Structure of compounds E(SnMe3)(4) (E = Si, Ge) as seen by high-resolution X-ray powder diffraction and solid-state NMR

R E  Dinnebier; P  Bernatowicz; X  Helluy; A  Sebald; M  Wunschel; A  Fitch; S  van Smaalen

Structure of compounds E(SnMe3)(4) (E = Si, Ge) as seen by high-resolution X-ray powder diffraction and solid-state NMR

R E Dinnebier, P Bernatowicz, X Helluy, A Sebald, M Wunschel, A Fitch, S van Smaalen

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The compounds tetrakis(trimethylstannyl)germane, Ge(SnMe3)(4) (1), and tetrakis(trimethylstannyl)silane, Si(SnMe3)(4) (2), have crystal structures with the quasispherical molecules in a closed-packed stacking. At room temperature both structures have the space group P (1) over bar (Z = 2) with a = 9.94457 (5), b = 14.52927 (8), c = 9.16021 (5) Angstrom, alpha = 90.53390 (30), beta = 111.73080 (30), gamma = 90.0049 (4)degrees, and V = 1229.414 (12) Angstrom(3) for (1) and a = 9.92009 (7), b = 14.51029 (11), c = 9.13585 (7) Angstrom, alpha = 90.4769 (4), beta = 111.6724 (4), gamma = 89.9877 (6)degrees, and V = 1222.037 (16) Angstrom(3) for (2). The molecules are found to be ordered as a result of steric interactions between neighboring molecules, as shown by analyzing the distances between the atoms. Upon heating, both compounds undergo a first-order phase transition at temperatures T-c = 348 +/- 5 K, as characterized by a relative jump of the lattice parameter of similar to 16%. At 353 K, both structures have the space group P<(1over bar> (Z = 4), with a = 14.2037 (2) Angstrom, and = 2865.52 (7) Angstrom(3) for (1) and a = 14.1346 (2) Angstrom, and = 2823.90 (7) Angstrom(3) for (2). Rietveld refinements were performed for the low-temperature phases measured at T = 295 K [R-wp = 0.0844 for (1), R-wp = 0.0940 for (2)] and for the high-temperature phases measured at T = 353 K [R-wp = 0.0891 for (1), R-wp = 0.0542 for (2)]. The combination of high-resolution X-ray powder diffraction measurements and variable-temperature magic-angle-spinning C-13, Si-29 and Sn-119 NMR experiments demonstrates low crystallographic and molecular (C-1) symmetries for the low-temperature phases of (1) and (2) at temperatures T < 348 +/- 5 K and high crystallographic symmetry due to rotational disorder for the high-temperature phases at temperatures T > 348 +/- 5 K.

Original language	English
Pages (from-to)	52-61
Number of pages	10
Journal	ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE
Volume	58
Publication status	Published - Feb 2002

Keywords

TETRAKIS(TRIMETHYLSILYL)METHANE C<SI(CH3)(3)>(4)
RIETVELD REFINEMENT
CRYSTAL-STRUCTURES
TEMPERATURE
DISORDER
TETRAKIS(TRIMETHYLSTANNYL)METHANE
SPECTROSCOPY
PHASE
ORDER

Cite this

@article{9cc9c406db7a46a795eff4950c23cf06,

title = "Structure of compounds E(SnMe3)(4) (E = Si, Ge) as seen by high-resolution X-ray powder diffraction and solid-state NMR",

abstract = "The compounds tetrakis(trimethylstannyl)germane, Ge(SnMe3)(4) (1), and tetrakis(trimethylstannyl)silane, Si(SnMe3)(4) (2), have crystal structures with the quasispherical molecules in a closed-packed stacking. At room temperature both structures have the space group P (1) over bar (Z = 2) with a = 9.94457 (5), b = 14.52927 (8), c = 9.16021 (5) Angstrom, alpha = 90.53390 (30), beta = 111.73080 (30), gamma = 90.0049 (4)degrees, and V = 1229.414 (12) Angstrom(3) for (1) and a = 9.92009 (7), b = 14.51029 (11), c = 9.13585 (7) Angstrom, alpha = 90.4769 (4), beta = 111.6724 (4), gamma = 89.9877 (6)degrees, and V = 1222.037 (16) Angstrom(3) for (2). The molecules are found to be ordered as a result of steric interactions between neighboring molecules, as shown by analyzing the distances between the atoms. Upon heating, both compounds undergo a first-order phase transition at temperatures T-c = 348 +/- 5 K, as characterized by a relative jump of the lattice parameter of similar to 16%. At 353 K, both structures have the space group P<(1over bar> (Z = 4), with a = 14.2037 (2) Angstrom, and = 2865.52 (7) Angstrom(3) for (1) and a = 14.1346 (2) Angstrom, and = 2823.90 (7) Angstrom(3) for (2). Rietveld refinements were performed for the low-temperature phases measured at T = 295 K [R-wp = 0.0844 for (1), R-wp = 0.0940 for (2)] and for the high-temperature phases measured at T = 353 K [R-wp = 0.0891 for (1), R-wp = 0.0542 for (2)]. The combination of high-resolution X-ray powder diffraction measurements and variable-temperature magic-angle-spinning C-13, Si-29 and Sn-119 NMR experiments demonstrates low crystallographic and molecular (C-1) symmetries for the low-temperature phases of (1) and (2) at temperatures T < 348 +/- 5 K and high crystallographic symmetry due to rotational disorder for the high-temperature phases at temperatures T > 348 +/- 5 K.",

keywords = "TETRAKIS(TRIMETHYLSILYL)METHANE C<SI(CH3)(3)>(4), RIETVELD REFINEMENT, CRYSTAL-STRUCTURES, TEMPERATURE, DISORDER, TETRAKIS(TRIMETHYLSTANNYL)METHANE, SPECTROSCOPY, PHASE, ORDER",

author = "Dinnebier, {R E} and P Bernatowicz and X Helluy and A Sebald and M Wunschel and A Fitch and {van Smaalen}, S",

year = "2002",

month = feb,

language = "English",

volume = "58",

pages = "52--61",

journal = "ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE",

issn = "0108-7681",

publisher = "International Union of Crystallography",

}

TY - JOUR

T1 - Structure of compounds E(SnMe3)(4) (E = Si, Ge) as seen by high-resolution X-ray powder diffraction and solid-state NMR

AU - Dinnebier, R E

AU - Bernatowicz, P

AU - Helluy, X

AU - Sebald, A

AU - Wunschel, M

AU - Fitch, A

AU - van Smaalen, S

PY - 2002/2

Y1 - 2002/2

N2 - The compounds tetrakis(trimethylstannyl)germane, Ge(SnMe3)(4) (1), and tetrakis(trimethylstannyl)silane, Si(SnMe3)(4) (2), have crystal structures with the quasispherical molecules in a closed-packed stacking. At room temperature both structures have the space group P (1) over bar (Z = 2) with a = 9.94457 (5), b = 14.52927 (8), c = 9.16021 (5) Angstrom, alpha = 90.53390 (30), beta = 111.73080 (30), gamma = 90.0049 (4)degrees, and V = 1229.414 (12) Angstrom(3) for (1) and a = 9.92009 (7), b = 14.51029 (11), c = 9.13585 (7) Angstrom, alpha = 90.4769 (4), beta = 111.6724 (4), gamma = 89.9877 (6)degrees, and V = 1222.037 (16) Angstrom(3) for (2). The molecules are found to be ordered as a result of steric interactions between neighboring molecules, as shown by analyzing the distances between the atoms. Upon heating, both compounds undergo a first-order phase transition at temperatures T-c = 348 +/- 5 K, as characterized by a relative jump of the lattice parameter of similar to 16%. At 353 K, both structures have the space group P<(1over bar> (Z = 4), with a = 14.2037 (2) Angstrom, and = 2865.52 (7) Angstrom(3) for (1) and a = 14.1346 (2) Angstrom, and = 2823.90 (7) Angstrom(3) for (2). Rietveld refinements were performed for the low-temperature phases measured at T = 295 K [R-wp = 0.0844 for (1), R-wp = 0.0940 for (2)] and for the high-temperature phases measured at T = 353 K [R-wp = 0.0891 for (1), R-wp = 0.0542 for (2)]. The combination of high-resolution X-ray powder diffraction measurements and variable-temperature magic-angle-spinning C-13, Si-29 and Sn-119 NMR experiments demonstrates low crystallographic and molecular (C-1) symmetries for the low-temperature phases of (1) and (2) at temperatures T < 348 +/- 5 K and high crystallographic symmetry due to rotational disorder for the high-temperature phases at temperatures T > 348 +/- 5 K.

AB - The compounds tetrakis(trimethylstannyl)germane, Ge(SnMe3)(4) (1), and tetrakis(trimethylstannyl)silane, Si(SnMe3)(4) (2), have crystal structures with the quasispherical molecules in a closed-packed stacking. At room temperature both structures have the space group P (1) over bar (Z = 2) with a = 9.94457 (5), b = 14.52927 (8), c = 9.16021 (5) Angstrom, alpha = 90.53390 (30), beta = 111.73080 (30), gamma = 90.0049 (4)degrees, and V = 1229.414 (12) Angstrom(3) for (1) and a = 9.92009 (7), b = 14.51029 (11), c = 9.13585 (7) Angstrom, alpha = 90.4769 (4), beta = 111.6724 (4), gamma = 89.9877 (6)degrees, and V = 1222.037 (16) Angstrom(3) for (2). The molecules are found to be ordered as a result of steric interactions between neighboring molecules, as shown by analyzing the distances between the atoms. Upon heating, both compounds undergo a first-order phase transition at temperatures T-c = 348 +/- 5 K, as characterized by a relative jump of the lattice parameter of similar to 16%. At 353 K, both structures have the space group P<(1over bar> (Z = 4), with a = 14.2037 (2) Angstrom, and = 2865.52 (7) Angstrom(3) for (1) and a = 14.1346 (2) Angstrom, and = 2823.90 (7) Angstrom(3) for (2). Rietveld refinements were performed for the low-temperature phases measured at T = 295 K [R-wp = 0.0844 for (1), R-wp = 0.0940 for (2)] and for the high-temperature phases measured at T = 353 K [R-wp = 0.0891 for (1), R-wp = 0.0542 for (2)]. The combination of high-resolution X-ray powder diffraction measurements and variable-temperature magic-angle-spinning C-13, Si-29 and Sn-119 NMR experiments demonstrates low crystallographic and molecular (C-1) symmetries for the low-temperature phases of (1) and (2) at temperatures T < 348 +/- 5 K and high crystallographic symmetry due to rotational disorder for the high-temperature phases at temperatures T > 348 +/- 5 K.

KW - TETRAKIS(TRIMETHYLSILYL)METHANE C<SI(CH3)(3)>(4)

KW - RIETVELD REFINEMENT

KW - CRYSTAL-STRUCTURES

KW - TEMPERATURE

KW - DISORDER

KW - TETRAKIS(TRIMETHYLSTANNYL)METHANE

KW - SPECTROSCOPY

KW - PHASE

KW - ORDER

M3 - Article

SN - 0108-7681

VL - 58

SP - 52

EP - 61

JO - ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE

JF - ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE

ER -