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The crystal structure of a metabolite of 4-chloro­bi­phenyl (PCB 3), 4-chloro-3',4'-di­hydroxybi­phenyl (C12H9ClO2), is described. The dihedral angle of the title compound is 43.1 (3)°, which is in reasonable agreement with the calculated value of 37.2°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008844/om6031sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008844/om6031Isup2.hkl
Contains datablock I

CCDC reference: 170762

Key indicators

  • Single-crystal X-ray study
  • T = 144 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.036
  • wR factor = 0.075
  • Data-to-parameter ratio = 15.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
STRVAL_01 From the CIF: _refine_ls_abs_structure_Flack 0.510 From the CIF: _refine_ls_abs_structure_Flack_su 0.060 Alert C Flack test results are ambiguous. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.40 From the CIF: _reflns_number_total 2175 Count of symmetry unique reflns 1235 Completeness (_total/calc) 176.11% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 940 Fraction of Friedel pairs measured 0.761 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) were commercially manufactured and available as complex mixtures for use in transformers, capacitors and hydraulic fluids where they impart chemical stability and fire retardency (Robertson & Hansen, 2001; Hansen, 1999). Their stability, lipophilic character and resistance to physical and biological decomposition contribute to the tendency of PCBs to accumulate in the food chain, where they persist and have become an environmental and human health hazard (Hansen, 1999). The varied mechanisms of PCB toxicity are still poorly understood, in part because the technical PCB products consist of many of the 209 possible PCB congeners.

PCBs are metabolized in vivo to hydroxy- and sulfur-containing metabolites. Hydroxylation proceeds primarily at the meta and para position either via an arene oxide or by direct insertion of a hydroxyl group (Letcher et al., 2000). One of the many unanswered questions is how the three dimensional structure of these important PCB metabolites determines their biological and toxic effects. Few crystal structures of PCB metabolites have been published, and improved knowledge about the three dimensional structure of PCB metabolites is urgently needed. 4-Chloro-3',4'-dihydroxybiphenyl, (I), is a major metabolite of 4-chlorobiphenyl (PCB 3) both in vivo and in vitro (McLean et al., 1996). We report here the crystal structure of this important metabolite.

The solid-state dihedral angle between the two phenyl rings of PCBs and their metabolites appears to depend on the degree of chlorination in the ortho position. According to published data, mono-ortho, di-ortho and tetra-ortho substituted PCBs show a dihedral-angle range of 49–58, 58–67 and 86–87°, respectively (summarized by Miao et al., 1997; see also Lehmler et al., 2001; Mannila & Rissanen, 1994; Singh et al., 1986). To the best of our knowledge, no crystal structures of metabolites of lower chlorinated PCBs such as 4-chlorobiphenyl have been published. The title compound shows a solid-state dihedral angle of 43.1 (3), which, as expected, is smaller than the dihedral angle of any ortho substituted PCB derivatives. The dihedral angle in aqueous solution was calculated to be 37.2°, which is close to the value observed in the solid state. The differences in the solid-state dihedral angle and the calculated angle are probably due to crystal packing effects.

Experimental top

4-Chloro-3',4'-dihydroxybiphenyl was synthesized in as described by McLean et al. (1996). Pale-yellow irregular crystals were obtained from n-hexanes/chloroform; m.p. = 415–416 K. The dihedral angle of the title compound was calculated with MM2* using GB/SA water solvent continuum as implemented by MacroModel 5.0 (Still et al., 1990).

Refinement top

Initial space group assignment as Pna21 was based upon systematic absences and intensity statistics. Space group Pnma was rejected because of the lack of a suitable solution and later by analysis of the structure. The assignment was confirmed by satisfactory solution and refinement in Pna21. There were no correlation coefficient matrix elements greater than 0.5. Nevertheless, the crystals are racemic twins, and this was accounted for using the SHELXL TWIN instruction. The hydroxyl H atoms were found in difference maps and refined using a riding model with U values set to 1.5Uiso of their corresponding O atoms.

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 Siemens SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELX97 and local programs.

Figures top
[Figure 1] Fig. 1. A view of 4-chloro-3',4'-dihydroxybiphenyl. Displacement ellipsoids are drawn at the 50% probability level.
(I) top
Crystal data top
C12H9ClO2Dx = 1.443 Mg m3
Mr = 220.64Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 4573 reflections
a = 18.358 (1) Åθ = 1.0–27.5°
b = 6.621 (2) ŵ = 0.35 mm1
c = 8.356 (3) ÅT = 144 K
V = 1015.7 (5) Å3Irregular fragment from large slab, pale yellow
Z = 40.32 × 0.18 × 0.18 mm
F(000) = 456
Data collection top
Nonius KappaCCD
diffractometer
1886 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
Graphite monochromatorθmax = 27.4°, θmin = 2.2°
Detector resolution: 18 pixels mm-1h = 2323
ω scans at fixed χ = 55°k = 88
8374 measured reflectionsl = 1010
2175 independent reflections
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)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075 w = 1/[σ2(Fo2) + (0.0296P)2 + 0.0647P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.006
2175 reflectionsΔρmax = 0.23 e Å3
137 parametersΔρmin = 0.22 e Å3
41 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.51 (6)
Crystal data top
C12H9ClO2V = 1015.7 (5) Å3
Mr = 220.64Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 18.358 (1) ŵ = 0.35 mm1
b = 6.621 (2) ÅT = 144 K
c = 8.356 (3) Å0.32 × 0.18 × 0.18 mm
Data collection top
Nonius KappaCCD
diffractometer
1886 reflections with I > 2σ(I)
8374 measured reflectionsRint = 0.038
2175 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.23 e Å3
S = 1.08Δρmin = 0.22 e Å3
2175 reflectionsAbsolute structure: Flack (1983)
137 parametersAbsolute structure parameter: 0.51 (6)
41 restraints
Special details top

Experimental. Space group assignment as non-centrosymmetric was based upon several factors including intensity distribution, E statistics, easy structure solution and refinement. Attempts at assignment of a centrosymmetric space group (Pnma) were unsuccessful. Nevertheless, the crystals are racemic twins, and this was accounted for using the SHELXL 'TWIN' instruction. There were no correlation coefficient matrix elements greater than 0.5.

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
O10.25796 (7)0.7503 (2)0.31412 (17)0.0277 (3)
H1O0.22740.86550.29300.042*
O20.24006 (6)0.9810 (2)0.05802 (16)0.0297 (3)
H2O0.23941.04920.02670.045*
Cl10.61061 (2)0.15826 (7)0.06978 (7)0.03645 (16)
C10.43988 (9)0.3339 (3)0.0469 (3)0.0231 (4)
C20.50969 (10)0.3637 (3)0.0166 (3)0.0277 (5)
H20.52110.48820.06740.033*
C30.56216 (11)0.2151 (3)0.0066 (3)0.0297 (5)
H30.60970.23840.04740.036*
C40.54492 (9)0.0323 (3)0.0633 (2)0.0267 (4)
C50.47682 (10)0.0032 (3)0.1256 (3)0.0310 (5)
H50.46540.13020.17230.037*
C60.42516 (10)0.1492 (3)0.1193 (2)0.0294 (5)
H60.37860.12690.16550.035*
C1'0.38429 (10)0.4973 (3)0.0410 (2)0.0248 (5)
C2'0.34265 (10)0.5393 (3)0.1762 (2)0.0226 (4)
H2'0.34690.45670.26870.027*
C3'0.29505 (10)0.7018 (3)0.1756 (2)0.0226 (4)
C4'0.28663 (10)0.8211 (3)0.0406 (2)0.0236 (5)
C5'0.32558 (11)0.7759 (3)0.0965 (3)0.0293 (5)
H5'0.31880.85430.19060.035*
C6'0.37483 (11)0.6151 (3)0.0966 (3)0.0284 (5)
H6'0.40200.58560.19040.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0313 (7)0.0276 (7)0.0242 (8)0.0077 (7)0.0049 (6)0.0072 (7)
O20.0329 (7)0.0302 (7)0.0261 (7)0.0061 (5)0.0011 (7)0.0121 (7)
Cl10.0342 (3)0.0339 (3)0.0413 (3)0.0088 (2)0.0030 (3)0.0040 (3)
C10.0253 (9)0.0224 (9)0.0217 (11)0.0039 (7)0.0010 (9)0.0003 (9)
C20.0311 (11)0.0249 (11)0.0272 (11)0.0055 (9)0.0040 (9)0.0010 (10)
C30.0276 (10)0.0302 (12)0.0314 (12)0.0027 (8)0.0080 (9)0.0003 (10)
C40.0266 (9)0.0282 (10)0.0252 (11)0.0019 (7)0.0035 (10)0.0055 (11)
C50.0337 (12)0.0241 (11)0.0353 (13)0.0019 (9)0.0040 (9)0.0030 (10)
C60.0248 (10)0.0300 (12)0.0333 (14)0.0049 (8)0.0037 (9)0.0002 (10)
C1'0.0256 (9)0.0246 (10)0.0243 (12)0.0045 (7)0.0026 (8)0.0012 (9)
C2'0.0263 (10)0.0213 (10)0.0202 (10)0.0034 (8)0.0009 (8)0.0048 (9)
C3'0.0210 (10)0.0267 (10)0.0202 (10)0.0035 (8)0.0011 (8)0.0021 (9)
C4'0.0228 (9)0.0241 (10)0.0238 (12)0.0017 (8)0.0019 (8)0.0060 (9)
C5'0.0354 (11)0.0312 (11)0.0211 (10)0.0013 (9)0.0012 (9)0.0062 (10)
C6'0.0342 (11)0.0312 (12)0.0197 (10)0.0018 (9)0.0031 (9)0.0046 (10)
Geometric parameters (Å, º) top
O1—C3'1.380 (2)C5—C61.386 (3)
O1—H1O0.9633C5—H50.9500
O2—C4'1.368 (2)C6—H60.9500
O2—H2O0.8400C1'—C2'1.392 (3)
Cl1—C41.7461 (18)C1'—C6'1.400 (3)
C1—C61.391 (3)C2'—C3'1.386 (3)
C1—C21.401 (3)C2'—H2'0.9500
C1—C1'1.488 (2)C3'—C4'1.386 (3)
C2—C31.379 (3)C4'—C5'1.383 (3)
C2—H20.9500C5'—C6'1.397 (3)
C3—C41.381 (3)C5'—H5'0.9500
C3—H30.9500C6'—H6'0.9500
C4—C51.375 (3)
C3'—O1—H1O108.5C1—C6—H6119.2
C4'—O2—H2O109.5C2'—C1'—C6'119.12 (17)
C6—C1—C2117.80 (16)C2'—C1'—C1119.66 (17)
C6—C1—C1'121.37 (16)C6'—C1'—C1121.18 (17)
C2—C1—C1'120.80 (16)C3'—C2'—C1'119.93 (17)
C3—C2—C1121.01 (18)C3'—C2'—H2'120.0
C3—C2—H2119.5C1'—C2'—H2'120.0
C1—C2—H2119.5O1—C3'—C2'119.27 (16)
C2—C3—C4119.40 (18)O1—C3'—C4'119.67 (16)
C2—C3—H3120.3C2'—C3'—C4'121.01 (16)
C4—C3—H3120.3O2—C4'—C5'125.32 (18)
C5—C4—C3121.24 (17)O2—C4'—C3'115.08 (17)
C5—C4—Cl1119.52 (15)C5'—C4'—C3'119.58 (17)
C3—C4—Cl1119.23 (14)C4'—C5'—C6'119.97 (19)
C4—C5—C6118.91 (18)C4'—C5'—H5'120.0
C4—C5—H5120.5C6'—C5'—H5'120.0
C6—C5—H5120.5C5'—C6'—C1'120.32 (19)
C5—C6—C1121.59 (18)C5'—C6'—H6'119.8
C5—C6—H6119.2C1'—C6'—H6'119.8
C6—C1—C2—C30.5 (3)C6'—C1'—C2'—C3'2.9 (3)
C1'—C1—C2—C3177.8 (2)C1—C1'—C2'—C3'174.73 (16)
C1—C2—C3—C41.8 (3)C1'—C2'—C3'—O1175.44 (16)
C2—C3—C4—C51.2 (3)C1'—C2'—C3'—C4'1.7 (3)
C2—C3—C4—Cl1177.91 (17)O1—C3'—C4'—O20.5 (2)
C3—C4—C5—C60.7 (3)C2'—C3'—C4'—O2177.64 (16)
Cl1—C4—C5—C6179.85 (15)O1—C3'—C4'—C5'177.99 (16)
C4—C5—C6—C12.1 (3)C2'—C3'—C4'—C5'0.9 (3)
C2—C1—C6—C51.5 (3)O2—C4'—C5'—C6'176.17 (17)
C1'—C1—C6—C5179.78 (19)C3'—C4'—C5'—C6'2.2 (3)
C6—C1—C1'—C2'43.1 (3)C4'—C5'—C6'—C1'0.9 (3)
C2—C1—C1'—C2'135.0 (2)C2'—C1'—C6'—C5'1.6 (3)
C6—C1—C1'—C6'139.3 (2)C1—C1'—C6'—C5'175.99 (17)
C2—C1—C1'—C6'42.6 (3)

Experimental details

Crystal data
Chemical formulaC12H9ClO2
Mr220.64
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)144
a, b, c (Å)18.358 (1), 6.621 (2), 8.356 (3)
V3)1015.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.32 × 0.18 × 0.18
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8374, 2175, 1886
Rint0.038
(sin θ/λ)max1)0.647
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.075, 1.08
No. of reflections2175
No. of parameters137
No. of restraints41
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.22
Absolute structureFlack (1983)
Absolute structure parameter0.51 (6)

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

 

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