(tert-Butyl isocyanide-κC)tri­chlorido­gallium(III)

Bourque, J.L.; Tashkandi, N.Y.; Baines, K.M.

doi:10.1107/S2414314616003898

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160389

doi:10.1107/S2414314616003898

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(tert-Butyl isocyanide-κC)trichloridogallium(III)

Jeremy L. Bourque,^a ^* Nada Y. Tashkandi ^a and Kim M. Baines ^a

^aDepartment of Chemistry, University of Western Ontario, London, ON, N6A 5B7, Canada
^*Correspondence e-mail: jbourqu5@uwo.ca

Edited by M. Weil, Vienna University of Technology, Austria (Received 1 March 2016; accepted 7 March 2016; online 11 March 2016)

The crystal structure of (tert-butyl isocyanide-κC)trichloridogallium(III), [GaCl₃(C₅H₉N)], features the first reported isocyanide–gallium trihalide complex. The Ga—C—N—C fragment is essentially linear. The methyl fragments of the tert-butyl group are eclipsed with the chloride ligands on the Ga atom. The molecule does not, however, exhibit threefold crystallographic symmetry, as it crystallizes within the P2₁/c space group.

Keywords: crystal structure; isocyanide complexes; Lewis acid–base complex; gallium trichloride.

CCDC reference: 1456425

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Chemical scheme

Structure description

The Ga—C—N—C fragment deviates only slightly from linearity with N1—C1—Ga1 and C1—N1—C2 angles of 179.26 (16) and 179.35 (18)°, respectively (Fig. 1). The angle between the Cl1—Ga1—C1 and N1—C2—C3 planes of 1.5 (2)° indicates a nearly perfect eclipsed conformation between the –C(CH₃)₃ and –GaCl₃ groups. In the crystal, there are no notable interactions between neighbouring molecules (Fig. 2).

Figure 1
The molecular structure of the title compound, showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.

Figure 2
Crystal packing of the title compound viewed along the b axis. Hydrogen atoms are omitted for clarity.

The synthesis of trialkylgallium–isocyanide complexes was reported by Kingsley et al. (2012 ). For adducts of isocyanides with other main group elements, see: Bertani et al. (2001 ); Casanova et al. (1965 ); Fisher et al. (1994 ); Green et al. (1987 ); Meller & Batka (1969 , 1970 ); Uhl et al. (1998 ). For an extensive theoretical study on main group element–isocyanide adducts, see: Timoshkin & Schaefer (2003 ).

Synthesis and crystallization

The title compound was obtained serendipitously from an attempted trapping experiment, involving the reaction of tert-butylisocyanide and tetramesityldisilene. GaCl₃ was added to act as a Lewis acid. X-ray quality single crystals were obtained from a solution of diethyl ether cooled to 253 K.

Refinement

Crystal data, data collection and refinement details are shown in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[GaCl₃(C₅H₉N)]
M_r	259.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	6.5170 (12), 19.393 (3), 8.5991 (16)
β (°)	102.287 (5)
V (Å³)	1061.9 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	10.00
Crystal size (mm)	0.23 × 0.17 × 0.11

Data collection
Diffractometer	Bruker–Nonius KappaCCD APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.557, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	10964, 1876, 1791
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.11
No. of reflections	1876
No. of parameters	127
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31
Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), XP (Sheldrick, 2008 ), cif2tables.py (Boyle, 2008 ).

Structural data

CCDC reference: 1456425

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616003898/wm4009sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616003898/wm4009Isup2.hkl

checkCIF report

Experimental top

Structure description top

The Ga—C—N—C fragment deviates only slightly from linearity with N1—C1—Ga1 and C1—N1—C2 angles of 179.26 (16) and 179.35 (18)°, respectively (Fig. 1). The angle between the Cl1—Ga1—C1 and N1—C2—C3 planes of 1.5 (2)° indicates a nearly perfect eclipsed conformation between the –C(CH₃)₃ and –GaCl₃ groups. There are no notable interactions between neighbouring molecules (Fig. 2).

The synthesis of trialkylgallium–isocyanide complexes was reported by Kingsley et al. (2012). For adducts of isocyanides with other main group elements, see: Bertani et al. (2001); Casanova et al. (1965); Fisher et al. (1994); Green et al. (1987); Meller & Batka (1969, 1970); Uhl et al. (1998). For an extensive theoretical study on main group element–isocyanide adducts, see: Timoshkin & Schaefer (2003).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: cif2tables.py (Boyle, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. Crystal packing of the title compound viewed along the b axis. Hydrogen atoms are omitted for clarity.

(tert-Butyl isocyanide-κC)trichloridogallium(III) top

Crystal data top

[GaCl₃(C₅H₉N)]	F(000) = 512
M_r = 259.20	D_x = 1.621 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 6.5170 (12) Å	Cell parameters from 6667 reflections
b = 19.393 (3) Å	θ = 4.6–66.7°
c = 8.5991 (16) Å	µ = 10.00 mm⁻¹
β = 102.287 (5)°	T = 110 K
V = 1061.9 (3) Å³	Needle, orange
Z = 4	0.23 × 0.17 × 0.11 mm

Data collection top

Bruker–Nonius KappaCCD APEXII diffractometer	1791 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.024
phi and ω scans	θ_max = 66.7°, θ_min = 4.6°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −7→7
T_min = 0.557, T_max = 0.753	k = −22→22
10964 measured reflections	l = −10→10
1876 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: difference Fourier map
wR(F²) = 0.055	All H-atom parameters refined
S = 1.11	w = 1/[σ²(F_o²) + (0.031P)² + 0.275P] where P = (F_o² + 2F_c²)/3
1876 reflections	(Δ/σ)_max = 0.002
127 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[GaCl₃(C₅H₉N)]	V = 1061.9 (3) Å³
M_r = 259.20	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 6.5170 (12) Å	µ = 10.00 mm⁻¹
b = 19.393 (3) Å	T = 110 K
c = 8.5991 (16) Å	0.23 × 0.17 × 0.11 mm
β = 102.287 (5)°

Data collection top

Bruker–Nonius KappaCCD APEXII diffractometer	1876 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1791 reflections with I > 2σ(I)
T_min = 0.557, T_max = 0.753	R_int = 0.024
10964 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.055	All H-atom parameters refined
S = 1.11	Δρ_max = 0.33 e Å⁻³
1876 reflections	Δρ_min = −0.31 e Å⁻³
127 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ga1	0.57250 (3)	0.61614 (2)	0.63792 (2)	0.02511 (9)
Cl1	0.53074 (7)	0.70861 (2)	0.76750 (5)	0.03418 (12)
Cl2	0.87880 (7)	0.60850 (3)	0.58522 (6)	0.03958 (13)
Cl3	0.48498 (7)	0.52514 (2)	0.75065 (5)	0.03701 (12)
C1	0.3619 (3)	0.62469 (9)	0.4270 (2)	0.0275 (4)
N1	0.2429 (2)	0.62920 (7)	0.31030 (16)	0.0247 (3)
C2	0.0869 (3)	0.63437 (10)	0.1590 (2)	0.0295 (4)
C3	−0.0287 (4)	0.70142 (13)	0.1670 (3)	0.0529 (6)
H3A	−0.133 (5)	0.7048 (15)	0.071 (4)	0.070 (8)*
H3B	−0.102 (5)	0.6985 (18)	0.241 (4)	0.082 (11)*
H3C	0.064 (4)	0.7425 (16)	0.171 (4)	0.065 (8)*
C4	0.2098 (4)	0.63342 (14)	0.0282 (2)	0.0452 (5)
H4A	0.114 (4)	0.6379 (13)	−0.068 (3)	0.047 (6)*
H4B	0.314 (4)	0.6705 (13)	0.038 (3)	0.048 (7)*
H4C	0.286 (5)	0.5912 (16)	0.029 (3)	0.058 (8)*
C5	−0.0554 (4)	0.57180 (13)	0.1521 (3)	0.0450 (5)
H5A	−0.160 (4)	0.5739 (13)	0.054 (3)	0.048 (6)*
H5B	0.017 (5)	0.5279 (16)	0.152 (3)	0.060 (8)*
H5C	−0.124 (5)	0.5744 (15)	0.238 (4)	0.062 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ga1	0.02527 (14)	0.02897 (14)	0.01932 (13)	−0.00094 (7)	0.00074 (9)	−0.00039 (7)
Cl1	0.0395 (2)	0.0326 (2)	0.0306 (2)	−0.00260 (17)	0.00762 (18)	−0.00620 (16)
Cl2	0.0283 (2)	0.0564 (3)	0.0345 (2)	−0.00090 (18)	0.00752 (18)	−0.00601 (19)
Cl3	0.0428 (3)	0.0308 (2)	0.0380 (2)	−0.00061 (17)	0.00984 (19)	0.00590 (17)
C1	0.0281 (9)	0.0294 (8)	0.0244 (9)	−0.0006 (6)	0.0044 (7)	−0.0010 (6)
N1	0.0253 (7)	0.0278 (7)	0.0207 (7)	0.0002 (5)	0.0040 (6)	−0.0019 (5)
C2	0.0278 (9)	0.0374 (9)	0.0196 (8)	0.0015 (7)	−0.0028 (7)	−0.0012 (7)
C3	0.0491 (13)	0.0528 (14)	0.0459 (13)	0.0199 (11)	−0.0142 (11)	−0.0072 (11)
C4	0.0473 (12)	0.0664 (15)	0.0206 (9)	−0.0050 (11)	0.0045 (9)	0.0018 (9)
C5	0.0424 (11)	0.0575 (14)	0.0308 (10)	−0.0171 (10)	−0.0016 (9)	−0.0067 (9)

Geometric parameters (Å, º) top

Ga1—C1	2.0351 (18)	C3—H3A	0.95 (3)
Ga1—Cl2	2.1441 (6)	C3—H3B	0.88 (4)
Ga1—Cl3	2.1481 (5)	C3—H3C	1.00 (3)
Ga1—Cl1	2.1589 (5)	C4—H4A	0.92 (3)
C1—N1	1.133 (2)	C4—H4B	0.98 (3)
N1—C2	1.474 (2)	C4—H4C	0.96 (3)
C2—C3	1.512 (3)	C5—H5A	0.96 (3)
C2—C4	1.513 (3)	C5—H5B	0.97 (3)
C2—C5	1.521 (3)	C5—H5C	0.94 (3)

C1—Ga1—Cl2	107.40 (5)	H3A—C3—H3B	103 (3)
C1—Ga1—Cl3	106.00 (5)	C2—C3—H3C	112.6 (17)
Cl2—Ga1—Cl3	112.78 (2)	H3A—C3—H3C	107 (2)
C1—Ga1—Cl1	104.90 (5)	H3B—C3—H3C	117 (3)
Cl2—Ga1—Cl1	113.07 (2)	C2—C4—H4A	107.3 (16)
Cl3—Ga1—Cl1	112.01 (2)	C2—C4—H4B	113.1 (14)
N1—C1—Ga1	179.26 (16)	H4A—C4—H4B	109 (2)
C1—N1—C2	179.35 (18)	C2—C4—H4C	111.2 (17)
N1—C2—C3	105.96 (15)	H4A—C4—H4C	110 (2)
N1—C2—C4	106.28 (15)	H4B—C4—H4C	106 (2)
C3—C2—C4	113.1 (2)	C2—C5—H5A	108.1 (15)
N1—C2—C5	106.27 (15)	C2—C5—H5B	114.0 (17)
C3—C2—C5	112.49 (19)	H5A—C5—H5B	107 (2)
C4—C2—C5	112.12 (18)	C2—C5—H5C	108.3 (18)
C2—C3—H3A	106.9 (18)	H5A—C5—H5C	109 (2)
C2—C3—H3B	109 (2)	H5B—C5—H5C	111 (2)

Experimental details

Crystal data
Chemical formula	[GaCl₃(C₅H₉N)]
M_r	259.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	6.5170 (12), 19.393 (3), 8.5991 (16)
β (°)	102.287 (5)
V (Å³)	1061.9 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	10.00
Crystal size (mm)	0.23 × 0.17 × 0.11

Data collection
Diffractometer	Bruker–Nonius KappaCCD APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2013)
T_min, T_max	0.557, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	10964, 1876, 1791
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.11
No. of reflections	1876
No. of parameters	127
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), XP (Sheldrick, 2008), cif2tables.py (Boyle, 2008).

Acknowledgements

We thank NSERC (Canada), the NSERC CGS program for a scholarship to JLB, the King Abdul Aziz University (Saudi Arabia) for a scholarship to NYT and the University of Western Ontario for financial support. We also thank Dr Paul D. Boyle for aid in the structure refinement.

References

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