1-Carb­oxy-2-hy­droxy­propan-1-aminium 4-methyl­benzene­sulfonate monohydrate

Prabu, P.; Thiruvalluvar, A.; Ramachandra Raja, C.

doi:10.1107/S241431461701848X

organic compounds

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ISSN: 2414-3146

Volume 3| Part 1| January 2018| x171848

https://doi.org/10.1107/S241431461701848X

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1-Carboxy-2-hydroxypropan-1-aminium 4-methylbenzenesulfonate monohydrate

P. Prabu,^a A. Thiruvalluvar ^b ^* and C. Ramachandra Raja ^a ‡

^aPostgraduate Research Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 001, Tamilnadu, India, and ^bKunthavai Naacchiyaar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 23 December 2017; accepted 30 December 2017; online 9 January 2018)

In the title hydrated salt, C₄H₁₀NO₃⁺·C₇H₇O₃S⁻·H₂O, an intramolecular C—H⋯O hydrogen bond in the cation generates an S(6) loop. In the crystal, carboxyl-O—H⋯O(sulfonate), hydroxyl-O—H⋯O(sulfonate), water-O—H⋯O(sulfonate, hydroxyl) and ammonium-N—H⋯O(water, carbonyl) hydrogen bonds link the components of the asymmetric unit into supramolecular layers parallel to (001).

Keywords: crystal structure; hydrated salt; p-toluenesulfonate; L-threonine; hydrogen bonding.

CCDC reference: 1814028

Structure description

Having a non-centrosymmetric crystal is an important requisite for second harmonic generation (Etter & Huang, 1992 ; Sarma et al., 1994 ). As part of our studies in this area, we now describe the crystal structure of the title hydrated molecular salt (Fig. 1), which crystallizes in the non-centrosymmetric space group P2₁. It crystallizes with one independent cation, an anion and a water molecule in the asymmetric unit.

Figure 1
A view of the asymmetric unit showing the atom numbering and displacement ellipsoids drawn at the 30% probability level. Dashed lines indicate hydrogen-bonding interactions.

There is an intramolecular C11—H11B⋯O5 hydrogen bond within the cation, which generates an S(6) ring, Table 1. The crystal structure features a variety of hydrogen bonds, as listed in Table 1. As seen from Fig. 2, the hydrogen bonds connect the constituents of the asymmetric unit into supramolecular layers that stack along the c-axis direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯O5	0.96	2.47	3.068 (4)	120
O5—H5A⋯O3	0.82	1.76	2.576 (3)	172
O6—H6A⋯O2ⁱ	0.82	1.90	2.713 (3)	172
O7—H7E⋯O1ⁱⁱ	0.88 (2)	1.98 (3)	2.770 (3)	149 (3)
O7—H7D⋯O6	0.88 (2)	1.88 (3)	2.741 (3)	166 (4)
N1—H1B⋯O7ⁱⁱⁱ	0.91 (2)	2.16 (2)	2.973 (3)	149 (2)
N1—H1C⋯O4ⁱⁱ	0.88 (2)	2.01 (2)	2.874 (3)	166 (3)
N1—H1A⋯O7^iv	0.90 (2)	1.92 (2)	2.769 (3)	155 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z]$ ; (iv) x, y-1, z.

Figure 2
The molecular packing of the title compound, viewed down the b axis. The hydrogen bonds are shown as blue lines.

Synthesis and crystallization

p-Toluenesulfonic acid monohydrate (1.902 g, 0.0099 mol) and L-threonine (1.191 g, 0.0099 mol) were mixed in deionized water. The solution was stirred well using a magnetic stirrer for about 4 h to obtain a homogeneous solution. Then, the solution was filtered and left to evaporate slowly. The colourless blocks used for the analysis were harvested after three weeks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Owing to obstruction from the beam-stop, the (001) reflection was omitted from the final cycles of the refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₁₀NO₃⁺·C₇H₇O₃S⁻·H₂O
M_r	309.33
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	8.0762 (4), 6.2486 (4), 14.5096 (10)
β (°)	92.161 (2)
V (Å³)	731.71 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.25
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.662, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8712, 3347, 2705
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.081, 1.02
No. of reflections	3347
No. of parameters	203
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19
Absolute structure	Flack x determined using 1035 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	0.06 (4)
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/1 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ), and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1814028

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461701848X/tk4043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461701848X/tk4043Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461701848X/tk4043Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S241431461701848X/tk4043Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018/1 (Sheldrick, 2015b), PLATON (Spek, 2009), and publCIF (Westrip, 2010).

1-Carboxy-2-hydroxypropan-1-aminium 4-methylbenzenesulfonate monohydrate top

Crystal data top

C₄H₁₀NO₃⁺·C₇H₇O₃S⁻·H₂O	D_x = 1.404 Mg m⁻³
M_r = 309.33	Melting point: 356 K
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.0762 (4) Å	Cell parameters from 3667 reflections
b = 6.2486 (4) Å	θ = 2.8–26.3°
c = 14.5096 (10) Å	µ = 0.25 mm⁻¹
β = 92.161 (2)°	T = 296 K
V = 731.71 (8) Å³	Block, colourless
Z = 2	0.15 × 0.15 × 0.10 mm
F(000) = 328

Data collection top

Bruker Kappa APEXII CCD diffractometer	3347 independent reflections
Radiation source: fine-focus sealed tube	2705 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scan	θ_max = 27.9°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.662, T_max = 0.746	k = −8→8
8712 measured reflections	l = −19→18

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0332P)² + 0.1196P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.19 e Å⁻³
3347 reflections	Δρ_min = −0.19 e Å⁻³
203 parameters	Absolute structure: Flack x determined using 1035 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
10 restraints	Absolute structure parameter: 0.06 (4)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C). The oxygen-bound H-atoms were either fixed with O—H = 0.82 or refined with a distance restraint of O—H = 0.82±0.02 Å, and with U_iso(H) set to 1.5U_equiv(O). The nitrogen-bound H-atoms were refined with a distance restraint of N—H = 0.90±0.02 Å, and with U_iso(H) set to 1.2U_equiv(N).

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

	x	y	z	U_iso*/U_eq
C1	0.1902 (4)	0.2622 (5)	0.3298 (2)	0.0322 (7)
C2	0.1609 (5)	0.1904 (6)	0.4177 (2)	0.0482 (9)
H2	0.116375	0.054961	0.426354	0.058*
C3	0.1979 (5)	0.3202 (7)	0.4928 (3)	0.0586 (11)
H3	0.176111	0.271176	0.551625	0.070*
C4	0.2667 (5)	0.5213 (6)	0.4826 (3)	0.0498 (10)
C5	0.2923 (4)	0.5914 (7)	0.3942 (2)	0.0488 (9)
H5	0.336603	0.726971	0.385569	0.059*
C6	0.2539 (4)	0.4652 (6)	0.3181 (2)	0.0428 (8)
H6	0.270923	0.516931	0.259131	0.051*
C7	0.3102 (7)	0.6609 (7)	0.5653 (3)	0.0764 (14)
H7A	0.299896	0.808749	0.548036	0.115*
H7B	0.422038	0.632250	0.586385	0.115*
H7C	0.236118	0.630136	0.613767	0.115*
C8	0.5860 (4)	0.2830 (5)	0.1146 (2)	0.0267 (7)
C9	0.7313 (3)	0.4344 (5)	0.1101 (2)	0.0241 (6)
H9	0.827748	0.370261	0.142508	0.029*
C10	0.6941 (4)	0.6526 (4)	0.1541 (2)	0.0287 (7)
H10	0.583673	0.699233	0.132162	0.034*
C11	0.6977 (5)	0.6436 (6)	0.2586 (2)	0.0496 (10)
H11A	0.804857	0.595975	0.281004	0.074*
H11B	0.614560	0.545714	0.278236	0.074*
H11C	0.676108	0.783559	0.282673	0.074*
O1	0.1064 (3)	0.2289 (4)	0.15625 (16)	0.0479 (6)
O2	0.0228 (3)	−0.0530 (5)	0.25880 (16)	0.0517 (7)
O3	0.3066 (3)	−0.0201 (3)	0.21803 (16)	0.0404 (6)
O4	0.4950 (3)	0.2474 (4)	0.04880 (15)	0.0439 (6)
O5	0.5713 (3)	0.2015 (4)	0.19660 (15)	0.0410 (6)
H5A	0.483804	0.135286	0.198317	0.061*
O6	0.8126 (3)	0.8011 (3)	0.12263 (15)	0.0414 (6)
H6A	0.877061	0.833342	0.165426	0.062*
O7	0.8692 (3)	1.0534 (3)	−0.02744 (18)	0.0394 (6)
S1	0.15216 (9)	0.09312 (13)	0.23372 (5)	0.0331 (2)
N1	0.7689 (3)	0.4662 (4)	0.01176 (17)	0.0268 (6)
H1B	0.865 (3)	0.542 (4)	0.007 (2)	0.033 (9)*
H1C	0.683 (3)	0.535 (5)	−0.013 (2)	0.060 (13)*
H1A	0.782 (4)	0.338 (4)	−0.016 (2)	0.050 (11)*
H7E	0.848 (4)	0.980 (5)	−0.0782 (17)	0.048 (11)*
H7D	0.836 (5)	0.983 (7)	0.0212 (19)	0.088 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0281 (16)	0.0385 (17)	0.0298 (17)	−0.0019 (14)	−0.0013 (13)	0.0071 (14)
C2	0.072 (3)	0.0402 (19)	0.0329 (19)	−0.0149 (19)	0.0013 (17)	0.0055 (17)
C3	0.089 (3)	0.059 (3)	0.027 (2)	−0.008 (2)	0.001 (2)	0.0055 (19)
C4	0.065 (2)	0.045 (2)	0.039 (2)	−0.0006 (18)	−0.0045 (18)	−0.0046 (17)
C5	0.063 (2)	0.0364 (18)	0.047 (2)	−0.010 (2)	0.0043 (17)	−0.001 (2)
C6	0.055 (2)	0.0408 (19)	0.0325 (19)	−0.0082 (18)	0.0049 (16)	0.0056 (16)
C7	0.113 (4)	0.067 (3)	0.048 (3)	−0.013 (3)	−0.007 (2)	−0.016 (2)
C8	0.0254 (15)	0.0237 (15)	0.0310 (17)	0.0018 (13)	0.0013 (13)	−0.0007 (13)
C9	0.0197 (14)	0.0263 (14)	0.0263 (16)	0.0000 (12)	−0.0005 (12)	0.0022 (13)
C10	0.0295 (16)	0.0270 (16)	0.0296 (16)	−0.0069 (12)	0.0021 (12)	−0.0037 (12)
C11	0.064 (2)	0.052 (2)	0.0335 (18)	−0.0228 (19)	0.0100 (16)	−0.0100 (16)
O1	0.0577 (15)	0.0567 (15)	0.0288 (13)	0.0011 (13)	−0.0049 (11)	0.0106 (12)
O2	0.0422 (13)	0.0725 (17)	0.0404 (14)	−0.0327 (13)	0.0031 (11)	−0.0002 (14)
O3	0.0371 (12)	0.0332 (12)	0.0513 (15)	−0.0043 (11)	0.0068 (11)	0.0016 (11)
O4	0.0415 (13)	0.0551 (15)	0.0346 (13)	−0.0247 (12)	−0.0061 (11)	0.0012 (11)
O5	0.0400 (13)	0.0454 (13)	0.0374 (13)	−0.0153 (11)	−0.0015 (10)	0.0100 (11)
O6	0.0561 (15)	0.0369 (13)	0.0311 (13)	−0.0210 (12)	0.0001 (11)	−0.0012 (11)
O7	0.0497 (14)	0.0287 (13)	0.0400 (14)	0.0014 (11)	0.0068 (11)	−0.0032 (12)
S1	0.0304 (4)	0.0405 (4)	0.0281 (4)	−0.0097 (4)	−0.0003 (3)	0.0048 (4)
N1	0.0252 (14)	0.0244 (13)	0.0310 (14)	−0.0014 (12)	0.0036 (11)	−0.0016 (12)

Geometric parameters (Å, º) top

C1—C2	1.381 (4)	C9—C10	1.539 (4)
C1—C6	1.381 (5)	C9—H9	0.9800
C1—S1	1.767 (3)	C10—O6	1.420 (3)
C2—C3	1.382 (5)	C10—C11	1.517 (4)
C2—H2	0.9300	C10—H10	0.9800
C3—C4	1.384 (5)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.378 (5)	C11—H11C	0.9600
C4—C7	1.513 (5)	O1—S1	1.445 (2)
C5—C6	1.383 (5)	O2—S1	1.445 (2)
C5—H5	0.9300	O3—S1	1.459 (2)
C6—H6	0.9300	O5—H5A	0.8200
C7—H7A	0.9600	O6—H6A	0.8200
C7—H7B	0.9600	O7—H7E	0.88 (2)
C7—H7C	0.9600	O7—H7D	0.88 (2)
C8—O4	1.204 (3)	N1—H1B	0.913 (19)
C8—O5	1.304 (3)	N1—H1C	0.88 (2)
C8—C9	1.511 (4)	N1—H1A	0.90 (2)
C9—N1	1.484 (4)

C2—C1—C6	119.3 (3)	N1—C9—H9	109.1
C2—C1—S1	120.2 (3)	C8—C9—H9	109.1
C6—C1—S1	120.5 (2)	C10—C9—H9	109.1
C1—C2—C3	119.9 (3)	O6—C10—C11	110.9 (2)
C1—C2—H2	120.1	O6—C10—C9	107.5 (2)
C3—C2—H2	120.1	C11—C10—C9	112.6 (3)
C2—C3—C4	121.6 (3)	O6—C10—H10	108.6
C2—C3—H3	119.2	C11—C10—H10	108.6
C4—C3—H3	119.2	C9—C10—H10	108.6
C5—C4—C3	117.5 (4)	C10—C11—H11A	109.5
C5—C4—C7	121.1 (4)	C10—C11—H11B	109.5
C3—C4—C7	121.4 (4)	H11A—C11—H11B	109.5
C4—C5—C6	121.7 (4)	C10—C11—H11C	109.5
C4—C5—H5	119.2	H11A—C11—H11C	109.5
C6—C5—H5	119.2	H11B—C11—H11C	109.5
C1—C6—C5	119.9 (3)	C8—O5—H5A	109.5
C1—C6—H6	120.0	C10—O6—H6A	109.5
C5—C6—H6	120.0	H7E—O7—H7D	111 (3)
C4—C7—H7A	109.5	O2—S1—O1	113.63 (15)
C4—C7—H7B	109.5	O2—S1—O3	111.30 (15)
H7A—C7—H7B	109.5	O1—S1—O3	111.00 (14)
C4—C7—H7C	109.5	O2—S1—C1	106.57 (15)
H7A—C7—H7C	109.5	O1—S1—C1	107.12 (16)
H7B—C7—H7C	109.5	O3—S1—C1	106.79 (14)
O4—C8—O5	125.3 (3)	C9—N1—H1B	109.9 (19)
O4—C8—C9	122.3 (3)	C9—N1—H1C	106 (2)
O5—C8—C9	112.4 (3)	H1B—N1—H1C	112 (2)
N1—C9—C8	108.2 (2)	C9—N1—H1A	110 (2)
N1—C9—C10	109.3 (2)	H1B—N1—H1A	108 (2)
C8—C9—C10	111.9 (2)	H1C—N1—H1A	110 (3)

C6—C1—C2—C3	−1.1 (5)	O4—C8—C9—C10	102.5 (3)
S1—C1—C2—C3	177.1 (3)	O5—C8—C9—C10	−76.5 (3)
C1—C2—C3—C4	−1.0 (6)	N1—C9—C10—O6	−42.8 (3)
C2—C3—C4—C5	2.0 (6)	C8—C9—C10—O6	−162.6 (2)
C2—C3—C4—C7	−178.7 (4)	N1—C9—C10—C11	−165.3 (2)
C3—C4—C5—C6	−1.1 (6)	C8—C9—C10—C11	74.9 (3)
C7—C4—C5—C6	179.7 (4)	C2—C1—S1—O2	27.8 (3)
C2—C1—C6—C5	2.0 (5)	C6—C1—S1—O2	−154.0 (3)
S1—C1—C6—C5	−176.2 (3)	C2—C1—S1—O1	149.7 (3)
C4—C5—C6—C1	−0.9 (5)	C6—C1—S1—O1	−32.1 (3)
O4—C8—C9—N1	−17.9 (4)	C2—C1—S1—O3	−91.3 (3)
O5—C8—C9—N1	163.1 (2)	C6—C1—S1—O3	86.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O5	0.96	2.47	3.068 (4)	120
O5—H5A···O3	0.82	1.76	2.576 (3)	172
O6—H6A···O2ⁱ	0.82	1.90	2.713 (3)	172
O7—H7E···O1ⁱⁱ	0.88 (2)	1.98 (3)	2.770 (3)	149 (3)
O7—H7D···O6	0.88 (2)	1.88 (3)	2.741 (3)	166 (4)
N1—H1B···O7ⁱⁱⁱ	0.91 (2)	2.16 (2)	2.973 (3)	149 (2)
N1—H1C···O4ⁱⁱ	0.88 (2)	2.01 (2)	2.874 (3)	166 (3)
N1—H1A···O7^iv	0.90 (2)	1.92 (2)	2.769 (3)	155 (3)

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

Footnotes

‡Additional correspondence author, e-mail: crraja_phy@yahoo.com.

Acknowledgements

The authors are grateful to the Sophisticated Analytical Instrument Facility (SAIF) in IITM, Chennai, India, for the single-crystal X-ray diffraction data.

Funding information

The funding for this research work was provided by the Council of Scientific and Industrial Research (CSIR), New Delhi, India (Scheme No. 03(1301)/13/EMR II to author CRR).

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