Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014328/bm1352sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014328/bm1352Isup2.hkl |
CCDC reference: 140936
To a suspension of 1-(Ph2P)-2-(CH3)-7,8-nido-C2B10H10 (0.034 g, 0.1 mmol; Kivekäs et al., 1994) in ethanol (30 ml), [Au(PPh3)(SC4H8)]ClO4 (0.096 g, 0.15 mmol) was added. The mixture was refluxed for 30 min and the complex (a white solid) filtered off and washed with ethanol (10 ml) (yield: 72%). Analysis calculated for C33H38AuB9P2: C 50.05, H 4.08%; found: C 49.65, H 4.6%. NMR data: 31P{1H} (AB system) 17.21 p.p.m., J = 327.5 Hz; 1H −2.25 (m, vr, 1H), 1.41 (s, 3H, CH3), 6.7–7.8 (m, br, 15H, C6H5) p.p.m. Single crystals were obtained from an n-heptane–dichloromethane solution.
The dichloromethane solvate molecule is disordered over an inversion centre; C—Cl bond lengths were restrained to be equal. The high displacement parameters of this molecule may indicate partial occupation. All non-H atoms, except solvent C atoms, were refined anisotropically. H atoms of the carbaborane open face were located in difference syntheses and refined freely, but with B—H distances restrained to be equal. The methyl H atoms were identified from difference syntheses, idealized and refined as a rigid group allowed to rotate but not tip. Other H were included using a riding model. A total of 433 restraints were applied, involving local phenyl-ring symmetry and light-atom displacement parameters, in addition to the B—H restraints. The largest feature of residual electron density (1.07 e Å−3) is 0.79 Å from the Au atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
[Au(C15H23B9P)(C18H15P)]·0.5CH2Cl2 | Z = 2 |
Mr = 833.29 | F(000) = 822 |
Triclinic, P1 | Dx = 1.481 Mg m−3 |
a = 11.3770 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.518 (1) Å | Cell parameters from 8011 reflections |
c = 15.4837 (12) Å | θ = 2–28° |
α = 69.925 (3)° | µ = 4.12 mm−1 |
β = 72.338 (3)° | T = 143 K |
γ = 66.953 (3)° | Irregular wedge, colourless |
V = 1869.1 (2) Å3 | 0.29 × 0.22 × 0.16 mm |
Bruker SMART 1000 CCD diffractometer | 10779 independent reflections |
Radiation source: fine-focus sealed tube | 9788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 8.192 pixels mm-1 | θmax = 30°, θmin = 1.4° |
ω scans | h = −15→16 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −17→17 |
Tmin = 0.400, Tmax = 0.518 | l = −21→21 |
22230 measured reflections |
Refinement on F2 | Primary atom site location: Patterson |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0291P)2] where P = (Fo2 + 2Fc2)/3 |
10779 reflections | (Δ/σ)max = 0.027 |
445 parameters | Δρmax = 1.07 e Å−3 |
443 restraints | Δρmin = −0.81 e Å−3 |
[Au(C15H23B9P)(C18H15P)]·0.5CH2Cl2 | γ = 66.953 (3)° |
Mr = 833.29 | V = 1869.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.3770 (8) Å | Mo Kα radiation |
b = 12.518 (1) Å | µ = 4.12 mm−1 |
c = 15.4837 (12) Å | T = 143 K |
α = 69.925 (3)° | 0.29 × 0.22 × 0.16 mm |
β = 72.338 (3)° |
Bruker SMART 1000 CCD diffractometer | 10779 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 9788 reflections with I > 2σ(I) |
Tmin = 0.400, Tmax = 0.518 | Rint = 0.017 |
22230 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 443 restraints |
wR(F2) = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 1.07 e Å−3 |
10779 reflections | Δρmin = −0.81 e Å−3 |
445 parameters |
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. Distance B—H 1.0557 (0.0152) B1 - H01 1.0700 (0.0152) B2 - H02A 1.0702 (0.0164) B2 - H02B 1.0736 (0.0148) B3 - H03 1.4497 (0.0271) B1 - H02B Angle HBH 110.20 (1.84) H02A - B2 - H02B Angle BHB 93.74 (1.67) B2 - H02B - B1 |
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. The dichloromethane solvate molecule is disordered over an inversion centre; C—Cl bond lengths were restrained to be equal. The high displacement parameters of this molecule may indicate partial occupation. All non-H atoms, except solvent C atoms, were refined anisotropically. H atoms of the carbaborane open face were located in difference syntheses and refined freely, but with B—H distances restrained to be equal. The methyl H atoms were identified from difference syntheses, idealized and refined as a rigid group allowed to rotate but not tip. Other H were included using a riding model. A total of 433 restraints were applied, involving local phenyl-ring symmetry (FLAT/SAME in SHELXL97; Sheldrick, 1997) and light-atom displacement parameters (DELU $C $B) in addition to the B—H restraints. The largest feature of residual electron density (1.07 e Å−3) is 0.79 Å from the Au atom. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Au | 0.294569 (7) | 0.514577 (6) | 0.275580 (5) | 0.02054 (2) | |
P1 | 0.15542 (4) | 0.70599 (4) | 0.28257 (3) | 0.01615 (8) | |
P2 | 0.43217 (5) | 0.32997 (4) | 0.25232 (3) | 0.02091 (9) | |
C1 | 0.01721 (16) | 0.75754 (15) | 0.22595 (11) | 0.0159 (3) | |
C2 | 0.04506 (17) | 0.74417 (16) | 0.12267 (12) | 0.0183 (3) | |
C3 | 0.18218 (18) | 0.69612 (19) | 0.07072 (13) | 0.0256 (4) | |
H3A | 0.2302 | 0.7509 | 0.0605 | 0.031* | |
H3B | 0.1795 | 0.6896 | 0.0101 | 0.031* | |
H3C | 0.2259 | 0.6167 | 0.1078 | 0.031* | |
C11 | 0.24231 (17) | 0.81368 (16) | 0.22694 (12) | 0.0186 (3) | |
C12 | 0.19030 (19) | 0.92600 (17) | 0.16855 (13) | 0.0241 (4) | |
H12 | 0.1059 | 0.9486 | 0.1560 | 0.029* | |
C13 | 0.2624 (2) | 1.0051 (2) | 0.12859 (15) | 0.0315 (4) | |
H13 | 0.2268 | 1.0818 | 0.0890 | 0.038* | |
C14 | 0.3857 (2) | 0.9723 (2) | 0.14645 (15) | 0.0328 (5) | |
H14 | 0.4349 | 1.0261 | 0.1187 | 0.039* | |
C15 | 0.4373 (2) | 0.8614 (2) | 0.20451 (15) | 0.0315 (4) | |
H15 | 0.5215 | 0.8396 | 0.2172 | 0.038* | |
C16 | 0.36690 (18) | 0.78184 (18) | 0.24439 (13) | 0.0246 (4) | |
H16 | 0.4033 | 0.7053 | 0.2838 | 0.030* | |
C21 | 0.09478 (18) | 0.71731 (16) | 0.40300 (12) | 0.0206 (3) | |
C22 | 0.0685 (2) | 0.82219 (19) | 0.42780 (14) | 0.0344 (5) | |
H22 | 0.0809 | 0.8916 | 0.3809 | 0.041* | |
C23 | 0.0243 (3) | 0.8256 (2) | 0.52109 (16) | 0.0495 (7) | |
H23 | 0.0063 | 0.8976 | 0.5377 | 0.059* | |
C24 | 0.0065 (3) | 0.7254 (2) | 0.58978 (16) | 0.0501 (7) | |
H24 | −0.0241 | 0.7285 | 0.6535 | 0.060* | |
C25 | 0.0331 (3) | 0.6207 (2) | 0.56590 (15) | 0.0456 (6) | |
H25 | 0.0206 | 0.5516 | 0.6132 | 0.055* | |
C26 | 0.0782 (2) | 0.61597 (18) | 0.47297 (14) | 0.0314 (4) | |
H26 | 0.0978 | 0.5432 | 0.4570 | 0.038* | |
C31 | 0.60289 (18) | 0.31324 (16) | 0.23430 (13) | 0.0224 (3) | |
C32 | 0.6408 (2) | 0.41605 (19) | 0.19330 (17) | 0.0358 (5) | |
H32 | 0.5771 | 0.4926 | 0.1785 | 0.043* | |
C33 | 0.7712 (2) | 0.4063 (2) | 0.17417 (18) | 0.0395 (5) | |
H33 | 0.7965 | 0.4765 | 0.1464 | 0.047* | |
C34 | 0.8645 (2) | 0.2957 (2) | 0.19520 (17) | 0.0356 (5) | |
H34 | 0.9537 | 0.2898 | 0.1819 | 0.043* | |
C35 | 0.8283 (2) | 0.19323 (19) | 0.23569 (17) | 0.0359 (5) | |
H35 | 0.8927 | 0.1170 | 0.2500 | 0.043* | |
C36 | 0.6976 (2) | 0.20148 (18) | 0.25549 (15) | 0.0298 (4) | |
H36 | 0.6730 | 0.1310 | 0.2834 | 0.036* | |
C41 | 0.39740 (18) | 0.20412 (17) | 0.34414 (13) | 0.0232 (4) | |
C42 | 0.4148 (2) | 0.09751 (18) | 0.32435 (14) | 0.0330 (5) | |
H42 | 0.4485 | 0.0892 | 0.2620 | 0.040* | |
C43 | 0.3829 (3) | 0.0035 (2) | 0.39556 (16) | 0.0399 (5) | |
H43 | 0.3951 | −0.0690 | 0.3820 | 0.048* | |
C44 | 0.3337 (2) | 0.0158 (2) | 0.48583 (16) | 0.0386 (5) | |
H44 | 0.3114 | −0.0483 | 0.5344 | 0.046* | |
C45 | 0.3163 (2) | 0.1208 (2) | 0.50647 (15) | 0.0409 (5) | |
H45 | 0.2832 | 0.1283 | 0.5690 | 0.049* | |
C46 | 0.3475 (2) | 0.2153 (2) | 0.43536 (14) | 0.0325 (4) | |
H46 | 0.3345 | 0.2878 | 0.4493 | 0.039* | |
C51 | 0.40975 (18) | 0.31485 (16) | 0.14640 (12) | 0.0209 (3) | |
C52 | 0.5137 (2) | 0.27239 (19) | 0.07808 (14) | 0.0286 (4) | |
H52 | 0.6006 | 0.2503 | 0.0856 | 0.034* | |
C53 | 0.4899 (2) | 0.2623 (2) | −0.00136 (15) | 0.0344 (5) | |
H53 | 0.5609 | 0.2321 | −0.0475 | 0.041* | |
C54 | 0.3642 (2) | 0.29575 (19) | −0.01359 (14) | 0.0302 (4) | |
H54 | 0.3489 | 0.2900 | −0.0686 | 0.036* | |
C55 | 0.2601 (2) | 0.3379 (2) | 0.05440 (16) | 0.0346 (5) | |
H55 | 0.1734 | 0.3604 | 0.0462 | 0.041* | |
C56 | 0.2827 (2) | 0.3469 (2) | 0.13438 (15) | 0.0317 (4) | |
H56 | 0.2113 | 0.3752 | 0.1811 | 0.038* | |
B1 | −0.0574 (2) | 0.85634 (19) | 0.06323 (14) | 0.0218 (4) | |
H01 | −0.030 (2) | 0.8906 (19) | −0.0097 (11) | 0.027 (6)* | |
B2 | −0.1739 (2) | 0.94821 (19) | 0.14447 (15) | 0.0232 (4) | |
H02A | −0.234 (2) | 1.0398 (14) | 0.1249 (15) | 0.028 (6)* | |
H02B | −0.0736 (17) | 0.940 (2) | 0.1147 (18) | 0.050 (8)* | |
B3 | −0.10664 (19) | 0.87126 (18) | 0.25025 (14) | 0.0194 (4) | |
H03 | −0.112 (2) | 0.9149 (18) | 0.3008 (13) | 0.021 (5)* | |
B4 | −0.0200 (2) | 0.64254 (18) | 0.21094 (13) | 0.0187 (4) | |
H4 | 0.0318 | 0.5437 | 0.2329 | 0.022* | |
B5 | −0.12371 (19) | 0.72534 (18) | 0.29432 (14) | 0.0191 (4) | |
H5 | −0.1416 | 0.6798 | 0.3710 | 0.023* | |
B6 | −0.2419 (2) | 0.84704 (19) | 0.23901 (15) | 0.0224 (4) | |
H6 | −0.3412 | 0.8831 | 0.2806 | 0.027* | |
B7 | −0.2141 (2) | 0.8395 (2) | 0.11944 (15) | 0.0234 (4) | |
H7 | −0.2936 | 0.8710 | 0.0793 | 0.028* | |
B8 | −0.0780 (2) | 0.71029 (19) | 0.10608 (14) | 0.0220 (4) | |
H8 | −0.0679 | 0.6557 | 0.0586 | 0.026* | |
B9 | −0.1897 (2) | 0.70441 (19) | 0.21366 (15) | 0.0221 (4) | |
H9 | −0.2546 | 0.6476 | 0.2369 | 0.027* | |
Cl1 | 0.5668 (6) | 0.3554 (6) | 0.4816 (4) | 0.217 (2) | 0.50 |
Cl2 | 0.5633 (6) | 0.5764 (6) | 0.4672 (5) | 0.244 (3) | 0.50 |
C99 | 0.5917 (9) | 0.4761 (8) | 0.4187 (7) | 0.094 (3)* | 0.50 |
H99A | 0.6841 | 0.4562 | 0.3863 | 0.112* | 0.50 |
H99B | 0.5382 | 0.5101 | 0.3698 | 0.112* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au | 0.02145 (4) | 0.01662 (3) | 0.02164 (4) | −0.00004 (2) | −0.00705 (2) | −0.00723 (2) |
P1 | 0.01644 (19) | 0.01485 (19) | 0.01604 (19) | −0.00315 (15) | −0.00430 (15) | −0.00381 (15) |
P2 | 0.0224 (2) | 0.0179 (2) | 0.0202 (2) | −0.00113 (17) | −0.00508 (17) | −0.00756 (17) |
C1 | 0.0159 (7) | 0.0174 (7) | 0.0147 (7) | −0.0061 (6) | −0.0025 (6) | −0.0040 (6) |
C2 | 0.0199 (8) | 0.0224 (8) | 0.0140 (7) | −0.0088 (6) | −0.0028 (6) | −0.0043 (6) |
C3 | 0.0202 (8) | 0.0355 (10) | 0.0202 (8) | −0.0075 (8) | −0.0003 (7) | −0.0111 (8) |
C11 | 0.0181 (8) | 0.0222 (8) | 0.0170 (8) | −0.0070 (7) | −0.0032 (6) | −0.0066 (6) |
C12 | 0.0263 (9) | 0.0255 (9) | 0.0233 (9) | −0.0133 (8) | −0.0084 (7) | −0.0007 (7) |
C13 | 0.0404 (12) | 0.0311 (10) | 0.0273 (10) | −0.0216 (9) | −0.0100 (9) | 0.0021 (8) |
C14 | 0.0366 (11) | 0.0443 (12) | 0.0292 (10) | −0.0286 (10) | −0.0020 (9) | −0.0090 (9) |
C15 | 0.0220 (9) | 0.0477 (13) | 0.0333 (11) | −0.0167 (9) | −0.0036 (8) | −0.0156 (9) |
C16 | 0.0196 (8) | 0.0296 (10) | 0.0258 (9) | −0.0059 (7) | −0.0071 (7) | −0.0086 (7) |
C21 | 0.0246 (9) | 0.0205 (8) | 0.0163 (8) | −0.0066 (7) | −0.0045 (7) | −0.0043 (6) |
C22 | 0.0565 (14) | 0.0236 (10) | 0.0221 (9) | −0.0135 (10) | −0.0039 (9) | −0.0072 (8) |
C23 | 0.091 (2) | 0.0349 (12) | 0.0262 (11) | −0.0234 (13) | −0.0047 (12) | −0.0138 (9) |
C24 | 0.085 (2) | 0.0479 (14) | 0.0186 (10) | −0.0270 (14) | −0.0012 (11) | −0.0108 (10) |
C25 | 0.0773 (19) | 0.0391 (13) | 0.0188 (10) | −0.0276 (13) | −0.0037 (11) | −0.0001 (9) |
C26 | 0.0496 (13) | 0.0241 (10) | 0.0213 (9) | −0.0152 (9) | −0.0069 (9) | −0.0029 (7) |
C31 | 0.0249 (9) | 0.0215 (8) | 0.0224 (8) | −0.0044 (7) | −0.0075 (7) | −0.0087 (7) |
C32 | 0.0349 (11) | 0.0214 (9) | 0.0476 (13) | −0.0060 (8) | −0.0125 (10) | −0.0043 (9) |
C33 | 0.0371 (12) | 0.0288 (11) | 0.0524 (14) | −0.0140 (9) | −0.0099 (11) | −0.0052 (10) |
C34 | 0.0300 (11) | 0.0352 (11) | 0.0442 (13) | −0.0114 (9) | −0.0096 (9) | −0.0104 (10) |
C35 | 0.0287 (10) | 0.0241 (10) | 0.0517 (14) | −0.0019 (8) | −0.0136 (10) | −0.0085 (9) |
C36 | 0.0309 (10) | 0.0206 (9) | 0.0368 (11) | −0.0057 (8) | −0.0110 (9) | −0.0054 (8) |
C41 | 0.0218 (9) | 0.0226 (9) | 0.0208 (8) | −0.0024 (7) | −0.0035 (7) | −0.0064 (7) |
C42 | 0.0455 (13) | 0.0259 (10) | 0.0225 (9) | −0.0094 (9) | 0.0005 (9) | −0.0089 (8) |
C43 | 0.0540 (15) | 0.0285 (11) | 0.0337 (11) | −0.0162 (10) | 0.0004 (10) | −0.0080 (9) |
C44 | 0.0377 (12) | 0.0365 (12) | 0.0296 (11) | −0.0125 (10) | 0.0023 (9) | −0.0011 (9) |
C45 | 0.0451 (13) | 0.0441 (13) | 0.0229 (10) | −0.0106 (11) | 0.0046 (9) | −0.0099 (9) |
C46 | 0.0364 (11) | 0.0326 (11) | 0.0259 (10) | −0.0065 (9) | −0.0009 (8) | −0.0141 (8) |
C51 | 0.0234 (9) | 0.0187 (8) | 0.0190 (8) | −0.0037 (7) | −0.0047 (7) | −0.0060 (6) |
C52 | 0.0254 (9) | 0.0372 (11) | 0.0243 (9) | −0.0082 (8) | −0.0033 (7) | −0.0126 (8) |
C53 | 0.0346 (11) | 0.0484 (13) | 0.0231 (10) | −0.0160 (10) | 0.0008 (8) | −0.0152 (9) |
C54 | 0.0425 (12) | 0.0315 (10) | 0.0239 (9) | −0.0174 (9) | −0.0100 (8) | −0.0062 (8) |
C55 | 0.0303 (11) | 0.0386 (12) | 0.0405 (12) | −0.0075 (9) | −0.0133 (9) | −0.0155 (10) |
C56 | 0.0245 (10) | 0.0385 (11) | 0.0344 (11) | −0.0053 (8) | −0.0049 (8) | −0.0185 (9) |
B1 | 0.0213 (9) | 0.0255 (10) | 0.0190 (9) | −0.0095 (8) | −0.0064 (7) | −0.0017 (7) |
B2 | 0.0203 (9) | 0.0206 (9) | 0.0261 (10) | −0.0055 (8) | −0.0067 (8) | −0.0022 (8) |
B3 | 0.0183 (9) | 0.0174 (9) | 0.0214 (9) | −0.0050 (7) | −0.0041 (7) | −0.0043 (7) |
B4 | 0.0223 (9) | 0.0184 (9) | 0.0174 (9) | −0.0081 (7) | −0.0031 (7) | −0.0058 (7) |
B5 | 0.0174 (9) | 0.0215 (9) | 0.0183 (9) | −0.0082 (7) | −0.0006 (7) | −0.0049 (7) |
B6 | 0.0170 (9) | 0.0243 (10) | 0.0249 (10) | −0.0067 (7) | −0.0020 (7) | −0.0070 (8) |
B7 | 0.0194 (9) | 0.0275 (10) | 0.0240 (10) | −0.0088 (8) | −0.0062 (8) | −0.0044 (8) |
B8 | 0.0230 (10) | 0.0263 (10) | 0.0204 (9) | −0.0123 (8) | −0.0038 (7) | −0.0054 (8) |
B9 | 0.0214 (9) | 0.0252 (10) | 0.0236 (10) | −0.0117 (8) | −0.0028 (7) | −0.0072 (8) |
Cl1 | 0.246 (6) | 0.266 (6) | 0.152 (4) | −0.089 (5) | −0.038 (4) | −0.062 (4) |
Cl2 | 0.200 (5) | 0.286 (7) | 0.318 (8) | −0.084 (5) | −0.058 (5) | −0.153 (6) |
Au—P2 | 2.3060 (5) | C42—C43 | 1.390 (3) |
Au—P1 | 2.3159 (5) | C43—C44 | 1.377 (3) |
P1—C11 | 1.8072 (18) | C44—C45 | 1.383 (3) |
P1—C21 | 1.8158 (18) | C45—C46 | 1.391 (3) |
P1—C1 | 1.8197 (17) | C51—C52 | 1.391 (3) |
P2—C41 | 1.808 (2) | C51—C56 | 1.393 (3) |
P2—C31 | 1.8130 (19) | C52—C53 | 1.392 (3) |
P2—C51 | 1.8153 (18) | C53—C54 | 1.377 (3) |
C1—C2 | 1.588 (2) | C54—C55 | 1.387 (3) |
C1—B3 | 1.621 (3) | C55—C56 | 1.388 (3) |
C1—B5 | 1.743 (2) | B1—B7 | 1.791 (3) |
C1—B4 | 1.753 (2) | B1—B8 | 1.802 (3) |
C2—C3 | 1.510 (2) | B1—B2 | 1.857 (3) |
C2—B1 | 1.631 (3) | B2—B6 | 1.776 (3) |
C2—B4 | 1.722 (3) | B2—B7 | 1.780 (3) |
C2—B8 | 1.721 (3) | B2—B3 | 1.815 (3) |
C11—C12 | 1.395 (2) | B3—B6 | 1.748 (3) |
C11—C16 | 1.399 (2) | B3—B5 | 1.784 (3) |
C12—C13 | 1.394 (3) | B4—B8 | 1.749 (3) |
C13—C14 | 1.386 (3) | B4—B9 | 1.770 (3) |
C14—C15 | 1.380 (3) | B4—B5 | 1.781 (3) |
C15—C16 | 1.385 (3) | B5—B6 | 1.750 (3) |
C21—C22 | 1.389 (3) | B5—B9 | 1.772 (3) |
C21—C26 | 1.392 (3) | B6—B9 | 1.790 (3) |
C22—C23 | 1.388 (3) | B6—B7 | 1.811 (3) |
C23—C24 | 1.378 (3) | B7—B8 | 1.769 (3) |
C24—C25 | 1.379 (3) | B7—B9 | 1.803 (3) |
C25—C26 | 1.387 (3) | B8—B9 | 1.761 (3) |
C31—C36 | 1.395 (3) | B1—H01 | 1.056 (15) |
C31—C32 | 1.397 (3) | B2—H02A | 1.070 (15) |
C32—C33 | 1.386 (3) | B2—H02B | 1.070 (16) |
C33—C34 | 1.378 (3) | B3—H03 | 1.074 (15) |
C34—C35 | 1.383 (3) | B1—H02B | 1.45 (3) |
C35—C36 | 1.393 (3) | Cl1—C99 | 1.571 (9) |
C41—C46 | 1.387 (3) | Cl2—C99 | 1.559 (8) |
C41—C42 | 1.397 (3) | ||
P2—Au—P1 | 174.041 (15) | B7—B1—B2 | 58.39 (12) |
C11—P1—C21 | 104.95 (8) | B8—B1—B2 | 107.35 (14) |
C11—P1—C1 | 106.93 (8) | B6—B2—B7 | 61.22 (12) |
C21—P1—C1 | 108.63 (8) | B6—B2—B3 | 58.23 (11) |
C11—P1—Au | 110.30 (6) | B7—B2—B3 | 105.49 (14) |
C21—P1—Au | 111.18 (6) | B6—B2—B1 | 105.23 (14) |
C1—P1—Au | 114.35 (6) | B7—B2—B1 | 58.94 (12) |
C41—P2—C31 | 109.24 (9) | B3—B2—B1 | 101.07 (13) |
C41—P2—C51 | 105.28 (9) | C1—B3—B6 | 105.46 (14) |
C31—P2—C51 | 106.42 (8) | C1—B3—B5 | 61.34 (11) |
C41—P2—Au | 113.87 (6) | B6—B3—B5 | 59.39 (11) |
C31—P2—Au | 113.12 (6) | C1—B3—B2 | 106.02 (14) |
C51—P2—Au | 108.33 (6) | B6—B3—B2 | 59.75 (12) |
C2—C1—B3 | 115.31 (14) | B5—B3—B2 | 109.19 (14) |
C2—C1—B5 | 112.04 (13) | C2—B4—B8 | 59.47 (11) |
B3—C1—B5 | 63.92 (11) | C2—B4—C1 | 54.38 (10) |
C2—C1—B4 | 61.82 (11) | B8—B4—C1 | 102.37 (13) |
B3—C1—B4 | 115.66 (13) | C2—B4—B9 | 104.70 (14) |
B5—C1—B4 | 61.25 (11) | B8—B4—B9 | 60.05 (12) |
C2—C1—P1 | 117.94 (12) | C1—B4—B9 | 103.06 (13) |
B3—C1—P1 | 118.82 (12) | C2—B4—B5 | 104.16 (13) |
B5—C1—P1 | 117.28 (11) | B8—B4—B5 | 108.28 (14) |
B4—C1—P1 | 114.54 (11) | C1—B4—B5 | 59.10 (10) |
C3—C2—C1 | 121.35 (15) | B9—B4—B5 | 59.88 (11) |
C3—C2—B1 | 117.57 (15) | C1—B5—B6 | 100.35 (13) |
C1—C2—B1 | 109.81 (14) | C1—B5—B9 | 103.38 (13) |
C3—C2—B4 | 117.37 (15) | B6—B5—B9 | 61.09 (12) |
C1—C2—B4 | 63.81 (11) | C1—B5—B4 | 59.65 (10) |
B1—C2—B4 | 115.85 (14) | B6—B5—B4 | 107.97 (14) |
C3—C2—B8 | 119.04 (15) | B9—B5—B4 | 59.78 (11) |
C1—C2—B8 | 111.00 (13) | C1—B5—B3 | 54.73 (10) |
B1—C2—B8 | 64.95 (12) | B6—B5—B3 | 59.27 (11) |
B4—C2—B8 | 61.05 (11) | B9—B5—B3 | 107.85 (14) |
C12—C11—C16 | 119.27 (17) | B4—B5—B3 | 106.56 (13) |
C12—C11—P1 | 122.95 (13) | B3—B6—B5 | 61.33 (11) |
C16—C11—P1 | 117.78 (14) | B3—B6—B2 | 62.02 (12) |
C13—C12—C11 | 119.89 (18) | B5—B6—B2 | 112.63 (14) |
C14—C13—C12 | 120.17 (19) | B3—B6—B9 | 108.67 (14) |
C15—C14—C13 | 120.12 (18) | B5—B6—B9 | 60.08 (12) |
C14—C15—C16 | 120.29 (18) | B2—B6—B9 | 110.31 (15) |
C15—C16—C11 | 120.26 (18) | B3—B6—B7 | 107.08 (14) |
C22—C21—C26 | 119.11 (17) | B5—B6—B7 | 108.16 (15) |
C22—C21—P1 | 122.26 (14) | B2—B6—B7 | 59.52 (12) |
C26—C21—P1 | 118.60 (14) | B9—B6—B7 | 60.08 (12) |
C23—C22—C21 | 120.0 (2) | B8—B7—B2 | 112.31 (15) |
C24—C23—C22 | 120.5 (2) | B8—B7—B1 | 60.80 (12) |
C23—C24—C25 | 119.9 (2) | B2—B7—B1 | 62.67 (12) |
C24—C25—C26 | 120.1 (2) | B8—B7—B9 | 59.06 (12) |
C25—C26—C21 | 120.33 (19) | B2—B7—B9 | 109.52 (14) |
C36—C31—C32 | 119.26 (18) | B1—B7—B9 | 107.36 (14) |
C36—C31—P2 | 122.40 (15) | B8—B7—B6 | 106.55 (14) |
C32—C31—P2 | 118.26 (15) | B2—B7—B6 | 59.26 (12) |
C33—C32—C31 | 120.0 (2) | B1—B7—B6 | 106.57 (14) |
C34—C33—C32 | 120.5 (2) | B9—B7—B6 | 59.40 (12) |
C33—C34—C35 | 120.0 (2) | C2—B8—B4 | 59.48 (11) |
C34—C35—C36 | 120.2 (2) | C2—B8—B9 | 105.12 (14) |
C35—C36—C31 | 120.00 (19) | B4—B8—B9 | 60.59 (12) |
C46—C41—C42 | 119.31 (19) | C2—B8—B7 | 102.51 (14) |
C46—C41—P2 | 119.40 (15) | B4—B8—B7 | 108.98 (15) |
C42—C41—P2 | 121.24 (14) | B9—B8—B7 | 61.41 (12) |
C43—C42—C41 | 120.22 (19) | C2—B8—B1 | 55.09 (11) |
C44—C43—C42 | 119.8 (2) | B4—B8—B1 | 106.30 (14) |
C43—C44—C45 | 120.6 (2) | B9—B8—B1 | 108.72 (15) |
C44—C45—C46 | 119.8 (2) | B7—B8—B1 | 60.19 (12) |
C41—C46—C45 | 120.3 (2) | B8—B9—B4 | 59.37 (11) |
C52—C51—C56 | 119.47 (17) | B8—B9—B5 | 108.11 (14) |
C52—C51—P2 | 122.62 (14) | B4—B9—B5 | 60.34 (11) |
C56—C51—P2 | 117.91 (14) | B8—B9—B6 | 107.82 (14) |
C51—C52—C53 | 119.81 (19) | B4—B9—B6 | 106.65 (14) |
C54—C53—C52 | 120.5 (2) | B5—B9—B6 | 58.83 (11) |
C53—C54—C55 | 119.97 (19) | B8—B9—B7 | 59.53 (12) |
C54—C55—C56 | 119.9 (2) | B4—B9—B7 | 106.54 (14) |
C55—C56—C51 | 120.27 (19) | B5—B9—B7 | 107.53 (14) |
C2—B1—B7 | 105.35 (14) | B6—B9—B7 | 60.53 (12) |
C2—B1—B8 | 59.95 (11) | H02A—B2—H02B | 110.2 (18) |
B7—B1—B8 | 59.01 (12) | B2—H02B—B1 | 93.7 (17) |
C2—B1—B2 | 107.61 (14) | Cl2—C99—Cl1 | 118.1 (7) |
Experimental details
Crystal data | |
Chemical formula | [Au(C15H23B9P)(C18H15P)]·0.5CH2Cl2 |
Mr | 833.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 143 |
a, b, c (Å) | 11.3770 (8), 12.518 (1), 15.4837 (12) |
α, β, γ (°) | 69.925 (3), 72.338 (3), 66.953 (3) |
V (Å3) | 1869.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.12 |
Crystal size (mm) | 0.29 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.400, 0.518 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22230, 10779, 9788 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.048, 0.99 |
No. of reflections | 10779 |
No. of parameters | 445 |
No. of restraints | 443 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.07, −0.81 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Au—P2 | 2.3060 (5) | C1—C2 | 1.588 (2) |
Au—P1 | 2.3159 (5) | C2—C3 | 1.510 (2) |
P1—C11 | 1.8072 (18) | B1—H01 | 1.056 (15) |
P1—C21 | 1.8158 (18) | B2—H02A | 1.070 (15) |
P1—C1 | 1.8197 (17) | B2—H02B | 1.070 (16) |
P2—C41 | 1.808 (2) | B3—H03 | 1.074 (15) |
P2—C31 | 1.8130 (19) | B1—H02B | 1.45 (3) |
P2—C51 | 1.8153 (18) | ||
P2—Au—P1 | 174.041 (15) | C41—P2—C51 | 105.28 (9) |
C11—P1—C21 | 104.95 (8) | C31—P2—C51 | 106.42 (8) |
C11—P1—C1 | 106.93 (8) | C41—P2—Au | 113.87 (6) |
C21—P1—C1 | 108.63 (8) | C31—P2—Au | 113.12 (6) |
C11—P1—Au | 110.30 (6) | C51—P2—Au | 108.33 (6) |
C21—P1—Au | 111.18 (6) | H02A—B2—H02B | 110.2 (18) |
C1—P1—Au | 114.35 (6) | B2—H02B—B1 | 93.7 (17) |
C41—P2—C31 | 109.24 (9) |
We are interested in closo- and nido-carborane derivatives, and have reported several complexes in which a gold moiety is coordinated to the anionic nido-diphosphine ligand 7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate(1–) (Crespo, Gimeno, Laguna & Jones, 1996; Crespo et al., 1997, 1998). We report here the structure of the neutral title complex 7-{diphenyl[(triphenylphosphine)aurio]phosphine(1+)-P}-8-methyl-7,8- dicarba-nido-undecaborate(1-) dichloromethane hemisolvate, (I). The synthetic reaction (see Experimental) results in the coordination of an {Au(PPh3)} fragment and partial degradation of the icosahedral carborane diphosphine 1-(Ph2P)-2-(CH3)-1,2-closo-C2B10H10. The product is the first reported gold derivative of the parent carbaborylphosphine and one of the few metallorganic derivatives described with the nido-diphosphine [7-(Ph2P)-8-(CH3)-7,8-nido-C2B9H10]− (cf. Viñas et al., 1996). [The `diphosphine' compound above only had one P atom ?]
The structural study of (I) (Fig. 1) reveals for the C2B9 cage a geometry corresponding to an icosahedron from which one vertex has been removed. The C1—C2 distance of 1.588 (2) Å is shorter than that found in the corresponding closo-phosphine 1-(Ph2P)-2-(CH3)-1,2-closo-C2B10H10 [1.702 (6) Å; Kivekäs et al., 1994], but very similar to those observed in the various ruthenium complexes, which range from 1.538 (9) Å in [Ru{7-(PPh2)-8-(CH3)-7,8-C2B9H10}2] (Viñas et al., 1995) to 1.561 (8) Å in [RuCl{7-(PPh2)-8-(CH3)-7,8-C2B9H10}(PPh3)2] (Viñas et al., 1996). The P1—Au—P2 fragment shows the linearity usually associated with two-coordinate gold(I) complexes, with Au—P distances of 2.3060 (5) and 2.3159 (5) Å, and a P—Au—P angle of 174.041 (15)°. A search of the Cambridge Structural Database (Allen & Kennard, 1993) for neutral molecules containing the P—Au—P group yielded 12 hits with a mean Au—P bond length of 2.317 Å.
The `extra' H atom (H2b) in the pentagonal C2B3 open face (atoms C1, C2, B1, B2 and B3; B2 bears two H atoms) is strongly bonded to the central B atom [B2—H2b 1.070 (16) Å], but can be considered as semi-bridging to B1 [B1—H2b 1.45 (3) Å]. This distance is similar to those in related derivatives such as [AuCl2{(PPh2)2C2B9H10}] (1.37 Å; Jones et al., 1997), [Au{(PPh2)2C2B9H10}{(PPh2)2C2B10H10] (1.35 Å; Crespo et al., 1997) or [Au2(C26H30B9C2)(C6F5)].CH2Cl2 [1.50 (8) Å; Crespo et al., 1998]. We attributed the imprecision of these values to the presence of heavy atoms; the current structure is appreciably more precise despite the presence of gold. We have observed a similar arrangement of H atoms in silver complexes of the open-face carborane ligand (Crespo, Gimeno, Jones & Laguna, 1996) and in the light-atom derivative [C2B9H10(SC5H4NH)2)](CF3SO3), in which the H atoms were freely refined, clearly showing the semi-bridging nature of this H atom [B—H distances 1.12 (3) and 1.39 (3) Å; Jones et al., 1997].