A monoclinic polymorph of 1,2-bis­[(1-methyl-1H-tetra­zol-5-yl)sulfan­yl]ethane (BMTTE)

Argibay-Otero, S.; Gómez-Paz, O.; Carballo, R.

doi:10.1107/S205698901701341X

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Volume 73| Part 10| October 2017| Pages 1523-1525

https://doi.org/10.1107/S205698901701341X

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A monoclinic polymorph of 1,2-bis[(1-methyl-1H-tetrazol-5-yl)sulfanyl]ethane (BMTTE)

Saray Argibay-Otero,^a Olaya Gómez-Paz ^a and Rosa Carballo ^a ^*

^aDepartamento de Química Inorgánica, Facultade de Química, Instituto de Investigación Sanitaria Galicia Sur – Universidade de Vigo, Campus Universitario, E-36310 Vigo, Galicia, Spain
^*Correspondence e-mail: rcrial@uvigo.es

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 13 September 2017; accepted 19 September 2017; online 25 September 2017)

The synthesis and crystal structure of a monoclinic (P2₁/c) polymorph of the title compound, C₆H₁₀S₂N₈, are reported. The molecule has pseudo-twofold rotational symmetry, with the tetrazole rings being inclined to one another by 5.50 (6)°. In the crystal, molecules are linked by C—H⋯N hydrogen bonds, forming chains propagating along [101] and enclosing R₂²(20) ring motifs. The chains are linked by offset π–π interactions involving the tetrazole rings [intercentroid distances vary from 3.3567 (7) to 3.4227 (7) Å], forming layers parallel to the ac plane. The crystal structure of the triclinic polymorph (P $[\overline{1}]$ ) has been described previously [Li et al. (2011 ). Acta Cryst. E67, o1669].

Keywords: crystal structure; polymorph; tetrazole-containing compounds; hydrogen bonding; π–π interactions.

CCDC reference: 1575392

1. Chemical context

Organic compounds such as the title compound (BMTTE) are frequently used as flexible ligands for the preparation of coordination polymers (Wang et al., 2010 ). A triclinic polymorph of the title compound has been described previously by Li et al., (2011). Here we describe the spectroscopic characterization and crystal structure of a new monoclinic polymorph of BMTTE, obtained by recrystallization and slow evaporation from a solution in CH₃CN. Such compounds have been used in coordination chemistry (Zhao et al., 2008 ) and in materials design (Wang et al., 2009 , 2010).

2. Structural commentary

The molecule structure of the title compound, Fig. 1, shows N—N and C—S bond distances and S—C—C—S and C—S—C—C torsion angles similar to the values observed in the triclinic form (Li et al., 2011). As shown by the molecular overlap of the two polymorphs (Fig. 2), drawn with Mercury (Macrae et al., 2008 ), there is only a slight difference in their geometry. The tetrazole rings (N1–N4/C1 and N5–N8/C4) are inclined to one another by 5.50 (6)° in the title polymorph and by 1.9 (2)° in the triclinic polymorph. While there are only small differences in the geometric parameters between the two polymorphic forms, they are enough to produce a different crystal packing.

Figure 1
Molecular structure of the title compound, the monoclinic polymorph of BMTTE, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
A molecular structure overlap (Mercury; Macrae et al., 2008

) of the title monoclinic polymorph of BMTTE (blue) and the triclinic polymorph (red; Li et al., 2011

3. Supramolecular features

In the crystal, molecules are linked by C—H⋯N hydrogen bonds, forming chains propagating along [101] and enclosing R₂²(20) ring motifs (Fig. 3 and Table 1). The chains are linked by offset π–π interactions involving the tetrazole rings, forming layers parallel to the ac plane, as shown in Fig. 4. The numerical details of these interactions are: Cg1⋯Cg1ⁱ = 3.365 (1) Å, α = 0°, interplanar distance = 3.2056 (4) Å, offset = 1.024 Å; Cg1⋯Cg2ⁱⁱ = 3.423 (1) Å, α = 5.5 (1)°, interplanar distances = 3.278 (4) and 3.321 (4) Å, offset = 0.83 Å; and Cg2⋯Cg2ⁱⁱⁱ = 3.4227 (7) Å, α = 0°, interplanar distance = 3.1346 (4) Å, offset = 1.201 Å; Cg1 and Cg2 are the centroids of the tetrazole rings N1–N4/C1 and N5–N8/C4, respectively; symmetry codes: (i) −x + 1, −y, −z; (ii) x − 1, y, z; (iii) −x + 2, −y, −z + 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯N8ⁱ	0.98	2.39	3.3533 (13)	168
C12—H12B⋯N4ⁱⁱ	0.98	2.36	3.3183 (13)	165
Symmetry codes: (i) -x+1, -y, -z; (ii) -x+2, -y, -z+1.

Figure 3
A partial view of the crystal packing of the title compound, showing details of the C—H⋯N hydrogen bonds (dashed lines, see Table 1

Figure 4
Crystal packing of the title compound, showing details of the C—H⋯N hydrogen bonds (dashed lines, see Table 1

) and examples of the π–π interactions (blue double-headed arrows).

As a result of these interactions, the molecules are packed very efficiently so that the Kitaigorodskii (1973 ) index is 72%. The crystal packing in the crystal of the triclinic polymorph is very similar, with a Kitaigorodskii index of 69% (PLATON; Spek, 2009 ).

4. Database survey

A search of the Cambridge Structural Database (CSD; version 5.38, last update May 2017; Groom et al., 2016 ) for the skeleton of the title compound gave 11 hits. Apart from the crystal structure of the triclinic polymorph of the title compound (CSD refcode EVAWUU; Li et al., 2011), and that of a diphenyl substituted compound, 1,2-bis(1-phenyl-1H-tetrazol-5-ylsulfanyl)ethane (IXAVUY; Wang et al., 2004 ), all the others involve coordination compounds of BMTTE.

5. Synthesis and crystallization

The title compound, (BMTTE), was synthesized by a slightly modified version of the procedure described by Li et al. (2011). 5-Mercapto-1-methyltetrazole (9.29 g, 0.08 mol) was added to a solution of sodium hydroxide (3.26 g, 0.08 mol) in EtOH (110 ml). The mixture was stirred at room temperature for one day. Dichloroethane (3.2 ml, 0.04 mol) in 6 ml of EtOH was then added dropwise and the mixture was refluxed for 18 h. The resulting white solid was filtered, washed with H₂O and dried in vacuo (yield 88%; m.p. 417–419 K). Analysis calculated for C₆H₁₀S₂N₈: N 43.38, C 27.90, H 3.90%; Found: N 42.31, C 27.85, H 3.28%. IR (cm⁻¹): 1469m, 1442m (1408m, 1391m) ν(ring); 1276m, 1222m, ω(CH–CH₂); 1169m, δ(CH); 1144m, 1078m, 1026m, δ(ring); 728m, 716m, γ(CH); 698s, ν(C—S). ¹H NMR (400 MHz, dmso-d₆) δ in ppm: 3.93 (s, 6H, Hb), 3.66 (s, 4H, Ha). MS–ESI: m/z (%) = 259 (100) [C₆H₁₀S₂N₈+H⁺]. Colourless prismatic crystals were obtained by slow evaporation of a solution in acetonitrile.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were included in calculated positions and treated as riding: C—H = 0.98–0.99 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₀N₈S₂
M_r	258.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.2456 (10), 13.7471 (17), 9.6878 (12)
β (°)	92.643 (4)
V (Å³)	1097.0 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.47
Crystal size (mm)	0.25 × 0.22 × 0.19

Data collection
Diffractometer	Bruker D8 Venture Photon 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.697, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	23909, 2725, 2620
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.057, 1.08
No. of reflections	2725
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.25
Computer programs: APEX3 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS2014 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1575392

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S205698901701341X/su5392sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901701341X/su5392Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901701341X/su5392Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S205698901701341X/su5392Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

1,2-Bis[(1-methyl-1H-tetrazol-5-yl)sulfanyl]ethane top

Crystal data top

C₆H₁₀N₈S₂	D_x = 1.564 Mg m⁻³
M_r = 258.34	Melting point: 144 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2456 (10) Å	Cell parameters from 9507 reflections
b = 13.7471 (17) Å	θ = 2.5–28.3°
c = 9.6878 (12) Å	µ = 0.47 mm⁻¹
β = 92.643 (4)°	T = 100 K
V = 1097.0 (2) Å³	Prism, colourless
Z = 4	0.25 × 0.22 × 0.19 mm
F(000) = 536

Data collection top

Bruker D8 Venture Photon 100 CMOS diffractometer	2620 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.024
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.697, T_max = 0.746	h = −10→11
23909 measured reflections	k = −18→18
2725 independent reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0262P)² + 0.493P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2725 reflections	Δρ_max = 0.36 e Å⁻³
148 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: (SHELXL2014; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0376 (18)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
S1	0.46814 (3)	0.19617 (2)	0.21662 (2)	0.01218 (8)
S2	0.99483 (3)	0.22655 (2)	0.31188 (3)	0.01382 (8)
N1	0.32833 (10)	0.04027 (6)	0.08604 (8)	0.01158 (16)
N2	0.33462 (11)	−0.05843 (6)	0.08543 (9)	0.01445 (17)
N3	0.44707 (11)	−0.08272 (6)	0.17676 (9)	0.01511 (18)
N4	0.51615 (11)	−0.00275 (6)	0.23918 (9)	0.01383 (17)
N5	1.15565 (10)	0.07099 (6)	0.42528 (8)	0.01085 (16)
N6	1.16663 (10)	−0.02693 (6)	0.41075 (9)	0.01411 (17)
N7	1.06184 (11)	−0.05083 (6)	0.31273 (9)	0.01451 (17)
N8	0.98081 (11)	0.02894 (6)	0.26071 (9)	0.01352 (17)
C1	0.44014 (11)	0.07287 (7)	0.18059 (10)	0.01056 (18)
C2	0.66415 (11)	0.19192 (7)	0.31250 (10)	0.01208 (19)
H2A	0.6649	0.2392	0.3896	0.014*
H2B	0.6818	0.1262	0.3520	0.014*
C3	0.79982 (12)	0.21624 (7)	0.21671 (10)	0.01285 (19)
H3A	0.7747	0.2784	0.1687	0.015*
H3B	0.8064	0.1647	0.1458	0.015*
C4	1.04182 (11)	0.10381 (7)	0.33269 (10)	0.01087 (18)
C11	0.21707 (12)	0.09470 (7)	−0.00653 (10)	0.0147 (2)
H11A	0.1360	0.1277	0.0476	0.022*
H11B	0.1624	0.0499	−0.0721	0.022*
H11C	0.2781	0.1431	−0.0572	0.022*
C12	1.25381 (12)	0.12395 (7)	0.52931 (10)	0.0152 (2)
H12A	1.3335	0.1642	0.4838	0.023*
H12B	1.3105	0.0776	0.5914	0.023*
H12C	1.1834	0.1656	0.5827	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01044 (12)	0.00922 (12)	0.01639 (13)	0.00092 (8)	−0.00455 (8)	0.00048 (8)
S2	0.01144 (13)	0.00868 (12)	0.02066 (14)	−0.00105 (8)	−0.00666 (9)	0.00047 (8)
N1	0.0121 (4)	0.0099 (4)	0.0125 (4)	0.0000 (3)	−0.0017 (3)	0.0000 (3)
N2	0.0164 (4)	0.0100 (4)	0.0170 (4)	0.0008 (3)	0.0007 (3)	−0.0005 (3)
N3	0.0153 (4)	0.0120 (4)	0.0178 (4)	0.0002 (3)	−0.0007 (3)	0.0006 (3)
N4	0.0140 (4)	0.0111 (4)	0.0162 (4)	0.0013 (3)	−0.0020 (3)	0.0019 (3)
N5	0.0110 (4)	0.0094 (4)	0.0119 (4)	0.0003 (3)	−0.0017 (3)	0.0007 (3)
N6	0.0156 (4)	0.0100 (4)	0.0168 (4)	0.0010 (3)	0.0019 (3)	0.0010 (3)
N7	0.0161 (4)	0.0115 (4)	0.0159 (4)	−0.0002 (3)	0.0007 (3)	−0.0003 (3)
N8	0.0150 (4)	0.0109 (4)	0.0145 (4)	−0.0013 (3)	−0.0014 (3)	−0.0010 (3)
C1	0.0091 (4)	0.0114 (4)	0.0111 (4)	0.0003 (3)	−0.0007 (3)	0.0007 (3)
C2	0.0107 (4)	0.0114 (4)	0.0136 (4)	0.0000 (3)	−0.0051 (3)	0.0002 (3)
C3	0.0108 (4)	0.0120 (4)	0.0153 (4)	−0.0006 (3)	−0.0048 (3)	0.0015 (3)
C4	0.0095 (4)	0.0115 (4)	0.0114 (4)	−0.0008 (3)	−0.0006 (3)	0.0004 (3)
C11	0.0137 (5)	0.0152 (5)	0.0144 (5)	0.0018 (4)	−0.0056 (4)	0.0008 (4)
C12	0.0152 (5)	0.0157 (5)	0.0140 (4)	−0.0022 (4)	−0.0062 (4)	−0.0003 (4)

Geometric parameters (Å, º) top

S1—C1	1.7438 (10)	N7—N8	1.3681 (12)
S1—C2	1.8276 (10)	N8—C4	1.3290 (12)
S2—C4	1.7409 (10)	C2—C3	1.5232 (14)
S2—C3	1.8218 (10)	C2—H2A	0.9900
N1—C1	1.3461 (12)	C2—H2B	0.9900
N1—N2	1.3578 (12)	C3—H3A	0.9900
N1—C11	1.4594 (12)	C3—H3B	0.9900
N2—N3	1.2956 (12)	C11—H11A	0.9800
N3—N4	1.3663 (12)	C11—H11B	0.9800
N4—C1	1.3278 (12)	C11—H11C	0.9800
N5—C4	1.3459 (12)	C12—H12A	0.9800
N5—N6	1.3569 (12)	C12—H12B	0.9800
N5—C12	1.4580 (12)	C12—H12C	0.9800
N6—N7	1.2964 (12)

C1—S1—C2	100.16 (4)	H2A—C2—H2B	108.2
C4—S2—C3	99.77 (5)	C2—C3—S2	111.39 (7)
C1—N1—N2	108.09 (8)	C2—C3—H3A	109.4
C1—N1—C11	129.71 (8)	S2—C3—H3A	109.4
N2—N1—C11	122.19 (8)	C2—C3—H3B	109.4
N3—N2—N1	106.31 (8)	S2—C3—H3B	109.4
N2—N3—N4	111.44 (8)	H3A—C3—H3B	108.0
C1—N4—N3	105.18 (8)	N8—C4—N5	108.99 (8)
C4—N5—N6	108.14 (8)	N8—C4—S2	127.81 (8)
C4—N5—C12	129.88 (8)	N5—C4—S2	123.14 (7)
N6—N5—C12	121.97 (8)	N1—C11—H11A	109.5
N7—N6—N5	106.38 (8)	N1—C11—H11B	109.5
N6—N7—N8	111.37 (8)	H11A—C11—H11B	109.5
C4—N8—N7	105.12 (8)	N1—C11—H11C	109.5
N4—C1—N1	108.98 (9)	H11A—C11—H11C	109.5
N4—C1—S1	128.32 (8)	H11B—C11—H11C	109.5
N1—C1—S1	122.69 (7)	N5—C12—H12A	109.5
C3—C2—S1	109.91 (7)	N5—C12—H12B	109.5
C3—C2—H2A	109.7	H12A—C12—H12B	109.5
S1—C2—H2A	109.7	N5—C12—H12C	109.5
C3—C2—H2B	109.7	H12A—C12—H12C	109.5
S1—C2—H2B	109.7	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···N8ⁱ	0.98	2.39	3.3533 (13)	168
C12—H12B···N4ⁱⁱ	0.98	2.36	3.3183 (13)	165

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

Funding information

Funding for this research was provided by: Ministry of Economy, Industry and Competitiveness (Spain) and European Regional Development Fund (EU) (CTQ2015-71211-REDT and CTQ2015-7091-R).

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