4-Amino-3-ammonio­benzene­sulfonate

Abstract

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,

• a = 5.602 (1) Å

• b = 8.4135 (15) Å

• c = 16.221 (3) Å

• β = 95.613 (2)°

• V = 760.9 (2) ų

• 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[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 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

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.

Supplementary Material

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—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⋯O3iv	0.86	2.46	3.047 (2)	126

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

C-bound H atoms and N(amino)-bound H atoms were geometrically positioned (C—H = 0.93 Å, N—H = 0.86 Å) and included in the riding model approximation, with U_iso(H) = 1.2 U_eq(C, N). H atoms attached to N(ammonio) were located from an electron density map, and isotropically refined with the N—H bond length restrained to 0.91 (3) Å.

Figures

Fig. 1.

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

Crystal data

C6H8N2O3S	F(000) = 392
Mr = 188.20	Dx = 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

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

Refinement

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(Fo2) + (0.0446P)2 + 0.3348P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
1490 reflections	Δρmax = 0.34 e Å−3
122 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···O3iv	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.