5,5′-[(1,4-Phenyl­enedimethyl­ene)bis­(sulfanedi­yl)]bis­(1-methyl-1H-1,2,3,4-tetra­zole)

He, D.-F.; Deng, J.-J.; Zhou, F.-J.; Liu, H.-S.; Wang, L.-M.

doi:10.1107/S1600536811043182

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3063

doi:10.1107/S1600536811043182

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5,5′-[(1,4-Phenylenedimethylene)bis(sulfanediyl)]bis(1-methyl-1H-1,2,3,4-tetrazole)

Dan-Feng He,^a ^* Jin-Jun Deng,^a Fu-Jiang Zhou,^b Hong-Sheng Liu ^a and Li-Min Wang ^a

^aDepartment of Chemistry and Chemical Engineering, Daqing Normal University, 163712 Daqing, Heilongjiang, People's Republic of China, and ^bDaQing Petrochemical Corporation, 163712 Daqing, Heilongjiang, People's Republic of China
^*Correspondence e-mail: hdf00@yeah.net

(Received 10 September 2011; accepted 18 October 2011; online 29 October 2011)

The title molecule, C₁₂H₁₄N₈S₂, has point symmetry $[\overline{1}]$ since it is situated on a crystallographic centre of symmetry. The 1-methyl/5-thio groups are in an antiperiplanar conformation. The dihedral angle between the benzene and tetrazole rings is 84.33 (2)°. In the crystal, C—H⋯N hydrogen bonds link molecules into ladder-like chains running along the b axis. There are also C—H⋯π interactions present in the crystal structure.

Related literature

For the pharmaceutical properties of ligands derived from tetrazole, see: Armour et al. (1996 ); Segarra et al. (1998 ); Bronisz (2002 ); Semenov (2002 ); Upadhayaya et al. (2004 ); Wang et al. (2004 ); She et al. (2006 ); Wei et al. (2011 ). For the synthesis of the title compound, see: Wang et al. (2005 ). For graph-set motifs, see: Etter et al. (1990 ).

Experimental

Crystal data

C₁₂H₁₄N₈S₂
M_r = 334.43
Monoclinic, C 2/c
a = 18.464 (4) Å
b = 7.6392 (18) Å
c = 13.625 (3) Å
β = 126.999 (4)°
V = 1534.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 296 K
0.25 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.916, T_max = 0.965
6541 measured reflections
1758 independent reflections
1412 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.116
S = 1.07
1758 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg_benzene is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯N2ⁱ	0.97	2.58	3.429 (3)	145
C6—H6A⋯Cg_benzeneⁱⁱ	0.96	2.82	3.545 (4)	133
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043182/fb2238sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043182/fb2238Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043182/fb2238Isup3.cml

checkCIF report

Comment top

In recent years, tetrazole compounds and their derivatives have received much attention because of their diverse pharmaceutical properties (Armour et al., 1996; Segarra et al., 1998; Bronisz, 2002; Semenov, 2002; Upadhayaya et al., 2004; Wang et al., 2004; She et al., 2006; Wei et al., 2011).

In order to search for a new tetrazole compound with higher bioactivity, the title compound has been synthesized and its crystal structure determined.

The title molecule, C₁₂H₁₄N₂S₈, has the point symmetry 1 since it is situated on the crystallographic centre of symmetry. 1-methyl-5-thio- moieties are in the antiperiplanar conformation. The dihedral angle between the benzene and tetrazole ring is 84.39 (2) °. The molecules are situated on the crystallographic centres of symmetry and therefore their point symmetry is 1. In the crystal structure, the molecules are linked by C—H···N hydrogen bonds (Tab. 1; Fig. 2) forming a ladder-like chain composed of the graph set motifs R²₂(22) (Etter et al. (1990). The chains are directed along the b axis.

Moreover, there are also C—H···ring-πi-electron interactions in the structure: (C6—H6A···Cg_benzeneⁱ: 0.96, 2.82, 3.545 (4) Å, 133 °; the symmetry code i: -x, y, 1/2 - z and C6ⁱⁱ—H6Aⁱⁱ···Cg_benzeneⁱⁱ: 0.96, 2.82, 3.545 (4) Å, 133 °; the symmetry code ii: x, -y, 1/2 + z).

Related literature top

For the pharmaceutical properties of ligands derived from tetrazole, see: Armour et al. (1996); Segarra et al. (1998); Bronisz (2002); Semenov (2002); Upadhayaya et al. (2004); Wang et al. (2004); She et al. (2006); Wei et al. (2011). For the synthesis of the title compound, see: Wang et al. (2005). For graph-set motifs, see Etter et al. (1990).

Experimental top

The title compound was synthesized according to the method reported in the literature (Wang et al., 2005). Colourless block-shaped crystals with approx. size 0.2 × 0.1 × 0.1 mm were obtained by slow evaporation from ethanol solution of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The title molecule with the displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The infinite ladder-like chains formed via C-H···N hydrogen bonds indicated by the dashed lines. The chains contain the graph set motifs R²₂(22) (Etter et al., 1990).

1-methyl-5-({4-[(1-methyl-1H-1,2,3,4-tetrazol-5- yl)sulfanylmethyl]phenyl}methylsulfanyl)-1H-1,2,3,4-tetrazole top

Crystal data top

C₁₂H₁₄N₈S₂	F(000) = 696
M_r = 334.43	D_x = 1.447 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2201 reflections
a = 18.464 (4) Å	θ = 3.0–26.9°
b = 7.6392 (18) Å	µ = 0.36 mm⁻¹
c = 13.625 (3) Å	T = 296 K
β = 126.999 (4)°	Block, colorless
V = 1534.8 (6) Å³	0.25 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	1758 independent reflections
Radiation source: fine-focus sealed tube	1412 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.6°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −19→24
T_min = 0.916, T_max = 0.965	k = −9→9
6541 measured reflections	l = −17→15

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0582P)² + 0.9815P] where P = (F_o² + 2F_c²)/3
1758 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³
27 constraints

Crystal data top

C₁₂H₁₄N₈S₂	V = 1534.8 (6) Å³
M_r = 334.43	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.464 (4) Å	µ = 0.36 mm⁻¹
b = 7.6392 (18) Å	T = 296 K
c = 13.625 (3) Å	0.25 × 0.10 × 0.10 mm
β = 126.999 (4)°

Data collection top

Bruker SMART APEXII diffractometer	1758 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1412 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.965	R_int = 0.024
6541 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	Δρ_max = 0.42 e Å⁻³
1758 reflections	Δρ_min = −0.26 e Å⁻³
101 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	0.15096 (4)	0.07607 (7)	0.36393 (5)	0.04497 (19)
N1	0.16911 (15)	0.3872 (3)	0.27877 (19)	0.0558 (5)
N2	0.15595 (18)	0.5580 (3)	0.2902 (2)	0.0697 (6)
N3	0.12550 (16)	0.5769 (3)	0.3536 (2)	0.0652 (6)
N4	0.11760 (12)	0.4145 (2)	0.38467 (16)	0.0452 (4)
C1	−0.07348 (14)	−0.1014 (3)	−0.03169 (19)	0.0413 (5)
H1	−0.1225	−0.1697	−0.0523	0.050*
C2	0.00541 (14)	−0.1013 (3)	0.08832 (19)	0.0413 (4)
H2	0.0087	−0.1696	0.1474	0.050*
C3	0.07963 (13)	0.0003 (3)	0.12106 (17)	0.0384 (4)
C4	0.16597 (14)	−0.0016 (3)	0.25088 (19)	0.0444 (5)
H4A	0.2107	0.0712	0.2549	0.053*
H4B	0.1894	−0.1202	0.2718	0.053*
C5	0.14563 (12)	0.2996 (3)	0.33927 (16)	0.0390 (4)
C6	0.08800 (19)	0.3838 (4)	0.4606 (3)	0.0640 (7)
H6A	0.0387	0.3017	0.4203	0.096*
H6B	0.0683	0.4921	0.4731	0.096*
H6C	0.1375	0.3371	0.5385	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0542 (3)	0.0439 (3)	0.0376 (3)	−0.0049 (2)	0.0280 (2)	−0.0001 (2)
N1	0.0711 (13)	0.0491 (11)	0.0643 (12)	−0.0057 (9)	0.0497 (11)	0.0038 (9)
N2	0.0895 (17)	0.0488 (12)	0.0893 (17)	−0.0011 (11)	0.0636 (15)	0.0105 (11)
N3	0.0751 (14)	0.0451 (12)	0.0819 (16)	0.0064 (10)	0.0507 (14)	0.0054 (10)
N4	0.0409 (9)	0.0459 (10)	0.0497 (10)	0.0017 (7)	0.0278 (8)	0.0002 (8)
C1	0.0418 (10)	0.0438 (11)	0.0449 (11)	−0.0055 (8)	0.0296 (9)	−0.0073 (8)
C2	0.0474 (11)	0.0421 (11)	0.0411 (10)	−0.0026 (9)	0.0303 (9)	−0.0021 (8)
C3	0.0387 (10)	0.0404 (10)	0.0391 (10)	−0.0002 (8)	0.0250 (8)	−0.0078 (8)
C4	0.0408 (10)	0.0467 (12)	0.0445 (11)	0.0022 (9)	0.0250 (9)	−0.0040 (9)
C5	0.0336 (9)	0.0449 (11)	0.0335 (9)	−0.0040 (8)	0.0176 (8)	−0.0014 (8)
C6	0.0681 (16)	0.0732 (17)	0.0717 (17)	−0.0009 (13)	0.0532 (15)	−0.0078 (13)

Geometric parameters (Å, º) top

S1—C5	1.732 (2)	C1—H1	0.9300
S1—C4	1.821 (2)	C2—C3	1.394 (3)
N1—C5	1.321 (3)	C2—H2	0.9300
N1—N2	1.353 (3)	C3—C1ⁱ	1.388 (3)
N2—N3	1.291 (3)	C3—C4	1.509 (3)
N3—N4	1.347 (3)	C4—H4A	0.9700
N4—C5	1.344 (3)	C4—H4B	0.9700
N4—C6	1.450 (3)	C6—H6A	0.9600
C1—C3ⁱ	1.388 (3)	C6—H6B	0.9600
C1—C2	1.389 (3)	C6—H6C	0.9600

C5—S1—C4	100.20 (10)	C3—C4—S1	113.41 (14)
C5—N1—N2	105.50 (19)	C3—C4—H4A	108.9
N3—N2—N1	111.44 (19)	S1—C4—H4A	108.9
N2—N3—N4	106.27 (19)	C3—C4—H4B	108.9
C5—N4—N3	108.20 (18)	S1—C4—H4B	108.9
C5—N4—C6	129.58 (19)	H4A—C4—H4B	107.7
N3—N4—C6	122.13 (19)	N1—C5—N4	108.57 (19)
C3ⁱ—C1—C2	120.44 (18)	N1—C5—S1	128.22 (17)
C3ⁱ—C1—H1	119.8	N4—C5—S1	123.19 (15)
C2—C1—H1	119.8	N4—C6—H6A	109.5
C1—C2—C3	120.64 (18)	N4—C6—H6B	109.5
C1—C2—H2	119.7	H6A—C6—H6B	109.5
C3—C2—H2	119.7	N4—C6—H6C	109.5
C1ⁱ—C3—C2	118.92 (18)	H6A—C6—H6C	109.5
C1ⁱ—C3—C4	120.31 (18)	H6B—C6—H6C	109.5
C2—C3—C4	120.77 (18)

C5—N1—N2—N3	−0.3 (3)	C5—S1—C4—C3	−76.96 (17)
N1—N2—N3—N4	−0.4 (3)	N2—N1—C5—N4	0.9 (2)
N2—N3—N4—C5	0.9 (3)	N2—N1—C5—S1	−177.38 (17)
N2—N3—N4—C6	177.8 (2)	N3—N4—C5—N1	−1.2 (2)
C3ⁱ—C1—C2—C3	0.0 (3)	C6—N4—C5—N1	−177.7 (2)
C1—C2—C3—C1ⁱ	0.0 (3)	N3—N4—C5—S1	177.23 (15)
C1—C2—C3—C4	−178.97 (18)	C6—N4—C5—S1	0.6 (3)
C1ⁱ—C3—C4—S1	119.20 (18)	C4—S1—C5—N1	−15.1 (2)
C2—C3—C4—S1	−61.8 (2)	C4—S1—C5—N4	166.87 (16)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···N2ⁱⁱ	0.97	2.58	3.429 (3)	145
C6—H6A···Cg_benzeneⁱⁱⁱ	0.96	2.82	3.545 (4)	133

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₈S₂
M_r	334.43
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	18.464 (4), 7.6392 (18), 13.625 (3)
β (°)	126.999 (4)
V (Å³)	1534.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.25 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.916, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	6541, 1758, 1412
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.116, 1.07
No. of reflections	1758
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.26

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···N2ⁱ	0.97	2.58	3.429 (3)	145
C6—H6A···Cg_benzeneⁱⁱ	0.96	2.82	3.545 (4)	133

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21171030).

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3063

doi:10.1107/S1600536811043182

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5,5′-[(1,4-Phenyl­enedi­methyl­ene)bis­­(sulfanedi­yl)]bis­­(1-methyl-1H-1,2,3,4-tetra­zole)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5,5′-[(1,4-Phenylenedimethylene)bis(sulfanediyl)]bis(1-methyl-1H-1,2,3,4-tetrazole)