N′-(4-Methoxy­benzo­yl)pyridine-2-carbohydrazide

Zhang, H.; Wang, Z.; Liu, Y.

doi:10.1107/S1600536810013437

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1145

https://doi.org/10.1107/S1600536810013437

Open

access

N′-(4-Methoxybenzoyl)pyridine-2-carbohydrazide

Hai Zhang,^a Zuoxiang Wang ^a ^* and Yan Liu ^a

^aSchool of Chemistry and Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: wangzx0908@yahoo.com.cn

(Received 19 March 2010; accepted 12 April 2010; online 24 April 2010)

The crystal structure of the title compound, C₁₄H₁₃N₃O₃, exhibits two intermolecular N—H⋯O hydrogen bonds.

Related literature

For general background to the coordination chemistry of pyridine derivatives, see: Koningsbruggen et al. (1997 ); Klingele & Brooker (2003 ); Suksrichavalit et al. (2009 ). For their biological activity, see: Tozkoparan et al. (2000 ); Grénman et al. (2003 ); Alagarsamy et al. (2008 ); Isloor et al. (2009 ). For their syntheses, see: Klingsberg (1958 ); Potts (1961 ).

Experimental

Crystal data

C₁₄H₁₃N₃O₃
M_r = 271.27
Monoclinic, P 2₁ /c
a = 14.836 (3) Å
b = 11.6078 (17) Å
c = 7.6499 (12) Å
β = 97.137 (11)°
V = 1307.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.18 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.976, T_max = 0.982
13109 measured reflections
2957 independent reflections
1909 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.143
S = 1.02
2957 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.85	2.11	2.9479 (19)	168
N2—H2A⋯O2ⁱⁱ	0.85	2.13	2.938 (2)	159
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013437/om2329sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013437/om2329Isup2.hkl

checkCIF report

Comment top

As the 1,2,4-triazole ring possesses strong electron donors, the coordination chemistry of 1,2,4-triazole derivatives has gained a great deal of attention in recent years (Koningsbruggen et al., 1997; Klingele & Brooker 2003; Suksrichavalit et al., 2009). Some 1,2,4-triazole compounds have biological activity (Tozkoparan et al., 2000; Grénman et al., 2003; Alagarsamy et al., 2008; Isloor et al., 2009). We report here the crystal structure of the title compound, which can be used to synthesize 3(or 5)-(2-pyridyl)-1,2,4-triazole derivatives (Klingsberg, 1958; Potts, 1961).

The stucture of the title compound is shown in Fig. 1. The structure displays two N—H···O intermolecular hydrogen bonds.

Related literature top

For general background to the coordination chemistry of pyridine derivatives, see: Koningsbruggen et al. (1997); Klingele & Brooker (2003); Suksrichavalit et al. (2009). For their biological activity, see: Tozkoparan et al. (2000); Grénman et al. (2003); Alagarsamy et al. (2008); Isloor et al. (2009). For their syntheses, see: Klingsberg (1958); Potts (1961).

Experimental top

The title compound was prepared by the reaction of 2-picolinyl hydrazide (2.75 g, 20 mmol) with 4-methoxybenzoyl chloride (3.5 g, 20 mmol) in 30 ml N,N-dimethylacetamide at room temperature. The colorless product was collected by recrystallization from ethanol, and the single crystals suitable for X-ray diffraction were selected.

Structure description top

The stucture of the title compound is shown in Fig. 1. The structure displays two N—H···O intermolecular hydrogen bonds.

For general background to the coordination chemistry of pyridine derivatives, see: Koningsbruggen et al. (1997); Klingele & Brooker (2003); Suksrichavalit et al. (2009). For their biological activity, see: Tozkoparan et al. (2000); Grénman et al. (2003); Alagarsamy et al. (2008); Isloor et al. (2009). For their syntheses, see: Klingsberg (1958); Potts (1961).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atomic labelling. Displacement ellipsoids are shown at 30% probability level.

N'-(4-Methoxybenzoyl)pyridine-2-carbohydrazide top

Crystal data top

C₁₄H₁₃N₃O₃	F(000) = 568
M_r = 271.27	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.836 (3) Å	Cell parameters from 2772 reflections
b = 11.6078 (17) Å	θ = 2.8–27.5°
c = 7.6499 (12) Å	µ = 0.10 mm⁻¹
β = 97.137 (11)°	T = 293 K
V = 1307.2 (4) Å³	Block, colorless
Z = 4	0.25 × 0.20 × 0.18 mm

Data collection top

Rigaku SCXmini diffractometer	2957 independent reflections
Radiation source: fine-focus sealed tube	1909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −19→19
T_min = 0.976, T_max = 0.982	k = −15→14
13109 measured reflections	l = −9→9

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)] = 0.053	H-atom parameters constrained
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.0677P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2957 reflections	Δρ_max = 0.16 e Å⁻³
183 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.041 (5)

Crystal data top

C₁₄H₁₃N₃O₃	V = 1307.2 (4) Å³
M_r = 271.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.836 (3) Å	µ = 0.10 mm⁻¹
b = 11.6078 (17) Å	T = 293 K
c = 7.6499 (12) Å	0.25 × 0.20 × 0.18 mm
β = 97.137 (11)°

Data collection top

Rigaku SCXmini diffractometer	2957 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1909 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.982	R_int = 0.053
13109 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
2957 reflections	Δρ_min = −0.18 e Å⁻³
183 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.91128 (11)	0.22439 (14)	0.9042 (2)	0.0411 (4)
C2	0.97228 (12)	0.13505 (15)	0.8969 (2)	0.0543 (5)
H2	0.9527	0.0595	0.9075	0.065*
C3	1.06100 (13)	0.15577 (17)	0.8744 (3)	0.0598 (5)
H3	1.1007	0.0944	0.8668	0.072*
C4	1.09167 (12)	0.26761 (16)	0.8629 (3)	0.0526 (5)
C5	1.03233 (13)	0.35724 (16)	0.8720 (3)	0.0569 (5)
H5	1.0525	0.4328	0.8656	0.068*
C6	0.94239 (12)	0.33527 (15)	0.8909 (2)	0.0520 (5)
H6	0.9023	0.3965	0.8946	0.062*
C7	0.81706 (11)	0.19679 (14)	0.9344 (2)	0.0433 (4)
C8	1.21797 (14)	0.3917 (2)	0.8418 (4)	0.0946 (9)
H8A	1.1887	0.4334	0.7421	0.142*
H8B	1.2819	0.3868	0.8340	0.142*
H8C	1.2083	0.4311	0.9482	0.142*
C9	0.52469 (11)	0.13673 (14)	0.8280 (2)	0.0432 (4)
C10	0.41189 (12)	0.18980 (18)	0.9872 (3)	0.0589 (5)
H10	0.3898	0.2394	1.0674	0.071*
C11	0.35667 (13)	0.10217 (18)	0.9177 (3)	0.0635 (6)
H11	0.2992	0.0919	0.9517	0.076*
C12	0.38794 (14)	0.03054 (18)	0.7977 (3)	0.0679 (6)
H12	0.3516	−0.0289	0.7473	0.081*
C13	0.47394 (13)	0.04696 (16)	0.7517 (3)	0.0572 (5)
H13	0.4970	−0.0015	0.6712	0.069*
C14	0.61801 (12)	0.15765 (15)	0.7797 (2)	0.0448 (4)
N1	0.75270 (10)	0.26729 (12)	0.8514 (2)	0.0500 (4)
H1A	0.7632	0.3096	0.7655	0.075*
N2	0.66187 (9)	0.24618 (13)	0.8666 (2)	0.0507 (4)
H2A	0.6435	0.2881	0.9461	0.076*
N3	0.49533 (9)	0.20769 (13)	0.9461 (2)	0.0507 (4)
O1	0.79830 (8)	0.11775 (10)	1.03016 (15)	0.0530 (4)
O2	0.65007 (9)	0.10076 (11)	0.66877 (17)	0.0590 (4)
O3	1.18109 (9)	0.27954 (12)	0.8433 (2)	0.0759 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0422 (9)	0.0415 (9)	0.0399 (9)	0.0003 (7)	0.0060 (7)	0.0012 (7)
C2	0.0473 (11)	0.0427 (10)	0.0740 (13)	−0.0009 (8)	0.0114 (9)	0.0056 (9)
C3	0.0489 (11)	0.0502 (11)	0.0822 (14)	0.0078 (9)	0.0150 (10)	0.0052 (10)
C4	0.0411 (10)	0.0567 (11)	0.0607 (11)	−0.0028 (8)	0.0090 (8)	0.0078 (9)
C5	0.0511 (11)	0.0447 (10)	0.0752 (14)	−0.0067 (9)	0.0089 (10)	0.0042 (9)
C6	0.0462 (10)	0.0426 (10)	0.0676 (12)	0.0032 (8)	0.0091 (9)	−0.0022 (9)
C7	0.0457 (10)	0.0427 (9)	0.0429 (9)	−0.0025 (8)	0.0117 (8)	−0.0026 (8)
C8	0.0509 (13)	0.0814 (17)	0.153 (3)	−0.0185 (11)	0.0175 (15)	0.0266 (17)
C9	0.0432 (10)	0.0418 (9)	0.0447 (9)	0.0065 (7)	0.0066 (8)	0.0058 (7)
C10	0.0438 (11)	0.0659 (13)	0.0696 (13)	−0.0007 (9)	0.0169 (10)	−0.0102 (10)
C11	0.0418 (10)	0.0664 (13)	0.0831 (14)	−0.0055 (10)	0.0110 (10)	0.0014 (12)
C12	0.0587 (13)	0.0552 (12)	0.0882 (16)	−0.0154 (10)	0.0035 (11)	−0.0051 (11)
C13	0.0620 (12)	0.0468 (10)	0.0631 (12)	0.0005 (9)	0.0095 (10)	−0.0055 (9)
C14	0.0452 (10)	0.0432 (10)	0.0468 (10)	0.0097 (8)	0.0092 (8)	0.0057 (8)
N1	0.0394 (8)	0.0553 (9)	0.0583 (10)	0.0028 (7)	0.0179 (7)	0.0104 (7)
N2	0.0401 (8)	0.0549 (9)	0.0601 (10)	0.0024 (7)	0.0183 (7)	−0.0033 (7)
N3	0.0400 (8)	0.0549 (9)	0.0583 (9)	−0.0009 (7)	0.0105 (7)	−0.0059 (7)
O1	0.0513 (8)	0.0525 (7)	0.0567 (8)	−0.0058 (6)	0.0124 (6)	0.0079 (6)
O2	0.0620 (8)	0.0579 (8)	0.0601 (8)	0.0135 (6)	0.0192 (6)	−0.0035 (6)
O3	0.0428 (7)	0.0719 (10)	0.1157 (13)	−0.0033 (7)	0.0201 (8)	0.0171 (9)

Geometric parameters (Å, º) top

C1—C6	1.375 (2)	C8—H8C	0.9600
C1—C2	1.382 (2)	C9—N3	1.335 (2)
C1—C7	1.480 (2)	C9—C13	1.373 (2)
C2—C3	1.370 (2)	C10—N3	1.331 (2)
C2—H2	0.9300	C10—C11	1.371 (3)
C3—C4	1.382 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.362 (3)
C4—O3	1.361 (2)	C11—H11	0.9300
C4—C5	1.370 (3)	C12—C13	1.378 (3)
C5—C6	1.384 (2)	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300
C6—H6	0.9300	C14—O2	1.2179 (19)
C7—O1	1.2276 (19)	C14—N2	1.347 (2)
C7—N1	1.354 (2)	C14—C9	1.496 (2)
C8—O3	1.413 (3)	N1—N2	1.389 (2)
C8—H8A	0.9600	N1—H1A	0.8500
C8—H8B	0.9600	N2—H2A	0.8500

C6—C1—C2	118.15 (16)	O2—C14—N2	123.43 (16)
C6—C1—C7	123.11 (15)	O2—C14—C9	122.51 (16)
C2—C1—C7	118.67 (15)	N2—C14—C9	114.04 (14)
C3—C2—C1	121.17 (17)	N3—C9—C13	123.25 (16)
C3—C2—H2	119.4	N3—C9—C14	117.16 (15)
C1—C2—H2	119.4	C13—C9—C14	119.59 (16)
C2—C3—C4	120.13 (17)	N3—C10—C11	123.56 (18)
C2—C3—H3	119.9	N3—C10—H10	118.2
C4—C3—H3	119.9	C11—C10—H10	118.2
O3—C4—C5	124.74 (17)	C12—C11—C10	118.49 (18)
O3—C4—C3	115.84 (17)	C12—C11—H11	120.8
C5—C4—C3	119.42 (17)	C10—C11—H11	120.8
C4—C5—C6	119.96 (17)	C11—C12—C13	119.42 (18)
C4—C5—H5	120.0	C11—C12—H12	120.3
C6—C5—H5	120.0	C13—C12—H12	120.3
C1—C6—C5	121.14 (16)	C9—C13—C12	118.22 (18)
C1—C6—H6	119.4	C9—C13—H13	120.9
C5—C6—H6	119.4	C12—C13—H13	120.9
O1—C7—N1	122.17 (16)	C7—N1—N2	119.30 (14)
O1—C7—C1	122.91 (16)	C7—N1—H1A	121.7
N1—C7—C1	114.89 (15)	N2—N1—H1A	116.1
O3—C8—H8A	109.5	C14—N2—N1	120.53 (14)
O3—C8—H8B	109.5	C14—N2—H2A	127.8
H8A—C8—H8B	109.5	N1—N2—H2A	111.0
O3—C8—H8C	109.5	C10—N3—C9	117.05 (16)
H8A—C8—H8C	109.5	C4—O3—C8	118.60 (16)
H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85	2.11	2.9479 (19)	168
N2—H2A···O2ⁱⁱ	0.85	2.13	2.938 (2)	159

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O₃
M_r	271.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.836 (3), 11.6078 (17), 7.6499 (12)
β (°)	97.137 (11)
V (Å³)	1307.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.976, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	13109, 2957, 1909
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.143, 1.02
No. of reflections	2957
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

C7—O1	1.2276 (19)	N1—N2	1.389 (2)
C7—N1	1.354 (2)	N1—H1A	0.8500
C14—O2	1.2179 (19)	N2—H2A	0.8500
C14—N2	1.347 (2)

O1—C7—N1	122.17 (16)	O2—C14—N2	123.43 (16)
O1—C7—C1	122.91 (16)	O2—C14—C9	122.51 (16)
N1—C7—C1	114.89 (15)	N2—C14—C9	114.04 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85	2.11	2.9479 (19)	168.0
N2—H2A···O2ⁱⁱ	0.85	2.13	2.938 (2)	158.9

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

Acknowledgements

We are grateful to the Jingye Pharmochemical Pilot Plant for financial assistance though project 8507041056.

References

Alagarsamy, V., Rupeshkumar, M., Kavitha, K., Meena, S., Shankar, D., Siddiqui, A. A. & Rajesh, R. (2008). Eur. J. Med. Chem. 43, 2331–2337. Web of Science CrossRef PubMed CAS Google Scholar
Grénman, H., Salmi, T., Mäki-Arvela, J., Eränen, K., Tirronen, E. & Pehkonen, A. (2003). Org. Process Res. Dev. 7, 942–950. Google Scholar
Isloor, A. M., Kalluraya, B. & Shetty, P. (2009). Eur. J. Med. Chem. 44, 3784–3787. Web of Science CrossRef PubMed CAS Google Scholar
Klingele, M. H. & Brooker, S. (2003). Coord. Chem. Rev. 241, 119–132. Web of Science CrossRef CAS Google Scholar
Klingsberg, E. (1958). J. Org. Chem. 23, 1086–1087. CrossRef CAS Web of Science Google Scholar
Koningsbruggen, P. J., Hassnoot, J. G., Kooijman, H., Reedijk, J. & Spek, A. L. (1997). Inorg. Chem. 36, 2487–2489. CSD CrossRef PubMed Web of Science Google Scholar
Potts, K. T. (1961). Chem. Rev. 61, 87–127. CrossRef CAS Web of Science Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suksrichavalit, T., Prachayasittikul, S., Nantasenamat, C., Isarankurai-Na-Ayudhyal, C. & Prachayasittikul, V. (2009). Eur. J. Inorg. Chem. 44, 3259–3265. CAS Google Scholar
Tozkoparan, B., Gokhan, N., Aktay, G., Yesilada, E. & Ertana, M. (2000). Eur. J. Med. Chem. 35, 743–750. Web of Science CrossRef PubMed CAS Google Scholar