2-(4-Sulfamoylphen­yl)hydrazin-1-ium chloride

Abstract

The hydrazinium residue in the cation of the title salt, C₆H₁₀N₃O₂S⁺·Cl⁻, is twisted out of the plane of the benzene ring to which it is attached [N—N—C—C torsion angle = 25.9 (2)°] and the amino group is almost perpendicular to the benzene ring [N—S—C—C torsion angle = 88.71 (16)°]. In the crystal, the cations are linked by N—H⋯O hydrogen bonds and π–π inter­actions [ring centroid distance = 3.7280 (11) Å], forming layers in the bc plane that are connected by N—H⋯Cl hydrogen bonds.

Related literature  

For background to the biological applications of related sulfonamides, see: Croitoru et al. (2004 ▶); Dogruer et al. (2010 ▶). For related structures, see: Asiri et al. (2011 ▶, 2012 ▶).

Experimental  

Crystal data  

• C₆H₁₀N₃O₂S⁺·Cl⁻

• M _r = 223.68

• Monoclinic,

• a = 10.2203 (8) Å

• b = 9.8883 (7) Å

• c = 9.1948 (8) Å

• β = 107.647 (9)°

• V = 885.51 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 0.64 mm⁻¹

• T = 100 K

• 0.35 × 0.30 × 0.25 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.808, T _max = 0.857

• 3570 measured reflections

• 2026 independent reflections

• 1767 reflections with I > 2σ(I)

• R _int = 0.024

Refinement  

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.084

• S = 1.03

• 2026 reflections

• 142 parameters

• 6 restraints

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

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.43 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812011452/hb6680Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.89 (1)	2.28 (1)	3.1319 (17)	162 (2)
N1—H2⋯O2i	0.88 (2)	2.03 (2)	2.835 (2)	152 (2)
N1—H3⋯Cl1ii	0.88 (2)	2.46 (2)	3.2136 (18)	144 (2)
N1—H3⋯O1iii	0.88 (2)	2.46 (2)	3.083 (2)	129 (2)
N2—H4⋯Cl1iv	0.89 (2)	2.67 (2)	3.3647 (16)	137 (2)
N3—H5⋯Cl1v	0.88 (1)	2.42 (2)	3.2656 (17)	163 (2)
N3—H6⋯Cl1vi	0.87 (1)	2.48 (2)	3.2467 (17)	147 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

Sulphonamides related to the title salt, 2-(4-sulfamoylphenyl)hydrazinium chloride (I), are known to possess pharmacological properties. For example, N-substituted pyrazolyl-benzensulfonamides are known to selectively inhibit COX–2 (Croitoru et al., 2004) and other derivatives were reported to exhibit anti-microbial and anti-fungal activities (Dogruer et al. 2010). The crystal and molecular structure of 2-(4-sulfamoylphenyl)hydrazinium chloride (I) is reported herein, as a continuation of structural studies of these systems (Asiri et al., 2011; Asiri et al., 2012).

The crystallographic asymmetric unit of (I) comprises a hydrazinium cation charge balanced by a chloride, Fig. 1. The hydrazinium residue is twisted out of the plane of the benzene ring to which it is attached as seen in the value of the N1—N2—C4—C3 torsion angle of 25.9 (2)°. The amino group occupies a position perpendicular to the benzene ring with the N3—S1—C1—C2 torsion angle being 88.71 (16)°; the ammonium and amino groups are orientated to opposite sides of the benzene ring.

The cations are linked by N—H···O hydrogen bonds, Table 1, and π—π interactions [ring centroid distance = 3.7280 (11) Å for symmetry operation: 1 - x, 1 - y, 1 - z] to form layers in the bc plane. The cations are connected to the chloride anions by N—H···Cl hydrogen bonds, Table 1, leading to a three-dimensional architecture.

Experimental

Diazotization of sulfonamide with NaNO₂/HCl followed by reduction with sodium sulfite afforded the title salt which was crystallized from ethanol as irregular light-brown chunks. Yield: 72%. M.pt. 488–490 K.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H = 0.95 Å, U_iso(H) = 1.2U_eq(C)] and were included in the refinement in the riding model approximation. The N—H atoms were located in a difference Fourier map, and were refined with a distance restraint of N—H = 0.88±0.01 Å; their U_iso values were refined.

Figures

Fig. 1.

The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.

Fig. 2.

A view in projection down the c axis of the unit-cell contents of (I). The N—H···O, N—H···Cl and π—π interactions are shown as orange, blue and purple dashed lines, respectively.

Crystal data

C6H10N3O2S+·Cl−	F(000) = 464
Mr = 223.68	Dx = 1.678 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2194 reflections
a = 10.2203 (8) Å	θ = 2.3–27.5°
b = 9.8883 (7) Å	µ = 0.64 mm−1
c = 9.1948 (8) Å	T = 100 K
β = 107.647 (9)°	Irregular, light-brown
V = 885.51 (12) Å3	0.35 × 0.30 × 0.25 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	2026 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1767 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.9°
ω scan	h = −13→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→12
Tmin = 0.808, Tmax = 0.857	l = −9→11
3570 measured reflections

Refinement

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0404P)2 + 0.3504P] where P = (Fo2 + 2Fc2)/3
2026 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.39 e Å−3
6 restraints	Δρmin = −0.43 e Å−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.86073 (5)	−0.03338 (4)	0.61107 (5)	0.01345 (14)
S1	0.21204 (4)	0.40936 (4)	0.48750 (5)	0.00899 (13)
O1	0.17687 (13)	0.36536 (13)	0.33148 (14)	0.0118 (3)
N3	0.13229 (16)	0.31234 (16)	0.57265 (18)	0.0114 (3)
N1	0.89021 (16)	0.26661 (17)	0.72569 (19)	0.0124 (3)
N2	0.80635 (16)	0.32732 (16)	0.80730 (17)	0.0119 (3)
O2	0.18027 (13)	0.54566 (12)	0.51886 (15)	0.0129 (3)
C1	0.38970 (18)	0.38531 (18)	0.5743 (2)	0.0095 (4)
C2	0.46066 (19)	0.28593 (18)	0.5230 (2)	0.0112 (4)
H2A	0.4148	0.2318	0.4374	0.013*
C3	0.59980 (19)	0.26604 (18)	0.5979 (2)	0.0108 (4)
H3A	0.6489	0.1979	0.5635	0.013*
C4	0.66731 (18)	0.34606 (18)	0.7235 (2)	0.0094 (4)
C5	0.59489 (19)	0.44578 (18)	0.7736 (2)	0.0119 (4)
H5A	0.6405	0.5005	0.8588	0.014*
C6	0.45657 (19)	0.46530 (18)	0.6994 (2)	0.0118 (4)
H6A	0.4073	0.5333	0.7338	0.014*
H1	0.874 (2)	0.1789 (11)	0.710 (3)	0.021 (6)*
H2	0.879 (2)	0.302 (2)	0.6347 (16)	0.027 (7)*
H3	0.9755 (12)	0.284 (2)	0.779 (2)	0.030 (7)*
H4	0.842 (2)	0.4043 (16)	0.851 (3)	0.032 (7)*
H5	0.145 (3)	0.339 (2)	0.6667 (14)	0.029 (7)*
H6	0.148 (2)	0.2263 (11)	0.564 (3)	0.024 (6)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0161 (2)	0.0110 (2)	0.0118 (2)	0.00202 (17)	0.00197 (18)	0.00096 (16)
S1	0.0077 (2)	0.0090 (2)	0.0098 (2)	0.00040 (16)	0.00203 (17)	0.00041 (16)
O1	0.0122 (6)	0.0137 (6)	0.0087 (6)	−0.0005 (5)	0.0018 (5)	0.0004 (5)
N3	0.0117 (8)	0.0114 (8)	0.0114 (8)	−0.0016 (6)	0.0041 (6)	−0.0003 (6)
N1	0.0074 (8)	0.0142 (8)	0.0154 (8)	0.0007 (6)	0.0030 (7)	−0.0008 (7)
N2	0.0094 (7)	0.0115 (7)	0.0133 (8)	0.0004 (6)	0.0014 (6)	−0.0020 (6)
O2	0.0119 (6)	0.0097 (6)	0.0163 (7)	0.0020 (5)	0.0029 (5)	0.0001 (5)
C1	0.0077 (8)	0.0104 (8)	0.0105 (9)	−0.0006 (7)	0.0028 (7)	0.0019 (7)
C2	0.0110 (8)	0.0108 (8)	0.0112 (9)	−0.0022 (7)	0.0025 (7)	−0.0017 (7)
C3	0.0105 (8)	0.0094 (8)	0.0135 (9)	0.0011 (7)	0.0052 (7)	0.0002 (7)
C4	0.0077 (8)	0.0096 (8)	0.0104 (8)	0.0002 (7)	0.0020 (7)	0.0043 (7)
C5	0.0136 (9)	0.0104 (8)	0.0106 (9)	−0.0011 (7)	0.0020 (7)	−0.0020 (7)
C6	0.0122 (9)	0.0111 (9)	0.0125 (9)	0.0009 (7)	0.0044 (7)	−0.0008 (7)

Geometric parameters (Å, º)

S1—O2	1.4358 (13)	N2—H4	0.887 (10)
S1—O1	1.4366 (13)	C1—C2	1.386 (3)
S1—N3	1.6076 (16)	C1—C6	1.392 (3)
S1—C1	1.7640 (18)	C2—C3	1.393 (3)
N3—H5	0.876 (10)	C2—H2A	0.9500
N3—H6	0.873 (10)	C3—C4	1.397 (3)
N1—N2	1.431 (2)	C3—H3A	0.9500
N1—H1	0.886 (10)	C4—C5	1.392 (3)
N1—H2	0.883 (10)	C5—C6	1.384 (3)
N1—H3	0.877 (10)	C5—H5A	0.9500
N2—C4	1.408 (2)	C6—H6A	0.9500
O2—S1—O1	118.78 (8)	C2—C1—C6	120.49 (16)
O2—S1—N3	106.47 (8)	C2—C1—S1	120.96 (14)
O1—S1—N3	107.17 (8)	C6—C1—S1	118.52 (14)
O2—S1—C1	107.46 (8)	C1—C2—C3	119.51 (16)
O1—S1—C1	108.83 (8)	C1—C2—H2A	120.2
N3—S1—C1	107.66 (8)	C3—C2—H2A	120.2
S1—N3—H5	110.8 (16)	C2—C3—C4	120.19 (17)
S1—N3—H6	113.8 (16)	C2—C3—H3A	119.9
H5—N3—H6	114 (2)	C4—C3—H3A	119.9
N2—N1—H1	112.5 (15)	C5—C4—C3	119.70 (16)
N2—N1—H2	113.9 (15)	C5—C4—N2	117.49 (16)
H1—N1—H2	106 (2)	C3—C4—N2	122.76 (16)
N2—N1—H3	106.2 (16)	C6—C5—C4	120.12 (17)
H1—N1—H3	113 (2)	C6—C5—H5A	119.9
H2—N1—H3	106 (2)	C4—C5—H5A	119.9
C4—N2—N1	115.70 (14)	C5—C6—C1	120.00 (17)
C4—N2—H4	110.0 (16)	C5—C6—H6A	120.0
N1—N2—H4	111.8 (17)	C1—C6—H6A	120.0
O2—S1—C1—C2	−156.96 (14)	C2—C3—C4—C5	0.0 (3)
O1—S1—C1—C2	−27.13 (17)	C2—C3—C4—N2	177.52 (17)
N3—S1—C1—C2	88.71 (16)	N1—N2—C4—C5	−156.52 (16)
O2—S1—C1—C6	25.25 (17)	N1—N2—C4—C3	25.9 (2)
O1—S1—C1—C6	155.08 (14)	C3—C4—C5—C6	0.1 (3)
N3—S1—C1—C6	−89.07 (16)	N2—C4—C5—C6	−177.47 (17)
C6—C1—C2—C3	0.3 (3)	C4—C5—C6—C1	−0.1 (3)
S1—C1—C2—C3	−177.48 (14)	C2—C1—C6—C5	−0.1 (3)
C1—C2—C3—C4	−0.2 (3)	S1—C1—C6—C5	177.71 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.89 (1)	2.28 (1)	3.1319 (17)	162 (2)
N1—H2···O2i	0.88 (2)	2.03 (2)	2.835 (2)	152 (2)
N1—H3···Cl1ii	0.88 (2)	2.46 (2)	3.2136 (18)	144 (2)
N1—H3···O1iii	0.88 (2)	2.46 (2)	3.083 (2)	129 (2)
N2—H4···Cl1iv	0.89 (2)	2.67 (2)	3.3647 (16)	137 (2)
N3—H5···Cl1v	0.88 (1)	2.42 (2)	3.2656 (17)	163 (2)
N3—H6···Cl1vi	0.87 (1)	2.48 (2)	3.2467 (17)	147 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y+1/2, −z+3/2; (iii) x+1, −y+1/2, z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x+1, y+1/2, −z+3/2; (vi) −x+1, −y, −z+1.