (3)	1.0489 (8)	0.0412 (14)
H11	1.3265	0.0130	1.1100	0.049*
C12	1.5183 (5)	0.0271 (3)	1.0690 (8)	0.0450 (16)
H12	1.5468	−0.0054	1.1432	0.054*
C13	1.6062 (5)	0.0623 (3)	0.9845 (8)	0.0434 (15)
H13	1.6958	0.0544	0.9987	0.052*
C14	1.5649 (5)	0.1092 (3)	0.8785 (7)	0.0363 (13)
H14	1.6264	0.1342	0.8197	0.044*
C15	1.4332 (5)	0.1210 (2)	0.8552 (6)	0.0301 (11)
H15	1.4057	0.1539	0.7815	0.036*
C16	1.1965 (5)	0.1821 (3)	0.5509 (6)	0.0324 (12)
H16A	1.1098	0.1964	0.5149	0.039*
H16B	1.2246	0.2108	0.6419	0.039*
C17	1.2895 (5)	0.1891 (3)	0.4068 (7)	0.0341 (13)
C18	1.5085 (5)	0.1752 (3)	0.3257 (7)	0.0379 (13)
H18A	1.5249	0.2208	0.2983	0.045*
H18B	1.4832	0.1522	0.2233	0.045*
C19	1.6257 (6)	0.1451 (3)	0.4004 (9)	0.0540 (18)
H19A	1.6477	0.1675	0.5034	0.081*
H19B	1.6979	0.1484	0.3225	0.081*
H19C	1.6084	0.0997	0.4244	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0411 (7)	0.0432 (7)	0.0301 (6)	0.0125 (7)	0.0059 (9)	0.0007 (7)
O1	0.0305 (19)	0.053 (2)	0.0245 (19)	−0.0032 (18)	0.0058 (18)	0.0061 (18)
O2	0.032 (2)	0.068 (3)	0.025 (2)	0.0022 (19)	0.0057 (17)	0.010 (2)
O3	0.045 (2)	0.110 (4)	0.032 (2)	0.016 (2)	0.011 (3)	0.031 (3)
C1	0.032 (7)	0.071 (8)	0.042 (6)	0.002 (5)	0.007 (5)	−0.020 (6)
C1*	0.060 (13)	0.036 (9)	0.032 (8)	−0.002 (7)	−0.005 (8)	−0.005 (6)
C2	0.049 (4)	0.073 (4)	0.027 (3)	0.001 (4)	0.006 (3)	−0.008 (3)
C3	0.024 (2)	0.026 (3)	0.026 (3)	0.002 (2)	0.002 (2)	0.006 (2)
C4	0.029 (2)	0.018 (2)	0.026 (3)	0.0025 (19)	0.002 (2)	0.002 (2)
C5	0.025 (3)	0.040 (3)	0.016 (2)	0.002 (2)	0.003 (2)	0.001 (2)
C6	0.036 (3)	0.034 (3)	0.026 (3)	−0.001 (2)	0.003 (2)	−0.005 (2)
C7	0.036 (3)	0.050 (4)	0.029 (3)	−0.007 (3)	−0.006 (3)	−0.008 (3)
C8	0.026 (3)	0.045 (3)	0.035 (3)	−0.003 (3)	0.006 (2)	−0.005 (3)
C9	0.025 (3)	0.036 (3)	0.029 (3)	−0.002 (2)	0.007 (2)	0.000 (2)
C10	0.030 (3)	0.034 (3)	0.026 (3)	0.003 (2)	−0.003 (2)	0.001 (2)
C11	0.037 (3)	0.047 (3)	0.040 (3)	−0.004 (3)	−0.005 (3)	0.005 (3)
C12	0.042 (3)	0.050 (4)	0.043 (4)	0.007 (3)	−0.012 (3)	0.016 (3)
C13	0.023 (2)	0.059 (4)	0.048 (4)	0.010 (3)	−0.004 (3)	−0.008 (3)
C14	0.029 (3)	0.046 (3)	0.034 (3)	−0.002 (3)	0.003 (3)	−0.005 (3)
C15	0.030 (3)	0.035 (3)	0.026 (3)	−0.003 (2)	−0.008 (2)	−0.001 (2)
C16	0.029 (3)	0.046 (3)	0.023 (3)	0.000 (2)	0.004 (2)	0.004 (2)
C17	0.029 (3)	0.046 (4)	0.027 (3)	0.000 (2)	0.005 (2)	0.003 (3)
C18	0.037 (3)	0.053 (3)	0.024 (3)	−0.006 (3)	0.010 (2)	0.007 (3)
C19	0.038 (3)	0.081 (5)	0.043 (4)	0.005 (3)	0.007 (3)	0.006 (4)

Geometric parameters (Å, º)

S1—C1*	1.806 (14)	C7—H7A	0.9900
S1—C1	1.816 (11)	C7—H7B	0.9900
S1—C3	1.880 (5)	C8—H8A	0.9900
O1—C3	1.421 (6)	C8—H8B	0.9900
O1—C2	1.442 (7)	C9—C10	1.506 (7)
O2—C17	1.335 (6)	C9—H9	0.9500
O2—C18	1.462 (6)	C10—C15	1.381 (7)
O3—C17	1.191 (7)	C10—C11	1.385 (8)
C1—C2	1.491 (13)	C11—C12	1.390 (8)
C1—H1A	0.9900	C11—H11	0.9500
C1—H1B	0.9900	C12—C13	1.352 (8)
C1*—C2	1.401 (15)	C12—H12	0.9500
C1*—H1*1	0.9900	C13—C14	1.366 (8)
C1*—H1*2	0.9900	C13—H13	0.9500
C2—H2A	0.9900	C14—C15	1.400 (7)
C2—H2B	0.9900	C14—H14	0.9500
C3—C8	1.499 (7)	C15—H15	0.9500
C3—C4	1.537 (6)	C16—C17	1.517 (7)
C4—C9	1.317 (7)	C16—H16A	0.9900
C4—C5	1.522 (7)	C16—H16B	0.9900
C5—C16	1.532 (7)	C18—C19	1.493 (8)
C5—C6	1.536 (7)	C18—H18A	0.9900
C5—H5	1.0000	C18—H18B	0.9900
C6—C7	1.528 (7)	C19—H19A	0.9800
C6—H6A	0.9900	C19—H19B	0.9800
C6—H6B	0.9900	C19—H19C	0.9800
C7—C8	1.541 (8)
C1*—S1—C1	32.7 (6)	C6—C7—H7B	109.7
C1*—S1—C3	86.8 (5)	C8—C7—H7B	109.7
C1—S1—C3	93.1 (4)	H7A—C7—H7B	108.2
C3—O1—C2	112.1 (4)	C3—C8—C7	111.4 (4)
C17—O2—C18	116.7 (4)	C3—C8—H8A	109.3
C2—C1—S1	103.2 (6)	C7—C8—H8A	109.3
C2—C1—H1A	111.1	C3—C8—H8B	109.3
S1—C1—H1A	111.1	C7—C8—H8B	109.3
C2—C1—H1B	111.1	H8A—C8—H8B	108.0
S1—C1—H1B	111.1	C4—C9—C10	129.1 (5)
H1A—C1—H1B	109.1	C4—C9—H9	115.4
C2—C1*—S1	107.6 (9)	C10—C9—H9	115.4
C2—C1*—H1*1	110.2	C15—C10—C11	118.8 (5)
S1—C1*—H1*1	110.2	C15—C10—C9	122.8 (5)
C2—C1*—H1*2	110.2	C11—C10—C9	118.3 (5)
S1—C1*—H1*2	110.2	C10—C11—C12	120.3 (5)
H1*1—C1*—H1*2	108.5	C10—C11—H11	119.9
C1*—C2—O1	113.4 (7)	C12—C11—H11	119.9
C1*—C2—C1	41.1 (8)	C13—C12—C11	121.0 (5)
O1—C2—C1	109.0 (6)	C13—C12—H12	119.5
C1*—C2—H2A	70.3	C11—C12—H12	119.5
O1—C2—H2A	109.9	C12—C13—C14	119.3 (5)
C1—C2—H2A	109.9	C12—C13—H13	120.3
C1*—C2—H2B	134.2	C14—C13—H13	120.3
O1—C2—H2B	109.9	C13—C14—C15	121.0 (5)
C1—C2—H2B	109.9	C13—C14—H14	119.5
H2A—C2—H2B	108.3	C15—C14—H14	119.5
O1—C3—C8	108.5 (4)	C10—C15—C14	119.5 (5)
O1—C3—C4	111.8 (4)	C10—C15—H15	120.2
C8—C3—C4	112.1 (4)	C14—C15—H15	120.2
O1—C3—S1	105.0 (3)	C17—C16—C5	113.3 (4)
C8—C3—S1	110.3 (4)	C17—C16—H16A	108.9
C4—C3—S1	108.8 (3)	C5—C16—H16A	108.9
C9—C4—C5	124.4 (4)	C17—C16—H16B	108.9
C9—C4—C3	119.3 (5)	C5—C16—H16B	108.9
C5—C4—C3	115.7 (4)	H16A—C16—H16B	107.7
C4—C5—C16	113.3 (4)	O3—C17—O2	124.2 (5)
C4—C5—C6	110.8 (4)	O3—C17—C16	125.4 (5)
C16—C5—C6	111.4 (4)	O2—C17—C16	110.4 (4)
C4—C5—H5	107.0	O2—C18—C19	105.8 (5)
C16—C5—H5	107.0	O2—C18—H18A	110.6
C6—C5—H5	107.0	C19—C18—H18A	110.6
C7—C6—C5	112.9 (4)	O2—C18—H18B	110.6
C7—C6—H6A	109.0	C19—C18—H18B	110.6
C5—C6—H6A	109.0	H18A—C18—H18B	108.7
C7—C6—H6B	109.0	C18—C19—H19A	109.5
C5—C6—H6B	109.0	C18—C19—H19B	109.5
H6A—C6—H6B	107.8	H19A—C19—H19B	109.5
C6—C7—C8	109.8 (5)	C18—C19—H19C	109.5
C6—C7—H7A	109.7	H19A—C19—H19C	109.5
C8—C7—H7A	109.7	H19B—C19—H19C	109.5
C1*—S1—C1—C2	−58.0 (10)	C3—C4—C5—C6	−46.1 (6)
C3—S1—C1—C2	21.2 (7)	C4—C5—C6—C7	50.9 (6)
C1—S1—C1*—C2	67.3 (13)	C16—C5—C6—C7	−76.1 (6)
C3—S1—C1*—C2	−33.5 (10)	C5—C6—C7—C8	−57.4 (6)
S1—C1*—C2—O1	25.3 (13)	O1—C3—C8—C7	−177.3 (4)
S1—C1*—C2—C1	−67.2 (11)	C4—C3—C8—C7	−53.4 (6)
C3—O1—C2—C1*	1.8 (11)	S1—C3—C8—C7	68.1 (5)
C3—O1—C2—C1	45.7 (7)	C6—C7—C8—C3	58.3 (6)
S1—C1—C2—C1*	63.9 (11)	C5—C4—C9—C10	5.4 (9)
S1—C1—C2—O1	−40.2 (8)	C3—C4—C9—C10	176.9 (5)
C2—O1—C3—C8	−144.5 (4)	C4—C9—C10—C15	38.6 (9)
C2—O1—C3—C4	91.4 (5)	C4—C9—C10—C11	−143.5 (6)
C2—O1—C3—S1	−26.5 (5)	C15—C10—C11—C12	−1.3 (9)
C1*—S1—C3—O1	33.9 (7)	C9—C10—C11—C12	−179.3 (6)
C1—S1—C3—O1	1.8 (5)	C10—C11—C12—C13	0.6 (10)
C1*—S1—C3—C8	150.7 (7)	C11—C12—C13—C14	0.3 (10)
C1—S1—C3—C8	118.6 (5)	C12—C13—C14—C15	−0.5 (9)
C1*—S1—C3—C4	−85.9 (7)	C11—C10—C15—C14	1.1 (8)
C1—S1—C3—C4	−118.0 (5)	C9—C10—C15—C14	179.0 (5)
O1—C3—C4—C9	−1.8 (7)	C13—C14—C15—C10	−0.3 (8)
C8—C3—C4—C9	−123.9 (5)	C4—C5—C16—C17	160.5 (4)
S1—C3—C4—C9	113.8 (5)	C6—C5—C16—C17	−73.7 (5)
O1—C3—C4—C5	170.5 (4)	C18—O2—C17—O3	2.5 (9)
C8—C3—C4—C5	48.4 (6)	C18—O2—C17—C16	−178.6 (4)
S1—C3—C4—C5	−73.9 (5)	C5—C16—C17—O3	120.7 (7)
C9—C4—C5—C16	−108.2 (6)	C5—C16—C17—O2	−58.2 (6)
C3—C4—C5—C16	79.9 (5)	C17—O2—C18—C19	−174.8 (5)
C9—C4—C5—C6	125.7 (5)

(VI) 2-(6-ethylidene-1-oxa-4-thiaspiro[4.5]decan-7-yl)ethyl 4-bromobenzoate

Crystal data

C19H23BrO3S	F(000) = 848
Mr = 411.34	Dx = 1.477 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 7.243 (2) Å	Cell parameters from 25 reflections
b = 11.541 (1) Å	θ = 20–30°
c = 22.180 (5) Å	µ = 4.20 mm^−1
β = 94.09 (2)°	T = 293 K
V = 1849.3 (7) Å^3	Needle, colourless
Z = 4	0.30 × 0.16 × 0.10 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2207 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.03
Graphite monochromator	θmax = 68°, θmin = 5°
ω/2θ scans	h = 0→8
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968)	k = 0→13
Tmin = 0.37, Tmax = 0.68	l = −26→26
3651 measured reflections	3 standard reflections every 200 reflections
3372 independent reflections	intensity decay: <0.1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0736P)^2 + 2.357P] where P = (Fo^2 + 2Fc^2)/3
3372 reflections	(Δ/σ)max < 0.01
217 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.83 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	1.21939 (9)	−0.37684 (6)	−0.32880 (3)	0.0713 (3)
S1	−0.2539 (2)	−0.36685 (12)	−0.04414 (6)	0.0555 (4)
O1	−0.1207 (5)	−0.2545 (3)	0.05246 (16)	0.0561 (10)
O2	0.4492 (5)	−0.3296 (3)	−0.17692 (14)	0.0468 (9)
O3	0.4897 (6)	−0.5198 (3)	−0.16423 (19)	0.0669 (11)
C1	−0.2675 (10)	−0.4330 (6)	0.0288 (3)	0.0734 (19)
H1A	−0.3885	−0.4208	0.0439	0.088*
H1B	−0.2439	−0.5156	0.0269	0.088*
C2	−0.1219 (11)	−0.3739 (6)	0.0675 (3)	0.0740 (19)
H2A	−0.1458	−0.3833	0.1097	0.089*
H2B	−0.0023	−0.4079	0.0613	0.089*
C3	−0.1267 (7)	−0.2373 (4)	−0.0112 (2)	0.0428 (11)
C4	0.0595 (6)	−0.2278 (4)	−0.0373 (2)	0.0383 (11)
C5	0.0341 (7)	−0.2095 (4)	−0.1055 (2)	0.0425 (11)
H5	−0.0458	−0.2723	−0.1217	0.051*
C6	−0.0726 (7)	−0.0961 (5)	−0.1178 (3)	0.0529 (13)
H6A	−0.0007	−0.0319	−0.1004	0.063*
H6B	−0.0903	−0.0836	−0.1611	0.063*
C7	−0.2558 (7)	−0.0993 (5)	−0.0916 (3)	0.0585 (15)
H7A	−0.3328	−0.1577	−0.1123	0.070*
H7B	−0.3165	−0.0249	−0.0979	0.070*
C8	−0.2376 (7)	−0.1266 (5)	−0.0239 (3)	0.0533 (13)
H8A	−0.1766	−0.0625	−0.0023	0.064*
H8B	−0.3599	−0.1354	−0.0093	0.064*
C9	0.2215 (7)	−0.2251 (5)	−0.0066 (2)	0.0486 (12)
H9	0.3210	−0.2182	−0.0306	0.058*
C10	0.2766 (9)	−0.2311 (6)	0.0602 (2)	0.0687 (18)
H10A	0.4088	−0.2256	0.0666	0.103*
H10B	0.2358	−0.3034	0.0760	0.103*
H10C	0.2202	−0.1682	0.0804	0.103*
C11	0.2104 (7)	−0.2135 (5)	−0.1396 (2)	0.0460 (12)
H11A	0.1821	−0.1871	−0.1807	0.055*
H11B	0.3012	−0.1610	−0.1204	0.055*
C12	0.2925 (7)	−0.3342 (5)	−0.1409 (2)	0.0497 (13)
H12A	0.3307	−0.3595	−0.1002	0.060*
H12B	0.2014	−0.3885	−0.1583	0.060*
C13	0.5375 (7)	−0.4287 (5)	−0.1841 (2)	0.0467 (12)
C14	0.7036 (7)	−0.4138 (4)	−0.2188 (2)	0.0421 (11)
C15	0.8280 (8)	−0.5035 (5)	−0.2202 (2)	0.0549 (14)
H15	0.8072	−0.5710	−0.1988	0.066*
C16	0.9834 (8)	−0.4955 (5)	−0.2526 (3)	0.0600 (15)
H16	1.0662	−0.5569	−0.2541	0.072*
C17	1.0120 (8)	−0.3923 (5)	−0.2832 (2)	0.0500 (13)
C18	0.8921 (8)	−0.3003 (5)	−0.2806 (2)	0.0565 (14)
H18	0.9149	−0.2311	−0.3003	0.068*
C19	0.7390 (7)	−0.3127 (5)	−0.2487 (2)	0.0531 (14)
H19	0.6565	−0.2512	−0.2472	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0631 (4)	0.0805 (5)	0.0740 (5)	0.0032 (4)	0.0311 (3)	−0.0040 (4)
S1	0.0572 (8)	0.0511 (8)	0.0589 (8)	−0.0150 (7)	0.0081 (6)	0.0042 (7)
O1	0.066 (2)	0.062 (2)	0.044 (2)	0.001 (2)	0.0207 (18)	−0.0003 (17)
O2	0.054 (2)	0.046 (2)	0.0434 (18)	−0.0013 (17)	0.0222 (16)	0.0017 (15)
O3	0.081 (3)	0.043 (2)	0.082 (3)	−0.009 (2)	0.035 (2)	−0.002 (2)
C1	0.092 (5)	0.061 (4)	0.071 (4)	−0.008 (4)	0.027 (4)	0.015 (3)
C2	0.100 (5)	0.073 (4)	0.051 (3)	0.011 (4)	0.014 (3)	0.017 (3)
C3	0.043 (3)	0.048 (3)	0.038 (3)	−0.003 (2)	0.009 (2)	−0.002 (2)
C4	0.040 (3)	0.038 (3)	0.037 (2)	0.000 (2)	0.006 (2)	0.001 (2)
C5	0.040 (3)	0.048 (3)	0.039 (3)	−0.008 (2)	0.002 (2)	0.003 (2)
C6	0.053 (3)	0.052 (3)	0.054 (3)	0.000 (3)	0.004 (3)	0.013 (3)
C7	0.045 (3)	0.052 (3)	0.077 (4)	0.005 (3)	0.002 (3)	0.014 (3)
C8	0.047 (3)	0.048 (3)	0.067 (3)	0.003 (3)	0.013 (3)	0.000 (3)
C9	0.046 (3)	0.056 (3)	0.043 (3)	−0.005 (2)	0.000 (2)	−0.005 (2)
C10	0.063 (4)	0.094 (5)	0.047 (3)	0.004 (4)	−0.009 (3)	−0.005 (3)
C11	0.048 (3)	0.051 (3)	0.040 (3)	−0.002 (2)	0.011 (2)	0.004 (2)
C12	0.051 (3)	0.056 (3)	0.044 (3)	−0.010 (3)	0.018 (2)	−0.001 (2)
C13	0.058 (3)	0.043 (3)	0.041 (3)	−0.009 (2)	0.011 (2)	−0.003 (2)
C14	0.050 (3)	0.042 (3)	0.035 (2)	−0.001 (2)	0.008 (2)	−0.007 (2)
C15	0.067 (4)	0.038 (3)	0.061 (3)	−0.001 (3)	0.016 (3)	−0.003 (3)
C16	0.062 (4)	0.050 (3)	0.070 (4)	0.007 (3)	0.018 (3)	−0.009 (3)
C17	0.062 (3)	0.053 (3)	0.035 (3)	0.003 (3)	0.005 (2)	−0.008 (2)
C18	0.072 (4)	0.050 (3)	0.050 (3)	0.011 (3)	0.017 (3)	0.013 (3)
C19	0.055 (3)	0.055 (3)	0.053 (3)	0.014 (3)	0.026 (3)	0.010 (3)

Geometric parameters (Å, º)

Br1—C17	1.878 (5)	C7—H7B	0.9700
S1—C1	1.798 (6)	C8—H8A	0.9700
S1—C3	1.876 (5)	C8—H8B	0.9700
O1—C2	1.418 (7)	C9—C10	1.507 (7)
O1—C3	1.423 (6)	C9—H9	0.9300
O2—C13	1.325 (6)	C10—H10A	0.9600
O2—C12	1.434 (5)	C10—H10B	0.9600
O3—C13	1.201 (6)	C10—H10C	0.9600
C1—C2	1.478 (9)	C11—C12	1.516 (7)
C1—H1A	0.9700	C11—H11A	0.9700
C1—H1B	0.9700	C11—H11B	0.9700
C2—H2A	0.9700	C12—H12A	0.9700
C2—H2B	0.9700	C12—H12B	0.9700
C3—C4	1.509 (6)	C13—C14	1.484 (7)
C3—C8	1.525 (7)	C14—C15	1.374 (7)
C4—C9	1.314 (7)	C14—C19	1.376 (7)
C4—C5	1.525 (6)	C15—C16	1.382 (7)
C5—C11	1.530 (6)	C15—H15	0.9300
C5—C6	1.534 (7)	C16—C17	1.393 (8)
C5—H5	0.9800	C16—H16	0.9300
C6—C7	1.487 (7)	C17—C18	1.375 (7)
C6—H6A	0.9700	C18—C19	1.365 (7)
C6—H6B	0.9700	C18—H18	0.9300
C7—C8	1.531 (8)	C19—H19	0.9300
C7—H7A	0.9700
C1—S1—C3	92.6 (3)	C3—C8—H8B	109.4
C2—O1—C3	111.6 (4)	C7—C8—H8B	109.4
C13—O2—C12	116.3 (4)	H8A—C8—H8B	108.0
C2—C1—S1	104.1 (4)	C4—C9—C10	132.2 (5)
C2—C1—H1A	110.9	C4—C9—H9	113.9
S1—C1—H1A	110.9	C10—C9—H9	113.9
C2—C1—H1B	110.9	C9—C10—H10A	109.5
S1—C1—H1B	110.9	C9—C10—H10B	109.5
H1A—C1—H1B	109.0	H10A—C10—H10B	109.5
O1—C2—C1	109.2 (5)	C9—C10—H10C	109.5
O1—C2—H2A	109.8	H10A—C10—H10C	109.5
C1—C2—H2A	109.8	H10B—C10—H10C	109.5
O1—C2—H2B	109.8	C12—C11—C5	112.3 (4)
C1—C2—H2B	109.8	C12—C11—H11A	109.1
H2A—C2—H2B	108.3	C5—C11—H11A	109.1
O1—C3—C4	115.2 (4)	C12—C11—H11B	109.1
O1—C3—C8	106.2 (4)	C5—C11—H11B	109.1
C4—C3—C8	110.0 (4)	H11A—C11—H11B	107.9
O1—C3—S1	104.8 (3)	O2—C12—C11	107.7 (4)
C4—C3—S1	109.6 (3)	O2—C12—H12A	110.2
C8—C3—S1	111.0 (4)	C11—C12—H12A	110.2
C9—C4—C3	126.3 (4)	O2—C12—H12B	110.2
C9—C4—C5	123.4 (4)	C11—C12—H12B	110.2
C3—C4—C5	110.1 (4)	H12A—C12—H12B	108.5
C4—C5—C11	116.1 (4)	O3—C13—O2	123.9 (5)
C4—C5—C6	108.5 (4)	O3—C13—C14	123.9 (5)
C11—C5—C6	111.4 (4)	O2—C13—C14	112.3 (4)
C4—C5—H5	106.7	C15—C14—C19	118.9 (5)
C11—C5—H5	106.7	C15—C14—C13	118.8 (5)
C6—C5—H5	106.7	C19—C14—C13	122.3 (5)
C7—C6—C5	111.2 (4)	C14—C15—C16	121.4 (5)
C7—C6—H6A	109.4	C14—C15—H15	119.3
C5—C6—H6A	109.4	C16—C15—H15	119.3
C7—C6—H6B	109.4	C15—C16—C17	117.7 (5)
C5—C6—H6B	109.4	C15—C16—H16	121.1
H6A—C6—H6B	108.0	C17—C16—H16	121.1
C6—C7—C8	111.8 (5)	C18—C17—C16	121.6 (5)
C6—C7—H7A	109.3	C18—C17—Br1	118.7 (4)
C8—C7—H7A	109.3	C16—C17—Br1	119.7 (4)
C6—C7—H7B	109.3	C19—C18—C17	118.7 (5)
C8—C7—H7B	109.3	C19—C18—H18	120.7
H7A—C7—H7B	107.9	C17—C18—H18	120.7
C3—C8—C7	111.2 (4)	C18—C19—C14	121.7 (5)
C3—C8—H8A	109.4	C18—C19—H19	119.2
C7—C8—H8A	109.4	C14—C19—H19	119.2
C3—S1—C1—C2	−19.3 (5)	S1—C3—C8—C7	−66.0 (5)
C3—O1—C2—C1	−46.7 (7)	C6—C7—C8—C3	−53.6 (6)
S1—C1—C2—O1	39.6 (6)	C3—C4—C9—C10	0.6 (10)
C2—O1—C3—C4	−91.7 (6)	C5—C4—C9—C10	174.3 (6)
C2—O1—C3—C8	146.4 (5)	C4—C5—C11—C12	69.2 (6)
C2—O1—C3—S1	28.8 (5)	C6—C5—C11—C12	−165.9 (5)
C1—S1—C3—O1	−4.2 (4)	C13—O2—C12—C11	−178.9 (4)
C1—S1—C3—C4	119.9 (4)	C5—C11—C12—O2	176.4 (4)
C1—S1—C3—C8	−118.4 (4)	C12—O2—C13—O3	2.8 (7)
O1—C3—C4—C9	−5.5 (7)	C12—O2—C13—C14	−176.6 (4)
C8—C3—C4—C9	114.4 (6)	O3—C13—C14—C15	−11.5 (8)
S1—C3—C4—C9	−123.4 (5)	O2—C13—C14—C15	167.9 (5)
O1—C3—C4—C5	−179.9 (4)	O3—C13—C14—C19	169.8 (6)
C8—C3—C4—C5	−60.0 (5)	O2—C13—C14—C19	−10.8 (7)
S1—C3—C4—C5	62.2 (4)	C19—C14—C15—C16	−2.3 (8)
C9—C4—C5—C11	12.9 (7)	C13—C14—C15—C16	178.8 (5)
C3—C4—C5—C11	−172.6 (4)	C14—C15—C16—C17	1.2 (8)
C9—C4—C5—C6	−113.6 (5)	C15—C16—C17—C18	1.0 (9)
C3—C4—C5—C6	61.0 (5)	C15—C16—C17—Br1	−179.3 (4)
C4—C5—C6—C7	−58.7 (6)	C16—C17—C18—C19	−2.0 (9)
C11—C5—C6—C7	172.2 (5)	Br1—C17—C18—C19	178.4 (4)
C5—C6—C7—C8	55.4 (6)	C17—C18—C19—C14	0.7 (9)
O1—C3—C8—C7	−179.3 (4)	C15—C14—C19—C18	1.4 (8)
C4—C3—C8—C7	55.4 (6)	C13—C14—C19—C18	−179.9 (5)