Bis(5-phenyl-1H-1,2,4-triazol-3-yl) disulfide dihydrate

Zhu, A.-X.; Liu, J.-N.; Li, Z.; Wang, H.-C.; Du, Y.-C.

doi:10.1107/S1600536811014607

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1208

doi:10.1107/S1600536811014607

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Bis(5-phenyl-1H-1,2,4-triazol-3-yl) disulfide dihydrate

Ai-Xin Zhu,^a ^* Jun-Na Liu,^b Zhen Li,^a Hong-Can Wang ^a and Yuan-Chao Du ^a

^aFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, People's Republic of China, and ^bSchool of Chemical Engineering, Henan University of Science and Technology, Luoyang 471003, People's Republic of China
^*Correspondence e-mail: zaxchem@126.com

(Received 2 April 2011; accepted 19 April 2011; online 29 April 2011)

A crystallographic twofold axis passing through the centre of the disulfide linkage in the title compound, C₁₆H₁₂N₆S₂·2H₂O, results in one-half of the molecule and one uncoordinated water molecule described in the asymmetric unit. In the molecule, the mean planes of the benzene and triazole rings are close to being coplanar and are separated by a dihedral angle of 2.08 (15)°. The triazole rings are twisted by a dihedral angle of 37.67 (6)° from the disulfide linkage. The crystal packing is stabilized by intermolecular N—H⋯O and O—H⋯N hydrogen bonds with the water molecules, forming a three-dimensional supramolecular network.

Related literature

For applications of 1,2,4-triazole and its derivatives in coordination chemistry, see: Zhang et al. (2005 ); Ouellette et al. (2007 ); Zhu et al. (2009 ). For the related structure of a 1,2,4-triazole-based disulfide compound, see: Jiang et al. (2007 ). For the previous synthesis of the title compound, see: El-Wareth & Sarhan (2000 ).

Experimental

Crystal data

C₁₆H₁₂N₆S₂·2H₂O
M_r = 388.47
Monoclinic, C 2/c
a = 12.3911 (13) Å
b = 14.7125 (16) Å
c = 10.2966 (11) Å
β = 104.125 (2)°
V = 1820.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.884, T_max = 0.945
7210 measured reflections
1953 independent reflections
1679 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.120
S = 1.06
1953 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1C⋯N3	0.90	2.02	2.9210 (19)	178
N1—H1B⋯O1ⁱ	0.86	1.90	2.7077 (19)	156
O1—H1D⋯N2ⁱⁱ	0.84	2.07	2.909 (2)	171
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014607/jj2087sup1.cif

Supporting information file. DOI: 10.1107/S1600536811014607/jj2087Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014607/jj2087Isup3.hkl

checkCIF report

Comment top

In the past few years, 1,2,4-triazole and its derivatives have attracted increasing attention as an N-heterocyclic aromatic ligand, since they can combine both imidazoles and pyrazoles in their coordination geometry. In addition, metal-triazolate frameworks can exhibit special luminescent, magnetic and favourable gas-adsorption abilities (Ouellette et al., 2007; Zhang et al., 2005; Zhu et al., 2009). 1,2,4-triazole based thiols and disulfides are important 1,2,4-triazole derivatives, and may exhibit a more diverse coordination geometry by combining heterocyclic nitrogen and sulfur donor atoms, and therefore affect biological activity behaviour. However, only one example of a crystallographic study on organic 1,2,4-triazole based disulfide compounds is found in the literature (Jiang et al. 2007). Although the synthesis of the compound 1,2-bis(5-phenyl-1H-1,2,4-triazol-3-yl)disulfide has been reported by El-Wareth & Sarhan (2000), no crystallographic study has been reported on the ligand and related metal coordination compounds. We reported herein another synthetic method and the crystal structure of the title compound.

A crystallographic 2-fold axis passing through the centroid of the disulfide linkage in the title compound, C₁₆H₁₂N₆S₂.2H₂O, results in one-half of the molecule and one uncoordinated water molecule described in the asymmetric unit (Fig. 1). In the molecule, the mean planes of the benzene and triazole rings are close to coplanar, separated by a dihedral angle of 2.08 (15)°. The triazole rings are twisted by a dihedral angle of 37.67 (6)° from the disulfide linkage. Crystal packing is stabilized by intermolecular N—H···O and O—H···N hydrogen bonds with the water molecules forming a three-dimensional supramolecular network (Fig. 2).

Related literature top

For applications of 1,2,4-triazole and its derivatives in coordination chemistry, see: Zhang et al. (2005); Ouellette et al. (2007); Zhu et al. (2009). For the related structure of a 1,2,4-triazole-based disulfide compound, see: Jiang et al. (2007). For the previous synthesis of the title compound, see: El-Wareth & Sarhan (2000).

Experimental top

A mixture of iron dichloride tetrahydrate (40 mg, 0.2 mmol), 3-phenyl-1H-1,2,4-triazole-5(4H)-thione (35 mg, 0.2 mmol), 8 ml methanol and 4 ml acetonitrile was stirred for 10 min, then filtered and allowed to stand at room temperature for about two weeks. Yellow polyhedron crystals suitable for X-ray diffraction were obtained.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Packing diagram of the title compound viewed down the a axis. O—H···N and N—H···O hydrogen bonds with the water molecule are shown with dashed lines.

5-phenyl-3-[(5-phenyl-1H-1,2,4-triazol-3-yl)disulfanyl]-1H-1,2,4-triazole dihydrate top

Crystal data top

C₁₆H₁₂N₆S₂·2H₂O	F(000) = 808
M_r = 388.47	D_x = 1.417 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3134 reflections
a = 12.3911 (13) Å	θ = 2.7–26.4°
b = 14.7125 (16) Å	µ = 0.32 mm⁻¹
c = 10.2966 (11) Å	T = 293 K
β = 104.125 (2)°	Polyhedron, yellow
V = 1820.4 (3) Å³	0.40 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	1953 independent reflections
Radiation source: fine-focus sealed tube	1679 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.884, T_max = 0.945	k = −18→18
7210 measured reflections	l = −13→13

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0691P)² + 0.5857P] where P = (F_o² + 2F_c²)/3
1953 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₂N₆S₂·2H₂O	V = 1820.4 (3) Å³
M_r = 388.47	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.3911 (13) Å	µ = 0.32 mm⁻¹
b = 14.7125 (16) Å	T = 293 K
c = 10.2966 (11) Å	0.40 × 0.20 × 0.18 mm
β = 104.125 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	1953 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1679 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.945	R_int = 0.023
7210 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
1953 reflections	Δρ_min = −0.18 e Å⁻³
118 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	0.43278 (4)	0.48004 (3)	0.16853 (5)	0.0605 (2)
N1	0.26234 (13)	0.68205 (9)	0.22572 (14)	0.0535 (4)
H1B	0.2373	0.7366	0.2112	0.064*
N2	0.33478 (13)	0.64316 (9)	0.16425 (15)	0.0554 (4)
N3	0.28640 (12)	0.54543 (9)	0.30878 (14)	0.0501 (3)
C1	0.13764 (18)	0.58140 (14)	0.4862 (2)	0.0673 (5)
H1A	0.1698	0.5240	0.4897	0.081*
C2	0.0682 (2)	0.60203 (17)	0.5693 (2)	0.0792 (6)
H2A	0.0543	0.5586	0.6288	0.095*
C3	0.01979 (18)	0.68669 (16)	0.5640 (2)	0.0729 (6)
H3A	−0.0284	0.6999	0.6180	0.087*
C4	0.0428 (2)	0.75119 (16)	0.4792 (2)	0.0723 (6)
H4A	0.0115	0.8088	0.4773	0.087*
C5	0.11194 (17)	0.73153 (13)	0.3963 (2)	0.0615 (5)
H5A	0.1270	0.7759	0.3388	0.074*
C6	0.15919 (13)	0.64584 (11)	0.39834 (16)	0.0478 (4)
C7	0.23446 (14)	0.62407 (11)	0.31284 (16)	0.0461 (4)
C8	0.34687 (14)	0.56106 (11)	0.21779 (17)	0.0503 (4)
O1	0.27936 (14)	0.35247 (9)	0.37303 (13)	0.0762 (5)
H1D	0.3018	0.3501	0.4572	0.091*
H1C	0.2833	0.4118	0.3533	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0728 (4)	0.0462 (3)	0.0721 (3)	−0.00574 (19)	0.0364 (3)	−0.01332 (19)
N1	0.0701 (9)	0.0405 (7)	0.0563 (8)	0.0046 (6)	0.0276 (7)	0.0048 (6)
N2	0.0731 (9)	0.0448 (8)	0.0561 (8)	−0.0012 (7)	0.0305 (7)	0.0014 (6)
N3	0.0584 (8)	0.0412 (7)	0.0564 (8)	−0.0014 (6)	0.0248 (6)	0.0027 (6)
C1	0.0780 (13)	0.0589 (11)	0.0745 (12)	0.0101 (9)	0.0371 (10)	0.0135 (9)
C2	0.0917 (16)	0.0835 (15)	0.0757 (14)	0.0031 (12)	0.0463 (12)	0.0154 (11)
C3	0.0697 (13)	0.0864 (15)	0.0716 (13)	0.0043 (11)	0.0347 (10)	−0.0062 (11)
C4	0.0757 (13)	0.0681 (13)	0.0813 (14)	0.0161 (10)	0.0347 (11)	−0.0006 (10)
C5	0.0693 (12)	0.0539 (10)	0.0671 (11)	0.0098 (9)	0.0278 (9)	0.0082 (8)
C6	0.0478 (8)	0.0494 (9)	0.0477 (8)	−0.0011 (7)	0.0142 (7)	0.0003 (7)
C7	0.0517 (9)	0.0405 (8)	0.0476 (8)	−0.0031 (6)	0.0150 (7)	0.0014 (6)
C8	0.0596 (10)	0.0420 (8)	0.0543 (9)	−0.0052 (7)	0.0233 (7)	−0.0033 (7)
O1	0.1323 (14)	0.0421 (7)	0.0576 (8)	−0.0052 (7)	0.0300 (8)	−0.0033 (5)

Geometric parameters (Å, º) top

S1—C8	1.7536 (17)	C2—C3	1.378 (3)
S1—S1ⁱ	2.0556 (11)	C2—H2A	0.9300
N1—C7	1.343 (2)	C3—C4	1.366 (3)
N1—N2	1.346 (2)	C3—H3A	0.9300
N1—H1B	0.8600	C4—C5	1.380 (3)
N2—C8	1.321 (2)	C4—H4A	0.9300
N3—C7	1.330 (2)	C5—C6	1.388 (2)
N3—C8	1.355 (2)	C5—H5A	0.9300
C1—C6	1.381 (2)	C6—C7	1.466 (2)
C1—C2	1.386 (3)	O1—H1D	0.8434
C1—H1A	0.9300	O1—H1C	0.9007

C8—S1—S1ⁱ	101.08 (6)	C3—C4—H4A	119.7
C7—N1—N2	110.73 (14)	C5—C4—H4A	119.7
C7—N1—H1B	124.6	C4—C5—C6	120.28 (19)
N2—N1—H1B	124.6	C4—C5—H5A	119.9
C8—N2—N1	102.31 (13)	C6—C5—H5A	119.9
C7—N3—C8	103.16 (14)	C1—C6—C5	119.04 (17)
C6—C1—C2	120.15 (19)	C1—C6—C7	119.78 (16)
C6—C1—H1A	119.9	C5—C6—C7	121.14 (16)
C2—C1—H1A	119.9	N3—C7—N1	109.05 (14)
C3—C2—C1	120.2 (2)	N3—C7—C6	126.37 (15)
C3—C2—H2A	119.9	N1—C7—C6	124.58 (15)
C1—C2—H2A	119.9	N2—C8—N3	114.73 (15)
C4—C3—C2	119.78 (19)	N2—C8—S1	121.06 (13)
C4—C3—H3A	120.1	N3—C8—S1	124.19 (13)
C2—C3—H3A	120.1	H1D—O1—H1C	104.4
C3—C4—C5	120.5 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···N3	0.90	2.02	2.9210 (19)	178
N1—H1B···O1ⁱⁱ	0.86	1.90	2.7077 (19)	156
O1—H1D···N2ⁱⁱⁱ	0.84	2.07	2.909 (2)	171

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂N₆S₂·2H₂O
M_r	388.47
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.3911 (13), 14.7125 (16), 10.2966 (11)
β (°)	104.125 (2)
V (Å³)	1820.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.40 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.884, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	7210, 1953, 1679
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.120, 1.06
No. of reflections	1953
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···N3	0.90	2.02	2.9210 (19)	178.0
N1—H1B···O1ⁱ	0.86	1.90	2.7077 (19)	155.6
O1—H1D···N2ⁱⁱ	0.84	2.07	2.909 (2)	170.9

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

Acknowledgements

The authors thank the Youth Foundation of Yunnan Normal University (grant No. 10QZ02), the Science Foundation of the Education Department of Yunnan Province (grant No. 2010Y004) and Henan University of Science and Technology for supporting this work.

References

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