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In the title compound, C12H7Cl3, the dihedral angle of the bi­phenyl moiety is 51.21 (5)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800021127/ob6018sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800021127/ob6018Isup2.hkl
Contains datablock I

CCDC reference: 159720

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.026
  • wR factor = 0.054
  • Data-to-parameter ratio = 16.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10 Absorption corrections should be applied. Tmin and Tmax expected: 0.826 0.944 RT(exp) = 1.144 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 2305 Count of symmetry unique reflns 1226 Completeness (_total/calc) 188.01% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1079 Fraction of Friedel pairs measured 0.880 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Polychlorinated biphenyls (PCBs) are persistent and widespread environmental contaminants (Hansen, 1999). Their lipophilic character and resistance to degradation contribute to the tendency of PCBs to accumulate in the food chain, where they present an environmental and human health hazard (Hansen, 1999). The three-dimensional structure of a PCB congener is strongly correlated with its toxicity. For example, derivatives without ortho chlorine substituents, also referred to as `co-planar PCBs', are known to bind to the Ah receptor, and their mechanism of toxicity is well investigated. Recently other targets with differing structural requirements have been identified as affecting several organ systems (Robertson & Hansen, 2001).

Out of 209 possible PCB congeners, only the crystal structures of seven PCB congeners have been described. The bond distances and bond angles in the title compound, (I), are similar to those found in other chlorinated biphenyls [summarized by Miao et al. (1997)]. The torsion angle between the two phenyl rings of PCBs appears to depend on the degree of chlorination at the ortho position. According to published data, mono-ortho, di-ortho and tetra-ortho substituted PCBs show dihedral angles of 49–52, 58–67 and 86–87°, respectively [summarized by Miao et al. (1997) and Singh et al. (1986)]. The dihedral angle of (I), 51.21 (5)°, is the same as those published for PCB congeners with one ortho substituent. The theoretical torsion angles of mono-ortho PCBs calculated by Höfler et al. (1988) are larger (60–72°) than those reported for the solid state. Thus, packing effects appear to influence the torsion angle between the two phenyl rings of PCBs in the solid state.

Experimental top

The title compound, (I), was synthesized in 70% yield by the palladium-catalyzed cross coupling of 4-chlorobenzene boronic acid and 2,3-dichlorobromobenzene (Lehmler & Robertson, 2001; Bauer et al., 1995). Colourless needles were obtained upon crystallization from methanol; m.p. 341–342 K.

Refinement top

Assignment of space group Cc based on systematic absences and intensity statistics. The possibility of the centrosymmetric space group C2/c was discounted by lack of a suitable solution and by the wholly satisfactory refinement in Cc. There were no substantial correlation coefficients in the variance-covariance matrix between parameters sensitive to a missing inversion centre. No formal absorption correction was applied. Face-indexed correction was not feasible because of the crystal morphology. Correction based on multiple measurements of equivalents was attempted but was deemed unsatisfactory. Anisotropic absorption is corrected in a reasonably approximate manner by the inter-frame scaling and merging of equivalents within the data-reduction program SCALEPACK (Otwinowski & Minor, 1997). Subsequent application of an empirical absorption correction based on ΔF2 made no substantive difference to either data or model and so the uncorrected data were employed in refinement.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELX97-2 (Sheldrick, 1997) and local procedures.

Figures top
[Figure 1] Fig. 1. A view of (I) with non-H atom displacement ellipsoids drawn at the 50% probability level.
2,3,4'-Trichlorobiphenyl top
Crystal data top
C12H7Cl3Dx = 1.605 Mg m3
Mr = 257.53Melting point = 68–69 K
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 3.901 (1) ÅCell parameters from 7599 reflections
b = 17.398 (2) Åθ = 1.0–27.5°
c = 15.749 (2) ŵ = 0.82 mm1
β = 94.51 (1)°T = 173 K
V = 1065.6 (3) Å3Irregular flattened needles, colourless
Z = 40.24 × 0.20 × 0.07 mm
F(000) = 520
Data collection top
Nonius KappaCCD
diffractometer
2197 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 27.5°, θmin = 2.3°
Detector resolution: 18 pixels mm-1h = 45
ω scans at fixed χ = 55°k = 2222
4022 measured reflectionsl = 2020
2305 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026 w = 1/[σ2(Fo2) + (0.0115P)2 + 0.3392P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.20 e Å3
2305 reflectionsΔρmin = 0.17 e Å3
137 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.0064 (7)
Primary atom site location: structure-invariant direct methodsAbsolute structure: (Flack, 1983), 1076 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (5)
Crystal data top
C12H7Cl3V = 1065.6 (3) Å3
Mr = 257.53Z = 4
Monoclinic, CcMo Kα radiation
a = 3.901 (1) ŵ = 0.82 mm1
b = 17.398 (2) ÅT = 173 K
c = 15.749 (2) Å0.24 × 0.20 × 0.07 mm
β = 94.51 (1)°
Data collection top
Nonius KappaCCD
diffractometer
2197 reflections with I > 2σ(I)
4022 measured reflectionsRint = 0.023
2305 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.054Δρmax = 0.20 e Å3
S = 1.07Δρmin = 0.17 e Å3
2305 reflectionsAbsolute structure: (Flack, 1983), 1076 Friedel pairs
137 parametersAbsolute structure parameter: 0.02 (5)
2 restraints
Special details top

Experimental. 1H-NMR (CDCl3, 400 MHz) δ 7.20 (d, J = 8.0 Hz, d, J = 2.0 Hz, 4-H), 7.25 ("t", J = 8.0 Hz, 5-H), 7.34 (AA'XX' system, 3',5'-H), 7.42 (AA'XX' system, 2',6'-H), 7.48 (d, J = 8.0 Hz, d, J = 2.0 Hz, 6-H); 13C-NMR (CDCl3, 100 MHz) δ 127.23 (C-6), 128.38 (C-2',6'), 129.43 (C-4$), 129.29 (C-5$), 129.50 (C-3',5'), 131.51 (C-2), 133.49 (C-4'*), 133.90 (C-3*), 137.57 (C-1'), 141.58 (C-1) (assignments with (*,$) are interchangeable); IR [cm-1]: 1445, 1415, 1384, 1093, 1013; MS m/z (relative intensity, %): 256 (100, C12H7Cl3.+), 220 (5, M-HCl), 186 (45, M—Cl2), 150 (14).

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.

Refinement of the Flack absolute structure parameter using the SHELXL97 commands TWIN and BASF gave -0.02 (5) for the present model and 1.02 (5) for its inverted counterpart.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3350 (5)0.62904 (10)0.90812 (11)0.0174 (4)
C20.2276 (5)0.64033 (11)0.99002 (12)0.0197 (4)
H20.12580.68781.00410.024*
C30.2689 (5)0.58249 (12)1.05089 (12)0.0230 (4)
H30.19230.58991.10610.028*
C40.4221 (5)0.51421 (11)1.03046 (12)0.0213 (4)
C50.5279 (5)0.50121 (11)0.95014 (13)0.0224 (4)
H50.63070.45370.93670.027*
C60.4816 (5)0.55854 (11)0.88965 (12)0.0212 (4)
H70.55140.54970.83400.025*
C70.2830 (5)0.68775 (11)0.83908 (11)0.0182 (4)
C80.3923 (5)0.76414 (11)0.84685 (11)0.0176 (4)
C90.3536 (5)0.81375 (11)0.77730 (11)0.0193 (4)
C100.2017 (5)0.78876 (12)0.69979 (12)0.0237 (5)
H100.17730.82280.65250.028*
C110.0853 (5)0.71345 (12)0.69176 (12)0.0234 (5)
H110.02380.69590.63930.028*
C120.1293 (5)0.66408 (12)0.76062 (11)0.0214 (4)
H120.05230.61250.75420.026*
Cl10.47874 (13)0.44278 (3)1.10768 (3)0.03361 (15)
Cl20.58842 (10)0.79900 (3)0.94221 (3)0.02358 (12)
Cl30.50181 (12)0.90755 (3)0.78489 (3)0.02713 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0162 (10)0.0186 (9)0.0171 (8)0.0017 (8)0.0008 (7)0.0022 (8)
C20.0199 (10)0.0201 (10)0.0192 (9)0.0002 (8)0.0019 (7)0.0021 (7)
C30.0226 (11)0.0286 (11)0.0182 (9)0.0020 (9)0.0033 (8)0.0002 (8)
C40.0178 (11)0.0228 (11)0.0230 (10)0.0037 (9)0.0012 (8)0.0048 (8)
C50.0220 (11)0.0176 (10)0.0277 (10)0.0015 (8)0.0026 (8)0.0035 (9)
C60.0230 (11)0.0228 (11)0.0183 (9)0.0016 (9)0.0052 (8)0.0032 (7)
C70.0153 (9)0.0213 (10)0.0184 (9)0.0023 (8)0.0037 (7)0.0001 (8)
C80.0176 (10)0.0199 (10)0.0153 (8)0.0028 (8)0.0026 (7)0.0039 (7)
C90.0177 (10)0.0188 (10)0.0218 (9)0.0030 (8)0.0050 (8)0.0007 (8)
C100.0257 (11)0.0266 (11)0.0190 (9)0.0051 (9)0.0031 (8)0.0036 (8)
C110.0213 (11)0.0304 (12)0.0184 (9)0.0003 (9)0.0005 (8)0.0033 (8)
C120.0229 (11)0.0213 (10)0.0205 (9)0.0026 (9)0.0053 (8)0.0043 (8)
Cl10.0389 (3)0.0306 (3)0.0314 (3)0.0023 (3)0.0032 (2)0.0135 (2)
Cl20.0287 (3)0.0216 (2)0.0198 (2)0.0015 (2)0.00219 (18)0.00353 (19)
Cl30.0350 (3)0.0182 (2)0.0290 (2)0.0007 (2)0.0073 (2)0.0005 (2)
Geometric parameters (Å, º) top
C1—C61.394 (3)C7—C121.392 (3)
C1—C21.401 (2)C7—C81.398 (3)
C1—C71.494 (3)C8—C91.393 (3)
C2—C31.391 (3)C8—Cl21.7401 (18)
C2—H20.9500C9—C101.384 (3)
C3—C41.379 (3)C9—Cl31.7323 (19)
C3—H30.9500C10—C111.389 (3)
C4—C51.380 (3)C10—H100.9500
C4—Cl11.7408 (19)C11—C121.384 (3)
C5—C61.381 (3)C11—H110.9500
C5—H50.9500C12—H120.9500
C6—H70.9500
C6—C1—C2118.22 (17)C12—C7—C8117.76 (17)
C6—C1—C7118.97 (16)C12—C7—C1117.91 (17)
C2—C1—C7122.73 (17)C8—C7—C1124.26 (16)
C3—C2—C1120.42 (18)C9—C8—C7120.43 (16)
C3—C2—H2119.8C9—C8—Cl2118.40 (15)
C1—C2—H2119.8C7—C8—Cl2121.15 (14)
C4—C3—C2119.44 (18)C10—C9—C8120.73 (17)
C4—C3—H3120.3C10—C9—Cl3118.30 (14)
C2—C3—H3120.3C8—C9—Cl3120.96 (14)
C3—C4—C5121.43 (18)C9—C10—C11119.38 (18)
C3—C4—Cl1119.04 (15)C9—C10—H10120.3
C5—C4—Cl1119.53 (16)C11—C10—H10120.3
C4—C5—C6118.80 (18)C12—C11—C10119.65 (18)
C4—C5—H5120.6C12—C11—H11120.2
C6—C5—H5120.6C10—C11—H11120.2
C5—C6—C1121.68 (17)C11—C12—C7122.02 (18)
C5—C6—H7119.2C11—C12—H12119.0
C1—C6—H7119.2C7—C12—H12119.0
C6—C1—C2—C30.3 (3)C12—C7—C8—C91.3 (3)
C7—C1—C2—C3177.21 (19)C1—C7—C8—C9175.68 (18)
C1—C2—C3—C41.1 (3)C12—C7—C8—Cl2179.78 (15)
C2—C3—C4—C51.6 (3)C1—C7—C8—Cl22.8 (3)
C2—C3—C4—Cl1178.98 (16)C7—C8—C9—C101.0 (3)
C3—C4—C5—C60.7 (3)Cl2—C8—C9—C10179.51 (17)
Cl1—C4—C5—C6179.89 (16)C7—C8—C9—Cl3177.66 (14)
C4—C5—C6—C10.7 (3)Cl2—C8—C9—Cl30.8 (2)
C2—C1—C6—C51.3 (3)C8—C9—C10—C110.4 (3)
C7—C1—C6—C5178.25 (18)Cl3—C9—C10—C11179.07 (15)
C6—C1—C7—C1248.0 (3)C9—C10—C11—C121.4 (3)
C2—C1—C7—C12128.8 (2)C10—C11—C12—C71.1 (3)
C6—C1—C7—C8129.0 (2)C8—C7—C12—C110.3 (3)
C2—C1—C7—C854.2 (3)C1—C7—C12—C11176.89 (18)

Experimental details

Crystal data
Chemical formulaC12H7Cl3
Mr257.53
Crystal system, space groupMonoclinic, Cc
Temperature (K)173
a, b, c (Å)3.901 (1), 17.398 (2), 15.749 (2)
β (°) 94.51 (1)
V3)1065.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.82
Crystal size (mm)0.24 × 0.20 × 0.07
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4022, 2305, 2197
Rint0.023
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.054, 1.07
No. of reflections2305
No. of parameters137
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.17
Absolute structure(Flack, 1983), 1076 Friedel pairs
Absolute structure parameter0.02 (5)

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1994), SHELX97-2 (Sheldrick, 1997) and local procedures.

Selected geometric parameters (Å, º) top
C1—C71.494 (3)C8—Cl21.7401 (18)
C4—Cl11.7408 (19)C9—Cl31.7323 (19)
C6—C1—C7—C1248.0 (3)C2—C1—C7—C854.2 (3)
 

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