Synthesis and crystal structures of 3-hy­droxy-2,4-dimethyl-2H-thio­phen-5-one and 3-hy­droxy-4-methyl-2H-thio­phen-5-one

Nashawi, A.; Lawson, C.P.; Abdel-Sattar, M.O.; Horst, J.H. ter; Coxon, G.D.; Kennedy, A.R.

doi:10.1107/S2056989020008269

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ISSN: 2056-9890

Volume 76| Part 7| July 2020| Pages 1158-1162

https://doi.org/10.1107/S2056989020008269

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Synthesis and crystal structures of 3-hydroxy-2,4-dimethyl-2H-thiophen-5-one and 3-hydroxy-4-methyl-2H-thiophen-5-one

Asma Nashawi,^a,^b Christopher P. Lawson,^a M. Omar Abdel-Sattar,^b,^c Joop H. ter Horst,^d Geoffrey D. Coxon ^a ^* and Alan R. Kennedy ^e

^aStrathclyde Institute for Pharmacy and Biomedical Sciences, University of Strathclyde, 161 Cathedral Street, Glasgow G4 0RE, Scotland, ^bDepartment of Pharmaceutical Chemistry, King Abdul Aziz University, Jeddah, 21589, Saudi Arabia, ^cDepartment of Chemistry, Al-Azhar University, Cairo, 11884, Egypt, ^dEPSRC Future Manufacturing Research Hub for Continuous Manufacture and Advanced Crystallisation (CMAC), Technology and Innovation Centre, University of Strathclyde, 99 George Street, Glasgow G1 1RD, Scotland, and ^eWestchem, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: geoff.coxon@strath.ac.uk

Edited by A. J. Lough, University of Toronto, Canada (Received 27 March 2020; accepted 22 June 2020; online 30 June 2020)

The structures of two hydroxy-thiophenone derivatives related to the antibiotic thiolactomycin are presented. These are the racemic 3-hydroxy-2,4-dimethyl-2H-thiophen-5-one, C₆H₈O₂S, and 3-hydroxy-4-methyl-2H-thiophen-5-one, C₅H₆O₂S. The main structural feature of both compounds is C(6) hydrogen-bonded chains formed between the OH and C=O groups. In achiral C₅H₆O₂S, these chains propagate only by translation, corresponding to x + 1, y, z + 1. However, in contrast, for racemic C₆H₈O₂S the hydrogen-bonded chains propagate through a −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z operation, giving chains lying parallel to the crystallographic b-axis direction that are composed of alternate R and S enantiomers. The crystals of 3-hydroxy-4-methyl-2H-thiophen-5-one were found to be twinned by a 180° rotation about the reciprocal 001 direction. In the final refinement the twin ratio refined to 0.568 (2):0.432 (2).

Keywords: crystal structure; hydroxy-thiophenone; hydrogen bonding.

CCDC references: 2011283; 2011284

1. Chemical context

Thiolactomycin (TLM) 1, (5R)-4-hydroxy-3,5-dimethyl-5-[(1E)-2-methylbuta-1,3-dienyl]thiophen-2-one, is a naturally occurring antibiotic isolated from Norcardia spp (Sasaki et al., 1982 ). Over the last three decades, synthetic efforts towards the synthesis of the single enantiomer and analogues have provided relatively complex solutions. These have exploited asymmetric synthesis, diasteromeric recrystallization or enzymatic resolution requiring between seven and eleven steps and thus have significantly restricted the development of this scaffold towards clinical application. For examples see Chambers & Thomas (1997 ), McFadden et al. (2002 ), Ohata & Terashima (2009 ), Kamal et al. (2008 ), Toyama et al. (2006 ) and Bommineni et al. (2016 ). Herein we present findings from our initial studies focused on the single-crystal determination of thiolactone analogues.

2. Structural commentary

The molecular structures of compounds 4 and 5 are shown in Figs. 1 and 2, respectively. As can be seen from Tables 1 and 2, equivalent geometric parameters in the two structures are similar, with the largest difference in bond length being found for the S1—C4 values [1.816 (3) and 1.799 (3) Å]. A notable structural difference is the orientation of the hydroxy groups containing the O2 atoms. In both structures, this O atom is coplanar with the SC₄ ring, but in structure 4 the H atom points towards C5 and is eclipsed by the C2=C3 double bond whilst in structure 5 the H atom points towards the CH₂ group and is eclipsed by the C3—C4 single bond. This change in orientation is associated with a change in the bond angles involving O2 [compare C4—C3—O2 angles of 113.4 (2) and 119.7 (3)°]. A search of the Cambridge Structural Database (version 5.40; Groom et al., 2016 ) found only three other structures with similar 4-hydroxy-thiophen-2-one cores. These are TLM itself (BIHKIM, Nawata et al., 1989 ) and two other derivatives (FIVKEA, Chambers et al., 1987 ; POXZOS, Kikionis et al., 2009 ). These have generally similar geometric parameters to those of 4 and 5. Two of the database structures have the same hydroxy group orientation as 5. Only POXZOS has the same hydroxy orientation as 4, and here this orientation is predetermined by the OH group participating in an intramolecular six-membered hydrogen-bonded ring. As with structures 4 and 5, in the database structures the orientation of the OH group is associated with systematic changes to the C—C—O bond angles involving OH.

Table 1
Selected geometric parameters (Å, °) for 4

S1—C1	1.778 (3)	C3—C2	1.351 (4)
S1—C4	1.816 (3)	C3—C4	1.507 (4)
O1—C1	1.238 (3)	C2—C1	1.434 (4)
O2—C3	1.326 (3)

C1—S1—C4	92.62 (12)	C3—C2—C1	112.3 (2)
O2—C3—C4	113.4 (2)	C2—C1—S1	112.1 (2)
C2—C3—C4	117.8 (2)	C3—C4—S1	105.16 (18)

Table 2
Selected geometric parameters (Å, °) for 5

S1—C1	1.775 (3)	C1—C2	1.440 (4)
S1—C4	1.799 (3)	C2—C3	1.347 (4)
O1—C1	1.231 (4)	C2—C5	1.502 (4)
O2—C3	1.332 (4)	C3—C4	1.499 (4)

C1—S1—C4	92.33 (15)	O2—C3—C4	119.7 (3)
C2—C1—S1	112.0 (2)	C2—C3—C4	117.2 (3)
C3—C2—C1	112.2 (3)	C3—C4—S1	106.2 (2)

Figure 1
The molecular structure of 4 with non-H atoms shown as 50% probability ellipsoids. H atoms are drawn as small spheres of arbitrary size.

Figure 2
The molecular structure of 5 with non-H atoms shown as 50% probability ellipsoids. H atoms are drawn as small spheres of arbitrary size.

3. Supramolecular features

The main supramolecular feature of both structures 4 and 5 is a one-dimensional C(6) hydrogen-bonded chain utilizing OH as the donor group and O1 as the acceptor group, see Tables 3 and 4. Behind these basic similarities there lies a great deal of difference in detail. In 5 the chains propagate by translations corresponding to x + 1, y, z + 1. This propagation by translation alone gives the repeating pattern shown in Fig. 3 where all of the SC₄ rings of the hydrogen-bonded unit are coplanar and all of the S atoms lie on the same side of the chain. When travelling along the b-axis direction, neighbouring chains bear their S atoms on different sides, giving the layered structure shown in Fig. 4. In contrast, for structure 4 the chain propagates through a −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z operation giving a chain lying parallel to the crystallographic b-axis direction. As shown in Fig. 5, this results in the neighbouring R and S enantiomers of the racemic chain having perpendicular relationships between the planes of their SC₄ rings. This different chain geometry gives a very different packing arrangement from that of structure 5, see Fig. 6. The only interchain contact significantly shorter than the sum of van der Waals radii in either structure occurs in structure 5. This is a C—H⋯O contact between the CH₂ group and the ketone O atom. Of the 4-hydroxy-thiophen-2-one structures described in the literature, both those of FIVKEA and BIHKIM (TLM) display the same C(6) hydrogen-bonded chain motif as 4 and 5. In both cases, the geometrical detail of the chain is similar to that found in 4, with the difference that both literature examples are enantiopure. The final structure, POXZOS, contains additional carboxylic acid and carbonyl groups and these strong hydrogen-bonding groups dominate the intermolecular contacts formed and so stop the formation of the otherwise common C(6) motif.

Table 3
Hydrogen-bond geometry (Å, °) for 4

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1H⋯O1ⁱ	0.88 (4)	1.77 (4)	2.621 (3)	164 (4)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Table 4
Hydrogen-bond geometry (Å, °) for 5

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1H⋯O1ⁱ	0.84 (5)	1.80 (5)	2.629 (3)	168 (5)
C4—H4B⋯O1ⁱⁱ	0.99	2.58	3.552 (4)	169
Symmetry codes: (i) x-1, y, z-1; (ii) x, y, z-1.

Figure 3
Part of the hydrogen-bonded chain motif present in the structure of 5. The chain extends parallel to the [101] direction.

Figure 4
Packing diagram for compound 5 in a view down the a axis. Note the alternating Me⋯Me and S⋯S layers.

Figure 5
Part of the hydrogen-bonded chain motif present in the structure of 4. The chain extends parallel to the cystallographic b axis.

Figure 6
Packing diagram for compound 4 with a view down the a axis.

4. Synthesis and crystallization

General synthesis of thiolactone analogues 4 and 5:

Bromine (1.1 eq) was added to a stirring solution of the corresponding oxoester (1 eq.) dissolved in chloroform (50 ml) at 273 K. The mixtures were allowed to warm to ambient temperature and stirred for 20 h before removing the solvent under vacuum. The resulting crude mixtures were dissolved in THF (50 ml) before adding trimethylamine (1.1 eq.) and thioacetic acid (1.1 eq.) and stirring at ambient temperature for a further 18 h. The resulting mixtures were reduced under vacuum to give dark-orange oils that were vacuum filtered over silica using petrol (40/60) and diethyl ether (5:2) as eluent before removing the solvent. The mixtures were dissolved in ethanol (50 ml) before adding a solution of sodium hydroxide (2 eq.) dissolved in water (20 ml) and stirring for 24 h at 333 K. After cooling, HCl (0.1M) was added until the solutions reached pH 5 before washing with ethyl acetate (3 × 50 ml) and drying over anhydrous magnesium sulfate. The mixtures were reduced under vacuum and precipitated using petrol (40/60) and diethyl ether to give the products as a solid. For 4, crystals suitable for crystallographic analysis were grown from a THF solution. For 5, crystals were grown from a toluene solution.

3-Hydroxy-2,4-dimethyl-2H-thiophen-5-one (4) Off-white solid (1.1 g, 22%): m.p. 408–409 K. ¹H NMR (CDCl₃) δ 4.12 (dd, J = 7.1, 1.3 Hz, 1H), 1.57 (d, J = 7.1 Hz, 4H). ¹³C NMR (CDCl₃) δ 197.16, 177.63, 111.32, 77.26, 77.21, 77.00, 76.75, 42.99, 18.80, 7.62.

3-Hydroxy-4-methyl-2H-thiophen-5-one (5)

Off-white solid (1.6 g, 18%): m.p. 397–398 K. ¹H NMR (CDCl₃) δ 3.94 (s, 2H), 1.68 (s, 3H). ¹³C NMR (CDCl₃) δ 195.1, 175.2, 111.2, 32.1, 7.2.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. For both structures, C-bound H atoms were placed in the expected geometric positions and treated in riding modes with C—H = 0.98, 0.99 and 1.00 Å for methyl, CH₂ and CH groups, respectively. U_iso(H) = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) for the other CH groups. The H atoms of the hydroxy groups were refined isotropically. Data collection on 5 was carried out by the National Crystallography Service (Cole & Gale, 2012 ). The crystals of 5 were found to be twinned by a 180° rotation about the reciprocal 001 direction. This feature was accounted for by producing a hklf 5 formatted datafile during data processing. In the final refinement the twin ratio refined to 0.568 (2):0.432 (2).

Table 5
Experimental details

	4	5
Crystal data
Chemical formula	C₆H₈O₂S	C₅H₆O₂S
M_r	144.18	130.16
Crystal system, space group	Orthorhombic, Pbca	Monoclinic, P2₁/c
Temperature (K)	123	100
a, b, c (Å)	9.286 (1), 11.4809 (8), 12.6469 (10)	4.1054 (3), 22.9727 (13), 6.1928 (5)
α, β, γ (°)	90, 90, 90	90, 103.728 (7), 90
V (Å³)	1348.3 (2)	567.37 (7)
Z	8	4
Radiation type	Cu Kα	Mo Kα
μ (mm⁻¹)	3.63	0.46
Crystal size (mm)	0.55 × 0.08 × 0.04	0.12 × 0.02 × 0.01

Data collection
Diffractometer	Oxford Diffraction Gemini S	Rigaku XtaLAB AFC12
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.323, 0.847	0.766, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4293, 1323, 1115	2121, 2121, 1955
R_int	0.049	0.026
(sin θ/λ)_max (Å⁻¹)	0.620	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.148, 1.07	0.050, 0.113, 1.19
No. of reflections	1323	2121
No. of parameters	88	79
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.29	0.43, −0.33
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), SIR92 (Altomare et al., 1994 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2020 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC references: 2011283; 2011284

Crystal structure: contains datablocks 4, 5, global. DOI: https://doi.org/10.1107/S2056989020008269/lh5954sup1.cif

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2056989020008269/lh59544sup2.hkl

Structure factors: contains datablock 5. DOI: https://doi.org/10.1107/S2056989020008269/lh59545sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020008269/lh59544sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989020008269/lh59545sup5.cml

checkCIF report

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

3-Hydroxy-2,4-dimethyl-2H-thiophen-5-one (4) top

Crystal data top

C₆H₈O₂S	D_x = 1.421 Mg m⁻³
M_r = 144.18	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 1393 reflections
a = 9.286 (1) Å	θ = 7.0–72.8°
b = 11.4809 (8) Å	µ = 3.63 mm⁻¹
c = 12.6469 (10) Å	T = 123 K
V = 1348.3 (2) Å³	Rod, colourless
Z = 8	0.55 × 0.08 × 0.04 mm
F(000) = 608

Data collection top

Oxford Diffraction Gemini S diffractometer	1115 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.049
ω scans	θ_max = 73.0°, θ_min = 7.0°
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2019)	h = −11→11
T_min = 0.323, T_max = 0.847	k = −13→10
4293 measured reflections	l = −15→12
1323 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.081P)² + 0.8472P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1323 reflections	Δρ_max = 0.67 e Å⁻³
88 parameters	Δρ_min = −0.29 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.84281 (8)	0.16688 (5)	0.67914 (5)	0.0327 (3)
O1	0.6506 (2)	0.17209 (14)	0.52486 (16)	0.0311 (5)
O2	0.9490 (2)	0.48890 (16)	0.62458 (16)	0.0329 (5)
C3	0.8868 (3)	0.3850 (2)	0.6199 (2)	0.0283 (6)
C6	0.9207 (4)	0.3465 (3)	0.8144 (2)	0.0374 (7)
H6A	0.9733	0.4199	0.8231	0.056*
H6B	0.9571	0.2890	0.8651	0.056*
H6C	0.8179	0.3597	0.8271	0.056*
C2	0.7822 (3)	0.3476 (2)	0.5539 (2)	0.0272 (6)
C1	0.7427 (3)	0.2288 (2)	0.57332 (19)	0.0281 (6)
C5	0.7097 (3)	0.4157 (2)	0.4680 (2)	0.0330 (6)
H5A	0.6367	0.4670	0.4990	0.049*
H5B	0.6636	0.3619	0.4182	0.049*
H5C	0.7815	0.4627	0.4304	0.049*
C4	0.9423 (3)	0.3008 (2)	0.7017 (2)	0.0302 (6)
H4	1.0472	0.2864	0.6892	0.036*
H1H	0.914 (5)	0.542 (3)	0.581 (3)	0.053 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0477 (5)	0.0172 (4)	0.0332 (4)	0.0017 (2)	−0.0059 (3)	0.0025 (2)
O1	0.0410 (11)	0.0178 (9)	0.0344 (10)	−0.0013 (7)	−0.0046 (7)	−0.0024 (7)
O2	0.0438 (11)	0.0188 (9)	0.0360 (10)	−0.0026 (8)	−0.0046 (8)	−0.0005 (7)
C3	0.0383 (13)	0.0172 (11)	0.0294 (12)	0.0014 (10)	0.0030 (10)	−0.0021 (9)
C6	0.0475 (17)	0.0328 (14)	0.0318 (14)	−0.0009 (12)	−0.0047 (12)	−0.0014 (11)
C2	0.0377 (14)	0.0178 (12)	0.0262 (11)	0.0024 (10)	0.0017 (10)	−0.0022 (9)
C1	0.0389 (14)	0.0187 (12)	0.0266 (11)	0.0046 (10)	0.0025 (10)	−0.0012 (9)
C5	0.0473 (15)	0.0183 (13)	0.0334 (13)	−0.0006 (11)	−0.0048 (11)	0.0004 (9)
C4	0.0352 (13)	0.0208 (12)	0.0346 (13)	0.0014 (10)	−0.0035 (10)	−0.0018 (10)

Geometric parameters (Å, º) top

S1—C1	1.778 (3)	C6—H6B	0.9800
S1—C4	1.816 (3)	C6—H6C	0.9800
O1—C1	1.238 (3)	C2—C1	1.434 (4)
O2—C3	1.326 (3)	C2—C5	1.498 (4)
O2—H1H	0.88 (4)	C5—H5A	0.9800
C3—C2	1.351 (4)	C5—H5B	0.9800
C3—C4	1.507 (4)	C5—H5C	0.9800
C6—C4	1.532 (4)	C4—H4	1.0000
C6—H6A	0.9800

C1—S1—C4	92.62 (12)	O1—C1—S1	121.6 (2)
C3—O2—H1H	116 (3)	C2—C1—S1	112.1 (2)
O2—C3—C2	128.8 (2)	C2—C5—H5A	109.5
O2—C3—C4	113.4 (2)	C2—C5—H5B	109.5
C2—C3—C4	117.8 (2)	H5A—C5—H5B	109.5
C4—C6—H6A	109.5	C2—C5—H5C	109.5
C4—C6—H6B	109.5	H5A—C5—H5C	109.5
H6A—C6—H6B	109.5	H5B—C5—H5C	109.5
C4—C6—H6C	109.5	C3—C4—C6	112.0 (2)
H6A—C6—H6C	109.5	C3—C4—S1	105.16 (18)
H6B—C6—H6C	109.5	C6—C4—S1	111.7 (2)
C3—C2—C1	112.3 (2)	C3—C4—H4	109.3
C3—C2—C5	127.3 (2)	C6—C4—H4	109.3
C1—C2—C5	120.4 (2)	S1—C4—H4	109.3
O1—C1—C2	126.3 (2)

O2—C3—C2—C1	−180.0 (2)	C4—S1—C1—O1	−179.6 (2)
C4—C3—C2—C1	−0.9 (3)	C4—S1—C1—C2	0.2 (2)
O2—C3—C2—C5	0.2 (5)	O2—C3—C4—C6	58.8 (3)
C4—C3—C2—C5	179.2 (2)	C2—C3—C4—C6	−120.4 (3)
C3—C2—C1—O1	−179.8 (3)	O2—C3—C4—S1	−179.77 (18)
C5—C2—C1—O1	0.0 (4)	C2—C3—C4—S1	1.0 (3)
C3—C2—C1—S1	0.4 (3)	C1—S1—C4—C3	−0.64 (19)
C5—C2—C1—S1	−179.8 (2)	C1—S1—C4—C6	121.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1H···O1ⁱ	0.88 (4)	1.77 (4)	2.621 (3)	164 (4)

Symmetry code: (i) −x+3/2, y+1/2, z.

3-Hydroxy-4-methyl-2H-thiophen-5-one (5) top

Crystal data top

C₅H₆O₂S	F(000) = 272
M_r = 130.16	D_x = 1.524 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.1054 (3) Å	Cell parameters from 1968 reflections
b = 22.9727 (13) Å	θ = 5.2–31.4°
c = 6.1928 (5) Å	µ = 0.46 mm⁻¹
β = 103.728 (7)°	T = 100 K
V = 567.37 (7) Å³	Needle, colourless
Z = 4	0.12 × 0.02 × 0.01 mm

Data collection top

Rigaku XtaLAB AFC12 diffractometer	1955 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	h = −5→5
T_min = 0.766, T_max = 1.000	k = −29→29
2121 measured reflections	l = −8→8
2121 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0078P)² + 1.3568P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max < 0.001
2121 reflections	Δρ_max = 0.43 e Å⁻³
79 parameters	Δρ_min = −0.33 e Å⁻³

Special details top

Refinement. Refined as a 2-component twin against a hklf 5 formatted datafile.

This datafile was created by CrysalisPro for twinning by a 180 degree rotation about rec 001.

Matrix used -0.9970 -0.0004 0.0038 0.0195 -0.9997 0.0133 0.7232 0.0009 0.9991

BASF refined to 0.432 (2).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.6910 (2)	0.70598 (3)	0.55558 (14)	0.0183 (2)
O1	0.8610 (6)	0.64486 (10)	0.9223 (4)	0.0231 (6)
O2	0.0808 (6)	0.58103 (10)	0.2795 (4)	0.0203 (5)
C1	0.6862 (8)	0.64503 (13)	0.7309 (5)	0.0164 (7)
C2	0.4606 (8)	0.60031 (13)	0.6216 (5)	0.0164 (7)
C3	0.3060 (8)	0.61502 (12)	0.4117 (5)	0.0155 (6)
C4	0.3963 (8)	0.67257 (13)	0.3276 (5)	0.0160 (6)
H4A	0.1943	0.6972	0.2798	0.019*
H4B	0.4987	0.6669	0.1996	0.019*
C5	0.4138 (10)	0.54539 (13)	0.7423 (6)	0.0213 (7)
H5A	0.2293	0.5227	0.6513	0.032*
H5B	0.3611	0.5553	0.8842	0.032*
H5C	0.6206	0.5224	0.7701	0.032*
H1H	0.003 (12)	0.597 (2)	0.156 (8)	0.045 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0204 (4)	0.0149 (3)	0.0183 (4)	−0.0017 (3)	0.0021 (3)	0.0002 (3)
O1	0.0287 (15)	0.0240 (11)	0.0138 (11)	0.0028 (10)	−0.0005 (10)	0.0007 (9)
O2	0.0211 (13)	0.0178 (10)	0.0187 (12)	−0.0034 (10)	−0.0017 (10)	0.0002 (9)
C1	0.0161 (17)	0.0162 (14)	0.0172 (15)	0.0052 (13)	0.0043 (12)	0.0002 (12)
C2	0.0182 (17)	0.0133 (13)	0.0189 (15)	0.0015 (12)	0.0067 (13)	0.0016 (12)
C3	0.0126 (14)	0.0138 (13)	0.0202 (16)	0.0013 (12)	0.0041 (13)	−0.0011 (12)
C4	0.0177 (16)	0.0146 (13)	0.0146 (14)	0.0001 (13)	0.0020 (12)	0.0012 (11)
C5	0.0261 (19)	0.0157 (14)	0.0226 (16)	−0.0006 (14)	0.0070 (15)	0.0044 (13)

Geometric parameters (Å, º) top

S1—C1	1.775 (3)	C2—C5	1.502 (4)
S1—C4	1.799 (3)	C3—C4	1.499 (4)
O1—C1	1.231 (4)	C4—H4A	0.9900
O2—C3	1.332 (4)	C4—H4B	0.9900
O2—H1H	0.84 (5)	C5—H5A	0.9800
C1—C2	1.440 (4)	C5—H5B	0.9800
C2—C3	1.347 (4)	C5—H5C	0.9800

C1—S1—C4	92.33 (15)	C3—C4—H4A	110.5
C3—O2—H1H	111 (3)	S1—C4—H4A	110.5
O1—C1—C2	127.8 (3)	C3—C4—H4B	110.5
O1—C1—S1	120.2 (3)	S1—C4—H4B	110.5
C2—C1—S1	112.0 (2)	H4A—C4—H4B	108.7
C3—C2—C1	112.2 (3)	C2—C5—H5A	109.5
C3—C2—C5	127.2 (3)	C2—C5—H5B	109.5
C1—C2—C5	120.6 (3)	H5A—C5—H5B	109.5
O2—C3—C2	123.0 (3)	C2—C5—H5C	109.5
O2—C3—C4	119.7 (3)	H5A—C5—H5C	109.5
C2—C3—C4	117.2 (3)	H5B—C5—H5C	109.5
C3—C4—S1	106.2 (2)

C4—S1—C1—O1	179.5 (3)	C5—C2—C3—O2	0.3 (5)
C4—S1—C1—C2	−1.2 (3)	C1—C2—C3—C4	1.4 (4)
O1—C1—C2—C3	179.4 (3)	C5—C2—C3—C4	−179.8 (3)
S1—C1—C2—C3	0.1 (4)	O2—C3—C4—S1	177.8 (3)
O1—C1—C2—C5	0.5 (5)	C2—C3—C4—S1	−2.1 (4)
S1—C1—C2—C5	−178.8 (3)	C1—S1—C4—C3	1.7 (2)
C1—C2—C3—O2	−178.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1H···O1ⁱ	0.84 (5)	1.80 (5)	2.629 (3)	168 (5)
C4—H4B···O1ⁱⁱ	0.99	2.58	3.552 (4)	169

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

Acknowledgements

The authors wish to thank the National Crystallographic Service at the University of Southampton for data collection on 5.

Funding information

The Saudi Arabia Universities External Joint Supervision Programme is thanked for funding a studentship (AN).

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