1,4-Bis(4-pyridylsulfanylmeth­yl)benzene

Abstract

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,

• a = 7.145 (1) Å

• b = 6.1667 (8) Å

• c = 17.954 (2) Å

• β = 90.391 (3)°

• V = 791.03 (18) ų

• 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[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, U_iso =1.2U_eq(C) for aromatic and 0.97 Å, U_iso = 1.2U_eq(C) for CH₂ atoms.

Figures

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.]

Crystal data

C18H16N2S2	F000 = 340
Mr = 324.45	Dx = 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 = 2.3–27.0º
b = 6.1667 (8) Å	µ = 0.33 mm−1
c = 17.954 (2) Å	T = 298 (2) K
β = 90.391 (3)º	Plate, colourless
V = 791.03 (18) Å3	0.35 × 0.20 × 0.15 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	893 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.074
Monochromator: graphite	θmax = 27.0º
T = 298(2) K	θmin = 2.3º
φ and ω scans	h = −9→7
Absorption correction: none	k = −7→7
4706 measured reflections	l = −21→22
1717 independent reflections

Refinement

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)] = 0.052	H-atom parameters constrained
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0516P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96	(Δ/σ)max = 0.001
1717 reflections	Δρmax = 0.32 e Å−3
100 parameters	Δρmin = −0.17 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

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.