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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1517.
Published online 2009 November 4. doi:  10.1107/S1600536809045589
PMCID: PMC2971890

Bis(2-amino­thia­zole-4-acetato)aquazinc(II)

Abstract

In the title compound, [Zn(C5H5N2O2S)2(H2O)], the central Zn atom (2 site symmetry) is five-coordinated by two N and three O atoms [Zn—N = 2.047 (3) Å, Zn—O = 2.099 (2) and 1.974 (4) Å] in a distorted square-pyramidal geometry. Besides one O atom from a water mol­ecule, two 2-amino­thia­zole-4-acetate ligands provide two N and two O atoms as coordinated atoms. In the crystal structure, inter­molecular O—H(...)O and N—H(...)O hydrogen bonds connect the mol­ecules into an infinite three-dimensional framework.

Related literature

For the pharmacological activity of potential metal-based drugs consisting of the thia­zole ligands and some physiologically active metal ions, see: Addison et al. (1984 [triangle]); Bolos et al. (1999 [triangle]); Chang et al. (1982 [triangle]); Dea et al. (2008 [triangle]). For related structures, see: Zhang et al. (2008a [triangle],b [triangle]); Sen et al. (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1517-scheme1.jpg

Experimental

Crystal data

  • [Zn(C5H5N2O2S)2(H2O)]
  • M r = 397.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1517-efi2.jpg
  • a = 11.715 (2) Å
  • b = 9.822 (2) Å
  • c = 12.580 (3) Å
  • β = 91.24 (3)°
  • V = 1447.2 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.01 mm−1
  • T = 295 K
  • 0.12 × 0.10 × 0.08 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.794, T max = 0.856
  • 4633 measured reflections
  • 1742 independent reflections
  • 1214 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.101
  • S = 1.02
  • 1742 reflections
  • 101 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT-Plus (Bruker, 2005 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045589/rk2177sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045589/rk2177Isup2.hkl

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

Acknowledgments

The National Natural Science Foundation of China (No. 20701010), the Natural Science Foundation of Guangxi Zhuangzu Autonomous Region (No. 0728094) and the Department of Education of Jiangxi Province [grant No. GanJiaoJiZi (2007)348] are acknowledged.

supplementary crystallographic information

Comment

Some potential metal-based drugs consisting of the thiazole ligands and some physiologically active metal ions are attracting more and more attention due to their potentially higher pharmacological activity than pure thiazole ligands (Addison et al., 1984; Bolos et al., 1999; Chang et al., 1982; Dea et al., 2008). Recently, we also made our efforts to synthesize such a class of complexes and have obtained two single crystals containing 1,3-thiazole ring (Zhang et al. 2008a,b). The evident coordination activity of ethyl 2-aminothiazole-4-acetate (EATA) has been shown using AgNO3 as metal salt because colourless crystals were obtained in high yield overnight even at room temperature. Herein, a new five-coordinated title complex Zn(C5H5N2O2S)2(H2O), I, was synthesized using EATA and ZnSO4 as starting materials under the aid of ultrasonic irradiation. The 2-amino-4-thiazole acetate (ATA) ligand in complex I possibly formed in situ by acidic hydrolysis of EATA under ultrasonic irradiation because the ethanol/water solution of EATA is normally slightly acidic due to the present of Zn2+ solution.

The resulting Zn complex is built up from distorted square-pyramidal N2O2+O units (Sen et al. 1997), the central Zn atom is five-coordinated by two N and three O atoms [Zn–N = 2.047 (3)Å; Zn–O = 2.099 (2)Å and 1.974 (4)Å]. Besides one O atom from water molecule, two ATA ligands provide two N and two O atoms as coordinated atoms (Fig. 1). In the crystal structure, the intermolecular O–H···O and N–H···O hydrogen bonds (Table 1) connect these molecules into a infinite three-dimensional framework (Fig. 2).

Experimental

The ethyl 2-aminothiazole-4-acetate (EATA) (1 mmol, 0.186 g) was dissolved in 5 ml of ethanol under magnetic stirring, followed by addition of 5 ml of distilled water. Then, ZnSO4 (1 mmol, 0.170 g) was added and dissolved after a 10-minutes ultrasonic treatment. The resulting pale-yellow solution was filtered and stayed at room temperature for half a month. Large amounts of colourless block single crystals were obtained in about 40% yield (based on Zn).

Refinement

All hydrogen atoms attached on C, N and O atoms have been refined in the riding mode on their carrier atom, with C–H = 0.93-0.97Å, N–H = 0.86Å, O–H = 0.85Å and Uiso(H) = 1.2Ueq(C, N) or Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
View of title molecular complex with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry codes: (i) -x+1, y, -z+1/2.
Fig. 2.
The crystal packing of I, showing formation of the three-dimensional network structure via the intermolecular O–H···O and N–H···O hydrogen bonds as denoted with dashed lines. All other hydrogen ...

Crystal data

[Zn(C5H5N2O2S)2(H2O)]F(000) = 808
Mr = 397.77Dx = 1.826 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1742 reflections
a = 11.715 (2) Åθ = 2.7–25.5°
b = 9.822 (2) ŵ = 2.01 mm1
c = 12.580 (3) ÅT = 295 K
β = 91.24 (3)°Block, colourless
V = 1447.2 (5) Å30.12 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer1742 independent reflections
Radiation source: fine-focus sealed tube1214 reflections with I > 2σ(I)
graphiteRint = 0.042
[var phi] and ω scansθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −15→9
Tmin = 0.794, Tmax = 0.856k = −10→12
4633 measured reflectionsl = −16→16

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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.046P)2] where P = (Fo2 + 2Fc2)/3
1742 reflections(Δ/σ)max < 0.001
101 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.42 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Zn10.50000.77073 (6)0.25000.03185 (19)
S10.42899 (9)0.81081 (12)0.60112 (7)0.0498 (3)
O10.32429 (19)0.7822 (3)0.21472 (18)0.0392 (6)
O20.16766 (19)0.9045 (3)0.19131 (17)0.0411 (6)
O30.50000.5698 (4)0.25000.0499 (10)
H30.55510.52410.22530.075*
N10.4607 (2)0.8338 (3)0.3999 (2)0.0329 (7)
N20.6077 (3)0.7192 (4)0.4935 (2)0.0536 (9)
H1A0.64590.70730.43660.064*
H1B0.63400.68930.55340.064*
C50.2579 (3)0.8773 (4)0.2413 (2)0.0302 (8)
C10.5089 (3)0.7835 (4)0.4888 (3)0.0382 (8)
C30.3572 (3)0.8988 (4)0.4224 (3)0.0349 (8)
C20.3275 (3)0.8960 (4)0.5241 (3)0.0432 (9)
H20.26120.93460.55020.052*
C40.2909 (3)0.9663 (4)0.3346 (3)0.0417 (9)
H4A0.33551.04200.30870.050*
H4B0.22171.00370.36400.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0295 (3)0.0373 (4)0.0286 (3)0.000−0.0023 (2)0.000
S10.0541 (7)0.0690 (8)0.0262 (5)−0.0060 (5)−0.0011 (4)0.0010 (4)
O10.0309 (13)0.0479 (16)0.0384 (14)0.0085 (11)−0.0078 (11)−0.0132 (12)
O20.0339 (14)0.0525 (17)0.0365 (14)0.0091 (11)−0.0070 (11)−0.0076 (12)
O30.031 (2)0.034 (2)0.085 (3)0.0000.0120 (18)0.000
N10.0329 (16)0.0388 (18)0.0266 (14)0.0008 (13)−0.0058 (12)0.0007 (12)
N20.049 (2)0.075 (3)0.0363 (18)0.0228 (18)−0.0075 (15)0.0126 (17)
C50.0248 (17)0.039 (2)0.0272 (17)−0.0004 (14)−0.0009 (13)0.0011 (14)
C10.044 (2)0.043 (2)0.0274 (18)−0.0075 (17)−0.0048 (15)0.0016 (15)
C30.0353 (19)0.036 (2)0.0331 (19)−0.0005 (15)−0.0062 (14)−0.0086 (15)
C20.039 (2)0.054 (3)0.037 (2)−0.0001 (18)−0.0008 (16)−0.0158 (17)
C40.041 (2)0.042 (2)0.042 (2)0.0084 (16)−0.0086 (16)−0.0108 (17)

Geometric parameters (Å, °)

Zn1—O31.974 (4)N1—C31.404 (4)
Zn1—N12.047 (3)N2—C11.319 (5)
Zn1—N1i2.047 (3)N2—H1A0.8600
Zn1—O1i2.099 (2)N2—H1B0.8600
Zn1—O12.099 (2)C5—C41.507 (5)
S1—C11.733 (4)C3—C21.335 (4)
S1—C21.733 (4)C3—C41.492 (5)
O1—C51.266 (4)C2—H20.9300
O2—C51.247 (3)C4—H4A0.9700
O3—H30.8500C4—H4B0.9700
N1—C11.336 (4)
O3—Zn1—N1107.61 (8)H1A—N2—H1B120.0
O3—Zn1—N1i107.61 (8)O2—C5—O1122.9 (3)
N1—Zn1—N1i144.78 (17)O2—C5—C4118.0 (3)
O3—Zn1—O1i93.07 (7)O1—C5—C4119.0 (3)
N1—Zn1—O1i91.60 (10)N2—C1—N1124.7 (3)
N1i—Zn1—O1i86.54 (10)N2—C1—S1121.8 (3)
O3—Zn1—O193.07 (7)N1—C1—S1113.6 (3)
N1—Zn1—O186.54 (10)C2—C3—N1115.4 (3)
N1i—Zn1—O191.60 (10)C2—C3—C4125.2 (3)
O1i—Zn1—O1173.87 (14)N1—C3—C4119.5 (3)
C1—S1—C289.73 (17)C3—C2—S1110.8 (3)
C5—O1—Zn1126.1 (2)C3—C2—H2124.6
Zn1—O3—H3121.8S1—C2—H2124.6
H3—O3—H3i116.3C3—C4—C5116.1 (3)
C1—N1—C3110.5 (3)C3—C4—H4A108.3
C1—N1—Zn1124.0 (3)C5—C4—H4A108.3
C3—N1—Zn1122.4 (2)C3—C4—H4B108.3
C1—N2—H1A120.0C5—C4—H4B108.3
C1—N2—H1B120.0H4A—C4—H4B107.4

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O2ii0.851.822.664 (3)170
N2—H1A···O1i0.862.082.822 (4)145
N2—H1B···O2iii0.862.002.844 (4)169

Symmetry codes: (ii) x+1/2, y−1/2, z; (i) −x+1, y, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2177).

References

  • Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.
  • Bolos, C. A., Fanourgakis, P. V., Christidis, P. C. & Nikolov, G. S. (1999). Polyhedron, 18, 1661–1668.
  • Bruker (2005). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chang, C. K., Myoung, S. K. & Ward, B. (1982). Chem. Commun. pp. 716–719.
  • Dea, S., Adhikari, S., Tilak-Jain, J., Menon, V. P. & Devasagayam, T. P. A. (2008). Chem. Biol. Interact. 173, 215–223.
  • Sen, S., Mitra, S., Kundu, P., Saha, M. K., Krüger, C. & Bruckmann, J. (1997). Polyhedron, 16, 2475–2481.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, L.-J., Shen, X.-C. & Liang, H. (2008a). Acta Cryst. E64, m1248. [PMC free article] [PubMed]
  • Zhang, L.-J., Shen, X.-C. & Liang, H. (2008b). Acta Cryst. E64, m1413–m1414. [PMC free article] [PubMed]

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