Layer architecture in 4-nitro­phenyl and 4-chloro­phenyl 3-nitro­benzene­sulfonate at 100 K

The structures of the title compounds, C₁₂H₈N₂O₇S and C₁₂H₈ClNO₅S, contain weak C—H...O interactions creating layers of mol­ecules which, taking the conformation of the mol­ecules into account, are arranged in an ABAB sequence. Both structures can be designated, therefore, as ordered racemates of rotameric species.

S1. Comment

Aromatic sulfonates are used in detecting specific organic anion-binding proteins in the liver plasma membrane (Yachi et al., 1989) and in many other fields (Spungin et al., 1992; Tharakan et al., 1992; Alford et al., 1991; Jiang et al., 1990; Narayanan & Krakow, 1983). The present X-ray study of compounds (I) and (II) was undertaken in order to determine their crystal and molecular structures. This study may serve as a forerunner both for an assessment of the biological significance of these compounds and for studies of the quantitative structure-activity relationships of aromatic sulfonates. \sch

The molecules of (I) and (II) are shown in Figs. 1 and 2, respectively. Ignoring the difference in the nature of the p-substituent of the phenol ring, NO₂ for (I) and Cl for (II), it is readily seen that the molecules of (I) and (II) are mirror images of one another. The mirror-image relationship is clearly brought about by rotational isomerism, i.e. the relative positions of two molecular fragments in terms of rotation about the C—S bond connecting them. Selected geometric parameters for both molecules are given in Table 3. Their internal geometries are clearly very similar and the torsion angles are entirely consistant with the mirror-image relationship between them noted above. The C—C distances within the 3-nitrophenyl and 4-nitrophenyl rings of (I) are in the ranges 1.370 (8)–1.394 (6) and 1.374 (6)–1.385 (6) Å, respectively, and for (II) the corresponding ranges are 1.375 (7)–1.393 (6) and 1.366 (8)–1.404 (7) Å. In (I), atoms N1, O1 and O2 deviate by 0.014 (7), 0.055 (7) and −0.028 (8) Å, respectively, from the C1–C6 mean plane, while atoms N2, O6 and O7 deviate from the C7–C12 mean plane by 0.085 (6), −0.164 (7) and −0.052 (7) Å, respectively. In (II), atoms N1, O1 and O2 deviate from the C1—C6 mean plane by 0.018 (8), −0.246 (9) and 0.274 (10) Å, respectively. The dihedral angles between the two aromatic planes are 57.7 (7) and 51.0 (2)° in (I) and (II), respectively. This is similar to the situation reported for other aromatic sulfonates (Vembu, Nallu, Durmus et al., 2004a,b), but is in contrast with the near coplanar orientation found in 2,4-dinitrophenyl 4-toluenesulfonate (Vembu, Nallu, Garrison & Youngs, 2003), 4-methoxyphenyl-4-toluenesulfonate (Vembu Nallu Garrison Hindi & Youngs, 2003) and 8-quinolyl 3-nitrobenzenesulfonate (Vembu Nallu Spencer & Howard, 2003). This difference arises from the synclinal C1—S—O5—C7 torsion angles in (I) and (II) [−62.6 (3) and 68.9 (4)°, respectively], as distinct from the anti-periplanar/anticlinal arrangement, e.g. 162.5 (2)° for the corresponding angle in 4-methoxyphenyl 4-toluenesulfonate, which permits the strain-relieving near-coplanar orientation of the aromatic species.

Weak intermolecular C—H···O interactions (Tables 1 and 2) of the type described by Desiraju & Steiner (1999) are present in both structures. In the structure of (I), the contacts C6—H6···O3ⁱ, C8—H8···O6ⁱⁱ and C12—H12···O4ⁱⁱⁱ (the first three entries in Table 1; symmetry codes as in Table 1) interconnect the molecules to form layers parallel to (001), as shown in Fig. 3. The molecules within any one layer are identical in conformation and orientation, because they are all related to one another by either cell translation or C-centring. For the layer shown, which contains the molecule in the asymmetric unit, the conformation of the molecules is, for convenience, designated as rotamer A. The neighbouring layers are related by the operation of the c glide of the space group Cc and the molecules within them are therefore of the other rotameric form, rotamer B. Thus the layers of molecules are stacked in the direction of c in an ABAB sequence when the conformation of the molecules is taken into account. For all layers, one surface is entirely occupied by the 4-nitrophenyl (phenol) rings, while the 3-nitrophenyl (sulphonate) rings protrude from the other surface and always in the positive direction of c (Fig. 4). Further, the interface between neighbouring layers is always the same and brings about, in addition to the C5—H5···O7^iv interaction (the fourth in Table 1; symmetry code as in Table 1), a number of close contacts between non-H atoms, of which O6···C4(x − 1/2, 3/2 − y, 1/2 + z]) of 3.132 (6) Å and O2···C10(x, 1 − y, z − 1/2) of 3.152 (6) Å are the shortest.

The structure of (II) contains nominally similar layers of molecules, again parallel to (001) (Fig. 5). Intermolecular contacts within these layers are typified by the contacts C4—H4···O3ⁱ, C8—H8···O2ⁱⁱ and C9—H9···O3ⁱⁱⁱ (the first three entries in Table 2; symmetry codes as in Table 2)·The molecules within the layer are identical in conformation and orientation, because they are related to one another purely by cell translation. In this case, while one surface of the layer is populated by the 3-nitrophenyl group, it is now the 4-chlorophenyl group which protrudes from the other surface (Fig. 6), the converse of the situation in the layers of (I) described above. The stacking of the layers in the c direction once again induces an ABAB pattern when the conformation of the molecules within the layers is taken into account, but the inversion in conformation from one layer to the next is now brought about by the operation of crystallographic centres of symmetry. The stacking of the layers (Fig. 6) now creates two distinct forms of interface between them. In the first, at or near z = 1/2, the interface is between the 3-nitrophenyl surfaces of a pair of layers. This permits the further interaction C6—H6···O4^iv (Table 2; symmetry code as in Table 2). At this interface, there is no significant overlap or π–π interaction between the phenyl rings. It is only at the other interface between the layers, at z = 0 and 1, that π–π interaction occurs, where it involves centrosymmetrically related pairs of 4-chlorophenyl rings, with a centroid-centroid separation and perpendicular distance between the ring planes of 3.725 and 3.415 Å, respectively. This is the only significant intermolecular interaction at this interface. This layer sequence can also be thought of in terms of double layers centred on the face-to-face interface at z = 1/2, which then interact with the creation of the π–π interactions at z = 0 and 1.

Rotational isomerism is present in both structures but the structures are completely ordered and may be designated as fully ordered racemates of rotameric species.

S2. Experimental

From the coeditor: Please supply missing data in the following. Both compounds were prepared by the addition of a solution of 3-nitrobenzenesulfonyl chloride (?.??? mg, 5 mmol) dissolved in acetone (5 ml) to a solution of the appropriate phenol (5 mmol) dissolved in NaOH (4 ml, 5% w/v ???) and thorough shaking of the mixture. The precipitated solid products [?.??? mg, 3.7 mmol, yield 74% for (I); ?.??? mg, 3.2 mmol, yield 64% for (II)] were recrystallized from ethanol.

S3. Refinement

All H atoms were included in calculated positions, with C—H 0.95 Å, and refined with a riding model. Their displacement parameters were tied to a common free variable which was refined.

Computing details

For both compounds, data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL and PLATON (Spek 2003).

Figures

	Fig. 1. A view of a molecule of (I), showing the atom-numbering scheme. Non-H atoms are shown as 50% probability displacement ellipsoids.
	Fig. 2. A view of a molecule of (II), showing the atom-numbering scheme. Non-H atoms are shown as 50% probability displacement ellipsoids.
	Fig. 3. Part of a layer of molecules of (I) parallel to (001). Non-H atoms are shown as 50% probability displacement ellipsoids and those H atoms involved in C—H···O contacts (dashed lines) are drawn as small spheres of arbitrary radii. Selected atoms are labelled. [Symmetry codes: (i) x − 1/2, y + 1/2, z; (ii) 1 + x, y, z; (iii) x − 1/2, y − 1/2, z; (iv) 1/2 + x, 1/2 + y, z; (v) 1/2 + x, y − 1/2, z.]
	Fig. 4. The cell of (I) viewed along a, showing the ABAB layer sequence. Intermolecular interactions at the layer interface as described in the text are represented by dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids and the H atoms involved in the C—H···O contacts are drawn as small spheres of arbitrary radii. Selected atoms are labelled. [Symmetry codes: (i) x, 2 − y, 1/2 + z; (ii) x, y, 1 + z; (iii) 1/2 + x, y − 1/2, z; (iv) 1/2 + x, 3/2 − y, 1/2 + z; (v) 1/2 + x, y − 1/2, 1 + z; (vi) x, y − 1,z; (vii) x, 1 − y, 1/2 + z; (viii) x, y − 1, 1 + z.]
	Fig. 5. Part of a layer of molecules of (II) parallel to (001). Non-H atoms are shown as 50% probability displacement ellipsoids and H-atoms involved in C—H···O contacts (dashed lines) are drawn as small spheres of arbitrary radii. Selected atoms are labelled. [Symmetry codes: (i) 1 + x, y, z; (ii) x, 1 + y, z; (iii) 1 + x, 1 + y, z.]
	Fig. 6. The cell of (II) viewed along a. Intermolecular interactions, one within the layers and the others at the layer interfaces, are represented by dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids and the H-atoms involved in the C—H···O contacts are drawn as small spheres of arbitrary radii. Selected atoms are labelled. [Symmetry codes: (i) 1 + x, y, z; (ii) x, 1 + y, z; (iii) −x, 1 − y, −z; (iv) 1 − x, −y, 1 − z; (v) −x, 1 − y, 1 − z; (vi) 1 − x, 1 − y, 1 − z; (vii) 1 + x, y, 1 + z.]

(I) 4-Nitrophenyl 3-nitrobenzenesulfonate

Crystal data

C12H8N2O7S	F(000) = 664
Mr = 324.26	Dx = 1.653 Mg m^−3
Monoclinic, Cc	Melting point = 417–420 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 7.891 (2) Å	Cell parameters from 1812 reflections
b = 8.798 (3) Å	θ = 3.5–26.2°
c = 18.829 (6) Å	µ = 0.29 mm^−1
β = 94.597 (5)°	T = 100 K
V = 1303.1 (7) Å^3	Block, colourless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2534 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
Graphite monochromator	θmax = 28.3°, θmin = 2.2°
ϕ and ω scans	h = −10→10
5467 measured reflections	k = −11→11
2971 independent reflections	l = −24→24

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)] = 0.061	Only H-atom displacement parameters refined
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0665P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2971 reflections	Δρmax = 0.57 e Å^−3
200 parameters	Δρmin = −0.30 e Å^−3
2 restraints	Absolute structure: (Flack, 1983; 1406 Friedel pairs)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (12)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
S	0.48248 (11)	0.69028 (11)	0.05119 (6)	0.0204 (2)
O1	0.1619 (4)	0.2721 (4)	−0.10566 (19)	0.0387 (9)
O2	−0.0332 (4)	0.3823 (5)	−0.17421 (18)	0.0462 (10)
O3	0.6046 (4)	0.5731 (3)	0.04517 (15)	0.0259 (7)
O4	0.5334 (4)	0.8459 (3)	0.05728 (17)	0.0278 (7)
O5	0.3919 (4)	0.6435 (3)	0.11973 (15)	0.0253 (7)
O6	−0.2877 (4)	0.8716 (4)	0.22788 (17)	0.0325 (8)
O7	−0.1189 (4)	1.0368 (4)	0.27959 (16)	0.0284 (7)
N1	0.0856 (5)	0.3840 (5)	−0.1285 (2)	0.0339 (10)
N2	−0.1471 (4)	0.9275 (4)	0.23988 (17)	0.0244 (8)
C1	0.3209 (5)	0.6774 (5)	−0.0173 (2)	0.0225 (8)
C2	0.2704 (5)	0.5354 (5)	−0.0442 (2)	0.0240 (9)
H2	0.3228	0.4446	−0.0261	0.024 (4)*
C3	0.1418 (5)	0.5321 (6)	−0.0977 (2)	0.0282 (10)
C4	0.0605 (6)	0.6618 (6)	−0.1242 (2)	0.0337 (11)
H4	−0.0294	0.6553	−0.1609	0.024 (4)*
C5	0.1120 (6)	0.7999 (6)	−0.0967 (3)	0.0350 (12)
H5	0.0580	0.8901	−0.1146	0.024 (4)*
C6	0.2412 (6)	0.8093 (6)	−0.0432 (3)	0.0319 (11)
H6	0.2758	0.9054	−0.0242	0.024 (4)*
C7	0.2556 (5)	0.7286 (5)	0.1444 (2)	0.0217 (9)
C8	0.2912 (5)	0.8498 (5)	0.1893 (2)	0.0213 (9)
H8	0.4044	0.8854	0.1987	0.024 (4)*
C9	0.1577 (5)	0.9186 (5)	0.2204 (2)	0.0218 (8)
H9	0.1769	1.0027	0.2517	0.024 (4)*
C10	−0.0041 (5)	0.8616 (5)	0.2047 (2)	0.0201 (8)
C11	−0.0397 (6)	0.7433 (5)	0.1577 (2)	0.0242 (9)
H11	−0.1532	0.7096	0.1469	0.024 (4)*
C12	0.0942 (6)	0.6749 (5)	0.1268 (2)	0.0255 (9)
H12	0.0750	0.5930	0.0943	0.024 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0205 (5)	0.0153 (4)	0.0255 (5)	0.0027 (4)	0.0015 (4)	−0.0050 (5)
O1	0.033 (2)	0.039 (2)	0.045 (2)	−0.0128 (17)	0.0095 (16)	−0.0165 (17)
O2	0.0275 (19)	0.073 (3)	0.038 (2)	−0.0119 (19)	0.0017 (16)	−0.0228 (18)
O3	0.0207 (15)	0.0230 (16)	0.0337 (17)	0.0071 (13)	−0.0002 (13)	−0.0085 (13)
O4	0.0281 (16)	0.0170 (15)	0.0389 (18)	−0.0025 (11)	0.0052 (14)	−0.0074 (13)
O5	0.0282 (16)	0.0234 (15)	0.0240 (15)	0.0091 (13)	0.0004 (12)	−0.0015 (12)
O6	0.0165 (16)	0.0406 (19)	0.0404 (18)	−0.0013 (14)	0.0020 (13)	−0.0013 (15)
O7	0.0262 (16)	0.0298 (17)	0.0297 (16)	0.0031 (14)	0.0048 (13)	−0.0022 (13)
N1	0.028 (2)	0.042 (3)	0.033 (2)	−0.007 (2)	0.0090 (19)	−0.013 (2)
N2	0.023 (2)	0.0242 (19)	0.026 (2)	0.0049 (16)	0.0029 (15)	0.0032 (16)
C1	0.020 (2)	0.021 (2)	0.027 (2)	0.0035 (17)	0.0028 (15)	−0.0028 (17)
C2	0.023 (2)	0.024 (2)	0.026 (2)	0.0024 (18)	0.0050 (16)	−0.0015 (17)
C3	0.019 (2)	0.037 (3)	0.030 (2)	−0.0015 (19)	0.0088 (18)	−0.009 (2)
C4	0.025 (2)	0.053 (3)	0.024 (2)	0.009 (2)	0.0016 (17)	−0.007 (2)
C5	0.033 (3)	0.044 (3)	0.028 (2)	0.017 (2)	0.001 (2)	0.002 (2)
C6	0.036 (3)	0.029 (2)	0.032 (2)	0.008 (2)	0.009 (2)	−0.001 (2)
C7	0.020 (2)	0.016 (2)	0.028 (2)	0.0043 (16)	−0.0015 (17)	0.0020 (16)
C8	0.022 (2)	0.0138 (19)	0.027 (2)	0.0018 (17)	−0.0030 (17)	0.0035 (17)
C9	0.021 (2)	0.022 (2)	0.0212 (19)	−0.0016 (17)	−0.0039 (15)	−0.0034 (17)
C10	0.023 (2)	0.018 (2)	0.0201 (19)	0.0068 (16)	0.0034 (15)	0.0049 (15)
C11	0.021 (2)	0.018 (2)	0.034 (2)	−0.0080 (17)	0.0020 (17)	0.0006 (17)
C12	0.031 (2)	0.015 (2)	0.030 (2)	0.0003 (19)	−0.0003 (18)	−0.0012 (17)

Geometric parameters (Å, º)

S—O3	1.422 (3)	C4—C5	1.370 (8)
S—O4	1.429 (3)	C4—H4	0.9500
S—O5	1.579 (3)	C5—C6	1.376 (7)
S—C1	1.743 (5)	C5—H5	0.9500
O1—N1	1.215 (6)	C6—H6	0.9500
O2—N1	1.221 (5)	C7—C12	1.374 (6)
O5—C7	1.419 (5)	C7—C8	1.376 (6)
O6—N2	1.218 (5)	C8—C9	1.385 (6)
O7—N2	1.227 (5)	C8—H8	0.9500
N1—C3	1.479 (6)	C9—C10	1.382 (6)
N2—C10	1.473 (5)	C9—H9	0.9500
C1—C6	1.390 (6)	C10—C11	1.380 (6)
C1—C2	1.394 (6)	C11—C12	1.384 (6)
C2—C3	1.372 (6)	C11—H11	0.9500
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.383 (7)
O3—S—O4	120.86 (18)	C4—C5—C6	120.7 (5)
O3—S—O5	103.33 (17)	C4—C5—H5	119.7
O4—S—O5	109.07 (17)	C6—C5—H5	119.7
O3—S—C1	110.76 (19)	C5—C6—C1	119.7 (5)
O4—S—C1	107.8 (2)	C5—C6—H6	120.2
O5—S—C1	103.60 (18)	C1—C6—H6	120.2
C7—O5—S	122.3 (3)	C12—C7—C8	123.6 (4)
O1—N1—O2	124.8 (4)	C12—C7—O5	116.9 (4)
O1—N1—C3	116.8 (4)	C8—C7—O5	119.2 (4)
O2—N1—C3	118.4 (5)	C7—C8—C9	118.3 (4)
O6—N2—O7	123.2 (4)	C7—C8—H8	120.8
O6—N2—C10	118.5 (4)	C9—C8—H8	120.8
O7—N2—C10	118.3 (3)	C10—C9—C8	118.1 (4)
C6—C1—C2	120.8 (4)	C10—C9—H9	120.9
C6—C1—S	119.3 (4)	C8—C9—H9	120.9
C2—C1—S	119.9 (3)	C11—C10—C9	123.2 (4)
C3—C2—C1	117.3 (4)	C11—C10—N2	117.5 (4)
C3—C2—H2	121.3	C9—C10—N2	119.3 (4)
C1—C2—H2	121.3	C10—C11—C12	118.3 (4)
C2—C3—C4	122.8 (4)	C10—C11—H11	120.8
C2—C3—N1	119.2 (4)	C12—C11—H11	120.8
C4—C3—N1	118.0 (4)	C7—C12—C11	118.3 (4)
C5—C4—C3	118.7 (4)	C7—C12—H12	120.9
C5—C4—H4	120.7	C11—C12—H12	120.9
C3—C4—H4	120.7
O3—S—O5—C7	−178.2 (3)	C4—C5—C6—C1	0.4 (7)
O4—S—O5—C7	52.1 (3)	C2—C1—C6—C5	−0.7 (7)
C1—S—O5—C7	−62.6 (3)	S—C1—C6—C5	−179.2 (4)
O3—S—C1—C6	−148.4 (3)	S—O5—C7—C12	99.3 (4)
O4—S—C1—C6	−14.1 (4)	S—O5—C7—C8	−86.6 (4)
O5—S—C1—C6	101.4 (4)	C12—C7—C8—C9	2.2 (6)
O3—S—C1—C2	33.1 (4)	O5—C7—C8—C9	−171.4 (3)
O4—S—C1—C2	167.4 (3)	C7—C8—C9—C10	0.0 (6)
O5—S—C1—C2	−77.1 (4)	C8—C9—C10—C11	−2.4 (6)
C6—C1—C2—C3	1.1 (6)	C8—C9—C10—N2	176.9 (4)
S—C1—C2—C3	179.6 (3)	O6—N2—C10—C11	2.5 (5)
C1—C2—C3—C4	−1.3 (6)	O7—N2—C10—C11	−177.1 (4)
C1—C2—C3—N1	179.2 (4)	O6—N2—C10—C9	−176.8 (4)
O1—N1—C3—C2	−2.3 (6)	O7—N2—C10—C9	3.6 (5)
O2—N1—C3—C2	177.2 (4)	C9—C10—C11—C12	2.4 (6)
O1—N1—C3—C4	178.2 (4)	N2—C10—C11—C12	−176.9 (4)
O2—N1—C3—C4	−2.3 (5)	C8—C7—C12—C11	−2.2 (7)
C2—C3—C4—C5	1.0 (6)	O5—C7—C12—C11	171.6 (4)
N1—C3—C4—C5	−179.5 (4)	C10—C11—C12—C7	−0.1 (6)
C3—C4—C5—C6	−0.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3^i	0.95	2.45	3.100 (5)	126
C12—H12···O4^ii	0.95	2.30	3.197 (5)	158
C8—H8···O6^iii	0.95	2.45	3.350 (5)	158
C5—H5···O7^iv	0.95	2.43	3.184 (6)	136

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

(II) 4-Chlorophenyl 3-nitrobenzenesulfonate

Crystal data

C12H8ClNO5S	Z = 2
Mr = 313.70	F(000) = 320
Triclinic, P1	Dx = 1.605 Mg m^−3
Hall symbol: -P 1	Melting point = 381–383 K
a = 7.556 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.562 (8) Å	Cell parameters from 3154 reflections
c = 10.851 (13) Å	θ = 2.6–28.2°
α = 67.86 (6)°	µ = 0.47 mm^−1
β = 89.93 (11)°	T = 100 K
γ = 87.01 (8)°	Block, colourless
V = 649.2 (13) Å^3	0.46 × 0.13 × 0.12 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	1713 independent reflections
Radiation source: fine-focus sealed tube	1261 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ϕ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −3→9
Tmin = 0.812, Tmax = 0.945	k = −10→9
5715 measured reflections	l = −14→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.183	Only H-atom displacement parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1188P)^2] where P = (Fo^2 + 2Fc^2)/3
1713 reflections	(Δ/σ)max < 0.001
182 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Experimental. The Tmin and Tmax values obtained from the SIZE instruction are listed above. The absorption correction was applied using SADABS and it gives 0.839 ratio of min/max transmission.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
S	0.29260 (15)	0.22971 (17)	0.34181 (13)	0.0153 (4)
Cl	−0.44453 (16)	0.2403 (2)	−0.03417 (14)	0.0332 (5)
N1	0.7084 (6)	−0.2434 (6)	0.3013 (5)	0.0220 (12)
O1	0.8112 (5)	−0.1331 (5)	0.2445 (4)	0.0321 (12)
O2	0.7443 (5)	−0.3948 (5)	0.3334 (5)	0.0344 (12)
O3	0.4564 (4)	0.2989 (5)	0.3550 (4)	0.0212 (10)
O4	0.1500 (4)	0.2328 (5)	0.4270 (4)	0.0196 (9)
O5	0.2338 (4)	0.3321 (4)	0.1909 (3)	0.0166 (9)
C1	0.3331 (6)	0.0219 (7)	0.3509 (5)	0.0127 (12)
C2	0.4995 (6)	−0.0244 (7)	0.3205 (5)	0.0145 (13)
H2	0.5899	0.0540	0.2936	0.014 (5)*
C3	0.5301 (6)	−0.1895 (7)	0.3305 (5)	0.0176 (14)
C4	0.4004 (6)	−0.3059 (7)	0.3674 (5)	0.0198 (14)
H4	0.4254	−0.4185	0.3736	0.014 (5)*
C5	0.2328 (7)	−0.2548 (7)	0.3952 (6)	0.0245 (15)
H5	0.1414	−0.3323	0.4196	0.014 (5)*
C6	0.1992 (6)	−0.0919 (7)	0.3875 (5)	0.0176 (14)
H6	0.0848	−0.0570	0.4070	0.014 (5)*
C7	0.0680 (6)	0.3043 (6)	0.1414 (5)	0.0146 (13)
C8	−0.0867 (6)	0.3675 (7)	0.1778 (5)	0.0175 (13)
H8	−0.0840	0.4222	0.2394	0.014 (5)*
C9	−0.2479 (6)	0.3490 (7)	0.1219 (6)	0.0212 (14)
H9	−0.3573	0.3907	0.1441	0.014 (5)*
C10	−0.2411 (6)	0.2673 (7)	0.0326 (5)	0.0188 (14)
C11	−0.0861 (6)	0.2077 (7)	−0.0052 (6)	0.0203 (14)
H11	−0.0873	0.1555	−0.0685	0.014 (5)*
C12	0.0736 (6)	0.2260 (7)	0.0525 (5)	0.0186 (14)
H12	0.1833	0.1850	0.0301	0.014 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0207 (6)	0.0133 (8)	0.0136 (8)	−0.0035 (4)	0.0015 (5)	−0.0068 (7)
Cl	0.0240 (7)	0.0527 (12)	0.0270 (9)	−0.0115 (6)	0.0004 (6)	−0.0186 (9)
N1	0.030 (2)	0.020 (3)	0.018 (3)	0.0007 (18)	0.000 (2)	−0.008 (3)
O1	0.037 (2)	0.021 (3)	0.035 (3)	−0.0033 (16)	0.0091 (19)	−0.006 (2)
O2	0.044 (2)	0.017 (3)	0.047 (3)	0.0056 (17)	0.005 (2)	−0.018 (3)
O3	0.0276 (18)	0.017 (2)	0.023 (2)	−0.0047 (14)	−0.0034 (16)	−0.011 (2)
O4	0.0310 (18)	0.016 (2)	0.015 (2)	−0.0008 (14)	0.0041 (16)	−0.010 (2)
O5	0.0201 (16)	0.016 (2)	0.014 (2)	−0.0008 (13)	−0.0004 (15)	−0.005 (2)
C1	0.022 (2)	0.009 (3)	0.009 (3)	−0.0013 (17)	−0.003 (2)	−0.005 (3)
C2	0.020 (2)	0.017 (3)	0.008 (3)	−0.0029 (18)	0.002 (2)	−0.006 (3)
C3	0.024 (2)	0.018 (3)	0.010 (3)	0.0004 (19)	−0.001 (2)	−0.004 (3)
C4	0.032 (3)	0.012 (3)	0.016 (3)	0.0006 (19)	−0.006 (2)	−0.005 (3)
C5	0.029 (3)	0.020 (4)	0.023 (3)	−0.012 (2)	0.000 (2)	−0.005 (3)
C6	0.019 (2)	0.015 (3)	0.015 (3)	−0.0016 (18)	0.002 (2)	−0.001 (3)
C7	0.019 (2)	0.009 (3)	0.016 (3)	−0.0009 (17)	0.000 (2)	−0.005 (3)
C8	0.029 (3)	0.013 (3)	0.014 (3)	−0.0023 (19)	0.002 (2)	−0.008 (3)
C9	0.023 (2)	0.016 (3)	0.024 (3)	−0.0045 (19)	0.007 (2)	−0.007 (3)
C10	0.024 (2)	0.016 (3)	0.015 (3)	−0.0064 (19)	0.002 (2)	−0.003 (3)
C11	0.027 (3)	0.021 (3)	0.017 (3)	−0.003 (2)	−0.002 (2)	−0.010 (3)
C12	0.023 (2)	0.015 (3)	0.018 (3)	−0.0042 (19)	0.009 (2)	−0.007 (3)

Geometric parameters (Å, º)

S—O4	1.424 (4)	C4—H4	0.9500
S—O3	1.430 (4)	C5—C6	1.375 (8)
S—O5	1.589 (4)	C5—H5	0.9500
S—C1	1.756 (6)	C6—H6	0.9500
Cl—C10	1.763 (6)	C7—C12	1.366 (8)
N1—O2	1.224 (6)	C7—C8	1.382 (7)
N1—O1	1.230 (5)	C12—C11	1.403 (7)
N1—C3	1.474 (7)	C12—H12	0.9500
O5—C7	1.430 (6)	C11—C10	1.377 (8)
C1—C2	1.375 (7)	C11—H11	0.9500
C1—C6	1.393 (6)	C10—C9	1.392 (9)
C2—C3	1.383 (8)	C9—C8	1.404 (7)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.384 (7)	C8—H8	0.9500
C4—C5	1.388 (8)
O4—S—O3	119.7 (3)	C6—C5—H5	120.0
O4—S—O5	109.9 (2)	C4—C5—H5	120.0
O3—S—O5	103.8 (2)	C5—C6—C1	120.0 (5)
O4—S—C1	108.8 (2)	C5—C6—H6	120.0
O3—S—C1	109.6 (2)	C1—C6—H6	120.0
O5—S—C1	103.9 (2)	C12—C7—C8	123.7 (5)
O2—N1—O1	124.1 (5)	C12—C7—O5	117.2 (4)
O2—N1—C3	118.1 (4)	C8—C7—O5	119.0 (5)
O1—N1—C3	117.8 (5)	C7—C12—C11	118.6 (5)
C7—O5—S	120.3 (3)	C7—C12—H12	120.7
C2—C1—C6	121.4 (5)	C11—C12—H12	120.7
C2—C1—S	118.2 (4)	C10—C11—C12	118.1 (6)
C6—C1—S	120.4 (4)	C10—C11—H11	120.9
C1—C2—C3	117.5 (4)	C12—C11—H11	121.0
C1—C2—H2	121.3	C11—C10—C9	123.7 (5)
C3—C2—H2	121.3	C11—C10—Cl	119.2 (5)
C2—C3—C4	122.6 (5)	C9—C10—Cl	117.1 (4)
C2—C3—N1	118.6 (4)	C10—C9—C8	117.4 (5)
C4—C3—N1	118.8 (5)	C10—C9—H9	121.3
C3—C4—C5	118.7 (6)	C8—C9—H9	121.3
C3—C4—H4	120.7	C7—C8—C9	118.5 (5)
C5—C4—H4	120.7	C7—C8—H8	120.7
C6—C5—C4	120.0 (5)	C9—C8—H8	120.7
O4—S—O5—C7	−47.3 (4)	N1—C3—C4—C5	179.8 (5)
O3—S—O5—C7	−176.5 (4)	C3—C4—C5—C6	−0.8 (8)
C1—S—O5—C7	68.9 (4)	C4—C5—C6—C1	0.4 (8)
O4—S—C1—C2	−155.5 (4)	C2—C1—C6—C5	0.8 (8)
O3—S—C1—C2	−23.0 (5)	S—C1—C6—C5	−179.5 (4)
O5—S—C1—C2	87.5 (4)	S—O5—C7—C12	−110.6 (5)
O4—S—C1—C6	24.7 (5)	S—O5—C7—C8	74.0 (5)
O3—S—C1—C6	157.2 (4)	C8—C7—C12—C11	−0.3 (7)
O5—S—C1—C6	−92.3 (4)	O5—C7—C12—C11	−175.5 (4)
C6—C1—C2—C3	−1.4 (8)	C7—C12—C11—C10	−1.0 (7)
S—C1—C2—C3	178.8 (4)	C12—C11—C10—C9	1.9 (8)
C1—C2—C3—C4	1.0 (8)	C12—C11—C10—Cl	−178.1 (4)
C1—C2—C3—N1	−178.7 (5)	C11—C10—C9—C8	−1.4 (8)
O2—N1—C3—C2	166.9 (5)	Cl—C10—C9—C8	178.6 (4)
O1—N1—C3—C2	−14.1 (8)	C12—C7—C8—C9	0.8 (7)
O2—N1—C3—C4	−12.9 (8)	O5—C7—C8—C9	175.9 (4)
O1—N1—C3—C4	166.2 (5)	C10—C9—C8—C7	0.1 (7)
C2—C3—C4—C5	0.1 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3^i	0.95	2.50	3.441 (8)	170
C8—H8···O2^ii	0.95	2.48	3.307 (8)	145
C9—H9···O3^iii	0.95	2.57	3.293 (8)	133
C6—H6···O4^iv	0.95	2.62	3.311 (7)	129

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