N-Hy­droxy­pyridine-4-carboxamide

Wu, Q.; Yin, H.

doi:10.1107/S1600536811025566

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1905

doi:10.1107/S1600536811025566

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N-Hydroxypyridine-4-carboxamide

Qingkun Wu ^a and Handong Yin ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 2 June 2011; accepted 29 June 2011; online 6 July 2011)

The title compound, C₆H₆N₂O₂, is approximately planar with an r.m.s. deviation for the non-H atoms of 0.052 Å. In the crystal, a two-dimensional array in the bc plane is stabilized by O—H⋯N and N—H⋯O hydrogen bonds.

Related literature

For background to the coordination chemistry of hydroxamic acid derivatives, see: Codd (2008 ). For related structures, see: Wang et al. (1988 ); Makhmudova et al. (2000 ); Golenya et al. (2007 ).

Experimental

Crystal data

C₆H₆N₂O₂
M_r = 138.13
Monoclinic, P 2₁ /c
a = 4.8765 (5) Å
b = 13.4476 (16) Å
c = 9.6656 (11) Å
β = 99.579 (1)°
V = 625.01 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.35 × 0.24 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.961, T_max = 0.983
3030 measured reflections
1092 independent reflections
769 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.115
S = 1.05
1092 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.82	1.92	2.721 (2)	166
N1—H2⋯O2ⁱⁱ	0.86	2.01	2.844 (2)	162
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025566/tk2754sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025566/tk2754Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025566/tk2754Isup3.cml

checkCIF report

Comment top

Hydroxamic acid, R1C(═O)N(R2)OH (R1 = alkyl/aryl; R2 = alkyl/aryl or H), relevant to chemical biology, coordinate a wide variety of metal ions predominantly as the monoanionic hydroxamato or as a dianionic (R2 = H) hydroximato O,O-bidentate chelate (Codd, 2008). To the best of our knowledge, while a large number of transition metal derivatives with hydroxamic acids have been reported, organoantimony complexes with hydroxamic acids are limited. To further extend this field and to construct novel structures of organoantimony, we choose to investigate reactions involving the title compound (I). Herein, we present its crystal structure determination.

In (I), the non-hydrogen atoms are in the same plane (Fig. 1) with the rms deviation being 0.052 Å. All the bond lengths and angles are normal and correspond to those observed in the related compounds (Wang et al., 1988; Makhmudova et al., 2000; Golenya et al., 2007). In the crystal structure, intermolecular O1—H1···N2 and N1—H2···O2 hydrogen bonds (Table 1) link the molecules into a two-dimensional array in the bc plane (Fig. 2).

Related literature top

For background to the coordination chemistry of hydroxamic acid derivatives, see: Codd (2008). For related structures, see: Wang et al. (1988); Makhmudova et al. (2000); Golenya et al. (2007).

Experimental top

4-pyridinecarboxylic acid was dissolved in methanol (50 mL) and concentrated sulfuric acid (5 mL) was added drop wise into the reactor. The mixture was then stirred and refluxed for 3 h, after which time the solution was adjusted to pH 8 by the use of a 5% sodium carbonate aqueous solution. Methyl 4-pyridinecarboxylate was obtained by extraction with diethyl ether. Yield: 61.6%. A mixture of hydroxylamine hydrochloride and sodium hydroxide was added drop wise to the methanol solution of methyl 4-pyridinecarboxylate. The reaction was allowed to continue at room temperature for 72 h, when the mixture was acidified to pH 5.5 by 5% HCl solution. The solvent was removed in vacuo and the product was recrystallized from water to give pale-red crystals. Yield: 82%, M.pt. 421 K.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing atom-labelling and 50% probability displacement ellipsoids.
	Fig. 2. The supramolecular 2-D array in the bc plane stabilised by N—H···O and O—H···N hydrogen bonds (dashed lines).

N-Hydroxypyridine-4-carboxamide top

Crystal data top

C₆H₆N₂O₂	F(000) = 288
M_r = 138.13	D_x = 1.468 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1066 reflections
a = 4.8765 (5) Å	θ = 2.6–26.0°
b = 13.4476 (16) Å	µ = 0.11 mm⁻¹
c = 9.6656 (11) Å	T = 298 K
β = 99.579 (1)°	Block, pale-red
V = 625.01 (12) Å³	0.35 × 0.24 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1092 independent reflections
Radiation source: fine-focus sealed tube	769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
T_min = 0.961, T_max = 0.983	k = −13→16
3030 measured reflections	l = −11→10

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0528P)² + 0.208P] where P = (F_o² + 2F_c²)/3
1092 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₆H₆N₂O₂	V = 625.01 (12) Å³
M_r = 138.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8765 (5) Å	µ = 0.11 mm⁻¹
b = 13.4476 (16) Å	T = 298 K
c = 9.6656 (11) Å	0.35 × 0.24 × 0.15 mm
β = 99.579 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1092 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	769 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.983	R_int = 0.024
3030 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.05	Δρ_max = 0.15 e Å⁻³
1092 reflections	Δρ_min = −0.16 e Å⁻³
92 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O2	0.1487 (3)	0.30086 (10)	0.06585 (14)	0.0430 (4)
O1	−0.1208 (3)	0.35086 (10)	0.27794 (16)	0.0437 (5)
H1	−0.0465	0.4055	0.2770	0.065*
N1	0.0809 (4)	0.27699 (12)	0.28861 (17)	0.0364 (5)
H2	0.1275	0.2453	0.3662	0.044*
C1	0.2019 (4)	0.25531 (14)	0.1785 (2)	0.0324 (5)
C2	0.4074 (4)	0.17092 (14)	0.1980 (2)	0.0331 (5)
N2	0.7903 (4)	0.01429 (13)	0.2167 (2)	0.0477 (5)
C6	0.5567 (5)	0.15118 (16)	0.0916 (2)	0.0420 (6)
H6	0.5325	0.1905	0.0114	0.050*
C3	0.4594 (6)	0.11050 (18)	0.3153 (2)	0.0570 (7)
H3	0.3672	0.1214	0.3908	0.068*
C5	0.7415 (5)	0.07300 (17)	0.1049 (2)	0.0462 (6)
H5	0.8377	0.0606	0.0313	0.055*
C4	0.6486 (6)	0.03405 (19)	0.3196 (3)	0.0659 (8)
H4	0.6790	−0.0061	0.3990	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0581 (10)	0.0425 (9)	0.0303 (8)	0.0067 (8)	0.0127 (7)	0.0035 (6)
O1	0.0467 (9)	0.0354 (8)	0.0525 (10)	0.0019 (7)	0.0187 (7)	−0.0029 (7)
N1	0.0442 (11)	0.0354 (10)	0.0312 (9)	0.0040 (8)	0.0107 (8)	−0.0002 (7)
C1	0.0404 (12)	0.0305 (10)	0.0272 (10)	−0.0053 (9)	0.0084 (9)	−0.0039 (9)
C2	0.0382 (12)	0.0292 (10)	0.0325 (11)	−0.0044 (9)	0.0078 (9)	−0.0043 (8)
N2	0.0514 (12)	0.0356 (10)	0.0584 (12)	0.0025 (9)	0.0162 (10)	0.0023 (9)
C6	0.0448 (13)	0.0485 (14)	0.0341 (12)	0.0047 (11)	0.0103 (10)	0.0022 (9)
C3	0.0782 (19)	0.0518 (15)	0.0495 (14)	0.0206 (13)	0.0353 (13)	0.0163 (11)
C5	0.0455 (14)	0.0488 (14)	0.0469 (14)	0.0045 (11)	0.0156 (11)	−0.0046 (11)
C4	0.090 (2)	0.0537 (16)	0.0620 (17)	0.0249 (15)	0.0364 (16)	0.0262 (13)

Geometric parameters (Å, º) top

O2—C1	1.239 (2)	N2—C5	1.327 (3)
O1—N1	1.390 (2)	N2—C4	1.329 (3)
O1—H1	0.8200	C6—C5	1.377 (3)
N1—C1	1.332 (2)	C6—H6	0.9300
N1—H2	0.8600	C3—C4	1.378 (3)
C1—C2	1.505 (3)	C3—H3	0.9300
C2—C6	1.381 (3)	C5—H5	0.9300
C2—C3	1.384 (3)	C4—H4	0.9300

N1—O1—H1	109.5	C5—C6—H6	120.2
C1—N1—O1	119.96 (16)	C2—C6—H6	120.2
C1—N1—H2	120.0	C4—C3—C2	119.5 (2)
O1—N1—H2	120.0	C4—C3—H3	120.2
O2—C1—N1	122.57 (19)	C2—C3—H3	120.2
O2—C1—C2	121.35 (17)	N2—C5—C6	123.8 (2)
N1—C1—C2	116.07 (17)	N2—C5—H5	118.1
C6—C2—C3	116.7 (2)	C6—C5—H5	118.1
C6—C2—C1	118.33 (18)	N2—C4—C3	123.8 (2)
C3—C2—C1	124.92 (18)	N2—C4—H4	118.1
C5—N2—C4	116.4 (2)	C3—C4—H4	118.1
C5—C6—C2	119.7 (2)

O1—N1—C1—O2	2.4 (3)	C1—C2—C6—C5	−178.48 (19)
O1—N1—C1—C2	−177.12 (15)	C6—C2—C3—C4	−1.3 (4)
O2—C1—C2—C6	6.1 (3)	C1—C2—C3—C4	178.6 (2)
N1—C1—C2—C6	−174.36 (18)	C4—N2—C5—C6	0.2 (3)
O2—C1—C2—C3	−173.7 (2)	C2—C6—C5—N2	−0.9 (3)
N1—C1—C2—C3	5.8 (3)	C5—N2—C4—C3	−0.1 (4)
C3—C2—C6—C5	1.4 (3)	C2—C3—C4—N2	0.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.82	1.92	2.721 (2)	166
N1—H2···O2ⁱⁱ	0.86	2.01	2.844 (2)	162

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

Experimental details

Crystal data
Chemical formula	C₆H₆N₂O₂
M_r	138.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.8765 (5), 13.4476 (16), 9.6656 (11)
β (°)	99.579 (1)
V (Å³)	625.01 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.24 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	3030, 1092, 769
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.115, 1.05
No. of reflections	1092
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.82	1.92	2.721 (2)	166
N1—H2···O2ⁱⁱ	0.86	2.01	2.844 (2)	162

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

Acknowledgements

We acknowledge the National Natural Science Foundation of China (20771053), the National Basic Research Program (No. 2010CB234601) and the Natural Science Foundation of Shandong Province (Y2008B48) for financial support.

References

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