5,5′-Diethyl-2,2′-(triazene-1,3-di­yl)di-1,3,4-thia­diazole

Zeng, H.-S.; Han, L.-N.; Kang, S.; Li, H.; Wang, H.

doi:10.1107/S1600536808033941

organic compounds

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Volume 64| Part 11| November 2008| Page o2166

doi:10.1107/S1600536808033941

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5,5′-Diethyl-2,2′-(triazene-1,3-diyl)di-1,3,4-thiadiazole

Hai-Su Zeng,^a Lu-Na Han,^a Si-shun Kang,^a Hai-lin Li ^a and Hai-bo Wang ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 14 October 2008; accepted 17 October 2008; online 22 October 2008)

In the molecule of the title compound, C₈H₁₁N₇S₂, the conformation about the N=N bond is trans and the thiadiazole rings are oriented at a dihedral angle of 2.92 (3)°. In the crystal structure, intermolecular N—H⋯S hydrogen bonds link the molecules into chains. There are π–π contacts between the thiadiazole rings [centroid-to-centroid distances = 3.699 (3) and 3.720 (2) Å].

Related literature

For general background, see: Bach et al. (1996 ); Clark & Hester (1991 ); Taniike et al. (1996 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₁₁N₇S₂
M_r = 269.36
Monoclinic, P 2₁ /c
a = 12.188 (2) Å
b = 9.1460 (18) Å
c = 12.790 (3) Å
β = 110.99 (3)°
V = 1331.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 294 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.926, T_max = 0.962
2431 measured reflections
2320 independent reflections
1468 reflections with I > 2σ(I)
R_int = 0.0047
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.178
S = 1.00
2320 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯S2ⁱ	0.86	2.84	3.631 (4)	154
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033941/hk2554sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033941/hk2554Isup2.hkl

checkCIF report

Comment top

The photophysical properties of azo compounds are of large interest in the development of nonlinear optical and optical data storage materials (Bach et al., 1996; Taniike et al., 1996; Clark & Hester, 1991). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (S1/N1/N2/C3/C4) and B (S2/N3/N4/C7/C8) are oriented at a dihedral angle of 2.92 (3)°. So, they are nearly coplanar.

In the crystal structure, intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contacts between the thiadiazole rings, Cg2···Cg2ⁱ and Cg2···Cg1ⁱⁱ [symmetry codes: (i) -x, 1 - y, -z; (ii) -x, -y, -z, where Cg1 and Cg2 are the centroids of the rings A (S1/N1/N2/C3/C4) and B (S2/N3/N4/C7/C8), respectively] may further stabilize the structure, with centroid–centroid distances of 3.699 (3) and 3.720 (2) Å, respectively.

Related literature top

For general background, see: Bach et al. (1996); Clark & Hester (1991); Taniike et al. (1996). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 5-amino-l,3,4-thiadiazole (5 mmol) was dissolved by heating in concentrated HCl (50 ml) in a water bath, after which the solution was cooled to 268 K and a solution of sodium nitrite (2.5 mmol) in water (3.5 ml) was added dropwise with stirring. The resulting bright-yellow diazonium solution was allowed to stand in ice for 30 min, after which a saturated solution of sodium acetate (100 ml, pH = 5) was added. The precipitate was removed by filtration, and purified by crystallization from toluene. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound.

5,5'-Diethyl-2,2'-(triazene-1,3-diyl)di-1,3,4-thiadiazole top

Crystal data top

C₈H₁₁N₇S₂	F(000) = 560
M_r = 269.36	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.188 (2) Å	θ = 9–12°
b = 9.1460 (18) Å	µ = 0.39 mm⁻¹
c = 12.790 (3) Å	T = 294 K
β = 110.99 (3)°	Block, yellow
V = 1331.1 (5) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1468 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.005
Graphite monochromator	θ_max = 25.3°, θ_min = 1.8°
ω/2θ scans	h = −14→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.926, T_max = 0.962	l = 0→14
2431 measured reflections	3 standard reflections every 120 min
2320 independent reflections	intensity decay: none

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.06P)² + 3.61P] where P = (F_o² + 2F_c²)/3
2320 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −1.06 e Å⁻³

Crystal data top

C₈H₁₁N₇S₂	V = 1331.1 (5) Å³
M_r = 269.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.188 (2) Å	µ = 0.39 mm⁻¹
b = 9.1460 (18) Å	T = 294 K
c = 12.790 (3) Å	0.20 × 0.10 × 0.10 mm
β = 110.99 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1468 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.005
T_min = 0.926, T_max = 0.962	3 standard reflections every 120 min
2431 measured reflections	intensity decay: none
2320 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.00	Δρ_max = 0.62 e Å⁻³
2320 reflections	Δρ_min = −1.06 e Å⁻³
142 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	1.26701 (14)	0.49714 (19)	0.57391 (10)	0.0675 (5)
S2	0.96258 (11)	0.18590 (15)	0.56999 (10)	0.0488 (4)
N1	1.3578 (5)	0.6450 (6)	0.4508 (4)	0.0804 (16)
N2	1.2634 (4)	0.5731 (5)	0.3737 (3)	0.0548 (11)
N3	0.7840 (4)	0.0373 (5)	0.4403 (3)	0.0554 (12)
N4	0.8301 (3)	0.1075 (5)	0.3694 (3)	0.0512 (11)
N5	0.9719 (4)	0.2610 (5)	0.3544 (3)	0.0515 (11)
H5A	0.9482	0.2556	0.2825	0.062*
N6	1.1099 (3)	0.4124 (5)	0.3558 (3)	0.0463 (10)
N7	1.0651 (3)	0.3422 (4)	0.4200 (3)	0.0417 (9)
C1	1.5073 (6)	0.6346 (8)	0.7641 (5)	0.092
H1B	1.5528	0.7039	0.8189	0.138*
H1C	1.5570	0.5558	0.7586	0.138*
H1D	1.4453	0.5968	0.7861	0.138*
C2	1.4558 (5)	0.7082 (7)	0.6535 (5)	0.073
H2A	1.5195	0.7411	0.6308	0.088*
H2B	1.4135	0.7943	0.6626	0.088*
C3	1.3715 (6)	0.6141 (9)	0.5586 (5)	0.090 (2)
C4	1.2070 (4)	0.4920 (6)	0.4245 (4)	0.0466 (12)
C5	0.7047 (6)	−0.0851 (8)	0.6080 (5)	0.0790 (19)
H5B	0.6879	−0.1221	0.6709	0.119*
H5C	0.7149	−0.1654	0.5640	0.119*
H5D	0.6406	−0.0251	0.5629	0.119*
C6	0.8141 (5)	0.0036 (7)	0.6486 (4)	0.0589 (14)
H6B	0.8787	−0.0567	0.6950	0.071*
H6C	0.8043	0.0837	0.6941	0.071*
C7	0.8436 (4)	0.0651 (6)	0.5493 (4)	0.0509 (13)
C8	0.9231 (4)	0.1912 (6)	0.4186 (4)	0.0465 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0757 (10)	0.0889 (12)	0.0315 (7)	−0.0236 (9)	0.0116 (6)	0.0029 (7)
S2	0.0510 (7)	0.0616 (8)	0.0329 (6)	−0.0063 (7)	0.0140 (5)	−0.0044 (6)
N1	0.073 (3)	0.099 (4)	0.062 (3)	−0.029 (3)	0.016 (3)	0.013 (3)
N2	0.053 (3)	0.066 (3)	0.043 (2)	−0.006 (2)	0.015 (2)	0.011 (2)
N3	0.045 (2)	0.074 (3)	0.049 (3)	−0.006 (2)	0.019 (2)	−0.012 (2)
N4	0.044 (2)	0.074 (3)	0.037 (2)	−0.005 (2)	0.0164 (19)	−0.010 (2)
N5	0.052 (3)	0.069 (3)	0.033 (2)	0.004 (2)	0.014 (2)	0.002 (2)
N6	0.049 (2)	0.057 (3)	0.032 (2)	−0.002 (2)	0.0141 (19)	0.0018 (19)
N7	0.038 (2)	0.049 (2)	0.036 (2)	0.0040 (18)	0.0114 (18)	−0.0001 (18)
C1	0.092	0.092	0.092	0.000	0.033	0.000
C2	0.073	0.073	0.073	0.000	0.026	0.000
C3	0.083 (4)	0.126 (6)	0.047 (3)	−0.045 (4)	0.008 (3)	0.010 (4)
C4	0.047 (3)	0.059 (3)	0.034 (2)	0.007 (3)	0.015 (2)	0.005 (2)
C5	0.084 (4)	0.095 (5)	0.065 (4)	−0.030 (4)	0.035 (3)	−0.004 (4)
C6	0.067 (3)	0.072 (4)	0.044 (3)	−0.019 (3)	0.029 (3)	−0.012 (3)
C7	0.048 (3)	0.061 (3)	0.043 (3)	−0.004 (3)	0.015 (2)	−0.010 (2)
C8	0.045 (3)	0.053 (3)	0.035 (2)	0.001 (2)	0.007 (2)	−0.006 (2)

Geometric parameters (Å, º) top

S1—C3	1.728 (6)	C1—H1B	0.9600
S1—C4	1.786 (5)	C1—H1C	0.9600
S2—C7	1.766 (5)	C1—H1D	0.9600
S2—C8	1.820 (5)	C2—C3	1.541 (8)
N1—N2	1.384 (6)	C2—H2A	0.9700
N1—C3	1.358 (7)	C2—H2B	0.9700
N2—C4	1.328 (6)	C4—N6	1.399 (6)
N3—N4	1.384 (6)	C5—C6	1.487 (7)
N3—C7	1.346 (6)	C5—H5B	0.9600
N4—C8	1.325 (6)	C5—H5C	0.9600
N5—N7	1.365 (5)	C5—H5D	0.9600
N5—C8	1.338 (6)	C6—C7	1.544 (7)
N5—H5A	0.8600	C6—H6B	0.9700
N6—N7	1.306 (5)	C6—H6C	0.9700
C1—C2	1.486 (7)

C3—S1—C4	86.0 (3)	N1—C3—S1	114.6 (5)
C7—S2—C8	88.1 (2)	C2—C3—S1	124.5 (5)
C3—N1—N2	113.1 (5)	N2—C4—N6	116.9 (4)
C4—N2—N1	111.2 (4)	N2—C4—S1	115.1 (4)
C7—N3—N4	113.3 (4)	N6—C4—S1	128.0 (4)
C8—N4—N3	115.8 (4)	C6—C5—H5B	109.5
N7—N5—H5A	125.1	C6—C5—H5C	109.5
C8—N5—N7	109.7 (4)	H5B—C5—H5C	109.5
C8—N5—H5A	125.1	C6—C5—H5D	109.5
N7—N6—C4	108.2 (4)	H5B—C5—H5D	109.5
N6—N7—N5	108.9 (4)	H5C—C5—H5D	109.5
C2—C1—H1B	109.5	C5—C6—C7	110.8 (4)
C2—C1—H1C	109.5	C5—C6—H6B	109.5
H1B—C1—H1C	109.5	C7—C6—H6B	109.5
C2—C1—H1D	109.5	C5—C6—H6C	109.5
H1B—C1—H1D	109.5	C7—C6—H6C	109.5
H1C—C1—H1D	109.5	H6B—C6—H6C	108.1
C1—C2—C3	115.6 (6)	N3—C7—C6	125.8 (5)
C1—C2—H2A	108.4	N3—C7—S2	112.5 (4)
C3—C2—H2A	108.4	C6—C7—S2	121.7 (4)
C1—C2—H2B	108.4	N4—C8—N5	118.5 (4)
C3—C2—H2B	108.4	N4—C8—S2	110.2 (4)
H2A—C2—H2B	107.4	N5—C8—S2	131.3 (4)
N1—C3—C2	119.3 (6)

C3—N1—N2—C4	1.1 (8)	N4—N3—C7—C6	179.9 (5)
N2—N1—C3—C2	−167.6 (6)	N4—N3—C7—S2	0.9 (6)
N2—N1—C3—S1	−1.5 (9)	C5—C6—C7—N3	−3.6 (8)
C1—C2—C3—N1	−153.7 (7)	C5—C6—C7—S2	175.3 (4)
C1—C2—C3—S1	41.7 (9)	C8—S2—C7—N3	−0.6 (4)
C4—S1—C3—N1	1.1 (6)	C8—S2—C7—C6	−179.6 (5)
C4—S1—C3—C2	166.4 (7)	N3—N4—C8—N5	179.6 (4)
C7—N3—N4—C8	−0.9 (6)	N3—N4—C8—S2	0.4 (5)
N1—N2—C4—N6	−179.5 (4)	N7—N5—C8—N4	179.4 (4)
N1—N2—C4—S1	−0.3 (6)	N7—N5—C8—S2	−1.6 (6)
C3—S1—C4—N2	−0.5 (5)	C7—S2—C8—N4	0.1 (4)
C3—S1—C4—N6	178.7 (5)	C7—S2—C8—N5	−178.9 (5)
N2—C4—N6—N7	−178.9 (4)	C4—N6—N7—N5	−178.5 (4)
S1—C4—N6—N7	1.9 (6)	C8—N5—N7—N6	−178.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···S2ⁱ	0.86	2.84	3.631 (4)	154

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₇S₂
M_r	269.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.188 (2), 9.1460 (18), 12.790 (3)
β (°)	110.99 (3)
V (Å³)	1331.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.926, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	2431, 2320, 1468
R_int	0.005
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.178, 1.00
No. of reflections	2320
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −1.06

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···S2ⁱ	0.86	2.84	3.631 (4)	154.00

Symmetry code: (i) x, −y+1/2, z−1/2.

References

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doi:10.1107/S1600536808033941

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