2-(2-Chloro­phen­oxy)acetohydrazide

Fun, H.-K.; Quah, C.K.; Isloor, A.M.; Sunil, D.; Shetty, P.

doi:10.1107/S1600536809051356

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages o31-o32

doi:10.1107/S1600536809051356

Open

access

2-(2-Chlorophenoxy)acetohydrazide

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Arun M. Isloor,^b Dhanya Sunil ^c and Prakash Shetty ^d

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India, ^cDepartment of Chemistry, Manipal Institute of Technology, Manipal University, 576 104, India, and ^dDepartment of Printing and Media Engineering, Manipal Institute of Technology, Manipal University, 576 104, India
^*Correspondence e-mail: hkfun@usm.my

(Received 26 November 2009; accepted 28 November 2009; online 4 December 2009)

In the title compound, C₈H₉ClN₂O₂, the acetohydrazide group is approximately planar, with the maximum deviation of 0.031 (2) Å. In the crystal, the molecules are linked by N—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds, with the acetohydrazide O atom accepting two C—H⋯O links and one N—H⋯O link. This results in infinite sheets lying parallel to (100).

Related literature

For general background to and biological properties of hydrazine derivatives, see: Rando et al. (2008 ); Kumar et al. (2009 ); Kamal et al. (2007 ); Masunari & Tavares (2007 ); Rando et al. (2002 ). For related structures, see: Fun et al. (2009 , 2010 ). For the preparation, see: Holla & Udupa (1992 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₈H₉ClN₂O₂
M_r = 200.62
Monoclinic, P 2₁ /c
a = 15.2384 (5) Å
b = 3.9269 (1) Å
c = 16.8843 (6) Å
β = 117.269 (2)°
V = 898.07 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 100 K
0.28 × 0.10 × 0.09 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan SADABS (Bruker, 2005 ) T_min = 0.897, T_max = 0.965
11351 measured reflections
2662 independent reflections
2029 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.121
S = 1.05
2662 reflections
130 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2ⁱ	0.83 (3)	2.20 (2)	2.930 (3)	148 (2)
N2—H1N2⋯O2ⁱⁱ	0.91 (3)	2.36 (2)	3.070 (2)	134 (2)
C1—H1A⋯O2ⁱⁱⁱ	0.93	2.54	3.443 (3)	164
C7—H7A⋯O2^iv	0.97	2.37	3.317 (2)	165
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) x, y+1, z; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051356/hb5257sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051356/hb5257Isup2.hkl

checkCIF report

Comment top

Hydrazine derivatives have been reported to possess several biological properties. 5-nitro-2-heterocyclic benzylidine hydrazides were found to possess antileishmanial activities (Rando et al., 2008). Many substituted benzoic acid furan-2-yl-methylene hydrazides showed potent antimicrobial properties(Kumar et al., 2009). Hydrazine derivatives were also associated with remarkable anticancer (Kamal et al., 2007), antibacterial (Masunari & Tavares, 2007) and tuberculostatic (Rando et al., 2002) activities.

The molecular structure is shown in Fig. 1. The acetohydrazide group (C7/C8/N1/N2/O2) is approximately planar, with the maximum deviation of 0.031 (2) Å for atom N1. Bond lengths and angles are within normal ranges, and comparable to closely related structures (Fun et al., 2009, 2010). In the solid state (Fig. 2), the molecules are linked via intermolecular N2—H1N2···O2, C1—H1A···O2 and C7—H7A···O2 trifurcated acceptor bonds, together with N1—H1N1···N2 hydrogen bonds, into infinite two-dimensional networks parallel to plane (1 0 0).

Related literature top

For general background to and biological properties of hydrazine derivatives, see: Rando et al. (2008); Kumar et al. (2009); Kamal et al. (2007); Masunari & Tavares (2007); Rando et al. (2002). For related structures, see: Fun et al. (2009, 2010). For the preparation, see: Holla & Udupa (1992). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

O-chloro phenol (11 ml, 1.00 mmol), ethyl chloroacetate (10.7 ml, 1.00 mmol) and potassium carbonate (20.75 g, 1.50 mmol) were refluxed in acetone (100 ml) at 80 °c for 18 h. The reaction mixture is then filtered, distilled to remove the acetone and poured into ice cold water with vigorous stirring. The ester, phenoxy ethyl acetate was extracted using ether. The solution was distilled to remove ether. Phenoxy ethyl acetate (8.2 ml, 0.50 mmol) was heated at 100 °C for 10h in an absolute alcohol medium (40 ml) with hydrazine hydrate (2.5 ml, 0.50 mmol). The reaction mixture was allowed to cool, the solid separated was filtered, dried and recrystallized from ethanol. The yield was found to be 7.1 g (71 %). M. p. 384-385 K (Holla & Udupa, 1992).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids.
	Fig. 2. The crystal structure of (I) viewed along the a axis. H atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

2-(2-Chlorophenoxy)acetohydrazide top

Crystal data top

C₈H₉ClN₂O₂	F(000) = 416
M_r = 200.62	D_x = 1.484 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3388 reflections
a = 15.2384 (5) Å	θ = 2.4–30.1°
b = 3.9269 (1) Å	µ = 0.39 mm⁻¹
c = 16.8843 (6) Å	T = 100 K
β = 117.269 (2)°	Block, colourless
V = 898.07 (5) Å³	0.28 × 0.10 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	2662 independent reflections
Radiation source: fine-focus sealed tube	2029 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 30.2°, θ_min = 1.5°
Absorption correction: multi-scan SADABS (Bruker, 2005)	h = −21→20
T_min = 0.897, T_max = 0.965	k = −5→4
11351 measured reflections	l = −22→23

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0585P)² + 0.3771P] where P = (F_o² + 2F_c²)/3
2662 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₈H₉ClN₂O₂	V = 898.07 (5) Å³
M_r = 200.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.2384 (5) Å	µ = 0.39 mm⁻¹
b = 3.9269 (1) Å	T = 100 K
c = 16.8843 (6) Å	0.28 × 0.10 × 0.09 mm
β = 117.269 (2)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2662 independent reflections
Absorption correction: multi-scan SADABS (Bruker, 2005)	2029 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.965	R_int = 0.050
11351 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.44 e Å⁻³
2662 reflections	Δρ_min = −0.30 e Å⁻³
130 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 2sigma(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
Cl1	0.69094 (3)	0.22956 (13)	0.86423 (3)	0.02146 (15)
O1	0.83867 (8)	0.0410 (4)	0.81001 (8)	0.0174 (3)
O2	1.09342 (9)	−0.0760 (4)	0.87110 (8)	0.0183 (3)
N1	1.01406 (11)	0.2382 (4)	0.93081 (10)	0.0158 (3)
N2	1.10162 (11)	0.3687 (5)	1.00234 (10)	0.0175 (3)
C1	0.72527 (14)	−0.1775 (5)	0.66271 (12)	0.0192 (4)
H1A	0.7768	−0.2398	0.6506	0.023*
C2	0.62775 (14)	−0.2331 (5)	0.59963 (12)	0.0232 (4)
H2A	0.6144	−0.3314	0.5452	0.028*
C3	0.55039 (14)	−0.1436 (6)	0.61715 (13)	0.0236 (4)
H3A	0.4855	−0.1815	0.5746	0.028*
C4	0.57002 (12)	0.0024 (5)	0.69829 (12)	0.0197 (4)
H4A	0.5185	0.0633	0.7105	0.024*
C5	0.66699 (13)	0.0571 (5)	0.76107 (12)	0.0177 (4)
C6	0.74518 (12)	−0.0283 (5)	0.74390 (11)	0.0161 (4)
C7	0.91785 (12)	−0.0685 (5)	0.79289 (11)	0.0154 (4)
H7A	0.9113	0.0356	0.7383	0.018*
H7B	0.9149	−0.3137	0.7851	0.018*
C8	1.01638 (12)	0.0305 (5)	0.86985 (11)	0.0147 (4)
H1N1	0.9633 (17)	0.307 (5)	0.9322 (14)	0.014 (5)*
H1N2	1.1345 (16)	0.478 (6)	0.9761 (14)	0.018 (6)*
H2N2	1.1333 (17)	0.195 (6)	1.0302 (16)	0.022 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0139 (2)	0.0305 (3)	0.0168 (2)	0.00075 (17)	0.00427 (15)	−0.00393 (19)
O1	0.0092 (5)	0.0272 (8)	0.0117 (6)	−0.0005 (5)	0.0012 (4)	−0.0029 (5)
O2	0.0137 (6)	0.0242 (8)	0.0163 (6)	0.0013 (5)	0.0063 (5)	−0.0006 (5)
N1	0.0092 (6)	0.0219 (8)	0.0123 (7)	0.0002 (6)	0.0016 (5)	−0.0024 (6)
N2	0.0113 (6)	0.0238 (9)	0.0114 (7)	−0.0012 (6)	−0.0002 (6)	−0.0012 (6)
C1	0.0177 (8)	0.0214 (10)	0.0142 (8)	−0.0010 (7)	0.0035 (7)	−0.0001 (7)
C2	0.0226 (9)	0.0242 (10)	0.0136 (8)	−0.0030 (8)	0.0003 (7)	−0.0023 (8)
C3	0.0145 (8)	0.0259 (11)	0.0201 (9)	−0.0035 (7)	−0.0011 (7)	−0.0010 (8)
C4	0.0113 (7)	0.0224 (10)	0.0205 (9)	−0.0013 (7)	0.0029 (7)	0.0006 (8)
C5	0.0154 (8)	0.0184 (10)	0.0140 (8)	−0.0007 (7)	0.0023 (6)	0.0002 (7)
C6	0.0115 (7)	0.0175 (9)	0.0140 (8)	−0.0011 (7)	0.0012 (6)	0.0019 (7)
C7	0.0124 (7)	0.0195 (10)	0.0116 (7)	−0.0005 (7)	0.0031 (6)	−0.0007 (7)
C8	0.0142 (7)	0.0162 (9)	0.0115 (7)	0.0002 (7)	0.0041 (6)	0.0032 (6)

Geometric parameters (Å, º) top

Cl1—C5	1.7443 (19)	C1—H1A	0.9300
O1—C6	1.3756 (19)	C2—C3	1.386 (3)
O1—C7	1.430 (2)	C2—H2A	0.9300
O2—C8	1.237 (2)	C3—C4	1.385 (3)
N1—C8	1.326 (2)	C3—H3A	0.9300
N1—N2	1.4231 (19)	C4—C5	1.385 (2)
N1—H1N1	0.83 (2)	C4—H4A	0.9300
N2—H1N2	0.91 (2)	C5—C6	1.390 (3)
N2—H2N2	0.84 (2)	C7—C8	1.519 (2)
C1—C6	1.391 (3)	C7—H7A	0.9700
C1—C2	1.393 (2)	C7—H7B	0.9700

C6—O1—C7	115.63 (14)	C5—C4—H4A	120.3
C8—N1—N2	122.15 (15)	C3—C4—H4A	120.3
C8—N1—H1N1	125.4 (15)	C4—C5—C6	121.25 (17)
N2—N1—H1N1	112.5 (15)	C4—C5—Cl1	119.09 (15)
N1—N2—H1N2	105.5 (13)	C6—C5—Cl1	119.65 (13)
N1—N2—H2N2	104.8 (16)	O1—C6—C5	116.80 (16)
H1N2—N2—H2N2	110 (2)	O1—C6—C1	124.09 (17)
C6—C1—C2	119.63 (18)	C5—C6—C1	119.11 (16)
C6—C1—H1A	120.2	O1—C7—C8	110.19 (14)
C2—C1—H1A	120.2	O1—C7—H7A	109.6
C3—C2—C1	120.73 (18)	C8—C7—H7A	109.6
C3—C2—H2A	119.6	O1—C7—H7B	109.6
C1—C2—H2A	119.6	C8—C7—H7B	109.6
C4—C3—C2	119.78 (17)	H7A—C7—H7B	108.1
C4—C3—H3A	120.1	O2—C8—N1	123.86 (16)
C2—C3—H3A	120.1	O2—C8—C7	119.11 (16)
C5—C4—C3	119.50 (18)	N1—C8—C7	117.00 (15)

C6—C1—C2—C3	−0.5 (3)	C4—C5—C6—C1	−1.3 (3)
C1—C2—C3—C4	−0.1 (3)	Cl1—C5—C6—C1	177.58 (15)
C2—C3—C4—C5	0.0 (3)	C2—C1—C6—O1	−179.16 (18)
C3—C4—C5—C6	0.7 (3)	C2—C1—C6—C5	1.1 (3)
C3—C4—C5—Cl1	−178.13 (16)	C6—O1—C7—C8	178.73 (15)
C7—O1—C6—C5	176.26 (16)	N2—N1—C8—O2	2.4 (3)
C7—O1—C6—C1	−3.5 (3)	N2—N1—C8—C7	−175.28 (16)
C4—C5—C6—O1	179.00 (18)	O1—C7—C8—O2	172.20 (16)
Cl1—C5—C6—O1	−2.1 (2)	O1—C7—C8—N1	−10.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.83 (3)	2.20 (2)	2.930 (3)	148 (2)
N2—H1N2···O2ⁱⁱ	0.91 (3)	2.36 (2)	3.070 (2)	134 (2)
C1—H1A···O2ⁱⁱⁱ	0.93	2.54	3.443 (3)	164
C7—H7A···O2^iv	0.97	2.37	3.317 (2)	165

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x, y+1, z; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₉ClN₂O₂
M_r	200.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	15.2384 (5), 3.9269 (1), 16.8843 (6)
β (°)	117.269 (2)
V (Å³)	898.07 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.28 × 0.10 × 0.09

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan SADABS (Bruker, 2005)
T_min, T_max	0.897, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	11351, 2662, 2029
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.121, 1.05
No. of reflections	2662
No. of parameters	130
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.30

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.83 (3)	2.20 (2)	2.930 (3)	148 (2)
N2—H1N2···O2ⁱⁱ	0.91 (3)	2.36 (2)	3.070 (2)	134 (2)
C1—H1A···O2ⁱⁱⁱ	0.93	2.54	3.443 (3)	164
C7—H7A···O2^iv	0.97	2.37	3.317 (2)	165

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x, y+1, z; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, y+1/2, −z+3/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ thanks USM for a Research Fellowship. AMI is grateful to the Director, NITK-Surathkal, India, for providing research facilities and the Head of the Department of Chemistry & Dean R&D, NITK Surathkal, for their encouragement.

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fun, H.-K., Quah, C. K., Isloor, A. M., Sunil, D. & Shetty, P. (2010). Acta Cryst. E66, o53–o54. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Quah, C. K., Sujith, K. V. & Kalluraya, B. (2009). Acta Cryst. E65, o1184–o1185. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Holla, B. S. & Udupa, K. V. (1992). Farmaco, 47, 305–318 PubMed CAS Web of Science Google Scholar
Kamal, A., Khan, N. A., Reddy, K. S. & Rohini, K. (2007). Bioorg. Med. Chem. 15, 1004–1013. Web of Science CrossRef PubMed CAS Google Scholar
Kumar, P., Narasimhan, B., Sharma, D., Judge, V. & Narang, R. (2009). Eur. J. Med. Chem. 44, 1853–1863. Web of Science CrossRef PubMed CAS Google Scholar
Masunari, A. & Tavares, L. C. (2007). Bioorg. Med. Chem. 15, 4229–4236. Web of Science CrossRef PubMed CAS Google Scholar
Rando, D. G., Avery, M. A., Tekwani, B. L., Khan, S. I. & Ferreira, E. I. (2008). Bioorg. Med. Chem. 16, 6724–6731. Web of Science CrossRef PubMed CAS Google Scholar
Rando, D. G., Sato, D. N., Siqueira, L., Malvezzi, A., Leite, C. Q. F., do Amaral, A. T., Ferreira, E. I. & Tavares, L. C. (2002). Bioorg. Med. Chem. 10, 557–560. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar