Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100019843/bk1569sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019843/bk1569IIIsup2.hkl |
CCDC reference: 162555
For related literature, see: Allen & Kennard (1993); Brill et al. (1971); Fischer & Gaines (1979); Gaines et al. (1974); Greenwood et al. (1986); Kennedy (1986); Lott & Gaines (1974); Lott et al. (1973).
Compound (III) was synthesized by adaption of the method of Lott & Gaines (1974) and recrystallized from a water, ethanol and CH2Cl2 solution by slow evaporation.
the cation dosorder was modelled by treating seven of the C atoms as split across the two sited [occupancy 0.735 (4): 0.265 (4)]. The atoms of the minor component were refined isotropically. H atoms of the borane cage were positioned as found in difference syntheses and were then allowed to ride on their parent B atoms with only their Uiso values refined. H atoms of the cation were placed in calculated positions and in a riding mode for the major disorder component but were omitted from the minor disorder component. The methyl orientations were obtained by refining torsional parameters. The largest residual electron-density peaks all lie in the vicinity of the disordered cation and have values of 1.02, 0.65 and 0.50 e Å-3.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. ORTEPII (Johnson, 1976) view of the anion of (III) with non-H atoms as 50% ellipsoids and H atoms as small spheres of arbitary size. |
(C16H36N)[Mn(CO)3(B9BrH12)] | F(000) = 1192 |
Mr = 570.72 | Dx = 1.239 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7469 (1) Å | Cell parameters from 34786 reflections |
b = 18.2581 (2) Å | θ = 1.8–27.5° |
c = 14.5558 (1) Å | µ = 1.76 mm−1 |
β = 101.352 (1)° | T = 150 K |
V = 3060.79 (5) Å3 | Plate, dark red |
Z = 4 | 0.20 × 0.20 × 0.05 mm |
Nonius Kappa CCD diffractometer | 6964 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 5105 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ϕ & ω scans to fill Ewald sphere | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (Blessing, 1997) | h = −15→15 |
Tmin = 0.710, Tmax = 0.916 | k = −22→23 |
34786 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difmap and geom |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.143 | w = 1/[σ2(Fo2) + (0.0796P)2 + 1.8574P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
6964 reflections | Δρmax = 1.02 e Å−3 |
353 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0048 (7) |
(C16H36N)[Mn(CO)3(B9BrH12)] | V = 3060.79 (5) Å3 |
Mr = 570.72 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.7469 (1) Å | µ = 1.76 mm−1 |
b = 18.2581 (2) Å | T = 150 K |
c = 14.5558 (1) Å | 0.20 × 0.20 × 0.05 mm |
β = 101.352 (1)° |
Nonius Kappa CCD diffractometer | 6964 independent reflections |
Absorption correction: multi-scan (Blessing, 1997) | 5105 reflections with I > 2σ(I) |
Tmin = 0.710, Tmax = 0.916 | Rint = 0.053 |
34786 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.143 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.02 e Å−3 |
6964 reflections | Δρmin = −0.52 e Å−3 |
353 parameters |
Experimental. Run at EPSRC service, Southampton 1/2000 |
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 | Occ. (<1) | |
Br1 | 0.17502 (3) | 0.445518 (18) | −0.00657 (2) | 0.04974 (14) | |
Mn1 | 0.39109 (4) | 0.30641 (2) | −0.04172 (3) | 0.03767 (15) | |
O1 | 0.4786 (3) | 0.34527 (15) | −0.21197 (17) | 0.0660 (7) | |
O2 | 0.1491 (3) | 0.28921 (15) | −0.1406 (2) | 0.0720 (8) | |
O3 | 0.4174 (3) | 0.14830 (12) | −0.07128 (19) | 0.0652 (7) | |
N1 | 0.3917 (3) | 0.05306 (14) | 0.21483 (18) | 0.0460 (6) | |
C1 | 0.4439 (3) | 0.32939 (17) | −0.1462 (2) | 0.0484 (7) | |
C2 | 0.2439 (3) | 0.29836 (17) | −0.1031 (2) | 0.0500 (8) | |
C3 | 0.4085 (3) | 0.21024 (18) | −0.0596 (2) | 0.0502 (8) | |
C4 | 0.5135 (4) | 0.0819 (2) | 0.2270 (3) | 0.0439 (10) | 0.735 (4) |
H4A | 0.5101 | 0.1360 | 0.2279 | 0.053* | 0.735 (4) |
H4B | 0.5568 | 0.0659 | 0.2892 | 0.053* | 0.735 (4) |
C5 | 0.5819 (4) | 0.0594 (2) | 0.1547 (3) | 0.0636 (10) | |
H5A | 0.5855 | 0.0052 | 0.1528 | 0.076* | |
H5B | 0.5409 | 0.0764 | 0.0924 | 0.076* | |
C6 | 0.7020 (4) | 0.0890 (3) | 0.1730 (4) | 0.0809 (12) | |
H6A | 0.6980 | 0.1430 | 0.1777 | 0.097* | |
H6B | 0.7435 | 0.0703 | 0.2344 | 0.097* | |
C7 | 0.7706 (5) | 0.0703 (3) | 0.1011 (4) | 0.0957 (16) | |
H7A | 0.7790 | 0.0170 | 0.0982 | 0.144* | |
H7B | 0.8476 | 0.0929 | 0.1177 | 0.144* | |
H7C | 0.7307 | 0.0886 | 0.0400 | 0.144* | |
C8 | 0.3853 (4) | −0.0283 (2) | 0.2023 (3) | 0.0477 (11) | 0.735 (4) |
H8A | 0.4054 | −0.0406 | 0.1412 | 0.057* | 0.735 (4) |
H8B | 0.3041 | −0.0441 | 0.1999 | 0.057* | 0.735 (4) |
C9 | 0.4645 (5) | −0.0722 (2) | 0.2790 (3) | 0.0447 (10) | 0.735 (4) |
H9A | 0.5464 | −0.0636 | 0.2743 | 0.054* | 0.735 (4) |
H9B | 0.4542 | −0.0544 | 0.3410 | 0.054* | 0.735 (4) |
C10 | 0.4401 (4) | −0.1536 (2) | 0.2723 (3) | 0.0770 (12) | |
H10A | 0.3578 | −0.1619 | 0.2761 | 0.092* | |
H10B | 0.4509 | −0.1713 | 0.2103 | 0.092* | |
C11 | 0.5134 (6) | −0.1969 (3) | 0.3448 (4) | 0.109 (2) | |
H11A | 0.5951 | −0.1852 | 0.3461 | 0.163* | |
H11B | 0.5000 | −0.2491 | 0.3312 | 0.163* | |
H11C | 0.4943 | −0.1855 | 0.4058 | 0.163* | |
C12 | 0.3199 (4) | 0.0910 (3) | 0.1272 (3) | 0.0512 (11) | 0.735 (4) |
H12A | 0.3364 | 0.1441 | 0.1338 | 0.061* | 0.735 (4) |
H12B | 0.3513 | 0.0740 | 0.0725 | 0.061* | 0.735 (4) |
C13 | 0.1984 (5) | 0.0829 (3) | 0.1040 (3) | 0.0855 (14) | |
H13A | 0.1650 | 0.1012 | 0.1570 | 0.103* | |
H13B | 0.1800 | 0.0301 | 0.0967 | 0.103* | |
C14 | 0.1396 (6) | 0.1223 (4) | 0.0154 (5) | 0.0765 (17) | 0.735 (4) |
H14A | 0.1668 | 0.1738 | 0.0215 | 0.092* | 0.735 (4) |
H14B | 0.1706 | 0.1007 | −0.0370 | 0.092* | 0.735 (4) |
C15 | 0.0218 (6) | 0.1245 (4) | −0.0123 (4) | 0.120 (2) | |
H15A | −0.0109 | 0.0768 | −0.0006 | 0.181* | |
H15B | 0.0016 | 0.1358 | −0.0793 | 0.181* | |
H15C | −0.0099 | 0.1624 | 0.0232 | 0.181* | |
C16 | 0.3422 (4) | 0.0747 (2) | 0.3011 (3) | 0.0463 (10) | 0.735 (4) |
H16A | 0.2664 | 0.0497 | 0.2956 | 0.056* | 0.735 (4) |
H16B | 0.3943 | 0.0536 | 0.3566 | 0.056* | 0.735 (4) |
C17 | 0.3245 (4) | 0.1500 (2) | 0.3219 (3) | 0.0691 (11) | |
H17A | 0.2672 | 0.1709 | 0.2695 | 0.083* | |
H17B | 0.3986 | 0.1764 | 0.3243 | 0.083* | |
C18 | 0.2837 (5) | 0.1649 (3) | 0.4104 (4) | 0.0584 (13) | 0.735 (4) |
H18A | 0.2113 | 0.1365 | 0.4080 | 0.070* | 0.735 (4) |
H18B | 0.3423 | 0.1441 | 0.4621 | 0.070* | 0.735 (4) |
C19 | 0.2610 (4) | 0.2385 (3) | 0.4364 (3) | 0.0841 (14) | |
H19A | 0.3278 | 0.2696 | 0.4322 | 0.126* | |
H19B | 0.2478 | 0.2390 | 0.5008 | 0.126* | |
H19C | 0.1919 | 0.2572 | 0.3939 | 0.126* | |
B1 | 0.3694 (3) | 0.39770 (19) | 0.1616 (2) | 0.0443 (8) | |
H1 | 0.3023 | 0.4172 | 0.1871 | 0.054 (10)* | |
B2 | 0.3541 (3) | 0.31217 (17) | 0.1022 (2) | 0.0386 (7) | |
H2 | 0.2782 | 0.2857 | 0.1207 | 0.069 (11)* | |
B3 | 0.4709 (3) | 0.3269 (2) | 0.1977 (3) | 0.0464 (8) | |
H3 | 0.4608 | 0.2916 | 0.2627 | 0.086 (14)* | |
B4 | 0.5142 (4) | 0.4211 (2) | 0.2168 (3) | 0.0526 (9) | |
H4 | 0.5321 | 0.4466 | 0.2917 | 0.060 (11)* | |
B5 | 0.3307 (3) | 0.39714 (17) | 0.0401 (2) | 0.0383 (7) | |
H5 | 0.3932 | 0.3988 | −0.0170 | 0.055 (10)* | |
B7 | 0.4987 (3) | 0.28217 (19) | 0.0983 (3) | 0.0453 (8) | |
HB7A | 0.5313 | 0.2252 | 0.1112 | 0.047 (9)* | |
HB7B | 0.5254 | 0.2993 | 0.0281 | 0.062 (11)* | |
B8 | 0.6046 (4) | 0.3556 (2) | 0.1774 (3) | 0.0561 (10) | |
HB8A | 0.6982 | 0.3327 | 0.2251 | 0.079 (13)* | |
HB8B | 0.6259 | 0.3869 | 0.1064 | 0.051 (9)* | |
B9 | 0.5933 (4) | 0.4469 (2) | 0.1351 (3) | 0.0579 (11) | |
H9 | 0.6672 | 0.4881 | 0.1527 | 0.085 (13)* | |
B10 | 0.4420 (3) | 0.46774 (19) | 0.1141 (2) | 0.0453 (8) | |
HB10A | 0.5181 | 0.4559 | 0.0580 | 0.066 (11)* | |
HB10B | 0.4224 | 0.5244 | 0.1077 | 0.045 (8)* | |
C41 | 0.4742 (14) | 0.0489 (8) | 0.1444 (11) | 0.064 (4)* | 0.265 (4) |
C81 | 0.4310 (14) | −0.0156 (10) | 0.2847 (11) | 0.069 (4)* | 0.265 (4) |
C91 | 0.414 (2) | −0.0893 (15) | 0.2368 (19) | 0.103 (7)* | 0.265 (4) |
C121 | 0.2699 (11) | 0.0328 (7) | 0.1631 (9) | 0.050 (3)* | 0.265 (4) |
C141 | 0.0977 (12) | 0.0805 (8) | 0.0510 (9) | 0.051 (3)* | 0.265 (4) |
C161 | 0.4066 (11) | 0.1187 (7) | 0.2697 (9) | 0.048 (3)* | 0.265 (4) |
C181 | 0.3429 (14) | 0.1975 (9) | 0.3897 (11) | 0.065 (4)* | 0.265 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0487 (2) | 0.0471 (2) | 0.0531 (2) | 0.01191 (13) | 0.00925 (14) | −0.00721 (13) |
Mn1 | 0.0456 (3) | 0.0278 (2) | 0.0418 (3) | 0.00217 (17) | 0.01376 (19) | −0.00031 (17) |
O1 | 0.099 (2) | 0.0572 (15) | 0.0511 (14) | −0.0025 (14) | 0.0363 (14) | 0.0023 (12) |
O2 | 0.0655 (18) | 0.0541 (16) | 0.087 (2) | −0.0084 (13) | −0.0078 (15) | −0.0170 (14) |
O3 | 0.104 (2) | 0.0311 (12) | 0.0697 (16) | 0.0108 (12) | 0.0395 (15) | −0.0004 (11) |
N1 | 0.0592 (17) | 0.0405 (14) | 0.0419 (14) | −0.0073 (12) | 0.0190 (12) | 0.0028 (11) |
C1 | 0.061 (2) | 0.0349 (15) | 0.0489 (18) | 0.0050 (14) | 0.0111 (15) | −0.0038 (13) |
C2 | 0.062 (2) | 0.0341 (16) | 0.0538 (19) | 0.0023 (14) | 0.0110 (16) | −0.0049 (14) |
C3 | 0.064 (2) | 0.0415 (18) | 0.0502 (18) | 0.0050 (15) | 0.0246 (16) | 0.0030 (14) |
C4 | 0.058 (3) | 0.037 (2) | 0.037 (2) | −0.0079 (18) | 0.0096 (18) | 0.0036 (17) |
C5 | 0.069 (2) | 0.053 (2) | 0.074 (3) | −0.0042 (17) | 0.028 (2) | 0.0005 (18) |
C6 | 0.077 (3) | 0.077 (3) | 0.091 (3) | 0.006 (2) | 0.022 (2) | 0.015 (2) |
C7 | 0.084 (3) | 0.106 (4) | 0.106 (4) | 0.008 (3) | 0.041 (3) | −0.007 (3) |
C8 | 0.062 (3) | 0.034 (2) | 0.049 (2) | −0.0108 (19) | 0.014 (2) | 0.0022 (18) |
C9 | 0.063 (3) | 0.034 (2) | 0.039 (2) | −0.004 (2) | 0.015 (2) | 0.0018 (17) |
C10 | 0.101 (3) | 0.044 (2) | 0.100 (3) | 0.003 (2) | 0.054 (3) | −0.004 (2) |
C11 | 0.162 (6) | 0.066 (3) | 0.100 (4) | 0.030 (3) | 0.029 (4) | 0.014 (3) |
C12 | 0.069 (3) | 0.045 (2) | 0.040 (2) | −0.008 (2) | 0.011 (2) | −0.0013 (18) |
C13 | 0.101 (4) | 0.091 (3) | 0.058 (2) | 0.021 (3) | 0.001 (2) | −0.023 (2) |
C14 | 0.075 (4) | 0.072 (4) | 0.080 (4) | 0.001 (3) | 0.008 (3) | −0.010 (3) |
C15 | 0.126 (5) | 0.137 (6) | 0.094 (4) | 0.046 (4) | 0.011 (4) | −0.015 (4) |
C16 | 0.061 (3) | 0.041 (2) | 0.040 (2) | −0.0089 (19) | 0.0188 (19) | 0.0022 (18) |
C17 | 0.064 (2) | 0.085 (3) | 0.059 (2) | 0.005 (2) | 0.0138 (18) | −0.013 (2) |
C18 | 0.071 (3) | 0.048 (3) | 0.058 (3) | −0.006 (2) | 0.017 (2) | −0.005 (2) |
C19 | 0.071 (3) | 0.095 (3) | 0.086 (3) | 0.006 (2) | 0.014 (2) | −0.033 (3) |
B1 | 0.058 (2) | 0.0320 (17) | 0.0441 (18) | −0.0035 (15) | 0.0139 (16) | −0.0015 (14) |
B2 | 0.0455 (19) | 0.0307 (16) | 0.0426 (17) | −0.0032 (13) | 0.0161 (14) | 0.0030 (13) |
B3 | 0.058 (2) | 0.0376 (18) | 0.0428 (18) | −0.0022 (16) | 0.0089 (16) | 0.0102 (14) |
B4 | 0.066 (2) | 0.045 (2) | 0.0433 (19) | −0.0134 (18) | 0.0023 (17) | 0.0048 (16) |
B5 | 0.0450 (18) | 0.0268 (15) | 0.0444 (17) | −0.0003 (13) | 0.0117 (14) | −0.0012 (13) |
B7 | 0.053 (2) | 0.0347 (17) | 0.0497 (19) | 0.0060 (15) | 0.0124 (16) | 0.0105 (15) |
B8 | 0.054 (2) | 0.057 (2) | 0.053 (2) | −0.0060 (18) | −0.0009 (17) | 0.0184 (18) |
B9 | 0.059 (2) | 0.053 (2) | 0.055 (2) | −0.0210 (19) | −0.0053 (18) | 0.0120 (18) |
B10 | 0.062 (2) | 0.0280 (16) | 0.0432 (18) | −0.0081 (15) | 0.0047 (16) | −0.0001 (14) |
Br1—B5 | 2.025 (3) | C13—C14 | 1.519 (8) |
Mn1—C2 | 1.789 (4) | C14—C15 | 1.363 (8) |
Mn1—C3 | 1.793 (3) | C16—C17 | 1.431 (6) |
Mn1—C1 | 1.802 (3) | C17—C18 | 1.484 (6) |
Mn1—B7 | 2.221 (4) | C18—C19 | 1.436 (7) |
Mn1—B2 | 2.224 (3) | B1—B5 | 1.737 (5) |
Mn1—B5 | 2.236 (3) | B1—B10 | 1.753 (5) |
O1—C1 | 1.149 (4) | B1—B3 | 1.768 (5) |
O2—C2 | 1.152 (4) | B1—B2 | 1.777 (5) |
O3—C3 | 1.151 (4) | B1—B4 | 1.785 (6) |
N1—C161 | 1.433 (13) | B2—B3 | 1.771 (5) |
N1—C8 | 1.497 (5) | B2—B5 | 1.789 (4) |
N1—C4 | 1.502 (5) | B2—B7 | 1.797 (5) |
N1—C121 | 1.525 (13) | B3—B8 | 1.736 (6) |
N1—C16 | 1.536 (5) | B3—B7 | 1.748 (5) |
N1—C41 | 1.546 (15) | B3—B4 | 1.801 (5) |
N1—C12 | 1.547 (5) | B4—B9 | 1.713 (6) |
N1—C81 | 1.623 (17) | B4—B8 | 1.769 (7) |
C4—C5 | 1.502 (6) | B4—B10 | 1.782 (5) |
C5—C6 | 1.485 (6) | B5—B10 | 1.994 (5) |
C6—C7 | 1.481 (7) | B7—B8 | 2.027 (6) |
C8—C9 | 1.531 (7) | B8—B9 | 1.773 (5) |
C9—C10 | 1.514 (6) | B9—B10 | 1.784 (6) |
C10—C11 | 1.456 (7) | C81—C91 | 1.51 (3) |
C12—C13 | 1.408 (7) | ||
C2—Mn1—C3 | 88.47 (15) | B10—B1—B4 | 60.5 (2) |
C2—Mn1—C1 | 93.30 (16) | B3—B1—B4 | 60.9 (2) |
C3—Mn1—C1 | 92.13 (14) | B2—B1—B4 | 115.2 (3) |
C2—Mn1—B7 | 139.58 (15) | B3—B2—B1 | 59.8 (2) |
C3—Mn1—B7 | 82.98 (15) | B3—B2—B5 | 106.5 (2) |
C1—Mn1—B7 | 126.32 (15) | B1—B2—B5 | 58.30 (18) |
C2—Mn1—B2 | 97.18 (14) | B3—B2—B7 | 58.7 (2) |
C3—Mn1—B2 | 103.43 (13) | B1—B2—B7 | 106.1 (2) |
C1—Mn1—B2 | 161.40 (14) | B5—B2—B7 | 107.5 (2) |
B7—Mn1—B2 | 47.69 (13) | B3—B2—Mn1 | 118.8 (2) |
C2—Mn1—B5 | 87.14 (14) | B1—B2—Mn1 | 118.68 (19) |
C3—Mn1—B5 | 149.36 (13) | B5—B2—Mn1 | 66.68 (15) |
C1—Mn1—B5 | 118.38 (13) | B7—B2—Mn1 | 66.06 (15) |
B7—Mn1—B5 | 80.89 (13) | B8—B3—B7 | 71.1 (2) |
B2—Mn1—B5 | 47.30 (12) | B8—B3—B1 | 108.0 (3) |
C161—N1—C8 | 153.7 (6) | B7—B3—B1 | 108.7 (2) |
C161—N1—C4 | 68.4 (5) | B8—B3—B2 | 119.9 (3) |
C8—N1—C4 | 112.7 (3) | B7—B3—B2 | 61.4 (2) |
C161—N1—C121 | 118.6 (7) | B1—B3—B2 | 60.3 (2) |
C8—N1—C121 | 71.3 (5) | B8—B3—B4 | 60.0 (2) |
C4—N1—C121 | 157.3 (5) | B7—B3—B4 | 118.7 (3) |
C161—N1—C16 | 49.7 (5) | B1—B3—B4 | 60.0 (2) |
C8—N1—C16 | 109.7 (3) | B2—B3—B4 | 114.7 (2) |
C4—N1—C16 | 108.5 (3) | B9—B4—B8 | 61.2 (2) |
C121—N1—C16 | 89.8 (5) | B9—B4—B10 | 61.3 (2) |
C161—N1—C41 | 112.8 (8) | B8—B4—B10 | 105.6 (3) |
C8—N1—C41 | 83.9 (6) | B9—B4—B1 | 110.6 (3) |
C4—N1—C41 | 52.3 (6) | B8—B4—B1 | 105.8 (3) |
C121—N1—C41 | 108.1 (8) | B10—B4—B1 | 58.9 (2) |
C16—N1—C41 | 160.6 (6) | B9—B4—B3 | 109.3 (3) |
C161—N1—C12 | 94.1 (5) | B8—B4—B3 | 58.2 (2) |
C8—N1—C12 | 109.8 (3) | B10—B4—B3 | 104.7 (2) |
C4—N1—C12 | 107.0 (3) | B1—B4—B3 | 59.1 (2) |
C121—N1—C12 | 52.8 (5) | B1—B5—B2 | 60.49 (19) |
C16—N1—C12 | 109.1 (3) | B1—B5—B10 | 55.53 (18) |
C41—N1—C12 | 77.6 (6) | B2—B5—B10 | 105.6 (2) |
C161—N1—C81 | 107.9 (8) | B1—B5—Br1 | 112.1 (2) |
C8—N1—C81 | 46.5 (6) | B2—B5—Br1 | 125.9 (2) |
C4—N1—C81 | 92.8 (6) | B10—B5—Br1 | 110.62 (18) |
C121—N1—C81 | 104.3 (8) | B1—B5—Mn1 | 120.0 (2) |
C16—N1—C81 | 78.0 (6) | B2—B5—Mn1 | 66.02 (14) |
C41—N1—C81 | 103.9 (8) | B10—B5—Mn1 | 121.6 (2) |
C12—N1—C81 | 154.7 (6) | Br1—B5—Mn1 | 120.32 (16) |
O1—C1—Mn1 | 178.6 (3) | B3—B7—B2 | 59.9 (2) |
O2—C2—Mn1 | 176.1 (3) | B3—B7—B8 | 54.2 (2) |
O3—C3—Mn1 | 178.7 (3) | B2—B7—B8 | 105.0 (2) |
C5—C4—N1 | 116.7 (3) | B3—B7—Mn1 | 120.1 (2) |
C6—C5—C4 | 113.2 (4) | B2—B7—Mn1 | 66.25 (16) |
C7—C6—C5 | 114.8 (4) | B8—B7—Mn1 | 124.4 (2) |
N1—C8—C9 | 115.0 (4) | B3—B8—B4 | 61.8 (2) |
C10—C9—C8 | 112.8 (4) | B3—B8—B9 | 109.6 (3) |
C11—C10—C9 | 114.1 (5) | B4—B8—B9 | 57.8 (2) |
C13—C12—N1 | 120.8 (4) | B3—B8—B7 | 54.7 (2) |
C12—C13—C14 | 115.1 (5) | B4—B8—B7 | 106.9 (3) |
C15—C14—C13 | 122.0 (6) | B9—B8—B7 | 115.4 (3) |
C17—C16—N1 | 121.0 (3) | B4—B9—B8 | 61.0 (2) |
C16—C17—C18 | 116.4 (4) | B4—B9—B10 | 61.2 (2) |
C19—C18—C17 | 120.6 (5) | B8—B9—B10 | 105.3 (3) |
B5—B1—B10 | 69.7 (2) | B1—B10—B4 | 60.6 (2) |
B5—B1—B3 | 108.9 (3) | B1—B10—B9 | 108.8 (3) |
B10—B1—B3 | 107.4 (3) | B4—B10—B9 | 57.4 (2) |
B5—B1—B2 | 61.21 (19) | B1—B10—B5 | 54.78 (18) |
B10—B1—B2 | 117.4 (3) | B4—B10—B5 | 107.3 (2) |
B3—B1—B2 | 60.0 (2) | B9—B10—B5 | 118.6 (3) |
B5—B1—B4 | 119.6 (3) | C91—C81—N1 | 113.7 (14) |
C2—Mn1—C1—O1 | 126 (14) | B2—B1—B5—Mn1 | −30.0 (2) |
C3—Mn1—C1—O1 | −146 (14) | B4—B1—B5—Mn1 | 74.3 (3) |
B7—Mn1—C1—O1 | −63 (14) | B3—B2—B5—B1 | −36.9 (2) |
B2—Mn1—C1—O1 | 1 (15) | B7—B2—B5—B1 | −98.5 (3) |
B5—Mn1—C1—O1 | 37 (14) | Mn1—B2—B5—B1 | −151.7 (2) |
C3—Mn1—C2—O2 | 32 (5) | B3—B2—B5—B10 | −3.3 (3) |
C1—Mn1—C2—O2 | 124 (5) | B1—B2—B5—B10 | 33.6 (2) |
B7—Mn1—C2—O2 | −46 (5) | B7—B2—B5—B10 | −64.9 (3) |
B2—Mn1—C2—O2 | −72 (5) | Mn1—B2—B5—B10 | −118.1 (2) |
B5—Mn1—C2—O2 | −118 (5) | B3—B2—B5—Br1 | −134.1 (2) |
C2—Mn1—C3—O3 | −26 (13) | B1—B2—B5—Br1 | −97.2 (3) |
C1—Mn1—C3—O3 | −119 (13) | B7—B2—B5—Br1 | 164.3 (2) |
B7—Mn1—C3—O3 | 115 (13) | Mn1—B2—B5—Br1 | 111.1 (2) |
B2—Mn1—C3—O3 | 71 (13) | B3—B2—B5—Mn1 | 114.8 (2) |
B5—Mn1—C3—O3 | 56 (13) | B1—B2—B5—Mn1 | 151.7 (2) |
C161—N1—C4—C5 | −156.6 (6) | B7—B2—B5—Mn1 | 53.22 (19) |
C8—N1—C4—C5 | 51.8 (4) | C2—Mn1—B5—B1 | 130.9 (3) |
C121—N1—C4—C5 | −44.0 (15) | C3—Mn1—B5—B1 | 48.8 (4) |
C16—N1—C4—C5 | 173.5 (3) | C1—Mn1—B5—B1 | −136.9 (2) |
C41—N1—C4—C5 | −10.2 (8) | B7—Mn1—B5—B1 | −10.3 (2) |
C12—N1—C4—C5 | −68.9 (4) | B2—Mn1—B5—B1 | 28.4 (2) |
C81—N1—C4—C5 | 95.2 (7) | C2—Mn1—B5—B2 | 102.49 (18) |
N1—C4—C5—C6 | −178.9 (3) | C3—Mn1—B5—B2 | 20.3 (3) |
C4—C5—C6—C7 | −177.7 (4) | C1—Mn1—B5—B2 | −165.29 (18) |
C161—N1—C8—C9 | −33.1 (14) | B7—Mn1—B5—B2 | −38.76 (17) |
C4—N1—C8—C9 | 53.8 (4) | C2—Mn1—B5—B10 | −163.4 (2) |
C121—N1—C8—C9 | −150.2 (6) | C3—Mn1—B5—B10 | 114.5 (3) |
C16—N1—C8—C9 | −67.3 (5) | C1—Mn1—B5—B10 | −71.2 (3) |
C41—N1—C8—C9 | 98.4 (7) | B7—Mn1—B5—B10 | 55.3 (2) |
C12—N1—C8—C9 | 172.9 (3) | B2—Mn1—B5—B10 | 94.1 (3) |
C81—N1—C8—C9 | −17.3 (8) | C2—Mn1—B5—Br1 | −16.40 (19) |
N1—C8—C9—C10 | 170.2 (3) | C3—Mn1—B5—Br1 | −98.5 (3) |
C8—C9—C10—C11 | −179.5 (4) | C1—Mn1—B5—Br1 | 75.8 (2) |
C161—N1—C12—C13 | −102.9 (6) | B7—Mn1—B5—Br1 | −157.65 (19) |
C8—N1—C12—C13 | 65.9 (5) | B2—Mn1—B5—Br1 | −118.9 (2) |
C4—N1—C12—C13 | −171.5 (4) | B8—B3—B7—B2 | −141.9 (2) |
C121—N1—C12—C13 | 20.3 (7) | B1—B3—B7—B2 | −38.7 (2) |
C16—N1—C12—C13 | −54.3 (5) | B4—B3—B7—B2 | −104.1 (3) |
C41—N1—C12—C13 | 144.7 (7) | B1—B3—B7—B8 | 103.2 (3) |
C81—N1—C12—C13 | 48.4 (16) | B2—B3—B7—B8 | 141.9 (2) |
N1—C12—C13—C14 | −179.2 (4) | B4—B3—B7—B8 | 37.8 (3) |
C12—C13—C14—C15 | −174.8 (6) | B8—B3—B7—Mn1 | −112.7 (3) |
C161—N1—C16—C17 | 27.1 (7) | B1—B3—B7—Mn1 | −9.5 (3) |
C8—N1—C16—C17 | −172.0 (4) | B2—B3—B7—Mn1 | 29.2 (2) |
C4—N1—C16—C17 | 64.5 (5) | B4—B3—B7—Mn1 | −74.9 (4) |
C121—N1—C16—C17 | −101.9 (6) | B1—B2—B7—B3 | 37.8 (2) |
C41—N1—C16—C17 | 56 (2) | B5—B2—B7—B3 | 99.0 (2) |
C12—N1—C16—C17 | −51.7 (5) | Mn1—B2—B7—B3 | 152.6 (2) |
C81—N1—C16—C17 | 153.4 (7) | B3—B2—B7—B8 | −31.2 (2) |
N1—C16—C17—C18 | −176.0 (4) | B1—B2—B7—B8 | 6.6 (3) |
C16—C17—C18—C19 | −178.6 (5) | B5—B2—B7—B8 | 67.8 (3) |
B5—B1—B2—B3 | 138.2 (3) | Mn1—B2—B7—B8 | 121.4 (2) |
B10—B1—B2—B3 | 95.1 (3) | B3—B2—B7—Mn1 | −152.6 (2) |
B4—B1—B2—B3 | 26.8 (2) | B1—B2—B7—Mn1 | −114.7 (2) |
B10—B1—B2—B5 | −43.1 (3) | B5—B2—B7—Mn1 | −53.58 (19) |
B3—B1—B2—B5 | −138.2 (3) | C2—Mn1—B7—B3 | −63.5 (3) |
B4—B1—B2—B5 | −111.4 (3) | C3—Mn1—B7—B3 | −142.8 (3) |
B5—B1—B2—B7 | 100.9 (2) | C1—Mn1—B7—B3 | 129.7 (2) |
B10—B1—B2—B7 | 57.8 (3) | B2—Mn1—B7—B3 | −27.4 (2) |
B3—B1—B2—B7 | −37.3 (2) | B5—Mn1—B7—B3 | 11.0 (2) |
B4—B1—B2—B7 | −10.5 (3) | C2—Mn1—B7—B2 | −36.1 (3) |
B5—B1—B2—Mn1 | 29.7 (2) | C3—Mn1—B7—B2 | −115.38 (18) |
B10—B1—B2—Mn1 | −13.3 (4) | C1—Mn1—B7—B2 | 157.14 (17) |
B3—B1—B2—Mn1 | −108.5 (2) | B5—Mn1—B7—B2 | 38.48 (16) |
B4—B1—B2—Mn1 | −81.7 (3) | C2—Mn1—B7—B8 | −128.5 (3) |
C2—Mn1—B2—B3 | −176.0 (2) | C3—Mn1—B7—B8 | 152.2 (3) |
C3—Mn1—B2—B3 | 93.9 (2) | C1—Mn1—B7—B8 | 64.7 (3) |
C1—Mn1—B2—B3 | −52.2 (5) | B2—Mn1—B7—B8 | −92.4 (3) |
B7—Mn1—B2—B3 | 26.7 (2) | B5—Mn1—B7—B8 | −53.9 (3) |
B5—Mn1—B2—B3 | −96.6 (3) | B7—B3—B8—B4 | 141.6 (3) |
C2—Mn1—B2—B1 | −106.7 (3) | B1—B3—B8—B4 | 37.4 (2) |
C3—Mn1—B2—B1 | 163.1 (2) | B2—B3—B8—B4 | 102.9 (3) |
C1—Mn1—B2—B1 | 17.1 (6) | B7—B3—B8—B9 | 107.8 (3) |
B7—Mn1—B2—B1 | 95.9 (3) | B1—B3—B8—B9 | 3.6 (4) |
B5—Mn1—B2—B1 | −27.4 (2) | B2—B3—B8—B9 | 69.1 (4) |
C2—Mn1—B2—B5 | −79.36 (18) | B4—B3—B8—B9 | −33.8 (3) |
C3—Mn1—B2—B5 | −169.50 (18) | B1—B3—B8—B7 | −104.2 (3) |
C1—Mn1—B2—B5 | 44.4 (5) | B2—B3—B8—B7 | −38.7 (3) |
B7—Mn1—B2—B5 | 123.3 (2) | B4—B3—B8—B7 | −141.6 (3) |
C2—Mn1—B2—B7 | 157.36 (17) | B9—B4—B8—B3 | −141.7 (3) |
C3—Mn1—B2—B7 | 67.22 (19) | B10—B4—B8—B3 | −97.9 (3) |
C1—Mn1—B2—B7 | −78.8 (5) | B1—B4—B8—B3 | −36.5 (2) |
B5—Mn1—B2—B7 | −123.3 (2) | B10—B4—B8—B9 | 43.9 (2) |
B5—B1—B3—B8 | 76.6 (3) | B1—B4—B8—B9 | 105.2 (3) |
B10—B1—B3—B8 | 2.7 (3) | B3—B4—B8—B9 | 141.7 (3) |
B2—B1—B3—B8 | 114.8 (3) | B9—B4—B8—B7 | −109.7 (3) |
B4—B1—B3—B8 | −37.4 (3) | B10—B4—B8—B7 | −65.9 (3) |
B5—B1—B3—B7 | 1.1 (3) | B1—B4—B8—B7 | −4.5 (3) |
B10—B1—B3—B7 | −72.8 (3) | B3—B4—B8—B7 | 32.0 (2) |
B2—B1—B3—B7 | 39.2 (2) | B2—B7—B8—B3 | 33.6 (2) |
B4—B1—B3—B7 | −113.0 (3) | Mn1—B7—B8—B3 | 104.8 (3) |
B5—B1—B3—B2 | −38.1 (2) | B3—B7—B8—B4 | −34.9 (2) |
B10—B1—B3—B2 | −112.1 (3) | B2—B7—B8—B4 | −1.3 (3) |
B4—B1—B3—B2 | −152.2 (3) | Mn1—B7—B8—B4 | 69.9 (3) |
B5—B1—B3—B4 | 114.0 (3) | B3—B7—B8—B9 | −96.8 (4) |
B10—B1—B3—B4 | 40.1 (2) | B2—B7—B8—B9 | −63.2 (4) |
B2—B1—B3—B4 | 152.2 (3) | Mn1—B7—B8—B9 | 8.0 (4) |
B1—B2—B3—B8 | −94.6 (3) | B10—B4—B9—B8 | −130.5 (3) |
B5—B2—B3—B8 | −58.4 (4) | B1—B4—B9—B8 | −97.2 (3) |
B7—B2—B3—B8 | 42.4 (3) | B3—B4—B9—B8 | −33.9 (3) |
Mn1—B2—B3—B8 | 13.6 (4) | B8—B4—B9—B10 | 130.5 (3) |
B1—B2—B3—B7 | −137.0 (2) | B1—B4—B9—B10 | 33.3 (3) |
B5—B2—B3—B7 | −100.7 (2) | B3—B4—B9—B10 | 96.6 (3) |
Mn1—B2—B3—B7 | −28.7 (2) | B3—B8—B9—B4 | 35.4 (3) |
B5—B2—B3—B1 | 36.3 (2) | B7—B8—B9—B4 | 94.7 (3) |
B7—B2—B3—B1 | 137.0 (2) | B3—B8—B9—B10 | −8.3 (4) |
Mn1—B2—B3—B1 | 108.3 (2) | B4—B8—B9—B10 | −43.7 (3) |
B1—B2—B3—B4 | −26.4 (3) | B7—B8—B9—B10 | 51.0 (4) |
B5—B2—B3—B4 | 9.9 (4) | B5—B1—B10—B4 | −144.6 (3) |
B7—B2—B3—B4 | 110.6 (3) | B3—B1—B10—B4 | −40.3 (3) |
Mn1—B2—B3—B4 | 81.9 (3) | B2—B1—B10—B4 | −105.0 (3) |
B5—B1—B4—B9 | 4.4 (4) | B5—B1—B10—B9 | −112.3 (3) |
B10—B1—B4—B9 | −34.3 (3) | B3—B1—B10—B9 | −8.0 (3) |
B3—B1—B4—B9 | 100.7 (3) | B2—B1—B10—B9 | −72.6 (4) |
B2—B1—B4—B9 | 74.2 (4) | B4—B1—B10—B9 | 32.3 (3) |
B5—B1—B4—B8 | −60.2 (3) | B3—B1—B10—B5 | 104.3 (3) |
B10—B1—B4—B8 | −98.9 (3) | B2—B1—B10—B5 | 39.6 (2) |
B3—B1—B4—B8 | 36.1 (2) | B4—B1—B10—B5 | 144.6 (3) |
B2—B1—B4—B8 | 9.6 (3) | B9—B4—B10—B1 | 143.1 (3) |
B5—B1—B4—B10 | 38.7 (3) | B8—B4—B10—B1 | 99.3 (3) |
B3—B1—B4—B10 | 135.0 (3) | B3—B4—B10—B1 | 38.8 (2) |
B2—B1—B4—B10 | 108.5 (3) | B8—B4—B10—B9 | −43.8 (3) |
B5—B1—B4—B3 | −96.4 (3) | B1—B4—B10—B9 | −143.1 (3) |
B10—B1—B4—B3 | −135.0 (3) | B3—B4—B10—B9 | −104.3 (3) |
B2—B1—B4—B3 | −26.5 (2) | B9—B4—B10—B5 | 113.4 (3) |
B8—B3—B4—B9 | 35.1 (3) | B8—B4—B10—B5 | 69.6 (3) |
B7—B3—B4—B9 | −7.0 (4) | B1—B4—B10—B5 | −29.7 (2) |
B1—B3—B4—B9 | −103.0 (3) | B3—B4—B10—B5 | 9.1 (3) |
B2—B3—B4—B9 | −76.6 (4) | B4—B9—B10—B1 | −33.6 (3) |
B7—B3—B4—B8 | −42.1 (3) | B8—B9—B10—B1 | 10.0 (4) |
B1—B3—B4—B8 | −138.1 (3) | B8—B9—B10—B4 | 43.6 (3) |
B2—B3—B4—B8 | −111.6 (3) | B4—B9—B10—B5 | −93.1 (3) |
B8—B3—B4—B10 | 99.4 (3) | B8—B9—B10—B5 | −49.5 (4) |
B7—B3—B4—B10 | 57.3 (4) | B2—B5—B10—B1 | −35.7 (2) |
B1—B3—B4—B10 | −38.7 (3) | Br1—B5—B10—B1 | 103.3 (2) |
B2—B3—B4—B10 | −12.2 (4) | Mn1—B5—B10—B1 | −106.8 (3) |
B8—B3—B4—B1 | 138.1 (3) | B1—B5—B10—B4 | 31.9 (3) |
B7—B3—B4—B1 | 96.1 (3) | B2—B5—B10—B4 | −3.8 (3) |
B2—B3—B4—B1 | 26.5 (3) | Br1—B5—B10—B4 | 135.2 (2) |
B10—B1—B5—B2 | 139.7 (3) | Mn1—B5—B10—B4 | −74.9 (3) |
B3—B1—B5—B2 | 37.6 (2) | B1—B5—B10—B9 | 93.7 (3) |
B4—B1—B5—B2 | 104.3 (3) | B2—B5—B10—B9 | 58.0 (3) |
B3—B1—B5—B10 | −102.1 (3) | Br1—B5—B10—B9 | −163.0 (2) |
B2—B1—B5—B10 | −139.7 (3) | Mn1—B5—B10—B9 | −13.1 (4) |
B4—B1—B5—B10 | −35.4 (3) | C161—N1—C81—C91 | 177.1 (14) |
B10—B1—B5—Br1 | −100.5 (2) | C8—N1—C81—C91 | 4.4 (11) |
B3—B1—B5—Br1 | 157.4 (2) | C4—N1—C81—C91 | −114.7 (14) |
B2—B1—B5—Br1 | 119.8 (2) | C121—N1—C81—C91 | 50.2 (15) |
B4—B1—B5—Br1 | −135.9 (3) | C16—N1—C81—C91 | 136.9 (14) |
B10—B1—B5—Mn1 | 109.7 (2) | C41—N1—C81—C91 | −62.9 (15) |
B3—B1—B5—Mn1 | 7.6 (3) | C12—N1—C81—C91 | 27 (2) |
Experimental details
Crystal data | |
Chemical formula | (C16H36N)[Mn(CO)3(B9BrH12)] |
Mr | 570.72 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 11.7469 (1), 18.2581 (2), 14.5558 (1) |
β (°) | 101.352 (1) |
V (Å3) | 3060.79 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.76 |
Crystal size (mm) | 0.20 × 0.20 × 0.05 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1997) |
Tmin, Tmax | 0.710, 0.916 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34786, 6964, 5105 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.143, 1.03 |
No. of reflections | 6964 |
No. of parameters | 353 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.02, −0.52 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, DENZO and COLLECT, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), SHELXL97.
Br1—B5 | 2.025 (3) | B2—B5 | 1.789 (4) |
Mn1—C2 | 1.789 (4) | B2—B7 | 1.797 (5) |
Mn1—C3 | 1.793 (3) | B3—B8 | 1.736 (6) |
Mn1—C1 | 1.802 (3) | B3—B7 | 1.748 (5) |
Mn1—B7 | 2.221 (4) | B3—B4 | 1.801 (5) |
Mn1—B2 | 2.224 (3) | B4—B9 | 1.713 (6) |
Mn1—B5 | 2.236 (3) | B4—B8 | 1.769 (7) |
B1—B5 | 1.737 (5) | B4—B10 | 1.782 (5) |
B1—B10 | 1.753 (5) | B5—B10 | 1.994 (5) |
B1—B3 | 1.768 (5) | B7—B8 | 2.027 (6) |
B1—B2 | 1.777 (5) | B8—B9 | 1.773 (5) |
B1—B4 | 1.785 (6) | B9—B10 | 1.784 (6) |
B2—B3 | 1.771 (5) |
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Reactions between [Mn(CO)5Br] and K[B9H14] have been shown to produce a range of nido-metalloboranes including salts of the [6-(CO)3-6-Mn(B9H13)]- anion and the neutral isomeric species [2-(THF)-6-(CO)3-6-Mn(B9H12)], (I), and [5-(THF)-6-(CO)3-6-Mn(B9H12)], (II) (Lott et al., 1973; Lott & Gaines, 1974). In our hands, the reaction also produces the previously unknown bromo-substituted anion [5-Br-6-(CO)3-6-Mn(B9H12)]- which we have isolated and characterized as the tetra-n-butylammonium salt (III). \sch
Crystallographic analysis of the dark red crystals obtained showed (III) to consist of discrete cations and anions which are separated by at least van der Waals distances. Although the n-butyl arms of the cation are rotationally disordered, the metalloborane anion seems to be unaffected. Fig. 1 shows that the coordination geometry about Mn1 is quasi-octahedral with the two bridging H atoms trans to carbonyl ligands. The main distortion from idealized geometry is the C1—Mn1—B2 angle of 161.4 (1)°. The terdentate bonding of the borane cage to manganese through only three boron atoms is relatively unusual and can be described as arising from a formal neutral {Mn(CO)3} vertex which contributes one electron and three orbitals to the cluster bonding (Kennedy, 1986). The only relevant compounds found in a search of the Cambridge Crystallographic Database (Allen & Kennard, 1993) were (I), (II), and the related zwitterion [8-{(C2H5)3N(CH2)4O}-6-(CO)3-6-Mn(B9H12)] (IV) (Gaines et al., 1974), although similar interactions have been proposed for other compounds (see for example Fischer & Gaines, 1979). These three compounds display non-symmetrical bonding to the metal as is shown by both their B5—B2 and B2—B7 distances [1.764 (6) and 1.807 (6) Å for (II), 1.783 (9) and 1.816 (10) Å for (IV)] and by their Mn—B bond lengths [ranges 2.206 (5) to 2.232 (4) and 2.209 (6) to 2.262 (7) Å for (II) and (IV), respectively]. A related Mo compound which also has a five-substituted halogen atom similar to (III), [5-Cl-6-(CO)2-6-(PPhMe2)2-6-Mo(B9H12)] (Greenwood et al., 1986), also shows non-symmetrical bonding. This contrasts with the more symmetrical bonding mode of (III), see Table 1. The B5—Br1 distance of 2.025 (3) Å lies near the upper limit found for B—Br bonds (range 1.881 to 2.052 Å for 3652 fragments), presumably as a consequence of electron withdrawal by the metal. The overall geometry of the boron cage is similar to that of B10H14 (Brill et al., 1971) but the two long B—B bonds B5—B10 and B7—B8 are now different from each other [1.994 (5) and 2.027 (6) Å] due to the unsymmetrical position of the halide substituent. The remaining B—B bond lengths range from 1.713 (5) to 1.801 (5) Å.