Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000114/cv6162sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000114/cv6162Isup2.hkl |
CCDC reference: 204688
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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
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.
All H atoms were refined in isotropic approximation; bond lengths C—H 0.92 (2)–0.98 (3) Å.
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.
C10H12S4·C6H4N2O4 | F(000) = 888 |
Mr = 428.55 | Dx = 1.553 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.184 (3) Å | Cell parameters from 969 reflections |
b = 6.871 (1) Å | θ = 12.0–28.4° |
c = 12.063 (1) Å | µ = 0.54 mm−1 |
β = 94.39 (1)° | T = 120 K |
V = 1833.3 (4) Å3 | Trapetzoid, black |
Z = 4 | 0.55 × 0.31 × 0.16 mm |
SMART 1K CCD area detector diffractometer | 2096 independent reflections |
Radiation source: fine-focus sealed tube | 1904 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 8 pixels mm-1 | θmax = 27.5°, θmin = 1.8° |
ω scans | h = −26→28 |
Absorption correction: integration SHELXTL (XPREP) (Bruker, 1998); before correction R(int) = 0.031 | k = −5→8 |
Tmin = 0.755, Tmax = 0.919 | l = −15→15 |
6260 measured reflections |
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)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.079 | All 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 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C10H12S4·C6H4N2O4 | V = 1833.3 (4) Å3 |
Mr = 428.55 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.184 (3) Å | µ = 0.54 mm−1 |
b = 6.871 (1) Å | T = 120 K |
c = 12.063 (1) Å | 0.55 × 0.31 × 0.16 mm |
β = 94.39 (1)° |
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 = 0.919 | Rint = 0.022 |
6260 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.079 | All H-atom parameters refined |
S = 1.15 | Δρmax = 0.31 e Å−3 |
2096 reflections | Δρmin = −0.26 e Å−3 |
150 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.436896 (18) | 0.64294 (6) | 0.88150 (3) | 0.01983 (12) | |
S2 | 0.417351 (18) | 0.65213 (6) | 0.63720 (3) | 0.01961 (12) | |
O1 | 0.36077 (6) | 0.1652 (2) | 0.88045 (11) | 0.0340 (3) | |
O2 | 0.33972 (6) | 0.1809 (2) | 0.70214 (11) | 0.0335 (3) | |
N | 0.37545 (7) | 0.1650 (2) | 0.78422 (12) | 0.0249 (3) | |
C1 | 0.46993 (7) | 0.6491 (2) | 0.75366 (12) | 0.0181 (3) | |
C2 | 0.36254 (7) | 0.6886 (2) | 0.82505 (13) | 0.0219 (3) | |
C3 | 0.35381 (7) | 0.6936 (2) | 0.71328 (13) | 0.0217 (3) | |
C4 | 0.31584 (8) | 0.7096 (3) | 0.90734 (16) | 0.0309 (4) | |
H41 | 0.2752 (12) | 0.726 (4) | 0.871 (2) | 0.051 (7)* | |
H42 | 0.3233 (13) | 0.820 (4) | 0.950 (2) | 0.057 (8)* | |
H43 | 0.3165 (13) | 0.602 (4) | 0.956 (2) | 0.065 (8)* | |
C5 | 0.29514 (8) | 0.7241 (3) | 0.64547 (16) | 0.0322 (4) | |
H51 | 0.2978 (14) | 0.820 (4) | 0.588 (3) | 0.069 (9)* | |
H52 | 0.2666 (13) | 0.771 (4) | 0.691 (2) | 0.058 (8)* | |
H53 | 0.2822 (15) | 0.610 (5) | 0.611 (3) | 0.081 (10)* | |
C6 | 0.44049 (7) | 0.1488 (2) | 0.76664 (13) | 0.0201 (3) | |
C7 | 0.45733 (7) | 0.1458 (2) | 0.65814 (13) | 0.0206 (3) | |
H7 | 0.4279 (9) | 0.145 (3) | 0.5963 (17) | 0.026 (5)* | |
C8 | 0.51838 (8) | 0.1464 (2) | 0.64109 (13) | 0.0209 (3) | |
H8 | 0.5310 (9) | 0.149 (3) | 0.5705 (17) | 0.026 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0223 (2) | 0.0231 (2) | 0.01442 (19) | 0.00037 (14) | 0.00328 (14) | 0.00103 (13) |
S2 | 0.0210 (2) | 0.0231 (2) | 0.01459 (19) | −0.00072 (14) | 0.00075 (14) | −0.00199 (13) |
O1 | 0.0287 (7) | 0.0454 (8) | 0.0292 (7) | −0.0061 (6) | 0.0109 (5) | −0.0060 (6) |
O2 | 0.0229 (6) | 0.0436 (8) | 0.0336 (7) | −0.0002 (6) | −0.0013 (5) | 0.0035 (6) |
N | 0.0226 (7) | 0.0234 (7) | 0.0290 (7) | −0.0029 (5) | 0.0039 (6) | −0.0010 (5) |
C1 | 0.0238 (8) | 0.0162 (7) | 0.0144 (7) | −0.0001 (6) | 0.0024 (5) | −0.0005 (5) |
C2 | 0.0196 (7) | 0.0234 (8) | 0.0228 (8) | −0.0024 (6) | 0.0025 (6) | −0.0014 (6) |
C3 | 0.0193 (7) | 0.0240 (8) | 0.0222 (7) | −0.0017 (6) | 0.0031 (6) | −0.0027 (6) |
C4 | 0.0248 (9) | 0.0425 (11) | 0.0263 (9) | −0.0018 (8) | 0.0080 (7) | −0.0008 (8) |
C5 | 0.0209 (8) | 0.0470 (12) | 0.0280 (9) | −0.0004 (8) | −0.0021 (7) | −0.0051 (8) |
C6 | 0.0203 (7) | 0.0158 (7) | 0.0247 (8) | −0.0016 (6) | 0.0036 (6) | 0.0004 (6) |
C7 | 0.0242 (8) | 0.0181 (7) | 0.0192 (7) | −0.0009 (6) | −0.0012 (6) | 0.0020 (5) |
C8 | 0.0268 (8) | 0.0180 (7) | 0.0182 (7) | 0.0009 (6) | 0.0035 (6) | 0.0014 (6) |
S1—C1 | 1.7579 (15) | C4—H42 | 0.92 (3) |
S1—C2 | 1.7638 (17) | C4—H43 | 0.94 (3) |
S2—C1 | 1.7560 (16) | C5—H51 | 0.97 (3) |
S2—C3 | 1.7632 (16) | C5—H52 | 0.93 (3) |
O1—N | 1.229 (2) | C5—H53 | 0.92 (3) |
O2—N | 1.225 (2) | C6—C8i | 1.384 (2) |
N—C6 | 1.478 (2) | C6—C7 | 1.388 (2) |
C1—C1i | 1.344 (3) | C7—C8 | 1.385 (2) |
C2—C3 | 1.348 (2) | C7—H7 | 0.95 (2) |
C2—C4 | 1.496 (2) | C8—C6i | 1.384 (2) |
C3—C5 | 1.498 (2) | C8—H8 | 0.92 (2) |
C4—H41 | 0.98 (3) | ||
C1—S1—C2 | 95.59 (7) | H41—C4—H43 | 110 (2) |
C1—S2—C3 | 95.40 (7) | H42—C4—H43 | 108 (2) |
O2—N—O1 | 124.15 (15) | C3—C5—H51 | 113.1 (18) |
O2—N—C6 | 117.96 (14) | C3—C5—H52 | 109.4 (17) |
O1—N—C6 | 117.87 (14) | H51—C5—H52 | 106 (2) |
C1i—C1—S2 | 123.33 (16) | C3—C5—H53 | 111 (2) |
C1i—C1—S1 | 122.70 (16) | H51—C5—H53 | 107 (3) |
S2—C1—S1 | 113.96 (9) | H52—C5—H53 | 111 (3) |
C3—C2—C4 | 127.42 (16) | C8i—C6—C7 | 123.33 (15) |
C3—C2—S1 | 116.70 (12) | C8i—C6—N | 118.42 (14) |
C4—C2—S1 | 115.83 (12) | C7—C6—N | 118.18 (15) |
C2—C3—C5 | 127.03 (15) | C8—C7—C6 | 118.46 (15) |
C2—C3—S2 | 117.20 (13) | C8—C7—H7 | 120.2 (12) |
C5—C3—S2 | 115.74 (12) | C6—C7—H7 | 121.3 (13) |
C2—C4—H41 | 111.9 (15) | C6i—C8—C7 | 118.18 (15) |
C2—C4—H42 | 110.3 (18) | C6i—C8—H8 | 121.2 (13) |
H41—C4—H42 | 106 (2) | C7—C8—H8 | 120.6 (13) |
C2—C4—H43 | 110.9 (18) |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C10H12S4·C6H4N2O4 |
Mr | 428.55 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 22.184 (3), 6.871 (1), 12.063 (1) |
β (°) | 94.39 (1) |
V (Å3) | 1833.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.55 × 0.31 × 0.16 |
Data collection | |
Diffractometer | SMART 1K CCD area detector diffractometer |
Absorption correction | Integration SHELXTL (XPREP) (Bruker, 1998); before correction R(int) = 0.031 |
Tmin, Tmax | 0.755, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6260, 2096, 1904 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.079, 1.15 |
No. of reflections | 2096 |
No. of parameters | 150 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
S1—C1 | 1.7579 (15) | C1—C1i | 1.344 (3) |
S1—C2 | 1.7638 (17) | C2—C3 | 1.348 (2) |
S2—C1 | 1.7560 (16) | C2—C4 | 1.496 (2) |
S2—C3 | 1.7632 (16) | C3—C5 | 1.498 (2) |
O1—N | 1.229 (2) | C6—C8i | 1.384 (2) |
O2—N | 1.225 (2) | C6—C7 | 1.388 (2) |
N—C6 | 1.478 (2) | C7—C8 | 1.385 (2) |
C1—S1—C2 | 95.59 (7) | C4—C2—S1 | 115.83 (12) |
C1—S2—C3 | 95.40 (7) | C2—C3—C5 | 127.03 (15) |
O2—N—O1 | 124.15 (15) | C2—C3—S2 | 117.20 (13) |
O2—N—C6 | 117.96 (14) | C5—C3—S2 | 115.74 (12) |
O1—N—C6 | 117.87 (14) | C8i—C6—C7 | 123.33 (15) |
C1i—C1—S2 | 123.33 (16) | C8i—C6—N | 118.42 (14) |
C1i—C1—S1 | 122.70 (16) | C7—C6—N | 118.18 (15) |
S2—C1—S1 | 113.96 (9) | C8—C7—C6 | 118.46 (15) |
C3—C2—C4 | 127.42 (16) | C6i—C8—C7 | 118.18 (15) |
C3—C2—S1 | 116.70 (12) |
Symmetry code: (i) −x+1, y, −z+3/2. |
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 C1═C1' 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 C1═C1' 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.