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Title: ROY Revisited, Again: The Eighth Solved Structure

Abstract

X-ray powder diffraction and crystal structure prediction (CSP) algorithms were used in synergy to establish the crystal structure of the eighth polymorph of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY), form R05. R05 crystallizes in the monoclinic space group P2_1 with lattice parameters a = 11.479(4) Å, b = 11.030(1) Å, c = 10.840(6) Å, β = 118.23(1)°. This is both the first acentric ROY polymorph, and the first with Z' > 1. The torsion angles defined by the S-C-N-C atom sequence of each molecule in the asymmetric unit are -34.0° and 44.9°. These angles fall between those previously determined for the red and orange forms of ROY. Hirshfeld surface analysis was employed to understand the crystal packing and intermolecular interactions in R05 and an updated energy stability ranking was determined using computational methods. Finally, although the application of CSP was critical to the structure solution of R05, energy stability rankings determined using a series of DFT vdW-inclusive models substantially deviate from experiment, indicating that ROY polymorphism continues to be a challenge for CSP.

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [1];  [6];  [2]
  1. New York Univ. (NYU), NY (United States). Dept. of Chemistry and Molecular Design Inst.
  2. Univ. of Nevada, Las Vegas, NV (United States). High Pressure Science and Engineering Center (HiPSEC), and Dept. of Physics and Astronomy
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-ray Science Division
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II), Photon Sciences Division
  5. New York Univ. (NYU), NY (United States). Dept. of Chemistry and Molecular Design Inst.; Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  6. New York Univ. (NYU), NY (United States). Dept. of Chemistry and Molecular Design Inst.; Waseda Univ., Shinjuku (Japan). Dept. of Advanced Science and Engineering
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1436447
Alternate Identifier(s):
OSTI ID: 1461212
Report Number(s):
BNL-203633-2018-JAAM
Journal ID: ISSN 1359-6640; FDISE6
Grant/Contract Number:  
SC0012704; NA0001982
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Name: Faraday Discussions; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Tan, Melissa, Shtukenberg, Alexander G., Zhu, Shengcai, Xu, Wenqian, Dooryhee, Eric, Nichols, Shane M., Ward, Michael David, Kahr, Bart, and Zhu, Qiang. ROY Revisited, Again: The Eighth Solved Structure. United States: N. p., 2018. Web. doi:10.1039/C8FD00039E.
Tan, Melissa, Shtukenberg, Alexander G., Zhu, Shengcai, Xu, Wenqian, Dooryhee, Eric, Nichols, Shane M., Ward, Michael David, Kahr, Bart, & Zhu, Qiang. ROY Revisited, Again: The Eighth Solved Structure. United States. doi:10.1039/C8FD00039E.
Tan, Melissa, Shtukenberg, Alexander G., Zhu, Shengcai, Xu, Wenqian, Dooryhee, Eric, Nichols, Shane M., Ward, Michael David, Kahr, Bart, and Zhu, Qiang. Mon . "ROY Revisited, Again: The Eighth Solved Structure". United States. doi:10.1039/C8FD00039E.
@article{osti_1436447,
title = {ROY Revisited, Again: The Eighth Solved Structure},
author = {Tan, Melissa and Shtukenberg, Alexander G. and Zhu, Shengcai and Xu, Wenqian and Dooryhee, Eric and Nichols, Shane M. and Ward, Michael David and Kahr, Bart and Zhu, Qiang},
abstractNote = {X-ray powder diffraction and crystal structure prediction (CSP) algorithms were used in synergy to establish the crystal structure of the eighth polymorph of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY), form R05. R05 crystallizes in the monoclinic space group P2_1 with lattice parameters a = 11.479(4) Å, b = 11.030(1) Å, c = 10.840(6) Å, β = 118.23(1)°. This is both the first acentric ROY polymorph, and the first with Z' > 1. The torsion angles defined by the S-C-N-C atom sequence of each molecule in the asymmetric unit are -34.0° and 44.9°. These angles fall between those previously determined for the red and orange forms of ROY. Hirshfeld surface analysis was employed to understand the crystal packing and intermolecular interactions in R05 and an updated energy stability ranking was determined using computational methods. Finally, although the application of CSP was critical to the structure solution of R05, energy stability rankings determined using a series of DFT vdW-inclusive models substantially deviate from experiment, indicating that ROY polymorphism continues to be a challenge for CSP.},
doi = {10.1039/C8FD00039E},
journal = {Faraday Discussions},
number = ,
volume = ,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}

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