Crystal structures and Hirshfeld surfaces of two 1,3-benzoxa­thiol-2-one derivatives

Chazin, E. de L.; Sanches, P. de S.; Vasconcelos, T.R.A.; Gomes, C.R.B.; Wardell, J.L.; Harrison, W.T.A.

doi:10.1107/S2056989017018072

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 1| January 2018| Pages 78-82

https://doi.org/10.1107/S2056989017018072

Open

access

Crystal structures and Hirshfeld surfaces of two 1,3-benzoxathiol-2-one derivatives

Eliza de L. Chazin,^a Paola de S. Sanches,^a Thatyana R. A. Vasconcelos,^a Claudia R. B. Gomes,^b James L. Wardell ^b,^c and William T. A. Harrison ^c ^*

^aUniversidade Federal Fluminense, Instituto de Química, Programa de Pós-Graduação em Química, Rua Outeiro de São João Batista s/no, Centro, Niterói, 24020-141, RJ, Brazil, ^bInstituto de Tecnologia em Fármacos – Farmanguinhos, Fiocruz. R. Sizenando, Nabuco, 100, Manguinhos, 21041-250, Rio de Janeiro, RJ, Brazil, and ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

Edited by G. S. Nichol, University of Edinburgh, Scotland (Received 28 September 2017; accepted 18 December 2017; online 1 January 2018)

The crystal structures of 6-methoxy-1,3-benzoxathiol-2-one, C₉H₈O₃S, (I), and 2-oxo-1,3-benzoxathiol-6-yl acetate, C₉H₆O₄S, (II), are described. Compound (I) is almost planar (r.m.s. deviation for the non-H atoms = 0.011 Å), whereas (II) shows a substantial twist between the fused-ring system and the acetate substituent [dihedral angle = 74.42 (3)°]. For both structures, the bond distances in the heterocyclic ring suggest that little if any conjugation occurs. In the crystal of (I), C—H⋯O hydrogen bonds link the molecules into [1-11] chains incorporating alternating R₂²(8) and R₂²(12) inversion dimers. The extended structure of (II) features C(7) [201] chains linked by C—H⋯O hydrogen bonds, with further C—H⋯O bonds and weak π–π stacking interactions connecting the chains into a three-dimensional network. Hirshfeld fingerprint analyses for (I) and (II) are presented and discussed.

Keywords: crystal structure; benzoxathiol-2-one; hydrogen bonds; Hirshfeld surface.

CCDC references: 1404758; 1404756

1. Chemical context

1,3-Benzoxathiol-2-one and its derivatives have various biological properties including antibacterial, antimycotic, antioxidant, antitumor and anti-inflammatory activities (Vellasco Júnior et al., 2011 ; Chazin et al., 2015 ). They also act as inhibitors of carbonic anhydrase II (Barrese et al., 2008 ) and monoamine oxidase (Mostert et al., 2016 ). The first synthesized 1,3-benzoxathiol-2-one, 6-hydroxy-1,3-benzoxathiol-2-one C₇H₄O₃S, also known as tioxolone or thioxolone, has been used for many years in the treatment of acne and other skin diseases (e.g. psoriasis) (Berg & Fiedler, 1959 ).

A recent study reported the syntheses and antifungal activities of some derivatives of tioxolone (Terra et al., 2018 ). In the present article we report the crystal structures and Hirshfeld surface analyses of two compounds with different substituents at the 6-position of the ring system obtained in that study, viz. 6-methoxy-1,3-benzoxathiol-2-one, C₉H₈O₃S, (I), and 2-oxo-1,3-benzoxathiol-6-yl acetate, C₉H₈O₃S, (II)..

2. Structural commentary

Compound (I) crystallizes in space group P $[\overline{1}]$ with one molecule in the asymmetric unit (Fig. 1), which is almost planar (r.m.s. deviation for the non-hydrogen atoms = 0.011 Å): the ethoxy side chain adopts an extended conformation [C6—O3—C8—C9 = 179.82 (12)°]. Within the oxathiol-2-one ring system, the C1—O1, C1=O2 and C1—S1 bond lengths are 1.3732 (18), 1.1905 (19) and 1.7766 (16)Å, respectively, and the O1—C1—S1 and C1—S1—C3 bond angles are 111.07 (11) and 90.62 (7)°, respectively. These distance data suggest that there is little if any conjugation (i.e. partial double-bond character) involving the C1—O1 and C1—S1 bonds with the C1=O2 group.

Figure 1
The molecular structure of (I)

, showing 50% displacement ellipsoids.

A single molecule of compound (II) makes up the asymmetric unit in space group P2₁/c (Fig. 2). The ring system is almost planar (r.m.s. deviation for C1–C7/O1/S1 = 0.032 Å) but there is a substantial twist about the C6—O3 bond, as indicated by the dihedral angle between the ring system and the acetate group of 74.42 (3)°. Key geometrical data for the heterocyclic ring are C1—O1 = 1.3864 (15), C1=O2 = 1.1936 (15), C1—S1 = 1.7709 (13) Å, O1—C1—S1 = 111.57 (8) and C1—S1—C3 = 90.43 (6)°. These data are similar to the equivalent values for (I) and again indicate a lack of significant electronic delocalization within the oxathiol-2-one ring system.

Figure 2
The molecular structure of (II)

, showing 50% displacement ellipsoids.

3. Supramolecular features

In the crystal of (I), the molecules are linked by C—H⋯O hydrogen bonds (Table 1). The C5—H5⋯O3ⁱ [symmetry code: (i) −x, 1 − y, −z] link generates inversion dimers featuring R₂²(8) loops. Based on its length, the C7—H7⋯O2ⁱⁱ [symmetry code: (ii) 1 − x, −y, 1 − z] bond is much weaker, but if it is considered significant, it generates a second inversion dimer [with an R₂²(12) graph-set symbol], which links the dimers into [1 $[\overline{1}]$ 1] chains (Fig. 3). No C—H⋯π interactions could be identified in the crystal of (I) and any aromatic π–π stacking must be extremely weak, as the shortest centroid–centroid separation is 3.9149 (10) Å.

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3ⁱ	0.95	2.48	3.432 (2)	175
C7—H7⋯O2ⁱⁱ	0.95	2.66	3.5983 (19)	170
Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y, -z+1.

Figure 3
Fragment of a [1 $[\overline{1}]$ 1] hydrogen-bonded chain in (I)

; all hydrogen atoms except H5 and H7 have been omitted for clarity. Symmetry codes as in Table 1

In the crystal of (II), C4—H4⋯O4ⁱ [symmetry code: (i) x − 1, $[1\over2]$ − y, z − $[1\over2]$ ] hydrogen bonds (Table 2) link the molecules into C(7) chains propagating in [201], with adjacent molecules in the chain related by c-glide symmetry (plus translation) (Fig. 4). The C9—H9C⋯O2ⁱⁱ [symmetry code: (ii) 1 − x, −y, 1 − z] bonds arising from the methyl group generate inversion dimers [R₂²(16) loops], which connect the chains into a three-dimensional network. There are no C—H⋯π bonds in the crystal of (II) but the packing is consolidated by weak aromatic π–π stacking between inversion-related C2–C7 benzene rings with a centroid–centroid separation of 3.7220 (8) Å.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O4ⁱ	0.95	2.35	3.2606 (15)	159
C9—H9C⋯O2ⁱⁱ	0.98	2.50	3.4030 (16)	153
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1.

Figure 4
Fragment of a [201] hydrogen-bonded chain in (II)

; all hydrogen atoms except H4 omitted for clarity. Symmetry codes as in Table 2

; additionally (iii) x − 2, y, z − 1.

4. Hirshfeld analyses

Hirshfeld surface fingerprint plots for (I) (Fig. 5), (II) (Fig. 6) and tioxolone (refcode: EVOQEL), which features classical O—H⋯O hydrogen bonds (Byres & Cox, 2004 ) (Fig. 7) were calculated with CrystalExplorer17 (Turner et al., 2017 ). The plot for EVOQEL has very pronounced `wingtip' features that correspond to the short, classical O—H⋯O hydrogen bond found in this structure (compare: McKinnon et al., 2007 ). In (I) and (II), the wingtips associated with the longer and presumably weaker C—H⋯O bonds are far less pronounced.

Figure 5
Hirshfeld fingerprint plot for (I)

Figure 6
Hirshfeld fingerprint plot for (II)

Figure 7
Hirshfeld fingerprint plot for tioxolone [atomic coordinates from Byres & Cox (2004

)].

When the fingerprint plots are decomposed into the separate types of contacts (McKinnon et al., 2007), some interesting differences arise (Table 3): as a percentage of surface interactions, H⋯H contacts (i.e. van der Waals interactions) are far more prominent in (I) than in (II), which is comparable with EVOQEL, whereas C⋯H/H⋯C contacts are similar for the three structures. The O⋯H/H⋯O contacts are the most important contributors in all three structures, and in (II) they actually contribute a higher percentage to the surface than in EVOQEL, despite the fact that EVOQEL features both O—H⋯O and C—H⋯O hydrogen bonds and only one of its hydrogen atoms is not involved in such bonds (Byres & Cox, 2004). The C⋯C contacts (associated with aromatic π–π stacking) contribute a small percentage in (I) and (II) and about twice the amount in EVOQEL where the shortest centroid–centroid separation is 3.508 (2) Å. Despite the small percentage for (II), the Hirshfeld surface (Fig. 8) clearly shows red spots associated with these contacts. The S⋯H/H⋯S contacts are similar in the three structures, and not insignificant at ∼10% of the surfaces, but they can hardly represent directional C—H⋯S hydrogen bonds, as the shortest H⋯S separations (3.21, 3.11 and 3.28 Å in (I), (II) and EVOQEL, respectively) are much longer than the van der Waals contact distance (Bondi, 1964 ) of 3.00 Å for H and S. Finally, S⋯O/O⋯S contacts have very different contributions in the three structures: negligible in (I), but clearly present in (II) and EVOQEL. This seems to correlate with the shortest S⋯O contact distances of 3.623 (2), 3.2742 (10) and 3.341 (2) Å for (I), (II) and EVOQEL, respectively: the distance in (II) is actually slightly shorter than the van der Waals contact distance of 3.32Å for sulfur and oxygen,

Table 3
Hirshfeld contact interactions (%)

Contact type	(I)	(II)	EVOQEL
H⋯H	28.7	14.8	13.5
O⋯H/H⋯O	30.1	39.5	36.0
C⋯H/H⋯C	11.3	13.4	8.6
S⋯H/H⋯S	11.1	10.8	8.8
C⋯C	5.9	4.4	10.4
S⋯O/O⋯S	1.5	7.0	10.1

Figure 8
Hirshfeld surface plot mapped over d_norm for (II)

showing red spots associated with short C⋯C and C⋯O contacts: the slightly smaller spots refer to the former.

5. Database survey

A survey of of the Cambridge Structural Database (Groom et al., 2016 : updated to September 2017) for the benzoxathiol-2-one fused ring system (any substituents) yielded just three matches, viz. 6-hydroxy-1,3-benzoxathiol-2-one (refcode: EVOQEL; Byres & Cox, 2004); N-(4,7-dimethyl-2-oxo-benzo[1,3]oxathiol-5-yl)-4-benzenesulfonamide (NAJQOG; Avdeenko et al., 2009 ); 7-phenyl-1,3-benzoxathiol-2-one (JOSGUV; Zhao et al., 2014 ). To this list may be added the structure of 6-methoxy-5-nitrobenzo[d][1,3]oxathiol-2-one (CCDC deposition number 1404755) as recently reported by Terra et al. (2017).

6. Synthesis and crystallization

Compounds (I) and (II) were prepared as described previously (Terra et al., 2018) and recrystallized from methanol solution as colourless plates of (I) and colourless blocks of (II).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The hydrogen atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding atoms. The constraint U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier) was applied in all cases. The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.

Table 4
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₉H₈O₃S	C₉H₆O₄S
M_r	196.21	210.20
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c
Temperature (K)	100	100
a, b, c (Å)	3.9149 (6), 10.3237 (12), 11.7003 (14)	5.6232 (5), 14.5650 (14), 10.8572 (11)
α, β, γ (°)	66.526 (6), 81.110 (9), 84.349 (9)	90, 96.045 (2), 90
V (Å³)	428.18 (10)	884.28 (15)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.35	0.35
Crystal size (mm)	0.17 × 0.17 × 0.03	0.26 × 0.11 × 0.08

Data collection
Diffractometer	Rigaku Saturn CCD	Rigaku Saturn CCD
Absorption correction	Multi-scan (FS_ABSCOR; Rigaku, 2013 )	Multi-scan (FS_ABSCOR; Rigaku, 2013)
T_min, T_max	0.714, 1.000	0.829, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5189, 1674, 1540	11487, 2028, 1903
R_int	0.040	0.036
(sin θ/λ)_max (Å⁻¹)	0.617	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.04	0.028, 0.081, 1.10
No. of reflections	1674	2028
No. of parameters	119	128
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.20	0.33, −0.21
Computer programs: CrystalClear (Rigaku, 2014 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1404758; 1404756

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989017018072/nk2242sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017018072/nk2242Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017018072/nk2242IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017018072/nk2242Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989017018072/nk2242IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: CrystalClear (Rigaku, 2014); cell refinement: CrystalClear (Rigaku, 2014); data reduction: CrystalClear (Rigaku, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

6-Methoxy-1,3-benzoxathiol-2-one (I) top

Crystal data top

C₉H₈O₃S	Z = 2
M_r = 196.21	F(000) = 204
Triclinic, P1	D_x = 1.522 Mg m⁻³
a = 3.9149 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3237 (12) Å	Cell parameters from 1390 reflections
c = 11.7003 (14) Å	θ = 1.9–27.5°
α = 66.526 (6)°	µ = 0.35 mm⁻¹
β = 81.110 (9)°	T = 100 K
γ = 84.349 (9)°	Plate, colourless
V = 428.18 (10) Å³	0.17 × 0.17 × 0.03 mm

Data collection top

Rigaku Saturn CCD diffractometer	1540 reflections with I > 2σ(I)
ω scans	R_int = 0.040
Absorption correction: multi-scan (FS_ABSCOR; Rigaku, 2013)	θ_max = 26.0°, θ_min = 1.9°
T_min = 0.714, T_max = 1.000	h = −4→4
5189 measured reflections	k = −12→12
1674 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0607P)² + 0.0766P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1674 reflections	Δρ_max = 0.52 e Å⁻³
119 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

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
C1	0.0898 (4)	0.15148 (16)	0.62375 (14)	0.0238 (3)
C2	0.1487 (4)	0.21490 (16)	0.40934 (14)	0.0221 (3)
C3	−0.0473 (4)	0.33140 (16)	0.41485 (14)	0.0221 (3)
C4	−0.1375 (4)	0.43830 (16)	0.30435 (15)	0.0238 (3)
H4	−0.2733	0.5190	0.3064	0.029*
C5	−0.0252 (4)	0.42431 (16)	0.19181 (15)	0.0245 (3)
H5	−0.0854	0.4961	0.1157	0.029*
C6	0.1770 (4)	0.30535 (16)	0.18846 (14)	0.0223 (3)
C7	0.2673 (4)	0.19732 (16)	0.29857 (14)	0.0230 (3)
H7	0.4028	0.1161	0.2975	0.028*
C8	0.4817 (4)	0.18554 (16)	0.06172 (15)	0.0240 (3)
H8A	0.3576	0.0970	0.1095	0.029*
H8B	0.7026	0.1773	0.0959	0.029*
C9	0.5494 (4)	0.21106 (18)	−0.07580 (15)	0.0283 (4)
H9A	0.6977	0.1336	−0.0867	0.042*
H9B	0.6651	0.3005	−0.1224	0.042*
H9C	0.3294	0.2157	−0.1077	0.042*
O1	0.2250 (3)	0.11453 (11)	0.52491 (10)	0.0244 (3)
O2	0.1322 (3)	0.07887 (11)	0.72936 (10)	0.0282 (3)
O3	0.2727 (3)	0.30495 (11)	0.07165 (10)	0.0251 (3)
S1	−0.14241 (9)	0.31705 (4)	0.57093 (3)	0.02391 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0236 (8)	0.0232 (7)	0.0273 (8)	−0.0042 (6)	−0.0017 (6)	−0.0124 (6)
C2	0.0220 (7)	0.0193 (7)	0.0254 (8)	−0.0039 (6)	−0.0056 (6)	−0.0076 (6)
C3	0.0218 (7)	0.0212 (7)	0.0264 (8)	−0.0034 (6)	−0.0037 (6)	−0.0117 (6)
C4	0.0228 (7)	0.0213 (8)	0.0301 (8)	0.0010 (6)	−0.0056 (6)	−0.0125 (6)
C5	0.0257 (8)	0.0216 (7)	0.0273 (8)	−0.0009 (6)	−0.0069 (6)	−0.0096 (6)
C6	0.0214 (7)	0.0222 (8)	0.0258 (7)	−0.0045 (6)	−0.0026 (6)	−0.0112 (6)
C7	0.0223 (7)	0.0201 (7)	0.0286 (8)	−0.0013 (6)	−0.0042 (6)	−0.0110 (6)
C8	0.0245 (7)	0.0216 (7)	0.0280 (8)	0.0002 (6)	−0.0040 (6)	−0.0120 (6)
C9	0.0289 (8)	0.0302 (8)	0.0288 (8)	−0.0026 (7)	−0.0007 (6)	−0.0153 (7)
O1	0.0290 (6)	0.0210 (5)	0.0239 (6)	0.0013 (4)	−0.0044 (4)	−0.0096 (4)
O2	0.0335 (6)	0.0260 (6)	0.0246 (6)	−0.0001 (5)	−0.0037 (5)	−0.0095 (5)
O3	0.0300 (6)	0.0221 (6)	0.0247 (6)	0.0026 (4)	−0.0044 (4)	−0.0112 (5)
S1	0.0252 (2)	0.0234 (2)	0.0259 (2)	0.00092 (16)	−0.00403 (16)	−0.01255 (17)

Geometric parameters (Å, º) top

C1—O2	1.1905 (19)	C5—H5	0.9500
C1—O1	1.3732 (18)	C6—O3	1.3617 (18)
C1—S1	1.7766 (16)	C6—C7	1.395 (2)
C2—C3	1.380 (2)	C7—H7	0.9500
C2—C7	1.383 (2)	C8—O3	1.4452 (18)
C2—O1	1.3926 (18)	C8—C9	1.508 (2)
C3—C4	1.394 (2)	C8—H8A	0.9900
C3—S1	1.7552 (16)	C8—H8B	0.9900
C4—C5	1.381 (2)	C9—H9A	0.9800
C4—H4	0.9500	C9—H9B	0.9800
C5—C6	1.405 (2)	C9—H9C	0.9800

O2—C1—O1	122.22 (14)	C2—C7—C6	116.34 (14)
O2—C1—S1	126.71 (12)	C2—C7—H7	121.8
O1—C1—S1	111.07 (11)	C6—C7—H7	121.8
C3—C2—C7	123.62 (14)	O3—C8—C9	107.02 (12)
C3—C2—O1	114.96 (13)	O3—C8—H8A	110.3
C7—C2—O1	121.41 (13)	C9—C8—H8A	110.3
C2—C3—C4	119.56 (14)	O3—C8—H8B	110.3
C2—C3—S1	110.37 (11)	C9—C8—H8B	110.3
C4—C3—S1	130.07 (12)	H8A—C8—H8B	108.6
C5—C4—C3	118.55 (14)	C8—C9—H9A	109.5
C5—C4—H4	120.7	C8—C9—H9B	109.5
C3—C4—H4	120.7	H9A—C9—H9B	109.5
C4—C5—C6	120.85 (14)	C8—C9—H9C	109.5
C4—C5—H5	119.6	H9A—C9—H9C	109.5
C6—C5—H5	119.6	H9B—C9—H9C	109.5
O3—C6—C7	123.91 (13)	C1—O1—C2	112.97 (12)
O3—C6—C5	115.01 (13)	C6—O3—C8	117.75 (12)
C7—C6—C5	121.08 (14)	C3—S1—C1	90.62 (7)

C7—C2—C3—C4	0.7 (2)	C5—C6—C7—C2	−0.4 (2)
O1—C2—C3—C4	179.88 (13)	O2—C1—O1—C2	−179.25 (14)
C7—C2—C3—S1	−179.08 (11)	S1—C1—O1—C2	0.23 (15)
O1—C2—C3—S1	0.14 (16)	C3—C2—O1—C1	−0.24 (18)
C2—C3—C4—C5	−0.3 (2)	C7—C2—O1—C1	178.99 (12)
S1—C3—C4—C5	179.33 (12)	C7—C6—O3—C8	−0.3 (2)
C3—C4—C5—C6	−0.3 (2)	C5—C6—O3—C8	179.90 (13)
C4—C5—C6—O3	−179.56 (13)	C9—C8—O3—C6	179.82 (12)
C4—C5—C6—C7	0.6 (2)	C2—C3—S1—C1	−0.01 (11)
C3—C2—C7—C6	−0.3 (2)	C4—C3—S1—C1	−179.71 (15)
O1—C2—C7—C6	−179.47 (13)	O2—C1—S1—C3	179.32 (15)
O3—C6—C7—C2	179.87 (13)	O1—C1—S1—C3	−0.13 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3ⁱ	0.95	2.48	3.432 (2)	175
C7—H7···O2ⁱⁱ	0.95	2.66	3.5983 (19)	170

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

2-Oxo-1,3-benzoxathiol-6-yl acetate (II) top

Crystal data top

C₉H₆O₄S	F(000) = 432
M_r = 210.20	D_x = 1.579 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.6232 (5) Å	Cell parameters from 3355 reflections
b = 14.5650 (14) Å	θ = 2.3–27.5°
c = 10.8572 (11) Å	µ = 0.35 mm⁻¹
β = 96.045 (2)°	T = 100 K
V = 884.28 (15) Å³	Block, colourless
Z = 4	0.26 × 0.11 × 0.08 mm

Data collection top

Rigaku Saturn CCD diffractometer	1903 reflections with I > 2σ(I)
ω scans	R_int = 0.036
Absorption correction: multi-scan (FS_ABSCOR; Rigaku, 2013)	θ_max = 27.5°, θ_min = 2.4°
T_min = 0.829, T_max = 1.000	h = −7→7
11487 measured reflections	k = −18→18
2028 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0423P)² + 0.328P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2028 reflections	Δρ_max = 0.33 e Å⁻³
128 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.1830 (2)	0.03032 (8)	0.18546 (11)	0.0210 (2)
C2	0.1514 (2)	0.07946 (8)	0.38446 (11)	0.0167 (2)
C3	−0.0602 (2)	0.11624 (8)	0.32717 (11)	0.0174 (2)
C4	−0.2186 (2)	0.16130 (8)	0.39666 (11)	0.0194 (2)
H4	−0.3625	0.1872	0.3580	0.023*
C5	−0.1609 (2)	0.16746 (8)	0.52441 (11)	0.0191 (2)
H5	−0.2657	0.1979	0.5742	0.023*
C6	0.0505 (2)	0.12894 (8)	0.57848 (10)	0.0175 (2)
C7	0.2139 (2)	0.08489 (8)	0.51080 (11)	0.0175 (2)
H7	0.3595	0.0601	0.5491	0.021*
C8	0.2608 (2)	0.18164 (8)	0.76657 (11)	0.0183 (2)
C9	0.2792 (2)	0.16577 (9)	0.90343 (11)	0.0222 (3)
H9A	0.1197	0.1535	0.9284	0.033*
H9B	0.3465	0.2204	0.9467	0.033*
H9C	0.3833	0.1129	0.9248	0.033*
O1	0.29007 (15)	0.03350 (6)	0.30638 (8)	0.01950 (19)
O2	0.27313 (17)	−0.00958 (7)	0.10631 (8)	0.0282 (2)
O3	0.08651 (15)	0.12684 (6)	0.70829 (7)	0.0207 (2)
O4	0.37694 (17)	0.23332 (7)	0.71088 (8)	0.0275 (2)
S1	−0.09135 (5)	0.09103 (2)	0.16863 (3)	0.02017 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0246 (6)	0.0209 (6)	0.0177 (6)	−0.0017 (5)	0.0030 (4)	0.0015 (4)
C2	0.0164 (5)	0.0158 (5)	0.0181 (6)	−0.0015 (4)	0.0026 (4)	−0.0003 (4)
C3	0.0194 (5)	0.0177 (5)	0.0148 (5)	−0.0023 (4)	−0.0004 (4)	0.0001 (4)
C4	0.0180 (5)	0.0194 (6)	0.0202 (6)	0.0019 (4)	−0.0009 (4)	0.0003 (4)
C5	0.0194 (5)	0.0185 (6)	0.0196 (6)	−0.0010 (4)	0.0028 (4)	−0.0020 (4)
C6	0.0208 (5)	0.0178 (5)	0.0137 (5)	−0.0055 (4)	0.0007 (4)	0.0004 (4)
C7	0.0158 (5)	0.0182 (6)	0.0178 (6)	−0.0017 (4)	−0.0008 (4)	0.0019 (4)
C8	0.0201 (5)	0.0182 (5)	0.0163 (5)	0.0003 (4)	0.0005 (4)	−0.0020 (4)
C9	0.0287 (6)	0.0235 (6)	0.0140 (5)	−0.0009 (5)	0.0007 (4)	−0.0007 (4)
O1	0.0190 (4)	0.0230 (4)	0.0167 (4)	0.0017 (3)	0.0025 (3)	−0.0010 (3)
O2	0.0336 (5)	0.0321 (5)	0.0200 (5)	0.0048 (4)	0.0076 (4)	−0.0030 (4)
O3	0.0239 (4)	0.0251 (5)	0.0128 (4)	−0.0076 (3)	0.0006 (3)	0.0003 (3)
O4	0.0317 (5)	0.0327 (5)	0.0176 (4)	−0.0140 (4)	0.0008 (4)	−0.0002 (4)
S1	0.02389 (18)	0.02219 (18)	0.01374 (17)	0.00119 (11)	−0.00123 (12)	0.00007 (10)

Geometric parameters (Å, º) top

C1—O2	1.1936 (15)	C5—H5	0.9500
C1—O1	1.3864 (15)	C6—C7	1.3923 (16)
C1—S1	1.7709 (13)	C6—O3	1.4030 (13)
C2—C7	1.3820 (17)	C7—H7	0.9500
C2—O1	1.3835 (14)	C8—O4	1.2008 (15)
C2—C3	1.3905 (16)	C8—O3	1.3665 (14)
C3—C4	1.3908 (16)	C8—C9	1.4965 (16)
C3—S1	1.7506 (12)	C9—H9A	0.9800
C4—C5	1.3936 (16)	C9—H9B	0.9800
C4—H4	0.9500	C9—H9C	0.9800
C5—C6	1.3875 (16)

O2—C1—O1	121.54 (12)	C7—C6—O3	119.12 (10)
O2—C1—S1	126.88 (10)	C2—C7—C6	115.92 (11)
O1—C1—S1	111.57 (8)	C2—C7—H7	122.0
C7—C2—O1	122.33 (10)	C6—C7—H7	122.0
C7—C2—C3	122.57 (11)	O4—C8—O3	122.31 (11)
O1—C2—C3	115.05 (10)	O4—C8—C9	127.77 (11)
C2—C3—C4	120.37 (11)	O3—C8—C9	109.92 (10)
C2—C3—S1	110.57 (9)	C8—C9—H9A	109.5
C4—C3—S1	128.97 (9)	C8—C9—H9B	109.5
C3—C4—C5	118.37 (11)	H9A—C9—H9B	109.5
C3—C4—H4	120.8	C8—C9—H9C	109.5
C5—C4—H4	120.8	H9A—C9—H9C	109.5
C6—C5—C4	119.62 (11)	H9B—C9—H9C	109.5
C6—C5—H5	120.2	C2—O1—C1	112.32 (9)
C4—C5—H5	120.2	C8—O3—C6	118.24 (9)
C5—C6—C7	123.14 (11)	C3—S1—C1	90.43 (6)
C5—C6—O3	117.42 (10)

C7—C2—C3—C4	0.48 (18)	C7—C2—O1—C1	174.88 (10)
O1—C2—C3—C4	177.81 (10)	C3—C2—O1—C1	−2.46 (14)
C7—C2—C3—S1	−176.35 (9)	O2—C1—O1—C2	−177.20 (11)
O1—C2—C3—S1	0.98 (13)	S1—C1—O1—C2	2.77 (12)
C2—C3—C4—C5	−0.77 (18)	O4—C8—O3—C6	2.67 (17)
S1—C3—C4—C5	175.41 (9)	C9—C8—O3—C6	−177.05 (10)
C3—C4—C5—C6	−0.02 (17)	C5—C6—O3—C8	−111.17 (12)
C4—C5—C6—C7	1.17 (18)	C7—C6—O3—C8	75.10 (14)
C4—C5—C6—O3	−172.28 (10)	C2—C3—S1—C1	0.52 (9)
O1—C2—C7—C6	−176.54 (10)	C4—C3—S1—C1	−175.96 (12)
C3—C2—C7—C6	0.60 (17)	O2—C1—S1—C3	178.09 (12)
C5—C6—C7—C2	−1.43 (17)	O1—C1—S1—C3	−1.88 (9)
O3—C6—C7—C2	171.91 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4ⁱ	0.95	2.35	3.2606 (15)	159
C9—H9C···O2ⁱⁱ	0.98	2.50	3.4030 (16)	153

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1.

Hirshfeld contact interactions (%) top

Contact type	(I)	(II)	EVOQEL
H···H	28.7	14.8	13.5
O···H/H···O	30.1	39.5	36.0
C···H/H···C	11.3	13.4	8.6
S···H/H···S	11.1	10.8	8.8
C···C	5.9	4.4	10.4
S···O/O···S	1.5	7.0	10.1

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the X-ray data collections.

References

Avdeenko, A. P., Pirozhenko, V. V., Konovalov, S. A., Roman'kov, D. A., Palamarchuk, G. V. & Shishkin, O. V. (2009). Russ. J. Org. Chem. 45, 408–416. CrossRef CAS Google Scholar
Barrese, A. A. III, Genis, C., Fisher, S. Z., Orwenyo, J. N., Kumara, M. T., Dutta, S. K., Phillips, E., Kiddle, J. J., Tu, C., Silverman, D. N., Govindasamy, L., Agbandje-McKenna, M., McKenna, R. & Tripp, B. C. (2008). Biochemistry, 47, 3174–3184. PubMed CAS Google Scholar
Berg, A. H. & Fiedler, H. (1959). US Patent 2,886,488. Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Byres, M. & Cox, P. J. (2004). Acta Cryst. C60, o395–o396. CrossRef CAS IUCr Journals Google Scholar
Chazin, E. L., Sanches, P. S., Lindgren, E. B., Vellasco Júnior, W. T., Pinto, L. C., Burbano, R. M. R., Yoneda, J. D., Leal, K. Z., Gomes, C. R. B., Wardell, J. L., Wardell, S. M. S. V., Montenegro, R. C. & Vasconcelos, T. R. A. (2015). Molecules, 20, 1968–1983. CrossRef PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. 3814–3816. Google Scholar
Mostert, S., Petzer, A. & Petzer, J. P. (2016). Bioorg. Med. Chem. Lett. 26, 1200–1204. CrossRef CAS PubMed Google Scholar
Rigaku (2013). PS_ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2014). CrysAlis PRO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Terra, L., Chazin, E. de L., Sanches, P. de S., Saito, M., de Souza, M. V. N., Gomes, C. R. B., Wardell, J. L., Wardell, S. M. S. V., Sathler, P. C., Silva, G. C. C., Lione, V. O., Kalil1, M., Joffily, A., Castro1, H. C. & Vasconcelos, T. R. A. (2018). Med. Chem. (Bentham) 14, 1–7 Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia, Nedlands, Western Australia; https://hirshfeldsurface.net. Google Scholar
Vellasco, W. T., Gomes, C. F. B. & Vasconcelos, T. R. A. (2011). Mini-Rev. Org. Chem. 8, 103–109. CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, Y., Xie, Y., Xia, C. & Huang, H. (2014). Adv. Synth. Catal. 356, 2471–2476. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 1| January 2018| Pages 78-82

https://doi.org/10.1107/S2056989017018072

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures and Hirshfeld surfaces of two 1,3-benzoxa­thiol-2-one derivatives

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld analyses

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structures and Hirshfeld surfaces of two 1,3-benzoxathiol-2-one derivatives

3. Supramolecular features