PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2542.
Published online 2009 September 26. doi:  10.1107/S1600536809038227
PMCID: PMC2970289

2-Methoxy­benzohydrazide

Abstract

The title compound, C8H10N2O2, crystallizes as two independent mol­ecules linked by N—H(...)N and N—H(...)O hydrogen bonds into a linear chain running along the a axis of the monoclinic unit cell. The intra- and inter­molecular hydrogen bonds are described as a two-ring R 2 2(10) motif. The six-membered R 1 1(6) rings formed by the intra­molecular inter­actions are almost planar (r.m.s. deviations 0.06 and 0.08 Å). In one mol­ecule, the aromatic and hydrogen-bonded rings are oriented at 4.8 (2)°, whereas in the other mol­ecule these rings are oriented at 6.1 (4)°.

Related literature

For related structures, see: Ashiq et al. (2009 [triangle]); Kallel et al. (1992 [triangle]); Saraogi et al. (2002 [triangle]). For the biological activity of hydrazides, see: Ara et al. (2007 [triangle]); El-Emam et al. (2004 [triangle]); Maqsood et al. (2006 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2542-scheme1.jpg

Experimental

Crystal data

  • C8H10N2O2
  • M r = 166.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2542-efi1.jpg
  • a = 7.6486 (5) Å
  • b = 10.7123 (7) Å
  • c = 20.4781 (13) Å
  • β = 95.563 (3)°
  • V = 1669.95 (19) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 296 K
  • 0.22 × 0.19 × 0.11 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: none
  • 15129 measured reflections
  • 2938 independent reflections
  • 1695 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.110
  • S = 1.02
  • 2938 reflections
  • 237 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [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/S1600536809038227/ng2643sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038227/ng2643Isup2.hkl

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

Acknowledgments

The authors thank the Higher Education Commission Pakistan for providing the diffractometer at GCU, Lahore, and Bana International for support in collecting the crystallographic data. The authors also thank the University of Karachi, Pakistan, for financial support (Dean of the Faculty of Science Research Grant).

supplementary crystallographic information

Comment

Hydrazides are known to have different biological activities and have been used for the synthesis of various heterocyclic compounds (El-Emam et al., 2004). In order to study the biological activity of 2-methoxybenzohydrazide, we undertook the synthesis of title compound and report its crystal structure in this paper. The title compound I was found to be antifungal (Maqsood et al., 2006) and phytotoxic (Ara et al., 2007). The unit cell contains two crystallographically unique molecules (Fig. 1). The structures of benzhydrazide (Kallel et al., 1992), para-chloro (Saraogi et al., 2002) and para-methoxy (Ashiq et al., 2009), analogues of (I) have already been reported.

The molecular packing diagram (Fig. 2) shows the presence of intermolecular hydrogen bonds of N—H···N and N—H···O types (details are given in Table 1) results in the formation of two ring motifs with graphic notation R22(10) (Bernstein et al., 1995), for each. Intramolecular interactions give rise six membered rings C (O2/C6/C1/C7/N1/H1N) and D (O4/C14/C9/C15/N3/H3N) R11(6) (Bernstein et al., 1995), in each molecule. In one molecule, the A and C rings are oriented at 4.8 (2)°, whereas in the other molecule, the B and D rings are oriented at 6.1 (4)°.

Experimental

All reagent-grade chemicals were obtained from Aldrich and Sigma Chemical companies and were used without further purification. To a solution of ethyl-2-methoxybenzoate (3.6 g, 20 mmol) in 75 ml e thanol, hydrazine hydrate (5.0 ml, 100 mmol) was added. The mixture was refluxed for 5 h and a solid was obtained upon removal of the solvent by rotary evaporation. The resulting solid was washed with hexane to afford 2-methoxybenzohydrazide (yield 78%) (Ara et al., 2007). Colourless single crystals of (I) were obtained by slow evaporation of methanol solution at room temperature.

Refinement

The Hydrogen atoms bonded to aryl and methyl Carbon atoms were positioned geometrically, with C—H = 0.93 Å and C—H = 0.96 Å respectively. The thermal parameter of H-atoms of methyl group was taken 1.5 times of the parent C-atom, whereas for aromatic H-atoms it was taken 1.2 times of their parent atoms. Atoms H1N, H21N, H22N H3N, H41N, H42N with N–H= 0.86 (2)–0.96 (2)Å are located in a difference Fourier map and constrained to ride on their parent atom, with Uiso(H) = 1.2Ueq(N).

Figures

Fig. 1.
ORTEP plot of the title compound with the ellipsoids drawn at the 40% probability level, showing the atomic labels.
Fig. 2.
A unit cell packing diagram of (I) showing hydrogen bonds drawn by dashed lines. Hydrogen atoms not involved in H-bonding have been omitted.

Crystal data

C8H10N2O2F(000) = 704
Mr = 166.18Dx = 1.322 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2389 reflections
a = 7.6486 (5) Åθ = 2.7–22.7°
b = 10.7123 (7) ŵ = 0.10 mm1
c = 20.4781 (13) ÅT = 296 K
β = 95.563 (3)°Needle, colourless
V = 1669.95 (19) Å30.22 × 0.19 × 0.11 mm
Z = 8

Data collection

Bruker Kappa APEXII CCD diffractometer1695 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
graphiteθmax = 25.0°, θmin = 2.0°
ω scansh = −9→9
15129 measured reflectionsk = −12→12
2938 independent reflectionsl = −24→24

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0442P)2 + 0.2288P] where P = (Fo2 + 2Fc2)/3
2938 reflections(Δ/σ)max < 0.001
237 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = −0.16 e Å3

Special details

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)

xyzUiso*/Ueq
O10.1822 (2)0.26307 (16)0.04342 (10)0.0827 (6)
O20.6697 (2)0.39866 (15)0.11303 (8)0.0656 (5)
N20.4302 (3)0.0831 (2)0.06058 (12)0.0615 (6)
N10.4586 (2)0.21149 (17)0.07266 (9)0.0525 (5)
H1N0.569 (3)0.235 (2)0.0811 (11)0.063*
H21N0.335 (3)0.066 (2)0.0792 (11)0.063*
H22N0.400 (3)0.081 (2)0.0191 (12)0.063*
C10.3759 (3)0.43070 (19)0.07062 (10)0.0437 (5)
C20.2404 (3)0.5132 (2)0.05221 (12)0.0618 (7)
H20.13170.48150.03590.074*
C30.2614 (5)0.6394 (3)0.05727 (14)0.0803 (9)
H30.16830.69250.04420.096*
C40.4197 (5)0.6872 (3)0.08160 (14)0.0802 (9)
H40.43410.77320.08530.096*
C50.5589 (4)0.6088 (2)0.10075 (12)0.0669 (7)
H50.66640.64190.11740.080*
C60.5379 (3)0.4812 (2)0.09505 (10)0.0486 (6)
C70.3323 (3)0.2961 (2)0.06103 (10)0.0462 (6)
C80.8411 (3)0.4463 (3)0.13126 (16)0.0977 (10)
H8A0.84300.48780.17290.147*
H8B0.87200.50450.09860.147*
H8C0.92390.37870.13460.147*
O31.10200 (18)0.94743 (13)0.10222 (7)0.0552 (4)
O40.64141 (19)0.94752 (16)0.19111 (7)0.0652 (5)
N30.8244 (2)1.01543 (17)0.09341 (9)0.0471 (5)
H3N0.720 (3)1.012 (2)0.1063 (10)0.057*
N40.8484 (3)1.1070 (2)0.04533 (11)0.0558 (5)
H41N0.862 (3)1.062 (2)0.0055 (12)0.067*
H42N0.950 (3)1.140 (2)0.0583 (11)0.067*
C90.9165 (3)0.85915 (19)0.17588 (10)0.0406 (5)
C101.0450 (3)0.7726 (2)0.19540 (11)0.0572 (6)
H101.14450.76820.17280.069*
C111.0305 (4)0.6926 (2)0.24713 (13)0.0740 (8)
H111.11780.63410.25870.089*
C120.8864 (4)0.7004 (3)0.28123 (13)0.0738 (8)
H120.87680.64760.31680.089*
C130.7564 (3)0.7843 (2)0.26394 (11)0.0615 (7)
H130.65910.78860.28780.074*
C140.7681 (3)0.8634 (2)0.21101 (10)0.0459 (5)
C150.9534 (3)0.94351 (18)0.12070 (10)0.0400 (5)
C160.4932 (4)0.9605 (4)0.22740 (15)0.1152 (13)
H16A0.43150.88250.22750.173*
H16B0.41641.02360.20750.173*
H16C0.53160.98420.27170.173*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0401 (10)0.0727 (12)0.1326 (16)−0.0064 (9)−0.0057 (10)0.0055 (11)
O20.0463 (10)0.0639 (11)0.0838 (12)−0.0039 (8)−0.0079 (8)−0.0035 (9)
N20.0550 (13)0.0518 (14)0.0805 (15)−0.0044 (10)0.0207 (12)−0.0025 (12)
N10.0415 (11)0.0404 (12)0.0756 (14)−0.0010 (10)0.0055 (10)−0.0032 (10)
C10.0458 (13)0.0462 (14)0.0409 (12)0.0049 (11)0.0136 (10)0.0060 (10)
C20.0587 (15)0.0638 (18)0.0644 (16)0.0143 (13)0.0142 (12)0.0144 (13)
C30.100 (2)0.061 (2)0.083 (2)0.0307 (18)0.0275 (18)0.0185 (16)
C40.123 (3)0.0454 (17)0.079 (2)0.0049 (19)0.045 (2)0.0001 (15)
C50.086 (2)0.0551 (17)0.0623 (17)−0.0126 (15)0.0217 (14)−0.0100 (13)
C60.0554 (14)0.0487 (15)0.0436 (13)0.0014 (12)0.0136 (11)0.0008 (11)
C70.0389 (13)0.0556 (15)0.0452 (13)0.0005 (12)0.0104 (10)0.0047 (11)
C80.0504 (16)0.114 (3)0.124 (3)−0.0211 (16)−0.0132 (16)−0.007 (2)
O30.0440 (9)0.0614 (10)0.0626 (10)0.0031 (7)0.0167 (7)0.0124 (8)
O40.0523 (10)0.0894 (13)0.0575 (10)0.0187 (9)0.0243 (8)0.0182 (9)
N30.0421 (11)0.0499 (12)0.0506 (11)0.0010 (9)0.0107 (9)0.0135 (9)
N40.0528 (12)0.0576 (14)0.0571 (13)−0.0035 (10)0.0063 (10)0.0184 (11)
C90.0446 (12)0.0366 (12)0.0410 (12)−0.0033 (10)0.0069 (10)−0.0014 (10)
C100.0569 (15)0.0503 (15)0.0657 (16)0.0051 (12)0.0131 (12)0.0071 (13)
C110.081 (2)0.0605 (17)0.0807 (19)0.0116 (14)0.0108 (16)0.0273 (15)
C120.089 (2)0.0649 (18)0.0679 (18)−0.0072 (16)0.0074 (16)0.0266 (15)
C130.0641 (17)0.0711 (18)0.0512 (15)−0.0101 (14)0.0149 (12)0.0114 (13)
C140.0463 (13)0.0507 (14)0.0406 (13)−0.0027 (11)0.0039 (10)0.0005 (11)
C150.0416 (12)0.0389 (12)0.0401 (12)−0.0015 (10)0.0079 (10)−0.0031 (10)
C160.078 (2)0.184 (4)0.093 (2)0.051 (2)0.0534 (18)0.039 (2)

Geometric parameters (Å, °)

O1—C71.222 (2)O3—C151.233 (2)
O2—C61.364 (3)O4—C141.356 (2)
O2—C81.423 (3)O4—C161.421 (3)
N2—N11.410 (3)N3—C151.331 (3)
N2—H21N0.88 (2)N3—N41.414 (2)
N2—H22N0.86 (2)N3—H3N0.87 (2)
N1—C71.329 (3)N4—H41N0.96 (2)
N1—H1N0.88 (2)N4—H42N0.87 (2)
C1—C21.386 (3)C9—C101.382 (3)
C1—C61.399 (3)C9—C141.403 (3)
C1—C71.488 (3)C9—C151.495 (3)
C2—C31.364 (4)C10—C111.375 (3)
C2—H20.9300C10—H100.9300
C3—C41.364 (4)C11—C121.363 (3)
C3—H30.9300C11—H110.9300
C4—C51.383 (4)C12—C131.362 (3)
C4—H40.9300C12—H120.9300
C5—C61.380 (3)C13—C141.385 (3)
C5—H50.9300C13—H130.9300
C8—H8A0.9600C16—H16A0.9600
C8—H8B0.9600C16—H16B0.9600
C8—H8C0.9600C16—H16C0.9600
C6—O2—C8118.5 (2)C14—O4—C16119.39 (19)
N1—N2—H21N104.3 (15)C15—N3—N4123.54 (18)
N1—N2—H22N102.9 (16)C15—N3—H3N120.8 (14)
H21N—N2—H22N105 (2)N4—N3—H3N115.5 (15)
C7—N1—N2122.49 (19)N3—N4—H41N105.8 (14)
C7—N1—H1N120.3 (15)N3—N4—H42N104.1 (15)
N2—N1—H1N116.3 (15)H41N—N4—H42N107 (2)
C2—C1—C6117.6 (2)C10—C9—C14117.5 (2)
C2—C1—C7115.5 (2)C10—C9—C15116.33 (18)
C6—C1—C7126.91 (19)C14—C9—C15126.12 (19)
C3—C2—C1122.1 (3)C11—C10—C9122.2 (2)
C3—C2—H2118.9C11—C10—H10118.9
C1—C2—H2118.9C9—C10—H10118.9
C2—C3—C4119.6 (3)C12—C11—C10119.1 (2)
C2—C3—H3120.2C12—C11—H11120.4
C4—C3—H3120.2C10—C11—H11120.4
C3—C4—C5120.4 (3)C13—C12—C11120.9 (2)
C3—C4—H4119.8C13—C12—H12119.6
C5—C4—H4119.8C11—C12—H12119.6
C6—C5—C4119.9 (3)C12—C13—C14120.4 (2)
C6—C5—H5120.1C12—C13—H13119.8
C4—C5—H5120.1C14—C13—H13119.8
O2—C6—C5122.8 (2)O4—C14—C13122.9 (2)
O2—C6—C1116.9 (2)O4—C14—C9117.24 (18)
C5—C6—C1120.3 (2)C13—C14—C9119.9 (2)
O1—C7—N1120.0 (2)O3—C15—N3121.28 (19)
O1—C7—C1120.8 (2)O3—C15—C9119.98 (19)
N1—C7—C1119.20 (19)N3—C15—C9118.72 (17)
O2—C8—H8A109.5O4—C16—H16A109.5
O2—C8—H8B109.5O4—C16—H16B109.5
H8A—C8—H8B109.5H16A—C16—H16B109.5
O2—C8—H8C109.5O4—C16—H16C109.5
H8A—C8—H8C109.5H16A—C16—H16C109.5
H8B—C8—H8C109.5H16B—C16—H16C109.5
C6—C1—C2—C30.1 (3)C14—C9—C10—C110.0 (3)
C7—C1—C2—C3−179.1 (2)C15—C9—C10—C11177.5 (2)
C1—C2—C3—C4−0.5 (4)C9—C10—C11—C12−1.3 (4)
C2—C3—C4—C50.4 (4)C10—C11—C12—C131.2 (4)
C3—C4—C5—C60.2 (4)C11—C12—C13—C140.2 (4)
C8—O2—C6—C5−7.4 (3)C16—O4—C14—C133.1 (3)
C8—O2—C6—C1173.2 (2)C16—O4—C14—C9−176.4 (2)
C4—C5—C6—O2−180.0 (2)C12—C13—C14—O4179.1 (2)
C4—C5—C6—C1−0.7 (3)C12—C13—C14—C9−1.5 (3)
C2—C1—C6—O2179.89 (18)C10—C9—C14—O4−179.18 (19)
C7—C1—C6—O2−1.1 (3)C15—C9—C14—O43.7 (3)
C2—C1—C6—C50.5 (3)C10—C9—C14—C131.3 (3)
C7—C1—C6—C5179.5 (2)C15—C9—C14—C13−175.8 (2)
N2—N1—C7—O15.1 (3)N4—N3—C15—O3−4.7 (3)
N2—N1—C7—C1−175.71 (19)N4—N3—C15—C9173.79 (19)
C2—C1—C7—O1−6.0 (3)C10—C9—C15—O3−11.5 (3)
C6—C1—C7—O1175.0 (2)C14—C9—C15—O3165.7 (2)
C2—C1—C7—N1174.84 (19)C10—C9—C15—N3169.98 (19)
C6—C1—C7—N1−4.2 (3)C14—C9—C15—N3−12.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H21N···O3i0.88 (2)2.27 (2)3.091 (3)155 (2)
N3—H3N···N2ii0.87 (2)2.44 (2)3.111 (3)134.2 (18)
N4—H41N···O3iii0.96 (2)2.25 (3)3.136 (3)152.3 (19)
N4—H42N···O1iv0.87 (2)2.26 (2)3.055 (3)153 (2)
N1—H1N···O20.89 (2)1.98 (2)2.655 (2)130.8 (17)
N3—H3N···O40.86 (2)2.01 (2)2.653 (2)129.9 (19)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2643).

References

  • Ara, R., Ashiq, U., Mahroof-Tahir, M., Maqsood, Z. T., Khan, K. M., Lodhi, M. A. & Choudhary, M. I. (2007). Chem. Biodivers.4, 58–71. [PubMed]
  • Ashiq, U., Jamal, R. A., Tahir, M. N., Yousuf, S. & Khan, I. U. (2009). Acta Cryst. E65, o1551. [PMC free article] [PubMed]
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • El-Emam, A. A., Al-Deeb, O. A., Al-Omar, M. & Lehmann, J. (2004). Bioorg. Med. Chem.12, 5107–5113. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Kallel, A., Amor, B. H., Svoboda, I. & Fuess, H. (1992). Z. Kristallogr.198, 137–140.
  • Maqsood, Z. T., Khan, K. M., Ashiq, U., Jamal, R. A., Chohan, Z. H., Mahroof-Tahir, M. & Supuran, C. T. (2006). J. Enzym. Inhib. Med. Chem.21, 37–42. [PubMed]
  • Saraogi, I., Mruthyunjayaswamy, B. H. M., Ijare, O. B., Jadegoud, Y. & Guru Row, T. N. (2002). Acta Cryst. E58, o1341–o1342.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography