research communications
Acridine form IX
aDepartment of Physics and Astronomy, Stony Brook, NY 11794-3800, USA, bDepartment of Chemistry, Ben Gurion University of the Negev, Beer Sheva, 84105, Israel, and cX-ray Science Division, Argonne National Laboratory, Lemont, IL 60439, USA
*Correspondence e-mail: pstephens@stonybrook.edu
We report a new polymorph of acridine, C13H9N, denoted form IX, obtained as thin needles by slow evaporation of a toluene solution. The structure was solved and refined from powder X-ray data. The structures of five unsolvated forms were previously known, but this is only the second with one molecule in the The melting point [differential scanning (DSC) onset] and heat of fusion are 108.8 (3) °C and 19.2 (4) kJ mol−1, respectively.
Keywords: crystal structure; powder diffraction; acridine; polymorph.
CCDC reference: 1869547
1. Chemical context
With the crystal structures of five forms already reported, acridine is already one of the more prolifically polymorphic molecules known [see Phillips (1956), Phillips et al. (1960), Mei & Wolf (2004), Braga et al. (2010), Kupka et al. (2012), and Lusi et al. (2015)]; two additional forms have been described, but structures were not reported, by Herbstein & Schmidt (1955) and Braga et al. (2010). This large number of observed forms seems particularly noteworthy in view of the fact that the molecule has zero degrees of flexibility, although perhaps counterintuitively, some 40 rigid molecules are observed to be polymorphic (Cruz-Cabeza & Bernstein, 2013).
2. Structural commentary
The form described here was previously predicted by Price & Price (unpublished) using CrystalPredictor (Karamertzanis & Pantilides, 2005) to generate a crystal energy landscape, limited to one independent molecule in the cell in the most common space groups. These were relaxed to mechanically stable structures with DMACRYS (Price et al., 2010). This new form corresponded to one of two structures with the lowest computed lattice energy. Further details are available in Schur et al. (2019). Geometry details for form IX are given in Table 1.
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3. Supramolecular features
The four molecules in the
are connected by a cycle of C⋯H (2.81 Å) and N⋯H (2.73 Å) contacts that are shorter than the sum of the van der Waals radii. There is also an H⋯H interaction of 2.29 Å.4. Synthesis and crystallization
Crystals were grown by slow evaporation from a toluene solution. Thin needles of form IX samples were taken from the walls of crystallization vials. The material was gently crushed and loaded into a glass capillary for powder diffraction measurements. Further details are available in Schur (2013).
5. details
Crystal data, data collection and structure . Data were collected at the high resolution powder diffractometer at the National Synchrotron Light Source beamline X16C, operated in step scanning mode. X-rays of wavelength 0.69979 Å were selected by a Si(111) channel cut monochromator. Diffracted X-rays were selected by a Ge(111) analyzer before an NaI(Tl) The sample of form IX was obtained concomitantly with forms III (1.4%) and VII (1.1%), which were included in the Rietveld fit, with atomic positions fixed at literature values.
details are summarized in Table 2The molecule was defined by a z-matrix for Mirror symmetry was imposed on bond distances and angles; 7 distances, 6 angles, and 11 torsions were refined. There is a single isotropic displacement parameter for all C and N atoms; that of H atoms is 1.5 times greater. All H atoms are tethered.
Standard uncertainties were calculated by a bootstrap method, described in Coelho (2016). As such, they reflect the propagation of statistical errors from the raw data and do not take account of systematic errors. Realistic estimates of the precision of measurements are somewhat larger.
The . Fig. 2 illustrates the atom-labeling scheme, and Fig. 3 shows the three-dimensional structure, with short intermolecular interactions shown as broken lines.
plot is shown in Fig. 1The ; Dollase, 1986), and anisotropic microstrain broadening (Stephens, 1999).
model included parameter 1.08 in the (100) direction (March, 1932Supporting information
CCDC reference: 1869547
https://doi.org/10.1107/S2056989019003645/eb2017sup1.cif
contains datablocks global, I. DOI:Rietveld powder data: contains datablock I. DOI: https://doi.org/10.1107/S2056989019003645/eb2017Isup2.rtv
Supporting information file. DOI: https://doi.org/10.1107/S2056989019003645/eb2017Isup3.cml
Data collection: spec; cell
TOPAS-Academic (Coelho, 2016); data reduction: TOPAS-Academic (Coelho, 2016); program(s) used to solve structure: TOPAS-Academic (Coelho, 2016); program(s) used to refine structure: TOPAS-Academic (Coelho, 2016); molecular graphics: Mercury (Macrae et al., 2008).C13H9N | Z = 4 |
Mr = 179.21 | Dx = 1.276 Mg m−3 |
Monoclinic, P21/n | Synchrotron radiation, λ = 0.699789 Å |
a = 11.28453 (11) Å | µ = 0.08 mm−1 |
b = 12.38182 (12) Å | T = 295 K |
c = 6.67905 (9) Å | Particle morphology: thin needles |
β = 92.0618 (6)° | yellow-white |
V = 932.61 (2) Å3 | cylinder, 8 × 1 mm |
Huber 401 diffractometer, Ge(111) analyzer crystal | Data collection mode: transmission |
Radiation source: National Synchrotron Light Source | Scan method: step |
Channel cut Si(111) monochromator | 2θmin = 2°, 2θmax = 35°, 2θstep = 0.005° |
Specimen mounting: 1 mm glass capillary, spun during data collection |
Least-squares matrix: full | 12 restraints |
Rp = 0.041 | 22 constraints |
Rwp = 0.050 | H-atom parameters not refined |
Rexp = 0.028 | Weighting scheme based on measured s.u.'s |
RBragg = 0.011 | (Δ/σ)max = 0.02 |
6601 data points | Background function: 9th order Chebyshev plus broad pseudo-Voigt |
Profile function: Convolution of Gaussian and Lorentzian, with anisotropic strain broadening per Stephens (1999). | Preferred orientation correction: March parameter 1.084 in (1 0 0) direction |
81 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1540 (5) | 0.1053 (19) | 0.045 (2) | 0.0474 (5)* | |
C1 | 0.1213 (11) | 0.003 (3) | −0.252 (4) | 0.0474 (5)* | |
C2 | 0.1640 (14) | −0.048 (2) | −0.417 (3) | 0.0474 (5)* | |
C3 | 0.2853 (15) | −0.0476 (11) | −0.4573 (15) | 0.0474 (5)* | |
C4 | 0.3633 (9) | 0.0068 (7) | −0.3327 (10) | 0.0474 (5)* | |
C5 | 0.4001 (2) | 0.1154 (2) | −0.0256 (3) | 0.0474 (5)* | |
C6 | 0.4263 (13) | 0.2290 (7) | 0.2776 (12) | 0.0474 (5)* | |
C7 | 0.379 (2) | 0.2748 (11) | 0.4427 (15) | 0.0474 (5)* | |
C8 | 0.256 (2) | 0.266 (2) | 0.471 (3) | 0.0474 (5)* | |
C9 | 0.1830 (18) | 0.210 (4) | 0.341 (6) | 0.0474 (5)* | |
C10 | 0.1992 (5) | 0.0588 (10) | −0.1120 (15) | 0.0474 (5)* | |
C11 | 0.3234 (4) | 0.0603 (4) | −0.1568 (6) | 0.0474 (5)* | |
C12 | 0.3543 (7) | 0.1655 (3) | 0.1406 (7) | 0.0474 (5)* | |
C13 | 0.2282 (7) | 0.1578 (9) | 0.1666 (17) | 0.0474 (5)* | |
H1 | 0.0388 (12) | 0.002 (4) | −0.229 (6) | 0.0711 (8)* | |
H2 | 0.1103 (18) | −0.086 (2) | −0.504 (4) | 0.0711 (8)* | |
H3 | 0.313 (2) | −0.0838 (17) | −0.572 (2) | 0.0711 (8)* | |
H4 | 0.4453 (10) | 0.0071 (13) | −0.3603 (18) | 0.0711 (8)* | |
H5 | 0.4825 (3) | 0.1185 (6) | −0.0491 (8) | 0.0711 (8)* | |
H6 | 0.5086 (12) | 0.2370 (14) | 0.256 (2) | 0.0711 (8)* | |
H7 | 0.428 (3) | 0.315 (2) | 0.535 (3) | 0.0711 (8)* | |
H8 | 0.224 (3) | 0.299 (3) | 0.586 (4) | 0.0711 (8)* | |
H9 | 0.1006 (19) | 0.205 (6) | 0.364 (7) | 0.0711 (8)* |
N1—C10 | 1.315 (18) | C9—C13 | 1.44 (4) |
N1—C13 | 1.317 (18) | C10—C11 | 1.444 (7) |
C1—C2 | 1.37 (3) | C12—C13 | 1.443 (11) |
C1—C10 | 1.44 (3) | C1—H1 | 0.95 |
C2—C3 | 1.41 (2) | C2—H2 | 0.95 |
C3—C4 | 1.367 (16) | C3—H3 | 0.95 |
C4—C11 | 1.435 (9) | C4—H4 | 0.95 |
C5—C11 | 1.389 (5) | C5—H5 | 0.95 |
C5—C12 | 1.388 (6) | C6—H6 | 0.95 |
C6—C7 | 1.366 (17) | C7—H7 | 0.95 |
C6—C12 | 1.436 (12) | C8—H8 | 0.95 |
C7—C8 | 1.41 (3) | C9—H9 | 0.95 |
C8—C9 | 1.36 (4) | ||
C10—N1—C13 | 116.9 (7) | N1—C13—C12 | 124.5 (9) |
C2—C1—C10 | 121.3 (12) | C9—C13—C12 | 116.5 (13) |
C1—C2—C3 | 121.7 (17) | C2—C1—H1 | 120 (4) |
C2—C3—C4 | 119.7 (13) | C10—C1—H1 | 119 (4) |
C3—C4—C11 | 120.8 (10) | C1—C2—H2 | 119 (2) |
C11—C5—C12 | 118.9 (4) | C3—C2—H2 | 119 (2) |
C7—C6—C12 | 120.9 (14) | C2—C3—H3 | 120 (2) |
C6—C7—C8 | 119.4 (15) | C4—C3—H3 | 120 (2) |
C7—C8—C9 | 122 (2) | C3—C4—H4 | 119.6 (12) |
C8—C9—C13 | 121.3 (18) | C11—C4—H4 | 119.6 (11) |
N1—C10—C1 | 118.9 (10) | C11—C5—H5 | 120.5 (4) |
N1—C10—C11 | 124.5 (8) | C12—C5—H5 | 120.6 (5) |
C1—C10—C11 | 116.6 (11) | C7—C6—H6 | 119.5 (15) |
C4—C11—C5 | 122.5 (5) | C12—C6—H6 | 119.6 (12) |
C4—C11—C10 | 120.0 (7) | C6—C7—H7 | 120 (3) |
C5—C11—C10 | 117.6 (5) | C8—C7—H7 | 120 (2) |
C5—C12—C6 | 122.4 (8) | C7—C8—H8 | 119 (3) |
C5—C12—C13 | 117.7 (6) | C9—C8—H8 | 120 (3) |
C6—C12—C13 | 119.8 (8) | C8—C9—H9 | 120 (5) |
N1—C13—C9 | 119.0 (13) | C13—C9—H9 | 119 (5) |
Footnotes
‡Deceased.
Acknowledgements
We are grateful for useful discussions with Sarah L. Price and Louise S. Price of University College, London.
Funding information
Funding for this research was provided by: United States–Israel Binational Science Foundation (grant No. 2004118); U.S. Department of Energy, Office of Basic Energy Sciences (contract No. DE-AC02-98CH10886).
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