4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone toluenesulfonic acid addition salt and salt crystals

1. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits an X-ray powder diffraction pattern comprising at least two peaks having 2-theta values selected from the group consisting of 5.68°, 12.11°, 16.04°, 17.03°, 18.16°, 19.00°, 21.67°, 22.55°, 23.48° and 24.30°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter.

2. The salt crystal according to claim 1 , wherein said salt crystal exhibits an X-ray powder diffraction pattern comprising at least five peaks having 2-theta values selected from the group consisting of: 5.68°, 12.11°, 16.04°, 17.03°, 18.16°, 19.00°, 21.67°, 22.55°, 23.48° and 24.30°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter.

3. The salt crystal according to claim 1 , wherein said salt crystal exhibits an X-ray powder diffraction pattern comprising the following peaks having 2-theta values: 5.6811°, 8.5140°, 11.3750°, 12.1088°, 13.3354°, 15.7948°, 16.0419°, 16.4461°, 17.0309°, 17.2606°, 17.5531°, 18.1581°, 18.9968°, 19.8889°, 20.7510°, 21.6724°, 22.25463°, 23.4815°, 23.7411°, 24.3006°, 25.9394°, 27.2321°, 28.3782°, 28.9055°, 29.6695°, 31.6106°, 32.2950°, 34.8530°, 37.5435°, 39.4972°, 40.2502° and 40.8303°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter.

4. The salt crystal according to claim 1 , wherein said salt crystal exhibits an X-ray powder diffraction pattern comprising peaks having the following D-spacing values: 15.543 Å, 7.303 Å, 5.520 Å, 5.202 Å, 4.882 Å, 4.668 Å, 4.097 Å, 3.940 Å, 3.786 Å and 3.660 Å; or the following 2-theta values: 5.68°, 12.11°, 16.04°, 17.03°, 18.16°, 19.00°, 21.67°, 22.55°, 23.48° and 24.30°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter.

5. The salt crystal according to claim 1 , wherein said salt crystal exhibits a Fourier transform infrared spectrometry band pattern comprising at least two bands selected from the group consisting of: 2952, 2824, 2581, 1687, 1617, 1599, 1506, 1328, 1231, 1162, 1010, 817, 681 and 569 wavenumber.

6. The salt crystal according to claim 1 , wherein said salt crystal exhibits a differential scanning calorimetry pattern comprising a peak temperature range of 180°-181° C.

7. The salt crystal according to claim 1 , wherein said salt crystal exhibits a thermogravimetric analysis profile comprising two regions of weight loss with a total weight loss of 0.5% through 200° C.

8. The salt crystal according to claim 1 , wherein said salt crystal is exhibits (i) an X-ray powder diffraction pattern comprising at least five peaks having 2-theta values selected from the group consisting of 5.68°, 12.11°, 16.04°, 17.03°, 18.16°, 19.00°, 21.67°, 22.55°, 23.48° and 24.30°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter; and (ii) a differential scanning calorimetry pattern according to FIG. 8 .

9. The salt crystal according to claim 1 , wherein said salt crystal exhibits (i) an X-ray powder diffraction pattern comprising at least five peaks having 2-theta values selected from the group consisting of 5.68°, 12.11°, 16.04°, 17.03°, 18.16°, 19.00°, 21.67°, 22.55°, 23.48° and 24.30°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter; and (ii) a differential scanning calorimetry pattern comprising a peak temperature range of 180°-181° C.

10. A pharmaceutical composition comprising the salt crystal according to claim 1 , together with a pharmaceutically acceptable diluent or carrier.

11. A pharmaceutical composition comprising the salt crystal according to claim 2 together with a pharmaceutically acceptable diluent or carrier.

12. A pharmaceutical composition comprising the salt crystal according to claim 9 , together with a pharmaceutically acceptable diluent or carrier.

13. A salt crystal according to claim 1 prepared from a process which comprises the steps of

a) reacting 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone free base with p-toluenesulfonic acid in the presence of 2-propanol; or

b) dissolving 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone toluenesulfonic acid addition salt in 2-propanol; and

c) optionally cooling the resulting solution or mixture from step (a) or (b) to 0°-25° C.

14. A process for the production of the salt crystal according to claim 1 , which process comprises the steps of:

a) reacting 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone free base with p-toluenesulfonic acid in the presence of ethanol or 2-propanol; or

b) dissolving 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone toluenesulfonic acid addition salt in the presence of 2-propanol; and

c) optionally cooling the resulting solution or mixture from step (a) or (b) to 0°-25° C.

15. The process according to claim 14 , which process comprises the steps of:

a) reacting 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone free base with p-toluenesulfonic acid in 2-5 mL of 2-propanol per gram of said free base; and

b) optionally cooling the resulting solution or mixture from step (a) to 0°-25° C.

16. A toluenesulfonic acid addition salt crystal of 4-((6bR,l0aS)-3-methyl-2,3,6b,9, 10,10a-hexahydro-1H-pyrido[3′,4′: 4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits an X-ray powder diffraction pattern comprising peaks having the following 2-theta values 8.559°, 11.411°, 12.198°, 13.354°, 16.076°, 17.093°, 18.209°, 19.031°, 19.998°, 22.611°, 23.495°, 24.335° and 29.710°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter.

17. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3- methyl-2,3,6b,9,10,10a-hexahydro-1H-pyridol[3′,4′: 4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits an X-ray powder diffraction pattern comprising the following peaks having 2-theta values: 4.1373°, 5.6541°, 8.2430°, 10.3839°, 11.3760°, 12.1103°, 13.3099°, 14.1235°, 14.4743°, 14.8763°, 15.3532°, 15.8535°, 16.4465°, 17.0544°, 17.9466°, 18.1622°, 18.6277°, 18.9621°, 19.8255°, 20.3507°, 20.6196°, 21.6034°, 22.4973°, 23.4609°, 24.3083°, 25.1377°, 26.0351°, 27.2489°, 29.0199°, 31.5733°, 35.0279°, 37.6449° and 39.4614°, wherein the X-ray powder diffraction data is collected on a diffractometer operating with a copper anode with a nickel filter; or an X-ray powder diffraction pattern comprising the following peaks having d-spacing values: 21.3573 Å, 15,63088 Å, 10.72658 Å, 8.51937 Å, 7.77853 Å, 7.30844 Å, 6.65232 Å, 6.27088 Å, 6.11969 Å, 5.95520 Å, 5.77130 Å, 5.59028 Å, 5.39000 Å, 5.19923 Å, 4.94274 Å, 4.88454 Å, 4.75350 Å, 4.68024 Å, 4.47833 Å, 4.36392 Å, 4.30762 Å, 4.11363 Å, 3.95215 Å, 3.79196 Å, 3.66167 Å, 3.54270 Å, 3.42260 Å, 3.27282 Å, 3.07701 Å, 2.83374 Å, 2.56178 Å, 2.38949 Å and 2.28359 Å.

18. A process for the production of the salt crystal according to claim 17 , which process comprises the steps of:

a) reacting 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′: 4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone free base with p-toluenesulfonic acid in the presence of ethanol; or

b) dissolving 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′: 4,5]pyrrolo[1,2,3-de]quinoxalin-8 (7H)-yl)-1-(4-fluorophenyl)-1-butanone toluenesulfonic acid addition salt in the presence of ethanol; and

c) optionally cooling the resulting solution or mixture from step (a) to (b) to 0 ° -25 ° C.

19. The process according to claim 18 , which process comprises the steps of:

a) reacting 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone free base with p-toluenesulfonic acid in 2-5 mL of ethanol per gram of said free base; and

b) optionally cooling the resulting solution or mixture from step (a) to 0°-25° C.

20. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits an X-ray powder diffraction pattern according to FIG. 7 , FIG. 7A or FIG. 7B .

21. A pharmaceutical composition comprising the salt crystal according to claim 20 , together with a pharmaceutically acceptable diluent or carrier.

22. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits a differential scanning calorimetry pattern according to FIG. 8 .

23. A pharmaceutical composition comprising the salt crystal according to claim 22 , together with a pharmaceutically acceptable diluent or carrier.

24. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-

25. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits an X-ray powder diffraction pattern according to FIG. 7 , FIG. 7A or FIG. 7B and a differential scanning calorimetry pattern or a thermogravimetric analysis profile according to FIG. 8 .

26. A pharmaceutical composition comprising the salt crystal according to claim 25 , together with a pharmaceutically acceptable diluent or carrier. 8 (7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits a thermogravimetric analysis profile according to FIG. 8 .

27. A toluenesulfonic acid addition salt crystal of 4-((6bR,10aS)-3-methyl-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxalin-8(7H)-yl)-1-(4-fluorophenyl)-1-butanone, wherein said salt crystal exhibits an X-ray powder diffraction pattern according to FIG. 9 or FIG. 10 .