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Acta Cryst. (2008). E64, m473    [ doi:10.1107/S1600536808004248 ]

Di-[mu]-tert-butanolato-bis[bis([eta]5-cyclopentadienyl)erbium(III)]

S. Pagano and W. Schnick

Abstract top

In the centrosymmetric title compound, [Er2(C5H5)4(C4H9O)2], each Er atom is in a distorted tetrahedral coordination environment, coordinated by two cyclopentadienyl rings and two tert-butoxy groups, forming a dimeric complex bridged through the tert-butoxy groups.

Comment top

By stirring [Er2{µ-η1:η2-OC(OBut)NH}Cp4] in THF the carbamato moiety decomposes to [Cp2ErtBuO]2 and an amorphous solid showing strong C=N vibrations (2190 cm-1) in the IR spectra. It is likely that the tert-butylcarbamato ligand splits up into tert-butanol and cyanate. Attempts to isolate a crystalline cyanato complex were unsuccessful as yet. The structure of [Cp2ErtBuO]2 is in accordance with a series of lanthanide-cyclopentadienyl-alcoholate-complexes synthesized so far (Schumann et al., 1995).

Related literature top

During our search for highly reactive molecular precursors, we characterized a series of lanthanide amide- (Baisch, Pagano, Zeuner, Barros et al., 2006) and carbamate complexes (Baisch, Pagano, Zeuner & Schnick, 2006). The synthesis of [Er2{µ-η1:η2-OC(OBut)NH}Cp4] and its application as a precursor is described by Zeuner et al. (2008). For related literature and a general overview on cyclopentadienyl-containing compounds of the lanthanides, see Schumann et al. (1995).

Experimental top

[Er2{µ-η1:η2-OC(OBut)NH}Cp4] was dissolved in dry THF and stirred for 12 h at 297 K. After evaporation of the solvent the orange residue was suspended in dry hexane. The filtrate was stored at 279 K to afford [Cp2ErtBuO]2 as pink crystals.

Refinement top

The H atoms were positioned geometrically and refined using a riding model: C(aromatic)–H = 0.95 Å with Uiso(H) = 1.2Ueq(C), and C(aliphatic)–H = 0.98 Å with Uiso(H) = 1.5Ueq(C).

Computing details top

Data collection: COLLLECT (Nonius, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H– atoms are omitted for clarity.
[Figure 2] Fig. 2. Crystal packing diagram of the title compound viewed along the a axis.
Di-µ-tert-butanolato-bis[bis(η5-cyclopentadienyl)erbium(III)] top
Crystal data top
[Er2(C5H5)4(C4H9O)2]F000 = 716
Mr = 741.10Dx = 1.928 Mg m−3
Monoclinic, P21/nMelting point: not measured K
Hall symbol: -P 2ynMo Kα radiation
λ = 0.71073 Å
a = 8.3905 (17) ÅCell parameters from 14322 reflections
b = 15.628 (3) Åθ = 3.1–27.5º
c = 9.950 (2) ŵ = 6.55 mm−1
β = 101.85 (3)ºT = 200 (2) K
V = 1276.9 (5) Å3Block, pink
Z = 20.13 × 0.07 × 0.04 mm
Data collection top
Nonius KappaCCD
diffractometer		2912 independent reflections
Radiation source: fine-focus sealed tube2578 reflections with I > \2s(I)
Monochromator: graphiteRint = 0.021
Detector resolution: 9 pixels mm-1θmax = 27.5º
T = 200(2) Kθmin = 3.2º
φ and ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		k = −20→20
Tmin = 0.594, Tmax = 0.783l = −12→12
5666 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.022  w = 1/[σ2(Fo2) + (0.025P)2 + 1.7644P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.053(Δ/σ)max = 0.002
S = 1.05Δρmax = 1.29 e Å−3
2912 reflectionsΔρmin = −1.23 e Å−3
149 parametersExtinction correction: (SHELXL97; Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0022 (2)
Secondary atom site location: difference Fourier map
Crystal data top
[Er2(C5H5)4(C4H9O)2]V = 1276.9 (5) Å3
Mr = 741.10Z = 2
Monoclinic, P21/nMo Kα
a = 8.3905 (17) ŵ = 6.55 mm−1
b = 15.628 (3) ÅT = 200 (2) K
c = 9.950 (2) Å0.13 × 0.07 × 0.04 mm
β = 101.85 (3)º
Data collection top
Nonius KappaCCD
diffractometer		2912 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		2578 reflections with I > \2s(I)
Tmin = 0.594, Tmax = 0.783Rint = 0.021
5666 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.022149 parameters
wR(F2) = 0.053H-atom parameters constrained
S = 1.05Δρmax = 1.29 e Å−3
2912 reflectionsΔρmin = −1.23 e Å−3
Special details top

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 (Å2) top
xyzUiso*/Ueq
Er10.080747 (15)0.036095 (8)0.666673 (13)0.01748 (7)
C150.2668 (4)−0.0762 (3)0.8373 (4)0.0332 (8)
H150.2131−0.11760.88210.040*
C130.3898 (5)0.0464 (3)0.7888 (5)0.0385 (9)
H130.43310.10280.79530.046*
C23−0.0655 (5)0.0983 (3)0.8573 (4)0.0396 (10)
H23−0.06830.06050.93150.048*
C25−0.1323 (5)0.1661 (2)0.6539 (4)0.0328 (8)
H25−0.18870.18350.56530.039*
C210.0166 (5)0.1986 (2)0.7245 (4)0.0349 (8)
H210.07970.24140.69190.042*
C110.3101 (4)−0.0858 (3)0.7084 (4)0.0312 (8)
H110.2906−0.13500.65130.037*
C220.0565 (5)0.1574 (3)0.8508 (4)0.0376 (9)
H220.15050.16790.92030.045*
C140.3175 (5)0.0055 (3)0.8874 (4)0.0391 (9)
H140.30530.02900.97280.047*
C120.3865 (4)−0.0107 (3)0.6790 (4)0.0339 (8)
H120.4288−0.00010.59900.041*
C24−0.1835 (5)0.1041 (3)0.7358 (4)0.0375 (9)
H24−0.28090.07150.71340.045*
O10.0788 (3)0.06891 (14)0.4454 (2)0.0195 (4)
C10.1512 (4)0.1414 (2)0.3870 (3)0.0246 (7)
C20.0347 (5)0.2174 (2)0.3640 (4)0.0343 (8)
H2A−0.06650.20070.30140.051*
H2B0.08530.26490.32380.051*
H2C0.01060.23540.45200.051*
C40.1903 (5)0.1155 (2)0.2497 (4)0.0328 (8)
H4A0.27190.06980.26420.049*
H4B0.23310.16510.20820.049*
H4C0.09100.09510.18830.049*
C30.3083 (5)0.1691 (3)0.4829 (4)0.0360 (9)
H3A0.28630.18200.57370.054*
H3B0.35120.22030.44570.054*
H3C0.38860.12280.49080.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Er10.01723 (10)0.01828 (10)0.01704 (10)0.00043 (5)0.00380 (6)−0.00140 (5)
C150.0310 (19)0.038 (2)0.0284 (19)0.0078 (16)0.0010 (14)0.0104 (16)
C130.0205 (18)0.041 (2)0.049 (2)−0.0049 (15)−0.0040 (16)0.0010 (19)
C230.058 (3)0.035 (2)0.033 (2)0.0116 (19)0.0257 (19)0.0020 (17)
C250.038 (2)0.0274 (19)0.033 (2)0.0108 (16)0.0053 (15)−0.0065 (15)
C210.045 (2)0.0218 (18)0.042 (2)−0.0023 (16)0.0192 (17)−0.0102 (16)
C110.0268 (18)0.036 (2)0.0295 (19)0.0109 (15)0.0022 (14)0.0029 (15)
C220.042 (2)0.038 (2)0.031 (2)0.0075 (17)0.0030 (16)−0.0179 (17)
C140.031 (2)0.054 (3)0.0276 (19)0.0070 (19)−0.0043 (15)−0.0051 (19)
C120.0188 (17)0.049 (2)0.035 (2)0.0079 (16)0.0079 (14)0.0053 (18)
C240.0297 (19)0.030 (2)0.058 (3)0.0028 (16)0.0221 (18)−0.0096 (19)
O10.0228 (11)0.0165 (11)0.0196 (11)−0.0040 (9)0.0050 (8)0.0020 (9)
C10.0294 (17)0.0178 (16)0.0278 (17)−0.0054 (13)0.0088 (13)0.0026 (13)
C20.045 (2)0.0182 (17)0.042 (2)−0.0002 (16)0.0144 (17)0.0095 (16)
C40.042 (2)0.0291 (19)0.0300 (18)−0.0063 (16)0.0147 (15)0.0041 (16)
C30.040 (2)0.033 (2)0.036 (2)−0.0147 (17)0.0101 (16)−0.0002 (17)
Geometric parameters (Å, °) top
Er1—O12.257 (2)C25—H250.9500
Er1—O1i2.262 (2)C21—C221.390 (6)
Er1—C132.633 (4)C21—H210.9500
Er1—C122.646 (3)C11—C121.397 (6)
Er1—C232.646 (4)C11—H110.9500
Er1—C242.673 (3)C22—H220.9500
Er1—C222.673 (4)C14—H140.9500
Er1—C112.679 (4)C12—H120.9500
Er1—C212.682 (4)C24—H240.9500
Er1—C142.685 (4)O1—C11.461 (4)
Er1—C252.692 (4)O1—Er1i2.262 (2)
Er1—C152.705 (4)C1—C31.523 (5)
C15—C141.405 (6)C1—C41.524 (5)
C15—C111.411 (5)C1—C21.525 (5)
C15—H150.9500C2—H2A0.9800
C13—C121.406 (6)C2—H2B0.9800
C13—C141.409 (6)C2—H2C0.9800
C13—H130.9500C4—H4A0.9800
C23—C221.391 (6)C4—H4B0.9800
C23—C241.399 (6)C4—H4C0.9800
C23—H230.9500C3—H3A0.9800
C25—C241.391 (6)C3—H3B0.9800
C25—C211.397 (5)C3—H3C0.9800
O1—Er1—O1i78.39 (8)Er1—C13—H13114.5
O1—Er1—C13104.21 (12)C22—C23—C24108.3 (4)
O1i—Er1—C13134.35 (11)C22—C23—Er175.9 (2)
O1—Er1—C1285.46 (10)C24—C23—Er175.8 (2)
O1i—Er1—C12107.00 (11)C22—C23—H23125.8
C13—Er1—C1230.90 (13)C24—C23—H23125.8
O1—Er1—C23134.74 (11)Er1—C23—H23114.7
O1i—Er1—C23107.78 (11)C24—C25—C21108.1 (4)
C13—Er1—C23101.80 (14)C24—C25—Er174.2 (2)
C12—Er1—C23131.01 (13)C21—C25—Er174.6 (2)
O1—Er1—C24108.69 (11)C24—C25—H25126.0
O1i—Er1—C2488.69 (11)C21—C25—H25126.0
C13—Er1—C24130.34 (14)Er1—C25—H25117.3
C12—Er1—C24160.99 (13)C22—C21—C25108.2 (4)
C23—Er1—C2430.49 (13)C22—C21—Er174.6 (2)
O1—Er1—C22121.39 (11)C25—C21—Er175.3 (2)
O1i—Er1—C22137.07 (11)C22—C21—H21125.9
C13—Er1—C2281.17 (13)C25—C21—H21125.9
C12—Er1—C22111.94 (13)Er1—C21—H21116.3
C23—Er1—C2230.31 (13)C12—C11—C15108.5 (4)
C24—Er1—C2250.05 (13)C12—C11—Er173.5 (2)
O1—Er1—C11100.02 (10)C15—C11—Er175.8 (2)
O1i—Er1—C1183.92 (11)C12—C11—H11125.8
C13—Er1—C1150.50 (13)C15—C11—H11125.8
C12—Er1—C1130.41 (12)Er1—C11—H11116.9
C23—Er1—C11125.04 (12)C21—C22—C23107.8 (4)
C24—Er1—C11148.22 (12)C21—C22—Er175.3 (2)
C22—Er1—C11123.46 (12)C23—C22—Er173.8 (2)
O1—Er1—C2191.86 (10)C21—C22—H22126.1
O1i—Er1—C21131.93 (10)C23—C22—H22126.1
C13—Er1—C2193.72 (13)Er1—C22—H22116.9
C12—Er1—C21119.13 (13)C15—C14—C13107.9 (4)
C23—Er1—C2149.88 (12)C15—C14—Er175.7 (2)
C24—Er1—C2149.84 (12)C13—C14—Er172.6 (2)
C22—Er1—C2130.08 (12)C15—C14—H14126.0
C11—Er1—C21144.01 (12)C13—C14—H14126.0
O1—Er1—C14133.98 (11)Er1—C14—H14117.7
O1i—Er1—C14122.53 (12)C11—C12—C13107.9 (3)
C13—Er1—C1430.70 (14)C11—C12—Er176.1 (2)
C12—Er1—C1450.61 (12)C13—C12—Er174.0 (2)
C23—Er1—C1481.56 (13)C12—C12—H12126.1
C24—Er1—C14111.95 (13)C13—C12—H12126.1
C22—Er1—C1473.34 (13)Er1—C12—H12116.0
C11—Er1—C1450.14 (13)C25—C24—C23107.6 (4)
C21—Er1—C1498.07 (13)C25—C24—Er175.8 (2)
O1—Er1—C2584.86 (10)C23—C24—Er173.7 (2)
O1i—Er1—C25101.80 (10)C25—C24—H24126.2
C13—Er1—C25123.85 (13)C23—C24—H24126.2
C12—Er1—C25147.00 (13)Er1—C24—H24116.5
C23—Er1—C2549.88 (12)C1—O1—Er1130.07 (19)
C24—Er1—C2530.06 (12)C1—O1—Er1i128.22 (18)
C22—Er1—C2549.74 (12)Er1—O1—Er1i101.61 (8)
C11—Er1—C25173.19 (12)O1—C1—C3110.4 (3)
C21—Er1—C2530.13 (12)O1—C1—C4109.6 (3)
C14—Er1—C25123.08 (13)C3—C1—C4108.6 (3)
O1—Er1—C15130.36 (10)O1—C1—C2110.9 (3)
O1i—Er1—C1592.60 (11)C3—C1—C2108.6 (3)
C13—Er1—C1550.45 (13)C4—C1—C2108.7 (3)
C12—Er1—C1550.39 (12)C1—C2—H2A109.5
C23—Er1—C1594.67 (12)C1—C2—H2B109.5
C24—Er1—C15119.92 (13)H2A—C2—H2B109.5
C22—Er1—C1598.37 (12)C1—C2—H2C109.5
C11—Er1—C1530.38 (11)H2A—C2—H2C109.5
C21—Er1—C15126.53 (12)H2B—C2—H2C109.5
C14—Er1—C1530.22 (14)C1—C4—H4A109.5
C25—Er1—C15144.28 (12)C1—C4—H4B109.5
C14—C15—C11107.6 (4)H4A—C4—H4B109.5
C14—C15—Er174.1 (2)C1—C4—H4C109.5
C11—C15—Er173.8 (2)H4A—C4—H4C109.5
C14—C15—H15126.2H4B—C4—H4C109.5
C11—C15—H15126.2C1—C3—H3A109.5
Er1—C15—H15117.9C1—C3—H3B109.5
C12—C13—C14108.1 (4)H3A—C3—H3B109.5
C12—C13—Er175.1 (2)C1—C3—H3C109.5
C14—C13—Er176.7 (2)H3A—C3—H3C109.5
C12—C13—H13125.9H3B—C3—H3C109.5
C14—C13—H13125.9
Symmetry codes: (i) −x, −y, −z+1.
Acknowledgements top

The authors are indebted to Dr Peter Meyer for performing thesingle-crystal X-ray diffractometry. Financial support by the Deutsche Forschungsgemeinschaft (DFG) (Schwerpunktprogramm SPP 1166, Lanthanoidspezifische Funktionalitäten in Molekül und Material, project SCHN377/10) and the Fonds der Chemischen Industrie is also gratefully acknowledged.

references
References top

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