Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802023723/ob6206sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802023723/ob6206Isup2.hkl |
CCDC reference: 204684
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.017 Å
- R factor = 0.063
- wR factor = 0.174
- Data-to-parameter ratio = 8.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_360 Alert C Short C(sp3)-C(sp3) Bond C(7) - C(8) = 1.40 Ang. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 74.15 From the CIF: _reflns_number_total 1303 Count of symmetry unique reflns 1302 Completeness (_total/calc) 100.08% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1 Fraction of Friedel pairs measured 0.001 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was synthesized according to the literature method of Tomura & Yamashita (1997). Orange crystals of (I) suitable for X-ray analysis were grown from a toluene solution.
All H atoms were placed in geometrically calculated positions and refined by using a riding model, with C—H set to 0.97 Å. The short C7—C8 bond length [1.40 (2) Å] may be due to the positional disorder of the C7 and C8 atoms. This type of the disorder is often observed in TTF derivatives with an ethylenedithio or ethylenedioxy group.
Data collection: CAD-4 EXPRESS Software (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS Software; data reduction: TEXSAN (Molecular Structure Corporation/Rigaku Corporation, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
C8H4N2O2S5 | F(000) = 648 |
Mr = 320.43 | Dx = 1.892 Mg m−3 |
Orthorhombic, Pna21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2c -2n | Cell parameters from 18 reflections |
a = 21.7363 (10) Å | θ = 14.1–42.7° |
b = 12.9552 (6) Å | µ = 9.43 mm−1 |
c = 3.9938 (5) Å | T = 296 K |
V = 1124.65 (16) Å3 | Needle, orange |
Z = 4 | 0.40 × 0.04 × 0.02 mm |
Enraf-Nonius CAD4 diffractometer | 791 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 74.2°, θmin = 4.0° |
ω–2θ scans | h = −27→0 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→16 |
Tmin = 0.116, Tmax = 0.834 | l = −4→0 |
1303 measured reflections | 3 standard reflections every 120 min |
1303 independent reflections | intensity decay: 0.4% |
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)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.174 | w = 1/[σ2(Fo2) + (0.0859P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1303 reflections | Δρmax = 0.61 e Å−3 |
154 parameters | Δρmin = −0.87 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (10) |
C8H4N2O2S5 | V = 1124.65 (16) Å3 |
Mr = 320.43 | Z = 4 |
Orthorhombic, Pna21 | Cu Kα radiation |
a = 21.7363 (10) Å | µ = 9.43 mm−1 |
b = 12.9552 (6) Å | T = 296 K |
c = 3.9938 (5) Å | 0.40 × 0.04 × 0.02 mm |
Enraf-Nonius CAD4 diffractometer | 791 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.116, Tmax = 0.834 | 3 standard reflections every 120 min |
1303 measured reflections | intensity decay: 0.4% |
1303 independent reflections |
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.174 | Δρmax = 0.61 e Å−3 |
S = 1.05 | Δρmin = −0.87 e Å−3 |
1303 reflections | Absolute structure: (Flack, 1983) |
154 parameters | Absolute structure parameter: 0.03 (10) |
1 restraint |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 6.8741 (0.0333) x + 3.9058 (0.0249) y + 3.5924 (0.0043) z = 6.0903 (0.0322) * −0.1884 (0.0062) S1 * −0.2435 (0.0062) S2 * −0.1307 (0.0063) S3 * −0.2440 (0.0060) S4 * 0.2684 (0.0070) S5 * 0.1640 (0.0114) O1 * 0.0838 (0.0105) O2 * 0.1699 (0.0104) N1 * 0.1283 (0.0105) N2 * −0.2052 (0.0138) C1 * 0.0320 (0.0138) C2 * 0.0094 (0.0138) C3 * −0.1888 (0.0144) C4 * 0.0472 (0.0129) C5 * 0.0151 (0.0139) C6 * −0.2029 (0.0171) C7 * 0.4854 (0.0137) C8 Rms deviation of fitted atoms = 0.2001 8.9585 (0.0542) x + 3.1201 (0.0352) y + 3.5094 (0.0060) z = 5.8997 (0.0420) Angle to previous plane (with approximate e.s.d.) = 6.61 (0.29) * −0.0482 (0.0074) S1 * −0.0522 (0.0075) S2 * 0.0011 (0.0071) S5 * 0.0029 (0.0086) N1 * 0.0064 (0.0086) N2 * 0.0680 (0.0089) C1 * 0.0110 (0.0131) C2 * 0.0111 (0.0132) C3 Rms deviation of fitted atoms = 0.0353 5.4544 (0.0728) x + 4.9899 (0.0399) y + 3.5468 (0.0058) z = 6.1595 (0.0419) Angle to previous plane (with approximate e.s.d.) = 12.43 (0.35) * −0.0341 (0.0072) S3 * −0.0516 (0.0073) S4 * −0.0087 (0.0076) O1 * 0.0044 (0.0073) O2 * 0.0514 (0.0085) C4 * 0.0140 (0.0115) C5 * 0.0245 (0.0126) C6 Rms deviation of fitted atoms = 0.0324 |
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 | ||
S1 | 0.30528 (12) | 0.8612 (2) | 0.1225 (12) | 0.0400 (10) | |
S2 | 0.37929 (13) | 1.0282 (2) | −0.2161 (11) | 0.0361 (8) | |
S3 | 0.42294 (13) | 0.7100 (2) | 0.0777 (11) | 0.0372 (8) | |
S4 | 0.49339 (12) | 0.8760 (2) | −0.2692 (10) | 0.0339 (9) | |
S5 | 0.21400 (13) | 1.1375 (2) | 0.1239 (13) | 0.0450 (10) | |
O1 | 0.5248 (4) | 0.5955 (6) | 0.089 (4) | 0.052 (3) | |
O2 | 0.5931 (3) | 0.7572 (6) | −0.240 (3) | 0.047 (3) | |
N1 | 0.2193 (4) | 1.0138 (7) | 0.221 (3) | 0.034 (3) | |
N2 | 0.2819 (4) | 1.1522 (6) | −0.061 (3) | 0.034 (3) | |
C1 | 0.3768 (5) | 0.9011 (8) | −0.062 (4) | 0.030 (3) | |
C2 | 0.2736 (5) | 0.9833 (8) | 0.112 (4) | 0.032 (3) | |
C3 | 0.3085 (5) | 1.0641 (8) | −0.049 (4) | 0.032 (3) | |
C4 | 0.4241 (5) | 0.8373 (8) | −0.079 (4) | 0.032 (3) | |
C5 | 0.5012 (5) | 0.6895 (8) | 0.000 (3) | 0.027 (3) | |
C6 | 0.5327 (5) | 0.7637 (8) | −0.150 (4) | 0.033 (3) | |
C7 | 0.5815 (6) | 0.5801 (12) | −0.105 (6) | 0.069 (6) | |
H7A | 0.6031 | 0.5199 | −0.0211 | 0.083* | |
H7B | 0.5712 | 0.5679 | −0.3376 | 0.083* | |
C8 | 0.6197 (5) | 0.6668 (9) | −0.080 (4) | 0.039 (4) | |
H8A | 0.6590 | 0.6514 | −0.1845 | 0.047* | |
H8B | 0.6273 | 0.6818 | 0.1540 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0326 (15) | 0.0237 (13) | 0.064 (3) | −0.0023 (11) | 0.010 (2) | 0.0012 (19) |
S2 | 0.0299 (14) | 0.0264 (14) | 0.052 (2) | 0.0008 (12) | 0.0046 (18) | 0.0042 (19) |
S3 | 0.0343 (15) | 0.0261 (13) | 0.051 (2) | −0.0009 (12) | 0.007 (2) | 0.0079 (19) |
S4 | 0.0296 (14) | 0.0257 (14) | 0.047 (2) | 0.0016 (11) | 0.0014 (17) | 0.0053 (16) |
S5 | 0.0346 (15) | 0.0323 (14) | 0.068 (3) | 0.0073 (13) | 0.002 (2) | −0.004 (2) |
O1 | 0.047 (5) | 0.034 (4) | 0.074 (8) | 0.008 (4) | −0.021 (7) | 0.013 (6) |
O2 | 0.028 (4) | 0.041 (5) | 0.071 (8) | 0.013 (4) | −0.001 (6) | 0.022 (6) |
N1 | 0.026 (4) | 0.029 (5) | 0.046 (8) | 0.000 (4) | 0.002 (6) | −0.003 (6) |
N2 | 0.021 (5) | 0.019 (4) | 0.063 (9) | 0.007 (4) | −0.001 (6) | 0.002 (5) |
C1 | 0.033 (6) | 0.019 (5) | 0.037 (8) | −0.005 (5) | 0.015 (7) | −0.001 (6) |
C2 | 0.035 (6) | 0.030 (6) | 0.031 (8) | −0.005 (5) | −0.006 (8) | −0.011 (7) |
C3 | 0.024 (6) | 0.021 (6) | 0.051 (10) | 0.002 (4) | 0.003 (7) | 0.010 (6) |
C4 | 0.025 (6) | 0.027 (6) | 0.043 (9) | −0.007 (5) | 0.006 (7) | 0.003 (7) |
C5 | 0.023 (5) | 0.024 (5) | 0.035 (9) | 0.009 (4) | −0.001 (6) | 0.002 (6) |
C6 | 0.031 (6) | 0.024 (6) | 0.045 (10) | 0.006 (5) | 0.007 (7) | 0.004 (7) |
C7 | 0.055 (9) | 0.082 (12) | 0.071 (14) | 0.053 (9) | −0.008 (10) | −0.007 (12) |
C8 | 0.030 (6) | 0.044 (7) | 0.045 (10) | 0.019 (6) | 0.002 (8) | −0.003 (8) |
S1—C2 | 1.726 (11) | O2—C6 | 1.363 (12) |
S1—C1 | 1.796 (12) | O2—C8 | 1.453 (14) |
S2—C3 | 1.740 (12) | N1—C2 | 1.317 (14) |
S2—C1 | 1.758 (12) | N2—C3 | 1.281 (12) |
S3—C5 | 1.751 (11) | C1—C4 | 1.322 (14) |
S3—C4 | 1.765 (12) | C2—C3 | 1.444 (16) |
S4—C6 | 1.754 (11) | C5—C6 | 1.323 (16) |
S4—C4 | 1.759 (12) | C7—C8 | 1.400 (18) |
S5—N1 | 1.653 (9) | C7—H7A | 0.9700 |
S5—N2 | 1.662 (10) | C7—H7B | 0.9700 |
O1—C5 | 1.369 (12) | C8—H8A | 0.9700 |
O1—C7 | 1.468 (19) | C8—H8B | 0.9700 |
S1···S5i | 3.541 (5) | S4···S2iv | 3.519 (5) |
S1···S5ii | 3.547 (5) | S5···S1v | 3.541 (5) |
S2···S4iii | 3.519 (5) | S5···S1vi | 3.547 (5) |
S3···S5i | 3.610 (5) | S5···S3v | 3.610 (5) |
C2—S1—C1 | 94.1 (6) | S4—C4—S3 | 115.6 (6) |
C3—S2—C1 | 95.1 (5) | C6—C5—O1 | 124.8 (10) |
C5—S3—C4 | 93.7 (5) | C6—C5—S3 | 118.2 (8) |
C6—S4—C4 | 93.6 (6) | O1—C5—S3 | 116.9 (8) |
N1—S5—N2 | 98.8 (5) | C5—C6—O2 | 124.9 (10) |
C5—O1—C7 | 107.3 (11) | C5—C6—S4 | 118.3 (8) |
C6—O2—C8 | 108.6 (9) | O2—C6—S4 | 116.7 (9) |
C2—N1—S5 | 106.0 (8) | C8—C7—O1 | 110.6 (12) |
C3—N2—S5 | 106.4 (8) | C8—C7—H7A | 109.5 |
C4—C1—S2 | 122.9 (9) | O1—C7—H7A | 109.5 |
C4—C1—S1 | 121.0 (9) | C8—C7—H7B | 109.5 |
S2—C1—S1 | 116.1 (6) | O1—C7—H7B | 109.5 |
N1—C2—C3 | 113.6 (10) | H7A—C7—H7B | 108.1 |
N1—C2—S1 | 128.6 (10) | C7—C8—O2 | 112.3 (11) |
C3—C2—S1 | 117.7 (9) | C7—C8—H8A | 109.1 |
N2—C3—C2 | 115.2 (10) | O2—C8—H8A | 109.1 |
N2—C3—S2 | 128.5 (9) | C7—C8—H8B | 109.1 |
C2—C3—S2 | 116.2 (8) | O2—C8—H8B | 109.1 |
C1—C4—S4 | 120.7 (9) | H8A—C8—H8B | 107.9 |
C1—C4—S3 | 123.7 (9) | ||
N2—S5—N1—C2 | 0.2 (12) | S1—C1—C4—S3 | −0.7 (18) |
N1—S5—N2—C3 | −0.1 (12) | C6—S4—C4—C1 | 173.3 (12) |
C3—S2—C1—C4 | −171.5 (13) | C6—S4—C4—S3 | −7.4 (10) |
C3—S2—C1—S1 | 8.5 (10) | C5—S3—C4—C1 | −173.9 (13) |
C2—S1—C1—C4 | 171.5 (12) | C5—S3—C4—S4 | 6.8 (9) |
C2—S1—C1—S2 | −8.4 (10) | C7—O1—C5—C6 | −18.5 (19) |
S5—N1—C2—C3 | −0.2 (16) | C7—O1—C5—S3 | 159.1 (11) |
S5—N1—C2—S1 | −177.2 (11) | C4—S3—C5—C6 | −3.2 (13) |
C1—S1—C2—N1 | −178.2 (15) | C4—S3—C5—O1 | 179.0 (12) |
C1—S1—C2—C3 | 4.9 (13) | O1—C5—C6—O2 | 1 (2) |
S5—N2—C3—C2 | 0.0 (16) | S3—C5—C6—O2 | −177.1 (11) |
S5—N2—C3—S2 | 177.0 (11) | O1—C5—C6—S4 | 176.1 (11) |
N1—C2—C3—N2 | 0 (2) | S3—C5—C6—S4 | −1.5 (17) |
S1—C2—C3—N2 | 177.5 (12) | C8—O2—C6—C5 | −12 (2) |
N1—C2—C3—S2 | −177.3 (12) | C8—O2—C6—S4 | 172.1 (10) |
S1—C2—C3—S2 | 0.1 (16) | C4—S4—C6—C5 | 5.4 (14) |
C1—S2—C3—N2 | 177.8 (15) | C4—S4—C6—O2 | −178.7 (11) |
C1—S2—C3—C2 | −5.2 (13) | C5—O1—C7—C8 | 49.7 (17) |
S2—C1—C4—S4 | −1.5 (18) | O1—C7—C8—O2 | −66.4 (18) |
S1—C1—C4—S4 | 178.5 (9) | C6—O2—C8—C7 | 44.5 (17) |
S2—C1—C4—S3 | 179.2 (9) |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) −x+1/2, y−1/2, z+1/2; (iii) −x+1, −y+2, z+1/2; (iv) −x+1, −y+2, z−1/2; (v) −x+1/2, y+1/2, z+1/2; (vi) −x+1/2, y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H4N2O2S5 |
Mr | 320.43 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 296 |
a, b, c (Å) | 21.7363 (10), 12.9552 (6), 3.9938 (5) |
V (Å3) | 1124.65 (16) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 9.43 |
Crystal size (mm) | 0.40 × 0.04 × 0.02 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.116, 0.834 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1303, 1303, 791 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.174, 1.05 |
No. of reflections | 1303 |
No. of parameters | 154 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.87 |
Absolute structure | (Flack, 1983) |
Absolute structure parameter | 0.03 (10) |
Computer programs: CAD-4 EXPRESS Software (Enraf-Nonius, 1992), CAD-4 EXPRESS Software, TEXSAN (Molecular Structure Corporation/Rigaku Corporation, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
S1—C2 | 1.726 (11) | O1—C5 | 1.369 (12) |
S1—C1 | 1.796 (12) | O1—C7 | 1.468 (19) |
S2—C3 | 1.740 (12) | O2—C6 | 1.363 (12) |
S2—C1 | 1.758 (12) | O2—C8 | 1.453 (14) |
S3—C5 | 1.751 (11) | N1—C2 | 1.317 (14) |
S3—C4 | 1.765 (12) | N2—C3 | 1.281 (12) |
S4—C6 | 1.754 (11) | C1—C4 | 1.322 (14) |
S4—C4 | 1.759 (12) | C2—C3 | 1.444 (16) |
S5—N1 | 1.653 (9) | C5—C6 | 1.323 (16) |
S5—N2 | 1.662 (10) | C7—C8 | 1.400 (18) |
S1···S5i | 3.541 (5) | S4···S2iv | 3.519 (5) |
S1···S5ii | 3.547 (5) | S5···S1v | 3.541 (5) |
S2···S4iii | 3.519 (5) | S5···S1vi | 3.547 (5) |
S3···S5i | 3.610 (5) | S5···S3v | 3.610 (5) |
C2—S1—C1 | 94.1 (6) | C3—C2—S1 | 117.7 (9) |
C3—S2—C1 | 95.1 (5) | N2—C3—C2 | 115.2 (10) |
C5—S3—C4 | 93.7 (5) | C2—C3—S2 | 116.2 (8) |
C6—S4—C4 | 93.6 (6) | S4—C4—S3 | 115.6 (6) |
N1—S5—N2 | 98.8 (5) | C6—C5—O1 | 124.8 (10) |
C5—O1—C7 | 107.3 (11) | C6—C5—S3 | 118.2 (8) |
C6—O2—C8 | 108.6 (9) | C5—C6—O2 | 124.9 (10) |
C2—N1—S5 | 106.0 (8) | C5—C6—S4 | 118.3 (8) |
C3—N2—S5 | 106.4 (8) | C8—C7—O1 | 110.6 (12) |
S2—C1—S1 | 116.1 (6) | C7—C8—O2 | 112.3 (11) |
N1—C2—C3 | 113.6 (10) |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) −x+1/2, y−1/2, z+1/2; (iii) −x+1, −y+2, z+1/2; (iv) −x+1, −y+2, z−1/2; (v) −x+1/2, y+1/2, z+1/2; (vi) −x+1/2, y+1/2, z−1/2. |
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In recent years tetrathiafulvalene (TTF) derivatives with a fused 1,2,5-thiadiazole ring have received much attention as component molecules for organic conducting solids (Tomura et al., 1993; Underhill et al., 1993; Naito et al., 1996; Tomura & Yamashita, 1997). Intermolecular interactions caused by S···N and S···S heteroatom contacts may increase the dimensionality in the solid state (Yamashita & Tomura, 1998). The title unsymmetrical TTF derivative (I) contains a fused 1,2,5-thiadiazole ring and an ethylenedioxy group. Two superconductors based on bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF) are known to date (Beno et al., 1990; Kahlich et al., 1991). We report here the molecular and crystal structures of (I).
Compound (I) crystallizes in the Pna21 space group. Its molecular structure is shown in Fig. 1 and selected geometric parameters are given in Table 1. The molecule of (I) is bent slightly at the central C1=C4 bond. The dihedral angle between the two least-squares planes (S1/S2/S5/N1/N2/C1/C2/C3 and S3/S4/O1/O2/C4/C5/C6) is 12.4 (4)°. The maximum and r.m.s. deviations of fitted atoms from the least-squares plane for all non-H atoms are 0.49 (1) for C8 and 0.20 Å, respectively. The geometric parameters of the 1,2,5-thiadiazole ring in (I) are almost same as those of 3,4-diphenyl-1,2,5-thiadiazole (Mellini & Merlino, 1976).
Fig. 2 shows the packing of (I), viewed along the c axis. A large number of short intermolecular S···S contacts within the sum of the corresponding van der Waals radii (Pauling, 1960) are observed (Table 2), but no short heteroatom contacts involving the N and O atoms exist in the crystal. Two types of dimers are formed via the short S···S contacts. One is composed of two parallel molecules and the other is formed by a T-shaped molecular arrangement. The molecules stack along the c axis, where the distance between the molecular planes is 3.59 (1) Å. TTF derivatives with a fused 1,2,5-thiadiazole ring tend to stack in a head-to-tail fashion (Tomura & Yamashita, 2001). In the stacking of (I), however, the molecules overlap face-to-face with each other.