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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1113.
Published online 2010 April 17. doi:  10.1107/S1600536810013048
PMCID: PMC2979154

1-Benzoyl-4-(2-nitro­phen­yl)semicarbazide

Abstract

The title compound, C14H12N4O4, was prepared by the reaction of 2-nitro­phenyl isocyanate with benzoyl­hydrazine. The dihedral angle between the rings is 71.49 (6)) Å. The mol­ecular conformation is stabilized by an intra­molecular N—H(...)O hydrogen bond, generating an S(6) ring. The crystal packing shows N—H(...)O hydrogen bonds.

Related literature

For the bioactivity of urea derivatives, see: Yip et al. (1986 [triangle]); Liu et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1113-scheme1.jpg

Experimental

Crystal data

  • C14H12N4O4
  • M r = 300.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1113-efi1.jpg
  • a = 4.655 (2) Å
  • b = 15.020 (7) Å
  • c = 10.005 (5) Å
  • β = 97.954 (7)°
  • V = 692.9 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 113 K
  • 0.20 × 0.16 × 0.12 mm

Data collection

  • Rigaku Saturn 724 CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.979, T max = 0.987
  • 5816 measured reflections
  • 1652 independent reflections
  • 1383 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.059
  • S = 0.96
  • 1652 reflections
  • 212 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013048/bt5244sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013048/bt5244Isup2.hkl

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

Acknowledgments

This work was supported by the Natural Science Foundation of Henan Province, China (grant No. 082300420110) and the Natural Science Foundation of Henan Province Education Department, China (grant No. 2007150036).

supplementary crystallographic information

Comment

Urea derivates are very interesting reagents due to their useful properties and important medical and biological applications. For example, aryl urea derivates have been found to inhibit cell division as weedicides, and homologous aryl urea derivates have also been researched as antibacterial activity. Thidiazuron, a substituted heterocyclic urea compound, mimicked the effect of benzyladenine(BA) in the Ca2+ + cytokinin system and the IAA + cytokinin systems systems. (Yip et al., 1986). Recently, better activity of sectiona benzoyl urea derivates were reported. (Liu et al., 2005). In order to discover further biologically active urea compounds, the title compound was synthesized and its crystal structure was determined (Fig. 1). The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bond. The crystal packing shows N—H···O hydrogen-bonds. (Fig. 2).

Experimental

2-nitrophenyl isocyanate(0.164 g, 1 mmol) and benzoyl hydrazine (0.136 g, 1 mmol) were milled and mixed thoroughly in an agate mortar. Then the mixture was put into a beaker and irradiated by microwave for 1 min. After the reaction was completed, the resulting mixture was dissolved in 95% ethanol and filtrated. The products separated and were collected by filtration. The title compound was recrystallized from ethanol and single crystals were obtained by slow evaporation.

Refinement

In the absence of anomalous scatterers, the absolute structure could not be determined and, therefore, Friedel pairs were merged. All H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.95 Å, and included in the refinement using a riding model, with Uiso(H) = 1.2Ueq(C). H atoms bonded to N were freely refined.

Figures

Fig. 1.
The asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
The packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C14H12N4O4F(000) = 312
Mr = 300.28Dx = 1.439 Mg m3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 2582 reflections
a = 4.655 (2) Åθ = 1.4–27.9°
b = 15.020 (7) ŵ = 0.11 mm1
c = 10.005 (5) ÅT = 113 K
β = 97.954 (7)°Prism, colorless
V = 692.9 (5) Å30.20 × 0.16 × 0.12 mm
Z = 2

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer1652 independent reflections
Radiation source: fine-focus sealed tube1383 reflections with I > 2σ(I)
graphiteRint = 0.033
Detector resolution: 14.68 pixels mm-1θmax = 27.9°, θmin = 1.4°
ω and [var phi] scansh = −4→6
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −16→19
Tmin = 0.979, Tmax = 0.987l = −13→12
5816 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059w = 1/[σ2(Fo2) + (0.0305P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.007
1652 reflectionsΔρmax = 0.17 e Å3
212 parametersΔρmin = −0.16 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.044 (4)

Special details

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 > 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
O10.4760 (3)−0.01804 (9)0.99297 (16)0.0318 (4)
O20.4185 (3)0.12193 (9)1.02923 (16)0.0305 (4)
O31.1178 (3)0.32395 (8)0.92954 (15)0.0224 (3)
O40.8286 (3)0.48594 (9)0.76324 (14)0.0256 (3)
N10.6951 (4)0.24346 (11)0.90518 (17)0.0191 (4)
H10.539 (5)0.2410 (13)0.936 (2)0.021 (6)*
N20.6976 (4)0.38858 (10)0.97176 (17)0.0172 (3)
H2A0.523 (5)0.3870 (12)0.958 (2)0.014 (5)*
N30.8310 (3)0.47099 (10)0.98749 (17)0.0183 (3)
H3A0.853 (5)0.4899 (15)1.073 (2)0.031 (6)*
N40.5259 (3)0.06040 (10)0.97133 (17)0.0220 (4)
C10.7987 (3)0.16832 (12)0.8453 (2)0.0169 (4)
C20.7208 (4)0.08059 (13)0.8735 (2)0.0186 (4)
C30.8283 (4)0.00766 (13)0.8095 (2)0.0238 (5)
H30.7730−0.05090.83100.029*
C41.0138 (4)0.02023 (13)0.7156 (2)0.0244 (5)
H41.0907−0.02930.67340.029*
C51.0872 (4)0.10670 (13)0.6832 (2)0.0228 (4)
H51.21080.11600.61650.027*
C60.9833 (4)0.17889 (12)0.7465 (2)0.0181 (4)
H61.03770.23720.72290.022*
C70.8559 (4)0.31947 (12)0.93330 (19)0.0165 (4)
C80.9025 (4)0.51379 (12)0.8784 (2)0.0189 (4)
C91.0848 (4)0.59575 (12)0.9075 (2)0.0202 (4)
C101.2623 (4)0.60775 (13)1.0298 (2)0.0228 (4)
H101.26380.56481.09960.027*
C111.4379 (4)0.68291 (13)1.0494 (2)0.0297 (5)
H111.55980.69101.13280.036*
C121.4367 (5)0.74538 (13)0.9493 (3)0.0337 (5)
H121.55760.79640.96360.040*
C131.2588 (5)0.73400 (15)0.8273 (3)0.0404 (6)
H131.25600.77760.75830.048*
C141.0851 (5)0.65894 (14)0.8064 (2)0.0339 (5)
H140.96560.65070.72240.041*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0371 (9)0.0231 (8)0.0370 (10)−0.0064 (6)0.0116 (7)0.0067 (7)
O20.0351 (8)0.0255 (8)0.0349 (10)0.0007 (7)0.0189 (7)0.0013 (7)
O30.0137 (6)0.0229 (7)0.0310 (8)−0.0021 (5)0.0050 (5)−0.0033 (6)
O40.0360 (8)0.0254 (7)0.0149 (8)−0.0060 (6)0.0018 (6)−0.0025 (6)
N10.0144 (8)0.0190 (8)0.0256 (10)−0.0022 (6)0.0089 (7)−0.0017 (7)
N20.0137 (8)0.0160 (8)0.0223 (9)−0.0024 (6)0.0036 (6)−0.0027 (7)
N30.0224 (8)0.0174 (8)0.0156 (9)−0.0034 (6)0.0045 (6)−0.0038 (7)
N40.0203 (8)0.0228 (9)0.0224 (10)−0.0023 (7)0.0007 (7)0.0040 (7)
C10.0114 (9)0.0190 (9)0.0196 (11)−0.0001 (7)−0.0002 (7)−0.0003 (8)
C20.0158 (9)0.0210 (9)0.0185 (10)−0.0010 (7)0.0011 (7)0.0002 (8)
C30.0229 (10)0.0180 (9)0.0295 (12)0.0005 (8)0.0002 (8)−0.0009 (8)
C40.0233 (10)0.0219 (10)0.0281 (12)0.0034 (8)0.0038 (8)−0.0063 (9)
C50.0191 (10)0.0281 (11)0.0217 (11)−0.0005 (8)0.0043 (8)−0.0013 (9)
C60.0150 (8)0.0198 (10)0.0199 (11)−0.0006 (7)0.0033 (7)0.0012 (8)
C70.0166 (9)0.0201 (9)0.0130 (10)−0.0006 (7)0.0024 (7)0.0018 (7)
C80.0205 (10)0.0182 (9)0.0181 (10)0.0011 (7)0.0033 (7)−0.0001 (8)
C90.0241 (10)0.0174 (9)0.0201 (10)−0.0005 (8)0.0066 (8)−0.0016 (8)
C100.0245 (10)0.0216 (10)0.0228 (11)−0.0028 (8)0.0055 (8)−0.0010 (8)
C110.0263 (11)0.0307 (11)0.0324 (13)−0.0058 (9)0.0049 (9)−0.0086 (10)
C120.0414 (13)0.0227 (11)0.0395 (15)−0.0104 (9)0.0148 (10)−0.0086 (10)
C130.0603 (16)0.0267 (12)0.0353 (16)−0.0126 (11)0.0107 (12)0.0065 (10)
C140.0503 (13)0.0265 (11)0.0238 (13)−0.0079 (10)0.0012 (10)0.0028 (9)

Geometric parameters (Å, °)

O1—N41.226 (2)C4—C51.393 (3)
O2—N41.233 (2)C4—H40.9500
O3—C71.227 (2)C5—C61.377 (3)
O4—C81.229 (2)C5—H50.9500
N1—C71.373 (2)C6—H60.9500
N1—C11.395 (2)C8—C91.500 (3)
N1—H10.83 (2)C9—C141.387 (3)
N2—C71.359 (2)C9—C101.390 (3)
N2—N31.384 (2)C10—C111.392 (3)
N2—H2A0.80 (2)C10—H100.9500
N3—C81.348 (3)C11—C121.371 (3)
N3—H3A0.90 (2)C11—H110.9500
N4—C21.456 (3)C12—C131.388 (3)
C1—C61.405 (3)C12—H120.9500
C1—C21.406 (3)C13—C141.386 (3)
C2—C31.396 (3)C13—H130.9500
C3—C41.374 (3)C14—H140.9500
C3—H30.9500
C7—N1—C1123.34 (16)C5—C6—C1121.51 (18)
C7—N1—H1116.3 (14)C5—C6—H6119.2
C1—N1—H1119.8 (14)C1—C6—H6119.2
C7—N2—N3117.57 (16)O3—C7—N2123.16 (16)
C7—N2—H2A120.0 (14)O3—C7—N1123.73 (17)
N3—N2—H2A118.2 (13)N2—C7—N1113.05 (15)
C8—N3—N2119.45 (16)O4—C8—N3121.89 (17)
C8—N3—H3A128.0 (15)O4—C8—C9122.59 (17)
N2—N3—H3A112.5 (15)N3—C8—C9115.49 (17)
O1—N4—O2122.58 (17)C14—C9—C10119.50 (18)
O1—N4—C2118.03 (17)C14—C9—C8118.53 (18)
O2—N4—C2119.39 (15)C10—C9—C8121.90 (17)
N1—C1—C6119.49 (16)C9—C10—C11119.69 (19)
N1—C1—C2123.91 (16)C9—C10—H10120.2
C6—C1—C2116.54 (16)C11—C10—H10120.2
C3—C2—C1121.65 (18)C12—C11—C10120.6 (2)
C3—C2—N4116.19 (16)C12—C11—H11119.7
C1—C2—N4122.16 (16)C10—C11—H11119.7
C4—C3—C2120.32 (19)C11—C12—C13120.0 (2)
C4—C3—H3119.8C11—C12—H12120.0
C2—C3—H3119.8C13—C12—H12120.0
C3—C4—C5119.01 (19)C14—C13—C12119.8 (2)
C3—C4—H4120.5C14—C13—H13120.1
C5—C4—H4120.5C12—C13—H13120.1
C6—C5—C4120.9 (2)C13—C14—C9120.4 (2)
C6—C5—H5119.5C13—C14—H14119.8
C4—C5—H5119.5C9—C14—H14119.8
C7—N2—N3—C867.4 (2)N3—N2—C7—O310.0 (3)
C7—N1—C1—C6−35.8 (3)N3—N2—C7—N1−172.79 (16)
C7—N1—C1—C2146.84 (18)C1—N1—C7—O3−12.5 (3)
N1—C1—C2—C3179.25 (18)C1—N1—C7—N2170.32 (17)
C6—C1—C2—C31.8 (2)N2—N3—C8—O47.0 (3)
N1—C1—C2—N4−1.2 (2)N2—N3—C8—C9−171.28 (16)
C6—C1—C2—N4−178.62 (16)O4—C8—C9—C1423.4 (3)
O1—N4—C2—C31.8 (2)N3—C8—C9—C14−158.26 (18)
O2—N4—C2—C3−178.46 (17)O4—C8—C9—C10−153.41 (19)
O1—N4—C2—C1−177.80 (17)N3—C8—C9—C1024.9 (2)
O2—N4—C2—C12.0 (2)C14—C9—C10—C110.0 (3)
C1—C2—C3—C4−0.4 (3)C8—C9—C10—C11176.84 (17)
N4—C2—C3—C4180.00 (16)C9—C10—C11—C120.2 (3)
C2—C3—C4—C5−1.4 (3)C10—C11—C12—C130.1 (3)
C3—C4—C5—C61.8 (3)C11—C12—C13—C14−0.7 (4)
C4—C5—C6—C1−0.4 (3)C12—C13—C14—C91.0 (4)
N1—C1—C6—C5−178.97 (17)C10—C9—C14—C13−0.6 (3)
C2—C1—C6—C5−1.4 (3)C8—C9—C14—C13−177.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O3i0.80 (2)2.10 (2)2.844 (2)154.8 (18)
N3—H3A···O4ii0.90 (2)1.95 (2)2.835 (2)167 (2)
N1—H1···O20.83 (2)2.13 (2)2.640 (2)119.8 (17)
N1—H1···O3i0.83 (2)2.32 (2)2.987 (2)138.7 (19)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5244).

References

  • Liu, X. P., Liu, A. P., Lin, L. Z., Wei, Z. Z., Huang, L. & Yu, K. (2005). Mod. Agrochem.4, 14–16.
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yip, W. K. & Yang, S. F. (1986). Plant Physiol.80, 515–519. [PubMed]

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