Imatinibium dipicrate

Jasinski, J.P.; Butcher, R.J.; Hakim Al-Arique, Q.N.M.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536810000577

Volume 66
Part 2
Pages o411-o412
February 2010

Received 5 December 2009
Accepted 5 January 2010
Online 20 January 2010

Key indicators
Single-crystal X-ray study
T = 110 K
Mean (C-C) = 0.004 Å
R = 0.059
wR = 0.158
Data-to-parameter ratio = 12.6
Details

Imatinibium dipicrate

Jerry P. Jasinski,^a ^* Ray J. Butcher,^b Q. N. M. Hakim Al-Arique,^c H. S. Yathirajan ^c and B. Narayana ^d

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA,^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA,^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^dDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
Correspondence e-mail: jjasinski@keene.edu

In the crystal structure of imatinibium dipicrate [systematic name: 1-methyl-4-(4-{4-methyl-3-[4-(3-pyridyl)pyrimidin-2-ylamino]anilinocarbonyl}benzyl)piperazine-1,4-diium dipicrate], C₂₉H₃₃N₇O²⁺·2C₆H₂N₃O₇^-, the imatinibium cation is protonated at both of the pyrimidine N atoms. Each of the two picrate anions interacts with the diprotonated cation through bifurcated N-HO hydrogen bonds forming R₁²(6) ring motifs. Also, an R₂²(24) graph set is formed between the benzamidium -NH- group and the 4-pyridyl N atom interacting through N-HN hydrogen-bond interactions. Additional weak C-HCg [pi] -ring and [pi] - [pi] intermolecular interactions are observed which also influence crystal packing.

Related literature

For related structures, see: Bindya et al. (2007); Harrison, Bindya et al. (2007); Harrison, Sreevidya et al. (2007); Jasinski et al. (2009a,b); Swamy et al. (2007); Szumma et al. (2000); Yathirajan et al. (2007a,b). For a rationally developed anticancer drug, see: Capdeville et al. (2002). For its use in chronic myeloid leukaemia, see: Moen et al. (2007). For puckering parameters, see: Cremer & Pople (1975).

Experimental

Crystal data

C₂₉H₃₃N₇O²⁺·2C₆H₂N₃O₇^-
M_r = 951.84
Triclinic, $[P \overline 1]$
a = 8.560 (1) Å
b = 10.734 (1) Å
c = 23.060 (1) Å
= 96.74 (3)°
= 92.69 (2)°
= 101.46 (7)°
V = 2056.9 (6) Å³
Z = 2
Cu K radiation
= 1.02 mm^-1
T = 110 K
0.45 × 0.39 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Cu) detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.596, T_max = 0.782
15890 measured reflections
8082 independent reflections
6946 reflections with I > 2(I)
R_int = 0.023

Refinement

R[F² > 2(F²)] = 0.059
wR(F²) = 0.158
S = 1.06
8082 reflections
640 parameters
H atoms treated by a mixture of independent and constrained refinement
_max = 0.50 e Å^-3
_min = -0.27 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N1-H1O1B	0.85 (3)	1.85 (3)	2.658 (3)	157 (3)
N1-H1O62B	0.85 (3)	2.35 (3)	2.890 (3)	122 (2)
N2-H2O1A	0.89 (4)	1.85 (4)	2.678 (3)	154 (3)
N2-H2O62A	0.89 (4)	2.41 (4)	3.009 (3)	125 (3)
N14-H14N31ⁱ	0.85 (3)	2.23 (3)	3.069 (3)	171 (3)
C5-H5BO41Aⁱⁱ	0.98	2.48	3.258 (4)	136
C4-H4BO42Bⁱⁱⁱ	0.99	2.33	3.199 (3)	146
C3-H3AO61B^iv	0.99	2.57	3.199 (3)	121
C3-H3BO1B	0.99	2.34	3.072 (3)	130
C12-H12AO42Bⁱⁱⁱ	0.95	2.63	3.423 (3)	142
C19-H19AO61B^v	0.98	2.50	3.435 (4)	159
C19-H19AN6B^v	0.98	2.65	3.541 (4)	152
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y, -z; (iii) x-1, y-1, z; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1.

Table 2
[pi] -Ring hydrogen-bond geometry (Å, °) for (I)

D-HA	D-H	HA	DA	D-HA
C33-H33ACg5^vi	0.95	2.90	3.545 (8)	127
Symmetry code: (vi) x + 1, y, z. Cg5 is the centroid of the C15-C21 ring.

Table 3
[pi] - [pi] stacking geometry (Å) for (I)

Cg2Cg7^v	3.740 (4)
Cg3Cg3^v	3.496 (7)
Cg6Cg6^vii	3.396 (0)
Symmetry codes: (v) -x + 1, -y + 1, -z + 1; (vii) -x + 2, -y + 2, -z. Cg2, Cg3, Cg6 and Cg7 are the centroids of the C25-C27/N28/C23/N4, C32-C34/C29//C30/N31, C1A-C6A and C1B-C6B rings, respectively.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL, enCIFer (Allen et al., 2004) and PLATON (Spek, 2009).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5129 ).

Acknowledgements

QNMHA thanks the University of Mysore for use of its research facilities. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

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Capdeville, R., Buchdunger, E., Zimmermann, J. & Matter, A. (2002). Nat. Rev. Drug Discov. 1, 493-502.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.
Harrison, W. T. A., Bindya, S., Ashok, M. A., Yathirajan, H. S. & Narayana, B. (2007). Acta Cryst. E63, o3143.
Harrison, W. T. A., Sreevidya, T. V., Narayana, B., Sarojini, B. K. & Yathirajan, H. S. (2007). Acta Cryst. E63, o3871.
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Jasinski, J. P., Butcher, R. J., Hakim Al-Arique, Q. N. M., Yathirajan, H. S. & Narayana, B. (2009b). Acta Cryst. E65, o2201-o2202.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.
Moen, M. D., Mckeage, K., Plosker, G. L. & Siddiqui, M. A. A. (2007). Drugs, 67, 299-320.
Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.
Swamy, M. T., Ashok, M. A., Yathirajan, H. S., Narayana, B. & Bolte, M. (2007). Acta Cryst. E63, o4919.
Szumma, A., Jurczak, J. & Urbanczyk-Lipkowska, Z. (2000). J. Mol. Struct. 526, 165-175.
Yathirajan, H. S., Ashok, M. A., Narayana Achar, B. & Bolte, M. (2007a). Acta Cryst. E63, o1691-o1692.
Yathirajan, H. S., Ashok, M. A., Narayana Achar, B. & Bolte, M. (2007b). Acta Cryst. E63, o1693-o1695.

organic compounds

Imatinibium dipicrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Acknowledgements

References