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

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 [Tb(Cbbpen)(NO₃)]. The mol­ecule lies on a twofold rotation axis and the Tb^III ion is eight-coordinate with a slightly distorted dodeca­hedral coordination geometry.

Abstract

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-κ² N,N′](nitrato-κ² O,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).

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 ▸).

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 + ]. 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.

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 + ].

Table 1. Selected bond lengths ().

Tb1O1	2.1947(13)	Tb1N3	2.5558(16)
Tb1O2	2.4764(15)	Tb1N1	2.891(2)
Tb1N2	2.5521(17)

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 (, ).

DHA	DH	HA	D A	DHA
C8H8BO3ii	0.99	2.37	3.338(3)	166

Symmetry code: (ii) .

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 + , y + , z; (iii) x − , y − , z].

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 ▸).

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.

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 ()	8.5947(6), 18.2401(17), 16.9272(13)
V (3)	2653.6(4)
Z	4
Radiation type	Mo K
(mm1)	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 > 2(I)] reflections	75009, 3320, 3289
R int	0.020
(sin /)max (1)	0.668
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.010, 0.027, 1.15
No. of reflections	3320
No. of parameters	178
H-atom treatment	H-atom parameters constrained
max, min (e 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 ▸).

Supplementary Material

CCDC reference: 1037922

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

[Tb(C28H28N4O2)(NO3)]	Dx = 1.686 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0139P)2 + 1.0428P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.027	(Δ/σ)max = 0.004
S = 1.15	Δρmax = 0.87 e Å−3
3320 reflections	Δρmin = −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

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.