Crystal structure of 2-amino-3-ethyl-4,5-di­hydro-1,3-thia­zol-3-ium 3-chloro­benzo­ate

Sara Maira M Hizam; Bohari M Yamin

doi:10.1107/S2056989015008385

. 2015 May 7;71(Pt 6):o378. doi: 10.1107/S2056989015008385

Crystal structure of 2-amino-3-ethyl-4,5-dihydro-1,3-thiazol-3-ium 3-chlorobenzoate

Sara Maira M Hizam ^a, Bohari M Yamin ^a,^*

PMCID: PMC4459344 PMID: 26090175

Abstract

The title salt, C₅H₁₁N₂S⁺·C₇H₄ClO₂ ⁻, comprises a 2-amino-3-ethyl-4,5-dihydro-1,3-thiazol-3-ium cation in which the five-membered ring adopts an envelope conformation with the methylene C adjacent to the S atom being the flap, and a planar 3-chlorobenzoate anion (r.m.s. deviation for the 10 non-H atoms = 0.021 Å). The most prominent feature of the crystal packing are N—H⋯O hydrogen bonds whereby the two amine H atoms bridge two carboxylate O atoms resulting in the formation of a centrosymmetric 12-membered {⋯HNH⋯OCO}₂ synthon involving two cations and two anions. These aggregates are linked by C—H⋯O interactions to form a supramolecular chain along the a-axis direction.

Keywords: crystal structure; salt; 3-chlorobenzoate anion; 2-amino-3-ethyl-4,5-dihydro-1,3-thiazol-3-ium cation; hydrogen bonding

Related literature

For the crystal structure of a related compound, see: Yamin & Zulkifli (2011 ▸). graphic file with name e-71-0o378-scheme1.jpg

Experimental

Crystal data

C₅H₁₁N₂S⁺·C₇H₄ClO₂ ⁻
M _r = 286.77
Triclinic,
a = 7.3376 (7) Å
b = 8.7987 (9) Å
c = 11.7068 (11) Å
α = 70.728 (3)°
β = 80.269 (3)°
γ = 71.531 (3)°
V = 674.95 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 296 K
0.37 × 0.32 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.856, T _max = 0.975
16295 measured reflections
3430 independent reflections
1957 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.142
S = 1.02
3430 reflections
171 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015008385/tk5367sup1.cif

e-71-0o378-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008385/tk5367Isup2.hkl

e-71-0o378-Isup2.hkl^{(168.2KB, hkl)}

Click here for additional data file.^{(5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015008385/tk5367Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015008385/tk5367fig1.tif

The molecular structure of the title salt with displacement ellipsoids drawn at 50% probability level.

Click here for additional data file.^{(1.4MB, tif)}

b . DOI: 10.1107/S2056989015008385/tk5367fig2.tif

A view of the crystal packing of the title salt viewed down b axis. The dashed lines indicate hydrogen bonds.

CCDC reference: 1062249

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2BO1ⁱ	0.87(2)	1.89(2)	2.730(3)	164(2)
N2H2CO2	0.86(2)	1.83(2)	2.680(3)	169(2)
C10H10BO1ⁱⁱ	0.97	2.46	3.297(4)	145

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank the Ministry of Higher Education of Malaysia and the Universiti Kebangsaan Malaysia for the research grant No. FGRS/2/2014/ST01/UKM/01/1.

supplementary crystallographic information

S1. Comment

It was reported previously that 3-nitro-4-chlorobenzoyl isothiocyanate reacted with piperidine to give 2,2,6,6-tetramethyl-4-oxopiperidin-1-ium 4-chloro-3-nitrobenzoate (Yamin & Zulkifli, 2011). Similarly, in this study, the reaction of 3-chlorobenzoyl isothiocyanate with 2-ethylaminoethanol also gave an unexpected product, i.e. the title salt, 3-ethylthiazoliden-3-ium-2-amine 3-chlorobenzoate (Fig. 1). The chlorobenzoate Cl1/(C1—C7)/O1/O2 anion is planar with maximum deviation of 0.018 (3) Å for the C3 atom from the least squares plane. The thiazoliden ring S1/N1/C8/C9/C10 is tilted with maximum deviation of 0.159 (3) Å for C10 atom from the least squares plane. The N1—C8 bond length of 1.320 (3) Å indicates the ring nitrogen atom N1 is protonated. In the crystal structure, the molecules are linked by intermolecular hydrogen bonds N2—H2B···O1, C2—H10B···O1, N2—H2C···O2 and C11—H11B···O2 (symmetry codes as in Table 1) to form a one-dimensional chain along the a axis (Fig. 2). A weak π.,.π interaction with the distance between (C1—C6) centroids of 3.534 () Å (2 - x, -1 - y ,3 - z) was observed.

S2. Experimental

An acetone solution (20 ml) of 2-(ethylamino)ethanol (0.01 mol, 0.8914 g m) was added into a two-necked round-bottomed flask containing an equimolar amount of 3-chlorobenzoylisothiocyanate (0.01 mol). The mixture was refluxed for about 3 h, filtered and left to evaporate at room temperature. The filtrate gave colourless crystals after 2 days of evaporation (yield 86.02%, m.pt: 368.2–369.5 K).