Aqua­(4-hydroxy­pyridine-2,6-dicarboxyl­ato)(1,10-phenanothroline)copper(II) 4.5-hydrate

Hossein Aghabozorg; Elham Motyeian; Janet Soleimannejad; Mohammad Ghadermazi; Jafar Attar Gharamaleki

doi:10.1107/S1600536807067207

. 2007 Dec 21;64(Pt 1):m252–m253. doi: 10.1107/S1600536807067207

Aqua(4-hydroxypyridine-2,6-dicarboxylato)(1,10-phenanothroline)copper(II) 4.5-hydrate

Hossein Aghabozorg ^a,^*, Elham Motyeian ^a, Janet Soleimannejad ^b, Mohammad Ghadermazi ^c, Jafar Attar Gharamaleki ^a

PMCID: PMC2915167 PMID: 21200591

Abstract

The title compound, [Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O or [Cu(hypydc)(phen)(H₂O)]·4.5H₂O (phen is 1,10-phenanthroline and hypydcH₂ is 4-hydroxypyridine-2,6-dicarboxylic acid), was obtained by the reaction of copper(II) nitrate hexahydrate with the proton-transfer compound (phenH)₂(hypydc) in aqueous solution. Both the cationic and the anionic fragments of the proton-transfer compound are involved in complexation. Each Cu^II atom has a distorted octahedral geometry. It is hexacoordinated by three O atoms and three N atoms, from one phen fragment (as bidentate ligand), one (hypydc)²⁻ unit (as tridentate ligand) and a water molecule. In the crystal structure, O—H⋯O and C—H⋯O hydrogen bonds, and π–π stacking interactions [centroid-to-centroid distance 3.5642 (11) Å] between the phen ring systems, contribute to the formation of a three-dimensional supramolecular structure.

Related literature

For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi et al. (2007 ▶); Aghabozorg, Attar Gharamaleki, Ghasemikhah et al. (2007 ▶); Aghabozorg, Daneshvar et al. (2007 ▶).

Experimental

Crystal data

[Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O
M _r = 523.94
Orthorhombic,
a = 18.686 (4) Å
b = 44.033 (8) Å
c = 10.3812 (18) Å
V = 8542 (3) Å³
Z = 16
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 296 (2) K
0.34 × 0.24 × 0.12 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.709, T _max = 0.881
59661 measured reflections
10800 independent reflections
9609 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.066
S = 1.01
10800 reflections
300 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ▶), with 4504 Friedel pairs
Flack parameter: 0.007 (4)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2005 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067207/su2032sup1.cif

e-64-0m252-sup1.cif^{(25KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067207/su2032Isup2.hkl

e-64-0m252-Isup2.hkl^{(323KB, 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
O5—H5A⋯O5W	0.85	1.73	2.5771 (14)	174
O6—H6D⋯O1ⁱ	0.85	1.88	2.7059 (12)	162
O6—H6C⋯O4ⁱⁱ	0.85	1.76	2.6048 (11)	174
O1W—H1C⋯O1ⁱⁱⁱ	0.85	1.97	2.8154 (12)	171
O2W—H2C⋯O3^iv	0.85	2.37	3.1062 (16)	145
O2W—H2D⋯O4W	0.85	1.90	2.7470 (16)	172
O3W—H3D⋯O2^v	0.85	1.93	2.7757 (13)	175
O3W—H3C⋯O4	0.85	1.90	2.7496 (13)	175
O4W—H4D⋯O3W	0.85	1.84	2.6834 (15)	171
O4W—H4C⋯O5ⁱ	0.85	2.26	3.0835 (16)	165
O5W—H5C⋯O1W	0.85	2.03	2.8604 (15)	164
O5W—H5D⋯O2W^vi	0.85	1.91	2.7204 (15)	159
C1—H1⋯O5^vii	0.93	2.41	3.1610 (18)	137
C3—H3⋯O3^viii	0.93	2.25	3.130 (2)	158
C8—H8⋯O3W^ix	0.93	2.42	3.315 (2)	161
C10—H10⋯O6	0.93	2.50	2.9995 (17)	114
C10—H10⋯O5W^x	0.93	2.42	3.1809 (19)	139

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

Acknowledgments

Financial support from Ilam University and the Teacher Training University is gratefully acknowledged.

supplementary crystallographic information

Comment

Non-covalent interactions, including hydrogen bonds, are of great importance in stabilizing structures in the solid state. We have synthesized several proton transfer compounds, some with remaining sites as electron donors that can coordinate to metal ions (Aghabozorg, Attar Gharamaleki, Ghadermazi et al., 2007; Aghabozorg, Attar Gharamaleki, Ghasemikhah et al., 2007; Aghabozorg, Daneshvar et al., 2007 and references therein). A wide range of different hydrogen bonds were observed in these compounds and water molecules of crystallization were also involved in hydrogen bonding. Here, we report on the synthesis and crystal structure of the title compound, (I).

The title complex crystallizes in the orthorhombic space group Fdd2, with sixteen molecules in the unit cell. The molecular structure is shown in Fig. 1. Both the cationic and anionic fragments of the starting proton transfer compound are involved in complexation. Each Cu^II atom has a distorted octahedral geometry. It is coordinated by one 1,10-phenanthroline ligand, (phen as bidentate ligand), one 4-hydroxypyridine-2,6-dicarboxylate group, [(hypydc)^2- as a tridentate ligand] and one coordinated water molecule. The axial bond lengths, Cu1—O2 and Cu1—O3 [2.3679 (9) and 2.3205 (11) Å, respectively] are longer than the equitoral metal-ligand bond lengths [1.9996 (8) - 2.0370 (9) Å], probabaly due to the Jahn-Teller effect. The dihedral angle between the planes passing through the (hypydc)^2– and (phen) fragments is 83.41 (4)°, indicating that these to units are almost perpendicular to one another.

In the crystal weak π-π stacking interactions [3.5642 (11) Å [1/4 + x, 1/4 - y, 1/4 + z] between the aromatic rings of the coordinated (phen) fragments are present (Fig. 2). The water molecules of crystallization are involved in the formation of hydrogen bonds, forming chains (Fig. 3 and Table 1). O—H···O and C—H···O hydrogen bonds, ion pairing and π–π stacking interactions all contribute to the formation of a supramolecular structure (Fig. 4).

Experimental

The proton transfer compound, (phenH)₂(hypydc), was prepared by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, hypydcH₂, with 1,10-phenanthroline, (phen). Cu(NO₃)₂.6H₂O (125 mg, 0.5 mmol) in water (20 ml) and the proton transfer compound, (phenH)₂(hypydc) (500 mg, 1.0 mmol) in water (20 ml), in a 1:2 molar ratio, were mixed. Blue crystals of (I) were obtained by the slow evaporation at room temperature.