1,4-Bis(4-pyridylsulfanylmeth­yl)benzene

Moon, S.-H.; Park, K.-M.

doi:10.1107/S1600536808017571

organic compounds

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Volume 64| Part 7| July 2008| Page o1285

doi:10.1107/S1600536808017571

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1,4-Bis(4-pyridylsulfanylmethyl)benzene

Suk-Hee Moon ^a and Ki-Min Park ^b ^*

^aSubdivision of Food Science, Kyungnam College of Information and Technology, Busan 616-701, Republic of Korea, and ^bResearch Institute of Natural Science, Gyeongsang National University, Jinju 660-701, Republic of Korea
^*Correspondence e-mail: kmpark@gnu.ac.kr

(Received 1 June 2008; accepted 11 June 2008; online 19 June 2008)

In the title compound, C₁₈H₁₆N₂S₂, a crystallographic inversion centre lies at the centre of the benzene ring, and the two terminal 4-mercaptopyridyl groups adopt an anti geometry. Each benzene ring makes a dihedral angle of 55.4 (1)° with the plane of the benzene fragment. The crystal structure is stabilized by C—H⋯π interactions between a benzene H atom and a pyridyl ring of a neighbouring molecule. In addition, the crystal structure exhibits intermolecular C—H⋯N interactions.

Related literature

For details of the preparation and related structures of 1,4-bis(2-pyridyl-sulfanylmethyl)benezene derivatives, see: Atherton et al. (1999 ); McMorran & Steel (2003 ); For the structures of Co(II) and Ag (I) complexes of 1,4-bis(2-pyridylsulfanylmethyl)benezene, see: Hartshorn & Steel (1998 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₈H₁₆N₂S₂
M_r = 324.45
Monoclinic, P 2₁ /c
a = 7.145 (1) Å
b = 6.1667 (8) Å
c = 17.954 (2) Å
β = 90.391 (3)°
V = 791.03 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 298 (2) K
0.35 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
4706 measured reflections
1717 independent reflections
893 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.121
S = 0.96
1717 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of N1/C1/C2/C3/C5 pyridyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N1ⁱ	0.93	2.61	3.484 (4)	158
C8—H8⋯Cgⁱⁱ	0.93	2.77	3.560 (4)	143
Symmetry codes: (i) $[-x-1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x, -y, -z+1.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017571/lx2058sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017571/lx2058Isup2.hkl

checkCIF report

Comment top

The reaction of α,α'-dibromo-p-xylene with 4-mercaptopyridine afforded the title compound, in which the crystallographic inversion centre lies on the centre of the benzene ring. Therefore, the asymmetric unit consists of a half of molecule and the two 4-mercaptopyridyl groups adopt an anti-geometry (Fig. 1). All bond lengths and angles show normal value (Allen et al., 1987). The dihedral angle between the plane of benzene and the terminal pyridyl ring is 55.4 (1)°, which is smaller than those of related structures (Atherton et al., 1999; Hartshorn & Steel, 1998).

The crystal packing (Fig. 2) is stabilized by C—H···π interactions between a benzene H atom and the pyridyl ring of neighbouring molecule, with a C8—H8···Cg separation of 2.77 Å (Fig. 2 and Table 1; Cg is the centroid of N1/C1/C2/C3/C5 pyridyl ring, symmetry code as in Fig. 2). The molecular packing (Fig. 2) is further stabilized by intermolecular C—H···N hydrogen bonds between a pyridyl H atom and the pyridine N atom of neighbouring molecule, with a C1—H1···N1ⁱ separation of 2.61 Å (Fig. 2 and Table 1; symmetry code as in Fig. 2).

Related literature top

For details of the preparation and related structures of 1,4-bis(2-pyridyl-sulfanylmethyl)benezene derivatives, see: Atherton et al. (1999); McMorran & Steel (2003); For the structures of Co(II) and Ag (I) complexes of 1,4-bis(2-pyridylsulfanylmethyl)benezene, see: Hartshorn & Steel (1998). Cg is the centroid of N1/C1/C2/C3/C5 pyridyl ring For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of α,α'-dibromo-p-xylene with 4-mercaptopyridine in acetonitrile according to reported methods (Atherton et al., 1999; McMorran & Steel, 2003). Single crystal suitable for X-ray analysis were obtained by evaporation of a solution of the title compound in acetonitrile.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. [Symmetry code: (i) -x + 1, -y + 1, -z + 1]
	Fig. 2. C—H···π and C—H···N interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x-1, y+1/2, -z+3/2; (iii) -x-1, y-1/2, -z+3/2; (iv) x+2, -y+1/2, z-1/2; (v) x+2, -y+3/2, z-1/2; (vi) -x, -y, -z+1;(vii) x+1, y+1, z.]

1,4-Bis(4-pyridylsulfanylmethyl)benzene top

Crystal data top

C₁₈H₁₆N₂S₂	F(000) = 340
M_r = 324.45	D_x = 1.362 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4706 reflections
a = 7.145 (1) Å	θ = 2.3–27.0°
b = 6.1667 (8) Å	µ = 0.33 mm⁻¹
c = 17.954 (2) Å	T = 298 K
β = 90.391 (3)°	Plate, colourless
V = 791.03 (18) Å³	0.35 × 0.20 × 0.15 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	893 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.074
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
ϕ and ω scans	h = −9→7
4706 measured reflections	k = −7→7
1717 independent reflections	l = −21→22

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0516P)²] where P = (F_o² + 2F_c²)/3
1717 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₈H₁₆N₂S₂	V = 791.03 (18) Å³
M_r = 324.45	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.145 (1) Å	µ = 0.33 mm⁻¹
b = 6.1667 (8) Å	T = 298 K
c = 17.954 (2) Å	0.35 × 0.20 × 0.15 mm
β = 90.391 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	893 reflections with I > 2σ(I)
4706 measured reflections	R_int = 0.074
1717 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 0.96	Δρ_max = 0.32 e Å⁻³
1717 reflections	Δρ_min = −0.17 e Å⁻³
100 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
S1	0.01648 (12)	0.27398 (12)	0.56971 (5)	0.0651 (3)
N1	−0.2740 (4)	−0.1917 (5)	0.72963 (13)	0.0677 (8)
C1	−0.3414 (4)	0.0057 (6)	0.71296 (17)	0.0632 (9)
H1	−0.4533	0.0486	0.7346	0.076*
C2	−0.2540 (4)	0.1478 (5)	0.66562 (16)	0.0587 (8)
H2	−0.3052	0.2842	0.6570	0.070*
C3	−0.0897 (4)	0.0876 (4)	0.63081 (15)	0.0501 (7)
C4	−0.0215 (4)	−0.1175 (5)	0.64684 (15)	0.0561 (8)
H4	0.0875	−0.1672	0.6245	0.067*
C5	−0.1161 (5)	−0.2463 (5)	0.69596 (15)	0.0593 (8)
H5	−0.0660	−0.3822	0.7065	0.071*
C6	0.2555 (4)	0.1735 (4)	0.56468 (16)	0.0620 (9)
H6A	0.3003	0.1373	0.6143	0.074*
H6B	0.2588	0.0430	0.5345	0.074*
C7	0.3805 (4)	0.3443 (4)	0.53083 (15)	0.0493 (7)
C8	0.4517 (4)	0.3178 (4)	0.46027 (16)	0.0537 (8)
H8	0.4190	0.1961	0.4325	0.064*
C9	0.4290 (4)	0.5300 (5)	0.56966 (15)	0.0554 (8)
H9	0.3801	0.5526	0.6169	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0593 (5)	0.0556 (5)	0.0806 (6)	0.0050 (4)	0.0101 (4)	0.0205 (4)
N1	0.0699 (19)	0.0749 (19)	0.0584 (16)	−0.0087 (15)	0.0095 (14)	0.0062 (14)
C1	0.051 (2)	0.079 (2)	0.059 (2)	−0.0008 (18)	0.0091 (16)	−0.0047 (18)
C2	0.057 (2)	0.0542 (18)	0.065 (2)	0.0081 (16)	−0.0015 (16)	−0.0020 (17)
C3	0.0483 (19)	0.0475 (17)	0.0546 (17)	−0.0018 (14)	−0.0016 (14)	−0.0025 (14)
C4	0.059 (2)	0.0474 (17)	0.0616 (19)	0.0032 (15)	0.0121 (16)	−0.0005 (16)
C5	0.066 (2)	0.0527 (18)	0.0595 (19)	0.0022 (17)	−0.0004 (17)	0.0065 (15)
C6	0.056 (2)	0.0492 (17)	0.081 (2)	0.0074 (14)	0.0188 (17)	0.0112 (16)
C7	0.0475 (18)	0.0459 (17)	0.0546 (18)	0.0039 (13)	0.0049 (15)	0.0074 (14)
C8	0.0600 (19)	0.0493 (17)	0.0519 (18)	−0.0006 (15)	0.0007 (15)	−0.0040 (15)
C9	0.060 (2)	0.0618 (19)	0.0443 (17)	0.0053 (17)	0.0105 (15)	0.0009 (15)

Geometric parameters (Å, º) top

S1—C3	1.764 (3)	C5—H5	0.9300
S1—C6	1.820 (3)	C6—C7	1.511 (4)
N1—C5	1.327 (4)	C6—H6A	0.9700
N1—C1	1.342 (4)	C6—H6B	0.9700
C1—C2	1.374 (4)	C7—C8	1.378 (3)
C1—H1	0.9300	C7—C9	1.383 (4)
C2—C3	1.385 (4)	C8—C9ⁱ	1.379 (4)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.385 (4)	C9—C8ⁱ	1.379 (4)
C4—C5	1.369 (4)	C9—H9	0.9300
C4—H4	0.9300

C3—S1—C6	102.52 (13)	C4—C5—H5	117.6
C5—N1—C1	115.7 (3)	C7—C6—S1	109.87 (18)
N1—C1—C2	123.6 (3)	C7—C6—H6A	109.7
N1—C1—H1	118.2	S1—C6—H6A	109.7
C2—C1—H1	118.2	C7—C6—H6B	109.7
C1—C2—C3	119.9 (3)	S1—C6—H6B	109.7
C1—C2—H2	120.1	H6A—C6—H6B	108.2
C3—C2—H2	120.1	C8—C7—C9	117.9 (3)
C2—C3—C4	116.7 (3)	C8—C7—C6	120.7 (3)
C2—C3—S1	118.4 (2)	C9—C7—C6	121.4 (3)
C4—C3—S1	124.9 (2)	C7—C8—C9ⁱ	120.7 (3)
C5—C4—C3	119.3 (3)	C7—C8—H8	119.7
C5—C4—H4	120.4	C9ⁱ—C8—H8	119.7
C3—C4—H4	120.4	C8ⁱ—C9—C7	121.3 (3)
N1—C5—C4	124.8 (3)	C8ⁱ—C9—H9	119.3
N1—C5—H5	117.6	C7—C9—H9	119.3

C5—N1—C1—C2	−1.4 (4)	C3—C4—C5—N1	1.2 (5)
N1—C1—C2—C3	1.6 (5)	C3—S1—C6—C7	−165.4 (2)
C1—C2—C3—C4	−0.4 (4)	S1—C6—C7—C8	−109.1 (3)
C1—C2—C3—S1	179.4 (2)	S1—C6—C7—C9	71.7 (3)
C6—S1—C3—C2	160.6 (2)	C9—C7—C8—C9ⁱ	1.5 (5)
C6—S1—C3—C4	−19.7 (3)	C6—C7—C8—C9ⁱ	−177.7 (2)
C2—C3—C4—C5	−0.9 (4)	C8—C7—C9—C8ⁱ	−1.5 (5)
S1—C3—C4—C5	179.3 (2)	C6—C7—C9—C8ⁱ	177.7 (3)
C1—N1—C5—C4	−0.1 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1ⁱⁱ	0.93	2.61	3.484 (4)	158
C8—H8···Cgⁱⁱⁱ	0.93	2.77	3.560 (4)	143

Symmetry codes: (ii) −x−1, y+1/2, −z+3/2; (iii) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₂S₂
M_r	324.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.145 (1), 6.1667 (8), 17.954 (2)
β (°)	90.391 (3)
V (Å³)	791.03 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.35 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4706, 1717, 893
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.121, 0.96
No. of reflections	1717
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.17

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1ⁱ	0.93	2.61	3.484 (4)	157.6
C8—H8···Cgⁱⁱ	0.93	2.77	3.560 (4)	143.0

Symmetry codes: (i) −x−1, y+1/2, −z+3/2; (ii) −x, −y, −z+1.

Acknowledgements

This work was supported by a Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–359-C00019).

References

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