4-Benzyl-3,5-dimethyl-1H-pyrazole

Wang, S.-Q.; Kong, C.

doi:10.1107/S1600536811045405

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3199

https://doi.org/10.1107/S1600536811045405

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4-Benzyl-3,5-dimethyl-1H-pyrazole

Su-Qing Wang ^a ^* and Cheng Kong ^b

^aMicroScale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bMicroScale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: wsuqing66@163.com

(Received 27 September 2011; accepted 29 October 2011; online 5 November 2011)

In the title molecule, C₁₂H₁₄N₂, the dihedral angle between the pyrazole and phenyl ring mean planes is 78.65 (19)°. In the crystal, molecules are linked by N—H⋯N hydrogen bonds into chains along [010].

Related literature

For the pharmacological activity of pyrazole derivatives, see: Adnan & Tarek (2004 ); Ashraf et al. (2003 ). For a related structure, see: Wang & Jian (2010 ). For standard bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₄N₂
M_r = 186.25
Monoclinic, P 2₁
a = 6.2303 (6) Å
b = 5.5941 (5) Å
c = 15.1364 (15) Å
β = 97.049 (1)°
V = 523.56 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 K
0.48 × 0.32 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.967, T_max = 0.989
2666 measured reflections
1023 independent reflections
756 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.107
S = 0.95
1023 reflections
127 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.86	2.09	2.946 (4)	170
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811045405/lh5342sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045405/lh5342Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045405/lh5342Isup3.cml

checkCIF report

Comment top

Pyrazole and its derivatives are an important class of N-heterocyclic compounds because they exhibit a broad spectrum of pharmacological activities such as antifungal (Adnan & Tarek, 2004), antitumor and antiangiogenic activities (Ashraf et al., 2003). As part of our research based on pyrazole derivatives and there complexes, the crystal structure of aquabis(3,5-dimethylpyrazolyl) copper(II) sulfate hydrate has been determined (Wang & Jian, 2010). As part of this ongoing search for new pyrazole compounds, the title compound was synthesized and its crystal structure is reported herein. In the title molecule (Fig. 1), bond lengths (Allen et al., 1987) and angles fall in normal ranges. The dihedral angle between the pyrazole ring (N1/N2/C2-C4) and the phenyl ring (C7-C11) is 78.65 (19)°. In the crystal, molecules are linked by N—H···N hydrogen bonds into one-dimensional chains along [010].

Related literature top

For the pharmacological activity of pyrazole derivatives, see: Adnan & Tarek (2004); Ashraf et al. (2003). For a related structure, see: Wang & Jian (2010). For standard bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 3-benzylpentane-2,4-dione (7.03 g, 0.037 mol) and hydrazine hydrate (2.20 g, 0.044 mol) was stirred with ice water for 4h. The reaction mixture was poured into ice water (100 ml) and the aqueous layer was extracted with ether. After being dried over anhydrous potassium carbonate, the organic layer was evaporated and the residue was purified. Single crystals were obtained by evaporation of an petroleum ether solution of (I) at room temperature over a period of several days.

Structure description top

For the pharmacological activity of pyrazole derivatives, see: Adnan & Tarek (2004); Ashraf et al. (2003). For a related structure, see: Wang & Jian (2010). For standard bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure, drawn with 30% probability ellipsoids and spheres of arbritrary size for the H atoms.

4-Benzyl-3,5-dimethyl-1H-pyrazole top

Crystal data top

C₁₂H₁₄N₂	F(000) = 200
M_r = 186.25	D_x = 1.181 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 648 reflections
a = 6.2303 (6) Å	θ = 2.7–20.1°
b = 5.5941 (5) Å	µ = 0.07 mm⁻¹
c = 15.1364 (15) Å	T = 298 K
β = 97.049 (1)°	Block, colorless
V = 523.56 (9) Å³	0.48 × 0.32 × 0.15 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1023 independent reflections
Radiation source: fine-focus sealed tube	756 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
T_min = 0.967, T_max = 0.989	k = −6→6
2666 measured reflections	l = −16→18

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0568P)²] where P = (F_o² + 2F_c²)/3
1023 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₂H₁₄N₂	V = 523.56 (9) Å³
M_r = 186.25	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.2303 (6) Å	µ = 0.07 mm⁻¹
b = 5.5941 (5) Å	T = 298 K
c = 15.1364 (15) Å	0.48 × 0.32 × 0.15 mm
β = 97.049 (1)°

Data collection top

Bruker SMART CCD diffractometer	1023 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	756 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.989	R_int = 0.043
2666 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	1 restraint
wR(F²) = 0.107	H-atom parameters constrained
S = 0.95	Δρ_max = 0.11 e Å⁻³
1023 reflections	Δρ_min = −0.13 e Å⁻³
127 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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	0.4939 (4)	0.1998 (6)	0.91543 (15)	0.0558 (7)
N2	0.6284 (4)	0.3826 (6)	0.94362 (13)	0.0536 (7)
H2	0.6092	0.4729	0.9880	0.064*
C1	0.9603 (5)	0.5915 (7)	0.91602 (19)	0.0672 (10)
H1A	0.9315	0.7234	0.8758	0.101*
H1B	1.0990	0.5241	0.9091	0.101*
H1C	0.9604	0.6464	0.9761	0.101*
C2	0.7922 (4)	0.4085 (6)	0.89629 (17)	0.0471 (7)
C3	0.7654 (4)	0.2339 (6)	0.83141 (16)	0.0451 (7)
C4	0.5795 (5)	0.1098 (6)	0.84614 (18)	0.0479 (8)
C5	0.4757 (5)	−0.0964 (8)	0.7964 (2)	0.0703 (10)
H5A	0.3904	−0.1838	0.8341	0.106*
H5B	0.5851	−0.1993	0.7779	0.106*
H5C	0.3842	−0.0398	0.7450	0.106*
C6	0.9109 (5)	0.1927 (8)	0.76133 (18)	0.0600 (9)
H6A	0.8811	0.0356	0.7356	0.072*
H6B	1.0597	0.1934	0.7891	0.072*
C7	0.8863 (5)	0.3750 (7)	0.68827 (18)	0.0548 (8)
C8	0.6936 (6)	0.4084 (9)	0.6353 (2)	0.0737 (10)
H8	0.5753	0.3144	0.6446	0.088*
C9	0.6716 (7)	0.5754 (9)	0.5699 (2)	0.0910 (14)
H9	0.5393	0.5939	0.5348	0.109*
C10	0.8423 (9)	0.7162 (9)	0.5551 (2)	0.0953 (14)
H10	0.8268	0.8309	0.5104	0.114*
C11	1.0345 (8)	0.6876 (9)	0.6063 (3)	0.0900 (14)
H11	1.1517	0.7829	0.5967	0.108*
C12	1.0566 (6)	0.5183 (8)	0.6721 (2)	0.0726 (11)
H12	1.1897	0.4998	0.7067	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0603 (15)	0.0557 (18)	0.0530 (14)	−0.0014 (16)	0.0135 (12)	0.0051 (16)
N2	0.0644 (16)	0.0562 (18)	0.0419 (12)	0.0048 (19)	0.0135 (11)	0.0001 (15)
C1	0.074 (2)	0.060 (2)	0.066 (2)	−0.012 (2)	0.0049 (17)	−0.0028 (19)
C2	0.0515 (17)	0.0453 (18)	0.0449 (14)	0.0028 (18)	0.0073 (12)	0.0069 (17)
C3	0.0527 (17)	0.0435 (19)	0.0393 (14)	0.0099 (17)	0.0063 (13)	0.0033 (15)
C4	0.0495 (17)	0.0473 (19)	0.0462 (16)	0.0033 (16)	0.0036 (14)	0.0014 (16)
C5	0.070 (2)	0.059 (2)	0.081 (2)	−0.005 (2)	0.0025 (17)	−0.007 (2)
C6	0.0623 (19)	0.064 (2)	0.0563 (17)	0.011 (2)	0.0169 (15)	−0.003 (2)
C7	0.064 (2)	0.057 (2)	0.0461 (15)	0.005 (2)	0.0173 (15)	−0.0083 (19)
C8	0.080 (2)	0.081 (3)	0.0602 (19)	−0.009 (3)	0.0101 (18)	0.005 (3)
C9	0.106 (3)	0.099 (4)	0.068 (2)	0.001 (3)	0.007 (2)	0.019 (3)
C10	0.158 (4)	0.073 (3)	0.060 (2)	−0.002 (4)	0.031 (3)	0.008 (2)
C11	0.124 (4)	0.081 (3)	0.074 (2)	−0.033 (3)	0.046 (3)	−0.016 (3)
C12	0.076 (2)	0.080 (3)	0.065 (2)	−0.012 (2)	0.0212 (19)	−0.009 (2)

Geometric parameters (Å, º) top

N1—C4	1.332 (3)	C6—C7	1.498 (5)
N1—N2	1.357 (4)	C6—H6A	0.9700
N2—C2	1.325 (3)	C6—H6B	0.9700
N2—H2	0.8600	C7—C8	1.372 (5)
C1—C2	1.469 (4)	C7—C12	1.375 (5)
C1—H1A	0.9600	C8—C9	1.357 (5)
C1—H1B	0.9600	C8—H8	0.9300
C1—H1C	0.9600	C9—C10	1.364 (6)
C2—C3	1.381 (5)	C9—H9	0.9300
C3—C4	1.392 (4)	C10—C11	1.353 (6)
C3—C6	1.495 (3)	C10—H10	0.9300
C4—C5	1.482 (5)	C11—C12	1.370 (6)
C5—H5A	0.9600	C11—H11	0.9300
C5—H5B	0.9600	C12—H12	0.9300
C5—H5C	0.9600

C4—N1—N2	103.9 (2)	C3—C6—C7	113.7 (3)
C2—N2—N1	113.5 (2)	C3—C6—H6A	108.8
C2—N2—H2	123.2	C7—C6—H6A	108.8
N1—N2—H2	123.2	C3—C6—H6B	108.8
C2—C1—H1A	109.5	C7—C6—H6B	108.8
C2—C1—H1B	109.5	H6A—C6—H6B	107.7
H1A—C1—H1B	109.5	C8—C7—C12	117.1 (4)
C2—C1—H1C	109.5	C8—C7—C6	121.8 (3)
H1A—C1—H1C	109.5	C12—C7—C6	121.1 (3)
H1B—C1—H1C	109.5	C9—C8—C7	121.6 (4)
N2—C2—C3	105.9 (3)	C9—C8—H8	119.2
N2—C2—C1	122.9 (3)	C7—C8—H8	119.2
C3—C2—C1	131.2 (3)	C8—C9—C10	120.4 (4)
C2—C3—C4	105.6 (2)	C8—C9—H9	119.8
C2—C3—C6	125.7 (3)	C10—C9—H9	119.8
C4—C3—C6	128.7 (3)	C11—C10—C9	119.4 (4)
N1—C4—C3	111.0 (3)	C11—C10—H10	120.3
N1—C4—C5	120.1 (3)	C9—C10—H10	120.3
C3—C4—C5	128.8 (3)	C10—C11—C12	120.1 (4)
C4—C5—H5A	109.5	C10—C11—H11	120.0
C4—C5—H5B	109.5	C12—C11—H11	120.0
H5A—C5—H5B	109.5	C11—C12—C7	121.4 (4)
C4—C5—H5C	109.5	C11—C12—H12	119.3
H5A—C5—H5C	109.5	C7—C12—H12	119.3
H5B—C5—H5C	109.5

C4—N1—N2—C2	−0.6 (3)	C2—C3—C6—C7	−74.5 (4)
N1—N2—C2—C3	0.7 (3)	C4—C3—C6—C7	105.8 (4)
N1—N2—C2—C1	−178.7 (3)	C3—C6—C7—C8	−60.6 (5)
N2—C2—C3—C4	−0.5 (3)	C3—C6—C7—C12	118.7 (3)
C1—C2—C3—C4	178.8 (3)	C12—C7—C8—C9	0.0 (5)
N2—C2—C3—C6	179.8 (3)	C6—C7—C8—C9	179.3 (3)
C1—C2—C3—C6	−1.0 (5)	C7—C8—C9—C10	−0.2 (6)
N2—N1—C4—C3	0.2 (3)	C8—C9—C10—C11	0.2 (7)
N2—N1—C4—C5	−179.9 (3)	C9—C10—C11—C12	0.0 (7)
C2—C3—C4—N1	0.1 (3)	C10—C11—C12—C7	−0.3 (6)
C6—C3—C4—N1	179.9 (3)	C8—C7—C12—C11	0.2 (5)
C2—C3—C4—C5	−179.8 (3)	C6—C7—C12—C11	−179.1 (3)
C6—C3—C4—C5	0.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.09	2.946 (4)	170

Symmetry code: (i) −x+1, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂
M_r	186.25
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	6.2303 (6), 5.5941 (5), 15.1364 (15)
β (°)	97.049 (1)
V (Å³)	523.56 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.48 × 0.32 × 0.15

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.967, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	2666, 1023, 756
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.107, 0.95
No. of reflections	1023
No. of parameters	127
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.13

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.09	2.946 (4)	170

Symmetry code: (i) −x+1, y+1/2, −z+2.

Acknowledgements

The authors would like to thank the Natural Science Foundation of Shandong Province (Y2008B23).

References

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