Supporting Information

Transcription

1 Supporting Information Wiley-VCH Weinheim, Germany

2 Screening for inclusion compounds and systematic construction of three-component solids via liquid-assisted grinding Tomislav Friščić, Andrew V. Trask, William Jones and W. D. Samuel Motherwell CONTENTS EXPERIMENTAL SECTION 3 FIGURE S1. X-ray powder diffraction patterns for samples of (dioxane). 5 FIGURE S2. X-ray powder diffraction patterns for samples of (thioxane). 6 FIGURE S3. FIGURE S4. FIGURE S5. FIGURE S6. FIGURE S7. FIGURE S8. FIGURE S9. FIGURE S10. acid and etrahydropyrane. acid and entamethylene sulfide. acid and 3,4-dihydropyrane. acid and cyclohexane. acid and cyclohexene acid and benzene. acid and 1,4-difluorobenzene. acid and norbornadiene

3 FIGURE S11. FIGURE S12. FIGURE S13. FIGURE S14. FIGURE S15. FIGURE S16. FIGURE S17. FIGURE S18. FIGURE S19. FIGURE S20. FIGURE S21. FIGURE S22. FIGURE S23. FIGURE S24. FIGURE S25. FIGURE S26. FIGURE S27. FIGURE S28. FIGURE S29. FIGURE S30. FIGURE S31. acid and tetrahydrofuran. acid and furan. acid and thiophene. acid and carbon tetrachloride. acid and nitromethane. acid and hexane. acid and dimethoxyethane. acid and acetonitrile. acid and methanol. acid and acetone. acid and dithiane. acid and norbornane. acid and 2-norbornene. acid and ferrocene. acid and iodoform. Solution 1 H NMR spectra of: a) (dioxane); b) (thioxane); c)1. CH 3 NO 2 samples prepared by crystallisation from solution. Solvent: DMSO-d 6. Solid-state 13 C CP-MAS spectra of samples of (dioxane) prepared by: a) crystallisation from solution; b) neat grinding; c)liquid-assisted grinding with acetonitrile. Thermal decomposition curves of samples of: a) (dioxane); b) (thioxane); c) 1. CH 3 NO 2 prepared by crystallization from solution. A wireframe representation of two layers of (dioxane) structure with color-coding applied to: a) atom types and b) each layer an guest molecules. A wireframe representation of two layers of (thioxane) structure with color-coding applied to: a) atom types and b) each layer an guest molecules. A wireframe representation of two layers of 1. CH 3 NO 2 structure with colorcoding applied to: a) atom types and b) each layer an guest molecules

4 EXPERIMENTAL SECTION All starting materials were commercially available from Sigma-Aldrich Company and were used without purification. Solution crystallization: 100 mg of a 1:1 mixture of caffeine and succinic acid was dissolved by heating in a minimum amount (typically 5 ml) of a liquid guest. In case of solid guests, the mixture and the equimolar amount of the guest were dissolved in a minimum amount of a 1:1 mixture of acetonitrile and methanol. Single crystals of 1. CH 3 NO 2 were obtained, along with crystals of succinic acid, by slow evaporation of a solution of caffeine (250 mg) and succinic acid (150 mg) in a 1:1 mixture of nitromethane and methanol (4 ml). Single crystals of 2 were obtained in a similar way. Neat grinding: 200 mg of an equimolar mixture of caffeine and succinic acid was ground for 20 minutes with a potential guest (5 drops in case of a liquid or an equimolar amount for a solid) at a frequency of 30 Hz 10 ml stainless steel grinding jars usinf a Retsch MM200 Mixer Mill. Two 7 mm diameter stainless steel balls were used fpr grinding each sample. Liquid-assisted grinding was performed in the same manner as neat grinding, but with the addition of 2 drops of acetonitrile during grinding. X-ray powder diffraction patterns were recorded on a Philips X'Pert Pro diffractometer equipped with an X'celerator RTMS detector, using Ni-filtered CuK α radiation. Thermogravimetric analyses were performed on a Mettler Toledo TGA/SDTA 851 thermal balance at a heating rate of 10 K min -1, in a dynamic atmosphere of nitrogen. Single crystal X-ray diffraction data were collected on a Nonius Kappa CCD diffractometer equipped with an Oxford Cryosystems cryostream, using MoK α radiation. 3

5 Crystal data: (dioxane), monoclinic, C2/m, a = (4) Ǻ, b = (2) Ǻ, c = (3) Ǻ, β = (3) o, Z = 4, R 1 = for 2371 reflections with F o > 4σ(F o ); (thioxane), monoclinic, C2/m, a = (4) Ǻ, b = (2) Ǻ, c = (5) Ǻ, β = (2) o, Z = 4, R 1 = for 2085 reflections with F o > 4σ(F o ); 1. CH 3 NO 2, monoclinic, C2/m, a = (5) Ǻ, b = (2) Ǻ, c = (5) Ǻ, β = (1) o, Z = 4, R 1 = for 1858 reflections with F o > 4σ(F o ); 2, triclinic, P-1, a = (2) Ǻ, b = (2) Ǻ, c = (2) Ǻ, α = (1) o, β = (1) o, γ = (1) o, Z = 2, R 1 = for 4009 reflections with F o > 4σ(F o ). 1 H NMR spectra of (dioxane), (thioxane) and 1. CH 3 NO 2 have been recorded on a Bruker 400 MHz spectrometer using DMSO-d 6 as the solvent. Solid-state 13 C CP- MAS spectra have been obtained on a Bruker Avance-AQS spectrometer, using 4 mm probes spinning at a frequency of 10 khz. 4

6 Figure S1. X-ray powder diffraction patterns for (dioxane) obtained by: a) crystallisation from solution; b) neat grinding and c) liquid-assisted grinding. 5

7 Figure S2. X-ray powder diffraction patterns for (thioxane) obtained by: a) crystallisation from solution; b) neat grinding and c) liquid-assisted grinding. 6

8 Figure S3. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid tetrahydropyrane; b) neat grinding with tetrahydropyrane and c) liquid-assisted grinding with tetrahydropyrane and acetonitrile. 7

9 Figure S4. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid pentamethylene sulfide; b) neat grinding with pentamethylene sulfide and c) liquid-assisted grinding with pentamethylene sulfide and acetonitrile. 8

10 Figure S5. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid 3,4-dihydropyrane; b) neat grinding with 3,4-dihydropyrane and c) liquid-assisted grinding with 3,4- dihydropyrane and acetonitrile. 9

11 Figure S6. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid cyclohexane sulfide; b) neat grinding with cyclohexane and c) liquid-assisted grinding with cyclohexane and acetonitrile. 10

12 Figure S7. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid cyclohexene; b) neat grinding with cyclohexene and c) liquid-assisted grinding with cyclohexene and acetonitrile. 11

13 Figure S8. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid benzene; b) neat grinding with benzene and c) liquid-assisted grinding with benzene and acetonitrile. 12

14 Figure S9. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid 1,4- difluorobenzene; b) neat grinding with 1,4-difluorobenzene and c) liquid-assisted grinding with 1,4-difluorobenzene and acetonitrile. 13

15 Figure S10. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid norbornadiene; b) neat grinding with norbornadiene and c) liquid-assisted grinding with norbornadiene and acetonitrile. 14

16 Figure S11. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid tetrahydrofuran; b) neat grinding with tetrahydrofuran and c) liquid-assisted grinding with tetrahydrofuran and acetonitrile. 15

17 Figure S12. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid furan; b) neat grinding with furan and c) liquid-assisted grinding with furan and acetonitrile. 16

18 Figure S13. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid thiophene; b) neat grinding with thiophene and c) liquid-assisted grinding with thiophene and acetonitrile. 17

19 Figure S14. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid carbon tetrachloride; b) neat grinding with carbon tetrachloride and c) liquid-assisted grinding with carbon tetrachloride and acetonitrile. 18

20 Figure S15. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid nitromethane; b) neat grinding with nitromethane and c) liquid-assisted grinding with nitromethane and acetonitrile. 19

21 Figure S16. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid hexane; b) neat grinding with hexane and c) liquid-assisted grinding with hexane and acetonitrile. 20

22 Figure S17. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid dimethoxyethane; b) neat grinding with dimethoxyethane and c) liquid-assisted grinding with dimethoxyethane and acetonitrile. 21

23 Figure S18. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid acetonitrile; b) neat grinding with acetonitrile. 22

24 Figure S19. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid methanol; b) neat grinding with methanol and c) liquid-assisted grinding with methanol and acetonitrile. 23

25 Figure S20. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine and succinic acid by: a) crystallisation from liquid acetone; b) neat grinding with acetone and c) liquid-assisted grinding with acetone and acetonitrile. 24

26 Figure S21. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine, succinic acid and dithiane by: a) crystallisation from a 1:1 (v/v) mixture of acetonitrile and methanol; b) neat grinding c) liquid-assisted grinding with acetonitrile. 25

27 Figure S22. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine, succinic acid and norbornane by: a) crystallisation from a 1:1 (v/v) mixture of acetonitrile and methanol; b) neat grinding c) liquid-assisted grinding with acetonitrile. 26

28 Figure S23. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine, succinic acid and 2-norbornene by: a) crystallisation from a 1:1 (v/v) mixture of acetonitrile and methanol; b) neat grinding c) liquid-assisted grinding with acetonitrile. 27

29 Figure S24. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine, succinic acid and ferrocene by: a) crystallisation from a 1:1 (v/v) mixture of acetonitrile and methanol; b) neat grinding c) liquid-assisted grinding with acetonitrile. 28

30 Figure S25. X-ray powder diffraction patterns of the product obtained from an equimolar mixture of caffeine, succinic acid and iodoform by: a) crystallisation from a 1:1 (v/v) mixture of acetonitrile and methanol; b) neat grinding c) liquid-assisted grinding with acetonitrile. 29

31 Figure S26. Solution 1 H NMR spectra of: a) (dioxane); b) 1. CH 3 NO 2 ; c) (thioxane) samples prepared by crystallisation from solution. Solvent: DMSO-d 6. Integrations of signals for dioxane, nitromethane and thioxane in the samples are consistent with formulas (dioxane), 1. CH 3 NO 2 and (thioxane). 30

32 Figure S27. Solid-state 13 C CP-MAS spectra of samples of (dioxane) prepared by: a) crystallisation from solution; b) neat grinding; c) liquid-assisted grinding with acetonitrile. 31

33 Figure S28. Thermal decomposition curves of samples of: a) (dioxane), calc = 15.7%; b) (thioxane), calc = 14.7% ; c) 1. CH 3 NO 2, calc = 16.4% prepared by crystallization from solution. The difference between observed and calculated weight losses can be ascribed to solvent loss during sample preparation, and in case of 1. CH 3 NO 2 also to presence of excess succinic acid in the sample. 32

34 Figure S29. A wireframe representation of two layers of (dioxane) structure with color-coding applied to: a) atom types and b) each layer an guest molecules. 33

35 Figure S30. A wireframe representation of two layers of (thioxane) structure with color-coding applied to: a) atom types and b) each layer an guest molecules. 34

36 Figure S31. A wireframe representation of two layers of 1. CH 3 NO 2 structure with colorcoding applied to: a) atom types and b) each layer an guest molecules. 35