Acta Cryst. (2009). E65, o1048 [ doi:10.1107/S1600536809013300 ]
The asymmetric unit of the title compound, C8H20N+·C9H16B11- or [Et4N][12-PhCC-closo-CB11H11], consists of one cation and one anion. The [12-PhCC-closo-CB11H11]- anion is close to possessing a non-crystallographic plane of mirror symmetry with a nearly linear B-C![[triple bond]](/logos/entities/z-tbnd_rmgif.gif)
C-C group, with B-CC and CC-C angles of 177.15 (16) and 176.64 (17)°, respectively.
[Et4N][12-PhCC-closo-CB11H11] was synthesized according to a published procedure (Finze, 2008). The spectroscopic data have been reported earlier (Finze, 2008). The salt was dissolved in acetonitrile and slow evaporation of the solvent resulted in colorless crystals.
All hydrogen atom positions were obtained from difference fourier maps. The hydrogen atoms of the methyl groups were included in the latest stages of the refinement with a riding model and for each methyl group a common Uiso value was refined. The positional parameters and the isotropic displacement parameters of all other hydrogen atoms were refined freely.
Data collection: CrysAlis CCD (Kuma, 2000); cell refinement: CrysAlis RED (Kuma, 2000); data reduction: CrysAlis RED (Kuma, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./br2103fig1thm.gif)
| Fig. 1. : The 12-phenylethinylcarba-closo-dodecaborate cation in [Et4N][12-PhCC-closo-CB11H11]. Hydrogen atoms are drawn with an arbitrary radius and the displacement ellipsoids are shown at the 40% probability level. |
![[Figure 2]](./br2103fig2thm.gif)
| Fig. 2. : The tetraethylammonium cation in [Et4N][12-PhCC-closo-CB11H11]. Hydrogen atoms are drawn with an arbitrary radius and the displacement ellipsoids are shown at the 40% probability level. |
| C8H20N+·C9H16B11− | Z = 2 |
| Mr = 373.38 | F(000) = 400 |
| Triclinic, P1 | Dx = 1.031 Mg m−3 |
| Hall symbol: -P 1 | Melting point: 433 K |
| a = 8.8201 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 12.0929 (11) Å | Cell parameters from 4623 reflections |
| c = 12.1858 (11) Å | θ = 6.8–20.7° |
| α = 81.032 (7)° | µ = 0.05 mm−1 |
| β = 79.899 (7)° | T = 293 K |
| γ = 71.553 (7)° | Block, colourless |
| V = 1206.82 (18) Å3 | 0.3 × 0.25 × 0.2 mm |
| Stoe Stadi CCD diffractometer | 3228 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.051 |
| graphite | θmax = 25.0°, θmin = 5.1° |
| ω scans | h = −10→10 |
| 17081 measured reflections | k = −14→14 |
| 4219 independent reflections | l = −14→14 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.01P)2 + 0.45P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max < 0.001 |
| 4219 reflections | Δρmax = 0.16 e Å−3 |
| 363 parameters | Δρmin = −0.15 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.037 (3) |
| C8H20N+·C9H16B11− | γ = 71.553 (7)° |
| Mr = 373.38 | V = 1206.82 (18) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.8201 (6) Å | Mo Kα radiation |
| b = 12.0929 (11) Å | µ = 0.05 mm−1 |
| c = 12.1858 (11) Å | T = 293 K |
| α = 81.032 (7)° | 0.3 × 0.25 × 0.2 mm |
| β = 79.899 (7)° |
| Stoe Stadi CCD diffractometer | 3228 reflections with I > 2σ(I) |
| 17081 measured reflections | Rint = 0.051 |
| 4219 independent reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | Δρmax = 0.16 e Å−3 |
| S = 1.00 | Δρmin = −0.15 e Å−3 |
| 4219 reflections | Absolute structure: ? |
| 363 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| N1 | 0.02767 (14) | 0.15270 (10) | 0.23820 (10) | 0.0443 (3) | |
| C11 | 0.1693 (2) | 0.11482 (16) | 0.30484 (17) | 0.0572 (4) | |
| H11A | 0.145 (2) | 0.1795 (17) | 0.3523 (15) | 0.075 (6)* | |
| H11B | 0.264 (2) | 0.1153 (15) | 0.2471 (15) | 0.067 (5)* | |
| C12 | 0.1927 (2) | −0.00116 (17) | 0.37487 (17) | 0.0756 (6) | |
| H12A | 0.0981 | 0.0009 | 0.4282 | 0.115 (5)* | |
| H12B | 0.2842 | −0.0170 | 0.4139 | 0.115 (5)* | |
| H12C | 0.2110 | −0.0617 | 0.3274 | 0.115 (5)* | |
| C13 | 0.0403 (3) | 0.06144 (18) | 0.16256 (17) | 0.0621 (5) | |
| H13A | 0.034 (2) | −0.0082 (16) | 0.2173 (15) | 0.071 (5)* | |
| H13B | −0.055 (2) | 0.0949 (16) | 0.1246 (15) | 0.074 (6)* | |
| C14 | 0.1930 (3) | 0.0312 (2) | 0.08048 (18) | 0.0937 (7) | |
| H14A | 0.1895 | −0.0262 | 0.0355 | 0.149 (6)* | |
| H14B | 0.2844 | 0.0001 | 0.1208 | 0.149 (6)* | |
| H14C | 0.2024 | 0.1005 | 0.0329 | 0.149 (6)* | |
| C15 | 0.0310 (3) | 0.26924 (16) | 0.17111 (18) | 0.0655 (5) | |
| H15A | 0.021 (2) | 0.3226 (17) | 0.2329 (15) | 0.074 (6)* | |
| H15B | 0.140 (2) | 0.2534 (16) | 0.1284 (16) | 0.075 (6)* | |
| C16 | −0.0984 (3) | 0.32222 (19) | 0.09677 (17) | 0.0891 (7) | |
| H16A | −0.0897 | 0.2691 | 0.0434 | 0.126 (5)* | |
| H16B | −0.0861 | 0.3948 | 0.0577 | 0.126 (5)* | |
| H16C | −0.2023 | 0.3366 | 0.1416 | 0.126 (5)* | |
| C17 | −0.12997 (19) | 0.16523 (15) | 0.31589 (15) | 0.0494 (4) | |
| H17A | −0.119 (2) | 0.0852 (16) | 0.3536 (14) | 0.062 (5)* | |
| H17B | −0.207 (2) | 0.1839 (14) | 0.2658 (14) | 0.060 (5)* | |
| C18 | −0.1717 (2) | 0.25361 (16) | 0.39823 (15) | 0.0660 (5) | |
| H18A | −0.1861 | 0.3305 | 0.3586 | 0.101 (4)* | |
| H18B | −0.0860 | 0.2361 | 0.4430 | 0.101 (4)* | |
| H18C | −0.2697 | 0.2509 | 0.4459 | 0.101 (4)* | |
| C1 | 0.8578 (2) | −0.42097 (13) | 0.37589 (14) | 0.0537 (4) | |
| H1 | 0.905 (2) | −0.5044 (15) | 0.4091 (13) | 0.064 (5)* | |
| B2 | 0.7262 (3) | −0.39328 (16) | 0.28148 (17) | 0.0561 (5) | |
| H2 | 0.6959 (19) | −0.4675 (14) | 0.2554 (13) | 0.064 (5)* | |
| B3 | 0.9243 (2) | −0.38352 (16) | 0.23998 (17) | 0.0555 (5) | |
| H3 | 1.012 (2) | −0.4499 (15) | 0.1888 (13) | 0.065 (5)* | |
| B4 | 0.9825 (2) | −0.33524 (16) | 0.35199 (17) | 0.0535 (5) | |
| H4 | 1.108 (2) | −0.3739 (14) | 0.3728 (13) | 0.064 (5)* | |
| B5 | 0.8195 (2) | −0.31531 (15) | 0.46186 (16) | 0.0516 (5) | |
| H5 | 0.8448 (19) | −0.3415 (14) | 0.5490 (14) | 0.062 (5)* | |
| B6 | 0.6607 (2) | −0.35139 (16) | 0.41916 (17) | 0.0560 (5) | |
| H6 | 0.588 (2) | −0.3994 (14) | 0.4814 (13) | 0.065 (5)* | |
| B7 | 0.7589 (2) | −0.27118 (15) | 0.19136 (16) | 0.0503 (4) | |
| H7 | 0.7377 (18) | −0.2580 (13) | 0.1044 (13) | 0.057 (4)* | |
| B8 | 0.5950 (2) | −0.25187 (16) | 0.30200 (17) | 0.0523 (5) | |
| H8 | 0.465 (2) | −0.2256 (14) | 0.2866 (13) | 0.067 (5)* | |
| B9 | 0.6529 (2) | −0.20266 (15) | 0.41506 (16) | 0.0496 (4) | |
| H9 | 0.5641 (19) | −0.1430 (14) | 0.4736 (13) | 0.057 (4)* | |
| B10 | 0.8521 (2) | −0.19299 (14) | 0.37266 (15) | 0.0463 (4) | |
| H10 | 0.8952 (18) | −0.1288 (13) | 0.4032 (12) | 0.054 (4)* | |
| B11 | 0.9180 (2) | −0.23517 (15) | 0.23469 (16) | 0.0486 (4) | |
| H11 | 1.002 (2) | −0.1994 (14) | 0.1743 (13) | 0.063 (5)* | |
| B12 | 0.7131 (2) | −0.15303 (14) | 0.27349 (14) | 0.0436 (4) | |
| C2 | 0.64183 (18) | −0.02308 (13) | 0.22826 (12) | 0.0467 (4) | |
| C3 | 0.58462 (17) | 0.07904 (13) | 0.19784 (12) | 0.0446 (4) | |
| C4 | 0.51356 (16) | 0.20251 (12) | 0.16824 (12) | 0.0420 (3) | |
| C5 | 0.46196 (19) | 0.27790 (14) | 0.25139 (15) | 0.0503 (4) | |
| H5A | 0.4757 (19) | 0.2488 (14) | 0.3277 (14) | 0.059 (5)* | |
| C6 | 0.3917 (2) | 0.39677 (15) | 0.22449 (18) | 0.0633 (5) | |
| H6A | 0.357 (2) | 0.4489 (17) | 0.2854 (16) | 0.078 (6)* | |
| C7 | 0.3720 (2) | 0.44060 (16) | 0.11525 (18) | 0.0662 (5) | |
| H7A | 0.318 (2) | 0.5237 (19) | 0.0958 (16) | 0.089 (6)* | |
| C8 | 0.4210 (2) | 0.36716 (16) | 0.03291 (18) | 0.0647 (5) | |
| H8A | 0.408 (2) | 0.3951 (16) | −0.0451 (16) | 0.074 (5)* | |
| C9 | 0.4921 (2) | 0.24830 (15) | 0.05830 (15) | 0.0536 (4) | |
| H9A | 0.530 (2) | 0.1947 (15) | −0.0011 (14) | 0.062 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0430 (7) | 0.0412 (7) | 0.0525 (7) | −0.0178 (6) | −0.0068 (6) | −0.0043 (5) |
| C11 | 0.0394 (9) | 0.0633 (11) | 0.0709 (12) | −0.0172 (8) | −0.0107 (9) | −0.0057 (9) |
| C12 | 0.0600 (12) | 0.0723 (13) | 0.0766 (13) | 0.0020 (10) | −0.0135 (10) | 0.0039 (10) |
| C13 | 0.0695 (13) | 0.0592 (11) | 0.0616 (11) | −0.0210 (10) | −0.0051 (10) | −0.0189 (9) |
| C14 | 0.1051 (18) | 0.0901 (16) | 0.0746 (14) | −0.0207 (13) | 0.0179 (13) | −0.0270 (12) |
| C15 | 0.0741 (13) | 0.0518 (10) | 0.0705 (12) | −0.0272 (10) | −0.0061 (11) | 0.0080 (9) |
| C16 | 0.1112 (18) | 0.0705 (13) | 0.0693 (13) | −0.0084 (12) | −0.0202 (13) | 0.0107 (10) |
| C17 | 0.0387 (9) | 0.0518 (10) | 0.0590 (10) | −0.0155 (7) | −0.0070 (8) | −0.0048 (8) |
| C18 | 0.0640 (12) | 0.0628 (11) | 0.0675 (11) | −0.0110 (9) | −0.0052 (9) | −0.0162 (9) |
| C1 | 0.0603 (10) | 0.0321 (8) | 0.0662 (10) | −0.0067 (7) | −0.0200 (8) | −0.0001 (7) |
| B2 | 0.0654 (13) | 0.0385 (9) | 0.0701 (12) | −0.0170 (9) | −0.0233 (10) | −0.0037 (9) |
| B3 | 0.0587 (12) | 0.0423 (10) | 0.0620 (12) | −0.0061 (9) | −0.0080 (10) | −0.0137 (9) |
| B4 | 0.0475 (11) | 0.0417 (9) | 0.0684 (12) | −0.0036 (8) | −0.0184 (9) | −0.0056 (8) |
| B5 | 0.0625 (12) | 0.0394 (9) | 0.0506 (10) | −0.0089 (8) | −0.0179 (9) | 0.0007 (8) |
| B6 | 0.0575 (12) | 0.0431 (10) | 0.0645 (12) | −0.0158 (9) | −0.0070 (10) | 0.0033 (9) |
| B7 | 0.0608 (12) | 0.0420 (9) | 0.0505 (10) | −0.0138 (8) | −0.0177 (9) | −0.0041 (8) |
| B8 | 0.0461 (11) | 0.0437 (10) | 0.0675 (12) | −0.0125 (8) | −0.0165 (9) | 0.0008 (8) |
| B9 | 0.0509 (11) | 0.0395 (9) | 0.0523 (10) | −0.0063 (8) | −0.0056 (9) | −0.0030 (8) |
| B10 | 0.0515 (10) | 0.0353 (8) | 0.0540 (10) | −0.0106 (8) | −0.0171 (8) | −0.0035 (7) |
| B11 | 0.0454 (10) | 0.0439 (9) | 0.0554 (11) | −0.0124 (8) | −0.0055 (8) | −0.0056 (8) |
| B12 | 0.0453 (10) | 0.0358 (8) | 0.0496 (10) | −0.0092 (7) | −0.0126 (8) | −0.0035 (7) |
| C2 | 0.0472 (9) | 0.0422 (9) | 0.0512 (9) | −0.0130 (7) | −0.0127 (7) | −0.0004 (7) |
| C3 | 0.0393 (8) | 0.0413 (8) | 0.0530 (9) | −0.0125 (7) | −0.0115 (7) | 0.0025 (7) |
| C4 | 0.0329 (7) | 0.0374 (7) | 0.0552 (9) | −0.0127 (6) | −0.0097 (6) | 0.0057 (7) |
| C5 | 0.0447 (9) | 0.0457 (9) | 0.0557 (10) | −0.0120 (7) | −0.0045 (7) | 0.0034 (7) |
| C6 | 0.0558 (11) | 0.0453 (9) | 0.0826 (13) | −0.0113 (8) | −0.0001 (10) | −0.0065 (9) |
| C7 | 0.0557 (11) | 0.0400 (9) | 0.0959 (15) | −0.0129 (8) | −0.0150 (10) | 0.0160 (10) |
| C8 | 0.0676 (12) | 0.0563 (11) | 0.0693 (12) | −0.0228 (9) | −0.0242 (10) | 0.0227 (10) |
| C9 | 0.0554 (10) | 0.0491 (9) | 0.0581 (10) | −0.0189 (8) | −0.0156 (8) | 0.0055 (8) |
| N1—C13 | 1.511 (2) | B3—H3 | 1.106 (17) |
| N1—C17 | 1.5173 (19) | B4—B5 | 1.767 (3) |
| N1—C11 | 1.519 (2) | B4—B10 | 1.768 (2) |
| N1—C15 | 1.521 (2) | B4—B11 | 1.772 (3) |
| C11—C12 | 1.498 (2) | B4—H4 | 1.112 (17) |
| C11—H11A | 0.991 (19) | B5—B10 | 1.764 (2) |
| C11—H11B | 0.996 (19) | B5—B9 | 1.768 (3) |
| C12—H12A | 0.9600 | B5—B6 | 1.771 (3) |
| C12—H12B | 0.9600 | B5—H5 | 1.101 (16) |
| C12—H12C | 0.9600 | B6—B8 | 1.771 (3) |
| C13—C14 | 1.509 (3) | B6—B9 | 1.771 (3) |
| C13—H13A | 1.000 (19) | B6—H6 | 1.117 (17) |
| C13—H13B | 0.973 (19) | B7—B12 | 1.773 (2) |
| C14—H14A | 0.9600 | B7—B11 | 1.777 (3) |
| C14—H14B | 0.9600 | B7—B8 | 1.778 (3) |
| C14—H14C | 0.9600 | B7—H7 | 1.087 (15) |
| C15—C16 | 1.501 (3) | B8—B12 | 1.779 (2) |
| C15—H15A | 1.041 (19) | B8—B9 | 1.791 (3) |
| C15—H15B | 0.98 (2) | B8—H8 | 1.127 (17) |
| C16—H16A | 0.9600 | B9—B10 | 1.778 (3) |
| C16—H16B | 0.9600 | B9—B12 | 1.782 (3) |
| C16—H16C | 0.9600 | B9—H9 | 1.118 (16) |
| C17—C18 | 1.497 (2) | B10—B12 | 1.777 (2) |
| C17—H17A | 0.987 (17) | B10—B11 | 1.778 (3) |
| C17—H17B | 0.942 (17) | B10—H10 | 1.101 (15) |
| C18—H18A | 0.9600 | B11—B12 | 1.785 (3) |
| C18—H18B | 0.9600 | B11—H11 | 1.092 (16) |
| C18—H18C | 0.9600 | B12—C2 | 1.548 (2) |
| C1—B5 | 1.692 (2) | C2—C3 | 1.202 (2) |
| C1—B4 | 1.698 (3) | C3—C4 | 1.4393 (19) |
| C1—B2 | 1.698 (2) | C4—C5 | 1.389 (2) |
| C1—B3 | 1.699 (3) | C4—C9 | 1.389 (2) |
| C1—B6 | 1.703 (3) | C5—C6 | 1.385 (2) |
| C1—H1 | 1.010 (17) | C5—H5A | 0.956 (16) |
| B2—B8 | 1.762 (3) | C6—C7 | 1.373 (3) |
| B2—B7 | 1.767 (3) | C6—H6A | 0.993 (19) |
| B2—B3 | 1.767 (3) | C7—C8 | 1.366 (3) |
| B2—B6 | 1.773 (3) | C7—H7A | 0.98 (2) |
| B2—H2 | 1.118 (16) | C8—C9 | 1.383 (2) |
| B3—B7 | 1.767 (3) | C8—H8A | 0.973 (18) |
| B3—B11 | 1.769 (3) | C9—H9A | 0.990 (17) |
| B3—B4 | 1.775 (3) | ||
| C13—N1—C17 | 106.34 (12) | C3—C2—B12 | 177.15 (16) |
| C13—N1—C11 | 110.83 (14) | C2—C3—C4 | 176.64 (17) |
| C17—N1—C11 | 110.72 (13) | C5—C4—C9 | 118.84 (14) |
| C13—N1—C15 | 111.48 (14) | C5—C4—C3 | 119.59 (14) |
| C17—N1—C15 | 111.00 (13) | C9—C4—C3 | 121.55 (14) |
| C11—N1—C15 | 106.54 (13) | C6—C5—C4 | 120.32 (16) |
| C12—C11—N1 | 115.71 (14) | C7—C6—C5 | 120.04 (19) |
| C14—C13—N1 | 115.43 (16) | C8—C7—C6 | 120.15 (17) |
| C16—C15—N1 | 115.55 (16) | C7—C8—C9 | 120.53 (18) |
| C18—C17—N1 | 116.43 (13) | C8—C9—C4 | 120.11 (18) |
| C2—C3—C4—C5 | 8(3) | C5—C6—C7—C8 | 0.2 (3) |
| C2—C3—C4—C9 | −171 (3) | C6—C7—C8—C9 | −0.5 (3) |
| C9—C4—C5—C6 | −0.6 (2) | C7—C8—C9—C4 | 0.2 (3) |
| C3—C4—C5—C6 | −179.29 (14) | C5—C4—C9—C8 | 0.3 (2) |
| C4—C5—C6—C7 | 0.4 (3) | C3—C4—C9—C8 | 178.98 (15) |
Financial support of the Fonds der Chemischen Industrie (FCI) is gratefully acknowledged.
Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Finze, M. (2008). Inorg. Chem. 47, 11857–11867.
Finze, M. (2009). Eur. J. Inorg. Chem. pp. 501–507.
Körbe, S., Schreiber, P. J. & Michl, J. (2006). Chem. Rev. 106, 5208–5249.
Kuma (2000). CrysAlis CCD and CrysAlis RED. Kuma Diffraction, Wrocław, Poland.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Carba-closo-dodecaborate anions with functional groups are potential building blocks for a variety of applications, for example ionic liquids and liquid crystals (Körbe, 2006). Recently, we have shown that {closo-CB11} clusters with one or two alkynyl groups bonded to boron are accessible by Pd-catalyzed Kumada-type cross-coupling reactions starting from the corresponding mono- and diiodinated clusters, respectively (Finze, 2008, 2009). The title compound [Et4N][12-PhCC-closo-CB11H11] crystallizes in the triclinic centrosymmetric space group P1 with one formula unit in the asymmetric unit. The bond lengths and angles in the [12-PhCC-closo-CB11H11]- anion in its [Et4N]+ salt are close to the values reported for the respective Cs+ salt (Finze, 2008). However, the quality of the data for the [Et4N]+ salt described herein is significantly better than the quality of the data obtained for the Cs+ salt. The thermal properties of [Et4N][12-PhCC-closo-CB11H11] were studied by differential scanning calorimetry (DSC). The salt melts at 433 K and is thermally stable up to 518 K.