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INTERMOLECULAR INTERACTIONS WITH PARTICIPATION OF  -SYSTEM IN SUPRAMOLECULAR COMPLEXES AND MOLECULAR CRYSTALS Oleg V. Shishkin STC “Institute for Single.

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Presentation on theme: "INTERMOLECULAR INTERACTIONS WITH PARTICIPATION OF  -SYSTEM IN SUPRAMOLECULAR COMPLEXES AND MOLECULAR CRYSTALS Oleg V. Shishkin STC “Institute for Single."— Presentation transcript:

1 INTERMOLECULAR INTERACTIONS WITH PARTICIPATION OF  -SYSTEM IN SUPRAMOLECULAR COMPLEXES AND MOLECULAR CRYSTALS Oleg V. Shishkin STC “Institute for Single Crystals”, National Academy of Science of Ukraine, Kharkiv, Ukraine

2 Intermolecular interactions as the main factor stabilizing supramolecular systems O.V.Shishkin, R.I.Zubatyuk, O.Yu.Zhovtyak, A.V.Kiriyak, S.A.Kotlyar, G.L.Kamalov. Struct.Chem., 2009, 20, 139. Structure of complex dication containing 3 molecules of 15-crown-5, 2 Li cations and 2 water molecules. X-ray diffraction data and calculations by B3LYP/6-311G(d,p) method

3 Aromatic fragments in supramolecular systems

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6 Stacking interactions between π-systems Structure of stacked dimer of N-methylated adenine-thymine Watson- Crick pairs of bases optimized by SCC-DFTB-D method O.V.Shishkin, M.Elstner, T.Frauencheim, S.Suhai, Int.J.Mol.Sci., 2003, 4, 537

7 D-H…π hydrogen bonds in molecular complexes and crystals Infinite chains formed by the O-H…π hydrogen bonds in crystals of tribromo substituted trityl alcohols D. Schollmeyer, O.V.Shishkin, T.Ruhl, M. O. Vysotsky, CrystEngComm, 2008, 10, 715

8 Possible hydrogen bonds for aromatic azines Case of pyridine monohydrate

9 Experimental observation of mixed O-H…N/O-H…  H-bonds Geometrical parameters of hydrogen bond: N…H Å O-H…N o C-C-N…H o E.M.Opozda, W.Lasocha, B.Wlodarczyk-Gajda, J. Mol. Struct., 2006, 784, 149

10 Competition of the O-H…N and O-H…  H-bonds in monohydrate of pyridine Contribution of lone pair and π-system into total energy of hydrogen bond obtained from NBO analysis. MP2/aug-cc-pvdz data O-H…N bond O-H…  bond O.V.Shishkin, I.S.Konovalova, L.Gorb, J.Leszczynski, Struct.Chem., 2009, 20, 37.

11 Mixed N-H…N/N-H…π hydrogen bonds in crystals of diaminotriazole (experimental change density distribution) d, Ǻ  (r), a. e.  2  (r), a. e. E cont, kcal/mol N6-Н…N3 2.46(1) I.S.Konovalova, Yu.V.Nelyubina, K.A.Lyssenko, B.V.Paponov, O.V.Shishkin, in preparation Contribution into total hydrogen bonding: Lone pair: 45 % π-system: 55 %

12 Competition between the O-H…N and O- H…  H-bonds in polyhydrates of guanine H-bondH…AD-H…A N(7)…H-O(W12) N(7)…H-O(W13) N(3)…H-O(W4) N(3)…H-O(W5) C(6)…H-O(W16) O. S. Sukhanov, O. V. Shishkin. L. Gorb, J. Leszczynski, Struct. Chem., 2008, 19, 171 Complex with 17 H 2 O B3LYP/6-311G(d,p)

13 Competition between the O-H…N and O-H…  H-bonds in polyhydrates of guanine NBO analysis of contributions of individual interactions into hydrogen bonding H-bondInteracting NOE(2), кcal/mol Contrib., % N(7)…H-O(W12) LP(N)  * (H-O) N(7)…H-O(W13) LP(N)  * (H-O)  (N-C)  * (H-O) N(3)…H-O(W4) LP(N)  * (H-O)  (N-C)  * (H-O) N(3)…H-O(W5) LP(N)  * (H-O)  (N-C)  * (H-O) C(6)…H-O(W16)  (C-C)  * (H-O)

14 Mixed hydrogen bonds in hydrated nucleic acid bases Distribution of water hydrogens around adenine and cytosine during Car-Parrinello molecular dynamics simulation A. Furmanchuk, O. Isayev, O. V. Shishkin, L.Gorb, J. Leszczynski, PCCP, 2010, 12, 3363

15 Mixed hydrogen bonds with participation of carbonyl group Geometrical parameters of the N-H…O hydrogen bond: H…O 2.12 Å; N-H…O 166 o С-С=O…H -69 o Contribution to total energy of hydrogen bonding from NBO analysis (M06- 2X/aug-cc-pvdz): Lone pair: 60% π-system: 40 % I.S.Konovalova, G.V.Palamarchuk, O.V.Hordienko, O.V.Shishkin, in preparation

16 What is the main motif of crystal packing (supramolecular architecture of molecular crystals)? HO O O OH Adipinic acid Case of relatively strong hydrogen bonds Crystal packing is packing of hydrogen bonded chains

17 What is the main motif of crystal packing (supramolecular architecture of molecular crystals)? S.V.Shishkina, O.V.Shishkin, R.Ya.Grygorash, A.V.Mazepa, I.M.Rakipov, V.V.Yakshin, S.A.Kotlyar, G.L.Kamalov, J.Mol.Struct., 2007, 832, 199

18 Crystal packing of bicyclic aziridines V.V.Dyakonenko, A.V.Zbruyev, V.A.Chebanov, S.M.Desenko, O.V.Shishkin, J.Struct.Chem., 2005, 46, 1110

19 Approach for determination of real crystal packing pattern Accurate determination of crystal structure Determination of molecules belonging to first coordination sphere of basic molecule using Dirichlet polyhedron Accurate quantum chemical calculations of energy of intermolecular interactions of basic molecule and molecules from its first coordination sphere Recognition of crystal fragments containing strongly bonded molecules

20 DimerSymmetryE int, kcal/mol Structure 1 1_1(-x, -y, 1-z) _2(-x, 1-y, 1-z) _3(-x, 1-y, -z) _4(x-1, y, z) _5(x+1, y, z) _6(1-x, 1-y, -z) _7(x, y, z-1) _8(x, y, z+1) _9(x, y-1, z+1) _10(x, y+1, z-1) _11(1+x, y, z-1) _12(x-1, y, z+1) _13(-1-x, -y, 2-z) _14(1-x, -y, 1-z) _15(-x, -y, 2-z) _16(1-x, 1-y, 1-z)-0.38 Energy of interaction of basic molecule and molecules from its first coordination sphere calculated by MP2/6-311G(d,p) method V.V.Dyakonenko, A.V.Maleev, A.I.Zbruyev, V.A.Chebanov, S.M.Desenko, O.V.Shishkin, CrystEngComm, 2010, 6, 1816

21 Layered structure of crystals of bicyclic aziridines Comp.InsideNeighbor Energy of interactions (kcal/mol) of basic molecules with molecules within the same layer and from neighboring layer (MP2/6-311G(d,p) data) V.V.Dyakonenko, A.V.Maleev, A.I.Zbruyev, V.A.Chebanov, S.M.Desenko, O.V.Shishkin, CrystEngComm, 2010, 12, 1816

22 Supramolecular architecture of crystal with stacking interaction E int =-21.8 kcal/mol E int =-10.3 kcal/mol MP2/6-311G(d,p) data O.V.Shishkin, V.V.Dyakonenko, A.V.Maleev, D. Schollmeyer, M.Vysotsky, CrystEngComm, in press

23 Supramolecular architecture of crystal with stacking interaction Total energy of interactions (kcal/mol) of basic molecule to molecules belonging to the same layer in the crystal MP2/6-311G(d,p) data LayerTotal in layer O.V.Shishkin, V.V.Dyakonenko, A.V.Maleev, D. Schollmeyer, M.Vysotsky, CrystEngComm, in press

24 Supramolecular architecture of hydrogen bonded crystals orthorhombic monoclinic Crystals structure of two polymorphic modifications of crystals of 3,4-diamino-1,2,4-triazole I.S.Konovalova, S.V.Shishkina, B.V.Paponov, O.V.Shishkin, CrystEngComm, 2010, 12, 909

25 Layered structure of monoclinic polymorph of 3,4-diamino-1,2,4-triazole Energy of interactions (MP2/aug-cc-pvdz): Inside layer: kcal/mol To neighboring layer: -3.6 kcal/mol I.S.Konovalova, S.V.Shishkina, B.V.Paponov, O.V.Shishkin, CrystEngComm, 2010, 12, 909

26 Layered structure of orthorhombic polymorph of 3,4-diamino-1,2,4-triazole Energy of interactions (MP2/aug-cc-pvdz): Inside layer: kcal/mol To neighboring layer: -1.5 kcal/mol I.S.Konovalova, S.V.Shishkina, B.V.Paponov, O.V.Shishkin, CrystEngComm, 2010, 12, 909

27 Conclusions π-System of aromatic and heteroaromatic rings represents very rich source of different types of weak intermolecular interactions influencing geometry and properties of supramolecular systems and molecular crystals. Combination of reliable experimental methods of structure determination and modern ab initio quantum-chemical methods leads to successful recognition and investigation of various weak intermolecular interactions. Application of reliable quantum-chemical methods of calculations of intermolecular interaction energy provides unambiguous recognition of main pattern of supramolecular architecture of molecular crystals and assemblies

28 Special thanks: Synthesis and crystal growth Prof. G.L.Kamalov and Dr.S.A.Kotlyar – A.V.Bogatsky Physico-Chemical Institute, Odessa, Ukraine. Dr. O.V.Hordienko – T.G.Shevchenko Kyiv National University, Ukraine Dr. M.O.Vysotsky – Mainz University,Germany Prof. S.M.Desenko, Dr. V.A.Chebanov – Division of Functional Materials Chemistry, SSI “Institute for Single Crystals”, Kharkiv, Ukraine Dr. B.V.Paponov – V.N.Karazin Kharkiv National University, Ukraine Experimental charge density distribution analysis Dr. K.A.Lyssenko, Dr. Yu.V.Nelyubina – A.N.Nesmeyanov Institute of Organoelement Compounds, Moscow, Russian Federation Analysis of crystal packing Dr. A. V. Maleev – Vladimir State Humanitarian University, Russian Federation Quantum-chemical calculations Prof. J. Leszczynski, Dr. L.Gorb, Dr. A.Furmanchuk, Dr. O Isayev – Jackson State University,USA

29 Very special thanks Department of X-Ray Diffraction Studies and Quantum Chemistry Irina S. Konovalova Viktoriya V. Dyakonenko Dr. Svitlana V. Shishkina Gennady V. Palamarchuk

30 Especially very special thanks: for your attention


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