Aqua­(2,2′-diamino-4,4′-bi-1,3-thia­zole-κ2 N 3,N 3′)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)zinc tetra­hydrate

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

doi:10.1107/S1600536811015145

. 2011 May 7;67(Pt 6):m683–m684. doi: 10.1107/S1600536811015145

Aqua(2,2′-diamino-4,4′-bi-1,3-thiazole-κ² N ³,N ^3′)(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)zinc tetrahydrate

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

PMCID: PMC3120585 PMID: 21754591

Abstract

The title compound, [Zn(C₇H₃NO₄)(C₆H₆N₄S₂)(H₂O)]·4H₂O, assumes a distorted octahedral coordination geometry around the Zn²⁺ cation, formed by a diaminobithiazole (DABT) molecule, a pyridine-2,6-dicarboxylate anion and a water molecule. The pyridine-2,6-dicarboxylate anion chelates to the Zn^II atom with a facial configuration. Within the chelating DABT ligand, the two thiazole rings are twisted by a dihedral angle of 14.52 (8)° with respect to each other. O—H⋯O and N—H⋯O hydrogen bonds occur in the crystal structure.

Related literature

For potential applications of transition metal complexes of 2,2′-diamino-4,4′-bi-1,3-thiazole (DABT), see: Sun et al. (1997 ▶). For general background to metal complexes with DABT, see: Liu et al. (2003 ▶). For related structures, see: Liu & Xu (2004 ▶, 2005 ▶); Liu et al. (2005 ▶).

Experimental

Crystal data

[Zn(C₇H₃NO₄)(C₆H₆N₄S₂)(H₂O)]·4H₂O
M _r = 518.82
Monoclinic,
a = 10.0529 (19) Å
b = 7.0833 (13) Å
c = 27.720 (6) Å
β = 93.960 (3)°
V = 1969.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 295 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.701, T _max = 0.796
9851 measured reflections
3471 independent reflections
2238 reflections with I > 2σ(I)
R _int = 0.074

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.119
S = 1.03
3471 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.60 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/S1600536811015145/ff2006sup1.cif

e-67-0m683-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015145/ff2006Isup2.hkl

e-67-0m683-Isup2.hkl^{(166.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn—N21	2.064 (4)
Zn—N11	2.092 (4)
Zn—N13	2.129 (4)
Zn—O1	2.213 (3)
Zn—O23	2.232 (4)
Zn—O21	2.260 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O22ⁱ	0.97	1.84	2.778 (5)	163
O1—H1B⋯O1W	0.96	1.87	2.827 (6)	174
O1W—H1WA⋯O4Wⁱⁱ	0.91	2.10	2.812 (6)	134
O1W—H1WB⋯O2Wⁱ	0.80	2.10	2.775 (6)	142
O2W—H2WA⋯O22	0.82	1.93	2.692 (6)	155
O2W—H2WB⋯O4Wⁱⁱⁱ	0.86	1.97	2.830 (6)	178
O3W—H3WA⋯O24	0.94	1.94	2.880 (6)	174
O3W—H3WB⋯O24^iv	0.96	1.80	2.694 (6)	153
O4W—H4WA⋯O2Wⁱⁱ	0.91	2.02	2.863 (6)	153
O4W—H4WB⋯O3W	0.88	1.92	2.783 (6)	167
N12—H12A⋯O1	0.97	2.00	2.873 (6)	149
N12—H12B⋯O21^v	0.83	2.19	2.984 (5)	161
N14—H14A⋯O3W^vi	0.88	2.44	3.043 (6)	126
N14—H14B⋯O1W^vii	0.86	2.19	3.022 (6)	162

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

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

supplementary crystallographic information

Comment

Transition metal complexes of 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown potential application in the field of soft magnetic material (Sun et al., 1997). As part of serial structural investigation of metal complexes with DABT (Liu et al., 2003), the title Zn^II complex was recently prepared and its X-ray structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The complex has a distorted octahedral coordinatation geometry formed by a DABT ligand, a pyridine-2,6-dicarboxylate anion and a coordinated water molecule.

Thiazole rings of DABT are not coplanar as same as in other complexes we have reported, the dihedral angle between the two thiazole rings is 14.51 (8) °. It is similar to the 17.23 (7) ° found in [Cr(C₄H₅NO₄)(C₆H₆N₄S₂)(H₂O)]Cl^.H₂O, (Liu & Xu, 2004). The distances of C16—N14 [1.335 (4) Å] and C16—N13[1.324 (4) Å] imply the existence of electron delocalization between thiazole rings and amino groups. This feature of electron delocalization of DABT can be found in some DABT complexes of Mn(II) (Liu & Xu, 2005), Co(II) (Liu et al., 2005), we have reported. The tridentate pyridine-2,6-dicarboxylate anion chelates to the Zn^II atom with a facial configuration with the maximum atomic deviation of 0.082 (3) Å (N21) to the main plane defined by C21 C22 C23 C24 C25 C26 C27 N21 O21 O22 O23 O24.

The extensive hydrogen bonding between lattice water molecules, complex and lattice water helps to stabilize the crystal structure as shown in Fig. 2. and Table 1.

Experimental

An aqueous solution (20 ml) containing DABT (1 mmol) and ZnCl₂ (1 mmol) was mixed with an aqueous solution (10 ml) of pyridine-2,6-dicarboxylic acid (1 mmol) and NaOH (2 mmol). The mixture was refluxed for 5 h. After cooling to room temperature the solution was filtered. Single crystals of (I) were obtained from the filtrate after 10 d.