4-Methyl-N-[2-(p-tolylsulfanyl)phenyl]benzene­sulfonamide

The title compound, C₂₀H₁₉NO₂S₂, is formed by a palladium–copper-catalyzed reaction between 4-methyl-N-[2-(prop-2-ynyl­sul­fanyl)­phenyl]­benzene­sul­fon­amide and p-iodo­toluene. The mol­ecules contain three essentially planar parts, namely an amino­thio­phenol moiety (A), a toluene­sulfone moiety excluding the oxo ligands (B) and a tolyl group (C), approximately orthogonal to each other; the dihedral angles A/B, A/C and B/C are 111.6 (1), 89.3 (1) and 101.4 (1)°, respectively. Intermolecular N—H...O hydrogen bonds link the mol­ecules into infinite one-dimensional chains.

S1. Comment

Metal-catalyzed heteroannulation is an important synthetic tool for the formation of a variety of heterocyclic systems of biological importance (Mukherjee et al., 2000; Kundu et al., 1999). During the synthesis of a sulfur containing heterocyclic compound, benzothiazine, (II), via a palladium-copper catalyzed reaction between 4-methyl-N-[2-(prop-2-ynylsulfanyl)phenyl]benzenesulfonamide, (I), and p-iodotoluene, the title compound, 4-methyl-N-[2-(p-tolylsulfanyl)phenyl]benzenesulfonamide, (III), was obtained through a novel depropargylation and S-arylation. The X-ray structural study of (III) was undertaken in order to establish the regio- and stereospecificities of the reaction. \sch

The structure of (III) consists of three essentially planar parts, (A, B, C), approximately orthogonal to each other. The central aminothiophenol moiety A (atoms C8—C13, N1, S2) is planar to within 0.031 (4) Å. The other two parts, p-toluenesulfone excluding the two oxo ligands (B: atoms C1—C7,S1) and p-tolyl (C: atoms C14—C20) with a maximum deviation of 0.025 (4) Å for an in-plane atom (C1) from the corresponding least-squares plane, are inclined by 101.4 (1)° with respect to each other. The dihedral angles A/B and A/C are 111.6 (1) and 89.3 (1)°, respectively. The torsion angle C5—S1—N1—C8 62.4 (3)° establishes a gauche conformation of the molecule when viewed along the S—N axis.

The geometric parameters of (III) agree well with those found in other substituted p-toluenesulfonamide structures (Parvez et al., 1999; Goswami et al., 1998; Bachechi et al., 1996; Gainsford & Lensink, 1996). The N atom with a bond angle sum of 349.5 (2)° indicates a pyramidal configuration. The angular disposition of the bonds about the sulfonyl S atom (S1) deviate significantly from that of regular tetrahedron. The widening of the O1—S1—O2 angle 119.1 (1)° from the ideal tetrahedral value is presumably the result of the repulsive interaction between the short S═O bonds (Table 1). The lack of π bonding in the branches among the phenyl rings precludes any possible π conjugation across the whole molecule. The aromatic nature of the rings is therefore localized within the rings and on their direct substituents. One of the sulfonyl O atoms, O1, is nearly coplanar with tolyl substituent [O1—S1—C5—C6 14.2 (3)°], the other sulfonyl O atom, O2, forms a torsion angle O2—S1—C5—C6 144.8 (3)°.

In the solid state, the molecules translated in the b direction are linked through N1—H8···O2 intermolecular hydrogen bonds (Table 2) to form infinite one-dimensional chains.

S2. Experimental

Compound (III) [m.p. 357 (1) K] was synthesized by stirring a mixture of 4-methyl-N-[2-(prop-2-ynylsulfanyl)phenyl]benzenesulfonamide, (I) (1.32 mmol) and p-iodotoluene (1.33 mmol) in the presence of bis(triphenylphosphine)palladium(II) chloride (0.04 mmol), cuprous iodide (0.52 mmol) and triethylamine (5.23 mmol) followed by refluxing with tetrahydrofuran for 36 h under an argon atmosphere. After usual workup, the crude product purified by column chromatography through silica gel using ethylacetate-petroleum spirit (333–353 K) mixture (1:9) as eluant yielded the title compound, (III). Single crystals suitable for X-ray analysis were obtained from CHCl₃ -light petroleum (333–353 K) mixture.

Elemental analysis: calculated for C₂₀H₁₉NS₂O₂: C 65.01, H 5.18, N 3.79%; found C 65.32, H 5.25, N 3.74%.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: MULTAN88 (Debaerdemaeker et al., 1988); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).

Figures

Fig. 1. ZORTEP (Zsolnai, 1995) view (50% probability level) of the molecule.

4-methyl-N-[2-(p-tolylsulfanyl)phenyl]benzenesulfonamide

Crystal data

C20H19NO2S2	F(000) = 388
Mr = 369.48	Dx = 1.335 Mg m^−3
Triclinic, P1	Melting point: 357(1) K K
a = 10.530 (4) Å	Cu Kα radiation, λ = 1.54180 Å
b = 11.873 (3) Å	Cell parameters from 25 reflections
c = 8.798 (4) Å	θ = 33.5–39.8°
α = 90.76 (4)°	µ = 2.73 mm^−1
β = 113.31 (4)°	T = 293 K
γ = 112.05 (2)°	Block, colourless
V = 919.2 (6) Å^3	0.35 × 0.25 × 0.20 mm
Z = 2

Data collection

Rigaku AFC5R diffractometer	2610 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.039
Graphite monochromator	θmax = 70.1°, θmin = 4.1°
ω–2θ scans	h = −12→12
Absorption correction: ψ scans (North et al., 1968)	k = −14→13
Tmin = 0.449, Tmax = 0.580	l = −9→10
3497 measured reflections	3 standard reflections every 150 reflections
3301 independent reflections	intensity decay: <3%

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)] = 0.049	Hydrogen site location: mixed
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0764P)^2 + 0.3704P] where P = (Fo^2 + 2Fc^2)/3
3301 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
S1	0.18019 (7)	0.44629 (6)	0.18887 (9)	0.0490 (2)
S2	−0.22384 (10)	0.13981 (7)	−0.17435 (10)	0.0672 (3)
O1	0.2756 (2)	0.45040 (19)	0.3596 (3)	0.0615 (5)
O2	0.1530 (2)	0.55371 (17)	0.1436 (3)	0.0600 (5)
N1	0.0105 (2)	0.3350 (2)	0.1370 (3)	0.0488 (5)
H8	−0.0658	0.3444	0.0357	0.063 (9)*
C1	0.4277 (4)	0.3007 (3)	−0.2599 (5)	0.0727 (9)
H1A	0.4253	0.3513	−0.3444	0.109*
H1B	0.3654	0.2154	−0.3134	0.109*
H1C	0.5304	0.3113	−0.1938	0.109*
C2	0.3682 (3)	0.3387 (2)	−0.1472 (4)	0.0545 (7)
C3	0.2613 (3)	0.3891 (3)	−0.2081 (4)	0.0584 (7)
H3	0.2286	0.4012	−0.3189	0.070*
C4	0.2029 (3)	0.4213 (3)	−0.1069 (4)	0.0577 (7)
H4	0.1309	0.4539	−0.1495	0.069*
C5	0.2536 (3)	0.4043 (2)	0.0593 (4)	0.0471 (6)
C6	0.3610 (3)	0.3562 (3)	0.1235 (4)	0.0567 (7)
H6	0.3955	0.3458	0.2351	0.068*
C7	0.4163 (3)	0.3237 (3)	0.0190 (4)	0.0601 (8)
H7	0.4879	0.2908	0.0618	0.072*
C8	−0.0115 (3)	0.2102 (2)	0.1575 (3)	0.0446 (6)
C9	0.0685 (3)	0.1868 (3)	0.3123 (4)	0.0558 (7)
H9	0.1391	0.2528	0.4013	0.067*
C10	0.0453 (3)	0.0667 (3)	0.3370 (4)	0.0629 (8)
H10	0.1017	0.0525	0.4408	0.076*
C11	−0.0624 (4)	−0.0317 (3)	0.2061 (4)	0.0643 (8)
H11	−0.0795	−0.1125	0.2217	0.077*
C12	−0.1439 (3)	−0.0095 (3)	0.0535 (4)	0.0601 (8)
H12	−0.2166	−0.0761	−0.0336	0.072*
C13	−0.1208 (3)	0.1102 (2)	0.0252 (3)	0.0472 (6)
C14	−0.3999 (3)	0.0050 (3)	−0.2546 (3)	0.0523 (7)
C15	−0.4254 (3)	−0.0922 (3)	−0.3672 (4)	0.0552 (7)
H15	−0.3499	−0.0887	−0.3992	0.066*
C16	−0.5640 (3)	−0.1950 (3)	−0.4326 (4)	0.0549 (7)
H16	−0.5803	−0.2596	−0.5089	0.066*
C17	−0.6787 (3)	−0.2038 (3)	−0.3870 (4)	0.0570 (7)
C18	−0.6509 (4)	−0.1049 (3)	−0.2746 (4)	0.0694 (9)
H18	−0.7259	−0.1078	−0.2422	0.083*
C19	−0.5129 (4)	−0.0016 (3)	−0.2096 (4)	0.0655 (8)
H19	−0.4969	0.0638	−0.1348	0.079*
C20	−0.8285 (4)	−0.3156 (4)	−0.4597 (5)	0.0857 (12)
H20A	−0.8882	−0.3112	−0.4028	0.129*
H20B	−0.8108	−0.3892	−0.4450	0.129*
H20C	−0.8820	−0.3177	−0.5777	0.129*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0432 (4)	0.0370 (3)	0.0512 (4)	0.0107 (3)	0.0116 (3)	0.0006 (3)
S2	0.0660 (5)	0.0461 (4)	0.0525 (5)	0.0077 (3)	0.0048 (4)	0.0122 (3)
O1	0.0538 (12)	0.0535 (12)	0.0513 (12)	0.0101 (9)	0.0097 (9)	−0.0007 (9)
O2	0.0553 (11)	0.0353 (10)	0.0754 (14)	0.0154 (9)	0.0183 (10)	0.0024 (9)
N1	0.0410 (12)	0.0450 (12)	0.0509 (13)	0.0144 (10)	0.0141 (10)	0.0041 (10)
C1	0.0556 (18)	0.066 (2)	0.084 (2)	0.0164 (16)	0.0268 (17)	−0.0083 (17)
C2	0.0410 (14)	0.0385 (14)	0.0674 (19)	0.0060 (11)	0.0179 (13)	−0.0021 (12)
C3	0.0524 (16)	0.0577 (17)	0.0520 (17)	0.0192 (14)	0.0136 (13)	0.0043 (13)
C4	0.0488 (16)	0.0569 (17)	0.0572 (18)	0.0233 (14)	0.0118 (13)	0.0070 (13)
C5	0.0396 (13)	0.0339 (12)	0.0553 (16)	0.0098 (10)	0.0137 (12)	0.0056 (11)
C6	0.0523 (16)	0.0489 (16)	0.0627 (18)	0.0217 (13)	0.0181 (14)	0.0157 (13)
C7	0.0450 (15)	0.0492 (16)	0.080 (2)	0.0198 (13)	0.0205 (15)	0.0118 (15)
C8	0.0386 (13)	0.0451 (14)	0.0485 (15)	0.0139 (11)	0.0207 (11)	0.0095 (11)
C9	0.0445 (15)	0.0562 (17)	0.0478 (16)	0.0096 (13)	0.0125 (12)	0.0100 (13)
C10	0.0469 (16)	0.068 (2)	0.0617 (19)	0.0173 (14)	0.0180 (14)	0.0298 (16)
C11	0.0555 (17)	0.0515 (17)	0.074 (2)	0.0161 (14)	0.0222 (16)	0.0267 (15)
C12	0.0564 (17)	0.0411 (15)	0.0620 (19)	0.0098 (13)	0.0154 (15)	0.0093 (13)
C13	0.0451 (14)	0.0402 (14)	0.0470 (15)	0.0109 (11)	0.0173 (12)	0.0094 (11)
C14	0.0541 (16)	0.0506 (15)	0.0407 (14)	0.0188 (13)	0.0122 (12)	0.0078 (12)
C15	0.0491 (15)	0.0560 (16)	0.0543 (17)	0.0196 (13)	0.0187 (13)	0.0056 (13)
C16	0.0507 (15)	0.0545 (16)	0.0488 (16)	0.0181 (13)	0.0151 (13)	−0.0003 (12)
C17	0.0491 (15)	0.0622 (18)	0.0472 (16)	0.0169 (14)	0.0149 (13)	0.0058 (13)
C18	0.0589 (19)	0.078 (2)	0.067 (2)	0.0214 (17)	0.0304 (17)	−0.0031 (17)
C19	0.072 (2)	0.0609 (19)	0.0560 (18)	0.0254 (16)	0.0231 (16)	−0.0027 (14)
C20	0.059 (2)	0.083 (3)	0.081 (3)	0.0009 (18)	0.0257 (19)	−0.008 (2)

Geometric parameters (Å, º)

S1—O1	1.427 (2)	C8—C13	1.402 (4)
S1—O2	1.437 (2)	C9—C10	1.389 (4)
S1—N1	1.647 (2)	C9—H9	0.9300
S1—C5	1.765 (3)	C10—C11	1.383 (5)
S2—C13	1.783 (3)	C10—H10	0.9300
S2—C14	1.790 (3)	C11—C12	1.370 (4)
N1—C8	1.437 (3)	C11—H11	0.9300
N1—H8	0.98	C12—C13	1.392 (4)
C1—C2	1.507 (4)	C12—H12	0.9300
C1—H1A	0.9600	C14—C19	1.372 (4)
C1—H1B	0.9600	C14—C15	1.383 (4)
C1—H1C	0.9600	C15—C16	1.390 (4)
C2—C7	1.384 (4)	C15—H15	0.9300
C2—C3	1.396 (4)	C16—C17	1.386 (4)
C3—C4	1.385 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.387 (4)
C4—C5	1.391 (4)	C17—C20	1.505 (4)
C4—H4	0.9300	C18—C19	1.388 (5)
C5—C6	1.383 (4)	C18—H18	0.9300
C6—C7	1.385 (4)	C19—H19	0.9300
C6—H6	0.9300	C20—H20A	0.9600
C7—H7	0.9300	C20—H20B	0.9600
C8—C9	1.386 (4)	C20—H20C	0.9600
O1—S1—O2	119.09 (13)	C8—C9—H9	119.4
O1—S1—N1	108.45 (13)	C10—C9—H9	119.4
O2—S1—N1	104.96 (12)	C11—C10—C9	119.5 (3)
O1—S1—C5	108.09 (13)	C11—C10—H10	120.2
O2—S1—C5	108.79 (13)	C9—C10—H10	120.2
N1—S1—C5	106.84 (12)	C12—C11—C10	119.6 (3)
C13—S2—C14	101.85 (14)	C12—C11—H11	120.2
C8—N1—S1	122.21 (18)	C10—C11—H11	120.2
C8—N1—H8	116	C11—C12—C13	121.8 (3)
S1—N1—H8	111	C11—C12—H12	119.1
C2—C1—H1A	109.5	C13—C12—H12	119.1
C2—C1—H1B	109.5	C12—C13—C8	118.7 (3)
H1A—C1—H1B	109.5	C12—C13—S2	122.0 (2)
C2—C1—H1C	109.5	C8—C13—S2	119.3 (2)
H1A—C1—H1C	109.5	C19—C14—C15	119.2 (3)
H1B—C1—H1C	109.5	C19—C14—S2	120.5 (2)
C7—C2—C3	117.8 (3)	C15—C14—S2	120.2 (2)
C7—C2—C1	121.3 (3)	C14—C15—C16	119.8 (3)
C3—C2—C1	120.9 (3)	C14—C15—H15	120.1
C4—C3—C2	121.4 (3)	C16—C15—H15	120.1
C4—C3—H3	119.3	C17—C16—C15	121.7 (3)
C2—C3—H3	119.3	C17—C16—H16	119.2
C3—C4—C5	119.1 (3)	C15—C16—H16	119.2
C3—C4—H4	120.4	C16—C17—C18	117.4 (3)
C5—C4—H4	120.4	C16—C17—C20	121.0 (3)
C6—C5—C4	120.7 (3)	C18—C17—C20	121.6 (3)
C6—C5—S1	120.1 (2)	C19—C18—C17	121.1 (3)
C4—C5—S1	119.2 (2)	C19—C18—H18	119.4
C5—C6—C7	118.9 (3)	C17—C18—H18	119.4
C5—C6—H6	120.5	C14—C19—C18	120.7 (3)
C7—C6—H6	120.5	C14—C19—H19	119.7
C2—C7—C6	122.1 (3)	C18—C19—H19	119.7
C2—C7—H7	119.0	C17—C20—H20A	109.5
C6—C7—H7	119.0	C17—C20—H20B	109.5
C9—C8—C13	119.1 (3)	H20A—C20—H20B	109.5
C9—C8—N1	120.1 (2)	C17—C20—H20C	109.5
C13—C8—N1	120.7 (2)	H20A—C20—H20C	109.5
C8—C9—C10	121.2 (3)	H20B—C20—H20C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H8···S2	0.98	2.55	3.025 (3)	109.9
N1—H8···O2^i	0.98	2.13	3.039 (4)	154.2

Symmetry code: (i) −x, −y+1, −z.