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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1753.
Published online 2009 July 4. doi:  10.1107/S1600536809024532
PMCID: PMC2977512

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

Abstract

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 [20An external file that holds a picture, illustration, etc.
Object name is e-65-o1753-efi1.jpg].

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-o1753-scheme1.jpg

Experimental

Crystal data

  • C7H11N2O2S+·Cl·H2O
  • M r = 240.70
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1753-efi2.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.122
  • S = 1.12
  • 2564 reflections
  • 133 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.21 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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].

Experimental

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.

Refinement

The H2 hydrogen atom was located in a difference Fourier map and refined freely. The water H atoms were also located in a difference Fourier map but not refined [Uiso(H) = 1.5Ueq(O)]. All other H atoms were placed geometrically and refined as riding, with C—H = 0.96-0.97 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(C) for methyl H atoms.

Figures

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.

Crystal data

C7H11N2O2S+·Cl·H2OF(000) = 504
Mr = 240.70Dx = 1.426 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2280 reflections
a = 10.637 (2) Åθ = 2.3–27.4°
b = 7.4463 (15) ŵ = 0.51 mm1
c = 15.082 (3) ÅT = 292 K
β = 110.22 (3)°Block, colourless
V = 1121.0 (4) Å30.40 × 0.32 × 0.28 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer2564 independent reflections
Radiation source: fine-focus sealed tube2097 reflections with I > 2σ(I)
graphiteRint = 0.037
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.821, Tmax = 0.868l = −19→19
11232 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.12w = 1/[σ2(Fo2) + (0.0547P)2 + 0.5076P] where P = (Fo2 + 2Fc2)/3
2564 reflections(Δ/σ)max = 0.012
133 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/Ueq
C10.5427 (2)0.4538 (3)0.14877 (16)0.0386 (5)
C20.3764 (2)0.2578 (3)0.06588 (16)0.0388 (5)
C30.3260 (3)0.0717 (3)0.0413 (2)0.0542 (7)
H3A0.24460.05630.05450.081*
H3B0.3920−0.01210.07810.081*
H3C0.30880.0508−0.02470.081*
C40.3170 (2)0.4157 (3)0.03211 (17)0.0411 (5)
C50.1833 (2)0.4419 (3)−0.03804 (17)0.0455 (6)
C60.0280 (3)0.6581 (4)−0.1270 (2)0.0616 (8)
H6A−0.04190.6052−0.10790.074*
H6B0.01990.6116−0.18880.074*
C70.0156 (3)0.8556 (5)−0.1302 (3)0.0850 (11)
H7A0.02480.9001−0.06860.128*
H7B−0.07060.8889−0.17420.128*
H7C0.08460.9063−0.15010.128*
Cl10.33656 (7)0.42792 (8)0.29075 (5)0.0540 (2)
N10.65955 (19)0.5069 (3)0.20741 (15)0.0499 (5)
H1A0.71820.42900.23800.060*
H1B0.67750.61970.21530.060*
N20.5037 (2)0.2825 (2)0.13088 (14)0.0391 (4)
O10.10510 (19)0.3235 (3)−0.07219 (16)0.0720 (6)
O20.15910 (17)0.6150 (2)−0.05873 (13)0.0544 (5)
O1W0.1705 (2)0.7502 (3)0.17716 (18)0.0799 (7)
H1C0.20760.63730.19370.120*
H1D0.08790.74430.15030.120*
S10.41995 (6)0.59887 (7)0.08238 (4)0.04234 (19)
H20.547 (2)0.198 (3)0.1547 (16)0.033 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0338 (11)0.0311 (10)0.0441 (12)0.0043 (8)0.0047 (9)0.0015 (9)
C20.0357 (11)0.0341 (11)0.0414 (11)−0.0007 (9)0.0067 (9)0.0003 (9)
C30.0496 (15)0.0364 (12)0.0625 (16)−0.0065 (11)0.0014 (12)0.0003 (11)
C40.0343 (11)0.0361 (11)0.0463 (12)0.0002 (9)0.0056 (9)0.0017 (10)
C50.0342 (12)0.0447 (13)0.0498 (13)0.0033 (10)0.0048 (10)0.0023 (11)
C60.0406 (14)0.0564 (16)0.0654 (17)0.0121 (12)−0.0103 (12)−0.0003 (13)
C70.0572 (19)0.0549 (18)0.110 (3)0.0138 (15)−0.0128 (18)0.0051 (18)
Cl10.0531 (4)0.0343 (3)0.0627 (4)−0.0034 (2)0.0047 (3)−0.0010 (3)
N10.0366 (10)0.0341 (10)0.0610 (13)0.0021 (8)−0.0061 (9)0.0015 (9)
N20.0359 (10)0.0284 (9)0.0443 (10)0.0058 (8)0.0028 (8)0.0030 (8)
O10.0430 (11)0.0534 (12)0.0924 (15)−0.0044 (9)−0.0112 (10)0.0004 (11)
O20.0409 (9)0.0456 (10)0.0582 (10)0.0083 (7)−0.0064 (8)0.0013 (8)
O1W0.0451 (11)0.0465 (11)0.1127 (17)−0.0019 (9)−0.0180 (11)−0.0051 (11)
S10.0357 (3)0.0299 (3)0.0515 (3)0.0048 (2)0.0024 (2)0.0036 (2)

Geometric parameters (Å, °)

C1—N11.313 (3)C6—O21.454 (3)
C1—N21.339 (3)C6—C71.476 (4)
C1—S11.724 (2)C6—H6A0.9700
C2—C41.348 (3)C6—H6B0.9700
C2—N21.382 (3)C7—H7A0.9600
C2—C31.486 (3)C7—H7B0.9600
C3—H3A0.9600C7—H7C0.9600
C3—H3B0.9600N1—H1A0.8600
C3—H3C0.9600N1—H1B0.8600
C4—C51.463 (3)N2—H20.79 (3)
C4—S11.750 (2)O1W—H1C0.9259
C5—O11.199 (3)O1W—H1D0.8324
C5—O21.330 (3)
N1—C1—N2125.3 (2)C7—C6—H6A110.3
N1—C1—S1123.57 (17)O2—C6—H6B110.3
N2—C1—S1111.12 (16)C7—C6—H6B110.3
C4—C2—N2111.61 (19)H6A—C6—H6B108.5
C4—C2—C3129.6 (2)C6—C7—H7A109.5
N2—C2—C3118.8 (2)C6—C7—H7B109.5
C2—C3—H3A109.5H7A—C7—H7B109.5
C2—C3—H3B109.5C6—C7—H7C109.5
H3A—C3—H3B109.5H7A—C7—H7C109.5
C2—C3—H3C109.5H7B—C7—H7C109.5
H3A—C3—H3C109.5C1—N1—H1A120.0
H3B—C3—H3C109.5C1—N1—H1B120.0
C2—C4—C5126.9 (2)H1A—N1—H1B120.0
C2—C4—S1112.00 (17)C1—N2—C2115.39 (18)
C5—C4—S1121.05 (17)C1—N2—H2125.1 (18)
O1—C5—O2124.2 (2)C2—N2—H2119.5 (18)
O1—C5—C4124.7 (2)C5—O2—C6116.1 (2)
O2—C5—C4111.1 (2)H1C—O1W—H1D111.3
O2—C6—C7107.3 (2)C1—S1—C489.88 (11)
O2—C6—H6A110.3

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1Wi0.861.942.789 (3)169
N1—H1B···Cl1ii0.862.303.135 (2)164
O1W—H1C···Cl10.932.253.118 (2)156
O1W—H1D···O1iii0.832.052.863 (3)167
N2—H2···Cl1i0.79 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2337).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Turan-Zitouni, G., Demirayak, E., Ozdemir, A., Kaplancikli, Z. A. & Yildiz, M. T. (2003). Eur. J. Med. Chem 39, 267–272. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography