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

Hizam, S.M.M.; Yamin, B.M.

doi:10.1107/S2056989015008385

organic compounds

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Volume 71| Part 6| June 2015| Page o378

doi:10.1107/S2056989015008385

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

Sara Maira M. Hizam ^a and Bohari M. Yamin ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor D.E., Malaysia
^*Correspondence e-mail: bohari@ukm.edu.my

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 27 April 2015; accepted 28 April 2015; online 7 May 2015)

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.

CCDC reference: 1062249

1. Related literature

For the crystal structure of a related compound, see: Yamin & Zulkifli (2011 ).

2. Experimental

2.1. Crystal data

C₅H₁₁N₂S⁺·C₇H₄ClO₂⁻
M_r = 286.77
Triclinic, $[P \overline 1]$
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1ⁱ	0.87 (2)	1.89 (2)	2.730 (3)	164 (2)
N2—H2C⋯O2	0.86 (2)	1.83 (2)	2.680 (3)	169 (2)
C10—H10B⋯O1ⁱⁱ	0.97	2.46	3.297 (4)	145
Symmetry codes: (i) -x+2, -y, -z+2; (ii) -x+1, -y, -z+2.

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 ).

Supporting information

CCDC reference: 1062249

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015008385/tk5367sup1.cif

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

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

checkCIF report

Comment top

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.

Related literature top

For the crystal structure of a related compound, see: Yamin & Zulkifli (2011).

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title salt with displacement ellipsoids drawn at 50% probability level.
	Fig. 2. A view of the crystal packing of the title salt viewed down b axis. The dashed lines indicate hydrogen bonds.

2-Amino-3-ethyl-4,5-dihydro-1,3-thiazol-3-ium 3-chlorobenzoate top

Crystal data top

C₅H₁₁N₂S⁺·C₇H₄ClO₂⁻	Z = 2
M_r = 286.77	F(000) = 300
Triclinic, P1	D_x = 1.411 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3376 (7) Å	Cell parameters from 6990 reflections
b = 8.7987 (9) Å	θ = 2.9–28.6°
c = 11.7068 (11) Å	µ = 0.43 mm⁻¹
α = 70.728 (3)°	T = 296 K
β = 80.269 (3)°	Slab, colourless
γ = 71.531 (3)°	0.37 × 0.32 × 0.06 mm
V = 674.95 (11) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3430 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
Detector resolution: 83.66 pixels mm^-1	θ_max = 28.6°, θ_min = 2.9°
ω scan	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −11→11
T_min = 0.856, T_max = 0.975	l = −15→15
16295 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0715P)²] where P = (F_o² + 2F_c²)/3
3430 reflections	(Δ/σ)_max < 0.001
171 parameters	Δρ_max = 0.31 e Å⁻³
2 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₅H₁₁N₂S⁺·C₇H₄ClO₂⁻	γ = 71.531 (3)°
M_r = 286.77	V = 674.95 (11) Å³
Triclinic, P1	Z = 2
a = 7.3376 (7) Å	Mo Kα radiation
b = 8.7987 (9) Å	µ = 0.43 mm⁻¹
c = 11.7068 (11) Å	T = 296 K
α = 70.728 (3)°	0.37 × 0.32 × 0.06 mm
β = 80.269 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3430 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1957 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.975	R_int = 0.064
16295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	2 restraints
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.31 e Å⁻³
3430 reflections	Δρ_min = −0.26 e Å⁻³
171 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
Cl1	1.18120 (11)	−0.25267 (10)	1.66658 (6)	0.0724 (3)
S1	0.48369 (9)	0.37155 (8)	0.90259 (5)	0.0493 (2)
O1	1.0531 (3)	−0.2998 (2)	1.16212 (16)	0.0570 (5)
O2	0.9540 (3)	−0.0771 (3)	1.22844 (19)	0.0855 (7)
N1	0.4326 (3)	0.1591 (3)	1.10804 (19)	0.0523 (6)
N2	0.7549 (3)	0.1491 (3)	1.0431 (2)	0.0514 (6)
H2B	0.835 (3)	0.189 (3)	0.9867 (19)	0.064 (9)*
H2C	0.810 (3)	0.068 (2)	1.1024 (17)	0.059 (8)*
C1	1.1263 (3)	−0.3301 (3)	1.3595 (2)	0.0383 (5)
C2	1.2154 (3)	−0.4996 (3)	1.3822 (2)	0.0459 (6)
H2A	1.2237	−0.5512	1.3230	0.055*
C3	1.2921 (4)	−0.5927 (3)	1.4918 (2)	0.0545 (7)
H3A	1.3509	−0.7072	1.5065	0.065*
C4	1.2829 (4)	−0.5184 (3)	1.5798 (2)	0.0523 (7)
H4A	1.3353	−0.5812	1.6537	0.063*
C5	1.1949 (3)	−0.3501 (3)	1.5564 (2)	0.0441 (6)
C6	1.1164 (3)	−0.2547 (3)	1.4475 (2)	0.0416 (6)
H6A	1.0571	−0.1405	1.4335	0.050*
C7	1.0367 (3)	−0.2280 (3)	1.2403 (2)	0.0468 (6)
C8	0.5708 (3)	0.2094 (3)	1.0315 (2)	0.0406 (6)
C9	0.2384 (4)	0.2374 (4)	1.0666 (3)	0.0713 (9)
H9A	0.1472	0.2595	1.1336	0.086*
H9B	0.2010	0.1635	1.0351	0.086*
C10	0.2390 (3)	0.3967 (4)	0.9701 (3)	0.0609 (8)
H10A	0.1996	0.4898	1.0043	0.073*
H10B	0.1511	0.4184	0.9096	0.073*
C11	0.4633 (5)	0.0131 (4)	1.2191 (3)	0.0694 (9)
H11A	0.3912	−0.0612	1.2173	0.083*
H11B	0.5988	−0.0486	1.2200	0.083*
C12	0.4029 (5)	0.0639 (4)	1.3300 (3)	0.0829 (10)
H12A	0.4251	−0.0338	1.3995	0.124*
H12B	0.2683	0.1232	1.3303	0.124*
H12C	0.4758	0.1357	1.3330	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0822 (6)	0.0905 (6)	0.0555 (5)	−0.0246 (5)	−0.0093 (4)	−0.0333 (4)
S1	0.0453 (4)	0.0562 (4)	0.0395 (4)	−0.0020 (3)	−0.0132 (3)	−0.0117 (3)
O1	0.0605 (11)	0.0701 (13)	0.0473 (10)	−0.0239 (9)	−0.0116 (9)	−0.0172 (10)
O2	0.1099 (18)	0.0587 (14)	0.0682 (14)	0.0216 (12)	−0.0489 (13)	−0.0156 (10)
N1	0.0438 (12)	0.0556 (14)	0.0474 (12)	−0.0072 (10)	−0.0040 (10)	−0.0085 (10)
N2	0.0411 (13)	0.0547 (15)	0.0449 (13)	0.0008 (11)	−0.0117 (11)	−0.0065 (11)
C1	0.0318 (12)	0.0416 (14)	0.0396 (13)	−0.0133 (10)	−0.0043 (10)	−0.0060 (10)
C2	0.0431 (14)	0.0437 (15)	0.0527 (15)	−0.0128 (11)	−0.0046 (12)	−0.0154 (12)
C3	0.0549 (16)	0.0369 (15)	0.0627 (18)	−0.0070 (12)	−0.0120 (14)	−0.0050 (13)
C4	0.0476 (15)	0.0547 (18)	0.0445 (14)	−0.0119 (13)	−0.0136 (12)	0.0011 (13)
C5	0.0371 (13)	0.0566 (16)	0.0417 (14)	−0.0189 (12)	−0.0008 (11)	−0.0138 (12)
C6	0.0366 (13)	0.0378 (13)	0.0473 (14)	−0.0087 (10)	−0.0045 (11)	−0.0096 (11)
C7	0.0361 (13)	0.0573 (18)	0.0436 (14)	−0.0125 (12)	−0.0091 (11)	−0.0080 (13)
C8	0.0463 (15)	0.0370 (13)	0.0376 (13)	−0.0010 (11)	−0.0101 (11)	−0.0167 (11)
C9	0.0454 (17)	0.095 (2)	0.0659 (19)	−0.0181 (16)	−0.0046 (14)	−0.0148 (18)
C10	0.0399 (15)	0.0683 (19)	0.0718 (19)	−0.0033 (13)	−0.0153 (14)	−0.0231 (16)
C11	0.074 (2)	0.0483 (17)	0.068 (2)	−0.0075 (15)	−0.0001 (16)	−0.0059 (15)
C12	0.100 (3)	0.075 (2)	0.063 (2)	−0.0175 (19)	−0.0161 (19)	−0.0080 (18)

Geometric parameters (Å, º) top

Cl1—C5	1.743 (3)	C3—H3A	0.9300
S1—C8	1.746 (2)	C4—C5	1.368 (4)
S1—C10	1.811 (3)	C4—H4A	0.9300
O1—C7	1.245 (3)	C5—C6	1.377 (3)
O2—C7	1.243 (3)	C6—H6A	0.9300
N1—C8	1.320 (3)	C9—C10	1.483 (4)
N1—C9	1.460 (3)	C9—H9A	0.9700
N1—C11	1.485 (3)	C9—H9B	0.9700
N2—C8	1.298 (3)	C10—H10A	0.9700
N2—H2B	0.866 (10)	C10—H10B	0.9700
N2—H2C	0.862 (10)	C11—C12	1.465 (4)
C1—C6	1.379 (3)	C11—H11A	0.9700
C1—C2	1.379 (3)	C11—H11B	0.9700
C1—C7	1.514 (3)	C12—H12A	0.9600
C2—C3	1.376 (3)	C12—H12B	0.9600
C2—H2A	0.9300	C12—H12C	0.9600
C3—C4	1.373 (4)

C8—S1—C10	90.90 (12)	N2—C8—N1	126.9 (2)
C8—N1—C9	115.4 (2)	N2—C8—S1	120.1 (2)
C8—N1—C11	125.1 (2)	N1—C8—S1	112.98 (17)
C9—N1—C11	118.6 (2)	N1—C9—C10	107.9 (2)
C8—N2—H2B	120.1 (19)	N1—C9—H9A	110.1
C8—N2—H2C	126.2 (18)	C10—C9—H9A	110.1
H2B—N2—H2C	114 (3)	N1—C9—H9B	110.1
C6—C1—C2	119.3 (2)	C10—C9—H9B	110.1
C6—C1—C7	120.2 (2)	H9A—C9—H9B	108.4
C2—C1—C7	120.5 (2)	C9—C10—S1	106.45 (18)
C3—C2—C1	120.3 (2)	C9—C10—H10A	110.4
C3—C2—H2A	119.8	S1—C10—H10A	110.4
C1—C2—H2A	119.8	C9—C10—H10B	110.4
C4—C3—C2	120.7 (2)	S1—C10—H10B	110.4
C4—C3—H3A	119.7	H10A—C10—H10B	108.6
C2—C3—H3A	119.7	C12—C11—N1	112.1 (3)
C5—C4—C3	118.6 (2)	C12—C11—H11A	109.2
C5—C4—H4A	120.7	N1—C11—H11A	109.2
C3—C4—H4A	120.7	C12—C11—H11B	109.2
C4—C5—C6	121.6 (2)	N1—C11—H11B	109.2
C4—C5—Cl1	119.55 (19)	H11A—C11—H11B	107.9
C6—C5—Cl1	118.8 (2)	C11—C12—H12A	109.5
C5—C6—C1	119.5 (2)	C11—C12—H12B	109.5
C5—C6—H6A	120.3	H12A—C12—H12B	109.5
C1—C6—H6A	120.3	C11—C12—H12C	109.5
O2—C7—O1	125.3 (2)	H12A—C12—H12C	109.5
O2—C7—C1	116.6 (2)	H12B—C12—H12C	109.5
O1—C7—C1	118.1 (2)

C6—C1—C2—C3	0.5 (4)	C2—C1—C7—O1	−3.0 (3)
C7—C1—C2—C3	−178.3 (2)	C9—N1—C8—N2	−174.0 (3)
C1—C2—C3—C4	−0.6 (4)	C11—N1—C8—N2	−5.0 (4)
C2—C3—C4—C5	0.3 (4)	C9—N1—C8—S1	4.8 (3)
C3—C4—C5—C6	0.0 (4)	C11—N1—C8—S1	173.7 (2)
C3—C4—C5—Cl1	179.99 (19)	C10—S1—C8—N2	−171.3 (2)
C4—C5—C6—C1	−0.1 (4)	C10—S1—C8—N1	9.8 (2)
Cl1—C5—C6—C1	179.95 (18)	C8—N1—C9—C10	−20.9 (4)
C2—C1—C6—C5	−0.2 (3)	C11—N1—C9—C10	169.4 (3)
C7—C1—C6—C5	178.6 (2)	N1—C9—C10—S1	26.1 (3)
C6—C1—C7—O2	−1.0 (3)	C8—S1—C10—C9	−20.7 (2)
C2—C1—C7—O2	177.8 (2)	C8—N1—C11—C12	112.8 (3)
C6—C1—C7—O1	178.2 (2)	C9—N1—C11—C12	−78.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1ⁱ	0.87 (2)	1.89 (2)	2.730 (3)	164 (2)
N2—H2C···O2	0.86 (2)	1.83 (2)	2.680 (3)	169 (2)
C10—H10B···O1ⁱⁱ	0.97	2.46	3.297 (4)	145

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1ⁱ	0.87 (2)	1.89 (2)	2.730 (3)	164 (2)
N2—H2C···O2	0.860 (19)	1.83 (2)	2.680 (3)	169 (2)
C10—H10B···O1ⁱⁱ	0.97	2.46	3.297 (4)	145

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

Acknowledgements

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.

References

Bruker (2009). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yamin, B. M. & Zulkifli, N. Z. (2011). Acta Cryst. E67, o1920. Web of Science CSD CrossRef IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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