The twinned crystal structure of μ-2,2′-bipyrimidine-1κ²N¹,N^1′:2κ²N³,N^3′-bis­{tris­[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato-κ²O,O′]terbium(III)} ethyl acetate solvate

The title compound, [Tb₂(C₂₄H₁₂F₉O₆S₃)₂(C₈H₆N₄)]·C₄H₈O₂, has two terbium(III) centers bridged by the polyazine ligand 2,2′-bipyrimidine (bpm), which is distorted from planarity by 7.0 (2)°. The terminal ligand 4,4,4-trifluoro-1-(2-thienyl)­butane-1,3-dione (tta) is bidentate, coordinating through the two O atoms, while the bridging ligand is bis-bidentate, coordinating through four equivalent N atoms. Both the complex and the ethyl acetate solvent mol­ecules are dis­ordered. The structure was refined as a non-merohedral twin.

S1. Comment

Terbium(III) ions and their complexes have been extensively used as probes for proteins and nucleic acids due, in part, to their long-lived (millisecond) excited-state lifetimes (Fu et al., 1999; Klakamp & Horrocks, 1990). β-Diketonates are used as antenna ligands to overcome the forbidden 4f–4f transitions of lanthanide metals, thereby increasing the emission intensity of these complexes. Bridging ligands such as 2,2'-bipyrimidine (bpm) have been primarily used to link transition metals through coordination by equivalent N atoms (Balzani et al., 1996). Heteronuclear bimetallic lanthanide/transition metal complexes bridged by bpm have been synthesized and structurally characterized (Shavaleev et al., 2005). In these mixed-metal complexes, the planarity of the bpm bridging ligand is maintained and electronic communication between the two metal centers is observed. Examples of homodinuclear lanthanide complexes bridged by bpm are sparse (Sultan et al., 2006). We present here the title compound, (I), i the first structural report of a homodinuclear Tb^III complex bridged by the polyazine ligand bpm.

The molecular structure of (I) is illustrated in Fig. 1. Each Tb^III ion is eight-coordinate and the complex is neutral. Lanthanide(III) complexes, and particularly Tb^III complexes, are very often eight-coordinate due to the large ionic radius of the metal. The coordination sphere around each Tb^III ion consists of six O atoms from three 4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dione (tta) ligands and two N atoms from the bpm ligand. Selected bond lengths and angles are given in Table 1. Both Tb centers are in a distorted square-antiprismatic geometry, a coordination geometry previously reported in heteronuclear bimetallic lanthanide/transition metal complexes bridged by bpm (Shavaleev et al., 2005). The approximate square planes at the Tb1 center are comprised of atoms O5, O6, N1 and N4, where the average deviation of these atoms from the mean plane is 0.306 (2) Å, and atoms O1, O2, O3 and O4, where the average deviation of these atoms from the mean plane is 0.300 (2) Å. The corresponding approximate square planes at Tb2 are comprised of atoms O9, O10, N2 and N3, with an average deviation of 0.131 (2) Å, and atoms O7, O8, O11 and O12, with an average deviation of 0.045 (2) Å (Fig. 1). These mean planes at the metal centers are nearly orthogonal, with a dihedral angle of 83.24(0.06)° at Tb1, while the corresponding value at Tb2 is 89.87 (7)°.

The intramolecular Tb1···Tb2 distance across the bridging bpm ligand is 6.7596 (5) Å. The only other relevant Ln^III···Ln^III distance documented to date is in the Eu^III···Eu^III bipyrimidine-bridged complex reported by Fernandes et al. (2005), which has a metal–metal distance of 6.856 (1) Å. The longer distance in the Eu^III complex is consistent with the larger ionic radius of Eu^III compared with Tb^III, due to lanthanide contraction.

The individual bpm rings are planar, with a mean deviation of 0.003 (3) Å for atoms N1, C1, C2, C3, N2 and C4, and of 0.007 (3) Å for atoms N4, C5, N3, C6, C7 and C8; they are rotated from planarity by 7.0 (2)°. In lanthanide–transition metal complexes bridged by bipyrimidine, the bridging ligand is planar (Shavaleev et al., 2005). The unusual non-planarity observed in this complex is due most likely to the steric crowding of the bulky Tb^III ions forcing a slight torsional twist of the bridging ligand.

Part of both the solvate and the complex are positionally disordered, as described in the Experimental section. Atom O13 of the solvate interacts weakly with the π system of the bpm ligand, based on the close O13···C4 and O13···C5 distances of 2.909 (7) and 2.799 (7) Å, respectively.

S2. Experimental

Synthesis of the Tb^III complex was accomplished as described previously by Sultan et al. (2006), by mixing the appropriate stoichiometries of an aqueous solution of TbCl₃ with a basic ethanolic solution containing bpm and tta. X-ray quality crystals were obtained by diffusion of hexanes into an ethyl acetate solution of the Tb^III complex, (I), at room temperature.

S3. Refinement

The refinement of the structure was complicated by twinning. The structure was identified as a non-merohedral twin using RLATT (Bruker, 1998). Two p4p files were written (GEMINI; Bruker, 2000) and combined into one twinp4p file that could be read by SAINT (Bruker, 2003). SAINT integrates with both orientation matrices and separates the twin components. Corrections for absorption and decay were applied using TWINABS. The twinning law is a 180° rotation about (001). The final refinements were performed with all unique reflections using HKLF 5 format in SHELXTL (Sheldrick, 2003). A partial structure solution was obtained by direct methods and the remaining non-H atoms were located with difference Fourier techniques. Two thiophene rings of the six tta ligands show positional disorder, which can be described as 180° rotations about the C—C bonds C27—C28 and C35—C36. The occupancies refined to 0.80:0.20 for the ring S3/C28–C31 and 0.50:0.50 for the ring S4/C36–C39. Concomitantly, we find atoms of different elements (S and C) sharing almost the same site. SADI and EADP constraints were used to achieve a stable refinement for this disorder. Furthermore, four out of six tta-CF₃ groups could be modeled as disordered groups. The refined model contained two or three positions for each of the F atoms with the following occupancies: F7/F8/F9 0.50:0.25:0.25; F10/F11/F12 0.55:0.45; F13/F14/F15 0.50:0.25:0.25; and F16/F17/F18 0.55:0.45. One SADI constraint was required for a stable refinement (C40—F10A and C40—F10B). Additionally, the ethyl acetate solvate molecule exhibits a 0.70:0.30 disorder of the terminal methyl group.

All non-disordered non-H atoms were refined with anisotropic atomic displacement parameters and disordered atoms were refined isotropically. The H atoms were calculated in idealized positions, with C—H distances in the range 0.95–0.99 Å, and included in the refinement as restrained atoms with appropriate occupancies, with U_iso(H) = 1.2U_eq(C). [Please check added text]

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme for a single component of the disordered structure. For clarity, C and F atoms have not been labeled. Displacement ellipsoids are drawn at the 20% probability level for C and F, and 50% for all others. H atoms and the solvate molecule have been omitted for clarity. Fig. 2. Please provide caption.

µ-2,2'-bipyrimidine-1κ²N¹,N1'^:2κ2^N3^,N3'^{- bis{tris[4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dionato-κ}2^{O,O']terbium(III)} ethyl acetate solvate}

Crystal data

[Tb2(C24H12F9O6S3)2(C8H6N4)]·C4H8O2	F(000) = 1852
Mr = 1891.14	Dx = 1.806 Mg m^−3
Triclinic, P1	Melting point = 536–538 K
a = 10.0301 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.1408 (11) Å	Cell parameters from 4046 reflections
c = 24.9919 (9) Å	θ = 2.3–27.9°
α = 85.820 (2)°	µ = 2.31 mm^−1
β = 86.556 (2)°	T = 140 K
γ = 80.066 (2)°	Columnar, pale-yellow
V = 3478.2 (4) Å^3	0.38 × 0.12 × 0.10 mm
Z = 2

Data collection

Bruker SMART 6000 CCD area-detector diffractometer	23700 independent reflections
Radiation source: fine-focus sealed tube	23095 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
ω scans	θmax = 27.9°, θmin = 0.8°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2002; Blessing, 1995)	h = −13→13
Tmin = 0.62, Tmax = 0.79	k = −17→17
23700 measured reflections	l = 0→32

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0577P)^2 + 15.0158P] where P = (Fo^2 + 2Fc^2)/3
23700 reflections	(Δ/σ)max = 0.003
944 parameters	Δρmax = 2.01 e Å^−3
4 restraints	Δρmin = −0.97 e Å^−3

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.

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 > σ(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	Occ. (<1)
Tb1	0.72239 (2)	1.233100 (16)	0.656112 (9)	0.01852 (6)
Tb2	1.05073 (2)	0.889387 (16)	0.826229 (9)	0.01908 (6)
S1	0.95900 (15)	1.47143 (12)	0.73977 (8)	0.0419 (4)
S2	1.08648 (13)	0.96614 (10)	0.59354 (7)	0.0320 (3)
S3A	0.3863 (2)	1.52036 (14)	0.58724 (8)	0.0327 (4)*	0.80
C29A	0.5605 (9)	1.6057 (6)	0.5332 (4)	0.031 (2)*	0.80
H29A	0.6436	1.6209	0.5176	0.038*	0.80
S3B	0.5872 (9)	1.6196 (7)	0.5264 (4)	0.038 (2)*	0.20
C29B	0.4144 (16)	1.5470 (18)	0.5871 (9)	0.031 (2)*	0.20
H29B	0.3787	1.5176	0.6189	0.038*	0.20
S4A	0.7046 (3)	1.0476 (3)	0.95515 (14)	0.0270 (8)*	0.50
C37A	0.8487 (19)	1.1577 (13)	1.0028 (8)	0.028 (3)*	0.50
H37A	0.9219	1.1834	1.0152	0.034*	0.50
S4B	0.8630 (6)	1.1703 (4)	1.0019 (3)	0.0491 (15)*	0.50
C37B	0.7094 (14)	1.0724 (10)	0.9550 (6)	0.028 (3)*	0.50
H37B	0.6764	1.0369	0.9293	0.034*	0.50
S5	1.41821 (17)	0.61028 (12)	0.87158 (8)	0.0467 (4)
S6	0.78335 (15)	0.80783 (13)	0.67773 (6)	0.0389 (3)
O2	0.7778 (3)	1.3522 (2)	0.70639 (15)	0.0231 (7)
O1	0.5322 (3)	1.2854 (2)	0.71083 (15)	0.0240 (7)
O3	0.5654 (4)	1.1623 (3)	0.61674 (16)	0.0294 (8)
O4	0.8396 (3)	1.0963 (2)	0.61590 (15)	0.0240 (7)
O5	0.8910 (3)	1.2904 (2)	0.60195 (15)	0.0250 (8)
O6	0.6173 (3)	1.3698 (2)	0.60740 (15)	0.0256 (8)
O8	0.9446 (4)	0.9803 (3)	0.89452 (15)	0.0271 (8)
O7	1.2104 (3)	0.9679 (3)	0.86062 (15)	0.0270 (8)
O10	1.1703 (4)	0.7444 (3)	0.86192 (16)	0.0301 (8)
O9	0.8953 (4)	0.8006 (2)	0.87069 (15)	0.0258 (8)
O12	0.9863 (4)	0.8247 (3)	0.75161 (15)	0.0267 (8)
O11	1.2443 (3)	0.8548 (3)	0.76883 (15)	0.0260 (8)
O14	0.7931 (6)	0.3256 (3)	0.8748 (2)	0.0549 (13)
O13	0.8399 (7)	0.1950 (4)	0.8284 (2)	0.0733 (17)
N1	0.7052 (4)	1.0935 (3)	0.72767 (17)	0.0202 (8)
N4	0.9361 (4)	1.1662 (3)	0.70751 (17)	0.0201 (8)
N2	0.8170 (4)	0.9786 (3)	0.79154 (17)	0.0205 (8)
N3	1.0528 (4)	1.0402 (3)	0.76405 (16)	0.0199 (8)
C1	0.5902 (5)	1.0598 (4)	0.7403 (2)	0.0259 (11)
H1	0.5112	1.0881	0.7221	0.031*
C2	0.5812 (5)	0.9861 (4)	0.7785 (2)	0.0276 (11)
H2	0.4981	0.9635	0.7871	0.033*
C3	0.6982 (5)	0.9463 (4)	0.8040 (2)	0.0237 (10)
H3	0.6956	0.8952	0.8308	0.028*
C4	0.8138 (4)	1.0506 (3)	0.75443 (19)	0.0177 (9)
C5	0.9424 (5)	1.0878 (3)	0.74077 (19)	0.0190 (9)
C6	1.1683 (5)	1.0755 (4)	0.7524 (2)	0.0242 (10)
H6	1.2499	1.0431	0.7674	0.029*
C7	1.1714 (5)	1.1575 (4)	0.7192 (2)	0.0268 (11)
H7	1.2527	1.1828	0.7117	0.032*
C8	1.0522 (5)	1.2008 (4)	0.6978 (2)	0.0257 (11)
H8	1.0515	1.2578	0.6751	0.031*
C9	0.4931 (5)	1.3686 (4)	0.7289 (2)	0.0252 (11)
C10	0.5671 (5)	1.4368 (4)	0.7379 (2)	0.0286 (11)
H10	0.5214	1.4960	0.7507	0.034*
C11	0.7105 (5)	1.4235 (3)	0.7290 (2)	0.0228 (10)
C12	0.7866 (5)	1.4929 (4)	0.7487 (2)	0.0243 (10)
C13	0.7375 (5)	1.5779 (3)	0.7770 (2)	0.0205 (10)
H13	0.6458	1.6014	0.7874	0.025*
C14	0.8531 (7)	1.6206 (4)	0.7867 (3)	0.0392 (14)
H14	0.8451	1.6794	0.8037	0.047*
C15	0.9737 (6)	1.5710 (4)	0.7700 (3)	0.0385 (14)
H15	1.0580	1.5905	0.7748	0.046*
C16	0.3398 (6)	1.3873 (4)	0.7439 (3)	0.0417 (16)
C17	0.5714 (5)	1.0875 (4)	0.5912 (2)	0.0256 (11)
C18	0.6805 (5)	1.0228 (4)	0.5757 (2)	0.0279 (11)
H18	0.6673	0.9708	0.5557	0.033*
C19	0.8145 (5)	1.0310 (3)	0.5885 (2)	0.0216 (10)
C20	0.9301 (5)	0.9616 (3)	0.5695 (2)	0.0238 (10)
C21	0.9383 (5)	0.8926 (3)	0.5313 (2)	0.0261 (11)
H21	0.8635	0.8792	0.5133	0.031*
C22	1.0740 (6)	0.8457 (4)	0.5235 (3)	0.0353 (13)
H22	1.1002	0.7967	0.4990	0.042*
C23	1.1629 (6)	0.8765 (4)	0.5539 (3)	0.0358 (14)
H23	1.2571	0.8513	0.5533	0.043*
C24	0.4308 (6)	1.0719 (5)	0.5765 (3)	0.0394 (15)
C25	0.8971 (5)	1.3751 (4)	0.5810 (2)	0.0259 (11)
C26	0.7944 (5)	1.4485 (4)	0.5706 (2)	0.0329 (13)
H26	0.8160	1.5072	0.5545	0.040*
C27	0.6565 (5)	1.4420 (4)	0.5825 (2)	0.0275 (11)
C28	0.5508 (5)	1.5229 (4)	0.5667 (2)	0.0266 (11)
C30	0.4296 (6)	1.6656 (4)	0.5249 (3)	0.0403 (14)
H30	0.4134	1.7245	0.5035	0.048*
C31	0.3356 (7)	1.6230 (5)	0.5529 (3)	0.0436 (15)
H31	0.2424	1.6511	0.5529	0.052*
C32	1.0433 (6)	1.3897 (5)	0.5661 (2)	0.0340 (13)
C33	1.2040 (5)	1.0310 (4)	0.8943 (2)	0.0288 (11)
C34	1.0964 (5)	1.0699 (4)	0.9266 (2)	0.0290 (12)
H34	1.1085	1.1164	0.9507	0.035*
C35	0.9679 (5)	1.0424 (4)	0.9250 (2)	0.0253 (11)
C36	0.8533 (5)	1.0868 (4)	0.9589 (2)	0.0271 (11)
C38	0.6287 (6)	1.1239 (5)	0.9987 (2)	0.0419 (16)
H38	0.5342	1.1298	1.0074	0.050*
C39	0.7049 (7)	1.1770 (5)	1.0214 (3)	0.0472 (16)
H39	0.6700	1.2226	1.0470	0.057*
C40	1.3370 (6)	1.0714 (5)	0.8945 (3)	0.0410 (15)
C41	0.9057 (6)	0.7298 (4)	0.9049 (2)	0.0286 (11)
C42	1.0204 (6)	0.6666 (4)	0.9186 (2)	0.0291 (12)
H42	1.0136	0.6162	0.9454	0.035*
C43	1.1492 (5)	0.6754 (4)	0.8934 (2)	0.0254 (11)
C44	1.2669 (6)	0.6010 (4)	0.9052 (2)	0.0310 (12)
C45	1.2785 (6)	0.5188 (4)	0.9429 (3)	0.0394 (14)
H45	1.2071	0.5005	0.9659	0.047*
C46	1.4135 (8)	0.4697 (5)	0.9402 (4)	0.058 (2)
H46	1.4432	0.4130	0.9620	0.070*
C47	1.4978 (7)	0.5093 (5)	0.9042 (3)	0.0519 (18)
H47	1.5909	0.4834	0.8980	0.062*
C48	0.7729 (6)	0.7166 (5)	0.9340 (3)	0.0405 (14)
C49	1.2709 (5)	0.7996 (4)	0.7305 (2)	0.0299 (12)
C50	1.1832 (5)	0.7595 (4)	0.7028 (2)	0.0321 (12)
H50	1.2194	0.7153	0.6766	0.039*
C51	1.0419 (5)	0.7809 (4)	0.7116 (2)	0.0250 (10)
C52	0.9511 (6)	0.7552 (4)	0.6738 (2)	0.0320 (12)
C53	0.9789 (7)	0.6929 (5)	0.6314 (3)	0.0434 (16)
H53	1.0651	0.6569	0.6220	0.052*
C54	0.8563 (8)	0.6927 (6)	0.6047 (3)	0.0512 (19)
H54	0.8529	0.6551	0.5749	0.061*
C55	0.7477 (7)	0.7492 (6)	0.6248 (3)	0.0495 (18)
H55	0.6600	0.7560	0.6111	0.059*
C56	1.4202 (6)	0.7822 (5)	0.7123 (3)	0.0399 (14)
C57	0.6099 (9)	0.2547 (7)	0.8550 (4)	0.075 (3)
H57A	0.5889	0.2008	0.8364	0.112*
H57B	0.5625	0.3154	0.8387	0.112*
H57C	0.5804	0.2483	0.8930	0.112*
C58	0.7576 (9)	0.2543 (5)	0.8504 (3)	0.0518 (18)
C59A	0.9347 (10)	0.3294 (6)	0.8742 (4)	0.072 (2)
H59A	0.9709	0.3436	0.8373	0.093*	0.70
H59B	0.9863	0.2679	0.8890	0.093*	0.70
C60A	0.9417 (16)	0.4120 (10)	0.9104 (6)	0.079 (4)*	0.70
H60A	0.8544	0.4290	0.9301	0.119*	0.70
H60B	0.9623	0.4681	0.8882	0.119*	0.70
H60C	1.0130	0.3912	0.9360	0.119*	0.70
H59C	0.9641	0.3259	0.8358	0.093*	0.30
H59D	0.9742	0.2665	0.8916	0.093*	0.30
C60B	1.017 (4)	0.398 (3)	0.8941 (16)	0.087 (11)*	0.30
H60D	1.1078	0.3873	0.8768	0.131*	0.30
H60E	1.0229	0.3872	0.9332	0.131*	0.30
H60F	0.9725	0.4643	0.8854	0.131*	0.30
F1	0.3071 (4)	1.3234 (4)	0.78192 (19)	0.0658 (13)
F2	0.2694 (4)	1.3763 (3)	0.70222 (19)	0.0559 (11)
F3	0.2961 (4)	1.4737 (3)	0.7602 (3)	0.092 (2)
F4	0.3779 (4)	1.1381 (3)	0.5394 (2)	0.0737 (15)
F5	0.3464 (4)	1.0757 (4)	0.6198 (2)	0.0742 (16)
F6	0.4293 (4)	0.9875 (3)	0.55660 (18)	0.0552 (11)
F7A	1.0971 (11)	1.3518 (8)	0.5269 (5)	0.040 (3)*	0.50
F8A	1.0516 (11)	1.4856 (8)	0.5526 (5)	0.028 (3)*	0.50
F9A	1.1244 (9)	1.3632 (8)	0.6073 (4)	0.023 (2)*	0.50
F7B	1.0783 (18)	1.3434 (14)	0.5162 (7)	0.030 (4)*	0.25
F8B	1.054 (2)	1.4909 (15)	0.5648 (8)	0.035 (6)*	0.25
F9B	1.1311 (16)	1.3377 (12)	0.5971 (7)	0.033 (5)*	0.25
F7C	1.1111 (15)	1.3114 (11)	0.5329 (6)	0.031 (3)*	0.25
F8C	1.0674 (15)	1.4598 (11)	0.5391 (6)	0.032 (4)*	0.25
F9C	1.1076 (16)	1.3877 (12)	0.6141 (7)	0.028 (5)*	0.25
F10A	1.4441 (8)	1.0158 (7)	0.8984 (4)	0.044 (3)*	0.55
F11A	1.3289 (7)	1.1448 (5)	0.9294 (3)	0.0359 (16)*	0.55
F12A	1.3647 (9)	1.1145 (6)	0.8480 (3)	0.036 (2)*	0.55
F10B	1.4467 (8)	0.9898 (7)	0.8964 (4)	0.032 (2)*	0.45
F11B	1.3529 (8)	1.1101 (6)	0.9398 (3)	0.0323 (18)*	0.45
F12B	1.3372 (11)	1.1372 (8)	0.8485 (4)	0.039 (3)*	0.45
F13A	0.6715 (8)	0.7269 (7)	0.8962 (3)	0.0380 (18)*	0.50
F14A	0.7723 (8)	0.6309 (6)	0.9596 (4)	0.0412 (18)*	0.50
F15A	0.7351 (9)	0.7853 (7)	0.9686 (4)	0.0447 (19)*	0.50
F13B	0.6619 (17)	0.7584 (13)	0.9140 (8)	0.047 (4)*	0.25
F14B	0.7547 (14)	0.6186 (10)	0.9379 (7)	0.033 (3)*	0.25
F15B	0.7652 (19)	0.7401 (16)	0.9849 (8)	0.060 (5)*	0.25
F13C	0.6989 (17)	0.7978 (11)	0.9486 (7)	0.042 (4)*	0.25
F15C	0.7860 (16)	0.6605 (13)	0.9809 (7)	0.047 (4)*	0.25
F14C	0.699 (2)	0.6818 (15)	0.9067 (8)	0.061 (5)*	0.25
F16A	1.4611 (7)	0.6971 (5)	0.6910 (3)	0.0409 (17)*	0.55
F17A	1.4537 (9)	0.8504 (6)	0.6812 (4)	0.044 (2)*	0.55
F18A	1.5006 (7)	0.7747 (6)	0.7586 (3)	0.0324 (18)*	0.55
F16B	1.4517 (9)	0.7237 (7)	0.6711 (4)	0.046 (2)*	0.45
F17B	1.4550 (10)	0.8720 (8)	0.6924 (4)	0.042 (3)*	0.45
F18B	1.4957 (12)	0.7521 (9)	0.7482 (5)	0.056 (3)*	0.45

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb1	0.01408 (11)	0.01832 (11)	0.02337 (12)	−0.00201 (8)	−0.00318 (9)	−0.00261 (10)
Tb2	0.01533 (11)	0.02011 (11)	0.02205 (12)	−0.00443 (8)	−0.00096 (9)	0.00038 (10)
S1	0.0255 (7)	0.0402 (8)	0.0628 (11)	−0.0093 (6)	−0.0001 (7)	−0.0147 (8)
S2	0.0201 (6)	0.0294 (7)	0.0475 (9)	−0.0029 (5)	−0.0055 (6)	−0.0084 (6)
S5	0.0336 (8)	0.0393 (8)	0.0625 (11)	0.0009 (6)	0.0022 (8)	0.0071 (8)
S6	0.0278 (7)	0.0567 (10)	0.0351 (8)	−0.0126 (7)	−0.0009 (6)	−0.0101 (7)
O2	0.0173 (17)	0.0233 (17)	0.0291 (19)	−0.0021 (13)	−0.0026 (14)	−0.0058 (15)
O1	0.0192 (17)	0.0217 (17)	0.031 (2)	−0.0028 (13)	−0.0014 (14)	−0.0014 (15)
O3	0.0187 (18)	0.032 (2)	0.040 (2)	−0.0048 (15)	−0.0072 (15)	−0.0117 (17)
O4	0.0154 (16)	0.0240 (18)	0.034 (2)	−0.0019 (13)	−0.0039 (14)	−0.0092 (15)
O5	0.0181 (17)	0.0259 (18)	0.030 (2)	−0.0016 (14)	0.0006 (14)	−0.0006 (15)
O6	0.0214 (18)	0.0253 (18)	0.029 (2)	−0.0021 (14)	−0.0034 (15)	0.0034 (15)
O8	0.0210 (18)	0.033 (2)	0.031 (2)	−0.0091 (15)	−0.0017 (15)	−0.0091 (16)
O7	0.0205 (18)	0.035 (2)	0.0267 (19)	−0.0080 (15)	−0.0039 (14)	−0.0011 (16)
O10	0.0223 (19)	0.0302 (19)	0.036 (2)	−0.0050 (15)	0.0012 (16)	0.0069 (16)
O9	0.0211 (18)	0.0239 (18)	0.032 (2)	−0.0052 (14)	0.0005 (15)	0.0001 (15)
O12	0.0207 (18)	0.034 (2)	0.0261 (19)	−0.0068 (15)	0.0025 (15)	−0.0067 (16)
O11	0.0206 (18)	0.0260 (18)	0.031 (2)	−0.0042 (14)	0.0013 (15)	−0.0018 (15)
O14	0.079 (4)	0.037 (3)	0.051 (3)	−0.012 (2)	−0.011 (3)	−0.006 (2)
O13	0.107 (5)	0.062 (3)	0.052 (3)	−0.013 (3)	0.011 (3)	−0.024 (3)
N1	0.0160 (19)	0.0195 (19)	0.026 (2)	−0.0024 (15)	0.0004 (16)	−0.0086 (16)
N4	0.018 (2)	0.0185 (19)	0.025 (2)	−0.0038 (15)	−0.0054 (16)	−0.0002 (16)
N2	0.0168 (19)	0.021 (2)	0.024 (2)	−0.0038 (15)	0.0003 (16)	−0.0031 (16)
N3	0.0167 (19)	0.023 (2)	0.021 (2)	−0.0053 (16)	−0.0010 (15)	0.0003 (16)
C1	0.015 (2)	0.029 (3)	0.034 (3)	−0.0003 (19)	−0.003 (2)	−0.004 (2)
C2	0.014 (2)	0.031 (3)	0.038 (3)	−0.005 (2)	0.003 (2)	0.000 (2)
C3	0.018 (2)	0.026 (2)	0.027 (3)	−0.0060 (19)	0.0017 (19)	0.002 (2)
C4	0.014 (2)	0.016 (2)	0.023 (2)	−0.0022 (17)	−0.0001 (18)	−0.0058 (18)
C5	0.019 (2)	0.020 (2)	0.019 (2)	−0.0045 (18)	−0.0017 (18)	−0.0055 (18)
C6	0.019 (2)	0.023 (2)	0.030 (3)	−0.0027 (19)	−0.005 (2)	0.003 (2)
C7	0.016 (2)	0.026 (3)	0.039 (3)	−0.007 (2)	0.000 (2)	0.001 (2)
C8	0.024 (3)	0.023 (2)	0.030 (3)	−0.006 (2)	−0.006 (2)	0.002 (2)
C9	0.017 (2)	0.028 (3)	0.029 (3)	−0.0003 (19)	−0.003 (2)	0.000 (2)
C10	0.019 (2)	0.027 (3)	0.040 (3)	−0.002 (2)	0.003 (2)	−0.014 (2)
C11	0.024 (3)	0.021 (2)	0.024 (3)	−0.0050 (19)	−0.001 (2)	−0.0015 (19)
C12	0.016 (2)	0.026 (3)	0.031 (3)	−0.0050 (19)	0.001 (2)	−0.004 (2)
C13	0.017 (2)	0.013 (2)	0.034 (3)	−0.0059 (17)	−0.007 (2)	−0.0040 (19)
C14	0.046 (4)	0.030 (3)	0.045 (4)	−0.015 (3)	0.001 (3)	−0.008 (3)
C15	0.029 (3)	0.037 (3)	0.054 (4)	−0.016 (2)	−0.002 (3)	−0.006 (3)
C16	0.023 (3)	0.038 (3)	0.067 (5)	−0.007 (2)	0.000 (3)	−0.017 (3)
C17	0.020 (2)	0.033 (3)	0.028 (3)	−0.012 (2)	−0.007 (2)	−0.002 (2)
C18	0.026 (3)	0.025 (3)	0.036 (3)	−0.009 (2)	−0.002 (2)	−0.010 (2)
C19	0.022 (2)	0.019 (2)	0.025 (3)	−0.0084 (19)	0.0004 (19)	−0.0005 (19)
C20	0.022 (2)	0.020 (2)	0.030 (3)	−0.0054 (19)	−0.001 (2)	−0.001 (2)
C21	0.022 (3)	0.021 (2)	0.033 (3)	−0.0017 (19)	0.005 (2)	0.002 (2)
C22	0.036 (3)	0.023 (3)	0.045 (4)	−0.002 (2)	0.006 (3)	−0.009 (2)
C23	0.019 (3)	0.025 (3)	0.061 (4)	0.000 (2)	0.003 (3)	−0.005 (3)
C24	0.023 (3)	0.055 (4)	0.045 (4)	−0.012 (3)	−0.001 (2)	−0.021 (3)
C25	0.023 (3)	0.036 (3)	0.019 (2)	−0.008 (2)	−0.0017 (19)	0.003 (2)
C26	0.024 (3)	0.034 (3)	0.041 (3)	−0.011 (2)	−0.011 (2)	0.016 (2)
C27	0.027 (3)	0.030 (3)	0.026 (3)	−0.006 (2)	−0.009 (2)	0.003 (2)
C28	0.024 (3)	0.028 (3)	0.027 (3)	−0.004 (2)	0.000 (2)	0.001 (2)
C30	0.056 (4)	0.025 (3)	0.036 (3)	0.003 (3)	−0.001 (3)	0.001 (2)
C31	0.037 (3)	0.046 (4)	0.039 (4)	0.011 (3)	0.003 (3)	0.004 (3)
C32	0.028 (3)	0.049 (4)	0.025 (3)	−0.010 (3)	−0.003 (2)	0.006 (3)
C33	0.026 (3)	0.036 (3)	0.027 (3)	−0.012 (2)	−0.008 (2)	0.003 (2)
C34	0.028 (3)	0.035 (3)	0.028 (3)	−0.012 (2)	−0.006 (2)	−0.006 (2)
C35	0.021 (2)	0.030 (3)	0.026 (3)	−0.010 (2)	−0.002 (2)	0.001 (2)
C36	0.028 (3)	0.030 (3)	0.023 (3)	−0.004 (2)	0.000 (2)	−0.006 (2)
C38	0.026 (3)	0.061 (4)	0.035 (4)	0.004 (3)	0.001 (3)	−0.008 (3)
C39	0.049 (4)	0.047 (4)	0.045 (4)	−0.002 (3)	−0.002 (3)	−0.015 (3)
C40	0.031 (3)	0.065 (4)	0.034 (3)	−0.023 (3)	0.002 (2)	−0.014 (3)
C41	0.035 (3)	0.023 (3)	0.032 (3)	−0.014 (2)	0.001 (2)	−0.005 (2)
C42	0.028 (3)	0.027 (3)	0.032 (3)	−0.009 (2)	0.002 (2)	0.006 (2)
C43	0.029 (3)	0.018 (2)	0.029 (3)	−0.005 (2)	−0.002 (2)	−0.002 (2)
C44	0.028 (3)	0.030 (3)	0.035 (3)	−0.005 (2)	−0.004 (2)	−0.003 (2)
C45	0.032 (3)	0.028 (3)	0.054 (4)	0.002 (2)	−0.005 (3)	0.010 (3)
C46	0.050 (4)	0.041 (4)	0.076 (6)	0.005 (3)	−0.010 (4)	0.023 (4)
C47	0.033 (3)	0.039 (4)	0.081 (6)	0.000 (3)	−0.010 (3)	0.005 (4)
C48	0.029 (3)	0.038 (3)	0.054 (4)	−0.010 (3)	0.007 (3)	0.003 (3)
C49	0.021 (3)	0.024 (3)	0.041 (3)	0.000 (2)	0.006 (2)	0.003 (2)
C50	0.023 (3)	0.037 (3)	0.035 (3)	−0.001 (2)	0.006 (2)	−0.014 (2)
C51	0.023 (3)	0.028 (3)	0.025 (3)	−0.007 (2)	0.003 (2)	−0.004 (2)
C52	0.024 (3)	0.035 (3)	0.041 (3)	−0.013 (2)	0.004 (2)	−0.010 (2)
C53	0.039 (3)	0.061 (4)	0.036 (3)	−0.024 (3)	0.010 (3)	−0.015 (3)
C54	0.058 (4)	0.071 (5)	0.035 (4)	−0.033 (4)	0.007 (3)	−0.026 (3)
C55	0.040 (4)	0.080 (5)	0.038 (4)	−0.035 (4)	−0.002 (3)	−0.009 (3)
C56	0.024 (3)	0.048 (4)	0.047 (4)	−0.005 (3)	0.005 (3)	−0.007 (3)
C57	0.083 (6)	0.070 (6)	0.077 (6)	−0.033 (5)	−0.023 (5)	0.019 (5)
C58	0.076 (5)	0.036 (4)	0.044 (4)	−0.011 (3)	−0.009 (4)	0.004 (3)
C59A	0.081 (6)	0.052 (5)	0.082 (7)	−0.015 (4)	−0.018 (5)	0.013 (4)
F1	0.034 (2)	0.101 (4)	0.063 (3)	−0.022 (2)	0.015 (2)	0.002 (3)
F2	0.0229 (18)	0.071 (3)	0.074 (3)	−0.0046 (17)	−0.0122 (18)	−0.005 (2)
F3	0.023 (2)	0.063 (3)	0.194 (6)	−0.0025 (19)	0.020 (3)	−0.074 (4)
F4	0.046 (3)	0.069 (3)	0.110 (4)	−0.008 (2)	−0.049 (3)	0.002 (3)
F5	0.029 (2)	0.131 (4)	0.077 (3)	−0.039 (2)	0.021 (2)	−0.059 (3)
F6	0.0268 (19)	0.072 (3)	0.077 (3)	−0.0213 (18)	−0.0043 (18)	−0.038 (2)

Geometric parameters (Å, º)

Tb1—O3	2.307 (3)	C18—C19	1.425 (7)
Tb1—O5	2.321 (3)	C18—H18	0.9500
Tb1—O1	2.325 (3)	C19—C20	1.464 (7)
Tb1—O2	2.332 (3)	C20—C21	1.401 (7)
Tb1—O6	2.332 (3)	C21—C22	1.417 (7)
Tb1—O4	2.343 (3)	C21—H21	0.9500
Tb1—N4	2.568 (4)	C22—C23	1.351 (9)
Tb1—N1	2.586 (4)	C22—H22	0.9500
Tb2—O8	2.308 (4)	C23—H23	0.9500
Tb2—O12	2.309 (4)	C24—F6	1.330 (7)
Tb2—O10	2.335 (4)	C24—F5	1.330 (7)
Tb2—O7	2.336 (3)	C24—F4	1.334 (8)
Tb2—O9	2.346 (3)	C25—C26	1.352 (8)
Tb2—O11	2.347 (4)	C25—C32	1.535 (7)
Tb2—N3	2.547 (4)	C26—C27	1.415 (7)
Tb2—N2	2.628 (4)	C26—H26	0.9500
S1—C15	1.678 (6)	C27—C28	1.467 (7)
S1—C12	1.708 (5)	C30—C31	1.341 (9)
S2—C23	1.712 (6)	C30—H30	0.9500
S2—C20	1.726 (5)	C31—H31	0.9500
S3A—C31	1.649 (6)	C32—F7A	1.205 (12)
S3A—C28	1.704 (6)	C32—F8C	1.209 (16)
C29A—C28	1.404 (10)	C32—F9B	1.301 (17)
C29A—C30	1.452 (10)	C32—F9A	1.342 (11)
C29A—H29A	0.9500	C32—F8A	1.389 (13)
S3B—C30	1.604 (9)	C32—F9C	1.392 (17)
S3B—C28	1.715 (12)	C32—F7B	1.448 (19)
C29B—C28	1.424 (13)	C32—F8B	1.45 (2)
C29B—C31	1.472 (13)	C32—F7C	1.478 (16)
C29B—H29B	0.9500	C33—C34	1.369 (8)
S4A—C38	1.649 (7)	C33—C40	1.540 (7)
S4A—C36	1.688 (6)	C34—C35	1.413 (7)
C37A—C39	1.47 (2)	C34—H34	0.9500
C37A—C36	1.533 (19)	C35—C36	1.463 (7)
C37A—H37A	0.9500	C38—C39	1.335 (9)
S4B—C39	1.620 (10)	C38—H38	0.9500
S4B—C36	1.672 (8)	C39—H39	0.9500
C37B—C38	1.479 (15)	C40—F10A	1.221 (10)
C37B—C36	1.502 (15)	C40—F12A	1.311 (10)
C37B—H37B	0.9500	C40—F11B	1.321 (10)
S5—C47	1.690 (7)	C40—F11A	1.392 (9)
S5—C44	1.711 (6)	C40—F12B	1.426 (12)
S6—C55	1.698 (7)	C40—F10B	1.451 (11)
S6—C52	1.718 (6)	C41—C42	1.374 (8)
O2—C11	1.263 (6)	C41—C48	1.513 (8)
O1—C9	1.280 (6)	C42—C43	1.424 (7)
O3—C17	1.266 (6)	C42—H42	0.9500
O4—C19	1.257 (6)	C43—C44	1.468 (8)
O5—C25	1.282 (6)	C44—C45	1.434 (8)
O6—C27	1.265 (6)	C45—C46	1.412 (9)
O8—C35	1.264 (6)	C45—H45	0.9500
O7—C33	1.261 (7)	C46—C47	1.355 (11)
O10—C43	1.247 (6)	C46—H46	0.9500
O9—C41	1.263 (6)	C47—H47	0.9500
O12—C51	1.265 (6)	C48—F14C	1.22 (2)
O11—C49	1.267 (7)	C48—F13B	1.279 (18)
O14—C58	1.323 (8)	C48—F13C	1.318 (17)
O14—C59A	1.430 (10)	C48—F14A	1.328 (10)
O13—C58	1.209 (9)	C48—F15B	1.33 (2)
N1—C1	1.335 (6)	C48—F15A	1.338 (11)
N1—C4	1.342 (6)	C48—F15C	1.366 (17)
N4—C5	1.331 (6)	C48—F13A	1.413 (11)
N4—C8	1.342 (6)	C48—F14B	1.425 (15)
N2—C4	1.323 (6)	C49—C50	1.370 (8)
N2—C3	1.360 (6)	C49—C56	1.522 (7)
N3—C5	1.334 (6)	C50—C51	1.404 (7)
N3—C6	1.348 (6)	C50—H50	0.9500
C1—C2	1.373 (7)	C51—C52	1.457 (7)
C1—H1	0.9500	C52—C53	1.411 (8)
C2—C3	1.382 (7)	C53—C54	1.434 (9)
C2—H2	0.9500	C53—H53	0.9500
C3—H3	0.9500	C54—C55	1.330 (10)
C4—C5	1.488 (6)	C54—H54	0.9500
C6—C7	1.379 (7)	C55—H55	0.9500
C6—H6	0.9500	C56—F18B	1.215 (13)
C7—C8	1.367 (7)	C56—F17A	1.274 (10)
C7—H7	0.9500	C56—F16A	1.342 (9)
C8—H8	0.9500	C56—F16B	1.357 (11)
C9—C10	1.353 (7)	C56—F17B	1.422 (12)
C9—C16	1.543 (8)	C56—F18A	1.437 (10)
C10—C11	1.424 (7)	C57—C58	1.478 (12)
C10—H10	0.9500	C57—H57A	0.9800
C11—C12	1.470 (7)	C57—H57B	0.9800
C12—C13	1.436 (7)	C57—H57C	0.9800
C13—C14	1.436 (7)	C59A—C60A	1.541 (17)
C13—H13	0.9500	C59A—H59A	0.9900
C14—C15	1.349 (9)	C59A—H59B	0.9900
C14—H14	0.9500	C60A—H60A	0.9800
C15—H15	0.9500	C60A—H60B	0.9800
C16—F3	1.309 (7)	C60A—H60C	0.9800
C16—F2	1.326 (8)	C60B—H60D	0.9800
C16—F1	1.328 (8)	C60B—H60E	0.9800
C17—C18	1.357 (8)	C60B—H60F	0.9800
C17—C24	1.534 (7)
O3—Tb1—O5	118.87 (14)	F4—C24—C17	111.6 (5)
O3—Tb1—O1	80.58 (13)	O5—C25—C26	128.7 (5)
O5—Tb1—O1	141.60 (12)	O5—C25—C32	112.4 (5)
O3—Tb1—O2	151.17 (12)	C26—C25—C32	118.9 (5)
O5—Tb1—O2	77.60 (13)	C25—C26—C27	123.3 (5)
O1—Tb1—O2	73.30 (12)	C25—C26—H26	118.4
O3—Tb1—O6	82.44 (13)	C27—C26—H26	118.4
O5—Tb1—O6	73.40 (12)	O6—C27—C26	123.5 (5)
O1—Tb1—O6	77.38 (13)	O6—C27—C28	116.8 (5)
O2—Tb1—O6	80.18 (12)	C26—C27—C28	119.7 (5)
O3—Tb1—O4	72.42 (12)	C29A—C28—C29B	99.7 (10)
O5—Tb1—O4	76.00 (12)	C29A—C28—C27	129.8 (6)
O1—Tb1—O4	142.06 (12)	C29B—C28—C27	129.9 (8)
O2—Tb1—O4	136.39 (12)	C29A—C28—S3A	110.4 (5)
O6—Tb1—O4	123.35 (13)	C27—C28—S3A	119.7 (4)
O3—Tb1—N4	133.52 (13)	C29B—C28—S3B	107.3 (8)
O5—Tb1—N4	77.70 (13)	C27—C28—S3B	121.8 (5)
O1—Tb1—N4	114.17 (13)	C31—C30—C29A	107.7 (6)
O2—Tb1—N4	70.31 (12)	C31—C30—S3B	120.8 (6)
O6—Tb1—N4	142.31 (12)	C31—C30—H30	126.2
O4—Tb1—N4	70.56 (12)	C29A—C30—H30	126.2
O3—Tb1—N1	81.29 (13)	S3B—C30—H30	113.0
O5—Tb1—N1	137.33 (12)	C30—C31—C29B	104.2 (9)
O1—Tb1—N1	74.34 (12)	C30—C31—S3A	118.1 (5)
O2—Tb1—N1	102.70 (13)	C30—C31—H31	121.0
O6—Tb1—N1	149.25 (12)	C29B—C31—H31	133.4
O4—Tb1—N1	75.62 (13)	S3A—C31—H31	121.0
N4—Tb1—N1	63.12 (12)	F7A—C32—F9A	108.2 (9)
O8—Tb2—O12	136.74 (13)	F7A—C32—F8A	101.4 (9)
O8—Tb2—O10	110.11 (14)	F9A—C32—F8A	105.7 (8)
O12—Tb2—O10	95.03 (14)	F8C—C32—F9C	107.0 (11)
O8—Tb2—O7	71.98 (12)	F9B—C32—F7B	100.4 (12)
O12—Tb2—O7	145.66 (13)	F9B—C32—F8B	111.5 (12)
O10—Tb2—O7	88.27 (13)	F7B—C32—F8B	116.1 (12)
O8—Tb2—O9	73.42 (13)	F8C—C32—F7C	101.2 (11)
O12—Tb2—O9	82.59 (13)	F9C—C32—F7C	110.7 (10)
O10—Tb2—O9	71.52 (12)	F7A—C32—C25	116.7 (7)
O7—Tb2—O9	130.29 (13)	F8C—C32—C25	121.5 (9)
O8—Tb2—O11	146.73 (12)	F9B—C32—C25	112.9 (9)
O12—Tb2—O11	72.64 (13)	F9A—C32—C25	111.8 (6)
O10—Tb2—O11	74.68 (13)	F8A—C32—C25	112.1 (6)
O7—Tb2—O11	75.37 (13)	F9C—C32—C25	106.8 (8)
O9—Tb2—O11	135.69 (12)	F7B—C32—C25	104.9 (8)
O8—Tb2—N3	90.97 (13)	F8B—C32—C25	110.6 (10)
O12—Tb2—N3	84.49 (13)	F7C—C32—C25	109.3 (7)
O10—Tb2—N3	147.92 (13)	O7—C33—C34	129.4 (5)
O7—Tb2—N3	75.23 (13)	O7—C33—C40	112.1 (5)
O9—Tb2—N3	139.59 (12)	C34—C33—C40	118.4 (5)
O11—Tb2—N3	74.60 (13)	C33—C34—C35	121.5 (5)
O8—Tb2—N2	72.95 (13)	C33—C34—H34	119.2
O12—Tb2—N2	66.81 (13)	C35—C34—H34	119.2
O10—Tb2—N2	145.55 (12)	O8—C35—C34	122.8 (5)
O7—Tb2—N2	123.57 (12)	O8—C35—C36	116.6 (4)
O9—Tb2—N2	77.05 (12)	C34—C35—C36	120.6 (5)
O11—Tb2—N2	122.41 (13)	C35—C36—C37B	124.7 (7)
N3—Tb2—N2	62.67 (12)	C35—C36—C37A	130.0 (8)
C15—S1—C12	92.1 (3)	C35—C36—S4B	124.0 (4)
C23—S2—C20	91.2 (3)	C37B—C36—S4B	111.0 (7)
C31—S3A—C28	91.3 (3)	C35—C36—S4A	117.2 (4)
C28—C29A—C30	112.6 (7)	C37A—C36—S4A	112.5 (8)
C28—C29A—H29A	123.7	C39—C38—C37B	109.3 (8)
C30—C29A—H29A	123.7	C39—C38—S4A	117.5 (5)
C30—S3B—C28	91.3 (6)	C39—C38—H38	121.2
C28—C29B—C31	111.8 (11)	C37B—C38—H38	128.8
C28—C29B—H29B	124.1	S4A—C38—H38	121.2
C31—C29B—H29B	124.1	C38—C39—C37A	113.2 (9)
C38—S4A—C36	91.8 (3)	C38—C39—S4B	119.3 (6)
C39—C37A—C36	104.3 (11)	C38—C39—H39	123.4
C39—C37A—H37A	127.8	C37A—C39—H39	123.4
C36—C37A—H37A	127.8	S4B—C39—H39	117.2
C39—S4B—C36	92.4 (4)	F10A—C40—F12A	97.9 (7)
C38—C37B—C36	107.0 (9)	F10A—C40—F11A	110.8 (7)
C38—C37B—H37B	126.5	F12A—C40—F11A	102.4 (7)
C36—C37B—H37B	126.5	F11B—C40—F12B	113.4 (7)
C47—S5—C44	92.2 (3)	F11B—C40—F10B	100.4 (7)
C55—S6—C52	92.0 (3)	F12B—C40—F10B	116.6 (7)
C11—O2—Tb1	134.5 (3)	F10A—C40—C33	119.3 (7)
C9—O1—Tb1	128.6 (3)	F12A—C40—C33	111.4 (6)
C17—O3—Tb1	134.6 (3)	F11B—C40—C33	113.5 (6)
C19—O4—Tb1	138.5 (3)	F11A—C40—C33	112.7 (5)
C25—O5—Tb1	130.5 (3)	F12B—C40—C33	105.9 (6)
C27—O6—Tb1	135.2 (3)	F10B—C40—C33	107.1 (6)
C35—O8—Tb2	139.8 (3)	O9—C41—C42	128.2 (5)
C33—O7—Tb2	134.0 (3)	O9—C41—C48	113.7 (5)
C43—O10—Tb2	138.7 (3)	C42—C41—C48	118.0 (5)
C41—O9—Tb2	134.0 (3)	C41—C42—C43	121.2 (5)
C51—O12—Tb2	138.3 (3)	C41—C42—H42	119.4
C49—O11—Tb2	131.6 (3)	C43—C42—H42	119.4
C58—O14—C59A	116.9 (7)	O10—C43—C42	123.9 (5)
C1—N1—C4	116.0 (4)	O10—C43—C44	116.6 (5)
C1—N1—Tb1	122.9 (3)	C42—C43—C44	119.5 (5)
C4—N1—Tb1	121.0 (3)	C45—C44—C43	130.0 (5)
C5—N4—C8	116.0 (4)	C45—C44—S5	111.7 (4)
C5—N4—Tb1	121.4 (3)	C43—C44—S5	118.3 (4)
C8—N4—Tb1	122.1 (3)	C46—C45—C44	108.7 (6)
C4—N2—C3	116.5 (4)	C46—C45—H45	125.6
C4—N2—Tb2	119.8 (3)	C44—C45—H45	125.6
C3—N2—Tb2	123.0 (3)	C47—C46—C45	115.1 (6)
C5—N3—C6	116.2 (4)	C47—C46—H46	122.4
C5—N3—Tb2	123.0 (3)	C45—C46—H46	122.4
C6—N3—Tb2	120.8 (3)	C46—C47—S5	112.2 (5)
N1—C1—C2	122.8 (5)	C46—C47—H47	123.9
N1—C1—H1	118.6	S5—C47—H47	123.9
C2—C1—H1	118.6	F14C—C48—F13C	104.5 (14)
C1—C2—C3	117.1 (5)	F13B—C48—F15B	105.8 (13)
C1—C2—H2	121.5	F14A—C48—F15A	109.4 (8)
C3—C2—H2	121.5	F14C—C48—F15C	106.6 (13)
N2—C3—C2	121.3 (5)	F13C—C48—F15C	103.7 (12)
N2—C3—H3	119.4	F14A—C48—F13A	105.8 (7)
C2—C3—H3	119.4	F15A—C48—F13A	107.2 (7)
N2—C4—N1	126.3 (4)	F13B—C48—F14B	101.6 (11)
N2—C4—C5	117.3 (4)	F15B—C48—F14B	103.9 (12)
N1—C4—C5	116.5 (4)	F14C—C48—C41	113.0 (11)
N4—C5—N3	126.3 (4)	F13B—C48—C41	119.0 (10)
N4—C5—C4	117.2 (4)	F13C—C48—C41	113.5 (8)
N3—C5—C4	116.5 (4)	F14A—C48—C41	115.1 (6)
N3—C6—C7	121.8 (5)	F15B—C48—C41	113.0 (9)
N3—C6—H6	119.1	F15A—C48—C41	110.1 (6)
C7—C6—H6	119.1	F15C—C48—C41	114.5 (8)
C8—C7—C6	117.1 (5)	F13A—C48—C41	108.8 (6)
C8—C7—H7	121.4	F14B—C48—C41	112.0 (7)
C6—C7—H7	121.4	O11—C49—C50	128.5 (5)
N4—C8—C7	122.6 (5)	O11—C49—C56	113.3 (5)
N4—C8—H8	118.7	C50—C49—C56	118.1 (5)
C7—C8—H8	118.7	C49—C50—C51	122.7 (5)
O1—C9—C10	129.3 (5)	C49—C50—H50	118.6
O1—C9—C16	112.2 (4)	C51—C50—H50	118.6
C10—C9—C16	118.5 (5)	O12—C51—C50	122.6 (5)
C9—C10—C11	122.8 (5)	O12—C51—C52	116.3 (5)
C9—C10—H10	118.6	C50—C51—C52	121.1 (5)
C11—C10—H10	118.6	C53—C52—C51	129.9 (5)
O2—C11—C10	123.0 (4)	C53—C52—S6	111.6 (5)
O2—C11—C12	117.4 (4)	C51—C52—S6	118.5 (4)
C10—C11—C12	119.6 (4)	C52—C53—C54	109.1 (6)
C13—C12—C11	129.3 (4)	C52—C53—H53	125.4
C13—C12—S1	112.7 (4)	C54—C53—H53	125.4
C11—C12—S1	118.0 (4)	C55—C54—C53	114.8 (6)
C12—C13—C14	107.2 (5)	C55—C54—H54	122.6
C12—C13—H13	126.4	C53—C54—H54	122.6
C14—C13—H13	126.4	C54—C55—S6	112.5 (5)
C15—C14—C13	115.1 (5)	C54—C55—H55	123.8
C15—C14—H14	122.5	S6—C55—H55	123.8
C13—C14—H14	122.5	F17A—C56—F16A	110.8 (7)
C14—C15—S1	112.8 (4)	F18B—C56—F16B	108.2 (9)
C14—C15—H15	123.6	F18B—C56—F17B	106.5 (8)
S1—C15—H15	123.6	F16B—C56—F17B	105.1 (8)
F3—C16—F2	107.8 (6)	F17A—C56—F18A	106.9 (6)
F3—C16—F1	108.5 (6)	F16A—C56—F18A	102.9 (6)
F2—C16—F1	105.1 (5)	F18B—C56—C49	113.9 (8)
F3—C16—C9	113.3 (5)	F17A—C56—C49	113.0 (6)
F2—C16—C9	110.5 (5)	F16A—C56—C49	113.5 (6)
F1—C16—C9	111.3 (5)	F16B—C56—C49	114.7 (6)
O3—C17—C18	129.9 (5)	F17B—C56—C49	107.9 (6)
O3—C17—C24	112.0 (5)	F18A—C56—C49	109.0 (6)
C18—C17—C24	118.1 (5)	C58—C57—H57A	109.5
C17—C18—C19	121.7 (5)	C58—C57—H57B	109.5
C17—C18—H18	119.2	H57A—C57—H57B	109.5
C19—C18—H18	119.2	C58—C57—H57C	109.5
O4—C19—C18	122.8 (5)	H57A—C57—H57C	109.5
O4—C19—C20	117.1 (4)	H57B—C57—H57C	109.5
C18—C19—C20	120.1 (4)	O13—C58—O14	122.3 (8)
C21—C20—C19	130.4 (5)	O13—C58—C57	125.1 (8)
C21—C20—S2	112.0 (4)	O14—C58—C57	112.6 (7)
C19—C20—S2	117.6 (4)	O14—C59A—C60A	103.6 (9)
C20—C21—C22	110.3 (5)	O14—C59A—H59A	111.0
C20—C21—H21	124.9	C60A—C59A—H59A	111.0
C22—C21—H21	124.9	O14—C59A—H59B	111.0
C23—C22—C21	114.2 (5)	C60A—C59A—H59B	111.0
C23—C22—H22	122.9	H59A—C59A—H59B	109.0
C21—C22—H22	122.9	C59A—C60A—H60A	109.5
C22—C23—S2	112.3 (4)	C59A—C60A—H60B	109.5
C22—C23—H23	123.8	H60A—C60A—H60B	109.5
S2—C23—H23	123.8	C59A—C60A—H60C	109.5
F6—C24—F5	106.0 (5)	H60A—C60A—H60C	109.5
F6—C24—F4	105.6 (5)	H60B—C60A—H60C	109.5
F5—C24—F4	108.5 (6)	H60D—C60B—H60E	109.5
F6—C24—C17	114.3 (5)	H60D—C60B—H60F	109.5
F5—C24—C17	110.5 (5)	H60E—C60B—H60F	109.5