2-[3,5-Bis(4-meth­oxy­phen­yl)-4,5-di­hydro-1H-pyrazol-1-yl]-4,6-bis­(4-meth­oxy­phen­yl)pyrimidine

Rajni Kant; Vivek K Gupta; Kamini Kapoor; S Samshuddin; B Narayana

doi:10.1107/S1600536812030516

. 2012 Jul 10;68(Pt 8):o2398. doi: 10.1107/S1600536812030516

2-[3,5-Bis(4-methoxyphenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4,6-bis(4-methoxyphenyl)pyrimidine

Rajni Kant ^a,^*, Vivek K Gupta ^a, Kamini Kapoor ^a, S Samshuddin ^b, B Narayana ^b

PMCID: PMC3414322 PMID: 22904855

Abstract

In the title compound, C₃₅H₃₂N₄O₄, the pyrazole ring forms a dihedral angle of 15.04 (8)° with the adjacent pyrimidine ring. The pyrimidine ring forms dihedral angles of 9.95 (8) and 1.86 (7)° with its adjacent methoxy-substituted benzene rings, whereas the equivalent angles are 80.24 (9) and 11.55 (9)° for the pyrazole ring and its adjacent benzene rings. The crystal packing features π–π interactions, the centroid–centroid distance between the pyrimidine and methoxyphenyl rings being 3.604 (1) Å. The pyrazole ring is nearly planar, with a maximum deviation of 0.020 (3) Å for the –CH₂– carbon.

Related literature

For biological importance of substituted pyrimidines, see: Fun et al. (2010 ▶); Jasinski et al. (2010 ▶); Baktır et al. (2011 ▶); Samshuddin et al. (2011 ▶); Betz et al. (2012 ▶). For related literature on substituted pyrimidines and their derivatives, see: Calabresi et al. (1975 ▶); El-Hashash et al. (1993 ▶); Fun et al. (2012 ▶).

Experimental

Crystal data

C₃₅H₃₂N₄O₄
M _r = 572.65
Monoclinic,
a = 21.637 (2) Å
b = 5.9532 (4) Å
c = 24.749 (2) Å
β = 109.519 (10)°
V = 3004.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.887, T _max = 1.000
12486 measured reflections
5824 independent reflections
3423 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.145
S = 1.05
5824 reflections
393 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 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 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812030516/bh2441sup1.cif

e-68-o2398-sup1.cif^{(35KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030516/bh2441Isup2.hkl

e-68-o2398-Isup2.hkl^{(279.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812030516/bh2441Isup3.cml

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

Acknowledgments

RK acknowledges the Department of Science and Technology for access to the single-crystal X-ray diffractometer sanctioned as a national facility under project No. SR/S2/CMP-47/2003. BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals.

supplementary crystallographic information

Comment

The importance of pyrimidines and analogous compounds in pharmaceutical and biological fields is well known. Some substituted pyrimidines and their derivatives have been reported to possess antimicrobial and antifungal activities (El-Hashash et al., 1993). It has incidental antiviral activity against herpes and vaccinia infections (Calabresi et al., 1975). With the development of clinically useful pyrimidine based antitumor and antiviral drugs there has been noticeable interest in synthetic manipulations of pyrimidines. In view of the biological importance of pyrimidines and in continuation of work on synthesis of various derivatives of chalcone (Samshuddin et al., 2011; Fun et al., 2010; Jasinski et al., 2010; Baktır et al., 2011; Betz et al., 2012), the title compound is prepared and its crystal structure is reported.

The molecule comprises of the pyrimidine ring, pyrazole ring, and four methoxy substituted benzene rings. All bond lengths and angles are normal and correspond to those observed in related structure (Fun et al., 2012). The six bond lengths in the pyrimidine ring lie in the range 1.337 (2)–1.396 (3) Å. The pyrimidine ring and pyrazole ring are individually planar with maximum deviations from the respective least-squares planes of: 0.010 (2) Å for C1 and 0.021 (3) Å for C26. Three intramolecular interactions C8—H8···N2, C20—H20···N6 and C41—H41···N24 are observed which lock the molecular conformation and thus eliminating conformational flexibility (Fig. 1). The pyrazole ring forms a dihedral angle of 15.04 (8)° with the adjacent pyrimidine ring (maximum deviation = -0.0176 (2) Å at atom C27). The pyrimidine ring forms dihedral angles of 9.95 (8) and 1.86 (7)° with its adjacent methoxy-substituted benzene rings (C15···C20 & C7···C12, respectively), whereas for pyrazole ring these angles are 80.24 (9) and 11.55 (9)° (C28···C33 & C36···C41, respectively). Molecules in the crystal are packed together to form layers, which appear to be extending diagonally along the ac plane (Fig. 2). Examination of non-bonded contacts reveals no classical intermolecular hydrogen bonds. The crystal structure is stabilized by π–π interaction between the pyrimidine ring of the molecule at (x, y, z) and benzene ring (C7···C12) at (1 - x, -y, 1 - z) [centroid separation = 3.604 (1) Å, interplanar spacing = 3.45 Å and centroid shift = 1.06 Å].

Experimental

A mixture of 4,4'-dimethoxy chalcone (2.68 g, 0.01 mol) and amino guanidine hydrochloride (0.065 g, 0.005 mol) in 25 ml e thanol was refluxed for 24 hrs in the presence of sodium ethoxide (2 ml). The reaction mixture was cooled to room temperature and refrigerated overnight. The solid product obtained was filtered and recrystallized from ethanol, affording a yellow powder. Single crystals were grown from DMF by slow evaporation method and the yield of the compound was 64% (m.p. 502 K).