PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o222.
Published online 2009 January 8. doi:  10.1107/S1600536808043389
PMCID: PMC2968256

3-(3-Amino­phenyl­sulfon­yl)aniline

Abstract

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 [triangle]); Holland (1988 [triangle]); McMohan et al. (1993 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o222-scheme1.jpg

Experimental

Crystal data

  • C12H12N2O2S
  • M r = 248.30
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o222-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.078
  • wR(F 2) = 0.218
  • S = 1.12
  • 4145 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.64 e Å−3
  • Δρmin = −0.26 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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%).

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH2) and C-H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).

Figures

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.

Crystal data

C12H12N2O2SF(000) = 520
Mr = 248.30Dx = 1.367 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1532 reflections
a = 8.6282 (17) Åθ = 2.4–32.0°
b = 8.8017 (18) ŵ = 0.26 mm1
c = 16.052 (3) ÅT = 298 K
β = 98.12 (3)°Colorless, yellow
V = 1206.8 (4) Å30.40 × 0.30 × 0.28 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer4145 independent reflections
Radiation source: fine-focus sealed tube2971 reflections with I > 2σ(I)
graphiteRint = 0.091
[var phi] and ω scansθmax = 32.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −12→12
Tmin = 0.910, Tmax = 0.933k = −12→13
18754 measured reflectionsl = −23→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.078Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.218H-atom parameters constrained
S = 1.12w = 1/[σ2(Fo2) + (0.0789P)2 + 0.6213P] where P = (Fo2 + 2Fc2)/3
4145 reflections(Δ/σ)max = 0.003
154 parametersΔρmax = 0.64 e Å3
0 restraintsΔρmin = −0.26 e Å3

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 (Å2)

xyzUiso*/Ueq
S10.25722 (7)0.35241 (8)0.12847 (4)0.0538 (2)
O10.2448 (2)0.4691 (2)0.06463 (15)0.0705 (6)
O20.3825 (2)0.3662 (3)0.19740 (15)0.0734 (6)
N10.4728 (5)−0.1878 (5)0.1176 (3)0.1187 (14)
H1A0.4757−0.27450.09330.142*
H1B0.5288−0.17220.16560.142*
N2−0.3243 (3)0.4789 (4)0.1136 (2)0.0844 (9)
H2B−0.41130.47780.13400.101*
H2A−0.31830.52520.06700.101*
C10.3714 (3)0.0656 (3)0.11930 (19)0.0633 (7)
H10.43080.08540.17110.076*
C20.3800 (4)−0.0758 (4)0.0805 (2)0.0765 (9)
C30.2912 (6)−0.1002 (5)0.0046 (3)0.0977 (13)
H30.2966−0.1946−0.02080.117*
C40.1948 (6)0.0077 (5)−0.0357 (3)0.0979 (13)
H40.1368−0.0127−0.08790.117*
C50.1844 (5)0.1493 (4)0.0026 (2)0.0785 (9)
H50.11870.2244−0.02340.094*
C60.2733 (3)0.1754 (3)0.07936 (18)0.0558 (6)
C70.0781 (3)0.3441 (3)0.16923 (16)0.0498 (5)
C8−0.0511 (3)0.4117 (3)0.12433 (16)0.0513 (5)
H8−0.04330.46050.07370.062*
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)
H10−0.29560.32510.25220.077*
C11−0.0704 (4)0.2637 (4)0.2746 (2)0.0735 (8)
H11−0.07800.21400.32500.088*
C120.0725 (4)0.2692 (4)0.24466 (19)0.0660 (7)
H120.16130.22420.27410.079*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0398 (3)0.0559 (4)0.0663 (4)−0.0023 (2)0.0092 (2)0.0031 (3)
O10.0610 (12)0.0647 (12)0.0897 (15)−0.0026 (9)0.0239 (11)0.0198 (11)
O20.0473 (10)0.0876 (15)0.0821 (14)−0.0077 (10)−0.0019 (10)−0.0096 (12)
N10.136 (3)0.095 (2)0.130 (3)0.045 (2)0.036 (3)−0.002 (2)
N20.0493 (13)0.108 (2)0.101 (2)0.0197 (14)0.0271 (14)0.0260 (18)
C10.0570 (15)0.0685 (17)0.0684 (17)0.0104 (12)0.0225 (13)0.0047 (14)
C20.084 (2)0.0656 (18)0.088 (2)0.0161 (16)0.0439 (19)0.0042 (16)
C30.135 (4)0.079 (2)0.089 (3)−0.002 (2)0.050 (3)−0.020 (2)
C40.124 (4)0.091 (3)0.079 (2)−0.004 (3)0.018 (2)−0.013 (2)
C50.083 (2)0.082 (2)0.0693 (19)0.0001 (18)0.0068 (17)−0.0018 (17)
C60.0501 (12)0.0577 (14)0.0627 (15)0.0024 (10)0.0182 (11)0.0013 (11)
C70.0449 (11)0.0504 (12)0.0552 (13)−0.0016 (9)0.0105 (10)−0.0026 (10)
C80.0450 (11)0.0535 (13)0.0572 (13)0.0022 (10)0.0131 (10)0.0021 (11)
C90.0466 (12)0.0540 (13)0.0652 (15)0.0025 (10)0.0155 (11)−0.0061 (11)
C100.0601 (15)0.0708 (18)0.0678 (17)−0.0050 (13)0.0272 (13)−0.0045 (13)
C110.0748 (19)0.087 (2)0.0623 (17)−0.0027 (16)0.0236 (15)0.0147 (16)
C120.0609 (16)0.0750 (19)0.0623 (16)0.0042 (14)0.0097 (13)0.0128 (14)

Geometric parameters (Å, °)

O1—S11.444 (2)C5—C61.376 (5)
O2—S11.439 (2)C5—H50.9300
N1—H1A0.8600C6—S11.760 (3)
N1—H1B0.8600C7—C81.375 (4)
N2—H2B0.8600C7—C121.386 (4)
N2—H2A0.8600C7—S11.763 (2)
C1—C61.382 (4)C8—C91.401 (3)
C1—C21.398 (4)C8—H80.9300
C1—H10.9300C9—N21.378 (4)
C2—N11.353 (5)C9—C101.390 (4)
C2—C31.361 (6)C10—C111.372 (5)
C3—C41.365 (6)C10—H100.9300
C3—H30.9300C11—C121.386 (4)
C4—C51.398 (5)C11—H110.9300
C4—H40.9300C12—H120.9300
O1—S1—C6108.32 (13)C6—C5—C4118.7 (4)
O1—S1—C7108.16 (12)C6—C5—H5120.6
O2—S1—O1117.27 (14)C4—C5—H5120.6
O2—S1—C6108.72 (14)C5—C6—C1121.7 (3)
O2—S1—C7108.72 (13)C5—C6—S1118.7 (2)
C6—S1—C7104.97 (12)C1—C6—S1119.6 (2)
C2—N1—H1A120.0C8—C7—C12122.6 (2)
C2—N1—H1B120.0C8—C7—S1118.43 (19)
H1A—N1—H1B120.0C12—C7—S1119.0 (2)
C9—N2—H2A120.0C7—C8—C9119.4 (2)
C9—N2—H2B120.0C7—C8—H8120.3
H2B—N2—H2A120.0C9—C8—H8120.3
C6—C1—C2119.0 (3)N2—C9—C10121.3 (2)
C6—C1—H1120.5N2—C9—C8120.5 (3)
C2—C1—H1120.5C10—C9—C8118.2 (3)
N1—C2—C3120.1 (4)C11—C10—C9121.4 (3)
N1—C2—C1121.2 (4)C11—C10—H10119.3
C3—C2—C1118.7 (3)C9—C10—H10119.3
C2—C3—C4122.9 (4)C10—C11—C12120.9 (3)
C2—C3—H3118.5C10—C11—H11119.5
C4—C3—H3118.5C12—C11—H11119.5
C3—C4—C5119.0 (4)C7—C12—C11117.5 (3)
C3—C4—H4120.5C7—C12—H12121.2
C5—C4—H4120.5C11—C12—H12121.2
C6—C1—C2—N1−179.1 (3)C9—C10—C11—C12−0.2 (5)
C6—C1—C2—C30.0 (4)C8—C7—C12—C110.0 (5)
N1—C2—C3—C4179.6 (4)S1—C7—C12—C11−179.5 (2)
C1—C2—C3—C40.4 (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—C60.6 (6)C1—C6—S1—O213.6 (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—O1142.1 (2)
C2—C1—C6—C5−0.1 (4)C5—C6—S1—C776.0 (3)
C2—C1—C6—S1178.4 (2)C1—C6—S1—C7−102.6 (2)
C12—C7—C8—C90.4 (4)C8—C7—S1—O2144.7 (2)
S1—C7—C8—C9179.9 (2)C12—C7—S1—O2−35.7 (3)
C7—C8—C9—N2177.2 (3)C8—C7—S1—O116.4 (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—C110.6 (5)C12—C7—S1—C680.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···O2i0.862.253.091 (5)166
N2—H2A···O1ii0.862.293.069 (4)151
N2—H2B···O2iii0.862.383.187 (4)156
C1—H1···O20.932.552.924 (4)104
C8—H8···O10.932.512.895 (3)105

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2599).

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.
  • Block, E. (1992). Angew. Chem. Int. Ed. Engl 31, 1135–1178.
  • Bruker (1998). SMART, SAINT, and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Holland, H. L. (1988). Chem. Rev 88, 473–485.
  • 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. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography