on the abundance of chiral crystals (an optimistic lecture for the conclusion of the conference)
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On the abundance of chiral crystals (An optimistic lecture for the conclusion of the conference) David Avnir Institute of Chemistry The Hebrew University of Jerusalem, Israel With Chaim Dryzun Department of Chemistry, ETH Zürich Lugano Campus, Switzerland - PowerPoint PPT PresentationTRANSCRIPT
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On the abundance of chiral crystals(An optimistic lecture for the conclusion of the conference)
David Avnir
Institute of ChemistryThe Hebrew University of Jerusalem, Israel
WithChaim Dryzun
Department of Chemistry, ETH ZürichLugano Campus, Switzerland
Chirality 2012, Fort Worth, Texas June 10 - June 13, 2012
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The unrecognized high abundance of chiral crystals * ~23% of all non-biological crystals are chiral(compared to only ~10% of all non-biological molecules )
* Only ~6% of these are labelled as chiral In numbers:there are out there ~100,000 crystals the chirality of which has been ignored
It means that:The library from which one can select enantioselective catalysts, sensing materials, and chromatographic materials is by far larger than envisaged so far.
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Questions to be addressed:
# Why was it overlooked?
# Why are chiral crystals much more common than chiral molecules?
# What are the practical implications of this finding?
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What is a chiral crystal?
What may be chiral in a crystal?
# The molecule
# The asymmetric unit
# The unit cell
# The space-group
# The macroscopic habit
H. D. Flack, Helv. Chim. Acta, 2003, 86, 905
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Class I:
The 165 space groups which contain at least one improper operation (inversion, mirror, glide or Sn operations).
Always achiral(although the 3D asymmetric unit is always chiral)
The classes of space groups
P m
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Class II: 22 chiral-helical space groups (11 enantiomeric pairs)
Contain at least one screw axis which is not the 21-screw axis.
Always chiraleven if the AU is achiral
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The confusing class III: 43 space groups that contain only proper rotations and the 21-screw rotation
Examples: P 21, P 4, the abundant P 21 21 21.
Despite the fact that there are no reflections, inversions etc., these space groups are achiral
Despite the fact that these space groups are achiral, the crystals which pack by them are always chiral
How can that be?
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# P21 is achiral because reflection of this mathematical entity results in unchanged P21
# P61 is chiral because its reflection results in P65
Despite the fact that there are no reflections, inversions etc., these 43 space groups are achiral
In general, a crystal may be chiral and yet belong to one of these 43 achiral space groups
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Despite the fact that these space groups are achiral, the crystals which pack by them are chiral
The reason for:
* An AU in 3D is always chiral. A chiral AU on which only proper operations are applied, must result in a chiral crystal.
* If the AU is achiral (0D, 1D, 2D) – then it will usually pack in a space group which has that achiral operation, coinciding with it.
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Class II and Class III are collectively known as the 65 Sohncke groups
II: 22 of the 65 are chiral (helical)III: 43 of the 65 are achiral Bottom line:
All of the 65 Sohncke groups - and only these groups - represent chiral crystals
The Sohncke symmetry space groups
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Wrong
H. D. Flack, Helv. Chim. Acta, 2003, 86, 905
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To remove the confusion we suggest:
Class I: 165 improper-achiral groupsAlways an achiral crystal
Class II: 22 helical-chiral groupsAlways a chiral crystal
Class III: 43 proper-achiral groupsAlways a chiral crystal
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If the space group contains only proper operations, the crystal is chiral
Proper operations: rotations, screw-rotations and translations
Achiral crystal - improper operations (mirror, inversion, S4, S6 or glide)
Simple tests for the chirality of a crystal
Santiago Alvarez’ Criterion:
A crystal is chiral if the symbol of its space group is composed only of a capital letter and simple numbers
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Number of reported non-biological crystal structures (CSD, ICSD):574,000
Chiral structures:131,000
% of all non-biological chiral crystals:23%
Number of structures reported as chiral:35,000 (6% only)
Number of chiral crystals not recognized as such: ~96,000
The numbers
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Measuring the degree of chirality
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G: The achiral symmetry point group which minimizes S(G)
Achiral molecule: S(G) = 0 The more chiral the molecule is, the higher is S(G)
The continuous chirality measure (CCM)
N
1k
2
2ˆ1min100 kk QQ
Nd)S(G
Mezey, Gilat, Kauzman, Osipov, Mislow, Ruch, Richards, Maruani
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S(TP)
[Ta(CCSitBu3)6]- [Ti2(-SMe)3(SMe)6]
2-[Zr(SC6H4-4-OMe)6]2-
1.88
18.8°
1.67
8.27
5.51
1.34
33.3°
4.45
3.94
2.16
30.4°
5.09
S(chir)
S(Oh)
The most chiral monodentate complex
With S. Alvarez, Europ. J. Inorg, Chem., 1499 (2001)
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The chirality of a unit-cell
1 sec
S(C2)=0.00
S(chirality)=4.51
S(Ci)=36.54
516 atoms
bis((2-phenoxo)-bis(triphenylphosphine)-copper), C84H70Cu2O2P4 (HEZXEP (P2)); Osakada, K.; Takizawa, T.; Tanaka, M.; Yamamoto, T. J. Organometallic Chem., 1994, 473, 359-369.
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Le Chatelier, H. Compt. Rend de I'Acad. Sciences 1889, 109, 264.
The optical rotation of quartz: More than 120 years ago Le Chatelier and his contemporaries
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0.97
1.02
1.07
1.12
1.17
98 298 498 698 898 1098
Temperature ( K)
0.54
0.56
0.58
0.6
0.62
0.64
Temperature (°K)
Le
Cha
telie
r
t
Chirality, SiSi4
Chirality t
120 years later: an exact match with quantitative chirality changes
D. Yogev, Tetrahedron: Asymmetry 18, 2295 (2007)
SiSi4
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Examples of publications on chiral crystals where terms such as “Chirality”, “Chiral”, “Optical activity”, etc., do not appear in the title, abstract and the whole text.
All are of class III, the 43 proper-achiral space groups
A chemist running a search which has any of these keywords, will simply miss 100,000 structures!
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Example 1: C25H18O2
CSD: ABUCOP, space group: P 2 21 21 (#18), CCM-UC = 11.15
S. Apel, S. Nitsche, K. Beketov, W. Seichter, J. Seidel, E. Weber, J. Chem. Soc., Perkin Trans. 2, 2001, 7, 1212
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CCM of one molecule = 2.82
Example 1: C25H18O2
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Example 2: C12H40Cs4N4Si4
CSD: JUFWUK, space group: P 3 2 (#195), CCM-UC = 0.47
Tesh, K. F.; Jones, B. D.; Hanusa, T. P.; Huffman, J.C. J. Am. Chem. Soc. 1992, 114, 6590.
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CCM of one molecule = 0.47
Example 2: C12H40Cs4N4Si4
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Example 3: C16H12N2O2
CSD: BIXLOJ, the most common proper-achiral group: P 21 21 21,(#19)CCM of the UC = 2.01
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Example 3: C16H12N2O2 (CSD code: BIXLOJ)
Space group: P 21 21 21 (#19)
CCM of one molecule inside the crystal = 0.19
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Example 4: NH3, Ammonia
Space group: P 21 3 (#198), UC-CCM = 1.89, CCM one molecule = 0
The terms “chirality”, “optical activity” etc’ do not appear in ANY of the publications on ammonia crystals !
Boese, R.; Niederpruem, N.; Blaeser, D.; Maulitz, A.H.; Antipin, M.; Yu.; Mallinson, P.R.J. Phys. Chem. B, 1997, 101, 5794–5799.
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Example 5: Crystallization of a racemate leads to a P21 chiral crystal
The pair of enantiomers in the AU are related by pseudo-inversion:the phenyl rings, which are twisted differently
Steinberg, A., Ergaz, I., Toscano, R.A., Glaser, R. 2011. Cryst. Growth Des. 11, 1262-1270.
(±)-(1RS,3SR,4RS)-1-Phenyl-cis-3,4-butano-3,4,5,6-tetrahydro-1H-2,5- benzoxazocine hydrochloride
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Why are chiral crystals much more common than chiral molecules?
% of all non-biological chiral crystals:23%
% of all non-biological molecules: ~10%
# Solution-achiral molecules need not crystallize in their equilibrium achiral structure
# They provide a very rich library of chiral conformers, which is the source of the abundance of chiral crystals
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Why was it overlooked?
* The confusion, even in text books, of what is a chiral crystal.
* For a crystallographer the chirality maybe obvious from the space-group. The cost: Chemists searching “chiral” will miss it.
* Crystallization from a racemic mixture results in a mixture of right- and left-handed crystals which needs to be separated
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Practical aspects: Chiral Silicate ZeolitesMost silicate-zolites are highly symmetric
ZSM-5, a silicate zeolite: NanAlnSi96-nO192•16H2O
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Chiral zeolites
Prime importance:* Enantioselective catalysis* Enantiomers separation* Enantioselective sensing
Known:Zeolite-like, open-pore crystals, MOF’s, etc.Out of over 700 zeolite structures only 5 are recognized as chiral
Desired:Chiral aluminosilicate zeolitesOnly one was reported
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We found 21(!) chiral silicate zeoliteswhich have been under the nose all the time!
a. Goosecreekite. b. Bikitaite. c. The two enantiomeric forms of Nabesite
Ch. Dryzun et al, J. Mater. Chem., 19, 2062 (2009)Editor’s Choice, Science, 323, 1266 (2009)
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Out of 120 classical silicate zeolites, we found 21 chiral zeolites, that were not recognized as such
That is very close to the 23% general abundance we foundAll belong to the non-helical Sohncke space groups
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Goosecreekite (GOO)
Chiral zincophosphate I
(CZP)α-Quartz
TT’4 2.05 2.94 0.55
SBU 0.86 0.37 ------
A.U. 14.76 1.28 0.00
Unit cell 4.90 8.91 1.28
The chirality values are comparable or larger than the chirality values of the known chiral zeotypes
and of quartz
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Adsorption of D-histidine (the lower curve) or L-histidine (the higher curve) on Goosecreekite (GOO): The heat flow per injection
The isothermal titration calorimetry (ITC) experiment
L-histidine
With Y. Mastai and A. Shvalb, Bar-Ilan
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Conclusion
There are some 100,000 unrecognized chiral crystals out there, waiting to be utilized for enantioselective catalysis, sensing, and separation.
C. Dryzun and D. Avnir, Chem. Commun., 2012, 48, 5874–5876, Special Chirality web themed issue
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