N-[(E)-Quinoxalin-2-ylmethyl­idene]-1H-indazol-5-amine

Leeju, P.; Arun, V.; Sebastian, M.; Varsha, G.; Varghese, D.; Yusuff, K.K.M.

doi:10.1107/S1600536809027822

organic compounds

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Volume 65| Part 8| August 2009| Page o1981

doi:10.1107/S1600536809027822

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N-[(E)-Quinoxalin-2-ylmethylidene]-1H-indazol-5-amine

P. Leeju,^a V. Arun,^a Manju Sebastian,^a G. Varsha,^a Digna Varghese ^a and K. K. M. Yusuff ^a ^*

^aDepartment of Applied Chemistry, Cochin University of Science and Technology, Cochin 682 022, Kerala, India
^*Correspondence e-mail: yusuff@cusat.ac.in.

(Received 18 June 2009; accepted 15 July 2009; online 25 July 2009)

In the title molecule, C₁₆H₁₁N₅, the mean planes of the quinoxaline and indazole fragments form a dihedral angle of 10.62 (5)°. In the crystal, weak intermolecular N—H⋯N hydrogen bonds link the molecules into zigzag chains extending in the [001] direction. The crystal packing also exhibits π–π interactions [centroid–centroid distances of 3.7080 (2) and 3.8220 (5) Å], which form stacks of the molecules parallel to the a axis.

Related literature

For related structures, see: Varghese et al. (2009 ); Varsha et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₁N₅
M_r = 273.30
Monoclinic, P 2₁ /c
a = 7.7015 (6) Å
b = 8.0330 (6) Å
c = 20.6034 (16) Å
β = 96.882 (2)°
V = 1265.47 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.45 × 0.27 × 0.08 mm

Data collection

Bruker Kappa APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.960, T_max = 0.993
16012 measured reflections
3597 independent reflections
2502 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.143
S = 1.03
3597 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N1ⁱⁱⁱ	0.86	2.31	3.1050 (15)	153
Symmetry code: (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global, schiflm. DOI: 10.1107/S1600536809027822/cv2578sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027822/cv2578Isup2.hkl

checkCIF report

Comment top

In view of synthesizing new quinoxaline based Schiff bases, we have undertaken the synthesis of the title compound, (1), and report here its crystal structure. In (1), the quinoxaline ring and indazole ring are each approximately planar, with the maximum deviations of 0.0254 (4) and 0.0213 (4) Å from the least square planes, respectively. A perspective drawing is depicted in figure 1 with the atomic numbering scheme. The compound is non-planar due to the twisting of rings with respect to azomethine group. Bond lengths and angles are in normal ranges and comparable to those in related structures (Varghese et al., 2009; Varsha et al., 2009). In the crystal structure, molecules are held together by π–π stacking interactions and N—H···N intermolecular hydrogen bonding.

Related literature top

For related structures, see: Varghese et al. (2009); Varsha et al. (2009). Cg1, Cg2 and Cg3 are centroids of the N1/N2/C1/C6–C8, C1–C6 and C10–C16 rings, respectively.

Experimental top

A hot solution of 5-aminoindazole (1 mmol) in ethanol (20 ml) was added slowly to a hot solution of quinoxaline-2-carboxaldehyde (1 mmol) in the same solvent (40 ml).The resulting mixture on cooling yielded the crude product of (1). Pale green crystals suitable for single-crystal XRD are obtained by slow evaporation of ethanolic solution of (1).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

N-[(E)-Quinoxalin-2-ylmethylidene]-1H-indazol-5-amine top

Crystal data top

C₁₆H₁₁N₅	F(000) = 568
M_r = 273.30	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2502 reflections
a = 7.7015 (6) Å	θ = 2.6–29.8°
b = 8.0330 (6) Å	µ = 0.09 mm⁻¹
c = 20.6034 (16) Å	T = 298 K
β = 96.882 (2)°	Plate, green
V = 1265.47 (17) Å³	0.45 × 0.27 × 0.08 mm
Z = 4

Data collection top

Bruker Kappa APEX CCD diffractometer	3597 independent reflections
Radiation source: fine-focus sealed tube	2502 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and ϕ scans	θ_max = 29.8°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
T_min = 0.960, T_max = 0.993	k = −11→10
16012 measured reflections	l = −28→26

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0715P)² + 0.2171P] where P = (F_o² + 2F_c²)/3
3597 reflections	(Δ/σ)_max = 0.003
190 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₆H₁₁N₅	V = 1265.47 (17) Å³
M_r = 273.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7015 (6) Å	µ = 0.09 mm⁻¹
b = 8.0330 (6) Å	T = 298 K
c = 20.6034 (16) Å	0.45 × 0.27 × 0.08 mm
β = 96.882 (2)°

Data collection top

Bruker Kappa APEX CCD diffractometer	3597 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2502 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.993	R_int = 0.024
16012 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
3597 reflections	Δρ_min = −0.26 e Å⁻³
190 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
N1	0.25032 (15)	0.66502 (15)	0.33833 (5)	0.0436 (3)
N2	0.14194 (13)	0.77204 (14)	0.45776 (5)	0.0392 (3)
N3	0.30313 (15)	0.37642 (14)	0.50779 (5)	0.0413 (3)
N4	0.38605 (15)	−0.08636 (16)	0.70573 (5)	0.0454 (3)
H4	0.3774	−0.0851	0.7470	0.054*
N5	0.42455 (17)	−0.22452 (16)	0.67229 (6)	0.0515 (3)
C1	0.18211 (15)	0.82051 (17)	0.34459 (6)	0.0368 (3)
C2	0.16182 (18)	0.9289 (2)	0.29041 (6)	0.0469 (3)
H2	0.1980	0.8960	0.2509	0.056*
C3	0.08916 (19)	1.0817 (2)	0.29612 (7)	0.0507 (4)
H3	0.0724	1.1511	0.2598	0.061*
C4	0.03910 (19)	1.1364 (2)	0.35576 (7)	0.0490 (4)
H4A	−0.0073	1.2426	0.3589	0.059*
C5	0.05790 (18)	1.03530 (18)	0.40912 (7)	0.0440 (3)
H5	0.0247	1.0724	0.4486	0.053*
C6	0.12780 (16)	0.87452 (17)	0.40443 (6)	0.0361 (3)
C7	0.26273 (18)	0.57069 (18)	0.39027 (6)	0.0436 (3)
H7	0.3088	0.4642	0.3877	0.052*
C8	0.20879 (16)	0.62367 (16)	0.45062 (6)	0.0374 (3)
C9	0.22517 (17)	0.51440 (18)	0.50816 (6)	0.0411 (3)
H9	0.1773	0.5475	0.5455	0.049*
C10	0.32246 (16)	0.27137 (17)	0.56339 (6)	0.0369 (3)
C11	0.36804 (16)	0.10932 (16)	0.55175 (6)	0.0375 (3)
H11	0.3848	0.0756	0.5098	0.045*
C12	0.38887 (16)	−0.00418 (17)	0.60359 (6)	0.0360 (3)
C13	0.36273 (15)	0.04951 (17)	0.66654 (6)	0.0365 (3)
C14	0.42856 (19)	−0.17552 (18)	0.61149 (6)	0.0460 (3)
H14	0.4543	−0.2451	0.5778	0.055*
C15	0.32249 (17)	0.21454 (18)	0.67939 (6)	0.0421 (3)
H15	0.3096	0.2496	0.7216	0.051*
C16	0.30258 (18)	0.32333 (18)	0.62789 (6)	0.0427 (3)
H16	0.2754	0.4339	0.6354	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0514 (6)	0.0477 (7)	0.0324 (5)	0.0016 (5)	0.0079 (4)	−0.0037 (5)
N2	0.0438 (6)	0.0433 (6)	0.0313 (5)	0.0018 (5)	0.0081 (4)	0.0014 (4)
N3	0.0508 (6)	0.0404 (6)	0.0333 (5)	−0.0004 (5)	0.0073 (4)	0.0023 (4)
N4	0.0577 (7)	0.0510 (7)	0.0279 (5)	−0.0001 (5)	0.0070 (5)	0.0050 (5)
N5	0.0698 (8)	0.0469 (7)	0.0377 (6)	0.0017 (6)	0.0070 (5)	0.0050 (5)
C1	0.0357 (6)	0.0445 (7)	0.0304 (6)	−0.0040 (5)	0.0046 (4)	−0.0005 (5)
C2	0.0492 (7)	0.0593 (9)	0.0333 (6)	−0.0023 (7)	0.0096 (5)	0.0060 (6)
C3	0.0494 (8)	0.0581 (9)	0.0453 (8)	−0.0007 (7)	0.0087 (6)	0.0184 (7)
C4	0.0473 (7)	0.0466 (8)	0.0536 (8)	0.0046 (6)	0.0085 (6)	0.0093 (7)
C5	0.0465 (7)	0.0465 (8)	0.0398 (7)	0.0042 (6)	0.0087 (5)	0.0011 (6)
C6	0.0355 (6)	0.0423 (7)	0.0307 (6)	−0.0030 (5)	0.0046 (4)	0.0000 (5)
C7	0.0530 (8)	0.0435 (8)	0.0347 (6)	0.0041 (6)	0.0065 (5)	−0.0026 (5)
C8	0.0401 (6)	0.0402 (7)	0.0322 (6)	−0.0015 (5)	0.0061 (5)	0.0006 (5)
C9	0.0452 (7)	0.0452 (8)	0.0338 (6)	0.0000 (6)	0.0087 (5)	0.0022 (5)
C10	0.0417 (6)	0.0405 (7)	0.0291 (6)	−0.0015 (5)	0.0071 (5)	0.0001 (5)
C11	0.0440 (6)	0.0435 (7)	0.0264 (5)	0.0002 (5)	0.0098 (5)	−0.0015 (5)
C12	0.0395 (6)	0.0406 (7)	0.0286 (6)	−0.0015 (5)	0.0067 (4)	−0.0007 (5)
C13	0.0367 (6)	0.0468 (8)	0.0264 (5)	−0.0026 (5)	0.0054 (4)	0.0012 (5)
C14	0.0604 (8)	0.0425 (8)	0.0356 (7)	0.0029 (6)	0.0075 (6)	0.0008 (6)
C15	0.0489 (7)	0.0516 (8)	0.0265 (6)	0.0014 (6)	0.0074 (5)	−0.0063 (5)
C16	0.0531 (7)	0.0420 (7)	0.0334 (6)	0.0038 (6)	0.0062 (5)	−0.0063 (5)

Geometric parameters (Å, º) top

N1—C7	1.3053 (17)	C5—C6	1.4070 (19)
N1—C1	1.3670 (17)	C5—H5	0.9300
N2—C8	1.3136 (17)	C7—C8	1.4225 (17)
N2—C6	1.3668 (16)	C7—H7	0.9300
N3—C9	1.2610 (18)	C8—C9	1.4684 (17)
N3—C10	1.4162 (16)	C9—H9	0.9300
N4—C13	1.3568 (17)	C10—C11	1.3768 (18)
N4—N5	1.3576 (17)	C10—C16	1.4185 (17)
N4—H4	0.8600	C11—C12	1.3989 (17)
N5—C14	1.3169 (17)	C11—H11	0.9300
C1—C2	1.4094 (18)	C12—C13	1.4039 (16)
C1—C6	1.4167 (17)	C12—C14	1.4150 (19)
C2—C3	1.360 (2)	C13—C15	1.3941 (19)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.402 (2)	C15—C16	1.3691 (18)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.3605 (19)	C16—H16	0.9300
C4—H4A	0.9300

Cg1···Cg3ⁱ	3.7080 (2)	Cg2···Cg3ⁱⁱ	3.8220 (5)

C7—N1—C1	116.38 (11)	N2—C8—C7	121.92 (12)
C8—N2—C6	116.81 (10)	N2—C8—C9	116.67 (11)
C9—N3—C10	121.52 (11)	C7—C8—C9	121.40 (12)
C13—N4—N5	112.15 (10)	N3—C9—C8	121.03 (12)
C13—N4—H4	123.9	N3—C9—H9	119.5
N5—N4—H4	123.9	C8—C9—H9	119.5
C14—N5—N4	105.65 (12)	C11—C10—N3	115.26 (11)
N1—C1—C2	119.81 (11)	C11—C10—C16	119.99 (12)
N1—C1—C6	121.24 (11)	N3—C10—C16	124.73 (12)
C2—C1—C6	118.94 (12)	C10—C11—C12	119.44 (11)
C3—C2—C1	119.78 (13)	C10—C11—H11	120.3
C3—C2—H2	120.1	C12—C11—H11	120.3
C1—C2—H2	120.1	C11—C12—C13	119.28 (12)
C2—C3—C4	121.20 (13)	C11—C12—C14	136.49 (12)
C2—C3—H3	119.4	C13—C12—C14	104.21 (11)
C4—C3—H3	119.4	N4—C13—C15	131.95 (11)
C5—C4—C3	120.49 (14)	N4—C13—C12	106.21 (12)
C5—C4—H4A	119.8	C15—C13—C12	121.83 (12)
C3—C4—H4A	119.8	N5—C14—C12	111.77 (12)
C4—C5—C6	119.80 (13)	N5—C14—H14	124.1
C4—C5—H5	120.1	C12—C14—H14	124.1
C6—C5—H5	120.1	C16—C15—C13	117.81 (11)
N2—C6—C5	119.47 (11)	C16—C15—H15	121.1
N2—C6—C1	120.78 (12)	C13—C15—H15	121.1
C5—C6—C1	119.75 (12)	C15—C16—C10	121.58 (13)
N1—C7—C8	122.85 (13)	C15—C16—H16	119.2
N1—C7—H7	118.6	C10—C16—H16	119.2
C8—C7—H7	118.6

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N1ⁱⁱⁱ	0.86	2.31	3.1050 (15)	153

Symmetry code: (iii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₁N₅
M_r	273.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.7015 (6), 8.0330 (6), 20.6034 (16)
β (°)	96.882 (2)
V (Å³)	1265.47 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.27 × 0.08

Data collection
Diffractometer	Bruker Kappa APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.960, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	16012, 3597, 2502
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.698

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.143, 1.03
No. of reflections	3597
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.26

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N1ⁱ	0.86	2.31	3.1050 (15)	152.9

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The X-ray data were collected on the diffractometer facilities at the Indian Institute of Technology, Madras, provided by the Department of Science and Technology. MS thanks the Kerala State Council for Science, Technology and the Environment, Trivandrum, Kerala, for support. DV acknowledges the Council of Scientific and Industrial Research (CSIR), India, for financial assistance.

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Varghese, D., Arun, V., Sebastian, M., Leeju, P., Varsha, G. & Yusuff, K. K. M. (2009). Acta Cryst. E65, o435. Web of Science CSD CrossRef IUCr Journals Google Scholar
Varsha, G., Arun, V., Sebastian, M., Leeju, P., Varghese, D. & Yusuff, K. K. M. (2009). Acta Cryst. E65, o919. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar