Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008067/br6095sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008067/br6095Isup2.hkl |
GaCl3 (Aldrich Chemical Company, 99.99%, H2O < 100 p.p.m.) was used as purchased. K2[PtCl4] was synthesized according to a literature procedure (Cherniaev, 1964). Toluene was dried prior to use. Carbon monoxide 99.9995% quality was used. The synthesis of the starting solution was performed in a glove-box under an inert atmosphere of dry nitrogen (< 1 p.p.m. H2O). Toluene (2.56 g) was added to the solid mixture of K2[PtCl4] (100 mg, 0.241 mmol) and GaCl3 (400 mg, 2.272 mmol). The colour of the solution turned red–brown. After 5–10 min, the liquid separated into two phases, viz. a lower dark brown and an upper light brown layer in an approximate 1:5 ratio by volume. Carbon monoxide was bubbled through the solution (both phases) at room temperature for 2 h. As a by-product, pale yellow crystals of the title compound formed, which were washed twice with toluene.
Data collection: KappaCCD Software (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: maXus (Mackay et al., 1998).
K[GaCl4] | Z = 4 |
Mr = 250.63 | Dx = 2.373 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2561 reflections |
a = 7.2230 (3) Å | θ = 4.2–27.1° |
b = 10.4377 (4) Å | µ = 5.91 mm−1 |
c = 9.3194 (4) Å | T = 297 K |
β = 93.290 (2)° | Irregular, colourless |
V = 701.45 (5) Å3 | 0.60 × 0.25 × 0.15 mm |
Nonius KappaCCD diffractometer | 1323 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
ϕ and ω scans | θmax = 27.1°, θmin = 4.2° |
Absorption correction: numerical (Herrendorf & B/"arnighausen, 1997) | h = −9→9 |
Tmin = 0.304, Tmax = 0.438 | k = −12→13 |
4148 measured reflections | l = −8→11 |
1537 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.047 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0335P)2 + 2.9803P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max < 0.001 |
1537 reflections | Δρmax = 0.90 e Å−3 |
55 parameters | Δρmin = −0.73 e Å−3 |
K[GaCl4] | V = 701.45 (5) Å3 |
Mr = 250.63 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.2230 (3) Å | µ = 5.91 mm−1 |
b = 10.4377 (4) Å | T = 297 K |
c = 9.3194 (4) Å | 0.60 × 0.25 × 0.15 mm |
β = 93.290 (2)° |
Nonius KappaCCD diffractometer | 1537 independent reflections |
Absorption correction: numerical (Herrendorf & B/"arnighausen, 1997) | 1323 reflections with I > 2σ(I) |
Tmin = 0.304, Tmax = 0.438 | Rint = 0.037 |
4148 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 55 parameters |
wR(F2) = 0.117 | 0 restraints |
S = 1.17 | Δρmax = 0.90 e Å−3 |
1537 reflections | Δρmin = −0.73 e Å−3 |
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 | ||
K | 0.1916 (3) | 0.30431 (16) | 0.1980 (2) | 0.0650 (5) | |
Ga | 0.74369 (8) | 0.55242 (6) | 0.31535 (6) | 0.0353 (2) | |
Cl1 | 0.4656 (2) | 0.92013 (17) | 0.67128 (18) | 0.0534 (4) | |
Cl2 | 0.7187 (3) | 0.71919 (19) | 0.4513 (2) | 0.0647 (5) | |
Cl3 | 0.0192 (2) | 0.03565 (18) | 0.3088 (2) | 0.0595 (5) | |
Cl4 | 0.1922 (3) | 0.62138 (19) | 0.5645 (2) | 0.0691 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
K | 0.0692 (10) | 0.0481 (9) | 0.0778 (11) | −0.0068 (7) | 0.0047 (8) | −0.0065 (8) |
Ga | 0.0326 (3) | 0.0387 (4) | 0.0353 (3) | −0.0009 (2) | 0.0075 (2) | −0.0021 (2) |
Cl1 | 0.0490 (8) | 0.0556 (9) | 0.0585 (9) | −0.0022 (7) | 0.0267 (7) | −0.0046 (7) |
Cl2 | 0.0658 (11) | 0.0675 (12) | 0.0601 (10) | 0.0158 (9) | −0.0025 (8) | −0.0303 (9) |
Cl3 | 0.0434 (8) | 0.0618 (10) | 0.0718 (11) | 0.0014 (7) | −0.0116 (8) | 0.0102 (9) |
Cl4 | 0.0779 (13) | 0.0587 (11) | 0.0698 (12) | −0.0099 (9) | −0.0031 (9) | 0.0251 (9) |
K—Cl3i | 3.196 (2) | Ga—Cl3i | 2.1730 (17) |
K—Cl4ii | 3.251 (3) | Cl1—Gavii | 2.1679 (15) |
K—Cl3 | 3.260 (2) | Cl1—Kviii | 3.310 (2) |
K—Cl2iii | 3.304 (3) | Cl1—Kiii | 3.572 (3) |
K—Cl1iv | 3.310 (2) | Cl2—Kiii | 3.304 (3) |
K—Cl2ii | 3.322 (3) | Cl2—Ki | 3.322 (3) |
K—Cl1iii | 3.572 (3) | Cl3—Gaii | 2.1730 (17) |
K—Cl4v | 3.727 (3) | Cl3—Kii | 3.196 (2) |
K—Cl1ii | 3.761 (3) | Cl4—Gaiii | 2.1677 (19) |
Ga—Cl2 | 2.1668 (17) | Cl4—Ki | 3.251 (3) |
Ga—Cl4iii | 2.1677 (19) | Cl4—Kv | 3.727 (3) |
Ga—Cl1vi | 2.1679 (15) | ||
Cl3i—K—Cl4ii | 103.39 (7) | Cl3—K—Cl4v | 71.36 (6) |
Cl3i—K—Cl3 | 156.67 (7) | Cl2iii—K—Cl4v | 62.52 (5) |
Cl4ii—K—Cl3 | 81.54 (7) | Cl1iv—K—Cl4v | 58.88 (5) |
Cl3i—K—Cl2iii | 89.11 (7) | Cl2ii—K—Cl4v | 68.18 (6) |
Cl4ii—K—Cl2iii | 131.02 (8) | Cl1iii—K—Cl4v | 117.31 (6) |
Cl3—K—Cl2iii | 71.32 (6) | Cl2—Ga—Cl4iii | 113.13 (9) |
Cl3i—K—Cl1iv | 70.25 (5) | Cl2—Ga—Cl1vi | 110.21 (8) |
Cl4ii—K—Cl1iv | 126.95 (8) | Cl4iii—Ga—Cl1vi | 106.67 (8) |
Cl3—K—Cl1iv | 125.14 (7) | Cl2—Ga—Cl3i | 106.05 (7) |
Cl2iii—K—Cl1iv | 101.94 (6) | Cl4iii—Ga—Cl3i | 111.20 (8) |
Cl3i—K—Cl2ii | 139.66 (8) | Cl1vi—Ga—Cl3i | 109.60 (8) |
Cl4ii—K—Cl2ii | 77.89 (6) | Gavii—Cl1—Kviii | 102.56 (7) |
Cl3—K—Cl2ii | 63.56 (5) | Gavii—Cl1—Kiii | 113.46 (7) |
Cl2iii—K—Cl2ii | 120.94 (8) | Kviii—Cl1—Kiii | 102.41 (5) |
Cl1iv—K—Cl2ii | 77.09 (6) | Ga—Cl2—Kiii | 120.04 (9) |
Cl3i—K—Cl1iii | 93.51 (6) | Ga—Cl2—Ki | 94.14 (7) |
Cl4ii—K—Cl1iii | 70.59 (6) | Kiii—Cl2—Ki | 123.63 (8) |
Cl3—K—Cl1iii | 66.28 (5) | Gaii—Cl3—Kii | 127.05 (9) |
Cl2iii—K—Cl1iii | 61.40 (5) | Gaii—Cl3—K | 95.75 (7) |
Cl1iv—K—Cl1iii | 157.67 (7) | Kii—Cl3—K | 112.44 (5) |
Cl2ii—K—Cl1iii | 123.49 (6) | Gaiii—Cl4—Ki | 145.42 (10) |
Cl3i—K—Cl4v | 111.34 (7) | Gaiii—Cl4—Kv | 90.67 (7) |
Cl4ii—K—Cl4v | 143.31 (7) | Ki—Cl4—Kv | 123.88 (7) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) −x, −y+1, −z+1; (vi) x+1/2, −y+3/2, z−1/2; (vii) x−1/2, −y+3/2, z+1/2; (viii) x+1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | K[GaCl4] |
Mr | 250.63 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 297 |
a, b, c (Å) | 7.2230 (3), 10.4377 (4), 9.3194 (4) |
β (°) | 93.290 (2) |
V (Å3) | 701.45 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.91 |
Crystal size (mm) | 0.60 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Numerical (Herrendorf & B/"arnighausen, 1997) |
Tmin, Tmax | 0.304, 0.438 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4148, 1537, 1323 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.117, 1.17 |
No. of reflections | 1537 |
No. of parameters | 55 |
Δρmax, Δρmin (e Å−3) | 0.90, −0.73 |
Computer programs: KappaCCD Software (Nonius, 1997), HKL SCALEPACK (Otwinowski & Minor 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), maXus (Mackay et al., 1998).
K—Cl3i | 3.196 (2) | K—Cl4v | 3.727 (3) |
K—Cl4ii | 3.251 (3) | K—Cl1ii | 3.761 (3) |
K—Cl3 | 3.260 (2) | Ga—Cl2 | 2.1668 (17) |
K—Cl2iii | 3.304 (3) | Ga—Cl4iii | 2.1677 (19) |
K—Cl1iv | 3.310 (2) | Ga—Cl1vi | 2.1679 (15) |
K—Cl2ii | 3.322 (3) | Ga—Cl3i | 2.1730 (17) |
K—Cl1iii | 3.572 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) −x, −y+1, −z+1; (vi) x+1/2, −y+3/2, z−1/2. |
The structure of K[GaCl4] consists of K+ ions and tetrahedral [GaCl4]− ions. The two ions are displayed in Fig. 1. Fig. 2 shows the arrangement in the unit cell. The K+ ion is coordinated by nine Cl− ions. The coordination polyhedron can be described as a tricapped trigonal prism. The anions show only a very slight distortion, with interatomic distances ranging from 2.1677 (19) to 2.1730 (17) Å. The angles are in the range 106.05 (7) to 113.13 (9)°, thus rather close to the ideal tetrahedral angle. The structure is isotypic with a number of other structures of the composition MI[MIIIX4], which have been published earlier. K[AlCl4] (Mairesse et al., 1978) and K[FeCl4] (Cerisier et al., 1988) have apparently the same structure. They were published in space group P21, though, thus lacking the inversion centre. Ga[AlCl4] (Staffel & Meyer, 1978) is reported with the same structure as the title compound.