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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1145.
Published online 2010 April 24. doi:  10.1107/S1600536810013437
PMCID: PMC2979049

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

Abstract

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 [triangle]); Klingele & Brooker (2003 [triangle]); Suksrichavalit et al. (2009 [triangle]). For their biological activity, see: Tozkoparan et al. (2000 [triangle]); Grénman et al. (2003 [triangle]); Alagarsamy et al. (2008 [triangle]); Isloor et al. (2009 [triangle]). For their syntheses, see: Klingsberg (1958 [triangle]); Potts (1961 [triangle]).

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Object name is e-66-o1145-scheme1.jpg

Experimental

Crystal data

  • C14H13N3O3
  • M r = 271.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1145-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.143
  • S = 1.02
  • 2957 reflections
  • 183 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013437/om2329Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, N atoms to which they are bonded, riding with C—H = 0.93 Å (aromatic), 0.96 Å (methyl) or N—H = 0.85 Å, with Uĩso~(H) = 1.2 or 1.5 times U~eq~(C).

Figures

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

Crystal data

C14H13N3O3F(000) = 568
Mr = 271.27Dx = 1.378 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.836 (3) ÅCell parameters from 2772 reflections
b = 11.6078 (17) Åθ = 2.8–27.5°
c = 7.6499 (12) ŵ = 0.10 mm1
β = 97.137 (11)°T = 293 K
V = 1307.2 (4) Å3Block, colorless
Z = 40.25 × 0.20 × 0.18 mm

Data collection

Rigaku SCXmini diffractometer2957 independent reflections
Radiation source: fine-focus sealed tube1909 reflections with I > 2σ(I)
graphiteRint = 0.053
CCD_Profile_fitting scansθmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)h = −19→19
Tmin = 0.976, Tmax = 0.982k = −15→14
13109 measured reflectionsl = −9→9

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.143w = 1/[σ2(Fo2) + (0.0677P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2957 reflectionsΔρmax = 0.16 e Å3
183 parametersΔρmin = −0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.041 (5)

Special details

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)

xyzUiso*/Ueq
C10.91128 (11)0.22439 (14)0.9042 (2)0.0411 (4)
C20.97228 (12)0.13505 (15)0.8969 (2)0.0543 (5)
H20.95270.05950.90750.065*
C31.06100 (13)0.15577 (17)0.8744 (3)0.0598 (5)
H31.10070.09440.86680.072*
C41.09167 (12)0.26761 (16)0.8629 (3)0.0526 (5)
C51.03233 (13)0.35724 (16)0.8720 (3)0.0569 (5)
H51.05250.43280.86560.068*
C60.94239 (12)0.33527 (15)0.8909 (2)0.0520 (5)
H60.90230.39650.89460.062*
C70.81706 (11)0.19679 (14)0.9344 (2)0.0433 (4)
C81.21797 (14)0.3917 (2)0.8418 (4)0.0946 (9)
H8A1.18870.43340.74210.142*
H8B1.28190.38680.83400.142*
H8C1.20830.43110.94820.142*
C90.52469 (11)0.13673 (14)0.8280 (2)0.0432 (4)
C100.41189 (12)0.18980 (18)0.9872 (3)0.0589 (5)
H100.38980.23941.06740.071*
C110.35667 (13)0.10217 (18)0.9177 (3)0.0635 (6)
H110.29920.09190.95170.076*
C120.38794 (14)0.03054 (18)0.7977 (3)0.0679 (6)
H120.3516−0.02890.74730.081*
C130.47394 (13)0.04696 (16)0.7517 (3)0.0572 (5)
H130.4970−0.00150.67120.069*
C140.61801 (12)0.15765 (15)0.7797 (2)0.0448 (4)
N10.75270 (10)0.26729 (12)0.8514 (2)0.0500 (4)
H1A0.76320.30960.76550.075*
N20.66187 (9)0.24618 (13)0.8666 (2)0.0507 (4)
H2A0.64350.28810.94610.076*
N30.49533 (9)0.20769 (13)0.9461 (2)0.0507 (4)
O10.79830 (8)0.11775 (10)1.03016 (15)0.0530 (4)
O20.65007 (9)0.10076 (11)0.66877 (17)0.0590 (4)
O31.18109 (9)0.27954 (12)0.8433 (2)0.0759 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0422 (9)0.0415 (9)0.0399 (9)0.0003 (7)0.0060 (7)0.0012 (7)
C20.0473 (11)0.0427 (10)0.0740 (13)−0.0009 (8)0.0114 (9)0.0056 (9)
C30.0489 (11)0.0502 (11)0.0822 (14)0.0078 (9)0.0150 (10)0.0052 (10)
C40.0411 (10)0.0567 (11)0.0607 (11)−0.0028 (8)0.0090 (8)0.0078 (9)
C50.0511 (11)0.0447 (10)0.0752 (14)−0.0067 (9)0.0089 (10)0.0042 (9)
C60.0462 (10)0.0426 (10)0.0676 (12)0.0032 (8)0.0091 (9)−0.0022 (9)
C70.0457 (10)0.0427 (9)0.0429 (9)−0.0025 (8)0.0117 (8)−0.0026 (8)
C80.0509 (13)0.0814 (17)0.153 (3)−0.0185 (11)0.0175 (15)0.0266 (17)
C90.0432 (10)0.0418 (9)0.0447 (9)0.0065 (7)0.0066 (8)0.0058 (7)
C100.0438 (11)0.0659 (13)0.0696 (13)−0.0007 (9)0.0169 (10)−0.0102 (10)
C110.0418 (10)0.0664 (13)0.0831 (14)−0.0055 (10)0.0110 (10)0.0014 (12)
C120.0587 (13)0.0552 (12)0.0882 (16)−0.0154 (10)0.0035 (11)−0.0051 (11)
C130.0620 (12)0.0468 (10)0.0631 (12)0.0005 (9)0.0095 (10)−0.0055 (9)
C140.0452 (10)0.0432 (10)0.0468 (10)0.0097 (8)0.0092 (8)0.0057 (8)
N10.0394 (8)0.0553 (9)0.0583 (10)0.0028 (7)0.0179 (7)0.0104 (7)
N20.0401 (8)0.0549 (9)0.0601 (10)0.0024 (7)0.0183 (7)−0.0033 (7)
N30.0400 (8)0.0549 (9)0.0583 (9)−0.0009 (7)0.0105 (7)−0.0059 (7)
O10.0513 (8)0.0525 (7)0.0567 (8)−0.0058 (6)0.0124 (6)0.0079 (6)
O20.0620 (8)0.0579 (8)0.0601 (8)0.0135 (6)0.0192 (6)−0.0035 (6)
O30.0428 (7)0.0719 (10)0.1157 (13)−0.0033 (7)0.0201 (8)0.0171 (9)

Geometric parameters (Å, °)

C1—C61.375 (2)C8—H8C0.9600
C1—C21.382 (2)C9—N31.335 (2)
C1—C71.480 (2)C9—C131.373 (2)
C2—C31.370 (2)C10—N31.331 (2)
C2—H20.9300C10—C111.371 (3)
C3—C41.382 (3)C10—H100.9300
C3—H30.9300C11—C121.362 (3)
C4—O31.361 (2)C11—H110.9300
C4—C51.370 (3)C12—C131.378 (3)
C5—C61.384 (2)C12—H120.9300
C5—H50.9300C13—H130.9300
C6—H60.9300C14—O21.2179 (19)
C7—O11.2276 (19)C14—N21.347 (2)
C7—N11.354 (2)C14—C91.496 (2)
C8—O31.413 (3)N1—N21.389 (2)
C8—H8A0.9600N1—H1A0.8500
C8—H8B0.9600N2—H2A0.8500
C6—C1—C2118.15 (16)O2—C14—N2123.43 (16)
C6—C1—C7123.11 (15)O2—C14—C9122.51 (16)
C2—C1—C7118.67 (15)N2—C14—C9114.04 (14)
C3—C2—C1121.17 (17)N3—C9—C13123.25 (16)
C3—C2—H2119.4N3—C9—C14117.16 (15)
C1—C2—H2119.4C13—C9—C14119.59 (16)
C2—C3—C4120.13 (17)N3—C10—C11123.56 (18)
C2—C3—H3119.9N3—C10—H10118.2
C4—C3—H3119.9C11—C10—H10118.2
O3—C4—C5124.74 (17)C12—C11—C10118.49 (18)
O3—C4—C3115.84 (17)C12—C11—H11120.8
C5—C4—C3119.42 (17)C10—C11—H11120.8
C4—C5—C6119.96 (17)C11—C12—C13119.42 (18)
C4—C5—H5120.0C11—C12—H12120.3
C6—C5—H5120.0C13—C12—H12120.3
C1—C6—C5121.14 (16)C9—C13—C12118.22 (18)
C1—C6—H6119.4C9—C13—H13120.9
C5—C6—H6119.4C12—C13—H13120.9
O1—C7—N1122.17 (16)C7—N1—N2119.30 (14)
O1—C7—C1122.91 (16)C7—N1—H1A121.7
N1—C7—C1114.89 (15)N2—N1—H1A116.1
O3—C8—H8A109.5C14—N2—N1120.53 (14)
O3—C8—H8B109.5C14—N2—H2A127.8
H8A—C8—H8B109.5N1—N2—H2A111.0
O3—C8—H8C109.5C10—N3—C9117.05 (16)
H8A—C8—H8C109.5C4—O3—C8118.60 (16)
H8B—C8—H8C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.852.112.9479 (19)168
N2—H2A···O2ii0.852.132.938 (2)159

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2329).

References

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