1-Azido-N′-(phenylsulfonyl)methan­imid­amide

Khan, I.U.; Mahmood, A.; Arshad, M.N.; Shahzad, S.A.

doi:10.1107/S1600536811037718

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2703

https://doi.org/10.1107/S1600536811037718

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1-Azido-N′-(phenylsulfonyl)methanimidamide

Islam Ullah Khan,^a ^* Ayyaz Mahmood,^a Muhammad Nadeem Arshad ^a ‡ and Sohail Anjum Shahzad ^a

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan
^*Correspondence e-mail: iuklodhi@yahoo.com, mnachemist@hotmail.com

(Received 11 September 2011; accepted 15 September 2011; online 30 September 2011)

In the title compound, C₇H₇N₅O₂S, the aromatic ring is oriented at dihedral angles of 79.46 (2) and 89.17 (2)°, respectively, with respect to the amino(azido)methyl and the S(6) six-membered ring motif generated by an intramolecular N—H⋯O interaction [N⋯O = 2.8901 (15) Å]. Intermolecular N—H⋯O hydrogen bonds [N⋯O = 2.9177 (15) and 2.9757 (15) Å] generate an infinite one-dimensional network along the base vector (010).

Related literature

For the synthesis, see: Mahmood et al. (2011 ). For related structures, see: Denny et al. (1980 ); Mahmood et al. (2011); Müller & Bärnighausen (1970 ). For graph-set notations, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₇N₅O₂S
M_r = 225.24
Triclinic, $[P \overline 1]$
a = 7.0399 (2) Å
b = 7.1714 (2) Å
c = 10.3670 (3) Å
α = 90.267 (1)°
β = 98.997 (1)°
γ = 110.358 (1)°
V = 483.67 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 296 K
0.35 × 0.31 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.896, T_max = 0.962
8598 measured reflections
2422 independent reflections
2246 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.097
S = 1.06
2422 reflections
143 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O1ⁱ	0.85 (1)	2.10 (1)	2.9177 (15)	163 (2)
N2—H2N⋯O2ⁱⁱ	0.84 (1)	2.23 (1)	2.9757 (15)	148 (2)
N2—H2N⋯O2	0.84 (1)	2.33 (2)	2.8901 (15)	125 (2)
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -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: PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811037718/pv2447sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037718/pv2447Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811037718/pv2447Isup3.cml

checkCIF report

Comment top

In continuation to our studies on sulfonamide derivatives we now report the structure of the title compound which is an analogue of the compound reported earlier (Mahmood et al., 2011),

In the title molecule (Fig. 1), the azido group (N3/N4/N5) carries cationic and anionic characters as observed in the previously report compound and reportedin the literature (Denny et al., 1980; Müller & Bärnighausen, 1970). The bond distance N4—N5 is 1.105 (19) Å, which clearly indicates its tripple bond character (N≡N = 1.10 Å) The other bond distances, C7—N1 = 1.3105 (15) Å & C7—N3 = 1.4022 (16) Å represent C to N double and single covalent bonds, respectively. The planer amino(azido)methyl (N1/C8/N2/N3/N4/N5) moiety (r. m. s. deviation of 0.0164 A°) is oriented at a dihedral angle of 79.46 (6)° with respect to the toluene ring. The intramolecular hydrogen bond N2—H2N···O2 produces a six membered ring motif S(6) (Bernstein et al., 1995) which is inclined almost perpendicular (89.17 (2)°) to the aromatic ring (C1—C6). The intermolecular hydrogen bonds are very much in accord with the corresponding hydrogen bonding reported in the previous analogue (Mahmood et al., 2011) as it forms dimers which are further connected through N—H···O type interactions and extended along the b axis (Table. 2, Figure. 2).

Related literature top

For the synthesis, see: Mahmood et al. (2011). For related structures, see: Denny et al. (1980); Mahmood et al. (2011); Müller & Bärnighausen (1970). For graph-set notations, see: Bernstein et al. (1995).

Experimental top

The titile compound was prepared in accordance with reported method (Mahmood et al., 2011) and recrystalized from a mixture of methanol and ethylacetate (1:1) by slow evaporation.

Structure description top

In continuation to our studies on sulfonamide derivatives we now report the structure of the title compound which is an analogue of the compound reported earlier (Mahmood et al., 2011),

For the synthesis, see: Mahmood et al. (2011). For related structures, see: Denny et al. (1980); Mahmood et al. (2011); Müller & Bärnighausen (1970). For graph-set notations, see: Bernstein et al. (1995).

Computing details top

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: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Thermal ellipsoid plot of the title compound drawn at 50% probability level showing the intramolecular hydrogen bonding via dshed line.
	Fig. 2. Unit cell packing diagram showing the hydrogen bonds via dshed lines, the hydrogen atoms not involved in hydrogen bonding have been omitted.

1-azido-N'-(phenylsulfonyl)methanimidamide top

Crystal data top

C₇H₇N₅O₂S	Z = 2
M_r = 225.24	F(000) = 232
Triclinic, P1	D_x = 1.547 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0399 (2) Å	Cell parameters from 6153 reflections
b = 7.1714 (2) Å	θ = 3.0–28.5°
c = 10.3670 (3) Å	µ = 0.32 mm⁻¹
α = 90.267 (1)°	T = 296 K
β = 98.997 (1)°	Plate, colourless
γ = 110.358 (1)°	0.35 × 0.31 × 0.12 mm
V = 483.67 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	2422 independent reflections
Radiation source: fine-focus sealed tube	2246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 28.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→9
T_min = 0.896, T_max = 0.962	k = −9→9
8598 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.059P)² + 0.1064P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2422 reflections	Δρ_max = 0.30 e Å⁻³
143 parameters	Δρ_min = −0.30 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.178 (13)

Crystal data top

C₇H₇N₅O₂S	γ = 110.358 (1)°
M_r = 225.24	V = 483.67 (2) Å³
Triclinic, P1	Z = 2
a = 7.0399 (2) Å	Mo Kα radiation
b = 7.1714 (2) Å	µ = 0.32 mm⁻¹
c = 10.3670 (3) Å	T = 296 K
α = 90.267 (1)°	0.35 × 0.31 × 0.12 mm
β = 98.997 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2422 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2246 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.962	R_int = 0.025
8598 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.30 e Å⁻³
2422 reflections	Δρ_min = −0.30 e Å⁻³
143 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.29872 (4)	0.66106 (4)	0.14334 (3)	0.03096 (13)
O1	0.22775 (17)	0.82450 (15)	0.15249 (12)	0.0501 (3)
O2	0.37880 (15)	0.63793 (15)	0.02689 (9)	0.0407 (2)
N4	−0.18866 (18)	0.17258 (17)	0.21333 (12)	0.0412 (3)
N3	−0.05785 (18)	0.12367 (17)	0.16650 (12)	0.0406 (3)
C7	0.10971 (19)	0.28677 (17)	0.14142 (11)	0.0297 (2)
N1	0.11035 (16)	0.46635 (15)	0.16629 (10)	0.0318 (2)
N2	0.24609 (19)	0.22835 (17)	0.09706 (13)	0.0405 (3)
H2N	0.346 (2)	0.310 (2)	0.0691 (19)	0.061*
H1N	0.230 (3)	0.1058 (15)	0.096 (2)	0.061*
N5	−0.3157 (2)	0.1915 (2)	0.25610 (18)	0.0632 (4)
C1	0.49613 (19)	0.69027 (18)	0.27813 (12)	0.0317 (3)
C2	0.6735 (2)	0.6594 (2)	0.26000 (14)	0.0415 (3)
H2	0.6882	0.6209	0.1775	0.050*
C3	0.8287 (3)	0.6865 (3)	0.36578 (18)	0.0598 (5)
H3	0.9484	0.6653	0.3549	0.072*
C4	0.8055 (3)	0.7449 (3)	0.48716 (18)	0.0676 (5)
H4	0.9109	0.7641	0.5579	0.081*
C6	0.4725 (3)	0.7480 (3)	0.40091 (15)	0.0498 (4)
H6	0.3525	0.7680	0.4125	0.060*
C5	0.6289 (3)	0.7752 (3)	0.50550 (17)	0.0650 (5)
H5	0.6150	0.8141	0.5882	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.03183 (19)	0.02277 (18)	0.04005 (19)	0.01043 (12)	0.00916 (12)	0.00792 (11)
O1	0.0508 (6)	0.0279 (5)	0.0787 (8)	0.0209 (5)	0.0146 (5)	0.0126 (5)
O2	0.0400 (5)	0.0447 (6)	0.0364 (5)	0.0115 (4)	0.0113 (4)	0.0105 (4)
N4	0.0348 (6)	0.0323 (6)	0.0514 (7)	0.0040 (5)	0.0105 (5)	0.0104 (5)
N3	0.0391 (6)	0.0269 (5)	0.0526 (7)	0.0052 (5)	0.0138 (5)	0.0038 (5)
C7	0.0306 (6)	0.0250 (5)	0.0314 (5)	0.0078 (4)	0.0040 (4)	0.0044 (4)
N1	0.0294 (5)	0.0253 (5)	0.0416 (5)	0.0092 (4)	0.0095 (4)	0.0040 (4)
N2	0.0444 (7)	0.0260 (5)	0.0560 (7)	0.0136 (5)	0.0194 (5)	0.0053 (5)
N5	0.0470 (8)	0.0558 (9)	0.0908 (11)	0.0143 (7)	0.0320 (8)	0.0185 (8)
C1	0.0327 (6)	0.0232 (5)	0.0370 (6)	0.0058 (4)	0.0086 (5)	0.0025 (4)
C2	0.0364 (7)	0.0482 (8)	0.0397 (6)	0.0144 (6)	0.0074 (5)	−0.0006 (6)
C3	0.0377 (8)	0.0830 (13)	0.0552 (9)	0.0204 (8)	0.0000 (7)	0.0004 (9)
C4	0.0518 (10)	0.0894 (15)	0.0448 (8)	0.0108 (10)	−0.0068 (7)	−0.0014 (8)
C6	0.0487 (8)	0.0557 (9)	0.0453 (8)	0.0155 (7)	0.0158 (6)	−0.0042 (7)
C5	0.0696 (12)	0.0791 (13)	0.0376 (7)	0.0152 (10)	0.0099 (8)	−0.0089 (8)

Geometric parameters (Å, º) top

S1—O1	1.4330 (10)	C1—C2	1.3811 (19)
S1—O2	1.4419 (10)	C1—C6	1.3885 (18)
S1—N1	1.6057 (11)	C2—C3	1.382 (2)
S1—C1	1.7650 (13)	C2—H2	0.9300
N4—N5	1.1055 (19)	C3—C4	1.376 (3)
N4—N3	1.2529 (17)	C3—H3	0.9300
N3—C7	1.4022 (16)	C4—C5	1.375 (3)
C7—N1	1.3105 (15)	C4—H4	0.9300
C7—N2	1.3134 (16)	C6—C5	1.379 (3)
N2—H2N	0.837 (9)	C6—H6	0.9300
N2—H1N	0.846 (9)	C5—H5	0.9300

O1—S1—O2	117.23 (7)	C6—C1—S1	119.38 (11)
O1—S1—N1	105.53 (6)	C1—C2—C3	119.31 (14)
O2—S1—N1	112.47 (6)	C1—C2—H2	120.3
O1—S1—C1	107.62 (7)	C3—C2—H2	120.3
O2—S1—C1	107.32 (6)	C4—C3—C2	119.78 (16)
N1—S1—C1	106.07 (6)	C4—C3—H3	120.1
N5—N4—N3	171.37 (15)	C2—C3—H3	120.1
N4—N3—C7	113.51 (11)	C5—C4—C3	121.01 (17)
N1—C7—N2	130.53 (12)	C5—C4—H4	119.5
N1—C7—N3	118.15 (11)	C3—C4—H4	119.5
N2—C7—N3	111.31 (11)	C5—C6—C1	119.30 (15)
C7—N1—S1	121.29 (9)	C5—C6—H6	120.4
C7—N2—H2N	120.8 (13)	C1—C6—H6	120.4
C7—N2—H1N	118.7 (13)	C4—C5—C6	119.79 (16)
H2N—N2—H1N	120.5 (18)	C4—C5—H5	120.1
C2—C1—C6	120.81 (13)	C6—C5—H5	120.1
C2—C1—S1	119.80 (10)

N4—N3—C7—N1	−1.19 (18)	O2—S1—C1—C6	169.50 (11)
N4—N3—C7—N2	177.67 (12)	N1—S1—C1—C6	−70.08 (12)
N2—C7—N1—S1	0.0 (2)	C6—C1—C2—C3	0.0 (2)
N3—C7—N1—S1	178.63 (9)	S1—C1—C2—C3	178.76 (13)
O1—S1—N1—C7	167.67 (11)	C1—C2—C3—C4	−0.5 (3)
O2—S1—N1—C7	38.71 (12)	C2—C3—C4—C5	0.6 (3)
C1—S1—N1—C7	−78.31 (11)	C2—C1—C6—C5	0.2 (2)
O1—S1—C1—C2	−136.24 (12)	S1—C1—C6—C5	−178.49 (14)
O2—S1—C1—C2	−9.24 (13)	C3—C4—C5—C6	−0.3 (4)
N1—S1—C1—C2	111.19 (12)	C1—C6—C5—C4	−0.1 (3)
O1—S1—C1—C6	42.49 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O1ⁱ	0.85 (1)	2.10 (1)	2.9177 (15)	163 (2)
N2—H2N···O2ⁱⁱ	0.84 (1)	2.23 (1)	2.9757 (15)	148 (2)
N2—H2N···O2	0.84 (1)	2.33 (2)	2.8901 (15)	125 (2)

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₅O₂S
M_r	225.24
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.0399 (2), 7.1714 (2), 10.3670 (3)
α, β, γ (°)	90.267 (1), 98.997 (1), 110.358 (1)
V (Å³)	483.67 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.35 × 0.31 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.896, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	8598, 2422, 2246
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.097, 1.06
No. of reflections	2422
No. of parameters	143
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.30

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O1ⁱ	0.846 (9)	2.099 (11)	2.9177 (15)	162.8 (19)
N2—H2N···O2ⁱⁱ	0.837 (9)	2.233 (13)	2.9757 (15)	147.8 (18)
N2—H2N···O2	0.837 (9)	2.330 (17)	2.8901 (15)	124.7 (16)

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

Footnotes

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

Acknowledgements

The authors acknowledge the Higher Education Commission of Pakistan for the purchase of the diffractometer under the grant for strengthening of the Materials Chemistry Laboratory at GC University, Lahore, Pakistan.

References

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