3-(3-Amino­phenyl­sulfon­yl)aniline

Ghazisaeidi, R.; Yousefi, M.

doi:10.1107/S1600536808043389

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o222

doi:10.1107/S1600536808043389

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3-(3-Aminophenylsulfonyl)aniline

Reza Ghazisaeidi ^a and Mohammad Yousefi ^b ^*

^aIslamic Azad University, Tehran South Branch, Tehran, Iran, and ^bIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran
^*Correspondence e-mail: myousefi50@yahoo.com

(Received 11 December 2008; accepted 19 December 2008; online 8 January 2009)

In the title compound, C₁₂H₁₂N₂O₂S, the aromatic rings are oriented at a dihedral angle of 79.48 (4)°. Intramolecular C—H⋯O hydrogen bonds result in the formation of two five-membered rings with envelope conformations. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules. π–π Contacts between the benzene rings, [centroid–centroid distance = 4.211 (3) Å] may further stabilize the structure.

Related literature

For general background, see: Block (1992 ); Holland (1988 ); McMohan et al. (1993 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₂N₂O₂S
M_r = 248.30
Monoclinic, P 2₁ /c
a = 8.6282 (17) Å
b = 8.8017 (18) Å
c = 16.052 (3) Å
β = 98.12 (3)°
V = 1206.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 (2) K
0.40 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.910, T_max = 0.933
18754 measured reflections
4145 independent reflections
2971 reflections with I > 2σ(I)
R_int = 0.091

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.218
S = 1.12
4145 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2ⁱ	0.86	2.25	3.091 (5)	166
N2—H2A⋯O1ⁱⁱ	0.86	2.29	3.069 (4)	151
N2—H2B⋯O2ⁱⁱⁱ	0.86	2.38	3.187 (4)	156
C1—H1⋯O2	0.93	2.55	2.924 (4)	104
C8—H8⋯O1	0.93	2.51	2.895 (3)	105
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) x-1, y, z.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808043389/hk2599sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043389/hk2599Isup2.hkl

checkCIF report

Comment top

Aryl sulfones and sulfoxides are interesting functional groups possessing manifold reactivity for conversion to a variety of organosulfur compounds in the fields of drugs and pharmaceuticals (Holland, 1988; Block, 1992). In particular, aryl sulfones have received much attention as powerful anti-HIV-1 agents (McMohan et al., 1993). We report herein the synthesis and crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C7-C12) are, of course, planar, and they are oriented at a dihedral angle of 79.48 (4)°. The intramolecular C-H···O hydrogen bonds (Table 1) result in the formations of two five-membered rings C (S1/O1/C7/C8/H8) and D (S1/O2/C1/C6/H1), having envelope conformations with atoms O1 and O2 displaced by -0.386 (4) Å and 0.300 (4) Å, respectively, from the planes of the other ring atoms.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the phenyl rings, Cg1—Cg1ⁱ [symmetry code: (i) 1 - x, -y, -z, where Cg1 is centroid of the ring A (C1-C6)] may further stabilize the structure, with centroid-centroid distance of 4.211 (3) Å.

Related literature top

For general background, see: Block (1992); Holland (1988); McMohan et al. (1993). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, a solution of 3,3'-diaminodiphenyl sulfone (0.52 g, 2.0 mmol) in methanol (10 ml) was added to a solution of pyrazinecarboxylic acid (0.51 g, 4.0 mmol) in methanol (20 ml), and the resulting yellow solution was stirred for 40 min at 313 K. It was left to evaporate slowly at room temperature. After one week, yellow prismatic crystals of the title compound were isolated (yield; 0.45 g, 86.5%).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

3-(3-Aminophenylsulfonyl)aniline top

Crystal data top

C₁₂H₁₂N₂O₂S	F(000) = 520
M_r = 248.30	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1532 reflections
a = 8.6282 (17) Å	θ = 2.4–32.0°
b = 8.8017 (18) Å	µ = 0.26 mm⁻¹
c = 16.052 (3) Å	T = 298 K
β = 98.12 (3)°	Colorless, yellow
V = 1206.8 (4) Å³	0.40 × 0.30 × 0.28 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4145 independent reflections
Radiation source: fine-focus sealed tube	2971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
ϕ and ω scans	θ_max = 32.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −12→12
T_min = 0.910, T_max = 0.933	k = −12→13
18754 measured reflections	l = −23→23

Refinement top

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.218	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0789P)² + 0.6213P] where P = (F_o² + 2F_c²)/3
4145 reflections	(Δ/σ)_max = 0.003
154 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₁₂N₂O₂S	V = 1206.8 (4) Å³
M_r = 248.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6282 (17) Å	µ = 0.26 mm⁻¹
b = 8.8017 (18) Å	T = 298 K
c = 16.052 (3) Å	0.40 × 0.30 × 0.28 mm
β = 98.12 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4145 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2971 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.933	R_int = 0.091
18754 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	0 restraints
wR(F²) = 0.218	H-atom parameters constrained
S = 1.12	Δρ_max = 0.64 e Å⁻³
4145 reflections	Δρ_min = −0.26 e Å⁻³
154 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.25722 (7)	0.35241 (8)	0.12847 (4)	0.0538 (2)
O1	0.2448 (2)	0.4691 (2)	0.06463 (15)	0.0705 (6)
O2	0.3825 (2)	0.3662 (3)	0.19740 (15)	0.0734 (6)
N1	0.4728 (5)	−0.1878 (5)	0.1176 (3)	0.1187 (14)
H1A	0.4757	−0.2745	0.0933	0.142*
H1B	0.5288	−0.1722	0.1656	0.142*
N2	−0.3243 (3)	0.4789 (4)	0.1136 (2)	0.0844 (9)
H2B	−0.4113	0.4778	0.1340	0.101*
H2A	−0.3183	0.5252	0.0670	0.101*
C1	0.3714 (3)	0.0656 (3)	0.11930 (19)	0.0633 (7)
H1	0.4308	0.0854	0.1711	0.076*
C2	0.3800 (4)	−0.0758 (4)	0.0805 (2)	0.0765 (9)
C3	0.2912 (6)	−0.1002 (5)	0.0046 (3)	0.0977 (13)
H3	0.2966	−0.1946	−0.0208	0.117*
C4	0.1948 (6)	0.0077 (5)	−0.0357 (3)	0.0979 (13)
H4	0.1368	−0.0127	−0.0879	0.117*
C5	0.1844 (5)	0.1493 (4)	0.0026 (2)	0.0785 (9)
H5	0.1187	0.2244	−0.0234	0.094*
C6	0.2733 (3)	0.1754 (3)	0.07936 (18)	0.0558 (6)
C7	0.0781 (3)	0.3441 (3)	0.16923 (16)	0.0498 (5)
C8	−0.0511 (3)	0.4117 (3)	0.12433 (16)	0.0513 (5)
H8	−0.0433	0.4605	0.0737	0.062*
C9	−0.1947 (3)	0.4063 (3)	0.15552 (18)	0.0545 (6)
C10	−0.2009 (4)	0.3306 (4)	0.2309 (2)	0.0645 (7)
H10	−0.2956	0.3251	0.2522	0.077*
C11	−0.0704 (4)	0.2637 (4)	0.2746 (2)	0.0735 (8)
H11	−0.0780	0.2140	0.3250	0.088*
C12	0.0725 (4)	0.2692 (4)	0.24466 (19)	0.0660 (7)
H12	0.1613	0.2242	0.2741	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0398 (3)	0.0559 (4)	0.0663 (4)	−0.0023 (2)	0.0092 (2)	0.0031 (3)
O1	0.0610 (12)	0.0647 (12)	0.0897 (15)	−0.0026 (9)	0.0239 (11)	0.0198 (11)
O2	0.0473 (10)	0.0876 (15)	0.0821 (14)	−0.0077 (10)	−0.0019 (10)	−0.0096 (12)
N1	0.136 (3)	0.095 (2)	0.130 (3)	0.045 (2)	0.036 (3)	−0.002 (2)
N2	0.0493 (13)	0.108 (2)	0.101 (2)	0.0197 (14)	0.0271 (14)	0.0260 (18)
C1	0.0570 (15)	0.0685 (17)	0.0684 (17)	0.0104 (12)	0.0225 (13)	0.0047 (14)
C2	0.084 (2)	0.0656 (18)	0.088 (2)	0.0161 (16)	0.0439 (19)	0.0042 (16)
C3	0.135 (4)	0.079 (2)	0.089 (3)	−0.002 (2)	0.050 (3)	−0.020 (2)
C4	0.124 (4)	0.091 (3)	0.079 (2)	−0.004 (3)	0.018 (2)	−0.013 (2)
C5	0.083 (2)	0.082 (2)	0.0693 (19)	0.0001 (18)	0.0068 (17)	−0.0018 (17)
C6	0.0501 (12)	0.0577 (14)	0.0627 (15)	0.0024 (10)	0.0182 (11)	0.0013 (11)
C7	0.0449 (11)	0.0504 (12)	0.0552 (13)	−0.0016 (9)	0.0105 (10)	−0.0026 (10)
C8	0.0450 (11)	0.0535 (13)	0.0572 (13)	0.0022 (10)	0.0131 (10)	0.0021 (11)
C9	0.0466 (12)	0.0540 (13)	0.0652 (15)	0.0025 (10)	0.0155 (11)	−0.0061 (11)
C10	0.0601 (15)	0.0708 (18)	0.0678 (17)	−0.0050 (13)	0.0272 (13)	−0.0045 (13)
C11	0.0748 (19)	0.087 (2)	0.0623 (17)	−0.0027 (16)	0.0236 (15)	0.0147 (16)
C12	0.0609 (16)	0.0750 (19)	0.0623 (16)	0.0042 (14)	0.0097 (13)	0.0128 (14)

Geometric parameters (Å, º) top

O1—S1	1.444 (2)	C5—C6	1.376 (5)
O2—S1	1.439 (2)	C5—H5	0.9300
N1—H1A	0.8600	C6—S1	1.760 (3)
N1—H1B	0.8600	C7—C8	1.375 (4)
N2—H2B	0.8600	C7—C12	1.386 (4)
N2—H2A	0.8600	C7—S1	1.763 (2)
C1—C6	1.382 (4)	C8—C9	1.401 (3)
C1—C2	1.398 (4)	C8—H8	0.9300
C1—H1	0.9300	C9—N2	1.378 (4)
C2—N1	1.353 (5)	C9—C10	1.390 (4)
C2—C3	1.361 (6)	C10—C11	1.372 (5)
C3—C4	1.365 (6)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.386 (4)
C4—C5	1.398 (5)	C11—H11	0.9300
C4—H4	0.9300	C12—H12	0.9300

O1—S1—C6	108.32 (13)	C6—C5—C4	118.7 (4)
O1—S1—C7	108.16 (12)	C6—C5—H5	120.6
O2—S1—O1	117.27 (14)	C4—C5—H5	120.6
O2—S1—C6	108.72 (14)	C5—C6—C1	121.7 (3)
O2—S1—C7	108.72 (13)	C5—C6—S1	118.7 (2)
C6—S1—C7	104.97 (12)	C1—C6—S1	119.6 (2)
C2—N1—H1A	120.0	C8—C7—C12	122.6 (2)
C2—N1—H1B	120.0	C8—C7—S1	118.43 (19)
H1A—N1—H1B	120.0	C12—C7—S1	119.0 (2)
C9—N2—H2A	120.0	C7—C8—C9	119.4 (2)
C9—N2—H2B	120.0	C7—C8—H8	120.3
H2B—N2—H2A	120.0	C9—C8—H8	120.3
C6—C1—C2	119.0 (3)	N2—C9—C10	121.3 (2)
C6—C1—H1	120.5	N2—C9—C8	120.5 (3)
C2—C1—H1	120.5	C10—C9—C8	118.2 (3)
N1—C2—C3	120.1 (4)	C11—C10—C9	121.4 (3)
N1—C2—C1	121.2 (4)	C11—C10—H10	119.3
C3—C2—C1	118.7 (3)	C9—C10—H10	119.3
C2—C3—C4	122.9 (4)	C10—C11—C12	120.9 (3)
C2—C3—H3	118.5	C10—C11—H11	119.5
C4—C3—H3	118.5	C12—C11—H11	119.5
C3—C4—C5	119.0 (4)	C7—C12—C11	117.5 (3)
C3—C4—H4	120.5	C7—C12—H12	121.2
C5—C4—H4	120.5	C11—C12—H12	121.2

C6—C1—C2—N1	−179.1 (3)	C9—C10—C11—C12	−0.2 (5)
C6—C1—C2—C3	0.0 (4)	C8—C7—C12—C11	0.0 (5)
N1—C2—C3—C4	179.6 (4)	S1—C7—C12—C11	−179.5 (2)
C1—C2—C3—C4	0.4 (6)	C10—C11—C12—C7	−0.1 (5)
C2—C3—C4—C5	−0.8 (7)	C5—C6—S1—O2	−167.8 (2)
C3—C4—C5—C6	0.6 (6)	C1—C6—S1—O2	13.6 (3)
C4—C5—C6—C1	−0.2 (5)	C5—C6—S1—O1	−39.4 (3)
C4—C5—C6—S1	−178.7 (3)	C1—C6—S1—O1	142.1 (2)
C2—C1—C6—C5	−0.1 (4)	C5—C6—S1—C7	76.0 (3)
C2—C1—C6—S1	178.4 (2)	C1—C6—S1—C7	−102.6 (2)
C12—C7—C8—C9	0.4 (4)	C8—C7—S1—O2	144.7 (2)
S1—C7—C8—C9	179.9 (2)	C12—C7—S1—O2	−35.7 (3)
C7—C8—C9—N2	177.2 (3)	C8—C7—S1—O1	16.4 (3)
C7—C8—C9—C10	−0.7 (4)	C12—C7—S1—O1	−164.1 (2)
N2—C9—C10—C11	−177.2 (3)	C8—C7—S1—C6	−99.1 (2)
C8—C9—C10—C11	0.6 (5)	C12—C7—S1—C6	80.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2ⁱ	0.86	2.25	3.091 (5)	166
N2—H2A···O1ⁱⁱ	0.86	2.29	3.069 (4)	151
N2—H2B···O2ⁱⁱⁱ	0.86	2.38	3.187 (4)	156
C1—H1···O2	0.93	2.55	2.924 (4)	104
C8—H8···O1	0.93	2.51	2.895 (3)	105

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₂S
M_r	248.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.6282 (17), 8.8017 (18), 16.052 (3)
β (°)	98.12 (3)
V (Å³)	1206.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.40 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.910, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	18754, 4145, 2971
R_int	0.091
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.218, 1.12
No. of reflections	4145
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.26

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2ⁱ	0.86	2.25	3.091 (5)	166.00
N2—H2A···O1ⁱⁱ	0.86	2.29	3.069 (4)	151.00
N2—H2B···O2ⁱⁱⁱ	0.86	2.38	3.187 (4)	156.00
C1—H1···O2	0.93	2.55	2.924 (4)	104.00
C8—H8···O1	0.93	2.51	2.895 (3)	105.00

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

Acknowledgements

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Block, E. (1992). Angew. Chem. Int. Ed. Engl. 31, 1135–1178. CrossRef Web of Science Google Scholar
Bruker (1998). SMART, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Holland, H. L. (1988). Chem. Rev. 88, 473–485. CrossRef CAS Web of Science Google Scholar
McMohan, J. B., Gulakowsky, R. J., Weislow, O. S., Schoktz, R. J., Narayanan, V. L., Clanton, D. J., Pedemonte, R., Wassmundt, F. W., Buckheit, R. W., Decker, W. D., White, E. L., Bader, J. P. & Boyd, M. R. (1993). Antimicrob. Agents Chemother. 37, 754–760. PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar