4-Iodo­benzohydrazide

Jamal, R.A.; Ashiq, U.; Arshad, M.N.; Maqsood, Z.T.; Khan, I.U.

doi:10.1107/S1600536808033898

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2188

doi:10.1107/S1600536808033898

Open

access

4-Iodobenzohydrazide

Rifat Ara Jamal,^a ^* Uzma Ashiq,^b Muhammad Nadeem Arshad,^c Zahida Tasneem Maqsood ^d and Islam Ullah Khan ^c

^aDepartment of Chemical Engineering, NED University of Engineering and Technology, Karachi 75270, Pakistan, ^bDepartment of Mathematics and Basic Sciences, NED University of Engineering and Technology, Karachi 75270, Pakistan, ^cDepartment of Chemistry, Government College University, Lahore, Pakistan, and ^dDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: rifat_jamal@yahoo.com

(Received 19 September 2008; accepted 17 October 2008; online 25 October 2008)

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 R₂²(6) and R₂²(10) graph-set notations, respectively.

Related literature

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

Experimental

Crystal data

C₇H₇IN₂O
M_r = 262.05
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.106
S = 1.05
2069 reflections
109 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −1.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.857 (10)	2.19 (3)	2.964 (5)	151 (5)
N2—H2A⋯O1ⁱⁱ	0.862 (10)	2.240 (14)	3.094 (5)	170 (5)
C3—H3⋯O1ⁱⁱⁱ	0.93	2.56	3.257 (5)	132
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808033898/pv2109sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	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.

4-Iodobenzohydrazide top

Crystal data top

C₇H₇IN₂O	F(000) = 992
M_r = 262.05	D_x = 2.072 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3495 reflections
a = 28.4394 (18) Å	θ = 1.4–28.3°
b = 4.4514 (3) Å	µ = 3.76 mm⁻¹
c = 13.3216 (9) Å	T = 296 K
β = 94.292 (2)°	Needle, colorless
V = 1681.72 (19) Å³	0.12 × 0.08 × 0.06 mm
Z = 8

Data collection top

Bruker KappaAPEXII CCD diffractometer	2069 independent reflections
Radiation source: fine-focus sealed tube	1645 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 28.3°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −37→37
T_min = 0.581, T_max = 0.806	k = −5→5
9236 measured reflections	l = −17→17

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0565P)² + 5.77P] where P = (F_o² + 2F_c²)/3
2069 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.55 e Å⁻³
3 restraints	Δρ_min = −1.33 e Å⁻³

Crystal data top

C₇H₇IN₂O	V = 1681.72 (19) Å³
M_r = 262.05	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 28.4394 (18) Å	µ = 3.76 mm⁻¹
b = 4.4514 (3) Å	T = 296 K
c = 13.3216 (9) Å	0.12 × 0.08 × 0.06 mm
β = 94.292 (2)°

Data collection top

Bruker KappaAPEXII CCD diffractometer	2069 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1645 reflections with I > 2σ(I)
T_min = 0.581, T_max = 0.806	R_int = 0.030
9236 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	3 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.55 e Å⁻³
2069 reflections	Δρ_min = −1.33 e Å⁻³
109 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
I1	0.215538 (11)	1.09655 (7)	0.64904 (2)	0.05339 (15)
O1	0.05919 (14)	0.3811 (8)	0.2873 (2)	0.0582 (10)
N1	0.03174 (13)	0.1851 (9)	0.4262 (2)	0.0404 (8)
H1A	0.0321 (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*
H2B	0.0127 (17)	−0.126 (9)	0.341 (3)	0.049*
C1	0.09627 (14)	0.5363 (10)	0.4445 (3)	0.0358 (8)
C2	0.09382 (15)	0.5693 (10)	0.5484 (3)	0.0403 (9)
H2	0.0695	0.4777	0.5799	0.048*
C3	0.12697 (15)	0.7356 (11)	0.6046 (3)	0.0441 (10)
H3	0.1244	0.7611	0.6733	0.053*
C4	0.16380 (15)	0.8638 (9)	0.5594 (3)	0.0397 (9)
C5	0.16696 (17)	0.8370 (11)	0.4566 (3)	0.0489 (11)
H5	0.1918	0.9256	0.4260	0.059*
C6	0.13267 (18)	0.6768 (12)	0.3998 (3)	0.0489 (11)
H6	0.1342	0.6637	0.3305	0.059*
C7	0.06129 (16)	0.3608 (9)	0.3801 (3)	0.0375 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0461 (2)	0.0498 (2)	0.0626 (2)	−0.00097 (13)	−0.00736 (14)	0.00125 (13)
O1	0.069 (2)	0.080 (3)	0.0273 (13)	−0.0221 (19)	0.0124 (14)	−0.0003 (14)
N1	0.0469 (19)	0.0465 (19)	0.0277 (14)	−0.0046 (17)	0.0010 (13)	0.0067 (14)
N2	0.050 (2)	0.0425 (19)	0.0302 (15)	0.0003 (17)	0.0039 (14)	0.0051 (15)
C1	0.0384 (19)	0.038 (2)	0.0317 (17)	0.0053 (17)	0.0080 (14)	0.0015 (16)
C2	0.039 (2)	0.051 (3)	0.0317 (17)	−0.0001 (18)	0.0109 (15)	0.0041 (17)
C3	0.043 (2)	0.054 (3)	0.0352 (18)	0.001 (2)	0.0049 (16)	0.0000 (19)
C4	0.036 (2)	0.039 (2)	0.044 (2)	0.0035 (16)	−0.0004 (16)	0.0018 (17)
C5	0.048 (2)	0.053 (3)	0.047 (2)	−0.008 (2)	0.0168 (19)	0.002 (2)
C6	0.055 (3)	0.056 (3)	0.038 (2)	−0.004 (2)	0.0156 (19)	0.001 (2)
C7	0.042 (2)	0.041 (2)	0.0309 (17)	0.0060 (17)	0.0088 (15)	0.0037 (15)

Geometric parameters (Å, º) top

I1—C4	2.098 (4)	C1—C7	1.486 (6)
O1—C7	1.237 (5)	C2—C3	1.375 (6)
N1—C7	1.332 (5)	C2—H2	0.9300
N1—N2	1.410 (6)	C3—C4	1.371 (6)
N1—H1A	0.857 (10)	C3—H3	0.9300
N2—H2A	0.862 (10)	C4—C5	1.384 (6)
N2—H2B	0.860 (10)	C5—C6	1.386 (7)
C1—C6	1.382 (6)	C5—H5	0.9300
C1—C2	1.398 (5)	C6—H6	0.9300

C7—N1—N2	123.3 (3)	C2—C3—H3	120.0
C7—N1—H1A	123 (3)	C3—C4—C5	120.5 (4)
N2—N1—H1A	114 (3)	C3—C4—I1	118.8 (3)
N1—N2—H2A	106 (3)	C5—C4—I1	120.7 (3)
N1—N2—H2B	107 (4)	C4—C5—C6	119.3 (4)
H2A—N2—H2B	112 (5)	C4—C5—H5	120.4
C6—C1—C2	118.3 (4)	C6—C5—H5	120.4
C6—C1—C7	118.6 (3)	C1—C6—C5	121.1 (4)
C2—C1—C7	123.1 (4)	C1—C6—H6	119.5
C3—C2—C1	120.8 (4)	C5—C6—H6	119.5
C3—C2—H2	119.6	O1—C7—N1	121.3 (4)
C1—C2—H2	119.6	O1—C7—C1	121.3 (4)
C4—C3—C2	120.0 (4)	N1—C7—C1	117.4 (3)
C4—C3—H3	120.0

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—O1	2.7 (7)
C2—C3—C4—C5	2.5 (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—O1	166.3 (4)
I1—C4—C5—C6	178.8 (4)	C6—C1—C7—N1	168.4 (4)
C2—C1—C6—C5	2.4 (7)	C2—C1—C7—N1	−12.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86 (1)	2.19 (3)	2.964 (5)	151 (5)
N2—H2A···O1ⁱⁱ	0.86 (1)	2.24 (1)	3.094 (5)	170 (5)
C3—H3···O1ⁱⁱⁱ	0.93	2.56	3.257 (5)	132

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

Experimental details

Crystal data
Chemical formula	C₇H₇IN₂O
M_r	262.05
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	28.4394 (18), 4.4514 (3), 13.3216 (9)
β (°)	94.292 (2)
V (Å³)	1681.72 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.76
Crystal size (mm)	0.12 × 0.08 × 0.06

Data collection
Diffractometer	Bruker KappaAPEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.581, 0.806
No. of measured, independent and observed [I > 2σ(I)] reflections	9236, 2069, 1645
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.106, 1.05
No. of reflections	2069
No. of parameters	109
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −1.33

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.857 (10)	2.19 (3)	2.964 (5)	151 (5)
N2—H2A···O1ⁱⁱ	0.862 (10)	2.240 (14)	3.094 (5)	170 (5)
C3—H3···O1ⁱⁱⁱ	0.93	2.56	3.257 (5)	132

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

Acknowledgements

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.

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. Web of Science CrossRef PubMed CAS Google Scholar
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. Web of Science CrossRef PubMed CAS Google Scholar
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. CSD CrossRef Google Scholar
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. Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kallel, A., Amor, B. H., Svoboda, I. & Fuess, H. (1992). Z. Kristallogr. 198, 137–140. CrossRef CAS Web of Science Google Scholar
Saraogi, I., Mruthyunjayaswamy, B. H. M., Ijare, O. B., Jadegoud, Y. & Guru Row, T. N. (2002). Acta Cryst. E58, o1341–o1342. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar