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Acta Cryst. (2007). E63, m2581    [ doi:10.1107/S1600536807045187 ]

Cubic di-[mu]-amido-bis[bis([eta]5-cyclopentadienyl)ytterbium(III)]

M. Zeuner and W. Schnick

Abstract top

The title compound, [Yb2(C5H5)4(NH2)2], was synthesized in a Parr high-pressure vessel starting from monoclinic [Cp2YbNH2]2 (where Cp = cyclopentadienyl). The complex is located on a special position of site symmetry mmm with just an eighth of the complex in the asymmetric unit. The Yb atom is in a distorted tetrahedral coordination environment, coordinated by two cyclopentadienyl rings and two amino groups forming a dimeric complex bridged through the amino groups. This compound represents the high-pressure cubic modification of monoclinic [Cp2YbNH2]2 obtained at 250 bar (1 bar = 105 Pa) under an atmosphere of argon.

Comment top

The stucture of the title compound, [Cp2YbNH2]2, shows the high-pressure cubic modification of the monoclinic compound [Cp2YbNH2]2. The assymetric unit consists of three C atoms, one N atom and one Yb atom (figure 1). Gometric parameters of the title compound are in the usual ranges. It crystalizes isotyp with cubic [Cp2ErNH2]2, which was the only cubic compound of the system [Cp2LnNH2]2 so far.

Related literature top

The monoclinic [Cp2YbNH2]2 complex was first described by Fischer & Fischer (1966). The first single X-ray diffraction data of this compound were presented by Baisch, Pagano, Zeuner, Barros et al. (2006). For related literature, see Schumann et al. (1995); Hayes & Thomas (1989); Hammel & Weidlein (1990); Baisch, Pagano, Zeuner & Schnick (2006).

Experimental top

Anhydrous ammonia was condensed at 195 K (dry ice, iPrOH) onto YpCp3 (4–10 mmol). The resulting colourless mixture was stirred rapidly for 5 h and then further stirred for additional 6 − 24 h without further cooling. After complete evaporation of residual ammonia the pale-coloured solid was dried under vakuum and sublimed under reduced pressure yielding green Cp3YbNH3. Heating of Cp3YbNH3 to 523 K yielded yellow monoclinic [Cp2YbNH2]2. Subsequent treatment of this compound to 250 bar yielded yellow cubic [Cp2YbNH2]2.

Refinement top

The H atoms bonded to C were positioned geometrically and refined using a riding model, C—H = 0.93 A and Uiso(H) = 1.2 Uiso(C). The amino H atom was freely refined.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

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.
[Figure 2] Fig. 2. shows the crystal packing diagram of the title compound viewed along the c axis.
di-µ-amido-bis[bis(η5-cyclopentadienyl)ytterbium(III)] top
Crystal data top
[Yb2(C5H5)4(NH2)2]Z = 6
Mr = 638.5F000 = 1788
Cubic, Im3Dx = 2.126 Mg m−3
Hall symbol: -I223Melting point: not measured K
a = 14.4104 (17) ÅMo Kα radiation
λ = 0.71073 Å
b = 14.4104 (17) ÅCell parameters from 6512 reflections
c = 14.4104 (17) Åθ = 4.6–60.9º
α = 90ºµ = 9.32 mm−1
β = 90ºT = 293 (2) K
γ = 90ºPlatelet, yellow
V = 2992.5 (6) Å30.22 × 0.17 × 0.12 mm
Data collection top
Stoe IPDS
diffractometer		843 independent reflections
Radiation source: fine-focus sealed tube578 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.080
T = 293(2) Kθmax = 30.4º
oscillation scansθmin = 2.8º
Absorption correction: multi-scan
correction based on equivalents (XPREP in SHELXTL-PLUS; Sheldrick, 1996)		h = −20→20
Tmin = 0.160, Tmax = 0.390k = −20→20
16043 measured reflectionsl = −20→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.051  w = 1/[σ2(Fo2) + (0.0285P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.87(Δ/σ)max < 0.001
843 reflectionsΔρmax = 0.58 e Å−3
36 parametersΔρmin = −0.50 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Yb2(C5H5)4(NH2)2]γ = 90º
Mr = 638.5V = 2992.5 (6) Å3
Cubic, Im3Z = 6
a = 14.4104 (17) ÅMo Kα
b = 14.4104 (17) ŵ = 9.32 mm−1
c = 14.4104 (17) ÅT = 293 (2) K
α = 90º0.22 × 0.17 × 0.12 mm
β = 90º
Data collection top
Stoe IPDS
diffractometer		843 independent reflections
Absorption correction: multi-scan
correction based on equivalents (XPREP in SHELXTL-PLUS; Sheldrick, 1996)		578 reflections with I > 2σ(I)
Tmin = 0.160, Tmax = 0.390Rint = 0.080
16043 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0251 restraint
wR(F2) = 0.051H atoms treated by a mixture of
independent and constrained refinement
S = 0.87Δρmax = 0.58 e Å−3
843 reflectionsΔρmin = −0.50 e Å−3
36 parameters
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
Yb10.50000.12174 (2)0.50000.03854 (11)
N10.50000.00000.6022 (4)0.0400 (14)
C10.3244 (3)0.1320 (4)0.4523 (4)0.0776 (17)
H10.30090.08540.41430.093*
C20.3644 (4)0.2112 (5)0.4235 (5)0.090 (2)
H20.37390.22860.36210.108*
C30.3888 (6)0.2621 (5)0.50000.105 (4)
H30.41670.32020.50000.126*
H110.551 (3)0.00000.638 (4)0.07 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Yb10.03668 (19)0.03207 (18)0.0469 (2)0.0000.0000.000
N10.044 (4)0.049 (4)0.026 (3)0.0000.0000.000
C10.040 (2)0.071 (3)0.122 (4)0.015 (2)−0.018 (2)−0.026 (3)
C20.068 (4)0.103 (5)0.100 (5)0.034 (4)−0.004 (3)0.036 (4)
C30.057 (5)0.036 (4)0.224 (14)0.018 (3)0.0000.000
Geometric parameters (Å, °) top
Yb1—N1i2.291 (4)Yb1—C1iv2.626 (5)
Yb1—N12.291 (4)Yb1—H112.75 (3)
Yb1—C3ii2.580 (6)N1—Yb1i2.291 (4)
Yb1—C32.580 (6)N1—H110.894 (10)
Yb1—C2iii2.588 (5)C1—C21.344 (8)
Yb1—C2ii2.588 (5)C1—C1iii1.376 (12)
Yb1—C22.588 (5)C1—H10.9300
Yb1—C2iv2.588 (5)C2—C31.369 (8)
Yb1—C1iii2.626 (5)C2—H20.9300
Yb1—C12.626 (5)C3—C2iii1.369 (8)
Yb1—C1ii2.626 (5)C3—H30.9300
N1i—Yb1—N180.1 (2)C2ii—Yb1—C1ii29.87 (19)
N1i—Yb1—C3ii126.87 (15)C2—Yb1—C1ii144.2 (2)
N1—Yb1—C3ii126.87 (15)C2iv—Yb1—C1ii49.90 (19)
N1i—Yb1—C3126.87 (15)C1iii—Yb1—C1ii148.9 (3)
N1—Yb1—C3126.87 (15)C1—Yb1—C1ii173.6 (2)
C3ii—Yb1—C376.8 (4)N1i—Yb1—C1iv82.80 (12)
N1i—Yb1—C2iii130.95 (16)N1—Yb1—C1iv102.21 (14)
N1—Yb1—C2iii96.19 (19)C3ii—Yb1—C1iv50.0 (2)
C3ii—Yb1—C2iii94.5 (3)C3—Yb1—C1iv123.7 (3)
C3—Yb1—C2iii30.72 (18)C2iii—Yb1—C1iv144.2 (2)
N1i—Yb1—C2ii130.95 (16)C2ii—Yb1—C1iv49.90 (19)
N1—Yb1—C2ii96.19 (19)C2—Yb1—C1iv126.0 (2)
C3ii—Yb1—C2ii30.72 (18)C2iv—Yb1—C1iv29.87 (19)
C3—Yb1—C2ii94.5 (3)C1iii—Yb1—C1iv173.6 (2)
C2iii—Yb1—C2ii98.1 (3)C1—Yb1—C1iv148.9 (3)
N1i—Yb1—C296.19 (19)C1ii—Yb1—C1iv30.4 (3)
N1—Yb1—C2130.95 (16)N1i—Yb1—H1188.7 (8)
C3ii—Yb1—C294.5 (3)N1—Yb1—H1117.5 (5)
C3—Yb1—C230.72 (18)C3ii—Yb1—H11109.6 (4)
C2iii—Yb1—C250.4 (3)C3—Yb1—H11131.6 (12)
C2ii—Yb1—C2120.2 (3)C2iii—Yb1—H11102.1 (13)
N1i—Yb1—C2iv96.19 (19)C2ii—Yb1—H1179.0 (4)
N1—Yb1—C2iv130.95 (16)C2—Yb1—H11145.7 (12)
C3ii—Yb1—C2iv30.72 (18)C2iv—Yb1—H11115.2 (10)
C3—Yb1—C2iv94.5 (3)C1iii—Yb1—H1195.8 (12)
C2iii—Yb1—C2iv120.2 (3)C1—Yb1—H11118.7 (9)
C2ii—Yb1—C2iv50.4 (3)C1ii—Yb1—H1165.9 (8)
C2—Yb1—C2iv98.1 (3)C1iv—Yb1—H1188.3 (12)
N1i—Yb1—C1iii102.21 (14)Yb1i—N1—Yb199.9 (2)
N1—Yb1—C1iii82.80 (12)Yb1i—N1—H11112 (3)
C3ii—Yb1—C1iii123.7 (3)Yb1—N1—H11112 (3)
C3—Yb1—C1iii50.0 (2)C2—C1—C1iii107.9 (4)
C2iii—Yb1—C1iii29.87 (19)C2—C1—Yb173.5 (3)
C2ii—Yb1—C1iii126.0 (2)C1iii—C1—Yb174.82 (13)
C2—Yb1—C1iii49.90 (19)C2—C1—H1126.0
C2iv—Yb1—C1iii144.2 (2)C1iii—C1—H1126.0
N1i—Yb1—C182.80 (12)Yb1—C1—H1117.7
N1—Yb1—C1102.21 (14)C1—C2—C3108.5 (7)
C3ii—Yb1—C1123.7 (3)C1—C2—Yb176.6 (3)
C3—Yb1—C150.0 (2)C3—C2—Yb174.3 (4)
C2iii—Yb1—C149.90 (19)C1—C2—H2125.8
C2ii—Yb1—C1144.2 (2)C3—C2—H2125.8
C2—Yb1—C129.87 (19)Yb1—C2—H2115.4
C2iv—Yb1—C1126.0 (2)C2iii—C3—C2107.2 (9)
C1iii—Yb1—C130.4 (3)C2iii—C3—Yb174.9 (3)
N1i—Yb1—C1ii102.21 (14)C2—C3—Yb174.9 (3)
N1—Yb1—C1ii82.80 (12)C2iii—C3—H3126.4
C3ii—Yb1—C1ii50.0 (2)C2—C3—H3126.4
C3—Yb1—C1ii123.7 (3)Yb1—C3—H3116.0
C2iii—Yb1—C1ii126.0 (2)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y, −z+1; (iii) x, y, −z+1; (iv) −x+1, y, z.
Acknowledgements top

The authors are indebted to Thomas Miller for performing the single-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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