5,6-Dimethyl-4-(thio-phen-2-yl)-1H-pyrazolo-[3,4-b]pyridin-3-amine.

In the title mol-ecule, C(12)H(12)N(4)S, the thio-phene ring is disordered over two orientations with a refined site-occupancy ratio of 0.777 (4):0.223 (4). The pyrazolo-pyridine ring system is essentially planar with an r.m.s. deviation of 0.0069 (3) Å and makes dihedral angles of 82.8 (2) and 72.6 (5)°, respectively, with the major and minor components of the thio-phene ring. In the crystal, mol-ecules are linked into a chain along the a axis by a pair of N-H⋯N(pyrazole) hydrogen bonds and a pair of N-H⋯N(pyridine) hydrogen bonds, both having a centrosymmetric R(2) (2)(8) graph-set motif. A C-H⋯π inter-action is also present.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to and bioactivity of pyrazole derivatives, see: Ali (2009 ▶); Bharate et al. (2008 ▶); Fu et al. (2010 ▶); Thumar & Patel (2011 ▶). For a related structure, see: Fun et al. (2011 ▶).

Experimental

Crystal data

C12H12N4S

M = 244.33

Monoclinic,

a = 10.0688 (2) Å

b = 8.0116 (2) Å

c = 15.7479 (3) Å

β = 106.809 (1)°

V = 1216.06 (5) Å3

Z = 4

Cu Kα radiation

μ = 2.22 mm−1

T = 296 K

0.44 × 0.33 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.445, T max = 0.746

15551 measured reflections

2379 independent reflections

2073 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.139

S = 1.05

2379 reflections

185 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812004126/is5063sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004126/is5063Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812004126/is5063Isup3.cml

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

C12H12N4S	F(000) = 512
Mr = 244.33	Dx = 1.334 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2379 reflections
a = 10.0688 (2) Å	θ = 4.6–72.1°
b = 8.0116 (2) Å	µ = 2.22 mm−1
c = 15.7479 (3) Å	T = 296 K
β = 106.809 (1)°	Block, orange
V = 1216.06 (5) Å3	0.44 × 0.33 × 0.14 mm
Z = 4

Bruker APEX DUO CCD area-detector diffractometer	2379 independent reflections
Radiation source: sealed tube	2073 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 72.1°, θmin = 4.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→12
Tmin = 0.445, Tmax = 0.746	k = −9→9
15551 measured reflections	l = −19→18

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0775P)2 + 0.3031P] where P = (Fo2 + 2Fc2)/3
2379 reflections	(Δ/σ)max = 0.001
185 parameters	Δρmax = 0.46 e Å−3
8 restraints	Δρmin = −0.34 e Å−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	−0.02326 (14)	0.27878 (19)	0.44140 (10)	0.0528 (4)
N2	0.17129 (16)	0.4642 (2)	0.48858 (12)	0.0599 (4)
H2A	0.1338	0.5370	0.5145	0.072*
N3	0.30572 (15)	0.4725 (2)	0.48332 (12)	0.0573 (4)
N4	0.44670 (17)	0.3121 (3)	0.41915 (12)	0.0628 (5)
C1	0.02348 (19)	0.0354 (2)	0.36199 (12)	0.0529 (4)
C2	−0.06290 (18)	0.1345 (2)	0.39940 (12)	0.0521 (4)
C3	0.10716 (17)	0.3269 (2)	0.44769 (11)	0.0479 (4)
C4	0.32418 (17)	0.3387 (2)	0.43924 (11)	0.0482 (4)
C5	0.20109 (16)	0.2394 (2)	0.41425 (10)	0.0445 (4)
C6	0.15813 (17)	0.0883 (2)	0.37008 (10)	0.0464 (4)
C7	0.2575 (2)	−0.0108 (2)	0.33742 (12)	0.0525 (4)
C8A	0.3425 (11)	−0.1330 (14)	0.3854 (6)	0.119 (4)	0.777 (4)
H8AA	0.3419	−0.1694	0.4414	0.143*	0.777 (4)
C9A	0.4344 (5)	−0.1978 (6)	0.3355 (3)	0.0991 (16)	0.777 (4)
H9AA	0.4944	−0.2875	0.3540	0.119*	0.777 (4)
C10A	0.4219 (5)	−0.1147 (5)	0.2621 (3)	0.0750 (11)	0.777 (4)
H10A	0.4759	−0.1361	0.2244	0.090*	0.777 (4)
S1A	0.29738 (18)	0.03657 (17)	0.24181 (9)	0.0761 (4)	0.777 (4)
C8B	0.3177 (14)	0.0482 (17)	0.2633 (8)	0.038 (3)*	0.223 (4)
H8BA	0.2986	0.1484	0.2323	0.045*	0.223 (4)
C9B	0.411 (3)	−0.083 (3)	0.2509 (16)	0.131 (9)*	0.223 (4)
H9BA	0.4619	−0.0808	0.2102	0.157*	0.223 (4)
C10B	0.411 (3)	−0.204 (3)	0.3054 (15)	0.131 (9)*	0.223 (4)
H10B	0.4560	−0.3040	0.3027	0.157*	0.223 (4)
S1B	0.3270 (16)	−0.1710 (17)	0.3810 (8)	0.168 (5)	0.223 (4)
C11	−0.0320 (3)	−0.1256 (3)	0.31546 (18)	0.0809 (7)
H11A	0.0367	−0.1750	0.2919	0.121*
H11B	−0.1144	−0.1031	0.2680	0.121*
H11C	−0.0536	−0.2011	0.3569	0.121*
C12	−0.2079 (2)	0.0787 (3)	0.39368 (16)	0.0687 (6)
H12A	−0.2504	0.1587	0.4230	0.103*
H12B	−0.2045	−0.0281	0.4219	0.103*
H12C	−0.2612	0.0700	0.3325	0.103*
H1N4	0.524 (2)	0.373 (3)	0.4497 (15)	0.067 (6)*
H2N4	0.456 (3)	0.214 (4)	0.4039 (19)	0.085 (8)*

	U11	U22	U33	U12	U13	U23
N1	0.0438 (7)	0.0573 (8)	0.0612 (8)	−0.0020 (6)	0.0212 (6)	−0.0079 (7)
N2	0.0477 (8)	0.0560 (9)	0.0829 (11)	−0.0053 (6)	0.0296 (8)	−0.0224 (8)
N3	0.0462 (8)	0.0569 (9)	0.0741 (10)	−0.0071 (6)	0.0259 (7)	−0.0156 (7)
N4	0.0468 (8)	0.0693 (11)	0.0791 (11)	−0.0066 (8)	0.0290 (8)	−0.0206 (9)
C1	0.0558 (10)	0.0527 (9)	0.0515 (9)	−0.0068 (7)	0.0177 (7)	−0.0069 (7)
C2	0.0481 (9)	0.0580 (10)	0.0514 (9)	−0.0072 (7)	0.0164 (7)	−0.0038 (7)
C3	0.0445 (8)	0.0484 (8)	0.0533 (9)	−0.0015 (7)	0.0184 (7)	−0.0052 (7)
C4	0.0433 (8)	0.0515 (9)	0.0526 (9)	−0.0011 (7)	0.0187 (7)	−0.0040 (7)
C5	0.0440 (8)	0.0467 (8)	0.0451 (8)	0.0012 (6)	0.0166 (6)	−0.0008 (6)
C6	0.0509 (9)	0.0483 (8)	0.0423 (8)	0.0006 (7)	0.0172 (7)	−0.0014 (6)
C7	0.0592 (10)	0.0499 (9)	0.0530 (9)	−0.0008 (8)	0.0235 (8)	−0.0081 (7)
C8A	0.153 (6)	0.121 (6)	0.117 (5)	0.085 (5)	0.092 (5)	0.027 (4)
C9A	0.118 (3)	0.107 (3)	0.083 (3)	0.069 (3)	0.047 (2)	0.003 (2)
C10A	0.081 (2)	0.073 (2)	0.090 (2)	0.0043 (16)	0.0528 (19)	−0.0218 (18)
S1A	0.0992 (9)	0.0783 (6)	0.0670 (7)	0.0156 (5)	0.0495 (7)	0.0042 (5)
S1B	0.243 (11)	0.120 (5)	0.121 (5)	0.095 (6)	0.023 (5)	−0.004 (4)
C11	0.0786 (15)	0.0764 (14)	0.0926 (16)	−0.0228 (12)	0.0326 (12)	−0.0328 (13)
C12	0.0530 (11)	0.0785 (13)	0.0775 (13)	−0.0143 (10)	0.0235 (10)	−0.0093 (11)

N1—C2	1.334 (2)	C7—S1A	1.709 (2)
N1—C3	1.344 (2)	C8A—C9A	1.472 (6)
N2—C3	1.342 (2)	C8A—H8AA	0.9300
N2—N3	1.381 (2)	C9A—C10A	1.308 (5)
N2—H2A	0.8600	C9A—H9AA	0.9300
N3—C4	1.319 (2)	C10A—S1A	1.706 (4)
N4—C4	1.376 (2)	C10A—H10A	0.9300
N4—H1N4	0.93 (2)	C8B—C9B	1.462 (19)
N4—H2N4	0.83 (3)	C8B—H8BA	0.9300
C1—C6	1.391 (2)	C9B—C10B	1.290 (17)
C1—C2	1.425 (3)	C9B—H9BA	0.9300
C1—C11	1.508 (3)	C10B—S1B	1.669 (17)
C2—C12	1.504 (3)	C10B—H10B	0.9300
C3—C5	1.397 (2)	C11—H11A	0.9600
C4—C5	1.429 (2)	C11—H11B	0.9600
C5—C6	1.401 (2)	C11—H11C	0.9600
C6—C7	1.481 (2)	C12—H12A	0.9600
C7—C8A	1.374 (9)	C12—H12B	0.9600
C7—S1B	1.527 (11)	C12—H12C	0.9600
C7—C8B	1.537 (14)
C2—N1—C3	115.52 (14)	S1B—C7—S1A	112.9 (5)
C3—N2—N3	110.79 (14)	C7—C8A—C9A	110.2 (5)
C3—N2—H2A	124.6	C7—C8A—H8AA	124.9
N3—N2—H2A	124.6	C9A—C8A—H8AA	124.9
C4—N3—N2	106.36 (14)	C10A—C9A—C8A	112.2 (4)
C4—N4—H1N4	118.1 (15)	C10A—C9A—H9AA	123.9
C4—N4—H2N4	113 (2)	C8A—C9A—H9AA	123.9
H1N4—N4—H2N4	120 (2)	C9A—C10A—S1A	113.9 (3)
C6—C1—C2	119.20 (15)	C9A—C10A—H10A	123.1
C6—C1—C11	121.27 (17)	S1A—C10A—H10A	123.1
C2—C1—C11	119.53 (18)	C10A—S1A—C7	91.41 (17)
N1—C2—C1	123.84 (16)	C9B—C8B—C7	106.8 (12)
N1—C2—C12	115.67 (17)	C9B—C8B—H8BA	126.6
C1—C2—C12	120.49 (17)	C7—C8B—H8BA	126.6
N2—C3—N1	126.49 (15)	C10B—C9B—C8B	109 (2)
N2—C3—C5	107.94 (15)	C10B—C9B—H9BA	125.5
N1—C3—C5	125.56 (15)	C8B—C9B—H9BA	125.5
N3—C4—N4	121.28 (16)	C9B—C10B—S1B	117.1 (19)
N3—C4—C5	110.77 (15)	C9B—C10B—H10B	121.5
N4—C4—C5	127.88 (16)	S1B—C10B—H10B	121.5
C3—C5—C6	118.39 (15)	C7—S1B—C10B	94.1 (11)
C3—C5—C4	104.14 (14)	C1—C11—H11A	109.5
C6—C5—C4	137.45 (15)	C1—C11—H11B	109.5
C1—C6—C5	117.49 (15)	H11A—C11—H11B	109.5
C1—C6—C7	122.94 (16)	C1—C11—H11C	109.5
C5—C6—C7	119.52 (15)	H11A—C11—H11C	109.5
C8A—C7—C6	124.5 (3)	H11B—C11—H11C	109.5
C6—C7—S1B	124.2 (5)	C2—C12—H12A	109.5
C8A—C7—C8B	108.5 (6)	C2—C12—H12B	109.5
C6—C7—C8B	123.6 (5)	H12A—C12—H12B	109.5
S1B—C7—C8B	111.7 (7)	C2—C12—H12C	109.5
C8A—C7—S1A	112.1 (3)	H12A—C12—H12C	109.5
C6—C7—S1A	122.78 (14)	H12B—C12—H12C	109.5
C3—N2—N3—C4	−0.3 (2)	C5—C6—C7—C8A	90.8 (7)
C3—N1—C2—C1	−0.6 (3)	C1—C6—C7—S1B	−72.2 (8)
C3—N1—C2—C12	178.93 (17)	C5—C6—C7—S1B	105.4 (8)
C6—C1—C2—N1	1.0 (3)	C1—C6—C7—C8B	116.5 (6)
C11—C1—C2—N1	−179.7 (2)	C5—C6—C7—C8B	−66.0 (6)
C6—C1—C2—C12	−178.53 (18)	C1—C6—C7—S1A	103.4 (2)
C11—C1—C2—C12	0.7 (3)	C5—C6—C7—S1A	−79.1 (2)
N3—N2—C3—N1	178.90 (17)	C6—C7—C8A—C9A	−176.1 (5)
N3—N2—C3—C5	0.3 (2)	S1B—C7—C8A—C9A	91 (3)
C2—N1—C3—N2	−178.20 (18)	C8B—C7—C8A—C9A	−16.4 (11)
C2—N1—C3—C5	0.1 (3)	S1A—C7—C8A—C9A	−5.3 (10)
N2—N3—C4—N4	177.36 (18)	C7—C8A—C9A—C10A	5.6 (11)
N2—N3—C4—C5	0.2 (2)	C8A—C9A—C10A—S1A	−3.3 (8)
N2—C3—C5—C6	178.62 (15)	C9A—C10A—S1A—C7	0.2 (4)
N1—C3—C5—C6	0.0 (3)	C8A—C7—S1A—C10A	3.1 (6)
N2—C3—C5—C4	−0.21 (19)	C6—C7—S1A—C10A	174.1 (2)
N1—C3—C5—C4	−178.79 (17)	S1B—C7—S1A—C10A	−9.9 (7)
N3—C4—C5—C3	0.0 (2)	C8B—C7—S1A—C10A	76 (3)
N4—C4—C5—C3	−176.92 (19)	C8A—C7—C8B—C9B	19.9 (13)
N3—C4—C5—C6	−178.47 (19)	C6—C7—C8B—C9B	179.8 (10)
N4—C4—C5—C6	4.6 (3)	S1B—C7—C8B—C9B	7.5 (12)
C2—C1—C6—C5	−0.8 (2)	S1A—C7—C8B—C9B	−91 (3)
C11—C1—C6—C5	179.96 (19)	C7—C8B—C9B—C10B	0.2 (18)
C2—C1—C6—C7	176.76 (17)	C8B—C9B—C10B—S1B	−7 (2)
C11—C1—C6—C7	−2.5 (3)	C8A—C7—S1B—C10B	−87 (3)
C3—C5—C6—C1	0.3 (2)	C6—C7—S1B—C10B	177.9 (10)
C4—C5—C6—C1	178.65 (19)	C8B—C7—S1B—C10B	−9.9 (13)
C3—C5—C6—C7	−177.34 (16)	S1A—C7—S1B—C10B	1.9 (13)
C4—C5—C6—C7	1.0 (3)	C9B—C10B—S1B—C7	11 (2)
C1—C6—C7—C8A	−86.7 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.08	2.937 (2)	171
N4—H1N4···N3ii	0.93 (2)	2.13 (2)	3.056 (3)	176 (2)
C12—H12B···Cg1iii	0.96	2.94	3.717 (2)	139

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C3/N1/C5/C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.08	2.937 (2)	171
N4—H1N4⋯N3ii	0.93 (2)	2.13 (2)	3.056 (3)	176 (2)
C12—H12B⋯Cg1iii	0.96	2.94	3.717 (2)	139

Symmetry codes: (i) ; (ii) ; (iii) .