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organic compounds
3-(3-Aminophenylsulfonyl)aniline
aIslamic Azad University, Tehran South Branch, Tehran, Iran, and bIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran
*Correspondence e-mail: myousefi50@yahoo.com
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 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
|
Refinement
|
|
Data collection: SMART (Bruker, 1998); cell 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
10.1107/S1600536808043389/hk2599sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808043389/hk2599Isup2.hkl
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%).
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).
Data collection: SMART (Bruker, 1998); cell
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).C12H12N2O2S | F(000) = 520 |
Mr = 248.30 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 4145 independent reflections |
Radiation source: fine-focus sealed tube | 2971 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
ϕ and ω scans | θmax = 32.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −12→12 |
Tmin = 0.910, Tmax = 0.933 | k = −12→13 |
18754 measured reflections | l = −23→23 |
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(Fo2) + (0.0789P)2 + 0.6213P] where P = (Fo2 + 2Fc2)/3 |
4145 reflections | (Δ/σ)max = 0.003 |
154 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C12H12N2O2S | V = 1206.8 (4) Å3 |
Mr = 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)° |
Bruker SMART CCD area-detector diffractometer | 4145 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2971 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.933 | Rint = 0.091 |
18754 measured reflections |
R[F2 > 2σ(F2)] = 0.078 | 0 restraints |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.64 e Å−3 |
4145 reflections | Δρmin = −0.26 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.910, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18754, 4145, 2971 |
Rint | 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 |
Δρmax, Δρmin (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).
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
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.