organic compounds
1-Carboxy-2-hydroxypropan-1-aminium 4-methylbenzenesulfonate monohydrate
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
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 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 of the title hydrated molecular salt (Fig. 1), which crystallizes in the non-centrosymmetric P21. It crystallizes with one independent cation, an anion and a water molecule in the asymmetric unit.
There is an intramolecular C11—H11B⋯O5 hydrogen bond within the cation, which generates an S(6) ring, Table 1. The features a variety of hydrogen bonds, as listed in Table 1. As seen from Fig. 2, the hydrogen bonds connect the constituents of the into supramolecular layers that stack along the c-axis direction.
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 . Owing to obstruction from the beam-stop, the (001) reflection was omitted from the final cycles of the refinement.
details are summarized in Table 2
|
Structural data
CCDC reference: 1814028
https://doi.org/10.1107/S241431461701848X/tk4043sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX2 (Bruker, 2004); cell
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).C4H10NO3+·C7H7O3S−·H2O | Dx = 1.404 Mg m−3 |
Mr = 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 |
Bruker Kappa APEXII CCD diffractometer | 3347 independent reflections |
Radiation source: fine-focus sealed tube | 2705 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω and φ scan | θmax = 27.9°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.662, Tmax = 0.746 | k = −8→8 |
8712 measured reflections | l = −19→18 |
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(Fo2) + (0.0332P)2 + 0.1196P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.081 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.19 e Å−3 |
3347 reflections | Δρmin = −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) |
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 Uiso(H) set to 1.2–1.5Uequiv(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 Uiso(H) set to 1.5Uequiv(O). The nitrogen-bound H-atoms were refined with a distance restraint of N—H = 0.90±0.02 Å, and with Uiso(H) set to 1.2Uequiv(N). |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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···O7iv | 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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