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The low-temperature crystal structures of perdeuterogermane (m.p. 108 K) and perdeuterostannane (m.p. 123 K) are reported. The structures have been characterized from low-temperature (5 K) high-resolution neutron powder diffraction experiments following sample preparation using in situ gas-condensation techniques. GeD4 crystallizes in an ortho­rhombic structure, space group P212121, with one molecule in the asymmetric unit, and with an average Ge-D bond length of 1.517 (3) Å. The SnD4 structure is monoclinic (space group C2/c), and the molecule is located on a twofold rotation axis with an average Sn-D bond length of 1.706 (3) Å. The crystal structures are discussed in relation to those of other tetrahedral molecules of group IV hydrides at low temperature, and evidence is presented that the crystal structure of silane, below 38 K, is isostructural with germane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768108010379/ws5063sup1.cif
Contains datablocks GeD4_5K, SnD4_5K

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768108010379/ws5063GeD4_5Ksup2.rtv
Contains datablock GeD4_5K

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768108010379/ws5063SnD4_5Ksup3.rtv
Contains datablock SnD4_5K

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108768108010379/ws5063sup4.pdf
Supplementary material

Computing details top

For both compounds, data collection: ISIS instrument control program (ICP); cell refinement: TOPAS-Academic (Coehlo); data reduction: Standard HRPD normalisation routines; program(s) used to refine structure: TOPAS.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
(GeD4_5K) perdeuterogermane top
Crystal data top
D4GeZ = 4
Mr = 80.65Dx = 1.966 Mg m3
Orthorhombic, P212121Melting point: 108 K
Hall symbol: P 2ac 2abTime-of-flight neutron radiation, λ = 1.24-5.36 Å
a = 7.35565 (17) ÅT = 5 K
b = 8.15934 (11) ÅParticle morphology: irregular powder
c = 4.53932 (11) Åcylinder, 25 × 11 mm
V = 272.44 (1) Å3
Data collection top
HRPD
diffractometer
Scan method: tof 30-130 ms
Specimen mounting: standard cylindrical vanadium sample holder
Refinement top
Least-squares matrix: fullProfile function: TOPAS TOF Pseudo-Voigt Profile function
Rp = 0.06145 parameters
Rwp = 0.0690 restraints
Rexp = 0.0430 constraints
R(F2) = 0.15705Weighting scheme based on measured s.u.'s
χ2 = 2.560(Δ/σ)max = 0.01
? data pointsBackground function: Shifted Chebyshev function (10 terms)
Excluded region(s): NonePreferred orientation correction: Spherical Harmonic ODF Spherical harmonic order= 6 The sample symmetry is: cylindrical (fiber texture) Index = 2 0 0 Coeff= 0.3104 Index = 2 0 2 Coeff= 0.9511 Index = 4 0 0 Coeff= 0.2995 Index = 4 0 2 Coeff= -0.2573 Index = 4 0 4 Coeff= -0.2003 Index = 6 0 0 Coeff= -0.7728 Index = 6 0 2 Coeff= -0.5283 Index = 6 0 4 Coeff= -0.4214 Index = 6 0 6 Coeff= 0.6972 Prefered orientation correction range: Min= 0.49389, Max= 1.59951
Crystal data top
D4GeV = 272.44 (1) Å3
Mr = 80.65Z = 4
Orthorhombic, P212121Time-of-flight neutron radiation, λ = 1.24-5.36 Å
a = 7.35565 (17) ÅT = 5 K
b = 8.15934 (11) Åcylinder, 25 × 11 mm
c = 4.53932 (11) Å
Data collection top
HRPD
diffractometer
Scan method: tof 30-130 ms
Specimen mounting: standard cylindrical vanadium sample holder
Refinement top
Rp = 0.061χ2 = 2.560
Rwp = 0.069? data points
Rexp = 0.04345 parameters
R(F2) = 0.157050 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ge0.4922 (5)0.3536 (3)0.3559 (5)0.0028 (5)*
D10.6327 (7)0.3211 (4)0.1148 (11)0.0391 (11)*
D20.3175 (8)0.4062 (6)0.1989 (10)0.0470 (14)*
D30.4605 (7)0.2034 (4)0.5311 (10)0.0407 (13)*
D40.5513 (6)0.4954 (6)0.5539 (10)0.0455 (15)*
Geometric parameters (Å, º) top
Ge—D11.528 (5)Ge—D31.480 (5)
Ge—D21.531 (6)Ge—D41.528 (6)
D1—Ge—D2106.4 (3)D2—Ge—D3110.4 (2)
D1—Ge—D3110.3 (2)D2—Ge—D4107.4 (3)
D1—Ge—D4111.1 (3)D3—Ge—D4110.8 (2)
(SnD4_5K) perdeuterostannane top
Crystal data top
D4SnV = 308.22 (1) Å3
Mr = 126.75Z = 4
Monoclinic, C2/cDx = 2.731 Mg m3
Hall symbol: -C 2ycMelting point: 123 K
a = 8.87431 (14) ÅTime-of-flight neutron radiation, λ = 1.24-5.36 Å
b = 4.54743 (7) ÅT = 5 K
c = 8.75705 (12) ÅParticle morphology: irregular powder
β = 119.2882 (10)°cylinder, 25 × 11 mm
Data collection top
HRPD
diffractometer
Scan method: tof 30-130 ms
Specimen mounting: standard cylindrical vanadium sample holder
Refinement top
Least-squares matrix: fullProfile function: TOPAS TOF Pseudo-Voigt Profile function
Rp = 0.11135 parameters
Rwp = 0.1240 restraints
Rexp = 0.0620 constraints
R(F2) = 0.13390Weighting scheme based on measured s.u.'s
χ2 = 4.121(Δ/σ)max = 0.02
? data pointsBackground function: Shifted Chebyshev function (10 terms)
Excluded region(s): NonePreferred orientation correction: Spherical Harmonic ODF Spherical harmonic order= 4 The sample symmetry is: cylindrical (fiber texture) Index = 2 0 -2 Coeff= -0.1205 Index = 2 0 0 Coeff= -0.0792 Index = 2 0 2 Coeff= -0.0205 Index = 4 0 -4 Coeff= 0.1646 Index = 4 0 -2 Coeff= 0.4387 Index = 4 0 0 Coeff= -0.4362 Index = 4 0 2 Coeff= 0.2127 Index = 4 0 4 Coeff= -0.0198 Prefered orientation correction range: Min= 0.81761, Max= 1.29987
Crystal data top
D4Snβ = 119.2882 (10)°
Mr = 126.75V = 308.22 (1) Å3
Monoclinic, C2/cZ = 4
a = 8.87431 (14) ÅTime-of-flight neutron radiation, λ = 1.24-5.36 Å
b = 4.54743 (7) ÅT = 5 K
c = 8.75705 (12) Åcylinder, 25 × 11 mm
Data collection top
HRPD
diffractometer
Scan method: tof 30-130 ms
Specimen mounting: standard cylindrical vanadium sample holder
Refinement top
Rp = 0.111χ2 = 4.121
Rwp = 0.124? data points
Rexp = 0.06235 parameters
R(F2) = 0.133900 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn0.50.4258 (5)0.250.0049 (8)*
D10.3237 (3)0.6461 (4)0.1965 (4)0.0302 (8)*
D20.5351 (3)0.2142 (5)0.4235 (3)0.0276 (8)*
Geometric parameters (Å, º) top
Sn—D11.719 (3)Sn—D21.693 (3)
Sn—D1i1.719 (3)Sn—D2i1.693 (3)
D1—Sn—D1i108.7 (2)D1i—Sn—D2110.07 (11)
D1—Sn—D2108.63 (14)D1i—Sn—D2i108.63 (14)
D1—Sn—D2i110.07 (11)D2—Sn—D2i110.7 (2)
Symmetry code: (i) x+1, y, z+1/2.

Experimental details

(GeD4_5K)(SnD4_5K)
Crystal data
Chemical formulaD4GeD4Sn
Mr80.65126.75
Crystal system, space groupOrthorhombic, P212121Monoclinic, C2/c
Temperature (K)55
a, b, c (Å)7.35565 (17), 8.15934 (11), 4.53932 (11)8.87431 (14), 4.54743 (7), 8.75705 (12)
α, β, γ (°)90, 90, 9090, 119.2882 (10), 90
V3)272.44 (1)308.22 (1)
Z44
Radiation typeTime-of-flight neutron, λ = 1.24-5.36 ÅTime-of-flight neutron, λ = 1.24-5.36 Å
Specimen shape, size (mm)Cylinder, 25 × 11Cylinder, 25 × 11
Data collection
DiffractometerHRPD
diffractometer
HRPD
diffractometer
Specimen mountingStandard cylindrical vanadium sample holderStandard cylindrical vanadium sample holder
Data collection mode??
Scan methodTof 30-130 msTof 30-130 ms
2θ values (°)2θmin = ? 2θmax = ? 2θstep = ?2θmin = ? 2θmax = ? 2θstep = ?
Refinement
R factors and goodness of fitRp = 0.061, Rwp = 0.069, Rexp = 0.043, R(F2) = 0.15705, χ2 = 2.560Rp = 0.111, Rwp = 0.124, Rexp = 0.062, R(F2) = 0.13390, χ2 = 4.121
No. of data points??
No. of parameters4535

Computer programs: ISIS instrument control program (ICP), TOPAS-Academic (Coehlo), Standard HRPD normalisation routines, TOPAS.

 

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