Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768107044618/av5094sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768107044618/av5094cbm_170Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768107044618/av5094cbm_100Ksup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768107044618/av5094cbm_1.04GPasup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768107044618/av5094cbm_1.72GPasup5.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108768107044618/av5094sup6.pdf |
CCDC references: 671599; 671600; 671601; 671602
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2004). Data reduction: CrysAlis RED (Oxford Diffraction, 2004) for cbm_170K, cbm_100K; CrysAlis RED (Oxford Diffraction, 2004); REDSHABS (Katrusiak, A. 2003) for cbm_1.04GPa, cbm_1.72GPa. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for cbm_170K, cbm_100K; SHELXS–97 (Sheldrick, 1997) for cbm_1.04GPa, cbm_1.72GPa. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for cbm_170K, cbm_100K; SHELXL–97 (Sheldrick, 1997) for cbm_1.04GPa, cbm_1.72GPa. For all compounds, molecular graphics: X-SEED 2.0; software used to prepare material for publication: SHELXL–97 (Sheldrick, 1997).
CH_{2}BrCl | D_{x} = 2.357 Mg m^{−}^{3} |
M_{r} = 129.39 | Melting point: 185 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.959 (2) Å | Cell parameters from 1010 reflections |
b = 4.4531 (9) Å | θ = 3.0–29.1° |
c = 14.873 (3) Å | µ = 11.73 mm^{−}^{1} |
β = 112.96 (3)° | T = 170 K |
V = 729.3 (3) Å^{3} | Irregular, colourless |
Z = 8 | 0.12 × 0.12 × 0.10 mm |
F(000) = 480 |
KM-4 CCD diffractometer | 909 independent reflections |
Radiation source: fine-focus sealed tube | 643 reflections with I > 2σ(I) |
Graphite monochromator | R_{int} = 0.109 |
ω–scans | θ_{max} = 29.1°, θ_{min} = 3.0° |
Absorption correction: multi-scan Correction for absorption was made using XEMP (SHELXTL, Sheldrick (1990)). | h = −15→16 |
T_{min} = 0.22, T_{max} = 0.32 | k = −4→5 |
2422 measured reflections | l = −20→19 |
Refinement on F^{2} | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F^{2} > 2σ(F^{2})] = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
wR(F^{2}) = 0.172 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0777P)^{2}] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
S = 1.15 | (Δ/σ)_{max} = 0.009 |
909 reflections | Δρ_{max} = 0.83 e Å^{−}^{3} |
36 parameters | Δρ_{min} = −0.66 e Å^{−}^{3} |
6 restraints | Extinction correction: SHELXL, Fc^{*}=kFc[1+0.001xFc^{2}λ^{3}/sin(2θ)]^{-1/4} |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.036 (4) |
CH_{2}BrCl | V = 729.3 (3) Å^{3} |
M_{r} = 129.39 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.959 (2) Å | µ = 11.73 mm^{−}^{1} |
b = 4.4531 (9) Å | T = 170 K |
c = 14.873 (3) Å | 0.12 × 0.12 × 0.10 mm |
β = 112.96 (3)° |
KM-4 CCD diffractometer | 909 independent reflections |
Absorption correction: multi-scan Correction for absorption was made using XEMP (SHELXTL, Sheldrick (1990)). | 643 reflections with I > 2σ(I) |
T_{min} = 0.22, T_{max} = 0.32 | R_{int} = 0.109 |
2422 measured reflections |
R[F^{2} > 2σ(F^{2})] = 0.066 | 6 restraints |
wR(F^{2}) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρ_{max} = 0.83 e Å^{−}^{3} |
909 reflections | Δρ_{min} = −0.66 e Å^{−}^{3} |
36 parameters |
Experimental. Data were collected at ambient pressure (100 kPa) and 170 K with the crystal obtained by the in situ low-temperature crystallization technique. |
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 F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Br1 | 0.09023 (3) | 0.6643 (2) | 0.13228 (7) | 0.0531 (5) | 0.508 (3) |
Cl1 | 0.09023 (3) | 0.6643 (2) | 0.13228 (7) | 0.0531 (5) | 0.492 (3) |
Br2 | 0.34640 (3) | 0.6410 (2) | 0.13258 (7) | 0.0495 (5) | 0.492 (3) |
Cl2 | 0.34640 (3) | 0.6410 (2) | 0.13258 (7) | 0.0495 (5) | 0.508 (3) |
C1 | 0.2014 (6) | 0.43217 (10) | 0.1066 (2) | 0.057 (2) | |
H1 | 0.16979 (17) | 0.3694 (12) | 0.0388 (4) | 0.069* | |
H2 | 0.22013 (17) | 0.2511 (2) | 0.1460 (3) | 0.069* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Br1 | 0.0468 (7) | 0.0539 (7) | 0.0632 (8) | −0.0041 (4) | 0.0265 (5) | −0.0092 (4) |
Cl1 | 0.0468 (7) | 0.0539 (7) | 0.0632 (8) | −0.0041 (4) | 0.0265 (5) | −0.0092 (4) |
Br2 | 0.0369 (6) | 0.0517 (7) | 0.0577 (8) | 0.0020 (4) | 0.0159 (5) | 0.0027 (4) |
Cl2 | 0.0369 (6) | 0.0517 (7) | 0.0577 (8) | 0.0020 (4) | 0.0159 (5) | 0.0027 (4) |
C1 | 0.066 (5) | 0.026 (3) | 0.085 (5) | 0.003 (3) | 0.034 (4) | −0.007 (3) |
Br1—C1 | 1.837 (6) | Br2—C1 | 1.871 (6) |
Cl1—C1 | 1.837 (6) | Cl2—C1 | 1.871 (6) |
Cl1—C1—Br1 | 0.00 (5) | Cl1—C1—Br2 | 111.41 (8) |
Cl1—C1—Cl2 | 111.41 (8) | Br1—C1—Br2 | 111.41 (8) |
Br1—C1—Cl2 | 111.41 (8) | Cl2—C1—Br2 | 0.00 (8) |
CH_{2}BrCl | D_{x} = 2.422 Mg m^{−}^{3} |
M_{r} = 129.39 | Melting point: 185 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.874 (2) Å | Cell parameters from 1948 reflections |
b = 4.4224 (9) Å | θ = 3.0–29.7° |
c = 14.582 (3) Å | µ = 12.05 mm^{−}^{1} |
β = 112.04 (3)° | T = 100 K |
V = 709.8 (2) Å^{3} | Irregular, colourless |
Z = 8 | 0.12 × 0.12 × 0.10 mm |
F(000) = 480 |
KM-4 CCD diffractometer | 923 independent reflections |
Radiation source: fine-focus sealed tube | 784 reflections with I > 2σ(I) |
Graphite monochromator | R_{int} = 0.078 |
ω–scans | θ_{max} = 29.7°, θ_{min} = 3.0° |
Absorption correction: multi-scan Correction for absorption was made using XEMP (SHELXTL, Sheldrick (1990)). | h = −16→15 |
T_{min} = 0.22, T_{max} = 0.32 | k = −4→6 |
3122 measured reflections | l = −19→19 |
Refinement on F^{2} | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F^{2} > 2σ(F^{2})] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F^{2}) = 0.128 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0553P)^{2} + 4.5134P] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
S = 1.12 | (Δ/σ)_{max} < 0.001 |
923 reflections | Δρ_{max} = 1.51 e Å^{−}^{3} |
36 parameters | Δρ_{min} = −0.72 e Å^{−}^{3} |
6 restraints | Extinction correction: SHELXL, Fc^{*}=kFc[1+0.001xFc^{2}λ^{3}/sin(2θ)]^{-1/4} |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0023 (9) |
CH_{2}BrCl | V = 709.8 (2) Å^{3} |
M_{r} = 129.39 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.874 (2) Å | µ = 12.05 mm^{−}^{1} |
b = 4.4224 (9) Å | T = 100 K |
c = 14.582 (3) Å | 0.12 × 0.12 × 0.10 mm |
β = 112.04 (3)° |
KM-4 CCD diffractometer | 923 independent reflections |
Absorption correction: multi-scan Correction for absorption was made using XEMP (SHELXTL, Sheldrick (1990)). | 784 reflections with I > 2σ(I) |
T_{min} = 0.22, T_{max} = 0.32 | R_{int} = 0.078 |
3122 measured reflections |
R[F^{2} > 2σ(F^{2})] = 0.051 | 6 restraints |
wR(F^{2}) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρ_{max} = 1.51 e Å^{−}^{3} |
923 reflections | Δρ_{min} = −0.72 e Å^{−}^{3} |
36 parameters |
Experimental. Data were collected at ambient pressure (100 kPa) and 100 K with the crystal obtained by the in situ low-temperature crystallization technique. |
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 F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Br1 | 0.08668 (3) | 0.67376 (15) | 0.13130 (5) | 0.0279 (3) | 0.475 (3) |
Cl1 | 0.08668 (3) | 0.67376 (15) | 0.13130 (5) | 0.0279 (3) | 0.525 (3) |
Br2 | 0.34594 (3) | 0.65355 (15) | 0.13301 (5) | 0.0279 (3) | 0.525 (3) |
Cl2 | 0.34594 (3) | 0.65355 (15) | 0.13301 (5) | 0.0279 (3) | 0.475 (3) |
C1 | 0.2026 (4) | 0.43547 (16) | 0.10799 (15) | 0.0295 (11) | |
H1 | 0.17142 (11) | 0.3738 (7) | 0.0391 (2) | 0.035* | |
H2 | 0.22127 (11) | 0.26233 (19) | 0.1520 (2) | 0.035* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Br1 | 0.0256 (5) | 0.0271 (4) | 0.0337 (5) | −0.0027 (3) | 0.0141 (3) | −0.0051 (3) |
Cl1 | 0.0256 (5) | 0.0271 (4) | 0.0337 (5) | −0.0027 (3) | 0.0141 (3) | −0.0051 (3) |
Br2 | 0.0215 (4) | 0.0282 (4) | 0.0329 (5) | 0.0008 (2) | 0.0089 (3) | 0.0019 (3) |
Cl2 | 0.0215 (4) | 0.0282 (4) | 0.0329 (5) | 0.0008 (2) | 0.0089 (3) | 0.0019 (3) |
C1 | 0.030 (3) | 0.018 (2) | 0.036 (3) | 0.0000 (19) | 0.007 (2) | −0.005 (2) |
Br1—C1 | 1.863 (4) | Br2—C1 | 1.870 (4) |
Cl1—C1 | 1.863 (4) | Cl2—C1 | 1.870 (4) |
Cl1—C1—Br1 | 0.00 (4) | Cl1—C1—Br2 | 110.70 (6) |
Cl1—C1—Cl2 | 110.70 (6) | Br1—C1—Br2 | 110.70 (6) |
Br1—C1—Cl2 | 110.70 (6) | Cl2—C1—Br2 | 0.00 (6) |
CH_{2}BrCl | D_{x} = 2.655 Mg m^{−}^{3} |
M_{r} = 129.39 | Melting point: 185 K |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
a = 4.1126 (8) Å | Cell parameters from 1476 reflections |
b = 8.0685 (16) Å | θ = 5.1–29.9° |
c = 9.755 (2) Å | µ = 13.21 mm^{−}^{1} |
V = 323.69 (11) Å^{3} | T = 295 K |
Z = 4 | Cylinder, colourless |
F(000) = 240 | 0.31 × 0.31 × 0.05 mm |
KM-4 CCD diffractometer | 160 independent reflections |
Radiation source: fine-focus sealed tube | 126 reflections with I > 2σ(I) |
Graphite monochromator | R_{int} = 0.083 |
ϕ– and ω–scans | θ_{max} = 29.9°, θ_{min} = 5.1° |
Absorption correction: numerical Correction for absorption of the diamond-anvil cell and the sample were made using program REDSHABS (Katrusiak, A. (2003) REDSHABS. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467). | h = −5→5 |
T_{min} = 0.18, T_{max} = 0.42 | k = −11→10 |
2144 measured reflections | l = −3→3 |
Refinement on F^{2} | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F^{2} > 2σ(F^{2})] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F^{2}) = 0.058 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0301P)^{2}] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
S = 1.05 | (Δ/σ)_{max} < 0.001 |
160 reflections | Δρ_{max} = 0.18 e Å^{−}^{3} |
25 parameters | Δρ_{min} = −0.23 e Å^{−}^{3} |
2 restraints | Extinction correction: SHELXL, Fc^{*}=kFc[1+0.001xFc^{2}λ^{3}/sin(2θ)]^{-1/4} |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (5) |
CH_{2}BrCl | V = 323.69 (11) Å^{3} |
M_{r} = 129.39 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 4.1126 (8) Å | µ = 13.21 mm^{−}^{1} |
b = 8.0685 (16) Å | T = 295 K |
c = 9.755 (2) Å | 0.31 × 0.31 × 0.05 mm |
KM-4 CCD diffractometer | 160 independent reflections |
Absorption correction: numerical Correction for absorption of the diamond-anvil cell and the sample were made using program REDSHABS (Katrusiak, A. (2003) REDSHABS. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467). | 126 reflections with I > 2σ(I) |
T_{min} = 0.18, T_{max} = 0.42 | R_{int} = 0.083 |
2144 measured reflections |
R[F^{2} > 2σ(F^{2})] = 0.030 | 2 restraints |
wR(F^{2}) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρ_{max} = 0.18 e Å^{−}^{3} |
160 reflections | Δρ_{min} = −0.23 e Å^{−}^{3} |
25 parameters |
Experimental. Data were collected at room temperature and pressure of 1.04 (5) GPa with the crystal obtained by the in situ high-pressure crystallization technique. Pressure was determined by monitoring the shift of the ruby R1-fluorescence line. |
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 F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The DAC imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Cl1 | 0.19106 (12) | 0.84807 (8) | 0.3854 (2) | 0.059 (18) | 0.50 |
Br1 | 0.19106 (12) | 0.84807 (8) | 0.3854 (2) | 0.052 (7) | 0.50 |
C1 | 0.0000 | 0.97434 (8) | 0.2500 | 0.048 (10) | |
H1 | −0.158 (3) | 1.0499 (16) | 0.2892 (2) | 0.057* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Cl1 | 0.074 (7) | 0.033 (3) | 0.07 (5) | 0.000 (3) | 0.008 (12) | −0.005 (12) |
Br1 | 0.053 (2) | 0.063 (2) | 0.04 (2) | 0.0197 (14) | 0.008 (4) | 0.008 (5) |
C1 | 0.066 (4) | 0.028 (3) | 0.05 (3) | 0.000 | −0.006 (8) | 0.000 |
Cl1—C1 | 1.8436 (15) | C1—Cl1^{i} | 1.8436 (15) |
Br1—C1 | 1.8436 (15) | C1—H1 | 0.9700 (1) |
C1—Br1^{i} | 1.8436 (15) | ||
Br1^{i}—C1—Cl1^{i} | 0.00 (3) | Cl1—C1—Br1 | 0.00 (9) |
Br1^{i}—C1—Cl1 | 112.91 (8) | Br1^{i}—C1—H1 | 110.1 (9) |
Cl1^{i}—C1—Cl1 | 112.91 (8) | Cl1^{i}—C1—H1 | 110.1 (9) |
Br1^{i}—C1—Br1 | 112.91 (8) | Cl1—C1—H1 | 110.52 (11) |
Cl1^{i}—C1—Br1 | 112.91 (8) | Br1—C1—H1 | 110.52 (11) |
Symmetry code: (i) −x, y, −z+1/2. |
CH_{2}BrCl | D_{x} = 2.802 Mg m^{−}^{3} |
M_{r} = 129.39 | Melting point: 185 K |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9929 (8) Å | Cell parameters from 1548 reflections |
b = 7.9351 (16) Å | θ = 5.1–29.6° |
c = 9.6808 (19) Å | µ = 13.94 mm^{−}^{1} |
V = 306.73 (11) Å^{3} | T = 295 K |
Z = 4 | Cylinder, colourless |
F(000) = 240 | 0.38 × 0.38 × 0.08 mm |
KM-4 CCD diffractometer | 295 independent reflections |
Radiation source: fine-focus sealed tube | 271 reflections with I > 2σ(I) |
Graphite monochromator | R_{int} = 0.057 |
ϕ– and ω–scans | θ_{max} = 29.6°, θ_{min} = 5.1° |
Absorption correction: numerical Correction for absorption of the diamond-anvil cell and the sample were made using program REDSHABS (Katrusiak, A. (2003) REDSHABS. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467). | h = −3→3 |
T_{min} = 0.13, T_{max} = 0.31 | k = −10→10 |
2283 measured reflections | l = −12→12 |
Refinement on F^{2} | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F^{2} > 2σ(F^{2})] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F^{2}) = 0.065 | w = 1/[σ^{2}(F_{o}^{2}) + (0.031P)^{2} + 0.0922P] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
S = 1.20 | (Δ/σ)_{max} < 0.001 |
295 reflections | Δρ_{max} = 0.35 e Å^{−}^{3} |
25 parameters | Δρ_{min} = −0.34 e Å^{−}^{3} |
2 restraints | Extinction correction: SHELXL, Fc^{*}=kFc[1+0.001xFc^{2}λ^{3}/sin(2θ)]^{-1/4} |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.005 (2) |
CH_{2}BrCl | V = 306.73 (11) Å^{3} |
M_{r} = 129.39 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 3.9929 (8) Å | µ = 13.94 mm^{−}^{1} |
b = 7.9351 (16) Å | T = 295 K |
c = 9.6808 (19) Å | 0.38 × 0.38 × 0.08 mm |
KM-4 CCD diffractometer | 295 independent reflections |
Absorption correction: numerical Correction for absorption of the diamond-anvil cell and the sample were made using program REDSHABS (Katrusiak, A. (2003) REDSHABS. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467). | 271 reflections with I > 2σ(I) |
T_{min} = 0.13, T_{max} = 0.31 | R_{int} = 0.057 |
2283 measured reflections |
R[F^{2} > 2σ(F^{2})] = 0.029 | 2 restraints |
wR(F^{2}) = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | Δρ_{max} = 0.35 e Å^{−}^{3} |
295 reflections | Δρ_{min} = −0.34 e Å^{−}^{3} |
25 parameters |
Experimental. Data were collected at room temperature and pressure of 1.72 (5) GPa with the crystal obtained by the in situ high-pressure crystallization technique. Pressure was determined by monitoring the shift of the ruby R1-fluorescence line. |
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 F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The DAC imposes severe restrictions on which reflections can be collected, resulting in a low data:parameter ratio. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Cl1 | 0.19596 (12) | 0.84967 (6) | 0.38649 (5) | 0.034 (3) | 0.50 |
Br1 | 0.19596 (12) | 0.84967 (6) | 0.38649 (5) | 0.0377 (17) | 0.50 |
C1 | 0.0000 | 0.98034 (8) | 0.2500 | 0.0353 (14) | |
H1 | −0.166 (3) | 1.0547 (16) | 0.2907 (3) | 0.042* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Cl1 | 0.048 (9) | 0.027 (4) | 0.027 (4) | 0.002 (3) | 0.016 (4) | −0.004 (3) |
Br1 | 0.038 (4) | 0.044 (2) | 0.032 (2) | 0.0114 (16) | −0.0010 (17) | 0.0061 (13) |
C1 | 0.036 (5) | 0.028 (2) | 0.042 (2) | 0.000 | −0.003 (2) | 0.000 |
Cl1—C1 | 1.8529 (6) | C1—Cl1^{i} | 1.8529 (6) |
Br1—C1 | 1.8529 (6) | C1—H1 | 0.9700 (1) |
C1—Br1^{i} | 1.8529 (6) | ||
Br1^{i}—C1—Cl1^{i} | 0.00 (3) | Cl1—C1—Br1 | 0.00 (3) |
Br1^{i}—C1—Cl1 | 111.94 (5) | Br1^{i}—C1—H1 | 110.0 (9) |
Cl1^{i}—C1—Cl1 | 111.94 (5) | Cl1^{i}—C1—H1 | 110.0 (9) |
Br1^{i}—C1—Br1 | 111.94 (5) | Cl1—C1—H1 | 109.82 (4) |
Cl1^{i}—C1—Br1 | 111.94 (5) | Br1—C1—H1 | 109.82 (4) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
(cbm_170K) | (cbm_100K) | (cbm_1.04GPa) | (cbm_1.72GPa) | |
Crystal data | ||||
Chemical formula | CH_{2}BrCl | CH_{2}BrCl | CH_{2}BrCl | CH_{2}BrCl |
M_{r} | 129.39 | 129.39 | 129.39 | 129.39 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Orthorhombic, Pbcn | Orthorhombic, Pbcn |
Temperature (K) | 170 | 100 | 295 | 295 |
a, b, c (Å) | 11.959 (2), 4.4531 (9), 14.873 (3) | 11.874 (2), 4.4224 (9), 14.582 (3) | 4.1126 (8), 8.0685 (16), 9.755 (2) | 3.9929 (8), 7.9351 (16), 9.6808 (19) |
α, β, γ (°) | 90, 112.96 (3), 90 | 90, 112.04 (3), 90 | 90, 90, 90 | 90, 90, 90 |
V (Å^{3}) | 729.3 (3) | 709.8 (2) | 323.69 (11) | 306.73 (11) |
Z | 8 | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm^{−}^{1}) | 11.73 | 12.05 | 13.21 | 13.94 |
Crystal size (mm) | 0.12 × 0.12 × 0.10 | 0.12 × 0.12 × 0.10 | 0.31 × 0.31 × 0.05 | 0.38 × 0.38 × 0.08 |
Data collection | ||||
Diffractometer | KM-4 CCD diffractometer | KM-4 CCD diffractometer | KM-4 CCD diffractometer | KM-4 CCD diffractometer |
Absorption correction | Multi-scan Correction for absorption was made using XEMP (SHELXTL, Sheldrick (1990)). | Multi-scan Correction for absorption was made using XEMP (SHELXTL, Sheldrick (1990)). | Numerical Correction for absorption of the diamond-anvil cell and the sample were made using program REDSHABS (Katrusiak, A. (2003) REDSHABS. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467). | Numerical Correction for absorption of the diamond-anvil cell and the sample were made using program REDSHABS (Katrusiak, A. (2003) REDSHABS. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467). |
T_{min}, T_{max} | 0.22, 0.32 | 0.22, 0.32 | 0.18, 0.42 | 0.13, 0.31 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2422, 909, 643 | 3122, 923, 784 | 2144, 160, 126 | 2283, 295, 271 |
R_{int} | 0.109 | 0.078 | 0.083 | 0.057 |
(sin θ/λ)_{max} (Å^{−}^{1}) | 0.684 | 0.696 | 0.702 | 0.696 |
Refinement | ||||
R[F^{2} > 2σ(F^{2})], wR(F^{2}), S | 0.066, 0.172, 1.15 | 0.051, 0.128, 1.12 | 0.030, 0.058, 1.05 | 0.029, 0.065, 1.20 |
No. of reflections | 909 | 923 | 160 | 295 |
No. of parameters | 36 | 36 | 25 | 25 |
No. of restraints | 6 | 6 | 2 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρ_{max}, Δρ_{min} (e Å^{−}^{3}) | 0.83, −0.66 | 1.51, −0.72 | 0.18, −0.23 | 0.35, −0.34 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2004); REDSHABS (Katrusiak, A. 2003), SHELXS97 (Sheldrick, 1990), SHELXS–97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL–97 (Sheldrick, 1997), X-SEED 2.0.