2-[N-(X-Chloro­phen­yl)carbamoyl]­benzene­sulfonamide (with X = 2 and 4)

The structures of 2-[N-(2-chloro­phenyl)­carbamoyl]­benzene­sulfon­amide and 2-[N-(4-chloro­phenyl)­carbamoyl]­benzene­sulfon­amide, both C₁₃H₁₁ClN₂O₃S, are stabilized by extensive intra- and inter­molecular hydrogen bonds. In both structures, sulfon­amide groups are hydrogen bonded via the N and O atoms and form chains of mol­ecules. The carbamoyl groups are also hydrogen bonded, involving the O and N atoms, further strengthening the polymeric chains running along the c and a axes in the 2- and 4-chloro derivatives, respectively. Carbamoylsulfonamide derivatives are novel compounds with a great potential for medicinal applications.

S1. Comment

Benzenesulfonamide derivatives are well known in the biological sciences for their antibacterial, anticancer and anti-HIV activities (Brzozowski, 1996; Stawinski, 1997; Alovero et al., 2001). In the field of catalysis, their chloro-derivatives are particularly important for carrying out a huge number of oxidation reactions wherein the reaction kinetics are very important (Shashikala & Rangappa, 2002; Puttaswamy et al., 2001). The crystal structures of a number of interesting derivatives of benzenesulfonamide have been reported recently (Clark et al., 2003; Vyas et al., 2003; Singh et al., 2004; Bocelli et al., 1995; Sutton & Cody, 1989; Furuya et al., 1989). While continuing our research on the synthesis of biologically important 1,2-benzothiazine derivatives (Siddiqui et al., 2007, 2008), we have devised a simple and straightforward route for the synthesis of o-[(chlorophenyl)carbamoyl] benzene sulfonamide derivatives directly from saccharin as starting material. The syntheses of only two unsubstituted o-cyclohexyl and o-phenylcarbamoylbenzene sulfonamide derivatives have been reported to date, utilizing N-vinylsulfobenzimide as starting material (Kiyoshi, 1959). Here, we report the syntheses and crystal structures of two new benzenesulfonamides, the 2-chloro- and 4-chlorophenyl derivatives of the title compound, (I) and (II), respectively.

The molecular structure of (I) is presented in Fig. 1. The mean planes of the C1–C6 and C8–C13 phenyl rings are inclined at 48.83 (8)° with respect to each other, while the carbamoyl group, O1/N2/C7, is inclined at 70.51 (13) and 29.6 (2)°, respectively, with these phenyl rings. The structure contains two distinct patterns of hydrogen bonds involving N—H···O-type intermolecular interactions (Fig. 2). The sulfonamide groups are hydrogen bonded via atoms N1 and O3, forming chains of molecules. The carbamoyl groups are also hydrogen bonded, involving atoms O1 and N2, thus resulting in two parallel hydrogen-bonding patterns and affording stability to the polymeric chains running parallel to the c axis. There are two non-classical intermolecular C—H···O hydrogen bonds and the structure is further stabilized by four additional intramolecular interactions, N1—H1NA···O1, C13—H13···O1, C2—H2···O3 and N2—H2N···Cl1, resulting in seven-, six-, five- and five-membered rings, representing S(7), S(6), S(5) and S(5) motifs, respectively (Bernstein et al., 1994); details of the hydrogen-bonding geometry are given in Table 1.

The molecular structure of (II) is presented in Fig. 3. The mean planes of the C1–C6 and C8–C13 phenyl rings are inclined at 42.92 (6)° with respect to each other, while the carbamoyl group, O1/N2/C7, is inclined at 57.10 (11) and 17.96 (18)°, respectively, with these phenyl rings. The structure of (II) also contains two patterns of hydrogen bonds (Fig. 4), similar to those observed in (I). The sulfonamide groups in (II) are hydrogen bonded via atoms N1 and O3, forming chains of molecules. The carbamoyl groups are also hydrogen bonded, involving atoms O1 and N2, thus resulting in two parallel hydrogen-bonding patterns and affording stability to the polymeric chains running parallel to the a axis. There are two non-classical C—H···O hydrogen bonds and the structure is further stabilized by three additional intramolecular interactions, N1—H1NA···O1, C13—H13···O1 and C2—H2···O3, resulting in seven-, six- and five-membered rings, representing S(7), S(6) and S(5) motifs, respectively; details of the hydrogen-bonding geometry are given in Table 2.

In both molecules, the conformation about the S—N bond is in agreement with the conformation of a handful of structures containing an o-C-substituted benzenesulfonamide fragment; there were 14 hits in the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002). The N1 atoms in both structures are tetrahedral, with angles at N1 in the ranges 105 (3)–120 (3)° (sum 338°) and 112 (2)–116 (3)° (sum 342°) for (I) and (II), respectively. The H atoms bonded to atom N1 and atoms O2 and O3 bonded to atom S1 are staggered, as observed in the compound with CSD refcode COYVER (Foresti et al., 1985). Several structures have been reported wherein the H and O atoms of the sulfonamide unit are eclipsed, e.g. refcodes ENIROI (Vyas et al., 2003), GUFQED01 (Clark et al., 2005) and ZZZULS01 (Tremayne et al., 2002). In a toluene sulfonamide (Helliwell et al., 1997), the C-substitents on N atom and the O atoms of the sulfonamide unit are also eclipsed. The N1—S1—C1—C6 torsion angles in (I) and (II) are -71.6 (3) and -76.1 (2)°, respectively. The corresponding angles in the structures quoted above vary between -18.95 (ZZZULS01) and -87.85° (ENIROI), depending on the substituents present on the benzene ring as well as on the inter- and intramolecular interactions between the substituents.

The molecular dimensions in the two structures are in agreement with the corresponding dimensions reported for similar structures quoted above (Clark et al., 2003; Vyas et al., 2003; Singh et al., 2004; Bocelli et al., 1995; Sutton & Cody, 1989; Furuya et al., 1989), with an average S═O distance of 1.435 (5) Å and S—N, S—C and Cl—C distances of 1.613 (3), 1.774 (3) and 1.734 (3) Å, respectively, in (I), and an average S═O distance of 1.433 (4) Å and S—N, S—C and Cl—C distances of 1.609 (2), 1.778 (2) and 1.739 (3) Å, respectively, in (II). The only minor difference in the bond lengths is observed for the N2—C7 bond [1.357 (4) and 1.340 (3) Å, in (I) and (II), respectively]. The bond angles at atoms N2 and C8 also reflect a slight influence of atom Cl1, which is bonded to atoms C9 and C11 in (I) and (II), respectively. Thus, the C7—N2—C8 bond angles are 126.0 (3) and 128.8 (2)° in (I) and (II), respectively, while the N2—C8—C9 and N2—C8—C13 bond angles have values of 119.1 (3) and 122.6 (3)° in (I), and 116.4 (2) and 123.8 (2)° in (II), respectively.

S2. Experimental

A suspension of saccharin (1.0 g, 5.46 mmol,) and o- or p-chloroaniline (5 ml, in excess) was stirred first at room temperature (1.5 h) and then at high temperature (373 K, 2–4 h). The resulting light-brown solution was cooled to room temperature, diluted in chloroform, and washed with dilute hydrochloric acid (2M, 2 × 20 ml) and water. The organic layer was dried over magnesium sulfate and then evaporated at reduced pressure (11 Torr; 1 Torr = 133.322 Pa) to obtain light-pink and colourless solid products, (I) and (II), respectively. The products were crystallized from MeOH–CHCl₃ (1:4 v/v) solutions by slow evaporation at 313 K.

Analysis for (I): IR (neat, ν_max, cm^-1): NH and NH₂ 3306 (br), CO 1662 (m), SO₂ 1342 and 1165 (s); ¹H NMR (300 MHz, acetone-d₆, δ, p.p.m.): 6.62 (s, 2H, NH₂), 7.30 (ddd, 1H, J = 1.46, 7.68 and 9.14 Hz, H4'), 7.34 (m, 1H, H5'), 7.46 (dd, 1H, J = 1.47 and 8.05 Hz, H3'), 7.73–7.83 (m, 2H, H6' and H4), 7.93 (d, 1H, J = 7.1 Hz, H5), 8.09 (dd, 2H, J = 1.46 and 7.32 Hz, H3 and H6), 9.51 (s, 1H, NH); ¹³C NMR (Frequency?, Medium?, δ, p.p.m.): 206.2, 133.2, 131.6, 131.5, 130.4, 129.7, 128.5, 128.3, 127.8, 127.1; yield: 1.16 g, 3.77 mmol, 69%; m.p. 382–383 K.

Analysis for (II): IR (neat, ν_max, cm^-1): NH 3355 (m), NH₂ 3265, 3235 (m), CO 1636 (s), SO₂ 1349, 1157 (s); ¹H NMR (300 MHz, DMSO-d₆, δ, p.p.m.): 6.91–7.10 (4H, m, C₆H₄), 7.32–7.53 (4H, m, C₆H₄), 10.55 (1H, s, NH); ¹³C NMR (Frequency?, Medium?, δ, p.p.m.): 165.7, 140.1, 138.1, 133.8, 131.4, 129.9, 129.9, 129.2, 129.0, 128.6, 124.2, 121.0, 120.3; yield: 1.32 g, 4.26 mmol, 78%; m.p. 475–476 K.

S3. Refinement

For both structures, H atoms bonded to C atoms were included in the refinements at geometrically idealized positions, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C). H atoms bonded to N atoms were allowed to refine with U_iso(H) = 1.2U_eq(N). The final difference maps were free of chemically significant features. An absolute structure could not be established by the Flack method (Flack, 1983) as a twin refinement gave a 0.55 (8):0.45 (8) mixture. Friedel pairs were, therefore, merged.

Computing details

For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A drawing of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are represented by dashed lines.
	Fig. 2. Intramolecular interactions (dashed lines) in the unit cell of (I) involving sulfonamide and carbamoyl groups, resulting in two parallel hydrogen-bonding patterns, thus forming polymeric chains running parallel to the c axis.
	Fig. 3. A drawing of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are represented by dashed lines.
	Fig. 4. Intramolecular interactions (dashed lines) in the unit cell of (II) involving sulfonamide and carbamoyl groups, resulting in two parallel hydrogen-bonding patterns, thus forming polymeric chains running parallel to the a axis.

(I) 2-[N-(2-chlorophenyl)carbamoyl]benzenesulfonamide

Crystal data

C13H11ClN2O3S	F(000) = 640
Mr = 310.75	Dx = 1.602 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2709 reflections
a = 15.734 (9) Å	θ = 2.3–27.5°
b = 10.614 (6) Å	µ = 0.47 mm^−1
c = 7.717 (3) Å	T = 173 K
V = 1288.7 (12) Å^3	Prism, colourless
Z = 4	0.18 × 0.12 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer	1571 independent reflections
Radiation source: fine-focus sealed tube	1353 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω and ϕ scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −20→20
Tmin = 0.921, Tmax = 0.968	k = −13→13
2709 measured reflections	l = −9→9

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.25P] where P = (Fo^2 + 2Fc^2)/3
1571 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.25 e Å^−3
1 restraint	Δρmin = −0.33 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.08066 (5)	0.81417 (7)	0.19375 (18)	0.0309 (2)
S1	0.02254 (4)	0.18986 (6)	0.19342 (12)	0.02041 (18)
O1	0.06897 (13)	0.3891 (2)	−0.1186 (3)	0.0254 (5)
O2	0.08444 (13)	0.2757 (2)	0.2632 (3)	0.0266 (5)
O3	−0.00651 (16)	0.0865 (2)	0.2966 (3)	0.0321 (6)
N1	0.06339 (17)	0.1298 (3)	0.0204 (4)	0.0246 (6)
H1NA	0.077 (2)	0.190 (3)	−0.061 (5)	0.030*
H1NB	0.031 (2)	0.069 (4)	−0.006 (5)	0.030*
N2	0.06043 (17)	0.5470 (2)	0.0823 (4)	0.0212 (6)
H2N	0.032 (2)	0.578 (3)	0.152 (5)	0.025*
C1	−0.06698 (18)	0.2832 (3)	0.1383 (4)	0.0194 (6)
C2	−0.1471 (2)	0.2402 (3)	0.1813 (5)	0.0261 (6)
H2	−0.1535	0.1631	0.2423	0.031*
C3	−0.2185 (2)	0.3101 (3)	0.1352 (5)	0.0302 (8)
H3	−0.2737	0.2801	0.1630	0.036*
C4	−0.2088 (2)	0.4231 (3)	0.0488 (5)	0.0261 (7)
H4	−0.2576	0.4701	0.0159	0.031*
C5	−0.12811 (19)	0.4688 (3)	0.0096 (5)	0.0251 (7)
H5	−0.1222	0.5476	−0.0476	0.030*
C6	−0.05605 (19)	0.4000 (3)	0.0533 (4)	0.0189 (6)
C7	0.03036 (18)	0.4440 (3)	−0.0020 (4)	0.0200 (6)
C8	0.1456 (2)	0.5914 (3)	0.0788 (4)	0.0208 (6)
C9	0.1629 (2)	0.7139 (3)	0.1360 (4)	0.0237 (7)
C10	0.2461 (2)	0.7571 (3)	0.1498 (5)	0.0301 (7)
H10	0.2570	0.8393	0.1935	0.036*
C11	0.3123 (2)	0.6815 (4)	0.1006 (5)	0.0334 (8)
H11	0.3691	0.7111	0.1092	0.040*
C12	0.2962 (2)	0.5612 (3)	0.0379 (5)	0.0302 (8)
H12	0.3420	0.5097	0.0004	0.036*
C13	0.21369 (19)	0.5157 (3)	0.0297 (5)	0.0274 (7)
H13	0.2036	0.4322	−0.0097	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0413 (4)	0.0190 (3)	0.0323 (4)	0.0002 (3)	0.0054 (4)	−0.0025 (4)
S1	0.0229 (4)	0.0181 (3)	0.0202 (3)	0.0010 (3)	0.0000 (3)	0.0007 (3)
O1	0.0300 (12)	0.0229 (11)	0.0234 (11)	−0.0029 (9)	0.0067 (9)	−0.0049 (9)
O2	0.0253 (11)	0.0250 (11)	0.0296 (11)	0.0013 (10)	−0.0077 (9)	−0.0052 (10)
O3	0.0400 (14)	0.0238 (11)	0.0324 (13)	0.0037 (11)	0.0048 (11)	0.0079 (11)
N1	0.0262 (14)	0.0218 (14)	0.0259 (14)	−0.0004 (12)	0.0007 (12)	−0.0051 (12)
N2	0.0258 (14)	0.0169 (13)	0.0209 (13)	−0.0005 (11)	0.0042 (10)	−0.0014 (11)
C1	0.0229 (15)	0.0159 (14)	0.0195 (13)	−0.0007 (12)	−0.0006 (12)	−0.0038 (11)
C2	0.0272 (15)	0.0224 (14)	0.0287 (16)	−0.0060 (13)	0.0037 (14)	0.0000 (16)
C3	0.0206 (15)	0.034 (2)	0.0362 (19)	−0.0066 (15)	0.0027 (14)	−0.0093 (15)
C4	0.0225 (16)	0.0239 (16)	0.0318 (17)	0.0047 (13)	−0.0033 (13)	−0.0047 (13)
C5	0.0275 (16)	0.0231 (16)	0.0246 (15)	0.0048 (13)	−0.0026 (13)	−0.0025 (13)
C6	0.0243 (16)	0.0164 (14)	0.0159 (14)	−0.0021 (12)	−0.0002 (12)	−0.0024 (11)
C7	0.0229 (15)	0.0151 (14)	0.0221 (14)	0.0020 (12)	−0.0026 (13)	0.0026 (12)
C8	0.0250 (16)	0.0191 (15)	0.0184 (14)	−0.0034 (13)	0.0002 (12)	0.0010 (12)
C9	0.0297 (17)	0.0215 (15)	0.0198 (14)	−0.0041 (13)	0.0019 (13)	0.0016 (12)
C10	0.0388 (18)	0.0242 (16)	0.0272 (17)	−0.0125 (15)	−0.0015 (14)	0.0031 (13)
C11	0.0315 (19)	0.041 (2)	0.0273 (18)	−0.0127 (16)	−0.0028 (15)	0.0058 (15)
C12	0.0236 (16)	0.0338 (18)	0.0332 (19)	0.0010 (15)	0.0028 (14)	0.0049 (15)
C13	0.0279 (16)	0.0215 (16)	0.0327 (18)	−0.0012 (14)	0.0018 (13)	0.0045 (13)

Geometric parameters (Å, º)

Cl1—C9	1.734 (3)	C3—H3	0.9500
S1—O3	1.431 (3)	C4—C5	1.392 (5)
S1—O2	1.438 (2)	C4—H4	0.9500
S1—N1	1.613 (3)	C5—C6	1.390 (4)
S1—C1	1.774 (3)	C5—H5	0.9500
O1—C7	1.232 (4)	C6—C7	1.499 (4)
N1—H1NA	0.93 (4)	C8—C13	1.393 (5)
N1—H1NB	0.85 (4)	C8—C9	1.400 (4)
N2—C7	1.357 (4)	C9—C10	1.392 (5)
N2—C8	1.420 (4)	C10—C11	1.369 (5)
N2—H2N	0.77 (4)	C10—H10	0.9500
C1—C2	1.381 (4)	C11—C12	1.388 (5)
C1—C6	1.413 (4)	C11—H11	0.9500
C2—C3	1.392 (5)	C12—C13	1.387 (4)
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.381 (5)	C13—H13	0.9500
O3—S1—O2	119.58 (18)	C4—C5—H5	119.7
O3—S1—N1	106.54 (15)	C5—C6—C1	118.3 (3)
O2—S1—N1	106.90 (15)	C5—C6—C7	120.4 (3)
O3—S1—C1	107.95 (14)	C1—C6—C7	121.0 (3)
O2—S1—C1	105.88 (14)	O1—C7—N2	124.0 (3)
N1—S1—C1	109.80 (18)	O1—C7—C6	120.5 (3)
S1—N1—H1NA	113 (2)	N2—C7—C6	115.5 (3)
S1—N1—H1NB	105 (3)	C13—C8—C9	118.2 (3)
H1NA—N1—H1NB	120 (3)	C13—C8—N2	122.6 (3)
C7—N2—C8	126.0 (3)	C9—C8—N2	119.1 (3)
C7—N2—H2N	118 (3)	C10—C9—C8	120.9 (3)
C8—N2—H2N	115 (3)	C10—C9—Cl1	118.7 (3)
C2—C1—C6	120.8 (3)	C8—C9—Cl1	120.4 (3)
C2—C1—S1	118.9 (2)	C11—C10—C9	120.1 (3)
C6—C1—S1	120.3 (2)	C11—C10—H10	120.0
C1—C2—C3	119.9 (3)	C9—C10—H10	120.0
C1—C2—H2	120.0	C10—C11—C12	119.8 (3)
C3—C2—H2	120.0	C10—C11—H11	120.1
C4—C3—C2	119.8 (3)	C12—C11—H11	120.1
C4—C3—H3	120.1	C13—C12—C11	120.5 (3)
C2—C3—H3	120.1	C13—C12—H12	119.7
C3—C4—C5	120.5 (3)	C11—C12—H12	119.7
C3—C4—H4	119.7	C12—C13—C8	120.5 (3)
C5—C4—H4	119.7	C12—C13—H13	119.8
C6—C5—C4	120.5 (3)	C8—C13—H13	119.8
C6—C5—H5	119.7
O3—S1—C1—C2	−6.8 (3)	C8—N2—C7—C6	166.7 (3)
O2—S1—C1—C2	−135.9 (3)	C5—C6—C7—O1	−106.9 (3)
N1—S1—C1—C2	109.0 (3)	C1—C6—C7—O1	67.9 (4)
O3—S1—C1—C6	172.7 (2)	C5—C6—C7—N2	72.0 (4)
O2—S1—C1—C6	43.5 (3)	C1—C6—C7—N2	−113.2 (3)
N1—S1—C1—C6	−71.6 (3)	C7—N2—C8—C13	−19.2 (5)
C6—C1—C2—C3	2.3 (5)	C7—N2—C8—C9	164.5 (3)
S1—C1—C2—C3	−178.2 (3)	C13—C8—C9—C10	−2.5 (5)
C1—C2—C3—C4	−1.0 (5)	N2—C8—C9—C10	174.0 (3)
C2—C3—C4—C5	−0.9 (5)	C13—C8—C9—Cl1	178.4 (3)
C3—C4—C5—C6	1.4 (5)	N2—C8—C9—Cl1	−5.1 (4)
C4—C5—C6—C1	0.0 (4)	C8—C9—C10—C11	2.7 (5)
C4—C5—C6—C7	174.9 (3)	Cl1—C9—C10—C11	−178.2 (3)
C2—C1—C6—C5	−1.8 (4)	C9—C10—C11—C12	−0.4 (5)
S1—C1—C6—C5	178.7 (2)	C10—C11—C12—C13	−1.9 (5)
C2—C1—C6—C7	−176.7 (3)	C11—C12—C13—C8	2.1 (5)
S1—C1—C6—C7	3.8 (4)	C9—C8—C13—C12	0.1 (5)
C8—N2—C7—O1	−14.5 (5)	N2—C8—C13—C12	−176.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Cl1	0.77 (4)	2.64 (4)	2.981 (3)	109 (3)
N1—H1NA···O1	0.93 (4)	2.16 (4)	2.955 (4)	144 (3)
N1—H1NB···O3^i	0.85 (4)	2.28 (4)	3.009 (4)	144 (3)
N2—H2N···O1^ii	0.77 (4)	2.40 (4)	3.152 (4)	163 (3)
C2—H2···O3	0.95	2.49	2.890 (4)	106
C13—H13···O1	0.95	2.32	2.881 (4)	117
C3—H3···O2^iii	0.95	2.44	3.380 (4)	173
C5—H5···O2^iv	0.95	2.45	3.382 (4)	167

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

(II) 2-[N-(4-chlorophenyl)carbamoyl]benzenesulfonamide

Crystal data

C13H11ClN2O3S	F(000) = 1280
Mr = 310.75	Dx = 1.572 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9119 reflections
a = 7.435 (2) Å	θ = 3.8–27.5°
b = 16.006 (6) Å	µ = 0.46 mm^−1
c = 22.061 (7) Å	T = 173 K
V = 2625.4 (15) Å^3	Prism, colourless
Z = 8	0.12 × 0.07 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer	3005 independent reflections
Radiation source: fine-focus sealed tube	2019 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ω and ϕ scans	θmax = 27.5°, θmin = 3.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −9→9
Tmin = 0.947, Tmax = 0.973	k = −19→20
9119 measured reflections	l = −28→28

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 0.61P] where P = (Fo^2 + 2Fc^2)/3
3005 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.73145 (11)	−0.04552 (5)	−0.20202 (3)	0.0473 (2)
S1	0.83054 (8)	0.22246 (4)	0.16281 (3)	0.02399 (18)
O1	0.5441 (2)	0.17758 (10)	0.05808 (7)	0.0264 (4)
O2	0.9182 (2)	0.17305 (11)	0.11770 (7)	0.0297 (4)
O3	0.9267 (2)	0.24784 (12)	0.21619 (7)	0.0327 (4)
N1	0.6573 (3)	0.17113 (14)	0.18574 (11)	0.0282 (5)
H1NA	0.591 (4)	0.1568 (18)	0.1589 (13)	0.034*
H1NB	0.608 (4)	0.1932 (18)	0.2160 (13)	0.034*
N2	0.7105 (3)	0.22676 (14)	−0.02088 (9)	0.0244 (5)
H2N	0.766 (4)	0.2681 (19)	−0.0304 (12)	0.029*
C1	0.7545 (3)	0.31503 (15)	0.12634 (10)	0.0212 (5)
C2	0.7717 (3)	0.39029 (16)	0.15648 (11)	0.0274 (6)
H2	0.8238	0.3918	0.1958	0.033*
C3	0.7130 (3)	0.46374 (16)	0.12940 (12)	0.0314 (6)
H3	0.7208	0.5152	0.1507	0.038*
C4	0.6435 (3)	0.46189 (16)	0.07169 (11)	0.0301 (6)
H4	0.6044	0.5122	0.0531	0.036*
C5	0.6302 (3)	0.38739 (16)	0.04059 (11)	0.0270 (6)
H5	0.5855	0.3873	0.0003	0.032*
C6	0.6816 (3)	0.31231 (15)	0.06751 (10)	0.0219 (5)
C7	0.6418 (3)	0.23174 (15)	0.03514 (10)	0.0219 (5)
C8	0.7000 (3)	0.15984 (16)	−0.06288 (10)	0.0237 (5)
C9	0.7565 (3)	0.17711 (17)	−0.12205 (10)	0.0284 (6)
H9	0.7881	0.2326	−0.1330	0.034*
C10	0.7668 (3)	0.11454 (18)	−0.16439 (11)	0.0326 (6)
H10	0.8072	0.1263	−0.2043	0.039*
C11	0.7176 (3)	0.03377 (18)	−0.14832 (11)	0.0312 (6)
C12	0.6573 (3)	0.01580 (17)	−0.09052 (11)	0.0303 (6)
H12	0.6220	−0.0395	−0.0802	0.036*
C13	0.6485 (3)	0.07950 (16)	−0.04747 (11)	0.0274 (6)
H13	0.6073	0.0677	−0.0076	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0590 (5)	0.0457 (5)	0.0372 (4)	−0.0022 (4)	0.0049 (3)	−0.0178 (3)
S1	0.0279 (3)	0.0230 (3)	0.0211 (3)	0.0025 (3)	−0.0011 (2)	0.0023 (2)
O1	0.0300 (8)	0.0260 (10)	0.0231 (8)	−0.0036 (8)	0.0022 (7)	0.0000 (7)
O2	0.0321 (9)	0.0282 (10)	0.0288 (9)	0.0073 (8)	0.0046 (7)	0.0005 (8)
O3	0.0398 (10)	0.0333 (10)	0.0250 (9)	0.0010 (8)	−0.0099 (8)	0.0030 (8)
N1	0.0346 (12)	0.0265 (13)	0.0233 (11)	0.0006 (10)	0.0029 (9)	0.0027 (9)
N2	0.0279 (11)	0.0226 (11)	0.0226 (10)	−0.0045 (9)	0.0012 (8)	−0.0003 (9)
C1	0.0236 (11)	0.0225 (13)	0.0177 (11)	0.0020 (10)	0.0025 (9)	0.0015 (10)
C2	0.0336 (13)	0.0249 (14)	0.0235 (12)	−0.0014 (11)	0.0006 (10)	−0.0006 (10)
C3	0.0376 (13)	0.0212 (13)	0.0353 (14)	−0.0019 (11)	0.0052 (11)	−0.0025 (11)
C4	0.0306 (13)	0.0235 (14)	0.0361 (14)	0.0031 (11)	0.0016 (11)	0.0091 (12)
C5	0.0283 (12)	0.0279 (14)	0.0248 (12)	0.0006 (11)	−0.0015 (10)	0.0066 (11)
C6	0.0215 (11)	0.0219 (13)	0.0223 (12)	−0.0015 (10)	0.0030 (9)	0.0026 (10)
C7	0.0216 (11)	0.0247 (14)	0.0194 (11)	0.0023 (10)	−0.0027 (9)	0.0020 (10)
C8	0.0208 (11)	0.0297 (14)	0.0205 (11)	0.0010 (10)	−0.0007 (9)	−0.0011 (10)
C9	0.0307 (13)	0.0320 (14)	0.0225 (12)	−0.0039 (11)	−0.0004 (10)	0.0006 (11)
C10	0.0352 (14)	0.0435 (17)	0.0190 (12)	−0.0019 (12)	0.0025 (10)	−0.0028 (11)
C11	0.0302 (12)	0.0376 (16)	0.0257 (13)	0.0010 (12)	−0.0024 (10)	−0.0090 (11)
C12	0.0331 (13)	0.0272 (14)	0.0305 (13)	−0.0034 (11)	0.0003 (11)	−0.0034 (11)
C13	0.0279 (12)	0.0296 (14)	0.0245 (12)	0.0004 (11)	0.0012 (10)	−0.0001 (11)

Geometric parameters (Å, º)

Cl1—C11	1.739 (3)	C3—H3	0.9500
S1—O2	1.429 (2)	C4—C5	1.379 (4)
S1—O3	1.436 (2)	C4—H4	0.9500
S1—N1	1.609 (2)	C5—C6	1.394 (3)
S1—C1	1.778 (2)	C5—H5	0.9500
O1—C7	1.239 (3)	C6—C7	1.503 (3)
N1—H1NA	0.80 (3)	C8—C13	1.384 (3)
N1—H1NB	0.84 (3)	C8—C9	1.399 (3)
N2—C7	1.340 (3)	C9—C10	1.372 (4)
N2—C8	1.418 (3)	C9—H9	0.9500
N2—H2N	0.81 (3)	C10—C11	1.390 (4)
C1—C2	1.382 (3)	C10—H10	0.9500
C1—C6	1.407 (3)	C11—C12	1.382 (4)
C2—C3	1.389 (4)	C12—C13	1.395 (3)
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.374 (4)	C13—H13	0.9500
O2—S1—O3	120.04 (11)	C6—C5—H5	119.5
O2—S1—N1	107.55 (12)	C5—C6—C1	118.2 (2)
O3—S1—N1	106.55 (12)	C5—C6—C7	118.9 (2)
O2—S1—C1	106.94 (10)	C1—C6—C7	122.7 (2)
O3—S1—C1	107.08 (11)	O1—C7—N2	124.0 (2)
N1—S1—C1	108.25 (11)	O1—C7—C6	121.4 (2)
S1—N1—H1NA	114 (2)	N2—C7—C6	114.5 (2)
S1—N1—H1NB	112 (2)	C13—C8—C9	119.7 (2)
H1NA—N1—H1NB	116 (3)	C13—C8—N2	123.8 (2)
C7—N2—C8	128.8 (2)	C9—C8—N2	116.4 (2)
C7—N2—H2N	112.7 (19)	C10—C9—C8	120.5 (3)
C8—N2—H2N	118.4 (19)	C10—C9—H9	119.7
C2—C1—C6	120.4 (2)	C8—C9—H9	119.7
C2—C1—S1	118.63 (17)	C9—C10—C11	119.4 (2)
C6—C1—S1	120.93 (18)	C9—C10—H10	120.3
C1—C2—C3	120.1 (2)	C11—C10—H10	120.3
C1—C2—H2	119.9	C12—C11—C10	121.0 (2)
C3—C2—H2	119.9	C12—C11—Cl1	119.7 (2)
C4—C3—C2	119.9 (2)	C10—C11—Cl1	119.32 (19)
C4—C3—H3	120.1	C11—C12—C13	119.4 (3)
C2—C3—H3	120.1	C11—C12—H12	120.3
C3—C4—C5	120.4 (2)	C13—C12—H12	120.3
C3—C4—H4	119.8	C8—C13—C12	119.9 (2)
C5—C4—H4	119.8	C8—C13—H13	120.0
C4—C5—C6	120.9 (2)	C12—C13—H13	120.0
C4—C5—H5	119.5
O2—S1—C1—C2	−139.24 (19)	C8—N2—C7—C6	179.1 (2)
O3—S1—C1—C2	−9.4 (2)	C5—C6—C7—O1	−119.2 (2)
N1—S1—C1—C2	105.1 (2)	C1—C6—C7—O1	55.1 (3)
O2—S1—C1—C6	39.5 (2)	C5—C6—C7—N2	56.7 (3)
O3—S1—C1—C6	169.33 (18)	C1—C6—C7—N2	−129.0 (2)
N1—S1—C1—C6	−76.1 (2)	C7—N2—C8—C13	−15.0 (4)
C6—C1—C2—C3	1.6 (4)	C7—N2—C8—C9	169.0 (2)
S1—C1—C2—C3	−179.72 (18)	C13—C8—C9—C10	−2.1 (4)
C1—C2—C3—C4	−2.3 (4)	N2—C8—C9—C10	174.1 (2)
C2—C3—C4—C5	0.6 (4)	C8—C9—C10—C11	1.1 (4)
C3—C4—C5—C6	2.0 (4)	C9—C10—C11—C12	0.5 (4)
C4—C5—C6—C1	−2.7 (3)	C9—C10—C11—Cl1	−179.79 (19)
C4—C5—C6—C7	171.9 (2)	C10—C11—C12—C13	−1.1 (4)
C2—C1—C6—C5	0.9 (3)	Cl1—C11—C12—C13	179.23 (18)
S1—C1—C6—C5	−177.79 (17)	C9—C8—C13—C12	1.5 (3)
C2—C1—C6—C7	−173.4 (2)	N2—C8—C13—C12	−174.3 (2)
S1—C1—C6—C7	7.9 (3)	C11—C12—C13—C8	0.0 (4)
C8—N2—C7—O1	−5.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1^i	0.81 (3)	2.32 (3)	3.028 (3)	146 (3)
N1—H1NA···O1	0.80 (3)	2.28 (3)	2.941 (3)	141 (3)
N1—H1NB···O3^ii	0.84 (3)	2.20 (3)	3.021 (3)	168 (3)
C12—H12···O1^iii	0.95	2.58	3.512 (3)	167
C2—H2···O3	0.95	2.47	2.874 (3)	106
C13—H13···O1	0.95	2.33	2.914 (3)	120

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