1-Methane­sulfonyl-1H-1,2,3-benzotriazole

Petr Štěpnička; Hana Solařová; Ivana Císařová

doi:10.1107/S1600536810040778

. 2010 Oct 20;66(Pt 11):o2840. doi: 10.1107/S1600536810040778

1-Methanesulfonyl-1H-1,2,3-benzotriazole

Petr Štěpnička ^a,^*, Hana Solařová ^a, Ivana Císařová ^a

PMCID: PMC3009158 PMID: 21589026

Abstract

The molecular geometry of the title compound, C₇H₇N₃O₂S, does not differ much from that of the previously reported 4-toluenesulfonyl analogue. Unlike the latter compound, however, molecules of the title compound associate primarily via π–π stacking interactions of their benzene rings [centroid–centroid distance = 3.5865 (8) Å], forming columnar stacks along the crystallographic 2₁ axes. These stacks are interconnected via weak C—H⋯O and C—H⋯N hydrogen bonds.

Related literature

For crystal structure of 1-(p-toluenesulfonyl)-1H-1,2,3-benzotriazole, see: Rodríguez et al. (2005 ▶). For the preparation of the title compound and examples of its synthetic use, see: Katritzky et al. (1992 ▶, 2000 ▶).

Experimental

Crystal data

C₇H₇N₃O₂S
M _r = 197.22
Monoclinic,
a = 9.3685 (3) Å
b = 7.0627 (2) Å
c = 12.4994 (3) Å
β = 92.984 (2)°
V = 825.93 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 150 K
0.50 × 0.30 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer
14989 measured reflections
1886 independent reflections
1674 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.082
S = 1.09
1886 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999) ▶; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810040778/im2237sup1.cif

e-66-o2840-sup1.cif^{(14KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040778/im2237Isup2.hkl

e-66-o2840-Isup2.hkl^{(92.9KB, hkl)}

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
C5—H5⋯O2ⁱ	0.93	2.55	3.270 (2)	135
C6—H6⋯O1ⁱⁱ	0.93	2.55	3.451 (2)	164
C8—H8B⋯N3ⁱⁱⁱ	0.96	2.61	3.446 (2)	145
C8—H8C⋯O2^iv	0.96	2.40	3.325 (2)	161

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

Financial support from the Ministry of Education of the Czech Republic (project No. MSM0021620857) is gratefully acknowledged.

supplementary crystallographic information

Comment

The title compound, 1-(methanesulfonyl)-1H-1,2,3-benzotriazole, is a useful and readily accessible organic reagent, acting as a convenient source of the benzotriazolyl anion. For instance, it reacts smoothly with carboxylic acids in the presence of a base to afford the corresponding 1-acyl-1H-1,2,3-benzotriazoles, which can be subsequently converted to amides in typically good yields (Katritzky et al., 2000).

The molecular structure of the title compound (Fig. 1) is rather unexceptional, particularly in view of the geometric data reported earlier for the related 1H-1,2,3-benzotriazole derivative, 1-(p-toluenesulfonyl)-1H-1,2,3-benzotriazole (Rodríguez et al., 2005). The N—N bonds within the triazole ring clearly maintain their localized character (cf. N1—N2 = 1.389 (2) Å, N3—N2 = 1.288 (2) Å), which is, however, not reflected in the adjacent bonds. The lengths of the remaining in-ring bonds, N1—C7A, C7A—C3A and C3A—N3, differ by less than ca 0.006 Å, while all in-ring angles span a range of 103.5 (1)–109.9 (1) °. On the other hand, the variation in the analogous parameters describing the geometry of the annelating benzene ring is less pronounced (cf. C—C = 1.371 (2)–1.408 (2) Å, C—C—C = 115.5 (1)–122.7 (1) °).

The methanesulfonyl group binds to the triazole ring somewhat unsymmetrically, which is best demonstrated by the difference in the S—N1—N2 (120.12 (9) °) and S—N1—C7A (129.8 (1) °) angles. Moreover, it is angularly distorted: The bond angles around sulfur span a range of 103.43 (6)–120.31 (7) ° with the N1—S—C8 and O1—S—O2 angles being the lower and upper limit, respectively. The remaining angles do not differ much in the pairs: N1—S—O(1/2) (ca 105 °, difference ca 0.4 °), C8—S1—O(1/2) (ca 110 °, difference ca 1.2 °). Indeed, such a variation in bond angles corresponds with distances to the sulfur atom (S—O1 1.425 (1), S—O2 1.419 (1), S—N1 1.692 (1), S—C8 1.744 (2) Å) as the most acute angle is associated with the shortest bonds.

In the crystal, molecules of the title compound assemble viaπ–π stacking interactions of their benzene rings (Fig. 2a). Since this interaction involves molecules related by the crystallographic 2₁ screw axes, it results in the formation of infinite columnar stacks in the direction of the crystallographic b axis. It is worth pointing out that the observed separation of the ring centroids [Cg···Cg (-x, 1/2 + y, 1/2-z; 3.5865 (8) Å] is slightly shorter than that reported for α-graphite (ca 3.65 Å), where, however, the rings are slipped by ca 1.42 Å. Finally, the neighboring columnar stacks are interlinked by soft C—H···O and C—H···N hydrogen bonds (Table 1) into a complicated three-dimensional array (Figs. 2b and 2c).

Experimental

The title compound was synthesized from 1H-1,2,3-benzotriazole and methanesulfonyl chloride as described in the literature with a yield of 91% (Katritzky et al., 2000). Crystals suitable for X-ray diffraction analysis were obtained by crystallization from warm benzene.