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From a solution of potassium tetra­chloro­platinate and gallium trichloride in benzene, potassium tetra­chloro­gallate, K[GaCl4], could be crystallized and its structure determined. The crystal structure is isotypic with Ga[AlCl4]. It consists of tetrahedral anions GaCl4- and potassium cations which are coordinated by Cl- in a tricapped trigonal prismatic geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008067/br6095sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008067/br6095Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](Ga-Cl) = 0.002 Å
  • R factor = 0.047
  • wR factor = 0.117
  • Data-to-parameter ratio = 27.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR) is > 1.50 Tmin and Tmax reported: 0.304 0.438 Tmin and Tmax expected: 0.183 0.412 RR = 1.558 Please check that your absorption correction is appropriate.

Comment top

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.

Experimental top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The K+ cation with the surrounding Cl ions and the GaCl4 anion in the structure of K[GaCl4]. Displacement ellipsoids are drawn at the 70% probability level.
[Figure 2] Fig. 2. The unit cell of K[GaCl4], viewed along a.
(I) top
Crystal data top
K[GaCl4]Z = 4
Mr = 250.63Dx = 2.373 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2561 reflections
a = 7.2230 (3) Åθ = 4.2–27.1°
b = 10.4377 (4) ŵ = 5.91 mm1
c = 9.3194 (4) ÅT = 297 K
β = 93.290 (2)°Irregular, colourless
V = 701.45 (5) Å30.60 × 0.25 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer
1323 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
ϕ and ω scansθmax = 27.1°, θmin = 4.2°
Absorption correction: numerical
(Herrendorf & B/"arnighausen, 1997)
h = 99
Tmin = 0.304, Tmax = 0.438k = 1213
4148 measured reflectionsl = 811
1537 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.047Secondary 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 reflectionsΔρmax = 0.90 e Å3
55 parametersΔρmin = 0.73 e Å3
Crystal data top
K[GaCl4]V = 701.45 (5) Å3
Mr = 250.63Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.2230 (3) ŵ = 5.91 mm1
b = 10.4377 (4) ÅT = 297 K
c = 9.3194 (4) Å0.60 × 0.25 × 0.15 mm
β = 93.290 (2)°
Data collection top
Nonius KappaCCD
diffractometer
1537 independent reflections
Absorption correction: numerical
(Herrendorf & B/"arnighausen, 1997)
1323 reflections with I > 2σ(I)
Tmin = 0.304, Tmax = 0.438Rint = 0.037
4148 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04755 parameters
wR(F2) = 0.1170 restraints
S = 1.17Δρmax = 0.90 e Å3
1537 reflectionsΔρmin = 0.73 e Å3
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.

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*/Ueq
K0.1916 (3)0.30431 (16)0.1980 (2)0.0650 (5)
Ga0.74369 (8)0.55242 (6)0.31535 (6)0.0353 (2)
Cl10.4656 (2)0.92013 (17)0.67128 (18)0.0534 (4)
Cl20.7187 (3)0.71919 (19)0.4513 (2)0.0647 (5)
Cl30.0192 (2)0.03565 (18)0.3088 (2)0.0595 (5)
Cl40.1922 (3)0.62138 (19)0.5645 (2)0.0691 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.0692 (10)0.0481 (9)0.0778 (11)0.0068 (7)0.0047 (8)0.0065 (8)
Ga0.0326 (3)0.0387 (4)0.0353 (3)0.0009 (2)0.0075 (2)0.0021 (2)
Cl10.0490 (8)0.0556 (9)0.0585 (9)0.0022 (7)0.0267 (7)0.0046 (7)
Cl20.0658 (11)0.0675 (12)0.0601 (10)0.0158 (9)0.0025 (8)0.0303 (9)
Cl30.0434 (8)0.0618 (10)0.0718 (11)0.0014 (7)0.0116 (8)0.0102 (9)
Cl40.0779 (13)0.0587 (11)0.0698 (12)0.0099 (9)0.0031 (9)0.0251 (9)
Geometric parameters (Å, º) top
K—Cl3i3.196 (2)Ga—Cl3i2.1730 (17)
K—Cl4ii3.251 (3)Cl1—Gavii2.1679 (15)
K—Cl33.260 (2)Cl1—Kviii3.310 (2)
K—Cl2iii3.304 (3)Cl1—Kiii3.572 (3)
K—Cl1iv3.310 (2)Cl2—Kiii3.304 (3)
K—Cl2ii3.322 (3)Cl2—Ki3.322 (3)
K—Cl1iii3.572 (3)Cl3—Gaii2.1730 (17)
K—Cl4v3.727 (3)Cl3—Kii3.196 (2)
K—Cl1ii3.761 (3)Cl4—Gaiii2.1677 (19)
Ga—Cl22.1668 (17)Cl4—Ki3.251 (3)
Ga—Cl4iii2.1677 (19)Cl4—Kv3.727 (3)
Ga—Cl1vi2.1679 (15)
Cl3i—K—Cl4ii103.39 (7)Cl3—K—Cl4v71.36 (6)
Cl3i—K—Cl3156.67 (7)Cl2iii—K—Cl4v62.52 (5)
Cl4ii—K—Cl381.54 (7)Cl1iv—K—Cl4v58.88 (5)
Cl3i—K—Cl2iii89.11 (7)Cl2ii—K—Cl4v68.18 (6)
Cl4ii—K—Cl2iii131.02 (8)Cl1iii—K—Cl4v117.31 (6)
Cl3—K—Cl2iii71.32 (6)Cl2—Ga—Cl4iii113.13 (9)
Cl3i—K—Cl1iv70.25 (5)Cl2—Ga—Cl1vi110.21 (8)
Cl4ii—K—Cl1iv126.95 (8)Cl4iii—Ga—Cl1vi106.67 (8)
Cl3—K—Cl1iv125.14 (7)Cl2—Ga—Cl3i106.05 (7)
Cl2iii—K—Cl1iv101.94 (6)Cl4iii—Ga—Cl3i111.20 (8)
Cl3i—K—Cl2ii139.66 (8)Cl1vi—Ga—Cl3i109.60 (8)
Cl4ii—K—Cl2ii77.89 (6)Gavii—Cl1—Kviii102.56 (7)
Cl3—K—Cl2ii63.56 (5)Gavii—Cl1—Kiii113.46 (7)
Cl2iii—K—Cl2ii120.94 (8)Kviii—Cl1—Kiii102.41 (5)
Cl1iv—K—Cl2ii77.09 (6)Ga—Cl2—Kiii120.04 (9)
Cl3i—K—Cl1iii93.51 (6)Ga—Cl2—Ki94.14 (7)
Cl4ii—K—Cl1iii70.59 (6)Kiii—Cl2—Ki123.63 (8)
Cl3—K—Cl1iii66.28 (5)Gaii—Cl3—Kii127.05 (9)
Cl2iii—K—Cl1iii61.40 (5)Gaii—Cl3—K95.75 (7)
Cl1iv—K—Cl1iii157.67 (7)Kii—Cl3—K112.44 (5)
Cl2ii—K—Cl1iii123.49 (6)Gaiii—Cl4—Ki145.42 (10)
Cl3i—K—Cl4v111.34 (7)Gaiii—Cl4—Kv90.67 (7)
Cl4ii—K—Cl4v143.31 (7)Ki—Cl4—Kv123.88 (7)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y+1, z+1; (iv) x1/2, y+3/2, z1/2; (v) x, y+1, z+1; (vi) x+1/2, y+3/2, z1/2; (vii) x1/2, y+3/2, z+1/2; (viii) x+1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaK[GaCl4]
Mr250.63
Crystal system, space groupMonoclinic, P21/n
Temperature (K)297
a, b, c (Å)7.2230 (3), 10.4377 (4), 9.3194 (4)
β (°) 93.290 (2)
V3)701.45 (5)
Z4
Radiation typeMo Kα
µ (mm1)5.91
Crystal size (mm)0.60 × 0.25 × 0.15
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionNumerical
(Herrendorf & B/"arnighausen, 1997)
Tmin, Tmax0.304, 0.438
No. of measured, independent and
observed [I > 2σ(I)] reflections
4148, 1537, 1323
Rint0.037
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.117, 1.17
No. of reflections1537
No. of parameters55
Δρmax, Δρmin (e Å3)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).

Selected bond lengths (Å) top
K—Cl3i3.196 (2)K—Cl4v3.727 (3)
K—Cl4ii3.251 (3)K—Cl1ii3.761 (3)
K—Cl33.260 (2)Ga—Cl22.1668 (17)
K—Cl2iii3.304 (3)Ga—Cl4iii2.1677 (19)
K—Cl1iv3.310 (2)Ga—Cl1vi2.1679 (15)
K—Cl2ii3.322 (3)Ga—Cl3i2.1730 (17)
K—Cl1iii3.572 (3)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y+1, z+1; (iv) x1/2, y+3/2, z1/2; (v) x, y+1, z+1; (vi) x+1/2, y+3/2, z1/2.
 

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