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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1634–o1635.
Published online 2009 June 20. doi:  10.1107/S160053680902279X
PMCID: PMC2969321

(E)-1-(4-Chloro­phen­yl)ethanone semi­carbazone

Abstract

In the title compound, C9H10ClN3O, the semicarbazone group is approximately planar, with an r.m.s. deviation from the mean plane of 0.054 (1) Å. The dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 30.46 (5)°. In the solid state, mol­ecules are linked via inter­molecular N—H(...)O and N—H(...)N hydrogen bonds, generating R 2 2(9) ring motifs which, together with R 2 2(8) ring motifs formed by pairs of inter­molecular N—H(...)O hydrogen bonds, lead to the formation of a seldom-observed mol­ecular trimer. Furthermore, N—H(...)O hydrogen bonds form R 2 1(7) ring motifs with C—H(...)O hydrogen bonds, further consolidating the crystal structure. Mol­ecules are linked by these inter­molecular inter­actions, forming two-dimensional networks parallel to (100).

Related literature

For the synthetic utility and applications of semicarbazone derivatives, see: Warren et al. (1977 [triangle]); Chandra & Gupta (2005 [triangle]); Jain et al. (2002 [triangle]); Pilgram (1978 [triangle]); Yogeeswari et al. (2004 [triangle]). For a related structure, see: Fun et al. (2009 [triangle]). For the preparation, see: Furniss et al. (1978 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For bond-length data, see: Allen et al. (1987 [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-o1634-scheme1.jpg

Experimental

Crystal data

  • C9H10ClN3O
  • M r = 211.65
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1634-efi6.jpg
  • a = 21.8191 (4) Å
  • b = 7.0484 (1) Å
  • c = 13.7249 (2) Å
  • β = 109.633 (1)°
  • V = 1988.04 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.35 mm−1
  • T = 100 K
  • 0.41 × 0.20 × 0.03 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.867, T max = 0.991
  • 28636 measured reflections
  • 3539 independent reflections
  • 2912 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.101
  • S = 1.04
  • 3539 reflections
  • 167 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.27 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/S160053680902279X/sj2631sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902279X/sj2631Isup2.hkl

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ thanks USM for a Research Fellowship. 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 numerous applications in the field of synthetic chemistry, such as 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 possess anticonvulsant activity (Yogeeswari et al., 2004). Herein we report the crystal structure of the title semicarbazone which may have commercial and synthetic importance.

The bond lengths (Allen et al., 1987) and angles in the molecule (Fig. 1) are within normal ranges, and are comparable to those observed in a closely related structure (Fun et al., 2009). The semicarbazone group (C9/C6/C7/N1/N2/C8/O1/N3) is approximately planar, with an r.m.s. deviation of 0.054 (1) Å for atom N2 while the dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 30.46 (5)°.

In the solid state, the molecules are linked via intermolecular N3—H2N3···O1 and N3—H1N3···N1 hydrogen bonds to generate R22(9) ring motifs which, together with the R22(8) ring motifs formed by pairs of intermolecular N2—H1N2···O1 hydrogen bonds, lead to the formation of a seldom-observed molecular trimer (Fig. 2). Furthermore, N2—H1N2···O1 hydrogen bonds form R21(7) ring motifs (Fig. 2) with C9—H9C···O1 hydrogen bonds to further consolidated the crystal structure. The molecules are linked by these intermolecular interactions to form two-dimensional networks parallel to the (1 0 0) plane.

Experimental

0.780 g (7.0 mmol) of semicarbazide hydrochloride and 0.698 g (8.5 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. To this (1 g, 6.5 mmol) of 4-choloacetophenone was added 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 1.1 g, 80.35%. M.p. 478–479 K.

Refinement

All hydrogen atoms were located from the difference Fourier map and refined freely.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Part of the crystal packing of the title compound, viewed along the a axis, showing the formation of a molecular trimer. Atom-numbering is shown for those non-H atoms involved in hydrogen bonds and intermolecular interactions are shown as dashed lines. ...

Crystal data

C9H10ClN3OF(000) = 880
Mr = 211.65Dx = 1.414 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6351 reflections
a = 21.8191 (4) Åθ = 3.1–32.1°
b = 7.0484 (1) ŵ = 0.35 mm1
c = 13.7249 (2) ÅT = 100 K
β = 109.633 (1)°Plate, colourless
V = 1988.04 (6) Å30.41 × 0.20 × 0.03 mm
Z = 8

Data collection

Bruker SMART APEXII CCD area-detector diffractometer3539 independent reflections
Radiation source: fine-focus sealed tube2912 reflections with I > 2σ(I)
graphiteRint = 0.052
[var phi] and ω scansθmax = 32.3°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −32→32
Tmin = 0.867, Tmax = 0.991k = −10→10
28636 measured reflectionsl = −20→20

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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.049P)2 + 1.2937P] where P = (Fo2 + 2Fc2)/3
3539 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = −0.27 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 e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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)

xyzUiso*/Ueq
Cl10.023375 (16)−0.37949 (4)0.13113 (2)0.02330 (9)
O10.28038 (4)0.80096 (12)0.13075 (6)0.01675 (17)
N10.18652 (5)0.38677 (13)0.08164 (7)0.01332 (18)
N20.22047 (5)0.53956 (13)0.06342 (7)0.01416 (18)
N30.24395 (6)0.61942 (14)0.23627 (8)0.0176 (2)
C10.11370 (6)−0.05633 (16)−0.01844 (9)0.0167 (2)
C20.08397 (6)−0.21004 (16)0.01146 (10)0.0178 (2)
C30.06045 (6)−0.18847 (16)0.09274 (9)0.0172 (2)
C40.06590 (6)−0.01713 (17)0.14505 (9)0.0184 (2)
C50.09612 (6)0.13476 (16)0.11541 (9)0.0167 (2)
C60.12052 (6)0.11705 (15)0.03359 (9)0.0136 (2)
C70.15469 (6)0.27915 (15)0.00516 (9)0.0137 (2)
C80.24965 (6)0.65995 (15)0.14448 (8)0.0136 (2)
C90.15172 (7)0.30648 (18)−0.10430 (9)0.0189 (2)
H10.1299 (8)−0.071 (2)−0.0751 (13)0.022 (4)*
H20.0807 (8)−0.332 (3)−0.0235 (13)0.029 (4)*
H40.0472 (8)−0.007 (2)0.2047 (13)0.026 (4)*
H50.0998 (8)0.254 (2)0.1502 (13)0.024 (4)*
H9A0.1211 (11)0.237 (3)−0.1478 (18)0.053 (6)*
H9B0.1901 (12)0.271 (3)−0.1107 (18)0.064 (7)*
H9C0.1416 (9)0.433 (3)−0.1261 (15)0.036 (5)*
H1N20.2197 (8)0.579 (3)0.0019 (14)0.028 (4)*
H1N30.2668 (8)0.684 (2)0.2863 (13)0.022 (4)*
H2N30.2271 (8)0.522 (2)0.2487 (12)0.020 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.02608 (17)0.01993 (15)0.02367 (16)−0.00699 (11)0.00806 (12)0.00422 (10)
O10.0227 (4)0.0154 (4)0.0128 (4)−0.0054 (3)0.0067 (3)−0.0010 (3)
N10.0157 (4)0.0121 (4)0.0120 (4)−0.0013 (3)0.0044 (3)0.0007 (3)
N20.0202 (5)0.0127 (4)0.0100 (4)−0.0042 (3)0.0056 (4)−0.0007 (3)
N30.0272 (6)0.0163 (4)0.0102 (4)−0.0065 (4)0.0076 (4)−0.0015 (3)
C10.0176 (5)0.0165 (5)0.0163 (5)−0.0024 (4)0.0064 (4)−0.0024 (4)
C20.0183 (6)0.0141 (5)0.0204 (6)−0.0024 (4)0.0055 (4)−0.0019 (4)
C30.0165 (5)0.0148 (5)0.0188 (5)−0.0024 (4)0.0039 (4)0.0037 (4)
C40.0200 (6)0.0194 (5)0.0166 (5)−0.0019 (4)0.0074 (4)0.0013 (4)
C50.0200 (6)0.0151 (5)0.0158 (5)−0.0013 (4)0.0073 (4)−0.0010 (4)
C60.0138 (5)0.0142 (5)0.0121 (5)−0.0004 (4)0.0034 (4)0.0013 (4)
C70.0158 (5)0.0127 (4)0.0121 (5)−0.0006 (4)0.0040 (4)0.0003 (4)
C80.0164 (5)0.0129 (4)0.0109 (5)−0.0002 (4)0.0040 (4)−0.0005 (4)
C90.0266 (7)0.0185 (5)0.0124 (5)−0.0052 (5)0.0077 (5)−0.0008 (4)

Geometric parameters (Å, °)

Cl1—C31.7410 (12)C2—C31.3842 (18)
O1—C81.2481 (13)C2—H20.977 (18)
N1—C71.2922 (14)C3—C41.3895 (17)
N1—N21.3768 (13)C4—C51.3882 (16)
N2—C81.3737 (14)C4—H41.033 (17)
N2—H1N20.883 (18)C5—C61.4006 (16)
N3—C81.3378 (14)C5—H50.958 (17)
N3—H1N30.835 (18)C6—C71.4863 (15)
N3—H2N30.826 (17)C7—C91.4943 (16)
C1—C21.3935 (16)C9—H9A0.88 (2)
C1—C61.3979 (15)C9—H9B0.91 (2)
C1—H10.963 (16)C9—H9C0.94 (2)
C7—N1—N2119.12 (9)C4—C5—C6120.81 (11)
C8—N2—N1117.86 (9)C4—C5—H5120.0 (10)
C8—N2—H1N2115.9 (12)C6—C5—H5119.1 (10)
N1—N2—H1N2125.4 (12)C1—C6—C5118.92 (10)
C8—N3—H1N3116.1 (12)C1—C6—C7120.97 (10)
C8—N3—H2N3124.2 (11)C5—C6—C7120.08 (10)
H1N3—N3—H2N3118.0 (16)N1—C7—C6114.71 (10)
C2—C1—C6120.63 (11)N1—C7—C9124.82 (10)
C2—C1—H1119.1 (10)C6—C7—C9120.46 (10)
C6—C1—H1120.3 (10)O1—C8—N3122.47 (10)
C3—C2—C1119.16 (11)O1—C8—N2119.73 (10)
C3—C2—H2120.4 (10)N3—C8—N2117.80 (10)
C1—C2—H2120.4 (10)C7—C9—H9A112.1 (14)
C2—C3—C4121.43 (11)C7—C9—H9B109.4 (15)
C2—C3—Cl1119.65 (9)H9A—C9—H9B107 (2)
C4—C3—Cl1118.92 (9)C7—C9—H9C111.6 (11)
C5—C4—C3119.04 (11)H9A—C9—H9C105.6 (19)
C5—C4—H4122.2 (10)H9B—C9—H9C110.9 (19)
C3—C4—H4118.7 (10)
C7—N1—N2—C8175.03 (10)C4—C5—C6—C7−177.97 (11)
C6—C1—C2—C30.79 (18)N2—N1—C7—C6179.22 (9)
C1—C2—C3—C4−0.05 (18)N2—N1—C7—C90.30 (17)
C1—C2—C3—Cl1−179.84 (9)C1—C6—C7—N1−146.43 (11)
C2—C3—C4—C5−0.55 (19)C5—C6—C7—N131.82 (15)
Cl1—C3—C4—C5179.24 (9)C1—C6—C7—C932.55 (16)
C3—C4—C5—C60.41 (18)C5—C6—C7—C9−149.20 (12)
C2—C1—C6—C5−0.92 (18)N1—N2—C8—O1−179.37 (10)
C2—C1—C6—C7177.35 (11)N1—N2—C8—N30.92 (16)
C4—C5—C6—C10.32 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1i0.884 (19)2.007 (19)2.8866 (12)173.3 (19)
N3—H1N3···N1ii0.835 (18)2.264 (18)3.0904 (14)170.5 (16)
N3—H2N3···O1iii0.826 (17)2.316 (17)3.0499 (13)148.4 (15)
C9—H9C···O1i0.94 (2)2.55 (2)3.2162 (16)128.1 (16)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2631).

References

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