1,3-Diphenyl-1H-pyrazole-4-carbaldehyde

Abdul Qayyum Ather; M Nawaz Tahir; Misbahul Ain Khan; Karamat Mehmood; Faryal Chaudhry

doi:10.1107/S1600536810045630

. 2010 Nov 13;66(Pt 12):o3170. doi: 10.1107/S1600536810045630

1,3-Diphenyl-1H-pyrazole-4-carbaldehyde

Abdul Qayyum Ather ^a,^b, M Nawaz Tahir ^c,^*, Misbahul Ain Khan ^a, Karamat Mehmood ^c, Faryal Chaudhry ^d

PMCID: PMC3011511 PMID: 21589466

Abstract

There are four molecules in the asymmetric unit of the title compound, C₁₆H₁₂N₂O. The dihedral angle between the phenyl rings in the molecules are 22.2 (2), 22.4 (2), 25.1 (3) and 41.9 (2)°. In the crystal, molecules form dimers due to intermolecular C—H⋯O hydrogen bonds, which result in one R ₂ ²(10) and two R ₂ ¹(7) ring motifs. Weak aromatic π–π stacking [centroid–centroid separation = 3.788 (3) Å] and C—H⋯π interactions may also consolidate the packing.

Related literature

For background and related structures, see: Ather et al. (2010a ▶,b ▶,c ▶,d ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₂N₂O
M _r = 248.28
Triclinic,
a = 10.1367 (9) Å
b = 15.5952 (16) Å
c = 16.7550 (15) Å
α = 95.932 (6)°
β = 90.135 (5)°
γ = 107.991 (6)°
V = 2504.1 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.32 × 0.16 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.982, T _max = 0.988
34716 measured reflections
8912 independent reflections
4643 reflections with I > 2σ(I)
R _int = 0.092

Refinement

R[F ² > 2σ(F ²)] = 0.090
wR(F ²) = 0.259
S = 1.04
8912 reflections
671 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045630/hb5729sup1.cif

e-66-o3170-sup1.cif^{(38.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045630/hb5729Isup2.hkl

e-66-o3170-Isup2.hkl^{(427.1KB, hkl)}

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

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

Cg5 is the centroid of the C17–C22 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O2ⁱ	0.93	2.38	3.299 (5)	168
C12—H12⋯O2ⁱ	0.93	2.45	3.373 (6)	175
C26—H26⋯O1ⁱ	0.93	2.38	3.298 (6)	169
C32—H32⋯O1ⁱ	0.93	2.55	3.423 (7)	156
C42—H42⋯O3ⁱⁱ	0.93	2.36	3.287 (7)	173
C44—H44⋯O3ⁱⁱ	0.93	2.57	3.495 (8)	175
C58—H58⋯O4ⁱⁱⁱ	0.93	2.44	3.353 (6)	165
C60—H60⋯O4ⁱⁱⁱ	0.93	2.49	3.330 (8)	150
C2—H2⋯Cg5^iv	0.93	2.86	3.689 (7)	149

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Bana International, Karachi, Pakistan.

supplementary crystallographic information

Comment

In continuation of our studies of pyrazole derivatives (Ather et al., 2010a,b,c,d), the title compound (I, Fig. 1) is being reported here.

The title compound consists of four molecules in the crystallographic asymmetric unit which differ from each other geometrically. In one molecule, the phenyl rings A (C1—C6), B (C11—C16) and pyrazole moiety C (C7—C11/N1/N2/O1) are planar with r. m. s. deviation of 0.0048, 0.0057 and 0.0178 Å, respectively. The dihedral angle between A/B, A/C and B/C is 41.93 (22), 43.62 (21)° and 1.97 (31)°, respectively. In second molecule, the phenyl rings D (C17—C22), E (C27—C32) and pyrazole moiety F (C23—C26/N3/N4/O2) are planar with r. m. s. deviation of 0.0046, 0.0067 and 0.0330 Å, respectively. The dihedral angle between D/E, D/F and E/F is 22.38 (22), 34.73 (15)° and 17.24 (25)°, respectively. These two molecules form dimers due to intermolecular H-bondings of C—H···O type with two R₂¹(7) and an R₂²(10) (Table 1, Fig. 2) ring motifs (Bernstein et al., 1995). In third molecule, the phenyl rings G (C33—C38), H (C43—C48) and pyrazole moiety I (C39—C42/N5/N6/O3) are planar with r. m. s. deviation of 0.0099, 0.0021 and 0.0292 Å, respectively. The dihedral angle between G/H, G/I and H/I is 25.07 (28), 27.78 (27)° and 3.81 (33)°, respectively. In fourth molecule, the phenyl rings J (C49—C54), K (C59—C64) and pyrazole moiety L (C55—C58/N7/N8/O4) are planar with r. m. s. deviation of 0.0049, 0.0029 and 0.0339 Å, respectively. The dihedral angle between J/K, J/L and K/L is 22.16 (24), 37.81 (18)° and 22.27 (25)°, respectively. Third and fourth molecules also form dimers due to intermolecular H-bondings of C—H···O type with two R₂¹(7) and an R₂²(10) (Table 1, Fig. 2). π···π interactions occurs between the pyrazole and benzene rings in each dimer. The separations between the centroids of pyrazole and benzene rings have values of 3.788 (3)Å. These π···π and C—H···π (Table 1) interactions may help to consolidate the packing.

Experimental

Phosphoryl chloride (5 ml) was added drop wise to cold N,N-dimethylformamide (DMF) (15 ml) with continuous stirring at 273–278 K for about 30 min. Acetophenon phenylhydrazone (3.15 g, 15 mmol) was separately dissolved in 5 ml of DMF and was added drop wise to the former cold mixture with the continuous stirring at 273–278 K for an hour. The resulting mixture was further stirred at 323–333 K for 5–6 h and cooled to room temperature. The crude product was poured into crushed ice which resulted into white precipitate. These precipitate were recrystallized in ethanol to obtain colorless needles of (I).