1,6-Bis(chloro­meth­yl)pyridine

Betz, R.; Gerber, T.; Schalekamp, H.

doi:10.1107/S1600536811020678

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1577

doi:10.1107/S1600536811020678

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1,6-Bis(chloromethyl)pyridine

Richard Betz,^a ^* Thomas Gerber ^a and Henk Schalekamp ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 26 May 2011; accepted 30 May 2011; online 4 June 2011)

In the title compound, C₇H₇Cl₂N, a halogenated derivative of 2,6-lutidine, the C—Cl vectors of the chloromethyl groups point at opposite sides of the aromatic plane to each other. A weak dispersive Cl⋯Cl contact [3.4342 (3) Å] connects the molecules into a chain along the [101] direction. A π–π interaction with a centroid–centroid distance of 3.7481 (5) Å is also observed.

Related literature

For the crystal structure of the hydrochloride of the title compound, see: Lozano & Jones (2004 ).

Experimental

Crystal data

C₇H₇Cl₂N
M_r = 176.04
Monoclinic, P 2₁ /c
a = 8.9927 (2) Å
b = 12.1581 (3) Å
c = 7.4893 (2) Å
β = 113.535 (1)°
V = 750.72 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 100 K
0.52 × 0.41 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.727, T_max = 0.872
6994 measured reflections
1845 independent reflections
1768 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.051
S = 1.09
1845 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020678/is2723sup1.cif

Supporting information file. DOI: 10.1107/S1600536811020678/is2723Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020678/is2723Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811020678/is2723Isup4.cml

checkCIF report

Comment top

Multidentate ligands are versatile complexation agents for a variety of main group elements as well as transition metals. In some cases, the assignment or the determination of oxidation states of coordinated transition metals relies heavily on the knowledge of metric parameters within the ligand. To enable comparative studies within a group of coordination compounds currently under investigation in our working group we determined the crystal structure of the title compound which serves as a starting material for one of the multidentate ligands applied thereof. The crystal structure of the hydrochloride of the title compound is apparent in the literature (Lozano & Jones, 2004).

In the molecule, the chloromethyl substituents are pointing at the two different sides of the plane defined by the atoms of the aromatic system. Intracyclic angles span a range from 117.41 (8)–123.38 (8) ° with the smallest angle on the nitrogen atom and the two biggest ones on the carbon atoms adjacent to it (Fig. 1).

The molecules in the crystal structure only interact via weak dispersive Cl···Cl contacts [Cl1···Cl2ⁱⁱ 3.4342 (3) Å; symmetry code: (ii) x - 1, y, z - 1] whose range falls by about 0.1 Å below the sum of van-der-Waals radii. These contacts connect the molecules to a chains along the [101] direction (Fig. 2). The closest distance between two π-systems was found at 3.7481 (5) Å. The packing of the compound in the crystal structure is shown in Figure 3.

Related literature top

For the crystal structure of the hydrochloride of the title compound, see: Lozano & Jones (2004).

Experimental top

The compound was obtained commercially (Aldrich). Crystals suitable for the X-ray diffraction study were taken directly from the provided product.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Intermolecular contacts, viewed along the b axis. Symmetry codes: (i) x + 1, y, z + 1; (ii) x - 1, y, z - 1.
	Fig. 3. Molecular packing of the title compound, viewed along the b axis. (anisotropic displacement ellipsoids drawn at 50% probability level).

1,6-Bis(chloromethyl)pyridine top

Crystal data top

C₇H₇Cl₂N	F(000) = 360
M_r = 176.04	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 346 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.9927 (2) Å	Cell parameters from 5840 reflections
b = 12.1581 (3) Å	θ = 2.5–28.3°
c = 7.4893 (2) Å	µ = 0.78 mm⁻¹
β = 113.535 (1)°	T = 100 K
V = 750.72 (3) Å³	Platelet, colourless
Z = 4	0.52 × 0.41 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1845 independent reflections
Radiation source: fine-focus sealed tube	1768 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
T_min = 0.727, T_max = 0.872	k = −14→16
6994 measured reflections	l = −9→9

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.051	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0223P)² + 0.2778P] where P = (F_o² + 2F_c²)/3
1845 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₇H₇Cl₂N	V = 750.72 (3) Å³
M_r = 176.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.9927 (2) Å	µ = 0.78 mm⁻¹
b = 12.1581 (3) Å	T = 100 K
c = 7.4893 (2) Å	0.52 × 0.41 × 0.18 mm
β = 113.535 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1845 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1768 reflections with I > 2σ(I)
T_min = 0.727, T_max = 0.872	R_int = 0.014
6994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.051	H-atom parameters constrained
S = 1.09	Δρ_max = 0.36 e Å⁻³
1845 reflections	Δρ_min = −0.18 e Å⁻³
91 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	−0.34591 (3)	0.401927 (19)	0.11753 (3)	0.01804 (7)
Cl2	0.47219 (3)	0.37996 (2)	0.61934 (3)	0.01866 (7)
N1	0.06320 (9)	0.35805 (7)	0.36585 (10)	0.01355 (16)
C1	−0.06797 (11)	0.30473 (8)	0.36501 (12)	0.01361 (17)
C2	−0.07993 (11)	0.19055 (8)	0.36280 (13)	0.01536 (18)
H2	−0.1747	0.1559	0.3626	0.018*
C3	0.04877 (11)	0.12810 (8)	0.36096 (13)	0.01600 (18)
H3	0.0435	0.0500	0.3585	0.019*
C4	0.18529 (11)	0.18224 (8)	0.36276 (13)	0.01472 (18)
H4	0.2757	0.1420	0.3624	0.018*
C5	0.18709 (10)	0.29671 (8)	0.36515 (12)	0.01296 (17)
C6	−0.20508 (12)	0.37527 (8)	0.36486 (13)	0.01779 (19)
H6A	−0.1617	0.4457	0.4317	0.021*
H6B	−0.2620	0.3375	0.4365	0.021*
C7	0.33299 (11)	0.35840 (8)	0.36959 (13)	0.01679 (19)
H7A	0.2991	0.4302	0.3033	0.020*
H7B	0.3872	0.3160	0.2998	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01397 (11)	0.02042 (12)	0.01663 (12)	0.00406 (8)	0.00284 (8)	0.00130 (8)
Cl2	0.01427 (11)	0.02260 (13)	0.01632 (12)	−0.00528 (8)	0.00316 (8)	−0.00105 (8)
N1	0.0133 (4)	0.0151 (4)	0.0111 (3)	0.0002 (3)	0.0037 (3)	−0.0007 (3)
C1	0.0118 (4)	0.0183 (4)	0.0093 (4)	0.0014 (3)	0.0027 (3)	−0.0005 (3)
C2	0.0126 (4)	0.0193 (4)	0.0131 (4)	−0.0030 (3)	0.0040 (3)	−0.0002 (3)
C3	0.0177 (4)	0.0136 (4)	0.0153 (4)	−0.0009 (3)	0.0050 (3)	−0.0006 (3)
C4	0.0134 (4)	0.0165 (4)	0.0137 (4)	0.0016 (3)	0.0048 (3)	−0.0008 (3)
C5	0.0118 (4)	0.0165 (4)	0.0093 (4)	−0.0014 (3)	0.0029 (3)	−0.0008 (3)
C6	0.0143 (4)	0.0243 (5)	0.0135 (4)	0.0042 (4)	0.0042 (3)	−0.0007 (3)
C7	0.0146 (4)	0.0218 (5)	0.0134 (4)	−0.0046 (3)	0.0049 (3)	−0.0021 (3)

Geometric parameters (Å, º) top

Cl1—C6	1.8074 (10)	C3—H3	0.9500
Cl2—C7	1.8068 (9)	C4—C5	1.3918 (13)
N1—C5	1.3425 (11)	C4—H4	0.9500
N1—C1	1.3438 (12)	C5—C7	1.5001 (12)
C1—C2	1.3920 (14)	C6—H6A	0.9900
C1—C6	1.5016 (13)	C6—H6B	0.9900
C2—C3	1.3888 (13)	C7—H7A	0.9900
C2—H2	0.9500	C7—H7B	0.9900
C3—C4	1.3883 (13)

C5—N1—C1	117.41 (8)	N1—C5—C7	116.23 (8)
N1—C1—C2	123.00 (8)	C4—C5—C7	120.39 (8)
N1—C1—C6	116.32 (8)	C1—C6—Cl1	110.02 (6)
C2—C1—C6	120.67 (8)	C1—C6—H6A	109.7
C3—C2—C1	118.98 (9)	Cl1—C6—H6A	109.7
C3—C2—H2	120.5	C1—C6—H6B	109.7
C1—C2—H2	120.5	Cl1—C6—H6B	109.7
C4—C3—C2	118.55 (9)	H6A—C6—H6B	108.2
C4—C3—H3	120.7	C5—C7—Cl2	109.50 (6)
C2—C3—H3	120.7	C5—C7—H7A	109.8
C3—C4—C5	118.68 (8)	Cl2—C7—H7A	109.8
C3—C4—H4	120.7	C5—C7—H7B	109.8
C5—C4—H4	120.7	Cl2—C7—H7B	109.8
N1—C5—C4	123.38 (8)	H7A—C7—H7B	108.2

C5—N1—C1—C2	−0.23 (12)	C1—N1—C5—C7	−178.98 (7)
C5—N1—C1—C6	−179.72 (7)	C3—C4—C5—N1	0.01 (13)
N1—C1—C2—C3	−0.14 (14)	C3—C4—C5—C7	179.26 (8)
C6—C1—C2—C3	179.33 (8)	N1—C1—C6—Cl1	91.43 (8)
C1—C2—C3—C4	0.44 (13)	C2—C1—C6—Cl1	−88.07 (9)
C2—C3—C4—C5	−0.38 (13)	N1—C5—C7—Cl2	90.05 (8)
C1—N1—C5—C4	0.29 (12)	C4—C5—C7—Cl2	−89.24 (9)

Experimental details

Crystal data
Chemical formula	C₇H₇Cl₂N
M_r	176.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.9927 (2), 12.1581 (3), 7.4893 (2)
β (°)	113.535 (1)
V (Å³)	750.72 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.52 × 0.41 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.727, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	6994, 1845, 1768
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.051, 1.09
No. of reflections	1845
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.18

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank Mr Barry Noble for helpful discussions.

References

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Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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