N-Benzyl­pyridine-2-sulfonamide

Chen, X.-P.; Han, S.-F.

doi:10.1107/S1600536809018054

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1414

doi:10.1107/S1600536809018054

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N-Benzylpyridine-2-sulfonamide

Xiao-Ping Chen ^a and Shou-Fa Han ^a ^*

^aDepartment of Chemistry and the Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: xpchen1217@163.com

(Received 7 May 2009; accepted 13 May 2009; online 29 May 2009)

The title compound, C₁₂H₁₂N₂O₂S, was obtained by the reaction of 2-mercaptopyridine and benzylamine. The dihedral angle between the benzene and pyridine rings is 75.75 (9)°. In the crystal, molecules are linked into chains along the c axis by N—H⋯O and N—H⋯N hydrogen bonds; the chains are cross-linked into a two-dimensional network parallel to the bc plane via C—H⋯O hydrogen bonds.

Related literature

For the synthesis, see: Wright et al. (2006 ). For applications of sulfonamides, see: Connor (1998 ). For the structure of N-benzylquinoline-8-sulfonamide, see: Andrighetti-Fröhner et al. (2006 ).

Experimental

Crystal data

C₁₂H₁₂N₂O₂S
M_r = 248.30
Monoclinic, P 2₁ /c
a = 11.099 (2) Å
b = 10.709 (2) Å
c = 9.513 (2) Å
β = 91.893 (4)°
V = 1130.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 173 K
0.50 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.823, T_max = 1.00 (expected range = 0.783–0.951)
5922 measured reflections
2195 independent reflections
2078 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.101
S = 1.00
2195 reflections
157 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.82 (2)	2.49 (2)	3.264 (2)	157 (2)
N1—H1⋯O1ⁱ	0.82 (2)	2.50 (2)	3.111 (2)	132 (2)
C4—H4⋯O1ⁱⁱ	0.95	2.52	3.406 (2)	154
C5—H5⋯O2ⁱⁱⁱ	0.95	2.51	3.121 (2)	122
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018054/ci2800sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018054/ci2800Isup2.hkl

checkCIF report

Comment top

Sulfonamides are an important category of pharmaceutical compounds with a broad spectrum of biological activities, as good antibacterials, diuretics, anticonvulsants, and HIV protease inhibitors (Connor, 1998).

The molecular structure of the title compound is shown in Fig. 1. Bond lengths and angles are comparable to those observed for N-benzylquinoline-8-sulfonamide (Andrighetti-Fröhner et al., 2006). The C1—S1—N1—C6 torsion angle is -71.85 (15)°. The dihedral angle between the benzene and pyridine rings is 75.75 (9)°.

Hydrogen bonding plays a significant role in stabilizing the crystal structure; see Table 1 for geometric parameters and symmetry operations. The molecules are linked into a chain along the c axis by N—H···O and N—H···N hydrogen bonds. The chains are cross-linked via C—H···O hydrogen bonds to form a two-dimensional network parallel to the bc plane.

Related literature top

For the synthesis, see: Wright et al. (2006). For applications of sulfonamides, see: Connor (1998). For the structure of N-benzylquinoline-8-sulfonamide, see: Andrighetti-Fröhner et al. (2006).

Experimental top

The title compound was synthesized using a similar synthetic method for the preparation of heteroaryl sulfonamides (Wright et al., 2006). 2-Mercaptopyridine (0.56 g, 5 mmol) was stirred in a mixture of 25 mL of dichloromethane and 25 mL of 1 M HCl in a 125 ml flask for 8 min at 263 to 268 K. Cold sodium hypochlorite (6% solution, 0.68 M, 26 ml, 18 mmol, 3.3 equiv) was then added dropwise with very rapid stirring, maintaining the internal temperature at 263 to 268 K. The mixture was stirred for 30 min at 263 to 268 K after the addition was completed, the mixture was transferred to a separatory funnel (pre-cooled with ice water) and the dichloromethane layer was rapidly separated and collected in a clean 125 ml flask cooled in a ice-salt bath. Benzylamine (1.1 ml, 10 mmol) was added with stirring, when the dichloromethane layer became a white suspension, the flask was removed to an ice-water bath and the suspension was stirred for 30 min at 273 K. The suspension was then washed with 1 M HCl, then with water and brine. Drying (MgSO₄) and concentration afforded the title compound as a white solid with 81% yield. Single crystals of the title compound were grown in a petroleum ether-ethyl acetate solution (3:1 v/v) by slow evaporation.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.

Figures top

Fig. 1. The molecular structure of the compound, with 50% probability displacement ellipsoids (arbitrary spheres for H atoms).

N-Benzylpyridine-2-sulfonamide top

Crystal data top

C₁₂H₁₂N₂O₂S	F(000) = 520
M_r = 248.30	D_x = 1.459 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4484 reflections
a = 11.099 (2) Å	θ = 2.6–28.2°
b = 10.709 (2) Å	µ = 0.28 mm⁻¹
c = 9.513 (2) Å	T = 173 K
β = 91.893 (4)°	Needle, colourless
V = 1130.1 (4) Å³	0.50 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART APEX area-detector diffractometer	2195 independent reflections
Radiation source: fine-focus sealed tube	2078 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→13
T_min = 0.823, T_max = 1.00	k = −11→13
5922 measured reflections	l = −11→11

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0567P)² + 0.7208P] where P = (F_o² + 2F_c²)/3
2195 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₂H₁₂N₂O₂S	V = 1130.1 (4) Å³
M_r = 248.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.099 (2) Å	µ = 0.28 mm⁻¹
b = 10.709 (2) Å	T = 173 K
c = 9.513 (2) Å	0.50 × 0.20 × 0.18 mm
β = 91.893 (4)°

Data collection top

Bruker SMART APEX area-detector diffractometer	2195 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2078 reflections with I > 2σ(I)
T_min = 0.823, T_max = 1.00	R_int = 0.021
5922 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.32 e Å⁻³
2195 reflections	Δρ_min = −0.40 e Å⁻³
157 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	0.29480 (4)	0.35956 (4)	−0.07138 (4)	0.02300 (15)
O1	0.23235 (11)	0.37287 (12)	−0.20382 (13)	0.0297 (3)
O2	0.35175 (11)	0.46543 (11)	−0.00687 (13)	0.0303 (3)
N1	0.20157 (13)	0.30466 (14)	0.03864 (16)	0.0247 (3)
H1	0.2331 (19)	0.299 (2)	0.118 (2)	0.030*
N2	0.37751 (14)	0.15428 (14)	−0.18353 (16)	0.0288 (3)
C1	0.40853 (15)	0.24506 (16)	−0.09461 (17)	0.0242 (4)
C2	0.51786 (16)	0.25414 (18)	−0.02210 (19)	0.0296 (4)
H2	0.5353	0.3219	0.0397	0.036*
C3	0.60085 (17)	0.16046 (19)	−0.0433 (2)	0.0336 (4)
H3	0.6775	0.1622	0.0041	0.040*
C4	0.57087 (17)	0.06477 (18)	−0.13383 (19)	0.0332 (4)
H4	0.6264	−0.0009	−0.1497	0.040*
C5	0.45909 (17)	0.06519 (18)	−0.20149 (19)	0.0329 (4)
H5	0.4393	−0.0014	−0.2640	0.039*
C6	0.11909 (16)	0.20325 (17)	−0.00404 (19)	0.0297 (4)
H6A	0.1627	0.1226	0.0006	0.036*
H6B	0.0903	0.2166	−0.1025	0.036*
C7	0.01310 (15)	0.19830 (16)	0.09002 (17)	0.0240 (4)
C8	−0.01617 (16)	0.08823 (16)	0.15529 (19)	0.0274 (4)
H8	0.0322	0.0162	0.1424	0.033*
C9	−0.11535 (16)	0.08132 (18)	0.23949 (19)	0.0321 (4)
H9	−0.1354	0.0046	0.2830	0.039*
C10	−0.18463 (17)	0.18527 (19)	0.2601 (2)	0.0345 (4)
H10	−0.2523	0.1809	0.3185	0.041*
C11	−0.15598 (17)	0.29609 (18)	0.1958 (2)	0.0353 (4)
H11	−0.2037	0.3683	0.2104	0.042*
C12	−0.05840 (17)	0.30255 (17)	0.1105 (2)	0.0301 (4)
H12	−0.0399	0.3790	0.0653	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0240 (2)	0.0224 (2)	0.0226 (2)	−0.00314 (15)	0.00148 (16)	0.00164 (15)
O1	0.0300 (6)	0.0336 (7)	0.0254 (7)	−0.0023 (5)	−0.0006 (5)	0.0055 (5)
O2	0.0312 (6)	0.0233 (6)	0.0364 (7)	−0.0054 (5)	−0.0001 (5)	0.0000 (5)
N1	0.0253 (7)	0.0274 (8)	0.0215 (7)	−0.0047 (6)	0.0020 (6)	−0.0024 (6)
N2	0.0323 (8)	0.0296 (8)	0.0245 (8)	−0.0012 (6)	0.0005 (6)	−0.0012 (6)
C1	0.0248 (8)	0.0264 (8)	0.0215 (8)	−0.0040 (7)	0.0046 (6)	0.0024 (6)
C2	0.0260 (9)	0.0326 (9)	0.0303 (9)	−0.0045 (7)	0.0012 (7)	0.0000 (7)
C3	0.0259 (9)	0.0405 (10)	0.0346 (10)	−0.0009 (8)	0.0040 (7)	0.0058 (8)
C4	0.0355 (10)	0.0352 (10)	0.0295 (9)	0.0068 (8)	0.0098 (7)	0.0040 (8)
C5	0.0415 (10)	0.0307 (9)	0.0266 (9)	0.0020 (8)	0.0039 (8)	−0.0030 (7)
C6	0.0315 (9)	0.0287 (9)	0.0293 (9)	−0.0085 (7)	0.0084 (7)	−0.0066 (7)
C7	0.0233 (8)	0.0270 (8)	0.0217 (8)	−0.0053 (7)	0.0000 (6)	−0.0029 (6)
C8	0.0276 (8)	0.0240 (8)	0.0306 (9)	−0.0019 (7)	0.0003 (7)	−0.0022 (7)
C9	0.0340 (9)	0.0310 (9)	0.0315 (9)	−0.0079 (8)	0.0042 (7)	0.0035 (8)
C10	0.0275 (9)	0.0421 (11)	0.0343 (10)	−0.0065 (8)	0.0088 (7)	−0.0059 (8)
C11	0.0292 (9)	0.0331 (10)	0.0438 (11)	0.0038 (8)	0.0020 (8)	−0.0049 (8)
C12	0.0329 (9)	0.0251 (9)	0.0323 (9)	−0.0015 (7)	−0.0008 (7)	0.0022 (7)

Geometric parameters (Å, º) top

S1—O1	1.4249 (13)	C5—H5	0.95
S1—O2	1.4268 (13)	C6—C7	1.502 (2)
S1—N1	1.6073 (15)	C6—H6A	0.99
S1—C1	1.7787 (18)	C6—H6B	0.99
N1—C6	1.469 (2)	C7—C8	1.376 (2)
N1—H1	0.82 (2)	C7—C12	1.387 (3)
N2—C1	1.327 (2)	C8—C9	1.385 (3)
N2—C5	1.330 (2)	C8—H8	0.95
C1—C2	1.379 (2)	C9—C10	1.371 (3)
C2—C3	1.381 (3)	C9—H9	0.95
C2—H2	0.95	C10—C11	1.377 (3)
C3—C4	1.373 (3)	C10—H10	0.95
C3—H3	0.95	C11—C12	1.376 (3)
C4—C5	1.379 (3)	C11—H11	0.95
C4—H4	0.95	C12—H12	0.95

O1—S1—O2	119.76 (8)	N1—C6—C7	110.77 (14)
O1—S1—N1	107.91 (8)	N1—C6—H6A	109.5
O2—S1—N1	107.23 (8)	C7—C6—H6A	109.5
O1—S1—C1	106.59 (8)	N1—C6—H6B	109.5
O2—S1—C1	107.16 (8)	C7—C6—H6B	109.5
N1—S1—C1	107.67 (8)	H6A—C6—H6B	108.1
C6—N1—S1	119.95 (12)	C8—C7—C12	118.78 (16)
C6—N1—H1	116.0 (15)	C8—C7—C6	120.01 (16)
S1—N1—H1	111.2 (15)	C12—C7—C6	121.20 (16)
C1—N2—C5	116.37 (15)	C7—C8—C9	120.72 (17)
N2—C1—C2	125.17 (17)	C7—C8—H8	119.6
N2—C1—S1	114.46 (13)	C9—C8—H8	119.6
C2—C1—S1	120.36 (14)	C10—C9—C8	119.98 (17)
C1—C2—C3	117.12 (17)	C10—C9—H9	120.0
C1—C2—H2	121.4	C8—C9—H9	120.0
C3—C2—H2	121.4	C9—C10—C11	119.85 (18)
C4—C3—C2	119.00 (18)	C9—C10—H10	120.1
C4—C3—H3	120.5	C11—C10—H10	120.1
C2—C3—H3	120.5	C12—C11—C10	120.18 (18)
C3—C4—C5	119.10 (18)	C12—C11—H11	119.9
C3—C4—H4	120.5	C10—C11—H11	119.9
C5—C4—H4	120.5	C11—C12—C7	120.48 (17)
N2—C5—C4	123.24 (17)	C11—C12—H12	119.8
N2—C5—H5	118.4	C7—C12—H12	119.8
C4—C5—H5	118.4

O1—S1—N1—C6	42.85 (16)	C2—C3—C4—C5	0.3 (3)
O2—S1—N1—C6	173.12 (13)	C1—N2—C5—C4	−0.4 (3)
C1—S1—N1—C6	−71.85 (15)	C3—C4—C5—N2	−0.1 (3)
C5—N2—C1—C2	0.8 (3)	S1—N1—C6—C7	−159.20 (13)
C5—N2—C1—S1	−178.54 (13)	N1—C6—C7—C8	−126.83 (17)
O1—S1—C1—N2	−34.71 (14)	N1—C6—C7—C12	54.6 (2)
O2—S1—C1—N2	−164.06 (12)	C12—C7—C8—C9	0.2 (3)
N1—S1—C1—N2	80.87 (14)	C6—C7—C8—C9	−178.38 (16)
O1—S1—C1—C2	145.94 (14)	C7—C8—C9—C10	−0.9 (3)
O2—S1—C1—C2	16.58 (16)	C8—C9—C10—C11	0.6 (3)
N1—S1—C1—C2	−98.49 (15)	C9—C10—C11—C12	0.3 (3)
N2—C1—C2—C3	−0.6 (3)	C10—C11—C12—C7	−1.0 (3)
S1—C1—C2—C3	178.71 (13)	C8—C7—C12—C11	0.7 (3)
C1—C2—C3—C4	0.0 (3)	C6—C7—C12—C11	179.29 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.82 (2)	2.49 (2)	3.264 (2)	157 (2)
N1—H1···O1ⁱ	0.82 (2)	2.50 (2)	3.111 (2)	132 (2)
C4—H4···O1ⁱⁱ	0.95	2.52	3.406 (2)	154
C5—H5···O2ⁱⁱⁱ	0.95	2.51	3.121 (2)	122

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₂S
M_r	248.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.099 (2), 10.709 (2), 9.513 (2)
β (°)	91.893 (4)
V (Å³)	1130.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.50 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.823, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	5922, 2195, 2078
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.101, 1.00
No. of reflections	2195
No. of parameters	157
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.40

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.82 (2)	2.49 (2)	3.264 (2)	157 (2)
N1—H1···O1ⁱ	0.82 (2)	2.50 (2)	3.111 (2)	132 (2)
C4—H4···O1ⁱⁱ	0.95	2.52	3.406 (2)	154
C5—H5···O2ⁱⁱⁱ	0.95	2.51	3.121 (2)	122

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

Acknowledgements

The authors thank the National Science Foundation of China (grant No. 20802060) for supporting this work.

References

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