1-(2-Chloro­eth­yl)-1H-pyrazolo­[3,4-d]pyrimidin-4(5H)-one

Khazi, M.I.A.; Fathima, N.; Belavagi, N.S.; Begum, N.S.; Khazi, I.M.

doi:10.1107/S1600536812025184

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2083

https://doi.org/10.1107/S1600536812025184

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1-(2-Chloroethyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one

Mohammed Iqbal A. Khazi,^a Nikhath Fathima,^b Ningaraddi S. Belavagi,^a Noor Shahina Begum ^b and I. M. Khazi ^a ^*

^aDepartment of Chemistry, Karnatak University, Dharwad 580 003, India, and ^bDepartment of Studies in Chemistry, Bangalore University, Bangalore 560 001, Karnataka, India
^*Correspondence e-mail: dr_imk@yahoo.com

(Received 24 May 2012; accepted 2 June 2012; online 13 June 2012)

In the title compound, C₇H₇ClN₄O, the pyrazolopyrimidine ring is essentially planar, the r.m.s. deviation of the fitted atoms being 0.0071 Å. The crystal structure features strong N—H⋯O hydrogen bonds and further consolidated by weak C—H⋯O, C—H⋯N and C—H⋯Cl interactions.

Related literature

For the biological activity of pyrazolopyrimidines, see: Carraro et al. (2006 ). For a related structure, see: Dolzhenko et al. (2009 ). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₇ClN₄O
M_r = 198.61
Monoclinic, P 2₁ /n
a = 4.6448 (1) Å
b = 8.0792 (1) Å
c = 22.7335 (4) Å
β = 93.554 (1)°
V = 851.46 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 296 K
0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.930, T_max = 0.937
7660 measured reflections
1548 independent reflections
1353 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.100
S = 0.87
1548 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.96	2.810 (2)	170
C5—H5A⋯N4ⁱⁱ	0.93	2.79	3.676 (2)	160
C2—H2A⋯Cl1ⁱⁱⁱ	0.97	2.84	3.779 (2)	164
C2—H2B⋯N2^iv	0.97	2.59	3.463 (2)	150
C3—H3⋯O1^v	0.93	2.35	3.254 (2)	163
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) x, y+1, z; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812025184/pv2552sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025184/pv2552Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025184/pv2552Isup3.cml

checkCIF report

Comment top

Pyrazolo[3,4-d]pyrimidines are purine analogues which exhibit a number of pharmacological properties such as antitryproliferative (Carraro et al., 2006).

In the title compound (Fig. 1), the fused pyrazolopyrimidine ring is substituted with 2-chloro-ethyl group on one side and the oxo group on the other side. The pyrazolopyrimidine ring is planar with the maximum deviation from the mean statistical plane being 0.0115 (14) Å for C3. The cis orientation of 2-chloro-ethyl group with respect to the C2—N2 bond is described by the torsion angle N2—C2—N3—C3, -2.204 (4)°.

The crystal structure is stabilized by some interesting features that comprise of intermolecular N—H···O, C—H···O, C—H···N and C—H···Cl interactions (Fig. 2 and Tab. 1). The C—H···O and the N—H···O interactions result in centrosymmetric head-to-head dimers corresponding to the graph set R²₂(10) and R²₂(8) motif (Bernstein et al., 1995). There are two types of C—H···N interactions, one of which forms a helix, the other forms sheets along the crystallographic b-axis. The C—H···Cl intermolecular interaction result in one dimensional molecular chain along b-axis. The bond lengths and bond angles in the title molecule agree very well with the corresponding bond distances and bond angles reported in a closely related compound (Dolzhenko et al., 2009).

Related literature top

For the biological activity of pyrazolopyrimidines, see: Carraro et al. (2006). For a related structure, see: Dolzhenko et al. (2009). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

A mixture of 5-amino-1-(2-chloro-ethyl)-1H-pyrazole-4-carbonitrile (1 g, 5.8 mmol) and formic acid (15 ml) was heated under reflux for 10 h. The excess of formic acid was removed under reduced pressure and the solid separated was washed with water and recrystallized from ethanol. (Yield = 0.86 g, 75% and m.p. = 470–472 K).

Structure description top

Pyrazolo[3,4-d]pyrimidines are purine analogues which exhibit a number of pharmacological properties such as antitryproliferative (Carraro et al., 2006).

For the biological activity of pyrazolopyrimidines, see: Carraro et al. (2006). For a related structure, see: Dolzhenko et al. (2009). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the intermolecular hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non participating in H-bonding were ommitted for clarity.

1-(2-Chloroethyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one top

Crystal data top

C₇H₇ClN₄O	F(000) = 416
M_r = 198.61	D_x = 1.565 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1548 reflections
a = 4.6448 (1) Å	θ = 1.8–25.2°
b = 8.0792 (1) Å	µ = 0.41 mm⁻¹
c = 22.7335 (4) Å	T = 296 K
β = 93.554 (1)°	Block, yellow
V = 851.46 (3) Å³	0.18 × 0.16 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD detector diffractometer	1548 independent reflections
Radiation source: fine-focus sealed tube	1353 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 25.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −5→5
T_min = 0.930, T_max = 0.937	k = −9→9
7660 measured reflections	l = −27→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 0.87	w = 1/[σ²(F_o²) + (0.0642P)² + 0.5291P] where P = (F_o² + 2F_c²)/3
1548 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₇H₇ClN₄O	V = 851.46 (3) Å³
M_r = 198.61	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.6448 (1) Å	µ = 0.41 mm⁻¹
b = 8.0792 (1) Å	T = 296 K
c = 22.7335 (4) Å	0.18 × 0.16 × 0.16 mm
β = 93.554 (1)°

Data collection top

Bruker SMART APEX CCD detector diffractometer	1548 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1353 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.937	R_int = 0.023
7660 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 0.87	Δρ_max = 0.19 e Å⁻³
1548 reflections	Δρ_min = −0.37 e Å⁻³
118 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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

	x	y	z	U_iso*/U_eq
Cl1	0.89765 (12)	0.64259 (8)	0.72864 (2)	0.0600 (2)
O1	0.5103 (3)	0.78930 (17)	0.99906 (6)	0.0516 (4)
N1	0.7733 (3)	0.95763 (18)	0.94256 (6)	0.0381 (4)
H1	0.7021	1.0429	0.9590	0.046*
N2	1.0887 (3)	0.86963 (19)	0.87124 (7)	0.0396 (4)
N3	1.0967 (3)	0.57267 (18)	0.86397 (6)	0.0376 (4)
N4	0.9763 (3)	0.43809 (19)	0.88974 (7)	0.0434 (4)
C5	0.9640 (4)	0.9842 (2)	0.90068 (8)	0.0401 (4)
H5A	1.0092	1.0935	0.8924	0.048*
C6	1.0057 (4)	0.7151 (2)	0.88711 (7)	0.0331 (4)
C1	1.2904 (4)	0.5504 (3)	0.81692 (8)	0.0418 (4)
H1A	1.4385	0.4711	0.8295	0.050*
H1B	1.3848	0.6548	0.8096	0.050*
C2	1.1398 (4)	0.4907 (2)	0.76054 (8)	0.0442 (5)
H2A	1.0330	0.3907	0.7683	0.053*
H2B	1.2826	0.4635	0.7327	0.053*
C4	0.6848 (4)	0.8026 (2)	0.96076 (7)	0.0371 (4)
C7	0.8174 (4)	0.6729 (2)	0.92974 (7)	0.0349 (4)
C3	0.8092 (4)	0.4993 (2)	0.92932 (8)	0.0424 (4)
H3	0.7002	0.4356	0.9538	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0545 (3)	0.0640 (4)	0.0607 (4)	0.0019 (2)	−0.0027 (3)	0.0011 (3)
O1	0.0692 (9)	0.0403 (8)	0.0488 (8)	−0.0011 (6)	0.0335 (7)	−0.0006 (6)
N1	0.0486 (8)	0.0314 (8)	0.0355 (8)	0.0000 (6)	0.0122 (6)	−0.0036 (6)
N2	0.0475 (9)	0.0357 (8)	0.0370 (8)	−0.0044 (7)	0.0137 (7)	−0.0006 (6)
N3	0.0437 (8)	0.0351 (8)	0.0354 (8)	0.0002 (6)	0.0121 (6)	−0.0014 (6)
N4	0.0550 (9)	0.0326 (8)	0.0436 (9)	0.0000 (7)	0.0117 (7)	0.0026 (7)
C5	0.0489 (10)	0.0352 (10)	0.0372 (9)	−0.0061 (8)	0.0098 (8)	0.0021 (8)
C6	0.0360 (9)	0.0343 (9)	0.0295 (8)	−0.0008 (7)	0.0060 (7)	−0.0005 (7)
C1	0.0397 (9)	0.0451 (11)	0.0418 (10)	0.0050 (8)	0.0132 (8)	−0.0037 (8)
C2	0.0505 (11)	0.0395 (11)	0.0442 (10)	0.0004 (8)	0.0159 (8)	−0.0060 (8)
C4	0.0452 (10)	0.0365 (10)	0.0304 (9)	−0.0030 (8)	0.0088 (7)	−0.0002 (7)
C7	0.0413 (9)	0.0347 (9)	0.0293 (8)	−0.0019 (7)	0.0076 (7)	0.0006 (7)
C3	0.0528 (11)	0.0364 (10)	0.0393 (10)	−0.0025 (8)	0.0141 (8)	0.0033 (8)

Geometric parameters (Å, º) top

Cl1—C2	1.788 (2)	C5—H5A	0.9300
O1—C4	1.231 (2)	C6—C7	1.388 (2)
N1—C5	1.357 (2)	C1—C2	1.501 (3)
N1—C4	1.389 (2)	C1—H1A	0.9700
N1—H1	0.8600	C1—H1B	0.9700
N2—C5	1.299 (2)	C2—H2A	0.9700
N2—C6	1.362 (2)	C2—H2B	0.9700
N3—C6	1.344 (2)	C4—C7	1.424 (2)
N3—N4	1.371 (2)	C7—C3	1.403 (3)
N3—C1	1.451 (2)	C3—H3	0.9300
N4—C3	1.320 (2)

C5—N1—C4	124.71 (15)	C2—C1—H1B	109.0
C5—N1—H1	117.6	H1A—C1—H1B	107.8
C4—N1—H1	117.6	C1—C2—Cl1	112.00 (14)
C5—N2—C6	111.97 (15)	C1—C2—H2A	109.2
C6—N3—N4	111.42 (13)	Cl1—C2—H2A	109.2
C6—N3—C1	128.26 (15)	C1—C2—H2B	109.2
N4—N3—C1	120.30 (15)	Cl1—C2—H2B	109.2
C3—N4—N3	105.48 (15)	H2A—C2—H2B	107.9
N2—C5—N1	125.45 (17)	O1—C4—N1	120.63 (16)
N2—C5—H5A	117.3	O1—C4—C7	127.58 (17)
N1—C5—H5A	117.3	N1—C4—C7	111.79 (14)
N3—C6—N2	125.45 (15)	C6—C7—C3	105.00 (16)
N3—C6—C7	106.86 (15)	C6—C7—C4	118.38 (16)
N2—C6—C7	127.68 (16)	C3—C7—C4	136.61 (17)
N3—C1—C2	113.08 (15)	N4—C3—C7	111.23 (16)
N3—C1—H1A	109.0	N4—C3—H3	124.4
C2—C1—H1A	109.0	C7—C3—H3	124.4
N3—C1—H1B	109.0

C6—N3—N4—C3	−0.1 (2)	C5—N1—C4—O1	−179.89 (18)
C1—N3—N4—C3	−178.72 (16)	C5—N1—C4—C7	−0.4 (2)
C6—N2—C5—N1	0.1 (3)	N3—C6—C7—C3	0.2 (2)
C4—N1—C5—N2	0.7 (3)	N2—C6—C7—C3	−179.13 (18)
N4—N3—C6—N2	179.28 (17)	N3—C6—C7—C4	−179.02 (15)
C1—N3—C6—N2	−2.2 (3)	N2—C6—C7—C4	1.6 (3)
N4—N3—C6—C7	−0.1 (2)	O1—C4—C7—C6	178.81 (19)
C1—N3—C6—C7	178.40 (17)	N1—C4—C7—C6	−0.6 (2)
C5—N2—C6—N3	179.47 (17)	O1—C4—C7—C3	−0.1 (4)
C5—N2—C6—C7	−1.3 (3)	N1—C4—C7—C3	−179.6 (2)
C6—N3—C1—C2	−108.1 (2)	N3—N4—C3—C7	0.2 (2)
N4—N3—C1—C2	70.3 (2)	C6—C7—C3—N4	−0.3 (2)
N3—C1—C2—Cl1	66.78 (19)	C4—C7—C3—N4	178.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	1.96	2.810 (2)	170
C5—H5A···N4ⁱⁱ	0.93	2.79	3.676 (2)	160
C2—H2A···Cl1ⁱⁱⁱ	0.97	2.84	3.779 (2)	164
C2—H2B···N2^iv	0.97	2.59	3.463 (2)	150
C3—H3···O1^v	0.93	2.35	3.254 (2)	163

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x, y+1, z; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+5/2, y−1/2, −z+3/2; (v) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₇H₇ClN₄O
M_r	198.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.6448 (1), 8.0792 (1), 22.7335 (4)
β (°)	93.554 (1)
V (Å³)	851.46 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.18 × 0.16 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.930, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	7660, 1548, 1353
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 0.87
No. of reflections	1548
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.37

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1996), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.860	1.958	2.810 (2)	170
C5—H5A···N4ⁱⁱ	0.930	2.789	3.676 (2)	160
C2—H2A···Cl1ⁱⁱⁱ	0.970	2.836	3.779 (2)	164
C2—H2B···N2^iv	0.970	2.587	3.463 (2)	150
C3—H3···O1^v	0.930	2.353	3.254 (2)	163

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x, y+1, z; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+5/2, y−1/2, −z+3/2; (v) −x+1, −y+1, −z+2.

Acknowledgements

IMK is thankful to the University Grants Commission (UGC), India, for financial assistance.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. 34, 1555–1573. CrossRef CAS Google Scholar
Bruker. (1998). SMART, SAINT-Plus and SADABS. Bruker Axs Inc., Madison, Wisconcin, USA. Google Scholar
Carraro, F., Naldini, A., Pucci, A., Locatelli, G. A., Maga, G., Schenone, S., Bruno, O., Ranise, A., Bondavalli, F., Brullo, C., Fossa, P., Menozzi, G., Mosti, L., Modugno, M., Tintori, C., Manetti, F. & Botta|, M. (2006). J. Med. Chem. 49, 1549–1561. Google Scholar
Dolzhenko, A. V., Pastorin, G., Dolzhenko, A. V., Tan, G. K. & Koh, L. L. (2009). Acta Cryst. E65, o1720–o1721. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar