Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014167/wn6036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014167/wn6036Isup2.hkl |
CCDC reference: 175320
Analysis of compound (II) showed the following: IR (CD2Cl2 solution, cm-1): 2001 (s), 1955 (s), ν(CO). Mass spectrum (EI, m/z): M+ 481–493 (487, most intense). NMR 1H (300 MHz, CD2Cl2, p.p.m.): δ 1.59; 11B (96 MHz, CD2Cl2, p.p.m.): δ 21.6; 19F (282 MHz, CD2Cl2, p.p.m.): δ -152.5 (very broad signal); 13C (75 MHz, CD2Cl2, p.p.m.): δ 13.7 (CH3); 13C signals for the CO and ring C atoms not observed.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (II) showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. |
[Mo(C8H12B2F2)2(CO)2] | F(000) = 1968 |
Mr = 487.55 | Dx = 1.643 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.9106 (10) Å | Cell parameters from 494 reflections |
b = 8.9361 (6) Å | θ = 3–50° |
c = 30.252 (2) Å | µ = 0.71 mm−1 |
β = 102.074 (9)° | T = 173 K |
V = 3941.7 (5) Å3 | Block, yellow |
Z = 8 | 0.5 × 0.3 × 0.3 mm |
Siemens CCD area-detector diffractometer | 9039 independent reflections |
Radiation source: fine-focus sealed tube | 7446 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans with narrow frames | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→19 |
Tmin = 0.573, Tmax = 0.730 | k = −8→11 |
24739 measured reflections | l = −39→38 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.053 | w = 1/[σ2(Fo2) + (0.0259P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.004 |
9039 reflections | Δρmax = 0.50 e Å−3 |
540 parameters | Δρmin = −0.61 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00059 (5) |
[Mo(C8H12B2F2)2(CO)2] | V = 3941.7 (5) Å3 |
Mr = 487.55 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.9106 (10) Å | µ = 0.71 mm−1 |
b = 8.9361 (6) Å | T = 173 K |
c = 30.252 (2) Å | 0.5 × 0.3 × 0.3 mm |
β = 102.074 (9)° |
Siemens CCD area-detector diffractometer | 9039 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 7446 reflections with I > 2σ(I) |
Tmin = 0.573, Tmax = 0.730 | Rint = 0.026 |
24739 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.50 e Å−3 |
9039 reflections | Δρmin = −0.61 e Å−3 |
540 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. |
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 | ||
Mo1 | 0.118430 (10) | 0.895528 (16) | 0.106372 (5) | 0.01529 (4) | |
C1 | 0.06972 (13) | 0.8590 (2) | 0.04129 (7) | 0.0240 (4) | |
O1 | 0.04511 (10) | 0.83535 (17) | 0.00340 (5) | 0.0352 (3) | |
C2 | 0.11510 (13) | 1.1090 (2) | 0.08756 (6) | 0.0243 (4) | |
O2 | 0.11014 (10) | 1.23185 (16) | 0.07697 (5) | 0.0356 (3) | |
B1 | 0.05369 (15) | 0.8163 (3) | 0.17645 (7) | 0.0248 (5) | |
B2 | −0.05420 (14) | 0.8603 (2) | 0.08570 (7) | 0.0230 (5) | |
B3 | 0.25254 (15) | 0.7275 (3) | 0.14741 (8) | 0.0292 (5) | |
B4 | 0.27317 (15) | 1.0012 (2) | 0.09956 (8) | 0.0249 (5) | |
F1 | 0.08575 (8) | 0.79000 (14) | 0.22113 (4) | 0.0342 (3) | |
F2 | −0.11559 (7) | 0.87392 (13) | 0.04538 (4) | 0.0303 (3) | |
F3 | 0.26152 (8) | 0.59715 (14) | 0.17107 (4) | 0.0428 (3) | |
F4 | 0.29780 (8) | 1.12666 (13) | 0.07880 (4) | 0.0352 (3) | |
C3 | 0.04805 (14) | 1.1077 (2) | 0.19211 (7) | 0.0300 (4) | |
H3A | −0.0082 | 1.1389 | 0.2014 | 0.045* | |
H3B | 0.0716 | 1.1911 | 0.1768 | 0.045* | |
H3C | 0.0941 | 1.0784 | 0.2188 | 0.045* | |
C4 | 0.02729 (12) | 0.9752 (2) | 0.15986 (6) | 0.0223 (4) | |
C5 | −0.03158 (12) | 0.9939 (2) | 0.11720 (6) | 0.0221 (4) | |
C6 | −0.07795 (13) | 1.1433 (2) | 0.10365 (7) | 0.0270 (4) | |
H6A | −0.1274 | 1.1585 | 0.1200 | 0.040* | |
H6B | −0.1035 | 1.1436 | 0.0711 | 0.040* | |
H6C | −0.0329 | 1.2241 | 0.1111 | 0.040* | |
C7 | −0.02945 (14) | 0.5775 (2) | 0.06584 (7) | 0.0308 (5) | |
H7A | −0.0735 | 0.5099 | 0.0754 | 0.046* | |
H7B | 0.0272 | 0.5228 | 0.0652 | 0.046* | |
H7C | −0.0556 | 0.6161 | 0.0356 | 0.046* | |
C8 | −0.00847 (12) | 0.7073 (2) | 0.09890 (6) | 0.0226 (4) | |
C9 | 0.04192 (13) | 0.6850 (2) | 0.14312 (6) | 0.0235 (4) | |
C10 | 0.06966 (14) | 0.5283 (2) | 0.15980 (7) | 0.0321 (5) | |
H10J | 0.0149 | 0.4713 | 0.1625 | 0.048* | |
H10K | 0.1115 | 0.5340 | 0.1894 | 0.048* | |
H10L | 0.1006 | 0.4783 | 0.1383 | 0.048* | |
C11 | 0.27131 (15) | 0.8797 (3) | 0.22355 (7) | 0.0439 (6) | |
H11A | 0.3357 | 0.9021 | 0.2368 | 0.066* | |
H11B | 0.2552 | 0.7819 | 0.2343 | 0.066* | |
H11C | 0.2320 | 0.9570 | 0.2326 | 0.066* | |
C12 | 0.25755 (13) | 0.8770 (2) | 0.17253 (6) | 0.0283 (4) | |
C13 | 0.26427 (13) | 1.0092 (2) | 0.14884 (6) | 0.0264 (4) | |
C14 | 0.27648 (15) | 1.1597 (3) | 0.17300 (8) | 0.0392 (5) | |
H14A | 0.3379 | 1.1651 | 0.1924 | 0.059* | |
H14B | 0.2303 | 1.1704 | 0.1916 | 0.059* | |
H14C | 0.2691 | 1.2404 | 0.1506 | 0.059* | |
C15 | 0.22395 (15) | 0.5757 (2) | 0.07059 (8) | 0.0371 (5) | |
H15A | 0.2802 | 0.5492 | 0.0605 | 0.056* | |
H15B | 0.1732 | 0.5852 | 0.0443 | 0.056* | |
H15C | 0.2096 | 0.4973 | 0.0907 | 0.056* | |
C16 | 0.23771 (12) | 0.7236 (2) | 0.09588 (7) | 0.0249 (4) | |
C17 | 0.25451 (12) | 0.8563 (2) | 0.07290 (6) | 0.0221 (4) | |
C18 | 0.25990 (13) | 0.8541 (2) | 0.02343 (6) | 0.0310 (5) | |
H18A | 0.3221 | 0.8265 | 0.0207 | 0.047* | |
H18B | 0.2450 | 0.9536 | 0.0103 | 0.047* | |
H18C | 0.2161 | 0.7808 | 0.0073 | 0.047* | |
Mo2 | 0.635253 (10) | 0.667490 (16) | 0.144034 (5) | 0.01456 (4) | |
C101 | 0.64875 (12) | 0.7194 (2) | 0.20863 (6) | 0.0229 (4) | |
O101 | 0.66209 (10) | 0.74962 (17) | 0.24640 (4) | 0.0341 (4) | |
C102 | 0.66101 (13) | 0.4597 (2) | 0.16570 (6) | 0.0250 (4) | |
O102 | 0.66956 (10) | 0.33844 (16) | 0.17830 (5) | 0.0365 (4) | |
B101 | 0.48716 (14) | 0.7310 (3) | 0.17005 (7) | 0.0236 (5) | |
B102 | 0.49326 (14) | 0.6813 (3) | 0.07644 (7) | 0.0253 (5) | |
B103 | 0.72851 (15) | 0.8539 (3) | 0.10422 (8) | 0.0293 (5) | |
B104 | 0.79139 (15) | 0.5618 (3) | 0.13769 (8) | 0.0269 (5) | |
F101 | 0.46801 (8) | 0.75863 (13) | 0.21132 (4) | 0.0324 (3) | |
F102 | 0.47775 (8) | 0.66100 (14) | 0.03081 (4) | 0.0369 (3) | |
F103 | 0.71376 (9) | 0.99352 (14) | 0.08663 (5) | 0.0467 (4) | |
F104 | 0.83624 (8) | 0.43080 (14) | 0.15060 (4) | 0.0422 (3) | |
C103 | 0.46876 (15) | 0.4454 (2) | 0.18314 (8) | 0.0371 (5) | |
H10G | 0.4026 | 0.4329 | 0.1805 | 0.056* | |
H10H | 0.4976 | 0.4696 | 0.2145 | 0.056* | |
H10I | 0.4949 | 0.3523 | 0.1743 | 0.056* | |
C104 | 0.48612 (12) | 0.5716 (2) | 0.15234 (6) | 0.0243 (4) | |
C105 | 0.49431 (12) | 0.5463 (2) | 0.10709 (7) | 0.0254 (4) | |
C106 | 0.48646 (15) | 0.3889 (2) | 0.08730 (7) | 0.0349 (5) | |
H10A | 0.4239 | 0.3517 | 0.0851 | 0.052* | |
H10B | 0.5298 | 0.3226 | 0.1069 | 0.052* | |
H10C | 0.5007 | 0.3912 | 0.0571 | 0.052* | |
C107 | 0.52507 (14) | 1.0166 (2) | 0.16278 (7) | 0.0318 (5) | |
H10D | 0.4701 | 1.0765 | 0.1513 | 0.048* | |
H10E | 0.5784 | 1.0649 | 0.1546 | 0.048* | |
H10F | 0.5347 | 1.0087 | 0.1957 | 0.048* | |
C108 | 0.51282 (12) | 0.8618 (2) | 0.14215 (6) | 0.0219 (4) | |
C109 | 0.51141 (12) | 0.8392 (2) | 0.09610 (6) | 0.0233 (4) | |
C110 | 0.51134 (15) | 0.9726 (2) | 0.06517 (7) | 0.0347 (5) | |
H11M | 0.4539 | 1.0284 | 0.0628 | 0.052* | |
H11N | 0.5167 | 0.9378 | 0.0351 | 0.052* | |
H11O | 0.5633 | 1.0379 | 0.0776 | 0.052* | |
C111 | 0.66774 (16) | 0.7386 (3) | 0.02298 (7) | 0.0487 (7) | |
H11G | 0.7184 | 0.7316 | 0.0070 | 0.073* | |
H11H | 0.6388 | 0.8372 | 0.0176 | 0.073* | |
H11I | 0.6223 | 0.6607 | 0.0118 | 0.073* | |
C112 | 0.70439 (13) | 0.7171 (3) | 0.07328 (6) | 0.0299 (5) | |
C113 | 0.73057 (13) | 0.5740 (2) | 0.09058 (6) | 0.0281 (4) | |
C114 | 0.71287 (16) | 0.4355 (3) | 0.06088 (8) | 0.0484 (7) | |
H11P | 0.7578 | 0.4308 | 0.0415 | 0.073* | |
H11Q | 0.6509 | 0.4405 | 0.0420 | 0.073* | |
H11R | 0.7184 | 0.3460 | 0.0800 | 0.073* | |
C115 | 0.78149 (15) | 0.9703 (2) | 0.18572 (8) | 0.0384 (5) | |
H11J | 0.8470 | 0.9949 | 0.1927 | 0.058* | |
H11K | 0.7613 | 0.9475 | 0.2138 | 0.058* | |
H11L | 0.7466 | 1.0557 | 0.1707 | 0.058* | |
C116 | 0.76526 (12) | 0.8348 (2) | 0.15459 (7) | 0.0251 (4) | |
C117 | 0.80070 (12) | 0.6928 (2) | 0.17047 (6) | 0.0240 (4) | |
C118 | 0.85520 (14) | 0.6700 (3) | 0.21833 (7) | 0.0360 (5) | |
H11D | 0.9194 | 0.6978 | 0.2199 | 0.054* | |
H11E | 0.8519 | 0.5647 | 0.2269 | 0.054* | |
H11F | 0.8295 | 0.7328 | 0.2392 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01401 (7) | 0.01448 (8) | 0.01732 (8) | −0.00037 (6) | 0.00318 (5) | −0.00074 (6) |
C1 | 0.0188 (9) | 0.0246 (11) | 0.0291 (10) | 0.0000 (8) | 0.0061 (8) | 0.0002 (8) |
O1 | 0.0292 (8) | 0.0525 (10) | 0.0224 (7) | −0.0037 (7) | 0.0021 (6) | −0.0057 (7) |
C2 | 0.0205 (9) | 0.0242 (11) | 0.0282 (10) | −0.0030 (8) | 0.0053 (8) | −0.0015 (8) |
O2 | 0.0329 (8) | 0.0212 (8) | 0.0528 (10) | −0.0011 (6) | 0.0097 (7) | 0.0054 (7) |
B1 | 0.0207 (11) | 0.0299 (13) | 0.0252 (11) | −0.0018 (9) | 0.0081 (9) | 0.0034 (9) |
B2 | 0.0152 (10) | 0.0270 (12) | 0.0281 (11) | −0.0016 (8) | 0.0078 (8) | 0.0006 (9) |
B3 | 0.0161 (11) | 0.0334 (13) | 0.0381 (13) | 0.0042 (9) | 0.0055 (10) | 0.0104 (11) |
B4 | 0.0183 (10) | 0.0257 (12) | 0.0309 (12) | −0.0019 (9) | 0.0057 (9) | −0.0021 (9) |
F1 | 0.0393 (7) | 0.0380 (7) | 0.0254 (6) | −0.0013 (6) | 0.0068 (5) | 0.0049 (5) |
F2 | 0.0223 (6) | 0.0341 (7) | 0.0318 (6) | 0.0027 (5) | −0.0007 (5) | −0.0026 (5) |
F3 | 0.0328 (7) | 0.0416 (8) | 0.0525 (8) | 0.0080 (6) | 0.0053 (6) | 0.0225 (6) |
F4 | 0.0337 (7) | 0.0289 (7) | 0.0470 (7) | −0.0082 (5) | 0.0178 (6) | 0.0005 (5) |
C3 | 0.0311 (11) | 0.0288 (11) | 0.0322 (11) | −0.0008 (9) | 0.0112 (9) | −0.0074 (9) |
C4 | 0.0209 (9) | 0.0237 (10) | 0.0247 (9) | −0.0022 (8) | 0.0102 (8) | −0.0027 (8) |
C5 | 0.0187 (9) | 0.0216 (10) | 0.0283 (10) | 0.0010 (7) | 0.0099 (8) | 0.0009 (8) |
C6 | 0.0253 (10) | 0.0214 (10) | 0.0354 (11) | 0.0047 (8) | 0.0090 (9) | 0.0004 (8) |
C7 | 0.0289 (11) | 0.0233 (11) | 0.0400 (12) | −0.0041 (8) | 0.0069 (9) | −0.0054 (9) |
C8 | 0.0193 (9) | 0.0201 (10) | 0.0299 (10) | −0.0027 (8) | 0.0087 (8) | −0.0018 (8) |
C9 | 0.0208 (9) | 0.0205 (10) | 0.0313 (10) | −0.0014 (7) | 0.0098 (8) | 0.0033 (8) |
C10 | 0.0318 (11) | 0.0223 (11) | 0.0429 (12) | −0.0003 (9) | 0.0092 (9) | 0.0063 (9) |
C11 | 0.0310 (12) | 0.0742 (18) | 0.0256 (11) | 0.0063 (11) | 0.0036 (9) | 0.0016 (11) |
C12 | 0.0155 (9) | 0.0436 (13) | 0.0242 (10) | 0.0005 (8) | 0.0005 (8) | 0.0004 (9) |
C13 | 0.0169 (9) | 0.0349 (12) | 0.0266 (10) | −0.0039 (8) | 0.0026 (8) | −0.0081 (8) |
C14 | 0.0303 (12) | 0.0454 (14) | 0.0418 (13) | −0.0112 (10) | 0.0073 (10) | −0.0209 (11) |
C15 | 0.0309 (12) | 0.0273 (12) | 0.0549 (14) | 0.0034 (9) | 0.0129 (10) | −0.0082 (10) |
C16 | 0.0169 (9) | 0.0229 (10) | 0.0350 (11) | 0.0027 (8) | 0.0058 (8) | −0.0032 (8) |
C17 | 0.0150 (9) | 0.0278 (11) | 0.0237 (9) | 0.0020 (7) | 0.0043 (7) | −0.0011 (8) |
C18 | 0.0238 (10) | 0.0431 (13) | 0.0277 (10) | −0.0004 (9) | 0.0087 (8) | −0.0048 (9) |
Mo2 | 0.01347 (7) | 0.01412 (8) | 0.01569 (7) | −0.00063 (6) | 0.00209 (5) | −0.00011 (6) |
C101 | 0.0184 (9) | 0.0243 (10) | 0.0259 (10) | −0.0007 (8) | 0.0047 (8) | 0.0018 (8) |
O101 | 0.0312 (8) | 0.0481 (10) | 0.0225 (8) | −0.0013 (7) | 0.0043 (6) | −0.0048 (6) |
C102 | 0.0202 (9) | 0.0260 (11) | 0.0281 (10) | 0.0008 (8) | 0.0036 (8) | −0.0017 (8) |
O102 | 0.0348 (8) | 0.0234 (8) | 0.0489 (9) | 0.0046 (6) | 0.0036 (7) | 0.0099 (7) |
B101 | 0.0162 (10) | 0.0274 (12) | 0.0272 (11) | 0.0016 (9) | 0.0046 (9) | 0.0013 (9) |
B102 | 0.0159 (10) | 0.0329 (14) | 0.0254 (11) | 0.0010 (9) | 0.0003 (9) | −0.0017 (9) |
B103 | 0.0192 (11) | 0.0305 (13) | 0.0391 (13) | −0.0026 (9) | 0.0082 (10) | 0.0095 (10) |
B104 | 0.0186 (11) | 0.0302 (13) | 0.0339 (12) | 0.0018 (9) | 0.0099 (9) | −0.0003 (10) |
F101 | 0.0316 (7) | 0.0393 (8) | 0.0293 (6) | 0.0048 (5) | 0.0134 (5) | 0.0005 (5) |
F102 | 0.0363 (7) | 0.0472 (8) | 0.0236 (6) | −0.0008 (6) | −0.0020 (5) | −0.0045 (5) |
F103 | 0.0339 (7) | 0.0379 (8) | 0.0663 (9) | −0.0061 (6) | 0.0056 (6) | 0.0240 (7) |
F104 | 0.0321 (7) | 0.0335 (7) | 0.0621 (9) | 0.0118 (6) | 0.0124 (6) | −0.0008 (6) |
C103 | 0.0302 (11) | 0.0290 (12) | 0.0560 (14) | −0.0010 (9) | 0.0178 (10) | 0.0099 (10) |
C104 | 0.0152 (9) | 0.0238 (10) | 0.0340 (10) | −0.0008 (7) | 0.0057 (8) | 0.0041 (8) |
C105 | 0.0180 (9) | 0.0225 (10) | 0.0330 (10) | −0.0018 (8) | −0.0010 (8) | −0.0035 (8) |
C106 | 0.0322 (12) | 0.0252 (11) | 0.0435 (12) | −0.0045 (9) | −0.0007 (10) | −0.0089 (9) |
C107 | 0.0317 (11) | 0.0231 (11) | 0.0396 (12) | 0.0014 (9) | 0.0051 (9) | −0.0027 (9) |
C108 | 0.0172 (9) | 0.0171 (10) | 0.0301 (10) | 0.0030 (7) | 0.0021 (8) | 0.0007 (7) |
C109 | 0.0182 (9) | 0.0232 (10) | 0.0273 (10) | 0.0027 (8) | 0.0022 (8) | 0.0063 (8) |
C110 | 0.0374 (12) | 0.0293 (12) | 0.0377 (12) | 0.0065 (9) | 0.0085 (10) | 0.0122 (9) |
C111 | 0.0335 (13) | 0.090 (2) | 0.0223 (11) | −0.0091 (13) | 0.0057 (10) | 0.0077 (11) |
C112 | 0.0189 (10) | 0.0507 (13) | 0.0213 (10) | −0.0047 (9) | 0.0069 (8) | −0.0003 (9) |
C113 | 0.0227 (10) | 0.0365 (12) | 0.0279 (10) | −0.0038 (9) | 0.0117 (8) | −0.0106 (9) |
C114 | 0.0394 (13) | 0.0594 (17) | 0.0492 (14) | −0.0103 (12) | 0.0157 (11) | −0.0323 (13) |
C115 | 0.0343 (12) | 0.0326 (13) | 0.0518 (14) | −0.0128 (10) | 0.0170 (11) | −0.0142 (10) |
C116 | 0.0170 (9) | 0.0287 (11) | 0.0317 (10) | −0.0064 (8) | 0.0098 (8) | −0.0034 (8) |
C117 | 0.0143 (9) | 0.0327 (12) | 0.0257 (10) | −0.0024 (8) | 0.0055 (7) | −0.0018 (8) |
C118 | 0.0232 (11) | 0.0544 (15) | 0.0290 (11) | −0.0001 (10) | 0.0023 (9) | 0.0007 (10) |
Mo1—C1 | 1.9780 (19) | Mo2—C101 | 1.9772 (19) |
Mo1—C2 | 1.988 (2) | Mo2—C102 | 1.980 (2) |
Mo1—C16 | 2.4208 (18) | Mo2—C116 | 2.4160 (18) |
Mo1—C4 | 2.4272 (17) | Mo2—C105 | 2.4199 (18) |
Mo1—C17 | 2.4749 (18) | Mo2—C117 | 2.4395 (18) |
Mo1—C5 | 2.4881 (18) | Mo2—C104 | 2.4446 (18) |
Mo1—C13 | 2.4983 (18) | Mo2—C113 | 2.5089 (18) |
Mo1—C8 | 2.5064 (18) | Mo2—C108 | 2.5113 (18) |
Mo1—B2 | 2.538 (2) | Mo2—B104 | 2.556 (2) |
Mo1—B4 | 2.541 (2) | Mo2—B101 | 2.558 (2) |
Mo1—C12 | 2.5689 (19) | Mo2—C109 | 2.5976 (18) |
Mo1—C9 | 2.5703 (18) | Mo2—C112 | 2.6009 (18) |
C1—O1 | 1.148 (2) | C101—O101 | 1.150 (2) |
C2—O2 | 1.141 (2) | C102—O102 | 1.147 (2) |
B1—F1 | 1.357 (2) | B101—F101 | 1.360 (2) |
B1—C4 | 1.530 (3) | B101—C104 | 1.521 (3) |
B1—C9 | 1.533 (3) | B101—C108 | 1.536 (3) |
B2—F2 | 1.369 (2) | B102—F102 | 1.363 (2) |
B2—C5 | 1.521 (3) | B102—C105 | 1.520 (3) |
B2—C8 | 1.543 (3) | B102—C109 | 1.533 (3) |
B3—F3 | 1.359 (3) | B103—F103 | 1.356 (3) |
B3—C16 | 1.528 (3) | B103—C116 | 1.517 (3) |
B3—C12 | 1.531 (3) | B103—C112 | 1.536 (3) |
B4—F4 | 1.372 (2) | B104—F104 | 1.364 (3) |
B4—C17 | 1.520 (3) | B104—C117 | 1.521 (3) |
B4—C13 | 1.526 (3) | B104—C113 | 1.525 (3) |
C3—C4 | 1.524 (3) | C103—C104 | 1.519 (3) |
C4—C5 | 1.411 (3) | C104—C105 | 1.418 (3) |
C5—C6 | 1.519 (2) | C105—C106 | 1.523 (3) |
C7—C8 | 1.521 (3) | C107—C108 | 1.513 (3) |
C8—C9 | 1.405 (3) | C108—C109 | 1.403 (3) |
C9—C10 | 1.517 (3) | C109—C110 | 1.515 (3) |
C11—C12 | 1.514 (3) | C111—C112 | 1.518 (3) |
C12—C13 | 1.396 (3) | C112—C113 | 1.406 (3) |
C13—C14 | 1.524 (3) | C113—C114 | 1.520 (3) |
C15—C16 | 1.519 (3) | C115—C116 | 1.521 (3) |
C16—C17 | 1.423 (3) | C116—C117 | 1.420 (3) |
C17—C18 | 1.516 (2) | C117—C118 | 1.518 (3) |
C1—Mo1—C2 | 83.77 (8) | C101—Mo2—C102 | 85.42 (8) |
C1—Mo1—C16 | 83.78 (7) | C101—Mo2—C116 | 79.12 (7) |
C2—Mo1—C16 | 123.12 (7) | C102—Mo2—C116 | 116.23 (7) |
C1—Mo1—C4 | 124.87 (7) | C101—Mo2—C105 | 117.41 (7) |
C2—Mo1—C4 | 85.71 (7) | C102—Mo2—C105 | 79.80 (7) |
C16—Mo1—C4 | 143.39 (7) | C116—Mo2—C105 | 158.96 (7) |
C1—Mo1—C17 | 74.40 (7) | C101—Mo2—C117 | 76.55 (7) |
C2—Mo1—C17 | 89.57 (7) | C102—Mo2—C117 | 82.26 (7) |
C16—Mo1—C17 | 33.77 (6) | C116—Mo2—C117 | 34.00 (6) |
C4—Mo1—C17 | 159.32 (6) | C105—Mo2—C117 | 156.04 (6) |
C1—Mo1—C5 | 92.08 (7) | C101—Mo2—C104 | 83.53 (7) |
C2—Mo1—C5 | 74.29 (7) | C102—Mo2—C104 | 75.81 (7) |
C16—Mo1—C5 | 161.25 (6) | C116—Mo2—C104 | 157.72 (6) |
C4—Mo1—C5 | 33.33 (6) | C105—Mo2—C104 | 33.88 (6) |
C17—Mo1—C5 | 160.15 (6) | C117—Mo2—C104 | 151.40 (6) |
C1—Mo1—C13 | 132.68 (7) | C101—Mo2—C113 | 139.54 (7) |
C2—Mo1—C13 | 73.99 (7) | C102—Mo2—C113 | 78.72 (7) |
C16—Mo1—C13 | 74.99 (6) | C116—Mo2—C113 | 75.18 (6) |
C4—Mo1—C13 | 94.96 (6) | C105—Mo2—C113 | 96.18 (6) |
C17—Mo1—C13 | 64.41 (6) | C117—Mo2—C113 | 64.64 (6) |
C5—Mo1—C13 | 119.90 (6) | C104—Mo2—C113 | 126.85 (6) |
C1—Mo1—C8 | 71.72 (7) | C101—Mo2—C108 | 77.50 (7) |
C2—Mo1—C8 | 130.16 (7) | C102—Mo2—C108 | 138.22 (7) |
C16—Mo1—C8 | 97.10 (6) | C116—Mo2—C108 | 97.72 (6) |
C4—Mo1—C8 | 74.91 (6) | C105—Mo2—C108 | 75.05 (6) |
C17—Mo1—C8 | 122.41 (6) | C117—Mo2—C108 | 128.60 (6) |
C5—Mo1—C8 | 64.32 (6) | C104—Mo2—C108 | 64.67 (6) |
C13—Mo1—C8 | 151.47 (6) | C113—Mo2—C108 | 136.27 (7) |
C1—Mo1—B2 | 65.92 (7) | C101—Mo2—B104 | 104.76 (7) |
C2—Mo1—B2 | 94.88 (7) | C102—Mo2—B104 | 64.01 (8) |
C16—Mo1—B2 | 128.62 (7) | C116—Mo2—B104 | 61.34 (7) |
C4—Mo1—B2 | 61.33 (7) | C105—Mo2—B104 | 121.10 (7) |
C17—Mo1—B2 | 139.26 (6) | C117—Mo2—B104 | 35.36 (7) |
C5—Mo1—B2 | 35.21 (6) | C104—Mo2—B104 | 137.77 (7) |
C13—Mo1—B2 | 154.94 (7) | C113—Mo2—B104 | 35.02 (7) |
C8—Mo1—B2 | 35.62 (6) | C108—Mo2—B104 | 157.33 (7) |
C1—Mo1—B4 | 97.54 (7) | C101—Mo2—B101 | 63.89 (7) |
C2—Mo1—B4 | 65.74 (7) | C102—Mo2—B101 | 103.08 (7) |
C16—Mo1—B4 | 61.36 (7) | C116—Mo2—B101 | 122.84 (7) |
C4—Mo1—B4 | 126.13 (7) | C105—Mo2—B101 | 61.27 (7) |
C17—Mo1—B4 | 35.25 (6) | C117—Mo2—B101 | 139.23 (7) |
C5—Mo1—B4 | 137.39 (7) | C104—Mo2—B101 | 35.30 (7) |
C13—Mo1—B4 | 35.24 (6) | C113—Mo2—B101 | 156.06 (7) |
C8—Mo1—B4 | 157.40 (7) | C108—Mo2—B101 | 35.27 (7) |
B2—Mo1—B4 | 156.54 (7) | B104—Mo2—B101 | 164.42 (7) |
C1—Mo1—C12 | 146.45 (7) | C101—Mo2—C109 | 109.07 (7) |
C2—Mo1—C12 | 104.64 (7) | C102—Mo2—C109 | 143.61 (7) |
C16—Mo1—C12 | 64.24 (6) | C116—Mo2—C109 | 99.51 (6) |
C4—Mo1—C12 | 88.45 (6) | C105—Mo2—C109 | 63.85 (6) |
C17—Mo1—C12 | 73.27 (6) | C117—Mo2—C109 | 132.87 (6) |
C5—Mo1—C12 | 121.46 (6) | C104—Mo2—C109 | 73.07 (6) |
C13—Mo1—C12 | 31.95 (6) | C113—Mo2—C109 | 105.62 (6) |
C8—Mo1—C12 | 119.88 (6) | C108—Mo2—C109 | 31.83 (6) |
B2—Mo1—C12 | 142.75 (7) | B104—Mo2—C109 | 136.76 (7) |
B4—Mo1—C12 | 59.22 (7) | B101—Mo2—C109 | 58.82 (6) |
C1—Mo1—C9 | 101.88 (7) | C101—Mo2—C112 | 142.89 (7) |
C2—Mo1—C9 | 147.05 (7) | C102—Mo2—C112 | 110.46 (7) |
C16—Mo1—C9 | 89.82 (6) | C116—Mo2—C112 | 63.78 (6) |
C4—Mo1—C9 | 64.24 (6) | C105—Mo2—C112 | 98.72 (6) |
C17—Mo1—C9 | 123.31 (6) | C117—Mo2—C112 | 72.92 (6) |
C5—Mo1—C9 | 73.09 (6) | C104—Mo2—C112 | 132.07 (6) |
C13—Mo1—C9 | 119.50 (6) | C113—Mo2—C112 | 31.87 (7) |
C8—Mo1—C9 | 32.09 (6) | C108—Mo2—C112 | 105.95 (7) |
B2—Mo1—C9 | 59.80 (6) | B104—Mo2—C112 | 58.48 (7) |
B4—Mo1—C9 | 143.10 (7) | B101—Mo2—C112 | 137.03 (7) |
C12—Mo1—C9 | 88.56 (6) | C109—Mo2—C112 | 78.33 (6) |
O1—C1—Mo1 | 177.02 (16) | O101—C101—Mo2 | 175.97 (16) |
O2—C2—Mo1 | 177.63 (17) | O102—C102—Mo2 | 175.21 (17) |
F1—B1—C4 | 120.05 (18) | F101—B101—C104 | 120.32 (18) |
F1—B1—C9 | 119.38 (18) | F101—B101—C108 | 119.36 (18) |
C4—B1—C9 | 120.55 (17) | C104—B101—C108 | 120.29 (17) |
F1—B1—Mo1 | 138.13 (14) | F101—B101—Mo2 | 133.09 (14) |
C4—B1—Mo1 | 66.07 (10) | C104—B101—Mo2 | 68.27 (10) |
C9—B1—Mo1 | 71.55 (10) | C108—B101—Mo2 | 70.70 (10) |
F2—B2—C5 | 120.54 (18) | F102—B102—C105 | 119.32 (18) |
F2—B2—C8 | 119.09 (17) | F102—B102—C109 | 119.63 (18) |
C5—B2—C8 | 120.37 (17) | C105—B102—C109 | 121.04 (18) |
F2—B2—Mo1 | 131.55 (13) | F102—B102—Mo2 | 136.23 (14) |
C5—B2—Mo1 | 70.60 (10) | C105—B102—Mo2 | 65.35 (10) |
C8—B2—Mo1 | 71.07 (10) | C109—B102—Mo2 | 72.09 (11) |
F3—B3—C16 | 119.7 (2) | F103—B103—C116 | 119.5 (2) |
F3—B3—C12 | 119.8 (2) | F103—B103—C112 | 119.7 (2) |
C16—B3—C12 | 120.52 (19) | C116—B103—C112 | 120.82 (19) |
F3—B3—Mo1 | 136.71 (14) | F103—B103—Mo2 | 135.02 (15) |
C16—B3—Mo1 | 66.00 (11) | C116—B103—Mo2 | 65.27 (10) |
C12—B3—Mo1 | 71.69 (11) | C112—B103—Mo2 | 72.25 (11) |
F4—B4—C17 | 119.35 (18) | F104—B104—C117 | 120.07 (19) |
F4—B4—C13 | 119.69 (18) | F104—B104—C113 | 119.27 (19) |
C17—B4—C13 | 120.96 (18) | C117—B104—C113 | 120.64 (19) |
F4—B4—Mo1 | 132.47 (14) | F104—B104—Mo2 | 134.04 (14) |
C17—B4—Mo1 | 70.00 (10) | C117—B104—Mo2 | 68.12 (10) |
C13—B4—Mo1 | 70.86 (11) | C113—B104—Mo2 | 70.79 (11) |
C5—C4—C3 | 119.85 (17) | C105—C104—C103 | 122.29 (18) |
C5—C4—B1 | 118.58 (17) | C105—C104—B101 | 119.53 (17) |
C3—C4—B1 | 120.46 (17) | C103—C104—B101 | 118.01 (18) |
C5—C4—Mo1 | 75.70 (10) | C105—C104—Mo2 | 72.10 (10) |
C3—C4—Mo1 | 125.99 (12) | C103—C104—Mo2 | 126.77 (13) |
B1—C4—Mo1 | 78.75 (11) | B101—C104—Mo2 | 76.43 (11) |
C4—C5—C6 | 120.79 (16) | C104—C105—B102 | 118.07 (18) |
C4—C5—B2 | 119.61 (17) | C104—C105—C106 | 120.76 (18) |
C6—C5—B2 | 119.46 (17) | B102—C105—C106 | 120.21 (18) |
C4—C5—Mo1 | 70.97 (10) | C104—C105—Mo2 | 74.01 (10) |
C6—C5—Mo1 | 130.23 (12) | B102—C105—Mo2 | 79.84 (11) |
B2—C5—Mo1 | 74.19 (10) | C106—C105—Mo2 | 125.63 (13) |
C9—C8—C7 | 120.93 (17) | C109—C108—C107 | 121.08 (17) |
C9—C8—B2 | 119.43 (17) | C109—C108—B101 | 118.84 (17) |
C7—C8—B2 | 119.12 (17) | C107—C108—B101 | 119.44 (17) |
C9—C8—Mo1 | 76.46 (11) | C109—C108—Mo2 | 77.47 (11) |
C7—C8—Mo1 | 128.22 (12) | C107—C108—Mo2 | 126.76 (13) |
B2—C8—Mo1 | 73.31 (10) | B101—C108—Mo2 | 74.03 (11) |
C8—C9—C10 | 120.14 (17) | C108—C109—C110 | 119.86 (18) |
C8—C9—B1 | 118.87 (17) | C108—C109—B102 | 118.82 (17) |
C10—C9—B1 | 120.14 (17) | C110—C109—B102 | 120.48 (18) |
C8—C9—Mo1 | 71.45 (10) | C108—C109—Mo2 | 70.69 (10) |
C10—C9—Mo1 | 134.83 (13) | C110—C109—Mo2 | 135.90 (13) |
B1—C9—Mo1 | 73.99 (11) | B102—C109—Mo2 | 73.74 (11) |
C13—C12—C11 | 120.03 (19) | C113—C112—C111 | 120.1 (2) |
C13—C12—B3 | 118.99 (18) | C113—C112—B103 | 119.05 (18) |
C11—C12—B3 | 120.17 (19) | C111—C112—B103 | 120.0 (2) |
C13—C12—Mo1 | 71.24 (11) | C113—C112—Mo2 | 70.46 (11) |
C11—C12—Mo1 | 135.10 (14) | C111—C112—Mo2 | 136.48 (14) |
B3—C12—Mo1 | 73.86 (11) | B103—C112—Mo2 | 73.54 (11) |
C12—C13—C14 | 121.00 (18) | C112—C113—C114 | 121.36 (19) |
C12—C13—B4 | 119.49 (18) | C112—C113—B104 | 118.53 (18) |
C14—C13—B4 | 118.94 (18) | C114—C113—B104 | 119.3 (2) |
C12—C13—Mo1 | 76.81 (11) | C112—C113—Mo2 | 77.68 (11) |
C14—C13—Mo1 | 127.54 (13) | C114—C113—Mo2 | 126.90 (14) |
B4—C13—Mo1 | 73.90 (11) | B104—C113—Mo2 | 74.19 (11) |
C17—C16—C15 | 119.85 (18) | C117—C116—B103 | 118.08 (18) |
C17—C16—B3 | 118.47 (18) | C117—C116—C115 | 120.14 (19) |
C15—C16—B3 | 120.60 (19) | B103—C116—C115 | 120.65 (19) |
C17—C16—Mo1 | 75.20 (11) | C117—C116—Mo2 | 73.91 (10) |
C15—C16—Mo1 | 126.34 (13) | B103—C116—Mo2 | 79.94 (11) |
B3—C16—Mo1 | 78.78 (11) | C115—C116—Mo2 | 126.41 (13) |
C16—C17—C18 | 121.53 (17) | C116—C117—C118 | 121.97 (18) |
C16—C17—B4 | 118.82 (17) | C116—C117—B104 | 119.37 (18) |
C18—C17—B4 | 119.54 (17) | C118—C117—B104 | 118.44 (18) |
C16—C17—Mo1 | 71.03 (10) | C116—C117—Mo2 | 72.09 (10) |
C18—C17—Mo1 | 128.55 (12) | C118—C117—Mo2 | 127.09 (13) |
B4—C17—Mo1 | 74.75 (11) | B104—C117—Mo2 | 76.52 (11) |
Experimental details
Crystal data | |
Chemical formula | [Mo(C8H12B2F2)2(CO)2] |
Mr | 487.55 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 14.9106 (10), 8.9361 (6), 30.252 (2) |
β (°) | 102.074 (9) |
V (Å3) | 3941.7 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.5 × 0.3 × 0.3 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.573, 0.730 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24739, 9039, 7446 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.053, 0.98 |
No. of reflections | 9039 |
No. of parameters | 540 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.61 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXTL.
The reaction of boron monofluoride with but-2-yne at low temperatures yields 1,4-difluoro-2,3,5,6-tetramethyl-1,4-diboracyclohexa-2,5-diene, (I) (Timms, 1968).
Reaction of (I), which is an analogue of duroquinone, with metal–carbonyl complexes displaces carbon monoxide thermally or under photolysis to yield complexes such as [Ni(CO)2(η6-C4Me4B2F2)] and [Ni(η6-C4Me4B2F2)2] (Maddren et al., 1975). The title compound, [Mo(CO)2(C4Me4B2F2)2], (II) (Fig. 1), was prepared by a sequential photolysis from [Mo(CO)6] and (I); photolysis of a mixture of [Mo(CO)6] with 1.5 equivalents of (I) yielded [Mo(CO)4(η6-C4Me4B2F2)] (Hawker, 1981) which, after further photolysis with another equivalent of (I), gave (II). Single crystals were grown from a solution of (II) in dichloromethane at 279 K.
Compound (II) crystallizes in space group P21/n with the asymmetric unit containing two independent molecules, each having C2 symmetry (Fig. 1). The complex consists of one Mo atom in a distorted pseudo-tetrahedral environment bonded to two carbonyl units and two conversely oriented η6-rings (angles between the MoB2 units = 45.4/70.7°). Each six-membered diboracycle acts as a 4 e- donor through two alkene entities, with Mo—Calkene bond lengths ranging between 2.415 (2) and 2.601 (2) Å. Back donation to the B—F units also occurs, leading to Mo—B contacts in the range 2.538 (2)–2.621 (2) Å. The rings are almost flat with the B atoms deviating from the Mo atom by between -0.172 and -0.165 Å (Mo deviations between 1.986 and 1.994 Å).