1,4,7,10-Tetra­oxacyclo­dodeca­ne–triphenyl­methane­thiol (1/2)

In the centrosymmetric formula unit of the title complex, C₈H₁₆O₄·2C₁₈H₁₆S, the 1,4,7,10-tetra­oxacyclo­dodecane mol­ecule adopts the biangular [66] conformation, and the triphenyl­methane­thiol mol­ecules are linked to the macrocycle via a long S—H...O hydrogen bond [S...O = 3.460 (2) Å and S—H...O = 161 (2)°]. Attractive inter­actions of phenyl groups in edge-to-face conformations combine inversion-related formula units into chains running along the [111] direction in the crystal structure. Association of the chains into sheets is achieved via C—H...π inter­actions.

S1. Comment

Thiols fulfill numerous functions in biological systems, including a central role in coordinating antioxidant defences (Sen & Packer, 2000). A search of the Cambridge Structural Database (CSD, Version 5.26, plus one 2005 update; Allen, 2002) revealed only a few examples of thiol-containing adducts with neutral organic molecules, predominantly with organic solvents or water. In 2-mercapto-6-methylpurine monohydrate (Srinivasan & Chandrasekaran, 1968) and in D-N-γ-L-glutamyl-L-cysteine ethyl ester monohydrate (Takimoto-Kamimura et al., 1990), the thiol functional group is involved in an S—H···O(water) hydrogen bond, while in the case of adducts with organic solvents, the thiol molecules exhibit a tendency to be self-assembling and the thiol functional group contributes to the overall system of hydrogen bonding via S—H···O(═C), C—H···S(SH) (Evans et al., 1993; Pyrka et al., 1992), S—H···S (Ung et al., 1994; Hardy et al., 1979) or S—H···π interactions (Walsdorff et al., 1997). Only one compound, namely bis(4-aminophenyl) disulfide 4-aminothiophenol (Vangala et al., 2002), exhibits assembly of different molecules via C—H···S hydrogen bonds.

For more than two decades, crown ethers have been a very useful tool for following interaction pathways between neutral molecules, including biologically important molecules. As a continuation of our contribution to this topic (Simonov et al., 2003), we report here the crystal structure of the title binary adduct, (I), of triphenylmethanethiol with 1,4,7,10-tetraoxacyclododecane (12-crown-4, 12 C4). Compound (I) is the first example of an adduct between a thiol and a crown ether to be structurally described. The main points of this report are the mode of mutual interaction in this binary system, and the similarities and differences in the crystal packing of triphenylmethanethiol itself and its binary adduct.

The published metal-free crystal structures of 12 C4 with neutral molecules include a ternary clathrate with γ-cyclodextrin and water (Kamitori et al., 1986), binary adducts of the general formula 12 C4.2D, where D is the zwitterion ⁺H₃NSO₃⁻ (Simonov et al., 1993), Ph₃SiOH (Babaian et al., 1990), (PhSO₂)₂NH (Wijaya et al., 1998), (EtSO₂)₂CH₂ (Michalides et al., 1995) or Me₂CNNHC(═S)NH₂ (Moers et al., 1999), and the binary adduct with dithiobisurea, (NH₂CSNH)₂, in a 1:1 ratio (Simonov et al., 2003). The structures of these adducts are held together by O—H···O, N—H···O or C—H···O hydrogen bonds between the respective substrate and 12 C4. No examples of crown ether complexes held together by S—H···O hydrogen bonds are known to date.

The centrosymmetric formula unit of (I) is shown in Fig. 1 and selected intramolecular geometric data are listed in Table 1. The geometries of both molecules are in reasonable agreement with the precise data obtained for crown ethers and triphenylmethanethiol itself (Bernardinelli et al., 1991). The macrocycle in (I) adopts the C_i symmetric and biangular [66]-conformation, which also occurs in pure 12 C4 (Groth, 1978), in the aforementioned 1:2 complexes and in several structures containing metal cations. The torsion angles of the 12 C4 ring are given in Table 1.

Within the centrosymmetric formula unit, the long S—H···O hydrogen bond (and its symmetry equivalent) links the thiol molecules to the crown ether. Inversion-related formula units are then associated into chains (Fig. 2) via attractive interactions ofthe phenyl groups in an edge-to-face (ef) conformation. This concerted intermolecular attraction uses six phenyl ef interactions from two inversion-related triphenylmethanethiol moieties. As shown in Fig. 2, the two Ph₃C groups approach each other such that each phenyl ring is interleaved between two rings on the other molecule, with two H atoms on each ring directed towards C atoms of a phenyl ring on the other molecule. This concerted motif, known as a sextuple phenyl embrace (SPE; Dance & Scudder, 1995), was primarily explored for the structures containing PPh₄⁺ cations or terminating XPh₃ ligands and covering P···P separations in the range 5.5–8.0 Å (Scudder & Dance, 2002). The SPE in (I) is characterized by the C1···C1(−x, 1 − y, −z) distance of 6.393 (3) Å, and three centroid–centroid distances between phenyl rings of 5.24, 5.29 and 5.51 Å [for comparison, the SPE with the 5-benzyloxy-1,3-benzene dicarbonic ligand incorporated in the Kagome lattice described by Perry et al. (2004) is characterized by centroid–centroid distances in the range 5.19–5.19 Å]. Finally, interchain crosslinking is achieved via C—H···π interactions the [C5—H5···Cg2ⁱ: C5···Cg2ⁱ = 3.679 (3) Å, H5···Cg2 = 2.99 Å and C5—H5···Cg2 = 132°, where Cg2 is the centroid of phenyl ring C8–C13; symmetry code: (i) x-1, y, z], resulting in the association of the chains into sheets.

Some similarities occurring in the supramolecular architecture of (I) and triphenylmethanethiol molecules in the pure form (CSD refcode SIZBAE, space group P1; Bernardinelli et al., 1991) are noteworthy. There are two independent molecules in the SIZBAE structure. For the molecule containing atom S1, there is one significant S—H···π interaction [S1—H1···Cg: H···Cg = 2.62 Å, S···Cg = 3.73 Å and S—H···Cg = 141 Å, where Cg is the centroid of ring C14–C19 at (1 − x, 2 − y, 1 − z)], which combines these molecules into centrosymmetric dimers. These dimers are further combined into chains via the SPE; the distance between the tetrahedral C atoms [C1···C1(1 − x, 1 − y, 1 − z) = 6.058 Å] and the centroid–centroid distances of the phenyl rings are 4.87, 4.99 and 5.44 Å. For the molecule containing atom S2, the SPE is characterized by the distance between the tetrahedral C atoms [C20···C20(1 − x, −y, 2 − z) = 6.312 Å] and the centroid–centroid distances the of phenyl rings are 5.12, 5.18 and 5.23 Å. Only the SPE interaction remains in (I), while the S—H···π contact is replaced by the S—H···O(crown) hydrogen bonds.

Comparison of (I) with the complex 12 C4.2Ph₃SiOH (CSD refcode SELFIY; Babaian et al., 1990) reveals that these two structures are isomorphous. Similar to (I), the structure of SELFIY is sustained by two inversion-related O—H···O hydrogen bonds (H···O = 1.91 Å and O—H···O = 2.756 Å) and the SPE an Si1···Si1(−x, 1 − y, −z) separation of 6.538 Å and centroid–centroid distances between phenyl rings equal to 5.19, 5.20 and 5.86 Å.

S2. Experimental

A solution of 12 C4 (0.176 g, 1 mmol) and Ph₃CSH (276 mg, 1 mmol) in a benzene–ethyl ether mixture (1:2 v/v, 4.5 ml) was stored for 1 d at 293 K in an open flask. Colourless transparent crystals of (I) suitable for X-ray analysis separated in a yield of 83% (0.303 g; m.p. 341–343 K). The crystals are soluble in methanol, ethanol, acetone and chloroform. ¹H NMR (CDCl₃, 300 MHz): δ 1.62 (s, 2H, SH), 3.71 (s, 16H, 12 C4), 7.22–7.30 (m, 30H, aromatic H). Analysis calculated for C₄₆H₄₈O₄S₂: C 75.79, H 6.64, S 8.80%; found: C 75.81, H 6.69, S 8.77%.

S3. Refinement

The S-bound H atom was located in a difference Fourier map and refined isotropically. C-bound H atoms were placed in calculated positions, with C—H distances of 0.93 or 0.97 Å, and were treated using a riding-model approximation, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of (I) in the crystal, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the asymmetric unit is numbered; unlabelled atoms are related by the symmetry code (1 − x, −y, 1 − z). Hydrogen bonds are shown as dashed lines.
	Fig. 2. The chain organization in (I) sustained by S—H···O hydrogen bonds and the SPE interactions. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, −y, 1 − z) and (−x, 1 − y, −z), respectively. Only H atoms mentioned in the Comment are shown.

1,4,7,10-Tetraoxacyclododecane–triphenylmethanethiol (1/2)

Crystal data

C8H16O4·2C19H16S	F(000) = 388
Mr = 728.96	Dx = 1.218 Mg m^−3
Triclinic, P1	Melting point = 341–343 K
a = 8.596 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.803 (1) Å	Cell parameters from 25 reflections
c = 12.353 (1) Å	θ = 4.8–12.5°
α = 84.35 (1)°	µ = 0.18 mm^−1
β = 89.18 (1)°	T = 293 K
γ = 73.61 (1)°	Prism, yellow
V = 993.7 (2) Å^3	0.40 × 0.36 × 0.21 mm
Z = 1

Data collection

Siemens P4 diffractometer	2730 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 26.0°, θmin = 2.2°
ω scans	h = 0→10
Absorption correction: empirical (using intensity measurements) (SHELXTL-Plus; Sheldrick, 1995)	k = −11→12
Tmin = 0.877, Tmax = 0.964	l = −15→15
4190 measured reflections	3 standard reflections every 97 reflections
3914 independent reflections	intensity decay: 13.6%

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 0.0975P] where P = (Fo^2 + 2Fc^2)/3
3914 reflections	(Δ/σ)max = 0.001
239 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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
S	0.24659 (7)	0.42993 (7)	0.37779 (4)	0.05985 (19)
H1	0.226 (3)	0.302 (3)	0.410 (2)	0.099 (8)*
O1	0.2470 (2)	0.09805 (19)	0.50275 (13)	0.0799 (5)
O2	0.4658 (2)	−0.09056 (18)	0.36564 (13)	0.0780 (5)
C1	0.1493 (2)	0.45193 (18)	0.24092 (13)	0.0389 (4)
C2	−0.0065 (2)	0.40525 (18)	0.25076 (14)	0.0415 (4)
C3	−0.1124 (3)	0.4436 (2)	0.33557 (18)	0.0575 (5)
H3	−0.0852	0.4928	0.3896	0.069*
C4	−0.2582 (3)	0.4093 (3)	0.3406 (2)	0.0736 (7)
H4	−0.3282	0.4363	0.3977	0.088*
C5	−0.2999 (3)	0.3363 (3)	0.2625 (2)	0.0719 (7)
H5	−0.3978	0.3134	0.2664	0.086*
C6	−0.1967 (3)	0.2969 (2)	0.1781 (2)	0.0674 (6)
H6	−0.2244	0.2468	0.1248	0.081*
C7	−0.0507 (2)	0.3316 (2)	0.17214 (17)	0.0529 (5)
H7	0.0183	0.3050	0.1145	0.063*
C8	0.2703 (2)	0.36263 (19)	0.16457 (14)	0.0398 (4)
C9	0.3407 (2)	0.2174 (2)	0.19310 (17)	0.0519 (5)
H9	0.3152	0.1755	0.2593	0.062*
C10	0.4473 (3)	0.1348 (2)	0.1253 (2)	0.0626 (6)
H10	0.4932	0.0381	0.1460	0.075*
C11	0.4865 (3)	0.1948 (3)	0.0266 (2)	0.0648 (6)
H11	0.5593	0.1391	−0.0190	0.078*
C12	0.4171 (3)	0.3370 (2)	−0.00341 (17)	0.0597 (5)
H12	0.4425	0.3778	−0.0701	0.072*
C13	0.3092 (2)	0.4210 (2)	0.06455 (15)	0.0484 (5)
H13	0.2625	0.5173	0.0428	0.058*
C14	0.1108 (2)	0.61228 (18)	0.20430 (13)	0.0403 (4)
C15	−0.0308 (3)	0.6842 (2)	0.14746 (15)	0.0514 (5)
H15	−0.1053	0.6355	0.1328	0.062*
C16	−0.0627 (3)	0.8289 (2)	0.11203 (19)	0.0697 (6)
H16	−0.1576	0.8757	0.0730	0.084*
C17	0.0449 (4)	0.9025 (3)	0.1343 (2)	0.0782 (8)
H17	0.0220	0.9996	0.1119	0.094*
C18	0.1854 (4)	0.8331 (3)	0.1895 (2)	0.0762 (7)
H18	0.2588	0.8829	0.2044	0.091*
C19	0.2196 (3)	0.6884 (2)	0.22349 (17)	0.0602 (6)
H19	0.3170	0.6417	0.2597	0.072*
C20	0.2523 (3)	0.1012 (3)	0.6174 (2)	0.0892 (9)
H20A	0.2822	0.0043	0.6525	0.107*
H20B	0.1457	0.1505	0.6425	0.107*
C21	0.2290 (3)	−0.0306 (3)	0.4679 (2)	0.0835 (8)
H21A	0.1706	−0.0091	0.3989	0.100*
H21B	0.1648	−0.0704	0.5205	0.100*
C22	0.3858 (3)	−0.1378 (3)	0.4553 (2)	0.0784 (7)
H22A	0.4517	−0.1507	0.5207	0.094*
H22B	0.3681	−0.2288	0.4440	0.094*
C23	0.6297 (3)	−0.1744 (3)	0.3528 (2)	0.0836 (8)
H23A	0.6457	−0.1954	0.2777	0.100*
H23B	0.6485	−0.2644	0.3980	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0645 (4)	0.0743 (4)	0.0392 (3)	−0.0177 (3)	−0.0106 (2)	−0.0024 (2)
O1	0.0922 (13)	0.0746 (11)	0.0612 (10)	−0.0067 (10)	0.0045 (9)	−0.0009 (8)
O2	0.0761 (11)	0.0785 (11)	0.0641 (10)	−0.0024 (9)	0.0055 (8)	0.0094 (8)
C1	0.0409 (10)	0.0433 (10)	0.0330 (8)	−0.0126 (8)	−0.0021 (7)	−0.0032 (7)
C2	0.0407 (10)	0.0372 (9)	0.0449 (9)	−0.0103 (8)	0.0001 (8)	0.0026 (7)
C3	0.0557 (13)	0.0609 (13)	0.0610 (12)	−0.0228 (10)	0.0162 (10)	−0.0131 (10)
C4	0.0607 (15)	0.0755 (17)	0.0894 (17)	−0.0275 (13)	0.0284 (13)	−0.0111 (13)
C5	0.0450 (12)	0.0642 (15)	0.110 (2)	−0.0248 (11)	0.0073 (13)	0.0010 (14)
C6	0.0561 (14)	0.0636 (14)	0.0882 (17)	−0.0242 (11)	−0.0120 (12)	−0.0118 (12)
C7	0.0473 (11)	0.0603 (13)	0.0546 (11)	−0.0192 (10)	−0.0026 (9)	−0.0100 (9)
C8	0.0355 (9)	0.0452 (10)	0.0409 (9)	−0.0139 (8)	−0.0013 (7)	−0.0069 (7)
C9	0.0547 (12)	0.0452 (11)	0.0552 (11)	−0.0131 (9)	0.0000 (9)	−0.0045 (9)
C10	0.0586 (13)	0.0458 (12)	0.0810 (16)	−0.0079 (10)	−0.0005 (12)	−0.0155 (11)
C11	0.0572 (13)	0.0660 (15)	0.0771 (15)	−0.0176 (11)	0.0147 (11)	−0.0361 (12)
C12	0.0601 (13)	0.0714 (15)	0.0537 (12)	−0.0257 (12)	0.0149 (10)	−0.0159 (10)
C13	0.0511 (11)	0.0500 (11)	0.0443 (10)	−0.0144 (9)	0.0042 (9)	−0.0065 (8)
C14	0.0477 (10)	0.0406 (10)	0.0340 (8)	−0.0138 (8)	0.0065 (7)	−0.0077 (7)
C15	0.0567 (12)	0.0483 (11)	0.0462 (10)	−0.0119 (9)	0.0022 (9)	0.0003 (8)
C16	0.0821 (17)	0.0535 (14)	0.0620 (14)	−0.0051 (12)	0.0072 (12)	0.0080 (10)
C17	0.123 (2)	0.0450 (13)	0.0657 (15)	−0.0243 (15)	0.0251 (16)	−0.0047 (11)
C18	0.114 (2)	0.0661 (16)	0.0690 (15)	−0.0550 (16)	0.0169 (15)	−0.0177 (13)
C19	0.0694 (14)	0.0625 (14)	0.0579 (12)	−0.0328 (12)	0.0005 (11)	−0.0083 (10)
C20	0.0799 (18)	0.113 (2)	0.0629 (15)	−0.0092 (17)	0.0150 (14)	−0.0080 (15)
C21	0.0701 (17)	0.103 (2)	0.0804 (17)	−0.0307 (16)	0.0009 (13)	−0.0036 (15)
C22	0.0900 (19)	0.0690 (16)	0.0739 (16)	−0.0215 (15)	0.0039 (14)	0.0012 (12)
C23	0.094 (2)	0.0798 (18)	0.0587 (14)	0.0078 (16)	0.0042 (13)	−0.0120 (12)

Geometric parameters (Å, º)

S—C1	1.8632 (17)	C11—H11	0.9300
S—H1	1.33 (3)	C12—C13	1.388 (3)
O1—C21	1.420 (3)	C12—H12	0.9300
O1—C20	1.421 (3)	C13—H13	0.9300
O2—C22	1.404 (3)	C14—C15	1.383 (3)
O2—C23	1.432 (3)	C14—C19	1.386 (3)
C1—C2	1.532 (2)	C15—C16	1.393 (3)
C1—C14	1.535 (2)	C15—H15	0.9300
C1—C8	1.536 (2)	C16—C17	1.369 (4)
C2—C7	1.382 (3)	C16—H16	0.9300
C2—C3	1.387 (3)	C17—C18	1.361 (4)
C3—C4	1.385 (3)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.389 (3)
C4—C5	1.365 (4)	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.372 (3)	C20—C23^i	1.467 (4)
C5—H5	0.9300	C20—H20A	0.9700
C6—C7	1.389 (3)	C20—H20B	0.9700
C6—H6	0.9300	C21—C22	1.474 (4)
C7—H7	0.9300	C21—H21A	0.9700
C8—C13	1.386 (2)	C21—H21B	0.9700
C8—C9	1.392 (3)	C22—H22A	0.9700
C9—C10	1.375 (3)	C22—H22B	0.9700
C9—H9	0.9300	C23—C20^i	1.467 (4)
C10—C11	1.380 (3)	C23—H23A	0.9700
C10—H10	0.9300	C23—H23B	0.9700
C11—C12	1.368 (3)
C1—S—H1	96.7 (12)	C12—C13—H13	119.7
C21—O1—C20	115.0 (2)	C15—C14—C19	117.88 (18)
C22—O2—C23	114.92 (19)	C15—C14—C1	121.03 (16)
C2—C1—C14	110.80 (14)	C19—C14—C1	121.05 (17)
C2—C1—C8	111.41 (14)	C14—C15—C16	120.6 (2)
C14—C1—C8	111.39 (14)	C14—C15—H15	119.7
C2—C1—S	109.48 (12)	C16—C15—H15	119.7
C14—C1—S	104.82 (11)	C17—C16—C15	120.3 (2)
C8—C1—S	108.70 (12)	C17—C16—H16	119.8
C7—C2—C3	118.05 (18)	C15—C16—H16	119.8
C7—C2—C1	121.14 (16)	C18—C17—C16	119.8 (2)
C3—C2—C1	120.69 (17)	C18—C17—H17	120.1
C4—C3—C2	120.7 (2)	C16—C17—H17	120.1
C4—C3—H3	119.6	C17—C18—C19	120.3 (2)
C2—C3—H3	119.6	C17—C18—H18	119.9
C5—C4—C3	120.6 (2)	C19—C18—H18	119.9
C5—C4—H4	119.7	C14—C19—C18	121.0 (2)
C3—C4—H4	119.7	C14—C19—H19	119.5
C4—C5—C6	119.7 (2)	C18—C19—H19	119.5
C4—C5—H5	120.2	O1—C20—C23^i	110.5 (2)
C6—C5—H5	120.2	O1—C20—H20A	109.5
C5—C6—C7	120.1 (2)	C23^i—C20—H20A	109.5
C5—C6—H6	120.0	O1—C20—H20B	109.5
C7—C6—H6	120.0	C23^i—C20—H20B	109.5
C2—C7—C6	120.9 (2)	H20A—C20—H20B	108.1
C2—C7—H7	119.5	O1—C21—C22	112.7 (2)
C6—C7—H7	119.5	O1—C21—H21A	109.1
C13—C8—C9	117.79 (17)	C22—C21—H21A	109.1
C13—C8—C1	122.00 (16)	O1—C21—H21B	109.1
C9—C8—C1	120.18 (16)	C22—C21—H21B	109.1
C10—C9—C8	121.23 (19)	H21A—C21—H21B	107.8
C10—C9—H9	119.4	O2—C22—C21	108.9 (2)
C8—C9—H9	119.4	O2—C22—H22A	109.9
C9—C10—C11	120.3 (2)	C21—C22—H22A	109.9
C9—C10—H10	119.8	O2—C22—H22B	109.9
C11—C10—H10	119.8	C21—C22—H22B	109.9
C12—C11—C10	119.3 (2)	H22A—C22—H22B	108.3
C12—C11—H11	120.3	O2—C23—C20^i	112.2 (2)
C10—C11—H11	120.3	O2—C23—H23A	109.2
C11—C12—C13	120.7 (2)	C20^i—C23—H23A	109.2
C11—C12—H12	119.7	O2—C23—H23B	109.2
C13—C12—H12	119.7	C20^i—C23—H23B	109.2
C8—C13—C12	120.65 (19)	H23A—C23—H23B	107.9
C8—C13—H13	119.7
C20—O1—C21—C22	−89.1 (3)	C22—O2—C23—C20^i	−106.5 (3)
O1—C21—C22—O2	−69.4 (3)	O2—C23—C20^i—O1^i	72.2 (3)
C21—C22—O2—C23	171.6 (2)	C23—C20^i—O1^i—C21^i	−141.6 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
S—H1···O1	1.33 (3)	2.17 (3)	3.460 (2)	161 (2)