Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101013075/bm1464sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013075/bm1464Isup2.hkl |
CCDC reference: 175083
For related literature, see: Aspley et al. (1999); Batsanov & Collings (2001); Beaumont & Davis (1967, 1968); Clyburne et al. (2001); Collings, Batsanov, Howard & Marder (2001); Collings, Roscoe, Thomas, Batsanov, Stimson, Howard & Marder (2001); Cooper et al. (1974); Potenza & Mastropaolo (1975); Rowland & Taylor (1996).
Slow evaporation of a solution of OFN (0.027 g, 0.1 mmol) and TTF (0.020 g, 0.1 mmol) in CH2Cl2 (1 ml) at room temperature, in a vial capped with a needle-pierced septum, for 2–3 d yielded yellow-brown blocks of (I) (m.p. 383–385 K; m.p. for TTF 393–396 K, m.p. for OFN 360–361 K). Gas chromatography and mass spectroscopy on a single-crystal of (I) dissolved in CH2Cl2 showed both compounds to be present. Elemental analysis: found (calculated): C 40.05 (40.34), H 0.80 (0.40)%. Cyclic voltammetry measurements were carried out in Bu4NPF6 as the supporting electrolyte at 293 K in MeCN, versus an Ag/AgCl reference electrode.
The value of Rint fell from 0.047 to 0.029 upon application of the absorption correction.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C10F8·C6H4S4 | Dx = 1.919 Mg m−3 |
Mr = 476.43 | Melting point = 383–385 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.581 (3) Å | Cell parameters from 992 reflections |
b = 6.321 (2) Å | θ = 12.0–26.4° |
c = 15.355 (2) Å | µ = 0.66 mm−1 |
β = 98.16 (1)° | T = 120 K |
V = 824.4 (4) Å3 | Plate, light brown |
Z = 2 | 0.45 × 0.40 × 0.08 mm |
F(000) = 472 |
SMART 1K CCD area-detector diffractometer | 2196 independent reflections |
Radiation source: fine-focus sealed tube | 1967 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 8 pixels mm-1 | θmax = 29.0°, θmin = 2.4° |
ω scans | h = −11→11 |
Absorption correction: integration (XPREP in SHELXTL; Bruker, 1997) | k = −8→8 |
Tmin = 0.763, Tmax = 0.962 | l = −20→20 |
9843 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0293P)2 + 0.3542P] where P = (Fo2 + 2Fc2)/3 |
2196 reflections | (Δ/σ)max = 0.001 |
135 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C10F8·C6H4S4 | V = 824.4 (4) Å3 |
Mr = 476.43 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.581 (3) Å | µ = 0.66 mm−1 |
b = 6.321 (2) Å | T = 120 K |
c = 15.355 (2) Å | 0.45 × 0.40 × 0.08 mm |
β = 98.16 (1)° |
SMART 1K CCD area-detector diffractometer | 2196 independent reflections |
Absorption correction: integration (XPREP in SHELXTL; Bruker, 1997) | 1967 reflections with I > 2σ(I) |
Tmin = 0.763, Tmax = 0.962 | Rint = 0.029 |
9843 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.35 e Å−3 |
2196 reflections | Δρmin = −0.23 e Å−3 |
135 parameters |
Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 5 sets of exposures; each set had a different ϕ and/or 2θ angles and each exposure (10 s) covered 0.3° in ω. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 144 duplicate reflections. |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.19709 (9) | 0.14546 (12) | 0.43977 (5) | 0.02391 (17) | |
F2 | 0.21917 (9) | 0.39832 (14) | 0.30206 (5) | 0.02555 (17) | |
F3 | 0.08230 (10) | 0.78456 (14) | 0.28991 (5) | 0.02926 (19) | |
F4 | −0.09014 (9) | 0.91991 (12) | 0.41203 (5) | 0.02452 (17) | |
C1 | 0.12486 (14) | 0.33419 (19) | 0.43619 (8) | 0.0180 (2) | |
C2 | 0.13760 (14) | 0.4619 (2) | 0.36604 (8) | 0.0193 (2) | |
C3 | 0.06509 (14) | 0.6616 (2) | 0.35923 (8) | 0.0205 (2) | |
C4 | −0.02138 (14) | 0.72853 (19) | 0.42206 (8) | 0.0185 (2) | |
C5 | −0.03762 (13) | 0.60177 (19) | 0.49626 (8) | 0.0164 (2) | |
S1 | 0.45778 (4) | 0.33523 (5) | 0.621254 (19) | 0.01977 (8) | |
S2 | 0.39284 (4) | 0.77437 (5) | 0.55687 (2) | 0.02025 (8) | |
C6 | 0.46906 (13) | 0.52274 (18) | 0.53701 (7) | 0.0154 (2) | |
C7 | 0.37310 (16) | 0.5111 (2) | 0.68906 (8) | 0.0241 (3) | |
H7 | 0.351 (2) | 0.462 (3) | 0.7446 (13) | 0.042 (5)* | |
C8 | 0.34297 (16) | 0.7066 (2) | 0.65972 (8) | 0.0239 (3) | |
H8 | 0.297 (2) | 0.817 (3) | 0.6906 (12) | 0.033 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0229 (4) | 0.0186 (4) | 0.0312 (4) | 0.0040 (3) | 0.0071 (3) | −0.0011 (3) |
F2 | 0.0230 (4) | 0.0350 (4) | 0.0205 (4) | 0.0005 (3) | 0.0094 (3) | −0.0033 (3) |
F3 | 0.0271 (4) | 0.0382 (5) | 0.0238 (4) | 0.0040 (3) | 0.0083 (3) | 0.0143 (3) |
F4 | 0.0228 (4) | 0.0194 (4) | 0.0319 (4) | 0.0047 (3) | 0.0061 (3) | 0.0077 (3) |
C1 | 0.0148 (5) | 0.0172 (5) | 0.0219 (5) | 0.0008 (4) | 0.0021 (4) | −0.0017 (4) |
C2 | 0.0148 (5) | 0.0263 (6) | 0.0173 (5) | −0.0011 (4) | 0.0041 (4) | −0.0027 (5) |
C3 | 0.0184 (5) | 0.0247 (6) | 0.0180 (5) | −0.0015 (5) | 0.0019 (4) | 0.0059 (5) |
C4 | 0.0151 (5) | 0.0179 (5) | 0.0223 (6) | 0.0005 (4) | 0.0013 (4) | 0.0032 (4) |
C5 | 0.0139 (5) | 0.0173 (5) | 0.0177 (5) | −0.0012 (4) | 0.0013 (4) | 0.0002 (4) |
S1 | 0.02621 (16) | 0.01667 (14) | 0.01697 (14) | 0.00035 (11) | 0.00496 (11) | 0.00083 (10) |
S2 | 0.02543 (16) | 0.01624 (14) | 0.02024 (15) | 0.00486 (11) | 0.00720 (11) | −0.00063 (11) |
C6 | 0.0160 (5) | 0.0142 (5) | 0.0157 (5) | 0.0012 (4) | 0.0016 (4) | −0.0001 (4) |
C7 | 0.0291 (7) | 0.0274 (7) | 0.0177 (6) | −0.0012 (5) | 0.0097 (5) | −0.0021 (5) |
C8 | 0.0273 (6) | 0.0259 (6) | 0.0204 (6) | 0.0017 (5) | 0.0101 (5) | −0.0052 (5) |
F1—C1 | 1.3419 (14) | C5—C5i | 1.437 (2) |
F2—C2 | 1.3459 (13) | S1—C7 | 1.7501 (13) |
F3—C3 | 1.3431 (14) | S1—C6 | 1.7672 (12) |
F4—C4 | 1.3452 (14) | S2—C8 | 1.7472 (13) |
C1—C2 | 1.3628 (17) | S2—C6 | 1.7628 (13) |
C1—C5i | 1.4213 (16) | C6—C6ii | 1.352 (2) |
C2—C3 | 1.4047 (18) | C7—C8 | 1.328 (2) |
C3—C4 | 1.3652 (17) | C7—H7 | 0.95 (2) |
C4—C5 | 1.4159 (16) | C8—H8 | 0.96 (2) |
C5—C1i | 1.4213 (16) | ||
F1—C1—C2 | 118.06 (11) | C4—C5—C5i | 118.46 (13) |
F1—C1—C5i | 120.75 (11) | C1i—C5—C5i | 118.30 (13) |
C2—C1—C5i | 121.19 (11) | C7—S1—C6 | 94.59 (6) |
F2—C2—C1 | 120.58 (12) | C8—S2—C6 | 94.57 (6) |
F2—C2—C3 | 118.99 (11) | C6ii—C6—S2 | 122.48 (12) |
C1—C2—C3 | 120.44 (11) | C6ii—C6—S1 | 122.79 (12) |
F3—C3—C4 | 120.83 (12) | S2—C6—S1 | 114.73 (6) |
F3—C3—C2 | 118.80 (11) | C8—C7—S1 | 117.81 (10) |
C4—C3—C2 | 120.37 (11) | C8—C7—H7 | 123.5 (12) |
F4—C4—C3 | 118.13 (11) | S1—C7—H7 | 118.7 (12) |
F4—C4—C5 | 120.62 (11) | C7—C8—S2 | 118.28 (10) |
C3—C4—C5 | 121.24 (11) | C7—C8—H8 | 125.7 (11) |
C4—C5—C1i | 123.24 (11) | S2—C8—H8 | 116.0 (11) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10F8·C6H4S4 |
Mr | 476.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 8.581 (3), 6.321 (2), 15.355 (2) |
β (°) | 98.16 (1) |
V (Å3) | 824.4 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.66 |
Crystal size (mm) | 0.45 × 0.40 × 0.08 |
Data collection | |
Diffractometer | SMART 1K CCD area-detector diffractometer |
Absorption correction | Integration (XPREP in SHELXTL; Bruker, 1997) |
Tmin, Tmax | 0.763, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9843, 2196, 1967 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.060, 1.06 |
No. of reflections | 2196 |
No. of parameters | 135 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.35, −0.23 |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Octafluoronaphthalene (OFN) forms stable 1:1 co-crystals with a variety of fused-ring aromatic hydrocarbons (Potenza & Mastropaolo, 1975; Collings, Roscoe et al., 2001) and with diphenylacetylene (Collings, Batsanov et al., 2001; Clyburne et al., 2001). The co-crystals comprise mixed stacks of parallel molecules and can be described as molecular complexes, showing no evidence of charge transfer (CT) either in their crystal structures or in UV-visible spectra (CT band). On the other hand, hexafluorobenzene can form genuine CT complexes, e.g. with aromatic amines (Beaumont & Davis, 1967, 1968) or with bis(benzene)chromium (Aspley et al., 1999), although its complexes with non-functionalized arenes also show no CT. To clarify the CT properties of OFN, we prepared its 1:1 complex, (I), with the facile electron donor tetrathiafulvalene (TTF). \sch
The crystal of (I) has a 1:1 TTF·OFN composition. Both molecules (Fig. 1) possess crystallographic Ci symmetry and are planar to within experimental error. They form an infinite stack, parallel to the a axis of the crystal (Fig. 2). The OFN and TTF molecules within a stack are not entirely parallel, but form a dihedral angle of 9.6 (1)°, with an average interplanar separation of 3.45 Å. This distortion may be due to short interstack contacts [F1···F4(x, y - 1, z) 2.827 (2) and F2···F3(-x, y - 1/2, 1/2 - z) 2.858 (2) Å, and their symmetry-related equivalents], compared with the standard van der Waals distance of 2.90 Å (Rowland & Taylor, 1996). In each case, a more parallel alignment of molecules in a stack would generate even shorter F···F contacts, as illustrated in Fig. 2 for the F2···F3 contacts. Adjacent stacks, symmetrically related by a 21 axis, have the same general direction, a, but the orientations of TTF planes within them differ by 33.1 (1)°, and the orientations of OFN planes by 48.8 (1)°. No intermolecular contacts, either within or between the stacks, are significantly shorter than the sums of the relevant van der Waals radii (Rowland & Taylor, 1996).
The bond distances in (I) are essentially the same as in crystals of pure TTF (Cooper et al., 1974) and OFN (Batsanov & Collings, 2001), showing the absence of CT in (I), despite the strong electron-donor ability of TTF. To our knowledge, the reduction potential of OFN has not been reported so far. Therefore, we undertook a cyclic voltammetry study of OFN, but observed no redox behaviour whatsoever in the range of 1.0 to -2.0 V. Thus, OFN behaves as an exceedingly poor electron acceptor, notwithstanding the apparent abundance of electronegative atoms in the molecule.