organic papers
Acta Cryst.(2005). E61, o539–o540 doi:10.1107/S160053680500293X Gao, Huo and Ng C
7H9NO4S
o539
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
3-Ammonio-4-methoxybenzenesulfonate
Shan Gao,aLi-Hua Huoaand Seik Weng Ngb*
a
College of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People’s Republic of China, andbDepartment of
Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 295 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.028 wRfactor = 0.084
Data-to-parameter ratio = 11.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
3–Amino-4-methoxybenzenesulfonic acid exists in the solid state in the zwitterionic form as 3-ammonio-4-methoxy-benzenesulfonate, C7H9NO4S. The zwitterions are linked by
the ammonium H atoms into a layer structure.
Comment
3-Amino-4-hydroxybezenesulfonic acid, like a number of arenesulfonic acids, adopts a layer structure in which the aromatic rings stack into sheets; the sulfonate groups are located on the top and bottom of the layers (Gunderman & Squattrito, 1996). The title compound, (I), which has a methoxy substituent in place of the hydroxy substituent, also adopts a layer structure in which the zwitterions are linked to each other by hydrogen bonds (Fig. 1). The ammonium unit serves as the donor site for three hydrogen bonds; however, two of the three sulfonate O atoms are engaged in hydrogen bonding (Table 2). The negative charge appears to be de-localized over only two of the three O atoms, as the O atom that is not engaged in the interactions is nearest to the S atom.
Experimental
The title compound was recovered unchanged in an unsuccessful reaction with calcium nitrate hexahydrate. The calcium salt (0.82 g, 3 mmol) was mixed with methoxybenzenesulfonic acid (1.22 g, 6 mmol) in water. Colorless prismatic crystals separated from the solution after several days. Analysis calculated for C7H9NO4S:
C 41.37, H 4.46, N 6.89%; found C 41.33, H 4.48, N 6.87%.
Crystal data
C7H9NO4S
Mr= 203.21
Triclinic,P1
a= 7.321 (2) A˚
b= 8.234 (2) A˚
c= 8.354 (2) A˚
= 62.05 (3) = 65.34 (3) = 74.04 (3)
V= 402.3 (1) A˚3
Z= 2
Dx= 1.678 Mg m
3
MoKradiation Cell parameters from 3869
reflections
= 3.1–27.5 = 0.38 mm1
T= 295 (2) K Prism, colorless 0.340.260.19 mm
Data collection
Rigaku R-AXIS RAPID diffractometer
!scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin= 0.810,Tmax= 0.931
3979 measured reflections
1830 independent reflections 1713 reflections withI> 2(I)
Rint= 0.011 max= 27.5
h=9!8
k=10!10
l=10!10
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.028
wR(F2) = 0.084
S= 1.04 1830 reflections 154 parameters
All H-atom parameters refined
w= 1/[2(F
o2) + (0.053P)2
+ 0.1821P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001 max= 0.33 e A˚
3
min=0.38 e A˚3
Table 1
Selected geometric parameters (A˚ ,).
S1—O1 1.465 (1) S1—O2 1.464 (1) S1—O3 1.445 (1) S1—C1 1.771 (2)
O4—C4 1.354 (2) O4—C7 1.434 (2) N1—C3 1.457 (2) O1—S1—O2 111.1 (1)
O1—S1—O3 114.4 (1) O2—S1—O3 112.6 (1) C1—S1—O1 105.0 (1) C1—S1—O2 105.4 (1) C1—S1—O3 107.6 (1) C4—O4—C7 117.8 (1)
C2—C1—C6 120.4 (1) C2—C1—S1 120.0 (1) C6—C1—S1 119.5 (1) C2—C3—N1 120.4 (1) C4—C3—N1 117.9 (1) O4—C4—C5 125.9 (1) O4—C4—C3 115.1 (1)
Table 2
Hydrogen-bonding geometry (A˚ ,).
D—H A D—H H A D A D—H A
N1—H1n1 O1i 0.86 (1) 1.98 (1) 2.829 (2) 171 (2) N1—H1n2 O2ii
0.86 (1) 1.93 (1) 2.770 (2) 169 (2) N1—H1n3 O1iii
0.86 (1) 2.10 (1) 2.878 (2) 151 (2)
Symmetry codes: (i)x;1þy;z1; (ii)x;1y;1z; (iii) 1x;1y;1z.
All H atoms were refined with distance restraints of N—H = 0.85 (1) A˚ and C—H = 0.95 (1) A˚.
Data collection:RAPID-AUTO (Rigaku, 1998); cell refinement:
RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:ORTEPII(Johnson, 1976); software used to prepare material for publication:SHELXL97.
We thank the National Natural Science Foundation of China (No. 20101003), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036) and the University of Malaya for supporting this study.
References
Gunderman, B. J. & Squattrito, P. J. (1996).Acta Cryst.C52, 940–942. Higashi, T. (1995).ABSCOR.Rigaku Corporation, Tokyo, Japan.
Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Rigaku (1998).RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., 9009 New Trails
Drive, The Woodlands, TX 77381-5209, USA.
[image:2.610.311.567.72.220.2]Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany.
Figure 1
supporting information
sup-1 Acta Cryst. (2005). E61, o539–o540
supporting information
Acta Cryst. (2005). E61, o539–o540 [https://doi.org/10.1107/S160053680500293X]
3-Ammonio-4-methoxybenzenesulfonate
Shan Gao, Li-Hua Huo and Seik Weng Ng
3-Ammonio-4-methoxybenzenesulfonate
Crystal data
C7H9NO4S Mr = 203.21
Triclinic, P1 Hall symbol: -P 1
a = 7.321 (2) Å
b = 8.234 (2) Å
c = 8.354 (2) Å
α = 62.05 (3)°
β = 65.34 (3)°
γ = 74.04 (3)°
V = 402.3 (1) Å3
Z = 2
F(000) = 212
Dx = 1.678 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3869 reflections
θ = 3.1–27.5°
µ = 0.38 mm−1 T = 295 K Prism, colorless 0.34 × 0.26 × 0.19 mm
Data collection
Rigaku R-AXIS RAPID diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin = 0.810, Tmax = 0.931
3979 measured reflections 1830 independent reflections 1713 reflections with I > 2σ(I)
Rint = 0.011
θmax = 27.5°, θmin = 3.1° h = −9→8
k = −10→10
l = −10→10
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.028 wR(F2) = 0.084 S = 1.04 1830 reflections 154 parameters 9 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
All H-atom parameters refined
w = 1/[σ2(F
o2) + (0.053P)2 + 0.1821P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.33 e Å−3
Δρmin = −0.38 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
S1 0.20715 (5) 0.17966 (4) 0.70736 (4) 0.0182 (1)
O2 0.1115 (2) 0.0881 (1) 0.6530 (2) 0.0252 (2)
O3 0.0620 (2) 0.2766 (2) 0.8221 (2) 0.0293 (3)
O4 0.6393 (2) 0.7397 (1) −0.0404 (1) 0.0241 (2)
N1 0.3040 (2) 0.8525 (2) 0.1882 (2) 0.0201 (2)
C1 0.3461 (2) 0.3464 (2) 0.4875 (2) 0.0185 (3)
C2 0.2715 (2) 0.5314 (2) 0.4307 (2) 0.0185 (3)
C3 0.3757 (2) 0.6567 (2) 0.2520 (2) 0.0178 (3)
C4 0.5540 (2) 0.6018 (2) 0.1294 (2) 0.0186 (3)
C5 0.6265 (2) 0.4157 (2) 0.1873 (2) 0.0218 (3)
C6 0.5224 (2) 0.2889 (2) 0.3667 (2) 0.0220 (3)
C7 0.8295 (3) 0.6943 (2) −0.1674 (2) 0.0306 (3)
H1n1 0.313 (3) 0.904 (3) 0.069 (2) 0.042 (6)*
H1n2 0.179 (2) 0.872 (3) 0.249 (3) 0.034 (5)*
H1n3 0.370 (3) 0.910 (3) 0.206 (3) 0.033 (5)*
H2 0.152 (2) 0.574 (2) 0.510 (2) 0.029 (5)*
H5 0.744 (2) 0.373 (3) 0.106 (2) 0.033 (5)*
H6 0.575 (3) 0.163 (1) 0.404 (2) 0.027 (4)*
H71 0.936 (3) 0.651 (3) −0.117 (3) 0.052 (6)*
H72 0.853 (3) 0.800 (2) −0.286 (2) 0.051 (6)*
H73 0.828 (3) 0.597 (2) −0.198 (3) 0.046 (6)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
S1 0.0171 (2) 0.0166 (2) 0.0171 (2) −0.0018 (1) −0.0062 (1) −0.0035 (1) O1 0.0238 (5) 0.0233 (5) 0.0243 (5) −0.0021 (4) −0.0128 (4) −0.0007 (4) O2 0.0216 (5) 0.0266 (5) 0.0277 (5) −0.0069 (4) −0.0078 (4) −0.0093 (4) O3 0.0292 (6) 0.0277 (5) 0.0241 (5) −0.0007 (4) −0.0032 (4) −0.0113 (4) O4 0.0213 (5) 0.0215 (5) 0.0186 (5) −0.0020 (4) −0.0020 (4) −0.0038 (4) N1 0.0170 (6) 0.0163 (5) 0.0213 (6) −0.0017 (4) −0.0056 (5) −0.0039 (4) C1 0.0178 (6) 0.0174 (6) 0.0179 (6) −0.0033 (5) −0.0067 (5) −0.0040 (5) C2 0.0164 (6) 0.0194 (6) 0.0183 (6) −0.0014 (5) −0.0059 (5) −0.0065 (5) C3 0.0169 (6) 0.0151 (6) 0.0202 (6) −0.0009 (5) −0.0084 (5) −0.0049 (5) C4 0.0169 (6) 0.0204 (6) 0.0177 (6) −0.0030 (5) −0.0067 (5) −0.0057 (5) C5 0.0171 (6) 0.0227 (7) 0.0228 (7) 0.0003 (5) −0.0047 (5) −0.0101 (5) C6 0.0210 (7) 0.0167 (6) 0.0251 (7) 0.0003 (5) −0.0082 (5) −0.0069 (5) C7 0.0248 (7) 0.0343 (8) 0.0226 (7) −0.0032 (6) 0.0002 (6) −0.0107 (6)
Geometric parameters (Å, º)
S1—O1 1.465 (1) C4—C5 1.391 (2)
S1—O2 1.464 (1) C5—C6 1.391 (2)
S1—O3 1.445 (1) N1—H1n1 0.86 (1)
S1—C1 1.771 (2) N1—H1n2 0.86 (1)
O4—C4 1.354 (2) N1—H1n3 0.86 (1)
O4—C7 1.434 (2) C2—H2 0.95 (1)
N1—C3 1.457 (2) C5—H5 0.95 (1)
supporting information
sup-3 Acta Cryst. (2005). E61, o539–o540
C1—C6 1.390 (2) C7—H71 0.95 (1)
C2—C3 1.384 (2) C7—H72 0.95 (1)
C3—C4 1.397 (2) C7—H73 0.95 (1)
O1—S1—O2 111.1 (1) C3—N1—H1n1 113 (2)
O1—S1—O3 114.4 (1) C3—N1—H1n2 112 (1)
O2—S1—O3 112.6 (1) H1n1—N1—H1n2 104 (2)
C1—S1—O1 105.0 (1) C3—N1—H1n3 110 (1)
C1—S1—O2 105.4 (1) H1n1—N1—H1n3 109 (2)
C1—S1—O3 107.6 (1) H1n2—N1—H1n3 108 (2)
C4—O4—C7 117.8 (1) C3—C2—H2 119 (1)
C2—C1—C6 120.4 (1) C1—C2—H2 122 (1)
C2—C1—S1 120.0 (1) C4—C5—H5 121 (1)
C6—C1—S1 119.5 (1) C6—C5—H5 119 (1)
C1—C2—C3 118.7 (1) C5—C6—H6 118 (1)
C2—C3—C4 121.7 (1) C1—C6—H6 121 (1)
C2—C3—N1 120.4 (1) O4—C7—H71 114 (2)
C4—C3—N1 117.9 (1) O4—C7—H72 106 (1)
O4—C4—C5 125.9 (1) H71—C7—H72 115 (2)
O4—C4—C3 115.1 (1) O4—C7—H73 114 (1)
C3—C4—C5 119.1 (1) H71—C7—H73 103 (2)
C4—C5—C6 119.5 (1) H72—C7—H73 105 (2)
C1—C6—C6 120.6 (1)
O3—S1—C1—C2 −17.6 (1) C7—O4—C4—C3 176.1 (1)
O2—S1—C1—C2 102.8 (1) C2—C3—C4—O4 −179.8 (1)
O1—S1—C1—C2 −139.8 (1) N1—C3—C4—O4 −1.3 (2)
O3—S1—C1—C6 166.9 (1) C2—C3—C4—C5 1.1 (2)
O2—S1—C1—C6 −72.7 (1) N1—C3—C4—C5 179.6 (1)
O1—S1—C1—C6 44.7 (1) O4—C4—C5—C6 −180.0 (1)
C6—C1—C2—C3 0.1 (2) C3—C4—C5—C6 −1.0 (2)
S1—C1—C2—C3 −175.3 (1) C4—C5—C6—C1 0.5 (2)
C1—C2—C3—C4 −0.7 (2) C2—C1—C6—C5 0.0 (2)
C1—C2—C3—N1 −179.1 (1) S1—C1—C6—C5 175.5 (1)
C7—O4—C4—C5 −4.9 (2)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N1—H1n1···O1i 0.86 (1) 1.98 (1) 2.829 (2) 171 (2)
N1—H1n2···O2ii 0.86 (1) 1.93 (1) 2.770 (2) 169 (2)
N1—H1n3···O1iii 0.86 (1) 2.10 (1) 2.878 (2) 151 (2)