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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1016.
Published online 2010 April 2. doi:  10.1107/S1600536810011797
PMCID: PMC2979083

2-Chloro-9-isopropyl-N,N-dimethyl-9H-purin-6-amine

Abstract

In the title compound, C10H14ClN5, the imidazole and pyrimidine rings are essentially planar [maximum deviation = 0.0013 (14) and 0.0207 (13) Å, respectively]. In the crystal, the mol­ecules are linked by weak C—H(...)N inter­actions into chains parallel to the c axis and the crystal packing is stabilized by additional weak C—H(...)N and C—H(...)Cl inter­actions.

Related literature

The title compound was prepared according to a modification of the procedure of Fiorini & Abel (1998 [triangle]). For the synthesis and/or biological activity of related compounds, see: Legraverend & Grierson (2006 [triangle]). For related structures, see: Kubicki & Codding (2001 [triangle]); Trávníček & Popa (2007 [triangle]); Rouchal et al. (2009a [triangle],b [triangle],c [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1016-scheme1.jpg

Experimental

Crystal data

  • C10H14ClN5
  • M r = 239.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1016-efi1.jpg
  • a = 12.0483 (3) Å
  • b = 8.7689 (2) Å
  • c = 11.5538 (3) Å
  • β = 109.965 (3)°
  • V = 1147.30 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.31 mm−1
  • T = 120 K
  • 0.40 × 0.40 × 0.30 mm

Data collection

  • Oxford Diffraction Xcalibur (Sapphire2 large Be window) diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 [triangle]) T min = 0.968, T max = 1.000
  • 13393 measured reflections
  • 2022 independent reflections
  • 1798 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.068
  • S = 1.05
  • 2022 reflections
  • 149 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011797/pk2238sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011797/pk2238Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The financial support of this work by the Czech Ministry of Education, project No. MSM 7088352101 is gratefully acknowledged.

supplementary crystallographic information

Comment

The heterocyclic system, imidazo[4,5-d]pyrimidine, commonly known as purine, was first named by Emil Fisher at the turn of the 19th century. A large number of variously substituted purines exhibit a wide range of biological activities (Legraverend & Grierson, 2006). They act as interferon inducers, adenosine receptor ligands, inhibitors of microtubule assembly, protein kinases, sulfotransferases and phosphodiesterases. The title molecule was prepared as a part of our research into the synthesis of novel trisubstituted purines.

The asymmetric unit of the title compound consists of a single purine molecule. Both imidazole and pyrimidine rings are nearly planar with maximum deviations from the mean plane being 0.0013 (14) Å for C4 (imidazole ring) and 0.0207 (13) Å for C2 (pyrimidine ring). Both carbon atoms of the dimethylamino substituent lie essentially in the pyrimidine mean plane as demonstrated by torsion angles C3—C2—N5—C7 and C3—C2—N5—C6, which are 4.3 (2)° and 175.90 (13)°, respectively. The torsion angle describing the orientation of isopropyl and purine ring, H8A—C8—N4—C4 is -163.55 (13)°. Molecules are linked into chains along the c axis by weak C4—H4···N1 interactions (Table 1, Fig. 2). Crystal packing is further stabilised by short C—H···N and C—H···Cl contacts (Table 1).

Experimental

The title compound was prepared according to a slightly modified literature procedure (Fiorini & Abel, 1998). 2,6-Dichloro-9-(propan-2-yl)-9H-purine (0.87 mmol, 196 mg) and methylamine hydrochloride (0.91 mmol, 61.5 mg) were dissolved in a mixture of DMF (2.5 ml) and N-ethyl-N-isopropylpropan-2-amine (1.74 mmol, 225 mg). The resulting solution was stirred at 90 °C for 2 hours. Subsequently, the mixture was diluted with water and extracted with diethyl ether. Combined organic layers were washed twice with brine and dried over Na2SO4. Crude product consisting of two compounds with relative abundances of 43% and 57% according to GC were obtained after evaporation of the solvent in vacuum. The products were identified as N-methyl and N,N-dimethyl derivatives. Column chromatography (silica gel; petroleum ether/ethyl acetate, v/v, 1/1) yielded the latter as a colourless crystalline powder (105 mg, 54%, mp 418–422 K). The crystal used for data collection was grown by spontaneous evaporation from deuterochloroform at room temperature.

Figures

Fig. 1.
An ellipsoid plot (50% probability) of the asymmetric unit. Hydrogen atoms are represented as arbitrary spheres.
Fig. 2.
A view of the crystal structure showing chains parallel to the a-axis linked via C—H···N contacts (dotted lines). H-atoms (except those which are involved in H-bonding) have been omitted for clarity.

Crystal data

C10H14ClN5F(000) = 504
Mr = 239.71Dx = 1.388 Mg m3
Monoclinic, P21/cMelting point = 422–418 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.7107 Å
a = 12.0483 (3) ÅCell parameters from 8720 reflections
b = 8.7689 (2) Åθ = 2.9–27.3°
c = 11.5538 (3) ŵ = 0.31 mm1
β = 109.965 (3)°T = 120 K
V = 1147.30 (5) Å3Block, colourless
Z = 40.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur (Sapphire2 large Be window) diffractometer2022 independent reflections
Radiation source: Enhance (Mo) X-ray Source1798 reflections with I > 2σ(I)
graphiteRint = 0.016
Detector resolution: 8.4 pixels mm-1θmax = 25.0°, θmin = 2.9°
ω scansh = −14→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)k = −9→10
Tmin = 0.968, Tmax = 1.000l = −13→13
13393 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0355P)2 + 0.4207P] where P = (Fo2 + 2Fc2)/3
2022 reflections(Δ/σ)max < 0.001
149 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

Experimental. CrysAlis RED (Oxford Diffraction Ltd, 2009). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
Cl10.78721 (3)0.18146 (4)0.33908 (3)0.02432 (12)
N10.80758 (9)−0.04481 (12)0.48883 (9)0.0166 (2)
N20.67313 (9)0.15775 (12)0.49228 (10)0.0179 (3)
N30.69089 (10)−0.14494 (13)0.72589 (10)0.0225 (3)
N40.82037 (10)−0.23853 (13)0.64258 (10)0.0184 (3)
N50.55582 (10)0.16106 (13)0.61327 (10)0.0197 (3)
C10.75175 (11)0.08580 (15)0.45552 (11)0.0168 (3)
C20.63956 (11)0.09009 (15)0.58130 (11)0.0169 (3)
C30.69562 (11)−0.04950 (15)0.63134 (11)0.0167 (3)
C40.76612 (12)−0.25408 (16)0.72857 (13)0.0229 (3)
H4A0.7816−0.33660.78510.027*
C50.77572 (11)−0.10713 (15)0.57988 (11)0.0157 (3)
C60.51096 (13)0.30962 (16)0.56040 (14)0.0256 (3)
H6A0.49330.30680.47110.038*
H6B0.57070.38800.59680.038*
H6C0.43880.33370.57780.038*
C70.51768 (12)0.10497 (17)0.71274 (13)0.0248 (3)
H7A0.5191−0.00680.71340.037*
H7B0.43720.14060.69980.037*
H7C0.57110.14350.79170.037*
C80.90697 (12)−0.34193 (16)0.61883 (13)0.0214 (3)
H8A0.9468−0.28490.56910.026*
C90.84438 (14)−0.47859 (18)0.54375 (14)0.0314 (4)
H9A0.7866−0.44330.46600.047*
H9B0.8038−0.53580.59040.047*
H9C0.9024−0.54470.52650.047*
C101.00104 (13)−0.38877 (18)0.73954 (14)0.0294 (3)
H10A1.0359−0.29740.78680.044*
H10B1.0627−0.44760.72210.044*
H10C0.9650−0.45150.78740.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0311 (2)0.0225 (2)0.02385 (19)0.00422 (14)0.01520 (15)0.00769 (13)
N10.0180 (5)0.0170 (6)0.0149 (5)−0.0002 (4)0.0058 (4)0.0005 (4)
N20.0189 (6)0.0173 (6)0.0176 (5)0.0002 (4)0.0062 (4)−0.0005 (4)
N30.0256 (6)0.0227 (6)0.0219 (6)0.0007 (5)0.0115 (5)0.0038 (5)
N40.0198 (6)0.0168 (6)0.0189 (6)0.0020 (4)0.0071 (5)0.0037 (5)
N50.0196 (6)0.0200 (6)0.0204 (6)0.0021 (5)0.0081 (5)−0.0020 (5)
C10.0192 (7)0.0170 (7)0.0136 (6)−0.0023 (5)0.0046 (5)−0.0003 (5)
C20.0162 (6)0.0174 (7)0.0152 (6)−0.0031 (5)0.0031 (5)−0.0048 (5)
C30.0169 (6)0.0174 (7)0.0155 (6)−0.0025 (5)0.0049 (5)−0.0019 (5)
C40.0267 (7)0.0221 (8)0.0219 (7)0.0014 (6)0.0109 (6)0.0067 (6)
C50.0149 (6)0.0153 (7)0.0149 (6)−0.0017 (5)0.0025 (5)−0.0016 (5)
C60.0264 (7)0.0228 (8)0.0280 (8)0.0070 (6)0.0097 (6)−0.0013 (6)
C70.0231 (7)0.0284 (8)0.0276 (7)−0.0006 (6)0.0148 (6)−0.0038 (6)
C80.0202 (7)0.0212 (7)0.0250 (7)0.0051 (6)0.0105 (6)0.0055 (6)
C90.0347 (9)0.0262 (8)0.0329 (8)0.0061 (7)0.0110 (7)−0.0036 (7)
C100.0225 (7)0.0306 (8)0.0326 (8)0.0044 (6)0.0064 (6)0.0094 (7)

Geometric parameters (Å, °)

Cl1—C11.7575 (13)C6—H6A0.9800
N1—C11.3174 (17)C6—H6B0.9800
N1—C51.3522 (17)C6—H6C0.9800
N2—C11.3230 (17)C7—H7A0.9800
N2—C21.3630 (17)C7—H7B0.9800
N3—C41.3112 (18)C7—H7C0.9800
N3—C31.3926 (17)C8—C91.520 (2)
N4—C51.3696 (17)C8—C101.5228 (19)
N4—C41.3698 (18)C8—H8A1.0000
N4—C81.4769 (17)C9—H9A0.9800
N5—C21.3402 (17)C9—H9B0.9800
N5—C71.4610 (18)C9—H9C0.9800
N5—C61.4618 (18)C10—H10A0.9800
C2—C31.4220 (19)C10—H10B0.9800
C3—C51.3900 (18)C10—H10C0.9800
C4—H4A0.9500
C1—N1—C5109.04 (11)N5—C6—H6C109.5
C1—N2—C2117.66 (11)H6A—C6—H6C109.5
C4—N3—C3104.13 (11)H6B—C6—H6C109.5
C5—N4—C4105.59 (11)N5—C7—H7A109.5
C5—N4—C8126.37 (11)N5—C7—H7B109.5
C4—N4—C8128.02 (11)H7A—C7—H7B109.5
C2—N5—C7121.94 (11)N5—C7—H7C109.5
C2—N5—C6120.29 (11)H7A—C7—H7C109.5
C7—N5—C6117.26 (11)H7B—C7—H7C109.5
N1—C1—N2132.14 (12)N4—C8—C9110.23 (11)
N1—C1—Cl1113.90 (10)N4—C8—C10110.34 (11)
N2—C1—Cl1113.95 (10)C9—C8—C10112.28 (12)
N5—C2—N2116.82 (12)N4—C8—H8A107.9
N5—C2—C3125.83 (12)C9—C8—H8A107.9
N2—C2—C3117.35 (11)C10—C8—H8A107.9
C5—C3—N3109.72 (11)C8—C9—H9A109.5
C5—C3—C2116.22 (12)C8—C9—H9B109.5
N3—C3—C2134.05 (12)H9A—C9—H9B109.5
N3—C4—N4114.04 (12)C8—C9—H9C109.5
N3—C4—H4A123.0H9A—C9—H9C109.5
N4—C4—H4A123.0H9B—C9—H9C109.5
N1—C5—N4125.94 (12)C8—C10—H10A109.5
N1—C5—C3127.51 (12)C8—C10—H10B109.5
N4—C5—C3106.52 (11)H10A—C10—H10B109.5
N5—C6—H6A109.5C8—C10—H10C109.5
N5—C6—H6B109.5H10A—C10—H10C109.5
H6A—C6—H6B109.5H10B—C10—H10C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4A···N1i0.952.493.3728 (18)154
C7—H7C···Cl1ii0.982.913.5981 (14)128
C7—H7B···N3iii0.982.753.584 (2)143
C9—H9A···N3iv0.982.733.6664 (18)161

Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y−1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2238).

References

  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Fiorini, M. T. & Abel, Ch. (1998). Tetrahedron Lett.39, 1827–1830.
  • Kubicki, M. & Codding, P. W. (2001). Acta Cryst. E57, o332–o334.
  • Legraverend, M. & Grierson, D. S. (2006). Bioorg. Med. Chem.14, 3987–4006. [PubMed]
  • Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst.41, 466–470.
  • Oxford Diffraction (2009). CrysAlis RED and CrysAlis CCD Oxford Diffraction Ltd, Yarnton, England.
  • Rouchal, M., Nečas, M., de Carvalho, F. P. & Vícha, R. (2009a). Acta Cryst. E65, o298–o299. [PMC free article] [PubMed]
  • Rouchal, M., Nečas, M. & Vícha, R. (2009b). Acta Cryst. E65, o1268. [PMC free article] [PubMed]
  • Rouchal, M., Nečas, M. & Vícha, R. (2009c). Acta Cryst. E65, o1676. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Trávníček, Z. & Popa, I. (2007). Acta Cryst. E63, o728–o730.

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