Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015432/bj1000sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015432/bj1000IVsup2.hkl |
CCDC reference: 158245
The title compound was isolated, along with its 10-methoxy isomer (V) from the reaction between [(RhCl2{η5-C5Me5})2] (100 mg, 162 µmol) and the [tmndaH]+ salt of the [SB8H11]- anion (Jones et al., 1989) (136 mg; 394 µmol; tmnda = 1,8-bisdimethylaminonaphthalene) in CH2Cl2 / MeOH (1:1, 30 ml) for 30 min. Filtration and repeated TLC (silica gel G) on the filtrate mixture, using CH2Cl2/hexane mixtures, revealed a mixture of several coloured components, from which it was possible to separate dark red (IV) (4 mg, 6 µmol, 4%) and amber (V) (10 mg, 15 µmol, 9%) in pure form (RF 0.28 and 0.35 respectively, liquid phase CH2Cl2/hexane 8:2). Crystals of compound (IV) were obtained from diffusion of hexane into a solution in CH2Cl2. Selected NMR data for CDCl3 solutions at 300 K {cluster resonances ordered as: assignment (11B)/p.p.m. [(1H)/p.p.m. for directly attached exo-hydrogen]}. [µ-6,9-Cl-8-(OMe)-6,9-(η5-C5Me5)2 -arachno-6,9,5-Rh2SB7H7] (IV): BH(1) +8.9 [+3.64], BH(2) -21.3 [+1.34], BH(3) +5.7 [+3.54], BH(4) -26.7 [+1.44], BH(7) +1.5 [+3.19], B(8) +27.4 [OMe substituted] and BH(10) +14.4 [+3.97], with δ(1H)(µ-7,8) -0.19, δ(1H)(C5Me5) at +1.69 and +1.56, δ(1H)(OMe) at +3.61; [µ-6,9-Cl-10-(OMe)-6,9-(η5-C5Me5)2 -arachno-6,9,5-Rh2SB7H7] (V) BH(1) +9.5 [+4.08], BH(2) -23.5 [+1.55], BH(3) +6.7 [+3.63], BH(4) -26.0 [+1.45], BH(7) +3.9 [+3.30], BH(8) +26.0 [+1.45] and B(10) +9.5 [OMe substituted], with δ(1H)(µ-7,8) -1.71, δ(1H)(C5Me5) at +1.71 and +1.62, δ(1H)(OMe) at +3.42; mass spectrometry (70 eV E·I.): each had a weak m/e(max) isotopomer envelope centred at 657 corresponding to the calculated molecular ion, [C21H40B7Cl101S1Rh2]+, with a principal fragmentation involving loss of Cl.
The final difference Fourier map showed two areas of diffuse electron density. Attempts to model these meaningfully as disordered solvent molecules were entirely unsuccessful. The contribution of these solvent `voids' was therefore `subtracted' from the measured data using the SQUEEZE routine of PLATON (van der Sluis & Spek, 1990). This program indicated an approximate total of 23 electrons in the two sites which, assuming both voids contain disordered hexane molecules, corresponds to approximately 0.11C6H14. However, an accurate determination of the stoichiometric quantity of solvent in the crystal is not possible, so no contribution from the solvent has been included in the calculations of molecular formula, F(000) value, and calculated density. Methyl-associated hydrogen atoms were constrained to calculated positions with isotropic displacement parameters equal to 1.5 × Ueq of the parent carbon atom. Cluster-associated hydrogen atoms were either located via Fourier difference syntheses (open face) or positioned in calculated positions (five-connected vertices) and assigned isotropic displacement parameters equal to 1.2 × Ueq of the parent boron atom. Although parameters associated with these atoms were used in structure factor calculations they were not included in refinement.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: PLATON (Spek, 2000) and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: WC (Thornton-Pett, 2000).
[Rh2(B7H7S)(C10H15)2(CH3O)Cl] | Dx = 1.563 Mg m−3 |
Mr = 657.53 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4 | Cell parameters from 37770 reflections |
Hall symbol: P -4 | θ = 1.0–27.5° |
a = 18.1926 (2) Å | µ = 1.37 mm−1 |
c = 8.4442 (1) Å | T = 150 K |
V = 2794.78 (5) Å3 | Prism, dark red |
Z = 4 | 0.60 × 0.19 × 0.15 mm |
F(000) = 1328 |
Nonius KappaCCD area detector diffractometer | 5488 independent reflections |
Radiation source: fine-focus sealed tube | 5465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
Standard procedure using manufacturer proprietary software (Nonius, 1999) scans | h = −22→22 |
Absorption correction: multi-scan (Blessing, 1995) | k = −22→22 |
Tmin = 0.495, Tmax = 0.822 | l = −9→10 |
50782 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0358P)2 + 4.4768P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.080 | (Δ/σ)max = 0.003 |
S = 1.14 | Δρmax = 0.40 e Å−3 |
5488 reflections | Δρmin = −0.60 e Å−3 |
310 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0086 (6) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.02 (4) |
[Rh2(B7H7S)(C10H15)2(CH3O)Cl] | Z = 4 |
Mr = 657.53 | Mo Kα radiation |
Tetragonal, P4 | µ = 1.37 mm−1 |
a = 18.1926 (2) Å | T = 150 K |
c = 8.4442 (1) Å | 0.60 × 0.19 × 0.15 mm |
V = 2794.78 (5) Å3 |
Nonius KappaCCD area detector diffractometer | 5488 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5465 reflections with I > 2σ(I) |
Tmin = 0.495, Tmax = 0.822 | Rint = 0.079 |
50782 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.080 | Δρmax = 0.40 e Å−3 |
S = 1.14 | Δρmin = −0.60 e Å−3 |
5488 reflections | Absolute structure: Flack (1983) |
310 parameters | Absolute structure parameter: −0.02 (4) |
0 restraints |
Experimental. The crystal was mounted under oil in random orientation. Data were collected using a mixture of area-detector ω and ϕ-exposures with the CCD detector positioned 29 mm from the sample. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 15° ϕ range. |
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 | ||
Rh6 | 0.988741 (18) | 0.308783 (19) | 0.33706 (4) | 0.02450 (11) | |
C61 | 1.1008 (2) | 0.3155 (3) | 0.2876 (6) | 0.0337 (10) | |
C62 | 1.0809 (2) | 0.3755 (3) | 0.3830 (6) | 0.0328 (10) | |
C63 | 1.0564 (3) | 0.3474 (3) | 0.5338 (6) | 0.0328 (10) | |
C64 | 1.0601 (3) | 0.2717 (3) | 0.5297 (6) | 0.0354 (11) | |
C65 | 1.0879 (3) | 0.2505 (3) | 0.3777 (6) | 0.0349 (11) | |
C66 | 1.1352 (3) | 0.3185 (4) | 0.1283 (6) | 0.0440 (13) | |
H66A | 1.1173 | 0.3619 | 0.0714 | 0.066* | |
H66B | 1.1223 | 0.2741 | 0.0688 | 0.066* | |
H66C | 1.1888 | 0.3214 | 0.1395 | 0.066* | |
C67 | 1.0909 (3) | 0.4497 (3) | 0.3438 (8) | 0.0465 (13) | |
H67A | 1.1429 | 0.4627 | 0.3558 | 0.070* | |
H67B | 1.0612 | 0.4804 | 0.4144 | 0.070* | |
H67C | 1.0757 | 0.4579 | 0.2339 | 0.070* | |
C68 | 1.0333 (3) | 0.3908 (3) | 0.6716 (7) | 0.0454 (13) | |
H68A | 0.9954 | 0.3638 | 0.7303 | 0.068* | |
H68B | 1.0133 | 0.4380 | 0.6359 | 0.068* | |
H68C | 1.0757 | 0.3995 | 0.7407 | 0.068* | |
C69 | 1.0384 (3) | 0.2214 (3) | 0.6603 (7) | 0.0451 (13) | |
H69A | 1.0812 | 0.2114 | 0.7275 | 0.068* | |
H69B | 1.0201 | 0.1752 | 0.6157 | 0.068* | |
H69C | 0.9997 | 0.2445 | 0.7239 | 0.068* | |
C70 | 1.1035 (3) | 0.1778 (3) | 0.3257 (8) | 0.0482 (13) | |
H70A | 1.1004 | 0.1756 | 0.2100 | 0.072* | |
H70B | 1.0678 | 0.1437 | 0.3720 | 0.072* | |
H70C | 1.1532 | 0.1639 | 0.3595 | 0.072* | |
Rh9 | 0.785635 (17) | 0.344798 (18) | 0.28884 (4) | 0.02386 (11) | |
C91 | 0.7176 (3) | 0.4090 (3) | 0.4566 (7) | 0.0363 (11) | |
C92 | 0.6971 (3) | 0.3361 (3) | 0.4660 (6) | 0.0359 (11) | |
C93 | 0.6731 (3) | 0.3157 (3) | 0.3151 (7) | 0.0413 (12) | |
C94 | 0.6806 (3) | 0.3760 (3) | 0.2111 (7) | 0.0427 (12) | |
C95 | 0.7052 (3) | 0.4348 (3) | 0.3021 (8) | 0.0435 (13) | |
C96 | 0.7443 (3) | 0.4500 (4) | 0.5952 (10) | 0.068 (2) | |
H96A | 0.7023 | 0.4675 | 0.6573 | 0.101* | |
H96B | 0.7736 | 0.4921 | 0.5598 | 0.101* | |
H96C | 0.7748 | 0.4178 | 0.6610 | 0.101* | |
C97 | 0.7013 (4) | 0.2899 (4) | 0.6122 (8) | 0.066 (2) | |
H97A | 0.6901 | 0.2387 | 0.5855 | 0.099* | |
H97B | 0.6655 | 0.3079 | 0.6900 | 0.099* | |
H97C | 0.7509 | 0.2930 | 0.6570 | 0.099* | |
C98 | 0.6414 (3) | 0.2468 (4) | 0.2653 (11) | 0.077 (3) | |
H98A | 0.6578 | 0.2075 | 0.3363 | 0.115* | |
H98B | 0.6571 | 0.2358 | 0.1569 | 0.115* | |
H98C | 0.5877 | 0.2504 | 0.2689 | 0.115* | |
C99 | 0.6553 (4) | 0.3819 (7) | 0.0430 (8) | 0.095 (4) | |
H99A | 0.6949 | 0.4025 | −0.0220 | 0.143* | |
H99B | 0.6122 | 0.4141 | 0.0376 | 0.143* | |
H99C | 0.6422 | 0.3330 | 0.0034 | 0.143* | |
C100 | 0.7135 (4) | 0.5096 (4) | 0.2467 (13) | 0.086 (3) | |
H10A | 0.7389 | 0.5095 | 0.1442 | 0.129* | |
H10B | 0.7424 | 0.5377 | 0.3236 | 0.129* | |
H10C | 0.6650 | 0.5322 | 0.2346 | 0.129* | |
B1 | 0.8735 (4) | 0.2217 (4) | 0.0659 (7) | 0.0405 (14) | |
H1 | 0.8666 | 0.1717 | −0.0101 | 0.049* | |
B2 | 0.9609 (3) | 0.2638 (4) | 0.0977 (7) | 0.0373 (12) | |
H2 | 1.0112 | 0.2402 | 0.0408 | 0.045* | |
B3 | 0.8963 (3) | 0.3048 (4) | −0.0186 (6) | 0.0379 (13) | |
H3 | 0.9042 | 0.3089 | −0.1498 | 0.045* | |
B4 | 0.8104 (3) | 0.2900 (4) | 0.0689 (7) | 0.0359 (13) | |
H4 | 0.7604 | 0.2836 | −0.0072 | 0.043* | |
S5 | 0.91537 (7) | 0.21050 (6) | 0.27978 (17) | 0.0352 (3) | |
B7 | 0.9507 (3) | 0.3580 (3) | 0.1056 (6) | 0.0298 (11) | |
H7 | 0.9839 | 0.3973 | 0.0588 | 0.036* | |
H78 | 0.9077 | 0.3872 | 0.1794 | 0.036* | |
B8 | 0.8529 (3) | 0.3768 (3) | 0.0843 (6) | 0.0279 (10) | |
B10 | 0.8186 (3) | 0.2385 (3) | 0.2407 (7) | 0.0368 (12) | |
H10 | 0.7743 | 0.1987 | 0.2705 | 0.044* | |
Cl69 | 0.88523 (6) | 0.35823 (6) | 0.46435 (13) | 0.0277 (2) | |
O81 | 0.82880 (19) | 0.4375 (2) | 0.0078 (4) | 0.0381 (8) | |
C81 | 0.8741 (3) | 0.4740 (3) | −0.0995 (7) | 0.0412 (12) | |
H81A | 0.9116 | 0.5018 | −0.0415 | 0.062* | |
H81B | 0.8445 | 0.5079 | −0.1634 | 0.062* | |
H81C | 0.8980 | 0.4381 | −0.1689 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh6 | 0.02247 (17) | 0.02950 (19) | 0.02152 (16) | 0.00049 (13) | 0.00129 (12) | −0.00361 (13) |
C61 | 0.025 (2) | 0.049 (3) | 0.027 (2) | −0.0015 (19) | −0.0004 (19) | −0.005 (2) |
C62 | 0.0153 (19) | 0.046 (3) | 0.038 (3) | 0.0017 (18) | −0.0023 (17) | −0.005 (2) |
C63 | 0.024 (2) | 0.049 (3) | 0.025 (2) | −0.002 (2) | −0.0031 (18) | −0.007 (2) |
C64 | 0.025 (2) | 0.055 (3) | 0.027 (2) | 0.007 (2) | 0.0005 (18) | 0.002 (2) |
C65 | 0.027 (2) | 0.049 (3) | 0.029 (2) | 0.011 (2) | −0.0020 (18) | −0.005 (2) |
C66 | 0.028 (2) | 0.072 (4) | 0.031 (3) | 0.004 (2) | 0.010 (2) | 0.004 (2) |
C67 | 0.037 (3) | 0.042 (3) | 0.060 (3) | −0.010 (2) | 0.002 (3) | −0.004 (3) |
C68 | 0.030 (2) | 0.069 (4) | 0.037 (3) | −0.005 (2) | 0.000 (2) | −0.024 (3) |
C69 | 0.037 (3) | 0.062 (3) | 0.036 (3) | 0.010 (2) | 0.002 (2) | 0.015 (3) |
C70 | 0.046 (3) | 0.045 (3) | 0.053 (3) | 0.020 (2) | 0.005 (3) | −0.004 (3) |
Rh9 | 0.02126 (17) | 0.02690 (18) | 0.02341 (16) | −0.00525 (12) | 0.00095 (12) | −0.00162 (13) |
C91 | 0.022 (2) | 0.038 (3) | 0.048 (3) | 0.0045 (19) | 0.005 (2) | −0.014 (2) |
C92 | 0.030 (2) | 0.042 (3) | 0.035 (2) | −0.001 (2) | 0.011 (2) | 0.000 (2) |
C93 | 0.023 (2) | 0.047 (3) | 0.054 (3) | −0.008 (2) | 0.005 (2) | −0.016 (3) |
C94 | 0.020 (2) | 0.074 (4) | 0.034 (3) | 0.001 (2) | 0.002 (2) | 0.000 (3) |
C95 | 0.026 (2) | 0.042 (3) | 0.062 (4) | 0.004 (2) | 0.010 (2) | 0.010 (3) |
C96 | 0.039 (3) | 0.080 (5) | 0.084 (5) | 0.000 (3) | −0.004 (3) | −0.053 (4) |
C97 | 0.066 (4) | 0.074 (5) | 0.058 (4) | 0.014 (4) | 0.033 (3) | 0.028 (3) |
C98 | 0.031 (3) | 0.075 (5) | 0.123 (7) | −0.025 (3) | 0.024 (4) | −0.053 (5) |
C99 | 0.036 (3) | 0.217 (12) | 0.033 (3) | 0.032 (5) | −0.008 (3) | −0.007 (5) |
C100 | 0.045 (3) | 0.052 (4) | 0.160 (9) | 0.021 (3) | 0.026 (5) | 0.050 (5) |
B1 | 0.040 (3) | 0.042 (3) | 0.039 (3) | −0.001 (3) | −0.003 (3) | −0.018 (3) |
B2 | 0.033 (3) | 0.054 (4) | 0.025 (2) | 0.000 (2) | −0.002 (2) | −0.011 (2) |
B3 | 0.029 (3) | 0.065 (4) | 0.020 (2) | 0.004 (3) | 0.002 (2) | −0.011 (2) |
B4 | 0.030 (3) | 0.048 (3) | 0.029 (3) | −0.005 (2) | −0.002 (2) | −0.019 (2) |
S5 | 0.0370 (6) | 0.0256 (5) | 0.0430 (6) | −0.0017 (4) | −0.0017 (5) | −0.0044 (5) |
B7 | 0.029 (2) | 0.040 (3) | 0.021 (2) | −0.002 (2) | 0.0028 (19) | 0.001 (2) |
B8 | 0.026 (2) | 0.035 (3) | 0.023 (2) | −0.001 (2) | 0.0005 (19) | 0.003 (2) |
B10 | 0.042 (3) | 0.030 (3) | 0.039 (3) | −0.006 (2) | −0.003 (2) | −0.008 (2) |
Cl69 | 0.0216 (5) | 0.0358 (6) | 0.0256 (5) | −0.0003 (4) | 0.0007 (4) | −0.0063 (4) |
O81 | 0.0296 (17) | 0.048 (2) | 0.0371 (19) | 0.0013 (15) | 0.0040 (14) | 0.0162 (16) |
C81 | 0.037 (3) | 0.053 (3) | 0.034 (2) | −0.010 (2) | −0.001 (2) | 0.014 (2) |
Rh6—C61 | 2.085 (4) | C93—C94 | 1.412 (8) |
Rh6—C62 | 2.105 (5) | C93—C98 | 1.441 (8) |
Rh6—C65 | 2.120 (5) | C94—C95 | 1.391 (9) |
Rh6—C63 | 2.184 (5) | C94—C99 | 1.495 (8) |
Rh6—C64 | 2.188 (5) | C95—C100 | 1.447 (8) |
Rh6—B2 | 2.238 (5) | C96—H96A | 0.9800 |
Rh6—B7 | 2.259 (5) | C96—H96B | 0.9800 |
Rh6—S5 | 2.2831 (12) | C96—H96C | 0.9800 |
Rh6—Cl69 | 2.3475 (11) | C97—H97A | 0.9800 |
C61—C62 | 1.405 (7) | C97—H97B | 0.9800 |
C61—C65 | 1.425 (8) | C97—H97C | 0.9800 |
C61—C66 | 1.485 (7) | C98—H98A | 0.9800 |
C62—C67 | 1.402 (7) | C98—H98B | 0.9800 |
C62—C63 | 1.443 (7) | C98—H98C | 0.9800 |
C63—C64 | 1.380 (7) | C99—H99A | 0.9800 |
C63—C68 | 1.467 (7) | C99—H99B | 0.9800 |
C64—C65 | 1.433 (7) | C99—H99C | 0.9800 |
C64—C69 | 1.486 (7) | C100—H10A | 0.9800 |
C65—C70 | 1.423 (7) | C100—H10B | 0.9800 |
C66—H66A | 0.9800 | C100—H10C | 0.9800 |
C66—H66B | 0.9800 | B1—B4 | 1.691 (9) |
C66—H66C | 0.9800 | B1—B3 | 1.723 (10) |
C67—H67A | 0.9800 | B1—B2 | 1.786 (9) |
C67—H67B | 0.9800 | B1—B10 | 1.808 (9) |
C67—H67C | 0.9800 | B1—S5 | 1.971 (6) |
C68—H68A | 0.9800 | B1—H1 | 1.12 |
C68—H68B | 0.9800 | B2—B3 | 1.702 (8) |
C68—H68C | 0.9800 | B2—B7 | 1.725 (8) |
C69—H69A | 0.9800 | B2—S5 | 1.998 (7) |
C69—H69B | 0.9800 | B2—H2 | 1.12 |
C69—H69C | 0.9800 | B3—B7 | 1.736 (8) |
C70—H70A | 0.9800 | B3—B4 | 1.750 (8) |
C70—H70B | 0.9800 | B3—B8 | 1.760 (8) |
C70—H70C | 0.9800 | B3—H3 | 1.12 |
Rh9—B10 | 2.066 (6) | B4—B10 | 1.733 (9) |
Rh9—C94 | 2.099 (5) | B4—B8 | 1.764 (8) |
Rh9—C93 | 2.126 (5) | B4—H4 | 1.12 |
Rh9—B4 | 2.156 (5) | S5—B10 | 1.863 (6) |
Rh9—B8 | 2.195 (5) | B7—B8 | 1.820 (7) |
Rh9—C95 | 2.199 (5) | B7—H7 | 1.02 |
Rh9—C92 | 2.203 (5) | B7—H78 | 1.13 |
Rh9—C91 | 2.214 (5) | B8—O81 | 1.351 (6) |
Rh9—Cl69 | 2.3536 (11) | B8—H78 | 1.29 |
C91—C92 | 1.379 (7) | B10—H10 | 1.11 |
C91—C95 | 1.405 (9) | O81—C81 | 1.394 (6) |
C91—C96 | 1.471 (8) | C81—H81A | 0.98 |
C92—C93 | 1.398 (8) | C81—H81B | 0.98 |
C92—C97 | 1.495 (8) | C81—H81C | 0.98 |
C61—Rh6—C62 | 39.16 (19) | C95—C94—Rh9 | 75.1 (3) |
C61—Rh6—C65 | 39.6 (2) | C93—C94—Rh9 | 71.5 (3) |
C62—Rh6—C65 | 65.2 (2) | C99—C94—Rh9 | 126.6 (4) |
C61—Rh6—C63 | 65.32 (18) | C94—C95—C91 | 108.0 (5) |
C62—Rh6—C63 | 39.25 (19) | C94—C95—C100 | 125.3 (7) |
C65—Rh6—C63 | 63.79 (19) | C91—C95—C100 | 126.7 (7) |
C61—Rh6—C64 | 65.60 (18) | C94—C95—Rh9 | 67.3 (3) |
C62—Rh6—C64 | 64.4 (2) | C91—C95—Rh9 | 72.0 (3) |
C65—Rh6—C64 | 38.82 (18) | C100—C95—Rh9 | 127.8 (4) |
C63—Rh6—C64 | 36.8 (2) | C91—C96—H96A | 109.5 |
C61—Rh6—B2 | 93.6 (2) | C91—C96—H96B | 109.5 |
C62—Rh6—B2 | 123.9 (2) | H96A—C96—H96B | 109.5 |
C65—Rh6—B2 | 99.0 (2) | C91—C96—H96C | 109.5 |
C63—Rh6—B2 | 158.8 (2) | H96A—C96—H96C | 109.5 |
C64—Rh6—B2 | 133.9 (2) | H96B—C96—H96C | 109.5 |
C61—Rh6—B7 | 95.93 (19) | C92—C97—H97A | 109.5 |
C62—Rh6—B7 | 100.1 (2) | C92—C97—H97B | 109.5 |
C65—Rh6—B7 | 126.82 (19) | H97A—C97—H97B | 109.5 |
C63—Rh6—B7 | 134.7 (2) | C92—C97—H97C | 109.5 |
C64—Rh6—B7 | 161.39 (19) | H97A—C97—H97C | 109.5 |
B2—Rh6—B7 | 45.1 (2) | H97B—C97—H97C | 109.5 |
C61—Rh6—S5 | 125.12 (15) | C93—C98—H98A | 109.5 |
C62—Rh6—S5 | 162.93 (14) | C93—C98—H98B | 109.5 |
C65—Rh6—S5 | 98.06 (15) | H98A—C98—H98B | 109.5 |
C63—Rh6—S5 | 137.97 (15) | C93—C98—H98C | 109.5 |
C64—Rh6—S5 | 105.25 (15) | H98A—C98—H98C | 109.5 |
B2—Rh6—S5 | 52.43 (17) | H98B—C98—H98C | 109.5 |
B7—Rh6—S5 | 87.02 (15) | C94—C99—H99A | 109.5 |
C61—Rh6—Cl69 | 148.62 (14) | C94—C99—H99B | 109.5 |
C62—Rh6—Cl69 | 109.46 (14) | H99A—C99—H99B | 109.5 |
C65—Rh6—Cl69 | 143.13 (13) | C94—C99—H99C | 109.5 |
C63—Rh6—Cl69 | 88.87 (13) | H99A—C99—H99C | 109.5 |
C64—Rh6—Cl69 | 104.68 (13) | H99B—C99—H99C | 109.5 |
B2—Rh6—Cl69 | 111.83 (15) | C95—C100—H10A | 109.5 |
B7—Rh6—Cl69 | 89.89 (14) | C95—C100—H10B | 109.5 |
S5—Rh6—Cl69 | 85.88 (4) | H10A—C100—H10B | 109.5 |
C62—C61—C65 | 107.2 (4) | C95—C100—H10C | 109.5 |
C62—C61—C66 | 126.9 (5) | H10A—C100—H10C | 109.5 |
C65—C61—C66 | 125.7 (5) | H10B—C100—H10C | 109.5 |
C62—C61—Rh6 | 71.2 (3) | B4—B1—B3 | 61.7 (4) |
C65—C61—Rh6 | 71.5 (3) | B4—B1—B2 | 106.6 (4) |
C66—C61—Rh6 | 126.6 (3) | B3—B1—B2 | 58.0 (3) |
C67—C62—C61 | 125.4 (5) | B4—B1—B10 | 59.3 (3) |
C67—C62—C63 | 126.1 (5) | B3—B1—B10 | 108.8 (4) |
C61—C62—C63 | 108.1 (5) | B2—B1—B10 | 107.2 (4) |
C67—C62—Rh6 | 128.0 (4) | B4—B1—S5 | 108.9 (4) |
C61—C62—Rh6 | 69.6 (3) | B3—B1—S5 | 112.1 (4) |
C63—C62—Rh6 | 73.3 (3) | B2—B1—S5 | 64.0 (3) |
C64—C63—C62 | 108.4 (4) | B10—B1—S5 | 58.9 (3) |
C64—C63—C68 | 124.8 (5) | B4—B1—H1 | 122 |
C62—C63—C68 | 126.8 (5) | B3—B1—H1 | 120 |
C64—C63—Rh6 | 71.7 (3) | B2—B1—H1 | 122 |
C62—C63—Rh6 | 67.4 (3) | B10—B1—H1 | 123 |
C68—C63—Rh6 | 127.9 (3) | S5—B1—H1 | 119 |
C63—C64—C65 | 108.0 (5) | B3—B2—B7 | 60.9 (4) |
C63—C64—C69 | 125.7 (5) | B3—B2—B1 | 59.1 (4) |
C65—C64—C69 | 126.4 (5) | B7—B2—B1 | 109.7 (4) |
C63—C64—Rh6 | 71.5 (3) | B3—B2—S5 | 111.8 (4) |
C65—C64—Rh6 | 68.0 (3) | B7—B2—S5 | 114.1 (3) |
C69—C64—Rh6 | 125.8 (4) | B1—B2—S5 | 62.5 (3) |
C70—C65—C61 | 125.0 (5) | B3—B2—Rh6 | 121.1 (4) |
C70—C65—C64 | 126.6 (5) | B7—B2—Rh6 | 68.1 (3) |
C61—C65—C64 | 108.3 (5) | B1—B2—Rh6 | 119.6 (4) |
C70—C65—Rh6 | 125.8 (4) | S5—B2—Rh6 | 64.94 (17) |
C61—C65—Rh6 | 68.9 (3) | B3—B2—H2 | 119 |
C64—C65—Rh6 | 73.1 (3) | B7—B2—H2 | 119 |
C61—C66—H66A | 109.5 | B1—B2—H2 | 120 |
C61—C66—H66B | 109.5 | S5—B2—H2 | 119 |
H66A—C66—H66B | 109.5 | Rh6—B2—H2 | 110 |
C61—C66—H66C | 109.5 | B2—B3—B1 | 62.9 (4) |
H66A—C66—H66C | 109.5 | B2—B3—B7 | 60.2 (3) |
H66B—C66—H66C | 109.5 | B1—B3—B7 | 112.2 (4) |
C62—C67—H67A | 109.5 | B2—B3—B4 | 107.8 (4) |
C62—C67—H67B | 109.5 | B1—B3—B4 | 58.3 (4) |
H67A—C67—H67B | 109.5 | B7—B3—B4 | 109.8 (4) |
C62—C67—H67C | 109.5 | B2—B3—B8 | 110.6 (4) |
H67A—C67—H67C | 109.5 | B1—B3—B8 | 109.9 (4) |
H67B—C67—H67C | 109.5 | B7—B3—B8 | 62.8 (3) |
C63—C68—H68A | 109.5 | B4—B3—B8 | 60.3 (3) |
C63—C68—H68B | 109.5 | B2—B3—H3 | 121 |
H68A—C68—H68B | 109.5 | B1—B3—H3 | 120 |
C63—C68—H68C | 109.5 | B7—B3—H3 | 119 |
H68A—C68—H68C | 109.5 | B4—B3—H3 | 123 |
H68B—C68—H68C | 109.5 | B8—B3—H3 | 120 |
C64—C69—H69A | 109.5 | B1—B4—B10 | 63.7 (4) |
C64—C69—H69B | 109.5 | B1—B4—B3 | 60.1 (4) |
H69A—C69—H69B | 109.5 | B10—B4—B3 | 111.1 (4) |
C64—C69—H69C | 109.5 | B1—B4—B8 | 111.2 (4) |
H69A—C69—H69C | 109.5 | B10—B4—B8 | 112.7 (4) |
H69B—C69—H69C | 109.5 | B3—B4—B8 | 60.1 (3) |
C65—C70—H70A | 109.5 | B1—B4—Rh9 | 119.7 (4) |
C65—C70—H70B | 109.5 | B10—B4—Rh9 | 63.1 (3) |
H70A—C70—H70B | 109.5 | B3—B4—Rh9 | 118.6 (3) |
C65—C70—H70C | 109.5 | B8—B4—Rh9 | 67.3 (3) |
H70A—C70—H70C | 109.5 | B1—B4—H4 | 118 |
H70B—C70—H70C | 109.5 | B10—B4—H4 | 120 |
B10—Rh9—C94 | 117.1 (2) | B3—B4—H4 | 120 |
B10—Rh9—C93 | 93.8 (2) | B8—B4—H4 | 119 |
C94—Rh9—C93 | 39.0 (2) | Rh9—B4—H4 | 112 |
B10—Rh9—B4 | 48.4 (2) | B10—S5—B1 | 56.2 (3) |
C94—Rh9—B4 | 92.6 (2) | B10—S5—B2 | 97.1 (3) |
C93—Rh9—B4 | 100.1 (2) | B1—S5—B2 | 53.5 (3) |
B10—Rh9—B8 | 86.1 (2) | B10—S5—Rh6 | 112.12 (18) |
C94—Rh9—B8 | 100.9 (2) | B1—S5—Rh6 | 109.8 (2) |
C93—Rh9—B8 | 133.2 (2) | B2—S5—Rh6 | 62.63 (17) |
B4—Rh9—B8 | 47.8 (2) | B2—B7—B3 | 58.9 (3) |
B10—Rh9—C95 | 154.2 (2) | B2—B7—B8 | 106.8 (4) |
C94—Rh9—C95 | 37.7 (2) | B3—B7—B8 | 59.3 (3) |
C93—Rh9—C95 | 62.6 (2) | B2—B7—Rh6 | 66.8 (3) |
B4—Rh9—C95 | 121.8 (2) | B3—B7—Rh6 | 118.4 (4) |
B8—Rh9—C95 | 102.3 (2) | B8—B7—Rh6 | 117.4 (3) |
B10—Rh9—C92 | 106.2 (2) | B2—B7—H7 | 128 |
C94—Rh9—C92 | 64.3 (2) | B3—B7—H7 | 120 |
C93—Rh9—C92 | 37.6 (2) | B8—B7—H7 | 114 |
B4—Rh9—C92 | 134.8 (2) | Rh6—B7—H7 | 116 |
B8—Rh9—C92 | 163.8 (2) | B2—B7—H78 | 124 |
C95—Rh9—C92 | 62.1 (2) | B3—B7—H78 | 102 |
B10—Rh9—C91 | 141.4 (2) | B8—B7—H78 | 45 |
C94—Rh9—C91 | 63.2 (2) | Rh6—B7—H78 | 86 |
C93—Rh9—C91 | 61.75 (19) | H7—B7—H78 | 107 |
B4—Rh9—C91 | 155.8 (2) | O81—B8—B3 | 121.2 (4) |
B8—Rh9—C91 | 132.5 (2) | O81—B8—B4 | 123.6 (4) |
C95—Rh9—C91 | 37.1 (2) | B3—B8—B4 | 59.6 (3) |
C92—Rh9—C91 | 36.4 (2) | O81—B8—B7 | 121.2 (4) |
B10—Rh9—Cl69 | 89.88 (17) | B3—B8—B7 | 58.0 (3) |
C94—Rh9—Cl69 | 150.44 (17) | B4—B8—B7 | 105.5 (4) |
C93—Rh9—Cl69 | 134.55 (17) | O81—B8—Rh9 | 114.3 (3) |
B4—Rh9—Cl69 | 115.44 (15) | B3—B8—Rh9 | 116.2 (3) |
B8—Rh9—Cl69 | 92.22 (14) | B4—B8—Rh9 | 64.9 (3) |
C95—Rh9—Cl69 | 113.78 (17) | B7—B8—Rh9 | 114.6 (3) |
C92—Rh9—Cl69 | 98.19 (14) | O81—B8—H78 | 115 |
C91—Rh9—Cl69 | 88.43 (14) | B3—B8—H78 | 93 |
C92—C91—C95 | 109.3 (5) | B4—B8—H78 | 121 |
C92—C91—C96 | 122.1 (6) | B7—B8—H78 | 38 |
C95—C91—C96 | 128.5 (6) | Rh9—B8—H78 | 89 |
C92—C91—Rh9 | 71.4 (3) | B4—B10—B1 | 57.0 (3) |
C95—C91—Rh9 | 70.9 (3) | B4—B10—S5 | 112.1 (4) |
C96—C91—Rh9 | 126.3 (4) | B1—B10—S5 | 64.9 (3) |
C91—C92—C93 | 106.7 (5) | B4—B10—Rh9 | 68.5 (3) |
C91—C92—C97 | 125.0 (6) | B1—B10—Rh9 | 118.6 (4) |
C93—C92—C97 | 128.3 (6) | S5—B10—Rh9 | 119.7 (3) |
C91—C92—Rh9 | 72.2 (3) | B4—B10—H10 | 119 |
C93—C92—Rh9 | 68.2 (3) | B1—B10—H10 | 118 |
C97—C92—Rh9 | 124.4 (4) | S5—B10—H10 | 118 |
C92—C93—C94 | 109.3 (5) | Rh9—B10—H10 | 111 |
C92—C93—C98 | 128.5 (6) | Rh6—Cl69—Rh9 | 106.82 (4) |
C94—C93—C98 | 122.2 (6) | B8—O81—C81 | 120.6 (4) |
C92—C93—Rh9 | 74.2 (3) | O81—C81—H81A | 109.5 |
C94—C93—Rh9 | 69.4 (3) | O81—C81—H81B | 109.5 |
C98—C93—Rh9 | 124.9 (4) | H81A—C81—H81B | 109.5 |
C95—C94—C93 | 106.5 (5) | O81—C81—H81C | 109.5 |
C95—C94—C99 | 124.6 (7) | H81A—C81—H81C | 109.5 |
C93—C94—C99 | 128.0 (7) | H81B—C81—H81C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [Rh2(B7H7S)(C10H15)2(CH3O)Cl] |
Mr | 657.53 |
Crystal system, space group | Tetragonal, P4 |
Temperature (K) | 150 |
a, c (Å) | 18.1926 (2), 8.4442 (1) |
V (Å3) | 2794.78 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.60 × 0.19 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD area detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.495, 0.822 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50782, 5488, 5465 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.080, 1.14 |
No. of reflections | 5488 |
No. of parameters | 310 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.60 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.02 (4) |
Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1996), DENZO-SMN, SHELXS97 (Sheldrick, 1990), PLATON (Spek, 2000) and SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), WC (Thornton-Pett, 2000).
Rh6—B2 | 2.238 (5) | B1—S5 | 1.971 (6) |
Rh6—B7 | 2.259 (5) | B2—B3 | 1.702 (8) |
Rh6—S5 | 2.2831 (12) | B2—B7 | 1.725 (8) |
Rh6—Cl69 | 2.3475 (11) | B2—S5 | 1.998 (7) |
Rh9—B10 | 2.066 (6) | B3—B7 | 1.736 (8) |
Rh9—B4 | 2.156 (5) | B3—B4 | 1.750 (8) |
Rh9—B8 | 2.195 (5) | B3—B8 | 1.760 (8) |
Rh9—Cl69 | 2.3536 (11) | B4—B10 | 1.733 (9) |
B1—B4 | 1.691 (9) | B4—B8 | 1.764 (8) |
B1—B3 | 1.723 (10) | S5—B10 | 1.863 (6) |
B1—B2 | 1.786 (9) | B7—B8 | 1.820 (7) |
B1—B10 | 1.808 (9) | B8—O81 | 1.351 (6) |
Rh6—Cl69—Rh9 | 106.82 (4) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Since the initial structure elucidation of the arachno and nido ten-vertex skeletons in borane cluster chemistry diagrammatically depicted in (I) (Van der Mass Reddy & Lipscomb, 1959; Kasper et al., 1950), there has been a fascination with bridging the 6,9 positions across the open face, either with a single atom as in (II) or a two-atom unit as in (III), but instances of both have been surprisingly rare. Several examples of structurally characterized one-atom bridges of the arachno skeleton have been reported. These include a phosphorus-bridged unit as in the [B10H12-µ-6,9-(PPh2)]- anion (Thornton-Pett et al., 1986), a sulfur-bridged unit as in the [B10H12-µ-6,9-(SMe)]- anion and related species (Binder & Hein, 1997, and references therein). Bridged nido skeletons have been structurally characterized containing an aluminium-bridged unit, [6,9-C2B8H12-µ-6,9-{Al(OEt)Me}] (Schubert et al., 1987), a tin bridge in [6,9-C2B8H12-µ-6,9-SnMe2] and related species (Kennedy et al., 1992; Nestor et al., 1993), as well as a nitrogen-bridged cluster in [5,10-C2B8H12-µ-6,9-(NHterBu)] and related species (Janoušek et al., 1992; Dörfler et al., 2000). In this paper we now report a chlorine bridge for the arachno-6,9,5-dimetallathiadecaborane cluster compound [µ-6,9-Cl-8-(OMe)-6,9-(η5-C5Me5)2-arachno-6,9,5-Rh2SB7H7], (IV) (Figure 1). A chlorine-bridged rhodium pair has been noted previously in the eleven-vertex dimetallathiaborane [2,3-(PPh3)2-3-Cl-µ-2,3-Cl-µ-2P,7C-(Ph2P-2-C6H4) -closo-2,3,1-Rh2SB9H8] (Ferguson et al., 1990), although the bridged rhodium atoms are adjacent in the contiguous {RhS2B9} cluster [Rh—Rh distance 2.6307 (9) Å], rather than apart, as in the present compound [Rh—Rh distance 3.7748 (5) Å]. There is a bromine-bridged metals-apart example reported, in [µ-Br(CO)6(B3H8)Mn2] (Chen et al., 1980). \sch
The asymmetric unit contains approximately 0.1 molecules of disordered CH2Cl2 solvent. The cluster structure is seen to be of the basic ten-vertex nido/arachno boat-shaped geometry, with a rhodium centre at each of the two 6,9 `prow' positions. The two Rh atoms are linked by a bridging Cl atom. An S atom occupies one of the open-face `gunwale' positions, and there is a hydrogen bridge at the opposing interboron `gunwale' position, consistent with the general arachno ten-vertex character that is also apparent from the formal Wadian (Wade, 1976) 16-electron {2n+6} arachno electron count. The compound could also be regarded as of 11-vertex `remote arachno' cluster constitution (Porterfield et al., 1990). Using simple electron counting rules, each of the formal octahedral rhodium(III) centres has two two-electron bonding vectors which are contributed to the cluster (Kennedy, 1998; Bould et al., 1999) and three which are directed towards the {η5-C5Me5} group. The sixth vector constitutes a two-electron bond with the bridging Cl atom, and one such from each rhodium generates the bridge. The two rhodium-chlorine distances of 2.3475 (11) and 2.3536 (11) Å are similar to those in the closo twelve-vertex species mentioned above [2.437 (2) and 2.448 (2) Å], and shorter than those in the doubly bridged rhodium dimer [{RhCl2(η5-C5Me5)}2] from which compound (IV) was prepared [2.401 (4) Å] (Hoard & Sharpe, 1993).