Crystal structure of an eight-coordinate terbium(III) ion chelated by N,N′-bis­(2-hy­droxy­benz­yl)-N,N′-bis­(pyridin-2-ylmeth­yl)ethyl­enedi­amine (bbpen2−) and nitrate

Gregório, T.; Rüdiger, A.L.; Nunes, G.G.; Soares, J.F.; Hughes, D.L.

doi:10.1107/S2056989014026826

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ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages 65-68

https://doi.org/10.1107/S2056989014026826

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Crystal structure of an eight-coordinate terbium(III) ion chelated by N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine (bbpen²⁻) and nitrate

Thaiane Gregório,^a André Luis Rüdiger,^a Giovana G. Nunes,^a Jaísa F. Soares ^a and David L. Hughes ^b ^*

^aDepartamento de Química, Universidade Federal do Paraná, Centro Politécnico, Jardim das Américas, 81530-900 Curitiba-PR, Brazil, and ^bSchool of Chemistry, University of East Anglia, Norwich NR4 7TJ, England
^*Correspondence e-mail: d.l.hughes@uea.ac.uk

Edited by A. J. Lough, University of Toronto, Canada (Received 24 November 2014; accepted 5 December 2014; online 1 January 2015)

The reaction of terbium(III) nitrate pentahydrate in acetonitrile with N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine (H₂bbpen), previously deprotonated with triethylamine, produced the mononuclear compound [N,N′-bis(2-oxidobenzyl-κO)-N,N′-bis(pyridin-2-ylmethyl-κN)ethylenediamine-κ²N,N′](nitrato-κ²O,O′)terbium(III), [Tb(C₂₈H₂₈N₄O₂)(NO₃)]. The molecule lies on a twofold rotation axis and the Tb^III ion is eight-coordinate with a slightly distorted dodecahedral coordination geometry. In the symmetry-unique part of the molecule, the pyridine and benzene rings are both essentially planar and form a dihedral angle of 61.42 (7)°. In the molecular structure, the N₄O₄ coordination environment is defined by the hexadentate bbpen ligand and the bidentate nitrate anion. In the crystal, a weak C—H⋯O hydrogen bond links molecules into a two-dimensional network parallel to (001).

Keywords: crystal structure; lanthanide; terbium(III); N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine; mononuclear; dodecahedral..

CCDC reference: 1037922

1. Chemical context

As far as biological and biomedical applications are concerned, complexes of polydentate ligands with a range of metal ions in different oxidation states have been synthesized to model active sites of metalloproteins and to shed light on the consequences of heavy-metal chelation in living organisms, among many other applications (Colotti et al., 2013 ; Nurchi et al., 2013 ; Sears, 2013 ; Happe & Hemschemeier, 2014 ). Pyridyl and phenolate groups have been incorporated into these ligands because of their potential to mimic the coordination environments provided by the amino acids histidine and tyrosine, respectively (Hancock, 2013 ; Lenze et al., 2013 ). In this context, the heterotrifunctional Lewis base N,N′-bis(2-hydroxybenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine (H₂bbpen) is suitable for the coordination of a range of p-, d- and f-block ions because of its versatile soft donor atoms in the pyridine rings and hard donors in the amine and phenolate groups (Neves et al., 1992 ; Schwingel et al., 1996 ). Electrochemical studies of the mononuclear [Mn(bbpen)]PF₆, for example, revealed that this complex mimics some of the redox features of the photosystem II (PSII) (Neves et al., 1992). Complexes of bbpen^2– with vanadium(III) and oxido-vanadium(IV) have been obtained as models of the vanadium-modified transferrin, the probable vanadium-transporting protein in higher organisms (Neves et al., 1991 , 1993 ). Iron complexes of bbpen^2– modified with electron-donating and -withdrawing groups (Me, Br, NO₂), in turn, have been synthesized to provide detailed chemical information on the enzymatic activity of iron-tyrosinate proteins (Lanznaster et al., 2006 ). This ligand has also been employed to prepare lanthanide(III), gallium(III) and indium(III) complexes for medicinal applications such as the development of new contrast agents for magnetic resonance imaging, MRI (Wong et al., 1995 , 1996 ; Setyawati et al., 2000 ).

More recently, lanthanide(III) chelate complexes have also attracted attention in the field of molecular magnetism due to their highly significant single-ion magnetic anisotropy (Sessoli & Powell, 2009 ; Luzon & Sessoli, 2012 ). Accordingly, a number of examples of mononuclear lanthanide complexes that exhibit single-molecule magnet (SMM) behaviour have been reported (Rinehart & Long, 2011 ; Chilton et al., 2013 ; Ungur et al., 2014 ; Zhang et al., 2014 ). Our interest in the class of lanthanide complexes in which two coordination sites are occupied by relatively labile ligands, as in the title complex, comes from the possibility of using them as starting materials for the preparation of heteronuclear aggregates of d- and f-block ions that present SMM features. In this case, the replacement of the labile ligands by specific bidentate metalloligands can give rise to heteronuclear metal aggregates in which desirable ferromagnetic or ferrimagnetic exchange interactions are favoured (Totaro et al., 2013 ; Westrup et al., 2014 ).

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The Tb^III ion is eight-coordinate with a dodecahedral array of N and O atoms (Table 1); the four N atoms of the O₂N₄-ligand (bbpen) form one plane, the four O atoms the other, with the phenolic O atoms in the B-sites (roughly equatorial) and the nitrate group O atoms in the A-sites (above and below the equatorial plane). The normals to the two planes are essentially perpendicular. A twofold rotation axis passes through O3 and N1 of the nitrate group, the terbium(III) atom and the mid-point of the C7—C7ⁱ bond [symmetry code (i) 1 − x, y, −z + $[{1\over 2}]$ ]. In the symmetry-unique part of the molecule, the pyridine and benzene rings are both essentially planar and form a dihedral angle of 61.42 (7)°. The eightfold coordination pattern might also be described as a distorted bicapped trigonal prism with O1 and N2 as the capping atoms. However, this ignores the symmetry of the coordination, e.g. O1 and O1ⁱ would occupy different sites in the coordination polyhedron. Also, some of the rectangular faces of the prism are difficult to identify. In contrast, the dodecahedral pattern incorporates the twofold symmetry and the distortion from the ideal geometry is minimal.

Table 1
Selected bond lengths (Å)

Tb1—O1	2.1947 (13)	Tb1—N3	2.5558 (16)
Tb1—O2	2.4764 (15)	Tb1—N1	2.891 (2)
Tb1—N2	2.5521 (17)

Figure 1
View of a molecule of [Tb(bbpen)(NO₃)], indicating the atom-numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (i) −x + 1, y, −z + $[{1\over 2}]$ ].

3. Supramolecular features

In the crystal, a weak C—H⋯O hydrogen bond (Table 2) links molecules into a two-dimensional network parallel to (001), Fig. 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O3ⁱⁱ	0.99	2.37	3.338 (3)	166
Symmetry code: (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
A sheet of molecules, lying in a plane normal to the c axis, linked through short `weak hydrogen bonds', as C8—H8B⋯O3ⁱⁱ [symmetry codes: (ii) x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (iii) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z].

4. Database survey

Some examples of complexes with bbpen^2– and related ligands with d-block metal ions appear in the literature (Xu et al., 2000 ; dos Anjos et al., 2006 ; Lanznaster et al., 2006; Golchoubian & Gholamnezhad, 2009 ; Thomas et al., 2010 ) as well as p-block metal(III) compounds (Wong et al., 1995, 1996) and related yttrium(III) and lanthanide(III) complexes (Setyawati et al., 2000; Yamada et al., 2010 ).

5. Synthesis and crystallization

Tb(NO₃)₃·5H₂O, ethylenediamine, salicylaldehyde, sodium borohydride, 2-picolyl-chloride hydrochloride and triethylamine were purchased from Aldrich and used without purification. N,N′-bis(salicylidene)ethylenediamine (H₂salen) (Diehl et al., 2007 ), N,N′-bis(2-hydroxybenzyl)ethylenediamine (H₂bben) and N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-pyridylmethyl)ethylenediamine (H₂bbpen) (Neves et al., 1992) were prepared as described in the literature. The preparation of the title complex was carried out under N₂(g) using standard Schlenk and glove-box techniques. Acetonitrile was dried with CaH₂ and distilled prior to use. A solution containing triethylamine (300 µl, 2.15 mmol) in acetonitrile (10 ml) was added to a suspension of H₂bbpen (0.454 g, 1.00 mmol) in acetonitrile (25 ml) under stirring, giving a clear light-orange solution. After 15 min, this solution was added to a colourless solution of Tb(NO₃)₃·5H₂O (0.434 g, 0.998 mmol) in acetonitrile (25 ml). A pale-yellow solution was obtained, which gave a 65% yield of the solid of the title compound upon cooling at 253 K for 2–3 days. Recrystallization of this solid by vapor diffusion of dimethoxyethane into the reaction mixture gave pale-pink crystals after two weeks at room temperature. These crystals are air-stable and insoluble in all common organic solvents.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were included in idealized positions (with C—H distances set at 0.97 and 0.93 Å for the methylene and trigonal–planar groups, respectively) and their U_iso values were set to ride (1.2×) on the U_eq values of the parent carbon atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Tb(C₂₈H₂₈N₄O₂)(NO₃)]
M_r	673.47
Crystal system, space group	Orthorhombic, C222₁
Temperature (K)	100
a, b, c (Å)	8.5947 (6), 18.2401 (17), 16.9272 (13)
V (Å³)	2653.6 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.71
Crystal size (mm)	0.43 × 0.20 × 0.20

Data collection
Diffractometer	Bruker D8 Venture/Photon 100 CMOS
Absorption correction	Multi-scan (SADABS2014/2; Bruker, 2014 )
T_min, T_max	0.581, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	75009, 3320, 3289
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.010, 0.027, 1.15
No. of reflections	3320
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.30
Absolute structure	Flack x determined using 1431 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons & Flack, 2004 )
Absolute structure parameter	−0.0107 (19)
Computer programs: APEX2 and SAINT (Bruker, 2010 ), SHELXS97 and SHELXL2013 (Sheldrick, 2008 ), ORTEPII (Johnson, 1976 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1037922

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026826/lh5741sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026826/lh5741Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008) and WinGX (Farrugia, 2012).

[N,N'-Bis(2-oxidobenzyl-κO)-N,N'-bis(pyridin-2-ylmethyl-κN)ethylenediamine-κ²N,N'](nitrato-κ²O,O')terbium(III) top

Crystal data top

[Tb(C₂₈H₂₈N₄O₂)(NO₃)]	D_x = 1.686 Mg m⁻³
M_r = 673.47	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C222₁	Cell parameters from 9558 reflections
a = 8.5947 (6) Å	θ = 2.9–28.3°
b = 18.2401 (17) Å	µ = 2.71 mm⁻¹
c = 16.9272 (13) Å	T = 100 K
V = 2653.6 (4) Å³	Prism, pale pink
Z = 4	0.43 × 0.20 × 0.20 mm
F(000) = 1344

Data collection top

Bruker D8 Venture/Photon 100 CMOS diffractometer	3320 independent reflections
Radiation source: fine-focus sealed tube	3289 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 10.4167 pixels mm^-1	θ_max = 28.4°, θ_min = 2.9°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS2014/2; Bruker, 2014)	k = −24→24
T_min = 0.581, T_max = 0.746	l = −22→22
75009 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.010	w = 1/[σ²(F_o²) + (0.0139P)² + 1.0428P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.027	(Δ/σ)_max = 0.004
S = 1.15	Δρ_max = 0.87 e Å⁻³
3320 reflections	Δρ_min = −0.30 e Å⁻³
178 parameters	Absolute structure: Flack x determined using 1431 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: −0.0107 (19)
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Tb1	0.5000	0.51826 (2)	0.2500	0.01172 (4)
O1	0.59854 (16)	0.54526 (8)	0.13398 (8)	0.0167 (3)
O2	0.4357 (2)	0.39605 (9)	0.30473 (10)	0.0312 (4)
O3	0.5000	0.29285 (11)	0.2500	0.0586 (9)
N1	0.5000	0.35974 (11)	0.2500	0.0293 (6)
N2	0.7540 (2)	0.49068 (9)	0.32221 (10)	0.0183 (3)
N3	0.66305 (19)	0.63257 (8)	0.27777 (9)	0.0130 (3)
C1	0.8272 (3)	0.42575 (12)	0.32538 (14)	0.0249 (4)
H1	0.7809	0.3851	0.2993	0.030*
C2	0.9672 (2)	0.41490 (13)	0.36483 (14)	0.0275 (5)
H2	1.0155	0.3681	0.3656	0.033*
C3	1.0342 (2)	0.47389 (13)	0.40282 (14)	0.0253 (5)
H3	1.1304	0.4685	0.4298	0.030*
C4	0.9590 (2)	0.54124 (13)	0.40111 (12)	0.0203 (4)
H4	1.0022	0.5823	0.4278	0.024*
C5	0.8200 (2)	0.54783 (11)	0.35990 (10)	0.0151 (3)
C6	0.7349 (2)	0.62034 (12)	0.35643 (12)	0.0160 (4)
H6A	0.6528	0.6212	0.3975	0.019*
H6B	0.8088	0.6606	0.3679	0.019*
C7	0.5652 (2)	0.69987 (10)	0.28069 (12)	0.0156 (3)
H7A	0.6323	0.7432	0.2719	0.019*
H7B	0.5190	0.7043	0.3340	0.019*
C8	0.7933 (2)	0.64051 (11)	0.21953 (12)	0.0162 (4)
H8A	0.8566	0.5952	0.2212	0.019*
H8B	0.8607	0.6814	0.2372	0.019*
C9	0.7479 (2)	0.65450 (12)	0.13510 (12)	0.0161 (4)
C10	0.6559 (2)	0.60220 (10)	0.09514 (11)	0.0155 (4)
C11	0.6273 (2)	0.61288 (12)	0.01400 (12)	0.0188 (4)
H11	0.5663	0.5782	−0.0142	0.023*
C12	0.6873 (3)	0.67359 (13)	−0.02515 (12)	0.0232 (4)
H12	0.6664	0.6801	−0.0798	0.028*
C13	0.7777 (3)	0.72492 (13)	0.01476 (14)	0.0251 (4)
H13	0.8186	0.7663	−0.0123	0.030*
C14	0.8073 (2)	0.71496 (11)	0.09491 (12)	0.0199 (4)
H14	0.8688	0.7498	0.1225	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.01260 (5)	0.01031 (5)	0.01225 (5)	0.000	0.00008 (7)	0.000
O1	0.0177 (6)	0.0180 (6)	0.0145 (6)	−0.0021 (5)	0.0023 (5)	−0.0009 (5)
O2	0.0439 (9)	0.0209 (7)	0.0287 (8)	−0.0086 (7)	−0.0077 (7)	0.0083 (6)
O3	0.096 (2)	0.0096 (8)	0.0704 (19)	0.000	−0.046 (3)	0.000
N1	0.0418 (14)	0.0119 (9)	0.0343 (13)	0.000	−0.028 (2)	0.000
N2	0.0170 (8)	0.0191 (8)	0.0188 (8)	0.0028 (7)	−0.0021 (6)	0.0002 (6)
N3	0.0124 (7)	0.0136 (7)	0.0128 (6)	0.0003 (6)	−0.0002 (5)	0.0006 (5)
C1	0.0244 (10)	0.0208 (10)	0.0294 (11)	0.0046 (8)	−0.0059 (9)	−0.0027 (8)
C2	0.0250 (14)	0.0275 (10)	0.0298 (10)	0.0106 (8)	−0.0037 (8)	0.0042 (8)
C3	0.0180 (13)	0.0364 (11)	0.0214 (9)	0.0023 (8)	−0.0036 (7)	0.0102 (8)
C4	0.0176 (11)	0.0282 (10)	0.0153 (8)	−0.0033 (7)	−0.0028 (6)	0.0061 (8)
C5	0.0147 (8)	0.0196 (9)	0.0110 (8)	0.0001 (7)	0.0013 (6)	0.0032 (7)
C6	0.0162 (9)	0.0181 (9)	0.0138 (9)	−0.0009 (8)	−0.0022 (7)	−0.0010 (8)
C7	0.0161 (8)	0.0110 (8)	0.0198 (8)	−0.0006 (7)	−0.0002 (7)	−0.0012 (7)
C8	0.0124 (8)	0.0210 (9)	0.0153 (8)	−0.0023 (7)	0.0007 (7)	0.0021 (7)
C9	0.0136 (9)	0.0209 (10)	0.0139 (9)	0.0017 (8)	0.0009 (7)	0.0012 (8)
C10	0.0130 (8)	0.0175 (9)	0.0158 (8)	0.0028 (7)	0.0024 (7)	0.0001 (7)
C11	0.0181 (9)	0.0231 (10)	0.0153 (9)	0.0024 (8)	0.0000 (7)	−0.0021 (8)
C12	0.0266 (11)	0.0286 (11)	0.0142 (9)	0.0029 (9)	−0.0004 (8)	0.0042 (8)
C13	0.0303 (11)	0.0238 (10)	0.0210 (11)	−0.0032 (9)	0.0013 (9)	0.0080 (8)
C14	0.0196 (9)	0.0208 (9)	0.0194 (10)	−0.0012 (8)	0.0002 (8)	0.0022 (8)

Geometric parameters (Å, º) top

Tb1—O1ⁱ	2.1947 (13)	C3—H3	0.9500
Tb1—O1	2.1947 (13)	C4—C5	1.389 (3)
Tb1—O2ⁱ	2.4764 (15)	C4—H4	0.9500
Tb1—O2	2.4764 (15)	C5—C6	1.513 (3)
Tb1—N2ⁱ	2.5521 (17)	C6—H6A	0.9900
Tb1—N2	2.5521 (17)	C6—H6B	0.9900
Tb1—N3ⁱ	2.5558 (16)	C7—C7ⁱ	1.529 (4)
Tb1—N3	2.5558 (16)	C7—H7A	0.9900
Tb1—N1	2.891 (2)	C7—H7B	0.9900
O1—C10	1.324 (2)	C8—C9	1.503 (3)
O2—N1	1.266 (2)	C8—H8A	0.9900
O3—N1	1.220 (3)	C8—H8B	0.9900
N1—O2ⁱ	1.266 (2)	C9—C14	1.393 (3)
N2—C1	1.342 (3)	C9—C10	1.412 (3)
N2—C5	1.347 (3)	C10—C11	1.409 (3)
N3—C6	1.485 (2)	C11—C12	1.390 (3)
N3—C7	1.489 (2)	C11—H11	0.9500
N3—C8	1.498 (2)	C12—C13	1.391 (3)
C1—C2	1.391 (3)	C12—H12	0.9500
C1—H1	0.9500	C13—C14	1.392 (3)
C2—C3	1.380 (3)	C13—H13	0.9500
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.388 (3)

O1ⁱ—Tb1—O1	154.07 (7)	C8—N3—Tb1	111.56 (11)
O1ⁱ—Tb1—O2ⁱ	128.52 (6)	N2—C1—C2	123.4 (2)
O1—Tb1—O2ⁱ	77.36 (6)	N2—C1—H1	118.3
O1ⁱ—Tb1—O2	77.36 (6)	C2—C1—H1	118.3
O1—Tb1—O2	128.52 (6)	C3—C2—C1	118.3 (2)
O2ⁱ—Tb1—O2	51.64 (9)	C3—C2—H2	120.9
O1ⁱ—Tb1—N2ⁱ	98.20 (5)	C1—C2—H2	120.9
O1—Tb1—N2ⁱ	86.89 (5)	C2—C3—C4	119.11 (19)
O2ⁱ—Tb1—N2ⁱ	80.45 (6)	C2—C3—H3	120.4
O2—Tb1—N2ⁱ	79.10 (6)	C4—C3—H3	120.4
O1ⁱ—Tb1—N2	86.89 (5)	C3—C4—C5	119.2 (2)
O1—Tb1—N2	98.20 (5)	C3—C4—H4	120.4
O2ⁱ—Tb1—N2	79.10 (6)	C5—C4—H4	120.4
O2—Tb1—N2	80.45 (6)	N2—C5—C4	122.21 (19)
N2ⁱ—Tb1—N2	157.26 (8)	N2—C5—C6	117.05 (16)
O1ⁱ—Tb1—N3ⁱ	76.70 (5)	C4—C5—C6	120.74 (19)
O1—Tb1—N3ⁱ	82.18 (5)	N3—C6—C5	111.54 (16)
O2ⁱ—Tb1—N3ⁱ	141.99 (5)	N3—C6—H6A	109.3
O2—Tb1—N3ⁱ	132.91 (6)	C5—C6—H6A	109.3
N2ⁱ—Tb1—N3ⁱ	66.65 (5)	N3—C6—H6B	109.3
N2—Tb1—N3ⁱ	135.88 (5)	C5—C6—H6B	109.3
O1ⁱ—Tb1—N3	82.18 (5)	H6A—C6—H6B	108.0
O1—Tb1—N3	76.70 (5)	N3—C7—C7ⁱ	113.05 (13)
O2ⁱ—Tb1—N3	132.91 (6)	N3—C7—H7A	109.0
O2—Tb1—N3	141.99 (5)	C7ⁱ—C7—H7A	109.0
N2ⁱ—Tb1—N3	135.88 (5)	N3—C7—H7B	109.0
N2—Tb1—N3	66.65 (5)	C7ⁱ—C7—H7B	109.0
N3ⁱ—Tb1—N3	70.67 (7)	H7A—C7—H7B	107.8
O1ⁱ—Tb1—N1	102.97 (4)	N3—C8—C9	116.63 (16)
O1—Tb1—N1	102.97 (4)	N3—C8—H8A	108.1
O2ⁱ—Tb1—N1	25.82 (4)	C9—C8—H8A	108.1
O2—Tb1—N1	25.82 (4)	N3—C8—H8B	108.1
N2ⁱ—Tb1—N1	78.63 (4)	C9—C8—H8B	108.1
N2—Tb1—N1	78.63 (4)	H8A—C8—H8B	107.3
N3ⁱ—Tb1—N1	144.67 (4)	C14—C9—C10	120.42 (18)
N3—Tb1—N1	144.67 (4)	C14—C9—C8	120.25 (19)
C10—O1—Tb1	139.80 (12)	C10—C9—C8	119.08 (19)
N1—O2—Tb1	95.73 (12)	O1—C10—C11	121.83 (18)
O3—N1—O2	121.55 (11)	O1—C10—C9	120.05 (17)
O3—N1—O2ⁱ	121.55 (11)	C11—C10—C9	118.13 (18)
O2—N1—O2ⁱ	116.9 (2)	C12—C11—C10	120.67 (19)
O3—N1—Tb1	180.0	C12—C11—H11	119.7
O2—N1—Tb1	58.45 (11)	C10—C11—H11	119.7
O2ⁱ—N1—Tb1	58.45 (11)	C11—C12—C13	120.8 (2)
C1—N2—C5	117.83 (17)	C11—C12—H12	119.6
C1—N2—Tb1	126.43 (14)	C13—C12—H12	119.6
C5—N2—Tb1	115.74 (12)	C12—C13—C14	119.2 (2)
C6—N3—C7	109.19 (15)	C12—C13—H13	120.4
C6—N3—C8	107.09 (15)	C14—C13—H13	120.4
C7—N3—C8	111.34 (15)	C13—C14—C9	120.8 (2)
C6—N3—Tb1	105.69 (12)	C13—C14—H14	119.6
C7—N3—Tb1	111.67 (11)	C9—C14—H14	119.6

Tb1—O2—N1—O3	180.000 (1)	Tb1—N3—C7—C7ⁱ	−38.2 (2)
Tb1—O2—N1—O2ⁱ	0.000 (1)	C6—N3—C8—C9	−179.19 (19)
C5—N2—C1—C2	−0.5 (3)	C7—N3—C8—C9	−59.9 (2)
Tb1—N2—C1—C2	178.82 (17)	Tb1—N3—C8—C9	65.61 (19)
N2—C1—C2—C3	0.2 (4)	N3—C8—C9—C14	125.3 (2)
C1—C2—C3—C4	0.8 (3)	N3—C8—C9—C10	−60.3 (3)
C2—C3—C4—C5	−1.3 (3)	Tb1—O1—C10—C11	−142.18 (16)
C1—N2—C5—C4	0.0 (3)	Tb1—O1—C10—C9	37.5 (3)
Tb1—N2—C5—C4	−179.43 (14)	C14—C9—C10—O1	−179.29 (18)
C1—N2—C5—C6	−179.33 (18)	C8—C9—C10—O1	6.3 (3)
Tb1—N2—C5—C6	1.2 (2)	C14—C9—C10—C11	0.4 (3)
C3—C4—C5—N2	0.9 (3)	C8—C9—C10—C11	−174.00 (18)
C3—C4—C5—C6	−179.80 (18)	O1—C10—C11—C12	179.21 (19)
C7—N3—C6—C5	173.14 (16)	C9—C10—C11—C12	−0.5 (3)
C8—N3—C6—C5	−66.2 (2)	C10—C11—C12—C13	0.3 (3)
Tb1—N3—C6—C5	52.88 (17)	C11—C12—C13—C14	−0.2 (4)
N2—C5—C6—N3	−38.3 (2)	C12—C13—C14—C9	0.1 (3)
C4—C5—C6—N3	142.41 (18)	C10—C9—C14—C13	−0.2 (3)
C6—N3—C7—C7ⁱ	−154.7 (2)	C8—C9—C14—C13	174.1 (2)
C8—N3—C7—C7ⁱ	87.2 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O3ⁱⁱ	0.99	2.37	3.338 (3)	166

Symmetry code: (ii) x+1/2, y+1/2, z.

Acknowledgements

Financial support from the Brazilian agencies CNPq (grant No. 307592/2012–0) and CAPES (grant PVE A099/2013) is gratefully acknowledged. The authors also thank CNPq, CAPES and Fundação Araucária (Brazil) for fellowships.

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