Tetra-μ-benzoato-κ4 O:O′;κ3 O:O,O′;κ3 O,O′:O′-bis­[(benzoato-κ2 O,O′)(1,10-phenanthroline-κ2 N,N′)terbium(III)] benzoic acid disolvate

Ping Howe Ooi; Siang Guan Teoh; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536810016788

. 2010 May 15;66(Pt 6):m644–m645. doi: 10.1107/S1600536810016788

Tetra-μ-benzoato-κ⁴ O:O′;κ³ O:O,O′;κ³ O,O′:O′-bis[(benzoato-κ² O,O′)(1,10-phenanthroline-κ² N,N′)terbium(III)] benzoic acid disolvate

Ping Howe Ooi ^a,^‡, Siang Guan Teoh ^a, Chin Sing Yeap ^b,^§, Hoong-Kun Fun ^b,^*,^¶

PMCID: PMC2979618 PMID: 21579294

Abstract

The asymmetric unit of the title complex, [Tb₂(C₇H₅O₂)₆(C₁₂H₈N₂)₂]·2C₇H₆O₂, consists of one-half of the complex molecule, which lies on a crystallographic inversion centre, and one benzoic acid solvent molecule. The two Tb^III ions are linked by four bridging benzoate ions, with a Tb⋯Tb distance of 3.9280 (6) Å. Additionally, each Tb^III ion is coordinated by one phenanthroline heterocycle and a bidentate benzoate ion. The irregular nine-coordinated geometry of the Tb^III ion is composed of seven O and two N atoms. The molecular structure is stabilized by intramolecular C—H⋯O hydrogen bonds. In the crystal structure, molecules are linked into chains along the a axis by intermolecular C—H⋯O hydrogen bonds. The crystal structure is further stabilized by intermolecular C—H⋯O and C—H⋯π interactions. Weak π–π interactions are also observed [centroid–centroid distances = 3.6275 (14)–3.6604 (14) Å].

Related literature

For general background to and applications of terbium(III) complexes, see: Xin et al. (2003 ▶); Tian et al. (2009 ▶). For related Ln–benzoato (Ln = lanthanide) complexes, see: Niu et al. (1999 ▶, 2002 ▶); Shi et al. (2001 ▶); Ooi et al. (2010a ▶,b ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Tb₂(C₇H₅O₂)₆(C₁₂H₈N₂)₂]·2C₇H₆O₂
M _r = 1649.14
Triclinic,
a = 9.5264 (15) Å
b = 12.719 (2) Å
c = 15.061 (2) Å
α = 74.836 (6)°
β = 78.345 (6)°
γ = 76.242 (6)°
V = 1691.7 (4) Å³
Z = 1
Mo Kα radiation
μ = 2.15 mm⁻¹
T = 100 K
0.59 × 0.27 × 0.13 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.364, T _max = 0.765
71560 measured reflections
11944 independent reflections
11553 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.018
wR(F ²) = 0.101
S = 1.20
11944 reflections
460 parameters
H-atom parameters constrained
Δρ_max = 1.41 e Å⁻³
Δρ_min = −2.25 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016788/rz2444sup1.cif

e-66-0m644-sup1.cif^{(38.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016788/rz2444Isup2.hkl

e-66-0m644-Isup2.hkl^{(583.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Tb1—O5ⁱ	2.3349 (14)
Tb1—O4ⁱ	2.3420 (15)
Tb1—O6	2.3490 (15)
Tb1—O3	2.4251 (15)
Tb1—O1	2.4669 (15)
Tb1—O2	2.4672 (15)
Tb1—N2	2.5370 (17)
Tb1—N1	2.5813 (18)
Tb1—O4	2.6057 (16)

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Symmetry code: (i) Inline graphic .

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

Cg1 is the centroid of the C35–C40 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1O8⋯O1	0.82	1.88	2.640 (3)	154
C2—H2A⋯O5ⁱ	0.93	2.40	3.036 (3)	125
C4—H4A⋯O2ⁱⁱ	0.93	2.45	3.172 (3)	135
C11—H11A⋯O6	0.93	2.40	2.969 (3)	120
C15—H15A⋯O7	0.93	2.58	3.448 (3)	155
C23—H23A⋯Cg1ⁱⁱⁱ	0.93	2.57	3.462 (3)	160

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

Acknowledgments

SGT and PHO thank Universiti Sains Malaysia (USM) for the University Grant (No. 1001/229/PKIMIA/815002) in this research. HKF and CSY thank USM for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). CSY also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

Lanthanide complexes, especially terbium and europium complexes possess excellent luminescence properties due to their narrow emission bands and are widely used in lighting devices (Xin et al., 2003). Rare-earth metals with benzoic acid and some of the derivatives or with mixed ligands have drawn great attention due to the various crystal structures and unique properties (Tian et al., 2009). The title compound (I) was synthesized and its structure was determined. Similar crystal structures with different lanthanides have been reported, such as lanthanum(III) (Shi et al., 2001), samarium(III) (Niu et al., 1999), gadolinium(III) (Niu et al., 2002) and neodymium(III) (Ooi et al., 2010a).

The asymmetric unit of (I) (Fig. 1) consists of one-half of the complex molecule and one benzoic acid. The complex molecule lies on a crystallographic inversion center. The geometric parameters and the configuration is very close to the related europium(III) complex (Ooi et al., 2010b). The two terbium(III) ions are linked by four benzoate ions, with an Tb–Tb distance of 3.9280 (6) Å. Among the four benzoate ions, two of them also behave as chelating ligands to the terbium(III) ions. Additionally, each terbium(III) ion is coordinated by one phenanthroline heterocycle and a bidentate benzoate ion. The irregular nine-coordinated geometry of the terbium(III) ion is completed by seven benzoate O atoms and two phenanthroline N atoms. Bond lengths of Tb–O and Tb–N are listed in Table 1.

In the crystal structure, intermolecular C4—H4A···O2 hydrogen bonds (Table 2) link the molecules into chains along the a axis (Fig. 2). The crystal structure is further stabilized by intermolecular O8—H1O8···O1, C15A—H15A···O7 and C23—H23A···Cg1 interactions (Table 2; Cg1 is the centroid of the C35–C40 phenyl ring). Intramolecular C2—H2A···O5 and C11—H11A···O6 hydrogen bonds (Table 2) stabilize the molecular structure. Weak π–π interactions of Cg2···Cg3^iv = 3.6604 (14) Å and Cg3···Cg3^iv = 3.6275 (14) Å [Cg2 and Cg3 are centroids of rings C8–C11/N2/C12 and C1/C5–C8/C12; symmetry code: (iv) 1-x, 1-y, 2-z] are observed.

Experimental

0.5 mmol of TbCl₃.6H₂O was dissolved in methanol and then was added into a solution (methanol-H₂O, 1.5:1) of 1,10-phenanthroline (0.5 mmol) and benzoic acid (1.5 mmol). The mixture was sealed in a tube, and heated directly to 403 K. After keeping at 403 K for 2 days, it was cooled to room temperature. Colourless block crystals of the title compound were obtained by filtration, and were washed with water and ethanol.