Glycinium 3-carb­oxy-4-hy­droxy­benzene­sulfonate

Thirunavukkarasu, A.; Silambarasan, A.; Kumar, R.M.; Umarani, P.R.; Chakkaravarthi, G.

doi:10.1107/S1600536814004590

organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o397

doi:10.1107/S1600536814004590

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Glycinium 3-carboxy-4-hydroxybenzenesulfonate

A. Thirunavukkarasu,^a A. Silambarasan,^a R. Mohan Kumar,^a P. R. Umarani ^b ^* and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bKunthavai Naacchiyaar Govt. Arts College (W), Thanjavur 613 007, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: kan_uma6@yahoo.com, chakkaravarthi_2005@yahoo.com

(Received 21 February 2014; accepted 27 February 2014; online 5 March 2014)

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.

CCDC reference: 989106

Related literature

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

Crystal data

C₂H₆NO₂⁺·C₇H₅O₆S⁻
M_r = 293.25
Monoclinic, P 2₁ /c
a = 5.3651 (3) Å
b = 24.7207 (15) Å
c = 8.6840 (5) Å
β = 90.170 (2)°
V = 1151.75 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 295 K
0.36 × 0.32 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.893, T_max = 0.910
21406 measured reflections
3694 independent reflections
3282 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.117
S = 1.20
3694 reflections
197 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O6	0.82 (1)	1.89 (2)	2.631 (2)	150 (4)
N1—H1A⋯O6	0.86 (1)	2.27 (3)	2.878 (2)	127 (3)
N1—H1A⋯O7ⁱ	0.86 (1)	2.46 (3)	3.134 (2)	135 (3)
N1—H1B⋯O3ⁱⁱ	0.87 (1)	2.06 (2)	2.876 (2)	157 (3)
N1—H1C⋯O3ⁱⁱⁱ	0.87 (1)	1.98 (2)	2.811 (2)	161 (3)
O5—H5A⋯O4^iv	0.82 (1)	1.92 (2)	2.702 (2)	159 (3)
O7—H7⋯O2^v	0.82 (1)	1.84 (1)	2.646 (2)	169 (3)
C2—H2⋯O5^iv	0.93	2.45	3.370 (2)	168
C9—H9A⋯O4^iv	0.97	2.33	3.292 (2)	172
C6—H6⋯O8^vi	0.93	2.46	3.273 (2)	147
C9—H9B⋯O2^vii	0.97	2.37	3.324 (2)	167
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (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) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

CCDC reference: 989106

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814004590/is5343sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814004590/is5343Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814004590/is5343Isup3.cml

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	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⁺·C₇H₅O₆S⁻	F(000) = 608
M_r = 293.25	D_x = 1.691 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9634 reflections
a = 5.3651 (3) Å	θ = 2.5–32.0°
b = 24.7207 (15) Å	µ = 0.32 mm⁻¹
c = 8.6840 (5) Å	T = 295 K
β = 90.170 (2)°	Block, colourless
V = 1151.75 (12) Å³	0.36 × 0.32 × 0.30 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	3694 independent reflections
Radiation source: fine-focus sealed tube	3282 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scan	θ_max = 32.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.893, T_max = 0.910	k = −36→36
21406 measured reflections	l = −12→12

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0325P)² + 1.2564P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max < 0.001
3694 reflections	Δρ_max = 0.49 e Å⁻³
197 parameters	Δρ_min = −0.53 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.071 (3)

Crystal data top

C₂H₆NO₂⁺·C₇H₅O₆S⁻	V = 1151.75 (12) Å³
M_r = 293.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.3651 (3) Å	µ = 0.32 mm⁻¹
b = 24.7207 (15) Å	T = 295 K
c = 8.6840 (5) Å	0.36 × 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)
T_min = 0.893, T_max = 0.910	R_int = 0.030
21406 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	6 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.49 e Å⁻³
3694 reflections	Δρ_min = −0.53 e Å⁻³
197 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5636 (3)	0.41186 (7)	0.7824 (2)	0.0177 (3)
C2	0.6669 (3)	0.46042 (7)	0.8273 (2)	0.0194 (3)
H2	0.8074	0.4607	0.8903	0.023*
C3	0.5608 (3)	0.50936 (7)	0.7784 (2)	0.0198 (3)
C4	0.3495 (4)	0.50846 (8)	0.6831 (2)	0.0244 (4)
C5	0.2445 (4)	0.45897 (8)	0.6403 (3)	0.0283 (4)
H5	0.1027	0.4583	0.5785	0.034*
C6	0.3505 (4)	0.41112 (8)	0.6893 (2)	0.0244 (4)
H6	0.2801	0.3783	0.6603	0.029*
C7	0.6683 (4)	0.56133 (7)	0.8269 (2)	0.0248 (4)
C8	0.8846 (4)	0.69748 (7)	0.6240 (2)	0.0213 (3)
C9	0.8379 (4)	0.71637 (8)	0.7865 (2)	0.0221 (3)
H9A	0.9096	0.6908	0.8589	0.026*
H9B	0.9166	0.7512	0.8028	0.026*
N1	0.5669 (3)	0.72092 (7)	0.81273 (19)	0.0219 (3)
O1	0.2384 (3)	0.55374 (7)	0.6301 (2)	0.0398 (4)
O2	0.8214 (3)	0.32854 (7)	0.69766 (18)	0.0377 (4)
O3	0.5004 (3)	0.31390 (6)	0.88206 (18)	0.0305 (3)
O4	0.8755 (3)	0.36047 (6)	0.9590 (2)	0.0364 (4)
O5	0.8540 (3)	0.55664 (6)	0.9256 (2)	0.0364 (4)
O6	0.5921 (3)	0.60513 (6)	0.7813 (2)	0.0380 (4)
O7	1.1214 (3)	0.68486 (8)	0.60241 (19)	0.0386 (4)
O8	0.7240 (3)	0.69592 (6)	0.52779 (16)	0.0278 (3)
S1	0.70129 (8)	0.349884 (16)	0.83495 (5)	0.01747 (12)
H1A	0.489 (6)	0.6942 (10)	0.771 (4)	0.059 (10)*
H1B	0.515 (6)	0.7512 (8)	0.774 (4)	0.059 (10)*
H1C	0.528 (6)	0.7171 (14)	0.9088 (15)	0.059 (10)*
H5A	0.910 (6)	0.5865 (7)	0.949 (4)	0.051 (9)*
H7	1.134 (6)	0.6766 (12)	0.5112 (15)	0.048 (9)*
H1	0.320 (6)	0.5791 (10)	0.665 (4)	0.064 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0206 (8)	0.0139 (7)	0.0186 (8)	−0.0001 (6)	−0.0015 (6)	−0.0008 (6)
C2	0.0198 (8)	0.0163 (7)	0.0219 (8)	−0.0006 (6)	−0.0050 (6)	−0.0003 (6)
C3	0.0229 (8)	0.0147 (7)	0.0218 (8)	−0.0006 (6)	−0.0037 (6)	0.0001 (6)
C4	0.0261 (9)	0.0201 (8)	0.0270 (9)	0.0030 (7)	−0.0065 (7)	0.0031 (7)
C5	0.0249 (9)	0.0258 (9)	0.0342 (11)	0.0013 (7)	−0.0141 (8)	−0.0010 (8)
C6	0.0249 (9)	0.0196 (8)	0.0286 (9)	−0.0025 (6)	−0.0071 (7)	−0.0034 (7)
C7	0.0292 (10)	0.0161 (7)	0.0291 (9)	−0.0014 (6)	−0.0055 (8)	0.0003 (7)
C8	0.0271 (9)	0.0181 (7)	0.0186 (8)	−0.0005 (6)	0.0015 (7)	0.0008 (6)
C9	0.0255 (9)	0.0238 (8)	0.0169 (8)	−0.0034 (7)	−0.0012 (6)	−0.0017 (6)
N1	0.0278 (8)	0.0198 (7)	0.0181 (7)	−0.0003 (6)	0.0008 (6)	−0.0003 (6)
O1	0.0426 (9)	0.0232 (7)	0.0534 (11)	0.0065 (7)	−0.0235 (8)	0.0052 (7)
O2	0.0510 (10)	0.0343 (8)	0.0279 (8)	0.0189 (7)	0.0124 (7)	0.0003 (6)
O3	0.0374 (8)	0.0217 (6)	0.0324 (8)	−0.0097 (6)	0.0019 (6)	0.0069 (6)
O4	0.0463 (9)	0.0209 (7)	0.0419 (9)	0.0003 (6)	−0.0261 (8)	−0.0003 (6)
O5	0.0452 (9)	0.0190 (7)	0.0449 (9)	−0.0059 (6)	−0.0232 (8)	−0.0013 (6)
O6	0.0492 (10)	0.0150 (6)	0.0496 (10)	0.0014 (6)	−0.0166 (8)	0.0022 (6)
O7	0.0282 (8)	0.0602 (11)	0.0274 (8)	0.0057 (7)	0.0009 (6)	−0.0083 (7)
O8	0.0328 (8)	0.0322 (7)	0.0183 (6)	0.0033 (6)	−0.0035 (5)	−0.0020 (5)
S1	0.0230 (2)	0.01263 (18)	0.0168 (2)	−0.00042 (14)	−0.00211 (14)	−0.00052 (13)

Geometric parameters (Å, º) top

C1—C2	1.378 (2)	C8—O7	1.322 (2)
C1—C6	1.399 (3)	C8—C9	1.508 (3)
C1—S1	1.7605 (17)	C9—N1	1.477 (3)
C2—C3	1.402 (2)	C9—H9A	0.9700
C2—H2	0.9300	C9—H9B	0.9700
C3—C4	1.402 (3)	N1—H1A	0.863 (10)
C3—C7	1.470 (2)	N1—H1B	0.866 (10)
C4—O1	1.348 (2)	N1—H1C	0.865 (10)
C4—C5	1.397 (3)	O1—H1	0.823 (10)
C5—C6	1.379 (3)	O2—S1	1.4559 (15)
C5—H5	0.9300	O3—S1	1.4570 (14)
C6—H6	0.9300	O4—S1	1.4478 (15)
C7—O6	1.223 (2)	O5—H5A	0.822 (10)
C7—O5	1.317 (2)	O7—H7	0.821 (10)
C8—O8	1.199 (2)

C2—C1—C6	120.16 (16)	O7—C8—C9	111.59 (17)
C2—C1—S1	121.11 (13)	N1—C9—C8	109.53 (15)
C6—C1—S1	118.69 (13)	N1—C9—H9A	109.8
C1—C2—C3	120.21 (16)	C8—C9—H9A	109.8
C1—C2—H2	119.9	N1—C9—H9B	109.8
C3—C2—H2	119.9	C8—C9—H9B	109.8
C4—C3—C2	119.48 (16)	H9A—C9—H9B	108.2
C4—C3—C7	119.94 (16)	C9—N1—H1A	111 (2)
C2—C3—C7	120.58 (16)	C9—N1—H1B	109 (2)
O1—C4—C5	117.33 (17)	H1A—N1—H1B	110 (3)
O1—C4—C3	122.96 (17)	C9—N1—H1C	112 (2)
C5—C4—C3	119.71 (17)	H1A—N1—H1C	102 (3)
C6—C5—C4	120.24 (18)	H1B—N1—H1C	113 (3)
C6—C5—H5	119.9	C4—O1—H1	106 (3)
C4—C5—H5	119.9	C7—O5—H5A	111 (2)
C5—C6—C1	120.18 (17)	C8—O7—H7	106 (2)
C5—C6—H6	119.9	O4—S1—O2	112.85 (11)
C1—C6—H6	119.9	O4—S1—O3	112.21 (10)
O6—C7—O5	122.70 (18)	O2—S1—O3	109.77 (10)
O6—C7—C3	123.42 (18)	O4—S1—C1	107.75 (8)
O5—C7—C3	113.88 (16)	O2—S1—C1	106.85 (9)
O8—C8—O7	125.65 (18)	O3—S1—C1	107.09 (9)
O8—C8—C9	122.73 (18)

C6—C1—C2—C3	−0.8 (3)	C4—C3—C7—O6	−4.4 (3)
S1—C1—C2—C3	177.08 (14)	C2—C3—C7—O6	175.9 (2)
C1—C2—C3—C4	−0.2 (3)	C4—C3—C7—O5	175.01 (19)
C1—C2—C3—C7	179.42 (18)	C2—C3—C7—O5	−4.7 (3)
C2—C3—C4—O1	−179.32 (19)	O8—C8—C9—N1	11.5 (2)
C7—C3—C4—O1	1.0 (3)	O7—C8—C9—N1	−170.32 (16)
C2—C3—C4—C5	1.2 (3)	C2—C1—S1—O4	16.02 (18)
C7—C3—C4—C5	−178.49 (19)	C6—C1—S1—O4	−166.12 (16)
O1—C4—C5—C6	179.4 (2)	C2—C1—S1—O2	−105.50 (17)
C3—C4—C5—C6	−1.1 (3)	C6—C1—S1—O2	72.36 (17)
C4—C5—C6—C1	0.1 (3)	C2—C1—S1—O3	136.93 (15)
C2—C1—C6—C5	0.8 (3)	C6—C1—S1—O3	−45.21 (17)
S1—C1—C6—C5	−177.06 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6	0.82 (1)	1.89 (2)	2.631 (2)	150 (4)
N1—H1A···O6	0.86 (1)	2.27 (3)	2.878 (2)	127 (3)
N1—H1A···O7ⁱ	0.86 (1)	2.46 (3)	3.134 (2)	135 (3)
N1—H1B···O3ⁱⁱ	0.87 (1)	2.06 (2)	2.876 (2)	157 (3)
N1—H1C···O3ⁱⁱⁱ	0.87 (1)	1.98 (2)	2.811 (2)	161 (3)
O5—H5A···O4^iv	0.82 (1)	1.92 (2)	2.702 (2)	159 (3)
O7—H7···O2^v	0.82 (1)	1.84 (1)	2.646 (2)	169 (3)
C2—H2···O5^iv	0.93	2.45	3.370 (2)	168
C9—H9A···O4^iv	0.97	2.33	3.292 (2)	172
C6—H6···O8^vi	0.93	2.46	3.273 (2)	147
C9—H9B···O2^vii	0.97	2.37	3.324 (2)	167

Symmetry codes: (i) x−1, 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···A	D—H	H···A	D···A	D—H···A
O1—H1···O6	0.823 (10)	1.89 (2)	2.631 (2)	150 (4)
N1—H1A···O6	0.863 (10)	2.27 (3)	2.878 (2)	127 (3)
N1—H1A···O7ⁱ	0.863 (10)	2.46 (3)	3.134 (2)	135 (3)
N1—H1B···O3ⁱⁱ	0.866 (10)	2.061 (16)	2.876 (2)	157 (3)
N1—H1C···O3ⁱⁱⁱ	0.865 (10)	1.978 (15)	2.811 (2)	161 (3)
O5—H5A···O4^iv	0.822 (10)	1.917 (15)	2.702 (2)	159 (3)
O7—H7···O2^v	0.821 (10)	1.835 (12)	2.646 (2)	169 (3)
C2—H2···O5^iv	0.93	2.45	3.370 (2)	168
C9—H9A···O4^iv	0.97	2.33	3.292 (2)	172
C6—H6···O8^vi	0.93	2.46	3.273 (2)	147
C9—H9B···O2^vii	0.97	2.37	3.324 (2)	167

Acknowledgements

The authors thank the SAIF, IIT, Madras, for the data collection.

References

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