supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

su2467 scheme

Acta Cryst. (2012). E68, o2247-o2248    [ doi:10.1107/S1600536812028644 ]

N'-(Adamantan-2-ylidene)benzohydrazide

M. S. Almutairi, A. A. El-Emam, N. R. El-Brollosy, M. Said-Abdelbaky and S. García-Granda

Abstract top

The title molecule, C17H20N2O, is a functionalized hydrazine with benzoyl and adamantyl substituents attached to the two hydrazine N atoms. In the crystal, molecules are linked via N-H...N hydrogen bonds, forming chains propagating along the a-axis direction. There are also C-H...O, C-H...N and C-H...[pi] interactions present within the chains.

Comment top

Derivatives of adamantane have long been known for their diverse biological activities including antiviral activity against the influenza (Togo et al., 1968) and HIV viruses (El-Emam et al., 2004). Moreover, adamantane derivatives were reported to exhibit marked antibacterial and anti-inflammatory activities (Kadi et al., 2007, 2010; El-Emam & Ibrahim, 1991). In continuation to our interest in the chemical and pharmacological properties of adamantane derivatives (Almutairi et al., 2012; El-Emam et al., 2012), we synthesized the title compound as a precursor for potential chemotherapeutic agents. Herein, we report on the synthesis and crystal structure of the title compound.

The title molecule, Fig. 1, is a functionalized hydrazine with benzoyl and adamantyl substituents attached to the two hydrazine nitrogen atoms, N1 and N2.

In the crystal, molecules are linked via N-H···N hydrogen bonds forming chains propagating along the a axis direction. There are also C-H···O, C-H···N and C-H···π interactions present within the chains (Table 1).

Related literature top

For the biological activity of adamantane derivatives, see: Togo et al. (1968); Kadi et al. (2007, 2010); Al-Deeb et al. (2006); El-Emam et al. (2004). For the biological activity of hydrazone derivatives, see: Zheng et al. (2009); Moldovan et al. (2011). For related adamantane structures, see: Almutairi et al. (2012); Rouchal et al. (2010; El-Emam et al. (2012). For related cyclic ketone hydrazone structures, see: Sankar et al. (2010); El-Emam & Ibrahim (1991); Kia et al. (2009); Kadi et al. (2011).

Experimental top

A mixture of benzohydrazide (1.36 g, 0.01 mol), 2-adamantanone (1.5 g, 0.01 mol), in ethanol (10 ml) was heated under reflux with stirring for 4 h. On cooling, the precipitated crystalline solid was filtered, dried and recrystallized from ethanol to yield 2.52 g (94%) of the title compound as colourless needle crystals [M.p. 517-519 K]. Spectroscopic data for the title compound are given in the archived CIF.

Refinement top

The NH H-atom was located in a difference electron-density map and freely refined. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C-H = 0.93, 0.97 and 0.96 Å for CH(aromatic), CH2 and CH(methine) H-atoms, respectively, with Uiso(H) = 1.2Ueq(parent C-atom).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis CCD (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title molecule with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level.
N'-(Adamantan-2-ylidene)benzohydrazide top
Crystal data top
C17H20N2OF(000) = 1152
Mr = 268.35Dx = 1.266 Mg m−3
Orthorhombic, PbcaCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ac 2abCell parameters from 1578 reflections
a = 7.9698 (3) Åθ = 3.3–70.4°
b = 17.5466 (8) ŵ = 0.62 mm−1
c = 20.1350 (8) ÅT = 120 K
V = 2815.7 (2) Å3Prism, colourless
Z = 80.26 × 0.08 × 0.02 mm
Data collection top
Oxford Diffraction Xcalibur Ruby Gemini
diffractometer		2634 independent reflections
Radiation source: Enhance (Cu) X-ray Source1859 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
Detector resolution: 10.2673 pixels mm-1θmax = 70.4°, θmin = 3.3°
ω scansh = −6→9
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)		k = −21→20
Tmin = 0.942, Tmax = 0.988l = −24→20
7280 measured reflections
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0662P)2]
where P = (Fo2 + 2Fc2)/3
2634 reflections(Δ/σ)max < 0.001
185 parametersΔρmax = 0.17 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C17H20N2OV = 2815.7 (2) Å3
Mr = 268.35Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 7.9698 (3) ŵ = 0.62 mm−1
b = 17.5466 (8) ÅT = 120 K
c = 20.1350 (8) Å0.26 × 0.08 × 0.02 mm
Data collection top
Oxford Diffraction Xcalibur Ruby Gemini
diffractometer		2634 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)		1859 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.988Rint = 0.052
7280 measured reflectionsθmax = 70.4°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.139Δρmax = 0.17 e Å−3
S = 1.03Δρmin = −0.23 e Å−3
2634 reflectionsAbsolute structure: ?
185 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. Spectroscopic data for the title compound:

1H NMR (CDCl3, 500.13MHz): δ 1.82–1.96 (m, 14H, Adamantane-H), 7.36–7.43 (m, 3H, Ar—H), 7.51–7.53 (m, 2H, Ar—H), 8.81 (s, 1H, NH). 13C NMR (CDCl3, 125.76MHz): δ 27.70, 31.82, 36.20, 37.93, 39.06, 164.47 (Adamantane-C), 127.29, 128.66, 131.73, 133.77 (Ar—C), 171.29 (C═O).

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 esds 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
O10.41632 (17)0.06584 (9)0.16083 (8)0.0312 (5)
N10.6033 (2)0.11608 (10)0.23403 (9)0.0235 (5)
N20.4774 (2)0.16129 (10)0.26108 (9)0.0223 (5)
C10.5611 (2)0.07181 (12)0.18124 (10)0.0246 (6)
C20.7017 (2)0.02971 (12)0.14858 (10)0.0249 (6)
C30.8416 (3)0.00356 (13)0.18307 (12)0.0293 (6)
C40.9655 (3)−0.03725 (14)0.14965 (14)0.0371 (8)
C50.9494 (3)−0.05134 (15)0.08214 (14)0.0401 (8)
C60.8098 (3)−0.02579 (14)0.04800 (12)0.0369 (7)
C70.6858 (3)0.01433 (13)0.08093 (11)0.0293 (6)
C80.5128 (2)0.20447 (12)0.31045 (10)0.0220 (6)
C90.6735 (3)0.21136 (13)0.34927 (10)0.0264 (6)
C100.6324 (3)0.18818 (14)0.42134 (11)0.0310 (7)
C110.7330 (3)0.29468 (14)0.34814 (11)0.0313 (7)
C120.4986 (3)0.24128 (14)0.45032 (11)0.0296 (6)
C130.3753 (2)0.25512 (12)0.33641 (10)0.0237 (6)
C140.3378 (3)0.23380 (14)0.40906 (11)0.0291 (6)
C150.4369 (3)0.33837 (13)0.33421 (11)0.0296 (7)
C160.5968 (3)0.34691 (13)0.37629 (11)0.0288 (6)
C170.5592 (3)0.32391 (14)0.44831 (10)0.0279 (6)
H1N0.716 (3)0.1276 (15)0.2457 (12)0.028 (6)*
H30.852300.013300.228300.0350*
H41.05900−0.055000.172600.0440*
H51.03280−0.078100.059800.0480*
H60.79920−0.035600.002800.0440*
H70.591600.031100.057900.0350*
H90.759800.177800.330700.0320*
H10A0.592000.136000.422200.0370*
H10B0.733300.190800.448200.0370*
H11A0.834500.299700.374400.0380*
H11B0.758500.309600.302900.0380*
H120.475400.226700.496400.0360*
H130.274000.249300.309300.0280*
H14A0.251900.267300.426800.0350*
H14B0.296500.181900.411300.0350*
H15A0.460200.352900.288700.0360*
H15B0.350100.371900.351300.0360*
H160.635300.399900.375000.0350*
H17A0.659700.329300.475100.0330*
H17B0.473500.357100.466600.0330*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0275 (7)0.0321 (9)0.0339 (8)0.0024 (7)−0.0040 (6)−0.0082 (7)
N10.0219 (8)0.0216 (9)0.0270 (9)0.0025 (7)0.0013 (7)−0.0049 (8)
N20.0230 (8)0.0205 (9)0.0235 (8)0.0016 (7)0.0015 (7)−0.0002 (7)
C10.0276 (10)0.0218 (11)0.0244 (10)0.0000 (9)0.0005 (8)0.0009 (9)
C20.0280 (10)0.0190 (10)0.0277 (11)−0.0026 (8)0.0062 (9)−0.0018 (9)
C30.0274 (10)0.0225 (11)0.0381 (12)−0.0009 (9)0.0020 (9)−0.0011 (10)
C40.0292 (11)0.0298 (13)0.0522 (15)0.0041 (10)0.0051 (10)−0.0029 (12)
C50.0431 (13)0.0270 (12)0.0501 (15)0.0032 (10)0.0223 (12)−0.0052 (12)
C60.0528 (14)0.0248 (12)0.0330 (12)−0.0033 (11)0.0161 (12)−0.0025 (10)
C70.0374 (11)0.0214 (11)0.0290 (11)−0.0013 (9)0.0022 (9)−0.0010 (9)
C80.0242 (9)0.0199 (10)0.0220 (10)−0.0005 (8)−0.0001 (8)0.0015 (9)
C90.0245 (9)0.0289 (12)0.0259 (10)0.0035 (9)−0.0012 (9)−0.0065 (9)
C100.0388 (11)0.0284 (13)0.0257 (11)0.0050 (10)−0.0087 (10)−0.0007 (10)
C110.0299 (10)0.0342 (13)0.0298 (11)−0.0096 (10)0.0010 (9)−0.0049 (10)
C120.0380 (11)0.0288 (12)0.0220 (10)0.0016 (10)0.0010 (9)0.0008 (9)
C130.0250 (9)0.0219 (11)0.0242 (10)0.0016 (8)0.0003 (8)−0.0014 (9)
C140.0307 (10)0.0270 (12)0.0296 (11)−0.0017 (9)0.0070 (9)−0.0039 (10)
C150.0371 (11)0.0235 (12)0.0282 (11)0.0032 (9)−0.0021 (9)0.0002 (9)
C160.0359 (11)0.0222 (11)0.0284 (11)−0.0055 (10)−0.0006 (9)−0.0017 (9)
C170.0313 (10)0.0276 (12)0.0248 (10)0.0014 (9)−0.0031 (9)−0.0060 (9)
Geometric parameters (Å, º) top
O1—C11.229 (2)C15—C161.538 (3)
N1—N21.390 (2)C16—C171.535 (3)
N1—C11.359 (3)C3—H30.9300
N2—C81.281 (3)C4—H40.9300
N1—H1N0.95 (2)C5—H50.9300
C1—C21.495 (3)C6—H60.9300
C2—C71.394 (3)C7—H70.9300
C2—C31.391 (3)C9—H90.9800
C3—C41.393 (3)C10—H10A0.9700
C4—C51.388 (4)C10—H10B0.9700
C5—C61.383 (3)C11—H11A0.9700
C6—C71.383 (3)C11—H11B0.9700
C8—C91.505 (3)C12—H120.9800
C8—C131.505 (3)C13—H130.9800
C9—C111.537 (3)C14—H14A0.9700
C9—C101.542 (3)C14—H14B0.9700
C10—C121.532 (3)C15—H15A0.9700
C11—C161.530 (3)C15—H15B0.9700
C12—C171.529 (3)C16—H160.9800
C12—C141.533 (3)C17—H17A0.9700
C13—C141.539 (3)C17—H17B0.9700
C13—C151.542 (3)
N2—N1—C1117.00 (15)C5—C6—H6120.00
N1—N2—C8118.84 (16)C7—C6—H6120.00
N2—N1—H1N117.7 (15)C2—C7—H7120.00
C1—N1—H1N123.3 (15)C6—C7—H7120.00
N1—C1—C2116.18 (15)C8—C9—H9111.00
O1—C1—C2120.97 (18)C10—C9—H9110.00
O1—C1—N1122.86 (18)C11—C9—H9110.00
C1—C2—C7117.22 (17)C9—C10—H10A110.00
C3—C2—C7119.77 (19)C9—C10—H10B110.00
C1—C2—C3122.97 (19)C12—C10—H10A110.00
C2—C3—C4119.8 (2)C12—C10—H10B110.00
C3—C4—C5120.0 (2)H10A—C10—H10B108.00
C4—C5—C6120.3 (2)C9—C11—H11A110.00
C5—C6—C7120.1 (2)C9—C11—H11B110.00
C2—C7—C6120.1 (2)C16—C11—H11A110.00
N2—C8—C13117.29 (16)C16—C11—H11B110.00
N2—C8—C9129.62 (18)H11A—C11—H11B108.00
C9—C8—C13113.07 (17)C10—C12—H12109.00
C8—C9—C11109.34 (18)C14—C12—H12109.00
C8—C9—C10106.66 (18)C17—C12—H12109.00
C10—C9—C11109.29 (18)C8—C13—H13110.00
C9—C10—C12110.24 (19)C14—C13—H13110.00
C9—C11—C16110.21 (19)C15—C13—H13110.00
C10—C12—C17110.30 (19)C12—C14—H14A110.00
C10—C12—C14108.88 (19)C12—C14—H14B110.00
C14—C12—C17109.33 (19)C13—C14—H14A110.00
C8—C13—C15108.53 (15)C13—C14—H14B110.00
C8—C13—C14109.15 (17)H14A—C14—H14B108.00
C14—C13—C15108.63 (17)C13—C15—H15A110.00
C12—C14—C13109.39 (18)C13—C15—H15B110.00
C13—C15—C16109.90 (18)C16—C15—H15A110.00
C11—C16—C15109.00 (18)C16—C15—H15B110.00
C11—C16—C17109.34 (19)H15A—C15—H15B108.00
C15—C16—C17109.46 (19)C11—C16—H16110.00
C12—C17—C16109.64 (18)C15—C16—H16110.00
C2—C3—H3120.00C17—C16—H16110.00
C4—C3—H3120.00C12—C17—H17A110.00
C3—C4—H4120.00C12—C17—H17B110.00
C5—C4—H4120.00C16—C17—H17A110.00
C4—C5—H5120.00C16—C17—H17B110.00
C6—C5—H5120.00H17A—C17—H17B108.00
C1—N1—N2—C8−179.23 (19)C9—C8—C13—C14−59.8 (2)
N2—N1—C1—O1−6.1 (3)C9—C8—C13—C1558.4 (2)
N2—N1—C1—C2174.01 (17)C8—C9—C10—C12−60.3 (2)
N1—N2—C8—C9−4.7 (3)C11—C9—C10—C1257.8 (2)
N1—N2—C8—C13177.34 (17)C8—C9—C11—C1657.4 (2)
O1—C1—C2—C3−148.1 (2)C10—C9—C11—C16−59.1 (2)
O1—C1—C2—C729.5 (3)C9—C10—C12—C1461.6 (2)
N1—C1—C2—C331.7 (3)C9—C10—C12—C17−58.3 (2)
N1—C1—C2—C7−150.6 (2)C9—C11—C16—C15−59.3 (2)
C1—C2—C3—C4178.1 (2)C9—C11—C16—C1760.3 (2)
C7—C2—C3—C40.5 (3)C10—C12—C14—C13−59.2 (2)
C1—C2—C7—C6−178.7 (2)C17—C12—C14—C1361.3 (2)
C3—C2—C7—C6−1.0 (3)C10—C12—C17—C1659.2 (2)
C2—C3—C4—C50.3 (4)C14—C12—C17—C16−60.5 (2)
C3—C4—C5—C6−0.8 (4)C8—C13—C14—C1257.5 (2)
C4—C5—C6—C70.3 (4)C15—C13—C14—C12−60.7 (2)
C5—C6—C7—C20.5 (4)C8—C13—C15—C16−58.7 (2)
N2—C8—C9—C10−117.8 (2)C14—C13—C15—C1659.8 (2)
N2—C8—C9—C11124.1 (2)C13—C15—C16—C1160.2 (2)
C13—C8—C9—C1060.2 (2)C13—C15—C16—C17−59.4 (2)
C13—C8—C9—C11−57.9 (2)C11—C16—C17—C12−59.9 (2)
N2—C8—C13—C14118.5 (2)C15—C16—C17—C1259.4 (2)
N2—C8—C13—C15−123.3 (2)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···N2i0.95 (2)2.17 (2)3.087 (2)162 (2)
C3—H3···O1i0.932.473.381 (3)167
C9—H9···O1i0.982.333.210 (3)149
C9—H9···N2i0.982.553.402 (3)145
C15—H15A···Cg1ii0.972.573.519 (3)164
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···N2i0.95 (2)2.17 (2)3.087 (2)162 (2)
C3—H3···O1i0.932.473.381 (3)167
C9—H9···O1i0.982.333.210 (3)149
C9—H9···N2i0.982.553.402 (3)145
C15—H15A···Cg1ii0.972.573.519 (3)164
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.
Acknowledgements top

The financial support of the Deanship of Scientific Research and the Research Center for Female Scientific and Medical Colleges, King Saud University, is greatly appreciated. Financial support from the Spanish Ministerio de Economía y Competitividad (MAT2010–15094, MAT2006–01997, Factoría de Cristalización – Consolider Ingenio 2010, and FPI grant BES-2011–046948 to MSM-A) and FEDER are gratefully acknowledged.

references
References top

Al-Deeb, O. A., Al-Omar, M. A., El-Brollosy, N. R., Habib, E. E., Ibrahim, T. M. & El-Emam, A. A. (2006). Arzneim. Forsch. Drug. Res. 56, 40–47.

Almutairi, M. S., Al-Shehri, M. M., El-Emam, A. A., Ng, S. W. & Tiekink, E. R. T. (2012). Acta Cryst. E68, o656.

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. App. Cryst. 27, 435.

El-Emam, A. A., Al-Deeb, O. A., Al-Omar, M. A. & Lehmann, J. (2004). Bioorg. Med. Chem. 12, 5107–5113.

El-Emam, A. A., Alrashood, K. A., Al-Tamimi, A.-M. S., Ng, S. W. & Tiekink, E. R. T. (2012). Acta Cryst. E68, o657–o658.

El-Emam, A. A. & Ibrahim, T. M. (1991). Arzneim. Forsch. Drug. Res. 41, 1260–1264.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Kadi, A. A., Al-Abdullah, E. S., Shehata, I. A., Habib, E. E., Ibrahim, T. M. & El- Emam, A. A. (2010). Eur. J. Med. Chem. 45, 5006–5011.

Kadi, A. A., Alanzi, A. M., El-Emam, A. A., Ng, S. W. & Tiekink, E. R. T. (2011). Acta Cryst. E67, o3127.

Kadi, A. A., El-Brollosy, N. R., Al-Deeb, O. A., Habib, E. E., Ibrahim, T. M. & El- Emam, A. A. (2007). Eur. J. Med. Chem. 42, 235–242.

Kia, R., Fun, H.-K. & Kargar, H. (2009). Acta Cryst. E65, o382.

Moldovan, C. M., Oniga, O., Pârvu, A., Tiperciuc, B., Verite, P. & Pîrnău, A. (2011). Eur. J. Med. Chem. 46, 526–534.

Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.

Rouchal, M., Nečas, M. & Vícha, R. (2010). Acta Cryst. E66, o1736.

Sankar, C., Pandiarajan, K., Thiruvalluvar, A. & Gayathri, P. (2010). Acta Cryst. E66, o2841.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Togo, Y., Hornick, R. B. & Dawkins, A. T. (1968). J. Am. Med. Assoc. 203, 1089–1094.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Zheng, L., Wu, L., Zhao, B., Dong, W. & Miao, J. (2009). Bioorg. Med. Chem. 17, 1957–1962.