5,8-Dibromo-2,11-dithia­[3,3](2,6)pyridino­paracyclo­phane

Li, S.-S.; Zhang, B.; Zhang, H.-L.

doi:10.1107/S1600536810028850

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2125

https://doi.org/10.1107/S1600536810028850

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5,8-Dibromo-2,11-dithia[3,3](2,6)pyridinoparacyclophane

Si-Si Li,^a ^* Bei Zhang ^a and Hong-Lin Zhang ^a

^aKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: 78766912@163.com

(Received 1 July 2010; accepted 20 July 2010; online 24 July 2010)

The title compound, C₁₅H₁₃Br₂NS₂ [systematic name: 1²,1⁵-dibromo-2,7-dithia-1(1,4)-benzena-5(2,6)-pyridinaoctaphane], contains a dibromo-substituted benzene ring and a pyridine ring that are linked by a pair of bridging —CH₂SCH₂— groups. There is a weak π–π interaction between the rings, the distance between the ring centroids being 3.572 (4) Å. The rings are not parallel, but form a dihedral angle of 18.29 (4)°.

Related literature

For the preparation of the title compound, see: Kay & Baek (1997 ); Scheytza et al. (1999 ); Xu et al. (2008 ). For further information on paracyclophane and its derivatives, see: Wang et al. (2006 ); Yamamoto et al. (1997 ).

Experimental

Crystal data

C₁₅H₁₃Br₂NS₂
M_r = 431.20
Monoclinic, P 2₁ /n
a = 8.9275 (15) Å
b = 18.879 (3) Å
c = 9.3213 (15) Å
β = 103.878 (3)°
V = 1525.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 5.58 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.452, T_max = 0.573
11428 measured reflections
3775 independent reflections
3018 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.078
S = 1.03
3775 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810028850/pk2253sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028850/pk2253Isup2.hkl

checkCIF report

Comment top

In our research, we have synthesized the title compound 5,8-dibromo-2,11-dithia[3,3] (2,6)pyridinoparacyclophane. In the crystal structure, there are no classical hydrogen bonds, but is a weak π–π interaction. The distance between the centroid of the pyridine ring and the centroid of the benzene ring is 3.574 (4) Å, in addition, the angle between pyridine ring and the benzene ring is 18.29 (4)°.

Related literature top

For the preparation of the title compound, see: Kay & Baek (1997); Scheytza et al. (1999); Xu et al. (2008). For further information on paracyclophane and its derivatives, see: Wang et al. (2006); Yamamoto et al. (1997).

Experimental top

The title compound was synthesized according to a modified literature procedure (Scheytza et al., 1999).

A solution with equimolar amounts of the dithiol(3.26g, 10mmol) and 2,6-bis(bromomethyl) pyridine in degassed THF (500 mL) was added dropwise under N₂ over 12 h to a refluxing solution of K₂CO₃(6.9g,50mmol) in EtOH (1.5 L). After an additional 2h at the reflux temperature, the mixture was cooled and the solvent. The resulting residue was treated with CH₂Cl₂ (500 mL) and water (500mL). The organic phase was separated, and the aqueous layer extracted with CH₂Cl₂ three times. The combined organic layers were dried over MgSO₄, then the solvent was removed, and the resulting solid was chromatographed on silica gel using CH₂Cl₂ as eluent. Colourless single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a dichloromethane-n-hexane (1:30) solution over a period of 6 hours.

Structure description top

For the preparation of the title compound, see: Kay & Baek (1997); Scheytza et al. (1999); Xu et al. (2008). For further information on paracyclophane and its derivatives, see: Wang et al. (2006); Yamamoto et al. (1997).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level.

1²,1⁵-dibromo-2,7-dithia-1(1,4)-benzena-5(2,6)-pyridinaoctaphane top

Crystal data top

C₁₅H₁₃Br₂NS₂	F(000) = 848
M_r = 431.20	D_x = 1.878 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4039 reflections
a = 8.9275 (15) Å	θ = 2.5–27.8°
b = 18.879 (3) Å	µ = 5.58 mm⁻¹
c = 9.3213 (15) Å	T = 298 K
β = 103.878 (3)°	Block, colorless
V = 1525.2 (4) Å³	0.16 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3775 independent reflections
Radiation source: fine-focus sealed tube	3018 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.452, T_max = 0.573	k = −25→25
11428 measured reflections	l = −10→12

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0414P)² + 0.2049P] where P = (F_o² + 2F_c²)/3
3775 reflections	(Δ/σ)_max = 0.002
181 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₅H₁₃Br₂NS₂	V = 1525.2 (4) Å³
M_r = 431.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9275 (15) Å	µ = 5.58 mm⁻¹
b = 18.879 (3) Å	T = 298 K
c = 9.3213 (15) Å	0.16 × 0.12 × 0.10 mm
β = 103.878 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3775 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3018 reflections with I > 2σ(I)
T_min = 0.452, T_max = 0.573	R_int = 0.026
11428 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.03	Δρ_max = 0.56 e Å⁻³
3775 reflections	Δρ_min = −0.46 e Å⁻³
181 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
Br1	0.63099 (3)	0.048688 (14)	0.87832 (3)	0.04897 (10)
Br2	0.22924 (4)	0.139645 (16)	0.22281 (3)	0.05124 (10)
C1	0.3799 (3)	0.03373 (12)	0.6206 (3)	0.0338 (5)
C2	0.5079 (3)	0.07344 (12)	0.6886 (3)	0.0334 (5)
C3	0.5520 (3)	0.13348 (12)	0.6246 (3)	0.0331 (5)
H3	0.6384	0.1587	0.6742	0.040*
C4	0.4686 (3)	0.15680 (13)	0.4867 (3)	0.0324 (5)
C5	0.3444 (3)	0.11522 (13)	0.4148 (3)	0.0338 (5)
C6	0.3002 (3)	0.05574 (12)	0.4802 (3)	0.0372 (5)
H6	0.2154	0.0298	0.4295	0.045*
C7	0.5137 (3)	0.22521 (13)	0.4279 (3)	0.0383 (6)
H7A	0.5180	0.2181	0.3259	0.046*
H7B	0.6168	0.2376	0.4835	0.046*
C8	0.3410 (3)	0.28873 (14)	0.6143 (3)	0.0371 (5)
H8A	0.4332	0.2727	0.6849	0.045*
H8B	0.3134	0.3346	0.6471	0.045*
C9	0.2123 (3)	0.23745 (12)	0.6156 (2)	0.0301 (5)
C10	0.0700 (3)	0.24389 (14)	0.5179 (3)	0.0382 (5)
H10	0.0501	0.2810	0.4505	0.046*
C11	−0.0417 (3)	0.19455 (15)	0.5220 (3)	0.0414 (6)
H11	−0.1389	0.1982	0.4580	0.050*
C12	−0.0085 (3)	0.13961 (13)	0.6216 (3)	0.0387 (6)
H12	−0.0819	0.1050	0.6243	0.046*
C13	0.1362 (3)	0.13660 (11)	0.7180 (3)	0.0308 (5)
C14	0.1781 (3)	0.07834 (13)	0.8309 (3)	0.0384 (6)
H14A	0.1171	0.0840	0.9034	0.046*
H14B	0.2858	0.0835	0.8820	0.046*
C15	0.3230 (3)	−0.02833 (13)	0.6927 (3)	0.0426 (6)
H15A	0.4036	−0.0430	0.7770	0.051*
H15B	0.3036	−0.0674	0.6232	0.051*
N1	0.2443 (2)	0.18540 (10)	0.7172 (2)	0.0302 (4)
S1	0.14839 (8)	−0.01069 (3)	0.75438 (8)	0.04531 (17)
S2	0.38563 (7)	0.29931 (3)	0.43559 (7)	0.03722 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.05493 (19)	0.04386 (16)	0.03946 (16)	0.00297 (12)	−0.00566 (13)	0.01018 (11)
Br2	0.0613 (2)	0.05608 (19)	0.02904 (15)	0.00966 (13)	−0.00356 (12)	−0.00142 (11)
C1	0.0373 (13)	0.0296 (11)	0.0345 (13)	0.0066 (9)	0.0086 (10)	−0.0027 (10)
C2	0.0351 (13)	0.0354 (12)	0.0282 (12)	0.0097 (10)	0.0047 (10)	0.0013 (9)
C3	0.0287 (12)	0.0383 (12)	0.0322 (12)	0.0040 (9)	0.0072 (10)	0.0009 (10)
C4	0.0294 (12)	0.0381 (12)	0.0320 (12)	0.0091 (9)	0.0122 (10)	0.0014 (10)
C5	0.0348 (13)	0.0402 (12)	0.0257 (11)	0.0097 (10)	0.0059 (9)	−0.0032 (10)
C6	0.0368 (13)	0.0375 (12)	0.0351 (13)	0.0034 (10)	0.0045 (11)	−0.0088 (10)
C7	0.0337 (13)	0.0467 (14)	0.0379 (13)	0.0047 (10)	0.0150 (10)	0.0061 (11)
C8	0.0401 (14)	0.0384 (13)	0.0332 (13)	−0.0020 (10)	0.0095 (11)	−0.0027 (10)
C9	0.0348 (12)	0.0311 (11)	0.0268 (11)	0.0025 (9)	0.0123 (9)	−0.0041 (9)
C10	0.0388 (13)	0.0422 (13)	0.0330 (13)	0.0072 (11)	0.0075 (10)	0.0056 (10)
C11	0.0263 (12)	0.0571 (16)	0.0394 (14)	0.0082 (11)	0.0049 (10)	0.0043 (12)
C12	0.0312 (13)	0.0447 (14)	0.0404 (14)	−0.0040 (10)	0.0092 (11)	−0.0022 (11)
C13	0.0314 (12)	0.0345 (12)	0.0283 (12)	0.0030 (9)	0.0105 (9)	−0.0032 (9)
C14	0.0462 (15)	0.0374 (13)	0.0332 (13)	0.0031 (11)	0.0122 (11)	0.0017 (10)
C15	0.0517 (16)	0.0303 (12)	0.0441 (15)	0.0008 (11)	0.0082 (12)	−0.0017 (11)
N1	0.0309 (10)	0.0332 (10)	0.0277 (10)	0.0038 (7)	0.0093 (8)	−0.0038 (8)
S1	0.0464 (4)	0.0343 (3)	0.0559 (4)	−0.0053 (3)	0.0138 (3)	0.0052 (3)
S2	0.0394 (3)	0.0376 (3)	0.0363 (3)	0.0021 (2)	0.0123 (3)	0.0090 (3)

Geometric parameters (Å, º) top

Br1—C2	1.903 (2)	C8—H8B	0.9700
Br2—C5	1.895 (2)	C9—N1	1.347 (3)
C1—C2	1.386 (3)	C9—C10	1.379 (3)
C1—C6	1.395 (3)	C10—C11	1.371 (4)
C1—C15	1.498 (4)	C10—H10	0.9300
C2—C3	1.381 (3)	C11—C12	1.377 (4)
C3—C4	1.393 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.386 (3)
C4—C5	1.392 (3)	C12—H12	0.9300
C4—C7	1.496 (3)	C13—N1	1.335 (3)
C5—C6	1.380 (3)	C13—C14	1.506 (3)
C6—H6	0.9300	C14—S1	1.820 (3)
C7—S2	1.819 (3)	C14—H14A	0.9700
C7—H7A	0.9700	C14—H14B	0.9700
C7—H7B	0.9700	C15—S1	1.817 (3)
C8—C9	1.505 (3)	C15—H15A	0.9700
C8—S2	1.814 (2)	C15—H15B	0.9700
C8—H8A	0.9700

C2—C1—C6	116.5 (2)	N1—C9—C10	122.3 (2)
C2—C1—C15	123.3 (2)	N1—C9—C8	116.2 (2)
C6—C1—C15	120.2 (2)	C10—C9—C8	121.5 (2)
C3—C2—C1	122.4 (2)	C11—C10—C9	118.9 (2)
C3—C2—Br1	116.22 (18)	C11—C10—H10	120.6
C1—C2—Br1	121.40 (18)	C9—C10—H10	120.6
C2—C3—C4	120.9 (2)	C10—C11—C12	119.3 (2)
C2—C3—H3	119.6	C10—C11—H11	120.3
C4—C3—H3	119.6	C12—C11—H11	120.3
C5—C4—C3	117.0 (2)	C11—C12—C13	119.0 (2)
C5—C4—C7	124.3 (2)	C11—C12—H12	120.5
C3—C4—C7	118.6 (2)	C13—C12—H12	120.5
C6—C5—C4	121.7 (2)	N1—C13—C12	122.0 (2)
C6—C5—Br2	117.85 (18)	N1—C13—C14	116.7 (2)
C4—C5—Br2	120.44 (19)	C12—C13—C14	121.3 (2)
C5—C6—C1	121.4 (2)	C13—C14—S1	114.34 (18)
C5—C6—H6	119.3	C13—C14—H14A	108.7
C1—C6—H6	119.3	S1—C14—H14A	108.7
C4—C7—S2	115.00 (17)	C13—C14—H14B	108.7
C4—C7—H7A	108.5	S1—C14—H14B	108.7
S2—C7—H7A	108.5	H14A—C14—H14B	107.6
C4—C7—H7B	108.5	C1—C15—S1	114.02 (17)
S2—C7—H7B	108.5	C1—C15—H15A	108.7
H7A—C7—H7B	107.5	S1—C15—H15A	108.7
C9—C8—S2	114.50 (16)	C1—C15—H15B	108.7
C9—C8—H8A	108.6	S1—C15—H15B	108.7
S2—C8—H8A	108.6	H15A—C15—H15B	107.6
C9—C8—H8B	108.6	C13—N1—C9	118.4 (2)
S2—C8—H8B	108.6	C15—S1—C14	103.75 (12)
H8A—C8—H8B	107.6	C8—S2—C7	103.29 (12)

C6—C1—C2—C3	2.6 (3)	S2—C8—C9—C10	−53.5 (3)
C15—C1—C2—C3	−175.3 (2)	N1—C9—C10—C11	−1.6 (4)
C6—C1—C2—Br1	−178.55 (17)	C8—C9—C10—C11	178.4 (2)
C15—C1—C2—Br1	3.6 (3)	C9—C10—C11—C12	−0.8 (4)
C1—C2—C3—C4	−0.2 (4)	C10—C11—C12—C13	1.5 (4)
Br1—C2—C3—C4	−179.17 (17)	C11—C12—C13—N1	0.1 (4)
C2—C3—C4—C5	−2.8 (3)	C11—C12—C13—C14	179.1 (2)
C2—C3—C4—C7	175.2 (2)	N1—C13—C14—S1	−126.8 (2)
C3—C4—C5—C6	3.5 (3)	C12—C13—C14—S1	54.2 (3)
C7—C4—C5—C6	−174.3 (2)	C2—C1—C15—S1	105.8 (2)
C3—C4—C5—Br2	−177.02 (16)	C6—C1—C15—S1	−71.9 (3)
C7—C4—C5—Br2	5.1 (3)	C12—C13—N1—C9	−2.4 (3)
C4—C5—C6—C1	−1.2 (4)	C14—C13—N1—C9	178.6 (2)
Br2—C5—C6—C1	179.31 (18)	C10—C9—N1—C13	3.2 (3)
C2—C1—C6—C5	−1.8 (3)	C8—C9—N1—C13	−176.80 (19)
C15—C1—C6—C5	176.1 (2)	C1—C15—S1—C14	−40.3 (2)
C5—C4—C7—S2	72.8 (3)	C13—C14—S1—C15	83.7 (2)
C3—C4—C7—S2	−105.0 (2)	C9—C8—S2—C7	−83.4 (2)
S2—C8—C9—N1	126.56 (19)	C4—C7—S2—C8	40.9 (2)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃Br₂NS₂
M_r	431.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.9275 (15), 18.879 (3), 9.3213 (15)
β (°)	103.878 (3)
V (Å³)	1525.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.58
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.452, 0.573
No. of measured, independent and observed [I > 2σ(I)] reflections	11428, 3775, 3018
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.03
No. of reflections	3775
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.46

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank Professor Sheng-Hua Liu for technical assistance and Dr Jian-Long Xia for the data collection.

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