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

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

doi:10.1107/S1600536808007848

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o772

doi:10.1107/S1600536808007848

Open

access

Substitutional disorder in the substituted nixantphos ligand C₃₉H₃₂Br_0.27Cl_0.73NOP₂

Thashree Marimuthu,^a Muhammad D. Bala ^a ^* and Holger B. Friedrich ^a

^aSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
^*Correspondence e-mail: bala@ukzn.ac.za

(Received 12 March 2008; accepted 21 March 2008; online 2 April 2008)

The structure of 10-(3-bromo/chloropropyl)-4,6-bis(diphenylphosphino)-10H-phenoxazine, C₃₉H₃₂Br_0.27Cl_0.73NOP₂, 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.

Related literature

For related literature see: Osiński et al. (2005 ); Ricken et al. (2006a ,b ); (Marimuthu et al., 2008 ); Deprele & Montchamp (2004 ); Laungani et al. (2008 ); van 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

Crystal data

C₃₉H₃₂Br_0.27Cl_0.73NOP₂
M_r = 639.83
Triclinic, $[P \overline 1]$
a = 10.0539 (3) Å
b = 11.4469 (3) Å
c = 14.5299 (3) Å
α = 69.544 (1)°
β = 83.283 (2)°
γ = 81.453 (1)°
V = 1545.52 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 173 (2) K
0.42 × 0.19 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: integration (XPREP; Bruker, 2005 ) T_min = 0.792, T_max = 0.908
24195 measured reflections
7458 independent reflections
5180 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.097
S = 0.94
7458 reflections
401 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.28 e Å⁻³

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

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536808007848/pv2073sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007848/pv2073Isup2.hkl

checkCIF report

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.).

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

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

C₃₉H₃₂Br_0.27Cl_0.73NOP₂	Z = 2
M_r = 639.83	F(000) = 665.6
Triclinic, P1	D_x = 1.375 Mg m⁻³
Hall symbol: -P 1	Melting point: 493(2) K
a = 10.0539 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4469 (3) Å	Cell parameters from 6264 reflections
c = 14.5299 (3) Å	θ = 2.5–28.2°
α = 69.544 (1)°	µ = 0.58 mm⁻¹
β = 83.283 (2)°	T = 173 K
γ = 81.453 (1)°	Prism, colourless
V = 1545.52 (7) Å³	0.42 × 0.19 × 0.17 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	7458 independent reflections
Radiation source: fine-focus sealed tube	5180 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ϕ and ω scans	θ_max = 28.0°, θ_min = 1.5°
Absorption correction: integration (XPREP; Bruker, 2005)	h = −13→12
T_min = 0.792, T_max = 0.908	k = −15→15
24195 measured reflections	l = −17→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0499P)²] where P = (F_o² + 2F_c²)/3
7458 reflections	(Δ/σ)_max = 0.006
401 parameters	Δρ_max = 0.36 e Å⁻³
2 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₃₉H₃₂Br_0.27Cl_0.73NOP₂	γ = 81.453 (1)°
M_r = 639.83	V = 1545.52 (7) Å³
Triclinic, P1	Z = 2
a = 10.0539 (3) Å	Mo Kα radiation
b = 11.4469 (3) Å	µ = 0.58 mm⁻¹
c = 14.5299 (3) Å	T = 173 K
α = 69.544 (1)°	0.42 × 0.19 × 0.17 mm
β = 83.283 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	7458 independent reflections
Absorption correction: integration (XPREP; Bruker, 2005)	5180 reflections with I > 2σ(I)
T_min = 0.792, T_max = 0.908	R_int = 0.051
24195 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	2 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 0.94	Δρ_max = 0.36 e Å⁻³
7458 reflections	Δρ_min = −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 C₃₉H₃₂Br_0.27Cl_0.73NOP₂: 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.12106 (16)	0.58921 (15)	0.41860 (12)	0.0285 (4)
C2	0.06839 (17)	0.70497 (16)	0.42572 (13)	0.0337 (4)
H2	0.0852	0.7255	0.4809	0.040*
C3	−0.00868 (18)	0.79126 (17)	0.35303 (13)	0.0360 (4)
H3	−0.0466	0.8690	0.3601	0.043*
C4	−0.03072 (17)	0.76542 (16)	0.27087 (13)	0.0326 (4)
H4	−0.0819	0.8261	0.2210	0.039*
C5	0.02184 (16)	0.65037 (15)	0.26046 (12)	0.0275 (4)
C6	0.09436 (16)	0.56450 (15)	0.33551 (12)	0.0285 (4)
C7	0.22129 (16)	0.36362 (15)	0.39245 (11)	0.0278 (4)
C8	0.26881 (17)	0.25469 (15)	0.37271 (12)	0.0283 (4)
C9	0.35333 (18)	0.16430 (16)	0.43904 (12)	0.0349 (4)
H9	0.3863	0.0875	0.4285	0.042*
C10	0.38889 (19)	0.18641 (17)	0.51980 (13)	0.0376 (4)
H10	0.4471	0.1249	0.5642	0.045*
C11	0.34067 (17)	0.29726 (16)	0.53695 (12)	0.0322 (4)
H11	0.3677	0.3119	0.5921	0.039*
C12	0.25368 (16)	0.38670 (15)	0.47466 (12)	0.0284 (4)
C13	0.22292 (18)	0.52225 (17)	0.57888 (12)	0.0348 (4)
H13A	0.2434	0.4414	0.6323	0.042*
H13B	0.1411	0.5677	0.6012	0.042*
C14	0.33988 (17)	0.59931 (17)	0.56022 (12)	0.0348 (4)
H14A	0.4163	0.5629	0.5255	0.042*
H14B	0.3124	0.6860	0.5168	0.042*
C15	0.38590 (18)	0.60363 (13)	0.65430 (13)	0.0417 (5)
H15A	0.3061	0.6182	0.6975	0.050*
H15B	0.4399	0.6746	0.6385	0.050*
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	−0.2878	0.6862	0.1412	0.048*
C23	−0.32390 (19)	0.8556 (2)	0.03611 (15)	0.0451 (5)
H23	−0.4193	0.8604	0.0467	0.054*
C24	−0.26619 (19)	0.95128 (18)	−0.03519 (13)	0.0409 (5)
H24	−0.3207	1.0222	−0.0746	0.049*
C25	−0.1281 (2)	0.9435 (2)	−0.04912 (14)	0.0481 (5)
H25	−0.0867	1.0091	−0.0988	0.058*
C26	−0.04918 (19)	0.84080 (18)	0.00873 (13)	0.0420 (5)
H26	0.0462	0.8374	−0.0012	0.050*
C31	0.15173 (17)	0.60609 (16)	0.08889 (12)	0.0327 (4)
C32	0.24948 (19)	0.6776 (2)	0.09138 (15)	0.0489 (5)
H32	0.2373	0.7233	0.1357	0.059*
C33	0.3658 (2)	0.6825 (2)	0.02890 (18)	0.0614 (6)
H33	0.4328	0.7318	0.0307	0.074*
C34	0.3846 (2)	0.6171 (2)	−0.03508 (16)	0.0588 (6)
H34	0.4641	0.6218	−0.0780	0.071*
C35	0.2896 (2)	0.5453 (2)	−0.03736 (16)	0.0567 (6)
H35	0.3026	0.4997	−0.0818	0.068*
C36	0.1751 (2)	0.53893 (18)	0.02441 (14)	0.0433 (5)
H36	0.1102	0.4873	0.0231	0.052*
C41	0.32148 (18)	0.09367 (15)	0.26043 (11)	0.0299 (4)
C42	0.45411 (19)	0.09954 (17)	0.22056 (13)	0.0374 (4)
H42	0.4897	0.1779	0.1972	0.045*
C43	0.53459 (19)	−0.00586 (19)	0.21437 (14)	0.0418 (5)
H43	0.6251	0.0000	0.1874	0.050*
C44	0.48400 (19)	−0.12036 (17)	0.24733 (13)	0.0380 (4)
H44	0.5392	−0.1932	0.2425	0.046*
C45	0.35297 (19)	−0.12821 (17)	0.28719 (12)	0.0370 (4)
H45	0.3178	−0.2068	0.3102	0.044*
C46	0.27231 (18)	−0.02186 (15)	0.29384 (12)	0.0318 (4)
H46	0.1822	−0.0282	0.3216	0.038*
C51	0.05273 (18)	0.19766 (15)	0.29170 (13)	0.0322 (4)
C52	−0.0264 (2)	0.21254 (18)	0.21515 (14)	0.0445 (5)
H52	0.0075	0.2503	0.1491	0.053*
C53	−0.1533 (2)	0.1735 (2)	0.23338 (17)	0.0534 (6)
H53	−0.2046	0.1821	0.1800	0.064*
C54	−0.2052 (2)	0.12224 (19)	0.32848 (17)	0.0494 (5)
H54	−0.2922	0.0946	0.3411	0.059*
C55	−0.13087 (19)	0.11098 (18)	0.40537 (15)	0.0423 (5)
H55	−0.1678	0.0782	0.4713	0.051*
C56	−0.00240 (18)	0.14728 (16)	0.38703 (13)	0.0347 (4)
H56	0.0488	0.1375	0.4407	0.042*
N1	0.19570 (15)	0.49747 (13)	0.49120 (10)	0.0332 (3)
O1	0.13571 (13)	0.44822 (11)	0.32597 (9)	0.0371 (3)
P1	−0.01140 (4)	0.60026 (4)	0.15924 (3)	0.02944 (12)
P2	0.22335 (5)	0.24299 (4)	0.25806 (3)	0.03152 (12)
Cl1	0.4842 (12)	0.4617 (8)	0.7179 (10)	0.0488 (6)	0.7338 (16)
Br1	0.4972 (14)	0.4545 (9)	0.7259 (12)	0.0488 (6)	0.2662 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0291 (9)	0.0290 (9)	0.0308 (9)	−0.0055 (7)	−0.0015 (7)	−0.0135 (7)
C2	0.0349 (10)	0.0347 (10)	0.0387 (10)	−0.0040 (8)	−0.0022 (8)	−0.0215 (8)
C3	0.0360 (10)	0.0317 (10)	0.0461 (11)	−0.0001 (8)	−0.0033 (8)	−0.0218 (8)
C4	0.0333 (9)	0.0284 (9)	0.0370 (9)	−0.0020 (8)	−0.0033 (7)	−0.0125 (8)
C5	0.0294 (9)	0.0250 (9)	0.0293 (8)	−0.0063 (7)	−0.0010 (7)	−0.0096 (7)
C6	0.0309 (9)	0.0251 (9)	0.0332 (9)	−0.0056 (7)	−0.0009 (7)	−0.0139 (7)
C7	0.0318 (9)	0.0251 (9)	0.0271 (8)	−0.0061 (7)	−0.0048 (7)	−0.0076 (7)
C8	0.0349 (9)	0.0243 (9)	0.0277 (8)	−0.0056 (7)	−0.0045 (7)	−0.0097 (7)
C9	0.0475 (11)	0.0240 (9)	0.0343 (9)	−0.0010 (8)	−0.0101 (8)	−0.0102 (7)
C10	0.0457 (11)	0.0325 (10)	0.0342 (10)	−0.0007 (8)	−0.0143 (8)	−0.0089 (8)
C11	0.0397 (10)	0.0321 (10)	0.0277 (9)	−0.0049 (8)	−0.0082 (7)	−0.0116 (7)
C12	0.0328 (9)	0.0281 (9)	0.0274 (8)	−0.0082 (7)	−0.0016 (7)	−0.0115 (7)
C13	0.0417 (10)	0.0361 (10)	0.0306 (9)	−0.0086 (8)	−0.0008 (8)	−0.0151 (8)
C14	0.0375 (10)	0.0350 (10)	0.0325 (9)	−0.0063 (8)	−0.0014 (8)	−0.0117 (8)
C15	0.0490 (12)	0.0382 (11)	0.0431 (11)	−0.0037 (9)	−0.0135 (9)	−0.0175 (9)
C21	0.0313 (9)	0.0306 (9)	0.0284 (9)	−0.0019 (7)	−0.0044 (7)	−0.0146 (7)
C22	0.0340 (10)	0.0389 (11)	0.0462 (11)	−0.0041 (9)	−0.0019 (8)	−0.0125 (9)
C23	0.0313 (10)	0.0525 (13)	0.0550 (12)	0.0018 (9)	−0.0081 (9)	−0.0236 (10)
C24	0.0470 (12)	0.0409 (11)	0.0354 (10)	0.0077 (9)	−0.0160 (9)	−0.0148 (9)
C25	0.0473 (12)	0.0459 (12)	0.0393 (11)	−0.0031 (10)	−0.0063 (9)	0.0004 (9)
C26	0.0334 (10)	0.0459 (12)	0.0394 (10)	−0.0040 (9)	−0.0043 (8)	−0.0050 (9)
C31	0.0317 (9)	0.0314 (10)	0.0314 (9)	0.0029 (8)	−0.0066 (7)	−0.0073 (8)
C32	0.0375 (11)	0.0573 (14)	0.0555 (13)	−0.0081 (10)	−0.0035 (9)	−0.0223 (11)
C33	0.0393 (12)	0.0654 (16)	0.0711 (16)	−0.0138 (11)	−0.0013 (11)	−0.0104 (13)
C34	0.0501 (14)	0.0506 (14)	0.0515 (13)	0.0140 (11)	0.0096 (10)	0.0004 (11)
C35	0.0631 (15)	0.0510 (14)	0.0477 (13)	0.0068 (12)	0.0093 (11)	−0.0159 (11)
C36	0.0486 (12)	0.0397 (11)	0.0410 (11)	0.0024 (9)	−0.0024 (9)	−0.0164 (9)
C41	0.0419 (10)	0.0256 (9)	0.0243 (8)	−0.0011 (8)	−0.0082 (7)	−0.0104 (7)
C42	0.0447 (11)	0.0349 (10)	0.0362 (10)	−0.0095 (9)	−0.0031 (8)	−0.0145 (8)
C43	0.0369 (10)	0.0507 (13)	0.0406 (11)	−0.0016 (9)	−0.0034 (8)	−0.0201 (9)
C44	0.0480 (11)	0.0346 (10)	0.0310 (9)	0.0104 (9)	−0.0113 (8)	−0.0140 (8)
C45	0.0548 (12)	0.0267 (9)	0.0287 (9)	−0.0029 (9)	−0.0051 (8)	−0.0082 (7)
C46	0.0409 (10)	0.0268 (9)	0.0278 (9)	−0.0024 (8)	−0.0019 (7)	−0.0100 (7)
C51	0.0421 (10)	0.0230 (9)	0.0366 (10)	0.0056 (8)	−0.0128 (8)	−0.0169 (7)
C52	0.0585 (13)	0.0376 (11)	0.0401 (11)	−0.0005 (10)	−0.0214 (9)	−0.0132 (9)
C53	0.0552 (13)	0.0475 (13)	0.0629 (14)	0.0005 (11)	−0.0333 (11)	−0.0189 (11)
C54	0.0403 (11)	0.0394 (12)	0.0740 (15)	0.0032 (9)	−0.0180 (11)	−0.0245 (11)
C55	0.0416 (11)	0.0380 (11)	0.0513 (12)	0.0013 (9)	−0.0038 (9)	−0.0222 (9)
C56	0.0386 (10)	0.0333 (10)	0.0382 (10)	0.0034 (8)	−0.0103 (8)	−0.0201 (8)
N1	0.0436 (9)	0.0305 (8)	0.0312 (8)	−0.0019 (7)	−0.0088 (7)	−0.0167 (6)
O1	0.0524 (8)	0.0265 (6)	0.0376 (7)	0.0075 (6)	−0.0200 (6)	−0.0169 (5)
P1	0.0326 (2)	0.0276 (2)	0.0302 (2)	−0.00380 (19)	−0.00480 (18)	−0.01137 (19)
P2	0.0463 (3)	0.0230 (2)	0.0269 (2)	−0.0012 (2)	−0.0079 (2)	−0.00993 (18)
Cl1	0.0433 (17)	0.0434 (7)	0.0459 (17)	−0.0032 (4)	−0.0128 (10)	0.0046 (7)
Br1	0.0433 (17)	0.0434 (7)	0.0459 (17)	−0.0032 (4)	−0.0128 (10)	0.0046 (7)

Geometric parameters (Å, º) top

C1—C2	1.386 (2)	C24—C25	1.373 (3)
C1—C6	1.395 (2)	C24—H24	0.9500
C1—N1	1.398 (2)	C25—C26	1.380 (3)
C2—C3	1.388 (2)	C25—H25	0.9500
C2—H2	0.9500	C26—H26	0.9500
C3—C4	1.375 (2)	C31—C32	1.380 (3)
C3—H3	0.9500	C31—C36	1.386 (3)
C4—C5	1.396 (2)	C31—P1	1.8253 (18)
C4—H4	0.9500	C32—C33	1.389 (3)
C5—C6	1.382 (2)	C32—H32	0.9500
C5—P1	1.8345 (16)	C33—C34	1.365 (3)
C6—O1	1.3837 (19)	C33—H33	0.9500
C7—O1	1.3799 (19)	C34—C35	1.360 (3)
C7—C8	1.381 (2)	C34—H34	0.9500
C7—C12	1.393 (2)	C35—C36	1.368 (3)
C8—C9	1.398 (2)	C35—H35	0.9500
C8—P2	1.8313 (16)	C36—H36	0.9500
C9—C10	1.379 (2)	C41—C46	1.385 (2)
C9—H9	0.9500	C41—C42	1.392 (2)
C10—C11	1.385 (2)	C41—P2	1.8335 (17)
C10—H10	0.9500	C42—C43	1.374 (3)
C11—C12	1.380 (2)	C42—H42	0.9500
C11—H11	0.9500	C43—C44	1.381 (3)
C12—N1	1.402 (2)	C43—H43	0.9500
C13—N1	1.461 (2)	C44—C45	1.378 (3)
C13—C14	1.517 (2)	C44—H44	0.9500
C13—H13A	0.9900	C45—C46	1.385 (2)
C13—H13B	0.9900	C45—H45	0.9500
C14—C15	1.512 (2)	C46—H46	0.9500
C14—H14A	0.9900	C51—C56	1.384 (2)
C14—H14B	0.9900	C51—C52	1.390 (2)
C15—Cl1	1.7770 (18)	C51—P2	1.8281 (18)
C15—Br1	1.9266 (19)	C52—C53	1.380 (3)
C15—H15A	0.9900	C52—H52	0.9500
C15—H15B	0.9900	C53—C54	1.372 (3)
C21—C26	1.381 (2)	C53—H53	0.9500
C21—C22	1.386 (2)	C54—C55	1.374 (3)
C21—P1	1.8338 (17)	C54—H54	0.9500
C22—C23	1.375 (3)	C55—C56	1.383 (2)
C22—H22	0.9500	C55—H55	0.9500
C23—C24	1.365 (3)	C56—H56	0.9500
C23—H23	0.9500

C2—C1—C6	117.26 (15)	C24—C25—H25	119.8
C2—C1—N1	122.98 (15)	C26—C25—H25	119.8
C6—C1—N1	119.74 (15)	C25—C26—C21	121.39 (18)
C1—C2—C3	120.70 (16)	C25—C26—H26	119.3
C1—C2—H2	119.7	C21—C26—H26	119.3
C3—C2—H2	119.7	C32—C31—C36	118.05 (18)
C4—C3—C2	120.72 (17)	C32—C31—P1	124.77 (15)
C4—C3—H3	119.6	C36—C31—P1	117.08 (14)
C2—C3—H3	119.6	C31—C32—C33	119.9 (2)
C3—C4—C5	120.29 (17)	C31—C32—H32	120.1
C3—C4—H4	119.9	C33—C32—H32	120.1
C5—C4—H4	119.9	C34—C33—C32	120.7 (2)
C6—C5—C4	117.78 (15)	C34—C33—H33	119.7
C6—C5—P1	117.69 (12)	C32—C33—H33	119.7
C4—C5—P1	124.31 (13)	C35—C34—C33	119.9 (2)
C5—C6—O1	115.95 (14)	C35—C34—H34	120.0
C5—C6—C1	123.20 (15)	C33—C34—H34	120.0
O1—C6—C1	120.80 (15)	C34—C35—C36	119.9 (2)
O1—C7—C8	115.32 (14)	C34—C35—H35	120.0
O1—C7—C12	121.59 (15)	C36—C35—H35	120.0
C8—C7—C12	123.07 (15)	C35—C36—C31	121.5 (2)
C7—C8—C9	117.72 (15)	C35—C36—H36	119.2
C7—C8—P2	117.39 (12)	C31—C36—H36	119.2
C9—C8—P2	124.82 (13)	C46—C41—C42	118.10 (16)
C10—C9—C8	120.13 (16)	C46—C41—P2	125.35 (14)
C10—C9—H9	119.9	C42—C41—P2	116.47 (13)
C8—C9—H9	119.9	C43—C42—C41	121.27 (17)
C9—C10—C11	120.73 (17)	C43—C42—H42	119.4
C9—C10—H10	119.6	C41—C42—H42	119.4
C11—C10—H10	119.6	C42—C43—C44	120.04 (18)
C12—C11—C10	120.61 (15)	C42—C43—H43	120.0
C12—C11—H11	119.7	C44—C43—H43	120.0
C10—C11—H11	119.7	C45—C44—C43	119.59 (17)
C11—C12—C7	117.69 (16)	C45—C44—H44	120.2
C11—C12—N1	123.19 (14)	C43—C44—H44	120.2
C7—C12—N1	119.11 (15)	C44—C45—C46	120.22 (17)
N1—C13—C14	112.39 (14)	C44—C45—H45	119.9
N1—C13—H13A	109.1	C46—C45—H45	119.9
C14—C13—H13A	109.1	C41—C46—C45	120.78 (17)
N1—C13—H13B	109.1	C41—C46—H46	119.6
C14—C13—H13B	109.1	C45—C46—H46	119.6
H13A—C13—H13B	107.9	C56—C51—C52	117.67 (17)
C15—C14—C13	112.46 (15)	C56—C51—P2	125.18 (13)
C15—C14—H14A	109.1	C52—C51—P2	117.13 (14)
C13—C14—H14A	109.1	C53—C52—C51	121.25 (19)
C15—C14—H14B	109.1	C53—C52—H52	119.4
C13—C14—H14B	109.1	C51—C52—H52	119.4
H14A—C14—H14B	107.8	C54—C53—C52	120.04 (18)
C14—C15—Cl1	111.5 (5)	C54—C53—H53	120.0
C14—C15—Br1	114.0 (6)	C52—C53—H53	120.0
C14—C15—H15A	109.3	C53—C54—C55	119.73 (19)
Cl1—C15—H15A	109.3	C53—C54—H54	120.1
Br1—C15—H15A	109.2	C55—C54—H54	120.1
C14—C15—H15B	109.3	C54—C55—C56	120.16 (19)
Cl1—C15—H15B	109.3	C54—C55—H55	119.9
Br1—C15—H15B	106.8	C56—C55—H55	119.9
H15A—C15—H15B	108.0	C55—C56—C51	121.07 (17)
C26—C21—C22	117.21 (17)	C55—C56—H56	119.5
C26—C21—P1	125.12 (13)	C51—C56—H56	119.5
C22—C21—P1	117.65 (13)	C1—N1—C12	119.14 (13)
C23—C22—C21	121.32 (17)	C1—N1—C13	120.04 (14)
C23—C22—H22	119.3	C12—N1—C13	120.59 (14)
C21—C22—H22	119.3	C7—O1—C6	118.58 (12)
C24—C23—C22	120.74 (18)	C31—P1—C21	100.52 (7)
C24—C23—H23	119.6	C31—P1—C5	102.11 (8)
C22—C23—H23	119.6	C21—P1—C5	101.24 (7)
C23—C24—C25	118.97 (18)	C51—P2—C8	102.00 (8)
C23—C24—H24	120.5	C51—P2—C41	101.66 (8)
C25—C24—H24	120.5	C8—P2—C41	100.58 (7)
C24—C25—C26	120.35 (18)

C6—C1—C2—C3	0.6 (2)	C43—C44—C45—C46	0.2 (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—C45	176.23 (13)
C2—C3—C4—C5	1.4 (3)	C44—C45—C46—C41	0.2 (3)
C3—C4—C5—C6	0.7 (2)	C56—C51—C52—C53	−2.7 (3)
C3—C4—C5—P1	175.10 (13)	P2—C51—C52—C53	175.83 (15)
C4—C5—C6—O1	175.16 (14)	C51—C52—C53—C54	1.9 (3)
P1—C5—C6—O1	0.4 (2)	C52—C53—C54—C55	0.6 (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—C51	1.3 (3)
C2—C1—C6—C5	1.6 (2)	C52—C51—C56—C55	1.1 (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—O1	2.9 (2)	C6—C1—N1—C12	6.2 (2)
O1—C7—C8—C9	−178.47 (14)	C2—C1—N1—C13	−0.9 (2)
C12—C7—C8—C9	0.0 (2)	C6—C1—N1—C13	−179.40 (14)
O1—C7—C8—P2	4.6 (2)	C11—C12—N1—C1	172.78 (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—C10	175.33 (14)	C7—C12—N1—C13	177.40 (14)
C8—C9—C10—C11	0.7 (3)	C14—C13—N1—C1	−80.73 (19)
C9—C10—C11—C12	1.4 (3)	C14—C13—N1—C12	93.60 (19)
C10—C11—C12—C7	−2.7 (2)	C8—C7—O1—C6	−173.86 (14)
C10—C11—C12—N1	176.35 (16)	C12—C7—O1—C6	7.7 (2)
O1—C7—C12—C11	−179.65 (14)	C5—C6—O1—C7	172.70 (14)
C8—C7—C12—C11	2.0 (2)	C1—C6—O1—C7	−9.8 (2)
O1—C7—C12—N1	1.3 (2)	C32—C31—P1—C21	81.38 (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—Cl1	77.1 (5)	C36—C31—P1—C5	161.09 (14)
C13—C14—C15—Br1	78.6 (6)	C26—C21—P1—C31	−17.74 (17)
C26—C21—C22—C23	−0.7 (3)	C22—C21—P1—C31	160.68 (14)
P1—C21—C22—C23	−179.23 (15)	C26—C21—P1—C5	87.00 (16)
C21—C22—C23—C24	1.1 (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—C31	109.61 (15)
C24—C25—C26—C21	0.9 (3)	C6—C5—P1—C21	−179.49 (13)
C22—C21—C26—C25	−0.3 (3)	C4—C5—P1—C21	6.13 (16)
P1—C21—C26—C25	178.11 (15)	C56—C51—P2—C8	−18.19 (16)
C36—C31—C32—C33	1.3 (3)	C52—C51—P2—C8	163.35 (14)
P1—C31—C32—C33	−174.94 (16)	C56—C51—P2—C41	85.44 (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—C36	0.1 (3)	C9—C8—P2—C51	102.50 (15)
C34—C35—C36—C31	1.2 (3)	C7—C8—P2—C41	174.69 (13)
C32—C31—C36—C35	−1.8 (3)	C9—C8—P2—C41	−1.97 (16)
P1—C31—C36—C35	174.67 (16)	C46—C41—P2—C51	−7.91 (16)
C46—C41—C42—C43	−0.1 (3)	C42—C41—P2—C51	168.68 (13)
P2—C41—C42—C43	−176.90 (14)	C46—C41—P2—C8	96.84 (15)
C41—C42—C43—C44	0.5 (3)	C42—C41—P2—C8	−86.57 (14)
C42—C43—C44—C45	−0.6 (3)

Experimental details

Crystal data
Chemical formula	C₃₉H₃₂Br_0.27Cl_0.73NOP₂
M_r	639.83
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	10.0539 (3), 11.4469 (3), 14.5299 (3)
α, β, γ (°)	69.544 (1), 83.283 (2), 81.453 (1)
V (Å³)	1545.52 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.42 × 0.19 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Integration (XPREP; Bruker, 2005)
T_min, T_max	0.792, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	24195, 7458, 5180
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.097, 0.94
No. of reflections	7458
No. of parameters	401
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003) and ORTEP-3 for Windows (Farrugia, 1997).

Acknowledgements

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

References

Bruker (2005). APEX2 and SAINT-NT (includes XPREP). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deprele, S. & Montchamp, J.-L. (2004). Org. Lett. 6, 3805–3808. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Laungani, A. C., Keller, M. & Breit, B. (2008). Acta Cryst. E64, m24–m25. Web of Science CSD CrossRef IUCr Journals Google Scholar
Leeuwen, P. W. N. M. van, Sandee, A. J., Reek, J. N. H. & Kamer, P. C. J. (2002). J. Mol. Catal. A Chem. 182–183, 107–123. Web of Science CrossRef Google Scholar
Marimuthu, T., Bala, M. D. & Friedrich, H. B. (2008). Acta Cryst. E64, o711. Web of Science CSD CrossRef IUCr Journals Google Scholar
Norman, N. C., Orpen, A. G., Quayle, M. J. & Robins, E. G. (2000). Acta Cryst. C56, 50–52. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Osiński, P. W., Schürmann, M., Preut, H., Haag, R. & Eilbracht, P. (2005). Acta Cryst. E61, o3115–o3116. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ricken, S., Osiński, P. W., Eilbracht, P. & Haag, R. (2006). J. Mol. Catal. A Chem. 257, 78–88. Web of Science CrossRef CAS Google Scholar
Ricken, S., Osinski, P. W., Schürmann, M., Preut, H. & Eilbracht, P. (2006a). Acta Cryst. E62, o1807–o1808. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ricken, S., Schürmann, M., Preut, H. & Eilbracht, P. (2006b). Acta Cryst. E62, o2637–o2638. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rotar, A., Varga, R. A. & Silvestru, C. (2008). Acta Cryst. E64, m45. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sandee, A. J., Reek, J. N. H., Kamer, P. C. J. & van Leeuwen, P. W. N. M. (2001). J. Am. Chem. Soc. 123, 8468–8476. Web of Science CrossRef PubMed CAS Google Scholar
Sandee, A. J., van der Veen, L. A., Reek, J. N. H., Kamer, P. C. J., Lutz, M., Spek, A. L. & van Leeuwen, P. W. N. M. (1999). Angew. Chem. Int. Ed. 38, 3231–3235. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Web, P. B., Kunene, T. E. & Cole-Hamilton, D. J. (2005). Green Chem. 7, 373–379. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.