Racemic N-methyl-4-[2-(methyl­sulfan­yl)­pyrimidin-4-yl]-1-(tetra­hydro­furan-3-yl)-1H-pyrazol-5-amine

Liu, Z.; Liu, K.K.-C.; Rheingold, A.L.; DiPasquale, A.; Yanovsky, A.

doi:10.1107/S1600536809014317

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1089

doi:10.1107/S1600536809014317

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Racemic N-methyl-4-[2-(methylsulfanyl)pyrimidin-4-yl]-1-(tetrahydrofuran-3-yl)-1H-pyrazol-5-amine

Zhengyu Liu,^a Kevin K.-C. Liu,^a Arnold L. Rheingold,^b Antonio DiPasquale ^b and Alex Yanovsky ^a ^*

^aPfizer Global Research and Development, La Jolla Laboratories, 10770 Science Center Drive, San Diego, CA 92121, USA, and ^bDepartment of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
^*Correspondence e-mail: alex.yanovsky@pfizer.com

(Received 14 April 2009; accepted 16 April 2009; online 22 April 2009)

The title compound, C₁₃H₁₇N₅OS, was obtained by cycloaddition of 2-[2-(methylsulfanyl)pyrimidin-4-yl]-3-oxopropanenitrile with (tetrahydrofuran-3-yl)hydrazine dihydrochloride and subsequent N-methylation of 4-[2-(methylsulfanyl)pyrimidin-4-yl]-1-(tetrahydrofuran-2-yl)-1H-pyrazol-5-amine with methyl iodide. The two molecules in the asymmetric unit have opposite absolute configurations and are related by a noncrystallographic inversion center. Both feature intramolecular N—H⋯N hydrogen bonds. The geometry of the molecules is similar to that observed in the structure of a single enantiomer of the title compound.

Related literature

For the structure of the R-enantiomer component of the racemic title compound, see: Liu et al. (2009a ). For details of the synthesis of the title compound, see: Liu et al. (2009a,b ).

Experimental

Crystal data

C₁₃H₁₇N₅OS
M_r = 291.38
Monoclinic, P 2₁ /n
a = 15.7404 (5) Å
b = 10.1515 (3) Å
c = 18.9644 (6) Å
β = 112.829 (1)°
V = 2792.92 (15) Å³
Z = 8
Cu Kα radiation
μ = 2.10 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker P4/APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.572, T_max = 0.679
18618 measured reflections
5007 independent reflections
4521 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.119
S = 1.05
5007 reflections
371 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N5	0.82 (2)	2.16 (2)	2.828 (2)	139 (2)
N8—H8N⋯N10	0.83 (2)	2.13 (2)	2.820 (2)	140 (2)

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-32 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014317/dn2448sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014317/dn2448Isup2.hkl

checkCIF report

Comment top

The title compound was obtained by cycloaddition of 2-(2-(methylsulfanyl)pyrimidin-4-yl)-3-oxopropanenitrile with (tetrahydrofuran-3-yl)hydrazine dihydrochloride and subsequent N-methylation of 4-(2-(methylsulfanyl)pyrimidin-4-yl) -1-(tetrahydrofuran-2-yl)-1H-pyrazol-5-amine with methyl iodide. As cycloaddition may potentially yield one of the two isomeric products differing in the position of the tetrahydrofuranyl substituent, present study was undertaken to establish which of the isomers is actually formed. The X-ray study showed that the product represents the title compound with amino and tetrahydrofuranyl substituents at the neighbouring atoms of the pyrazolyl ring.

There are two molecules in the asymmetric unit (Fig. 1). The molecules are chemically and conformationally identical, but have opposite absolute configurations; moreover, the structure provides an interesting case of almost precise, though non-crystallographic inversion symmetry. The local inversion center has approximate coordinates of -0.001, 0.134, 0.249. Such arrangement may be facilitated by the weak interactions between the H atoms of methyl groups C8 and C21 and the π-electron densities of pyrazolyl rings N6-N7-C18-C19-C20 and N1-N2-C5-C6-C7 respectively: the distances between the methyl C atoms and the centroids of the corresponding rings are 3.520 Å and 3.589 Å.

The geometry of the molecules is very similar to that observed in the structure of single enantiomer obtained by chiral separation of the title compound (Liu et al., 2009a). The methylsulfanylpyrimidine group and pyrazolyl ring lie approximately in one plane; maximum deviations of the C10 and C18 atoms in each of the two molecules are 0.033 (2) Å and 0.037 (2) Å respectively; displacements of methyl C8 and C21 atoms are 0.967 (2) Å and 1.020 (2) Å. Orientation of the tetrahydrofuran ring can be characterized by the dihedral angles 75.6 (1)° and 77.8 (1) formed by the pyrimidine-pyrazolyl planes with the C2-C3-C4 and C15-C16-C17 planes in each of the two molecules respectively.

The secondary amino groups in both molecules (N3 and N8) form intramolecular H-bonds with the N atoms of the pyrimidine rings (N5 and N10 respectively; Table 2).

Related literature top

For the structure of the R-enantiomer component of the racemic title compound, see: Liu et al. (2009a). For details of the synthesis of the title compound, see: Liu et al. (2009a,b).

Experimental top

The detailed descriptions of the synthesis of the title compound are given in Liu et al. (2009a) and Liu et al. (2009b).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Two independent molecules in the structure of the title compound with the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level; H atoms are represented as circles with arbitrary small radius.

Racemic N-methyl-4-[2-(methylsulfanyl)pyrimidin-4-yl]- 1-(tetrahydrofuran-3-yl)-1H-pyrazol-5-amine top

Crystal data top

C₁₃H₁₇N₅OS	F(000) = 1232
M_r = 291.38	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 1033 reflections
a = 15.7404 (5) Å	θ = 4.9–54.9°
b = 10.1515 (3) Å	µ = 2.10 mm⁻¹
c = 18.9644 (6) Å	T = 100 K
β = 112.829 (1)°	Block, colorless
V = 2792.92 (15) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Bruker P4/APEX CCD diffractometer	5007 independent reflections
Radiation source: fine-focus sealed tube	4521 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 68.6°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −18→18
T_min = 0.572, T_max = 0.679	k = −11→12
18618 measured reflections	l = −22→21

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0596P)² + 1.859P] where P = (F_o² + 2F_c²)/3
5007 reflections	(Δ/σ)_max = 0.001
371 parameters	Δρ_max = 0.88 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₃H₁₇N₅OS	V = 2792.92 (15) Å³
M_r = 291.38	Z = 8
Monoclinic, P2₁/n	Cu Kα radiation
a = 15.7404 (5) Å	µ = 2.10 mm⁻¹
b = 10.1515 (3) Å	T = 100 K
c = 18.9644 (6) Å	0.30 × 0.20 × 0.20 mm
β = 112.829 (1)°

Data collection top

Bruker P4/APEX CCD diffractometer	5007 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4521 reflections with I > 2σ(I)
T_min = 0.572, T_max = 0.679	R_int = 0.030
18618 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.88 e Å⁻³
5007 reflections	Δρ_min = −0.32 e Å⁻³
371 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	0.22461 (16)	−0.1765 (2)	0.31756 (13)	0.0393 (5)
H1A	0.1969	−0.2521	0.2834	0.047*
H1B	0.2861	−0.1583	0.3170	0.047*
C2	0.16265 (14)	−0.0551 (2)	0.29178 (11)	0.0310 (4)
H2A	0.0969	−0.0805	0.2670	0.037*
H2B	0.1794	−0.0008	0.2558	0.037*
C3	0.18197 (12)	0.01907 (18)	0.36747 (10)	0.0213 (4)
H3	0.2191	0.0998	0.3691	0.026*
C4	0.24143 (13)	−0.07910 (18)	0.42835 (11)	0.0249 (4)
H4A	0.3068	−0.0511	0.4489	0.030*
H4B	0.2204	−0.0836	0.4712	0.030*
C5	−0.01506 (12)	0.02935 (18)	0.41206 (10)	0.0208 (4)
H5	−0.0595	−0.0101	0.4279	0.025*
C6	−0.01006 (12)	0.16645 (17)	0.40075 (10)	0.0199 (4)
C7	0.06411 (12)	0.17913 (17)	0.37729 (10)	0.0196 (4)
C8	0.11656 (13)	0.29925 (19)	0.28860 (11)	0.0263 (4)
H8A	0.1802	0.2726	0.2992	0.039*
H8B	0.1069	0.3899	0.2693	0.039*
H8C	0.0740	0.2402	0.2501	0.039*
C9	−0.06565 (12)	0.27261 (18)	0.41090 (10)	0.0203 (4)
C10	−0.13890 (13)	0.25167 (19)	0.43403 (11)	0.0256 (4)
H10	−0.1566	0.1654	0.4423	0.031*
C11	−0.18401 (13)	0.3611 (2)	0.44425 (11)	0.0289 (4)
H11	−0.2330	0.3485	0.4611	0.035*
C12	−0.09392 (12)	0.49396 (18)	0.40780 (10)	0.0231 (4)
C13	0.02328 (15)	0.6340 (2)	0.35791 (13)	0.0331 (5)
H13A	0.0731	0.5852	0.3971	0.050*
H13B	0.0462	0.7201	0.3499	0.050*
H13C	0.0015	0.5842	0.3099	0.050*
C14	−0.23088 (16)	0.4429 (2)	0.17690 (13)	0.0387 (5)
H14A	−0.2920	0.4220	0.1775	0.046*
H14B	−0.2054	0.5207	0.2098	0.046*
C15	−0.16593 (14)	0.3254 (2)	0.20499 (11)	0.0324 (5)
H15A	−0.1816	0.2714	0.2417	0.039*
H15B	−0.1009	0.3544	0.2295	0.039*
C16	−0.18296 (12)	0.24857 (18)	0.13061 (10)	0.0220 (4)
H16	−0.2189	0.1669	0.1297	0.026*
C17	−0.24264 (13)	0.34274 (19)	0.06774 (11)	0.0271 (4)
H17A	−0.2190	0.3484	0.0265	0.033*
H17B	−0.3071	0.3110	0.0454	0.033*
C18	0.01589 (12)	0.24134 (17)	0.08857 (10)	0.0204 (4)
H18	0.0601	0.2813	0.0726	0.025*
C19	0.01176 (12)	0.10435 (17)	0.10037 (10)	0.0191 (4)
C20	−0.06290 (12)	0.09089 (17)	0.12278 (9)	0.0188 (3)
C21	−0.11957 (13)	−0.03136 (19)	0.20869 (11)	0.0262 (4)
H21A	−0.0808	0.0312	0.2471	0.039*
H21B	−0.1069	−0.1210	0.2293	0.039*
H21C	−0.1847	−0.0103	0.1958	0.039*
C22	0.06828 (11)	−0.00076 (18)	0.09110 (9)	0.0193 (4)
C23	0.14461 (12)	0.02003 (18)	0.07200 (10)	0.0224 (4)
H23	0.1631	0.1063	0.0646	0.027*
C24	0.19188 (12)	−0.08969 (19)	0.06428 (11)	0.0247 (4)
H24	0.2430	−0.0772	0.0502	0.030*
C25	0.09580 (12)	−0.22284 (18)	0.09390 (10)	0.0216 (4)
C26	−0.03578 (16)	−0.3636 (2)	0.12571 (14)	0.0366 (5)
H26A	−0.0215	−0.3133	0.1730	0.055*
H26B	−0.0608	−0.4498	0.1308	0.055*
H26C	−0.0814	−0.3155	0.0829	0.055*
N1	0.09784 (10)	0.05689 (15)	0.37756 (8)	0.0199 (3)
N2	0.04867 (10)	−0.03777 (15)	0.39826 (8)	0.0217 (3)
N3	0.09942 (11)	0.29183 (15)	0.35925 (9)	0.0220 (3)
N4	−0.16316 (11)	0.48479 (16)	0.43195 (10)	0.0283 (4)
N5	−0.04410 (10)	0.39615 (15)	0.39708 (8)	0.0212 (3)
N6	−0.09717 (10)	0.21269 (14)	0.12244 (8)	0.0197 (3)
N7	−0.04837 (10)	0.30785 (14)	0.10218 (8)	0.0215 (3)
N8	−0.09920 (11)	−0.02230 (15)	0.13985 (9)	0.0215 (3)
N9	0.16958 (10)	−0.21327 (16)	0.07561 (9)	0.0249 (3)
N10	0.04399 (10)	−0.12520 (15)	0.10180 (8)	0.0200 (3)
O1	0.23183 (11)	−0.20351 (14)	0.39248 (9)	0.0365 (4)
O2	−0.23835 (12)	0.46761 (15)	0.10208 (9)	0.0398 (4)
S1	−0.07026 (3)	0.65654 (5)	0.38885 (3)	0.02884 (14)
S2	0.06756 (3)	−0.38593 (4)	0.10801 (3)	0.02817 (14)
H3N	0.0715 (16)	0.355 (2)	0.3657 (13)	0.034*
H8N	−0.0682 (16)	−0.085 (2)	0.1349 (13)	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0401 (12)	0.0408 (13)	0.0374 (12)	0.0094 (10)	0.0153 (9)	−0.0107 (10)
C2	0.0277 (10)	0.0418 (12)	0.0246 (10)	0.0030 (9)	0.0113 (8)	−0.0049 (8)
C3	0.0195 (8)	0.0206 (9)	0.0254 (9)	0.0011 (7)	0.0106 (7)	0.0006 (7)
C4	0.0231 (9)	0.0236 (9)	0.0296 (10)	0.0047 (7)	0.0120 (8)	0.0033 (7)
C5	0.0199 (8)	0.0209 (9)	0.0222 (9)	−0.0021 (7)	0.0087 (7)	0.0011 (7)
C6	0.0193 (8)	0.0195 (9)	0.0207 (8)	−0.0008 (7)	0.0075 (7)	0.0006 (7)
C7	0.0184 (8)	0.0184 (8)	0.0209 (8)	−0.0011 (7)	0.0063 (7)	−0.0005 (7)
C8	0.0240 (9)	0.0270 (10)	0.0272 (9)	0.0014 (8)	0.0091 (7)	0.0066 (8)
C9	0.0183 (8)	0.0200 (9)	0.0205 (8)	0.0001 (7)	0.0054 (7)	0.0005 (7)
C10	0.0228 (9)	0.0240 (10)	0.0313 (10)	−0.0004 (7)	0.0120 (8)	0.0028 (7)
C11	0.0230 (9)	0.0306 (10)	0.0366 (11)	0.0020 (8)	0.0153 (8)	0.0025 (8)
C12	0.0199 (8)	0.0225 (9)	0.0239 (9)	0.0006 (7)	0.0051 (7)	−0.0018 (7)
C13	0.0408 (11)	0.0218 (10)	0.0438 (12)	−0.0044 (8)	0.0242 (10)	−0.0009 (8)
C14	0.0423 (12)	0.0363 (12)	0.0386 (12)	0.0071 (10)	0.0168 (10)	−0.0073 (9)
C15	0.0290 (10)	0.0423 (12)	0.0265 (10)	0.0078 (9)	0.0114 (8)	−0.0052 (9)
C16	0.0209 (8)	0.0214 (9)	0.0257 (9)	0.0022 (7)	0.0113 (7)	0.0010 (7)
C17	0.0253 (9)	0.0277 (10)	0.0298 (10)	0.0070 (8)	0.0123 (8)	0.0044 (8)
C18	0.0207 (8)	0.0178 (9)	0.0235 (9)	−0.0015 (7)	0.0092 (7)	−0.0009 (7)
C19	0.0191 (8)	0.0180 (9)	0.0195 (8)	−0.0013 (7)	0.0066 (7)	−0.0007 (6)
C20	0.0195 (8)	0.0166 (8)	0.0188 (8)	−0.0008 (7)	0.0057 (6)	−0.0006 (6)
C21	0.0281 (9)	0.0249 (10)	0.0263 (9)	0.0018 (8)	0.0112 (8)	0.0062 (7)
C22	0.0177 (8)	0.0204 (9)	0.0172 (8)	−0.0002 (7)	0.0040 (6)	−0.0005 (6)
C23	0.0201 (8)	0.0209 (9)	0.0252 (9)	−0.0019 (7)	0.0078 (7)	0.0000 (7)
C24	0.0174 (8)	0.0267 (10)	0.0295 (10)	0.0019 (7)	0.0084 (7)	−0.0005 (7)
C25	0.0213 (8)	0.0195 (9)	0.0217 (9)	0.0019 (7)	0.0057 (7)	−0.0009 (7)
C26	0.0449 (12)	0.0194 (10)	0.0575 (14)	−0.0029 (9)	0.0329 (11)	0.0000 (9)
N1	0.0189 (7)	0.0181 (7)	0.0243 (7)	−0.0004 (6)	0.0102 (6)	0.0012 (6)
N2	0.0231 (7)	0.0177 (7)	0.0251 (8)	−0.0026 (6)	0.0101 (6)	0.0021 (6)
N3	0.0229 (8)	0.0170 (7)	0.0292 (8)	−0.0001 (6)	0.0134 (6)	0.0018 (6)
N4	0.0225 (8)	0.0264 (9)	0.0378 (9)	0.0030 (6)	0.0136 (7)	−0.0009 (7)
N5	0.0189 (7)	0.0209 (8)	0.0217 (7)	−0.0006 (6)	0.0058 (6)	−0.0010 (6)
N6	0.0205 (7)	0.0166 (7)	0.0235 (7)	0.0006 (6)	0.0101 (6)	0.0010 (6)
N7	0.0225 (7)	0.0172 (7)	0.0251 (8)	−0.0016 (6)	0.0098 (6)	0.0006 (6)
N8	0.0235 (8)	0.0160 (7)	0.0282 (8)	0.0016 (6)	0.0136 (6)	0.0020 (6)
N9	0.0192 (7)	0.0231 (8)	0.0311 (8)	0.0031 (6)	0.0085 (6)	−0.0017 (6)
N10	0.0201 (7)	0.0180 (7)	0.0204 (7)	−0.0002 (6)	0.0063 (6)	−0.0011 (6)
O1	0.0445 (9)	0.0246 (7)	0.0426 (8)	0.0084 (6)	0.0194 (7)	−0.0002 (6)
O2	0.0538 (10)	0.0272 (8)	0.0448 (9)	0.0133 (7)	0.0260 (8)	0.0044 (6)
S1	0.0310 (3)	0.0180 (2)	0.0391 (3)	0.00095 (18)	0.0152 (2)	−0.00141 (18)
S2	0.0329 (3)	0.0160 (2)	0.0385 (3)	0.00297 (18)	0.0170 (2)	0.00048 (18)

Geometric parameters (Å, º) top

C1—O1	1.408 (3)	C14—H14A	0.9900
C1—C2	1.529 (3)	C14—H14B	0.9900
C1—H1A	0.9900	C15—C16	1.541 (3)
C1—H1B	0.9900	C15—H15A	0.9900
C2—C3	1.543 (2)	C15—H15B	0.9900
C2—H2A	0.9900	C16—N6	1.464 (2)
C2—H2B	0.9900	C16—C17	1.533 (2)
C3—N1	1.461 (2)	C16—H16	1.0000
C3—C4	1.537 (2)	C17—O2	1.415 (2)
C3—H3	1.0000	C17—H17A	0.9900
C4—O1	1.415 (2)	C17—H17B	0.9900
C4—H4A	0.9900	C18—N7	1.322 (2)
C4—H4B	0.9900	C18—C19	1.414 (2)
C5—N2	1.320 (2)	C18—H18	0.9500
C5—C6	1.415 (2)	C19—C20	1.403 (2)
C5—H5	0.9500	C19—C22	1.443 (2)
C6—C7	1.407 (2)	C20—N6	1.348 (2)
C6—C9	1.447 (2)	C20—N8	1.377 (2)
C7—N1	1.349 (2)	C21—N8	1.463 (2)
C7—N3	1.372 (2)	C21—H21A	0.9800
C8—N3	1.468 (2)	C21—H21B	0.9800
C8—H8A	0.9800	C21—H21C	0.9800
C8—H8B	0.9800	C22—N10	1.358 (2)
C8—H8C	0.9800	C22—C23	1.399 (2)
C9—N5	1.351 (2)	C23—C24	1.378 (3)
C9—C10	1.400 (2)	C23—H23	0.9500
C10—C11	1.372 (3)	C24—N9	1.342 (2)
C10—H10	0.9500	C24—H24	0.9500
C11—N4	1.341 (3)	C25—N10	1.328 (2)
C11—H11	0.9500	C25—N9	1.338 (2)
C12—N5	1.329 (2)	C25—S2	1.7614 (19)
C12—N4	1.339 (2)	C26—S2	1.798 (2)
C12—S1	1.7594 (19)	C26—H26A	0.9800
C13—S1	1.799 (2)	C26—H26B	0.9800
C13—H13A	0.9800	C26—H26C	0.9800
C13—H13B	0.9800	N1—N2	1.383 (2)
C13—H13C	0.9800	N3—H3N	0.82 (2)
C14—O2	1.400 (3)	N6—N7	1.378 (2)
C14—C15	1.526 (3)	N8—H8N	0.83 (2)

O1—C1—C2	105.75 (16)	H15A—C15—H15B	109.1
O1—C1—H1A	110.6	N6—C16—C17	112.64 (14)
C2—C1—H1A	110.6	N6—C16—C15	112.50 (15)
O1—C1—H1B	110.6	C17—C16—C15	103.46 (15)
C2—C1—H1B	110.6	N6—C16—H16	109.4
H1A—C1—H1B	108.7	C17—C16—H16	109.4
C1—C2—C3	102.99 (15)	C15—C16—H16	109.4
C1—C2—H2A	111.2	O2—C17—C16	107.18 (15)
C3—C2—H2A	111.2	O2—C17—H17A	110.3
C1—C2—H2B	111.2	C16—C17—H17A	110.3
C3—C2—H2B	111.2	O2—C17—H17B	110.3
H2A—C2—H2B	109.1	C16—C17—H17B	110.3
N1—C3—C4	112.99 (14)	H17A—C17—H17B	108.5
N1—C3—C2	112.86 (14)	N7—C18—C19	112.69 (16)
C4—C3—C2	103.01 (15)	N7—C18—H18	123.7
N1—C3—H3	109.3	C19—C18—H18	123.7
C4—C3—H3	109.3	C20—C19—C18	103.83 (15)
C2—C3—H3	109.3	C20—C19—C22	126.39 (16)
O1—C4—C3	107.29 (15)	C18—C19—C22	129.77 (16)
O1—C4—H4A	110.3	N6—C20—N8	124.39 (16)
C3—C4—H4A	110.3	N6—C20—C19	106.85 (15)
O1—C4—H4B	110.3	N8—C20—C19	128.72 (16)
C3—C4—H4B	110.3	N8—C21—H21A	109.5
H4A—C4—H4B	108.5	N8—C21—H21B	109.5
N2—C5—C6	112.72 (15)	H21A—C21—H21B	109.5
N2—C5—H5	123.6	N8—C21—H21C	109.5
C6—C5—H5	123.6	H21A—C21—H21C	109.5
C7—C6—C5	103.87 (15)	H21B—C21—H21C	109.5
C7—C6—C9	126.33 (16)	N10—C22—C23	119.94 (16)
C5—C6—C9	129.80 (16)	N10—C22—C19	116.56 (15)
N1—C7—N3	124.83 (16)	C23—C22—C19	123.50 (16)
N1—C7—C6	106.75 (15)	C24—C23—C22	117.31 (17)
N3—C7—C6	128.40 (16)	C24—C23—H23	121.3
N3—C8—H8A	109.5	C22—C23—H23	121.3
N3—C8—H8B	109.5	N9—C24—C23	123.55 (17)
H8A—C8—H8B	109.5	N9—C24—H24	118.2
N3—C8—H8C	109.5	C23—C24—H24	118.2
H8A—C8—H8C	109.5	N10—C25—N9	127.40 (17)
H8B—C8—H8C	109.5	N10—C25—S2	118.83 (14)
N5—C9—C10	120.07 (16)	N9—C25—S2	113.77 (13)
N5—C9—C6	117.08 (15)	S2—C26—H26A	109.5
C10—C9—C6	122.86 (16)	S2—C26—H26B	109.5
C11—C10—C9	117.09 (17)	H26A—C26—H26B	109.5
C11—C10—H10	121.5	S2—C26—H26C	109.5
C9—C10—H10	121.5	H26A—C26—H26C	109.5
N4—C11—C10	123.96 (17)	H26B—C26—H26C	109.5
N4—C11—H11	118.0	C7—N1—N2	112.18 (14)
C10—C11—H11	118.0	C7—N1—C3	128.07 (15)
N5—C12—N4	127.39 (18)	N2—N1—C3	119.35 (14)
N5—C12—S1	119.05 (14)	C5—N2—N1	104.46 (14)
N4—C12—S1	113.57 (14)	C7—N3—C8	120.42 (15)
S1—C13—H13A	109.5	C7—N3—H3N	109.2 (17)
S1—C13—H13B	109.5	C8—N3—H3N	113.3 (17)
H13A—C13—H13B	109.5	C12—N4—C11	114.28 (16)
S1—C13—H13C	109.5	C12—N5—C9	117.16 (16)
H13A—C13—H13C	109.5	C20—N6—N7	112.26 (14)
H13B—C13—H13C	109.5	C20—N6—C16	127.71 (15)
O2—C14—C15	105.96 (16)	N7—N6—C16	119.47 (14)
O2—C14—H14A	110.5	C18—N7—N6	104.35 (14)
C15—C14—H14A	110.5	C20—N8—C21	121.13 (15)
O2—C14—H14B	110.5	C20—N8—H8N	107.4 (17)
C15—C14—H14B	110.5	C21—N8—H8N	113.2 (16)
H14A—C14—H14B	108.7	C25—N9—C24	114.62 (16)
C14—C15—C16	102.77 (16)	C25—N10—C22	117.17 (15)
C14—C15—H15A	111.2	C1—O1—C4	105.24 (15)
C16—C15—H15A	111.2	C14—O2—C17	106.04 (16)
C14—C15—H15B	111.2	C12—S1—C13	102.24 (9)
C16—C15—H15B	111.2	C25—S2—C26	102.10 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N5	0.82 (2)	2.16 (2)	2.828 (2)	139 (2)
N8—H8N···N10	0.83 (2)	2.13 (2)	2.820 (2)	140 (2)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₇N₅OS
M_r	291.38
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	15.7404 (5), 10.1515 (3), 18.9644 (6)
β (°)	112.829 (1)
V (Å³)	2792.92 (15)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.10
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker P4/APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.572, 0.679
No. of measured, independent and observed [I > 2σ(I)] reflections	18618, 5007, 4521
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.119, 1.05
No. of reflections	5007
No. of parameters	371
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-32 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N5	0.82 (2)	2.16 (2)	2.828 (2)	139 (2)
N8—H8N···N10	0.83 (2)	2.13 (2)	2.820 (2)	140 (2)

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. 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
Liu, Z., Liu, K. K.-C., Elleraas, J., Rheingold, A. L., DiPasquale, A. & Yanovsky, A. (2009a). Acta Cryst. E65, o616. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, Z., Liu, K. K.-C., Elleraas, J., Rheingold, A. L., DiPasquale, A. & Yanovsky, A. (2009b). Acta Cryst. E65, o697. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Racemic N-methyl-4-[2-(methyl­sulfan­yl)­pyrimidin-4-yl]-1-(tetra­hydro­furan-3-yl)-1H-pyrazol-5-amine

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organic compounds

Racemic N-methyl-4-[2-(methylsulfanyl)pyrimidin-4-yl]-1-(tetrahydrofuran-3-yl)-1H-pyrazol-5-amine