supplementary materials


gk2571 scheme

Acta Cryst. (2013). E69, m339    [ doi:10.1107/S1600536813013470 ]

Bis[[mu]-1,3-bis(diphenylphosphanyl)propane-[kappa]2P:P']digold(I) tetrachloridonickelate(II) diethyl ether monosolvate

A. Igashira-Kamiyama, T. Itai, Y. Arai and T. Konno

Abstract top

The title compound, [Au2(C27H26P2)2][NiCl4]·C4H10O, consists of a digold(I) complex cation, an [NiCl4]2- complex anion and a diethyl ether solvent molecule. Two 1,3-bis(diphenylphosphanyl)propane (dppp) ligands bridge two AuI atoms, forming a metallacycle in which each of the AuI atoms is coordinated in a slightly distorted linear environment by two P atoms. In the complex anion, the NiII atom is coordinated by four chloride ligands in a distorted tetrahedral geometry. The complex cation and the complex anion form a cation-anion pair through two Au...Cl contacts of 3.040 (1) and 3.021 (2) Å. One of the phenyl groups of the dppp ligand is disordered over two positions with equal occupancies.

Comment top

In recent years, diphosphine-bridged cyclic digold(I) complexes have attracted considerable attention because of their intriguing photophysical properties that originate from the presence of an aurophilic interaction between gold(I) ions. A typical example is [Au2(dppm)2]2+ (dppm = bis(diphenylphosphanyl)methane), which is easily prepared from dppm having a methylene linker between two P atoms, in combination with an AuI ion. Analogous digold(I) complexes having a longer linker between two P atoms, such as 1,2-bis(diphenylphosphanyl)ethane (dppe) and 1,3-bis(diphenylphosphanyl)propane (dppp), have also been prepared, but only a few of them have been structurally characterized to date (Allen, 2002).

Recently, we started to investigate the creation of diphosphine-bridged digold(I) metalloligands and their coordination behavior toward various metal ions, with the aim of the rational construction of heterometallic multinuclear and metallosupramolecular structures (Lee et al., 2012; Igashira-Kamiyama et al., 2012; Hashimoto et al., 2010). In the course of this study, we found the formation of a diphosphine-bridged digold(I) complex, [Au2(dppp)2]2+ (dppp = 1,3-bis(diphenylphosphanyl)propane), which is cocrystallized with [NiCl4]2– to give single-crystals of [Au2(dppp)2][NiCl4].Et2O (I). Here, we report the synthesis and crystal structure of (I).

Treatment of [Au2Cl2(dppp)] (Mirabelli et al., 1987) with 1 equiv of N,N'-ethylene-bis-D-penicillamine (Howard-Lock et al., 1986; Blondeau et al., 1967) in ethanol/water in the presence of KOH gave a white powder. When this powder was reacted with NiCl2.6H2O in ethanol, blue needle crystals of [Au2(dppp)2][NiCl4].Et2O (I) were obtained by the vapor diffusion of diethylether into the reaction solution.

Compound (I) crystallized in a centrosymmetric space group P21/n, which contains one digold(I) complex cation, one nickel(II) complex anion and one solvate diethylether molecule in the asymmetric unit. The complex cation has a cyclic digold(I) structure in [Au2(dppp)2]2+, in which two dppp ligands bridge two AuI atoms. Each AuI atom adopts a slightly distorted linear geometry (176.68 (5)°, 177.98 (5)°) coordinated by two P atoms from two different dppp ligands (Fig. 1). The Au–P bond distances (2.3013 (13)–2.3129 (13) Å) are within the range observed for [Au2(dppp)2]2[Mo8O26], [Au2(dppp)2]2[PMo8O26] and [Au2(dppp)2](CF3CO2)2 (Au–P = 2.271–2.324 Å) (Gruber et al., 2010; Brandys et al., 2001). In the complex-cation of (I), two AuI atoms and four P atoms are deviated from co-planarity, with the dihedral angle between two Au2P2 planes being 21.94 (2)°. This structural feature is different from those found in [Au2(dppp)2]2[Mo8O26], [Au2(dppp)2]2[PMo8O26] and [Au2(dppp)2](CF3CO2)2, in which all the AuI and P atoms in each complex-cation are located nearly on the same plane (Gruber et al., 2010; Brandys et al., 2001). The distance between two AuI atoms in [Au2(dppp)2]2+ is 5.5424 (4) Å, indicative of the absence of an aurophilic interaction. In (I), a nickel(II) complex-anion, [NiCl4]2–, which has a distorted tetrahedral geometry, coexists with [Au2(dppp)2]2+ to balance the total charge. Note that [Au2(dppp)2]2+ and [NiCl4]2– are connected to each other through two Au···Cl bonding interactions (3.040 (1) Å and 3.021 (2) Å), while any other significant intermolecular interactions do not exist in (I) (Fig. 2).

Related literature top

For closely related structures, see: Gruber & Jansen (2010); Brandys & Puddephatt (2001). For related studies, see: Igashira-Kamiyama et al. (2012); Lee et al. (2012); Lim et al. (2011); Hashimoto et al. (2010). For the starting material, see: Howard-Lock et al. (1986); Blondeau et al. (1967); Mirabelli et al. (1987). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a white suspension containing 0.15 g (0.17 mmol) of [Au2Cl2(dppp)] in 300 ml of EtOH was added 0.056 g (0.17 mmol) of N,N'-ethylene-bis-D-penicillamine dissolved in 3 ml of a 0.1 M KOH aqueous solution. The mixture was stirred at room temperature for 3 h. The resulting colorless solution was evaporated to dryness, and then the residue was washed with H2O to give a white powder (0.15 g). When 2.5 mg (0.01 mmol) of NiCl2.6H2O was added to a suspension of this white powder (10 mg) in 1 ml of EtOH, followed by stirring at room temperature for 3 h, a clear red orange solution was obtained. Vapor diffusion of diethylether into the resulting red orange solution afforded a small amount of blue needle crystals of [Au2(dppp)2][NiCl4].Et2O.

Refinement top

H atoms were placed at calculated positions [C–H = 0.99 (methylene) or 0.95 Å (phenyl)] and refined as riding with Uiso(H) = 1.2Ueq(C). One phenyl ring is disordered over two positions (C7–C12 and C13–C18) with site occupancies of 0.5. The FLAT and SIMU restraints were used to model the disordered phenyl ring.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2000); cell refinement: PROCESS-AUTO (Rigaku, 2000); data reduction: PROCESS-AUTO (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG 2009 (Kabuto et al., 2009); software used to prepare material for publication: Yadokari-XG 2009 (Kabuto et al., 2009).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound with the atom-numbering scheme. H atoms are omitted for clarity.
[Figure 2] Fig. 2. Crystal packing of the title compound. H atoms are omitted for clarity.
Bis[µ-1,3-bis(diphenylphosphanyl)propane-κ2P:P']digold(I) tetrachloridonickelate(II) diethyl ether monosolvate top
Crystal data top
[Au2(C27H26P2)2][NiCl4]·C4H10OF(000) = 2928
Mr = 1493.40Dx = 1.709 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ynCell parameters from 2299 reflections
a = 18.9290 (5) Åθ = 4.1–27.6°
b = 16.1945 (7) ŵ = 5.70 mm1
c = 19.0895 (17) ÅT = 200 K
β = 97.368 (7)°Needle, blue
V = 5803.5 (6) Å30.28 × 0.05 × 0.03 mm
Z = 4
Data collection top
Rigaku R-AXIS VII
diffractometer
13273 independent reflections
Radiation source: fine-focus sealed tube10666 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = 2224
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 2021
Tmin = 0.580, Tmax = 0.773l = 2424
45449 measured reflections
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0332P)2 + 5.0632P]
where P = (Fo2 + 2Fc2)/3
13273 reflections(Δ/σ)max = 0.001
685 parametersΔρmax = 1.16 e Å3
78 restraintsΔρmin = 0.88 e Å3
Crystal data top
[Au2(C27H26P2)2][NiCl4]·C4H10OV = 5803.5 (6) Å3
Mr = 1493.40Z = 4
Monoclinic, P21/nMo Kα radiation
a = 18.9290 (5) ŵ = 5.70 mm1
b = 16.1945 (7) ÅT = 200 K
c = 19.0895 (17) Å0.28 × 0.05 × 0.03 mm
β = 97.368 (7)°
Data collection top
Rigaku R-AXIS VII
diffractometer
13273 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
10666 reflections with I > 2σ(I)
Tmin = 0.580, Tmax = 0.773Rint = 0.042
45449 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.083Δρmax = 1.16 e Å3
S = 1.14Δρmin = 0.88 e Å3
13273 reflectionsAbsolute structure: ?
685 parametersFlack parameter: ?
78 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*/UeqOcc. (<1)
Au10.779915 (10)0.834674 (12)0.074536 (10)0.03063 (6)
Au20.549659 (10)0.900739 (12)0.218117 (10)0.02907 (6)
P10.73666 (7)0.70192 (8)0.05633 (7)0.0304 (3)
P20.53747 (7)0.76109 (8)0.23538 (7)0.0285 (3)
P30.81787 (6)0.96902 (8)0.09657 (7)0.0271 (3)
P40.56077 (6)1.03989 (8)0.19661 (7)0.0266 (3)
C10.7040 (3)0.6692 (3)0.1377 (3)0.0324 (12)
H10.68370.61290.13130.039*
H20.74430.66700.17620.039*
C20.6472 (2)0.7282 (3)0.1583 (3)0.0306 (11)
H30.60570.72700.12100.037*
H40.66660.78500.16050.037*
C30.6218 (2)0.7075 (3)0.2294 (2)0.0296 (11)
H50.65800.72510.26860.036*
H60.61490.64710.23330.036*
C40.7729 (2)1.0247 (3)0.1619 (3)0.0289 (11)
H70.78781.00080.20920.035*
H80.78811.08320.16300.035*
C50.6909 (2)1.0206 (3)0.1457 (3)0.0348 (12)
H90.67601.04240.09760.042*
H100.67540.96220.14660.042*
C60.6541 (2)1.0700 (3)0.1987 (3)0.0304 (11)
H110.65681.12960.18770.036*
H120.67941.06100.24680.036*
C70.802 (2)0.623 (3)0.0354 (17)0.055 (4)0.50
C80.7861 (11)0.5432 (14)0.0384 (9)0.064 (4)0.50
H130.74240.52640.05370.077*0.50
C90.8353 (12)0.4825 (17)0.0181 (13)0.070 (4)0.50
H140.82550.42530.02180.085*0.50
C100.8946 (13)0.5076 (15)0.0057 (11)0.075 (4)0.50
H150.92530.46810.02280.090*0.50
C110.9112 (9)0.5852 (10)0.0060 (10)0.078 (3)0.50
H160.95590.60150.01910.094*0.50
C120.8637 (8)0.6454 (10)0.0129 (9)0.067 (3)0.50
H170.87510.70230.00970.081*0.50
C130.7966 (16)0.622 (3)0.0378 (12)0.030 (3)0.50
C140.7708 (9)0.5416 (12)0.0162 (8)0.042 (3)0.50
H180.72100.53170.00940.051*0.50
C150.8156 (8)0.4794 (15)0.0055 (11)0.049 (3)0.50
H190.79830.42650.00990.059*0.50
C160.8907 (12)0.4968 (14)0.0186 (9)0.056 (3)0.50
H200.92360.45480.01010.067*0.50
C170.9153 (7)0.5694 (9)0.0421 (8)0.056 (3)0.50
H210.96520.57850.05160.068*0.50
C180.8683 (7)0.6319 (9)0.0526 (7)0.045 (3)0.50
H220.88660.68330.07080.054*0.50
C190.6622 (3)0.6947 (3)0.0140 (3)0.0304 (11)
C200.6632 (3)0.7447 (3)0.0737 (3)0.0430 (14)
H230.70140.78210.07640.052*
C210.6076 (3)0.7395 (4)0.1294 (3)0.0500 (16)
H240.60870.77270.17030.060*
C220.5512 (3)0.6863 (4)0.1253 (3)0.0525 (17)
H250.51300.68390.16270.063*
C230.5506 (3)0.6369 (3)0.0668 (3)0.0469 (15)
H260.51230.59960.06470.056*
C240.6050 (3)0.6407 (3)0.0109 (3)0.0404 (13)
H270.60340.60670.02940.048*
C250.5129 (3)0.7377 (3)0.3220 (3)0.0354 (12)
C260.4619 (3)0.6787 (3)0.3322 (3)0.0456 (15)
H280.43990.64720.29340.055*
C270.4431 (4)0.6658 (4)0.3999 (4)0.0574 (18)
H290.40710.62690.40690.069*
C280.4769 (4)0.7097 (4)0.4565 (4)0.072 (2)
H300.46490.70020.50260.086*
C290.5281 (5)0.7671 (4)0.4462 (3)0.078 (2)
H310.55120.79730.48520.093*
C300.5462 (4)0.7811 (4)0.3794 (3)0.0577 (18)
H320.58160.82090.37280.069*
C310.4727 (2)0.7128 (3)0.1696 (3)0.0279 (11)
C320.4813 (3)0.6337 (3)0.1438 (3)0.0432 (14)
H330.52020.60070.16380.052*
C330.4338 (3)0.6028 (4)0.0894 (3)0.0498 (15)
H340.44010.54830.07280.060*
C340.3779 (3)0.6490 (4)0.0588 (3)0.0518 (16)
H350.34640.62740.02040.062*
C350.3675 (3)0.7272 (4)0.0841 (3)0.0485 (15)
H360.32770.75910.06440.058*
C360.4150 (3)0.7590 (3)0.1381 (3)0.0366 (12)
H370.40830.81350.15420.044*
C370.8062 (2)1.0336 (3)0.0176 (3)0.0303 (11)
C380.7747 (3)1.0013 (4)0.0457 (3)0.0444 (14)
H380.76110.94480.04810.053*
C390.7627 (3)1.0501 (5)0.1058 (3)0.0565 (18)
H390.74051.02770.14910.068*
C400.7836 (3)1.1317 (5)0.1014 (4)0.0618 (19)
H400.77631.16550.14230.074*
C410.8145 (3)1.1645 (4)0.0391 (4)0.0562 (18)
H410.82761.22110.03670.067*
C420.8268 (3)1.1151 (3)0.0208 (3)0.0422 (14)
H420.84951.13770.06390.051*
C430.9125 (2)0.9708 (3)0.1293 (3)0.0269 (11)
C440.9617 (3)0.9585 (3)0.0813 (3)0.0345 (12)
H430.94570.95660.03200.041*
C451.0339 (3)0.9489 (3)0.1052 (3)0.0396 (13)
H441.06660.94010.07210.048*
C461.0583 (3)0.9520 (3)0.1762 (3)0.0377 (13)
H451.10760.94550.19200.045*
C471.0108 (3)0.9648 (3)0.2241 (3)0.0363 (12)
H461.02760.96790.27310.044*
C480.9377 (3)0.9733 (3)0.2010 (3)0.0318 (11)
H470.90520.98090.23450.038*
C490.5141 (2)1.0717 (3)0.1118 (2)0.0265 (10)
C500.5378 (3)1.1376 (3)0.0733 (3)0.0341 (12)
H480.58041.16640.09000.041*
C510.4972 (3)1.1601 (3)0.0095 (3)0.0434 (14)
H490.51231.20500.01700.052*
C520.4360 (3)1.1183 (4)0.0153 (3)0.0420 (14)
H500.40931.13400.05880.050*
C530.4130 (3)1.0534 (3)0.0231 (3)0.0409 (14)
H510.37021.02510.00640.049*
C540.4522 (3)1.0298 (3)0.0853 (3)0.0343 (12)
H520.43680.98420.11080.041*
C550.5201 (3)1.1036 (3)0.2596 (3)0.0320 (12)
C560.5434 (3)1.1835 (3)0.2746 (3)0.0463 (15)
H530.58331.20460.25490.056*
C570.5084 (4)1.2322 (4)0.3184 (3)0.0583 (18)
H540.52461.28690.32890.070*
C580.4510 (4)1.2029 (5)0.3467 (4)0.067 (2)
H550.42721.23760.37630.081*
C590.4271 (4)1.1241 (5)0.3329 (4)0.069 (2)
H560.38691.10400.35280.083*
C600.4624 (3)1.0732 (4)0.2892 (3)0.0530 (16)
H570.44681.01810.28000.064*
Ni10.79494 (3)0.85982 (4)0.34081 (3)0.03311 (16)
Cl10.81798 (9)0.81747 (9)0.23347 (7)0.0496 (4)
Cl20.68553 (8)0.91672 (11)0.32021 (9)0.0624 (5)
Cl30.87604 (7)0.96027 (8)0.37596 (7)0.0377 (3)
Cl40.77899 (8)0.74535 (9)0.40236 (8)0.0508 (4)
O10.2306 (3)0.4928 (4)0.2151 (3)0.0986 (18)
C610.2757 (5)0.5546 (8)0.2001 (6)0.125 (4)
H580.26430.57020.14980.150*
H590.32520.53370.20720.150*
C620.2710 (6)0.6288 (8)0.2443 (8)0.171 (6)
H600.30410.67090.23120.257*
H610.28350.61420.29420.257*
H620.22230.65050.23690.257*
C630.2334 (7)0.4189 (7)0.1756 (5)0.125 (4)
H630.27980.39120.18890.151*
H640.22860.43190.12460.151*
C640.1743 (8)0.3632 (7)0.1905 (7)0.174 (6)
H650.17640.31180.16370.260*
H660.12850.39050.17640.260*
H670.17930.35070.24110.260*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.02931 (11)0.03070 (12)0.03187 (11)0.00375 (8)0.00394 (8)0.00447 (8)
Au20.03258 (11)0.02486 (11)0.02932 (11)0.00187 (8)0.00220 (8)0.00207 (8)
P10.0302 (7)0.0293 (7)0.0310 (7)0.0001 (6)0.0014 (6)0.0036 (6)
P20.0322 (7)0.0262 (7)0.0271 (7)0.0005 (6)0.0038 (5)0.0034 (5)
P30.0232 (7)0.0300 (7)0.0283 (7)0.0020 (5)0.0043 (5)0.0013 (5)
P40.0250 (7)0.0248 (7)0.0297 (7)0.0018 (5)0.0029 (5)0.0008 (5)
C10.038 (3)0.023 (3)0.034 (3)0.003 (2)0.004 (2)0.002 (2)
C20.026 (3)0.029 (3)0.036 (3)0.000 (2)0.003 (2)0.002 (2)
C30.031 (3)0.026 (3)0.031 (3)0.004 (2)0.000 (2)0.004 (2)
C40.029 (3)0.028 (3)0.029 (3)0.005 (2)0.004 (2)0.003 (2)
C50.027 (3)0.038 (3)0.039 (3)0.001 (2)0.002 (2)0.009 (2)
C60.032 (3)0.027 (3)0.031 (3)0.007 (2)0.000 (2)0.007 (2)
C70.046 (8)0.048 (7)0.077 (8)0.005 (6)0.026 (6)0.011 (7)
C80.057 (8)0.055 (7)0.084 (8)0.013 (6)0.019 (6)0.008 (7)
C90.063 (8)0.054 (7)0.098 (9)0.015 (7)0.020 (7)0.007 (7)
C100.065 (7)0.061 (7)0.104 (9)0.019 (6)0.026 (7)0.011 (7)
C110.063 (7)0.064 (7)0.111 (8)0.004 (6)0.023 (7)0.009 (7)
C120.051 (7)0.055 (7)0.100 (8)0.002 (5)0.026 (6)0.012 (6)
C130.023 (6)0.036 (6)0.030 (5)0.003 (5)0.005 (5)0.006 (5)
C140.030 (6)0.042 (6)0.053 (6)0.001 (5)0.001 (5)0.010 (5)
C150.035 (6)0.044 (6)0.067 (7)0.006 (5)0.005 (5)0.003 (5)
C160.040 (6)0.057 (7)0.072 (7)0.014 (5)0.012 (6)0.005 (6)
C170.034 (5)0.067 (6)0.068 (6)0.009 (5)0.006 (5)0.002 (5)
C180.030 (5)0.052 (6)0.052 (5)0.010 (4)0.003 (5)0.008 (5)
C190.030 (3)0.030 (3)0.029 (3)0.007 (2)0.003 (2)0.005 (2)
C200.047 (3)0.040 (3)0.043 (3)0.002 (3)0.008 (3)0.002 (3)
C210.064 (4)0.056 (4)0.028 (3)0.014 (3)0.003 (3)0.001 (3)
C220.058 (4)0.050 (4)0.043 (4)0.017 (3)0.021 (3)0.015 (3)
C230.039 (3)0.034 (3)0.063 (4)0.003 (3)0.010 (3)0.013 (3)
C240.045 (3)0.026 (3)0.047 (3)0.005 (2)0.007 (3)0.002 (2)
C250.048 (3)0.029 (3)0.031 (3)0.007 (2)0.010 (2)0.007 (2)
C260.054 (4)0.042 (4)0.043 (3)0.001 (3)0.015 (3)0.004 (3)
C270.078 (5)0.043 (4)0.059 (4)0.001 (3)0.036 (4)0.010 (3)
C280.129 (7)0.053 (4)0.040 (4)0.007 (5)0.038 (4)0.005 (3)
C290.138 (7)0.066 (5)0.029 (4)0.020 (5)0.009 (4)0.004 (3)
C300.087 (5)0.051 (4)0.035 (3)0.019 (4)0.006 (3)0.003 (3)
C310.026 (3)0.027 (3)0.032 (3)0.003 (2)0.009 (2)0.002 (2)
C320.046 (3)0.032 (3)0.049 (4)0.002 (3)0.005 (3)0.002 (3)
C330.052 (4)0.035 (3)0.061 (4)0.005 (3)0.003 (3)0.010 (3)
C340.048 (4)0.061 (4)0.043 (4)0.009 (3)0.004 (3)0.006 (3)
C350.034 (3)0.062 (4)0.048 (4)0.009 (3)0.003 (3)0.002 (3)
C360.035 (3)0.038 (3)0.037 (3)0.004 (2)0.002 (2)0.004 (2)
C370.023 (3)0.037 (3)0.033 (3)0.006 (2)0.011 (2)0.005 (2)
C380.034 (3)0.064 (4)0.034 (3)0.003 (3)0.002 (2)0.009 (3)
C390.043 (4)0.092 (6)0.035 (3)0.016 (4)0.006 (3)0.010 (3)
C400.058 (4)0.077 (5)0.053 (4)0.034 (4)0.018 (3)0.030 (4)
C410.063 (4)0.049 (4)0.062 (4)0.019 (3)0.028 (4)0.020 (3)
C420.043 (3)0.042 (4)0.045 (3)0.013 (3)0.019 (3)0.004 (3)
C430.028 (3)0.019 (3)0.033 (3)0.001 (2)0.005 (2)0.002 (2)
C440.035 (3)0.040 (3)0.029 (3)0.004 (2)0.005 (2)0.001 (2)
C450.030 (3)0.044 (3)0.047 (3)0.005 (2)0.016 (3)0.008 (3)
C460.023 (3)0.038 (3)0.051 (4)0.000 (2)0.003 (2)0.004 (3)
C470.035 (3)0.039 (3)0.034 (3)0.004 (2)0.002 (2)0.001 (2)
C480.030 (3)0.030 (3)0.037 (3)0.000 (2)0.010 (2)0.000 (2)
C490.025 (3)0.027 (3)0.029 (3)0.006 (2)0.008 (2)0.001 (2)
C500.035 (3)0.027 (3)0.042 (3)0.003 (2)0.011 (2)0.002 (2)
C510.056 (4)0.039 (3)0.036 (3)0.014 (3)0.012 (3)0.012 (3)
C520.041 (3)0.052 (4)0.032 (3)0.021 (3)0.001 (3)0.002 (3)
C530.039 (3)0.046 (4)0.036 (3)0.001 (3)0.003 (3)0.006 (3)
C540.033 (3)0.031 (3)0.039 (3)0.002 (2)0.003 (2)0.003 (2)
C550.034 (3)0.035 (3)0.028 (3)0.008 (2)0.005 (2)0.002 (2)
C560.062 (4)0.037 (4)0.041 (3)0.009 (3)0.013 (3)0.000 (3)
C570.087 (5)0.043 (4)0.048 (4)0.014 (4)0.017 (4)0.008 (3)
C580.089 (6)0.067 (5)0.051 (4)0.036 (4)0.027 (4)0.002 (4)
C590.066 (5)0.084 (6)0.065 (5)0.013 (4)0.037 (4)0.002 (4)
C600.051 (4)0.051 (4)0.063 (4)0.003 (3)0.031 (3)0.005 (3)
Ni10.0343 (4)0.0337 (4)0.0296 (4)0.0045 (3)0.0027 (3)0.0019 (3)
Cl10.0703 (10)0.0470 (9)0.0309 (7)0.0074 (7)0.0042 (7)0.0045 (6)
Cl20.0373 (8)0.0790 (12)0.0660 (11)0.0071 (8)0.0121 (7)0.0174 (9)
Cl30.0343 (7)0.0340 (7)0.0437 (8)0.0041 (6)0.0011 (6)0.0060 (6)
Cl40.0627 (10)0.0424 (9)0.0474 (9)0.0060 (7)0.0077 (7)0.0110 (7)
O10.106 (5)0.114 (5)0.080 (4)0.022 (4)0.031 (4)0.001 (4)
C610.063 (6)0.172 (11)0.138 (10)0.017 (7)0.002 (6)0.068 (9)
C620.128 (10)0.147 (11)0.220 (16)0.082 (9)0.050 (10)0.032 (11)
C630.191 (12)0.114 (9)0.075 (7)0.044 (8)0.029 (7)0.010 (6)
C640.281 (18)0.105 (9)0.134 (11)0.074 (11)0.023 (11)0.022 (8)
Geometric parameters (Å, º) top
Au1—P12.3109 (13)C29—H310.9500
Au1—P32.3129 (13)C30—H320.9500
Au2—P22.3013 (13)C31—C321.389 (7)
Au2—P42.3050 (13)C31—C361.395 (7)
P1—C131.78 (4)C32—C331.378 (7)
P1—C191.820 (5)C32—H330.9500
P1—C11.822 (5)C33—C341.364 (8)
P1—C71.87 (5)C33—H340.9500
P2—C251.815 (5)C34—C351.378 (8)
P2—C311.816 (5)C34—H350.9500
P2—C31.833 (5)C35—C361.377 (7)
P3—C431.820 (5)C35—H360.9500
P3—C371.824 (5)C36—H370.9500
P3—C41.834 (5)C37—C421.377 (7)
P4—C491.816 (5)C37—C381.379 (7)
P4—C61.828 (5)C38—C391.388 (8)
P4—C551.829 (5)C38—H380.9500
C1—C21.528 (7)C39—C401.378 (9)
C1—H10.9900C39—H390.9500
C1—H20.9900C40—C411.363 (9)
C2—C31.535 (6)C40—H400.9500
C2—H30.9900C41—C421.390 (8)
C2—H40.9900C41—H410.9500
C3—H50.9900C42—H420.9500
C3—H60.9900C43—C481.391 (7)
C4—C51.545 (6)C43—C441.402 (7)
C4—H70.9900C44—C451.393 (7)
C4—H80.9900C44—H430.9500
C5—C61.526 (6)C45—C461.375 (7)
C5—H90.9900C45—H440.9500
C5—H100.9900C46—C471.379 (7)
C6—H110.9900C46—H450.9500
C6—H120.9900C47—C481.405 (7)
C7—C81.33 (5)C47—H460.9500
C7—C121.34 (4)C48—H470.9500
C8—C91.44 (3)C49—C541.392 (7)
C8—H130.9500C49—C501.403 (7)
C9—C101.33 (3)C50—C511.402 (7)
C9—H140.9500C50—H480.9500
C10—C111.30 (3)C51—C521.373 (8)
C10—H150.9500C51—H490.9500
C11—C121.40 (2)C52—C531.383 (8)
C11—H160.9500C52—H500.9500
C12—H170.9500C53—C541.372 (7)
C13—C181.36 (3)C53—H510.9500
C13—C141.44 (4)C54—H520.9500
C14—C151.35 (2)C55—C601.383 (7)
C14—H180.9500C55—C561.384 (7)
C15—C161.44 (3)C56—C571.379 (8)
C15—H190.9500C56—H530.9500
C16—C171.32 (2)C57—C581.359 (9)
C16—H200.9500C57—H540.9500
C17—C181.380 (17)C58—C591.368 (10)
C17—H210.9500C58—H550.9500
C18—H220.9500C59—C601.401 (8)
C19—C241.400 (7)C59—H560.9500
C19—C201.401 (7)C60—H570.9500
C20—C211.399 (7)Ni1—Cl42.2359 (15)
C20—H230.9500Ni1—Cl22.2548 (16)
C21—C221.382 (8)Ni1—Cl12.2558 (15)
C21—H240.9500Ni1—Cl32.2780 (14)
C22—C231.375 (8)O1—C611.370 (10)
C22—H250.9500O1—C631.418 (10)
C23—C241.386 (7)C61—C621.477 (15)
C23—H260.9500C61—H580.9900
C24—H270.9500C61—H590.9900
C25—C301.384 (7)C62—H600.9800
C25—C261.390 (7)C62—H610.9800
C26—C271.399 (8)C62—H620.9800
C26—H280.9500C63—C641.492 (14)
C27—C281.380 (9)C63—H630.9900
C27—H290.9500C63—H640.9900
C28—C291.375 (9)C64—H650.9800
C28—H300.9500C64—H660.9800
C29—C301.379 (8)C64—H670.9800
P1—Au1—P3176.68 (5)C29—C28—H30120.0
P2—Au2—P4177.98 (5)C27—C28—H30120.0
C13—P1—C19105.0 (8)C28—C29—C30120.4 (6)
C13—P1—C1104.7 (10)C28—C29—H31119.8
C19—P1—C1107.1 (2)C30—C29—H31119.8
C19—P1—C7105.8 (11)C29—C30—C25120.4 (6)
C1—P1—C7106.9 (12)C29—C30—H32119.8
C13—P1—Au1118.7 (11)C25—C30—H32119.8
C19—P1—Au1113.35 (17)C32—C31—C36117.5 (5)
C1—P1—Au1107.16 (16)C32—C31—P2122.9 (4)
C7—P1—Au1116.0 (14)C36—C31—P2119.3 (4)
C25—P2—C31108.1 (2)C33—C32—C31120.5 (5)
C25—P2—C3106.5 (2)C33—C32—H33119.8
C31—P2—C3105.6 (2)C31—C32—H33119.8
C25—P2—Au2112.19 (17)C34—C33—C32121.2 (6)
C31—P2—Au2113.28 (16)C34—C33—H34119.4
C3—P2—Au2110.65 (16)C32—C33—H34119.4
C43—P3—C37106.5 (2)C33—C34—C35119.5 (6)
C43—P3—C4106.4 (2)C33—C34—H35120.2
C37—P3—C4105.2 (2)C35—C34—H35120.2
C43—P3—Au1110.24 (15)C36—C35—C34119.7 (5)
C37—P3—Au1112.76 (18)C36—C35—H36120.1
C4—P3—Au1115.17 (16)C34—C35—H36120.1
C49—P4—C6107.6 (2)C35—C36—C31121.5 (5)
C49—P4—C55103.2 (2)C35—C36—H37119.2
C6—P4—C55108.8 (2)C31—C36—H37119.2
C49—P4—Au2112.99 (16)C42—C37—C38119.4 (5)
C6—P4—Au2111.52 (16)C42—C37—P3120.6 (4)
C55—P4—Au2112.28 (17)C38—C37—P3119.9 (4)
C2—C1—P1111.4 (3)C37—C38—C39121.0 (6)
C2—C1—H1109.4C37—C38—H38119.5
P1—C1—H1109.4C39—C38—H38119.5
C2—C1—H2109.4C40—C39—C38118.7 (6)
P1—C1—H2109.4C40—C39—H39120.6
H1—C1—H2108.0C38—C39—H39120.6
C1—C2—C3113.7 (4)C41—C40—C39120.9 (6)
C1—C2—H3108.8C41—C40—H40119.5
C3—C2—H3108.8C39—C40—H40119.5
C1—C2—H4108.8C40—C41—C42120.1 (6)
C3—C2—H4108.8C40—C41—H41120.0
H3—C2—H4107.7C42—C41—H41120.0
C2—C3—P2109.0 (3)C37—C42—C41119.9 (6)
C2—C3—H5109.9C37—C42—H42120.1
P2—C3—H5109.9C41—C42—H42120.1
C2—C3—H6109.9C48—C43—C44118.4 (4)
P2—C3—H6109.9C48—C43—P3122.4 (4)
H5—C3—H6108.3C44—C43—P3118.7 (4)
C5—C4—P3112.7 (3)C45—C44—C43120.5 (5)
C5—C4—H7109.1C45—C44—H43119.7
P3—C4—H7109.1C43—C44—H43119.7
C5—C4—H8109.1C46—C45—C44120.7 (5)
P3—C4—H8109.1C46—C45—H44119.7
H7—C4—H8107.8C44—C45—H44119.7
C6—C5—C4112.2 (4)C45—C46—C47119.7 (5)
C6—C5—H9109.2C45—C46—H45120.2
C4—C5—H9109.2C47—C46—H45120.2
C6—C5—H10109.2C46—C47—C48120.4 (5)
C4—C5—H10109.2C46—C47—H46119.8
H9—C5—H10107.9C48—C47—H46119.8
C5—C6—P4111.6 (3)C43—C48—C47120.4 (5)
C5—C6—H11109.3C43—C48—H47119.8
P4—C6—H11109.3C47—C48—H47119.8
C5—C6—H12109.3C54—C49—C50119.4 (5)
P4—C6—H12109.3C54—C49—P4118.5 (4)
H11—C6—H12108.0C50—C49—P4122.1 (4)
C8—C7—C12120 (4)C51—C50—C49118.5 (5)
C8—C7—P1119 (3)C51—C50—H48120.8
C12—C7—P1121 (3)C49—C50—H48120.8
C7—C8—C9119 (2)C52—C51—C50121.0 (5)
C7—C8—H13120.4C52—C51—H49119.5
C9—C8—H13120.4C50—C51—H49119.5
C10—C9—C8119 (2)C51—C52—C53120.1 (5)
C10—C9—H14120.4C51—C52—H50120.0
C8—C9—H14120.4C53—C52—H50120.0
C11—C10—C9121 (2)C54—C53—C52119.9 (5)
C11—C10—H15119.5C54—C53—H51120.0
C9—C10—H15119.5C52—C53—H51120.0
C10—C11—C12120.6 (17)C53—C54—C49121.0 (5)
C10—C11—H16119.7C53—C54—H52119.5
C12—C11—H16119.7C49—C54—H52119.5
C7—C12—C11120 (3)C60—C55—C56119.7 (5)
C7—C12—H17120.0C60—C55—P4119.3 (4)
C11—C12—H17120.0C56—C55—P4120.9 (4)
C18—C13—C14117 (3)C57—C56—C55119.7 (6)
C18—C13—P1121 (2)C57—C56—H53120.2
C14—C13—P1121 (2)C55—C56—H53120.2
C15—C14—C13121.8 (18)C58—C57—C56120.8 (6)
C15—C14—H18119.1C58—C57—H54119.6
C13—C14—H18119.1C56—C57—H54119.6
C14—C15—C16116.9 (19)C57—C58—C59120.7 (6)
C14—C15—H19121.5C57—C58—H55119.7
C16—C15—H19121.5C59—C58—H55119.7
C17—C16—C15122 (2)C58—C59—C60119.4 (6)
C17—C16—H20119.0C58—C59—H56120.3
C15—C16—H20119.0C60—C59—H56120.3
C16—C17—C18119.7 (15)C55—C60—C59119.7 (6)
C16—C17—H21120.1C55—C60—H57120.1
C18—C17—H21120.1C59—C60—H57120.1
C13—C18—C17122 (2)Cl4—Ni1—Cl2104.33 (6)
C13—C18—H22118.9Cl4—Ni1—Cl1106.27 (6)
C17—C18—H22118.9Cl2—Ni1—Cl1104.24 (7)
C24—C19—C20119.1 (5)Cl4—Ni1—Cl3124.65 (6)
C24—C19—P1122.6 (4)Cl2—Ni1—Cl3109.20 (6)
C20—C19—P1118.3 (4)Cl1—Ni1—Cl3106.45 (6)
C21—C20—C19119.8 (5)C61—O1—C63116.0 (8)
C21—C20—H23120.1O1—C61—C62113.0 (9)
C19—C20—H23120.1O1—C61—H58109.0
C22—C21—C20120.4 (6)C62—C61—H58109.0
C22—C21—H24119.8O1—C61—H59109.0
C20—C21—H24119.8C62—C61—H59109.0
C23—C22—C21119.7 (5)H58—C61—H59107.8
C23—C22—H25120.2C61—C62—H60109.5
C21—C22—H25120.2C61—C62—H61109.5
C22—C23—C24121.2 (6)H60—C62—H61109.5
C22—C23—H26119.4C61—C62—H62109.5
C24—C23—H26119.4H60—C62—H62109.5
C23—C24—C19119.8 (5)H61—C62—H62109.5
C23—C24—H27120.1O1—C63—C64109.2 (9)
C19—C24—H27120.1O1—C63—H63109.8
C30—C25—C26119.5 (5)C64—C63—H63109.8
C30—C25—P2118.2 (4)O1—C63—H64109.8
C26—C25—P2122.4 (4)C64—C63—H64109.8
C25—C26—C27119.7 (6)H63—C63—H64108.3
C25—C26—H28120.1C63—C64—H65109.5
C27—C26—H28120.1C63—C64—H66109.5
C28—C27—C26119.9 (6)H65—C64—H66109.5
C28—C27—H29120.1C63—C64—H67109.5
C26—C27—H29120.1H65—C64—H67109.5
C29—C28—C27120.1 (6)H66—C64—H67109.5
C13—P1—C1—C2175.8 (10)C26—C25—C30—C291.1 (9)
C19—P1—C1—C264.6 (4)P2—C25—C30—C29178.4 (5)
C7—P1—C1—C2177.7 (13)C25—P2—C31—C3291.2 (5)
Au1—P1—C1—C257.3 (4)C3—P2—C31—C3222.5 (5)
P1—C1—C2—C3175.6 (3)Au2—P2—C31—C32143.8 (4)
C1—C2—C3—P2163.2 (3)C25—P2—C31—C3695.1 (4)
C25—P2—C3—C2177.4 (3)C3—P2—C31—C36151.1 (4)
C31—P2—C3—C267.7 (4)Au2—P2—C31—C3629.9 (4)
Au2—P2—C3—C255.2 (4)C36—C31—C32—C330.4 (8)
C43—P3—C4—C5173.8 (3)P2—C31—C32—C33174.2 (4)
C37—P3—C4—C573.4 (4)C31—C32—C33—C340.9 (9)
Au1—P3—C4—C551.4 (4)C32—C33—C34—C351.9 (10)
P3—C4—C5—C6177.7 (3)C33—C34—C35—C362.4 (9)
C4—C5—C6—P4162.3 (4)C34—C35—C36—C312.0 (9)
C49—P4—C6—C567.3 (4)C32—C31—C36—C351.0 (8)
C55—P4—C6—C5178.5 (4)P2—C31—C36—C35175.0 (4)
Au2—P4—C6—C557.1 (4)C43—P3—C37—C4258.1 (4)
C19—P1—C7—C867 (2)C4—P3—C37—C4254.6 (4)
C1—P1—C7—C847 (2)Au1—P3—C37—C42179.1 (3)
Au1—P1—C7—C8166.4 (17)C43—P3—C37—C38123.6 (4)
C19—P1—C7—C12108 (2)C4—P3—C37—C38123.8 (4)
C1—P1—C7—C12138 (2)Au1—P3—C37—C382.5 (4)
Au1—P1—C7—C1218 (3)C42—C37—C38—C390.9 (8)
C12—C7—C8—C91 (3)P3—C37—C38—C39177.4 (4)
P1—C7—C8—C9176.4 (18)C37—C38—C39—C400.7 (8)
C7—C8—C9—C103 (2)C38—C39—C40—C411.0 (9)
C8—C9—C10—C115 (4)C39—C40—C41—C421.4 (9)
C9—C10—C11—C126 (4)C38—C37—C42—C411.4 (8)
C8—C7—C12—C111 (4)P3—C37—C42—C41177.0 (4)
P1—C7—C12—C11176.9 (16)C40—C41—C42—C371.6 (9)
C10—C11—C12—C74 (3)C37—P3—C43—C48141.5 (4)
C19—P1—C13—C18146.0 (17)C4—P3—C43—C4829.6 (5)
C1—P1—C13—C18101 (2)Au1—P3—C43—C4895.9 (4)
C7—P1—C13—C1840 (31)C37—P3—C43—C4446.8 (4)
Au1—P1—C13—C1818 (2)C4—P3—C43—C44158.7 (4)
C19—P1—C13—C1443.2 (19)Au1—P3—C43—C4475.8 (4)
C1—P1—C13—C1469.5 (16)C48—C43—C44—C450.2 (7)
Au1—P1—C13—C14171.1 (13)P3—C43—C44—C45171.8 (4)
C18—C13—C14—C155 (2)C43—C44—C45—C460.6 (8)
P1—C13—C14—C15176.5 (17)C44—C45—C46—C470.0 (8)
C13—C14—C15—C162 (2)C45—C46—C47—C481.0 (8)
C14—C15—C16—C172 (3)C44—C43—C48—C470.8 (7)
C15—C16—C17—C182 (3)P3—C43—C48—C47172.5 (4)
C14—C13—C18—C175 (3)C46—C47—C48—C431.4 (7)
P1—C13—C18—C17176.5 (14)C6—P4—C49—C54155.1 (4)
C16—C17—C18—C132 (2)C55—P4—C49—C5489.9 (4)
C13—P1—C19—C2485.3 (12)Au2—P4—C49—C5431.6 (4)
C1—P1—C19—C2425.6 (5)C6—P4—C49—C5026.1 (5)
C7—P1—C19—C2488.2 (15)C55—P4—C49—C5088.8 (4)
Au1—P1—C19—C24143.6 (4)Au2—P4—C49—C50149.6 (4)
C13—P1—C19—C2094.0 (12)C54—C49—C50—C511.1 (7)
C1—P1—C19—C20155.1 (4)P4—C49—C50—C51177.7 (4)
C7—P1—C19—C2091.0 (15)C49—C50—C51—C520.6 (8)
Au1—P1—C19—C2037.1 (4)C50—C51—C52—C530.6 (8)
C24—C19—C20—C210.6 (8)C51—C52—C53—C541.2 (8)
P1—C19—C20—C21178.7 (4)C52—C53—C54—C491.7 (8)
C19—C20—C21—C221.1 (8)C50—C49—C54—C531.7 (7)
C20—C21—C22—C231.5 (9)P4—C49—C54—C53177.1 (4)
C21—C22—C23—C241.4 (9)C49—P4—C55—C6092.3 (5)
C22—C23—C24—C190.9 (9)C6—P4—C55—C60153.6 (5)
C20—C19—C24—C230.5 (8)Au2—P4—C55—C6029.7 (5)
P1—C19—C24—C23178.7 (4)C49—P4—C55—C5683.7 (5)
C31—P2—C25—C30167.5 (5)C6—P4—C55—C5630.4 (5)
C3—P2—C25—C3079.4 (5)Au2—P4—C55—C56154.3 (4)
Au2—P2—C25—C3041.8 (5)C60—C55—C56—C570.7 (9)
C31—P2—C25—C2612.0 (5)P4—C55—C56—C57175.3 (5)
C3—P2—C25—C26101.1 (5)C55—C56—C57—C580.4 (9)
Au2—P2—C25—C26137.7 (4)C56—C57—C58—C590.7 (11)
C30—C25—C26—C272.1 (8)C57—C58—C59—C600.0 (11)
P2—C25—C26—C27177.4 (4)C56—C55—C60—C591.4 (9)
C25—C26—C27—C282.2 (9)P4—C55—C60—C59174.6 (5)
C26—C27—C28—C291.3 (11)C58—C59—C60—C551.1 (10)
C27—C28—C29—C300.2 (12)C63—O1—C61—C62178.7 (9)
C28—C29—C30—C250.1 (11)C61—O1—C63—C64171.8 (9)
Selected bond lengths (Å) top
Au1—P12.3109 (13)Ni1—Cl42.2359 (15)
Au1—P32.3129 (13)Ni1—Cl22.2548 (16)
Au2—P22.3013 (13)Ni1—Cl12.2558 (15)
Au2—P42.3050 (13)Ni1—Cl32.2780 (14)
Acknowledgements top

This work was supported by a Grant-in Aid for Science Research (No. 23350026) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

references
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