4-[3-(Biphenyl-4-yl)-1-phenyl-4,5-di­hydro-1H-pyrazol-5-yl]-3-(4-meth­oxy­phen­yl)-1-phenyl-1H-pyrazole dioxane monosolvate

Hoong-Kun Fun; Suhana Arshad; Shridhar Malladi; Arun M Isloor; Kammasandra Nanjunda Shivananda

doi:10.1107/S1600536812009117

. 2012 Mar 7;68(Pt 4):o972–o973. doi: 10.1107/S1600536812009117

4-[3-(Biphenyl-4-yl)-1-phenyl-4,5-dihydro-1H-pyrazol-5-yl]-3-(4-methoxyphenyl)-1-phenyl-1H-pyrazole dioxane monosolvate

Hoong-Kun Fun ^a,^*,^‡, Suhana Arshad ^a, Shridhar Malladi ^b, Arun M Isloor ^b, Kammasandra Nanjunda Shivananda ^c

PMCID: PMC3343947 PMID: 22590028

Abstract

In the title compound, C₃₇H₃₀N₄O·C₄H₈O₂, the dihedral angle between the pyrazole and dihydropyrazole rings is 74.09 (10)°. In the crystal, the components are linked into centrosymmetric tetramers (two main molecules and two solvent molecules) by C—H⋯O hydrogen bonds. C—H⋯π and π–π [shortest centroid-centroid separation = 3.6546 (9) Å] interactions are also observed.

Related literature

For the biological and pharmacological activity of pyrazolines, see, for example: Sahu et al. (2008 ▶). 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 ▶).

Experimental

Crystal data

C₃₇H₃₀N₄O·C₄H₈O₂
M _r = 634.75
Triclinic,
a = 11.1189 (2) Å
b = 13.0541 (2) Å
c = 13.0852 (2) Å
α = 117.309 (1)°
β = 90.468 (1)°
γ = 98.558 (1)°
V = 1662.48 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.26 × 0.19 × 0.05 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.979, T _max = 0.996
31208 measured reflections
9701 independent reflections
5913 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.126
S = 1.01
9701 reflections
433 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 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/S1600536812009117/hb6659sup1.cif

e-68-0o972-sup1.cif^{(41.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009117/hb6659Isup2.hkl

e-68-0o972-Isup2.hkl^{(474.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812009117/hb6659Isup3.cml

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

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

Cg1, Cg3 and Cg5 are the centroids of the N1/N2/C7/C14/C16, C1–C6 and C32–C37 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯O2	0.95	2.28	3.202 (2)	164
C41—H41B⋯O1ⁱ	0.99	2.54	3.344 (3)	139
C1—H1A⋯Cg1ⁱ	0.95	2.88	3.412 (2)	117
C33—H33A⋯Cg3ⁱⁱ	0.95	2.79	3.6748 (19)	155
C35—H35A⋯Cg1ⁱⁱⁱ	0.95	2.82	3.684 (2)	151
C41—H41A⋯Cg5^iv	0.99	2.83	3.682 (2)	145

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

Acknowledgments

HKF and SA thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). SA thanks the Malaysian Government and USM for the Academic Staff Training Scheme (ASTS) award. AMI is thankful to the Board of Research in Nuclear Sciences, Government of India for the Young Scientist award. AMI also thanks the Vision Group on Science & Technology, Government of Karnataka, India, for the Best Research Paper award.

supplementary crystallographic information

Comment

Pyrazolines are well-known and important nitrogen containing five-membered heterocyclic compounds with biological and pharmacological activities such as analgesic properties (Sahu et al., 2008). As part of our investigations of this area, we have synthesized the title compound to study its crystal structure (Fig. 1).

The solvent 1,4-dioxane ring (O2/O3/C39–C42) adopts a chair conformation (Cremer & Pople, 1975) with puckering parameters Q= 0.567 (2) Å, Θ= 179.0 (2)° and Φ= 302 (6)°. The ring A (N1/N2/C7/C14/C16), B (N3/N4/C17/C24/C25), C (C1–C6), D (C8–C13), E (C18–C23), F (C26–C31) and G (C32–C37) are essentially planar. The dihedral angle between the least-square planes of the rings are A/B = 74.09 (10)°, A/C = 42.50 (10)°, A/D = 8.04 (11)°, A/E = 86.29 (9)°, A/F = 77.25 (9)°, A/G = 83.37 (9)°, B/C = 55.81 (8)°, B/D = 74.18 (10)°, B/E = 19.64 (8)°, B/F = 3.18 (8)°, B/G = 30.67 (8)°, C/D = 49.32 (9)°, C/E = 71.40 (8)°, C/F = 57.94 (8)°, C/G = 86.47 (8)°, D/E = 86.48 (9)°, D/F = 77.36 (9)°, D/G = 86.35 (9)°, E/F = 16.50 (7)°, E/F = 20.45 (7)° and F/G = 28.72 (7)°.

The crystal structure is shown in Fig. 2. The molecules are linked into centrosymmetric tetramers (two main molecules and two solvent molecules) via C14—H14A···O2 and C41—H41B···O1 hydrogen bonds (Table 1). C—H···π interactions (Table 1) and π···π interactions of Cg2···Cg1 = 3.6546 (9) Å (symmetry code: x,y,z) and Cg2···Cg4 = 3.7773 (10) Å (symmetry code: 2-x,1-y,-z) further stabilized the crystal structure. [Cg1, Cg2 , Cg3, Cg4 and Cg5 are the centroids of the N1/N2/C7/C14/C16, N3/N4/C17/C24/C25, C1–C6, C26–C31 and C32–C37 rings, respectively].

Experimental

A mixture of (E)-1-(biphenyl-4-yl)-3-(3-(4-methoxyphenyl)-1-phenyl-1 H-pyrazol-4-yl)prop-2-en-1-one (0.456 g, 1.0 mmol) and phenylhydrazine (0.162 g, 1.5 mmol) was refluxed in glacial acetic acid for 4 h. The mixture was then cooled to room temperature and resulting solid was filtered and dried to get title compound. Yield: 0.31 g, 56.77%. M.p.: 437–439 K. 1,4-Dioxane was used as crystallization solvent to yield colourless plates.