(E)-1-(4-Bromo­phen­yl)ethan-1-one semicarbazone

Fun, H.-K.; Goh, J.H.; Padaki, M.; Malladi, S.; Isloor, A.M.

doi:10.1107/S1600536809022284

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages o1591-o1592

doi:10.1107/S1600536809022284

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(E)-1-(4-Bromophenyl)ethan-1-one semicarbazone

Hoong-Kun Fun,^a ^*‡ Jia Hao Goh,^a Mahesh Padaki,^b Shridhar Malladi ^b and Arun M. Isloor ^b

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

(Received 10 June 2009; accepted 11 June 2009; online 17 June 2009)

In the title compound, C₉H₁₀BrN₃O, the hydrazone portion and aliphatic chain are essentially coplanar [maximum deviation 0.057 (15) Å] and the mean plane makes a dihedral angle of 70.9 (6)° with the benzene ring. The main feature of the crystal structure is the intermolecular N—H⋯O hydrogen bond, which links molecules into zigzag chains along the a axis. These chains are further stacked along the b axis. The crystal structure features non-classical intermolecular C—H⋯O interactions. The crystal studied was a nonmerohedral twin, with a twin ratio of 0.505 (1):0.495 (1).

Related literature

For general background and applications of semicarbazone derivatives, see: Chandra & Gupta (2005 ); Jain et al. (2002 ); Pilgram (1978 ); Warren et al. (1977 ); Yogeeswari et al. (2004 ). For the preparation, see: Furniss et al. (1978 ). For bond-length data, see: Allen et al. (1987 ). For a related structure, see: Fun et al. (2009 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₉H₁₀BrN₃O
M_r = 256.11
Monoclinic, P 2₁ /c
a = 17.6700 (8) Å
b = 7.3426 (4) Å
c = 7.9082 (4) Å
β = 102.953 (3)°
V = 999.93 (9) Å³
Z = 4
Mo Kα radiation
μ = 4.08 mm⁻¹
T = 100 K
0.22 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.466, T_max = 0.733
12017 measured reflections
2945 independent reflections
2105 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.249
S = 1.16
2945 reflections
129 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 3.03 e Å⁻³
Δρ_min = −1.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1ⁱ	0.86	2.21	3.052 (12)	168
N3—H3A⋯O1ⁱⁱ	0.86	2.03	2.885 (13)	171
C9—H9A⋯O1ⁱⁱⁱ	0.96	2.51	3.34 (2)	144
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+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/S1600536809022284/ng2596sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022284/ng2596Isup2.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. Semicarbazones find immerse applications in the field of synthetic chemistry, such as in medicinal chemistry (Warren et al., 1977), organometalics (Chandra & Gupta, 2005), polymers (Jain et al., 2002) and herbicides (Pilgram, 1978). 4-Sulphamoylphenyl semicarbazones were synthesized and were found to posses anticonvulsant activity (Yogeeswari et al., 2004). We hereby report the crystal structure of the semicarbazone of commercial importance keeping in view of their synthetic importance.

The bond lengths (Allen et al., 1987) and angles in the molecule (Fig. 1) are within normal ranges and are comparable to a closely related structure (Fun et al., 2009). Atoms C7, C8, N1, N2, N3 and O1 lie on the same plane with a maximum deviation of 0.057 (15) Å for atom N1. This plane makes dihedral angle of 70.9 (6)° with the C1-C6 benzene ring.

In the crystal packing (Fig. 2), N3—H3A···O1 hydrogen bonds link the molecules into one-dimensional zig-zag extended chains along the a axis. These chains are further stacked along the b axis and thus forming two-dimensional extended networks parallel to the ab plane. The crystal structure is further stabilized by intermolecular C9—H9A···O1 interactions.

Related literature top

For general background and applications of semicarbazone derivatives, see: Chandra & Gupta (2005); Jain et al. (2002); Pilgram (1978); Warren et al. (1977); Yogeeswari et al. (2004). For the preparation, see: Furniss et al. (1978). For bond-length data, see: Allen et al. (1987). For a related structure, see: Fun et al. (2009). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

0.57 g (5.11 mmol) of semicarbazide hydrochloride and 0.54 g (6.60 mmol) of crystallized sodium acetate was dissolved in 10 ml of water (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. 1 g (5.02 mmol) 4-Bromoacetophenone was added to this and shaken well. A little alcohol was added to dissolve the turbidity. It was shaken for 10 more minutes and allowed to stand. The semicarbazone crystallizes on standing for 6 h. The separated crystals were filtered, washed with cold water and recrystallized from alcohol. Yield was found to be 1.158 g, 90.05 %. M.p. 479-481 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 the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Intermolecular interactions are shown as dashed lines.

(E)-1-(4-Bromophenyl)ethan-1-one semicarbazone top

Crystal data top

C₉H₁₀BrN₃O	F(000) = 512
M_r = 256.11	D_x = 1.701 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3514 reflections
a = 17.6700 (8) Å	θ = 3.0–28.2°
b = 7.3426 (4) Å	µ = 4.08 mm⁻¹
c = 7.9082 (4) Å	T = 100 K
β = 102.953 (3)°	Block, colourless
V = 999.93 (9) Å³	0.22 × 0.12 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2945 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 30.2°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −24→24
T_min = 0.466, T_max = 0.733	k = −10→10
12017 measured reflections	l = −11→11

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.249	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.1217P)² + 9.4338P] where P = (F_o² + 2F_c²)/3
2945 reflections	(Δ/σ)_max < 0.000
129 parameters	Δρ_max = 3.03 e Å⁻³
1 restraint	Δρ_min = −1.11 e Å⁻³

Crystal data top

C₉H₁₀BrN₃O	V = 999.93 (9) Å³
M_r = 256.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.6700 (8) Å	µ = 4.08 mm⁻¹
b = 7.3426 (4) Å	T = 100 K
c = 7.9082 (4) Å	0.22 × 0.12 × 0.08 mm
β = 102.953 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2945 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2105 reflections with I > 2σ(I)
T_min = 0.466, T_max = 0.733	R_int = 0.053
12017 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	1 restraint
wR(F²) = 0.249	H-atom parameters constrained
S = 1.16	Δρ_max = 3.03 e Å⁻³
2945 reflections	Δρ_min = −1.11 e Å⁻³
129 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
Br1	0.03467 (5)	0.43707 (10)	0.2675 (2)	0.0212 (2)
N3	0.4198 (6)	0.1238 (13)	0.8352 (16)	0.034 (2)
H3A	0.4430	0.0237	0.8214	0.041*
H3B	0.3772	0.1214	0.8704	0.041*
N1	0.3450 (5)	0.4205 (11)	0.899 (2)	0.039 (3)
N2	0.4105 (5)	0.4401 (11)	0.8290 (14)	0.027 (2)
H2B	0.4257	0.5459	0.8038	0.032*
O1	0.5113 (4)	0.2902 (11)	0.7512 (13)	0.032 (2)
C1	0.1856 (7)	0.6630 (14)	0.6881 (14)	0.026 (2)
H1A	0.1894	0.7729	0.7479	0.032*
C2	0.1231 (6)	0.6387 (14)	0.5429 (16)	0.027 (2)
H2A	0.0876	0.7317	0.5050	0.032*
C3	0.1165 (6)	0.4722 (15)	0.4594 (13)	0.023 (2)
C4	0.1698 (7)	0.3367 (14)	0.5184 (14)	0.025 (2)
H4A	0.1638	0.2236	0.4642	0.030*
C5	0.2310 (7)	0.3651 (14)	0.6544 (16)	0.028 (2)
H5A	0.2671	0.2725	0.6885	0.033*
C6	0.2409 (6)	0.5321 (14)	0.7448 (17)	0.027 (2)
C7	0.3094 (5)	0.5625 (12)	0.911 (3)	0.0244 (19)
C8	0.4503 (7)	0.2840 (13)	0.8017 (14)	0.025 (2)
C9	0.3368 (5)	0.7556 (12)	0.914 (3)	0.030 (2)
H9A	0.3911	0.7610	0.9682	0.045*
H9B	0.3081	0.8292	0.9779	0.045*
H9C	0.3288	0.8004	0.7971	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0269 (4)	0.0173 (4)	0.0201 (8)	−0.0037 (3)	0.0067 (17)	−0.0023 (5)
N3	0.039 (5)	0.013 (4)	0.057 (7)	0.000 (4)	0.026 (5)	−0.004 (5)
N1	0.019 (3)	0.015 (4)	0.083 (11)	0.001 (3)	0.011 (6)	−0.004 (6)
N2	0.033 (5)	0.009 (4)	0.043 (6)	0.001 (3)	0.018 (4)	−0.004 (4)
O1	0.029 (3)	0.037 (5)	0.038 (4)	−0.003 (3)	0.021 (4)	−0.001 (5)
C1	0.043 (6)	0.013 (4)	0.023 (5)	−0.003 (4)	0.008 (5)	−0.004 (4)
C2	0.023 (5)	0.019 (4)	0.039 (6)	−0.005 (4)	0.008 (5)	−0.003 (5)
C3	0.020 (4)	0.034 (6)	0.016 (4)	−0.001 (4)	0.008 (4)	0.005 (4)
C4	0.035 (5)	0.019 (5)	0.019 (5)	−0.008 (4)	0.002 (4)	0.004 (4)
C5	0.033 (5)	0.013 (4)	0.034 (6)	0.000 (4)	0.004 (5)	−0.005 (4)
C6	0.024 (5)	0.020 (5)	0.040 (6)	0.000 (4)	0.014 (5)	0.004 (4)
C7	0.021 (3)	0.016 (3)	0.036 (6)	0.003 (3)	0.005 (8)	−0.016 (6)
C8	0.046 (6)	0.007 (4)	0.024 (5)	0.007 (4)	0.009 (5)	−0.002 (4)
C9	0.022 (4)	0.011 (3)	0.060 (8)	−0.003 (3)	0.018 (8)	0.009 (8)

Geometric parameters (Å, º) top

Br1—C3	1.865 (10)	C2—C3	1.382 (16)
N3—C8	1.344 (14)	C2—H2A	0.9300
N3—H3A	0.8600	C3—C4	1.378 (15)
N3—H3B	0.8600	C4—C5	1.359 (15)
N1—C7	1.233 (11)	C4—H4A	0.9300
N1—N2	1.397 (9)	C5—C6	1.410 (15)
N2—C8	1.387 (12)	C5—H5A	0.9300
N2—H2B	0.8600	C6—C7	1.59 (2)
O1—C8	1.232 (13)	C7—C9	1.496 (12)
C1—C6	1.373 (15)	C9—H9A	0.9600
C1—C2	1.415 (16)	C9—H9B	0.9600
C1—H1A	0.9300	C9—H9C	0.9600

C8—N3—H3A	120.0	C4—C5—C6	121.4 (11)
C8—N3—H3B	120.0	C4—C5—H5A	119.3
H3A—N3—H3B	120.0	C6—C5—H5A	119.3
C7—N1—N2	115.2 (10)	C1—C6—C5	116.4 (11)
C8—N2—N1	118.1 (8)	C1—C6—C7	121.7 (9)
C8—N2—H2B	121.0	C5—C6—C7	121.8 (9)
N1—N2—H2B	121.0	N1—C7—C9	129.3 (10)
C6—C1—C2	123.1 (10)	N1—C7—C6	97.0 (12)
C6—C1—H1A	118.5	C9—C7—C6	109.2 (13)
C2—C1—H1A	118.5	O1—C8—N3	121.0 (9)
C3—C2—C1	117.8 (10)	O1—C8—N2	122.1 (9)
C3—C2—H2A	121.1	N3—C8—N2	116.9 (10)
C1—C2—H2A	121.1	C7—C9—H9A	109.5
C4—C3—C2	119.9 (10)	C7—C9—H9B	109.5
C4—C3—Br1	121.5 (8)	H9A—C9—H9B	109.5
C2—C3—Br1	118.6 (8)	C7—C9—H9C	109.5
C5—C4—C3	121.3 (10)	H9A—C9—H9C	109.5
C5—C4—H4A	119.4	H9B—C9—H9C	109.5
C3—C4—H4A	119.4

C7—N1—N2—C8	−176.1 (14)	C4—C5—C6—C7	176.3 (13)
C6—C1—C2—C3	2.4 (17)	N2—N1—C7—C9	−20 (3)
C1—C2—C3—C4	0.1 (15)	N2—N1—C7—C6	101.6 (13)
C1—C2—C3—Br1	−179.9 (8)	C1—C6—C7—N1	−174.6 (12)
C2—C3—C4—C5	−2.4 (16)	C5—C6—C7—N1	9.4 (17)
Br1—C3—C4—C5	177.5 (9)	C1—C6—C7—C9	−38.6 (17)
C3—C4—C5—C6	2.4 (18)	C5—C6—C7—C9	145.3 (12)
C2—C1—C6—C5	−2.4 (17)	N1—N2—C8—O1	−175.3 (12)
C2—C1—C6—C7	−178.7 (12)	N1—N2—C8—N3	3.9 (16)
C4—C5—C6—C1	0.0 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1ⁱ	0.86	2.21	3.052 (12)	168
N3—H3A···O1ⁱⁱ	0.86	2.03	2.885 (13)	171
C9—H9A···O1ⁱⁱⁱ	0.96	2.51	3.34 (2)	144

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀BrN₃O
M_r	256.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	17.6700 (8), 7.3426 (4), 7.9082 (4)
β (°)	102.953 (3)
V (Å³)	999.93 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.08
Crystal size (mm)	0.22 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.466, 0.733
No. of measured, independent and observed [I > 2σ(I)] reflections	12017, 2945, 2105
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.707

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.249, 1.16
No. of reflections	2945
No. of parameters	129
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.03, −1.11

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—H2B···O1ⁱ	0.8600	2.2100	3.052 (12)	168.00
N3—H3A···O1ⁱⁱ	0.8600	2.0300	2.885 (13)	171.00
C9—H9A···O1ⁱⁱⁱ	0.9600	2.5100	3.34 (2)	144.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and JHG thank Universiti Sains Malaysia for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). JHG thanks the Malaysia Government and Universiti Sains Malaysia for a student assistantship under the Science Fund (Grant No. 305/PFIZIK/613312). 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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