N-[Amino­(azido)­meth­yl­idene]-4-methyl­benzene­sulfonamide

In the title mol­ecule, C₈H₁₀N₅O₂S, the amino­(azido)­methyl and p-toluene­sulfonyl moieties are inclined almost at right angles with respect to each other, making a dihedral angle of 83.49 (6)°. An intra­molecular N—H⋯O hydrogen bond gives rise to the formation of six-membered ring with graph-set motif S(6). In the crystal, inter­molecular N—H⋯O hydrogen bonding is responsible for the formation of dimers about inversion centers, which are linked through another N—H⋯O inter­action along the b axis.

Related literature

For the synthesis, see: Arshad et al. (2009). For the biological activity of sulfonamides, see: Moree et al. (1991); Arshad et al. (2008); Gennarti et al. (1994). For related structures, see: Denny et al. (1980); Müller & Bärnighausen (1970). For graph-set notation, see: Bernstein et al. (1995).

Experimental

Crystal data

• C₈H₉N₅O₂S

• M_r = 239.26

• Triclinic,

• a = 6.8986 (2) Å

• b = 7.2146 (2) Å

• c = 11.3771 (3) Å

• α = 92.244 (1)°

• β = 93.615 (1)°

• γ = 110.505 (1)°

• V = 528.18 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.30 mm⁻¹

• T = 296 K

• 0.34 × 0.17 × 0.17 mm

Data collection

• Bruker APEXII CCD diffractometer

• 8664 measured reflections

• 2549 independent reflections

• 2343 reflections with I > 2σ(I)

• R_int = 0.020

Refinement

• R[F² > 2σ(F²)] = 0.031

• wR(F²) = 0.088

• S = 1.09

• 2549 reflections

• 152 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O2^i	0.80 (2)	2.24 (2)	2.9459 (16)	148 (2)
N2—H3N⋯O1^ii	0.89 (2)	2.08 (2)	2.9481 (15)	164 (2)
N2—H2N⋯O2	0.80 (2)	2.34 (2)	2.8862 (16)	127 (2)
Symmetry codes: (i) -x+2, -y, -z; (ii) x, y-1, z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

Sulfonamides are an important class of pharmaceutical compounds (Moree et al., 1991), they exhibit a broad spectrum of biological activites which include antibacterial, diuretic, hypoglycermic, anti-convulsant, HIV protease inhibitors and for the treatment of inflammatory rheumatic and non-rheumatic processes including onsets and traumatologic lesions (Arshad et al., 2008; Gennarti et al., 1994). Herein, we report the crystal structure of the title compound.

In the title compound (Fig. 1), the azido group consisting of three nitrogen atoms carries cationic and anionic characters (Denny et al., 1980; Muller & Barnighausen, 1970). The bond distance N4—N5 is 1.112 (2) Å, which is nearly equal to a ≡bond distance between two nitrogen atoms i.e. 1.10 Å. The amino(azido)methyl (N1/C8/N2/N3/N4/N5) moiety is almost planer with r. m. s. deviation of 0.0156 Å and is oriented at a dihedral angle of 83.19 (5)° with respect to the toluene ring (C1–C7). The molecule exhibits both inter- and intra-molecular hydrogen bonding. The intermolecular hydrogen bonds result in dimers about inversion centers which are further connected through N—H···O type interactions and extended along the b axis (Tab. 1 & Fig. 2). The intramolecular hydrogen bonding N2—H2N···O2 gives rise to the formation of a six membered ring motif which can be represented mathematically as S₁¹(6) (Bernstein et al., 1995).

Related literature

For the synthesis, see: Arshad et al. (2009). For the biological activity of sulfonamides, see: Moree et al. (1991); Arshad et al. (2008); Gennarti et al. (1994). For related structures, see: Denny et al. (1980); Müller & Bärnighausen (1970). For graph-set notation, see: Bernstein et al. (1995).

S2. Experimental

A mixture of 5-aminotetrazole monohydrate (4.85 mmol, 0.5 g) and p-toluenesulfonyl chloride (4.85 mmol, 0.92 g) was stirred in distilled water (10 ml) at room temperature while pH was maintained at 9–10 in accordance with (Arshad et al., 2009). The completion of the reaction was checked by TLC. As the reaction completed, the precipitates obtained were filtered, washed with distilled water and finally dried. Suitable crystals for X-ray analysis were grown from mixture of methanol and ethyl acetate (1:1) by slow evaporation. Yield of the reaction was 84% (0.97 g). mp 408–413 K.

S3. Refinement

All H atoms were positioned geometrically with C_methyl—H = 0.96 Å, C_aromatic—H = 0.93 Å & N1—H = 0.8600 Å and treated as riding on their parent atoms with U_iso(H) = 1.2U_eq for aromatic & N1 H-atoms and 1.5U_eq for methyl H-atoms. The hydrogen atoms for primary amino group were located via fourier map allowed to refine with U_iso(H) = 1.5 U_eq(N).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: WinGX (Farrugia, 1999).

Figures

	Fig. 1. Labelled diagram of the title molecule with thermal ellipsoids drawn at 50% probability level.
	Fig. 2. Unit cell packing diagram of the title compound showing hydrogen bonds by dshed lines; H-atoms not involved in H-bonds have been excluded for clarity.

N-[Amino(azido)methylidene]-4-methylbenzenesulfonamide

Crystal data

C8H9N5O2S	Z = 2
Mr = 239.26	F(000) = 248
Triclinic, P1	Dx = 1.504 Mg m^−3
Hall symbol: -P 1	Melting point: 444(2) K
a = 6.8986 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2146 (2) Å	Cell parameters from 7120 reflections
c = 11.3771 (3) Å	θ = 3.0–28.3°
α = 92.244 (1)°	µ = 0.30 mm^−1
β = 93.615 (1)°	T = 296 K
γ = 110.505 (1)°	Needle, colourless
V = 528.18 (3) Å^3	0.34 × 0.17 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer	2343 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 28.3°, θmin = 3.2°
ϕ and ω scans	h = −9→9
8664 measured reflections	k = −9→9
2549 independent reflections	l = −15→14

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0384P)^2 + 0.179P] where P = (Fo^2 + 2Fc^2)/3
2549 reflections	(Δ/σ)max = 0.004
152 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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. The reflection 0 0 1 has been omitted as this was obscured by beamstop.

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

	x	y	z	Uiso*/Ueq
S1	0.77484 (4)	0.16023 (4)	0.12702 (3)	0.02808 (11)
O1	0.70020 (17)	0.32207 (14)	0.13239 (11)	0.0459 (3)
O2	0.87648 (15)	0.13621 (15)	0.02394 (8)	0.0370 (2)
N1	0.57940 (16)	−0.03376 (15)	0.14825 (9)	0.0291 (2)
N2	0.7254 (2)	−0.27167 (18)	0.08497 (12)	0.0383 (3)
H2N	0.825 (3)	−0.194 (3)	0.0593 (18)	0.057*
H3N	0.710 (3)	−0.399 (3)	0.0848 (18)	0.057*
N3	0.40903 (18)	−0.37488 (16)	0.15282 (11)	0.0368 (3)
N4	0.27278 (18)	−0.32615 (17)	0.19944 (11)	0.0381 (3)
N5	0.1395 (2)	−0.3067 (2)	0.24161 (15)	0.0586 (4)
C1	1.3707 (4)	0.2513 (3)	0.55842 (19)	0.0833 (8)
H1A	1.3230	0.1326	0.6002	0.125*
H1B	1.3738	0.3624	0.6088	0.125*
H1C	1.5079	0.2718	0.5354	0.125*
C2	1.2249 (3)	0.2310 (2)	0.44945 (14)	0.0514 (4)
C3	1.0431 (3)	0.2697 (3)	0.45779 (14)	0.0578 (5)
H3	1.0116	0.3084	0.5309	0.069*
C4	0.9072 (3)	0.2521 (2)	0.35961 (14)	0.0468 (4)
H4	0.7868	0.2807	0.3664	0.056*
C5	0.95280 (19)	0.19123 (17)	0.25110 (11)	0.0301 (3)
C6	1.1336 (2)	0.1525 (2)	0.24079 (13)	0.0391 (3)
H6	1.1648	0.1128	0.1678	0.047*
C7	1.2684 (3)	0.1733 (3)	0.34053 (15)	0.0508 (4)
H7	1.3904	0.1478	0.3335	0.061*
C8	0.58221 (18)	−0.21318 (17)	0.12696 (10)	0.0275 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02984 (17)	0.02068 (16)	0.03386 (18)	0.00862 (11)	0.00265 (11)	0.00626 (11)
O1	0.0493 (6)	0.0259 (5)	0.0674 (7)	0.0189 (4)	0.0042 (5)	0.0108 (5)
O2	0.0366 (5)	0.0402 (5)	0.0313 (5)	0.0090 (4)	0.0053 (4)	0.0083 (4)
N1	0.0278 (5)	0.0233 (5)	0.0357 (5)	0.0081 (4)	0.0037 (4)	0.0035 (4)
N2	0.0397 (6)	0.0250 (5)	0.0526 (7)	0.0129 (5)	0.0117 (5)	0.0047 (5)
N3	0.0366 (6)	0.0243 (5)	0.0458 (6)	0.0054 (4)	0.0072 (5)	0.0039 (4)
N4	0.0360 (6)	0.0283 (5)	0.0438 (6)	0.0028 (4)	0.0057 (5)	0.0077 (5)
N5	0.0480 (8)	0.0493 (8)	0.0766 (10)	0.0108 (6)	0.0250 (7)	0.0119 (7)
C1	0.0957 (16)	0.0691 (13)	0.0535 (11)	−0.0045 (12)	−0.0346 (11)	0.0146 (10)
C2	0.0585 (10)	0.0377 (8)	0.0402 (8)	−0.0029 (7)	−0.0128 (7)	0.0082 (6)
C3	0.0735 (12)	0.0533 (10)	0.0311 (7)	0.0038 (8)	0.0057 (7)	−0.0045 (7)
C4	0.0470 (8)	0.0470 (8)	0.0410 (8)	0.0101 (7)	0.0089 (6)	−0.0059 (6)
C5	0.0334 (6)	0.0212 (5)	0.0317 (6)	0.0045 (4)	0.0024 (5)	0.0021 (4)
C6	0.0391 (7)	0.0417 (7)	0.0366 (7)	0.0153 (6)	−0.0015 (5)	−0.0002 (6)
C7	0.0441 (8)	0.0537 (9)	0.0513 (9)	0.0154 (7)	−0.0110 (7)	0.0039 (7)
C8	0.0301 (6)	0.0233 (5)	0.0271 (5)	0.0073 (4)	−0.0009 (4)	0.0036 (4)

Geometric parameters (Å, º)

S1—O1	1.4324 (10)	C1—H1B	0.9600
S1—O2	1.4387 (10)	C1—H1C	0.9600
S1—N1	1.6064 (10)	C2—C7	1.376 (3)
S1—C5	1.7648 (13)	C2—C3	1.385 (3)
N1—C8	1.3147 (15)	C3—C4	1.384 (3)
N2—C8	1.3104 (17)	C3—H3	0.9300
N2—H2N	0.80 (2)	C4—C5	1.385 (2)
N2—H3N	0.89 (2)	C4—H4	0.9300
N3—N4	1.2523 (17)	C5—C6	1.381 (2)
N3—C8	1.4034 (15)	C6—C7	1.389 (2)
N4—N5	1.112 (2)	C6—H6	0.9300
C1—C2	1.515 (2)	C7—H7	0.9300
C1—H1A	0.9600
O1—S1—O2	117.13 (6)	C3—C2—C1	120.33 (19)
O1—S1—N1	105.65 (6)	C4—C3—C2	121.43 (15)
O2—S1—N1	112.85 (6)	C4—C3—H3	119.3
O1—S1—C5	107.75 (6)	C2—C3—H3	119.3
O2—S1—C5	107.55 (6)	C3—C4—C5	119.15 (16)
N1—S1—C5	105.20 (6)	C3—C4—H4	120.4
C8—N1—S1	121.49 (9)	C5—C4—H4	120.4
C8—N2—H2N	120.4 (15)	C6—C5—C4	120.34 (13)
C8—N2—H3N	119.0 (13)	C6—C5—S1	120.58 (10)
H2N—N2—H3N	120.6 (19)	C4—C5—S1	119.08 (11)
N4—N3—C8	113.81 (11)	C5—C6—C7	119.34 (14)
N5—N4—N3	171.56 (14)	C5—C6—H6	120.3
C2—C1—H1A	109.5	C7—C6—H6	120.3
C2—C1—H1B	109.5	C2—C7—C6	121.31 (16)
H1A—C1—H1B	109.5	C2—C7—H7	119.3
C2—C1—H1C	109.5	C6—C7—H7	119.3
H1A—C1—H1C	109.5	N2—C8—N1	130.52 (12)
H1B—C1—H1C	109.5	N2—C8—N3	111.45 (11)
C7—C2—C3	118.41 (15)	N1—C8—N3	118.03 (11)
C7—C2—C1	121.3 (2)
O1—S1—N1—C8	166.90 (10)	O1—S1—C5—C4	41.58 (13)
O2—S1—N1—C8	37.71 (12)	O2—S1—C5—C4	168.70 (11)
C5—S1—N1—C8	−79.26 (11)	N1—S1—C5—C4	−70.78 (12)
C8—N3—N4—N5	−177.3 (11)	C4—C5—C6—C7	0.6 (2)
C7—C2—C3—C4	−0.2 (3)	S1—C5—C6—C7	−178.38 (12)
C1—C2—C3—C4	−179.94 (16)	C3—C2—C7—C6	−0.5 (3)
C2—C3—C4—C5	1.0 (3)	C1—C2—C7—C6	179.26 (16)
C3—C4—C5—C6	−1.2 (2)	C5—C6—C7—C2	0.3 (2)
C3—C4—C5—S1	177.75 (12)	S1—N1—C8—N2	−2.0 (2)
O1—S1—C5—C6	−139.43 (11)	S1—N1—C8—N3	177.16 (9)
O2—S1—C5—C6	−12.31 (13)	N4—N3—C8—N2	176.19 (12)
N1—S1—C5—C6	108.21 (11)	N4—N3—C8—N1	−3.12 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2^i	0.80 (2)	2.24 (2)	2.9459 (16)	148 (2)
N2—H3N···O1^ii	0.89 (2)	2.08 (2)	2.9481 (15)	164 (2)
N2—H2N···O2	0.80 (2)	2.34 (2)	2.8862 (16)	127 (2)

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

 

Footnotes

‡X-ray Diffraction and Physical Laboratory, Department of Physics, School of Physical Sciences, University of the Punjab, Quaid-e-Azam Campus, Lahore 54590, Pakistan.