N′-[(1E)-1-(4-Chloro­phen­yl)ethyl­idene]formohydrazide

Shafiq, Z.; Yaqub, M.; Tahir, M.N.; Nawaz, M.H.; Iqbal, M.S.

doi:10.1107/S1600536809037143

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2494

doi:10.1107/S1600536809037143

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N′-[(1E)-1-(4-Chlorophenyl)ethylidene]formohydrazide

Zahid Shafiq,^a Muhammad Yaqub,^a M. Nawaz Tahir,^b Mian Hasnain Nawaz ^a and M. Saeed Iqbal ^c ^*

^aDepartment of Chemistry, Bahauddin Zakariya University, Multan-60800, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 5 September 2009; accepted 14 September 2009; online 19 September 2009)

The structure of the title compound, C₉H₉ClN₂O, consists of centrosymmetric dimers due to intermolecular N—H⋯O hydrogen bonding, forming R₂²(8) ring motifs. The dihedral angle between the p-chlorophenyl unit and the remaining heavy-atom group is 6.77 (17)°.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For a related structure, see: Guo (2007 ).

Experimental

Crystal data

C₉H₉ClN₂O
M_r = 196.63
Monoclinic, P 2₁ /c
a = 5.9373 (5) Å
b = 6.2178 (4) Å
c = 25.3495 (18) Å
β = 93.900 (4)°
V = 933.66 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.914, T_max = 0.940
9690 measured reflections
2311 independent reflections
1426 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.150
S = 1.05
2311 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.8600	2.0800	2.920 (3)	164.00
Symmetry code: (i) -x, -y, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037143/bq2157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037143/bq2157Isup2.hkl

checkCIF report

Comment top

Schiff bases are important intermediates in a number of enzymatic reactions involving interaction of an enzyme with an amino or a carbonyl group of the substrate. The title compound (I, Fig. 1), has been prepared as a derivative.

The crystal structures of N'-(1-(4-Chlorophenyl)ethylidene)propionohydrazide (Guo, 2007) has been published which differs from the title compound (I) due to the attachment of ethyl moiety instead of H-atom with the carbonyl group.

In the title compound, due to intermolecular H-bonding the molecules are dimerized forming 8-membered R₂²(8) ring motifs (Table 1, Fig. 2) (Bernstein et al., 1995). The p-Clorophenyl moiety A (C1—C6, Cl1) and the remaining heavy atoms group B (C8, C7, N1, N2 C9, O1) are almost planar with r.m.s. deviations of 0.007 and 0.009 Å, respectively, with a 6.77 (17)° dihedral angle between them.

Related literature top

For hydrogen-bond motifs, see: Bernstein et al. (1995). For a related structure, see: Guo (2007).

Experimental top

formohydrazide (1 g, 0.017 mol) was dissolved in ethanol (10 ml) and stirred. To this solution 4-Chlororoacetophenone (2.067 ml, 0.017 mol) was added dropwise and refluxed for 30 min. During refluxing precipitates were formed and the reaction mixture was further heated for 2 h. The completion of reaction was monitored by TLC. The solution was cooled to room temperature and the crued solid was collected by suction filtration. The precipitates were washed with hot ethanol, filtered and dried. The colorless prisms of title compound (I) were obtained by crystallization of the crude material in 1,4-dioxan.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules are dimerized and form ring motifs.

N'-[(1E)-1-(4-Chlorophenyl)ethylidene]formohydrazide top

Crystal data top

C₉H₉ClN₂O	F(000) = 408
M_r = 196.63	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1864 reflections
a = 5.9373 (5) Å	θ = 2.3–28.0°
b = 6.2178 (4) Å	µ = 0.37 mm⁻¹
c = 25.3495 (18) Å	T = 296 K
β = 93.900 (4)°	Prismatic, colorless
V = 933.66 (12) Å³	0.25 × 0.22 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2311 independent reflections
Radiation source: fine-focus sealed tube	1426 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 3.2°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
T_min = 0.914, T_max = 0.940	l = −33→32
9690 measured 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0631P)² + 0.2896P] where P = (F_o² + 2F_c²)/3
2311 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₉ClN₂O	V = 933.66 (12) Å³
M_r = 196.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9373 (5) Å	µ = 0.37 mm⁻¹
b = 6.2178 (4) Å	T = 296 K
c = 25.3495 (18) Å	0.25 × 0.22 × 0.18 mm
β = 93.900 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2311 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1426 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.940	R_int = 0.025
9690 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
2311 reflections	Δρ_min = −0.20 e Å⁻³
119 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Cl1	0.38204 (13)	1.27773 (12)	0.21878 (3)	0.0806 (3)
O1	0.2494 (3)	0.0349 (3)	−0.03180 (7)	0.0740 (7)
N1	0.1941 (3)	0.4376 (3)	0.06100 (7)	0.0500 (6)
N2	0.1350 (3)	0.2578 (3)	0.03140 (7)	0.0536 (7)
C1	0.1329 (3)	0.6969 (3)	0.12510 (8)	0.0447 (7)
C2	0.0192 (4)	0.7732 (4)	0.16716 (9)	0.0611 (9)
C3	0.0928 (4)	0.9511 (4)	0.19580 (10)	0.0654 (9)
C4	0.2836 (4)	1.0560 (4)	0.18273 (9)	0.0523 (8)
C5	0.3992 (4)	0.9858 (4)	0.14095 (10)	0.0622 (9)
C6	0.3239 (4)	0.8092 (4)	0.11281 (9)	0.0593 (8)
C7	0.0599 (4)	0.5018 (3)	0.09485 (8)	0.0481 (7)
C8	−0.1579 (4)	0.3947 (4)	0.10580 (11)	0.0743 (10)
C9	0.2786 (4)	0.1908 (4)	−0.00268 (10)	0.0623 (9)
H2	−0.11039	0.70239	0.17636	0.0733*
H2A	0.00968	0.19185	0.03497	0.0644*
H3	0.01322	0.99959	0.22383	0.0785*
H5	0.52814	1.05794	0.13180	0.0746*
H6	0.40342	0.76308	0.08454	0.0712*
H9	0.41191	0.26791	−0.00468	0.0747*
H81	−0.13024	0.24613	0.11431	0.1115*
H82	−0.26116	0.40444	0.07507	0.1115*
H83	−0.22185	0.46470	0.13504	0.1115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0897 (6)	0.0672 (5)	0.0858 (5)	−0.0185 (3)	0.0123 (4)	−0.0250 (3)
O1	0.0641 (12)	0.0777 (12)	0.0818 (12)	−0.0196 (9)	0.0177 (9)	−0.0322 (10)
N1	0.0503 (11)	0.0477 (10)	0.0521 (10)	−0.0062 (8)	0.0042 (8)	−0.0047 (8)
N2	0.0498 (11)	0.0522 (12)	0.0592 (12)	−0.0094 (9)	0.0059 (9)	−0.0090 (9)
C1	0.0426 (12)	0.0427 (11)	0.0491 (12)	−0.0028 (9)	0.0055 (9)	0.0032 (9)
C2	0.0555 (15)	0.0653 (15)	0.0647 (15)	−0.0166 (12)	0.0207 (11)	−0.0094 (11)
C3	0.0656 (17)	0.0681 (16)	0.0649 (15)	−0.0096 (13)	0.0224 (12)	−0.0138 (12)
C4	0.0548 (14)	0.0467 (12)	0.0553 (13)	−0.0031 (10)	0.0032 (10)	−0.0035 (9)
C5	0.0566 (15)	0.0567 (14)	0.0756 (16)	−0.0178 (11)	0.0215 (12)	−0.0066 (12)
C6	0.0558 (14)	0.0593 (14)	0.0658 (14)	−0.0143 (11)	0.0252 (11)	−0.0120 (11)
C7	0.0454 (12)	0.0467 (12)	0.0524 (12)	−0.0047 (10)	0.0048 (10)	0.0036 (9)
C8	0.0589 (16)	0.0718 (18)	0.0944 (19)	−0.0237 (13)	0.0209 (14)	−0.0215 (14)
C9	0.0531 (15)	0.0669 (16)	0.0677 (16)	−0.0143 (12)	0.0107 (12)	−0.0152 (12)

Geometric parameters (Å, º) top

Cl1—C4	1.733 (3)	C4—C5	1.372 (3)
O1—C9	1.224 (3)	C5—C6	1.368 (3)
N1—N2	1.379 (3)	C7—C8	1.497 (3)
N1—C7	1.274 (3)	C2—H2	0.9300
N2—C9	1.322 (3)	C3—H3	0.9300
N2—H2A	0.8600	C5—H5	0.9300
C1—C2	1.384 (3)	C6—H6	0.9300
C1—C7	1.484 (3)	C8—H81	0.9600
C1—C6	1.385 (3)	C8—H82	0.9600
C2—C3	1.378 (3)	C8—H83	0.9600
C3—C4	1.367 (3)	C9—H9	0.9300

Cl1···C4ⁱ	3.535 (2)	H2···C8	2.6200
O1···N2ⁱⁱ	2.920 (3)	H2···H83	1.9000
O1···C8ⁱⁱ	3.288 (3)	H2A···C8	2.4600
O1···C9ⁱⁱⁱ	3.202 (3)	H2A···H81	2.2500
O1···H2Aⁱⁱ	2.0800	H2A···H82	2.3600
O1···H6^iv	2.8300	H2A···O1ⁱⁱ	2.0800
O1···H9ⁱⁱⁱ	2.8600	H2A···C9ⁱⁱ	3.0100
O1···H81ⁱⁱ	2.7800	H5···C8^ix	2.9100
N2···O1ⁱⁱ	2.920 (3)	H5···H81^ix	2.4100
N1···H6	2.4300	H6···N1	2.4300
N2···H81	2.7100	H6···O1^iv	2.8300
N2···H82	2.8200	H6···C9^iv	2.9100
C4···Cl1^v	3.535 (2)	H6···H9^iv	2.3700
C7···C9^vi	3.537 (3)	H9···O1ⁱⁱⁱ	2.8600
C8···O1ⁱⁱ	3.288 (3)	H9···H6^iv	2.3700
C9···O1ⁱⁱⁱ	3.202 (3)	H81···N2	2.7100
C9···C9ⁱⁱⁱ	3.537 (3)	H81···C3^x	3.0000
C9···C7^vi	3.537 (3)	H81···H2A	2.2500
C2···H83	2.5000	H81···H5^viii	2.4100
C3···H81^vii	3.0000	H81···O1ⁱⁱ	2.7800
C8···H2A	2.4600	H82···N2	2.8200
C8···H5^viii	2.9100	H82···H2A	2.3600
C8···H2	2.6200	H83···C2	2.5000
C9···H2Aⁱⁱ	3.0100	H83···H2	1.9000
C9···H6^iv	2.9100

N2—N1—C7	118.23 (18)	O1—C9—N2	124.9 (2)
N1—N2—C9	117.37 (18)	C1—C2—H2	119.00
C9—N2—H2A	121.00	C3—C2—H2	119.00
N1—N2—H2A	121.00	C2—C3—H3	120.00
C6—C1—C7	120.71 (19)	C4—C3—H3	120.00
C2—C1—C7	122.53 (18)	C4—C5—H5	120.00
C2—C1—C6	116.75 (19)	C6—C5—H5	120.00
C1—C2—C3	121.8 (2)	C1—C6—H6	119.00
C2—C3—C4	119.6 (2)	C5—C6—H6	119.00
Cl1—C4—C5	119.44 (19)	C7—C8—H81	109.00
Cl1—C4—C3	120.45 (19)	C7—C8—H82	109.00
C3—C4—C5	120.1 (2)	C7—C8—H83	109.00
C4—C5—C6	119.7 (2)	H81—C8—H82	109.00
C1—C6—C5	122.1 (2)	H81—C8—H83	109.00
N1—C7—C1	115.47 (19)	H82—C8—H83	109.00
N1—C7—C8	124.97 (19)	O1—C9—H9	118.00
C1—C7—C8	119.56 (19)	N2—C9—H9	118.00

C7—N1—N2—C9	−178.5 (2)	C6—C1—C2—C3	−0.5 (3)
N2—N1—C7—C8	1.0 (3)	C7—C1—C2—C3	178.1 (2)
N2—N1—C7—C1	−179.61 (17)	C6—C1—C7—C8	−174.7 (2)
N1—N2—C9—O1	−179.6 (2)	C1—C2—C3—C4	−0.2 (4)
C2—C1—C6—C5	0.6 (3)	C2—C3—C4—C5	0.8 (4)
C7—C1—C6—C5	−178.0 (2)	C2—C3—C4—Cl1	−179.02 (19)
C2—C1—C7—C8	6.7 (3)	Cl1—C4—C5—C6	179.14 (19)
C6—C1—C7—N1	5.9 (3)	C3—C4—C5—C6	−0.7 (4)
C2—C1—C7—N1	−172.7 (2)	C4—C5—C6—C1	−0.1 (4)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x, −y, −z; (iii) −x+1, −y, −z; (iv) −x+1, −y+1, −z; (v) −x+1, y−1/2, −z+1/2; (vi) −x, −y+1, −z; (vii) x, y+1, z; (viii) x−1, y−1, z; (ix) x+1, y+1, z; (x) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱⁱ	0.8600	2.0800	2.920 (3)	164.00

Symmetry code: (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₉H₉ClN₂O
M_r	196.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.9373 (5), 6.2178 (4), 25.3495 (18)
β (°)	93.900 (4)
V (Å³)	933.66 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.25 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.914, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	9690, 2311, 1426
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.150, 1.05
No. of reflections	2311
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.8600	2.0800	2.920 (3)	164.00

Symmetry code: (i) −x, −y, −z.

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore, and for technical support, respectively.

References

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