A cationic hydro­xo-bridged dinuclear gallium complex

The crystal structure of μ-hydro­xo-bis{[N-iso­propyl-2-(isopropyl­amino)­tropon­imino-N,N′](methyl)gallium(II)} tetrakis(pentafluorophenyl)borate (troponimine is 2,4,6-cycloheptatrien-1-imine), [Ga₂(C₁₄H₂₂N₂)₂(OH)]B(C₆H₅)₄, is discussed. The two (ⁱPr₂-ATI)GaMe (ATI is aminotroponimime) units of the dinuclear cation are linked by a bridging hydro­xo group and are both slightly twisted from planarity.

S1. Comment

In recent reports we have described the synthesis, structures and reactivity of several classes of cationic group 13 alkyl complexes, some of which polymerize ethylene (Coles & Jordan, 1997; Ihara et al., 1998; Radzewich et al., 1998; Radzewich et al., 1999; Korolev et al., 1999; Dagorne et al., 2000). During these studies we found that the cationic Ga methyl complex [{ⁱPr₂—ATI}Ga(Me)(NMe₂Ph)][B(C₆F₅)₄] (ATA is aminotroponimine) is hydrolyzed to the cationic dinuclear Ga hydroxo complex [({ⁱPr₂—ATI}GaMe)₂(µ-OH)][B(C₆F₅)₄], (II), the molecular structure of which is presented here. \sch

Compound (II) crystallizes as discrete ({ⁱPr₂—ATI}GaMe)₂(µ-OH)⁺ cations and B(C₆F₅)₄^- anions with no close cation-anion contacts. The B(C₆F₅)₄^- anion has a slightly distorted tetrahedral structure. The C29—B—C41 [103.3 (3)°] and C35—B—C47 [101.5 (3)°] bond angles are smaller than the ideal tetrahedral angle (109.47°), which is compensated for by opening of the other C—B—C angles [113.1 (3)° average]. The C₆F₅ rings are normal. The cation of (II) contains two {ⁱPr₂—ATI}GaMe units which are linked through the Ga centers by a hydroxo bridge (Figure 1). The Ga1—O [1.935 (2) Å] and Ga2—O [1.947 (2) Å] bond distances and the Ga—O—Ga bond angle [140.87 (11)°] are very similar to those in {(^tBu)₂Ga(µ-OH)}₃ [Ga—O 1.957 (5) Å average; Ga- O—Ga 143.0 (2)° average], which contains three hydroxo bridges (Atwood et al., 1993). The two {ⁱPr₂—ATI}GaMe units of (II) exhibit very similar structures. Both Ga centers adopt a distorted tetrahedral geometry. The N1—Ga1—N2 [84.25 (12)°] and N3—Ga2—N4 [84.44 (11)°] bond angles are comparable to those in {ⁱPr₂—ATI}AlMe₂ [83.3 (2)°] and {Me₂—ATI}₂GaI [80.5 (2)° average] (Dias & Jin, 1995, 1996). The small N—Ga—N bond angles in (II) are compensated for by the opening of the N—Ga—C angles [126 (3)° average]. The N—Ga—O bond angles [105 (2)° average] and C—Ga—O bond angles [107 (1)° average] are similar. The Ga—N bond distances in (II) [1.916 (2) Å average] are shorter than those in {Me₂—ATI}₂GaI [1.97 (2) Å average; Dias & Jin, 1996] which is expected due to the higher charge and lower coordination number of (II). The aminotroponiminate C—N bond distances of (II) fall in the range 1.341 (4)–1.352 (4) Å, and thus are intermediate between the normal C_sp²-N single bond (1.47 Å) and C═N double bond (1.29 Å) distances, which is consistent with significant delocalization of the π-electrons within the ATI unit. However, the five-membered N—C—C—N—Ga rings are slightly twisted as is manifested by the key torsion angles Ga1—N1—C5—C11 [6.0 (4)°] and Ga2—N3—C19—C25 [12.0 (3)°]. Additionally, the seven-membered rings of the ATI ligands are also slightly twisted [torsion angles: C9—C10—C11—C5 12.0 (6) and C23—C24—C25—C19 13.1 (5)°]. The Ga—C bond distances in (II) [1.941 (3) Å average] are comparable to those in {^tBuC(NⁱPr)₂}GaMe₂.{^tBuC(NⁱPr)₂}GaMe⁺ [1.950 (3) Å average; Dagorne et al., 2000] and are slightly shorter than those in [Me₂Ga(NH₂^tBu)₂]Br [1.98 (2) Å average; Atwood et al., 1992].

Related literature

For related literature, see: Atwood et al. (1992, 1993); Coles & Jordan (1997); Dagorne et al. (2000); Dias & Jin (1995, 1996); Ihara et al. (1998); Korolev et al. (1999); Radzewich et al. (1998, 1999).

S2. Experimental

A resealable J-Young NMR tube was charged with {^IPr₂—ATI}GaMe₂ (152 mg, 0.500 mmol) and [NHMe₂Ph][B(C₆F₅)₄] (395 mg, 0.500 mmol), and C₆D₅Cl (0.5 ml) was added at 296 K. The tube was shaken to yield a clear orange solution, which was immediately analyzed by ¹H, ¹³C, ¹¹B and ¹⁹F NMR spectroscopy, which showed that quantitative conversion to [{ⁱPr₂– ATI}Ga(Me)(NMe₂Ph)][B(C₆F₅)₄], (I), had occurred. The volume of the solution was reduced to ca 0.1 ml under vacuum and wet pentane (ca 1 ml) was slowly added. Phase separation occurred. The tube was left at 296 K for 3 d which resulted in the formation of yellow-orange crystals of [({ⁱPr₂—ATI}GaMe)₂(µ-OH)][B(C₆F₅)₄], (II), at the phase boundary.

S3. Refinement

C—H distances were constrained to values in the range 0.95–0.99 Å, depending upon atom type, with U_iso = 1.2U_eq(C), and 1.5U_eq(C) for methyl groups. The O—H distance was constrained to be 0.84 Å. All hydrogen atoms were included in the structure factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients. The H atom of the hydroxo group was located from the difference map but subsequently refined with an idealized geometry.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Molecular structure of (II). The displacement ellipsoids are shown at 30% probability level.

(II)

Crystal data

[Ga2(C14H22N2)2(OH)]B(C6F5)4	F(000) = 2560
Mr = 1272.17	Dx = 1.611 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 17.7211 (8) Å	Cell parameters from 7833 reflections
b = 16.0050 (7) Å	θ = 2–26°
c = 18.5655 (9) Å	µ = 1.14 mm^−1
β = 94.904 (1)°	T = 173 K
V = 5246.4 (4) Å^3	Block, yellow
Z = 4	0.35 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD-1000 diffractometer	10732 independent reflections
Radiation source: fine-focus sealed tube	6612 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
phi scans	θmax = 26.4°, θmin = 1.5°
Absorption correction: empirical (SADABS; Blessing, 1995)	h = −22→22
Tmin = 0.691, Tmax = 0.726	k = −20→20
47660 measured reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.054	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.005P)^2] where P = (Fo^2 + 2Fc^2)/3
10732 reflections	(Δ/σ)max = 0.001
732 parameters	Δρmax = 0.50 e Å^−3
1 restraint	Δρmin = −0.39 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ga1	0.43553 (2)	0.71162 (2)	0.23242 (2)	0.02837 (11)
Ga2	0.60889 (2)	0.73960 (2)	0.35170 (2)	0.02866 (11)
O	0.54077 (11)	0.70446 (13)	0.26945 (11)	0.0310 (6)
H	0.5683	0.6736	0.2367	0.037*
F1	0.54895 (11)	0.41092 (12)	0.22594 (10)	0.0411 (6)
F2	0.64576 (12)	0.52513 (13)	0.19083 (11)	0.0513 (6)
F3	0.72845 (12)	0.50429 (13)	0.07430 (11)	0.0547 (7)
F4	0.70902 (11)	0.36315 (13)	−0.00638 (11)	0.0490 (6)
F5	0.60471 (11)	0.25082 (12)	0.02219 (10)	0.0397 (5)
F6	0.47363 (11)	0.35774 (12)	−0.00208 (10)	0.0465 (6)
F7	0.36514 (13)	0.32972 (15)	−0.10456 (12)	0.0660 (7)
F8	0.26533 (12)	0.20141 (15)	−0.09382 (12)	0.0713 (8)
F9	0.28165 (12)	0.09795 (14)	0.02304 (12)	0.0626 (7)
F10	0.39677 (11)	0.11849 (12)	0.12324 (11)	0.0448 (6)
F11	0.60965 (11)	0.23210 (13)	0.26234 (10)	0.0440 (6)
F12	0.69891 (13)	0.10426 (14)	0.30182 (13)	0.0651 (7)
F13	0.70523 (12)	−0.03183 (14)	0.21344 (13)	0.0700 (8)
F14	0.62286 (12)	−0.03134 (13)	0.08315 (13)	0.0636 (7)
F15	0.52747 (12)	0.09032 (12)	0.04638 (11)	0.0462 (6)
F16	0.47199 (11)	0.14510 (12)	0.27172 (10)	0.0461 (6)
F17	0.37921 (12)	0.18965 (13)	0.36808 (12)	0.0577 (7)
F18	0.29988 (12)	0.33473 (15)	0.35455 (12)	0.0660 (7)
F19	0.31993 (12)	0.43809 (14)	0.24154 (11)	0.0563 (7)
F20	0.41411 (11)	0.39682 (12)	0.14333 (11)	0.0423 (6)
N1	0.41606 (15)	0.82922 (17)	0.22576 (15)	0.0280 (7)
N2	0.37712 (14)	0.71711 (18)	0.31457 (13)	0.0267 (7)
N3	0.55021 (14)	0.80825 (16)	0.40977 (14)	0.0268 (7)
N4	0.59556 (15)	0.65587 (16)	0.42373 (14)	0.0285 (7)
B	0.5066 (2)	0.2505 (2)	0.1367 (2)	0.0282 (10)
C1	0.4192 (2)	0.6294 (2)	0.15568 (18)	0.0459 (11)
H1A	0.4085	0.5749	0.1766	0.069*
H1B	0.4647	0.6253	0.1294	0.069*
H1C	0.3762	0.6466	0.1223	0.069*
C2	0.43840 (19)	0.8834 (2)	0.16624 (18)	0.0314 (9)
H2	0.4597	0.9367	0.1874	0.038*
C3	0.49924 (19)	0.8393 (2)	0.12779 (19)	0.0441 (11)
H3A	0.5433	0.8287	0.1621	0.066*
H3B	0.5142	0.8745	0.0883	0.066*
H3C	0.4794	0.7861	0.1081	0.066*
C4	0.3700 (2)	0.9037 (2)	0.11406 (18)	0.0437 (11)
H4A	0.3494	0.8520	0.0920	0.065*
H4B	0.3853	0.9412	0.0762	0.065*
H4C	0.3312	0.9310	0.1404	0.065*
C5	0.37794 (18)	0.8594 (2)	0.27960 (18)	0.0276 (9)
C6	0.36641 (19)	0.9456 (2)	0.28921 (19)	0.0360 (10)
H6	0.3866	0.9795	0.2535	0.043*
C7	0.3314 (2)	0.9906 (2)	0.3407 (2)	0.0431 (11)
H7	0.3367	1.0495	0.3375	0.052*
C8	0.2902 (2)	0.9636 (3)	0.3957 (2)	0.0493 (12)
H8	0.2701	1.0051	0.4252	0.059*
C9	0.2757 (2)	0.8816 (3)	0.4116 (2)	0.0454 (11)
H9	0.2423	0.8736	0.4484	0.054*
C10	0.3022 (2)	0.8088 (2)	0.38244 (19)	0.0386 (10)
H10	0.2831	0.7594	0.4025	0.046*
C11	0.35203 (18)	0.7940 (2)	0.32868 (18)	0.0271 (9)
C12	0.3497 (2)	0.6421 (2)	0.35076 (18)	0.0323 (9)
H12	0.3427	0.6565	0.4022	0.039*
C13	0.27361 (19)	0.6156 (2)	0.31370 (19)	0.0439 (11)
H13A	0.2372	0.6613	0.3160	0.066*
H13B	0.2551	0.5663	0.3382	0.066*
H13C	0.2795	0.6019	0.2630	0.066*
C14	0.4076 (2)	0.5722 (2)	0.34998 (19)	0.0414 (10)
H14A	0.4156	0.5580	0.2999	0.062*
H14B	0.3889	0.5230	0.3743	0.062*
H14C	0.4555	0.5906	0.3752	0.062*
C15	0.70459 (18)	0.7645 (2)	0.31287 (19)	0.0455 (11)
H15A	0.7043	0.8225	0.2960	0.068*
H15B	0.7117	0.7270	0.2723	0.068*
H15C	0.7461	0.7566	0.3507	0.068*
C16	0.5401 (2)	0.8995 (2)	0.40318 (18)	0.0302 (9)
H16	0.4849	0.9126	0.4026	0.036*
C17	0.5685 (2)	0.9299 (2)	0.33331 (18)	0.0408 (10)
H17A	0.6237	0.9237	0.3356	0.061*
H17B	0.5551	0.9889	0.3260	0.061*
H17C	0.5452	0.8968	0.2929	0.061*
C18	0.5821 (2)	0.9439 (2)	0.46765 (19)	0.0432 (11)
H18A	0.5615	0.9256	0.5124	0.065*
H18B	0.5756	1.0044	0.4622	0.065*
H18C	0.6361	0.9300	0.4697	0.065*
C19	0.51850 (18)	0.7653 (2)	0.46221 (18)	0.0261 (9)
C20	0.46100 (19)	0.7990 (2)	0.50067 (18)	0.0338 (10)
H20	0.4470	0.8543	0.4865	0.041*
C21	0.4203 (2)	0.7673 (3)	0.5556 (2)	0.0434 (11)
H21	0.3806	0.8021	0.5695	0.052*
C22	0.4291 (2)	0.6930 (3)	0.5928 (2)	0.0461 (11)
H22	0.3951	0.6822	0.6285	0.055*
C23	0.4822 (2)	0.6339 (2)	0.58290 (19)	0.0439 (11)
H23	0.4838	0.5892	0.6167	0.053*
C24	0.5342 (2)	0.6280 (2)	0.53201 (19)	0.0380 (10)
H24	0.5662	0.5804	0.5377	0.046*
C25	0.54865 (19)	0.6794 (2)	0.47295 (18)	0.0270 (9)
C26	0.6361 (2)	0.5755 (2)	0.42798 (19)	0.0407 (10)
H26	0.6054	0.5345	0.4537	0.049*
C27	0.6449 (2)	0.5427 (2)	0.35286 (18)	0.0470 (11)
H27A	0.5948	0.5363	0.3267	0.070*
H27B	0.6705	0.4884	0.3562	0.070*
H27C	0.6751	0.5822	0.3269	0.070*
C28	0.7119 (2)	0.5864 (3)	0.4714 (2)	0.0641 (14)
H28A	0.7416	0.6291	0.4485	0.096*
H28B	0.7395	0.5333	0.4730	0.096*
H28C	0.7037	0.6039	0.5207	0.096*
C29	0.56798 (18)	0.3251 (2)	0.12379 (18)	0.0261 (9)
C30	0.5843 (2)	0.3962 (2)	0.16481 (18)	0.0304 (9)
C31	0.6356 (2)	0.4566 (2)	0.14900 (19)	0.0332 (10)
C32	0.6771 (2)	0.4466 (2)	0.0906 (2)	0.0369 (10)
C33	0.6662 (2)	0.3759 (2)	0.04957 (19)	0.0328 (10)
C34	0.6133 (2)	0.3187 (2)	0.06630 (19)	0.0315 (9)
C35	0.44315 (19)	0.2381 (2)	0.06674 (19)	0.0301 (9)
C36	0.4293 (2)	0.2905 (2)	0.0074 (2)	0.0332 (9)
C37	0.3720 (2)	0.2781 (3)	−0.0464 (2)	0.0432 (11)
C38	0.3218 (2)	0.2141 (3)	−0.0416 (2)	0.0469 (11)
C39	0.3308 (2)	0.1617 (3)	0.0166 (2)	0.0426 (11)
C40	0.3903 (2)	0.1742 (2)	0.0679 (2)	0.0345 (10)
C41	0.56073 (19)	0.1677 (2)	0.15406 (19)	0.0289 (9)
C42	0.6087 (2)	0.1660 (2)	0.2166 (2)	0.0336 (10)
C43	0.6562 (2)	0.1011 (3)	0.2382 (2)	0.0424 (11)
C44	0.6598 (2)	0.0336 (3)	0.1940 (3)	0.0472 (12)
C45	0.6171 (2)	0.0327 (2)	0.1294 (2)	0.0404 (11)
C46	0.5682 (2)	0.0984 (2)	0.1108 (2)	0.0340 (10)
C47	0.45152 (18)	0.2706 (2)	0.20261 (18)	0.0283 (9)
C48	0.4374 (2)	0.2204 (2)	0.26080 (19)	0.0331 (9)
C49	0.3879 (2)	0.2413 (3)	0.3115 (2)	0.0394 (10)
C50	0.3483 (2)	0.3139 (3)	0.3050 (2)	0.0425 (11)
C51	0.3584 (2)	0.3651 (2)	0.2483 (2)	0.0378 (10)
C52	0.40804 (19)	0.3428 (2)	0.1991 (2)	0.0307 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0293 (2)	0.0312 (3)	0.0247 (2)	−0.0019 (2)	0.00239 (18)	−0.0010 (2)
Ga2	0.0260 (2)	0.0330 (3)	0.0273 (2)	0.0012 (2)	0.00360 (18)	−0.0019 (2)
O	0.0270 (14)	0.0395 (15)	0.0270 (14)	0.0055 (12)	0.0055 (11)	−0.0080 (12)
F1	0.0505 (14)	0.0421 (13)	0.0323 (13)	−0.0144 (11)	0.0124 (11)	−0.0104 (10)
F2	0.0672 (17)	0.0453 (14)	0.0423 (14)	−0.0277 (12)	0.0105 (12)	−0.0125 (11)
F3	0.0584 (16)	0.0601 (16)	0.0471 (15)	−0.0323 (13)	0.0139 (12)	−0.0044 (12)
F4	0.0459 (14)	0.0654 (16)	0.0380 (14)	−0.0155 (12)	0.0167 (11)	−0.0052 (12)
F5	0.0442 (13)	0.0402 (13)	0.0364 (12)	−0.0062 (11)	0.0132 (10)	−0.0109 (11)
F6	0.0486 (15)	0.0436 (14)	0.0457 (14)	−0.0047 (12)	−0.0045 (11)	0.0084 (11)
F7	0.0648 (18)	0.0744 (18)	0.0546 (17)	0.0121 (14)	−0.0193 (14)	0.0054 (14)
F8	0.0415 (15)	0.099 (2)	0.0702 (18)	0.0013 (14)	−0.0150 (13)	−0.0304 (15)
F9	0.0443 (15)	0.0711 (18)	0.0743 (18)	−0.0271 (13)	0.0165 (13)	−0.0351 (14)
F10	0.0459 (15)	0.0404 (14)	0.0503 (15)	−0.0131 (11)	0.0171 (12)	−0.0097 (12)
F11	0.0451 (14)	0.0502 (15)	0.0361 (13)	0.0055 (11)	0.0004 (11)	−0.0049 (11)
F12	0.0518 (17)	0.0794 (19)	0.0635 (18)	0.0168 (14)	0.0012 (14)	0.0248 (15)
F13	0.0521 (16)	0.0498 (16)	0.112 (2)	0.0216 (13)	0.0314 (15)	0.0312 (15)
F14	0.0631 (17)	0.0328 (14)	0.101 (2)	−0.0001 (12)	0.0421 (15)	−0.0152 (14)
F15	0.0494 (15)	0.0415 (14)	0.0494 (15)	−0.0019 (11)	0.0134 (12)	−0.0185 (12)
F16	0.0561 (15)	0.0358 (13)	0.0493 (15)	0.0024 (12)	0.0224 (12)	0.0064 (11)
F17	0.0664 (17)	0.0647 (17)	0.0456 (15)	−0.0141 (13)	0.0265 (13)	−0.0026 (13)
F18	0.0476 (16)	0.100 (2)	0.0538 (16)	0.0072 (14)	0.0234 (13)	−0.0288 (14)
F19	0.0448 (15)	0.0615 (16)	0.0608 (16)	0.0245 (13)	−0.0061 (12)	−0.0267 (13)
F20	0.0461 (14)	0.0371 (13)	0.0434 (14)	0.0088 (11)	0.0020 (11)	−0.0017 (11)
N1	0.0267 (18)	0.0314 (18)	0.0261 (18)	−0.0037 (14)	0.0044 (15)	0.0019 (15)
N2	0.0274 (17)	0.0304 (18)	0.0226 (17)	−0.0057 (15)	0.0035 (13)	0.0014 (15)
N3	0.0256 (17)	0.0244 (18)	0.0302 (18)	−0.0001 (14)	0.0019 (14)	−0.0036 (14)
N4	0.0324 (19)	0.0270 (18)	0.0261 (18)	0.0081 (15)	0.0034 (14)	−0.0010 (15)
B	0.030 (3)	0.025 (3)	0.030 (2)	−0.003 (2)	0.006 (2)	−0.003 (2)
C1	0.057 (3)	0.049 (3)	0.032 (2)	−0.012 (2)	0.001 (2)	−0.008 (2)
C2	0.030 (2)	0.034 (2)	0.030 (2)	−0.0063 (19)	0.0040 (19)	0.0029 (19)
C3	0.042 (3)	0.054 (3)	0.038 (3)	−0.007 (2)	0.011 (2)	0.009 (2)
C4	0.048 (3)	0.047 (3)	0.035 (2)	0.001 (2)	0.003 (2)	0.011 (2)
C5	0.019 (2)	0.033 (2)	0.029 (2)	−0.0012 (18)	−0.0066 (17)	−0.0007 (19)
C6	0.034 (2)	0.033 (2)	0.041 (3)	−0.0002 (19)	−0.001 (2)	0.001 (2)
C7	0.045 (3)	0.034 (3)	0.047 (3)	0.004 (2)	−0.010 (2)	−0.010 (2)
C8	0.053 (3)	0.054 (3)	0.040 (3)	0.015 (2)	−0.003 (2)	−0.020 (2)
C9	0.036 (3)	0.066 (3)	0.035 (3)	0.006 (2)	0.008 (2)	−0.010 (2)
C10	0.035 (2)	0.047 (3)	0.034 (2)	−0.002 (2)	0.006 (2)	−0.002 (2)
C11	0.021 (2)	0.036 (2)	0.025 (2)	−0.0011 (18)	−0.0013 (17)	−0.0038 (19)
C12	0.038 (3)	0.035 (2)	0.024 (2)	−0.006 (2)	0.0067 (19)	0.0023 (18)
C13	0.036 (3)	0.044 (3)	0.053 (3)	−0.013 (2)	0.009 (2)	0.001 (2)
C14	0.044 (3)	0.036 (2)	0.042 (3)	−0.008 (2)	−0.007 (2)	0.009 (2)
C15	0.034 (2)	0.052 (3)	0.051 (3)	0.000 (2)	0.010 (2)	−0.003 (2)
C16	0.031 (2)	0.025 (2)	0.034 (2)	0.0020 (18)	0.0016 (19)	−0.0042 (18)
C17	0.046 (3)	0.032 (2)	0.044 (3)	−0.001 (2)	0.001 (2)	0.003 (2)
C18	0.044 (3)	0.035 (2)	0.049 (3)	−0.002 (2)	0.000 (2)	−0.014 (2)
C19	0.024 (2)	0.030 (2)	0.023 (2)	−0.0041 (18)	−0.0024 (17)	−0.0064 (18)
C20	0.030 (2)	0.036 (2)	0.035 (2)	0.0050 (19)	0.0033 (19)	−0.0045 (19)
C21	0.035 (2)	0.058 (3)	0.038 (3)	0.004 (2)	0.012 (2)	−0.015 (2)
C22	0.047 (3)	0.059 (3)	0.034 (3)	−0.008 (2)	0.015 (2)	−0.002 (2)
C23	0.058 (3)	0.047 (3)	0.027 (2)	−0.008 (2)	0.009 (2)	0.003 (2)
C24	0.045 (3)	0.038 (3)	0.031 (2)	0.004 (2)	0.006 (2)	0.001 (2)
C25	0.027 (2)	0.032 (2)	0.022 (2)	−0.0016 (18)	−0.0020 (17)	−0.0025 (18)
C26	0.057 (3)	0.032 (2)	0.035 (2)	0.013 (2)	0.010 (2)	0.002 (2)
C27	0.058 (3)	0.039 (3)	0.047 (3)	0.008 (2)	0.018 (2)	−0.010 (2)
C28	0.067 (3)	0.070 (3)	0.053 (3)	0.039 (3)	−0.012 (3)	−0.005 (3)
C29	0.025 (2)	0.030 (2)	0.023 (2)	0.0006 (18)	−0.0011 (17)	−0.0002 (18)
C30	0.032 (2)	0.038 (2)	0.021 (2)	−0.0036 (19)	0.0058 (18)	−0.0006 (19)
C31	0.043 (3)	0.032 (2)	0.024 (2)	−0.014 (2)	0.000 (2)	−0.0058 (19)
C32	0.035 (3)	0.041 (3)	0.034 (2)	−0.019 (2)	0.002 (2)	0.005 (2)
C33	0.031 (2)	0.046 (3)	0.022 (2)	−0.006 (2)	0.0066 (18)	0.000 (2)
C34	0.032 (2)	0.033 (2)	0.029 (2)	−0.0033 (19)	−0.0004 (19)	−0.0059 (19)
C35	0.028 (2)	0.028 (2)	0.035 (2)	0.0003 (18)	0.0111 (18)	−0.0085 (19)
C36	0.028 (2)	0.033 (2)	0.039 (2)	−0.003 (2)	0.0050 (19)	−0.009 (2)
C37	0.038 (3)	0.049 (3)	0.042 (3)	0.012 (2)	0.000 (2)	−0.005 (2)
C38	0.024 (2)	0.065 (3)	0.050 (3)	0.005 (2)	−0.005 (2)	−0.028 (3)
C39	0.033 (3)	0.045 (3)	0.052 (3)	−0.009 (2)	0.015 (2)	−0.026 (2)
C40	0.033 (2)	0.035 (2)	0.037 (3)	0.000 (2)	0.010 (2)	−0.009 (2)
C41	0.029 (2)	0.028 (2)	0.031 (2)	−0.0016 (18)	0.0128 (19)	−0.0008 (19)
C42	0.036 (3)	0.030 (2)	0.036 (3)	0.000 (2)	0.012 (2)	0.000 (2)
C43	0.034 (3)	0.053 (3)	0.041 (3)	0.002 (2)	0.009 (2)	0.016 (2)
C44	0.033 (3)	0.035 (3)	0.077 (4)	0.009 (2)	0.026 (3)	0.019 (3)
C45	0.039 (3)	0.023 (2)	0.064 (3)	−0.002 (2)	0.029 (2)	−0.003 (2)
C46	0.035 (3)	0.032 (2)	0.037 (3)	−0.004 (2)	0.016 (2)	−0.003 (2)
C47	0.025 (2)	0.028 (2)	0.032 (2)	−0.0005 (18)	0.0042 (18)	−0.0053 (18)
C48	0.033 (2)	0.028 (2)	0.040 (2)	−0.0008 (19)	0.0102 (19)	−0.005 (2)
C49	0.041 (3)	0.046 (3)	0.033 (2)	−0.015 (2)	0.013 (2)	−0.007 (2)
C50	0.026 (2)	0.061 (3)	0.042 (3)	0.001 (2)	0.011 (2)	−0.024 (2)
C51	0.030 (3)	0.039 (3)	0.043 (3)	0.007 (2)	−0.003 (2)	−0.017 (2)
C52	0.027 (2)	0.032 (2)	0.033 (2)	−0.0032 (19)	0.0001 (19)	−0.0055 (19)

Geometric parameters (Å, º)

Ga1—N1	1.916 (3)	C5—C11	1.486 (4)
Ga1—N2	1.917 (3)	C6—C7	1.384 (5)
Ga1—O	1.935 (2)	C7—C8	1.375 (5)
Ga1—C1	1.943 (3)	C8—C9	1.374 (5)
Ga2—N3	1.909 (3)	C9—C10	1.383 (5)
Ga2—N4	1.922 (3)	C10—C11	1.408 (4)
Ga2—C15	1.940 (3)	C12—C14	1.518 (4)
Ga2—O	1.947 (2)	C12—C13	1.521 (4)
F1—C30	1.363 (3)	C16—C17	1.511 (4)
F2—C31	1.348 (4)	C16—C18	1.529 (4)
F3—C32	1.349 (4)	C19—C20	1.401 (4)
F4—C33	1.353 (4)	C19—C25	1.483 (4)
F5—C34	1.361 (4)	C20—C21	1.395 (4)
F6—C36	1.353 (4)	C21—C22	1.377 (5)
F7—C37	1.357 (4)	C22—C23	1.358 (5)
F8—C38	1.348 (4)	C23—C24	1.378 (4)
F9—C39	1.354 (4)	C24—C25	1.412 (4)
F10—C40	1.359 (4)	C26—C27	1.510 (4)
F11—C42	1.356 (4)	C26—C28	1.516 (5)
F12—C43	1.348 (4)	C29—C30	1.386 (4)
F13—C44	1.351 (4)	C29—C34	1.394 (4)
F14—C45	1.346 (4)	C30—C31	1.376 (4)
F15—C46	1.349 (4)	C31—C32	1.370 (4)
F16—C48	1.359 (4)	C32—C33	1.369 (4)
F17—C49	1.355 (4)	C33—C34	1.365 (4)
F18—C50	1.352 (4)	C35—C40	1.387 (4)
F19—C51	1.353 (4)	C35—C36	1.390 (5)
F20—C52	1.360 (4)	C36—C37	1.376 (5)
N1—C5	1.343 (4)	C37—C38	1.364 (5)
N1—C2	1.485 (4)	C38—C39	1.366 (5)
N2—C11	1.341 (4)	C39—C40	1.373 (5)
N2—C12	1.478 (4)	C41—C42	1.380 (4)
N3—C19	1.352 (4)	C41—C46	1.383 (4)
N3—C16	1.475 (4)	C42—C43	1.375 (5)
N4—C25	1.341 (4)	C43—C44	1.361 (5)
N4—C26	1.472 (4)	C44—C45	1.363 (5)
B—C29	1.648 (5)	C45—C46	1.387 (5)
B—C41	1.651 (5)	C47—C48	1.386 (4)
B—C35	1.655 (5)	C47—C52	1.387 (4)
B—C47	1.660 (5)	C48—C49	1.382 (4)
C2—C3	1.517 (4)	C49—C50	1.357 (5)
C2—C4	1.521 (4)	C50—C51	1.359 (5)
C5—C6	1.409 (4)	C51—C52	1.368 (5)
N1—Ga1—N2	84.25 (12)	F1—C30—C29	120.7 (3)
N1—Ga1—O	104.12 (10)	C31—C30—C29	124.7 (3)
N2—Ga1—O	106.83 (10)	F2—C31—C32	119.8 (3)
N1—Ga1—C1	127.12 (13)	F2—C31—C30	120.4 (3)
N2—Ga1—C1	123.91 (14)	C32—C31—C30	119.8 (3)
O—Ga1—C1	107.39 (13)	F3—C32—C33	120.4 (3)
N3—Ga2—N4	84.44 (11)	F3—C32—C31	121.1 (3)
N3—Ga2—C15	128.85 (13)	C33—C32—C31	118.5 (3)
N4—Ga2—C15	124.42 (14)	F4—C33—C34	120.9 (3)
N3—Ga2—O	106.14 (10)	F4—C33—C32	119.4 (3)
N4—Ga2—O	103.86 (10)	C34—C33—C32	119.7 (3)
C15—Ga2—O	105.73 (12)	F5—C34—C33	116.3 (3)
Ga1—O—Ga2	140.87 (11)	F5—C34—C29	118.5 (3)
C5—N1—C2	121.8 (3)	C33—C34—C29	125.2 (3)
C5—N1—Ga1	113.9 (2)	C40—C35—C36	112.5 (3)
C2—N1—Ga1	124.3 (2)	C40—C35—B	119.4 (3)
C11—N2—C12	121.9 (3)	C36—C35—B	127.7 (3)
C11—N2—Ga1	114.1 (2)	F6—C36—C37	114.9 (4)
C12—N2—Ga1	123.0 (2)	F6—C36—C35	121.2 (3)
C19—N3—C16	120.5 (3)	C37—C36—C35	123.9 (4)
C19—N3—Ga2	113.2 (2)	F7—C37—C38	119.6 (4)
C16—N3—Ga2	126.2 (2)	F7—C37—C36	120.0 (4)
C25—N4—C26	122.5 (3)	C38—C37—C36	120.4 (4)
C25—N4—Ga2	113.5 (2)	F8—C38—C37	121.0 (4)
C26—N4—Ga2	123.9 (2)	F8—C38—C39	120.3 (4)
C29—B—C41	103.3 (3)	C37—C38—C39	118.6 (4)
C29—B—C35	112.7 (3)	F9—C39—C38	120.0 (4)
C41—B—C35	113.7 (3)	F9—C39—C40	120.6 (4)
C29—B—C47	113.8 (3)	C38—C39—C40	119.3 (4)
C41—B—C47	112.3 (3)	F10—C40—C39	116.1 (4)
C35—B—C47	101.5 (3)	F10—C40—C35	118.8 (3)
N1—C2—C3	108.9 (3)	C39—C40—C35	125.2 (4)
N1—C2—C4	110.5 (3)	C42—C41—C46	112.9 (3)
C3—C2—C4	111.1 (3)	C42—C41—B	119.1 (3)
N1—C5—C6	122.3 (3)	C46—C41—B	127.8 (3)
N1—C5—C11	113.8 (3)	F11—C42—C43	115.6 (4)
C6—C5—C11	123.8 (3)	F11—C42—C41	119.0 (3)
C7—C6—C5	132.5 (4)	C43—C42—C41	125.4 (4)
C8—C7—C6	130.3 (4)	F12—C43—C44	120.4 (4)
C9—C8—C7	125.5 (4)	F12—C43—C42	120.7 (4)
C8—C9—C10	130.1 (4)	C44—C43—C42	118.9 (4)
C9—C10—C11	132.4 (4)	F13—C44—C43	120.8 (4)
N2—C11—C10	122.1 (3)	F13—C44—C45	120.0 (4)
N2—C11—C5	113.7 (3)	C43—C44—C45	119.2 (4)
C10—C11—C5	124.1 (3)	F14—C45—C44	120.2 (4)
N2—C12—C14	110.2 (3)	F14—C45—C46	119.9 (4)
N2—C12—C13	109.5 (3)	C44—C45—C46	119.9 (4)
C14—C12—C13	111.3 (3)	F15—C46—C41	121.4 (3)
N3—C16—C17	110.1 (3)	F15—C46—C45	115.1 (4)
N3—C16—C18	110.3 (3)	C41—C46—C45	123.6 (4)
C17—C16—C18	110.3 (3)	C48—C47—C52	112.5 (3)
N3—C19—C20	122.4 (3)	C48—C47—B	128.2 (3)
N3—C19—C25	113.6 (3)	C52—C47—B	119.1 (3)
C20—C19—C25	123.9 (3)	F16—C48—C49	114.7 (3)
C21—C20—C19	132.6 (4)	F16—C48—C47	121.4 (3)
C22—C21—C20	129.6 (4)	C49—C48—C47	123.9 (4)
C23—C22—C21	125.8 (4)	F17—C49—C50	119.9 (4)
C22—C23—C24	130.7 (4)	F17—C49—C48	120.1 (4)
C23—C24—C25	132.0 (4)	C50—C49—C48	120.0 (4)
N4—C25—C24	122.0 (3)	F18—C50—C49	120.3 (4)
N4—C25—C19	114.0 (3)	F18—C50—C51	120.8 (4)
C24—C25—C19	123.9 (3)	C49—C50—C51	119.0 (4)
N4—C26—C27	110.0 (3)	F19—C51—C50	119.6 (4)
N4—C26—C28	109.5 (3)	F19—C51—C52	120.7 (4)
C27—C26—C28	112.0 (3)	C50—C51—C52	119.6 (4)
C30—C29—C34	112.0 (3)	F20—C52—C51	116.1 (3)
C30—C29—B	128.7 (3)	F20—C52—C47	119.0 (3)
C34—C29—B	119.3 (3)	C51—C52—C47	124.9 (4)
F1—C30—C31	114.6 (3)
N1—Ga1—O—Ga2	57.8 (2)	C30—C31—C32—C33	−0.3 (6)
N2—Ga1—O—Ga2	−30.4 (2)	F3—C32—C33—F4	1.8 (5)
C1—Ga1—O—Ga2	−165.26 (19)	C31—C32—C33—F4	−177.0 (3)
N3—Ga2—O—Ga1	−4.6 (2)	F3—C32—C33—C34	−179.2 (3)
N4—Ga2—O—Ga1	83.5 (2)	C31—C32—C33—C34	1.9 (6)
C15—Ga2—O—Ga1	−144.10 (19)	F4—C33—C34—F5	−2.3 (5)
N2—Ga1—N1—C5	3.6 (2)	C32—C33—C34—F5	178.7 (3)
O—Ga1—N1—C5	−102.3 (2)	F4—C33—C34—C29	178.3 (3)
C1—Ga1—N1—C5	132.5 (2)	C32—C33—C34—C29	−0.6 (6)
N2—Ga1—N1—C2	−174.7 (3)	C30—C29—C34—F5	178.6 (3)
O—Ga1—N1—C2	79.3 (3)	B—C29—C34—F5	0.6 (5)
C1—Ga1—N1—C2	−45.9 (3)	C30—C29—C34—C33	−2.1 (5)
N1—Ga1—N2—C11	−0.3 (2)	B—C29—C34—C33	179.9 (3)
O—Ga1—N2—C11	102.7 (2)	C29—B—C35—C40	176.3 (3)
C1—Ga1—N2—C11	−131.9 (2)	C41—B—C35—C40	59.3 (4)
N1—Ga1—N2—C12	168.6 (3)	C47—B—C35—C40	−61.6 (4)
O—Ga1—N2—C12	−88.3 (2)	C29—B—C35—C36	−11.7 (5)
C1—Ga1—N2—C12	37.1 (3)	C41—B—C35—C36	−128.7 (4)
N4—Ga2—N3—C19	−10.2 (2)	C47—B—C35—C36	110.4 (4)
C15—Ga2—N3—C19	−140.8 (2)	C40—C35—C36—F6	178.2 (3)
O—Ga2—N3—C19	92.6 (2)	B—C35—C36—F6	5.7 (5)
N4—Ga2—N3—C16	167.6 (3)	C40—C35—C36—C37	−3.2 (5)
C15—Ga2—N3—C16	37.0 (3)	B—C35—C36—C37	−175.6 (3)
O—Ga2—N3—C16	−89.6 (3)	F6—C36—C37—F7	2.5 (5)
N3—Ga2—N4—C25	6.2 (2)	C35—C36—C37—F7	−176.3 (3)
C15—Ga2—N4—C25	140.4 (2)	F6—C36—C37—C38	−177.6 (3)
O—Ga2—N4—C25	−99.1 (2)	C35—C36—C37—C38	3.7 (6)
N3—Ga2—N4—C26	−170.2 (3)	F7—C37—C38—F8	−0.2 (6)
C15—Ga2—N4—C26	−36.0 (3)	C36—C37—C38—F8	179.9 (3)
O—Ga2—N4—C26	84.5 (3)	F7—C37—C38—C39	178.5 (3)
C5—N1—C2—C3	163.1 (3)	C36—C37—C38—C39	−1.4 (6)
Ga1—N1—C2—C3	−18.6 (4)	F8—C38—C39—F9	−1.7 (6)
C5—N1—C2—C4	−74.6 (4)	C37—C38—C39—F9	179.6 (3)
Ga1—N1—C2—C4	103.7 (3)	F8—C38—C39—C40	177.9 (3)
C2—N1—C5—C6	−9.6 (5)	C37—C38—C39—C40	−0.8 (6)
Ga1—N1—C5—C6	172.0 (2)	F9—C39—C40—F10	1.2 (5)
C2—N1—C5—C11	172.5 (3)	C38—C39—C40—F10	−178.4 (3)
Ga1—N1—C5—C11	−6.0 (4)	F9—C39—C40—C35	−179.2 (3)
N1—C5—C6—C7	−178.1 (4)	C38—C39—C40—C35	1.2 (6)
C11—C5—C6—C7	−0.4 (6)	C36—C35—C40—F10	−179.7 (3)
C5—C6—C7—C8	−6.9 (7)	B—C35—C40—F10	−6.5 (5)
C6—C7—C8—C9	0.8 (7)	C36—C35—C40—C39	0.8 (5)
C7—C8—C9—C10	5.8 (7)	B—C35—C40—C39	173.9 (3)
C8—C9—C10—C11	0.7 (7)	C29—B—C41—C42	66.3 (4)
C12—N2—C11—C10	4.6 (5)	C35—B—C41—C42	−171.3 (3)
Ga1—N2—C11—C10	173.7 (3)	C47—B—C41—C42	−56.7 (4)
C12—N2—C11—C5	−171.8 (3)	C29—B—C41—C46	−109.8 (4)
Ga1—N2—C11—C5	−2.7 (3)	C35—B—C41—C46	12.6 (5)
C9—C10—C11—N2	171.9 (4)	C47—B—C41—C46	127.2 (4)
C9—C10—C11—C5	−12.0 (6)	C46—C41—C42—F11	177.0 (3)
N1—C5—C11—N2	5.7 (4)	B—C41—C42—F11	0.4 (5)
C6—C5—C11—N2	−172.2 (3)	C46—C41—C42—C43	−4.0 (5)
N1—C5—C11—C10	−170.6 (3)	B—C41—C42—C43	179.4 (3)
C6—C5—C11—C10	11.5 (5)	F11—C42—C43—F12	1.5 (5)
C11—N2—C12—C14	−156.4 (3)	C41—C42—C43—F12	−177.5 (3)
Ga1—N2—C12—C14	35.5 (4)	F11—C42—C43—C44	−178.2 (3)
C11—N2—C12—C13	80.8 (4)	C41—C42—C43—C44	2.8 (6)
Ga1—N2—C12—C13	−87.4 (3)	F12—C43—C44—F13	0.9 (6)
C19—N3—C16—C17	−169.8 (3)	C42—C43—C44—F13	−179.4 (3)
Ga2—N3—C16—C17	12.5 (4)	F12—C43—C44—C45	−178.8 (3)
C19—N3—C16—C18	68.2 (4)	C42—C43—C44—C45	0.9 (6)
Ga2—N3—C16—C18	−109.5 (3)	F13—C44—C45—F14	−3.4 (6)
C16—N3—C19—C20	15.9 (5)	C43—C44—C45—F14	176.4 (3)
Ga2—N3—C19—C20	−166.1 (2)	F13—C44—C45—C46	177.4 (3)
C16—N3—C19—C25	−165.9 (3)	C43—C44—C45—C46	−2.9 (6)
Ga2—N3—C19—C25	12.0 (3)	C42—C41—C46—F15	−178.0 (3)
N3—C19—C20—C21	179.7 (4)	B—C41—C46—F15	−1.7 (5)
C25—C19—C20—C21	1.7 (6)	C42—C41—C46—C45	1.8 (5)
C19—C20—C21—C22	5.4 (7)	B—C41—C46—C45	178.1 (3)
C20—C21—C22—C23	0.6 (7)	F14—C45—C46—F15	2.1 (5)
C21—C22—C23—C24	−6.4 (7)	C44—C45—C46—F15	−178.7 (3)
C22—C23—C24—C25	−1.5 (7)	F14—C45—C46—C41	−177.8 (3)
C26—N4—C25—C24	−0.8 (5)	C44—C45—C46—C41	1.5 (6)
Ga2—N4—C25—C24	−177.2 (3)	C29—B—C47—C48	−128.7 (4)
C26—N4—C25—C19	175.2 (3)	C41—B—C47—C48	−11.8 (5)
Ga2—N4—C25—C19	−1.2 (4)	C35—B—C47—C48	110.0 (4)
C23—C24—C25—N4	−170.6 (4)	C29—B—C47—C52	57.0 (4)
C23—C24—C25—C19	13.9 (6)	C41—B—C47—C52	173.9 (3)
N3—C19—C25—N4	−7.1 (4)	C35—B—C47—C52	−64.3 (4)
C20—C19—C25—N4	171.0 (3)	C52—C47—C48—F16	177.1 (3)
N3—C19—C25—C24	168.8 (3)	B—C47—C48—F16	2.4 (6)
C20—C19—C25—C24	−13.1 (5)	C52—C47—C48—C49	−2.5 (5)
C25—N4—C26—C27	146.6 (3)	B—C47—C48—C49	−177.1 (3)
Ga2—N4—C26—C27	−37.4 (4)	F16—C48—C49—F17	2.4 (5)
C25—N4—C26—C28	−89.9 (4)	C47—C48—C49—F17	−178.0 (3)
Ga2—N4—C26—C28	86.1 (3)	F16—C48—C49—C50	−178.0 (3)
C41—B—C29—C30	−114.7 (4)	C47—C48—C49—C50	1.6 (6)
C35—B—C29—C30	122.3 (4)	F17—C49—C50—F18	−0.4 (5)
C47—B—C29—C30	7.4 (5)	C48—C49—C50—F18	−179.9 (3)
C41—B—C29—C34	63.0 (4)	F17—C49—C50—C51	179.4 (3)
C35—B—C29—C34	−60.1 (4)	C48—C49—C50—C51	−0.2 (6)
C47—B—C29—C34	−175.0 (3)	F18—C50—C51—F19	0.5 (5)
C34—C29—C30—F1	−176.1 (3)	C49—C50—C51—F19	−179.3 (3)
B—C29—C30—F1	1.7 (5)	F18—C50—C51—C52	179.7 (3)
C34—C29—C30—C31	3.7 (5)	C49—C50—C51—C52	−0.1 (6)
B—C29—C30—C31	−178.5 (3)	F19—C51—C52—F20	−1.7 (5)
F1—C30—C31—F2	−2.5 (5)	C50—C51—C52—F20	179.1 (3)
C29—C30—C31—F2	177.7 (3)	F19—C51—C52—C47	178.1 (3)
F1—C30—C31—C32	177.1 (3)	C50—C51—C52—C47	−1.2 (6)
C29—C30—C31—C32	−2.7 (6)	C48—C47—C52—F20	−177.9 (3)
F2—C31—C32—F3	0.4 (5)	B—C47—C52—F20	−2.7 (5)
C30—C31—C32—F3	−179.2 (3)	C48—C47—C52—C51	2.3 (5)
F2—C31—C32—C33	179.3 (3)	B—C47—C52—C51	177.5 (3)