N-p-Tolyl-1,3-selenazolo[5,4-b]pyridin-2-amine

Wu, Z.; Li, Y.; Zhou, H.; Zhou, M.

doi:10.1107/S1600536813023659

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1497

doi:10.1107/S1600536813023659

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N-p-Tolyl-1,3-selenazolo[5,4-b]pyridin-2-amine

Zhaojun Wu,^a Yiqun Li,^a Hua Zhou ^b ^* and Meiyun Zhou ^a

^aDepartment of Chemistry, Jinan University, Guangzhou 510632, People's Republic of China, and ^bDepartment of Food Science and Technology, Jinan, University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: zhouhua5460@jnu.edu.cn

(Received 6 August 2013; accepted 22 August 2013; online 4 September 2013)

In the title compound, C₁₃H₁₁N₃Se, the dihedral angle between the mean plane of the fused selenoazolopyridine ring system and the p-toluidine ring is 14.260 (5)°. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, forming zigzag chains extending along the b-axis direction.

Related literature

For the bioactivity of organoselenium, see: Garud et al. (2007 ); Ling et al. (2010 ); Plamen et al. (2010 ). For crystallographic studies on selenazolo derivatives, see: Plamen et al. (2004 ).

Experimental

Crystal data

C₁₃H₁₁N₃Se
M_r = 288.21
Orthorhombic, P b c a
a = 13.138 (2) Å
b = 10.0323 (19) Å
c = 17.838 (3) Å
V = 2351.2 (7) Å³
Z = 8
Cu Kα radiation
μ = 4.15 mm⁻¹
T = 153 K
0.30 × 0.30 × 0.20 mm

Data collection

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.369, T_max = 0.491
5248 measured reflections
1863 independent reflections
1423 reflections with I > 2σI)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.094
wR(F²) = 0.314
S = 1.28
1863 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 1.47 e Å⁻³
Δρ_min = −2.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10⋯N1ⁱ	0.88	2.11	2.983 (16)	175
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2010 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813023659/zs2275sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023659/zs2275Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813023659/zs2275Isup3.cml

checkCIF report

Comment top

Since the discovery of the importance of Se as a microelement in bacteria and animals, and the function of the selenoenzyme glutathione peroxidase (GPx) as an antioxidant, the interest in organoselenium compounds has increased significantly (Garud et al., 2007; Ling et al., 2010; Plamen et al., 2004, 2010). The design and synthesis of organoselenium compounds, especially Se-containing heterocycles, are our current interest. The title molecule, C₁₃H₁₁N₃Se, (Fig. 1) is built up from two fused rings, viz. the selenazolo and pyridine rings, linked to a p-toluidine group. The dihedral angle between these two ring systems is 14.260 (5)°. In the crystal, the molecules are linked by intermolecular N—H···N hydrogen bonds (Table 1), giving one-dimensional zigzag chains extending along b.

Related literature top

For the bioactivity of organoselenium, see: Garud et al. (2007); Ling et al. (2010); Plamen et al. (2010). For crystallographic studies on selenazolo derivatives, see: Plamen et al. (2004).

Experimental top

To a stirred solution of N-p-tolylformamide (10 mmol) in toluene (100 ml) in an ice bath, Et₃N (4.0 g, 40 mmol) and Se black powder were added. Phosgene (8 g of a 20% solution in toluene) was then added slowly over 30 min. giving an exothermic reaction. After complete addition, the suspension was heated under reflux for 10 h (TLC control). The mixture was filtered and washed with several portions of toluene, and the filtrate was then concentrated, affording the raw isoselenocyanatobenzene. This was added to a stirred solution of 2-chloropyridin-3-amine (1.28 g, 10 mmol) in 2-propanol at room temperature, and the mixture was heated to reflux for 6 h. After filtration, the precipitate was collected as a yellow solid. The impure product was dissolved in CCl₂H₂ at room temperature. Yellow crystals suitable for X-ray analysis (80.2% yield) grew over a period of one week when the solution was exposed to the air.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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, 2010) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

N-p-Tolyl-1,3-selenazolo[5,4-b]pyridin-2-amine top

Crystal data top

C₁₃H₁₁N₃Se	F(000) = 1152
M_r = 288.21	D_x = 1.628 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7867 reflections
a = 13.138 (2) Å	θ = 1.3–61.9°
b = 10.0323 (19) Å	µ = 4.15 mm⁻¹
c = 17.838 (3) Å	T = 153 K
V = 2351.2 (7) Å³	Prism, yellow
Z = 8	0.30 × 0.30 × 0.20 mm

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	1863 independent reflections
Radiation source: fine-focus sealed tube	1423 reflections with I > 2s˘I)
Graphite monochromator	R_int = 0.064
Detector resolution: 16.0288 pixels mm^-1	θ_max = 63.6°, θ_min = 6.0°
ω scans	h = −15→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→11
T_min = 0.369, T_max = 0.491	l = −13→20
5248 measured reflections

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)] = 0.094	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.314	H-atom parameters constrained
S = 1.28	w = 1/[σ²(F_o²) + (0.0796P)² + 53.5115P] where P = (F_o² + 2F_c²)/3
1863 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 1.47 e Å⁻³
0 restraints	Δρ_min = −2.49 e Å⁻³

Crystal data top

C₁₃H₁₁N₃Se	V = 2351.2 (7) Å³
M_r = 288.21	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 13.138 (2) Å	µ = 4.15 mm⁻¹
b = 10.0323 (19) Å	T = 153 K
c = 17.838 (3) Å	0.30 × 0.30 × 0.20 mm

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	1863 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1423 reflections with I > 2s˘I)
T_min = 0.369, T_max = 0.491	R_int = 0.064
5248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.094	0 restraints
wR(F²) = 0.314	H-atom parameters constrained
S = 1.28	w = 1/[σ²(F_o²) + (0.0796P)² + 53.5115P] where P = (F_o² + 2F_c²)/3
1863 reflections	Δρ_max = 1.47 e Å⁻³
155 parameters	Δρ_min = −2.49 e Å⁻³

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
C2	0.1440 (11)	0.5123 (17)	0.1134 (9)	0.058 (4)
H2	0.1245	0.5846	0.0821	0.069*
C3	0.2452 (11)	0.4817 (14)	0.1192 (8)	0.049 (3)
H3	0.2937	0.5321	0.0917	0.058*
C4	0.2779 (10)	0.3779 (13)	0.1647 (7)	0.042 (3)
H4	0.3483	0.3586	0.1694	0.050*
C6	0.1034 (9)	0.3460 (16)	0.1916 (7)	0.045 (3)
C5	0.2051 (9)	0.3016 (13)	0.2038 (7)	0.035 (3)
C8	0.1441 (10)	0.1537 (15)	0.2778 (7)	0.041 (3)
C11	0.2188 (10)	−0.0164 (13)	0.3649 (7)	0.038 (3)
C16	0.3195 (10)	0.0139 (14)	0.3591 (8)	0.045 (3)
H16	0.3399	0.0836	0.3263	0.054*
C15	0.3925 (11)	−0.0535 (18)	0.3993 (8)	0.059 (4)
H15	0.4618	−0.0279	0.3942	0.071*
C14	0.3684 (12)	−0.1555 (19)	0.4460 (8)	0.058 (4)
C13	0.2672 (13)	−0.189 (2)	0.4510 (8)	0.064 (5)
H13	0.2482	−0.2601	0.4834	0.077*
C12	0.1923 (12)	−0.1245 (16)	0.4116 (7)	0.052 (4)
H12	0.1234	−0.1523	0.4156	0.063*
C17	0.4499 (16)	−0.2322 (19)	0.4884 (9)	0.074 (5)
H17A	0.4471	−0.3265	0.4742	0.110*
H17B	0.4380	−0.2236	0.5425	0.110*
H17C	0.5170	−0.1960	0.4760	0.110*
N1	0.0717 (9)	0.4456 (15)	0.1496 (7)	0.058 (4)
N9	0.2255 (8)	0.1982 (14)	0.2518 (6)	0.049 (3)
N10	0.1388 (8)	0.0493 (14)	0.3276 (7)	0.054 (3)
H10	0.0772	0.0197	0.3375	0.065*
Se7	0.01740 (10)	0.22670 (19)	0.24564 (9)	0.0504 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.048 (8)	0.060 (10)	0.066 (10)	0.007 (8)	−0.001 (7)	−0.012 (8)
C3	0.053 (8)	0.028 (7)	0.065 (9)	0.000 (6)	0.001 (7)	0.010 (7)
C4	0.038 (7)	0.035 (8)	0.052 (8)	0.001 (6)	0.000 (6)	0.015 (6)
C6	0.028 (6)	0.066 (10)	0.041 (7)	−0.006 (7)	−0.001 (5)	−0.006 (7)
C5	0.031 (6)	0.032 (7)	0.043 (7)	−0.006 (5)	0.001 (5)	−0.007 (6)
C8	0.036 (7)	0.048 (8)	0.040 (7)	0.016 (6)	0.002 (6)	−0.005 (6)
C11	0.051 (8)	0.032 (7)	0.031 (6)	0.006 (6)	0.005 (5)	−0.003 (6)
C16	0.040 (7)	0.042 (8)	0.052 (8)	0.004 (6)	0.005 (6)	0.017 (7)
C15	0.039 (7)	0.082 (13)	0.056 (9)	0.003 (8)	0.004 (7)	0.004 (9)
C14	0.060 (9)	0.078 (12)	0.036 (7)	0.013 (8)	0.001 (6)	0.007 (8)
C13	0.067 (11)	0.084 (14)	0.041 (8)	−0.006 (9)	0.005 (7)	0.017 (9)
C12	0.055 (9)	0.059 (10)	0.043 (7)	−0.005 (8)	0.004 (7)	−0.006 (7)
C17	0.094 (14)	0.066 (12)	0.061 (10)	0.011 (10)	−0.010 (9)	0.007 (9)
N1	0.036 (6)	0.089 (11)	0.048 (7)	0.018 (7)	−0.007 (5)	0.000 (7)
N9	0.024 (6)	0.082 (10)	0.042 (6)	0.005 (5)	0.002 (4)	0.012 (6)
N10	0.025 (5)	0.082 (10)	0.054 (7)	−0.001 (6)	0.001 (5)	−0.009 (7)
Se7	0.0237 (9)	0.0734 (13)	0.0542 (10)	−0.0005 (7)	−0.0003 (6)	−0.0021 (8)

Geometric parameters (Å, º) top

C2—N1	1.33 (2)	C11—N10	1.408 (17)
C2—C3	1.37 (2)	C11—C12	1.41 (2)
C2—H2	0.9500	C16—C15	1.38 (2)
C3—C4	1.388 (18)	C16—H16	0.9500
C3—H3	0.9500	C15—C14	1.36 (2)
C4—C5	1.410 (17)	C15—H15	0.9500
C4—H4	0.9500	C14—C13	1.37 (2)
C6—N1	1.316 (19)	C14—C17	1.52 (2)
C6—C5	1.425 (18)	C13—C12	1.37 (2)
C6—Se7	1.907 (14)	C13—H13	0.9500
C5—N9	1.371 (17)	C12—H12	0.9500
C8—N9	1.248 (17)	C17—H17A	0.9800
C8—N10	1.375 (18)	C17—H17B	0.9800
C8—Se7	1.907 (12)	C17—H17C	0.9800
C11—C16	1.362 (19)	N10—H10	0.8800

N1—C2—C3	123.0 (16)	C14—C15—C16	121.9 (14)
N1—C2—H2	118.5	C14—C15—H15	119.1
C3—C2—H2	118.5	C16—C15—H15	119.1
C2—C3—C4	120.8 (14)	C15—C14—C13	116.8 (15)
C2—C3—H3	119.6	C15—C14—C17	121.6 (15)
C4—C3—H3	119.6	C13—C14—C17	121.6 (16)
C3—C4—C5	119.2 (12)	C12—C13—C14	123.0 (16)
C3—C4—H4	120.4	C12—C13—H13	118.5
C5—C4—H4	120.4	C14—C13—H13	118.5
N1—C6—C5	128.4 (12)	C13—C12—C11	119.3 (14)
N1—C6—Se7	125.2 (10)	C13—C12—H12	120.4
C5—C6—Se7	106.4 (10)	C11—C12—H12	120.4
N9—C5—C4	126.0 (11)	C14—C17—H17A	109.5
N9—C5—C6	121.0 (11)	C14—C17—H17B	109.5
C4—C5—C6	113.0 (12)	H17A—C17—H17B	109.5
N9—C8—N10	123.7 (12)	C14—C17—H17C	109.5
N9—C8—Se7	119.9 (11)	H17A—C17—H17C	109.5
N10—C8—Se7	116.3 (9)	H17B—C17—H17C	109.5
C16—C11—N10	125.7 (12)	C6—N1—C2	115.7 (12)
C16—C11—C12	117.2 (13)	C8—N9—C5	109.6 (11)
N10—C11—C12	117.1 (12)	C8—N10—C11	128.7 (11)
C11—C16—C15	121.8 (13)	C8—N10—H10	115.7
C11—C16—H16	119.1	C11—N10—H10	115.7
C15—C16—H16	119.1	C8—Se7—C6	82.9 (6)

N1—C2—C3—C4	−1 (2)	N10—C11—C12—C13	−177.9 (13)
C2—C3—C4—C5	2 (2)	C5—C6—N1—C2	1 (2)
C3—C4—C5—N9	−178.7 (13)	Se7—C6—N1—C2	−176.5 (11)
C3—C4—C5—C6	−1.3 (18)	C3—C2—N1—C6	−1 (2)
N1—C6—C5—N9	177.7 (14)	N10—C8—N9—C5	179.9 (12)
Se7—C6—C5—N9	−4.7 (15)	Se7—C8—N9—C5	2.3 (17)
N1—C6—C5—C4	0 (2)	C4—C5—N9—C8	179.0 (13)
Se7—C6—C5—C4	177.8 (9)	C6—C5—N9—C8	1.8 (18)
N10—C11—C16—C15	178.2 (14)	N9—C8—N10—C11	8 (2)
C12—C11—C16—C15	−3 (2)	Se7—C8—N10—C11	−174.5 (11)
C11—C16—C15—C14	1 (2)	C16—C11—N10—C8	1 (2)
C16—C15—C14—C13	0 (2)	C12—C11—N10—C8	−177.8 (13)
C16—C15—C14—C17	178.1 (15)	N9—C8—Se7—C6	−4.1 (12)
C15—C14—C13—C12	0 (3)	N10—C8—Se7—C6	178.1 (11)
C17—C14—C13—C12	−177.8 (15)	N1—C6—Se7—C8	−178.1 (13)
C14—C13—C12—C11	−2 (3)	C5—C6—Se7—C8	4.2 (9)
C16—C11—C12—C13	3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···N1ⁱ	0.88	2.11	2.983 (16)	175

Symmetry code: (i) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···N1ⁱ	0.88	2.11	2.983 (16)	175

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

This work was supported by grants from the National Natural Science Fund (Nos. 31000816 and 21071062) and the high-performance computing platform of Jinan University.

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