[2,6-Bis(biphenyl-4-yl)-4-hy­droxy-4-(pyridin-2-yl)cyclo­hexane-1,3-di­yl]bis­[(pyridin-2-yl)methanone]–butan-2-one (1/1)

Hoong-Kun Fun; Chin Wei Ooi; S Samshuddin; B Narayana; B K Sarojini

doi:10.1107/S1600536812019241

. 2012 May 5;68(Pt 6):o1633–o1634. doi: 10.1107/S1600536812019241

[2,6-Bis(biphenyl-4-yl)-4-hydroxy-4-(pyridin-2-yl)cyclohexane-1,3-diyl]bis[(pyridin-2-yl)methanone]–butan-2-one (1/1)

Hoong-Kun Fun ^a,^*,^‡, Chin Wei Ooi ^a, S Samshuddin ^b, B Narayana ^b, B K Sarojini ^c

PMCID: PMC3379237 PMID: 22719435

Abstract

In the title solvate, C₄₇H₃₇N₃O₃·C₄H₈O, the cyclohexane ring adopts a chair conformation and the plane through its near coplanar atoms forms dihedral angles of 82.58 (7), 89.27 (7), 60.30 (8), 54.54 (7) and 72.03 (7)°, respectively, with the three pyridine rings and the two attached benzene rings. The rings of the biphenyl units are twisted from each other, making dihedral angles of 35.27 (7) and 45.41 (7)°. All the rings are in equatorial orientations in the cyclohexane ring, except for the C=O-bonded pyridine ring in position 1, which is axial. Intramolecular O—H⋯N and C—H⋯O hydrogen bonds form one S(5) and three S(6) ring motifs. In the crystal, molecules are linked via C—H⋯O hydrogen bonds into a chain along the c axis. The crystal structure also features weak C—H⋯π interactions and aromatic π–π stacking [centroid–centroid distances = 3.5856 (10) and 3.7090 (9) Å].

Related literature

For a related structure, see: Schormann & Egert (1996 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-68-o1633-scheme1.jpg

Experimental

Crystal data

C₄₇H₃₇N₃O₃·C₄H₈O
M _r = 763.90
Monoclinic,
a = 13.7269 (9) Å
b = 25.3723 (16) Å
c = 11.4574 (7) Å
β = 100.643 (1)°
V = 3921.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.38 × 0.22 × 0.17 mm

Data collection

Bruker APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.969, T _max = 0.987
41041 measured reflections
10584 independent reflections
7594 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.143
S = 0.99
10584 reflections
529 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019241/hb6756sup1.cif

e-68-o1633-sup1.cif^{(47.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019241/hb6756Isup2.hkl

e-68-o1633-Isup2.hkl^{(517.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019241/hb6756Isup3.cml

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

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

Cg2 is the centroid of the N2/C20–C24 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1	0.90 (2)	1.92 (2)	2.5615 (18)	127.0 (19)
C16—H16A⋯O3	0.97	2.46	3.0730 (19)	121
C18—H18A⋯O3	0.98	2.39	3.0603 (19)	125
C26—H26A⋯O1ⁱ	0.93	2.53	3.3079 (19)	142
C27—H27A⋯O4ⁱⁱ	0.93	2.56	3.464 (2)	163
C3—H3A⋯Cg2ⁱⁱⁱ	0.93	2.96	3.7821 (17)	148

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

Acknowledgments

HKF and CWO thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). CWO also thanks the Malaysian Goverment and USM for the award of the post of Research Officer under Research University Grant No. 1001/PFIZIK/811160. BN thanks the UGC for financial assistance through the SAP and BSR one-time grant for the purchase of chemicals. SS thanks Mangalore University for the research facilities.

supplementary crystallographic information

Comment

The crystal structure of fully cyclo-substituted cyclohexane, 1r,9t,16t-trioxahexaspiro[2.0.3.0.2.0.3.0.2.0.3.0]heneicosane, has been reported (Schormann & Egert, 1996). As part of our studies in this area, the title compound (I) was prepared and its crystal structure is now reported.

The central cyclohexane (C13–C18) ring adopts a chair conformation (Cremer & Pople, 1975) with puckering parameters Q=0.5932 (16) Å, θ=4.69 (15)°, φ=274.6 (19)° and the plane through the coplanar atoms (C13/C15/C16/C18) form dihedral angles of 82.58 (7), 89.27 (7), 60.30 (8), 54.54 (7), and 72.03 (7)° repectively with three pyridines (N1/C25–C29, N2/C20–C24 and N3/C31–C35) rings and two attached phenyl (C7–C12 and C36–C41) rings. The phenyl rings of biphenyl (C1–C6/C7–C12 and C36–C41/C42–C47) are slightly twisted from each other with the dihedral angles of 35.27 (7) and 45.41 (7)°, respectively. Intramolecular O1—H1O1···N1, C16—H16A···O3 and C18—H18A···O3 hydrogen bonds (Table 1) form one S(5) and three S(6) ring motifs (Bernstein et al., 1995). The bond lengths are comparable to those in the related structure (Schormann & Egert, 1996).

In the crystal (Fig. 2), the molecules are linked via intermolecular C26—H26A···O1 and C27—H27A···O4 hydrogen bonds into a chain along the c axis. The crystal structure is further stabilized by C—H···π interactions (Table 1), involving the N2/C20–C24 ring (centroid Cg2). Weak π—π interactions were observed with Cg1···Cg2 = 3.5856 (10) Å [symmetry code: X, Y, Z] and Cg8···Cg8 = 3.7090 (9) Å [symmetry code: –X, –Y, –Z], where Cg1, Cg2 and Cg8 are the centroids of N1/C25–C29, N2/C20–C24 and C42–C47 rings, respectively.

Experimental

To a mixture of 2-acetyl pyridine (0.363 g, 0.003 mole) and biphenyl-4-carboxaldehyde (0.42 g, 0.002 mole) in 30 ml ethanol, 10 ml of 10% potassium hydroxide solution was added and stirred at 15–20 °C for 4 h and kept at room temperature overnight. The precipitate formed was collected by filtration and purified by recrystallization from acetone. The proposed mechanism is shown in Fig. 3. Colourless blocks were grown from EMK by the slow evaporation method and the yield of the compound was 74%. (M.p.: 518 K).