Some chalcones derived from thio-phene-3-carbaldehyde: synthesis and crystal structures.

The synthesis, spectroscopic data and crystal and mol-ecular structures of four 3-(3-phenyl-prop-1-ene-3-one-1-yl)thio-phene derivatives, namely 1-(4-hydroxy-phen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C13H10O2S, (1), 1-(4-meth-oxy-phen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C14H12O2S, (2), 1-(4-eth-oxy-phen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C15H14O2S, (3), and 1-(4--bromophen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C13H9BrOS, (4), are described. The four chalcones have been synthesized by reaction of thio-phene-3-carbaldehyde with an aceto-phenone derivative in an absolute ethanol solution containing potassium hydroxide, and differ in the substituent at the para position of the phenyl ring: -OH for 1, -OCH3 for 2, -OCH2CH3 for 3 and -Br for 4. The thio-phene ring in 4 was found to be disordered over two orientations with occupancies 0.702 (4) and 0.298 (4). The configuration about the C=C bond is E. The thio-phene and phenyl rings are inclined by 4.73 (12) for 1, 12.36 (11) for 2, 17.44 (11) for 3 and 46.1 (6) and 48.6 (6)° for 4, indicating that the -OH derivative is almost planar and the -Br derivative deviates the most from planarity. However, the substituent has no real influence on the bond distances in the α,β-unsaturated carbonyl moiety. The mol-ecular packing of 1 features chain formation in the a-axis direction by O-H⋯O contacts. In the case of 2 and 3, the packing is characterized by dimer formation through C-H⋯O inter-actions. In addition, C-H⋯π(thio-phene) inter-actions in 2 and C-H⋯S(thio-phene) inter-actions in 3 contribute to the three-dimensional architecture. The presence of C-H⋯π(thio-phene) contacts in the crystal of 4 results in chain formation in the c-axis direction. The Hirshfeld surface analysis shows that for all four derivatives, the highest contribution to surface contacts arises from contacts in which H atoms are involved.

Chemical context

Chalcones, typically referred to as Michael acceptors, can react with nucleophiles at the electrophilic β-position of the unsaturated system (Amslinger, 2010 ▸). Many chalcone deriv­atives containing an α,β-unsaturated carbonyl show potential biological applications such as being effective against amyloid β-induced cytotoxicity (Bukhari et al., 2014 ▸) and irreversibly angiotensin-converting enzyme inhibitors (Hea-Young Park Choo et al., 2000 ▸).

Thio­phene, C4H4S, belongs to a class of aromatic five-membered heterocycles containing one S heteroatom. Many thio­phene derivatives exhibit biological activities: anti­bacterial (Mishra et al., 2012 ▸), anti­allergic (Gillespie et al., 1985 ▸), analgesic (Laddi et al., 1998 ▸), and act as anti-inflammatory agents (Ferreira et al., 2006 ▸), anti­oxidant agents (Jarak et al., 2005 ▸) and anti­tumor agents (Gadad et al., 1994 ▸). With the introduction of a thio­phene ring into chalcones, it was hoped to design chalcones with inter­esting new structures and properties. The addition of the thio­phene ring to an α,β-unsaturated carbonyl group has also been investigated for a substitution at the Cα atom of the thio­phene ring (Harrison et al., 2006 ▸).

Recently, some thio­phene derivatives, such as N-(4-oxo-2-sulfanyl­idene-1,3-thia­zolidin-3-yl)-2-(thio­phen-3-yl)acetamide (Vu Quoc et al., 2017 ▸) and 4-phenyl-3-(thio­phen-3-yl-meth­yl)-1H-1,2,4-triazole-5(4H)-thione (Vu Quoc et al., 2018 ▸), were synthesized by us and their crystal structures were investigated by X-ray diffraction.

In this study, we present the synthesis and crystal structure of four chalcones (1–4) containing a thio­phene ring: 3-(3-phenyl­prop-1-ene-3-one-1-yl)thio­phene derivatives contain­ing –OH, –OCH3, –OCH2CH3 and –Br at the para position of the phenyl ring.

Structural commentary

The asymmetric units of 1, 2, 3 and 4 are illustrated in Figs. 1 ▸, 2 ▸, 3 ▸ and 4 ▸, respectively. The thio­phene group in 4 is disordered over two orientations by a rotation of about 180° about the C3—C6 bond in a 0.702 (4): 0.298 (4) ratio. Chalcone 1 bearing the –OH substituent is almost planar, with the dihedral angle between the thio­phene and phenyl rings being 4.73 (12)°. For the other chalcones, the deviation from planarity is significant, as illustrated by the dihedral angles: 12.36 (11)° for 2, 17.44 (11)° for 3 and 46.1 (6) and 48.6 (6)° for 4. The C6=C7 bond lengths [1.329 (3) Å for 1, 1.328 (3) Å for 2, 1.319 (3) Å for 3 and 1.325 (5) Å for 4] are almost identical. The configuration of the C6=C7 bond can be described as E [torsion angles C3—C6—C7—C8 are −175.4 (2), −177.8 (2), 179.75 (18) and −174.3 (3)° for 1–4, respectively]. For 1, this E configuration gives rise to an intra­molecular C6—H6⋯O9 inter­action (Table 1 ▸). The substituent at the para-position of the phenyl ring has no significant influence on the C8=O9 bond length [1.232 (3) Å in 1, 1.228 (3) Å in 2, 1.224 (2) Å in 3 and 1.224 (4) Å in 4].

Figure 1

The mol­eculare structure of 1 showing 50% displacement ellipsoids.

Figure 2

The mol­eculare structure of 2 showing 50% displacement ellipsoids.

Figure 3

The mol­eculare structure of 3 showing 50% displacement ellipsoids.

Figure 4

The mol­eculare structure of 4 showing 50% displacement ellipsoids. The minor-disorder component is shown in light blue.

Table 1

Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O16—H16⋯O9i	0.82	1.86	2.667 (2)	167
C6—H6⋯O9	0.93	2.46	2.785 (3)	100
C11—H11⋯O16ii	0.93	2.55	3.425 (3)	157

Symmetry codes: (i) ; (ii) .

Supra­molecular features

In chalcone derivative 1, which crystallizes in the ortho­rhom­bic space group Pbca, the –OH substituent is involved as donor in inter­molecular O16—H16⋯O9i [symmetry code: (i) x + , y,  − z] hydrogen bonding, resulting in the formation of chains of mol­ecules running in the a-axis direction (Fig. 5 ▸, Table 1 ▸). As acceptor, the –OH substituent inter­acts by inter­molecular C11—H11⋯O16 hydrogen bonding (Fig. 5 ▸, Table 1 ▸).

Figure 5

Partial crystal packing of 1 showing the inter­molecular hydrogen-bonding inter­actions as red dashed lines (see Table 1 ▸ for details).

Crystals of 2–4 belong to the monoclinic space group P21/c. The crystal packing of 2 is characterized by inversion-dimer formation between the meth­oxy groups by weak C17—H17B⋯O16i inter­actions [H17⋯O16i = 2.61 Å; symmetry code (i): −x + 1, −y + 2, −z + 2] and C—H⋯π(thio­phene) inter­actions (C5—H5⋯Cg1ii and C11—H11⋯Cg1iii; for details see Table 2 ▸ and Fig. 6 ▸).

Table 2

Hydrogen-bond geometry (Å, °) for 2

Cg1 is the centroid of the S1/C2–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cg1ii	0.93	2.94	3.602 (2)	129
C11—H11⋯Cg1iii	0.93	2.99	3.598 (2)	125

Symmetry codes: (ii) ; (iii) .

Figure 6

Partial crystal packing of 2 showing dimer formation through C—H⋯O (red dashed lines) and C—H⋯π inter­actions [grey dashed lines; Cg1 is the centroid of the thio­phene ring; symmetry codes: (i) −x + 1, −y + 2, z + 2, (ii) x, −y + , z + , (iii) −x, y − , −z + ].

In the packing of 3, C2—H2⋯O9i inter­actions result in dimeric units forming rings of (14) graph-set motif [symmetry code (i): 1 − x, 1 − y, 2 − z; Table 3 ▸, Fig. 7 ▸]. In addition, two weaker inter­actions are present in the packing. Inversion dimers are formed by C14—H14⋯O16ii inter­actions [H14⋯O16ii = 2.71 Å; symmetry code: (ii) −x + 2, −y + 1, −z + 2] enclosing an (8) ring motif. Chains of mol­ecules running in the a-axis direction are the consequence of C18iii—H18A iii⋯S1 inter­actions [H18A iii⋯S1 = 3.05 Å; symmetry code: (iii) x − 1, y, z]. These inter­molecular inter­actions result in the formation of sheets of mol­ecules parallel to the ac plane (Fig. 7 ▸).

Table 3

Hydrogen-bond geometry (Å, °) for 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O9i	0.93	2.47	3.324 (2)	153

Symmetry code: (i) .

Figure 7

Formation of sheets of mol­ecules of 3 by C—H⋯O and C—H⋯S inter­actions [red dashed lines; symmetry codes: (i) −x + 1, −y + 1, −z + 2, (ii) −x + 2, −y + 1, −z + 2, (iii) x − 1, y, z]

In the packing of 4, chains running in the c-axis direction are formed by C5—H5⋯π(thio­phene) inter­actions (Table 4 ▸, Fig. 8 ▸). At the other side of the mol­ecule, the closest contact for the Br16 atom is with H14 [Br16⋯H14i = 3.23 Å; Fig.8]. The shortest Br⋯Br distance [4.4621 (11) Å] in the crystal packing is Br16⋯Br16ii [symmetry code: (ii) −x + 2, −y + 1, −z + 2].

Table 4

Hydrogen-bond geometry (Å, °) for 4

Cg1 and Cg2 are the centroids of the major- and minor-disorder components of the thio­phene ring, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5A—H5A⋯Cg1i	0.93	2.80	3.493 (14)	132
C5A—H5A⋯Cg2i	0.93	2.85	3.52 (2)	130

Symmetry code: (i) .

Figure 8

Chains of mol­ecules in 4 running in the c-axis direction formed by C5A—H5A⋯Cg1i inter­actions [grey dashed lines, Cg1 is the centroid of the major-disorder component of the thio­phene ring; symmetry code: (i) x,  − y, z − ].

No voids or π–π stackings are observed in the crystal packing of 1–4.

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, update of February 2019; Groom et al., 2016 ▸) for 3-(3-thien­yl)prop-2-en-1-one gave three hits, viz. AYUPIU (Shalini et al., 2011 ▸), IBIRUJ (Oyarce et al., 2017 ▸) and UNAJIE (Baggio et al., 2016 ▸).

The configuration about the double bonds in the symmet­rical 1,5-bis­(thio­phen-3-yl)penta-1,4-dien-3-one (AYUPIU; Shalini et al., 2011 ▸) is twice E. The dihedral angle between the terminal thio­phene rings is 15.45 (10)°. In the crystal packing, C—H⋯O inter­actions link the mol­ecules into arrays in the ac plane that are further connected by C—H⋯π inter­actions.

Both thio­phene rings in 3-hy­droxy-1-(thio­phen-2-yl)-3-(thio­phen-3-yl)prop-2-en-1-one (IBIRUJ; Oyarce et al., 2017 ▸) are disordered; the major-disorder components are inclined to each other by 12.1 (3)°. Chains of mol­ecules running in the c-axis direction are formed through C—H⋯O inter­actions.

In the crystal of 1,3-bis­(3-thien­yl)prop-2-en-1-one (UNAJIE; Baggio et al., 2016 ▸), the stereochemistry about the double bond is E and the dihedral angle between the thio­phene rings is 8.88 (10)°. Columns of stacking mol­ecules along [010] indicate that π–π inter­actions play an important role in the crystal packing, together with C—H⋯O hydrogen bonds between the columns.

A search for 1-phenyl-3-(2-thien­yl)prop-2-en-1-one allowing substitution at the phenyl ring resulted in 19 hits of which the compound 1-(4-bromo­phen­yl)-3-(2-thien­yl)prop-2-en-1-one (GENXED; Patil et al., 2006 ▸; GENXED01; Arshad et al., 2017 ▸) is the 2-thienyl derivative of 4. In addition to similar cell parameters, the thio­phene ring also shows rotational disorder [ratio 0.791 (2):0.209 (2) for GENXED; Patil et al., 2006 ▸] and the angles between thio­phene and phenyl rings are comparable [46.49 (11) and 48.4 (3)° for GENXED; Patil et al., 2006 ▸].

Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ▸) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ▸) were performed using CrystalExplorer (Turner et al., 2017 ▸). The Hirshfeld surfaces of compounds 1–4 mapped over d norm are given in Fig. 9 ▸. The relative distributions from the different inter­atomic contacts to the Hirshfeld surfaces are presented in Table 5 ▸.

Figure 9

The Hirshfeld surface mapped over d norm for (a) compound 1 in the range −0.704 to 1.267 a.u., (b) compound 2 in the range −0.059 to 1.101 a.u., (c) compound 3 in the range −0.200 to 1.439 a.u. and (d) compound 4 in the range 0.007 to 0.942 a.u.

Table 5

Percentage contributions of inter­atomic contacts to the Hirshfeld surfaces for compounds (1–4)

Contact	1	2	3	4
H⋯H	28.8	33.5	44.5	28.5
S⋯H/H⋯S	13.0	11.6	10.2	3.9
C⋯H/H⋯C	30.4	33.9	22.1	32.6
O⋯H/H⋯O	18.5	15.8	13.8	11.1
C⋯C	3.2	0.7	4.5	2.4
C⋯S/S⋯C	3.7	0.9	3.5	0.0
S⋯S	0.0	1.5	0.0	0.0
S⋯O/O⋯S	0.3	0.0	0.1	0.0
C⋯O/O⋯C	1.8	1.6	1.0	1.0
O⋯O	0.0	0.6	0.0	0.0
Br⋯S/S⋯Br				2.8
Br⋯C/C⋯Br				0.6
Br⋯H/H⋯Br				16.5
Br⋯O/O⋯Br				0.0
Br⋯Br				0.5

The bright-red spots in Fig. 9 ▸ a near atoms O16 and O9 are indicative for the O16—H16⋯O9 hydrogen bond in the crystal packing of 1. The additional faint-red spots illustrate C—H⋯O inter­actions. The most significant contributions to the Hirshfeld surface are from C⋯H/H⋯C (30.4%), H⋯H (28.8%) and O⋯H/H⋯O (18.5%) contacts (Table 5 ▸).

For compound 2, the donor and acceptor of the relatively weak C17—H17B⋯O16 inter­action are viewed as diminutive red spots near atoms H17B and O16 in Fig. 9 ▸ b. The C—H⋯π(thio­phene) inter­actions are indicated by the high contribution from C⋯H/H⋯C contacts (33.9%) to the Hirshfeld surface (Table 5 ▸).

The bright-red spots in Fig. 9 ▸ c near atoms O9 and H2 of 3 refer to the strong C2—H2⋯O9 dimer formation, while the faint-red spots near atoms O16 and H14 are indicative for the relatively weak C14—H14⋯O16 dimer formation. Near atom C2 another faint-red spot refers to a contact (2.73 Å) with atom H5.

The Hirshfeld surface mapped over d norm for 4 (Fig. 9 ▸ d) shows no short inter­atomic contacts. Again the C—H⋯π inter­action with the disordered thio­phene ring is reflected in the high contribution from C⋯H/H⋯C contacts (32.6%) to the Hirshfeld surface (Table 5 ▸).

For the four derivatives, the largest contributions of inter­atomic contacts to the Hirshfeld surface are contacts in which H atoms are involved (Table 5 ▸).

Synthesis and crystallization

The reaction scheme to synthesize the title compounds 1–4 is given in Fig. 10 ▸.

Figure 10

Reaction scheme for the title compounds 1–4.

In a 250 mL beaker, thio­phene-3-carbaldehyde (0.1 mole) and substituted aceto­phenone (0.1 mol) were dissolved in ethanol (100 mL). To this mixture, a 50% KOH (10 mL) solution was added and the mixture was stirred by a magnetic stirrer for 5 h at room temperature until a precipitate appeared. The products 1–4 were obtained as solids, which were filtered under low pressure and recrystallized from ethanol.

Yellow crystals; yield 90%; m.p. 388 K; IR (Nicolet Impact 410 FT–IR, KBr, cm−1): 3456.8 (OH), 2983.3 (CH aromatic, alkene), 1643.1 (C=O), 1596.8 (C=C, C=N), 1037.4 [–CH=(trans)]; 1H NMR [Bruker XL-500, 500 MHz, d 6-CDCl3, δ (ppm), J (Hz)]: 6.93 (d, 2H, J = 9.0, H11,11′), 7.34 (d, 1H, J = 15.5, H7), 7.37 (d, 1H, J = 2, J = 3, H2), 7.41 (dd, 1H, J = 5, H4), 7.59 (dd, 1H, J = 5.5, H5), 7.79 (d, 1H, J = 15.5, H6), 7.98 (d, 2H, J = 8.5, H10,10′). 13C NMR [Bruker XL-500, 125 MHz, d 6-CDCl3, δ (ppm)]: 121.63 (C2); 128.79 (C3), 126.98 (C4); 125.26 (C5); 131.39 (C6); 131.07 (C7); 189.0 (C8); 159.84 (C9); 138.33 (C10,10′); 137.64 (C11,11′); 115.4 (C12). Calculation for C13H10O2S: M = 230 au.

White crystals; yield 70%; m.p. 378 K; IR (Nicolet Impact 410 FT–IR, KBr, cm−1): 3009.3 (CH alkane), 2974.3 (CH aromatic, alkene), 1651.1 (C=O), 1597.5 (C=C, C=N), 1017.2 [–CH=(trans)]; 1H NMR [Bruker XL-500, 500 MHz, d 6-CDCl3, δ (ppm), J (Hz)]: 3.89 (s, 3H, OCH3), 6.98 (d, 2H, J = 9.0, H11,11′), 7.35 (d, 1H, J = 15.5, H7), 7.36 (dd, 1H, J = 2.5, J = 5, H2), 7.42 (d, 1H, J = 5, H4), 7.58 (dd, 1H, J = 2.5, H5), 7.79 (d, 1H, J = 16, H6), 8.02 (d, 2H, J = 9, H10,10′). 13C NMR [Bruker XL-500, 125 MHz, d 6-CDCl3, δ (ppm)]: 121.70 (C2), 128.68 (C3), 126.94 (C4), 125.28 (C5), 131.19 (C6), 130.74 (C7), 188.96 (C8), 163.41 (C9), 138.37 (C10,10′), 137.44 (C11,11′), 113.85 (C12), 55.5 (OCH3). Calculation for C14H12O2S: M = 244 au.

White crystals; yield 50%; m.p. 380 K; IR (Nicolet Impact 410 FT–IR, KBr, cm−1): 3010.6 (CH alkane), 2983.3 (CH aromatic, alkene), 1657.1 (C=O), 1596.7 (C=C, C=N), 1011.4 [–CH=(trans)]; 1H NMR [Bruker XL-500, 500 MHz, d 6-CDCl3, δ (ppm), J (Hz)]: 1.53 (t, 3H, J = 7, OCH2CH 3), 4.12 (q, 2H, J = 7, 7, OCH 2CH3), 6.96 (d, 2H, J = 9.0, H11,11′), 7.36 (d, 1H, J = 15.5, H7), 7.36 (d, 1H, J = 2, J = 3, H2), 7.42 (dd, 1H, J = 1.5, J = 5, H4), 7.58 (dd, 1H, J = 1.5, J = 5.5, H5), 7.78 (d, 1H, J = 15.5, H6), 8.01 (d, 2H, J = 9, H10,10′). 13C NMR [Bruker XL-500, 125 MHz, d 6-CDCl3, δ (ppm)]: 121.73 (C2); 128.63 (C3), 126.93 (C4); 125.29 (C5); 131.00 (C6); 130.75 (C7); 188.96 (C8); 162.85 (C9); 138.4 (C10,10′); 137.37 (C11,11′); 114.3 (C12); 63.80 (OCH2CH3); 14.7 (OCH2 CH3). Calculation for C15H14O2S: M = 258 au.

Bright-yellow crystals; yield 99%; m.p. 353 K; IR (Nicolet Impact 410 FT–IR, KBr, cm−1): 3090.7 (CH aromatic, alkene), 1654.5 (C=O), 1595.8 (C=C, C=N), 1006.1 [–CH=(trans)]; 1H NMR [Bruker XL-500, 500 MHz, d 6-CDCl3, δ (ppm), J (Hz)]: 6.69 (d, 2H, J = 9.0, H11,11′), 7.35 (d, 1H, J = 15.5, H7), 7.36 (dd, 1H, J = 3, J = 5.5, H2), 7.41 (d, 1H, J = 5.5, H4), 7.56 (dd, 1H, J = 3, H5), 7.77(d, 1H, J = 15.5, H6), 7.91 (d, 2H, J = 8.5, H10,10′). 13C NMR [Bruker XL-500, 125 MHz, d 6-CDCl3, δ (ppm)]: 121.29 (C2), 127.81 (C3), 127.18 (C4), 125.21 (C5), 129.97 (C6), 131.93 (C7), 189.66 (C8), 138.81 (C9), 138.81 (C10,10′), 138.05(C11,11′), 129.50 (C12). Calculation for C13H9OSBr: M = 293 au.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6 ▸.

Table 6

Experimental details

	1	3	2	4
Crystal data
Chemical formula	C13H10O2S	C14H12O2S	C15H14O2S	C13H9BrOS
M r	230.27	244.30	258.32	293.17
Crystal system, space group	Orthorhombic, P b c a	Monoclinic, P21/c	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	294	294	294	293
a, b, c (Å)	11.0808 (5), 9.0251 (5), 22.8157 (10)	16.4118 (13), 5.8387 (5), 12.6456 (9)	16.5120 (8), 7.7851 (5), 10.4913 (5)	14.1245 (7), 14.2016 (13), 5.8809 (4)
α, β, γ (°)	90, 90, 90	90, 97.279 (7), 90	90, 96.813 (4), 90	90, 98.081 (6), 90
V (Å3)	2281.69 (19)	1201.98 (16)	1339.11 (13)	1167.93 (15)
Z	8	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	0.26	0.26	0.23	3.67
Crystal size (mm)	0.4 × 0.3 × 0.07	0.45 × 0.3 × 0.15	0.5 × 0.35 × 0.15	0.4 × 0.4 × 0.05
Data collection
Diffractometer	SuperNova, single source at offset/far, Eos	SuperNova, single source at offset/far, Eos	SuperNova, single source at offset/far, Eos	SuperNova, single source at offset/far, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)
T min, T max	0.522, 1.000	0.803, 1.000	0.733, 1.000	0.367, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9745, 2333, 1814	5075, 2457, 1771	13246, 2734, 2162	12050, 2392, 1683
R int	0.019	0.021	0.035	0.045
(sin θ/λ)max (Å−1)	0.625	0.625	0.625	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.049, 0.134, 1.05	0.046, 0.118, 1.04	0.047, 0.141, 1.05	0.043, 0.107, 1.02
No. of reflections	2333	2457	2734	2392
No. of parameters	146	156	165	158
No. of restraints	0	0	0	20
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.20, −0.35	0.16, −0.26	0.19, −0.28	0.40, −0.46

Computer programs: CrysAlis PRO (Rigaku OD, 2018 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

All H atoms were placed in idealized positions and refined in riding mode, with U iso(H) values assigned as 1.2U eq of the parent atoms (1.5 times for methyl groups), with C—H distances of 0.93 (aromatic and =CH), 0.96 (CH3) and 0.97 Å (CH2), and O—H distances of 0.82 Å (rotating OH).

In 4, the thio­phene ring was disordered over two positions [population parameters 0.702 (4) and 0.298 (4)] and was refined with restraints for the bond lengths and angles in the ring. The anisotropic temperature factors for atoms S1, C2, C4 and C5 in both orientations were constrained to be equal. In the final cycles of refinement, two and one outliers were omitted for 1 and 2, respectively.

Crystal structure: contains datablock(s) 1, 2, 3, 4. DOI: 10.1107/S2056989019007503/lh5905sup1.cif

Structure factors: contains datablock(s) 1. DOI: 10.1107/S2056989019007503/lh59051sup2.hkl

Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989019007503/lh59052sup3.hkl

Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989019007503/lh59053sup4.hkl

Structure factors: contains datablock(s) 4. DOI: 10.1107/S2056989019007503/lh59054sup5.hkl

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Supporting information file. DOI: 10.1107/S2056989019007503/lh59051sup6.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019007503/lh59052sup7.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019007503/lh59053sup8.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019007503/lh59054sup9.cml

CCDC references: 1918095, 1918094, 1918093, 1918092

Additional supporting information: crystallographic information; 3D view; checkCIF report

C13H10O2S	Dx = 1.341 Mg m−3
Mr = 230.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3900 reflections
a = 11.0808 (5) Å	θ = 3.0–27.0°
b = 9.0251 (5) Å	µ = 0.26 mm−1
c = 22.8157 (10) Å	T = 294 K
V = 2281.69 (19) Å3	Block, yellow
Z = 8	0.4 × 0.3 × 0.07 mm
F(000) = 960

SuperNova, single source at offset/far, Eos diffractometer	2333 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	1814 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 15.9631 pixels mm-1	θmax = 26.4°, θmin = 2.6°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −4→11
Tmin = 0.522, Tmax = 1.000	l = −27→28
9745 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049	H-atom parameters constrained
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0463P)2 + 1.4972P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2333 reflections	Δρmax = 0.20 e Å−3
146 parameters	Δρmin = −0.35 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.89495 (8)	0.20994 (11)	0.39007 (3)	0.0907 (3)
C2	0.8168 (2)	0.3325 (4)	0.43118 (11)	0.0783 (8)
H2	0.749344	0.383495	0.417667	0.094*
C3	0.8629 (2)	0.3490 (3)	0.48637 (9)	0.0533 (6)
C4	0.9650 (2)	0.2575 (3)	0.49383 (11)	0.0637 (7)
H4	1.008933	0.252750	0.528507	0.076*
C5	0.9932 (2)	0.1760 (3)	0.44462 (11)	0.0704 (7)
H5	1.058032	0.110896	0.441931	0.085*
C6	0.8079 (2)	0.4425 (3)	0.53031 (10)	0.0550 (6)
H6	0.738492	0.493292	0.519204	0.066*
C7	0.8460 (2)	0.4637 (3)	0.58489 (9)	0.0521 (5)
H7	0.918191	0.420470	0.596709	0.062*
C8	0.77790 (19)	0.5528 (2)	0.62690 (9)	0.0486 (5)
O9	0.67534 (14)	0.5953 (2)	0.61457 (7)	0.0621 (5)
C10	0.83162 (18)	0.5889 (2)	0.68496 (9)	0.0458 (5)
C11	0.9339 (2)	0.5188 (3)	0.70693 (10)	0.0511 (5)
H11	0.973899	0.449440	0.683877	0.061*
C12	0.9773 (2)	0.5503 (3)	0.76226 (10)	0.0536 (6)
H12	1.044085	0.499832	0.776762	0.064*
C13	0.92110 (19)	0.6570 (2)	0.79603 (9)	0.0477 (5)
C14	0.8212 (2)	0.7312 (3)	0.77412 (10)	0.0545 (6)
H14	0.784258	0.804822	0.796302	0.065*
C15	0.77688 (19)	0.6960 (3)	0.71980 (10)	0.0518 (5)
H15	0.708722	0.744893	0.705920	0.062*
O16	0.95988 (15)	0.6936 (2)	0.85077 (6)	0.0601 (5)
H16	1.025310	0.654151	0.857006	0.090*

	U11	U22	U33	U12	U13	U23
S1	0.0964 (6)	0.1162 (8)	0.0596 (4)	0.0193 (5)	−0.0060 (4)	−0.0214 (4)
C2	0.0726 (17)	0.104 (2)	0.0583 (15)	0.0212 (17)	−0.0110 (13)	−0.0091 (15)
C3	0.0502 (12)	0.0622 (14)	0.0475 (12)	0.0007 (11)	0.0014 (10)	0.0023 (11)
C4	0.0598 (14)	0.0797 (17)	0.0515 (13)	0.0102 (13)	−0.0034 (11)	0.0004 (12)
C5	0.0670 (15)	0.0795 (19)	0.0647 (16)	0.0183 (15)	0.0016 (13)	−0.0065 (14)
C6	0.0479 (12)	0.0638 (15)	0.0533 (13)	0.0051 (11)	0.0010 (10)	0.0052 (11)
C7	0.0478 (12)	0.0562 (13)	0.0522 (12)	0.0038 (10)	0.0000 (10)	0.0012 (10)
C8	0.0475 (12)	0.0483 (12)	0.0500 (12)	−0.0017 (10)	0.0024 (9)	0.0060 (10)
O9	0.0497 (9)	0.0816 (12)	0.0550 (9)	0.0138 (9)	−0.0052 (7)	−0.0024 (8)
C10	0.0427 (11)	0.0441 (12)	0.0507 (12)	−0.0017 (9)	0.0037 (9)	0.0038 (9)
C11	0.0498 (12)	0.0477 (12)	0.0558 (13)	0.0051 (10)	−0.0003 (10)	−0.0054 (10)
C12	0.0482 (12)	0.0522 (13)	0.0604 (14)	0.0072 (11)	−0.0063 (10)	−0.0014 (11)
C13	0.0466 (11)	0.0492 (12)	0.0474 (11)	−0.0054 (10)	0.0022 (9)	0.0005 (10)
C14	0.0498 (12)	0.0562 (14)	0.0577 (13)	0.0065 (11)	0.0043 (10)	−0.0082 (11)
C15	0.0442 (11)	0.0523 (13)	0.0590 (13)	0.0079 (10)	−0.0022 (10)	0.0005 (11)
O16	0.0580 (10)	0.0712 (11)	0.0510 (9)	0.0040 (9)	−0.0045 (7)	−0.0082 (8)

S1—C2	1.689 (3)	C8—C10	1.488 (3)
S1—C5	1.682 (3)	C10—C11	1.392 (3)
C2—H2	0.9300	C10—C15	1.391 (3)
C2—C3	1.367 (3)	C11—H11	0.9300
C3—C4	1.411 (3)	C11—C12	1.380 (3)
C3—C6	1.446 (3)	C12—H12	0.9300
C4—H4	0.9300	C12—C13	1.382 (3)
C4—C5	1.378 (3)	C13—C14	1.387 (3)
C5—H5	0.9300	C13—O16	1.361 (2)
C6—H6	0.9300	C14—H14	0.9300
C6—C7	1.329 (3)	C14—C15	1.370 (3)
C7—H7	0.9300	C15—H15	0.9300
C7—C8	1.461 (3)	O16—H16	0.8200
C8—O9	1.232 (3)
C5—S1—C2	92.31 (13)	O9—C8—C10	120.3 (2)
S1—C2—H2	123.5	C11—C10—C8	123.2 (2)
C3—C2—S1	113.0 (2)	C15—C10—C8	119.10 (19)
C3—C2—H2	123.5	C15—C10—C11	117.7 (2)
C2—C3—C4	110.3 (2)	C10—C11—H11	119.4
C2—C3—C6	123.0 (2)	C12—C11—C10	121.3 (2)
C4—C3—C6	126.6 (2)	C12—C11—H11	119.4
C3—C4—H4	123.3	C11—C12—H12	120.1
C5—C4—C3	113.3 (2)	C11—C12—C13	119.8 (2)
C5—C4—H4	123.3	C13—C12—H12	120.1
S1—C5—H5	124.5	C12—C13—C14	119.7 (2)
C4—C5—S1	111.0 (2)	O16—C13—C12	122.6 (2)
C4—C5—H5	124.5	O16—C13—C14	117.8 (2)
C3—C6—H6	116.6	C13—C14—H14	120.0
C7—C6—C3	126.9 (2)	C15—C14—C13	120.0 (2)
C7—C6—H6	116.6	C15—C14—H14	120.0
C6—C7—H7	119.0	C10—C15—H15	119.3
C6—C7—C8	122.0 (2)	C14—C15—C10	121.4 (2)
C8—C7—H7	119.0	C14—C15—H15	119.3
C7—C8—C10	119.85 (19)	C13—O16—H16	109.5
O9—C8—C7	119.9 (2)
S1—C2—C3—C4	0.1 (3)	C7—C8—C10—C15	167.8 (2)
S1—C2—C3—C6	−177.0 (2)	C8—C10—C11—C12	−176.7 (2)
C2—S1—C5—C4	0.5 (3)	C8—C10—C15—C14	178.6 (2)
C2—C3—C4—C5	0.3 (4)	O9—C8—C10—C11	165.4 (2)
C2—C3—C6—C7	179.4 (3)	O9—C8—C10—C15	−13.6 (3)
C3—C4—C5—S1	−0.5 (3)	C10—C11—C12—C13	−2.3 (4)
C3—C6—C7—C8	−175.4 (2)	C11—C10—C15—C14	−0.5 (3)
C4—C3—C6—C7	2.7 (4)	C11—C12—C13—C14	0.3 (3)
C5—S1—C2—C3	−0.3 (3)	C11—C12—C13—O16	−179.7 (2)
C6—C3—C4—C5	177.3 (2)	C12—C13—C14—C15	1.6 (3)
C6—C7—C8—O9	9.1 (4)	C13—C14—C15—C10	−1.5 (4)
C6—C7—C8—C10	−172.3 (2)	C15—C10—C11—C12	2.4 (3)
C7—C8—C10—C11	−13.2 (3)	O16—C13—C14—C15	−178.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16···O9i	0.82	1.86	2.667 (2)	167
C6—H6···O9	0.93	2.46	2.785 (3)	100
C11—H11···O16ii	0.93	2.55	3.425 (3)	157

C14H12O2S	F(000) = 512
Mr = 244.30	Dx = 1.350 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.4118 (13) Å	Cell parameters from 1920 reflections
b = 5.8387 (5) Å	θ = 3.2–27.3°
c = 12.6456 (9) Å	µ = 0.26 mm−1
β = 97.279 (7)°	T = 294 K
V = 1201.98 (16) Å3	Block, white
Z = 4	0.45 × 0.3 × 0.15 mm

SuperNova, single source at offset/far, Eos diffractometer	2457 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	1771 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 15.9631 pixels mm-1	θmax = 26.4°, θmin = 2.5°
ω scans	h = −19→20
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −4→7
Tmin = 0.803, Tmax = 1.000	l = −15→15
5075 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046	w = 1/[σ2(Fo2) + (0.0416P)2 + 0.3903P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.118	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.16 e Å−3
2457 reflections	Δρmin = −0.26 e Å−3
156 parameters	Extinction correction: SHELXL-2016/4 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0141 (16)

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.

	x	y	z	Uiso*/Ueq
S1	0.04793 (4)	0.76040 (12)	0.07886 (5)	0.0654 (3)
C2	0.10560 (14)	0.9740 (4)	0.14100 (16)	0.0519 (6)
H2	0.116506	1.111424	0.108336	0.062*
C3	0.13426 (12)	0.9216 (4)	0.24447 (15)	0.0421 (5)
C4	0.10869 (13)	0.6985 (4)	0.27105 (18)	0.0494 (6)
H4	0.122905	0.631591	0.337572	0.059*
C5	0.06133 (14)	0.5929 (4)	0.18926 (18)	0.0558 (6)
H5	0.039091	0.447129	0.193370	0.067*
C6	0.18106 (12)	1.0798 (4)	0.31699 (16)	0.0463 (5)
H6	0.191362	1.224036	0.290462	0.056*
C7	0.21052 (13)	1.0373 (4)	0.41779 (16)	0.0477 (5)
H7	0.202752	0.892707	0.445659	0.057*
C8	0.25502 (13)	1.2111 (4)	0.48691 (17)	0.0468 (5)
O9	0.25416 (11)	1.4134 (3)	0.46020 (13)	0.0657 (5)
C10	0.30162 (12)	1.1378 (4)	0.58960 (15)	0.0430 (5)
C11	0.28855 (13)	0.9319 (4)	0.63854 (16)	0.0499 (6)
H11	0.249747	0.830772	0.605098	0.060*
C12	0.33136 (13)	0.8718 (4)	0.73559 (16)	0.0522 (6)
H12	0.320424	0.733792	0.767704	0.063*
C13	0.39048 (13)	1.0180 (4)	0.78457 (16)	0.0467 (5)
C14	0.40604 (15)	1.2229 (4)	0.73538 (19)	0.0588 (7)
H14	0.446764	1.320516	0.767118	0.071*
C15	0.36170 (15)	1.2817 (4)	0.64040 (18)	0.0565 (6)
H15	0.371979	1.421195	0.609103	0.068*
O16	0.43757 (9)	0.9765 (3)	0.87912 (11)	0.0586 (5)
C17	0.42397 (17)	0.7696 (5)	0.93373 (19)	0.0679 (7)
H17A	0.367631	0.762376	0.946635	0.102*
H17B	0.459086	0.765633	1.000460	0.102*
H17C	0.436021	0.641159	0.890914	0.102*

	U11	U22	U33	U12	U13	U23
S1	0.0659 (4)	0.0704 (5)	0.0552 (4)	0.0009 (3)	−0.0104 (3)	−0.0052 (3)
C2	0.0571 (13)	0.0487 (14)	0.0489 (12)	0.0044 (11)	0.0019 (10)	0.0049 (11)
C3	0.0414 (11)	0.0426 (13)	0.0418 (11)	0.0067 (9)	0.0036 (9)	0.0015 (10)
C4	0.0497 (12)	0.0462 (14)	0.0515 (12)	0.0020 (10)	0.0033 (10)	0.0054 (11)
C5	0.0510 (13)	0.0420 (13)	0.0730 (15)	−0.0027 (11)	0.0029 (11)	−0.0003 (12)
C6	0.0475 (12)	0.0419 (13)	0.0489 (12)	0.0019 (10)	0.0042 (10)	0.0038 (10)
C7	0.0507 (12)	0.0444 (13)	0.0470 (12)	−0.0033 (10)	0.0027 (10)	0.0024 (11)
C8	0.0487 (12)	0.0454 (14)	0.0469 (12)	−0.0009 (10)	0.0086 (9)	0.0006 (11)
O9	0.0854 (13)	0.0450 (10)	0.0631 (10)	−0.0029 (9)	−0.0039 (9)	0.0039 (9)
C10	0.0458 (11)	0.0421 (12)	0.0415 (11)	−0.0038 (10)	0.0072 (9)	−0.0039 (10)
C11	0.0523 (13)	0.0500 (14)	0.0455 (12)	−0.0152 (11)	−0.0013 (10)	−0.0011 (11)
C12	0.0595 (14)	0.0490 (14)	0.0465 (12)	−0.0131 (11)	0.0007 (10)	0.0038 (11)
C13	0.0449 (12)	0.0523 (14)	0.0420 (11)	−0.0022 (10)	0.0026 (9)	−0.0064 (11)
C14	0.0611 (14)	0.0541 (15)	0.0578 (14)	−0.0200 (12)	−0.0058 (11)	−0.0068 (12)
C15	0.0686 (15)	0.0452 (14)	0.0544 (13)	−0.0158 (12)	0.0027 (11)	0.0005 (11)
O16	0.0583 (10)	0.0640 (11)	0.0495 (9)	−0.0088 (8)	−0.0083 (7)	−0.0020 (8)
C17	0.0807 (18)	0.0666 (18)	0.0513 (14)	−0.0019 (14)	−0.0108 (12)	0.0017 (13)

S1—C2	1.697 (2)	C10—C11	1.381 (3)
S1—C5	1.696 (2)	C10—C15	1.390 (3)
C2—H2	0.9300	C11—H11	0.9300
C2—C3	1.368 (3)	C11—C12	1.380 (3)
C3—C4	1.422 (3)	C12—H12	0.9300
C3—C6	1.451 (3)	C12—C13	1.379 (3)
C4—H4	0.9300	C13—C14	1.387 (3)
C4—C5	1.360 (3)	C13—O16	1.361 (2)
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C14—C15	1.367 (3)
C6—C7	1.328 (3)	C15—H15	0.9300
C7—H7	0.9300	O16—C17	1.423 (3)
C7—C8	1.471 (3)	C17—H17A	0.9600
C8—O9	1.228 (3)	C17—H17B	0.9600
C8—C10	1.484 (3)	C17—H17C	0.9600
C5—S1—C2	92.07 (11)	C15—C10—C8	119.1 (2)
S1—C2—H2	123.8	C10—C11—H11	119.0
C3—C2—S1	112.49 (18)	C12—C11—C10	122.0 (2)
C3—C2—H2	123.8	C12—C11—H11	119.0
C2—C3—C4	110.8 (2)	C11—C12—H12	120.3
C2—C3—C6	123.5 (2)	C13—C12—C11	119.5 (2)
C4—C3—C6	125.60 (19)	C13—C12—H12	120.3
C3—C4—H4	123.4	C12—C13—C14	119.44 (19)
C5—C4—C3	113.1 (2)	O16—C13—C12	125.0 (2)
C5—C4—H4	123.4	O16—C13—C14	115.54 (19)
S1—C5—H5	124.3	C13—C14—H14	119.9
C4—C5—S1	111.50 (18)	C15—C14—C13	120.2 (2)
C4—C5—H5	124.3	C15—C14—H14	119.9
C3—C6—H6	117.0	C10—C15—H15	119.3
C7—C6—C3	125.9 (2)	C14—C15—C10	121.4 (2)
C7—C6—H6	117.0	C14—C15—H15	119.3
C6—C7—H7	118.8	C13—O16—C17	118.08 (18)
C6—C7—C8	122.3 (2)	O16—C17—H17A	109.5
C8—C7—H7	118.8	O16—C17—H17B	109.5
C7—C8—C10	118.9 (2)	O16—C17—H17C	109.5
O9—C8—C7	120.8 (2)	H17A—C17—H17B	109.5
O9—C8—C10	120.3 (2)	H17A—C17—H17C	109.5
C11—C10—C8	123.42 (19)	H17B—C17—H17C	109.5
C11—C10—C15	117.43 (19)
S1—C2—C3—C4	1.0 (2)	C8—C10—C11—C12	−178.1 (2)
S1—C2—C3—C6	−176.32 (16)	C8—C10—C15—C14	179.6 (2)
C2—S1—C5—C4	−0.02 (19)	O9—C8—C10—C11	162.0 (2)
C2—C3—C4—C5	−1.1 (3)	O9—C8—C10—C15	−17.9 (3)
C2—C3—C6—C7	−179.7 (2)	C10—C11—C12—C13	−1.6 (4)
C3—C4—C5—S1	0.6 (3)	C11—C10—C15—C14	−0.3 (4)
C3—C6—C7—C8	−177.8 (2)	C11—C12—C13—C14	−0.1 (3)
C4—C3—C6—C7	3.3 (4)	C11—C12—C13—O16	−178.9 (2)
C5—S1—C2—C3	−0.60 (18)	C12—C13—C14—C15	1.6 (4)
C6—C3—C4—C5	176.2 (2)	C12—C13—O16—C17	−1.6 (3)
C6—C7—C8—O9	13.0 (3)	C13—C14—C15—C10	−1.4 (4)
C6—C7—C8—C10	−166.6 (2)	C14—C13—O16—C17	179.5 (2)
C7—C8—C10—C11	−18.4 (3)	C15—C10—C11—C12	1.8 (3)
C7—C8—C10—C15	161.7 (2)	O16—C13—C14—C15	−179.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cg1i	0.93	2.94	3.602 (2)	129
C11—H11···Cg1ii	0.93	2.99	3.598 (2)	125

C15H14O2S	F(000) = 544
Mr = 258.32	Dx = 1.281 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.5120 (8) Å	Cell parameters from 4827 reflections
b = 7.7851 (5) Å	θ = 3.3–27.9°
c = 10.4913 (5) Å	µ = 0.23 mm−1
β = 96.813 (4)°	T = 294 K
V = 1339.11 (13) Å3	Block, white
Z = 4	0.5 × 0.35 × 0.15 mm

SuperNova, single source at offset/far, Eos diffractometer	2734 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2162 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.035
Detector resolution: 15.9631 pixels mm-1	θmax = 26.4°, θmin = 2.5°
ω scans	h = −20→20
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −9→9
Tmin = 0.733, Tmax = 1.000	l = −12→13
13246 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.047	w = 1/[σ2(Fo2) + (0.0633P)2 + 0.4069P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.141	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.19 e Å−3
2734 reflections	Δρmin = −0.28 e Å−3
165 parameters	Extinction correction: SHELXL-2016/4 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0073 (17)

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.

	x	y	z	Uiso*/Ueq
S1	0.28921 (3)	0.41932 (9)	0.57261 (6)	0.0697 (3)
C2	0.35583 (12)	0.4427 (3)	0.70816 (19)	0.0558 (5)
H2	0.340852	0.481608	0.785855	0.067*
C3	0.43322 (11)	0.3985 (2)	0.69052 (17)	0.0458 (4)
C4	0.43736 (12)	0.3435 (3)	0.56166 (18)	0.0551 (5)
H4	0.485324	0.307932	0.531318	0.066*
C5	0.36332 (13)	0.3486 (3)	0.4872 (2)	0.0588 (5)
H5	0.354921	0.317238	0.401153	0.071*
C6	0.50131 (12)	0.4082 (2)	0.79107 (18)	0.0483 (5)
H6	0.489859	0.443268	0.871763	0.058*
C7	0.57803 (12)	0.3718 (3)	0.77867 (18)	0.0518 (5)
H7	0.591201	0.335993	0.699110	0.062*
C8	0.64340 (12)	0.3860 (3)	0.88615 (17)	0.0490 (5)
O9	0.62809 (9)	0.3934 (2)	0.99739 (13)	0.0670 (5)
C10	0.72986 (12)	0.3954 (2)	0.85742 (17)	0.0476 (5)
C11	0.75356 (12)	0.3597 (3)	0.73833 (18)	0.0540 (5)
H11	0.714251	0.329023	0.671266	0.065*
C12	0.83455 (13)	0.3684 (3)	0.7166 (2)	0.0594 (5)
H12	0.849281	0.344313	0.635592	0.071*
C13	0.89322 (13)	0.4129 (3)	0.8157 (2)	0.0568 (5)
C14	0.87043 (13)	0.4512 (3)	0.9360 (2)	0.0618 (6)
H14	0.909675	0.483056	1.002823	0.074*
C15	0.79065 (13)	0.4420 (3)	0.95555 (19)	0.0571 (5)
H15	0.776104	0.467265	1.036427	0.069*
O16	0.97471 (9)	0.4227 (2)	0.80525 (16)	0.0762 (5)
C17	1.00141 (16)	0.3853 (4)	0.6849 (3)	0.0901 (9)
H17A	0.978364	0.467414	0.621098	0.108*
H17B	0.983604	0.271209	0.656990	0.108*
C18	1.09277 (17)	0.3952 (5)	0.6991 (4)	0.1138 (13)
H18A	1.111988	0.364258	0.619307	0.171*
H18B	1.115025	0.317438	0.765128	0.171*
H18C	1.109771	0.510223	0.721773	0.171*

	U11	U22	U33	U12	U13	U23
S1	0.0502 (4)	0.0898 (5)	0.0684 (4)	0.0040 (3)	0.0052 (3)	0.0000 (3)
C2	0.0549 (12)	0.0668 (13)	0.0479 (11)	0.0079 (10)	0.0153 (9)	0.0016 (9)
C3	0.0481 (10)	0.0477 (10)	0.0430 (10)	0.0015 (8)	0.0115 (8)	0.0017 (8)
C4	0.0505 (11)	0.0663 (13)	0.0500 (11)	0.0015 (9)	0.0128 (9)	−0.0087 (9)
C5	0.0619 (13)	0.0676 (13)	0.0472 (11)	0.0005 (10)	0.0072 (9)	−0.0116 (10)
C6	0.0522 (11)	0.0544 (11)	0.0397 (9)	0.0043 (8)	0.0118 (8)	0.0013 (8)
C7	0.0507 (11)	0.0654 (13)	0.0400 (10)	0.0021 (9)	0.0090 (8)	−0.0020 (9)
C8	0.0506 (11)	0.0582 (12)	0.0387 (10)	0.0054 (9)	0.0077 (8)	0.0025 (8)
O9	0.0584 (9)	0.1032 (13)	0.0407 (8)	0.0094 (8)	0.0111 (6)	0.0024 (7)
C10	0.0506 (11)	0.0527 (11)	0.0393 (9)	0.0030 (8)	0.0047 (8)	0.0035 (8)
C11	0.0491 (11)	0.0707 (14)	0.0422 (10)	−0.0022 (9)	0.0049 (8)	−0.0041 (9)
C12	0.0534 (12)	0.0780 (15)	0.0476 (11)	−0.0027 (10)	0.0098 (9)	−0.0075 (10)
C13	0.0461 (11)	0.0669 (14)	0.0580 (12)	−0.0025 (9)	0.0089 (9)	0.0003 (10)
C14	0.0550 (12)	0.0813 (16)	0.0472 (11)	−0.0048 (11)	−0.0020 (9)	−0.0035 (10)
C15	0.0553 (12)	0.0759 (14)	0.0398 (10)	0.0003 (10)	0.0045 (9)	−0.0005 (9)
O16	0.0476 (9)	0.1096 (15)	0.0726 (11)	−0.0107 (8)	0.0115 (7)	−0.0139 (9)
C17	0.0590 (15)	0.121 (2)	0.095 (2)	−0.0131 (14)	0.0279 (14)	−0.0264 (17)
C18	0.0593 (16)	0.135 (3)	0.153 (3)	−0.0193 (16)	0.0391 (18)	−0.049 (2)

S1—C2	1.701 (2)	C11—H11	0.9300
S1—C5	1.692 (2)	C11—C12	1.385 (3)
C2—H2	0.9300	C12—H12	0.9300
C2—C3	1.357 (3)	C12—C13	1.379 (3)
C3—C4	1.427 (3)	C13—C14	1.392 (3)
C3—C6	1.450 (3)	C13—O16	1.365 (3)
C4—H4	0.9300	C14—H14	0.9300
C4—C5	1.371 (3)	C14—C15	1.359 (3)
C5—H5	0.9300	C15—H15	0.9300
C6—H6	0.9300	O16—C17	1.416 (3)
C6—C7	1.319 (3)	C17—H17A	0.9700
C7—H7	0.9300	C17—H17B	0.9700
C7—C8	1.470 (3)	C17—C18	1.500 (4)
C8—O9	1.224 (2)	C18—H18A	0.9600
C8—C10	1.496 (3)	C18—H18B	0.9600
C10—C11	1.381 (3)	C18—H18C	0.9600
C10—C15	1.398 (3)
C5—S1—C2	92.34 (10)	C12—C11—H11	119.3
S1—C2—H2	123.7	C11—C12—H12	120.2
C3—C2—S1	112.62 (15)	C13—C12—C11	119.60 (19)
C3—C2—H2	123.7	C13—C12—H12	120.2
C2—C3—C4	110.92 (18)	C12—C13—C14	119.8 (2)
C2—C3—C6	123.30 (17)	O16—C13—C12	124.39 (19)
C4—C3—C6	125.79 (17)	O16—C13—C14	115.84 (19)
C3—C4—H4	123.5	C13—C14—H14	120.1
C5—C4—C3	113.01 (18)	C15—C14—C13	119.78 (19)
C5—C4—H4	123.5	C15—C14—H14	120.1
S1—C5—H5	124.4	C10—C15—H15	119.1
C4—C5—S1	111.11 (15)	C14—C15—C10	121.80 (19)
C4—C5—H5	124.4	C14—C15—H15	119.1
C3—C6—H6	117.0	C13—O16—C17	118.30 (18)
C7—C6—C3	126.00 (18)	O16—C17—H17A	110.0
C7—C6—H6	117.0	O16—C17—H17B	110.0
C6—C7—H7	118.8	O16—C17—C18	108.5 (2)
C6—C7—C8	122.31 (18)	H17A—C17—H17B	108.4
C8—C7—H7	118.8	C18—C17—H17A	110.0
C7—C8—C10	118.74 (16)	C18—C17—H17B	110.0
O9—C8—C7	121.26 (18)	C17—C18—H18A	109.5
O9—C8—C10	119.99 (17)	C17—C18—H18B	109.5
C11—C10—C8	123.51 (17)	C17—C18—H18C	109.5
C11—C10—C15	117.56 (18)	H18A—C18—H18B	109.5
C15—C10—C8	118.92 (17)	H18A—C18—H18C	109.5
C10—C11—H11	119.3	H18B—C18—H18C	109.5
C10—C11—C12	121.47 (19)
S1—C2—C3—C4	−0.1 (2)	C8—C10—C15—C14	179.3 (2)
S1—C2—C3—C6	179.55 (15)	O9—C8—C10—C11	168.8 (2)
C2—S1—C5—C4	−0.05 (18)	O9—C8—C10—C15	−10.9 (3)
C2—C3—C4—C5	0.1 (3)	C10—C11—C12—C13	0.3 (3)
C2—C3—C6—C7	−177.9 (2)	C11—C10—C15—C14	−0.4 (3)
C3—C4—C5—S1	0.0 (2)	C11—C12—C13—C14	−1.0 (3)
C3—C6—C7—C8	179.75 (18)	C11—C12—C13—O16	178.9 (2)
C4—C3—C6—C7	1.8 (3)	C12—C13—C14—C15	1.0 (3)
C5—S1—C2—C3	0.11 (18)	C12—C13—O16—C17	0.2 (3)
C6—C3—C4—C5	−179.58 (19)	C13—C14—C15—C10	−0.3 (4)
C6—C7—C8—O9	17.1 (3)	C13—O16—C17—C18	−177.0 (2)
C6—C7—C8—C10	−161.57 (19)	C14—C13—O16—C17	−179.9 (2)
C7—C8—C10—C11	−12.6 (3)	C15—C10—C11—C12	0.4 (3)
C7—C8—C10—C15	167.75 (19)	O16—C13—C14—C15	−178.9 (2)
C8—C10—C11—C12	−179.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O9i	0.93	2.47	3.324 (2)	153

C13H9BrOS	F(000) = 584
Mr = 293.17	Dx = 1.667 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.1245 (7) Å	Cell parameters from 4399 reflections
b = 14.2016 (13) Å	θ = 2.9–27.3°
c = 5.8809 (4) Å	µ = 3.67 mm−1
β = 98.081 (6)°	T = 293 K
V = 1167.93 (15) Å3	Plate, yellow
Z = 4	0.4 × 0.4 × 0.05 mm

SuperNova, single source at offset/far, Eos diffractometer	2392 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	1683 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.045
Detector resolution: 15.9631 pixels mm-1	θmax = 26.4°, θmin = 2.9°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −17→17
Tmin = 0.367, Tmax = 1.000	l = −7→7
12050 measured reflections

Refinement on F2	20 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H-atom parameters constrained
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.0407P)2 + 0.7623P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
2392 reflections	Δρmax = 0.40 e Å−3
158 parameters	Δρmin = −0.46 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.07255 (13)	0.3898 (2)	0.4329 (4)	0.0574 (6)	0.702 (4)
S1B	0.1418 (5)	0.3457 (7)	0.2749 (13)	0.0574 (6)	0.298 (4)
C2A	0.1532 (7)	0.412 (2)	0.663 (3)	0.048 (3)	0.702 (4)
H2A	0.137355	0.439712	0.795694	0.058*	0.702 (4)
C2B	0.2476 (16)	0.341 (5)	0.438 (6)	0.048 (3)	0.298 (4)
H2B	0.301123	0.310516	0.397088	0.058*	0.298 (4)
C3	0.2452 (2)	0.3858 (2)	0.6388 (5)	0.0417 (8)
C4A	0.2461 (7)	0.3456 (17)	0.416 (2)	0.048 (3)	0.702 (4)
H4A	0.302496	0.326195	0.365401	0.058*	0.702 (4)
C4B	0.1551 (18)	0.422 (5)	0.664 (6)	0.048 (3)	0.298 (4)
H4B	0.142572	0.455562	0.792513	0.058*	0.298 (4)
C5A	0.1586 (7)	0.3375 (9)	0.2809 (18)	0.053 (3)	0.702 (4)
H5A	0.146845	0.309732	0.136500	0.063*	0.702 (4)
C5B	0.0855 (10)	0.4021 (19)	0.475 (3)	0.053 (3)	0.298 (4)
H5B	0.020804	0.416891	0.461047	0.063*	0.298 (4)
C6	0.3264 (2)	0.3933 (2)	0.8186 (6)	0.0451 (8)
H6	0.313682	0.414696	0.960622	0.054*
C7	0.4168 (2)	0.3729 (2)	0.8023 (6)	0.0485 (9)
H7	0.433284	0.356673	0.659823	0.058*
C8	0.4916 (3)	0.3752 (2)	1.0027 (6)	0.0460 (8)
O9	0.4718 (2)	0.3764 (2)	1.1988 (4)	0.0676 (8)
C10	0.5938 (2)	0.3754 (2)	0.9658 (5)	0.0403 (8)
C11	0.6238 (2)	0.4075 (2)	0.7646 (6)	0.0451 (8)
H11	0.578794	0.428136	0.644229	0.054*
C12	0.7202 (3)	0.4092 (3)	0.7410 (6)	0.0470 (8)
H12	0.740087	0.432427	0.607649	0.056*
C13	0.7860 (2)	0.3760 (2)	0.9180 (6)	0.0434 (8)
C14	0.7584 (3)	0.3438 (3)	1.1203 (6)	0.0491 (9)
H14	0.803570	0.322082	1.239069	0.059*
C15	0.6624 (2)	0.3447 (2)	1.1429 (6)	0.0447 (8)
H15	0.643292	0.324227	1.279603	0.054*
Br16	0.91660 (3)	0.37156 (4)	0.88024 (8)	0.0730 (2)

	U11	U22	U33	U12	U13	U23
S1A	0.0459 (8)	0.0718 (14)	0.0532 (11)	0.0051 (8)	0.0029 (6)	−0.0014 (9)
S1B	0.0459 (8)	0.0718 (14)	0.0532 (11)	0.0051 (8)	0.0029 (6)	−0.0014 (9)
C2A	0.044 (4)	0.056 (10)	0.045 (4)	0.006 (4)	0.010 (3)	−0.004 (4)
C2B	0.044 (4)	0.056 (10)	0.045 (4)	0.006 (4)	0.010 (3)	−0.004 (4)
C3	0.0453 (19)	0.0398 (19)	0.0417 (18)	−0.0020 (15)	0.0115 (15)	0.0021 (15)
C4A	0.052 (4)	0.051 (5)	0.043 (5)	−0.002 (3)	0.013 (3)	−0.006 (5)
C4B	0.052 (4)	0.051 (5)	0.043 (5)	−0.002 (3)	0.013 (3)	−0.006 (5)
C5A	0.058 (6)	0.055 (5)	0.051 (4)	0.015 (4)	0.025 (4)	−0.013 (3)
C5B	0.058 (6)	0.055 (5)	0.051 (4)	0.015 (4)	0.025 (4)	−0.013 (3)
C6	0.045 (2)	0.051 (2)	0.0416 (19)	−0.0044 (16)	0.0107 (15)	−0.0040 (15)
C7	0.047 (2)	0.054 (2)	0.0452 (19)	−0.0018 (17)	0.0105 (16)	−0.0068 (16)
C8	0.0447 (19)	0.050 (2)	0.045 (2)	0.0020 (16)	0.0112 (16)	−0.0036 (16)
O9	0.0531 (16)	0.107 (3)	0.0450 (15)	0.0056 (14)	0.0139 (12)	0.0000 (14)
C10	0.0455 (19)	0.0372 (18)	0.0386 (18)	−0.0011 (15)	0.0075 (15)	−0.0038 (14)
C11	0.049 (2)	0.050 (2)	0.0350 (18)	0.0028 (17)	0.0007 (15)	0.0004 (15)
C12	0.054 (2)	0.051 (2)	0.0366 (18)	−0.0055 (17)	0.0101 (16)	0.0013 (16)
C13	0.0382 (18)	0.045 (2)	0.048 (2)	−0.0061 (15)	0.0075 (15)	−0.0056 (16)
C14	0.051 (2)	0.050 (2)	0.0426 (19)	−0.0004 (17)	−0.0036 (16)	0.0041 (16)
C15	0.050 (2)	0.048 (2)	0.0363 (18)	−0.0041 (17)	0.0062 (15)	0.0021 (15)
Br16	0.0430 (3)	0.0970 (4)	0.0803 (4)	−0.0074 (2)	0.0128 (2)	0.0047 (2)

S1A—C2A	1.671 (8)	C6—H6	0.9300
C2A—H2A	0.9300	C6—C7	1.325 (5)
S1B—C2B	1.661 (16)	C7—H7	0.9300
C2B—H2B	0.9300	C7—C8	1.469 (5)
C2A—C3	1.378 (9)	C8—O9	1.224 (4)
C2B—C3	1.347 (16)	C8—C10	1.489 (5)
C4A—H4A	0.9300	C10—C11	1.389 (5)
C4B—H4B	0.9300	C10—C15	1.390 (5)
S1A—C5A	1.770 (8)	C11—H11	0.9300
C4A—C5A	1.378 (11)	C11—C12	1.388 (5)
C5A—H5A	0.9300	C12—H12	0.9300
S1B—C5B	1.708 (15)	C12—C13	1.378 (5)
C4B—C5B	1.407 (16)	C13—C14	1.381 (5)
C5B—H5B	0.9300	C13—Br16	1.890 (3)
C3—C4A	1.431 (8)	C14—H14	0.9300
C3—C4B	1.400 (16)	C14—C15	1.381 (5)
C3—C6	1.451 (5)	C15—H15	0.9300
C4A—C5A—S1A	107.3 (6)	C7—C6—C3	127.0 (3)
C4B—C5B—S1B	107.4 (9)	C7—C6—H6	116.5
S1A—C2A—H2A	122.9	C6—C7—H7	119.0
S1B—C2B—H2B	124.6	C6—C7—C8	121.9 (3)
C5A—C4A—C3	116.0 (7)	C8—C7—H7	119.0
C5A—C4A—H4A	122.0	C7—C8—C10	119.1 (3)
C5B—C4B—H4B	123.6	O9—C8—C7	121.5 (3)
C2A—S1A—C5A	92.8 (4)	O9—C8—C10	119.5 (3)
S1A—C5A—H5A	126.3	C11—C10—C8	122.9 (3)
C4A—C5A—H5A	126.3	C11—C10—C15	118.5 (3)
C2B—S1B—C5B	95.2 (7)	C15—C10—C8	118.6 (3)
C4B—C5B—H5B	126.3	C10—C11—H11	119.6
S1B—C5B—H5B	126.3	C12—C11—C10	120.8 (3)
C2A—C3—C4A	109.4 (5)	C12—C11—H11	119.6
C2B—C3—C4B	113.8 (9)	C11—C12—H12	120.5
C4A—C3—C6	126.0 (4)	C13—C12—C11	119.1 (3)
C4B—C3—C6	122.2 (7)	C13—C12—H12	120.5
C2B—C3—C6	124.0 (7)	C12—C13—C14	121.5 (3)
C2A—C3—C6	124.5 (5)	C12—C13—Br16	119.2 (3)
C3—C6—H6	116.5	C14—C13—Br16	119.3 (3)
C3—C2A—S1A	114.3 (5)	C13—C14—H14	120.7
C3—C2B—S1B	110.7 (9)	C15—C14—C13	118.7 (3)
C3—C2A—H2A	122.9	C15—C14—H14	120.7
C3—C2B—H2B	124.6	C10—C15—H15	119.3
C3—C4A—H4A	122.0	C14—C15—C10	121.5 (3)
C3—C4B—H4B	123.6	C14—C15—H15	119.3
C3—C4B—C5B	112.7 (11)
C2A—S1A—C5A—C4A	−3 (2)	C6—C3—C4B—C5B	−176 (3)
C2B—S1B—C5B—C4B	4 (5)	C6—C7—C8—O9	15.6 (6)
C5B—S1B—C2B—C3	−4 (5)	C6—C7—C8—C10	−164.9 (3)
C5A—S1A—C2A—C3	2 (2)	C7—C8—C10—C11	24.4 (5)
S1A—C2A—C3—C4A	0 (2)	C7—C8—C10—C15	−157.6 (3)
S1B—C2B—C3—C4B	2 (5)	C8—C10—C11—C12	177.8 (3)
S1B—C2B—C3—C6	179.7 (18)	C8—C10—C15—C14	−179.4 (3)
S1A—C2A—C3—C6	−176.6 (10)	O9—C8—C10—C11	−156.0 (4)
C2A—C3—C6—C7	−177.0 (17)	O9—C8—C10—C15	22.0 (5)
C2B—C3—C6—C7	13 (4)	C10—C11—C12—C13	1.8 (5)
C4A—C3—C6—C7	6.9 (15)	C11—C10—C15—C14	−1.3 (5)
C4B—C3—C6—C7	−170 (4)	C11—C12—C13—C14	−2.0 (5)
C2A—C3—C4A—C5A	−3 (2)	C11—C12—C13—Br16	176.5 (3)
C2B—C3—C4B—C5B	1 (6)	C12—C13—C14—C15	0.5 (5)
C3—C4B—C5B—S1B	−4 (7)	C13—C14—C15—C10	1.2 (5)
C3—C4A—C5A—S1A	4 (2)	C15—C10—C11—C12	−0.2 (5)
C3—C6—C7—C8	−174.3 (3)	Br16—C13—C14—C15	−177.9 (3)
C6—C3—C4A—C5A	173.8 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C5A—H5A···Cg1i	0.93	2.80	3.493 (14)	132
C5A—H5A···Cg2i	0.93	2.85	3.52 (2)	130