3-(4-Fluoro­benzo­yl)-4-(4-fluoro­phen­yl)-4-hy­droxy-2,6-di­phenyl­cyclo­hexane-1,1-dicarbo­nitrile

B Narayana; M Sapnakumari; Balladka K Sarojini; Jerry P Jasinski

doi:10.1107/S1600536814012197

. 2014 May 31;70(Pt 6):o736–o737. doi: 10.1107/S1600536814012197

3-(4-Fluorobenzoyl)-4-(4-fluorophenyl)-4-hydroxy-2,6-diphenylcyclohexane-1,1-dicarbonitrile

B Narayana ^a, M Sapnakumari ^a, Balladka K Sarojini ^b, Jerry P Jasinski ^c,^*

PMCID: PMC4051101 PMID: 24940301

Abstract

In the title compound, C₃₃H₂₄F₂N₂O₂, the cyclohexane ring adopts a slightly distorted chair conformation. The dihedral angle between the planes of the phenyl rings is 71.80 (9)°, while the planes of the fluorophenyl and fluorobenzoyl rings are inclined to one another by 31.04 (10)°. The dihedral angles between the planes of the phenyl ring adjacent to the 4-hydroxy group and those of the the fluorophenyl and fluorobenzoyl rings are 51.64 (10) and 34.31 (10)°, respectively, while the corresponding angles for the phenyl ring adjacent to the 3-(4-fluorobenzoyl) group are 57.51 (9) and 85.02 (10)°, respectively. An intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked via pairs of O—H⋯N hydrogen bonds, forming inversion dimers. The dimers are linked via C—H⋯N and C—H⋯O hydrogen bonds, forming chains along the c-axis direction. C—H⋯F hydrogen bonds link the chains into sheets lying parallel to the bc plane.

Related literature

For related structures, see: Sadikhova et al. (2011 ▶); Echeverria et al. (1995 ▶). For ring puckering parameters, see Cremer & Pople (1975 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₃₃H₂₄F₂N₂O₂
M _r = 518.54
Triclinic,
a = 10.9336 (10) Å
b = 11.5258 (4) Å
c = 11.8490 (7) Å
α = 89.440 (4)°
β = 62.687 (7)°
γ = 89.296 (5)°
V = 1326.60 (17) Å³
Z = 2
Cu Kα radiation
μ = 0.74 mm⁻¹
T = 173 K
0.44 × 0.32 × 0.14 mm

Data collection

Agilent Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.884, T _max = 1.000
8616 measured reflections
5042 independent reflections
4307 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.139
S = 1.06
5042 reflections
353 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶; Palatinus & van der Lee, 2008 ▶; Palatinus et al., 2012 ▶).; program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814012197/su2739sup1.cif

e-70-0o736-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012197/su2739Isup2.hkl

e-70-0o736-Isup2.hkl^{(276.4KB, hkl)}

Click here for additional data file.^{(9.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814012197/su2739Isup3.cml

CCDC reference: 1005354

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84	2.14	2.8086 (16)	136
O1—H1⋯N1ⁱ	0.84	2.55	3.2071 (18)	136
C15—H15⋯N2ⁱⁱ	0.95	2.55	3.388 (2)	148
C23—H23⋯O2ⁱ	0.95	2.49	3.394 (2)	160
C29—H29⋯O1ⁱ	0.95	2.49	3.398 (2)	160
C24—H24⋯F2ⁱⁱⁱ	0.95	2.58	3.443 (2)	152

Open in a new tab

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

Acknowledgments

BN thanks the UGC for financial assistance through the SAP and a BSR one-time grant for the purchase of chemicals. MS thanks the DST, New Delhi, for providing financial help for the research work through the INSPIRE Research Fellowship scheme. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

1. Comment

In order to prepare the pyran derivative, (2E)-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one was reacted with malanonitrile in the presence of a catalytic amount of ethanoic KOH. Instead of the pyran derivative, the title compound was obtained and we report herein on its crystal structure. The crystal structures of related compounds have been reported (Sadikhova et al., 2011; Echeverria et al., 1995).

In the molecule of the title compound, Fig. 1, the cyclohexane ring adopts a slightly distorted chair conformation [puckering parameters Q, θ, and φ = 0.5873 (17) Å, 7.19 (17)° and 50.9 (13)°, respectively; Cremer & Pople, 1975]. The dihedral angle between the phenyl rings (C22-C27 and C28-C33) is 71.80 (9)° while the fluorophenyl (C14–C19) and fluorobenzoyl (C8–C13) rings are inclined to one another by 31.04 (10)°. The dihedral angle between the phenyl ring adjacent to the 4-hydroxy group [C22–C27] and the fluorophenyl and fluorobenzoyl rings is 51.64 (10) and 34.31 (10) °, respectively, while the corresponding angles for the phenyl ring adjacent to the 3-(4-fluorobenzoyl) group [C8–C13] are 57.51 (9) and 85.02 (10) °, respectively. Bond lengths are in normal ranges (Allen et al., 1987). There is an intramolecular O—H···O hydrogen bond generating an S(6) ring motif (Table 1).

In the crystal, molecules are linked via O-H···N hydrogen bonds forming inversion dimers. The dimers are linked via C-H···N and C-H···O hydrogen bonds forming chains along [001]. C-H···F hydrogen bonds link the chains to form sheets lying parallel to the bc plane (Table 1 and Fig. 2).

2. Experimental

A mixture of (2E)-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one (4.52g, 0.02 mol) and malanonitrile (0.55ml, 0.01 mol) in 30 ml ethanol in the presence of a catalytic amount of ethanoic KOH was stirred at room temperature for 6 h. The precipitate obtained was collected by filtration and purified by recrystallization from ethanol. Prismatic colourless crystals were grown from ethanol by the slow evaporation method (M.p. 497–499 K).