organic compounds
Substitutional disorder in the substituted nixantphos ligand C39H32Br0.27Cl0.73NOP2
aSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
*Correspondence e-mail: bala@ukzn.ac.za
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.
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
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Data collection: APEX2 (Bruker, 2005); cell 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
10.1107/S1600536808007848/pv2073sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808007848/pv2073Isup2.hkl
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.).
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.
Data collection: APEX2 (Bruker, 2005); cell
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).Fig. 1. Molecular structure of (I) with thermal ellipsoids shown at 50% probability levels. |
C39H32Br0.27Cl0.73NOP2 | Z = 2 |
Mr = 639.83 | F(000) = 665.6 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII CCD area-detector diffractometer | 7458 independent reflections |
Radiation source: fine-focus sealed tube | 5180 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.5° |
Absorption correction: integration (XPREP; Bruker, 2005) | h = −13→12 |
Tmin = 0.792, Tmax = 0.908 | k = −15→15 |
24195 measured reflections | l = −17→19 |
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(Fo2) + (0.0499P)2] where P = (Fo2 + 2Fc2)/3 |
7458 reflections | (Δ/σ)max = 0.006 |
401 parameters | Δρmax = 0.36 e Å−3 |
2 restraints | Δρmin = −0.28 e Å−3 |
C39H32Br0.27Cl0.73NOP2 | γ = 81.453 (1)° |
Mr = 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)° |
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 = 0.908 | Rint = 0.051 |
24195 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 2 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.36 e Å−3 |
7458 reflections | Δρmin = −0.28 e Å−3 |
401 parameters |
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. |
x | y | z | Uiso*/Ueq | 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) |
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) |
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 | C39H32Br0.27Cl0.73NOP2 |
Mr | 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) |
Tmin, Tmax | 0.792, 0.908 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24195, 7458, 5180 |
Rint | 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 |
Δρmax, Δρmin (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
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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.
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.