International Union of Crystallography Commission on Mathematical and

Theoretical Crystallography

Summer Schools on Mathematical Crystallography Nancy, France, 21 June - 2 July 2010

Program

Abstracts of Poster Presentations

21 June: PRE-SCHOOL DAY Introduction to crystal symmetry; space groups, Hermann-Mauguin symbols, exercises on the International Tables for Crystallography

22-25 JUNE: SCHOOL ON TOPOLOGICAL CRYSTAL CHEMISTRY: THEORY AND PRACTICE

THEORY Periodic Structures and Crystal Chemistry... aka the Topological Approach to Crystal Chemistry Graph, Nets & Tilings (Quotient Graphs & Natural Tilings) Topological Analysis of Entanglement : interpenetration, polycatenation & more Computer crystallochemical analysis: an overview Applied computer crystallochemical analysis PRACTICE WITH PROGRAMS TOPOS, Systre, 3dt Module 1. Standard topological analysis and classification of nets in MOFs (Metal-Organic Frameworks), organic and inorganic crystals Creating a database from CIF, SHELX or Systre formats Computing adjacency matrix (complete set of interatomic bonds) for chemical compounds with different chemical

bonding (valence, H bonding, specific interactions, intermetallic compounds) Visualizing 0D, 1D, 2D and 3D structures Standard simplified representations of MOFs or hydrogen-bonded organic crystals Computing topological indices (coordination sequences, point, Schläfli and vertex symbols) Topological identification of nets. Working with TTD collection and Systre Taxonomy of nets. Working with TTO collection Module 2. Special topological methods of searching for building units in crystal structures Special methods of simplification. Edge nets and ring nets. Analysis of synthons Standard cluster representation of MOFs Nanocluster representation of intermetallic compounds Module 3. Analysis of entanglements in MOFs and molecular crystals Visualization, topological analysis and classification of interpenetrating MOFs Detection and description of other types of entanglement in MOFs: polycatenation, self-catenation and

polythreading Module 4. Analysis of microporous materials and fast-ion conductors with natural tilings Computing natural tilings and their parameters. Visualizing tiles and tilings (TOPOS & 3dt). Simple and isohedral

tilings. Constructing dual nets Analysis of zeolites and other microporous materials, constructing migration paths in fast-ion conductors Module 5. Crystal design and topological relations between crystal structures Group-subgroup relations in periodic nets. Subnets and supernets Maximum-symmetry embedding of the periodic net, working with the Systre program Mappings between space-group symmetry and topology of the periodic net Searching for topological relations between nets and working with net relation graph Applications of net relations to crystal design, reconstructive phase transitions, taxonomy of crystal structures

26-27 JUNE: PREPARATION TO THE SECOND SCHOOL

Basic facts on crystallographic groups Point groups. Elements of point symmetry. Groups, subgroups and theorem of Lagrange. Generators. Classes of

conjugation. Abelian groups and cyclic groups. Crystallographic point groups and abstract groups. Generation of point groups by composition series. Classification of crystallographic point groups.

Crystallographic symmetry operations and their presentation by matrices. Space groups. Translation groups and coset decompositions of space groups. Symmorphic and non-symmorphic space groups. Generation of space groups by composition series.

Group-subgroup relations of point and space groups.

28 JUNE TO 2 JULY: SCHOOL ON IRREDUCIBLE REPRESENTATIONS OF SPACE GROUPS

Representations of crystallographic groups (3 days) 1. General remarks on representations. Representations of discrete groups. Equivalence of representations.

Unitary representations. Invariant subspaces and reducibility. Theorem of orthogonality. Characters of representations and character tables.

2. Representations of point groups. Representations of Abelian groups: cyclic groups and direct products of cyclic groups. Character tables of representations of point groups. Online databases for point-group representations.

3. Induction procedure for the derivation of the representations of crystallographic groups. Subduced and induced representations. Conjugate representations and orbits. Little groups, allowed representations and induction theorem. Induction procedure for indices 2 and 3. Representations of some point groups by the induction procedure.

4. Representations of space groups. Representation of the translation group. Star of a representation. Little groups and small representations. Representations of symmorphic and non-symmorphic groups. Online tools for the derivation of space-group representations.

Applications of representations theory in solid-state physics and chemistry (2 days) 1. Vibrations in molecules and solids

i. Molecular dynamics. Small oscillations and normal modes. Zero modes and vibrational modes. Mechanical and vibrational representations. Dynamical matrix in symmetry adapted coordinates. Degeneracy.

ii. Electronic energy bands and phonon spectra. Assignment of small representations. Compatibility relations. Symmetry-adapted bases. Partial diagonalization of the dynamical matrix. Anticrossing.

iii. Direct products of irreducible representations and selection rules - general formulation. Selection rules in molecular spectroscopy: rotational and vibrational absorption, infrared and Raman effect. Direct products of space-group representations and selection rules. Online tools for infrared and Raman selection rules.

2. Structural phase transitions i. Representation theory tools in the analysis of phase transitions. Primary and secondary order

parameters; couplings and faintness index. Order parameter direction and isotropy subgroups. Group-theoretical formulation of the necessary conditions for second-order phase transitions.

ii. Symmetry-mode analysis of structural phase transitions. Hierarchy of modes. Symmetry-modes applications in structure refinement. Online tools for symmetry-mode analysis.

Schedule

9.00-10.30 - morning session I 10:30-11:00 - coffee break 11.00-12.30 - morning session II 12:30-14:00 - lunch 14.00-16.00 - afternoon session I 16:00-16:30 - coffee break 16.30-19.00 - afternoon session II

Abstracts of poster presentations

Peculiarities of molecular structure and intermolecular interactions in the Cu(II) and Pd(II) complexes with salicylaldehyde thiosemicarbazones derivatives

Bon V.V., Orysyk S.I., Pekhnyo V.I. (V.I.Vernadskii Institute of General and Inorganic Chemistry of Ukrainian NAS, Kyiv, Ukraine) volodimir.bon@gmail.com

Thiosemicarbazones and their metal complexes attract constant scientific interest due to their antimicrobial, antifungal and antitumoral activities [1, 2]. The structure of thiosemicarbazones metalla complexes is studied thoroughly. On the other hand, there are only few works reporting the structure of 1:2 square-planar thiosemicarbazone complexes with with different coordination modes of the ligands [3]. The present work reports synthesis and X-ray diffraction study of Cu(II) (1a, 2a) and Pd(II) (3a) coordination compounds with Salicylaldehyde 4-Phenyl- and 4-allylthiosemicarbazones (Fig.1). Depending on synthesis condition, the complexes with M:L ratio 1:1 and 1:2 has been obtained. The molecular structures of synthesized compounds show square-planar geometry of central atom. One of ligand molecules coordinates in tridentate manner via thioamide sulphur, azomethine nitrogen and phenyl oxygen, creating two chelate rings, which is coplanar with aromatic ring. Square-planar coordination environment of central atom completes by the pyridine molecule in the case of 1:1 complex or by monodentally coordinated ligand molecule in the case of 1:2 complexes. The crystal structure of (1b) creates polymeric 2D network of weak N-H…S and C-H…O H-bonds (Fig.2). The crystal packing of (2b) display zig-zag structure along the c direction and layered structure along b direction. The layers are stabilized by H-bonds network and weak intermolecular Cu-N interaction. Compound 3 isolated in two different polymorphic modifications, which differ mostly in intermolecular interactions. The crystal structure of monoclinic polymorph (3m) characterized by weak intermolecular Pd(1)…S(2) and Pd(1)…N(4) interactions along the 001 direction with distance parameters 3.625(1) and 3.459(3) Å respectively. At the same time, triclinic modification (3t) shows Pd(1)…H(18) = 2.930(4) Å interaction, located in perpendicular direction to coordination polyhedron.

1a 2a 3a

Figure 1 General view of the compounds 1a, 1b and 1c. Thermal ellipsoids are shown at 50% probability. Dashed lines indicate intramolecular H-bonds.

1 2

3m 3t

Figure 2 Crystal packing diagrams for investigated compounds. Dashed lines indicate intermolecular interactions.

[1] Stanojkovic, T. P., Kovala-Demertzi, D., Primikyri, A., Garcia-Santo, I., Castineiras, A., Juranic, Z. & Demertzis, M. (2010). J. Inorg. Biochem. 104, P.467–476

[2] Garoufilis, A., Hadjikakou, S. K. & Hadjiliadis, N. (2009). Coord. Chem. Rev. 253, P.1384–1397 [3] Papathanasis L., Demertzis M. A., Yadav P. N., Kovala-Demertzi D., Prentjas Ch., Castiňeiras A., Skoulika S, West D. X. (2004)

Inorg. Chim. Acta. 357 P.4113–4120

HYDROGEN BONDED SUPRAMOLECULAR TOPOLOGIES OF H2PO4- ANION-

TEMPLATED NETWORKS IN DIHYROGEN PHOSPHATE SALTS.

R. Jagan and K. Sivakumar Department of Physics, Anna University, Chennai, India-600 025

The construction of organic-inorganic hybrid compounds has been of considerable interest and challenging in recent years, not only because they are a powerful means of generating self assembled supramolecular architecture but also their potential for providing new materials with magnetic, semiconducting, optical and electrolytic properties. Orthophosphoric acid (H3PO4), an inorganic oxy-acid, forms dihydrogen phosphate salts with organic amines in which the H2PO4

- anions acts as a template for the assembly of cations paving the way for the assembly of cations. We have prepared crystal structures of molecular adducts of aromatic and cyclic amines with orthophosphoric acid (H3PO4) resulting in 2-chloroanilinium dihydrogen phosphate (1), 4-chloroanilinium dihydrogen phosphate (2), 2-benzylaminopyriinium dihydrogen phosphate (3), piperazinium (bis) dihydrogen phosphate (4). In compounds 1 and 3 the H2PO4

- anions form templated infinite chains but with double stranded (Figure 1) and spiral (Figure 3) like topologies in which the cation are assembled to form a organic-inorganic hybrid supramolecular framework. In compounds 2, 4 the anions form extended two dimensional grids (Figures 2 & 4) with different dimensions and topologies. In 3 the piperazinium cations bound with the anions, resembles a host-guest inclusions type of supramolecular architecture whereas in 2 the 4-chloroanilinium cation are pendant on both the faces of the two dimensional grid. We have done an analysis with 85 dihydrogen phosphate structures (excluding structures with solvents, and disorders) and interpreted with our observations. These observations demonstrate the ability to construct H2PO4

- anionic framework and the preferred topologies can be designed by choosing the appropriate choice of counter molecule.

(1) (2)

(3) (4) Figures: Formation of H2PO4

- anionic topologies and the linking of cations through O-H…O and N-H…O hydrogen bonds exhibiting different self assembled supramolecular architecture for compounds 1, 2, 3 and 4.

HYDROGEN BONDED SUPRAMOLECULAR TOPOLOGIES IN ORGANIC PICRATE SALTS AND THE PREDCTION OF SUPRAMOLECULAR ARCHITECHTURE IN NH+, NH2

+

AND NH3+

SUBSTITUTED CATIONS

K. Sivakumar and R. Jagan Department of Physics, Anna University, Chennai, India-600 025

The concept of viewing crystal structure as network can simplify complex crystalline structural features into easily identifiable network topologies based on the chemical and structural information of the constituent building blocks. A series of picrate salts were crystallized and investigated in our laboratory to understand the nature of the supramolecular network formed through non-covalent interactions. The crystal structures for the salts of Picric acid with triethylamine(1), 1,4-diazabicyclo[2.2.2]octanamine(2), Piperidine(3), Dicyclohexylamine(4), 4-Fluoroaniline(5), Cyclooctanamine(6), Furan-2-yl-methanamine(7), Hexanamine(8), Cyclohexylamine(9), 2-chloroaniline(10), 4-Methylaniline(11), 3-methylaniline(12) were investigated. From the structures we observed that picrates show a variety of N-H…O hydrogen bonded network topologies like molecular chains, tapes, ribbons and two dimensional sheets. The architecture of these topologies are decided by the nature of protonated groups namely NH+(1, 2), NH2

+(3, 4) and NH3+(5-12).

The NH3+ substituted cations shows layered topologies like infinite two dimensional sheets (11,12), motif

assisted chains and tapes (5-10) when compared to structures with NH+ and NH2+ protonated groups.

Interestingly in NH+ and NH2+ based structures, C-H…O interactions along with N-H…O hydrogen bond

play active role in generating supramolecular assemblies leading infinite chains(4) and three dimensional networks (1-3). In addition to the above investigation, hydrogen bonding networks in picrate salts have examined and compared with our observation using CSD taking the 263 organic picrate salts. Excluding structures with solvates, multi functional groups, non-hydrogen structures, structures with unique amine group categorized under NH+, NH2

+, NH3+

were examined for N-H…O hydrogen bond assisted supramolecular patterns. From the results supramolecular ar architectures can be predicted by choosing the amino group substitution for the designing of new solids.

NN

N

O

O

O

O O-

N N

N

O

O

O

OO-

O O

O O

N N

H

H

H

H

HH

NN

N

O

O

O

O O-

N N

N

O

O

O

OO-

O O

O O

N N

H

H

H

HH

H

D

R42(8)

R12(6)

O

O

O

O O-

N N

N

O

O

O

O-O

O O

O O

NH

H

NH

H

R44(12)

R12(6)

D

NN

N

O

O

O

O -O

O O

N

H

R12(6)

Schematic representation of some hydrogen bonded motifs formed in picrates.

SELF ASSEMBLED SUPRAMOLECULAR ARCHITECTURES EXHIBTED BY SOME ORGANIC HYDROGEN PHTHALATE SALTS

K. Sivakumar and R. Jagan

Department of Physics, Anna University, Chennai, India-600 025 Intermolecular hydrogen bond is an efficient tool to regulate molecular arrangement in a crystal structure. Supramolecular framework strategy may be utilized in the deliberate design of organic solids maintaining controlled and ordered architecture, which further leads to desired chemical, physical and optical properties. Aromatic carboxylic acids have been most used for their ability to form strong and directional hydrogen bonds. A series of organic salts formed from phthalic acids namely 4-chloroanilinium hydrogen phthalate (1), 2-hydroxyanilinium hydrogen phthalate (2), 3-hydroxyanilinium hydrogen phthalate (3) and 4-dimethylaminopyridinium hydrogen phthalate (4) were investigated. The hydrogen phthalate ions of 2-4 show a short intramolecular O—H…O hydrogen bond, with O…O distances ranging from 2.3832 (15) to 2.3860 (14) Å. A variety of supramolecular hydrogen bonded frameworks involving interactions between aminium cations and hydrogen phthalate anions are observed. Compound 1 forms a two-dimensional supramolecular sheet of anions and cations extending in the (100) plane, whereas 2 has a supramolecular chain running parallel to the [100] direction. The inversion-related antiparallel supramolecular chains are interlinked by N-H…O hydrogen bonds, forming an infinite supramolecular anionic-cationic framework extending along the [100] direction. In 3 the anions and cations form supramolecular tape through N-H…O and O-H…O hydrogen bonds. Parallel arrays of these chains are further linked through N1-H…O hydrogen bonds, thus building up an extended two-dimensional network parallel to (001). In 4 the anions and cations are linked to form one dimensional chain through alternate N-H…O and C-H…O interactions.

(1) (2)

(3) (4) Figure: Some of the self assembled supramolecular frameworks generated by compounds 1, 2, 3 and 4.

Synthesis and Characterization of new Zinc (II) Coordination Polymers Bearing Aminobenzoic Linkers.

Jymmy Restrepo-Guisao, Marta E. G. Mosquera, Pilar Gómez-Sal

Universidad de Alcalá, Campus Universitario, 28805-Alcalá de Henares, Madrid, España.

e-mail:jirg04@gmail.com

The reactions of ZnII with various organic linkers have been broadly studied for the preparation of carboxylate complexes. Although many coordination polymers with ZnII have been already described in the literature, the synthesis of these compounds continues to attract interest due to its application in the field of molecular materials with magnetic1 and photoluminescent2 properties.

Our research is focused in the preparation of Zn(II) coordination polymers with carboxylate ligands, in particular we are carrying out a very detail study of the Zn(II)/p-aminobenzoic acid system. In this contribution, we aim to report the synthesis and characterization of the new coordination polymers resulting from our investigations. As such, we have isolated structures with different dimensionality (3D, 2D and 1D) showing the carboxylate group with different coordination modes: bridging or monodentated, {[Zn2(μ-4-aba)(4-aba)(μ-N3)2]}n, {[Zn(4-aba)](OH)}n, {[Zn(μ-4-aba)(4-aba)(H2O)]•(H2O)}n. The possibility of obtaining this structural disparity using very similar reaction conditions can be attributed to the lability of the Zn(II) carboxylate complexes in solution and the capability of the carboxylate group to switch from one coordination mode to another through an energetically accessible pathway.3 In the isolated polymers it is remarkable the structure shown in the picture than can be described as a zinc hydroxide coordination polymer pillared by p-aba bridging ligands.

Figure 1. Compound {[Zn(4-aba)](OH)}n

[1] Eddaoudi, M.; Li, H.; and Yhagui, O. M., J. Am. Chem. Soc., 2000, 122 (7), 1391–1397. [2] Dai, F.; He, H.; and Gaon, D., Inorg. Chim. Acta. 2009, 362, 3987-3992. [3] Kumar, U.; Thomas, J.; and Thirupathi, N., Inorg. Chem. , 2010, 49, 62-72.

Nickel Metal-Organic Frameworks with polymetallic Secondary Building Units

Josefina Perles, Javier Torroba, Miguel Cortijo, Santiago Herrero, Reyes Jiménez-Aparicio, José L. Priego, M. Rosario Torres, Francisco A. Urbanos

Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Madrid, Spain jperles@quim.ucm.es

Metal-Organic Frameworks, or MOFs, are promising materials in many fields such as gas storage, separation, ion exchange or catalysis, and they also show interesting magnetic, electric and optical properties [1]. Accordingly, the studies on the synthesis and characterisation of infinite one-, two- and three-dimensional coordination networks have experienced a rapid

growth in the last 20 years. One of the advantages of MOFs, compared to other well known porous solids (e. g. zeolites), is the possibility to modify the shape and dimensions of the pores defined by the framework with a careful choice of metal nodes and linkers. There is a wealth of organic ligands to be used as connectors between many transition metals and rare-earths with different coordination numbers and geometries. Furthermore, the existence of SBUs (Secondary Building Units) allows the design of new structures in which the nodes are metal-containing aggregates [2]. This approach can result in the formation of frameworks with new topologies and interesting properties derived from them.

Figure 1. Secondary Building Unit consisting of four edge-sharing octahedra. Oxygen and nitrogen atoms are represented as red and blue spheres, respectively.

In this abstract we present an isomorphous series of new three-dimensional Metal-Organic Frameworks containing a tetranickel SBU with ten points of extension. The SBU consists of four edge-sharing NiA6 octahedra, (A= O, N), as depicted in figure 1. The compounds, with formula [Ni4(RCO2)(NC5H4CO2)5(OH)2]n where R=(MeO)mC6H5-m, display a three-dimensional framework where the nickel atoms are coordinated to the hydroxyde anions and two different organic ligands: isonicotinate and phenylcarboxylate. Both hydroxyde (μ3-OH) and phenylcarboxylate (μ3-

1κO,2κO,3κO’) ligands are coordinated to nickel atoms from the same SBU. The isonicotinate ligands, however, act as linkers between SBUs displaying three different coordination modes: μ-1κN,2κO; μ3-1κN,2κO,3κO’ and μ4-1κN,2:3κ2O,4κO’.

Figure 2. Schematic view of two members of the series (m=0 and m=3) along the a axis with the isonicotinate anions depicted as N–CO2 axes.

Each SBU is connected to nine adjacent units, giving rise to three- and four-membered channels parallel to the a axis (figure 2). The aromatic groups of the phenylcarboxylate ligands are located in the square four-membered channels. The rings from the phenylcarboxylate ligands adopt a different position depending on the number of methoxy substituents (m), as can be seen in figure 2. For instance, the angle between the ring and the bc plane is 31.9° for the benzoate derivative (m=0), and 59.7° in the case of the MOF containing 3,4,5-trimethoxybenzoate (m=3).

[1] Metal-organic framewoks issue (2009) Chem. Soc. Rev., 38, 5, 1201-1508. [2] Tranchemontagne, D. J.; Mendoza-Cortés, J. L.; O’Keeffe, M.; Yaghi, O. M. (2009) Chem. Soc. Rev., 38, 1257-1283.

Phase Determination with Direct Methods

Amani Direm et Nourredine Benali-Cherif (Laboratoire des Structures, Propriétés et Interactions Inter Atomiques LASPI2A, Institut des Sciences et Technique.Centre Universitaire ‘’Abbes Laghrour,

Khenchela 40000, Algérie) Amani_Direm@yahoo.fr The crystal structure determination with X-Ray diffraction provides very important information about the arrangement of the atoms in the crystalline compounds which can be used to understand their different physical and chemical properties. In an X-ray diffraction experiment, we measure the intensities of reflections and perform a Fourier synthesis. The calculation of an electron density map, which provides an interpretable picture of a molecule, requires both intensities and phases. Unfortunately, the most important parameter we need for locating the atoms in the unit cell : ‘’the phase value” is lost. This severe lack of information is the so-called ‘’phase problem’’ of crystallography. The standard techniques and approaches (Multan [1, 2], ShelXD [3], Sir99 [4], etc.), developed in order to solve this problem, are based on the application of direct methods which estimate the phases of the Fourier transform of the scattering density from the observed intensities. We will describe in detail the different steps and procedures followed for the structural resolution of our compounds [5].

Figure 1 Main steps in a typical direct methods procedure [6].

[1] Germain G & Woolfson M M (1968) Acta Cryst, B24, 91-96. [2] Main P, Fiske S J, Hull S E, Lessinger L, Germain G, Declercq J P & Woolfson M M (1980) MULTAN80: A System of Computer

Programs for the Automatic Solution of Crystal Structures from X-ray Diffraction Data, University of York and Louvain. [3] Sheldrick G M (1998) (ed. S. Fortier) In: Direct Methods for Solving Macromolecular Structure, Dordrecht: Kluwer Academic

Publishers. [4] Burla M C, Camalli M, Carrozzini B, Cascarano G L, Giacovazzo C, Polidori G & Spagna R (1999) Acta Cryst, A55, 991-999. [5] Benali-Cherif N, Direm A, Allouche F & Soudani S (2007) Acta Cryst, E63, 2272–2274. [6] Giacovazzo C, Capitelli F, Cuocci C & Ianigro M (2002) Direct methods and Applications to Electron Crystallography, Elsevier

Science (USA).

MODIFICATION OF THE TRIANGULAR HOST MOLECULES LEADING TO INCLUSION OF ETHYL ACETATE IN THEIR INNER CAVITY

Agnieszka Plutecka and Urszula Rychlewska (Department of Chemistry, Adam Mickiewicz University, Poznan, Poland) agnieszk@amu.edu.pl, urszular@amu.edu.pl

Investigated macrocyles were obtained through [3+3] cyclocondensation between enantiomerically pure trans-1,2-diaminecyclohexane and terephtalic aldehyde. Due to their triangular molecular shape and a presence of imine or amine groups, we called them trianglimines or trianglamines.

Figure 3 Type of host molecules: trianglimine, trianglamine and bridged trianglamine.

While trianglamine displays considerable ring flexibility that allows inter- and intramolecular inclusion of various type of solvent molecules, trianglimine and methylene bridged trianglamine possess more rigid skeletons. The focus of this study was to investigate the ability of trianglimine, trianglamine and bridged trianglamine to include ethyl acetate into their inner cavity. In all investigated crystals the host molecules pack in stacks: in trianglimine crystals [1], the ethyl acetate places itself in between the host molecules forming a stack, while in trianglamine and bridged trianglamine crystals the guest molecules enter into the inner cavity of the host. Moreover, the trianglamine crystal structure displays host/guest disorder which is a result of the conformational flexibility of the macrocyclic skeleton. The host molecules either allow or prevent the solvent molecules to enter into the intramolecular cavity [2]. At variance, bridged trianglamine crystallizes with two symmetry independent host molecules and the two molecules adopt different conformations, each resembling one of the two conformational states adopted by the disordered host molecules in non-bridged trianglamine. One of these molecules allows while the other prevents the guest molecules to enter into the inner cavity. Our studies demonstrate that trianglimine cavity is too small to accommodate the ethyl acetate molecule, while the trianglamine host is too flexible to allow the full control of the intramolecular inclusion. Bridged trianglamine, with rigid macrocycle and well defined inner cavity is best suited for ethyl acetate inclusion.

Figure 4 Inclusion of ethyl acetate molecules within the host matrices of trianglimine, trianglamine and bridged trianglamine (from left

to right, respectively).

This work was supported by Foundation for Polish Science (FOCUS fellowship). Studied compounds have been synthesized in Dept. of Organic Stereochemistry Adam Mickiewicz University, Poznań, Poland. [1] Gawroński J, Kolbon H, Kwit M, Katrusiak A (2000) J. Org. Chem. 65:5768–5773. [2] Gawroński J, Gawrońska K, Grajewski J, Kwit M, Plutecka A, Rychlewska U (2006) Chem. Eur. J. 12:1807–1817.

Diphenic acid based Indium MOFs as selective heterogeneous catalysts

M. Celeste Bernini (Instituto de Ciencia de Materiales de Madrid), Manuela E. Medina (Instituto de Ciencia de Materiales de Madrid), Ana E. Platero-Prats (Instituto de Ciencia de Materiales de Madrid), Enrique Gutiérrez-Puebla (Instituto de Ciencia de Materiales de Madrid), Marta Iglesias (Instituto de Ciencia de Materiales de Madrid), Elena López-Torres (Universidad Autónoma de Madrid), M. Ángeles Monge (Instituto de Ciencia de Materiales de Madrid) and Natalia Snejko (Instituto de Ciencia de Materiales de Madrid) (celeste.bernini@icmm.csic.es, memedina@icmm.csic.es, aplatero@icmm.csic.es).

Metal-organic frameworks (MOFs) have been recognized for their great potential to act as crystalline functional solid state materials with interesting structural properties and promising applications, such as gas storage/separation, drug delivery and heterogeneous catalysis [1,2].

We have been engaged for long time in the design of Indium MOFs, which have been proved to be active as Lewis and redox heterogeneous catalysts [3,4]. In this sense, we present here the hydrothermal synthesis and crystal structure of two new In MOFs based on diphenic acid and nitrogenated tether ligands: compound 1 with 1,10-phenantroline and compound 2 with 2,2’-bipyridyl. Besides, reaction with 2,2’-bipyridyl under certain conditions also leads to the formation of two dimeric precursors (compounds 3 and 4), which have been also characterisazed by single crystal X-Ray Diffraction.

Moreover, the potential applications of these MOFs have been also explored. Thus, the preliminary results in aldehydes acetalization and selective sulfides oxidation as heterogeneous catalysts tests are also shown. It is worth highlighting that, for both reactions the best results were obtained using compound 1. These results can be explained taking into account the structural features of this MOF.

1 2

Figure 5 . The figure shows the two new In MOFs based on diphenic acid and nitrogenated tether ligands: compound 1 with 1,10-phenantroline and compound 2 with 2,2’-bipyridyl.

[1] Li, J. R.; Kuppler, R. J.; Zhou, H.C. (2009) Chem. Soc. Rev. 38, (5), 1477-1504. [2] Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, (5), 1450-1459. [3] Gándara, F.; Gómez-Lor, B.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Proserpio, D. M.; Snejko, N. (2007) Chem. Mater. 20, (1), 72-76. [4] Gómez-Lor, B.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Ruiz-Valero, C.; Snejko, N., (2002) Inorg. Chem. 41(9), 2429-2432.

Knowledge-guided screening tools for identification of porous materials for CO2 separation

Maciej Haranczyk

Computational Research Division, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720 Email: MHaranczyk@lbl.gov

Porous materials such as zeolites and metal organic frameworks (MOFs) are important materials for energy-related applications. Zeolites, for example, have been widely used as catalysts for oil refinement. MOFs can be used as materials for gas storage or separation. Chemists and material scientists need to identify best porous materials for these applications. Along this line of research databases of possible structures are being developed and they could in principle be screened for the best structure of any desired property. There are, however, a number of technical challenges that currently prevents such screening. One of them is a lack of automated tools for analysis of void space of porous materials. Each structure has to be analyzed by a researcher using visualization tools. Other challenge comes from the fact that the computational cost of molecular simulations that need to be run to predict properties of these materials prohibits their application in the characterization of the entire database of structures, which would be needed to perform screening for new materials.

The goal of our project is to develop new techniques for fast screening of databases of porous materials. In our approach, the computational effort required to characterize the entire library of structures in order to perform screening is reduced to a large extent by a knowledge-based and similarity-based selection of structures to undergo characterization. The development of the proposed approach involves three steps: (1) development of structure descriptors and structure similarity measures operating on them. These tools are based on advancements in the field of applied mathematics, in particular, computational geometry, applied topology, numerical PDEs and machine learning tools; (2) selection and computational characterization of an initial set of structures, and then (3) knowledge extraction and execution based on variety of techniques, including similarity-based and machine learning methods.

Structural Rearrangements and Photoreactivity in the Solid State

Goutam Kumar Kole (Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore-117543), Jagadese J. Vittal(Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore-117543),

chmjjv@nus.edu.sg

The photochemical [2+2] cycloaddition reactions in the solid state have been very well studied in the past. Although it is possible to align the C=C bonds favorable for the photoreactions, this does not guarantee the reaction to take place in the crystals. For example, a number of compounds containing C=C bonds do not undergo photodimerization in the solid state despite satisfying Schmidt’s criteria, whereas there are a number of cases where photocyclization is not expected, surprisingly found to be reactive. Crystal structure analyses of these systems exhibiting unexpected photoreactivity unraveled several pieces of new information about the mobility of the molecules. Of the organic molecules studied so far, trans 1,2-bis(4-pyridyl)ethene (bpe) containing two pyridyl nitrogen atoms has been extensively investigated in our laboratory. For instance, a ladder coordination polymer where infinite pairs of C=C bonds in bpe are aligned has been found to undergo single-crystal to single-crystal structural transformation under UV light. Whereas a Ag(I) 1D coordination polymer reorganized to a ladder structure upon desolvation and further undergoes [2+2] cycloaddition under UV irradiation quantitatively. Similar observation has been observed in another 1D coordination polymer also. On the other hand, during the grinding process the infinitely packed trans-3-(4-pyridyl) acrylic acid salt in head-to-head fashion with one third of C=C bonds in crisscross fashion in the single crystals takes up a water molecule and rearranges to form isolated pairs congenial for [2+2] cycloaddition quantitatively. Similarly, cycloaddition reaction in a triple-stranded ladder coordination polymer has been found to take place in two steps via cooperative molecular movements of the partially dimerized products formed initially. We will highlight the role of solvents in the structural rearrangements to assist the alignment of C=C bonds for [2+2] cycloaddition reactions in this poster. [1] Toh N. L., Nagarathinam M., Vittal J. J. (2005) Angew. Chem. Int. Ed. 44: 2237 –2241 [2] Peedikakkal A. M. P., Vittal J. J. (2008) Chem. Eur. J. 14: 5329-5334 [3] Nagarathinam M., Vittal J. J. (2008) Chem. Commun. 438-440 [4] Peedikakkal A. M. P., Vittal J. J. (2010) Inorg. Chem. 49: 10-12 [5] Kole G. K., Koh L. L., Lee S. Y., Lee S. S., Vittal J. J. (2010) Chem. Commun. 46: 3660 - 3662 [6] Kole G. K., Tan G. K., Vittal J. J. (2010) Org. Lett. 12: 128-131