Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017996/vj1111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017996/vj1111Isup2.hkl |
CCDC reference: 170160
Complex (I) was isolated from the reaction of LaCp'3 with one equivalent of benzenethiol in THF, followed by crystallization from a toluene–THF solution at 263 K. The complex is very sensitive to air and moisture; therefore, all manipulations were conducted under purified argon using Schlenk techniques. A crystal suitable for analysis was sealed in a thin-walled glass capillary.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I) showing 40% probability displacement ellipsoids and the atom-numbering scheme [symmetry code: (i) 1 - x, -y, -z]. H atoms have been omitted for clarity. |
[La2(C6H7)4(C6H5S)2(C4H8O)2]·2C4H8O | Dx = 1.406 Mg m−3 |
Mr = 1101.07 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1535 (11) Å | Cell parameters from 6888 reflections |
b = 17.337 (2) Å | θ = 4.7–52.7° |
c = 16.637 (2) Å | µ = 1.74 mm−1 |
β = 100.031 (2)° | T = 298 K |
V = 2599.8 (5) Å3 | Prismatic, colourless |
Z = 2 | 0.70 × 0.45 × 0.40 mm |
F(000) = 1120 |
Bruker SMART CCD area-detector diffractometer | 4585 independent reflections |
Radiation source: fine-focus sealed tube | 3679 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.345, Tmax = 0.498 | k = −16→20 |
10479 measured reflections | l = −16→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.045P)2 + 3.4381P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.003 |
4585 reflections | Δρmax = 0.63 e Å−3 |
272 parameters | Δρmin = −0.58 e Å−3 |
10 restraints | Extinction correction: SHELXL97, Fc*=3DkFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0025 (3) |
[La2(C6H7)4(C6H5S)2(C4H8O)2]·2C4H8O | V = 2599.8 (5) Å3 |
Mr = 1101.07 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.1535 (11) Å | µ = 1.74 mm−1 |
b = 17.337 (2) Å | T = 298 K |
c = 16.637 (2) Å | 0.70 × 0.45 × 0.40 mm |
β = 100.031 (2)° |
Bruker SMART CCD area-detector diffractometer | 4585 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3679 reflections with I > 2σ(I) |
Tmin = 0.345, Tmax = 0.498 | Rint = 0.025 |
10479 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 10 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.63 e Å−3 |
4585 reflections | Δρmin = −0.58 e Å−3 |
272 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 | ||
La1 | 0.60330 (3) | 0.063780 (14) | 0.135744 (15) | 0.04470 (13) | |
S1 | 0.56907 (17) | 0.06436 (7) | −0.04544 (8) | 0.0618 (4) | |
O1 | 0.7739 (4) | 0.1781 (2) | 0.1058 (2) | 0.0636 (9) | |
C1 | 0.4132 (14) | 0.0980 (7) | 0.2457 (7) | 0.128 (4) | |
H1A | 0.4117 | 0.0701 | 0.2967 | 0.153* | |
C2 | 0.3209 (11) | 0.0831 (6) | 0.1740 (11) | 0.139 (5) | |
H2A | 0.2420 | 0.0442 | 0.1662 | 0.167* | |
C3 | 0.3321 (8) | 0.1426 (7) | 0.1233 (5) | 0.110 (3) | |
H3A | 0.2637 | 0.1529 | 0.0723 | 0.132* | |
C4 | 0.4311 (8) | 0.1937 (4) | 0.1627 (6) | 0.091 (2) | |
H4A | 0.4464 | 0.2461 | 0.1438 | 0.109* | |
C5 | 0.4838 (8) | 0.1663 (6) | 0.2405 (5) | 0.101 (2) | |
C6 | 0.5797 (14) | 0.2051 (9) | 0.3101 (7) | 0.244 (9) | |
H6A | 0.5196 | 0.2367 | 0.3388 | 0.366* | |
H6B | 0.6514 | 0.2368 | 0.2900 | 0.366* | |
H6C | 0.6300 | 0.1669 | 0.3466 | 0.366* | |
C7 | 0.8943 (7) | 0.0266 (4) | 0.2154 (4) | 0.0814 (18) | |
H7A | 0.9830 | 0.0570 | 0.2114 | 0.098* | |
C8 | 0.8122 (9) | 0.0347 (5) | 0.2742 (4) | 0.095 (2) | |
H8A | 0.8357 | 0.0699 | 0.3207 | 0.115* | |
C9 | 0.7168 (9) | −0.0261 (6) | 0.2706 (5) | 0.099 (2) | |
H9A | 0.6624 | −0.0411 | 0.3140 | 0.119* | |
C10 | 0.7378 (8) | −0.0717 (3) | 0.2072 (5) | 0.089 (2) | |
H10A | 0.6978 | −0.1239 | 0.1969 | 0.106* | |
C11 | 0.8510 (7) | −0.0393 (4) | 0.1704 (4) | 0.0776 (17) | |
C12 | 0.9157 (11) | −0.0696 (6) | 0.0991 (6) | 0.150 (4) | |
H12A | 0.9976 | −0.1032 | 0.1187 | 0.225* | |
H12B | 0.9498 | −0.0271 | 0.0702 | 0.225* | |
H12C | 0.8411 | −0.0976 | 0.0630 | 0.225* | |
C13 | 0.5856 (5) | 0.1524 (3) | −0.0964 (3) | 0.0551 (12) | |
C14 | 0.6645 (7) | 0.1557 (4) | −0.1600 (4) | 0.0780 (16) | |
H14A | 0.7053 | 0.1109 | −0.1775 | 0.094* | |
C15 | 0.6832 (8) | 0.2255 (5) | −0.1979 (4) | 0.096 (2) | |
H15A | 0.7372 | 0.2272 | −0.2403 | 0.115* | |
C16 | 0.6242 (9) | 0.2905 (5) | −0.1740 (5) | 0.104 (3) | |
H16A | 0.6390 | 0.3371 | −0.1992 | 0.125* | |
C17 | 0.5424 (8) | 0.2886 (4) | −0.1127 (5) | 0.096 (2) | |
H17A | 0.4990 | 0.3334 | −0.0970 | 0.115* | |
C18 | 0.5245 (7) | 0.2194 (3) | −0.0742 (4) | 0.0766 (16) | |
H18A | 0.4696 | 0.2184 | −0.0321 | 0.092* | |
C19 | 0.7844 (9) | 0.2563 (4) | 0.1355 (5) | 0.108 (3) | |
H19A | 0.8220 | 0.2571 | 0.1937 | 0.130* | |
H19B | 0.6876 | 0.2807 | 0.1255 | 0.130* | |
C20 | 0.8863 (11) | 0.2972 (4) | 0.0914 (6) | 0.126 (3) | |
H20A | 0.9710 | 0.3165 | 0.1293 | 0.151* | |
H20B | 0.8364 | 0.3404 | 0.0614 | 0.151* | |
C21 | 0.9350 (9) | 0.2407 (4) | 0.0345 (5) | 0.104 (2) | |
H21A | 0.8853 | 0.2503 | −0.0210 | 0.125* | |
H21B | 1.0413 | 0.2441 | 0.0364 | 0.125* | |
C22 | 0.8949 (6) | 0.1657 (4) | 0.0619 (4) | 0.0801 (17) | |
H22A | 0.8642 | 0.1318 | 0.0157 | 0.096* | |
H22B | 0.9786 | 0.1424 | 0.0974 | 0.096* | |
O2 | 0.152 (3) | 0.9135 (10) | 0.3713 (9) | 0.405 (14) | |
C23 | 0.274 (3) | 0.9617 (13) | 0.3802 (13) | 0.340 (16) | |
H23A | 0.2706 | 0.9959 | 0.3338 | 0.408* | |
H23B | 0.3662 | 0.9331 | 0.3890 | 0.408* | |
C24 | 0.250 (3) | 1.0049 (8) | 0.4562 (16) | 0.358 (16) | |
H24A | 0.3327 | 1.0380 | 0.4781 | 0.429* | |
H24B | 0.1579 | 1.0338 | 0.4482 | 0.429* | |
C25 | 0.243 (3) | 0.9324 (15) | 0.5064 (8) | 0.364 (18) | |
H25A | 0.3400 | 0.9081 | 0.5204 | 0.437* | |
H25B | 0.2039 | 0.9426 | 0.5557 | 0.437* | |
C26 | 0.138 (3) | 0.8843 (10) | 0.4462 (14) | 0.313 (14) | |
H26A | 0.1653 | 0.8302 | 0.4504 | 0.375* | |
H26B | 0.0367 | 0.8896 | 0.4557 | 0.375* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.04480 (18) | 0.04271 (18) | 0.04795 (18) | 0.00054 (11) | 0.01188 (11) | −0.00308 (12) |
S1 | 0.0907 (10) | 0.0456 (7) | 0.0477 (6) | −0.0213 (6) | 0.0079 (6) | 0.0050 (5) |
O1 | 0.060 (2) | 0.056 (2) | 0.076 (2) | −0.0103 (17) | 0.0149 (17) | −0.0045 (17) |
C1 | 0.143 (9) | 0.133 (8) | 0.137 (8) | 0.052 (7) | 0.107 (7) | 0.041 (7) |
C2 | 0.078 (6) | 0.101 (7) | 0.264 (16) | −0.020 (5) | 0.104 (8) | −0.062 (9) |
C3 | 0.060 (4) | 0.157 (8) | 0.107 (6) | 0.046 (5) | −0.001 (4) | −0.044 (6) |
C4 | 0.088 (5) | 0.063 (4) | 0.134 (6) | 0.024 (4) | 0.057 (5) | −0.002 (4) |
C5 | 0.087 (5) | 0.124 (7) | 0.095 (5) | 0.012 (5) | 0.029 (4) | −0.051 (5) |
C6 | 0.179 (11) | 0.34 (2) | 0.189 (12) | 0.091 (12) | −0.036 (9) | −0.181 (13) |
C7 | 0.058 (3) | 0.086 (4) | 0.091 (5) | −0.008 (3) | −0.012 (3) | 0.016 (4) |
C8 | 0.106 (6) | 0.104 (5) | 0.065 (4) | 0.014 (5) | −0.018 (4) | −0.014 (4) |
C9 | 0.100 (5) | 0.126 (7) | 0.074 (4) | 0.022 (5) | 0.020 (4) | 0.042 (5) |
C10 | 0.078 (4) | 0.054 (4) | 0.123 (6) | −0.002 (3) | −0.014 (4) | 0.022 (4) |
C11 | 0.067 (4) | 0.083 (4) | 0.076 (4) | 0.027 (3) | −0.005 (3) | 0.000 (3) |
C12 | 0.140 (8) | 0.177 (10) | 0.132 (7) | 0.097 (7) | 0.019 (6) | −0.022 (6) |
C13 | 0.058 (3) | 0.050 (3) | 0.054 (3) | −0.016 (2) | 0.002 (2) | 0.012 (2) |
C14 | 0.087 (4) | 0.078 (4) | 0.073 (4) | −0.014 (3) | 0.025 (3) | 0.010 (3) |
C15 | 0.099 (5) | 0.106 (6) | 0.087 (5) | −0.028 (4) | 0.029 (4) | 0.032 (4) |
C16 | 0.102 (5) | 0.083 (5) | 0.118 (6) | −0.025 (4) | −0.008 (5) | 0.050 (5) |
C17 | 0.099 (5) | 0.058 (4) | 0.126 (6) | 0.004 (3) | 0.006 (5) | 0.019 (4) |
C18 | 0.085 (4) | 0.059 (3) | 0.086 (4) | 0.000 (3) | 0.016 (3) | 0.015 (3) |
C19 | 0.125 (6) | 0.067 (4) | 0.147 (7) | −0.029 (4) | 0.062 (5) | −0.031 (4) |
C20 | 0.157 (8) | 0.074 (5) | 0.156 (8) | −0.043 (5) | 0.053 (7) | −0.001 (5) |
C21 | 0.103 (5) | 0.090 (5) | 0.128 (6) | −0.023 (4) | 0.044 (5) | 0.006 (5) |
C22 | 0.058 (3) | 0.079 (4) | 0.108 (5) | −0.009 (3) | 0.030 (3) | −0.006 (3) |
O2 | 0.60 (4) | 0.30 (2) | 0.271 (19) | −0.14 (2) | −0.04 (2) | 0.085 (15) |
C23 | 0.49 (4) | 0.182 (18) | 0.41 (4) | −0.11 (2) | 0.24 (3) | 0.02 (2) |
C24 | 0.61 (5) | 0.126 (14) | 0.33 (3) | 0.00 (2) | 0.07 (3) | −0.057 (18) |
C25 | 0.55 (5) | 0.34 (4) | 0.148 (15) | −0.05 (3) | −0.08 (2) | 0.011 (18) |
C26 | 0.54 (4) | 0.210 (19) | 0.23 (2) | −0.14 (2) | 0.17 (3) | −0.033 (17) |
La1—C1 | 2.799 (7) | C12—H12A | 0.96 |
La1—C2 | 2.788 (7) | C12—H12B | 0.96 |
La1—C3 | 2.810 (6) | C12—H12C | 0.96 |
La1—C4 | 2.829 (6) | C13—C18 | 1.367 (8) |
La1—C5 | 2.839 (6) | C13—C14 | 1.382 (7) |
La1—C7 | 2.834 (6) | C14—C15 | 1.389 (9) |
La1—C8 | 2.772 (6) | C14—H14A | 0.93 |
La1—C9 | 2.781 (6) | C15—C16 | 1.339 (11) |
La1—C10 | 2.817 (6) | C15—H15A | 0.93 |
La1—C11 | 2.866 (5) | C16—C17 | 1.367 (11) |
La1—O1 | 2.624 (3) | C16—H16A | 0.93 |
La1—S1 | 2.9758 (13) | C17—C18 | 1.383 (8) |
S1—C13 | 1.766 (5) | C17—H17A | 0.93 |
S1—La1i | 2.9760 (13) | C18—H18A | 0.93 |
O1—C19 | 1.441 (7) | C19—C20 | 1.465 (10) |
O1—C22 | 1.444 (6) | C19—H19A | 0.97 |
C1—C5 | 1.359 (13) | C19—H19B | 0.97 |
C1—C2 | 1.361 (14) | C20—C21 | 1.483 (11) |
C1—H1A | 0.98 | C20—H20A | 0.97 |
C2—C3 | 1.347 (13) | C20—H20B | 0.97 |
C2—H2A | 0.98 | C21—C22 | 1.447 (9) |
C3—C4 | 1.351 (11) | C21—H21A | 0.97 |
C3—H3A | 0.98 | C21—H21B | 0.97 |
C4—C5 | 1.383 (11) | C22—H22A | 0.97 |
C4—H4A | 0.98 | C22—H22B | 0.97 |
C5—C6 | 1.487 (12) | O2—C26 | 1.37 (3) |
C6—H6A | 0.96 | O2—C23 | 1.38 (4) |
C6—H6B | 0.96 | C23—C24 | 1.52 (3) |
C6—H6C | 0.96 | C23—H23A | 0.97 |
C7—C8 | 1.342 (10) | C23—H23B | 0.97 |
C7—C11 | 1.385 (9) | C24—C25 | 1.52 (3) |
C7—H7A | 0.98 | C24—H24A | 0.97 |
C8—C9 | 1.363 (11) | C24—H24B | 0.97 |
C8—H8A | 0.98 | C25—C26 | 1.51 (3) |
C9—C10 | 1.359 (10) | C25—H25A | 0.97 |
C9—H9A | 0.98 | C25—H25B | 0.97 |
C10—C11 | 1.408 (10) | C26—H26A | 0.97 |
C10—H10A | 0.98 | C26—H26B | 0.97 |
C11—C12 | 1.510 (10) | ||
O1—La1—C8 | 87.0 (2) | H6A—C6—H6C | 109.5 |
O1—La1—C9 | 115.2 (2) | H6B—C6—H6C | 109.5 |
C8—La1—C9 | 28.4 (2) | C8—C7—C11 | 109.7 (6) |
O1—La1—C2 | 124.0 (2) | C8—C7—La1 | 73.6 (4) |
C8—La1—C2 | 111.4 (4) | C11—C7—La1 | 77.2 (3) |
C9—La1—C2 | 96.5 (4) | C8—C7—H7A | 124.7 |
O1—La1—C1 | 115.0 (3) | C11—C7—H7A | 124.7 |
C8—La1—C1 | 85.0 (3) | La1—C7—H7A | 124.7 |
C9—La1—C1 | 77.2 (3) | C7—C8—C9 | 108.9 (7) |
C2—La1—C1 | 28.2 (3) | C7—C8—La1 | 78.8 (4) |
O1—La1—C3 | 99.6 (3) | C9—C8—La1 | 76.1 (4) |
C8—La1—C3 | 128.5 (2) | C7—C8—H8A | 124.6 |
C9—La1—C3 | 122.2 (3) | C9—C8—H8A | 124.6 |
C2—La1—C3 | 27.8 (3) | La1—C8—H8A | 124.6 |
C1—La1—C3 | 45.8 (3) | C10—C9—C8 | 107.9 (7) |
O1—La1—C10 | 118.60 (16) | C10—C9—La1 | 77.4 (4) |
C8—La1—C10 | 46.4 (2) | C8—C9—La1 | 75.4 (4) |
C9—La1—C10 | 28.1 (2) | C10—C9—H9A | 125.2 |
C2—La1—C10 | 111.0 (4) | C8—C9—H9A | 125.2 |
C1—La1—C10 | 100.2 (3) | La1—C9—H9A | 125.2 |
C3—La1—C10 | 138.8 (3) | C9—C10—C11 | 108.7 (6) |
O1—La1—C4 | 78.21 (17) | C9—C10—La1 | 74.5 (4) |
C8—La1—C4 | 109.6 (3) | C11—C10—La1 | 77.6 (3) |
C9—La1—C4 | 117.3 (3) | C9—C10—H10A | 125.0 |
C2—La1—C4 | 45.9 (2) | C11—C10—H10A | 125.0 |
C1—La1—C4 | 45.6 (2) | La1—C10—H10A | 125.0 |
C3—La1—C4 | 27.7 (2) | C7—C11—C10 | 104.9 (6) |
C10—La1—C4 | 144.2 (3) | C7—C11—C12 | 126.6 (8) |
O1—La1—C7 | 73.65 (16) | C10—C11—C12 | 128.5 (8) |
C8—La1—C7 | 27.7 (2) | C7—C11—La1 | 74.7 (3) |
C9—La1—C7 | 46.1 (2) | C10—C11—La1 | 73.7 (3) |
C2—La1—C7 | 138.9 (4) | C12—C11—La1 | 117.6 (4) |
C1—La1—C7 | 112.5 (3) | C11—C12—H12A | 109.5 |
C3—La1—C7 | 153.0 (2) | C11—C12—H12B | 109.5 |
C10—La1—C7 | 46.15 (19) | H12A—C12—H12B | 109.5 |
C4—La1—C7 | 127.7 (2) | C11—C12—H12C | 109.5 |
O1—La1—C5 | 87.1 (2) | H12A—C12—H12C | 109.5 |
C8—La1—C5 | 83.5 (2) | H12B—C12—H12C | 109.5 |
C9—La1—C5 | 89.2 (3) | C18—C13—C14 | 117.8 (5) |
C2—La1—C5 | 46.6 (3) | C18—C13—S1 | 122.0 (4) |
C1—La1—C5 | 27.9 (3) | C14—C13—S1 | 120.2 (4) |
C3—La1—C5 | 46.4 (2) | C13—C14—C15 | 120.3 (6) |
C10—La1—C5 | 116.7 (3) | C13—C14—H14A | 119.9 |
C4—La1—C5 | 28.3 (2) | C15—C14—H14A | 119.9 |
C7—La1—C5 | 106.7 (2) | C16—C15—C14 | 120.8 (7) |
O1—La1—C11 | 91.88 (17) | C16—C15—H15A | 119.6 |
C8—La1—C11 | 46.5 (2) | C14—C15—H15A | 119.6 |
C9—La1—C11 | 46.9 (2) | C15—C16—C17 | 120.1 (6) |
C2—La1—C11 | 139.6 (4) | C15—C16—H16A | 119.9 |
C1—La1—C11 | 124.1 (2) | C17—C16—H16A | 119.9 |
C3—La1—C11 | 167.5 (3) | C16—C17—C18 | 119.4 (7) |
C10—La1—C11 | 28.7 (2) | C16—C17—H17A | 120.3 |
C4—La1—C11 | 155.2 (2) | C18—C17—H17A | 120.3 |
C7—La1—C11 | 28.13 (18) | C13—C18—C17 | 121.6 (6) |
C5—La1—C11 | 130.0 (2) | C13—C18—H18A | 119.2 |
O1—La1—S1 | 76.48 (8) | C17—C18—H18A | 119.2 |
C8—La1—S1 | 141.10 (18) | O1—C19—C20 | 107.1 (6) |
C9—La1—S1 | 141.1 (2) | O1—C19—H19A | 110.3 |
C2—La1—S1 | 107.0 (4) | C20—C19—H19A | 110.3 |
C1—La1—S1 | 133.9 (3) | O1—C19—H19B | 110.3 |
C3—La1—S1 | 89.33 (18) | C20—C19—H19B | 110.3 |
C10—La1—S1 | 113.03 (19) | H19A—C19—H19B | 108.5 |
C4—La1—S1 | 101.23 (19) | C19—C20—C21 | 106.7 (6) |
C7—La1—S1 | 113.50 (16) | C19—C20—H20A | 110.4 |
C5—La1—S1 | 129.5 (2) | C21—C20—H20A | 110.4 |
C11—La1—S1 | 98.39 (13) | C19—C20—H20B | 110.4 |
C13—S1—La1 | 119.13 (17) | C21—C20—H20B | 110.4 |
C13—S1—La1i | 119.03 (16) | H20A—C20—H20B | 108.6 |
La1—S1—La1i | 117.51 (4) | C22—C21—C20 | 105.7 (6) |
C19—O1—C22 | 107.6 (4) | C22—C21—H21A | 110.6 |
C19—O1—La1 | 130.7 (3) | C20—C21—H21A | 110.6 |
C22—O1—La1 | 121.2 (3) | C22—C21—H21B | 110.6 |
C5—C1—C2 | 109.8 (9) | C20—C21—H21B | 110.6 |
C5—C1—La1 | 77.7 (4) | H21A—C21—H21B | 108.7 |
C2—C1—La1 | 75.4 (4) | O1—C22—C21 | 106.5 (5) |
C5—C1—H1A | 124.4 | O1—C22—H22A | 110.4 |
C2—C1—H1A | 124.4 | C21—C22—H22A | 110.4 |
La1—C1—H1A | 124.4 | O1—C22—H22B | 110.4 |
C3—C2—C1 | 107.4 (9) | C21—C22—H22B | 110.4 |
C3—C2—La1 | 77.0 (4) | H22A—C22—H22B | 108.6 |
C1—C2—La1 | 76.4 (5) | C26—O2—C23 | 109.1 (9) |
C3—C2—H2A | 125.3 | O2—C23—C24 | 99.1 (10) |
C1—C2—H2A | 125.3 | O2—C23—H23A | 112.0 |
La1—C2—H2A | 125.3 | C24—C23—H23A | 111.9 |
C2—C3—C4 | 108.4 (9) | O2—C23—H23B | 112.0 |
C2—C3—La1 | 75.2 (4) | C24—C23—H23B | 111.9 |
C4—C3—La1 | 76.9 (4) | H23A—C23—H23B | 109.6 |
C2—C3—H3A | 125.1 | C25—C24—C23 | 94.3 (9) |
C4—C3—H3A | 125.1 | C25—C24—H24A | 112.9 |
La1—C3—H3A | 125.1 | C23—C24—H24A | 112.9 |
C3—C4—C5 | 108.9 (8) | C25—C24—H24B | 112.9 |
C3—C4—La1 | 75.4 (4) | C23—C24—H24B | 112.9 |
C5—C4—La1 | 76.3 (4) | H24A—C24—H24B | 110.3 |
C3—C4—H4A | 124.9 | C26—C25—C24 | 100.1 (9) |
C5—C4—H4A | 124.9 | C26—C25—H25A | 111.8 |
La1—C4—H4A | 124.9 | C24—C25—H25A | 111.8 |
C1—C5—C4 | 105.4 (8) | C26—C25—H25B | 111.8 |
C1—C5—C6 | 124.6 (12) | C24—C25—H25B | 111.8 |
C4—C5—C6 | 129.5 (11) | H25A—C25—H25B | 109.5 |
C1—C5—La1 | 74.4 (4) | O2—C26—C25 | 104.3 (8) |
C4—C5—La1 | 75.5 (3) | O2—C26—H26A | 110.9 |
C6—C5—La1 | 121.5 (6) | C25—C26—H26A | 110.9 |
C5—C6—H6A | 109.5 | O2—C26—H26B | 110.9 |
C5—C6—H6B | 109.5 | C25—C26—H26B | 110.9 |
H6A—C6—H6B | 109.5 | H26A—C26—H26B | 108.9 |
C5—C6—H6C | 109.5 |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [La2(C6H7)4(C6H5S)2(C4H8O)2]·2C4H8O |
Mr | 1101.07 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.1535 (11), 17.337 (2), 16.637 (2) |
β (°) | 100.031 (2) |
V (Å3) | 2599.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.70 × 0.45 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.345, 0.498 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10479, 4585, 3679 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.097, 1.07 |
No. of reflections | 4585 |
No. of parameters | 272 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.58 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
La1—C1 | 2.799 (7) | La1—C9 | 2.781 (6) |
La1—C2 | 2.788 (7) | La1—C10 | 2.817 (6) |
La1—C3 | 2.810 (6) | La1—C11 | 2.866 (5) |
La1—C4 | 2.829 (6) | La1—O1 | 2.624 (3) |
La1—C5 | 2.839 (6) | La1—S1 | 2.9758 (13) |
La1—C7 | 2.834 (6) | S1—La1i | 2.9760 (13) |
La1—C8 | 2.772 (6) |
Symmetry code: (i) −x+1, −y, −z. |
The synthesis of lanthanide–thiolate compounds is of current interest as these compounds are used in organic synthesis (Taniguchi et al., 1994), as rational molecular precursors to materials (Brewer et al., 1994) and as an initiator for syndiospecific polymerization of methyl methacrylate (Nakayama et al., 1996). While studying the catalytic properties of organolanthanide thiolates, we obtained di-µ-phenylthio-bis[bis(η5-methylcyclopentadienyl)(tetrahydrofuran)- lanthanum(III)] bis(tetrahydrofuran) solvate, (I), from the reaction of Cp'3La (Cp' is η5-methylcyclopentadienyl) with benzenethiol in a 1:1 molar ratio in tetrahydrofuran (THF). \sch
The crystal structure determination of (I) demonstrates that the complex is a centrosymmetric binuclear molecule, with the benzenethiol ligands as bridging groups. The La atom is coordinated by two Cp' rings, two benzenethiol S atoms and one THF O atom, forming a distorted trigonal-bipyramid geometry, giving the central metal a formal coordination number of nine if the Cp' group is regarded as occupying three coordination sites.
The two La—S distances in (I) are not equal (Table 1) and have an average value of 2.9759 Å, the average being consistent with that found in the related sulfur-bridged complex [Ce(Me3CC5H4)2(µ-SCHMe2)]2 [2.882 (6) Å; Stults et al., 1990], once the difference in the ionic radii of the metal atoms has been taken into consideration.
The La—S—La angle in (I) [117.51 (4)°] is larger than that found in the complex [Yb(C5H5)2(µ-SCH2CH2CH2CH3)]2, (II) [94.43 (8)°; Wu et al., 1996]. However, the S—La—S angle in (I) [62.5 (1)°] is much smaller than that found in (II) [85.57 (8)°]. The Cp'centroid—La distances in (I) [2.565 (7) and 2.562 (6) Å] are much longer than those observed for the Cp'centroid—Yb distances in (II) (2.315 and 2.412 Å). These differences may be due to the difference in the ionic radii of the metal atoms in (I) and (II).