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The radical cation salt ET(NCS)0.77 [bis(ethylenedithio)tetra­thiafulvalene thiocyanate (1/0.77)] has been prepared for the first time by electrocrystallization and its crystal and electronic structure at 110 K was investigated. The unit-cell dimensions are orthorhombic, a = 6.638 (1), b = 8.309 (2), c = 28.776 (6) Å, V = 1587.1 (6) Å3, space group Pbcm, Z = 4. The compound has a layered structure. The ET radical cations of the conducting cationic layer build stacks. In the anionic layer the thiocyanate groups form polymeric chains where they are oriented in a `head-to-tail' mode. The structure has short intermolecular contacts of the cation-cation, anion-anion and cation-anion types, which leads to the formation of a three-dimensional structure of intermolecular interactions. This phenomenon is very rare in molecular conductors. Tight binding band structure calculations suggest, however, that the interlayer interactions through the anions are weak and that the incomplete occupation of the anion sites is the reason for the activated conductivity of the salt.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768101019322/av0048sup1.cif
Contains datablocks 55555abs, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768101019322/av0048sup2.hkl
Contains datablock g

CCDC reference: 180221

Computing details top

Program(s) used to solve structure: SHELXS93 (Sheldrick, 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(55555abs) top
Crystal data top
C10.77H8N0.77S8.77F(000) = 873
Mr = 429.37Dx = 1.797 Mg m3
Orthorhombic, PbcmMo Kα radiation, λ = 0.71069 Å
a = 6.638 (1) ŵ = 1.21 mm1
b = 8.309 (2) ÅT = 110 K
c = 28.776 (6) ÅRhombic plates, black
V = 1587.1 (6) Å30.38 × 0.33 × 0.25 mm
Z = 4
Data collection top
Bruker AXS SMART 1000
diffractometer
1533 independent reflections
Radiation source: fine-focus sealed tube1288 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ω–scanningθmax = 30.1°, θmin = 2.8°
Absorption correction: semiempirical (using intensity measurements)h = 94
k = 115
3049 measured reflectionsl = 3915
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.057Secondary atom site location: difference Fourier map
wR(F2) = 0.141Hydrogen site location: inferred from neighbouring sites
S = 0.88H-atom parameters not defined?
1533 reflectionsCalculated w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
103 parameters(Δ/σ)max = 0.057
Special details top

Experimental. omega-scanning, scanning pitch 0.3degree, frame measuring time 30 s.

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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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
xyzUiso*/UeqOcc. (<1)
S10.7771 (3)0.4456 (3)0.75000.0477 (6)0.771 (4)
S20.34671 (12)0.36754 (10)0.55491 (3)0.02360 (19)
S30.77278 (12)0.42920 (11)0.53610 (3)0.0264 (2)
S40.41971 (13)0.17472 (11)0.63959 (3)0.0264 (2)
S50.92725 (13)0.23599 (14)0.61279 (4)0.0428 (3)
N10.914 (4)0.1034 (14)0.75000.340 (13)0.808 (18)
C10.847 (2)0.223 (3)0.75000.170 (9)0.70 (2)
C20.5205 (5)0.2779 (4)0.59233 (11)0.0202 (7)
C30.7175 (5)0.3036 (4)0.58273 (11)0.0236 (8)
C40.5246 (5)0.4563 (3)0.51915 (11)0.0210 (7)
C50.8215 (6)0.1316 (6)0.66082 (13)0.0537 (14)
H5A0.91870.12870.68550.080*
H5B0.80030.02280.65070.080*
C60.6304 (6)0.1811 (6)0.67913 (15)0.0543 (14)
H6A0.59750.12150.70670.080*
H6B0.64940.29140.68800.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0408 (11)0.0694 (15)0.0330 (9)0.0030 (11)0.0000.000
S20.0148 (4)0.0327 (4)0.0233 (3)0.0004 (4)0.0009 (3)0.0017 (4)
S30.0136 (3)0.0358 (4)0.0298 (4)0.0031 (4)0.0037 (3)0.0072 (4)
S40.0165 (4)0.0368 (5)0.0259 (4)0.0014 (4)0.0007 (3)0.0053 (4)
S50.0141 (4)0.0638 (7)0.0504 (6)0.0015 (5)0.0029 (4)0.0295 (5)
N10.86 (4)0.131 (8)0.031 (5)0.253 (13)0.0000.000
C10.127 (10)0.37 (3)0.016 (5)0.149 (12)0.0000.000
C20.0171 (14)0.0224 (15)0.0211 (14)0.0028 (14)0.0004 (12)0.0012 (13)
C30.0168 (14)0.0262 (16)0.0278 (15)0.0003 (14)0.0032 (13)0.0045 (14)
C40.0147 (14)0.0187 (16)0.0296 (15)0.0016 (13)0.0009 (13)0.0005 (13)
C50.030 (2)0.102 (4)0.0286 (18)0.013 (2)0.0003 (16)0.020 (2)
C60.0226 (19)0.099 (4)0.041 (2)0.010 (2)0.0115 (17)0.013 (3)
Geometric parameters (Å, º) top
S1—C11.91 (2)S5—C31.733 (3)
S2—C41.731 (3)S5—C51.776 (4)
S2—C21.745 (3)N1—C11.09 (3)
S3—C41.733 (3)C2—C31.354 (5)
S3—C31.739 (3)C4—C4i1.360 (6)
S4—C21.741 (3)C5—C61.434 (6)
S4—C61.804 (4)
C4—S2—C295.60 (15)C2—C3—S5128.6 (3)
C4—S3—C395.41 (15)C2—C3—S3117.1 (2)
C2—S4—C6100.42 (18)S5—C3—S3114.20 (18)
C3—S5—C5103.25 (17)C4i—C4—S2123.1 (3)
N1—C1—S1170.19 (17)C4i—C4—S3121.7 (3)
C3—C2—S4127.5 (3)S2—C4—S3115.20 (17)
C3—C2—S2116.5 (2)C6—C5—S5119.5 (3)
S4—C2—S2115.98 (18)C5—C6—S4116.5 (3)
Symmetry code: (i) x+1, y+1, z+1.
 

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