Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009902/fg1603sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009902/fg1603IIsup2.hkl |
CCDC reference: 152601
A mixture of [tBuC(NiPr)2]GaMe2 (200 mg, 0.706 mmol) and [Ph3C][[B(C6F5)4] (326 mg, 0.353 mmol) in benzene (1 ml) was stirred for 1 h at 296 K. The benzene was removed under vacuum and the resulting yellow oil was analyzed by 1H NMR (C6D5Cl), which established that (I) had formed quantitatively along with 0.5 equivalents of Ph3CMe (Dagorne et al., 2000). The solvent was removed under vacuum and the resulting oil was taken up in a 1:9 C6H5Cl–pentane solvent mixture (1 ml). The solution was stored at 243 K for 2 d, after which time, pale-yellow crystals of (II) had formed.
The chlorobenzene solvent molecule was disordered over two sites, with occupancies of 0.648 and 0.352 for the Cl atom. A rotatation of approximately 120° about an axis through the center and perpedicular to the plane of the benzene ring produces the second Cl-atom site from the first. Due to apparent high thermal motion, each site was modelled with two rigid groups (C—C = 1.4 Å, C—Cl = 1.74 Å, C—H = 0.95 Å, all angles = 120°) of partial and equal occupancy. Two group isotropic displacement parameters were used for the C atoms, one for each site. Anisotropic displacement parameters were used for the Cl atoms, with those in close proximity (i.e. of the same site) constrained to be the same. The O–H bonds of the water molecule were restrained to be 0.84 Å and the H···H intramolecular distance was restrained to be 1.33 Å. The hydroxyl and water H-atom locations were supported by difference-map peaks from SHELXL `omit' maps.
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The [Ga12Me12(µ3-O)8(µ-OH)6]2+ dication of (II). Displacement ellipsoids are shown at the 35% probability level. |
[Ga12C12H42O14](C24F20B)2·2C6H5Cl·2H2O | Z = 1 |
Mr = 2866.32 | F(000) = 1392 |
Triclinic, P1 | Dx = 1.938 Mg m−3 |
a = 13.532 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.223 (5) Å | Cell parameters from 40 reflections |
c = 12.755 (3) Å | θ = 11.2–14.9° |
α = 101.98 (2)° | µ = 3.42 mm−1 |
β = 106.91 (2)° | T = 210 K |
γ = 83.71 (2)° | Prism, pale yellow |
V = 2455.7 (11) Å3 | 0.34 × 0.28 × 0.18 mm |
Enraf-Nonius CAD-4 diffractometer | 4561 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.073 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
θ–2θ scans | h = −16→16 |
Absorption correction: ψ scans (MolEN; Fair, 1990) | k = −18→18 |
Tmin = 0.329, Tmax = 0.540 | l = −15→6 |
10851 measured reflections | 4 standard reflections every 120 min |
8067 independent reflections | intensity decay: 15.2% |
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)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0413P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.009 |
8067 reflections | Δρmax = 0.55 e Å−3 |
620 parameters | Δρmin = −0.76 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (3) |
[Ga12C12H42O14](C24F20B)2·2C6H5Cl·2H2O | γ = 83.71 (2)° |
Mr = 2866.32 | V = 2455.7 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 13.532 (3) Å | Mo Kα radiation |
b = 15.223 (5) Å | µ = 3.42 mm−1 |
c = 12.755 (3) Å | T = 210 K |
α = 101.98 (2)° | 0.34 × 0.28 × 0.18 mm |
β = 106.91 (2)° |
Enraf-Nonius CAD-4 diffractometer | 4561 reflections with I > 2σ(I) |
Absorption correction: ψ scans (MolEN; Fair, 1990) | Rint = 0.073 |
Tmin = 0.329, Tmax = 0.540 | 4 standard reflections every 120 min |
10851 measured reflections | intensity decay: 15.2% |
8067 independent reflections |
R[F2 > 2σ(F2)] = 0.056 | 3 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.55 e Å−3 |
8067 reflections | Δρmin = −0.76 e Å−3 |
620 parameters |
Experimental. During refinement of the data versus. the model, a number of poorly fitting data prompted a closer examination of the raw data. This led to the discovery of an intermittant electronic problem. A failing cable caused some data to be recorded with zero or near zero intensity. The faulty data were identified in two ways. First, an examination of equivalent reflections in poor agreement (one with zero intensity, the other significantly above zero) led to the rejection of approximately 400 redundant data. Second, when the refinement was near convergence, the F(obs) - F(calc) listing was checked for data with large negative values. These data were checked and those with a reflection profile characteristic of the problem (partially or totally flat) were removed (approximately 520 reflections) from the data set and the final refinement was completed with the corrected data set. |
Geometry. Note: Two orientations for the chlorobenzene were found and due to high thermal motion each orientation was modelled with two rigid groups of equal occupancy and the same the thermal parameters. This model places site C135 within 3.11 Å of a symmetry equivalent position. The actual average position of the C atom in this orientation is approximated by the average of sites C125+C135. The same symmetry operation that gives a close contact for C135 gives a contact distance of 3.67 Å for the averaged site position (C125+C135). 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) | |
Ga1 | −0.02716 (6) | 0.61462 (7) | 0.72588 (8) | 0.0395 (3) | |
Ga2 | −0.12731 (6) | 0.68139 (7) | 0.49122 (8) | 0.0393 (3) | |
Ga3 | 0.00431 (6) | 0.60410 (7) | 0.31370 (8) | 0.0380 (3) | |
Ga4 | 0.12123 (6) | 0.67728 (7) | 0.57710 (8) | 0.0390 (3) | |
Ga5 | 0.21804 (6) | 0.48995 (7) | 0.46133 (8) | 0.0383 (3) | |
Ga6 | 0.19113 (6) | 0.51130 (7) | 0.70914 (8) | 0.0384 (3) | |
C1 | −0.0722 (7) | 0.6618 (7) | 0.8566 (7) | 0.059 (3) | |
H1A | −0.0286 | 0.7088 | 0.9025 | 0.088* | |
H1B | −0.0681 | 0.6146 | 0.8976 | 0.088* | |
H1C | −0.1424 | 0.6854 | 0.8353 | 0.088* | |
C2 | −0.1809 (7) | 0.8022 (6) | 0.5236 (9) | 0.068 (3) | |
H2A | −0.1686 | 0.8364 | 0.4737 | 0.103* | |
H2B | −0.1472 | 0.8286 | 0.5991 | 0.103* | |
H2C | −0.2540 | 0.8024 | 0.5141 | 0.103* | |
C3 | −0.0387 (7) | 0.6729 (6) | 0.2004 (9) | 0.061 (3) | |
H3A | −0.1013 | 0.6503 | 0.1478 | 0.091* | |
H3B | 0.0142 | 0.6689 | 0.1630 | 0.091* | |
H3C | −0.0511 | 0.7345 | 0.2324 | 0.091* | |
C4 | 0.2086 (6) | 0.7753 (6) | 0.5933 (7) | 0.049 (2) | |
H4A | 0.2606 | 0.7802 | 0.6636 | 0.074* | |
H4B | 0.1671 | 0.8305 | 0.5905 | 0.074* | |
H4C | 0.2412 | 0.7635 | 0.5339 | 0.074* | |
C5 | 0.3608 (6) | 0.4564 (7) | 0.4715 (8) | 0.056 (3) | |
H5A | 0.3738 | 0.4566 | 0.4015 | 0.084* | |
H5B | 0.3766 | 0.3972 | 0.4891 | 0.084* | |
H5C | 0.4035 | 0.4985 | 0.5290 | 0.084* | |
C6 | 0.3008 (6) | 0.5546 (7) | 0.8401 (6) | 0.049 (2) | |
H6A | 0.3373 | 0.5045 | 0.8722 | 0.073* | |
H6B | 0.2717 | 0.5945 | 0.8936 | 0.073* | |
H6C | 0.3478 | 0.5862 | 0.8195 | 0.073* | |
O7 | 0.1262 (3) | 0.3968 (4) | 0.4158 (4) | 0.0375 (14) | |
O8 | −0.0539 (3) | 0.4933 (4) | 0.2882 (4) | 0.0369 (14) | |
O9 | 0.1802 (4) | 0.5611 (4) | 0.5844 (5) | 0.0391 (14) | |
O10 | 0.0014 (4) | 0.6555 (4) | 0.4569 (4) | 0.0406 (15) | |
O11 | 0.0611 (4) | 0.6916 (4) | 0.6995 (5) | 0.0447 (15) | |
H11 | 0.0760 | 0.7383 | 0.7481 | 0.054* | |
O12 | −0.2113 (4) | 0.6128 (4) | 0.3535 (5) | 0.0461 (16) | |
H12 | −0.2623 | 0.6411 | 0.3174 | 0.055* | |
O13 | 0.1478 (4) | 0.5621 (4) | 0.3521 (5) | 0.0476 (16) | |
H13 | 0.1842 | 0.5773 | 0.3164 | 0.057* | |
B10 | −0.6254 (6) | 0.7575 (6) | 0.2496 (7) | 0.029 (2) | |
C11 | −0.6665 (6) | 0.6538 (6) | 0.1930 (8) | 0.044 (2) | |
F12 | −0.4992 (3) | 0.5922 (3) | 0.2695 (4) | 0.0524 (14) | |
C12 | −0.5963 (5) | 0.5769 (7) | 0.2022 (7) | 0.041 (2) | |
F13 | −0.5487 (4) | 0.4240 (4) | 0.1796 (5) | 0.0667 (16) | |
C13 | −0.6187 (6) | 0.4927 (7) | 0.1584 (8) | 0.046 (2) | |
F14 | −0.7441 (4) | 0.3892 (4) | 0.0406 (5) | 0.0769 (18) | |
C14 | −0.7202 (6) | 0.4741 (6) | 0.0949 (8) | 0.047 (2) | |
F15 | −0.8851 (4) | 0.5296 (4) | 0.0057 (5) | 0.0724 (18) | |
C15 | −0.7923 (7) | 0.5454 (8) | 0.0758 (8) | 0.056 (3) | |
F16 | −0.8383 (3) | 0.6956 (4) | 0.0962 (4) | 0.0532 (14) | |
C16 | −0.7630 (6) | 0.6307 (7) | 0.1220 (8) | 0.048 (2) | |
C21 | −0.5524 (5) | 0.7643 (5) | 0.1639 (7) | 0.034 (2) | |
F22 | −0.3850 (3) | 0.7414 (4) | 0.2903 (4) | 0.0539 (14) | |
C22 | −0.4445 (7) | 0.7549 (6) | 0.1844 (8) | 0.050 (3) | |
F23 | −0.2833 (3) | 0.7483 (4) | 0.1466 (5) | 0.0641 (16) | |
C23 | −0.3920 (6) | 0.7564 (7) | 0.1103 (10) | 0.060 (3) | |
C24 | −0.4376 (7) | 0.7656 (7) | 0.0060 (9) | 0.055 (3) | |
F24 | −0.3879 (5) | 0.7701 (4) | −0.0679 (5) | 0.0763 (18) | |
F25 | −0.5989 (4) | 0.7798 (4) | −0.1314 (4) | 0.0754 (18) | |
C25 | −0.5480 (8) | 0.7717 (7) | −0.0285 (8) | 0.060 (3) | |
F26 | −0.7038 (4) | 0.7759 (4) | 0.0148 (4) | 0.0570 (14) | |
C26 | −0.5977 (6) | 0.7712 (6) | 0.0498 (8) | 0.049 (2) | |
C31 | −0.5615 (6) | 0.7729 (6) | 0.3796 (7) | 0.044 (2) | |
F32 | −0.4895 (4) | 0.9015 (4) | 0.3638 (4) | 0.0545 (14) | |
C32 | −0.5005 (6) | 0.8429 (6) | 0.4285 (8) | 0.045 (2) | |
F33 | −0.3912 (5) | 0.9382 (4) | 0.5800 (5) | 0.0794 (19) | |
C33 | −0.4515 (7) | 0.8670 (7) | 0.5398 (9) | 0.061 (3) | |
F34 | −0.4135 (5) | 0.8359 (5) | 0.7215 (4) | 0.095 (2) | |
C34 | −0.4604 (9) | 0.8133 (8) | 0.6121 (9) | 0.068 (3) | |
F35 | −0.5342 (4) | 0.6922 (5) | 0.6367 (5) | 0.082 (2) | |
C35 | −0.5247 (7) | 0.7415 (8) | 0.5664 (7) | 0.055 (3) | |
F36 | −0.6279 (4) | 0.6488 (4) | 0.4219 (4) | 0.0587 (15) | |
C36 | −0.5707 (6) | 0.7224 (7) | 0.4551 (8) | 0.049 (2) | |
C41 | −0.7184 (6) | 0.8388 (7) | 0.2436 (7) | 0.043 (2) | |
F42 | −0.7987 (4) | 0.7506 (4) | 0.3270 (5) | 0.0590 (15) | |
C42 | −0.7970 (6) | 0.8263 (7) | 0.2928 (8) | 0.046 (2) | |
F43 | −0.9431 (4) | 0.8789 (5) | 0.3586 (5) | 0.0777 (19) | |
C43 | −0.8720 (6) | 0.8934 (8) | 0.3068 (8) | 0.056 (3) | |
F44 | −0.9501 (4) | 1.0379 (4) | 0.2838 (5) | 0.0816 (19) | |
C44 | −0.8765 (7) | 0.9704 (8) | 0.2734 (9) | 0.067 (3) | |
C45 | −0.8003 (7) | 0.9841 (6) | 0.2209 (8) | 0.049 (2) | |
F45 | −0.8000 (5) | 1.0628 (4) | 0.1894 (5) | 0.0822 (19) | |
F46 | −0.6533 (4) | 0.9399 (4) | 0.1677 (5) | 0.0607 (15) | |
C46 | −0.7212 (6) | 0.9205 (7) | 0.2146 (8) | 0.055 (3) | |
O90 | 0.1099 (6) | 0.8402 (6) | 0.8557 (8) | 0.088 (2) | |
H90A | 0.088 | 0.882 | 0.820 | 0.105* | |
H90B | 0.1743 | 0.844 | 0.878 | 0.105* | |
Cl01 | −1.132 (3) | 0.927 (3) | 0.088 (4) | 0.116 (8) | 0.315 (5) |
C101 | −1.232 (2) | 0.9610 (17) | 0.150 (2) | 0.100 (5)* | 0.315 (5) |
C102 | −1.325 (2) | 0.996 (3) | 0.089 (2) | 0.100 (5)* | 0.315 (5) |
H102 | −1.3338 | 1.0014 | 0.0151 | 0.120* | 0.315 (5) |
C103 | −1.406 (2) | 1.024 (3) | 0.138 (3) | 0.100 (5)* | 0.315 (5) |
H103 | −1.4679 | 1.0474 | 0.0968 | 0.120* | 0.315 (5) |
C104 | −1.393 (2) | 1.016 (3) | 0.247 (3) | 0.100 (5)* | 0.315 (5) |
H104 | −1.4467 | 1.0344 | 0.2802 | 0.120* | 0.315 (5) |
C105 | −1.300 (3) | 0.981 (3) | 0.308 (3) | 0.100 (5)* | 0.315 (5) |
H105 | −1.2915 | 0.9755 | 0.3819 | 0.120* | 0.315 (5) |
C106 | −1.220 (2) | 0.953 (3) | 0.259 (3) | 0.100 (5)* | 0.315 (5) |
H106 | −1.1575 | 0.9296 | 0.3002 | 0.120* | 0.315 (5) |
Cl11 | −1.111 (3) | 0.895 (3) | 0.076 (4) | 0.116 (8) | 0.315 (5) |
C111 | −1.207 (2) | 0.9370 (18) | 0.141 (3) | 0.100 (5)* | 0.315 (5) |
C112 | −1.303 (3) | 0.968 (3) | 0.080 (2) | 0.100 (5)* | 0.315 (5) |
H112 | −1.3151 | 0.9669 | 0.0043 | 0.120* | 0.315 (5) |
C113 | −1.380 (2) | 1.001 (3) | 0.133 (3) | 0.100 (5)* | 0.315 (5) |
H113 | −1.4433 | 1.0223 | 0.0918 | 0.120* | 0.315 (5) |
C114 | −1.361 (2) | 1.003 (3) | 0.246 (3) | 0.100 (5)* | 0.315 (5) |
H114 | −1.4124 | 1.0257 | 0.2813 | 0.120* | 0.315 (5) |
C115 | −1.266 (3) | 0.972 (3) | 0.307 (3) | 0.100 (5)* | 0.315 (5) |
H115 | −1.2532 | 0.9736 | 0.3832 | 0.120* | 0.315 (5) |
C116 | −1.189 (2) | 0.939 (3) | 0.255 (3) | 0.100 (5)* | 0.315 (5) |
H116 | −1.1250 | 0.9182 | 0.2957 | 0.120* | 0.315 (5) |
Cl21 | −1.293 (6) | 1.026 (7) | 0.431 (4) | 0.145 (9) | 0.185 (5) |
C121 | −1.279 (4) | 1.000 (4) | 0.297 (3) | 0.085 (8)* | 0.185 (5) |
C122 | −1.187 (4) | 0.958 (4) | 0.278 (3) | 0.085 (8)* | 0.185 (5) |
H122 | −1.1339 | 0.9434 | 0.3372 | 0.102* | 0.185 (5) |
C123 | −1.176 (3) | 0.938 (4) | 0.170 (4) | 0.085 (8)* | 0.185 (5) |
H123 | −1.1152 | 0.9100 | 0.1579 | 0.102* | 0.185 (5) |
C124 | −1.256 (4) | 0.960 (4) | 0.082 (3) | 0.085 (8)* | 0.185 (5) |
H124 | −1.2489 | 0.9470 | 0.0100 | 0.102* | 0.185 (5) |
C125 | −1.348 (3) | 1.003 (4) | 0.101 (4) | 0.085 (8)* | 0.185 (5) |
H125 | −1.4012 | 1.0175 | 0.0414 | 0.102* | 0.185 (5) |
C126 | −1.359 (3) | 1.023 (4) | 0.208 (4) | 0.085 (8)* | 0.185 (5) |
H126 | −1.4199 | 1.0509 | 0.2208 | 0.102* | 0.185 (5) |
Cl31 | −1.294 (6) | 1.013 (7) | 0.400 (4) | 0.145 (9) | 0.18 |
C131 | −1.292 (4) | 0.994 (4) | 0.261 (3) | 0.085 (8)* | 0.185 (5) |
C132 | −1.200 (3) | 0.967 (4) | 0.233 (3) | 0.085 (8)* | 0.185 (5) |
H132 | −1.1395 | 0.9592 | 0.2891 | 0.102* | 0.185 (5) |
C133 | −1.199 (3) | 0.951 (4) | 0.123 (3) | 0.085 (8)* | 0.185 (5) |
H133 | −1.1370 | 0.9332 | 0.1041 | 0.102* | 0.185 (5) |
C134 | −1.289 (4) | 0.963 (4) | 0.040 (3) | 0.085 (8)* | 0.185 (5) |
H134 | −1.2883 | 0.9525 | −0.0346 | 0.102* | 0.185 (5) |
C135 | −1.381 (3) | 0.990 (4) | 0.067 (4) | 0.085 (8)* | 0.185 (5) |
H135 | −1.4420 | 0.9977 | 0.0117 | 0.102* | 0.185 (5) |
C136 | −1.383 (3) | 1.006 (4) | 0.178 (4) | 0.085 (8)* | 0.185 (5) |
H136 | −1.4445 | 1.0236 | 0.1967 | 0.102* | 0.185 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ga1 | 0.0226 (4) | 0.0617 (7) | 0.0356 (6) | 0.0006 (4) | 0.0117 (4) | 0.0080 (5) |
Ga2 | 0.0209 (4) | 0.0522 (7) | 0.0435 (6) | 0.0053 (4) | 0.0099 (4) | 0.0082 (5) |
Ga3 | 0.0206 (4) | 0.0570 (7) | 0.0387 (6) | 0.0011 (4) | 0.0097 (4) | 0.0132 (5) |
Ga4 | 0.0214 (4) | 0.0534 (7) | 0.0410 (6) | −0.0029 (4) | 0.0083 (4) | 0.0060 (5) |
Ga5 | 0.0153 (4) | 0.0602 (7) | 0.0409 (6) | 0.0028 (4) | 0.0110 (4) | 0.0106 (5) |
Ga6 | 0.0180 (4) | 0.0610 (7) | 0.0344 (6) | −0.0003 (4) | 0.0064 (4) | 0.0069 (5) |
C1 | 0.061 (6) | 0.085 (8) | 0.021 (5) | −0.002 (6) | −0.002 (4) | 0.005 (5) |
C2 | 0.051 (6) | 0.047 (6) | 0.084 (8) | 0.007 (5) | −0.012 (6) | 0.010 (6) |
C3 | 0.033 (5) | 0.053 (7) | 0.096 (8) | 0.001 (4) | 0.018 (5) | 0.015 (6) |
C4 | 0.033 (5) | 0.060 (7) | 0.052 (6) | −0.016 (4) | 0.011 (4) | 0.000 (5) |
C5 | 0.035 (5) | 0.078 (8) | 0.052 (6) | 0.016 (5) | 0.014 (4) | 0.014 (5) |
C6 | 0.047 (5) | 0.079 (7) | 0.024 (5) | −0.007 (5) | 0.018 (4) | 0.003 (5) |
O7 | 0.015 (2) | 0.057 (4) | 0.041 (3) | 0.008 (2) | 0.010 (2) | 0.011 (3) |
O8 | 0.015 (2) | 0.064 (4) | 0.035 (3) | −0.005 (2) | 0.005 (2) | 0.016 (3) |
O9 | 0.033 (3) | 0.046 (4) | 0.046 (4) | −0.002 (3) | 0.020 (3) | 0.014 (3) |
O10 | 0.021 (3) | 0.050 (4) | 0.047 (4) | 0.001 (2) | 0.012 (3) | −0.002 (3) |
O11 | 0.042 (3) | 0.043 (4) | 0.048 (4) | −0.004 (3) | 0.017 (3) | −0.002 (3) |
O12 | 0.025 (3) | 0.054 (4) | 0.048 (4) | 0.006 (3) | −0.007 (3) | 0.011 (3) |
O13 | 0.019 (3) | 0.069 (4) | 0.061 (4) | −0.005 (3) | 0.014 (3) | 0.021 (3) |
B10 | 0.012 (4) | 0.045 (6) | 0.029 (5) | 0.001 (4) | 0.005 (4) | 0.005 (4) |
C11 | 0.028 (4) | 0.049 (6) | 0.062 (6) | 0.004 (4) | 0.029 (4) | 0.005 (5) |
F12 | 0.029 (2) | 0.071 (4) | 0.055 (3) | 0.010 (2) | 0.007 (2) | 0.018 (3) |
C12 | 0.015 (4) | 0.068 (7) | 0.040 (5) | 0.000 (4) | 0.005 (4) | 0.013 (5) |
F13 | 0.055 (3) | 0.061 (4) | 0.086 (4) | 0.001 (3) | 0.024 (3) | 0.014 (3) |
C13 | 0.033 (5) | 0.051 (6) | 0.052 (6) | 0.011 (4) | 0.018 (4) | 0.005 (5) |
F14 | 0.052 (3) | 0.081 (5) | 0.087 (4) | −0.005 (3) | 0.019 (3) | −0.011 (4) |
C14 | 0.036 (5) | 0.038 (6) | 0.060 (6) | −0.003 (4) | 0.010 (4) | −0.004 (5) |
F15 | 0.032 (3) | 0.106 (5) | 0.059 (4) | −0.009 (3) | −0.002 (3) | −0.011 (3) |
C15 | 0.039 (5) | 0.084 (8) | 0.049 (6) | −0.014 (5) | 0.016 (5) | 0.009 (6) |
F16 | 0.028 (2) | 0.072 (4) | 0.053 (3) | 0.005 (2) | 0.004 (2) | 0.012 (3) |
C16 | 0.028 (5) | 0.063 (7) | 0.049 (6) | 0.002 (4) | 0.008 (4) | 0.008 (5) |
C21 | 0.010 (3) | 0.030 (5) | 0.055 (6) | 0.000 (3) | 0.000 (4) | 0.005 (4) |
F22 | 0.020 (2) | 0.085 (4) | 0.052 (3) | 0.008 (2) | 0.007 (2) | 0.013 (3) |
C22 | 0.036 (5) | 0.046 (6) | 0.070 (7) | −0.002 (4) | 0.021 (5) | 0.005 (5) |
F23 | 0.021 (2) | 0.093 (4) | 0.075 (4) | 0.005 (3) | 0.017 (2) | 0.009 (3) |
C23 | 0.019 (4) | 0.076 (8) | 0.082 (8) | 0.004 (4) | 0.008 (5) | 0.016 (6) |
C24 | 0.034 (5) | 0.059 (7) | 0.072 (8) | −0.007 (4) | 0.022 (5) | −0.003 (6) |
F24 | 0.081 (4) | 0.105 (5) | 0.066 (4) | 0.002 (4) | 0.050 (3) | 0.027 (4) |
F25 | 0.075 (4) | 0.111 (5) | 0.045 (4) | 0.000 (4) | 0.011 (3) | 0.033 (3) |
C25 | 0.052 (6) | 0.082 (8) | 0.041 (6) | −0.009 (5) | 0.002 (5) | 0.011 (6) |
F26 | 0.041 (3) | 0.076 (4) | 0.047 (3) | 0.001 (3) | 0.000 (2) | 0.014 (3) |
C26 | 0.027 (4) | 0.057 (7) | 0.057 (6) | 0.003 (4) | 0.005 (4) | 0.010 (5) |
C31 | 0.030 (4) | 0.057 (7) | 0.038 (5) | 0.007 (4) | 0.005 (4) | 0.005 (5) |
F32 | 0.043 (3) | 0.061 (4) | 0.055 (3) | 0.000 (3) | 0.008 (2) | 0.009 (3) |
C32 | 0.038 (5) | 0.052 (6) | 0.044 (6) | 0.008 (4) | 0.015 (5) | 0.007 (5) |
F33 | 0.069 (4) | 0.082 (5) | 0.062 (4) | 0.003 (3) | 0.005 (3) | −0.018 (3) |
C33 | 0.041 (5) | 0.050 (7) | 0.069 (8) | 0.012 (5) | 0.001 (5) | −0.013 (6) |
F34 | 0.099 (5) | 0.138 (6) | 0.028 (3) | 0.010 (4) | 0.010 (3) | −0.007 (4) |
C34 | 0.069 (7) | 0.078 (9) | 0.047 (7) | 0.049 (7) | 0.023 (6) | 0.005 (7) |
F35 | 0.066 (4) | 0.129 (6) | 0.057 (4) | 0.024 (4) | 0.023 (3) | 0.035 (4) |
C35 | 0.055 (6) | 0.077 (8) | 0.020 (5) | 0.016 (5) | −0.001 (5) | 0.009 (5) |
F36 | 0.054 (3) | 0.077 (4) | 0.043 (3) | 0.010 (3) | 0.009 (3) | 0.019 (3) |
C36 | 0.023 (4) | 0.063 (7) | 0.058 (7) | 0.013 (4) | 0.012 (4) | 0.013 (6) |
C41 | 0.020 (4) | 0.073 (7) | 0.036 (5) | 0.007 (4) | 0.000 (4) | 0.026 (5) |
F42 | 0.037 (3) | 0.066 (4) | 0.082 (4) | 0.006 (3) | 0.025 (3) | 0.023 (3) |
C42 | 0.037 (5) | 0.052 (6) | 0.055 (6) | 0.007 (4) | 0.022 (4) | 0.015 (5) |
F43 | 0.042 (3) | 0.125 (6) | 0.075 (4) | 0.001 (3) | 0.037 (3) | 0.010 (4) |
C43 | 0.013 (4) | 0.083 (8) | 0.060 (7) | −0.005 (5) | −0.002 (4) | −0.001 (6) |
F44 | 0.057 (4) | 0.069 (4) | 0.109 (5) | 0.022 (3) | 0.025 (3) | 0.005 (4) |
C44 | 0.028 (5) | 0.067 (8) | 0.081 (8) | 0.010 (5) | −0.007 (5) | −0.002 (6) |
C45 | 0.049 (6) | 0.037 (6) | 0.057 (6) | 0.004 (4) | 0.015 (5) | 0.004 (5) |
F45 | 0.076 (4) | 0.063 (4) | 0.101 (5) | 0.024 (3) | 0.020 (4) | 0.023 (4) |
F46 | 0.043 (3) | 0.066 (4) | 0.075 (4) | 0.007 (3) | 0.016 (3) | 0.022 (3) |
C46 | 0.027 (5) | 0.071 (8) | 0.055 (6) | 0.011 (5) | 0.000 (4) | 0.005 (6) |
O90 | 0.084 (6) | 0.072 (6) | 0.091 (7) | 0.005 (5) | 0.005 (5) | 0.011 (5) |
Cl01 | 0.115 (14) | 0.13 (3) | 0.105 (10) | −0.019 (12) | 0.043 (7) | 0.002 (14) |
Cl11 | 0.115 (14) | 0.13 (3) | 0.105 (10) | −0.019 (12) | 0.043 (7) | 0.002 (14) |
Cl21 | 0.144 (11) | 0.13 (2) | 0.17 (2) | −0.030 (12) | 0.058 (19) | 0.02 (2) |
Cl31 | 0.144 (11) | 0.13 (2) | 0.17 (2) | −0.030 (12) | 0.058 (19) | 0.02 (2) |
Ga1—O8i | 1.879 (6) | C25—C26 | 1.358 (13) |
Ga1—O7i | 1.898 (5) | F26—C26 | 1.373 (9) |
Ga1—O11 | 1.901 (6) | C31—C32 | 1.351 (12) |
Ga1—C1 | 1.915 (9) | C31—C36 | 1.390 (12) |
Ga2—O7i | 1.843 (6) | F32—C32 | 1.380 (10) |
Ga2—O10 | 1.898 (5) | C32—C33 | 1.370 (13) |
Ga2—C2 | 1.910 (9) | F33—C33 | 1.350 (11) |
Ga2—O12 | 1.950 (5) | C33—C34 | 1.392 (15) |
Ga3—O10 | 1.842 (5) | F34—C34 | 1.342 (11) |
Ga3—O8 | 1.868 (6) | C34—C35 | 1.392 (15) |
Ga3—C3 | 1.879 (10) | F35—C35 | 1.324 (11) |
Ga3—O13 | 1.929 (5) | C35—C36 | 1.356 (12) |
Ga4—O9 | 1.868 (6) | F36—C36 | 1.355 (11) |
Ga4—O10 | 1.884 (5) | C41—C46 | 1.362 (13) |
Ga4—O11 | 1.925 (5) | C41—C42 | 1.430 (11) |
Ga4—C4 | 1.945 (8) | F42—C42 | 1.319 (10) |
Ga5—O7 | 1.875 (5) | C42—C43 | 1.381 (12) |
Ga5—O9 | 1.881 (5) | F43—C43 | 1.374 (11) |
Ga5—C5 | 1.917 (8) | C43—C44 | 1.318 (14) |
Ga5—O13 | 1.920 (6) | F44—C44 | 1.365 (11) |
Ga6—O9 | 1.863 (5) | C44—C45 | 1.436 (14) |
Ga6—O8i | 1.876 (5) | C45—F45 | 1.341 (10) |
Ga6—O12i | 1.916 (6) | C45—C46 | 1.372 (12) |
Ga6—C6 | 1.934 (8) | F46—C46 | 1.320 (11) |
C1—H1A | 0.9600 | O90—H90A | 0.842 |
C1—H1B | 0.9600 | O90—H90B | 0.838 |
C1—H1C | 0.9600 | Cl01—C101 | 1.7400 |
C2—H2A | 0.9600 | C101—C102 | 1.3900 |
C2—H2B | 0.9600 | C101—C106 | 1.3900 |
C2—H2C | 0.9600 | C102—C103 | 1.3900 |
C3—H3A | 0.9600 | C102—H102 | 0.9300 |
C3—H3B | 0.9600 | C103—C104 | 1.3900 |
C3—H3C | 0.9600 | C103—H103 | 0.9300 |
C4—H4A | 0.9600 | C104—C105 | 1.3900 |
C4—H4B | 0.9600 | C104—H104 | 0.9300 |
C4—H4C | 0.9600 | C105—C106 | 1.3900 |
C5—H5A | 0.9600 | C105—H105 | 0.9300 |
C5—H5B | 0.9600 | C106—H106 | 0.9300 |
C5—H5C | 0.9600 | Cl11—C111 | 1.7400 |
C6—H6A | 0.9600 | C111—C112 | 1.3900 |
C6—H6B | 0.9600 | C111—C116 | 1.3900 |
C6—H6C | 0.9600 | C112—C113 | 1.3900 |
O7—Ga2i | 1.843 (6) | C112—H112 | 0.9300 |
O7—Ga1i | 1.898 (5) | C113—C114 | 1.3900 |
O8—Ga6i | 1.876 (5) | C113—H113 | 0.9300 |
O8—Ga1i | 1.879 (6) | C114—C115 | 1.3900 |
O11—H11 | 0.8400 | C114—H114 | 0.9300 |
O12—Ga6i | 1.916 (6) | C115—C116 | 1.3900 |
O12—H12 | 0.8400 | C115—H115 | 0.9300 |
O13—H13 | 0.8400 | C116—H116 | 0.9300 |
B10—C31 | 1.613 (12) | Cl21—C121 | 1.7400 |
B10—C41 | 1.662 (12) | C121—C126 | 1.3900 |
B10—C11 | 1.677 (12) | C121—C122 | 1.3900 |
B10—C21 | 1.696 (11) | C122—C123 | 1.3900 |
C11—C16 | 1.389 (11) | C122—H122 | 0.9300 |
C11—C12 | 1.425 (12) | C123—C124 | 1.3900 |
F12—C12 | 1.358 (8) | C123—H123 | 0.9300 |
C12—C13 | 1.317 (12) | C124—C125 | 1.3900 |
F13—C13 | 1.348 (10) | C124—H124 | 0.9300 |
C13—C14 | 1.402 (12) | C125—C126 | 1.3900 |
F14—C14 | 1.357 (10) | C125—H125 | 0.9300 |
C14—C15 | 1.389 (13) | C126—H126 | 0.9300 |
F15—C15 | 1.326 (10) | Cl31—C131 | 1.7400 |
C15—C16 | 1.361 (13) | C131—C136 | 1.3900 |
F16—C16 | 1.357 (10) | C131—C132 | 1.3900 |
C21—C22 | 1.403 (11) | C132—C133 | 1.3900 |
C21—C26 | 1.427 (12) | C132—H132 | 0.9300 |
F22—C22 | 1.401 (10) | C133—C134 | 1.3900 |
C22—C23 | 1.343 (13) | C133—H133 | 0.9300 |
F23—C23 | 1.406 (9) | C134—C135 | 1.3900 |
C23—C24 | 1.324 (13) | C134—H134 | 0.9300 |
C24—F24 | 1.324 (10) | C135—C136 | 1.3900 |
C24—C25 | 1.428 (12) | C135—H135 | 0.9300 |
F25—C25 | 1.317 (10) | C136—H136 | 0.9300 |
O8i—Ga1—O7i | 102.2 (2) | F22—C22—C21 | 118.2 (8) |
O8i—Ga1—O11 | 98.5 (2) | C24—C23—C22 | 123.1 (8) |
O7i—Ga1—O11 | 97.5 (2) | C24—C23—F23 | 119.1 (9) |
O8i—Ga1—C1 | 122.3 (3) | C22—C23—F23 | 117.8 (9) |
O7i—Ga1—C1 | 118.9 (3) | F24—C24—C23 | 124.5 (9) |
O11—Ga1—C1 | 113.1 (4) | F24—C24—C25 | 118.0 (10) |
O7i—Ga2—O10 | 104.3 (2) | C23—C24—C25 | 117.5 (9) |
O7i—Ga2—C2 | 119.2 (4) | F25—C25—C26 | 121.7 (9) |
O10—Ga2—C2 | 121.4 (4) | F25—C25—C24 | 121.0 (9) |
O7i—Ga2—O12 | 97.8 (2) | C26—C25—C24 | 117.2 (9) |
O10—Ga2—O12 | 96.9 (2) | C25—C26—F26 | 116.4 (8) |
C2—Ga2—O12 | 112.7 (3) | C25—C26—C21 | 127.5 (8) |
O10—Ga3—O8 | 104.1 (2) | F26—C26—C21 | 116.0 (8) |
O10—Ga3—C3 | 119.8 (4) | C32—C31—C36 | 112.8 (9) |
O8—Ga3—C3 | 117.9 (3) | C32—C31—B10 | 122.4 (9) |
O10—Ga3—O13 | 96.1 (2) | C36—C31—B10 | 124.5 (8) |
O8—Ga3—O13 | 97.8 (2) | C31—C32—C33 | 126.9 (10) |
C3—Ga3—O13 | 117.0 (3) | C31—C32—F32 | 118.7 (8) |
O9—Ga4—O10 | 101.8 (2) | C33—C32—F32 | 114.3 (9) |
O9—Ga4—O11 | 97.7 (2) | F33—C33—C32 | 122.1 (11) |
O10—Ga4—O11 | 99.6 (2) | F33—C33—C34 | 119.3 (10) |
O9—Ga4—C4 | 119.8 (3) | C32—C33—C34 | 118.4 (10) |
O10—Ga4—C4 | 121.7 (3) | F34—C34—C35 | 123.6 (11) |
O11—Ga4—C4 | 112.0 (3) | F34—C34—C33 | 119.4 (12) |
O7—Ga5—O9 | 103.2 (2) | C35—C34—C33 | 116.9 (10) |
O7—Ga5—C5 | 117.0 (3) | F35—C35—C36 | 122.9 (11) |
O9—Ga5—C5 | 120.1 (3) | F35—C35—C34 | 116.2 (9) |
O7—Ga5—O13 | 98.1 (2) | C36—C35—C34 | 120.9 (11) |
O9—Ga5—O13 | 98.0 (2) | F36—C36—C35 | 114.4 (10) |
C5—Ga5—O13 | 116.7 (3) | F36—C36—C31 | 121.6 (8) |
O9—Ga6—O8i | 104.4 (2) | C35—C36—C31 | 124.0 (10) |
O9—Ga6—O12i | 98.9 (3) | C46—C41—C42 | 116.1 (8) |
O8i—Ga6—O12i | 97.2 (2) | C46—C41—B10 | 128.7 (8) |
O9—Ga6—C6 | 115.5 (3) | C42—C41—B10 | 114.3 (8) |
O8i—Ga6—C6 | 123.1 (3) | F42—C42—C43 | 118.5 (8) |
O12i—Ga6—C6 | 113.6 (3) | F42—C42—C41 | 120.5 (8) |
Ga1—C1—H1A | 109.5 | C43—C42—C41 | 120.9 (9) |
Ga1—C1—H1B | 109.5 | C44—C43—F43 | 119.5 (9) |
H1A—C1—H1B | 109.5 | C44—C43—C42 | 122.2 (10) |
Ga1—C1—H1C | 109.5 | F43—C43—C42 | 118.3 (10) |
H1A—C1—H1C | 109.5 | C43—C44—F44 | 124.2 (11) |
H1B—C1—H1C | 109.5 | C43—C44—C45 | 118.3 (9) |
Ga2—C2—H2A | 109.5 | F44—C44—C45 | 117.5 (10) |
Ga2—C2—H2B | 109.5 | F45—C45—C46 | 120.0 (9) |
H2A—C2—H2B | 109.5 | F45—C45—C44 | 120.1 (8) |
Ga2—C2—H2C | 109.5 | C46—C45—C44 | 119.5 (10) |
H2A—C2—H2C | 109.5 | F46—C46—C41 | 121.8 (8) |
H2B—C2—H2C | 109.5 | F46—C46—C45 | 115.4 (10) |
Ga3—C3—H3A | 109.5 | C41—C46—C45 | 122.5 (10) |
Ga3—C3—H3B | 109.5 | H90A—O90—H90B | 105.2 |
H3A—C3—H3B | 109.5 | C102—C101—C106 | 120.0 |
Ga3—C3—H3C | 109.5 | C102—C101—Cl01 | 120.0 |
H3A—C3—H3C | 109.5 | C106—C101—Cl01 | 120.0 |
H3B—C3—H3C | 109.5 | C101—C102—C103 | 120.0 |
Ga4—C4—H4A | 109.5 | C101—C102—H102 | 120.0 |
Ga4—C4—H4B | 109.5 | C103—C102—H102 | 120.0 |
H4A—C4—H4B | 109.5 | C104—C103—C102 | 120.0 |
Ga4—C4—H4C | 109.5 | C104—C103—H103 | 120.0 |
H4A—C4—H4C | 109.5 | C102—C103—H103 | 120.0 |
H4B—C4—H4C | 109.5 | C105—C104—C103 | 120.0 |
Ga5—C5—H5A | 109.5 | C105—C104—H104 | 120.0 |
Ga5—C5—H5B | 109.5 | C103—C104—H104 | 120.0 |
H5A—C5—H5B | 109.5 | C106—C105—C104 | 120.0 |
Ga5—C5—H5C | 109.5 | C106—C105—H105 | 120.0 |
H5A—C5—H5C | 109.5 | C104—C105—H105 | 120.0 |
H5B—C5—H5C | 109.5 | C105—C106—C101 | 120.0 |
Ga6—C6—H6A | 109.5 | C105—C106—H106 | 120.0 |
Ga6—C6—H6B | 109.5 | C101—C106—H106 | 120.0 |
H6A—C6—H6B | 109.5 | C112—C111—C116 | 120.0 |
Ga6—C6—H6C | 109.5 | C112—C111—Cl11 | 120.0 |
H6A—C6—H6C | 109.5 | C116—C111—Cl11 | 120.0 |
H6B—C6—H6C | 109.5 | C111—C112—C113 | 120.0 |
Ga2i—O7—Ga5 | 120.9 (3) | C111—C112—H112 | 120.0 |
Ga2i—O7—Ga1i | 119.4 (3) | C113—C112—H112 | 120.0 |
Ga5—O7—Ga1i | 119.7 (3) | C114—C113—C112 | 120.0 |
Ga3—O8—Ga6i | 120.1 (3) | C114—C113—H113 | 120.0 |
Ga3—O8—Ga1i | 120.7 (2) | C112—C113—H113 | 120.0 |
Ga6i—O8—Ga1i | 118.9 (3) | C113—C114—C115 | 120.0 |
Ga6—O9—Ga4 | 120.0 (3) | C113—C114—H114 | 120.0 |
Ga6—O9—Ga5 | 119.4 (3) | C115—C114—H114 | 120.0 |
Ga4—O9—Ga5 | 120.5 (3) | C116—C115—C114 | 120.0 |
Ga3—O10—Ga4 | 123.5 (3) | C116—C115—H115 | 120.0 |
Ga3—O10—Ga2 | 119.8 (3) | C114—C115—H115 | 120.0 |
Ga4—O10—Ga2 | 116.6 (3) | C111—C116—C115 | 120.0 |
Ga1—O11—Ga4 | 129.0 (3) | C111—C116—H116 | 120.0 |
Ga1—O11—H11 | 115.5 | C115—C116—H116 | 120.0 |
Ga4—O11—H11 | 115.5 | C126—C121—C122 | 120.0 |
Ga6i—O12—Ga2 | 127.7 (3) | C126—C121—Cl21 | 120.0 |
Ga6i—O12—H12 | 116.2 | C122—C121—Cl21 | 120.0 |
Ga2—O12—H12 | 116.2 | C123—C122—C121 | 120.0 |
Ga5—O13—Ga3 | 128.5 (3) | C123—C122—H122 | 120.0 |
Ga5—O13—H13 | 115.8 | C121—C122—H122 | 120.0 |
Ga3—O13—H13 | 115.8 | C124—C123—C122 | 120.0 |
C31—B10—C41 | 103.7 (6) | C124—C123—H123 | 120.0 |
C31—B10—C11 | 115.9 (7) | C122—C123—H123 | 120.0 |
C41—B10—C11 | 114.9 (6) | C123—C124—C125 | 120.0 |
C31—B10—C21 | 113.3 (6) | C123—C124—H124 | 120.0 |
C41—B10—C21 | 110.9 (7) | C125—C124—H124 | 120.0 |
C11—B10—C21 | 98.3 (6) | C126—C125—C124 | 120.0 |
C16—C11—C12 | 111.4 (8) | C126—C125—H125 | 120.0 |
C16—C11—B10 | 127.3 (8) | C124—C125—H125 | 120.0 |
C12—C11—B10 | 120.8 (7) | C121—C126—C125 | 120.0 |
C13—C12—F12 | 117.4 (8) | C121—C126—H126 | 120.0 |
C13—C12—C11 | 126.3 (8) | C125—C126—H126 | 120.0 |
F12—C12—C11 | 116.1 (8) | C136—C131—C132 | 120.0 |
C12—C13—F13 | 121.7 (8) | C136—C131—Cl31 | 120.0 |
C12—C13—C14 | 118.9 (8) | C132—C131—Cl31 | 120.0 |
F13—C13—C14 | 119.3 (9) | C133—C132—C131 | 120.0 |
F14—C14—C15 | 120.2 (8) | C133—C132—H132 | 120.0 |
F14—C14—C13 | 120.5 (8) | C131—C132—H132 | 120.0 |
C15—C14—C13 | 118.8 (9) | C132—C133—C134 | 120.0 |
F15—C15—C16 | 121.3 (9) | C132—C133—H133 | 120.0 |
F15—C15—C14 | 119.5 (9) | C134—C133—H133 | 120.0 |
C16—C15—C14 | 119.0 (8) | C135—C134—C133 | 120.0 |
F16—C16—C15 | 114.4 (8) | C135—C134—H134 | 120.0 |
F16—C16—C11 | 120.3 (9) | C133—C134—H134 | 120.0 |
C15—C16—C11 | 125.3 (9) | C134—C135—C136 | 120.0 |
C22—C21—C26 | 108.9 (8) | C134—C135—H135 | 120.0 |
C22—C21—B10 | 128.9 (8) | C136—C135—H135 | 120.0 |
C26—C21—B10 | 121.9 (6) | C131—C136—C135 | 120.0 |
C23—C22—F22 | 116.1 (8) | C131—C136—H136 | 120.0 |
C23—C22—C21 | 125.7 (9) | C135—C136—H136 | 120.0 |
O9—Ga5—O7—Ga2i | −62.6 (3) | F23—C23—C24—F24 | −1.9 (16) |
C5—Ga5—O7—Ga2i | 71.6 (4) | C22—C23—C24—C25 | −1.6 (16) |
O13—Ga5—O7—Ga2i | −162.9 (3) | F23—C23—C24—C25 | 178.7 (9) |
O9—Ga5—O7—Ga1i | 115.0 (3) | F24—C24—C25—F25 | 1.4 (15) |
C5—Ga5—O7—Ga1i | −110.8 (4) | C23—C24—C25—F25 | −179.1 (10) |
O13—Ga5—O7—Ga1i | 14.8 (3) | F24—C24—C25—C26 | −177.0 (9) |
O10—Ga3—O8—Ga6i | 62.3 (3) | C23—C24—C25—C26 | 2.5 (15) |
C3—Ga3—O8—Ga6i | −73.2 (5) | F25—C25—C26—F26 | 2.5 (15) |
O13—Ga3—O8—Ga6i | 160.6 (3) | C24—C25—C26—F26 | −179.1 (8) |
O10—Ga3—O8—Ga1i | −111.6 (3) | F25—C25—C26—C21 | −179.1 (9) |
C3—Ga3—O8—Ga1i | 113.0 (4) | C24—C25—C26—C21 | −0.7 (16) |
O13—Ga3—O8—Ga1i | −13.3 (3) | C22—C21—C26—C25 | −1.8 (14) |
O8i—Ga6—O9—Ga4 | 62.0 (3) | B10—C21—C26—C25 | −175.8 (9) |
O12i—Ga6—O9—Ga4 | 161.9 (3) | C22—C21—C26—F26 | 176.6 (7) |
C6—Ga6—O9—Ga4 | −76.5 (4) | B10—C21—C26—F26 | 2.6 (12) |
O8i—Ga6—O9—Ga5 | −112.7 (3) | C41—B10—C31—C32 | −71.4 (10) |
O12i—Ga6—O9—Ga5 | −12.8 (3) | C11—B10—C31—C32 | 161.6 (7) |
C6—Ga6—O9—Ga5 | 108.9 (4) | C21—B10—C31—C32 | 49.0 (11) |
O10—Ga4—O9—Ga6 | −114.9 (3) | C41—B10—C31—C36 | 101.8 (9) |
O11—Ga4—O9—Ga6 | −13.4 (3) | C11—B10—C31—C36 | −25.2 (11) |
C4—Ga4—O9—Ga6 | 107.5 (4) | C21—B10—C31—C36 | −137.8 (8) |
O10—Ga4—O9—Ga5 | 59.6 (3) | C36—C31—C32—C33 | −1.0 (13) |
O11—Ga4—O9—Ga5 | 161.2 (3) | B10—C31—C32—C33 | 173.0 (8) |
C4—Ga4—O9—Ga5 | −77.9 (4) | C36—C31—C32—F32 | −176.4 (7) |
O7—Ga5—O9—Ga6 | 61.5 (3) | B10—C31—C32—F32 | −2.5 (12) |
C5—Ga5—O9—Ga6 | −71.0 (5) | C31—C32—C33—F33 | 179.4 (8) |
O13—Ga5—O9—Ga6 | 161.8 (3) | F32—C32—C33—F33 | −4.9 (12) |
O7—Ga5—O9—Ga4 | −113.2 (3) | C31—C32—C33—C34 | 2.7 (14) |
C5—Ga5—O9—Ga4 | 114.4 (4) | F32—C32—C33—C34 | 178.4 (8) |
O13—Ga5—O9—Ga4 | −12.8 (3) | F33—C33—C34—F34 | 3.5 (13) |
O8—Ga3—O10—Ga4 | 113.3 (3) | C32—C33—C34—F34 | −179.7 (8) |
C3—Ga3—O10—Ga4 | −112.2 (4) | F33—C33—C34—C35 | 179.1 (8) |
O13—Ga3—O10—Ga4 | 13.7 (4) | C32—C33—C34—C35 | −4.1 (13) |
O8—Ga3—O10—Ga2 | −62.1 (4) | F34—C34—C35—F35 | −3.1 (14) |
C3—Ga3—O10—Ga2 | 72.3 (5) | C33—C34—C35—F35 | −178.6 (8) |
O13—Ga3—O10—Ga2 | −161.7 (3) | F34—C34—C35—C36 | 179.5 (8) |
O9—Ga4—O10—Ga3 | −61.8 (4) | C33—C34—C35—C36 | 4.1 (14) |
O11—Ga4—O10—Ga3 | −161.9 (3) | F35—C35—C36—F36 | 0.5 (13) |
C4—Ga4—O10—Ga3 | 74.8 (5) | C34—C35—C36—F36 | 177.7 (8) |
O9—Ga4—O10—Ga2 | 113.8 (3) | F35—C35—C36—C31 | −179.7 (8) |
O11—Ga4—O10—Ga2 | 13.7 (4) | C34—C35—C36—C31 | −2.5 (14) |
C4—Ga4—O10—Ga2 | −109.7 (4) | C32—C31—C36—F36 | −179.4 (7) |
O7i—Ga2—O10—Ga3 | 112.4 (3) | B10—C31—C36—F36 | 6.8 (13) |
C2—Ga2—O10—Ga3 | −109.5 (5) | C32—C31—C36—C35 | 0.8 (13) |
O12—Ga2—O10—Ga3 | 12.5 (4) | B10—C31—C36—C35 | −173.0 (8) |
O7i—Ga2—O10—Ga4 | −63.3 (3) | C31—B10—C41—C46 | 97.3 (10) |
C2—Ga2—O10—Ga4 | 74.8 (5) | C11—B10—C41—C46 | −135.1 (9) |
O12—Ga2—O10—Ga4 | −163.2 (3) | C21—B10—C41—C46 | −24.7 (12) |
O8i—Ga1—O11—Ga4 | 52.4 (4) | C31—B10—C41—C42 | −71.5 (9) |
O7i—Ga1—O11—Ga4 | −51.2 (4) | C11—B10—C41—C42 | 56.1 (10) |
C1—Ga1—O11—Ga4 | −177.0 (4) | C21—B10—C41—C42 | 166.5 (7) |
O9—Ga4—O11—Ga1 | −52.1 (4) | C46—C41—C42—F42 | −177.8 (8) |
O10—Ga4—O11—Ga1 | 51.3 (4) | B10—C41—C42—F42 | −7.5 (12) |
C4—Ga4—O11—Ga1 | −178.7 (4) | C46—C41—C42—C43 | 1.5 (13) |
O7i—Ga2—O12—Ga6i | −51.2 (4) | B10—C41—C42—C43 | 171.8 (8) |
O10—Ga2—O12—Ga6i | 54.3 (4) | F42—C42—C43—C44 | −179.0 (9) |
C2—Ga2—O12—Ga6i | −177.4 (5) | C41—C42—C43—C44 | 1.7 (15) |
O7—Ga5—O13—Ga3 | 51.4 (4) | F42—C42—C43—F43 | 1.8 (13) |
O9—Ga5—O13—Ga3 | −53.3 (4) | C41—C42—C43—F43 | −177.5 (8) |
C5—Ga5—O13—Ga3 | 177.2 (4) | F43—C43—C44—F44 | −1.9 (15) |
O10—Ga3—O13—Ga5 | 52.7 (4) | C42—C43—C44—F44 | 178.9 (9) |
O8—Ga3—O13—Ga5 | −52.4 (4) | F43—C43—C44—C45 | 179.1 (8) |
C3—Ga3—O13—Ga5 | −179.3 (5) | C42—C43—C44—C45 | 0.0 (15) |
C31—B10—C11—C16 | 136.6 (9) | C43—C44—C45—F45 | −177.6 (9) |
C41—B10—C11—C16 | 15.4 (12) | F44—C44—C45—F45 | 3.4 (13) |
C21—B10—C11—C16 | −102.4 (9) | C43—C44—C45—C46 | −4.9 (14) |
C31—B10—C11—C12 | −52.5 (10) | F44—C44—C45—C46 | 176.1 (8) |
C41—B10—C11—C12 | −173.7 (7) | C42—C41—C46—F46 | −179.5 (8) |
C21—B10—C11—C12 | 68.5 (9) | B10—C41—C46—F46 | 11.9 (14) |
C16—C11—C12—C13 | −5.4 (14) | C42—C41—C46—C45 | −6.5 (13) |
B10—C11—C12—C13 | −177.6 (8) | B10—C41—C46—C45 | −175.2 (8) |
C16—C11—C12—F12 | 179.6 (7) | F45—C45—C46—F46 | −5.5 (13) |
B10—C11—C12—F12 | 7.4 (12) | C44—C45—C46—F46 | −178.2 (8) |
F12—C12—C13—F13 | 0.6 (13) | F45—C45—C46—C41 | −178.8 (8) |
C11—C12—C13—F13 | −174.4 (8) | C44—C45—C46—C41 | 8.4 (14) |
F12—C12—C13—C14 | 175.6 (8) | C106—C101—C102—C103 | 0.0 |
C11—C12—C13—C14 | 0.7 (15) | Cl01—C101—C102—C103 | 180.0 |
C12—C13—C14—F14 | 174.4 (9) | C101—C102—C103—C104 | 0.0 |
F13—C13—C14—F14 | −10.4 (14) | C102—C103—C104—C105 | 0.0 |
C12—C13—C14—C15 | 3.3 (14) | C103—C104—C105—C106 | 0.0 |
F13—C13—C14—C15 | 178.5 (8) | C104—C105—C106—C101 | 0.0 |
F14—C14—C15—F15 | 1.2 (14) | C102—C101—C106—C105 | 0.0 |
C13—C14—C15—F15 | 172.4 (8) | Cl01—C101—C106—C105 | 180.0 |
F14—C14—C15—C16 | −173.1 (9) | C116—C111—C112—C113 | 0.0 |
C13—C14—C15—C16 | −2.0 (15) | Cl11—C111—C112—C113 | 180.0 |
F15—C15—C16—F16 | 4.3 (13) | C111—C112—C113—C114 | 0.0 |
C14—C15—C16—F16 | 178.6 (8) | C112—C113—C114—C115 | 0.0 |
F15—C15—C16—C11 | −177.7 (8) | C113—C114—C115—C116 | 0.0 |
C14—C15—C16—C11 | −3.4 (15) | C112—C111—C116—C115 | 0.0 |
C12—C11—C16—F16 | −175.4 (8) | Cl11—C111—C116—C115 | 180.0 |
B10—C11—C16—F16 | −3.8 (14) | C114—C115—C116—C111 | 0.0 |
C12—C11—C16—C15 | 6.7 (14) | C126—C121—C122—C123 | 0.0 |
B10—C11—C16—C15 | 178.3 (9) | Cl21—C121—C122—C123 | 180.0 |
C31—B10—C21—C22 | 20.5 (12) | C121—C122—C123—C124 | 0.0 |
C41—B10—C21—C22 | 136.7 (9) | C122—C123—C124—C125 | 0.0 |
C11—B10—C21—C22 | −102.5 (9) | C123—C124—C125—C126 | 0.0 |
C31—B10—C21—C26 | −166.8 (8) | C122—C121—C126—C125 | 0.0 |
C41—B10—C21—C26 | −50.6 (10) | Cl21—C121—C126—C125 | 180.0 |
C11—B10—C21—C26 | 70.2 (9) | C124—C125—C126—C121 | 0.0 |
C26—C21—C22—C23 | 2.9 (13) | C136—C131—C132—C133 | 0.0 |
B10—C21—C22—C23 | 176.3 (9) | Cl31—C131—C132—C133 | 180.0 |
C26—C21—C22—F22 | −176.2 (7) | C131—C132—C133—C134 | 0.0 |
B10—C21—C22—F22 | −2.8 (13) | C132—C133—C134—C135 | 0.0 |
F22—C22—C23—C24 | 177.7 (9) | C133—C134—C135—C136 | 0.0 |
C21—C22—C23—C24 | −1.4 (17) | C132—C131—C136—C135 | 0.0 |
F22—C22—C23—F23 | −2.5 (13) | Cl31—C131—C136—C135 | 180.0 |
C21—C22—C23—F23 | 178.3 (8) | C134—C135—C136—C131 | 0.0 |
C22—C23—C24—F24 | 177.9 (9) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O90 | 0.84 | 1.85 | 2.686 (10) | 179 |
O12—H12···F22 | 0.84 | 2.13 | 2.924 (7) | 157 |
O90—H90A···F44ii | 0.84 | 2.33 | 3.090 (10) | 150 |
O90—H90B···F26iii | 0.84 | 2.36 | 2.955 (10) | 129 |
Symmetry codes: (ii) −x−1, −y+2, −z+1; (iii) x+1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ga12C12H42O14](C24F20B)2·2C6H5Cl·2H2O |
Mr | 2866.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 210 |
a, b, c (Å) | 13.532 (3), 15.223 (5), 12.755 (3) |
α, β, γ (°) | 101.98 (2), 106.91 (2), 83.71 (2) |
V (Å3) | 2455.7 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.42 |
Crystal size (mm) | 0.34 × 0.28 × 0.18 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scans (MolEN; Fair, 1990) |
Tmin, Tmax | 0.329, 0.540 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10851, 8067, 4561 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.122, 1.11 |
No. of reflections | 8067 |
No. of parameters | 620 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.76 |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, MolEN (Fair, 1990), SHELXTL (Sheldrick, 1995), SHELXL97 (Sheldrick, 1997), SHELXTL.
Ga1—O8i | 1.879 (6) | Ga4—O9 | 1.868 (6) |
Ga1—O7i | 1.898 (5) | Ga4—O10 | 1.884 (5) |
Ga1—O11 | 1.901 (6) | Ga4—O11 | 1.925 (5) |
Ga1—C1 | 1.915 (9) | Ga4—C4 | 1.945 (8) |
Ga2—O7i | 1.843 (6) | Ga5—O7 | 1.875 (5) |
Ga2—O10 | 1.898 (5) | Ga5—O9 | 1.881 (5) |
Ga2—C2 | 1.910 (9) | Ga5—C5 | 1.917 (8) |
Ga2—O12 | 1.950 (5) | Ga5—O13 | 1.920 (6) |
Ga3—O10 | 1.842 (5) | Ga6—O9 | 1.863 (5) |
Ga3—O8 | 1.868 (6) | Ga6—O8i | 1.876 (5) |
Ga3—C3 | 1.879 (10) | Ga6—O12i | 1.916 (6) |
Ga3—O13 | 1.929 (5) | Ga6—C6 | 1.934 (8) |
O8i—Ga1—O7i | 102.2 (2) | O9—Ga5—C5 | 120.1 (3) |
O8i—Ga1—O11 | 98.5 (2) | O7—Ga5—O13 | 98.1 (2) |
O7i—Ga1—O11 | 97.5 (2) | O9—Ga5—O13 | 98.0 (2) |
O8i—Ga1—C1 | 122.3 (3) | C5—Ga5—O13 | 116.7 (3) |
O7i—Ga1—C1 | 118.9 (3) | O9—Ga6—O8i | 104.4 (2) |
O11—Ga1—C1 | 113.1 (4) | O9—Ga6—O12i | 98.9 (3) |
O7i—Ga2—O10 | 104.3 (2) | O8i—Ga6—O12i | 97.2 (2) |
O7i—Ga2—C2 | 119.2 (4) | O9—Ga6—C6 | 115.5 (3) |
O10—Ga2—C2 | 121.4 (4) | O8i—Ga6—C6 | 123.1 (3) |
O7i—Ga2—O12 | 97.8 (2) | O12i—Ga6—C6 | 113.6 (3) |
O10—Ga2—O12 | 96.9 (2) | Ga2i—O7—Ga5 | 120.9 (3) |
C2—Ga2—O12 | 112.7 (3) | Ga2i—O7—Ga1i | 119.4 (3) |
O10—Ga3—O8 | 104.1 (2) | Ga5—O7—Ga1i | 119.7 (3) |
O10—Ga3—C3 | 119.8 (4) | Ga3—O8—Ga6i | 120.1 (3) |
O8—Ga3—C3 | 117.9 (3) | Ga3—O8—Ga1i | 120.7 (2) |
O10—Ga3—O13 | 96.1 (2) | Ga6i—O8—Ga1i | 118.9 (3) |
O8—Ga3—O13 | 97.8 (2) | Ga6—O9—Ga4 | 120.0 (3) |
C3—Ga3—O13 | 117.0 (3) | Ga6—O9—Ga5 | 119.4 (3) |
O9—Ga4—O10 | 101.8 (2) | Ga4—O9—Ga5 | 120.5 (3) |
O9—Ga4—O11 | 97.7 (2) | Ga3—O10—Ga4 | 123.5 (3) |
O10—Ga4—O11 | 99.6 (2) | Ga3—O10—Ga2 | 119.8 (3) |
O9—Ga4—C4 | 119.8 (3) | Ga4—O10—Ga2 | 116.6 (3) |
O10—Ga4—C4 | 121.7 (3) | Ga1—O11—Ga4 | 129.0 (3) |
O11—Ga4—C4 | 112.0 (3) | Ga6i—O12—Ga2 | 127.7 (3) |
O7—Ga5—O9 | 103.2 (2) | Ga5—O13—Ga3 | 128.5 (3) |
O7—Ga5—C5 | 117.0 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O90 | 0.84 | 1.85 | 2.686 (10) | 179 |
O12—H12···F22 | 0.84 | 2.13 | 2.924 (7) | 157 |
O90—H90A···F44ii | 0.84 | 2.33 | 3.090 (10) | 150 |
O90—H90B···F26iii | 0.84 | 2.36 | 2.955 (10) | 129 |
Symmetry codes: (ii) −x−1, −y+2, −z+1; (iii) x+1, y, z+1. |
In recent reports, we have described the chemistry of novel cationic group 13 alkyl complexes, some of which polymerize ethylene (Coles & Jordan, 1997; Ihara et al., 1998; Radzewich et al., 1998, 1999; Korolev et al., 1999; Dagorne et al., 2000). In the course of these studies, we found that the dinuclear cationic Ga–amidinate complex [{tBuC(NiPr)2}GaMe2.{tBuC(NiPr)2}GaMe][B(C6F5)4], (I), is hydrolyzed to the unexpected dicationic gallium–oxo–hydroxide cage compound [Ga12Me12(µ3-O)8(µ-OH)6][B(C6F5)4]2 2H2O, (II). The molecular structure of (II) solvated with chlorobenzene is reported here.
Compound (II) crystallizes as [Ga12Me12(µ3-O)8(µ-OH)6]2+ dications (Fig. 1) that are associated with the hydrate molecules and the [B(C6F5)4]− anions by hydrogen bonds and one O—H···π-ring interaction. Two chlorobenzene solvate molecules are also present in the crystal structure. The dication of (II) adopts a cage structure that is composed of 12 fused six-membered Ga3O3 rings and is positioned on a center of symmetry. Each Ga–Me unit is coordinated to two µ3-O atoms and one µ-OH group. The cage structure of the [Ga12Me12(µ3-O)8(µ-OH)6]2+ dication is very similar to that of the neutral gallium–oxo–hydroxide complex Ga12tBu12(µ3-O)8(µ-O)2(µ-OH)4 (Barron et al., 1995), which is a doubly deprotonated analogue of (II). The Ga centers in (II) exhibit slightly distorted tetrahedral geometries. The O—Ga—O bond angles [average 100 (3)°] are smaller than the ideal tetrahedral value, which is compensated for by an opening of the O—Ga—C bond angles [average 118 (3)°]. The Ga—(µ3-O) bond distances [average 1.87 (2) Å] are comparable to the Ga—O bond distances in gallium oxide (1.87–1.89 Å; Barron et al., 1995) and to the Ga—(µ3-O) distances in Ga12tBu12(µ3-O)8(µ-O)2(µ-OH)4 (1.878–1.915 Å; Barron et al., 1995) and Ga6Mes6(µ3-O)4(µ3-OH)4·6THF (Mes is mesityl; 1.855–1.896 Å; Roesky et al., 1994). The µ3-O centers exhibit trigonal–planar geometry. The Ga—(µ-OH) bond distances [average 1.92 (2) Å] are similar to those in the dinuclear Ga cation [(iPr2—ATI)GaMe]2(µ-OH)+ [1.941 (3) Å; Guzei et al., 2000] and the neutral Ga dimer [{CH(SiMe3)2}2Ga(µ-OH)]2 [average 1.96 (1) Å; Uhl et al., 1996]. The Ga—(µ-OH)—Ga bond angles [average 128.4 (8)°] are nearly identical to those in Ga12tBu12(µ3-O)8(µ-O)2(µ-OH)4 [average 129.1 (1) Å; Barron et al. 1995]. The Ga—C bond distances [average 1.92 (2) Å] in (II) are significantly shorter than those in Ga12tBu12(µ3-O)8(µ-O)2(µ-OH)4 [average 1.98 (1) Å] due to the difference in cluster charge (dication versus neutral) and alkyl group size (Me versus tBu). The Ga—C distances in (II) are also shorter than those in [(iPr2—ATI)GaMe]2(µ-OH)+ [1.941 (3) Å; Guzei et al., 2000] and (I) [average 1.950 (3) Å; Dagorne et al., 2000].
The hydrate molecules and the [B(C6F5)4]− anions of (II) are hydrogen bonded to the [Ga12Me12(µ3-O)8(µ-OH)6]2+ dication through the Ga(µ-OH) groups. There are four unique hydrogen bonds (Table 2) and one O—H···π-ring interaction. The strongest interaction is between the O11—H11 group and the O90 water molecule, and can be considered as a moderate strength hydrogen bond (Jeffrey, 1997). Similar hydrogen bonds are present in Ga6Mes6(µ3-O)4(µ3-OH)4·6THF, in which the tetrahydrofuran molecules are hydrogen bonded to the µ3-OH group, and in Me2Ga(µ-OH)(µ-Me2Pz)GaMe2·HOCH2Me2pz (pz is pyrazolyl), in which the OH group of the HOCH2Me2pz molecule is hydrogen bonded to the µ-OH group (Roesky et al., 1994; Trotter et al., 1988). The second hydrogen bond in (II) is the O12—H12···F22 interaction which is longer than that in 2-fluoro-1,1,2-triphenyl ethanol [F···O = 2.73 (4) Å; Desmarteau et al., 1992]. The other two hydrogen bonds are from the O90 water H atoms to F atoms of the anion. Hydrogen bonds from O—H donors to organic C—F groups are not common and may be ascribed, in the present case, to the electrostatic attraction between the [Ga12Me12(µ3-O)8(µ-OH)6]2+ dication and the [B(C6F5)4]− anions (Desiraju & Steiner, 1999). Additionally an O—H···π-ring interaction is present between the O13 H atom and the (C11–C16)i phenyl ring: H13···π-ring = 3.11 Å, O13—H13···π-ring centroid = 159° [the coordinates for the ring centroid are 0.30717, 0.56226, 0.14106; symmetry code: (i) 1 + x, y, z]
The [B(C6F5)4]− anion in (II) adopts a slightly distorted tetrahedral structure. The C22—F22 bond distance is slightly longer than other C—F bond distances and may be due to the O12—H12—F22 hydrogen bond.