Tetra-μ-benzoato-κ4O:O′;κ3O:O,O′;κ3O,O′:O′-bis­[(benzoato-κ2O,O′)(1,10-phenanthroline-κ2N,N′)terbium(III)] benzoic acid disolvate

Ooi, P.H.; Teoh, S.G.; Yeap, C.S.; Fun, H.-K.

doi:10.1107/S1600536810016788

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages m644-m645

https://doi.org/10.1107/S1600536810016788

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Tetra-μ-benzoato-κ⁴O:O′;κ³O:O,O′;κ³O,O′:O′-bis[(benzoato-κ²O,O′)(1,10-phenanthroline-κ²N,N′)terbium(III)] benzoic acid disolvate

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

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 28 April 2010; accepted 7 May 2010; online 15 May 2010)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.018
wR(F²) = 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

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)
Symmetry code: (i) -x+2, -y, -z+2.

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

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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016788/rz2444Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title complex, showing 20% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. The suffix A corresponds to the symmetry code [-x+2, -y, -z+2].
	Fig. 2. The crystal structure of the title complex, viewed along the a axis, showing four chains along a axis. The benzoic acid solvent molecules have been omitted for clarity. Intermolecular hydrogen bonds are shown as dashed lines.

Tetra-µ-benzoato-κ⁴O:O';κ³O:O,O'; κ³O,O':O'-bis[(benzoato-κ²O,O')(1,10- phenanthroline-κ²N,N')terbium(III)] benzoic acid disolvate top

Crystal data top

[Tb₂(C₇H₅O₂)₆(C₁₂H₈N₂)₂]·2C₇H₆O₂	Z = 1
M_r = 1649.14	F(000) = 824
Triclinic, P1	D_x = 1.619 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5264 (15) Å	Cell parameters from 9691 reflections
b = 12.719 (2) Å	θ = 4.5–40.3°
c = 15.061 (2) Å	µ = 2.15 mm⁻¹
α = 74.836 (6)°	T = 100 K
β = 78.345 (6)°	Block, colourless
γ = 76.242 (6)°	0.59 × 0.27 × 0.13 mm
V = 1691.7 (4) Å³

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	11944 independent reflections
Radiation source: fine-focus sealed tube	11553 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 32.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.364, T_max = 0.765	k = −19→19
71560 measured reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.0746P)² + 0.5014P] where P = (F_o² + 2F_c²)/3
11944 reflections	(Δ/σ)_max = 0.006
460 parameters	Δρ_max = 1.41 e Å⁻³
0 restraints	Δρ_min = −2.25 e Å⁻³

Crystal data top

[Tb₂(C₇H₅O₂)₆(C₁₂H₈N₂)₂]·2C₇H₆O₂	γ = 76.242 (6)°
M_r = 1649.14	V = 1691.7 (4) Å³
Triclinic, P1	Z = 1
a = 9.5264 (15) Å	Mo Kα radiation
b = 12.719 (2) Å	µ = 2.15 mm⁻¹
c = 15.061 (2) Å	T = 100 K
α = 74.836 (6)°	0.59 × 0.27 × 0.13 mm
β = 78.345 (6)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	11944 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	11553 reflections with I > 2σ(I)
T_min = 0.364, T_max = 0.765	R_int = 0.025
71560 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.20	Δρ_max = 1.41 e Å⁻³
11944 reflections	Δρ_min = −2.25 e Å⁻³
460 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Tb1	0.854736 (8)	0.139249 (6)	0.983123 (5)	0.00821 (4)
O1	0.81573 (17)	0.27589 (13)	0.83589 (10)	0.0136 (2)
O2	0.99273 (17)	0.28773 (13)	0.90388 (10)	0.0142 (3)
O3	0.71754 (17)	0.05736 (13)	1.12842 (10)	0.0151 (3)
O4	0.92371 (16)	−0.05516 (13)	1.09240 (10)	0.0125 (2)
O5	1.20586 (16)	−0.01538 (12)	1.08640 (10)	0.0125 (2)
O6	1.01879 (16)	0.13125 (12)	1.08315 (10)	0.0128 (2)
N1	0.57889 (18)	0.21253 (14)	0.97767 (12)	0.0117 (3)
N2	0.73763 (19)	0.29920 (14)	1.06183 (12)	0.0119 (3)
C1	0.5069 (2)	0.29323 (16)	1.02408 (13)	0.0118 (3)
C2	0.5018 (2)	0.17375 (17)	0.93360 (15)	0.0153 (3)
H2A	0.5502	0.1190	0.9015	0.018*
C3	0.3507 (2)	0.21131 (19)	0.93312 (16)	0.0179 (4)
H3A	0.3009	0.1819	0.9013	0.022*
C4	0.2774 (2)	0.29236 (18)	0.98047 (16)	0.0172 (4)
H4A	0.1775	0.3187	0.9808	0.021*
C5	0.3556 (2)	0.33437 (16)	1.02809 (14)	0.0143 (3)
C6	0.2861 (2)	0.4186 (2)	1.07950 (16)	0.0196 (4)
H6A	0.1858	0.4447	1.0830	0.024*
C7	0.3645 (3)	0.46038 (19)	1.12277 (16)	0.0190 (4)
H7A	0.3176	0.5152	1.1552	0.023*
C8	0.5192 (2)	0.42095 (17)	1.11911 (14)	0.0150 (3)
C9	0.6044 (3)	0.46323 (18)	1.16243 (15)	0.0180 (4)
H9A	0.5608	0.5164	1.1970	0.022*
C10	0.7530 (3)	0.42479 (18)	1.15290 (15)	0.0184 (4)
H10A	0.8116	0.4523	1.1802	0.022*
C11	0.8150 (3)	0.34356 (19)	1.10146 (15)	0.0160 (4)
H11A	0.9159	0.3193	1.0946	0.019*
C12	0.5909 (2)	0.33772 (16)	1.06979 (13)	0.0120 (3)
C13	0.9288 (2)	0.31535 (16)	0.83381 (13)	0.0117 (3)
C14	0.9857 (2)	0.39245 (16)	0.74819 (13)	0.0132 (3)
C15	0.8946 (2)	0.45653 (17)	0.68380 (14)	0.0154 (3)
H15A	0.7970	0.4505	0.6929	0.019*
C16	0.9508 (3)	0.52973 (19)	0.60562 (15)	0.0204 (4)
H16A	0.8900	0.5739	0.5633	0.024*
C17	1.0978 (3)	0.5369 (2)	0.59085 (16)	0.0234 (4)
H17A	1.1347	0.5859	0.5387	0.028*
C18	1.1888 (3)	0.4715 (2)	0.65327 (16)	0.0222 (4)
H18A	1.2873	0.4753	0.6425	0.027*
C19	1.1326 (2)	0.39948 (18)	0.73292 (15)	0.0165 (3)
H19A	1.1934	0.3563	0.7756	0.020*
C20	0.8169 (2)	−0.02502 (16)	1.15246 (13)	0.0113 (3)
C21	0.8118 (2)	−0.08378 (16)	1.25201 (13)	0.0119 (3)
C22	0.6784 (2)	−0.0938 (2)	1.30829 (15)	0.0180 (4)
H22A	0.5919	−0.0662	1.2831	0.022*
C23	0.6744 (3)	−0.1448 (2)	1.40201 (16)	0.0234 (4)
H23A	0.5852	−0.1519	1.4396	0.028*
C24	0.8026 (3)	−0.1851 (2)	1.43949 (16)	0.0232 (4)
H24A	0.7993	−0.2187	1.5024	0.028*
C25	0.9368 (3)	−0.1757 (2)	1.38402 (15)	0.0211 (4)
H25A	1.0230	−0.2035	1.4096	0.025*
C26	0.9411 (2)	−0.12441 (18)	1.28979 (14)	0.0156 (3)
H26A	1.0303	−0.1174	1.2523	0.019*
C27	1.1338 (2)	0.07212 (17)	1.11195 (13)	0.0114 (3)
C28	1.1887 (2)	0.11019 (17)	1.18255 (13)	0.0123 (3)
C29	1.3377 (2)	0.09517 (17)	1.18401 (13)	0.0133 (3)
H29A	1.4044	0.0546	1.1451	0.016*
C30	1.3869 (2)	0.1408 (2)	1.24357 (15)	0.0178 (4)
H30A	1.4866	0.1326	1.2431	0.021*
C31	1.2878 (3)	0.1983 (2)	1.30368 (18)	0.0250 (5)
H31A	1.3213	0.2286	1.3435	0.030*
C32	1.1377 (3)	0.2110 (3)	1.30473 (19)	0.0289 (5)
H32A	1.0712	0.2481	1.3462	0.035*
C33	1.0880 (2)	0.1681 (2)	1.24358 (16)	0.0198 (4)
H33A	0.9883	0.1778	1.2431	0.024*
O7	0.5748 (2)	0.39406 (17)	0.65710 (15)	0.0275 (4)
O8	0.7119 (2)	0.22746 (16)	0.70482 (13)	0.0232 (3)
H1O8	0.7180	0.2548	0.7472	0.035*
C34	0.6364 (2)	0.3025 (2)	0.64473 (16)	0.0182 (4)
C35	0.6377 (3)	0.2640 (2)	0.55910 (16)	0.0204 (4)
C36	0.7126 (3)	0.1611 (3)	0.5463 (2)	0.0314 (6)
H36A	0.7601	0.1113	0.5933	0.038*
C37	0.7172 (4)	0.1314 (4)	0.4626 (3)	0.0471 (10)
H37A	0.7685	0.0621	0.4536	0.056*
C38	0.6459 (4)	0.2047 (4)	0.3932 (2)	0.0448 (9)
H38A	0.6503	0.1851	0.3373	0.054*
C39	0.5691 (4)	0.3057 (3)	0.40607 (19)	0.0409 (9)
H39A	0.5201	0.3541	0.3592	0.049*
C40	0.5630 (4)	0.3373 (3)	0.48907 (18)	0.0290 (5)
H40B	0.5098	0.4063	0.4977	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.00733 (6)	0.00899 (6)	0.00856 (6)	−0.00089 (3)	−0.00166 (3)	−0.00267 (3)
O1	0.0125 (6)	0.0153 (6)	0.0137 (6)	−0.0053 (5)	−0.0031 (5)	−0.0015 (5)
O2	0.0145 (6)	0.0148 (6)	0.0135 (6)	−0.0041 (5)	−0.0041 (5)	−0.0012 (5)
O3	0.0120 (6)	0.0155 (6)	0.0137 (6)	0.0016 (5)	−0.0005 (5)	−0.0009 (5)
O4	0.0110 (6)	0.0155 (6)	0.0114 (5)	−0.0027 (5)	0.0005 (4)	−0.0052 (5)
O5	0.0111 (6)	0.0112 (6)	0.0162 (6)	−0.0001 (5)	−0.0036 (5)	−0.0056 (5)
O6	0.0123 (6)	0.0129 (6)	0.0140 (6)	0.0006 (5)	−0.0055 (5)	−0.0047 (5)
N1	0.0100 (6)	0.0117 (6)	0.0133 (6)	−0.0016 (5)	−0.0019 (5)	−0.0033 (5)
N2	0.0117 (7)	0.0103 (6)	0.0144 (7)	−0.0006 (5)	−0.0039 (5)	−0.0038 (5)
C1	0.0095 (7)	0.0115 (7)	0.0132 (7)	−0.0010 (6)	−0.0017 (6)	−0.0016 (6)
C2	0.0132 (8)	0.0156 (8)	0.0190 (8)	−0.0026 (7)	−0.0056 (7)	−0.0049 (6)
C3	0.0131 (8)	0.0191 (9)	0.0231 (9)	−0.0046 (7)	−0.0076 (7)	−0.0024 (7)
C4	0.0103 (8)	0.0156 (8)	0.0230 (9)	−0.0016 (7)	−0.0034 (7)	0.0001 (7)
C5	0.0098 (7)	0.0115 (7)	0.0182 (8)	0.0005 (6)	−0.0011 (6)	−0.0007 (6)
C6	0.0123 (8)	0.0211 (9)	0.0208 (9)	−0.0001 (7)	0.0028 (7)	−0.0034 (7)
C7	0.0172 (9)	0.0174 (9)	0.0183 (9)	0.0024 (7)	0.0025 (7)	−0.0059 (7)
C8	0.0160 (8)	0.0123 (8)	0.0141 (7)	0.0011 (6)	−0.0003 (6)	−0.0037 (6)
C9	0.0240 (10)	0.0142 (8)	0.0153 (8)	0.0009 (7)	−0.0027 (7)	−0.0071 (6)
C10	0.0236 (10)	0.0154 (8)	0.0187 (9)	−0.0010 (7)	−0.0066 (7)	−0.0082 (7)
C11	0.0162 (9)	0.0178 (9)	0.0173 (9)	−0.0042 (7)	−0.0051 (7)	−0.0070 (7)
C12	0.0114 (7)	0.0127 (7)	0.0113 (7)	−0.0019 (6)	−0.0001 (6)	−0.0032 (6)
C13	0.0114 (8)	0.0116 (7)	0.0126 (7)	−0.0021 (6)	−0.0021 (6)	−0.0032 (6)
C14	0.0159 (8)	0.0128 (7)	0.0111 (7)	−0.0048 (6)	−0.0003 (6)	−0.0028 (6)
C15	0.0190 (9)	0.0139 (8)	0.0127 (7)	−0.0019 (7)	−0.0023 (6)	−0.0031 (6)
C16	0.0290 (11)	0.0172 (9)	0.0133 (8)	−0.0050 (8)	−0.0025 (7)	−0.0007 (7)
C17	0.0335 (12)	0.0222 (10)	0.0147 (8)	−0.0130 (9)	0.0014 (8)	−0.0018 (7)
C18	0.0248 (11)	0.0269 (11)	0.0177 (9)	−0.0154 (9)	0.0022 (8)	−0.0046 (8)
C19	0.0173 (9)	0.0181 (9)	0.0159 (8)	−0.0072 (7)	−0.0013 (7)	−0.0046 (7)
C20	0.0098 (7)	0.0130 (7)	0.0110 (7)	−0.0032 (6)	−0.0006 (6)	−0.0024 (6)
C21	0.0120 (7)	0.0111 (7)	0.0113 (7)	−0.0016 (6)	−0.0006 (6)	−0.0017 (5)
C22	0.0144 (9)	0.0232 (10)	0.0148 (8)	−0.0069 (7)	−0.0003 (7)	0.0002 (7)
C23	0.0208 (10)	0.0307 (12)	0.0154 (9)	−0.0106 (9)	0.0016 (7)	0.0021 (8)
C24	0.0264 (11)	0.0269 (11)	0.0129 (8)	−0.0065 (9)	−0.0020 (8)	0.0020 (7)
C25	0.0204 (10)	0.0266 (11)	0.0147 (8)	−0.0022 (8)	−0.0061 (7)	−0.0014 (7)
C26	0.0146 (8)	0.0183 (9)	0.0133 (8)	−0.0021 (7)	−0.0025 (6)	−0.0033 (6)
C27	0.0111 (8)	0.0137 (8)	0.0107 (7)	−0.0038 (6)	−0.0019 (6)	−0.0037 (6)
C28	0.0118 (7)	0.0151 (8)	0.0118 (7)	−0.0025 (6)	−0.0027 (6)	−0.0055 (6)
C29	0.0122 (8)	0.0151 (8)	0.0141 (7)	−0.0018 (6)	−0.0033 (6)	−0.0053 (6)
C30	0.0156 (9)	0.0245 (10)	0.0174 (8)	−0.0053 (8)	−0.0049 (7)	−0.0086 (7)
C31	0.0202 (10)	0.0392 (13)	0.0236 (10)	−0.0056 (9)	−0.0043 (8)	−0.0201 (10)
C32	0.0206 (10)	0.0470 (16)	0.0279 (11)	−0.0046 (10)	−0.0008 (9)	−0.0278 (11)
C33	0.0130 (8)	0.0307 (11)	0.0194 (9)	−0.0010 (8)	−0.0019 (7)	−0.0149 (8)
O7	0.0284 (9)	0.0259 (9)	0.0323 (9)	0.0025 (7)	−0.0143 (8)	−0.0129 (7)
O8	0.0244 (8)	0.0232 (8)	0.0253 (8)	0.0009 (7)	−0.0132 (7)	−0.0091 (6)
C34	0.0146 (8)	0.0219 (9)	0.0198 (9)	−0.0035 (7)	−0.0049 (7)	−0.0061 (7)
C35	0.0173 (9)	0.0289 (11)	0.0193 (9)	−0.0096 (8)	−0.0028 (7)	−0.0084 (8)
C36	0.0209 (11)	0.0417 (15)	0.0413 (15)	−0.0014 (10)	−0.0090 (10)	−0.0269 (12)
C37	0.0299 (14)	0.073 (3)	0.057 (2)	−0.0113 (16)	−0.0017 (14)	−0.050 (2)
C38	0.0393 (17)	0.082 (3)	0.0297 (14)	−0.0327 (19)	0.0044 (12)	−0.0306 (16)
C39	0.057 (2)	0.061 (2)	0.0171 (10)	−0.0429 (19)	−0.0069 (11)	−0.0013 (11)
C40	0.0395 (14)	0.0340 (13)	0.0197 (10)	−0.0232 (12)	−0.0092 (9)	0.0011 (9)

Geometric parameters (Å, º) top

Tb1—O5ⁱ	2.3349 (14)	C15—H15A	0.9300
Tb1—O4ⁱ	2.3420 (15)	C16—C17	1.394 (4)
Tb1—O6	2.3490 (15)	C16—H16A	0.9300
Tb1—O3	2.4251 (15)	C17—C18	1.380 (4)
Tb1—O1	2.4669 (15)	C17—H17A	0.9300
Tb1—O2	2.4672 (15)	C18—C19	1.402 (3)
Tb1—N2	2.5370 (17)	C18—H18A	0.9300
Tb1—N1	2.5813 (18)	C19—H19A	0.9300
Tb1—O4	2.6057 (16)	C20—C21	1.487 (3)
Tb1—C13	2.8367 (19)	C21—C22	1.391 (3)
Tb1—C20	2.8633 (19)	C21—C26	1.391 (3)
Tb1—Tb1ⁱ	3.9280 (6)	C22—C23	1.388 (3)
O1—C13	1.284 (2)	C22—H22A	0.9300
O2—C13	1.254 (2)	C23—C24	1.379 (4)
O3—C20	1.262 (3)	C23—H23A	0.9300
O4—C20	1.274 (2)	C24—C25	1.391 (3)
O4—Tb1ⁱ	2.3420 (15)	C24—H24A	0.9300
O5—C27	1.269 (2)	C25—C26	1.395 (3)
O5—Tb1ⁱ	2.3348 (14)	C25—H25A	0.9300
O6—C27	1.259 (2)	C26—H26A	0.9300
N1—C2	1.328 (3)	C27—C28	1.501 (3)
N1—C1	1.364 (2)	C28—C29	1.390 (3)
N2—C11	1.330 (3)	C28—C33	1.404 (3)
N2—C12	1.358 (3)	C29—C30	1.390 (3)
C1—C5	1.406 (3)	C29—H29A	0.9300
C1—C12	1.441 (3)	C30—C31	1.385 (3)
C2—C3	1.406 (3)	C30—H30A	0.9300
C2—H2A	0.9300	C31—C32	1.398 (4)
C3—C4	1.378 (3)	C31—H31A	0.9300
C3—H3A	0.9300	C32—C33	1.389 (3)
C4—C5	1.401 (3)	C32—H32A	0.9300
C4—H4A	0.9300	C33—H33A	0.9300
C5—C6	1.440 (3)	O7—C34	1.217 (3)
C6—C7	1.353 (4)	O8—C34	1.316 (3)
C6—H6A	0.9300	O8—H1O8	0.8200
C7—C8	1.434 (3)	C34—C35	1.491 (3)
C7—H7A	0.9300	C35—C36	1.376 (4)
C8—C9	1.407 (3)	C35—C40	1.400 (4)
C8—C12	1.415 (3)	C36—C37	1.397 (4)
C9—C10	1.375 (3)	C36—H36A	0.9300
C9—H9A	0.9300	C37—C38	1.378 (7)
C10—C11	1.400 (3)	C37—H37A	0.9300
C10—H10A	0.9300	C38—C39	1.359 (6)
C11—H11A	0.9300	C38—H38A	0.9300
C13—C14	1.493 (3)	C39—C40	1.397 (4)
C14—C19	1.391 (3)	C39—H39A	0.9300
C14—C15	1.396 (3)	C40—H40B	0.9300
C15—C16	1.396 (3)

O5ⁱ—Tb1—O4ⁱ	74.50 (5)	C10—C9—C8	119.06 (19)
O5ⁱ—Tb1—O6	136.68 (5)	C10—C9—H9A	120.5
O4ⁱ—Tb1—O6	78.07 (5)	C8—C9—H9A	120.5
O5ⁱ—Tb1—O3	88.57 (5)	C9—C10—C11	119.1 (2)
O4ⁱ—Tb1—O3	126.68 (5)	C9—C10—H10A	120.5
O6—Tb1—O3	81.63 (5)	C11—C10—H10A	120.5
O5ⁱ—Tb1—O1	85.28 (5)	N2—C11—C10	123.6 (2)
O4ⁱ—Tb1—O1	89.11 (5)	N2—C11—H11A	118.2
O6—Tb1—O1	127.31 (5)	C10—C11—H11A	118.2
O3—Tb1—O1	140.33 (5)	N2—C12—C8	122.55 (18)
O5ⁱ—Tb1—O2	126.18 (5)	N2—C12—C1	118.12 (17)
O4ⁱ—Tb1—O2	73.03 (5)	C8—C12—C1	119.32 (18)
O6—Tb1—O2	74.65 (5)	O2—C13—O1	119.67 (18)
O3—Tb1—O2	145.10 (5)	O2—C13—C14	119.87 (18)
O1—Tb1—O2	52.80 (5)	O1—C13—C14	120.46 (18)
O5ⁱ—Tb1—N2	141.13 (5)	O2—C13—Tb1	60.23 (10)
O4ⁱ—Tb1—N2	143.06 (5)	O1—C13—Tb1	60.29 (10)
O6—Tb1—N2	76.18 (5)	C14—C13—Tb1	170.03 (14)
O3—Tb1—N2	74.81 (5)	C19—C14—C15	120.02 (18)
O1—Tb1—N2	85.87 (5)	C19—C14—C13	118.85 (18)
O2—Tb1—N2	74.91 (5)	C15—C14—C13	121.13 (18)
O5ⁱ—Tb1—N1	77.20 (5)	C16—C15—C14	119.5 (2)
O4ⁱ—Tb1—N1	145.78 (5)	C16—C15—H15A	120.2
O6—Tb1—N1	136.14 (5)	C14—C15—H15A	120.2
O3—Tb1—N1	70.78 (5)	C17—C16—C15	120.2 (2)
O1—Tb1—N1	69.64 (5)	C17—C16—H16A	119.9
O2—Tb1—N1	110.26 (5)	C15—C16—H16A	119.9
N2—Tb1—N1	64.24 (5)	C18—C17—C16	120.2 (2)
O5ⁱ—Tb1—O4	75.20 (5)	C18—C17—H17A	119.9
O4ⁱ—Tb1—O4	75.02 (5)	C16—C17—H17A	119.9
O6—Tb1—O4	65.64 (5)	C17—C18—C19	119.9 (2)
O3—Tb1—O4	51.71 (5)	C17—C18—H18A	120.0
O1—Tb1—O4	157.45 (5)	C19—C18—H18A	120.0
O2—Tb1—O4	133.00 (5)	C14—C19—C18	120.0 (2)
N2—Tb1—O4	116.44 (5)	C14—C19—H19A	120.0
N1—Tb1—O4	115.60 (5)	C18—C19—H19A	120.0
O5ⁱ—Tb1—C13	105.11 (6)	O3—C20—O4	120.25 (18)
O4ⁱ—Tb1—C13	77.50 (6)	O3—C20—C21	119.52 (17)
O6—Tb1—C13	100.82 (6)	O4—C20—C21	120.18 (18)
O3—Tb1—C13	155.23 (5)	O3—C20—Tb1	57.25 (10)
O1—Tb1—C13	26.87 (5)	O4—C20—Tb1	65.44 (10)
O2—Tb1—C13	26.18 (5)	C21—C20—Tb1	161.59 (13)
N2—Tb1—C13	81.81 (6)	C22—C21—C26	119.98 (18)
N1—Tb1—C13	91.87 (6)	C22—C21—C20	120.43 (18)
O4—Tb1—C13	151.34 (5)	C26—C21—C20	119.53 (17)
O5ⁱ—Tb1—C20	85.27 (6)	C23—C22—C21	120.0 (2)
O4ⁱ—Tb1—C20	101.22 (6)	C23—C22—H22A	120.0
O6—Tb1—C20	67.92 (5)	C21—C22—H22A	120.0
O3—Tb1—C20	25.96 (5)	C24—C23—C22	120.0 (2)
O1—Tb1—C20	163.59 (5)	C24—C23—H23A	120.0
O2—Tb1—C20	142.47 (5)	C22—C23—H23A	120.0
N2—Tb1—C20	93.14 (6)	C23—C24—C25	120.6 (2)
N1—Tb1—C20	95.17 (5)	C23—C24—H24A	119.7
O4—Tb1—C20	26.41 (5)	C25—C24—H24A	119.7
C13—Tb1—C20	168.56 (6)	C24—C25—C26	119.5 (2)
O5ⁱ—Tb1—Tb1ⁱ	70.80 (4)	C24—C25—H25A	120.3
O4ⁱ—Tb1—Tb1ⁱ	39.85 (4)	C26—C25—H25A	120.3
O6—Tb1—Tb1ⁱ	66.62 (4)	C21—C26—C25	119.9 (2)
O3—Tb1—Tb1ⁱ	86.85 (4)	C21—C26—H26A	120.0
O1—Tb1—Tb1ⁱ	127.12 (4)	C25—C26—H26A	120.0
O2—Tb1—Tb1ⁱ	106.16 (4)	O6—C27—O5	125.75 (18)
N2—Tb1—Tb1ⁱ	140.52 (4)	O6—C27—C28	116.05 (18)
N1—Tb1—Tb1ⁱ	141.23 (4)	O5—C27—C28	118.20 (18)
O4—Tb1—Tb1ⁱ	35.17 (3)	C29—C28—C33	119.88 (18)
C13—Tb1—Tb1ⁱ	116.94 (4)	C29—C28—C27	120.82 (17)
C20—Tb1—Tb1ⁱ	61.44 (4)	C33—C28—C27	119.16 (18)
C13—O1—Tb1	92.84 (12)	C30—C29—C28	120.00 (19)
C13—O2—Tb1	93.60 (12)	C30—C29—H29A	120.0
C20—O3—Tb1	96.79 (12)	C28—C29—H29A	120.0
C20—O4—Tb1ⁱ	164.95 (14)	C31—C30—C29	120.2 (2)
C20—O4—Tb1	88.14 (12)	C31—C30—H30A	119.9
Tb1ⁱ—O4—Tb1	104.98 (5)	C29—C30—H30A	119.9
C27—O5—Tb1ⁱ	132.94 (13)	C30—C31—C32	120.2 (2)
C27—O6—Tb1	141.05 (13)	C30—C31—H31A	119.9
C2—N1—C1	117.85 (18)	C32—C31—H31A	119.9
C2—N1—Tb1	123.32 (14)	C33—C32—C31	119.8 (2)
C1—N1—Tb1	118.81 (12)	C33—C32—H32A	120.1
C11—N2—C12	117.72 (18)	C31—C32—H32A	120.1
C11—N2—Tb1	121.72 (14)	C32—C33—C28	119.9 (2)
C12—N2—Tb1	120.44 (12)	C32—C33—H33A	120.1
N1—C1—C5	122.49 (18)	C28—C33—H33A	120.1
N1—C1—C12	118.00 (17)	C34—O8—H1O8	109.5
C5—C1—C12	119.50 (18)	O7—C34—O8	123.5 (2)
N1—C2—C3	123.3 (2)	O7—C34—C35	123.8 (2)
N1—C2—H2A	118.4	O8—C34—C35	112.7 (2)
C3—C2—H2A	118.4	C36—C35—C40	119.7 (2)
C4—C3—C2	119.08 (19)	C36—C35—C34	122.1 (2)
C4—C3—H3A	120.5	C40—C35—C34	118.2 (2)
C2—C3—H3A	120.5	C35—C36—C37	119.9 (3)
C3—C4—C5	118.96 (19)	C35—C36—H36A	120.1
C3—C4—H4A	120.5	C37—C36—H36A	120.1
C5—C4—H4A	120.5	C38—C37—C36	120.1 (4)
C4—C5—C1	118.35 (19)	C38—C37—H37A	120.0
C4—C5—C6	122.03 (19)	C36—C37—H37A	120.0
C1—C5—C6	119.62 (19)	C39—C38—C37	120.4 (3)
C7—C6—C5	121.1 (2)	C39—C38—H38A	119.8
C7—C6—H6A	119.5	C37—C38—H38A	119.8
C5—C6—H6A	119.5	C38—C39—C40	120.6 (3)
C6—C7—C8	120.6 (2)	C38—C39—H39A	119.7
C6—C7—H7A	119.7	C40—C39—H39A	119.7
C8—C7—H7A	119.7	C39—C40—C35	119.3 (3)
C9—C8—C12	117.9 (2)	C39—C40—H40B	120.4
C9—C8—C7	122.18 (19)	C35—C40—H40B	120.4
C12—C8—C7	119.9 (2)

O5ⁱ—Tb1—O1—C13	−137.88 (12)	C9—C10—C11—N2	−1.2 (3)
O4ⁱ—Tb1—O1—C13	−63.36 (12)	C11—N2—C12—C8	−0.9 (3)
O6—Tb1—O1—C13	10.87 (14)	Tb1—N2—C12—C8	175.14 (14)
O3—Tb1—O1—C13	140.10 (12)	C11—N2—C12—C1	177.66 (18)
O2—Tb1—O1—C13	5.85 (11)	Tb1—N2—C12—C1	−6.3 (2)
N2—Tb1—O1—C13	80.01 (12)	C9—C8—C12—N2	−1.1 (3)
N1—Tb1—O1—C13	144.03 (13)	C7—C8—C12—N2	178.23 (19)
O4—Tb1—O1—C13	−108.03 (15)	C9—C8—C12—C1	−179.56 (18)
C20—Tb1—O1—C13	167.10 (17)	C7—C8—C12—C1	−0.3 (3)
Tb1ⁱ—Tb1—O1—C13	−76.32 (12)	N1—C1—C12—N2	1.9 (3)
O5ⁱ—Tb1—O2—C13	40.92 (14)	C5—C1—C12—N2	−177.64 (18)
O4ⁱ—Tb1—O2—C13	96.20 (13)	N1—C1—C12—C8	−179.53 (18)
O6—Tb1—O2—C13	178.13 (13)	C5—C1—C12—C8	0.9 (3)
O3—Tb1—O2—C13	−132.94 (12)	Tb1—O2—C13—O1	10.6 (2)
O1—Tb1—O2—C13	−6.00 (11)	Tb1—O2—C13—C14	−168.50 (16)
N2—Tb1—O2—C13	−102.38 (13)	Tb1—O1—C13—O2	−10.6 (2)
N1—Tb1—O2—C13	−47.79 (13)	Tb1—O1—C13—C14	168.50 (16)
O4—Tb1—O2—C13	145.35 (11)	O5ⁱ—Tb1—C13—O2	−146.80 (12)
C20—Tb1—O2—C13	−177.43 (11)	O4ⁱ—Tb1—C13—O2	−76.88 (12)
Tb1ⁱ—Tb1—O2—C13	118.66 (12)	O6—Tb1—C13—O2	−1.83 (13)
O5ⁱ—Tb1—O3—C20	82.13 (13)	O3—Tb1—C13—O2	91.64 (17)
O4ⁱ—Tb1—O3—C20	12.74 (15)	O1—Tb1—C13—O2	169.4 (2)
O6—Tb1—O3—C20	−55.54 (12)	N2—Tb1—C13—O2	72.32 (12)
O1—Tb1—O3—C20	162.97 (11)	N1—Tb1—C13—O2	135.96 (12)
O2—Tb1—O3—C20	−102.83 (14)	O4—Tb1—C13—O2	−60.11 (17)
N2—Tb1—O3—C20	−133.41 (13)	C20—Tb1—C13—O2	7.9 (3)
N1—Tb1—O3—C20	159.07 (14)	Tb1ⁱ—Tb1—C13—O2	−70.97 (12)
O4—Tb1—O3—C20	9.94 (11)	O5ⁱ—Tb1—C13—O1	43.82 (12)
C13—Tb1—O3—C20	−153.24 (15)	O4ⁱ—Tb1—C13—O1	113.73 (12)
Tb1ⁱ—Tb1—O3—C20	11.28 (12)	O6—Tb1—C13—O1	−171.22 (11)
O5ⁱ—Tb1—O4—C20	−109.90 (12)	O3—Tb1—C13—O1	−77.75 (18)
O4ⁱ—Tb1—O4—C20	172.54 (14)	O2—Tb1—C13—O1	−169.4 (2)
O6—Tb1—O4—C20	89.07 (12)	N2—Tb1—C13—O1	−97.07 (12)
O3—Tb1—O4—C20	−9.78 (11)	N1—Tb1—C13—O1	−33.43 (12)
O1—Tb1—O4—C20	−140.77 (14)	O4—Tb1—C13—O1	130.51 (12)
O2—Tb1—O4—C20	124.05 (11)	C20—Tb1—C13—O1	−161.5 (2)
N2—Tb1—O4—C20	30.26 (13)	Tb1ⁱ—Tb1—C13—O1	119.65 (11)
N1—Tb1—O4—C20	−42.28 (12)	O2—C13—C14—C19	24.2 (3)
C13—Tb1—O4—C20	155.58 (14)	O1—C13—C14—C19	−154.9 (2)
Tb1ⁱ—Tb1—O4—C20	172.54 (14)	O2—C13—C14—C15	−156.1 (2)
O5ⁱ—Tb1—O4—Tb1ⁱ	77.56 (6)	O1—C13—C14—C15	24.8 (3)
O4ⁱ—Tb1—O4—Tb1ⁱ	0.0	C19—C14—C15—C16	−1.8 (3)
O6—Tb1—O4—Tb1ⁱ	−83.46 (6)	C13—C14—C15—C16	178.46 (19)
O3—Tb1—O4—Tb1ⁱ	177.68 (9)	C14—C15—C16—C17	1.5 (3)
O1—Tb1—O4—Tb1ⁱ	46.69 (15)	C15—C16—C17—C18	0.1 (4)
O2—Tb1—O4—Tb1ⁱ	−48.49 (8)	C16—C17—C18—C19	−1.4 (4)
N2—Tb1—O4—Tb1ⁱ	−142.27 (5)	C15—C14—C19—C18	0.5 (3)
N1—Tb1—O4—Tb1ⁱ	145.18 (5)	C13—C14—C19—C18	−179.75 (19)
C13—Tb1—O4—Tb1ⁱ	−16.96 (13)	C17—C18—C19—C14	1.1 (3)
C20—Tb1—O4—Tb1ⁱ	−172.54 (14)	Tb1—O3—C20—O4	−18.7 (2)
O5ⁱ—Tb1—O6—C27	19.0 (2)	Tb1—O3—C20—C21	158.78 (15)
O4ⁱ—Tb1—O6—C27	−32.5 (2)	Tb1ⁱ—O4—C20—O3	168.3 (4)
O3—Tb1—O6—C27	97.9 (2)	Tb1—O4—C20—O3	17.25 (19)
O1—Tb1—O6—C27	−112.1 (2)	Tb1ⁱ—O4—C20—C21	−9.1 (6)
O2—Tb1—O6—C27	−107.9 (2)	Tb1—O4—C20—C21	−160.22 (16)
N2—Tb1—O6—C27	174.2 (2)	Tb1ⁱ—O4—C20—Tb1	151.1 (5)
N1—Tb1—O6—C27	148.63 (19)	O5ⁱ—Tb1—C20—O3	−96.46 (13)
O4—Tb1—O6—C27	46.3 (2)	O4ⁱ—Tb1—C20—O3	−169.61 (12)
C13—Tb1—O6—C27	−107.1 (2)	O6—Tb1—C20—O3	118.32 (13)
C20—Tb1—O6—C27	75.0 (2)	O1—Tb1—C20—O3	−41.4 (3)
Tb1ⁱ—Tb1—O6—C27	7.7 (2)	O2—Tb1—C20—O3	113.70 (13)
O5ⁱ—Tb1—N1—C2	−7.84 (15)	N2—Tb1—C20—O3	44.60 (13)
O4ⁱ—Tb1—N1—C2	26.9 (2)	N1—Tb1—C20—O3	−19.80 (13)
O6—Tb1—N1—C2	−155.01 (14)	O4—Tb1—C20—O3	−162.27 (19)
O3—Tb1—N1—C2	−100.83 (16)	C13—Tb1—C20—O3	108.0 (3)
O1—Tb1—N1—C2	81.83 (16)	Tb1ⁱ—Tb1—C20—O3	−167.15 (14)
O2—Tb1—N1—C2	116.32 (16)	O5ⁱ—Tb1—C20—O4	65.81 (11)
N2—Tb1—N1—C2	177.22 (17)	O4ⁱ—Tb1—C20—O4	−7.35 (14)
O4—Tb1—N1—C2	−74.30 (16)	O6—Tb1—C20—O4	−79.41 (11)
C13—Tb1—N1—C2	97.24 (16)	O3—Tb1—C20—O4	162.27 (19)
C20—Tb1—N1—C2	−91.79 (16)	O1—Tb1—C20—O4	120.83 (19)
Tb1ⁱ—Tb1—N1—C2	−42.63 (18)	O2—Tb1—C20—O4	−84.03 (14)
O5ⁱ—Tb1—N1—C1	170.48 (14)	N2—Tb1—C20—O4	−153.13 (11)
O4ⁱ—Tb1—N1—C1	−154.75 (12)	N1—Tb1—C20—O4	142.47 (11)
O6—Tb1—N1—C1	23.32 (17)	C13—Tb1—C20—O4	−89.8 (3)
O3—Tb1—N1—C1	77.50 (14)	Tb1ⁱ—Tb1—C20—O4	−4.89 (9)
O1—Tb1—N1—C1	−99.84 (14)	O5ⁱ—Tb1—C20—C21	178.0 (4)
O2—Tb1—N1—C1	−65.36 (14)	O4ⁱ—Tb1—C20—C21	104.8 (4)
N2—Tb1—N1—C1	−4.46 (13)	O6—Tb1—C20—C21	32.8 (4)
O4—Tb1—N1—C1	104.02 (14)	O3—Tb1—C20—C21	−85.6 (4)
C13—Tb1—N1—C1	−84.44 (14)	O1—Tb1—C20—C21	−127.0 (4)
C20—Tb1—N1—C1	86.54 (14)	O2—Tb1—C20—C21	28.1 (5)
Tb1ⁱ—Tb1—N1—C1	135.70 (12)	N2—Tb1—C20—C21	−41.0 (4)
O5ⁱ—Tb1—N2—C11	173.53 (14)	N1—Tb1—C20—C21	−105.4 (4)
O4ⁱ—Tb1—N2—C11	−26.2 (2)	O4—Tb1—C20—C21	112.2 (5)
O6—Tb1—N2—C11	20.83 (16)	C13—Tb1—C20—C21	22.4 (6)
O3—Tb1—N2—C11	105.76 (16)	Tb1ⁱ—Tb1—C20—C21	107.3 (4)
O1—Tb1—N2—C11	−109.23 (16)	O3—C20—C21—C22	34.3 (3)
O2—Tb1—N2—C11	−56.70 (16)	O4—C20—C21—C22	−148.2 (2)
N1—Tb1—N2—C11	−178.59 (18)	Tb1—C20—C21—C22	108.8 (4)
O4—Tb1—N2—C11	74.21 (17)	O3—C20—C21—C26	−142.7 (2)
C13—Tb1—N2—C11	−82.50 (16)	O4—C20—C21—C26	34.8 (3)
C20—Tb1—N2—C11	87.18 (16)	Tb1—C20—C21—C26	−68.2 (5)
Tb1ⁱ—Tb1—N2—C11	40.54 (19)	C26—C21—C22—C23	−0.4 (3)
O5ⁱ—Tb1—N2—C12	−2.31 (19)	C20—C21—C22—C23	−177.4 (2)
O4ⁱ—Tb1—N2—C12	157.94 (13)	C21—C22—C23—C24	0.4 (4)
O6—Tb1—N2—C12	−155.01 (15)	C22—C23—C24—C25	−0.4 (4)
O3—Tb1—N2—C12	−70.09 (14)	C23—C24—C25—C26	0.5 (4)
O1—Tb1—N2—C12	74.93 (14)	C22—C21—C26—C25	0.4 (3)
O2—Tb1—N2—C12	127.46 (15)	C20—C21—C26—C25	177.4 (2)
N1—Tb1—N2—C12	5.57 (13)	C24—C25—C26—C21	−0.4 (4)
O4—Tb1—N2—C12	−101.64 (14)	Tb1—O6—C27—O5	2.0 (3)
C13—Tb1—N2—C12	101.65 (15)	Tb1—O6—C27—C28	−178.08 (14)
C20—Tb1—N2—C12	−88.66 (15)	Tb1ⁱ—O5—C27—O6	−20.6 (3)
Tb1ⁱ—Tb1—N2—C12	−135.30 (12)	Tb1ⁱ—O5—C27—C28	159.49 (13)
C2—N1—C1—C5	1.2 (3)	O6—C27—C28—C29	−145.65 (19)
Tb1—N1—C1—C5	−177.18 (14)	O5—C27—C28—C29	34.2 (3)
C2—N1—C1—C12	−178.29 (18)	O6—C27—C28—C33	30.1 (3)
Tb1—N1—C1—C12	3.3 (2)	O5—C27—C28—C33	−150.0 (2)
C1—N1—C2—C3	−0.4 (3)	C33—C28—C29—C30	−2.2 (3)
Tb1—N1—C2—C3	177.95 (16)	C27—C28—C29—C30	173.52 (19)
N1—C2—C3—C4	0.0 (3)	C28—C29—C30—C31	2.0 (3)
C2—C3—C4—C5	−0.4 (3)	C29—C30—C31—C32	−0.1 (4)
C3—C4—C5—C1	1.1 (3)	C30—C31—C32—C33	−1.6 (5)
C3—C4—C5—C6	−179.6 (2)	C31—C32—C33—C28	1.4 (4)
N1—C1—C5—C4	−1.6 (3)	C29—C28—C33—C32	0.5 (4)
C12—C1—C5—C4	177.89 (18)	C27—C28—C33—C32	−175.3 (2)
N1—C1—C5—C6	179.11 (19)	O7—C34—C35—C36	177.8 (3)
C12—C1—C5—C6	−1.4 (3)	O8—C34—C35—C36	−0.8 (3)
C4—C5—C6—C7	−178.0 (2)	O7—C34—C35—C40	−0.4 (4)
C1—C5—C6—C7	1.2 (3)	O8—C34—C35—C40	−179.0 (2)
C5—C6—C7—C8	−0.5 (3)	C40—C35—C36—C37	1.8 (4)
C6—C7—C8—C9	179.3 (2)	C34—C35—C36—C37	−176.4 (3)
C6—C7—C8—C12	0.1 (3)	C35—C36—C37—C38	−0.6 (5)
C12—C8—C9—C10	1.9 (3)	C36—C37—C38—C39	−0.8 (5)
C7—C8—C9—C10	−177.4 (2)	C37—C38—C39—C40	0.9 (5)
C8—C9—C10—C11	−0.9 (3)	C38—C39—C40—C35	0.3 (4)
C12—N2—C11—C10	2.0 (3)	C36—C35—C40—C39	−1.7 (4)
Tb1—N2—C11—C10	−173.94 (17)	C34—C35—C40—C39	176.5 (2)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is 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

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

Experimental details

Crystal data
Chemical formula	[Tb₂(C₇H₅O₂)₆(C₁₂H₈N₂)₂]·2C₇H₆O₂
M_r	1649.14
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.5264 (15), 12.719 (2), 15.061 (2)
α, β, γ (°)	74.836 (6), 78.345 (6), 76.242 (6)
V (Å³)	1691.7 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.15
Crystal size (mm)	0.59 × 0.27 × 0.13

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.364, 0.765
No. of measured, independent and observed [I > 2σ(I)] reflections	71560, 11944, 11553
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.101, 1.20
No. of reflections	11944
No. of parameters	460
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.41, −2.25

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

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

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is centroid of the C35–C40 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O8···O1	0.8200	1.8800	2.640 (3)	154
C2—H2A···O5ⁱ	0.9300	2.4000	3.036 (3)	125
C4—H4A···O2ⁱⁱ	0.9300	2.4500	3.172 (3)	135
C11—H11A···O6	0.9300	2.4000	2.969 (3)	120
C15—H15A···O7	0.9300	2.5800	3.448 (3)	155
C23—H23A···Cg1ⁱⁱⁱ	0.9300	2.5700	3.462 (3)	160

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

Footnotes

‡Additional correspondence author, e-mail: howieooi83@gmail.com.

§Thomson Reuters ResearcherID: A-5523-2009.

¶Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

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.

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