Crystal structure of 1-methyl-4-methyl­sulfanyl-1H-pyrazolo­[3,4-d]pyrimidine

El Fal, M.; Ramli, Y.; Essassi, E.M.; Saadi, M.; El Ammari, L.

doi:10.1107/S1600536814025239

organic compounds

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Volume 70| Part 12| December 2014| Page o1281

doi:10.1107/S1600536814025239

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Crystal structure of 1-methyl-4-methylsulfanyl-1H-pyrazolo[3,4-d]pyrimidine

Mohammed El Fal,^a ^* Youssef Ramli,^b El Mokhtar Essassi,^a Mohamed Saadi ^c and Lahcen El Ammari ^c

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétences Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bMedicinal Chemistry Laboratory, Faculty of Medicine and Pharmacy, Mohammed V University, Rabat, Morocco, and ^cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: elfal_mohammed@yahoo.fr

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 15 November 2014; accepted 17 November 2014; online 21 November 2014)

In the title compound, C₇H₈N₄S, the non-H atoms of the pyrazolo[3,4-d]pyrimidine ring system and the methylsulfanyl group lie on a crystallographic mirror plane. In the crystal, molecules are linked via a number of π–π interactions [centroid–centroid distances vary from 3.452 (7) to 3.6062 (8) Å], forming a three-dimensional structure.

Keywords: crystal structure; 1H-pyrazolo[3,4-d]pyrimidine; pharmacological and biochemical properties; π–π interactions.

CCDC reference: 1034638

1. Related literature

For similar compounds, see: El Fal et al. (2013 , 2014a ,b ); Ouzidan et al. (2011 ). For pharmacological and biochemical properties of pyrazolo[3,4-d]pyrimidine-4(5H)-thione derivatives, see: Chauhan & Kumar (2013 ); Venkatesan et al. (2014 ); Rashad et al. (2011 ).

2. Experimental

2.1. Crystal data

C₇H₈N₄S
M_r = 180.23
Orthorhombic, P b c m
a = 7.9309 (14) Å
b = 15.335 (3) Å
c = 6.7158 (12) Å
V = 816.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 296 K
0.37 × 0.28 × 0.19 mm

2.2. Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.637, T_max = 0.746
2970 measured reflections
1227 independent reflections
1017 reflections with I > 2σ(I)
R_int = 0.017

2.3. Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.129
S = 1.09
1227 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1034638

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814025239/tk5348sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814025239/tk5348Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814025239/tk5348Isup3.cml

checkCIF report

Structural commentary top

Synthesis of 1H-pyrazolo [3,4-d] pyrimidine-4-thiol derivatives has received considerable attention due to their biological activity especially as antimicrobial (Chauhan et al., 2013), antitubercular (Venkatesan et al., 2014) and anticancer (Rashad et al., 2011) agents. During the search for new antibacterial agents synthesis, some 1H-pyrazolo[3,4-d] pyrimidine-4-thiol derivatives were prepared (El Fal et al., 2013, 2014a, 2014b; Ouzidan et al., 2011). These compounds are currently under investigation for possible biological activity.

The molecule of the title compound is build up from two fused five- and six-membered rings linked to methylsulfanyl group. All non hydrogen atoms of the molecule are coplanar as shown in Fig. 1. In the crystal, the molecules are linked together by a number of π–π interactions [centroid–centroid distances vary from 3.452 (7) to 3.6062 (8) Å], forming a three-dimensional structure.

Synthesis and crystallization top

To a solution of 1H-pyrazolo [3,4-d] pyrimidine-4-thiol (0.5 g, 3.28 mmol) dissolved in DMF (20 ml) was added iodomethane (0.43 ml, 6.62 mmol), potassium carbonate (0.93 g, 7.1 mmol) and a catalytic amount of tetra-n-butylammonium bromide (0.1 g, 0.4 mmol). The mixture was stirred for 48 h and monitored by thin layer chromatography. The mixture was filtered and the solvent was removed in vacuo. The solid obtained was crystallized from ethanol to give the title compound as orange crystals (yield: 65%).

Refinement top

The H atoms were located in a difference map and treated as riding with C—H = 0.93 Å (aromatic) and C—H = 0.96 Å (methyl), and with U_iso(H) = 1.2 U_eq (aromatic) and U_iso(H) = 1.5 U_eq (methyl).

Related literature top

For similar compounds, see: El Fal et al. (2013, 2014a,b); Ouzidan et al. (2011). For pharmacological and biochemical properties of pyrazolo[3,4-d]pyrimidine-4(5H)-thione derivatives, see: Chauhan & Kumar (2013); Venkatesan et al. (2014); Rashad et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

1-Methyl-4-methylsulfanyl-1H-pyrazolo[3,4-d]pyrimidine top

Crystal data top

C₇H₈N₄S	F(000) = 376
M_r = 180.23	D_x = 1.466 Mg m⁻³
Orthorhombic, Pbcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2c 2b	Cell parameters from 1227 reflections
a = 7.9309 (14) Å	θ = 2.6–29.6°
b = 15.335 (3) Å	µ = 0.34 mm⁻¹
c = 6.7158 (12) Å	T = 296 K
V = 816.8 (3) Å³	Block, orange
Z = 4	0.37 × 0.28 × 0.19 mm

Data collection top

Bruker X8 APEX diffractometer	1227 independent reflections
Radiation source: fine-focus sealed tube	1017 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 29.6°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→4
T_min = 0.637, T_max = 0.746	k = −21→19
2970 measured reflections	l = −3→9

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0694P)² + 0.3181P] where P = (F_o² + 2F_c²)/3
1227 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₈N₄S	V = 816.8 (3) Å³
M_r = 180.23	Z = 4
Orthorhombic, Pbcm	Mo Kα radiation
a = 7.9309 (14) Å	µ = 0.34 mm⁻¹
b = 15.335 (3) Å	T = 296 K
c = 6.7158 (12) Å	0.37 × 0.28 × 0.19 mm

Data collection top

Bruker X8 APEX diffractometer	1227 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1017 reflections with I > 2σ(I)
T_min = 0.637, T_max = 0.746	R_int = 0.017
2970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.09	Δρ_max = 0.44 e Å⁻³
1227 reflections	Δρ_min = −0.29 e Å⁻³
73 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.5519 (3)	0.06804 (13)	0.2500	0.0393 (5)
H1	0.4928	0.0156	0.2500	0.047*
C2	0.5516 (3)	0.21199 (12)	0.2500	0.0279 (4)
C3	0.7675 (3)	0.30515 (13)	0.2500	0.0322 (4)
H3	0.8763	0.3277	0.2500	0.039*
C4	0.7284 (2)	0.21512 (11)	0.2500	0.0264 (4)
C5	0.8115 (3)	0.13396 (11)	0.2500	0.0285 (4)
C6	0.3247 (3)	0.32714 (15)	0.2500	0.0450 (6)
H6A	0.3121	0.3658	0.1386	0.068*
H6B	0.2414	0.2818	0.2500	0.068*
C7	1.0858 (3)	0.02097 (16)	0.2500	0.0483 (6)
H7A	0.9865	−0.0148	0.2500	0.072*
H7B	1.1499	0.0095	0.1316	0.072*
N1	0.7221 (2)	0.06053 (10)	0.2500	0.0348 (4)
N2	0.4577 (2)	0.13910 (11)	0.2500	0.0369 (4)
N3	0.4970 (2)	0.29563 (11)	0.2500	0.0323 (4)
N4	0.6289 (3)	0.35277 (10)	0.2500	0.0349 (4)
S1	1.03110 (7)	0.13414 (4)	0.2500	0.0447 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0316 (10)	0.0218 (9)	0.0644 (15)	−0.0024 (7)	0.000	0.000
C2	0.0294 (9)	0.0221 (8)	0.0321 (9)	0.0016 (7)	0.000	0.000
C3	0.0301 (10)	0.0230 (8)	0.0434 (11)	−0.0032 (7)	0.000	0.000
C4	0.0280 (9)	0.0216 (8)	0.0295 (9)	−0.0008 (6)	0.000	0.000
C5	0.0295 (9)	0.0232 (9)	0.0329 (9)	0.0005 (7)	0.000	0.000
C6	0.0329 (11)	0.0330 (11)	0.0692 (16)	0.0095 (9)	0.000	0.000
C7	0.0376 (12)	0.0393 (12)	0.0680 (17)	0.0119 (10)	0.000	0.000
N1	0.0307 (9)	0.0199 (7)	0.0536 (11)	0.0005 (6)	0.000	0.000
N2	0.0290 (9)	0.0250 (9)	0.0568 (12)	−0.0015 (6)	0.000	0.000
N3	0.0318 (8)	0.0221 (7)	0.0429 (9)	0.0024 (6)	0.000	0.000
N4	0.0399 (10)	0.0211 (7)	0.0439 (10)	−0.0021 (6)	0.000	0.000
S1	0.0264 (3)	0.0316 (3)	0.0761 (5)	0.00110 (18)	0.000	0.000

Geometric parameters (Å, º) top

C1—N2	1.321 (3)	C5—N1	1.331 (2)
C1—N1	1.355 (3)	C5—S1	1.741 (2)
C1—H1	0.9300	C6—N3	1.449 (3)
C2—N2	1.343 (3)	C6—H6A	0.9598
C2—N3	1.354 (2)	C6—H6B	0.9599
C2—C4	1.403 (3)	C7—S1	1.789 (3)
C3—N4	1.319 (3)	C7—H7A	0.9600
C3—C4	1.415 (2)	C7—H7B	0.9599
C3—H3	0.9300	N3—N4	1.365 (3)
C4—C5	1.408 (2)

N2—C1—N1	129.3 (2)	C4—C5—S1	117.82 (14)
N2—C1—H1	115.3	N3—C6—H6A	107.7
N1—C1—H1	115.3	N3—C6—H6B	114.1
N2—C2—N3	127.68 (18)	H6A—C6—H6B	112.1
N2—C2—C4	125.63 (18)	S1—C7—H7A	110.8
N3—C2—C4	106.69 (17)	S1—C7—H7B	107.8
N4—C3—C4	110.97 (17)	H7A—C7—H7B	109.3
N4—C3—H3	124.5	C5—N1—C1	117.33 (17)
C4—C3—H3	124.5	C1—N2—C2	111.89 (18)
C2—C4—C5	115.96 (17)	C2—N3—N4	111.29 (17)
C2—C4—C3	104.60 (16)	C2—N3—C6	128.13 (19)
C5—C4—C3	139.45 (19)	N4—N3—C6	120.59 (17)
N1—C5—C4	119.88 (19)	C3—N4—N3	106.45 (16)
N1—C5—S1	122.30 (14)	C5—S1—C7	103.95 (11)

Experimental details

Crystal data
Chemical formula	C₇H₈N₄S
M_r	180.23
Crystal system, space group	Orthorhombic, Pbcm
Temperature (K)	296
a, b, c (Å)	7.9309 (14), 15.335 (3), 6.7158 (12)
V (Å³)	816.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.37 × 0.28 × 0.19

Data collection
Diffractometer	Bruker X8 APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.637, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	2970, 1227, 1017
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.694

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.129, 1.09
No. of reflections	1227
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.29

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chauhan, M. & Kumar, R. (2013). Bioorg. Med. Chem. 21, 5657–5668. Web of Science CrossRef CAS PubMed Google Scholar
El Fal, M., Ramli, Y., Essassi, E. M., Saadi, M. & El Ammari, L. (2013). Acta Cryst. E69, o1650. CSD CrossRef IUCr Journals Google Scholar
El Fal, M., Ramli, Y., Essassi, E. M., Saadi, M. & El Ammari, L. (2014a). Acta Cryst. E70, o1005–o1006. CSD CrossRef IUCr Journals Google Scholar
El Fal, M., Ramli, Y., Essassi, E. M., Saadi, M. & El Ammari, L. (2014b). Acta Cryst. E70, o1038. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ouzidan, Y., Essassi, E. M., Luis, S. V., Bolte, M. & El Ammari, L. (2011). Acta Cryst. E67, o1822. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rashad, A. E., Mahmoud, A. E. & Ali, M. M. (2011). Eur. J. Med. Chem. 46, 1019–1026. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Venkatesan, G., Paira, P., Cheong, S. L., Vamsikrishna, K., Federico, S., Klotz, K., Spalluto, G. & Pastorin, G. (2014). Bioorg. Med. Chem. 22, 1751–1765. Web of Science CSD CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 12| December 2014| Page o1281

doi:10.1107/S1600536814025239

Open

access