3,6-Dimethyl-1-phenyl-4-(2-thien-yl)-8-(2-thienylmethyl-ene)-5,6,7,8-tetra-hydro-1H-pyrazolo[3,4-b][1,6]naphthyridine.

In the mol-ecule of the title compound, C(26)H(22)N(4)S(2), the pyrazole ring is oriented at a dihedral angle of 0.85 (3)° with respect to the adjacent naphthyridine ring, while the other ring of naphthyridine adopts an envelope conformation. The dihedral angle between phenyl and pyrazole rings is 87.65 (3)°. In the crystal structure, weak inter-molecular C-H⋯N inter-actions link the mol-ecules into chains. The π-π contacts between the naphthyridine rings and the naphthyridine and thio-phene rings [centroid-centroid distances = 3.766 (3) and 3.878 (3) Å] may further stabilize the structure. A weak C-H⋯π inter-action is also present.

Related literature

For the biological activity of naphthyridines, see: Abou et al. (2001 ▶); Aleem et al. (2002 ▶); Blagg et al. (2003 ▶); Ohta et al. (2004 ▶). For the biological properties of pyrazolopyridine derivatives, see: Lynck et al. (1988 ▶); Fucini et al. (2008 ▶); Warshakoon et al. (2006 ▶). They are also active against gram positive and gram negative bacteria, see: El-Dean et al. (1991 ▶) and inhibit cholesterol formation, see: Fujikawa et al. (1989 ▶, 1990 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C26H22N4S2

M = 454.60

Triclinic,

a = 10.7187 (16) Å

b = 10.9704 (19) Å

c = 11.153 (2) Å

α = 109.785 (2)°

β = 102.364 (1)°

γ = 104.201 (1)°

V = 1131.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 298 K

0.18 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.955, T max = 0.960

5846 measured reflections

3918 independent reflections

2322 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.176

S = 1.00

3918 reflections

291 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014810/hk2672sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014810/hk2672Isup2.hkl

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

C26H22N4S2	Z = 2
Mr = 454.60	F(000) = 476
Triclinic, P1	Dx = 1.335 Mg m−3
Hall symbol: -P 1	Melting point = 452–453 K
a = 10.7187 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9704 (19) Å	Cell parameters from 1616 reflections
c = 11.153 (2) Å	θ = 2.3–24.8°
α = 109.785 (2)°	µ = 0.26 mm−1
β = 102.364 (1)°	T = 298 K
γ = 104.201 (1)°	Block, yellow
V = 1131.0 (3) Å3	0.18 × 0.17 × 0.16 mm

Bruker SMART CCD area-detector diffractometer	3918 independent reflections
Radiation source: fine-focus sealed tube	2322 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
Tmin = 0.955, Tmax = 0.960	k = −12→13
5846 measured reflections	l = −13→13

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0957P)2] where P = (Fo2 + 2Fc2)/3
3918 reflections	(Δ/σ)max < 0.001
291 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	1.09086 (12)	0.85725 (11)	1.54317 (11)	0.0768 (4)
S2	0.32900 (12)	0.10633 (12)	1.04051 (11)	0.0826 (4)
N1	0.5616 (3)	0.2524 (3)	1.5917 (3)	0.0481 (7)
N2	0.4340 (3)	0.1519 (3)	1.5362 (3)	0.0529 (8)
N3	0.6907 (3)	0.4256 (3)	1.5345 (3)	0.0442 (7)
N4	0.7120 (3)	0.5378 (3)	1.2194 (3)	0.0507 (7)
C1	0.3741 (3)	0.1548 (3)	1.4219 (3)	0.0477 (9)
C2	0.4614 (3)	0.2600 (3)	1.3994 (3)	0.0432 (8)
C3	0.5805 (3)	0.3207 (3)	1.5104 (3)	0.0417 (8)
C4	0.4568 (3)	0.3106 (3)	1.2988 (3)	0.0416 (8)
C5	0.5739 (3)	0.4802 (4)	1.2173 (3)	0.0518 (9)
H5A	0.5198	0.4087	1.1282	0.062*
H5B	0.5338	0.5520	1.2358	0.062*
C6	0.5706 (3)	0.4201 (3)	1.3199 (3)	0.0432 (8)
C7	0.6845 (3)	0.4735 (3)	1.4386 (3)	0.0417 (8)
C8	0.8071 (3)	0.5867 (3)	1.4584 (3)	0.0435 (8)
C9	0.7958 (4)	0.6439 (4)	1.3528 (4)	0.0565 (10)
H9A	0.7567	0.7160	1.3767	0.068*
H9B	0.8861	0.6849	1.3509	0.068*
C10	0.6506 (3)	0.2705 (3)	1.7162 (3)	0.0458 (8)
C11	0.5969 (4)	0.2282 (4)	1.8042 (4)	0.0588 (10)
H11	0.5032	0.1886	1.7824	0.071*
C12	0.6838 (4)	0.2456 (4)	1.9247 (4)	0.0659 (11)
H12	0.6477	0.2174	1.9836	0.079*
C13	0.8214 (4)	0.3032 (4)	1.9589 (4)	0.0690 (11)
H13	0.8788	0.3151	2.0405	0.083*
C14	0.8741 (4)	0.3437 (4)	1.8704 (4)	0.0643 (11)
H14	0.9679	0.3820	1.8923	0.077*
C15	0.7896 (4)	0.3281 (4)	1.7496 (4)	0.0555 (10)
H15	0.8265	0.3564	1.6911	0.067*
C16	0.2334 (4)	0.0573 (4)	1.3364 (4)	0.0625 (11)
H16A	0.2020	−0.0031	1.3773	0.094*
H16B	0.2341	0.0036	1.2485	0.094*
H16C	0.1737	0.1087	1.3284	0.094*
C17	0.3367 (3)	0.2461 (3)	1.1741 (3)	0.0459 (8)
C18	0.2173 (3)	0.2811 (4)	1.1483 (3)	0.0498 (9)
H18	0.2016	0.3556	1.2057	0.060*
C19	0.1251 (4)	0.1809 (5)	1.0180 (4)	0.0675 (11)
H19	0.0395	0.1832	0.9821	0.081*
C20	0.1702 (4)	0.0850 (4)	0.9523 (4)	0.0657 (11)
H20	0.1202	0.0143	0.8675	0.079*
C21	0.7112 (4)	0.5941 (4)	1.1182 (4)	0.0688 (11)
H21A	0.6811	0.6719	1.1425	0.103*
H21B	0.6506	0.5245	1.0320	0.103*
H21C	0.8015	0.6230	1.1136	0.103*
C22	0.9196 (3)	0.6288 (3)	1.5629 (3)	0.0482 (9)
H22	0.9119	0.5826	1.6186	0.058*
C23	1.0514 (4)	0.7338 (3)	1.6046 (3)	0.0480 (9)
C24	1.1687 (3)	0.7475 (3)	1.7027 (3)	0.0425 (8)
H24	1.1705	0.6932	1.7511	0.051*
C25	1.2830 (4)	0.8555 (4)	1.7167 (4)	0.0665 (11)
H25	1.3696	0.8787	1.7750	0.080*
C26	1.2548 (4)	0.9214 (4)	1.6380 (4)	0.0740 (13)
H26	1.3193	0.9945	1.6364	0.089*

	U11	U22	U33	U12	U13	U23
S1	0.0715 (8)	0.0687 (7)	0.0740 (8)	−0.0057 (6)	0.0132 (6)	0.0382 (6)
S2	0.0723 (8)	0.0782 (8)	0.0661 (7)	0.0296 (6)	0.0035 (6)	0.0026 (6)
N1	0.0430 (17)	0.0511 (17)	0.0446 (16)	0.0028 (14)	0.0117 (14)	0.0245 (14)
N2	0.0424 (17)	0.0533 (18)	0.0526 (18)	−0.0015 (14)	0.0116 (14)	0.0248 (15)
N3	0.0400 (16)	0.0432 (15)	0.0403 (15)	0.0046 (13)	0.0104 (13)	0.0154 (13)
N4	0.0521 (18)	0.0571 (17)	0.0439 (16)	0.0121 (15)	0.0142 (14)	0.0278 (15)
C1	0.042 (2)	0.047 (2)	0.048 (2)	0.0066 (16)	0.0138 (16)	0.0192 (17)
C2	0.0382 (19)	0.0431 (18)	0.0415 (18)	0.0080 (15)	0.0127 (15)	0.0140 (15)
C3	0.0405 (19)	0.0447 (18)	0.0362 (18)	0.0095 (16)	0.0102 (15)	0.0177 (15)
C4	0.0378 (19)	0.0428 (18)	0.0402 (18)	0.0126 (15)	0.0104 (15)	0.0147 (15)
C5	0.049 (2)	0.057 (2)	0.051 (2)	0.0140 (18)	0.0126 (17)	0.0300 (18)
C6	0.042 (2)	0.0457 (19)	0.0436 (19)	0.0134 (16)	0.0157 (16)	0.0204 (16)
C7	0.0414 (19)	0.0432 (18)	0.0415 (19)	0.0128 (16)	0.0150 (16)	0.0192 (16)
C8	0.046 (2)	0.0409 (18)	0.0402 (18)	0.0103 (16)	0.0160 (16)	0.0157 (15)
C9	0.056 (2)	0.056 (2)	0.057 (2)	0.0079 (19)	0.0181 (19)	0.0306 (19)
C10	0.047 (2)	0.0435 (19)	0.045 (2)	0.0110 (16)	0.0141 (17)	0.0204 (16)
C11	0.055 (2)	0.065 (2)	0.054 (2)	0.0109 (19)	0.0169 (19)	0.029 (2)
C12	0.075 (3)	0.080 (3)	0.054 (2)	0.025 (2)	0.026 (2)	0.040 (2)
C13	0.070 (3)	0.086 (3)	0.052 (2)	0.029 (2)	0.012 (2)	0.033 (2)
C14	0.050 (2)	0.072 (3)	0.063 (3)	0.017 (2)	0.008 (2)	0.027 (2)
C15	0.055 (2)	0.062 (2)	0.053 (2)	0.0169 (19)	0.0186 (19)	0.0284 (19)
C16	0.048 (2)	0.061 (2)	0.063 (2)	−0.0026 (19)	0.0112 (19)	0.027 (2)
C17	0.044 (2)	0.0469 (19)	0.0428 (19)	0.0086 (16)	0.0146 (16)	0.0186 (16)
C18	0.041 (2)	0.058 (2)	0.0372 (18)	0.0101 (17)	0.0098 (16)	0.0105 (17)
C19	0.047 (2)	0.089 (3)	0.072 (3)	0.026 (2)	0.014 (2)	0.043 (3)
C20	0.055 (2)	0.061 (2)	0.049 (2)	0.001 (2)	−0.0019 (19)	0.0084 (19)
C21	0.072 (3)	0.083 (3)	0.059 (2)	0.018 (2)	0.021 (2)	0.045 (2)
C22	0.051 (2)	0.0463 (19)	0.047 (2)	0.0076 (17)	0.0196 (18)	0.0229 (17)
C23	0.051 (2)	0.0436 (19)	0.0426 (19)	0.0065 (17)	0.0194 (17)	0.0146 (16)
C24	0.0415 (19)	0.0375 (17)	0.0444 (19)	0.0098 (15)	0.0167 (16)	0.0132 (15)
C25	0.047 (2)	0.072 (3)	0.061 (2)	0.011 (2)	0.017 (2)	0.011 (2)
C26	0.064 (3)	0.060 (2)	0.068 (3)	−0.014 (2)	0.025 (2)	0.016 (2)

S1—C26	1.672 (5)	C11—C12	1.384 (5)
S1—C23	1.718 (4)	C11—H11	0.9300
S2—C20	1.689 (4)	C12—C13	1.363 (5)
S2—C17	1.708 (3)	C12—H12	0.9300
N1—C3	1.375 (4)	C13—C14	1.379 (6)
N1—N2	1.381 (3)	C13—H13	0.9300
N1—C10	1.424 (4)	C14—C15	1.381 (5)
N2—C1	1.314 (4)	C14—H14	0.9300
N3—C3	1.334 (4)	C15—H15	0.9300
N3—C7	1.338 (4)	C16—H16A	0.9600
N4—C5	1.451 (4)	C16—H16B	0.9600
N4—C9	1.455 (4)	C16—H16C	0.9600
N4—C21	1.458 (4)	C17—C18	1.423 (5)
C1—C2	1.428 (4)	C18—C19	1.438 (5)
C1—C16	1.493 (5)	C18—H18	0.9300
C2—C3	1.398 (4)	C19—C20	1.325 (5)
C2—C4	1.407 (4)	C19—H19	0.9300
C4—C6	1.398 (4)	C20—H20	0.9300
C4—C17	1.487 (4)	C21—H21A	0.9600
C5—C6	1.504 (5)	C21—H21B	0.9600
C5—H5A	0.9700	C21—H21C	0.9600
C5—H5B	0.9700	C22—C23	1.448 (4)
C6—C7	1.420 (4)	C22—H22	0.9300
C7—C8	1.486 (4)	C23—C24	1.417 (5)
C8—C22	1.336 (5)	C24—C25	1.417 (5)
C8—C9	1.508 (5)	C24—H24	0.9300
C9—H9A	0.9700	C25—C26	1.344 (6)
C9—H9B	0.9700	C25—H25	0.9300
C10—C15	1.379 (5)	C26—H26	0.9300
C10—C11	1.389 (5)
C26—S1—C23	93.1 (2)	C13—C12—H12	119.3
C20—S2—C17	92.60 (19)	C11—C12—H12	119.3
C3—N1—N2	110.2 (3)	C12—C13—C14	118.9 (4)
C3—N1—C10	130.4 (3)	C12—C13—H13	120.5
N2—N1—C10	119.4 (3)	C14—C13—H13	120.5
C1—N2—N1	107.4 (3)	C13—C14—C15	121.0 (4)
C3—N3—C7	114.8 (3)	C13—C14—H14	119.5
C5—N4—C9	110.4 (3)	C15—C14—H14	119.5
C5—N4—C21	110.0 (3)	C10—C15—C14	119.8 (4)
C9—N4—C21	110.6 (3)	C10—C15—H15	120.1
N2—C1—C2	110.4 (3)	C14—C15—H15	120.1
N2—C1—C16	120.6 (3)	C1—C16—H16A	109.5
C2—C1—C16	129.0 (3)	C1—C16—H16B	109.5
C3—C2—C4	117.5 (3)	H16A—C16—H16B	109.5
C3—C2—C1	105.4 (3)	C1—C16—H16C	109.5
C4—C2—C1	137.1 (3)	H16A—C16—H16C	109.5
N3—C3—N1	126.3 (3)	H16B—C16—H16C	109.5
N3—C3—C2	127.1 (3)	C18—C17—C4	128.8 (3)
N1—C3—C2	106.6 (3)	C18—C17—S2	111.7 (2)
C6—C4—C2	117.1 (3)	C4—C17—S2	119.5 (3)
C6—C4—C17	122.2 (3)	C17—C18—C19	108.0 (3)
C2—C4—C17	120.6 (3)	C17—C18—H18	126.0
N4—C5—C6	111.5 (3)	C19—C18—H18	126.0
N4—C5—H5A	109.3	C20—C19—C18	115.7 (4)
C6—C5—H5A	109.3	C20—C19—H19	122.2
N4—C5—H5B	109.3	C18—C19—H19	122.2
C6—C5—H5B	109.3	C19—C20—S2	112.1 (3)
H5A—C5—H5B	108.0	C19—C20—H20	124.0
C4—C6—C7	119.5 (3)	S2—C20—H20	124.0
C4—C6—C5	120.5 (3)	N4—C21—H21A	109.5
C7—C6—C5	120.0 (3)	N4—C21—H21B	109.5
N3—C7—C6	124.0 (3)	H21A—C21—H21B	109.5
N3—C7—C8	116.7 (3)	N4—C21—H21C	109.5
C6—C7—C8	119.3 (3)	H21A—C21—H21C	109.5
C22—C8—C7	119.9 (3)	H21B—C21—H21C	109.5
C22—C8—C9	124.1 (3)	C8—C22—C23	131.3 (3)
C7—C8—C9	115.9 (3)	C8—C22—H22	114.4
N4—C9—C8	112.0 (3)	C23—C22—H22	114.4
N4—C9—H9A	109.2	C24—C23—C22	123.9 (3)
C8—C9—H9A	109.2	C24—C23—S1	109.9 (2)
N4—C9—H9B	109.2	C22—C23—S1	126.2 (3)
C8—C9—H9B	109.2	C23—C24—C25	110.4 (3)
H9A—C9—H9B	107.9	C23—C24—H24	124.8
C15—C10—C11	119.6 (3)	C25—C24—H24	124.8
C15—C10—N1	120.7 (3)	C26—C25—C24	114.0 (4)
C11—C10—N1	119.7 (3)	C26—C25—H25	123.0
C12—C11—C10	119.4 (4)	C24—C25—H25	123.0
C12—C11—H11	120.3	C25—C26—S1	112.5 (3)
C10—C11—H11	120.3	C25—C26—H26	123.7
C13—C12—C11	121.3 (4)	S1—C26—H26	123.7
C3—N1—N2—C1	0.9 (4)	C6—C7—C8—C9	4.5 (5)
C10—N1—N2—C1	−178.9 (3)	C5—N4—C9—C8	62.2 (4)
N1—N2—C1—C2	−0.7 (4)	C21—N4—C9—C8	−175.8 (3)
N1—N2—C1—C16	179.8 (3)	C22—C8—C9—N4	143.5 (3)
N2—C1—C2—C3	0.3 (4)	C7—C8—C9—N4	−34.4 (4)
C16—C1—C2—C3	179.7 (3)	C3—N1—C10—C15	−24.3 (6)
N2—C1—C2—C4	178.8 (4)	N2—N1—C10—C15	155.4 (3)
C16—C1—C2—C4	−1.8 (7)	C3—N1—C10—C11	156.4 (3)
C7—N3—C3—N1	179.3 (3)	N2—N1—C10—C11	−23.9 (5)
C7—N3—C3—C2	−1.6 (5)	C15—C10—C11—C12	0.5 (6)
N2—N1—C3—N3	178.5 (3)	N1—C10—C11—C12	179.8 (3)
C10—N1—C3—N3	−1.8 (6)	C10—C11—C12—C13	−0.1 (6)
N2—N1—C3—C2	−0.7 (4)	C11—C12—C13—C14	−0.5 (6)
C10—N1—C3—C2	179.0 (3)	C12—C13—C14—C15	0.8 (6)
C4—C2—C3—N3	2.2 (5)	C11—C10—C15—C14	−0.2 (6)
C1—C2—C3—N3	−178.9 (3)	N1—C10—C15—C14	−179.5 (3)
C4—C2—C3—N1	−178.6 (3)	C13—C14—C15—C10	−0.4 (6)
C1—C2—C3—N1	0.3 (4)	C6—C4—C17—C18	−90.7 (4)
C3—C2—C4—C6	−1.7 (5)	C2—C4—C17—C18	91.2 (4)
C1—C2—C4—C6	180.0 (4)	C6—C4—C17—S2	92.1 (4)
C3—C2—C4—C17	176.6 (3)	C2—C4—C17—S2	−86.1 (4)
C1—C2—C4—C17	−1.8 (6)	C20—S2—C17—C18	−2.6 (3)
C9—N4—C5—C6	−58.1 (4)	C20—S2—C17—C4	175.1 (3)
C21—N4—C5—C6	179.6 (3)	C4—C17—C18—C19	−174.7 (3)
C2—C4—C6—C7	0.8 (5)	S2—C17—C18—C19	2.8 (4)
C17—C4—C6—C7	−177.4 (3)	C17—C18—C19—C20	−1.6 (5)
C2—C4—C6—C5	−180.0 (3)	C18—C19—C20—S2	−0.4 (5)
C17—C4—C6—C5	1.8 (5)	C17—S2—C20—C19	1.7 (3)
N4—C5—C6—C4	−151.4 (3)	C7—C8—C22—C23	179.2 (3)
N4—C5—C6—C7	27.8 (4)	C9—C8—C22—C23	1.3 (6)
C3—N3—C7—C6	0.6 (5)	C8—C22—C23—C24	−166.9 (4)
C3—N3—C7—C8	−177.7 (3)	C8—C22—C23—S1	12.1 (6)
C4—C6—C7—N3	−0.3 (5)	C26—S1—C23—C24	1.5 (3)
C5—C6—C7—N3	−179.5 (3)	C26—S1—C23—C22	−177.6 (3)
C4—C6—C7—C8	177.9 (3)	C22—C23—C24—C25	177.2 (3)
C5—C6—C7—C8	−1.3 (5)	S1—C23—C24—C25	−1.9 (3)
N3—C7—C8—C22	4.8 (5)	C23—C24—C25—C26	1.4 (4)
C6—C7—C8—C22	−173.6 (3)	C24—C25—C26—S1	−0.2 (5)
N3—C7—C8—C9	−177.2 (3)	C23—S1—C26—C25	−0.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···N2i	0.93	2.57	3.445 (3)	157
C20—H20···Cg6ii	0.93	2.93	3.680 (3)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C26—H26⋯N2i	0.93	2.57	3.445 (3)	157
C20—H20⋯Cg6ii	0.93	2.93	3.680 (3)	139

Symmetry codes: (i) ; (ii) . Cg6 is the centroid of the S1/C23–C26 ring.