2,2',5',6-Tetra­chloro-4-[(1S)-1-methyl­prop­oxy]biphen­yl

In the title mol­ecule, C₁₆H₁₄Cl₄O, the dihedral angle between the least-square planes of the benzene rings is 84.40 (7)°. No unusual intermolecular interactions are present.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.081
• Data-to-parameter ratio = 19.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT791_ALERT_4_G Note: The Model has Chirality at C7     (Verify)          S
PLAT850_ALERT_4_G Check Flack Parameter Exact Value 0.00 and su ..       0.06
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The title compound was synthesized as an intermediate in ongoing efforts to synthesize atropisomerically pure hydroxylated polychlorinated biphenyls (PCBs) for metabolism and toxicological studies (Lehmler et al., 2010; Warner et al., 2009). The dihedral angle between the two phenyl rings of the title compound, an important determinant of the toxicity of PCBs, was 84.40 (7)°. Comparable solid state dihedral (82–83°) have been reported for structurally related PCB derivatives with three ortho chlorine substituents (Lehmler et al., 2005; Rissanen et al., 1988b). Slightly larger (84–87°) dihedral angles have been observed for PCB derivatives with four ortho chlorine substituents (Pedersen, 1975; Singh & McKinney, 1979). Smaller solid state dihedral angles have been reported for PCB derivatives with zero, one or two ortho chlorine substituents due to the smaller steric demand of multiple hydrogen substituents in ortho position (Mannila & Rissanen, 1994; Miao et al., 1996; Rissanen et al., 1988a; Shaikh et al., 2008; Singh et al., 1986; van der Sluis et al., 1990; Vyas et al., 2006).

Related literature

For related literature about polychlorinated biphenyls, see: Lehmler et al. (2010); Warner et al. (2009). For crystal structures of PCB derivatives with two or less ortho chlorine substituents, see: Mannila & Rissanen (1994); Miao et al. (1996); Rissanen et al. (1988a); Shaikh et al. (2008); Singh et al. (1986); van der Sluis et al. (1990); Vyas et al. (2006). For crystal structures of PCB derivatives with three ortho chlorine substituents, see: Lehmler et al. (2005); Rissanen et al. (1988b). For crystal structures of PCB derivatives with four ortho chlorine substituents, see: Pedersen (1975); Singh & McKinney (1979). For literature about the Mitsunobu reaction, see: Fujita et al. (2001).

S2. Experimental

The title compound was synthesized by the Mitsunobu reaction of 2,2',5',6-tetrachloro-biphenyl-4-ol with (R)-isobutanol in THF (Fujita et al., 2001). Crystals suitable for crystal structure analysis were obtained by slowly evaporating a methanolic solution of the title compound.

S3. Refinement

H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained distances of 0.98 Å (RCH₃), 0.99 Å (R₂CH₂), 1.00 Å (R₃CH), 0.95 Å (C_sp2H), and with U_iso(H) values set to either 1.2U_eq or 1.5U_eq (RCH₃) of the attached atom. The absolute configuration was determined from 1625 Friedel pairs [Flack 'x' = 0.00 (6)].

Computing details

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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures

Fig. 1. View of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.

2,2',5',6-Tetrachloro-4-[(1S)-1-methylpropoxy]biphenyl

Crystal data

C16H14Cl4O	F(000) = 744
Mr = 364.07	Dx = 1.459 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2184 reflections
a = 10.3301 (2) Å	θ = 1.0–27.5°
b = 10.5415 (2) Å	µ = 0.71 mm^−1
c = 15.2160 (3) Å	T = 90 K
V = 1656.94 (6) Å^3	Plate, colourless
Z = 4	0.25 × 0.25 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer	3797 independent reflections
Radiation source: fine-focus sealed tube	3351 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 9.1 pixels mm^-1	θmax = 27.5°, θmin = 2.4°
ω scans at fixed χ = 55°	h = −13→13
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −13→13
Tmin = 0.843, Tmax = 0.946	l = −19→19
22321 measured reflections

Refinement

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)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0401P)^2 + 0.5301P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
3797 reflections	Δρmax = 0.30 e Å^−3
192 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1625 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (6)

Special details

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-value wR and goodness of fit S are based on F². Conventional R-values R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-values based on F² are statistically about twice as large as those based on F, and R-values based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.09110 (15)	0.46820 (16)	0.13102 (10)	0.0267 (4)
Cl1	0.32228 (5)	0.50012 (5)	0.42961 (3)	0.02188 (13)
Cl2	0.53731 (6)	0.28777 (6)	0.14184 (4)	0.02615 (14)
Cl3	0.44229 (6)	0.14044 (5)	0.36487 (4)	0.02755 (14)
Cl4	0.86539 (7)	0.55656 (7)	0.40389 (4)	0.03806 (18)
C1'	0.5425 (2)	0.3734 (2)	0.33248 (14)	0.0207 (5)
C1	0.4219 (2)	0.3999 (2)	0.28166 (14)	0.0188 (5)
C2	0.3142 (2)	0.4581 (2)	0.31899 (14)	0.0185 (4)
C3	0.2007 (2)	0.4834 (2)	0.27365 (14)	0.0206 (5)
H3	0.1296	0.5237	0.3018	0.025*
C4	0.1940 (2)	0.4478 (2)	0.18498 (15)	0.0215 (5)
C5	0.2990 (2)	0.3874 (2)	0.14558 (15)	0.0217 (5)
H5	0.2945	0.3625	0.0857	0.026*
C6	0.4089 (2)	0.3641 (2)	0.19355 (14)	0.0194 (5)
C7	−0.0337 (2)	0.5044 (2)	0.16686 (15)	0.0243 (5)
H7	−0.0453	0.4652	0.2262	0.029*
C8	−0.1328 (2)	0.4502 (2)	0.10372 (16)	0.0274 (5)
H8A	−0.1179	0.4871	0.0447	0.033*
H8B	−0.2203	0.4764	0.1232	0.033*
C9	−0.1291 (3)	0.3067 (3)	0.0965 (2)	0.0373 (7)
H9A	−0.0428	0.2797	0.0773	0.056*
H9B	−0.1938	0.2785	0.0536	0.056*
H9C	−0.1484	0.2691	0.1539	0.056*
C10	−0.0439 (3)	0.6479 (2)	0.17430 (17)	0.0325 (6)
H10A	0.0290	0.6802	0.2089	0.049*
H10B	−0.1254	0.6703	0.2034	0.049*
H10C	−0.0419	0.6855	0.1154	0.049*
C2'	0.5617 (2)	0.2565 (2)	0.37208 (15)	0.0235 (5)
C3'	0.6732 (3)	0.2293 (2)	0.41872 (16)	0.0303 (6)
H3'	0.6846	0.1480	0.4446	0.036*
C4'	0.7682 (3)	0.3210 (3)	0.42750 (17)	0.0315 (6)
H4'	0.8454	0.3033	0.4592	0.038*
C5'	0.7492 (2)	0.4387 (3)	0.38960 (15)	0.0265 (5)
C6'	0.6381 (2)	0.4661 (2)	0.34183 (15)	0.0232 (5)
H6'	0.6272	0.5472	0.3157	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0178 (8)	0.0421 (11)	0.0203 (8)	0.0042 (7)	−0.0031 (7)	−0.0005 (8)
Cl1	0.0234 (3)	0.0254 (3)	0.0169 (2)	0.0005 (2)	0.0008 (2)	−0.0006 (2)
Cl2	0.0243 (3)	0.0305 (3)	0.0237 (3)	0.0061 (2)	0.0010 (2)	−0.0041 (2)
Cl3	0.0366 (3)	0.0196 (3)	0.0264 (3)	−0.0011 (2)	−0.0004 (3)	0.0009 (2)
Cl4	0.0238 (3)	0.0563 (4)	0.0341 (3)	−0.0085 (3)	−0.0017 (3)	−0.0120 (3)
C1'	0.0194 (12)	0.0243 (11)	0.0182 (10)	0.0029 (10)	0.0008 (9)	−0.0018 (9)
C1	0.0194 (12)	0.0159 (10)	0.0212 (11)	0.0010 (9)	−0.0003 (9)	0.0032 (8)
C2	0.0201 (12)	0.0185 (10)	0.0168 (10)	−0.0016 (9)	0.0004 (9)	0.0018 (9)
C3	0.0198 (12)	0.0215 (12)	0.0205 (10)	0.0017 (9)	0.0020 (9)	−0.0004 (9)
C4	0.0194 (12)	0.0240 (11)	0.0209 (11)	−0.0024 (10)	−0.0016 (9)	0.0032 (10)
C5	0.0230 (12)	0.0238 (11)	0.0182 (11)	−0.0001 (9)	−0.0013 (10)	−0.0013 (9)
C6	0.0174 (11)	0.0185 (11)	0.0223 (11)	−0.0011 (9)	0.0040 (9)	0.0004 (9)
C7	0.0178 (12)	0.0292 (11)	0.0258 (11)	0.0039 (10)	−0.0020 (9)	−0.0002 (10)
C8	0.0209 (12)	0.0294 (13)	0.0319 (12)	0.0032 (11)	−0.0061 (11)	−0.0004 (11)
C9	0.0304 (14)	0.0307 (14)	0.0507 (17)	0.0060 (12)	−0.0084 (14)	−0.0089 (13)
C10	0.0313 (14)	0.0272 (13)	0.0388 (14)	0.0007 (12)	−0.0068 (12)	−0.0012 (11)
C2'	0.0278 (13)	0.0237 (11)	0.0189 (11)	0.0045 (10)	−0.0021 (10)	−0.0035 (9)
C3'	0.0382 (15)	0.0269 (13)	0.0258 (12)	0.0154 (11)	−0.0072 (11)	−0.0039 (10)
C4'	0.0281 (14)	0.0423 (16)	0.0243 (12)	0.0143 (12)	−0.0086 (11)	−0.0104 (11)
C5'	0.0168 (12)	0.0398 (14)	0.0228 (12)	−0.0010 (11)	−0.0001 (10)	−0.0090 (11)
C6'	0.0213 (12)	0.0274 (12)	0.0210 (11)	0.0013 (10)	0.0000 (9)	−0.0008 (9)

Geometric parameters (Å, º)

O1—C4	1.360 (3)	C7—C10	1.520 (3)
O1—C7	1.451 (3)	C7—H7	1.0000
Cl1—C2	1.743 (2)	C8—C9	1.518 (4)
Cl2—C6	1.739 (2)	C8—H8A	0.9900
Cl3—C2'	1.740 (3)	C8—H8B	0.9900
Cl4—C5'	1.741 (3)	C9—H9A	0.9800
C1'—C2'	1.386 (3)	C9—H9B	0.9800
C1'—C6'	1.396 (3)	C9—H9C	0.9800
C1'—C1	1.493 (3)	C10—H10A	0.9800
C1—C2	1.391 (3)	C10—H10B	0.9800
C1—C6	1.399 (3)	C10—H10C	0.9800
C2—C3	1.386 (3)	C2'—C3'	1.383 (3)
C3—C4	1.402 (3)	C3'—C4'	1.384 (4)
C3—H3	0.9500	C3'—H3'	0.9500
C4—C5	1.393 (3)	C4'—C5'	1.382 (4)
C5—C6	1.372 (3)	C4'—H4'	0.9500
C5—H5	0.9500	C5'—C6'	1.389 (3)
C7—C8	1.515 (3)	C6'—H6'	0.9500
C4—O1—C7	120.62 (17)	C7—C8—H8B	108.8
C2'—C1'—C6'	118.5 (2)	C9—C8—H8B	108.8
C2'—C1'—C1	120.7 (2)	H8A—C8—H8B	107.7
C6'—C1'—C1	120.8 (2)	C8—C9—H9A	109.5
C2—C1—C6	115.7 (2)	C8—C9—H9B	109.5
C2—C1—C1'	122.57 (19)	H9A—C9—H9B	109.5
C6—C1—C1'	121.7 (2)	C8—C9—H9C	109.5
C3—C2—C1	123.9 (2)	H9A—C9—H9C	109.5
C3—C2—Cl1	118.18 (17)	H9B—C9—H9C	109.5
C1—C2—Cl1	117.91 (17)	C7—C10—H10A	109.5
C2—C3—C4	118.0 (2)	C7—C10—H10B	109.5
C2—C3—H3	121.0	H10A—C10—H10B	109.5
C4—C3—H3	121.0	C7—C10—H10C	109.5
O1—C4—C5	114.89 (19)	H10A—C10—H10C	109.5
O1—C4—C3	125.2 (2)	H10B—C10—H10C	109.5
C5—C4—C3	119.9 (2)	C3'—C2'—C1'	121.8 (2)
C6—C5—C4	119.8 (2)	C3'—C2'—Cl3	118.48 (18)
C6—C5—H5	120.1	C1'—C2'—Cl3	119.76 (18)
C4—C5—H5	120.1	C2'—C3'—C4'	119.7 (2)
C5—C6—C1	122.7 (2)	C2'—C3'—H3'	120.2
C5—C6—Cl2	118.25 (17)	C4'—C3'—H3'	120.2
C1—C6—Cl2	119.03 (18)	C5'—C4'—C3'	119.1 (2)
O1—C7—C8	105.22 (18)	C5'—C4'—H4'	120.4
O1—C7—C10	110.6 (2)	C3'—C4'—H4'	120.4
C8—C7—C10	112.1 (2)	C4'—C5'—C6'	121.5 (2)
O1—C7—H7	109.6	C4'—C5'—Cl4	119.38 (19)
C8—C7—H7	109.6	C6'—C5'—Cl4	119.1 (2)
C10—C7—H7	109.6	C5'—C6'—C1'	119.5 (2)
C7—C8—C9	113.9 (2)	C5'—C6'—H6'	120.3
C7—C8—H8A	108.8	C1'—C6'—H6'	120.3
C9—C8—H8A	108.8
C2'—C1'—C1—C2	94.3 (3)	C2—C1—C6—Cl2	−178.73 (16)
C6'—C1'—C1—C2	−85.2 (3)	C1'—C1—C6—Cl2	−0.5 (3)
C2'—C1'—C1—C6	−83.9 (3)	C4—O1—C7—C8	−149.7 (2)
C6'—C1'—C1—C6	96.7 (3)	C4—O1—C7—C10	89.1 (3)
C6—C1—C2—C3	−1.5 (3)	O1—C7—C8—C9	61.7 (3)
C1'—C1—C2—C3	−179.7 (2)	C10—C7—C8—C9	−178.1 (2)
C6—C1—C2—Cl1	177.90 (17)	C6'—C1'—C2'—C3'	−1.2 (3)
C1'—C1—C2—Cl1	−0.4 (3)	C1—C1'—C2'—C3'	179.3 (2)
C1—C2—C3—C4	0.2 (3)	C6'—C1'—C2'—Cl3	177.88 (16)
Cl1—C2—C3—C4	−179.12 (18)	C1—C1'—C2'—Cl3	−1.6 (3)
C7—O1—C4—C5	166.6 (2)	C1'—C2'—C3'—C4'	0.9 (4)
C7—O1—C4—C3	−14.0 (3)	Cl3—C2'—C3'—C4'	−178.25 (19)
C2—C3—C4—O1	−178.5 (2)	C2'—C3'—C4'—C5'	0.3 (4)
C2—C3—C4—C5	0.8 (3)	C3'—C4'—C5'—C6'	−1.0 (4)
O1—C4—C5—C6	178.9 (2)	C3'—C4'—C5'—Cl4	177.56 (19)
C3—C4—C5—C6	−0.6 (3)	C4'—C5'—C6'—C1'	0.7 (3)
C4—C5—C6—C1	−0.8 (3)	Cl4—C5'—C6'—C1'	−177.93 (17)
C4—C5—C6—Cl2	179.69 (18)	C2'—C1'—C6'—C5'	0.4 (3)
C2—C1—C6—C5	1.7 (3)	C1—C1'—C6'—C5'	179.9 (2)
C1'—C1—C6—C5	−180.0 (2)