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In the title complex, C10F8·C6H4S4, planar centrosymmetric mol­ecules of tetra­thia­fulvalene and octa­fluoro­naphthalene, inclined to each other by 9.6 (1)°, form a mixed stack which does not exhibit charge transfer. Adjacent stacks pack in a herring-bone motif.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101013075/bm1464sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013075/bm1464Isup2.hkl
Contains datablock I

CCDC reference: 175083

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

The value of Rint fell from 0.047 to 0.029 upon application of the absorption correction.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecules of TTF (solid bonds) and OFN (hollow bonds) in (I), projected onto the mean plane of OFN. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are related through inversion centres to their unprimed equivalents.
[Figure 2] Fig. 2. The crystal packing of (I). H atoms have been omitted for clarity and dashed lines indicate interstack F2···F3 contacts of 2.858 (2) Å.
Octafluoronaphthalene-tetrathiafulvalene (1/1) top
Crystal data top
C10F8·C6H4S4Dx = 1.919 Mg m3
Mr = 476.43Melting point = 383–385 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.581 (3) ÅCell parameters from 992 reflections
b = 6.321 (2) Åθ = 12.0–26.4°
c = 15.355 (2) ŵ = 0.66 mm1
β = 98.16 (1)°T = 120 K
V = 824.4 (4) Å3Plate, light brown
Z = 20.45 × 0.40 × 0.08 mm
F(000) = 472
Data collection top
SMART 1K CCD area-detector
diffractometer
2196 independent reflections
Radiation source: fine-focus sealed tube1967 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 8 pixels mm-1θmax = 29.0°, θmin = 2.4°
ω scansh = 1111
Absorption correction: integration
(XPREP in SHELXTL; Bruker, 1997)
k = 88
Tmin = 0.763, Tmax = 0.962l = 2020
9843 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)] = 0.023Hydrogen site location: difference Fourier map
wR(F2) = 0.060All 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 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C10F8·C6H4S4V = 824.4 (4) Å3
Mr = 476.43Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.581 (3) ŵ = 0.66 mm1
b = 6.321 (2) ÅT = 120 K
c = 15.355 (2) Å0.45 × 0.40 × 0.08 mm
β = 98.16 (1)°
Data collection top
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 = 0.962Rint = 0.029
9843 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.060All H-atom parameters refined
S = 1.06Δρmax = 0.35 e Å3
2196 reflectionsΔρmin = 0.23 e Å3
135 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F10.19709 (9)0.14546 (12)0.43977 (5)0.02391 (17)
F20.21917 (9)0.39832 (14)0.30206 (5)0.02555 (17)
F30.08230 (10)0.78456 (14)0.28991 (5)0.02926 (19)
F40.09014 (9)0.91991 (12)0.41203 (5)0.02452 (17)
C10.12486 (14)0.33419 (19)0.43619 (8)0.0180 (2)
C20.13760 (14)0.4619 (2)0.36604 (8)0.0193 (2)
C30.06509 (14)0.6616 (2)0.35923 (8)0.0205 (2)
C40.02138 (14)0.72853 (19)0.42206 (8)0.0185 (2)
C50.03762 (13)0.60177 (19)0.49626 (8)0.0164 (2)
S10.45778 (4)0.33523 (5)0.621254 (19)0.01977 (8)
S20.39284 (4)0.77437 (5)0.55687 (2)0.02025 (8)
C60.46906 (13)0.52274 (18)0.53701 (7)0.0154 (2)
C70.37310 (16)0.5111 (2)0.68906 (8)0.0241 (3)
H70.351 (2)0.462 (3)0.7446 (13)0.042 (5)*
C80.34297 (16)0.7066 (2)0.65972 (8)0.0239 (3)
H80.297 (2)0.817 (3)0.6906 (12)0.033 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0229 (4)0.0186 (4)0.0312 (4)0.0040 (3)0.0071 (3)0.0011 (3)
F20.0230 (4)0.0350 (4)0.0205 (4)0.0005 (3)0.0094 (3)0.0033 (3)
F30.0271 (4)0.0382 (5)0.0238 (4)0.0040 (3)0.0083 (3)0.0143 (3)
F40.0228 (4)0.0194 (4)0.0319 (4)0.0047 (3)0.0061 (3)0.0077 (3)
C10.0148 (5)0.0172 (5)0.0219 (5)0.0008 (4)0.0021 (4)0.0017 (4)
C20.0148 (5)0.0263 (6)0.0173 (5)0.0011 (4)0.0041 (4)0.0027 (5)
C30.0184 (5)0.0247 (6)0.0180 (5)0.0015 (5)0.0019 (4)0.0059 (5)
C40.0151 (5)0.0179 (5)0.0223 (6)0.0005 (4)0.0013 (4)0.0032 (4)
C50.0139 (5)0.0173 (5)0.0177 (5)0.0012 (4)0.0013 (4)0.0002 (4)
S10.02621 (16)0.01667 (14)0.01697 (14)0.00035 (11)0.00496 (11)0.00083 (10)
S20.02543 (16)0.01624 (14)0.02024 (15)0.00486 (11)0.00720 (11)0.00063 (11)
C60.0160 (5)0.0142 (5)0.0157 (5)0.0012 (4)0.0016 (4)0.0001 (4)
C70.0291 (7)0.0274 (7)0.0177 (6)0.0012 (5)0.0097 (5)0.0021 (5)
C80.0273 (6)0.0259 (6)0.0204 (6)0.0017 (5)0.0101 (5)0.0052 (5)
Geometric parameters (Å, º) top
F1—C11.3419 (14)C5—C5i1.437 (2)
F2—C21.3459 (13)S1—C71.7501 (13)
F3—C31.3431 (14)S1—C61.7672 (12)
F4—C41.3452 (14)S2—C81.7472 (13)
C1—C21.3628 (17)S2—C61.7628 (13)
C1—C5i1.4213 (16)C6—C6ii1.352 (2)
C2—C31.4047 (18)C7—C81.328 (2)
C3—C41.3652 (17)C7—H70.95 (2)
C4—C51.4159 (16)C8—H80.96 (2)
C5—C1i1.4213 (16)
F1—C1—C2118.06 (11)C4—C5—C5i118.46 (13)
F1—C1—C5i120.75 (11)C1i—C5—C5i118.30 (13)
C2—C1—C5i121.19 (11)C7—S1—C694.59 (6)
F2—C2—C1120.58 (12)C8—S2—C694.57 (6)
F2—C2—C3118.99 (11)C6ii—C6—S2122.48 (12)
C1—C2—C3120.44 (11)C6ii—C6—S1122.79 (12)
F3—C3—C4120.83 (12)S2—C6—S1114.73 (6)
F3—C3—C2118.80 (11)C8—C7—S1117.81 (10)
C4—C3—C2120.37 (11)C8—C7—H7123.5 (12)
F4—C4—C3118.13 (11)S1—C7—H7118.7 (12)
F4—C4—C5120.62 (11)C7—C8—S2118.28 (10)
C3—C4—C5121.24 (11)C7—C8—H8125.7 (11)
C4—C5—C1i123.24 (11)S2—C8—H8116.0 (11)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC10F8·C6H4S4
Mr476.43
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)8.581 (3), 6.321 (2), 15.355 (2)
β (°) 98.16 (1)
V3)824.4 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.66
Crystal size (mm)0.45 × 0.40 × 0.08
Data collection
DiffractometerSMART 1K CCD area-detector
diffractometer
Absorption correctionIntegration
(XPREP in SHELXTL; Bruker, 1997)
Tmin, Tmax0.763, 0.962
No. of measured, independent and
observed [I > 2σ(I)] reflections
9843, 2196, 1967
Rint0.029
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.060, 1.06
No. of reflections2196
No. of parameters135
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.35, 0.23

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

 

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