4-Amino-3-ammonio­benzene­sulfonate

Liu, J.-L.; Du, C.-J.; Wang, L.-S.

doi:10.1107/S1600536810048063

organic compounds

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4-Amino-3-ammoniobenzenesulfonate

Jian-Lian Liu,^a ^* Chao-Jun Du ^a,^b and Li-Sheng Wang ^b

^aDepartment of Chemical and Biochemical Engineering, Nanyang Institute of Technology, 473004 Nanyang, Henan, People's Republic of China, and ^bSchool of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing, People's Republic of China
^*Correspondence e-mail: jlliu@yahoo.cn

(Received 15 November 2010; accepted 18 November 2010; online 24 November 2010)

The title compound, C₆H₈N₂O₃S, crystallized as a sulfonate–aminium zwitterion. In the crystal, intermolecular N—H⋯O hydrogen bonds generate an extensive three-dimensional network, which consolidates the packing.

Related literature

For the crystal structures of isomers of the title compound, see: Rubin-Preminger & Bernstein (2003 ). For details of the synthesis, see: Miranda et al. (2008 ).

Experimental

Crystal data

C₆H₈N₂O₃S
M_r = 188.20
Monoclinic, P 2₁ /c
a = 5.602 (1) Å
b = 8.4135 (15) Å
c = 16.221 (3) Å
β = 95.613 (2)°
V = 760.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 295 K
0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.875, T_max = 0.944
4039 measured reflections
1490 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.087
S = 1.09
1490 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.92 (3)	1.86 (3)	2.778 (2)	178 (2)
N1—H1C⋯O1ⁱⁱ	0.92 (3)	1.89 (3)	2.792 (2)	165 (2)
N1—H1A⋯O2ⁱⁱⁱ	0.90 (2)	1.88 (3)	2.759 (2)	165 (2)
N2—H2B⋯O3^iv	0.86	2.46	3.047 (2)	126
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z+2; (iii) -x+1, -y, -z+2; (iv) -x, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810048063/cv2799sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048063/cv2799Isup2.hkl

checkCIF report

Comment top

The title compound (I) (Fig. 1) is a zwitterion of 4-amino-3-ammoniobenzenesulfonate. The bond lengths and angles in (I) are normal and comparable with those observed in the related compounds (Rubin-Preminger & Bernstein, 2003). In the crystal structure, intermolecular N—H···O hydrogen bonds generate an extensive three-dumensional network which consolidate the crystal packing.

Related literature top

For the crystal structures of isomers of the title compound, see: Rubin-Preminger & Bernstein (2003). For details of the synthesis, see: Miranda et al. (2008).

Experimental top

The title compound was synthesized according to the method reported in the literature (Miranda et al., 2008). Orange single crystals suitable for X-ray diffraction were obtained by slow evaporation of a water solution of the compound.

Structure description top

For the crystal structures of isomers of the title compound, see: Rubin-Preminger & Bernstein (2003). For details of the synthesis, see: Miranda et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.

4-Amino-3-ammoniobenzenesulfonate top

Crystal data top

C₆H₈N₂O₃S	F(000) = 392
M_r = 188.20	D_x = 1.643 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2332 reflections
a = 5.602 (1) Å	θ = 2.4–27.7°
b = 8.4135 (15) Å	µ = 0.39 mm⁻¹
c = 16.221 (3) Å	T = 295 K
β = 95.613 (2)°	Block, orange
V = 760.9 (2) Å³	0.35 × 0.25 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1490 independent reflections
Radiation source: fine-focus sealed tube	1351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.875, T_max = 0.944	k = −9→10
4039 measured reflections	l = −17→19

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0446P)² + 0.3348P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1490 reflections	Δρ_max = 0.34 e Å⁻³
122 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (3)

Crystal data top

C₆H₈N₂O₃S	V = 760.9 (2) Å³
M_r = 188.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.602 (1) Å	µ = 0.39 mm⁻¹
b = 8.4135 (15) Å	T = 295 K
c = 16.221 (3) Å	0.35 × 0.25 × 0.15 mm
β = 95.613 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1490 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1351 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.944	R_int = 0.019
4039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.34 e Å⁻³
1490 reflections	Δρ_min = −0.33 e Å⁻³
122 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
C1	0.1329 (3)	0.2272 (2)	1.04906 (10)	0.0265 (4)
C2	0.1963 (3)	0.15996 (19)	0.97641 (10)	0.0263 (4)
H2	0.3348	0.0988	0.9769	0.032*
C3	0.0532 (3)	0.18407 (19)	0.90339 (10)	0.0263 (4)
C4	−0.1567 (3)	0.2754 (2)	0.90017 (10)	0.0300 (4)
C5	−0.2178 (3)	0.3403 (2)	0.97466 (11)	0.0341 (4)
H5	−0.3570	0.4005	0.9747	0.041*
C6	−0.0764 (3)	0.3168 (2)	1.04811 (11)	0.0314 (4)
H6	−0.1207	0.3608	1.0970	0.038*
H1A	0.266 (4)	0.065 (3)	0.8377 (14)	0.052 (7)*
H1B	0.132 (4)	0.185 (3)	0.7858 (16)	0.045 (6)*
H1C	0.012 (4)	0.033 (3)	0.8111 (15)	0.055 (7)*
N1	0.1219 (3)	0.1112 (2)	0.82725 (9)	0.0304 (3)
N2	−0.2985 (3)	0.3022 (2)	0.82732 (11)	0.0502 (5)
H2B	−0.4260	0.3592	0.8274	0.060*
H2A	−0.2597	0.2619	0.7818	0.060*
O1	0.1572 (3)	0.16078 (16)	1.20518 (8)	0.0413 (4)
O2	0.4779 (3)	0.07161 (18)	1.12735 (8)	0.0518 (4)
O3	0.4413 (2)	0.34942 (17)	1.16250 (8)	0.0424 (4)
S1	0.31916 (8)	0.20155 (5)	1.14202 (2)	0.02874 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0281 (9)	0.0290 (8)	0.0218 (8)	0.0004 (6)	−0.0011 (6)	−0.0005 (6)
C2	0.0269 (8)	0.0274 (8)	0.0243 (8)	0.0028 (6)	0.0004 (6)	0.0009 (6)
C3	0.0302 (9)	0.0259 (8)	0.0222 (8)	0.0004 (6)	0.0005 (6)	−0.0006 (6)
C4	0.0303 (9)	0.0298 (8)	0.0285 (9)	0.0012 (7)	−0.0045 (7)	0.0012 (7)
C5	0.0277 (9)	0.0369 (9)	0.0368 (10)	0.0073 (7)	−0.0004 (7)	−0.0027 (7)
C6	0.0309 (9)	0.0363 (9)	0.0275 (9)	0.0036 (7)	0.0045 (7)	−0.0054 (7)
N1	0.0352 (9)	0.0334 (8)	0.0217 (7)	0.0054 (7)	−0.0010 (6)	−0.0001 (6)
N2	0.0538 (11)	0.0559 (11)	0.0364 (9)	0.0241 (9)	−0.0188 (8)	−0.0073 (8)
O1	0.0556 (9)	0.0457 (8)	0.0228 (6)	−0.0086 (6)	0.0054 (6)	−0.0029 (5)
O2	0.0625 (9)	0.0574 (9)	0.0324 (7)	0.0326 (8)	−0.0104 (6)	−0.0080 (6)
O3	0.0452 (8)	0.0432 (8)	0.0366 (7)	−0.0086 (6)	−0.0072 (6)	−0.0032 (6)
S1	0.0343 (3)	0.0307 (3)	0.0203 (2)	0.00447 (16)	−0.00195 (17)	−0.00273 (15)

Geometric parameters (Å, º) top

C1—C2	1.385 (2)	C5—H5	0.9300
C1—C6	1.393 (2)	C6—H6	0.9300
C1—S1	1.7611 (17)	N1—H1A	0.90 (2)
C2—C3	1.379 (2)	N1—H1B	0.92 (3)
C2—H2	0.9300	N1—H1C	0.92 (3)
C3—C4	1.401 (2)	N2—H2B	0.8600
C3—N1	1.464 (2)	N2—H2A	0.8600
C4—N2	1.376 (2)	O1—S1	1.4739 (14)
C4—C5	1.399 (2)	O2—S1	1.4435 (14)
C5—C6	1.379 (2)	O3—S1	1.4428 (14)

C2—C1—C6	119.85 (15)	C1—C6—H6	120.0
C2—C1—S1	119.92 (13)	C3—N1—H1A	109.1 (15)
C6—C1—S1	120.23 (13)	C3—N1—H1B	111.8 (14)
C3—C2—C1	119.66 (15)	H1A—N1—H1B	108 (2)
C3—C2—H2	120.2	C3—N1—H1C	108.5 (14)
C1—C2—H2	120.2	H1A—N1—H1C	108 (2)
C2—C3—C4	121.88 (15)	H1B—N1—H1C	111 (2)
C2—C3—N1	118.96 (15)	C4—N2—H2B	120.0
C4—C3—N1	119.16 (15)	C4—N2—H2A	120.0
N2—C4—C5	120.55 (16)	H2B—N2—H2A	120.0
N2—C4—C3	122.25 (16)	O3—S1—O2	113.91 (10)
C5—C4—C3	117.20 (15)	O3—S1—O1	110.55 (8)
C6—C5—C4	121.48 (16)	O2—S1—O1	111.67 (9)
C6—C5—H5	119.3	O3—S1—C1	108.61 (8)
C4—C5—H5	119.3	O2—S1—C1	105.94 (8)
C5—C6—C1	119.93 (16)	O1—S1—C1	105.68 (8)
C5—C6—H6	120.0

C6—C1—C2—C3	0.9 (3)	C4—C5—C6—C1	0.2 (3)
S1—C1—C2—C3	−178.25 (13)	C2—C1—C6—C5	−1.0 (3)
C1—C2—C3—C4	0.0 (3)	S1—C1—C6—C5	178.15 (14)
C1—C2—C3—N1	−179.58 (15)	C2—C1—S1—O3	106.55 (15)
C2—C3—C4—N2	178.93 (17)	C6—C1—S1—O3	−72.59 (16)
N1—C3—C4—N2	−1.5 (3)	C2—C1—S1—O2	−16.19 (17)
C2—C3—C4—C5	−0.8 (3)	C6—C1—S1—O2	164.66 (15)
N1—C3—C4—C5	178.80 (16)	C2—C1—S1—O1	−134.81 (14)
N2—C4—C5—C6	−179.04 (18)	C6—C1—S1—O1	46.04 (17)
C3—C4—C5—C6	0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.92 (3)	1.86 (3)	2.778 (2)	178 (2)
N1—H1C···O1ⁱⁱ	0.92 (3)	1.89 (3)	2.792 (2)	165 (2)
N1—H1A···O2ⁱⁱⁱ	0.90 (2)	1.88 (3)	2.759 (2)	165 (2)
N2—H2B···O3^iv	0.86	2.46	3.047 (2)	126

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

Experimental details

Crystal data
Chemical formula	C₆H₈N₂O₃S
M_r	188.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	5.602 (1), 8.4135 (15), 16.221 (3)
β (°)	95.613 (2)
V (Å³)	760.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.875, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	4039, 1490, 1351
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.087, 1.09
No. of reflections	1490
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.33

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.92 (3)	1.86 (3)	2.778 (2)	178 (2)
N1—H1C···O1ⁱⁱ	0.92 (3)	1.89 (3)	2.792 (2)	165 (2)
N1—H1A···O2ⁱⁱⁱ	0.90 (2)	1.88 (3)	2.759 (2)	165 (2)
N2—H2B···O3^iv	0.86	2.46	3.047 (2)	126.2

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

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Miranda, F. da S., Signori, A. M., Vicente, J., de Souza, B., Priebe, J. P., Szpoganicz, B., Sanches, N. G. & Neves, A. (2008). Tetrahedron, 64, 5410–5415. Google Scholar
Rubin-Preminger, J. M. & Bernstein, J. (2003). Helv. Chim. Acta, 86, 3037–3054. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3281

https://doi.org/10.1107/S1600536810048063

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