ZB-14. X-Ray Crystallography

 

Head of the Group: Prof. Tadeusz Lis

M.Sc. 1970, Ph.D. 1973, D.Sc. 1979, Prof. 1994

 

Research staff

Prof. Ciunik Leszek Zbigniew

Dr. Białońska Agata

Dr. Ślepokura Katarzyna

Krawczyk Marta, M Sc.

Krawczyk Monika, M Sc.

Kwiecień Anna, M.Sc.

 

 

Research topics

 

• The study of crystal and molecular structure of coordination compounds of transition metals and lanthanides,
compounds of biological importance.

• Analysis of experimental electron densities in crystals.

• Weak intermolecular interactions in crystals.

• Determination of absolute configuration.

• Conformation analysis of organic compounds (X-ray, molecular mechanics and semiempirical methods).

 

 

Special equipment

Two powder diffractometers: URD-6 and Dron.

 

 

Recent research achievements

 

Studies on racemic resolution of N-protected amino acids by fractional crystallization of strychninium and
brucinium salts concern:

– role of intermolecular interactions in molecular recognition,

influence of solvent on racemic resolution.

Comparison of several crystal structures of brucinium and strychninium salts with different N-protected
amino acids points at the importance of alkaloid self-assemblies in molecular recognition. Simultaneously,
various donor/acceptor capabilities of amino acid derivatives control acceptors’ access of resolving agent
self-assemblies and therefore racemic resolution. Excellent illustration of above tendency is observed during
racemic resolution of of N-benzoyl- and N-phthaloyl-DL-alanine by brucine and strychnine. In the case of first
amino acid derivative R.O. Gould and M.D. Walkinshaw (J. Am. Chem. Soc., 1984, 106, 7840) obtained
strychninium N-benzoyl-L-
α-alanine and brucinium N-benzoyl-D-α-alanine and in the case of second derivative
the strychninium N-phthaloyl-D-alanine and brucinium N-phthaloyl-L-alanine were obtained [6].

 

 

78

 

 

An interest in synthesis and structural investigations of some crucial biological intermediates (organic phosphate
esters like PEP, phosphoaminoacids or small sugars, e.g. dihydroxyacetone, DHA and sugar phosphates, e.g.
dihydroxyacetone phosphate, DHAP, shown in Fig. 1) is the consequence of their biological functions and application.
The method of the synthesis of stable (even at room temperature) DHAP salt has been worked out, which allowed us
to determine DHAP structure in solid state for the first time. The structural investigations have revealed that DHAP may exist in two monomeric forms as well as in dimeric form (see Fig. 1). The latter has not been mentioned in the literature so far, and its possible role in biochemical processes has not been taken into consideration.

 

 

 

 

Dihydroxyacetone phosphate anions in monomeric ketone form: DHAP2– (left) and in dimeric form: (DHAP-dimer)2 (right)

 

 

Selected papers

1.         Lis T.
Preparation, structure and magnetic properties of a dodecanuclear mixed-valence manganese carboxylate.
Acta Crystallogr., Sect. B: Struct. Sci., 1980, 36, 2042–2046.

2.         Olijnik V., Głowiak T., Mys’kiv M.
Copper(I) nitrate
π-complexation: Synthesis and crystal structure of
[(CH2=CH–CH2)2NH2][Cu(NO3)2].
J. Chem. Cryst., 1995, 25, 621–624.

3.          Ciunik Z., Desiraju G.R.
Area correction of multi-atom–acceptor hydrogen bond frequency distributions.
Chem. Commun., 2001, 703–704.

4.         Berski S., Ciunik Z., Drabent K., Latajka Z., Panek J.
Dominant role of C–Br×××N halogen bond in molecular self-organization. Crystallographic and quantum-chemical study of Schiff-base-containing triazoles.
J. Phys. Chem. B., 2004, 108, 12327–12332.

5.          Ozeryanskii V.A., Pozharskii A.F., Bieńko A.J., Sawka-Dobrowolska W., Sobczyk L.
[NHN]+ hydrogen bonding in protonated 1,8-bis(dimethyloamino-2,7-dimethoxynaphtalene. X-ray diffraction, infrared, and theoretical ab initio and DFT studies.
J. Phys. Chem. A., 2005, 109, 1637–1642.

6.         Białońska A., Ciunik Z.
When in the presence of the strong hydrogen bonds, the weak hydrogen bonds gain an importance.
CrystEngComm, 2006, 8, 66–74.

7.         Białońska A., Ciunik Z.
Intermolecular hinge—a new function of the C–H…p hydrogen bond.
CrystEngComm, 2007, 9, 570–573.

8.          Ślepokura K.
Structure of cyclic dihydroxyacetone phosphate dimethyl acetal, a cyclic DHAP precursor, in the crystalline state.
Carbohydr. Res. 2008, 343, 113–131.

9.         Hołyńska, M., Lis, T.
Remarkably stable dinuclear, diamagnetic rhenium(VI) salts with the [ReOCl4OReOCl4]2- anion.
Dalton Trans. 2009, 19, 3840–3846.

10.      Ślepokura K., Lis T.
Dihydroxyacetone phosphate, DHAP, in the crystalline state: monomeric and dimeric forms.
Carbohydr. Res.
2010, 345, 512–529.