5,5′-(Disulfanedi­yl)bis­(1-methyl-1H-tetra­zole)

Cui, A.-Y.; Liu, J.-L.

doi:10.1107/S1600536811029862

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2184

doi:10.1107/S1600536811029862

Open

access

5,5′-(Disulfanediyl)bis(1-methyl-1H-tetrazole)

Ai-Yun Cui ^a,^b and Jing-Lin Liu ^a,^c ^*

^aFaculty of Chemistry, Northeast Normal University, 130024 Changchun, Jilin, People's Republic of China, ^bInstitute of Functional Nano and Soft Materials (FUNSOM), Soochow University, 215123 Suzhou, Jiangsu, People's Republic of China, and ^cCollege of Chemistry and Chemical Engineering, Inner Mongolia University for the Nationalities, 028042 Tongliao, Inner Mongolia, People's Republic of China
^*Correspondence e-mail: liujinglin@imun.edu.cn

(Received 7 July 2011; accepted 23 July 2011; online 30 July 2011)

In the title molecule, C₄H₆N₈S₂, two tetrazole rings linked by a disulfide bridge form a dihedral angle of 71.32 (7)° [C—S—S—C torsion angle = −80.51 (10)°]. In the crystal, strong intermolecular π–π interactions between the tetrazole rings [centroid–centroid distance = 3.285 (3) Å] link pairs of molecules into centrosymmetric dimers. Weak intermolecular C—H⋯N hydrogen bonds further link these dimers, related by translation in the [100] direction, into columns.

Related literature

For related structures, see: Kim et al. (2003 ); Brito et al. (2007 ); Tamilselvi & Mugesh (2010 ). For their use as ligands in transition-metal coordination chemistry, see: She et al. (2006 ); Carballo et al. (2009 ); Wang et al. (2010 ); Aromi et al. (2011 ).

Experimental

Crystal data

C₄H₆N₈S₂
M_r = 230.29
Monoclinic, P 2₁ /n
a = 6.3232 (3) Å
b = 8.1625 (3) Å
c = 18.3623 (7) Å
β = 98.906 (2)°
V = 936.31 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 296 K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.812, T_max = 0.899
8223 measured reflections
1606 independent reflections
1527 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.106
S = 1.09
1606 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4C⋯N6ⁱ	0.96	2.61	3.518 (4)	158
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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/S1600536811029862/cv5132sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029862/cv5132Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811029862/cv5132Isup3.cml

checkCIF report

Comment top

In recent years, the interesting coordination chemistry and increasingly biomedical properties of complexes derived from bis(1-methyl-1H-tetrazol) disulfide ligand have received much attention (Kim et al., 2003; She et al., 2006; Brito et al., 2007; Carballo et al., 2009; Tamilselvi & Mugesh, 2010; Wang et al., 2010). Herein we report the synthesis and crystal structure of the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in the related compounds (Kim et al., 2003; Brito et al., 2007; Tamilselvi & Mugesh, 2010) The dihedral angle between the two tetrazol rings is 71.32 (7) °. The S—S bond length is 2.0474 (8) Å. The C—S—S—C torsion angle of -80.51 (10) ° compares well with that of -79.71 (10) ° reported by Tamilselvi & Mugesh (2010). The C—S—S—C torsion angle in two bis-tetrazol disulfides reported by Kim et al. (2003) and Brito et al. (2007) are 81.54 (5) ° and 80.42 (6) °, respectively.

In the crystal structure, strong intermolecular π—π interaction between the tetrazole rings [centroid-centroid distance of 3.285 (3) Å] link two molecules into centrosymmetric dimer. Weak intermolecular C—H···N hydrogen bonds (Table 1) link further these dimers related by translation in [100] into columns.

Related literature top

For related structures, see: Kim et al. (2003); Brito et al. (2007); Tamilselvi & Mugesh (2010). For their use as ligands in transition-metal coordination chemistry, see: She et al. (2006); Carballo et al. (2009); Wang et al. (2010); Aromi et al. (2011).

Experimental top

A water solution (5 ml) of Fe(NO₃)₃ (0.25 mmol) was added slowly to the water solution (15 ml) of 1-methyl-5-mercaptotetrazole (0.10 mmol). The reaction mixture was stirred at room temperature for 3 h. The solvent was removed and the solid product recrystallized from ethanol. After six days, the colourless crystals suitable for X-ray diffraction were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (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. View of (I) showing the atomic labeling and 30% probability displacement ellipsoids.

5,5'-(Disulfanediyl)bis(1-methyl-1H-tetrazole) top

Crystal data top

C₄H₆N₈S₂	F(000) = 472
M_r = 230.29	D_x = 1.634 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9988 reflections
a = 6.3232 (3) Å	θ = 2.5–40.5°
b = 8.1625 (3) Å	µ = 0.54 mm⁻¹
c = 18.3623 (7) Å	T = 296 K
β = 98.906 (2)°	Block, colourless
V = 936.31 (7) Å³	0.40 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1606 independent reflections
Radiation source: fine-focus sealed tube	1527 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→5
T_min = 0.812, T_max = 0.899	k = −9→9
8223 measured reflections	l = −21→21

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0575P)² + 0.6856P] where P = (F_o² + 2F_c²)/3
1606 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₄H₆N₈S₂	V = 936.31 (7) Å³
M_r = 230.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.3232 (3) Å	µ = 0.54 mm⁻¹
b = 8.1625 (3) Å	T = 296 K
c = 18.3623 (7) Å	0.40 × 0.20 × 0.20 mm
β = 98.906 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1606 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1527 reflections with I > 2σ(I)
T_min = 0.812, T_max = 0.899	R_int = 0.019
8223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.09	Δρ_max = 0.38 e Å⁻³
1606 reflections	Δρ_min = −0.35 e Å⁻³
127 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	0.21952 (9)	0.05034 (7)	0.39949 (3)	0.0367 (2)
S2	0.13427 (9)	0.20613 (8)	0.47738 (3)	0.0427 (2)
N2	0.2328 (4)	0.3565 (3)	0.24114 (12)	0.0461 (5)
N1	0.1217 (3)	0.2818 (2)	0.28933 (11)	0.0393 (5)
C1	0.2630 (3)	0.1878 (2)	0.32986 (11)	0.0296 (4)
N4	0.4531 (3)	0.2035 (2)	0.30732 (10)	0.0348 (4)
N6	0.7056 (3)	0.3555 (3)	0.55018 (13)	0.0484 (5)
N5	0.5698 (3)	0.2755 (3)	0.49736 (12)	0.0448 (5)
C3	0.3824 (4)	0.2790 (3)	0.52098 (12)	0.0351 (5)
N8	0.4035 (3)	0.3574 (2)	0.58550 (10)	0.0386 (4)
N3	0.4312 (3)	0.3089 (3)	0.25086 (11)	0.0430 (5)
C2	0.6534 (4)	0.1195 (4)	0.33142 (15)	0.0503 (6)
H2B	0.6382	0.0491	0.3722	0.075*
H2C	0.7640	0.1985	0.3465	0.075*
H2A	0.6908	0.0551	0.2915	0.075*
N7	0.6092 (3)	0.4054 (3)	0.60292 (12)	0.0485 (5)
C4	0.2441 (5)	0.3978 (4)	0.63164 (16)	0.0627 (8)
H4C	0.1080	0.3535	0.6101	0.094*
H4A	0.2330	0.5146	0.6355	0.094*
H4B	0.2858	0.3518	0.6799	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0401 (4)	0.0366 (3)	0.0343 (3)	−0.0056 (2)	0.0089 (2)	0.0033 (2)
S2	0.0329 (3)	0.0600 (4)	0.0367 (3)	−0.0085 (2)	0.0095 (2)	−0.0078 (2)
N2	0.0515 (12)	0.0450 (11)	0.0406 (11)	−0.0020 (9)	0.0028 (9)	0.0106 (9)
N1	0.0344 (10)	0.0417 (10)	0.0408 (11)	0.0010 (8)	0.0024 (8)	0.0035 (8)
C1	0.0268 (10)	0.0327 (10)	0.0293 (10)	−0.0033 (8)	0.0041 (8)	−0.0015 (8)
N4	0.0300 (9)	0.0411 (10)	0.0337 (10)	−0.0034 (7)	0.0065 (8)	0.0021 (7)
N6	0.0352 (11)	0.0539 (12)	0.0547 (13)	−0.0054 (9)	0.0024 (10)	0.0047 (10)
N5	0.0364 (11)	0.0549 (12)	0.0439 (11)	−0.0038 (9)	0.0088 (9)	0.0025 (9)
C3	0.0346 (12)	0.0382 (12)	0.0326 (11)	−0.0034 (9)	0.0051 (9)	0.0065 (9)
N8	0.0379 (10)	0.0422 (10)	0.0348 (10)	−0.0049 (8)	0.0028 (8)	0.0005 (8)
N3	0.0453 (12)	0.0498 (11)	0.0348 (10)	−0.0081 (9)	0.0090 (9)	0.0071 (8)
C2	0.0261 (11)	0.0749 (18)	0.0508 (14)	0.0049 (11)	0.0086 (10)	0.0060 (13)
N7	0.0397 (11)	0.0527 (12)	0.0503 (12)	−0.0071 (9)	−0.0023 (10)	0.0009 (10)
C4	0.0513 (16)	0.092 (2)	0.0472 (15)	−0.0110 (16)	0.0141 (13)	−0.0212 (15)

Geometric parameters (Å, º) top

S1—C1	1.754 (2)	N5—C3	1.324 (3)
S1—S2	2.0474 (8)	C3—N8	1.335 (3)
S2—C3	1.752 (2)	N8—N7	1.349 (3)
N2—N3	1.299 (3)	N8—C4	1.452 (3)
N2—N1	1.357 (3)	C2—H2B	0.9600
N1—C1	1.317 (3)	C2—H2C	0.9600
C1—N4	1.337 (3)	C2—H2A	0.9600
N4—N3	1.338 (3)	C4—H4C	0.9600
N4—C2	1.448 (3)	C4—H4A	0.9600
N6—N7	1.287 (3)	C4—H4B	0.9600
N6—N5	1.359 (3)

C1—S1—S2	101.53 (7)	C3—N8—C4	130.1 (2)
C3—S2—S1	102.49 (8)	N7—N8—C4	121.8 (2)
N3—N2—N1	111.26 (18)	N2—N3—N4	106.28 (18)
C1—N1—N2	104.84 (19)	N4—C2—H2B	109.5
N1—C1—N4	109.43 (19)	N4—C2—H2C	109.5
N1—C1—S1	127.98 (17)	H2B—C2—H2C	109.5
N4—C1—S1	122.48 (16)	N4—C2—H2A	109.5
C1—N4—N3	108.17 (18)	H2B—C2—H2A	109.5
C1—N4—C2	130.23 (19)	H2C—C2—H2A	109.5
N3—N4—C2	121.46 (19)	N6—N7—N8	106.3 (2)
N7—N6—N5	111.64 (19)	N8—C4—H4C	109.5
C3—N5—N6	104.7 (2)	N8—C4—H4A	109.5
N5—C3—N8	109.2 (2)	H4C—C4—H4A	109.5
N5—C3—S2	128.82 (19)	N8—C4—H4B	109.5
N8—C3—S2	121.87 (17)	H4C—C4—H4B	109.5
C3—N8—N7	108.06 (19)	H4A—C4—H4B	109.5

C1—S1—S2—C3	−80.51 (10)	S1—S2—C3—N5	17.9 (2)
N3—N2—N1—C1	0.9 (3)	S1—S2—C3—N8	−165.44 (17)
N2—N1—C1—N4	−0.2 (2)	N5—C3—N8—N7	0.3 (3)
N2—N1—C1—S1	−176.46 (16)	S2—C3—N8—N7	−176.89 (16)
S2—S1—C1—N1	−65.6 (2)	N5—C3—N8—C4	177.5 (3)
S2—S1—C1—N4	118.62 (17)	S2—C3—N8—C4	0.3 (4)
N1—C1—N4—N3	−0.5 (2)	N1—N2—N3—N4	−1.2 (3)
S1—C1—N4—N3	175.98 (15)	C1—N4—N3—N2	1.0 (2)
N1—C1—N4—C2	−176.1 (2)	C2—N4—N3—N2	177.1 (2)
S1—C1—N4—C2	0.4 (3)	N5—N6—N7—N8	0.3 (3)
N7—N6—N5—C3	−0.1 (3)	C3—N8—N7—N6	−0.4 (3)
N6—N5—C3—N8	−0.2 (3)	C4—N8—N7—N6	−177.8 (2)
N6—N5—C3—S2	176.80 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···N6ⁱ	0.96	2.61	3.518 (4)	158

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₄H₆N₈S₂
M_r	230.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.3232 (3), 8.1625 (3), 18.3623 (7)
β (°)	98.906 (2)
V (Å³)	936.31 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.812, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	8223, 1606, 1527
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.106, 1.09
No. of reflections	1606
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35

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—H4C···N6ⁱ	0.96	2.61	3.518 (4)	157.5

Symmetry code: (i) x−1, y, z.

Acknowledgements

This work was supported by the China Postdoctoral Science Foundation (grant No. 20080431049) and the Scientific Research Foundation for Doctors, Inner Mongolia University for the Nationalities (grant No. BS214).

References

Aromi, G., Barrios, L. A., Roubeau, O. & Gamez, P. (2011). Coord. Chem. Rev. 255, 485–546. CAS Google Scholar
Brito, I., Cárdenas, A., Mundaca, A., Villalobos, H. & López-Rodríguez, M. (2007). Acta Cryst. E63, o2581–o2583. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carballo, R., Covelo, B., Fernandez-Hermida, N., Lago, A. B. & Vazquez-Lopez, M. (2009). CrystEngComm, 11, 817–826. Web of Science CSD CrossRef CAS Google Scholar
Kim, Y. J., Han, J. T., Kang, S., Han, W. S. & Lee, S. J. (2003). Dalton Trans. pp. 3357–3364. Web of Science CSD CrossRef Google Scholar
She, J.-B., Zhang, G.-F., Dou, Y.-L., Fan, X.-Z. & Li, J.-Z. (2006). Acta Cryst. E62, o402–o404. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tamilselvi, A. & Mugesh, G. (2010). Bioorg. Med. Chem. Lett. 20, 3692–3697. Web of Science CSD CrossRef CAS PubMed Google Scholar
Wang, X. L., Hu, H. L., Tian, A. X., Lin, H. Y. & Li, J. (2010). Inorg. Chem. 49, 10299–10306. Web of Science CSD CrossRef CAS PubMed Google Scholar