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The title compound, [GaCl2(C3H10NSi)(C4H8O)], is the tetra­hydro­furan-coordinated monomer of the previously structurally characterized dimer [GaN(H)SiMe3Cl2]2. The title compound consists of discrete monomeric mol­ecules with two crystallographically independent mol­ecules within the unit cell. The crystal structure is composed of a Ga atom in a four-coordinate tetrahedral arrangement, with Ga-N distances of 2.025 (3) and 2.026 (3) Å in the two independent mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010000247X/bk1507sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010000247X/bk1507Isup2.hkl
Contains datablock I

CCDC reference: 145530

Comment top

During the course of examining (II) (Wiberg & Schmid, 1966) as a potential synthon for the preparation of a novel zinc amide, it was mixed with a solution of Me2Zn in toluene. However, the only compound to be isolated from the reaction, after crystallization from tetrahydrofuran (THF) and work-up, was the title compound, (I), which is the THF-coordinated monomer of the starting material, the previously structurally characterized dimer [GaN(H)SiMe3Cl2]2, (II) (Nutt et al., 1985). \scheme

Compound (I) has two crystallographically independent molecules within the unit cell. The crystal structure consists of discrete monomers, with the molecular structure consisting of a Ga atom bonded to two Cl atoms, an O atom from the coordinated THF molecule, which shows some disorder, and the N atom of the amino group. The N atom is further bonded to an Si atom from the trimethylsilyl ligand and to an H atom.

The bond distances in (I) are comparable with those in the starting compound, (II), which is a dimer consisting of a four-membered (GaN)2 ring with the trimethylsilyl ligands on adjacent N atoms trans to one another. The Ga—Cl and N—Si interatomic distances in (I) are Ga1—Cl1 2.2178 (10), Ga1—Cl2 2.2182 (9), Ga2—Cl3 2.2226 (9) and Ga2—Cl4 2.2218 (10) Å, and N1—Si1 1.791 (3) and N2—Si2 1.800 (2) Å (for the crystallographically independent molecules 1 and 2, respectively). The corresponding values in (II) are Ga—Cl 2.150 (2) and 2.136 (2) Å, and N—Si 1.805 (4) Å. The Ga—N interatomic distances in (I) are slightly longer than those found in (II): Ga1—N1 2.026 (3) and Ga2—N2 2.025 (2) Å in (I), and Ga—N 1.974 (4) and 1.964 (4) Å in (II), with this bond lengthening most likely occurring due to the electron-releasing effect of the coordinated THF molecule.

The Ga—O distances [Ga1—O1 2.048 (2) and Ga2—O2 2.041 (2) Å] are within the range found in the other two structually characterized gallium complexes possessing a coordinated THF molecule and a Ga—Cl interaction, [GaSi(SiMe3)3Cl2(C4H8O)] [2.010 (3) Å; Linti et al., 1996] and PhClGaSi(SiMe3)·THF [2.061 (3) Å]. The interatomic angles about the four-coordinate Ga atom deviate from those of an ideal tetrahedron, with the most acute being O1—Ga1—Cl1 102.87 (7) and O2—Ga2—Cl3 101.55 (7)° (molecules 1 and 2, respectively) and the most obtuse being Cl2—Ga1—Cl1 119.27 (4) and Cl4—Ga2—Cl3 119.23 (4)°.

Experimental top

A 2M toluene solution of Me2Zn (1.1 ml, 2.186 mmol) was added dropwise to a vigorously stirred ether solution of (II) (1.00 g, 2.18 mmol) at 195 K. The resulting reaction mixture was warmed to room temperature and stirred for 18 h. The solvent volume was removed by vacuum pump and the remaining white residue extracted in THF. Filtration through Celite, reduction of the solvent volume followed by overlayering with pentane, afforded, after solvent diffusion over a period of days at 238 K, compound (I) as white colourless crystals. Crystals suitable for an X-ray structural determination were grown using solvent diffusion, by placing saturated THF solutions of (I) overlayered with pentane at 238 K for several days (yield 40%). Spectroscopic analysis: 1H-NMR (3000 MHz, C6D6, δ, p.p.m.): 0.234 (s, SiMe3), 1.214 (m, furan), 2.785 (2.785 s, NH), 3.626 (m, furan); 13C-NMR (500 MHz, C6D6, δ, p.p.m.): 5.593 (SiMe3), 19.404 (furan), 63.964 (furan).

Refinement top

H-atom positions were calculated for the ordered C atoms and were refined as riding. H atoms on N were located from difference Fourier maps and their coordinates were fixed during refinement. All H-atom displacement parameters were refined isotropically. Both of the THF ligands exhibited disorder; atoms C6, C7 and C13 were split into two positions and refined with occupancies of 0.5. H atoms were not calculated on atoms C5, C6, C7, C12, C13 and C14 of the disordered THF ligands.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97.

Figures top
[Figure 1] Fig. 1. The ORTEP (Johnson, 1968) representation of (I), showing the disorder in the THF ligands. Displacement ellipsoids are at the 30% probability level and all H atoms have been omitted for clarity.
Dichloro(tetrahydrofuran-O)[(trimethylsilyl)amido-N]gallium(III) top
Crystal data top
[Ga(C3H10NSi)Cl2(C4H8O)]Z = 4
Mr = 300.93F(000) = 616
Triclinic, P1Dx = 1.433 Mg m3
a = 9.4539 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.8134 (3) ÅCell parameters from 7048 reflections
c = 12.8999 (3) Åθ = 1.6–28.4°
α = 86.918 (1)°µ = 2.41 mm1
β = 83.194 (1)°T = 193 K
γ = 77.308 (1)°Cube, colourless
V = 1395.02 (6) Å30.44 × 0.29 × 0.24 mm
Data collection top
Siemens SMART 1K CCD
diffractometer
4826 reflections with I > 2σ(I)
ω scansRint = 0.024
Absorption correction: multi-scan
(Blessing, 1995)
θmax = 28.4°
Tmin = 0.392, Tmax = 0.563h = 1212
12575 measured reflectionsk = 1515
6380 independent reflectionsl = 1616
Refinement top
Refinement on F2 w = 1/[σ2(Fo2) + (0.0514P)2 + 0.8048P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.038(Δ/σ)max = 0.001
wR(F2) = 0.108Δρmax = 0.96 e Å3
S = 1.03Δρmin = 0.51 e Å3
6380 reflectionsExtinction correction: SHELXL97 (Sheldrick, 1997)
261 parametersExtinction coefficient: 0.0004 (5)
H atoms treated by a mixture of independent and constrained refinement
Crystal data top
[Ga(C3H10NSi)Cl2(C4H8O)]γ = 77.308 (1)°
Mr = 300.93V = 1395.02 (6) Å3
Triclinic, P1Z = 4
a = 9.4539 (2) ÅMo Kα radiation
b = 11.8134 (3) ŵ = 2.41 mm1
c = 12.8999 (3) ÅT = 193 K
α = 86.918 (1)°0.44 × 0.29 × 0.24 mm
β = 83.194 (1)°
Data collection top
Siemens SMART 1K CCD
diffractometer
6380 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
4826 reflections with I > 2σ(I)
Tmin = 0.392, Tmax = 0.563Rint = 0.024
12575 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038261 parameters
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.96 e Å3
6380 reflectionsΔρmin = 0.51 e Å3
Special details top

Experimental. A crystal of the title compound was selected and mounted on a glass fibre while in a stream of cold argon gas and placed immediately on a Siemens SMART 1 K CCD diffractometer at 173 K under a stream of cold nitrogen gas. Graphite monochromated Mo—Kα radiation was used (λ Å). Reflections were collected with a frame width of 0.3° in ω scans and a counting time of 30 s per frame at a crystal-to-detector distance of 4.911 cm. The double-pass method of scanning was used to reduce any noise. The first 50 frames of data were recollected at the conclusion of data collection to monitor crystal decay.

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Ga10.45992 (4)0.49750 (3)0.71387 (3)0.03747 (12)
Ga20.52816 (4)0.01645 (3)0.79044 (3)0.03677 (11)
Si10.78047 (10)0.30826 (8)0.68609 (7)0.0385 (2)
Si20.20911 (9)0.09996 (7)0.81756 (7)0.03112 (19)
Cl10.29953 (11)0.57772 (9)0.60453 (7)0.0598 (3)
Cl20.56211 (10)0.61067 (7)0.79950 (8)0.0493 (2)
Cl30.68233 (10)0.00461 (10)0.90170 (7)0.0569 (3)
Cl40.42694 (10)0.13652 (7)0.69627 (8)0.0498 (2)
N10.6004 (3)0.3582 (2)0.6485 (2)0.0329 (6)
H10.55380.30090.65670.057 (12)*
N20.3899 (3)0.1160 (2)0.85525 (19)0.0301 (5)
H2D0.37490.09990.92850.056 (11)*
O10.3356 (3)0.4260 (2)0.82922 (18)0.0464 (6)
O20.6625 (2)0.1235 (2)0.68397 (18)0.0418 (6)
C10.8876 (4)0.4154 (4)0.6338 (3)0.0568 (10)
H1A0.87990.42800.56120.084 (9)*
H1B0.98700.38700.64470.084 (9)*
H1C0.85120.48650.66870.084 (9)*
C20.7672 (5)0.2999 (4)0.8301 (3)0.0604 (12)
H2A0.73200.37550.85680.081 (9)*
H2B0.86090.26820.85160.081 (9)*
H2C0.70200.25160.85610.081 (9)*
C30.8531 (4)0.1619 (3)0.6308 (3)0.0520 (10)
H3A0.80010.10850.66500.070 (8)*
H3B0.95330.13710.64090.070 (8)*
H3C0.84310.16550.55820.070 (8)*
C40.1924 (5)0.4064 (5)0.8195 (4)0.0686 (13)
H4A0.19710.35270.76630.122 (16)*
H4B0.12810.47700.80260.122 (16)*
C50.1423 (7)0.3598 (7)0.9207 (5)0.113 (2)
C60.2197 (11)0.3844 (9)0.9954 (8)0.069 (2)*0.50
C6A0.2707 (12)0.3141 (10)0.9785 (9)0.076 (3)*0.50
C70.3583 (15)0.4212 (10)0.9417 (8)0.056 (3)0.50
C7A0.3884 (15)0.3614 (11)0.9199 (9)0.063 (3)0.50
C80.2253 (4)0.1045 (3)0.6735 (3)0.0453 (8)
H8A0.27170.04480.64380.060 (7)*
H8B0.13090.09320.65110.060 (7)*
H8C0.28170.17780.65140.060 (7)*
C90.1333 (4)0.2227 (3)0.8791 (3)0.0503 (9)
H9A0.19080.29380.85280.082 (9)*
H9B0.03580.21450.86340.082 (9)*
H9C0.13430.22260.95260.082 (9)*
C100.1021 (4)0.0417 (3)0.8642 (3)0.0464 (9)
H10A0.10920.04680.93650.073 (8)*
H10B0.00280.04900.85330.073 (8)*
H10C0.13920.10230.82660.073 (8)*
C110.8071 (4)0.1896 (4)0.7018 (3)0.0526 (10)
H11A0.80020.25270.74960.082 (11)*
H11B0.86140.14170.72930.082 (11)*
C120.8773 (5)0.2324 (5)0.5984 (4)0.0845 (17)
C130.7802 (14)0.2017 (11)0.5231 (10)0.086 (3)*0.50
C13A0.7532 (9)0.2480 (7)0.5394 (6)0.0460 (17)*0.50
C140.6326 (5)0.1422 (5)0.5792 (3)0.0789 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ga10.0389 (2)0.0380 (2)0.0322 (2)0.00129 (15)0.00541 (15)0.00218 (14)
Ga20.0318 (2)0.0458 (2)0.0345 (2)0.01039 (15)0.00483 (15)0.00531 (15)
Si10.0384 (5)0.0412 (5)0.0319 (5)0.0042 (4)0.0101 (4)0.0034 (4)
Si20.0275 (4)0.0387 (4)0.0277 (4)0.0075 (3)0.0055 (3)0.0008 (3)
Cl10.0551 (6)0.0739 (7)0.0370 (5)0.0168 (5)0.0131 (4)0.0077 (4)
Cl20.0507 (5)0.0357 (4)0.0613 (6)0.0053 (4)0.0091 (4)0.0100 (4)
Cl30.0415 (5)0.0998 (8)0.0378 (5)0.0281 (5)0.0064 (4)0.0182 (5)
Cl40.0514 (5)0.0403 (4)0.0618 (6)0.0154 (4)0.0168 (4)0.0071 (4)
N10.0330 (14)0.0314 (13)0.0342 (14)0.0052 (11)0.0082 (11)0.0010 (11)
N20.0255 (13)0.0378 (13)0.0269 (13)0.0052 (10)0.0051 (10)0.0016 (10)
O10.0388 (13)0.0692 (17)0.0343 (13)0.0189 (12)0.0061 (10)0.0063 (11)
O20.0292 (12)0.0599 (15)0.0317 (12)0.0018 (10)0.0029 (9)0.0077 (10)
C10.044 (2)0.068 (3)0.062 (3)0.0153 (19)0.0090 (19)0.008 (2)
C20.076 (3)0.057 (2)0.038 (2)0.015 (2)0.021 (2)0.0023 (17)
C30.054 (2)0.050 (2)0.044 (2)0.0080 (17)0.0017 (17)0.0079 (17)
C40.048 (2)0.097 (4)0.069 (3)0.032 (2)0.014 (2)0.001 (3)
C50.090 (4)0.180 (7)0.083 (4)0.079 (5)0.021 (3)0.003 (4)
C70.065 (7)0.086 (8)0.021 (4)0.029 (7)0.001 (4)0.007 (5)
C7A0.067 (8)0.097 (9)0.035 (6)0.039 (7)0.014 (5)0.024 (6)
C80.051 (2)0.057 (2)0.0338 (18)0.0191 (17)0.0117 (16)0.0022 (15)
C90.046 (2)0.061 (2)0.048 (2)0.0237 (18)0.0077 (17)0.0124 (18)
C100.0335 (18)0.054 (2)0.046 (2)0.0045 (15)0.0060 (15)0.0008 (16)
C110.0327 (19)0.072 (3)0.046 (2)0.0054 (18)0.0074 (16)0.0024 (19)
C120.051 (3)0.129 (5)0.057 (3)0.022 (3)0.003 (2)0.032 (3)
C140.053 (3)0.132 (4)0.034 (2)0.029 (3)0.0143 (18)0.036 (2)
Geometric parameters (Å, º) top
Ga1—N12.026 (3)O1—C71.489 (12)
Ga1—O12.048 (2)O2—C141.451 (4)
Ga1—Cl12.2178 (10)O2—C111.456 (4)
Ga1—Cl22.2182 (9)C4—C51.456 (7)
Ga2—N22.025 (2)C5—C61.357 (11)
Ga2—O22.041 (2)C5—C6A1.485 (12)
Ga2—Cl42.2218 (10)C6—C6A0.887 (12)
Ga2—Cl32.2226 (9)C6—C71.546 (16)
Si1—N11.791 (3)C6—C7A1.742 (16)
Si1—C11.842 (4)C6A—C7A1.467 (16)
Si1—C21.846 (4)C6A—C71.679 (16)
Si1—C31.861 (4)C7—C7A0.758 (13)
Si2—N21.800 (2)C11—C121.480 (6)
Si2—C101.846 (4)C12—C131.395 (13)
Si2—C81.850 (3)C12—C13A1.521 (9)
Si2—C91.856 (4)C13—C13A0.667 (13)
O1—C7A1.441 (12)C13—C141.533 (13)
O1—C41.444 (4)C13A—C141.559 (9)
N1—Ga1—O1103.78 (10)C4—C5—C6A108.6 (6)
N1—Ga1—Cl1110.14 (8)C6A—C6—C579.9 (11)
O1—Ga1—Cl1102.87 (7)C6A—C6—C782.4 (11)
N1—Ga1—Cl2114.85 (8)C5—C6—C7108.7 (8)
O1—Ga1—Cl2103.65 (8)C6A—C6—C7A57.3 (10)
Cl1—Ga1—Cl2119.27 (4)C5—C6—C7A96.7 (8)
N2—Ga2—O2102.82 (10)C7—C6—C7A25.8 (5)
N2—Ga2—Cl4115.13 (7)C6—C6A—C7A92.2 (12)
O2—Ga2—Cl4104.55 (7)C6—C6A—C564.1 (10)
N2—Ga2—Cl3110.87 (8)C7A—C6A—C5104.3 (9)
O2—Ga2—Cl3101.55 (7)C6—C6A—C766.0 (11)
Cl4—Ga2—Cl3119.23 (4)C7A—C6A—C726.8 (6)
N1—Si1—C1107.09 (16)C5—C6A—C796.4 (8)
N1—Si1—C2108.18 (17)C7A—C7—O171.5 (15)
C1—Si1—C2110.6 (2)C7A—C7—C691.7 (18)
N1—Si1—C3107.12 (16)O1—C7—C6102.5 (9)
C1—Si1—C3112.86 (19)C7A—C7—C6A60.8 (16)
C2—Si1—C3110.71 (18)O1—C7—C6A96.9 (8)
N2—Si2—C10107.20 (15)C6—C7—C6A31.6 (5)
N2—Si2—C8107.64 (14)C7—C7A—O178.5 (17)
C10—Si2—C8111.11 (17)C7—C7A—C6A92.4 (19)
N2—Si2—C9107.52 (15)O1—C7A—C6A109.5 (10)
C10—Si2—C9112.08 (18)C7—C7A—C662.5 (17)
C8—Si2—C9111.05 (18)O1—C7A—C695.7 (8)
Si1—N1—Ga1122.06 (14)C6A—C7A—C630.6 (5)
Si2—N2—Ga2122.10 (13)O2—C11—C12105.6 (3)
C7A—O1—C4108.2 (6)C13—C12—C11110.6 (6)
C7A—O1—C729.9 (5)C13—C12—C13A26.0 (5)
C4—O1—C7109.2 (6)C11—C12—C13A105.3 (4)
C7A—O1—Ga1125.5 (5)C13A—C13—C1287.6 (16)
C4—O1—Ga1124.6 (2)C13A—C13—C1479.8 (15)
C7—O1—Ga1123.8 (5)C12—C13—C14107.4 (8)
C14—O2—C11109.8 (3)C13—C13A—C1266.4 (14)
C14—O2—Ga2126.1 (2)C13—C13A—C1475.4 (14)
C11—O2—Ga2124.1 (2)C12—C13A—C14100.1 (5)
O1—C4—C5106.0 (4)O2—C14—C13105.0 (6)
C6—C5—C4110.2 (6)O2—C14—C13A105.4 (4)
C6—C5—C6A36.0 (5)C13—C14—C13A24.9 (5)

Experimental details

Crystal data
Chemical formula[Ga(C3H10NSi)Cl2(C4H8O)]
Mr300.93
Crystal system, space groupTriclinic, P1
Temperature (K)193
a, b, c (Å)9.4539 (2), 11.8134 (3), 12.8999 (3)
α, β, γ (°)86.918 (1), 83.194 (1), 77.308 (1)
V3)1395.02 (6)
Z4
Radiation typeMo Kα
µ (mm1)2.41
Crystal size (mm)0.44 × 0.29 × 0.24
Data collection
DiffractometerSiemens SMART 1K CCD
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.392, 0.563
No. of measured, independent and
observed [I > 2σ(I)] reflections
12575, 6380, 4826
Rint0.024
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.108, 1.03
No. of reflections6380
No. of parameters261
No. of restraints?
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.96, 0.51

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.

 

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