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In the anion of the title salt, C2H6NO2+·C7H5O6S, the dihedral angle between the carb­oxy­lic acid group and the benzene ring is 5.02 (12)°. In the crystal, the anions are linked into inversion dimers through pairs of O—H...O hydrogen bonds between the carb­oxy­lic acid groups and sulfonate O atoms. A pair of C—H...O inter­actions is also observed within each dimer. The anion dimers and the cations are linked into a three-dimensional network by N—H...O, O—H...O and C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814004590/is5343sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536814004590/is5343Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536814004590/is5343Isup3.cml
Supplementary material

CCDC reference: 989106

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.049
  • wR factor = 0.117
  • Data-to-parameter ratio = 18.8

checkCIF/PLATON results

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Alert level C PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.1 Note PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 5.033 Check PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 7 Why ?
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 10 Note PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 6 Note PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 301 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 6 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Non-linear optical materials have recently invoked a large amount of interest due to their potential application in harmonic generation, optical information processing, optical storage and two photon pumped lasers (Yang et al., 2005; Kumar et al., 2009). We herein, report the crystal structure of the title compound (I), (Fig. 1). The geometric parameters of the title compound are comparable with the reported structures (Krishnakumar et al., 2012; Sudhahar et al., 2013).

In the molecular structure, the cation and anion are linked by N—H···O and O—H···O hydrogen bonds. In the anion, the dihedral angle between the carboxyl group and the benzene ring is 5.02 (12)°. The crystal structure exhibits intermolecular N—H···O, O—H···O and C—H···O (Table 1 & Fig. 2) interactions.

Related literature top

For background to non-linear optical materials, see: Yang et al. (2005); Kumar et al. (2009). For related structures, see: Krishnakumar et al. (2012); Sudhahar et al. (2013).

Experimental top

The title compound was obtained by slow evaporation from an aqueous solution of glycine (C2H5NO2, 0.75 g) and 3-carboxy-4-hydroxybenzenesulfonic acid (C7H6O6S, 2.18 g) at room temperature. The good quality crystals suitable for X-ray diffraction were collected in the period of 20 days.

Refinement top

H atoms of the NH3 and OH groups were located in a difference Fourier map and refined freely, with bond-length restraints of N—H = 0.86 (1) Å and O—H = 0.82 (1) Å. The C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 and Uiso(H) = 1.2Ueq(C) for CH and C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for CH2.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. A packing diagram of the title compound, viewed down the a axis. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.
Glycinium 3-carboxy-4-hydroxybenzenesulfonate top
Crystal data top
C2H6NO2+·C7H5O6SF(000) = 608
Mr = 293.25Dx = 1.691 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9634 reflections
a = 5.3651 (3) Åθ = 2.5–32.0°
b = 24.7207 (15) ŵ = 0.32 mm1
c = 8.6840 (5) ÅT = 295 K
β = 90.170 (2)°Block, colourless
V = 1151.75 (12) Å30.36 × 0.32 × 0.30 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3694 independent reflections
Radiation source: fine-focus sealed tube3282 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω and ϕ scanθmax = 32.1°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.893, Tmax = 0.910k = 3636
21406 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117 w = 1/[σ2(Fo2) + (0.0325P)2 + 1.2564P]
where P = (Fo2 + 2Fc2)/3
S = 1.20(Δ/σ)max < 0.001
3694 reflectionsΔρmax = 0.49 e Å3
197 parametersΔρmin = 0.53 e Å3
6 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.071 (3)
Crystal data top
C2H6NO2+·C7H5O6SV = 1151.75 (12) Å3
Mr = 293.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.3651 (3) ŵ = 0.32 mm1
b = 24.7207 (15) ÅT = 295 K
c = 8.6840 (5) Å0.36 × 0.32 × 0.30 mm
β = 90.170 (2)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3694 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3282 reflections with I > 2σ(I)
Tmin = 0.893, Tmax = 0.910Rint = 0.030
21406 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0496 restraints
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.20Δρmax = 0.49 e Å3
3694 reflectionsΔρmin = 0.53 e Å3
197 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5636 (3)0.41186 (7)0.7824 (2)0.0177 (3)
C20.6669 (3)0.46042 (7)0.8273 (2)0.0194 (3)
H20.80740.46070.89030.023*
C30.5608 (3)0.50936 (7)0.7784 (2)0.0198 (3)
C40.3495 (4)0.50846 (8)0.6831 (2)0.0244 (4)
C50.2445 (4)0.45897 (8)0.6403 (3)0.0283 (4)
H50.10270.45830.57850.034*
C60.3505 (4)0.41112 (8)0.6893 (2)0.0244 (4)
H60.28010.37830.66030.029*
C70.6683 (4)0.56133 (7)0.8269 (2)0.0248 (4)
C80.8846 (4)0.69748 (7)0.6240 (2)0.0213 (3)
C90.8379 (4)0.71637 (8)0.7865 (2)0.0221 (3)
H9A0.90960.69080.85890.026*
H9B0.91660.75120.80280.026*
N10.5669 (3)0.72092 (7)0.81273 (19)0.0219 (3)
O10.2384 (3)0.55374 (7)0.6301 (2)0.0398 (4)
O20.8214 (3)0.32854 (7)0.69766 (18)0.0377 (4)
O30.5004 (3)0.31390 (6)0.88206 (18)0.0305 (3)
O40.8755 (3)0.36047 (6)0.9590 (2)0.0364 (4)
O50.8540 (3)0.55664 (6)0.9256 (2)0.0364 (4)
O60.5921 (3)0.60513 (6)0.7813 (2)0.0380 (4)
O71.1214 (3)0.68486 (8)0.60241 (19)0.0386 (4)
O80.7240 (3)0.69592 (6)0.52779 (16)0.0278 (3)
S10.70129 (8)0.349884 (16)0.83495 (5)0.01747 (12)
H1A0.489 (6)0.6942 (10)0.771 (4)0.059 (10)*
H1B0.515 (6)0.7512 (8)0.774 (4)0.059 (10)*
H1C0.528 (6)0.7171 (14)0.9088 (15)0.059 (10)*
H5A0.910 (6)0.5865 (7)0.949 (4)0.051 (9)*
H71.134 (6)0.6766 (12)0.5112 (15)0.048 (9)*
H10.320 (6)0.5791 (10)0.665 (4)0.064 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0206 (8)0.0139 (7)0.0186 (8)0.0001 (6)0.0015 (6)0.0008 (6)
C20.0198 (8)0.0163 (7)0.0219 (8)0.0006 (6)0.0050 (6)0.0003 (6)
C30.0229 (8)0.0147 (7)0.0218 (8)0.0006 (6)0.0037 (6)0.0001 (6)
C40.0261 (9)0.0201 (8)0.0270 (9)0.0030 (7)0.0065 (7)0.0031 (7)
C50.0249 (9)0.0258 (9)0.0342 (11)0.0013 (7)0.0141 (8)0.0010 (8)
C60.0249 (9)0.0196 (8)0.0286 (9)0.0025 (6)0.0071 (7)0.0034 (7)
C70.0292 (10)0.0161 (7)0.0291 (9)0.0014 (6)0.0055 (8)0.0003 (7)
C80.0271 (9)0.0181 (7)0.0186 (8)0.0005 (6)0.0015 (7)0.0008 (6)
C90.0255 (9)0.0238 (8)0.0169 (8)0.0034 (7)0.0012 (6)0.0017 (6)
N10.0278 (8)0.0198 (7)0.0181 (7)0.0003 (6)0.0008 (6)0.0003 (6)
O10.0426 (9)0.0232 (7)0.0534 (11)0.0065 (7)0.0235 (8)0.0052 (7)
O20.0510 (10)0.0343 (8)0.0279 (8)0.0189 (7)0.0124 (7)0.0003 (6)
O30.0374 (8)0.0217 (6)0.0324 (8)0.0097 (6)0.0019 (6)0.0069 (6)
O40.0463 (9)0.0209 (7)0.0419 (9)0.0003 (6)0.0261 (8)0.0003 (6)
O50.0452 (9)0.0190 (7)0.0449 (9)0.0059 (6)0.0232 (8)0.0013 (6)
O60.0492 (10)0.0150 (6)0.0496 (10)0.0014 (6)0.0166 (8)0.0022 (6)
O70.0282 (8)0.0602 (11)0.0274 (8)0.0057 (7)0.0009 (6)0.0083 (7)
O80.0328 (8)0.0322 (7)0.0183 (6)0.0033 (6)0.0035 (5)0.0020 (5)
S10.0230 (2)0.01263 (18)0.0168 (2)0.00042 (14)0.00211 (14)0.00052 (13)
Geometric parameters (Å, º) top
C1—C21.378 (2)C8—O71.322 (2)
C1—C61.399 (3)C8—C91.508 (3)
C1—S11.7605 (17)C9—N11.477 (3)
C2—C31.402 (2)C9—H9A0.9700
C2—H20.9300C9—H9B0.9700
C3—C41.402 (3)N1—H1A0.863 (10)
C3—C71.470 (2)N1—H1B0.866 (10)
C4—O11.348 (2)N1—H1C0.865 (10)
C4—C51.397 (3)O1—H10.823 (10)
C5—C61.379 (3)O2—S11.4559 (15)
C5—H50.9300O3—S11.4570 (14)
C6—H60.9300O4—S11.4478 (15)
C7—O61.223 (2)O5—H5A0.822 (10)
C7—O51.317 (2)O7—H70.821 (10)
C8—O81.199 (2)
C2—C1—C6120.16 (16)O7—C8—C9111.59 (17)
C2—C1—S1121.11 (13)N1—C9—C8109.53 (15)
C6—C1—S1118.69 (13)N1—C9—H9A109.8
C1—C2—C3120.21 (16)C8—C9—H9A109.8
C1—C2—H2119.9N1—C9—H9B109.8
C3—C2—H2119.9C8—C9—H9B109.8
C4—C3—C2119.48 (16)H9A—C9—H9B108.2
C4—C3—C7119.94 (16)C9—N1—H1A111 (2)
C2—C3—C7120.58 (16)C9—N1—H1B109 (2)
O1—C4—C5117.33 (17)H1A—N1—H1B110 (3)
O1—C4—C3122.96 (17)C9—N1—H1C112 (2)
C5—C4—C3119.71 (17)H1A—N1—H1C102 (3)
C6—C5—C4120.24 (18)H1B—N1—H1C113 (3)
C6—C5—H5119.9C4—O1—H1106 (3)
C4—C5—H5119.9C7—O5—H5A111 (2)
C5—C6—C1120.18 (17)C8—O7—H7106 (2)
C5—C6—H6119.9O4—S1—O2112.85 (11)
C1—C6—H6119.9O4—S1—O3112.21 (10)
O6—C7—O5122.70 (18)O2—S1—O3109.77 (10)
O6—C7—C3123.42 (18)O4—S1—C1107.75 (8)
O5—C7—C3113.88 (16)O2—S1—C1106.85 (9)
O8—C8—O7125.65 (18)O3—S1—C1107.09 (9)
O8—C8—C9122.73 (18)
C6—C1—C2—C30.8 (3)C4—C3—C7—O64.4 (3)
S1—C1—C2—C3177.08 (14)C2—C3—C7—O6175.9 (2)
C1—C2—C3—C40.2 (3)C4—C3—C7—O5175.01 (19)
C1—C2—C3—C7179.42 (18)C2—C3—C7—O54.7 (3)
C2—C3—C4—O1179.32 (19)O8—C8—C9—N111.5 (2)
C7—C3—C4—O11.0 (3)O7—C8—C9—N1170.32 (16)
C2—C3—C4—C51.2 (3)C2—C1—S1—O416.02 (18)
C7—C3—C4—C5178.49 (19)C6—C1—S1—O4166.12 (16)
O1—C4—C5—C6179.4 (2)C2—C1—S1—O2105.50 (17)
C3—C4—C5—C61.1 (3)C6—C1—S1—O272.36 (17)
C4—C5—C6—C10.1 (3)C2—C1—S1—O3136.93 (15)
C2—C1—C6—C50.8 (3)C6—C1—S1—O345.21 (17)
S1—C1—C6—C5177.06 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O60.82 (1)1.89 (2)2.631 (2)150 (4)
N1—H1A···O60.86 (1)2.27 (3)2.878 (2)127 (3)
N1—H1A···O7i0.86 (1)2.46 (3)3.134 (2)135 (3)
N1—H1B···O3ii0.87 (1)2.06 (2)2.876 (2)157 (3)
N1—H1C···O3iii0.87 (1)1.98 (2)2.811 (2)161 (3)
O5—H5A···O4iv0.82 (1)1.92 (2)2.702 (2)159 (3)
O7—H7···O2v0.82 (1)1.84 (1)2.646 (2)169 (3)
C2—H2···O5iv0.932.453.370 (2)168
C9—H9A···O4iv0.972.333.292 (2)172
C6—H6···O8vi0.932.463.273 (2)147
C9—H9B···O2vii0.972.373.324 (2)167
Symmetry codes: (i) x1, y, z; (ii) x+1, y+1/2, z+3/2; (iii) x+1, y+1, z+2; (iv) x+2, y+1, z+2; (v) x+2, y+1, z+1; (vi) x+1, y+1, z+1; (vii) x+2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O60.823 (10)1.89 (2)2.631 (2)150 (4)
N1—H1A···O60.863 (10)2.27 (3)2.878 (2)127 (3)
N1—H1A···O7i0.863 (10)2.46 (3)3.134 (2)135 (3)
N1—H1B···O3ii0.866 (10)2.061 (16)2.876 (2)157 (3)
N1—H1C···O3iii0.865 (10)1.978 (15)2.811 (2)161 (3)
O5—H5A···O4iv0.822 (10)1.917 (15)2.702 (2)159 (3)
O7—H7···O2v0.821 (10)1.835 (12)2.646 (2)169 (3)
C2—H2···O5iv0.932.453.370 (2)168
C9—H9A···O4iv0.972.333.292 (2)172
C6—H6···O8vi0.932.463.273 (2)147
C9—H9B···O2vii0.972.373.324 (2)167
Symmetry codes: (i) x1, y, z; (ii) x+1, y+1/2, z+3/2; (iii) x+1, y+1, z+2; (iv) x+2, y+1, z+2; (v) x+2, y+1, z+1; (vi) x+1, y+1, z+1; (vii) x+2, y+1/2, z+3/2.
 

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