research communications
of Pigment Red 254 from X-ray powder diffraction data
aInstitute of Geology, Karelian Research Centre, Russian Academy of Sciences, Pushkinskaya 11, 185910 Petrozavodsk, Russian Federation
*Correspondence e-mail: ivashevskaja@yahoo.com
The 18H10Cl2N2O2; 3,6-bis(4-chlorophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione] was solved from laboratory X-ray powder diffraction data using the simulated annealing method followed by because the very low solubility of the pigment in all solvents impedes the growth of single crystals suitable for X-ray analysis. The molecule lies across an inversion center. The dihedral angle between the benzene ring and the pyrrole ring in the unique part of the molecule is 11.1 (2)°. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming chains along [110] incorporating R22(8) rings.
of Pigment Red 254 [P.R. 254, CKeywords: powder diffraction; Pigment Red 254; diketopyrrolo-pyrrole (DPP) pigments; simulated annealing; Rietveld refinement.
CCDC reference: 1517793
1. Chemical context
Within the range of diketopyrrolo-pyrrole (DPP) pigments presently offered to the market, P.R. 254 plays the most important role (Herbst & Hunger, 2004), this commercially available type the pigment being widely used in industrial paints, for example for automotive finishes, and plastics which are processed at high temperature. P.R. 254 affords medium shades of red in full shades, while reductions made with a white paint are somewhat bluish red. The pigment demonstrates excellent fastness to organic solvents and weather-fastness, as well as good coloristic and fastness properties. It also shows good hiding power and high tinctorial strength.
The pigment exhibits very low solubility in all solvents, impeding the growth of single crystals suitable for X-ray analyses. Pigments are not dissolved in their application media, but finely dispersed. Consequently the final product properties depend on the
of the pigments. The was successfully solved from laboratory X-ray powder diffraction data using the simulated annealing method followed by Rietveld refinement.2. Structural commentary
The molecule of the title compound (Fig. 1) lies across an inversion center. The dihedral angle between the benzene (C1–C6) and pyrrole (N1/C7–C9/C8 rings is 11.1 (2)°. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming one-dimensional chains along [110] incorporating (8) rings.que part of the molecule (C1/C2/C3/C4/C5/C6) and the pyrrole ring [C7/C9/N1/C8/C8(−x + 1, −y + 1, −z + 1)] is 11.1 (2)°. An intramolecular C—H⋯O hydrogen bond occurs (Table 1).
3. Supramolecular features
In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming chains along [110] incorporating (8) rings (Fig. 2). In addition, π–π stacking interactions between symmetry-related benzene rings with a centroid–centroid distance of 3.871 (2)° connect these chains along [100] (Fig. 3).
4. Synthesis and crystallization
The technical product P.R. 254 (TR008.052.11-F) supplied by Clariant Produkte (Deutschland) GmbH was taken as is.
5. Refinement
Crystal data, data collection and structure . was carried out with TOPAS (Coelho, 2007) using all diffraction data. The TOPAS input file (including all crystallographic constraints and chemical restraints) was generated automatically by the DASH-to-TOPAS link.
details are summarized in Table 2
|
Simulated annealing method (SA) was used to solve the et al., 2016). The half of the molecule has three flexible torsion angles, which combined with three translational and three orientational corresponds to a total of nine The program DASH (David et al., 2006) was used for structure solution. DASH allows the torsion angles to be restricted to intervals that significantly reduce the search space. These three flexible torsion angles and their allowed ranges are shown in Fig. 4. The powder pattern was truncated to a real space resolution of 2.6 Å, which for Cu Kα1 radiation corresponds to 34.6° in 2θ. The background was subtracted with a Bayesian high-pass filter (David & Sivia, 2001). The number of SA runs was increased to 50 to get better statistics regarding reproducibility. The background subtraction, Pawley and SA algorithms were used as implemented in the program DASH.
from the powder pattern in The starting molecular geometry was built from known of similar compound from the Cambridge Structural Database (CSD; GroomAccurate peak positions for indexing were obtained by fitting 20 manually selected peaks with an asymmetry-corrected Voigt function. Indexing was done with the program DICVOL91 (Boultif & Louër, 1991). A triclinic was determined with M(20) = 40.7 (de Wolff et al., 1968), F(20) = 82.8 (Smith & Snyder, 1979). From volume considerations, the can contain one molecule of P.R. 254 (Z = 1). The molecule has an inversion centre, which means the must consist of a one half of the molecule.
Pawley ) was carried out for refining the background, unit-cell parameters, zero-point error, peak-width and peak-asymmetry parameters. It allows extracting integrated intensities and their correlations. All intensities were refined without reference to a structural model and the result is the best fit that is theoretically possible: Rwp = 13.57, Rexp = 11.20, χ2 = 1.467.
(Pawley, 1981Suitable chemical restraints were applied for all bond lengths, valence angles and the planarity of the aromatic ring systems (including the five-membered condensed system). Anisotropic peak broadening was included to allow the peak profiles to be described accurately. The discrepancies between the observed and the calculated profile appeared to systematically depend on the hkl indices of the reflections, indicating in the [001] direction. The March–Dollase formula (Dollase, 1986) was used. The diffraction profiles and the differences between the measured and calculated profiles are shown in Fig. 5.
Supporting information
CCDC reference: 1517793
https://doi.org/10.1107/S2056989017003309/lh5832sup1.cif
contains datablocks global, I. DOI:Rietveld powder data: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003309/lh5832Isup2.rtv
Supporting information file. DOI: https://doi.org/10.1107/S2056989017003309/lh5832Isup3.cml
Data collection: WINXPOW (Stoe & Cie, 2004); cell
TOPAS-Academic (Coelho, 2007); data reduction: DASH3.1 (David et al., 2006); program(s) used to solve structure: DASH3.1 (David et al., 2006); program(s) used to refine structure: TOPAS-Academic (Coelho, 2007); molecular graphics: Mercury (Macrae et al., 2008).C18H10Cl2N2O2 | V = 380.45 (3) Å3 |
Mr = 357.19 | Z = 1 |
Triclinic, P1 | Dx = 1.57 Mg m−3 |
a = 3.871 (1) Å | Cu Kα1 radiation, λ = 1.54056 Å |
b = 6.553 (1) Å | T = 293 K |
c = 15.292 (1) Å | Particle morphology: powder |
α = 92.773 (3)° | red |
β = 94.656 (3)° | flat_sheet, 10 × 10 mm |
γ = 99.627 (2)° |
Stoe Stadi-P with linear PSD diffractometer | Data collection mode: transmission |
Radiation source: sealed X-ray tube | Scan method: step |
Primary focussing, Ge 111 monochromator | 2θmin = 2.00°, 2θmax = 60.00°, 2θstep = 0.01° |
Specimen mounting: sample was prepared between two polyacetate films |
Refinement on Inet | 115 parameters |
Least-squares matrix: full with fixed elements per cycle | 44 restraints |
Rp = 6.506 | 0 constraints |
Rwp = 8.578 | All H-atom parameters refined |
Rexp = 7.467 | Weighting scheme based on measured s.u.'s w = 1/σ[Yobs)2 |
5800 data points | (Δ/σ)max = 0.001 |
Excluded region(s): none | Background function: Chebyshev function with 20 terms |
Profile function: fundamental parameters | Preferred orientation correction: March–Dollase formula (Dollase, 1986), (001) direction |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8418 (7) | 0.4738 (6) | 0.6911 (3) | 0.05373 | |
C2 | 0.7516 (10) | 0.2631 (7) | 0.7088 (3) | 0.05373 | |
C3 | 0.8543 (9) | 0.1967 (6) | 0.7905 (3) | 0.05373 | |
C4 | 1.0452 (8) | 0.3351 (7) | 0.8528 (3) | 0.05373 | |
C5 | 1.1403 (8) | 0.5402 (7) | 0.8377 (3) | 0.05373 | |
C6 | 1.0380 (9) | 0.6065 (7) | 0.7573 (3) | 0.05373 | |
C7 | 0.7380 (7) | 0.5404 (6) | 0.6038 (3) | 0.05373 | |
C8 | 0.4818 (10) | 0.5527 (8) | 0.4587 (4) | 0.05373 | |
C9 | 0.8702 (6) | 0.7478 (4) | 0.5715 (2) | 0.05373 | |
H2 | 0.606 (5) | 0.157 (2) | 0.6614 (15) | 0.06447 | |
H3 | 0.796 (4) | 0.039 (2) | 0.8095 (13) | 0.06447 | |
H5 | 1.286 (4) | 0.644 (2) | 0.8892 (16) | 0.06447 | |
H6 | 1.113 (4) | 0.767 (2) | 0.7484 (14) | 0.06447 | |
H7 | 0.774 (5) | 0.879 (2) | 0.4529 (17) | 0.06447 | |
O1 | 1.0679 (7) | 0.8859 (6) | 0.6108 (3) | 0.05373 | |
N1 | 0.7025 (7) | 0.7478 (5) | 0.4806 (3) | 0.05373 | |
Cl1 | 1.1601 (7) | 0.2385 (4) | 0.9528 (3) | 0.05373 |
C1—C2 | 1.411 (6) | C3—H3 | 1.08 (2) |
C1—C6 | 1.388 (5) | C5—H5 | 1.07 (2) |
C1—C7 | 1.470 (6) | C6—H6 | 1.06 (1) |
C2—C3 | 1.392 (6) | C9—O1 | 1.186 (4) |
C3—C4 | 1.362 (6) | C9—N1 | 1.485 (5) |
C4—C5 | 1.369 (6) | N1—C8 | 1.422 (5) |
C5—C6 | 1.374 (6) | N1—H7 | 0.98 (2) |
C7—C9 | 1.492 (5) | C4—Cl1 | 1.736 (6) |
C2—H2 | 1.04 (2) | ||
C2—C1—C6 | 117.3 (4) | C2—C3—H3 | 125 (1) |
C2—C1—C7 | 119.3 (3) | C4—C3—H3 | 115 (1) |
C6—C1—C7 | 123.4 (3) | C6—C5—H5 | 122 (1) |
C1—C2—C3 | 120.0 (3) | C4—C5—H5 | 119 (1) |
C1—C6—C5 | 122.5 (4) | C7—C9—O1 | 126.8 (4) |
C1—C7—C9 | 124.4 (3) | C7—C9—N1 | 106.4 (2) |
C2—C3—C4 | 119.8 (4) | C9—N1—C8 | 108.8 (4) |
C6—C5—C4 | 118.5 (4) | O1—C9—N1 | 126.8 (3) |
C3—C4—C5 | 121.8 (4) | C3—C4—Cl1 | 116.6 (4) |
C1—C2—H2 | 120 (1) | C5—C4—Cl1 | 121.6 (3) |
C3—C2—H2 | 119.7 (9) | C9—N1—H7 | 113 (1) |
C1—C6—H6 | 121 (1) | C8—N1—H7 | 138 (1) |
C5—C6—H6 | 116 (1) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H7···O1i | 0.985 (17) | 1.904 (18) | 2.884 (5) | 173 (2) |
C2—H2···O1ii | 1.04 (2) | 2.542 (18) | 3.489 (6) | 151.2 (16) |
C2—H2···N1iii | 1.04 (2) | 2.55 (2) | 3.255 (6) | 124.8 (11) |
C6—H6···O1 | 1.062 (14) | 2.28 (2) | 2.959 (6) | 119.9 (14) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+1, −z+1. |
Acknowledgements
Professor Dr Martin Schmidt (Frankfurt University) is gratefully acknowledged for the technical product P.R. 254 (TR008.052.11-F). Dr Lothar Fink and Edith Alig (Frankfurt University) are gratefully acknowledged for the collection of the powder diffraction patterns.
Funding information
Funding for this research was provided by: Deutscher Akademischer Austauschdienst, Forschungsaufenthalte für Hochschullehrer und Wissenschaftlerhttps://doi.org/10.13039/501100001655.
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