(Z)-Ethyl 2-cyano-2-{2-[5,6-dimethyl-4-(thio-phen-2-yl)-1H-pyrazolo-[3,4-b]pyridin-3-yl]hydrazinylidene}acetate.

In the title compound, C(17)H(16)N(6)O(2)S, an intra-molecular N-H⋯O inter-action generates an S(6) ring. The pyridine ring makes a dihedral angle of 71.38 (11)° with the thio-phene ring. In the crystal, mol-ecules are linked by a pair of N-H⋯N hydrogen bonds, forming an inversion dimer. The dimers are stacked in columns along the b axis through weak inter-molecular C-H⋯N hydrogen bonds.

Related literature

For applications of pyrazole derivatives, see: Casas et al. (2007 ▶); Habeeb et al. (2001 ▶); Hashimoto et al. (2002 ▶); Ranatunge et al. (2004 ▶); Singh et al. (2005 ▶); Elzein et al. (2006 ▶). For previous reports on the diazotization of heterocyclic amines, see: Abdel-Aziz et al. (2008 ▶); Hamdy et al. (2007 ▶); Dawood et al. (2005 ▶); Farag et al. (2004 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C17H16N6O2S

M = 368.42

Monoclinic,

a = 8.0672 (5) Å

b = 10.6460 (7) Å

c = 20.5892 (13) Å

β = 90.332 (1)°

V = 1768.24 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.47 × 0.22 × 0.13 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.908, T max = 0.974

33610 measured reflections

4782 independent reflections

3518 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.219

S = 1.06

4782 reflections

238 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.68 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/S1600536811028911/is2753sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028911/is2753Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811028911/is2753Isup3.cml

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

C17H16N6O2S	F(000) = 768
Mr = 368.42	Dx = 1.384 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8773 reflections
a = 8.0672 (5) Å	θ = 2.7–28.9°
b = 10.6460 (7) Å	µ = 0.21 mm−1
c = 20.5892 (13) Å	T = 296 K
β = 90.332 (1)°	Block, yellow
V = 1768.24 (19) Å3	0.47 × 0.22 × 0.13 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	4782 independent reflections
Radiation source: fine-focus sealed tube	3518 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 29.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.908, Tmax = 0.974	k = −14→14
33610 measured reflections	l = −28→28

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.219	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1182P)2 + 0.809P] where P = (Fo2 + 2Fc2)/3
4782 reflections	(Δ/σ)max = 0.001
238 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.68 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.3443 (3)	0.6604 (2)	0.08593 (9)	0.0832 (7)
O2	0.4554 (3)	0.80464 (18)	0.01904 (9)	0.0674 (5)
N1	−0.0513 (2)	0.07181 (16)	0.08467 (9)	0.0443 (4)
N2	0.0682 (3)	0.16420 (17)	−0.01066 (9)	0.0527 (5)
H1N2	0.0709	0.1009	−0.0392	0.063*
N3	0.1472 (3)	0.27295 (17)	−0.02803 (9)	0.0514 (5)
N4	0.2184 (2)	0.46227 (16)	0.02614 (8)	0.0447 (4)
H1N4	0.2299	0.5014	0.0617	0.054*
N5	0.2772 (2)	0.51079 (17)	−0.02755 (8)	0.0441 (4)
N6	0.4563 (4)	0.7030 (3)	−0.13610 (14)	0.0921 (9)
C1	0.0215 (3)	0.16591 (18)	0.05219 (9)	0.0413 (4)
C2	−0.0843 (3)	0.09562 (19)	0.14668 (10)	0.0418 (4)
C3	−0.0472 (2)	0.21163 (18)	0.17806 (10)	0.0407 (4)
C4	0.0297 (2)	0.30706 (17)	0.14358 (9)	0.0370 (4)
C5	0.0674 (2)	0.28297 (17)	0.07806 (9)	0.0375 (4)
C6	0.1458 (3)	0.34311 (19)	0.02462 (9)	0.0419 (4)
C7	0.3502 (3)	0.6208 (2)	−0.02605 (10)	0.0465 (5)
C8	0.4084 (3)	0.6659 (3)	−0.08754 (13)	0.0588 (6)
C9	0.3807 (3)	0.6957 (2)	0.03246 (12)	0.0554 (6)
C10	0.4980 (4)	0.8842 (3)	0.07369 (16)	0.0752 (8)
H10A	0.5939	0.9350	0.0631	0.090*
H10B	0.5258	0.8326	0.1110	0.090*
C11	0.3568 (6)	0.9662 (4)	0.0894 (2)	0.1057 (13)
H11A	0.3878	1.0224	0.1238	0.158*
H11B	0.2646	0.9158	0.1029	0.158*
H11C	0.3261	1.0140	0.0516	0.158*
C12	0.0656 (2)	0.43206 (17)	0.17233 (9)	0.0385 (4)
S1	0.21437 (12)	0.45313 (7)	0.23040 (5)	0.0874 (4)
C13	−0.0232 (3)	0.54559 (17)	0.16053 (11)	0.0471 (5)
H13A	−0.1118	0.5552	0.1319	0.056*
C14	0.0476 (3)	0.6427 (2)	0.20046 (14)	0.0605 (7)
H14A	0.0110	0.7255	0.1989	0.073*
C15	0.1673 (4)	0.6062 (3)	0.23924 (14)	0.0674 (7)
H15A	0.2207	0.6591	0.2686	0.081*
C16	−0.1660 (4)	−0.0089 (2)	0.18327 (13)	0.0591 (6)
H16A	−0.1719	−0.0823	0.1563	0.089*
H16B	−0.2759	0.0161	0.1954	0.089*
H16C	−0.1024	−0.0275	0.2217	0.089*
C17	−0.1005 (4)	0.2290 (2)	0.24741 (12)	0.0590 (6)
H17A	−0.0752	0.3130	0.2612	0.089*
H17B	−0.0426	0.1702	0.2746	0.089*
H17C	−0.2177	0.2149	0.2506	0.089*

	U11	U22	U33	U12	U13	U23
O1	0.1284 (19)	0.0709 (13)	0.0503 (10)	−0.0409 (13)	0.0105 (11)	−0.0096 (9)
O2	0.0854 (13)	0.0548 (10)	0.0619 (11)	−0.0234 (9)	−0.0050 (9)	0.0013 (8)
N1	0.0605 (10)	0.0309 (8)	0.0415 (9)	−0.0040 (7)	−0.0020 (7)	−0.0093 (6)
N2	0.0854 (14)	0.0356 (9)	0.0372 (9)	−0.0096 (9)	0.0032 (9)	−0.0098 (7)
N3	0.0774 (13)	0.0385 (9)	0.0384 (9)	−0.0054 (9)	0.0012 (8)	−0.0044 (7)
N4	0.0599 (11)	0.0372 (8)	0.0371 (8)	−0.0072 (7)	0.0009 (7)	−0.0031 (6)
N5	0.0515 (10)	0.0407 (9)	0.0401 (9)	−0.0024 (7)	−0.0033 (7)	0.0010 (7)
N6	0.120 (2)	0.094 (2)	0.0626 (15)	−0.0126 (17)	0.0142 (15)	0.0220 (14)
C1	0.0559 (11)	0.0300 (9)	0.0381 (9)	−0.0006 (8)	−0.0031 (8)	−0.0071 (7)
C2	0.0488 (10)	0.0325 (9)	0.0441 (10)	−0.0020 (8)	0.0013 (8)	−0.0064 (7)
C3	0.0467 (10)	0.0355 (9)	0.0400 (9)	0.0001 (8)	0.0033 (8)	−0.0090 (7)
C4	0.0420 (9)	0.0296 (8)	0.0394 (9)	0.0022 (7)	−0.0028 (7)	−0.0094 (7)
C5	0.0460 (10)	0.0285 (8)	0.0379 (9)	0.0012 (7)	−0.0033 (7)	−0.0060 (7)
C6	0.0539 (11)	0.0341 (9)	0.0375 (9)	−0.0010 (8)	−0.0024 (8)	−0.0036 (7)
C7	0.0519 (11)	0.0434 (11)	0.0443 (11)	−0.0040 (9)	−0.0033 (9)	0.0029 (8)
C8	0.0656 (15)	0.0572 (14)	0.0536 (13)	−0.0080 (12)	−0.0014 (11)	0.0084 (11)
C9	0.0665 (14)	0.0486 (12)	0.0512 (12)	−0.0124 (11)	0.0006 (10)	−0.0013 (10)
C10	0.088 (2)	0.0700 (18)	0.0674 (17)	−0.0241 (16)	−0.0069 (15)	−0.0054 (14)
C11	0.123 (3)	0.104 (3)	0.090 (3)	0.005 (3)	0.022 (2)	−0.018 (2)
C12	0.0471 (10)	0.0322 (9)	0.0362 (9)	−0.0007 (7)	−0.0024 (7)	−0.0092 (7)
S1	0.1022 (6)	0.0517 (4)	0.1075 (7)	0.0073 (4)	−0.0565 (5)	−0.0211 (4)
C13	0.0628 (13)	0.0254 (8)	0.0529 (12)	−0.0027 (8)	−0.0138 (10)	−0.0069 (8)
C14	0.0720 (16)	0.0301 (10)	0.0795 (17)	0.0007 (10)	0.0077 (13)	−0.0153 (10)
C15	0.0914 (19)	0.0490 (13)	0.0617 (15)	−0.0171 (13)	−0.0097 (14)	−0.0215 (11)
C16	0.0800 (16)	0.0428 (11)	0.0544 (13)	−0.0172 (11)	0.0066 (12)	−0.0038 (10)
C17	0.0762 (16)	0.0506 (13)	0.0504 (12)	−0.0084 (12)	0.0185 (11)	−0.0156 (10)

O1—C9	1.202 (3)	C7—C8	1.436 (3)
O2—C9	1.337 (3)	C7—C9	1.464 (3)
O2—C10	1.448 (3)	C10—C11	1.472 (5)
N1—C2	1.330 (3)	C10—H10A	0.9700
N1—C1	1.342 (3)	C10—H10B	0.9700
N2—C1	1.350 (3)	C11—H11A	0.9600
N2—N3	1.370 (3)	C11—H11B	0.9600
N2—H1N2	0.8953	C11—H11C	0.9600
N3—C6	1.317 (3)	C12—C13	1.425 (3)
N4—N5	1.312 (2)	C12—S1	1.704 (2)
N4—C6	1.398 (3)	S1—C15	1.683 (3)
N4—H1N4	0.8475	C13—C14	1.438 (3)
N5—C7	1.311 (3)	C13—H13A	0.9300
N6—C8	1.144 (3)	C14—C15	1.309 (4)
C1—C5	1.404 (2)	C14—H14A	0.9300
C2—C3	1.425 (3)	C15—H15A	0.9300
C2—C16	1.498 (3)	C16—H16A	0.9600
C3—C4	1.388 (3)	C16—H16B	0.9600
C3—C17	1.505 (3)	C16—H16C	0.9600
C4—C5	1.408 (3)	C17—H17A	0.9600
C4—C12	1.484 (2)	C17—H17B	0.9600
C5—C6	1.424 (3)	C17—H17C	0.9600
C9—O2—C10	116.9 (2)	O2—C10—H10A	109.7
C2—N1—C1	115.27 (17)	C11—C10—H10A	109.7
C1—N2—N3	111.82 (16)	O2—C10—H10B	109.7
C1—N2—H1N2	130.4	C11—C10—H10B	109.7
N3—N2—H1N2	116.9	H10A—C10—H10B	108.2
C6—N3—N2	104.96 (17)	C10—C11—H11A	109.5
N5—N4—C6	119.50 (17)	C10—C11—H11B	109.5
N5—N4—H1N4	119.8	H11A—C11—H11B	109.5
C6—N4—H1N4	120.6	C10—C11—H11C	109.5
C7—N5—N4	119.77 (18)	H11A—C11—H11C	109.5
N1—C1—N2	126.38 (17)	H11B—C11—H11C	109.5
N1—C1—C5	126.08 (18)	C13—C12—C4	126.55 (17)
N2—C1—C5	107.51 (18)	C13—C12—S1	111.06 (14)
N1—C2—C3	123.90 (19)	C4—C12—S1	122.20 (15)
N1—C2—C16	115.61 (18)	C15—S1—C12	92.58 (12)
C3—C2—C16	120.49 (19)	C12—C13—C14	108.4 (2)
C4—C3—C2	119.73 (18)	C12—C13—H13A	125.8
C4—C3—C17	121.76 (18)	C14—C13—H13A	125.8
C2—C3—C17	118.46 (19)	C15—C14—C13	115.1 (2)
C3—C4—C5	117.16 (16)	C15—C14—H14A	122.5
C3—C4—C12	122.62 (17)	C13—C14—H14A	122.5
C5—C4—C12	120.17 (17)	C14—C15—S1	112.84 (18)
C1—C5—C4	117.84 (18)	C14—C15—H15A	123.6
C1—C5—C6	102.90 (16)	S1—C15—H15A	123.6
C4—C5—C6	139.26 (18)	C2—C16—H16A	109.5
N3—C6—N4	121.85 (19)	C2—C16—H16B	109.5
N3—C6—C5	112.78 (18)	H16A—C16—H16B	109.5
N4—C6—C5	125.35 (17)	C2—C16—H16C	109.5
N5—C7—C8	115.3 (2)	H16A—C16—H16C	109.5
N5—C7—C9	125.4 (2)	H16B—C16—H16C	109.5
C8—C7—C9	119.3 (2)	C3—C17—H17A	109.5
N6—C8—C7	179.0 (3)	C3—C17—H17B	109.5
O1—C9—O2	125.0 (2)	H17A—C17—H17B	109.5
O1—C9—C7	122.8 (2)	C3—C17—H17C	109.5
O2—C9—C7	112.1 (2)	H17A—C17—H17C	109.5
O2—C10—C11	109.7 (3)	H17B—C17—H17C	109.5
C1—N2—N3—C6	−1.2 (3)	N5—N4—C6—N3	6.0 (3)
C6—N4—N5—C7	−177.88 (19)	N5—N4—C6—C5	−175.59 (19)
C2—N1—C1—N2	179.4 (2)	C1—C5—C6—N3	0.5 (2)
C2—N1—C1—C5	1.5 (3)	C4—C5—C6—N3	179.5 (2)
N3—N2—C1—N1	−176.7 (2)	C1—C5—C6—N4	−178.0 (2)
N3—N2—C1—C5	1.6 (3)	C4—C5—C6—N4	1.0 (4)
C1—N1—C2—C3	0.1 (3)	N4—N5—C7—C8	−179.3 (2)
C1—N1—C2—C16	179.9 (2)	N4—N5—C7—C9	3.1 (4)
N1—C2—C3—C4	−0.8 (3)	C10—O2—C9—O1	1.3 (4)
C16—C2—C3—C4	179.4 (2)	C10—O2—C9—C7	−177.5 (2)
N1—C2—C3—C17	176.4 (2)	N5—C7—C9—O1	2.0 (4)
C16—C2—C3—C17	−3.4 (3)	C8—C7—C9—O1	−175.5 (3)
C2—C3—C4—C5	0.0 (3)	N5—C7—C9—O2	−179.2 (2)
C17—C3—C4—C5	−177.1 (2)	C8—C7—C9—O2	3.3 (3)
C2—C3—C4—C12	177.37 (18)	C9—O2—C10—C11	−87.7 (3)
C17—C3—C4—C12	0.3 (3)	C3—C4—C12—C13	−103.8 (3)
N1—C1—C5—C4	−2.2 (3)	C5—C4—C12—C13	73.5 (3)
N2—C1—C5—C4	179.51 (18)	C3—C4—C12—S1	70.8 (2)
N1—C1—C5—C6	177.1 (2)	C5—C4—C12—S1	−111.9 (2)
N2—C1—C5—C6	−1.2 (2)	C13—C12—S1—C15	−0.9 (2)
C3—C4—C5—C1	1.3 (3)	C4—C12—S1—C15	−176.20 (19)
C12—C4—C5—C1	−176.08 (18)	C4—C12—C13—C14	177.2 (2)
C3—C4—C5—C6	−177.6 (2)	S1—C12—C13—C14	2.2 (3)
C12—C4—C5—C6	5.0 (4)	C12—C13—C14—C15	−2.9 (3)
N2—N3—C6—N4	178.99 (19)	C13—C14—C15—S1	2.3 (4)
N2—N3—C6—C5	0.4 (3)	C12—S1—C15—C14	−0.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···N1i	0.89	2.07	2.941 (3)	165
N4—H1N4···O1	0.85	1.99	2.642 (3)	133
C13—H13A···N5ii	0.93	2.62	3.463 (3)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯N1i	0.89	2.07	2.941 (3)	165
N4—H1N4⋯O1	0.85	1.99	2.642 (3)	133
C13—H13A⋯N5ii	0.93	2.62	3.463 (3)	151

Symmetry codes: (i) ; (ii) .