The title compound, 2C
10H
12S
82+·C
2O
42-·2Cl
-, displays packing
via hydrogen bonds. The oxalate anion possesses exact
and approximate
D2h symmetry. Cationic columns of stacked donor molecules have weaker lateral interactions, forming layers. The Cl
- and C
2O
42- anions form anionic layers. The two layers alternate in the crystal structure.
Supporting information
CCDC reference: 274322
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.039
- wR factor = 0.093
- Data-to-parameter ratio = 21.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 49 Perc.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C11
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. O2 .. 3.14 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A .. CL1 .. 2.85 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 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
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Nonius, 1997–2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97.
Bis[tetrakis(methylsulfanyl)tetrathiafulvalenium] oxalate dichloride
top
Crystal data top
2C10H12S82+·C2O42−·2Cl− | F(000) = 956 |
Mr = 936.28 | Dx = 1.683 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 27130 reflections |
a = 10.0277 (2) Å | θ = 3.3–27.5° |
b = 7.9202 (2) Å | µ = 1.11 mm−1 |
c = 23.2669 (6) Å | T = 296 K |
β = 90.985 (1)° | Block, black |
V = 1847.62 (8) Å3 | 0.18 × 0.17 × 0.10 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4255 independent reflections |
Radiation source: fine-focus sealed tube | 2090 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
Detector resolution: 9 pixels mm-1 | θmax = 27.7°, θmin = 3.5° |
φ and ω scans | h = −12→13 |
Absorption correction: multi-scan (Blessing, 1995) | k = −10→10 |
Tmin = 0.825, Tmax = 0.897 | l = −30→30 |
24473 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0398P)2] where P = (Fo2 + 2Fc2)/3 |
4255 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.53 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 | Uiso*/Ueq | |
Cl1 | −0.02175 (9) | 0.76906 (12) | 0.33706 (4) | 0.0735 (3) | |
S1 | 0.61009 (7) | 0.57673 (10) | 0.36766 (3) | 0.0449 (2) | |
S2 | 0.32218 (7) | 0.57273 (10) | 0.38137 (3) | 0.0441 (2) | |
S3 | 0.64634 (7) | 0.74126 (10) | 0.49407 (3) | 0.0412 (2) | |
S4 | 0.35783 (7) | 0.72968 (10) | 0.50834 (3) | 0.0410 (2) | |
S5 | 0.58997 (8) | 0.41284 (13) | 0.25021 (4) | 0.0613 (3) | |
S6 | 0.27490 (8) | 0.41386 (12) | 0.26387 (3) | 0.0564 (3) | |
S7 | 0.69007 (8) | 0.93152 (11) | 0.60582 (3) | 0.0525 (2) | |
S8 | 0.37461 (7) | 0.91132 (11) | 0.62290 (3) | 0.0503 (2) | |
O1 | 0.0184 (4) | 0.6982 (5) | 0.47481 (18) | 0.1500 (16) | |
O2 | −0.0339 (4) | 0.4778 (6) | 0.42835 (13) | 0.1626 (18) | |
C1 | 0.4771 (3) | 0.6190 (4) | 0.41072 (12) | 0.0376 (7) | |
C2 | 0.4924 (2) | 0.6877 (4) | 0.46525 (12) | 0.0371 (7) | |
C3 | 0.5162 (3) | 0.4894 (4) | 0.31176 (11) | 0.0389 (7) | |
C4 | 0.3820 (3) | 0.4880 (4) | 0.31787 (11) | 0.0391 (7) | |
C5 | 0.5845 (3) | 0.8377 (4) | 0.55535 (11) | 0.0348 (7) | |
C6 | 0.4500 (3) | 0.8308 (4) | 0.56181 (11) | 0.0374 (7) | |
C7 | 0.7631 (3) | 0.4249 (4) | 0.26666 (13) | 0.0625 (10) | |
H7A | 0.8128 | 0.3846 | 0.2345 | 0.094* | |
H7B | 0.7831 | 0.3567 | 0.2998 | 0.094* | |
H7C | 0.7870 | 0.5401 | 0.2746 | 0.094* | |
C8 | 0.1231 (3) | 0.3760 (5) | 0.30084 (13) | 0.0649 (10) | |
H8A | 0.0567 | 0.3343 | 0.2742 | 0.097* | |
H8B | 0.0925 | 0.4794 | 0.3176 | 0.097* | |
H8C | 0.1384 | 0.2938 | 0.3306 | 0.097* | |
C9 | 0.8474 (3) | 0.9385 (4) | 0.57050 (13) | 0.0580 (10) | |
H9A | 0.9130 | 0.9890 | 0.5956 | 0.087* | |
H9B | 0.8388 | 1.0044 | 0.5360 | 0.087* | |
H9C | 0.8746 | 0.8259 | 0.5610 | 0.087* | |
C10 | 0.2012 (3) | 0.9018 (5) | 0.60364 (14) | 0.0667 (11) | |
H10A | 0.1493 | 0.9437 | 0.6349 | 0.100* | |
H10B | 0.1766 | 0.7870 | 0.5956 | 0.100* | |
H10C | 0.1847 | 0.9697 | 0.5701 | 0.100* | |
C11 | −0.0038 (4) | 0.5488 (6) | 0.47230 (16) | 0.0704 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.1048 (8) | 0.0686 (7) | 0.0467 (5) | 0.0092 (6) | −0.0090 (5) | 0.0026 (5) |
S1 | 0.0384 (4) | 0.0548 (6) | 0.0416 (5) | −0.0017 (4) | 0.0020 (3) | −0.0116 (4) |
S2 | 0.0363 (4) | 0.0563 (6) | 0.0394 (4) | 0.0006 (4) | −0.0032 (3) | −0.0107 (4) |
S3 | 0.0336 (4) | 0.0498 (6) | 0.0401 (4) | −0.0006 (4) | −0.0011 (3) | −0.0100 (4) |
S4 | 0.0333 (4) | 0.0505 (6) | 0.0391 (4) | 0.0025 (4) | −0.0022 (3) | −0.0081 (4) |
S5 | 0.0558 (5) | 0.0863 (8) | 0.0419 (5) | 0.0015 (5) | 0.0073 (4) | −0.0186 (5) |
S6 | 0.0550 (5) | 0.0780 (7) | 0.0361 (5) | −0.0129 (5) | −0.0040 (4) | −0.0111 (4) |
S7 | 0.0468 (5) | 0.0652 (6) | 0.0450 (5) | −0.0015 (4) | −0.0089 (4) | −0.0157 (4) |
S8 | 0.0478 (5) | 0.0632 (6) | 0.0399 (5) | 0.0052 (4) | 0.0036 (4) | −0.0119 (4) |
O1 | 0.160 (3) | 0.073 (2) | 0.219 (4) | 0.006 (2) | 0.076 (3) | 0.058 (3) |
O2 | 0.174 (3) | 0.260 (5) | 0.0533 (19) | −0.050 (3) | −0.003 (2) | −0.046 (3) |
C1 | 0.0322 (15) | 0.0390 (19) | 0.0414 (18) | 0.0012 (14) | −0.0042 (13) | −0.0025 (14) |
C2 | 0.0323 (16) | 0.038 (2) | 0.0409 (17) | 0.0013 (13) | −0.0032 (13) | 0.0014 (14) |
C3 | 0.0490 (19) | 0.0375 (19) | 0.0302 (16) | 0.0006 (15) | 0.0022 (14) | −0.0018 (14) |
C4 | 0.0459 (18) | 0.039 (2) | 0.0318 (16) | −0.0030 (15) | −0.0012 (13) | −0.0014 (14) |
C5 | 0.0374 (17) | 0.0347 (19) | 0.0322 (16) | 0.0011 (13) | −0.0035 (13) | −0.0023 (13) |
C6 | 0.0439 (18) | 0.038 (2) | 0.0300 (16) | 0.0039 (14) | −0.0019 (14) | −0.0008 (13) |
C7 | 0.054 (2) | 0.074 (3) | 0.060 (2) | 0.0002 (18) | 0.0201 (18) | −0.0013 (19) |
C8 | 0.0425 (18) | 0.100 (3) | 0.052 (2) | 0.0005 (19) | −0.0097 (16) | −0.011 (2) |
C9 | 0.0415 (18) | 0.071 (3) | 0.061 (2) | −0.0092 (17) | −0.0115 (16) | −0.0061 (18) |
C10 | 0.0445 (19) | 0.099 (3) | 0.057 (2) | 0.0158 (19) | 0.0072 (16) | −0.013 (2) |
C11 | 0.058 (2) | 0.089 (4) | 0.064 (3) | −0.001 (2) | 0.016 (2) | 0.011 (2) |
Geometric parameters (Å, º) top
S1—C1 | 1.715 (3) | O2—C11 | 1.201 (5) |
S1—C3 | 1.736 (3) | C1—C2 | 1.387 (4) |
S2—C1 | 1.725 (3) | C3—C4 | 1.355 (4) |
S2—C4 | 1.739 (3) | C5—C6 | 1.360 (4) |
S3—C2 | 1.725 (3) | C7—H7A | 0.9600 |
S3—C5 | 1.741 (3) | C7—H7B | 0.9600 |
S4—C2 | 1.727 (3) | C7—H7C | 0.9600 |
S4—C6 | 1.733 (3) | C8—H8A | 0.9600 |
S5—C3 | 1.733 (3) | C8—H8B | 0.9600 |
S5—C7 | 1.774 (3) | C8—H8C | 0.9600 |
S6—C4 | 1.741 (3) | C9—H9A | 0.9600 |
S6—C8 | 1.787 (3) | C9—H9B | 0.9600 |
S7—C5 | 1.735 (3) | C9—H9C | 0.9600 |
S7—C9 | 1.792 (3) | C10—H10A | 0.9600 |
S8—C6 | 1.742 (3) | C10—H10B | 0.9600 |
S8—C10 | 1.790 (3) | C10—H10C | 0.9600 |
O1—C11 | 1.205 (5) | C11—C11i | 1.504 (7) |
| | | |
C1—S1—C3 | 95.64 (13) | S5—C7—H7B | 109.5 |
C1—S2—C4 | 95.55 (14) | H7A—C7—H7B | 109.5 |
C2—S3—C5 | 95.57 (13) | S5—C7—H7C | 109.5 |
C2—S4—C6 | 95.36 (13) | H7A—C7—H7C | 109.5 |
C3—S5—C7 | 103.46 (14) | H7B—C7—H7C | 109.5 |
C4—S6—C8 | 103.27 (14) | S6—C8—H8A | 109.5 |
C5—S7—C9 | 103.57 (13) | S6—C8—H8B | 109.5 |
C6—S8—C10 | 102.34 (14) | H8A—C8—H8B | 109.5 |
C2—C1—S1 | 122.4 (2) | S6—C8—H8C | 109.5 |
C2—C1—S2 | 122.0 (2) | H8A—C8—H8C | 109.5 |
S1—C1—S2 | 115.54 (16) | H8B—C8—H8C | 109.5 |
C1—C2—S3 | 122.4 (2) | S7—C9—H9A | 109.5 |
C1—C2—S4 | 122.1 (2) | S7—C9—H9B | 109.5 |
S3—C2—S4 | 115.45 (16) | H9A—C9—H9B | 109.5 |
C4—C3—S5 | 121.5 (2) | S7—C9—H9C | 109.5 |
C4—C3—S1 | 116.8 (2) | H9A—C9—H9C | 109.5 |
S5—C3—S1 | 121.67 (16) | H9B—C9—H9C | 109.5 |
C3—C4—S2 | 116.3 (2) | S8—C10—H10A | 109.5 |
C3—C4—S6 | 121.9 (2) | S8—C10—H10B | 109.5 |
S2—C4—S6 | 121.71 (16) | H10A—C10—H10B | 109.5 |
C6—C5—S7 | 122.5 (2) | S8—C10—H10C | 109.5 |
C6—C5—S3 | 116.1 (2) | H10A—C10—H10C | 109.5 |
S7—C5—S3 | 121.35 (15) | H10B—C10—H10C | 109.5 |
C5—C6—S4 | 117.2 (2) | O2—C11—O1 | 123.0 (5) |
C5—C6—S8 | 121.3 (2) | O2—C11—C11i | 119.9 (6) |
S4—C6—S8 | 121.41 (16) | O1—C11—C11i | 117.2 (6) |
S5—C7—H7A | 109.5 | | |
| | | |
C3—S1—C1—C2 | 177.5 (3) | S5—C3—C4—S6 | −1.4 (4) |
C3—S1—C1—S2 | −3.3 (2) | S1—C3—C4—S6 | 176.86 (16) |
C4—S2—C1—C2 | −177.7 (2) | C1—S2—C4—C3 | −1.5 (3) |
C4—S2—C1—S1 | 3.1 (2) | C1—S2—C4—S6 | −178.88 (19) |
S1—C1—C2—S3 | 1.5 (4) | C8—S6—C4—C3 | 162.0 (3) |
S2—C1—C2—S3 | −177.72 (16) | C8—S6—C4—S2 | −20.7 (2) |
S1—C1—C2—S4 | −179.92 (16) | C9—S7—C5—C6 | −170.1 (3) |
S2—C1—C2—S4 | 0.9 (4) | C9—S7—C5—S3 | 11.7 (2) |
C5—S3—C2—C1 | 173.1 (2) | C2—S3—C5—C6 | 3.7 (2) |
C5—S3—C2—S4 | −5.57 (19) | C2—S3—C5—S7 | −178.03 (18) |
C6—S4—C2—C1 | −173.4 (2) | S7—C5—C6—S4 | −178.89 (15) |
C6—S4—C2—S3 | 5.29 (19) | S3—C5—C6—S4 | −0.7 (3) |
C7—S5—C3—C4 | −174.7 (3) | S7—C5—C6—S8 | −1.9 (4) |
C7—S5—C3—S1 | 7.1 (2) | S3—C5—C6—S8 | 176.37 (15) |
C1—S1—C3—C4 | 2.3 (3) | C2—S4—C6—C5 | −2.8 (3) |
C1—S1—C3—S5 | −179.46 (18) | C2—S4—C6—S8 | −179.79 (18) |
S5—C3—C4—S2 | −178.80 (16) | C10—S8—C6—C5 | 170.7 (3) |
S1—C3—C4—S2 | −0.5 (3) | C10—S8—C6—S4 | −12.4 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···Cl1 | 0.96 | 2.61 | 3.543 (4) | 165 |
C8—H8A···Cl1ii | 0.96 | 2.66 | 3.454 (3) | 141 |
C7—H7A···Cl1iii | 0.96 | 2.85 | 3.780 (3) | 163 |
C9—H9A···Cl1iv | 0.96 | 2.69 | 3.594 (3) | 157 |
C9—H9A···Cl1iv | 0.96 | 2.69 | 3.594 (3) | 157 |
C8—H8C···S7v | 0.96 | 2.87 | 3.744 (4) | 152 |
Symmetry codes: (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+1. |