2,2'-Diamino-4,4'-bi-1,3-thia-zolium bis-(3-nitro-benzoate).

In the title salt, C(6)H(8)N(4)S(2) (2+)·2C(7)H(4)NO(4) (-), the diprotonated diamino-bithia-zole dication is located on an inversion center. The carboxyl-ate 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 carboxyl-ate functionality of the anion generate supra-molecular 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

C6H8N4S2 2+·2C7H4NO4 −

M = 532.51

Triclinic,

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[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.140

S = 1.08

1880 reflections

164 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.35 e Å−3

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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005856/bh2208sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H8N4S22+·2C7H4NO4−	Z = 1
Mr = 532.51	F(000) = 274
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0733P)2 + 0.0511P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
1880 reflections	Δρmax = 0.24 e Å−3
164 parameters	Δρmin = −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

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) .