Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016100/cf6203sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016100/cf6203Isup2.hkl |
CCDC reference: 198316
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.005 Å
- R factor = 0.035
- wR factor = 0.093
- Data-to-parameter ratio = 28.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Author response: The data were measured on an area-detector. |
DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
Author response: The data were measured on an area-detector. |
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
Colourless crystals of the title compound were obtained from a solution of 0.07 g (0.4 mmol) GaCl3 and 0.5 ml tetrahydrofuran in 20 ml pentane at 267 K. The NMR spectra were recorded on a Bruker AM 250 spectrometer. GaCl3.thf: 1H-NMR (C6D6, internal TMS): δ 0.82 (m; CH2), 3.42 (m; OCH2). 13C{1H}NMR (C6D6, internal TMS): δ 24.6 (s; CH2), 71.8 (s; OCH2).
All H atoms were located in a difference Fourier synthesis. They were refined with fixed individual displacement parameters [U(H) = 1.2 Ueq(C)], using a riding model with C—H = 0.99 Å.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.
[Ga(C4H8O)Cl3] | F(000) = 244 |
Mr = 248.17 | Dx = 1.819 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yb | Cell parameters from 7266 reflections |
a = 6.2048 (9) Å | θ = 3.8–29.8° |
b = 10.3980 (11) Å | µ = 3.85 mm−1 |
c = 7.3089 (10) Å | T = 173 K |
β = 106.085 (11)° | Plate, colourless |
V = 453.09 (10) Å3 | 0.30 × 0.20 × 0.10 mm |
Z = 2 |
STOE IPDS II two-circle diffractometer | 1356 independent reflections |
Radiation source: fine-focus sealed tube | 1200 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
ω scans | θmax = 29.8°, θmin = 3.8° |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | h = −8→7 |
Tmin = 0.392, Tmax = 0.700 | k = −14→14 |
6794 measured reflections | l = −10→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.2393P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
1356 reflections | Δρmax = 0.66 e Å−3 |
47 parameters | Δρmin = −1.01 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (6) |
[Ga(C4H8O)Cl3] | V = 453.09 (10) Å3 |
Mr = 248.17 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 6.2048 (9) Å | µ = 3.85 mm−1 |
b = 10.3980 (11) Å | T = 173 K |
c = 7.3089 (10) Å | 0.30 × 0.20 × 0.10 mm |
β = 106.085 (11)° |
STOE IPDS II two-circle diffractometer | 1356 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | 1200 reflections with I > 2σ(I) |
Tmin = 0.392, Tmax = 0.700 | Rint = 0.070 |
6794 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.66 e Å−3 |
1356 reflections | Δρmin = −1.01 e Å−3 |
47 parameters |
Experimental. |
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. |
x | y | z | Uiso*/Ueq | ||
Ga1 | 0.43452 (6) | 0.2500 | 0.62919 (5) | 0.03059 (16) | |
Cl1 | 0.75135 (17) | 0.2500 | 0.56595 (16) | 0.0540 (3) | |
Cl2 | 0.37313 (15) | 0.07687 (9) | 0.76462 (13) | 0.0619 (3) | |
O1 | 0.2102 (5) | 0.2500 | 0.3882 (4) | 0.0391 (6) | |
C1 | 0.1263 (7) | 0.3663 (3) | 0.2771 (5) | 0.0587 (9) | |
H1A | 0.0408 | 0.4206 | 0.3437 | 0.070* | |
H1B | 0.2520 | 0.4174 | 0.2562 | 0.070* | |
C2 | −0.0193 (9) | 0.3195 (4) | 0.0959 (5) | 0.0785 (13) | |
H2A | −0.1738 | 0.3518 | 0.0781 | 0.094* | |
H2B | 0.0355 | 0.3518 | −0.0106 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ga1 | 0.0276 (2) | 0.0329 (2) | 0.0286 (2) | 0.000 | 0.00337 (14) | 0.000 |
Cl1 | 0.0355 (5) | 0.0812 (8) | 0.0482 (5) | 0.000 | 0.0165 (4) | 0.000 |
Cl2 | 0.0547 (5) | 0.0619 (5) | 0.0611 (5) | −0.0124 (4) | 0.0028 (4) | 0.0292 (4) |
O1 | 0.0415 (14) | 0.0309 (12) | 0.0357 (12) | 0.000 | −0.0047 (10) | 0.000 |
C1 | 0.067 (2) | 0.0387 (14) | 0.0530 (17) | −0.0087 (15) | −0.0128 (15) | 0.0144 (12) |
C2 | 0.106 (3) | 0.064 (2) | 0.0430 (16) | 0.031 (2) | −0.0179 (18) | −0.0066 (15) |
Ga1—O1 | 1.919 (3) | C1—H1A | 0.990 |
Ga1—Cl2 | 2.1388 (8) | C1—H1B | 0.990 |
Ga1—Cl1 | 2.1405 (11) | C2—C2i | 1.446 (9) |
O1—C1 | 1.469 (3) | C2—H2A | 0.990 |
C1—C2 | 1.464 (5) | C2—H2B | 0.990 |
O1—Ga1—Cl2 | 104.36 (5) | C2—C1—H1B | 110.7 |
Cl2—Ga1—Cl2i | 114.63 (6) | O1—C1—H1B | 110.7 |
O1—Ga1—Cl1 | 106.13 (10) | H1A—C1—H1B | 108.8 |
Cl2—Ga1—Cl1 | 113.08 (3) | C2i—C2—C1 | 109.4 (2) |
C1—O1—C1i | 110.8 (3) | C2i—C2—H2A | 109.8 |
C1—O1—Ga1 | 124.27 (16) | C1—C2—H2A | 109.8 |
C2—C1—O1 | 105.2 (3) | C2i—C2—H2B | 109.8 |
C2—C1—H1A | 110.7 | C1—C2—H2B | 109.8 |
O1—C1—H1A | 110.7 | H2A—C2—H2B | 108.2 |
Cl2—Ga1—O1—C1 | 155.4 (3) | C1i—O1—C1—C2 | 2.0 (6) |
Cl1—Ga1—O1—C1 | −85.0 (3) | Ga1—O1—C1—C2 | 173.1 (3) |
Cl2—Ga1—O1—C1i | −34.7 (3) | O1—C1—C2—C2i | −1.2 (4) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Ga(C4H8O)Cl3] |
Mr | 248.17 |
Crystal system, space group | Monoclinic, P21/m |
Temperature (K) | 173 |
a, b, c (Å) | 6.2048 (9), 10.3980 (11), 7.3089 (10) |
β (°) | 106.085 (11) |
V (Å3) | 453.09 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.85 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | STOE IPDS II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.392, 0.700 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6794, 1356, 1200 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.699 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.093, 1.04 |
No. of reflections | 1356 |
No. of parameters | 47 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −1.01 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
Ga1—O1 | 1.919 (3) | Ga1—Cl1 | 2.1405 (11) |
Ga1—Cl2 | 2.1388 (8) | ||
O1—Ga1—Cl2 | 104.36 (5) | O1—Ga1—Cl1 | 106.13 (10) |
Cl2—Ga1—Cl2i | 114.63 (6) | Cl2—Ga1—Cl1 | 113.08 (3) |
Symmetry code: (i) x, −y+1/2, z. |
We report here the X-ray crystal structure analysis of GaCl3.thf (thf = C4H8O). The halides of Ga(I), Ga(II), and Ga(III) have been used in the synthesis of new gallium clusters (Donchev et al., 2001). The synthesis of these clusters depends on the oxidation state of Ga in the halides on the one hand and the solvent on the other. GaCl3 features a cyclic, dimeric arrangement in non-donor solvents such as alkanes and benzene. By contrast, monomeric adducts of GaCl3 are formed in the presence of Lewis bases. Given this background, we became interested in the reaction of GaCl3.thf with the bulky siloxides tBu3SiONa and tBu2PhSiONa (Lerner et al., 2002). Therefore, we prepared a solution of GaCl3.thf in pentane. Colourless crystals of the title compound, (I), were grown from this solution at 267 K. GaCl3.C4H8O is isostructural with AlCl3.C4H8O (Engelhardt et al., 1996). The molecule is located on a mirror plane; the Ga atom, the O atom and one of the Cl atoms lie in this plane. All other atoms occupy general positions.