supplementary material - csiro publishing · 10.1071/ch17334_ac csiro 2018 australian journal of...
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10.1071/CH17334_AC
CSIRO 2018
Australian Journal of Chemistry 2018, 71(2 & 3), 81-86
SUPPLEMENTARY MATERIAL
A Novel Strategy to Introduce 18F Positron Emitting Radionuclide in Gallium Nitrate
Complex: Synthesis, NMR, X-Ray Crystal Structure, and Preliminary Studies on
Radiolabelling with 18F
Taracad K. Venkatachalam,A,C Paul V. Bernhardt,B Damion H. R. Stimson,A Gregory K.
Pierens,A Rajiv Bhalla,A and David C. ReutensA
ACenter for Advanced Imaging, The University of Queensland, Brisbane, Qld 4072, Australia. BSchool of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld
4072, Australia. CCorresponding author. Email: [email protected]
Table S1: Crystal parameters for compound 2
Identification code 1704v4
Empirical formula C20 H22 Ga N7 O3 S2.C4 H8 O
Formula weight 614.39
Temperature 190(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P1
Unit cell dimensions a = 9.6254(8) Å = 91.738(7)°.
b = 10.5932(8) Å = 104.572(7)°.
c = 14.1321(13) Å = 91.280(6)°.
Volume 1393.3(2) Å3
Z 2
Density (calculated) 1.464 Mg/m3
Absorption coefficient 1.181 mm-1
F(000) 636
Crystal size 0.5 x 0.2 x 0.2 mm3
Theta range for data collection 3.45 to 25.00°.
Index ranges -11<=h<=8, -12<=k<=12, -16<=l<=16
Reflections collected 9328
Independent reflections 4900 [R(int) = 0.0338]
Completeness to theta = 25.00° 99.7 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 1 and 0.95931
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 4900 / 0 / 343
Goodness-of-fit on F2 1.033
Final R indices [I>2sigma(I)] R1 = 0.0413, wR2 = 0.0885
R indices (all data) R1 = 0.0558, wR2 = 0.0972
Largest diff. peak and hole 0.366 and -0.310 e.Å-3
Table S2: Selected bond lengths (Å) for Compound 2
N(2)-N(3) 1.365(3) N(3)-Ga(1) 2.037(3) N(4)- N(5) 1.370(3) N(4)-Ga(1) 2.056(2) N(7)-O(3) 1.212(3) N(7)-O(2) 1.231(4) N(7)-O(1) 1.312(3) O(1)-Ga(1) 2.2808(9) S(1)-Ga(1) 2.2808(9) S(2)-Ga(1) 2.2874(9)
Table S3. Selected bond angles (˚) for Compound 2
C(2)-N(3)-Ga(1) 118.1(2) N(2)-N(3)-Ga(1) 120.89(16) C(3)-N(4)-N(5) 120.9(3) C(3)-N(4)-Ga(1) 117.48(19) N(5)-N(4)-Ga(1) 121.12(19) C(4)-N(5)-N(4) 111.7(2) C(4)-N(6)-C(15) 130.6(3) O(3)-N(7)-O(2) 124.1(3) O(3)-N(7)-O(1) 117.3(3) O(2)-N(7)-O(1) 118.6(3) N(7)-O(1)-Ga(1) 116.7(2) C(21)-O(4)-C(24) 106.9(4) C(1)-S(1)-Ga(1) 94.62(11) C(4)-S(2)-Ga(1) 94.65(10) O(1)-Ga(1)-N(3) 93.04(9) O(1)-Ga(1)-N(4) 90.53(9) N(3)-Ga(1)-N(4) 75.82(10) O(1)-Ga(1)-S(1) 107.02(7) N(3)-Ga(1)-S(1) 83.69(8) N(4)-Ga(1)-S(1) 153.73(7) O(1)-Ga(1)-S(2) 108.89(7) N(3)-Ga(1)-S(2) 149.31(7) N(4)-Ga(1)-S(2) 82.60(7) S(1)-Ga(1)-S(2) 108.84(3)
Crystal packing diagram for symmetrical diethyl diphenyl dithiosemicarbazone gallium nitrate
(Compound 2)
Table S4. Crystal data and structure refinement for Compound 4
Identification code 1710v10
Empirical formula C19 H20 F Ga N6 S2
Formula weight 485.25
Temperature 190(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P21/n
Unit cell dimensions a = 12.8771(8) Å = 90°.
b = 12.0711(7) Å = 115.102(8)°.
c = 14.9367(12) Å = 90°.
Volume 2102.5(2) Å3
Z 4
Density (calculated) 1.533 Mg/m3
Absorption coefficient 1.534 mm-1
F(000) 992
Crystal size 0.2 x 0.1 x 0.1 mm3
Theta range for data collection 3.23 to 25.00°.
Index ranges -13<=h<=15, -14<=k<=14, -17<=l<=17
Reflections collected 8950
Independent reflections 3688 [R(int) = 0.0667]
Completeness to theta = 25.00° 99.8 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 1 and 0.98401
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 3688 / 0 / 264
Goodness-of-fit on F2 1.047
Final R indices [I>2sigma(I)] R1 = 0.0651, wR2 = 0.1214
R indices (all data) R1 = 0.1119, wR2 = 0.1408
Largest diff. peak and hole 0.649 and -0.477 e.Å-3
Table S5. Bond lengths [Å] and angles [°] for compound 4.
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C(1)-N(2) 1.304(6)
C(1)-N(1) 1.364(6)
C(1)-S(1) 1.765(6)
C(2)-N(3) 1.290(7)
C(2)-C(3) 1.467(7)
C(2)-C(5) 1.530(8)
C(3)-N(4) 1.283(7)
C(3)-C(6) 1.502(7)
C(4)-N(5) 1.313(7)
C(4)-N(6) 1.349(7)
C(4)-S(2) 1.753(6)
C(6)-C(7) 1.508(10)
C(8)-C(13) 1.370(7)
C(8)-C(9) 1.396(7)
C(8)-N(1) 1.407(7)
C(9)-C(10) 1.367(8)
C(10)-C(11) 1.349(8)
C(11)-C(12) 1.387(8)
C(12)-C(13) 1.376(8)
C(14)-C(15) 1.382(8)
C(14)-C(19) 1.391(8)
C(14)-N(6) 1.430(6)
C(15)-C(16) 1.397(7)
C(16)-C(17) 1.356(8)
C(17)-C(18) 1.382(9)
C(18)-C(19) 1.387(7)
N(2)-N(3) 1.382(6)
N(3)-Ga(1) 2.042(5)
N(4)-N(5) 1.364(6)
N(4)-Ga(1) 2.035(4)
F(1)-Ga(1) 1.948(3)
S(1)-Ga(1) 2.2984(14)
S(2)-Ga(1) 2.2911(18)
N(2)-C(1)-N(1) 120.2(5)
N(2)-C(1)-S(1) 127.1(4)
N(1)-C(1)-S(1) 112.7(4)
N(3)-C(2)-C(3) 113.4(5)
N(3)-C(2)-C(5) 124.2(5)
C(3)-C(2)-C(5) 122.2(5)
N(4)-C(3)-C(2) 114.3(5)
N(4)-C(3)-C(6) 123.2(5)
C(2)-C(3)-C(6) 122.4(6)
N(5)-C(4)-N(6) 119.9(5)
N(5)-C(4)-S(2) 126.6(5)
N(6)-C(4)-S(2) 113.5(5)
C(3)-C(6)-C(7) 112.6(6)
C(13)-C(8)-C(9) 119.5(5)
C(13)-C(8)-N(1) 124.9(5)
C(9)-C(8)-N(1) 115.6(5)
C(10)-C(9)-C(8) 119.9(6)
C(11)-C(10)-C(9) 120.9(6)
C(10)-C(11)-C(12) 119.6(6)
C(13)-C(12)-C(11) 120.6(6)
C(8)-C(13)-C(12) 119.6(5)
C(15)-C(14)-C(19) 120.1(5)
C(15)-C(14)-N(6) 124.5(5)
C(19)-C(14)-N(6) 115.3(5)
C(14)-C(15)-C(16) 118.4(6)
C(17)-C(16)-C(15) 122.0(6)
C(16)-C(17)-C(18) 119.5(6)
C(17)-C(18)-C(19) 120.0(6)
C(18)-C(19)-C(14) 120.0(6)
C(1)-N(1)-C(8) 131.2(5)
C(1)-N(2)-N(3) 111.4(4)
C(2)-N(3)-N(2) 121.4(5)
C(2)-N(3)-Ga(1) 116.9(4)
N(2)-N(3)-Ga(1) 121.5(3)
C(3)-N(4)-N(5) 120.9(5)
C(3)-N(4)-Ga(1) 117.1(4)
N(5)-N(4)-Ga(1) 121.9(4)
C(4)-N(5)-N(4) 112.3(5)
C(4)-N(6)-C(14) 130.1(5)
C(1)-S(1)-Ga(1) 94.32(18)
C(4)-S(2)-Ga(1) 94.5(2)
F(1)-Ga(1)-N(4) 102.67(15)
F(1)-Ga(1)-N(3) 99.97(17)
N(4)-Ga(1)-N(3) 75.92(18)
F(1)-Ga(1)-S(2) 105.08(11)
N(4)-Ga(1)-S(2) 83.24(15)
N(3)-Ga(1)-S(2) 150.34(14)
F(1)-Ga(1)-S(1) 106.69(9)
N(4)-Ga(1)-S(1) 146.23(14)
N(3)-Ga(1)-S(1) 82.84(13)
S(2)-Ga(1)-S(1) 104.50(6)
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Overlay of 1H NMR of (1) starting symmetrical diethyl diphenyl dithiosemicarbazone gallium
nitrate (Compound 2) and (2) 19F exchanged symmetrical diethyl diphenyl dithiosemicarbazone
gallium fluoride complex (Note the change in the chemical shift values for the NH and one of the
ortho protons of the phenyl ring. Other tall peaks are due to residual methanol/H2O solvent
signals.)
Radio HPLC of exchange of nitrate complex of symmetrical diethyl diphenyl dithiosemicarbazone gallium (Compound 2) to the corresponding 18F complex (note: the peak at 22.5 minutes represents the radiolabeled product.
HPLC profile for UV trace during exchange reaction of nitrate to 18F in gallium complex. (the UV peak of the 18F substituted compound is buried under the nitrate compound at 22.5 minutes).
Radio and UV trace after exchange with 18F (the largest peak at 2 minutes is due to free 18F-
HPLC radio chromatogram for exchange of 18F with unsymmetrical methyl-ethyl-diphenyl-
dithiosemicarbazone nitrate complex (Compound 1).