5-Fluoro-3-phenyl-N′-(4-propyl­cyclo­hexyl­idene)-1H-indole-2-carbohydrazide

Sevim Türktekin Çelikesir; Mehmet Akkurt; Gökçe Cihan Üstündağ; Orhan Büyükgüngör

doi:10.1107/S1600536813018333

. 2013 Jul 6;69(Pt 8):o1202. doi: 10.1107/S1600536813018333

5-Fluoro-3-phenyl-N′-(4-propylcyclohexylidene)-1H-indole-2-carbohydrazide

Sevim Türktekin Çelikesir ^a, Mehmet Akkurt ^a,^*, Gökçe Cihan Üstündağ ^b, Orhan Büyükgüngör ^c

PMCID: PMC3793713 PMID: 24109300

Abstract

In the title compound, C₂₄H₂₆FN₃O, the cyclohexane ring adopts a chair conformation; the propyl substituent is in an equatorial orientation and the bond-angle sum at the C atom bonded to the carbohydrazide N atom is 360.0°. The dihedral angle between the 1H-indole ring system and the phenyl ring is 82.77 (13)°. A weak intramolecular C—H⋯π contact occurs. In the crystal, pairs of molecules related by a crystallographic twofold axis are linked by bifurcated N—H⋯(O,N) hydrogen bonds; a C—H⋯O interaction occurs between the same pair. The dimers are linked by C—H⋯F and C—H⋯π interactions, generating a three-dimensional network.

Related literature

For the design and synthesis of indolylhydrazones and their cyclization products, spirothiazolidinones, as potential antituberculosis and anticancer agents, see: Akkurt et al. (2010 ▶, 2013 ▶); Cihan-Üstündağ & Çapan (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). graphic file with name e-69-o1202-scheme1.jpg

Experimental

Crystal data

C₂₄H₂₆FN₃O
M _r = 391.48
Tetragonal,
a = 22.6986 (11) Å
c = 8.4480 (5) Å
V = 4352.6 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.63 × 0.46 × 0.28 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (Stoe & Cie, 2002 ▶) T _min = 0.957, T _max = 0.978
15640 measured reflections
4531 independent reflections
3430 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.092
S = 1.03
4531 reflections
267 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813018333/hb7101sup1.cif

e-69-o1202-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018333/hb7101Isup2.hkl

e-69-o1202-Isup2.hkl^{(248.6KB, hkl)}

Click here for additional data file.^{(8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813018333/hb7101Isup3.cml

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

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

Cg1, Cg2 and Cg3 are the centroids of the 1H-pyrrole (N1/C1/C6/C7/C14), benzene (C1–C6) and phenyl (C8–C13) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.50	3.048 (4)	123
N1—H1⋯N3ⁱ	0.86	2.32	3.170 (3)	168
C2—H2⋯O1ⁱ	0.93	2.51	3.112 (4)	123
C5—H5⋯F1ⁱⁱ	0.93	2.52	3.383 (3)	154
C3—H3⋯Cg3ⁱⁱⁱ	0.93	2.82	3.708 (3)	160
C11—H11⋯Cg1^iv	0.93	2.89	3.683 (3)	144
C17—H17A⋯Cg2^v	0.97	2.81	3.571 (3)	136
C17—H17B⋯Cg3	0.97	2.90	3.810 (4)	157

Open in a new tab

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund). This work was supported by the Scientific Research Projects Unit of İstanbul University (project No. T-471/25062004).

supplementary crystallographic information

Comment

Recently our work has been focused on the design and synthesis of novel indolylhydrazones and their cyclization products spirothiazolidinones as potential antituberculosis and anticancer agents (Akkurt et al., 2010, 2013; Cihan-Üstündağ & Çapan, 2012). Within this context, we here report the synthesis and crystal structure of the title compound.

As shown in Fig. 1, the (C16–C21) cyclohexane ring of the title compound adopts a chair conformation with the puckering parameters of Q(T) = 0.540 (4) Å, θ = 176.6 (4) ° and φ = 129 (12) °. The 1H-indole ring system makes a dihedral angle of 82.77 (13) ° with the C8–C13 phenyl ring. The N1–C14–C15–O1, N1–C14–C15–N2, C14–C15–N2–N3, C15–N2–N3–C16, N2–N3–C16–C17 and C19–C22–C23–C24 torsion angles are 11.3 (4), -167.4 (3), 174.2 (2), 174.8 (3), -1.1 (5) and 176.7 (5) °, respectively.

In the crystal, molecules are linked by N—H···O, N—H···N, C—H···O, C—H···F hydrogen bonds, forming layers parallel to the (110) plane (Table 1, Fig. 2). In addition, C—H···π interactions also contribute to the cohesion of the crystal packing.

Experimental

A mixture of 5-fluoro-3-phenyl-1H-indole-2-carbohydrazide (0.005 mol) and 4-propyl cyclohexanone (0.007 mol) was refluxed in 15 ml ethanol for 5 h. The precipitate obtained was purified by recrystallization from an ethanol-water mixture to yield colourless prisms.

Yield: 78%, mp.: 446–447.5 K. IR(KBr): υ_max 3366, 3243 (N—H), 1690 (C=O) cm^{-1. 1}H-NMR (DMSO-d₆/500 MHz): δ 0.78–0.88 (m and t, 4H, J= 7.3 Hz, 4-CH₂CH₂CH₃, CH/CH₂-cyc.*), 1.04–1.07 (m, 1H, CH/CH₂-cyc.), 1.15 (br. d, 2H, J=6.3 Hz, 4-CH₂CH₂CH₃-cyc.), 1.27 (br. quin, 2H, 4-CH₂CH₂CH₃-cyc.), 1.47 (br. d, 2H,J=14.9 Hz, CH/CH₂-cyc.), 1.59 (d, 1H, J=12.7 Hz, CH/CH₂-cyc.), 1.70–1.88 (m, 2H, CH/CH₂-cyc.), 2.13 (s, 1H, CH/CH₂-cyc.), 2.30 (s, 1H, CH/CH₂-cyc.), 7.12 (br. t, 2H, J=8.8 Hz, H4, H6-ind.), 7.42–7.50 (m, 6H, H7, 3-C₆H₅-ind.), 9.44 (s, 1H, CONH), 12.02 (s, 1H, NH) p.p.m.. ¹³C-NMR (Proton decoupled, DMSO-d₆/100 MHz): δ 14.61 (4-CH₂CH₂CH₃-cyc.), 20.05 (4-CH₂CH₂CH₃-cyc.), 25.83 (CH₂-cyc.), 32.00 (CH₂-cyc.), 33.03 (CH₂-cyc.), 34.43 (CH₂-cyc.), 35.91 (CH-cyc.), 38.18 (4-CH₂CH₂CH₃-cyc.), 105.02 (d, J=23.7 Hz, C4-ind.), 113.17 (d, J=26.0 Hz, C6-ind.), 114.28 (C7-ind.), 117.96 (C3-ind.), 127.36 (d, C3a-ind.), 127.89 (3-C₆H₅(C4)-ind.), 129.46 (3-C₆H₅(C3,C5)-ind.), 129.99 (C2-ind.), 130.53 (3-C₆H₅(C2,C6)-ind.), 132.79** (C7a-ind.), 133.72** (3-C₆H₅(C1)-ind.), 158.03 (C=N), 158.08 (d, J=233.6 Hz, C5-ind.), 161.94 (C=O) p.p.m.. MS (APCI+) m/z(%) 392 (MH⁺, 90). Analysis calculated for C₂₄H₂₆FN₃O : C, 73.63; H, 6.69; N, 10.73%. Found: C, 73.43; H, 6.62; N, 10.51%.(*cyc.=cyclohexylidene, br.=broad, quin.=quintet, ind.=indole, ** interchangeable).