(1Z)-1-(2,4-Dichloro­phen­yl)ethan-1-one semicarbazone

Fun, H.-K.; Balasubramani, K.; Vijesh, A.M.; Malladii, S.; Isloor, A.M.

doi:10.1107/S1600536809029900

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2072

doi:10.1107/S1600536809029900

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(1Z)-1-(2,4-Dichlorophenyl)ethan-1-one semicarbazone

Hoong-Kun Fun,^a ^*‡ Kasthuri Balasubramani,^a A. M. Vijesh,^b § Shridhar Malladii ^c and Arun M. Isloor ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 Universiti Sains Malaysia, Penang, Malaysia, ^bSeQuent Scientific Limited, No. 120 A&B, Industrial Area, Baikampady, New Bangalore, Karnataka 575 011, India, and ^cDepartment of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India
^*Correspondence e-mail: hkfun@usm.my

(Received 7 July 2009; accepted 28 July 2009; online 8 August 2009)

In the title compound, C₉H₉Cl₂N₃O, the semicarbazone group is approximately planar, with an r.m.s deviation from the mean plane of 0.011 (2) Å. The dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 38.76 (9)°. The crystal structure is further stabilized by N—H⋯O and C—H⋯O hydrogen bonding.

Related literature

For applications of semicarbazone derivatives, see: Warren et al. (1977 ); Chandra & Gupta (2005 ); Jain et al. (2002 ); Pilgram (1978 ); Yogeeswari et al. (2004 ); For semicarbazide preparations, see: Furniss et al. (1978 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₉Cl₂N₃O
M_r = 246.09
Monoclinic, C 2/c
a = 37.8079 (17) Å
b = 3.8097 (2) Å
c = 14.4920 (7) Å
β = 98.852 (2)°
V = 2062.52 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 100 K
0.42 × 0.14 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.707, T_max = 0.974
32124 measured reflections
4202 independent reflections
3654 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.192
S = 1.11
4202 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 3.37 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.85 (3)	2.07 (3)	2.907 (2)	168 (3)
N3—H2N3⋯O1ⁱⁱ	0.81 (4)	2.13 (4)	2.924 (2)	164 (4)
C9—H9A⋯O1ⁱⁱⁱ	0.96	2.59	3.465 (2)	152
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+2, -z.

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/S1600536809029900/bq2153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029900/bq2153Isup2.hkl

checkCIF report

Comment top

In organic chemistry, a semicarbazone is a derivative of an aldehyde or ketone formed by a condensation between a ketone or aldehyde and semicarbazide. They find immense applications in the field of synthetic chemistry, such as medicinal chemistry (Warren et al., 1977), organometallics (Chandra & Gupta, 2005), polymers (Jain et al., 2002) and herbicides (Pilgram, 1978). 4-Sulphamoylphenyl semicarbazones were synthesized and were found to possess anticonvulsant activity (Yogeeswari et al., 2004). Keeping in view of their biological importance, we hereby reporting crystal structure of the semicarbazone of commercial importance.

The semicarbazone group (Fig. 1) (C9/C6/C7/N1/N2/C8/O1/N3) is approximately planar, with an r.m.s deviation of 0.011 (2)Å for atom N1, while the dihedral angle between the least-squares plane through the semicarbazone group and the benzene ring is 38.76 (9)°. The molecules are linked via N—H···O hydrogen bonds to generate R₂²(8) ring motifs (Bernstein et al. 1995). These motifs are further connected through C—H···O hydrogen bonds to form a one-dimensional chain along the [0 1 0] direction (Fig. 2).

Related literature top

For applications of semicarbazone derivatives, see: Warren et al. (1977); Chandra & Gupta (2005); Jain et al. (2002); Pilgram (1978); Yogeeswari et al. (2004); For semicarbazide preparation, see: Furniss et al. (1978). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

3.16 g (28.3 mmol) of semicarbazide hydrochloride and 2.83 g (34.5 mmol) of crystallized sodium acetate was dissolved in 25 ml of water (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. (5.0 g, 26.5 mmol) of 2,4-dichloroacetophenone in 25 ml of ethanol was then added and the mixture stirred well for 6 h. The separated semicarbazone was filtered, washed with chilled water and recrystallized from an ethanol-DMF mixture. Yield was found to be 5.23 g, 86.02%. M.p. 501–503 K.

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 and the atom numbering scheme.
	Fig. 2. An one-dimensional chain of (I) with R₂²(8) ring motifs along the [010] direction. Dashed lines indicate the hydrogen bonding.

(1Z)-1-(2,4-Dichlorophenyl)ethan-1-one semicarbazone top

Crystal data top

C₉H₉Cl₂N₃O	F(000) = 1008
M_r = 246.09	D_x = 1.585 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9961 reflections
a = 37.8079 (17) Å	θ = 2.9–34.0°
b = 3.8097 (2) Å	µ = 0.60 mm⁻¹
c = 14.4920 (7) Å	T = 100 K
β = 98.852 (2)°	Plate, colorless
V = 2062.52 (17) Å³	0.42 × 0.14 × 0.04 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4202 independent reflections
Radiation source: fine-focus sealed tube	3654 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 34.1°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −59→58
T_min = 0.707, T_max = 0.974	k = −5→5
32124 measured reflections	l = −22→22

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.1176P)² + 5.115P] where P = (F_o² + 2F_c²)/3
4202 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 3.37 e Å⁻³
0 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

C₉H₉Cl₂N₃O	V = 2062.52 (17) Å³
M_r = 246.09	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 37.8079 (17) Å	µ = 0.60 mm⁻¹
b = 3.8097 (2) Å	T = 100 K
c = 14.4920 (7) Å	0.42 × 0.14 × 0.04 mm
β = 98.852 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4202 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3654 reflections with I > 2σ(I)
T_min = 0.707, T_max = 0.974	R_int = 0.037
32124 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 3.37 e Å⁻³
4202 reflections	Δρ_min = −0.82 e Å⁻³
149 parameters

Special details top

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

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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
Cl1	0.254197 (12)	1.14825 (12)	0.14159 (3)	0.01486 (13)
Cl2	0.149699 (12)	0.64254 (12)	−0.11406 (3)	0.01413 (13)
O1	−0.00572 (4)	0.4635 (5)	0.11828 (10)	0.0162 (3)
N1	0.08094 (4)	0.7191 (5)	0.08948 (11)	0.0127 (3)
N2	0.04458 (4)	0.6666 (5)	0.06771 (12)	0.0141 (3)
N3	0.04484 (5)	0.5433 (7)	0.22395 (13)	0.0222 (4)
C1	0.14889 (5)	1.0482 (6)	0.14140 (13)	0.0132 (3)
H1A	0.1327	1.0954	0.1819	0.016*
C2	0.18500 (5)	1.1187 (5)	0.17051 (14)	0.0132 (3)
H2A	0.1928	1.2131	0.2293	0.016*
C3	0.20913 (5)	1.0451 (5)	0.10974 (13)	0.0120 (3)
C4	0.19805 (5)	0.9013 (5)	0.02261 (13)	0.0124 (3)
H4A	0.2145	0.8508	−0.0172	0.015*
C5	0.16165 (5)	0.8336 (5)	−0.00436 (13)	0.0112 (3)
C6	0.13617 (5)	0.9086 (5)	0.05322 (13)	0.0112 (3)
C7	0.09697 (5)	0.8539 (5)	0.02541 (13)	0.0116 (3)
C8	0.02647 (5)	0.5559 (6)	0.13727 (14)	0.0152 (3)
C9	0.07833 (5)	0.9765 (5)	−0.06811 (13)	0.0123 (3)
H9A	0.0571	1.1034	−0.0601	0.018*
H9B	0.0720	0.7772	−0.1078	0.018*
H9C	0.0940	1.1272	−0.0962	0.018*
H1N2	0.0320 (9)	0.660 (8)	0.014 (2)	0.016 (7)*
H1N3	0.0663 (10)	0.636 (10)	0.231 (3)	0.028 (9)*
H2N3	0.0324 (10)	0.484 (10)	0.262 (3)	0.028 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0092 (2)	0.0180 (2)	0.0168 (2)	−0.00196 (13)	0.00036 (15)	−0.00011 (14)
Cl2	0.0141 (2)	0.0179 (2)	0.0105 (2)	−0.00169 (14)	0.00232 (15)	−0.00251 (14)
O1	0.0090 (6)	0.0283 (8)	0.0111 (6)	−0.0027 (5)	0.0010 (5)	0.0002 (5)
N1	0.0076 (6)	0.0192 (7)	0.0111 (7)	−0.0008 (5)	0.0009 (5)	0.0005 (5)
N2	0.0084 (6)	0.0238 (8)	0.0097 (7)	−0.0026 (5)	0.0005 (5)	0.0012 (5)
N3	0.0114 (7)	0.0461 (12)	0.0088 (7)	−0.0060 (8)	0.0002 (6)	0.0043 (7)
C1	0.0100 (7)	0.0191 (8)	0.0104 (7)	−0.0019 (6)	0.0016 (6)	−0.0020 (6)
C2	0.0114 (7)	0.0163 (8)	0.0114 (7)	−0.0007 (6)	0.0005 (6)	−0.0018 (6)
C3	0.0082 (7)	0.0140 (8)	0.0135 (8)	−0.0007 (6)	0.0006 (6)	0.0011 (6)
C4	0.0119 (7)	0.0126 (7)	0.0130 (8)	−0.0005 (6)	0.0027 (6)	−0.0004 (6)
C5	0.0113 (7)	0.0127 (7)	0.0097 (7)	0.0001 (5)	0.0021 (6)	−0.0005 (5)
C6	0.0104 (7)	0.0130 (7)	0.0101 (7)	−0.0007 (6)	0.0015 (5)	0.0013 (6)
C7	0.0099 (7)	0.0141 (8)	0.0105 (7)	−0.0007 (5)	0.0009 (6)	−0.0003 (5)
C8	0.0109 (7)	0.0234 (9)	0.0116 (8)	−0.0011 (7)	0.0025 (6)	0.0017 (7)
C9	0.0107 (7)	0.0140 (8)	0.0114 (7)	−0.0011 (6)	−0.0010 (6)	0.0017 (6)

Geometric parameters (Å, º) top

Cl1—C3	1.7403 (19)	C1—H1A	0.9300
Cl2—C5	1.7436 (19)	C2—C3	1.391 (3)
O1—C8	1.256 (2)	C2—H2A	0.9300
N1—C7	1.291 (2)	C3—C4	1.381 (3)
N1—N2	1.377 (2)	C4—C5	1.395 (3)
N2—C8	1.369 (2)	C4—H4A	0.9300
N2—H1N2	0.85 (3)	C5—C6	1.398 (3)
N3—C8	1.339 (3)	C6—C7	1.489 (3)
N3—H1N3	0.88 (4)	C7—C9	1.503 (3)
N3—H2N3	0.81 (4)	C9—H9A	0.9600
C1—C2	1.392 (3)	C9—H9B	0.9600
C1—C6	1.399 (3)	C9—H9C	0.9600

C7—N1—N2	117.12 (16)	C4—C5—C6	122.38 (17)
C8—N2—N1	118.08 (16)	C4—C5—Cl2	116.02 (14)
C8—N2—H1N2	113 (2)	C6—C5—Cl2	121.59 (15)
N1—N2—H1N2	128 (2)	C5—C6—C1	116.83 (17)
C8—N3—H1N3	115 (2)	C5—C6—C7	123.95 (17)
C8—N3—H2N3	112 (3)	C1—C6—C7	119.21 (16)
H1N3—N3—H2N3	131 (4)	N1—C7—C6	114.76 (16)
C2—C1—C6	122.24 (17)	N1—C7—C9	124.43 (17)
C2—C1—H1A	118.9	C6—C7—C9	120.65 (16)
C6—C1—H1A	118.9	O1—C8—N3	122.71 (18)
C3—C2—C1	118.53 (17)	O1—C8—N2	120.16 (18)
C3—C2—H2A	120.7	N3—C8—N2	117.11 (18)
C1—C2—H2A	120.7	C7—C9—H9A	109.5
C4—C3—C2	121.52 (17)	C7—C9—H9B	109.5
C4—C3—Cl1	118.62 (14)	H9A—C9—H9B	109.5
C2—C3—Cl1	119.83 (15)	C7—C9—H9C	109.5
C3—C4—C5	118.48 (17)	H9A—C9—H9C	109.5
C3—C4—H4A	120.8	H9B—C9—H9C	109.5
C5—C4—H4A	120.8

C7—N1—N2—C8	−173.82 (19)	Cl2—C5—C6—C7	−3.6 (3)
C6—C1—C2—C3	−0.4 (3)	C2—C1—C6—C5	1.6 (3)
C1—C2—C3—C4	−0.7 (3)	C2—C1—C6—C7	−177.46 (18)
C1—C2—C3—Cl1	177.08 (15)	N2—N1—C7—C6	179.31 (17)
C2—C3—C4—C5	0.7 (3)	N2—N1—C7—C9	4.0 (3)
Cl1—C3—C4—C5	−177.15 (14)	C5—C6—C7—N1	137.72 (19)
C3—C4—C5—C6	0.5 (3)	C1—C6—C7—N1	−43.3 (3)
C3—C4—C5—Cl2	−178.54 (15)	C5—C6—C7—C9	−46.8 (3)
C4—C5—C6—C1	−1.6 (3)	C1—C6—C7—C9	132.2 (2)
Cl2—C5—C6—C1	177.39 (15)	N1—N2—C8—O1	−171.2 (2)
C4—C5—C6—C7	177.37 (18)	N1—N2—C8—N3	7.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.85 (3)	2.07 (3)	2.907 (2)	168 (3)
N3—H2N3···O1ⁱⁱ	0.81 (4)	2.13 (4)	2.924 (2)	164 (4)
C9—H9A···O1ⁱⁱⁱ	0.96	2.59	3.465 (2)	152

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

Experimental details

Crystal data
Chemical formula	C₉H₉Cl₂N₃O
M_r	246.09
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	37.8079 (17), 3.8097 (2), 14.4920 (7)
β (°)	98.852 (2)
V (Å³)	2062.52 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.42 × 0.14 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.707, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	32124, 4202, 3654
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.789

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.192, 1.11
No. of reflections	4202
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	3.37, −0.82

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
N2—H1N2···O1ⁱ	0.85 (3)	2.07 (3)	2.907 (2)	168 (3)
N3—H2N3···O1ⁱⁱ	0.81 (4)	2.13 (4)	2.924 (2)	164 (4)
C9—H9A···O1ⁱⁱⁱ	0.96	2.59	3.465 (2)	151.9

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India.

Acknowledgements

HKF and KBS thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. KBS thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. AMI is grateful to the Head of the Department of Chemistry and the Director, NITK, Surathkal, India, for providing research facilities.

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