The crystal structures of 4,10-dibromo-anthanthrone (Pigment Red 168; 4,10-dibromo-dibenzo[
def,
mno]chrysene-6,12-dione), 4,10-dichloro- and 4,10-diiodo-anthanthrone have been determined by single-crystal X-ray analyses. The dibromo and diiodo derivatives crystallize in
P2
1/
c,
Z = 2, the dichloro derivative in
,
Z = 1. The molecular structures are almost identical and the unit-cell parameters show some similarities for all three compounds, but the crystal structures are neither isotypic to another nor to the unsubstituted anthanthrone, which crystallizes in
P2
1/
c,
Z = 8. In order to explain why the four anthanthrone derivatives have four different crystal structures, lattice-energy minimizations were performed using anisotropic atom–atom model potentials as well as using the semi-classical density sums (SCDS-Pixel) approach. The calculations showed the crystal structures of the dichloro and the diiodo derivatives to be the most stable ones for the corresponding compound; whereas for dibromo-anthanthrone the calculations suggest that the dichloro and diiodo structure types should be more stable than the experimentally observed structure. An experimental search for new polymorphs of dibromo-anthanthrone was carried out, but the experiments were hampered by the remarkable insolubility of the compound. A metastable nanocrystalline second polymorph of the dibromo derivative does exist, but it is not isostructural to the dichloro or diiodo compound. In order to determine the crystal structure of this phase, crystal structure predictions were performed in various space groups, using anisotropic atom–atom potentials. For all low-energy structures, X-ray powder patterns were calculated and compared with the experimental diagram, which consisted of a few broad lines only. It turned out that the crystallinity of this phase was not sufficient to determine which of the calculated structures corresponds to the actual structure of this nanocrystalline polymorph.
Supporting information
CCDC references: 798609; 798610; 798611
Data collection: R3m/V-software (Siemens) for pu280, pu288; R3m/V-software (Sioemens) for pu287. Cell refinement: R3m/V-software (Siemens) for pu280, pu288; R3m/V-software (Sioemens) for pu287. Data reduction: R3m/V-software (Siemens) for pu280, pu288; R3m/V-software (Sioemens) for pu287. For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL-Plus97 (Sheldrick, 1997).
'4,10-Dibromo-anthanthrone, alpha-phase' (pu280)
top
Crystal data top
| C22H8Br2O2 | Dx = 2.032 Mg m−3 |
| Mr = 464.10 | Melting point > 300 K |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
| a = 3.865 (1) Å | Cell parameters from 25 reflections |
| b = 19.424 (2) Å | θ = 4.5–24.0° |
| c = 10.113 (1) Å | µ = 5.36 mm−1 |
| β = 92.56 (1)° | T = 293 K |
| V = 758.5 (2) Å3 | Plate, red |
| Z = 2 | 0.50 × 0.25 × 0.01 mm |
| F(000) = 452 | |
Data collection top
R3m/V (Siemens)
diffractometer | 1499 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.026 |
| Graphite monochromator | θmax = 28.1°, θmin = 2.1° |
| ω–2θ scans | h = −5→5 |
| Absorption correction: ψ scan | k = 0→25 |
| Tmin = 0.218, Tmax = 0.948 | l = −13→13 |
| 3661 measured reflections | 1 standard reflections every 69 reflections |
| 1838 independent reflections | intensity decay: <1% |
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)] = 0.044 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.118 | All H-atom parameters refined |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0803P)2 + 0.1814P]
where P = (Fo2 + 2Fc2)/3 |
| 1838 reflections | (Δ/σ)max < 0.001 |
| 134 parameters | Δρmax = 0.55 e Å−3 |
| 0 restraints | Δρmin = −0.58 e Å−3 |
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 | |
| C01 | 0.2997 (9) | −0.19363 (18) | 0.0111 (4) | 0.0353 (7) | |
| C02 | 0.2213 (10) | −0.22540 (18) | 0.1302 (4) | 0.0406 (8) | |
| C03 | 0.0647 (9) | −0.18868 (19) | 0.2269 (4) | 0.0374 (7) | |
| C04 | −0.0190 (9) | −0.11848 (16) | 0.2087 (3) | 0.0304 (7) | |
| C05 | 0.0539 (8) | −0.08627 (16) | 0.0862 (3) | 0.0277 (6) | |
| C06 | −0.0361 (7) | −0.01604 (16) | 0.0635 (3) | 0.0269 (6) | |
| C07 | 0.1726 (8) | 0.07663 (18) | −0.3070 (3) | 0.0321 (7) | |
| C08 | 0.2574 (9) | 0.00979 (19) | −0.2847 (3) | 0.0343 (7) | |
| C09 | 0.1921 (8) | −0.02116 (16) | −0.1614 (3) | 0.0291 (6) | |
| C10 | 0.3004 (9) | −0.09342 (17) | −0.1398 (3) | 0.0316 (7) | |
| C11 | 0.2147 (8) | −0.12559 (17) | −0.0119 (3) | 0.0301 (7) | |
| H01 | 0.429 (11) | −0.220 (2) | −0.055 (4) | 0.040 (11)* | |
| H02 | 0.271 (8) | −0.2695 (17) | 0.159 (3) | 0.017 (8)* | |
| H03 | 0.041 (12) | −0.207 (3) | 0.308 (5) | 0.066 (15)* | |
| H08 | 0.384 (12) | −0.020 (2) | −0.351 (5) | 0.054 (13)* | |
| Br1 | 0.26710 (10) | 0.11466 (2) | −0.47457 (4) | 0.04355 (18) | |
| O1 | 0.4590 (9) | −0.12517 (13) | −0.2226 (3) | 0.0473 (7) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C01 | 0.0380 (18) | 0.0255 (16) | 0.0421 (18) | 0.0025 (13) | −0.0023 (14) | −0.0017 (13) |
| C02 | 0.047 (2) | 0.0272 (17) | 0.047 (2) | 0.0009 (15) | −0.0057 (16) | 0.0060 (14) |
| C03 | 0.0398 (18) | 0.0332 (17) | 0.0388 (18) | −0.0013 (14) | −0.0035 (14) | 0.0074 (14) |
| C04 | 0.0303 (15) | 0.0285 (15) | 0.0320 (16) | −0.0034 (12) | −0.0035 (12) | 0.0028 (11) |
| C05 | 0.0286 (14) | 0.0263 (14) | 0.0280 (14) | −0.0023 (12) | −0.0007 (11) | −0.0012 (12) |
| C06 | 0.0258 (14) | 0.0261 (14) | 0.0286 (15) | −0.0036 (11) | −0.0015 (11) | −0.0009 (11) |
| C07 | 0.0321 (16) | 0.0359 (17) | 0.0282 (14) | −0.0085 (13) | 0.0003 (12) | 0.0067 (12) |
| C08 | 0.0360 (17) | 0.0373 (18) | 0.0295 (15) | −0.0015 (14) | 0.0025 (13) | −0.0016 (13) |
| C09 | 0.0305 (15) | 0.0272 (15) | 0.0296 (14) | −0.0023 (12) | 0.0000 (12) | −0.0031 (12) |
| C10 | 0.0336 (16) | 0.0302 (16) | 0.0311 (15) | −0.0016 (13) | 0.0022 (12) | −0.0039 (13) |
| C11 | 0.0324 (16) | 0.0251 (16) | 0.0326 (16) | −0.0015 (12) | −0.0021 (12) | −0.0035 (11) |
| Br1 | 0.0465 (3) | 0.0503 (3) | 0.0344 (2) | −0.00144 (16) | 0.00691 (15) | 0.01158 (14) |
| O1 | 0.0681 (19) | 0.0342 (14) | 0.0407 (15) | 0.0112 (12) | 0.0141 (13) | −0.0060 (10) |
Geometric parameters (Å, º) top
| C01—C11 | 1.379 (5) | C06—C09i | 1.385 (4) |
| C01—C02 | 1.399 (5) | C06—C06i | 1.465 (6) |
| C01—H01 | 0.99 (4) | C07—C08 | 1.356 (5) |
| C02—C03 | 1.373 (5) | C07—C04i | 1.433 (5) |
| C02—H02 | 0.92 (3) | C07—Br1 | 1.899 (3) |
| C03—C04 | 1.412 (5) | C08—C09 | 1.417 (4) |
| C03—H03 | 0.90 (5) | C08—H08 | 1.02 (5) |
| C04—C05 | 1.427 (4) | C09—C06i | 1.385 (4) |
| C04—C07i | 1.433 (5) | C09—C10 | 1.478 (5) |
| C05—C11 | 1.417 (4) | C10—O1 | 1.226 (4) |
| C05—C06 | 1.424 (4) | C10—C11 | 1.487 (5) |
| | | |
| C11—C01—C02 | 120.6 (3) | C05—C06—C06i | 119.6 (3) |
| C11—C01—H01 | 120 (2) | C08—C07—C04i | 122.2 (3) |
| C02—C01—H01 | 119 (2) | C08—C07—Br1 | 117.8 (3) |
| C03—C02—C01 | 120.2 (3) | C04i—C07—Br1 | 120.0 (2) |
| C03—C02—H02 | 110 (2) | C07—C08—C09 | 120.1 (3) |
| C01—C02—H02 | 129 (2) | C07—C08—H08 | 123 (3) |
| C02—C03—C04 | 121.0 (3) | C09—C08—H08 | 117 (3) |
| C02—C03—H03 | 120 (3) | C06i—C09—C08 | 120.5 (3) |
| C04—C03—H03 | 118 (3) | C06i—C09—C10 | 121.3 (3) |
| C03—C04—C05 | 119.0 (3) | C08—C09—C10 | 118.2 (3) |
| C03—C04—C07i | 123.8 (3) | O1—C10—C09 | 121.6 (3) |
| C05—C04—C07i | 117.2 (3) | O1—C10—C11 | 121.3 (3) |
| C11—C05—C06 | 121.0 (3) | C09—C10—C11 | 117.0 (3) |
| C11—C05—C04 | 118.8 (3) | C01—C11—C05 | 120.5 (3) |
| C06—C05—C04 | 120.2 (3) | C01—C11—C10 | 119.2 (3) |
| C09i—C06—C05 | 119.7 (3) | C05—C11—C10 | 120.3 (3) |
| C09i—C06—C06i | 120.7 (4) | | |
| | | |
| C11—C01—C02—C03 | −1.3 (6) | C07—C08—C09—C10 | −177.9 (3) |
| C01—C02—C03—C04 | −0.2 (6) | C06i—C09—C10—O1 | −175.1 (3) |
| C02—C03—C04—C05 | 1.5 (5) | C08—C09—C10—O1 | 3.8 (5) |
| C02—C03—C04—C07i | −178.0 (3) | C06i—C09—C10—C11 | 3.7 (4) |
| C03—C04—C05—C11 | −1.3 (5) | C08—C09—C10—C11 | −177.4 (3) |
| C07i—C04—C05—C11 | 178.2 (3) | C02—C01—C11—C05 | 1.5 (5) |
| C03—C04—C05—C06 | 178.3 (3) | C02—C01—C11—C10 | −179.8 (3) |
| C07i—C04—C05—C06 | −2.1 (4) | C06—C05—C11—C01 | −179.8 (3) |
| C11—C05—C06—C09i | −179.8 (3) | C04—C05—C11—C01 | −0.2 (5) |
| C04—C05—C06—C09i | 0.6 (4) | C06—C05—C11—C10 | 1.5 (4) |
| C11—C05—C06—C06i | 0.5 (5) | C04—C05—C11—C10 | −178.9 (3) |
| C04—C05—C06—C06i | −179.1 (3) | O1—C10—C11—C01 | −3.4 (5) |
| C04i—C07—C08—C09 | 0.6 (5) | C09—C10—C11—C01 | 177.8 (3) |
| Br1—C07—C08—C09 | −179.9 (2) | O1—C10—C11—C05 | 175.3 (3) |
| C07—C08—C09—C06i | 1.1 (5) | C09—C10—C11—C05 | −3.5 (4) |
| Symmetry code: (i) −x, −y, −z. |
'4,10-diiodo-anthanthrone' (pu287)
top
Crystal data top
| C22H8I2O2 | Dx = 2.309 Mg m−3 |
| Mr = 558.08 | Melting point > 300 K |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71072 Å |
| a = 4.202 (1) Å | Cell parameters from 25 reflections |
| b = 20.956 (4) Å | θ = 3.5–23.5° |
| c = 9.276 (2) Å | µ = 3.93 mm−1 |
| β = 100.63 (3)° | T = 293 K |
| V = 802.8 (3) Å3 | Needle, red |
| Z = 2 | 0.38 × 0.08 × 0.04 mm |
| F(000) = 524 | |
Data collection top
R3m/V (Siemens)
diffractometer | 1277 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.080 |
| Graphite monochromator | θmax = 28.1°, θmin = 1.9° |
| ω–2θ scans | h = −5→5 |
| Absorption correction: ψ scan | k = 0→27 |
| Tmin = 0.278, Tmax = 0.337 | l = −12→12 |
| 3914 measured reflections | 1 standard reflections every 69 reflections |
| 1965 independent reflections | intensity decay: <1% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.099 | Riding |
| S = 0.98 | w = 1/[σ2(Fo2) + (0.0268P)2]
where P = (Fo2 + 2Fc2)/3 |
| 1965 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.78 e Å−3 |
| 0 restraints | Δρmin = −0.62 e Å−3 |
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 | |
| C01 | −0.6629 (15) | −0.0254 (3) | −0.3524 (8) | 0.0426 (15) | |
| H01A | −0.7582 | 0.0052 | −0.4195 | 0.051* | |
| C02 | −0.7531 (16) | −0.0890 (3) | −0.3743 (8) | 0.0474 (16) | |
| H02A | −0.9084 | −0.1009 | −0.4547 | 0.057* | |
| C03 | −0.6102 (14) | −0.1339 (3) | −0.2758 (7) | 0.0428 (15) | |
| H03A | −0.6725 | −0.1763 | −0.2904 | 0.051* | |
| C04 | −0.3734 (13) | −0.1181 (2) | −0.1537 (7) | 0.0333 (13) | |
| C05 | −0.2823 (13) | −0.0522 (3) | −0.1321 (7) | 0.0330 (13) | |
| C06 | −0.0459 (13) | −0.0334 (3) | −0.0101 (7) | 0.0308 (12) | |
| C07 | 0.2127 (14) | 0.1636 (3) | 0.0507 (7) | 0.0367 (14) | |
| C08 | −0.0120 (14) | 0.1447 (3) | −0.0650 (7) | 0.0378 (14) | |
| H08A | −0.1121 | 0.1751 | −0.1313 | 0.045* | |
| C09 | −0.0976 (13) | 0.0800 (3) | −0.0872 (6) | 0.0319 (12) | |
| C10 | −0.3482 (15) | 0.0620 (3) | −0.2160 (7) | 0.0397 (14) | |
| C11 | −0.4361 (13) | −0.0067 (2) | −0.2338 (7) | 0.0358 (13) | |
| O1 | −0.4752 (12) | 0.1020 (2) | −0.3042 (5) | 0.0608 (15) | |
| I1 | 0.31891 (10) | 0.261059 (19) | 0.08029 (6) | 0.04868 (17) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C01 | 0.049 (4) | 0.036 (3) | 0.039 (4) | 0.002 (3) | 0.000 (3) | 0.004 (3) |
| C02 | 0.051 (4) | 0.046 (4) | 0.043 (4) | −0.004 (3) | 0.002 (3) | −0.006 (3) |
| C03 | 0.052 (4) | 0.026 (3) | 0.053 (4) | −0.003 (3) | 0.017 (3) | −0.007 (3) |
| C04 | 0.039 (3) | 0.023 (3) | 0.041 (3) | 0.000 (2) | 0.013 (3) | 0.005 (3) |
| C05 | 0.040 (3) | 0.024 (3) | 0.037 (3) | 0.000 (2) | 0.012 (3) | 0.000 (3) |
| C06 | 0.036 (3) | 0.024 (3) | 0.035 (3) | 0.001 (2) | 0.012 (2) | −0.001 (2) |
| C07 | 0.044 (3) | 0.022 (3) | 0.047 (4) | −0.001 (2) | 0.014 (3) | −0.001 (3) |
| C08 | 0.049 (3) | 0.026 (3) | 0.041 (4) | 0.005 (2) | 0.018 (3) | 0.007 (3) |
| C09 | 0.041 (3) | 0.025 (3) | 0.031 (3) | 0.003 (2) | 0.009 (2) | 0.004 (2) |
| C10 | 0.052 (4) | 0.028 (3) | 0.038 (4) | 0.008 (3) | 0.004 (3) | 0.006 (3) |
| C11 | 0.043 (4) | 0.026 (3) | 0.040 (4) | 0.001 (2) | 0.010 (3) | 0.002 (3) |
| O1 | 0.074 (3) | 0.034 (2) | 0.062 (4) | 0.002 (2) | −0.017 (3) | 0.008 (2) |
| I1 | 0.0523 (3) | 0.02271 (19) | 0.0701 (3) | −0.00457 (19) | 0.00879 (19) | −0.0004 (2) |
Geometric parameters (Å, º) top
| C01—C11 | 1.373 (8) | C06—C09i | 1.389 (8) |
| C01—C02 | 1.391 (9) | C06—C06i | 1.456 (11) |
| C01—H01A | 0.9300 | C07—C08 | 1.351 (8) |
| C02—C03 | 1.370 (9) | C07—C04i | 1.427 (8) |
| C02—H02A | 0.9300 | C07—I1 | 2.098 (5) |
| C03—C04 | 1.402 (8) | C08—C09 | 1.409 (8) |
| C03—H03A | 0.9300 | C08—H08A | 0.9300 |
| C04—C07i | 1.427 (8) | C09—C06i | 1.389 (8) |
| C04—C05 | 1.437 (8) | C09—C10 | 1.488 (8) |
| C05—C11 | 1.412 (7) | C10—O1 | 1.222 (7) |
| C05—C06 | 1.417 (8) | C10—C11 | 1.489 (8) |
| | | |
| C11—C01—C02 | 121.3 (6) | C05—C06—C06i | 120.0 (6) |
| C11—C01—H01A | 119.3 | C08—C07—C04i | 120.7 (5) |
| C02—C01—H01A | 119.3 | C08—C07—I1 | 119.3 (4) |
| C03—C02—C01 | 119.1 (6) | C04i—C07—I1 | 119.9 (4) |
| C03—C02—H02A | 120.4 | C07—C08—C09 | 121.4 (5) |
| C01—C02—H02A | 120.4 | C07—C08—H08A | 119.3 |
| C02—C03—C04 | 122.4 (6) | C09—C08—H08A | 119.3 |
| C02—C03—H03A | 118.8 | C06i—C09—C08 | 120.8 (5) |
| C04—C03—H03A | 118.8 | C06i—C09—C10 | 120.2 (5) |
| C03—C04—C07i | 124.2 (5) | C08—C09—C10 | 119.0 (5) |
| C03—C04—C05 | 118.0 (5) | O1—C10—C09 | 121.4 (5) |
| C07i—C04—C05 | 117.8 (5) | O1—C10—C11 | 121.3 (6) |
| C11—C05—C06 | 120.8 (5) | C09—C10—C11 | 117.3 (5) |
| C11—C05—C04 | 118.6 (5) | C01—C11—C05 | 120.5 (5) |
| C06—C05—C04 | 120.5 (5) | C01—C11—C10 | 119.1 (5) |
| C09i—C06—C05 | 118.7 (5) | C05—C11—C10 | 120.4 (5) |
| C09i—C06—C06i | 121.3 (6) | | |
| | | |
| C11—C01—C02—C03 | −0.5 (12) | C07—C08—C09—C10 | 179.6 (6) |
| C01—C02—C03—C04 | −0.5 (11) | C06i—C09—C10—O1 | −179.1 (7) |
| C02—C03—C04—C07i | −178.3 (7) | C08—C09—C10—O1 | 1.6 (10) |
| C02—C03—C04—C05 | 0.5 (10) | C06i—C09—C10—C11 | 0.4 (9) |
| C03—C04—C05—C11 | 0.4 (9) | C08—C09—C10—C11 | −178.8 (6) |
| C07i—C04—C05—C11 | 179.3 (6) | C02—C01—C11—C05 | 1.5 (11) |
| C03—C04—C05—C06 | 179.6 (6) | C02—C01—C11—C10 | 179.9 (7) |
| C07i—C04—C05—C06 | −1.5 (9) | C06—C05—C11—C01 | 179.4 (6) |
| C11—C05—C06—C09i | 179.7 (6) | C04—C05—C11—C01 | −1.3 (9) |
| C04—C05—C06—C09i | 0.6 (9) | C06—C05—C11—C10 | 1.0 (9) |
| C11—C05—C06—C06i | −1.2 (11) | C04—C05—C11—C10 | −179.7 (6) |
| C04—C05—C06—C06i | 179.6 (6) | O1—C10—C11—C01 | 0.5 (11) |
| C04i—C07—C08—C09 | 0.7 (10) | C09—C10—C11—C01 | −179.1 (6) |
| I1—C07—C08—C09 | −178.3 (5) | O1—C10—C11—C05 | 178.9 (7) |
| C07—C08—C09—C06i | 0.3 (10) | C09—C10—C11—C05 | −0.6 (9) |
| Symmetry code: (i) −x, −y, −z. |
'4,10-Dichloro-anthanthrone' (pu288)
top
Crystal data top
| C22H8Cl2O2 | F(000) = 190 |
| Mr = 375.18 | Dx = 1.693 Mg m−3 |
| Triclinic, P_1 | Melting point > 300 K |
| a = 3.795 (1) Å | Mo Kα radiation, λ = 0.71072 Å |
| b = 9.527 (1) Å | Cell parameters from 25 reflections |
| c = 10.662 (1) Å | θ = 4.5–24.0° |
| α = 105.78 (1)° | µ = 0.46 mm−1 |
| β = 93.27 (1)° | T = 293 K |
| γ = 95.26 (1)° | Plate, orange |
| V = 368.04 (11) Å3 | 0.51 × 0.05 × 0.02 mm |
| Z = 1 | |
Data collection top
R3m/V (Siemens)
diffractometer | 842 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.091 |
| Graphite monochromator | θmax = 28.1°, θmin = 2.0° |
| ω–2θ scans | h = −5→5 |
| Absorption correction: ψ scan | k = −12→12 |
| Tmin = 0.973, Tmax = 0.991 | l = −14→14 |
| 3548 measured reflections | 1 standard reflections every 69 reflections |
| 1774 independent reflections | intensity decay: <1% |
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)] = 0.071 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.178 | All H-atom parameters refined |
| S = 0.93 | w = 1/[σ2(Fo2) + (0.0685P)2]
where P = (Fo2 + 2Fc2)/3 |
| 1774 reflections | (Δ/σ)max < 0.001 |
| 134 parameters | Δρmax = 0.40 e Å−3 |
| 0 restraints | Δρmin = −0.45 e Å−3 |
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 | |
| C01 | 0.1611 (13) | −0.4177 (5) | −0.1222 (5) | 0.0341 (11) | |
| C02 | 0.0342 (14) | −0.4797 (5) | −0.2518 (5) | 0.0403 (12) | |
| C03 | −0.1114 (14) | −0.3947 (5) | −0.3236 (4) | 0.0364 (12) | |
| C04 | −0.1422 (12) | −0.2445 (5) | −0.2644 (4) | 0.0295 (10) | |
| C05 | −0.0233 (12) | −0.1824 (4) | −0.1315 (4) | 0.0269 (10) | |
| C06 | −0.0598 (11) | −0.0314 (4) | −0.0684 (4) | 0.0249 (9) | |
| C07 | 0.2934 (13) | 0.1530 (5) | 0.3335 (4) | 0.0317 (11) | |
| C08 | 0.3311 (13) | 0.0092 (5) | 0.2740 (4) | 0.0343 (11) | |
| C09 | 0.2136 (12) | −0.0514 (4) | 0.1409 (4) | 0.0279 (10) | |
| C10 | 0.2648 (13) | −0.2075 (5) | 0.0785 (4) | 0.0337 (11) | |
| C11 | 0.1315 (12) | −0.2716 (4) | −0.0601 (4) | 0.0283 (10) | |
| H01 | 0.270 (13) | −0.470 (5) | −0.076 (4) | 0.037 (13)* | |
| H02 | 0.066 (14) | −0.575 (6) | −0.302 (4) | 0.049 (14)* | |
| H03 | −0.201 (11) | −0.440 (4) | −0.416 (4) | 0.024 (11)* | |
| H08 | 0.427 (14) | −0.055 (6) | 0.323 (5) | 0.054 (15)* | |
| O1 | 0.4278 (10) | −0.2779 (3) | 0.1395 (3) | 0.0465 (10) | |
| Cl1 | 0.4434 (4) | 0.22487 (14) | 0.49922 (11) | 0.0470 (4) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C01 | 0.039 (3) | 0.018 (2) | 0.048 (3) | 0.010 (2) | 0.008 (2) | 0.011 (2) |
| C02 | 0.051 (3) | 0.018 (2) | 0.046 (3) | 0.004 (2) | 0.009 (2) | −0.001 (2) |
| C03 | 0.043 (3) | 0.024 (2) | 0.036 (2) | 0.001 (2) | 0.006 (2) | −0.0005 (19) |
| C04 | 0.032 (3) | 0.023 (2) | 0.033 (2) | 0.006 (2) | 0.0045 (18) | 0.0065 (18) |
| C05 | 0.033 (3) | 0.016 (2) | 0.032 (2) | 0.0040 (19) | 0.0074 (18) | 0.0070 (17) |
| C06 | 0.027 (3) | 0.0162 (19) | 0.033 (2) | 0.0037 (18) | 0.0064 (17) | 0.0083 (16) |
| C07 | 0.038 (3) | 0.030 (2) | 0.024 (2) | 0.004 (2) | −0.0011 (18) | 0.0040 (17) |
| C08 | 0.044 (3) | 0.027 (2) | 0.035 (2) | 0.009 (2) | 0.002 (2) | 0.012 (2) |
| C09 | 0.034 (3) | 0.015 (2) | 0.036 (2) | 0.0058 (19) | −0.0003 (19) | 0.0091 (17) |
| C10 | 0.037 (3) | 0.023 (2) | 0.042 (2) | 0.005 (2) | 0.003 (2) | 0.0110 (19) |
| C11 | 0.028 (3) | 0.017 (2) | 0.041 (2) | 0.0025 (19) | 0.0021 (19) | 0.0094 (18) |
| O1 | 0.061 (3) | 0.0259 (18) | 0.054 (2) | 0.0145 (18) | −0.0081 (17) | 0.0141 (15) |
| Cl1 | 0.0667 (10) | 0.0367 (7) | 0.0324 (6) | 0.0097 (6) | −0.0079 (5) | 0.0022 (5) |
Geometric parameters (Å, º) top
| C01—C02 | 1.384 (6) | C06—C09i | 1.387 (5) |
| C01—C11 | 1.388 (6) | C06—C06i | 1.446 (7) |
| C01—H01 | 0.90 (4) | C07—C08 | 1.369 (6) |
| C02—C03 | 1.385 (7) | C07—C04i | 1.423 (6) |
| C02—H02 | 0.94 (5) | C07—Cl1 | 1.752 (4) |
| C03—C04 | 1.417 (6) | C08—C09 | 1.407 (6) |
| C03—H03 | 0.99 (4) | C08—H08 | 0.99 (5) |
| C04—C05 | 1.409 (5) | C09—C06i | 1.387 (5) |
| C04—C07i | 1.423 (6) | C09—C10 | 1.491 (6) |
| C05—C11 | 1.427 (6) | C10—O1 | 1.234 (5) |
| C05—C06 | 1.437 (5) | C10—C11 | 1.476 (6) |
| | | |
| C02—C01—C11 | 121.0 (4) | C05—C06—C06i | 120.0 (5) |
| C02—C01—H01 | 121 (3) | C08—C07—C04i | 122.0 (4) |
| C11—C01—H01 | 118 (3) | C08—C07—Cl1 | 118.2 (3) |
| C01—C02—C03 | 120.3 (4) | C04i—C07—Cl1 | 119.9 (3) |
| C01—C02—H02 | 125 (3) | C07—C08—C09 | 119.4 (4) |
| C03—C02—H02 | 114 (3) | C07—C08—H08 | 122 (3) |
| C02—C03—C04 | 120.5 (4) | C09—C08—H08 | 119 (3) |
| C02—C03—H03 | 120 (2) | C06i—C09—C08 | 121.5 (4) |
| C04—C03—H03 | 120 (2) | C06i—C09—C10 | 120.5 (4) |
| C05—C04—C03 | 119.2 (4) | C08—C09—C10 | 118.0 (4) |
| C05—C04—C07i | 118.1 (4) | O1—C10—C11 | 121.5 (4) |
| C03—C04—C07i | 122.6 (4) | O1—C10—C09 | 120.7 (4) |
| C04—C05—C11 | 119.2 (4) | C11—C10—C09 | 117.7 (4) |
| C04—C05—C06 | 120.3 (4) | C01—C11—C05 | 119.7 (4) |
| C11—C05—C06 | 120.4 (4) | C01—C11—C10 | 120.3 (4) |
| C09i—C06—C05 | 118.7 (4) | C05—C11—C10 | 120.0 (4) |
| C09i—C06—C06i | 121.3 (5) | | |
| | | |
| C11—C01—C02—C03 | 2.8 (8) | C07—C08—C09—C10 | 178.9 (5) |
| C01—C02—C03—C04 | −1.9 (8) | C06i—C09—C10—O1 | 173.9 (4) |
| C02—C03—C04—C05 | −0.1 (7) | C08—C09—C10—O1 | −5.0 (7) |
| C02—C03—C04—C07i | −179.3 (5) | C06i—C09—C10—C11 | −2.8 (6) |
| C03—C04—C05—C11 | 1.2 (7) | C08—C09—C10—C11 | 178.2 (4) |
| C07i—C04—C05—C11 | −179.6 (4) | C02—C01—C11—C05 | −1.7 (7) |
| C03—C04—C05—C06 | −178.4 (4) | C02—C01—C11—C10 | 179.4 (5) |
| C07i—C04—C05—C06 | 0.8 (6) | C04—C05—C11—C01 | −0.3 (7) |
| C04—C05—C06—C09i | 0.0 (6) | C06—C05—C11—C01 | 179.3 (4) |
| C11—C05—C06—C09i | −179.6 (4) | C04—C05—C11—C10 | 178.6 (4) |
| C04—C05—C06—C06i | 179.5 (5) | C06—C05—C11—C10 | −1.8 (6) |
| C11—C05—C06—C06i | −0.1 (7) | O1—C10—C11—C01 | 5.4 (7) |
| C04i—C07—C08—C09 | −0.8 (8) | C09—C10—C11—C01 | −177.9 (4) |
| Cl1—C07—C08—C09 | −179.9 (4) | O1—C10—C11—C05 | −173.5 (5) |
| C07—C08—C09—C06i | −0.1 (7) | C09—C10—C11—C05 | 3.2 (6) |
| Symmetry code: (i) −x, −y, −z. |
journal menu
research papers
, Z = 1. The molecular structures are almost identical and the unit-cell parameters show some similarities for all three compounds, but the crystal structures are neither isotypic to another nor to the unsubstituted anthanthrone, which crystallizes in P21/c, Z = 8. In order to explain why the four anthanthrone derivatives have four different crystal structures, lattice-energy minimizations were performed using anisotropic atom–atom model potentials as well as using the semi-classical density sums (SCDS-Pixel) approach. The calculations showed the crystal structures of the dichloro and the diiodo derivatives to be the most stable ones for the corresponding compound; whereas for dibromo-anthanthrone the calculations suggest that the dichloro and diiodo structure types should be more stable than the experimentally observed structure. An experimental search for new polymorphs of dibromo-anthanthrone was carried out, but the experiments were hampered by the remarkable insolubility of the compound. A metastable nanocrystalline second polymorph of the dibromo derivative does exist, but it is not isostructural to the dichloro or diiodo compound. In order to determine the crystal structure of this phase, crystal structure predictions were performed in various space groups, using anisotropic atom–atom potentials. For all low-energy structures, X-ray powder patterns were calculated and compared with the experimental diagram, which consisted of a few broad lines only. It turned out that the crystallinity of this phase was not sufficient to determine which of the calculated structures corresponds to the actual structure of this nanocrystalline polymorph.
