Thermally induced order–disorder transition in crystals of lithium complexes of 1,5-Bis[2-(diphenylphosphorylmethyl)phenoxy]-3-oxapenthane [LiL](ClO{sub 4}) and [LiL](NCS): Effect of the anion on the temperature of transition
- Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation)
- Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry (Russian Federation)
Compounds of 1,5-bis[2-(diphenylphosphorylmethyl)phenoxy]-3-oxapenthane (L) with lithium salts LiXL, where Х{sup –} = ClO{sub 4}, NCS, or I, and LiBrL ⋅ 2H{sub 2}O, are synthesized. The IR spectra and the thermal behavior of complexes are studied. X-ray diffraction studies of isostructural [LiL](ClO{sub 4}) (I) and [LiL](NCS) (II) crystals are performed. In the [LiL]{sup +} complex, the ligand coordinates the Li atom by five O atoms, forming an environment in the shape of a trigonal bipyramid [in II at 174 K, the Li–O bonds are1.829(3)–2.341(3) Å]. It is found that crystals I and II undergo a reversible phase transition of the order–disorder type with the change of symmetry (P2{sub 1}/n ↔ P1̄). The temperatures of transition of crystals I and II differ by ~70°. This distinction is explained by different types of disordering of the phenyl rings of the L ligand in the monoclinic phase, namely, dynamic in I and static in II. The analysis of intermolecular contacts allows one to relate the state of disordering of ligand L in the crystal to the strength of its interactions with the anion: in II the NCS{sup –} anion is firmly fixed by the С–Н···S and С–Н···N hydrogen bonds (at 174 K, H···S is 2.77 and H···N is 2.36 Å); in I the С–Н···О interactions of the ClO4̄ anion with the ligand are weaker (at 215 K, Н···О ≥ 2.37 Å) and the anion is disordered.
- OSTI ID:
- 22722852
- Journal Information:
- Crystallography Reports, Journal Name: Crystallography Reports Journal Issue: 4 Vol. 60; ISSN 1063-7745; ISSN CYSTE3
- Country of Publication:
- United States
- Language:
- English
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