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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1591–o1592.
Published online 2009 June 17. doi:  10.1107/S1600536809022284
PMCID: PMC2969411

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

Abstract

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 [triangle]); Jain et al. (2002 [triangle]); Pilgram (1978 [triangle]); Warren et al. (1977 [triangle]); Yogeeswari et al. (2004 [triangle]). For the preparation, see: Furniss et al. (1978 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For a related structure, see: Fun et al. (2009 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1591-scheme1.jpg

Experimental

Crystal data

  • C9H10BrN3O
  • M r = 256.11
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1591-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.080
  • wR(F 2) = 0.249
  • S = 1.16
  • 2945 reflections
  • 129 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 3.03 e Å−3
  • Δρmin = −1.11 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022284/ng2596sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022284/ng2596Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The H-atoms bound to N2 and N3 was located from the difference Fourier map and refined freely. The rest of the hydrogen atoms were placed in calculated positions, with C—H = 0.93 Å, Uiso = 1.2Ueq(C) for aromatic, and C—H = 0.96 Å, Uiso = 1.5Ueq(C) for CH3 atom. A rotating group model was used for the methyl group. The N1—N2 bond was restrained with a N—N bond distance of 1.37 (1) Å. The crystal studied was a twin with the refined BASF parameter of 0.495 (1).

The final difference Fourier map had a peak/hole in the vicnity of Br1.

Figures

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.

Crystal data

C9H10BrN3OF(000) = 512
Mr = 256.11Dx = 1.701 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3514 reflections
a = 17.6700 (8) Åθ = 3.0–28.2°
b = 7.3426 (4) ŵ = 4.08 mm1
c = 7.9082 (4) ÅT = 100 K
β = 102.953 (3)°Block, colourless
V = 999.93 (9) Å30.22 × 0.12 × 0.08 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer2945 independent reflections
Radiation source: fine-focus sealed tube2105 reflections with I > 2σ(I)
graphiteRint = 0.053
[var phi] and ω scansθmax = 30.2°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −24→24
Tmin = 0.466, Tmax = 0.733k = −10→10
12017 measured reflectionsl = −11→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.080Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.249H-atom parameters constrained
S = 1.16w = 1/[σ2(Fo2) + (0.1217P)2 + 9.4338P] where P = (Fo2 + 2Fc2)/3
2945 reflections(Δ/σ)max < 0.000
129 parametersΔρmax = 3.03 e Å3
1 restraintΔρmin = −1.11 e Å3

Special details

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)

xyzUiso*/Ueq
Br10.03467 (5)0.43707 (10)0.2675 (2)0.0212 (2)
N30.4198 (6)0.1238 (13)0.8352 (16)0.034 (2)
H3A0.44300.02370.82140.041*
H3B0.37720.12140.87040.041*
N10.3450 (5)0.4205 (11)0.899 (2)0.039 (3)
N20.4105 (5)0.4401 (11)0.8290 (14)0.027 (2)
H2B0.42570.54590.80380.032*
O10.5113 (4)0.2902 (11)0.7512 (13)0.032 (2)
C10.1856 (7)0.6630 (14)0.6881 (14)0.026 (2)
H1A0.18940.77290.74790.032*
C20.1231 (6)0.6387 (14)0.5429 (16)0.027 (2)
H2A0.08760.73170.50500.032*
C30.1165 (6)0.4722 (15)0.4594 (13)0.023 (2)
C40.1698 (7)0.3367 (14)0.5184 (14)0.025 (2)
H4A0.16380.22360.46420.030*
C50.2310 (7)0.3651 (14)0.6544 (16)0.028 (2)
H5A0.26710.27250.68850.033*
C60.2409 (6)0.5321 (14)0.7448 (17)0.027 (2)
C70.3094 (5)0.5625 (12)0.911 (3)0.0244 (19)
C80.4503 (7)0.2840 (13)0.8017 (14)0.025 (2)
C90.3368 (5)0.7556 (12)0.914 (3)0.030 (2)
H9A0.39110.76100.96820.045*
H9B0.30810.82920.97790.045*
H9C0.32880.80040.79710.045*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0269 (4)0.0173 (4)0.0201 (8)−0.0037 (3)0.0067 (17)−0.0023 (5)
N30.039 (5)0.013 (4)0.057 (7)0.000 (4)0.026 (5)−0.004 (5)
N10.019 (3)0.015 (4)0.083 (11)0.001 (3)0.011 (6)−0.004 (6)
N20.033 (5)0.009 (4)0.043 (6)0.001 (3)0.018 (4)−0.004 (4)
O10.029 (3)0.037 (5)0.038 (4)−0.003 (3)0.021 (4)−0.001 (5)
C10.043 (6)0.013 (4)0.023 (5)−0.003 (4)0.008 (5)−0.004 (4)
C20.023 (5)0.019 (4)0.039 (6)−0.005 (4)0.008 (5)−0.003 (5)
C30.020 (4)0.034 (6)0.016 (4)−0.001 (4)0.008 (4)0.005 (4)
C40.035 (5)0.019 (5)0.019 (5)−0.008 (4)0.002 (4)0.004 (4)
C50.033 (5)0.013 (4)0.034 (6)0.000 (4)0.004 (5)−0.005 (4)
C60.024 (5)0.020 (5)0.040 (6)0.000 (4)0.014 (5)0.004 (4)
C70.021 (3)0.016 (3)0.036 (6)0.003 (3)0.005 (8)−0.016 (6)
C80.046 (6)0.007 (4)0.024 (5)0.007 (4)0.009 (5)−0.002 (4)
C90.022 (4)0.011 (3)0.060 (8)−0.003 (3)0.018 (8)0.009 (8)

Geometric parameters (Å, °)

Br1—C31.865 (10)C2—C31.382 (16)
N3—C81.344 (14)C2—H2A0.9300
N3—H3A0.8600C3—C41.378 (15)
N3—H3B0.8600C4—C51.359 (15)
N1—C71.233 (11)C4—H4A0.9300
N1—N21.397 (9)C5—C61.410 (15)
N2—C81.387 (12)C5—H5A0.9300
N2—H2B0.8600C6—C71.59 (2)
O1—C81.232 (13)C7—C91.496 (12)
C1—C61.373 (15)C9—H9A0.9600
C1—C21.415 (16)C9—H9B0.9600
C1—H1A0.9300C9—H9C0.9600
C8—N3—H3A120.0C4—C5—C6121.4 (11)
C8—N3—H3B120.0C4—C5—H5A119.3
H3A—N3—H3B120.0C6—C5—H5A119.3
C7—N1—N2115.2 (10)C1—C6—C5116.4 (11)
C8—N2—N1118.1 (8)C1—C6—C7121.7 (9)
C8—N2—H2B121.0C5—C6—C7121.8 (9)
N1—N2—H2B121.0N1—C7—C9129.3 (10)
C6—C1—C2123.1 (10)N1—C7—C697.0 (12)
C6—C1—H1A118.5C9—C7—C6109.2 (13)
C2—C1—H1A118.5O1—C8—N3121.0 (9)
C3—C2—C1117.8 (10)O1—C8—N2122.1 (9)
C3—C2—H2A121.1N3—C8—N2116.9 (10)
C1—C2—H2A121.1C7—C9—H9A109.5
C4—C3—C2119.9 (10)C7—C9—H9B109.5
C4—C3—Br1121.5 (8)H9A—C9—H9B109.5
C2—C3—Br1118.6 (8)C7—C9—H9C109.5
C5—C4—C3121.3 (10)H9A—C9—H9C109.5
C5—C4—H4A119.4H9B—C9—H9C109.5
C3—C4—H4A119.4
C7—N1—N2—C8−176.1 (14)C4—C5—C6—C7176.3 (13)
C6—C1—C2—C32.4 (17)N2—N1—C7—C9−20 (3)
C1—C2—C3—C40.1 (15)N2—N1—C7—C6101.6 (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—N19.4 (17)
Br1—C3—C4—C5177.5 (9)C1—C6—C7—C9−38.6 (17)
C3—C4—C5—C62.4 (18)C5—C6—C7—C9145.3 (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—N33.9 (16)
C4—C5—C6—C10.0 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···O1i0.862.213.052 (12)168
N3—H3A···O1ii0.862.032.885 (13)171
C9—H9A···O1iii0.962.513.34 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2596).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography