3-Methyl-1,5-diphenyl-4,5-dihydro-1H-pyrazole

Manjula, M.; Jayaroopa, P.; Manjunath, B.C.; Ajay kumar, K.; Lokanath, N.K.

doi:10.1107/S1600536813007575

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o602

doi:10.1107/S1600536813007575

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3-Methyl-1,5-diphenyl-4,5-dihydro-1H-pyrazole

M. Manjula,^a P. Jayaroopa,^b B. C. Manjunath,^a K. Ajay kumar ^b and N. K. Lokanath ^a ^*

^aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, and ^bPost Graduate Department of Chemistry, Yuvaraja's College, University of Mysore, Mysore 570 006, India
^*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

(Received 6 March 2013; accepted 19 March 2013; online 28 March 2013)

In the title compound, C₁₆H₁₆N₂, the dihydropyrazole ring adopts a shallow envelope conformation, with the C atom bearing the phenyl group displaced by 0.298 (2) Å from the other atoms (r.m.s. deviation = 0.015 Å). The dihedral angles between the four near coplanar atoms of the central ring and the N- and C-bonded phenyl groups are 13.49 (13) and 82.22 (16)°, respectively.

Related literature

For background to pyrazoles, see: Govindaraju et al. (2012 ); Jayaroopa et al. (2013 ); Kalirajan et al. (2013 ); Mariappan et al. (2010 ); Shyama et al. (2009 ). For related structures, see: Baktır et al. (2011 ); Fun et al. (2011 ).

Experimental

Crystal data

C₁₆H₁₆N₂
M_r = 236.31
Monoclinic, C c
a = 18.1224 (17) Å
b = 7.8055 (6) Å
c = 12.5057 (13) Å
β = 132.207 (9)°
V = 1310.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 301 K
0.32 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
11856 measured reflections
2973 independent reflections
2362 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.131
S = 0.91
2973 reflections
165 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.10 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: Mercury.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813007575/hb7053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813007575/hb7053Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813007575/hb7053Isup3.cml

checkCIF report

Comment top

Pyrazoles are five-member heterocycles with two nitrogen atoms in a ring at 1,2-positions. They have been efficiently transformed in to a potential medicinally and pharmaceutically important molecule. Pyrazole derivatives have known to exhibit diverse biological applications such as antidiabetic, anaesthetic, antifungal (Jayaroopa et al., 2013), antiandrogenic, antioxidant, analgesic and anti-inflammatory activities. In addition, they have also showed potential anti-bacterial (Govindaraju et al., 2012), anticancer (Kalirajan et al., 2013), antiamoebic, potent and selective inhibitors of tissue-nonspecific alkaline phosphatase (Shyama et al., 2009), anti-inflammatory and protein kinase C inhibitor (Mariappan et al., 2010) properties.

we have synthesized the title compound to study its crystal structure in order to understand the structure-activity relationship for its biological activity.

The title compound C₁₆ H₁₆ N₂, contains two benzene rings (C1-C6 and C8-C13), these two rings are attached to the central pyrazole ring and the molecules are connected by non classical hydrogen bonds. The dihydropyrazole ring is a shallow envelope, with atom C7 displaced from the other four atoms by 0.298 (2)Å. The dihedral angles between the four near coplanar atoms of the central ring and the N- and C-bonded phenyl groups are 13.49 (13) and 82.22 (16)°, respectively. Bond lengths and bond angles are within normal ranges and are comparable to related structures (Baktır et al., 2011 & Fun et al., 2011).

Related literature top

For background to pyrazoles, see: Govindaraju et al. (2012); Jayaroopa et al. (2013); Kalirajan et al. (2013); Mariappan et al. (2010); Shyama et al. (2009). For related structures, see: Baktır et al. (2011); Fun et al. (2011).

Experimental top

A mixture of 4-phenylbut-3-en-2-one (0.05 mmol), phenyl hydrazine hydrochloride (0.05 mmol) and sodium acetate (0.05 mmol) in ethyl alcohol (25 ml) was stirred at room temperature for 1 h. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was poured into ice cold water. The solid formed was separated and crystallized with acetonitrile to get the title compound as yellow blocks.

Flash Point: 178 ° C. ¹H NMR (CDCl3): δ 2.015 (s, 3H, CH3), 2.619–2.671 (q, 1H, C4—H), 3.475–3.536 (q, 1H, C4—H), 5.108–5.146 (q, 1H, C5—H), 6.622–6.655 (t, 1H, Ar—H), 6.805–6.829 (d, 2H, Ar—H), 7.061–7.097 (t, 2H, Ar—H), 7.230–7.373 (m, 5H, Ar—H).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: Mercury (Macrae et al., 2006).

Figures top

	Fig. 1. ORTEP diagram of the title molecule with 50% probability ellipsoids.
	Fig. 2. Packing diagram of molecule, viewed along the crystallographic b axis.

3-Methyl-1,5-diphenyl-4,5-dihydro-1H-pyrazole top

Crystal data top

C₁₆H₁₆N₂	F(000) = 504
M_r = 236.31	D_x = 1.198 Mg m⁻³
Monoclinic, Cc	Melting point = 363–365 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 18.1224 (17) Å	Cell parameters from 2973 reflections
b = 7.8055 (6) Å	θ = 3.0–27.6°
c = 12.5057 (13) Å	µ = 0.07 mm⁻¹
β = 132.207 (9)°	T = 301 K
V = 1310.3 (3) Å³	Block, pale yellow
Z = 4	0.32 × 0.20 × 0.18 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2362 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.6°, θ_min = 3.0°
Detector resolution: 16.0839 pixels mm^-1	h = −23→23
ω scans	k = −10→10
11856 measured reflections	l = −16→16
2973 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2973 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.14 e Å⁻³
2 restraints	Δρ_min = −0.10 e Å⁻³

Crystal data top

C₁₆H₁₆N₂	V = 1310.3 (3) Å³
M_r = 236.31	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 18.1224 (17) Å	µ = 0.07 mm⁻¹
b = 7.8055 (6) Å	T = 301 K
c = 12.5057 (13) Å	0.32 × 0.20 × 0.18 mm
β = 132.207 (9)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2362 reflections with I > 2σ(I)
11856 measured reflections	R_int = 0.033
2973 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 0.91	Δρ_max = 0.14 e Å⁻³
2973 reflections	Δρ_min = −0.10 e Å⁻³
165 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.57189 (12)	0.5350 (3)	0.53221 (17)	0.0583 (6)
N2	0.63012 (12)	0.5538 (2)	0.49747 (18)	0.0528 (5)
C1	0.43700 (15)	0.4218 (3)	0.2954 (2)	0.0539 (6)
C2	0.34060 (17)	0.3632 (3)	0.1948 (2)	0.0683 (7)
C3	0.27852 (16)	0.3631 (3)	0.2214 (3)	0.0694 (7)
C4	0.31410 (16)	0.4245 (3)	0.3516 (3)	0.0617 (7)
C5	0.41076 (14)	0.4857 (2)	0.4546 (2)	0.0529 (6)
C6	0.47391 (13)	0.4829 (2)	0.42818 (19)	0.0439 (5)
C7	0.62148 (15)	0.5986 (2)	0.6767 (2)	0.0487 (5)
C8	0.58591 (12)	0.7740 (2)	0.67789 (18)	0.0425 (5)
C9	0.53469 (16)	0.8844 (3)	0.5615 (2)	0.0558 (6)
C10	0.50989 (18)	1.0475 (3)	0.5715 (3)	0.0710 (8)
C11	0.53636 (18)	1.1018 (3)	0.6979 (3)	0.0725 (9)
C12	0.58650 (17)	0.9929 (3)	0.8138 (3)	0.0644 (8)
C13	0.61057 (14)	0.8294 (3)	0.80360 (19)	0.0502 (6)
C14	0.73007 (16)	0.6028 (3)	0.7433 (2)	0.0618 (6)
C15	0.71843 (15)	0.5947 (2)	0.6134 (2)	0.0563 (6)
C16	0.8000 (2)	0.6260 (4)	0.6152 (4)	0.0878 (11)
H1	0.47760	0.42050	0.27480	0.0650*
H2	0.31700	0.32270	0.10660	0.0820*
H3	0.21360	0.32240	0.15260	0.0830*
H4	0.27280	0.42500	0.37110	0.0740*
H5	0.43330	0.52860	0.54160	0.0640*
H7	0.61430	0.51580	0.72810	0.0580*
H9	0.51670	0.84890	0.47570	0.0670*
H10	0.47520	1.12070	0.49240	0.0850*
H11	0.52030	1.21200	0.70480	0.0870*
H12	0.60430	1.02910	0.89940	0.0770*
H13	0.64380	0.75570	0.88220	0.0600*
H14A	0.76320	0.70760	0.79730	0.0740*
H14B	0.76730	0.50530	0.80630	0.0740*
H16A	0.77370	0.62300	0.51830	0.1320*
H16B	0.85000	0.53900	0.67170	0.1320*
H16C	0.82900	0.73640	0.65690	0.1320*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0465 (9)	0.0796 (11)	0.0514 (9)	−0.0147 (8)	0.0339 (8)	−0.0253 (8)
N2	0.0518 (9)	0.0527 (8)	0.0596 (9)	−0.0064 (7)	0.0397 (8)	−0.0083 (7)
C1	0.0477 (11)	0.0618 (11)	0.0449 (9)	0.0008 (8)	0.0281 (9)	−0.0037 (9)
C2	0.0521 (12)	0.0800 (14)	0.0474 (11)	−0.0079 (10)	0.0231 (10)	−0.0109 (10)
C3	0.0457 (11)	0.0665 (13)	0.0668 (14)	−0.0070 (9)	0.0259 (11)	−0.0034 (10)
C4	0.0532 (11)	0.0519 (10)	0.0866 (15)	0.0036 (9)	0.0497 (11)	0.0054 (10)
C5	0.0551 (11)	0.0494 (10)	0.0590 (11)	−0.0021 (8)	0.0403 (10)	−0.0077 (8)
C6	0.0413 (9)	0.0383 (7)	0.0461 (9)	0.0022 (7)	0.0269 (8)	−0.0015 (7)
C7	0.0479 (9)	0.0476 (9)	0.0425 (9)	−0.0016 (7)	0.0271 (8)	−0.0040 (7)
C8	0.0391 (8)	0.0454 (8)	0.0420 (8)	−0.0051 (7)	0.0269 (7)	−0.0026 (7)
C9	0.0574 (11)	0.0567 (11)	0.0491 (10)	0.0004 (8)	0.0341 (9)	0.0071 (8)
C10	0.0650 (14)	0.0544 (11)	0.0800 (16)	0.0095 (10)	0.0431 (13)	0.0199 (11)
C11	0.0664 (14)	0.0499 (12)	0.110 (2)	0.0015 (9)	0.0628 (15)	−0.0042 (12)
C12	0.0686 (14)	0.0652 (13)	0.0789 (15)	−0.0099 (10)	0.0575 (13)	−0.0201 (11)
C13	0.0490 (10)	0.0567 (10)	0.0457 (10)	−0.0039 (8)	0.0322 (9)	−0.0032 (8)
C14	0.0480 (11)	0.0595 (11)	0.0545 (11)	0.0037 (9)	0.0249 (9)	−0.0119 (9)
C15	0.0463 (11)	0.0505 (10)	0.0644 (12)	−0.0024 (8)	0.0340 (10)	−0.0060 (9)
C16	0.0631 (15)	0.105 (2)	0.100 (2)	−0.0193 (14)	0.0567 (15)	−0.0180 (16)

Geometric parameters (Å, º) top

N1—N2	1.393 (4)	C14—C15	1.492 (3)
N1—C6	1.381 (3)	C15—C16	1.484 (6)
N1—C7	1.462 (3)	C1—H1	0.9300
N2—C15	1.284 (3)	C2—H2	0.9300
C1—C2	1.375 (4)	C3—H3	0.9300
C1—C6	1.393 (3)	C4—H4	0.9300
C2—C3	1.371 (5)	C5—H5	0.9300
C3—C4	1.373 (4)	C7—H7	0.9800
C4—C5	1.387 (4)	C9—H9	0.9300
C5—C6	1.388 (4)	C10—H10	0.9300
C7—C8	1.518 (3)	C11—H11	0.9300
C7—C14	1.538 (4)	C12—H12	0.9300
C8—C9	1.381 (3)	C13—H13	0.9300
C8—C13	1.384 (3)	C14—H14A	0.9700
C9—C10	1.383 (4)	C14—H14B	0.9700
C10—C11	1.375 (4)	C16—H16A	0.9600
C11—C12	1.371 (4)	C16—H16B	0.9600
C12—C13	1.382 (4)	C16—H16C	0.9600

N2—N1—C6	120.09 (17)	C2—C3—H3	121.00
N2—N1—C7	112.6 (2)	C4—C3—H3	121.00
C6—N1—C7	126.7 (2)	C3—C4—H4	120.00
N1—N2—C15	107.8 (2)	C5—C4—H4	119.00
C2—C1—C6	120.1 (3)	C4—C5—H5	120.00
C1—C2—C3	121.6 (2)	C6—C5—H5	120.00
C2—C3—C4	118.6 (3)	N1—C7—H7	110.00
C3—C4—C5	121.0 (3)	C8—C7—H7	110.00
C4—C5—C6	120.2 (2)	C14—C7—H7	110.00
N1—C6—C1	120.5 (3)	C8—C9—H9	120.00
N1—C6—C5	121.00 (18)	C10—C9—H9	120.00
C1—C6—C5	118.5 (2)	C9—C10—H10	120.00
N1—C7—C8	113.95 (16)	C11—C10—H10	120.00
N1—C7—C14	100.2 (2)	C10—C11—H11	120.00
C8—C7—C14	111.89 (18)	C12—C11—H11	120.00
C7—C8—C9	122.80 (19)	C11—C12—H12	120.00
C7—C8—C13	118.56 (16)	C13—C12—H12	120.00
C9—C8—C13	118.55 (19)	C8—C13—H13	120.00
C8—C9—C10	120.5 (2)	C12—C13—H13	120.00
C9—C10—C11	120.3 (2)	C7—C14—H14A	111.00
C10—C11—C12	119.7 (2)	C7—C14—H14B	111.00
C11—C12—C13	120.1 (3)	C15—C14—H14A	111.00
C8—C13—C12	120.8 (2)	C15—C14—H14B	111.00
C7—C14—C15	102.47 (18)	H14A—C14—H14B	109.00
N2—C15—C14	113.4 (3)	C15—C16—H16A	109.00
N2—C15—C16	122.1 (2)	C15—C16—H16B	109.00
C14—C15—C16	124.5 (2)	C15—C16—H16C	109.00
C2—C1—H1	120.00	H16A—C16—H16B	110.00
C6—C1—H1	120.00	H16A—C16—H16C	110.00
C1—C2—H2	119.00	H16B—C16—H16C	109.00
C3—C2—H2	119.00

C6—N1—N2—C15	−176.91 (18)	C4—C5—C6—N1	−176.63 (19)
C7—N1—N2—C15	11.2 (2)	C4—C5—C6—C1	1.7 (3)
N2—N1—C6—C1	10.6 (3)	N1—C7—C8—C9	−18.0 (4)
N2—N1—C6—C5	−171.14 (17)	N1—C7—C8—C13	165.6 (2)
C7—N1—C6—C1	−178.8 (2)	C14—C7—C8—C9	94.8 (3)
C7—N1—C6—C5	−0.5 (3)	C14—C7—C8—C13	−81.6 (3)
N2—N1—C7—C8	101.5 (3)	N1—C7—C14—C15	17.20 (19)
N2—N1—C7—C14	−18.2 (2)	C8—C7—C14—C15	−103.93 (19)
C6—N1—C7—C8	−69.7 (3)	C7—C8—C9—C10	−175.5 (3)
C6—N1—C7—C14	170.6 (2)	C13—C8—C9—C10	0.8 (4)
N1—N2—C15—C14	1.8 (2)	C7—C8—C13—C12	175.1 (3)
N1—N2—C15—C16	−179.6 (2)	C9—C8—C13—C12	−1.4 (4)
C6—C1—C2—C3	0.1 (3)	C8—C9—C10—C11	0.3 (5)
C2—C1—C6—N1	177.2 (2)	C9—C10—C11—C12	−0.8 (6)
C2—C1—C6—C5	−1.1 (3)	C10—C11—C12—C13	0.2 (6)
C1—C2—C3—C4	0.5 (4)	C11—C12—C13—C8	0.9 (5)
C2—C3—C4—C5	0.1 (4)	C7—C14—C15—N2	−12.9 (2)
C3—C4—C5—C6	−1.1 (3)	C7—C14—C15—C16	168.6 (2)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂
M_r	236.31
Crystal system, space group	Monoclinic, Cc
Temperature (K)	301
a, b, c (Å)	18.1224 (17), 7.8055 (6), 12.5057 (13)
β (°)	132.207 (9)
V (Å³)	1310.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.32 × 0.20 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11856, 2973, 2362
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.131, 0.91
No. of reflections	2973
No. of parameters	165
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.10

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).

Acknowledgements

MM thanks the IOE, University of Mysore, for the award of a fellowship. We thank the Solid Sate and Structural Chemistry Unit, IISc, Bangalore, for the data collection.

References

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