3-(4-Chloro­phenyl­diazen­yl)-1-methyl-1,4,5,6-tetra­hydro­pyridine

Meneghetti, F.; Bombieri, G.; Tonelli, M.

doi:10.1107/S1600536808018217

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1297

doi:10.1107/S1600536808018217

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3-(4-Chlorophenyldiazenyl)-1-methyl-1,4,5,6-tetrahydropyridine

Fiorella Meneghetti,^a ^* Gabriella Bombieri ^a and Michele Tonelli ^b

^aInstitute of Pharmaceutical and Toxicological Chemistry, `P.Pratesi', University of Milano, via L. Mangiagalli 25, 20133 Milano, Italy, and ^bDepartment of Pharmaceutical Chemistry, University of Genova, viale Benedetto XV, 16132 Genova, Italy
^*Correspondence e-mail: fiorella.meneghetti@unimi.it

(Received 30 May 2008; accepted 16 June 2008; online 19 June 2008)

The title compound, C₁₂H₁₄ClN₃, represents the planar azoenamine tautomer. The benzene ring forms a dihedral angle of 2.5 (1)° with the azoenamine group. Electron delocalization is indicated by the values of the bond lengths in the chain. The tetrahydropyridine ring adopts a half-chair conformation and the dihedral angle between the least-squares plane defined by the five coplanar C atoms and the azoenamine unit is 2.0 (1)°, while the envelope-flap C atom lies out of this plane by 0.579 (2) Å. The molecular packing is governed by van der Waals interactions through the stacking of adjacent molecules, resulting in a two-dimensional sheet structure.

Related literature

Arylazoenamines are useful templates for the investigation of the role of substituents on the benzene ring in the treatment of arylhydrazones with acids (Canu Boido et al., 1993 ). For related literature, see: Boido Canu et al. (1988 ); Sparatore et al. (1990 ); Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₂H₁₄ClN₃
M_r = 235.71
Triclinic, $[P \overline 1]$
a = 6.251 (2) Å
b = 8.483 (3) Å
c = 11.824 (4) Å
α = 77.590 (10)°
β = 78.450 (10)°
γ = 87.01 (2)°
V = 599.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 (2) K
0.6 × 0.5 × 0.4 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
3028 measured reflections
2893 independent reflections
1803 reflections with I > 2σ(I)
R_int = 0.014
3 standard reflections frequency: 120 min intensity decay: <1%

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.191
S = 1.04
2893 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018217/fj2123sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018217/fj2123Isup2.hkl

checkCIF report

Comment top

In order to define the influence exerted by the chloro-benzene nucleus on the yields of azoenamines, the hydrazone-hydrazoene tautomerism has been investigated by X-ray analysis of the derivative 1 (Fig. 1). The results could be an useful tool to understand the antimicrobial properties of arylazoenamine compounds (Canu Boido et al., 1993). As this compound could resonate with the amphoionic structure, the X-ray analysis allowed the identification of the tautomer (Fig. 2). The extended conformation of the azoenamine skeleton is characterized by the torsion angles N3—C8—C7—N2 of 179.2 (1)°, C8—C7—N2—N1 of 179.2 (1)°, C7—N2—N1—C5 of 179.0 (1)° and N2—N1—C5—C4 of 176.9 (1)°, indicating the quite coplanarity of the aromatic ring with the azoenamine moiety. This allows a certain degree of electron delocalization, beginning at the phenyl moiety and extending through the double bond, as shown by the shortening of the bond lenghts N2—C7 of 1.361 (4)Å and C8—N3 of 1.361 (4) Å. The half chair conformation of the tetrahydropyridine ring is defined by the puckering parameter of ϕ2=173.3 (1)° and QT=0.426 (4)Å (Cremer & Pople, 1975). The molecular packing is governed by the van der Waals interactions through the stacking of adjacent molecules, resulting in a two-dimesional sheet structure (Fig. 3).

Related literature top

Arylazoenamines are useful templates for the investigation of the role of substituents on the benzene ring in the treatment of arylhydrazones with acids (Canu Boido et al., 1993). For related literature, see: Boido Canu et al., (1988); Sparatore et al., (1990).

For related literature, see: Cremer & Pople (1975).

Experimental top

The title compound derives from the azo-coupling reaction with acids between 2-formyl-1-methylpyrrolidine and p-chlorophenylhydrazine (Canu Boido et al., 1993). Single crystal of 1 were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. : Chemical scheme of the two tautomers of 1.
	Fig. 2. : The molecular structure of the title compound, showing atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 3. : Packing diagram of 1, showing the two-dimensional sheet structure formed by the molecular stacking.

3-(4-Chlorophenyldiazenyl)-1-methyl-1,4,5,6-tetrahydropyridine top

Crystal data top

C₁₂H₁₄ClN₃	Z = 2
M_r = 235.71	F(000) = 248
Triclinic, P1	D_x = 1.305 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.251 (2) Å	Cell parameters from 25 reflections
b = 8.483 (3) Å	θ = 9–10°
c = 11.824 (4) Å	µ = 0.30 mm⁻¹
α = 77.59 (1)°	T = 293 K
β = 78.45 (1)°	Prism, red
γ = 87.01 (2)°	0.6 × 0.5 × 0.4 mm
V = 599.9 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.014
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 3.9°
Graphite monochromator	h = −8→8
Non–profiled ω/2θ scans	k = −11→10
3028 measured reflections	l = −15→0
2893 independent reflections	3 standard reflections every 120 min
1803 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.117P)² + 0.0064P] where P = (F_o² + 2F_c²)/3
2893 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₂H₁₄ClN₃	γ = 87.01 (2)°
M_r = 235.71	V = 599.9 (4) Å³
Triclinic, P1	Z = 2
a = 6.251 (2) Å	Mo Kα radiation
b = 8.483 (3) Å	µ = 0.30 mm⁻¹
c = 11.824 (4) Å	T = 293 K
α = 77.59 (1)°	0.6 × 0.5 × 0.4 mm
β = 78.45 (1)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.014
3028 measured reflections	3 standard reflections every 120 min
2893 independent reflections	intensity decay: <1%
1803 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
2893 reflections	Δρ_min = −0.50 e Å⁻³
146 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Cl1	−0.62912 (9)	0.77463 (8)	0.36467 (7)	0.0818 (3)
N1	0.1713 (3)	0.4296 (2)	0.18348 (17)	0.0586 (5)
N2	0.2811 (3)	0.3554 (2)	0.26078 (17)	0.0577 (5)
N3	0.7609 (3)	0.1111 (2)	0.27394 (19)	0.0677 (6)
C1	−0.3925 (3)	0.6722 (2)	0.3139 (2)	0.0592 (6)
C2	−0.0779 (3)	0.5151 (3)	0.3523 (2)	0.0630 (6)
H2	0.0076	0.4626	0.4052	0.076*
C3	−0.3383 (4)	0.6673 (3)	0.1976 (2)	0.0670 (6)
H3	−0.4274	0.7175	0.1459	0.080*
C4	−0.1496 (4)	0.5873 (3)	0.1563 (2)	0.0631 (6)
H4	−0.1117	0.5847	0.0766	0.076*
C5	−0.0155 (3)	0.5106 (2)	0.2336 (2)	0.0562 (5)
C6	−0.2651 (3)	0.5964 (3)	0.3933 (2)	0.0645 (6)
H6	−0.3047	0.6002	0.4728	0.077*
C7	0.4609 (3)	0.2732 (2)	0.2171 (2)	0.0585 (6)
C8	0.5789 (3)	0.1961 (3)	0.2987 (2)	0.0600 (6)
H8	0.5286	0.2036	0.3769	0.072*
C9	0.5288 (4)	0.2646 (3)	0.0908 (2)	0.0698 (6)
H9A	0.6038	0.3629	0.0471	0.084*
H9B	0.4007	0.2552	0.0581	0.084*
C10	0.6793 (5)	0.1200 (4)	0.0783 (3)	0.0841 (8)
H10A	0.5929	0.0225	0.1014	0.101*
H10B	0.7492	0.1302	−0.0039	0.101*
C11	0.8530 (4)	0.1044 (3)	0.1526 (3)	0.0780 (8)
H11A	0.9306	0.0027	0.1504	0.094*
H11B	0.9574	0.1908	0.1194	0.094*
C12	0.8856 (4)	0.0404 (3)	0.3635 (3)	0.0819 (8)
H12A	0.8063	0.0531	0.4394	0.123*
H12B	1.0237	0.0936	0.3467	0.123*
H12C	0.9096	−0.0724	0.3637	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0537 (4)	0.0776 (5)	0.1070 (6)	0.0248 (3)	−0.0085 (3)	−0.0163 (4)
N1	0.0465 (9)	0.0571 (10)	0.0711 (12)	0.0101 (7)	−0.0116 (8)	−0.0129 (9)
N2	0.0441 (9)	0.0510 (9)	0.0756 (12)	0.0059 (7)	−0.0095 (8)	−0.0111 (8)
N3	0.0461 (9)	0.0618 (11)	0.0926 (15)	0.0147 (8)	−0.0137 (10)	−0.0136 (10)
C1	0.0427 (10)	0.0480 (11)	0.0835 (17)	0.0082 (8)	−0.0106 (10)	−0.0101 (10)
C2	0.0450 (11)	0.0723 (14)	0.0733 (16)	0.0150 (10)	−0.0188 (10)	−0.0154 (11)
C3	0.0579 (12)	0.0606 (13)	0.0815 (17)	0.0182 (10)	−0.0213 (12)	−0.0102 (12)
C4	0.0609 (13)	0.0565 (12)	0.0695 (14)	0.0132 (10)	−0.0151 (11)	−0.0089 (10)
C5	0.0435 (10)	0.0486 (11)	0.0755 (15)	0.0036 (8)	−0.0115 (10)	−0.0116 (10)
C6	0.0494 (11)	0.0736 (14)	0.0701 (14)	0.0142 (10)	−0.0117 (10)	−0.0176 (11)
C7	0.0439 (10)	0.0527 (11)	0.0768 (15)	0.0064 (9)	−0.0087 (10)	−0.0131 (10)
C8	0.0459 (10)	0.0569 (12)	0.0748 (14)	0.0070 (9)	−0.0118 (10)	−0.0101 (10)
C9	0.0559 (12)	0.0736 (15)	0.0780 (16)	0.0154 (11)	−0.0117 (11)	−0.0170 (12)
C10	0.0721 (16)	0.0881 (19)	0.096 (2)	0.0231 (14)	−0.0126 (14)	−0.0356 (16)
C11	0.0522 (13)	0.0751 (16)	0.106 (2)	0.0177 (11)	−0.0069 (13)	−0.0291 (15)
C12	0.0600 (14)	0.0723 (16)	0.111 (2)	0.0158 (12)	−0.0264 (14)	−0.0085 (14)

Geometric parameters (Å, º) top

Cl1—C1	1.743 (2)	C6—H6	0.9300
N1—N2	1.289 (3)	C7—C8	1.366 (3)
N1—C5	1.414 (3)	C7—C9	1.484 (4)
N2—C7	1.363 (3)	C8—H8	0.9300
N3—C8	1.331 (3)	C9—C10	1.521 (3)
N3—C11	1.447 (3)	C9—H9A	0.9700
N3—C12	1.448 (3)	C9—H9B	0.9700
C1—C3	1.358 (4)	C10—C11	1.512 (4)
C1—C6	1.383 (3)	C10—H10A	0.9700
C2—C6	1.383 (3)	C10—H10B	0.9700
C2—C5	1.388 (4)	C11—H11A	0.9700
C2—H2	0.9300	C11—H11B	0.9700
C3—C4	1.385 (3)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.398 (3)	C12—H12C	0.9600
C4—H4	0.9300

N2—N1—C5	112.81 (19)	N3—C8—H8	117.8
N1—N2—C7	115.1 (2)	C7—C8—H8	117.8
C8—N3—C11	119.8 (2)	C7—C9—C10	110.2 (2)
C8—N3—C12	121.7 (2)	C7—C9—H9A	109.6
C11—N3—C12	118.06 (19)	C10—C9—H9A	109.6
C3—C1—C6	121.5 (2)	C7—C9—H9B	109.6
C3—C1—Cl1	119.29 (18)	C10—C9—H9B	109.6
C6—C1—Cl1	119.2 (2)	H9A—C9—H9B	108.1
C6—C2—C5	121.1 (2)	C11—C10—C9	112.6 (2)
C6—C2—H2	119.5	C11—C10—H10A	109.1
C5—C2—H2	119.5	C9—C10—H10A	109.1
C1—C3—C4	119.7 (2)	C11—C10—H10B	109.1
C1—C3—H3	120.2	C9—C10—H10B	109.1
C4—C3—H3	120.2	H10A—C10—H10B	107.8
C3—C4—C5	120.5 (2)	N3—C11—C10	111.89 (19)
C3—C4—H4	119.7	N3—C11—H11A	109.2
C5—C4—H4	119.7	C10—C11—H11A	109.2
C2—C5—C4	118.33 (19)	N3—C11—H11B	109.2
C2—C5—N1	125.3 (2)	C10—C11—H11B	109.2
C4—C5—N1	116.3 (2)	H11A—C11—H11B	107.9
C2—C6—C1	118.9 (2)	N3—C12—H12A	109.5
C2—C6—H6	120.6	N3—C12—H12B	109.5
C1—C6—H6	120.6	H12A—C12—H12B	109.5
N2—C7—C8	115.1 (2)	N3—C12—H12C	109.5
N2—C7—C9	124.0 (2)	H12A—C12—H12C	109.5
C8—C7—C9	120.91 (19)	H12B—C12—H12C	109.5
N3—C8—C7	124.5 (2)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄ClN₃
M_r	235.71
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.251 (2), 8.483 (3), 11.824 (4)
α, β, γ (°)	77.59 (1), 78.45 (1), 87.01 (2)
V (Å³)	599.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.6 × 0.5 × 0.4

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3028, 2893, 1803
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.191, 1.04
No. of reflections	2893
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.50

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

References

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