Aqua­(2,2′-diamino-4,4′-bi-1,3-thia­zole-κ2 N 3,N 3′)(thio­diacetato-κ3 O,S,O′)nickel(II) monohydrate

Yan-Li Wang; Guang-Jun Chang; Bing-Xin Liu

doi:10.1107/S1600536811015157

. 2011 May 7;67(Pt 6):m681. doi: 10.1107/S1600536811015157

Aqua(2,2′-diamino-4,4′-bi-1,3-thiazole-κ² N ³,N ^3′)(thiodiacetato-κ³ O,S,O′)nickel(II) monohydrate

Yan-Li Wang ^a, Guang-Jun Chang ^a, Bing-Xin Liu ^a,^*

PMCID: PMC3120560 PMID: 21754589

Abstract

In the title compound, [Ni(C₄H₄O₄S)(C₆H₆N₄S₂)(H₂O)]·H₂O, the Ni^II cation assumes a distorted octahedral coordination geometry formed by a diaminobithiazole (DABT) ligand, a thiodiacetate (TDA) dianion and a coordinated water molecule. The tridentate TDA chelates to the Ni cation in a facial configuration, and both chelating rings display the envelope conformations. The two thiazole rings of the DABT ligand are twisted with respect to each other, making a dihedral angle of 9.96 (9)°. Extensive O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For general background to diaminobithiazole complexes, see: Waring (1981 ▶); Fisher et al. (1985 ▶). For the synthesis, see: Erlenmeyer (1948 ▶). For related structures, see: Liu et al. (2002 ▶).

Experimental

Crystal data

[Ni(C₄H₄O₄S)(C₆H₆N₄S₂)(H₂O)]·H₂O
M _r = 441.14
Monoclinic,
a = 11.856 (4) Å
b = 12.197 (4) Å
c = 12.507 (4) Å
β = 114.622 (3)°
V = 1644.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 295 K
0.30 × 0.24 × 0.18 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.638, T _max = 0.750
8263 measured reflections
2888 independent reflections
2627 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.061
S = 1.06
2888 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015157/xu5191sup1.cif

e-67-0m681-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015157/xu5191Isup2.hkl

e-67-0m681-Isup2.hkl^{(138.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni—O1	2.0763 (14)
Ni—O21	2.0944 (14)
Ni—O23	2.0357 (14)
Ni—N11	2.0634 (15)
Ni—N13	2.1094 (16)
Ni—S21	2.4461 (7)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O1W	0.85	1.91	2.7540	173
O1—H1B⋯O22ⁱ	0.79	1.97	2.7399	162
N12—H12A⋯O24ⁱⁱ	0.81	2.09	2.8785	166
N12—H12B⋯O23	0.87	2.09	2.8807	152
N14—H14A⋯O21ⁱ	0.83	2.20	2.9378	149
O1W—H1WA⋯O24ⁱ	0.85	2.01	2.8616	177
O1W—H1WB⋯O22ⁱⁱⁱ	0.84	1.91	2.7493	173

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The project was supported by the Foundation of Shanghai University, China.

supplementary crystallographic information

Comment

Transition metal complexes of DABT have shown potential application in some fields, such as the effective inhibitors of DNA synthesis of the tumor cells (Waring, 1981; Fisher et al., 1985). As part of a series of investigations of metal complexes of DABT, the title Ni^II complex, (I), was prepared in the laboratory and its X-ray structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The complex has a distorted octahedral coordination geometry formed by one of DABT, one of TDA and one of coordinated water.

The tridentate TDA chelates to Ni^II atom in an envelope configuration. Two carboxyl groups of TDA monodentately coordinate to the Ni^II atom. Uncoordinated carboxyl oxygen atoms O22 and O24 are hydrogen bonded to the hydrogen atoms of coordinated water of the neighboring complex molecule, as shown in Fig. 2 and Table 1. Othervize, coordinated carboxyl oxygen atom O1 is hydrogen bonded to the hydrogen atoms of lattice watter molecule of the neighboring complex molecule and within complex respectively. The atom O22 and O24 hydrogen bonnded to amino group of DABT of neighboring complex and lattice water within complex respectively.

The DABT chelates to the Ni^II atom with a near coplanar configuration, the angle of two thiazole rings being 9.96 (11) °. The bond distance 1.462 (3) Å of C13—C14 correspond to C—C single bonds between sp2-hybridized C atoms (C—C = 1.483 Å). The C—N(amino) bond (C11—N12 = 1.323 (2) Å) distance is shorter than 1.354 (2) Å in free DABT and the other one (C16—N14 =1.353 (3) Å) distance is similar to 1.354 (2) Å in free DABT (Liu et al., 2002). The C—N bond within thiazole ring one distance (C11—N11 = 1.323 (2) Å) is longer than 1.309 (2) Å and the other one (C16—N13 = 1.313 (2) Å) is similar to 1.309 (2) Å in free DABT within thiazole rings (Liu et al., 2002), this suggests the existence of electron delocalization within one thiazole ring of DABT.

Experimental

The DABT was prepared according to the literature (Erlenmeyer, 1948). An aqueous solution (20 ml) containing DABT (1 mmol) and NiCl₂ (1 mmol) was mixed with an aqueous solution (10 ml) of thiodiacetic acid (1 mmol) and NaOH (2 mmol). The mixture was refluxed for 5 h. The solution was filtered after cooling to room temperature. Green single crystals were obtained from the filtrate after 7 d.