2-(4-Bromo­phen­oxy)propanohydrazide

Akhtar, T.; Khawar Rauf, M.; Ebihara, M.; Hameed, S.

doi:10.1107/S1600536809003134

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o441

doi:10.1107/S1600536809003134

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2-(4-Bromophenoxy)propanohydrazide

Tashfeen Akhtar,^a M. Khawar Rauf,^a Masahiro Ebihara ^b and Shahid Hameed ^a ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
^*Correspondence e-mail: shameed@qau.edu.pk

(Received 15 January 2009; accepted 26 January 2009; online 31 January 2009)

The title compound, C₉H₁₁BrN₂O₂, is an important intermediate for the synthesis of heterocyclic compounds such as azoles, 2,5-disubstituted-1,3,4-oxadiazoles and 5-substituted 2-mercapto-1,3,4-oxadiazoles. The bromophenoxy group subtends a dihedral angle of 82.81 (7)° with the plane passing through the propanohydrazide moiety. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds that form columns extending along the b axis.

Related literature

For carboxyhydrazide derivatives with biological activities, see: Belkadi & Othman (2006 ); Goswami et al. (1984 ); Akhtar et al. (2008 ); Akhtar, Hameed et al. (2007 ); Ahmad et al. (1996 ); Akhtar et al. (2006 ); For related structures, see: Akhtar, Khawar Rauf et al. (2007 ); Zheng (2008 ).

Experimental

Crystal data

C₉H₁₁BrN₂O₂
M_r = 259.11
Monoclinic, P 2₁ /c
a = 10.2598 (14) Å
b = 4.8009 (7) Å
c = 23.322 (3) Å
β = 112.712 (6)°
V = 1059.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.86 mm⁻¹
T = 113 (2) K
0.50 × 0.30 × 0.20 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: integration (NUMABS; Higashi, 1999) T_min = 0.531, T_max = 0.759
8296 measured reflections
2418 independent reflections
2201 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.076
S = 1.20
2418 reflections
137 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.85 (3)	1.97 (3)	2.812 (3)	170 (3)
N2—H2A⋯O1ⁱⁱ	0.83 (3)	2.33 (3)	3.127 (3)	161 (3)
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y, -z+1.

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97 and TEXSAN.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003134/si2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003134/si2151Isup2.hkl

checkCIF report

Comment top

Carboxylic acid hydrazides are important biological agents and intermediates in the synthesis of biologically active heterocycles with two nitrogen atoms at adjacent positions (Belkadi & Othman, 2006). The hydrazides when treated with isocyanates or isothiocyanates afford semicarbazides and thiosemicarbazides, respectively (Goswami et al., 1984). These are important intermediates in the synthesis of azoles under acidic or basic conditions (Akhtar et al., 2007a; Ahmad et al., 1996). In continuation of our previous studies (Akhtar et al., 2006; Akhtar et al., 2007b), the title compound, 2-(4-bromophenoxy)propane hydrazide,was synthesized as an intermediate in the synthesis of certain azole derivatives (Akhtar et al., 2008). The C—N bond length of 1.330 (3)Å is similar to C—N 1.321 (3) Å, indicating the single bond character.The N1—N2 bond length of 1.415 (3) Å in the title compound is longer than the N—N distance [1.366 (3)Å] in the crystal structure of N-propionyl-N'-(3-hydroxy-2-naphthoyl)hydrazide (Zheng, 2008). The Bromo group is coplanar with the phenyl plane C3/C4/C5/C6/C7/C8 with deviation from the plane of 0.030 (4) Å. The molecular packing diagram (Fig. 2) shows the presence of two intermolecular N—H···O hydrogen bonds, (Table 1), one of which is generated via translation along [0 1 0], the other via inversion symmetry.

Related literature top

For carboxyhydrazide derivatives with biological activities, see: Belkadi & Othman (2006); Goswami et al. (1984); Akhtar et al. (2008); Akhtar, Hameed et al. (2007); Ahmad et al. (1996); Akhtar et al. (2006); For related structures, see: Akhtar, Khawar Rauf et al. (2007); Zheng (2008).

Experimental top

Methyl 2-(4-bromophenoxy)propionate (5.0 g, 0.0193 mol) was dissolved in methanol (20 ml) and hydrazine hydrate (80%, 3.50 mL, 0.0679 mol) added slowly with stirring. The reaction mixture was set to reflux. After completion of the reaction (TLC, 6 hrs), the reaction mixture was concentrated and poured to water. The precipitated solid was filtered and recrystallized from ethanol/ water. The spectroscopic and physical characterization data will be reported separately.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and TEXSAN (Molecular Structure Corporation & Rigaku, 2004).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. View of the N—H···O hydrogen bonded molecules. The unit cell has been omitted for clarity.

2-(4-Bromophenoxy)propanohydrazide top

Crystal data top

C₉H₁₁BrN₂O₂	F(000) = 520
M_r = 259.11	D_x = 1.624 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 2804 reflections
a = 10.2598 (14) Å	θ = 3.4–27.5°
b = 4.8009 (7) Å	µ = 3.86 mm⁻¹
c = 23.322 (3) Å	T = 113 K
β = 112.712 (6)°	Block, colorless
V = 1059.7 (3) Å³	0.50 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2201 reflections with I > 2σ(I)
Detector resolution: 14.62 pixels mm^-1	R_int = 0.039
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: integration (NUMABS; Higashi, 1999)	h = −13→11
T_min = 0.531, T_max = 0.759	k = −6→4
8296 measured reflections	l = −26→30
2418 independent reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.0037P)² + 1.6325P] where P = (F_o² + 2F_c²)/3
2418 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

C₉H₁₁BrN₂O₂	V = 1059.7 (3) Å³
M_r = 259.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.2598 (14) Å	µ = 3.86 mm⁻¹
b = 4.8009 (7) Å	T = 113 K
c = 23.322 (3) Å	0.50 × 0.30 × 0.20 mm
β = 112.712 (6)°

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2418 independent reflections
Absorption correction: integration (NUMABS; Higashi, 1999)	2201 reflections with I > 2σ(I)
T_min = 0.531, T_max = 0.759	R_int = 0.039
8296 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.59 e Å⁻³
2418 reflections	Δρ_min = −0.75 e Å⁻³
137 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
C1	0.4780 (3)	0.1909 (5)	0.40801 (12)	0.0143 (5)
O1	0.4868 (2)	−0.0616 (4)	0.41874 (9)	0.0203 (4)
N1	0.5635 (2)	0.3771 (4)	0.44658 (11)	0.0162 (5)
H1	0.551 (3)	0.551 (6)	0.4399 (14)	0.019*
N2	0.6750 (3)	0.3047 (5)	0.50307 (11)	0.0200 (5)
H2A	0.643 (3)	0.205 (7)	0.5240 (15)	0.024*
H2B	0.740 (3)	0.209 (6)	0.4928 (14)	0.024*
C2	0.3698 (3)	0.3120 (6)	0.34780 (13)	0.0188 (6)
H2	0.3260	0.4839	0.3568	0.023*
O2	0.2635 (2)	0.1095 (4)	0.31761 (9)	0.0199 (4)
C3	0.1643 (3)	0.0534 (5)	0.34207 (13)	0.0164 (5)
C4	0.0672 (3)	−0.1518 (6)	0.31070 (12)	0.0180 (5)
H4	0.0761	−0.2460	0.2766	0.022*
C5	−0.0425 (3)	−0.2199 (6)	0.32900 (13)	0.0205 (6)
H5	−0.1092	−0.3595	0.3076	0.025*
C6	−0.0528 (3)	−0.0808 (6)	0.37882 (14)	0.0222 (6)
C7	0.0439 (3)	0.1215 (6)	0.41093 (14)	0.0218 (6)
H7	0.0353	0.2140	0.4453	0.026*
C8	0.1534 (3)	0.1881 (6)	0.39257 (13)	0.0190 (6)
H8	0.2208	0.3256	0.4145	0.023*
Br1	−0.20430 (4)	−0.16915 (9)	0.403569 (18)	0.04154 (13)
C9	0.4395 (4)	0.3772 (7)	0.30247 (15)	0.0332 (8)
H9A	0.4827	0.2076	0.2943	0.050*
H9B	0.5125	0.5194	0.3204	0.050*
H9C	0.3682	0.4466	0.2634	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0158 (13)	0.0134 (12)	0.0163 (13)	−0.0004 (10)	0.0090 (11)	0.0010 (10)
O1	0.0227 (11)	0.0116 (9)	0.0254 (11)	−0.0004 (8)	0.0079 (9)	0.0015 (8)
N1	0.0194 (12)	0.0079 (10)	0.0167 (12)	0.0010 (9)	0.0020 (10)	0.0014 (9)
N2	0.0196 (12)	0.0209 (12)	0.0168 (12)	0.0003 (10)	0.0041 (10)	0.0026 (10)
C2	0.0176 (13)	0.0184 (13)	0.0176 (14)	−0.0041 (11)	0.0035 (11)	0.0023 (11)
O2	0.0209 (10)	0.0220 (10)	0.0152 (10)	−0.0090 (8)	0.0053 (8)	−0.0031 (8)
C3	0.0145 (13)	0.0166 (13)	0.0146 (13)	0.0008 (10)	0.0017 (11)	0.0041 (10)
C4	0.0186 (13)	0.0177 (13)	0.0140 (13)	0.0000 (11)	0.0023 (11)	−0.0006 (11)
C5	0.0178 (14)	0.0194 (14)	0.0194 (15)	−0.0039 (11)	0.0018 (11)	0.0008 (11)
C6	0.0165 (14)	0.0272 (15)	0.0218 (15)	0.0005 (11)	0.0062 (12)	0.0047 (12)
C7	0.0212 (15)	0.0216 (15)	0.0200 (15)	0.0031 (11)	0.0049 (12)	−0.0021 (11)
C8	0.0159 (13)	0.0182 (13)	0.0176 (14)	−0.0010 (11)	0.0006 (11)	−0.0019 (11)
Br1	0.02723 (18)	0.0649 (3)	0.0383 (2)	−0.01613 (17)	0.01901 (15)	−0.01174 (19)
C9	0.0321 (18)	0.043 (2)	0.0216 (16)	−0.0163 (15)	0.0075 (14)	0.0044 (14)

Geometric parameters (Å, º) top

C1—O1	1.234 (3)	C4—C5	1.389 (4)
C1—N1	1.330 (3)	C4—H4	0.9500
C1—C2	1.529 (4)	C5—C6	1.379 (4)
N1—N2	1.415 (3)	C5—H5	0.9500
N1—H1	0.85 (3)	C6—C7	1.384 (4)
N2—H2A	0.83 (3)	C6—Br1	1.903 (3)
N2—H2B	0.92 (3)	C7—C8	1.385 (4)
C2—O2	1.427 (3)	C7—H7	0.9500
C2—C9	1.520 (4)	C8—H8	0.9500
C2—H2	1.0000	C9—H9A	0.9800
O2—C3	1.372 (3)	C9—H9B	0.9800
C3—C8	1.385 (4)	C9—H9C	0.9800
C3—C4	1.392 (4)

O1—C1—N1	123.1 (2)	C5—C4—H4	119.8
O1—C1—C2	122.0 (2)	C3—C4—H4	119.8
N1—C1—C2	114.9 (2)	C6—C5—C4	118.7 (3)
C1—N1—N2	123.4 (2)	C6—C5—H5	120.7
C1—N1—H1	121 (2)	C4—C5—H5	120.7
N2—N1—H1	115 (2)	C5—C6—C7	121.6 (3)
N1—N2—H2A	109 (2)	C5—C6—Br1	119.0 (2)
N1—N2—H2B	107 (2)	C7—C6—Br1	119.4 (2)
H2A—N2—H2B	111 (3)	C6—C7—C8	119.5 (3)
O2—C2—C9	105.8 (2)	C6—C7—H7	120.3
O2—C2—C1	109.9 (2)	C8—C7—H7	120.3
C9—C2—C1	110.3 (2)	C3—C8—C7	119.8 (3)
O2—C2—H2	110.3	C3—C8—H8	120.1
C9—C2—H2	110.3	C7—C8—H8	120.1
C1—C2—H2	110.3	C2—C9—H9A	109.5
C3—O2—C2	118.5 (2)	C2—C9—H9B	109.5
O2—C3—C8	125.4 (2)	H9A—C9—H9B	109.5
O2—C3—C4	114.6 (2)	C2—C9—H9C	109.5
C8—C3—C4	120.1 (3)	H9A—C9—H9C	109.5
C5—C4—C3	120.4 (3)	H9B—C9—H9C	109.5

O1—C1—N1—N2	1.5 (4)	O2—C3—C4—C5	−177.1 (2)
C2—C1—N1—N2	−176.7 (2)	C8—C3—C4—C5	1.1 (4)
O1—C1—C2—O2	15.9 (4)	C3—C4—C5—C6	−0.2 (4)
N1—C1—C2—O2	−165.9 (2)	C4—C5—C6—C7	−0.6 (4)
O1—C1—C2—C9	−100.3 (3)	C4—C5—C6—Br1	179.2 (2)
N1—C1—C2—C9	77.9 (3)	C5—C6—C7—C8	0.4 (4)
C9—C2—O2—C3	−166.8 (2)	Br1—C6—C7—C8	−179.3 (2)
C1—C2—O2—C3	74.1 (3)	O2—C3—C8—C7	176.8 (2)
C2—O2—C3—C8	3.5 (4)	C4—C3—C8—C7	−1.3 (4)
C2—O2—C3—C4	−178.3 (2)	C6—C7—C8—C3	0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (3)	1.97 (3)	2.812 (3)	170 (3)
N2—H2A···O1ⁱⁱ	0.83 (3)	2.33 (3)	3.127 (3)	161 (3)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁BrN₂O₂
M_r	259.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	10.2598 (14), 4.8009 (7), 23.322 (3)
β (°)	112.712 (6)
V (Å³)	1059.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.86
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	Integration (NUMABS; Higashi, 1999)
T_min, T_max	0.531, 0.759
No. of measured, independent and observed [I > 2σ(I)] reflections	8296, 2418, 2201
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.076, 1.20
No. of reflections	2418
No. of parameters	137
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.75

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SIR97 (Altomare et al., 1999), ORTEPII (Johnson, 1976), SHELXL97 (Sheldrick, 2008) and TEXSAN (Molecular Structure Corporation & Rigaku, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (3)	1.97 (3)	2.812 (3)	170 (3)
N2—H2A···O1ⁱⁱ	0.83 (3)	2.33 (3)	3.127 (3)	161 (3)

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

Acknowledgements

MKR is grateful to the HEC–Pakistan for financial support for a PhD program under scholarship No. ILC-0363104.

References

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