Crystal structure of 2-(4-methyl­piperazin-1-yl)quinoline-3-carbaldehyde

Nivedita Desai, R.; Sreenivasa, S.; Naveen, S.; Lokanath, N.K.; Suchetan, P.A.; Aruna Kumar, D.B.

doi:10.1107/S2056989015020186

organic compounds

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Volume 71| Part 11| November 2015| Pages o900-o901

https://doi.org/10.1107/S2056989015020186

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Crystal structure of 2-(4-methylpiperazin-1-yl)quinoline-3-carbaldehyde

R Nivedita Desai,^a S Sreenivasa,^a ^* S. Naveen,^b N. K. Lokanath,^c P. A. Suchetan ^a and D. B. Aruna Kumar ^a

^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

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 16 October 2015; accepted 26 October 2015; online 31 October 2015)

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

C₁₅H₁₇N₃O
M_r = 255.32
Monoclinic, P 2₁ /n
a = 12.3282 (4) Å
b = 5.8935 (2) Å
c = 18.9202 (7) Å
β = 103.591 (2)°
V = 1336.18 (8) Å³
Z = 4
Cu Kα radiation
μ = 0.65 mm⁻¹
T = 296 K
0.28 × 0.26 × 0.24 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.838, T_max = 0.859
9762 measured reflections
2181 independent reflections
1859 reflections with I > 2σ(I)
R_int = 0.048

2.3. Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.162
S = 1.06
2181 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: 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

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015020186/gk2647sup1.cif

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

checkCIF report

Introduction top

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.

Experimental top

Synthesis and crystallization top

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 chromatography. 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 (27^oC).

Refinement top

Crystal data, data collection and structure refinement 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).

Results and discussion top

The crystal packing of the compound does not feature any specific strong or weak intermolecular interactions.

Related literature top

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).

Structure description top

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).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

2-(4-Methylpiperazin-1-yl)quinoline-3-carbaldehyde top

Crystal data top

C₁₅H₁₇N₃O	Prism
M_r = 255.32	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2181 independent reflections
Radiation source: fine-focus sealed tube	1859 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
phi and φ scans	θ_max = 64.5°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.838, T_max = 0.859	k = −6→6
9762 measured reflections	l = −21→21

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1151P)² + 0.0654P] where P = (F_o² + 2F_c²)/3
2181 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₅H₁₇N₃O	V = 1336.18 (8) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2181 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1859 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.859	R_int = 0.048
9762 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
2181 reflections	Δρ_min = −0.24 e Å⁻³
173 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.838, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	9762, 2181, 1859
R_int	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
Δρ_max, Δρ_min (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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Volume 71| Part 11| November 2015| Pages o900-o901

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