research communications
Decachlorocyclopentasilanes coordinated by pairs of chloride anions, with different cations, but the same solvent molecules
aInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
*Correspondence e-mail: bolte@chemie.uni-frankfurt.de
We have determined the crystal structures of two decachlorocyclopentasilanes, namely bis(tetra-n-butylammonium) dichloride decachlorocyclopentasilane dichloromethane disolvate, 2C16H36N+·2Cl−·Si5Cl10·2CH2Cl2, (I), and bis(tetraethylammonium) dichloride decachlorocyclopentasilane dichloromethane disolvate, 2C8H20N+·2Cl−·Si5Cl10·2CH2Cl2, (II), both of which crystallize with discrete cations, anions, and solvent molecules. In (I), the complete decachlorocyclopentasilane ring is generated by a crystallographic twofold rotation axis. In (II), one cation is located on a general position and the other two are disordered about centres of inversion. These are the first structures featuring the structural motif of a five-membered cyclopentasilane ring coordinated from both sides by a chloride ion. The extended structures of (I) and (II) feature numerous C—H⋯Cl interactions. In (II), the N atoms are located on centres of inversion and as a result, the ethylene chains are disordered over equally occupied orientations.
1. Chemical context
The title compounds are the first known halide diadducts of the long-known perchlorinated cyclopentasilane Si5Cl10 (Hengge & Kovar, 1977). Their structures can be seen as inverse-sandwich complexes, in which two chloride ions lie above and below the planar five-membered silicon ring.
In the recent years, new and facile synthetic protocols for the Cl− diadduct [Si6Cl14]2– of dodecachlorocyclohexasilane have been developed. It can either be prepared through the chloride-induced of Si2Cl6, which leads directly to [Si6Cl14]2– (Tillmann et al., 2012, 2014; Tillmann, Moxter et al., 2015), or the Lewis acidic uncomplexed Si6Cl12 can be used as the starting material. In the latter case, mere addition of soluble chloride salts [R4N]Cl (R = nBu or Et) leads to the formation of [Si6Cl14]2– (Dai et al., 2010). Given this background, it was of interest to investigate the and ability of Si5Cl10 to bind Cl− ions.
2. Structural commentary
Bis(tetra-n-butylammonium) dichloride decachlorocyclopentasilane dichloromethane disolvate, 2C16H36N+·2Cl−·Si5Cl10·2CH2Cl2, (I), crystallizes with discrete cations, anions, and solvent molecules (Fig. 1). The five-membered decachlorocyclopentasilane ring is located on a twofold rotation axis. The Si—Cl bond lengths range from 2.081 (3) Å for Si2—Cl21 to 2.100 (3) Å for Si2—Cl22. The Si—Si bond lengths do not vary markedly: they range from 2.339 (3) Å (Si1—Si2) to 2.347 (3) Å (Si2—Si3).
The almost planar ring (r.m.s. deviation 0.002 Å) is coordinated by two chloride anions located above and below the ring. The distances of the chloride ions to the Si atoms [Cl1⋯Si1 2.907 (3), Cl1⋯Si2 2.914 (3), Cl1⋯Si3 2.930 (3) Å,] show that the chloride ions are located almost exactly above the centroid of the ring [distance Cl1⋯Cg = 2.1434 (16) Å].
Bis(tetraethylammonium) dichloride decachlorocyclopentasilane dichloromethane disolvate, 2C8H20N+·2Cl−·Si5Cl10·2CH2Cl2, (II), crystallizes as (I) with discrete cations, anions, and solvent molecules (Fig. 2). The Si—Cl bonds again lie in a quite narrow range [2.0805 (9) Å (Si1—Cl12) to 2.1102 (8) Å (Si2—Cl22)] and the Si—Si bond lengths are also very similar [2.3386 (8) Å (Si1—Si2) to 2.3473 (7) Å (Si4—Si5)].
The five-membered decachlorocyclopentasilane ring is almost planar (r.m.s. deviation = 0.017 Å) and coordinated by two chloride anions located above and below the ring with a Cl⋯Cg distance of 2.1781 (5) Å for Cl1 and 2.1237 (5) Å for Cl2. The Cl⋯Si distances range from 2.9381 (7) Å (Cl1⋯Si5) to 2.9645 (7) Å (Cl1⋯Si2) and from 2.8759 (8) Å (Cl2⋯Si2) to 2.9510 (7) Å (Cl2⋯Si5). Since the Cl⋯Si distances have a broader range for Cl2, it can be said that this ion is slightly displaced from a position directly over the ring centroid.
It is interesting to note that (I) and (II) have – apart from the different cations – the same molecular stoichiometry, i.e. one Si5Cl10 ring coordinated by two chloride anions, two cations and two solvent dichloromethane molecules. However, since (I) has twofold rotation symmetry, there are only half of the chemical entities in the asymmetric unit.
3. Supramolecular features
The components of (I) and (II) are linked by a plethora of C—H⋯Cl contacts (Tables 1 and 2, respectively); in particular the chloride ions are surrounded by C—H groups. For an example, see Fig. 3. As a result of the disorder of the N2 and N3 cations in (II), a plot showing the coordination of the Cl ions looks extremely crowded and is therefore omitted.
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4. Database survey
The present structures are the first examples of a decachlorocyclopentasilane ring coordinated by two anions. There are only two structures of a decachlorocyclopentasilane ring in the CSD (Version 5.38 of November 2016 plus three updates; Groom et al., 2016), namely decachlorocyclopentasilane 4-methylbenzonitrile solvate (refcode ELAFON; Dai et al., 2010) and decachlorocyclopentasilane acetonitrile solvate (ELAFIH; Dai et al., 2010). In both of them, the decachlorocyclopentasilane ring is almost planar (0.017 Å for ELAFON and 0.001 Å for ELAFIH) and shows almost no variation in the Si—Si (2.358–2.368 Å for ELAFON and 2.342–2.349 Å for ELAFIH) and Si—Cl (2.030–2.059 Å for ELAFON and 2.034– 2.038 Å for ELAFIH) bond lengths.
The distance of the N atom to the centroid of the ring is 2.152 and 2.196 Å for ELAFON and 2.234 Å for ELAFIH. This difference could be due to the steric demand of the benzene ring in ELAFIH. The N⋯Cg distances are in the same range as the Cl⋯Cg distances in (I) and (II).
Mean values of the structural parameters of the four compared structures and dichloride dodecachlorocyclohexasilanes (Tillmann, Lerner & Bolte, 2015) are compiled in Table 3. It is remarkable that the Si—Si and Si—Cl bond lengths do not vary significantly between the five and six-membered Si rings, but the Cl⋯Cg distance in the dodecachlorocyclohexasilanes is significantly shorter than for decachlorocyclopentasilane. This might be due to the fact that the Cl ligands form a narrower cone in five- compared to six-membered rings.
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5. Synthesis and crystallization
The addition of a solution of [R4N]Cl (R = nBu or Et) in CH2Cl2 at 195 K to a solution of Si5Cl10 in CH2Cl2 furnished the Cl− diadducts [R4N]2[Si5Cl12] (R = nBu or Et) (Fig. 4). Crystals of [R4N]2[Si5Cl12] (R = nBu or Et) could be harvested after storage of the reaction solution for one week at 195 K in 89% and 93% yield, respectively. Both adducts are stable in the solid phase under inert conditions. However, in solution a rapid transformation of [nBu4N]2[Si5Cl12] to [nBu4N]2[Si6Cl14] and [nBu4N]2[Si7Cl16] (Fig. 5) can be observed via 29Si NMR spectroscopy (for the NMR spectrum see Fig. S1 in the Supporting information), while [Et4N]2[Si5Cl12] is not soluble. For comparison, a 29Si CP/MAS NMR spectrum of single crystals of [nBu4N]2[Si5Cl12] was recorded (Fig. S2 in the Supporting information).
6. details
Crystal data, data collection and structure . H atoms were refined using a riding model, with Cmethyl—H = 0.98 Å or Cmethylene—H = 0.99 Å and with Uiso(H) = 1.5Ueq(Cmethyl) or 1.2Ueq(C).
details are summarized in Table 4
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The Cl atoms of the dichloromethane solvent molecule in (I) have rather large displacement ellipsoids, but since no valid disorder model for splitting this molecule could be found, with enlarged ADPs was preferred. In (II), atoms N2 and N3 are located on centres of inversion. As a result, the ethylene chains are disordered over equally occupied orientations.
Supporting information
https://doi.org/10.1107/S2056989017016310/hb7717sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016310/hb7717Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017016310/hb7717IIsup3.hkl
Fig. S1. 29Si NMR spectra. DOI: https://doi.org/10.1107/S2056989017016310/hb7717sup4.pdf
Fig. S2. 29Si CP/MAS NMR spectrum. DOI: https://doi.org/10.1107/S2056989017016310/hb7717sup5.pdf
For both structures, data collection: X-AREA (Stoe & Cie, 2001); cell
X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and publCIF (Westrip, 2010).2C16H36N+·2Cl−·Si5Cl10·2CH2Cl2 | F(000) = 2544 |
Mr = 1220.61 | Dx = 1.341 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.9091 (15) Å | Cell parameters from 30920 reflections |
b = 15.7423 (7) Å | θ = 3.3–25.8° |
c = 19.8734 (16) Å | µ = 0.85 mm−1 |
β = 112.451 (6)° | T = 173 K |
V = 6045.7 (7) Å3 | Needle, colourless |
Z = 4 | 0.27 × 0.16 × 0.12 mm |
Stoe IPDS II two-circle diffractometer | 4428 reflections with I > 2σ(I) |
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.060 |
ω scans | θmax = 25.8°, θmin = 3.3° |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −25→25 |
Tmin = 0.543, Tmax = 1.000 | k = −18→19 |
32650 measured reflections | l = −24→24 |
5699 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.103 | H-atom parameters constrained |
wR(F2) = 0.199 | w = 1/[σ2(Fo2) + (0.0209P)2 + 98.7944P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max < 0.001 |
5699 reflections | Δρmax = 1.50 e Å−3 |
258 parameters | Δρmin = −1.46 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.44920 (9) | 0.65838 (13) | 0.63371 (9) | 0.0392 (4) | |
Si1 | 0.55353 (9) | 0.75962 (13) | 0.74394 (10) | 0.0312 (4) | |
Si2 | 0.58692 (10) | 0.61853 (14) | 0.73977 (10) | 0.0329 (4) | |
Si3 | 0.5000 | 0.53144 (19) | 0.7500 | 0.0368 (7) | |
Cl11 | 0.55030 (11) | 0.83349 (15) | 0.65484 (12) | 0.0536 (5) | |
Cl12 | 0.62942 (10) | 0.82642 (15) | 0.82814 (12) | 0.0535 (6) | |
Cl21 | 0.60720 (11) | 0.58866 (16) | 0.64782 (11) | 0.0534 (6) | |
Cl22 | 0.68493 (9) | 0.59548 (15) | 0.82099 (11) | 0.0499 (5) | |
Cl31 | 0.46207 (13) | 0.44593 (15) | 0.66352 (15) | 0.0667 (7) | |
N1 | 0.3868 (3) | 0.7205 (4) | 0.4082 (3) | 0.0278 (12) | |
C1 | 0.4614 (3) | 0.6993 (5) | 0.4564 (4) | 0.0309 (15) | |
H1A | 0.4668 | 0.6368 | 0.4578 | 0.037* | |
H1B | 0.4699 | 0.7185 | 0.5065 | 0.037* | |
C2 | 0.5172 (4) | 0.7380 (5) | 0.4335 (4) | 0.0373 (17) | |
H2A | 0.5102 | 0.7188 | 0.3838 | 0.045* | |
H2B | 0.5135 | 0.8008 | 0.4329 | 0.045* | |
C3 | 0.5881 (4) | 0.7115 (6) | 0.4859 (4) | 0.047 (2) | |
H3A | 0.5894 | 0.6489 | 0.4913 | 0.056* | |
H3B | 0.5969 | 0.7367 | 0.5343 | 0.056* | |
C4 | 0.6455 (4) | 0.7395 (6) | 0.4601 (6) | 0.060 (3) | |
H4A | 0.6905 | 0.7210 | 0.4956 | 0.090* | |
H4B | 0.6375 | 0.7137 | 0.4127 | 0.090* | |
H4C | 0.6450 | 0.8015 | 0.4557 | 0.090* | |
C5 | 0.3758 (4) | 0.8156 (5) | 0.3999 (4) | 0.0351 (16) | |
H5A | 0.3258 | 0.8265 | 0.3728 | 0.042* | |
H5B | 0.4007 | 0.8374 | 0.3700 | 0.042* | |
C6 | 0.3994 (4) | 0.8659 (5) | 0.4706 (4) | 0.0440 (19) | |
H6A | 0.3744 | 0.8457 | 0.5010 | 0.053* | |
H6B | 0.4495 | 0.8568 | 0.4981 | 0.053* | |
C7 | 0.3852 (4) | 0.9597 (5) | 0.4545 (5) | 0.055 (2) | |
H7A | 0.3348 | 0.9685 | 0.4288 | 0.066* | |
H7B | 0.4082 | 0.9787 | 0.4219 | 0.066* | |
C8 | 0.4110 (5) | 1.0135 (6) | 0.5234 (6) | 0.078 (3) | |
H8A | 0.4008 | 1.0734 | 0.5104 | 0.116* | |
H8B | 0.3877 | 0.9957 | 0.5554 | 0.116* | |
H8C | 0.4611 | 1.0059 | 0.5485 | 0.116* | |
C9 | 0.3385 (3) | 0.6853 (5) | 0.4418 (4) | 0.0303 (15) | |
H9A | 0.2910 | 0.7045 | 0.4120 | 0.036* | |
H9B | 0.3513 | 0.7107 | 0.4908 | 0.036* | |
C10 | 0.3372 (4) | 0.5894 (5) | 0.4494 (4) | 0.0396 (17) | |
H10A | 0.3273 | 0.5623 | 0.4015 | 0.047* | |
H10B | 0.3830 | 0.5693 | 0.4835 | 0.047* | |
C11 | 0.2824 (4) | 0.5642 (5) | 0.4778 (4) | 0.044 (2) | |
H11A | 0.2364 | 0.5815 | 0.4420 | 0.053* | |
H11B | 0.2906 | 0.5951 | 0.5237 | 0.053* | |
C12 | 0.2818 (4) | 0.4698 (6) | 0.4915 (5) | 0.059 (2) | |
H12A | 0.2455 | 0.4567 | 0.5097 | 0.088* | |
H12B | 0.2727 | 0.4389 | 0.4459 | 0.088* | |
H12C | 0.3268 | 0.4525 | 0.5276 | 0.088* | |
C13 | 0.3714 (4) | 0.6817 (5) | 0.3333 (3) | 0.0348 (16) | |
H13A | 0.4026 | 0.7085 | 0.3125 | 0.042* | |
H13B | 0.3834 | 0.6206 | 0.3400 | 0.042* | |
C14 | 0.2978 (4) | 0.6896 (6) | 0.2779 (4) | 0.0412 (18) | |
H14A | 0.2839 | 0.7501 | 0.2711 | 0.049* | |
H14B | 0.2657 | 0.6589 | 0.2953 | 0.049* | |
C15 | 0.2940 (4) | 0.6515 (7) | 0.2051 (4) | 0.057 (2) | |
H15A | 0.3294 | 0.6789 | 0.1907 | 0.068* | |
H15B | 0.3049 | 0.5901 | 0.2118 | 0.068* | |
C16 | 0.2249 (5) | 0.6627 (9) | 0.1459 (5) | 0.083 (4) | |
H16A | 0.2251 | 0.6375 | 0.1009 | 0.124* | |
H16B | 0.1898 | 0.6346 | 0.1594 | 0.124* | |
H16C | 0.2143 | 0.7234 | 0.1383 | 0.124* | |
C1L | 0.1235 (8) | 0.4569 (8) | 0.2807 (9) | 0.110 (5) | |
H1L1 | 0.1317 | 0.4857 | 0.3275 | 0.132* | |
H1L2 | 0.0904 | 0.4924 | 0.2416 | 0.132* | |
Cl1L | 0.19998 (18) | 0.4539 (3) | 0.2681 (2) | 0.1200 (15) | |
Cl2L | 0.0881 (5) | 0.3685 (5) | 0.2810 (5) | 0.294 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0321 (9) | 0.0584 (12) | 0.0230 (8) | −0.0037 (9) | 0.0059 (7) | −0.0024 (8) |
Si1 | 0.0233 (9) | 0.0364 (11) | 0.0327 (10) | −0.0031 (8) | 0.0092 (8) | −0.0029 (8) |
Si2 | 0.0281 (9) | 0.0417 (12) | 0.0302 (10) | 0.0050 (9) | 0.0124 (8) | −0.0018 (9) |
Si3 | 0.0373 (15) | 0.0330 (16) | 0.0421 (16) | 0.000 | 0.0174 (13) | 0.000 |
Cl11 | 0.0498 (11) | 0.0575 (14) | 0.0576 (13) | −0.0087 (10) | 0.0251 (10) | 0.0109 (11) |
Cl12 | 0.0345 (10) | 0.0572 (14) | 0.0600 (13) | −0.0137 (9) | 0.0082 (9) | −0.0193 (11) |
Cl21 | 0.0526 (12) | 0.0739 (15) | 0.0441 (11) | 0.0101 (11) | 0.0302 (10) | −0.0056 (10) |
Cl22 | 0.0276 (9) | 0.0708 (15) | 0.0470 (11) | 0.0139 (9) | 0.0095 (8) | 0.0056 (10) |
Cl31 | 0.0663 (15) | 0.0501 (13) | 0.0859 (18) | −0.0109 (12) | 0.0315 (13) | −0.0313 (13) |
N1 | 0.027 (3) | 0.032 (3) | 0.028 (3) | 0.003 (2) | 0.014 (2) | 0.002 (2) |
C1 | 0.025 (3) | 0.036 (4) | 0.030 (4) | 0.002 (3) | 0.009 (3) | 0.000 (3) |
C2 | 0.044 (4) | 0.035 (4) | 0.039 (4) | −0.006 (3) | 0.023 (3) | −0.005 (3) |
C3 | 0.030 (4) | 0.065 (6) | 0.045 (4) | −0.006 (4) | 0.014 (3) | −0.011 (4) |
C4 | 0.045 (5) | 0.054 (6) | 0.096 (7) | −0.011 (4) | 0.043 (5) | −0.018 (5) |
C5 | 0.032 (4) | 0.035 (4) | 0.040 (4) | 0.009 (3) | 0.015 (3) | 0.003 (3) |
C6 | 0.052 (5) | 0.039 (4) | 0.046 (4) | 0.001 (4) | 0.024 (4) | −0.007 (4) |
C7 | 0.042 (5) | 0.038 (5) | 0.082 (7) | 0.005 (4) | 0.020 (4) | −0.012 (4) |
C8 | 0.063 (6) | 0.052 (6) | 0.116 (9) | −0.004 (5) | 0.033 (6) | −0.034 (6) |
C9 | 0.024 (3) | 0.042 (4) | 0.025 (3) | 0.000 (3) | 0.010 (3) | 0.003 (3) |
C10 | 0.039 (4) | 0.043 (4) | 0.041 (4) | −0.002 (4) | 0.019 (3) | 0.003 (4) |
C11 | 0.028 (4) | 0.057 (5) | 0.049 (5) | 0.001 (4) | 0.016 (3) | 0.016 (4) |
C12 | 0.043 (5) | 0.059 (6) | 0.079 (7) | −0.005 (4) | 0.027 (5) | 0.019 (5) |
C13 | 0.040 (4) | 0.043 (4) | 0.025 (3) | 0.004 (3) | 0.017 (3) | −0.002 (3) |
C14 | 0.036 (4) | 0.055 (5) | 0.030 (4) | −0.003 (4) | 0.010 (3) | −0.005 (3) |
C15 | 0.044 (5) | 0.082 (7) | 0.045 (5) | 0.005 (5) | 0.018 (4) | −0.005 (5) |
C16 | 0.056 (6) | 0.150 (12) | 0.035 (5) | 0.004 (7) | 0.009 (4) | −0.019 (6) |
C1L | 0.143 (13) | 0.077 (9) | 0.149 (13) | 0.017 (9) | 0.100 (11) | −0.003 (9) |
Cl1L | 0.087 (2) | 0.168 (4) | 0.114 (3) | −0.022 (2) | 0.048 (2) | −0.065 (3) |
Cl2L | 0.471 (12) | 0.237 (7) | 0.350 (10) | −0.225 (8) | 0.355 (10) | −0.183 (7) |
Si1—Cl12 | 2.097 (3) | C7—H7A | 0.9900 |
Si1—Cl11 | 2.098 (3) | C7—H7B | 0.9900 |
Si1—Si2 | 2.339 (3) | C8—H8A | 0.9800 |
Si1—Si1i | 2.341 (4) | C8—H8B | 0.9800 |
Si2—Cl21 | 2.081 (3) | C8—H8C | 0.9800 |
Si2—Cl22 | 2.100 (3) | C9—C10 | 1.519 (10) |
Si2—Si3 | 2.347 (3) | C9—H9A | 0.9900 |
Si3—Cl31 | 2.086 (3) | C9—H9B | 0.9900 |
Si3—Cl31i | 2.086 (3) | C10—C11 | 1.509 (9) |
Si3—Si2i | 2.347 (3) | C10—H10A | 0.9900 |
N1—C9 | 1.513 (8) | C10—H10B | 0.9900 |
N1—C5 | 1.515 (9) | C11—C12 | 1.513 (12) |
N1—C1 | 1.523 (8) | C11—H11A | 0.9900 |
N1—C13 | 1.525 (8) | C11—H11B | 0.9900 |
C1—C2 | 1.531 (9) | C12—H12A | 0.9800 |
C1—H1A | 0.9900 | C12—H12B | 0.9800 |
C1—H1B | 0.9900 | C12—H12C | 0.9800 |
C2—C3 | 1.510 (10) | C13—C14 | 1.518 (10) |
C2—H2A | 0.9900 | C13—H13A | 0.9900 |
C2—H2B | 0.9900 | C13—H13B | 0.9900 |
C3—C4 | 1.538 (10) | C14—C15 | 1.539 (10) |
C3—H3A | 0.9900 | C14—H14A | 0.9900 |
C3—H3B | 0.9900 | C14—H14B | 0.9900 |
C4—H4A | 0.9800 | C15—C16 | 1.485 (12) |
C4—H4B | 0.9800 | C15—H15A | 0.9900 |
C4—H4C | 0.9800 | C15—H15B | 0.9900 |
C5—C6 | 1.521 (10) | C16—H16A | 0.9800 |
C5—H5A | 0.9900 | C16—H16B | 0.9800 |
C5—H5B | 0.9900 | C16—H16C | 0.9800 |
C6—C7 | 1.516 (11) | C1L—Cl2L | 1.578 (14) |
C6—H6A | 0.9900 | C1L—Cl1L | 1.711 (13) |
C6—H6B | 0.9900 | C1L—H1L1 | 0.9900 |
C7—C8 | 1.522 (13) | C1L—H1L2 | 0.9900 |
Cl12—Si1—Cl11 | 99.57 (12) | C6—C7—H7B | 109.2 |
Cl12—Si1—Si2 | 111.06 (11) | C8—C7—H7B | 109.2 |
Cl11—Si1—Si2 | 114.22 (11) | H7A—C7—H7B | 107.9 |
Cl12—Si1—Si1i | 112.32 (12) | C7—C8—H8A | 109.5 |
Cl11—Si1—Si1i | 111.28 (12) | C7—C8—H8B | 109.5 |
Si2—Si1—Si1i | 108.28 (6) | H8A—C8—H8B | 109.5 |
Cl21—Si2—Cl22 | 99.76 (11) | C7—C8—H8C | 109.5 |
Cl21—Si2—Si1 | 114.16 (12) | H8A—C8—H8C | 109.5 |
Cl22—Si2—Si1 | 110.71 (12) | H8B—C8—H8C | 109.5 |
Cl21—Si2—Si3 | 111.61 (12) | N1—C9—C10 | 116.6 (6) |
Cl22—Si2—Si3 | 113.15 (11) | N1—C9—H9A | 108.1 |
Si1—Si2—Si3 | 107.47 (10) | C10—C9—H9A | 108.1 |
Cl31—Si3—Cl31i | 99.6 (2) | N1—C9—H9B | 108.1 |
Cl31—Si3—Si2 | 111.65 (9) | C10—C9—H9B | 108.1 |
Cl31i—Si3—Si2 | 112.64 (9) | H9A—C9—H9B | 107.3 |
Cl31—Si3—Si2i | 112.64 (9) | C11—C10—C9 | 110.0 (6) |
Cl31i—Si3—Si2i | 111.65 (9) | C11—C10—H10A | 109.7 |
Si2—Si3—Si2i | 108.50 (16) | C9—C10—H10A | 109.7 |
C9—N1—C5 | 108.1 (5) | C11—C10—H10B | 109.7 |
C9—N1—C1 | 109.8 (5) | C9—C10—H10B | 109.7 |
C5—N1—C1 | 111.2 (5) | H10A—C10—H10B | 108.2 |
C9—N1—C13 | 110.9 (5) | C10—C11—C12 | 112.6 (7) |
C5—N1—C13 | 108.8 (5) | C10—C11—H11A | 109.1 |
C1—N1—C13 | 108.0 (5) | C12—C11—H11A | 109.1 |
N1—C1—C2 | 116.1 (6) | C10—C11—H11B | 109.1 |
N1—C1—H1A | 108.3 | C12—C11—H11B | 109.1 |
C2—C1—H1A | 108.3 | H11A—C11—H11B | 107.8 |
N1—C1—H1B | 108.3 | C11—C12—H12A | 109.5 |
C2—C1—H1B | 108.3 | C11—C12—H12B | 109.5 |
H1A—C1—H1B | 107.4 | H12A—C12—H12B | 109.5 |
C3—C2—C1 | 110.1 (6) | C11—C12—H12C | 109.5 |
C3—C2—H2A | 109.6 | H12A—C12—H12C | 109.5 |
C1—C2—H2A | 109.6 | H12B—C12—H12C | 109.5 |
C3—C2—H2B | 109.6 | C14—C13—N1 | 116.9 (6) |
C1—C2—H2B | 109.6 | C14—C13—H13A | 108.1 |
H2A—C2—H2B | 108.1 | N1—C13—H13A | 108.1 |
C2—C3—C4 | 112.1 (7) | C14—C13—H13B | 108.1 |
C2—C3—H3A | 109.2 | N1—C13—H13B | 108.1 |
C4—C3—H3A | 109.2 | H13A—C13—H13B | 107.3 |
C2—C3—H3B | 109.2 | C13—C14—C15 | 108.9 (6) |
C4—C3—H3B | 109.2 | C13—C14—H14A | 109.9 |
H3A—C3—H3B | 107.9 | C15—C14—H14A | 109.9 |
C3—C4—H4A | 109.5 | C13—C14—H14B | 109.9 |
C3—C4—H4B | 109.5 | C15—C14—H14B | 109.9 |
H4A—C4—H4B | 109.5 | H14A—C14—H14B | 108.3 |
C3—C4—H4C | 109.5 | C16—C15—C14 | 112.5 (7) |
H4A—C4—H4C | 109.5 | C16—C15—H15A | 109.1 |
H4B—C4—H4C | 109.5 | C14—C15—H15A | 109.1 |
N1—C5—C6 | 115.6 (6) | C16—C15—H15B | 109.1 |
N1—C5—H5A | 108.4 | C14—C15—H15B | 109.1 |
C6—C5—H5A | 108.4 | H15A—C15—H15B | 107.8 |
N1—C5—H5B | 108.4 | C15—C16—H16A | 109.5 |
C6—C5—H5B | 108.4 | C15—C16—H16B | 109.5 |
H5A—C5—H5B | 107.4 | H16A—C16—H16B | 109.5 |
C7—C6—C5 | 110.1 (7) | C15—C16—H16C | 109.5 |
C7—C6—H6A | 109.6 | H16A—C16—H16C | 109.5 |
C5—C6—H6A | 109.6 | H16B—C16—H16C | 109.5 |
C7—C6—H6B | 109.6 | Cl2L—C1L—Cl1L | 116.2 (8) |
C5—C6—H6B | 109.6 | Cl2L—C1L—H1L1 | 108.2 |
H6A—C6—H6B | 108.2 | Cl1L—C1L—H1L1 | 108.2 |
C6—C7—C8 | 112.3 (8) | Cl2L—C1L—H1L2 | 108.2 |
C6—C7—H7A | 109.2 | Cl1L—C1L—H1L2 | 108.2 |
C8—C7—H7A | 109.2 | H1L1—C1L—H1L2 | 107.4 |
C9—N1—C1—C2 | −174.3 (6) | C5—N1—C9—C10 | 175.4 (6) |
C5—N1—C1—C2 | −54.8 (7) | C1—N1—C9—C10 | −63.2 (7) |
C13—N1—C1—C2 | 64.6 (7) | C13—N1—C9—C10 | 56.1 (8) |
N1—C1—C2—C3 | −179.8 (6) | N1—C9—C10—C11 | −175.2 (6) |
C1—C2—C3—C4 | 172.9 (7) | C9—C10—C11—C12 | −176.1 (7) |
C9—N1—C5—C6 | 68.4 (7) | C9—N1—C13—C14 | 55.2 (8) |
C1—N1—C5—C6 | −52.2 (7) | C5—N1—C13—C14 | −63.6 (8) |
C13—N1—C5—C6 | −171.0 (6) | C1—N1—C13—C14 | 175.6 (6) |
N1—C5—C6—C7 | −179.9 (6) | N1—C13—C14—C15 | 176.8 (7) |
C5—C6—C7—C8 | −177.3 (7) | C13—C14—C15—C16 | −175.4 (9) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cl1 | 0.99 | 2.88 | 3.686 (7) | 139 |
C2—H2A···Cl31ii | 0.99 | 2.89 | 3.596 (8) | 129 |
C5—H5A···Cl22iii | 0.99 | 2.99 | 3.945 (7) | 163 |
C9—H9B···Cl1 | 0.99 | 2.91 | 3.652 (7) | 132 |
C1L—H1L1···Cl12iii | 0.99 | 2.96 | 3.528 (13) | 119 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+3/2, z−1/2. |
2C8H20N+·2Cl−·Si5Cl10·2CH2Cl2 | Z = 2 |
Mr = 996.20 | F(000) = 1016 |
Triclinic, P1 | Dx = 1.525 Mg m−3 |
a = 10.3596 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.9612 (5) Å | Cell parameters from 153722 reflections |
c = 16.0205 (6) Å | θ = 3.3–30.8° |
α = 89.959 (3)° | µ = 1.17 mm−1 |
β = 72.484 (3)° | T = 173 K |
γ = 79.534 (3)° | Block, colourless |
V = 2169.29 (15) Å3 | 0.23 × 0.23 × 0.20 mm |
Stoe IPDS II two-circle diffractometer | 11976 reflections with I > 2σ(I) |
ω scans | Rint = 0.043 |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | θmax = 30.5°, θmin = 3.4° |
Tmin = 0.408, Tmax = 1.000 | h = −14→14 |
62962 measured reflections | k = −19→19 |
13044 independent reflections | l = −22→22 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0683P)2 + 1.6519P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
13044 reflections | Δρmax = 0.87 e Å−3 |
409 parameters | Δρmin = −0.84 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.68362 (5) | 0.71247 (4) | 0.37887 (3) | 0.03357 (10) | |
Cl2 | 0.55394 (6) | 0.71721 (4) | 0.14756 (3) | 0.03425 (11) | |
Si1 | 0.79603 (6) | 0.63165 (4) | 0.19539 (4) | 0.03316 (12) | |
Si2 | 0.74595 (6) | 0.80223 (4) | 0.20699 (4) | 0.02939 (11) | |
Si3 | 0.51729 (5) | 0.85241 (4) | 0.29623 (3) | 0.02570 (10) | |
Si4 | 0.42527 (5) | 0.71172 (4) | 0.33588 (3) | 0.02431 (10) | |
Si5 | 0.59853 (6) | 0.57465 (4) | 0.27696 (4) | 0.02724 (11) | |
Cl11 | 0.97197 (6) | 0.57714 (6) | 0.23162 (6) | 0.0628 (2) | |
Cl12 | 0.86579 (9) | 0.57414 (5) | 0.06642 (4) | 0.0632 (2) | |
Cl21 | 0.88627 (7) | 0.86092 (6) | 0.25209 (5) | 0.05179 (16) | |
Cl22 | 0.78501 (6) | 0.86177 (4) | 0.08273 (4) | 0.04303 (13) | |
Cl31 | 0.49581 (7) | 0.94164 (4) | 0.40573 (4) | 0.04399 (13) | |
Cl32 | 0.39997 (6) | 0.94686 (4) | 0.23306 (4) | 0.04020 (12) | |
Cl41 | 0.33929 (5) | 0.71094 (4) | 0.47227 (3) | 0.03436 (10) | |
Cl42 | 0.24659 (5) | 0.71209 (4) | 0.29964 (4) | 0.03703 (11) | |
Cl51 | 0.63586 (6) | 0.47736 (4) | 0.36927 (4) | 0.04057 (12) | |
Cl52 | 0.53223 (8) | 0.48498 (4) | 0.20041 (4) | 0.04831 (15) | |
N1 | 0.27041 (18) | 0.79721 (13) | −0.00541 (11) | 0.0299 (3) | |
C1 | 0.2204 (4) | 0.7299 (2) | 0.06657 (18) | 0.0551 (7) | |
H1A | 0.1238 | 0.7262 | 0.0717 | 0.066* | |
H1B | 0.2206 | 0.7590 | 0.1228 | 0.066* | |
C2 | 0.3050 (4) | 0.62647 (19) | 0.0530 (2) | 0.0551 (7) | |
H2A | 0.2656 | 0.5882 | 0.1024 | 0.083* | |
H2B | 0.3034 | 0.5959 | −0.0016 | 0.083* | |
H2C | 0.4004 | 0.6288 | 0.0497 | 0.083* | |
C3 | 0.2867 (3) | 0.7533 (2) | −0.09498 (16) | 0.0438 (5) | |
H3A | 0.3641 | 0.6966 | −0.1089 | 0.053* | |
H3B | 0.3126 | 0.8021 | −0.1387 | 0.053* | |
C4 | 0.1610 (4) | 0.7201 (3) | −0.1052 (3) | 0.0648 (9) | |
H4A | 0.1816 | 0.6928 | −0.1651 | 0.097* | |
H4B | 0.1357 | 0.6701 | −0.0636 | 0.097* | |
H4C | 0.0842 | 0.7759 | −0.0934 | 0.097* | |
C5 | 0.1640 (3) | 0.89268 (19) | 0.0117 (2) | 0.0470 (6) | |
H5A | 0.1863 | 0.9314 | −0.0407 | 0.056* | |
H5B | 0.0721 | 0.8767 | 0.0192 | 0.056* | |
C6 | 0.1555 (3) | 0.9554 (2) | 0.0910 (2) | 0.0545 (7) | |
H6A | 0.0852 | 1.0145 | 0.0967 | 0.082* | |
H6B | 0.1306 | 0.9187 | 0.1438 | 0.082* | |
H6C | 0.2451 | 0.9736 | 0.0837 | 0.082* | |
C7 | 0.4085 (3) | 0.81784 (18) | −0.00349 (18) | 0.0412 (5) | |
H7A | 0.3980 | 0.8424 | 0.0566 | 0.049* | |
H7B | 0.4756 | 0.7554 | −0.0155 | 0.049* | |
C8 | 0.4683 (3) | 0.8892 (2) | −0.0662 (2) | 0.0517 (6) | |
H8A | 0.5568 | 0.8970 | −0.0594 | 0.078* | |
H8B | 0.4826 | 0.8651 | −0.1264 | 0.078* | |
H8C | 0.4048 | 0.9523 | −0.0540 | 0.078* | |
N2 | 0.0000 | 0.5000 | 0.5000 | 0.0260 (4) | |
C21 | −0.0005 (4) | 0.6091 (3) | 0.5117 (3) | 0.0331 (8) | 0.5 |
H21A | −0.0855 | 0.6483 | 0.5040 | 0.040* | 0.5 |
H21B | 0.0800 | 0.6270 | 0.4675 | 0.040* | 0.5 |
C21' | 0.0128 (5) | 0.5139 (3) | 0.5909 (3) | 0.0350 (8) | 0.5 |
H21C | 0.1013 | 0.4755 | 0.5941 | 0.042* | 0.5 |
H21D | −0.0633 | 0.4912 | 0.6352 | 0.042* | 0.5 |
C22 | 0.0063 (3) | 0.6300 (3) | 0.6105 (2) | 0.0638 (9) | |
H22A | 0.0061 | 0.6994 | 0.6197 | 0.096* | 0.5 |
H22B | −0.0740 | 0.6122 | 0.6536 | 0.096* | 0.5 |
H22C | 0.0908 | 0.5910 | 0.6173 | 0.096* | 0.5 |
H22D | 0.0144 | 0.6403 | 0.6690 | 0.096* | 0.5 |
H22E | 0.0823 | 0.6518 | 0.5665 | 0.096* | 0.5 |
H22F | −0.0818 | 0.6675 | 0.6075 | 0.096* | 0.5 |
C23 | 0.1319 (4) | 0.4394 (3) | 0.5085 (3) | 0.0294 (7) | 0.5 |
H23A | 0.1285 | 0.3693 | 0.5040 | 0.035* | 0.5 |
H23B | 0.1411 | 0.4544 | 0.5666 | 0.035* | 0.5 |
C23' | 0.1182 (4) | 0.5289 (3) | 0.4300 (3) | 0.0321 (7) | 0.5 |
H23C | 0.1196 | 0.5986 | 0.4398 | 0.039* | 0.5 |
H23D | 0.1063 | 0.5197 | 0.3717 | 0.039* | 0.5 |
C24 | 0.2624 (2) | 0.4624 (2) | 0.4327 (2) | 0.0533 (7) | |
H24A | 0.3471 | 0.4228 | 0.4389 | 0.080* | 0.5 |
H24B | 0.2538 | 0.4467 | 0.3753 | 0.080* | 0.5 |
H24C | 0.2662 | 0.5317 | 0.4377 | 0.080* | 0.5 |
H24D | 0.3391 | 0.4813 | 0.3871 | 0.080* | 0.5 |
H24E | 0.2743 | 0.4723 | 0.4903 | 0.080* | 0.5 |
H24F | 0.2610 | 0.3935 | 0.4224 | 0.080* | 0.5 |
N3 | 0.0000 | 1.0000 | 0.5000 | 0.0324 (5) | |
C31 | −0.0124 (7) | 1.0998 (4) | 0.5376 (4) | 0.0522 (13) | 0.5 |
H31A | −0.0599 | 1.1032 | 0.6015 | 0.063* | 0.5 |
H31B | −0.0684 | 1.1477 | 0.5106 | 0.063* | 0.5 |
C31' | 0.1452 (5) | 1.0189 (5) | 0.4881 (4) | 0.0509 (13) | 0.5 |
H31C | 0.2003 | 1.0076 | 0.4255 | 0.061* | 0.5 |
H31D | 0.1910 | 0.9729 | 0.5221 | 0.061* | 0.5 |
C32 | 0.1392 (6) | 1.1271 (4) | 0.5199 (3) | 0.0956 (17) | |
H32A | 0.1294 | 1.1930 | 0.5450 | 0.143* | 0.5 |
H32B | 0.1941 | 1.0803 | 0.5474 | 0.143* | 0.5 |
H32C | 0.1855 | 1.1246 | 0.4566 | 0.143* | 0.5 |
H32D | 0.2330 | 1.1379 | 0.5118 | 0.143* | 0.5 |
H32E | 0.0951 | 1.1727 | 0.4856 | 0.143* | 0.5 |
H32F | 0.0857 | 1.1380 | 0.5821 | 0.143* | 0.5 |
C33 | −0.0905 (5) | 1.0176 (4) | 0.5927 (3) | 0.0412 (10) | 0.5 |
H33A | −0.1850 | 1.0092 | 0.5967 | 0.049* | 0.5 |
H33B | −0.0952 | 1.0851 | 0.6140 | 0.049* | 0.5 |
C33' | 0.0691 (5) | 0.9243 (4) | 0.5529 (3) | 0.0459 (11) | 0.5 |
H33C | 0.1629 | 0.9350 | 0.5479 | 0.055* | 0.5 |
H33D | 0.0765 | 0.8572 | 0.5296 | 0.055* | 0.5 |
C34 | −0.0250 (4) | 0.9384 (3) | 0.6531 (2) | 0.0724 (11) | |
H34A | −0.0833 | 0.9490 | 0.7144 | 0.109* | 0.5 |
H34B | −0.0212 | 0.8719 | 0.6318 | 0.109* | 0.5 |
H34C | 0.0683 | 0.9475 | 0.6490 | 0.109* | 0.5 |
H34D | 0.0162 | 0.8916 | 0.6879 | 0.109* | 0.5 |
H34E | −0.0314 | 1.0050 | 0.6756 | 0.109* | 0.5 |
H34F | −0.1175 | 0.9274 | 0.6574 | 0.109* | 0.5 |
C1L | 0.1880 (4) | 0.3162 (2) | 0.1144 (2) | 0.0565 (7) | |
H1L1 | 0.2330 | 0.2960 | 0.0516 | 0.068* | |
H1L2 | 0.0997 | 0.3611 | 0.1200 | 0.068* | |
Cl1A | 0.29537 (8) | 0.37721 (5) | 0.15334 (6) | 0.05663 (17) | |
Cl1B | 0.15522 (9) | 0.21224 (6) | 0.17452 (6) | 0.05883 (18) | |
C2L | 0.4865 (4) | 0.7900 (3) | 0.6208 (2) | 0.0642 (8) | |
H2L1 | 0.5201 | 0.8228 | 0.5657 | 0.077* | |
H2L2 | 0.4831 | 0.7222 | 0.6050 | 0.077* | |
Cl2A | 0.60192 (10) | 0.78831 (6) | 0.68194 (6) | 0.0634 (2) | |
Cl2B | 0.32076 (10) | 0.85079 (10) | 0.67916 (6) | 0.0828 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0361 (2) | 0.0429 (3) | 0.0274 (2) | −0.01369 (19) | −0.01464 (17) | 0.00581 (17) |
Cl2 | 0.0424 (3) | 0.0357 (2) | 0.0271 (2) | −0.00201 (19) | −0.01742 (18) | −0.00062 (16) |
Si1 | 0.0284 (2) | 0.0311 (3) | 0.0307 (3) | 0.0042 (2) | −0.0012 (2) | 0.0051 (2) |
Si2 | 0.0258 (2) | 0.0307 (3) | 0.0279 (2) | −0.00452 (19) | −0.00314 (19) | 0.00405 (19) |
Si3 | 0.0266 (2) | 0.0229 (2) | 0.0245 (2) | −0.00328 (17) | −0.00405 (18) | −0.00117 (17) |
Si4 | 0.0239 (2) | 0.0234 (2) | 0.0246 (2) | −0.00303 (17) | −0.00662 (17) | −0.00054 (16) |
Si5 | 0.0287 (2) | 0.0228 (2) | 0.0295 (2) | −0.00127 (18) | −0.00988 (19) | −0.00119 (18) |
Cl11 | 0.0288 (3) | 0.0663 (4) | 0.0855 (5) | 0.0061 (3) | −0.0147 (3) | 0.0272 (4) |
Cl12 | 0.0766 (5) | 0.0475 (3) | 0.0344 (3) | 0.0162 (3) | 0.0127 (3) | −0.0050 (2) |
Cl21 | 0.0423 (3) | 0.0669 (4) | 0.0530 (3) | −0.0301 (3) | −0.0132 (3) | 0.0083 (3) |
Cl22 | 0.0427 (3) | 0.0432 (3) | 0.0342 (2) | −0.0043 (2) | −0.0008 (2) | 0.0144 (2) |
Cl31 | 0.0582 (3) | 0.0344 (2) | 0.0360 (3) | −0.0095 (2) | −0.0090 (2) | −0.0121 (2) |
Cl32 | 0.0410 (3) | 0.0302 (2) | 0.0445 (3) | 0.00368 (19) | −0.0119 (2) | 0.00648 (19) |
Cl41 | 0.0336 (2) | 0.0416 (3) | 0.0253 (2) | −0.01096 (19) | −0.00306 (17) | 0.00253 (17) |
Cl42 | 0.0285 (2) | 0.0429 (3) | 0.0433 (3) | −0.00619 (18) | −0.01663 (19) | 0.0021 (2) |
Cl51 | 0.0404 (3) | 0.0343 (2) | 0.0516 (3) | −0.0089 (2) | −0.0198 (2) | 0.0174 (2) |
Cl52 | 0.0629 (4) | 0.0337 (3) | 0.0529 (3) | −0.0081 (2) | −0.0251 (3) | −0.0133 (2) |
N1 | 0.0310 (8) | 0.0304 (8) | 0.0275 (7) | −0.0052 (6) | −0.0080 (6) | 0.0030 (6) |
C1 | 0.0746 (19) | 0.0423 (13) | 0.0395 (12) | −0.0160 (13) | −0.0016 (12) | 0.0076 (10) |
C2 | 0.085 (2) | 0.0343 (12) | 0.0522 (15) | −0.0151 (13) | −0.0287 (15) | 0.0117 (10) |
C3 | 0.0530 (14) | 0.0456 (12) | 0.0365 (11) | −0.0105 (10) | −0.0187 (10) | −0.0010 (9) |
C4 | 0.069 (2) | 0.0598 (18) | 0.087 (2) | −0.0171 (15) | −0.0524 (19) | −0.0019 (16) |
C5 | 0.0357 (11) | 0.0378 (12) | 0.0634 (16) | −0.0041 (9) | −0.0110 (11) | 0.0002 (11) |
C6 | 0.0512 (15) | 0.0407 (13) | 0.0554 (15) | −0.0079 (11) | 0.0070 (12) | −0.0096 (11) |
C7 | 0.0378 (11) | 0.0392 (11) | 0.0498 (13) | −0.0028 (9) | −0.0208 (10) | 0.0006 (9) |
C8 | 0.0378 (12) | 0.0480 (14) | 0.0643 (17) | −0.0150 (10) | −0.0042 (11) | −0.0017 (12) |
N2 | 0.0230 (9) | 0.0267 (10) | 0.0268 (10) | −0.0036 (8) | −0.0063 (8) | 0.0051 (8) |
C21 | 0.0329 (18) | 0.0228 (16) | 0.040 (2) | −0.0042 (14) | −0.0058 (16) | 0.0055 (14) |
C21' | 0.0330 (19) | 0.043 (2) | 0.0293 (17) | −0.0049 (16) | −0.0108 (15) | 0.0050 (15) |
C22 | 0.0471 (15) | 0.073 (2) | 0.0663 (19) | −0.0141 (14) | −0.0078 (13) | −0.0342 (16) |
C23 | 0.0252 (16) | 0.0297 (17) | 0.0327 (17) | −0.0030 (13) | −0.0095 (14) | 0.0056 (14) |
C23' | 0.0275 (17) | 0.0336 (18) | 0.0322 (18) | −0.0082 (14) | −0.0031 (14) | 0.0067 (14) |
C24 | 0.0240 (9) | 0.0589 (16) | 0.0671 (17) | −0.0074 (10) | 0.0005 (10) | −0.0163 (13) |
N3 | 0.0243 (10) | 0.0345 (12) | 0.0329 (11) | 0.0000 (9) | −0.0037 (9) | −0.0037 (9) |
C31 | 0.072 (4) | 0.037 (2) | 0.040 (2) | −0.006 (2) | −0.009 (2) | −0.0055 (19) |
C31' | 0.030 (2) | 0.081 (4) | 0.043 (3) | −0.015 (2) | −0.0107 (18) | 0.013 (2) |
C32 | 0.146 (4) | 0.103 (3) | 0.080 (3) | −0.084 (3) | −0.061 (3) | 0.023 (2) |
C33 | 0.034 (2) | 0.049 (2) | 0.0292 (18) | 0.0039 (18) | 0.0004 (16) | −0.0031 (17) |
C33' | 0.033 (2) | 0.055 (3) | 0.045 (2) | 0.0018 (19) | −0.0118 (19) | 0.009 (2) |
C34 | 0.083 (2) | 0.110 (3) | 0.0381 (14) | −0.048 (2) | −0.0207 (15) | 0.0216 (16) |
C1L | 0.0620 (17) | 0.0570 (16) | 0.0647 (18) | −0.0176 (14) | −0.0369 (15) | 0.0150 (13) |
Cl1A | 0.0500 (3) | 0.0452 (3) | 0.0797 (5) | −0.0104 (3) | −0.0265 (3) | 0.0018 (3) |
Cl1B | 0.0613 (4) | 0.0527 (4) | 0.0685 (5) | −0.0195 (3) | −0.0237 (4) | 0.0092 (3) |
C2L | 0.0639 (19) | 0.078 (2) | 0.0503 (16) | 0.0043 (16) | −0.0266 (14) | −0.0118 (15) |
Cl2A | 0.0746 (5) | 0.0622 (4) | 0.0588 (4) | 0.0015 (4) | −0.0367 (4) | −0.0093 (3) |
Cl2B | 0.0612 (5) | 0.1170 (9) | 0.0576 (5) | 0.0084 (5) | −0.0143 (4) | 0.0110 (5) |
Si1—Cl12 | 2.0805 (9) | C22—H22B | 0.9800 |
Si1—Cl11 | 2.0906 (9) | C22—H22C | 0.9800 |
Si1—Si2 | 2.3386 (8) | C22—H22D | 0.9800 |
Si1—Si5 | 2.3469 (8) | C22—H22E | 0.9800 |
Si2—Cl21 | 2.0910 (8) | C22—H22F | 0.9800 |
Si2—Cl22 | 2.1102 (8) | C23—C24 | 1.604 (5) |
Si2—Si3 | 2.3465 (7) | C23—H23A | 0.9900 |
Si3—Cl31 | 2.0849 (7) | C23—H23B | 0.9900 |
Si3—Cl32 | 2.0967 (8) | C23'—C24 | 1.622 (5) |
Si3—Si4 | 2.3419 (7) | C23'—H23C | 0.9900 |
Si4—Cl41 | 2.0977 (7) | C23'—H23D | 0.9900 |
Si4—Cl42 | 2.0993 (7) | C24—H24A | 0.9800 |
Si4—Si5 | 2.3473 (7) | C24—H24B | 0.9800 |
Si5—Cl51 | 2.0814 (7) | C24—H24C | 0.9800 |
Si5—Cl52 | 2.0890 (8) | C24—H24D | 0.9800 |
N1—C3 | 1.510 (3) | C24—H24E | 0.9800 |
N1—C1 | 1.516 (3) | C24—H24F | 0.9800 |
N1—C7 | 1.519 (3) | N3—C31ii | 1.487 (5) |
N1—C5 | 1.533 (3) | N3—C31 | 1.487 (5) |
C1—C2 | 1.526 (4) | N3—C33ii | 1.491 (4) |
C1—H1A | 0.9900 | N3—C33 | 1.491 (4) |
C1—H1B | 0.9900 | N3—C31'ii | 1.530 (5) |
C2—H2A | 0.9800 | N3—C31' | 1.530 (5) |
C2—H2B | 0.9800 | N3—C33'ii | 1.561 (5) |
C2—H2C | 0.9800 | N3—C33' | 1.561 (5) |
C3—C4 | 1.511 (4) | C31—C32 | 1.625 (8) |
C3—H3A | 0.9900 | C31—H31A | 0.9900 |
C3—H3B | 0.9900 | C31—H31B | 0.9900 |
C4—H4A | 0.9800 | C31'—C32 | 1.579 (8) |
C4—H4B | 0.9800 | C31'—H31C | 0.9900 |
C4—H4C | 0.9800 | C31'—H31D | 0.9900 |
C5—C6 | 1.514 (4) | C32—H32A | 0.9800 |
C5—H5A | 0.9900 | C32—H32B | 0.9800 |
C5—H5B | 0.9900 | C32—H32C | 0.9800 |
C6—H6A | 0.9800 | C32—H32D | 0.9800 |
C6—H6B | 0.9800 | C32—H32E | 0.9800 |
C6—H6C | 0.9800 | C32—H32F | 0.9800 |
C7—C8 | 1.495 (4) | C33—C34 | 1.656 (6) |
C7—H7A | 0.9900 | C33—H33A | 0.9900 |
C7—H7B | 0.9900 | C33—H33B | 0.9900 |
C8—H8A | 0.9800 | C33'—C34 | 1.599 (6) |
C8—H8B | 0.9800 | C33'—H33C | 0.9900 |
C8—H8C | 0.9800 | C33'—H33D | 0.9900 |
N2—C23'i | 1.508 (4) | C34—H34A | 0.9800 |
N2—C23' | 1.508 (4) | C34—H34B | 0.9800 |
N2—C23i | 1.514 (4) | C34—H34C | 0.9800 |
N2—C23 | 1.514 (4) | C34—H34D | 0.9800 |
N2—C21'i | 1.517 (4) | C34—H34E | 0.9800 |
N2—C21' | 1.517 (4) | C34—H34F | 0.9800 |
N2—C21 | 1.533 (4) | C1L—Cl1A | 1.765 (3) |
N2—C21i | 1.533 (4) | C1L—Cl1B | 1.769 (3) |
C21—C22 | 1.633 (6) | C1L—H1L1 | 0.9900 |
C21—H21A | 0.9900 | C1L—H1L2 | 0.9900 |
C21—H21B | 0.9900 | C2L—Cl2B | 1.746 (4) |
C21'—C22 | 1.636 (6) | C2L—Cl2A | 1.757 (3) |
C21'—H21C | 0.9900 | C2L—H2L1 | 0.9900 |
C21'—H21D | 0.9900 | C2L—H2L2 | 0.9900 |
C22—H22A | 0.9800 | ||
Cl12—Si1—Cl11 | 98.50 (4) | C21—C22—H22A | 109.5 |
Cl12—Si1—Si2 | 113.28 (3) | C21—C22—H22B | 109.5 |
Cl11—Si1—Si2 | 111.32 (4) | H22A—C22—H22B | 109.5 |
Cl12—Si1—Si5 | 111.49 (4) | C21—C22—H22C | 109.5 |
Cl11—Si1—Si5 | 113.90 (4) | H22A—C22—H22C | 109.5 |
Si2—Si1—Si5 | 108.23 (3) | H22B—C22—H22C | 109.5 |
Cl21—Si2—Cl22 | 98.77 (4) | C21'—C22—H22D | 109.5 |
Cl21—Si2—Si1 | 112.27 (4) | C21'—C22—H22E | 109.5 |
Cl22—Si2—Si1 | 111.72 (3) | H22D—C22—H22E | 109.5 |
Cl21—Si2—Si3 | 112.69 (3) | C21'—C22—H22F | 109.5 |
Cl22—Si2—Si3 | 113.01 (3) | H22D—C22—H22F | 109.5 |
Si1—Si2—Si3 | 108.26 (3) | H22E—C22—H22F | 109.5 |
Cl31—Si3—Cl32 | 100.07 (3) | N2—C23—C24 | 110.3 (3) |
Cl31—Si3—Si4 | 111.69 (3) | N2—C23—H23A | 109.6 |
Cl32—Si3—Si4 | 111.61 (3) | C24—C23—H23A | 109.6 |
Cl31—Si3—Si2 | 114.12 (3) | N2—C23—H23B | 109.6 |
Cl32—Si3—Si2 | 111.88 (3) | C24—C23—H23B | 109.6 |
Si4—Si3—Si2 | 107.47 (3) | H23A—C23—H23B | 108.1 |
Cl41—Si4—Cl42 | 98.87 (3) | N2—C23'—C24 | 109.6 (3) |
Cl41—Si4—Si3 | 111.22 (3) | N2—C23'—H23C | 109.7 |
Cl42—Si4—Si3 | 112.22 (3) | C24—C23'—H23C | 109.7 |
Cl41—Si4—Si5 | 112.75 (3) | N2—C23'—H23D | 109.7 |
Cl42—Si4—Si5 | 113.01 (3) | C24—C23'—H23D | 109.7 |
Si3—Si4—Si5 | 108.60 (3) | H23C—C23'—H23D | 108.2 |
Cl51—Si5—Cl52 | 99.88 (3) | C23—C24—H24A | 109.5 |
Cl51—Si5—Si1 | 113.02 (3) | C23—C24—H24B | 109.5 |
Cl52—Si5—Si1 | 112.15 (3) | H24A—C24—H24B | 109.5 |
Cl51—Si5—Si4 | 114.27 (3) | C23—C24—H24C | 109.5 |
Cl52—Si5—Si4 | 110.11 (3) | H24A—C24—H24C | 109.5 |
Si1—Si5—Si4 | 107.38 (3) | H24B—C24—H24C | 109.5 |
C3—N1—C1 | 111.90 (19) | C23'—C24—H24D | 109.5 |
C3—N1—C7 | 108.98 (18) | C23'—C24—H24E | 109.5 |
C1—N1—C7 | 109.2 (2) | H24D—C24—H24E | 109.5 |
C3—N1—C5 | 108.79 (19) | C23'—C24—H24F | 109.5 |
C1—N1—C5 | 108.2 (2) | H24D—C24—H24F | 109.5 |
C7—N1—C5 | 109.76 (17) | H24E—C24—H24F | 109.5 |
N1—C1—C2 | 115.0 (2) | C31ii—N3—C31 | 180.0 (4) |
N1—C1—H1A | 108.5 | C31ii—N3—C33ii | 66.3 (3) |
C2—C1—H1A | 108.5 | C31—N3—C33ii | 113.7 (3) |
N1—C1—H1B | 108.5 | C31ii—N3—C33 | 113.7 (3) |
C2—C1—H1B | 108.5 | C31—N3—C33 | 66.3 (3) |
H1A—C1—H1B | 107.5 | C33ii—N3—C33 | 180.0 |
C1—C2—H2A | 109.5 | C31'ii—N3—C31' | 180.0 (7) |
C1—C2—H2B | 109.5 | C31'ii—N3—C33'ii | 72.4 (3) |
H2A—C2—H2B | 109.5 | C31'—N3—C33'ii | 107.6 (3) |
C1—C2—H2C | 109.5 | C31'ii—N3—C33' | 107.6 (3) |
H2A—C2—H2C | 109.5 | C31'—N3—C33' | 72.4 (3) |
H2B—C2—H2C | 109.5 | C33'ii—N3—C33' | 180.0 (3) |
N1—C3—C4 | 115.5 (2) | N3—C31—C32 | 110.4 (4) |
N1—C3—H3A | 108.4 | N3—C31—H31A | 109.6 |
C4—C3—H3A | 108.4 | C32—C31—H31A | 109.6 |
N1—C3—H3B | 108.4 | N3—C31—H31B | 109.6 |
C4—C3—H3B | 108.4 | C32—C31—H31B | 109.6 |
H3A—C3—H3B | 107.5 | H31A—C31—H31B | 108.1 |
C3—C4—H4A | 109.5 | N3—C31'—C32 | 110.7 (4) |
C3—C4—H4B | 109.5 | N3—C31'—H31C | 109.5 |
H4A—C4—H4B | 109.5 | C32—C31'—H31C | 109.5 |
C3—C4—H4C | 109.5 | N3—C31'—H31D | 109.5 |
H4A—C4—H4C | 109.5 | C32—C31'—H31D | 109.5 |
H4B—C4—H4C | 109.5 | H31C—C31'—H31D | 108.1 |
C6—C5—N1 | 115.2 (2) | C31—C32—H32A | 109.5 |
C6—C5—H5A | 108.5 | C31—C32—H32B | 109.5 |
N1—C5—H5A | 108.5 | H32A—C32—H32B | 109.5 |
C6—C5—H5B | 108.5 | C31—C32—H32C | 109.5 |
N1—C5—H5B | 108.5 | H32A—C32—H32C | 109.5 |
H5A—C5—H5B | 107.5 | H32B—C32—H32C | 109.5 |
C5—C6—H6A | 109.5 | C31'—C32—H32D | 109.5 |
C5—C6—H6B | 109.5 | C31'—C32—H32E | 109.5 |
H6A—C6—H6B | 109.5 | H32D—C32—H32E | 109.5 |
C5—C6—H6C | 109.5 | C31'—C32—H32F | 109.5 |
H6A—C6—H6C | 109.5 | H32D—C32—H32F | 109.5 |
H6B—C6—H6C | 109.5 | H32E—C32—H32F | 109.5 |
C8—C7—N1 | 116.3 (2) | N3—C33—C34 | 108.3 (3) |
C8—C7—H7A | 108.2 | N3—C33—H33A | 110.0 |
N1—C7—H7A | 108.2 | C34—C33—H33A | 110.0 |
C8—C7—H7B | 108.2 | N3—C33—H33B | 110.0 |
N1—C7—H7B | 108.2 | C34—C33—H33B | 110.0 |
H7A—C7—H7B | 107.4 | H33A—C33—H33B | 108.4 |
C7—C8—H8A | 109.5 | N3—C33'—C34 | 107.8 (3) |
C7—C8—H8B | 109.5 | N3—C33'—H33C | 110.1 |
H8A—C8—H8B | 109.5 | C34—C33'—H33C | 110.1 |
C7—C8—H8C | 109.5 | N3—C33'—H33D | 110.1 |
H8A—C8—H8C | 109.5 | C34—C33'—H33D | 110.1 |
H8B—C8—H8C | 109.5 | H33C—C33'—H33D | 108.5 |
C23'i—N2—C23' | 180.0 | C33—C34—H34A | 109.5 |
C23i—N2—C23 | 180.0 (3) | C33—C34—H34B | 109.5 |
C23'i—N2—C21'i | 111.7 (2) | H34A—C34—H34B | 109.5 |
C23'—N2—C21'i | 68.3 (2) | C33—C34—H34C | 109.5 |
C23'i—N2—C21' | 68.3 (2) | H34A—C34—H34C | 109.5 |
C23'—N2—C21' | 111.7 (2) | H34B—C34—H34C | 109.5 |
C21'i—N2—C21' | 180.0 | C33'—C34—H34D | 109.5 |
C23i—N2—C21 | 69.5 (2) | C33'—C34—H34E | 109.5 |
C23—N2—C21 | 110.5 (2) | H34D—C34—H34E | 109.5 |
C23i—N2—C21i | 110.5 (2) | C33'—C34—H34F | 109.5 |
C23—N2—C21i | 69.5 (2) | H34D—C34—H34F | 109.5 |
C21—N2—C21i | 180.0 (4) | H34E—C34—H34F | 109.5 |
N2—C21—C22 | 107.8 (3) | Cl1A—C1L—Cl1B | 110.64 (16) |
N2—C21—H21A | 110.2 | Cl1A—C1L—H1L1 | 109.5 |
C22—C21—H21A | 110.2 | Cl1B—C1L—H1L1 | 109.5 |
N2—C21—H21B | 110.2 | Cl1A—C1L—H1L2 | 109.5 |
C22—C21—H21B | 110.2 | Cl1B—C1L—H1L2 | 109.5 |
H21A—C21—H21B | 108.5 | H1L1—C1L—H1L2 | 108.1 |
N2—C21'—C22 | 108.4 (3) | Cl2B—C2L—Cl2A | 111.70 (18) |
N2—C21'—H21C | 110.0 | Cl2B—C2L—H2L1 | 109.3 |
C22—C21'—H21C | 110.0 | Cl2A—C2L—H2L1 | 109.3 |
N2—C21'—H21D | 110.0 | Cl2B—C2L—H2L2 | 109.3 |
C22—C21'—H21D | 110.0 | Cl2A—C2L—H2L2 | 109.3 |
H21C—C21'—H21D | 108.4 | H2L1—C2L—H2L2 | 107.9 |
C3—N1—C1—C2 | 52.6 (3) | C23'i—N2—C21'—C22 | −117.4 (3) |
C7—N1—C1—C2 | −68.1 (3) | C23'—N2—C21'—C22 | 62.6 (3) |
C5—N1—C1—C2 | 172.4 (3) | C21—N2—C23—C24 | −62.3 (3) |
C1—N1—C3—C4 | 53.9 (3) | C21i—N2—C23—C24 | 117.7 (3) |
C7—N1—C3—C4 | 174.8 (2) | C21'i—N2—C23'—C24 | −119.9 (3) |
C5—N1—C3—C4 | −65.6 (3) | C21'—N2—C23'—C24 | 60.1 (3) |
C3—N1—C5—C6 | −168.9 (2) | C33ii—N3—C31—C32 | −49.5 (5) |
C1—N1—C5—C6 | 69.3 (3) | C33—N3—C31—C32 | 130.5 (5) |
C7—N1—C5—C6 | −49.8 (3) | C33'ii—N3—C31'—C32 | 57.8 (4) |
C3—N1—C7—C8 | 61.8 (3) | C33'—N3—C31'—C32 | −122.2 (4) |
C1—N1—C7—C8 | −175.7 (2) | C31ii—N3—C33—C34 | 60.0 (5) |
C5—N1—C7—C8 | −57.2 (3) | C31—N3—C33—C34 | −120.0 (5) |
C23i—N2—C21—C22 | 118.2 (3) | C31'ii—N3—C33'—C34 | −58.6 (5) |
C23—N2—C21—C22 | −61.8 (3) | C31'—N3—C33'—C34 | 121.4 (5) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cl42 | 0.99 | 2.99 | 3.829 (3) | 144 |
C2—H2C···Cl2 | 0.98 | 2.95 | 3.753 (3) | 139 |
C3—H3A···Cl52iii | 0.99 | 2.79 | 3.643 (3) | 144 |
C3—H3B···Cl2Biv | 0.99 | 2.98 | 3.804 (3) | 142 |
C5—H5B···Cl22v | 0.99 | 2.89 | 3.850 (3) | 165 |
C6—H6B···Cl21v | 0.98 | 2.86 | 3.630 (3) | 136 |
C7—H7A···Cl2 | 0.99 | 2.86 | 3.394 (2) | 115 |
C22—H22C···Cl51vi | 0.98 | 2.89 | 3.847 (4) | 165 |
C22—H22E···Cl41 | 0.98 | 2.90 | 3.859 (3) | 165 |
C23—H23B···Cl1vi | 0.99 | 2.98 | 3.465 (4) | 111 |
C23′—H23C···Cl42 | 0.99 | 2.87 | 3.497 (4) | 122 |
C24—H24C···Cl41 | 0.98 | 2.84 | 3.793 (3) | 164 |
C24—H24E···Cl51vi | 0.98 | 2.81 | 3.771 (3) | 165 |
C24—H24F···Cl2Avi | 0.98 | 2.92 | 3.778 (3) | 147 |
C31′—H31C···Cl31 | 0.99 | 2.95 | 3.434 (5) | 111 |
C32—H32F···Cl21vii | 0.98 | 2.76 | 3.584 (4) | 142 |
C33—H33A···Cl32ii | 0.99 | 2.94 | 3.515 (4) | 118 |
C33′—H33D···Cl41 | 0.99 | 2.98 | 3.630 (5) | 124 |
C34—H34A···Cl1Bi | 0.98 | 2.93 | 3.556 (3) | 123 |
C34—H34C···Cl2B | 0.98 | 2.89 | 3.716 (4) | 142 |
C34—H34A···Cl1Bi | 0.98 | 2.93 | 3.556 (3) | 123 |
C1L—H1L1···Cl12iii | 0.99 | 2.90 | 3.421 (3) | 114 |
C2L—H2L2···Cl41 | 0.99 | 2.96 | 3.465 (3) | 113 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z; (iv) x, y, z−1; (v) x−1, y, z; (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y+2, −z+1. |
X = Cl for (I) and (II) and X = N for ELAFON and ELAFIH. The row for Si6Cl12 contains data for dichloride dodecachlorohexasilanes (Tillmann, Lerner & Bolte, 2015). |
Structure | Si—Si | Si—Cl | X···Cg |
(I) | 2.342 | 2.092 | 2.143 |
(II) | 2.344 | 2.092 | 2.151 |
ELAFON | 2.363 | 2.049 | 2.174 |
ELAFIH | 2.348 | 2.036 | 2.234 |
Si6Cl12 | 2.322 | 2.078 | 1.90 |
Footnotes
‡Correspondence e-mail for synthetic work: Matthias.Wagner@chemie.uni-frankfurt.de.
Acknowledgements
The authors wish to thank Johanna Becker-Baldus for the recording of the 29Si CP/MAS NMR spectrum.
References
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