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Three flame retardants with very similar molecular structures showing three different packing patterns have been studied. The crystal structure of 2,2',6,6'-tetrachloro-4,4'-propane-2,2-diyldiphenol, C
15H
12Cl
4O
2, can be described as a packing of sheets. The packing shows a very short intermolecular Cl
Cl contact distance of 3.094 (2) Å between pairs of molecules inside each sheet. The crystal structure of 2,2',6-tribromo-4,4'-propane-2,2-diyldiphenol, C
15H
13Br
3O
2, can be described as a packing of doubly stranded helical square tubes. These square helices are interconnected through Br
Br contacts between different helices. Finally, a previously known structure, 2,2',6,6'-tetrabromo-4,4'-propane-2,2-diyldiphenol [Simonov, Cheban, Rotaru & Bels'skii (1986).
Kristallografiya,
31, 397-399], C
15H
12Br
4O
2, which is the most commonly used flame retardant and which has twofold rotational symmetry, has been refined in the correct absolute configuration. The structure shows large differences from the chloro analogue with regard to packing, van der Waals distances and hydrogen-bond distances.
Supporting information
CCDC references: 175084; 175085; 175086
All compounds were re-crystallized from ethanol at ambient temperature. Original
source?
For (I), the H atoms were placed geometrically. The hydroxyl groups were allowed
to rotate freely around the C—O bond, using the AFIX83 instruction in
SHELXL97 (Sheldrick, 1997). The hydroxyl H atoms converged to a
position that could be interpreted as a favourable conformation for the
formation of a hydrogen-bonded chain of molecules. For (II), the spacegroup
was determined from reflection conditions, indicating the unique space group
Fdd2 (43). The Flack parameter (Flack, 1983) was refined as a scale factor of
this model and of the inverted model. The refined value of the Flack parameter
in this model was 0.49 (2); thus, a merging of Friedel-related reflections was
done for the final model. The total number of 2936 reflections gave 1559
unique reflections plus 1377 Friedel-related equivalents. The merging of
reflection data improved wR2 and R1 without affecting s.u.s by more than
approximately 10%. All coordinates and derived distances etc. were
equal to within 1 s.u. of the corresponding quantities. The highest residual
electron-density peak (1.50 e Å-3) was located at (0.0814, 0.0417,
0.4149), 1.16 Å from H8, and should not be interpreted as an additional
atom. Compound (II) is a strong absorber of Mo Kα radiation. Thus a possible
cause for the residual peak is an imperfect absorption correction. The applied
absorption correction decreased the internal R value from 0.25 to 0.06,
but the remaining absorption effects could be an explanation of the positive
ghost peak. However, the residual peak can also be interpreted as a ripple in
the residual density map. For (III), the high internal R value is, to a
large extent, dependent on the weak scattering from the crystal. Thus
Rint is dominated by a large fraction of weak reflections. Of 1625
unique reflections in total, only 539 fulfil the criterion I ≥ 3σ(I). The
internal R value calculated from these 539 reflections is 0.0634; the
corresponding wR2 = 0.0464 and R1 = 0.0419, thus indicating insignificant
differences to the refinement with all reflections present. The applied
absorption correction did not affect the internal R value as much, but
wR2 and R1 were significantly lowered, as expected. The total number of
reflections (1625) was composed of 990 unique reflections and 635 Friedel
equivalents. The Friedel equivalents were not averaged, as the four Br atoms
of each molecule give a considerable contribution to anomalous dispersion
effects and no signs of twinning were detectable. The present model was
refined in P43212 (96), instead of the inverse spacegroup P41212 (92)
previously used by Simonov et al. (1986). The Flack parameter clearly
indicates that P43212 (96) is the correct space group. This change of
absolute configuration eliminates some of the anomalous bonding distances
previously reported by Simonov et al. (1986). For all three compounds,
C—H distances were constrained to 0.93–0.96 Å, O—H distances to 0.82 Å and Uiso(H) to 1.2 or 1.5 times Ueq of the parent atom.
Query.
Data collection: DIF4 (Stoe, 1988) for (I); EXPOSE (Stoe, 1997) for (II), (III). Cell refinement: DIF4 for (I); CELL (Stoe, 1997) for (II), (III). Data reduction: REDU4 (Stoe, 1988) for (I); INTEGRATE (Stoe, 1997) for (II), (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996).
(I) 3,5,3',5'-Tetrachloro-4,4'-dihydroxy-diphenyl-dimethl-methane
top
Crystal data top
C15H12Cl4O2 | F(000) = 1488 |
Mr = 366.05 | Dx = 1.550 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 56 reflections |
a = 25.675 (9) Å | θ = 7.5–10.7° |
b = 11.602 (3) Å | µ = 0.75 mm−1 |
c = 10.530 (4) Å | T = 293 K |
V = 3136.6 (17) Å3 | Prism, light yellow |
Z = 8 | 0.23 × 0.16 × 0.13 mm |
Data collection top
Stoe AED2 diffractometer | 1267 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 25.0°, θmin = 1.6° |
θ/2θ scans | h = −1→30 |
Absorption correction: numerical (X-RED; Stoe, 1997) | k = −1→13 |
Tmin = 0.843, Tmax = 0.906 | l = −1→12 |
3572 measured reflections | 4 standard reflections every 90 min |
2771 independent reflections | intensity decay: <1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.01P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2771 reflections | Δρmax = 0.28 e Å−3 |
191 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00102 (11) |
Crystal data top
C15H12Cl4O2 | V = 3136.6 (17) Å3 |
Mr = 366.05 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 25.675 (9) Å | µ = 0.75 mm−1 |
b = 11.602 (3) Å | T = 293 K |
c = 10.530 (4) Å | 0.23 × 0.16 × 0.13 mm |
Data collection top
Stoe AED2 diffractometer | 1267 reflections with I > 2σ(I) |
Absorption correction: numerical (X-RED; Stoe, 1997) | Rint = 0.061 |
Tmin = 0.843, Tmax = 0.906 | 4 standard reflections every 90 min |
3572 measured reflections | intensity decay: <1% |
2771 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.28 e Å−3 |
2771 reflections | Δρmin = −0.32 e Å−3 |
191 parameters | |
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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.53872 (4) | −0.02927 (10) | 0.10785 (10) | 0.0478 (3) | |
Cl2 | 0.63226 (4) | −0.27957 (9) | 0.47048 (12) | 0.0512 (3) | |
Cl3 | 0.50709 (4) | 0.35165 (10) | 0.44769 (13) | 0.0644 (4) | |
Cl4 | 0.65296 (4) | 0.54535 (10) | 0.15129 (12) | 0.0560 (4) | |
O1 | 0.55563 (9) | −0.23293 (19) | 0.2637 (3) | 0.0468 (9) | |
H1 | 0.5623 | −0.2884 | 0.3091 | 0.070* | |
O2 | 0.55271 (10) | 0.5328 (2) | 0.2787 (3) | 0.0530 (9) | |
H2 | 0.5247 | 0.5242 | 0.3150 | 0.080* | |
C1 | 0.68558 (14) | 0.1512 (4) | 0.3862 (4) | 0.0319 (11) | |
C2 | 0.73417 (14) | 0.1468 (4) | 0.3003 (4) | 0.0536 (14) | |
H2A | 0.7538 | 0.0784 | 0.3188 | 0.080* | |
H2B | 0.7554 | 0.2134 | 0.3158 | 0.080* | |
H2C | 0.7236 | 0.1458 | 0.2129 | 0.080* | |
C3 | 0.70328 (15) | 0.1513 (4) | 0.5260 (4) | 0.0498 (13) | |
H3A | 0.7239 | 0.0839 | 0.5423 | 0.075* | |
H3B | 0.6733 | 0.1510 | 0.5804 | 0.075* | |
H3C | 0.7237 | 0.2190 | 0.5424 | 0.075* | |
C4 | 0.65264 (14) | 0.0458 (3) | 0.3535 (4) | 0.0269 (9) | |
C5 | 0.65745 (14) | −0.0588 (3) | 0.4160 (4) | 0.0315 (11) | |
H5 | 0.6822 | −0.0663 | 0.4798 | 0.038* | |
C6 | 0.62650 (14) | −0.1521 (3) | 0.3860 (4) | 0.0305 (10) | |
C7 | 0.58851 (14) | −0.1448 (3) | 0.2918 (4) | 0.0324 (11) | |
C8 | 0.58480 (13) | −0.0415 (3) | 0.2275 (3) | 0.0291 (10) | |
C9 | 0.61605 (13) | 0.0506 (3) | 0.2552 (4) | 0.0311 (10) | |
H9 | 0.6129 | 0.1178 | 0.2077 | 0.037* | |
C10 | 0.65273 (15) | 0.2592 (3) | 0.3609 (4) | 0.0273 (10) | |
C11 | 0.66843 (14) | 0.3491 (3) | 0.2842 (4) | 0.0348 (11) | |
H11 | 0.7018 | 0.3491 | 0.2498 | 0.042* | |
C12 | 0.63489 (16) | 0.4391 (3) | 0.2581 (4) | 0.0351 (10) | |
C13 | 0.58500 (16) | 0.4435 (3) | 0.3084 (4) | 0.0383 (12) | |
C14 | 0.57022 (14) | 0.3537 (4) | 0.3886 (4) | 0.0384 (12) | |
C15 | 0.60333 (15) | 0.2652 (3) | 0.4148 (4) | 0.0336 (11) | |
H15 | 0.5927 | 0.2073 | 0.4700 | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0507 (7) | 0.0459 (6) | 0.0469 (7) | 0.0012 (6) | −0.0230 (6) | 0.0019 (7) |
Cl2 | 0.0589 (7) | 0.0346 (6) | 0.0601 (8) | −0.0002 (6) | −0.0110 (7) | 0.0171 (7) |
Cl3 | 0.0478 (7) | 0.0542 (7) | 0.0913 (11) | 0.0121 (7) | 0.0256 (8) | 0.0075 (9) |
Cl4 | 0.0557 (7) | 0.0460 (7) | 0.0662 (8) | −0.0114 (7) | −0.0090 (7) | 0.0228 (7) |
O1 | 0.0474 (17) | 0.0246 (14) | 0.068 (2) | −0.0036 (15) | −0.0077 (19) | 0.0030 (18) |
O2 | 0.0372 (17) | 0.0332 (15) | 0.089 (3) | 0.0030 (16) | −0.0101 (18) | 0.001 (2) |
C1 | 0.032 (2) | 0.029 (2) | 0.034 (3) | 0.002 (2) | −0.004 (2) | 0.000 (3) |
C2 | 0.036 (3) | 0.044 (3) | 0.081 (4) | 0.002 (3) | 0.007 (3) | 0.004 (3) |
C3 | 0.053 (3) | 0.039 (3) | 0.058 (3) | −0.010 (3) | −0.023 (3) | −0.002 (3) |
C4 | 0.027 (2) | 0.024 (2) | 0.029 (2) | 0.005 (2) | 0.003 (2) | 0.000 (2) |
C5 | 0.028 (2) | 0.037 (3) | 0.029 (3) | 0.006 (2) | −0.009 (2) | 0.004 (2) |
C6 | 0.034 (2) | 0.026 (2) | 0.032 (3) | 0.003 (2) | −0.003 (2) | 0.008 (2) |
C7 | 0.033 (2) | 0.025 (2) | 0.040 (3) | −0.001 (2) | −0.002 (2) | −0.006 (2) |
C8 | 0.033 (2) | 0.030 (2) | 0.025 (2) | 0.007 (2) | −0.006 (2) | 0.002 (2) |
C9 | 0.036 (2) | 0.026 (2) | 0.031 (2) | 0.002 (2) | 0.004 (2) | 0.003 (2) |
C10 | 0.028 (2) | 0.026 (2) | 0.028 (3) | −0.003 (2) | −0.006 (2) | −0.002 (2) |
C11 | 0.029 (2) | 0.033 (2) | 0.042 (3) | −0.008 (2) | 0.000 (2) | −0.003 (3) |
C12 | 0.042 (3) | 0.024 (2) | 0.040 (3) | −0.006 (2) | −0.007 (2) | 0.004 (2) |
C13 | 0.038 (3) | 0.027 (2) | 0.049 (3) | 0.000 (2) | −0.016 (2) | −0.004 (3) |
C14 | 0.038 (2) | 0.028 (2) | 0.050 (3) | −0.001 (2) | 0.007 (2) | −0.002 (3) |
C15 | 0.044 (3) | 0.025 (2) | 0.031 (3) | −0.002 (2) | 0.001 (2) | −0.001 (2) |
Geometric parameters (Å, º) top
Cl1—C8 | 1.734 (4) | C3—H3C | 0.9600 |
Cl2—C6 | 1.732 (4) | C4—C5 | 1.386 (5) |
Cl3—C14 | 1.736 (4) | C4—C9 | 1.399 (5) |
Cl4—C12 | 1.732 (4) | C5—C6 | 1.380 (5) |
O1—C7 | 1.359 (4) | C5—H5 | 0.9300 |
O1—H1 | 0.8200 | C6—C7 | 1.394 (5) |
O2—C13 | 1.363 (4) | C7—C8 | 1.379 (5) |
O2—H2 | 0.8200 | C8—C9 | 1.368 (5) |
C1—C4 | 1.526 (5) | C9—H9 | 0.9300 |
C1—C10 | 1.533 (5) | C10—C11 | 1.380 (5) |
C1—C3 | 1.540 (6) | C10—C15 | 1.391 (5) |
C1—C2 | 1.542 (5) | C11—C12 | 1.381 (5) |
C2—H2A | 0.9600 | C11—H11 | 0.9300 |
C2—H2B | 0.9600 | C12—C13 | 1.387 (5) |
C2—H2C | 0.9600 | C13—C14 | 1.394 (5) |
C3—H3A | 0.9600 | C14—C15 | 1.361 (5) |
C3—H3B | 0.9600 | C15—H15 | 0.9300 |
| | | |
C7—O1—H1 | 109.5 | C7—C6—Cl2 | 118.5 (3) |
C13—O2—H2 | 109.5 | O1—C7—C8 | 120.3 (4) |
C4—C1—C10 | 108.1 (3) | O1—C7—C6 | 123.0 (4) |
C4—C1—C3 | 112.3 (4) | C8—C7—C6 | 116.8 (4) |
C10—C1—C3 | 109.2 (3) | C9—C8—C7 | 122.2 (3) |
C4—C1—C2 | 106.8 (3) | C9—C8—Cl1 | 119.4 (3) |
C10—C1—C2 | 111.7 (3) | C7—C8—Cl1 | 118.3 (3) |
C3—C1—C2 | 108.8 (3) | C8—C9—C4 | 121.4 (4) |
C1—C2—H2A | 109.5 | C8—C9—H9 | 119.3 |
C1—C2—H2B | 109.5 | C4—C9—H9 | 119.3 |
H2A—C2—H2B | 109.5 | C11—C10—C15 | 117.9 (4) |
C1—C2—H2C | 109.5 | C11—C10—C1 | 124.0 (4) |
H2A—C2—H2C | 109.5 | C15—C10—C1 | 118.1 (3) |
H2B—C2—H2C | 109.5 | C10—C11—C12 | 120.4 (4) |
C1—C3—H3A | 109.5 | C10—C11—H11 | 119.8 |
C1—C3—H3B | 109.5 | C12—C11—H11 | 119.8 |
H3A—C3—H3B | 109.5 | C11—C12—C13 | 121.9 (4) |
C1—C3—H3C | 109.5 | C11—C12—Cl4 | 120.0 (3) |
H3A—C3—H3C | 109.5 | C13—C12—Cl4 | 118.0 (3) |
H3B—C3—H3C | 109.5 | O2—C13—C12 | 120.1 (4) |
C5—C4—C9 | 116.4 (4) | O2—C13—C14 | 122.8 (4) |
C5—C4—C1 | 123.0 (3) | C12—C13—C14 | 117.1 (4) |
C9—C4—C1 | 120.5 (3) | C15—C14—C13 | 121.1 (4) |
C6—C5—C4 | 121.8 (4) | C15—C14—Cl3 | 120.0 (3) |
C6—C5—H5 | 119.1 | C13—C14—Cl3 | 118.8 (3) |
C4—C5—H5 | 119.1 | C14—C15—C10 | 121.6 (4) |
C5—C6—C7 | 121.2 (4) | C14—C15—H15 | 119.2 |
C5—C6—Cl2 | 120.2 (3) | C10—C15—H15 | 119.2 |
| | | |
C10—C1—C4—C5 | −148.3 (4) | C4—C1—C10—C11 | −125.9 (4) |
C3—C1—C4—C5 | −27.8 (5) | C3—C1—C10—C11 | 111.7 (4) |
C2—C1—C4—C5 | 91.4 (5) | C2—C1—C10—C11 | −8.7 (5) |
C10—C1—C4—C9 | 32.9 (5) | C4—C1—C10—C15 | 51.7 (4) |
C3—C1—C4—C9 | 153.3 (4) | C3—C1—C10—C15 | −70.7 (4) |
C2—C1—C4—C9 | −87.5 (4) | C2—C1—C10—C15 | 168.9 (4) |
C9—C4—C5—C6 | −2.3 (6) | C15—C10—C11—C12 | −2.8 (6) |
C1—C4—C5—C6 | 178.8 (3) | C1—C10—C11—C12 | 174.8 (4) |
C4—C5—C6—C7 | −0.6 (6) | C10—C11—C12—C13 | 0.8 (6) |
C4—C5—C6—Cl2 | −177.6 (3) | C10—C11—C12—Cl4 | −174.6 (3) |
C5—C6—C7—O1 | −176.8 (4) | C11—C12—C13—O2 | −178.9 (3) |
Cl2—C6—C7—O1 | 0.3 (5) | Cl4—C12—C13—O2 | −3.5 (5) |
C5—C6—C7—C8 | 2.3 (6) | C11—C12—C13—C14 | 1.1 (6) |
Cl2—C6—C7—C8 | 179.4 (3) | Cl4—C12—C13—C14 | 176.5 (3) |
O1—C7—C8—C9 | 178.0 (3) | O2—C13—C14—C15 | 179.2 (4) |
C6—C7—C8—C9 | −1.0 (6) | C12—C13—C14—C15 | −0.8 (6) |
O1—C7—C8—Cl1 | −1.9 (5) | O2—C13—C14—Cl3 | 3.1 (6) |
C6—C7—C8—Cl1 | 179.0 (3) | C12—C13—C14—Cl3 | −176.9 (3) |
C7—C8—C9—C4 | −1.9 (6) | C13—C14—C15—C10 | −1.3 (6) |
Cl1—C8—C9—C4 | 178.0 (3) | Cl3—C14—C15—C10 | 174.7 (3) |
C5—C4—C9—C8 | 3.5 (5) | C11—C10—C15—C14 | 3.1 (6) |
C1—C4—C9—C8 | −177.5 (4) | C1—C10—C15—C14 | −174.7 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.11 | 2.723 (3) | 131 |
O2—H2···O2ii | 0.82 | 2.22 | 2.773 (5) | 125 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y, −z+1/2. |
(II) 3,3',5'-Tribromo-4,4'-dihydroxy-diphenyl-dimethyl-methane
top
Crystal data top
C15H13Br3O2 | F(000) = 3584 |
Mr = 464.98 | Dx = 2.034 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 1230 reflections |
a = 19.545 (3) Å | θ = 1.7–26.1° |
b = 30.971 (4) Å | µ = 7.97 mm−1 |
c = 10.0335 (19) Å | T = 293 K |
V = 6073.6 (16) Å3 | Prism, colourless |
Z = 16 | 0.31 × 0.27 × 0.22 mm |
Data collection top
Stoe IPDS area-detector diffractometer | 1559 independent reflections |
Radiation source: fine-focus sealed tube | 1500 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 6.0 pixels mm-1 | θmax = 25.9°, θmin = 2.4° |
area detector scans | h = −23→23 |
Absorption correction: numerical (X-RED; Stoe, 1997) | k = −36→37 |
Tmin = 0.086, Tmax = 0.167 | l = −12→12 |
10060 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
1559 reflections | (Δ/σ)max = 0.001 |
185 parameters | Δρmax = 1.50 e Å−3 |
1 restraint | Δρmin = −0.41 e Å−3 |
Crystal data top
C15H13Br3O2 | V = 6073.6 (16) Å3 |
Mr = 464.98 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 19.545 (3) Å | µ = 7.97 mm−1 |
b = 30.971 (4) Å | T = 293 K |
c = 10.0335 (19) Å | 0.31 × 0.27 × 0.22 mm |
Data collection top
Stoe IPDS area-detector diffractometer | 1559 independent reflections |
Absorption correction: numerical (X-RED; Stoe, 1997) | 1500 reflections with I > 2σ(I) |
Tmin = 0.086, Tmax = 0.167 | Rint = 0.066 |
10060 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 1 restraint |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.16 | Δρmax = 1.50 e Å−3 |
1559 reflections | Δρmin = −0.41 e Å−3 |
185 parameters | |
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 | x | y | z | Uiso*/Ueq | |
Br1 | 0.04130 (3) | 0.251655 (17) | 0.20723 (6) | 0.01990 (14) | |
Br2 | 0.36051 (3) | 0.238662 (17) | −0.14632 (5) | 0.02046 (14) | |
Br3 | 0.26465 (4) | 0.400527 (18) | −0.32651 (5) | 0.02824 (16) | |
O1 | 0.3320 (2) | 0.31433 (13) | −0.3416 (4) | 0.0237 (9) | |
H1 | 0.3586 | 0.2938 | −0.3424 | 0.036* | |
O2 | 0.0917 (2) | 0.24357 (14) | 0.5008 (4) | 0.0245 (9) | |
H2 | 0.0524 | 0.2436 | 0.4722 | 0.037* | |
C1 | 0.2617 (3) | 0.35635 (16) | 0.1956 (5) | 0.0138 (11) | |
C2 | 0.2242 (3) | 0.39992 (16) | 0.2086 (6) | 0.0178 (12) | |
H2A | 0.1791 | 0.3975 | 0.1714 | 0.027* | |
H2B | 0.2493 | 0.4218 | 0.1616 | 0.027* | |
H2C | 0.2209 | 0.4077 | 0.3010 | 0.027* | |
C3 | 0.3334 (3) | 0.3616 (2) | 0.2562 (6) | 0.0219 (12) | |
H3A | 0.3297 | 0.3746 | 0.3427 | 0.033* | |
H3B | 0.3607 | 0.3796 | 0.1993 | 0.033* | |
H3C | 0.3546 | 0.3337 | 0.2644 | 0.033* | |
C4 | 0.2189 (3) | 0.32320 (16) | 0.2718 (5) | 0.0120 (10) | |
C5 | 0.1617 (3) | 0.30387 (15) | 0.2131 (5) | 0.0118 (9) | |
H5 | 0.1521 | 0.3088 | 0.1236 | 0.014* | |
C6 | 0.1194 (3) | 0.27745 (17) | 0.2879 (5) | 0.0134 (10) | |
C7 | 0.1320 (3) | 0.26925 (17) | 0.4211 (6) | 0.0157 (11) | |
C8 | 0.1889 (3) | 0.28782 (18) | 0.4793 (6) | 0.0189 (11) | |
H8 | 0.1986 | 0.2825 | 0.5686 | 0.023* | |
C9 | 0.2314 (3) | 0.31417 (17) | 0.4056 (5) | 0.0158 (11) | |
H9 | 0.2695 | 0.3263 | 0.4464 | 0.019* | |
C10 | 0.2724 (3) | 0.34332 (16) | 0.0512 (5) | 0.0110 (10) | |
C11 | 0.2603 (3) | 0.37152 (16) | −0.0552 (6) | 0.0162 (11) | |
H11 | 0.2390 | 0.3979 | −0.0391 | 0.019* | |
C12 | 0.2795 (3) | 0.36073 (17) | −0.1853 (5) | 0.0155 (11) | |
C13 | 0.3108 (3) | 0.32183 (18) | −0.2145 (5) | 0.0142 (10) | |
C14 | 0.3197 (3) | 0.29320 (16) | −0.1094 (5) | 0.0135 (10) | |
C15 | 0.3013 (3) | 0.30340 (17) | 0.0206 (5) | 0.0140 (10) | |
H15 | 0.3083 | 0.2833 | 0.0882 | 0.017* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0136 (3) | 0.0242 (3) | 0.0219 (3) | −0.0077 (2) | −0.0028 (2) | 0.0005 (2) |
Br2 | 0.0214 (3) | 0.0202 (3) | 0.0197 (3) | 0.0047 (2) | 0.0039 (2) | −0.0015 (2) |
Br3 | 0.0455 (4) | 0.0232 (3) | 0.0160 (3) | 0.0082 (3) | −0.0032 (2) | 0.0040 (2) |
O1 | 0.029 (2) | 0.029 (2) | 0.0128 (18) | 0.0070 (18) | −0.0002 (16) | −0.0004 (16) |
O2 | 0.019 (2) | 0.032 (2) | 0.022 (2) | −0.0091 (19) | 0.0000 (18) | 0.0102 (17) |
C1 | 0.008 (3) | 0.016 (2) | 0.018 (3) | −0.0016 (19) | 0.000 (2) | −0.002 (2) |
C2 | 0.024 (3) | 0.012 (3) | 0.018 (3) | 0.001 (2) | 0.006 (2) | −0.002 (2) |
C3 | 0.016 (3) | 0.032 (3) | 0.019 (3) | −0.012 (2) | −0.001 (2) | −0.005 (2) |
C4 | 0.009 (3) | 0.014 (2) | 0.014 (2) | 0.0008 (19) | 0.0012 (19) | 0.0001 (19) |
C5 | 0.012 (3) | 0.013 (2) | 0.010 (2) | 0.0000 (19) | 0.0000 (19) | 0.0004 (19) |
C6 | 0.006 (3) | 0.016 (2) | 0.019 (3) | 0.0038 (19) | −0.002 (2) | −0.002 (2) |
C7 | 0.017 (3) | 0.013 (2) | 0.017 (3) | 0.003 (2) | 0.004 (2) | 0.004 (2) |
C8 | 0.023 (3) | 0.023 (3) | 0.011 (2) | 0.001 (2) | −0.001 (2) | 0.005 (2) |
C9 | 0.014 (3) | 0.019 (3) | 0.014 (3) | −0.004 (2) | −0.004 (2) | 0.002 (2) |
C10 | 0.006 (2) | 0.015 (2) | 0.012 (2) | −0.0034 (19) | 0.0007 (18) | 0.0011 (19) |
C11 | 0.017 (3) | 0.015 (2) | 0.016 (3) | 0.003 (2) | −0.002 (2) | −0.001 (2) |
C12 | 0.018 (3) | 0.015 (2) | 0.014 (2) | 0.001 (2) | −0.004 (2) | 0.004 (2) |
C13 | 0.012 (3) | 0.022 (2) | 0.009 (2) | −0.003 (2) | −0.0035 (19) | −0.004 (2) |
C14 | 0.007 (3) | 0.015 (2) | 0.018 (3) | 0.0018 (19) | −0.0023 (19) | −0.002 (2) |
C15 | 0.010 (3) | 0.016 (3) | 0.016 (3) | 0.001 (2) | 0.000 (2) | 0.002 (2) |
Geometric parameters (Å, º) top
Br1—C6 | 1.903 (5) | C4—C9 | 1.393 (7) |
Br2—C14 | 1.905 (5) | C4—C5 | 1.398 (7) |
Br3—C12 | 1.900 (5) | C5—C6 | 1.385 (7) |
O1—C13 | 1.361 (7) | C5—H5 | 0.9300 |
O1—H1 | 0.8200 | C6—C7 | 1.382 (7) |
O2—C7 | 1.376 (7) | C7—C8 | 1.381 (8) |
O2—H2 | 0.8200 | C8—C9 | 1.380 (8) |
C1—C10 | 1.520 (7) | C8—H8 | 0.9300 |
C1—C4 | 1.528 (7) | C9—H9 | 0.9300 |
C1—C3 | 1.537 (7) | C10—C15 | 1.393 (7) |
C1—C2 | 1.541 (7) | C10—C11 | 1.400 (7) |
C2—H2A | 0.9600 | C11—C12 | 1.398 (8) |
C2—H2B | 0.9600 | C11—H11 | 0.9300 |
C2—H2C | 0.9600 | C12—C13 | 1.383 (8) |
C3—H3A | 0.9600 | C13—C14 | 1.388 (7) |
C3—H3B | 0.9600 | C14—C15 | 1.390 (7) |
C3—H3C | 0.9600 | C15—H15 | 0.9300 |
| | | |
C13—O1—H1 | 109.5 | C5—C6—Br1 | 119.8 (4) |
C7—O2—H2 | 109.5 | O2—C7—C8 | 117.1 (5) |
C10—C1—C4 | 112.0 (4) | O2—C7—C6 | 124.4 (5) |
C10—C1—C3 | 106.2 (4) | C8—C7—C6 | 118.5 (5) |
C4—C1—C3 | 111.8 (5) | C9—C8—C7 | 120.2 (5) |
C10—C1—C2 | 112.3 (4) | C9—C8—H8 | 119.9 |
C4—C1—C2 | 106.6 (4) | C7—C8—H8 | 119.9 |
C3—C1—C2 | 107.9 (5) | C8—C9—C4 | 122.1 (5) |
C1—C2—H2A | 109.5 | C8—C9—H9 | 119.0 |
C1—C2—H2B | 109.5 | C4—C9—H9 | 119.0 |
H2A—C2—H2B | 109.5 | C15—C10—C11 | 117.1 (5) |
C1—C2—H2C | 109.5 | C15—C10—C1 | 120.1 (4) |
H2A—C2—H2C | 109.5 | C11—C10—C1 | 122.6 (5) |
H2B—C2—H2C | 109.5 | C12—C11—C10 | 121.1 (5) |
C1—C3—H3A | 109.5 | C12—C11—H11 | 119.4 |
C1—C3—H3B | 109.5 | C10—C11—H11 | 119.4 |
H3A—C3—H3B | 109.5 | C13—C12—C11 | 121.7 (5) |
C1—C3—H3C | 109.5 | C13—C12—Br3 | 118.3 (4) |
H3A—C3—H3C | 109.5 | C11—C12—Br3 | 120.0 (4) |
H3B—C3—H3C | 109.5 | O1—C13—C12 | 118.8 (5) |
C9—C4—C5 | 117.4 (5) | O1—C13—C14 | 124.4 (5) |
C9—C4—C1 | 121.4 (5) | C12—C13—C14 | 116.8 (5) |
C5—C4—C1 | 121.0 (5) | C13—C14—C15 | 122.4 (5) |
C6—C5—C4 | 120.2 (5) | C13—C14—Br2 | 118.1 (4) |
C6—C5—H5 | 119.9 | C15—C14—Br2 | 119.5 (4) |
C4—C5—H5 | 119.9 | C14—C15—C10 | 120.8 (5) |
C7—C6—C5 | 121.7 (5) | C14—C15—H15 | 119.6 |
C7—C6—Br1 | 118.5 (4) | C10—C15—H15 | 119.6 |
| | | |
C10—C1—C4—C9 | 144.8 (5) | C2—C1—C10—C15 | −175.6 (5) |
C3—C1—C4—C9 | 25.8 (7) | C4—C1—C10—C11 | 130.4 (5) |
C2—C1—C4—C9 | −92.0 (6) | C3—C1—C10—C11 | −107.3 (6) |
C10—C1—C4—C5 | −41.3 (6) | C2—C1—C10—C11 | 10.4 (7) |
C3—C1—C4—C5 | −160.4 (5) | C15—C10—C11—C12 | −3.1 (8) |
C2—C1—C4—C5 | 81.8 (6) | C1—C10—C11—C12 | 171.1 (5) |
C9—C4—C5—C6 | 1.0 (7) | C10—C11—C12—C13 | 0.4 (9) |
C1—C4—C5—C6 | −173.1 (5) | C10—C11—C12—Br3 | −178.1 (4) |
C4—C5—C6—C7 | −0.2 (8) | C11—C12—C13—O1 | −176.1 (5) |
C4—C5—C6—Br1 | 179.6 (4) | Br3—C12—C13—O1 | 2.4 (7) |
C5—C6—C7—O2 | 179.5 (5) | C11—C12—C13—C14 | 2.6 (8) |
Br1—C6—C7—O2 | −0.2 (7) | Br3—C12—C13—C14 | −178.8 (4) |
C5—C6—C7—C8 | −0.5 (8) | O1—C13—C14—C15 | 175.6 (5) |
Br1—C6—C7—C8 | 179.7 (4) | C12—C13—C14—C15 | −3.0 (8) |
O2—C7—C8—C9 | −179.6 (5) | O1—C13—C14—Br2 | −2.9 (7) |
C6—C7—C8—C9 | 0.5 (8) | C12—C13—C14—Br2 | 178.4 (4) |
C7—C8—C9—C4 | 0.3 (9) | C13—C14—C15—C10 | 0.4 (8) |
C5—C4—C9—C8 | −1.0 (8) | Br2—C14—C15—C10 | 178.9 (4) |
C1—C4—C9—C8 | 173.0 (5) | C11—C10—C15—C14 | 2.7 (8) |
C4—C1—C10—C15 | −55.7 (7) | C1—C10—C15—C14 | −171.6 (5) |
C3—C1—C10—C15 | 66.7 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.18 | 2.818 (5) | 134 |
Symmetry code: (i) −x+1/2, −y+1/2, z−1. |
(III) 3,3',5,5'-Tetrabromo-4,4'-dihydroxy-diphenyl-dimethyl-methane
top
Crystal data top
C15H12Br4O2 | Dx = 2.158 Mg m−3 |
Mr = 543.89 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43212 | Cell parameters from 1720 reflections |
Hall symbol: P 41n 2abw | θ = 1.7–26.1° |
a = 12.0038 (16) Å | µ = 9.62 mm−1 |
c = 11.618 (3) Å | T = 293 K |
V = 1674.1 (5) Å3 | Prism, colourless |
Z = 4 | 0.15 × 0.14 × 0.12 mm |
F(000) = 1032 | |
Data collection top
Stoe IPDS area-detector diffractometer | 1625 independent reflections |
Radiation source: fine-focus sealed tube | 915 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.171 |
Detector resolution: 6.0 pixels mm-1 | θmax = 25.9°, θmin = 2.4° |
area detector scans | h = −14→14 |
Absorption correction: numerical (X-RED; Stoe, 1997) | k = −14→14 |
Tmin = 0.236, Tmax = 0.302 | l = −14→14 |
13032 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.01P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.81 | (Δ/σ)max = 0.001 |
1625 reflections | Δρmax = 0.42 e Å−3 |
98 parameters | Δρmin = −0.39 e Å−3 |
26 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (3) |
Crystal data top
C15H12Br4O2 | Z = 4 |
Mr = 543.89 | Mo Kα radiation |
Tetragonal, P43212 | µ = 9.62 mm−1 |
a = 12.0038 (16) Å | T = 293 K |
c = 11.618 (3) Å | 0.15 × 0.14 × 0.12 mm |
V = 1674.1 (5) Å3 | |
Data collection top
Stoe IPDS area-detector diffractometer | 1625 independent reflections |
Absorption correction: numerical (X-RED; Stoe, 1997) | 915 reflections with I > 2σ(I) |
Tmin = 0.236, Tmax = 0.302 | Rint = 0.171 |
13032 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.060 | Δρmax = 0.42 e Å−3 |
S = 0.81 | Δρmin = −0.39 e Å−3 |
1625 reflections | Absolute structure: Flack (1983) |
98 parameters | Absolute structure parameter: 0.03 (3) |
26 restraints | |
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 | x | y | z | Uiso*/Ueq | |
Br1 | 0.14857 (8) | 0.55894 (7) | 0.18353 (8) | 0.0590 (3) | |
Br2 | 0.38816 (7) | 0.15045 (7) | 0.18750 (8) | 0.0533 (3) | |
C1 | 0.4670 (6) | 0.4670 (6) | 0.5000 | 0.035 (3) | |
C2 | 0.5901 (6) | 0.4518 (7) | 0.4685 (7) | 0.048 (3) | |
H2A | 0.6047 | 0.3744 | 0.4540 | 0.073* | |
H2B | 0.6358 | 0.4770 | 0.5311 | 0.073* | |
H2C | 0.6068 | 0.4944 | 0.4007 | 0.073* | |
C3 | 0.3971 (6) | 0.4312 (6) | 0.3961 (6) | 0.0286 (19) | |
C4 | 0.3171 (6) | 0.4986 (6) | 0.3447 (7) | 0.033 (2) | |
H4 | 0.3040 | 0.5689 | 0.3754 | 0.039* | |
C5 | 0.2560 (6) | 0.4648 (7) | 0.2491 (6) | 0.0326 (19) | |
C6 | 0.2740 (6) | 0.3579 (8) | 0.2021 (7) | 0.038 (2) | |
C7 | 0.3546 (7) | 0.2887 (6) | 0.2513 (6) | 0.0328 (19) | |
C8 | 0.4104 (6) | 0.3260 (6) | 0.3479 (6) | 0.033 (2) | |
H8 | 0.4604 | 0.2774 | 0.3830 | 0.040* | |
O1 | 0.2159 (6) | 0.3255 (5) | 0.1073 (5) | 0.0598 (18) | |
H1 | 0.1905 | 0.2629 | 0.1177 | 0.090* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0506 (6) | 0.0730 (7) | 0.0534 (6) | 0.0257 (6) | −0.0076 (6) | 0.0146 (6) |
Br2 | 0.0608 (6) | 0.0385 (5) | 0.0606 (6) | −0.0011 (5) | −0.0017 (5) | −0.0083 (5) |
C1 | 0.032 (4) | 0.032 (4) | 0.042 (7) | −0.003 (7) | 0.001 (4) | −0.001 (4) |
C2 | 0.045 (6) | 0.052 (6) | 0.048 (6) | −0.009 (5) | −0.003 (5) | 0.010 (5) |
C3 | 0.032 (4) | 0.028 (4) | 0.026 (5) | −0.002 (4) | −0.004 (3) | 0.010 (3) |
C4 | 0.037 (5) | 0.028 (4) | 0.033 (5) | 0.006 (4) | 0.010 (4) | 0.003 (4) |
C5 | 0.039 (5) | 0.029 (5) | 0.029 (5) | −0.001 (4) | 0.008 (4) | 0.008 (4) |
C6 | 0.027 (4) | 0.059 (5) | 0.028 (5) | −0.010 (4) | −0.005 (4) | 0.004 (5) |
C7 | 0.027 (4) | 0.035 (5) | 0.036 (5) | 0.000 (4) | −0.007 (4) | 0.007 (4) |
C8 | 0.035 (5) | 0.026 (5) | 0.038 (5) | 0.009 (4) | 0.000 (4) | 0.003 (4) |
O1 | 0.062 (4) | 0.069 (6) | 0.048 (4) | −0.016 (4) | −0.019 (3) | 0.001 (3) |
Geometric parameters (Å, º) top
Br1—C5 | 1.877 (7) | C3—C8 | 1.391 (10) |
Br2—C7 | 1.862 (7) | C4—C5 | 1.391 (10) |
C1—C3 | 1.532 (9) | C4—H4 | 0.9300 |
C1—C3i | 1.532 (9) | C5—C6 | 1.412 (11) |
C1—C2i | 1.533 (9) | C6—O1 | 1.360 (9) |
C1—C2 | 1.533 (9) | C6—C7 | 1.397 (10) |
C2—H2A | 0.9600 | C7—C8 | 1.381 (9) |
C2—H2B | 0.9600 | C8—H8 | 0.9300 |
C2—H2C | 0.9600 | O1—H1 | 0.8200 |
C3—C4 | 1.389 (9) | | |
| | | |
C3—C1—C3i | 108.3 (8) | C3—C4—H4 | 118.8 |
C3—C1—C2i | 113.1 (4) | C5—C4—H4 | 118.8 |
C3i—C1—C2i | 107.9 (5) | C4—C5—C6 | 119.6 (7) |
C3—C1—C2 | 107.9 (5) | C4—C5—Br1 | 120.7 (6) |
C3i—C1—C2 | 113.1 (4) | C6—C5—Br1 | 119.7 (6) |
C2i—C1—C2 | 106.6 (10) | O1—C6—C7 | 121.1 (8) |
C1—C2—H2A | 109.5 | O1—C6—C5 | 119.6 (8) |
C1—C2—H2B | 109.5 | C7—C6—C5 | 119.2 (7) |
H2A—C2—H2B | 109.5 | C8—C7—C6 | 118.4 (7) |
C1—C2—H2C | 109.5 | C8—C7—Br2 | 120.5 (6) |
H2A—C2—H2C | 109.5 | C6—C7—Br2 | 121.1 (6) |
H2B—C2—H2C | 109.5 | C7—C8—C3 | 124.4 (7) |
C4—C3—C8 | 115.8 (7) | C7—C8—H8 | 117.8 |
C4—C3—C1 | 123.6 (6) | C3—C8—H8 | 117.8 |
C8—C3—C1 | 120.5 (6) | C6—O1—H1 | 109.5 |
C3—C4—C5 | 122.5 (7) | | |
| | | |
C3i—C1—C3—C4 | 111.5 (8) | Br1—C5—C6—O1 | 2.1 (10) |
C2i—C1—C3—C4 | −8.0 (10) | C4—C5—C6—C7 | −1.2 (11) |
C2—C1—C3—C4 | −125.7 (7) | Br1—C5—C6—C7 | 179.7 (5) |
C3i—C1—C3—C8 | −67.9 (6) | O1—C6—C7—C8 | −179.7 (7) |
C2i—C1—C3—C8 | 172.6 (8) | C5—C6—C7—C8 | 2.8 (11) |
C2—C1—C3—C8 | 54.9 (9) | O1—C6—C7—Br2 | 1.4 (10) |
C8—C3—C4—C5 | −1.7 (11) | C5—C6—C7—Br2 | −176.2 (6) |
C1—C3—C4—C5 | 178.9 (7) | C6—C7—C8—C3 | −4.2 (12) |
C3—C4—C5—C6 | 0.6 (11) | Br2—C7—C8—C3 | 174.8 (6) |
C3—C4—C5—Br1 | 179.7 (5) | C4—C3—C8—C7 | 3.5 (11) |
C4—C5—C6—O1 | −178.7 (7) | C1—C3—C8—C7 | −177.1 (7) |
Symmetry code: (i) y, x, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1ii | 0.82 | 3.13 | 3.11 (1) | 81 |
Symmetry code: (ii) y, x, −z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C15H12Cl4O2 | C15H13Br3O2 | C15H12Br4O2 |
Mr | 366.05 | 464.98 | 543.89 |
Crystal system, space group | Orthorhombic, Pbcn | Orthorhombic, Fdd2 | Tetragonal, P43212 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 25.675 (9), 11.602 (3), 10.530 (4) | 19.545 (3), 30.971 (4), 10.0335 (19) | 12.0038 (16), 12.0038 (16), 11.618 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 3136.6 (17) | 6073.6 (16) | 1674.1 (5) |
Z | 8 | 16 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.75 | 7.97 | 9.62 |
Crystal size (mm) | 0.23 × 0.16 × 0.13 | 0.31 × 0.27 × 0.22 | 0.15 × 0.14 × 0.12 |
|
Data collection |
Diffractometer | Stoe AED2 diffractometer | Stoe IPDS area-detector diffractometer | Stoe IPDS area-detector diffractometer |
Absorption correction | Numerical (X-RED; Stoe, 1997) | Numerical (X-RED; Stoe, 1997) | Numerical (X-RED; Stoe, 1997) |
Tmin, Tmax | 0.843, 0.906 | 0.086, 0.167 | 0.236, 0.302 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3572, 2771, 1267 | 10060, 1559, 1500 | 13032, 1625, 915 |
Rint | 0.061 | 0.066 | 0.171 |
(sin θ/λ)max (Å−1) | 0.596 | 0.614 | 0.614 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.075, 1.07 | 0.026, 0.063, 1.16 | 0.039, 0.060, 0.81 |
No. of reflections | 2771 | 1559 | 1625 |
No. of parameters | 191 | 185 | 98 |
No. of restraints | 0 | 1 | 26 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.32 | 1.50, −0.41 | 0.42, −0.39 |
Absolute structure | ? | ? | Flack (1983) |
Absolute structure parameter | ? | ? | 0.03 (3) |
Selected geometric parameters (Å, º) for (I) topCl1—C8 | 1.734 (4) | Cl3—C14 | 1.736 (4) |
Cl2—C6 | 1.732 (4) | Cl4—C12 | 1.732 (4) |
| | | |
C4—C1—C10 | 108.1 (3) | C9—C4—C1 | 120.5 (3) |
C4—C1—C3 | 112.3 (4) | O1—C7—C8 | 120.3 (4) |
C10—C1—C3 | 109.2 (3) | O1—C7—C6 | 123.0 (4) |
C4—C1—C2 | 106.8 (3) | C11—C10—C15 | 117.9 (4) |
C10—C1—C2 | 111.7 (3) | C11—C10—C1 | 124.0 (4) |
C3—C1—C2 | 108.8 (3) | C15—C10—C1 | 118.1 (3) |
C5—C4—C9 | 116.4 (4) | O2—C13—C12 | 120.1 (4) |
C5—C4—C1 | 123.0 (3) | O2—C13—C14 | 122.8 (4) |
| | | |
C10—C1—C4—C5 | −148.3 (4) | C2—C1—C4—C9 | −87.5 (4) |
C3—C1—C4—C5 | −27.8 (5) | C9—C4—C5—C6 | −2.3 (6) |
C2—C1—C4—C5 | 91.4 (5) | C1—C4—C5—C6 | 178.8 (3) |
C10—C1—C4—C9 | 32.9 (5) | C15—C10—C11—C12 | −2.8 (6) |
C3—C1—C4—C9 | 153.3 (4) | C1—C10—C11—C12 | 174.8 (4) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.113 | 2.723 (3) | 131 |
O2—H2···O2ii | 0.82 | 2.221 | 2.773 (5) | 125 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topBr1—C6 | 1.903 (5) | C1—C4 | 1.528 (7) |
Br2—C14 | 1.905 (5) | C1—C3 | 1.537 (7) |
Br3—C12 | 1.900 (5) | C1—C2 | 1.541 (7) |
C1—C10 | 1.520 (7) | | |
| | | |
C10—C1—C4 | 112.0 (4) | C5—C4—C1 | 121.0 (5) |
C10—C1—C3 | 106.2 (4) | O2—C7—C8 | 117.1 (5) |
C4—C1—C3 | 111.8 (5) | O2—C7—C6 | 124.4 (5) |
C10—C1—C2 | 112.3 (4) | C15—C10—C11 | 117.1 (5) |
C4—C1—C2 | 106.6 (4) | C15—C10—C1 | 120.1 (4) |
C3—C1—C2 | 107.9 (5) | C11—C10—C1 | 122.6 (5) |
C9—C4—C5 | 117.4 (5) | O1—C13—C12 | 118.8 (5) |
C9—C4—C1 | 121.4 (5) | O1—C13—C14 | 124.4 (5) |
| | | |
C10—C1—C4—C9 | 144.8 (5) | C2—C1—C4—C5 | 81.8 (6) |
C3—C1—C4—C9 | 25.8 (7) | C9—C4—C5—C6 | 1.0 (7) |
C2—C1—C4—C9 | −92.0 (6) | C1—C4—C5—C6 | −173.1 (5) |
C10—C1—C4—C5 | −41.3 (6) | C15—C10—C11—C12 | −3.1 (8) |
C3—C1—C4—C5 | −160.4 (5) | C1—C10—C11—C12 | 171.1 (5) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.18 | 2.818 (5) | 134 |
Symmetry code: (i) −x+1/2, −y+1/2, z−1. |
Selected geometric parameters (Å, º) for (III) topBr1—C5 | 1.877 (7) | C1—C3 | 1.532 (9) |
Br2—C7 | 1.862 (7) | C1—C2 | 1.533 (9) |
| | | |
C3—C1—C3i | 108.3 (8) | C4—C3—C1 | 123.6 (6) |
C3—C1—C2i | 113.1 (4) | C8—C3—C1 | 120.5 (6) |
C3—C1—C2 | 107.9 (5) | O1—C6—C7 | 121.1 (8) |
C2i—C1—C2 | 106.6 (10) | O1—C6—C5 | 119.6 (8) |
C4—C3—C8 | 115.8 (7) | | |
| | | |
C3i—C1—C3—C4 | 111.5 (8) | C2i—C1—C3—C8 | 172.6 (8) |
C2i—C1—C3—C4 | −8.0 (10) | C2—C1—C3—C8 | 54.9 (9) |
C2—C1—C3—C4 | −125.7 (7) | C8—C3—C4—C5 | −1.7 (11) |
C3i—C1—C3—C8 | −67.9 (6) | C1—C3—C4—C5 | 178.9 (7) |
Symmetry code: (i) y, x, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1ii | 0.82 | 3.13 | 3.11 (1) | 81 |
Symmetry code: (ii) y, x, −z. |
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In recent years, several reports have indicated that the widespread use of flame retardants is responsible for the bioaccumulation of these compounds in nature. The decomposition of flame retardants in the natural environment and the products obtained from these is a long-running project in our department. The goal is a better understanding of the reactivity of these compounds in the environment.
The different substances observed in decomposition experiments that mimic realistic circumstances in the natural environment indicate large differences among the decomposition products, depending on the halogen substitution pattern and on whether the reactant is in aqueous solution or in the solid state.
The title compounds are members of a class collectively named `halogenated bisphenols', which are used as reactive flame retardants. This means that they are not only mixed together with a prefabricated plastic material but also take part in the polymerization process, where they are covalently bound into the polymer. The salient feature of reactive flame retardants is thus that they migrate less easily to the environment, due to this covalent bonding to the polymer. The corresponding additive flame retardants, which are simply mixed into a pre-produced polymer, migrate more easily (Kuryla & Papa, 1979).
The three title compounds, 2,2',6,6'-tetrachloro-4,4'-propane-2,2-diyldiphenol, (I), 2,2',6,-tribromo-4,4'-propane-2,2-diyldiphenol, (II) and 2,2',6,6'-tetrabromo-4,4'-propane-2,2-diyldiphenol, (III), are three common flame retardants with pseudo-isomorphous molecular structures (Figs. 1–3), but exhibiting very different crystal structures. \sch
The first two of the title compounds, (I) and (II), represent previously unknown structures, while the third, (III), has been reported previously by Simonov et al. (1986). Diffraction data have been remeasured for (III), and we have changed the absolute configuration of the molecule and also the space group, from P41212 (92) to P43212 (96), as these two constitute an enantiomorphic space-group pair. Some anomalous bond distances found with the refinement in P41212 (92) are shown to be absent when refining the structure model with the correct absolute configuration in P43212 (96).
The crystal structure of (I) is built up by a packing of sheets of hydrogen-bonded molecules, further stabilized by a very short intermolecular Cl···Cl contact: Cl1···Cl1i = 3.094 (2) Å [symmetry code: (i) 1 - x, -y, -z]. This is shorter than is observed in most of the well determined (R ≤ 10%) and non-disordered similar structures in the Cambridge Structural Database (CSD; Allen & Kennard, 1993), for instance, triphenylchloromethane (Dunand & Gerdil, 1982), where the shortest intermolecular Cl···Cl distance is 3.210 Å, which is itself considered to be very short (Desiraju, 1989). A similarly short intermolecular inter-halogen distance does not occur in the bromo analogue, (III).
The shortest intermolecular O···O contact distance in (I), O1···O2ii 2.723 (3) Å [symmetry code: (ii) x, y - 1, z], is also shorter than the corresponding shortest intermolecular O···O contact distance in (III) [O···O 3.11 (1) Å], thus indicating stronger hydrogen bonding between the molecules of (I) along the b axis.
Regarding the close similarity of the molecular structures, a reasonable conjecture would be that the tetrachlorobisphenol in (I) should have a rather similar structure to the brominated analogue in (III). The present investigation shows that this is not the case at all, neither concerning space group nor packing of the molecules. Further investigations will be carried out to elucidate the physical background to the close Cl···Cl contact in (I), whether it is a consequence or a reason for the packing of (I).
The hydrogen-bonding scheme in (I) cannot be deduced with certainty, since at least two schemes are possible (Fig. 4). The conformations of the four hydroxyl groups are restricted by the space-group symmetry. One can speculate on other hydrogen-bond schemes which break the space-group symmetry, e.g. with the four hydroxyl groups pointing to each other in a circular pattern, or a disordered hydrogen-bond scheme. This possible violation of the space-group symmetry by the H atoms cannot be detected in the diffraction data.
The second compound, (II), differs from the most commonly used flame retardant, (III), only by the lack of one Br atom, yet it crystallizes in a totally different structure. The crystal structure of (II) can be described as a packing of square helices running along the c axis. Each helix is built of two strands of hydrogen-bonded molecules of (II), further stabilized by interactions between the halogens and the aromatic ring systems. Three molecules of each strand in the helices are shown in Fig. 5. The two strands fit together to make up a square-type double helix in the ab plane. The shortest Br···Br distances (3.71–4.21 Å) correspond to intermolecular Br···Br contacts between different helices.
In contrast with the plausible hydrogen-bonding pattern of (II), no appreciable hydrogen bonding can be deduced from the packing of (III). Here, the molecules preferentially pack in long chains, with interactions between the aromatic rings and the aliphatic central part of the molecule, to give the packing pattern shown in Fig. 6, which is completely different from (II). The rather long intermolecular O···O contacts in (III) (>= 3.1 Å) may contribute to a minor stabilization of the structure of (III). The reported position for atom H1 involved in the possible hydrogen bond is that derived from the least-squares calculations. A geometrically computed position for H1 (0.2458, 0.2955, 0.0487) gives a linear link to the plausible acceptor O1iii [symmetry code: (iii) y, x, -z]. Atom H1 and the symmetry-related H1 cannot both be linearly directed to the corresponding acceptor, but there is a possibility of a hydrogen positional disorder around atom O1, giving some slight stabilization due to intermolecular hydrogen bonds in (III).
Compound (II) exhibits much shorter intermolecular O···O distances compared with (III), so the contribution from hydrogen bonds to the stabilization of the structure is probably much larger for (II) than for (III). Similar Br···Br contact distances exist in both (II) and (III). In (II), the intermolecular Br···Br distances are >3.71 Å; in (III), these distances are >3.93 Å. This also indicates slightly stronger intermolecular bonding involving the Br···Br contacts for (II) compared with (III).
Both rings of (I) are planar, to within 0.013 Å for C4—C9 and 0.010 Å for C10—C15. Atom Cl1 involved in the very short intermolecular Cl···Cl contact is within 0.007 (5) Å of the plane defined by the C atoms in the aromatic ring. Atom O1 of the C4—C9 ring has the largest deviation from the ring plane. This can be interpreted as originating from effects by the short intermolecular O1···O2ii contact. The substituents of the second ring deviate more from the ring plane: deviations are 0.103 (5) for Cl4, 0.037 (5) for O2 and 0.098 (6) Å for Cl3. The angle between the two ring planes is 64.0 (1)° and this is smaller than corresponding interplanar angles of most of the similar structures from the CSD. There are seven structures with the 4,4'-dihydroxy-diphenyl-dimethyl-methane skeleton available in the CSD. One of them exhibits an interplanar angle of 64°, but the others have interplanar angles in the range 72–96°. The compound with the smallest angle, 2,2',6,6'-tetranitro-4,4'-isopropylidenediphenol (CSD refcode BIDJED; Wang et al., 1982) is also heavily affected by intermolecular bonding effects, similar to those present in (I). Smaller interplanar angles shown by similar compounds from the CSD are only present when either heavily steric interactions occur or a direct covalent bond restricts the conformation of the different rings.
Both rings of (II) are planar, to within 0.007 Å for C4—C9 and 0.02 Å for C10—C15. The ring with two Br substituents is more puckered than that with only one Br substituent. Most conspicuous are the deviations from the ring plane of the two hydroxyl O atoms: 0.108 (7) for O1 and 0.019 (7) Å for O2. These deviations can be described as a function of steric interaction. Atom O2 is pushed away by the close contact from Br1 and stays approximately in the ring plane, while atom O1 is pushed out of the ring plane, as it is situated in between two close Br substituents (Br2 and Br3). It is rather strange that the angular distortion found for O2 is also present for O1; the difference is mostly the out-of-plane deviation of O1. Both ring planes are defined solely by the C atoms in each ring. The angle between the two ring planes is 81.8 (2)°.
The ring of (III) is planar to within 0.011 Å (C3—C8). The two atoms deviating most from this plane are Br1 [0.022 (1) Å] and Br2 [0.118 (10) Å]. In this compound, the angular distortion of atom O1 with respect to the ring is much less than the corresponding distortions in the dibromo-substituted ring of (II). The ring plane is defined solely by the C atoms in the ring. The angle between the ring plane and the plane of the symmetry-related ring is 80.2 (2)°