Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102007722/sk1545sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102007722/sk1545IIIsup2.hkl |
CCDC reference: 188631
The synthesis of (II) was carried out according to the method of Hünig et al. (1964). To a solution of 5-(ethoxycarbonyl)-2-(ethylthio)-3,4-dimethyl-1,3-thiazolium tetrafluoroborate, (I) (1.00 g, 3 mmol), in acetonitrile (5 ml) and ethanol (5 ml), hydrazine hydrate (0.073 ml, 1.5 mmol) and triethylamine (0.84 ml, 6 mmol) were added. The mixture was strirred under an inert athmosphere at room temperature for 1 h. The yellow precipitate which formed was filtered off, washed with ethanol and recrystallized from acetonitrile to give donor (II) in 70% yield [m.p. 535 K]. Spectroscopic analysis: 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 1.33 (t, 6H), 2.53 (s, 6H), 3.40 (s, 6H), 4.25 (q, 4H); elemental analysis, found (calculated): C 48.30 (48.23), H 5.57 (5.56), N 14.09 (14.06), S 16.21 (16.09)%. Cyclic voltammetry measurements were carried out in Bu4NPF6 as the supporting electrolyte at room temperature in CH2Cl2, versus SCE (please define). The title complex was prepared by mixing a hot acetonitrile solution of TCNQ (0.042 g, 0.2 mmol) with a hot dichloromethane solution of (II) (0.04 g, 0.1 mmol). Dark purple crystals of (III), suitable for X-ray diffraction studies, were obtained by slow evaporation of the solution at room temperature.
H atoms were introduced at calculated positions, with C—H = 0.93–0.97 Å, included in structure factor calculations and refined using a riding model.
Data collection: EXPOSE in IPDS (Stoe, 1999); cell refinement: SELECT and CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Please provide missing details.
C16H22N4O4S2·C12H4N4 | F(000) = 628 |
Mr = 602.70 | Dx = 1.361 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 20.960 (4) Å | Cell parameters from 4723 reflections |
b = 6.8198 (14) Å | θ = 2.1–25.9° |
c = 11.730 (2) Å | µ = 0.23 mm−1 |
β = 118.67 (3)° | T = 293 K |
V = 1471.2 (5) Å3 | Parallelepiped, dark purple |
Z = 2 | 0.3 × 0.3 × 0.3 mm |
Stoe IPDS area-detector diffractometer | 1135 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 26.1°, θmin = 2.2° |
Detector resolution: 6.66 pixels mm-1 | h = −25→25 |
rotation, ϕ increment 2° scans | k = −7→7 |
7171 measured reflections | l = −14→14 |
1526 independent 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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.073P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
1526 reflections | Δρmax = 0.26 e Å−3 |
128 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.039 (5) |
C16H22N4O4S2·C12H4N4 | V = 1471.2 (5) Å3 |
Mr = 602.70 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 20.960 (4) Å | µ = 0.23 mm−1 |
b = 6.8198 (14) Å | T = 293 K |
c = 11.730 (2) Å | 0.3 × 0.3 × 0.3 mm |
β = 118.67 (3)° |
Stoe IPDS area-detector diffractometer | 1135 reflections with I > 2σ(I) |
7171 measured reflections | Rint = 0.036 |
1526 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.26 e Å−3 |
1526 reflections | Δρmin = −0.25 e Å−3 |
128 parameters |
Experimental. Data were collected with an area detector (Stoe IPDS) with a crystal-to-plate distance of 70 mm (θmax = 26.11°) and with a ϕ increment of 2°. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.93046 (4) | 0.0000 | 0.14076 (6) | 0.0438 (3) | |
N1 | 0.84242 (12) | 0.0000 | −0.1060 (2) | 0.0436 (6) | |
N2 | 0.96518 (12) | 0.0000 | −0.0549 (2) | 0.0450 (6) | |
O1 | 0.74318 (12) | 0.0000 | 0.1450 (2) | 0.0732 (8) | |
O2 | 0.86127 (12) | 0.0000 | 0.2948 (2) | 0.0628 (6) | |
C1 | 0.91603 (14) | 0.0000 | −0.0187 (2) | 0.0397 (6) | |
C2 | 0.81787 (18) | 0.0000 | −0.2451 (3) | 0.0654 (9) | |
H2A | 0.8593 | 0.0000 | −0.2595 | 0.098* | |
H2B | 0.7891 | 0.1149 | −0.2838 | 0.098* | 0.50 |
H2C | 0.7891 | −0.1149 | −0.2838 | 0.098* | 0.50 |
C3 | 0.79813 (15) | 0.0000 | −0.0492 (3) | 0.0436 (6) | |
C4 | 0.71770 (17) | 0.0000 | −0.1329 (3) | 0.0621 (8) | |
H4A | 0.7061 | 0.0000 | −0.2226 | 0.093* | |
H4B | 0.6976 | 0.1149 | −0.1149 | 0.093* | 0.50 |
H4C | 0.6976 | −0.1149 | −0.1149 | 0.093* | 0.50 |
C5 | 0.83581 (15) | 0.0000 | 0.0817 (3) | 0.0440 (7) | |
C6 | 0.80676 (17) | 0.0000 | 0.1731 (3) | 0.0514 (7) | |
C7 | 0.8427 (2) | 0.0000 | 0.3991 (3) | 0.0826 (12) | |
H7A | 0.8143 | −0.1155 | 0.3936 | 0.099* | 0.50 |
H7B | 0.8143 | 0.1155 | 0.3936 | 0.099* | 0.50 |
C8 | 0.9117 (3) | 0.0000 | 0.5219 (4) | 0.1019 (16) | |
H8A | 0.9017 | 0.0000 | 0.5937 | 0.153* | |
H8B | 0.9392 | 0.1149 | 0.5260 | 0.153* | 0.50 |
H8C | 0.9392 | −0.1149 | 0.5260 | 0.153* | 0.50 |
N3 | 0.67704 (19) | 0.0000 | 0.4391 (3) | 0.0955 (12) | |
N4 | 0.44881 (17) | 0.0000 | 0.3475 (3) | 0.0851 (11) | |
C9 | 0.54219 (16) | 0.0000 | 0.2641 (3) | 0.0503 (7) | |
C10 | 0.61769 (19) | 0.0000 | 0.3622 (3) | 0.0631 (9) | |
C11 | 0.49044 (17) | 0.0000 | 0.3110 (3) | 0.0592 (9) | |
C12 | 0.57484 (15) | 0.0000 | 0.0888 (3) | 0.0448 (7) | |
H12 | 0.6241 | 0.0000 | 0.1488 | 0.054* | |
C13 | 0.52179 (14) | 0.0000 | 0.1345 (2) | 0.0427 (6) | |
C14 | 0.55422 (14) | 0.0000 | −0.0378 (2) | 0.0452 (7) | |
H14 | 0.5894 | 0.0000 | −0.0645 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0422 (4) | 0.0556 (5) | 0.0404 (4) | 0.000 | 0.0253 (3) | 0.000 |
N1 | 0.0432 (12) | 0.0513 (15) | 0.0407 (11) | 0.000 | 0.0237 (10) | 0.000 |
N2 | 0.0438 (12) | 0.0552 (17) | 0.0441 (11) | 0.000 | 0.0275 (10) | 0.000 |
O1 | 0.0549 (14) | 0.104 (2) | 0.0822 (16) | 0.000 | 0.0498 (13) | 0.000 |
O2 | 0.0639 (14) | 0.0871 (18) | 0.0558 (13) | 0.000 | 0.0437 (11) | 0.000 |
C1 | 0.0444 (15) | 0.0368 (16) | 0.0438 (13) | 0.000 | 0.0258 (12) | 0.000 |
C2 | 0.0582 (19) | 0.092 (3) | 0.0418 (15) | 0.000 | 0.0205 (14) | 0.000 |
C3 | 0.0421 (14) | 0.0397 (17) | 0.0567 (15) | 0.000 | 0.0300 (12) | 0.000 |
C4 | 0.0437 (16) | 0.066 (2) | 0.074 (2) | 0.000 | 0.0262 (15) | 0.000 |
C5 | 0.0438 (15) | 0.0461 (18) | 0.0542 (16) | 0.000 | 0.0332 (13) | 0.000 |
C6 | 0.0585 (18) | 0.051 (2) | 0.0620 (18) | 0.000 | 0.0429 (15) | 0.000 |
C7 | 0.090 (3) | 0.117 (4) | 0.068 (2) | 0.000 | 0.060 (2) | 0.000 |
C8 | 0.106 (4) | 0.156 (5) | 0.061 (2) | 0.000 | 0.054 (2) | 0.000 |
N3 | 0.0587 (19) | 0.154 (4) | 0.0551 (16) | 0.000 | 0.0121 (16) | 0.000 |
N4 | 0.0633 (19) | 0.147 (3) | 0.0493 (15) | 0.000 | 0.0304 (15) | 0.000 |
C9 | 0.0470 (16) | 0.057 (2) | 0.0446 (14) | 0.000 | 0.0201 (12) | 0.000 |
C10 | 0.056 (2) | 0.085 (3) | 0.0447 (15) | 0.000 | 0.0213 (15) | 0.000 |
C11 | 0.0523 (18) | 0.085 (3) | 0.0372 (13) | 0.000 | 0.0187 (13) | 0.000 |
C12 | 0.0354 (13) | 0.0496 (19) | 0.0467 (14) | 0.000 | 0.0176 (11) | 0.000 |
C13 | 0.0437 (15) | 0.0406 (17) | 0.0438 (13) | 0.000 | 0.0211 (12) | 0.000 |
C14 | 0.0389 (14) | 0.0496 (18) | 0.0475 (15) | 0.000 | 0.0212 (12) | 0.000 |
S1—C1 | 1.746 (2) | C5—C6 | 1.465 (4) |
S1—C5 | 1.760 (3) | C7—C8 | 1.473 (6) |
N1—C3 | 1.378 (3) | C7—H7A | 0.9700 |
N1—C1 | 1.383 (3) | C7—H7B | 0.9700 |
N1—C2 | 1.457 (4) | C8—H8A | 0.9600 |
N2—C1 | 1.289 (3) | C8—H8B | 0.9600 |
N2—N2i | 1.410 (5) | C8—H8C | 0.9600 |
O1—C6 | 1.209 (4) | N3—C10 | 1.133 (4) |
O2—C6 | 1.333 (4) | N4—C11 | 1.142 (4) |
O2—C7 | 1.451 (3) | C9—C13 | 1.367 (4) |
C2—H2A | 0.9600 | C9—C11 | 1.433 (4) |
C2—H2B | 0.9600 | C9—C10 | 1.443 (4) |
C2—H2C | 0.9600 | C12—C14 | 1.332 (4) |
C3—C5 | 1.349 (4) | C12—C13 | 1.448 (4) |
C3—C4 | 1.489 (4) | C12—H12 | 0.9300 |
C4—H4A | 0.9600 | C13—C14ii | 1.446 (4) |
C4—H4B | 0.9600 | C14—C13ii | 1.446 (4) |
C4—H4C | 0.9600 | C14—H14 | 0.9300 |
C1—S1—C5 | 89.73 (12) | O1—C6—C5 | 126.2 (3) |
C3—N1—C1 | 114.4 (2) | O2—C6—C5 | 109.8 (2) |
C3—N1—C2 | 125.7 (2) | O2—C7—C8 | 106.8 (3) |
C1—N1—C2 | 119.9 (2) | O2—C7—H7A | 110.4 |
C1—N2—N2i | 109.8 (2) | C8—C7—H7A | 110.4 |
C6—O2—C7 | 117.6 (3) | O2—C7—H7B | 110.4 |
N2—C1—N1 | 122.7 (2) | C8—C7—H7B | 110.4 |
N2—C1—S1 | 126.7 (2) | H7A—C7—H7B | 108.6 |
N1—C1—S1 | 110.59 (18) | C7—C8—H8A | 109.5 |
N1—C2—H2A | 109.5 | C7—C8—H8B | 109.5 |
N1—C2—H2B | 109.5 | H8A—C8—H8B | 109.5 |
H2A—C2—H2B | 109.5 | C7—C8—H8C | 109.5 |
N1—C2—H2C | 109.5 | H8A—C8—H8C | 109.5 |
H2A—C2—H2C | 109.5 | H8B—C8—H8C | 109.5 |
H2B—C2—H2C | 109.5 | C13—C9—C11 | 122.4 (3) |
C5—C3—N1 | 112.8 (2) | C13—C9—C10 | 121.7 (3) |
C5—C3—C4 | 127.5 (2) | C11—C9—C10 | 115.9 (3) |
N1—C3—C4 | 119.6 (2) | N3—C10—C9 | 179.9 (4) |
C3—C4—H4A | 109.5 | N4—C11—C9 | 179.5 (3) |
C3—C4—H4B | 109.5 | C14—C12—C13 | 121.1 (2) |
H4A—C4—H4B | 109.5 | C14—C12—H12 | 119.5 |
C3—C4—H4C | 109.5 | C13—C12—H12 | 119.5 |
H4A—C4—H4C | 109.5 | C9—C13—C14ii | 120.8 (2) |
H4B—C4—H4C | 109.5 | C9—C13—C12 | 121.7 (2) |
C3—C5—C6 | 127.7 (3) | C14ii—C13—C12 | 117.5 (2) |
C3—C5—S1 | 112.43 (18) | C12—C14—C13ii | 121.4 (3) |
C6—C5—S1 | 119.9 (2) | C12—C14—H14 | 119.3 |
O1—C6—O2 | 124.0 (3) | C13ii—C14—H14 | 119.3 |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C16H22N4O4S2·C12H4N4 |
Mr | 602.70 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 20.960 (4), 6.8198 (14), 11.730 (2) |
β (°) | 118.67 (3) |
V (Å3) | 1471.2 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.3 × 0.3 × 0.3 |
Data collection | |
Diffractometer | Stoe IPDS area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7171, 1526, 1135 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.108, 0.97 |
No. of reflections | 1526 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.25 |
Computer programs: EXPOSE in IPDS (Stoe, 1999), SELECT and CELL in IPDS, INTEGRATE in IPDS, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), Please provide missing details.
S1—C1 | 1.746 (2) | N3—C10 | 1.133 (4) |
S1—C5 | 1.760 (3) | N4—C11 | 1.142 (4) |
N1—C3 | 1.378 (3) | C9—C13 | 1.367 (4) |
N1—C1 | 1.383 (3) | C9—C11 | 1.433 (4) |
N1—C2 | 1.457 (4) | C9—C10 | 1.443 (4) |
N2—C1 | 1.289 (3) | C12—C14 | 1.332 (4) |
N2—N2i | 1.410 (5) | C12—C13 | 1.448 (4) |
C3—C5 | 1.349 (4) | C13—C14ii | 1.446 (4) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z. |
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Extended dithiadiazafulvalenes (DTDAF) which possess an azino spacer group between the two thiazole rings are interesting candidates for the synthesis of molecular materials (Barlow et al., 1976). Indeed, the insertion of an azino spacer group induces a wider difference between the two oxidation potentials of the donor than for DTDAF alone (Hünig et al., 1974). Therefore, the window of potential stability of the cation radical species is increased. In the course of our study on azino-DTDAF compounds and their ability to form complexes with various organic acceptors, we prepared the title complex, (III). \sch
The azino-DTDAF derivative, (II), was prepared using the thiazolium salt, (I), as the starting material (Bellec et al., 1999). This salt reacts in a basic medium with hydrazine monohydrate to afford (III). The strategy used is outlined in the Scheme (Hünig et al., 1964). The title complex, (III), was obtained by mixing a solution of the donor (II) with a solution of TCNQ.
The crystal structure determination of (III) reveals a stoichiometry of one donor molecule for one TCNQ molecule (Fig. 1). Both molecules possess crystallographic Ci symmetry. The planar donor and TCNQ molecules form infinite alternating stacks along the b axis, wherein the planes of the donor and the acceptor are parallel, with an interplanar separation of b/2 (3.41 Å) (Fig. 2). Interestingly, within the stacks, the long axis of the TCNQ is perpendicular to that of the donor.
No short intermolecular contacts, either within or between the stacks, are observed. The bond distances of the TCNQ in (III) are essentially the same as in crystals of pure TCNQ (Long et al., 1965).
Using the empirical formula of Kistenmacher (Kistenmacher et al., 1982), which correlates bond lengths with the formal charge of the TCNQ in various charge-transfer salts, we found no charge transfer on TCNQ in (III). Therefore, complex (III) is neutral. This was confirmed by the nitrile stretching absorption band in the FT—IR spectra, νCN = 2218 cm-1, which is close to the value for neutral TCNQ (νCN = 2224 cm-1). This neutral complex finds its origin in the difference between the redox potential of the donor and the acceptor. Indeed, the azino-DTDAF derivative (II) oxidizes at E1 = 0.48 V, far above the reduction potential of TCNQ (E1 = 0.20 V versus SCE).