organic compounds
3-Methyl-5-(4-methylpiperazin-1-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde
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
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).
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).
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 .
details are summarized in Table 2Structural data
CCDC reference: 1509001
https://doi.org/10.1107/S2414314616015935/hb4084sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX2 (Bruker, 2013); cell
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).C16H20N4O | F(000) = 1216 |
Mr = 284.36 | Dx = 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 |
Bruker X8 Proteum CCD diffractometer | 2540 independent reflections |
Radiation source: fine-focus sealed tube | 2027 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 10.7 pixels mm-1 | θmax = 64.5°, θmin = 5.4° |
φ and ω scans | h = −20→20 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −11→10 |
Tmin = 0.824, Tmax = 0.851 | l = −15→21 |
14169 measured reflections |
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(Fo2) + (0.0579P)2 + 0.1549P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2540 reflections | Δρmax = 0.18 e Å−3 |
193 parameters | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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.
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