Tetra-μ(3)-tert-butano-lato-tetra-thallium(I).

The title compound, [Tl(4)(C(4)H(9)O)(4)], featuring a (Tl-O)(4) cube, crystallizes with a quarter-mol-ecule (located on a special position of site symmetry ..) and a half-mol-ecule (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 recta-ngular 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 = 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810047550/kj2165sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047550/kj2165Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[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

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

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)

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
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*

	U11	U22	U33	U12	U13	U23
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)

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)