1H-1,2,4-Triazol-4-ium (3,4-dichloro­phen­yl)methane­sulfonate

Zhang, L.; Damu, G.L.V.; Lv, J.-S.; Geng, R.-X.; Zhou, C.-H.

doi:10.1107/S1600536811053062

organic compounds

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Volume 68| Part 1| January 2012| Page o131

doi:10.1107/S1600536811053062

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1H-1,2,4-Triazol-4-ium (3,4-dichlorophenyl)methanesulfonate

Ling Zhang,^a Guri L. V. Damu,^a Jing-Song Lv,^a Rong-Xia Geng ^a ^* and Cheng-He Zhou ^a ^*

^aLaboratory of Bioorganic & Medicinal Chemistry, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: geng0712@swu.edu.cn, zhouch@swu.edu.cn

(Received 4 December 2011; accepted 9 December 2011; online 14 December 2011)

In the title molecular salt, C₂H₄N₃⁺·C₇H₅Cl₂O₃S⁻, C—C—S angle [112.25 (18)°] deviates slightly from that expected for ideal sp³-hybridization geometry. In the crystal, the components are linked by N—H⋯O and bifurcated N—H⋯(O,O) hydrogen bonds into chains parallel to [110].

Related literature

For applications of triazole compounds, see: Sen et al. (2010 ); Subbaraman et al. (2009 ); Wang & Zhou (2011 ); Zhou et al. (2009 ); Bai et al. (2007 ); Chang et al.(2011 ).

Experimental

Crystal data

C₂H₄N₃⁺·C₇H₅Cl₂O₃S⁻
M_r = 310.15
Triclinic, $[P \overline 1]$
a = 5.2430 (6) Å
b = 8.2970 (8) Å
c = 14.5656 (15) Å
α = 94.330 (5)°
β = 98.387 (6)°
γ = 92.292 (5)°
V = 624.22 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.820, T_max = 0.846
8971 measured reflections
2196 independent reflections
2000 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.124
S = 1.03
2196 reflections
180 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1M⋯O1ⁱ	0.85 (4)	1.96 (4)	2.709 (3)	146 (4)
N3—H4M⋯O2ⁱⁱ	0.79 (4)	2.08 (4)	2.768 (3)	146 (3)
N3—H4M⋯O2ⁱⁱⁱ	0.79 (4)	2.54 (3)	3.089 (3)	128 (3)
Symmetry codes: (i) x, y+1, z; (ii) x-1, y, z; (iii) -x, -y, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811053062/lh5392sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053062/lh5392Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053062/lh5392Isup3.cml

checkCIF report

Comment top

Triazole is a unique molecule which could exert diverse non-covalent interactions and endow triazole derivatives to exhibit various potential appplications in medicinal chemistry (Wang & Zhou, 2011), argrochemical and chemical fields (Bai et al., 2007) and material science (Chang et al., 2011). Work has shown that triazole derivatives could be used as proton transport facilitators for sulfonic acid based membranes for high temperature fuel cell operations (Sen et al., 2010; Subbaraman et al., 2009). Our interest is to investigate the intreractions of triazole compounds with diverse anions for the formation of supramolecular drugs (Zhou et al., 2009). Herein we report the crystal structure of title compound.

In the molecular structure the title compound (Fig. 1) there is a slight deviation of the C2—C1—S1 angle (112.25°) in terms ideal sp³ hybridization geometry. In the crystal, the components are linked by N—H···O hydrogen bonds and bifurcated N—H···(O,O) into one dimensional chains along [110].

Related literature top

For applications of triazole compounds, see: Sen et al. (2010); Subbaraman et al. (2009); Wang & Zhou (2011); Zhou et al. (2009); Bai et al. (2007); Chang et al.(2011).

Experimental top

A crystal of title the compound suitable for X-ray analysis was grown from the solution of 1,2,4-triazole and (3,4-dichlorophenyl)methanesulfonic acid in methanol by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level.

1H-1,2,4-Triazol-4-ium (3,4-dichlorophenyl)methanesulfonate top

Crystal data top

C₂H₄N₃⁺·C₇H₅Cl₂O₃S⁻	Z = 2
M_r = 310.15	F(000) = 316
Triclinic, P1	D_x = 1.650 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2430 (6) Å	Cell parameters from 4951 reflections
b = 8.2970 (8) Å	θ = 2.8–27.5°
c = 14.5656 (15) Å	µ = 0.69 mm⁻¹
α = 94.330 (5)°	T = 296 K
β = 98.387 (6)°	Block, colorless
γ = 92.292 (5)°	0.30 × 0.28 × 0.25 mm
V = 624.22 (11) Å³

Data collection top

Bruker SMART CCD diffractometer	2196 independent reflections
Radiation source: fine-focus sealed tube	2000 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ scans and ω scans with κ offsets	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.820, T_max = 0.846	k = −9→9
8971 measured reflections	l = −17→17

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0656P)² + 0.6305P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2196 reflections	Δρ_max = 0.69 e Å⁻³
180 parameters	Δρ_min = −0.60 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.064 (7)

Crystal data top

C₂H₄N₃⁺·C₇H₅Cl₂O₃S⁻	γ = 92.292 (5)°
M_r = 310.15	V = 624.22 (11) Å³
Triclinic, P1	Z = 2
a = 5.2430 (6) Å	Mo Kα radiation
b = 8.2970 (8) Å	µ = 0.69 mm⁻¹
c = 14.5656 (15) Å	T = 296 K
α = 94.330 (5)°	0.30 × 0.28 × 0.25 mm
β = 98.387 (6)°

Data collection top

Bruker SMART CCD diffractometer	2196 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2000 reflections with I > 2σ(I)
T_min = 0.820, T_max = 0.846	R_int = 0.030
8971 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.69 e Å⁻³
2196 reflections	Δρ_min = −0.60 e Å⁻³
180 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
H4M	−0.257 (7)	0.126 (5)	0.067 (2)	0.059 (10)*
C1	0.5971 (5)	−0.1996 (3)	0.24949 (19)	0.0405 (6)
H1A	0.4222	−0.1654	0.2491	0.049*
H1B	0.6118	−0.2993	0.2801	0.049*
C2	0.7822 (5)	−0.0722 (3)	0.30368 (18)	0.0393 (6)
C3	0.7467 (7)	0.0915 (4)	0.2965 (2)	0.0522 (8)
H3	0.6021	0.1240	0.2589	0.063*
C4	0.9246 (8)	0.2072 (4)	0.3449 (2)	0.0577 (9)
C5	1.1357 (8)	0.1603 (4)	0.4029 (2)	0.0634 (9)
C6	1.1715 (8)	−0.0016 (5)	0.4095 (3)	0.0751 (11)
H6	1.3146	−0.0343	0.4478	0.090*
C7	0.9978 (7)	−0.1156 (4)	0.3600 (2)	0.0560 (8)
H7	1.0266	−0.2248	0.3647	0.067*
C8	0.1007 (6)	0.1330 (3)	0.1058 (2)	0.0448 (7)
C10	−0.1080 (5)	0.3440 (3)	0.0826 (2)	0.0404 (6)
Cl1	0.8778 (3)	0.40861 (12)	0.33114 (10)	0.1080 (5)
Cl2	1.3556 (3)	0.30086 (16)	0.46816 (10)	0.1064 (5)
N1	0.1333 (4)	0.3833 (3)	0.10869 (16)	0.0393 (6)
N2	0.2733 (4)	0.2507 (3)	0.12354 (19)	0.0476 (6)
N3	−0.1339 (4)	0.1855 (3)	0.08066 (18)	0.0423 (6)
O1	0.4994 (3)	−0.3828 (2)	0.09619 (13)	0.0383 (5)
O2	0.5688 (4)	−0.0964 (2)	0.08476 (13)	0.0417 (5)
O3	0.9286 (3)	−0.2589 (2)	0.13509 (14)	0.0446 (5)
S1	0.65640 (11)	−0.23697 (7)	0.13202 (4)	0.0291 (2)
H3M	0.132 (7)	0.035 (5)	0.108 (3)	0.070 (11)*
H2M	−0.232 (8)	0.408 (5)	0.070 (3)	0.069 (11)*
H1M	0.197 (8)	0.480 (5)	0.111 (3)	0.069 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0418 (15)	0.0362 (14)	0.0448 (15)	−0.0018 (11)	0.0112 (12)	0.0037 (11)
C2	0.0474 (16)	0.0346 (14)	0.0369 (13)	0.0005 (11)	0.0119 (12)	0.0001 (11)
C3	0.067 (2)	0.0388 (16)	0.0495 (16)	0.0047 (14)	0.0037 (14)	0.0031 (13)
C4	0.089 (3)	0.0335 (16)	0.0525 (18)	−0.0047 (16)	0.0240 (18)	−0.0040 (13)
C5	0.069 (2)	0.057 (2)	0.060 (2)	−0.0170 (17)	0.0137 (17)	−0.0196 (16)
C6	0.069 (2)	0.061 (2)	0.083 (3)	0.0053 (18)	−0.020 (2)	−0.0160 (19)
C7	0.060 (2)	0.0419 (17)	0.0606 (19)	0.0051 (14)	−0.0021 (15)	−0.0072 (14)
C8	0.0402 (16)	0.0259 (14)	0.0685 (19)	0.0036 (11)	0.0082 (13)	0.0052 (13)
C10	0.0316 (14)	0.0324 (14)	0.0553 (16)	0.0028 (11)	0.0013 (12)	0.0011 (12)
Cl1	0.1756 (14)	0.0328 (5)	0.1118 (9)	−0.0042 (6)	0.0125 (9)	0.0028 (5)
Cl2	0.1059 (10)	0.0813 (8)	0.1162 (10)	−0.0352 (7)	−0.0009 (7)	−0.0397 (7)
N1	0.0373 (13)	0.0243 (12)	0.0543 (14)	−0.0071 (9)	0.0030 (10)	0.0023 (10)
N2	0.0283 (12)	0.0420 (14)	0.0704 (16)	0.0012 (10)	0.0000 (11)	0.0059 (12)
N3	0.0267 (12)	0.0332 (12)	0.0651 (16)	−0.0091 (10)	0.0086 (11)	−0.0048 (11)
O1	0.0332 (10)	0.0229 (9)	0.0571 (11)	−0.0051 (7)	0.0052 (8)	−0.0026 (8)
O2	0.0462 (11)	0.0250 (9)	0.0518 (11)	−0.0040 (8)	−0.0012 (8)	0.0092 (8)
O3	0.0264 (10)	0.0443 (11)	0.0617 (12)	−0.0004 (8)	0.0071 (8)	−0.0051 (9)
S1	0.0251 (4)	0.0196 (3)	0.0417 (4)	−0.0026 (2)	0.0042 (2)	0.0009 (2)

Geometric parameters (Å, º) top

C1—C2	1.500 (4)	C7—H7	0.9300
C1—S1	1.790 (3)	C8—N2	1.289 (4)
C1—H1A	0.9700	C8—N3	1.332 (4)
C1—H1B	0.9700	C8—H3M	0.84 (4)
C2—C7	1.374 (4)	C10—N1	1.288 (4)
C2—C3	1.388 (4)	C10—N3	1.314 (4)
C3—C4	1.387 (5)	C10—H2M	0.86 (4)
C3—H3	0.9300	N1—N2	1.360 (3)
C4—C5	1.378 (6)	N1—H1M	0.86 (4)
C4—Cl1	1.721 (3)	N3—H4M	0.79 (4)
C5—C6	1.373 (6)	O1—S1	1.4538 (17)
C5—Cl2	1.732 (3)	O2—S1	1.4550 (19)
C6—C7	1.371 (5)	O3—S1	1.4405 (19)
C6—H6	0.9300

C2—C1—S1	112.25 (18)	C6—C7—H7	119.3
C2—C1—H1A	109.2	C2—C7—H7	119.3
S1—C1—H1A	109.2	N2—C8—N3	111.8 (3)
C2—C1—H1B	109.2	N2—C8—H3M	124 (3)
S1—C1—H1B	109.2	N3—C8—H3M	124 (3)
H1A—C1—H1B	107.9	N1—C10—N3	106.9 (3)
C7—C2—C3	118.1 (3)	N1—C10—H2M	128 (3)
C7—C2—C1	120.3 (3)	N3—C10—H2M	126 (3)
C3—C2—C1	121.6 (3)	C10—N1—N2	111.6 (2)
C4—C3—C2	120.7 (3)	C10—N1—H1M	123 (3)
C4—C3—H3	119.7	N2—N1—H1M	125 (3)
C2—C3—H3	119.7	C8—N2—N1	103.0 (2)
C5—C4—C3	120.0 (3)	C10—N3—C8	106.8 (2)
C5—C4—Cl1	120.9 (3)	C10—N3—H4M	131 (3)
C3—C4—Cl1	119.0 (3)	C8—N3—H4M	122 (3)
C6—C5—C4	119.2 (3)	O3—S1—O1	112.59 (11)
C6—C5—Cl2	119.2 (3)	O3—S1—O2	113.48 (12)
C4—C5—Cl2	121.6 (3)	O1—S1—O2	111.99 (11)
C7—C6—C5	120.5 (4)	O3—S1—C1	107.50 (13)
C7—C6—H6	119.7	O1—S1—C1	104.86 (12)
C5—C6—H6	119.7	O2—S1—C1	105.69 (13)
C6—C7—C2	121.4 (3)

S1—C1—C2—C7	−96.9 (3)	C5—C6—C7—C2	−0.9 (6)
S1—C1—C2—C3	81.1 (3)	C3—C2—C7—C6	1.2 (5)
C7—C2—C3—C4	0.1 (5)	C1—C2—C7—C6	179.3 (3)
C1—C2—C3—C4	−177.9 (3)	N3—C10—N1—N2	0.8 (3)
C2—C3—C4—C5	−1.8 (5)	N3—C8—N2—N1	0.4 (3)
C2—C3—C4—Cl1	178.0 (2)	C10—N1—N2—C8	−0.7 (3)
C3—C4—C5—C6	2.2 (5)	N1—C10—N3—C8	−0.5 (3)
Cl1—C4—C5—C6	−177.7 (3)	N2—C8—N3—C10	0.0 (4)
C3—C4—C5—Cl2	−177.3 (3)	C2—C1—S1—O3	48.8 (2)
Cl1—C4—C5—Cl2	2.8 (4)	C2—C1—S1—O1	168.79 (19)
C4—C5—C6—C7	−0.8 (6)	C2—C1—S1—O2	−72.7 (2)
Cl2—C5—C6—C7	178.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1M···O1ⁱ	0.85 (4)	1.96 (4)	2.709 (3)	146 (4)
N3—H4M···O2ⁱⁱ	0.79 (4)	2.08 (4)	2.768 (3)	146 (3)
N3—H4M···O2ⁱⁱⁱ	0.79 (4)	2.54 (3)	3.089 (3)	128 (3)

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

Experimental details

Crystal data
Chemical formula	C₂H₄N₃⁺·C₇H₅Cl₂O₃S⁻
M_r	310.15
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.2430 (6), 8.2970 (8), 14.5656 (15)
α, β, γ (°)	94.330 (5), 98.387 (6), 92.292 (5)
V (Å³)	624.22 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.30 × 0.28 × 0.25

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.820, 0.846
No. of measured, independent and observed [I > 2σ(I)] reflections	8971, 2196, 2000
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.124, 1.03
No. of reflections	2196
No. of parameters	180
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.60

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1M···O1ⁱ	0.85 (4)	1.96 (4)	2.709 (3)	146 (4)
N3—H4M···O2ⁱⁱ	0.79 (4)	2.08 (4)	2.768 (3)	146 (3)
N3—H4M···O2ⁱⁱⁱ	0.79 (4)	2.54 (3)	3.089 (3)	128 (3)

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

Acknowledgements

This work was partially supported by the Natural Science Foundation of China (21172181), the Specialized Research Fund for the Doctoral Program of Higher Education of China (SRFDP 20110182110007) and the Fundamental Research Funds for the Central Universities (XDJK2011D007).

References

Bai, X., Zhou, C.-H. & Mi, J.-L. (2007). Chem. Res. Appl. 19, 721–729. CAS Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chang, J.-J., Wang, Y., Zhang, H.-Z., Zhou, C.-H., Geng, R.-X. & Ji, Q.-G. (2011). Chem. J. Chin. Univ. 32, 1970–1985. CAS Google Scholar
Sen, U., Bozkurt, A. & Ata, A. (2010). J. Power Sources, 195, 7720–7726. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Subbaraman, R., Ghassemi, H. & Zawodzinski, T. Jr (2009). Solid State Ionics, 180, 1143–1150. Web of Science CrossRef CAS Google Scholar
Wang, Y. & Zhou, C.-H. (2011). Sci. Sin. Chem. 41, 1429–1456. CrossRef Google Scholar
Zhou, C.-H., Gan, L.-L., Zhang, Y.-Y., Zhang, F.-F., Wang, G.-Z., Jin, L. & Geng, R. X. (2009). Sci. China Ser. B, 52, 415–458. Web of Science CrossRef CAS Google Scholar