Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009939/dn1012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009939/dn1012Isup2.hkl |
CCDC reference: 193399
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.
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?
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.
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. |
[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) Å3 | Prismatic, colourless |
Z = 4 | 0.25 × 0.20 × 0.17 mm |
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 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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.203 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.1083P)2] where P = (Fo2 + 2Fc2)/3 |
10324 reflections | (Δ/σ)max = 0.001 |
721 parameters | Δρmax = 1.44 e Å−3 |
11 restraints | Δρmin = −1.09 e Å−3 |
[Tb(C27H35N3)2Cl(H2O)](ClO4)2·2C2H6O | V = 6481 (2) Å3 |
Mr = 1306.58 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.392 (3) Å | µ = 1.27 mm−1 |
b = 21.233 (4) Å | T = 143 K |
c = 22.172 (4) Å | 0.25 × 0.20 × 0.17 mm |
β = 106.95 (3)° |
MAR345 IPDS diffractometer | 5193 reflections with I > 2σ(I) |
34863 measured reflections | Rint = 0.066 |
10324 independent reflections |
R[F2 > 2σ(F2)] = 0.065 | 11 restraints |
wR(F2) = 0.203 | H-atom parameters constrained |
S = 0.97 | Δρmax = 1.44 e Å−3 |
10324 reflections | Δρmin = −1.09 e Å−3 |
721 parameters |
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. |
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 |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
Crystal data | |
Chemical formula | [Tb(C27H35N3)2Cl(H2O)](ClO4)2·2C2H6O |
Mr | 1306.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 143 |
a, b, c (Å) | 14.392 (3), 21.233 (4), 22.172 (4) |
β (°) | 106.95 (3) |
V (Å3) | 6481 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.25 × 0.20 × 0.17 |
Data collection | |
Diffractometer | MAR345 IPDS diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34863, 10324, 5193 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.581 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.203, 0.97 |
No. of reflections | 10324 |
No. of parameters | 721 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.44, −1.09 |
Computer programs: MAR345 Software (marresearch, 19??), marHKL (release 1.9.1), based on HKL (Otwinowski & Minor, 1997), marHKL, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Tb1—O1 | 2.383 (6) | Tb1—N1 | 2.515 (7) |
Tb1—N3 | 2.503 (7) | Tb1—N6 | 2.531 (7) |
Tb1—N4 | 2.506 (7) | Tb1—N2 | 2.558 (8) |
Tb1—N5 | 2.510 (7) | Tb1—Cl1 | 2.633 (3) |
O1—Tb1—N3 | 100.6 (2) | N1—Tb1—N6 | 127.9 (2) |
O1—Tb1—N4 | 142.5 (2) | O1—Tb1—N2 | 75.5 (2) |
N3—Tb1—N4 | 82.8 (2) | N3—Tb1—N2 | 128.1 (2) |
O1—Tb1—N5 | 152.7 (2) | N4—Tb1—N2 | 131.2 (2) |
N3—Tb1—N5 | 87.7 (2) | N5—Tb1—N2 | 78.9 (2) |
N4—Tb1—N5 | 63.9 (2) | N1—Tb1—N2 | 64.2 (2) |
O1—Tb1—N1 | 75.6 (2) | N6—Tb1—N2 | 147.7 (2) |
N3—Tb1—N1 | 64.8 (2) | O1—Tb1—Cl1 | 85.52 (19) |
N4—Tb1—N1 | 135.9 (2) | N3—Tb1—Cl1 | 151.87 (17) |
N5—Tb1—N1 | 84.8 (2) | N4—Tb1—Cl1 | 76.22 (17) |
O1—Tb1—N6 | 79.4 (2) | N5—Tb1—Cl1 | 99.41 (19) |
N3—Tb1—N6 | 76.2 (2) | N1—Tb1—Cl1 | 142.61 (18) |
N4—Tb1—N6 | 65.1 (2) | N6—Tb1—Cl1 | 78.08 (18) |
N5—Tb1—N6 | 127.9 (2) | N2—Tb1—Cl1 | 80.07 (18) |
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 EuIII and, particularly, with TbIII. 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 LaIII and an anionic species with 11-coordinate LaIII (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 LaIII 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 TbIII 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 TbIII 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 TbIII can be described as a distorted bicapped trigonal prism (Porai-Koshits & Aslanov, 1972).