4-Guanidinobenzene­sulfonic acid

Wang, W.-F.; Wei, C.-M.; Zhu, H.-J.

doi:10.1107/S1600536809012355

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o980

doi:10.1107/S1600536809012355

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4-Guanidinobenzenesulfonic acid

Wei-Feng Wang,^a,^b Chang-Mei Wei ^b ^* and Hong-Jun Zhu ^a ^*

^aCollege of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bDepartment of Chemistry of Huaiyin Teachers College, Jangsu Key Laboratory for the Chemistry of Low-Dimensional Materials, Huaian 223300, People's Republic of China
^*Correspondence e-mail: wangyyx2008@163.com,

(Received 20 February 2009; accepted 2 April 2009; online 8 April 2009)

In the zwitterionic title compound (systematic name: 4-{[amino(inimio)methyl]amino}benzenesulfonate), C₇H₉N₃O₃S, the dihedral angle between the plane of the guanidine grouping and the benzene ring system is 44.87 (7)°. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds involving all the potential donors.

Related literature

For the synthesis, see: Hofbens & Rath (1981 ). For the effect of guanidine salts on protein structure and their inhibitory effect on various physiological activities, see: Miyake et al. (2008 ).

Experimental

Crystal data

C₇H₉N₃O₃S
M_r = 215.24
Orthorhombic, P b c a
a = 7.9967 (9) Å
b = 11.9200 (13) Å
c = 19.721 (2) Å
V = 1879.8 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.35 × 0.3 × 0.2 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.902, T_max = 0.944
10292 measured reflections
2156 independent reflections
1544 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.110
S = 1.02
2156 reflections
163 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H5⋯O2ⁱ	0.80 (3)	2.00 (3)	2.802 (2)	171 (2)
N2—H6⋯O2ⁱⁱ	0.88 (3)	2.02 (3)	2.851 (2)	158 (2)
N2—H7⋯O3ⁱⁱⁱ	0.89 (3)	2.07 (3)	2.913 (3)	160 (2)
N3—H8⋯O1ⁱⁱⁱ	0.91 (3)	2.03 (3)	2.924 (3)	167 (3)
N3—H9⋯O3^iv	0.83 (3)	2.34 (3)	2.928 (3)	129 (2)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: 10.1107/S1600536809012355/bq2128sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012355/bq2128Isup2.hkl

checkCIF report

Comment top

Guanidine is known to interact strongly with various substances of biological origin in their molecules forming ionic pairs through ionic bonds and hydrogen bonding. Research on guanidine salts in the field of biochemistry have dealt mainly with their effect on protein structure and inhibitory effect on various physiological activities (Miyake et al., 2008). The full molecule of the title compound, (I), (Fig. 1), is a big hyperconjugation system because the bond lengths of N1—C7 (1.329 (3)Å), C7—N2 (1.313 (3)Å) and C7—N3 (1.327 (3)Å) are averaged, and the bond lengths of S1—O1 (1.4546 (15)Å), S1—O2 (1.4619 (15)Å) and S1—O3 (1.4457 (15)Å) are also averaged. Meanwhile, the bond lengths of C3—N1 (1.327 (3)Å) and C6—S1 (1.770 (2)Å) become shorter than standard values (C—N = 1.47–1.50Å and C—S = 1.82Å). In addition, in (I) C2-C3-N1-C7 form a torsion angle of 42.3 (3)° and C1-C6-S1-O1 form a torsion angle of -69.91 (18)°. The dihedral angle between the plane of the guanidine group and the benzene ring system is 44.87 (7)°, while the dihedral angle between the benzene ring and the adjacent S1O1O2 group is 84.76 (7)°. The crystal packing is stabilized by intermolecular N—H···O hydrogen bonds involving all the potential donors.

Related literature top

For the synthesis, see: Hofbens & Rath (1981). For the effect of guanidine salts on protein structure and their inhibitory effect on various physiological activities, see: Miyake et al. (2008).

Experimental top

The title compound was synthesized by 4-aminobenzenesulfonic acid (3.5 g, 0.02 mol), 50% amino nitrile (3.5 g, 0.04 mol) and 37% hydrochloric acid (3.4 ml) in the ethanol boil point temperature for 24 h with stirring (Hofbens & Rath, 1981). The reaction mixture was reduced pressure distillation to obtain the rough solid, then dissolved in water. The solid residue was filtered and the filtrate was kept at room temperature. Colorless crystals of the title compound were obtained after a few days. The crystal used for data collection was obtained by slow evaporation from a saturated water solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 atom labels and 40% probability displacement ellipsoids for non-H atoms.

4-{[amino(inimio)methyl]amino}benzenesulfonate top

Crystal data top

C₇H₉N₃O₃S	D_x = 1.521 Mg m⁻³
M_r = 215.24	Melting point > 300 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2125 reflections
a = 7.9967 (9) Å	θ = 3.2–25.9°
b = 11.9200 (13) Å	µ = 0.33 mm⁻¹
c = 19.721 (2) Å	T = 296 K
V = 1879.8 (4) Å³	Block, colourless
Z = 8	0.35 × 0.3 × 0.2 mm
F(000) = 896

Data collection top

Bruker SMART APEXII CCD diffractometer	2156 independent reflections
Radiation source: fine-focus sealed tube	1544 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.902, T_max = 0.944	k = −15→13
10292 measured reflections	l = −24→25

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.054P)² + 0.6089P] where P = (F_o² + 2F_c²)/3
2156 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₇H₉N₃O₃S	V = 1879.8 (4) Å³
M_r = 215.24	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.9967 (9) Å	µ = 0.33 mm⁻¹
b = 11.9200 (13) Å	T = 296 K
c = 19.721 (2) Å	0.35 × 0.3 × 0.2 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2156 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1544 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.944	R_int = 0.040
10292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.24 e Å⁻³
2156 reflections	Δρ_min = −0.31 e Å⁻³
163 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	0.0397 (3)	0.48689 (18)	0.26624 (10)	0.0329 (5)
C2	0.0470 (3)	0.53779 (18)	0.32882 (11)	0.0338 (5)
C3	0.1174 (2)	0.64333 (17)	0.33506 (10)	0.0316 (5)
C4	0.1778 (3)	0.69826 (18)	0.27833 (11)	0.0356 (5)
C5	0.1684 (3)	0.64822 (17)	0.21529 (11)	0.0346 (5)
C6	0.1005 (2)	0.54177 (16)	0.20961 (10)	0.0291 (4)
C7	0.1541 (3)	0.65879 (18)	0.45879 (10)	0.0349 (5)
H1	−0.006 (3)	0.4173 (19)	0.2604 (12)	0.044 (6)*
H2	−0.004 (3)	0.504 (2)	0.3685 (11)	0.043 (6)*
H3	0.230 (3)	0.765 (2)	0.2812 (11)	0.045 (7)*
H4	0.210 (3)	0.6900 (18)	0.1779 (13)	0.043 (6)*
H5	0.101 (3)	0.767 (2)	0.3958 (12)	0.049 (7)*
H6	0.253 (3)	0.523 (2)	0.4302 (14)	0.055 (8)*
H7	0.236 (3)	0.529 (2)	0.5062 (14)	0.058 (8)*
H8	0.178 (3)	0.700 (2)	0.5536 (15)	0.072 (9)*
H9	0.098 (3)	0.787 (2)	0.5079 (13)	0.052 (8)*
N1	0.1200 (3)	0.70124 (16)	0.39801 (10)	0.0412 (5)
N2	0.2066 (3)	0.55499 (17)	0.46566 (11)	0.0439 (5)
N3	0.1313 (3)	0.7218 (2)	0.51347 (11)	0.0532 (6)
O1	0.21174 (19)	0.38280 (13)	0.13149 (8)	0.0451 (4)
O2	−0.07907 (17)	0.43211 (12)	0.12279 (7)	0.0376 (4)
O3	0.1335 (2)	0.55807 (12)	0.07941 (8)	0.0494 (5)
S1	0.09167 (7)	0.47441 (4)	0.12971 (2)	0.03204 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0413 (11)	0.0274 (11)	0.0300 (11)	−0.0057 (9)	−0.0014 (9)	0.0013 (8)
C2	0.0401 (10)	0.0355 (12)	0.0258 (11)	−0.0029 (9)	0.0007 (9)	0.0027 (9)
C3	0.0386 (10)	0.0276 (10)	0.0287 (11)	0.0059 (9)	−0.0034 (9)	−0.0024 (8)
C4	0.0467 (12)	0.0233 (10)	0.0368 (12)	−0.0024 (9)	−0.0033 (10)	−0.0017 (9)
C5	0.0451 (11)	0.0260 (11)	0.0327 (12)	−0.0013 (10)	0.0034 (10)	0.0034 (9)
C6	0.0348 (10)	0.0256 (10)	0.0268 (10)	0.0012 (8)	−0.0011 (8)	−0.0012 (8)
C7	0.0442 (11)	0.0343 (11)	0.0262 (11)	0.0069 (10)	−0.0028 (9)	−0.0045 (9)
N1	0.0665 (13)	0.0261 (10)	0.0311 (10)	0.0095 (9)	−0.0096 (9)	−0.0053 (8)
N2	0.0691 (13)	0.0396 (11)	0.0231 (10)	0.0176 (10)	−0.0035 (10)	−0.0027 (8)
N3	0.0846 (16)	0.0421 (13)	0.0329 (12)	0.0172 (12)	−0.0051 (11)	−0.0121 (10)
O1	0.0532 (9)	0.0373 (9)	0.0448 (10)	0.0100 (7)	0.0017 (7)	−0.0085 (7)
O2	0.0465 (8)	0.0309 (8)	0.0355 (9)	−0.0020 (7)	−0.0086 (7)	−0.0012 (6)
O3	0.0869 (12)	0.0336 (9)	0.0278 (8)	−0.0105 (9)	0.0088 (8)	0.0034 (6)
S1	0.0474 (3)	0.0247 (3)	0.0240 (3)	−0.0011 (2)	0.0010 (2)	−0.00080 (19)

Geometric parameters (Å, º) top

C1—C2	1.376 (3)	C7—N2	1.313 (3)
C1—C6	1.383 (3)	C7—N3	1.327 (3)
C1—H1	0.91 (2)	C7—N1	1.329 (3)
C2—C3	1.384 (3)	N1—H5	0.80 (3)
C2—H2	0.97 (2)	N2—H6	0.88 (3)
C3—C4	1.383 (3)	N2—H7	0.89 (3)
C3—N1	1.421 (3)	N3—H8	0.91 (3)
C4—C5	1.381 (3)	N3—H9	0.83 (3)
C4—H3	0.90 (2)	O1—S1	1.4546 (15)
C5—C6	1.385 (3)	O2—S1	1.4619 (15)
C5—H4	0.95 (2)	O3—S1	1.4457 (15)
C6—S1	1.770 (2)

C2—C1—C6	120.1 (2)	N2—C7—N3	119.6 (2)
C2—C1—H1	122.0 (15)	N2—C7—N1	121.1 (2)
C6—C1—H1	117.9 (15)	N3—C7—N1	119.3 (2)
C1—C2—C3	119.9 (2)	C7—N1—C3	127.30 (19)
C1—C2—H2	121.6 (14)	C7—N1—H5	117.4 (18)
C3—C2—H2	118.4 (14)	C3—N1—H5	115.2 (18)
C4—C3—C2	120.0 (2)	C7—N2—H6	117.3 (17)
C4—C3—N1	118.13 (19)	C7—N2—H7	120.1 (17)
C2—C3—N1	121.70 (19)	H6—N2—H7	117 (2)
C5—C4—C3	120.3 (2)	C7—N3—H8	119.0 (18)
C5—C4—H3	117.6 (14)	C7—N3—H9	117.9 (19)
C3—C4—H3	122.0 (14)	H8—N3—H9	121 (3)
C4—C5—C6	119.3 (2)	O3—S1—O1	112.45 (10)
C4—C5—H4	116.9 (14)	O3—S1—O2	112.95 (10)
C6—C5—H4	123.7 (14)	O1—S1—O2	111.09 (9)
C1—C6—C5	120.40 (19)	O3—S1—C6	106.78 (9)
C1—C6—S1	119.37 (15)	O1—S1—C6	107.02 (9)
C5—C6—S1	120.22 (15)	O2—S1—C6	106.07 (9)

C6—C1—C2—C3	−0.9 (3)	N2—C7—N1—C3	6.7 (4)
C1—C2—C3—C4	1.1 (3)	N3—C7—N1—C3	−171.9 (2)
C1—C2—C3—N1	176.8 (2)	C4—C3—N1—C7	−141.9 (2)
C2—C3—C4—C5	−0.1 (3)	C2—C3—N1—C7	42.3 (3)
N1—C3—C4—C5	−176.0 (2)	C1—C6—S1—O3	169.46 (17)
C3—C4—C5—C6	−1.1 (3)	C5—C6—S1—O3	−10.8 (2)
C2—C1—C6—C5	−0.2 (3)	C1—C6—S1—O1	−69.91 (18)
C2—C1—C6—S1	179.46 (16)	C5—C6—S1—O1	109.79 (18)
C4—C5—C6—C1	1.2 (3)	C1—C6—S1—O2	48.76 (18)
C4—C5—C6—S1	−178.46 (16)	C5—C6—S1—O2	−131.54 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H5···O2ⁱ	0.80 (3)	2.00 (3)	2.802 (2)	171 (2)
N2—H6···O2ⁱⁱ	0.88 (3)	2.02 (3)	2.851 (2)	158 (2)
N2—H7···O3ⁱⁱⁱ	0.89 (3)	2.07 (3)	2.913 (3)	160 (2)
N3—H8···O1ⁱⁱⁱ	0.91 (3)	2.03 (3)	2.924 (3)	167 (3)
N3—H9···O3^iv	0.83 (3)	2.34 (3)	2.928 (3)	129 (2)

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

Experimental details

Crystal data
Chemical formula	C₇H₉N₃O₃S
M_r	215.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	7.9967 (9), 11.9200 (13), 19.721 (2)
V (Å³)	1879.8 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.35 × 0.3 × 0.2

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.902, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	10292, 2156, 1544
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.110, 1.02
No. of reflections	2156
No. of parameters	163
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.31

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H5···O2ⁱ	0.80 (3)	2.00 (3)	2.802 (2)	171 (2)
N2—H6···O2ⁱⁱ	0.88 (3)	2.02 (3)	2.851 (2)	158 (2)
N2—H7···O3ⁱⁱⁱ	0.89 (3)	2.07 (3)	2.913 (3)	160 (2)
N3—H8···O1ⁱⁱⁱ	0.91 (3)	2.03 (3)	2.924 (3)	167 (3)
N3—H9···O3^iv	0.83 (3)	2.34 (3)	2.928 (3)	129 (2)

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

Acknowledgements

We are grateful to the Science Foundation of Jiangsu Education Bureau (05KJD 150039), the Professor Foundation of Huaiyin Teachers Collage (05 HSJS018) and the Science Foundation of Jangsu Key Laboratory for the Chemistry of Low-Dimensional Materials (JSKC 06028) for financial support.

References

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Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hofbens, J. & Rath, H. J. (1981). Arch Pharm, 8, 731–733. Google Scholar
Miyake, M., Yamada, K. & Oyama, N. (2008). Langmuir, 24, 8527–8528. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar