Methyl (4-oxo-1-phenyl-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-5-yl)acetate

The title compound, C₁₄H₁₂N₄O₃, a pyrazolopyrimidine derivative, displays normal geometrical parameters. The dihedral angle between the mean planes of the pyrazolopyrimidine unit and the phenyl ring is 26.14 (4)°. The non-H atoms of the ester side chain are coplanar (r.m.s. deviation = 0.009 Å) and this plane is almost perpendicular [dihedral angle = 84.31 (4)°] to the central ring system.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.035
• wR factor = 0.096
• Data-to-parameter ratio = 15.2

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S1. Comment

Pyrazolo[3,4-d]pyrimidines and their derivatives are of interest as potential bioactive molecules. Various pyrazolopyrimidine derivatives are reported to have antileishmanial, antihypertensive, antibacterial and antifungal, antiangiogenic, antiinflammatory and analgesic activities. The title compound, a new pyrazolopyrimidine derivative, (I), C₁₄H₁₂N₄O₃, has been synthesized and its crystal structure determined.

Related literature

For related structures, see: Wen et al. (2004); Oliveira-Campos et al. (2006) and Portilla et al. (2005). For background literature, see: Garg et al. (1990); El-Feky & Abd El-Samii (1996); Ismail, et al. (2003); Devesa, et al. (2004) and Russo et al. (1993).

S2. Experimental

4-Hydroxy-1-phenyl pyrazolo[3,4-d]pyrimidine (21.2 g, 0.1 mol) in 180 ml acetone was stirred with anhydrous potassium carbonate (16.5 g, 0.12 mol) at room temperature and methyl chloroacetate (12.2 g, 0.1 mol) was added to it drop-wise. The reaction mixture was then refluxed for 8 h. Progress of the reaction was monitored by TLC. The acetone was distilled out and the residue was diluted with 250 ml water. The solid obtained was filtered, washed with water and then recrystallized from methanol to obtain the title compound as colourless needles (Yield: 95%; m.p.: 421–424 K). Crystals of (I) suitable for X-ray diffraction were obtained from acetone by slow evaporation. Analysis for (I), C₁₄H₁₂N₄O₃: Found (Calculated): C: 59.01 (59.15); H: 4.11 (4.25); N: 19.62% (19.71%). ¹H-NMR (400 MHz, CDCl₃): δ 3.78 (s, 3H, –CH₃), 4.73 (s, 2H, –CH₂), 7.34 (t, 1H, ArH), 7.48 (t, 2H, ArH), 7.94 (s, 1H, ArH), 7.99 (d (J = 6.08), 1H, ArH), 8.23 (s, 1H, ArH).

S3. Refinement

The H atoms were found in a difference map, repositioned in idealized locations (C—H = 0.95–0.99 Å) and refined as riding with U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(C_methyl). The methyl group was allowed to rotate but not to tip to best fit the electron density.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Perspective view of (I) with the atom numbering; displacement ellipsoids are at the 50% probability level (arbitrary spheres for the H atoms).

Methyl (4-oxo-1-phenyl-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-5-yl)acetate

Crystal data

C14H12N4O3	Z = 2
Mr = 284.28	F(000) = 296
Triclinic, P1	Dx = 1.471 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8628 (8) Å	Cell parameters from 5143 reflections
b = 7.6128 (9) Å	θ = 3.9–26.8°
c = 12.4949 (16) Å	µ = 0.11 mm^−1
α = 87.036 (10)°	T = 173 K
β = 89.608 (11)°	Block, colourless
γ = 79.973 (8)°	0.45 × 0.43 × 0.42 mm
V = 641.97 (13) Å^3

Data collection

Stoe IPDSII two-circle diffractometer	2601 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 27.6°, θmin = 3.7°
ω scans	h = −8→8
6143 measured reflections	k = −9→9
2914 independent reflections	l = −16→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0504P)^2 + 0.1857P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2914 reflections	Δρmax = 0.28 e Å^−3
192 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.070 (7)

Special details

Experimental. ;

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.39377 (13)	0.15427 (12)	0.60302 (7)	0.0202 (2)
N2	0.59660 (13)	0.14301 (13)	0.61111 (7)	0.0234 (2)
C3	0.65154 (16)	0.22729 (14)	0.52324 (9)	0.0228 (2)
H3	0.7840	0.2402	0.5073	0.027*
C4	0.48698 (15)	0.29526 (14)	0.45657 (8)	0.0207 (2)
C5	0.32439 (15)	0.24664 (14)	0.51033 (8)	0.0193 (2)
N6	0.13029 (13)	0.28745 (13)	0.47750 (7)	0.0228 (2)
C7	0.10838 (16)	0.38329 (15)	0.38733 (9)	0.0237 (2)
H7	−0.0225	0.4156	0.3599	0.028*
N8	0.25607 (14)	0.44203 (13)	0.32814 (7)	0.0233 (2)
C9	0.45997 (16)	0.40085 (14)	0.35729 (8)	0.0224 (2)
O9	0.58579 (13)	0.45707 (12)	0.30136 (7)	0.0298 (2)
C11	0.28917 (16)	0.08388 (14)	0.69005 (8)	0.0209 (2)
C12	0.37358 (19)	0.06459 (19)	0.79214 (10)	0.0332 (3)
H12	0.4986	0.0979	0.8036	0.040*
C13	0.2726 (2)	−0.0040 (2)	0.87694 (10)	0.0412 (3)
H13	0.3298	−0.0178	0.9465	0.049*
C14	0.0892 (2)	−0.05258 (17)	0.86134 (10)	0.0320 (3)
H14	0.0208	−0.0982	0.9199	0.038*
C15	0.00682 (17)	−0.03376 (15)	0.75916 (9)	0.0264 (2)
H15	−0.1185	−0.0668	0.7480	0.032*
C16	0.10647 (16)	0.03323 (15)	0.67283 (9)	0.0239 (2)
H16	0.0505	0.0443	0.6030	0.029*
C21	0.20561 (18)	0.55468 (15)	0.23041 (9)	0.0269 (2)
H21A	0.2833	0.6529	0.2277	0.032*
H21B	0.0636	0.6085	0.2319	0.032*
C22	0.24787 (16)	0.44799 (16)	0.13065 (9)	0.0241 (2)
O22	0.28503 (14)	0.28799 (12)	0.12993 (7)	0.0346 (2)
O23	0.23286 (13)	0.55953 (12)	0.04324 (6)	0.0327 (2)
C23	0.2652 (2)	0.4720 (2)	−0.05810 (10)	0.0403 (3)
H23A	0.3964	0.3966	−0.0576	0.061*
H23B	0.2571	0.5626	−0.1173	0.061*
H23C	0.1638	0.3980	−0.0676	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0177 (4)	0.0235 (4)	0.0201 (4)	−0.0055 (3)	0.0006 (3)	0.0001 (3)
N2	0.0173 (4)	0.0279 (5)	0.0256 (5)	−0.0057 (3)	0.0007 (3)	−0.0013 (4)
C3	0.0193 (5)	0.0253 (5)	0.0250 (5)	−0.0063 (4)	0.0032 (4)	−0.0035 (4)
C4	0.0207 (5)	0.0222 (5)	0.0207 (5)	−0.0070 (4)	0.0042 (4)	−0.0035 (4)
C5	0.0203 (5)	0.0203 (5)	0.0183 (5)	−0.0060 (4)	0.0023 (4)	−0.0027 (4)
N6	0.0199 (4)	0.0281 (5)	0.0210 (4)	−0.0061 (3)	0.0003 (3)	0.0002 (3)
C7	0.0220 (5)	0.0282 (5)	0.0215 (5)	−0.0061 (4)	0.0005 (4)	−0.0012 (4)
N8	0.0272 (5)	0.0262 (5)	0.0172 (4)	−0.0068 (4)	0.0014 (3)	0.0007 (3)
C9	0.0254 (5)	0.0234 (5)	0.0198 (5)	−0.0073 (4)	0.0049 (4)	−0.0043 (4)
O9	0.0311 (4)	0.0340 (5)	0.0262 (4)	−0.0118 (3)	0.0097 (3)	0.0009 (3)
C11	0.0229 (5)	0.0205 (5)	0.0194 (5)	−0.0048 (4)	0.0030 (4)	−0.0001 (4)
C12	0.0319 (6)	0.0483 (7)	0.0231 (6)	−0.0183 (5)	−0.0025 (5)	0.0032 (5)
C13	0.0460 (8)	0.0622 (9)	0.0196 (6)	−0.0232 (7)	−0.0031 (5)	0.0061 (6)
C14	0.0373 (7)	0.0366 (6)	0.0238 (6)	−0.0125 (5)	0.0074 (5)	0.0031 (5)
C15	0.0248 (5)	0.0268 (6)	0.0283 (6)	−0.0074 (4)	0.0046 (4)	0.0014 (4)
C16	0.0235 (5)	0.0268 (5)	0.0218 (5)	−0.0063 (4)	0.0004 (4)	0.0011 (4)
C21	0.0340 (6)	0.0269 (5)	0.0196 (5)	−0.0062 (5)	0.0008 (4)	0.0023 (4)
C22	0.0211 (5)	0.0324 (6)	0.0202 (5)	−0.0094 (4)	0.0017 (4)	0.0021 (4)
O22	0.0459 (5)	0.0322 (5)	0.0276 (4)	−0.0115 (4)	0.0041 (4)	−0.0029 (3)
O23	0.0375 (5)	0.0406 (5)	0.0188 (4)	−0.0053 (4)	0.0035 (3)	0.0053 (3)
C23	0.0387 (7)	0.0624 (9)	0.0191 (6)	−0.0070 (6)	0.0040 (5)	−0.0018 (5)

Geometric parameters (Å, º)

N1—C5	1.3672 (13)	C12—H12	0.9500
N1—N2	1.3838 (12)	C13—C14	1.3898 (19)
N1—C11	1.4311 (13)	C13—H13	0.9500
N2—C3	1.3286 (14)	C14—C15	1.3904 (17)
C3—C4	1.4148 (15)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.3949 (15)
C4—C5	1.3933 (14)	C15—H15	0.9500
C4—C9	1.4379 (15)	C16—H16	0.9500
C5—N6	1.3745 (13)	C21—C22	1.5216 (16)
N6—C7	1.3052 (14)	C21—H21A	0.9900
C7—N8	1.3739 (14)	C21—H21B	0.9900
C7—H7	0.9500	C22—O22	1.2007 (15)
N8—C9	1.4253 (15)	C22—O23	1.3415 (13)
N8—C21	1.4629 (14)	O23—C23	1.4591 (16)
C9—O9	1.2274 (13)	C23—H23A	0.9800
C11—C12	1.3947 (16)	C23—H23B	0.9800
C11—C16	1.3956 (15)	C23—H23C	0.9800
C12—C13	1.3908 (17)
C5—N1—N2	110.59 (8)	C14—C13—C12	120.96 (11)
C5—N1—C11	130.25 (9)	C14—C13—H13	119.5
N2—N1—C11	119.01 (8)	C12—C13—H13	119.5
C3—N2—N1	106.00 (9)	C13—C14—C15	119.36 (11)
N2—C3—C4	111.14 (9)	C13—C14—H14	120.3
N2—C3—H3	124.4	C15—C14—H14	120.3
C4—C3—H3	124.4	C14—C15—C16	120.59 (11)
C5—C4—C3	105.19 (9)	C14—C15—H15	119.7
C5—C4—C9	120.20 (10)	C16—C15—H15	119.7
C3—C4—C9	134.53 (10)	C15—C16—C11	119.38 (10)
N1—C5—N6	126.48 (9)	C15—C16—H16	120.3
N1—C5—C4	107.09 (9)	C11—C16—H16	120.3
N6—C5—C4	126.42 (10)	N8—C21—C22	111.45 (9)
C7—N6—C5	112.58 (9)	N8—C21—H21A	109.3
N6—C7—N8	126.36 (10)	C22—C21—H21A	109.3
N6—C7—H7	116.8	N8—C21—H21B	109.3
N8—C7—H7	116.8	C22—C21—H21B	109.3
C7—N8—C9	123.41 (9)	H21A—C21—H21B	108.0
C7—N8—C21	119.58 (10)	O22—C22—O23	125.04 (11)
C9—N8—C21	117.01 (9)	O22—C22—C21	125.21 (10)
O9—C9—N8	120.64 (10)	O23—C22—C21	109.73 (10)
O9—C9—C4	128.34 (11)	C22—O23—C23	114.78 (10)
N8—C9—C4	111.00 (9)	O23—C23—H23A	109.5
C12—C11—C16	120.46 (10)	O23—C23—H23B	109.5
C12—C11—N1	119.03 (10)	H23A—C23—H23B	109.5
C16—C11—N1	120.51 (9)	O23—C23—H23C	109.5
C13—C12—C11	119.24 (11)	H23A—C23—H23C	109.5
C13—C12—H12	120.4	H23B—C23—H23C	109.5
C11—C12—H12	120.4
C5—N1—N2—C3	−0.39 (12)	C5—C4—C9—O9	178.62 (11)
C11—N1—N2—C3	−176.28 (9)	C3—C4—C9—O9	2.3 (2)
N1—N2—C3—C4	0.16 (12)	C5—C4—C9—N8	0.20 (14)
N2—C3—C4—C5	0.12 (12)	C3—C4—C9—N8	−176.09 (11)
N2—C3—C4—C9	176.79 (11)	C5—N1—C11—C12	−152.52 (12)
N2—N1—C5—N6	−178.17 (10)	N2—N1—C11—C12	22.44 (15)
C11—N1—C5—N6	−2.88 (18)	C5—N1—C11—C16	28.25 (17)
N2—N1—C5—C4	0.47 (12)	N2—N1—C11—C16	−156.79 (10)
C11—N1—C5—C4	175.76 (10)	C16—C11—C12—C13	−0.7 (2)
C3—C4—C5—N1	−0.35 (11)	N1—C11—C12—C13	−179.91 (12)
C9—C4—C5—N1	−177.61 (9)	C11—C12—C13—C14	−0.3 (2)
C3—C4—C5—N6	178.29 (10)	C12—C13—C14—C15	0.6 (2)
C9—C4—C5—N6	1.03 (16)	C13—C14—C15—C16	0.0 (2)
N1—C5—N6—C7	177.41 (10)	C14—C15—C16—C11	−0.90 (18)
C4—C5—N6—C7	−0.97 (16)	C12—C11—C16—C15	1.26 (17)
C5—N6—C7—N8	−0.33 (16)	N1—C11—C16—C15	−179.52 (10)
N6—C7—N8—C9	1.61 (18)	C7—N8—C21—C22	−101.82 (12)
N6—C7—N8—C21	−177.63 (11)	C9—N8—C21—C22	78.89 (12)
C7—N8—C9—O9	−179.96 (10)	N8—C21—C22—O22	12.05 (16)
C21—N8—C9—O9	−0.71 (15)	N8—C21—C22—O23	−169.38 (9)
C7—N8—C9—C4	−1.40 (14)	O22—C22—O23—C23	0.15 (17)
C21—N8—C9—C4	177.86 (9)	C21—C22—O23—C23	−178.43 (10)