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Acta Cryst. (2009). E65, o2360    [ doi:10.1107/S1600536809035284 ]

4-Phenylsemicarbazide

U. Ashiq, R. A. Jamal, M. N. Arshad, Z. T. Maqsood and I. U. Khan

Abstract top

The title compound, C7H9N3O, crystallizes with two independent molecules per asymmetric unit. The structure is stabilized by four distinct intermolecular N-H...O hydrogen bonds. Four intramolecular interactions of the N-H...N and C-H...O types are also observed.

Comment top

Hydrazides are known to have different biological activities (Ashiq, Ara et al., 2008; Ara et al., 2007). In order to study the biological activity of 4-phenylsemicarbazide, we undertook the synthesis of title compound and report its crystal structure in this paper. The title compound was found to be active against urease enzyme (Ara et al., 2007). The structures of benzhydrazide (Kallel et al., 1992), para-chloro (Saraogi et al., 2002), para-bromo (Ashiq, Jamal et al., 2008), para-iodo (Jamal et al., 2008), para-methoxy (Ashiq, Jamal et al., 2009) and para-hydroxy (Jamal et al., 2009) analogues have already been reported.

The unit cell contains two crystallographically unique molecules, whose molecular structures are presented in Fig. 1. The bond distances and bond angles are similar to the corresponding distances and angles reported in the structures quoted above. The molecular packing diagram (Fig. 2) shows the presence of four intermolecular hydrogen bonds and four intramolecular hydrogen interactions. In the crystal structure, two adjacent molecules are held together by intermolecular hydrogen bonds between the N12—H12N···O21, N13—H14N···O11, N22—H22N···O11 and N23—H23N···O21 (details are given in Table 1).

Related literature top

For related structures see: Ashiq, Jamal et al. (2008, 2009); Jamal et al. (2008, 2009); Kallel et al. (1992); Saraogi et al. (2002); For the biological activity of hydrazides, see: Ara et al. (2007); Ashiq, Ara et al. (2008).

Experimental top

All reagent-grade chemicals were obtained from Aldrich and Sigma Chemical companies and were used without further purification. To a solution of phenyl urea (34 g, 0.25 moles) in 50 ml ethanol, hydrazine hydrate (25.0 ml, 0.45 moles) was added. The mixture was refluxed for 24 h and solid 4-phenylsemicarbazide was obtained upon removal of the solvent by rotary evaporation (yield 79%).

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic C-atoms, and for N1 and N2 atoms were taken from fourier synthesis and their coordinates were refined with N—H = 0.849 (16)–0.918 (17)Å with Uiso set to 1.2Ueq of their parent atoms.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP diagram of the title compound with the ellipsoids drawn at the 50% probability level, showing the atomic labels.
[Figure 2] Fig. 2. A packing diagram viewed down the c axis showing hydrogen bonds drawn as dashed lines. Hydrogen atoms not involved in H-bonding have been omitted.
4-Phenylsemicarbazide top
Crystal data top
C7H9N3OF(000) = 640
Mr = 151.17Dx = 1.316 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3838 reflections
a = 16.5984 (10) Åθ = 2.5–24.4°
b = 8.8862 (4) ŵ = 0.09 mm−1
c = 10.3518 (6) ÅT = 296 K
β = 91.359 (3)°Needle, colourless
V = 1526.43 (14) Å30.43 × 0.15 × 0.12 mm
Z = 8
Data collection top
Bruker Kappa APEXII CCD
diffractometer		3500 independent reflections
Radiation source: fine-focus sealed tube2258 reflections with I > 2σ(I)
graphiteRint = 0.030
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −21→20
Tmin = 0.979, Tmax = 0.990k = −6→11
15394 measured reflectionsl = −13→13
Refinement top
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) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0459P)2 + 0.1614P]
where P = (Fo2 + 2Fc2)/3
3500 reflections(Δ/σ)max < 0.001
223 parametersΔρmax = 0.16 e Å−3
0 restraintsΔρmin = −0.15 e Å−3
Crystal data top
C7H9N3OV = 1526.43 (14) Å3
Mr = 151.17Z = 8
Monoclinic, P21/cMo Kα radiation
a = 16.5984 (10) ŵ = 0.09 mm−1
b = 8.8862 (4) ÅT = 296 K
c = 10.3518 (6) Å0.43 × 0.15 × 0.12 mm
β = 91.359 (3)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer		3500 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2258 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.990Rint = 0.030
15394 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107Δρmax = 0.16 e Å−3
S = 1.03Δρmin = −0.15 e Å−3
3500 reflectionsAbsolute structure: ?
223 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
xyzUiso*/Ueq
O110.01604 (6)0.79747 (12)0.48141 (10)0.0553 (4)
N110.09359 (7)0.58992 (13)0.44101 (12)0.0427 (4)
N12−0.01754 (7)0.64373 (13)0.31698 (11)0.0438 (4)
N13−0.00041 (8)0.51513 (16)0.24513 (14)0.0506 (5)
C110.15892 (8)0.60879 (14)0.52831 (12)0.0354 (4)
C120.16095 (9)0.71248 (16)0.62779 (13)0.0439 (5)
C130.22909 (10)0.72368 (18)0.70707 (15)0.0508 (5)
C140.29449 (9)0.63342 (19)0.68932 (15)0.0554 (6)
C150.29205 (10)0.52914 (19)0.59133 (16)0.0572 (6)
C160.22502 (9)0.51619 (17)0.51125 (14)0.0462 (5)
C170.03011 (8)0.68266 (15)0.41816 (13)0.0378 (5)
O210.17516 (6)0.28317 (12)0.23819 (10)0.0529 (4)
N210.28009 (7)0.40092 (15)0.13966 (13)0.0500 (5)
N220.15623 (8)0.38933 (15)0.04272 (12)0.0488 (4)
N230.18846 (8)0.47117 (17)−0.05959 (13)0.0514 (5)
C210.34464 (8)0.38042 (16)0.22790 (14)0.0433 (5)
C220.34917 (9)0.26384 (18)0.31535 (15)0.0509 (5)
C230.41651 (9)0.2490 (2)0.39537 (16)0.0593 (6)
C240.47943 (10)0.3476 (2)0.38889 (17)0.0643 (6)
C250.47515 (10)0.4626 (2)0.30239 (18)0.0707 (7)
C260.40834 (9)0.48014 (19)0.22223 (17)0.0596 (6)
C270.20285 (8)0.35311 (15)0.14604 (14)0.0405 (5)
H11N0.0960 (9)0.5210 (18)0.3845 (15)0.0510*
H120.116800.774400.641400.0530*
H12N−0.0624 (9)0.6927 (17)0.3025 (14)0.0530*
H130.230300.794000.773600.0610*
H13N−0.0413 (10)0.4498 (19)0.2569 (15)0.0610*
H140.340000.642400.742800.0660*
H14N0.0017 (10)0.5393 (19)0.1621 (17)0.0610*
H150.336100.466600.579000.0690*
H160.224100.445000.445400.0550*
H21N0.2880 (10)0.4551 (18)0.0733 (16)0.0600*
H220.307000.195300.320600.0610*
H22N0.1043 (10)0.3598 (17)0.0395 (15)0.0590*
H230.419000.170400.454700.0710*
H23N0.1844 (10)0.4143 (19)−0.1336 (16)0.0620*
H240.524600.336200.442900.0770*
H24N0.1591 (10)0.5550 (19)−0.0679 (15)0.0620*
H250.517800.530100.297200.0850*
H260.406100.559700.163900.0720*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0570 (7)0.0548 (7)0.0534 (7)0.0192 (5)−0.0156 (5)−0.0142 (5)
N110.0424 (7)0.0419 (7)0.0434 (7)0.0079 (6)−0.0090 (6)−0.0063 (5)
N120.0394 (7)0.0465 (7)0.0449 (7)0.0100 (6)−0.0088 (6)−0.0061 (6)
N130.0484 (8)0.0510 (8)0.0519 (8)0.0034 (6)−0.0074 (7)−0.0105 (7)
C110.0355 (7)0.0362 (7)0.0345 (7)−0.0003 (6)0.0002 (6)0.0061 (6)
C120.0433 (8)0.0468 (8)0.0416 (8)0.0066 (7)−0.0014 (6)−0.0018 (7)
C130.0546 (10)0.0539 (9)0.0435 (9)−0.0006 (8)−0.0050 (7)−0.0052 (7)
C140.0438 (9)0.0679 (11)0.0537 (10)0.0002 (8)−0.0136 (7)0.0009 (8)
C150.0435 (9)0.0658 (11)0.0619 (10)0.0155 (8)−0.0063 (8)−0.0005 (8)
C160.0438 (8)0.0480 (9)0.0464 (9)0.0087 (7)−0.0042 (7)−0.0025 (7)
C170.0372 (8)0.0392 (8)0.0370 (8)0.0024 (6)−0.0014 (6)0.0032 (6)
O210.0386 (6)0.0680 (7)0.0520 (7)−0.0068 (5)−0.0024 (5)0.0135 (5)
N210.0380 (7)0.0630 (9)0.0488 (8)−0.0090 (6)−0.0040 (6)0.0102 (6)
N220.0372 (7)0.0595 (8)0.0495 (8)−0.0050 (6)−0.0050 (6)0.0095 (6)
N230.0517 (8)0.0591 (9)0.0432 (8)0.0001 (6)−0.0026 (6)0.0044 (7)
C210.0340 (8)0.0526 (9)0.0433 (8)−0.0017 (6)0.0008 (6)−0.0063 (7)
C220.0384 (8)0.0566 (10)0.0578 (10)−0.0019 (7)0.0009 (7)0.0013 (8)
C230.0455 (10)0.0743 (12)0.0579 (10)0.0094 (8)−0.0022 (8)0.0068 (9)
C240.0405 (9)0.0906 (13)0.0612 (11)0.0034 (9)−0.0121 (8)−0.0091 (10)
C250.0445 (10)0.0823 (13)0.0846 (13)−0.0177 (9)−0.0116 (9)−0.0025 (11)
C260.0488 (10)0.0628 (11)0.0669 (11)−0.0135 (8)−0.0044 (8)0.0043 (8)
C270.0355 (8)0.0419 (8)0.0440 (8)−0.0013 (6)−0.0016 (6)−0.0033 (7)
Geometric parameters (Å, °) top
O11—C171.2375 (17)C12—C131.385 (2)
O21—C271.2362 (17)C13—C141.366 (2)
N11—C111.4051 (18)C14—C151.374 (2)
N11—C171.3541 (18)C15—C161.376 (2)
N12—N131.3964 (18)C12—H120.9300
N12—C171.3427 (18)C13—H130.9300
N11—H11N0.849 (16)C14—H140.9300
N12—H12N0.872 (15)C15—H150.9300
N13—H14N0.887 (18)C16—H160.9300
N13—H13N0.904 (17)C21—C221.377 (2)
N21—C211.4032 (19)C21—C261.382 (2)
N21—C271.3537 (18)C22—C231.382 (2)
N22—C271.3443 (19)C23—C241.366 (2)
N22—N231.4013 (19)C24—C251.360 (3)
N21—H21N0.852 (16)C25—C261.378 (2)
N22—H22N0.901 (16)C22—H220.9300
N23—H23N0.919 (17)C23—H230.9300
N23—H24N0.893 (17)C24—H240.9300
C11—C121.3817 (19)C25—H250.9300
C11—C161.386 (2)C26—H260.9300
C11—N11—C17128.70 (12)C13—C12—H12120.00
N13—N12—C17120.18 (12)C14—C13—H13119.00
C11—N11—H11N118.8 (10)C12—C13—H13119.00
C17—N11—H11N111.6 (10)C15—C14—H14120.00
C17—N12—H12N119.4 (10)C13—C14—H14120.00
N13—N12—H12N120.0 (10)C16—C15—H15120.00
N12—N13—H14N109.3 (11)C14—C15—H15120.00
H13N—N13—H14N109.5 (15)C15—C16—H16120.00
N12—N13—H13N106.9 (11)C11—C16—H16120.00
C21—N21—C27129.56 (13)C22—C21—C26118.72 (14)
N23—N22—C27120.18 (12)N21—C21—C22123.69 (13)
C21—N21—H21N117.9 (11)N21—C21—C26117.53 (13)
C27—N21—H21N112.4 (11)C21—C22—C23119.79 (14)
C27—N22—H22N119.5 (10)C22—C23—C24121.19 (16)
N23—N22—H22N120.4 (10)C23—C24—C25119.10 (16)
H23N—N23—H24N110.4 (15)C24—C25—C26120.69 (16)
N22—N23—H24N106.8 (10)C21—C26—C25120.50 (16)
N22—N23—H23N108.8 (11)O21—C27—N21124.42 (13)
C12—C11—C16119.04 (13)O21—C27—N22121.12 (13)
N11—C11—C16116.64 (12)N21—C27—N22114.46 (13)
N11—C11—C12124.32 (12)C21—C22—H22120.00
C11—C12—C13119.65 (14)C23—C22—H22120.00
C12—C13—C14121.24 (14)C22—C23—H23119.00
C13—C14—C15119.07 (15)C24—C23—H23119.00
C14—C15—C16120.69 (15)C23—C24—H24120.00
C11—C16—C15120.30 (14)C25—C24—H24120.00
N11—C17—N12114.90 (12)C24—C25—H25120.00
O11—C17—N11124.42 (13)C26—C25—H25120.00
O11—C17—N12120.67 (12)C21—C26—H26120.00
C11—C12—H12120.00C25—C26—H26120.00
C17—N11—C11—C1214.9 (2)C16—C11—C12—C131.0 (2)
C17—N11—C11—C16−164.97 (14)N11—C11—C16—C15178.94 (13)
C11—N11—C17—O11−6.6 (2)C11—C12—C13—C14−0.3 (2)
C11—N11—C17—N12171.74 (13)C12—C13—C14—C15−0.4 (2)
N13—N12—C17—O11179.06 (13)C13—C14—C15—C160.5 (2)
N13—N12—C17—N110.66 (18)C14—C15—C16—C110.2 (2)
C21—N21—C27—O212.2 (2)N21—C21—C22—C23177.50 (14)
C27—N21—C21—C2224.3 (2)C26—C21—C22—C230.2 (2)
C27—N21—C21—C26−158.35 (15)N21—C21—C26—C25−177.24 (15)
C21—N21—C27—N22−178.53 (14)C22—C21—C26—C250.2 (2)
N23—N22—C27—N21−0.5 (2)C21—C22—C23—C24−0.5 (2)
N23—N22—C27—O21178.77 (13)C22—C23—C24—C250.3 (3)
N11—C11—C12—C13−178.84 (13)C23—C24—C25—C260.1 (3)
C12—C11—C16—C15−0.9 (2)C24—C25—C26—C21−0.4 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N11—H11N···N130.849 (16)2.130 (15)2.6149 (19)116.0 (13)
N12—H12N···O21i0.872 (15)2.071 (15)2.9386 (15)172.8 (14)
N13—H14N···O11ii0.887 (18)2.383 (17)3.2149 (18)156.1 (15)
N21—H21N···N230.852 (16)2.130 (17)2.6093 (19)115.3 (14)
N22—H22N···O11iii0.901 (16)2.079 (17)2.9784 (17)175.9 (14)
N23—H23N···O21iv0.919 (17)2.203 (17)3.0850 (18)160.5 (15)
C12—H12···O110.932.332.9119 (18)120
C22—H22···O210.932.462.9833 (18)116
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N11—H11N···N130.849 (16)2.130 (15)2.6149 (19)116.0 (13)
N12—H12N···O21i0.872 (15)2.071 (15)2.9386 (15)172.8 (14)
N13—H14N···O11ii0.887 (18)2.383 (17)3.2149 (18)156.1 (15)
N21—H21N···N230.852 (16)2.130 (17)2.6093 (19)115.3 (14)
N22—H22N···O11iii0.901 (16)2.079 (17)2.9784 (17)175.9 (14)
N23—H23N···O21iv0.919 (17)2.203 (17)3.0850 (18)160.5 (15)
C12—H12···O110.932.332.9119 (18)120
C22—H22···O210.932.462.9833 (18)116
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2.
Acknowledgements top

The authors thank the Higher Education Commission Pakistan for providing the diffractometer at GCU, Lahore, and Bana International for their support in collecting the crystallographic data.

references
References top

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