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Variable Temperature and Variable Temperature and Pressure Techniques for Pressure Techniques for in situin situ
CrystallizationCrystallization
Roland BoeseRoland Boesecontributions contributions
from:from:D. BläserD. Bläser
V.R. ThalladiV.R. ThalladiC. SchauerteC. Schauerte
M. T. KirchnerM. T. Kirchner
Erice, 16. 6. 2004Erice, 16. 6. 2004
A. GehrkeA. Gehrke
Variable Temperature and Variable Temperature and Pressure Techniques for Pressure Techniques for in situin situ
CrystallizationCrystallization
Erice, 16. 6. 2004Erice, 16. 6. 2004
Roland BoeseRoland Boesefinancial aid:financial aid:
DFGDFGSFBSFB452452 ratiopharmratiopharm
In situ - Crystallization
What is it?
Crystallization on the diffractometer in capillaries
In situ - Crystallization
Why should we do so?Why should we do so?
• Crystals grown outside cannot be transferred to the Crystals grown outside cannot be transferred to the diffractometer without damagediffractometer without damage
• Better control on crystallization processBetter control on crystallization process
In situ - Crystallization
How to do it?How to do it?
• Fill capillaryFill capillary• Mount itMount it• Switch on LT-deviceSwitch on LT-device• Grow crystalGrow crystal• Check crystal qualityCheck crystal quality• Collect dataCollect data• Solve structureSolve structure
Fill capillaryFill capillary
Fill capillaryFill capillary
Fill capillaryFill capillary
Transfer to DiffractometerTransfer to Diffractometer
DetectorDetector
X-ray-SourceX-ray-Source
CoolingCooling
ObservationObservation
LaserLaser
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up again Why?
TTmeltmelt
TT
VVcrystal growthcrystal growthVVnucleationnucleation
metastable regionmetastable regioncritical size
critical size
we need to heat!we need to heat!
In situ - Crystallization
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up againwith fingerswith fingers
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up againwith spatulumwith spatulum
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up againwith heated wire (loop)with heated wire (loop)
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up againwith heated platewith heated plate
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up againwith IR-radiationwith IR-radiation
In situ - Crystallization
How to crystallize?How to crystallize?• Simply cool downSimply cool down• And warm up againAnd warm up againwith IR-laserwith IR-laser
In situ - Crystallization
Why with laser?Why with laser?• Simply cool downSimply cool down• And warm up againAnd warm up againwith IR-laserwith IR-laser
In situ - Crystallization
Why with laser?Why with laser?• Simply cool downSimply cool down• And warm up againAnd warm up againwith IR-laserwith IR-laser
Advantages:Advantages:growing from bottom to topgrowing from bottom to topoptical observationoptical observationno mechanical break of no mechanical break of
capillarycapillarycontrol on heatcontrol on heatcontrol on positioncontrol on positionhigh temperature gradienthigh temperature gradient
COCO22 laser laser
laser diodelaser diode
mirrormirror
ZnSeZnSe--lenslens
turning turning mirrormirror
LT-deviceLT-device
OOptical ptical HHeating and eating and CCrystallization rystallization DDeviceevice
O.H.C.D.
url:
http://www.ohcd-system.com
In situ - Crystallization
undistorted crystallization zone
In situ - Crystallization
… … and Polymorphism studiesand Polymorphism studies
Meat to the
bones
• What for?What for?
• LiquidsLiquids• GasesGases• SolutSolutionionss• Phase transitionsPhase transitions• Trapping of chemical reaction products Trapping of chemical reaction products • Co-crystalsCo-crystals• ClathratesClathrates
• n-nonanen-nonane– ‘‘rotator' phaserotator' phase
circumvent of disordered phasescircumvent of disordered phases
In situ crystallizationIn situ crystallization
25
20
15
10
5
0
-80 -70 -60 -50 -40 -30 -20
-57.03°C-57.03°Cphase transitionphase transition
-54.08°C-54.08°Cmelting pointmelting point
temperature (°C)
hea
t tr
ansf
er(m
W)
DSC heating curve of DSC heating curve of nn-nonane-nonane
shattershatter crystallizationcrystallization
crystallizationcrystallizationfrom solutionfrom solution
ordered phase
melt
rotator phase
• no crystal seedsno crystal seeds– temperature shockstemperature shocks– ultrasonicultrasonic– external seedingexternal seeding– internal seedinginternal seeding
• for ethylenglykol with phenazine (template effect)for ethylenglykol with phenazine (template effect)
problemsproblems
Crystallization techniquesCrystallization techniques
• ethylen glykolethylen glykol– glassy stateglassy state
In situ - Crystallization
phenazine
1,2-diphenyl-ethylene glycol
1,2-diphenyl-ethylene glycol
OH • • •N bridges
OH • • •N bridges
OH • • •N bridges
OH • • •N bridges
ethylen glykol
ethylen glykol oo
o
oo
phenazine
phenazine
Crystallization techniquesCrystallization techniques
crystal structure of ethylen glykolcrystal structure of ethylen glykol
R. Boese, H.-C. Weiss,Acta Crystallogr. 1998, C54, 24.
PyridinePyridine
N H N HN H N H
expected packing pattern
realized:
• D. Mootz and H.-G. Wussow, J. Chem. Phys., 1981, 75, 1517.
• no linear CH···N
• Z' = 4
• no thermodynamic minimum (calculated, S. Price et al., Cryst Eng. Comm. 2002)
DSCs DSCs pyridine and perdeutero-pyridine in pyridine and perdeutero-pyridine in
pentanepentane
-100 -80 -60 -40 -20 0 20Temperatur /°C
-8
-7
-6
-5
-4
-3
-2
-1
0
DSC /(mW/mg)
Kompl.Peakausw : Fläche:Onset:
58.34 J/g-60.8 °C
Kompl.Peakausw : Fläche: -80.19 J/g
Onset*: -72.2 °C
[5.2][5.4] Exo
-100 -80 -60 -40 -20 0 20Temperatur /°C
-4.00
-3.50
-3.00
-2.50
-2.00
-1.50
-1.00
-0.50
0.0
DSC /(mW/mg)
Onset*: -66.7 °C Onset*: -55.1 °C
Kompl.Peakausw : Fläche: 6.137 J/g
Kompl.Peakausw : Fläche: 51.09 J/g
Kompl.Peakausw : Fläche: -53.51 J/g
Onset*: -81.0 °C
[7.2][7.4]
Exo
pyridine perdeutero-pyridine
PyridinePyridine
PyridinePyridine
perdeutero-perdeutero-PyridinePyridine
perdeutero-perdeutero-PyridinePyridine
Same form found by S. Parsons for high pressure form, but also for the non-deuterated pyridine!
α-Form α-Form PP2211//n,n, 107.138°, 107.138°,5.8216, 10.4597, 8.9402Å,5.8216, 10.4597, 8.9402Å,V = 520, ρ = 0.908 g/cm³V = 520, ρ = 0.908 g/cm³
α-Form α-Form PP2211//n,n, 107.138°, 107.138°,5.8216, 10.4597, 8.9402Å,5.8216, 10.4597, 8.9402Å,V = 520, ρ = 0.908 g/cm³V = 520, ρ = 0.908 g/cm³
ß-Form ß-Form PP2211//c,c, 107.209°, 107.209°,7.2414, 8.1909, 10.8014Å, 7.2414, 8.1909, 10.8014Å, V = 612, V = 612, ρ ρ = 0.913 g/cm³= 0.913 g/cm³
ß-Form ß-Form PP2211//c,c, 107.209°, 107.209°,7.2414, 8.1909, 10.8014Å, 7.2414, 8.1909, 10.8014Å, V = 612, V = 612, ρ ρ = 0.913 g/cm³= 0.913 g/cm³
molecular complexes and networksmolecular complexes and networks
Aceton + AcetyleneAceton + AcetyleneAceton + AcetyleneAceton + Acetylene
1 : 1
2 : 1
O
C-H···O
EthynylbenzeneEthynylbenzene + Pyrazine + Pyrazine
N N
??N N
P-Diethinylbenzene + PyridinP-Diethinylbenzene + Pyridin
sublimation energies in kJ/mol
-45.0
-58.7
N N
N N
1x
2x
-162.4
-164.6stabilization by
2.2 kJ/mol
N N
N
-53.3
-75.5
2x
1x
-182.1
-169.6
destabilization by 12.5 kJ/mol
data by Martin U. Schmidt, Frankfurt
(ESP charges, Dreiding2.21, optimized)
Option 1Option 1
N N
NN
NN NN Option 2Option 2
Acetylene + PyridinAcetylene + Pyridin
Acetylene + PyridinAcetylene + Pyridin
Option 3Option 3
Option 4Option 4
OO
OO OO
Acetylene + ….Acetylene + ….
Option 5Option 5O
O
O
O
Acetylene + ….Acetylene + ….
Option 6Option 6
Acetylene + AcetyleneAcetylene + Acetylene
Option 7Option 7
π
π
π
π
π
π
π
π
Acetylene + Acetylene + π-System
in situin situ Cocrystallization Cocrystallizationof Gaseous Compoundsof Gaseous CompoundsAcetylene + AcetonAcetylene + Aceton
Acetylene + Acetylene + BenzeneBenzene
Acetylene + Acetylene + DimethylpyrazineDimethylpyrazineAcetylene + WaterAcetylene + Water
Water + MethaneWater + Methane
Water + Methane + Water + Methane + PropanePropane Water + Methane + Water + Methane + AdamantaneAdamantane
Water + Water + PropanePropane
GashydratesGashydrates
Acetylene + Acetylene + DioxaneDioxaneAcetylene + PyridinAcetylene + Pyridin
Acetylene + MethanolAcetylene + MethanolAcetylene + Acetylene + DimethylpyridinDimethylpyridinAcetylene + Di-Acetylene + Di-terttert-butylpyridin-butylpyridin
Acetylene + DMSOAcetylene + DMSO
molecular complexes and networksmolecular complexes and networks
DMSO + AcetyleneDMSO + Acetylene
Acetylene + BenzeneAcetylene + Benzene
8.21 8.21 ÅÅ
Acetylene + BenzeneAcetylene + Benzene
1.097 ÅÅ at 201K
1.157 ÅÅ at 123K
compare
1.20 ÅÅ Di-tert-butylethyne
Acetylene + Benzene
Acetylene + MethanolAcetylene + Methanol
Cmcm
Cmc21
Acetylene + MethanolAcetylene + Methanol
Acetylene + MethanolAcetylene + Methanol
Acetylene + MethanolAcetylene + Methanol
Space group P Space group P 221122112211
a a = 4.573, = 4.573, b b = 7.327, = 7.327, c c = = 13.158 Å 13.158 Å
Space groupSpace group CmcCmc2211
a a = = 6.417, 6.417, b b = = 7.228, 7.228, c c = = 4.652 4.652 ÅÅ
gas hydrates
below the oceans we have twice as much methane in clathrates than the eqivalent of all
known fossile fuel in the world
up to 10% of the off-shore conveying costs for natural gas is spent to avoid gas hydrates
in the sensitive equilibrium methane/water, natural gas is released by heating the oceans,
which is again the most effective geenhouse gas
GashydratesGashydrates
• Methane + Methane + WaterWater• Temperature:Temperature: below 8 °C below 8 °C • pressurepressure above 20 bar above 20 bar
Evaluation: Single ‚Frame‘Evaluation: Single ‚Frame‘
Multiple Single Crystals Multiple Single Crystals (‚oligocrystalline‘ material)(‚oligocrystalline‘ material)
'oligo'-diffractometry'oligo'-diffractometry
powder-diffractometrypowder-diffractometry
single crystal-diffractometrysingle crystal-diffractometry
occurenceoccurenceeconomical relevanceeconomical relevanceecological relevanceecological relevance
GashydratesGashydrates
'burning ice'
'burning ice'
O-H···OO-H···ODodecahedroDodecahedro
nnMethane (without Methane (without H‘s)H‘s)
Tetrakai-Tetrakai-decahedrodecahedronnMethane (with H‘s)Methane (with H‘s)
PropanPropanee
Hexakai-Hexakai-decahedrondecahedron Form IForm IForm IIForm II
GashydratesGashydrates
PropanPropanee
Hexakai-Hexakai-decahedrondecahedron Form IIForm II
GashydratesGashydrates
GashydrateGashydrate
GashydrateGashydrate
GashydrateGashydrate
GashydrateGashydrate
GashydrateGashydrate
GashydrateGashydrate
GashydrateGashydrate
Acetylen + Acetylen + WasserWasser