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Acta Cryst. (2009). E65, o518    [ doi:10.1107/S1600536809004474 ]

4-(4-Carboxybenzyl)-1-methylpiperazin-1-ium picrate

H. Li, Q. N. M. Hakim Al-arique, H. S. Yathirajan, B. Narayana and A. R. Ramesha

Abstract top

The title compound, C13H19N2O2+·C6H2N3O7-, is a salt obtained by cocrystallization of 4-[(4-methylpiperazin-1-yl)methyl]benzoic acid and picric acid. The cations adopt an `L-shaped' conformation and are linked into chains along [010] by O-H...N hydrogen bonds. The NH group of each piperazinium ring forms a hydrogen bond to the phenolate O atom of a picrate anion, and the picrate anions form face-to-face contacts with an interplanar separation of 3.023 (1) Å.

Comment top

4-[(4-Methylpiperazin-1-yl)methyl]benzoic acid is an intermediate in the synthesis of Imatinib, a drug used to treat certain types of cancer. Its mesylate salt is currently marketed by Novartis as Gleevec (Druker et al., 2001). Picric acid forms salts or charge-transfer complexes with many organic compounds. Crystal structures of picrate complexes with organic compounds of pharmaceutical importance viz., desipraminium picrate (Swamy et al., 2007) and amitriptylinium picrate (Bindya et al., 2007) have been reported. A three-dimensional network in piperazine-1,4-diium-picrate-piperazine (1/2/1) is reported recently (Wang & Jia, 2008).

Related literature top

For general background, see: Druker et al. (2001). For related structures, see: Swamy et al. (2007); Bindya et al. (2007); Sarojini et al. (2007); Wang & Jia (2008).

Experimental top

The title compound was prepared by taking equimolar quantities of picric acid (0.92 g, 2 mmol) and 4-[(4-methylpiperazin-1-yl)methyl]benzoic acid (0.47 g, 2 mmol) and dissolving them in water. The solution was stirred well at room temperature and slow evaporation of the solution resulted in the formation of the yellow coloured salt (yield 95%). Crystals suitable for single-crystal X-ray diffraction were grown from dimethyl formamide solvent.

Refinement top

H atoms bound to C atoms were placed at calculated positions and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The H atom of the OH group was also placed geometrically and allowed to ride with Uiso(H) = 1.5Ueq(O). The H atom of the NH group was located in a difference Fourier map and refined isotropically without restraint.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
4-(4-Carboxybenzyl)-1-methylpiperazin-1-ium picrate top
Crystal data top
C13H19N2O2+·C6H2N3O7−Z = 2
Mr = 463.41F(000) = 484
Triclinic, P1Dx = 1.501 Mg m−3
Hall symbol: -P 1Melting point = 510–504 K
a = 7.3020 (12) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.5993 (16) ÅCell parameters from 1962 reflections
c = 15.131 (3) Åθ = 2.5–26.9°
α = 86.448 (2)°µ = 0.12 mm−1
β = 79.145 (2)°T = 296 K
γ = 79.950 (2)°Block, colourless
V = 1025.2 (3) Å30.30 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer		3565 independent reflections
Radiation source: fine-focus sealed tube2745 reflections with I > 2σ(I)
graphiteRint = 0.016
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −8→6
Tmin = 0.965, Tmax = 0.976k = −11→9
5373 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0447P)2 + 0.2218P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3565 reflectionsΔρmax = 0.18 e Å−3
305 parametersΔρmin = −0.17 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.023 (2)
Crystal data top
C13H19N2O2+·C6H2N3O7−γ = 79.950 (2)°
Mr = 463.41V = 1025.2 (3) Å3
Triclinic, P1Z = 2
a = 7.3020 (12) ÅMo Kα radiation
b = 9.5993 (16) ŵ = 0.12 mm−1
c = 15.131 (3) ÅT = 296 K
α = 86.448 (2)°0.30 × 0.20 × 0.20 mm
β = 79.145 (2)°
Data collection top
Bruker SMART CCD
diffractometer		3565 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2745 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.976Rint = 0.016
5373 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104Δρmax = 0.18 e Å−3
S = 1.06Δρmin = −0.17 e Å−3
3565 reflectionsAbsolute structure: ?
305 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5333 (3)1.0778 (2)0.14228 (14)0.0426 (5)
C20.6431 (3)1.0691 (2)0.05175 (13)0.0438 (5)
C30.7751 (3)0.9547 (2)0.02127 (13)0.0430 (5)
H30.83950.9546−0.03790.052*
C40.8126 (3)0.8398 (2)0.07793 (12)0.0379 (4)
C50.7175 (2)0.83776 (19)0.16598 (12)0.0359 (4)
H50.74220.75950.20390.043*
C60.5870 (3)0.9521 (2)0.19627 (12)0.0372 (4)
C70.1636 (3)1.33630 (19)0.60024 (12)0.0366 (4)
C80.1280 (2)1.18702 (18)0.60753 (11)0.0320 (4)
C90.2178 (3)1.09572 (19)0.53938 (12)0.0380 (4)
H90.29431.12920.48920.046*
C100.1949 (3)0.95535 (19)0.54527 (12)0.0391 (4)
H100.25570.89540.49890.047*
C110.0818 (2)0.90303 (18)0.61993 (12)0.0349 (4)
C12−0.0108 (2)0.99528 (18)0.68722 (12)0.0361 (4)
H12−0.08970.96220.73670.043*
C130.0123 (2)1.13606 (18)0.68187 (12)0.0348 (4)
H13−0.04941.19640.72790.042*
C140.0608 (3)0.74891 (19)0.62770 (13)0.0413 (5)
H14A−0.06400.74130.66160.050*
H14B0.06770.71560.56770.050*
C150.3984 (3)0.6541 (2)0.62183 (12)0.0399 (5)
H15A0.42810.74880.62080.048*
H15B0.40630.62820.56010.048*
C160.5410 (3)0.5522 (2)0.66450 (12)0.0415 (5)
H16A0.51960.45620.65980.050*
H16B0.66740.55910.63240.050*
C170.3292 (3)0.5816 (2)0.80965 (12)0.0402 (5)
H17A0.31890.60460.87210.048*
H17B0.29850.48750.80830.048*
C180.1914 (3)0.68674 (19)0.76667 (12)0.0375 (4)
H18A0.06390.68460.79910.045*
H18B0.21900.78130.77010.045*
C190.6653 (3)0.4834 (2)0.80485 (15)0.0598 (6)
H19A0.65950.51210.86510.090*
H19B0.79030.48410.77100.090*
H19C0.63550.38960.80650.090*
N10.6141 (3)1.1856 (2)−0.01420 (15)0.0587 (5)
N20.9524 (2)0.71935 (19)0.04516 (11)0.0471 (4)
N30.4925 (2)0.9427 (2)0.28970 (11)0.0469 (4)
N40.2038 (2)0.65332 (14)0.67160 (9)0.0340 (4)
N50.5264 (2)0.58329 (17)0.76126 (10)0.0375 (4)
O10.4059 (2)1.17657 (15)0.17135 (11)0.0614 (4)
O20.5114 (3)1.2956 (2)0.00975 (14)0.0921 (6)
O30.6952 (3)1.16659 (19)−0.09220 (12)0.0799 (6)
O41.0379 (2)0.72647 (18)−0.03240 (10)0.0680 (5)
O50.9804 (2)0.61680 (16)0.09632 (11)0.0649 (5)
O60.4639 (2)0.82634 (18)0.32167 (10)0.0633 (4)
O70.4470 (2)1.05126 (19)0.33248 (10)0.0707 (5)
O80.1067 (2)1.40458 (13)0.67570 (8)0.0445 (4)
H80.13971.48250.66910.067*
O90.2400 (2)1.38891 (15)0.53152 (9)0.0605 (4)
H5A0.551 (3)0.669 (2)0.7674 (13)0.045 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0386 (11)0.0359 (11)0.0586 (13)−0.0106 (8)−0.0166 (9)−0.0054 (9)
C20.0462 (12)0.0407 (11)0.0508 (12)−0.0163 (9)−0.0195 (10)0.0092 (9)
C30.0449 (11)0.0537 (13)0.0350 (10)−0.0208 (10)−0.0079 (9)0.0021 (9)
C40.0359 (10)0.0421 (11)0.0355 (10)−0.0087 (8)−0.0032 (8)−0.0036 (8)
C50.0377 (10)0.0382 (10)0.0345 (10)−0.0097 (8)−0.0102 (8)−0.0007 (8)
C60.0368 (10)0.0426 (11)0.0348 (10)−0.0100 (8)−0.0079 (8)−0.0059 (8)
C70.0393 (10)0.0345 (10)0.0353 (10)−0.0079 (8)−0.0036 (8)−0.0002 (8)
C80.0339 (9)0.0298 (9)0.0334 (9)−0.0060 (7)−0.0086 (8)−0.0001 (7)
C90.0457 (11)0.0366 (10)0.0307 (9)−0.0071 (8)−0.0045 (8)0.0000 (8)
C100.0491 (11)0.0327 (10)0.0349 (10)−0.0028 (8)−0.0081 (9)−0.0067 (8)
C110.0360 (10)0.0296 (10)0.0423 (10)−0.0070 (7)−0.0141 (8)0.0004 (8)
C120.0311 (10)0.0339 (10)0.0415 (10)−0.0064 (7)−0.0026 (8)0.0042 (8)
C130.0327 (9)0.0311 (10)0.0378 (10)−0.0029 (7)−0.0008 (8)−0.0027 (8)
C140.0461 (11)0.0317 (10)0.0503 (11)−0.0104 (8)−0.0157 (9)−0.0015 (8)
C150.0448 (11)0.0371 (10)0.0347 (10)−0.0087 (8)0.0013 (8)0.0020 (8)
C160.0423 (11)0.0371 (11)0.0385 (10)−0.0016 (8)0.0047 (8)−0.0018 (8)
C170.0392 (10)0.0418 (11)0.0348 (10)−0.0040 (8)0.0030 (8)−0.0016 (8)
C180.0349 (10)0.0371 (10)0.0380 (10)−0.0026 (8)−0.0013 (8)−0.0070 (8)
C190.0513 (13)0.0579 (14)0.0596 (14)0.0144 (11)−0.0087 (11)0.0092 (11)
N10.0678 (13)0.0507 (12)0.0688 (14)−0.0265 (10)−0.0316 (11)0.0184 (10)
N20.0420 (10)0.0529 (11)0.0439 (10)−0.0091 (8)0.0012 (8)−0.0076 (8)
N30.0368 (9)0.0614 (12)0.0420 (9)−0.0061 (8)−0.0046 (7)−0.0111 (9)
N40.0385 (8)0.0289 (8)0.0338 (8)−0.0064 (6)−0.0031 (6)−0.0028 (6)
N50.0363 (9)0.0317 (9)0.0407 (9)−0.0006 (7)−0.0023 (7)−0.0001 (7)
O10.0513 (9)0.0413 (9)0.0904 (12)−0.0006 (7)−0.0138 (8)−0.0095 (8)
O20.1085 (16)0.0526 (11)0.1104 (16)0.0045 (11)−0.0328 (12)0.0230 (11)
O30.1177 (16)0.0729 (12)0.0587 (11)−0.0338 (11)−0.0321 (11)0.0242 (9)
O40.0656 (10)0.0825 (12)0.0461 (9)−0.0069 (9)0.0138 (8)−0.0138 (8)
O50.0638 (10)0.0524 (10)0.0677 (10)0.0059 (8)−0.0006 (8)0.0038 (8)
O60.0623 (10)0.0701 (11)0.0503 (9)−0.0117 (8)0.0055 (7)0.0075 (8)
O70.0693 (11)0.0822 (12)0.0591 (10)−0.0126 (9)0.0035 (8)−0.0371 (9)
O80.0599 (9)0.0308 (7)0.0409 (7)−0.0161 (6)0.0051 (6)−0.0049 (6)
O90.0948 (12)0.0441 (9)0.0388 (8)−0.0271 (8)0.0105 (8)0.0014 (6)
Geometric parameters (Å, °) top
C1—O11.244 (2)C14—H14B0.970
C1—C21.450 (3)C15—N41.479 (2)
C1—C61.453 (3)C15—C161.509 (3)
C2—C31.369 (3)C15—H15A0.970
C2—N11.466 (3)C15—H15B0.970
C3—C41.375 (3)C16—N51.493 (2)
C3—H30.930C16—H16A0.970
C4—C51.382 (2)C16—H16B0.970
C4—N21.447 (2)C17—N51.490 (2)
C5—C61.362 (2)C17—C181.505 (2)
C5—H50.930C17—H17A0.970
C6—N31.456 (2)C17—H17B0.970
C7—O91.209 (2)C18—N41.476 (2)
C7—O81.313 (2)C18—H18A0.970
C7—C81.494 (2)C18—H18B0.970
C8—C91.385 (2)C19—N51.489 (2)
C8—C131.391 (2)C19—H19A0.960
C9—C101.382 (3)C19—H19B0.960
C9—H90.930C19—H19C0.960
C10—C111.390 (3)N1—O21.215 (3)
C10—H100.930N1—O31.226 (3)
C11—C121.386 (2)N2—O41.225 (2)
C11—C141.509 (2)N2—O51.227 (2)
C12—C131.386 (2)N3—O71.223 (2)
C12—H120.930N3—O61.226 (2)
C13—H130.930N5—H5A0.89 (2)
C14—N41.491 (2)O8—H80.820
C14—H14A0.970
O1—C1—C2125.88 (19)C16—C15—H15A109.3
O1—C1—C6122.99 (19)N4—C15—H15B109.3
C2—C1—C6111.10 (16)C16—C15—H15B109.3
C3—C2—C1123.83 (18)H15A—C15—H15B108.0
C3—C2—N1115.70 (19)N5—C16—C15111.14 (14)
C1—C2—N1120.46 (19)N5—C16—H16A109.4
C2—C3—C4120.19 (18)C15—C16—H16A109.4
C2—C3—H3119.9N5—C16—H16B109.4
C4—C3—H3119.9C15—C16—H16B109.4
C3—C4—C5120.72 (17)H16A—C16—H16B108.0
C3—C4—N2119.81 (17)N5—C17—C18110.62 (15)
C5—C4—N2119.47 (17)N5—C17—H17A109.5
C6—C5—C4118.97 (17)C18—C17—H17A109.5
C6—C5—H5120.5N5—C17—H17B109.5
C4—C5—H5120.5C18—C17—H17B109.5
C5—C6—C1125.15 (17)H17A—C17—H17B108.1
C5—C6—N3115.99 (17)N4—C18—C17110.48 (14)
C1—C6—N3118.84 (16)N4—C18—H18A109.6
O9—C7—O8123.05 (17)C17—C18—H18A109.6
O9—C7—C8123.12 (16)N4—C18—H18B109.6
O8—C7—C8113.82 (15)C17—C18—H18B109.6
C9—C8—C13119.15 (16)H18A—C18—H18B108.1
C9—C8—C7118.80 (16)N5—C19—H19A109.5
C13—C8—C7122.01 (15)N5—C19—H19B109.5
C10—C9—C8120.65 (17)H19A—C19—H19B109.5
C10—C9—H9119.7N5—C19—H19C109.5
C8—C9—H9119.7H19A—C19—H19C109.5
C9—C10—C11120.59 (16)H19B—C19—H19C109.5
C9—C10—H10119.7O2—N1—O3122.7 (2)
C11—C10—H10119.7O2—N1—C2119.6 (2)
C12—C11—C10118.64 (16)O3—N1—C2117.7 (2)
C12—C11—C14120.67 (16)O4—N2—O5123.64 (17)
C10—C11—C14120.69 (16)O4—N2—C4117.71 (17)
C13—C12—C11121.00 (17)O5—N2—C4118.64 (16)
C13—C12—H12119.5O7—N3—O6123.34 (18)
C11—C12—H12119.5O7—N3—C6118.32 (18)
C12—C13—C8119.95 (16)O6—N3—C6118.34 (17)
C12—C13—H13120.0C18—N4—C15110.02 (14)
C8—C13—H13120.0C18—N4—C14112.50 (13)
N4—C14—C11115.44 (15)C15—N4—C14111.92 (14)
N4—C14—H14A108.4C17—N5—C19111.33 (15)
C11—C14—H14A108.4C17—N5—C16109.59 (15)
N4—C14—H14B108.4C19—N5—C16112.03 (15)
C11—C14—H14B108.4C17—N5—H5A106.5 (13)
H14A—C14—H14B107.5C19—N5—H5A105.9 (13)
N4—C15—C16111.45 (14)C16—N5—H5A111.3 (13)
N4—C15—H15A109.3C7—O8—H8109.5
O1—C1—C2—C3−176.28 (19)C9—C8—C13—C120.4 (3)
C6—C1—C2—C32.0 (3)C7—C8—C13—C12−177.54 (16)
O1—C1—C2—N12.5 (3)C12—C11—C14—N4−90.9 (2)
C6—C1—C2—N1−179.22 (16)C10—C11—C14—N488.9 (2)
C1—C2—C3—C4−1.1 (3)N4—C15—C16—N5−55.9 (2)
N1—C2—C3—C4−179.94 (17)N5—C17—C18—N459.5 (2)
C2—C3—C4—C50.3 (3)C3—C2—N1—O2−173.7 (2)
C2—C3—C4—N2−179.94 (17)C1—C2—N1—O27.4 (3)
C3—C4—C5—C6−0.7 (3)C3—C2—N1—O36.7 (3)
N2—C4—C5—C6179.59 (16)C1—C2—N1—O3−172.20 (18)
C4—C5—C6—C11.9 (3)C3—C4—N2—O42.3 (3)
C4—C5—C6—N3−179.92 (16)C5—C4—N2—O4−177.91 (17)
O1—C1—C6—C5175.93 (18)C3—C4—N2—O5−178.37 (18)
C2—C1—C6—C5−2.4 (3)C5—C4—N2—O51.4 (3)
O1—C1—C6—N3−2.2 (3)C5—C6—N3—O7146.71 (18)
C2—C1—C6—N3179.41 (16)C1—C6—N3—O7−35.0 (2)
O9—C7—C8—C913.3 (3)C5—C6—N3—O6−32.8 (2)
O8—C7—C8—C9−165.86 (16)C1—C6—N3—O6145.57 (18)
O9—C7—C8—C13−168.83 (19)C17—C18—N4—C15−58.31 (19)
O8—C7—C8—C1312.1 (2)C17—C18—N4—C14176.17 (15)
C13—C8—C9—C10−0.7 (3)C16—C15—N4—C1856.68 (19)
C7—C8—C9—C10177.30 (16)C16—C15—N4—C14−177.48 (15)
C8—C9—C10—C11−0.3 (3)C11—C14—N4—C1864.0 (2)
C9—C10—C11—C121.5 (3)C11—C14—N4—C15−60.5 (2)
C9—C10—C11—C14−178.33 (16)C18—C17—N5—C19178.02 (17)
C10—C11—C12—C13−1.8 (3)C18—C17—N5—C16−57.47 (19)
C14—C11—C12—C13178.01 (16)C15—C16—N5—C1755.6 (2)
C11—C12—C13—C80.9 (3)C15—C16—N5—C19179.69 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8···N4i0.821.792.6006 (19)172
N5—H5A···O1ii0.89 (2)1.89 (2)2.734 (2)156.9 (18)
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8···N4i0.821.792.6006 (19)172
N5—H5A···O1ii0.89 (2)1.89 (2)2.734 (2)156.9 (18)
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

QNMHA thanks R. L. Fine Chem, Bangalore, for a gift sample of 4-[(4-methylpiperazin-1-yl)methyl]benzoic acid. HSY thanks the University of Mysore for research facilities.

references
References top

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