catena-Poly[[[diaqua­[3-(pyridin-4-yl)benzoato-[kappa]²O,O']terbium(III)]-bis­[[mu]-3-(pyridin-4-yl)benzoato-[kappa]²O:O']] monohydrate]

In the title compound, {[Tb(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O}_n, the Tb^III cation is in an eight-coordinate environment, ligated by six carboxyl­ate O atoms from five 3-(pyridin-4-yl)benzoate (L) ligands and by two O atoms from water mol­ecules. The cations are bridged by the carboxyl­ate O atoms of the L ligands to form a two-stranded polymeric chain which is assembled into a three-dimensional supra­molecular network through regular inter­chain O-H...N hydrogen bonding. On excitation at 320 nm, the title compound displays a series of emissions, which were assigned to the characteristic electronic transitions of Tb^III.

S1. Comment

In recent years, aromatic carboxylic acid ligands have been extensively investigated for the construction of metal–organic frameworks (MOFs) with attracting topologies and properties (Huang et al., 2007). In particular, lanthanide MOFs of aromatic carboxylic acid ligands which have potential applications in medical imaging, sensors and electro-optical devices have drawn considerable current attention (Amghouz et al., 2012). 3-(Pyridin-4-yl)benzoic acid (HL), with both a pyridyl group and a benzoic acid group, is a typical unsymmetrical spacer, and up to now only a series of its transition metal coordination complexes have been synthesized and characterized (Wu et al., 2011). We report here the synthesis, structure and photoluminescence of the first lanthanide complex of HL, the title complex, (I).

In complex (I), the Tb^III cation is in an eight-coordinate environment, ligated by six carboxylate O atoms from five L ligands and by two O atoms from water molecules (Fig. 1). The Tb—O bonds fall in the normal range [2.276 (2)–2.516 (3) Å; Reference for standard data?]. The deprotonated L ligands are bidentate and display two coordination modes of the carboxylate groups, namely chelating and bridging; the N atoms of the pyridyl groups do not take part in the coordination.

Complex (I) forms a two-stranded polymeric chain, constructed from two L ligands bridging pairs of Tb^III cations side by side and two further L ligands chelating them up and down; the metal–metal separation is 4.883 Å (Fig. 2), similar to the literature value (Zhou et al., 2008). These chains of (I) are connected by interchain O—H···N hydrogen bonds between the coordinated water molecules (as donors) and the uncoordinated pyridyl groups of the L ligands (as acceptors), leading to the formation of a three-dimensional network structure with the solvent water molecules residing in the accessible void (Fig. 3 and Table 3).

The luminescent spectra of the free HL molecule and (I) were measured in the solid state at room temperature. As shown in Fig. 4, free HL displays strong luminescence with a single broad strong band centred at 418 nm, corresponding to excitation at 318 nm. When excited with light of the same wavelength, (I) displays the characteristic narrow emissions of Tb^III, which correspond to transitions from the ⁵d₄ energy level up to the ⁷f_j (j = 3, 4, 5 and 6) energy levels. The most intense emission is around 542–545 nm, which is attributed to the ⁵d₄–⁷f₅ transition. Other emissions at 621, 579–590 and 489 nm can be assigned to ⁵d₄–⁷f₃, ⁵d₄–⁷f₄ and ⁵d₄–⁷f₆, respectively. The obvious splitting of the three higher-energy emissions is due to crystal-field splitting (Yatsimirskii & Davidenko, 1979).

Related literature

For related literature, see: Amghouz et al. (2012); Huang et al. (2007); Wu et al. (2011); Yatsimirskii & Davidenko (1979); Zhou et al. (2008).

S2. Experimental

For the preparation of the title compound, (I), a mixture of TbCl₃ (0.027 g, 0.1 mmol), HL (0.060 g, 0.3 mmol), NaOH (0.012 g, 0.3 mmol), deionized water (7.5 ml) and dimethylformamide (7.5 ml) was sealed into a 25 ml Teflon-lined stainless steel autoclave. The autoclave was heated at 413 K for 4 d. After cooling slowly to room temperature, pink block-shaped crystals of (I) suitable for X-ray analysis were obtained in 59% yield (based on Tb). Selected IR (KBr pellet, ν, cm^-1): 3093 (w), 3421 (m), 1609 (m), 1557 (m), 1437 (w), 1309 (s), 1069 (w), 680 (m), 624 (w). IR spectra were recorded on a Bruker VECTOR22 spectrophotometer with KBr pellets in the 400–4000 cm^-1 region. The fluorescent spectra were determined on a Hitachi F-4500 fluorophotometer in the solid state at room temperature.

S3. Refinement

The H atoms of the coordinated water molecules were located from difference Fourier maps and refined with geometrical restraints [O—H = 0.85 (1) Å and H···H = 1.35 (2) Å]. The H atoms of the solvent water could not be found and accordingly were not included in the model. H atoms attached to C atoms were generated geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å. In all cases, U_iso(H) values were taken as 1.2U_eq(host).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environment of the Tb^III atom in (I), with atom O9 omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 2, -y + 2, -z + 1; (ii) -x + 1, -y + 2, -z + 1.]
	Fig. 2. A view of the infinite two-stranded chain bridged by L in (I). The Tb^III atoms run along the a axis.
	Fig. 3. A view of the three-dimensional network structure in (I), formed by regular interchain hydrogen-bonding interactions (dashed lines).
	Fig. 4. The solid-state photoluminescent spectra of (I) (lower line; red in the electronic version of the paper) and the free ligand HL (upper line; purple) at room temperature.

catena-Poly[[[diaqua[3-(pyridin-4-yl)benzoato- κ²O,O']terbium(III)]-bis[µ-3-(pyridin-4-yl)benzoato- κ²O:O']] monohydrate]

Crystal data

[Tb(C12H8NO2)3(H2O)2]·H2O	Z = 2
Mr = 807.55	F(000) = 808
Triclinic, P1	Dx = 1.660 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7093 (10) Å	Cell parameters from 4019 reflections
b = 13.9463 (14) Å	θ = 2.4–27.3°
c = 14.0767 (14) Å	µ = 2.25 mm^−1
α = 118.086 (2)°	T = 296 K
β = 104.170 (2)°	Block, pink
γ = 90.036 (2)°	0.37 × 0.21 × 0.17 mm
V = 1615.5 (3) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	5657 independent reflections
Radiation source: fine-focus sealed tube	4513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.490, Tmax = 0.701	k = −14→16
8244 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0376P)^2] where P = (Fo^2 + 2Fc^2)/3
5657 reflections	(Δ/σ)max = 0.001
454 parameters	Δρmax = 1.18 e Å^−3
6 restraints	Δρmin = −0.90 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tb1	0.747618 (18)	1.001657 (14)	0.497225 (14)	0.02260 (7)
O1	0.7929 (3)	0.8222 (2)	0.3497 (2)	0.0352 (6)
O2	0.6165 (3)	0.8185 (2)	0.4213 (2)	0.0325 (6)
O3	0.8841 (3)	0.9122 (2)	0.5894 (2)	0.0338 (6)
O4	1.0974 (3)	0.9546 (2)	0.5787 (2)	0.0349 (6)
O5	0.5790 (3)	0.9691 (2)	0.3274 (2)	0.0337 (6)
O6	0.3805 (3)	0.9742 (2)	0.3792 (2)	0.0319 (6)
O7	0.6491 (3)	1.1719 (2)	0.5345 (3)	0.0380 (7)
H7A	0.570 (2)	1.180 (3)	0.549 (3)	0.046*
H7B	0.683 (4)	1.2332 (17)	0.545 (3)	0.046*
O8	0.9216 (3)	1.1498 (2)	0.6556 (2)	0.0348 (6)
H8A	1.0092 (15)	1.150 (3)	0.658 (3)	0.042*
H8B	0.919 (4)	1.201 (2)	0.7190 (17)	0.042*
O9	0.6201 (6)	0.7721 (4)	0.6139 (4)	0.1095 (16)
N1	0.8725 (5)	0.3118 (3)	−0.1489 (3)	0.0531 (10)
N2	0.7725 (5)	0.3785 (3)	0.5892 (4)	0.0590 (11)
N3	−0.3300 (5)	0.7985 (4)	−0.0405 (4)	0.0751 (14)
C1	0.6915 (4)	0.7692 (3)	0.3546 (3)	0.0289 (8)
C2	0.6568 (4)	0.6478 (3)	0.2803 (3)	0.0311 (9)
C3	0.5530 (4)	0.5894 (3)	0.2922 (4)	0.0395 (10)
H3	0.5109	0.6246	0.3504	0.047*
C4	0.5119 (5)	0.4781 (3)	0.2174 (4)	0.0491 (12)
H4	0.4421	0.4393	0.2258	0.059*
C5	0.5732 (5)	0.4250 (3)	0.1312 (4)	0.0449 (11)
H5	0.5430	0.3510	0.0805	0.054*
C6	0.6808 (4)	0.4816 (3)	0.1193 (3)	0.0355 (9)
C7	0.7210 (4)	0.5931 (3)	0.1944 (3)	0.0317 (9)
H7	0.7922	0.6317	0.1871	0.038*
C8	0.7492 (5)	0.4226 (3)	0.0273 (3)	0.0385 (10)
C9	0.6655 (6)	0.3645 (4)	−0.0819 (4)	0.0584 (13)
H9	0.5662	0.3604	−0.0992	0.070*
C10	0.7337 (6)	0.3120 (4)	−0.1654 (4)	0.0655 (15)
H10	0.6762	0.2739	−0.2390	0.079*
C11	0.9518 (6)	0.3662 (4)	−0.0438 (4)	0.0553 (13)
H11	1.0507	0.3671	−0.0293	0.066*
C12	0.8949 (5)	0.4223 (4)	0.0464 (4)	0.0491 (11)
H12	0.9551	0.4593	0.1191	0.059*
C13	1.0152 (4)	0.9035 (3)	0.6012 (3)	0.0258 (8)
C14	1.0770 (4)	0.8252 (3)	0.6399 (3)	0.0276 (8)
C15	1.2235 (4)	0.8356 (3)	0.6839 (3)	0.0382 (10)
H15	1.2835	0.8926	0.6921	0.046*
C16	1.2802 (5)	0.7609 (4)	0.7156 (4)	0.0503 (12)
H16	1.3783	0.7684	0.7472	0.060*
C17	1.1893 (5)	0.6740 (4)	0.7000 (4)	0.0505 (12)
H17	1.2282	0.6234	0.7207	0.061*
C18	1.0431 (4)	0.6614 (3)	0.6546 (3)	0.0358 (9)
C19	0.9876 (4)	0.7398 (3)	0.6270 (3)	0.0306 (9)
H19	0.8890	0.7348	0.5995	0.037*
C20	0.9489 (5)	0.5649 (3)	0.6336 (3)	0.0397 (10)
C21	0.8013 (6)	0.5565 (4)	0.6047 (5)	0.0632 (15)
H21	0.7565	0.6137	0.6002	0.076*
C22	0.7202 (6)	0.4632 (4)	0.5824 (5)	0.0729 (17)
H22	0.6210	0.4597	0.5609	0.088*
C23	0.9150 (7)	0.3872 (4)	0.6182 (4)	0.0600 (14)
H23	0.9569	0.3300	0.6250	0.072*
C24	1.0043 (6)	0.4759 (4)	0.6388 (4)	0.0542 (13)
H24	1.1030	0.4756	0.6564	0.065*
C25	0.4454 (4)	0.9651 (3)	0.3090 (3)	0.0269 (8)
C26	0.3583 (4)	0.9469 (3)	0.1963 (3)	0.0313 (9)
C27	0.4263 (5)	0.9470 (4)	0.1201 (4)	0.0475 (12)
H27	0.5256	0.9622	0.1400	0.057*
C28	0.3453 (5)	0.9243 (5)	0.0150 (4)	0.0645 (15)
H28	0.3903	0.9259	−0.0356	0.077*
C29	0.1974 (5)	0.8992 (4)	−0.0162 (4)	0.0526 (13)
H29	0.1447	0.8816	−0.0884	0.063*
C30	0.1266 (4)	0.9000 (3)	0.0590 (3)	0.0355 (9)
C31	0.2100 (4)	0.9251 (3)	0.1652 (3)	0.0320 (9)
H31	0.1649	0.9273	0.2173	0.038*
C32	−0.0308 (4)	0.8685 (3)	0.0253 (4)	0.0392 (10)
C33	−0.1044 (5)	0.8755 (4)	0.1014 (4)	0.0498 (12)
H33	−0.0555	0.9044	0.1768	0.060*
C34	−0.2486 (5)	0.8397 (4)	0.0652 (5)	0.0631 (14)
H34	−0.2933	0.8444	0.1184	0.076*
C35	−0.2606 (6)	0.7944 (5)	−0.1125 (5)	0.0787 (18)
H35	−0.3134	0.7685	−0.1866	0.094*
C36	−0.1148 (5)	0.8260 (5)	−0.0846 (4)	0.0643 (14)
H36	−0.0728	0.8188	−0.1399	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb1	0.02166 (10)	0.02110 (10)	0.02875 (11)	0.00374 (7)	0.01367 (7)	0.01186 (8)
O1	0.0318 (15)	0.0264 (15)	0.0449 (16)	0.0003 (12)	0.0206 (13)	0.0106 (13)
O2	0.0277 (15)	0.0241 (14)	0.0425 (16)	0.0030 (11)	0.0207 (12)	0.0084 (12)
O3	0.0249 (15)	0.0353 (16)	0.0491 (17)	0.0085 (12)	0.0129 (12)	0.0255 (14)
O4	0.0385 (16)	0.0394 (17)	0.0437 (16)	0.0067 (13)	0.0223 (13)	0.0282 (14)
O5	0.0227 (15)	0.0455 (17)	0.0358 (15)	0.0043 (12)	0.0118 (12)	0.0203 (14)
O6	0.0312 (15)	0.0409 (17)	0.0305 (14)	0.0082 (12)	0.0177 (12)	0.0184 (13)
O7	0.0344 (17)	0.0251 (15)	0.064 (2)	0.0091 (13)	0.0270 (15)	0.0228 (15)
O8	0.0253 (15)	0.0340 (16)	0.0360 (16)	0.0016 (12)	0.0140 (12)	0.0073 (13)
O9	0.124 (4)	0.115 (4)	0.125 (4)	0.053 (3)	0.051 (3)	0.078 (3)
N1	0.072 (3)	0.036 (2)	0.052 (3)	0.017 (2)	0.037 (2)	0.013 (2)
N2	0.080 (3)	0.036 (2)	0.074 (3)	0.002 (2)	0.036 (3)	0.030 (2)
N3	0.037 (3)	0.083 (4)	0.085 (4)	−0.008 (2)	0.011 (2)	0.028 (3)
C1	0.027 (2)	0.025 (2)	0.031 (2)	0.0040 (16)	0.0090 (17)	0.0102 (17)
C2	0.030 (2)	0.028 (2)	0.035 (2)	0.0058 (17)	0.0124 (17)	0.0133 (18)
C3	0.043 (3)	0.030 (2)	0.046 (3)	0.0053 (19)	0.025 (2)	0.014 (2)
C4	0.052 (3)	0.035 (3)	0.064 (3)	0.000 (2)	0.031 (2)	0.019 (2)
C5	0.049 (3)	0.022 (2)	0.052 (3)	0.0029 (19)	0.017 (2)	0.007 (2)
C6	0.041 (2)	0.026 (2)	0.035 (2)	0.0104 (18)	0.0143 (19)	0.0098 (18)
C7	0.028 (2)	0.031 (2)	0.037 (2)	0.0069 (17)	0.0138 (17)	0.0150 (19)
C8	0.047 (3)	0.023 (2)	0.043 (2)	0.0094 (19)	0.019 (2)	0.0104 (19)
C9	0.055 (3)	0.057 (3)	0.045 (3)	0.024 (3)	0.016 (2)	0.010 (2)
C10	0.081 (4)	0.059 (3)	0.040 (3)	0.025 (3)	0.017 (3)	0.011 (3)
C11	0.058 (3)	0.040 (3)	0.066 (3)	0.009 (2)	0.032 (3)	0.017 (3)
C12	0.048 (3)	0.042 (3)	0.044 (3)	0.002 (2)	0.020 (2)	0.007 (2)
C13	0.029 (2)	0.024 (2)	0.0229 (19)	0.0037 (16)	0.0086 (15)	0.0099 (16)
C14	0.028 (2)	0.030 (2)	0.029 (2)	0.0055 (16)	0.0113 (16)	0.0165 (18)
C15	0.030 (2)	0.041 (3)	0.049 (3)	0.0018 (19)	0.0122 (19)	0.026 (2)
C16	0.030 (2)	0.058 (3)	0.075 (3)	0.008 (2)	0.007 (2)	0.045 (3)
C17	0.049 (3)	0.047 (3)	0.071 (3)	0.016 (2)	0.014 (2)	0.042 (3)
C18	0.043 (3)	0.030 (2)	0.042 (2)	0.0074 (18)	0.019 (2)	0.020 (2)
C19	0.030 (2)	0.030 (2)	0.037 (2)	0.0036 (17)	0.0137 (17)	0.0187 (19)
C20	0.056 (3)	0.029 (2)	0.042 (2)	0.006 (2)	0.021 (2)	0.021 (2)
C21	0.060 (3)	0.045 (3)	0.109 (5)	0.010 (2)	0.035 (3)	0.050 (3)
C22	0.059 (4)	0.055 (3)	0.120 (5)	0.005 (3)	0.038 (3)	0.049 (4)
C23	0.098 (5)	0.030 (3)	0.062 (3)	0.009 (3)	0.025 (3)	0.029 (3)
C24	0.065 (3)	0.041 (3)	0.063 (3)	0.008 (2)	0.013 (3)	0.032 (3)
C25	0.029 (2)	0.023 (2)	0.030 (2)	0.0040 (16)	0.0133 (16)	0.0118 (17)
C26	0.027 (2)	0.036 (2)	0.033 (2)	0.0048 (17)	0.0120 (17)	0.0170 (19)
C27	0.033 (2)	0.077 (4)	0.039 (3)	0.001 (2)	0.0142 (19)	0.032 (3)
C28	0.043 (3)	0.114 (5)	0.052 (3)	−0.002 (3)	0.018 (2)	0.051 (3)
C29	0.041 (3)	0.083 (4)	0.039 (3)	0.000 (3)	0.006 (2)	0.037 (3)
C30	0.032 (2)	0.040 (2)	0.035 (2)	0.0064 (18)	0.0105 (18)	0.018 (2)
C31	0.030 (2)	0.036 (2)	0.034 (2)	0.0053 (17)	0.0144 (17)	0.0166 (19)
C32	0.031 (2)	0.039 (2)	0.045 (3)	0.0075 (19)	0.0088 (19)	0.020 (2)
C33	0.031 (2)	0.063 (3)	0.056 (3)	0.008 (2)	0.011 (2)	0.030 (3)
C34	0.039 (3)	0.079 (4)	0.081 (4)	0.010 (3)	0.023 (3)	0.044 (3)
C35	0.046 (3)	0.095 (5)	0.063 (4)	−0.010 (3)	0.001 (3)	0.019 (3)
C36	0.045 (3)	0.089 (4)	0.045 (3)	0.004 (3)	0.012 (2)	0.023 (3)

Geometric parameters (Å, º)

Tb1—O4^i	2.275 (2)	C11—C12	1.392 (6)
Tb1—O6^ii	2.279 (2)	C11—H11	0.9300
Tb1—O5	2.380 (2)	C12—H12	0.9300
Tb1—O3	2.384 (2)	C13—C14	1.500 (5)
Tb1—O7	2.429 (2)	C14—C15	1.383 (5)
Tb1—O8	2.431 (3)	C14—C19	1.386 (5)
Tb1—O2	2.459 (2)	C15—C16	1.381 (6)
Tb1—O1	2.515 (3)	C15—H15	0.9300
Tb1—C1	2.858 (4)	C16—C17	1.396 (6)
O1—C1	1.265 (4)	C16—H16	0.9300
O2—C1	1.270 (4)	C17—C18	1.380 (6)
O3—C13	1.256 (4)	C17—H17	0.9300
O4—C13	1.258 (4)	C18—C19	1.390 (5)
O4—Tb1^i	2.275 (2)	C18—C20	1.492 (5)
O5—C25	1.255 (4)	C19—H19	0.9300
O6—C25	1.256 (4)	C20—C24	1.379 (6)
O6—Tb1^ii	2.279 (2)	C20—C21	1.379 (6)
O7—H7A	0.843 (10)	C21—C22	1.381 (6)
O7—H7B	0.849 (10)	C21—H21	0.9300
O8—H8A	0.844 (10)	C22—H22	0.9300
O8—H8B	0.847 (10)	C23—C24	1.379 (6)
N1—C10	1.311 (6)	C23—H23	0.9300
N1—C11	1.320 (6)	C24—H24	0.9300
N2—C22	1.321 (6)	C25—C26	1.504 (5)
N2—C23	1.331 (6)	C26—C31	1.386 (5)
N3—C35	1.329 (7)	C26—C27	1.390 (5)
N3—C34	1.337 (6)	C27—C28	1.378 (6)
C1—C2	1.495 (5)	C27—H27	0.9300
C2—C3	1.385 (5)	C28—C29	1.387 (6)
C2—C7	1.390 (5)	C28—H28	0.9300
C3—C4	1.390 (6)	C29—C30	1.393 (6)
C3—H3	0.9300	C29—H29	0.9300
C4—C5	1.372 (6)	C30—C31	1.388 (5)
C4—H4	0.9300	C30—C32	1.483 (5)
C5—C6	1.397 (6)	C31—H31	0.9300
C5—H5	0.9300	C32—C36	1.388 (6)
C6—C7	1.392 (5)	C32—C33	1.395 (6)
C6—C8	1.487 (5)	C33—C34	1.371 (6)
C7—H7	0.9300	C33—H33	0.9300
C8—C12	1.374 (6)	C34—H34	0.9300
C8—C9	1.377 (6)	C35—C36	1.384 (7)
C9—C10	1.388 (6)	C35—H35	0.9300
C9—H9	0.9300	C36—H36	0.9300
C10—H10	0.9300
O4^i—Tb1—O6^ii	158.37 (10)	N1—C10—C9	125.2 (5)
O4^i—Tb1—O5	82.29 (9)	N1—C10—H10	117.4
O6^ii—Tb1—O5	106.67 (9)	C9—C10—H10	117.4
O4^i—Tb1—O3	103.68 (9)	N1—C11—C12	123.3 (5)
O6^ii—Tb1—O3	81.17 (9)	N1—C11—H11	118.4
O5—Tb1—O3	143.14 (10)	C12—C11—H11	118.4
O4^i—Tb1—O7	89.52 (9)	C8—C12—C11	119.6 (4)
O6^ii—Tb1—O7	74.89 (9)	C8—C12—H12	120.2
O5—Tb1—O7	73.20 (10)	C11—C12—H12	120.2
O3—Tb1—O7	141.96 (10)	O3—C13—O4	123.3 (3)
O4^i—Tb1—O8	74.94 (10)	O3—C13—C14	118.9 (3)
O6^ii—Tb1—O8	85.97 (9)	O4—C13—C14	117.7 (3)
O5—Tb1—O8	138.71 (9)	C15—C14—C19	120.2 (3)
O3—Tb1—O8	76.63 (10)	C15—C14—C13	119.9 (3)
O7—Tb1—O8	72.64 (10)	C19—C14—C13	119.8 (3)
O4^i—Tb1—O2	125.46 (9)	C16—C15—C14	119.6 (4)
O6^ii—Tb1—O2	76.17 (9)	C16—C15—H15	120.2
O5—Tb1—O2	74.96 (9)	C14—C15—H15	120.2
O3—Tb1—O2	72.14 (9)	C15—C16—C17	119.6 (4)
O7—Tb1—O2	127.88 (9)	C15—C16—H16	120.2
O8—Tb1—O2	145.91 (10)	C17—C16—H16	120.2
O4^i—Tb1—O1	74.03 (9)	C18—C17—C16	121.5 (4)
O6^ii—Tb1—O1	126.95 (9)	C18—C17—H17	119.2
O5—Tb1—O1	75.06 (9)	C16—C17—H17	119.2
O3—Tb1—O1	71.96 (9)	C17—C18—C19	117.9 (4)
O7—Tb1—O1	145.87 (10)	C17—C18—C20	120.5 (3)
O8—Tb1—O1	128.34 (9)	C19—C18—C20	121.5 (4)
O2—Tb1—O1	52.53 (8)	C14—C19—C18	121.1 (4)
O4^i—Tb1—C1	99.78 (10)	C14—C19—H19	119.5
O6^ii—Tb1—C1	101.65 (10)	C18—C19—H19	119.5
O5—Tb1—C1	73.28 (10)	C24—C20—C21	115.2 (4)
O3—Tb1—C1	69.86 (10)	C24—C20—C18	121.9 (4)
O7—Tb1—C1	143.55 (11)	C21—C20—C18	122.9 (4)
O8—Tb1—C1	143.82 (10)	C20—C21—C22	120.0 (4)
O2—Tb1—C1	26.28 (9)	C20—C21—H21	120.0
O1—Tb1—C1	26.25 (9)	C22—C21—H21	120.0
C1—O1—Tb1	92.2 (2)	N2—C22—C21	125.1 (5)
C1—O2—Tb1	94.7 (2)	N2—C22—H22	117.5
C13—O3—Tb1	126.2 (2)	C21—C22—H22	117.5
C13—O4—Tb1^i	163.8 (2)	N2—C23—C24	124.0 (4)
C25—O5—Tb1	126.7 (2)	N2—C23—H23	118.0
C25—O6—Tb1^ii	175.8 (2)	C24—C23—H23	118.0
Tb1—O7—H7A	119 (2)	C23—C24—C20	120.8 (5)
Tb1—O7—H7B	133 (2)	C23—C24—H24	119.6
H7A—O7—H7B	107 (2)	C20—C24—H24	119.6
Tb1—O8—H8A	119 (2)	O6—C25—O5	123.5 (3)
Tb1—O8—H8B	135 (2)	O6—C25—C26	118.3 (3)
H8A—O8—H8B	105 (2)	O5—C25—C26	118.2 (3)
C10—N1—C11	116.3 (4)	C31—C26—C27	119.3 (4)
C22—N2—C23	114.8 (4)	C31—C26—C25	120.5 (3)
C35—N3—C34	114.8 (5)	C27—C26—C25	120.1 (3)
O1—C1—O2	120.6 (3)	C28—C27—C26	119.4 (4)
O1—C1—C2	120.3 (3)	C28—C27—H27	120.3
O2—C1—C2	119.1 (3)	C26—C27—H27	120.3
O1—C1—Tb1	61.54 (19)	C27—C28—C29	120.7 (4)
O2—C1—Tb1	59.05 (18)	C27—C28—H28	119.7
C2—C1—Tb1	178.0 (3)	C29—C28—H28	119.7
C3—C2—C7	119.1 (4)	C28—C29—C30	120.9 (4)
C3—C2—C1	119.9 (3)	C28—C29—H29	119.5
C7—C2—C1	120.9 (3)	C30—C29—H29	119.5
C2—C3—C4	120.0 (4)	C31—C30—C29	117.4 (4)
C2—C3—H3	120.0	C31—C30—C32	121.0 (4)
C4—C3—H3	120.0	C29—C30—C32	121.5 (4)
C5—C4—C3	120.6 (4)	C26—C31—C30	122.2 (4)
C5—C4—H4	119.7	C26—C31—H31	118.9
C3—C4—H4	119.7	C30—C31—H31	118.9
C4—C5—C6	120.3 (4)	C36—C32—C33	115.0 (4)
C4—C5—H5	119.8	C36—C32—C30	122.8 (4)
C6—C5—H5	119.8	C33—C32—C30	122.1 (4)
C7—C6—C5	118.6 (4)	C34—C33—C32	120.1 (5)
C7—C6—C8	121.5 (4)	C34—C33—H33	119.9
C5—C6—C8	119.9 (4)	C32—C33—H33	119.9
C2—C7—C6	121.2 (4)	N3—C34—C33	125.1 (5)
C2—C7—H7	119.4	N3—C34—H34	117.5
C6—C7—H7	119.4	C33—C34—H34	117.5
C12—C8—C9	117.5 (4)	N3—C35—C36	124.3 (5)
C12—C8—C6	122.6 (4)	N3—C35—H35	117.8
C9—C8—C6	119.9 (4)	C36—C35—H35	117.8
C8—C9—C10	118.1 (5)	C35—C36—C32	120.6 (5)
C8—C9—H9	121.0	C35—C36—H36	119.7
C10—C9—H9	121.0	C32—C36—H36	119.7

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O2^ii	0.84 (1)	1.95 (1)	2.786 (4)	174 (3)
O7—H7B···N2^iii	0.85 (1)	1.95 (1)	2.790 (4)	173 (4)
O8—H8A···O1^i	0.84 (1)	2.00 (1)	2.823 (4)	166 (4)
O8—H8B···N1^iv	0.85 (1)	1.94 (1)	2.773 (4)	168 (3)

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x, y+1, z; (iv) x, y+1, z+1.