N,N′-Bis(1,3-thia­zol-2-yl)methyl­ene­diamine

Salimi, F.; Sahebalzamani, H.; Maleki, M.; Notash, B.

doi:10.1107/S1600536811047659

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3320

https://doi.org/10.1107/S1600536811047659

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N,N′-Bis(1,3-thiazol-2-yl)methylenediamine

Farshid Salimi,^a ^* Hajar Sahebalzamani,^a Masume Maleki ^a and Behrouz Notash ^b

^aDepartment of Chemistry, Faculty of Science, Ardabil Branch, Islamic Azad University, Ardabil, Iran, and ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: salimif@yahoo.com

(Received 5 November 2011; accepted 10 November 2011; online 16 November 2011)

In the title compound, C₇H₈N₄S₂, the dihedral angle between the thiazoline rings is 71.25 (13)°. In the crystal, intermolecular N—H⋯N hydrogen bonds connect the molecules into zigzag chains parallel to the ab plane.

Related literature

For applications of thiazole compounds see: Raman et al. (2000 ); Karimian (2009 ); Shi et al. (1996 ). For related structures containing an aminothiazole moiety, see: Odabaşoğlu & Büyükgüngör, (2006 ); Zhao et al. (2006 ).

Experimental

Crystal data

C₇H₈N₄S₂
M_r = 212.31
Monoclinic, P 2₁ /n
a = 7.8598 (16) Å
b = 8.9291 (18) Å
c = 13.672 (3) Å
β = 96.39 (3)°
V = 953.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 298 K
0.45 × 0.35 × 0.3 mm

Data collection

Stoe IPDS 2T diffractometer
7352 measured reflections
2551 independent reflections
1544 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.162
S = 1.10
2551 reflections
126 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.85 (2)	2.07 (2)	2.918 (4)	171 (4)
N3—H3A⋯N4ⁱⁱ	0.85 (2)	2.07 (2)	2.919 (3)	179 (4)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-RED; 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 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811047659/bt5707sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047659/bt5707Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811047659/bt5707Isup3.cml

checkCIF report

Comment top

The thiazole ring and its derivatives are of great importance in biological systems due to their vast range of biological activities such as anti-inflammatory, analgesic and antipyretic (Raman et al., 2000; Karimian, 2009), especially against certain breast carcinoma cell lines (Shi et al. 1996).

The asymmetric unit of the title compound (Fig. 1) is composed of one N,N'-bis(2-thiazol-yl)methylenediamin molecule. Bond lengths are in the normal range of thiazole compounds (Odabaşoğlu & Büyükgüngör, 2006; Zhao, et al. 2006). The crystal structure is stabilized by intermolecular N—H···N hydrogen bonds, which link the molecules into zigzag chains (Table 1 & Fig. 2).

Related literature top

For applications of thiazole compounds see: Raman et al. (2000); Karimian (2009); Shi et al. (1996). For related structures containing an aminothiazole moiety, see: Odabaşoğlu & Büyükgüngör, (2006); Zhao et al. (2006).

Experimental top

A mixture of formaldehyde (5 mmol) and 2-aminothiazole (10 mmol) and formic acid (0.88 mmol) was added with stirring at room temperature for 24 hrs.The resulting yellow solid was filtered and washed with cold acetonitrile. Single crystals of the title compound were obtained by recrystallization of the colorless solid from acetonitrile.

Structure description top

For applications of thiazole compounds see: Raman et al. (2000); Karimian (2009); Shi et al. (1996). For related structures containing an aminothiazole moiety, see: Odabaşoğlu & Büyükgüngör, (2006); Zhao et al. (2006).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title compound. The intermolecular N—H···N hydrogen bonds are shown as green dashed lines.

N,N'-Bis(1,3-thiazol-2-yl)methylenediamine top

Crystal data top

C₇H₈N₄S₂	F(000) = 440
M_r = 212.31	D_x = 1.479 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2551 reflections
a = 7.8598 (16) Å	θ = 2.9–29.2°
b = 8.9291 (18) Å	µ = 0.52 mm⁻¹
c = 13.672 (3) Å	T = 298 K
β = 96.39 (3)°	Block, colorless
V = 953.6 (3) Å³	0.45 × 0.35 × 0.3 mm
Z = 4

Data collection top

Stoe IPDS 2T diffractometer	1544 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.055
Graphite monochromator	θ_max = 29.2°, θ_min = 2.9°
Detector resolution: 0.15 mm pixels mm^-1	h = −10→10
rotation method scans	k = −10→12
7352 measured reflections	l = −18→16
2551 independent reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0781P)²] where P = (F_o² + 2F_c²)/3
2551 reflections	(Δ/σ)_max < 0.001
126 parameters	Δρ_max = 0.35 e Å⁻³
2 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₇H₈N₄S₂	V = 953.6 (3) Å³
M_r = 212.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.8598 (16) Å	µ = 0.52 mm⁻¹
b = 8.9291 (18) Å	T = 298 K
c = 13.672 (3) Å	0.45 × 0.35 × 0.3 mm
β = 96.39 (3)°

Data collection top

Stoe IPDS 2T diffractometer	1544 reflections with I > 2σ(I)
7352 measured reflections	R_int = 0.055
2551 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	2 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.35 e Å⁻³
2551 reflections	Δρ_min = −0.33 e Å⁻³
126 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	0.17187 (10)	0.85527 (11)	0.66273 (7)	0.0600 (3)
S2	0.38487 (10)	0.58898 (11)	0.36382 (7)	0.0638 (3)
N2	0.2786 (3)	0.9024 (3)	0.4824 (2)	0.0534 (7)
N3	0.1223 (3)	0.6689 (3)	0.4651 (2)	0.0517 (7)
N4	0.1924 (3)	0.4157 (3)	0.4539 (2)	0.0503 (6)
C1	0.3071 (4)	0.9249 (3)	0.5804 (2)	0.0458 (7)
C5	0.2187 (3)	0.5568 (3)	0.4343 (2)	0.0445 (6)
N1	0.4391 (3)	0.9984 (3)	0.6235 (2)	0.0540 (7)
C3	0.4335 (4)	1.0032 (4)	0.7244 (3)	0.0609 (9)
H3	0.5177	1.0521	0.7658	0.073*
C4	0.1332 (4)	0.8213 (4)	0.4347 (3)	0.0543 (8)
H4A	0.0294	0.8727	0.4476	0.065*
H4B	0.1386	0.8234	0.3642	0.065*
C6	0.3067 (4)	0.3273 (4)	0.4103 (3)	0.0596 (9)
H6	0.3066	0.2236	0.4161	0.072*
C2	0.3025 (4)	0.9349 (5)	0.7596 (3)	0.0663 (10)
H2	0.2841	0.9306	0.8255	0.080*
C7	0.4177 (4)	0.3987 (4)	0.3592 (3)	0.0637 (9)
H7	0.5004	0.3523	0.3261	0.076*
H3A	0.031 (3)	0.645 (4)	0.489 (2)	0.053 (9)*
H2A	0.358 (4)	0.924 (5)	0.447 (3)	0.084 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0549 (4)	0.0643 (6)	0.0650 (5)	−0.0030 (4)	0.0247 (4)	0.0069 (4)
S2	0.0533 (5)	0.0637 (6)	0.0801 (6)	−0.0071 (4)	0.0333 (4)	−0.0008 (5)
N2	0.0617 (15)	0.0475 (16)	0.0529 (16)	−0.0179 (12)	0.0145 (12)	0.0007 (12)
N3	0.0445 (13)	0.0392 (15)	0.0749 (18)	−0.0073 (10)	0.0228 (12)	−0.0046 (12)
N4	0.0464 (13)	0.0423 (15)	0.0648 (17)	−0.0020 (10)	0.0173 (11)	0.0001 (12)
C1	0.0502 (15)	0.0326 (15)	0.0568 (18)	0.0012 (11)	0.0156 (13)	0.0033 (13)
C5	0.0365 (12)	0.0482 (17)	0.0498 (16)	−0.0050 (11)	0.0098 (11)	−0.0066 (14)
N1	0.0539 (15)	0.0482 (16)	0.0615 (16)	−0.0081 (11)	0.0131 (12)	−0.0041 (13)
C3	0.0624 (19)	0.066 (2)	0.0543 (19)	0.0030 (16)	0.0080 (15)	−0.0124 (16)
C4	0.0527 (16)	0.0458 (18)	0.065 (2)	−0.0034 (13)	0.0072 (14)	0.0001 (15)
C6	0.0561 (16)	0.0466 (19)	0.078 (2)	0.0090 (14)	0.0169 (15)	−0.0049 (17)
C2	0.067 (2)	0.084 (3)	0.0508 (19)	0.0105 (18)	0.0172 (16)	−0.0026 (18)
C7	0.0522 (17)	0.067 (2)	0.075 (2)	0.0116 (15)	0.0218 (16)	−0.0061 (18)

Geometric parameters (Å, º) top

S1—C2	1.735 (4)	N4—C6	1.380 (4)
S1—C1	1.746 (3)	C1—N1	1.311 (4)
S2—C7	1.721 (4)	N1—C3	1.385 (5)
S2—C5	1.731 (3)	C3—C2	1.332 (5)
N2—C1	1.349 (4)	C3—H3	0.9300
N2—C4	1.446 (4)	C4—H4A	0.9700
N2—H2A	0.850 (19)	C4—H4B	0.9700
N3—C5	1.351 (4)	C6—C7	1.338 (5)
N3—C4	1.428 (4)	C6—H6	0.9300
N3—H3A	0.850 (18)	C2—H2	0.9300
N4—C5	1.309 (4)	C7—H7	0.9300

C2—S1—C1	89.70 (17)	C2—C3—H3	121.4
C7—S2—C5	88.96 (16)	N1—C3—H3	121.4
C1—N2—C4	123.9 (3)	N3—C4—N2	114.6 (3)
C1—N2—H2A	118 (3)	N3—C4—H4A	108.6
C4—N2—H2A	117 (3)	N2—C4—H4A	108.6
C5—N3—C4	124.1 (3)	N3—C4—H4B	108.6
C5—N3—H3A	117 (2)	N2—C4—H4B	108.6
C4—N3—H3A	116 (2)	H4A—C4—H4B	107.6
C5—N4—C6	109.7 (3)	C7—C6—N4	116.5 (3)
N1—C1—N2	123.8 (3)	C7—C6—H6	121.7
N1—C1—S1	113.4 (2)	N4—C6—H6	121.7
N2—C1—S1	122.8 (2)	C3—C2—S1	109.1 (3)
N4—C5—N3	122.8 (2)	C3—C2—H2	125.4
N4—C5—S2	114.8 (2)	S1—C2—H2	125.4
N3—C5—S2	122.3 (2)	C6—C7—S2	110.0 (2)
C1—N1—C3	110.6 (3)	C6—C7—H7	125.0
C2—C3—N1	117.2 (3)	S2—C7—H7	125.0

C4—N2—C1—N1	179.9 (3)	N2—C1—N1—C3	179.9 (3)
C4—N2—C1—S1	1.1 (4)	S1—C1—N1—C3	−1.1 (3)
C2—S1—C1—N1	1.1 (3)	C1—N1—C3—C2	0.5 (5)
C2—S1—C1—N2	−179.9 (3)	C5—N3—C4—N2	−77.4 (4)
C6—N4—C5—N3	178.0 (3)	C1—N2—C4—N3	−60.5 (4)
C6—N4—C5—S2	−0.9 (4)	C5—N4—C6—C7	0.3 (5)
C4—N3—C5—N4	−171.6 (3)	N1—C3—C2—S1	0.3 (4)
C4—N3—C5—S2	7.2 (5)	C1—S1—C2—C3	−0.8 (3)
C7—S2—C5—N4	1.0 (3)	N4—C6—C7—S2	0.4 (5)
C7—S2—C5—N3	−177.9 (3)	C5—S2—C7—C6	−0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.85 (2)	2.07 (2)	2.918 (4)	171 (4)
N3—H3A···N4ⁱⁱ	0.85 (2)	2.07 (2)	2.919 (3)	179 (4)

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

Experimental details

Crystal data
Chemical formula	C₇H₈N₄S₂
M_r	212.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.8598 (16), 8.9291 (18), 13.672 (3)
β (°)	96.39 (3)
V (Å³)	953.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.45 × 0.35 × 0.3

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7352, 2551, 1544
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.162, 1.10
No. of reflections	2551
No. of parameters	126
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.33

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.850 (19)	2.07 (2)	2.918 (4)	171 (4)
N3—H3A···N4ⁱⁱ	0.850 (18)	2.070 (18)	2.919 (3)	179 (4)

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

Acknowledgements

We are grateful to the Islamic Azad University, Ardabil Branch, for financial support.

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