CRYSTALLINE POLYMORPHS OF THE FREE BASE OF 2-HYDROXY-6-((2-(1-ISOPROPYL-1H-PYRAZOL-5-YL)PYRIDIN-3-YL)METHOXY)BENZALDEHYDE

1 .- 20 . (canceled)

21 . A method of increasing oxygen affinity of hemoglobin S in a patient in need thereof comprising administering to the patient in need thereof a crystalline ansolvate of Compound 1:

wherein the crystalline ansolvate is characterized by at least one X-ray powder diffraction peak (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

22 . The method of claim 21 , wherein the crystalline ansolvate is characterized by at least two X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

23 . The method of claim 21 , wherein the crystalline ansolvate is characterized by at least three powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

24 . The method of claim 21 , wherein the crystalline ansolvate is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

25 . The method of claim 21 , wherein the crystalline ansolvate is characterized by an X-ray powder diffraction pattern (Cu Kα radiation) substantially similar to that of FIG. 5 .

26 . The method of claim 21 , wherein the crystalline ansolvate of Compound 1 is substantially free of a solvated polymorph of Compound 1.

27 . The method of claim 21 , wherein the crystalline ansolvate of Compound 1 is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ), and less than about 25 mole %, 10 mole %, or 5 mole % of one or more of crystalline Form I, Material N, or amorphous forms of Compound 1.

28 . A method of increasing oxygen affinity of hemoglobin S in a patient in need thereof comprising administering to the patient in need thereof a pharmaceutical composition comprising a crystalline ansolvate of Compound 1:

and at least one pharmaceutically acceptable excipient, wherein the crystalline ansolvate is characterized by at least one X-ray powder diffraction peak (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

29 . The method of claim 28 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least two X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

30 . The method of claim 28 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least three X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

31 . The method of claim 28 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

32 . The method of claim 28 , wherein the crystalline ansolvate of the pharmaceutical composition of Compound 1 is substantially free of a solvated polymorph of Compound 1.

33 . The method of claim 28 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ), and less than about 25 mole %, 10 mole %, or 5 mole % of one or more of crystalline Form I, Material N, or amorphous forms of Compound 1.

34 . A method of treating sickle cell disease in a patient having sickle cell disease comprising administering to the patient in need thereof a crystalline ansolvate of Compound 1:

wherein the crystalline ansolvate is characterized by at least one X-ray powder diffraction peak (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

35 . The method of claim 34 , wherein the crystalline ansolvate is characterized by at least two X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

36 . The method of claim 34 , wherein the crystalline ansolvate is characterized by at least three X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

37 . The method of claim 34 , wherein the crystalline ansolvate is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

38 . The method of claim 34 , wherein the crystalline ansolvate is characterized by an X-ray powder diffraction pattern (Cu Kα radiation) substantially similar to that of FIG. 5 .

39 . The method of claim 34 , wherein the crystalline ansolvate of Compound 1 is substantially free of a solvated polymorph of Compound 1.

40 . The method of claim 34 , wherein the crystalline ansolvate of Compound 1 is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ), and less than about 25 mole %, 10 mole %, or 5 mole % of one or more of crystalline Form I, Material N, or amorphous forms of Compound 1.

41 . A method of treating sickle cell disease in a patient having sickle cell disease comprising administering to the patient in need thereof a pharmaceutical composition comprising a crystalline ansolvate of Compound 1:

and at least one pharmaceutically acceptable excipient, wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least one X-ray powder diffraction peak (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

42 . The method of claim 41 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least two X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

43 . The method of claim 41 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least three X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

44 . The method of claim 41 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

45 . The method of claim 41 , wherein the crystalline ansolvate of the pharmaceutical composition is substantially free of a solvated polymorph of Compound 1.

46 . The method of claim 41 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ), and less than about 25 mole %, 10 mole %, or 5 mole % of one or more of crystalline Form I, Material N, or amorphous forms of Compound 1.

47 . A method of treating pulmonary disorder in a patient having a pulmonary disorder comprising administering to the patient in need thereof a crystalline ansolvate of Compound 1:

wherein the crystalline ansolvate is characterized by at least one X-ray powder diffraction peak (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

48 . The method of claim 47 , wherein the crystalline ansolvate is characterized by at least two X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

49 . The method of claim 47 , wherein the crystalline ansolvate is characterized by at least three X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

50 . The method of claim 47 , wherein the crystalline ansolvate is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

51 . The method of claim 47 , wherein the crystalline ansolvate is substantially free of a solvated polymorph of Compound 1.

52 . The method of claim 47 , wherein the crystalline ansolvate is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ), and less than about 25 mole %, 10 mole %, or 5 mole % of one or more of crystalline Form I, Material N, or amorphous forms of Compound 1.

53 . A method of treating pulmonary disorder in a patient having a pulmonary disorder comprising administering to the patient in need thereof a pharmaceutical composition comprising a crystalline ansolvate of Compound 1:

wherein the crystalline ansolvate is characterized by at least one X-ray powder diffraction peak (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

54 . The method of claim 53 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least two X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

55 . The method of claim 53 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by at least three X-ray powder diffraction peaks (Cu Kα radiation) selected from 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

56 . The method of claim 53 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ).

57 . The method of claim 53 , wherein the crystalline ansolvate of the pharmaceutical composition is substantially free of a solvated polymorph of Compound 1.

58 . The method of claim 53 , wherein the crystalline ansolvate of the pharmaceutical composition is characterized by X-ray powder diffraction peaks (Cu Kα radiation) of 13.37°, 14.37°, 19.95° and 23.92°2θ (each ±0.2°2θ), and less than about 25 mole %, 10 mole %, or 5 mole % of one or more of crystalline Form I, Material N, or amorphous forms of Compound 1.