Bis(2-amino­benzothia­zol-3-ium) bis­(7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxyl­ato-κ3 O 2,O 3,O 7)zincate hexa­hydrate

Fan Zhang; Tian-Xi Lv; Jie Feng; Qiu-Yue Lin

doi:10.1107/S1600536812017886

. 2012 Apr 28;68(Pt 5):m684. doi: 10.1107/S1600536812017886

Bis(2-aminobenzothiazol-3-ium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato-κ³ O ²,O ³,O ⁷)zincate hexahydrate

Fan Zhang ^a,^b, Tian-Xi Lv ^b, Jie Feng ^b, Qiu-Yue Lin ^a,^b,^*

PMCID: PMC3344404 PMID: 22590166

Abstract

In the title hydrated molecular salt, (C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O, which is isotypic with its Mn^II, Co^II and Ni^II analogues, the Zn²⁺ ion lies on a crystallographic inversion centre and a distorted ZnO₆ octahedral coordination geometry arises from the two doubly deprotonated O,O′,O′′-tridentate ligands. In the crystal, the components are linked by N—H⋯O_a, N—H⋯O_w, O_w—H⋯O_a and O_w—H⋯O_w hydrogen bonds (w = water and a = anion).

Related literature

For background to the applications of norcantharidin (systematic name: 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride), see: Zeng & Lu (2006 ▶). For the isotypic Mn^II, Co^II and Ni^II structures, see: Wang et al. (2010a ▶,b ▶, 2012 ▶).

Experimental

Crystal data

(C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O
M _r = 844.21
Triclinic,
a = 6.6983 (7) Å
b = 10.1497 (11) Å
c = 13.2082 (14) Å
α = 90.172 (7)°
β = 91.097 (7)°
γ = 99.251 (7)°
V = 886.11 (16) Å³
Z = 1
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 296 K
0.12 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.914, T _max = 0.951
11657 measured reflections
3108 independent reflections
1839 reflections with I > 2σ(I)
R _int = 0.228

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.087
S = 0.91
3108 reflections
241 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812017886/hb6746sup1.cif

e-68-0m684-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017886/hb6746Isup2.hkl

e-68-0m684-Isup2.hkl^{(152.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn1—O1	2.014 (2)
Zn1—O3	2.132 (2)
Zn1—O5	2.176 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.86	1.82	2.675 (4)	173
N2—H2A⋯O3ⁱ	0.86	2.00	2.853 (4)	172
N2—H2B⋯O2Wⁱⁱ	0.86	2.02	2.838 (4)	158
O1W—H1WA⋯O4	0.85	2.01	2.818 (3)	160
O1W—H1WB⋯O2W	0.85	1.95	2.793 (4)	170
O2W—H2WA⋯O2	0.85	1.85	2.683 (3)	167
O2W—H2WB⋯O3W	0.85	1.92	2.765 (3)	170
O3W—H3WA⋯O1Wⁱⁱ	0.85	2.21	3.024 (3)	160
O3W—H3WB⋯O1Wⁱⁱⁱ	0.85	2.00	2.793 (4)	156

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

Acknowledgments

The authors thank the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301) for financial support.

supplementary crystallographic information

Comment

7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride (norcantharidin), as a traditional Chinese drug, has great anti-cancer activity. (Zeng et al., 2006). A isostructural manganese complex (Wang et al., 2010a) and a cobalt complex (Wang et al., 2010b) has been reported. The molecular structure of the title complex is shown in Fig.1. The zinc atom is six-coordinated in a distorted octahedral coordination mode, binding to two bridging O atoms of the bicycloheptane unit and four carboxylate O atoms of two symmetry-related and fully deprotonated ligands. 2-aminobenzothiazole don't involved the coordination, and N atom of thiazole ring is protonated.The crystal structure is stabilized by N—H···O hydrogen-bonding interactions between the cations and anions and O—H···O hydrogen bonds including the crystal water molecules.

Experimental

A mixture of 0.5 mmol norcantharidin, 0.5 mmol zinc acetate, 0.5 mmol 2-aminobenzothiazole and 15 mL distilled water was sealed in a 25 mL Teflon-lined stainless vessel and heated at 443 K for 3 d, then cooled slowly to room temperature. The solution was filtered and colourless blocks were recovered.