The title complex, C
14H
20O
4S
8+.BF
4-, is a charge-transfer complex with typical charges for the donor and anion of +1 and -1, respectively. Two centrosymmetrically related donors form a face-to-face
-dimer with a strong intermolecular S
S interaction. These
-dimers stack along the
a axis to form a donor column. The structure is extensively hydrogen bonded.
Supporting information
CCDC reference: 143327
Crystals were obtained by electrocrystallization of 10 mg
2,3,4,5-tetrakis[(2-hydroxyethyl)thio]tetrathiafulvalene dissolved in 50 ml
1,1,2-trichloromethane with 4.96 mg KBF4 and 7.1 mg dibenzo-18-crown-6 in an
H-shaped tube. A constant current of 1.0 µA was applied to the supernatant
using platinum electrodes for two weeks.
Data collection: DENZO and SCALEPACK (Otwinowski & Minor, 1997); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
4,5-bis[(2-hydroxyethyl)thio]-2-{4,5-bis[(2-hydroxyethyl)thio]-1,3-dithiol-2-
ylidene}-1,3-dithiole
top
Crystal data top
C14H20O4S8+·BF4− | Z = 2 |
Mr = 595.59 | F(000) = 610 |
Triclinic, P1 | Dx = 1.671 Mg m−3 |
a = 9.7070 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.5750 (6) Å | Cell parameters from 3980 reflections |
c = 11.5920 (7) Å | θ = 0.9–25.4° |
α = 71.333 (3)° | µ = 0.81 mm−1 |
β = 85.678 (4)° | T = 293 K |
γ = 73.601 (3)° | Block, dark green |
V = 1183.58 (11) Å3 | 0.25 × 0.15 × 0.10 mm |
Data collection top
MacScience DIP 2030K image-plate system diffractometer | 3623 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.4°, θmin = 2.5° |
Detector resolution: 0.84 pixels mm-1 | h = −11→0 |
ω scans | k = −13→13 |
3980 measured reflections | l = −13→13 |
3980 independent reflections | |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0676P)2 + 1.9465P] where P = (Fo2 + 2Fc2)/3 |
3980 reflections | (Δ/σ)max = 0.001 |
284 parameters | Δρmax = 0.80 e Å−3 |
21 restraints | Δρmin = −0.47 e Å−3 |
Crystal data top
C14H20O4S8+·BF4− | γ = 73.601 (3)° |
Mr = 595.59 | V = 1183.58 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7070 (5) Å | Mo Kα radiation |
b = 11.5750 (6) Å | µ = 0.81 mm−1 |
c = 11.5920 (7) Å | T = 293 K |
α = 71.333 (3)° | 0.25 × 0.15 × 0.10 mm |
β = 85.678 (4)° | |
Data collection top
MacScience DIP 2030K image-plate system diffractometer | 3623 reflections with I > 2σ(I) |
3980 measured reflections | Rint = 0.000 |
3980 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 21 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.80 e Å−3 |
3980 reflections | Δρmin = −0.47 e Å−3 |
284 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.31412 (11) | 0.71973 (9) | 0.86598 (8) | 0.0440 (2) | |
S2 | 0.51616 (10) | 0.53811 (9) | 0.76734 (8) | 0.0433 (2) | |
S3 | 0.19900 (11) | 0.49342 (9) | 1.05265 (9) | 0.0463 (3) | |
S4 | 0.40813 (11) | 0.30952 (9) | 0.96116 (8) | 0.0450 (2) | |
S5 | 0.37452 (13) | 0.94793 (9) | 0.68362 (9) | 0.0529 (3) | |
S6 | 0.61704 (13) | 0.73837 (11) | 0.57268 (9) | 0.0550 (3) | |
S7 | 0.06311 (12) | 0.29691 (10) | 1.21829 (9) | 0.0531 (3) | |
S8 | 0.31853 (13) | 0.08637 (10) | 1.13017 (9) | 0.0551 (3) | |
F1 | 0.8136 (7) | 0.3574 (4) | 0.6852 (5) | 0.171 (2) | |
F2 | 0.8134 (5) | 0.2442 (4) | 0.8731 (3) | 0.1185 (14) | |
F3 | 0.8909 (4) | 0.1478 (4) | 0.7339 (4) | 0.1159 (14) | |
F4 | 0.6640 (4) | 0.2395 (5) | 0.7453 (6) | 0.172 (2) | |
O1 | 0.2341 (7) | 0.8653 (4) | 0.4824 (4) | 0.1145 (18) | |
H1 | 0.2185 | 0.8634 | 0.4145 | 0.172* | |
O2 | 0.7894 (4) | 0.7111 (4) | 0.3641 (3) | 0.0765 (10) | |
H2 | 0.8166 | 0.7417 | 0.2952 | 0.115* | |
O3 | −0.1941 (4) | 0.3611 (4) | 1.3698 (3) | 0.0819 (11) | |
H3 | −0.2005 | 0.2928 | 1.4168 | 0.123* | |
O4 | 0.1144 (4) | 0.2241 (4) | 0.8847 (3) | 0.0767 (10) | |
H4 | 0.0274 | 0.2520 | 0.8723 | 0.115* | |
B1 | 0.7951 (5) | 0.2473 (4) | 0.7570 (4) | 0.0591 (12) | |
C1 | 0.3818 (4) | 0.5646 (3) | 0.8699 (3) | 0.0404 (8) | |
C2 | 0.3337 (4) | 0.4655 (3) | 0.9513 (3) | 0.0400 (8) | |
C3 | 0.4056 (4) | 0.7827 (3) | 0.7373 (3) | 0.0414 (8) | |
C4 | 0.5021 (4) | 0.6984 (3) | 0.6914 (3) | 0.0399 (8) | |
C5 | 0.1955 (4) | 0.3362 (3) | 1.1154 (3) | 0.0411 (8) | |
C6 | 0.2942 (4) | 0.2501 (3) | 1.0732 (3) | 0.0427 (8) | |
C7 | 0.2022 (5) | 0.9987 (4) | 0.6063 (4) | 0.0640 (12) | |
H7A | 0.1565 | 1.0845 | 0.6042 | 0.080* | |
H7B | 0.1425 | 0.9471 | 0.6536 | 0.080* | |
C8 | 0.2087 (7) | 0.9902 (5) | 0.4798 (5) | 0.0791 (16) | |
H8A | 0.1200 | 1.0398 | 0.4379 | 0.080* | |
H8B | 0.2846 | 1.0241 | 0.4365 | 0.080* | |
C9 | 0.6041 (5) | 0.6376 (4) | 0.4832 (4) | 0.0547 (10) | |
H9A | 0.5070 | 0.6327 | 0.4829 | 0.080* | |
H9B | 0.6651 | 0.5536 | 0.5173 | 0.080* | |
C10 | 0.6517 (6) | 0.6946 (5) | 0.3574 (4) | 0.0664 (12) | |
H10A | 0.6548 | 0.6410 | 0.3083 | 0.080* | |
H10B | 0.5852 | 0.7753 | 0.3208 | 0.080* | |
C11 | 0.0099 (5) | 0.4286 (4) | 1.2806 (4) | 0.0551 (10) | |
H11A | −0.0526 | 0.5009 | 1.2249 | 0.080* | |
H11B | 0.0930 | 0.4515 | 1.2949 | 0.080* | |
C12 | −0.0675 (5) | 0.3859 (5) | 1.3979 (4) | 0.0608 (11) | |
H12A | −0.0065 | 0.3109 | 1.4518 | 0.080* | |
H12B | −0.0927 | 0.4506 | 1.4371 | 0.080* | |
C13 | 0.2945 (7) | 0.0442 (5) | 0.9961 (5) | 0.0771 (14) | |
H13A | 0.3250 | −0.0464 | 1.0165 | 0.080* | |
H13B | 0.3572 | 0.0774 | 0.9336 | 0.080* | |
C14 | 0.1493 (7) | 0.0900 (5) | 0.9450 (6) | 0.0829 (16) | |
H14A | 0.1430 | 0.0474 | 0.8877 | 0.080* | |
H14B | 0.0821 | 0.0708 | 1.0094 | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0496 (5) | 0.0433 (5) | 0.0387 (5) | −0.0155 (4) | 0.0064 (4) | −0.0111 (4) |
S2 | 0.0482 (5) | 0.0418 (5) | 0.0394 (5) | −0.0159 (4) | 0.0062 (4) | −0.0101 (4) |
S3 | 0.0515 (6) | 0.0409 (5) | 0.0445 (5) | −0.0176 (5) | 0.0094 (4) | −0.0083 (4) |
S4 | 0.0551 (6) | 0.0443 (5) | 0.0377 (5) | −0.0184 (5) | 0.0044 (4) | −0.0123 (4) |
S5 | 0.0678 (7) | 0.0407 (5) | 0.0525 (6) | −0.0224 (5) | −0.0057 (5) | −0.0096 (4) |
S6 | 0.0688 (7) | 0.0634 (7) | 0.0463 (5) | −0.0399 (6) | 0.0189 (5) | −0.0204 (5) |
S7 | 0.0606 (6) | 0.0530 (6) | 0.0503 (6) | −0.0298 (5) | 0.0140 (5) | −0.0129 (4) |
S8 | 0.0755 (8) | 0.0412 (5) | 0.0462 (5) | −0.0202 (5) | −0.0053 (5) | −0.0051 (4) |
F1 | 0.223 (6) | 0.096 (3) | 0.163 (5) | −0.045 (4) | 0.093 (4) | −0.016 (3) |
F2 | 0.139 (4) | 0.140 (3) | 0.088 (2) | −0.025 (3) | 0.007 (2) | −0.065 (2) |
F3 | 0.117 (3) | 0.109 (3) | 0.123 (3) | 0.019 (2) | −0.019 (2) | −0.076 (2) |
F4 | 0.085 (3) | 0.187 (5) | 0.280 (7) | −0.024 (3) | −0.042 (4) | −0.124 (5) |
O1 | 0.208 (6) | 0.084 (3) | 0.071 (3) | −0.068 (3) | −0.030 (3) | −0.018 (2) |
O2 | 0.080 (2) | 0.099 (3) | 0.064 (2) | −0.046 (2) | 0.0266 (18) | −0.0294 (19) |
O3 | 0.063 (2) | 0.111 (3) | 0.071 (2) | −0.044 (2) | 0.0024 (17) | −0.011 (2) |
O4 | 0.070 (2) | 0.088 (3) | 0.074 (2) | −0.032 (2) | −0.0093 (18) | −0.0163 (19) |
B1 | 0.064 (3) | 0.054 (3) | 0.063 (3) | −0.013 (3) | 0.006 (2) | −0.027 (2) |
C1 | 0.046 (2) | 0.0441 (19) | 0.0321 (17) | −0.0187 (17) | 0.0020 (14) | −0.0083 (14) |
C2 | 0.047 (2) | 0.0424 (19) | 0.0308 (16) | −0.0186 (17) | 0.0018 (14) | −0.0071 (14) |
C3 | 0.049 (2) | 0.0419 (19) | 0.0350 (17) | −0.0205 (17) | 0.0006 (15) | −0.0066 (14) |
C4 | 0.046 (2) | 0.0424 (19) | 0.0343 (17) | −0.0211 (17) | 0.0026 (14) | −0.0084 (14) |
C5 | 0.050 (2) | 0.0427 (19) | 0.0323 (17) | −0.0225 (17) | −0.0003 (14) | −0.0047 (14) |
C6 | 0.052 (2) | 0.0411 (19) | 0.0368 (18) | −0.0202 (18) | −0.0002 (15) | −0.0080 (15) |
C7 | 0.065 (3) | 0.048 (2) | 0.069 (3) | −0.008 (2) | −0.013 (2) | −0.008 (2) |
C8 | 0.110 (5) | 0.064 (3) | 0.061 (3) | −0.037 (3) | −0.025 (3) | 0.002 (2) |
C9 | 0.062 (3) | 0.063 (3) | 0.049 (2) | −0.028 (2) | 0.0101 (19) | −0.0232 (19) |
C10 | 0.077 (3) | 0.088 (3) | 0.047 (2) | −0.036 (3) | 0.009 (2) | −0.027 (2) |
C11 | 0.054 (2) | 0.051 (2) | 0.060 (2) | −0.020 (2) | 0.0089 (19) | −0.0139 (19) |
C12 | 0.055 (3) | 0.071 (3) | 0.058 (3) | −0.022 (2) | 0.009 (2) | −0.020 (2) |
C13 | 0.097 (4) | 0.060 (3) | 0.081 (3) | −0.025 (3) | 0.008 (3) | −0.028 (3) |
C14 | 0.093 (4) | 0.075 (3) | 0.091 (4) | −0.039 (3) | −0.017 (3) | −0.022 (3) |
Geometric parameters (Å, º) top
S1—C1 | 1.715 (4) | O4—H4 | 0.8200 |
S1—C3 | 1.736 (4) | C1—C2 | 1.403 (5) |
S2—C1 | 1.727 (4) | C3—C4 | 1.361 (5) |
S2—C4 | 1.751 (4) | C5—C6 | 1.361 (6) |
S3—C2 | 1.722 (4) | C7—C8 | 1.497 (7) |
S3—C5 | 1.740 (4) | C7—H7A | 0.9599 |
S4—C2 | 1.715 (4) | C7—H7B | 0.9639 |
S4—C6 | 1.738 (4) | C8—H8A | 0.9549 |
S5—C3 | 1.754 (4) | C8—H8B | 0.9645 |
S5—C7 | 1.811 (5) | C9—C10 | 1.494 (6) |
S6—C4 | 1.734 (3) | C9—H9A | 0.9600 |
S6—C9 | 1.825 (4) | C9—H9B | 0.9572 |
S7—C5 | 1.742 (4) | C10—H10A | 0.9602 |
S7—C11 | 1.821 (4) | C10—H10B | 0.9567 |
S8—C6 | 1.748 (4) | C11—C12 | 1.511 (6) |
S8—C13 | 1.820 (5) | C11—H11A | 0.9552 |
F1—B1 | 1.333 (5) | C11—H11B | 0.9584 |
F2—B1 | 1.358 (5) | C12—H12A | 0.9555 |
F3—B1 | 1.349 (5) | C12—H12B | 0.9613 |
F4—B1 | 1.321 (5) | C13—C14 | 1.456 (8) |
O1—C8 | 1.387 (6) | C13—H13A | 0.9592 |
O1—H1 | 0.8200 | C13—H13B | 0.9654 |
O2—C10 | 1.414 (6) | C14—H14A | 0.9595 |
O2—H2 | 0.8200 | C14—H14B | 0.9659 |
O3—C12 | 1.421 (5) | S4—S1i | 3.356 (1) |
O3—H3 | 0.8200 | S3—S2i | 3.456 (1) |
O4—C14 | 1.434 (6) | | |
| | | |
C1—S1—C3 | 95.98 (17) | O1—C8—C7 | 110.7 (4) |
C1—S2—C4 | 95.67 (17) | O1—C8—H8A | 109.7 |
C2—S3—C5 | 95.67 (18) | C7—C8—H8A | 109.4 |
C2—S4—C6 | 95.78 (17) | O1—C8—H8B | 109.5 |
C3—S5—C7 | 102.11 (19) | C7—C8—H8B | 109.3 |
C4—S6—C9 | 101.87 (18) | H8A—C8—H8B | 108.3 |
C5—S7—C11 | 102.88 (18) | C10—C9—S6 | 107.3 (3) |
C6—S8—C13 | 103.4 (2) | C10—C9—H9A | 111.3 |
C8—O1—H1 | 109.5 | S6—C9—H9A | 109.8 |
C10—O2—H2 | 109.5 | C10—C9—H9B | 109.4 |
C12—O3—H3 | 109.5 | S6—C9—H9B | 110.6 |
C14—O4—H4 | 109.5 | H9A—C9—H9B | 108.4 |
F4—B1—F1 | 111.5 (5) | O2—C10—C9 | 109.0 (4) |
F4—B1—F3 | 109.0 (4) | O2—C10—H10A | 109.9 |
F1—B1—F3 | 111.7 (4) | C9—C10—H10A | 110.6 |
F4—B1—F2 | 108.4 (4) | O2—C10—H10B | 109.4 |
F1—B1—F2 | 106.2 (4) | C9—C10—H10B | 109.1 |
F3—B1—F2 | 109.9 (4) | H10A—C10—H10B | 108.8 |
C2—C1—S1 | 122.8 (3) | C12—C11—S7 | 107.4 (3) |
C2—C1—S2 | 122.0 (3) | C12—C11—H11A | 109.8 |
S1—C1—S2 | 115.18 (19) | S7—C11—H11A | 110.5 |
C1—C2—S4 | 122.9 (3) | C12—C11—H11B | 111.0 |
C1—C2—S3 | 121.5 (3) | S7—C11—H11B | 109.9 |
S4—C2—S3 | 115.59 (19) | H11A—C11—H11B | 108.3 |
C4—C3—S1 | 116.7 (3) | O3—C12—C11 | 108.3 (4) |
C4—C3—S5 | 125.7 (3) | O3—C12—H12A | 110.2 |
S1—C3—S5 | 117.5 (2) | C11—C12—H12A | 109.6 |
C3—C4—S6 | 124.9 (3) | O3—C12—H12B | 109.7 |
C3—C4—S2 | 115.9 (3) | C11—C12—H12B | 110.5 |
S6—C4—S2 | 119.1 (2) | H12A—C12—H12B | 108.6 |
C6—C5—S3 | 116.3 (3) | C14—C13—S8 | 115.8 (4) |
C6—C5—S7 | 123.2 (3) | C14—C13—H13A | 108.9 |
S3—C5—S7 | 120.3 (2) | S8—C13—H13A | 108.3 |
C5—C6—S4 | 116.5 (3) | C14—C13—H13B | 108.0 |
C5—C6—S8 | 124.2 (3) | S8—C13—H13B | 108.3 |
S4—C6—S8 | 119.2 (2) | H13A—C13—H13B | 107.3 |
C8—C7—S5 | 114.9 (4) | O4—C14—C13 | 110.3 (4) |
C8—C7—H7A | 109.4 | O4—C14—H14A | 109.5 |
S5—C7—H7A | 108.4 | C13—C14—H14A | 109.2 |
C8—C7—H7B | 108.0 | O4—C14—H14B | 110.1 |
S5—C7—H7B | 108.6 | C13—C14—H14B | 109.5 |
H7A—C7—H7B | 107.3 | H14A—C14—H14B | 108.4 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4ii | 0.82 | 2.09 | 2.891 (5) | 166 |
O1—H1···F3ii | 0.82 | 2.15 | 2.930 (5) | 143 |
O1—H1···F4ii | 0.82 | 2.55 | 3.224 (7) | 153 |
O3—H3···O1iii | 0.82 | 1.93 | 2.748 (6) | 174 |
O4—H4···F2iv | 0.82 | 2.10 | 2.875 (6) | 157 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+2; (iv) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | C14H20O4S8+·BF4− |
Mr | 595.59 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.7070 (5), 11.5750 (6), 11.5920 (7) |
α, β, γ (°) | 71.333 (3), 85.678 (4), 73.601 (3) |
V (Å3) | 1183.58 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.25 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | MacScience DIP 2030K image-plate system diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3980, 3980, 3623 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.604 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.149, 1.08 |
No. of reflections | 3980 |
No. of parameters | 284 |
No. of restraints | 21 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.47 |
Selected geometric parameters (Å, º) topS1—C1 | 1.715 (4) | F2—B1 | 1.358 (5) |
S1—C3 | 1.736 (4) | F3—B1 | 1.349 (5) |
S2—C1 | 1.727 (4) | F4—B1 | 1.321 (5) |
S2—C4 | 1.751 (4) | O1—C8 | 1.387 (6) |
S3—C2 | 1.722 (4) | O2—C10 | 1.414 (6) |
S3—C5 | 1.740 (4) | O3—C12 | 1.421 (5) |
S4—C2 | 1.715 (4) | O4—C14 | 1.434 (6) |
S4—C6 | 1.738 (4) | C1—C2 | 1.403 (5) |
S5—C3 | 1.754 (4) | C3—C4 | 1.361 (5) |
S5—C7 | 1.811 (5) | C5—C6 | 1.361 (6) |
S6—C4 | 1.734 (3) | C7—C8 | 1.497 (7) |
S6—C9 | 1.825 (4) | C9—C10 | 1.494 (6) |
S7—C5 | 1.742 (4) | C11—C12 | 1.511 (6) |
S7—C11 | 1.821 (4) | C13—C14 | 1.456 (8) |
S8—C6 | 1.748 (4) | S4—S1i | 3.356 (1) |
S8—C13 | 1.820 (5) | S3—S2i | 3.456 (1) |
F1—B1 | 1.333 (5) | | |
| | | |
C1—S1—C3 | 95.98 (17) | C4—C3—S1 | 116.7 (3) |
C1—S2—C4 | 95.67 (17) | C4—C3—S5 | 125.7 (3) |
C2—S3—C5 | 95.67 (18) | S1—C3—S5 | 117.5 (2) |
C2—S4—C6 | 95.78 (17) | C3—C4—S6 | 124.9 (3) |
C3—S5—C7 | 102.11 (19) | C3—C4—S2 | 115.9 (3) |
C4—S6—C9 | 101.87 (18) | S6—C4—S2 | 119.1 (2) |
C5—S7—C11 | 102.88 (18) | C6—C5—S3 | 116.3 (3) |
C6—S8—C13 | 103.4 (2) | C6—C5—S7 | 123.2 (3) |
F4—B1—F1 | 111.5 (5) | S3—C5—S7 | 120.3 (2) |
F4—B1—F3 | 109.0 (4) | C5—C6—S4 | 116.5 (3) |
F1—B1—F3 | 111.7 (4) | C5—C6—S8 | 124.2 (3) |
F4—B1—F2 | 108.4 (4) | S4—C6—S8 | 119.2 (2) |
F1—B1—F2 | 106.2 (4) | C8—C7—S5 | 114.9 (4) |
F3—B1—F2 | 109.9 (4) | O1—C8—C7 | 110.7 (4) |
C2—C1—S1 | 122.8 (3) | C10—C9—S6 | 107.3 (3) |
C2—C1—S2 | 122.0 (3) | O2—C10—C9 | 109.0 (4) |
S1—C1—S2 | 115.18 (19) | C12—C11—S7 | 107.4 (3) |
C1—C2—S4 | 122.9 (3) | O3—C12—C11 | 108.3 (4) |
C1—C2—S3 | 121.5 (3) | C14—C13—S8 | 115.8 (4) |
S4—C2—S3 | 115.59 (19) | O4—C14—C13 | 110.3 (4) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4ii | 0.820 | 2.089 | 2.891 (5) | 165.6 |
O1—H1···F3ii | 0.820 | 2.145 | 2.930 (5) | 142.6 |
O1—H1···F4ii | 0.820 | 2.546 | 3.224 (7) | 152.8 |
O3—H3···O1iii | 0.820 | 1.932 | 2.748 (6) | 173.8 |
O4—H4···F2iv | 0.820 | 2.104 | 2.875 (6) | 156.5 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+2; (iv) x−1, y, z. |
The structures of many charge-transfer complexes with the donor containing a tetrathiafulvalene (TTF) unit have been reported (Endres, 1981; Bechgarrd et al., 1997; Katayama et al., 1985; Endres, 1987). Studies of the relationship between physical properties and structure have shown the co-existence of high electric conductivity and non-covalent interactions in complexes, such as hydrogen bonds and enhanced van der Waals forces. We have prepared a new charge-transfer complex, (I), with the possibility of hydrogen bonding between donor and acceptor components. The title complex is a charge-transfer complex with one donor and one BF4- anion in the asymmetric unit. In the donor, bond distances and angles at S are dependent on the hybridization state of the C atoms to which S is bonded, so S—Csp3 is longer that S—Csp2 and angles are wider in the case of an sp2-hydridized C atom. The S—Csp3 bond distance is longer than reported values on derivatives of TTF and S—Csp2 bond distances are similar (Saitoh et al., 1995; Katayama et al., 1985; Brunn et al., 1987; Endres, 1981). C═C bond distances in the TTF core are in the same range as in TTF+ cores. C—C bond distances in the 2-hydroxyethyl groups are similar to C—C bond distances in the ethyl group in BEDT–TTF (Saitoh et al., 1995). C—O bond distances range from 1.385 (6) to 1.433 (7) Å. With the exception of the four 2-hydroxyethyl groups, all the atoms in the donor are close to coplanar with a deviation of 0.20 Å, owing to a charge-transfer interaction between donor and anion. All four 2-hydroxyethyl groups depart from this plane in the same direction and form a U-type structure not reported previously (Batsanov et al., 1995).
Parallel pairs of donors related by a centre of symmetry lie face-to-face and form an X-type donor dimer with a strong π–π interaction. Donor dimers stack along the a axis to form a donor column. The intermolecular S···S contacts in the π-dimer are significantly shorter than the sum of van der Waals radii, 3.7 Å, but no strong intermolecular contacts exist between dimers in a column. The anion is tetrahedral with bond distances and angles similar to reported values (Hursthouse et al., 1995; Saitoh et al., 1995). Owing to the –OH group in the donor and strongly electronegative element in the anion, a lot of hydrogen bonds of types O—H···F and O—H···O exist in the title complex. This phase is an insulator at room temperature, corresponding to the theory of Pierles distortion in low-dimensional conductors. Experiments on physical properties are in progress.