Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016753/sk1337sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016753/sk1337BEDT-TTFsup2.hkl |
CCDC reference: 144631
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999).
C10H8S8 | F(000) = 784 |
Mr = 384.64 | Dx = 1.794 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6583 (1) Å | Cell parameters from 425 reflections |
b = 13.733 (2) Å | θ = 20.5–34.1° |
c = 17.414 (1) Å | µ = 1.23 mm−1 |
β = 116.57 (1)° | T = 100 K |
V = 1424.1 (1) Å3 | Needles, orange |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
SMART Siemens CCD diffractometer | 3251 independent reflections |
Radiation source: fine-focus sealed tube | 2714 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 27.4°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | h = −8→8 |
Tmin = 0.768, Tmax = 0.915 | k = −17→17 |
12398 measured reflections | l = −22→22 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0191P)2 + 1.0583P] where P = (Fo2 + 2Fc2)/3 |
3251 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C10H8S8 | V = 1424.1 (1) Å3 |
Mr = 384.64 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.6583 (1) Å | µ = 1.23 mm−1 |
b = 13.733 (2) Å | T = 100 K |
c = 17.414 (1) Å | 0.20 × 0.15 × 0.10 mm |
β = 116.57 (1)° |
SMART Siemens CCD diffractometer | 3251 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | 2714 reflections with I > 2σ(I) |
Tmin = 0.768, Tmax = 0.915 | Rint = 0.037 |
12398 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.35 e Å−3 |
3251 reflections | Δρmin = −0.36 e Å−3 |
163 parameters |
Experimental. The sample was cooled at a rate of 2 K min-1. A half sphere was collected based on ω scans at values of Φ = 0, 88, 180°. Frames were collected at 0.3° intervals and at 20 s per frame. At the end of these runs, the first 100 frames were repeated in order to check that no alteration had occurred. |
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 | ||
S2 | 0.21293 (8) | 0.85826 (4) | 0.04260 (3) | 0.01247 (12) | |
S6 | 0.14782 (9) | 0.69753 (4) | −0.08621 (3) | 0.01417 (12) | |
S4 | 0.30107 (8) | 0.98716 (4) | 0.21250 (3) | 0.01312 (11) | |
S5 | −0.39553 (9) | 0.72435 (4) | −0.15221 (3) | 0.01568 (12) | |
S1 | −0.27815 (8) | 0.88339 (4) | −0.02020 (3) | 0.01156 (11) | |
S3 | −0.18790 (8) | 1.00502 (4) | 0.15326 (3) | 0.01180 (11) | |
S8 | 0.42843 (9) | 1.05090 (4) | 0.39193 (3) | 0.01408 (12) | |
S7 | −0.16013 (9) | 1.06906 (4) | 0.31922 (4) | 0.01596 (12) | |
C17 | 0.0339 (3) | 0.77851 (14) | −0.03902 (13) | 0.0111 (4) | |
C10 | 0.0304 (3) | 0.95583 (15) | 0.13432 (13) | 0.0109 (4) | |
C16 | −0.1892 (3) | 0.79056 (14) | −0.06840 (13) | 0.0108 (4) | |
C11 | −0.0116 (3) | 1.02797 (14) | 0.26384 (13) | 0.0114 (4) | |
C15 | −0.0068 (3) | 0.90362 (14) | 0.06337 (13) | 0.0111 (4) | |
C13 | 0.0651 (3) | 1.07854 (16) | 0.42725 (13) | 0.0144 (4) | |
H132 | 0.0105 | 1.1155 | 0.4630 | 0.017* | |
H131 | 0.1060 | 1.0124 | 0.4519 | 0.017* | |
C12 | 0.2119 (3) | 1.02056 (14) | 0.29065 (13) | 0.0111 (4) | |
C14 | 0.2736 (4) | 1.12825 (15) | 0.43150 (14) | 0.0148 (4) | |
H142 | 0.3728 | 1.1466 | 0.4917 | 0.018* | |
H141 | 0.2289 | 1.1887 | 0.3970 | 0.018* | |
C19 | −0.0312 (4) | 0.73258 (16) | −0.19720 (13) | 0.0147 (4) | |
H192 | −0.0140 | 0.8034 | −0.2030 | 0.018* | |
H191 | 0.0225 | 0.6987 | −0.2347 | 0.018* | |
C18 | −0.2788 (4) | 0.71025 (18) | −0.22912 (14) | 0.0199 (5) | |
H182 | −0.3051 | 0.6423 | −0.2503 | 0.024* | |
H181 | −0.3649 | 0.7530 | −0.2789 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S2 | 0.0094 (2) | 0.0162 (2) | 0.0109 (3) | 0.00037 (19) | 0.0037 (2) | −0.00320 (19) |
S6 | 0.0153 (3) | 0.0143 (2) | 0.0134 (3) | 0.00399 (19) | 0.0069 (2) | −0.00112 (19) |
S4 | 0.0093 (2) | 0.0206 (3) | 0.0093 (2) | −0.00016 (19) | 0.0040 (2) | −0.0039 (2) |
S5 | 0.0146 (3) | 0.0202 (3) | 0.0132 (3) | −0.0070 (2) | 0.0070 (2) | −0.0061 (2) |
S1 | 0.0092 (2) | 0.0139 (2) | 0.0100 (2) | 0.00088 (18) | 0.0029 (2) | −0.00227 (19) |
S3 | 0.0089 (2) | 0.0164 (2) | 0.0088 (2) | 0.00107 (19) | 0.00284 (19) | −0.0018 (2) |
S8 | 0.0103 (2) | 0.0221 (3) | 0.0083 (3) | 0.0002 (2) | 0.0028 (2) | −0.0036 (2) |
S7 | 0.0115 (2) | 0.0251 (3) | 0.0131 (3) | −0.0016 (2) | 0.0071 (2) | −0.0061 (2) |
C17 | 0.0145 (10) | 0.0103 (9) | 0.0091 (10) | −0.0006 (8) | 0.0059 (8) | −0.0011 (7) |
C10 | 0.0075 (9) | 0.0130 (9) | 0.0103 (10) | −0.0003 (7) | 0.0023 (8) | 0.0008 (8) |
C16 | 0.0146 (10) | 0.0099 (9) | 0.0084 (10) | −0.0004 (8) | 0.0054 (8) | −0.0018 (8) |
C11 | 0.0139 (10) | 0.0115 (9) | 0.0087 (10) | −0.0008 (8) | 0.0051 (8) | −0.0017 (8) |
C15 | 0.0095 (9) | 0.0117 (9) | 0.0118 (10) | 0.0012 (7) | 0.0046 (8) | 0.0006 (8) |
C13 | 0.0156 (10) | 0.0185 (10) | 0.0117 (10) | −0.0004 (8) | 0.0085 (9) | −0.0034 (8) |
C12 | 0.0143 (10) | 0.0119 (9) | 0.0077 (9) | −0.0007 (8) | 0.0055 (8) | −0.0008 (7) |
C14 | 0.0136 (10) | 0.0171 (10) | 0.0130 (11) | −0.0008 (8) | 0.0053 (9) | −0.0041 (8) |
C19 | 0.0202 (11) | 0.0162 (10) | 0.0099 (10) | −0.0022 (8) | 0.0085 (9) | 0.0001 (8) |
C18 | 0.0193 (12) | 0.0287 (12) | 0.0126 (11) | −0.0031 (9) | 0.0080 (9) | −0.0046 (9) |
S2—C17 | 1.768 (2) | S3—C11 | 1.778 (2) |
S2—C15 | 1.770 (2) | S8—C12 | 1.757 (2) |
S6—C17 | 1.745 (2) | S8—C14 | 1.817 (2) |
S6—C19 | 1.824 (2) | S7—C11 | 1.755 (2) |
S4—C10 | 1.758 (2) | S7—C13 | 1.811 (2) |
S4—C12 | 1.771 (2) | C17—C16 | 1.347 (3) |
S5—C16 | 1.746 (2) | C10—C15 | 1.352 (3) |
S5—C18 | 1.835 (2) | C11—C12 | 1.350 (3) |
S1—C15 | 1.762 (2) | C13—C14 | 1.518 (3) |
S1—C16 | 1.768 (2) | C19—C18 | 1.517 (3) |
S3—C10 | 1.763 (2) | ||
C17—S2—C15 | 93.47 (10) | C17—C16—S1 | 117.06 (15) |
C17—S6—C19 | 96.61 (10) | S5—C16—S1 | 117.83 (12) |
C10—S4—C12 | 94.51 (10) | C12—C11—S7 | 129.74 (16) |
C16—S5—C18 | 103.49 (10) | C12—C11—S3 | 116.91 (16) |
C15—S1—C16 | 93.92 (10) | S7—C11—S3 | 113.01 (11) |
C10—S3—C11 | 94.05 (10) | C10—C15—S1 | 122.65 (16) |
C12—S8—C14 | 99.75 (10) | C10—C15—S2 | 122.88 (16) |
C11—S7—C13 | 100.70 (10) | S1—C15—S2 | 114.29 (11) |
C16—C17—S6 | 122.49 (16) | C14—C13—S7 | 113.38 (15) |
C16—C17—S2 | 117.49 (15) | C11—C12—S8 | 127.73 (16) |
S6—C17—S2 | 119.64 (12) | C11—C12—S4 | 116.77 (16) |
C15—C10—S4 | 122.88 (16) | S8—C12—S4 | 115.22 (12) |
C15—C10—S3 | 123.01 (16) | C13—C14—S8 | 112.34 (15) |
S4—C10—S3 | 113.99 (12) | C18—C19—S6 | 115.01 (15) |
C17—C16—S5 | 125.08 (16) | C19—C18—S5 | 117.19 (16) |
Experimental details
Crystal data | |
Chemical formula | C10H8S8 |
Mr | 384.64 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 6.6583 (1), 13.733 (2), 17.414 (1) |
β (°) | 116.57 (1) |
V (Å3) | 1424.1 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.23 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | SMART Siemens CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.768, 0.915 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12398, 3251, 2714 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.061, 1.09 |
No. of reflections | 3251 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.36 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999).
The BEDT-TTF molecule, (I), is used to build the very well known (BEDT-TTF)xn+Xn- salts which exhibit such a diversity of physical and structural properties (Williams et al., 1992). In our aim to correlate structural and conducting properties in this series we assume that knowledge of the low-temperature structural properties of the neutral molecule will be important. Indeed, one uses the room temperature intramolecular structural parameters of this molecule as a reference to analyse the intramolecular structural parameters of the corresponding cation in the corresponding family salts. \sch
In particular we developed a statistical method to give an estimation of the charge carried by the BEDT-TTF cation in such salts (Guionneau et al., 1997) from a combination of the averaged values of the four central bond lengths. This method shows the linear variation of the charge with the distance δ = (b+c)-(a+d) where b and c are the averaged values of the central S—S bond lengths while a and d are the averaged values of the central C—C bond lengths. The estimation of the charge carried, Q, in such a way was obtained with an accuracy of 10%, the equation of linear variation was found to be Q=6.347–7.463δ. The central bond lengths of the neutral BEDT-TTF molecule were used as a reference point to obtain this equation. In order to know if we could use this method with low-temperature data of BEDT-TTF salts we needed to compare the values of δ for the room temperature and a temperature of around 100 K for which a lot of structural data are available in the studied series. The averaged central bond length values are close at room temperature and 100 K: a = 1.343 (4), b = 1.756 (3), c = 1.760 (3), d = 1.333 (4) Å (Guionneau et al., 1997) and a = 1.352 (4), b = 1.763 (3), c = 1.771 (3) and d = 1.349 (4) Å, respectively. The associated δ values are so very close at room temperature [0.840 (15) Å] and 100 K [0.834 (15) Å]. The small difference between these two values (-0.006 Å) corresponds to a difference in the charge estimation (+0.04 e-) which appears lower than the accuracy of the method (0.10 e-). It also shows that the charge calculated with this method from low-temperature data could be slightly overestimated as suspected in Gaultier et al. (1999). Thus, these results seem to confirm the validity of the δ method as a rough but quick and easy tool to estimate the charge partition in BEDT-TTF salts. Such a partition has been calculated using this method and successfully explains the conducting properties of some organic conductors (Martin et al., 1999; Coronado et al., 1998). It has also been used to show the change in the degree of ionicity that can occur when cooling (Gaultier et al., 1999; Guionneau et al., 1998).
In general, one of the features of the BEDT-TTF entities is the disorder that can affect the ethylene extremities. At room temperature such a disorder often appears in BEDT-TTF molecule based salts. It was also found in neutral BEDT-TTF (Kobayashi et al., 1986; Guionneau et al., 1997). One of the commonly used estimates of the disordering is the deviation from the normal corresponding C—C bond lengths (around 1.53 Å). In the title molecule, ethylene groups (C13—C14 and C18—C19) bond lengths are much closer from the normal values at 100 K [1.518 (3) Å and 1.517 (3) Å, respectively] than at room temperature [1.467 (3) Å and 1.421 Å]. Moreover, at 100 K, the displacement parameters of the ethylene carbon atoms appear to be of the same order of magnitude as those of the other carbon atoms of the molecule at room temperature while they are three times higher at room temperature. Such a thermal ordering of the neutral BEDT-TTF should be kept in mind when trying to understand the BEDT-TTF entities intramolecular changes that may occur by cooling in the corresponding salts.
The molecular packing of BEDT-TTF at room temperature, described as based on dimers (Kobayashi et al., 1986), remains identical at 100 K. It is worth noting that this behaviour is different from that of the TTF crystals where TTF or tetrathiofulvalene corresponds to the core of the BEDT-TTF molecule, which undergo a structural transition at low temperature (Batsanov, 1998).