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The structures of in situ pressure-frozen chlorotrimethylsilane crystals, (CH3)3SiCl, have been determined at 0.23, 0.30 and 0.58 GPa. The molecular arrangements in the low-temperature and high-pressure phases are two-dimensionally isostructural, but different in the third perpendicular direction. Consequently, a striking similarity exists between the unit-cell dimensions of these polymorphs. The absence of short Cl...Cl contacts, both in the low-temperature or pressure-frozen phases of (CH3)3SiCl, has been rationalized in terms of the favoured packing patterns and comparable energies of halogen...halogen interactions and other van der Waals forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105037766/av5043sup1.cif
Contains datablocks tmcs1, tmcs2, tmcs3

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768105037766/av5043tmcs1sup2.hkl
Contains datablock tmcs

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768105037766/av5043tmcs2sup3.hkl
Contains datablock dwa2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768105037766/av5043tmcs3sup4.hkl
Contains datablock trzy3

CCDC references: 298302; 298303; 298304

Computing details top

For all compounds, data collection: CrysAlis (Oxford Diffraction, 2004); cell refinement: CrysAlis (Oxford Diffraction, 2004); data reduction: CrysAlis (Oxford Diffraction, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
(tmcs1) chlorotrimethylsilane top
Crystal data top
C3H9ClSiDx = 1.153 Mg m3
Mr = 108.64Melting point: 215 K
Orthorhombic, Pmn21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2Cell parameters from 839 reflections
a = 7.785 (2) Åθ = 4.2–27.4°
b = 6.43 (3) ŵ = 0.66 mm1
c = 6.254 (3) ÅT = 293 K
V = 313.0 (15) Å3Disc, colourless
Z = 20.46 × 0.46 × 0.18 × 0.23 (radius) mm
F(000) = 116
Data collection top
Kuma KM4CCD κ geometry
diffractometer
194 independent reflections
Radiation source: fine-focus sealed tube170 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
ω scansθmax = 27.4°, θmin = 4.2°
Absorption correction: analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.
Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467
h = 1010
Tmin = 0.41, Tmax = 0.94k = 11
1793 measured reflectionsl = 88
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.032 w = 1/[σ2(Fo2) + (0.0568P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.083(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.08 e Å3
194 reflectionsΔρmin = 0.11 e Å3
29 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.19 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.6 (3)
Crystal data top
C3H9ClSiV = 313.0 (15) Å3
Mr = 108.64Z = 2
Orthorhombic, Pmn21Mo Kα radiation
a = 7.785 (2) ŵ = 0.66 mm1
b = 6.43 (3) ÅT = 293 K
c = 6.254 (3) Å0.46 × 0.46 × 0.18 × 0.23 (radius) mm
Data collection top
Kuma KM4CCD κ geometry
diffractometer
194 independent reflections
Absorption correction: analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.
Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467
170 reflections with I > 2σ(I)
Tmin = 0.41, Tmax = 0.94Rint = 0.075
1793 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.083Δρmax = 0.08 e Å3
S = 1.01Δρmin = 0.11 e Å3
194 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
29 parametersAbsolute structure parameter: 0.6 (3)
1 restraint
Special details top

Experimental. High-pressure measurement at 0.23 GPa.

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*/UeqOcc. (<1)
Cl10.00000.361 (2)0.4727 (5)0.153 (13)
Si10.00000.6592 (17)0.3753 (2)0.0402 (7)*
C10.00000.699 (4)0.0771 (13)0.06 (2)
H110.00000.84530.04610.068*
H120.10070.63600.01660.068*0.50
H12A0.10070.63600.01660.068*0.50
C20.1922 (9)0.826 (6)0.4857 (11)0.07 (2)
H210.27030.71330.45560.089*
H220.17650.83790.63770.089*
H230.23850.95170.43110.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.086 (2)0.28 (4)0.088 (2)0.0000.0000.011 (5)
C10.061 (4)0.05 (7)0.059 (4)0.0000.0000.046 (13)
C20.068 (4)0.08 (6)0.077 (4)0.026 (8)0.011 (3)0.045 (10)
Geometric parameters (Å, º) top
Cl1—Si12.010 (15)Si1—C21.964 (19)
Si1—C11.882 (9)Si1—C2i1.964 (19)
C1—Si1—C2105.9 (7)C1—Si1—Cl1115.4 (10)
C1—Si1—C2i105.9 (7)C2—Si1—Cl1114.3 (10)
C2—Si1—C2i99.3 (16)C2i—Si1—Cl1114.3 (10)
Symmetry code: (i) x, y, z.
(tmcs2) chlorotrimethylsilane top
Crystal data top
C3H9ClSiDx = 1.160 Mg m3
Mr = 108.64Melting point: 215 K
Orthorhombic, Pmn21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2Cell parameters from 989 reflections
a = 7.768 (2) Åθ = 4.2–22.5°
b = 6.42 (2) ŵ = 0.66 mm1
c = 6.233 (2) ÅT = 293 K
V = 311.0 (11) Å3Disc, colourless
Z = 20.44 × 0.44 × 0.18 × 0.22 (radius) mm
F(000) = 116
Data collection top
Kuma KM4CCD κ geometry
diffractometer
164 independent reflections
Radiation source: fine-focus sealed tube158 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ω scansθmax = 22.5°, θmin = 4.2°
Absorption correction: analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.
Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467
h = 88
Tmin = 0.40, Tmax = 0.94k = 22
1473 measured reflectionsl = 66
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.032 w = 1/[σ2(Fo2) + (0.0448P)2 + 0.0802P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.082(Δ/σ)max = 0.223
S = 1.22Δρmax = 0.11 e Å3
164 reflectionsΔρmin = 0.09 e Å3
32 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.018 (17)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.2 (4)
Crystal data top
C3H9ClSiV = 311.0 (11) Å3
Mr = 108.64Z = 2
Orthorhombic, Pmn21Mo Kα radiation
a = 7.768 (2) ŵ = 0.66 mm1
b = 6.42 (2) ÅT = 293 K
c = 6.233 (2) Å0.44 × 0.44 × 0.18 × 0.22 (radius) mm
Data collection top
Kuma KM4CCD κ geometry
diffractometer
164 independent reflections
Absorption correction: analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.
Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467
158 reflections with I > 2σ(I)
Tmin = 0.40, Tmax = 0.94Rint = 0.057
1473 measured reflectionsθmax = 22.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082(Δ/σ)max = 0.223
S = 1.22Δρmax = 0.11 e Å3
164 reflectionsΔρmin = 0.09 e Å3
32 parametersAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
1 restraintAbsolute structure parameter: 0.2 (4)
Special details top

Experimental. High-pressure measurement at 0.3 GPa.

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*/UeqOcc. (<1)
Cl10.00000.393 (2)0.4611 (5)0.087 (10)
Si10.00000.693 (2)0.3624 (4)0.072 (7)
C10.00000.700 (4)0.0724 (15)0.034 (16)
H110.00000.84170.02470.041*
H120.10090.63040.01930.041*0.50
H12A0.10090.63040.01930.041*0.50
C20.1988 (13)0.815 (4)0.4743 (18)0.095 (15)
H210.29720.76480.39740.114*
H220.21150.78490.62410.114*
H230.18980.96180.45510.114*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0707 (19)0.11 (3)0.081 (2)0.0000.0000.004 (8)
Si10.0462 (16)0.13 (2)0.0433 (17)0.0000.0000.016 (5)
C10.049 (5)0.00 (5)0.053 (5)0.0000.0000.002 (12)
C20.072 (5)0.16 (5)0.054 (4)0.014 (10)0.013 (4)0.016 (11)
Geometric parameters (Å, º) top
Cl1—Si12.02 (2)Si1—C21.869 (15)
Si1—C11.808 (10)Si1—C2i1.869 (15)
C1—Si1—C2111.3 (5)C1—Si1—Cl1109.2 (10)
C1—Si1—C2i111.3 (5)C2—Si1—Cl1106.8 (7)
C2—Si1—C2i111.4 (14)C2i—Si1—Cl1106.8 (7)
Symmetry code: (i) x, y, z.
(tmcs3) chlorotrimethylsilane top
Crystal data top
C3H9ClSiDx = 1.205 Mg m3
Mr = 108.64Melting point: 215 K
Orthorhombic, Pmn21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2Cell parameters from 798 reflections
a = 7.668 (2) Åθ = 4.2–24.9°
b = 6.34 (2) ŵ = 0.69 mm1
c = 6.159 (2) ÅT = 293 K
V = 299.4 (11) Å3Disc, colourless
Z = 20.42 × 0.42 × 0.18 × 0.21 (radius) mm
F(000) = 116
Data collection top
Kuma KM4CCD κ geometry
diffractometer
199 independent reflections
Radiation source: fine-focus sealed tube193 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
ω scansθmax = 24.9°, θmin = 4.2°
Absorption correction: analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.
Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467
h = 99
Tmin = 0.41, Tmax = 0.92k = 22
1697 measured reflectionsl = 77
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.0395P)2 + 0.1814P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.092(Δ/σ)max < 0.001
S = 1.27Δρmax = 0.17 e Å3
199 reflectionsΔρmin = 0.19 e Å3
29 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.031 (17)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.0 (4)
Crystal data top
C3H9ClSiV = 299.4 (11) Å3
Mr = 108.64Z = 2
Orthorhombic, Pmn21Mo Kα radiation
a = 7.668 (2) ŵ = 0.69 mm1
b = 6.34 (2) ÅT = 293 K
c = 6.159 (2) Å0.42 × 0.42 × 0.18 × 0.21 (radius) mm
Data collection top
Kuma KM4CCD κ geometry
diffractometer
199 independent reflections
Absorption correction: analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.
Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467
193 reflections with I > 2σ(I)
Tmin = 0.41, Tmax = 0.92Rint = 0.060
1697 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092Δρmax = 0.17 e Å3
S = 1.27Δρmin = 0.19 e Å3
199 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
29 parametersAbsolute structure parameter: 0.0 (4)
1 restraint
Special details top

Experimental. High-pressure measurement at 0.58 GPa.

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*/UeqOcc. (<1)
Cl10.00000.3912 (19)0.4721 (5)0.084 (6)
Si10.00000.6887 (15)0.3702 (4)0.046 (5)
C10.00000.694 (4)0.0740 (14)0.045 (2)*
H110.00000.83750.02470.054*
H120.10220.62340.02070.054*0.50
H12A0.10220.62340.02070.054*0.50
C20.2020 (11)0.815 (3)0.4833 (16)0.068 (14)
H210.29830.76290.40310.081*
H220.21490.77850.63160.081*
H230.19740.96220.47000.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0595 (18)0.125 (18)0.0667 (15)0.0000.0000.000 (7)
Si10.0391 (13)0.064 (15)0.0360 (11)0.0000.0000.011 (5)
C20.064 (4)0.09 (4)0.045 (3)0.013 (9)0.012 (3)0.002 (11)
Geometric parameters (Å, º) top
Cl1—Si11.988 (14)Si1—C21.878 (12)
Si1—C11.825 (9)Si1—C2i1.878 (12)
C1—Si1—C2111.3 (5)C1—Si1—Cl1109.4 (10)
C1—Si1—C2i111.3 (5)C2—Si1—Cl1106.7 (7)
C2—Si1—C2i111.2 (12)C2i—Si1—Cl1106.7 (7)
Symmetry code: (i) x, y, z.

Experimental details

(tmcs1)(tmcs2)(tmcs3)
Crystal data
Chemical formulaC3H9ClSiC3H9ClSiC3H9ClSi
Mr108.64108.64108.64
Crystal system, space groupOrthorhombic, Pmn21Orthorhombic, Pmn21Orthorhombic, Pmn21
Temperature (K)293293293
a, b, c (Å)7.785 (2), 6.43 (3), 6.254 (3)7.768 (2), 6.42 (2), 6.233 (2)7.668 (2), 6.34 (2), 6.159 (2)
V3)313.0 (15)311.0 (11)299.4 (11)
Z222
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.660.660.69
Crystal size (mm)0.46 × 0.46 × 0.18 × 0.23 (radius)0.44 × 0.44 × 0.18 × 0.22 (radius)0.42 × 0.42 × 0.18 × 0.21 (radius)
Data collection
DiffractometerKuma KM4CCD κ geometry
diffractometer
Kuma KM4CCD κ geometry
diffractometer
Kuma KM4CCD κ geometry
diffractometer
Absorption correctionAnalytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.

Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467

Analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.

Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467

Analytical
Katrusiak, A. (2003). REDSHADE - Program for correcting reflections intensities for DAC absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań.

Katrusiak, A. (2004). Z. Kristallogr. 219, 461-467

Tmin, Tmax0.41, 0.940.40, 0.940.41, 0.92
No. of measured, independent and
observed [I > 2σ(I)] reflections
1793, 194, 170 1473, 164, 158 1697, 199, 193
Rint0.0750.0570.060
θmax (°)27.422.524.9
(sin θ/λ)max1)0.6470.5370.592
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.083, 1.01 0.032, 0.082, 1.22 0.039, 0.092, 1.27
No. of reflections194164199
No. of parameters293229
No. of restraints111
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
(Δ/σ)max< 0.0010.223< 0.001
Δρmax, Δρmin (e Å3)0.08, 0.110.11, 0.090.17, 0.19
Absolute structureFlack H D (1983), Acta Cryst. A39, 876-881Flack H D (1983), Acta Cryst. A39, 876-881Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter0.6 (3)0.2 (4)0.0 (4)

Computer programs: CrysAlis (Oxford Diffraction, 2004), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1990).

 

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