5-Chloro-2-(phenyl­diazen­yl)pyridine

Thies, S.; Näther, C.; Herges, R.

doi:10.1107/S1600536811047556

organic compounds

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Volume 67| Part 12| December 2011| Page o3298

https://doi.org/10.1107/S1600536811047556

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5-Chloro-2-(phenyldiazenyl)pyridine

Steffen Thies,^a Christian Näther ^b ^* and Rainer Herges ^a ^*

^aInstitut für Organische Chemie, Universität Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, and ^bInstitut für Anorganische Chemie, Universität Kiel, Otto-Hahn-Platz 6/7, 24118 Kiel, Germany
^*Correspondence e-mail: cnaether@ac.uni-kiel.de, rherges@oc.uni-kiel.de

(Received 1 November 2011; accepted 9 November 2011; online 12 November 2011)

In the title compound, C₁₁H₈ClN₃, the azo group adopts a trans conformation and the dihedral angle between the six-membered rings is 15.47 (8)°.

Related literature

For background to this work, see: Thies et al. (2010 , 2011 ); Venkataramani et al. (2011 ). For the structure of a bis(5-chloro-2-(phenylazo)pyridine)dichloro–ruthenium(II) complex, see: Hansongnern et al. (2008 ).

Experimental

Crystal data

C₁₁H₈ClN₃
M_r = 217.65
Monoclinic, P 2₁ /c
a = 6.1136 (2) Å
b = 9.0940 (4) Å
c = 18.6839 (8) Å
β = 91.459 (3)°
V = 1038.43 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Stoe IPDS-2 diffractometer
19329 measured reflections
2818 independent reflections
2456 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.117
S = 1.15
2818 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2008 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811047556/bt5703sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047556/bt5703Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811047556/bt5703Isup3.cml

checkCIF report

Comment top

We recently reported about a change of the spin state by association/dissociation of photodissociable ligands (PDL's) at square planar Ni(II) porphyrine complexes (Thies et al. 2010, Thies et al. 2011, Venkataramani et al., 2011). Within this project the title compound, was obtained as an intermediate in the synthesis of 5-methoxy-2-phenylazopyridine which can be used as PDL. For the identification of this intermediate a structure determination was performed.

In the structure of the title compound, the 5-chloro-2-phenylazopyridine molecules, are not coplanar. Both 6-membered rings are twisted by 15.47 (8) °. The azo group is in a trans configuration and the torsion angle C1—N2—N3—C6 amounts to 178.5 (2) °). In the crystal structure the molecules exhibit a sandwich herringbone arrangement with neighbouring molecules stacked onto each other. The molecules are also linked by weak C—H···N interactions.

Related literature top

For background to this work, see: Thies et al. (2010, 2011); Venkataramani et al. (2011). For the structure of a bis(5-chloro-2-(phenylazo)pyridine)dichloro–ruthenium(II) complex, see: Hansongnern et al. (2008).

Experimental top

Synthesis of 5-Chloro-2-phenylazopyridine

A mixture of sodium hydroxide (12.0 ml of 25%), pyridine (8.00 ml) and 2-amino-5-chlorpyridine (15.6 mmol, 2.00 g) (Merck) was stirred at 80 °C. Nitrosobenzene (16.0 mmol, 1.71 g) dissolved in pyridine (60.0 ml) was added dropwise during a period of 45 min. The mixture was stirred for additional 30 min at 80 °C and stirred at RT for 72 h. The reaction mixture was extracted with toluene. The combined organic layer was dried over magnesium sulfate. After removal of the solvent, recrystallization with diethylether afforded red crystalls in 36% yield.

mp.: 84.5–87 °C

¹H-NMR (600 MHz, 300 K, CDCl₃, TMS): δ = 8.69 (d, ⁴J=2.4 Hz, 1H, 6-H), 8.04- 8.03 (m, 2H, 2`-H), 7.87 (dd, ⁴J=2.5 Hz, ³J=8.5 Hz, 1H, 4-H), 7.81 (d, ³J=8.5 Hz, 1H, 3-H), 7.53–7.56 (m, 3H, 3`-H, 4`-H) p.p.m.. ¹³C-NMR (150 MHz, 300 K, CDCl₃, TMS): δ = 161.0 (C2), 152.3 (C10), 148.4 (C6), 138.1 (C4), 133.6 (C5), 132.5 (C40), 129.2 (C30), 123.7 (C20), 115.9 (C3) p.p.m.. MS (EI, 70 eV): m/z(%)= 217 (1) [M]⁺, 105 (89) [M—C₅H₃NCl]⁺. MS (CI, Isobutan): m/z(%)= 218 (100) [M+H]⁺. UV/Vis (Toluol): λ(_max)(lg ε)= 315 nm (4.058), 448 nm (2.494).

Structure description top

For background to this work, see: Thies et al. (2010, 2011); Venkataramani et al. (2011). For the structure of a bis(5-chloro-2-(phenylazo)pyridine)dichloro–ruthenium(II) complex, see: Hansongnern et al. (2008).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. : Crystal structure of the title compound with view in the direction of the crystallographic c axis.

5-Chloro-2-(phenyldiazenyl)pyridine top

Crystal data top

C₁₁H₈ClN₃	F(000) = 448
M_r = 217.65	D_x = 1.392 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1136 (2) Å	Cell parameters from 23258 reflections
b = 9.0940 (4) Å	θ = 2.2–29.2°
c = 18.6839 (8) Å	µ = 0.33 mm⁻¹
β = 91.459 (3)°	T = 293 K
V = 1038.43 (7) Å³	Block, colourless
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Stoe IPDS-2 diffractometer	2456 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 29.2°, θ_min = 2.2°
ω scans	h = −7→8
19329 measured reflections	k = −12→12
2818 independent reflections	l = −25→25

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0494P)² + 0.1607P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
2818 reflections	Δρ_max = 0.22 e Å⁻³
137 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: 0.013 (2)

Crystal data top

C₁₁H₈ClN₃	V = 1038.43 (7) Å³
M_r = 217.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1136 (2) Å	µ = 0.33 mm⁻¹
b = 9.0940 (4) Å	T = 293 K
c = 18.6839 (8) Å	0.3 × 0.2 × 0.2 mm
β = 91.459 (3)°

Data collection top

Stoe IPDS-2 diffractometer	2456 reflections with I > 2σ(I)
19329 measured reflections	R_int = 0.028
2818 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.15	Δρ_max = 0.22 e Å⁻³
2818 reflections	Δρ_min = −0.17 e Å⁻³
137 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	0.82419 (7)	−0.02057 (5)	0.37109 (2)	0.07091 (17)
C1	0.4709 (2)	0.27818 (16)	0.51393 (7)	0.0521 (3)
C2	0.4706 (3)	0.12003 (19)	0.42028 (8)	0.0610 (4)
H2	0.3950	0.0699	0.3840	0.073*
N1	0.3601 (2)	0.20937 (16)	0.46186 (7)	0.0620 (3)
C3	0.6925 (2)	0.09777 (16)	0.42821 (7)	0.0529 (3)
C4	0.8081 (2)	0.17112 (19)	0.48142 (9)	0.0605 (4)
H4	0.9585	0.1591	0.4872	0.073*
C5	0.6949 (2)	0.26232 (18)	0.52564 (8)	0.0586 (4)
H5	0.7666	0.3125	0.5627	0.070*
N2	0.3334 (2)	0.37225 (14)	0.55510 (7)	0.0588 (3)
N3	0.4247 (2)	0.41302 (15)	0.61134 (7)	0.0593 (3)
C6	0.2969 (3)	0.51050 (16)	0.65384 (8)	0.0559 (3)
C7	0.3993 (3)	0.5565 (2)	0.71665 (9)	0.0685 (4)
H7	0.5377	0.5211	0.7292	0.082*
C8	0.2973 (4)	0.6544 (2)	0.76071 (9)	0.0773 (5)
H8	0.3672	0.6861	0.8027	0.093*
C9	0.0916 (4)	0.7056 (2)	0.74256 (10)	0.0778 (5)
H9	0.0224	0.7721	0.7723	0.093*
C10	−0.0123 (3)	0.6581 (2)	0.68026 (11)	0.0750 (5)
H10	−0.1523	0.6919	0.6686	0.090*
C11	0.0890 (3)	0.56153 (19)	0.63543 (9)	0.0626 (4)
H11	0.0192	0.5307	0.5932	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0752 (3)	0.0732 (3)	0.0646 (3)	0.0099 (2)	0.00810 (19)	−0.00282 (19)
C1	0.0511 (7)	0.0541 (7)	0.0511 (7)	−0.0032 (6)	−0.0005 (6)	0.0062 (6)
C2	0.0545 (8)	0.0704 (9)	0.0577 (8)	−0.0019 (7)	−0.0079 (6)	−0.0056 (7)
N1	0.0487 (6)	0.0749 (8)	0.0619 (7)	0.0003 (6)	−0.0077 (5)	−0.0061 (6)
C3	0.0534 (7)	0.0551 (7)	0.0502 (7)	−0.0004 (6)	0.0027 (6)	0.0077 (6)
C4	0.0429 (7)	0.0727 (9)	0.0658 (9)	−0.0039 (6)	−0.0015 (6)	0.0023 (7)
C5	0.0510 (7)	0.0670 (9)	0.0575 (8)	−0.0113 (6)	−0.0050 (6)	−0.0028 (7)
N2	0.0553 (7)	0.0622 (7)	0.0587 (7)	−0.0034 (6)	−0.0047 (5)	0.0004 (6)
N3	0.0580 (7)	0.0654 (7)	0.0540 (7)	−0.0035 (6)	−0.0044 (5)	0.0024 (6)
C6	0.0605 (8)	0.0544 (8)	0.0529 (7)	−0.0063 (6)	0.0053 (6)	0.0058 (6)
C7	0.0691 (10)	0.0797 (11)	0.0565 (8)	0.0001 (8)	−0.0019 (7)	−0.0023 (8)
C8	0.0968 (14)	0.0797 (12)	0.0554 (9)	−0.0021 (10)	0.0015 (9)	−0.0046 (8)
C9	0.1020 (14)	0.0649 (10)	0.0675 (10)	0.0085 (10)	0.0238 (10)	0.0046 (8)
C10	0.0705 (10)	0.0715 (11)	0.0835 (12)	0.0104 (8)	0.0104 (9)	0.0137 (9)
C11	0.0639 (9)	0.0614 (9)	0.0623 (9)	−0.0049 (7)	−0.0011 (7)	0.0069 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.7288 (15)	N3—C6	1.435 (2)
C1—N1	1.3278 (19)	C6—C7	1.381 (2)
C1—C5	1.389 (2)	C6—C11	1.388 (2)
C1—N2	1.436 (2)	C7—C8	1.373 (3)
C2—N1	1.322 (2)	C7—H7	0.9300
C2—C3	1.376 (2)	C8—C9	1.375 (3)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.377 (2)	C9—C10	1.381 (3)
C4—C5	1.370 (2)	C9—H9	0.9300
C4—H4	0.9300	C10—C11	1.372 (3)
C5—H5	0.9300	C10—H10	0.9300
N2—N3	1.2341 (17)	C11—H11	0.9300

N1—C1—C5	123.29 (15)	C7—C6—C11	120.09 (15)
N1—C1—N2	112.26 (13)	C7—C6—N3	114.62 (14)
C5—C1—N2	124.44 (13)	C11—C6—N3	125.27 (14)
N1—C2—C3	123.00 (14)	C8—C7—C6	120.23 (17)
N1—C2—H2	118.5	C8—C7—H7	119.9
C3—C2—H2	118.5	C6—C7—H7	119.9
C2—N1—C1	117.49 (13)	C7—C8—C9	119.86 (18)
C2—C3—C4	119.51 (14)	C7—C8—H8	120.1
C2—C3—Cl1	119.90 (12)	C9—C8—H8	120.1
C4—C3—Cl1	120.59 (12)	C8—C9—C10	120.02 (18)
C5—C4—C3	118.09 (14)	C8—C9—H9	120.0
C5—C4—H4	121.0	C10—C9—H9	120.0
C3—C4—H4	121.0	C11—C10—C9	120.62 (18)
C4—C5—C1	118.60 (14)	C11—C10—H10	119.7
C4—C5—H5	120.7	C9—C10—H10	119.7
C1—C5—H5	120.7	C10—C11—C6	119.17 (16)
N3—N2—C1	112.15 (13)	C10—C11—H11	120.4
N2—N3—C6	114.60 (13)	C6—C11—H11	120.4

Experimental details

Crystal data
Chemical formula	C₁₁H₈ClN₃
M_r	217.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.1136 (2), 9.0940 (4), 18.6839 (8)
β (°)	91.459 (3)
V (Å³)	1038.43 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19329, 2818, 2456
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.15
No. of reflections	2818
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft via SFB 677.

References

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