(5-Amino­isophthalato-κN)triaqua­(1,10-phenanthroline-κ2 N,N′)cobalt(II) trihydrate

Kou-Lin Zhang; Guo-Wang Diao; Seik Weng Ng

doi:10.1107/S1600536810040560

. 2010 Oct 20;66(Pt 11):m1421. doi: 10.1107/S1600536810040560

(5-Aminoisophthalato-κN)triaqua(1,10-phenanthroline-κ² N,N′)cobalt(II) trihydrate

Kou-Lin Zhang ^a, Guo-Wang Diao ^a, Seik Weng Ng ^b,^*

PMCID: PMC3009302 PMID: 21588848

Abstract

The Co^II atom in the title compound, [Co(C₈H₅NO₄)(C₁₂H₈N₂)(H₂O)₃]·3H₂O, is six-coordinated in a CoN₃O₃ octahedral geometry; the water-coordinated Co^II atom is chelated by the N-heterocycle. An intermolecular N—H⋯O hydrogen bond occurs. The carboxylate entity coordinates through the amino group. The carboxylate donor unit, coordinated and uncoordinated water molecules interact through O—H⋯O and N—H⋯O hydrogen bonds, generating a tightly-held three-dimensional cage-like network.

Related literature

For related structures, see: He et al. (2006 ▶); Wu et al. (2002a ▶,b ▶).

Experimental

Crystal data

[Co(C₈H₅NO₄)(C₁₂H₈N₂)(H₂O)₃]·3H₂O
M _r = 526.36
Monoclinic,
a = 10.1182 (2) Å
b = 13.9659 (2) Å
c = 16.2850 (2) Å
β = 95.827 (1)°
V = 2289.34 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.803, T _max = 1.000
18954 measured reflections
5683 independent reflections
5120 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.086
S = 1.04
5683 reflections
363 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040560/si2299sup1.cif

e-66-m1421-sup1.cif^{(25.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040560/si2299Isup2.hkl

e-66-m1421-Isup2.hkl^{(278.2KB, 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—H1w1⋯O6wⁱ	0.83 (1)	1.90 (1)	2.734 (1)	175 (2)
O1w—H1w2⋯O2ⁱⁱ	0.84 (1)	1.81 (1)	2.646 (1)	173 (2)
O2w—H2w1⋯O5wⁱ	0.83 (1)	1.93 (1)	2.761 (1)	174 (2)
O2w—H2w2⋯O4ⁱⁱⁱ	0.85 (1)	1.94 (1)	2.790 (1)	173 (2)
O3w—H3w1⋯O5w^iv	0.84 (1)	2.16 (2)	2.909 (2)	148 (2)
O3w—H3w2⋯O3ⁱⁱ	0.85 (1)	1.86 (1)	2.694 (1)	167 (2)
O4w—H4w1⋯O6w^v	0.85 (1)	1.98 (1)	2.811 (2)	169 (2)
O4w—H4w2⋯O2^iv	0.85 (1)	2.05 (1)	2.864 (2)	161 (3)
O5w—H5w1⋯O1	0.85 (1)	1.89 (1)	2.716 (2)	164 (2)
O5w—H5w2⋯O3^vi	0.85 (1)	1.90 (1)	2.719 (1)	161 (2)
O6w—H6w1⋯O1	0.85 (1)	1.82 (1)	2.665 (1)	174 (2)
O6w—H6w2⋯O4ⁱⁱⁱ	0.85 (1)	1.94 (1)	2.784 (1)	174 (2)
N1—H1N1⋯O4w	0.85 (1)	2.06 (1)	2.906 (2)	169 (2)
N1—H1N2⋯O4ⁱⁱⁱ	0.84 (1)	2.30 (1)	3.110 (2)	161 (2)

Open in a new tab

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

Acknowledgments

We thank the Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu Province, the National Natural Science Foundation of China (grant No. 20773107), Yangzhou University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The dianion of 5-aminoisophthalic acid binds to cobalt(II) in a bridging µ₄-manner in the monoaqua derivative (Wu et al., 2002a), and the carboxyl oxygen as well as the amino nitrogen atoms are all involved in bonding in the three-dimensional network structure. A diaqua dihydrate has also been reported; the compound has the monoanion in µ₂ bridging that gives rise to a chain motif (Wu et al., 2002b). The 4,4'-bipyridine spacer ligand lowers the dimensionality of cobalt 5-aminoisophthalate, and the diqua adduct, which crystallizes as a DMF solvate, exists as linear chains (He et al., 2006). The present 1,10-phenanthroline adduct is a triaqua trihydrate (Scheme I) in which the 5-aminosophthlate dianion binds only through the neutral amino donor site; the coordinated water molecules comprise the fac points of the octahedron around the metal atom (Fig. 1). The zwitterionic dianion, the coordinated and lattice water molecules interact through hydrogen bonds (Table 2) to furnish a tightly-held, three-dimensional network. Pairs of phenanthroline units show π···π interactions about a center-of-inversion at a distance of ca 3.5 Å (Fig. 2).

Experimental

Cobalt(II) nitrate hexahydrate (0.048 g, 0.165 mmol) dissolved in water (5 ml) was added to a mixture of 5-amino-isophthalic acid (0.030 g, 0.165 mmol) and sodium hydroxidie (0.013 g, 0.330 mmol) dissolved in water (5 ml). To this solution was added 1,10-phenanthroline (0.033 g, 0.165 mmol) dissolved in methanol (10 ml). The mixture was filtered and set aside for the growth of deep red crystals (35% yield based on the acid). CHN elemental analaysis. Calc. for C₂₀H₂₅C_ON₃O₁₀: C 45.63, H 4.79, N 7.98%. Found: C, 45.49; H, 4.89; N,7.91%.