2,2′-Diamino-4,4′-bi-1,3-thia­zolium bis­(3-nitro­benzoate)

Liu, B.-X.; Yu, Y.-P.; Lin, Y.-Y.; Du, M.

doi:10.1107/S1600536809005856

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o590

doi:10.1107/S1600536809005856

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2,2′-Diamino-4,4′-bi-1,3-thiazolium bis(3-nitrobenzoate)

Bing-Xin Liu,^a ^* Yan-Ping Yu,^a Yuan-Yuan Lin ^a and Mei Du ^a

^aDepartment of Chemistry, Shanghai University, People's Republic of China
^*Correspondence e-mail: r5744011@yahoo.com.cn

(Received 9 November 2008; accepted 18 February 2009; online 25 February 2009)

In the title salt, C₆H₈N₄S₂²⁺·2C₇H₄NO₄⁻, the diprotonated diaminobithiazole dication is located on an inversion center. The carboxylate group of the anion is twisted with respect to the benzene ring, with a dihedral angle of 13.6 (4)°. N—H⋯O hydrogen bonds involving the amino and ammonium groups of the dication and the carboxylate functionality of the anion generate supramolecular chains in the crystal.

Related literature

For applications of complexes including 2,2′-diamino-4,4′-bi-1,3-thiazole as ligand, see: Sun et al. (1997 ); Waring (1981 ); Fisher et al. (1985 ). For related structures, see: Liu et al. (2003 , 2005 ).

Experimental

Crystal data

C₆H₈N₄S₂²⁺·2C₇H₄NO₄⁻
M_r = 532.51
Triclinic, $[P \overline 1]$
a = 6.5670 (13) Å
b = 7.4538 (15) Å
c = 12.301 (2) Å
α = 74.747 (2)°
β = 89.721 (2)°
γ = 70.483 (2)°
V = 545.26 (19) Å³
Z = 1
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 295 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.940, T_max = 0.955
2771 measured reflections
1880 independent reflections
1325 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.140
S = 1.08
1880 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11A⋯O22	0.95	1.71	2.627 (4)	161
N12—H12B⋯O21	0.92	1.86	2.770 (4)	171
N12—H12A⋯O21ⁱ	0.90	2.08	2.830 (4)	140
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); 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: 10.1107/S1600536809005856/bh2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005856/bh2208Isup2.hkl

checkCIF report

Comment top

Transition metal complexes of 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown potential applications in the field of soft magnetic material (Sun et al., 1997) and biological activities, such as the effective inhibition of DNA synthesis in tumor cells (Waring, 1981; Fisher et al., 1985). As part of a serial structural investigation of metal complexes with DABT (Liu et al., 2003), while preparing the Mn^II complex of DABT, the title H₂DABT²⁺ salt was unexpectedly obtained, and its X-ray structure is presented here.

The structure of the title salt is shown in Fig. 1. The diprotonated DABT dication, H₂DABT, is located on an inversion center while the 3-nitrobenzoate anion is placed in general position. The H₂DABT moiety displays a trans planar configuration, which agrees with that found in the neutral DABT (Liu et al., 2003). The C—N(amino) bond length of 1.333 (4) Å is similar to the C—N(thiazole ring) bond length, 1.316 (4) Å, indicating electron delocalization between the amino and thiazole groups. It is notable that the protonated N atoms form hydrogen bonds to O atoms of carboxylate groups of 3-nitrobenzoate anions, to form supramolecular chains. This feature is consistent with those found in the H₂DABT salt formed with 2-nitrobenzoate, which we reported previously (Liu et al., 2005).

The carboxylate group of 3-nitrobenzoate anion is twisted with respect to the benzene plane, with a dihedral angle of 13.6 (4)°, which is comparable with 13.1 (2)° found in the 2-nitrobenzoate H₂DABT salt (Liu et al., 2005). This distortion allows the formation of the observed supramolecular structure (Fig. 2).

Related literature top

For applications of complexes including 2,2'-diamino-4,4'-bi-1,3-thiazole as ligand, see: Sun et al. (1997); Waring (1981); Fisher et al. (1985). For related structures, see: Liu et al. (2003, 2005).

Experimental top

An ethanol-water solution (1:1, 30 ml) of DABT (0.20 g, 1 mmol) and MnCl₂.4H₂O (0.20 g, 1 mmol) was mixed with another aqueous solution (10 ml) of 3-nitrobenzoic acid (0.33 g, 2 mmol) and NaOH (0.08 g, 2 mmol). The mixture was refluxed for 6 h. After cooling to room temperature, the solution was filtered. Yellow single crystals were obtained from the filtrate after 5 d.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); 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 molecular structure of the title salt, with 30% probability displacement ellipsoids (arbitrary spheres for H atoms), dashed lines showing the hydrogen bonding within the complex [symmetry code: (i) 2 - x,1 - y,1 - z].
	Fig. 2. The unit cell packing diagram showing hydrogen bondings between thiazole rings and carboxyl groups of 3-nitrobenzoate anions.

2,2'-Diamino-4,4'-bi-1,3-thiazolium bis(3-nitrobenzoate) top

Crystal data top

C₆H₈N₄S₂²⁺·2C₇H₄NO₄⁻	Z = 1
M_r = 532.51	F(000) = 274
Triclinic, P1	D_x = 1.622 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5670 (13) Å	Cell parameters from 1780 reflections
b = 7.4538 (15) Å	θ = 2.0–25.0°
c = 12.301 (2) Å	µ = 0.31 mm⁻¹
α = 74.747 (2)°	T = 295 K
β = 89.721 (2)°	Prism, yellow
γ = 70.483 (2)°	0.20 × 0.18 × 0.15 mm
V = 545.26 (19) Å³

Data collection top

Bruker APEXII diffractometer	1880 independent reflections
Radiation source: fine-focus sealed tube	1325 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
ω scans	h = −7→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −8→8
T_min = 0.940, T_max = 0.955	l = −14→12
2771 measured reflections

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)] = 0.051	H-atom parameters constrained
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0733P)² + 0.0511P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1880 reflections	Δρ_max = 0.24 e Å⁻³
164 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.013 (5)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₆H₈N₄S₂²⁺·2C₇H₄NO₄⁻	γ = 70.483 (2)°
M_r = 532.51	V = 545.26 (19) Å³
Triclinic, P1	Z = 1
a = 6.5670 (13) Å	Mo Kα radiation
b = 7.4538 (15) Å	µ = 0.31 mm⁻¹
c = 12.301 (2) Å	T = 295 K
α = 74.747 (2)°	0.20 × 0.18 × 0.15 mm
β = 89.721 (2)°

Data collection top

Bruker APEXII diffractometer	1880 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1325 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.955	R_int = 0.018
2771 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.08	Δρ_max = 0.24 e Å⁻³
1880 reflections	Δρ_min = −0.35 e Å⁻³
164 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N11	0.8309 (4)	0.3447 (4)	0.4956 (2)	0.0409 (7)
H11A	0.7922	0.3044	0.5705	0.049*
N12	0.6759 (5)	0.1415 (4)	0.4388 (2)	0.0573 (8)
H12A	0.6577	0.0819	0.3869	0.069*
H12B	0.5903	0.1378	0.4984	0.069*
S11	0.97982 (15)	0.25520 (13)	0.31830 (7)	0.0483 (3)
C12	1.0789 (5)	0.4030 (5)	0.3738 (2)	0.0398 (8)
H12	1.1856	0.4523	0.3432	0.048*
C11	0.9837 (5)	0.4382 (4)	0.4663 (2)	0.0358 (7)
C13	0.8101 (5)	0.2415 (5)	0.4254 (3)	0.0422 (8)
O21	0.4454 (4)	0.1470 (3)	0.62785 (19)	0.0555 (7)
O22	0.6468 (4)	0.2977 (4)	0.6861 (2)	0.0613 (7)
O23	0.3437 (6)	0.3196 (5)	1.1652 (2)	0.0933 (11)
O24	0.6375 (4)	0.2992 (4)	1.0836 (2)	0.0616 (7)
N21	0.4533 (6)	0.2964 (4)	1.0853 (2)	0.0539 (8)
C21	0.3836 (5)	0.2210 (4)	0.8031 (3)	0.0386 (7)
C22	0.4661 (5)	0.2654 (4)	0.8919 (3)	0.0395 (8)
H22	0.5923	0.2963	0.8868	0.047*
C23	0.3564 (5)	0.2627 (4)	0.9888 (3)	0.0419 (8)
C24	0.1652 (6)	0.2268 (5)	0.9973 (3)	0.0537 (9)
H24	0.0916	0.2314	1.0618	0.064*
C25	0.0836 (6)	0.1837 (5)	0.9081 (3)	0.0561 (10)
H25	−0.0461	0.1585	0.9124	0.067*
C26	0.1939 (5)	0.1776 (5)	0.8120 (3)	0.0474 (8)
H26	0.1403	0.1441	0.7532	0.057*
C27	0.5007 (5)	0.2205 (5)	0.6972 (3)	0.0429 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0525 (17)	0.0566 (16)	0.0301 (14)	−0.0364 (14)	0.0145 (12)	−0.0167 (13)
N12	0.078 (2)	0.081 (2)	0.0511 (18)	−0.0614 (18)	0.0273 (15)	−0.0379 (16)
S11	0.0631 (6)	0.0653 (6)	0.0383 (5)	−0.0408 (5)	0.0183 (4)	−0.0267 (4)
C12	0.0464 (19)	0.0569 (19)	0.0322 (17)	−0.0337 (16)	0.0140 (14)	−0.0186 (15)
C11	0.0422 (18)	0.0414 (17)	0.0304 (17)	−0.0233 (15)	0.0065 (13)	−0.0092 (14)
C13	0.051 (2)	0.0550 (19)	0.0349 (18)	−0.0319 (17)	0.0131 (15)	−0.0186 (16)
O21	0.0740 (17)	0.0766 (16)	0.0456 (14)	−0.0524 (14)	0.0194 (12)	−0.0322 (13)
O22	0.0789 (18)	0.0976 (19)	0.0507 (15)	−0.0702 (16)	0.0340 (13)	−0.0407 (14)
O23	0.124 (3)	0.138 (3)	0.0601 (19)	−0.078 (2)	0.0518 (18)	−0.057 (2)
O24	0.0703 (18)	0.0725 (17)	0.0531 (16)	−0.0340 (15)	0.0039 (13)	−0.0236 (13)
N21	0.076 (2)	0.0540 (18)	0.0406 (18)	−0.0319 (17)	0.0166 (16)	−0.0155 (14)
C21	0.0428 (19)	0.0377 (17)	0.0396 (18)	−0.0201 (15)	0.0107 (14)	−0.0099 (14)
C22	0.0401 (18)	0.0433 (17)	0.0429 (19)	−0.0228 (15)	0.0125 (14)	−0.0142 (15)
C23	0.0459 (19)	0.0469 (18)	0.0389 (19)	−0.0227 (16)	0.0132 (15)	−0.0132 (15)
C24	0.050 (2)	0.061 (2)	0.054 (2)	−0.0255 (19)	0.0257 (17)	−0.0140 (18)
C25	0.041 (2)	0.069 (2)	0.062 (3)	−0.0305 (19)	0.0158 (18)	−0.011 (2)
C26	0.043 (2)	0.053 (2)	0.051 (2)	−0.0274 (17)	0.0062 (16)	−0.0096 (17)
C27	0.051 (2)	0.0515 (19)	0.0365 (18)	−0.0282 (17)	0.0112 (15)	−0.0157 (16)

Geometric parameters (Å, º) top

N11—C13	1.333 (4)	O24—N21	1.217 (4)
N11—C11	1.398 (4)	N21—C23	1.466 (4)
N11—H11A	0.9526	C21—C22	1.383 (4)
N12—C13	1.316 (4)	C21—C26	1.384 (4)
N12—H12A	0.8973	C21—C27	1.510 (4)
N12—H12B	0.9215	C22—C23	1.388 (4)
S11—C13	1.726 (3)	C22—H22	0.9300
S11—C12	1.727 (3)	C23—C24	1.367 (5)
C12—C11	1.339 (4)	C24—C25	1.378 (5)
C12—H12	0.9300	C24—H24	0.9300
C11—C11ⁱ	1.456 (5)	C25—C26	1.386 (5)
O21—C27	1.242 (4)	C25—H25	0.9300
O22—C27	1.263 (4)	C26—H26	0.9300
O23—N21	1.230 (4)

C13—N11—C11	113.5 (2)	C22—C21—C27	119.8 (3)
C13—N11—H11A	116.6	C26—C21—C27	120.5 (3)
C11—N11—H11A	124.5	C21—C22—C23	118.6 (3)
C13—N12—H12A	120.5	C21—C22—H22	120.7
C13—N12—H12B	121.6	C23—C22—H22	120.7
H12A—N12—H12B	117.7	C24—C23—C22	122.3 (3)
C13—S11—C12	90.11 (14)	C24—C23—N21	119.6 (3)
C11—C12—S11	111.9 (2)	C22—C23—N21	118.1 (3)
C11—C12—H12	124.0	C23—C24—C25	118.6 (3)
S11—C12—H12	124.0	C23—C24—H24	120.7
C12—C11—N11	112.7 (3)	C25—C24—H24	120.7
C12—C11—C11ⁱ	128.3 (3)	C24—C25—C26	120.4 (3)
N11—C11—C11ⁱ	119.0 (3)	C24—C25—H25	119.8
N12—C13—N11	122.9 (3)	C26—C25—H25	119.8
N12—C13—S11	125.3 (2)	C21—C26—C25	120.3 (3)
N11—C13—S11	111.8 (2)	C21—C26—H26	119.8
O24—N21—O23	122.9 (3)	C25—C26—H26	119.8
O24—N21—C23	119.1 (3)	O21—C27—O22	125.3 (3)
O23—N21—C23	118.0 (3)	O21—C27—C21	118.0 (3)
C22—C21—C26	119.7 (3)	O22—C27—C21	116.7 (3)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O22	0.95	1.71	2.627 (4)	161
N12—H12B···O21	0.92	1.86	2.770 (4)	171
N12—H12A···O21ⁱⁱ	0.90	2.08	2.830 (4)	140

Symmetry code: (ii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₈N₄S₂²⁺·2C₇H₄NO₄⁻
M_r	532.51
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	6.5670 (13), 7.4538 (15), 12.301 (2)
α, β, γ (°)	74.747 (2), 89.721 (2), 70.483 (2)
V (Å³)	545.26 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.940, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	2771, 1880, 1325
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.140, 1.08
No. of reflections	1880
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.35

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altomare et al., 1993), 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
N11—H11A···O22	0.95	1.71	2.627 (4)	161
N12—H12B···O21	0.92	1.86	2.770 (4)	171
N12—H12A···O21ⁱ	0.90	2.08	2.830 (4)	140

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The project was supported by the Educational Development Foundation of Shanghai Educational Committee, China (No. AB0448).

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