Aquachlorobis(4,4′,4′′-tri-tert-butyl-2,2′;6′,2′′-terpyridine-κ³N)terbium(III) diperchlorate ethanol disolvate

In the title compound, [TbCl(C₂₇H₃₅N₃)₂(H₂O)](ClO₄)₂·2C₂H₆O, the Tb^III ion has a coordination number of eight, composed of two tridentate substituted-ter­pyridine ligands, a water mol­ecule and a bound Cl⁻ anion. The first coordination shell can be described as a distorted bicapped trigonal prism. The dihedral angles between pyridine rings belonging to the same tpy ligand range from 5.2 (5) to 16.8 (5)°.

S1. Comment

As part of our ongoing research programme on lanthanide coordination compounds (Bünzli et al., 2000), we are interested in the interplay between ligand structure and the photophysical properties of the complexes formed. Progress in these areas over the last two decades has led, for example, to the introduction of several commercially available fluoro-immunoassays based on highly luminescent lanthanide complexes (Hemmilä et al., 1995; Mathis, 1998). We have recently shown (Mürner et al., 2000) that the introduction of simple alkane ligands in the 4-positions of the parent compound 2,2';6',2''-terpyridine (tpy) greatly enhances the quantum yields of metal-centred luminescence in complexes with Eu^III and, particularly, with Tb^III. During our efforts to obtain X-ray quality crystals of the complexes [Ln(L¹)₃](ClO₄)₃ (where L¹ is 4,4',4''-tri-tert-butyl-2,2';6',2''-terpyridine), we obtained crystals that, instead of the expected tris complex, were comprised of the title compound, [Tb(L¹)₂(H₂O)Cl](ClO₄)₂·2C₂H₆O, (I). \sch

Complexes of the types [Ln(L)X₃] (X is NO₃^- or a halogenide) and [Ln(L)₃]³⁺ (L is tpy or its derivatives) have been reported in the literature with essentially all the rare earths. The most recent examples are a series of papers by White (Semenova et al., 1999; Semenova & White, 1999a,b), and by Drew et al. (2000). Until very recently, only one X-ray structure of a complex in the lanthanide-tpy system displaying a 1:2 metal to ligand stoichiometry was described. The salt [La(tpy)₂(NO₃)₂][La(tpy)(NO₃)₄] contains a cationic species with ten-coordinate La^III and an anionic species with 11-coordinate La^III (Frechette & Bensimon, 1995). Structures of the analogous complexes [Ln(tpy)₂(NO₃)₂][Ln(tpy)(NO₃)₄] (Ln is Nd, Sm, Tb, Dy or Ho) have recently been reported (References?). In these compounds, both the cation and the anion display a coordination number of ten, with one of the four nitrate ligands in the anion binding only in a monodentate fashion. This contrasts the with La^III structure (Frechette & Bensimon, 1995), where all four nitrates act as bidentate ligands in the anion.

For the complexes [Ln(tpy)₂(NO₃)₂][Ln(tpy)(NO₃)₄] (Ln is La, Sm, Dy or Ho), dihedral angles between pyridine rings of up to 29° were observed. For Ln = Tb or Nd, on the other hand, both tpy ligands are close to planarity (inter-pyridine angles < 10°). Large deviations from planarity in the ligands were also observed in the structures of [Ln(tpy)₃]³⁺ complexes (Skelton et al., 1996; Semenova et al., 1999). In contrast, the complex [Tb(tpy)Cl(H₂O)₄]Cl₂·3H₂O (Kepert et al., 1994) displays dihedral angles of 9.4 and 10.6°. In the title compound, (I), the dihedral angles between pyridine rings in the same molecule of L1 vary between 5.2 (5) and 16.8 (5)°. We conclude that, overall, the complexed ligand L¹ displays a nearly planar conformation. The reasons for the distortions in tpy ligands bound to lanthanide cations remain unclear, especially if one considers the different behaviour displayed by neighbours in the series (e.g. Tb and Dy).

All bond lengths between the central cation and the ligand atoms in (I) are comparable with those in the Tb^III mono-tpy complex (Kepert et al., 1994). A noteworthy exception is that the bonds between the Tb and the N atoms of the two peripheral pyridine rings are not equal in (I). The observed Tb—N bonds are all slightly shorter than in the cation [Tb(tpy)₂(NO₃)₂]⁺ (Drew et al., 2000), where non-equal bond lengths between Tb^III and peripheral pyridine N atoms are seen in only one of the tpy molecules. In the present case, and in contrast with other structures of rare earth complexes, (I) displays neither a mono- nor a bidentate binding of the perchlorate anions. Instead, a purely ionic behaviour is observed.

Hydrogen bonding interactions can be detected between the coordinated water molecule and the ethanol solvate. Weaker interactions are apparent between the coordinated Cl and the ethanol solvate, and between perchlorate and C—H fragments on the pyridine rings. The coordination polyhedron for Tb^III can be described as a distorted bicapped trigonal prism (Porai-Koshits & Aslanov, 1972).

S2. Experimental

The synthesis of and analytical data for the parent compound, [Tb(L¹)₃](ClO₄)₃, (II), have been described elsewhere (Reference?). Suitable crystals of (I) formed upon slow evaporation of a MeCN-EtOH-pentane solution of (II) under non-anhydrous conditions. We attribute the presence of a Cl^- counterion to the unintentional use of a solvent contaminated with traces of hydrochloric acid.

S3. Refinement

From refinement of the site occupancies, there was evidence that atoms Cl1 and O1 are disordered, but a satisfactory disordered model could not be obtained. One EtOH molecule was found to be affected by disorder. A three-component model with isotropic displacement parameters was employed (occupancy factor 0.33 for all atoms). H atoms belonging to the solvent molecules and to the coordinating water were omitted. The remaining H atoms were placed in calculated positions and refined as riding, with C—H = 0.95–0.98 Å. Is this added text correct?

Computing details

Data collection: MAR345 Software (marresearch, 19??); cell refinement: marHKL (release 1.9.1), based on HKL (Otwinowski & Minor, 1997); data reduction: marHKL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the cation of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.

Aquachlorobis(4,4',4''-tri-tert-butyl-2,2';6',2''-terpyridine- κ³N)terbium(III) diperchlorate ethanol disolvate

Crystal data

[Tb(C27H35N3)2Cl(H2O)](ClO4)2·2C2H6O	F(000) = 2712
Mr = 1306.58	Dx = 1.339 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
a = 14.392 (3) Å	Cell parameters from 708 reflections
b = 21.233 (4) Å	θ = 1.4–12.2°
c = 22.172 (4) Å	µ = 1.27 mm^−1
β = 106.95 (3)°	T = 143 K
V = 6481 (2) Å^3	Prismatic, colourless
Z = 4	0.25 × 0.20 × 0.17 mm

Data collection

MAR345 IPDS diffractometer	5193 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 24.4°, θmin = 3.2°
ϕ scan (Δϕ = 3°; exp. time 180 s)	h = −16→16
34863 measured reflections	k = −24→24
10324 independent reflections	l = −24→25

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.203	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1083P)^2] where P = (Fo^2 + 2Fc^2)/3
10324 reflections	(Δ/σ)max = 0.001
721 parameters	Δρmax = 1.44 e Å^−3
11 restraints	Δρmin = −1.09 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	−0.07277 (4)	0.12549 (2)	0.116711 (18)	0.07378 (19)
Cl1	0.0216 (3)	0.08586 (15)	0.03852 (14)	0.1199 (11)
O1	−0.2160 (5)	0.0974 (3)	0.0356 (3)	0.0889 (19)
N1	−0.1897 (6)	0.0904 (3)	0.1750 (3)	0.0703 (18)
N2	−0.0878 (6)	0.0064 (4)	0.1287 (3)	0.0745 (19)
N3	−0.1372 (6)	0.2114 (4)	0.1707 (3)	0.0731 (19)
N4	0.0733 (5)	0.1957 (3)	0.1398 (3)	0.0679 (17)
N5	0.0551 (6)	0.1064 (3)	0.2195 (3)	0.0734 (19)
N6	−0.0885 (6)	0.2188 (4)	0.0433 (3)	0.0736 (19)
C1	−0.2437 (7)	0.1321 (4)	0.1947 (3)	0.070 (2)
C2	−0.3273 (7)	0.1174 (4)	0.2117 (3)	0.069 (2)
H2	−0.3631	0.1494	0.2250	0.083*
C3	−0.3567 (7)	0.0549 (4)	0.2087 (4)	0.075 (2)
C4	−0.2999 (7)	0.0114 (5)	0.1882 (4)	0.078 (2)
H4	−0.3169	−0.0320	0.1861	0.094*
C5	−0.2207 (7)	0.0301 (4)	0.1713 (4)	0.071 (2)
C6	−0.1612 (7)	−0.0175 (4)	0.1492 (4)	0.072 (2)
C7	−0.1793 (7)	−0.0808 (4)	0.1499 (4)	0.074 (2)
H7	−0.2307	−0.0953	0.1652	0.088*
C8	−0.1238 (7)	−0.1243 (5)	0.1285 (4)	0.075 (2)
C9	−0.0512 (8)	−0.1007 (5)	0.1080 (4)	0.082 (3)
H9	−0.0123	−0.1283	0.0918	0.098*
C10	−0.0332 (8)	−0.0367 (5)	0.1107 (4)	0.086 (3)
H10	0.0217	−0.0223	0.0991	0.103*
C11	−0.2066 (7)	0.1998 (4)	0.2002 (4)	0.070 (2)
C12	−0.2416 (7)	0.2461 (4)	0.2325 (4)	0.074 (2)
H12	−0.2896	0.2356	0.2526	0.089*
C13	−0.2066 (7)	0.3075 (4)	0.2356 (4)	0.079 (2)
C14	−0.1371 (7)	0.3196 (4)	0.2051 (4)	0.073 (2)
H14	−0.1104	0.3606	0.2057	0.088*
C15	−0.1075 (8)	0.2710 (4)	0.1738 (4)	0.078 (2)
H15	−0.0612	0.2811	0.1523	0.094*
C16	−0.1478 (8)	−0.1951 (5)	0.1237 (4)	0.087 (3)
C17	−0.2323 (9)	−0.2111 (5)	0.1512 (5)	0.105 (4)
H17A	−0.2165	−0.1959	0.1948	0.157*
H17B	−0.2418	−0.2569	0.1505	0.157*
H17C	−0.2920	−0.1908	0.1258	0.157*
C18	−0.0597 (10)	−0.2326 (6)	0.1625 (6)	0.120 (4)
H18A	−0.0032	−0.2227	0.1479	0.179*
H18B	−0.0737	−0.2778	0.1572	0.179*
H18C	−0.0456	−0.2214	0.2071	0.179*
C19	−0.1748 (11)	−0.2157 (6)	0.0546 (5)	0.120 (4)
H19A	−0.2406	−0.2011	0.0326	0.181*
H19B	−0.1724	−0.2617	0.0523	0.181*
H19C	−0.1287	−0.1974	0.0345	0.181*
C20	−0.4454 (8)	0.0336 (5)	0.2270 (4)	0.086 (3)
C21	−0.4959 (9)	−0.0231 (5)	0.1855 (5)	0.103 (3)
H21A	−0.5547	−0.0347	0.1967	0.154*
H21B	−0.4513	−0.0591	0.1929	0.154*
H21C	−0.5134	−0.0111	0.1409	0.154*
C22	−0.4113 (9)	0.0150 (6)	0.2957 (5)	0.104 (3)
H22A	−0.4663	−0.0014	0.3085	0.156*
H22B	−0.3842	0.0519	0.3213	0.156*
H22C	−0.3613	−0.0177	0.3017	0.156*
C23	−0.5209 (9)	0.0856 (6)	0.2193 (5)	0.104 (3)
H23A	−0.5425	0.0992	0.1751	0.156*
H23B	−0.4921	0.1214	0.2462	0.156*
H23C	−0.5767	0.0697	0.2316	0.156*
C24	−0.2465 (8)	0.3579 (5)	0.2707 (5)	0.089 (3)
C25	−0.3577 (8)	0.3634 (6)	0.2388 (7)	0.114 (4)
H25A	−0.3830	0.4000	0.2559	0.172*
H25B	−0.3900	0.3251	0.2471	0.172*
H25C	−0.3701	0.3686	0.1932	0.172*
C26	−0.1997 (9)	0.4222 (5)	0.2672 (5)	0.098 (3)
H26A	−0.1299	0.4199	0.2888	0.147*
H26B	−0.2296	0.4541	0.2875	0.147*
H26C	−0.2097	0.4336	0.2229	0.147*
C27	−0.2256 (10)	0.3364 (5)	0.3397 (5)	0.105 (4)
H27A	−0.1555	0.3310	0.3584	0.158*
H27B	−0.2586	0.2962	0.3411	0.158*
H27C	−0.2495	0.3682	0.3635	0.158*
C28	0.0793 (7)	0.2388 (4)	0.0966 (3)	0.068 (2)
C29	0.1668 (7)	0.2679 (4)	0.0983 (4)	0.067 (2)
H29	0.1689	0.2963	0.0656	0.081*
C30	0.2508 (7)	0.2563 (4)	0.1465 (3)	0.070 (2)
C31	0.2419 (7)	0.2112 (4)	0.1905 (4)	0.074 (2)
H31	0.2975	0.2006	0.2243	0.088*
C32	0.1550 (7)	0.1817 (4)	0.1864 (3)	0.068 (2)
C33	0.1443 (6)	0.1336 (4)	0.2325 (3)	0.065 (2)
C34	0.2188 (7)	0.1193 (4)	0.2862 (3)	0.067 (2)
H34	0.2802	0.1392	0.2934	0.080*
C35	0.2041 (8)	0.0749 (4)	0.3307 (4)	0.078 (2)
C36	0.1138 (8)	0.0479 (4)	0.3166 (4)	0.077 (2)
H36	0.1004	0.0174	0.3443	0.092*
C37	0.0404 (7)	0.0651 (4)	0.2614 (4)	0.077 (2)
H37	−0.0221	0.0466	0.2537	0.092*
C38	−0.0115 (7)	0.2561 (4)	0.0478 (3)	0.069 (2)
C39	−0.0169 (7)	0.3099 (4)	0.0122 (3)	0.069 (2)
H39	0.0396	0.3350	0.0175	0.083*
C40	−0.1037 (7)	0.3282 (4)	−0.0314 (4)	0.072 (2)
C41	−0.1832 (7)	0.2889 (5)	−0.0373 (4)	0.085 (3)
H41	−0.2438	0.2980	−0.0673	0.101*
C42	−0.1731 (8)	0.2363 (5)	0.0010 (4)	0.089 (3)
H42	−0.2289	0.2111	−0.0025	0.107*
C43	0.2890 (7)	0.0588 (5)	0.3890 (4)	0.083 (3)
C44	0.3131 (9)	0.1193 (5)	0.4288 (5)	0.105 (4)
H44A	0.3347	0.1520	0.4047	0.157*
H44B	0.3649	0.1105	0.4677	0.157*
H44C	0.2550	0.1338	0.4392	0.157*
C45	0.3778 (8)	0.0387 (5)	0.3699 (4)	0.093 (3)
H45A	0.3621	0.0014	0.3429	0.140*
H45B	0.4311	0.0288	0.4078	0.140*
H45C	0.3977	0.0731	0.3469	0.140*
C46	0.2575 (9)	0.0069 (7)	0.4264 (5)	0.122 (4)
H46A	0.2023	0.0216	0.4399	0.183*
H46B	0.3116	−0.0038	0.4634	0.183*
H46C	0.2384	−0.0305	0.3997	0.183*
C47	0.3453 (7)	0.2914 (5)	0.1539 (4)	0.077 (2)
C48	0.3672 (7)	0.3320 (5)	0.2133 (4)	0.086 (3)
H48A	0.3140	0.3619	0.2095	0.129*
H48B	0.4279	0.3551	0.2183	0.129*
H48C	0.3737	0.3050	0.2501	0.129*
C49	0.4274 (7)	0.2438 (5)	0.1589 (4)	0.085 (3)
H49A	0.4364	0.2182	0.1970	0.128*
H49B	0.4877	0.2664	0.1613	0.128*
H49C	0.4106	0.2164	0.1218	0.128*
C50	0.3381 (8)	0.3360 (5)	0.0974 (4)	0.089 (3)
H50A	0.3216	0.3115	0.0582	0.134*
H50B	0.4006	0.3571	0.1031	0.134*
H50C	0.2875	0.3675	0.0951	0.134*
C51	−0.1125 (8)	0.3885 (5)	−0.0702 (4)	0.081 (3)
C52	−0.0139 (8)	0.4214 (5)	−0.0607 (4)	0.088 (3)
H52A	0.0124	0.4341	−0.0165	0.132*
H52B	−0.0228	0.4588	−0.0878	0.132*
H52C	0.0313	0.3923	−0.0719	0.132*
C53	−0.1555 (9)	0.3736 (5)	−0.1399 (4)	0.091 (3)
H53A	−0.1132	0.3438	−0.1531	0.137*
H53B	−0.1610	0.4124	−0.1645	0.137*
H53C	−0.2200	0.3548	−0.1470	0.137*
C54	−0.1804 (9)	0.4336 (5)	−0.0493 (5)	0.099 (3)
H54A	−0.2446	0.4141	−0.0572	0.149*
H54B	−0.1864	0.4730	−0.0730	0.149*
H54C	−0.1537	0.4424	−0.0041	0.149*
Cl2	0.07942 (19)	0.41399 (11)	0.16149 (10)	0.0797 (6)
O2	0.1298 (5)	0.4125 (3)	0.1143 (3)	0.0850 (17)
O3	−0.0237 (5)	0.4173 (4)	0.1293 (3)	0.097 (2)
O4	0.1093 (6)	0.4684 (3)	0.2006 (3)	0.096 (2)
O5	0.1004 (6)	0.3579 (3)	0.1994 (3)	0.097 (2)
Cl3	−0.4655 (2)	0.27952 (16)	−0.14365 (12)	0.1007 (8)
O6	−0.5624 (5)	0.2967 (4)	−0.1756 (3)	0.102 (2)
O7	−0.4051 (6)	0.2874 (5)	−0.1841 (4)	0.122 (3)
O8	−0.4313 (7)	0.3172 (7)	−0.0898 (5)	0.195 (6)
O9	−0.4643 (8)	0.2144 (6)	−0.1271 (4)	0.152 (4)
O10	−0.1822 (9)	0.0132 (6)	−0.0491 (4)	0.169 (5)
C55	−0.2379 (14)	−0.0318 (7)	−0.0800 (9)	0.154 (6)
C56	−0.2901 (17)	−0.0564 (14)	−0.0399 (10)	0.255 (14)
O11A	−0.419 (3)	0.2455 (13)	0.0283 (14)	0.159 (11)*	0.33
C57A	−0.365 (3)	0.2908 (16)	0.0681 (16)	0.133 (13)*	0.33
C58A	−0.399 (3)	0.3573 (14)	0.0516 (17)	0.124 (12)*	0.33
O11B	−0.3855 (18)	0.1319 (13)	0.0432 (11)	0.119 (7)*	0.33
C57B	−0.470 (3)	0.095 (2)	0.0309 (15)	0.131 (13)*	0.33
C58B	−0.533 (3)	0.102 (3)	−0.0355 (17)	0.160 (18)*	0.33
O11C	−0.3915 (16)	0.1525 (10)	−0.0091 (9)	0.093 (5)*	0.33
C57C	−0.453 (3)	0.1816 (19)	0.024 (2)	0.150 (16)*	0.33
C58C	−0.548 (4)	0.143 (5)	0.006 (5)	0.34 (6)*	0.33

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb1	0.0813 (3)	0.0697 (3)	0.0727 (3)	−0.0060 (3)	0.0261 (2)	0.00066 (19)
Cl1	0.171 (3)	0.095 (2)	0.1165 (19)	−0.014 (2)	0.078 (2)	−0.0083 (15)
O1	0.099 (5)	0.079 (4)	0.081 (3)	−0.007 (4)	0.015 (3)	0.008 (3)
N1	0.080 (5)	0.054 (4)	0.088 (4)	0.003 (4)	0.041 (4)	−0.002 (3)
N2	0.081 (5)	0.072 (5)	0.070 (4)	0.000 (4)	0.022 (4)	0.000 (3)
N3	0.081 (5)	0.069 (5)	0.075 (4)	−0.008 (4)	0.032 (4)	0.007 (3)
N4	0.070 (5)	0.063 (4)	0.072 (4)	0.006 (4)	0.023 (3)	0.001 (3)
N5	0.073 (5)	0.074 (5)	0.072 (4)	−0.001 (4)	0.018 (3)	0.009 (3)
N6	0.074 (5)	0.074 (5)	0.077 (4)	−0.002 (4)	0.027 (4)	0.006 (3)
C1	0.080 (6)	0.063 (5)	0.064 (4)	−0.005 (5)	0.017 (4)	0.005 (4)
C2	0.072 (6)	0.070 (6)	0.071 (4)	−0.002 (5)	0.030 (4)	0.004 (4)
C3	0.077 (6)	0.074 (6)	0.072 (5)	−0.019 (5)	0.019 (4)	0.005 (4)
C4	0.081 (7)	0.073 (6)	0.088 (5)	−0.005 (5)	0.035 (5)	0.003 (4)
C5	0.069 (6)	0.064 (6)	0.082 (5)	−0.001 (5)	0.028 (4)	0.006 (4)
C6	0.076 (6)	0.066 (6)	0.079 (5)	0.002 (5)	0.032 (4)	0.003 (4)
C7	0.080 (6)	0.060 (6)	0.084 (5)	−0.008 (5)	0.030 (4)	−0.005 (4)
C8	0.081 (6)	0.075 (6)	0.074 (5)	0.006 (5)	0.031 (4)	0.000 (4)
C9	0.097 (8)	0.077 (7)	0.077 (5)	−0.008 (5)	0.034 (5)	−0.001 (4)
C10	0.072 (6)	0.092 (8)	0.098 (6)	−0.003 (6)	0.031 (5)	0.008 (5)
C11	0.070 (6)	0.062 (5)	0.078 (5)	0.000 (4)	0.022 (4)	0.003 (4)
C12	0.068 (6)	0.073 (6)	0.086 (5)	0.001 (5)	0.030 (4)	0.004 (4)
C13	0.075 (6)	0.069 (6)	0.098 (6)	0.002 (5)	0.032 (5)	0.003 (4)
C14	0.072 (6)	0.055 (5)	0.095 (5)	−0.010 (4)	0.029 (5)	−0.004 (4)
C15	0.093 (7)	0.064 (6)	0.087 (5)	0.006 (5)	0.042 (5)	0.004 (4)
C16	0.097 (8)	0.072 (6)	0.095 (6)	0.003 (6)	0.035 (5)	−0.008 (5)
C17	0.130 (10)	0.090 (8)	0.113 (7)	−0.025 (7)	0.065 (7)	−0.004 (6)
C18	0.111 (10)	0.080 (8)	0.160 (10)	−0.004 (7)	0.025 (8)	0.009 (7)
C19	0.173 (13)	0.099 (9)	0.096 (7)	−0.033 (9)	0.049 (7)	−0.018 (6)
C20	0.083 (7)	0.081 (7)	0.099 (6)	−0.008 (6)	0.034 (5)	0.008 (5)
C21	0.097 (8)	0.071 (7)	0.144 (8)	−0.028 (6)	0.042 (7)	−0.007 (6)
C22	0.095 (8)	0.109 (9)	0.117 (7)	−0.003 (7)	0.046 (6)	0.017 (6)
C23	0.089 (8)	0.096 (8)	0.139 (8)	−0.004 (7)	0.051 (6)	0.005 (7)
C24	0.095 (8)	0.071 (7)	0.108 (7)	−0.011 (5)	0.044 (6)	−0.007 (5)
C25	0.073 (7)	0.095 (9)	0.178 (11)	0.000 (6)	0.041 (7)	−0.032 (7)
C26	0.105 (8)	0.072 (7)	0.124 (7)	−0.010 (6)	0.045 (6)	−0.019 (5)
C27	0.137 (10)	0.078 (7)	0.120 (7)	−0.026 (7)	0.068 (7)	−0.031 (6)
C28	0.081 (6)	0.064 (5)	0.061 (4)	0.002 (5)	0.023 (4)	−0.004 (4)
C29	0.075 (6)	0.061 (5)	0.073 (5)	−0.002 (4)	0.034 (4)	0.000 (4)
C30	0.080 (6)	0.064 (5)	0.069 (4)	−0.006 (5)	0.026 (4)	−0.006 (4)
C31	0.085 (7)	0.067 (6)	0.070 (4)	−0.001 (5)	0.023 (4)	0.001 (4)
C32	0.078 (6)	0.061 (5)	0.070 (4)	0.001 (5)	0.031 (4)	0.003 (3)
C33	0.068 (6)	0.063 (5)	0.069 (4)	−0.002 (4)	0.027 (4)	−0.005 (4)
C34	0.069 (5)	0.064 (5)	0.073 (4)	−0.004 (4)	0.029 (4)	−0.006 (4)
C35	0.093 (7)	0.070 (6)	0.078 (5)	−0.001 (5)	0.036 (5)	0.001 (4)
C36	0.093 (7)	0.073 (6)	0.078 (5)	−0.009 (5)	0.046 (5)	0.000 (4)
C37	0.085 (7)	0.069 (6)	0.074 (5)	−0.004 (5)	0.022 (4)	0.004 (4)
C38	0.069 (6)	0.070 (6)	0.069 (4)	−0.004 (5)	0.024 (4)	−0.001 (4)
C39	0.076 (6)	0.066 (6)	0.071 (4)	−0.003 (4)	0.032 (4)	0.006 (4)
C40	0.076 (6)	0.071 (6)	0.073 (5)	0.005 (5)	0.027 (4)	0.005 (4)
C41	0.068 (6)	0.093 (7)	0.082 (5)	−0.009 (6)	0.005 (4)	0.008 (5)
C42	0.076 (7)	0.091 (8)	0.096 (6)	−0.011 (6)	0.020 (5)	0.008 (5)
C43	0.081 (7)	0.095 (7)	0.072 (5)	0.007 (6)	0.022 (4)	0.016 (4)
C44	0.110 (9)	0.107 (9)	0.088 (6)	0.022 (7)	0.012 (5)	−0.005 (5)
C45	0.089 (7)	0.105 (8)	0.094 (6)	0.026 (6)	0.038 (5)	0.014 (5)
C46	0.101 (9)	0.148 (12)	0.111 (7)	0.008 (8)	0.023 (6)	0.046 (7)
C47	0.072 (6)	0.079 (6)	0.081 (5)	0.009 (5)	0.024 (4)	0.007 (4)
C48	0.073 (6)	0.074 (6)	0.111 (6)	0.000 (5)	0.025 (5)	0.005 (5)
C49	0.071 (6)	0.091 (7)	0.101 (6)	0.004 (5)	0.037 (5)	0.005 (5)
C50	0.077 (7)	0.093 (7)	0.100 (6)	−0.013 (6)	0.030 (5)	0.017 (5)
C51	0.085 (7)	0.091 (7)	0.065 (5)	0.007 (6)	0.020 (4)	−0.006 (4)
C52	0.093 (8)	0.087 (7)	0.087 (5)	−0.005 (6)	0.030 (5)	0.017 (5)
C53	0.114 (8)	0.080 (7)	0.081 (5)	0.001 (6)	0.030 (5)	0.011 (4)
C54	0.110 (9)	0.086 (8)	0.101 (6)	0.006 (7)	0.029 (6)	0.010 (5)
Cl2	0.0903 (17)	0.0703 (15)	0.0833 (12)	0.0012 (12)	0.0327 (11)	−0.0008 (10)
O2	0.097 (5)	0.076 (4)	0.089 (4)	0.007 (4)	0.039 (3)	0.003 (3)
O3	0.082 (5)	0.098 (5)	0.108 (4)	−0.004 (4)	0.024 (4)	−0.006 (4)
O4	0.116 (6)	0.079 (5)	0.092 (4)	−0.008 (4)	0.031 (4)	−0.007 (3)
O5	0.106 (6)	0.084 (5)	0.111 (4)	0.010 (4)	0.046 (4)	0.018 (3)
Cl3	0.0782 (18)	0.126 (3)	0.0963 (15)	0.0097 (16)	0.0232 (13)	−0.0070 (15)
O6	0.072 (5)	0.128 (6)	0.104 (4)	0.006 (4)	0.022 (3)	−0.013 (4)
O7	0.093 (6)	0.153 (8)	0.134 (6)	0.019 (5)	0.055 (5)	0.022 (5)
O8	0.104 (7)	0.297 (17)	0.159 (7)	0.004 (9)	−0.001 (6)	−0.126 (10)
O9	0.141 (8)	0.166 (10)	0.159 (7)	0.025 (7)	0.057 (6)	0.066 (7)
O10	0.192 (12)	0.159 (10)	0.125 (7)	0.018 (9)	−0.004 (6)	−0.018 (6)
C55	0.194 (17)	0.082 (9)	0.220 (16)	−0.058 (11)	0.113 (14)	−0.034 (10)
C56	0.22 (3)	0.28 (3)	0.21 (2)	−0.05 (2)	−0.026 (18)	0.09 (2)

Geometric parameters (Å, º)

Tb1—O1	2.383 (6)	C27—H27B	0.9800
Tb1—N3	2.503 (7)	C27—H27C	0.9800
Tb1—N4	2.506 (7)	C28—C29	1.395 (12)
Tb1—N5	2.510 (7)	C28—C38	1.479 (12)
Tb1—N1	2.515 (7)	C29—C30	1.382 (12)
Tb1—N6	2.531 (7)	C29—H29	0.9500
Tb1—N2	2.558 (8)	C30—C31	1.400 (12)
Tb1—Cl1	2.633 (3)	C30—C47	1.517 (13)
N1—C1	1.333 (11)	C31—C32	1.378 (12)
N1—C5	1.351 (11)	C31—H31	0.9500
N2—C10	1.341 (13)	C32—C33	1.485 (11)
N2—C6	1.365 (11)	C33—C34	1.384 (12)
N3—C15	1.331 (11)	C34—C35	1.425 (12)
N3—C11	1.366 (11)	C34—H34	0.9500
N4—C28	1.344 (10)	C35—C36	1.370 (13)
N4—C32	1.351 (11)	C35—C43	1.535 (13)
N5—C37	1.339 (11)	C36—C37	1.412 (13)
N5—C33	1.358 (11)	C36—H36	0.9500
N6—C38	1.343 (11)	C37—H37	0.9500
N6—C42	1.354 (12)	C38—C39	1.378 (12)
C1—C2	1.397 (13)	C39—C40	1.394 (12)
C1—C11	1.525 (12)	C39—H39	0.9500
C2—C3	1.388 (12)	C40—C41	1.392 (13)
C2—H2	0.9500	C40—C51	1.527 (13)
C3—C4	1.395 (13)	C41—C42	1.384 (14)
C3—C20	1.517 (13)	C41—H41	0.9500
C4—C5	1.360 (12)	C42—H42	0.9500
C4—H4	0.9500	C43—C45	1.519 (14)
C5—C6	1.495 (12)	C43—C46	1.526 (15)
C6—C7	1.371 (12)	C43—C44	1.539 (14)
C7—C8	1.392 (13)	C44—H44A	0.9800
C7—H7	0.9500	C44—H44B	0.9800
C8—C9	1.351 (14)	C44—H44C	0.9800
C8—C16	1.539 (13)	C45—H45A	0.9800
C9—C10	1.382 (14)	C45—H45B	0.9800
C9—H9	0.9500	C45—H45C	0.9800
C10—H10	0.9500	C46—H46A	0.9800
C11—C12	1.395 (12)	C46—H46B	0.9800
C12—C13	1.393 (13)	C46—H46C	0.9800
C12—H12	0.9500	C47—C48	1.528 (13)
C13—C14	1.385 (13)	C47—C49	1.534 (13)
C13—C24	1.530 (14)	C47—C50	1.550 (12)
C14—C15	1.377 (12)	C48—H48A	0.9800
C14—H14	0.9500	C48—H48B	0.9800
C15—H15	0.9500	C48—H48C	0.9800
C16—C19	1.530 (13)	C49—H49A	0.9800
C16—C18	1.532 (15)	C49—H49B	0.9800
C16—C17	1.549 (15)	C49—H49C	0.9800
C17—H17A	0.9800	C50—H50A	0.9800
C17—H17B	0.9800	C50—H50B	0.9800
C17—H17C	0.9800	C50—H50C	0.9800
C18—H18A	0.9800	C51—C53	1.521 (12)
C18—H18B	0.9800	C51—C54	1.534 (14)
C18—H18C	0.9800	C51—C52	1.539 (14)
C19—H19A	0.9800	C52—H52A	0.9800
C19—H19B	0.9800	C52—H52B	0.9800
C19—H19C	0.9800	C52—H52C	0.9800
C20—C22	1.511 (13)	C53—H53A	0.9800
C20—C23	1.524 (15)	C53—H53B	0.9800
C20—C21	1.559 (14)	C53—H53C	0.9800
C21—H21A	0.9800	C54—H54A	0.9800
C21—H21B	0.9800	C54—H54B	0.9800
C21—H21C	0.9800	C54—H54C	0.9800
C22—H22A	0.9800	Cl2—O4	1.434 (7)
C22—H22B	0.9800	Cl2—O2	1.435 (6)
C22—H22C	0.9800	Cl2—O5	1.438 (7)
C23—H23A	0.9800	Cl2—O3	1.449 (8)
C23—H23B	0.9800	Cl3—O8	1.402 (9)
C23—H23C	0.9800	Cl3—O6	1.416 (7)
C24—C26	1.535 (14)	Cl3—O7	1.428 (8)
C24—C27	1.539 (14)	Cl3—O9	1.430 (11)
C24—C25	1.553 (16)	O10—C55	1.306 (13)
C25—H25A	0.9800	C55—C56	1.422 (17)
C25—H25B	0.9800	O11A—C57A	1.383 (19)
C25—H25C	0.9800	C57A—C58A	1.506 (19)
C26—H26A	0.9800	O11B—C57B	1.403 (19)
C26—H26B	0.9800	C57B—C58B	1.492 (19)
C26—H26C	0.9800	O11C—C57C	1.45 (4)
C27—H27A	0.9800	C57C—C58C	1.54 (2)
O1—Tb1—N3	100.6 (2)	C24—C25—H25C	109.5
O1—Tb1—N4	142.5 (2)	H25A—C25—H25C	109.5
N3—Tb1—N4	82.8 (2)	H25B—C25—H25C	109.5
O1—Tb1—N5	152.7 (2)	C24—C26—H26A	109.5
N3—Tb1—N5	87.7 (2)	C24—C26—H26B	109.5
N4—Tb1—N5	63.9 (2)	H26A—C26—H26B	109.5
O1—Tb1—N1	75.6 (2)	C24—C26—H26C	109.5
N3—Tb1—N1	64.8 (2)	H26A—C26—H26C	109.5
N4—Tb1—N1	135.9 (2)	H26B—C26—H26C	109.5
N5—Tb1—N1	84.8 (2)	C24—C27—H27A	109.5
O1—Tb1—N6	79.4 (2)	C24—C27—H27B	109.5
N3—Tb1—N6	76.2 (2)	H27A—C27—H27B	109.5
N4—Tb1—N6	65.1 (2)	C24—C27—H27C	109.5
N5—Tb1—N6	127.9 (2)	H27A—C27—H27C	109.5
N1—Tb1—N6	127.9 (2)	H27B—C27—H27C	109.5
O1—Tb1—N2	75.5 (2)	N4—C28—C29	121.8 (8)
N3—Tb1—N2	128.1 (2)	N4—C28—C38	117.7 (8)
N4—Tb1—N2	131.2 (2)	C29—C28—C38	120.5 (7)
N5—Tb1—N2	78.9 (2)	C30—C29—C28	121.4 (7)
N1—Tb1—N2	64.2 (2)	C30—C29—H29	119.3
N6—Tb1—N2	147.7 (2)	C28—C29—H29	119.3
O1—Tb1—Cl1	85.52 (19)	C29—C30—C31	115.1 (8)
N3—Tb1—Cl1	151.87 (17)	C29—C30—C47	123.4 (7)
N4—Tb1—Cl1	76.22 (17)	C31—C30—C47	121.5 (8)
N5—Tb1—Cl1	99.41 (19)	C32—C31—C30	122.0 (8)
N1—Tb1—Cl1	142.61 (18)	C32—C31—H31	119.0
N6—Tb1—Cl1	78.08 (18)	C30—C31—H31	119.0
N2—Tb1—Cl1	80.07 (18)	N4—C32—C31	121.4 (7)
C1—N1—C5	115.9 (8)	N4—C32—C33	115.8 (8)
C1—N1—Tb1	120.8 (6)	C31—C32—C33	122.7 (8)
C5—N1—Tb1	120.5 (5)	N5—C33—C34	122.4 (7)
C10—N2—C6	115.0 (8)	N5—C33—C32	115.3 (7)
C10—N2—Tb1	124.8 (6)	C34—C33—C32	122.2 (8)
C6—N2—Tb1	120.0 (6)	C33—C34—C35	120.5 (8)
C15—N3—C11	114.5 (8)	C33—C34—H34	119.8
C15—N3—Tb1	124.1 (6)	C35—C34—H34	119.8
C11—N3—Tb1	121.4 (6)	C36—C35—C34	116.1 (8)
C28—N4—C32	118.2 (8)	C36—C35—C43	124.7 (8)
C28—N4—Tb1	118.8 (5)	C34—C35—C43	119.2 (9)
C32—N4—Tb1	121.0 (5)	C35—C36—C37	120.7 (8)
C37—N5—C33	117.5 (7)	C35—C36—H36	119.7
C37—N5—Tb1	120.9 (6)	C37—C36—H36	119.7
C33—N5—Tb1	121.4 (5)	N5—C37—C36	122.8 (9)
C38—N6—C42	116.4 (8)	N5—C37—H37	118.6
C38—N6—Tb1	119.8 (5)	C36—C37—H37	118.6
C42—N6—Tb1	123.7 (6)	N6—C38—C39	122.6 (8)
N1—C1—C2	124.7 (8)	N6—C38—C28	116.2 (7)
N1—C1—C11	115.4 (8)	C39—C38—C28	121.0 (8)
C2—C1—C11	119.9 (8)	C38—C39—C40	121.2 (9)
C3—C2—C1	118.4 (9)	C38—C39—H39	119.4
C3—C2—H2	120.8	C40—C39—H39	119.4
C1—C2—H2	120.8	C41—C40—C39	116.3 (8)
C2—C3—C4	116.7 (9)	C41—C40—C51	121.3 (8)
C2—C3—C20	122.8 (9)	C39—C40—C51	122.4 (8)
C4—C3—C20	120.5 (9)	C42—C41—C40	119.4 (9)
C5—C4—C3	121.0 (9)	C42—C41—H41	120.3
C5—C4—H4	119.5	C40—C41—H41	120.3
C3—C4—H4	119.5	N6—C42—C41	124.0 (9)
N1—C5—C4	123.2 (9)	N6—C42—H42	118.0
N1—C5—C6	116.7 (8)	C41—C42—H42	118.0
C4—C5—C6	120.0 (9)	C45—C43—C46	110.9 (9)
N2—C6—C7	122.5 (8)	C45—C43—C35	110.9 (7)
N2—C6—C5	115.5 (8)	C46—C43—C35	109.1 (9)
C7—C6—C5	122.0 (8)	C45—C43—C44	109.0 (9)
C6—C7—C8	121.1 (9)	C46—C43—C44	110.2 (9)
C6—C7—H7	119.4	C35—C43—C44	106.7 (8)
C8—C7—H7	119.4	C43—C44—H44A	109.5
C9—C8—C7	116.5 (9)	C43—C44—H44B	109.5
C9—C8—C16	121.2 (9)	H44A—C44—H44B	109.5
C7—C8—C16	122.1 (9)	C43—C44—H44C	109.5
C8—C9—C10	120.2 (10)	H44A—C44—H44C	109.5
C8—C9—H9	119.9	H44B—C44—H44C	109.5
C10—C9—H9	119.9	C43—C45—H45A	109.5
N2—C10—C9	124.5 (10)	C43—C45—H45B	109.5
N2—C10—H10	117.7	H45A—C45—H45B	109.5
C9—C10—H10	117.7	C43—C45—H45C	109.5
N3—C11—C12	122.9 (8)	H45A—C45—H45C	109.5
N3—C11—C1	114.8 (8)	H45B—C45—H45C	109.5
C12—C11—C1	122.3 (8)	C43—C46—H46A	109.5
C13—C12—C11	120.4 (8)	C43—C46—H46B	109.5
C13—C12—H12	119.8	H46A—C46—H46B	109.5
C11—C12—H12	119.8	C43—C46—H46C	109.5
C14—C13—C12	116.8 (8)	H46A—C46—H46C	109.5
C14—C13—C24	123.5 (9)	H46B—C46—H46C	109.5
C12—C13—C24	119.7 (8)	C30—C47—C48	108.8 (7)
C15—C14—C13	118.7 (9)	C30—C47—C49	109.4 (8)
C15—C14—H14	120.6	C48—C47—C49	110.4 (7)
C13—C14—H14	120.6	C30—C47—C50	111.5 (7)
N3—C15—C14	126.7 (9)	C48—C47—C50	107.5 (8)
N3—C15—H15	116.7	C49—C47—C50	109.3 (8)
C14—C15—H15	116.7	C47—C48—H48A	109.5
C19—C16—C18	109.9 (10)	C47—C48—H48B	109.5
C19—C16—C8	109.5 (8)	H48A—C48—H48B	109.5
C18—C16—C8	109.7 (9)	C47—C48—H48C	109.5
C19—C16—C17	109.4 (10)	H48A—C48—H48C	109.5
C18—C16—C17	106.3 (9)	H48B—C48—H48C	109.5
C8—C16—C17	112.0 (8)	C47—C49—H49A	109.5
C16—C17—H17A	109.5	C47—C49—H49B	109.5
C16—C17—H17B	109.5	H49A—C49—H49B	109.5
H17A—C17—H17B	109.5	C47—C49—H49C	109.5
C16—C17—H17C	109.5	H49A—C49—H49C	109.5
H17A—C17—H17C	109.5	H49B—C49—H49C	109.5
H17B—C17—H17C	109.5	C47—C50—H50A	109.5
C16—C18—H18A	109.5	C47—C50—H50B	109.5
C16—C18—H18B	109.5	H50A—C50—H50B	109.5
H18A—C18—H18B	109.5	C47—C50—H50C	109.5
C16—C18—H18C	109.5	H50A—C50—H50C	109.5
H18A—C18—H18C	109.5	H50B—C50—H50C	109.5
H18B—C18—H18C	109.5	C53—C51—C40	109.8 (8)
C16—C19—H19A	109.5	C53—C51—C54	109.3 (8)
C16—C19—H19B	109.5	C40—C51—C54	107.9 (8)
H19A—C19—H19B	109.5	C53—C51—C52	108.6 (8)
C16—C19—H19C	109.5	C40—C51—C52	112.5 (8)
H19A—C19—H19C	109.5	C54—C51—C52	108.6 (9)
H19B—C19—H19C	109.5	C51—C52—H52A	109.5
C22—C20—C3	107.2 (8)	C51—C52—H52B	109.5
C22—C20—C23	108.3 (9)	H52A—C52—H52B	109.5
C3—C20—C23	112.4 (9)	C51—C52—H52C	109.5
C22—C20—C21	110.5 (9)	H52A—C52—H52C	109.5
C3—C20—C21	110.9 (8)	H52B—C52—H52C	109.5
C23—C20—C21	107.4 (9)	C51—C53—H53A	109.5
C20—C21—H21A	109.5	C51—C53—H53B	109.5
C20—C21—H21B	109.5	H53A—C53—H53B	109.5
H21A—C21—H21B	109.5	C51—C53—H53C	109.5
C20—C21—H21C	109.5	H53A—C53—H53C	109.5
H21A—C21—H21C	109.5	H53B—C53—H53C	109.5
H21B—C21—H21C	109.5	C51—C54—H54A	109.5
C20—C22—H22A	109.5	C51—C54—H54B	109.5
C20—C22—H22B	109.5	H54A—C54—H54B	109.5
H22A—C22—H22B	109.5	C51—C54—H54C	109.5
C20—C22—H22C	109.5	H54A—C54—H54C	109.5
H22A—C22—H22C	109.5	H54B—C54—H54C	109.5
H22B—C22—H22C	109.5	O4—Cl2—O2	109.4 (4)
C20—C23—H23A	109.5	O4—Cl2—O5	109.8 (4)
C20—C23—H23B	109.5	O2—Cl2—O5	110.1 (4)
H23A—C23—H23B	109.5	O4—Cl2—O3	110.0 (5)
C20—C23—H23C	109.5	O2—Cl2—O3	107.7 (4)
H23A—C23—H23C	109.5	O5—Cl2—O3	109.8 (5)
H23B—C23—H23C	109.5	O8—Cl3—O6	109.2 (6)
C13—C24—C26	111.1 (8)	O8—Cl3—O7	109.9 (7)
C13—C24—C27	107.7 (9)	O6—Cl3—O7	110.3 (5)
C26—C24—C27	110.7 (8)	O8—Cl3—O9	111.1 (8)
C13—C24—C25	108.1 (8)	O6—Cl3—O9	108.3 (6)
C26—C24—C25	108.6 (9)	O7—Cl3—O9	108.0 (6)
C27—C24—C25	110.6 (10)	O10—C55—C56	107.3 (17)
C24—C25—H25A	109.5	O11A—C57A—C58A	114 (2)
C24—C25—H25B	109.5	O11B—C57B—C58B	112 (2)
H25A—C25—H25B	109.5	O11C—C57C—C58C	106 (3)
O1—Tb1—N1—C1	−95.7 (6)	C6—C7—C8—C9	0.8 (13)
N3—Tb1—N1—C1	13.6 (6)	C6—C7—C8—C16	−175.0 (8)
N4—Tb1—N1—C1	60.2 (7)	C7—C8—C9—C10	1.9 (14)
N5—Tb1—N1—C1	103.5 (6)	C16—C8—C9—C10	177.7 (8)
N6—Tb1—N1—C1	−31.8 (7)	C6—N2—C10—C9	4.6 (13)
N2—Tb1—N1—C1	−176.3 (7)	Tb1—N2—C10—C9	−169.3 (6)
Cl1—Tb1—N1—C1	−157.8 (5)	C8—C9—C10—N2	−4.9 (15)
O1—Tb1—N1—C5	64.8 (6)	C15—N3—C11—C12	−1.8 (12)
N3—Tb1—N1—C5	174.1 (7)	Tb1—N3—C11—C12	177.7 (6)
N4—Tb1—N1—C5	−139.3 (6)	C15—N3—C11—C1	177.8 (7)
N5—Tb1—N1—C5	−96.0 (6)	Tb1—N3—C11—C1	−2.7 (9)
N6—Tb1—N1—C5	128.7 (6)	N1—C1—C11—N3	14.7 (10)
N2—Tb1—N1—C5	−15.8 (6)	C2—C1—C11—N3	−167.3 (7)
Cl1—Tb1—N1—C5	2.7 (8)	N1—C1—C11—C12	−165.8 (8)
O1—Tb1—N2—C10	104.6 (7)	C2—C1—C11—C12	12.3 (12)
N3—Tb1—N2—C10	−163.1 (6)	N3—C11—C12—C13	0.5 (13)
N4—Tb1—N2—C10	−45.0 (8)	C1—C11—C12—C13	−179.1 (8)
N5—Tb1—N2—C10	−85.0 (7)	C11—C12—C13—C14	0.4 (13)
N1—Tb1—N2—C10	−174.6 (7)	C11—C12—C13—C24	179.4 (9)
N6—Tb1—N2—C10	64.7 (9)	C12—C13—C14—C15	0.2 (13)
Cl1—Tb1—N2—C10	16.7 (7)	C24—C13—C14—C15	−178.7 (9)
O1—Tb1—N2—C6	−69.1 (6)	C11—N3—C15—C14	2.5 (13)
N3—Tb1—N2—C6	23.2 (7)	Tb1—N3—C15—C14	−177.0 (7)
N4—Tb1—N2—C6	141.3 (6)	C13—C14—C15—N3	−1.8 (15)
N5—Tb1—N2—C6	101.3 (6)	C9—C8—C16—C19	−59.6 (13)
N1—Tb1—N2—C6	11.7 (6)	C7—C8—C16—C19	116.0 (11)
N6—Tb1—N2—C6	−109.0 (7)	C9—C8—C16—C18	61.1 (12)
Cl1—Tb1—N2—C6	−157.0 (6)	C7—C8—C16—C18	−123.3 (11)
O1—Tb1—N3—C15	−116.9 (7)	C9—C8—C16—C17	178.8 (9)
N4—Tb1—N3—C15	25.3 (7)	C7—C8—C16—C17	−5.6 (12)
N5—Tb1—N3—C15	89.3 (7)	C2—C3—C20—C22	−92.6 (10)
N1—Tb1—N3—C15	174.6 (7)	C4—C3—C20—C22	86.9 (10)
N6—Tb1—N3—C15	−40.8 (7)	C2—C3—C20—C23	26.3 (12)
N2—Tb1—N3—C15	163.3 (6)	C4—C3—C20—C23	−154.2 (9)
Cl1—Tb1—N3—C15	−16.4 (9)	C2—C3—C20—C21	146.6 (9)
O1—Tb1—N3—C11	63.6 (6)	C4—C3—C20—C21	−33.9 (12)
N4—Tb1—N3—C11	−154.2 (6)	C14—C13—C24—C26	0.1 (14)
N5—Tb1—N3—C11	−90.2 (6)	C12—C13—C24—C26	−178.8 (9)
N1—Tb1—N3—C11	−4.8 (6)	C14—C13—C24—C27	−121.3 (10)
N6—Tb1—N3—C11	139.8 (7)	C12—C13—C24—C27	59.8 (12)
N2—Tb1—N3—C11	−16.2 (7)	C14—C13—C24—C25	119.1 (11)
Cl1—Tb1—N3—C11	164.1 (5)	C12—C13—C24—C25	−59.8 (12)
O1—Tb1—N4—C28	7.0 (8)	C32—N4—C28—C29	1.0 (11)
N3—Tb1—N4—C28	−91.0 (6)	Tb1—N4—C28—C29	−163.3 (6)
N5—Tb1—N4—C28	178.0 (7)	C32—N4—C28—C38	−177.0 (7)
N1—Tb1—N4—C28	−132.5 (6)	Tb1—N4—C28—C38	18.7 (9)
N6—Tb1—N4—C28	−13.0 (6)	N4—C28—C29—C30	−3.5 (12)
N2—Tb1—N4—C28	133.3 (6)	C38—C28—C29—C30	174.4 (7)
Cl1—Tb1—N4—C28	70.1 (6)	C28—C29—C30—C31	3.5 (12)
O1—Tb1—N4—C32	−156.9 (5)	C28—C29—C30—C47	−174.0 (8)
N3—Tb1—N4—C32	105.1 (6)	C29—C30—C31—C32	−1.4 (12)
N5—Tb1—N4—C32	14.1 (5)	C47—C30—C31—C32	176.2 (8)
N1—Tb1—N4—C32	63.6 (7)	C28—N4—C32—C31	1.2 (12)
N6—Tb1—N4—C32	−176.8 (6)	Tb1—N4—C32—C31	165.1 (6)
N2—Tb1—N4—C32	−30.5 (7)	C28—N4—C32—C33	−179.6 (7)
Cl1—Tb1—N4—C32	−93.8 (6)	Tb1—N4—C32—C33	−15.6 (9)
O1—Tb1—N5—C37	−18.2 (10)	C30—C31—C32—N4	−1.0 (13)
N3—Tb1—N5—C37	90.7 (7)	C30—C31—C32—C33	179.8 (8)
N4—Tb1—N5—C37	173.8 (7)	C37—N5—C33—C34	1.0 (12)
N1—Tb1—N5—C37	25.8 (7)	Tb1—N5—C33—C34	−173.9 (6)
N6—Tb1—N5—C37	161.1 (6)	C37—N5—C33—C32	−176.6 (7)
N2—Tb1—N5—C37	−38.9 (7)	Tb1—N5—C33—C32	8.6 (10)
Cl1—Tb1—N5—C37	−116.7 (7)	N4—C32—C33—N5	4.5 (11)
O1—Tb1—N5—C33	156.5 (6)	C31—C32—C33—N5	−176.3 (8)
N3—Tb1—N5—C33	−94.6 (7)	N4—C32—C33—C34	−173.0 (7)
N4—Tb1—N5—C33	−11.5 (6)	C31—C32—C33—C34	6.2 (12)
N1—Tb1—N5—C33	−159.5 (7)	N5—C33—C34—C35	−0.3 (12)
N6—Tb1—N5—C33	−24.2 (8)	C32—C33—C34—C35	177.0 (8)
N2—Tb1—N5—C33	135.8 (7)	C33—C34—C35—C36	0.4 (12)
Cl1—Tb1—N5—C33	58.0 (6)	C33—C34—C35—C43	178.4 (8)
O1—Tb1—N6—C38	−161.7 (6)	C34—C35—C36—C37	−1.3 (13)
N3—Tb1—N6—C38	94.5 (6)	C43—C35—C36—C37	−179.1 (9)
N4—Tb1—N6—C38	6.2 (6)	C33—N5—C37—C36	−1.8 (13)
N5—Tb1—N6—C38	18.7 (7)	Tb1—N5—C37—C36	173.1 (6)
N1—Tb1—N6—C38	136.1 (6)	C35—C36—C37—N5	2.0 (14)
N2—Tb1—N6—C38	−122.4 (7)	C42—N6—C38—C39	0.7 (12)
Cl1—Tb1—N6—C38	−74.0 (6)	Tb1—N6—C38—C39	−175.5 (6)
O1—Tb1—N6—C42	22.4 (7)	C42—N6—C38—C28	176.6 (8)
N3—Tb1—N6—C42	−81.4 (7)	Tb1—N6—C38—C28	0.4 (10)
N4—Tb1—N6—C42	−169.8 (8)	N4—C28—C38—N6	−12.5 (11)
N5—Tb1—N6—C42	−157.3 (7)	C29—C28—C38—N6	169.4 (7)
N1—Tb1—N6—C42	−39.8 (8)	N4—C28—C38—C39	163.4 (8)
N2—Tb1—N6—C42	61.7 (9)	C29—C28—C38—C39	−14.6 (12)
Cl1—Tb1—N6—C42	110.0 (7)	N6—C38—C39—C40	−0.8 (13)
C5—N1—C1—C2	0.6 (11)	C28—C38—C39—C40	−176.5 (7)
Tb1—N1—C1—C2	162.0 (6)	C38—C39—C40—C41	−0.7 (12)
C5—N1—C1—C11	178.5 (7)	C38—C39—C40—C51	178.3 (8)
Tb1—N1—C1—C11	−20.1 (9)	C39—C40—C41—C42	2.2 (14)
N1—C1—C2—C3	0.6 (12)	C51—C40—C41—C42	−176.8 (9)
C11—C1—C2—C3	−177.2 (7)	C38—N6—C42—C41	1.0 (14)
C1—C2—C3—C4	−0.4 (11)	Tb1—N6—C42—C41	177.0 (8)
C1—C2—C3—C20	179.1 (8)	C40—C41—C42—N6	−2.5 (16)
C2—C3—C4—C5	−1.0 (12)	C36—C35—C43—C45	124.6 (10)
C20—C3—C4—C5	179.5 (8)	C34—C35—C43—C45	−53.3 (12)
C1—N1—C5—C4	−2.1 (12)	C36—C35—C43—C46	2.2 (14)
Tb1—N1—C5—C4	−163.5 (6)	C34—C35—C43—C46	−175.6 (9)
C1—N1—C5—C6	179.9 (7)	C36—C35—C43—C44	−116.8 (11)
Tb1—N1—C5—C6	18.5 (10)	C34—C35—C43—C44	65.4 (11)
C3—C4—C5—N1	2.3 (13)	C29—C30—C47—C48	112.6 (9)
C3—C4—C5—C6	−179.7 (8)	C31—C30—C47—C48	−64.8 (11)
C10—N2—C6—C7	−1.7 (12)	C29—C30—C47—C49	−126.7 (9)
Tb1—N2—C6—C7	172.6 (6)	C31—C30—C47—C49	55.9 (10)
C10—N2—C6—C5	178.1 (7)	C29—C30—C47—C50	−5.7 (12)
Tb1—N2—C6—C5	−7.6 (9)	C31—C30—C47—C50	176.9 (8)
N1—C5—C6—N2	−6.9 (11)	C41—C40—C51—C53	−53.6 (12)
C4—C5—C6—N2	175.1 (8)	C39—C40—C51—C53	127.4 (9)
N1—C5—C6—C7	173.0 (8)	C41—C40—C51—C54	65.5 (11)
C4—C5—C6—C7	−5.1 (12)	C39—C40—C51—C54	−113.5 (10)
N2—C6—C7—C8	−0.9 (13)	C41—C40—C51—C52	−174.7 (9)
C5—C6—C7—C8	179.2 (8)	C39—C40—C51—C52	6.3 (12)