Aqua­bis(2-amino-1,3-thia­zole-4-acetato-κ² O,N ³)nickel(II)

Abstract

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,

• a = 12.0875 (12) Å

• b = 9.1278 (9) Å

• c = 12.7715 (12) Å

• β = 95.1190 (10)°

• V = 1403.5 (2) ų

• 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[F ² > 2σ(F ²)] = 0.024

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were placed in calculated positions and treated using a riding-model approximation with C—H = 0.93, with U_iso(H) = 1.2U_eq(C); O—H = 0.82 and N—H = 0.86 Å, U_iso(H)=1.5U_eq(O,N).

Figures

Fig. 1.

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

Crystal data

[Ni(C5H5N2O2S)2(H2O)]	F(000) = 800
Mr = 391.07	Dx = 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

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

Refinement

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(Fo2) + (0.034P)2 + 2.301P] where P = (Fo2 + 2Fc2)/3
1231 reflections	(Δ/σ)max < 0.001
102 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, y, −z+1/2.

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