Download citation
Download citation
link to html
Tetra­methyl­tetra­thia­fulvalene and 1,4-di­nitro­benzene co-crystallize in a mixed-stack 1:1 complex, C10H12S4·C6H4N2O4, without appreciable charge transfer. Both molecules lie on the same crystallographic twofold axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000114/cv6162sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000114/cv6162Isup2.hkl
Contains datablock I

CCDC reference: 204688

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.028
  • wR factor = 0.079
  • Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The title complex, (I), was prepared in the course of our studies of tetrathiafulvalene (TTF) based charge-transfer (CT) systems (John et al., 2000; Moore et al., 2001; Batsanov et al., 2001 and references therein). Whilst many hundreds of TTF derivatives have been studied structurally, a survey of the Cambridge Crystallographic Database (Allen, 2002) found only seven complexes containing the 1,4-dinitrobenzene (DNB) moiety.

The structure contains mixed stacks of alternating molecules of the donor tetramethyltetrathiafulvalene (TMTTF) and acceptor DNB. Both molecules lie on (and perpendicular to) the same crystallographic twofold axis, resulting in the maximum overlap between these molecules (Fig. 1). In this, (I) differs from the 1:1 complex (II) between unsubstituted TTF and DNB (Bryce et al., 1982), where mixed stacks also exist, but the overlap between adjacent molecules is only partial. Alternatively, the motif of (I) can be described as layers, parallel to the (0 1 0) plane. Molecules in a layer are arranged in a checker-board order, each donor molecule surrounded by four acceptor ones, and vice versa.

The average interplanar separation in the stack of (I) is shorter than in (II), 3.44 Å versus. 3.64 Å, even making allowance for the different temperatures of these studies, 120 versus 295 K. Thus, linear expansion of pure DNB (di Rienzo et al., 1980; Tonogaki et al., 1993) in the same temperature range does not exceed 1%. However, the molecular geometries in (I) give no indication of CT. Comparison of the TMTTF molecules in (I) and in the crystal of pure TMTTF (Batsanov et al., 2001) show marginal (4 e.s.d.) differences in C1C1' bond lengths [1.344 (3) versus 1.358 (2) Å], while the C—S bond lengths, which give the most reliable measure of the positive charge on a TTF moiety (Clemente & Marzotto, 1996), are identical. Likewise, bond distances in the DNB moiety are essentially the same as in the structure of DNB itself (Tonogaki et al., 1993). Thus (I) can be best described as a molecular complex.

Both the TMTTF and DNB molecules in (I) are not strictly planar, but show a boat-like distortion (note that within a stack, all molecules are concaved in the same direction). The TMTTF molecule is folded along the S1···S2 and S1'···S2' vectors by 11.63 (4)°. It is also twisted by 2.78 (1)° around the central C1C1' bond. In the DNB molecule, the benzene ring is folded along the C7···C8' and C7'···C8 vectors by 1.64 (1)°, while the nitro-group plane C6/N/O1/O2 is inclined to the C7/C6/C8' plane by 4.22 (4)°. In the structures of pure components (see above), the DNB molecule is practically planar, and the TMTTF molecule is folded (by 6.5°) along the S···S vectors in a chair-like fashion.

Experimental top

Tetramethyltetrathiafulvalene TMTTF (3.5 mg, 0.013 mmol) was dissolved in hot chloroform (2 ml) and DNB (2.3 mg, 0.013 mmol) was added. The mixture was stirred until full dissolution and the solution was left to stand in a jar at room temperature allowing very slow evaporation of the solvent for several days, resulting in dark green crystals of (I). The same complex was obtained when benzene was used as a solvent, whereas from acetonitrile or dioxane the crystals of starting TMTTF were crystallized first from the solution, perhaps due to a solubility effect.

Refinement top

All H atoms were refined in isotropic approximation; bond lengths C—H 0.92 (2)–0.98 (3) Å.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Tetramethyltetrathiafulvalene and 1,4-dinitrobenzene molecules in (I), parallel projection on the (0 1 0) plane. Displacement ellipsoids are drawn at the 50% probability level. Atoms symmetrically dependent via the twofold axis are primed.
[Figure 2] Fig. 2. The stacking motif in (I).
4,4',5,5'-tetramethyltetrathiafulvalene 1,4-dinitrobenzene top
Crystal data top
C10H12S4·C6H4N2O4F(000) = 888
Mr = 428.55Dx = 1.553 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 22.184 (3) ÅCell parameters from 969 reflections
b = 6.871 (1) Åθ = 12.0–28.4°
c = 12.063 (1) ŵ = 0.54 mm1
β = 94.39 (1)°T = 120 K
V = 1833.3 (4) Å3Trapetzoid, black
Z = 40.55 × 0.31 × 0.16 mm
Data collection top
SMART 1K CCD area detector
diffractometer
2096 independent reflections
Radiation source: fine-focus sealed tube1904 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Detector resolution: 8 pixels mm-1θmax = 27.5°, θmin = 1.8°
ω scansh = 2628
Absorption correction: integration
SHELXTL (XPREP) (Bruker, 1998); before correction R(int) = 0.031
k = 58
Tmin = 0.755, Tmax = 0.919l = 1515
6260 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)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.079All H-atom parameters refined
S = 1.15 w = 1/[σ2(Fo2) + (0.0316P)2 + 2.5429P]
where P = (Fo2 + 2Fc2)/3
2096 reflections(Δ/σ)max = 0.001
150 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C10H12S4·C6H4N2O4V = 1833.3 (4) Å3
Mr = 428.55Z = 4
Monoclinic, C2/cMo Kα radiation
a = 22.184 (3) ŵ = 0.54 mm1
b = 6.871 (1) ÅT = 120 K
c = 12.063 (1) Å0.55 × 0.31 × 0.16 mm
β = 94.39 (1)°
Data collection top
SMART 1K CCD area detector
diffractometer
2096 independent reflections
Absorption correction: integration
SHELXTL (XPREP) (Bruker, 1998); before correction R(int) = 0.031
1904 reflections with I > 2σ(I)
Tmin = 0.755, Tmax = 0.919Rint = 0.022
6260 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.079All H-atom parameters refined
S = 1.15Δρmax = 0.31 e Å3
2096 reflectionsΔρmin = 0.26 e Å3
150 parameters
Special details top

Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 4 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (15 s exposure) covering 0.3° in ω. Crystal to detector distance 4.57 cm. The absense of crystal decay was confirmed by repeating 50 initial frames at the end of data collection and comparing 212 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
S10.436896 (18)0.64294 (6)0.88150 (3)0.01983 (12)
S20.417351 (18)0.65213 (6)0.63720 (3)0.01961 (12)
O10.36077 (6)0.1652 (2)0.88045 (11)0.0340 (3)
O20.33972 (6)0.1809 (2)0.70214 (11)0.0335 (3)
N0.37545 (7)0.1650 (2)0.78422 (12)0.0249 (3)
C10.46993 (7)0.6491 (2)0.75366 (12)0.0181 (3)
C20.36254 (7)0.6886 (2)0.82505 (13)0.0219 (3)
C30.35381 (7)0.6936 (2)0.71328 (13)0.0217 (3)
C40.31584 (8)0.7096 (3)0.90734 (16)0.0309 (4)
H410.2752 (12)0.726 (4)0.871 (2)0.051 (7)*
H420.3233 (13)0.820 (4)0.950 (2)0.057 (8)*
H430.3165 (13)0.602 (4)0.956 (2)0.065 (8)*
C50.29514 (8)0.7241 (3)0.64547 (16)0.0322 (4)
H510.2978 (14)0.820 (4)0.588 (3)0.069 (9)*
H520.2666 (13)0.771 (4)0.691 (2)0.058 (8)*
H530.2822 (15)0.610 (5)0.611 (3)0.081 (10)*
C60.44049 (7)0.1488 (2)0.76664 (13)0.0201 (3)
C70.45733 (7)0.1458 (2)0.65814 (13)0.0206 (3)
H70.4279 (9)0.145 (3)0.5963 (17)0.026 (5)*
C80.51838 (8)0.1464 (2)0.64109 (13)0.0209 (3)
H80.5310 (9)0.149 (3)0.5705 (17)0.026 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0223 (2)0.0231 (2)0.01442 (19)0.00037 (14)0.00328 (14)0.00103 (13)
S20.0210 (2)0.0231 (2)0.01459 (19)0.00072 (14)0.00075 (14)0.00199 (13)
O10.0287 (7)0.0454 (8)0.0292 (7)0.0061 (6)0.0109 (5)0.0060 (6)
O20.0229 (6)0.0436 (8)0.0336 (7)0.0002 (6)0.0013 (5)0.0035 (6)
N0.0226 (7)0.0234 (7)0.0290 (7)0.0029 (5)0.0039 (6)0.0010 (5)
C10.0238 (8)0.0162 (7)0.0144 (7)0.0001 (6)0.0024 (5)0.0005 (5)
C20.0196 (7)0.0234 (8)0.0228 (8)0.0024 (6)0.0025 (6)0.0014 (6)
C30.0193 (7)0.0240 (8)0.0222 (7)0.0017 (6)0.0031 (6)0.0027 (6)
C40.0248 (9)0.0425 (11)0.0263 (9)0.0018 (8)0.0080 (7)0.0008 (8)
C50.0209 (8)0.0470 (12)0.0280 (9)0.0004 (8)0.0021 (7)0.0051 (8)
C60.0203 (7)0.0158 (7)0.0247 (8)0.0016 (6)0.0036 (6)0.0004 (6)
C70.0242 (8)0.0181 (7)0.0192 (7)0.0009 (6)0.0012 (6)0.0020 (5)
C80.0268 (8)0.0180 (7)0.0182 (7)0.0009 (6)0.0035 (6)0.0014 (6)
Geometric parameters (Å, º) top
S1—C11.7579 (15)C4—H420.92 (3)
S1—C21.7638 (17)C4—H430.94 (3)
S2—C11.7560 (16)C5—H510.97 (3)
S2—C31.7632 (16)C5—H520.93 (3)
O1—N1.229 (2)C5—H530.92 (3)
O2—N1.225 (2)C6—C8i1.384 (2)
N—C61.478 (2)C6—C71.388 (2)
C1—C1i1.344 (3)C7—C81.385 (2)
C2—C31.348 (2)C7—H70.95 (2)
C2—C41.496 (2)C8—C6i1.384 (2)
C3—C51.498 (2)C8—H80.92 (2)
C4—H410.98 (3)
C1—S1—C295.59 (7)H41—C4—H43110 (2)
C1—S2—C395.40 (7)H42—C4—H43108 (2)
O2—N—O1124.15 (15)C3—C5—H51113.1 (18)
O2—N—C6117.96 (14)C3—C5—H52109.4 (17)
O1—N—C6117.87 (14)H51—C5—H52106 (2)
C1i—C1—S2123.33 (16)C3—C5—H53111 (2)
C1i—C1—S1122.70 (16)H51—C5—H53107 (3)
S2—C1—S1113.96 (9)H52—C5—H53111 (3)
C3—C2—C4127.42 (16)C8i—C6—C7123.33 (15)
C3—C2—S1116.70 (12)C8i—C6—N118.42 (14)
C4—C2—S1115.83 (12)C7—C6—N118.18 (15)
C2—C3—C5127.03 (15)C8—C7—C6118.46 (15)
C2—C3—S2117.20 (13)C8—C7—H7120.2 (12)
C5—C3—S2115.74 (12)C6—C7—H7121.3 (13)
C2—C4—H41111.9 (15)C6i—C8—C7118.18 (15)
C2—C4—H42110.3 (18)C6i—C8—H8121.2 (13)
H41—C4—H42106 (2)C7—C8—H8120.6 (13)
C2—C4—H43110.9 (18)
Symmetry code: (i) x+1, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC10H12S4·C6H4N2O4
Mr428.55
Crystal system, space groupMonoclinic, C2/c
Temperature (K)120
a, b, c (Å)22.184 (3), 6.871 (1), 12.063 (1)
β (°) 94.39 (1)
V3)1833.3 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.54
Crystal size (mm)0.55 × 0.31 × 0.16
Data collection
DiffractometerSMART 1K CCD area detector
diffractometer
Absorption correctionIntegration
SHELXTL (XPREP) (Bruker, 1998); before correction R(int) = 0.031
Tmin, Tmax0.755, 0.919
No. of measured, independent and
observed [I > 2σ(I)] reflections
6260, 2096, 1904
Rint0.022
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.079, 1.15
No. of reflections2096
No. of parameters150
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.31, 0.26

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C11.7579 (15)C1—C1i1.344 (3)
S1—C21.7638 (17)C2—C31.348 (2)
S2—C11.7560 (16)C2—C41.496 (2)
S2—C31.7632 (16)C3—C51.498 (2)
O1—N1.229 (2)C6—C8i1.384 (2)
O2—N1.225 (2)C6—C71.388 (2)
N—C61.478 (2)C7—C81.385 (2)
C1—S1—C295.59 (7)C4—C2—S1115.83 (12)
C1—S2—C395.40 (7)C2—C3—C5127.03 (15)
O2—N—O1124.15 (15)C2—C3—S2117.20 (13)
O2—N—C6117.96 (14)C5—C3—S2115.74 (12)
O1—N—C6117.87 (14)C8i—C6—C7123.33 (15)
C1i—C1—S2123.33 (16)C8i—C6—N118.42 (14)
C1i—C1—S1122.70 (16)C7—C6—N118.18 (15)
S2—C1—S1113.96 (9)C8—C7—C6118.46 (15)
C3—C2—C4127.42 (16)C6i—C8—C7118.18 (15)
C3—C2—S1116.70 (12)
Symmetry code: (i) x+1, y, z+3/2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds