N′-(Adamantan-2-yl­idene)thio­phene-2-carbohydrazide

Adnan A Kadi; Amer M Alanzi; Ali A El-Emam; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811044758

. 2011 Oct 29;67(Pt 11):o3127. doi: 10.1107/S1600536811044758

N′-(Adamantan-2-ylidene)thiophene-2-carbohydrazide

Adnan A Kadi ^a, Amer M Alanzi ^a, Ali A El-Emam ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3247511 PMID: 22220129

Abstract

In the title molecule, C₁₅H₁₈N₂OS, a small twist is noted, with the dihedral angle between the central carbohydrazone residue (r.m.s. deviation = 0.029 Å) and the thiophene ring being 12.47 (10)°. The syn arrangement of the amide H and carbonyl O atoms allows for the formation of centrosymmetric dimers via N—H⋯O hydrogen bonds. These are linked in the three-dimensional structure by C—H⋯π interactions. The thiophene ring is disordered over two co-planar orientations, the major component having a site-occupancy factor of 0.833 (2).

Related literature

For the biological activity of adamantane derivatives see: Vernier et al. (1969 ▶); El-Emam et al. (2004 ▶). For background to our work into the biological activity of adamantane derivatives, see: Kadi et al. (2010 ▶); Al-Omar et al. (2010 ▶). For a related structure, see: Al-Tamimi et al. (2010 ▶).

Experimental

Crystal data

C₁₅H₁₈N₂OS
M _r = 274.37
Monoclinic,
a = 16.7262 (2) Å
b = 12.5663 (1) Å
c = 13.5562 (2) Å
β = 102.473 (1)°
V = 2782.08 (6) Å³
Z = 8
Cu Kα radiation
μ = 2.01 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.584, T _max = 0.690
5687 measured reflections
2849 independent reflections
2671 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.087
S = 1.04
2849 reflections
189 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811044758/hg5127sup1.cif

e-67-o3127-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044758/hg5127Isup2.hkl

e-67-o3127-Isup2.hkl^{(139.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811044758/hg5127Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the S1,C1–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.93 (2)	1.92 (2)	2.844 (1)	173 (2)
C13—H13⋯Cg1ⁱⁱ	1.00	2.61	3.5791 (16)	163
C15—H15a⋯Cg1ⁱⁱⁱ	0.99	2.69	3.5683 (16)	148

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We thank the Deanship of Scientific Research and the Research Center of the College of Pharmacy, King Saud University, and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Derivatives of adamantane have long been known for their diverse biological activities including anti-viral activity against the influenza (Vernier et al., 1969) and HIV viruses (El-Emam et al., 2004). In continuation of our interest in the chemical and pharmacological properties of adamantane derivatives (Kadi et al., 2010; Al-Omar et al., 2010; Al-Tamimi et al., 2010), we synthesized the title compound, N'-(2-thienylcarbonyl)-2-adamantanone hydrazone, (I), as a potential chemotherapeutic agent. Herein, the crystal and molecular structures are described.

A small twist is noted in the molecule of (I), Fig. 1, as seen in the value of the dihedral between the thiophene ring and the central carbohydrazone residue (O1,N1,N2,C4,C5; r.m.s. deviation = 0.029 Å) being 12.47 (10)°. In the major component of the disordered molecule, the thiophene-S atom is proximate to the hydrazone-N atom, S1···N1 = 2.7797 (11) Å, whereas in the minor component, the C3'—H3' atom is 2.29 Å from N2. The amide-H and carbonyl-O atoms are syn. This arrangement allows for the formation of centrosymmetric dimers, Fig. 2 and Table 1, and eight-membered {···HNCO}₂ synthons. The dimers thus formed are consolidated in the crystal packing by C—H···π interactions, Fig. 3 and Table 1.

Experimental

Thiophene-2-carbohydrazide (1.42 g, 0.01 mol) and 2-adamantanone (1.5 g, 0.01 mol) were heated in ethanol (10 ml) for 4 h. The solid that separated upon cooling was collected and recrystallized from ethanol to yield 2.44 g (98%) of C₁₅H₁₈N₂OS as colourless crystals, M.pt. 464–467 K. The formulation was established by solution NMR spectroscopy. ¹H-NMR (CDCl₃): δ 1.91–2.05 (m, 14 adamantyl-H), 7.12 (s, 1 thienyl H), 7.60–7.63 (m, 1 thienyl H), 8.17 (s, 1 thienyl H), 10.04 (s, 1 amino H) p.p.m.. ¹³C-NMR: 27.78, 30.86, 36.38, 37.81, 39.21, 163.32 (adamantyl), 129.25, 133.78,134.30, 134.90 (thienyl)), 164.15 (carbonyl) p.p.m..