Aqua­bis(2-amino-1,3-thia­zole-4-acetato-κ2O,N3)nickel(II)

He, Q.-F.; Li, D.-S.; Zhao, J.; Ke, X.-J.; Li, C.

doi:10.1107/S1600536809017978

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m666

doi:10.1107/S1600536809017978

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Aquabis(2-amino-1,3-thiazole-4-acetato-κ²O,N³)nickel(II)

Qiu-Fen He,^a Dong-Sheng Li,^a ^* Jun Zhao,^a Xi-Jun Ke ^a and Cai Li ^a

^aCollege of Mechanical & Materials Engineering, Functional Materials Research Institute, China Three Gorges University, Yichang 443002, People's Republic of China
^*Correspondence e-mail: lidongsheng1@126.com

(Received 27 April 2009; accepted 13 May 2009; online 20 May 2009)

In the crystal structure of the title compound, [Ni(C₅H₅N₂O₂S)₂(H₂O)], the Ni^II cation is located on a twofold rotation axis and chelated by two 2-amino-1,3-thiazole-4-acetate (ata) anions in the basal coordination plane; a water molecule located on the same twofold rotation axis completes the distorted square-pyramidal coordination geometry. Intermolecular O—H⋯O and N—H⋯O hydrogen bonding, as well as π–π stacking between parallel thiazole rings [centroid–centroid distance 3.531 (8) Å], helps to stabilize the crystal structure.

Related literature

For general background to the potential use of discrete and polymeric metal-organic complexes as functional materials in catalysis, molecular recognition, separation and non-linear optics, see: Batten & Robson (1998 ); Fujita et al. (1994 ); Han et al. (2008 ); Wu et al. (2001 ).

Experimental

Crystal data

[Ni(C₅H₅N₂O₂S)₂(H₂O)]
M_r = 391.07
Monoclinic, C 2/c
a = 12.0875 (12) Å
b = 9.1278 (9) Å
c = 12.7715 (12) Å
β = 95.1190 (10)°
V = 1403.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.821, T_max = 0.904
3487 measured reflections
1231 independent reflections
1119 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.065
S = 1.01
1231 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O1	2.0243 (15)
Ni1—O3	1.999 (2)
Ni1—N2	2.0465 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.10	2.816 (3)	140
N1—H1B⋯O2ⁱⁱ	0.86	1.99	2.839 (3)	170
O3—H3⋯O2ⁱⁱⁱ	0.82	1.94	2.7211 (19)	158
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017978/xu2518sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017978/xu2518Isup2.hkl

checkCIF report

Comment top

The rational design and synthesis of novel discrete and polymeric metal-organic complexes have attracted intense interest owing to the realisation of their potential for use as functional materials in catalysis, molecular recognition, separation, and nonlinear optics (Batten & Robson, 1998; Fujita et al., 1994). As for the construction of these inorganic/organic hybrid materials, carboxylate ligands have proven to be an efficacious choice (Wu et al., 2001). The employment of multifunctional ligands bearing both anionic and neutral donor atoms, such as nicotinate, isonicotinate, and various pyridinedicarboxylates, has resulted in the preparation of many functional coordination polymers, some with intriguing optical or gas sorption properties (Han et al., 2008). Herein we report the hydrothermal synthesis, structural characterization of the title complex.

The molecular structure of the title complex is shown in Fig. 1. The Ni^II ion is located on a twofold rotation axis and has a slightly distorted square-pyramidal geometry formed by two oxygen atoms, two nitrogen atoms from ata ligands and one coordinated water molecules (Table 1). The amido N atoms forms N—H···O hydrogen bonds with carboxylate O atoms, linking the molecules into one dimentional chains, which are then linked into a two-dimensional sheet by aromatic π-π stacking between S1-thiazole and S1ⁱ-thiazole [symmetry code: (i) -x, 1 - y, 1 - z] rings [centroid–centroid distance 3.531 (8) Å]. Furthermore, the two-dimensional layers are extended to a three-dimensional supramolecular structure by O—H···O hydrogen bonds (Table 2).

Related literature top

For general background to the potential use of discrete and polymeric metal-organic complexes as functional materials in catalysis, molecular recognition, separation and non-linear optics, see: Batten & Robson (1998); Fujita et al. (1994); Han et al. (2008); Wu et al. (2001).

Experimental top

A mixture of Ni(CH₃COOH)₂.4H₂O (0.025 g, 0.1 mmol), 2-amino-4-thiazoleacetic acid (0.0316 g, 0.2 mmol) and distilled water (10 ml) was sealed in a 25 ml Teflon-lined stainless autoclave. The pH value of the mixture was adjusted to 6 by a aqueous solution of NaOH (0.1 mol/L), and then heated at 393 K for 3 d. Green crystals were obtained on cooling to room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with thermal ellipsoids plotted at 50% probability [symmetry code: (i) -x, y, -z + 1/2].

Aquabis(2-amino-1,3-thiazole-4-acetato-κ²O,N³)nickel(II) top

Crystal data top

[Ni(C₅H₅N₂O₂S)₂(H₂O)]	F(000) = 800
M_r = 391.07	D_x = 1.851 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2106 reflections
a = 12.0875 (12) Å	θ = 2.8–25.0°
b = 9.1278 (9) Å	µ = 1.71 mm⁻¹
c = 12.7715 (12) Å	T = 293 K
β = 95.119 (1)°	Prism, green
V = 1403.5 (2) Å³	0.12 × 0.10 × 0.06 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1231 independent reflections
Radiation source: fine-focus sealed tube	1119 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
CCD Profile fitting scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.821, T_max = 0.904	k = −5→10
3487 measured reflections	l = −15→14

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.034P)² + 2.301P] where P = (F_o² + 2F_c²)/3
1231 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Ni(C₅H₅N₂O₂S)₂(H₂O)]	V = 1403.5 (2) Å³
M_r = 391.07	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.0875 (12) Å	µ = 1.71 mm⁻¹
b = 9.1278 (9) Å	T = 293 K
c = 12.7715 (12) Å	0.12 × 0.10 × 0.06 mm
β = 95.119 (1)°

Data collection top

Bruker SMART CCD diffractometer	1231 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1119 reflections with I > 2σ(I)
T_min = 0.821, T_max = 0.904	R_int = 0.014
3487 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.01	Δρ_max = 0.31 e Å⁻³
1231 reflections	Δρ_min = −0.29 e Å⁻³
102 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
Ni1	0.0000	0.69428 (4)	0.2500	0.02321 (14)
N1	0.10680 (18)	0.7919 (2)	0.49121 (17)	0.0423 (6)
H1A	0.1428	0.7976	0.4363	0.051*
H1B	0.1341	0.8297	0.5496	0.051*
N2	−0.04038 (14)	0.6630 (2)	0.40062 (14)	0.0264 (4)
O1	−0.16405 (12)	0.68137 (17)	0.20264 (12)	0.0314 (4)
O2	−0.33123 (12)	0.5835 (2)	0.19153 (12)	0.0369 (4)
O3	0.0000	0.9133 (2)	0.2500	0.0401 (6)
H3	0.0570	0.9433	0.2270	0.060*
C1	−0.23701 (16)	0.5998 (2)	0.23761 (16)	0.0254 (5)
C2	−0.20703 (19)	0.5149 (3)	0.33761 (18)	0.0336 (5)
H2A	−0.2751	0.4820	0.3650	0.040*
H2B	−0.1657	0.4283	0.3204	0.040*
C3	0.00918 (19)	0.7248 (3)	0.48595 (17)	0.0295 (5)
C4	−0.14006 (17)	0.5971 (2)	0.42235 (17)	0.0280 (5)
C5	−0.16604 (19)	0.6117 (3)	0.52138 (18)	0.0364 (6)
H5	−0.2299	0.5739	0.5468	0.044*
S1	−0.06560 (5)	0.71004 (8)	0.59589 (5)	0.03934 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0186 (2)	0.0286 (2)	0.0224 (2)	0.000	0.00139 (15)	0.000
N1	0.0395 (12)	0.0586 (15)	0.0285 (11)	−0.0167 (11)	0.0017 (9)	−0.0117 (10)
N2	0.0241 (9)	0.0319 (10)	0.0229 (9)	−0.0007 (8)	0.0009 (7)	−0.0001 (8)
O1	0.0225 (8)	0.0422 (9)	0.0291 (9)	−0.0047 (7)	0.0005 (6)	0.0090 (7)
O2	0.0217 (8)	0.0551 (11)	0.0327 (9)	−0.0077 (7)	−0.0033 (6)	0.0127 (8)
O3	0.0262 (12)	0.0300 (12)	0.0666 (17)	0.000	0.0190 (12)	0.000
C1	0.0217 (11)	0.0292 (11)	0.0252 (11)	0.0004 (9)	0.0016 (9)	−0.0006 (9)
C2	0.0290 (11)	0.0352 (13)	0.0354 (13)	−0.0065 (10)	−0.0038 (10)	0.0099 (11)
C3	0.0294 (12)	0.0343 (13)	0.0246 (12)	0.0031 (10)	0.0014 (9)	−0.0006 (10)
C4	0.0239 (10)	0.0314 (12)	0.0281 (12)	0.0023 (9)	−0.0004 (9)	0.0071 (10)
C5	0.0278 (12)	0.0504 (15)	0.0311 (13)	0.0004 (11)	0.0039 (10)	0.0096 (12)
S1	0.0384 (4)	0.0570 (4)	0.0230 (3)	0.0039 (3)	0.0044 (3)	−0.0030 (3)

Geometric parameters (Å, º) top

Ni1—O1	2.0243 (15)	O2—C1	1.243 (3)
Ni1—O1ⁱ	2.0243 (15)	O3—H3	0.8200
Ni1—O3	1.999 (2)	C1—C2	1.510 (3)
Ni1—N2	2.0465 (18)	C2—C4	1.494 (3)
Ni1—N2ⁱ	2.0465 (18)	C2—H2A	0.9700
N1—C3	1.326 (3)	C2—H2B	0.9700
N1—H1A	0.8600	C3—S1	1.742 (2)
N1—H1B	0.8600	C4—C5	1.337 (3)
N2—C3	1.322 (3)	C5—S1	1.726 (3)
N2—C4	1.397 (3)	C5—H5	0.9300
O1—C1	1.266 (3)

O3—Ni1—O1	93.34 (5)	O2—C1—C2	118.64 (19)
O3—Ni1—O1ⁱ	93.34 (5)	O1—C1—C2	118.57 (18)
O1—Ni1—O1ⁱ	173.33 (9)	C4—C2—C1	115.36 (19)
O3—Ni1—N2	98.02 (5)	C4—C2—H2A	108.4
O1—Ni1—N2	87.90 (7)	C1—C2—H2A	108.4
O1ⁱ—Ni1—N2	91.17 (7)	C4—C2—H2B	108.4
O3—Ni1—N2ⁱ	98.02 (5)	C1—C2—H2B	108.4
O1—Ni1—N2ⁱ	91.17 (7)	H2A—C2—H2B	107.5
O1ⁱ—Ni1—N2ⁱ	87.90 (7)	N2—C3—N1	125.1 (2)
N2—Ni1—N2ⁱ	163.96 (11)	N2—C3—S1	113.70 (17)
C3—N1—H1A	120.0	N1—C3—S1	121.23 (17)
C3—N1—H1B	120.0	C5—C4—N2	115.1 (2)
H1A—N1—H1B	120.0	C5—C4—C2	125.3 (2)
C3—N2—C4	110.83 (19)	N2—C4—C2	119.58 (19)
C3—N2—Ni1	125.93 (16)	C4—C5—S1	111.14 (18)
C4—N2—Ni1	121.96 (14)	C4—C5—H5	124.4
C1—O1—Ni1	128.58 (14)	S1—C5—H5	124.4
Ni1—O3—H3	109.5	C5—S1—C3	89.19 (11)
O2—C1—O1	122.8 (2)

O3—Ni1—N2—C3	−50.65 (19)	C4—N2—C3—N1	177.7 (2)
O1—Ni1—N2—C3	−143.73 (19)	Ni1—N2—C3—N1	−15.1 (3)
O1ⁱ—Ni1—N2—C3	42.88 (19)	C4—N2—C3—S1	−1.8 (2)
N2ⁱ—Ni1—N2—C3	129.35 (19)	Ni1—N2—C3—S1	165.31 (11)
O3—Ni1—N2—C4	115.15 (16)	C3—N2—C4—C5	1.4 (3)
O1—Ni1—N2—C4	22.08 (17)	Ni1—N2—C4—C5	−166.37 (17)
O1ⁱ—Ni1—N2—C4	−151.32 (17)	C3—N2—C4—C2	−177.3 (2)
N2ⁱ—Ni1—N2—C4	−64.85 (16)	Ni1—N2—C4—C2	15.0 (3)
O3—Ni1—O1—C1	−135.01 (18)	C1—C2—C4—C5	126.8 (3)
N2—Ni1—O1—C1	−37.09 (19)	C1—C2—C4—N2	−54.7 (3)
N2ⁱ—Ni1—O1—C1	126.88 (19)	N2—C4—C5—S1	−0.3 (3)
Ni1—O1—C1—O2	−167.76 (16)	C2—C4—C5—S1	178.27 (18)
Ni1—O1—C1—C2	10.2 (3)	C4—C5—S1—C3	−0.6 (2)
O2—C1—C2—C4	−140.5 (2)	N2—C3—S1—C5	1.44 (19)
O1—C1—C2—C4	41.5 (3)	N1—C3—S1—C5	−178.2 (2)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.10	2.816 (3)	140
N1—H1B···O2ⁱⁱ	0.86	1.99	2.839 (3)	170
O3—H3···O2ⁱⁱⁱ	0.82	1.94	2.7211 (19)	158

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

Experimental details

Crystal data
Chemical formula	[Ni(C₅H₅N₂O₂S)₂(H₂O)]
M_r	391.07
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.0875 (12), 9.1278 (9), 12.7715 (12)
β (°)	95.119 (1)
V (Å³)	1403.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.12 × 0.10 × 0.06

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.821, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	3487, 1231, 1119
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.065, 1.01
No. of reflections	1231
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.29

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—O1	2.0243 (15)	Ni1—N2	2.0465 (18)
Ni1—O3	1.999 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.10	2.816 (3)	140.1
N1—H1B···O2ⁱⁱ	0.86	1.99	2.839 (3)	169.6
O3—H3···O2ⁱⁱⁱ	0.82	1.94	2.7211 (19)	158

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

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (grant No. 20773104), the Program for New Century Excellent Talents in Universities (NCET-06–0891), the Natural Science Foundation of Hubei Province of China (2008CDB030) and the Important Project of Hubei Provincial Education Office (Z20091301).

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