Crystal structures of 4-meth-oxy-N-(4-methyl-phenyl)benzene-sulfonamide and N-(4-fluoro-phenyl)-4-meth-oxy-benzene-sulfonamide.

Crystal structures of two N-(ar-yl)aryl-sulfonamides, namely, 4-meth-oxy-N-(4-methyl-phen-yl)benzene-sulfonamide, C14H15NO3S, (I), and N-(4-fluoro-phen-yl)-4-meth-oxy-benzene-sulfonamide, C13H12FNO3S, (II), were determined and analyzed. In (I), the benzene-sulfonamide ring is disordered over two orientations, in a 0.516 (7):0.484 (7) ratio, which are inclined to each other at 28.0 (1)°. In (I), the major component of the sulfonyl benzene ring and the aniline ring form a dihedral angle of 63.36 (19)°, while in (II), the planes of the two benzene rings form a dihedral angle of 44.26 (13)°. In the crystal structure of (I), N-H⋯O hydrogen bonds form infinite C(4) chains extended in [010], and inter-molecular C-H⋯πar-yl inter-actions link these chains into layers parallel to the ab plane. The crystal structure of (II) features N-H⋯O hydrogen bonds forming infinite one dimensional C(4) chains along [001]. Further, a pair of C-H⋯O inter-molecular inter-actions consolidate the crystal packing of (II) into a three-dimensional supra-molecular architecture.

Chemical context

Sulfonamide drugs were the first among the chemotherapeutic agents to be used for curing and preventing bacterial infection in human beings (Shiva Prasad et al., 2011 ▸). They play a vital role as a key constituent in a number of biologically active mol­ecules. Up to now, sulfonamides have been known to exhibit a wide variety of biological activities, such as anti­bacterial (Subhakara Reddy et al., 2012 ▸; Himel et al., 1971 ▸), anti­fungal (Hanafy et al., 2007 ▸), anti­inflamatory (Kuçukguzel et al., 2013 ▸), anti­tumor (Ghorab et al., 2011 ▸), anti­cancer (Mansour et al., 2011 ▸), anti-HIV (Sahu et al., 2007 ▸) and anti­tubercular activities (Vora & Mehta, 2012 ▸). In recent years, extensive research studies have been carried out on the synthesis and evaluation of pharmacological activities of mol­ecules containing the sulfonamide moiety for different activities, and have been reported to be important pharmacophores (Mohan et al., 2013 ▸).

With these considerations in mind and based on our structural study of N-(4-substituted-phen­yl)-4-meth­oxy­benzene­sulfonamides (Vinola et al., 2015 ▸), we report herein the crystal structures of 4-meth­oxy-N-(4-methyl­phen­yl)benzene­sulfonamide, (I), and N-(4-fluoro­phen­yl)-4-meth­oxy­benzene­sulfonamide, (II).

Structural commentary

In (I) (Fig. 1 ▸), the benzene­sulfonamide ring is disordered due to rotation across the Car—S(O2) bond over two orientations, with atoms C2, C3, C5 and C6 occupying two positions with a 0.516 (7):0.484 (7) ratio. The dihedral angle between the two parts of disordered benzene ring, i.e. C1/C2A/C3A/C4/C5A/C6A and C1/C2B/C3B/C4/C5B/C6B, is 28.0 (1)°. The dihedral angle between the sulfonyl benzene ring (considering the major component) and the aniline ring is 63.36 (19)°, and the N—C bond in the C—SO2—NH—C segment has a gauche torsion with respect to the S=O bonds. Further, the mol­ecule is twisted at the S—N bond, with a C1—S1—N1—C7 torsion angle of 66.33 (19)°. The meth­oxy group in the sulfonyl­benzene ring is in the same plane as that of the major component of the disordered sulfonyl­benzene ring, the torsion angle C5A—C4—O3—C14 being −176.2 (4)°, while it deviates slightly from planarity with respect to the minor component, the C5B—C4—O3—C14 torsion angle being 165.9 (4)°.

Figure 1

A view of (I), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Only the major component of the disordered benzene ring is shown.

In (II) (Fig. 2 ▸), the dihedral angle between the two benzene rings of 44.26 (13)° is less than that observed in (I), and the N—C bond in the C—SO2—NH—C segment has a gauche torsion with respect to the S=O bonds. Further, the mol­ecule is twisted at the S—N bond, with a C1—S1—N1—C7 torsion angle of 68.4 (2)°. Similar to (I), the meth­oxy group in the sulfonyl­benzene ring is in the same plane as that of the sulfonyl­benzene ring, the C5—C4—O3—C13 torsion angle being 177.0 (2)°.

Figure 2

A view of (II), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

In the crystal structure of (I), N1—H1⋯O2 hydrogen bonds (Table 1 ▸) link the mol­ecules into infinite one-dimensional C(4) chains along [010]. Neighbouring C(4) chains are inter­connected via C—H⋯πar­yl inter­actions (Table 1 ▸) into layers (Fig. 3 ▸) parallel to the ab plane.

Table 1

Hydrogen-bond geometry (Å, °) for (I)

Cg is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.89 (1)	2.13 (1)	3.010 (2)	170 (2)
C14—H14B⋯Cg ii	0.96	2.70	3.541 (2)	146
C9—H9⋯Cg iii	0.93	2.87	3.560 (2)	132

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 3

A portion of the crystal packing of (I), viewed approximately along [010] and showing inter­molecular hydrogen bonds as thin blue lines. Only the major component of the disordered benzene ring is shown. H atoms not involved in hydrogen bonding have been omitted for clarity.

The crystal structure of (II) features N1—H1⋯O2 hydrogen bonds (Fig. 4 ▸ and Table 2 ▸), forming infinite one-dimensional C(4) chains along [001]. Further, weak inter­molecular C—H⋯O inter­actions (Table 2 ▸) consolidate the crystal packing of (II), leading to a three-dimensional supra­molecular architecture (Fig. 5 ▸).

Figure 4

An N—H⋯O hydrogen-bonded (thin blue lines) chain of mol­ecules in the crystal structure of (II).

Table 2

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.90 (1)	2.06 (1)	2.951 (3)	171 (3)
C6—H6⋯O1ii	0.93	2.55	3.192 (3)	127
C13—H13B⋯O3iii	0.96	2.60	3.468 (3)	151

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 5

A portion of the crystal packing of (II). Thin blue lines denote inter­molecular C—H⋯O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

Database survey

Three N-(4-substituted-phen­yl)-4-meth­oxy­benzene­sul­fon­am­ides (Vinola et al., 2015 ▸), namely, 4-meth­oxy-N-(phen­yl)benzene­sulfonamide, (III), 4-meth­oxy-N-(4-meth­oxy­phen­yl)benzene­sulfonamide, (IV), and N-(4-chloro­phen­yl)-4-meth­oxy­benzene­sulfonamide, (V), have been reported previously. Compounds (IV) and (V) crystallize in monoclinic syngony, while compound (III) crystallizes in ortho­rhom­bic syngony. The dihedral angles between the two benzene rings in (III), (IV) and (V) are 55.1 (1), 56.3 (1) and 42.6 (1)°, respectively. Comparison of the dihedral angles between the two benzene rings in (I)–(V) shows that, when an electron-donating substituent is introduced into the para position of the aniline ring of (I) it results in a slight increase in the dihedral angle, whereas, when an electron-withdrawing substituent is introduced it decreases the dihedral angle. Further, the mol­ecules of (III), (IV) and (V) are twisted at the S—N bond, with C1—S1—N1—C7 torsion angles of −72.9 (1), 66.2 (1) and 72.5 (1)°, respectively. These values are similar to those observed in (I) and (II).

Comparison of the crystal structures (I) and (V) shows that the effect of introducing an electron-donating substituent into the para position of the aniline ring of (I) is quite different than that due to electron-withdrawing substituents. The crystal structure of (III) features N—H⋯O hydrogen bonds that form C(4) chains, and thus, the supra­molecular architecture is one-dimensional. In (IV), one N—H⋯O hydrogen bond and two alternating C—H⋯πar­yl (centroid of aniline ring) inter­actions direct a two-dimensional architecture. This is quite similar to the crystal structure of (I). Thus, the methyl and meth­oxy groups on the aniline ring have similar influence on the crystal structures of these compounds. However, the crystal structures of (II) and (V) are very different. The crystal structure of (V) features N—H⋯O hydrogen bonds that form C(4) chains. Further, (V) does not feature any structuredirecting inter­molecular inter­actions, and thus, the structure is one-dimensional. In contrast to this, the crystal structure of (II) features an N—H⋯O and two C—H⋯O inter­actions, leading to a three-dimensional architecture. Thus, the Cl and F atoms on the aniline ring have very different influences on the crystal structures of these compounds.

Synthesis and crystallization

Compounds (I) and (II) were prepared according to the literature method of Vinola et al. (2015 ▸). The purity of the compounds were checked by determining the melting points. Single crystals used for X-ray diffraction studies were obtained by slow evaporation of ethanol solutions of the compounds at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The amino H atoms were located in a difference map and were refined isotropically with the bond-length restraint N—H = 0.90 (1) Å. To improve considerably the values of R1, wR2, and S (goodness-of-fit), a partially obscured reflection (i.e. 100) was omitted from the final refinement of (I). The two parts (A and B) of the disordered benzene­sulfonyl ring in (I) were restrained to be planar (FLAT instruction), and thus, the r.m.s. deviations (considering non-H atoms) observed for the planes defining the two rings are 0.047 (1) (major-component ring A) and 0.054 (1) Å (minor-component ring B). The disordered atoms (C2, C3, C5 and C6) in both components were isotropically refined, and the C—C bond lengths were restrained to 1.391 (1) Å.

Table 3

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C14H15NO3S	C13H12FNO3S
M r	277.33	281.30
Crystal system, space group	Monoclinic, P21/c	Orthorhombic, P n a21
Temperature (K)	296	296
a, b, c (Å)	14.5604 (5), 5.2459 (2), 17.6094 (6)	20.2188 (13), 12.1199 (8), 5.1770 (3)
α, β, γ (°)	90, 95.205 (2), 90	90, 90, 90
V (Å3)	1339.50 (8)	1268.62 (14)
Z	4	4
Radiation type	Cu Kα	Cu Kα
μ (mm−1)	2.19	2.44
Crystal size (mm)	0.33 × 0.27 × 0.21	0.32 × 0.27 × 0.22
Data collection
Diffractometer	Bruker APEXII	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2009 ▸)	Multi-scan (SADABS; Bruker, 2009 ▸)
T min, T max	0.517, 0.632	0.481, 0.585
No. of measured, independent and observed [I > 2σ(I)] reflections	7071, 2139, 2047	5438, 1830, 1784
R int	0.042	0.037
(sin θ/λ)max (Å−1)	0.583	0.583
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.048, 0.145, 1.12	0.034, 0.100, 1.09
No. of reflections	2139	1830
No. of parameters	175	177
No. of restraints	19	2
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
Δρmax, Δρmin (e Å−3)	0.45, −0.43	0.30, −0.35
Absolute structure	–	Flack (1983 ▸), 973 Friedel pairs
Absolute structure parameter	–	0.08 (2)

Computer programs: APEX2, SAINT-Plus and XPREP (Bruker, 2009 ▸), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989015019787/cv5497sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019787/cv5497Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015019787/cv5497Isup4.cml

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989015019787/cv5497IIsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015019787/cv5497IIsup5.cml

CCDC reference: 1432501

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

C14H15NO3S	Prism
Mr = 277.33	Dx = 1.375 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 14.5604 (5) Å	Cell parameters from 178 reflections
b = 5.2459 (2) Å	θ = 5.0–64.1°
c = 17.6094 (6) Å	µ = 2.19 mm−1
β = 95.205 (2)°	T = 296 K
V = 1339.50 (8) Å3	Prism, colourless
Z = 4	0.33 × 0.27 × 0.21 mm
F(000) = 584

Bruker APEXII diffractometer	2047 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
Graphite monochromator	θmax = 64.1°, θmin = 5.0°
phi and φ scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −5→6
Tmin = 0.517, Tmax = 0.632	l = −20→20
7071 measured reflections	1 standard reflections every 1 reflections
2139 independent reflections	intensity decay: 0.1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.095P)2 + 0.6515P] where P = (Fo2 + 2Fc2)/3
2139 reflections	(Δ/σ)max = 0.001
175 parameters	Δρmax = 0.45 e Å−3
19 restraints	Δρmin = −0.43 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
H1	0.7020 (19)	0.376 (2)	0.4174 (15)	0.033 (7)*
C1	0.87525 (15)	0.0577 (4)	0.41335 (12)	0.0223 (5)
C2A	0.9220 (3)	0.2925 (9)	0.4259 (2)	0.0227 (12)*	0.516 (7)
H2A	0.8960	0.4215	0.4532	0.027*	0.516 (7)
C3A	1.0070 (3)	0.3298 (9)	0.3973 (3)	0.0243 (12)*	0.516 (7)
H3A	1.0392	0.4819	0.4057	0.029*	0.516 (7)
C2B	0.9452 (3)	0.1901 (9)	0.4561 (3)	0.0230 (13)*	0.484 (7)
H2B	0.9355	0.2534	0.5040	0.028*	0.484 (7)
C3B	1.0299 (3)	0.2268 (10)	0.4262 (3)	0.0231 (13)*	0.484 (7)
H3B	1.0768	0.3160	0.4540	0.028*	0.484 (7)
C4	1.04337 (15)	0.1285 (4)	0.35455 (12)	0.0226 (5)
C5A	0.9913 (3)	−0.0795 (10)	0.3344 (3)	0.0190 (14)*	0.516 (7)
H5A	1.0125	−0.1992	0.3011	0.023*	0.516 (7)
C6A	0.9068 (4)	−0.1143 (11)	0.3631 (3)	0.0199 (16)*	0.516 (7)
H6A	0.8710	−0.2557	0.3483	0.024*	0.516 (7)
C5B	0.9778 (4)	−0.0372 (12)	0.3192 (4)	0.0215 (16)*	0.484 (7)
H5B	0.9903	−0.1226	0.2750	0.026*	0.484 (7)
C6B	0.8942 (4)	−0.0756 (12)	0.3492 (3)	0.0191 (17)*	0.484 (7)
H6B	0.8514	−0.1900	0.3264	0.023*	0.484 (7)
S1	0.76759 (3)	0.02277 (10)	0.45066 (3)	0.0195 (3)
O3	1.12308 (11)	0.1523 (3)	0.32071 (9)	0.0257 (4)
O1	0.77618 (12)	0.1184 (3)	0.52696 (8)	0.0288 (4)
O2	0.73662 (11)	−0.2332 (3)	0.43553 (9)	0.0239 (4)
N1	0.69436 (13)	0.2136 (3)	0.40319 (10)	0.0209 (5)
C10	0.60286 (15)	0.1132 (4)	0.16969 (13)	0.0233 (5)
C7	0.66683 (14)	0.1726 (4)	0.32369 (12)	0.0190 (5)
C11	0.66087 (17)	0.3146 (5)	0.19337 (13)	0.0269 (5)
H11	0.6785	0.4311	0.1576	0.032*
C9	0.57863 (15)	−0.0581 (5)	0.22474 (14)	0.0251 (5)
H9	0.5409	−0.1957	0.2099	0.030*
C14	1.18279 (18)	0.3601 (5)	0.34384 (17)	0.0401 (7)
H14A	1.1496	0.5177	0.3367	0.060*
H14B	1.2345	0.3610	0.3137	0.060*
H14C	1.2043	0.3410	0.3967	0.060*
C8	0.60898 (15)	−0.0295 (4)	0.30080 (13)	0.0219 (5)
H8	0.5908	−0.1449	0.3366	0.026*
C12	0.69271 (16)	0.3439 (4)	0.26919 (12)	0.0236 (5)
H12	0.7317	0.4791	0.2839	0.028*
C13	0.56880 (18)	0.0780 (6)	0.08674 (14)	0.0363 (6)
H13A	0.6139	−0.0147	0.0614	0.054*
H13B	0.5589	0.2417	0.0631	0.054*
H13C	0.5119	−0.0155	0.0831	0.054*

	U11	U22	U33	U12	U13	U23
C1	0.0253 (12)	0.0218 (12)	0.0201 (11)	−0.0001 (10)	0.0032 (9)	−0.0043 (9)
C4	0.0233 (11)	0.0225 (12)	0.0222 (11)	0.0006 (9)	0.0021 (9)	0.0015 (9)
S1	0.0239 (4)	0.0169 (4)	0.0181 (4)	−0.0004 (2)	0.0046 (2)	−0.00107 (18)
O3	0.0223 (8)	0.0264 (9)	0.0290 (8)	−0.0022 (7)	0.0056 (7)	0.0003 (7)
O1	0.0336 (9)	0.0348 (10)	0.0187 (8)	0.0010 (8)	0.0062 (7)	−0.0046 (7)
O2	0.0294 (9)	0.0151 (8)	0.0277 (8)	−0.0003 (7)	0.0046 (7)	0.0038 (6)
N1	0.0286 (10)	0.0129 (10)	0.0220 (10)	0.0015 (8)	0.0061 (8)	−0.0028 (7)
C10	0.0199 (11)	0.0249 (13)	0.0254 (12)	0.0060 (9)	0.0027 (9)	−0.0035 (9)
C7	0.0186 (11)	0.0154 (11)	0.0236 (11)	0.0038 (8)	0.0046 (9)	−0.0017 (8)
C11	0.0322 (13)	0.0231 (12)	0.0258 (12)	0.0017 (10)	0.0060 (10)	0.0025 (9)
C9	0.0187 (11)	0.0223 (12)	0.0339 (13)	−0.0017 (10)	0.0008 (9)	−0.0041 (10)
C14	0.0262 (13)	0.0385 (15)	0.0570 (18)	−0.0111 (12)	0.0118 (12)	−0.0074 (13)
C8	0.0177 (11)	0.0179 (11)	0.0305 (13)	−0.0004 (9)	0.0042 (9)	0.0032 (9)
C12	0.0294 (12)	0.0145 (11)	0.0274 (12)	−0.0036 (9)	0.0051 (9)	−0.0021 (9)
C13	0.0329 (14)	0.0476 (17)	0.0281 (13)	0.0003 (13)	0.0019 (11)	−0.0059 (12)

C1—C6A	1.371 (5)	S1—O2	1.4340 (17)
C1—C6B	1.378 (5)	S1—N1	1.6360 (19)
C1—C2B	1.395 (5)	O3—C14	1.430 (3)
C1—C2A	1.415 (5)	N1—C7	1.437 (3)
C1—S1	1.763 (2)	N1—H1	0.893 (10)
C2A—C3A	1.391 (5)	C10—C9	1.391 (3)
C2A—H2A	0.9300	C10—C11	1.393 (3)
C3A—C4	1.426 (5)	C10—C13	1.511 (3)
C3A—H3A	0.9300	C7—C8	1.391 (3)
C2B—C3B	1.397 (6)	C7—C12	1.392 (3)
C2B—H2B	0.9300	C11—C12	1.382 (3)
C3B—C4	1.394 (5)	C11—H11	0.9300
C3B—H3B	0.9300	C9—C8	1.380 (3)
C4—C5A	1.358 (5)	C9—H9	0.9300
C4—O3	1.358 (3)	C14—H14A	0.9600
C4—C5B	1.395 (5)	C14—H14B	0.9600
C5A—C6A	1.385 (6)	C14—H14C	0.9600
C5A—H5A	0.9300	C8—H8	0.9300
C6A—H6A	0.9300	C12—H12	0.9300
C5B—C6B	1.385 (6)	C13—H13A	0.9600
C5B—H5B	0.9300	C13—H13B	0.9600
C6B—H6B	0.9300	C13—H13C	0.9600
S1—O1	1.4291 (16)
C6A—C1—C2B	113.9 (3)	O1—S1—O2	120.18 (10)
C6B—C1—C2B	120.3 (3)	O1—S1—N1	105.25 (10)
C6A—C1—C2A	119.3 (3)	O2—S1—N1	107.39 (9)
C6B—C1—C2A	116.1 (3)	O1—S1—C1	107.99 (10)
C6A—C1—S1	122.2 (3)	O2—S1—C1	107.66 (10)
C6B—C1—S1	120.2 (3)	N1—S1—C1	107.83 (10)
C2B—C1—S1	118.7 (2)	C4—O3—C14	117.83 (18)
C2A—C1—S1	117.6 (2)	C7—N1—S1	121.15 (14)
C3A—C2A—C1	119.8 (4)	C7—N1—H1	115.7 (17)
C3A—C2A—H2A	120.1	S1—N1—H1	112.5 (18)
C1—C2A—H2A	120.1	C9—C10—C11	117.8 (2)
C2A—C3A—C4	118.1 (4)	C9—C10—C13	120.9 (2)
C2A—C3A—H3A	120.9	C11—C10—C13	121.3 (2)
C4—C3A—H3A	120.9	C8—C7—C12	119.2 (2)
C1—C2B—C3B	119.5 (4)	C8—C7—N1	120.31 (19)
C1—C2B—H2B	120.3	C12—C7—N1	120.4 (2)
C3B—C2B—H2B	120.3	C12—C11—C10	121.0 (2)
C4—C3B—C2B	119.4 (4)	C12—C11—H11	119.5
C4—C3B—H3B	120.3	C10—C11—H11	119.5
C2B—C3B—H3B	120.3	C8—C9—C10	121.8 (2)
C5A—C4—O3	116.0 (3)	C8—C9—H9	119.1
C5A—C4—C3B	114.4 (3)	C10—C9—H9	119.1
O3—C4—C3B	124.1 (3)	O3—C14—H14A	109.5
O3—C4—C5B	116.0 (3)	O3—C14—H14B	109.5
C3B—C4—C5B	119.2 (3)	H14A—C14—H14B	109.5
C5A—C4—C3A	120.5 (3)	O3—C14—H14C	109.5
O3—C4—C3A	122.4 (2)	H14A—C14—H14C	109.5
C5B—C4—C3A	115.1 (3)	H14B—C14—H14C	109.5
C4—C5A—C6A	120.3 (4)	C9—C8—C7	119.8 (2)
C4—C5A—H5A	119.9	C9—C8—H8	120.1
C6A—C5A—H5A	119.9	C7—C8—H8	120.1
C1—C6A—C5A	120.6 (4)	C11—C12—C7	120.4 (2)
C1—C6A—H6A	119.7	C11—C12—H12	119.8
C5A—C6A—H6A	119.7	C7—C12—H12	119.8
C6B—C5B—C4	120.7 (5)	C10—C13—H13A	109.5
C6B—C5B—H5B	119.7	C10—C13—H13B	109.5
C4—C5B—H5B	119.7	H13A—C13—H13B	109.5
C1—C6B—C5B	119.2 (5)	C10—C13—H13C	109.5
C1—C6B—H6B	120.4	H13A—C13—H13C	109.5
C5B—C6B—H6B	120.4	H13B—C13—H13C	109.5
C6A—C1—C2A—C3A	−10.4 (6)	S1—C1—C6B—C5B	177.4 (5)
C6B—C1—C2A—C3A	−26.8 (6)	C4—C5B—C6B—C1	1.9 (9)
C2B—C1—C2A—C3A	79.3 (5)	C6A—C1—S1—O1	145.9 (4)
S1—C1—C2A—C3A	−179.7 (3)	C6B—C1—S1—O1	163.2 (4)
C1—C2A—C3A—C4	1.2 (6)	C2B—C1—S1—O1	−7.0 (3)
C6A—C1—C2B—C3B	27.0 (6)	C2A—C1—S1—O1	−45.0 (3)
C6B—C1—C2B—C3B	11.9 (6)	C6A—C1—S1—O2	14.8 (4)
C2A—C1—C2B—C3B	−80.4 (5)	C6B—C1—S1—O2	32.1 (4)
S1—C1—C2B—C3B	−177.9 (3)	C2B—C1—S1—O2	−138.2 (3)
C1—C2B—C3B—C4	−0.6 (6)	C2A—C1—S1—O2	−176.2 (3)
C2B—C3B—C4—C5A	−27.1 (6)	C6A—C1—S1—N1	−100.8 (4)
C2B—C3B—C4—O3	−179.6 (3)	C6B—C1—S1—N1	−83.5 (4)
C2B—C3B—C4—C5B	−9.8 (6)	C2B—C1—S1—N1	106.3 (3)
C2B—C3B—C4—C3A	82.0 (6)	C2A—C1—S1—N1	68.2 (3)
C2A—C3A—C4—C5A	8.2 (6)	C5A—C4—O3—C14	−176.2 (4)
C2A—C3A—C4—O3	176.2 (3)	C3B—C4—O3—C14	−24.1 (4)
C2A—C3A—C4—C3B	−80.1 (6)	C5B—C4—O3—C14	165.9 (4)
C2A—C3A—C4—C5B	25.4 (6)	C3A—C4—O3—C14	15.3 (4)
O3—C4—C5A—C6A	−177.0 (4)	O1—S1—N1—C7	−178.58 (16)
C3B—C4—C5A—C6A	28.1 (7)	O2—S1—N1—C7	−49.43 (18)
C5B—C4—C5A—C6A	−82.9 (14)	C1—S1—N1—C7	66.33 (19)
C3A—C4—C5A—C6A	−8.3 (7)	S1—N1—C7—C8	71.9 (2)
C6B—C1—C6A—C5A	92.3 (16)	S1—N1—C7—C12	−112.4 (2)
C2B—C1—C6A—C5A	−26.5 (7)	C9—C10—C11—C12	−0.5 (3)
C2A—C1—C6A—C5A	10.5 (7)	C13—C10—C11—C12	−179.2 (2)
S1—C1—C6A—C5A	179.3 (4)	C11—C10—C9—C8	1.3 (3)
C4—C5A—C6A—C1	−1.2 (8)	C13—C10—C9—C8	180.0 (2)
C5A—C4—C5B—C6B	86.0 (14)	C10—C9—C8—C7	−1.2 (3)
O3—C4—C5B—C6B	179.8 (5)	C12—C7—C8—C9	0.4 (3)
C3B—C4—C5B—C6B	9.2 (8)	N1—C7—C8—C9	176.2 (2)
C3A—C4—C5B—C6B	−27.4 (7)	C10—C11—C12—C7	−0.3 (3)
C6A—C1—C6B—C5B	−80.7 (16)	C8—C7—C12—C11	0.4 (3)
C2B—C1—C6B—C5B	−12.5 (8)	N1—C7—C12—C11	−175.4 (2)
C2A—C1—C6B—C5B	25.2 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.89 (1)	2.13 (1)	3.010 (2)	170 (2)
C14—H14B···Cgii	0.96	2.70	3.541 (2)	146
C9—H9···Cgiii	0.93	2.87	3.560 (2)	132

C13H12FNO3S	Prism
Mr = 281.30	Dx = 1.473 Mg m−3
Orthorhombic, Pna21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 143 reflections
a = 20.2188 (13) Å	θ = 4.3–64.1°
b = 12.1199 (8) Å	µ = 2.44 mm−1
c = 5.1770 (3) Å	T = 296 K
V = 1268.62 (14) Å3	Prism, colourless
Z = 4	0.32 × 0.27 × 0.22 mm
F(000) = 584

Bruker APEXII diffractometer	1784 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 64.1°, θmin = 4.3°
phi and φ scans	h = −22→23
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −13→14
Tmin = 0.481, Tmax = 0.585	l = −5→5
5438 measured reflections	1 standard reflections every 1 reflections
1830 independent reflections	intensity decay: 0.1%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0719P)2] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
1830 reflections	Δρmax = 0.30 e Å−3
177 parameters	Δρmin = −0.35 e Å−3
2 restraints	Absolute structure: Flack (1983), 973 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (2)

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S1	0.77164 (2)	0.42206 (4)	0.40154 (13)	0.0172 (2)
F1	0.96703 (8)	−0.00461 (12)	0.4446 (3)	0.0328 (4)
O1	0.75213 (8)	0.53031 (14)	0.4790 (4)	0.0229 (4)
O2	0.79392 (9)	0.40209 (15)	0.1426 (4)	0.0234 (4)
O3	0.56267 (8)	0.10112 (16)	0.6458 (4)	0.0289 (5)
N1	0.83314 (9)	0.38833 (18)	0.5945 (4)	0.0179 (5)
C10	0.93385 (12)	0.0915 (2)	0.4822 (6)	0.0245 (6)
C6	0.70105 (11)	0.2317 (2)	0.3318 (5)	0.0224 (6)
H6	0.7303	0.2162	0.1979	0.027*
C8	0.85326 (11)	0.1947 (2)	0.7108 (5)	0.0229 (6)
H8	0.8215	0.2003	0.8401	0.028*
C7	0.86643 (11)	0.2844 (2)	0.5534 (5)	0.0181 (5)
C4	0.60893 (10)	0.1812 (2)	0.5970 (6)	0.0216 (6)
C2	0.66316 (11)	0.3540 (2)	0.6686 (6)	0.0221 (5)
H2	0.6672	0.4199	0.7591	0.027*
C5	0.65224 (10)	0.15819 (19)	0.3967 (6)	0.0234 (5)
H5	0.6482	0.0924	0.3056	0.028*
C11	0.94793 (12)	0.1792 (2)	0.3219 (6)	0.0277 (6)
H11	0.9794	0.1731	0.1917	0.033*
C12	0.91355 (11)	0.2773 (2)	0.3611 (5)	0.0240 (6)
H12	0.9224	0.3382	0.2575	0.029*
C3	0.61372 (11)	0.2795 (2)	0.7337 (5)	0.0234 (6)
H3	0.5843	0.2952	0.8667	0.028*
C1	0.70619 (12)	0.3303 (2)	0.4696 (5)	0.0186 (5)
C13	0.51905 (13)	0.1183 (2)	0.8577 (6)	0.0330 (7)
H13A	0.5443	0.1268	1.0134	0.049*
H13B	0.4901	0.0560	0.8745	0.049*
H13C	0.4933	0.1837	0.8281	0.049*
C9	0.88759 (13)	0.0962 (2)	0.6755 (6)	0.0261 (6)
H9	0.8794	0.0353	0.7801	0.031*
H1	0.8245 (14)	0.399 (2)	0.763 (2)	0.023 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0222 (3)	0.0161 (3)	0.0134 (3)	−0.0004 (2)	−0.0004 (2)	−0.0003 (2)
F1	0.0403 (8)	0.0248 (8)	0.0333 (10)	0.0127 (6)	0.0008 (8)	−0.0014 (8)
O1	0.0286 (8)	0.0160 (9)	0.0241 (10)	0.0003 (7)	−0.0029 (7)	−0.0009 (7)
O2	0.0280 (9)	0.0249 (10)	0.0172 (10)	−0.0017 (8)	0.0010 (8)	−0.0009 (8)
O3	0.0258 (9)	0.0260 (10)	0.0349 (13)	−0.0065 (8)	0.0066 (9)	−0.0040 (9)
N1	0.0228 (9)	0.0193 (11)	0.0117 (11)	−0.0006 (8)	0.0019 (9)	−0.0019 (9)
C10	0.0262 (12)	0.0222 (14)	0.0251 (15)	0.0056 (11)	−0.0031 (11)	−0.0029 (11)
C6	0.0239 (11)	0.0208 (13)	0.0225 (15)	0.0030 (10)	0.0038 (10)	−0.0064 (11)
C8	0.0221 (10)	0.0265 (15)	0.0202 (14)	0.0010 (10)	0.0050 (10)	0.0016 (11)
C7	0.0202 (11)	0.0186 (13)	0.0155 (13)	−0.0019 (10)	−0.0016 (9)	−0.0015 (10)
C4	0.0201 (11)	0.0181 (13)	0.0265 (14)	−0.0009 (9)	−0.0039 (11)	0.0023 (11)
C2	0.0268 (12)	0.0202 (13)	0.0193 (13)	−0.0003 (10)	−0.0019 (10)	−0.0052 (11)
C5	0.0258 (11)	0.0183 (12)	0.0261 (14)	−0.0003 (9)	−0.0027 (11)	−0.0081 (13)
C11	0.0279 (11)	0.0306 (15)	0.0246 (17)	0.0054 (12)	0.0065 (11)	−0.0005 (12)
C12	0.0275 (11)	0.0227 (12)	0.0218 (14)	0.0003 (10)	0.0065 (11)	0.0023 (11)
C3	0.0234 (11)	0.0268 (14)	0.0201 (14)	−0.0002 (11)	0.0034 (10)	−0.0032 (11)
C1	0.0212 (11)	0.0182 (12)	0.0162 (12)	0.0018 (10)	−0.0026 (9)	−0.0010 (10)
C13	0.0272 (12)	0.0401 (15)	0.0316 (17)	−0.0092 (12)	0.0027 (12)	0.0013 (14)
C9	0.0316 (13)	0.0208 (14)	0.0260 (16)	−0.0008 (11)	−0.0004 (12)	0.0050 (12)

S1—O1	1.4275 (18)	C8—H8	0.9300
S1—O2	1.435 (2)	C7—C12	1.380 (3)
S1—N1	1.647 (2)	C4—C5	1.385 (4)
S1—C1	1.764 (2)	C4—C3	1.390 (4)
F1—C10	1.358 (3)	C2—C1	1.378 (4)
O3—C4	1.371 (3)	C2—C3	1.388 (4)
O3—C13	1.423 (3)	C2—H2	0.9300
N1—C7	1.444 (3)	C5—H5	0.9300
N1—H1	0.898 (10)	C11—C12	1.392 (4)
C10—C9	1.371 (4)	C11—H11	0.9300
C10—C11	1.378 (4)	C12—H12	0.9300
C6—C5	1.372 (3)	C3—H3	0.9300
C6—C1	1.395 (3)	C13—H13A	0.9600
C6—H6	0.9300	C13—H13B	0.9600
C8—C7	1.385 (4)	C13—H13C	0.9600
C8—C9	1.394 (4)	C9—H9	0.9300
O1—S1—O2	120.28 (11)	C1—C2—H2	120.0
O1—S1—N1	105.44 (11)	C3—C2—H2	120.0
O2—S1—N1	106.74 (11)	C6—C5—C4	120.5 (2)
O1—S1—C1	108.44 (11)	C6—C5—H5	119.8
O2—S1—C1	108.41 (11)	C4—C5—H5	119.8
N1—S1—C1	106.77 (11)	C10—C11—C12	117.9 (2)
C4—O3—C13	117.5 (2)	C10—C11—H11	121.1
C7—N1—S1	118.62 (16)	C12—C11—H11	121.1
C7—N1—H1	111.3 (19)	C7—C12—C11	120.2 (2)
S1—N1—H1	113.8 (19)	C7—C12—H12	119.9
F1—C10—C9	118.5 (2)	C11—C12—H12	119.9
F1—C10—C11	118.3 (2)	C2—C3—C4	118.9 (2)
C9—C10—C11	123.3 (2)	C2—C3—H3	120.5
C5—C6—C1	119.0 (2)	C4—C3—H3	120.5
C5—C6—H6	120.5	C2—C1—C6	120.9 (2)
C1—C6—H6	120.5	C2—C1—S1	119.40 (19)
C7—C8—C9	120.0 (2)	C6—C1—S1	119.56 (19)
C7—C8—H8	120.0	O3—C13—H13A	109.5
C9—C8—H8	120.0	O3—C13—H13B	109.5
C12—C7—C8	120.5 (2)	H13A—C13—H13B	109.5
C12—C7—N1	118.9 (2)	O3—C13—H13C	109.5
C8—C7—N1	120.5 (2)	H13A—C13—H13C	109.5
O3—C4—C5	115.2 (2)	H13B—C13—H13C	109.5
O3—C4—C3	124.1 (2)	C10—C9—C8	118.1 (3)
C5—C4—C3	120.7 (2)	C10—C9—H9	121.0
C1—C2—C3	120.0 (2)	C8—C9—H9	121.0
O1—S1—N1—C7	−176.37 (18)	C1—C2—C3—C4	0.5 (4)
O2—S1—N1—C7	−47.4 (2)	O3—C4—C3—C2	179.3 (2)
C1—S1—N1—C7	68.4 (2)	C5—C4—C3—C2	−0.8 (4)
C9—C8—C7—C12	−0.1 (4)	C3—C2—C1—C6	−0.2 (4)
C9—C8—C7—N1	−177.5 (2)	C3—C2—C1—S1	−176.4 (2)
S1—N1—C7—C12	80.1 (3)	C5—C6—C1—C2	0.1 (4)
S1—N1—C7—C8	−102.5 (2)	C5—C6—C1—S1	176.26 (19)
C13—O3—C4—C5	177.0 (2)	O1—S1—C1—C2	−27.8 (2)
C13—O3—C4—C3	−3.0 (4)	O2—S1—C1—C2	−159.9 (2)
C1—C6—C5—C4	−0.3 (4)	N1—S1—C1—C2	85.4 (2)
O3—C4—C5—C6	−179.4 (2)	O1—S1—C1—C6	156.0 (2)
C3—C4—C5—C6	0.7 (4)	O2—S1—C1—C6	23.8 (2)
F1—C10—C11—C12	179.8 (2)	N1—S1—C1—C6	−90.8 (2)
C9—C10—C11—C12	0.5 (4)	F1—C10—C9—C8	−179.3 (2)
C8—C7—C12—C11	0.6 (4)	C11—C10—C9—C8	0.0 (4)
N1—C7—C12—C11	178.0 (2)	C7—C8—C9—C10	−0.2 (4)
C10—C11—C12—C7	−0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.90 (1)	2.06 (1)	2.951 (3)	171 (3)
C6—H6···O1ii	0.93	2.55	3.192 (3)	127
C13—H13B···O3iii	0.96	2.60	3.468 (3)	151