Bis(carboxy­meth­yl)ammonium 4-toluene­sulfonate

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536808026214

organic compounds

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Volume 64| Part 9| September 2008| Page o1798

doi:10.1107/S1600536808026214

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Bis(carboxymethyl)ammonium 4-toluenesulfonate

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 8 August 2008; accepted 14 August 2008; online 20 August 2008)

The iminodiacetic acid component of the title salt, C₄H₈NO₄⁺·C₇H₇SO₃⁻, is protonated at the N atom. The cation uses the ammonium group to form hydrogen bonds to the O atoms of two adjacent sulfonate groups. In addition, the carboxylic acid portions of the cation form hydrogen bonds to the sulfonate groups. The hydrogen-bonding interactions give rise to a layer structure.

Related literature

For the crystal structures of iminodiacetic acid hydrohalides, see: Oskarsson (1973 , 1974a ,b , 1976 ).

Experimental

Crystal data

C₄H₈NO₄⁺·C₇H₇O₃S⁻
M_r = 305.30
Orthorhombic, P b c a
a = 9.9291 (2) Å
b = 10.3636 (2) Å
c = 25.8862 (5) Å
V = 2663.72 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 (2) K
0.27 × 0.27 × 0.27 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.929, T_max = 0.929
20842 measured reflections
3059 independent reflections
2560 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.119
S = 1.15
3059 reflections
198 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.88 (1)	2.02 (1)	2.885 (2)	167 (2)
N1—H1N2⋯O3ⁱⁱ	0.88 (1)	2.06 (2)	2.792 (2)	140 (2)
O5—H5O⋯O1	0.84 (1)	1.79 (1)	2.607 (2)	164 (3)
O7—H7O⋯O2ⁱⁱⁱ	0.84 (1)	1.85 (1)	2.659 (2)	160 (3)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y-1, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026214/bh2187sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808026214/bh2187Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of iminodiacetic acid hydrohalides, see: Oskarsson (1973, 1974a,b, 1976).

Experimental top

Iminodiacetic acid (0.55 g, 4 mmol) and p-toluenesulfonic acid (0.65 g, 4 mmol) were heated in toluene (100 ml) for 1 h. Crystals were isolated from the cool solution after several days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of (C₄H₈NO₄)⁺(C₇H₇O₃S)^- at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Bis(carboxymethyl)ammonium 4-toluenesulfonate top

Crystal data top

C₄H₈NO₄⁺·C₇H₇O₃S⁻	F(000) = 1280
M_r = 305.30	D_x = 1.523 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4293 reflections
a = 9.9291 (2) Å	θ = 2.9–27.2°
b = 10.3636 (2) Å	µ = 0.28 mm⁻¹
c = 25.8862 (5) Å	T = 100 K
V = 2663.72 (9) Å³	Triangular block, colorless
Z = 8	0.27 × 0.27 × 0.27 mm

Data collection top

Bruker SMART APEX diffractometer	3059 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→7
T_min = 0.930, T_max = 0.930	k = −13→13
20842 measured reflections	l = −33→33

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0644P)² + 0.8206P] where P = (F_o² + 2F_c²)/3
3059 reflections	(Δ/σ)_max = 0.001
198 parameters	Δρ_max = 0.42 e Å⁻³
4 restraints	Δρ_min = −0.50 e Å⁻³
0 constraints

Crystal data top

C₄H₈NO₄⁺·C₇H₇O₃S⁻	V = 2663.72 (9) Å³
M_r = 305.30	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.9291 (2) Å	µ = 0.28 mm⁻¹
b = 10.3636 (2) Å	T = 100 K
c = 25.8862 (5) Å	0.27 × 0.27 × 0.27 mm

Data collection top

Bruker SMART APEX diffractometer	3059 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2560 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.930	R_int = 0.048
20842 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	4 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.42 e Å⁻³
3059 reflections	Δρ_min = −0.50 e Å⁻³
198 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.49041 (5)	0.84948 (4)	0.358654 (17)	0.01248 (14)
O1	0.55419 (15)	0.74172 (13)	0.38508 (5)	0.0195 (3)
O2	0.56209 (14)	0.88382 (13)	0.31102 (5)	0.0163 (3)
O3	0.34727 (14)	0.83294 (13)	0.35029 (5)	0.0190 (3)
O4	0.40223 (14)	0.52637 (13)	0.30853 (5)	0.0171 (3)
O5	0.51261 (16)	0.49339 (13)	0.38301 (5)	0.0199 (3)
H5O	0.510 (3)	0.5747 (10)	0.3841 (10)	0.034 (7)*
O6	0.20627 (14)	0.17528 (13)	0.21695 (5)	0.0176 (3)
O7	0.29656 (14)	−0.02406 (13)	0.22217 (5)	0.0163 (3)
H7O	0.229 (2)	−0.047 (3)	0.2048 (10)	0.051 (9)*
N1	0.37466 (17)	0.27383 (15)	0.28845 (6)	0.0129 (3)
H1N1	0.402 (3)	0.316 (2)	0.2610 (7)	0.031 (7)*
H1N2	0.2899 (11)	0.296 (2)	0.2924 (8)	0.014 (5)*
C1	0.50864 (19)	0.98391 (18)	0.40013 (7)	0.0141 (4)
C2	0.3995 (2)	1.02980 (19)	0.42797 (8)	0.0187 (4)
H2	0.3146	0.9879	0.4256	0.022*
C3	0.4152 (2)	1.1376 (2)	0.45941 (8)	0.0212 (4)
H3	0.3404	1.1681	0.4788	0.025*
C4	0.5374 (2)	1.20164 (19)	0.46306 (7)	0.0183 (4)
C5	0.6471 (2)	1.15329 (19)	0.43556 (8)	0.0191 (4)
H5	0.7319	1.1952	0.4380	0.023*
C6	0.6335 (2)	1.04440 (19)	0.40462 (7)	0.0171 (4)
H6	0.7093	1.0112	0.3866	0.021*
C7	0.5517 (2)	1.3217 (2)	0.49545 (8)	0.0247 (5)
H7A	0.4636	1.3631	0.4993	0.037*
H7B	0.6142	1.3815	0.4785	0.037*
H7C	0.5868	1.2985	0.5296	0.037*
C8	0.45172 (19)	0.45546 (18)	0.34029 (7)	0.0137 (4)
C9	0.45326 (19)	0.31071 (18)	0.33494 (7)	0.0137 (4)
H9A	0.5472	0.2798	0.3315	0.016*
H9B	0.4132	0.2705	0.3660	0.016*
C10	0.3811 (2)	0.13288 (17)	0.27813 (7)	0.0142 (4)
H10A	0.3570	0.0845	0.3098	0.017*
H10B	0.4738	0.1085	0.2680	0.017*
C11	0.28461 (19)	0.09925 (18)	0.23534 (7)	0.0132 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0104 (2)	0.0118 (2)	0.0153 (2)	−0.00084 (17)	−0.00072 (16)	0.00057 (16)
O1	0.0240 (8)	0.0125 (7)	0.0221 (7)	−0.0013 (6)	−0.0072 (6)	0.0031 (5)
O2	0.0164 (7)	0.0158 (7)	0.0168 (7)	−0.0021 (6)	0.0028 (5)	−0.0016 (5)
O3	0.0109 (7)	0.0226 (8)	0.0233 (7)	−0.0016 (6)	−0.0006 (6)	−0.0024 (5)
O4	0.0169 (7)	0.0148 (7)	0.0197 (7)	0.0007 (6)	−0.0025 (5)	0.0007 (5)
O5	0.0293 (9)	0.0111 (7)	0.0192 (7)	−0.0007 (6)	−0.0092 (6)	−0.0014 (5)
O6	0.0156 (7)	0.0155 (7)	0.0217 (7)	−0.0016 (6)	−0.0030 (5)	0.0033 (5)
O7	0.0134 (7)	0.0143 (7)	0.0211 (7)	−0.0023 (6)	−0.0006 (6)	−0.0043 (5)
N1	0.0123 (8)	0.0109 (8)	0.0154 (8)	0.0011 (6)	−0.0002 (6)	0.0000 (6)
C1	0.0144 (9)	0.0131 (9)	0.0149 (8)	−0.0001 (7)	−0.0003 (7)	0.0010 (7)
C2	0.0148 (10)	0.0198 (10)	0.0215 (9)	−0.0019 (8)	0.0032 (8)	0.0004 (8)
C3	0.0190 (11)	0.0217 (10)	0.0228 (10)	0.0025 (8)	0.0066 (8)	−0.0020 (8)
C4	0.0237 (11)	0.0162 (10)	0.0150 (9)	0.0007 (8)	−0.0001 (8)	0.0004 (7)
C5	0.0145 (10)	0.0225 (10)	0.0202 (9)	−0.0045 (8)	0.0002 (8)	−0.0023 (8)
C6	0.0130 (9)	0.0199 (10)	0.0183 (9)	0.0004 (8)	0.0014 (7)	−0.0027 (7)
C7	0.0276 (12)	0.0219 (11)	0.0247 (10)	−0.0011 (9)	0.0010 (9)	−0.0067 (8)
C8	0.0102 (9)	0.0150 (9)	0.0161 (8)	−0.0005 (7)	0.0005 (7)	0.0004 (7)
C9	0.0125 (9)	0.0133 (9)	0.0152 (9)	0.0002 (7)	−0.0026 (7)	0.0000 (7)
C10	0.0132 (9)	0.0095 (8)	0.0200 (9)	0.0004 (7)	−0.0017 (7)	−0.0009 (7)
C11	0.0108 (9)	0.0132 (9)	0.0157 (8)	−0.0019 (7)	0.0028 (7)	0.0012 (7)

Geometric parameters (Å, º) top

S1—O3	1.4478 (14)	C2—H2	0.9500
S1—O1	1.4547 (14)	C3—C4	1.386 (3)
S1—O2	1.4675 (13)	C3—H3	0.9500
S1—C1	1.768 (2)	C4—C5	1.394 (3)
O4—C8	1.207 (2)	C4—C7	1.507 (3)
O5—C8	1.320 (2)	C5—C6	1.390 (3)
O5—H5o	0.84 (1)	C5—H5	0.9500
O6—C11	1.205 (2)	C6—H6	0.9500
O7—C11	1.328 (2)	C7—H7A	0.9800
O7—H7o	0.84 (1)	C7—H7B	0.9800
N1—C9	1.484 (2)	C7—H7C	0.9800
N1—C10	1.486 (2)	C8—C9	1.507 (3)
N1—H1n1	0.88 (1)	C9—H9A	0.9900
N1—H1n2	0.88 (1)	C9—H9B	0.9900
C1—C2	1.385 (3)	C10—C11	1.505 (3)
C1—C6	1.394 (3)	C10—H10A	0.9900
C2—C3	1.391 (3)	C10—H10B	0.9900

O3—S1—O1	114.00 (9)	C4—C5—H5	119.7
O3—S1—O2	112.28 (8)	C5—C6—C1	119.93 (18)
O1—S1—O2	111.72 (8)	C5—C6—H6	120.0
O3—S1—C1	106.53 (9)	C1—C6—H6	120.0
O1—S1—C1	105.95 (9)	C4—C7—H7A	109.5
O2—S1—C1	105.63 (8)	C4—C7—H7B	109.5
C8—O5—H5O	108.2 (18)	H7A—C7—H7B	109.5
C11—O7—H7O	110 (2)	C4—C7—H7C	109.5
C9—N1—C10	112.10 (14)	H7A—C7—H7C	109.5
C9—N1—H1N1	111.7 (17)	H7B—C7—H7C	109.5
C10—N1—H1N1	109.4 (16)	O4—C8—O5	125.13 (18)
C9—N1—H1N2	110.2 (14)	O4—C8—C9	123.20 (17)
C10—N1—H1N2	108.3 (15)	O5—C8—C9	111.66 (15)
H1N1—N1—H1N2	105 (2)	N1—C9—C8	109.01 (15)
C2—C1—C6	119.85 (18)	N1—C9—H9A	109.9
C2—C1—S1	120.41 (15)	C8—C9—H9A	109.9
C6—C1—S1	119.73 (15)	N1—C9—H9B	109.9
C1—C2—C3	119.53 (19)	C8—C9—H9B	109.9
C1—C2—H2	120.2	H9A—C9—H9B	108.3
C3—C2—H2	120.2	N1—C10—C11	109.43 (15)
C4—C3—C2	121.46 (18)	N1—C10—H10A	109.8
C4—C3—H3	119.3	C11—C10—H10A	109.8
C2—C3—H3	119.3	N1—C10—H10B	109.8
C3—C4—C5	118.49 (18)	C11—C10—H10B	109.8
C3—C4—C7	121.06 (19)	H10A—C10—H10B	108.2
C5—C4—C7	120.4 (2)	O6—C11—O7	125.83 (17)
C6—C5—C4	120.68 (19)	O6—C11—C10	123.36 (17)
C6—C5—H5	119.7	O7—C11—C10	110.79 (16)

O3—S1—C1—C2	16.35 (19)	C3—C4—C5—C6	0.9 (3)
O1—S1—C1—C2	−105.40 (17)	C7—C4—C5—C6	−178.42 (18)
O2—S1—C1—C2	135.94 (16)	C4—C5—C6—C1	1.2 (3)
O3—S1—C1—C6	−163.36 (15)	C2—C1—C6—C5	−2.3 (3)
O1—S1—C1—C6	74.89 (17)	S1—C1—C6—C5	177.39 (15)
O2—S1—C1—C6	−43.77 (18)	C10—N1—C9—C8	175.26 (15)
C6—C1—C2—C3	1.3 (3)	O4—C8—C9—N1	−5.4 (3)
S1—C1—C2—C3	−178.42 (15)	O5—C8—C9—N1	175.76 (15)
C1—C2—C3—C4	0.9 (3)	C9—N1—C10—C11	172.17 (15)
C2—C3—C4—C5	−1.9 (3)	N1—C10—C11—O6	−6.8 (3)
C2—C3—C4—C7	177.37 (19)	N1—C10—C11—O7	174.56 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱ	0.88 (1)	2.02 (1)	2.885 (2)	167 (2)
N1—H1N2···O3ⁱⁱ	0.88 (1)	2.06 (2)	2.792 (2)	140 (2)
O5—H5O···O1	0.84 (1)	1.79 (1)	2.607 (2)	164 (3)
O7—H7O···O2ⁱⁱⁱ	0.84 (1)	1.85 (1)	2.659 (2)	160 (3)

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

Experimental details

Crystal data
Chemical formula	C₄H₈NO₄⁺·C₇H₇O₃S⁻
M_r	305.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	9.9291 (2), 10.3636 (2), 25.8862 (5)
V (Å³)	2663.72 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.27 × 0.27 × 0.27

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.930, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	20842, 3059, 2560
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.119, 1.15
No. of reflections	3059
No. of parameters	198
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.50

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱ	0.88 (1)	2.02 (1)	2.885 (2)	167 (2)
N1—H1N2···O3ⁱⁱ	0.88 (1)	2.06 (2)	2.792 (2)	140 (2)
O5—H5O···O1	0.84 (1)	1.79 (1)	2.607 (2)	164 (3)
O7—H7O···O2ⁱⁱⁱ	0.84 (1)	1.85 (1)	2.659 (2)	160 (3)

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

Acknowledgements

We thank the University of Malaya for funding this study (SF022/2007 A, FS339/2008 A) and also for the purchase of the diffractometer.

References

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