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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2318.
Published online 2009 September 5. doi:  10.1107/S1600536809033911
PMCID: PMC2970445

7-Chloro-5-(2-ethoxy­phen­yl)-1-methyl-3-propyl-2,6-dihydro-1H-pyrazolo[4,3-d]pyrimidine

Abstract

In the title compound, C17H21ClN4O, the benzene ring is oriented at dihedral angles of 1.59 (3) and 1.27 (3)° with respect to the pyrimidine and pyrazole rings, while the dihedral angle between the pyrimidine and pyrazole rings is 0.83 (3)°. An intra­molecular N—H(...)O hydrogen bond results in the formation of a planar (r.m.s. deviation 0.004 Å) six-membered ring.

Related literature

For a related structure, see: Rajesh & Joshi (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o2318-scheme1.jpg

Experimental

Crystal data

  • C17H21ClN4O
  • M r = 332.83
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2318-efi1.jpg
  • a = 4.6700 (9) Å
  • b = 11.647 (2) Å
  • c = 16.064 (3) Å
  • α = 78.56 (3)°
  • β = 86.75 (3)°
  • γ = 79.81 (3)°
  • V = 842.7 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 294 K
  • 0.30 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.932, T max = 0.977
  • 3470 measured reflections
  • 3061 independent reflections
  • 2353 reflections with I > 2σ(I)
  • R int = 0.033
  • 3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.182
  • S = 1.00
  • 3061 reflections
  • 208 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.52 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033911/hk2761sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033911/hk2761Isup2.hkl

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

Acknowledgments

The authors thank the Innovation Fund for Doctoral Theses (BSCX200811) and Nanjing University of Technology for support.

supplementary crystallographic information

Comment

Some derivatives of 5-(2-ethoxyphenyl)-1-methyl-3-propyl-1,6-dihydro-7H -pyrazolo[4,3-d]pyrimidin-7-one are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C3-C8), B (N1/N2/C9-C12) and C (N3/N4/C10/C11/C13) are, of course, planar. The dihedral angles between them are A/B = 1.59 (3), A/C = 1.27 (3) and B/C = 0.83 (3) °. The intramolecular N-H···O hydrogen bond (Table 1) results in the formation of a planar six-membered ring D (O1/N1/C3/C8/C9/H1A), which is oriented with respect to the other rings at dihedral angles of A/D = 1.01 (3), B/D = 0.63 (3) and C/D = 0.83 (3) °. So, the rings are almost coplanar.

Experimental

For the preparation of the title compound, 5-(2-ethoxyphenyl)-1-methyl-3-propyl -1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one (15.6 g) and phosphorus trichloride (13.7 g) were added into carbon tetrachloride (100 ml) at 345-350 K. The gross products were extracted with n-hexane, dried under vaccum, and then recrystallized in dichloromethane. Finally the title compound is obtained (yield; 1.5 g) (Rajesh et al., 2007). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement

H atoms were positioned geometrically with N-H = 0.86 Å (for NH) and C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.

Crystal data

C17H21ClN4OZ = 2
Mr = 332.83F(000) = 352
Triclinic, P1Dx = 1.312 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.6700 (9) ÅCell parameters from 25 reflections
b = 11.647 (2) Åθ = 9–13°
c = 16.064 (3) ŵ = 0.24 mm1
α = 78.56 (3)°T = 294 K
β = 86.75 (3)°BlocK, yellow
γ = 79.81 (3)°0.30 × 0.10 × 0.10 mm
V = 842.7 (3) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer2353 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.033
graphiteθmax = 25.3°, θmin = 1.3°
ω/2θ scansh = 0→5
Absorption correction: ψ scan (North et al., 1968)k = −13→13
Tmin = 0.932, Tmax = 0.977l = −19→19
3470 measured reflections3 standard reflections every 120 min
3061 independent reflections intensity decay: 1%

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)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.1P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3
3061 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = −0.52 e Å3

Special details

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)

xyzUiso*/Ueq
Cl0.45734 (19)0.18716 (7)0.56202 (5)0.0581 (3)
O10.4864 (5)0.49028 (18)0.68108 (14)0.0528 (6)
N10.6871 (5)0.2658 (2)0.68131 (14)0.0420 (6)
H1A0.57530.33130.66130.050*
N21.0314 (5)0.1732 (2)0.78486 (14)0.0414 (6)
N31.1345 (6)−0.1091 (2)0.72458 (16)0.0506 (7)
H3A1.2075−0.18280.72690.061*
N40.9354 (6)−0.0435 (2)0.66884 (16)0.0466 (6)
C10.1508 (7)0.5709 (3)0.5722 (2)0.0605 (9)
H1B0.02840.64160.54430.091*
H1C0.03350.51190.59560.091*
H1D0.28930.54100.53190.091*
C20.3079 (7)0.5992 (3)0.6417 (2)0.0550 (8)
H2B0.42780.65870.61890.066*
H2C0.17030.62970.68290.066*
C30.6554 (7)0.4882 (3)0.74759 (19)0.0452 (7)
C40.6545 (8)0.5877 (3)0.7839 (2)0.0597 (9)
H4A0.53250.65870.76320.072*
C50.8344 (9)0.5806 (3)0.8503 (2)0.0671 (10)
H5A0.83250.64700.87440.081*
C61.0161 (9)0.4770 (3)0.8812 (2)0.0635 (9)
H6A1.13840.47350.92570.076*
C71.0177 (7)0.3782 (3)0.8465 (2)0.0528 (8)
H7A1.14180.30820.86830.063*
C80.8384 (6)0.3800 (3)0.77958 (18)0.0428 (7)
C90.8566 (6)0.2674 (2)0.74811 (17)0.0393 (6)
C101.0325 (6)0.0743 (2)0.75138 (17)0.0397 (6)
C110.8671 (6)0.0690 (2)0.68347 (17)0.0398 (6)
C120.6759 (6)0.1717 (2)0.64296 (17)0.0389 (6)
C131.1973 (6)−0.0409 (3)0.77464 (19)0.0443 (7)
C140.8296 (8)−0.0978 (3)0.6049 (2)0.0606 (9)
H14A0.9214−0.17950.61160.091*
H14B0.8752−0.05620.54930.091*
H14C0.6226−0.09340.61160.091*
C151.3994 (7)−0.0863 (3)0.84708 (19)0.0502 (8)
H15A1.4993−0.02320.85510.060*
H15B1.5449−0.15060.83320.060*
C161.2456 (9)−0.1304 (5)0.9283 (2)0.0868 (14)
H16A1.0974−0.06610.94090.104*
H16B1.1471−0.19360.91970.104*
C171.4345 (10)−0.1757 (5)1.0040 (2)0.0865 (13)
H17A1.3173−0.20211.05270.130*
H17B1.5283−0.11321.01470.130*
H17C1.5793−0.24100.99320.130*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0624 (5)0.0586 (5)0.0533 (5)−0.0064 (4)−0.0254 (4)−0.0076 (4)
O10.0595 (13)0.0387 (11)0.0578 (13)0.0041 (10)−0.0213 (11)−0.0087 (9)
N10.0438 (13)0.0384 (13)0.0421 (13)−0.0020 (10)−0.0136 (11)−0.0050 (10)
N20.0417 (13)0.0432 (13)0.0385 (12)−0.0065 (10)−0.0090 (10)−0.0040 (10)
N30.0554 (16)0.0390 (13)0.0539 (15)0.0040 (12)−0.0135 (12)−0.0079 (11)
N40.0530 (15)0.0395 (13)0.0472 (14)−0.0013 (11)−0.0119 (12)−0.0106 (11)
C10.0518 (19)0.061 (2)0.063 (2)0.0071 (16)−0.0128 (16)−0.0078 (17)
C20.0521 (19)0.0433 (17)0.063 (2)0.0070 (14)−0.0095 (16)−0.0055 (15)
C30.0453 (16)0.0440 (16)0.0469 (17)−0.0074 (13)−0.0020 (13)−0.0102 (13)
C40.065 (2)0.0452 (18)0.070 (2)−0.0044 (16)−0.0089 (18)−0.0163 (16)
C50.081 (3)0.057 (2)0.072 (2)−0.0113 (19)−0.012 (2)−0.0298 (18)
C60.074 (2)0.065 (2)0.057 (2)−0.0163 (19)−0.0199 (18)−0.0194 (17)
C70.0583 (19)0.0499 (18)0.0516 (18)−0.0076 (15)−0.0168 (15)−0.0102 (14)
C80.0430 (16)0.0428 (16)0.0432 (15)−0.0088 (13)−0.0052 (13)−0.0068 (12)
C90.0376 (14)0.0407 (15)0.0383 (14)−0.0069 (12)−0.0037 (12)−0.0037 (12)
C100.0399 (15)0.0404 (15)0.0374 (14)−0.0049 (12)−0.0043 (12)−0.0044 (12)
C110.0409 (15)0.0400 (15)0.0379 (14)−0.0066 (12)−0.0045 (12)−0.0048 (12)
C120.0376 (14)0.0413 (15)0.0377 (14)−0.0097 (12)−0.0031 (12)−0.0040 (12)
C130.0419 (16)0.0431 (16)0.0441 (16)−0.0004 (12)−0.0055 (13)−0.0042 (13)
C140.074 (2)0.0503 (19)0.061 (2)−0.0034 (17)−0.0181 (18)−0.0203 (16)
C150.0476 (17)0.0463 (17)0.0524 (18)0.0036 (13)−0.0128 (14)−0.0060 (14)
C160.060 (2)0.135 (4)0.057 (2)−0.028 (2)−0.0162 (19)0.014 (2)
C170.081 (3)0.117 (4)0.055 (2)−0.024 (3)−0.015 (2)0.010 (2)

Geometric parameters (Å, °)

Cl—C121.660 (3)C5—C61.367 (5)
O1—C21.439 (4)C5—H5A0.9300
O1—C31.358 (4)C6—C71.373 (5)
N1—C91.374 (3)C6—H6A0.9300
N1—C121.369 (4)C7—C81.395 (4)
N1—H1A0.8600C7—H7A0.9300
N2—C91.304 (4)C8—C91.484 (4)
N2—C101.363 (4)C10—C111.389 (4)
N3—N41.350 (3)C10—C131.414 (4)
N3—C131.315 (4)C11—C121.425 (4)
N3—H3A0.8600C13—C151.493 (4)
N4—C111.356 (4)C14—H14A0.9600
N4—C141.458 (4)C14—H14B0.9600
C1—C21.489 (5)C14—H14C0.9600
C1—H1B0.9600C15—C161.497 (5)
C1—H1C0.9600C15—H15A0.9700
C1—H1D0.9600C15—H15B0.9700
C2—H2B0.9700C16—C171.496 (5)
C2—H2C0.9700C16—H16A0.9700
C3—C41.396 (4)C16—H16B0.9700
C3—C81.412 (4)C17—H17A0.9600
C4—C51.375 (5)C17—H17B0.9600
C4—H4A0.9300C17—H17C0.9600
C3—O1—C2120.4 (2)C3—C8—C9125.6 (3)
C12—N1—C9127.4 (2)N2—C9—N1122.1 (3)
C12—N1—H1A116.3N2—C9—C8119.1 (3)
C9—N1—H1A116.3N1—C9—C8118.8 (2)
C9—N2—C10114.6 (2)N2—C10—C11125.1 (3)
C13—N3—N4108.1 (2)N2—C10—C13129.4 (3)
C13—N3—H3A125.9C11—C10—C13105.4 (3)
N4—N3—H3A125.9N4—C11—C10106.8 (2)
N3—N4—C11110.3 (2)N4—C11—C12132.7 (3)
N3—N4—C14119.5 (2)C10—C11—C12120.5 (3)
C11—N4—C14130.2 (3)N1—C12—C11110.1 (2)
C2—C1—H1B109.5N1—C12—Cl120.5 (2)
C2—C1—H1C109.5C11—C12—Cl129.4 (2)
H1B—C1—H1C109.5N3—C13—C10109.3 (3)
C2—C1—H1D109.5N3—C13—C15122.6 (3)
H1B—C1—H1D109.5C10—C13—C15127.9 (3)
H1C—C1—H1D109.5N4—C14—H14A109.5
O1—C2—C1106.9 (3)N4—C14—H14B109.5
O1—C2—H2B110.3H14A—C14—H14B109.5
C1—C2—H2B110.3N4—C14—H14C109.5
O1—C2—H2C110.3H14A—C14—H14C109.5
C1—C2—H2C110.3H14B—C14—H14C109.5
H2B—C2—H2C108.6C13—C15—C16112.7 (3)
O1—C3—C4122.6 (3)C13—C15—H15A109.1
O1—C3—C8117.3 (3)C16—C15—H15A109.1
C4—C3—C8120.1 (3)C13—C15—H15B109.1
C5—C4—C3119.9 (3)C16—C15—H15B109.1
C5—C4—H4A120.0H15A—C15—H15B107.8
C3—C4—H4A120.0C17—C16—C15115.6 (3)
C6—C5—C4120.8 (3)C17—C16—H16A108.4
C6—C5—H5A119.6C15—C16—H16A108.4
C4—C5—H5A119.6C17—C16—H16B108.4
C5—C6—C7119.9 (3)C15—C16—H16B108.4
C5—C6—H6A120.1H16A—C16—H16B107.5
C7—C6—H6A120.1C16—C17—H17A109.5
C6—C7—C8121.8 (3)C16—C17—H17B109.5
C6—C7—H7A119.1H17A—C17—H17B109.5
C8—C7—H7A119.1C16—C17—H17C109.5
C7—C8—C3117.5 (3)H17A—C17—H17C109.5
C7—C8—C9116.9 (3)H17B—C17—H17C109.5
C3—O1—C2—C1−179.6 (3)C6—C7—C8—C9−179.3 (3)
C2—O1—C3—C43.4 (5)O1—C3—C8—C7178.4 (3)
C2—O1—C3—C8−176.2 (3)C4—C3—C8—C7−1.2 (5)
C12—N1—C9—N2−1.2 (5)O1—C3—C8—C9−1.6 (5)
C12—N1—C9—C8179.2 (3)C4—C3—C8—C9178.8 (3)
C9—N1—C12—C111.1 (4)C7—C8—C9—N21.4 (4)
C9—N1—C12—Cl−179.6 (2)C3—C8—C9—N2−178.6 (3)
C10—N2—C9—N10.4 (4)C7—C8—C9—N1−179.0 (3)
C10—N2—C9—C8180.0 (2)C3—C8—C9—N11.1 (4)
C9—N2—C10—C110.3 (4)N2—C10—C11—N4178.7 (3)
C9—N2—C10—C13178.9 (3)C13—C10—C11—N4−0.2 (3)
C13—N3—N4—C11−0.4 (3)N2—C10—C11—C12−0.3 (4)
C13—N3—N4—C14179.3 (3)C13—C10—C11—C12−179.1 (3)
N4—N3—C13—C100.2 (3)N4—C11—C12—N1−179.1 (3)
N4—N3—C13—C15176.7 (3)C10—C11—C12—N1−0.4 (4)
N3—N4—C11—C100.3 (3)N4—C11—C12—Cl1.7 (5)
C14—N4—C11—C10−179.3 (3)C10—C11—C12—Cl−179.6 (2)
N3—N4—C11—C12179.1 (3)N2—C10—C13—N3−178.9 (3)
C14—N4—C11—C12−0.5 (6)C11—C10—C13—N3−0.1 (3)
O1—C3—C4—C5−178.9 (3)N2—C10—C13—C154.9 (5)
C8—C3—C4—C50.7 (5)C11—C10—C13—C15−176.3 (3)
C3—C4—C5—C60.3 (6)N3—C13—C15—C16−90.3 (4)
C4—C5—C6—C7−0.7 (6)C10—C13—C15—C1685.5 (4)
C5—C6—C7—C80.2 (6)C13—C15—C16—C17−179.2 (4)
C6—C7—C8—C30.7 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.861.912.616 (3)138

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2761).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Rajesh, K. & Joshi, Y. C. (2007). Arkivoc, pp. 142–149.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography