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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2188.
Published online 2008 October 25. doi:  10.1107/S1600536808033898
PMCID: PMC2959674

4-Iodo­benzohydrazide

Abstract

In the structure of the title compound, C7H7IN2O, the hydrazide group is inclined at 13.3 (3)° with respect to the benzene ring. The structure is stabilized by inter­molecular N—H(...)N and N—H(...)O hydrogen bonds involving the hydrazide group, resulting in six- and ten-membered rings with R 2 2(6) and R 2 2(10) graph-set notations, respectively.

Related literature

For related structures, see: Kallel et al. (1992 [triangle]); Saraogi et al. (2002 [triangle]); Ashiq, Jamal et al. (2008 [triangle]). For related literature, see: Ara et al. (2007 [triangle]); Ashiq, Ara et al. (2008 [triangle]); Bernstein et al. (1994 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2188-scheme1.jpg

Experimental

Crystal data

  • C7H7IN2O
  • M r = 262.05
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2188-efi1.jpg
  • a = 28.4394 (18) Å
  • b = 4.4514 (3) Å
  • c = 13.3216 (9) Å
  • β = 94.292 (2)°
  • V = 1681.72 (19) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.76 mm−1
  • T = 296 (2) K
  • 0.12 × 0.08 × 0.06 mm

Data collection

  • Bruker KappaAPEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.581, T max = 0.806
  • 9236 measured reflections
  • 2069 independent reflections
  • 1645 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.106
  • S = 1.05
  • 2069 reflections
  • 109 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.55 e Å−3
  • Δρmin = −1.33 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 [triangle]); 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/S1600536808033898/pv2109sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033898/pv2109Isup2.hkl

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

Acknowledgments

The authors thank the Higher Education Commission, Pakistan, for providing the Kappa APEXII X-ray diffractometer at GCU, Lahore, and BANA International for their support in collecting the crystallographic data.

supplementary crystallographic information

Comment

The title compound and its oxovanadium(IV) complex were investigated for their α-glucosidase inhibitory and urease activities. Free hydrazide ligand was found to be inactive, whereas its oxovanadium(IV) complex was found to be a potent inhibitor of α-glucosidase (Ashiq, Ara et al., 2008) and urease (Ara et al., 2007). Continuing our studies on the enzyme inhibition behavior of the title compound, (I), and to investigate the change in its activity due to complexation with vanadium center, we have synthesized (I) and report its crystal structure in this paper. The structures of benzhydrazide (Kallel et al., 1992), para-chloro (Saraogi et al., 2002) and para-bromo (Ashiq, Jamal et al., 2008) analogues of (I) have already been reported.

The molecule of the title compound (Fig. 1) is far from planar as is evident from the dihedral angle of 13.3 (3)° between the mean-planes of the phenyl ring (C1-C6) and the hydrazide moiety (N1/N2/O1/C7). The bond distances and bond angles in (I) are similar to the corersponding distances and angles reported in the structures quoted above. The molecules of (I) are involved in two types of hydrogen bonds involving hydrazide moiety. On one hand, the molecules lying about inversion centers form six membered rings via N1—H1A···N2i hydrogen bonding. On the other hand, the molecules related by c-glide form ten membered rings via N2—H2A···O1ii; detail of the hydrogen bonding have been presented in Table 1 and depicted in Fig. 2. The six and ten membered rings represent R22(6) and R22(10) graph set patterns, respectively (Bernstein et al., 1994).

Experimental

All reagent-grade chemicals were obtained from Aldrich and Sigma Chemical companies and were used without further purification. To a solution of ethyl-4-iodobenzoate (5.5 g, 20 mmol) in 75 ml ethanol, 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 4-iodobenzohydrazide (yield 84%).

Refinement

H-atoms bonded to N-atoms were located from a difference map and were included in the refinement at those positions (using DFIX command with N—H = 0.86 (1) Å) while the aryl H-atoms were positioned geometrically in a riding mode, with C—H = 0.93 Å; for all H-atoms, Uiso = 1.2 times Ueq of the parent atoms.

Figures

Fig. 1.
ORTEP plot of the title compound with the ellipsoids drawn at the 50% probability level.
Fig. 2.
The hydrogen bonding patterns of (I) represented by dashed lines in the unit cell; H-atoms not involved in H-bonds have been excluded.

Crystal data

C7H7IN2OF(000) = 992
Mr = 262.05Dx = 2.072 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3495 reflections
a = 28.4394 (18) Åθ = 1.4–28.3°
b = 4.4514 (3) ŵ = 3.76 mm1
c = 13.3216 (9) ÅT = 296 K
β = 94.292 (2)°Needle, colorless
V = 1681.72 (19) Å30.12 × 0.08 × 0.06 mm
Z = 8

Data collection

Bruker KappaAPEXII CCD diffractometer2069 independent reflections
Radiation source: fine-focus sealed tube1645 reflections with I > 2σ(I)
graphiteRint = 0.030
ω scansθmax = 28.3°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −37→37
Tmin = 0.581, Tmax = 0.806k = −5→5
9236 measured reflectionsl = −17→17

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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0565P)2 + 5.77P] where P = (Fo2 + 2Fc2)/3
2069 reflections(Δ/σ)max = 0.001
109 parametersΔρmax = 0.55 e Å3
3 restraintsΔρmin = −1.32 e Å3

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
I10.215538 (11)1.09655 (7)0.64904 (2)0.05339 (15)
O10.05919 (14)0.3811 (8)0.2873 (2)0.0582 (10)
N10.03174 (13)0.1851 (9)0.4262 (2)0.0404 (8)
H1A0.0321 (18)0.170 (11)0.4905 (9)0.049*
N2−0.00239 (14)0.0017 (10)0.3743 (2)0.0408 (8)
H2A−0.0195 (16)0.119 (9)0.335 (3)0.049*
H2B0.0127 (17)−0.126 (9)0.341 (3)0.049*
C10.09627 (14)0.5363 (10)0.4445 (3)0.0358 (8)
C20.09382 (15)0.5693 (10)0.5484 (3)0.0403 (9)
H20.06950.47770.57990.048*
C30.12697 (15)0.7356 (11)0.6046 (3)0.0441 (10)
H30.12440.76110.67330.053*
C40.16380 (15)0.8638 (9)0.5594 (3)0.0397 (9)
C50.16696 (17)0.8370 (11)0.4566 (3)0.0489 (11)
H50.19180.92560.42600.059*
C60.13267 (18)0.6768 (12)0.3998 (3)0.0489 (11)
H60.13420.66370.33050.059*
C70.06129 (16)0.3608 (9)0.3801 (3)0.0375 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.0461 (2)0.0498 (2)0.0626 (2)−0.00097 (13)−0.00736 (14)0.00125 (13)
O10.069 (2)0.080 (3)0.0273 (13)−0.0221 (19)0.0124 (14)−0.0003 (14)
N10.0469 (19)0.0465 (19)0.0277 (14)−0.0046 (17)0.0010 (13)0.0067 (14)
N20.050 (2)0.0425 (19)0.0302 (15)0.0003 (17)0.0039 (14)0.0051 (15)
C10.0384 (19)0.038 (2)0.0317 (17)0.0053 (17)0.0080 (14)0.0015 (16)
C20.039 (2)0.051 (3)0.0317 (17)−0.0001 (18)0.0109 (15)0.0041 (17)
C30.043 (2)0.054 (3)0.0352 (18)0.001 (2)0.0049 (16)0.0000 (19)
C40.036 (2)0.039 (2)0.044 (2)0.0035 (16)−0.0004 (16)0.0018 (17)
C50.048 (2)0.053 (3)0.047 (2)−0.008 (2)0.0168 (19)0.002 (2)
C60.055 (3)0.056 (3)0.038 (2)−0.004 (2)0.0156 (19)0.001 (2)
C70.042 (2)0.041 (2)0.0309 (17)0.0060 (17)0.0088 (15)0.0037 (15)

Geometric parameters (Å, °)

I1—C42.098 (4)C1—C71.486 (6)
O1—C71.237 (5)C2—C31.375 (6)
N1—C71.332 (5)C2—H20.9300
N1—N21.410 (6)C3—C41.371 (6)
N1—H1A0.857 (10)C3—H30.9300
N2—H2A0.862 (10)C4—C51.384 (6)
N2—H2B0.860 (10)C5—C61.386 (7)
C1—C61.382 (6)C5—H50.9300
C1—C21.398 (5)C6—H60.9300
C7—N1—N2123.3 (3)C2—C3—H3120.0
C7—N1—H1A123 (3)C3—C4—C5120.5 (4)
N2—N1—H1A114 (3)C3—C4—I1118.8 (3)
N1—N2—H2A106 (3)C5—C4—I1120.7 (3)
N1—N2—H2B107 (4)C4—C5—C6119.3 (4)
H2A—N2—H2B112 (5)C4—C5—H5120.4
C6—C1—C2118.3 (4)C6—C5—H5120.4
C6—C1—C7118.6 (3)C1—C6—C5121.1 (4)
C2—C1—C7123.1 (4)C1—C6—H6119.5
C3—C2—C1120.8 (4)C5—C6—H6119.5
C3—C2—H2119.6O1—C7—N1121.3 (4)
C1—C2—H2119.6O1—C7—C1121.3 (4)
C4—C3—C2120.0 (4)N1—C7—C1117.4 (3)
C4—C3—H3120.0
C6—C1—C2—C3−0.5 (7)C7—C1—C6—C5−178.3 (4)
C7—C1—C2—C3−179.6 (4)C4—C5—C6—C1−1.9 (8)
C1—C2—C3—C4−2.0 (7)N2—N1—C7—O12.7 (7)
C2—C3—C4—C52.5 (7)N2—N1—C7—C1−178.5 (4)
C2—C3—C4—I1−176.8 (3)C6—C1—C7—O1−12.8 (6)
C3—C4—C5—C6−0.6 (7)C2—C1—C7—O1166.3 (4)
I1—C4—C5—C6178.8 (4)C6—C1—C7—N1168.4 (4)
C2—C1—C6—C52.4 (7)C2—C1—C7—N1−12.4 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.86 (1)2.19 (3)2.964 (5)151 (5)
N2—H2A···O1ii0.86 (1)2.24 (1)3.094 (5)170 (5)
C3—H3···O1iii0.932.563.257 (5)132

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2109).

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., Ara, R., Mahroof-Tahir, M., Maqsood, Z. T., Khan, K. M., Khan, S. N., Siddiqui, H. & Choudhary, M. I. (2008). Chem. Biodivers.5, 82–92. [PubMed]
  • Ashiq, U., Jamal, R. A., Mahroof-Tahir, M., Keramidas, A. D., Maqsood, Z. T., Khan, K. M. & Tahir, M. N. (2008). Anal. Sci. X, 24, 103–104.
  • Bernstein, J., Etter, M. C. & Leiserowitz, L. (1994). Structure Correlation, edited by H.-B. Bürgi & J. D. Dunitz, Vol. 2, pp. 431–507. New York: VCH.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Kallel, A., Amor, B. H., Svoboda, I. & Fuess, H. (1992). Z. Kristallogr.198, 137–140.
  • 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