3-Methyl-5-(4-methyl­piperazin-1-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde

Sunitha, V.M.; Manju, N.; Naveen, S.; Kalluraya, B.; Lokanath, N.K.; Manjunath, H.R.

doi:10.1107/S2414314616015935

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161593

https://doi.org/10.1107/S2414314616015935

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3-Methyl-5-(4-methylpiperazin-1-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde

V. M. Sunitha,^a N. Manju,^b S. Naveen,^c B. Kalluraya,^b N. K. Lokanath ^d and H. R. Manjunath ^e ^*

^aDepartment of Physics, Shri Pillappa College of Engineering, Bengaluru 560 089, India, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, ^cInstitution of Excellence, University of Mysore, Manasagangotri, Mysore 570 006, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^eDepartment of Physics, Acharya Institute of Technology, Soldevanahalli, Bengaluru 560 107, India
^*Correspondence e-mail: manjunathhr@acharya.ac.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 6 October 2016; accepted 9 October 2016; online 15 November 2016)

In the title compound, C₁₆H₂₀N₄O, the dihedral angle between the pyrazole and phenyl rings is 53.86 (12)°. The piperazine ring adopts a chair conformation with the exocyclic N—C bonds in equatorial orientations. In the crystal, molecules are linked by very weak C—H⋯O hydrogen bonds to generate [010] C(8) chains, with adjacent molecules related by translation.

Keywords: crystal structure; pyrazole; hydrogen bonding.

CCDC reference: 1509001

Structure description

Piperazine derivatives are found in biologically active compounds across many therapeutic areas and display antipsychotic (Chaudhary et al., 2006 ) and antifungal (Upadhayaya et al., 2004 ) behaviours. As part of our ongoing studies in this area (Girisha et al., 2010 ), herein we report the synthesis and structure of the title compound (Fig. 1).

Figure 1
A view of the title compound, with displacement ellipsoids for non-H atoms drawn at the 50% probability level.

The dihedral angle between the pyrazole (r.m.s. deviation = 0.012 Å) and phenyl rings is 53.86 (12)°. The piperazine ring adopts a chair conformation with the exocyclic N—C bonds in equatorial orientations. The piperazine ring bisects the plane of the pyrazole ring which is evident from the dihedral angle value of 53.57 (10)° between the mean planes of the pyrazole and piperazine (all atoms) rings.

In the crystal, the molecules are linked by weak C—H⋯O hydrogen bonds (Table 1) to generate [010] C(8) chains, with adjacent molecules related by translation (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O8ⁱ	0.97	2.60	3.4753 (19)	151
Symmetry code: (i) x, y+1, z.

Figure 2
Packing diagram of the title molecule, viewed down the c axis. The dashed lines represent hydrogen bonds.

Synthesis and crystallization

After synthesis and purification (Girisha et al., 2010), the title compound was dissolved in ethanol and the solution was gently heated and left undisturbed. After slow evaporation of the solvent, colourless blocks grew after 10 d.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₂₀N₄O
M_r	284.36
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	17.1027 (13), 9.4885 (8), 18.6837 (16)
V (Å³)	3032.0 (4)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	0.65
Crystal size (mm)	0.30 × 0.27 × 0.25

Data collection
Diffractometer	Bruker X8 Proteum CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.824, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	14169, 2540, 2027
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.585

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.117, 1.07
No. of reflections	2540
No. of parameters	193
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008).

Structural data

CCDC reference: 1509001

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616015935/hb4084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616015935/hb4084Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015935/hb4084Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).

3-Methyl-5-(4-methylpiperazin-1-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde top

Crystal data top

C₁₆H₂₀N₄O	F(000) = 1216
M_r = 284.36	D_x = 1.246 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2501 reflections
a = 17.1027 (13) Å	θ = 5.4–64.5°
b = 9.4885 (8) Å	µ = 0.65 mm⁻¹
c = 18.6837 (16) Å	T = 293 K
V = 3032.0 (4) Å³	Block, colorless
Z = 8	0.30 × 0.27 × 0.25 mm

Data collection top

Bruker X8 Proteum CCD diffractometer	2540 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
Detector resolution: 10.7 pixels mm^-1	θ_max = 64.5°, θ_min = 5.4°
φ and ω scans	h = −20→20
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −11→10
T_min = 0.824, T_max = 0.851	l = −15→21
14169 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0579P)² + 0.1549P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2540 reflections	Δρ_max = 0.18 e Å⁻³
193 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0020 (3)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.38513 (6)	0.16761 (12)	0.60098 (8)	0.0434 (3)
N2	0.40285 (7)	0.03759 (14)	0.63048 (8)	0.0514 (4)
C3	0.40416 (7)	−0.05029 (17)	0.57596 (10)	0.0474 (4)
C4	0.38990 (7)	0.01950 (15)	0.51072 (9)	0.0418 (4)
C5	0.37799 (6)	0.16018 (14)	0.52887 (9)	0.0385 (4)
C6	0.42103 (10)	−0.20264 (18)	0.58809 (12)	0.0706 (6)
H6A	0.4270	−0.2198	0.6384	0.106*
H6B	0.4684	−0.2279	0.5637	0.106*
H6C	0.3786	−0.2583	0.5699	0.106*
C7	0.39904 (8)	−0.03138 (17)	0.43884 (10)	0.0524 (5)
H7	0.3933	0.0342	0.4022	0.063*
O8	0.41359 (7)	−0.15167 (12)	0.42117 (8)	0.0698 (4)
N9	0.36366 (6)	0.27099 (12)	0.48325 (7)	0.0427 (3)
C10	0.28918 (7)	0.27548 (16)	0.44428 (9)	0.0485 (4)
H10A	0.2501	0.3235	0.4729	0.058*
H10B	0.2710	0.1803	0.4352	0.058*
C11	0.30008 (8)	0.35158 (16)	0.37487 (10)	0.0506 (4)
H11A	0.3354	0.2984	0.3446	0.061*
H11B	0.2502	0.3588	0.3504	0.061*
N12	0.33155 (6)	0.49159 (12)	0.38653 (7)	0.0417 (3)
C13	0.40635 (7)	0.48233 (16)	0.42350 (9)	0.0449 (4)
H13A	0.4272	0.5763	0.4308	0.054*
H13B	0.4432	0.4300	0.3943	0.054*
C14	0.39691 (8)	0.41040 (16)	0.49448 (9)	0.0481 (4)
H14A	0.4473	0.4022	0.5179	0.058*
H14B	0.3627	0.4655	0.5250	0.058*
C15	0.33932 (9)	0.56944 (18)	0.31972 (10)	0.0586 (5)
H15A	0.3725	0.5181	0.2875	0.088*
H15B	0.3619	0.6602	0.3292	0.088*
H15C	0.2887	0.5813	0.2984	0.088*
C16	0.37949 (7)	0.28622 (16)	0.64745 (9)	0.0441 (4)
C17	0.31364 (8)	0.37036 (18)	0.64642 (10)	0.0541 (5)
H17	0.2717	0.3478	0.6169	0.065*
C18	0.31068 (10)	0.48774 (19)	0.68942 (11)	0.0641 (5)
H18	0.2670	0.5461	0.6882	0.077*
C19	0.37206 (11)	0.51924 (19)	0.73435 (11)	0.0712 (6)
H19	0.3700	0.5991	0.7631	0.085*
C20	0.43651 (10)	0.4323 (2)	0.73658 (10)	0.0679 (5)
H20	0.4773	0.4526	0.7678	0.081*
C21	0.44102 (8)	0.31600 (18)	0.69310 (9)	0.0542 (4)
H21	0.4848	0.2580	0.6943	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0510 (6)	0.0348 (7)	0.0443 (9)	0.0023 (5)	0.0005 (5)	0.0027 (7)
N2	0.0608 (7)	0.0412 (7)	0.0522 (10)	0.0021 (5)	0.0014 (6)	0.0104 (7)
C3	0.0460 (7)	0.0369 (8)	0.0592 (12)	−0.0010 (6)	0.0036 (7)	0.0031 (9)
C4	0.0430 (6)	0.0336 (8)	0.0487 (11)	−0.0025 (5)	0.0012 (6)	−0.0002 (8)
C5	0.0374 (6)	0.0333 (7)	0.0449 (10)	−0.0029 (5)	−0.0012 (6)	0.0007 (8)
C6	0.0827 (10)	0.0402 (9)	0.0888 (17)	0.0069 (8)	0.0030 (10)	0.0140 (11)
C7	0.0571 (7)	0.0400 (9)	0.0599 (13)	−0.0068 (6)	0.0025 (7)	−0.0051 (9)
O8	0.0849 (7)	0.0421 (7)	0.0823 (11)	−0.0028 (5)	0.0116 (7)	−0.0181 (7)
N9	0.0454 (5)	0.0322 (6)	0.0503 (9)	−0.0062 (5)	−0.0128 (5)	0.0032 (6)
C10	0.0425 (6)	0.0428 (8)	0.0602 (11)	−0.0067 (6)	−0.0113 (7)	0.0043 (9)
C11	0.0513 (7)	0.0465 (9)	0.0539 (12)	−0.0036 (6)	−0.0160 (7)	0.0004 (9)
N12	0.0448 (5)	0.0360 (6)	0.0444 (8)	0.0025 (4)	−0.0066 (5)	0.0026 (7)
C13	0.0442 (6)	0.0367 (8)	0.0537 (11)	−0.0041 (6)	−0.0084 (6)	0.0036 (8)
C14	0.0564 (7)	0.0353 (8)	0.0526 (11)	−0.0091 (6)	−0.0155 (7)	0.0030 (9)
C15	0.0707 (9)	0.0535 (9)	0.0516 (11)	0.0013 (7)	−0.0105 (8)	0.0085 (10)
C16	0.0518 (7)	0.0412 (8)	0.0393 (9)	−0.0028 (6)	0.0083 (6)	0.0001 (8)
C17	0.0532 (7)	0.0559 (10)	0.0531 (11)	0.0049 (7)	0.0080 (7)	−0.0026 (10)
C18	0.0740 (9)	0.0576 (10)	0.0606 (13)	0.0113 (8)	0.0231 (9)	−0.0026 (11)
C19	0.0965 (13)	0.0579 (10)	0.0590 (14)	−0.0083 (9)	0.0274 (11)	−0.0154 (11)
C20	0.0754 (10)	0.0754 (12)	0.0529 (12)	−0.0176 (9)	0.0050 (9)	−0.0138 (12)
C21	0.0562 (7)	0.0587 (9)	0.0477 (11)	−0.0031 (7)	0.0002 (7)	−0.0040 (10)

Geometric parameters (Å, º) top

N1—C5	1.354 (2)	N12—C15	1.457 (2)
N1—N2	1.3848 (16)	N12—C13	1.4566 (16)
N1—C16	1.4247 (19)	C13—C14	1.500 (2)
N2—C3	1.317 (2)	C13—H13A	0.9700
C3—C4	1.408 (2)	C13—H13B	0.9700
C3—C6	1.491 (2)	C14—H14A	0.9700
C4—C5	1.3921 (18)	C14—H14B	0.9700
C4—C7	1.436 (2)	C15—H15A	0.9600
C5—N9	1.3756 (18)	C15—H15B	0.9600
C6—H6A	0.9600	C15—H15C	0.9600
C6—H6B	0.9600	C16—C17	1.381 (2)
C6—H6C	0.9600	C16—C21	1.384 (2)
C7—O8	1.2140 (18)	C17—C18	1.374 (2)
C7—H7	0.9300	C17—H17	0.9300
N9—C14	1.4551 (17)	C18—C19	1.377 (3)
N9—C10	1.4678 (16)	C18—H18	0.9300
C10—C11	1.496 (2)	C19—C20	1.377 (3)
C10—H10A	0.9700	C19—H19	0.9300
C10—H10B	0.9700	C20—C21	1.373 (2)
C11—N12	1.4498 (18)	C20—H20	0.9300
C11—H11A	0.9700	C21—H21	0.9300
C11—H11B	0.9700

C5—N1—N2	111.67 (12)	C11—N12—C13	110.00 (11)
C5—N1—C16	129.89 (13)	C15—N12—C13	110.91 (11)
N2—N1—C16	118.42 (14)	N12—C13—C14	110.61 (11)
C3—N2—N1	105.07 (14)	N12—C13—H13A	109.5
N2—C3—C4	111.64 (14)	C14—C13—H13A	109.5
N2—C3—C6	119.98 (17)	N12—C13—H13B	109.5
C4—C3—C6	128.37 (17)	C14—C13—H13B	109.5
C5—C4—C3	105.38 (15)	H13A—C13—H13B	108.1
C5—C4—C7	124.49 (15)	N9—C14—C13	109.16 (13)
C3—C4—C7	129.24 (14)	N9—C14—H14A	109.8
N1—C5—N9	126.34 (13)	C13—C14—H14A	109.8
N1—C5—C4	106.21 (13)	N9—C14—H14B	109.8
N9—C5—C4	127.44 (16)	C13—C14—H14B	109.8
C3—C6—H6A	109.5	H14A—C14—H14B	108.3
C3—C6—H6B	109.5	N12—C15—H15A	109.5
H6A—C6—H6B	109.5	N12—C15—H15B	109.5
C3—C6—H6C	109.5	H15A—C15—H15B	109.5
H6A—C6—H6C	109.5	N12—C15—H15C	109.5
H6B—C6—H6C	109.5	H15A—C15—H15C	109.5
O8—C7—C4	126.37 (17)	H15B—C15—H15C	109.5
O8—C7—H7	116.8	C17—C16—C21	120.72 (16)
C4—C7—H7	116.8	C17—C16—N1	120.23 (14)
C5—N9—C14	122.40 (12)	C21—C16—N1	119.05 (13)
C5—N9—C10	118.97 (10)	C18—C17—C16	119.38 (16)
C14—N9—C10	112.60 (11)	C18—C17—H17	120.3
N9—C10—C11	109.62 (11)	C16—C17—H17	120.3
N9—C10—H10A	109.7	C17—C18—C19	120.28 (16)
C11—C10—H10A	109.7	C17—C18—H18	119.9
N9—C10—H10B	109.7	C19—C18—H18	119.9
C11—C10—H10B	109.7	C18—C19—C20	119.90 (18)
H10A—C10—H10B	108.2	C18—C19—H19	120.0
N12—C11—C10	111.00 (13)	C20—C19—H19	120.0
N12—C11—H11A	109.4	C21—C20—C19	120.57 (17)
C10—C11—H11A	109.4	C21—C20—H20	119.7
N12—C11—H11B	109.4	C19—C20—H20	119.7
C10—C11—H11B	109.4	C20—C21—C16	119.10 (15)
H11A—C11—H11B	108.0	C20—C21—H21	120.4
C11—N12—C15	111.71 (13)	C16—C21—H21	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O8ⁱ	0.97	2.60	3.4753 (19)	151

Symmetry code: (i) x, y+1, z.

Acknowledgements

The authors thank the Institution of Excellence, Vijnana Bhavana, University of Mysore, Mysuru for providing the single-crystal X-ray diffractometer facility.

References

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