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

Zhang, L.-J.; Shen, X.-C.; Yang, Y.; Liang, H.

doi:10.1107/S1600536809045589

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1517

doi:10.1107/S1600536809045589

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

Lai-Jun Zhang,^a,^b ^* Xing-Can Shen,^b Yan Yang ^c and Hong Liang ^b ^*

^aDepartment of Chemistry, Shangrao Normal University, Shangrao 334001, People's Republic of China, ^bKey Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education), School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, People's Republic of China, and ^cDepartment of Chemistry and Biology, Yulin Teachers' College, Yulin 537000, People's Republic of China
^*Correspondence e-mail: ljzhang@sru.jx.cn, hliang@mailbox.gxnu.edu.cn

(Received 22 October 2009; accepted 29 October 2009; online 4 November 2009)

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 ); Bolos et al. (1999 ); Chang et al. (1982 ); Dea et al. (2008 ). For related structures, see: Zhang et al. (2008a ,b ); Sen et al. (1997 ).

Experimental

Crystal data

[Zn(C₅H₅N₂O₂S)₂(H₂O)]
M_r = 397.77
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.041
wR(F²) = 0.101
S = 1.02
1742 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.85	1.82	2.664 (3)	170
N2—H1A⋯O1ⁱⁱ	0.86	2.08	2.822 (4)	145
N2—H1B⋯O2ⁱⁱⁱ	0.86	2.00	2.844 (4)	169
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus; 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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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); Bolos et al. (1999); Chang et al. (1982); Dea et al. (2008). For related structures, see: Zhang et al. (2008a,b); Sen et al. (1997).

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); 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).

Figures top

	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 atoms were omitted for clarity.

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

Crystal data top

[Zn(C₅H₅N₂O₂S)₂(H₂O)]	F(000) = 808
M_r = 397.77	D_x = 1.826 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1742 reflections
a = 11.715 (2) Å	θ = 2.7–25.5°
b = 9.822 (2) Å	µ = 2.01 mm⁻¹
c = 12.580 (3) Å	T = 295 K
β = 91.24 (3)°	Block, colourless
V = 1447.2 (5) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1742 independent reflections
Radiation source: fine-focus sealed tube	1214 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→9
T_min = 0.794, T_max = 0.856	k = −10→12
4633 measured reflections	l = −16→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.046P)²] where P = (F_o² + 2F_c²)/3
1742 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Zn(C₅H₅N₂O₂S)₂(H₂O)]	V = 1447.2 (5) Å³
M_r = 397.77	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.715 (2) Å	µ = 2.01 mm⁻¹
b = 9.822 (2) Å	T = 295 K
c = 12.580 (3) Å	0.12 × 0.10 × 0.08 mm
β = 91.24 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1742 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1214 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.856	R_int = 0.042
4633 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	Δρ_max = 0.37 e Å⁻³
1742 reflections	Δρ_min = −0.43 e Å⁻³
101 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.77073 (6)	0.2500	0.03185 (19)
S1	0.42899 (9)	0.81081 (12)	0.60112 (7)	0.0498 (3)
O1	0.32429 (19)	0.7822 (3)	0.21472 (18)	0.0392 (6)
O2	0.16766 (19)	0.9045 (3)	0.19131 (17)	0.0411 (6)
O3	0.5000	0.5698 (4)	0.2500	0.0499 (10)
H3	0.5551	0.5241	0.2253	0.075*
N1	0.4607 (2)	0.8338 (3)	0.3999 (2)	0.0329 (7)
N2	0.6077 (3)	0.7192 (4)	0.4935 (2)	0.0536 (9)
H1A	0.6459	0.7073	0.4366	0.064*
H1B	0.6340	0.6893	0.5534	0.064*
C5	0.2579 (3)	0.8773 (4)	0.2413 (2)	0.0302 (8)
C1	0.5089 (3)	0.7835 (4)	0.4888 (3)	0.0382 (8)
C3	0.3572 (3)	0.8988 (4)	0.4224 (3)	0.0349 (8)
C2	0.3275 (3)	0.8960 (4)	0.5241 (3)	0.0432 (9)
H2	0.2612	0.9346	0.5502	0.052*
C4	0.2909 (3)	0.9663 (4)	0.3346 (3)	0.0417 (9)
H4A	0.3355	1.0420	0.3087	0.050*
H4B	0.2217	1.0037	0.3640	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0295 (3)	0.0373 (4)	0.0286 (3)	0.000	−0.0023 (2)	0.000
S1	0.0541 (7)	0.0690 (8)	0.0262 (5)	−0.0060 (5)	−0.0011 (4)	0.0010 (4)
O1	0.0309 (13)	0.0479 (16)	0.0384 (14)	0.0085 (11)	−0.0078 (11)	−0.0132 (12)
O2	0.0339 (14)	0.0525 (17)	0.0365 (14)	0.0091 (11)	−0.0070 (11)	−0.0076 (12)
O3	0.031 (2)	0.034 (2)	0.085 (3)	0.000	0.0120 (18)	0.000
N1	0.0329 (16)	0.0388 (18)	0.0266 (14)	0.0008 (13)	−0.0058 (12)	0.0007 (12)
N2	0.049 (2)	0.075 (3)	0.0363 (18)	0.0228 (18)	−0.0075 (15)	0.0126 (17)
C5	0.0248 (17)	0.039 (2)	0.0272 (17)	−0.0004 (14)	−0.0009 (13)	0.0011 (14)
C1	0.044 (2)	0.043 (2)	0.0274 (18)	−0.0075 (17)	−0.0048 (15)	0.0016 (15)
C3	0.0353 (19)	0.036 (2)	0.0331 (19)	−0.0005 (15)	−0.0062 (14)	−0.0086 (15)
C2	0.039 (2)	0.054 (3)	0.037 (2)	−0.0001 (18)	−0.0008 (16)	−0.0158 (17)
C4	0.041 (2)	0.042 (2)	0.042 (2)	0.0084 (16)	−0.0086 (16)	−0.0108 (17)

Geometric parameters (Å, º) top

Zn1—O3	1.974 (4)	N1—C3	1.404 (4)
Zn1—N1	2.047 (3)	N2—C1	1.319 (5)
Zn1—N1ⁱ	2.047 (3)	N2—H1A	0.8600
Zn1—O1ⁱ	2.099 (2)	N2—H1B	0.8600
Zn1—O1	2.099 (2)	C5—C4	1.507 (5)
S1—C1	1.733 (4)	C3—C2	1.335 (4)
S1—C2	1.733 (4)	C3—C4	1.492 (5)
O1—C5	1.266 (4)	C2—H2	0.9300
O2—C5	1.247 (3)	C4—H4A	0.9700
O3—H3	0.8500	C4—H4B	0.9700
N1—C1	1.336 (4)

O3—Zn1—N1	107.61 (8)	H1A—N2—H1B	120.0
O3—Zn1—N1ⁱ	107.61 (8)	O2—C5—O1	122.9 (3)
N1—Zn1—N1ⁱ	144.78 (17)	O2—C5—C4	118.0 (3)
O3—Zn1—O1ⁱ	93.07 (7)	O1—C5—C4	119.0 (3)
N1—Zn1—O1ⁱ	91.60 (10)	N2—C1—N1	124.7 (3)
N1ⁱ—Zn1—O1ⁱ	86.54 (10)	N2—C1—S1	121.8 (3)
O3—Zn1—O1	93.07 (7)	N1—C1—S1	113.6 (3)
N1—Zn1—O1	86.54 (10)	C2—C3—N1	115.4 (3)
N1ⁱ—Zn1—O1	91.60 (10)	C2—C3—C4	125.2 (3)
O1ⁱ—Zn1—O1	173.87 (14)	N1—C3—C4	119.5 (3)
C1—S1—C2	89.73 (17)	C3—C2—S1	110.8 (3)
C5—O1—Zn1	126.1 (2)	C3—C2—H2	124.6
Zn1—O3—H3	121.8	S1—C2—H2	124.6
H3—O3—H3ⁱ	116.3	C3—C4—C5	116.1 (3)
C1—N1—C3	110.5 (3)	C3—C4—H4A	108.3
C1—N1—Zn1	124.0 (3)	C5—C4—H4A	108.3
C3—N1—Zn1	122.4 (2)	C3—C4—H4B	108.3
C1—N2—H1A	120.0	C5—C4—H4B	108.3
C1—N2—H1B	120.0	H4A—C4—H4B	107.4

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱⁱ	0.85	1.82	2.664 (3)	170
N2—H1A···O1ⁱ	0.86	2.08	2.822 (4)	145
N2—H1B···O2ⁱⁱⁱ	0.86	2.00	2.844 (4)	169

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

Experimental details

Crystal data
Chemical formula	[Zn(C₅H₅N₂O₂S)₂(H₂O)]
M_r	397.77
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	11.715 (2), 9.822 (2), 12.580 (3)
β (°)	91.24 (3)
V (Å³)	1447.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.01
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.794, 0.856
No. of measured, independent and observed [I > 2σ(I)] reflections	4633, 1742, 1214
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.101, 1.02
No. of reflections	1742
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.43

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.85	1.82	2.664 (3)	169.7
N2—H1A···O1ⁱⁱ	0.86	2.08	2.822 (4)	144.6
N2—H1B···O2ⁱⁱⁱ	0.86	2.00	2.844 (4)	168.5

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

Acknowledgements

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.

References

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