3,5-Dimethyl-1-phenyl-1H-pyrazole-4-carbaldehyde

Al-Youbi, A.O.; Asiri, A.M.; Faidallah, H.M.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812010240

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1051

doi:10.1107/S1600536812010240

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3,5-Dimethyl-1-phenyl-1H-pyrazole-4-carbaldehyde

Abdulrahman O. Al-Youbi,^a,^b ‡ Abdullah M. Asiri,^a,^b Hassan M. Faidallah,^a Seik Weng Ng ^c,^a and Edward R. T. Tiekink ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, ^bThe Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, PO Box 80203, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 6 March 2012; accepted 8 March 2012; online 14 March 2012)

In the title molecule, C₁₂H₁₂N₂O, the five- and six-membered rings form a dihedral angle of 68.41 (16)°. The aldehyde group is nearly coplanar with the pyrazole ring [C—C—C—O torsion angle = −0.4 (5)°]. The three-dimensional architecture is sustained by weak C—H⋯O and C—H⋯π interactions.

Related literature

For the anti-bacterial properties of pyrazole derivatives, see: Kane et al. (2003 ). For related structures, see: Asiri et al. (2012a ,b ).

Experimental

Crystal data

C₁₂H₁₂N₂O
M_r = 200.24
Monoclinic, P 2₁ /c
a = 6.6264 (4) Å
b = 6.7497 (4) Å
c = 22.6203 (12) Å
β = 94.785 (5)°
V = 1008.19 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.979, T_max = 0.996
6376 measured reflections
2335 independent reflections
1951 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.194
S = 1.23
2335 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1ⁱ	0.95	2.43	3.315 (4)	155
C11—H11⋯Cg1ⁱⁱ	0.95	2.71	3.509 (4)	142
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); 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 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812010240/xu5480sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010240/xu5480Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812010240/xu5480Isup3.cml

checkCIF report

Comment top

In continuation of structural studies of pyrazole derivatives (Asiri et al., 2012a; Asiri et al., 2012b), motivated by their putative biological activity (Kane et al., 2003), the title compound, 3,5-dimethyl-1-phenyl-1H-4-pyrazole-3-carboxaldehyde (I), was investigated crystallographically.

In (I), Fig. 1, there is a twist about the single bond linking the five- and six-membered rings with the N2—N1—C7—C8 torsion angle being -112.1 (3) °; the dihedral angle between the rings is 68.41 (16) °. The aldehyde group is co-planar with the pyrazole ring to which it is connected as seen in the value of the C2—C3—C6—O1 torsion angle of -0.4 (5)°.

Molecules are connected into the three-dimensional architecture by C—H···O and C—H···π interactions, Fig. 2 and Table 1.

Related literature top

For the anti-bacterial properties of pyrazole derivatives, see: Kane et al. (2003). For related structures, see: Asiri et al. (2012a,b).

Experimental top

To a cold solution of N,N-dimethylformamide (1.46 g, 20 mmol), freshly distilled phosphorous oxychloride (1.54 g, 10 mmol) was added with stirring over a period of 30 min. A solution of 3,5-dimethyl-1-phenyl-1H-4-pyrazole-3-carboxaldehyde (1.72 g, 10 mmol) in N,N-dimethylformamide (15 ml) was added drop-wise while maintaining the temperature between 273–278 K. The resulting mixture was heated under reflux for 1 h, cooled and poured with continuous stirring into crushed ice. After 15 min, the precipitate was filtered and crystallized from aqueous ethanol to give needles. Yield: 69%. M.pt: 397–399 K.

Structure description top

Molecules are connected into the three-dimensional architecture by C—H···O and C—H···π interactions, Fig. 2 and Table 1.

For the anti-bacterial properties of pyrazole derivatives, see: Kane et al. (2003). For related structures, see: Asiri et al. (2012a,b).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view in projection down the a axis of the unit-cell contents of (I). The C—H···O and C—H···π interactions are shown as orange and purple dashed lines, respectively.

3,5-Dimethyl-1-phenyl-1H-pyrazole-4-carbaldehyde top

Crystal data top

C₁₂H₁₂N₂O	F(000) = 424
M_r = 200.24	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2660 reflections
a = 6.6264 (4) Å	θ = 2.7–27.5°
b = 6.7497 (4) Å	µ = 0.09 mm⁻¹
c = 22.6203 (12) Å	T = 100 K
β = 94.785 (5)°	Prism, colourless
V = 1008.19 (10) Å³	0.25 × 0.15 × 0.05 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2335 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1951 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.035
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 3.1°
ω scan	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→6
T_min = 0.979, T_max = 0.996	l = −29→29
6376 measured 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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H-atom parameters constrained
S = 1.23	w = 1/[σ²(F_o²) + (0.0317P)² + 2.9806P] where P = (F_o² + 2F_c²)/3
2335 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₂H₁₂N₂O	V = 1008.19 (10) Å³
M_r = 200.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6264 (4) Å	µ = 0.09 mm⁻¹
b = 6.7497 (4) Å	T = 100 K
c = 22.6203 (12) Å	0.25 × 0.15 × 0.05 mm
β = 94.785 (5)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2335 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1951 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.996	R_int = 0.035
6376 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	0 restraints
wR(F²) = 0.194	H-atom parameters constrained
S = 1.23	Δρ_max = 0.43 e Å⁻³
2335 reflections	Δρ_min = −0.31 e Å⁻³
138 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.2480 (3)	0.6126 (4)	0.58330 (9)	0.0215 (5)
N1	0.2395 (4)	0.2683 (4)	0.40971 (10)	0.0148 (5)
N2	0.2307 (4)	0.1335 (4)	0.45524 (11)	0.0195 (6)
C1	0.2332 (6)	0.1451 (5)	0.56361 (14)	0.0276 (8)
H1A	0.1190	0.0526	0.5626	0.041*
H1B	0.2177	0.2463	0.5940	0.041*
H1C	0.3600	0.0727	0.5730	0.041*
C2	0.2378 (5)	0.2431 (5)	0.50395 (13)	0.0172 (6)
C3	0.2500 (4)	0.4477 (5)	0.49014 (13)	0.0148 (6)
C4	0.2499 (4)	0.4563 (5)	0.42869 (13)	0.0153 (6)
C5	0.2611 (6)	0.6283 (5)	0.38750 (14)	0.0236 (7)
H5A	0.1524	0.6179	0.3555	0.035*
H5B	0.3925	0.6280	0.3706	0.035*
H5C	0.2456	0.7519	0.4094	0.035*
C6	0.2550 (4)	0.6179 (5)	0.52932 (13)	0.0167 (6)
H6	0.2644	0.7448	0.5116	0.020*
C7	0.2304 (4)	0.1953 (4)	0.34975 (12)	0.0143 (6)
C8	0.4000 (5)	0.2103 (5)	0.31798 (14)	0.0208 (7)
H8	0.5214	0.2683	0.3354	0.025*
C9	0.3893 (5)	0.1389 (5)	0.25999 (14)	0.0235 (7)
H9	0.5033	0.1502	0.2374	0.028*
C10	0.2120 (5)	0.0509 (5)	0.23500 (13)	0.0203 (7)
H10	0.2060	0.0009	0.1956	0.024*
C11	0.0447 (5)	0.0363 (5)	0.26753 (13)	0.0182 (6)
H11	−0.0756	−0.0246	0.2505	0.022*
C12	0.0520 (5)	0.1106 (4)	0.32508 (13)	0.0165 (6)
H12	−0.0636	0.1034	0.3472	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0239 (11)	0.0255 (12)	0.0150 (10)	−0.0002 (10)	0.0007 (8)	−0.0037 (9)
N1	0.0210 (12)	0.0131 (12)	0.0105 (11)	−0.0012 (10)	0.0024 (9)	0.0006 (9)
N2	0.0305 (14)	0.0157 (13)	0.0126 (12)	−0.0021 (11)	0.0031 (10)	0.0009 (10)
C1	0.048 (2)	0.0210 (17)	0.0140 (15)	−0.0048 (16)	0.0052 (14)	0.0023 (13)
C2	0.0219 (15)	0.0166 (14)	0.0134 (14)	−0.0009 (12)	0.0020 (11)	0.0008 (11)
C3	0.0144 (13)	0.0171 (14)	0.0133 (13)	−0.0012 (12)	0.0031 (10)	−0.0005 (11)
C4	0.0157 (13)	0.0157 (15)	0.0140 (14)	−0.0013 (12)	−0.0020 (11)	0.0000 (11)
C5	0.0401 (19)	0.0145 (15)	0.0160 (15)	−0.0003 (15)	0.0016 (13)	−0.0004 (12)
C6	0.0170 (14)	0.0173 (15)	0.0157 (14)	−0.0012 (12)	0.0012 (11)	−0.0024 (12)
C7	0.0218 (14)	0.0092 (13)	0.0118 (13)	0.0006 (11)	0.0004 (11)	0.0001 (10)
C8	0.0211 (15)	0.0238 (16)	0.0175 (15)	−0.0033 (13)	0.0017 (12)	−0.0043 (13)
C9	0.0230 (15)	0.0280 (18)	0.0205 (15)	−0.0003 (14)	0.0075 (12)	−0.0071 (14)
C10	0.0298 (17)	0.0183 (15)	0.0129 (14)	0.0024 (13)	0.0012 (12)	−0.0031 (12)
C11	0.0242 (15)	0.0139 (14)	0.0155 (14)	−0.0013 (12)	−0.0038 (11)	−0.0001 (12)
C12	0.0206 (14)	0.0140 (14)	0.0149 (13)	−0.0016 (12)	0.0024 (11)	0.0008 (11)

Geometric parameters (Å, º) top

O1—C6	1.226 (4)	C5—H5B	0.9800
N1—C4	1.339 (4)	C5—H5C	0.9800
N1—N2	1.379 (3)	C6—H6	0.9500
N1—C7	1.439 (4)	C7—C12	1.387 (4)
N2—C2	1.325 (4)	C7—C8	1.388 (4)
C1—C2	1.506 (4)	C8—C9	1.394 (4)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—C10	1.393 (5)
C1—H1C	0.9800	C9—H9	0.9500
C2—C3	1.419 (4)	C10—C11	1.385 (4)
C3—C4	1.391 (4)	C10—H10	0.9500
C3—C6	1.450 (4)	C11—C12	1.392 (4)
C4—C5	1.494 (4)	C11—H11	0.9500
C5—H5A	0.9800	C12—H12	0.9500

C4—N1—N2	112.9 (2)	H5A—C5—H5C	109.5
C4—N1—C7	128.6 (2)	H5B—C5—H5C	109.5
N2—N1—C7	118.5 (2)	O1—C6—C3	125.8 (3)
C2—N2—N1	104.6 (2)	O1—C6—H6	117.1
C2—C1—H1A	109.5	C3—C6—H6	117.1
C2—C1—H1B	109.5	C12—C7—C8	121.4 (3)
H1A—C1—H1B	109.5	C12—C7—N1	119.2 (3)
C2—C1—H1C	109.5	C8—C7—N1	119.4 (3)
H1A—C1—H1C	109.5	C7—C8—C9	118.8 (3)
H1B—C1—H1C	109.5	C7—C8—H8	120.6
N2—C2—C3	111.0 (3)	C9—C8—H8	120.6
N2—C2—C1	119.9 (3)	C10—C9—C8	120.3 (3)
C3—C2—C1	129.1 (3)	C10—C9—H9	119.9
C4—C3—C2	105.4 (3)	C8—C9—H9	119.9
C4—C3—C6	125.2 (3)	C11—C10—C9	120.0 (3)
C2—C3—C6	129.4 (3)	C11—C10—H10	120.0
N1—C4—C3	106.1 (3)	C9—C10—H10	120.0
N1—C4—C5	122.7 (3)	C10—C11—C12	120.3 (3)
C3—C4—C5	131.3 (3)	C10—C11—H11	119.8
C4—C5—H5A	109.5	C12—C11—H11	119.8
C4—C5—H5B	109.5	C7—C12—C11	119.1 (3)
H5A—C5—H5B	109.5	C7—C12—H12	120.4
C4—C5—H5C	109.5	C11—C12—H12	120.4

C4—N1—N2—C2	−0.6 (3)	C6—C3—C4—C5	2.2 (5)
C7—N1—N2—C2	−178.7 (3)	C4—C3—C6—O1	177.3 (3)
N1—N2—C2—C3	0.3 (3)	C2—C3—C6—O1	−0.4 (5)
N1—N2—C2—C1	−179.5 (3)	C4—N1—C7—C12	−110.1 (4)
N2—C2—C3—C4	0.0 (4)	N2—N1—C7—C12	67.7 (4)
C1—C2—C3—C4	179.8 (3)	C4—N1—C7—C8	70.2 (4)
N2—C2—C3—C6	178.1 (3)	N2—N1—C7—C8	−112.1 (3)
C1—C2—C3—C6	−2.2 (6)	C12—C7—C8—C9	0.2 (5)
N2—N1—C4—C3	0.6 (3)	N1—C7—C8—C9	179.9 (3)
C7—N1—C4—C3	178.5 (3)	C7—C8—C9—C10	−1.1 (5)
N2—N1—C4—C5	179.9 (3)	C8—C9—C10—C11	0.8 (5)
C7—N1—C4—C5	−2.2 (5)	C9—C10—C11—C12	0.5 (5)
C2—C3—C4—N1	−0.3 (3)	C8—C7—C12—C11	1.1 (5)
C6—C3—C4—N1	−178.5 (3)	N1—C7—C12—C11	−178.7 (3)
C2—C3—C4—C5	−179.6 (3)	C10—C11—C12—C7	−1.4 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.95	2.43	3.315 (4)	155
C11—H11···Cg1ⁱⁱ	0.95	2.71	3.509 (4)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O
M_r	200.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.6264 (4), 6.7497 (4), 22.6203 (12)
β (°)	94.785 (5)
V (Å³)	1008.19 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.15 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.979, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	6376, 2335, 1951
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.194, 1.23
No. of reflections	2335
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.31

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.95	2.43	3.315 (4)	155
C11—H11···Cg1ⁱⁱ	0.95	2.71	3.509 (4)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2.

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors are grateful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing the research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Asiri, A. M., Al-Youbi, A. O., Ng, S. W. & Tiekink, E. R. T. (2012a). Acta Cryst. E68, o794. CSD CrossRef IUCr Journals Google Scholar
Asiri, A. M., Faidallah, H. M., Ng, S. W. & Tiekink, E. R. T. (2012b). Acta Cryst. E68, o764. CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kane, J. L. Jr, Hirth, B. H., Laing, D., Gourlie, B. B., Nahill, S. & Barsomian, G. (2003). Bioorg. Med. Chem. Lett. 13, 4463–4466. Web of Science CrossRef PubMed CAS Google Scholar
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doi:10.1107/S1600536812010240

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