Crystals of the title chiral compound, C6H8N4S22+·C4H4O62−, were obtained from a solution containing diaminobithiazole (DABT) and racemic tartaric acid. The crystal structure consists of a protonated DABT dications (H2DABT) and (2R,3R)-tartrate dianions linked via hydrogen bonding. An overlapped arrangement and a centroid-to-centroid separation of 3.4620 (11) Å between nearly parallel thiazole rings of adjacent H2DABT cations indicate the existence of π–π stacking in the crystal structure.
Supporting information
CCDC reference: 269892
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.076
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ?
PLAT322_ALERT_2_C Check Hybridisation of S2 in Main Residue . ?
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.50
From the CIF: _reflns_number_total 3030
Count of symmetry unique reflns 1750
Completeness (_total/calc) 173.14%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1280
Fraction of Friedel pairs measured 0.731
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 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); software used to prepare material for publication: WinGX (Farrugia, 1999).
2,2'-Diamino-4,4'-bi-1,3-thiazolium (2
R,3
R)-tartrate
top
Crystal data top
C6H8N4S22+·C4H4O62− | Dx = 1.755 Mg m−3 |
Mr = 348.36 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P3221 | Cell parameters from 3278 reflections |
Hall symbol: P 32 2" | θ = 2.5–26.0° |
a = 11.0122 (7) Å | µ = 0.44 mm−1 |
c = 18.8285 (14) Å | T = 295 K |
V = 1977.4 (2) Å3 | Prism, yellow |
Z = 6 | 0.40 × 0.33 × 0.31 mm |
F(000) = 1080 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 3030 independent reflections |
Radiation source: fine-focus sealed tube | 2895 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.835, Tmax = 0.878 | l = −24→23 |
18080 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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0407P)2 + 0.5513P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3030 reflections | Δρmax = 0.18 e Å−3 |
199 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1280 Friedel Pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (6) |
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 | Uiso*/Ueq | |
S1 | 0.19828 (6) | −0.07871 (5) | 0.39358 (3) | 0.03867 (12) | |
S2 | 0.09436 (6) | 0.45087 (5) | 0.43278 (3) | 0.04235 (13) | |
N1 | 0.31206 (17) | 0.18704 (18) | 0.39482 (8) | 0.0321 (3) | |
H1 | 0.3775 | 0.2771 | 0.3944 | 0.050* | |
N2 | 0.4722 (2) | 0.1122 (2) | 0.37104 (10) | 0.0463 (4) | |
H2A | 0.5046 | 0.0591 | 0.3737 | 0.050* | |
H2B | 0.5417 | 0.2014 | 0.3622 | 0.050* | |
N3 | −0.02272 (17) | 0.18381 (16) | 0.42103 (8) | 0.0304 (3) | |
H3 | −0.0855 | 0.0956 | 0.4239 | 0.050* | |
N4 | −0.1839 (2) | 0.2604 (2) | 0.43696 (10) | 0.0447 (4) | |
H4A | −0.2475 | 0.1756 | 0.4413 | 0.050* | |
H4B | −0.2084 | 0.3155 | 0.4542 | 0.050* | |
C1 | 0.3440 (2) | 0.0869 (2) | 0.38547 (10) | 0.0340 (4) | |
C2 | 0.0946 (2) | −0.0043 (2) | 0.40895 (10) | 0.0338 (4) | |
H2 | −0.0014 | −0.0553 | 0.4175 | 0.041* | |
C3 | 0.17032 (19) | 0.1364 (2) | 0.40704 (9) | 0.0293 (4) | |
C4 | −0.0545 (2) | 0.2844 (2) | 0.43048 (10) | 0.0328 (4) | |
C5 | 0.1990 (2) | 0.3756 (2) | 0.42163 (11) | 0.0394 (4) | |
H5 | 0.2964 | 0.4259 | 0.4197 | 0.047* | |
C6 | 0.1211 (2) | 0.2354 (2) | 0.41610 (9) | 0.0301 (4) | |
O1 | 0.97093 (16) | 0.61372 (17) | 0.58530 (9) | 0.0443 (4) | |
O2 | 0.92489 (16) | 0.78120 (15) | 0.55299 (8) | 0.0430 (3) | |
O3 | 0.52424 (16) | 0.44140 (17) | 0.42107 (9) | 0.0464 (4) | |
O4 | 0.66525 (16) | 0.40504 (17) | 0.35003 (8) | 0.0474 (4) | |
O5 | 0.72860 (16) | 0.40769 (14) | 0.53231 (7) | 0.0389 (3) | |
H5A | 0.7624 | 0.4069 | 0.5803 | 0.050* | |
O6 | 0.89572 (15) | 0.58660 (18) | 0.41414 (8) | 0.0449 (4) | |
H6A | 0.8747 | 0.5461 | 0.3714 | 0.050* | |
C7 | 0.8974 (2) | 0.6547 (2) | 0.55649 (10) | 0.0332 (4) | |
C8 | 0.75943 (19) | 0.54780 (19) | 0.52094 (10) | 0.0306 (4) | |
H8 | 0.6829 | 0.5588 | 0.5404 | 0.037* | |
C9 | 0.7704 (2) | 0.5772 (2) | 0.44086 (10) | 0.0330 (4) | |
H9 | 0.7757 | 0.6677 | 0.4334 | 0.040* | |
C10 | 0.6418 (2) | 0.4645 (2) | 0.40095 (10) | 0.0348 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0430 (3) | 0.0349 (2) | 0.0427 (2) | 0.0230 (2) | −0.0002 (2) | −0.0040 (2) |
S2 | 0.0391 (3) | 0.0310 (2) | 0.0589 (3) | 0.0190 (2) | 0.0031 (2) | −0.0006 (2) |
N1 | 0.0312 (8) | 0.0334 (8) | 0.0331 (7) | 0.0173 (7) | 0.0001 (6) | −0.0004 (6) |
N2 | 0.0377 (10) | 0.0488 (11) | 0.0605 (11) | 0.0276 (9) | 0.0013 (8) | −0.0038 (9) |
N3 | 0.0290 (8) | 0.0288 (8) | 0.0329 (7) | 0.0141 (7) | 0.0020 (6) | 0.0002 (6) |
N4 | 0.0357 (9) | 0.0409 (10) | 0.0627 (11) | 0.0230 (8) | 0.0032 (8) | −0.0025 (9) |
C1 | 0.0353 (10) | 0.0418 (10) | 0.0301 (9) | 0.0232 (9) | −0.0026 (7) | −0.0026 (8) |
C2 | 0.0336 (10) | 0.0359 (10) | 0.0345 (8) | 0.0194 (8) | 0.0001 (7) | −0.0028 (8) |
C3 | 0.0291 (9) | 0.0355 (10) | 0.0250 (8) | 0.0174 (8) | 0.0004 (7) | −0.0015 (7) |
C4 | 0.0321 (10) | 0.0323 (9) | 0.0350 (9) | 0.0169 (8) | 0.0012 (7) | 0.0017 (7) |
C5 | 0.0344 (10) | 0.0379 (11) | 0.0486 (11) | 0.0201 (9) | 0.0034 (9) | 0.0007 (9) |
C6 | 0.0313 (9) | 0.0332 (9) | 0.0287 (8) | 0.0183 (8) | 0.0018 (7) | 0.0009 (7) |
O1 | 0.0416 (8) | 0.0422 (8) | 0.0526 (8) | 0.0236 (7) | −0.0082 (7) | 0.0044 (7) |
O2 | 0.0384 (8) | 0.0278 (7) | 0.0620 (9) | 0.0159 (6) | −0.0121 (7) | −0.0051 (7) |
O3 | 0.0307 (7) | 0.0453 (9) | 0.0625 (9) | 0.0185 (7) | −0.0058 (7) | −0.0131 (7) |
O4 | 0.0433 (9) | 0.0498 (9) | 0.0433 (7) | 0.0189 (7) | 0.0004 (7) | −0.0103 (7) |
O5 | 0.0484 (9) | 0.0269 (7) | 0.0384 (7) | 0.0164 (6) | 0.0003 (6) | 0.0015 (5) |
O6 | 0.0320 (8) | 0.0627 (11) | 0.0382 (7) | 0.0224 (8) | 0.0030 (6) | 0.0014 (7) |
C7 | 0.0343 (9) | 0.0328 (10) | 0.0338 (8) | 0.0178 (8) | −0.0001 (8) | 0.0001 (7) |
C8 | 0.0286 (9) | 0.0274 (9) | 0.0360 (8) | 0.0142 (7) | 0.0013 (7) | −0.0009 (7) |
C9 | 0.0292 (9) | 0.0329 (9) | 0.0364 (8) | 0.0152 (8) | −0.0004 (7) | 0.0030 (7) |
C10 | 0.0347 (10) | 0.0326 (9) | 0.0382 (9) | 0.0177 (8) | −0.0019 (8) | 0.0017 (8) |
Geometric parameters (Å, º) top
S1—C1 | 1.731 (2) | C2—H2 | 0.9300 |
S1—C2 | 1.730 (2) | C3—C6 | 1.451 (3) |
S2—C4 | 1.745 (2) | C5—C6 | 1.344 (3) |
S2—C5 | 1.735 (2) | C5—H5 | 0.9300 |
N1—C1 | 1.326 (3) | O1—C7 | 1.233 (2) |
N1—C3 | 1.389 (2) | O2—C7 | 1.270 (2) |
N1—H1 | 0.8880 | O3—C10 | 1.247 (3) |
N2—C1 | 1.324 (3) | O4—C10 | 1.259 (2) |
N2—H2A | 0.8246 | O5—C8 | 1.421 (2) |
N2—H2B | 0.9094 | O5—H5A | 0.9798 |
N3—C4 | 1.330 (3) | O6—C9 | 1.423 (2) |
N3—C6 | 1.392 (2) | O6—H6A | 0.8935 |
N3—H3 | 0.8673 | C7—C8 | 1.534 (3) |
N4—C4 | 1.319 (3) | C8—C9 | 1.534 (2) |
N4—H4A | 0.8464 | C8—H8 | 0.9800 |
N4—H4B | 0.8423 | C9—C10 | 1.534 (3) |
C2—C3 | 1.343 (3) | C9—H9 | 0.9800 |
| | | |
C1—S1—C2 | 90.0 (1) | C6—C5—S2 | 111.27 (15) |
C4—S2—C5 | 89.7 (1) | C6—C5—H5 | 124.4 |
C1—N1—C3 | 113.56 (17) | S2—C5—H5 | 124.4 |
C1—N1—H1 | 121.6 | C5—C6—N3 | 113.98 (16) |
C3—N1—H1 | 124.8 | C5—C6—C3 | 127.51 (18) |
C1—N2—H2A | 129.3 | N3—C6—C3 | 118.50 (17) |
C1—N2—H2B | 119.9 | C8—O5—H5A | 105.3 |
H2A—N2—H2B | 110.4 | C9—O6—H6A | 106.4 |
C4—N3—C6 | 112.81 (16) | O1—C7—O2 | 125.74 (19) |
C4—N3—H3 | 122.0 | O1—C7—C8 | 119.36 (17) |
C6—N3—H3 | 124.6 | O2—C7—C8 | 114.90 (16) |
C4—N4—H4A | 116.4 | O5—C8—C7 | 112.04 (15) |
C4—N4—H4B | 126.5 | O5—C8—C9 | 109.13 (15) |
H4A—N4—H4B | 111.8 | C7—C8—C9 | 108.87 (15) |
N2—C1—N1 | 123.4 (2) | O5—C8—H8 | 108.9 |
N2—C1—S1 | 124.67 (17) | C7—C8—H8 | 108.9 |
N1—C1—S1 | 111.90 (15) | C9—C8—H8 | 108.9 |
C3—C2—S1 | 111.43 (15) | O6—C9—C10 | 110.84 (16) |
C3—C2—H2 | 124.3 | O6—C9—C8 | 109.55 (15) |
S1—C2—H2 | 124.3 | C10—C9—C8 | 111.55 (16) |
C2—C3—N1 | 113.12 (17) | O6—C9—H9 | 108.3 |
C2—C3—C6 | 127.88 (18) | C10—C9—H9 | 108.3 |
N1—C3—C6 | 119.00 (17) | C8—C9—H9 | 108.3 |
N4—C4—N3 | 123.6 (2) | O3—C10—O4 | 126.0 (2) |
N4—C4—S2 | 124.15 (17) | O3—C10—C9 | 117.46 (18) |
N3—C4—S2 | 112.24 (14) | O4—C10—C9 | 116.55 (18) |
| | | |
C3—N1—C1—N2 | 177.93 (18) | C4—N3—C6—C3 | 178.86 (15) |
C3—N1—C1—S1 | −1.5 (2) | C2—C3—C6—C5 | 172.3 (2) |
C2—S1—C1—N2 | −178.76 (18) | N1—C3—C6—C5 | −7.6 (3) |
C2—S1—C1—N1 | 0.65 (15) | C2—C3—C6—N3 | −6.6 (3) |
C1—S1—C2—C3 | 0.36 (15) | N1—C3—C6—N3 | 173.50 (16) |
S1—C2—C3—N1 | −1.3 (2) | O1—C7—C8—O5 | 5.4 (2) |
S1—C2—C3—C6 | 178.81 (14) | O2—C7—C8—O5 | −174.63 (17) |
C1—N1—C3—C2 | 1.8 (2) | O1—C7—C8—C9 | −115.40 (19) |
C1—N1—C3—C6 | −178.26 (15) | O2—C7—C8—C9 | 64.6 (2) |
C6—N3—C4—N4 | −179.65 (18) | O5—C8—C9—O6 | −71.6 (2) |
C6—N3—C4—S2 | 0.7 (2) | C7—C8—C9—O6 | 50.9 (2) |
C5—S2—C4—N4 | 179.55 (19) | O5—C8—C9—C10 | 51.5 (2) |
C5—S2—C4—N3 | −0.79 (16) | C7—C8—C9—C10 | 174.05 (15) |
C4—S2—C5—C6 | 0.68 (16) | O6—C9—C10—O3 | 177.16 (18) |
S2—C5—C6—N3 | −0.4 (2) | C8—C9—C10—O3 | 54.8 (2) |
S2—C5—C6—C3 | −179.37 (14) | O6—C9—C10—O4 | −3.7 (2) |
C4—N3—C6—C5 | −0.2 (2) | C8—C9—C10—O4 | −126.08 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3 | 0.89 | 1.79 | 2.647 (2) | 161 |
N2—H2A···O1i | 0.82 | 2.04 | 2.819 (3) | 158 |
N2—H2B···O4 | 0.91 | 1.97 | 2.867 (3) | 169 |
N3—H3···O2ii | 0.87 | 1.77 | 2.622 (2) | 169 |
N4—H4A···O1ii | 0.85 | 2.05 | 2.864 (2) | 160 |
N4—H4B···O5iii | 0.84 | 2.09 | 2.889 (3) | 157 |
O5—H5A···O4iv | 0.98 | 2.06 | 2.975 (2) | 154 |
O6—H6A···O4 | 0.89 | 2.08 | 2.612 (2) | 118 |
C2—H2···O2ii | 0.93 | 2.36 | 3.216 (3) | 153 |
C5—H5···O3 | 0.93 | 2.43 | 3.280 (3) | 152 |
C8—H8···O3v | 0.98 | 2.59 | 3.552 (3) | 165 |
Symmetry codes: (i) y, x−1, −z+1; (ii) y−1, x−1, −z+1; (iii) x−1, y, z; (iv) −x+y+1, −x+1, z+1/3; (v) y, x, −z+1. |