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Acta Cryst. (2008). E64, m205    [ doi:10.1107/S1600536807066238 ]

[4'-(2-Bromo-5-pyridyl)-2,2':6',2''-terpyridine-[kappa]3N,N',N'']bis(triphenylphosphine-[kappa]P)copper(I) tetrafluoridoborate dichloromethane hemisolvate

M. I. J. Polson, G. S. Hanan and N. J. Taylor

Abstract top

In the title complex, [Cu(C20H13BrN4)(C18H15P)2]BF4·0.5CH2Cl2, the copper(I) cation adopts a distorted tetrahedral arrangement, coordinated by two triphenylphosphine ligands and two N atoms of the potentially tridentate terpyridine ligand. One half-molecule of dichloromethane crystallizes with the complex. The chlorine atoms are disordered over two sites with occupancies fixed at 0.30 and 0.20 respectively. The N donor atom of the central pyridine interacts weakly with the copper centre at a distance of 3.071 Å.

Comment top

To fully characterize a family of multi-nuclear ruthenium complexes (Loiseau et al., 2002) we undertook to synthesize the the key bridging ligand 2:6:2''':6'''tetra-2-pyridyl-4,5':2',2'':5'',4'''tetrapyridine. Initial attempts at the synthesis by nickel catalysed homocoupling of 4'-(2-bromo-5-pyridyl)2,2':6',2''terpyridine failed, presumably due to the free terpyridine unit sequestering the nickel from the catalyst (Loiseau et al., 2002). The title complex, (I), Fig 1, crystallized as part of this work. The copper(I) cation adopts a distorted tetrahedral arrangement with the additional pyridine interacting weakly with the copper centre at a distance of 3.071 Å). Two other structures of copper (I) terpyridine bis-triphenylphosphine complexes were found in the literature (Ainscough et al., 1994; Feng et al., 2002). In both of these structures, the terpyridine ligand coordinates through all three N atoms giving a pentacoordinate complex. Despite the long N14—Cu1 distance there is an interaction, albeit somewhat weak. If there were no interaction it is likely that the N14 nitrogen of the loosely bound pyridine ring would rotate to adopt a s-trans arrangement, which is much more commonly seen in uncoordinated polypyridine ligands (Fitchett et al., 2005).

Related literature top

For general background see: Loiseau et al. (2002); Fitchett et al. (2005). For related structures see: Ainscough et al. (1994); Feng et al. (2002).

Experimental top

4'-(2-bromo-5-pyridyl)2,2':6',2''terpyridine (100 mg) and bis-triphenylphosphine bis-acetonitrile copper(I) tetrafloroborate (194 mg) were stirred in dichloromethane (20 ml) under argon for 1 h. After the colour had changed from colourless to yellow, the solution was evaporated to dryness, redissolved in a mimimum of dichloromethane and crystals suitable for X-ray crystallography were grown by diffusion with diethyl ether. Yield (191 mg, 70%)

Refinement top

One half molecule of dichloromethane crystallizes with the compound (1) with the chlorine atoms disordered over two sites with occupancies of fixed at 0.30 and 0.20 respectively. The hydrogen atoms of this hemi-solvate were not included in the refinement. All other H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.97 Å, Uiso = 1.2Ueq (C) for CH2 atoms.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Version 1.08; Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (1), showing displacement ellipsoids at the 50% probability level. H atoms have been omitted for clarity.
[4'-(2-Bromo-5-pyridyl)-2,2':6',2''-terpyridine-\ κ3N,N',N'']bis(triphenylphosphine-κP)copper(I) tetrafluoridoborate dichloromethane hemisolvate top
Crystal data top
[Cu(C20H13BrN4)(C18H15P)2]BF4·0.5CH2Cl2Z = 2
Mr = 1106.61F000 = 1126
Triclinic, P1Dx = 1.389 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 13.8900 (5) ÅCell parameters from 6660 reflections
b = 13.9623 (6) Åθ = 2.4–29.9º
c = 15.2549 (5) ŵ = 1.33 mm−1
α = 72.358 (1)ºT = 150 (1) K
β = 83.6520 (11)ºPrism, yellow
γ = 69.821 (1)º0.34 × 0.30 × 0.26 mm
V = 2646.23 (16) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		9368 independent reflections
Radiation source: fine-focus sealed tube7361 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 150(1) Kθmax = 25.1º
ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Bruker,2000)		h = −16→16
Tmin = 0.627, Tmax = 0.698k = −16→16
22637 measured reflectionsl = −18→18
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)] = 0.061H-atom parameters constrained
wR(F2) = 0.209  w = 1/[σ2(Fo2) + (0.020P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
9368 reflectionsΔρmax = 1.37 e Å−3
676 parametersΔρmin = −0.80 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C20H13BrN4)(C18H15P)2]BF4·0.5CH2Cl2γ = 69.821 (1)º
Mr = 1106.61V = 2646.23 (16) Å3
Triclinic, P1Z = 2
a = 13.8900 (5) ÅMo Kα
b = 13.9623 (6) ŵ = 1.33 mm−1
c = 15.2549 (5) ÅT = 150 (1) K
α = 72.358 (1)º0.34 × 0.30 × 0.26 mm
β = 83.6520 (11)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		9368 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker,2000)		7361 reflections with I > 2σ(I)
Tmin = 0.627, Tmax = 0.698Rint = 0.022
22637 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.061676 parameters
wR(F2) = 0.209H-atom parameters constrained
S = 1.05Δρmax = 1.37 e Å−3
9368 reflectionsΔρmin = −0.80 e Å−3
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)
Cu10.20583 (3)0.25255 (3)0.24907 (3)0.04279 (18)
P10.14443 (7)0.14203 (7)0.36391 (6)0.0424 (2)
P20.14842 (7)0.43189 (7)0.22730 (6)0.0421 (2)
Br10.92793 (5)0.11921 (7)−0.14023 (5)0.1063 (3)
C10.2577 (3)0.1842 (3)0.0794 (2)0.0425 (8)
N20.1746 (2)0.2181 (2)0.1297 (2)0.0445 (7)
C30.0854 (3)0.2164 (3)0.1056 (3)0.0512 (9)
H30.02710.23950.14010.061*
C40.0758 (3)0.1823 (3)0.0324 (3)0.0561 (10)
H40.01270.18140.01850.067*
C50.1597 (4)0.1501 (4)−0.0192 (3)0.0620 (11)
H50.15500.1285−0.07000.074*
C60.2523 (3)0.1499 (4)0.0052 (3)0.0566 (10)
H60.31120.1266−0.02860.068*
C70.3570 (3)0.1824 (3)0.1106 (2)0.0441 (8)
N80.3551 (2)0.1939 (2)0.19544 (19)0.0411 (6)
C90.4458 (3)0.1841 (3)0.2282 (2)0.0443 (8)
C100.5351 (3)0.1692 (3)0.1767 (3)0.0500 (9)
H100.59550.16380.20180.060*
C110.5357 (3)0.1621 (3)0.0882 (3)0.0527 (9)
C120.4434 (3)0.1683 (3)0.0561 (3)0.0522 (9)
H120.44010.1630−0.00280.063*
C130.4479 (3)0.1911 (3)0.3233 (3)0.0481 (9)
N140.3784 (3)0.2734 (4)0.3441 (3)0.0770 (12)
C150.3831 (4)0.2848 (5)0.4277 (4)0.093 (2)
H150.33560.34350.44260.111*
C160.4552 (4)0.2135 (4)0.4927 (3)0.0720 (13)
H160.45580.22340.55020.086*
C170.5253 (4)0.1286 (4)0.4703 (3)0.0802 (15)
H170.57460.07880.51250.096*
C180.5220 (4)0.1176 (4)0.3841 (3)0.0754 (14)
H180.56990.06050.36720.090*
C190.6294 (3)0.1514 (4)0.0300 (3)0.0568 (10)
C200.7254 (3)0.1068 (4)0.0688 (3)0.0617 (11)
H200.73020.08180.13250.074*
N210.8130 (3)0.0976 (4)0.0186 (3)0.0759 (11)
C220.8033 (4)0.1336 (4)−0.0706 (3)0.0706 (13)
C230.7126 (4)0.1801 (6)−0.1162 (3)0.094 (2)
H230.70980.2065−0.17990.113*
C240.6260 (4)0.1859 (6)−0.0639 (3)0.0886 (18)
H240.56270.2142−0.09280.106*
C250.2110 (3)−0.0005 (3)0.3844 (3)0.0464 (8)
C260.2852 (3)−0.0364 (3)0.3229 (3)0.0553 (10)
H260.29970.01250.27100.066*
C270.3377 (4)−0.1427 (4)0.3369 (3)0.0652 (12)
H270.3861−0.16540.29390.078*
C280.3195 (4)−0.2154 (4)0.4136 (4)0.0664 (12)
H280.3567−0.28730.42380.080*
C290.2447 (4)−0.1817 (4)0.4767 (4)0.0714 (13)
H290.2309−0.23110.52860.086*
C300.1917 (4)−0.0750 (3)0.4616 (3)0.0627 (11)
H300.1420−0.05250.50380.075*
C310.1328 (3)0.1546 (3)0.4806 (2)0.0470 (8)
C320.0418 (3)0.1829 (4)0.5276 (3)0.0614 (11)
H32−0.01960.19460.50060.074*
C330.0415 (4)0.1939 (4)0.6151 (3)0.0769 (14)
H33−0.02050.21460.64590.092*
C340.1310 (5)0.1749 (4)0.6562 (3)0.0814 (15)
H340.13050.18110.71530.098*
C350.2224 (4)0.1463 (5)0.6098 (4)0.0791 (14)
H350.28390.13370.63710.095*
C360.2222 (4)0.1364 (4)0.5239 (3)0.0690 (12)
H360.28440.11680.49320.083*
C370.0140 (3)0.1617 (3)0.3331 (3)0.0479 (9)
C38−0.0562 (3)0.2630 (4)0.3151 (3)0.0592 (10)
H38−0.03760.31680.32490.071*
C39−0.1537 (4)0.2871 (4)0.2829 (3)0.0755 (14)
H39−0.19980.35610.27040.091*
C40−0.1806 (4)0.2059 (5)0.2698 (4)0.0886 (18)
H40−0.24630.22030.24960.106*
C41−0.1129 (4)0.1057 (5)0.2861 (4)0.0846 (16)
H41−0.13220.05230.27630.102*
C42−0.0139 (4)0.0821 (4)0.3176 (3)0.0675 (12)
H420.03270.01350.32790.081*
C430.2107 (3)0.5033 (3)0.1301 (3)0.0493 (9)
C440.1596 (4)0.5978 (3)0.0671 (3)0.0603 (11)
H440.08970.63020.07480.072*
C450.2102 (4)0.6449 (4)−0.0066 (3)0.0719 (13)
H450.17410.7088−0.04790.086*
C460.3115 (5)0.5999 (4)−0.0199 (4)0.0875 (16)
H460.34540.6324−0.06970.105*
C470.3642 (5)0.5046 (5)0.0416 (6)0.122 (3)
H470.43360.47190.03190.146*
C480.3150 (4)0.4572 (4)0.1173 (5)0.097 (2)
H480.35180.39450.15960.116*
C490.0116 (3)0.5008 (3)0.1992 (3)0.0460 (8)
C50−0.0272 (3)0.4842 (3)0.1281 (3)0.0564 (10)
H500.01590.43920.09550.068*
C51−0.1297 (4)0.5335 (4)0.1045 (3)0.0687 (12)
H51−0.15480.52330.05520.082*
C52−0.1947 (4)0.5982 (4)0.1549 (4)0.0745 (13)
H52−0.26370.63160.13960.089*
C53−0.1570 (4)0.6124 (4)0.2264 (4)0.0788 (14)
H53−0.20120.65370.26140.095*
C54−0.0542 (3)0.5666 (4)0.2483 (3)0.0645 (11)
H54−0.02900.57980.29590.077*
C550.1621 (3)0.4779 (3)0.3233 (3)0.0533 (10)
C560.1300 (4)0.4313 (4)0.4090 (3)0.0671 (12)
H560.10310.37680.41640.080*
C570.1369 (5)0.4640 (5)0.4846 (4)0.0859 (16)
H570.11530.43110.54220.103*
C580.1750 (6)0.5437 (7)0.4745 (5)0.114 (3)
H580.17990.56550.52520.137*
C590.2066 (6)0.5925 (6)0.3891 (6)0.115 (2)
H590.23250.64750.38230.138*
C600.2000 (4)0.5602 (4)0.3137 (4)0.0809 (15)
H600.22120.59380.25610.097*
F10.6777 (3)0.8864 (3)0.1912 (2)0.1053 (11)
F20.5358 (3)0.9296 (3)0.2740 (3)0.1141 (12)
F30.6069 (4)0.7686 (4)0.2744 (5)0.195 (3)
F40.5314 (5)0.8907 (7)0.1460 (3)0.210 (3)
B10.5864 (5)0.8693 (5)0.2184 (4)0.0722 (15)
Cl10.5274 (16)0.480 (2)0.2408 (12)0.357 (16)0.30
Cl20.5825 (17)0.5107 (10)0.3935 (10)0.198 (6)0.30
Cl30.5682 (8)0.5078 (11)0.2081 (10)0.135 (4)0.20
Cl40.572 (2)0.458 (2)0.394 (2)0.253 (16)0.20
C1S0.538 (2)0.5698 (13)0.2990 (17)0.179 (11)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0430 (3)0.0470 (3)0.0407 (3)−0.0171 (2)0.00886 (19)−0.0164 (2)
P10.0416 (5)0.0477 (5)0.0399 (5)−0.0176 (4)0.0068 (4)−0.0144 (4)
P20.0424 (5)0.0432 (5)0.0417 (5)−0.0145 (4)0.0020 (4)−0.0140 (4)
Br10.0707 (4)0.1666 (7)0.1063 (5)−0.0550 (4)0.0471 (3)−0.0720 (5)
C10.0425 (19)0.050 (2)0.0368 (18)−0.0154 (16)0.0010 (15)−0.0143 (15)
N20.0435 (17)0.0546 (18)0.0385 (15)−0.0180 (14)0.0016 (13)−0.0164 (14)
C30.045 (2)0.062 (2)0.048 (2)−0.0187 (18)0.0017 (17)−0.0188 (18)
C40.049 (2)0.068 (3)0.056 (2)−0.021 (2)−0.0093 (18)−0.019 (2)
C50.067 (3)0.077 (3)0.055 (2)−0.023 (2)−0.004 (2)−0.037 (2)
C60.051 (2)0.077 (3)0.049 (2)−0.020 (2)0.0080 (18)−0.033 (2)
C70.0419 (19)0.054 (2)0.0382 (18)−0.0168 (16)0.0023 (15)−0.0160 (16)
N80.0414 (16)0.0501 (16)0.0341 (14)−0.0162 (13)0.0010 (12)−0.0141 (13)
C90.0401 (19)0.051 (2)0.0398 (18)−0.0117 (16)0.0002 (15)−0.0141 (16)
C100.040 (2)0.069 (2)0.046 (2)−0.0213 (18)0.0035 (16)−0.0202 (19)
C110.041 (2)0.068 (2)0.052 (2)−0.0188 (18)0.0099 (17)−0.0246 (19)
C120.051 (2)0.071 (3)0.0404 (19)−0.0231 (19)0.0051 (16)−0.0229 (19)
C130.043 (2)0.063 (2)0.0420 (19)−0.0186 (17)0.0001 (16)−0.0193 (18)
N140.057 (2)0.105 (3)0.060 (2)0.007 (2)−0.0119 (18)−0.045 (2)
C150.069 (3)0.129 (5)0.069 (3)0.015 (3)−0.016 (3)−0.061 (3)
C160.066 (3)0.110 (4)0.049 (2)−0.028 (3)−0.005 (2)−0.036 (3)
C170.085 (4)0.086 (3)0.059 (3)−0.006 (3)−0.027 (3)−0.021 (3)
C180.081 (3)0.070 (3)0.062 (3)0.004 (2)−0.025 (2)−0.025 (2)
C190.047 (2)0.079 (3)0.055 (2)−0.025 (2)0.0132 (18)−0.032 (2)
C200.045 (2)0.080 (3)0.056 (2)−0.017 (2)0.0085 (18)−0.022 (2)
N210.052 (2)0.098 (3)0.079 (3)−0.023 (2)0.016 (2)−0.035 (2)
C220.058 (3)0.107 (4)0.065 (3)−0.039 (3)0.027 (2)−0.045 (3)
C230.069 (3)0.182 (6)0.052 (3)−0.061 (4)0.021 (2)−0.047 (3)
C240.052 (3)0.163 (6)0.055 (3)−0.039 (3)0.005 (2)−0.037 (3)
C250.050 (2)0.047 (2)0.047 (2)−0.0210 (17)0.0045 (16)−0.0153 (16)
C260.061 (2)0.055 (2)0.051 (2)−0.0209 (19)0.0088 (19)−0.0172 (19)
C270.065 (3)0.061 (3)0.075 (3)−0.019 (2)0.012 (2)−0.035 (2)
C280.065 (3)0.050 (2)0.087 (3)−0.017 (2)−0.002 (2)−0.025 (2)
C290.081 (3)0.051 (2)0.075 (3)−0.028 (2)−0.003 (3)0.000 (2)
C300.066 (3)0.060 (3)0.061 (3)−0.024 (2)0.015 (2)−0.017 (2)
C310.052 (2)0.051 (2)0.0407 (19)−0.0201 (17)0.0067 (16)−0.0157 (16)
C320.056 (2)0.076 (3)0.052 (2)−0.023 (2)0.0119 (19)−0.021 (2)
C330.081 (3)0.095 (4)0.055 (3)−0.027 (3)0.023 (2)−0.032 (3)
C340.123 (5)0.082 (3)0.049 (3)−0.039 (3)0.005 (3)−0.029 (2)
C350.075 (3)0.104 (4)0.070 (3)−0.028 (3)−0.008 (3)−0.042 (3)
C360.058 (3)0.094 (3)0.065 (3)−0.022 (2)0.005 (2)−0.042 (3)
C370.047 (2)0.057 (2)0.0415 (19)−0.0252 (18)0.0051 (16)−0.0085 (17)
C380.054 (2)0.066 (3)0.056 (2)−0.026 (2)0.0071 (19)−0.010 (2)
C390.053 (3)0.085 (3)0.070 (3)−0.018 (2)−0.002 (2)−0.001 (3)
C400.064 (3)0.114 (5)0.081 (4)−0.045 (3)−0.021 (3)0.007 (3)
C410.084 (4)0.094 (4)0.088 (4)−0.048 (3)−0.026 (3)−0.013 (3)
C420.068 (3)0.073 (3)0.065 (3)−0.032 (2)−0.010 (2)−0.011 (2)
C430.049 (2)0.049 (2)0.056 (2)−0.0223 (17)0.0070 (17)−0.0179 (18)
C440.058 (2)0.054 (2)0.060 (2)−0.019 (2)0.002 (2)−0.004 (2)
C450.078 (3)0.069 (3)0.063 (3)−0.032 (3)0.001 (2)−0.003 (2)
C460.092 (4)0.072 (3)0.084 (4)−0.035 (3)0.029 (3)−0.002 (3)
C470.058 (3)0.094 (4)0.171 (7)−0.018 (3)0.045 (4)0.000 (4)
C480.054 (3)0.067 (3)0.127 (5)−0.015 (2)0.019 (3)0.020 (3)
C490.045 (2)0.0449 (19)0.047 (2)−0.0159 (16)0.0026 (16)−0.0111 (16)
C500.055 (2)0.059 (2)0.054 (2)−0.0156 (19)−0.0010 (19)−0.0178 (19)
C510.066 (3)0.071 (3)0.069 (3)−0.025 (2)−0.018 (2)−0.010 (2)
C520.050 (3)0.075 (3)0.086 (3)−0.012 (2)−0.004 (2)−0.015 (3)
C530.052 (3)0.084 (3)0.089 (4)0.001 (2)0.003 (2)−0.037 (3)
C540.056 (3)0.070 (3)0.063 (3)−0.007 (2)0.002 (2)−0.029 (2)
C550.050 (2)0.053 (2)0.057 (2)−0.0073 (18)−0.0081 (18)−0.0253 (19)
C560.074 (3)0.070 (3)0.054 (3)−0.013 (2)−0.001 (2)−0.026 (2)
C570.086 (4)0.105 (4)0.060 (3)−0.003 (3)−0.005 (3)−0.044 (3)
C580.109 (5)0.132 (6)0.115 (6)0.002 (4)−0.028 (4)−0.093 (5)
C590.132 (6)0.125 (5)0.135 (6)−0.057 (5)−0.007 (5)−0.083 (5)
C600.093 (4)0.082 (3)0.091 (4)−0.044 (3)0.002 (3)−0.041 (3)
F10.095 (2)0.166 (3)0.081 (2)−0.066 (2)0.0291 (17)−0.056 (2)
F20.109 (3)0.126 (3)0.115 (3)−0.034 (2)0.037 (2)−0.063 (2)
F30.139 (4)0.091 (3)0.313 (8)−0.025 (3)0.088 (5)−0.045 (4)
F40.169 (5)0.441 (11)0.108 (3)−0.177 (6)0.006 (3)−0.116 (5)
B10.075 (4)0.082 (4)0.062 (3)−0.025 (3)0.016 (3)−0.030 (3)
Cl10.31 (2)0.76 (5)0.216 (14)−0.42 (3)0.076 (14)−0.20 (2)
Cl20.311 (19)0.125 (9)0.140 (10)−0.073 (10)−0.049 (11)0.004 (8)
Cl30.090 (6)0.201 (11)0.159 (11)−0.066 (7)0.003 (6)−0.096 (9)
Cl40.27 (2)0.20 (2)0.20 (2)−0.12 (2)−0.069 (17)0.14 (2)
C1S0.27 (3)0.078 (9)0.20 (2)−0.092 (13)0.14 (2)−0.066 (12)
Geometric parameters (Å, °) top
Cu1—N82.121 (3)C32—C331.389 (7)
Cu1—N22.142 (3)C32—H320.9300
Cu1—P12.2621 (10)C33—C341.362 (8)
Cu1—P22.2788 (10)C33—H330.9300
P1—C311.826 (4)C34—C351.376 (8)
P1—C251.824 (4)C34—H340.9300
P1—C371.829 (4)C35—C361.360 (7)
P2—C551.819 (4)C35—H350.9300
P2—C431.832 (4)C36—H360.9300
P2—C491.841 (4)C37—C381.377 (6)
Br1—C221.910 (4)C37—C421.386 (6)
C1—N21.339 (5)C38—C391.387 (6)
C1—C61.374 (5)C38—H380.9300
C1—C71.498 (5)C39—C401.382 (8)
N2—C31.340 (5)C39—H390.9300
C3—C41.375 (6)C40—C411.355 (8)
C3—H30.9300C40—H400.9300
C4—C51.352 (6)C41—C421.403 (7)
C4—H40.9300C41—H410.9300
C5—C61.376 (6)C42—H420.9300
C5—H50.9300C43—C441.380 (6)
C6—H60.9300C43—C481.386 (6)
C7—N81.347 (5)C44—C451.374 (6)
C7—C121.374 (5)C44—H440.9300
N8—C91.355 (5)C45—C461.349 (7)
C9—C101.380 (5)C45—H450.9300
C9—C131.488 (5)C46—C471.382 (9)
C10—C111.383 (5)C46—H460.9300
C10—H100.9300C47—C481.383 (8)
C11—C121.387 (6)C47—H470.9300
C11—C191.481 (5)C48—H480.9300
C12—H120.9300C49—C501.374 (6)
C13—N141.319 (5)C49—C541.388 (6)
C13—C181.371 (6)C50—C511.384 (6)
N14—C151.345 (6)C50—H500.9300
C15—C161.382 (7)C51—C521.388 (7)
C15—H150.9300C51—H510.9300
C16—C171.358 (7)C52—C531.354 (7)
C16—H160.9300C52—H520.9300
C17—C181.377 (7)C53—C541.381 (7)
C17—H170.9300C53—H530.9300
C18—H180.9300C54—H540.9300
C19—C241.366 (7)C55—C561.374 (6)
C19—C201.376 (6)C55—C601.385 (6)
C20—N211.353 (6)C56—C571.386 (7)
C20—H200.9300C56—H560.9300
N21—C221.304 (6)C57—C581.352 (10)
C22—C231.359 (7)C57—H570.9300
C23—C241.360 (7)C58—C591.376 (11)
C23—H230.9300C58—H580.9300
C24—H240.9300C59—C601.379 (8)
C25—C261.382 (5)C59—H590.9300
C25—C301.386 (6)C60—H600.9300
C26—C271.370 (6)F1—B11.368 (7)
C26—H260.9300F2—B11.346 (6)
C27—C281.362 (7)F3—B11.355 (8)
C27—H270.9300F4—B11.313 (8)
C28—C291.394 (7)Cl1—Cl30.835 (16)
C28—H280.9300Cl1—C1S1.79 (3)
C29—C301.374 (6)Cl1—Cl42.39 (4)
C29—H290.9300Cl2—Cl40.79 (3)
C30—H300.9300Cl2—C1S1.51 (3)
C31—C321.376 (6)Cl3—C1S1.79 (2)
C31—C361.379 (6)Cl4—C1S1.74 (3)
N8—Cu1—N277.85 (11)C31—C32—C33120.2 (4)
N8—Cu1—P1119.66 (8)C31—C32—H32119.9
N2—Cu1—P1102.16 (8)C33—C32—H32119.9
N8—Cu1—P2113.91 (8)C34—C33—C32120.6 (5)
N2—Cu1—P2109.81 (9)C34—C33—H33119.7
P1—Cu1—P2121.80 (4)C32—C33—H33119.7
C31—P1—C25101.36 (17)C33—C34—C35119.6 (4)
C31—P1—C37104.69 (18)C33—C34—H34120.2
C25—P1—C37104.55 (18)C35—C34—H34120.2
C31—P1—Cu1120.24 (12)C36—C35—C34119.6 (5)
C25—P1—Cu1116.95 (12)C36—C35—H35120.2
C37—P1—Cu1107.44 (12)C34—C35—H35120.2
C55—P2—C43104.72 (19)C35—C36—C31122.2 (5)
C55—P2—C49102.07 (17)C35—C36—H36118.9
C43—P2—C49102.12 (17)C31—C36—H36118.9
C55—P2—Cu1116.80 (13)C38—C37—C42118.7 (4)
C43—P2—Cu1113.20 (13)C38—C37—P1118.2 (3)
C49—P2—Cu1116.11 (12)C42—C37—P1122.8 (3)
N2—C1—C6121.6 (3)C37—C38—C39122.0 (4)
N2—C1—C7116.2 (3)C37—C38—H38119.0
C6—C1—C7122.2 (3)C39—C38—H38119.0
C1—N2—C3117.6 (3)C40—C39—C38118.3 (5)
C1—N2—Cu1114.3 (2)C40—C39—H39120.9
C3—N2—Cu1127.8 (3)C38—C39—H39120.9
N2—C3—C4123.2 (4)C41—C40—C39121.0 (5)
N2—C3—H3118.4C41—C40—H40119.5
C4—C3—H3118.4C39—C40—H40119.5
C5—C4—C3119.0 (4)C40—C41—C42120.4 (5)
C5—C4—H4120.5C40—C41—H41119.8
C3—C4—H4120.5C42—C41—H41119.8
C4—C5—C6118.7 (4)C37—C42—C41119.5 (5)
C4—C5—H5120.7C37—C42—H42120.2
C6—C5—H5120.7C41—C42—H42120.2
C1—C6—C5120.0 (4)C44—C43—C48118.2 (4)
C1—C6—H6120.0C44—C43—P2124.1 (3)
C5—C6—H6120.0C48—C43—P2117.7 (3)
N8—C7—C12123.3 (3)C45—C44—C43121.1 (4)
N8—C7—C1115.3 (3)C45—C44—H44119.4
C12—C7—C1121.4 (3)C43—C44—H44119.4
C7—N8—C9116.4 (3)C46—C45—C44121.0 (5)
C7—N8—Cu1114.5 (2)C46—C45—H45119.5
C9—N8—Cu1128.1 (2)C44—C45—H45119.5
N8—C9—C10122.7 (3)C45—C46—C47119.0 (5)
N8—C9—C13118.0 (3)C45—C46—H46120.5
C10—C9—C13119.2 (3)C47—C46—H46120.5
C9—C10—C11120.6 (3)C46—C47—C48120.9 (5)
C9—C10—H10119.7C46—C47—H47119.6
C11—C10—H10119.7C48—C47—H47119.6
C10—C11—C12116.5 (3)C43—C48—C47119.8 (5)
C10—C11—C19121.5 (4)C43—C48—H48120.1
C12—C11—C19122.0 (4)C47—C48—H48120.1
C7—C12—C11120.4 (3)C50—C49—C54118.9 (4)
C7—C12—H12119.8C50—C49—P2118.5 (3)
C11—C12—H12119.8C54—C49—P2122.7 (3)
N14—C13—C18122.4 (4)C49—C50—C51120.9 (4)
N14—C13—C9116.7 (3)C49—C50—H50119.6
C18—C13—C9120.8 (4)C51—C50—H50119.6
C13—N14—C15117.6 (4)C50—C51—C52119.6 (4)
N14—C15—C16123.1 (5)C50—C51—H51120.2
N14—C15—H15118.4C52—C51—H51120.2
C16—C15—H15118.4C53—C52—C51119.5 (4)
C17—C16—C15118.2 (4)C53—C52—H52120.2
C17—C16—H16120.9C51—C52—H52120.2
C15—C16—H16120.9C52—C53—C54121.2 (5)
C16—C17—C18118.9 (4)C52—C53—H53119.4
C16—C17—H17120.5C54—C53—H53119.4
C18—C17—H17120.5C53—C54—C49119.9 (4)
C13—C18—C17119.7 (4)C53—C54—H54120.1
C13—C18—H18120.2C49—C54—H54120.1
C17—C18—H18120.2C56—C55—C60118.4 (4)
C24—C19—C20116.4 (4)C56—C55—P2118.4 (3)
C24—C19—C11122.6 (4)C60—C55—P2123.2 (4)
C20—C19—C11121.0 (4)C55—C56—C57121.2 (5)
N21—C20—C19123.1 (4)C55—C56—H56119.4
N21—C20—H20118.4C57—C56—H56119.4
C19—C20—H20118.4C58—C57—C56119.9 (6)
C22—N21—C20116.8 (4)C58—C57—H57120.0
N21—C22—C23125.0 (4)C56—C57—H57120.0
N21—C22—Br1116.1 (4)C57—C58—C59120.0 (5)
C23—C22—Br1118.8 (4)C57—C58—H58120.0
C22—C23—C24116.7 (5)C59—C58—H58120.0
C22—C23—H23121.6C58—C59—C60120.4 (6)
C24—C23—H23121.6C58—C59—H59119.8
C23—C24—C19121.9 (5)C60—C59—H59119.8
C23—C24—H24119.1C59—C60—C55120.2 (6)
C19—C24—H24119.1C59—C60—H60119.9
C26—C25—C30118.1 (4)C55—C60—H60119.9
C26—C25—P1119.7 (3)F4—B1—F2110.9 (6)
C30—C25—P1122.2 (3)F4—B1—F3114.6 (7)
C27—C26—C25121.2 (4)F2—B1—F3103.3 (5)
C27—C26—H26119.4F4—B1—F1109.8 (5)
C25—C26—H26119.4F2—B1—F1109.9 (5)
C28—C27—C26120.4 (4)F3—B1—F1108.1 (5)
C28—C27—H27119.8Cl3—Cl1—C1S76.2 (18)
C26—C27—H27119.8Cl3—Cl1—Cl4103.8 (16)
C27—C28—C29119.8 (4)C1S—Cl1—Cl446.5 (10)
C27—C28—H28120.1Cl4—Cl2—C1S93 (3)
C29—C28—H28120.1Cl1—Cl3—C1S76.9 (19)
C30—C29—C28119.4 (4)Cl2—Cl4—C1S60 (2)
C30—C29—H29120.3Cl2—Cl4—Cl1107 (3)
C28—C29—H29120.3C1S—Cl4—Cl148.5 (11)
C29—C30—C25121.1 (4)Cl2—C1S—Cl1111.1 (13)
C29—C30—H30119.4Cl2—C1S—Cl427.1 (12)
C25—C30—H30119.4Cl1—C1S—Cl485.0 (16)
C32—C31—C36117.9 (4)Cl2—C1S—Cl3121.0 (14)
C32—C31—P1124.9 (3)Cl1—C1S—Cl327.0 (6)
C36—C31—P1117.2 (3)Cl4—C1S—Cl3100.4 (16)
Acknowledgements top

The authors thank the NSERC of Canada for funding. MIJP also thanks the Foundation of Research Science and Technology for funding.

references
References top

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