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The title compound, C6H8N4S22+·C4H2O42−, consists of a di­amino­bi­thia­zole (DABT) cation and a fumarate anion. The cation and anion are both located on inversion centers. Both ions display a planar configuration and link to each other through hydrogen bonding between carboxyl and amino groups, as well as through weak C—H...O hydrogen bonding between thia­zole and carboxyl groups. The C—N(amino) bond distance of 1.323 (4) Å suggests the existence of electron delocalization between the thia­zole ring and the amino group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803010006/ww6084sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803010006/ww6084Isup2.hkl
Contains datablock I

CCDC reference: 214830

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.050
  • wR factor = 0.137
  • Data-to-parameter ratio = 14.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Transition metal complexes with 2,2'-diamine-4,4'-bithiazole (DABT) or its derivatives have shown interesting properties and potential application in any fields (Waring, 1981; Fisher et al., 1985). A series of metal complexes with BADT has been prepared in our laboratory (Liu et al., 2001). As a part of this investigation, the X-ray structure of the title BADT fumarate, (I), is presented here.

The structure of (I) is shown in Fig. 1 and consists of a protonated DABT cation and a fumarate anion, both being located around an individual crystallographic inversion center. The DABT cation displays a planar trans configuration, which agrees with that found in 2,2'-diamino-4,4'-1,3-thiazolium dichloride (Liu et al., 2002), but differs from the cis configuration found in DABT metal complexes (Tian et al., 1996; Liu et al., 2001). The N3—C2 distance of 1.333 (4) Å within the DABT cation is identical to the values of 1.335 (6) and 1.322 (3) Å found in the dichloride (Liu et al., 2002) and the CuII complex (Liu et al., 2001), respectively, but significantly longer than the distance of 1.309 (2) Å in the neutral DABT molecule (Liu et al., 2003). The N2—C2 bond distance of 1.323 (4) Å suggests the existence of the electron delocalization between the thiazole ring and the amino group.

The carboxyl groups of the fumarate anion are coplanar with the carbon skeleton, the maximum atomic deviation from the mean plane defined by all atoms of the fumarate being 0.0806 (14) Å (O1). The fumarate anions link with DABT cations through classic hydrogen bonding between the carboxyl and amino groups and weak C—H···O hydrogen bonding between the carboxyl and thiazole ring, forming a three-dimensional supramolecular structure, as shown in Fig. 2.

Experimental top

Fine crystals of DABT were obtained in the manner reported by Erlenmeyer (1948). Single crystals of (I) were obtained from an aqueous solution, as a by-product, during the preparation of a BADT complex of MnII bridged by fumarate.

Refinement top

Amine H atoms were located in a difference Fourier map and were included in the final cycles of refinement, with fixed positional parameters and Uiso of values of 0.04 Å2. Other H atoms were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å, and included in the final cycles of refinement as riding, with Uiso(H) = 1.2Ueq of the carrier atoms.

Computing details top

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), shown with 50% probability displacement ellipsoids, with dashed lines indicating the hydrogen bonding. [Symmetry codes: (i) 2 − x, −y, −z; (ii) −x, 1 − y, −z.]
[Figure 2] Fig. 2. A molecular packing of (I), with dashed lines showing the hydrogen bonding.
(I) top
Crystal data top
C6H8N4S22+·C4H2O42F(000) = 324
Mr = 314.34Dx = 1.750 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybcCell parameters from 3028 reflections
a = 5.2834 (17) Åθ = 3.2–26.5°
b = 7.936 (3) ŵ = 0.47 mm1
c = 14.370 (5) ÅT = 298 K
β = 98.164 (6)°Prism, colorless
V = 596.4 (4) Å30.32 × 0.28 × 0.20 mm
Z = 2
Data collection top
Rigaku R-AXIS-RAPID
diffractometer
1359 independent reflections
Radiation source: fine-focus sealed tube874 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.095
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 2.9°
ω scansh = 56
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 109
Tmin = 0.86, Tmax = 0.91l = 1818
3650 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.062P)2 + 0.0525P]
where P = (Fo2 + 2Fc2)/3
1359 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.68 e Å3
Crystal data top
C6H8N4S22+·C4H2O42V = 596.4 (4) Å3
Mr = 314.34Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.2834 (17) ŵ = 0.47 mm1
b = 7.936 (3) ÅT = 298 K
c = 14.370 (5) Å0.32 × 0.28 × 0.20 mm
β = 98.164 (6)°
Data collection top
Rigaku R-AXIS-RAPID
diffractometer
1359 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
874 reflections with I > 2σ(I)
Tmin = 0.86, Tmax = 0.91Rint = 0.095
3650 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.06Δρmax = 0.58 e Å3
1359 reflectionsΔρmin = 0.68 e Å3
91 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
xyzUiso*/Ueq
S10.99312 (15)0.11891 (9)0.21681 (5)0.0211 (3)
C70.0974 (6)0.4669 (4)0.0178 (2)0.0191 (7)
H70.10630.48400.08130.023*
C51.1150 (6)0.1190 (4)0.1112 (2)0.0190 (7)
H51.25370.18340.09900.023*
N20.6014 (5)0.0968 (3)0.22327 (17)0.0214 (6)
C20.7659 (6)0.0298 (3)0.1725 (2)0.0177 (7)
C40.9820 (6)0.0132 (4)0.04877 (19)0.0185 (7)
O10.4498 (4)0.2836 (3)0.00883 (15)0.0216 (5)
N30.7857 (5)0.0730 (3)0.08446 (16)0.0169 (6)
H30.68850.14610.05290.020*
C60.3048 (6)0.3654 (3)0.0386 (2)0.0181 (7)
O20.3233 (4)0.3637 (3)0.12609 (14)0.0229 (5)
H210.49600.16760.19950.040*
H220.58550.05930.27800.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0264 (5)0.0203 (4)0.0167 (4)0.0048 (3)0.0030 (3)0.0013 (3)
C70.028 (2)0.0133 (14)0.0161 (14)0.0003 (12)0.0019 (13)0.0011 (11)
C50.0217 (18)0.0178 (15)0.0182 (15)0.0029 (12)0.0055 (13)0.0022 (12)
N20.0276 (16)0.0204 (13)0.0168 (12)0.0047 (11)0.0054 (11)0.0026 (10)
C20.0210 (17)0.0133 (14)0.0177 (15)0.0008 (12)0.0010 (12)0.0015 (11)
C40.0181 (16)0.0172 (15)0.0195 (15)0.0033 (12)0.0000 (13)0.0028 (12)
O10.0218 (13)0.0212 (12)0.0219 (11)0.0045 (9)0.0040 (9)0.0020 (9)
N30.0190 (15)0.0153 (13)0.0162 (12)0.0023 (10)0.0016 (11)0.0003 (9)
C60.0244 (18)0.0118 (14)0.0188 (15)0.0035 (12)0.0054 (13)0.0012 (11)
O20.0248 (13)0.0242 (12)0.0186 (11)0.0071 (9)0.0004 (9)0.0006 (9)
Geometric parameters (Å, º) top
S1—C51.731 (3)N2—H210.829
S1—C21.738 (3)N2—H220.856
C7—C7i1.322 (6)C2—N31.330 (4)
C7—C61.501 (4)C4—N31.399 (4)
C7—H70.930C4—C4ii1.456 (6)
C5—C41.351 (4)O1—C61.273 (4)
C5—H50.930N3—H30.860
N2—C21.323 (4)C6—O21.248 (3)
C5—S1—C290.18 (14)N2—C2—S1123.0 (2)
C7i—C7—C6123.5 (3)N3—C2—S1112.3 (2)
C7i—C7—H7118.2C5—C4—N3113.8 (3)
C6—C7—H7118.2C5—C4—C4ii127.0 (4)
C4—C5—S1111.0 (2)N3—C4—C4ii119.2 (3)
C4—C5—H5124.5C2—N3—C4112.7 (3)
S1—C5—H5124.5C2—N3—H3123.7
C2—N2—H21120.0C4—N3—H3123.7
C2—N2—H22121.6O2—C6—O1124.5 (3)
H21—N2—H22117.8O2—C6—C7119.8 (3)
N2—C2—N3124.6 (3)O1—C6—C7115.7 (2)
Symmetry codes: (i) x, y+1, z; (ii) x+2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H21···O20.832.022.831 (3)164
N2—H22···O2iii0.862.092.832 (3)145
N3—H3···O10.861.802.658 (3)172
C5—H5···O1ii0.932.313.181 (4)155
Symmetry codes: (ii) x+2, y, z; (iii) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H8N4S22+·C4H2O42
Mr314.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)5.2834 (17), 7.936 (3), 14.370 (5)
β (°) 98.164 (6)
V3)596.4 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.32 × 0.28 × 0.20
Data collection
DiffractometerRigaku R-AXIS-RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.86, 0.91
No. of measured, independent and
observed [I > 2σ(I)] reflections
3650, 1359, 874
Rint0.095
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.137, 1.06
No. of reflections1359
No. of parameters91
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.58, 0.68

Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC and Rigaku, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and XP (Siemens, 1994), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H21···O20.832.022.831 (3)164
N2—H22···O2i0.862.092.832 (3)145
N3—H3···O10.861.802.658 (3)172
C5—H5···O1ii0.932.313.181 (4)155
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+2, y, z.
 

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