Acta Crystallographica Section E: Structure Reports Online

Acta Crystallogr Sect E Struct Rep Online. 66(Pt 12): m1621-m1621

Tetra-μ₃-tert-butanolato-tetrathallium(I)

Florian Blasberga, Hans-Wolfram Lernera, Michael Boltea*

a. Institut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: bolte@chemie.uni-frankfurt.de

© Blasberg et al. 2010

DOI: 10.1107/S1600536810047550

Published online: 20 November 2010

Abstract

The title compound, [Tl₄(C₄H₉O)₄], featuring a (Tl—O)₄ cube, crystallizes with a quarter-molecule (located on a special position of site symmetry ..) and a half-molecule (located on a special position of site symmetry 23.) in the asymmetric unit. The Tl—O bond distances range from 2.463 (12) to 2.506 (12) Å. All O—Tl—O bond angles are smaller than 90° whereas the Tl—O—Tl angles are wider than a rectangular angle.

Related literature

For the use of bulky silyl chalcogenolate ligands of the type ESiR ₃ ⁻ and alkyl chalcogenolates E(alkyl)⁻ (E = O, S, Se, Te) with especially bulky alkoxides to stabilize transition metal centres, see: Wolczanski (2009 ▶); Kückmann et al. (2005 ▶, 2008 ▶, 2010 ▶). For substitution reactions of transition metal atoms, see: Kern et al. (2008 ▶); Lerner et al. (2002 ▶, 2005 ▶). The title compound was prepared according to a slightly changed published procedure, see: Schmidbaur et al. (1968 ▶).

Experimental

Crystal data

[Tl₄(C₄H₉O)₄]

M r = 1109.93

Cubic,

a = 17.1500 (15) Å

V = 5044.2 (8) Å³

Z = 8

Mo Kα radiation

μ = 25.49 mm⁻¹

T = 173 K

0.21 × 0.18 × 0.10 mm

Data collection

Stoe IPDS II two-circle diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2009 ▶; Blessing, 1995 ▶) T min = 0.075, T max = 0.185

13612 measured reflections

1489 independent reflections

1226 reflections with I > 2σ(I)

R int = 0.084

Refinement

R[F ² > 2σ(F ²)] = 0.042

wR(F ²) = 0.083

S = 1.00

1489 reflections

73 parameters

6 restraints

H-atom parameters constrained

Δρmax = 1.77 e Å⁻³

Δρmin = −1.01 e Å⁻³

Absolute structure: Flack (1983 ▶), 711 Friedel pairs

Flack parameter: 0.00 (7)

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2165).

supplementary crystallographic information

Comment

In a number of recent studies bulky silyl chalcogenolate ligands of the type ESiR₃⁻ and alkyl chalcogenolates E(alkyl)⁻ (E = O, S, Se, Te) with especially bulky alkoxides have been used to stabilize transition metal centers (Wolczanski, 2009; Kückmann et al. 2005, 2008, 2010). In macromolecular chemistry, these ligands have also found application. Chalcogen-based ligands offer a variety of possible binding modes. Chalcogenolates are often found bridging two or more metal ions. Normally, transition metal complexes possess 6 e⁻ thiolate ligands in a µ₃-binding mode. Recently, however, we have shown that the anion of the mixed-valence Mn(I/II) complex Na(thf)₆[(OC)₃Mn(µ-SSitBu₃)₃MnSSitBu₃] contains a terminal thiolate ligand with a linear Mn—S—Si unit (Kückmann et al. 2008). The prerequisite for six-electron donation (2 σ- and 4 π-electrons) comparable with Cp⁻ is thus fulfilled. One approach is to create such complexes by substitution reactions of transition metal halogenides with alkali metal alkoxides as M⁺[OC(CH₃)₃]⁻ or alkali metal siloxides M⁺[OSiR₃]- (Kern et al. 2008; Lerner et al. 2005, 2002). In most cases the reactions that occur between alkali metal alkoxides and transition metal halides are not quantitative. Another approach to complexes with chalcogen coordination is to start from thallium alkoxides which react almost quantitatively with transition metal chlorides due to the poor solubility of TlCl. In this paper we report the synthesis and the crystal structure of [TlOtBu]₄. The title compound [TlOtBu]₄ was prepared according to a slightly changed published procedure (Schmidbaur et al. 1968), as shown in Fig. 2. The following modifications have been made in our approach: thallium ethoxide was used instead of thallium methoxide and potassium tert-butoxide was substituted for sodium tert-butoxide.

Experimental

In a flame-dried vial 1.1 ml thallium ethoxide (3.77 g, 15.1 mmol) was added to 1.70 g potassium tert-butoxide (15.1 mmol) in 50 ml benzene. After flame-sealing, the vial was heated to 80 °C for four days. The vial was opened, the crude reaction mixture filtered hot under an nitrogen atmosphere, the solid residue was washed with 20 ml benzene and the combined filtrates evaporated to dryness. The remaining colorless solid was suspended in ether and allowed to settle. A sample of the supernatant was transferred to a flame-dried Schlenk vessel and stored at -35°C. After two days colorless crystals of the composition [TlOtBu]₄ deposited and were separated from the mother liquor (Yield 15%).

Refinement

H atoms were located in a difference map, but geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(H) = 1.5 Ueq(C)] and with C—H = 0.98 Å.

Figures

Fig. 1.View larger versionFig. 1. Perspective view of one of the two independent molecules of the title compound with the atom numbering scheme for the symmetry independent atoms; displacement ellipsoids are at the 50% probability level; H atoms are omitted for clarity.

Fig. 2.View larger versionFig. 2. Preparation of the title compound.

Crystal data

See full table

Data collection

See full table

Refinement

See full table

Special details

See full table

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

See full table

Atomic displacement parameters (Å²)

See full table

Geometric parameters (Å, °)

See full table

Symmetry codes: (i) −x+3/2, −z+3/2, y−1/2; (ii) −x+3/2, z+1/2, −y+3/2; (iii) −x+1, y, −z+1; (iv) −x+1, −y+1, z; (v) −z+1, −x+1, y; (vi) −y+1, z, −x+1; (vii) x, −y+2, −z+1.

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References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Kern, B., Vitze, H., Bolte, M., Wagner, M. & Lerner, H.-W. (2008). Z. Anorg. Allg. Chem.634, 1830–1832.

Kückmann, T. I., Hermsen, M., Bolte, M., Wagner, M. & Lerner, H.-W. (2005). Inorg. Chem.44, 3449–3458.

Kückmann, T. I., Schödel, F., Sänger, I., Bolte, M., Wagner, M. & Lerner, H.-W. (2008). Organometallics, 27, 3272–3278.

Kückmann, T. I., Schödel, F., Sänger, I., Bolte, M., Wagner, M. & Lerner, H.-W. (2010). Eur. J. Inorg. Chem. pp. 468–475.

Lerner, H.-W., Scholz, S. & Bolte, M. (2002). Organometallics, 21, 3827–3830.

Lerner, H.-W., Scholz, S., Wiberg, N., Polborn, K., Bolte, M. & Wagner, M. (2005). Z. Anorg. Allg. Chem.631, 1863–1870.

Schmidbaur, H., Bergfeld, M. & Schindler, F. (1968). Z. Anorg. Allg. Chem.363, 73–83.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.

Wolczanski, P. T. (2009). Chem. Commun. pp. 740–757.

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Fig. 1.

Perspective view of one of the two independent molecules of the title compound with the atom numbering scheme for the symmetry independent atoms; displacement ellipsoids are at the 50% probability level; H atoms are omitted for clarity.

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Fig. 2.

Preparation of the title compound.

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[Tl₄(C₄H₉O)₄] | Dx = 2.923 Mg m⁻³
Mr = 1109.93 | Mo Kα radiation, λ = 0.71073 Å
Cubic, P43n | Cell parameters from 7201 reflections
Hall symbol: P -4n 2 3 | θ = 3.4–25.9°
a = 17.1500 (15) Å | µ = 25.49 mm⁻¹
V = 5044.2 (8) Å³ | T = 173 K
Z = 8 | Plate, colourless
F(000) = 3904 | 0.21 × 0.18 × 0.10 mm

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Stoe IPDS II two-circle diffractometer | 1489 independent reflections
Radiation source: fine-focus sealed tube | 1226 reflections with I > 2σ(I)
graphite | Rint = 0.084
ω scans | θmax = 25.0°, θmin = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −18→20
Tmin = 0.075, Tmax = 0.185 | k = −19→20
13612 measured reflections | l = −20→18

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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)] = 0.042 | H-atom parameters constrained
wR(F²) = 0.083 | w = 1/[σ²(Fo²) + (0.037P)²] where P = (Fo² + 2Fc²)/3
S = 1.00 | (Δ/σ)max = 0.001
1489 reflections | Δρmax = 1.77 e Å⁻³
73 parameters | Δρmin = −1.01 e Å⁻³
6 restraints | Absolute structure: Flack (1983), 711 Friedel pairs
Primary atom site location: structure-invariant direct methods | Flack parameter: 0.00 (7)

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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.

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| x | y | z | Uiso*/Ueq |
Tl1 | 0.66760 (4) | 0.91953 (4) | 0.57229 (3) | 0.02168 (17) |
O1 | 0.8130 (7) | 0.9310 (7) | 0.5635 (7) | 0.022 (2) |
C1 | 0.8550 (13) | 0.8777 (10) | 0.6115 (13) | 0.029 (4) |
C2 | 0.9386 (12) | 0.8950 (18) | 0.6078 (19) | 0.059 (8) |
H2A | 0.9478 | 0.9485 | 0.6256 | 0.088* |
H2B | 0.9569 | 0.8895 | 0.5539 | 0.088* |
H2C | 0.9671 | 0.8586 | 0.6414 | 0.088* |
C3 | 0.8400 (19) | 0.7958 (10) | 0.583 (2) | 0.059 (7) |
H3A | 0.7839 | 0.7853 | 0.5844 | 0.089* |
H3B | 0.8669 | 0.7588 | 0.6177 | 0.089* |
H3C | 0.8596 | 0.7901 | 0.5301 | 0.089* |
C4 | 0.8261 (16) | 0.8852 (14) | 0.6961 (12) | 0.041 (6) |
H4A | 0.8368 | 0.9380 | 0.7153 | 0.061* |
H4B | 0.8533 | 0.8472 | 0.7290 | 0.061* |
H4C | 0.7698 | 0.8753 | 0.6980 | 0.061* |
Tl1A | 0.42129 (4) | 0.42129 (4) | 0.42129 (4) | 0.0223 (2) |
O1A | 0.5652 (6) | 0.4348 (6) | 0.4348 (6) | 0.020 (4) |
C1A | 0.6118 (13) | 0.3882 (13) | 0.3882 (13) | 0.020 (7) |
C2A | 0.6960 (12) | 0.3942 (13) | 0.4110 (14) | 0.035 (5) |
H2A1 | 0.7125 | 0.4488 | 0.4086 | 0.053* |
H2A2 | 0.7277 | 0.3631 | 0.3751 | 0.053* |
H2A3 | 0.7027 | 0.3746 | 0.4643 | 0.053* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
Tl1 | 0.0231 (3) | 0.0211 (3) | 0.0208 (3) | −0.0047 (3) | 0.0036 (3) | 0.0011 (3)
O1 | 0.031 (6) | 0.020 (6) | 0.015 (6) | 0.005 (5) | −0.005 (5) | 0.009 (5)
C1 | 0.036 (10) | 0.016 (9) | 0.034 (12) | 0.012 (8) | −0.009 (9) | 0.003 (8)
C2 | 0.023 (10) | 0.065 (16) | 0.09 (2) | 0.006 (12) | 0.006 (13) | 0.040 (14)
C3 | 0.09 (2) | 0.007 (8) | 0.08 (2) | 0.007 (11) | −0.018 (18) | 0.008 (12)
C4 | 0.063 (16) | 0.041 (13) | 0.019 (10) | 0.018 (11) | 0.007 (10) | 0.003 (8)
Tl1A | 0.0223 (2) | 0.0223 (2) | 0.0223 (2) | −0.0035 (3) | −0.0035 (3) | −0.0035 (3)
O1A | 0.020 (4) | 0.020 (4) | 0.020 (4) | 0.005 (5) | 0.005 (5) | −0.005 (5)
C1A | 0.020 (7) | 0.020 (7) | 0.020 (7) | 0.003 (8) | 0.003 (8) | −0.003 (8)
C2A | 0.025 (8) | 0.041 (8) | 0.041 (9) | 0.011 (6) | 0.007 (7) | −0.010 (7)

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Tl1—O1i | 2.463 (12) | C4—H4A | 0.9800
Tl1—O1ii | 2.493 (11) | C4—H4B | 0.9800
Tl1—O1 | 2.506 (12) | C4—H4C | 0.9800
O1—C1 | 1.42 (2) | Tl1A—O1A | 2.490 (8)
O1—Tl1ii | 2.463 (12) | Tl1A—O1Aiii | 2.490 (8)
O1—Tl1i | 2.492 (11) | Tl1A—O1Aiv | 2.490 (8)
C1—C2 | 1.47 (3) | O1A—C1A | 1.38 (4)
C1—C3 | 1.51 (3) | O1A—Tl1Aiii | 2.490 (8)
C1—C4 | 1.54 (3) | O1A—Tl1Aiv | 2.490 (8)
C2—H2A | 0.9800 | C1A—C2Av | 1.50 (2)
C2—H2B | 0.9800 | C1A—C2Avi | 1.50 (2)
C2—H2C | 0.9800 | C1A—C2A | 1.50 (2)
C3—H3A | 0.9800 | C2A—H2A1 | 0.9800
C3—H3B | 0.9800 | C2A—H2A2 | 0.9800
C3—H3C | 0.9800 | C2A—H2A3 | 0.9800
O1i—Tl1—O1ii | 81.0 (4) | H3B—C3—H3C | 109.5
O1i—Tl1—O1 | 78.3 (4) | C1—C4—H4A | 109.5
O1ii—Tl1—O1 | 77.8 (4) | C1—C4—H4B | 109.5
O1i—Tl1—Tl1vii | 41.8 (3) | H4A—C4—H4B | 109.5
O1ii—Tl1—Tl1vii | 41.2 (3) | C1—C4—H4C | 109.5
O1—Tl1—Tl1vii | 84.3 (2) | H4A—C4—H4C | 109.5
C1—O1—Tl1ii | 119.7 (10) | H4B—C4—H4C | 109.5
C1—O1—Tl1i | 119.3 (11) | O1A—Tl1A—O1Aiii | 78.9 (6)
Tl1ii—O1—Tl1i | 97.0 (4) | O1A—Tl1A—O1Aiv | 78.9 (6)
C1—O1—Tl1 | 114.7 (11) | O1Aiii—Tl1A—O1Aiv | 78.9 (6)
Tl1ii—O1—Tl1 | 101.8 (4) | C1A—O1A—Tl1Aiii | 117.7 (11)
Tl1i—O1—Tl1 | 101.0 (4) | C1A—O1A—Tl1Aiv | 117.7 (11)
O1—C1—C2 | 109.8 (17) | Tl1Aiii—O1A—Tl1Aiv | 100.1 (5)
O1—C1—C3 | 109.2 (17) | C1A—O1A—Tl1A | 117.7 (11)
C2—C1—C3 | 110 (2) | Tl1Aiii—O1A—Tl1A | 100.1 (5)
O1—C1—C4 | 109.1 (16) | Tl1Aiv—O1A—Tl1A | 100.1 (5)
C2—C1—C4 | 110 (2) | O1A—C1A—C2Av | 111.4 (15)
C3—C1—C4 | 109 (2) | O1A—C1A—C2Avi | 111.4 (15)
C1—C2—H2A | 109.5 | C2Av—C1A—C2Avi | 107.4 (16)
C1—C2—H2B | 109.5 | O1A—C1A—C2A | 111.4 (15)
H2A—C2—H2B | 109.5 | C2Av—C1A—C2A | 107.4 (16)
C1—C2—H2C | 109.5 | C2Avi—C1A—C2A | 107.4 (16)
H2A—C2—H2C | 109.5 | C1A—C2A—H2A1 | 109.5
H2B—C2—H2C | 109.5 | C1A—C2A—H2A2 | 109.5
C1—C3—H3A | 109.5 | H2A1—C2A—H2A2 | 109.5
C1—C3—H3B | 109.5 | C1A—C2A—H2A3 | 109.5
H3A—C3—H3B | 109.5 | H2A1—C2A—H2A3 | 109.5
C1—C3—H3C | 109.5 | H2A2—C2A—H2A3 | 109.5
H3A—C3—H3C | 109.5 |  |
O1i—Tl1—O1—C1 | −137.9 (13) | Tl1—O1—C1—C4 | −53.8 (18)
O1ii—Tl1—O1—C1 | 139.0 (13) | O1Aiii—Tl1A—O1A—C1A | 139.7 (13)
Tl1vii—Tl1—O1—C1 | −179.8 (12) | O1Aiv—Tl1A—O1A—C1A | −139.7 (13)
O1i—Tl1—O1—Tl1ii | 91.4 (5) | O1Aiii—Tl1A—O1A—Tl1Aiii | 10.8 (5)
O1ii—Tl1—O1—Tl1ii | 8.2 (4) | O1Aiv—Tl1A—O1A—Tl1Aiii | 91.49 (15)
Tl1vii—Tl1—O1—Tl1ii | 49.5 (3) | O1Aiii—Tl1A—O1A—Tl1Aiv | −91.49 (15)
O1i—Tl1—O1—Tl1i | −8.2 (4) | O1Aiv—Tl1A—O1A—Tl1Aiv | −10.8 (5)
O1ii—Tl1—O1—Tl1i | −91.4 (5) | Tl1Aiii—O1A—C1A—C2Av | 68.4 (10)
Tl1vii—Tl1—O1—Tl1i | −50.1 (3) | Tl1Aiv—O1A—C1A—C2Av | −171.6 (10)
Tl1ii—O1—C1—C2 | −53 (2) | Tl1A—O1A—C1A—C2Av | −51.6 (10)
Tl1i—O1—C1—C2 | 66 (2) | Tl1Aiii—O1A—C1A—C2Avi | −171.6 (10)
Tl1—O1—C1—C2 | −174.2 (19) | Tl1Aiv—O1A—C1A—C2Avi | −51.6 (10)
Tl1ii—O1—C1—C3 | −173.5 (18) | Tl1A—O1A—C1A—C2Avi | 68.4 (10)
Tl1i—O1—C1—C3 | −55 (2) | Tl1Aiii—O1A—C1A—C2A | −51.6 (10)
Tl1—O1—C1—C3 | 65 (2) | Tl1Aiv—O1A—C1A—C2A | 68.4 (10)
Tl1ii—O1—C1—C4 | 67.6 (19) | Tl1A—O1A—C1A—C2A | −171.6 (10)
Tl1i—O1—C1—C4 | −173.7 (14) |  |

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