research communications
Redetermination of the
of 2-oxo-1,3-thiazolidin-4-iminium chlorideaDepartment of Chemistry, Selvamm Arts and Science College, Namakkal, Tamilnadu, India, bDepartment of Chemistry, St. Joseph University, Nagaland 797 115, India, and cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800, USM, Penang, Malaysia
*Correspondence e-mail: chemmk70@gmail.com
In the redetermination of the title compound, C3H5N2OS+·CI−, the consists of one independent 2-oxo-1,3-thiazolidin-4-iminium cation and one independent chloride anion. The cation interacts with a chloride anion via N—H⋯Cl hydrogen bonds forming a supramolecular chain along [010]. These supramolecular chains are further extended by weak C—H⋯Cl and C—H⋯O interactions, forming a two-dimensional network parallel to (001). The is further stabilized by weak C—O⋯π interactions, supporting a three-dimensional architecture. The structure was previously determined by Ananthamurthy & Murthy [Z. Kristallogr. (1975). 8, 356–367] but has been redetermined with higher precision to allow the hydrogen-bonding patterns and supramolecular interactions to be investigated.
Keywords: crystal structure; thiourea; chloroacetic acid; thiazolidine; hydrogen bonding.
CCDC reference: 1901297
1. Chemical context
Thiourea and its derivatives are an important group of organic compounds because of their diverse application in fields such as medicine, agriculture, coordination, and analytical chemistry (Saeed et al., 2010, 2014). The complexes with thiourea derivatives expressing biological activity have been successfully screened for various biological actions such as antibacterial, antifungal, anticancer, antioxidant, anti-inflammatory, antimalarial, antiviral activity, as anti-HIV agents and also as catalysts (Saeed et al., 2010). Thiazolidine derivatives show antitumor activity as well as a broad range of biological activities including antibactericidal, fungicidal, anti-angiogenesis, antidiabetic and antimicrobial (Singh et al., 1981; Saeed & Florke, 2006; Rizos et al., 2016). Thiourea derivatives are used as phase-change materials for thermal energy storage (Alkan et al., 2011). In addition, metal complexes of thiourea derivatives are also studied for their relationship to NLO materials (Rajasekaran et al., 2003; Ushasree et al., 2000). Thiourea derivatives find applications related to their uses as synthons in supramolecular chemistry (Saeed & Florke, 2006). Organic and inorganic complexes of thiourea derivatives form well-defined non-covalent supramolecular architectures via multiple hydrogen bonds involving the N, S and O atoms. We report herein the molecular structure and supramolecular architecture of the title salt, C3H5N2SO+CI−, (I), formed from the reaction of thiourea with monochloro acetic acid. A determination of this was performed by Ananthamurthy & Murthy (1975). However, while the authors could identify the as Pbca and determine the cell parameters [a = 9.53 (1), b = 17.61 (5), c = 7.71 (1) Å], these were not accurate enough to examine the hydrogen-bonding patterns and supramolecular interactions that are described here.
2. Structural commentary
The consists of one 2-imino-4-oxo-1,3-thiazolidine cation and one hydrochloride anion (Fig. 1). In the cation, the C3=N1 bond has double-bond character. The C3—N1 and C3—N2 bond distances indicate between the amino N1 and imino N2 groups. The exocylic bond [C3—N1 = 1.2930 (17) Å] is short and its length is comparable with that of the endocylic C3—N2 bond [1.3432 (16) Å], confirming the C3=N1 double-bond assignment. The bond lengths and angles agree with those reported for similar structures (Ananthamurthy & Murthy, 1975; Xuan et al., 2003; Vedavathi & Vijayan, 1981).
of the title compound (I)3. Supramolecular features
The 2-imino-4-oxo-1,3-thiazolidine cation interacts with the chlorine anion in the via the N2—H4⋯Cl hydrogen bond (Table 1) and with symmetry-related Cl−anions via N1—H1⋯Cl and N1—H3⋯Cl hydrogen bonds, forming supramolecular chains along [010] (Fig. 2). The chlorine anion interacts with the N2 atom and the exocyclic N1 atom of the thiazolidine moiety through the N2—H4⋯Cl hydrogen bond and the pair of N1—H1⋯Cl and N1—H3⋯Cl hydrogen bonds, forming R24(12) ring motifs in the [010] plane (Fig. 3). This motif is further connected on the other side by R48(20) ring motifs, generating a sheet-like structure parallel to (001) (Fig. 4). The supramolecular sheets and crystal packing are further stabilized by weak C—H⋯Cl, C—H⋯O and C=O⋯π interactions (Table 1, Fig. 5). All of these interactions combine to generate a three-dimensional supramolecular architecture (Fig. 6).
4. Database survey
The crystal structures of a number of related and substituted thiourea derivatives and thiazoline salts and their metal complexes have also been investigated in a variety of crystalline environments. These include DL-2-amino-2-thiazoline-4-carboxylic acid trihydrate (Xuan et al., 2003), 2-amino-1,3-thiazoline hydrochloride (Vedavathi & Vijayan, 1981), N-(4-chlorobenzoyl)-N,N-diphenylthiourea (Arslan et al., 2003a), 1-(4-chloro-benzoyl)-3-naphthalen-1-yl-thiourea (Arslan et al., 2003b) and 1–(4–chlorophenyl)–3–(4–μethylbenzoyl)thiourea (Saeed & Floörke, 2006). N—H⋯Cl hydrogen bonds play a major role in building up the supramolecular architectures of many related crystal structures (for examples, see: Diallo et al., 2014; Yamuna et al., 2014; Plater & Harrison, 2016; Khongsuk et al., 2015).
5. Synthesis and crystallization
Hot ethanol solutions of thiourea (32 mg) and chloro acetic acid (37 mg) were mixed in a 1:1 molar ratio. The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week, light-yellow prismatic crystals suitable for single-crystal X-ray analysis were obtained.
6. Refinement
Crystal data, data collection and structure . All H atoms were initially located in difference-Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and N—H = 0.86 and with Uiso(H) = 1.2Ueq(C,N).
details are summarized in Table 2
|
Supporting information
CCDC reference: 1901297
https://doi.org/10.1107/S2056989019003189/jj2207sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019003189/jj2207Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019003189/jj2207Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).C3H5N2OS+·Cl− | Dx = 1.671 Mg m−3 |
Mr = 152.60 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 1800 reflections |
a = 7.5106 (11) Å | θ = 2.4–30.2° |
b = 9.3140 (13) Å | µ = 0.87 mm−1 |
c = 17.343 (3) Å | T = 296 K |
V = 1213.2 (3) Å3 | Prism, yellow |
Z = 8 | 0.54 × 0.45 × 0.25 mm |
F(000) = 624 |
Bruker SMART APEXII DUO CCD area detector diffractometer | 1798 independent reflections |
Radiation source: fine-focus sealed tube | 1554 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
phi and ω scans | θmax = 30.2°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.683, Tmax = 0.832 | k = −10→13 |
7517 measured reflections | l = −24→20 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0384P)2 + 0.4007P] where P = (Fo2 + 2Fc2)/3 |
1798 reflections | (Δ/σ)max = 0.001 |
73 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.37439 (5) | −0.01239 (4) | 0.86421 (2) | 0.03155 (11) | |
O1 | 0.67766 (16) | 0.25652 (11) | 0.75866 (7) | 0.0389 (2) | |
N1 | 0.3380 (2) | 0.18329 (15) | 0.97467 (7) | 0.0409 (3) | |
H1 | 0.3567 | 0.2663 | 0.9949 | 0.049* | |
H3 | 0.2747 | 0.1209 | 0.9988 | 0.049* | |
C3 | 0.40497 (18) | 0.15240 (14) | 0.90803 (7) | 0.0270 (3) | |
C2 | 0.51618 (18) | 0.03829 (13) | 0.78499 (7) | 0.0272 (3) | |
H5 | 0.6172 | −0.0263 | 0.7817 | 0.033* | |
H2 | 0.4507 | 0.0336 | 0.7368 | 0.033* | |
C1 | 0.57886 (18) | 0.18932 (13) | 0.79961 (7) | 0.0264 (3) | |
N2 | 0.50511 (14) | 0.24392 (11) | 0.86677 (6) | 0.0268 (2) | |
H4 | 0.5224 | 0.3312 | 0.8812 | 0.032* | |
Cl1 | 0.63837 (5) | 0.54422 (4) | 0.91839 (2) | 0.03440 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0393 (2) | 0.02303 (17) | 0.03232 (19) | −0.00807 (13) | 0.00667 (13) | −0.00457 (12) |
O1 | 0.0438 (6) | 0.0310 (5) | 0.0418 (6) | −0.0042 (5) | 0.0099 (5) | 0.0066 (4) |
N1 | 0.0593 (9) | 0.0310 (6) | 0.0325 (6) | −0.0057 (6) | 0.0111 (6) | −0.0077 (5) |
C3 | 0.0311 (6) | 0.0224 (5) | 0.0275 (6) | −0.0007 (5) | −0.0013 (5) | −0.0025 (4) |
C2 | 0.0301 (6) | 0.0255 (6) | 0.0261 (6) | −0.0020 (5) | 0.0015 (5) | −0.0030 (4) |
C1 | 0.0281 (6) | 0.0223 (5) | 0.0289 (6) | 0.0021 (5) | −0.0022 (5) | 0.0028 (4) |
N2 | 0.0312 (5) | 0.0188 (5) | 0.0304 (5) | −0.0014 (4) | −0.0018 (4) | −0.0022 (4) |
Cl1 | 0.0453 (2) | 0.02841 (18) | 0.02950 (18) | −0.00821 (13) | 0.00436 (13) | −0.00460 (12) |
S1—C3 | 1.7280 (13) | C3—N2 | 1.3432 (16) |
S1—C2 | 1.8013 (14) | C2—C1 | 1.5049 (18) |
O1—C1 | 1.2027 (17) | C2—H5 | 0.9700 |
N1—C3 | 1.2930 (17) | C2—H2 | 0.9700 |
N1—H1 | 0.8600 | C1—N2 | 1.3865 (17) |
N1—H3 | 0.8600 | N2—H4 | 0.8600 |
C3—S1—C2 | 91.38 (6) | C1—C2—H2 | 110.2 |
C3—N1—H1 | 120.0 | S1—C2—H2 | 110.2 |
C3—N1—H3 | 120.0 | H5—C2—H2 | 108.5 |
H1—N1—H3 | 120.0 | O1—C1—N2 | 123.48 (12) |
N1—C3—N2 | 123.56 (12) | O1—C1—C2 | 125.45 (12) |
N1—C3—S1 | 122.62 (11) | N2—C1—C2 | 111.06 (11) |
N2—C3—S1 | 113.82 (9) | C3—N2—C1 | 116.00 (11) |
C1—C2—S1 | 107.55 (9) | C3—N2—H4 | 122.0 |
C1—C2—H5 | 110.2 | C1—N2—H4 | 122.0 |
S1—C2—H5 | 110.2 | ||
C2—S1—C3—N1 | −176.63 (14) | N1—C3—N2—C1 | 174.68 (14) |
C2—S1—C3—N2 | 2.92 (11) | S1—C3—N2—C1 | −4.87 (15) |
C3—S1—C2—C1 | −0.44 (10) | O1—C1—N2—C3 | −176.60 (14) |
S1—C2—C1—O1 | 179.02 (12) | C2—C1—N2—C3 | 4.40 (16) |
S1—C2—C1—N2 | −2.00 (13) |
Cg1 is the centroid of the S1/N1/C1–C3 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.86 | 2.32 | 3.1484 (15) | 162 |
N1—H3···Cl1ii | 0.86 | 2.34 | 3.1903 (15) | 170 |
N2—H4···Cl1 | 0.86 | 2.26 | 3.1026 (12) | 166 |
C2—H2···Cl1iii | 0.97 | 2.78 | 3.7137 (14) | 163 |
C2—H5···O1iv | 0.97 | 2.57 | 3.5190 (18) | 165 |
C1—O1···Cg1v | 1.20 (1) | 3.13 (1) | 3.9430 (15) | 125 (1) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1/2, −y+1/2, −z+2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+3/2, y−1/2, z; (v) x+1/2, y, −z+3/2. |
References
Alkan, C., Tek, Y. & Kahraman, D. (2011). Turk. J. Chem. 35, 769–777. CAS Google Scholar
Ananthamurthy, R. V. & Murthy, B. V. R. (1975). Z. Kristallogr. 8, 356–367. Google Scholar
Arslan, H., Flörke, U. & Külcü, N. (2003b). J. Chem. Crystallogr. 33, 919–924. Web of Science CrossRef CAS Google Scholar
Arslan, H., Flörke, U. & Külcü, N. (2003a). Acta Cryst. E59, o641–o642. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Diallo, W., Diop, L., Plasseraud, L. & Cattey, H. (2014). Acta Cryst. E70, o618–o619. CrossRef IUCr Journals Google Scholar
Khongsuk, P., Prabpai, S. & Kongsaeree, P. (2015). Acta Cryst. E71, o608–o609. CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Plater, M. J. & Harrison, W. T. A. (2016). Acta Cryst. E72, 604–607. CrossRef IUCr Journals Google Scholar
Rajasekaran, R., Kumar, R. M., Jayavel, R. & Ramasamy, P. (2003). J. Cryst. Growth, 252, 317–327. CrossRef CAS Google Scholar
Rizos, C. V., Kei, A. & Elisaf, M. S. (2016). Arch. Toxicol. 90, 1861–1881. Web of Science CrossRef CAS PubMed Google Scholar
Saeed, A. & Flörke, U. (2006). Acta Cryst. E62, o2403–o2405. CrossRef IUCr Journals Google Scholar
Saeed, A., Flörke, U. & Erben, M. F. (2014). J. Sulfur Chem. 35, 318–355. CrossRef CAS Google Scholar
Saeed, S., Rashid, N., Jones, P. G., Ali, M. & Hussain, R. (2010). Eur. J. Med. Chem. 45, 1323–1331. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singh, S. P., Parmar, S. S., Raman, K. & Stenberg, V. I. (1981). Chem. Rev. 81, 175–203. CrossRef CAS Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ushasree, P. M., Muralidharan, R., Jayavel, R. & Ramasamy, P. J. (2000). J. Cryst. Growth, 218, 365–371. CrossRef CAS Google Scholar
Vedavathi, B. M. & Vijayan, K. (1981). Acta Cryst. B37, 475–477. CrossRef CAS IUCr Journals Google Scholar
Xuan, R.-C., Hu, W.-X., Yang, Z.-Y. & Xuan, R.-R. (2003). Acta Cryst. E59, o1707–o1709. Web of Science CrossRef IUCr Journals Google Scholar
Yamuna, T. S., Jasinski, J. P., Kaur, M., Anderson, B. J. & Yathirajan, H. S. (2014). Acta Cryst. E70, 203–206. CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.