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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054724/mg2036sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054724/mg2036Isup2.hkl
Contains datablock I

CCDC reference: 674183

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](n-C) = 0.008 Å
  • R factor = 0.049
  • wR factor = 0.105
  • Data-to-parameter ratio = 36.7

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT761_ALERT_1_A CIF Contains no X-H Bonds ...................... ? PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles .......... ?
Alert level C PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Sn1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Sn2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Sn3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Sn4 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 36
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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 Ge1 - xSnx and Ge1 - x-ySnxSiy 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.

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C–H = 0.96 Å and Uiso(H) = 1.5 times Ueq(C).

Structure description 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 Ge1 - xSnx and Ge1 - x-ySnxSiy 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) °.

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
[Figure 1] 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
Mr = 727.76F(000) = 680
Triclinic, P1Dx = 1.962 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1666 (7) ÅCell parameters from 6668 reflections
b = 9.9521 (7) Åθ = 2.2–27.5°
c = 14.5400 (14) ŵ = 5.19 mm1
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 tube4466 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
ω scanθmax = 27.6°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1111
Tmin = 0.317, Tmax = 0.460k = 1212
12284 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0304P)2]
where P = (Fo2 + 2Fc2)/3
5646 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 1.09 e Å3
0 restraintsΔρmin = 1.01 e Å3
Crystal data top
[GeSn4(CH3)12]γ = 111.736 (1)°
Mr = 727.76V = 1232.06 (17) Å3
Triclinic, P1Z = 2
a = 9.1666 (7) ÅMo Kα radiation
b = 9.9521 (7) ŵ = 5.19 mm1
c = 14.5400 (14) ÅT = 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)
Tmin = 0.317, Tmax = 0.460Rint = 0.085
12284 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.01Δρmax = 1.09 e Å3
5646 reflectionsΔρmin = 1.01 e Å3
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
xyzUiso*/Ueq
Ge10.75863 (7)0.73542 (6)0.75103 (5)0.04589 (16)
Sn10.76633 (5)0.47736 (5)0.75113 (4)0.05566 (14)
Sn20.67526 (5)0.79813 (5)0.91050 (3)0.05480 (14)
Sn30.55868 (5)0.75649 (5)0.63013 (3)0.05205 (13)
Sn41.03424 (5)0.92048 (5)0.70999 (3)0.05197 (13)
C1A0.5374 (9)0.3234 (8)0.7776 (6)0.084 (2)
H1AA0.54000.22780.77760.125*
H1AB0.46590.32960.73060.125*
H1AC0.50300.34320.83640.125*
C1B0.9275 (9)0.4584 (9)0.8546 (7)0.092 (3)
H1BA0.92840.36230.85340.138*
H1BB0.89490.47760.91410.138*
H1BC1.03110.52700.84240.138*
C1C0.8419 (9)0.4301 (9)0.6205 (6)0.084 (2)
H1CA0.84420.33440.62140.126*
H1CB0.94510.49900.60800.126*
H1CC0.77020.43550.57340.126*
C2A0.8272 (9)0.7754 (10)1.0181 (6)0.088 (3)
H2AA0.79390.79921.07620.132*
H2AB0.93320.83951.00670.132*
H2AC0.82240.67741.01940.132*
C2B0.6866 (10)1.0148 (8)0.9115 (6)0.087 (2)
H2BA0.65561.03710.97070.131*
H2BB0.61721.02640.86510.131*
H2BC0.79221.07900.89930.131*
C2C0.4400 (9)0.6608 (10)0.9404 (6)0.088 (3)
H2CA0.41160.68580.99960.132*
H2CB0.43210.56190.94090.132*
H2CC0.37030.67300.89430.132*
C3A0.6191 (9)0.7151 (9)0.4940 (5)0.085 (2)
H3AA0.54310.72360.45090.128*
H3AB0.62020.61910.49090.128*
H3AC0.72120.78400.47920.128*
C3B0.3259 (8)0.6064 (8)0.6589 (6)0.076 (2)
H3BA0.25390.61600.61340.115*
H3BB0.29520.62660.71870.115*
H3BC0.32470.50950.65750.115*
C3C0.5645 (8)0.9736 (8)0.6319 (6)0.075 (2)
H3CA0.49090.98280.58740.112*
H3CB0.66831.03930.61720.112*
H3CC0.53710.99590.69200.112*
C4A1.2038 (8)0.9083 (9)0.8092 (6)0.081 (2)
H4AA1.30580.97690.79380.121*
H4AB1.20580.81250.80880.121*
H4AC1.17560.92990.86930.121*
C4B1.0969 (8)0.8697 (9)0.5750 (5)0.078 (2)
H4BA1.19900.93790.55930.117*
H4BB1.02100.87480.53060.117*
H4BC1.09860.77380.57520.117*
C4C1.0413 (9)1.1383 (7)0.7095 (6)0.080 (2)
H4CA1.14511.20330.69400.120*
H4CB1.01481.16250.76930.120*
H4CC0.96741.14680.66480.120*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ge10.0459 (3)0.0435 (3)0.0477 (4)0.0158 (3)0.0020 (3)0.0011 (3)
Sn10.0596 (3)0.0444 (2)0.0628 (3)0.0192 (2)0.0006 (2)0.0007 (2)
Sn20.0586 (3)0.0588 (3)0.0469 (3)0.0216 (2)0.0030 (2)0.0002 (2)
Sn30.0501 (2)0.0549 (3)0.0501 (3)0.0183 (2)0.00229 (19)0.0012 (2)
Sn40.0469 (2)0.0507 (3)0.0549 (3)0.01392 (19)0.00327 (19)0.0024 (2)
C1A0.079 (5)0.058 (4)0.102 (7)0.012 (4)0.009 (5)0.015 (4)
C1B0.086 (6)0.081 (6)0.119 (8)0.042 (5)0.015 (5)0.022 (5)
C1C0.098 (6)0.080 (5)0.080 (6)0.039 (5)0.011 (5)0.021 (4)
C2A0.091 (6)0.110 (7)0.068 (6)0.045 (5)0.023 (4)0.006 (5)
C2B0.120 (7)0.072 (5)0.076 (6)0.041 (5)0.003 (5)0.012 (4)
C2C0.071 (5)0.105 (7)0.082 (6)0.025 (5)0.022 (4)0.018 (5)
C3A0.102 (6)0.091 (6)0.051 (5)0.022 (5)0.010 (4)0.011 (4)
C3B0.055 (4)0.082 (5)0.084 (6)0.016 (4)0.006 (4)0.003 (4)
C3C0.080 (5)0.060 (4)0.086 (6)0.028 (4)0.000 (4)0.009 (4)
C4A0.063 (4)0.102 (6)0.080 (6)0.035 (4)0.020 (4)0.016 (5)
C4B0.079 (5)0.084 (5)0.069 (5)0.026 (4)0.029 (4)0.006 (4)
C4C0.094 (6)0.049 (4)0.094 (7)0.022 (4)0.009 (5)0.009 (4)
Geometric parameters (Å, º) top
Ge1—Sn42.5912 (7)Sn2—C2C2.132 (7)
Ge1—Sn32.5917 (8)Sn2—C2A2.152 (7)
Ge1—Sn12.5952 (7)Sn3—C3A2.141 (7)
Ge1—Sn22.5953 (8)Sn3—C3C2.141 (7)
Sn1—C1A2.130 (7)Sn3—C3B2.148 (7)
Sn1—C1C2.139 (8)Sn4—C4C2.145 (7)
Sn1—C1B2.156 (7)Sn4—C4A2.147 (7)
Sn2—C2B2.120 (8)Sn4—C4B2.162 (7)
Sn4—Ge1—Sn3108.29 (3)C2B—Sn2—Ge1110.0 (2)
Sn4—Ge1—Sn1109.08 (3)C2C—Sn2—Ge1110.9 (3)
Sn3—Ge1—Sn1111.09 (3)C2A—Sn2—Ge1111.2 (2)
Sn4—Ge1—Sn2109.91 (3)C3A—Sn3—C3C107.0 (3)
Sn3—Ge1—Sn2107.59 (3)C3A—Sn3—C3B108.5 (3)
Sn1—Ge1—Sn2110.83 (3)C3C—Sn3—C3B110.3 (3)
C1A—Sn1—C1C108.9 (3)C3A—Sn3—Ge1111.5 (2)
C1A—Sn1—C1B109.3 (3)C3C—Sn3—Ge1108.7 (2)
C1C—Sn1—C1B108.0 (3)C3B—Sn3—Ge1110.9 (2)
C1A—Sn1—Ge1109.4 (2)C4C—Sn4—C4A108.0 (3)
C1C—Sn1—Ge1110.3 (2)C4C—Sn4—C4B108.7 (3)
C1B—Sn1—Ge1111.0 (2)C4A—Sn4—C4B109.4 (3)
C2B—Sn2—C2C107.9 (3)C4C—Sn4—Ge1112.1 (2)
C2B—Sn2—C2A108.2 (3)C4A—Sn4—Ge1109.6 (2)
C2C—Sn2—C2A108.6 (3)C4B—Sn4—Ge1109.0 (2)

Experimental details

Crystal data
Chemical formula[GeSn4(CH3)12]
Mr727.76
Crystal system, space groupTriclinic, 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)
V3)1232.06 (17)
Z2
Radiation typeMo Kα
µ (mm1)5.19
Crystal size (mm)0.22 × 0.22 × 0.15
Data collection
DiffractometerBruker SMART APEX
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.317, 0.460
No. of measured, independent and
observed [I > 2σ(I)] reflections
12284, 5646, 4466
Rint0.085
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.105, 1.01
No. of reflections5646
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.09, 1.01

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

 

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