organic compounds
of 2-(4-methylpiperazin-1-yl)quinoline-3-carbaldehyde
aDepartment of Chemistry, University College of Science, Tumkur University, Tumkur 572 103, India, bInstitution of Excellence, University of Mysore, Mysuru-6, India, and cDepartment of Physics, University of Mysore, Mysuru-6, India
*Correspondence e-mail: drsreenivasa@yahoo.co.in
In the title compound, C15H17N3O, the aldehyde group is twisted relative to the quinoline group by17.6 (2)° due to the presence of a bulky piperazinyl group in the ortho position. The piperazine N atom attached to the aromatic ring is sp3-hybridized and the dihedral angle between the mean planes through the the six piperazine ring atoms and through the quinoline ring system is 40.59 (7)°. Both piperazine substituents are in equatorial positions.
Keywords: crystal structure; quinolines; piperazines.
CCDC reference: 1433198
1. Related literature
For biological activity of quinoline derivatives, see: Nasveld et al. (2005); Eswaran et al. (2009); Leatham et al. (1983); Muruganantham et al. (2004); Maguire et al. (1994); Wilson et al. (1992); Strekowski et al. (1991). For photonic and electronic properties of poly-substituted quinolines, see: Gyoten et al. (2003).
2. Experimental
2.1. Crystal data
|
2.3. Refinement
|
Data collection: APEX2 (Bruker, 2009); cell APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus and XPREP (Bruker, 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., 2008); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 1433198
https://doi.org/10.1107/S2056989015020186/gk2647sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015020186/gk2647Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015020186/gk2647Isup3.cml
Quinoline and its derivatives have been well known in pharmaceutical chemistry because of their wide spectrum of biological activities and their presence in naturally occurring compounds. They have been shown to possess antimalarial (Nasveld et al., 2005), antibiotic (Eswaran et al., 2009), anticancer (Denny et al., 1983), anti-inflammatory (Muruganantham et al., 2004), antihypertensive (Maguire et al., 1994), tyrokinase PDGF-RTK inhibition (Wilson et al., 1992) and anti-HIV properties (Strekowski et al., 1991). In addition, polysubstituted quinoline can achieve hierchical self-assembly into variety of meso and nano structures with enhanced photonic and electronic properties (Gyoten et al., 2003). In this view the title compound was synthesized to study its crystal structure.
2-Chloroquinoline-3-carbaldehyde (0.42 g, 0.00351 mmol), N-methyl piperazine (0.14 g, 0.00351 mmol) and anhydrous K2CO3 (1.0 g, 0.002920 mmol) were refluxed for 24 hrs in DMF. The progress of the reaction was monitored by thin layer
After the completion of the reaction, the reaction mixture was poured into water and extracted to ethyl acetate. The organic layer was washed with water, dried and concentrated under vacuum using rotary evaporator. Single crystals of the title compound were obtained by slow evaporation of the ethyl acetate solution at room temperature (27oC).Crystal data, data collection and structure
details are summarized in Table 1. All H atoms were positioned with idealized geometry using a riding model with C—H = 0.93-0.97 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent C atom).Quinoline and its derivatives have been well known in pharmaceutical chemistry because of their wide spectrum of biological activities and their presence in naturally occurring compounds. They have been shown to possess antimalarial (Nasveld et al., 2005), antibiotic (Eswaran et al., 2009), anticancer (Denny et al., 1983), anti-inflammatory (Muruganantham et al., 2004), antihypertensive (Maguire et al., 1994), tyrokinase PDGF-RTK inhibition (Wilson et al., 1992) and anti-HIV properties (Strekowski et al., 1991). In addition, polysubstituted quinoline can achieve hierchical self-assembly into variety of meso and nano structures with enhanced photonic and electronic properties (Gyoten et al., 2003). In this view the title compound was synthesized to study its crystal structure.
The crystal packing of the compound does not feature any specific strong or weak intermolecular interactions.
For biological activity of quinoline derivatives, see: Nasveld et al. (2005); Eswaran et al. (2009); Leatham et al. (1983); Muruganantham et al. (2004); Maguire et al. (1994); Wilson et al. (1992); Strekowski et al. (1991). For photonic and electronic properties of poly-substituted quinolines, see: Gyoten et al. (2003).
2-Chloroquinoline-3-carbaldehyde (0.42 g, 0.00351 mmol), N-methyl piperazine (0.14 g, 0.00351 mmol) and anhydrous K2CO3 (1.0 g, 0.002920 mmol) were refluxed for 24 hrs in DMF. The progress of the reaction was monitored by thin layer
After the completion of the reaction, the reaction mixture was poured into water and extracted to ethyl acetate. The organic layer was washed with water, dried and concentrated under vacuum using rotary evaporator. Single crystals of the title compound were obtained by slow evaporation of the ethyl acetate solution at room temperature (27oC). detailsCrystal data, data collection and structure
details are summarized in Table 1. All H atoms were positioned with idealized geometry using a riding model with C—H = 0.93-0.97 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the Ueq of the parent C atom).Data collection: APEX2 (Bruker, 2009); cell
APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus and XPREP (Bruker, 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., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. |
C15H17N3O | Prism |
Mr = 255.32 | Dx = 1.269 Mg m−3 |
Monoclinic, P21/n | Melting point: 384 K |
Hall symbol: -P 2yn | Cu Kα radiation, λ = 1.54178 Å |
a = 12.3282 (4) Å | Cell parameters from 143 reflections |
b = 5.8935 (2) Å | θ = 3.9–64.5° |
c = 18.9202 (7) Å | µ = 0.65 mm−1 |
β = 103.591 (2)° | T = 296 K |
V = 1336.18 (8) Å3 | Prism, colourless |
Z = 4 | 0.28 × 0.26 × 0.24 mm |
F(000) = 544 |
Bruker APEXII CCD diffractometer | 2181 independent reflections |
Radiation source: fine-focus sealed tube | 1859 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
phi and φ scans | θmax = 64.5°, θmin = 3.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −14→14 |
Tmin = 0.838, Tmax = 0.859 | k = −6→6 |
9762 measured reflections | l = −21→21 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1151P)2 + 0.0654P] where P = (Fo2 + 2Fc2)/3 |
2181 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C15H17N3O | V = 1336.18 (8) Å3 |
Mr = 255.32 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 12.3282 (4) Å | µ = 0.65 mm−1 |
b = 5.8935 (2) Å | T = 296 K |
c = 18.9202 (7) Å | 0.28 × 0.26 × 0.24 mm |
β = 103.591 (2)° |
Bruker APEXII CCD diffractometer | 2181 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1859 reflections with I > 2σ(I) |
Tmin = 0.838, Tmax = 0.859 | Rint = 0.048 |
9762 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.22 e Å−3 |
2181 reflections | Δρmin = −0.24 e Å−3 |
173 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | 0.44347 (10) | 0.7887 (2) | 0.60405 (6) | 0.0446 (4) | |
N2 | 0.31637 (10) | 0.4894 (2) | 0.58318 (6) | 0.0443 (4) | |
N3 | 0.15374 (11) | 0.2821 (2) | 0.46867 (7) | 0.0492 (4) | |
O1 | 0.33529 (13) | 0.4038 (3) | 0.79890 (7) | 0.0800 (5) | |
C1 | 0.38623 (12) | 0.6362 (3) | 0.63074 (7) | 0.0415 (4) | |
C2 | 0.39605 (12) | 0.6082 (3) | 0.70773 (8) | 0.0435 (4) | |
C3 | 0.46317 (13) | 0.7537 (3) | 0.75426 (8) | 0.0456 (4) | |
H3 | 0.4690 | 0.7410 | 0.8040 | 0.055* | |
C4 | 0.52382 (12) | 0.9229 (3) | 0.72789 (8) | 0.0429 (4) | |
C5 | 0.59503 (14) | 1.0786 (3) | 0.77313 (9) | 0.0517 (5) | |
H5 | 0.6035 | 1.0718 | 0.8232 | 0.062* | |
C6 | 0.65119 (15) | 1.2380 (3) | 0.74416 (10) | 0.0571 (5) | |
H6 | 0.6980 | 1.3397 | 0.7744 | 0.068* | |
C7 | 0.63874 (16) | 1.2497 (3) | 0.66853 (10) | 0.0580 (5) | |
H7 | 0.6768 | 1.3606 | 0.6490 | 0.070* | |
C8 | 0.57153 (14) | 1.1003 (3) | 0.62334 (9) | 0.0516 (5) | |
H8 | 0.5648 | 1.1094 | 0.5734 | 0.062* | |
C9 | 0.51232 (12) | 0.9326 (3) | 0.65156 (8) | 0.0430 (4) | |
C10 | 0.19665 (13) | 0.5037 (3) | 0.58101 (8) | 0.0477 (4) | |
H10A | 0.1659 | 0.6413 | 0.5560 | 0.057* | |
H10B | 0.1861 | 0.5100 | 0.6302 | 0.057* | |
C11 | 0.13648 (13) | 0.3007 (3) | 0.54226 (9) | 0.0517 (5) | |
H11A | 0.1635 | 0.1642 | 0.5694 | 0.062* | |
H11B | 0.0573 | 0.3142 | 0.5399 | 0.062* | |
C12 | 0.27299 (14) | 0.2697 (3) | 0.47221 (9) | 0.0522 (5) | |
H12A | 0.2846 | 0.2582 | 0.4234 | 0.063* | |
H12B | 0.3038 | 0.1347 | 0.4988 | 0.063* | |
C13 | 0.33266 (14) | 0.4768 (3) | 0.50926 (8) | 0.0516 (5) | |
H13A | 0.4117 | 0.4670 | 0.5106 | 0.062* | |
H13B | 0.3031 | 0.6123 | 0.4824 | 0.062* | |
C14 | 0.09682 (18) | 0.0831 (4) | 0.43236 (9) | 0.0660 (6) | |
H14A | 0.1106 | 0.0708 | 0.3846 | 0.099* | |
H14B | 0.0181 | 0.0973 | 0.4285 | 0.099* | |
H14C | 0.1242 | −0.0501 | 0.4600 | 0.099* | |
C15 | 0.34545 (14) | 0.4132 (3) | 0.73732 (9) | 0.0561 (5) | |
H15 | 0.3201 | 0.2913 | 0.7067 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0470 (7) | 0.0482 (8) | 0.0386 (7) | −0.0039 (6) | 0.0102 (6) | 0.0002 (5) |
N2 | 0.0423 (7) | 0.0538 (9) | 0.0381 (7) | −0.0054 (6) | 0.0119 (5) | −0.0038 (6) |
N3 | 0.0541 (8) | 0.0505 (9) | 0.0400 (7) | −0.0114 (6) | 0.0047 (6) | 0.0021 (6) |
O1 | 0.0885 (10) | 0.1024 (13) | 0.0487 (8) | −0.0299 (8) | 0.0151 (7) | 0.0178 (7) |
C1 | 0.0400 (8) | 0.0462 (9) | 0.0389 (8) | 0.0020 (6) | 0.0102 (6) | 0.0015 (6) |
C2 | 0.0408 (8) | 0.0503 (10) | 0.0392 (8) | 0.0025 (6) | 0.0088 (6) | 0.0038 (7) |
C3 | 0.0456 (9) | 0.0556 (10) | 0.0348 (8) | 0.0055 (7) | 0.0076 (6) | 0.0042 (7) |
C4 | 0.0402 (8) | 0.0467 (9) | 0.0407 (8) | 0.0049 (6) | 0.0077 (6) | 0.0001 (6) |
C5 | 0.0529 (10) | 0.0568 (11) | 0.0431 (8) | 0.0002 (8) | 0.0064 (7) | −0.0061 (7) |
C6 | 0.0583 (10) | 0.0557 (11) | 0.0549 (10) | −0.0102 (8) | 0.0086 (8) | −0.0100 (8) |
C7 | 0.0640 (11) | 0.0530 (11) | 0.0576 (10) | −0.0139 (8) | 0.0155 (8) | −0.0007 (8) |
C8 | 0.0574 (10) | 0.0544 (11) | 0.0439 (8) | −0.0055 (8) | 0.0142 (7) | 0.0014 (7) |
C9 | 0.0427 (8) | 0.0458 (10) | 0.0402 (8) | 0.0020 (6) | 0.0090 (6) | −0.0002 (6) |
C10 | 0.0450 (9) | 0.0568 (11) | 0.0420 (8) | −0.0011 (7) | 0.0117 (6) | 0.0002 (7) |
C11 | 0.0481 (9) | 0.0603 (11) | 0.0465 (9) | −0.0097 (7) | 0.0108 (7) | 0.0025 (7) |
C12 | 0.0614 (10) | 0.0561 (11) | 0.0402 (8) | −0.0041 (7) | 0.0143 (7) | −0.0042 (7) |
C13 | 0.0513 (9) | 0.0644 (11) | 0.0424 (8) | −0.0112 (8) | 0.0180 (7) | −0.0056 (7) |
C14 | 0.0820 (13) | 0.0605 (12) | 0.0491 (10) | −0.0239 (9) | 0.0026 (9) | 0.0008 (8) |
C15 | 0.0567 (10) | 0.0634 (12) | 0.0449 (9) | −0.0096 (8) | 0.0050 (7) | 0.0107 (8) |
N1—C1 | 1.315 (2) | C6—H6 | 0.9300 |
N1—C9 | 1.375 (2) | C7—C8 | 1.364 (3) |
N2—C1 | 1.391 (2) | C7—H7 | 0.9300 |
N2—C13 | 1.4607 (18) | C8—C9 | 1.406 (2) |
N2—C10 | 1.4693 (19) | C8—H8 | 0.9300 |
N3—C14 | 1.454 (2) | C10—C11 | 1.505 (2) |
N3—C12 | 1.458 (2) | C10—H10A | 0.9700 |
N3—C11 | 1.461 (2) | C10—H10B | 0.9700 |
O1—C15 | 1.202 (2) | C11—H11A | 0.9700 |
C1—C2 | 1.442 (2) | C11—H11B | 0.9700 |
C2—C3 | 1.361 (2) | C12—C13 | 1.510 (2) |
C2—C15 | 1.479 (2) | C12—H12A | 0.9700 |
C3—C4 | 1.406 (2) | C12—H12B | 0.9700 |
C3—H3 | 0.9300 | C13—H13A | 0.9700 |
C4—C5 | 1.411 (2) | C13—H13B | 0.9700 |
C4—C9 | 1.419 (2) | C14—H14A | 0.9600 |
C5—C6 | 1.357 (3) | C14—H14B | 0.9600 |
C5—H5 | 0.9300 | C14—H14C | 0.9600 |
C6—C7 | 1.404 (3) | C15—H15 | 0.9300 |
C1—N1—C9 | 118.40 (12) | N2—C10—C11 | 110.18 (13) |
C1—N2—C13 | 116.58 (12) | N2—C10—H10A | 109.6 |
C1—N2—C10 | 116.60 (12) | C11—C10—H10A | 109.6 |
C13—N2—C10 | 109.84 (11) | N2—C10—H10B | 109.6 |
C14—N3—C12 | 110.53 (15) | C11—C10—H10B | 109.6 |
C14—N3—C11 | 110.40 (13) | H10A—C10—H10B | 108.1 |
C12—N3—C11 | 109.34 (12) | N3—C11—C10 | 111.00 (13) |
N1—C1—N2 | 118.89 (12) | N3—C11—H11A | 109.4 |
N1—C1—C2 | 122.74 (14) | C10—C11—H11A | 109.4 |
N2—C1—C2 | 118.32 (13) | N3—C11—H11B | 109.4 |
C3—C2—C1 | 118.36 (14) | C10—C11—H11B | 109.4 |
C3—C2—C15 | 119.41 (14) | H11A—C11—H11B | 108.0 |
C1—C2—C15 | 121.90 (15) | N3—C12—C13 | 110.89 (14) |
C2—C3—C4 | 120.69 (14) | N3—C12—H12A | 109.5 |
C2—C3—H3 | 119.7 | C13—C12—H12A | 109.5 |
C4—C3—H3 | 119.7 | N3—C12—H12B | 109.5 |
C3—C4—C5 | 123.55 (14) | C13—C12—H12B | 109.5 |
C3—C4—C9 | 117.08 (14) | H12A—C12—H12B | 108.0 |
C5—C4—C9 | 119.36 (15) | N2—C13—C12 | 108.90 (13) |
C6—C5—C4 | 120.59 (15) | N2—C13—H13A | 109.9 |
C6—C5—H5 | 119.7 | C12—C13—H13A | 109.9 |
C4—C5—H5 | 119.7 | N2—C13—H13B | 109.9 |
C5—C6—C7 | 120.09 (16) | C12—C13—H13B | 109.9 |
C5—C6—H6 | 120.0 | H13A—C13—H13B | 108.3 |
C7—C6—H6 | 120.0 | N3—C14—H14A | 109.5 |
C8—C7—C6 | 120.80 (16) | N3—C14—H14B | 109.5 |
C8—C7—H7 | 119.6 | H14A—C14—H14B | 109.5 |
C6—C7—H7 | 119.6 | N3—C14—H14C | 109.5 |
C7—C8—C9 | 120.59 (15) | H14A—C14—H14C | 109.5 |
C7—C8—H8 | 119.7 | H14B—C14—H14C | 109.5 |
C9—C8—H8 | 119.7 | O1—C15—C2 | 123.51 (18) |
N1—C9—C8 | 118.78 (13) | O1—C15—H15 | 118.2 |
N1—C9—C4 | 122.64 (14) | C2—C15—H15 | 118.2 |
C8—C9—C4 | 118.56 (15) |
Experimental details
Crystal data | |
Chemical formula | C15H17N3O |
Mr | 255.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 12.3282 (4), 5.8935 (2), 18.9202 (7) |
β (°) | 103.591 (2) |
V (Å3) | 1336.18 (8) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.28 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.838, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9762, 2181, 1859 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.585 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.162, 1.06 |
No. of reflections | 2181 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.24 |
Computer programs: APEX2 (Bruker, 2009), APEX2 and SAINT-Plus (Bruker, 2009), SAINT-Plus and XPREP (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008).
Acknowledgements
The authors are thankful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, Mysuru, for providing the single-crystal X-ray diffraction facility. RND, SS, PAS and DBAK are thankful to Tumkur University for providing laboratory facilities to carry out this work.
References
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