Iodido(tri-tert-butyl­phosphane-κP)gold(I)

Sänger, I.; Lerner, H.-W.; Sinke, T.; Bolte, M.

doi:10.1107/S1600536812018569

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m708

doi:10.1107/S1600536812018569

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Iodido(tri-tert-butylphosphane-κP)gold(I)

Inge Sänger,^a Hans-Wolfram Lerner,^a Tanja Sinke ^a and Michael Bolte ^a ^*

^aInstitut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 17 April 2012; accepted 25 April 2012; online 28 April 2012)

The Au^I atom of the title compound, [AuI(C₁₂H₂₇P)], shows an almost linear coordination, with a P—Au—I angle of 178.52 (3)° [Au—P = 2.2723 (14) Å and Au—I = 2.5626 (6) Å].

Related literature

For synthetic background, see: Schödel et al. (2006 ). For a related compound, [Au(^tBu₃P)Cl], see: Schmidbaur et al. (1992 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[AuI(C₁₂H₂₇P)]
M_r = 526.17
Triclinic, $[P \overline 1]$
a = 7.8198 (11) Å
b = 8.9417 (13) Å
c = 12.3507 (19) Å
α = 85.325 (12)°
β = 72.840 (12)°
γ = 80.411 (12)°
V = 813.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 11.02 mm⁻¹
T = 173 K
0.19 × 0.17 × 0.15 mm

Data collection

Stoe IPDS-II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009 ; Blessing, 1995 ) T_min = 0.229, T_max = 0.289
16028 measured reflections
3761 independent reflections
3615 reflections with I > 2σ(I)
R_int = 0.095

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.11
3761 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 2.30 e Å⁻³
Δρ_min = −2.56 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018569/ng5264sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018569/ng5264Isup2.hkl

checkCIF report

Comment top

Recently we have shown that [Au(PF₃)Cl] could be synthesized when AuCl was treated with PF₃ in toluene at low temperature (208 K) (Schödel et al., 2006). The solid-state structure of [Au(PF₃)Cl] reveals attractive interactions between the gold atoms [3.3495 (9) Å]. For closed-shell atoms like Au(I), these interactions can only be rationalized by relativistic effects. In this paper we report the structure of the gold phosphane complex [Au(P^tBu₃)I] which we obtained from the reaction of AuI with P^tBu₃ at room temperature. In this context it should be noted that Schmidbaur and coworkers had synthesized the related chloro complex [Au(P^tBu₃)Cl] from tetrachloroauric acid and ^tBu₃P (Schmidbaur et al., 1992).

The gold centre of the title compound shows an essentially linear coordination with a P—Au—I angle of 178.52 (3)°. A search in the Cambridge Crystallographic Database (CSD, Version 5.33 of November 2011, plus one update; Allen, 2002) yielded mean values of 2.28 (3) Å for a Au—P bond and of 2.55 (5) Å for a Au—I bond. These values compare well with 2.2723 (14) Å for Au1—P1 and 2.5626 (6) Å for Au1—I1. The crystal packing does not reveal any short intermolecular Au···Au, Au···I nor I···I contact. The shortest values found are: Au1···Au1ⁱ 5.8551 (9) Å, Au1···I1ⁱ 4.9305 (9) Å, I1···Iⁱ 5.2412 (12) Å [symmetry operator (i): -x + 2, -y, -z + 1]. For comparison, the shortest Au···Au contact in [Au(PF₃)Cl] (Schödel et al., 2006) amounts to 3.3495 (9) Å. It is remarkable that [Au(P^tBu₃)Cl] (Schmidbaur et al., 1992) is not isostructural with the title compound and does not show any close Au···Au contact, neither. The shortest Au···Au distance is 6.665 Å.

Related literature top

For synthetic background, see: Schödel et al. (2006). For a related compound, [Au(^tBu₃P)Cl], see: Schmidbaur et al. (1992). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

A mixture of ^tBu₃P (0.008 g, 0.04 mmol) and AuI (0.012 g, 0.04 mmol) was treated with 3 ml THF. The reaction mixture was stirred for 18 h at room temperature. After filtration single crystals of [Au(^tBu₃P)I] were obtained after 10 days at room temperature (yield 53%).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A perspective view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound with view onto the ac plane. H atoms are omitted.
	Fig. 3. Reaction scheme for the synthesis obtaining the title compound.

Iodido(tri-tert-butylphosphane-κP)gold(I) top

Crystal data top

[AuI(C₁₂H₂₇P)]	Z = 2
M_r = 526.17	F(000) = 492
Triclinic, P1	D_x = 2.149 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8198 (11) Å	Cell parameters from 39755 reflections
b = 8.9417 (13) Å	θ = 3.3–28.0°
c = 12.3507 (19) Å	µ = 11.02 mm⁻¹
α = 85.325 (12)°	T = 173 K
β = 72.840 (12)°	Block, colourless
γ = 80.411 (12)°	0.19 × 0.17 × 0.15 mm
V = 813.1 (2) Å³

Data collection top

Stoe IPDS-II two-circle diffractometer	3761 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	3615 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	R_int = 0.095
ω scans	θ_max = 27.7°, θ_min = 3.3°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −10→10
T_min = 0.229, T_max = 0.289	k = −11→11
16028 measured reflections	l = −16→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0492P)² + 0.9212P] where P = (F_o² + 2F_c²)/3
3761 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 2.30 e Å⁻³
0 restraints	Δρ_min = −2.56 e Å⁻³

Crystal data top

[AuI(C₁₂H₂₇P)]	γ = 80.411 (12)°
M_r = 526.17	V = 813.1 (2) Å³
Triclinic, P1	Z = 2
a = 7.8198 (11) Å	Mo Kα radiation
b = 8.9417 (13) Å	µ = 11.02 mm⁻¹
c = 12.3507 (19) Å	T = 173 K
α = 85.325 (12)°	0.19 × 0.17 × 0.15 mm
β = 72.840 (12)°

Data collection top

Stoe IPDS-II two-circle diffractometer	3761 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	3615 reflections with I > 2σ(I)
T_min = 0.229, T_max = 0.289	R_int = 0.095
16028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.11	Δρ_max = 2.30 e Å⁻³
3761 reflections	Δρ_min = −2.56 e Å⁻³
136 parameters

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

	x	y	z	U_iso*/U_eq
Au1	0.89137 (2)	0.02882 (2)	0.290901 (16)	0.03077 (9)
I1	1.10032 (6)	−0.20111 (4)	0.34174 (4)	0.04174 (12)
P1	0.70393 (18)	0.22883 (15)	0.24297 (11)	0.0274 (3)
C1	0.4772 (7)	0.2434 (6)	0.3541 (5)	0.0321 (10)
C2	0.6803 (8)	0.1940 (7)	0.0984 (5)	0.0388 (12)
C3	0.8073 (7)	0.4076 (6)	0.2365 (5)	0.0353 (11)
C11	0.3543 (8)	0.3980 (6)	0.3512 (5)	0.0376 (12)
H11A	0.4167	0.4800	0.3611	0.056*
H11B	0.2411	0.3986	0.4126	0.056*
H11C	0.3272	0.4130	0.2781	0.056*
C12	0.3772 (8)	0.1166 (7)	0.3382 (5)	0.0400 (12)
H12A	0.4539	0.0183	0.3394	0.060*
H12B	0.3498	0.1329	0.2653	0.060*
H12C	0.2642	0.1177	0.3997	0.060*
C13	0.5073 (8)	0.2136 (6)	0.4724 (5)	0.0365 (12)
H13A	0.5857	0.1162	0.4739	0.055*
H13B	0.3905	0.2104	0.5298	0.055*
H13C	0.5647	0.2951	0.4887	0.055*
C21	0.6591 (10)	0.0242 (7)	0.0937 (6)	0.0486 (15)
H21A	0.7595	−0.0414	0.1138	0.073*
H21B	0.6603	0.0028	0.0169	0.073*
H21C	0.5442	0.0046	0.1475	0.073*
C22	0.5239 (10)	0.2946 (8)	0.0668 (6)	0.0487 (14)
H22A	0.4102	0.2819	0.1247	0.073*
H22B	0.5182	0.2657	−0.0068	0.073*
H22C	0.5426	0.4009	0.0621	0.073*
C23	0.8575 (10)	0.2151 (9)	0.0076 (5)	0.0547 (17)
H23A	0.9589	0.1506	0.0274	0.082*
H23B	0.8753	0.3216	0.0034	0.082*
H23C	0.8516	0.1868	−0.0661	0.082*
C31	1.0123 (8)	0.3756 (8)	0.1775 (6)	0.0461 (14)
H31A	1.0668	0.2878	0.2152	0.069*
H31B	1.0678	0.4645	0.1822	0.069*
H31C	1.0327	0.3542	0.0978	0.069*
C32	0.7902 (9)	0.4473 (7)	0.3588 (5)	0.0412 (13)
H32A	0.6619	0.4691	0.4013	0.062*
H32B	0.8485	0.5366	0.3573	0.062*
H32C	0.8492	0.3612	0.3957	0.062*
C33	0.7229 (9)	0.5455 (7)	0.1780 (6)	0.0475 (15)
H33A	0.5926	0.5665	0.2157	0.071*
H33B	0.7427	0.5244	0.0982	0.071*
H33C	0.7793	0.6339	0.1826	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.03084 (14)	0.02475 (13)	0.03615 (14)	−0.00018 (9)	−0.01127 (9)	0.00028 (9)
I1	0.0430 (2)	0.02648 (19)	0.0591 (3)	0.00003 (15)	−0.02362 (19)	0.00232 (17)
P1	0.0271 (6)	0.0246 (6)	0.0288 (6)	−0.0015 (5)	−0.0069 (5)	−0.0001 (5)
C1	0.028 (2)	0.024 (2)	0.039 (3)	−0.0002 (18)	−0.004 (2)	−0.002 (2)
C2	0.041 (3)	0.040 (3)	0.035 (3)	0.001 (2)	−0.013 (2)	−0.002 (2)
C3	0.033 (3)	0.032 (3)	0.041 (3)	−0.008 (2)	−0.012 (2)	0.007 (2)
C11	0.030 (3)	0.029 (2)	0.048 (3)	0.004 (2)	−0.007 (2)	0.000 (2)
C12	0.041 (3)	0.038 (3)	0.043 (3)	−0.013 (2)	−0.013 (2)	0.004 (2)
C13	0.044 (3)	0.031 (3)	0.031 (3)	−0.006 (2)	−0.006 (2)	0.003 (2)
C21	0.057 (4)	0.047 (3)	0.049 (3)	0.004 (3)	−0.029 (3)	−0.018 (3)
C22	0.051 (4)	0.049 (3)	0.046 (3)	0.004 (3)	−0.020 (3)	0.002 (3)
C23	0.056 (4)	0.066 (4)	0.031 (3)	−0.001 (3)	0.000 (3)	−0.001 (3)
C31	0.033 (3)	0.051 (3)	0.053 (4)	−0.013 (3)	−0.010 (3)	0.012 (3)
C32	0.051 (3)	0.033 (3)	0.046 (3)	−0.014 (2)	−0.018 (3)	−0.002 (2)
C33	0.045 (3)	0.033 (3)	0.060 (4)	−0.005 (2)	−0.013 (3)	0.014 (3)

Geometric parameters (Å, º) top

Au1—P1	2.2723 (14)	C13—H13B	0.9800
Au1—I1	2.5626 (6)	C13—H13C	0.9800
P1—C1	1.887 (5)	C21—H21A	0.9800
P1—C3	1.894 (5)	C21—H21B	0.9800
P1—C2	1.904 (6)	C21—H21C	0.9800
C1—C12	1.535 (7)	C22—H22A	0.9800
C1—C13	1.544 (8)	C22—H22B	0.9800
C1—C11	1.551 (7)	C22—H22C	0.9800
C2—C22	1.521 (9)	C23—H23A	0.9800
C2—C23	1.533 (9)	C23—H23B	0.9800
C2—C21	1.562 (9)	C23—H23C	0.9800
C3—C33	1.531 (8)	C31—H31A	0.9800
C3—C31	1.540 (8)	C31—H31B	0.9800
C3—C32	1.543 (8)	C31—H31C	0.9800
C11—H11A	0.9800	C32—H32A	0.9800
C11—H11B	0.9800	C32—H32B	0.9800
C11—H11C	0.9800	C32—H32C	0.9800
C12—H12A	0.9800	C33—H33A	0.9800
C12—H12B	0.9800	C33—H33B	0.9800
C12—H12C	0.9800	C33—H33C	0.9800
C13—H13A	0.9800

P1—Au1—I1	178.52 (3)	C1—C13—H13C	109.5
C1—P1—C3	110.4 (2)	H13A—C13—H13C	109.5
C1—P1—C2	110.7 (3)	H13B—C13—H13C	109.5
C3—P1—C2	110.2 (3)	C2—C21—H21A	109.5
C1—P1—Au1	108.63 (17)	C2—C21—H21B	109.5
C3—P1—Au1	108.65 (18)	H21A—C21—H21B	109.5
C2—P1—Au1	108.20 (19)	C2—C21—H21C	109.5
C12—C1—C13	106.2 (4)	H21A—C21—H21C	109.5
C12—C1—C11	108.7 (5)	H21B—C21—H21C	109.5
C13—C1—C11	109.6 (4)	C2—C22—H22A	109.5
C12—C1—P1	109.0 (4)	C2—C22—H22B	109.5
C13—C1—P1	109.1 (4)	H22A—C22—H22B	109.5
C11—C1—P1	114.0 (4)	C2—C22—H22C	109.5
C22—C2—C23	109.0 (5)	H22A—C22—H22C	109.5
C22—C2—C21	109.0 (5)	H22B—C22—H22C	109.5
C23—C2—C21	105.5 (6)	C2—C23—H23A	109.5
C22—C2—P1	115.0 (4)	C2—C23—H23B	109.5
C23—C2—P1	108.8 (4)	H23A—C23—H23B	109.5
C21—C2—P1	109.1 (4)	C2—C23—H23C	109.5
C33—C3—C31	109.3 (5)	H23A—C23—H23C	109.5
C33—C3—C32	109.0 (5)	H23B—C23—H23C	109.5
C31—C3—C32	105.3 (5)	C3—C31—H31A	109.5
C33—C3—P1	115.0 (4)	C3—C31—H31B	109.5
C31—C3—P1	109.6 (4)	H31A—C31—H31B	109.5
C32—C3—P1	108.1 (4)	C3—C31—H31C	109.5
C1—C11—H11A	109.5	H31A—C31—H31C	109.5
C1—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	C3—C32—H32A	109.5
C1—C11—H11C	109.5	C3—C32—H32B	109.5
H11A—C11—H11C	109.5	H32A—C32—H32B	109.5
H11B—C11—H11C	109.5	C3—C32—H32C	109.5
C1—C12—H12A	109.5	H32A—C32—H32C	109.5
C1—C12—H12B	109.5	H32B—C32—H32C	109.5
H12A—C12—H12B	109.5	C3—C33—H33A	109.5
C1—C12—H12C	109.5	C3—C33—H33B	109.5
H12A—C12—H12C	109.5	H33A—C33—H33B	109.5
H12B—C12—H12C	109.5	C3—C33—H33C	109.5
C1—C13—H13A	109.5	H33A—C33—H33C	109.5
C1—C13—H13B	109.5	H33B—C33—H33C	109.5
H13A—C13—H13B	109.5

C3—P1—C1—C12	166.5 (4)	Au1—P1—C2—C23	−72.5 (5)
C2—P1—C1—C12	44.2 (5)	C1—P1—C2—C21	−76.8 (5)
Au1—P1—C1—C12	−74.4 (4)	C3—P1—C2—C21	160.8 (4)
C3—P1—C1—C13	−77.9 (4)	Au1—P1—C2—C21	42.1 (4)
C2—P1—C1—C13	159.8 (3)	C1—P1—C3—C33	−75.2 (5)
Au1—P1—C1—C13	41.1 (4)	C2—P1—C3—C33	47.4 (5)
C3—P1—C1—C11	44.9 (5)	Au1—P1—C3—C33	165.8 (4)
C2—P1—C1—C11	−77.4 (4)	C1—P1—C3—C31	161.1 (4)
Au1—P1—C1—C11	163.9 (4)	C2—P1—C3—C31	−76.3 (5)
C1—P1—C2—C22	46.0 (5)	Au1—P1—C3—C31	42.1 (4)
C3—P1—C2—C22	−76.4 (5)	C1—P1—C3—C32	46.8 (5)
Au1—P1—C2—C22	164.9 (4)	C2—P1—C3—C32	169.4 (4)
C1—P1—C2—C23	168.6 (4)	Au1—P1—C3—C32	−72.2 (4)
C3—P1—C2—C23	46.2 (5)

Experimental details

Crystal data
Chemical formula	[AuI(C₁₂H₂₇P)]
M_r	526.17
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.8198 (11), 8.9417 (13), 12.3507 (19)
α, β, γ (°)	85.325 (12), 72.840 (12), 80.411 (12)
V (Å³)	813.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.02
Crystal size (mm)	0.19 × 0.17 × 0.15

Data collection
Diffractometer	Stoe IPDS-II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)
T_min, T_max	0.229, 0.289
No. of measured, independent and observed [I > 2σ(I)] reflections	16028, 3761, 3615
R_int	0.095
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.096, 1.11
No. of reflections	3761
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.30, −2.56

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

References

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