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1,4-Dibromobenzene melts at a considerably higher temperature than the 1,2- and 1,3-isomers. This melting-point difference is consistent with the molecular symmetry, as described by Carnelley's rule, and with the frequency of Br...Br halogen bonds. The lowest melting point of 1,3-dibromobenzene correlates with its two symmetry-independent molecules, indicating their inability to pack closely. Single crystals of 1,2- and 1,3-dibromobenzene have been grown under isochoric conditions in a diamond–anvil cell and at isobaric conditions in a glass capillary. Their structures have been determined in situ by X-ray diffraction. At 295 K 1,2-dibromobenzene crystallizes at 0.2 GPa as orthorhombic, space group Pbca, Z′ = 1, and 1,3-dibromobenzene at 0.3 GPa as orthorhombic, space group P212121, Z′ = 2. The same crystal phases are formed at ambient pressure by freezing these liquids below 256.15 and 248.45 K, respectively. The third isomer, 1,4-dibromobenzene, is a solid at room temperature and crystallizes as monoclinic, space group P21/a. Striking relations between the structures and melting points of the corresponding dibromobenzene and dichlorobenzene isomers have been discussed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614011445/zb5043sup1.cif
Contains datablocks m-dibromobenzene_3kbar, m-dibromobenzene_260K, m-dibromobenzene_100K, o-dibromobenzene_2kbar, o-dibromobenzene_100K, o-dibromobenzene_250K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011445/zb5043m-dibromobenzene_3kbarsup2.hkl
Contains datablock mdbb3kbar

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011445/zb5043m-dibromobenzene_260Ksup3.hkl
Contains datablock mdbb260k

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011445/zb5043m-dibromobenzene_100Ksup4.hkl
Contains datablock mdbb100k

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011445/zb5043o-dibromobenzene_2kbarsup5.hkl
Contains datablock odbb2kbar

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011445/zb5043o-dibromobenzene_100Ksup6.hkl
Contains datablock odbb100k

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614011445/zb5043o-dibromobenzene_250Ksup7.hkl
Contains datablock odbb250k

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614011445/zb5043sup8.pdf
Tables of intermolecular distances and angles in halogen bonds; table comparing the dichlorobenzene and dibromobenzene isomers.

CCDC references: 1003646; 1003647; 1003648; 1003649; 1003650; 1003651

Computing details top

For all compounds, data collection: CrysAlis PRO (Agilent Technologies, 2014); cell refinement: CrysAlis PRO (Agilent Technologies, 2014); data reduction: CrysAlis PRO (Agilent Technologies, 2014); REDSHADE (Katrusiak, A. 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

(m-dibromobenzene_3kbar) 1,3-dibromobenzene top
Crystal data top
C6H4Br2F(000) = 880
Mr = 235.89Dx = 2.276 Mg m3
Orthorhombic, P212121Melting point: 266 K
a = 4.106 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.899 (3) ŵ = 11.66 mm1
c = 26.001 (5) ÅT = 295 K
V = 1377.1 (5) Å3Cylinder, colourless
Z = 80.35 × 0.35 × 0.1 × 0.35 (radius) mm
Data collection top
KM-4 CCD
diffractometer
1412 independent reflections
Radiation source: fine-focus sealed tube797 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.115
φ– and ω–scansθmax = 25.0°, θmin = 3.3°
Absorption correction: analytical
Corrections for absorption of the diamond-anvil cell and the sample were made using program REDSHADE [Katrusiak, A. (2003) REDSHADE. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467].
h = 44
Tmin = 0.093, Tmax = 0.288k = 1414
9097 measured reflectionsl = 1919
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042 w = 1/[σ2(Fo2) + (0.P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.34 e Å3
1412 reflectionsΔρmin = 0.35 e Å3
87 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00483 (18)
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: 0.70 (3)
Special details top

Experimental. Data were collected at room temperature and pressure of 0.30 (5) GPa on a crystal obtained by the high-pressure in situ crystallization technique. Pressure was calibrated by monitoring the shift of the R1 ruby fluorescence line. [Mao, H·K., Xu, J., Bell, P·M., (1986) J. Geophys. Res. 91, 4673–4676].

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
Br1A0.1603 (3)0.16423 (7)0.90763 (7)0.0654 (8)
Br3A0.6990 (3)0.53294 (8)0.82864 (8)0.0684 (8)
C1A0.269 (2)0.3069 (7)0.9168 (7)0.046 (3)*
C2A0.417 (2)0.3571 (8)0.8777 (6)0.051 (3)*
H2A0.46600.32230.84740.061*
C3A0.497 (2)0.4613 (7)0.8834 (7)0.040 (3)*
C4A0.410 (2)0.5094 (8)0.9264 (8)0.053 (3)*
H4A0.46430.57910.92980.064*
C5A0.240 (2)0.4618 (8)0.9675 (7)0.078 (4)*
H5A0.17670.49860.99660.093*
C6A0.172 (2)0.3554 (8)0.9617 (6)0.061 (4)*
H6A0.06450.31870.98740.074*
Br1B0.0867 (3)0.30936 (9)0.55211 (8)0.0673 (8)
Br3B0.0744 (3)0.22207 (9)0.76359 (8)0.0706 (8)
C1B0.039 (2)0.3425 (8)0.6179 (7)0.055 (3)*
C2B0.052 (2)0.2811 (7)0.6629 (7)0.041 (3)*
H2B0.17370.22080.65920.049*
C3B0.040 (2)0.3118 (8)0.7084 (7)0.046 (4)*
C4B0.215 (2)0.3996 (7)0.7197 (6)0.053 (3)*
H4B0.27290.41760.75310.063*
C5B0.300 (2)0.4597 (7)0.6769 (7)0.042 (3)*
H5B0.41780.52020.68280.050*
C6B0.221 (2)0.4351 (7)0.6252 (7)0.051 (4)*
H6B0.28360.47700.59780.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0726 (8)0.0552 (8)0.068 (3)0.0148 (7)0.0019 (11)0.0024 (7)
Br3A0.0696 (9)0.0635 (9)0.072 (3)0.0168 (7)0.0074 (11)0.0147 (8)
Br1B0.0803 (9)0.0986 (11)0.023 (3)0.0056 (8)0.0010 (12)0.0006 (8)
Br3B0.0772 (8)0.0815 (10)0.053 (3)0.0010 (7)0.0065 (12)0.0119 (8)
Geometric parameters (Å, º) top
Br1A—C1A1.908 (10)Br1B—C1B1.837 (17)
Br3A—C3A1.889 (16)Br3B—C3B1.902 (16)
C1A—C2A1.351 (18)C1B—C6B1.422 (12)
C1A—C6A1.383 (19)C1B—C2B1.46 (2)
C2A—C3A1.391 (11)C2B—C3B1.30 (2)
C3A—C4A1.33 (2)C3B—C4B1.373 (12)
C4A—C5A1.42 (2)C4B—C5B1.40 (2)
C5A—C6A1.408 (12)C5B—C6B1.42 (2)
C2A—C1A—C6A123.2 (12)C6B—C1B—C2B118.9 (16)
C2A—C1A—Br1A118.3 (13)C6B—C1B—Br1B117.8 (11)
C6A—C1A—Br1A118.3 (12)C2B—C1B—Br1B123.2 (11)
C1A—C2A—C3A119.4 (15)C3B—C2B—C1B119.3 (12)
C4A—C3A—C2A118.5 (14)C2B—C3B—C4B126.6 (16)
C4A—C3A—Br3A121.6 (10)C2B—C3B—Br3B115.4 (10)
C2A—C3A—Br3A119.8 (10)C4B—C3B—Br3B118.0 (13)
C3A—C4A—C5A124.4 (13)C3B—C4B—C5B114.7 (16)
C6A—C5A—C4A116.1 (15)C4B—C5B—C6B124.8 (12)
C1A—C6A—C5A118.3 (14)C5B—C6B—C1B115.7 (14)
(m-dibromobenzene_260K) 1,3-dibromobenzene top
Crystal data top
C6H4Br2F(000) = 880
Mr = 235.89Dx = 2.234 Mg m3
Orthorhombic, P212121Melting point: 266 K
a = 4.1264 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.9505 (13) ŵ = 11.44 mm1
c = 26.257 (2) ÅT = 260 K
V = 1403.1 (2) Å3Block, colourless
Z = 80.3 × 0.3 × 0.3 mm
Data collection top
KM-4 CCD
diffractometer
3621 independent reflections
Radiation source: fine-focus sealed tube1976 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
ω–scansθmax = 29.8°, θmin = 2.2°
Absorption correction: multi-scan
CrysAlisPro (Agilent Technologies, 2014). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 54
Tmin = 0.038, Tmax = 1.000k = 1617
13571 measured reflectionsl = 3635
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.114 w = 1/[σ2(Fo2) + (0.038P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3621 reflectionsΔρmax = 0.43 e Å3
85 parametersΔρmin = 0.36 e Å3
0 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (3)
Special details top

Experimental. Crystal grown in situ in a 0.3 mm glass capillary.

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
Br1A0.1640 (2)0.16460 (7)0.90745 (4)0.0829 (3)
Br3A0.6981 (3)0.53185 (7)0.82852 (4)0.0852 (3)
C1A0.2684 (17)0.3074 (6)0.9160 (3)0.0612 (19)*
C2A0.4271 (19)0.3569 (6)0.8771 (3)0.0607 (19)*
H2A0.48920.32170.84780.073*
C3A0.491 (2)0.4603 (6)0.8828 (3)0.068 (2)*
C4A0.408 (2)0.5122 (7)0.9260 (3)0.081 (2)*
H4A0.45950.58170.92970.097*
C5A0.249 (2)0.4603 (7)0.9637 (4)0.086 (3)*
H5A0.18940.49590.99300.103*
C6A0.175 (2)0.3583 (6)0.9600 (3)0.076 (2)*
H6A0.06640.32410.98600.092*
Br1B0.0880 (3)0.30918 (8)0.55237 (3)0.0875 (3)
Br3B0.0720 (2)0.22241 (8)0.76288 (3)0.0839 (3)
C1B0.0349 (19)0.3466 (6)0.6195 (3)0.0607 (19)*
C2B0.0506 (19)0.2827 (6)0.6590 (3)0.0584 (18)*
H2B0.16410.22180.65310.070*
C3B0.038 (2)0.3118 (6)0.7082 (3)0.066 (2)*
C4B0.216 (2)0.4003 (6)0.7174 (3)0.068 (2)*
H4B0.27530.41840.75040.082*
C5B0.303 (2)0.4610 (7)0.6769 (3)0.076 (2)*
H5B0.42130.52090.68250.091*
C6B0.217 (2)0.4345 (6)0.6281 (3)0.069 (2)*
H6B0.28210.47550.60090.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0901 (7)0.0682 (5)0.0906 (6)0.0145 (5)0.0002 (6)0.0058 (5)
Br3A0.0840 (7)0.0734 (6)0.0983 (7)0.0153 (5)0.0104 (6)0.0155 (5)
Br1B0.0940 (7)0.1064 (7)0.0620 (5)0.0044 (6)0.0010 (5)0.0014 (5)
Br3B0.0904 (7)0.0959 (7)0.0654 (5)0.0022 (5)0.0069 (5)0.0106 (5)
Geometric parameters (Å, º) top
Br1A—C1A1.912 (7)Br1B—C1B1.897 (7)
Br3A—C3A1.903 (8)Br3B—C3B1.899 (8)
C1A—C2A1.372 (10)C1B—C2B1.373 (10)
C1A—C6A1.386 (10)C1B—C6B1.383 (11)
C2A—C3A1.372 (10)C2B—C3B1.396 (10)
C3A—C4A1.361 (11)C3B—C4B1.382 (10)
C4A—C5A1.366 (11)C4B—C5B1.370 (10)
C5A—C6A1.358 (11)C5B—C6B1.372 (10)
C2A—C1A—C6A122.1 (7)C2B—C1B—C6B120.9 (7)
C2A—C1A—Br1A118.2 (6)C2B—C1B—Br1B118.6 (6)
C6A—C1A—Br1A119.7 (6)C6B—C1B—Br1B120.5 (6)
C3A—C2A—C1A117.7 (7)C1B—C2B—C3B118.0 (7)
C4A—C3A—C2A121.7 (8)C4B—C3B—C2B121.7 (8)
C4A—C3A—Br3A119.7 (6)C4B—C3B—Br3B120.1 (6)
C2A—C3A—Br3A118.6 (6)C2B—C3B—Br3B118.2 (6)
C3A—C4A—C5A118.8 (8)C5B—C4B—C3B118.6 (8)
C6A—C5A—C4A122.3 (9)C4B—C5B—C6B121.0 (8)
C5A—C6A—C1A117.4 (9)C5B—C6B—C1B119.8 (8)
(m-dibromobenzene_100K) 1,3-dibromobenzene top
Crystal data top
C6H4Br2F(000) = 880
Mr = 235.89Dx = 2.329 Mg m3
Orthorhombic, P212121Melting point: 266 K
a = 4.0412 (12) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.806 (5) ŵ = 11.94 mm1
c = 25.996 (11) ÅT = 100 K
V = 1345.3 (9) Å3Block, colourless
Z = 80.3 × 0.3 × 0.3 mm
Data collection top
KM-4 CCD
diffractometer
3579 independent reflections
Radiation source: fine-focus sealed tube2895 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ω–scansθmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan
CrysAlisPro (Agilent Technologies, 2014). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 54
Tmin = 0.070, Tmax = 1.000k = 1716
13797 measured reflectionsl = 3535
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.065 w = 1/[σ2(Fo2) + (0.038P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.85(Δ/σ)max = 0.002
3579 reflectionsΔρmax = 0.68 e Å3
85 parametersΔρmin = 0.59 e Å3
0 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.05 (2)
Special details top

Experimental. Crystal grown in situ in a 0.3 mm glass capillary.

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
Br1A0.15961 (12)0.16294 (3)0.907462 (19)0.02160 (12)
Br3A0.70554 (13)0.53293 (4)0.827200 (18)0.02174 (12)
C1A0.2701 (11)0.3058 (3)0.91590 (17)0.0170 (9)*
C2A0.4307 (12)0.3565 (3)0.87628 (16)0.0156 (9)*
H2A0.49110.32140.84640.019*
C3A0.4976 (11)0.4603 (4)0.88277 (17)0.0173 (10)*
C4A0.4169 (13)0.5139 (4)0.92666 (17)0.0214 (10)*
H4A0.47110.58410.93030.026*
C5A0.2523 (12)0.4606 (4)0.96553 (19)0.0240 (11)*
H5A0.19200.49620.99530.029*
C6A0.1767 (13)0.3567 (3)0.96098 (18)0.0215 (10)*
H6A0.06680.32130.98710.026*
Br1B0.09831 (13)0.30960 (4)0.551033 (17)0.02238 (12)
Br3B0.07284 (13)0.22031 (4)0.763572 (17)0.02231 (12)
C1B0.0360 (12)0.3457 (3)0.61880 (16)0.0150 (9)*
C2B0.0573 (12)0.2812 (3)0.65855 (16)0.0154 (9)*
H2B0.18030.22100.65260.018*
C3B0.0403 (12)0.3098 (3)0.70815 (17)0.0172 (10)*
C4B0.2192 (13)0.3986 (3)0.71758 (18)0.0182 (10)*
H4B0.28010.41590.75100.022*
C5B0.3084 (12)0.4622 (4)0.67688 (17)0.0189 (10)*
H5B0.42740.52310.68290.023*
C6B0.2201 (12)0.4350 (3)0.62671 (17)0.0175 (10)*
H6B0.28430.47650.59910.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0242 (3)0.0169 (2)0.0237 (2)0.0046 (2)0.0003 (2)0.00116 (18)
Br3A0.0221 (3)0.0186 (2)0.0246 (2)0.0047 (2)0.0025 (2)0.00427 (19)
Br1B0.0242 (3)0.0290 (3)0.0139 (2)0.0015 (2)0.0004 (2)0.00041 (18)
Br3B0.0242 (3)0.0267 (3)0.0160 (2)0.0007 (2)0.0028 (2)0.00345 (18)
Geometric parameters (Å, º) top
Br1A—C1A1.896 (4)Br1B—C1B1.901 (4)
Br3A—C3A1.912 (5)Br3B—C3B1.897 (4)
C1A—C2A1.380 (6)C1B—C2B1.376 (6)
C1A—C6A1.393 (6)C1B—C6B1.380 (6)
C2A—C3A1.368 (6)C2B—C3B1.397 (6)
C3A—C4A1.370 (6)C3B—C4B1.370 (6)
C4A—C5A1.389 (6)C4B—C5B1.383 (6)
C5A—C6A1.371 (6)C5B—C6B1.396 (6)
C2A—C1A—C6A122.4 (4)C2B—C1B—C6B122.3 (4)
C2A—C1A—Br1A118.6 (3)C2B—C1B—Br1B118.1 (3)
C6A—C1A—Br1A119.0 (3)C6B—C1B—Br1B119.6 (3)
C1A—C2A—C3A117.3 (4)C1B—C2B—C3B117.3 (4)
C4A—C3A—C2A122.8 (4)C4B—C3B—C2B122.1 (4)
C4A—C3A—Br3A119.3 (3)C4B—C3B—Br3B119.5 (3)
C2A—C3A—Br3A117.8 (3)C2B—C3B—Br3B118.3 (3)
C3A—C4A—C5A118.3 (4)C5B—C4B—C3B119.3 (4)
C6A—C5A—C4A121.4 (5)C4B—C5B—C6B120.1 (4)
C5A—C6A—C1A117.8 (5)C5B—C6B—C1B118.9 (4)
(o-dibromobenzene_2kbar) 1,2-dibromobenzene top
Crystal data top
C6H4Br2F(000) = 880
Mr = 235.89Dx = 2.239 Mg m3
Orthorhombic, PbcaMelting point: 278 K
a = 7.837 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 15.258 (3) ŵ = 11.47 mm1
c = 11.706 (2) ÅT = 295 K
V = 1399.8 (5) Å3Cylinder, colourless
Z = 80.4 × 0.4 × 0.1 × 0.4 (radius) mm
Data collection top
KM-4 CCD
diffractometer
898 independent reflections
Radiation source: fine-focus sealed tube502 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
φ– and ω–scansθmax = 25.0°, θmin = 3.2°
Absorption correction: analytical
Corrections for absorption of the diamond-anvil cell and the sample were made using program REDSHADE [Katrusiak, A. (2003) REDSHADE. Adam Mickiewicz University Poznań; Katrusiak, A. (2004) Z. Kristallogr. 219, 461-467].
h = 89
Tmin = 0.494, Tmax = 0.911k = 1718
8086 measured reflectionsl = 1113
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.070P)2]
where P = (Fo2 + 2Fc2)/3
898 reflections(Δ/σ)max < 0.001
43 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.40 e Å3
Special details top

Experimental. Data were collected at room temperature and pressure of 0.20 (5) GPa on a crystal obtained by the high-pressure in situ crystallization technique. Pressure was calibrated by monitoring the shift of the R1 ruby fluorescence line. [Mao, H·K., Xu, J., Bell, P·M., (1986) J. Geophys. Res. 91, 4673–4676].

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
Br10.21942 (17)0.43175 (6)0.48052 (13)0.0843 (6)
Br20.42681 (18)0.42932 (8)0.73334 (12)0.0931 (6)
C10.2545 (11)0.3274 (5)0.5631 (9)0.046 (2)*
C20.3370 (14)0.3252 (5)0.6653 (9)0.058 (3)*
C30.3639 (15)0.2475 (7)0.7223 (9)0.076 (3)*
H30.42090.24640.79200.092*
C40.3038 (14)0.1714 (6)0.6731 (11)0.077 (3)*
H40.32320.11840.71010.092*
C50.2183 (15)0.1711 (7)0.5737 (12)0.084 (4)*
H50.17550.11900.54390.101*
C60.1943 (13)0.2515 (6)0.5149 (9)0.064 (3)*
H60.13860.25270.44480.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1093 (14)0.0597 (7)0.0839 (14)0.0027 (6)0.0182 (7)0.0149 (6)
Br20.0768 (14)0.1032 (10)0.0992 (16)0.0048 (7)0.0206 (7)0.0349 (7)
Geometric parameters (Å, º) top
Br1—C11.883 (8)C2—C31.377 (13)
Br2—C21.911 (9)C3—C41.379 (13)
C1—C21.361 (14)C4—C51.343 (16)
C1—C61.372 (12)C5—C61.419 (13)
C2—C1—C6120.3 (8)C3—C2—Br2117.2 (9)
C2—C1—Br1122.7 (7)C2—C3—C4118.1 (11)
C6—C1—Br1116.9 (7)C5—C4—C3122.3 (11)
C1—C2—C3121.3 (9)C4—C5—C6118.9 (11)
C1—C2—Br2121.4 (7)C1—C6—C5119.0 (11)
(o-dibromobenzene_100K) 1,2-dibromobenzene top
Crystal data top
C6H4Br2F(000) = 880
Mr = 235.89Dx = 2.333 Mg m3
Orthorhombic, PbcaMelting point: 278 K
a = 7.6473 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 15.1550 (15) ŵ = 11.95 mm1
c = 11.5909 (12) ÅT = 100 K
V = 1343.3 (2) Å3Block, colourless
Z = 80.3 × 0.3 × 0.3 mm
Data collection top
KM-4 CCD
diffractometer
1815 independent reflections
Radiation source: fine-focus sealed tube1304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.104
ω–scansθmax = 29.8°, θmin = 2.7°
Absorption correction: multi-scan
CrysAlisPro (Agilent Technologies, 2014). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 910
Tmin = 0.109, Tmax = 1.000k = 2020
11683 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.045P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.40(Δ/σ)max < 0.001
1815 reflectionsΔρmax = 1.23 e Å3
44 parametersΔρmin = 2.14 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0017 (4)
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
Br10.21818 (10)0.43299 (4)0.47840 (5)0.0286 (3)
Br20.42670 (9)0.43161 (5)0.73435 (6)0.0320 (3)
C10.2537 (7)0.3274 (4)0.5621 (5)0.0200 (12)*
C20.3389 (8)0.3265 (4)0.6680 (5)0.0245 (13)*
C30.3644 (9)0.2473 (4)0.7243 (5)0.0275 (14)*
H30.42390.24610.79420.033*
C40.3025 (9)0.1701 (5)0.6779 (6)0.0336 (15)*
H40.31910.11700.71680.040*
C50.2151 (9)0.1713 (4)0.5728 (6)0.0290 (14)*
H50.17310.11900.54150.035*
C60.1909 (8)0.2494 (4)0.5153 (5)0.0226 (13)*
H60.13250.25020.44500.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0409 (5)0.0201 (4)0.0247 (4)0.0008 (2)0.0062 (3)0.0056 (2)
Br20.0306 (4)0.0369 (5)0.0286 (4)0.0012 (3)0.0059 (3)0.0133 (3)
Geometric parameters (Å, º) top
Br1—C11.888 (6)C2—C31.377 (9)
Br2—C21.894 (6)C3—C41.372 (9)
C1—C21.391 (8)C4—C51.391 (9)
C1—C61.388 (8)C5—C61.368 (9)
C2—C1—C6120.2 (6)C3—C2—Br2119.3 (5)
C2—C1—Br1121.8 (4)C4—C3—C2120.4 (6)
C6—C1—Br1118.0 (4)C5—C4—C3120.1 (7)
C1—C2—C3119.4 (6)C4—C5—C6120.1 (6)
C1—C2—Br2121.3 (4)C5—C6—C1119.9 (6)
(o-dibromobenzene_250K) 1,2-dibromobenzene top
Crystal data top
C6H4Br2F(000) = 880
Mr = 235.89Dx = 2.242 Mg m3
Orthorhombic, PbcaMelting point: 278 K
a = 7.8346 (19) ÅMo Kα radiation, λ = 0.71073 Å
b = 15.270 (4) ŵ = 11.49 mm1
c = 11.684 (3) ÅT = 250 K
V = 1397.8 (6) Å3Block, colourless
Z = 80.3 × 0.3 × 0.3 mm
Data collection top
KM-4 CCD
diffractometer
1815 independent reflections
Radiation source: fine-focus sealed tube804 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
ω–scansθmax = 29.4°, θmin = 3.2°
Absorption correction: multi-scan
CrysAlisPro (Agilent Technologies, 2014). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 1010
Tmin = 0.106, Tmax = 1.000k = 2020
8812 measured reflectionsl = 167
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.045P)2]
where P = (Fo2 + 2Fc2)/3
1815 reflections(Δ/σ)max < 0.001
43 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.44 e Å3
Special details top

Experimental. Crystal grown in situ in a 0.3 mm glass capillary.

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
Br10.21941 (13)0.43189 (6)0.48039 (8)0.0859 (4)
Br20.42600 (12)0.42951 (7)0.73268 (8)0.0940 (4)
C10.2566 (9)0.3275 (4)0.5614 (6)0.0571 (17)*
C20.3403 (10)0.3275 (5)0.6646 (6)0.0662 (19)*
C30.3612 (10)0.2481 (5)0.7203 (7)0.077 (2)*
H30.41640.24680.79080.092*
C40.3021 (11)0.1708 (6)0.6736 (7)0.085 (3)*
H40.32150.11800.71110.102*
C50.2164 (11)0.1720 (6)0.5736 (7)0.084 (3)*
H50.17310.12020.54350.100*
C60.1926 (9)0.2498 (5)0.5158 (6)0.069 (2)*
H60.13390.25040.44660.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1062 (7)0.0649 (6)0.0865 (6)0.0011 (5)0.0153 (5)0.0136 (4)
Br20.0775 (6)0.1062 (8)0.0984 (7)0.0042 (5)0.0166 (5)0.0321 (5)
Geometric parameters (Å, º) top
Br1—C11.876 (7)C2—C31.387 (10)
Br2—C21.873 (7)C3—C41.380 (10)
C1—C21.373 (10)C4—C51.348 (11)
C1—C61.394 (9)C5—C61.380 (10)
C2—C1—C6120.5 (7)C3—C2—Br2119.1 (6)
C2—C1—Br1121.1 (5)C4—C3—C2121.6 (8)
C6—C1—Br1118.3 (5)C5—C4—C3119.9 (9)
C1—C2—C3117.9 (7)C4—C5—C6120.2 (9)
C1—C2—Br2123.0 (5)C5—C6—C1119.8 (7)
 

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