2-Amino-5-ethoxy­carbonyl-4-methyl­thia­zol-3-ium chloride monohydrate

Lin, J.R.; Zhao, H.

doi:10.1107/S1600536809024532

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1753

doi:10.1107/S1600536809024532

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2-Amino-5-ethoxycarbonyl-4-methylthiazol-3-ium chloride monohydrate

Jin Rui Lin ^a and Hong Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 17 June 2009; accepted 26 June 2009; online 4 July 2009)

In the crystal structure of the title compound, C₇H₁₁N₂O₂S⁺·Cl⁻·H₂O, the cations, anions and water molecules are linked by intermolecular N—H⋯O, N—H⋯Cl, O—H⋯O and O—H⋯Cl hydrogen bonds, forming layers stacked along [20 $[\overline{1}]$ ].

Related literature

For the biological activity of thiazole derivatives, see: Turan-Zitouni et al. (2003 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₁₁N₂O₂S⁺·Cl⁻·H₂O
M_r = 240.70
Monoclinic, P 2₁ /c
a = 10.637 (2) Å
b = 7.4463 (15) Å
c = 15.082 (3) Å
β = 110.22 (3)°
V = 1121.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 292 K
0.40 × 0.32 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.821, T_max = 0.868
11232 measured reflections
2564 independent reflections
2097 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.122
S = 1.12
2564 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1Wⁱ	0.86	1.94	2.789 (3)	169
N1—H1B⋯Cl1ⁱⁱ	0.86	2.30	3.135 (2)	164
O1W—H1C⋯Cl1	0.93	2.25	3.118 (2)	156
O1W—H1D⋯O1ⁱⁱⁱ	0.83	2.05	2.863 (3)	167
N2—H2⋯Cl1ⁱ	0.79 (3)	2.35 (3)	3.141 (2)	173 (2)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024532/rz2337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024532/rz2337Isup2.hkl

checkCIF report

Comment top

Heterocyclic compounds containing the thiazole ring have recently received much attention for their broad-spectrum biological activities (Turan-Zitouni et al., 2003). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1), contains 5-(ethoxycarbonyl)-4-methylthiazol-2-aminium cations, chloride anions and water molecules in the stoichiometric ratio of 1:1:1. The cation is approximately planar, the maximum displacement being 0.062 (2) Å for atom O1. Bond lengths (Allen et al., 1987) and angles have normal values. In the crystal structure (Fig. 2), cations, anions and water molecules are linked by intermolecular N—H···O, N—H···Cl, O—H···O and O—H···Cl hydrogen bonds (Table 1) to form layers stacked along [2 0 1].

Related literature top

For the biological activity of thiazole derivatives, see: Turan-Zitouni et al. (2003). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of thiourea (0.2 mol), ethyl acetoacetate (0.1 mol) and I₂ (0.1 mol) was stirred for 15 hours at 120°C. After refluxing the mixture with chlorhydric acid, the title compound was obtained. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of a 95% ethanol/water solution at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title compound, showing the structure along the b axis. Intermolecular H bonds are shown as dashed lined.

2-Amino-5-ethoxycarbonyl-4-methylthiazol-3-ium chloride monohydrate top

Crystal data top

C₇H₁₁N₂O₂S⁺·Cl⁻·H₂O	F(000) = 504
M_r = 240.70	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2280 reflections
a = 10.637 (2) Å	θ = 2.3–27.4°
b = 7.4463 (15) Å	µ = 0.51 mm⁻¹
c = 15.082 (3) Å	T = 292 K
β = 110.22 (3)°	Block, colourless
V = 1121.0 (4) Å³	0.40 × 0.32 × 0.28 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2564 independent reflections
Radiation source: fine-focus sealed tube	2097 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.821, T_max = 0.868	l = −19→19
11232 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0547P)² + 0.5076P] where P = (F_o² + 2F_c²)/3
2564 reflections	(Δ/σ)_max = 0.012
133 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₇H₁₁N₂O₂S⁺·Cl⁻·H₂O	V = 1121.0 (4) Å³
M_r = 240.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.637 (2) Å	µ = 0.51 mm⁻¹
b = 7.4463 (15) Å	T = 292 K
c = 15.082 (3) Å	0.40 × 0.32 × 0.28 mm
β = 110.22 (3)°

Data collection top

Rigaku SCXmini diffractometer	2564 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2097 reflections with I > 2σ(I)
T_min = 0.821, T_max = 0.868	R_int = 0.037
11232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.48 e Å⁻³
2564 reflections	Δρ_min = −0.21 e Å⁻³
133 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
C1	0.5427 (2)	0.4538 (3)	0.14877 (16)	0.0386 (5)
C2	0.3764 (2)	0.2578 (3)	0.06588 (16)	0.0388 (5)
C3	0.3260 (3)	0.0717 (3)	0.0413 (2)	0.0542 (7)
H3A	0.2446	0.0563	0.0545	0.081*
H3B	0.3920	−0.0121	0.0781	0.081*
H3C	0.3088	0.0508	−0.0247	0.081*
C4	0.3170 (2)	0.4157 (3)	0.03211 (17)	0.0411 (5)
C5	0.1833 (2)	0.4419 (3)	−0.03804 (17)	0.0455 (6)
C6	0.0280 (3)	0.6581 (4)	−0.1270 (2)	0.0616 (8)
H6A	−0.0419	0.6052	−0.1079	0.074*
H6B	0.0199	0.6116	−0.1888	0.074*
C7	0.0156 (3)	0.8556 (5)	−0.1302 (3)	0.0850 (11)
H7A	0.0248	0.9001	−0.0686	0.128*
H7B	−0.0706	0.8889	−0.1742	0.128*
H7C	0.0846	0.9063	−0.1501	0.128*
Cl1	0.33656 (7)	0.42792 (8)	0.29075 (5)	0.0540 (2)
N1	0.65955 (19)	0.5069 (3)	0.20741 (15)	0.0499 (5)
H1A	0.7182	0.4290	0.2380	0.060*
H1B	0.6775	0.6197	0.2153	0.060*
N2	0.5037 (2)	0.2825 (2)	0.13088 (14)	0.0391 (4)
O1	0.10510 (19)	0.3235 (3)	−0.07219 (16)	0.0720 (6)
O2	0.15910 (17)	0.6150 (2)	−0.05873 (13)	0.0544 (5)
O1W	0.1705 (2)	0.7502 (3)	0.17716 (18)	0.0799 (7)
H1C	0.2076	0.6373	0.1937	0.120*
H1D	0.0879	0.7443	0.1503	0.120*
S1	0.41995 (6)	0.59887 (7)	0.08238 (4)	0.04234 (19)
H2	0.547 (2)	0.198 (3)	0.1547 (16)	0.033 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0338 (11)	0.0311 (10)	0.0441 (12)	0.0043 (8)	0.0047 (9)	0.0015 (9)
C2	0.0357 (11)	0.0341 (11)	0.0414 (11)	−0.0007 (9)	0.0067 (9)	0.0003 (9)
C3	0.0496 (15)	0.0364 (12)	0.0625 (16)	−0.0065 (11)	0.0014 (12)	0.0003 (11)
C4	0.0343 (11)	0.0361 (11)	0.0463 (12)	0.0002 (9)	0.0056 (9)	0.0017 (10)
C5	0.0342 (12)	0.0447 (13)	0.0498 (13)	0.0033 (10)	0.0048 (10)	0.0023 (11)
C6	0.0406 (14)	0.0564 (16)	0.0654 (17)	0.0121 (12)	−0.0103 (12)	−0.0003 (13)
C7	0.0572 (19)	0.0549 (18)	0.110 (3)	0.0138 (15)	−0.0128 (18)	0.0051 (18)
Cl1	0.0531 (4)	0.0343 (3)	0.0627 (4)	−0.0034 (2)	0.0047 (3)	−0.0010 (3)
N1	0.0366 (10)	0.0341 (10)	0.0610 (13)	0.0021 (8)	−0.0061 (9)	0.0015 (9)
N2	0.0359 (10)	0.0284 (9)	0.0443 (10)	0.0058 (8)	0.0028 (8)	0.0030 (8)
O1	0.0430 (11)	0.0534 (12)	0.0924 (15)	−0.0044 (9)	−0.0112 (10)	0.0004 (11)
O2	0.0409 (9)	0.0456 (10)	0.0582 (10)	0.0083 (7)	−0.0064 (8)	0.0013 (8)
O1W	0.0451 (11)	0.0465 (11)	0.1127 (17)	−0.0019 (9)	−0.0180 (11)	−0.0051 (11)
S1	0.0357 (3)	0.0299 (3)	0.0515 (3)	0.0048 (2)	0.0024 (2)	0.0036 (2)

Geometric parameters (Å, º) top

C1—N1	1.313 (3)	C6—O2	1.454 (3)
C1—N2	1.339 (3)	C6—C7	1.476 (4)
C1—S1	1.724 (2)	C6—H6A	0.9700
C2—C4	1.348 (3)	C6—H6B	0.9700
C2—N2	1.382 (3)	C7—H7A	0.9600
C2—C3	1.486 (3)	C7—H7B	0.9600
C3—H3A	0.9600	C7—H7C	0.9600
C3—H3B	0.9600	N1—H1A	0.8600
C3—H3C	0.9600	N1—H1B	0.8600
C4—C5	1.463 (3)	N2—H2	0.79 (3)
C4—S1	1.750 (2)	O1W—H1C	0.9259
C5—O1	1.199 (3)	O1W—H1D	0.8324
C5—O2	1.330 (3)

N1—C1—N2	125.3 (2)	C7—C6—H6A	110.3
N1—C1—S1	123.57 (17)	O2—C6—H6B	110.3
N2—C1—S1	111.12 (16)	C7—C6—H6B	110.3
C4—C2—N2	111.61 (19)	H6A—C6—H6B	108.5
C4—C2—C3	129.6 (2)	C6—C7—H7A	109.5
N2—C2—C3	118.8 (2)	C6—C7—H7B	109.5
C2—C3—H3A	109.5	H7A—C7—H7B	109.5
C2—C3—H3B	109.5	C6—C7—H7C	109.5
H3A—C3—H3B	109.5	H7A—C7—H7C	109.5
C2—C3—H3C	109.5	H7B—C7—H7C	109.5
H3A—C3—H3C	109.5	C1—N1—H1A	120.0
H3B—C3—H3C	109.5	C1—N1—H1B	120.0
C2—C4—C5	126.9 (2)	H1A—N1—H1B	120.0
C2—C4—S1	112.00 (17)	C1—N2—C2	115.39 (18)
C5—C4—S1	121.05 (17)	C1—N2—H2	125.1 (18)
O1—C5—O2	124.2 (2)	C2—N2—H2	119.5 (18)
O1—C5—C4	124.7 (2)	C5—O2—C6	116.1 (2)
O2—C5—C4	111.1 (2)	H1C—O1W—H1D	111.3
O2—C6—C7	107.3 (2)	C1—S1—C4	89.88 (11)
O2—C6—H6A	110.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wⁱ	0.86	1.94	2.789 (3)	169
N1—H1B···Cl1ⁱⁱ	0.86	2.30	3.135 (2)	164
O1W—H1C···Cl1	0.93	2.25	3.118 (2)	156
O1W—H1D···O1ⁱⁱⁱ	0.83	2.05	2.863 (3)	167
N2—H2···Cl1ⁱ	0.79 (3)	2.35 (3)	3.141 (2)	173 (2)

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

Experimental details

Crystal data
Chemical formula	C₇H₁₁N₂O₂S⁺·Cl⁻·H₂O
M_r	240.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	10.637 (2), 7.4463 (15), 15.082 (3)
β (°)	110.22 (3)
V (Å³)	1121.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.40 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.821, 0.868
No. of measured, independent and observed [I > 2σ(I)] reflections	11232, 2564, 2097
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.122, 1.12
No. of reflections	2564
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wⁱ	0.86	1.94	2.789 (3)	168.8
N1—H1B···Cl1ⁱⁱ	0.86	2.30	3.135 (2)	163.9
O1W—H1C···Cl1	0.93	2.25	3.118 (2)	155.8
O1W—H1D···O1ⁱⁱⁱ	0.83	2.05	2.863 (3)	166.9
N2—H2···Cl1ⁱ	0.79 (3)	2.35 (3)	3.141 (2)	173 (2)

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

Acknowledgements

Financial support from the Southeast University Fund for Young Researchers (4007041027) is gratefully acknowledged.

References

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Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turan-Zitouni, G., Demirayak, E., Ozdemir, A., Kaplancikli, Z. A. & Yildiz, M. T. (2003). Eur. J. Med. Chem. 39, 267–272. Web of Science CrossRef Google Scholar