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Acta Cryst. (2008). E64, o772    [ doi:10.1107/S1600536808007848 ]

Substitutional disorder in the substituted nixantphos ligand C39H32Br0.27Cl0.73NOP2

T. Marimuthu, M. D. Bala and H. B. Friedrich

Abstract top

The structure of 10-(3-bromo/chloropropyl)-4,6-bis(diphenylphosphino)-10H-phenoxazine, C39H32Br0.27Cl0.73NOP2, shows chloro/bromo substitutional disorder in a 3:1 ratio. For application as a ligand in catalysis, the intramolecular P...P distance of 4.263 (2) Å is relevant. The phenoxazine ring system is essentially planar.

Comment top

As part of our ongoing investigation of scorpionate-type ligands (Marimuthu et al., 2008) the title ligand, a diphenylphosphine xanthene based compound, (I) has been prepared in our laboratory. The synthesis strategy involved the addition of an alkyl chain to the amine to form a tridentate ligand. Unlike other scorpionate ligands, (I) has a mixed donor arrangement consisting of N, O & P and it has been used as a precursor in the synthesis of modified nixantphos ligands for continuous flow homogenous hydroformylation of alkenes using supercritical fluids (Web et al., 2005). The functionalization of the nitrogen has been reported in the literature, where the subsequent compounds were successfully immobilized on silica (Sandee et al., 1999, 2001; van Leeuwen et al., 2002), polystyrene (Deprele & Montchamp, 2004) and dendritic supports (Ricken et al., 2006).

The structure of (I) contains chloro- and bromo- substituted alkyl chains in 3:1 ratio (Fig. 1) with an essentially planar phenoxazine ring [with maximum deviation of 0.113 (3) Å for O1] joining the two diphenylphosphino groups. The intramolecular P—P distance of 4.263 (2) Å in (I) compares well to 4.255 (2) Å reported for the precursor nixantphos (Marimuthu et al., 2008). The bond lengths for C—O range from 1.380 (2) to 1.384 (2) and for C—N from 1.398 (2) to 1.402 (2) Å. The bond angles involving the P atoms range from 100.52 (7) to 102.11 (8)°.

The substitutional disorder observed in the halide site of (I) was modelled as 3:1 Cl to Br. The source of the disorder is the sodium hydride induced alkylation using 1-bromo-3-chloropropane adapted for this work. The ligand 1-bromo-3-chloropropane is symmetrical with a chloride and a bromide functionality on either side of a propyl chain, hence a competitive substitution reaction between the two leaving groups. The model of the disordered halide site is in agreement with Br as the more basic and better leaving group than Cl. Other cases of halide substitutional disorder have been reported in the literature (Norman et al., 2000; Laungani et al., 2008; Rotar et al., 2008) and it is interesting to note that all contain only Cl/Br disorder in the 3:1 ratio.

Related literature top

For related literature see: Osiński et al. (2005); Ricken et al. (2006a,b); (Marimuthu et al., 2008).

For related literature, see: Deprele & Montchamp (2004); Laungani et al. (2008); Leeuwen et al. (2002); Norman et al. (2000); Ricken et al. (2006); Rotar et al. (2008); Sandee et al. (1999, 2001); Web et al. (2005).

Experimental top

Synthesis adapted from literature (Web et al., 2005). Yield: 74% of colourless crystals of (I) grown from a solution of dichloromethane/ethanol (1:1) at room temperature, m.p. 493 K (dec.).

Refinement top

All hydrogen atoms were located from a difference map then positioned geometrically and allowed to ride on their respective parent atoms (C—H = 0.95 - 0.99 Å) with Uiso(H) = 1.2 Ueq(C) for aryl H or 1.5 Ueq(C) for CH2. The structure contains substitutional disorder in which Cl1 and Br1 occupy the same position. These were refined with C—Cl and C—Br distances restrained to 1.78 and 1.93 Å and final occupancies for Cl1 and Br1 were 0.734 (2) and 0.266 (2), respectively.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) with thermal ellipsoids shown at 50% probability levels.
10-(3-bromo/chloropropyl)-4,6-bis(diphenylphosphino)-10H-phenoxazine top
Crystal data top
C39H32Br0.27Cl0.73NOP2Z = 2
Mr = 639.83F000 = 665.6
Triclinic, P1Dx = 1.375 Mg m−3
Hall symbol: -P 1Melting point: 493(2) K
a = 10.0539 (3) ÅMo Kα radiation
λ = 0.71073 Å
b = 11.4469 (3) ÅCell parameters from 6264 reflections
c = 14.5299 (3) Åθ = 2.5–28.2º
α = 69.544 (1)ºµ = 0.58 mm−1
β = 83.283 (2)ºT = 173 (2) K
γ = 81.453 (1)ºPrism, colourless
V = 1545.52 (7) Å30.42 × 0.19 × 0.17 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		7458 independent reflections
Radiation source: fine-focus sealed tube5180 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.051
T = 173(2) Kθmax = 28.0º
φ and ω scansθmin = 1.5º
Absorption correction: integration
(XPREP; Bruker, 2005)		h = −13→12
Tmin = 0.792, Tmax = 0.908k = −15→15
24195 measured reflectionsl = −17→19
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)] = 0.041H-atom parameters constrained
wR(F2) = 0.097  w = 1/[σ2(Fo2) + (0.0499P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max = 0.006
7458 reflectionsΔρmax = 0.36 e Å−3
401 parametersΔρmin = −0.28 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C39H32Br0.27Cl0.73NOP2γ = 81.453 (1)º
Mr = 639.83V = 1545.52 (7) Å3
Triclinic, P1Z = 2
a = 10.0539 (3) ÅMo Kα
b = 11.4469 (3) ŵ = 0.58 mm−1
c = 14.5299 (3) ÅT = 173 (2) K
α = 69.544 (1)º0.42 × 0.19 × 0.17 mm
β = 83.283 (2)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		7458 independent reflections
Absorption correction: integration
(XPREP; Bruker, 2005)		5180 reflections with I > 2σ(I)
Tmin = 0.792, Tmax = 0.908Rint = 0.051
24195 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0412 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 0.94Δρmax = 0.36 e Å−3
7458 reflectionsΔρmin = −0.28 e Å−3
401 parameters
Special details top

Experimental. Spectroscopic analysis: 1H NMR (400 MHz,CDCl3, δ, p.p.m.) = 2.13(m, 2H; CH), 2.16(m, 2H; CH), 3.52(m, 2H; CH), 3.69(m, 2H; CH), 6.0(d, 2H; J(H,H) = 7.5 Hz,), 6.34(bd, 2H; J(H,H) = 7.5 Hz,), 6.65(t, 2H J(H,H) = 7.8 Hz), 7.18 – 7.21(bs, 20H); 13C NMR (400 MHz, CDCl3, δ, p.p.m.); = 27.5(ClCH2), 30.8(BrCH2), 41.8(NCH2), 42.6(NCH2), 42.6(NCH2), 111.6(CH), 123.7(CH), 125.5 (C), 128.1(CH), 132.8(CN), 133.8(C),136.8(C),147.0(CO) 31P NMR (600 MHz,CDCl3, δ, p.p.m.) = -19.0; FTIR: cm-1 = 1552(s), 1462(s), 1433(s), 1418(s), 1380(s), 1274(s CN), 1257(m),1206(m), 1092(m), 765(m), 747(m), 722(m), 697(s).516(s), 496(s), 433(s), 400(s); Calculated for C39H32Br0.27Cl0.73NOP2: C=72.03; H= 4.96; N= 2.15; Found C=71.55; H= 4.95; N= 2.26.

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)
C10.12106 (16)0.58921 (15)0.41860 (12)0.0285 (4)
C20.06839 (17)0.70497 (16)0.42572 (13)0.0337 (4)
H20.08520.72550.48090.040*
C3−0.00868 (18)0.79126 (17)0.35303 (13)0.0360 (4)
H3−0.04660.86900.36010.043*
C4−0.03072 (17)0.76542 (16)0.27087 (13)0.0326 (4)
H4−0.08190.82610.22100.039*
C50.02184 (16)0.65037 (15)0.26046 (12)0.0275 (4)
C60.09436 (16)0.56450 (15)0.33551 (12)0.0285 (4)
C70.22129 (16)0.36362 (15)0.39245 (11)0.0278 (4)
C80.26881 (17)0.25469 (15)0.37271 (12)0.0283 (4)
C90.35333 (18)0.16430 (16)0.43904 (12)0.0349 (4)
H90.38630.08750.42850.042*
C100.38889 (19)0.18641 (17)0.51980 (13)0.0376 (4)
H100.44710.12490.56420.045*
C110.34067 (17)0.29726 (16)0.53695 (12)0.0322 (4)
H110.36770.31190.59210.039*
C120.25368 (16)0.38670 (15)0.47466 (12)0.0284 (4)
C130.22292 (18)0.52225 (17)0.57888 (12)0.0348 (4)
H13A0.24340.44140.63230.042*
H13B0.14110.56770.60120.042*
C140.33988 (17)0.59931 (17)0.56022 (12)0.0348 (4)
H14A0.41630.56290.52550.042*
H14B0.31240.68600.51680.042*
C150.38590 (18)0.60363 (13)0.65430 (13)0.0417 (5)
H15A0.30610.61820.69750.050*
H15B0.43990.67460.63850.050*
C21−0.10597 (16)0.74294 (16)0.08074 (12)0.0288 (4)
C22−0.24546 (18)0.75239 (18)0.09281 (14)0.0403 (4)
H22−0.28780.68620.14120.048*
C23−0.32390 (19)0.8556 (2)0.03611 (15)0.0451 (5)
H23−0.41930.86040.04670.054*
C24−0.26619 (19)0.95128 (18)−0.03519 (13)0.0409 (5)
H24−0.32071.0222−0.07460.049*
C25−0.1281 (2)0.9435 (2)−0.04912 (14)0.0481 (5)
H25−0.08671.0091−0.09880.058*
C26−0.04918 (19)0.84080 (18)0.00873 (13)0.0420 (5)
H260.04620.8374−0.00120.050*
C310.15173 (17)0.60609 (16)0.08889 (12)0.0327 (4)
C320.24948 (19)0.6776 (2)0.09138 (15)0.0489 (5)
H320.23730.72330.13570.059*
C330.3658 (2)0.6825 (2)0.02890 (18)0.0614 (6)
H330.43280.73180.03070.074*
C340.3846 (2)0.6171 (2)−0.03508 (16)0.0588 (6)
H340.46410.6218−0.07800.071*
C350.2896 (2)0.5453 (2)−0.03736 (16)0.0567 (6)
H350.30260.4997−0.08180.068*
C360.1751 (2)0.53893 (18)0.02441 (14)0.0433 (5)
H360.11020.48730.02310.052*
C410.32148 (18)0.09367 (15)0.26043 (11)0.0299 (4)
C420.45411 (19)0.09954 (17)0.22056 (13)0.0374 (4)
H420.48970.17790.19720.045*
C430.53459 (19)−0.00586 (19)0.21437 (14)0.0418 (5)
H430.62510.00000.18740.050*
C440.48400 (19)−0.12036 (17)0.24733 (13)0.0380 (4)
H440.5392−0.19320.24250.046*
C450.35297 (19)−0.12821 (17)0.28719 (12)0.0370 (4)
H450.3178−0.20680.31020.044*
C460.27231 (18)−0.02186 (15)0.29384 (12)0.0318 (4)
H460.1822−0.02820.32160.038*
C510.05273 (18)0.19766 (15)0.29170 (13)0.0322 (4)
C52−0.0264 (2)0.21254 (18)0.21515 (14)0.0445 (5)
H520.00750.25030.14910.053*
C53−0.1533 (2)0.1735 (2)0.23338 (17)0.0534 (6)
H53−0.20460.18210.18000.064*
C54−0.2052 (2)0.12224 (19)0.32848 (17)0.0494 (5)
H54−0.29220.09460.34110.059*
C55−0.13087 (19)0.11098 (18)0.40537 (15)0.0423 (5)
H55−0.16780.07820.47130.051*
C56−0.00240 (18)0.14728 (16)0.38703 (13)0.0347 (4)
H560.04880.13750.44070.042*
N10.19570 (15)0.49747 (13)0.49120 (10)0.0332 (3)
O10.13571 (13)0.44822 (11)0.32597 (9)0.0371 (3)
P1−0.01140 (4)0.60026 (4)0.15924 (3)0.02944 (12)
P20.22335 (5)0.24299 (4)0.25806 (3)0.03152 (12)
Cl10.4842 (12)0.4617 (8)0.7179 (10)0.0488 (6)0.7338 (16)
Br10.4972 (14)0.4545 (9)0.7259 (12)0.0488 (6)0.2662 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0291 (9)0.0290 (9)0.0308 (9)−0.0055 (7)−0.0015 (7)−0.0135 (7)
C20.0349 (10)0.0347 (10)0.0387 (10)−0.0040 (8)−0.0022 (8)−0.0215 (8)
C30.0360 (10)0.0317 (10)0.0461 (11)−0.0001 (8)−0.0033 (8)−0.0218 (8)
C40.0333 (9)0.0284 (9)0.0370 (9)−0.0020 (8)−0.0033 (7)−0.0125 (8)
C50.0294 (9)0.0250 (9)0.0293 (8)−0.0063 (7)−0.0010 (7)−0.0096 (7)
C60.0309 (9)0.0251 (9)0.0332 (9)−0.0056 (7)−0.0009 (7)−0.0139 (7)
C70.0318 (9)0.0251 (9)0.0271 (8)−0.0061 (7)−0.0048 (7)−0.0076 (7)
C80.0349 (9)0.0243 (9)0.0277 (8)−0.0056 (7)−0.0045 (7)−0.0097 (7)
C90.0475 (11)0.0240 (9)0.0343 (9)−0.0010 (8)−0.0101 (8)−0.0102 (7)
C100.0457 (11)0.0325 (10)0.0342 (10)−0.0007 (8)−0.0143 (8)−0.0089 (8)
C110.0397 (10)0.0321 (10)0.0277 (9)−0.0049 (8)−0.0082 (7)−0.0116 (7)
C120.0328 (9)0.0281 (9)0.0274 (8)−0.0082 (7)−0.0016 (7)−0.0115 (7)
C130.0417 (10)0.0361 (10)0.0306 (9)−0.0086 (8)−0.0008 (8)−0.0151 (8)
C140.0375 (10)0.0350 (10)0.0325 (9)−0.0063 (8)−0.0014 (8)−0.0117 (8)
C150.0490 (12)0.0382 (11)0.0431 (11)−0.0037 (9)−0.0135 (9)−0.0175 (9)
C210.0313 (9)0.0306 (9)0.0284 (9)−0.0019 (7)−0.0044 (7)−0.0146 (7)
C220.0340 (10)0.0389 (11)0.0462 (11)−0.0041 (9)−0.0019 (8)−0.0125 (9)
C230.0313 (10)0.0525 (13)0.0550 (12)0.0018 (9)−0.0081 (9)−0.0236 (10)
C240.0470 (12)0.0409 (11)0.0354 (10)0.0077 (9)−0.0160 (9)−0.0148 (9)
C250.0473 (12)0.0459 (12)0.0393 (11)−0.0031 (10)−0.0063 (9)0.0004 (9)
C260.0334 (10)0.0459 (12)0.0394 (10)−0.0040 (9)−0.0043 (8)−0.0050 (9)
C310.0317 (9)0.0314 (10)0.0314 (9)0.0029 (8)−0.0066 (7)−0.0073 (8)
C320.0375 (11)0.0573 (14)0.0555 (13)−0.0081 (10)−0.0035 (9)−0.0223 (11)
C330.0393 (12)0.0654 (16)0.0711 (16)−0.0138 (11)−0.0013 (11)−0.0104 (13)
C340.0501 (14)0.0506 (14)0.0515 (13)0.0140 (11)0.0096 (10)0.0004 (11)
C350.0631 (15)0.0510 (14)0.0477 (13)0.0068 (12)0.0093 (11)−0.0159 (11)
C360.0486 (12)0.0397 (11)0.0410 (11)0.0024 (9)−0.0024 (9)−0.0164 (9)
C410.0419 (10)0.0256 (9)0.0243 (8)−0.0011 (8)−0.0082 (7)−0.0104 (7)
C420.0447 (11)0.0349 (10)0.0362 (10)−0.0095 (9)−0.0031 (8)−0.0145 (8)
C430.0369 (10)0.0507 (13)0.0406 (11)−0.0016 (9)−0.0034 (8)−0.0201 (9)
C440.0480 (11)0.0346 (10)0.0310 (9)0.0104 (9)−0.0113 (8)−0.0140 (8)
C450.0548 (12)0.0267 (9)0.0287 (9)−0.0029 (9)−0.0051 (8)−0.0082 (7)
C460.0409 (10)0.0268 (9)0.0278 (9)−0.0024 (8)−0.0019 (7)−0.0100 (7)
C510.0421 (10)0.0230 (9)0.0366 (10)0.0056 (8)−0.0128 (8)−0.0169 (7)
C520.0585 (13)0.0376 (11)0.0401 (11)−0.0005 (10)−0.0214 (9)−0.0132 (9)
C530.0552 (13)0.0475 (13)0.0629 (14)0.0005 (11)−0.0333 (11)−0.0189 (11)
C540.0403 (11)0.0394 (12)0.0740 (15)0.0032 (9)−0.0180 (11)−0.0245 (11)
C550.0416 (11)0.0380 (11)0.0513 (12)0.0013 (9)−0.0038 (9)−0.0222 (9)
C560.0386 (10)0.0333 (10)0.0382 (10)0.0034 (8)−0.0103 (8)−0.0201 (8)
N10.0436 (9)0.0305 (8)0.0312 (8)−0.0019 (7)−0.0088 (7)−0.0167 (6)
O10.0524 (8)0.0265 (6)0.0376 (7)0.0075 (6)−0.0200 (6)−0.0169 (5)
P10.0326 (2)0.0276 (2)0.0302 (2)−0.00380 (19)−0.00480 (18)−0.01137 (19)
P20.0463 (3)0.0230 (2)0.0269 (2)−0.0012 (2)−0.0079 (2)−0.00993 (18)
Cl10.0433 (17)0.0434 (7)0.0459 (17)−0.0032 (4)−0.0128 (10)0.0046 (7)
Br10.0433 (17)0.0434 (7)0.0459 (17)−0.0032 (4)−0.0128 (10)0.0046 (7)
Geometric parameters (Å, °) top
C1—C21.386 (2)C24—C251.373 (3)
C1—C61.395 (2)C24—H240.9500
C1—N11.398 (2)C25—C261.380 (3)
C2—C31.388 (2)C25—H250.9500
C2—H20.9500C26—H260.9500
C3—C41.375 (2)C31—C321.380 (3)
C3—H30.9500C31—C361.386 (3)
C4—C51.396 (2)C31—P11.8253 (18)
C4—H40.9500C32—C331.389 (3)
C5—C61.382 (2)C32—H320.9500
C5—P11.8345 (16)C33—C341.365 (3)
C6—O11.3837 (19)C33—H330.9500
C7—O11.3799 (19)C34—C351.360 (3)
C7—C81.381 (2)C34—H340.9500
C7—C121.393 (2)C35—C361.368 (3)
C8—C91.398 (2)C35—H350.9500
C8—P21.8313 (16)C36—H360.9500
C9—C101.379 (2)C41—C461.385 (2)
C9—H90.9500C41—C421.392 (2)
C10—C111.385 (2)C41—P21.8335 (17)
C10—H100.9500C42—C431.374 (3)
C11—C121.380 (2)C42—H420.9500
C11—H110.9500C43—C441.381 (3)
C12—N11.402 (2)C43—H430.9500
C13—N11.461 (2)C44—C451.378 (3)
C13—C141.517 (2)C44—H440.9500
C13—H13A0.9900C45—C461.385 (2)
C13—H13B0.9900C45—H450.9500
C14—C151.512 (2)C46—H460.9500
C14—H14A0.9900C51—C561.384 (2)
C14—H14B0.9900C51—C521.390 (2)
C15—Cl11.7770 (18)C51—P21.8281 (18)
C15—Br11.9266 (19)C52—C531.380 (3)
C15—H15A0.9900C52—H520.9500
C15—H15B0.9900C53—C541.372 (3)
C21—C261.381 (2)C53—H530.9500
C21—C221.386 (2)C54—C551.374 (3)
C21—P11.8338 (17)C54—H540.9500
C22—C231.375 (3)C55—C561.383 (2)
C22—H220.9500C55—H550.9500
C23—C241.365 (3)C56—H560.9500
C23—H230.9500
C2—C1—C6117.26 (15)C24—C25—H25119.8
C2—C1—N1122.98 (15)C26—C25—H25119.8
C6—C1—N1119.74 (15)C25—C26—C21121.39 (18)
C1—C2—C3120.70 (16)C25—C26—H26119.3
C1—C2—H2119.7C21—C26—H26119.3
C3—C2—H2119.7C32—C31—C36118.05 (18)
C4—C3—C2120.72 (17)C32—C31—P1124.77 (15)
C4—C3—H3119.6C36—C31—P1117.08 (14)
C2—C3—H3119.6C31—C32—C33119.9 (2)
C3—C4—C5120.29 (17)C31—C32—H32120.1
C3—C4—H4119.9C33—C32—H32120.1
C5—C4—H4119.9C34—C33—C32120.7 (2)
C6—C5—C4117.78 (15)C34—C33—H33119.7
C6—C5—P1117.69 (12)C32—C33—H33119.7
C4—C5—P1124.31 (13)C35—C34—C33119.9 (2)
C5—C6—O1115.95 (14)C35—C34—H34120.0
C5—C6—C1123.20 (15)C33—C34—H34120.0
O1—C6—C1120.80 (15)C34—C35—C36119.9 (2)
O1—C7—C8115.32 (14)C34—C35—H35120.0
O1—C7—C12121.59 (15)C36—C35—H35120.0
C8—C7—C12123.07 (15)C35—C36—C31121.5 (2)
C7—C8—C9117.72 (15)C35—C36—H36119.2
C7—C8—P2117.39 (12)C31—C36—H36119.2
C9—C8—P2124.82 (13)C46—C41—C42118.10 (16)
C10—C9—C8120.13 (16)C46—C41—P2125.35 (14)
C10—C9—H9119.9C42—C41—P2116.47 (13)
C8—C9—H9119.9C43—C42—C41121.27 (17)
C9—C10—C11120.73 (17)C43—C42—H42119.4
C9—C10—H10119.6C41—C42—H42119.4
C11—C10—H10119.6C42—C43—C44120.04 (18)
C12—C11—C10120.61 (15)C42—C43—H43120.0
C12—C11—H11119.7C44—C43—H43120.0
C10—C11—H11119.7C45—C44—C43119.59 (17)
C11—C12—C7117.69 (16)C45—C44—H44120.2
C11—C12—N1123.19 (14)C43—C44—H44120.2
C7—C12—N1119.11 (15)C44—C45—C46120.22 (17)
N1—C13—C14112.39 (14)C44—C45—H45119.9
N1—C13—H13A109.1C46—C45—H45119.9
C14—C13—H13A109.1C41—C46—C45120.78 (17)
N1—C13—H13B109.1C41—C46—H46119.6
C14—C13—H13B109.1C45—C46—H46119.6
H13A—C13—H13B107.9C56—C51—C52117.67 (17)
C15—C14—C13112.46 (15)C56—C51—P2125.18 (13)
C15—C14—H14A109.1C52—C51—P2117.13 (14)
C13—C14—H14A109.1C53—C52—C51121.25 (19)
C15—C14—H14B109.1C53—C52—H52119.4
C13—C14—H14B109.1C51—C52—H52119.4
H14A—C14—H14B107.8C54—C53—C52120.04 (18)
C14—C15—Cl1111.5 (5)C54—C53—H53120.0
C14—C15—Br1114.0 (6)C52—C53—H53120.0
C14—C15—H15A109.3C53—C54—C55119.73 (19)
Cl1—C15—H15A109.3C53—C54—H54120.1
Br1—C15—H15A109.2C55—C54—H54120.1
C14—C15—H15B109.3C54—C55—C56120.16 (19)
Cl1—C15—H15B109.3C54—C55—H55119.9
Br1—C15—H15B106.8C56—C55—H55119.9
H15A—C15—H15B108.0C55—C56—C51121.07 (17)
C26—C21—C22117.21 (17)C55—C56—H56119.5
C26—C21—P1125.12 (13)C51—C56—H56119.5
C22—C21—P1117.65 (13)C1—N1—C12119.14 (13)
C23—C22—C21121.32 (17)C1—N1—C13120.04 (14)
C23—C22—H22119.3C12—N1—C13120.59 (14)
C21—C22—H22119.3C7—O1—C6118.58 (12)
C24—C23—C22120.74 (18)C31—P1—C21100.52 (7)
C24—C23—H23119.6C31—P1—C5102.11 (8)
C22—C23—H23119.6C21—P1—C5101.24 (7)
C23—C24—C25118.97 (18)C51—P2—C8102.00 (8)
C23—C24—H24120.5C51—P2—C41101.66 (8)
C25—C24—H24120.5C8—P2—C41100.58 (7)
C24—C25—C26120.35 (18)
C6—C1—C2—C30.6 (2)C43—C44—C45—C460.2 (3)
N1—C1—C2—C3−177.93 (15)C42—C41—C46—C45−0.3 (2)
C1—C2—C3—C4−2.2 (3)P2—C41—C46—C45176.23 (13)
C2—C3—C4—C51.4 (3)C44—C45—C46—C410.2 (3)
C3—C4—C5—C60.7 (2)C56—C51—C52—C53−2.7 (3)
C3—C4—C5—P1175.10 (13)P2—C51—C52—C53175.83 (15)
C4—C5—C6—O1175.16 (14)C51—C52—C53—C541.9 (3)
P1—C5—C6—O10.4 (2)C52—C53—C54—C550.6 (3)
C4—C5—C6—C1−2.3 (2)C53—C54—C55—C56−2.2 (3)
P1—C5—C6—C1−177.06 (13)C54—C55—C56—C511.3 (3)
C2—C1—C6—C51.6 (2)C52—C51—C56—C551.1 (3)
N1—C1—C6—C5−179.76 (15)P2—C51—C56—C55−177.33 (14)
C2—C1—C6—O1−175.72 (15)C2—C1—N1—C12−175.29 (15)
N1—C1—C6—O12.9 (2)C6—C1—N1—C126.2 (2)
O1—C7—C8—C9−178.47 (14)C2—C1—N1—C13−0.9 (2)
C12—C7—C8—C90.0 (2)C6—C1—N1—C13−179.40 (14)
O1—C7—C8—P24.6 (2)C11—C12—N1—C1172.78 (15)
C12—C7—C8—P2−176.93 (12)C7—C12—N1—C1−8.2 (2)
C7—C8—C9—C10−1.3 (2)C11—C12—N1—C13−1.6 (2)
P2—C8—C9—C10175.33 (14)C7—C12—N1—C13177.40 (14)
C8—C9—C10—C110.7 (3)C14—C13—N1—C1−80.73 (19)
C9—C10—C11—C121.4 (3)C14—C13—N1—C1293.60 (19)
C10—C11—C12—C7−2.7 (2)C8—C7—O1—C6−173.86 (14)
C10—C11—C12—N1176.35 (16)C12—C7—O1—C67.7 (2)
O1—C7—C12—C11−179.65 (14)C5—C6—O1—C7172.70 (14)
C8—C7—C12—C112.0 (2)C1—C6—O1—C7−9.8 (2)
O1—C7—C12—N11.3 (2)C32—C31—P1—C2181.38 (17)
C8—C7—C12—N1−177.05 (15)C36—C31—P1—C21−94.87 (15)
N1—C13—C14—C15−168.77 (14)C32—C31—P1—C5−22.66 (18)
C13—C14—C15—Cl177.1 (5)C36—C31—P1—C5161.09 (14)
C13—C14—C15—Br178.6 (6)C26—C21—P1—C31−17.74 (17)
C26—C21—C22—C23−0.7 (3)C22—C21—P1—C31160.68 (14)
P1—C21—C22—C23−179.23 (15)C26—C21—P1—C587.00 (16)
C21—C22—C23—C241.1 (3)C22—C21—P1—C5−94.58 (14)
C22—C23—C24—C25−0.5 (3)C6—C5—P1—C31−76.01 (14)
C23—C24—C25—C26−0.5 (3)C4—C5—P1—C31109.61 (15)
C24—C25—C26—C210.9 (3)C6—C5—P1—C21−179.49 (13)
C22—C21—C26—C25−0.3 (3)C4—C5—P1—C216.13 (16)
P1—C21—C26—C25178.11 (15)C56—C51—P2—C8−18.19 (16)
C36—C31—C32—C331.3 (3)C52—C51—P2—C8163.35 (14)
P1—C31—C32—C33−174.94 (16)C56—C51—P2—C4185.44 (16)
C31—C32—C33—C34−0.1 (3)C52—C51—P2—C41−93.02 (14)
C32—C33—C34—C35−0.6 (3)C7—C8—P2—C51−80.83 (14)
C33—C34—C35—C360.1 (3)C9—C8—P2—C51102.50 (15)
C34—C35—C36—C311.2 (3)C7—C8—P2—C41174.69 (13)
C32—C31—C36—C35−1.8 (3)C9—C8—P2—C41−1.97 (16)
P1—C31—C36—C35174.67 (16)C46—C41—P2—C51−7.91 (16)
C46—C41—C42—C43−0.1 (3)C42—C41—P2—C51168.68 (13)
P2—C41—C42—C43−176.90 (14)C46—C41—P2—C896.84 (15)
C41—C42—C43—C440.5 (3)C42—C41—P2—C8−86.57 (14)
C42—C43—C44—C45−0.6 (3)
Acknowledgements top

We thank Dr Manuel Fernandez for the data collection, SASOL, THRIP and the University of KwaZulu-Natal for financial support.

references
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