Tetra­aqua­bis­[N,N′-bis­(pyridin-3-yl­methyl­idene)benzene-1,4-diamine]­zinc dinitrate 1.49-hydrate

Li Kong; Haihui Yu; Jibo Zhang; Weiyi Cui

doi:10.1107/S1600536811046915

. 2011 Nov 12;67(Pt 12):m1752. doi: 10.1107/S1600536811046915

Tetraaquabis[N,N′-bis(pyridin-3-ylmethylidene)benzene-1,4-diamine]zinc dinitrate 1.49-hydrate

Li Kong ^a, Haihui Yu ^b,^*, Jibo Zhang ^a, Weiyi Cui ^a

PMCID: PMC3238659 PMID: 22199550

Abstract

In the title compound, [Zn(C₁₈H₁₄N₄)₂(H₂O)₄](NO₃)₂·1.49H₂O, the Zn^II atom, lying on an inversion center, is coordinated by two N atoms from two N,N′-bis(pyridin-3-ylmethylidene)benzene-1,4-diamine ligands and four water molecules in a distorted octahedral geometry. The nitrate anion is disordered over two sets of sites, with an occupancy ratio of 0.744 (4):0.256 (4). The uncoordinated water molecule is also disordered with an occupancy factor of 0.744 (4). O—H⋯O and O—H⋯N hydrogen bonds link the complex cations, nitrate anions and uncoordinated water molecules into a supramolecular layer parallel to (102).

Related literature

For background to the design and synthesis of zinc complexes with Schiff-base ligands and their potential applications as fluorescent probes, see: Su et al. (1999 ▶); Ye et al. (2005 ▶). For the synthesis of the ligand, see: Ye et al. (2004 ▶).

Experimental

Crystal data

[Zn(C₁₈H₁₄N₄)₂(H₂O)₄](NO₃)₂·1.49H₂O
M _r = 860.95
Triclinic,
a = 8.5664 (17) Å
b = 9.928 (2) Å
c = 12.496 (3) Å
α = 81.47 (3)°
β = 71.55 (3)°
γ = 78.78 (3)°
V = 984.6 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 295 K
0.48 × 0.28 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.731, T _max = 0.885
9721 measured reflections
4462 independent reflections
3908 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.141
S = 1.14
4462 reflections
305 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046915/hy2483sup1.cif

e-67-m1752-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046915/hy2483Isup2.hkl

e-67-m1752-Isup2.hkl^{(218.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O4ⁱ	0.87	1.87	2.725 (4)	170
O1W—H1A⋯O4′ⁱ	0.87	2.23	3.035 (13)	154
O1W—H1B⋯O3W	0.86	2.03	2.859 (13)	161
O1W—H1B⋯O3′	0.86	1.82	2.65 (3)	161
O2W—H2A⋯N4ⁱⁱ	0.85	1.92	2.706 (3)	152
O2W—H2B⋯O3ⁱⁱⁱ	0.86	1.96	2.761 (3)	155
O3W—H3A⋯O3^iv	0.88	2.36	3.073 (12)	139
O3W—H3A⋯O5^iv	0.88	2.38	3.112 (13)	142
O3W—H3B⋯O4	0.88	1.95	2.824 (13)	169

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

Acknowledgments

This work was supported financially by the Natural Science Foundation of Jilin Province (grant Nos. 2010178 and 2011073).

supplementary crystallographic information

Comment

Bipyridine-type ligands have been extensively investigated in recent years, owing to their simple structures, readily availabilities and predictable formation of network structures. Moreover, when introduced in double Schiff-base, a great deal of metal–organic frameworks with unusual network patterns and novel properties can be achieved due to the specific geometry including the different relative orientation of N-donors and the zigzag conformation of the space moiety between the two terminal coordination groups. For background to the design and syntheses of zinc complexes with Schiff-base and their potential applications as fluorescent probes, see: Su et al. (1999); Ye et al. (2005).

In the title compound (Fig. 1), the Zn^II ion lies on an inversion center and is coordinated in a distorted octahedral geometry by two N atoms from two N,N'-bis(3-pyridylmethylene)-p-phenylenediamine (L) ligands in the axial positions and four O atoms of four coordinated water molecules in the equatorial positions. The Zn—O distances are 2.0705 (17) and 2.1691 (19) Å and the Zn—N distance is 2.1462 (19) Å. As shown in Fig. 2, the complex cations, nitrate anions and uncoordinated water molecules are connected by O—H···O hydrogen bonds (Table 1), forming a layer structure.

Experimental

The ligand L was prepared according to the previous method (Ye et al., 2004). 1,4-Diaminobenzene (2.14 mg, 10 mmol) was dissolved in methanol (20 ml), followed by addition of 3-pyridinecarboxaldehyde (4.24 mg, 40 mmol). The mixture was stirred at room temperature for 2 h and then filtered. The resulting yellow crystalline solid was washed with methanol several times and dried in air. A solution of Zn(NO₃)₂ (35.9 mg, 0.2 mmol) in acetonitrile (10 ml) was slowly layered onto a solution of L (117 mg, 0.625 mmol) in methylene chloride (12 ml). Diffusion between the two phases over two weeks produced colorless crystals of the title compound.