4-Sulfamoylanilinium chloride

Zaouali Zgolli, D.; Boughzala, H.; Driss, A.

doi:10.1107/S1600536810019471

organic compounds

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Volume 66| Part 6| June 2010| Page o1488

https://doi.org/10.1107/S1600536810019471

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4-Sulfamoylanilinium chloride

Donia Zaouali Zgolli,^a ^* Habib Boughzala ^a and Ahmed Driss ^a

^aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences, El Manar, 2092 Tunis, Tunisia
^*Correspondence e-mail: donia_zgolli@hotmail.com

(Received 14 May 2010; accepted 24 May 2010; online 29 May 2010)

In the crystal structure of the title compound, C₆H₉N₂O₂S⁺·Cl⁻, the chloride anions are sandwiched between layers of 4-sulfonamidoanilinium anions. The components interact by way of N—H⋯Cl and N—H⋯O hydrogen bonds, building up a three-dimensional network.

Related literature

For the biological activity of diamines, see: Pasini & Zunino (1987 ); Otsuka et al. (1990 ); Michalson & Smuszkovicz (1989 ); Reedijk et al. (1996 ). For their use in asymmetric catalysis, see: Blaser (1992 ). For related structures, see: Chatterjee et al. (1981 ); Gelbrich et al. (2008 ); Gelmboldt et al. (2004 ); Smith et al. (2001 ).

Experimental

Crystal data

C₆H₉N₂O₂S⁺·Cl⁻
M_r = 208.66
Orthorhombic, P b n b
a = 7.4608 (2) Å
b = 7.7278 (2) Å
c = 31.694 (2) Å
V = 1827.35 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.982, T_max = 0.994
2906 measured reflections
1989 independent reflections
1442 reflections with I > 2σ(I)
R_int = 0.033
2 standard reflections every 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.182
S = 1.07
1989 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.89	2.30	3.122 (3)	153
N1—H1B⋯Cl1ⁱ	0.89	2.32	3.097 (3)	146
N1—H1C⋯Cl1ⁱⁱ	0.89	2.33	3.189 (3)	162
N2—H21⋯O1ⁱⁱⁱ	0.84	2.22	2.963 (5)	147
N2—H22⋯O2^iv	0.85	2.17	3.019 (5)	178
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (iii) $[x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810019471/dn2568sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019471/dn2568Isup2.hkl

checkCIF report

Comment top

The diamine compounds are important in biologically active natural products (Pasini & Zunino, 1987; Otsuka et al., 1990), in medicinal chemistry (Michalson & Smuszkovicz, 1989; Reedijk, 1996). They are also used as chiral auxiliaries and chiral ligands in asymmetric catalysis (Blaser, 1992). Here, a new member of this family, (C₆H₉N₂O₂S)⁺.Cl^-, is presented.

It was obtained during our investigations in organic chloride hybrids field. The crystal structure of the title compound contains a discrete cation with a protonated amino group (C₆H₉N₂O₂S)⁺.Cl^- and a halide anion (Fig 1).

The molecular structure including both terminal N atoms has an all-trans conformation. The nitrogen N1 position is protonated in this structure and participates in hydrogen bonding with the chlorine anions. The layered crystal packing of 4-sulfonamidoanilinium chloride is shown in Fig 2. The cations form alterning layers of hydrophobic and hydrophilic zones along the c axis.

The chloride ions are located in the interlayer space. Two types of classical hydrogen bonds are observed: N—H···Cl and N—H···O . These interaction bonds link the cations and the anions together, forming a three-dimensional network and reinforcing the ionic structure cohesion ((Fig 3, Table 1). The organic cations interacts with the Cl^- anion via hydrogen bonds, with N1—H···Cl distances ranging between 3.098 (3) Å and 3.191 (3) Å.

The packing is further consolidated through π-π stacking between symetry related benzene (3/2-x,-1/2+y,z) rings with centroid-to-centroid distance of 3.890 (2) Å and centroid-to-plane of 3.65 Å resulting in a slippage of 21°.

Selected geometrical parameters in (C₆H₉N₂O₂S)⁺ cation agree with those found in similar compounds, such as 4-aminobenzenesulfonamide (C₆H₈N₂O₂S) (Gelbrich et al., 2008), 4-homosulfanilamide hydrochloride (Chatterjee et al., 1981), bis(4-Aminosulfonyl)benzeneammonium hexafluorosilicate ( Gelmboldt et al.,2004) and 4-sulfonamidoanilinium 3,5-dinitrosalicylate (C₆H₉N₂O₂S⁺.C₇H₃N₂O₇) (Smith et al., 2001).

Related literature top

For the biological activity of diamines, see: Pasini & Zunino (1987); Otsuka et al. (1990); Michalson & Smuszkovicz (1989); Reedijk et al. (1996). For their use in asymmetric catalysis, see: Blaser (1992). For related structures, see: Chatterjee et al. (1981); Gelbrich et al. (2008); Gelmboldt et al. (2004); Smith et al. (2001).

Experimental top

Colourless crystals of 4-sulfonamidoanilinium chloride suitable for single crystal X-ray analysis were obtained by slow evaporation at room temperature of an ethanol solution of sulphanilamide (Fluka, Purity >97%) and hydrochloric acid.

Structure description top

For the biological activity of diamines, see: Pasini & Zunino (1987); Otsuka et al. (1990); Michalson & Smuszkovicz (1989); Reedijk et al. (1996). For their use in asymmetric catalysis, see: Blaser (1992). For related structures, see: Chatterjee et al. (1981); Gelbrich et al. (2008); Gelmboldt et al. (2004); Smith et al. (2001).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 top

	Fig. 1. Chemical diagram of the title compound.
	Fig. 2. Part of the crystal structure illustrating the alternating layers of hydrophobic and hydrophilic zones, viewed along the b axis. H atoms have been omitted for clarity.
	Fig. 3. The crystal packing of the title compound, viewed along the a axis showing the N—H···Cl/O interactions (dotted line). H atoms not involved in hydrogen bonding (dashe dlines) have been omitted for clarity. Displacement ellipsoids are drawn at 50%probability level.

4-Sulfamoylanilinium chloride top

Crystal data top

C₆H₉N₂O₂S⁺·Cl⁻	F(000) = 864
M_r = 208.66	D_x = 1.517 Mg m⁻³
Orthorhombic, Pbnb	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2ab	Cell parameters from 25 reflections
a = 7.4608 (2) Å	θ = 10–15°
b = 7.7278 (2) Å	µ = 0.61 mm⁻¹
c = 31.694 (2) Å	T = 298 K
V = 1827.35 (13) Å³	Prism, colourless
Z = 8	0.3 × 0.2 × 0.1 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1442 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.0°, θ_min = 2.6°
Non–profiled ω/2θ scans	h = −9→2
Absorption correction: ψ scan (North et al., 1968)	k = −1→9
T_min = 0.982, T_max = 0.994	l = −1→40
2906 measured reflections	2 standard reflections every 120 min
1989 independent reflections	intensity decay: none

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1231P)² + 0.2341P] where P = (F_o² + 2F_c²)/3
1989 reflections	(Δ/σ)_max = 0.001
110 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₆H₉N₂O₂S⁺·Cl⁻	V = 1827.35 (13) Å³
M_r = 208.66	Z = 8
Orthorhombic, Pbnb	Mo Kα radiation
a = 7.4608 (2) Å	µ = 0.61 mm⁻¹
b = 7.7278 (2) Å	T = 298 K
c = 31.694 (2) Å	0.3 × 0.2 × 0.1 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1442 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.033
T_min = 0.982, T_max = 0.994	2 standard reflections every 120 min
2906 measured reflections	intensity decay: none
1989 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.07	Δρ_max = 0.42 e Å⁻³
1989 reflections	Δρ_min = −0.44 e Å⁻³
110 parameters

Special details top

Experimental. Number of psi-scan sets used was 5 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied (North et al., 1968).

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 > 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	−0.01848 (14)	0.91801 (12)	0.80899 (3)	0.0494 (3)
O1	0.0885 (5)	1.0213 (4)	0.78197 (10)	0.0826 (11)
O2	−0.1835 (5)	0.9862 (4)	0.82564 (9)	0.0718 (10)
N1	0.4306 (4)	0.7241 (3)	0.95815 (9)	0.0394 (6)
H1A	0.4863	0.8185	0.9675	0.059*
H1B	0.5114	0.6443	0.9512	0.059*
H1C	0.3596	0.6828	0.9783	0.059*
N2	−0.0703 (5)	0.7452 (5)	0.78407 (10)	0.0623 (9)
H21	0.0127	0.7023	0.7694	0.075*
H22	−0.1381	0.6733	0.7963	0.075*
C1	0.3224 (4)	0.7679 (3)	0.92096 (9)	0.0317 (6)
C2	0.1373 (4)	0.7587 (4)	0.92407 (10)	0.0402 (7)
H2	0.0833	0.7210	0.9489	0.048*
C3	0.0345 (4)	0.8064 (5)	0.88976 (10)	0.0433 (7)
H3	−0.0898	0.8026	0.8915	0.052*
C4	0.1162 (4)	0.8597 (4)	0.85296 (9)	0.0368 (7)
C5	0.3026 (5)	0.8677 (4)	0.84957 (11)	0.0438 (8)
H5	0.3563	0.9039	0.8246	0.053*
C6	0.4060 (4)	0.8208 (4)	0.88399 (11)	0.0444 (7)
H6	0.5304	0.8246	0.8824	0.053*
Cl1	0.72981 (10)	1.00078 (9)	0.97197 (3)	0.0408 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0590 (6)	0.0496 (5)	0.0396 (5)	0.0060 (4)	−0.0092 (4)	0.0052 (4)
O1	0.097 (3)	0.084 (2)	0.066 (2)	−0.0156 (19)	−0.015 (2)	0.0379 (16)
O2	0.0707 (18)	0.084 (2)	0.0607 (19)	0.0399 (17)	−0.0180 (16)	−0.0076 (15)
N1	0.0340 (12)	0.0321 (13)	0.0521 (16)	−0.0016 (10)	−0.0096 (11)	0.0030 (11)
N2	0.067 (2)	0.075 (2)	0.0450 (17)	−0.0057 (18)	−0.0046 (16)	−0.0158 (15)
C1	0.0284 (12)	0.0237 (12)	0.0432 (16)	0.0010 (11)	−0.0005 (12)	−0.0017 (11)
C2	0.0327 (15)	0.0508 (17)	0.0373 (15)	−0.0017 (14)	0.0024 (12)	0.0058 (13)
C3	0.0273 (13)	0.0593 (19)	0.0431 (18)	0.0005 (14)	−0.0008 (13)	0.0031 (15)
C4	0.0395 (16)	0.0311 (14)	0.0397 (17)	0.0025 (12)	−0.0044 (13)	−0.0011 (12)
C5	0.0416 (17)	0.0449 (18)	0.0450 (19)	−0.0025 (14)	0.0098 (13)	0.0050 (14)
C6	0.0306 (14)	0.0488 (18)	0.0536 (19)	−0.0019 (14)	0.0052 (14)	0.0001 (15)
Cl1	0.0310 (4)	0.0328 (5)	0.0586 (6)	−0.0038 (3)	0.0016 (3)	0.0013 (3)

Geometric parameters (Å, º) top

S1—O1	1.417 (3)	C1—C2	1.386 (4)
S1—O2	1.439 (4)	C1—C6	1.389 (4)
S1—N2	1.599 (3)	C2—C3	1.381 (4)
S1—C4	1.776 (3)	C2—H2	0.9300
N1—C1	1.468 (4)	C3—C4	1.379 (4)
N1—H1A	0.8900	C3—H3	0.9300
N1—H1B	0.8900	C4—C5	1.396 (5)
N1—H1C	0.8900	C5—C6	1.384 (5)
N2—H21	0.8433	C5—H5	0.9300
N2—H22	0.8457	C6—H6	0.9300

O1—S1—O2	119.8 (2)	C6—C1—N1	119.9 (3)
O1—S1—N2	107.9 (2)	C3—C2—C1	118.9 (3)
O2—S1—N2	106.3 (2)	C3—C2—H2	120.5
O1—S1—C4	107.35 (18)	C1—C2—H2	120.5
O2—S1—C4	106.81 (16)	C4—C3—C2	120.0 (3)
N2—S1—C4	108.23 (17)	C4—C3—H3	120.0
C1—N1—H1A	109.5	C2—C3—H3	120.0
C1—N1—H1B	109.5	C3—C4—C5	121.2 (3)
H1A—N1—H1B	109.5	C3—C4—S1	119.3 (2)
C1—N1—H1C	109.5	C5—C4—S1	119.5 (2)
H1A—N1—H1C	109.5	C6—C5—C4	118.9 (3)
H1B—N1—H1C	109.5	C6—C5—H5	120.5
S1—N2—H21	115.1	C4—C5—H5	120.5
S1—N2—H22	117.9	C5—C6—C1	119.4 (3)
H21—N2—H22	115.7	C5—C6—H6	120.3
C2—C1—C6	121.5 (3)	C1—C6—H6	120.3
C2—C1—N1	118.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89	2.30	3.122 (3)	153
N1—H1B···Cl1ⁱ	0.89	2.32	3.097 (3)	146
N1—H1C···Cl1ⁱⁱ	0.89	2.33	3.189 (3)	162
N2—H21···O1ⁱⁱⁱ	0.84	2.22	2.963 (5)	147
N2—H22···O2^iv	0.85	2.17	3.019 (5)	178

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂O₂S⁺·Cl⁻
M_r	208.66
Crystal system, space group	Orthorhombic, Pbnb
Temperature (K)	298
a, b, c (Å)	7.4608 (2), 7.7278 (2), 31.694 (2)
V (Å³)	1827.35 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.982, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	2906, 1989, 1442
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.182, 1.07
No. of reflections	1989
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.44

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89	2.30	3.122 (3)	152.9
N1—H1B···Cl1ⁱ	0.89	2.32	3.097 (3)	145.5
N1—H1C···Cl1ⁱⁱ	0.89	2.33	3.189 (3)	162.1
N2—H21···O1ⁱⁱⁱ	0.84	2.22	2.963 (5)	147.2
N2—H22···O2^iv	0.85	2.17	3.019 (5)	178.0

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

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