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Tatiana E.Gorelik, Galina Matveeva, Ute Kolb

Institute of Physical Chemistry,Johannes-Gutenberg University

Mainz, Germany

APPLICATION OFAUTOMATED ELECTRON DIFFRACTION

TO STRUCTURAL INVESTIGATIONOF MOLECULAR CRYSTALS

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Sponsored by The International Centre for Diffraction Data

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Transmission electron microscope (TEM) Imaging High-resolution imaging

Elemental analysis (EDX)

Electron diffraction

APPLICATION OF AUTOMATED ELECTRON DIFFRACTION TO STRUCTURAL INVESTIGATION OF MOLECULAR CRYSTALS

APPLICATION OF AUTOMATED ELECTRON DIFFRACTION TO STRUCTURAL INVESTIGATION OF MOLECULAR CRYSTALS

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Single crystal electron diffraction: tilt seriesPowder electron diffraction

Pawley and Rietveldrefinements using electrondiffraction from L12-typeintermetallic Au3Fe1-xnanocrystals duringtheir in-situorder–disorder transition

Zhiping Luo, YolandaVasquez, James F.Bondi,Raymond E.Schaak

Ultramicroscopy, 2011

APPLICATION OF AUTOMATED ELECTRON DIFFRACTION TO STRUCTURAL INVESTIGATION OF MOLECULAR CRYSTALS

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Single crystal electron diffraction: tilt seriesPowder electron diffraction

Pawley and Rietveldrefinements using electrondiffraction from L12-typeintermetallic Au3Fe1-xnanocrystals duringtheir in-situorder–disorder transition

Zhiping Luo, YolandaVasquez, James F.Bondi,Raymond E.Schaak

Ultramicroscopy, 2011

Structure solution using zonal electron diffraction data: historical overview

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Rigamonti, R., La struttura della catena paraffinica studiata mediante i raggi dielettroni, Gazzetta Chimica Italiana 66 174-182 (1936)

D.L. Dorset, Structural electron crystallography, Plenum New York (1995)

Voigt-Martin et al., The use of simulation mehods to obtain the structure andconformation of 10-cyano-9,9‘-bianthryl by electron diffraction and high-resolution imaging, Ultramicrocopy 57, 29-43 (1995)

Organic samples

Biological samples2D Protein crystals

Dorset, D.L., Direct structure analysis in protein electron crystallography:crystallographic phases for halorhodopsin to 6Å resolution, Proc Natl Acad SciUSA 92(22), 10074–10078 (1995)

Weirich et al. A crystal structure determined with 0.02 Å accuracy with electronmicroscopy, Nature 382, 144 (1996)

Hovmöller et al., Accurate atomic positions from electron microscopy, Nature311, 238-241 (1984)

Inorganic samples(thin)

→ Solution using structure factor phases derived from HRTEMKühlbrandt, W. et al. Atomic model of plant-light harvesting complex by electroncrystallography, Nature 367, 614, (1997) – 3.4 Å resolution

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Automated electron Diffraction Tomography (ADT):collection of the complete reciprocal data rather than zonal patterns

AUTOMATED ELECTRON DIFFRACTION: THE EXPERIMENT

Towards automated diffraction tomography. Part I - Data AcquisitionU. Kolb, T. Gorelik, C. Kubel, M.T. Otten and D. Hubert,Ultramicroscopy, 107, 507-513 (2007).

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AUTOMATED ELECTRON DIFFRACTION: DATA PROCESSING

Automated electron Diffraction Tomography (ADT):collection of the complete reciprocal data rather than zonal patterns

Towards automated diffraction tomography. Part II - cell parameter determinationU. Kolb, T. Gorelik, M.T. Otten, Ultramicroscopy, 108, 763-772 (2008).

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AUTOMATED ELECTRON DIFFRACTION: DATA PROCESSING

Automated electron Diffraction Tomography (ADT):collection of the complete reciprocal data rather than zonal patterns

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Minerals:Mullite Al6Si2O13

SarrabusiteCharoite-96Charoite-90

Intermetallicnanophases:ZnSb, Zn8Sb7

Ca-compounds:Calcite, Vaterite

Calcium silicate hydrateCa5Si6O17·5H2O

Metal OrganicFrameworks (MOF):

MUF-4lBasolite

High pressure phases:HP hydrous Al-pyroxene

(Mg2Al(OH)2AlSiO6)

Organic-inorganichybrids:

ECS3, ECS5

Organic:NLO-active material

Organic pigmentsAmides

Zeolites:ZSM-5 (NaxAlxSi96-xO192)

Natrolite Na2Al2Si3O10·2H2OIM-5

RKL 040

Phosphates:SrP3N5O

Ba6Br3P12N17O9

Oxides:Na2W4O13Li2Ti3NiO8

NaHTi3O7·H2ONa2Ti6O13

MORE THAN 30 STRUCTURES ARE SOLVED FROM ADT DATA BY NOW (16 OUT OF THEM - NEW)

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agglomeratedcrystalsZn8Sb7 ~40 nm

AUTOMATED ELECTRON DIFFRACTION TOMOGRAPHY

small crystals radiation damage

disorder

200 nm

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Radiation damage: CNBA

STEM vs. TEM;Distribute the dose (crystal bending!);Cool the sample

e-dose rate:0.2-0.3 e/A2s

ELECTRON BEAM DAMAGE

STEM

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Orthorombic paracetamol (Pcab)

ADT As given byHaisa et al., 1974

11.4 A 11.805 A

17.4 A 17.164 A

7.6 A 7.393 A

90.1° 90°

90.0° 90°

88.1°* 90°

Projection (010):extinctions along c* direction(b-glide plane)

Material provided by Elena Boldyreva,Novosibirsk State University

ADT: UNIL CELL PARAMETERS DETERMINATION

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Orthorombic paracetamol (Pcab)

ADT As given byHaisa et al., 1974

11.4 A 11.805 A

17.4 A 17.164 A

7.6 A 7.393 A

90.1° 90°

90.0° 90°

88.1°* 90°

Projection (010):extinctions along c* direction(b-glide plane)

Material provided by Elena Boldyreva,Novosibirsk State University

ADT: UNIL CELL PARAMETERS DETERMINATION

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ADT: STACKING FAULTS - DISORDER

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Conclusion

Caution during data acquisition

Lattice cell parameters determination is always possible …

Alternative structure solution approaches formedium-resolution data

Direct methods structure solution for high resolution data

APPLICATION OF AUTOMATED ELECTRON DIFFRACTION TO STRUCTURAL INVESTIGATION OF MOLECULAR CRYSTALS

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Group

Ute Kolb

Galina MatveevaEnrico MugnaioliAndrew StewartIryna Andrusenko

Sebastian SchlittUlrich Heil

Rudolf WurfelRobert Branscheid

Financial support SFB 625

Max Otten, FEI, Eindhoven, The NetherlandsJacco van de Streek, Avant-garde Materials Simulation, FreiburgMartin U. Schmidt, University of Frankfurt-am-MainAndreas F.M. Kilbinger, Institute of Organic Chemistry, Mainz