1,10-Phenanthrolin-1-ium nitrate–aqua­bis­(4-hydroxy­benzoato-κ2 O,O′)(nitrato-κ2 O,O′)(1,10-phenanthroline-κ2 N,N′)erbium(III)–1,10-phenanthroline–water (1/1/0.5/2)

Fwu Ming Shen; Shie Fu Lush

doi:10.1107/S1600536810051767

. 2010 Dec 15;67(Pt 1):m86–m87. doi: 10.1107/S1600536810051767

1,10-Phenanthrolin-1-ium nitrate–aquabis(4-hydroxybenzoato-κ² O,O′)(nitrato-κ² O,O′)(1,10-phenanthroline-κ² N,N′)erbium(III)–1,10-phenanthroline–water (1/1/0.5/2)

Fwu Ming Shen ^a, Shie Fu Lush ^b,^*

PMCID: PMC3050183 PMID: 21522602

Abstract

In the title compound, C₁₂H₉N₂ ⁺·NO₃ ⁻·[Er(C₇H₅O₃)₂(NO₃)(C₁₂H₈N₂)(H₂O)]·0.5C₁₂H₈N₂·2H₂O, the water-molecule-coordinated Er^III ion is chelated by one 1,10-phenanthroline (phen) ligand, two 4-hydroxybenzoate anions and one nitrate anion in a monocapped square-antiprismatic coordination geometry. The uncoordinating phen molecule is approximately parallel to the 1,10-phenanthrolin-1-ium (Hphen) anion [dihedral angle = 3.3 (4)°]. The centroid–centroid distance of 3.801 (5) Å between pyridine rings suggests the existence of π–π stacking. The crystal structure contains an extensive network of classical O—H⋯O and N—H⋯O and weak C—H⋯O hydrogen bonds. C—H⋯π interactions between phen and 4-hydroxybenzoate is also present in the crystal structure. In the crystal, the uncoordinating phen is equally disordered over two sites about an inversion center.

Related literature

For a related hydrothermal substitution reaction, see: Xiong et al. (2001 ▶). For related structures, see: Liu et al. (2007 ▶, 2010 ▶); Neelgund et al. (2007 ▶).

Experimental

Crystal data

C₁₂H₉N₂ ⁺·NO₃ ⁻·[Er(C₇H₅O₃)₂(NO₃)(C₁₂H₈N₂)(H₂O)]·0.5C₁₂H₈N₂·2H₂O
M _r = 1071.07
Triclinic,
a = 10.9464 (2) Å
b = 11.3682 (3) Å
c = 19.2638 (5) Å
α = 77.108 (2)°
β = 84.790 (2)°
γ = 67.250 (2)°
V = 2154.95 (10) Å³
Z = 2
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 97 K
0.35 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Gemini-S CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.629, T _max = 0.694
16237 measured reflections
7710 independent reflections
6632 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.105
S = 1.05
7710 reflections
583 parameters
H-atom parameters constrained
Δρ_max = 2.48 e Å⁻³
Δρ_min = −1.41 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051767/xu5103sup1.cif

e-67-00m86-sup1.cif^{(44.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051767/xu5103Isup2.hkl

e-67-00m86-Isup2.hkl^{(377.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Er1—O1	2.470 (4)
Er1—O2	2.376 (4)
Er1—O3W	2.358 (3)
Er1—O4	2.372 (3)
Er1—O5	2.399 (3)
Er1—O6	2.366 (4)
Er1—O7	2.433 (4)
Er1—N1	2.461 (4)
Er1—N2	2.489 (4)

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

Cg4 is the centroid of the C32–C37 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2ⁱ	0.82	2.55	3.270 (6)	148
O1W—H1A⋯O6ⁱ	0.82	2.22	2.875 (6)	137
O1W—H1B⋯O12ⁱ	0.82	2.06	2.872 (10)	172
O2W—H2A⋯O9ⁱⁱ	0.82	1.94	2.737 (8)	164
O2W—H2B⋯O11ⁱ	0.82	2.01	2.789 (10)	157
O3W—H3A⋯O5ⁱⁱⁱ	0.82	1.90	2.671 (5)	155
O3W—H3B⋯O7ⁱⁱⁱ	0.82	2.16	2.836 (5)	140
N4—H4⋯O2W	0.86	1.91	2.725 (9)	157
O8—H8⋯O1W^iv	0.82	1.87	2.659 (6)	160
O9—H9⋯O11^v	0.82	2.09	2.803 (12)	145
O9—H9⋯O12^v	0.82	2.43	3.172 (12)	151
C34—H34⋯O3^v	0.93	2.43	3.256 (8)	148
C48—H48⋯O12^vi	0.93	2.27	3.046 (11)	141
C62—H62⋯O1^vii	0.93	2.55	3.387 (10)	150
C70—H70⋯O13ⁱ	0.93	2.35	3.244 (13)	161
C83—H83⋯Cg4ⁱⁱ	0.93	2.78	3.628 (9)	152

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

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

The coordination chemistry of erbium (III) with N and O donor ligands has been investigated in the past decade and numbers of erbium (III) complexes with different donor ligands have been synthesized and studied by X-ray crystallography (Liu et al., 2010; Neelgund et al., 2007; Liu et al., 2007). The title compound was recently obtained from the reaction of erbium nitrate, sodium benzoate and phen in an methanol-water mixture, and its crystal structure is reported here. Since no 4-hydrobenzoic acid ligand is present in the starting reaction mixture, it may be derived from the benzoic acid via in situ substitution(Xiong et al., 2001) under hydrothermal condition.

The Er^III ion is nine-coordinated by two N atoms of a phen ligand, four carboxylate O atoms of two 4-hydroxybenzoate anions, two O atoms of nitrate anion and one O atom of a water molecule. The resulting coordination geometry is a monocapped square antiprismatic coordination (Table 1 and Fig. 1).

The phen molecule is approximately parallel to 1,10-phenanthrolinium (Hphen), making dihedral angle of 3.3 (4)°.The centroid-centroid distance between N4-pyridine and N7-pyridine rings is 3.801 (5) Å, indictative of π—π interaction.The crystal structure contain an extensive network of classical (O—H···O, N—H···O) and weak (C—H···O) hydrogen bonds (Table 2 and Fig. 2).

In addition, C—H···π interaction (C83—H83···Cg4(C32—C37); full details and symmetry code are given in Table 2.) between phen and 4-hydroxybenzoate is present in the crystal structure.

Experimental

Erbium trinitrate solution was prepared by dissolving Er(NO₃)₃.6H₂O (0.4631 g, 1.00 mmole) at room temperature with stirring. The ligand solution was prepared by dissolving benzoic acid (0.4889 g, 4 mmole) and 1,10-phenanthroline (4 mmole) in 20 ml methanol at room temperature. The pH of the ligand solution was adjusted to about 6 with 2 N NaOH. The Er solution was added drop wise and slowly to the ligand solution. The reaction mixture was stirred for 2 h at room temperature. Pink crystals were obtained at room temperature over a period 3 months.