Gallium hydride and monovalent indium compounds that feature tris­(pyrazol­yl)hydro­borate ligands

The tris­(pyrazol­yl)hydro­borate compounds [tris­(3,5-dimethyl-1H-pyrazol-1-yl-[kappa]N²)hydro­borato]indium(I), [In(C₁₅H₂₂BN₆)], abbreviated as [Tp^Me₂]In, and [tris­(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-[kappa]N²)hydro­borato]indium(I), [In(C₂₄H₄₀BN₆)], abbreviated as [Tp^But,Me]In, represent well defined examples of three-coordinate monovalent indium. In both compounds, the geometry at indium is pyramidal and natural bond orbital (NBO) calculations indicate that the indium lone pair occupies an orbital that is primarily 5s in character. The trivalent gallium hydride compound hydrido[tris­(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-[kappa]N²)hydroborato]gallium(III) tetra­chlorido­gallium(III), [Ga(C₂₄H₄₀BN₆)H][GaCl₄], abbreviated as {[Tp^But,Me]GaH}[GaCl₄], is obtained via reaction of [Tp^But,Me]Tl with [HGaCl₂]₂, and the Ga-H bond length of 1.49 (6) Å compares favorably with the mean value of 1.50 Å for structurally characterized gallium hydride compounds that are listed in the Cambridge Structural Database.

S1. Comment

Since its introduction by Trofimenko in 1966 (Trofimenko, 1966), the poly(pyrazolylborate) ligand system, and most notably the bis- and tris(pyrazolyl)hydroborate derivatives, denoted [Bp^R,^R'] and [Tp^R,^R'], respectively, has proven to be of immense value to coordination chemists (Trofimenko, 1999, 2004; Parkin, 1995; Kitajima & Tolman, 1995; Pettinari, 2008; Santini et al., 2010; Armbruster et al., 2009). Furthermore, the poly(pyrazolylborate) ligand system has also inspired the creation of a variety of related ligands, as exemplified by tris(mercaptoimidazolyl)hydroborate and tris(imidazolylidene)hydroborate derivatives (Spicer & Reglinski, 2009; Parkin, 2007; Smith, 2008). We report here the application of [Tp^R,^R'] ligands to Group 13 element chemistry, with specific emphasis on the structural characterization of trivalent gallium hydride and monovalent indium compounds.

Although a large variety of tris(pyrazolyl)hydroborate complexes of the Group 13 metals have been reported, the majority of these investigations pertain to trivalent complexes (Reger, 1996). For example, the first tris(pyrazolyl)hydroborate indium complex, namely trivalent [Tp^Me,Me]InCl₂.MeCN, was reported in 1988 (Cowley et al., 1988). Nevertheless, despite the prominence of trivalent compounds, the [Tp^R,^R'] ligand system is also capable of affording monovalent compounds, as illustrated by our report of the use of the sterically demanding tris(3,5-di-tert-butylpyrazolyl)hydroborate ligand [Tp^Bu,Bu] ligand to synthesize [Tp^Bu,Bu]Ga, the first monomeric monovalent gallium compound (Kuchta, Bonanno & Parkin, 1996 or Kuchta, Dias et al., 1996 ?). Moreover, trifluoromethyl substituents have likewise been shown to enable the isolation of monovalent [Tp^CF₃^,CF₃]Ga (Dias & Jin, 2000).

Sterically demanding substituents have also allowed for the synthesis of monovalent indium derivatives of [Tp^R,^R'], as illustrated by [Tp^Ph]In (Frazer et al., 1994), [Tp^Bu]In (Kuchta, Bonanno & Parkin, 1996 or Kuchta, Dias et al., 1996 ?; Dias et al., 1995), [Tp^Bu,Bu]In (Dias et al., 1995) and [Tp^CF₃^,CF₃]In (Dias & Jin, 1996, 2000). However, despite the fact that monovalent [Tp^R,^R']In has been isolated when the [Tp^R,^R'] ligand features bulky substituents, efforts to synthesize the methyl counterpart, [Tp^Me,Me]In, have been unsuccessful (Dias & Jin, 1996, 2000; Frazer et al., 1994). Specifically, rather than yield the required [Tp^Me,Me]In, the reaction of [Tp^Me,Me]K with InI gives the trivalent complex [In(Tp^Me,Me)₂]I (Frazer et al., 1992). It is, therefore, significant that we have been able to isolate [tris(3,5-dimethyl-1H-pyrazol-1-yl-κN²)hydroborato]indium(I), (I), abbreviated as [Tp^Me,Me]In, from the reaction of [Tp^Me,Me]K with InCl (see Scheme 1). The compound was structurally characterized by X-ray diffraction (Fig. 1). In addition, we have also isolated and structurally characterized [tris(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-κN²)hydroborato]indium(I), (II), abbreviated as [Tp^Bu,Me]In (Fig. 2), and have previously reported the Tl counterpart (Yoon & Parkin, 1995).

Since [Tp^Me,Me]In, (I), and [Tp^Bu,Me]In, (II), possess a common 5-methyl substituent, comparison of their structures provides a means of assessing the impact of a 3-methyl versus a 3-tert-butyl substituent and, interestingly, the In—N bond lengths of (I) (average 2.367 Å; Table 2) are only slightly shorter than those of (II) (average 2.411 Å; Table 3). For comparison, the range of In—N bond lengths is 1.93–2.93 Å (average 2.28 Å) in the Cambridge Structural Database (CSD, Version 5.34; Allen, 2002). In this regard, the In—N bonds in all of these monovalent (Parkin, 2006) [Tp^R,^R']In compounds are considerably longer than those in trivalent compounds such as [Tp^Me,Me]InCl₂.MeCN (Cowley et al., 1988), [In{Tp^Me,Me}]⁺ (Frazer et al., 1992), [Tp^Bu,Bu]InSe (Kuchta & Parkin, 1995), and [WIn{Tp^Me,Me}(CO)₅] (Reger et al., 1994).

The structural characterization of (II) also completes the series of compounds [Tp^Bu,^R]In for which the 5-R substituent is H, Me and Bu. It is of note that only the Bu substituent is sufficiently large to cause a significant propeller-like twist, such that the In···B axis is not coincident with the pyrazolyl planes and the molecular geometry deviates considerably from C_3v symmetry. However, despite this twist, the coordination geometry about the In atom is similar in all three compounds (Tables 2–4).

The most interesting feature of (I) and (II) is that the N—In—N angles are very acute, such that the indium centers are highly pyramidal. A simple measure of the degree of the pyramidality (P) is provided by the deviation of the sum of the N—In—N bond angles from 360°, i.e. P = 360° - Σ(N—In—N), and the values of P for (I) (126.0°) and (II) (121.4°) are in the range observed for other monovalent [Tp^R,^R']In compounds (Table 4). Furthermore, the indium centers of all of the monovalent [Tp^R,^R']In compounds are distinctly more pyramidal than those of the [Tp^R,^R']In fragments in four-, five- and six-coordinate compounds. For example, the pyramidalities of indium in four-coordinate [Tp^Bu,Bu]InSe (Kuchta & Parkin, 1995) and [WIn{Tp^Me,Me}(CO)₅] (Reger et al., 1994) are 100.7 and 111.7°, respectively. It is also of note that the pyramidality of indium in all of the three-coordinate [Tp^R,^R']In derivatives (120.3–145.4°) is significantly greater than that of the tris(mercaptoimidazolyl)hydroborate counterpart, In[Tm^Bu] (96.3°; Yurkerwich et al., 2008). Although In[Tm^Bu] differs from [Tp^R,^R']In in that the former has an S3 coordination environment, the reduced pyramidality of the former is presumably a consequence of the greater flexibility of the [Tm^Bu] ligand due to the greater chelate ring size.

With respect to comparisons within the [Tp^R,^R']In series of complexes, the most interesting observation is that the trifluoromethyl derivative [Tp^CF₃^,CF₃]In is significantly more pyramidal (145.4°) than the other derivatives (120.3–126.0°). In this regard, the average In—N bond for [Tp^CF₃^,CF₃]In (2.578 Å) is longer than those in other [Tp^R,^R']In derivatives (2.367–2.488 Å), as summarized in Table 4. Density functional theory (DFT; B3LYP level; see Refinement for details) calculations reproduce this trend, with [Tp^CF₃^,CF₃]In having the longest In—N bonds and the most pyramidal indium center. Furthermore, a natural bond orbital (NBO) analysis (Weinhold & Landis, 2005; Weinhold, 2012; Glendening et al., 2012) indicates that the highest occupied orbital of each of the [Tp^R,^R']In compounds is an indium spⁿ lone-pair hybrid orbital (Fig. 3), for which [Tp^CF₃^,CF₃]In (95.8°) and (I) (90.7°) possess the greatest and least amount of 5s character, respectively. Finally, the pyramidality of the In atom in [Tp^R,^R']In is intermediate between those of gallium and thallium, as illustrated by the values for [Tp^Bu,Bu]Ga (107.3°; Dias & Jin, 2000), [Tp^Bu,Bu]In (120.3°; Frazer et al., 1994) and [Tp^Bu,Bu]Tl (125.8°; Dowling et al., 1995), a trend that is anticipated on the basis of the variation in the covalent radii of Ga (1.22 Å), In (1.42 Å) and Tl (1.45 Å) (Cordero et al., 2008).

In addition to the synthesis of monovalent [Tp^Bu,Bu]Ga (Kuchta, Bonanno & Parkin, 1996 or Kuchta, Dias et al., 1996 ?), we have previously employed [Tp^R,^R'] ligands to afford a variety of trivalent gallium compounds, including [Tp^Bu,Bu]Ga→ GaI₃ (Kuchta, Bonanno & Parkin, 1996 or Kuchta, Dias et al., 1996 ?), [Tp^Me,Me]Ga→ GaX₃ (X = Cl, I), [Tp^Me,Me]GaGaI₂GaI₂(Hpz^Me₂) and [Tp^Me,Me]Ga(GaI₂)₂Ga[Tp^Me,Me] (Yurkerwich & Parkin, 2010). We now report that a tris(pyrazolyl)hydroborate ligand can be used to obtain a gallium hydride complex. Specifically, hydrido[tris(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-κN²)hydroborato]gallium(III) tetrachloridogallium(III), [Ga(Tp^Bu,Me)H][GaCl₄], (III), may be obtained via the reaction of [Tp^Bu,Me]Tl with [HGaCl₂]₂ (Nogai & Schmidbaur, 2002; Alexander & Cole, 2008), as illustrated in Scheme 2.

The molecular structure of (III) has been determined by X-ray diffraction, as illustrated in Fig. 4, thereby demonstrating that the compound consists of a discrete monomeric cationic gallium species that features a terminal hydride ligand. In this regard, tris(pyrazolyl)hydroborate ligands have been employed to synthesize several other monomeric [Tp^R,^R']MH compounds, namely [Tp^Bu]BeH (Han & Parkin, 1992), [Tp^Bu]ZnH (Looney et al., 1995; Han et al., 1991), [Tp^Bu,Me]ZnH (Bergquist & Parkin, 1999), [Tp^Ph,Me]ZnH (Rombach et al., 2002), [Tp^Bu]CdH (Reger et al., 1993) and [Tp^Bu,Me]CoH (Jewson et al., 1999). For comparison, selected bond-length data are summarized in Table 5. It is of note that the Ga—H bond length of 1.49 (6) Å compares favorably with the mean value of 1.50 Å for structurally characterized gallium hydride compounds that are listed in the CSD, and also with the value in the DFT geometry-optimized [Ga(Tp^Bu,Me)H]⁺ cation (1.53 Å). The Ga–N bonds of [Ga(Tp^Bu,Me)H]⁺ (Table 6) are comparable with, although slightly shorter than, the average values in related trivalent [Tp^R,^R']Ga compounds, [Ga(Tp^Me,Me)₂]⁺ (2.064 Å; Cowley et al., 1988), [Tp^Bu,Bu]GaTe (2.060 Å; Kuchta & Parkin, 1997) and [FeGa(Tp^Me,Me)(CO)₄] (1.990 Å; Reger et al., 1994), but all of these bonds are distinctly shorter than that for the monovalent gallium compound [Tp^Bu,Bu]Ga (2.230 Å; Kuchta, Bonanno & Parkin, 1996 or Kuchta, Dias et al., 1996 ?).

In conclusion, tris(pyrazolyl)hydroborate ligation has been used to isolate mononuclear examples of trivalent gallium hydride and monovalent indium complexes, namely [Ga(Tp^Bu,Me)H][GaCl₄], [Tp^Me,Me]In and [Tp^Bu,Me]In, all of which have been structurally characterized by X-ray diffraction.

Related literature

For related literature, see: Alexander & Cole (2008); Allen (2002); Armbruster et al. (2009); Bergquist & Parkin (1999); Burger & Bercaw (1987); Cordero et al. (2008); Cowley et al. (1988); Dias & Jin (1996, 2000); Dias et al. (1995); Dowling et al. (1995); Frazer et al. (1992, 1994); Glendening et al. (2001, 2012); Han & Parkin (1992); Han et al. (1991); Jewson et al. (1999); Kitajima & Tolman (1995); Kuchta & Parkin (1995, 1997); Kuchta, Bonanno & Parkin (1996); Kuchta, Dias, Bott & Parkin (1996); Looney et al. (1995); McNally et al. (1987); Nogai & Schmidbaur (2002); Parkin (1995, 2006, 2007); Pettinari (2008); Reger (1996); Reger et al. (1993, 1994); Rombach et al. (2002); Santini et al. (2010); Schrödinger (2009); Shriver & Drezdzon (1986); Smith (2008); Spicer & Reglinski (2009); Trofimenko (1966, 1967, 1999, 2004); Trofimenko et al. (1992); Weinhold (2012); Weinhold & Landis (2005); Yoon & Parkin (1995); Yurkerwich & Parkin (2010); Yurkerwich et al. (2008).

S2. Experimental

All manipulations were performed using a combination of glove-box, high vacuum and Schlenk techniques under a nitrogen or argon atmosphere (McNally et al., 1987; Burger & Bercaw, 1987; Shriver & Drezdzon, 1986). Solvents were purified and degassed by standard procedures. [Tp^Me,Me]In, (I), was synthesized by the reaction of InCl with [Tp^Me,Me]K (Trofimenko, 1967) and crystals suitable for X-ray diffraction were obtained from a solution in benzene. [Tp^Bu,Me]In, (II), was synthesized by the reaction of InCl with [Tp^Bu,Me]Tl (Trofimenko et al., 1992) and crystals suitable for X-ray diffraction were obtained from a solution in benzene. [Ga(Tp^Bu,Me)H][GaCl₄], (III), was synthesized via the reaction of [Tp^Bu,Me]Tl (Trofimenko et al., 1992) with (HGaCl₂)₂ and crystals suitable for X-ray diffraction were obtained from a solution in benzene.

S3. Refinement

Calculations were carried out using density functional theory (DFT) as implemented in the JAGUAR7.6 (release 110) suite of ab initio quantum chemistry programs (Schrödinger, 2009). Geometry optimizations were performed with the B3LYP density functional using the 6–31G** (H, B, C, N, S) and LAV3P (In, Ga) basis set, and NBO calculations were performed with the program NBO (Glendening et al., 2001), as implemented in the JAGUAR suite of programs, using the 6–31G** and LAV3P basis sets.

[Tp^Bu,Me]In resides on a mirror plane and, although the structure can be refined reasonably well neglecting disorder, the displacement parameters associated with the pyrazolyl group on the mirror plane are poorly behaved. The structure was therefore modeled as two components using noncrystallographic symmetry restraints, and they refined to site occupancies of 0.488 and 0.512. In addition, rigid-bond and geometric restraints were used to improve the model.

The H atom on boron in (III) was refined isotropically with Uiso = 1.2UisoB, while that for (I) was restrained to a B—H distance of 1.10 (2)Å, with Uiso = 1.2UisoB and that for (II) was restrained to a B—H distance of 1.07 (2)Å. The H atom on gallium in (III) was refined isotropically with no restraints. All other H atoms were placed in calculated positions, with U_iso(H) = 1.2U_iso(Csp²) or 1.5U_iso(Csp³).

Computing details

Data collection: SMART (Bruker, 2007) for (I), (III); APEX2 (Bruker, 2007) for (II). Cell refinement: SMART (Bruker, 2007) for (I), (III); SAINT (Bruker, 2007) for (II). For all compounds, data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), with the atom-numbering scheme. [Please provide a revised plot with C atoms labelled as well] Displacement ellipsoids are drawn at the 30% probability level. C- and N-bound H atoms have been omitted for clarity. Atoms marked with a prime (') are at the symmetry position (x, -y + 1/2, z).

Fig. 2. The molecular structure of (II), with the atom-numbering scheme. [Please provide a revised plot with C atoms labelled as well] Only one of the disordered components is shown [Which?]. Displacement ellipsoids are drawn at the 30% probability level. C- and N-bound H atoms have been omitted for clarity. Atoms marked with a prime (') are at the symmetry position (-x - 1/2, y, z).

Fig. 3. Highest occupied NBOs of geometry-optimized (I) (left) and [Tp^CF₃^,CF₃]In (right).

Fig. 4. The molecular structure of the cation of (III), with the atom-numbering scheme. [Please provide a revised plot with C atoms labelled as well] Displacement ellipsoids are drawn at the 30% probability level. C- and N-bound H atoms have been omitted for clarity.

(I) [Tris(3,5-dimethyl-1H-pyrazol-1-yl-κN²)hydroborato]indium(I)

Crystal data

[In(C15H22BN6)]	Dx = 1.535 Mg m^−3
Mr = 412.02	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 9848 reflections
a = 17.1939 (7) Å	θ = 2.4–32.2°
b = 13.3487 (5) Å	µ = 1.33 mm^−1
c = 7.7658 (3) Å	T = 125 K
V = 1782.38 (12) Å^3	Block, colourless
Z = 4	0.20 × 0.10 × 0.10 mm
F(000) = 832

Data collection

Bruker SMART CCD area-detector diffractometer	2311 independent reflections
Radiation source: fine-focus sealed tube	2124 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ϕ and ω scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2007)	h = −22→22
Tmin = 0.776, Tmax = 0.878	k = −17→17
23607 measured reflections	l = −10→10

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0388P)^2 + 2.7729P] where P = (Fo^2 + 2Fc^2)/3
2311 reflections	(Δ/σ)max = 0.001
120 parameters	Δρmax = 0.86 e Å^−3
1 restraint	Δρmin = −0.56 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	Occ. (<1)
In1	0.183897 (13)	0.2500	0.90716 (3)	0.01583 (9)
B1	0.3871 (2)	0.2500	0.9081 (5)	0.0166 (7)
H1	0.4515 (11)	0.2500	0.905 (5)	0.020*
N11	0.35660 (17)	0.2500	1.0958 (4)	0.0189 (6)
C11	0.3966 (2)	0.2500	1.2460 (5)	0.0233 (7)
N12	0.27834 (17)	0.2500	1.1292 (4)	0.0177 (6)
C12	0.3431 (2)	0.2500	1.3796 (4)	0.0248 (7)
H12A	0.3538	0.2500	1.4996	0.030*
C13	0.2699 (2)	0.2500	1.3004 (4)	0.0201 (7)
C14	0.4836 (2)	0.2500	1.2550 (6)	0.0340 (9)
H14A	0.5051	0.2500	1.1381	0.051*
H14B	0.5013	0.1901	1.3164	0.051*	0.50
H14C	0.5013	0.3099	1.3164	0.051*	0.50
C15	0.1912 (2)	0.2500	1.3824 (5)	0.0273 (8)
H15A	0.1511	0.2500	1.2926	0.041*
H15B	0.1854	0.3099	1.4541	0.041*	0.50
H15C	0.1854	0.1901	1.4541	0.041*	0.50
N21	0.35699 (11)	0.15535 (15)	0.8142 (2)	0.0171 (4)
C21	0.39666 (14)	0.07833 (18)	0.7421 (3)	0.0210 (5)
N22	0.27854 (11)	0.13922 (14)	0.7947 (2)	0.0170 (4)
C22	0.34355 (15)	0.01168 (18)	0.6752 (3)	0.0225 (5)
H22A	0.3545	−0.0493	0.6170	0.027*
C23	0.27008 (14)	0.05217 (17)	0.7104 (3)	0.0192 (4)
C24	0.48369 (15)	0.0719 (2)	0.7427 (4)	0.0304 (6)
H24A	0.5053	0.1310	0.8003	0.046*
H24B	0.5028	0.0692	0.6238	0.046*
H24C	0.5000	0.0114	0.8042	0.046*
C25	0.19127 (14)	0.0111 (2)	0.6717 (4)	0.0239 (5)
H25A	0.1515	0.0576	0.7143	0.036*
H25B	0.1851	−0.0540	0.7284	0.036*
H25C	0.1854	0.0029	0.5470	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
In1	0.01785 (13)	0.01438 (13)	0.01524 (13)	0.000	−0.00005 (8)	0.000
B1	0.0213 (17)	0.0121 (15)	0.0165 (16)	0.000	−0.0010 (13)	0.000
N11	0.0208 (14)	0.0180 (13)	0.0179 (13)	0.000	−0.0033 (11)	0.000
C11	0.0291 (18)	0.0190 (15)	0.0218 (17)	0.000	−0.0092 (14)	0.000
N12	0.0218 (14)	0.0181 (13)	0.0132 (13)	0.000	−0.0005 (10)	0.000
C12	0.036 (2)	0.0232 (17)	0.0148 (15)	0.000	−0.0076 (14)	0.000
C13	0.0278 (17)	0.0156 (15)	0.0170 (15)	0.000	−0.0020 (13)	0.000
C14	0.0265 (19)	0.044 (2)	0.031 (2)	0.000	−0.0112 (16)	0.000
C15	0.035 (2)	0.029 (2)	0.0181 (17)	0.000	0.0054 (14)	0.000
N21	0.0187 (9)	0.0152 (9)	0.0176 (9)	0.0012 (7)	−0.0005 (7)	−0.0006 (7)
C21	0.0242 (12)	0.0175 (10)	0.0213 (11)	0.0021 (9)	0.0040 (9)	0.0013 (9)
N22	0.0196 (9)	0.0156 (9)	0.0156 (9)	−0.0004 (7)	−0.0001 (7)	−0.0008 (7)
C22	0.0303 (12)	0.0149 (10)	0.0224 (12)	0.0010 (10)	0.0046 (10)	−0.0036 (9)
C23	0.0263 (11)	0.0149 (10)	0.0166 (10)	0.0001 (9)	0.0000 (9)	−0.0005 (8)
C24	0.0248 (12)	0.0258 (13)	0.0406 (16)	0.0052 (10)	0.0046 (11)	−0.0026 (12)
C25	0.0283 (13)	0.0175 (11)	0.0259 (13)	−0.0024 (9)	−0.0017 (10)	−0.0057 (10)

Geometric parameters (Å, º)

In1—N22	2.3658 (19)	N12—C13	1.338 (4)
In1—N22^i	2.3659 (19)	C12—C13	1.400 (5)
In1—N12	2.369 (3)	C13—C15	1.496 (5)
B1—H1	1.109 (19)	N21—C21	1.355 (3)
B1—N21^i	1.548 (3)	N21—N22	1.374 (3)
B1—N21	1.548 (3)	C21—C22	1.377 (3)
B1—N11	1.548 (5)	C21—C24	1.499 (4)
N11—C11	1.354 (4)	N22—C23	1.342 (3)
N11—N12	1.370 (4)	C22—C23	1.401 (3)
C11—C12	1.387 (5)	C23—C25	1.492 (3)
C11—C14	1.498 (5)
N22—In1—N22^i	77.37 (9)	C11—C12—C13	105.5 (3)
N22—In1—N12	78.30 (7)	N12—C13—C12	109.8 (3)
N22^i—In1—N12	78.30 (7)	N12—C13—C15	121.4 (3)
H1—B1—N21^i	108.9 (10)	C12—C13—C15	128.8 (3)
H1—B1—N21	108.9 (10)	C21—N21—N22	109.24 (19)
N21^i—B1—N21	109.4 (3)	C21—N21—B1	130.2 (2)
H1—B1—N11	111 (2)	N22—N21—B1	120.5 (2)
N21^i—B1—N11	109.28 (19)	N21—C21—C22	108.2 (2)
N21—B1—N11	109.28 (19)	N21—C21—C24	123.0 (2)
C11—N11—N12	109.6 (3)	C22—C21—C24	128.8 (2)
C11—N11—B1	129.7 (3)	C23—N22—N21	107.21 (19)
N12—N11—B1	120.7 (3)	C23—N22—In1	130.31 (16)
N11—C11—C12	107.9 (3)	N21—N22—In1	122.44 (13)
N11—C11—C14	123.2 (4)	C21—C22—C23	106.0 (2)
C12—C11—C14	128.9 (4)	N22—C23—C22	109.4 (2)
C13—N12—N11	107.1 (3)	N22—C23—C25	121.0 (2)
C13—N12—In1	130.5 (2)	C22—C23—C25	129.6 (2)
N11—N12—In1	122.36 (19)

Symmetry code: (i) x, −y+1/2, z.

(II) \ [Tris(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-\ κN²)hydroborato]indium(I)

Crystal data

[In(C24H40BN6)]	Dx = 1.306 Mg m^−3
Mr = 538.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Ama2	Cell parameters from 9981 reflections
a = 16.6414 (8) Å	θ = 2.4–30.7°
b = 15.8504 (7) Å	µ = 0.89 mm^−1
c = 10.3779 (5) Å	T = 125 K
V = 2737.4 (2) Å^3	Block, colourless
Z = 4	0.30 × 0.15 × 0.10 mm
F(000) = 1120

Data collection

Bruker APEXII CCD area-detector diffractometer	4378 independent reflections
Radiation source: fine-focus sealed tube	4151 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 30.7°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2007)	h = −23→23
Tmin = 0.777, Tmax = 0.917	k = −22→22
22008 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.043	w = 1/[σ^2(Fo^2) + (0.0173P)^2 + 1.2139P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.004
4378 reflections	Δρmax = 0.29 e Å^−3
295 parameters	Δρmin = −0.25 e Å^−3
797 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.051 (15)

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. The structure was modeled by including two components with occupancies of 48.8% and 51.2%.

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	Occ. (<1)
In1	−0.2500	−0.1758 (5)	−0.6586 (5)	0.0209 (3)	0.488 (7)
B1	−0.2500	−0.3426 (6)	−0.4384 (14)	0.0162 (12)	0.488 (7)
H1	−0.2500	−0.395 (4)	−0.371 (6)	0.036 (12)*	0.488 (7)
N11	−0.1759 (6)	−0.3514 (5)	−0.5267 (11)	0.0126 (10)	0.488 (7)
N12	−0.1541 (5)	−0.2881 (6)	−0.6101 (11)	0.0108 (13)	0.488 (7)
C11	−0.1177 (6)	−0.4114 (5)	−0.5267 (9)	0.0133 (9)	0.488 (7)
C12	−0.0576 (6)	−0.3911 (6)	−0.6145 (9)	0.0129 (11)	0.488 (7)
H12A	−0.0100	−0.4213	−0.6349	0.016*	0.488 (7)
C13	−0.0851 (6)	−0.3150 (6)	−0.6647 (9)	0.0187 (16)	0.488 (7)
C14	−0.0466 (8)	−0.2630 (7)	−0.7719 (11)	0.024 (2)	0.488 (7)
C15	−0.0991 (15)	−0.2547 (17)	−0.8913 (19)	0.0303 (15)	0.488 (7)
H15A	−0.1466	−0.2207	−0.8708	0.045*	0.488 (7)
H15B	−0.1160	−0.3109	−0.9199	0.045*	0.488 (7)
H15C	−0.0684	−0.2272	−0.9602	0.045*	0.488 (7)
C16	0.0322 (10)	−0.3061 (10)	−0.8108 (18)	0.046 (3)	0.488 (7)
H16A	0.0664	−0.3127	−0.7346	0.069*	0.488 (7)
H16B	0.0600	−0.2715	−0.8750	0.069*	0.488 (7)
H16C	0.0205	−0.3617	−0.8475	0.069*	0.488 (7)
C17	−0.0266 (12)	−0.1738 (8)	−0.7232 (16)	0.040 (3)	0.488 (7)
H17A	−0.0753	−0.1477	−0.6879	0.060*	0.488 (7)
H17B	−0.0064	−0.1396	−0.7948	0.060*	0.488 (7)
H17C	0.0145	−0.1773	−0.6558	0.060*	0.488 (7)
C18	−0.1208 (9)	−0.4861 (6)	−0.4388 (10)	0.0231 (13)	0.488 (7)
H18A	−0.1225	−0.4669	−0.3491	0.035*	0.488 (7)
H18B	−0.0729	−0.5211	−0.4521	0.035*	0.488 (7)
H18C	−0.1690	−0.5194	−0.4576	0.035*	0.488 (7)
N21	−0.2500	−0.2583 (4)	−0.3660 (7)	0.0168 (10)	0.488 (7)
N22	−0.2500	−0.1807 (5)	−0.4277 (7)	0.0183 (14)	0.488 (7)
C21	−0.2500	−0.2470 (5)	−0.2367 (7)	0.0208 (13)	0.488 (7)
C22	−0.2500	−0.1616 (5)	−0.2142 (7)	0.0270 (13)	0.488 (7)
H22A	−0.2500	−0.1347	−0.1323	0.032*	0.488 (7)
C23	−0.2500	−0.1218 (4)	−0.3331 (8)	0.0239 (15)	0.488 (7)
C24	−0.2500	−0.0287 (4)	−0.3668 (7)	0.0288 (14)	0.488 (7)
C25	−0.2500	0.0233 (5)	−0.2427 (8)	0.049 (2)	0.488 (7)
H25A	−0.2018	0.0100	−0.1924	0.073*	0.244 (3)
H25B	−0.2980	0.0096	−0.1920	0.073*	0.244 (3)
H25C	−0.2503	0.0835	−0.2642	0.073*	0.488 (7)
C26	−0.3255 (4)	−0.0055 (4)	−0.4426 (6)	0.0368 (13)	0.488 (7)
H26A	−0.3270	−0.0378	−0.5231	0.055*	0.488 (7)
H26B	−0.3248	0.0550	−0.4624	0.055*	0.488 (7)
H26C	−0.3732	−0.0187	−0.3910	0.055*	0.488 (7)
C27	−0.2500	−0.3189 (5)	−0.1437 (7)	0.0391 (13)	0.488 (7)
H27A	−0.2500	−0.3723	−0.1913	0.059*	0.488 (7)
H27B	−0.2981	−0.3158	−0.0894	0.059*	0.244 (3)
H27C	−0.2019	−0.3158	−0.0894	0.059*	0.244 (3)
In2	−0.2500	−0.1749 (4)	−0.6762 (4)	0.0209 (3)	0.512 (7)
B2	−0.2500	−0.3242 (6)	−0.4384 (13)	0.0162 (12)	0.512 (7)
H2	−0.2500	−0.371 (4)	−0.363 (6)	0.036 (12)*	0.512 (7)
N31	−0.1716 (6)	−0.3355 (5)	−0.5174 (10)	0.0126 (10)	0.512 (7)
N32	−0.1539 (6)	−0.2824 (7)	−0.6213 (12)	0.0226 (19)	0.512 (7)
C31	−0.1154 (6)	−0.3971 (5)	−0.5059 (8)	0.0133 (9)	0.512 (7)
C32	−0.0598 (6)	−0.3780 (6)	−0.5967 (9)	0.0198 (16)	0.512 (7)
H32A	−0.0120	−0.4094	−0.6114	0.024*	0.512 (7)
C33	−0.0819 (5)	−0.3062 (6)	−0.6656 (9)	0.0164 (14)	0.512 (7)
C34	−0.0371 (7)	−0.2584 (7)	−0.7707 (9)	0.0201 (17)	0.512 (7)
C35	−0.0897 (15)	−0.2539 (16)	−0.8928 (18)	0.0303 (15)	0.512 (7)
H35A	−0.0646	−0.2161	−0.9556	0.045*	0.512 (7)
H35B	−0.1431	−0.2324	−0.8701	0.045*	0.512 (7)
H35C	−0.0949	−0.3104	−0.9302	0.045*	0.512 (7)
C36	0.0410 (9)	−0.3027 (8)	−0.8071 (17)	0.035 (2)	0.512 (7)
H36A	0.0669	−0.2721	−0.8780	0.052*	0.512 (7)
H36B	0.0294	−0.3606	−0.8343	0.052*	0.512 (7)
H36C	0.0771	−0.3037	−0.7324	0.052*	0.512 (7)
C37	−0.0200 (10)	−0.1689 (6)	−0.7231 (15)	0.027 (2)	0.512 (7)
H37A	0.0159	−0.1404	−0.7839	0.041*	0.512 (7)
H37B	0.0056	−0.1714	−0.6381	0.041*	0.512 (7)
H37C	−0.0706	−0.1375	−0.7167	0.041*	0.512 (7)
C38	−0.1225 (9)	−0.4706 (5)	−0.4156 (9)	0.0231 (13)	0.512 (7)
H38A	−0.0729	−0.5038	−0.4182	0.035*	0.512 (7)
H38B	−0.1679	−0.5061	−0.4418	0.035*	0.512 (7)
H38C	−0.1315	−0.4498	−0.3278	0.035*	0.512 (7)
N41	−0.2500	−0.2358 (4)	−0.3752 (7)	0.0168 (10)	0.512 (7)
N42	−0.2500	−0.1636 (5)	−0.4483 (7)	0.0225 (15)	0.512 (7)
C41	−0.2500	−0.2154 (5)	−0.2485 (6)	0.0221 (13)	0.512 (7)
C42	−0.2500	−0.1286 (5)	−0.2395 (6)	0.0253 (12)	0.512 (7)
H42A	−0.2500	−0.0958	−0.1628	0.030*	0.512 (7)
C43	−0.2500	−0.0986 (4)	−0.3657 (7)	0.0215 (13)	0.512 (7)
C44	−0.2500	−0.0084 (4)	−0.4145 (7)	0.0305 (14)	0.512 (7)
C45	−0.2500	0.0520 (4)	−0.3001 (8)	0.0457 (18)	0.512 (7)
H45A	−0.2021	0.0420	−0.2474	0.069*	0.256 (3)
H45B	−0.2983	0.0425	−0.2480	0.069*	0.256 (3)
H45C	−0.2497	0.1103	−0.3315	0.069*	0.512 (7)
C46	−0.3263 (3)	0.0086 (4)	−0.4933 (6)	0.0356 (12)	0.512 (7)
H46A	−0.3248	−0.0247	−0.5730	0.053*	0.512 (7)
H46B	−0.3293	0.0687	−0.5147	0.053*	0.512 (7)
H46C	−0.3736	−0.0075	−0.4427	0.053*	0.512 (7)
C47	−0.2500	−0.2795 (5)	−0.1438 (6)	0.0391 (13)	0.512 (7)
H47A	−0.2500	−0.2510	−0.0600	0.059*	0.512 (7)
H47B	−0.2019	−0.3149	−0.1512	0.059*	0.256 (3)
H47C	−0.2981	−0.3149	−0.1512	0.059*	0.256 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
In1	0.02145 (6)	0.01882 (12)	0.0224 (9)	0.000	0.000	0.0042 (7)
B1	0.0161 (10)	0.015 (4)	0.0176 (10)	0.000	0.000	0.008 (3)
N11	0.0146 (9)	0.006 (2)	0.0168 (13)	−0.0051 (16)	−0.0030 (9)	−0.0014 (18)
N12	0.008 (2)	0.016 (2)	0.009 (2)	0.0039 (19)	−0.0006 (14)	0.0027 (17)
C11	0.0162 (8)	0.010 (2)	0.014 (2)	−0.0027 (14)	−0.0066 (14)	−0.0081 (16)
C12	0.0128 (18)	0.010 (2)	0.016 (2)	0.0033 (16)	0.0044 (15)	−0.0071 (19)
C13	0.016 (2)	0.025 (3)	0.016 (3)	−0.0101 (19)	0.002 (3)	−0.009 (3)
C14	0.013 (3)	0.026 (3)	0.034 (4)	−0.002 (2)	0.004 (2)	−0.004 (2)
C15	0.023 (4)	0.0474 (11)	0.0203 (8)	−0.008 (2)	0.0022 (18)	0.0036 (7)
C16	0.024 (4)	0.075 (6)	0.039 (5)	−0.002 (3)	0.015 (3)	0.018 (4)
C17	0.041 (6)	0.047 (5)	0.031 (5)	−0.021 (4)	0.000 (4)	0.015 (4)
C18	0.0223 (10)	0.019 (3)	0.028 (3)	0.003 (2)	−0.002 (2)	0.002 (2)
N21	0.0190 (9)	0.016 (3)	0.0157 (12)	0.000	0.000	0.0025 (18)
N22	0.019 (2)	0.018 (3)	0.018 (2)	0.000	0.000	−0.005 (2)
C21	0.018 (2)	0.028 (4)	0.017 (3)	0.000	0.000	−0.002 (3)
C22	0.023 (2)	0.033 (4)	0.025 (3)	0.000	0.000	−0.006 (2)
C23	0.018 (2)	0.019 (3)	0.035 (4)	0.000	0.000	−0.006 (2)
C24	0.022 (2)	0.024 (3)	0.040 (4)	0.000	0.000	−0.008 (2)
C25	0.059 (4)	0.036 (4)	0.050 (4)	0.000	0.000	−0.024 (3)
C26	0.040 (2)	0.018 (2)	0.052 (4)	0.0045 (17)	−0.005 (3)	0.003 (2)
C27	0.0412 (17)	0.058 (4)	0.018 (2)	0.000	0.000	0.011 (3)
In2	0.02145 (6)	0.01882 (12)	0.0224 (9)	0.000	0.000	0.0042 (7)
B2	0.0161 (10)	0.015 (4)	0.0176 (10)	0.000	0.000	0.008 (3)
N31	0.0146 (9)	0.006 (2)	0.0168 (13)	−0.0051 (16)	−0.0030 (9)	−0.0014 (18)
N32	0.026 (3)	0.021 (2)	0.020 (3)	−0.0080 (19)	0.001 (2)	0.0100 (18)
C31	0.0162 (8)	0.010 (2)	0.014 (2)	−0.0027 (14)	−0.0066 (14)	−0.0081 (16)
C32	0.018 (2)	0.017 (3)	0.025 (3)	0.0072 (18)	−0.0031 (18)	−0.010 (2)
C33	0.014 (2)	0.0115 (15)	0.024 (3)	0.0012 (16)	−0.008 (3)	0.002 (3)
C34	0.011 (3)	0.035 (3)	0.015 (3)	−0.0120 (19)	−0.0004 (16)	0.009 (2)
C35	0.023 (4)	0.0474 (11)	0.0203 (8)	−0.008 (2)	0.0022 (18)	0.0036 (7)
C36	0.016 (3)	0.037 (3)	0.051 (6)	0.007 (2)	0.013 (2)	0.006 (3)
C37	0.024 (3)	0.023 (3)	0.035 (5)	−0.014 (2)	−0.003 (3)	0.002 (3)
C38	0.0223 (10)	0.019 (3)	0.028 (3)	0.003 (2)	−0.002 (2)	0.002 (2)
N41	0.0190 (9)	0.016 (3)	0.0157 (12)	0.000	0.000	0.0025 (18)
N42	0.028 (3)	0.015 (3)	0.024 (3)	0.000	0.000	0.001 (2)
C41	0.021 (2)	0.029 (4)	0.017 (2)	0.000	0.000	0.004 (3)
C42	0.022 (2)	0.037 (3)	0.017 (3)	0.000	0.000	−0.012 (2)
C43	0.017 (2)	0.025 (3)	0.023 (3)	0.000	0.000	−0.005 (2)
C44	0.036 (3)	0.017 (3)	0.039 (4)	0.000	0.000	−0.009 (2)
C45	0.034 (3)	0.034 (3)	0.069 (5)	0.000	0.000	−0.027 (3)
C46	0.033 (2)	0.024 (2)	0.050 (3)	0.0034 (16)	−0.006 (2)	0.001 (2)
C47	0.0412 (17)	0.058 (4)	0.018 (2)	0.000	0.000	0.011 (3)

Geometric parameters (Å, º)

In1—N22	2.397 (7)	In2—N42	2.372 (8)
In1—N12	2.443 (7)	In2—N32	2.405 (8)
In1—N12^i	2.443 (7)	In2—N32^i	2.405 (8)
B1—H1	1.08 (2)	B2—H2	1.08 (2)
B1—N21	1.533 (9)	B2—N41	1.547 (8)
B1—N11	1.543 (9)	B2—N31^i	1.551 (8)
B1—N11^i	1.543 (9)	B2—N31	1.551 (8)
B1—H1	1.08 (2)	B2—H1	1.32 (3)
B1—H2	0.90 (4)	B2—H2	1.08 (2)
N11—C11	1.358 (9)	N31—C31	1.358 (8)
N11—N12	1.374 (9)	N31—N32	1.399 (9)
N12—C13	1.349 (8)	N32—C33	1.338 (9)
C11—C12	1.391 (9)	C31—C32	1.355 (9)
C11—C18	1.495 (9)	C31—C38	1.500 (9)
C12—C13	1.391 (9)	C32—C33	1.393 (9)
C12—H12A	0.9500	C32—H32A	0.9500
C13—C14	1.526 (9)	C33—C34	1.522 (8)
C14—C15	1.522 (10)	C34—C36	1.525 (9)
C14—C16	1.532 (10)	C34—C37	1.530 (9)
C14—C17	1.538 (10)	C34—C35	1.542 (9)
C15—H15A	0.9800	C35—H35A	0.9800
C15—H15B	0.9800	C35—H35B	0.9800
C15—H15C	0.9800	C35—H35C	0.9800
C16—H16A	0.9800	C36—H36A	0.9800
C16—H16B	0.9800	C36—H36B	0.9800
C16—H16C	0.9800	C36—H36C	0.9800
C17—H17A	0.9800	C37—H37A	0.9800
C17—H17B	0.9800	C37—H37B	0.9800
C17—H17C	0.9800	C37—H37C	0.9800
C18—H18A	0.9800	C38—H38A	0.9800
C18—H18B	0.9800	C38—H38B	0.9800
C18—H18C	0.9800	C38—H38C	0.9800
N21—C21	1.354 (8)	N41—C41	1.354 (8)
N21—N22	1.387 (7)	N41—N42	1.374 (7)
N22—C23	1.355 (8)	N42—C43	1.340 (8)
C21—C22	1.375 (8)	C41—C42	1.380 (9)
C21—C27	1.493 (8)	C41—C47	1.488 (8)
C22—C23	1.386 (9)	C42—C43	1.394 (8)
C22—H22A	0.9500	C42—H42A	0.9500
C23—C24	1.516 (9)	C43—C44	1.516 (8)
C24—C26^i	1.528 (7)	C44—C45	1.525 (8)
C24—C26	1.528 (7)	C44—C46	1.535 (6)
C24—C25	1.529 (8)	C44—C46^i	1.535 (6)
C25—H25A	0.9800	C45—H45A	0.9800
C25—H25B	0.9800	C45—H45B	0.9800
C25—H25C	0.9800	C45—H45C	0.9800
C26—H26A	0.9800	C46—H46A	0.9800
C26—H26B	0.9800	C46—H46B	0.9800
C26—H26C	0.9800	C46—H46C	0.9800
C27—H27A	0.9800	C47—H47A	0.9800
C27—H27B	0.9800	C47—H47B	0.9800
C27—H27C	0.9800	C47—H47C	0.9800
N22—In1—N12	76.7 (3)	N31—B2—H1	100.5 (19)
N22—In1—N12^i	76.7 (3)	H2—B2—H2	0 (3)
N12—In1—N12^i	81.6 (6)	N41—B2—H2	109 (4)
H1—B1—N21	110 (5)	N31^i—B2—H2	108 (2)
H1—B1—N11	108 (2)	N31—B2—H2	108 (2)
N21—B1—N11	111.7 (6)	H1—B2—H2	14 (7)
H1—B1—N11^i	108 (2)	C31—N31—N32	110.8 (7)
N21—B1—N11^i	111.7 (6)	C31—N31—B2	128.0 (7)
N11—B1—N11^i	106.2 (12)	N32—N31—B2	121.1 (8)
H1—B1—H1	0 (3)	C33—N32—N31	106.5 (7)
N21—B1—H1	110 (5)	C33—N32—In2	135.5 (6)
N11—B1—H1	108 (2)	N31—N32—In2	117.9 (6)
N11^i—B1—H1	108 (2)	C32—C31—N31	104.4 (7)
H1—B1—H2	20 (8)	C32—C31—C38	131.5 (8)
N21—B1—H2	91 (5)	N31—C31—C38	124.0 (8)
N11—B1—H2	118 (2)	C31—C32—C33	111.0 (7)
N11^i—B1—H2	118 (2)	C31—C32—H32A	124.5
H1—B1—H2	20 (8)	C33—C32—H32A	124.5
C11—N11—N12	108.9 (7)	N32—C33—C32	106.9 (7)
C11—N11—B1	129.3 (8)	N32—C33—C34	123.0 (7)
N12—N11—B1	121.3 (7)	C32—C33—C34	130.1 (7)
C13—N12—N11	105.0 (7)	C33—C34—C36	111.5 (8)
C13—N12—In1	134.4 (7)	C33—C34—C37	108.7 (9)
N11—N12—In1	119.3 (5)	C36—C34—C37	110.4 (9)
N11—C11—C12	110.5 (7)	C33—C34—C35	109.5 (11)
N11—C11—C18	122.0 (8)	C36—C34—C35	107.6 (10)
C12—C11—C18	127.5 (8)	C37—C34—C35	109.1 (10)
C11—C12—C13	102.1 (7)	C34—C35—H35A	109.5
C11—C12—H12A	128.9	C34—C35—H35B	109.5
C13—C12—H12A	128.9	H35A—C35—H35B	109.5
N12—C13—C12	113.4 (7)	C34—C35—H35C	109.5
N12—C13—C14	119.5 (8)	H35A—C35—H35C	109.5
C12—C13—C14	127.1 (7)	H35B—C35—H35C	109.5
C15—C14—C13	113.5 (12)	C34—C36—H36A	109.5
C15—C14—C16	108.4 (11)	C34—C36—H36B	109.5
C13—C14—C16	108.1 (9)	H36A—C36—H36B	109.5
C15—C14—C17	108.2 (11)	C34—C36—H36C	109.5
C13—C14—C17	110.3 (9)	H36A—C36—H36C	109.5
C16—C14—C17	108.2 (11)	H36B—C36—H36C	109.5
C14—C16—H16A	109.5	C34—C37—H37A	109.5
C14—C16—H16B	109.5	C34—C37—H37B	109.5
H16A—C16—H16B	109.5	H37A—C37—H37B	109.5
C14—C16—H16C	109.5	C34—C37—H37C	109.5
H16A—C16—H16C	109.5	H37A—C37—H37C	109.5
H16B—C16—H16C	109.5	H37B—C37—H37C	109.5
C21—N21—N22	109.9 (6)	C31—C38—H38A	109.5
C21—N21—B1	126.9 (7)	C31—C38—H38B	109.5
N22—N21—B1	123.2 (7)	H38A—C38—H38B	109.5
C23—N22—N21	106.1 (6)	C31—C38—H38C	109.5
C23—N22—In1	134.6 (6)	H38A—C38—H38C	109.5
N21—N22—In1	119.4 (5)	H38B—C38—H38C	109.5
N21—C21—C22	107.4 (6)	C41—N41—N42	109.7 (5)
N21—C21—C27	122.7 (6)	C41—N41—B2	128.9 (7)
C22—C21—C27	130.0 (6)	N42—N41—B2	121.4 (7)
C21—C22—C23	107.3 (6)	C43—N42—N41	106.7 (6)
C21—C22—H22A	126.4	C43—N42—In2	134.1 (5)
C23—C22—H22A	126.4	N41—N42—In2	119.2 (5)
N22—C23—C22	109.4 (6)	N41—C41—C42	107.7 (5)
N22—C23—C24	120.2 (7)	N41—C41—C47	123.1 (6)
C22—C23—C24	130.4 (6)	C42—C41—C47	129.2 (6)
C23—C24—C26^i	110.7 (4)	C41—C42—C43	106.0 (5)
C23—C24—C26	110.7 (4)	C41—C42—H42A	127.0
C26^i—C24—C26	110.7 (7)	C43—C42—H42A	127.0
C23—C24—C25	109.3 (6)	N42—C43—C42	109.8 (6)
C26^i—C24—C25	107.7 (4)	N42—C43—C44	120.7 (6)
C26—C24—C25	107.7 (4)	C42—C43—C44	129.4 (6)
C24—C25—H25A	109.5	C43—C44—C45	109.4 (6)
C24—C25—H25B	109.5	C43—C44—C46	110.1 (3)
H25A—C25—H25B	109.5	C45—C44—C46	107.8 (4)
C24—C25—H25C	109.5	C43—C44—C46^i	110.1 (3)
H25A—C25—H25C	109.5	C45—C44—C46^i	107.8 (4)
H25B—C25—H25C	109.5	C46—C44—C46^i	111.7 (6)
C21—C27—H27A	109.5	C44—C45—H45A	109.5
C21—C27—H27B	109.5	C44—C45—H45B	109.5
H27A—C27—H27B	109.5	H45A—C45—H45B	109.5
C21—C27—H27C	109.5	C44—C45—H45C	109.5
H27A—C27—H27C	109.5	H45A—C45—H45C	109.5
H27B—C27—H27C	109.5	H45B—C45—H45C	109.5
N42—In2—N32	79.5 (3)	C44—C46—H46A	109.5
N42—In2—N32^i	79.5 (3)	C44—C46—H46B	109.5
N32—In2—N32^i	83.3 (6)	H46A—C46—H46B	109.5
H2—B2—N41	109 (4)	C44—C46—H46C	109.5
H2—B2—N31^i	108 (2)	H46A—C46—H46C	109.5
N41—B2—N31^i	109.2 (5)	H46B—C46—H46C	109.5
H2—B2—N31	108 (2)	C41—C47—H47A	109.5
N41—B2—N31	109.2 (5)	C41—C47—H47B	109.5
N31^i—B2—N31	114.5 (11)	H47A—C47—H47B	109.5
H2—B2—H1	14 (7)	C41—C47—H47C	109.5
N41—B2—H1	123 (4)	H47A—C47—H47C	109.5
N31^i—B2—H1	100.5 (19)	H47B—C47—H47C	109.5
H1—B1—N11—C11	0 (4)	H2—B2—N31—C31	6 (4)
N21—B1—N11—C11	121.6 (11)	N41—B2—N31—C31	123.6 (10)
N11^i—B1—N11—C11	−116.4 (11)	N31^i—B2—N31—C31	−113.7 (11)
H1—B1—N11—N12	−171 (4)	H2—B2—N31—N32	−179 (4)
N21—B1—N11—N12	−49.1 (15)	N41—B2—N31—N32	−61.5 (13)
N11^i—B1—N11—N12	72.8 (13)	N31^i—B2—N31—N32	61.2 (13)
C11—N11—N12—C13	3.9 (13)	C31—N31—N32—C33	−6.5 (14)
B1—N11—N12—C13	176.4 (10)	B2—N31—N32—C33	177.8 (9)
C11—N11—N12—In1	172.6 (7)	C31—N31—N32—In2	174.6 (7)
B1—N11—N12—In1	−15.0 (15)	B2—N31—N32—In2	−1.1 (15)
N22—In1—N12—C13	−145.1 (13)	N42—In2—N32—C33	−135.8 (15)
N12^i—In1—N12—C13	136.7 (11)	N32^i—In2—N32—C33	143.7 (12)
N22—In1—N12—N11	50.4 (9)	N42—In2—N32—N31	42.8 (10)
N12^i—In1—N12—N11	−27.9 (12)	N32^i—In2—N32—N31	−37.7 (13)
N12—N11—C11—C12	−2.6 (12)	N32—N31—C31—C32	4.6 (11)
B1—N11—C11—C12	−174.3 (10)	B2—N31—C31—C32	180.0 (9)
N12—N11—C11—C18	175.8 (10)	N32—N31—C31—C38	−171.6 (10)
B1—N11—C11—C18	4.1 (15)	B2—N31—C31—C38	3.7 (14)
N11—C11—C12—C13	0.2 (8)	N31—C31—C32—C33	−1.1 (7)
C18—C11—C12—C13	−178.1 (9)	C38—C31—C32—C33	174.7 (9)
N11—N12—C13—C12	−4.0 (13)	N31—N32—C33—C32	5.4 (13)
In1—N12—C13—C12	−170.1 (9)	In2—N32—C33—C32	−175.9 (11)
N11—N12—C13—C14	175.1 (10)	N31—N32—C33—C34	−173.9 (10)
In1—N12—C13—C14	9.0 (17)	In2—N32—C33—C34	5 (2)
C11—C12—C13—N12	2.4 (9)	C31—C32—C33—N32	−2.8 (9)
C11—C12—C13—C14	−176.6 (10)	C31—C32—C33—C34	176.4 (10)
N12—C13—C14—C15	−62.4 (16)	N32—C33—C34—C36	−176.7 (13)
C12—C13—C14—C15	116.6 (13)	C32—C33—C34—C36	4.2 (13)
N12—C13—C14—C16	177.4 (13)	N32—C33—C34—C37	61.5 (14)
C12—C13—C14—C16	−3.6 (14)	C32—C33—C34—C37	−117.7 (10)
N12—C13—C14—C17	59.3 (15)	N32—C33—C34—C35	−57.7 (16)
C12—C13—C14—C17	−121.7 (11)	C32—C33—C34—C35	123.1 (12)
H1—B1—N21—C21	0.000 (3)	H2—B2—N41—C41	0.000 (3)
N11—B1—N21—C21	−120.7 (8)	N31^i—B2—N41—C41	117.1 (7)
N11^i—B1—N21—C21	120.6 (8)	N31—B2—N41—C41	−117.1 (7)
H1—B1—N21—N22	180.000 (3)	H2—B2—N41—N42	180.000 (3)
N11—B1—N21—N22	59.3 (8)	N31^i—B2—N41—N42	−62.9 (7)
N11^i—B1—N21—N22	−59.4 (8)	N31—B2—N41—N42	62.9 (7)
C21—N21—N22—C23	0.000 (1)	C41—N41—N42—C43	0.000 (1)
B1—N21—N22—C23	180.000 (1)	B2—N41—N42—C43	180.000 (1)
C21—N21—N22—In1	180.000 (1)	C41—N41—N42—In2	180.0
B1—N21—N22—In1	0.000 (2)	B2—N41—N42—In2	0.000 (1)
N12—In1—N22—C23	137.8 (3)	N32—In2—N42—C43	137.5 (3)
N12^i—In1—N22—C23	−137.8 (3)	N32^i—In2—N42—C43	−137.5 (3)
N12—In1—N22—N21	−42.2 (3)	N32—In2—N42—N41	−42.5 (3)
N12^i—In1—N22—N21	42.2 (3)	N32^i—In2—N42—N41	42.5 (3)
N22—N21—C21—C22	0.000 (1)	N42—N41—C41—C42	0.0
B1—N21—C21—C22	180.000 (1)	B2—N41—C41—C42	180.000 (1)
N22—N21—C21—C27	180.000 (1)	N42—N41—C41—C47	180.000 (1)
B1—N21—C21—C27	0.000 (2)	B2—N41—C41—C47	0.000 (2)
N21—C21—C22—C23	0.000 (1)	N41—C41—C42—C43	0.000 (1)
C27—C21—C22—C23	180.000 (1)	C47—C41—C42—C43	180.0
N21—N22—C23—C22	0.000 (1)	N41—N42—C43—C42	0.000 (1)
In1—N22—C23—C22	180.000 (1)	In2—N42—C43—C42	180.0
N21—N22—C23—C24	180.000 (1)	N41—N42—C43—C44	180.000 (1)
In1—N22—C23—C24	0.000 (1)	In2—N42—C43—C44	0.000 (1)
C21—C22—C23—N22	0.000 (1)	C41—C42—C43—N42	0.000 (1)
C21—C22—C23—C24	180.000 (1)	C41—C42—C43—C44	180.000 (1)
N22—C23—C24—C26^i	−61.6 (4)	N42—C43—C44—C45	180.0
C22—C23—C24—C26^i	118.4 (4)	C42—C43—C44—C45	0.0
N22—C23—C24—C26	61.6 (4)	N42—C43—C44—C46	61.8 (4)
C22—C23—C24—C26	−118.4 (4)	C42—C43—C44—C46	−118.2 (4)
N22—C23—C24—C25	180.000 (1)	N42—C43—C44—C46^i	−61.8 (4)
C22—C23—C24—C25	0.000 (1)	C42—C43—C44—C46^i	118.2 (4)

Symmetry code: (i) −x−1/2, y, z.

(III) \ Hydrido[tris(3-tert-butyl-5-methyl-1H-pyrazol-1-yl-\ κN²)hydroborato]gallium(III) tetrachloridogallium(III),

Crystal data

[Ga(C24H40BN6)H][GaCl4]	F(000) = 1448
Mr = 705.68	Dx = 1.407 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5170 (15) Å	Cell parameters from 2436 reflections
b = 17.753 (3) Å	θ = 2.4–21.5°
c = 19.763 (3) Å	µ = 1.96 mm^−1
β = 93.952 (3)°	T = 125 K
V = 3331.2 (9) Å^3	Plate, colourless
Z = 4	0.08 × 0.03 × 0.02 mm

Data collection

Bruker SMART CCD area-detector diffractometer	5876 independent reflections
Radiation source: fine-focus sealed tube	3039 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.243
ϕ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2007)	h = −11→11
Tmin = 0.859, Tmax = 0.962	k = −21→21
35586 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.025P)^2] where P = (Fo^2 + 2Fc^2)/3
5876 reflections	(Δ/σ)max < 0.001
353 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.52796 (7)	−0.11754 (4)	0.75445 (4)	0.0172 (2)
H1	0.482 (6)	−0.182 (3)	0.797 (3)	0.027 (18)*
Ga2	0.80991 (9)	0.21620 (5)	0.51098 (4)	0.0290 (2)
Cl1	0.6764 (2)	0.27063 (13)	0.58040 (12)	0.0631 (7)
Cl2	0.9045 (3)	0.29659 (14)	0.44610 (13)	0.0732 (8)
Cl3	0.9818 (2)	0.15992 (12)	0.56903 (11)	0.0418 (6)
Cl4	0.6811 (2)	0.13766 (12)	0.44944 (11)	0.0527 (6)
B1	0.6191 (8)	0.0058 (5)	0.6682 (4)	0.020 (2)
H2	0.651 (6)	0.050 (3)	0.637 (3)	0.024*
N11	0.4566 (5)	0.0057 (3)	0.6716 (3)	0.0201 (14)
C11	0.3581 (7)	0.0522 (4)	0.6427 (3)	0.0228 (17)
N12	0.3936 (5)	−0.0477 (3)	0.7105 (3)	0.0198 (14)
C12	0.2297 (7)	0.0283 (4)	0.6630 (4)	0.0249 (18)
H12A	0.1410	0.0505	0.6503	0.030*
C13	0.2518 (7)	−0.0340 (4)	0.7051 (3)	0.0185 (16)
C14	0.1502 (6)	−0.0784 (4)	0.7430 (3)	0.0201 (17)
C15	0.0004 (7)	−0.0592 (5)	0.7155 (4)	0.043 (2)
H15A	−0.0197	−0.0063	0.7255	0.064*
H15B	−0.0667	−0.0917	0.7371	0.064*
H15C	−0.0083	−0.0671	0.6663	0.064*
C16	0.1666 (8)	−0.0593 (5)	0.8180 (4)	0.042 (2)
H16A	0.1458	−0.0058	0.8243	0.064*
H16B	0.2635	−0.0698	0.8355	0.064*
H16C	0.1012	−0.0899	0.8425	0.064*
C17	0.1685 (7)	−0.1641 (4)	0.7322 (4)	0.035 (2)
H17A	0.2585	−0.1805	0.7544	0.053*
H17B	0.1673	−0.1748	0.6835	0.053*
H17C	0.0913	−0.1912	0.7517	0.053*
C18	0.3942 (7)	0.1178 (4)	0.6006 (3)	0.0290 (18)
H18A	0.4490	0.1007	0.5633	0.044*
H18B	0.4498	0.1540	0.6287	0.044*
H18C	0.3074	0.1421	0.5820	0.044*
N21	0.6633 (5)	−0.0716 (3)	0.6413 (3)	0.0179 (13)
C21	0.7379 (7)	−0.0899 (4)	0.5883 (4)	0.0220 (18)
N22	0.6283 (5)	−0.1372 (3)	0.6741 (3)	0.0197 (14)
C22	0.7480 (7)	−0.1676 (4)	0.5863 (3)	0.0210 (17)
H22A	0.7931	−0.1963	0.5535	0.025*
C23	0.6810 (7)	−0.1960 (4)	0.6406 (3)	0.0185 (16)
C24	0.6637 (7)	−0.2763 (4)	0.6629 (3)	0.0213 (17)
C25	0.7483 (8)	−0.2890 (4)	0.7295 (4)	0.046 (2)
H25A	0.8473	−0.2764	0.7244	0.069*
H25B	0.7411	−0.3420	0.7428	0.069*
H25C	0.7115	−0.2569	0.7645	0.069*
C26	0.5075 (8)	−0.2955 (4)	0.6694 (4)	0.045 (2)
H26A	0.4704	−0.2644	0.7050	0.067*
H26B	0.4985	−0.3488	0.6811	0.067*
H26C	0.4541	−0.2855	0.6262	0.067*
C27	0.7192 (9)	−0.3285 (4)	0.6092 (4)	0.052 (3)
H27A	0.8182	−0.3166	0.6032	0.078*
H27B	0.6636	−0.3213	0.5661	0.078*
H27C	0.7115	−0.3810	0.6239	0.078*
C28	0.7950 (8)	−0.0326 (4)	0.5427 (4)	0.032 (2)
H28A	0.8572	0.0019	0.5695	0.047*
H28B	0.7171	−0.0041	0.5201	0.047*
H28C	0.8485	−0.0578	0.5086	0.047*
N31	0.6834 (5)	0.0148 (3)	0.7418 (3)	0.0168 (13)
C31	0.7637 (7)	0.0693 (4)	0.7730 (3)	0.0202 (17)
N32	0.6586 (5)	−0.0395 (3)	0.7898 (3)	0.0163 (13)
C32	0.7914 (7)	0.0493 (4)	0.8398 (4)	0.0240 (18)
H32A	0.8453	0.0773	0.8733	0.029*
C33	0.7268 (7)	−0.0189 (4)	0.8490 (3)	0.0208 (17)
C34	0.7202 (8)	−0.0639 (4)	0.9131 (3)	0.0280 (19)
C35	0.8147 (9)	−0.0263 (5)	0.9695 (4)	0.055 (3)
H35A	0.9128	−0.0272	0.9573	0.082*
H35B	0.8069	−0.0538	1.0121	0.082*
H35C	0.7847	0.0260	0.9751	0.082*
C36	0.7734 (7)	−0.1441 (4)	0.9029 (4)	0.032 (2)
H36A	0.7078	−0.1708	0.8709	0.049*
H36B	0.7799	−0.1706	0.9465	0.049*
H36C	0.8667	−0.1422	0.8848	0.049*
C37	0.5678 (8)	−0.0651 (4)	0.9346 (4)	0.039 (2)
H37A	0.5082	−0.0935	0.9012	0.059*
H37C	0.5326	−0.0134	0.9372	0.059*
H37D	0.5656	−0.0892	0.9791	0.059*
C38	0.8094 (8)	0.1369 (4)	0.7359 (4)	0.032 (2)
H38C	0.7265	0.1630	0.7152	0.047*
H38D	0.8702	0.1213	0.7003	0.047*
H38A	0.8616	0.1708	0.7676	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0138 (4)	0.0193 (4)	0.0185 (4)	0.0004 (4)	0.0019 (3)	0.0008 (4)
Ga2	0.0323 (5)	0.0248 (5)	0.0303 (5)	0.0068 (4)	0.0037 (4)	0.0039 (4)
Cl1	0.0606 (16)	0.0637 (17)	0.0660 (17)	0.0216 (13)	0.0124 (13)	−0.0239 (14)
Cl2	0.0654 (17)	0.0650 (17)	0.089 (2)	−0.0020 (14)	0.0020 (14)	0.0549 (16)
Cl3	0.0333 (12)	0.0471 (14)	0.0453 (14)	0.0103 (10)	0.0039 (10)	0.0192 (11)
Cl4	0.0771 (17)	0.0407 (14)	0.0379 (13)	−0.0003 (12)	−0.0135 (12)	−0.0022 (11)
B1	0.021 (5)	0.017 (5)	0.022 (5)	−0.005 (4)	−0.005 (4)	0.005 (4)
N11	0.019 (3)	0.019 (3)	0.023 (4)	0.003 (3)	0.005 (3)	0.001 (3)
C11	0.023 (4)	0.015 (4)	0.029 (5)	0.005 (3)	−0.005 (3)	0.006 (4)
N12	0.012 (3)	0.021 (3)	0.026 (4)	0.002 (3)	0.006 (3)	0.000 (3)
C12	0.019 (4)	0.021 (4)	0.033 (5)	0.006 (3)	−0.011 (4)	0.001 (4)
C13	0.015 (4)	0.024 (4)	0.017 (4)	0.002 (3)	0.005 (3)	−0.007 (3)
C14	0.011 (4)	0.022 (4)	0.027 (5)	0.004 (3)	0.001 (3)	−0.001 (4)
C15	0.016 (4)	0.051 (6)	0.062 (6)	0.008 (4)	0.001 (4)	0.015 (5)
C16	0.040 (5)	0.051 (6)	0.037 (6)	−0.011 (4)	0.011 (4)	−0.001 (5)
C17	0.026 (5)	0.026 (5)	0.055 (6)	−0.002 (4)	0.015 (4)	0.006 (4)
C18	0.029 (4)	0.025 (4)	0.031 (4)	0.004 (4)	−0.008 (3)	0.003 (4)
N21	0.019 (3)	0.015 (3)	0.019 (4)	−0.001 (3)	−0.002 (3)	0.002 (3)
C21	0.013 (4)	0.029 (5)	0.024 (5)	0.001 (3)	0.003 (3)	0.008 (4)
N22	0.019 (3)	0.020 (3)	0.020 (3)	−0.001 (3)	0.002 (3)	−0.004 (3)
C22	0.026 (4)	0.017 (4)	0.020 (4)	0.002 (3)	0.006 (3)	−0.001 (3)
C23	0.021 (4)	0.019 (4)	0.016 (4)	−0.002 (3)	0.003 (3)	−0.002 (3)
C24	0.030 (4)	0.016 (4)	0.020 (4)	0.000 (3)	0.011 (3)	−0.002 (3)
C25	0.054 (6)	0.026 (5)	0.057 (6)	0.012 (4)	−0.005 (5)	0.012 (4)
C26	0.049 (6)	0.024 (5)	0.063 (6)	−0.005 (4)	0.018 (5)	0.006 (4)
C27	0.084 (7)	0.026 (5)	0.051 (6)	−0.009 (5)	0.036 (5)	−0.002 (4)
C28	0.047 (5)	0.023 (4)	0.028 (5)	0.004 (4)	0.021 (4)	0.002 (4)
N31	0.011 (3)	0.020 (3)	0.020 (3)	0.002 (3)	0.005 (2)	0.004 (3)
C31	0.018 (4)	0.020 (4)	0.023 (5)	−0.001 (3)	0.007 (3)	−0.010 (4)
N32	0.013 (3)	0.021 (3)	0.015 (3)	0.000 (3)	0.003 (3)	0.001 (3)
C32	0.025 (4)	0.026 (4)	0.019 (5)	−0.007 (4)	−0.006 (3)	−0.001 (4)
C33	0.021 (4)	0.027 (4)	0.015 (4)	−0.003 (3)	0.003 (3)	−0.009 (3)
C34	0.038 (5)	0.033 (5)	0.013 (4)	−0.017 (4)	−0.001 (4)	−0.002 (4)
C35	0.079 (7)	0.066 (7)	0.017 (5)	−0.027 (5)	−0.009 (5)	0.014 (4)
C36	0.029 (5)	0.039 (5)	0.028 (5)	0.005 (4)	−0.003 (4)	0.015 (4)
C37	0.045 (5)	0.047 (5)	0.027 (5)	−0.006 (4)	0.008 (4)	−0.003 (4)
C38	0.040 (5)	0.017 (4)	0.039 (5)	−0.008 (4)	0.009 (4)	0.002 (4)

Geometric parameters (Å, º)

Ga1—H1	1.49 (6)	N21—C21	1.346 (8)
Ga1—N22	1.941 (5)	N21—N22	1.385 (7)
Ga1—N12	1.942 (5)	C21—C22	1.383 (9)
Ga1—N32	1.958 (5)	C21—C28	1.486 (9)
Ga2—Cl2	2.156 (2)	N22—C23	1.350 (8)
Ga2—Cl1	2.161 (2)	C22—C23	1.380 (8)
Ga2—Cl4	2.173 (2)	C23—C24	1.506 (9)
Ga2—Cl3	2.175 (2)	C24—C25	1.511 (9)
B1—N21	1.542 (9)	C24—C27	1.530 (9)
B1—N31	1.547 (9)	C24—C26	1.539 (9)
B1—N11	1.553 (9)	N31—C31	1.355 (8)
N11—C11	1.346 (8)	N31—N32	1.384 (7)
N11—N12	1.383 (7)	C31—C32	1.375 (9)
C11—C12	1.378 (9)	C31—C38	1.486 (9)
C11—C18	1.486 (9)	N32—C33	1.349 (8)
N12—C13	1.368 (8)	C32—C33	1.376 (9)
C12—C13	1.391 (9)	C33—C34	1.502 (9)
C13—C14	1.489 (9)	C34—C36	1.529 (10)
C14—C16	1.518 (9)	C34—C35	1.536 (10)
C14—C15	1.529 (9)	C34—C37	1.540 (9)
C14—C17	1.547 (9)
H1—Ga1—N22	120 (2)	N22—N21—B1	120.6 (5)
H1—Ga1—N12	122 (2)	N21—C21—C22	107.7 (6)
N22—Ga1—N12	95.4 (2)	N21—C21—C28	122.7 (6)
H1—Ga1—N32	123 (2)	C22—C21—C28	129.6 (7)
N22—Ga1—N32	94.8 (2)	C23—N22—N21	108.2 (5)
N12—Ga1—N32	95.2 (2)	C23—N22—Ga1	139.5 (5)
Cl2—Ga2—Cl1	111.67 (11)	N21—N22—Ga1	112.3 (4)
Cl2—Ga2—Cl4	109.53 (10)	C23—C22—C21	107.8 (6)
Cl1—Ga2—Cl4	107.98 (10)	N22—C23—C22	107.8 (6)
Cl2—Ga2—Cl3	106.75 (9)	N22—C23—C24	122.5 (6)
Cl1—Ga2—Cl3	108.91 (10)	C22—C23—C24	129.7 (6)
Cl4—Ga2—Cl3	112.04 (9)	C23—C24—C25	109.5 (6)
N21—B1—N31	108.4 (6)	C23—C24—C27	108.7 (5)
N21—B1—N11	108.0 (6)	C25—C24—C27	109.0 (6)
N31—B1—N11	106.9 (6)	C23—C24—C26	111.0 (6)
C11—N11—N12	109.9 (5)	C25—C24—C26	110.8 (6)
C11—N11—B1	130.3 (6)	C27—C24—C26	107.8 (6)
N12—N11—B1	119.8 (5)	C31—N31—N32	107.7 (5)
N11—C11—C12	107.1 (6)	C31—N31—B1	132.5 (6)
N11—C11—C18	122.5 (6)	N32—N31—B1	119.9 (5)
C12—C11—C18	130.4 (6)	N31—C31—C32	108.5 (6)
C13—N12—N11	107.3 (5)	N31—C31—C38	121.8 (6)
C13—N12—Ga1	139.9 (5)	C32—C31—C38	129.7 (7)
N11—N12—Ga1	112.9 (4)	C33—N32—N31	108.1 (5)
C11—C12—C13	108.5 (6)	C33—N32—Ga1	139.2 (5)
N12—C13—C12	107.2 (6)	N31—N32—Ga1	112.5 (4)
N12—C13—C14	122.5 (6)	C31—C32—C33	107.3 (6)
C12—C13—C14	130.2 (6)	N32—C33—C32	108.5 (6)
C13—C14—C16	110.2 (6)	N32—C33—C34	122.8 (6)
C13—C14—C15	109.0 (6)	C32—C33—C34	128.7 (6)
C16—C14—C15	109.1 (6)	C33—C34—C36	110.5 (6)
C13—C14—C17	111.6 (6)	C33—C34—C35	109.0 (6)
C16—C14—C17	110.4 (6)	C36—C34—C35	108.5 (6)
C15—C14—C17	106.4 (6)	C33—C34—C37	109.6 (6)
C21—N21—N22	108.5 (5)	C36—C34—C37	110.5 (6)
C21—N21—B1	130.9 (6)	C35—C34—C37	108.7 (6)