The discrete role of chlorine substitutions in the conformation and supra­molecular architecture of aryl­sulfonamides

Two aryl­sulfonamide derivatives, N-(4-acetyl­phen­yl)benzene­sulfonamide, C₁₄H₁₃NO₃S, and N-(4-acetyl­phen­yl)-2,5-di­chloro­benzene­sulfonamide, C₁₄H₁₁Cl₂NO₃S, differing by the absence or presence of two chloro substituents on one of the phenyl rings, were synthesized and characterized in order to establish structural relationships and the role of chloro sub­stitution on the molecular conformation and crystal assembly. Both aryl­sulfonamides form inversion-related dimers through C-H...[pi] and [pi]-[pi] interactions. These dimers pack in a similar way in the two structures. The substitution of two H atoms at the 2- and 5-positions of one phenyl ring by Cl atoms did not substanti­ally alter the molecular conformation or the inter­molecular architecture displayed by the unsubstituted sulfonamide. The structural information controlling the assembly of such compounds in their crystal phases is in the (phen­yl)benzene­sulfonamide mol­ecular framework.

S1. Comment

Compounds containing a sulfonamide group, SO₂NH, are known to be powerful inhibitors of carbonic anhydrases. They are among the most widely used antibacterial agents in the world, mainly due to their low cost, low toxicity and excellent activity against common bacterial diseases (Ozbek et al., 2007). The sulfonamide group occurs in many biologically active compounds, including antimicrobial, antithyroid, antitumor and antimalarial drugs (Ozdemir et al., 2009; Seo et al., 2010; Dominguez et al., 2005; Connor, 1998; Hanson et al., 1999). In addition, several substituted aromatic and heterocyclic sulfonamides have been synthesized and evaluated for their potential therapeutic use as antiglaucoma agents (Remko et al., 2010).

In this study, two arylsulfonamide derivatives, differing in two chlorine substitutions on one of their two phenyl rings, were synthesized and characterized by X-ray diffraction, in order to establish structural relationships and the chlorine role in the conformation and crystal assembly: N-(4-acetylphenyl)benzenesulfonamide, C₁₄H₁₃NO₃S, (I), and N-(4-acetylphenyl)-2,5-dichlorobenzenesulfonamide, C₁₄H₁₁Cl₂NO₃S, (II). Based on such knowledge, pharmacological profiles of these compounds could be further rationalized.

Despite the significant molecular differences between the two compounds determined here, sulfonamides (I) and (II) exhibit similar intramolecular geometry (Fig. 1). A superposition of their molecular backbones shows the conformational similarity between the two compounds (Fig. 2), except for a slight rotation on the sulfamyl bridge bond axis (see text below). As a practice in analyzing the intramolecular features of small molecules determined by X-ray diffraction, the geometric parameters of sulfonamides (I) and (II) were submitted to a Mogul check (Bruno et al., 2004). All geometric values agree with those of other reported sulfonamide structures (e.g. Perlovich et al., 2011; Martins et al., 2009; Drebushchak et al., 2006, 2007). A near-90° angle between the two aromatic rings is a remarkable intramolecular feature observed in other related bioactive sulfonamides and was found in both structures (I) and (II). The planes through phenyl A and B form an angle of 88.27 (8)° in (I) and 75.72 (8)° in (II) suggesting that their relationship is related to hindrance effects involving the two rings A and B. However, the assignment of structural features as a result of only intermolecular forces is a very difficult exercise.

Not only are the molecular structures of sulfonamides (I) and (II) similar but so also are the supramolecular assemblies. In both structures, infinite one-dimensional chains are formed along the [010] direction by translation-related molecules (Fig. 3). Each chain is therefore composed of only one enantiomorph. In (I), these chains are created by a classical N1—H1···O3ⁱ [symmetry code: (i) x, y + 1, z] hydrogen bond and a non-classical C9—H9···O1ⁱⁱ [symmetry code: (ii) x, y - 1, z] one, while the bifurcated N1—H1···O3ⁱ and C12—H12···O3ⁱ hydrogen-bond interactions connect such ribbons in (II). Geometric parameters of the hydrogen-bond interactions are shown in Tables 1 and 2. Enantiopure chains are stacked parallel to the direction [100] to create layers where the neighboring ribbon is composed of the same enantiomorph [in the case of the structure of sulfonamide (II)] or the other one [in the case of the structure of sulfonamide (I)].

The hydrogen-bond patterns that assemble the chains differ between (I) and (II), as mentioned above. This can be viewed as a result of displacing molecules of (II) onto the (100) plane when compared to (I) (Fig. 4). Such displacement is related to the formation of a halogen–π interaction between the 2₁-screw axis symmetry-related molecules of (II). The occurrence of this intermolecular contact is supported by the short distance between Cl2 and the centroid of ring A (CgA) [3.528 (7) Å]. This halogen–π interaction Cl2···CgAⁱⁱⁱ [symmetry code: (iii) - x + 1, y - 1/2, - z - 1/2], along with halogen–halogen contacts Cl1···Cl2^iv [symmetry code: (iv) x, - y + 1.5, z + 1/2] and Cl1···Cl1^v [symmetry code: (v) - x + 1, - y + 2, - z], occurring in (II), are the main differences between the crystal structures of the two sulfonamides.

Besides the three-dimensional connection of the [100]-stacked [010] chains along the c axis, these halogen–π and halogen–halogen interactions, together with the dipole–dipole O2···C13^vi [symmetry code: (vi) - x + 2, y - 1/2, - z + 1/2] contact occurring between the sulfonyl and carbonyl groups of 2₁-screw axis symmetry-related molecules of (II) stacked parallel to the [100] direction, are responsible for the most significant conformational difference between the two compounds reported in this study: there is a conformational flexibility on the bridge connecting two phenyl rings, which features a slight rotation on the N1—S1 bond axis of (II) if the sulfamyl moiety conformation of (I) is used as a reference. The values of the dihedral angles X—N1—S1—Y (Table 3) deviate by approximately 15° between the two sulfonamides, which is in agreement with the rotation mentioned above.

No dipole–dipole O2···C13 interaction occurs in (I). In this structure, along the direction [010], the C5—H5···O1^vii [symmetry code: (vii) - x + 1, y - 1/2, - z + 1.5] hydrogen bond also connects 2₁-screw axis symmetry-related molecules of (I) assembled into different one-dimensional chains made up of only one enantiomorph.

Additionally, both structures are stabilized by C—H···π and π···π interactions. The two sulfonamides are characterized by the formation of inversion-related dimers. The contacts C4—H4···CgB^iix [symmetry code: (iix) - x + 1, - y, - z + 1] and CgA···CgA^iix assemble these pairs of molecules in (I). Likewise, the contacts C4—H4···CgB^ix [symmetry code: (ix) - x + 1, - y + 1, - z] and CgA···CgA^ix play such a role in (II) (Fig. 5). These dimers can be considered the building units of both crystal architectures, while their interaction patterns differ between the structures (I) and (II). Contributing to stabilization of the dimers of (II), there are two other halogen–halogen Cl1···Cl2^ix contacts between inversion-related molecules kept in contact by the face-to-face and face-to-edge stacking interactions.

In conclusion, it was possible to characterize the existence of several classical and non-classical hydrogen bonds and π–π stacking interactions contributing to stabilization of the crystal packing of both compounds. Although the substitution of two H atoms at positions 2 and 5 of ring A, by chlorine atoms, did not alter greatly the conformation and the intermolecular architecture of the two sulfonamide analogs, despite halogen–π, halogen–halogen and dipole–dipole interactions present only in (II), it plays a discrete role in the conformation, which differs slightly from that of (I). This reveals that the structural information required to assemble such compounds in their crystal phases is in the (phenyl)benzenesulfonamide molecular framework.

Related literature

For related literature, see: Bruno et al. (2004); Connor (1998); Dominguez et al. (2005); Drebushchak et al. (2006, 2007); Hanson et al. (1999); Martins et al. (2009); Ozbek et al. (2007); Ozdemir et al. (2009); Perlovich et al. (2011); Remko et al. (2010); Seo et al. (2010).

S2. Experimental

Compounds (I) and (II) were obtained by equimolar coupling between benzene sulfonyl chloride or 2,5-dichlorobenzene sulfonyl chloride and 4-amineacetophenone in dichloromethane or acetone as solvent. The reactions were performed at 343 K for about 6 h. The precipitate was re-crystallized in suitable solvents to obtain the single crystals. The reaction yields were 54 and 55% for compounds (I) and (II), respectively.

S3. Refinement

The non-hydrogen atoms were refined anisotropically. All C—H H atoms were placed geometrically and refined using a riding model, with U_iso(H) = 1.2U_eq (C or N). The C—H distances were fixed for CH₃ groups at 0.96 Å, and for aromatic groups at 0.93 Å. The hydrogen H1 bonded to nitrogen was found from the difference Fourier map and its positional parameters were refined freely.

Computing details

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecular structures of (I) and (II), showing the atom- and ring-labeling schemes. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. A superposition of sulfonamides (I) (grey) and (II) (black). H atoms have been omitted for clarity.
	Fig. 3. Infinite one-dimensional chains of (a) (I) and (b) (II), growing along the [010] direction. [Symmetry codes: (i) x, y + 1, z; (ii) x, y - 1, z; (vi) -x + 2, y - 1/2, -z + 1/2.]
	Fig. 4. The halogen–π interaction occurring only in the structure of (II). [Symmetry code: (iii) -x + 1, y - 1/2, -z - 1/2.]
	Fig. 5. The C—H···π and π–π interactions in the structures of (a) (I) and (b) (II). [Symmetry codes: (iix) -x + 1, -y, -z + 1; (ix) -x + 1, -y + 1, -z.] [Please redraw with labels not overlapping the elements of the figure. Also note that "iix" is not a roman numeral.]

(I) N-(4-acetylphenyl)benzenesulfonamide

Crystal data

C14H13NO3S	F(000) = 576
Mr = 275.31	Dx = 1.357 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.0007 (5) Å	Cell parameters from 5393 reflections
b = 8.3615 (4) Å	θ = 2.9–27.5°
c = 12.5179 (6) Å	µ = 0.24 mm^−1
β = 98.118 (3)°	T = 293 K
V = 1347.13 (10) Å^3	Prism, colourless
Z = 4	0.4 × 0.4 × 0.35 mm

Data collection

Nonius KappaCCD diffractometer	2214 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	Rint = 0.046
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
Detector resolution: 9 pixels mm^-1	h = −16→16
CCD rotation images, thick slices scans	k = −10→8
9368 measured reflections	l = −15→16
3006 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0766P)^2 + 0.3229P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3006 reflections	Δρmax = 0.25 e Å^−3
177 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (8)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.28211 (4)	0.17624 (6)	0.71698 (4)	0.0559 (2)
O1	0.25289 (14)	0.33631 (18)	0.73879 (14)	0.0722 (5)
O2	0.29545 (13)	0.0609 (2)	0.80164 (12)	0.0707 (5)
O3	0.12667 (13)	−0.61566 (18)	0.48557 (13)	0.0682 (4)
N1	0.19035 (13)	0.1157 (2)	0.62299 (14)	0.0553 (4)
H1	0.1663 (19)	0.195 (3)	0.584 (2)	0.066*
C1	0.39650 (16)	0.1802 (2)	0.65658 (16)	0.0533 (5)
C2	0.39932 (19)	0.2771 (3)	0.5673 (2)	0.0696 (6)
H2	0.3417	0.3376	0.5393	0.084*
C3	0.4889 (2)	0.2821 (4)	0.5208 (2)	0.0856 (8)
H3	0.4917	0.3459	0.4604	0.103*
C4	0.5743 (2)	0.1936 (4)	0.5626 (3)	0.0898 (8)
H4	0.6347	0.1985	0.5309	0.108*
C5	0.5705 (2)	0.0986 (4)	0.6505 (3)	0.0911 (9)
H5	0.6287	0.0397	0.6788	0.109*
C6	0.48082 (19)	0.0891 (3)	0.6981 (2)	0.0728 (7)
H6	0.4777	0.0224	0.7569	0.087*
C7	0.18028 (14)	−0.0372 (2)	0.57524 (15)	0.0473 (4)
C8	0.21204 (16)	−0.1768 (2)	0.63070 (16)	0.0537 (5)
H8	0.2482	−0.1713	0.7002	0.064*
C9	0.18986 (15)	−0.3233 (2)	0.58241 (16)	0.0507 (5)
H9	0.2116	−0.416	0.62	0.061*
C10	0.13564 (14)	−0.3354 (2)	0.47862 (15)	0.0472 (4)
C11	0.10813 (19)	−0.1941 (3)	0.42331 (17)	0.0629 (6)
H11	0.0737	−0.1991	0.353	0.075*
C12	0.13066 (18)	−0.0473 (2)	0.47025 (17)	0.0620 (5)
H12	0.1125	0.0456	0.4312	0.074*
C13	0.10407 (15)	−0.4947 (2)	0.43357 (16)	0.0514 (5)
C14	0.03893 (18)	−0.5070 (3)	0.32538 (17)	0.0645 (6)
H14A	0.0273	−0.6176	0.307	0.097*
H14B	0.0743	−0.4563	0.2721	0.097*
H14C	−0.0266	−0.455	0.3276	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0663 (4)	0.0490 (3)	0.0515 (3)	−0.0054 (2)	0.0056 (2)	−0.0056 (2)
O1	0.0854 (11)	0.0533 (9)	0.0774 (11)	−0.0009 (7)	0.0098 (8)	−0.0196 (8)
O2	0.0904 (11)	0.0707 (10)	0.0494 (8)	−0.0129 (8)	0.0038 (7)	0.0034 (7)
O3	0.0851 (11)	0.0452 (8)	0.0727 (10)	−0.0006 (7)	0.0059 (8)	0.0009 (7)
N1	0.0599 (10)	0.0428 (9)	0.0609 (10)	−0.0011 (7)	0.0007 (7)	−0.0015 (8)
C1	0.0569 (10)	0.0471 (10)	0.0534 (11)	−0.0043 (8)	−0.0006 (8)	−0.0022 (8)
C2	0.0688 (14)	0.0679 (14)	0.0713 (14)	0.0025 (11)	0.0072 (11)	0.0178 (11)
C3	0.0857 (18)	0.0902 (19)	0.0842 (18)	−0.0042 (15)	0.0236 (14)	0.0192 (15)
C4	0.0646 (15)	0.102 (2)	0.106 (2)	−0.0042 (14)	0.0236 (14)	−0.0026 (18)
C5	0.0639 (15)	0.097 (2)	0.108 (2)	0.0174 (14)	−0.0007 (14)	0.0047 (18)
C6	0.0726 (14)	0.0694 (15)	0.0724 (15)	0.0089 (11)	−0.0029 (11)	0.0118 (12)
C7	0.0473 (9)	0.0428 (10)	0.0518 (10)	−0.0029 (7)	0.0071 (7)	−0.0003 (8)
C8	0.0597 (11)	0.0496 (11)	0.0489 (10)	−0.0006 (8)	−0.0021 (8)	0.0015 (8)
C9	0.0555 (10)	0.0436 (10)	0.0514 (10)	0.0023 (8)	0.0023 (8)	0.0049 (8)
C10	0.0479 (9)	0.0453 (10)	0.0480 (10)	0.0004 (7)	0.0058 (7)	−0.0003 (8)
C11	0.0798 (14)	0.0545 (12)	0.0489 (11)	0.0015 (10)	−0.0091 (10)	0.0020 (9)
C12	0.0816 (14)	0.0446 (11)	0.0551 (11)	0.0027 (9)	−0.0063 (10)	0.0072 (9)
C13	0.0509 (10)	0.0506 (11)	0.0539 (11)	−0.0009 (8)	0.0116 (8)	−0.0050 (9)
C14	0.0713 (13)	0.0650 (14)	0.0561 (12)	−0.0063 (10)	0.0052 (10)	−0.0118 (10)

Geometric parameters (Å, º)

S1—O2	1.4251 (16)	C6—H6	0.93
S1—O1	1.4281 (16)	C7—C12	1.383 (3)
S1—N1	1.6331 (17)	C7—C8	1.391 (3)
S1—C1	1.761 (2)	C8—C9	1.378 (3)
O3—C13	1.216 (2)	C8—H8	0.93
N1—C7	1.410 (2)	C9—C10	1.392 (3)
N1—H1	0.85 (2)	C9—H9	0.93
C1—C6	1.375 (3)	C10—C11	1.390 (3)
C1—C2	1.386 (3)	C10—C13	1.482 (3)
C2—C3	1.374 (4)	C11—C12	1.375 (3)
C2—H2	0.93	C11—H11	0.93
C3—C4	1.375 (4)	C12—H12	0.93
C3—H3	0.93	C13—C14	1.496 (3)
C4—C5	1.364 (4)	C14—H14A	0.96
C4—H4	0.93	C14—H14B	0.96
C5—C6	1.384 (4)	C14—H14C	0.96
C5—H5	0.93
O2—S1—O1	119.98 (11)	C12—C7—C8	119.28 (18)
O2—S1—N1	109.02 (9)	C12—C7—N1	117.47 (17)
O1—S1—N1	103.95 (10)	C8—C7—N1	123.13 (17)
O2—S1—C1	108.09 (10)	C9—C8—C7	119.87 (18)
O1—S1—C1	109.15 (10)	C9—C8—H8	120.1
N1—S1—C1	105.77 (9)	C7—C8—H8	120.1
C7—N1—S1	126.95 (14)	C8—C9—C10	121.40 (18)
C7—N1—H1	117.0 (17)	C8—C9—H9	119.3
S1—N1—H1	110.1 (17)	C10—C9—H9	119.3
C6—C1—C2	121.2 (2)	C11—C10—C9	117.66 (18)
C6—C1—S1	120.26 (18)	C11—C10—C13	122.44 (17)
C2—C1—S1	118.53 (16)	C9—C10—C13	119.80 (17)
C3—C2—C1	118.7 (2)	C12—C11—C10	121.44 (19)
C3—C2—H2	120.6	C12—C11—H11	119.3
C1—C2—H2	120.6	C10—C11—H11	119.3
C2—C3—C4	120.6 (3)	C11—C12—C7	120.23 (19)
C2—C3—H3	119.7	C11—C12—H12	119.9
C4—C3—H3	119.7	C7—C12—H12	119.9
C5—C4—C3	120.1 (3)	O3—C13—C10	120.73 (18)
C5—C4—H4	120	O3—C13—C14	119.40 (19)
C3—C4—H4	120	C10—C13—C14	119.80 (18)
C4—C5—C6	120.6 (2)	C13—C14—H14A	109.5
C4—C5—H5	119.7	C13—C14—H14B	109.5
C6—C5—H5	119.7	H14A—C14—H14B	109.5
C1—C6—C5	118.7 (2)	C13—C14—H14C	109.5
C1—C6—H6	120.6	H14A—C14—H14C	109.5
C5—C6—H6	120.6	H14B—C14—H14C	109.5
O2—S1—N1—C7	−48.6 (2)	C12—C7—C8—C9	−2.8 (3)
O1—S1—N1—C7	−177.62 (17)	N1—C7—C8—C9	173.15 (19)
C1—S1—N1—C7	67.46 (19)	C7—C8—C9—C10	−0.2 (3)
O2—S1—C1—C6	−4.2 (2)	C8—C9—C10—C11	2.6 (3)
O1—S1—C1—C6	127.89 (19)	C8—C9—C10—C13	−173.90 (18)
N1—S1—C1—C6	−120.81 (19)	C9—C10—C11—C12	−1.9 (3)
O2—S1—C1—C2	176.07 (17)	C13—C10—C11—C12	174.4 (2)
O1—S1—C1—C2	−51.9 (2)	C10—C11—C12—C7	−1.0 (4)
N1—S1—C1—C2	59.42 (19)	C8—C7—C12—C11	3.4 (3)
C6—C1—C2—C3	−0.6 (4)	N1—C7—C12—C11	−172.8 (2)
S1—C1—C2—C3	179.2 (2)	C11—C10—C13—O3	−177.6 (2)
C1—C2—C3—C4	−0.5 (4)	C9—C10—C13—O3	−1.4 (3)
C2—C3—C4—C5	0.5 (5)	C11—C10—C13—C14	−0.9 (3)
C3—C4—C5—C6	0.5 (5)	C9—C10—C13—C14	175.41 (19)
C2—C1—C6—C5	1.6 (4)	H1—N1—S1—O2	159.7 (18)
S1—C1—C6—C5	−178.2 (2)	H1—N1—S1—O1	30.7 (18)
C4—C5—C6—C1	−1.6 (4)	H1—N1—C7—C12	−1.2 (19)
S1—N1—C7—C12	−151.28 (18)	H1—N1—C7—C8	−177.3 (18)
S1—N1—C7—C8	32.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.85 (2)	2.03 (3)	2.879 (2)	173 (2)
C9—H9···O1^ii	0.93	2.56	3.486 (2)	172
C5—H5···O1^iii	0.93	2.42	3.332 (3)	165

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+3/2.

(II) N-(4-acetylphenyl)-2,5-dichlorobenzenesulfonamide

Crystal data

C14H11Cl2NO3S	F(000) = 704
Mr = 344.2	Dx = 1.548 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.3622 (2) Å	Cell parameters from 3123 reflections
b = 8.1542 (2) Å	θ = 2.9–26.4°
c = 15.6845 (3) Å	µ = 0.59 mm^−1
β = 120.184 (1)°	T = 293 K
V = 1477.24 (5) Å^3	Prism, colourless
Z = 4	0.4 × 0.35 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer	2463 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	Rint = 0.026
Graphite monochromator	θmax = 26.4°, θmin = 3.0°
Detector resolution: 9 pixels mm^-1	h = −16→16
CCD rotation images, thick slices scans	k = −10→10
5653 measured reflections	l = −19→19
2972 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0933P)^2 + 0.2084P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2972 reflections	Δρmax = 0.39 e Å^−3
195 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.090 (10)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.79530 (4)	0.83233 (6)	0.05550 (4)	0.0488 (2)
O1	0.78207 (15)	1.0059 (2)	0.04572 (12)	0.0646 (5)
O2	0.86360 (12)	0.7506 (2)	0.02183 (11)	0.0587 (4)
O3	0.86046 (18)	0.0499 (2)	0.30593 (13)	0.0757 (5)
Cl1	0.58980 (6)	0.88625 (9)	0.11029 (5)	0.0732 (3)
Cl2	0.50412 (8)	0.43227 (11)	−0.23775 (6)	0.0994 (3)
N1	0.84773 (16)	0.7941 (2)	0.17204 (13)	0.0491 (4)
H1	0.843 (2)	0.873 (3)	0.2009 (19)	0.059*
C1	0.65667 (17)	0.7376 (2)	−0.00887 (14)	0.0468 (4)
C2	0.56785 (19)	0.7677 (3)	0.01157 (17)	0.0547 (5)
C3	0.4597 (2)	0.6985 (3)	−0.0476 (2)	0.0668 (7)
H3	0.4001	0.7209	−0.035	0.08*
C4	0.4394 (2)	0.5974 (3)	−0.12460 (18)	0.0665 (6)
H4	0.3666	0.5513	−0.1639	0.08*
C5	0.5276 (2)	0.5648 (3)	−0.14309 (17)	0.0620 (6)
C6	0.63559 (19)	0.6352 (3)	−0.08694 (15)	0.0533 (5)
H6	0.6939	0.6141	−0.1014	0.064*
C7	0.85437 (16)	0.6392 (2)	0.21386 (14)	0.0431 (4)
C8	0.85919 (17)	0.4930 (3)	0.17005 (15)	0.0490 (5)
H8	0.8599	0.4952	0.1111	0.059*
C9	0.86294 (18)	0.3449 (2)	0.21407 (15)	0.0486 (5)
H9	0.8649	0.2479	0.1838	0.058*
C10	0.86377 (17)	0.3386 (2)	0.30333 (14)	0.0445 (4)
C11	0.86201 (18)	0.4858 (3)	0.34761 (14)	0.0502 (5)
H11	0.8647	0.4838	0.408	0.06*
C12	0.85640 (19)	0.6345 (2)	0.30348 (15)	0.0498 (5)
H12	0.854	0.7316	0.3335	0.06*
C13	0.86630 (18)	0.1773 (2)	0.34830 (15)	0.0505 (5)
C14	0.8753 (2)	0.1724 (3)	0.44720 (19)	0.0639 (6)
H14A	0.885	0.0609	0.4698	0.096*
H14B	0.8059	0.2167	0.4421	0.096*
H14C	0.9406	0.2363	0.4932	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0608 (4)	0.0406 (3)	0.0460 (3)	−0.0073 (2)	0.0277 (3)	0.00152 (19)
O1	0.0927 (12)	0.0398 (9)	0.0597 (9)	−0.0103 (7)	0.0371 (9)	0.0049 (7)
O2	0.0635 (9)	0.0652 (10)	0.0587 (9)	−0.0076 (7)	0.0390 (7)	−0.0026 (8)
O3	0.1229 (15)	0.0365 (8)	0.0684 (10)	−0.0005 (9)	0.0487 (10)	−0.0052 (8)
Cl1	0.0878 (5)	0.0713 (5)	0.0708 (4)	0.0182 (3)	0.0474 (4)	−0.0007 (3)
Cl2	0.1377 (7)	0.0885 (6)	0.0706 (5)	−0.0490 (5)	0.0513 (5)	−0.0308 (4)
N1	0.0637 (10)	0.0370 (9)	0.0448 (9)	−0.0048 (7)	0.0260 (8)	−0.0030 (7)
C1	0.0541 (10)	0.0386 (10)	0.0468 (10)	0.0006 (8)	0.0248 (8)	0.0066 (8)
C2	0.0626 (12)	0.0465 (11)	0.0572 (12)	0.0073 (9)	0.0316 (10)	0.0085 (9)
C3	0.0570 (13)	0.0652 (15)	0.0787 (16)	0.0075 (11)	0.0345 (12)	0.0177 (13)
C4	0.0581 (13)	0.0627 (15)	0.0621 (14)	−0.0085 (11)	0.0178 (11)	0.0109 (12)
C5	0.0752 (14)	0.0516 (13)	0.0490 (11)	−0.0115 (11)	0.0237 (11)	0.0024 (10)
C6	0.0674 (13)	0.0461 (11)	0.0473 (11)	−0.0051 (9)	0.0295 (10)	0.0010 (9)
C7	0.0463 (9)	0.0388 (10)	0.0408 (9)	−0.0029 (7)	0.0193 (8)	−0.0011 (7)
C8	0.0602 (11)	0.0456 (11)	0.0450 (10)	0.0032 (9)	0.0291 (9)	−0.0006 (8)
C9	0.0597 (11)	0.0400 (10)	0.0490 (11)	0.0047 (8)	0.0295 (9)	−0.0045 (8)
C10	0.0501 (10)	0.0387 (10)	0.0418 (9)	0.0013 (7)	0.0210 (8)	−0.0006 (8)
C11	0.0680 (12)	0.0417 (11)	0.0441 (10)	0.0016 (9)	0.0306 (10)	−0.0019 (8)
C12	0.0674 (12)	0.0367 (10)	0.0449 (10)	0.0003 (9)	0.0280 (9)	−0.0038 (8)
C13	0.0582 (11)	0.0389 (11)	0.0523 (11)	−0.0002 (8)	0.0263 (10)	−0.0001 (8)
C14	0.0894 (17)	0.0458 (12)	0.0682 (15)	−0.0013 (11)	0.0484 (13)	0.0057 (10)

Geometric parameters (Å, º)

S1—O1	1.4250 (17)	C6—H6	0.93
S1—O2	1.4282 (16)	C7—C12	1.393 (3)
S1—N1	1.6253 (18)	C7—C8	1.394 (3)
S1—C1	1.780 (2)	C8—C9	1.379 (3)
O3—C13	1.214 (3)	C8—H8	0.93
Cl1—C2	1.721 (2)	C9—C10	1.395 (3)
Cl2—C5	1.733 (3)	C9—H9	0.93
N1—C7	1.406 (3)	C10—C11	1.393 (3)
N1—H1	0.81 (3)	C10—C13	1.485 (3)
C1—C6	1.389 (3)	C11—C12	1.379 (3)
C1—C2	1.398 (3)	C11—H11	0.93
C2—C3	1.385 (4)	C12—H12	0.93
C3—C4	1.372 (4)	C13—C14	1.495 (3)
C3—H3	0.93	C14—H14A	0.96
C4—C5	1.373 (4)	C14—H14B	0.96
C4—H4	0.93	C14—H14C	0.96
C5—C6	1.382 (3)
O1—S1—O2	119.42 (9)	C12—C7—C8	119.47 (18)
O1—S1—N1	105.75 (9)	C12—C7—N1	117.39 (17)
O2—S1—N1	109.40 (10)	C8—C7—N1	123.14 (18)
O1—S1—C1	109.44 (10)	C9—C8—C7	120.07 (19)
O2—S1—C1	105.31 (9)	C9—C8—H8	120
N1—S1—C1	106.97 (9)	C7—C8—H8	120
C7—N1—S1	125.98 (14)	C8—C9—C10	120.99 (18)
C7—N1—H1	117.2 (19)	C8—C9—H9	119.5
S1—N1—H1	111.5 (18)	C10—C9—H9	119.5
C6—C1—C2	119.26 (19)	C11—C10—C9	118.32 (18)
C6—C1—S1	116.93 (15)	C11—C10—C13	121.92 (18)
C2—C1—S1	123.71 (16)	C9—C10—C13	119.76 (18)
C3—C2—C1	119.6 (2)	C12—C11—C10	121.18 (18)
C3—C2—Cl1	118.68 (18)	C12—C11—H11	119.4
C1—C2—Cl1	121.66 (17)	C10—C11—H11	119.4
C4—C3—C2	120.8 (2)	C11—C12—C7	119.93 (19)
C4—C3—H3	119.6	C11—C12—H12	120
C2—C3—H3	119.6	C7—C12—H12	120
C3—C4—C5	119.4 (2)	O3—C13—C10	121.2 (2)
C3—C4—H4	120.3	O3—C13—C14	119.6 (2)
C5—C4—H4	120.3	C10—C13—C14	119.16 (18)
C4—C5—C6	121.1 (2)	C13—C14—H14A	109.5
C4—C5—Cl2	119.79 (19)	C13—C14—H14B	109.5
C6—C5—Cl2	119.1 (2)	H14A—C14—H14B	109.5
C5—C6—C1	119.7 (2)	C13—C14—H14C	109.5
C5—C6—H6	120.2	H14A—C14—H14C	109.5
C1—C6—H6	120.2	H14B—C14—H14C	109.5
O1—S1—N1—C7	166.97 (17)	S1—C1—C6—C5	−176.60 (16)
O2—S1—N1—C7	−63.21 (19)	S1—N1—C7—C12	−154.54 (17)
C1—S1—N1—C7	50.4 (2)	S1—N1—C7—C8	25.6 (3)
O1—S1—C1—C6	117.80 (16)	C12—C7—C8—C9	1.7 (3)
O2—S1—C1—C6	−11.75 (18)	N1—C7—C8—C9	−178.51 (19)
N1—S1—C1—C6	−128.08 (16)	C7—C8—C9—C10	−1.0 (3)
O1—S1—C1—C2	−58.62 (19)	C8—C9—C10—C11	−0.7 (3)
O2—S1—C1—C2	171.84 (17)	C8—C9—C10—C13	179.22 (19)
N1—S1—C1—C2	55.51 (19)	C9—C10—C11—C12	1.7 (3)
C6—C1—C2—C3	−1.6 (3)	C13—C10—C11—C12	−178.17 (19)
S1—C1—C2—C3	174.78 (17)	C10—C11—C12—C7	−1.1 (3)
C6—C1—C2—Cl1	177.22 (16)	C8—C7—C12—C11	−0.6 (3)
S1—C1—C2—Cl1	−6.4 (3)	N1—C7—C12—C11	179.53 (18)
C1—C2—C3—C4	1.6 (4)	C11—C10—C13—O3	175.3 (2)
Cl1—C2—C3—C4	−177.18 (19)	C9—C10—C13—O3	−4.6 (3)
C2—C3—C4—C5	−0.1 (4)	C11—C10—C13—C14	−4.2 (3)
C3—C4—C5—C6	−1.5 (4)	C9—C10—C13—C14	175.9 (2)
C3—C4—C5—Cl2	178.01 (19)	H1—N1—S1—O2	143.6 (19)
C4—C5—C6—C1	1.6 (3)	H1—N1—S1—O1	13.8 (19)
Cl2—C5—C6—C1	−177.96 (16)	H1—N1—C7—C12	−3 (2)
C2—C1—C6—C5	0.0 (3)	H1—N1—C7—C8	177 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.81 (3)	2.11 (3)	2.903 (2)	166 (2)
C12—H12···O3^i	0.93	2.64	3.388 (2)	137

Symmetry code: (i) x, y+1, z.