Redetermination of tetra­kis(trimethyl­stann­yl)germane

Bauer, M.; Groy, T.L.; Kouvetakis, J.

doi:10.1107/S1600536807054724

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m49

https://doi.org/10.1107/S1600536807054724

Open

access

Redetermination of tetrakis(trimethylstannyl)germane

Matthew Bauer,^a Thomas L. Groy ^a ^* and John Kouvetakis ^a

^aDepartment of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287-1604, USA
^*Correspondence e-mail: tgroy@asu.edu

(Received 11 October 2007; accepted 30 October 2007; online 6 December 2007)

Redetermination of the structure of the title compound, [Ge(SnMe₃)₄] or [GeSn₄(CH₃)₁₂], previously refined from powder diffraction data only [Dinnebier, Bernatowicz, Helluy, Sebald, Wunschel, Fitch & van Smaalen et al. (2002 ). Acta Cryst. B58, 52–61], confirms that four bulky trimethylstannyl ligands surround the central Ge atom (site symmetry 1) in a tetrahedral coordination.

Related literature

For related literature, see: Dinnebier et al. (2002); Wrackmeyer & Bernatowicz (1999 ); Chizmeshya et al. (2003 ).

Experimental

Crystal data

[GeSn₄(CH₃)₁₂]
M_r = 727.76
Triclinic, $[P \overline 1]$
a = 9.1666 (7) Å
b = 9.9521 (7) Å
c = 14.5400 (14) Å
α = 90.033 (2)°
β = 90.546 (1)°
γ = 111.736 (1)°
V = 1232.06 (17) Å³
Z = 2
Mo Kα radiation
μ = 5.19 mm⁻¹
T = 298 (2) K
0.22 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.317, T_max = 0.460
12284 measured reflections
5646 independent reflections
4466 reflections with I > 2σ(I)
R_int = 0.085

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.105
S = 1.01
5646 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 1.09 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1997 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807054724/mg2036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807054724/mg2036Isup2.hkl

checkCIF report

Comment top

The structure of the Ge[Sn(CH₃)₃]₄ cluster has been previously determined by powder X-ray diffraction and magic angle spinning NMR spectroscopy (Dinnebier et al., 2002). Here, we have developed a new synthetic route to form Ge[Sn(CH₃)₃]₄ in high yields (80–90%) and, for the first time, adequately sized crystals suitable for a single-crystal structure determination. The long-term objective is to use this bonding information to understand structural trends in recently developed Ge_{1 -}_xSn_x and Ge_{1 -}_x_-_ySn_xSi_y semiconductor alloys, including unusual deviations from Vegard's Law (Chizmeshya et al., 2003). Various tetrahedral cluster compounds with the general formula A(BH₃)₄ (where {A, B}= {Si, Ge, Sn}) are potentially viable low-temperature CVD precursors of Group IV alloys with highly metastable compositions and structures that cannot be obtained by conventional growth routes.

The central Ge atom is tetrahedrally coordinated with four Me₃Sn ligands. The average Ge—Sn distance of 2.5934 (8) Å agrees well with the predicted value of 2.5680 Å for a Ge(SnH₃)₄ analogue (Chizmeshya et al., 2003). In the previous structure determination using powder data, estimated standard deviations for bond lengths and angles are given as 0.04 Å and 0.1°, respectively. In the current determination, an improvement in precision for the structure can be seen in the Ge—Sn core bond lengths, which range from 2.5912 (7) to 2.5953 (8) Å, and bond angles, which range from 107.59 (3) to 111.09 (3) °.

Related literature top

For related literature, see: Dinnebier et al. (2002); Wrackmeyer & Bernatowicz (1999); Chizmeshya et al. (2003).

Experimental top

After addition of GeH₄ (0.1 g; 1.3 mmol) to Me₃SnNMe₂ (1.0 g; 5 mmol) at -196 °C, the mixture was warmed to room temperature and stirred for 24 h. The volatiles were identified as HNMe₂ and small amounts of GeH₄ by gas phase IR spectroscopy and were removed at room temperature in vacuo.

GeH₄ + 4 Me₃SnNMe₂ => Ge[Sn(CH₃)₃]₄ + 4 HNMe₂

The white solid was recrystallized from a saturated toluene solution at -20 °C and the purity was confirmed by matching the IR spectrum, powder XRD pattern, 1H NMR spectrum, and melting point with the published data (Dinnebier et al., 2002; Wrackmeyer & Bernatowicz, 1999). This represents a simpler alternative than the multistepped reaction, hydrolysis, and separation procedure required with the reaction of Me₃SnLi and GeCl₄ in tetrahydrofuran. Larger crystals, suitable for single-crystal XRD, were grown by subliming the pure powder in a sealed quartz tube held at 100 °C on one end and room temperature on the other. In contrast, sublimation at 135 °C in vacuo yields only microcrystalline powders.

Structure description top

For related literature, see: Dinnebier et al. (2002); Wrackmeyer & Bernatowicz (1999); Chizmeshya et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

Fig. 1. Structure of Ge[Sn(CH₃)₃]₄. (Ellipsoids are drawn at the 50% probability level.)

tetrakis(trimethylstannyl)germane top

Crystal data top

[GeSn₄(CH₃)₁₂]	Z = 2
M_r = 727.76	F(000) = 680
Triclinic, P1	D_x = 1.962 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1666 (7) Å	Cell parameters from 6668 reflections
b = 9.9521 (7) Å	θ = 2.2–27.5°
c = 14.5400 (14) Å	µ = 5.19 mm⁻¹
α = 90.033 (2)°	T = 298 K
β = 90.546 (1)°	Block, colorless
γ = 111.736 (1)°	0.22 × 0.22 × 0.15 mm
V = 1232.06 (17) Å³

Data collection top

Bruker SMART APEX diffractometer	5646 independent reflections
Radiation source: fine-focus sealed tube	4466 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
ω scan	θ_max = 27.6°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
T_min = 0.317, T_max = 0.460	k = −12→12
12284 measured reflections	l = −18→18

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0304P)²] where P = (F_o² + 2F_c²)/3
5646 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 1.09 e Å⁻³
0 restraints	Δρ_min = −1.01 e Å⁻³

Crystal data top

[GeSn₄(CH₃)₁₂]	γ = 111.736 (1)°
M_r = 727.76	V = 1232.06 (17) Å³
Triclinic, P1	Z = 2
a = 9.1666 (7) Å	Mo Kα radiation
b = 9.9521 (7) Å	µ = 5.19 mm⁻¹
c = 14.5400 (14) Å	T = 298 K
α = 90.033 (2)°	0.22 × 0.22 × 0.15 mm
β = 90.546 (1)°

Data collection top

Bruker SMART APEX diffractometer	5646 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	4466 reflections with I > 2σ(I)
T_min = 0.317, T_max = 0.460	R_int = 0.085
12284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.01	Δρ_max = 1.09 e Å⁻³
5646 reflections	Δρ_min = −1.01 e Å⁻³
154 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

	x	y	z	U_iso*/U_eq
Ge1	0.75863 (7)	0.73542 (6)	0.75103 (5)	0.04589 (16)
Sn1	0.76633 (5)	0.47736 (5)	0.75113 (4)	0.05566 (14)
Sn2	0.67526 (5)	0.79813 (5)	0.91050 (3)	0.05480 (14)
Sn3	0.55868 (5)	0.75649 (5)	0.63013 (3)	0.05205 (13)
Sn4	1.03424 (5)	0.92048 (5)	0.70999 (3)	0.05197 (13)
C1A	0.5374 (9)	0.3234 (8)	0.7776 (6)	0.084 (2)
H1AA	0.5400	0.2278	0.7776	0.125*
H1AB	0.4659	0.3296	0.7306	0.125*
H1AC	0.5030	0.3432	0.8364	0.125*
C1B	0.9275 (9)	0.4584 (9)	0.8546 (7)	0.092 (3)
H1BA	0.9284	0.3623	0.8534	0.138*
H1BB	0.8949	0.4776	0.9141	0.138*
H1BC	1.0311	0.5270	0.8424	0.138*
C1C	0.8419 (9)	0.4301 (9)	0.6205 (6)	0.084 (2)
H1CA	0.8442	0.3344	0.6214	0.126*
H1CB	0.9451	0.4990	0.6080	0.126*
H1CC	0.7702	0.4355	0.5734	0.126*
C2A	0.8272 (9)	0.7754 (10)	1.0181 (6)	0.088 (3)
H2AA	0.7939	0.7992	1.0762	0.132*
H2AB	0.9332	0.8395	1.0067	0.132*
H2AC	0.8224	0.6774	1.0194	0.132*
C2B	0.6866 (10)	1.0148 (8)	0.9115 (6)	0.087 (2)
H2BA	0.6556	1.0371	0.9707	0.131*
H2BB	0.6172	1.0264	0.8651	0.131*
H2BC	0.7922	1.0790	0.8993	0.131*
C2C	0.4400 (9)	0.6608 (10)	0.9404 (6)	0.088 (3)
H2CA	0.4116	0.6858	0.9996	0.132*
H2CB	0.4321	0.5619	0.9409	0.132*
H2CC	0.3703	0.6730	0.8943	0.132*
C3A	0.6191 (9)	0.7151 (9)	0.4940 (5)	0.085 (2)
H3AA	0.5431	0.7236	0.4509	0.128*
H3AB	0.6202	0.6191	0.4909	0.128*
H3AC	0.7212	0.7840	0.4792	0.128*
C3B	0.3259 (8)	0.6064 (8)	0.6589 (6)	0.076 (2)
H3BA	0.2539	0.6160	0.6134	0.115*
H3BB	0.2952	0.6266	0.7187	0.115*
H3BC	0.3247	0.5095	0.6575	0.115*
C3C	0.5645 (8)	0.9736 (8)	0.6319 (6)	0.075 (2)
H3CA	0.4909	0.9828	0.5874	0.112*
H3CB	0.6683	1.0393	0.6172	0.112*
H3CC	0.5371	0.9959	0.6920	0.112*
C4A	1.2038 (8)	0.9083 (9)	0.8092 (6)	0.081 (2)
H4AA	1.3058	0.9769	0.7938	0.121*
H4AB	1.2058	0.8125	0.8088	0.121*
H4AC	1.1756	0.9299	0.8693	0.121*
C4B	1.0969 (8)	0.8697 (9)	0.5750 (5)	0.078 (2)
H4BA	1.1990	0.9379	0.5593	0.117*
H4BB	1.0210	0.8748	0.5306	0.117*
H4BC	1.0986	0.7738	0.5752	0.117*
C4C	1.0413 (9)	1.1383 (7)	0.7095 (6)	0.080 (2)
H4CA	1.1451	1.2033	0.6940	0.120*
H4CB	1.0148	1.1625	0.7693	0.120*
H4CC	0.9674	1.1468	0.6648	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0459 (3)	0.0435 (3)	0.0477 (4)	0.0158 (3)	0.0020 (3)	0.0011 (3)
Sn1	0.0596 (3)	0.0444 (2)	0.0628 (3)	0.0192 (2)	−0.0006 (2)	0.0007 (2)
Sn2	0.0586 (3)	0.0588 (3)	0.0469 (3)	0.0216 (2)	0.0030 (2)	0.0002 (2)
Sn3	0.0501 (2)	0.0549 (3)	0.0501 (3)	0.0183 (2)	−0.00229 (19)	−0.0012 (2)
Sn4	0.0469 (2)	0.0507 (3)	0.0549 (3)	0.01392 (19)	0.00327 (19)	0.0024 (2)
C1A	0.079 (5)	0.058 (4)	0.102 (7)	0.012 (4)	0.009 (5)	0.015 (4)
C1B	0.086 (6)	0.081 (6)	0.119 (8)	0.042 (5)	−0.015 (5)	0.022 (5)
C1C	0.098 (6)	0.080 (5)	0.080 (6)	0.039 (5)	0.011 (5)	−0.021 (4)
C2A	0.091 (6)	0.110 (7)	0.068 (6)	0.045 (5)	−0.023 (4)	−0.006 (5)
C2B	0.120 (7)	0.072 (5)	0.076 (6)	0.041 (5)	0.003 (5)	−0.012 (4)
C2C	0.071 (5)	0.105 (7)	0.082 (6)	0.025 (5)	0.022 (4)	0.018 (5)
C3A	0.102 (6)	0.091 (6)	0.051 (5)	0.022 (5)	0.010 (4)	−0.011 (4)
C3B	0.055 (4)	0.082 (5)	0.084 (6)	0.016 (4)	0.006 (4)	−0.003 (4)
C3C	0.080 (5)	0.060 (4)	0.086 (6)	0.028 (4)	0.000 (4)	0.009 (4)
C4A	0.063 (4)	0.102 (6)	0.080 (6)	0.035 (4)	−0.020 (4)	−0.016 (5)
C4B	0.079 (5)	0.084 (5)	0.069 (5)	0.026 (4)	0.029 (4)	0.006 (4)
C4C	0.094 (6)	0.049 (4)	0.094 (7)	0.022 (4)	0.009 (5)	0.009 (4)

Geometric parameters (Å, º) top

Ge1—Sn4	2.5912 (7)	Sn2—C2C	2.132 (7)
Ge1—Sn3	2.5917 (8)	Sn2—C2A	2.152 (7)
Ge1—Sn1	2.5952 (7)	Sn3—C3A	2.141 (7)
Ge1—Sn2	2.5953 (8)	Sn3—C3C	2.141 (7)
Sn1—C1A	2.130 (7)	Sn3—C3B	2.148 (7)
Sn1—C1C	2.139 (8)	Sn4—C4C	2.145 (7)
Sn1—C1B	2.156 (7)	Sn4—C4A	2.147 (7)
Sn2—C2B	2.120 (8)	Sn4—C4B	2.162 (7)

Sn4—Ge1—Sn3	108.29 (3)	C2B—Sn2—Ge1	110.0 (2)
Sn4—Ge1—Sn1	109.08 (3)	C2C—Sn2—Ge1	110.9 (3)
Sn3—Ge1—Sn1	111.09 (3)	C2A—Sn2—Ge1	111.2 (2)
Sn4—Ge1—Sn2	109.91 (3)	C3A—Sn3—C3C	107.0 (3)
Sn3—Ge1—Sn2	107.59 (3)	C3A—Sn3—C3B	108.5 (3)
Sn1—Ge1—Sn2	110.83 (3)	C3C—Sn3—C3B	110.3 (3)
C1A—Sn1—C1C	108.9 (3)	C3A—Sn3—Ge1	111.5 (2)
C1A—Sn1—C1B	109.3 (3)	C3C—Sn3—Ge1	108.7 (2)
C1C—Sn1—C1B	108.0 (3)	C3B—Sn3—Ge1	110.9 (2)
C1A—Sn1—Ge1	109.4 (2)	C4C—Sn4—C4A	108.0 (3)
C1C—Sn1—Ge1	110.3 (2)	C4C—Sn4—C4B	108.7 (3)
C1B—Sn1—Ge1	111.0 (2)	C4A—Sn4—C4B	109.4 (3)
C2B—Sn2—C2C	107.9 (3)	C4C—Sn4—Ge1	112.1 (2)
C2B—Sn2—C2A	108.2 (3)	C4A—Sn4—Ge1	109.6 (2)
C2C—Sn2—C2A	108.6 (3)	C4B—Sn4—Ge1	109.0 (2)

Experimental details

Crystal data
Chemical formula	[GeSn₄(CH₃)₁₂]
M_r	727.76
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.1666 (7), 9.9521 (7), 14.5400 (14)
α, β, γ (°)	90.033 (2), 90.546 (1), 111.736 (1)
V (Å³)	1232.06 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.19
Crystal size (mm)	0.22 × 0.22 × 0.15

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.317, 0.460
No. of measured, independent and observed [I > 2σ(I)] reflections	12284, 5646, 4466
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.105, 1.01
No. of reflections	5646
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.09, −1.01

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Bruker, 1997).

Acknowledgements

We express our gratitude to the National Science Foundation for their contribution toward the purchase of the single-crystal instrumentation used in this study through Award #CHE-9808440.

References

Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2002). SADABS, SMART (Version 5.625) and SAINT (Version 6.28A). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chizmeshya, A. V. G., Bauer, M. R. & Kouvetakis, J. (2003). Chem. Mater. 15, 2511–2519. Web of Science CrossRef CAS Google Scholar
Dinnebier, R. E., Bernatowicz, P., Helluy, X., Sebald, A., Wunschel, M., Fitch, A. & van Smaalen, S. (2002). Acta Cryst. B58, 52–61. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Wrackmeyer, B. & Bernatowicz, P. (1999). Magn. Reson. Chem. 37, 418–420. CrossRef CAS Google Scholar