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The title compound, C12H3Cl6NO2, has a dihedral angle of 83.92 (8)° between the benzene rings. It was obtained as an inter­mediate in the synthesis of 3-hydr­oxy PCB 136 by nitration of PCB 136.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806001334/ac6228sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806001334/ac6228Isup2.hkl
Contains datablock I

CCDC reference: 298355

Key indicators

  • Single-crystal X-ray study
  • T = 90 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.042
  • wR factor = 0.100
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT430_ALERT_2_A Short Inter D...A Contact O1' .. O1' .. 1.98 Ang.
Author Response: The CIFCHECK program appears to have generated an alert because of close contact between a disordered oxygen atom in a minor-component (12% occupancy) nitrate group and a symmetry generated copy of itself. No such close contact exists in the actual structure, it is simply a consequence of the nature of the disorder. The _publ_section_exptl_refinement section contains a description of the disorder.
PLAT431_ALERT_2_A Short Inter HL..A Contact  Cl2'   ..  O2'     ..       2.70 Ang.
Author Response: This short contact is between a minor component (12%) of a disordered Cl atom and a symmetry-generated copy of an oxygen on a minor component (12%) nitrate group. Given the low-occupancy factor for these minor components and the fact that they are superimposed on the major components, their refined coordinates are expected to be of low accuracy. One has to be careful with restraints during least-squares refinement to maintain a chemically sensible model, and in this case, use of the normal battery of SAME, SADI etc. restraints was not quite able to keep the geometry of the minor component as similar as we would like to that of the major component. Since the minor component is so small (12%), the major component is clearly the most important. The corresponding contact for the major component counterpart of this is 2.983, which although a bit short is a much more sensible value. The nature of the disorder is described in the _publ_section_exptl_refinement section. Clearly the least-squares process has a difficult time simultaneously refining the position of 12% of a nitrate superimposed on 88% of a Cl and 12% of a Cl superimposed on 88% of a nitrate. Further refinement with tighter restraints or constraints on minor component geometry do not yield any further insights into the structure of this compound.

Alert level B PLAT432_ALERT_2_B Short Inter X...Y Contact C5 .. O2' .. 2.91 Ang.
Alert level C PLAT301_ALERT_3_C Main Residue Disorder ......................... 16.00 Perc. PLAT431_ALERT_2_C Short Inter HL..A Contact Cl2 .. O2 .. 2.98 Ang.
Author Response: This short contact is between a minor component (12%) of a disordered Cl atom and a symmetry-generated copy of an oxygen on a minor component (12%) nitrate group. Given the low-occupancy factor for these minor components and the fact that they are superimposed on the major components, their refined coordinates are expected to be of low accuracy. One has to be careful with restraints during least-squares refinement to maintain a chemically sensible model, and in this case, use of the normal battery of SAME, SADI etc. restraints was not quite able to keep the geometry of the minor component as similar as we would like to that of the major component. Since the minor component is so small (12%), the major component is clearly the most important. The corresponding contact for the major component counterpart of this is 2.983, which although a bit short is a much more sensible value. The nature of the disorder is described in the _publ_section_exptl_refinement section. Clearly the least-squares process has a difficult time simultaneously refining the position of 12% of a nitrate superimposed on 88% of a Cl and 12% of a Cl superimposed on 88% of a nitrate. Further refinement with tighter restraints or constraints on minor component geometry do not yield any further insights into the structure of this compound.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl5    ..  O1      ..       3.14 Ang.
Author Response: This short contact is between a minor component (12%) of a disordered Cl atom and a symmetry-generated copy of an oxygen on a minor component (12%) nitrate group. Given the low-occupancy factor for these minor components and the fact that they are superimposed on the major components, their refined coordinates are expected to be of low accuracy. One has to be careful with restraints during least-squares refinement to maintain a chemically sensible model, and in this case, use of the normal battery of SAME, SADI etc. restraints was not quite able to keep the geometry of the minor component as similar as we would like to that of the major component. Since the minor component is so small (12%), the major component is clearly the most important. The corresponding contact for the major component counterpart of this is 2.983, which although a bit short is a much more sensible value. The nature of the disorder is described in the _publ_section_exptl_refinement section. Clearly the least-squares process has a difficult time simultaneously refining the position of 12% of a nitrate superimposed on 88% of a Cl and 12% of a Cl superimposed on 88% of a nitrate. Further refinement with tighter restraints or constraints on minor component geometry do not yield any further insights into the structure of this compound.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl6    ..  O1'     ..       3.01 Ang.
Author Response: This short contact is between a minor component (12%) of a disordered Cl atom and a symmetry-generated copy of an oxygen on a minor component (12%) nitrate group. Given the low-occupancy factor for these minor components and the fact that they are superimposed on the major components, their refined coordinates are expected to be of low accuracy. One has to be careful with restraints during least-squares refinement to maintain a chemically sensible model, and in this case, use of the normal battery of SAME, SADI etc. restraints was not quite able to keep the geometry of the minor component as similar as we would like to that of the major component. Since the minor component is so small (12%), the major component is clearly the most important. The corresponding contact for the major component counterpart of this is 2.983, which although a bit short is a much more sensible value. The nature of the disorder is described in the _publ_section_exptl_refinement section. Clearly the least-squares process has a difficult time simultaneously refining the position of 12% of a nitrate superimposed on 88% of a Cl and 12% of a Cl superimposed on 88% of a nitrate. Further refinement with tighter restraints or constraints on minor component geometry do not yield any further insights into the structure of this compound.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2'   ..  O2'     ..       3.11 Ang.
Author Response: This short contact is between a minor component (12%) of a disordered Cl atom and a symmetry-generated copy of an oxygen on a minor component (12%) nitrate group. Given the low-occupancy factor for these minor components and the fact that they are superimposed on the major components, their refined coordinates are expected to be of low accuracy. One has to be careful with restraints during least-squares refinement to maintain a chemically sensible model, and in this case, use of the normal battery of SAME, SADI etc. restraints was not quite able to keep the geometry of the minor component as similar as we would like to that of the major component. Since the minor component is so small (12%), the major component is clearly the most important. The corresponding contact for the major component counterpart of this is 2.983, which although a bit short is a much more sensible value. The nature of the disorder is described in the _publ_section_exptl_refinement section. Clearly the least-squares process has a difficult time simultaneously refining the position of 12% of a nitrate superimposed on 88% of a Cl and 12% of a Cl superimposed on 88% of a nitrate. Further refinement with tighter restraints or constraints on minor component geometry do not yield any further insights into the structure of this compound.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C4     ..  O1'     ..       2.93 Ang.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       2.00 Deg.
              N1'  -C3   -CL2     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       9.20 Deg.
              N1   -C5   -CL2'    1.555   1.555   1.555

2 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 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 0 ALERT type 4 Improvement, methodology, query or suggestion

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 (Sheldrick, 1994); software used to prepare material for publication: SHELX97-2 (Sheldrick, 1997) and local procedures.

2,2',3,3',6,6'-Hexachloro-5-nitro-1,1'-biphenyl top
Crystal data top
C12H3Cl6NO2F(000) = 800
Mr = 405.85Dx = 1.879 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3326 reflections
a = 12.1073 (2) Åθ = 1.0–27.5°
b = 16.3810 (5) ŵ = 1.20 mm1
c = 7.5813 (4) ÅT = 90 K
β = 107.4219 (14)°Block cut from rod, yellow
V = 1434.62 (9) Å30.25 × 0.20 × 0.20 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
3280 independent reflections
Radiation source: fine-focus sealed tube2544 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 18 pixels mm-1θmax = 27.5°, θmin = 1.8°
ω scans at fixed χ = 55°h = 1515
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 2121
Tmin = 0.742, Tmax = 0.796l = 99
5940 measured reflections
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0381P)2 + 1.8622P]
where P = (Fo2 + 2Fc2)/3
3280 reflections(Δ/σ)max = 0.002
207 parametersΔρmax = 0.65 e Å3
20 restraintsΔρmin = 0.41 e Å3
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.

The ring with the NO2 substituent is disordered. This was modelled with major and minor components for the Cl and the NO2. Some resraints were used to maintain the geometry of the disordered parts.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.32816 (6)0.04170 (4)0.50062 (9)0.02591 (18)
Cl20.0854 (2)0.07297 (11)0.2114 (2)0.0259 (4)0.880 (4)
N1'0.084 (6)0.0615 (8)0.231 (3)0.026 (17)*0.120 (4)
O1'0.0407 (15)0.0472 (10)0.072 (2)0.028 (5)*0.120 (4)
O2'0.1057 (16)0.1253 (10)0.315 (2)0.032 (5)*0.120 (4)
Cl30.17149 (7)0.23375 (5)0.72135 (10)0.03124 (19)
Cl40.43141 (6)0.17323 (5)0.49570 (9)0.02545 (18)
Cl50.66240 (6)0.19969 (5)0.82349 (10)0.02769 (18)
Cl60.23880 (6)0.03511 (5)0.97899 (9)0.02959 (19)
N10.0637 (4)0.1921 (3)0.4076 (8)0.0272 (12)0.880 (4)
O10.1546 (2)0.1641 (2)0.3258 (5)0.0582 (10)0.880 (4)
O20.0451 (2)0.2622 (2)0.4636 (5)0.0490 (9)0.880 (4)
Cl2'0.0639 (11)0.2133 (7)0.410 (2)0.025 (3)*0.120 (4)
C10.2343 (2)0.09375 (17)0.5985 (4)0.0189 (6)
C20.2167 (2)0.02602 (17)0.4817 (3)0.0191 (6)
C30.1100 (2)0.01338 (17)0.3488 (4)0.0198 (6)
C40.0220 (2)0.06932 (18)0.3288 (4)0.0215 (6)
H40.05050.06100.23780.026*
C50.0392 (2)0.13725 (18)0.4410 (4)0.0209 (6)
C60.1448 (2)0.15058 (17)0.5764 (4)0.0197 (6)
C1'0.3459 (2)0.10483 (16)0.7497 (4)0.0189 (6)
C2'0.4419 (2)0.14049 (17)0.7173 (4)0.0200 (6)
C3'0.5445 (2)0.15131 (17)0.8597 (4)0.0220 (6)
C4'0.5523 (2)0.12411 (18)1.0359 (4)0.0230 (6)
H4'0.62270.13031.13280.028*
C5'0.4582 (2)0.08809 (18)1.0717 (4)0.0232 (6)
H5'0.46360.06951.19260.028*
C6'0.3556 (2)0.07930 (18)0.9293 (4)0.0212 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0222 (4)0.0262 (4)0.0250 (3)0.0058 (3)0.0005 (3)0.0037 (3)
Cl20.0232 (7)0.0271 (6)0.0254 (6)0.0056 (5)0.0042 (5)0.0053 (5)
Cl30.0256 (4)0.0321 (4)0.0321 (4)0.0059 (3)0.0027 (3)0.0111 (3)
Cl40.0214 (4)0.0321 (4)0.0220 (3)0.0025 (3)0.0052 (3)0.0045 (3)
Cl50.0170 (4)0.0309 (4)0.0335 (4)0.0041 (3)0.0051 (3)0.0004 (3)
Cl60.0231 (4)0.0439 (5)0.0211 (3)0.0090 (3)0.0057 (3)0.0017 (3)
N10.020 (2)0.024 (3)0.035 (2)0.0032 (19)0.0040 (13)0.000 (2)
O10.0174 (15)0.063 (2)0.081 (2)0.0083 (14)0.0059 (14)0.0288 (18)
O20.0272 (16)0.0280 (18)0.080 (2)0.0077 (12)0.0015 (14)0.0067 (17)
C10.0147 (14)0.0235 (15)0.0189 (12)0.0036 (11)0.0056 (10)0.0017 (11)
C20.0164 (14)0.0228 (15)0.0174 (12)0.0002 (11)0.0042 (10)0.0028 (11)
C30.0201 (14)0.0220 (14)0.0178 (12)0.0055 (12)0.0066 (11)0.0020 (11)
C40.0129 (14)0.0308 (16)0.0191 (13)0.0033 (12)0.0021 (10)0.0022 (12)
C50.0144 (14)0.0260 (15)0.0214 (13)0.0034 (11)0.0040 (11)0.0036 (12)
C60.0177 (14)0.0231 (15)0.0190 (13)0.0026 (11)0.0068 (11)0.0003 (11)
C1'0.0167 (14)0.0190 (14)0.0193 (13)0.0025 (11)0.0026 (11)0.0035 (11)
C2'0.0208 (14)0.0195 (14)0.0193 (13)0.0030 (11)0.0054 (11)0.0004 (11)
C3'0.0178 (14)0.0202 (15)0.0273 (14)0.0014 (11)0.0057 (11)0.0035 (12)
C4'0.0175 (14)0.0237 (15)0.0232 (14)0.0023 (11)0.0010 (11)0.0012 (11)
C5'0.0216 (15)0.0260 (16)0.0192 (13)0.0006 (12)0.0020 (11)0.0001 (11)
C6'0.0180 (14)0.0222 (15)0.0225 (13)0.0007 (11)0.0048 (11)0.0000 (11)
Geometric parameters (Å, º) top
Cl1—C21.719 (3)C1—C1'1.498 (4)
Cl2—C31.729 (3)C2—C31.395 (4)
N1'—O1'1.182 (18)C3—C41.379 (4)
N1'—O2'1.211 (18)C4—C51.378 (4)
N1'—C31.494 (6)C4—H40.9500
Cl3—C61.719 (3)C5—C61.397 (4)
Cl4—C2'1.731 (3)C1'—C2'1.388 (4)
Cl5—C3'1.724 (3)C1'—C6'1.395 (4)
Cl6—C6'1.727 (3)C2'—C3'1.392 (4)
N1—O11.183 (6)C3'—C4'1.385 (4)
N1—O21.222 (7)C4'—C5'1.380 (4)
N1—C51.494 (6)C4'—H4'0.9500
Cl2'—C51.729 (3)C5'—C6'1.388 (4)
C1—C21.396 (4)C5'—H5'0.9500
C1—C61.400 (4)
O1'—N1'—O2'131.9 (14)C4—C5—Cl2'121.9 (6)
O1'—N1'—C3113.3 (15)C6—C5—Cl2'116.9 (6)
O2'—N1'—C3114.8 (16)N1—C5—Cl2'9.2 (7)
O1—N1—O2126.3 (5)C5—C6—C1119.3 (2)
O1—N1—C5117.0 (5)C5—C6—Cl3123.3 (2)
O2—N1—C5116.7 (4)C1—C6—Cl3117.4 (2)
C2—C1—C6119.1 (2)C2'—C1'—C6'118.0 (2)
C2—C1—C1'120.9 (2)C2'—C1'—C1121.8 (2)
C6—C1—C1'119.9 (2)C6'—C1'—C1120.3 (2)
C3—C2—C1120.6 (2)C1'—C2'—C3'121.1 (2)
C3—C2—Cl1119.9 (2)C1'—C2'—Cl4118.7 (2)
C1—C2—Cl1119.5 (2)C3'—C2'—Cl4120.2 (2)
C4—C3—C2119.9 (2)C4'—C3'—C2'119.6 (3)
C4—C3—N1'117 (2)C4'—C3'—Cl5118.8 (2)
C2—C3—N1'123 (2)C2'—C3'—Cl5121.6 (2)
C4—C3—Cl2119.3 (2)C5'—C4'—C3'120.4 (3)
C2—C3—Cl2120.8 (2)C5'—C4'—H4'119.8
N1'—C3—Cl22 (3)C3'—C4'—H4'119.8
C5—C4—C3120.0 (2)C4'—C5'—C6'119.4 (3)
C5—C4—H4120.0C4'—C5'—H5'120.3
C3—C4—H4120.0C6'—C5'—H5'120.3
C4—C5—C6121.1 (3)C5'—C6'—C1'121.5 (3)
C4—C5—N1114.6 (3)C5'—C6'—Cl6118.3 (2)
C6—C5—N1124.3 (3)C1'—C6'—Cl6120.2 (2)
C6—C1—C2—C32.3 (4)N1—C5—C6—Cl31.3 (5)
C1'—C1—C2—C3175.9 (2)Cl2'—C5—C6—Cl35.0 (6)
C6—C1—C2—Cl1177.1 (2)C2—C1—C6—C51.5 (4)
C1'—C1—C2—Cl14.8 (4)C1'—C1—C6—C5176.7 (2)
C1—C2—C3—C41.8 (4)C2—C1—C6—Cl3179.1 (2)
Cl1—C2—C3—C4177.5 (2)C1'—C1—C6—Cl32.8 (3)
C1—C2—C3—N1'175 (2)C2—C1—C1'—C2'84.4 (4)
Cl1—C2—C3—N1'6 (2)C6—C1—C1'—C2'97.5 (3)
C1—C2—C3—Cl2176.8 (2)C2—C1—C1'—C6'95.8 (3)
Cl1—C2—C3—Cl23.9 (3)C6—C1—C1'—C6'82.4 (3)
O1'—N1'—C3—C451 (6)C6'—C1'—C2'—C3'0.7 (4)
O2'—N1'—C3—C4127 (4)C1—C1'—C2'—C3'179.2 (3)
O1'—N1'—C3—C2132 (4)C6'—C1'—C2'—Cl4179.6 (2)
O2'—N1'—C3—C250 (6)C1—C1'—C2'—Cl40.3 (4)
C2—C3—C4—C50.5 (4)C1'—C2'—C3'—C4'1.8 (4)
N1'—C3—C4—C5176 (2)Cl4—C2'—C3'—C4'179.4 (2)
Cl2—C3—C4—C5178.1 (2)C1'—C2'—C3'—Cl5177.0 (2)
C3—C4—C5—C60.3 (4)Cl4—C2'—C3'—Cl51.9 (3)
C3—C4—C5—N1178.9 (3)C2'—C3'—C4'—C5'1.4 (4)
C3—C4—C5—Cl2'174.8 (6)Cl5—C3'—C4'—C5'177.4 (2)
O1—N1—C5—C417.9 (6)C3'—C4'—C5'—C6'0.0 (4)
O2—N1—C5—C4160.2 (4)C4'—C5'—C6'—C1'1.1 (4)
O1—N1—C5—C6160.6 (4)C4'—C5'—C6'—Cl6179.2 (2)
O2—N1—C5—C621.3 (7)C2'—C1'—C6'—C5'0.8 (4)
C4—C5—C6—C10.2 (4)C1—C1'—C6'—C5'179.4 (3)
N1—C5—C6—C1178.2 (3)C2'—C1'—C6'—Cl6179.6 (2)
Cl2'—C5—C6—C1175.5 (6)C1—C1'—C6'—Cl60.3 (4)
C4—C5—C6—Cl3179.7 (2)
 

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