4,5:4′,5′-Bis(methyl­enedithio)tetrathia­fulvalenium dichloride

Xiao, X.-W.; Xu, W.; Xu, H.; Zhang, D.-Q.; Zhu, D.-B.

doi:10.1107/S1600536804032350

4,5:4′,5′-Bis(methylenedithio)tetrathiafulvalenium dichloride

X.-W. Xiao, W. Xu, H. Xu, D.-Q. Zhang and D.-B. Zhu

The title compound, C₈H₄S ${}_{8}^{\,2+}$ ·2Cl⁻, was prepared electrochemically. To our knowledge, it is the first dication salt of tris(methylenedithio)tetrathiafulvalene (BMDT-TTF). The asymmetric unit consists of two chloride anions and one dication, all three located on mirror planes. In the crystal structure, the BMDT-TTF cations form dimers, which are linked by short S

S and S

Cl contacts, leading to a layered structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804032350/nc6006sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804032350/nc6006Isup2.hkl Contains datablock I

CCDC reference: 250103

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.007 Å
R factor = 0.060
wR factor = 0.177
Data-to-parameter ratio = 19.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT722_ALERT_1_A Angle   Calc       94.00, Rep      108.80 Dev...      14.80 Deg.
              S1   -C1   -H1A     6.565   1.555   1.555
PLAT722_ALERT_1_A Angle   Calc       94.00, Rep      108.80 Dev...      14.80 Deg.
              S1   -C1   -H1B     6.565   1.555   1.555
PLAT722_ALERT_1_A Angle   Calc       93.00, Rep      108.30 Dev...      15.30 Deg.
              S4   -C6   -H6A     6.565   1.555   1.555
PLAT722_ALERT_1_A Angle   Calc       93.00, Rep      108.30 Dev...      15.30 Deg.
              S4   -C6   -H6B     6.565   1.555   1.555

Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95
PLAT431_ALERT_2_B Short Inter HL..A Contact  Cl1    ..  Cl2     ..       3.16 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT085_ALERT_2_C SHELXL default weighting scheme is not optimized          ?
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature         293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature ....        293
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.69 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.55
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  S2      ..       3.28 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  S2      ..       3.28 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  S1      ..       3.44 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  S1      ..       3.44 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2    ..  S3      ..       3.31 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2    ..  S3      ..       3.31 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2    ..  S4      ..       3.36 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2    ..  S4      ..       3.36 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.36 Ratio
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C8 H4 S8
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              Cl

   4 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  21 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  13 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL.

4,5:4',5'-Bis(methylenedithio)tetrathiafulvalenium dichloride top

Crystal data top

C₈H₄S₈²⁺·2Cl⁻	F(000) = 856
M_r = 427.49	D_x = 1.901 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 2778 reflections
a = 15.405 (3) Å	θ = 2.7–27.5°
b = 8.8860 (18) Å	µ = 1.53 mm⁻¹
c = 11.105 (2) Å	T = 293 K
β = 100.75 (3)°	Block, black
V = 1493.5 (5) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1739 independent reflections
Radiation source: fine-focus sealed tube	893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 0.76 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
φ or ω?? scans	h = −19→19
Absorption correction: empirical (using intensity measurements) (Abscor; Higashi, 1995).	k = −11→11
T_min = 0.714, T_max = 0.753	l = −14→14
2778 measured 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.177	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
1739 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

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	U_iso*/U_eq
S1	0.28027 (8)	0.16859 (14)	0.24601 (11)	0.0533 (4)
S2	0.13512 (7)	0.16669 (13)	0.01393 (11)	0.0432 (3)
S3	−0.00455 (7)	−0.16625 (14)	−0.23965 (10)	0.0431 (4)
S4	−0.13176 (9)	−0.16906 (14)	−0.48822 (12)	0.0549 (4)
C1	0.3403 (6)	0.0000	0.2908 (10)	0.102 (4)
H1A	0.3934	0.0000	0.2556	0.123*
H1B	0.3586	0.0000	0.3793	0.123*
C2	0.2074 (3)	0.0772 (5)	0.1299 (4)	0.0398 (10)
C3	0.0958 (4)	0.0000	−0.0563 (5)	0.0396 (14)
C4	0.0347 (4)	0.0000	−0.1692 (6)	0.0385 (14)
C5	−0.0693 (2)	−0.0773 (5)	−0.3630 (4)	0.0393 (10)
C6	−0.1826 (6)	0.0000	−0.5488 (8)	0.090 (3)
H6A	−0.1848	0.0000	−0.6366	0.109*
H6B	−0.2431	0.0000	−0.5355	0.109*
Cl1	−0.17968 (15)	−0.5000	−0.1364 (2)	0.0775 (7)
Cl2	−0.07192 (13)	−0.5000	−0.3520 (2)	0.0766 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0561 (8)	0.0509 (8)	0.0450 (7)	−0.0076 (6)	−0.0108 (6)	−0.0023 (6)
S2	0.0462 (6)	0.0380 (7)	0.0405 (6)	−0.0038 (5)	−0.0049 (5)	0.0011 (5)
S3	0.0428 (6)	0.0384 (7)	0.0424 (7)	0.0022 (5)	−0.0064 (5)	−0.0030 (5)
S4	0.0573 (8)	0.0520 (8)	0.0465 (7)	−0.0001 (6)	−0.0131 (6)	−0.0066 (6)
C1	0.104 (7)	0.064 (6)	0.109 (8)	0.000	−0.060 (6)	0.000
C2	0.034 (2)	0.042 (3)	0.041 (2)	−0.0019 (18)	0.0017 (18)	0.0027 (19)
C3	0.039 (3)	0.040 (4)	0.037 (3)	0.000	0.000 (3)	0.000
C4	0.039 (3)	0.035 (3)	0.038 (3)	0.000	0.000 (3)	0.000
C5	0.031 (2)	0.044 (3)	0.038 (2)	0.0010 (18)	−0.0050 (18)	−0.0008 (19)
C6	0.103 (7)	0.060 (6)	0.084 (7)	0.000	−0.046 (5)	0.000
Cl1	0.0889 (15)	0.0551 (13)	0.0822 (16)	0.000	−0.0004 (12)	0.000
Cl2	0.0739 (14)	0.0605 (14)	0.0855 (16)	0.000	−0.0104 (11)	0.000

Geometric parameters (Å, º) top

S1—C2	1.744 (4)	C3—C4	1.420 (8)
S1—C1	1.782 (4)	C3—S2ⁱ	1.730 (3)
S2—C3	1.730 (3)	C4—S3ⁱ	1.727 (3)
S2—C2	1.731 (4)	C5—C5ⁱ	1.374 (9)
S3—C4	1.727 (3)	C6—S4ⁱ	1.768 (4)
S3—C5	1.728 (4)	C1—H1A	0.9700
S4—C5	1.739 (4)	C1—H1B	0.9700
S4—C6	1.768 (4)	C6—H6A	0.9700
C1—S1ⁱ	1.782 (4)	C6—H6B	0.9700
C2—C2ⁱ	1.372 (9)

C2—S1—C1	92.5 (3)	C5ⁱ—C5—S4	117.96 (14)
C3—S2—C2	93.7 (2)	C5ⁱ—C5—S3	117.21 (14)
C4—S3—C5	94.0 (2)	S4—C5—S3	124.8 (3)
C5—S4—C6	92.6 (3)	S4ⁱ—C6—S4	116.3 (4)
S1ⁱ—C1—S1	114.4 (4)	S1—C1—H1A	108.8
C2ⁱ—C2—S1	117.76 (14)	S1ⁱⁱ—C1—H1A	108.8
C2ⁱ—C2—S2	117.36 (15)	S1—C1—H1B	108.8
S1—C2—S2	124.9 (3)	S1ⁱⁱ—C1—H1B	108.8
C4—C3—S2	121.11 (17)	H1A—C1—H1B	107.7
C4—C3—S2ⁱ	121.11 (17)	S4—C6—H6A	108.3
S2—C3—S2ⁱ	117.8 (3)	S4ⁱⁱ—C6—H6A	108.3
C3—C4—S3	121.20 (17)	S4—C6—H6B	108.3
C3—C4—S3ⁱ	121.20 (17)	S4ⁱⁱ—C6—H6B	108.3
S3—C4—S3ⁱ	117.6 (3)	H6A—C6—H6B	107.4

Symmetry codes: (i) x, −y, z; (ii) x, −y+1, z.

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4,5:4′,5′-Bis(methyl­enedithio)tetrathia­fulvalenium dichloride

Supporting information

Key indicators

checkCIF/PLATON results

4,5:4′,5′-Bis(methylenedithio)tetrathiafulvalenium dichloride