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Acta Cryst. (2007). E63, m2522    [ doi:10.1107/S1600536807041384 ]

Tris[diphenyl(4-tolyl)phosphane]-1[kappa]2P,2[kappa]P-[mu]-di-iodido-1:2[kappa]4I-dicopper(I)

G. Steyl

Abstract top

The title complex, [Cu2I2(C19H17P)3], was obtained by refluxing two equivalents of P(4-TolPh2) (4-Tol is 4-tolyl) with one equivalent of CuI in acetonitrile. Two distinct copper(I) centres are bridged by two iodide atoms with a Cu...Cu separation of 2.7807 (9) Å, one with a trigonal coordination geometry and one Cu-P bond of 2.2209 (11) Å, and the second with a distorted tetrahedral coordination geometry and two Cu-P bonds of 2.2562 (12) and 2.2601 (11) Å. No hydrogen bonding, intercalation or stacking interactions were found in the crystal structure. One I atom is disordered over two positions, with occupancies of ca 0.79 and 0.21, and the H atoms of the methyl groups are each disordered equally over two positions.

Comment top

The title complex, (I), is an extension of the previously investigated PPh3 (Eller et al., 1977; Liang et al., 1999) and P(4-Tol)3 (Meijboom, 2006) derivatives. The complex forms part of a range of copper(I) complexes with an iodido molecule coordinated to the metal centre. The range of coordination modes in which the iodido moiety can coordinate to the metal range from single to three centered interactions (i.e. cubane structures).

The title complex presents the most commonly observed coordination pattern for iodido copper(I) complexes, with two distinct copper(I) centres linked via an iodido bridge, see Fig. 1. Compared to previously published structures of the PPh3 (Eller et al., 1977; Liang et al., 1999) and P(4-Tol)3 (Meijboom, 2006) complexes no significant structural effect could be observed when one of the aryl substituents is functionalized. There are no significant intercalation or stacking interactions in the title compound.

Related literature top

Structurally related µ-iodido copper(I) complexes have been reported for PPh3 (Eller et al., 1977; Liang et al., 1999) and P(4-Tol)3 (Meijboom, 2006).

Experimental top

The title compound was obtained by refluxing two equivalents of P(4-TolPh2) with one equivalent of CuI in acetonitrile for six hours. On cooling crystals suitable for X-ray crystallography were obtained. (Yield: 50%)

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.96 Å and with Uiso(H) = 1.2 times Ueq(C aromatic) and Uiso(H) = 1.5 times Ueq(C methyl).

Atom I1 has been treated as disordered between two positions with the refined occupancies of 0.79 (4) and 0.21 (4), respectively.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. Only the major component of the disordered atom I1 is shown. Hydrogen atoms are omitted for clarity.
Tris[diphenyl(4-tolyl)phosphane]-1κ2P,2κP-µ-di-iodido-1:2κ4I-dicopper(I) top
Crystal data top
[Cu2I2(C19H17P)3]Z = 2
Mr = 1209.77F000 = 1204
Triclinic, P1Dx = 1.587 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 13.984 (2) ÅCell parameters from 9818 reflections
b = 14.092 (5) Åθ = 2.6–27.6º
c = 16.084 (3) ŵ = 2.19 mm−1
α = 103.948 (2)ºT = 100 (2) K
β = 101.743 (3)ºBlock, colourless
γ = 117.769 (4)º0.16 × 0.15 × 0.07 mm
V = 2531.1 (11) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		11001 independent reflections
Radiation source: fine-focus sealed tube8657 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
Detector resolution: 512 pixels mm-1θmax = 27.0º
T = 100(2) Kθmin = 2.2º
φ and ω scansh = −17→17
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		k = −18→18
Tmin = 0.721, Tmax = 0.862l = −20→20
44264 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.077  w = 1/[σ2(Fo2) + (0.0282P)2 + 2.0291P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.010
11001 reflectionsΔρmax = 0.89 e Å−3
581 parametersΔρmin = −0.97 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2I2(C19H17P)3]γ = 117.769 (4)º
Mr = 1209.77V = 2531.1 (11) Å3
Triclinic, P1Z = 2
a = 13.984 (2) ÅMo Kα
b = 14.092 (5) ŵ = 2.19 mm−1
c = 16.084 (3) ÅT = 100 (2) K
α = 103.948 (2)º0.16 × 0.15 × 0.07 mm
β = 101.743 (3)º
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		11001 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		8657 reflections with I > 2σ(I)
Tmin = 0.721, Tmax = 0.862Rint = 0.047
44264 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034581 parameters
wR(F2) = 0.077H-atom parameters constrained
S = 1.03Δρmax = 0.89 e Å−3
11001 reflectionsΔρmin = −0.97 e Å−3
Special details top

Experimental. A disorder is observed on the methyl moieties of the tolyl group as well as one of the iodido groups.

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)
I10.7341 (3)0.5527 (3)0.3950 (3)0.0229 (3)0.79 (4)
I20.71959 (2)0.307168 (19)0.154947 (17)0.03187 (7)
Cu20.79801 (3)0.51480 (3)0.25878 (3)0.02518 (10)
Cu10.59671 (3)0.33342 (3)0.25824 (3)0.02458 (10)
P20.43984 (7)0.31991 (8)0.16951 (6)0.0260 (2)
P10.57986 (8)0.20772 (8)0.32759 (7)0.0274 (2)
P30.94695 (7)0.65489 (8)0.24280 (6)0.0264 (2)
C110.7117 (3)0.2117 (3)0.3774 (2)0.0267 (7)
C410.3348 (3)0.3020 (3)0.2255 (2)0.0289 (8)
C310.5205 (3)0.2125 (3)0.4187 (3)0.0326 (8)
C721.0760 (3)0.5883 (3)0.3379 (3)0.0343 (9)
H721.01380.55550.35690.041*
C210.4767 (3)0.0587 (3)0.2438 (3)0.0332 (8)
C460.3639 (3)0.3952 (3)0.3024 (2)0.0337 (8)
H460.43280.46660.32090.040*
C510.4678 (3)0.4474 (3)0.1426 (2)0.0287 (8)
C340.4276 (3)0.2242 (3)0.5571 (3)0.0391 (9)
C150.8127 (4)0.1300 (4)0.4397 (3)0.0391 (9)
H150.81050.06890.45370.047*
C560.5720 (3)0.5111 (3)0.1320 (2)0.0310 (8)
H560.62430.48770.13800.037*
C610.3544 (3)0.1981 (3)0.0583 (2)0.0287 (8)
C260.3589 (3)0.0108 (3)0.2253 (3)0.0416 (10)
H260.33440.05010.26140.050*
C910.9365 (3)0.6554 (3)0.1282 (2)0.0313 (8)
C430.1619 (4)0.1836 (4)0.2508 (3)0.0500 (11)
H430.09400.11180.23360.060*
C160.7105 (3)0.1195 (3)0.3960 (3)0.0336 (8)
H160.63990.05010.37870.040*
C810.9948 (3)0.8033 (3)0.3089 (2)0.0334 (8)
C320.4914 (3)0.2935 (3)0.4438 (2)0.0266 (7)
H320.50320.34510.41440.032*
C220.5116 (3)−0.0002 (3)0.1875 (3)0.0421 (10)
H220.59020.03230.19790.051*
C120.8182 (3)0.3118 (3)0.4001 (2)0.0320 (8)
H120.82120.37380.38740.038*
C640.2260 (3)0.0081 (3)−0.1122 (3)0.0381 (9)
C940.9349 (4)0.6509 (6)−0.0475 (3)0.0674 (11)
C841.0531 (7)1.0281 (4)0.3995 (4)0.085 (2)
H841.07291.10310.43140.102*
C140.9178 (4)0.2301 (4)0.4626 (3)0.0394 (9)
H140.98670.23710.49190.047*
C450.2910 (3)0.3828 (4)0.3517 (3)0.0411 (10)
H450.31030.44620.40200.049*
C440.1903 (4)0.2768 (4)0.3260 (3)0.0509 (11)
H440.14170.26810.35930.061*
C620.3765 (3)0.1103 (3)0.0388 (2)0.0320 (8)
H620.43500.11480.08260.038*
C330.4449 (3)0.2995 (3)0.5119 (2)0.0303 (8)
H330.42530.35430.52730.036*
C540.5225 (4)0.6445 (4)0.1023 (3)0.0469 (11)
H540.54080.71040.08920.056*
C130.9202 (3)0.3201 (3)0.4416 (3)0.0370 (9)
H130.99120.38730.45560.044*
C660.2666 (3)0.1889 (3)−0.0092 (3)0.0339 (8)
H660.25020.24650.00230.041*
C960.9597 (3)0.7513 (4)0.1066 (3)0.0400 (9)
H960.97620.81860.15110.048*
C630.3125 (3)0.0162 (3)−0.0451 (3)0.0366 (9)
H630.3277−0.0423−0.05650.044*
C3410.3806 (4)0.2300 (4)0.6334 (3)0.0543 (12)
H34A0.36600.29120.64320.081*0.50
H34B0.43640.24530.68900.081*0.50
H34C0.30940.15720.61660.081*0.50
H34D0.37520.17130.65600.081*0.50
H34E0.30490.21720.61010.081*0.50
H34F0.43180.30530.68260.081*0.50
C360.4995 (5)0.1357 (4)0.4628 (4)0.0637 (15)
H360.51640.07890.44640.076*
C520.3906 (3)0.4840 (4)0.1322 (3)0.0393 (9)
H520.32000.44280.13910.047*
C711.0733 (3)0.6445 (3)0.2791 (3)0.0338 (8)
C650.2040 (3)0.0956 (3)−0.0927 (3)0.0373 (9)
H650.14580.0912−0.13670.045*
C831.1370 (5)1.0091 (4)0.3875 (3)0.0772 (18)
H831.21361.07160.40930.093*
C761.1659 (3)0.6917 (4)0.2500 (3)0.0545 (13)
H761.16430.72900.20970.065*
C731.1714 (4)0.5807 (4)0.3689 (3)0.0485 (11)
H731.17390.54400.40950.058*
C230.4298 (4)−0.1069 (3)0.1161 (3)0.0500 (11)
H230.4539−0.14700.08030.060*
C240.3130 (4)−0.1541 (4)0.0979 (3)0.0545 (12)
H240.2583−0.22470.04880.065*
C420.2340 (3)0.1957 (4)0.2002 (3)0.0399 (9)
H420.21410.13220.14950.048*
C930.9070 (5)0.5532 (5)−0.0271 (3)0.0646 (14)
H930.88760.4852−0.07250.077*
C920.9076 (4)0.5550 (4)0.0590 (3)0.0538 (12)
H920.88850.48840.07090.065*
C741.2623 (4)0.6276 (5)0.3394 (4)0.0650 (15)
H741.32560.62140.35940.078*
C950.9587 (4)0.7487 (4)0.0200 (3)0.0503 (11)
H950.97440.81420.00710.060*
C250.2777 (3)−0.0957 (4)0.1531 (3)0.0505 (11)
H250.1989−0.12800.14170.061*
C530.4185 (4)0.5809 (4)0.1118 (3)0.0495 (11)
H530.36580.60380.10440.059*
C821.1094 (4)0.8966 (4)0.3427 (3)0.0513 (12)
H821.16740.88410.33560.062*
C751.2603 (4)0.6834 (5)0.2808 (4)0.0665 (15)
H751.32250.71570.26180.080*
C550.5994 (4)0.6088 (3)0.1126 (3)0.0399 (9)
H550.67030.65100.10650.048*
C350.4539 (5)0.1422 (4)0.5305 (4)0.0652 (15)
H350.44060.08950.55900.078*
C850.9388 (6)0.9366 (4)0.3647 (4)0.0785 (18)
H850.88130.95040.37120.094*
C9410.9443 (4)0.6557 (5)−0.1376 (3)0.0674 (11)
H94A0.92520.5815−0.17740.101*0.50
H94B1.02220.7144−0.12740.101*0.50
H94C0.89130.6741−0.16590.101*0.50
H94D0.96730.7318−0.13640.101*0.50
H94E0.87030.5989−0.18640.101*0.50
H94F1.00120.6392−0.14790.101*0.50
C860.9093 (4)0.8241 (4)0.3200 (3)0.0518 (12)
H860.83220.76240.29730.062*
C6410.1583 (4)−0.0910 (4)−0.2036 (3)0.0666 (14)
H64A0.1027−0.0816−0.24050.100*0.50
H64B0.1185−0.1626−0.19510.100*0.50
H64C0.2102−0.0926−0.23400.100*0.50
H64D0.1849−0.1429−0.20590.100*0.50
H64E0.1691−0.0619−0.25130.100*0.50
H64F0.0774−0.1320−0.21240.100*0.50
I30.722 (2)0.5469 (15)0.381 (2)0.032 (2)0.21 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0197 (5)0.0244 (4)0.0226 (8)0.0103 (4)0.0102 (5)0.0076 (5)
I20.02803 (13)0.02857 (12)0.03736 (15)0.01492 (10)0.01749 (11)0.00656 (10)
Cu20.0211 (2)0.0268 (2)0.0296 (2)0.01260 (18)0.01282 (18)0.01188 (18)
Cu10.0204 (2)0.0253 (2)0.0295 (2)0.01191 (18)0.01177 (18)0.01153 (17)
P20.0199 (4)0.0307 (5)0.0274 (5)0.0134 (4)0.0108 (4)0.0103 (4)
P10.0255 (5)0.0243 (4)0.0364 (5)0.0127 (4)0.0175 (4)0.0142 (4)
P30.0201 (4)0.0342 (5)0.0292 (5)0.0140 (4)0.0132 (4)0.0167 (4)
C110.0314 (19)0.0310 (18)0.0241 (18)0.0186 (16)0.0150 (15)0.0128 (15)
C410.0267 (18)0.039 (2)0.0270 (19)0.0203 (17)0.0122 (15)0.0156 (16)
C310.031 (2)0.0285 (19)0.045 (2)0.0149 (17)0.0230 (18)0.0194 (17)
C720.0271 (19)0.048 (2)0.036 (2)0.0200 (18)0.0178 (17)0.0240 (18)
C210.030 (2)0.0240 (18)0.042 (2)0.0104 (16)0.0158 (17)0.0147 (16)
C460.032 (2)0.045 (2)0.030 (2)0.0241 (18)0.0125 (16)0.0164 (17)
C510.0289 (19)0.0340 (19)0.0253 (19)0.0191 (17)0.0092 (15)0.0109 (15)
C340.035 (2)0.042 (2)0.045 (2)0.0176 (19)0.0267 (19)0.0211 (19)
C150.056 (3)0.048 (2)0.037 (2)0.039 (2)0.023 (2)0.0245 (19)
C560.030 (2)0.036 (2)0.0268 (19)0.0179 (17)0.0081 (16)0.0133 (16)
C610.0206 (17)0.0327 (19)0.031 (2)0.0111 (15)0.0133 (15)0.0127 (15)
C260.033 (2)0.035 (2)0.060 (3)0.0150 (18)0.024 (2)0.025 (2)
C910.0231 (18)0.052 (2)0.031 (2)0.0232 (18)0.0162 (16)0.0229 (18)
C430.033 (2)0.049 (3)0.063 (3)0.015 (2)0.029 (2)0.022 (2)
C160.040 (2)0.0307 (19)0.037 (2)0.0187 (18)0.0224 (18)0.0175 (16)
C810.037 (2)0.032 (2)0.028 (2)0.0117 (17)0.0124 (17)0.0189 (16)
C320.0214 (17)0.0294 (18)0.0263 (19)0.0112 (15)0.0092 (14)0.0122 (15)
C220.034 (2)0.034 (2)0.046 (3)0.0110 (18)0.0178 (19)0.0087 (18)
C120.034 (2)0.0312 (19)0.037 (2)0.0185 (17)0.0172 (17)0.0169 (16)
C640.026 (2)0.040 (2)0.029 (2)0.0082 (17)0.0095 (16)0.0056 (17)
C940.069 (2)0.130 (3)0.050 (2)0.073 (3)0.0374 (19)0.054 (2)
C840.146 (6)0.032 (3)0.055 (3)0.024 (4)0.058 (4)0.018 (2)
C140.041 (2)0.052 (3)0.039 (2)0.033 (2)0.0169 (19)0.0219 (19)
C450.042 (2)0.061 (3)0.036 (2)0.035 (2)0.0214 (19)0.021 (2)
C440.042 (3)0.067 (3)0.059 (3)0.032 (2)0.036 (2)0.030 (2)
C620.0234 (18)0.040 (2)0.030 (2)0.0169 (17)0.0099 (16)0.0108 (16)
C330.0219 (18)0.035 (2)0.030 (2)0.0142 (16)0.0089 (15)0.0089 (16)
C540.061 (3)0.042 (2)0.049 (3)0.033 (2)0.021 (2)0.024 (2)
C130.032 (2)0.040 (2)0.041 (2)0.0200 (18)0.0159 (18)0.0168 (18)
C660.0263 (19)0.035 (2)0.037 (2)0.0137 (17)0.0114 (17)0.0148 (17)
C960.031 (2)0.059 (3)0.044 (2)0.026 (2)0.0173 (18)0.033 (2)
C630.029 (2)0.037 (2)0.036 (2)0.0175 (18)0.0109 (17)0.0058 (17)
C3410.063 (3)0.052 (3)0.069 (3)0.036 (2)0.045 (3)0.031 (2)
C360.101 (4)0.063 (3)0.104 (4)0.064 (3)0.086 (4)0.067 (3)
C520.040 (2)0.058 (3)0.041 (2)0.035 (2)0.0236 (19)0.025 (2)
C710.0265 (19)0.051 (2)0.033 (2)0.0224 (18)0.0168 (16)0.0226 (18)
C650.0251 (19)0.041 (2)0.033 (2)0.0138 (18)0.0045 (16)0.0105 (17)
C830.084 (4)0.043 (3)0.040 (3)−0.005 (3)0.002 (3)0.017 (2)
C760.034 (2)0.098 (4)0.059 (3)0.038 (3)0.028 (2)0.058 (3)
C730.043 (2)0.080 (3)0.050 (3)0.042 (2)0.022 (2)0.043 (2)
C230.046 (3)0.036 (2)0.044 (3)0.010 (2)0.018 (2)0.0043 (19)
C240.046 (3)0.034 (2)0.048 (3)0.002 (2)0.009 (2)0.009 (2)
C420.032 (2)0.047 (2)0.047 (2)0.0217 (19)0.0223 (19)0.0200 (19)
C930.094 (4)0.099 (4)0.042 (3)0.076 (4)0.037 (3)0.031 (3)
C920.072 (3)0.076 (3)0.045 (3)0.052 (3)0.033 (2)0.036 (2)
C740.039 (3)0.117 (4)0.077 (4)0.054 (3)0.030 (3)0.062 (3)
C950.040 (2)0.086 (3)0.051 (3)0.039 (2)0.027 (2)0.048 (3)
C250.024 (2)0.039 (2)0.066 (3)0.0012 (18)0.014 (2)0.023 (2)
C530.067 (3)0.063 (3)0.048 (3)0.054 (3)0.026 (2)0.025 (2)
C820.043 (3)0.044 (3)0.041 (3)0.008 (2)0.001 (2)0.023 (2)
C750.041 (3)0.123 (5)0.078 (4)0.053 (3)0.039 (3)0.069 (3)
C550.044 (2)0.040 (2)0.036 (2)0.021 (2)0.0130 (19)0.0207 (18)
C350.104 (4)0.064 (3)0.102 (4)0.064 (3)0.085 (4)0.067 (3)
C850.126 (5)0.048 (3)0.100 (4)0.050 (3)0.088 (4)0.043 (3)
C9410.069 (2)0.130 (3)0.050 (2)0.073 (3)0.0374 (19)0.054 (2)
C860.068 (3)0.038 (2)0.069 (3)0.030 (2)0.050 (3)0.029 (2)
C6410.046 (3)0.069 (3)0.064 (3)0.027 (3)0.013 (2)0.008 (3)
I30.034 (4)0.0266 (16)0.030 (5)0.012 (2)0.015 (4)0.008 (2)
Geometric parameters (Å, °) top
I1—Cu22.561 (4)C84—H840.9300
I1—Cu12.747 (4)C14—C131.376 (5)
I2—Cu22.5421 (10)C14—H140.9300
I2—Cu12.7033 (8)C45—C441.375 (6)
Cu2—P32.2209 (11)C45—H450.9300
Cu2—I32.469 (17)C44—H440.9300
Cu2—Cu12.7807 (9)C62—C631.385 (5)
Cu1—P22.2562 (12)C62—H620.9300
Cu1—P12.2601 (12)C33—H330.9300
Cu1—I32.62 (2)C54—C531.373 (6)
P2—C611.820 (4)C54—C551.382 (5)
P2—C411.826 (3)C54—H540.9300
P2—C511.832 (4)C13—H130.9300
P1—C111.824 (4)C66—C651.377 (5)
P1—C211.825 (4)C66—H660.9300
P1—C311.828 (4)C96—C951.382 (5)
P3—C811.813 (4)C96—H960.9300
P3—C911.822 (4)C63—H630.9300
P3—C711.829 (4)C341—H34A0.9600
C11—C121.383 (5)C341—H34B0.9600
C11—C161.395 (5)C341—H34C0.9600
C41—C421.379 (5)C341—H34D0.9600
C41—C461.391 (5)C341—H34E0.9600
C31—C321.382 (5)C341—H34F0.9600
C31—C361.386 (5)C36—C351.373 (6)
C72—C711.378 (5)C36—H360.9300
C72—C731.389 (5)C52—C531.377 (6)
C72—H720.9300C52—H520.9300
C21—C261.388 (5)C71—C761.390 (5)
C21—C221.394 (5)C65—H650.9300
C46—C451.388 (5)C83—C821.395 (7)
C46—H460.9300C83—H830.9300
C51—C561.384 (5)C76—C751.381 (6)
C51—C521.396 (5)C76—H760.9300
C34—C351.371 (5)C73—C741.376 (6)
C34—C331.384 (5)C73—H730.9300
C34—C3411.508 (5)C23—C241.377 (6)
C15—C141.372 (5)C23—H230.9300
C15—C161.380 (5)C24—C251.384 (6)
C15—H150.9300C24—H240.9300
C56—C551.379 (5)C42—H420.9300
C56—H560.9300C93—C921.377 (6)
C61—C621.390 (5)C93—H930.9300
C61—C661.395 (5)C92—H920.9300
C26—C251.387 (6)C74—C751.369 (6)
C26—H260.9300C74—H740.9300
C91—C961.384 (5)C95—H950.9300
C91—C921.389 (6)C25—H250.9300
C43—C441.378 (6)C53—H530.9300
C43—C421.397 (5)C82—H820.9300
C43—H430.9300C75—H750.9300
C16—H160.9300C55—H550.9300
C81—C821.389 (5)C35—H350.9300
C81—C861.392 (5)C85—C861.386 (6)
C32—C331.389 (5)C85—H850.9300
C32—H320.9300C941—H94A0.9600
C22—C231.385 (5)C941—H94B0.9600
C22—H220.9300C941—H94C0.9600
C12—C131.383 (5)C941—H94D0.9600
C12—H120.9300C941—H94E0.9600
C64—C651.385 (5)C941—H94F0.9600
C64—C631.387 (5)C86—H860.9300
C64—C6411.490 (6)C641—H64A0.9600
C94—C951.376 (7)C641—H64B0.9600
C94—C931.387 (7)C641—H64C0.9600
C94—C9411.496 (6)C641—H64D0.9600
C84—C831.359 (8)C641—H64E0.9600
C84—C851.378 (8)C641—H64F0.9600
Cu2—I1—Cu163.07 (9)C95—C96—H96119.5
Cu2—I2—Cu163.941 (18)C91—C96—H96119.5
P3—Cu2—I3124.3 (4)C62—C63—C64120.8 (4)
P3—Cu2—I2116.50 (3)C62—C63—H63119.6
I3—Cu2—I2118.7 (4)C64—C63—H63119.6
P3—Cu2—I1122.44 (9)C34—C341—H34A109.5
I3—Cu2—I14.6 (7)C34—C341—H34B109.5
I2—Cu2—I1119.85 (9)H34A—C341—H34B109.5
P3—Cu2—Cu1173.43 (3)C34—C341—H34C109.5
I3—Cu2—Cu159.4 (5)H34A—C341—H34C109.5
I2—Cu2—Cu160.85 (2)H34B—C341—H34C109.5
I1—Cu2—Cu161.74 (9)C34—C341—H34D109.5
P2—Cu1—P1121.94 (4)H34A—C341—H34D141.1
P2—Cu1—I3104.5 (6)H34B—C341—H34D56.3
P1—Cu1—I3110.1 (6)H34C—C341—H34D56.3
P2—Cu1—I2109.14 (4)C34—C341—H34E109.5
P1—Cu1—I2102.33 (3)H34A—C341—H34E56.3
I3—Cu1—I2108.3 (3)H34B—C341—H34E141.1
P2—Cu1—I1107.95 (9)H34C—C341—H34E56.3
P1—Cu1—I1106.56 (11)H34D—C341—H34E109.5
I3—Cu1—I13.8 (7)C34—C341—H34F109.5
I2—Cu1—I1108.23 (7)H34A—C341—H34F56.3
P2—Cu1—Cu2109.66 (4)H34B—C341—H34F56.3
P1—Cu1—Cu2128.35 (3)H34C—C341—H34F141.1
I3—Cu1—Cu254.4 (3)H34D—C341—H34F109.5
I2—Cu1—Cu255.21 (2)H34E—C341—H34F109.5
I1—Cu1—Cu255.19 (8)C35—C36—C31120.9 (4)
C61—P2—C41103.73 (16)C35—C36—H36119.6
C61—P2—C51104.49 (16)C31—C36—H36119.6
C41—P2—C51103.13 (16)C53—C52—C51120.3 (4)
C61—P2—Cu1116.33 (12)C53—C52—H52119.9
C41—P2—Cu1111.73 (12)C51—C52—H52119.9
C51—P2—Cu1115.91 (11)C72—C71—C76119.4 (3)
C11—P1—C21104.78 (16)C72—C71—P3118.2 (3)
C11—P1—C31104.50 (17)C76—C71—P3122.4 (3)
C21—P1—C31102.44 (17)C66—C65—C64121.2 (4)
C11—P1—Cu1116.45 (12)C66—C65—H65119.4
C21—P1—Cu1109.69 (13)C64—C65—H65119.4
C31—P1—Cu1117.40 (12)C84—C83—C82120.6 (5)
C81—P3—C91102.06 (17)C84—C83—H83119.7
C81—P3—C71105.71 (18)C82—C83—H83119.7
C91—P3—C71102.79 (16)C75—C76—C71120.1 (4)
C81—P3—Cu2116.76 (12)C75—C76—H76119.9
C91—P3—Cu2119.02 (12)C71—C76—H76119.9
C71—P3—Cu2108.92 (13)C74—C73—C72119.7 (4)
C12—C11—C16118.2 (3)C74—C73—H73120.1
C12—C11—P1118.7 (3)C72—C73—H73120.1
C16—C11—P1123.1 (3)C24—C23—C22120.5 (4)
C42—C41—C46119.2 (3)C24—C23—H23119.8
C42—C41—P2121.8 (3)C22—C23—H23119.8
C46—C41—P2118.6 (3)C23—C24—C25119.5 (4)
C32—C31—C36117.5 (3)C23—C24—H24120.2
C32—C31—P1119.4 (3)C25—C24—H24120.2
C36—C31—P1123.0 (3)C41—C42—C43119.8 (4)
C71—C72—C73120.1 (3)C41—C42—H42120.1
C71—C72—H72119.9C43—C42—H42120.1
C73—C72—H72119.9C92—C93—C94121.3 (5)
C26—C21—C22119.1 (3)C92—C93—H93119.4
C26—C21—P1118.8 (3)C94—C93—H93119.4
C22—C21—P1121.3 (3)C93—C92—C91120.7 (4)
C45—C46—C41120.7 (4)C93—C92—H92119.7
C45—C46—H46119.7C91—C92—H92119.7
C41—C46—H46119.7C75—C74—C73120.5 (4)
C56—C51—C52118.1 (3)C75—C74—H74119.7
C56—C51—P2117.9 (3)C73—C74—H74119.7
C52—C51—P2124.0 (3)C94—C95—C96121.2 (5)
C35—C34—C33118.1 (4)C94—C95—H95119.4
C35—C34—C341119.9 (4)C96—C95—H95119.4
C33—C34—C341122.0 (4)C24—C25—C26120.5 (4)
C14—C15—C16120.4 (4)C24—C25—H25119.8
C14—C15—H15119.8C26—C25—H25119.8
C16—C15—H15119.8C54—C53—C52121.4 (4)
C55—C56—C51121.0 (3)C54—C53—H53119.3
C55—C56—H56119.5C52—C53—H53119.3
C51—C56—H56119.5C81—C82—C83119.8 (5)
C62—C61—C66118.0 (3)C81—C82—H82120.1
C62—C61—P2119.5 (3)C83—C82—H82120.1
C66—C61—P2122.4 (3)C74—C75—C76120.0 (4)
C25—C26—C21120.1 (4)C74—C75—H75120.0
C25—C26—H26119.9C76—C75—H75120.0
C21—C26—H26119.9C56—C55—C54120.6 (4)
C96—C91—C92117.9 (4)C56—C55—H55119.7
C96—C91—P3123.9 (3)C54—C55—H55119.7
C92—C91—P3118.1 (3)C34—C35—C36121.7 (4)
C44—C43—C42120.8 (4)C34—C35—H35119.1
C44—C43—H43119.6C36—C35—H35119.1
C42—C43—H43119.6C84—C85—C86120.1 (5)
C15—C16—C11120.8 (4)C84—C85—H85119.9
C15—C16—H16119.6C86—C85—H85119.9
C11—C16—H16119.6C94—C941—H94A109.5
C82—C81—C86119.1 (4)C94—C941—H94B109.5
C82—C81—P3123.7 (3)H94A—C941—H94B109.5
C86—C81—P3117.0 (3)C94—C941—H94C109.5
C31—C32—C33121.4 (3)H94A—C941—H94C109.5
C31—C32—H32119.3H94B—C941—H94C109.5
C33—C32—H32119.3C94—C941—H94D109.5
C23—C22—C21120.3 (4)H94A—C941—H94D141.1
C23—C22—H22119.9H94B—C941—H94D56.3
C21—C22—H22119.9H94C—C941—H94D56.3
C13—C12—C11120.5 (3)C94—C941—H94E109.5
C13—C12—H12119.8H94A—C941—H94E56.3
C11—C12—H12119.8H94B—C941—H94E141.1
C65—C64—C63118.3 (3)H94C—C941—H94E56.3
C65—C64—C641120.2 (4)H94D—C941—H94E109.5
C63—C64—C641121.5 (4)C94—C941—H94F109.5
C95—C94—C93117.9 (4)H94A—C941—H94F56.3
C95—C94—C941119.1 (5)H94B—C941—H94F56.3
C93—C94—C941123.0 (5)H94C—C941—H94F141.1
C83—C84—C85120.3 (5)H94D—C941—H94F109.5
C83—C84—H84119.9H94E—C941—H94F109.5
C85—C84—H84119.9C85—C86—C81120.1 (5)
C15—C14—C13119.3 (4)C85—C86—H86119.9
C15—C14—H14120.3C81—C86—H86119.9
C13—C14—H14120.3C64—C641—H64A109.5
C44—C45—C46120.0 (4)C64—C641—H64B109.5
C44—C45—H45120.0H64A—C641—H64B109.5
C46—C45—H45120.0C64—C641—H64C109.5
C45—C44—C43119.6 (4)H64A—C641—H64C109.5
C45—C44—H44120.2H64B—C641—H64C109.5
C43—C44—H44120.2C64—C641—H64D109.5
C63—C62—C61120.8 (3)H64A—C641—H64D141.1
C63—C62—H62119.6H64B—C641—H64D56.3
C61—C62—H62119.6H64C—C641—H64D56.3
C34—C33—C32120.3 (3)C64—C641—H64E109.5
C34—C33—H33119.9H64A—C641—H64E56.3
C32—C33—H33119.9H64B—C641—H64E141.1
C53—C54—C55118.7 (4)H64C—C641—H64E56.3
C53—C54—H54120.7H64D—C641—H64E109.5
C55—C54—H54120.7C64—C641—H64F109.5
C14—C13—C12120.8 (4)H64A—C641—H64F56.3
C14—C13—H13119.6H64B—C641—H64F56.3
C12—C13—H13119.6H64C—C641—H64F141.1
C65—C66—C61120.8 (3)H64D—C641—H64F109.5
C65—C66—H66119.6H64E—C641—H64F109.5
C61—C66—H66119.6Cu2—I3—Cu166.2 (5)
C95—C96—C91121.0 (4)
Cu1—I2—Cu2—P3−173.20 (4)C41—P2—C61—C6667.2 (3)
Cu1—I2—Cu2—I314.0 (8)C51—P2—C61—C66−40.5 (3)
Cu1—I2—Cu2—I119.07 (12)Cu1—P2—C61—C66−169.7 (3)
Cu1—I1—Cu2—P3174.12 (4)C22—C21—C26—C251.6 (6)
Cu1—I1—Cu2—I358 (6)P1—C21—C26—C25170.9 (3)
Cu1—I1—Cu2—I2−18.90 (11)C81—P3—C91—C96−1.2 (3)
Cu2—I2—Cu1—P2101.10 (4)C71—P3—C91—C96−110.6 (3)
Cu2—I2—Cu1—P1−128.43 (4)Cu2—P3—C91—C96129.0 (3)
Cu2—I2—Cu1—I3−12.1 (7)C81—P3—C91—C92176.4 (3)
Cu2—I2—Cu1—I1−16.15 (11)C71—P3—C91—C9267.0 (3)
Cu2—I1—Cu1—P2−101.86 (7)Cu2—P3—C91—C92−53.4 (3)
Cu2—I1—Cu1—P1125.57 (7)C14—C15—C16—C11−2.5 (6)
Cu2—I1—Cu1—I3−76 (5)C12—C11—C16—C153.0 (5)
Cu2—I1—Cu1—I216.15 (10)P1—C11—C16—C15−175.4 (3)
I3—Cu2—Cu1—P294.1 (8)C91—P3—C81—C82−80.2 (3)
I2—Cu2—Cu1—P2−100.12 (4)C71—P3—C81—C8226.9 (4)
I1—Cu2—Cu1—P298.64 (12)Cu2—P3—C81—C82148.2 (3)
I3—Cu2—Cu1—P1−88.4 (8)C91—P3—C81—C8695.2 (3)
I2—Cu2—Cu1—P177.40 (4)C71—P3—C81—C86−157.6 (3)
I1—Cu2—Cu1—P1−83.83 (12)Cu2—P3—C81—C86−36.4 (4)
I2—Cu2—Cu1—I3165.8 (8)C36—C31—C32—C331.2 (6)
I1—Cu2—Cu1—I34.5 (8)P1—C31—C32—C33179.3 (3)
I3—Cu2—Cu1—I2−165.8 (8)C26—C21—C22—C23−2.2 (6)
I1—Cu2—Cu1—I2−161.24 (12)P1—C21—C22—C23−171.2 (3)
I3—Cu2—Cu1—I1−4.5 (8)C16—C11—C12—C13−1.2 (5)
I2—Cu2—Cu1—I1161.24 (12)P1—C11—C12—C13177.2 (3)
P1—Cu1—P2—C61−71.29 (14)C16—C15—C14—C130.1 (6)
I3—Cu1—P2—C61163.3 (4)C41—C46—C45—C441.6 (6)
I2—Cu1—P2—C6147.57 (13)C46—C45—C44—C43−0.6 (7)
I1—Cu1—P2—C61164.99 (15)C42—C43—C44—C45−0.2 (7)
Cu2—Cu1—P2—C61106.42 (13)C66—C61—C62—C63−0.5 (5)
P1—Cu1—P2—C4147.54 (13)P2—C61—C62—C63179.7 (3)
I3—Cu1—P2—C41−77.9 (4)C35—C34—C33—C32−2.1 (6)
I2—Cu1—P2—C41166.41 (13)C341—C34—C33—C32178.2 (4)
I1—Cu1—P2—C41−76.17 (16)C31—C32—C33—C340.6 (5)
Cu2—Cu1—P2—C41−134.74 (13)C15—C14—C13—C121.6 (6)
P1—Cu1—P2—C51165.29 (12)C11—C12—C13—C14−1.1 (6)
I3—Cu1—P2—C5139.9 (4)C62—C61—C66—C650.0 (5)
I2—Cu1—P2—C51−75.85 (12)P2—C61—C66—C65179.8 (3)
I1—Cu1—P2—C5141.57 (15)C92—C91—C96—C95−2.5 (5)
Cu2—Cu1—P2—C51−17.00 (13)P3—C91—C96—C95175.0 (3)
P2—Cu1—P1—C11168.14 (12)C61—C62—C63—C641.1 (6)
I3—Cu1—P1—C11−69.0 (4)C65—C64—C63—C62−1.0 (6)
I2—Cu1—P1—C1146.01 (12)C641—C64—C63—C62178.5 (4)
I1—Cu1—P1—C11−67.51 (14)C32—C31—C36—C35−1.5 (7)
Cu2—Cu1—P1—C11−9.12 (13)P1—C31—C36—C35−179.5 (4)
P2—Cu1—P1—C2149.40 (13)C56—C51—C52—C530.0 (6)
I3—Cu1—P1—C21172.3 (4)P2—C51—C52—C53−179.9 (3)
I2—Cu1—P1—C21−72.73 (13)C73—C72—C71—C761.0 (6)
I1—Cu1—P1—C21173.76 (14)C73—C72—C71—P3−178.5 (3)
Cu2—Cu1—P1—C21−127.85 (12)C81—P3—C71—C72103.8 (3)
P2—Cu1—P1—C31−66.91 (15)C91—P3—C71—C72−149.5 (3)
I3—Cu1—P1—C3156.0 (4)Cu2—P3—C71—C72−22.4 (3)
I2—Cu1—P1—C31170.96 (14)C81—P3—C71—C76−75.7 (4)
I1—Cu1—P1—C3157.44 (16)C91—P3—C71—C7631.0 (4)
Cu2—Cu1—P1—C31115.84 (14)Cu2—P3—C71—C76158.1 (3)
I3—Cu2—P3—C81−13.1 (8)C61—C66—C65—C640.0 (6)
I2—Cu2—P3—C81174.51 (13)C63—C64—C65—C660.5 (6)
I1—Cu2—P3—C81−18.10 (19)C641—C64—C65—C66−179.0 (4)
I3—Cu2—P3—C91−136.3 (8)C85—C84—C83—C82−2.3 (8)
I2—Cu2—P3—C9151.32 (14)C72—C71—C76—C75−0.7 (7)
I1—Cu2—P3—C91−141.29 (18)P3—C71—C76—C75178.8 (4)
I3—Cu2—P3—C71106.5 (8)C71—C72—C73—C74−1.1 (7)
I2—Cu2—P3—C71−65.93 (13)C21—C22—C23—C242.3 (7)
I1—Cu2—P3—C71101.46 (18)C22—C23—C24—C25−1.8 (7)
C21—P1—C11—C12143.9 (3)C46—C41—C42—C431.0 (6)
C31—P1—C11—C12−108.8 (3)P2—C41—C42—C43173.7 (3)
Cu1—P1—C11—C1222.5 (3)C44—C43—C42—C410.0 (7)
C21—P1—C11—C16−37.8 (3)C95—C94—C93—C92−2.6 (7)
C31—P1—C11—C1669.6 (3)C941—C94—C93—C92175.2 (5)
Cu1—P1—C11—C16−159.2 (2)C94—C93—C92—C91−0.1 (7)
C61—P2—C41—C4222.6 (4)C96—C91—C92—C932.6 (6)
C51—P2—C41—C42131.4 (3)P3—C91—C92—C93−175.0 (4)
Cu1—P2—C41—C42−103.4 (3)C72—C73—C74—C751.0 (8)
C61—P2—C41—C46−164.6 (3)C93—C94—C95—C962.7 (7)
C51—P2—C41—C46−55.9 (3)C941—C94—C95—C96−175.2 (4)
Cu1—P2—C41—C4669.3 (3)C91—C96—C95—C94−0.1 (6)
C11—P1—C31—C32128.9 (3)C23—C24—C25—C261.2 (7)
C21—P1—C31—C32−122.0 (3)C21—C26—C25—C24−1.1 (7)
Cu1—P1—C31—C32−1.8 (3)C55—C54—C53—C520.7 (7)
C11—P1—C31—C36−53.1 (4)C51—C52—C53—C54−0.8 (6)
C21—P1—C31—C3655.9 (4)C86—C81—C82—C830.3 (6)
Cu1—P1—C31—C36176.1 (4)P3—C81—C82—C83175.6 (3)
C11—P1—C21—C26150.4 (3)C84—C83—C82—C811.0 (7)
C31—P1—C21—C2641.6 (4)C73—C74—C75—C76−0.8 (9)
Cu1—P1—C21—C26−83.9 (3)C71—C76—C75—C740.6 (8)
C11—P1—C21—C22−40.5 (4)C51—C56—C55—C54−0.8 (6)
C31—P1—C21—C22−149.4 (3)C53—C54—C55—C560.1 (6)
Cu1—P1—C21—C2285.2 (3)C33—C34—C35—C361.8 (8)
C42—C41—C46—C45−1.8 (6)C341—C34—C35—C36−178.4 (5)
P2—C41—C46—C45−174.7 (3)C31—C36—C35—C340.0 (9)
C61—P2—C51—C56−95.7 (3)C83—C84—C85—C862.3 (9)
C41—P2—C51—C56156.2 (3)C84—C85—C86—C81−1.0 (8)
Cu1—P2—C51—C5633.8 (3)C82—C81—C86—C85−0.3 (7)
C61—P2—C51—C5284.3 (3)P3—C81—C86—C85−176.0 (4)
C41—P2—C51—C52−23.9 (4)P3—Cu2—I3—Cu1173.59 (9)
Cu1—P2—C51—C52−146.3 (3)I2—Cu2—I3—Cu1−14.2 (8)
C52—C51—C56—C550.7 (5)I1—Cu2—I3—Cu1−119 (6)
P2—C51—C56—C55−179.3 (3)P2—Cu1—I3—Cu2−104.0 (4)
C41—P2—C61—C62−113.0 (3)P1—Cu1—I3—Cu2123.4 (4)
C51—P2—C61—C62139.2 (3)I2—Cu1—I3—Cu212.3 (7)
Cu1—P2—C61—C6210.1 (3)I1—Cu1—I3—Cu2101 (5)
Table 1
Selected geometric parameters (Å, °) top
I1—Cu22.561 (4)Cu2—P32.2209 (11)
I1—Cu12.747 (4)Cu2—Cu12.7807 (9)
I2—Cu22.5421 (10)Cu1—P22.2562 (12)
I2—Cu12.7033 (8)Cu1—P12.2601 (12)
Cu2—I1—Cu163.07 (9)Cu2—I2—Cu163.941 (18)
Acknowledgements top

Financial assistance from the University of the Free State and Professor A. Roodt is gratefully acknowledged. Mr L. Kirsten is acknowledged for the data collection. Part of this material is based on work supported by the South African National Research Foundation (NRF) under grant No. GUN 2068915. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NRF.

references
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