Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034575/ya2055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034575/ya2055Isup2.hkl |
CCDC reference: 657611
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.007 Å
- R factor = 0.040
- wR factor = 0.095
- Data-to-parameter ratio = 21.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.24 Ratio
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.94
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.935 Tmax scaled 0.471 Tmin scaled 0.313
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A solution of LiDmp (0.81 g, 2.54 mmol) and Er(C5H4Me)3 (1.03 g, 2.54 mmol) in 20 ml of toluene was stirred for 14 h under an atmosphere of purified argon, after which all volatile materials were removed under reduced pressure. The remaining solid was extracted with a 1:4 mixture of toluene and n-heptane (ca 15 ml) and solid by-products were separated by filtration. Storage of the resulting pink solution in a 248 K freezer overnight afforded pale pink crystals of (I) (yield 61%), which were suitable for X-ray study.
m.p. 427–428 K (dec); EI—MS (70 eV, 420 K): m/z (%) 314.2 (100) [Dmp+], 324.0 (13) [{Er(C5H4Me)2}+], 558.2 (4.1)[{DmpErC5H4Me}+], 639.2 (2.6) [M+]. Anal. Calcd for C36H39Er: C, 67.67; H, 6.15. Found: C, 67.65; H, 6.30.
The H atoms were positioned geometrically at distances of 0.95 (Aryl-H), 0.98 (CH3) and 1.00 Å (MeC5H3—H) and refined in a riding model approximation, including free rotation for methyl groups. A common isotropic displacement parameter was refined for H atoms belonging to the CH (aryl), CH (C5H4Me) CH3 (Mes) and CH3 (C5H4Me) groups. The highest residual density of 1.05 e A°-3 and the deepest hole of -1.52 e A°-3 are located near the Er atom.
Although base-stabilized bis(cyclopentadienyl)lanthanide aryls of the composition ArLnCp'2(thf) (Cp' =Cp, Cp*) have been known for more than three decades and were extensively studied (Tsutsui & Ely, 1975; Schumann et al., 1995), the corresponding Lewis-donor-free systems received much less attention. Earlier we have reported the first structurally characterized examples of this type, which are kinetically stabilized by the bulky Dmp ligand (Niemeyer & Hauber, 1999).
The crystal structure of the title compound, (I), is made up of monomeric units (Fig.1). The erbium atom is coordinated by two η5-bonded methylcyclopentadienyl ligands (their centroids are X5 and X5') and the ipso carbon atom C11 of the Dmp substituent. With 2.434 (4) Å the Er—C11 bond length is practically identical to the average Er—C distance of 2.431 Å in the solvated erbium organyl [Er(Ph)3(thf)3] (Bochkarev et al.,1995). The metal-carbon distances to the η5-coordinated methylcyclopentadienyl rings [average Er–C = 2.629 Å] are typical for other bis(cyclopentadienyl) complexes (Schumann et al., 1995).
The most interesting aspect of the solid-state structure of (I) is additional metal-π-arene interaction (Bochkarev, 2002) involving the Er atom and one of the mesityl rings of the terphenyl substituent, which is reflected in dramatically different Er···C21 and Er···C61 distances [Er···C21 = 3.077 (4) Å; Er···C61 = 3.945 (4) Å] as well as quite different Er—C11—C12 and Er—C11—C16 angles [136.0 (3)° and 108.4 (3)° respectively]. This interaction also causes a noticeable pyramidalization of the metal coordination: taking the centroids of the methylcyclopentadienyl rings and C11 as a reference, the sum of the angles around Er is calculated to be 353.6°. Alternatively, the degree of pyramidalization may be characterized by the displacement of the metal atom from the least-squares plane defined by X5, X5' and C11, which amounts to 0.348 (4) Å.
For other structurally characterized bis(cyclopentadienyl)lanthanide aryls, see Niemeyer & Hauber(1999). For a review of lanthanide···π-arene interactions, see Bochkarev (2002). For related literature, see: Bochkarev et al. (1995); Schumann et al. (1995); Tsutsui & Ely (1975).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005) and SHELXTL (Sheldrick, 1998)'; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids. H atoms have been omitted. |
[Er(C6H7)2(C24H25)] | F(000) = 1292 |
Mr = 638.93 | Dx = 1.510 Mg m−3 |
Monoclinic, P21/c | Melting point: 428 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71069 Å |
a = 9.6758 (9) Å | Cell parameters from 48 reflections |
b = 18.126 (1) Å | θ = 6.0–12.5° |
c = 16.248 (2) Å | µ = 3.01 mm−1 |
β = 99.428 (7)° | T = 173 K |
V = 2811.1 (5) Å3 | Prism, pale pink |
Z = 4 | 0.50 × 0.30 × 0.25 mm |
Siemens P4 diffractometer | 5572 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.071 |
Graphite monochromator | θmax = 29.0°, θmin = 2.1° |
ω scans | h = −13→13 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→24 |
Tmin = 0.335, Tmax = 0.504 | l = 0→22 |
8124 measured reflections | 2 standard reflections every 298 reflections |
7465 independent reflections | intensity decay: none |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | Only H-atom displacement parameters refined |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0351P)2] where P = (Fo2 + 2Fc2)/3 |
7465 reflections | (Δ/σ)max = 0.001 |
346 parameters | Δρmax = 1.05 e Å−3 |
0 restraints | Δρmin = −1.52 e Å−3 |
[Er(C6H7)2(C24H25)] | V = 2811.1 (5) Å3 |
Mr = 638.93 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.6758 (9) Å | µ = 3.01 mm−1 |
b = 18.126 (1) Å | T = 173 K |
c = 16.248 (2) Å | 0.50 × 0.30 × 0.25 mm |
β = 99.428 (7)° |
Siemens P4 diffractometer | 5572 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.071 |
Tmin = 0.335, Tmax = 0.504 | 2 standard reflections every 298 reflections |
8124 measured reflections | intensity decay: none |
7465 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.095 | Only H-atom displacement parameters refined |
S = 1.07 | Δρmax = 1.05 e Å−3 |
7465 reflections | Δρmin = −1.52 e Å−3 |
346 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 | ||
Er | 0.78480 (2) | 0.160221 (10) | 0.337742 (12) | 0.02371 (6) | |
C11 | 0.5701 (4) | 0.0878 (2) | 0.3177 (3) | 0.0220 (8) | |
C12 | 0.5970 (4) | 0.0191 (2) | 0.2803 (2) | 0.0203 (7) | |
C13 | 0.5040 (5) | −0.0397 (2) | 0.2735 (3) | 0.0272 (9) | |
H13A | 0.5275 | −0.0848 | 0.2494 | 0.034 (5)* | |
C14 | 0.3776 (5) | −0.0330 (2) | 0.3016 (3) | 0.0281 (9) | |
H14A | 0.3141 | −0.0733 | 0.2975 | 0.034 (5)* | |
C15 | 0.3442 (5) | 0.0339 (2) | 0.3362 (3) | 0.0266 (9) | |
H15A | 0.2569 | 0.0393 | 0.3551 | 0.034 (5)* | |
C16 | 0.4383 (4) | 0.0931 (2) | 0.3432 (2) | 0.0207 (8) | |
C21 | 0.7283 (4) | 0.0143 (2) | 0.2413 (2) | 0.0211 (8) | |
C22 | 0.7303 (5) | 0.0528 (2) | 0.1659 (3) | 0.0260 (9) | |
C23 | 0.8529 (5) | 0.0517 (2) | 0.1304 (3) | 0.0304 (10) | |
H23A | 0.8558 | 0.0793 | 0.0810 | 0.034 (5)* | |
C24 | 0.9699 (5) | 0.0117 (2) | 0.1648 (3) | 0.0277 (9) | |
C25 | 0.9613 (4) | −0.0306 (2) | 0.2358 (3) | 0.0260 (9) | |
H25A | 1.0391 | −0.0601 | 0.2589 | 0.034 (5)* | |
C26 | 0.8426 (5) | −0.0307 (2) | 0.2736 (2) | 0.0234 (8) | |
C31 | 0.9460 (5) | 0.1945 (3) | 0.4850 (3) | 0.0296 (9) | |
C32 | 1.0263 (5) | 0.1502 (2) | 0.4400 (3) | 0.0291 (9) | |
H32A | 1.1198 | 0.1637 | 0.4258 | 0.045 (6)* | |
C33 | 0.9663 (5) | 0.0792 (3) | 0.4322 (3) | 0.0307 (10) | |
H33A | 1.0121 | 0.0340 | 0.4140 | 0.045 (6)* | |
C34 | 0.8454 (5) | 0.0800 (3) | 0.4707 (3) | 0.0297 (9) | |
H34A | 0.7922 | 0.0354 | 0.4840 | 0.045 (6)* | |
C35 | 0.8312 (5) | 0.1508 (3) | 0.5022 (3) | 0.0302 (9) | |
H35A | 0.7636 | 0.1654 | 0.5397 | 0.045 (6)* | |
C41 | 0.7264 (6) | 0.3005 (2) | 0.3245 (3) | 0.0317 (10) | |
C42 | 0.8693 (5) | 0.2952 (2) | 0.3166 (3) | 0.0316 (10) | |
H42A | 0.9480 | 0.3207 | 0.3533 | 0.045 (6)* | |
C43 | 0.8798 (6) | 0.2591 (3) | 0.2417 (3) | 0.0378 (11) | |
H43A | 0.9668 | 0.2544 | 0.2164 | 0.045 (6)* | |
C44 | 0.7445 (6) | 0.2425 (3) | 0.2023 (3) | 0.0397 (12) | |
H44A | 0.7193 | 0.2234 | 0.1440 | 0.045 (6)* | |
C45 | 0.6479 (5) | 0.2677 (3) | 0.2522 (3) | 0.0358 (11) | |
H45A | 0.5440 | 0.2708 | 0.2349 | 0.045 (6)* | |
C61 | 0.3927 (4) | 0.1652 (2) | 0.3759 (2) | 0.0220 (7) | |
C62 | 0.3219 (5) | 0.2171 (2) | 0.3206 (3) | 0.0257 (9) | |
C63 | 0.2844 (5) | 0.2850 (2) | 0.3510 (3) | 0.0280 (9) | |
H63A | 0.2375 | 0.3202 | 0.3130 | 0.034 (5)* | |
C64 | 0.3137 (5) | 0.3025 (3) | 0.4350 (3) | 0.0301 (9) | |
C65 | 0.3779 (5) | 0.2494 (3) | 0.4898 (3) | 0.0291 (9) | |
H65A | 0.3959 | 0.2603 | 0.5478 | 0.034 (5)* | |
C66 | 0.4170 (4) | 0.1805 (2) | 0.4627 (3) | 0.0251 (9) | |
C221 | 0.5983 (5) | 0.0849 (3) | 0.1176 (3) | 0.0344 (10) | |
H22A | 0.6203 | 0.1111 | 0.0685 | 0.064 (5)* | |
H22B | 0.5571 | 0.1195 | 0.1531 | 0.064 (5)* | |
H22C | 0.5315 | 0.0452 | 0.0996 | 0.064 (5)* | |
C241 | 1.0993 (5) | 0.0103 (3) | 0.1238 (3) | 0.0390 (11) | |
H24A | 1.1133 | 0.0590 | 0.1004 | 0.064 (5)* | |
H24B | 1.0874 | −0.0266 | 0.0791 | 0.064 (5)* | |
H24C | 1.1811 | −0.0025 | 0.1654 | 0.064 (5)* | |
C261 | 0.8379 (5) | −0.0808 (2) | 0.3474 (3) | 0.0291 (9) | |
H26A | 0.9334 | −0.0953 | 0.3718 | 0.064 (5)* | |
H26B | 0.7829 | −0.1249 | 0.3289 | 0.064 (5)* | |
H26C | 0.7942 | −0.0546 | 0.3893 | 0.064 (5)* | |
C311 | 0.9865 (7) | 0.2687 (3) | 0.5224 (4) | 0.0454 (13) | |
H31A | 1.0307 | 0.2625 | 0.5807 | 0.144 (17)* | |
H31B | 0.9026 | 0.2995 | 0.5198 | 0.144 (17)* | |
H31C | 1.0526 | 0.2925 | 0.4911 | 0.144 (17)* | |
C411 | 0.6647 (6) | 0.3360 (3) | 0.3947 (4) | 0.0454 (12) | |
H41A | 0.6583 | 0.3894 | 0.3860 | 0.144 (17)* | |
H41B | 0.7249 | 0.3256 | 0.4481 | 0.144 (17)* | |
H41C | 0.5709 | 0.3159 | 0.3956 | 0.144 (17)* | |
C621 | 0.2827 (6) | 0.1990 (3) | 0.2291 (3) | 0.0356 (11) | |
H62A | 0.2570 | 0.2445 | 0.1976 | 0.064 (5)* | |
H62B | 0.2030 | 0.1649 | 0.2210 | 0.064 (5)* | |
H62C | 0.3627 | 0.1760 | 0.2091 | 0.064 (5)* | |
C641 | 0.2815 (6) | 0.3791 (3) | 0.4654 (3) | 0.0434 (13) | |
H64A | 0.1865 | 0.3935 | 0.4398 | 0.064 (5)* | |
H64B | 0.3490 | 0.4146 | 0.4498 | 0.064 (5)* | |
H64C | 0.2881 | 0.3784 | 0.5263 | 0.064 (5)* | |
C661 | 0.4763 (5) | 0.1222 (3) | 0.5246 (3) | 0.0349 (10) | |
H66A | 0.5096 | 0.1453 | 0.5788 | 0.064 (5)* | |
H66B | 0.5545 | 0.0973 | 0.5048 | 0.064 (5)* | |
H66C | 0.4032 | 0.0861 | 0.5306 | 0.064 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Er | 0.02356 (9) | 0.02370 (9) | 0.02381 (9) | −0.00197 (9) | 0.00372 (6) | 0.00470 (8) |
C11 | 0.024 (2) | 0.0229 (18) | 0.0203 (19) | −0.0004 (16) | 0.0064 (16) | 0.0027 (15) |
C12 | 0.0199 (18) | 0.0242 (18) | 0.0165 (17) | 0.0038 (15) | 0.0024 (14) | 0.0027 (15) |
C13 | 0.029 (2) | 0.024 (2) | 0.028 (2) | 0.0015 (17) | 0.0027 (18) | 0.0004 (16) |
C14 | 0.024 (2) | 0.026 (2) | 0.035 (2) | −0.0014 (17) | 0.0031 (18) | 0.0007 (17) |
C15 | 0.0185 (19) | 0.029 (2) | 0.033 (2) | −0.0001 (17) | 0.0067 (17) | 0.0016 (17) |
C16 | 0.0192 (18) | 0.0269 (19) | 0.0162 (17) | 0.0022 (15) | 0.0034 (15) | 0.0028 (15) |
C21 | 0.0239 (19) | 0.0208 (17) | 0.0191 (18) | 0.0002 (15) | 0.0047 (15) | −0.0009 (15) |
C22 | 0.029 (2) | 0.0266 (19) | 0.0231 (19) | 0.0033 (17) | 0.0057 (17) | 0.0013 (17) |
C23 | 0.040 (3) | 0.029 (2) | 0.024 (2) | 0.0041 (19) | 0.0121 (19) | 0.0057 (17) |
C24 | 0.026 (2) | 0.030 (2) | 0.030 (2) | −0.0007 (18) | 0.0121 (18) | −0.0058 (18) |
C25 | 0.0197 (19) | 0.028 (2) | 0.031 (2) | 0.0051 (16) | 0.0049 (17) | −0.0051 (17) |
C26 | 0.029 (2) | 0.025 (2) | 0.0170 (18) | 0.0031 (17) | 0.0075 (16) | −0.0025 (15) |
C31 | 0.030 (2) | 0.030 (2) | 0.028 (2) | −0.0001 (19) | 0.0023 (18) | 0.0002 (18) |
C32 | 0.0214 (19) | 0.036 (2) | 0.028 (2) | −0.0030 (18) | 0.0008 (16) | −0.0011 (18) |
C33 | 0.033 (2) | 0.030 (2) | 0.027 (2) | 0.0061 (19) | −0.0002 (19) | 0.0020 (18) |
C34 | 0.031 (2) | 0.032 (2) | 0.025 (2) | −0.0036 (18) | 0.0003 (18) | 0.0075 (18) |
C35 | 0.026 (2) | 0.040 (3) | 0.025 (2) | −0.0020 (19) | 0.0072 (17) | 0.0000 (18) |
C41 | 0.042 (3) | 0.021 (2) | 0.033 (2) | 0.0034 (19) | 0.009 (2) | 0.0077 (17) |
C42 | 0.034 (2) | 0.026 (2) | 0.035 (2) | −0.0040 (19) | 0.009 (2) | 0.0056 (18) |
C43 | 0.044 (3) | 0.034 (2) | 0.040 (3) | −0.002 (2) | 0.021 (2) | 0.006 (2) |
C44 | 0.055 (3) | 0.039 (3) | 0.026 (2) | −0.003 (2) | 0.008 (2) | 0.006 (2) |
C45 | 0.037 (3) | 0.030 (2) | 0.040 (3) | 0.002 (2) | 0.003 (2) | 0.018 (2) |
C61 | 0.0174 (17) | 0.0259 (19) | 0.0238 (18) | 0.0000 (16) | 0.0067 (14) | −0.0015 (16) |
C62 | 0.028 (2) | 0.028 (2) | 0.022 (2) | 0.0033 (17) | 0.0074 (16) | −0.0003 (16) |
C63 | 0.027 (2) | 0.027 (2) | 0.030 (2) | 0.0081 (18) | 0.0054 (19) | 0.0019 (17) |
C64 | 0.027 (2) | 0.032 (2) | 0.032 (2) | 0.0030 (18) | 0.0086 (19) | −0.0054 (19) |
C65 | 0.026 (2) | 0.038 (2) | 0.025 (2) | 0.0007 (19) | 0.0102 (18) | −0.0052 (18) |
C66 | 0.0171 (18) | 0.035 (2) | 0.024 (2) | −0.0003 (16) | 0.0060 (16) | 0.0032 (16) |
C221 | 0.037 (3) | 0.037 (2) | 0.028 (2) | 0.009 (2) | 0.001 (2) | 0.0080 (19) |
C241 | 0.040 (3) | 0.047 (3) | 0.035 (3) | 0.000 (2) | 0.019 (2) | 0.000 (2) |
C261 | 0.035 (2) | 0.029 (2) | 0.024 (2) | 0.0021 (19) | 0.0050 (18) | 0.0021 (17) |
C311 | 0.053 (3) | 0.039 (3) | 0.045 (3) | −0.002 (3) | 0.007 (3) | −0.006 (2) |
C411 | 0.052 (3) | 0.044 (3) | 0.042 (3) | 0.008 (3) | 0.014 (2) | 0.001 (2) |
C621 | 0.045 (3) | 0.039 (3) | 0.022 (2) | 0.008 (2) | 0.001 (2) | 0.0015 (19) |
C641 | 0.050 (3) | 0.039 (3) | 0.042 (3) | 0.006 (2) | 0.010 (3) | −0.012 (2) |
C661 | 0.035 (3) | 0.047 (3) | 0.024 (2) | −0.001 (2) | 0.0079 (19) | 0.005 (2) |
Er—C11 | 2.434 (4) | C41—C45 | 1.420 (7) |
Er—C31 | 2.706 (5) | C41—C411 | 1.516 (7) |
Er—C32 | 2.642 (4) | C42—C43 | 1.400 (7) |
Er—C33 | 2.591 (4) | C42—H42A | 1.0000 |
Er—C34 | 2.591 (4) | C43—C44 | 1.393 (8) |
Er—C35 | 2.641 (4) | C43—H43A | 1.0000 |
Er—C41 | 2.606 (4) | C44—C45 | 1.410 (7) |
Er—C42 | 2.620 (4) | C44—H44A | 1.0000 |
Er—C43 | 2.639 (5) | C45—H45A | 1.0000 |
Er—C44 | 2.635 (5) | C61—C62 | 1.400 (6) |
Er—C45 | 2.623 (4) | C61—C66 | 1.419 (6) |
C11—C16 | 1.407 (6) | C62—C63 | 1.398 (6) |
C11—C12 | 1.427 (5) | C62—C621 | 1.509 (6) |
C12—C13 | 1.388 (6) | C63—C64 | 1.384 (6) |
C12—C21 | 1.512 (5) | C63—H63A | 0.9500 |
C13—C14 | 1.379 (6) | C64—C65 | 1.387 (7) |
C13—H13A | 0.9500 | C64—C641 | 1.523 (7) |
C14—C15 | 1.396 (6) | C65—C66 | 1.397 (6) |
C14—H14A | 0.9500 | C65—H65A | 0.9500 |
C15—C16 | 1.399 (6) | C66—C661 | 1.506 (6) |
C15—H15A | 0.9500 | C221—H22A | 0.9800 |
C16—C61 | 1.505 (6) | C221—H22B | 0.9800 |
C21—C26 | 1.406 (6) | C221—H22C | 0.9800 |
C21—C22 | 1.413 (6) | C241—H24A | 0.9800 |
C22—C23 | 1.402 (6) | C241—H24B | 0.9800 |
C22—C221 | 1.502 (6) | C241—H24C | 0.9800 |
C23—C24 | 1.383 (6) | C261—H26A | 0.9800 |
C23—H23A | 0.9500 | C261—H26B | 0.9800 |
C24—C25 | 1.398 (6) | C261—H26C | 0.9800 |
C24—C241 | 1.512 (6) | C311—H31A | 0.9800 |
C25—C26 | 1.388 (6) | C311—H31B | 0.9800 |
C25—H25A | 0.9500 | C311—H31C | 0.9800 |
C26—C261 | 1.509 (6) | C411—H41A | 0.9800 |
C31—C32 | 1.403 (6) | C411—H41B | 0.9800 |
C31—C35 | 1.429 (6) | C411—H41C | 0.9800 |
C31—C311 | 1.501 (7) | C621—H62A | 0.9800 |
C32—C33 | 1.409 (6) | C621—H62B | 0.9800 |
C32—H32A | 1.0000 | C621—H62C | 0.9800 |
C33—C34 | 1.414 (7) | C641—H64A | 0.9800 |
C33—H33A | 1.0000 | C641—H64B | 0.9800 |
C34—C35 | 1.396 (6) | C641—H64C | 0.9800 |
C34—H34A | 1.0000 | C661—H66A | 0.9800 |
C35—H35A | 1.0000 | C661—H66B | 0.9800 |
C41—C42 | 1.412 (7) | C661—H66C | 0.9800 |
C11—Er—C34 | 83.11 (14) | C35—C34—C33 | 108.0 (4) |
C11—Er—C33 | 104.71 (14) | C35—C34—Er | 76.5 (3) |
C34—Er—C33 | 31.67 (15) | C33—C34—Er | 74.2 (2) |
C11—Er—C41 | 110.29 (15) | C35—C34—H34A | 125.4 |
C34—Er—C41 | 129.28 (15) | C33—C34—H34A | 125.4 |
C33—Er—C41 | 135.95 (16) | Er—C34—H34A | 125.4 |
C11—Er—C42 | 139.83 (14) | C34—C35—C31 | 108.2 (4) |
C34—Er—C42 | 126.92 (15) | C34—C35—Er | 72.5 (3) |
C33—Er—C42 | 114.29 (15) | C31—C35—Er | 77.0 (3) |
C41—Er—C42 | 31.35 (15) | C34—C35—H35A | 125.4 |
C11—Er—C45 | 89.10 (15) | C31—C35—H35A | 125.4 |
C34—Er—C45 | 152.19 (16) | Er—C35—H35A | 125.4 |
C33—Er—C45 | 165.78 (16) | C42—C41—C45 | 107.2 (4) |
C41—Er—C45 | 31.51 (15) | C42—C41—C411 | 127.5 (5) |
C42—Er—C45 | 51.54 (16) | C45—C41—C411 | 125.2 (5) |
C11—Er—C44 | 100.81 (15) | C42—C41—Er | 74.9 (3) |
C34—Er—C44 | 175.50 (16) | C45—C41—Er | 74.9 (3) |
C33—Er—C44 | 144.02 (16) | C411—C41—Er | 117.3 (3) |
C41—Er—C44 | 51.54 (16) | C43—C42—C41 | 108.8 (5) |
C42—Er—C44 | 50.84 (16) | C43—C42—Er | 75.3 (3) |
C45—Er—C44 | 31.11 (16) | C41—C42—Er | 73.8 (3) |
C11—Er—C43 | 131.29 (16) | C43—C42—H42A | 125.2 |
C34—Er—C43 | 145.23 (16) | C41—C42—H42A | 125.2 |
C33—Er—C43 | 117.89 (17) | Er—C42—H42A | 125.2 |
C41—Er—C43 | 51.68 (15) | C44—C43—C42 | 107.7 (5) |
C42—Er—C43 | 30.87 (15) | C44—C43—Er | 74.5 (3) |
C45—Er—C43 | 51.42 (16) | C42—C43—Er | 73.8 (3) |
C44—Er—C43 | 30.63 (17) | C44—C43—H43A | 125.7 |
C11—Er—C35 | 95.75 (14) | C42—C43—H43A | 125.7 |
C34—Er—C35 | 30.93 (14) | Er—C43—H43A | 125.7 |
C33—Er—C35 | 51.49 (15) | C43—C44—C45 | 109.1 (5) |
C41—Er—C35 | 98.37 (15) | C43—C44—Er | 74.9 (3) |
C42—Er—C35 | 100.84 (15) | C45—C44—Er | 74.0 (3) |
C45—Er—C35 | 124.86 (16) | C43—C44—H44A | 125.1 |
C44—Er—C35 | 149.23 (16) | C45—C44—H44A | 125.1 |
C43—Er—C35 | 128.62 (16) | Er—C44—H44A | 125.1 |
C11—Er—C32 | 133.97 (14) | C44—C45—C41 | 107.2 (5) |
C34—Er—C32 | 51.76 (14) | C44—C45—Er | 74.9 (3) |
C33—Er—C32 | 31.22 (14) | C41—C45—Er | 73.6 (3) |
C41—Er—C32 | 106.06 (15) | C44—C45—H45A | 125.9 |
C42—Er—C32 | 83.34 (15) | C41—C45—H45A | 125.9 |
C45—Er—C32 | 134.59 (15) | Er—C45—H45A | 125.9 |
C44—Er—C32 | 123.99 (16) | C62—C61—C66 | 119.4 (4) |
C43—Er—C32 | 93.49 (16) | C62—C61—C16 | 119.8 (4) |
C35—Er—C32 | 51.18 (14) | C66—C61—C16 | 120.7 (4) |
C11—Er—C31 | 126.72 (14) | C63—C62—C61 | 119.5 (4) |
C34—Er—C31 | 51.14 (14) | C63—C62—C621 | 120.1 (4) |
C33—Er—C31 | 50.93 (14) | C61—C62—C621 | 120.4 (4) |
C41—Er—C31 | 86.26 (15) | C64—C63—C62 | 121.8 (4) |
C42—Er—C31 | 75.78 (15) | C64—C63—H63A | 119.1 |
C45—Er—C31 | 117.76 (15) | C62—C63—H63A | 119.1 |
C44—Er—C31 | 126.43 (16) | C63—C64—C65 | 118.2 (4) |
C43—Er—C31 | 99.25 (16) | C63—C64—C641 | 120.5 (4) |
C35—Er—C31 | 30.97 (14) | C65—C64—C641 | 121.2 (4) |
C32—Er—C31 | 30.40 (14) | C64—C65—C66 | 122.2 (4) |
C16—C11—C12 | 114.9 (4) | C64—C65—H65A | 118.9 |
C12—C11—Er | 108.4 (3) | C66—C65—H65A | 118.9 |
C16—C11—Er | 136.0 (3) | C65—C66—C61 | 118.6 (4) |
C13—C12—C11 | 122.9 (4) | C65—C66—C661 | 120.6 (4) |
C13—C12—C21 | 120.0 (4) | C61—C66—C661 | 120.7 (4) |
C11—C12—C21 | 116.9 (4) | C22—C221—H22A | 109.5 |
C14—C13—C12 | 120.2 (4) | C22—C221—H22B | 109.5 |
C14—C13—H13A | 119.9 | H22A—C221—H22B | 109.5 |
C12—C13—H13A | 119.9 | C22—C221—H22C | 109.5 |
C13—C14—C15 | 119.1 (4) | H22A—C221—H22C | 109.5 |
C13—C14—H14A | 120.4 | H22B—C221—H22C | 109.5 |
C15—C14—H14A | 120.4 | C24—C241—H24A | 109.5 |
C14—C15—C16 | 120.5 (4) | C24—C241—H24B | 109.5 |
C14—C15—H15A | 119.8 | H24A—C241—H24B | 109.5 |
C16—C15—H15A | 119.8 | C24—C241—H24C | 109.5 |
C15—C16—C11 | 122.2 (4) | H24A—C241—H24C | 109.5 |
C15—C16—C61 | 118.0 (4) | H24B—C241—H24C | 109.5 |
C11—C16—C61 | 119.7 (4) | C26—C261—H26A | 109.5 |
C26—C21—C22 | 119.3 (4) | C26—C261—H26B | 109.5 |
C26—C21—C12 | 122.7 (3) | H26A—C261—H26B | 109.5 |
C22—C21—C12 | 117.8 (4) | C26—C261—H26C | 109.5 |
C23—C22—C21 | 118.8 (4) | H26A—C261—H26C | 109.5 |
C23—C22—C221 | 119.7 (4) | H26B—C261—H26C | 109.5 |
C21—C22—C221 | 120.9 (4) | C31—C311—H31A | 109.5 |
C24—C23—C22 | 122.2 (4) | C31—C311—H31B | 109.5 |
C24—C23—H23A | 118.9 | H31A—C311—H31B | 109.5 |
C22—C23—H23A | 118.9 | C31—C311—H31C | 109.5 |
C23—C24—C25 | 117.8 (4) | H31A—C311—H31C | 109.5 |
C23—C24—C241 | 120.8 (4) | H31B—C311—H31C | 109.5 |
C25—C24—C241 | 121.3 (4) | C41—C411—H41A | 109.5 |
C26—C25—C24 | 122.1 (4) | C41—C411—H41B | 109.5 |
C26—C25—H25A | 118.9 | H41A—C411—H41B | 109.5 |
C24—C25—H25A | 118.9 | C41—C411—H41C | 109.5 |
C25—C26—C21 | 119.4 (4) | H41A—C411—H41C | 109.5 |
C25—C26—C261 | 119.2 (4) | H41B—C411—H41C | 109.5 |
C21—C26—C261 | 121.4 (4) | C62—C621—H62A | 109.5 |
C32—C31—C35 | 107.4 (4) | C62—C621—H62B | 109.5 |
C32—C31—C311 | 126.4 (5) | H62A—C621—H62B | 109.5 |
C35—C31—C311 | 125.3 (4) | C62—C621—H62C | 109.5 |
C32—C31—Er | 72.3 (3) | H62A—C621—H62C | 109.5 |
C35—C31—Er | 72.0 (3) | H62B—C621—H62C | 109.5 |
C311—C31—Er | 129.7 (3) | C64—C641—H64A | 109.5 |
C31—C32—C33 | 108.3 (4) | C64—C641—H64B | 109.5 |
C31—C32—Er | 77.3 (3) | H64A—C641—H64B | 109.5 |
C33—C32—Er | 72.4 (3) | C64—C641—H64C | 109.5 |
C31—C32—H32A | 125.3 | H64A—C641—H64C | 109.5 |
C33—C32—H32A | 125.3 | H64B—C641—H64C | 109.5 |
Er—C32—H32A | 125.3 | C66—C661—H66A | 109.5 |
C32—C33—C34 | 108.1 (4) | C66—C661—H66B | 109.5 |
C32—C33—Er | 76.4 (3) | H66A—C661—H66B | 109.5 |
C34—C33—Er | 74.2 (3) | C66—C661—H66C | 109.5 |
C32—C33—H33A | 125.4 | H66A—C661—H66C | 109.5 |
C34—C33—H33A | 125.4 | H66B—C661—H66C | 109.5 |
Er—C33—H33A | 125.4 |
Experimental details
Crystal data | |
Chemical formula | [Er(C6H7)2(C24H25)] |
Mr | 638.93 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 9.6758 (9), 18.126 (1), 16.248 (2) |
β (°) | 99.428 (7) |
V (Å3) | 2811.1 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.01 |
Crystal size (mm) | 0.50 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Siemens P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.335, 0.504 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8124, 7465, 5572 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.095, 1.07 |
No. of reflections | 7465 |
No. of parameters | 346 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 1.05, −1.52 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005) and SHELXTL (Sheldrick, 1998)', SHELXTL.
Er—C11 | 2.434 (4) | Er—C41 | 2.606 (4) |
Er—C31 | 2.706 (5) | Er—C42 | 2.620 (4) |
Er—C32 | 2.642 (4) | Er—C43 | 2.639 (5) |
Er—C33 | 2.591 (4) | Er—C44 | 2.635 (5) |
Er—C34 | 2.591 (4) | Er—C45 | 2.623 (4) |
Er—C35 | 2.641 (4) | ||
C12—C11—Er | 108.4 (3) | C16—C11—Er | 136.0 (3) |
Although base-stabilized bis(cyclopentadienyl)lanthanide aryls of the composition ArLnCp'2(thf) (Cp' =Cp, Cp*) have been known for more than three decades and were extensively studied (Tsutsui & Ely, 1975; Schumann et al., 1995), the corresponding Lewis-donor-free systems received much less attention. Earlier we have reported the first structurally characterized examples of this type, which are kinetically stabilized by the bulky Dmp ligand (Niemeyer & Hauber, 1999).
The crystal structure of the title compound, (I), is made up of monomeric units (Fig.1). The erbium atom is coordinated by two η5-bonded methylcyclopentadienyl ligands (their centroids are X5 and X5') and the ipso carbon atom C11 of the Dmp substituent. With 2.434 (4) Å the Er—C11 bond length is practically identical to the average Er—C distance of 2.431 Å in the solvated erbium organyl [Er(Ph)3(thf)3] (Bochkarev et al.,1995). The metal-carbon distances to the η5-coordinated methylcyclopentadienyl rings [average Er–C = 2.629 Å] are typical for other bis(cyclopentadienyl) complexes (Schumann et al., 1995).
The most interesting aspect of the solid-state structure of (I) is additional metal-π-arene interaction (Bochkarev, 2002) involving the Er atom and one of the mesityl rings of the terphenyl substituent, which is reflected in dramatically different Er···C21 and Er···C61 distances [Er···C21 = 3.077 (4) Å; Er···C61 = 3.945 (4) Å] as well as quite different Er—C11—C12 and Er—C11—C16 angles [136.0 (3)° and 108.4 (3)° respectively]. This interaction also causes a noticeable pyramidalization of the metal coordination: taking the centroids of the methylcyclopentadienyl rings and C11 as a reference, the sum of the angles around Er is calculated to be 353.6°. Alternatively, the degree of pyramidalization may be characterized by the displacement of the metal atom from the least-squares plane defined by X5, X5' and C11, which amounts to 0.348 (4) Å.