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Acta Cryst. (2007). E63, m1761    [ doi:10.1107/S1600536807024592 ]

[mu]-1,2-Bis(diphenylphosphino)ethane-[kappa]2P:P-bis[trichloridogallium(III)]

F. Cheng, A. L. Hector, W. Levason, G. Reid, M. Webster and W. Zhang

Abstract top

The centrosymmetric molecule of the title compound, [(GaCl3)2(C26H24P2)] or [(GaCl3)2{[mu]-Ph2P(CH2)2PPh2}], consists of two pseudo-tetrahedral Ga centres coordinated by three Cl atoms [Ga-Cl = 2.1608 (8)-2.1648 (8) Å] and bridged by the diphosphane ligand [Ga-P = 2.3854 (8) Å].

Comment top

Gallium nitride, phosphide, and arsenide are compound semi-conductors (III-V materials) of key importance in the electronics industries; for example GaN, GaP and GaAs are used extensively in LED applications and GaAs is also widely used in integrated circuits, displays and solar cells (O'Brien & Pickett, 2004; Grant, 1993). Gallium halide and gallium alkyl complexes of organo-phosphorus or -arsenic ligands are precursors for the manufacture of GaP and GaAs (O'Brien & Pickett, 2004) and in the course of such an investigation, we obtained the title complex by combination of anhydrous GaCl3 and Ph2P(CH2)2PPh2 in Et2O.

The presence of two coincident Ga—Cl vibrations in the IR and Raman spectra and the 71Ga NMR chemical shift of δ = 267 are consistent with the presence of pseudo-tetrahedral gallium centres (Cl3P donor sets) (Cheng et al., 2007; Baker et al., 1997). Colourless crystals of the title compound were obtained from CH2Cl2/n-hexane, and the structure determination confirms the deduction from the spectroscopic data.

The molecule (Figure 1) has a centre of symmetry which places the GaCl3 groups in an anti arrangement. Comparison with the structure of [(I3Ga)2{µ-Ph2P(CH2)2PPh2}] reported previously (Brown et al., 1997) shows a very similar conformation, although in this case not determined by symmetry. The d(Ga—P) in the present chloro-complex of 2.3854 (8) Å) is shorter than the d(Ga—P) in the corresponding iodo-complex (2.404 (9), 2.410 (9) Å) consistent with weaker Lewis acidity of GaI3.

Similar trends in bond lengths are observed in the [GaX3(PPh3)] (X = Cl or I) complexes (Cheng et al., 2007; Baker et al., 1997).

Related literature top

For related literature, see: Baker et al. (1997); Brown et al. (1997); Cheng et al. (2007); Grant (1993); O'Brien & Pickett (2004).

Experimental top

A solution of Ph2P(CH2)2PPh2 (0.156 g, 0.39 mmol) in anhydrous Et2O (5 cm3) was added dropwise to a stirred solution of GaCl3 (0.137 g, 0.78 mmol) in Et2O (4 cm3). After stirring at room temperature for 15 h, the resultant white precipitate was filtered off, washed with Et2O and dried in vacuo. Yield: 63%. Required for C26H24Cl6Ga2P2: C, 41.6; H, 3.1. Found: C, 41.6; H, 3.3%. 1H NMR (CDCl3): δ = 7.71–7.44 (m, [20H], Ph), 2.92 (d, [4H], CH2). 31P{1H} NMR (CDCl3): δ = -7.6 (relative to external 85% H3PO4). 71Ga NMR: δ = 267 (relative to [Ga(H2O)6]3+ in water). IR (Nujol): ν(Ga—Cl) = 390(s), 351(m) cm-1; Raman: ν(Ga—Cl) = 389(m), 352(s) cm-1.

Crystals were obtained by vapour diffusion of n-hexane into a CH2Cl2 solution of the complex.

Refinement top

H atoms were placed in calculated positions (C—H = 0.95 (aromatic), 0.99 Å (CH2)) and refined as riding; Uiso(H) was set equal to 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of [(GaCl3)2{Ph2P(CH2)2PPh2}], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are omitted for clarity. Symmetry operation: (a) -x, 1 - y, -z.
µ-1,2-Bis(diphenylphosphino)ethane-bis[trichloridogallium(III)] top
Crystal data top
[(GaCl3)2(C26H24P2)]Z = 1
Mr = 750.53F(000) = 374
Triclinic, P1Dx = 1.630 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3586 (10) ÅCell parameters from 3379 reflections
b = 9.457 (2) Åθ = 2.9–27.5°
c = 11.644 (2) ŵ = 2.41 mm−1
α = 66.137 (8)°T = 120 K
β = 77.057 (10)°Plate, colourless
γ = 65.54 (1)°0.20 × 0.20 × 0.04 mm
V = 764.4 (2) Å3
Data collection top
Nonius KappaCCD area-detector
diffractometer		3469 independent reflections
Radiation source: Nonius rotating anode2672 reflections with I > 2σ(I)
graphiteRint = 0.046
φ and ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −10→10
Tmin = 0.645, Tmax = 0.908k = −12→12
15738 measured reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0287P)2 + 0.6686P]
where P = (Fo2 + 2Fc2)/3
3469 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.64 e Å−3
Crystal data top
[(GaCl3)2(C26H24P2)]γ = 65.54 (1)°
Mr = 750.53V = 764.4 (2) Å3
Triclinic, P1Z = 1
a = 8.3586 (10) ÅMo Kα radiation
b = 9.457 (2) ŵ = 2.41 mm−1
c = 11.644 (2) ÅT = 120 K
α = 66.137 (8)°0.20 × 0.20 × 0.04 mm
β = 77.057 (10)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		3469 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2672 reflections with I > 2σ(I)
Tmin = 0.645, Tmax = 0.908Rint = 0.046
15738 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.073Δρmax = 0.56 e Å−3
S = 1.01Δρmin = −0.64 e Å−3
3469 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Ga10.32216 (4)0.20961 (3)0.22313 (3)0.01933 (9)
Cl10.35788 (9)−0.00419 (9)0.39476 (7)0.03122 (18)
Cl20.48454 (9)0.15689 (9)0.06153 (7)0.03109 (17)
Cl30.35063 (9)0.41397 (9)0.24547 (8)0.03397 (18)
P10.02504 (8)0.28638 (8)0.18155 (6)0.01615 (15)
C1−0.1279 (3)0.3960 (3)0.2806 (2)0.0173 (5)
C2−0.0817 (3)0.3569 (3)0.4008 (2)0.0221 (6)
H20.02490.26870.43140.026*
C3−0.1914 (4)0.4470 (3)0.4752 (3)0.0256 (6)
H3−0.16050.41980.55730.031*
C4−0.3461 (3)0.5766 (3)0.4307 (3)0.0219 (6)
H4−0.41990.63920.48180.026*
C5−0.3935 (3)0.6153 (3)0.3124 (3)0.0231 (6)
H5−0.49980.70430.28220.028*
C6−0.2857 (3)0.5241 (3)0.2372 (2)0.0195 (6)
H6−0.31950.54910.15650.023*
C7−0.0119 (3)0.1020 (3)0.2033 (2)0.0176 (5)
C80.1053 (4)−0.0017 (3)0.1387 (3)0.0226 (6)
H80.19850.02740.08390.027*
C90.0850 (4)−0.1466 (3)0.1550 (3)0.0258 (6)
H90.1638−0.21700.11090.031*
C10−0.0500 (4)−0.1892 (3)0.2357 (3)0.0248 (6)
H10−0.0640−0.28870.24670.030*
C11−0.1646 (3)−0.0873 (3)0.3003 (3)0.0254 (6)
H11−0.2563−0.11780.35610.030*
C12−0.1467 (3)0.0590 (3)0.2843 (3)0.0211 (6)
H12−0.22610.12910.32850.025*
C13−0.0181 (3)0.4203 (3)0.0182 (2)0.0174 (5)
H13A0.05690.3586−0.03780.021*
H13B−0.14260.44980.00520.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ga10.02001 (16)0.01879 (16)0.02054 (17)−0.00612 (12)0.00056 (11)−0.01015 (12)
Cl10.0287 (4)0.0259 (4)0.0247 (4)−0.0010 (3)−0.0019 (3)−0.0043 (3)
Cl20.0270 (4)0.0394 (4)0.0267 (4)−0.0085 (3)0.0062 (3)−0.0193 (3)
Cl30.0343 (4)0.0321 (4)0.0482 (5)−0.0150 (3)−0.0018 (3)−0.0239 (4)
P10.0197 (3)0.0142 (3)0.0162 (3)−0.0075 (3)0.0014 (3)−0.0069 (3)
C10.0207 (13)0.0138 (12)0.0190 (13)−0.0077 (10)0.0024 (10)−0.0078 (10)
C20.0219 (14)0.0201 (14)0.0185 (14)−0.0032 (11)−0.0017 (11)−0.0057 (11)
C30.0323 (16)0.0272 (15)0.0186 (14)−0.0092 (12)0.0008 (12)−0.0122 (12)
C40.0221 (14)0.0204 (14)0.0255 (15)−0.0093 (11)0.0078 (11)−0.0134 (12)
C50.0172 (13)0.0197 (14)0.0296 (16)−0.0048 (11)0.0013 (11)−0.0096 (12)
C60.0204 (13)0.0213 (14)0.0183 (14)−0.0094 (11)−0.0022 (10)−0.0060 (11)
C70.0203 (13)0.0138 (12)0.0174 (13)−0.0061 (10)−0.0048 (10)−0.0025 (10)
C80.0264 (14)0.0216 (14)0.0219 (14)−0.0125 (11)0.0042 (11)−0.0088 (12)
C90.0348 (16)0.0199 (14)0.0248 (15)−0.0095 (12)0.0005 (12)−0.0117 (12)
C100.0310 (15)0.0177 (14)0.0283 (16)−0.0120 (12)−0.0078 (12)−0.0043 (12)
C110.0214 (14)0.0207 (14)0.0329 (16)−0.0116 (11)0.0011 (12)−0.0059 (12)
C120.0202 (13)0.0154 (13)0.0259 (15)−0.0049 (10)−0.0006 (11)−0.0078 (11)
C130.0223 (13)0.0185 (13)0.0132 (13)−0.0081 (11)0.0004 (10)−0.0073 (11)
Geometric parameters (Å, °) top
Ga1—Cl12.1608 (8)C5—H50.9500
Ga1—Cl22.1648 (8)C6—H60.9500
Ga1—Cl32.1620 (8)C7—C121.385 (4)
Ga1—P12.3854 (8)C7—C81.399 (4)
P1—C11.802 (2)C8—C91.383 (4)
P1—C71.804 (3)C8—H80.9500
P1—C131.825 (3)C9—C101.383 (4)
C1—C21.396 (4)C9—H90.9500
C1—C61.394 (3)C10—C111.383 (4)
C2—C31.382 (4)C10—H100.9500
C2—H20.9500C11—C121.386 (4)
C3—C41.385 (4)C11—H110.9500
C3—H30.9500C12—H120.9500
C4—C51.381 (4)C13—C13i1.532 (5)
C4—H40.9500C13—H13A0.9900
C5—C61.391 (4)C13—H13B0.9900
Cl1—Ga1—Cl2114.33 (3)C5—C6—C1119.8 (2)
Cl1—Ga1—Cl3112.70 (3)C5—C6—H6120.1
Cl3—Ga1—Cl2110.48 (3)C1—C6—H6120.1
Cl1—Ga1—P1103.11 (3)C12—C7—C8120.2 (2)
Cl2—Ga1—P1106.38 (3)C12—C7—P1122.0 (2)
Cl3—Ga1—P1109.27 (3)C8—C7—P1117.67 (19)
C1—P1—C7111.46 (12)C9—C8—C7119.7 (2)
C1—P1—C13107.72 (12)C9—C8—H8120.1
C7—P1—C13105.83 (11)C7—C8—H8120.1
C1—P1—Ga1111.15 (9)C8—C9—C10120.0 (3)
C7—P1—Ga1108.80 (8)C8—C9—H9120.0
C13—P1—Ga1111.78 (9)C10—C9—H9120.0
C2—C1—C6119.7 (2)C11—C10—C9120.2 (2)
C2—C1—P1118.82 (19)C11—C10—H10119.9
C6—C1—P1121.4 (2)C9—C10—H10119.9
C3—C2—C1119.9 (2)C10—C11—C12120.6 (2)
C3—C2—H2120.1C10—C11—H11119.7
C1—C2—H2120.1C12—C11—H11119.7
C4—C3—C2120.3 (3)C7—C12—C11119.3 (2)
C4—C3—H3119.9C7—C12—H12120.3
C2—C3—H3119.9C11—C12—H12120.3
C3—C4—C5120.3 (2)C13i—C13—P1112.4 (2)
C3—C4—H4119.9C13i—C13—H13A109.1
C5—C4—H4119.9P1—C13—H13A109.1
C4—C5—C6120.1 (2)C13i—C13—H13B109.1
C4—C5—H5120.0P1—C13—H13B109.1
C6—C5—H5120.0H13A—C13—H13B107.8
Cl1—Ga1—P1—C177.84 (9)C4—C5—C6—C1−1.4 (4)
Cl3—Ga1—P1—C1−42.24 (9)C2—C1—C6—C51.9 (4)
Cl2—Ga1—P1—C1−161.53 (9)P1—C1—C6—C5−174.51 (19)
Cl1—Ga1—P1—C7−45.25 (9)C1—P1—C7—C122.0 (3)
Cl3—Ga1—P1—C7−165.34 (9)C13—P1—C7—C12−114.9 (2)
Cl2—Ga1—P1—C775.37 (9)Ga1—P1—C7—C12124.9 (2)
Cl1—Ga1—P1—C13−161.76 (9)C1—P1—C7—C8−175.6 (2)
Cl3—Ga1—P1—C1378.15 (9)C13—P1—C7—C867.5 (2)
Cl2—Ga1—P1—C13−41.14 (9)Ga1—P1—C7—C8−52.7 (2)
C7—P1—C1—C290.2 (2)C12—C7—C8—C90.7 (4)
C13—P1—C1—C2−154.1 (2)P1—C7—C8—C9178.3 (2)
Ga1—P1—C1—C2−31.3 (2)C7—C8—C9—C10−0.5 (4)
C7—P1—C1—C6−93.3 (2)C8—C9—C10—C11−0.1 (4)
C13—P1—C1—C622.3 (2)C9—C10—C11—C120.6 (4)
Ga1—P1—C1—C6145.10 (18)C8—C7—C12—C11−0.2 (4)
C6—C1—C2—C3−0.9 (4)P1—C7—C12—C11−177.8 (2)
P1—C1—C2—C3175.6 (2)C10—C11—C12—C7−0.4 (4)
C1—C2—C3—C4−0.6 (4)C1—P1—C13—C13i64.0 (3)
C2—C3—C4—C51.0 (4)C7—P1—C13—C13i−176.6 (2)
C3—C4—C5—C6−0.1 (4)Ga1—P1—C13—C13i−58.4 (3)
Symmetry codes: (i) −x, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
Ga1—Cl12.1608 (8)P1—C11.802 (2)
Ga1—Cl22.1648 (8)P1—C71.804 (3)
Ga1—Cl32.1620 (8)P1—C131.825 (3)
Ga1—P12.3854 (8)
Cl1—Ga1—Cl2114.33 (3)Cl3—Ga1—P1109.27 (3)
Cl1—Ga1—Cl3112.70 (3)C1—P1—C7111.46 (12)
Cl3—Ga1—Cl2110.48 (3)C1—P1—C13107.72 (12)
Cl1—Ga1—P1103.11 (3)C7—P1—C13105.83 (11)
Cl2—Ga1—P1106.38 (3)
Acknowledgements top

The authors thank RCUK for support (grant No. EP/C006731/1).

references
References top

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