2,2′-[2,3,5,6-Tetra­methyl-p-phenyl­ene­bis(methyl­enethio)]bis­(pyridine N-oxide)

Ravindran Durai Nayagam, B.; Jebas, S.R.; Grace, S.; Schollmeyer, D.

doi:10.1107/S1600536807068766

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o409

doi:10.1107/S1600536807068766

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2,2′-[2,3,5,6-Tetramethyl-p-phenylenebis(methylenethio)]bis(pyridine N-oxide)

B. Ravindran Durai Nayagam,^a ^* Samuel Robinson Jebas,^b Selvarathi Grace ^a and Dieter Schollmeyer ^c

^aDepartment of Chemistry, Popes College, Sawyerpuram, Tamilnadu, India, ^bDepartment of Physics, Karunya University, Coimbatore 641114, India, and ^cInstitut für Organische Chemie, Universität Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: b_ravidurai@yahoo.com

(Received 15 December 2007; accepted 29 December 2007; online 9 January 2008)

Molecules of the title compound, C₂₂H₂₄N₂O₂S₂, lie across centres of inversion. The two thiopyridine N-oxide groups adopt a stepped trans configuration with respect to the benzene ring, by virtue of the symmetry. The oxopyridinium ring forms a dihedral angle of 79.9 (2)° with the benzene ring. The crystal structure is stabilized by a strong π–π interaction between the pyridinium rings of adjacent molecules [ring centroid–centroid distance = 3.464 (3) Å].

Related literature

For bond-length data, see: Allen et al. (1987 ). For biological activities of N-oxide derivatives, see: Bovin et al. (1992 ); Katsuyuki et al. (1991 ); Leonard et al. (1955 ); Lobana & Bhatia (1989 ); Symons & West (1985 ). For a related structure, see: Hartung et al. (1996 ).

Experimental

Crystal data

C₂₂H₂₄N₂O₂S₂
M_r = 412.55
Monoclinic, P 2₁ /c
a = 11.8431 (13) Å
b = 9.0108 (9) Å
c = 9.7551 (10) Å
β = 112.611 (9)°
V = 961.01 (17) Å³
Z = 2
Cu Kα radiation
μ = 2.68 mm⁻¹
T = 193 (2) K
0.10 × 0.10 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.80, T_max = 0.87
1929 measured reflections
1813 independent reflections
1200 reflections with I > 2σ(I)
R_int = 0.077
3 standard reflections frequency: 60 min intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.170
S = 0.99
1813 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068766/ci2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068766/ci2548Isup2.hkl

checkCIF report

Comment top

N-Oxides and their derivatives show a broad spectrum of biological activity, such as antifungal, antibacterial, antimicrobial and antibiotic activities (Lobana & Bhatia, 1989; Symons et al., 1985). These compounds are also found to be involved in DNA strand scission under physiological conditions (Katsuyuki et al., 1991; Bovin et al., 1992). Pyridine N-oxides bearing a sulfur group in position 2 display significant antimicrobial activity (Leonard et al., 1955).

The asymmetric unit of the title compound consists of one half of a centrosymmetric molecule. The two thiopyridine-N-oxide groups adopt a stepped trans conformation with respect to the benzene ring, by virtue of the symmetry. The oxopyridinium ring forms a dihedral angle of 79.9 (2)° with the benzene ring. The N—O bond length is in good agreement with the mean value of 1.304 (15)Å reported in the literature for pyridine N-oxides (Allen et al., 1987). As observed in a similar structure (Hartung et al., 1996), the S atom is bent significantly towards the N-oxide O atom [N9—C8—S7 = 111.4 (3)°].

The crystal packing is stabilized by a strong π-π interaction between the pyridinium rings of adjacent molecules at (x, y, z) and (-x, 2 - y, -z), with a ring centroid to centroid distance of 3.464 (3) Å.

Related literature top

For bond-length data, see: Allen et al. (1987). For biological activities of N-oxides derivatives, see: Bovin et al. (1992); Katsuyuki et al. (1991); Leonard et al. (1955); Lobana & Bhatia (1989); Symons & West (1985). For a related structure, see: Hartung et al. (1996).

Experimental top

A mixture of 1,4-bis(bromomethyl)durene (0.320, 1 mmol) and 1-hydroxypyridine-2-thione sodium salt (0.298,2 mmol) in water (30 ml) and methanol (30 ml) was heated at 333 K with stirring for 30 min. The compound formed was filtered off, and dried (0.34 g, 82%). The compound was recrystallized from chloroform-methanol (1:2 v/v).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. Atoms labelled with the suffix a are generated by the symmetry operations (1 - x, 1 - y, 1 - z).

2,2'-[2,3,5,6-Tetramethyl-p-phenylenebis(methylenethio)]bis(pyridine N-oxide) top

Crystal data top

C₂₂H₂₄N₂O₂S₂	F(000) = 436
M_r = 412.55	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.8431 (13) Å	θ = 15–29.3°
b = 9.0108 (9) Å	µ = 2.68 mm⁻¹
c = 9.7551 (10) Å	T = 193 K
β = 112.611 (9)°	Block, colourless
V = 961.01 (17) Å³	0.10 × 0.10 × 0.05 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.077
ω/2θ scans	θ_max = 70°, θ_min = 4.0°
Absorption correction: ψ scan (North et al., 1968)	h = −14→13
T_min = 0.80, T_max = 0.87	k = 0→10
1929 measured reflections	l = 0→11
1813 independent reflections	3 standard reflections every 60 min
1200 reflections with I > 2σ(I)	intensity decay: 3%

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.057	w = 1/[σ²(F_o²) + (0.1008P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.170	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.42 e Å⁻³
1813 reflections	Δρ_min = −0.41 e Å⁻³
129 parameters

Crystal data top

C₂₂H₂₄N₂O₂S₂	V = 961.01 (17) Å³
M_r = 412.55	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 11.8431 (13) Å	µ = 2.68 mm⁻¹
b = 9.0108 (9) Å	T = 193 K
c = 9.7551 (10) Å	0.10 × 0.10 × 0.05 mm
β = 112.611 (9)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1200 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.077
T_min = 0.80, T_max = 0.87	3 standard reflections every 60 min
1929 measured reflections	intensity decay: 3%
1813 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 0.99	Δρ_max = 0.42 e Å⁻³
1813 reflections	Δρ_min = −0.41 e Å⁻³
129 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.

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

	x	y	z	U_iso*/U_eq
C1	0.4444 (3)	0.6186 (4)	0.4063 (4)	0.0220 (8)
C2	0.5351 (3)	0.6459 (4)	0.5463 (4)	0.0234 (8)
C3	0.4077 (3)	0.4715 (4)	0.3606 (4)	0.0243 (8)
C4	0.5706 (4)	0.8042 (4)	0.5965 (4)	0.0305 (9)
H4A	0.5049	0.8714	0.5374	0.046*
H4B	0.646	0.8299	0.583	0.046*
H4C	0.5838	0.8136	0.7017	0.046*
C5	0.3044 (4)	0.4452 (4)	0.2124 (4)	0.0347 (10)
H5A	0.2428	0.5233	0.1942	0.052*
H5B	0.267	0.3484	0.2132	0.052*
H5C	0.3365	0.447	0.1336	0.052*
C6	0.3835 (3)	0.7458 (4)	0.3017 (4)	0.0258 (8)
H6A	0.3528	0.7114	0.1973	0.031*
H6B	0.4429	0.827	0.3138	0.031*
S7	0.25697 (9)	0.81142 (11)	0.34802 (10)	0.0290 (3)
C8	0.1962 (3)	0.9526 (4)	0.2167 (4)	0.0254 (8)
N9	0.1042 (3)	1.0262 (4)	0.2392 (4)	0.0293 (7)
C10	0.0488 (4)	1.1435 (4)	0.1524 (5)	0.0340 (10)
H10	−0.0123	1.1969	0.1725	0.041*
C11	0.0792 (4)	1.1863 (4)	0.0363 (5)	0.0347 (9)
H11	0.0394	1.2683	−0.0242	0.042*
C12	0.1688 (4)	1.1083 (5)	0.0083 (5)	0.0358 (10)
H12	0.1889	1.1346	−0.0739	0.043*
C13	0.2287 (4)	0.9925 (4)	0.0998 (4)	0.0287 (9)
H13	0.2918	0.9405	0.0826	0.034*
O14	0.0730 (3)	0.9825 (4)	0.3471 (3)	0.0443 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.032 (2)	0.0160 (17)	0.0218 (18)	0.0012 (15)	0.0144 (16)	0.0009 (14)
C2	0.0280 (19)	0.0172 (17)	0.0262 (19)	−0.0026 (14)	0.0117 (15)	−0.0053 (15)
C3	0.0294 (19)	0.0227 (19)	0.0217 (17)	−0.0043 (15)	0.0106 (15)	−0.0028 (15)
C4	0.038 (2)	0.0189 (19)	0.033 (2)	−0.0065 (17)	0.0124 (18)	−0.0023 (17)
C5	0.044 (2)	0.025 (2)	0.031 (2)	−0.0021 (19)	0.0101 (19)	−0.0028 (18)
C6	0.0303 (19)	0.0221 (17)	0.026 (2)	0.0011 (16)	0.0116 (16)	−0.0001 (16)
S7	0.0373 (5)	0.0247 (5)	0.0282 (5)	0.0039 (4)	0.0160 (4)	0.0041 (4)
C8	0.028 (2)	0.0183 (18)	0.0265 (19)	−0.0018 (15)	0.0065 (16)	−0.0063 (15)
N9	0.0308 (17)	0.0260 (17)	0.0300 (17)	0.0000 (14)	0.0102 (14)	−0.0034 (14)
C10	0.030 (2)	0.025 (2)	0.038 (2)	0.0035 (16)	0.0031 (18)	−0.0069 (18)
C11	0.035 (2)	0.0224 (19)	0.037 (2)	−0.0048 (18)	0.0027 (17)	−0.0011 (19)
C12	0.039 (2)	0.031 (2)	0.034 (2)	−0.0059 (18)	0.0102 (18)	0.0004 (18)
C13	0.035 (2)	0.0233 (19)	0.0249 (19)	−0.0011 (16)	0.0086 (17)	0.0008 (16)
O14	0.055 (2)	0.0477 (19)	0.0421 (18)	0.0125 (16)	0.0316 (16)	0.0064 (15)

Geometric parameters (Å, º) top

C1—C2	1.398 (5)	C11—C12	1.384 (6)
C1—C3	1.412 (5)	C12—C13	1.379 (6)
C1—C6	1.520 (5)	C4—H4A	0.98
C2—C3ⁱ	1.389 (5)	C4—H4B	0.98
C2—C4	1.514 (5)	C4—H4C	0.98
C3—C2ⁱ	1.389 (5)	C5—H5A	0.98
C3—C5	1.511 (5)	C5—H5B	0.98
C6—S7	1.822 (4)	C5—H5C	0.98
S7—C8	1.752 (4)	C6—H6A	0.99
C8—N9	1.364 (5)	C6—H6B	0.99
C8—C13	1.384 (5)	C10—H10	0.95
N9—O14	1.303 (4)	C11—H11	0.95
N9—C10	1.355 (5)	C12—H12	0.95
C10—C11	1.369 (6)	C13—H13	0.95

C2—C1—C3	120.1 (3)	C2—C4—H4C	109
C2—C1—C6	120.8 (3)	H4A—C4—H4B	109
C3—C1—C6	119.2 (3)	H4A—C4—H4C	109
C3ⁱ—C2—C1	120.2 (3)	H4B—C4—H4C	109
C3ⁱ—C2—C4	120.1 (3)	C3—C5—H5A	109
C1—C2—C4	119.7 (3)	C3—C5—H5B	110
C2ⁱ—C3—C1	119.7 (3)	C3—C5—H5C	109
C2ⁱ—C3—C5	121.2 (3)	H5A—C5—H5B	109
C1—C3—C5	119.1 (3)	H5A—C5—H5C	109
C1—C6—S7	107.5 (2)	H5B—C5—H5C	110
C8—S7—C6	101.51 (18)	S7—C6—H6A	110
N9—C8—C13	119.9 (4)	S7—C6—H6B	110
N9—C8—S7	111.4 (3)	C1—C6—H6A	110
C13—C8—S7	128.7 (3)	C1—C6—H6B	110
O14—N9—C10	121.4 (4)	H6A—C6—H6B	108
O14—N9—C8	118.4 (3)	N9—C10—H10	119
C10—N9—C8	120.2 (4)	C11—C10—H10	119
N9—C10—C11	121.2 (4)	C10—C11—H11	120
C10—C11—C12	119.1 (4)	C12—C11—H11	120
C13—C12—C11	119.9 (4)	C11—C12—H12	120
C12—C13—C8	119.6 (4)	C13—C12—H12	120
C2—C4—H4A	109	C8—C13—H13	120
C2—C4—H4B	109	C12—C13—H13	120

C3—C1—C2—C3ⁱ	2.0 (6)	C6—S7—C8—C13	5.8 (4)
C6—C1—C2—C3ⁱ	−178.3 (3)	C13—C8—N9—O14	177.6 (3)
C3—C1—C2—C4	−177.7 (3)	S7—C8—N9—O14	−1.6 (4)
C6—C1—C2—C4	1.9 (5)	C13—C8—N9—C10	−3.5 (5)
C2—C1—C3—C2ⁱ	−2.0 (6)	S7—C8—N9—C10	177.3 (3)
C6—C1—C3—C2ⁱ	178.3 (3)	O14—N9—C10—C11	−177.9 (4)
C2—C1—C3—C5	176.5 (3)	C8—N9—C10—C11	3.2 (6)
C6—C1—C3—C5	−3.1 (5)	N9—C10—C11—C12	−0.4 (6)
C2—C1—C6—S7	−86.0 (4)	C10—C11—C12—C13	−2.1 (6)
C3—C1—C6—S7	93.6 (4)	C11—C12—C13—C8	1.8 (6)
C1—C6—S7—C8	−178.8 (2)	N9—C8—C13—C12	1.0 (6)
C6—S7—C8—N9	−175.2 (3)	S7—C8—C13—C12	−180.0 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₄N₂O₂S₂
M_r	412.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	193
a, b, c (Å)	11.8431 (13), 9.0108 (9), 9.7551 (10)
β (°)	112.611 (9)
V (Å³)	961.01 (17)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.68
Crystal size (mm)	0.10 × 0.10 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.80, 0.87
No. of measured, independent and observed [I > 2σ(I)] reflections	1929, 1813, 1200
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.170, 0.99
No. of reflections	1813
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.41

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

References

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