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

Abstract

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,

• a = 6.3232 (3) Å

• b = 8.1625 (3) Å

• c = 18.3623 (7) Å

• β = 98.906 (2)°

• V = 936.31 (7) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811029862/cv5132Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed in idealized positions and refined using a riding model (C—H = 0.96 Å) with U_iso(H) = 1.5 U_eq(C).

Figures

Fig. 1.

View of (I) showing the atomic labeling and 30% probability displacement ellipsoids.

Crystal data

C4H6N8S2	F(000) = 472
Mr = 230.29	Dx = 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

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

Refinement

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(Fo2) + (0.0575P)2 + 0.6856P] where P = (Fo2 + 2Fc2)/3
1606 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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	0.21952 (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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) x−1, y, z.