Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004170/fg1596sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004170/fg1596Isup2.hkl |
CCDC reference: 147648
Compound (I) was obtained in the reaction of [Rh(CH{PPh2=N-p-tolyl}2)(COD)] with about 10 equivalents of MeI in benzene (Imhoff et al., 1995). Brown crystals suitable for X-ray diffraction were grown by slow diffusion of hexane into a room temperature solution of the compound in (1:1) benzene-dichloromethane.
X-ray data were collected with a sufficiently large collimator tube to ensure a homogeneous X-ray beam at the crystal by use of a Zr β-filter rather than the graphite monochromator (Alexander & Smith, 1962).
All hydrogen atoms, with the exception of H1 on C1, were constrained and allowed to ride on their carbon atoms with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(methyl). Methyl-H atoms were refined as rigid groups which allow for rotation around the C—C bonds, whilst maintaining a tetrahedral geometry at the C atom. H1 was located from a difference Fourier map and its coordinates allowed to refine with the isotropic displacement parameter constrained to Uiso(H) = 1.2Ueq(C1); the C1—H1 bond length refined to 0.98 (3) Å.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: DIRDIF (Beurskens, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: PLATON.
Fig. 1. Plot of (I) with 30% probability displacement ellipsoids. H atoms have been omitted for clarity. |
C41H41N2P2+·I− | F(000) = 1536 |
Mr = 750.60 | Dx = 1.385 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 13.3126 (5) Å | θ = 14.0–18.0° |
b = 14.3251 (5) Å | µ = 1.01 mm−1 |
c = 18.9767 (7) Å | T = 295 K |
β = 95.819 (3)° | Block, brown |
V = 3600.3 (2) Å3 | 0.40 × 0.30 × 0.13 mm |
Z = 4 |
Enraf Nonius CAD-4F diffractometer | 5992 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.000 |
Graphite monochromator | θmax = 28.0°, θmin = 1.5° |
ω/2θ scans | h = −17→17 |
Absorption correction: ψ scan (North et al., 1968) | k = −18→0 |
Tmin = 0.788, Tmax = 0.877 | l = 0→24 |
8582 measured reflections | 3 standard reflections every 60 min |
8582 independent reflections | intensity decay: 1.0% |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0489P)2 + 3.4354P] where P = (Fo2 + 2Fc2)/3 |
8582 reflections | (Δ/σ)max = 0.003 |
423 parameters | Δρmax = 1.35 e Å−3 |
0 restraints | Δρmin = −0.97 e Å−3 |
C41H41N2P2+·I− | V = 3600.3 (2) Å3 |
Mr = 750.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.3126 (5) Å | µ = 1.01 mm−1 |
b = 14.3251 (5) Å | T = 295 K |
c = 18.9767 (7) Å | 0.40 × 0.30 × 0.13 mm |
β = 95.819 (3)° |
Enraf Nonius CAD-4F diffractometer | 5992 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.788, Tmax = 0.877 | 3 standard reflections every 60 min |
8582 measured reflections | intensity decay: 1.0% |
8582 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.35 e Å−3 |
8582 reflections | Δρmin = −0.97 e Å−3 |
423 parameters |
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 | ||
P1 | 0.70774 (5) | 0.22908 (5) | 0.20870 (4) | 0.03127 (16) | |
P2 | 0.75940 (6) | 0.01665 (5) | 0.21083 (4) | 0.03257 (17) | |
N1 | 0.80742 (19) | 0.29886 (17) | 0.21373 (14) | 0.0379 (6) | |
N2 | 0.66219 (19) | −0.05518 (18) | 0.21320 (14) | 0.0409 (6) | |
C1 | 0.7284 (2) | 0.1223 (2) | 0.17440 (16) | 0.0338 (6) | |
H1 | 0.723 (2) | 0.125 (2) | 0.1224 (17) | 0.037 (9)* | |
C2 | 0.6057 (2) | 0.2817 (2) | 0.15102 (15) | 0.0357 (6) | |
C3 | 0.6031 (3) | 0.3760 (2) | 0.13516 (18) | 0.0472 (8) | |
H3 | 0.6548 | 0.4148 | 0.1544 | 0.057* | |
C4 | 0.5243 (3) | 0.4130 (3) | 0.0910 (2) | 0.0573 (10) | |
H4 | 0.5228 | 0.4767 | 0.0814 | 0.069* | |
C5 | 0.4478 (3) | 0.3565 (3) | 0.06124 (19) | 0.0547 (9) | |
H5 | 0.3952 | 0.3817 | 0.0312 | 0.066* | |
C6 | 0.4496 (2) | 0.2628 (3) | 0.07619 (19) | 0.0527 (9) | |
H6 | 0.3982 | 0.2244 | 0.0560 | 0.063* | |
C7 | 0.5276 (2) | 0.2251 (2) | 0.12108 (17) | 0.0438 (7) | |
H7 | 0.5278 | 0.1616 | 0.1313 | 0.053* | |
C8 | 0.6730 (2) | 0.2260 (2) | 0.29823 (16) | 0.0370 (6) | |
C9 | 0.5745 (2) | 0.2077 (2) | 0.31212 (19) | 0.0468 (8) | |
H9 | 0.5240 | 0.2004 | 0.2750 | 0.056* | |
C10 | 0.5518 (3) | 0.2004 (3) | 0.3817 (2) | 0.0610 (10) | |
H10 | 0.4862 | 0.1868 | 0.3911 | 0.073* | |
C11 | 0.6258 (3) | 0.2131 (3) | 0.4366 (2) | 0.0651 (11) | |
H11 | 0.6099 | 0.2089 | 0.4831 | 0.078* | |
C12 | 0.7230 (3) | 0.2319 (3) | 0.42324 (19) | 0.0572 (9) | |
H12 | 0.7728 | 0.2405 | 0.4607 | 0.069* | |
C13 | 0.7473 (3) | 0.2379 (3) | 0.35474 (18) | 0.0473 (8) | |
H13 | 0.8135 | 0.2500 | 0.3460 | 0.057* | |
C14 | 0.8098 (3) | 0.3909 (2) | 0.2490 (2) | 0.0502 (8) | |
H14A | 0.8680 | 0.3945 | 0.2832 | 0.075* | |
H14B | 0.7498 | 0.3988 | 0.2724 | 0.075* | |
H14C | 0.8134 | 0.4392 | 0.2143 | 0.075* | |
C15 | 0.8963 (2) | 0.2792 (2) | 0.17885 (16) | 0.0363 (6) | |
C16 | 0.9005 (3) | 0.2991 (2) | 0.10848 (18) | 0.0465 (8) | |
H16 | 0.8435 | 0.3218 | 0.0815 | 0.056* | |
C17 | 0.9891 (3) | 0.2855 (3) | 0.0775 (2) | 0.0547 (9) | |
H17 | 0.9905 | 0.2979 | 0.0295 | 0.066* | |
C18 | 1.0759 (3) | 0.2539 (3) | 0.1168 (2) | 0.0531 (9) | |
C19 | 1.0706 (2) | 0.2334 (3) | 0.1875 (2) | 0.0526 (9) | |
H19 | 1.1274 | 0.2103 | 0.2145 | 0.063* | |
C20 | 0.9822 (2) | 0.2467 (2) | 0.21863 (18) | 0.0462 (8) | |
H20 | 0.9804 | 0.2338 | 0.2665 | 0.055* | |
C21 | 1.1731 (3) | 0.2429 (4) | 0.0831 (3) | 0.0810 (14) | |
H21A | 1.2263 | 0.2253 | 0.1186 | 0.121* | |
H21B | 1.1900 | 0.3009 | 0.0619 | 0.121* | |
H21C | 1.1649 | 0.1953 | 0.0473 | 0.121* | |
C22 | 0.6704 (3) | −0.1469 (2) | 0.2488 (2) | 0.0503 (8) | |
H22A | 0.6196 | −0.1519 | 0.2811 | 0.076* | |
H22B | 0.7360 | −0.1530 | 0.2744 | 0.076* | |
H22C | 0.6609 | −0.1956 | 0.2139 | 0.076* | |
C23 | 0.5665 (2) | −0.0399 (2) | 0.17224 (18) | 0.0410 (7) | |
C24 | 0.5508 (3) | −0.0704 (3) | 0.1033 (2) | 0.0578 (10) | |
H24 | 0.6035 | −0.0977 | 0.0821 | 0.069* | |
C25 | 0.4572 (4) | −0.0607 (3) | 0.0655 (3) | 0.0753 (13) | |
H25 | 0.4477 | −0.0822 | 0.0191 | 0.090* | |
C26 | 0.3786 (3) | −0.0205 (3) | 0.0946 (3) | 0.0736 (13) | |
C27 | 0.3935 (3) | 0.0104 (3) | 0.1639 (3) | 0.0727 (14) | |
H27 | 0.3407 | 0.0386 | 0.1844 | 0.087* | |
C28 | 0.4882 (3) | −0.0005 (3) | 0.2035 (2) | 0.0540 (9) | |
H28 | 0.4975 | 0.0187 | 0.2505 | 0.065* | |
C29 | 0.2744 (4) | −0.0103 (4) | 0.0527 (4) | 0.121 (3) | |
H29A | 0.2238 | −0.0042 | 0.0850 | 0.182* | |
H29B | 0.2605 | −0.0645 | 0.0236 | 0.182* | |
H29C | 0.2738 | 0.0442 | 0.0232 | 0.182* | |
C30 | 0.8141 (2) | 0.0214 (2) | 0.30156 (16) | 0.0370 (6) | |
C31 | 0.7527 (2) | 0.0092 (2) | 0.35614 (17) | 0.0445 (8) | |
H31 | 0.6841 | −0.0022 | 0.3453 | 0.053* | |
C32 | 0.7924 (3) | 0.0138 (3) | 0.42560 (19) | 0.0535 (9) | |
H32 | 0.7512 | 0.0047 | 0.4618 | 0.064* | |
C33 | 0.8939 (3) | 0.0320 (3) | 0.4415 (2) | 0.0604 (10) | |
H33 | 0.9208 | 0.0354 | 0.4886 | 0.072* | |
C34 | 0.9558 (3) | 0.0453 (3) | 0.3885 (2) | 0.0619 (10) | |
H34 | 1.0239 | 0.0589 | 0.3997 | 0.074* | |
C35 | 0.9164 (3) | 0.0382 (3) | 0.31857 (19) | 0.0488 (8) | |
H35 | 0.9586 | 0.0446 | 0.2827 | 0.059* | |
C36 | 0.8512 (2) | −0.0341 (2) | 0.15745 (16) | 0.0370 (6) | |
C37 | 0.8521 (3) | −0.1285 (2) | 0.14133 (19) | 0.0479 (8) | |
H37 | 0.8040 | −0.1680 | 0.1575 | 0.057* | |
C38 | 0.9246 (3) | −0.1641 (3) | 0.1012 (2) | 0.0552 (9) | |
H38 | 0.9245 | −0.2274 | 0.0904 | 0.066* | |
C39 | 0.9959 (3) | −0.1072 (3) | 0.0773 (2) | 0.0552 (9) | |
H39 | 1.0448 | −0.1318 | 0.0510 | 0.066* | |
C40 | 0.9954 (3) | −0.0128 (3) | 0.0924 (2) | 0.0536 (9) | |
H40 | 1.0437 | 0.0261 | 0.0758 | 0.064* | |
C41 | 0.9233 (2) | 0.0238 (2) | 0.13203 (18) | 0.0456 (8) | |
H41 | 0.9230 | 0.0875 | 0.1418 | 0.055* | |
I1 | 0.25447 (2) | 0.118402 (18) | 0.374177 (18) | 0.06976 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0296 (3) | 0.0310 (4) | 0.0334 (4) | −0.0001 (3) | 0.0038 (3) | 0.0016 (3) |
P2 | 0.0316 (4) | 0.0300 (4) | 0.0361 (4) | −0.0014 (3) | 0.0031 (3) | 0.0027 (3) |
N1 | 0.0360 (13) | 0.0341 (13) | 0.0443 (15) | −0.0055 (10) | 0.0079 (11) | −0.0045 (11) |
N2 | 0.0391 (14) | 0.0345 (13) | 0.0479 (16) | −0.0073 (11) | −0.0013 (12) | 0.0083 (12) |
C1 | 0.0397 (15) | 0.0308 (14) | 0.0312 (15) | −0.0012 (12) | 0.0045 (12) | 0.0012 (12) |
C2 | 0.0330 (15) | 0.0385 (16) | 0.0357 (16) | 0.0046 (12) | 0.0042 (12) | 0.0035 (13) |
C3 | 0.053 (2) | 0.0397 (17) | 0.0476 (19) | 0.0025 (15) | −0.0005 (15) | 0.0005 (15) |
C4 | 0.073 (3) | 0.0448 (19) | 0.054 (2) | 0.0216 (18) | 0.0020 (19) | 0.0064 (17) |
C5 | 0.046 (2) | 0.073 (3) | 0.044 (2) | 0.0239 (18) | 0.0006 (15) | 0.0064 (18) |
C6 | 0.0337 (17) | 0.076 (3) | 0.048 (2) | 0.0008 (17) | 0.0028 (14) | 0.0008 (19) |
C7 | 0.0369 (16) | 0.0465 (18) | 0.0476 (19) | −0.0034 (14) | 0.0019 (14) | 0.0062 (15) |
C8 | 0.0412 (16) | 0.0355 (15) | 0.0354 (16) | 0.0041 (13) | 0.0097 (12) | 0.0029 (13) |
C9 | 0.0400 (17) | 0.0498 (19) | 0.052 (2) | 0.0025 (14) | 0.0130 (15) | 0.0007 (16) |
C10 | 0.056 (2) | 0.063 (2) | 0.070 (3) | 0.0041 (18) | 0.034 (2) | 0.005 (2) |
C11 | 0.085 (3) | 0.071 (3) | 0.043 (2) | 0.011 (2) | 0.025 (2) | 0.0062 (19) |
C12 | 0.070 (2) | 0.061 (2) | 0.041 (2) | 0.010 (2) | 0.0061 (17) | 0.0005 (17) |
C13 | 0.0478 (19) | 0.052 (2) | 0.0423 (19) | 0.0054 (15) | 0.0054 (15) | 0.0017 (15) |
C14 | 0.054 (2) | 0.0400 (18) | 0.057 (2) | −0.0055 (15) | 0.0044 (16) | −0.0102 (16) |
C15 | 0.0354 (15) | 0.0340 (15) | 0.0398 (17) | −0.0073 (12) | 0.0054 (12) | −0.0020 (13) |
C16 | 0.0474 (19) | 0.0497 (19) | 0.0426 (19) | 0.0013 (15) | 0.0056 (15) | 0.0033 (15) |
C17 | 0.063 (2) | 0.059 (2) | 0.045 (2) | −0.0047 (18) | 0.0218 (17) | 0.0001 (17) |
C18 | 0.0428 (19) | 0.048 (2) | 0.071 (3) | −0.0139 (15) | 0.0190 (18) | −0.0149 (18) |
C19 | 0.0336 (17) | 0.057 (2) | 0.066 (2) | −0.0023 (15) | −0.0033 (15) | −0.0047 (19) |
C20 | 0.0419 (17) | 0.051 (2) | 0.0444 (19) | −0.0077 (15) | −0.0015 (14) | 0.0031 (15) |
C21 | 0.054 (2) | 0.084 (3) | 0.110 (4) | −0.012 (2) | 0.037 (2) | −0.028 (3) |
C22 | 0.054 (2) | 0.0398 (17) | 0.057 (2) | −0.0089 (15) | 0.0052 (17) | 0.0140 (16) |
C23 | 0.0357 (16) | 0.0365 (16) | 0.0507 (19) | −0.0097 (13) | 0.0035 (14) | 0.0059 (14) |
C24 | 0.049 (2) | 0.067 (2) | 0.057 (2) | −0.0077 (18) | 0.0013 (17) | −0.0022 (19) |
C25 | 0.070 (3) | 0.079 (3) | 0.071 (3) | −0.018 (2) | −0.020 (2) | 0.008 (2) |
C26 | 0.048 (2) | 0.060 (3) | 0.107 (4) | −0.016 (2) | −0.019 (2) | 0.024 (3) |
C27 | 0.040 (2) | 0.050 (2) | 0.131 (4) | −0.0030 (17) | 0.023 (2) | 0.020 (3) |
C28 | 0.0472 (19) | 0.047 (2) | 0.070 (2) | −0.0072 (16) | 0.0164 (17) | 0.0025 (18) |
C29 | 0.064 (3) | 0.095 (4) | 0.191 (7) | −0.015 (3) | −0.053 (4) | 0.048 (4) |
C30 | 0.0391 (16) | 0.0339 (15) | 0.0372 (16) | 0.0002 (12) | −0.0006 (12) | 0.0040 (13) |
C31 | 0.0447 (18) | 0.0458 (18) | 0.0427 (19) | −0.0016 (14) | 0.0027 (14) | 0.0048 (14) |
C32 | 0.065 (2) | 0.054 (2) | 0.0416 (19) | 0.0023 (18) | 0.0067 (17) | 0.0080 (16) |
C33 | 0.074 (3) | 0.062 (2) | 0.042 (2) | 0.006 (2) | −0.0112 (18) | 0.0049 (18) |
C34 | 0.045 (2) | 0.071 (3) | 0.065 (3) | −0.0003 (18) | −0.0173 (18) | 0.006 (2) |
C35 | 0.0400 (17) | 0.054 (2) | 0.051 (2) | −0.0003 (15) | −0.0028 (15) | 0.0069 (16) |
C36 | 0.0390 (16) | 0.0356 (15) | 0.0363 (16) | 0.0009 (12) | 0.0034 (12) | 0.0003 (13) |
C37 | 0.058 (2) | 0.0364 (17) | 0.050 (2) | −0.0002 (15) | 0.0091 (16) | 0.0016 (15) |
C38 | 0.074 (3) | 0.0399 (19) | 0.053 (2) | 0.0108 (18) | 0.0135 (19) | −0.0061 (16) |
C39 | 0.055 (2) | 0.064 (2) | 0.049 (2) | 0.0109 (18) | 0.0169 (17) | −0.0051 (18) |
C40 | 0.0468 (19) | 0.059 (2) | 0.058 (2) | −0.0022 (17) | 0.0166 (16) | −0.0003 (18) |
C41 | 0.0446 (18) | 0.0398 (17) | 0.054 (2) | −0.0013 (14) | 0.0121 (15) | −0.0017 (15) |
I1 | 0.06647 (18) | 0.04617 (15) | 0.0939 (2) | 0.00539 (12) | −0.00543 (15) | −0.00224 (14) |
P1—N1 | 1.656 (3) | C21—H21A | 0.9600 |
P1—C1 | 1.696 (3) | C21—H21B | 0.9600 |
P1—C8 | 1.806 (3) | C21—H21C | 0.9600 |
P1—C2 | 1.820 (3) | C22—H22A | 0.9600 |
P2—N2 | 1.658 (3) | C22—H22B | 0.9600 |
P2—C1 | 1.697 (3) | C22—H22C | 0.9600 |
P2—C30 | 1.801 (3) | C23—C28 | 1.372 (5) |
P2—C36 | 1.816 (3) | C23—C24 | 1.375 (5) |
N1—C15 | 1.441 (4) | C24—C25 | 1.380 (6) |
N1—C14 | 1.477 (4) | C24—H24 | 0.9300 |
N2—C23 | 1.440 (4) | C25—C26 | 1.360 (7) |
N2—C22 | 1.477 (4) | C25—H25 | 0.9300 |
C1—H1 | 0.98 (3) | C26—C27 | 1.381 (7) |
C2—C3 | 1.384 (4) | C26—C29 | 1.534 (6) |
C2—C7 | 1.393 (4) | C27—C28 | 1.410 (6) |
C3—C4 | 1.380 (5) | C27—H27 | 0.9300 |
C3—H3 | 0.9300 | C28—H28 | 0.9300 |
C4—C5 | 1.377 (6) | C29—H29A | 0.9600 |
C4—H4 | 0.9300 | C29—H29B | 0.9600 |
C5—C6 | 1.371 (5) | C29—H29C | 0.9600 |
C5—H5 | 0.9300 | C30—C35 | 1.389 (4) |
C6—C7 | 1.384 (5) | C30—C31 | 1.394 (4) |
C6—H6 | 0.9300 | C31—C32 | 1.371 (5) |
C7—H7 | 0.9300 | C31—H31 | 0.9300 |
C8—C9 | 1.387 (4) | C32—C33 | 1.379 (5) |
C8—C13 | 1.394 (4) | C32—H32 | 0.9300 |
C9—C10 | 1.388 (5) | C33—C34 | 1.377 (6) |
C9—H9 | 0.9300 | C33—H33 | 0.9300 |
C10—C11 | 1.371 (6) | C34—C35 | 1.380 (5) |
C10—H10 | 0.9300 | C34—H34 | 0.9300 |
C11—C12 | 1.370 (6) | C35—H35 | 0.9300 |
C11—H11 | 0.9300 | C36—C37 | 1.387 (4) |
C12—C13 | 1.374 (5) | C36—C41 | 1.392 (4) |
C12—H12 | 0.9300 | C37—C38 | 1.385 (5) |
C13—H13 | 0.9300 | C37—H37 | 0.9300 |
C14—H14A | 0.9600 | C38—C39 | 1.363 (5) |
C14—H14B | 0.9600 | C38—H38 | 0.9300 |
C14—H14C | 0.9600 | C39—C40 | 1.382 (5) |
C15—C16 | 1.372 (4) | C39—H39 | 0.9300 |
C15—C20 | 1.384 (4) | C40—C41 | 1.382 (5) |
C16—C17 | 1.384 (5) | C40—H40 | 0.9300 |
C16—H16 | 0.9300 | C41—H41 | 0.9300 |
C17—C18 | 1.387 (5) | P1—P2 | 3.1192 (11) |
C17—H17 | 0.9300 | P1—N2 | 4.119 (3) |
C18—C19 | 1.382 (5) | P2—N1 | 4.092 (3) |
C18—C21 | 1.509 (5) | N1—C1 | 2.812 (4) |
C19—C20 | 1.383 (5) | N1—N2 | 5.427 (3) |
C19—H19 | 0.9300 | N2—C1 | 2.813 (4) |
C20—H20 | 0.9300 | ||
N1—P1—C1 | 113.99 (14) | C19—C20—C15 | 120.3 (3) |
N1—P1—C8 | 103.94 (14) | C19—C20—H20 | 119.9 |
C1—P1—C8 | 113.95 (14) | C15—C20—H20 | 119.9 |
N1—P1—C2 | 109.26 (14) | C18—C21—H21A | 109.5 |
C1—P1—C2 | 106.43 (14) | C18—C21—H21B | 109.5 |
C8—P1—C2 | 109.20 (14) | H21A—C21—H21B | 109.5 |
N2—P2—C1 | 113.96 (14) | C18—C21—H21C | 109.5 |
N2—P2—C30 | 103.81 (14) | H21A—C21—H21C | 109.5 |
C1—P2—C30 | 114.43 (14) | H21B—C21—H21C | 109.5 |
N2—P2—C36 | 109.75 (14) | N2—C22—H22A | 109.5 |
C1—P2—C36 | 106.21 (15) | N2—C22—H22B | 109.5 |
C30—P2—C36 | 108.60 (14) | H22A—C22—H22B | 109.5 |
C15—N1—C14 | 113.7 (2) | N2—C22—H22C | 109.5 |
C15—N1—P1 | 123.1 (2) | H22A—C22—H22C | 109.5 |
C14—N1—P1 | 123.0 (2) | H22B—C22—H22C | 109.5 |
C23—N2—C22 | 113.7 (2) | C28—C23—C24 | 119.6 (3) |
C23—N2—P2 | 122.8 (2) | C28—C23—N2 | 119.9 (3) |
C22—N2—P2 | 122.9 (2) | C24—C23—N2 | 120.4 (3) |
P1—C1—P2 | 133.64 (19) | C23—C24—C25 | 120.3 (4) |
C3—C2—C7 | 118.6 (3) | C23—C24—H24 | 119.9 |
C3—C2—P1 | 122.4 (2) | C25—C24—H24 | 119.9 |
C7—C2—P1 | 119.0 (2) | C26—C25—C24 | 121.5 (5) |
C4—C3—C2 | 120.5 (3) | C26—C25—H25 | 119.2 |
C4—C3—H3 | 119.7 | C24—C25—H25 | 119.2 |
C2—C3—H3 | 119.7 | C25—C26—C27 | 118.7 (4) |
C5—C4—C3 | 120.6 (3) | C25—C26—C29 | 121.5 (6) |
C5—C4—H4 | 119.7 | C27—C26—C29 | 119.9 (5) |
C3—C4—H4 | 119.7 | C26—C27—C28 | 120.4 (4) |
C6—C5—C4 | 119.6 (3) | C26—C27—H27 | 119.8 |
C6—C5—H5 | 120.2 | C28—C27—H27 | 119.8 |
C4—C5—H5 | 120.2 | C23—C28—C27 | 119.5 (4) |
C5—C6—C7 | 120.4 (4) | C23—C28—H28 | 120.3 |
C5—C6—H6 | 119.8 | C27—C28—H28 | 120.3 |
C7—C6—H6 | 119.8 | C26—C29—H29A | 109.5 |
C6—C7—C2 | 120.4 (3) | C26—C29—H29B | 109.5 |
C6—C7—H7 | 119.8 | H29A—C29—H29B | 109.5 |
C2—C7—H7 | 119.8 | C26—C29—H29C | 109.5 |
C9—C8—C13 | 119.2 (3) | H29A—C29—H29C | 109.5 |
C9—C8—P1 | 121.4 (3) | H29B—C29—H29C | 109.5 |
C13—C8—P1 | 119.4 (2) | C35—C30—C31 | 119.0 (3) |
C8—C9—C10 | 119.7 (3) | C35—C30—P2 | 121.4 (3) |
C8—C9—H9 | 120.1 | C31—C30—P2 | 119.6 (2) |
C10—C9—H9 | 120.1 | C32—C31—C30 | 120.7 (3) |
C11—C10—C9 | 120.2 (4) | C32—C31—H31 | 119.7 |
C11—C10—H10 | 119.9 | C30—C31—H31 | 119.7 |
C9—C10—H10 | 119.9 | C31—C32—C33 | 119.5 (3) |
C12—C11—C10 | 120.4 (4) | C31—C32—H32 | 120.2 |
C12—C11—H11 | 119.8 | C33—C32—H32 | 120.2 |
C10—C11—H11 | 119.8 | C34—C33—C32 | 120.8 (3) |
C11—C12—C13 | 120.3 (4) | C34—C33—H33 | 119.6 |
C11—C12—H12 | 119.9 | C32—C33—H33 | 119.6 |
C13—C12—H12 | 119.9 | C33—C34—C35 | 119.6 (4) |
C12—C13—C8 | 120.2 (3) | C33—C34—H34 | 120.2 |
C12—C13—H13 | 119.9 | C35—C34—H34 | 120.2 |
C8—C13—H13 | 119.9 | C34—C35—C30 | 120.3 (3) |
N1—C14—H14A | 109.5 | C34—C35—H35 | 119.8 |
N1—C14—H14B | 109.5 | C30—C35—H35 | 119.8 |
H14A—C14—H14B | 109.5 | C37—C36—C41 | 118.9 (3) |
N1—C14—H14C | 109.5 | C37—C36—P2 | 122.4 (2) |
H14A—C14—H14C | 109.5 | C41—C36—P2 | 118.8 (2) |
H14B—C14—H14C | 109.5 | C38—C37—C36 | 120.2 (3) |
C16—C15—C20 | 119.2 (3) | C38—C37—H37 | 119.9 |
C16—C15—N1 | 121.5 (3) | C36—C37—H37 | 119.9 |
C20—C15—N1 | 119.1 (3) | C39—C38—C37 | 120.6 (3) |
C15—C16—C17 | 120.3 (3) | C39—C38—H38 | 119.7 |
C15—C16—H16 | 119.8 | C37—C38—H38 | 119.7 |
C17—C16—H16 | 119.8 | C38—C39—C40 | 119.9 (3) |
C16—C17—C18 | 121.1 (3) | C38—C39—H39 | 120.1 |
C16—C17—H17 | 119.4 | C40—C39—H39 | 120.1 |
C18—C17—H17 | 119.4 | C39—C40—C41 | 120.2 (3) |
C19—C18—C17 | 118.0 (3) | C39—C40—H40 | 119.9 |
C19—C18—C21 | 121.3 (4) | C41—C40—H40 | 119.9 |
C17—C18—C21 | 120.7 (4) | C40—C41—C36 | 120.2 (3) |
C18—C19—C20 | 121.0 (3) | C40—C41—H41 | 119.9 |
C18—C19—H19 | 119.5 | C36—C41—H41 | 119.9 |
C20—C19—H19 | 119.5 | ||
C1—P1—N1—C15 | 12.6 (3) | N1—C15—C16—C17 | 175.5 (3) |
C8—P1—N1—C15 | 137.2 (2) | C15—C16—C17—C18 | −1.5 (6) |
C2—P1—N1—C15 | −106.3 (3) | C16—C17—C18—C19 | 2.0 (6) |
C1—P1—N1—C14 | −173.1 (3) | C16—C17—C18—C21 | −177.7 (4) |
C8—P1—N1—C14 | −48.4 (3) | C17—C18—C19—C20 | −1.9 (5) |
C2—P1—N1—C14 | 68.0 (3) | C21—C18—C19—C20 | 177.8 (4) |
C1—P2—N2—C23 | 15.4 (3) | C18—C19—C20—C15 | 1.4 (5) |
C30—P2—N2—C23 | 140.6 (3) | C16—C15—C20—C19 | −0.9 (5) |
C36—P2—N2—C23 | −103.5 (3) | N1—C15—C20—C19 | −175.5 (3) |
C1—P2—N2—C22 | −174.0 (3) | C22—N2—C23—C28 | 89.4 (4) |
C30—P2—N2—C22 | −48.8 (3) | P2—N2—C23—C28 | −99.2 (3) |
C36—P2—N2—C22 | 67.1 (3) | C22—N2—C23—C24 | −86.0 (4) |
N1—P1—C1—P2 | 96.4 (3) | P2—N2—C23—C24 | 85.4 (4) |
C8—P1—C1—P2 | −22.7 (3) | C28—C23—C24—C25 | 0.7 (6) |
C2—P1—C1—P2 | −143.1 (2) | N2—C23—C24—C25 | 176.1 (3) |
N2—P2—C1—P1 | 99.8 (3) | C23—C24—C25—C26 | 0.5 (7) |
C30—P2—C1—P1 | −19.5 (3) | C24—C25—C26—C27 | −0.5 (7) |
C36—P2—C1—P1 | −139.3 (2) | C24—C25—C26—C29 | −179.6 (4) |
N1—P1—C2—C3 | −19.6 (3) | C25—C26—C27—C28 | −0.6 (6) |
C1—P1—C2—C3 | −143.1 (3) | C29—C26—C27—C28 | 178.5 (4) |
C8—P1—C2—C3 | 93.5 (3) | C24—C23—C28—C27 | −1.8 (5) |
N1—P1—C2—C7 | 159.9 (2) | N2—C23—C28—C27 | −177.3 (3) |
C1—P1—C2—C7 | 36.4 (3) | C26—C27—C28—C23 | 1.8 (6) |
C8—P1—C2—C7 | −87.1 (3) | N2—P2—C30—C35 | 151.2 (3) |
C7—C2—C3—C4 | 0.5 (5) | C1—P2—C30—C35 | −83.9 (3) |
P1—C2—C3—C4 | 179.9 (3) | C36—P2—C30—C35 | 34.5 (3) |
C2—C3—C4—C5 | −1.0 (6) | N2—P2—C30—C31 | −29.5 (3) |
C3—C4—C5—C6 | 0.6 (6) | C1—P2—C30—C31 | 95.3 (3) |
C4—C5—C6—C7 | 0.2 (6) | C36—P2—C30—C31 | −146.2 (3) |
C5—C6—C7—C2 | −0.7 (5) | C35—C30—C31—C32 | 0.2 (5) |
C3—C2—C7—C6 | 0.4 (5) | P2—C30—C31—C32 | −179.1 (3) |
P1—C2—C7—C6 | −179.1 (3) | C30—C31—C32—C33 | 0.9 (5) |
N1—P1—C8—C9 | 153.9 (3) | C31—C32—C33—C34 | −0.3 (6) |
C1—P1—C8—C9 | −81.4 (3) | C32—C33—C34—C35 | −1.4 (6) |
C2—P1—C8—C9 | 37.4 (3) | C33—C34—C35—C30 | 2.5 (6) |
N1—P1—C8—C13 | −29.1 (3) | C31—C30—C35—C34 | −1.9 (5) |
C1—P1—C8—C13 | 95.5 (3) | P2—C30—C35—C34 | 177.4 (3) |
C2—P1—C8—C13 | −145.7 (3) | N2—P2—C36—C37 | −18.2 (3) |
C13—C8—C9—C10 | −0.8 (5) | C1—P2—C36—C37 | −141.8 (3) |
P1—C8—C9—C10 | 176.2 (3) | C30—P2—C36—C37 | 94.7 (3) |
C8—C9—C10—C11 | 1.4 (6) | N2—P2—C36—C41 | 162.1 (2) |
C9—C10—C11—C12 | −0.9 (6) | C1—P2—C36—C41 | 38.4 (3) |
C10—C11—C12—C13 | −0.1 (6) | C30—P2—C36—C41 | −85.1 (3) |
C11—C12—C13—C8 | 0.7 (6) | C41—C36—C37—C38 | 0.6 (5) |
C9—C8—C13—C12 | −0.2 (5) | P2—C36—C37—C38 | −179.1 (3) |
P1—C8—C13—C12 | −177.2 (3) | C36—C37—C38—C39 | 0.3 (6) |
C14—N1—C15—C16 | −93.3 (4) | C37—C38—C39—C40 | −0.9 (6) |
P1—N1—C15—C16 | 81.6 (4) | C38—C39—C40—C41 | 0.5 (6) |
C14—N1—C15—C20 | 81.3 (4) | C39—C40—C41—C36 | 0.4 (6) |
P1—N1—C15—C20 | −103.9 (3) | C37—C36—C41—C40 | −1.0 (5) |
C20—C15—C16—C17 | 0.9 (5) | P2—C36—C41—C40 | 178.8 (3) |
Experimental details
Crystal data | |
Chemical formula | C41H41N2P2+·I− |
Mr | 750.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 13.3126 (5), 14.3251 (5), 18.9767 (7) |
β (°) | 95.819 (3) |
V (Å3) | 3600.3 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.01 |
Crystal size (mm) | 0.40 × 0.30 × 0.13 |
Data collection | |
Diffractometer | Enraf Nonius CAD-4F diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.788, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8582, 8582, 5992 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.121, 1.03 |
No. of reflections | 8582 |
No. of parameters | 423 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.35, −0.97 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), SET4 (de Boer & Duisenberg, 1984), HELENA (Spek, 1997), DIRDIF (Beurskens, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), PLATON.
P1—N1 | 1.656 (3) | P2—C30 | 1.801 (3) |
P1—C1 | 1.696 (3) | P2—C36 | 1.816 (3) |
P1—C8 | 1.806 (3) | N1—C15 | 1.441 (4) |
P1—C2 | 1.820 (3) | N1—C14 | 1.477 (4) |
P2—N2 | 1.658 (3) | N2—C23 | 1.440 (4) |
P2—C1 | 1.697 (3) | N2—C22 | 1.477 (4) |
N1—P1—C1 | 113.99 (14) | C1—P2—C36 | 106.21 (15) |
N1—P1—C8 | 103.94 (14) | C30—P2—C36 | 108.60 (14) |
C1—P1—C8 | 113.95 (14) | C15—N1—C14 | 113.7 (2) |
N1—P1—C2 | 109.26 (14) | C15—N1—P1 | 123.1 (2) |
C1—P1—C2 | 106.43 (14) | C14—N1—P1 | 123.0 (2) |
C8—P1—C2 | 109.20 (14) | C23—N2—C22 | 113.7 (2) |
N2—P2—C1 | 113.96 (14) | C23—N2—P2 | 122.8 (2) |
N2—P2—C30 | 103.81 (14) | C22—N2—P2 | 122.9 (2) |
C1—P2—C30 | 114.43 (14) | P1—C1—P2 | 133.64 (19) |
N2—P2—C36 | 109.75 (14) |
The amino-[(R2P-NXR')CR"] and iminophosphoranyl ligands [(R2P=NR')CXR"] are essentially tautomeric forms, their basicity and reactivity altered by changing the groups at either phosphorus (R = Me, Ph), nitrogen (X = H, Me; R' = H, Me, Ph, C6H4Y-4 where Y = Me, NO2) or methylide carbon (R" = H, Me, SiMe3). The iminophosphoranyl ligands and their mono-anions, are known to coordinate in various forms to electron rich metals such as RhI, IrI, PdII and PtII. They donate one, two or four electrons to the metal centre, ligating via nitrogen and methylide carbon atoms, producing chelating, ylid and terdentate species (Avis et al., 1995; Imhoff et al., 1991, 1995).
The title compound, (I), was unexpectedly synthesized in the reaction of [Rh(CH{PPh2=N-p-tolyl}2)(COD)] with MeI, involving formation of [Rh(COD)I]2 and the transfer of Me groups to nitrogen. The formation of the discrete cation-anion pair, shown in Figure 1, is distinct from a similar reaction of [Rh(CH{PPh2=N-p-tolyl}2)(COD)] with HCl (Imhoff et al., 1995) which resulted in protonation at one N and the methanide C. The cationic ligand (I) consists of two (N-methyl-N-p-tolylamino)diphenylphosphoranyl units attached via the phosphorus to a common methylide moiety. The P—N bond distances [1.656 (3) and 1.657 (3) Å] are typical of those found in aminophosphonium groups of metal complexes (Avis, et al., 1995, 1997; Imhoff, et al., 1989, 1993), but are significantly longer than those found in iminophosphoranyl ligands such as (Ph2P=NC6H4Me-4)2CH2 (Imhoff, et al., 1990) and (Ph2P=NC6H4Me-4)2CHMe (Avis et al., 1996). The P—N bond characteristics in these imino species were attributed to a p π (N) − d π (P) interaction. The nitrogen atoms in (I) are also sp2 hybridized but planar (nitrogen bond angles given in Table 1), producing little or no overlap between the nitrogen lone pair and the phosphorus d orbital. Both phosphorus atoms exhibit distorted tetrahedral geometries, with angles ranging from 103.96 (14)–114.01 (14)° around P1, and 103.84 (14)–114.40 (15)° for P2. \sch
The N—C and P—C(Ph) bond distances are in good agreement with values observed in related systems. The P—C(H) distances of 1.696 (3) and 1.697 (3) Å are comparable to those found in the [Ph3P=CH-PPh3]+ cation (Carroll & Titus, 1977), Na[PhCHPPh2CHPPh2] (Schmidbaur et al., 1980) and (MeSi)2CPh2-CHPPh2CH(MeSi)2 (Appel et al., 1984). These values lie between those expected for single and double P—C bonds, resulting in partial double-bond characteristics. The molecule possesses non-crystallographic C2-symmetry, considering the equivalence of bond lengths and bond angles around the N—P—C—P—N core. The puckering of the P—C—P component leads to a distorted trigonal geometry at C1, P1—C1—P2 = 133.0 (4)°, and reduces the overall symmetry to C1. The widening of this angle from the ideal 120° is possibly caused by steric repulsions between adjacent phenyl groups on the phosphorus atoms.
Only the P—C(H)—P distances have non-integral bond orders so presumably the charge is localized within the P—C—P component, as depicted by the mesomeric structure in the chemical scheme. Further delocalization, over the whole N—P—C—P—N skeleton, is precluded because of the non-planar arrangement of the atoms. The diffuse nature of the positive charge, and possibly steric hindrance, isolates the iodide anion from the cation. The shortest contacts between the iodide and adjacent aminophosphoranyl molecules involves interactions with methyl or phenyl H atoms: I1···H14Ci [3.15 Å], I1···H37ii [3.20 Å] and I1···H10 of 3.22 Å, [Symmetry codes: (i) 1 − x, −1/2 + y, 1/2 − z, (ii) 1 − x, 1/2 + y, 1/2 − z].