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Symmetry-controlled rearrangements in Piedfort Units (PU) of 2,4,6-triaryloxy-1,3,5-triazines

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Abstract

2,4,6-triaryloxy-1,3,5-triazines (POT) form in general molecular diads, termed as Piedfort Units (PU), in their crystals and their clathrates. Their bulky phenyl substituents (R = Me, F, Cl, Br, I, CN) in ortho, meta or para position substantially hinder internal rotations. Instead, non-crystallographic rotations (ncr) or translations (nct) are the bridges between the semirigid homologues or analogues, occasionally polymorphs. They occur in the space groups R3c (161), \(R\bar 3\) (148), \(P\bar 3c1\) (165), P63/m (176), \(P\bar 31c\) (163), P21/c (14), Ia (9), and \(P\bar 1\) (2). In each group, the molecules are close to be isometrical, while these groups are linked by non-crystallographic symmetries termed morphotropism. The observed non-crystallographic symmetries are virtual between the homologues and real between their dimorphs. Real ncr’s were also found between 4-RPOTs and their clathrate forms. It is demonstrated how e.g. toluene induces real nrc’s in its clathrate with 4-IPOT.

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Notes

  1. “Because evidently impossible to define isomorphism precisely, we shall apply the term isostuctural to crystals in which there is essentially the same arrangement of geometrically similar structural units. Although it is not more precise than isomorphous this term refers to the general nature of the structure rather than the shape of the crystals.”

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Acknowledgments

The authors thank Professors László Bihátsi and Mátyás Czugler for their valuable advices to the PhD work of N. B. Báthori (Budapest). P. B. and A. K. acknowledge the support from the Hungarian Scientific Research Foundation (OTKA K-100801).

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Authors and Affiliations

  1. Research Group of Chemical Crystallography, Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, H-1117 Budapest, Magyar Tudósok körútja 2., Budapest, P.O. Box 206, 1519, Hungary

    Petra Bombicz & Alajos Kálmán

  2. Department of Chemistry, Cape Peninsula University of Technology, P.O. Box 652, 8000, Cape Town, South Africa

    Nikoletta B. Báthori

Authors
  1. Petra Bombicz
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  2. Nikoletta B. Báthori
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  3. Alajos Kálmán
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Corresponding author

Correspondence to Petra Bombicz.

Additional information

Dedicated to Professor Magdolna Hargittai on the occasion of her 70th birthday.

Appendix

Appendix

Graphic abbreviations:

  • POT⊥C 3 Perpendicular to the C 3 axis of the POT molecule

  • POT∥C 3 Parallel to the C 3 axis of the POT molecule

Crystal data and details of structure determination and refinement of 4-IPOT, 4-IPOT_TOL, 4-iPrPOT and 2-MePOT:

4-IPOT [30]

Crystal data: (2,4,6-tris(4-iodophenoxy)-1,3,5-triazine (C21H12I3N3O3, Ms = 735.04, trigonal R3c (No. 161) a = b = 24.831(5), c = 6.627(1) Å, α = β = 90°, γ = 120°, V = 3538.7(1) Å3, Z = 6, Dc (g cm−3) = 2.069, μ (mm−1) = 4.00 (size 0.14 × 0.02 × 0.02 mm), colourless needles from acetonitrile.

X-ray data: R-Axis Rapid, 93(2)K, λ(MoKα) = 0.71070 Å, θ = 3.28–23.24°, N tot = 30080 Nobs = 1064/91, [I > 2σI] = 968, R m = 0.104 (abs. num.c.) Max/min trans 0.9243/0.6043. R 1, wR 2 [I > 2σI] = 0.0391, 0.0604, R 1, wR 2 (total) = 0.0445, 0.0620, [e Å−3] −0.27/0.294

4-IPOT_TOL [30]

Crystal data: (2,4,6-tris(4-iodolphenoxy)-1,3,5-triazine·toluene clathrate (C21H12N3O3I3·C7H8), Ms = 827.19, trigonal \(R\bar 3\) (No. 148) a = b = 15.592(1), c = 18.359(2) Å, α = β = 90°, γ = 120°, V = 3865.3 (7) Å3, Z = 6, Dc (g cm−3) = 2.189, μ (mm−1) = 28.824 (size 0.50 × 0.30 × 0.30 mm) colourless prisms from toluene.

X-ray data: R-Axis Rapid, 98(2)K, λ(CuKα) = 1.5418 Å, θ = 0.9–73.2.0°, N tot = 17538, Nobs = 1655/198, [I > 2σI] = 1285, R m = 0.338 (abs. cylinder), Max/min trans 0.0006/0.0271. R 1, wR 2 [I > 2σI] = 0.1264/0.3056, R 1, wR 2 (total) = 0.1373/0.3246, [e Å−3] −3.347/3.349.

4-iPrPOT [30]

Crystal data: (2,4,6-tris(4-isopropylphenoxy)-1,3,5-triazine (C30H33N3O3, Ms = 483.59, trigonal R3c (No. 161) a = b = 24.259(1), c = 7.805(1) Å, α = β = 90°, γ = 120°, V = 3977.9 (6) Å3, Z = 6, Dc (g cm−3) = 1.211, μ (mm−1) = 0.101 (size 0.40 × 0.30 × 0.06 mm) colourless prisms from dichloromethane.

X-ray data: R-Axis Rapid, 99(2)K, λ(MoKα) = 0.71070 Å, θ = 3.34–27.32° N tot = 19346 Nobs = 2030/123, [I > 2σI] = 1413, R m = 0.163 (abs. num.c.) Max/min trans 0.9961/0.9961. R 1, wR 2 [I > 2σI] = 0.0708, 0.1149, R 1, wR 2 (total) = 0.1090, 0.1320, [e Å−3] −0.214/0.231

2-MePOT [30]

Crystal data: (2,4,6-tris(2-methylphenoxy)-1,3,5-triazine (C24H21N3O, Ms = 399.44, trigonal R3c (No. 161) a = b = 20.593(1), c = 8.605(1) Å α = β = 90°, γ = 120°, V = 3160.6 (5) Å3, Z = 6, Dc (g cm−3) = 1.259, μ (mm−1) = 0.684 (size 0.11 × 0.15 × 0.29 mm) colourless prisms from toluene.

X-ray data: R-Axis Rapid, 173(2)K, λ(CuKα) = 1.5418 Å, θ = 7.45–71.78° N tot = 14029, Nobs = 1355/92, [I > 2σI] = 890, R m = 0.140 (abs. num.c.) Max/min trans 0.9286/0.8263, R 1, wR 2 [I > 2σI] = 0.0447/0.1017, R 1, wR 2 (total) = 0.0592/0.1063, [e Å−3] −0.09/0.08

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Bombicz, P., Báthori, N.B. & Kálmán, A. Symmetry-controlled rearrangements in Piedfort Units (PU) of 2,4,6-triaryloxy-1,3,5-triazines. Struct Chem 26, 1611–1619 (2015). https://doi.org/10.1007/s11224-015-0659-8

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