Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100016589/av1063sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016589/av1063Isup2.hkl |
CCDC reference: 159980
For related literature, see: Bock & Heigel (2000, 2000); Bock et al. (1998); Bock, Hauck, Näther, Rösch, Staufer & Häberlein (1995); Bock, Havlas, Krenzel & Sievert (2000); Bock, Heigel & Nagel (2000); Bock, Schödel, Havlas & Herrmann (1995); Excoffon et al. (1991); Gloux et al. (1987); Sheldrick (1986, 1997).
Preparation and crystallization: From sodium (0.1 g, 4.3 mmol) by gentle heating at 10-5 mbar a mirror is generated on the wall of a dried Schlenk trap. Addition of tris(phenylthio)methane (100 mg, 0.2 mmol) in aprotic tetramethylethylenediamine (10 ml) produces a yellow solution, which after one day of standing at room temperature is covered with a layer aprotic n-hexane (10 ml). After one week, yellow crystals are collected from the trap wall near the phase border line.
Structure determination: The structure was solved with SHELXS86 (Sheldrick, 1986) and refinement accomplished with SHELXL97 (Sheldrick, 1997), molecular graphics: XP (Siemens XTL-PC). Data were corrected for Lorentz and polarization effects. All C, S, N and Na have been refined with anisotropic displacement parameters, all H atoms were located from the difference map and placed on idealized positions using a riding model with distances C—Hphenyl = 0.95 Å, C—Hmethylene = 0.99 Å and C—Hmethyl = 0.98 Å. The torsion of the methyl H atoms and the isotropic displacement parameters of all H atoms (groupwise for methyl and methylen H atoms) were refined.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTLPC/XP; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Na+·C6H5S−·C6H16N2 | Z = 2 |
Mr = 248.36 | F(000) = 268 |
Triclinic, P1 | Dx = 1.187 Mg m−3 |
a = 5.944 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.200 (2) Å | Cell parameters from 81 reflections |
c = 11.899 (2) Å | θ = 8.5–18° |
α = 62.58 (1)° | µ = 0.24 mm−1 |
β = 87.14 (2)° | T = 180 K |
γ = 81.32 (2)° | Block, yellow |
V = 694.9 (2) Å3 | 0.60 × 0.42 × 0.25 mm |
Siemens P4 four circle diffractometer | Rint = 0.043 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 1.9° |
Graphite monochromator | h = −1→7 |
θ–2θ scans | k = −13→13 |
3921 measured reflections | l = −15→15 |
3066 independent reflections | 4 standard reflections every 100 reflections |
2636 reflections with I > 2σ(I) | intensity decay: <5% |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.1435P] where P = (Fo2 + 2Fc2)/3 |
3066 reflections | (Δ/σ)max < 0.001 |
149 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Na+·C6H5S−·C6H16N2 | γ = 81.32 (2)° |
Mr = 248.36 | V = 694.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.944 (1) Å | Mo Kα radiation |
b = 11.200 (2) Å | µ = 0.24 mm−1 |
c = 11.899 (2) Å | T = 180 K |
α = 62.58 (1)° | 0.60 × 0.42 × 0.25 mm |
β = 87.14 (2)° |
Siemens P4 four circle diffractometer | Rint = 0.043 |
3921 measured reflections | 4 standard reflections every 100 reflections |
3066 independent reflections | intensity decay: <5% |
2636 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.34 e Å−3 |
3066 reflections | Δρmin = −0.21 e Å−3 |
149 parameters |
Experimental. The count of measured symmetry unique reflections to theta 30 is not complete but ratio data parameter 20.6 is quite good. |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.28669 (6) | 0.36592 (3) | 0.00593 (3) | 0.02952 (11) | |
Na1 | 0.20232 (10) | 0.65095 (6) | −0.09001 (5) | 0.03402 (15) | |
C11 | 0.2423 (2) | 0.35842 (13) | −0.13519 (12) | 0.0268 (3) | |
C12 | 0.0259 (2) | 0.38947 (17) | −0.19132 (13) | 0.0367 (3) | |
H12 | −0.1018 | 0.4138 | −0.1511 | 0.044* | |
C13 | −0.0071 (3) | 0.38566 (18) | −0.30345 (14) | 0.0417 (4) | |
H13 | −0.1563 | 0.4077 | −0.3391 | 0.050* | |
C14 | 0.1739 (3) | 0.35034 (17) | −0.36429 (14) | 0.0408 (4) | |
H14 | 0.1508 | 0.3478 | −0.4415 | 0.049* | |
C15 | 0.3888 (3) | 0.31874 (18) | −0.31119 (15) | 0.0413 (4) | |
H15 | 0.5150 | 0.2942 | −0.3523 | 0.050* | |
C16 | 0.4231 (2) | 0.32232 (16) | −0.19853 (13) | 0.0336 (3) | |
H16 | 0.5729 | 0.2997 | −0.1635 | 0.040* | |
N1 | 0.29374 (19) | 0.75373 (12) | −0.32466 (10) | 0.0297 (2) | |
N2 | 0.16160 (19) | 0.90602 (12) | −0.16959 (11) | 0.0319 (3) | |
C1 | 0.5352 (3) | 0.7097 (2) | −0.32441 (17) | 0.0511 (5) | |
H1A | 0.5630 | 0.6109 | −0.2929 | 0.077* | |
H1B | 0.6151 | 0.7338 | −0.2693 | 0.077* | |
H1C | 0.5912 | 0.7545 | −0.4108 | 0.077* | |
C2 | 0.1784 (3) | 0.7152 (2) | −0.40627 (15) | 0.0460 (4) | |
H2A | 0.0133 | 0.7365 | −0.4013 | 0.069* | |
H2B | 0.2196 | 0.6174 | −0.3782 | 0.069* | |
H2C | 0.2251 | 0.7657 | −0.4939 | 0.069* | |
C3 | 0.2412 (3) | 0.90096 (16) | −0.37395 (13) | 0.0387 (3) | |
H3A | 0.0768 | 0.9288 | −0.3961 | 0.046* | |
H3B | 0.3261 | 0.9451 | −0.4528 | 0.046* | |
C4 | 0.2984 (3) | 0.95221 (17) | −0.28344 (15) | 0.0400 (3) | |
H4A | 0.4613 | 0.9212 | −0.2582 | 0.048* | |
H4B | 0.2750 | 1.0528 | −0.3276 | 0.048* | |
C5 | −0.0746 (3) | 0.97054 (19) | −0.19733 (18) | 0.0469 (4) | |
H5A | −0.1594 | 0.9402 | −0.1185 | 0.070* | |
H5B | −0.1427 | 0.9454 | −0.2553 | 0.070* | |
H5C | −0.0806 | 1.0695 | −0.2368 | 0.070* | |
C6 | 0.2568 (3) | 0.94047 (18) | −0.07953 (16) | 0.0426 (4) | |
H6A | 0.1688 | 0.9080 | −0.0018 | 0.064* | |
H6B | 0.2499 | 1.0393 | −0.1167 | 0.064* | |
H6C | 0.4156 | 0.8973 | −0.0596 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.03234 (17) | 0.02730 (19) | 0.02845 (17) | −0.00377 (12) | −0.00031 (11) | −0.01245 (13) |
Na1 | 0.0476 (3) | 0.0251 (3) | 0.0265 (3) | −0.0068 (2) | 0.0074 (2) | −0.0097 (2) |
C11 | 0.0286 (6) | 0.0231 (6) | 0.0272 (6) | −0.0084 (5) | 0.0024 (5) | −0.0089 (5) |
C12 | 0.0271 (6) | 0.0461 (9) | 0.0323 (7) | −0.0075 (6) | 0.0030 (5) | −0.0138 (6) |
C13 | 0.0349 (7) | 0.0528 (10) | 0.0349 (7) | −0.0151 (7) | −0.0028 (6) | −0.0152 (7) |
C14 | 0.0508 (9) | 0.0438 (9) | 0.0345 (7) | −0.0179 (7) | 0.0014 (6) | −0.0204 (7) |
C15 | 0.0429 (8) | 0.0475 (10) | 0.0417 (8) | −0.0086 (7) | 0.0079 (6) | −0.0276 (7) |
C16 | 0.0289 (6) | 0.0379 (8) | 0.0361 (7) | −0.0051 (6) | 0.0015 (5) | −0.0186 (6) |
N1 | 0.0328 (6) | 0.0296 (6) | 0.0258 (5) | −0.0080 (5) | 0.0032 (4) | −0.0111 (4) |
N2 | 0.0305 (6) | 0.0285 (6) | 0.0371 (6) | −0.0066 (5) | 0.0047 (4) | −0.0150 (5) |
C1 | 0.0363 (8) | 0.0733 (13) | 0.0458 (9) | 0.0054 (8) | −0.0032 (6) | −0.0326 (9) |
C2 | 0.0461 (9) | 0.0585 (11) | 0.0413 (8) | −0.0185 (8) | 0.0023 (7) | −0.0264 (8) |
C3 | 0.0460 (8) | 0.0326 (8) | 0.0298 (7) | −0.0091 (6) | 0.0026 (6) | −0.0070 (6) |
C4 | 0.0443 (8) | 0.0353 (8) | 0.0429 (8) | −0.0186 (6) | 0.0131 (6) | −0.0175 (6) |
C5 | 0.0325 (7) | 0.0429 (9) | 0.0638 (10) | −0.0036 (6) | −0.0004 (7) | −0.0236 (8) |
C6 | 0.0448 (8) | 0.0396 (9) | 0.0476 (8) | −0.0011 (7) | −0.0040 (7) | −0.0245 (7) |
S1—C11 | 1.7542 (14) | C12—C13 | 1.379 (2) |
S1—Na1 | 2.8219 (8) | C13—C14 | 1.377 (2) |
S1—Na1i | 3.0310 (8) | C14—C15 | 1.376 (2) |
S1—Na1ii | 3.1966 (8) | C15—C16 | 1.385 (2) |
Na1—N2 | 2.5375 (14) | N1—C1 | 1.445 (2) |
Na1—N1 | 2.5482 (13) | N1—C3 | 1.460 (2) |
Na1—S1i | 3.0310 (8) | N1—C2 | 1.4634 (19) |
Na1—S1ii | 3.1966 (8) | N2—C5 | 1.4570 (19) |
Na1—Na1i | 4.1323 (12) | N2—C6 | 1.458 (2) |
C11—C16 | 1.3983 (19) | N2—C4 | 1.4613 (18) |
C11—C12 | 1.3994 (18) | C3—C4 | 1.506 (2) |
C11—S1—Na1 | 98.21 (5) | C16—C11—S1 | 121.47 (10) |
C11—S1—Na1i | 95.56 (4) | C12—C11—S1 | 122.18 (11) |
Na1—S1—Na1i | 89.751 (18) | C13—C12—C11 | 121.85 (14) |
C11—S1—Na1ii | 118.28 (4) | C14—C13—C12 | 120.72 (14) |
Na1—S1—Na1ii | 92.662 (19) | C15—C14—C13 | 118.82 (14) |
Na1i—S1—Na1ii | 145.28 (2) | C14—C15—C16 | 120.78 (14) |
N2—Na1—N1 | 73.60 (4) | C15—C16—C11 | 121.50 (13) |
N2—Na1—S1 | 174.95 (4) | C1—N1—C3 | 111.97 (13) |
N1—Na1—S1 | 106.93 (3) | C1—N1—C2 | 108.35 (13) |
N2—Na1—S1i | 93.77 (3) | C3—N1—C2 | 108.11 (12) |
N1—Na1—S1i | 120.38 (3) | C1—N1—Na1 | 103.32 (9) |
S1—Na1—S1i | 90.249 (18) | C3—N1—Na1 | 106.29 (9) |
N2—Na1—S1ii | 87.62 (3) | C2—N1—Na1 | 118.81 (9) |
N1—Na1—S1ii | 93.31 (3) | C5—N2—C6 | 108.55 (13) |
S1—Na1—S1ii | 87.338 (19) | C5—N2—C4 | 111.76 (13) |
S1i—Na1—S1ii | 145.28 (2) | C6—N2—C4 | 108.64 (12) |
N2—Na1—Na1i | 136.76 (4) | C5—N2—Na1 | 112.35 (10) |
N1—Na1—Na1i | 124.73 (4) | C6—N2—Na1 | 111.95 (9) |
S1—Na1—Na1i | 47.179 (15) | C4—N2—Na1 | 103.50 (9) |
S1i—Na1—Na1i | 43.070 (14) | N1—C3—C4 | 114.21 (12) |
S1ii—Na1—Na1i | 124.83 (2) | N2—C4—C3 | 113.28 (12) |
C16—C11—C12 | 116.35 (13) | ||
C11—S1—Na1—N2 | −121.6 (4) | N2—Na1—N1—C3 | −7.31 (9) |
Na1i—S1—Na1—N2 | 142.8 (4) | S1—Na1—N1—C3 | 177.94 (8) |
Na1ii—S1—Na1—N2 | −2.6 (4) | S1i—Na1—N1—C3 | 77.35 (9) |
C11—S1—Na1—N1 | −26.41 (5) | S1ii—Na1—N1—C3 | −93.84 (9) |
Na1i—S1—Na1—N1 | −122.00 (4) | Na1i—Na1—N1—C3 | 128.74 (9) |
Na1ii—S1—Na1—N1 | 92.66 (3) | N2—Na1—N1—C2 | −129.34 (12) |
C11—S1—Na1—S1i | 95.59 (4) | S1—Na1—N1—C2 | 55.91 (12) |
Na1i—S1—Na1—S1i | 0.0 | S1i—Na1—N1—C2 | −44.67 (12) |
Na1ii—S1—Na1—S1i | −145.35 (2) | S1ii—Na1—N1—C2 | 144.13 (11) |
C11—S1—Na1—S1ii | −119.07 (4) | Na1i—Na1—N1—C2 | 6.72 (13) |
Na1i—S1—Na1—S1ii | 145.35 (2) | N1—Na1—N2—C5 | 98.91 (11) |
Na1ii—S1—Na1—S1ii | 0.0 | S1—Na1—N2—C5 | −164.4 (4) |
C11—S1—Na1—Na1i | 95.59 (4) | S1i—Na1—N2—C5 | −21.68 (11) |
Na1ii—S1—Na1—Na1i | −145.35 (2) | S1ii—Na1—N2—C5 | −166.93 (11) |
Na1—S1—C11—C16 | 108.64 (12) | Na1i—Na1—N2—C5 | −24.73 (13) |
Na1i—S1—C11—C16 | −160.81 (11) | N1—Na1—N2—C6 | −138.63 (10) |
Na1ii—S1—C11—C16 | 11.12 (14) | S1—Na1—N2—C6 | −41.9 (4) |
Na1—S1—C11—C12 | −70.63 (12) | S1i—Na1—N2—C6 | 100.78 (9) |
Na1i—S1—C11—C12 | 19.93 (12) | S1ii—Na1—N2—C6 | −44.47 (9) |
Na1ii—S1—C11—C12 | −168.15 (10) | Na1i—Na1—N2—C6 | 97.73 (10) |
C16—C11—C12—C13 | −0.5 (2) | N1—Na1—N2—C4 | −21.81 (9) |
S1—C11—C12—C13 | 178.83 (13) | S1—Na1—N2—C4 | 74.9 (4) |
C11—C12—C13—C14 | 0.2 (3) | S1i—Na1—N2—C4 | −142.40 (9) |
C12—C13—C14—C15 | 0.0 (3) | S1ii—Na1—N2—C4 | 72.35 (9) |
C13—C14—C15—C16 | 0.0 (3) | Na1i—Na1—N2—C4 | −145.45 (8) |
C14—C15—C16—C11 | −0.3 (3) | C1—N1—C3—C4 | −75.09 (16) |
C12—C11—C16—C15 | 0.5 (2) | C2—N1—C3—C4 | 165.63 (13) |
S1—C11—C16—C15 | −178.82 (12) | Na1—N1—C3—C4 | 37.04 (14) |
N2—Na1—N1—C1 | 110.71 (11) | C5—N2—C4—C3 | −70.22 (18) |
S1—Na1—N1—C1 | −64.05 (11) | C6—N2—C4—C3 | 170.03 (13) |
S1i—Na1—N1—C1 | −164.63 (10) | Na1—N2—C4—C3 | 50.90 (14) |
S1ii—Na1—N1—C1 | 24.17 (11) | N1—C3—C4—N2 | −65.32 (18) |
Na1i—Na1—N1—C1 | −113.24 (11) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | Na+·C6H5S−·C6H16N2 |
Mr | 248.36 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 5.944 (1), 11.200 (2), 11.899 (2) |
α, β, γ (°) | 62.58 (1), 87.14 (2), 81.32 (2) |
V (Å3) | 694.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.60 × 0.42 × 0.25 |
Data collection | |
Diffractometer | Siemens P4 four circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3921, 3066, 2636 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.094, 1.05 |
No. of reflections | 3066 |
No. of parameters | 149 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.21 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTLPC/XP.
S1—Na1 | 2.8219 (8) | Na1—S1i | 3.0310 (8) |
Na1—N2 | 2.5375 (14) | Na1—S1ii | 3.1966 (8) |
Na1—N1 | 2.5482 (13) | Na1—Na1i | 4.1323 (12) |
N2—Na1—N1 | 73.60 (4) | S1—Na1—S1i | 90.249 (18) |
N2—Na1—S1 | 174.95 (4) | N2—Na1—S1ii | 87.62 (3) |
N1—Na1—S1 | 106.93 (3) | N1—Na1—S1ii | 93.31 (3) |
N2—Na1—S1i | 93.77 (3) | S1—Na1—S1ii | 87.338 (19) |
N1—Na1—S1i | 120.38 (3) | S1i—Na1—S1ii | 145.28 (2) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |
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Strong phenyl/phenyl interactions stabilize the dimer of tris(phenylthio)methane, even in the gas phase (Bock, Havlas et al., 2000). An attempt to add negative charge by reduction with sodium metal failed due to tris(phenylthio)methane decomposition to thiophenolate, which crystallizes in the presence of a sodium metal mirror and of tetramethylethylenediamine (I) to another lipophilically wrapped polyion aggregate (Bock, Hauck et al., 1995; Bock, Schödel et al., 1995; Bock, Beck et al., 1998; Bock, Heigel & Nagel, 2000; Bock & Heigel, 2000a,b). \sch
The sodium cations form distorted trigonal bipyramides with sulfur centers of the thiophenolates and N centers of tetramethylethylenediamine. The axial positions are occupied by S1, N2 and the equatorial positions by S1A, S1B and N1 [Fig. 1; symmetry codes: (A) -x, 1 - y, -z; (B) 1 - x, 1 - y, -z]. These interatomic contacts agree with the sum of van der waals radii. Nevertheless, the interaction of the sodium cation to S1A and S1B decreases but the geometry of a trigonal bipyramid is well defined (Fig. 1). The sodium cations are connected by Na—S—Na bridges to infinite chains along the a axis with alternate distances Na—Na of 4.132 (1) Å and 4.361 (1) Å (Fig. 2a). The C—S bonding of the thiophenolate has a distance of 1.754 Å, that is in mean band of 1.77 (3) calculated for the distances C—S of 472 crystal structures including thiophenolate registered in the Cambridge Structural Database. The bonding C—S of thiophenolates shows a broad variety in length obviously independent of the cation. Therefore bis(tetra-n-butylammonium)tetrakis(benzenethiolatoiron) containing only iron cations exhibits distances C—S with maximum differences of 0.04 Å in every published crystal structure (Guiodong et al., 1987; Gloux et al., 1987; Excoffon et al., 1991). The lipophilical wrapping by phenyl rings and methyl groups (Fig.2: B) is responsible for the kinetic stability of the polyion aggregate in analogy to the hexameric tetraphenylimidodiphosphate sodium (Bock, Schödel et al., 1995).