5-Amino-3-(4-pyrid­yl)isoxazole

Yao, Z.; Deng, J.-C.

doi:10.1107/S160053680706309X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o131

https://doi.org/10.1107/S160053680706309X

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5-Amino-3-(4-pyridyl)isoxazole

Zheng Yao ^a and Jian-Cheng Deng ^a ^*

^aCollege of Chemistry, Xiangtan University, Hunan 411105, People's Republic of China
^*Correspondence e-mail: djcwye@163.com

(Received 22 October 2007; accepted 25 November 2007; online 6 December 2007)

In the title compound, C₈H₇N₃O, there are two independent molecules in the asymmetric unit, in which the angles between the pyridine ring and the isoxazole ring are 35.8 (6) and 10.6 (2)°. The crystal packing is stabilized by N—H⋯N hydrogen bonds, which result in the molecules forming a two-dimensional supramolecular layer.

Related literature

The title compound was prepared according to a known procedure (Schmidt et al., 1966 ). For hydrogen-bond motif definitions, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₇N₃O
M_r = 161.17
Monoclinic, P 2₁ /c
a = 14.6411 (13) Å
b = 10.9272 (10) Å
c = 10.0060 (9) Å
β = 106.9870 (10)°
V = 1531.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 187 (2) K
0.42 × 0.18 × 0.10 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.960, T_max = 0.990
8396 measured reflections
3018 independent reflections
2509 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.120
S = 1.02
3018 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N4	0.88	2.09	2.970 (2)	177
N3—H3B⋯N2ⁱ	0.88	2.20	3.077 (2)	169
N6—H6A⋯N1ⁱⁱ	0.88	2.12	2.976 (2)	164
N6—H6B⋯N5ⁱⁱⁱ	0.88	2.09	2.970 (2)	174
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z+1; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680706309X/bv2079sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706309X/bv2079Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is an intermediate for our drug development program. Its structure is shown in Fig. 1. The asymmetric unit was formed by two independent molecules, in which the angles between the pyridine ring and the isoxazole ring are 35.8 (6)° and 10.6 (2)° respectively. Four types of N—H···N hydrogen bonds in the structure are present, which generate two rings, R₄⁴(18) and R₄⁴(28) (Bernstein et al., 1995). These hydrogen bonds extend the monomer into a two-dimensional supramolecular layer (Fig. 2 and Table 1).

Related literature top

The title compound was prepared according to a known procedure (Schmidt et al., 1966). For hydrogen-bond motif definitions, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared according to a known procedure (Schmidt et al., 1966). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a ethanol solution at room temperature.

Structure description top

The title compound was prepared according to a known procedure (Schmidt et al., 1966). For hydrogen-bond motif definitions, see: Bernstein et al. (1995).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

	Fig. 1. A view of (I), with the atom-labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. View of the three-dimensional supramolecular structure in (I). Dashed lines indicate hydrogen bonds.

5-amino-3-(4-pyridyl)isoxazole top

Crystal data top

C₈H₇N₃O	F(000) = 672
M_r = 161.17	D_x = 1.398 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2830 reflections
a = 14.6411 (13) Å	θ = 2.4–25.9°
b = 10.9272 (10) Å	µ = 0.10 mm⁻¹
c = 10.0060 (9) Å	T = 187 K
β = 106.987 (1)°	Block, colourless
V = 1531.0 (2) Å³	0.42 × 0.18 × 0.10 mm
Z = 8

Data collection top

Bruker APEX CCD area-detector diffractometer	3018 independent reflections
Radiation source: fine-focus sealed tube	2509 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 26.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→14
T_min = 0.960, T_max = 0.990	k = −10→13
8396 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.07P)² + 0.2315P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3018 reflections	Δρ_max = 0.23 e Å⁻³
218 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (10)

Crystal data top

C₈H₇N₃O	V = 1531.0 (2) Å³
M_r = 161.17	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.6411 (13) Å	µ = 0.10 mm⁻¹
b = 10.9272 (10) Å	T = 187 K
c = 10.0060 (9) Å	0.42 × 0.18 × 0.10 mm
β = 106.987 (1)°

Data collection top

Bruker APEX CCD area-detector diffractometer	3018 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2509 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.990	R_int = 0.025
8396 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
3018 reflections	Δρ_min = −0.23 e Å⁻³
218 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
O1	0.46333 (7)	0.85688 (9)	0.20940 (11)	0.0346 (3)
O2	0.00420 (8)	0.88480 (9)	0.77638 (11)	0.0336 (3)
N1	0.79693 (9)	0.83254 (13)	−0.07659 (13)	0.0383 (3)
N2	0.52225 (9)	0.80823 (11)	0.13072 (13)	0.0337 (3)
N3	0.44141 (10)	1.03237 (12)	0.31848 (14)	0.0388 (3)
H3A	0.3946	0.9950	0.3407	0.047*
H3B	0.4558	1.1086	0.3447	0.047*
N4	0.28672 (10)	0.90935 (13)	0.40458 (14)	0.0398 (3)
N5	0.06798 (9)	0.93321 (11)	0.70626 (14)	0.0359 (3)
N6	−0.06051 (10)	0.70441 (11)	0.81376 (14)	0.0377 (3)
H6A	−0.0927	0.7458	0.8606	0.045*
H6B	−0.0675	0.6246	0.8048	0.045*
C1	0.72429 (11)	0.75481 (15)	−0.08875 (15)	0.0358 (4)
H1	0.7222	0.6830	−0.1430	0.043*
C2	0.65244 (11)	0.77244 (14)	−0.02749 (15)	0.0346 (4)
H2	0.6026	0.7141	−0.0398	0.042*
C3	0.65383 (10)	0.87660 (13)	0.05244 (14)	0.0271 (3)
C4	0.72841 (11)	0.95824 (14)	0.06540 (16)	0.0368 (4)
H4	0.7322	1.0310	0.1188	0.044*
C5	0.79718 (12)	0.93253 (15)	−0.00027 (18)	0.0419 (4)
H5	0.8477	0.9896	0.0096	0.050*
C6	0.58040 (10)	0.89855 (13)	0.12468 (13)	0.0270 (3)
C7	0.49043 (11)	0.97363 (13)	0.24510 (14)	0.0289 (3)
C8	0.56482 (10)	1.00383 (13)	0.19470 (14)	0.0292 (3)
H8	0.5984	1.0793	0.2049	0.035*
C9	0.29569 (12)	0.80896 (15)	0.48351 (17)	0.0399 (4)
H9	0.3461	0.7540	0.4845	0.048*
C10	0.23625 (11)	0.77991 (14)	0.56385 (16)	0.0351 (4)
H10	0.2452	0.7065	0.6170	0.042*
C11	0.16304 (10)	0.86076 (13)	0.56504 (14)	0.0286 (3)
C12	0.15291 (11)	0.96543 (14)	0.48390 (15)	0.0331 (4)
H12	0.1038	1.0227	0.4820	0.040*
C13	0.21520 (12)	0.98536 (15)	0.40568 (16)	0.0379 (4)
H13	0.2068	1.0570	0.3496	0.045*
C14	0.09696 (10)	0.83758 (13)	0.65003 (14)	0.0272 (3)
C15	0.05754 (11)	0.72799 (13)	0.67909 (15)	0.0310 (3)
H15	0.0689	0.6476	0.6514	0.037*
C16	−0.00128 (10)	0.76260 (13)	0.75652 (14)	0.0274 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0346 (6)	0.0288 (6)	0.0488 (6)	−0.0019 (4)	0.0251 (5)	−0.0016 (5)
O2	0.0403 (6)	0.0237 (5)	0.0474 (6)	−0.0025 (4)	0.0294 (5)	−0.0020 (4)
N1	0.0352 (7)	0.0459 (8)	0.0394 (7)	0.0043 (6)	0.0198 (6)	0.0003 (6)
N2	0.0330 (7)	0.0304 (7)	0.0443 (7)	0.0000 (5)	0.0216 (6)	−0.0034 (5)
N3	0.0443 (8)	0.0306 (7)	0.0545 (8)	−0.0018 (6)	0.0347 (7)	−0.0025 (6)
N4	0.0369 (8)	0.0452 (8)	0.0452 (7)	−0.0045 (6)	0.0242 (6)	−0.0018 (6)
N5	0.0415 (8)	0.0270 (7)	0.0502 (8)	−0.0038 (6)	0.0303 (6)	0.0000 (6)
N6	0.0488 (8)	0.0247 (7)	0.0527 (8)	−0.0031 (6)	0.0353 (7)	−0.0018 (6)
C1	0.0382 (9)	0.0391 (9)	0.0328 (8)	0.0022 (7)	0.0146 (7)	−0.0053 (7)
C2	0.0331 (8)	0.0370 (9)	0.0361 (8)	−0.0039 (7)	0.0138 (7)	−0.0038 (7)
C3	0.0270 (7)	0.0287 (8)	0.0268 (7)	0.0030 (6)	0.0098 (6)	0.0026 (6)
C4	0.0364 (9)	0.0340 (9)	0.0458 (9)	−0.0031 (7)	0.0209 (7)	−0.0060 (7)
C5	0.0382 (9)	0.0418 (9)	0.0538 (10)	−0.0065 (7)	0.0263 (8)	−0.0063 (8)
C6	0.0251 (7)	0.0283 (7)	0.0284 (7)	0.0005 (6)	0.0088 (6)	0.0043 (6)
C7	0.0321 (8)	0.0258 (8)	0.0313 (7)	0.0020 (6)	0.0129 (6)	0.0030 (6)
C8	0.0308 (8)	0.0269 (7)	0.0343 (7)	−0.0030 (6)	0.0164 (6)	−0.0006 (6)
C9	0.0351 (9)	0.0421 (10)	0.0491 (9)	0.0051 (7)	0.0225 (7)	0.0015 (8)
C10	0.0353 (8)	0.0328 (8)	0.0417 (8)	0.0037 (7)	0.0181 (7)	0.0040 (7)
C11	0.0270 (7)	0.0300 (8)	0.0312 (7)	−0.0035 (6)	0.0124 (6)	−0.0026 (6)
C12	0.0336 (8)	0.0314 (8)	0.0398 (8)	0.0011 (6)	0.0193 (7)	0.0023 (7)
C13	0.0431 (9)	0.0347 (9)	0.0423 (9)	−0.0030 (7)	0.0225 (7)	0.0038 (7)
C14	0.0266 (7)	0.0268 (7)	0.0301 (7)	0.0015 (6)	0.0113 (6)	0.0017 (6)
C15	0.0387 (8)	0.0223 (7)	0.0386 (8)	0.0016 (6)	0.0214 (7)	0.0006 (6)
C16	0.0309 (7)	0.0227 (7)	0.0322 (7)	0.0010 (6)	0.0150 (6)	0.0016 (6)

Geometric parameters (Å, º) top

O1—C7	1.3527 (17)	C3—C4	1.386 (2)
O1—N2	1.4295 (14)	C3—C6	1.4798 (18)
O2—C16	1.3490 (17)	C4—C5	1.382 (2)
O2—N5	1.4237 (14)	C4—H4	0.9500
N1—C5	1.332 (2)	C5—H5	0.9500
N1—C1	1.339 (2)	C6—C8	1.3999 (19)
N2—C6	1.3164 (18)	C7—C8	1.3677 (19)
N3—C7	1.3319 (18)	C8—H8	0.9500
N3—H3A	0.8800	C9—C10	1.383 (2)
N3—H3B	0.8800	C9—H9	0.9500
N4—C9	1.336 (2)	C10—C11	1.392 (2)
N4—C13	1.339 (2)	C10—H10	0.9500
N5—C14	1.3145 (17)	C11—C12	1.385 (2)
N6—C16	1.3322 (18)	C11—C14	1.4847 (18)
N6—H6A	0.8800	C12—C13	1.3816 (19)
N6—H6B	0.8800	C12—H12	0.9500
C1—C2	1.377 (2)	C13—H13	0.9500
C1—H1	0.9500	C14—C15	1.3963 (19)
C2—C3	1.388 (2)	C15—C16	1.3692 (19)
C2—H2	0.9500	C15—H15	0.9500

C7—O1—N2	108.58 (10)	N3—C7—O1	115.87 (13)
C16—O2—N5	108.34 (10)	N3—C7—C8	134.62 (14)
C5—N1—C1	116.20 (13)	O1—C7—C8	109.51 (12)
C6—N2—O1	104.42 (11)	C7—C8—C6	104.48 (12)
C7—N3—H3A	120.0	C7—C8—H8	127.8
C7—N3—H3B	120.0	C6—C8—H8	127.8
H3A—N3—H3B	120.0	N4—C9—C10	124.22 (15)
C9—N4—C13	116.52 (13)	N4—C9—H9	117.9
C14—N5—O2	104.82 (10)	C10—C9—H9	117.9
C16—N6—H6A	120.0	C9—C10—C11	118.44 (14)
C16—N6—H6B	120.0	C9—C10—H10	120.8
H6A—N6—H6B	120.0	C11—C10—H10	120.8
N1—C1—C2	124.11 (14)	C12—C11—C10	118.03 (13)
N1—C1—H1	117.9	C12—C11—C14	120.03 (13)
C2—C1—H1	117.9	C10—C11—C14	121.94 (13)
C1—C2—C3	119.13 (14)	C13—C12—C11	119.13 (14)
C1—C2—H2	120.4	C13—C12—H12	120.4
C3—C2—H2	120.4	C11—C12—H12	120.4
C4—C3—C2	117.40 (13)	N4—C13—C12	123.65 (15)
C4—C3—C6	120.98 (13)	N4—C13—H13	118.2
C2—C3—C6	121.60 (13)	C12—C13—H13	118.2
C5—C4—C3	119.20 (14)	N5—C14—C15	112.83 (12)
C5—C4—H4	120.4	N5—C14—C11	117.08 (12)
C3—C4—H4	120.4	C15—C14—C11	130.08 (12)
N1—C5—C4	123.96 (15)	C16—C15—C14	104.33 (12)
N1—C5—H5	118.0	C16—C15—H15	127.8
C4—C5—H5	118.0	C14—C15—H15	127.8
N2—C6—C8	113.02 (12)	N6—C16—O2	115.30 (12)
N2—C6—C3	118.22 (13)	N6—C16—C15	135.03 (14)
C8—C6—C3	128.72 (13)	O2—C16—C15	109.67 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N4	0.88	2.09	2.970 (2)	177
N3—H3B···N2ⁱ	0.88	2.20	3.077 (2)	169
N6—H6A···N1ⁱⁱ	0.88	2.12	2.976 (2)	164
N6—H6B···N5ⁱⁱⁱ	0.88	2.09	2.970 (2)	174

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z+1; (iii) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₇N₃O
M_r	161.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	187
a, b, c (Å)	14.6411 (13), 10.9272 (10), 10.0060 (9)
β (°)	106.987 (1)
V (Å³)	1531.0 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.42 × 0.18 × 0.10

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.960, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	8396, 3018, 2509
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.120, 1.02
No. of reflections	3018
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N4	0.88	2.09	2.970 (2)	177
N3—H3B···N2ⁱ	0.88	2.20	3.077 (2)	169
N6—H6A···N1ⁱⁱ	0.88	2.12	2.976 (2)	164
N6—H6B···N5ⁱⁱⁱ	0.88	2.09	2.970 (2)	174

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z+1; (iii) −x, y−1/2, −z+3/2.

Acknowledgements

This work was supported by the National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Changchun, China.

References

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