Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104014908/jz1629sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014908/jz1629Isup2.hkl |
CCDC reference: 248131
The title compound was prepared according to a modified version of the published procedure of Sollot & Howard (1962). Ferrocene (30 g, 0.16 mol) and freshly sublimed AlCl3 (4.33 g, 0.032 mol) were added to degassed heptane (100 ml), in a vessel equipped with a reflux condenser and a dropping funnel containing PCl3 (2.84 ml, 0.03262 mol) in degassed heptane (100 ml). The solution in the dropping funnel was added to the mixture over a period of 1 h, after which the mixture was refluxed (ca 373 K) for 24 h. The mixture was then decanted and the remaining solids extracted successively with hot benzene and water. The combined benzene extracts were dried (Na2SO4) and the remaining solid purified with column chromatography [acetone-CHCl3, 1:4; RF(O═PFc3) = 0.3]. Purified (I) crystallized as yellow crystals by slow evaporation from the acetone-chloroform solution (yield 0.5 g, 2.6%). Red crystals were obtained from the reaction with [Rh(Cl)(CO)2]2 and (I) (1:4 Molar? ratio) in dichloromethane. Spectroscopic data: 1H NMR (CDCl3, 300 MHz): 4.08 (d, 27H) p.p.m; 31P NMR{H} (CDCl3, 121.46 MHz): 30.3 (s) p.p.m.
Aromatic H atoms were placed in geometrically idealized positions (C—H = 0.97–0.98 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The positions of the water H atoms were determined from a Fourier difference map and their coordinates were refined isotropically.
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus and XPREP (Bruker, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Fe3(C5H5)3(C15H12OP)]·H2O | Z = 2 |
Mr = 620.05 | F(000) = 636 |
Triclinic, P1 | Dx = 1.60 Mg m−3 Dm = 1.585 Mg m−3 Dm measured by flotation in aqueous NaI |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.010 (2) Å | Cell parameters from 966 reflections |
b = 11.900 (2) Å | θ = 3–28° |
c = 11.920 (2) Å | µ = 1.76 mm−1 |
α = 76.51 (3)° | T = 293 K |
β = 70.23 (3)° | Cuboid, red |
γ = 78.13 (3)° | 0.4 × 0.24 × 0.18 mm |
V = 1286.8 (5) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 5233 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→13 |
Tmin = 0.583, Tmax = 0.728 | k = −15→15 |
8973 measured reflections | l = −15→15 |
6181 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0338P)2 + 0.4474P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.073 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.39 e Å−3 |
6181 reflections | Δρmin = −0.47 e Å−3 |
333 parameters |
[Fe3(C5H5)3(C15H12OP)]·H2O | γ = 78.13 (3)° |
Mr = 620.05 | V = 1286.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.010 (2) Å | Mo Kα radiation |
b = 11.900 (2) Å | µ = 1.76 mm−1 |
c = 11.920 (2) Å | T = 293 K |
α = 76.51 (3)° | 0.4 × 0.24 × 0.18 mm |
β = 70.23 (3)° |
Bruker SMART 1K CCD area-detector diffractometer | 6181 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 5233 reflections with I > 2σ(I) |
Tmin = 0.583, Tmax = 0.728 | Rint = 0.015 |
8973 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.39 e Å−3 |
6181 reflections | Δρmin = −0.47 e Å−3 |
333 parameters |
Experimental. The intensity data were collected on a Siemens SMART CCD 1 K diffractometer using an exposure time of 20 s/frame. A total of 1315 frames were collected with a frame width of 0.3° covering up to θ = 28.28° with 96.9% completeness accomplished. Completeness of 99.3% was accomplished up to τ = 25.0°. The first 50 frames were recollected at the end of the data collection to check for decay; none was found. |
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. |
x | y | z | Uiso*/Ueq | ||
Fe2 | 0.09336 (3) | 0.58435 (2) | 0.75437 (2) | 0.03328 (7) | |
Fe3 | 0.21413 (3) | 0.11026 (2) | 0.63929 (3) | 0.03791 (8) | |
Fe1 | 0.54383 (3) | 0.23521 (2) | 0.90588 (3) | 0.03445 (7) | |
P | 0.31181 (5) | 0.31827 (4) | 0.74038 (4) | 0.02688 (9) | |
O1 | 0.42564 (14) | 0.35459 (12) | 0.62545 (12) | 0.0394 (3) | |
C31 | 0.14271 (19) | 0.40881 (14) | 0.75791 (16) | 0.0304 (3) | |
C51 | 0.27151 (19) | 0.17459 (14) | 0.75733 (16) | 0.0312 (4) | |
C11 | 0.35639 (18) | 0.31478 (15) | 0.87439 (16) | 0.0303 (3) | |
C52 | 0.1338 (2) | 0.13758 (17) | 0.81366 (18) | 0.0397 (4) | |
H52 | 0.0492 | 0.1845 | 0.8464 | 0.048* | |
C15 | 0.4289 (2) | 0.39738 (16) | 0.89415 (19) | 0.0382 (4) | |
H15 | 0.4594 | 0.4639 | 0.84 | 0.046* | |
C12 | 0.3289 (2) | 0.22699 (17) | 0.98143 (17) | 0.0368 (4) | |
H12 | 0.283 | 0.1626 | 0.9939 | 0.044* | |
C35 | 0.0772 (2) | 0.46366 (16) | 0.66451 (18) | 0.0380 (4) | |
H35 | 0.1183 | 0.4629 | 0.582 | 0.046* | |
C22 | 0.6494 (2) | 0.0830 (2) | 0.8469 (2) | 0.0522 (5) | |
H22 | 0.608 | 0.0197 | 0.8475 | 0.063* | |
C13 | 0.3839 (2) | 0.25528 (19) | 1.06515 (19) | 0.0453 (5) | |
H13 | 0.3798 | 0.2127 | 1.142 | 0.054* | |
C21 | 0.6773 (2) | 0.1789 (2) | 0.7518 (2) | 0.0513 (5) | |
H21 | 0.6572 | 0.1899 | 0.679 | 0.062* | |
C33 | −0.0830 (2) | 0.50057 (17) | 0.8468 (2) | 0.0451 (5) | |
H33 | −0.1651 | 0.5279 | 0.9044 | 0.054* | |
C55 | 0.3707 (2) | 0.07452 (17) | 0.7209 (2) | 0.0441 (5) | |
H55 | 0.4687 | 0.0727 | 0.6823 | 0.053* | |
C61 | 0.2301 (3) | 0.2289 (2) | 0.4823 (2) | 0.0561 (6) | |
H61 | 0.2678 | 0.2987 | 0.4623 | 0.067* | |
C32 | 0.0423 (2) | 0.43285 (15) | 0.87065 (17) | 0.0352 (4) | |
H32 | 0.0565 | 0.4085 | 0.9463 | 0.042* | |
C42 | 0.1984 (3) | 0.67139 (18) | 0.8204 (2) | 0.0524 (6) | |
H42 | 0.2296 | 0.6433 | 0.8883 | 0.063* | |
C53 | 0.1477 (3) | 0.01709 (19) | 0.8113 (2) | 0.0521 (6) | |
H53 | 0.0738 | −0.0286 | 0.8423 | 0.063* | |
C54 | 0.2925 (3) | −0.02151 (18) | 0.7542 (2) | 0.0537 (6) | |
H54 | 0.3306 | −0.097 | 0.7404 | 0.064* | |
C62 | 0.0854 (3) | 0.2142 (2) | 0.5430 (2) | 0.0600 (6) | |
H62 | 0.0112 | 0.2725 | 0.5697 | 0.072* | |
C23 | 0.6947 (3) | 0.0991 (2) | 0.9411 (3) | 0.0660 (7) | |
H23 | 0.6882 | 0.0489 | 1.0147 | 0.079* | |
C45 | 0.1910 (3) | 0.7133 (2) | 0.6254 (2) | 0.0620 (7) | |
H45 | 0.2169 | 0.7176 | 0.5421 | 0.074* | |
C14 | 0.4455 (2) | 0.35869 (18) | 1.0121 (2) | 0.0456 (5) | |
H14 | 0.4896 | 0.3957 | 1.0479 | 0.055* | |
C44 | 0.0585 (3) | 0.76071 (17) | 0.6992 (2) | 0.0553 (6) | |
H44 | −0.0185 | 0.8017 | 0.6732 | 0.066* | |
C65 | 0.3082 (4) | 0.1200 (2) | 0.4572 (2) | 0.0700 (8) | |
H65 | 0.4059 | 0.1049 | 0.4181 | 0.084* | |
C64 | 0.2091 (4) | 0.0375 (2) | 0.5031 (3) | 0.0801 (10) | |
H64 | 0.2309 | −0.0415 | 0.4987 | 0.096* | |
C63 | 0.0727 (4) | 0.0960 (3) | 0.5560 (3) | 0.0725 (8) | |
H63 | −0.0111 | 0.0624 | 0.5932 | 0.087* | |
C34 | −0.0618 (2) | 0.51928 (18) | 0.7212 (2) | 0.0462 (5) | |
H34 | −0.1276 | 0.561 | 0.682 | 0.055* | |
C43 | 0.0633 (3) | 0.73506 (17) | 0.8194 (2) | 0.0510 (5) | |
H43 | −0.01 | 0.7564 | 0.8866 | 0.061* | |
C41 | 0.2778 (3) | 0.6578 (2) | 0.7010 (2) | 0.0579 (6) | |
H41 | 0.3707 | 0.6193 | 0.6758 | 0.069* | |
C25 | 0.7410 (3) | 0.2554 (3) | 0.7858 (3) | 0.0693 (8) | |
H25 | 0.7705 | 0.3256 | 0.7397 | 0.083* | |
C24 | 0.7519 (3) | 0.2058 (3) | 0.9031 (3) | 0.0754 (9) | |
H24 | 0.7901 | 0.2379 | 0.9475 | 0.09* | |
O2 | 0.6279 (2) | 0.5060 (2) | 0.58941 (19) | 0.0680 (5) | |
H1 | 0.583 (4) | 0.458 (3) | 0.603 (3) | 0.082 (11)* | |
H2 | 0.612 (4) | 0.550 (3) | 0.525 (4) | 0.106 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe2 | 0.04236 (15) | 0.02183 (12) | 0.03498 (14) | −0.00229 (10) | −0.01289 (11) | −0.00402 (10) |
Fe3 | 0.04915 (17) | 0.03017 (14) | 0.04302 (16) | −0.00990 (12) | −0.01976 (13) | −0.01058 (11) |
Fe1 | 0.03312 (14) | 0.03203 (14) | 0.04300 (16) | −0.00251 (10) | −0.01755 (11) | −0.00868 (11) |
P | 0.0296 (2) | 0.0223 (2) | 0.0307 (2) | −0.00468 (16) | −0.01033 (17) | −0.00577 (16) |
O1 | 0.0390 (7) | 0.0404 (7) | 0.0360 (7) | −0.0115 (6) | −0.0066 (6) | −0.0038 (6) |
C31 | 0.0360 (9) | 0.0229 (8) | 0.0351 (9) | −0.0026 (7) | −0.0148 (7) | −0.0057 (7) |
C51 | 0.0365 (9) | 0.0252 (8) | 0.0374 (9) | −0.0042 (7) | −0.0166 (7) | −0.0081 (7) |
C11 | 0.0311 (8) | 0.0263 (8) | 0.0366 (9) | −0.0015 (7) | −0.0142 (7) | −0.0081 (7) |
C52 | 0.0430 (11) | 0.0391 (10) | 0.0398 (10) | −0.0140 (8) | −0.0112 (8) | −0.0070 (8) |
C15 | 0.0457 (11) | 0.0276 (9) | 0.0496 (11) | −0.0035 (8) | −0.0231 (9) | −0.0109 (8) |
C12 | 0.0358 (9) | 0.0358 (10) | 0.0380 (10) | −0.0057 (8) | −0.0116 (8) | −0.0042 (8) |
C35 | 0.0485 (11) | 0.0316 (9) | 0.0400 (10) | −0.0020 (8) | −0.0222 (9) | −0.0081 (8) |
C22 | 0.0514 (13) | 0.0407 (11) | 0.0666 (15) | 0.0105 (10) | −0.0246 (11) | −0.0186 (11) |
C13 | 0.0508 (12) | 0.0503 (12) | 0.0370 (10) | −0.0011 (9) | −0.0193 (9) | −0.0079 (9) |
C21 | 0.0414 (11) | 0.0564 (14) | 0.0519 (13) | 0.0016 (10) | −0.0093 (10) | −0.0162 (11) |
C33 | 0.0357 (10) | 0.0327 (10) | 0.0598 (13) | −0.0004 (8) | −0.0080 (9) | −0.0082 (9) |
C55 | 0.0441 (11) | 0.0315 (10) | 0.0647 (13) | 0.0045 (8) | −0.0260 (10) | −0.0185 (9) |
C61 | 0.0883 (18) | 0.0469 (13) | 0.0430 (12) | −0.0210 (12) | −0.0292 (12) | −0.0030 (10) |
C32 | 0.0391 (10) | 0.0263 (8) | 0.0368 (9) | −0.0043 (7) | −0.0089 (8) | −0.0033 (7) |
C42 | 0.0730 (16) | 0.0340 (11) | 0.0607 (14) | −0.0154 (10) | −0.0305 (12) | −0.0066 (10) |
C53 | 0.0733 (16) | 0.0394 (11) | 0.0539 (13) | −0.0285 (11) | −0.0270 (12) | 0.0016 (9) |
C54 | 0.0797 (17) | 0.0246 (9) | 0.0694 (15) | −0.0038 (10) | −0.0405 (13) | −0.0089 (9) |
C62 | 0.0728 (17) | 0.0604 (15) | 0.0622 (15) | −0.0089 (13) | −0.0429 (13) | −0.0073 (12) |
C23 | 0.0616 (15) | 0.0694 (17) | 0.0720 (17) | 0.0272 (13) | −0.0407 (14) | −0.0234 (14) |
C45 | 0.100 (2) | 0.0374 (12) | 0.0418 (12) | −0.0271 (13) | −0.0076 (13) | 0.0014 (9) |
C14 | 0.0557 (12) | 0.0427 (11) | 0.0516 (12) | 0.0002 (9) | −0.0303 (10) | −0.0189 (9) |
C44 | 0.0775 (17) | 0.0241 (10) | 0.0638 (15) | −0.0034 (10) | −0.0292 (13) | 0.0017 (9) |
C65 | 0.100 (2) | 0.0636 (16) | 0.0459 (13) | −0.0097 (15) | −0.0137 (14) | −0.0218 (12) |
C64 | 0.151 (3) | 0.0518 (15) | 0.0626 (17) | −0.0298 (18) | −0.050 (2) | −0.0189 (13) |
C63 | 0.098 (2) | 0.0794 (19) | 0.0689 (18) | −0.0397 (18) | −0.0489 (17) | −0.0081 (15) |
C34 | 0.0445 (11) | 0.0346 (10) | 0.0661 (14) | 0.0017 (8) | −0.0302 (10) | −0.0080 (9) |
C43 | 0.0679 (15) | 0.0276 (10) | 0.0542 (13) | −0.0067 (9) | −0.0096 (11) | −0.0144 (9) |
C41 | 0.0517 (13) | 0.0376 (12) | 0.0773 (17) | −0.0160 (10) | −0.0040 (12) | −0.0115 (11) |
C25 | 0.0346 (12) | 0.0679 (17) | 0.098 (2) | −0.0134 (11) | 0.0009 (13) | −0.0262 (16) |
C24 | 0.0376 (12) | 0.101 (2) | 0.111 (2) | 0.0105 (13) | −0.0372 (15) | −0.059 (2) |
O2 | 0.0701 (12) | 0.0823 (14) | 0.0552 (11) | −0.0402 (11) | −0.0202 (9) | 0.0083 (10) |
Fe2—C31 | 2.0391 (17) | C61—C65 | 1.409 (4) |
Fe3—C51 | 2.0311 (17) | C61—C62 | 1.411 (4) |
Fe1—C11 | 2.0340 (18) | C61—H61 | 0.93 |
P—O1 | 1.4941 (15) | C32—H32 | 0.93 |
P—C31 | 1.7846 (19) | C42—C41 | 1.405 (4) |
P—C51 | 1.7872 (17) | C42—C43 | 1.410 (3) |
P—C11 | 1.7879 (18) | C42—H42 | 0.93 |
C31—C32 | 1.430 (3) | C53—C54 | 1.407 (4) |
C31—C35 | 1.440 (2) | C53—H53 | 0.93 |
C51—C52 | 1.425 (3) | C54—H54 | 0.93 |
C51—C55 | 1.434 (3) | C62—C63 | 1.406 (4) |
C11—C12 | 1.433 (3) | C62—H62 | 0.93 |
C11—C15 | 1.437 (2) | C23—C24 | 1.414 (4) |
C52—C53 | 1.418 (3) | C23—H23 | 0.93 |
C52—H52 | 0.93 | C45—C44 | 1.409 (4) |
C15—C14 | 1.429 (3) | C45—C41 | 1.421 (4) |
C15—H15 | 0.93 | C45—H45 | 0.93 |
C12—C13 | 1.420 (3) | C14—H14 | 0.93 |
C12—H12 | 0.93 | C44—C43 | 1.409 (3) |
C35—C34 | 1.423 (3) | C44—H44 | 0.93 |
C35—H35 | 0.93 | C65—C64 | 1.425 (4) |
C22—C21 | 1.406 (3) | C65—H65 | 0.93 |
C22—C23 | 1.409 (3) | C64—C63 | 1.406 (5) |
C22—H22 | 0.93 | C64—H64 | 0.93 |
C13—C14 | 1.407 (3) | C63—H63 | 0.93 |
C13—H13 | 0.93 | C34—H34 | 0.93 |
C21—C25 | 1.410 (4) | C43—H43 | 0.93 |
C21—H21 | 0.93 | C41—H41 | 0.93 |
C33—C34 | 1.409 (3) | C25—C24 | 1.416 (4) |
C33—C32 | 1.422 (3) | C25—H25 | 0.93 |
C33—H33 | 0.93 | C24—H24 | 0.93 |
C55—C54 | 1.422 (3) | O2—H1 | 0.75 (3) |
C55—H55 | 0.93 | O2—H2 | 0.86 (4) |
O1—P—C31 | 114.50 (9) | C62—C61—H61 | 125.7 |
O1—P—C51 | 113.87 (9) | C33—C32—C31 | 108.01 (17) |
C31—P—C51 | 104.30 (8) | C33—C32—H32 | 126 |
O1—P—C11 | 113.96 (8) | C31—C32—H32 | 126 |
C31—P—C11 | 105.20 (9) | C41—C42—C43 | 108.1 (2) |
C51—P—C11 | 103.87 (8) | C41—C42—H42 | 126 |
C32—C31—C35 | 107.33 (16) | C43—C42—H42 | 126 |
C32—C31—P | 125.41 (14) | C54—C53—C52 | 108.20 (19) |
C35—C31—P | 127.11 (14) | C54—C53—H53 | 125.9 |
C32—C31—Fe2 | 69.56 (10) | C52—C53—H53 | 125.9 |
C35—C31—Fe2 | 69.41 (10) | C53—C54—C55 | 108.43 (18) |
P—C31—Fe2 | 129.64 (10) | C53—C54—H54 | 125.8 |
C52—C51—C55 | 107.14 (16) | C55—C54—H54 | 125.8 |
C52—C51—P | 125.86 (14) | C63—C62—C61 | 108.1 (3) |
C55—C51—P | 126.98 (15) | C63—C62—H62 | 126 |
C52—C51—Fe3 | 69.72 (11) | C61—C62—H62 | 126 |
C55—C51—Fe3 | 69.55 (11) | C22—C23—C24 | 107.4 (3) |
P—C51—Fe3 | 127.29 (10) | C22—C23—H23 | 126.3 |
C12—C11—C15 | 107.26 (16) | C24—C23—H23 | 126.3 |
C12—C11—P | 126.05 (13) | C44—C45—C41 | 107.9 (2) |
C15—C11—P | 126.68 (14) | C44—C45—H45 | 126.1 |
C12—C11—Fe1 | 69.85 (11) | C41—C45—H45 | 126.1 |
C15—C11—Fe1 | 69.32 (10) | C13—C14—C15 | 108.54 (17) |
P—C11—Fe1 | 125.03 (10) | C13—C14—H14 | 125.7 |
C53—C52—C51 | 108.42 (19) | C15—C14—H14 | 125.7 |
C53—C52—H52 | 125.8 | C45—C44—C43 | 107.9 (2) |
C51—C52—H52 | 125.8 | C45—C44—H44 | 126 |
C14—C15—C11 | 107.57 (17) | C43—C44—H44 | 126 |
C14—C15—H15 | 126.2 | C61—C65—C64 | 107.1 (3) |
C11—C15—H15 | 126.2 | C61—C65—H65 | 126.5 |
C13—C12—C11 | 108.18 (17) | C64—C65—H65 | 126.5 |
C13—C12—H12 | 125.9 | C63—C64—C65 | 108.3 (2) |
C11—C12—H12 | 125.9 | C63—C64—H64 | 125.9 |
C34—C35—C31 | 107.64 (18) | C65—C64—H64 | 125.9 |
C34—C35—H35 | 126.2 | C62—C63—C64 | 108.0 (3) |
C31—C35—H35 | 126.2 | C62—C63—H63 | 126 |
C21—C22—C23 | 108.6 (2) | C64—C63—H63 | 126 |
C21—C22—H22 | 125.7 | C33—C34—C35 | 108.53 (18) |
C23—C22—H22 | 125.7 | C33—C34—H34 | 125.7 |
C14—C13—C12 | 108.45 (18) | C35—C34—H34 | 125.7 |
C14—C13—H13 | 125.8 | C44—C43—C42 | 108.3 (2) |
C12—C13—H13 | 125.8 | C44—C43—H43 | 125.9 |
C22—C21—C25 | 108.2 (2) | C42—C43—H43 | 125.9 |
C22—C21—H21 | 125.9 | C42—C41—C45 | 107.9 (2) |
C25—C21—H21 | 125.9 | C42—C41—H41 | 126.1 |
C34—C33—C32 | 108.49 (18) | C45—C41—H41 | 126.1 |
C34—C33—H33 | 125.8 | C21—C25—C24 | 107.5 (3) |
C32—C33—H33 | 125.8 | C21—C25—H25 | 126.3 |
C54—C55—C51 | 107.80 (19) | C24—C25—H25 | 126.3 |
C54—C55—H55 | 126.1 | C23—C24—C25 | 108.4 (2) |
C51—C55—H55 | 126.1 | C23—C24—H24 | 125.8 |
C65—C61—C62 | 108.5 (2) | C25—C24—H24 | 125.8 |
C65—C61—H61 | 125.7 | H1—O2—H2 | 103 (3) |
C21—C11—P—O1 | −45.39 (9) | Fe1—C11—P—O1 | −49.29 (13) |
C41—C31—P—O1 | −51.27 (10) | Fe2—C31—P—O1 | −56.11 (14) |
C61—C51—P—O1 | −50.69 (10) | Fe3—C51—P—O1 | −54.49 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1 | 0.75 (3) | 2.10 (3) | 2.843 (3) | 167 (3) |
O2—H2···O1i | 0.86 (4) | 2.00 (4) | 2.860 (3) | 178 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Fe3(C5H5)3(C15H12OP)]·H2O |
Mr | 620.05 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.010 (2), 11.900 (2), 11.920 (2) |
α, β, γ (°) | 76.51 (3), 70.23 (3), 78.13 (3) |
V (Å3) | 1286.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.76 |
Crystal size (mm) | 0.4 × 0.24 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.583, 0.728 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8973, 6181, 5233 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.073, 1.03 |
No. of reflections | 6181 |
No. of parameters | 333 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.47 |
Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SAINT-Plus and XPREP (Bruker, 1999), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), WinGX (Farrugia, 1999).
P—O1 | 1.4941 (15) | P—C51 | 1.7872 (17) |
P—C31 | 1.7846 (19) | P—C11 | 1.7879 (18) |
O1—P—C31 | 114.50 (9) | O1—P—C11 | 113.96 (8) |
O1—P—C51 | 113.87 (9) | ||
C21—C11—P—O1 | −45.39 (9) | Fe1—C11—P—O1 | −49.29 (13) |
C41—C31—P—O1 | −51.27 (10) | Fe2—C31—P—O1 | −56.11 (14) |
C61—C51—P—O1 | −50.69 (10) | Fe3—C51—P—O1 | −54.49 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1 | 0.75 (3) | 2.10 (3) | 2.843 (3) | 167 (3) |
O2—H2···O1i | 0.86 (4) | 2.00 (4) | 2.860 (3) | 178 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Fe(X) | Fe-X | θtor1 | θtor2 | θtor3 | θT | Footnote |
O | 1.4941 (15) | -47.6 | -49.3 | -45.4 | 211 | (TW) |
-55.2 | -56.2 | -51.3 | ||||
-54.6 | -54.4 | -50.6 | ||||
I | 2.426 (12) | -46.3 | -47.3 | -45.4 | 198 | (i) |
-162.0 | -161.2 | -167.6 | ||||
-49.2 | -49.3 | -52.0 | ||||
CH2 | 1.630 | 56.3 | 57.2 | 51.5 | 200 | (ii) |
63.5 | 62.7 | 58.8 | ||||
64.5 | 64.3 | 61.3 |
Notes: (TW) = this work; θtor1 = X-P-Cg1-Cg2; θtor2 = X-P-C-Fe; θtor3 = X-P-C-C; θT = Tolman cone angle (Tolman, 1977); (i) Gridunova et al. (1982); (ii) Schmidbaur et al. (1989). |
As part of a systematic investigation into the steric demand of phosphine ligands in various model Pt-group metal complexes, we have unexpectedly isolated crystals of triferrocenylphosphine oxide (PFc3═O), (I), previously reported but not structurally characterized by Sollot & Howard (1962). The yellow crystalline solid obtained was at first thought to be unoxidized PFc3, and was tested in reaction with [Rh(Cl)(CO)2]2 in an attempt to synthesize the well known [MCl(CO)(XY3)2] Vaska-type complexes (M is Rh or Ir, X is P, As or Sb, and Y is aryl or alkyl), which often crystallize with ease. However, no reaction was observed (IR and 31P NMR spectroscopy) and crystals, now red in colour, were isolated from the mixture. The spectroscopic data of these were similar to those of the yellow crystalline compound (see Experimental). The change in colour can probably be attributed to the variation in solvent between the two synthetic steps, resulting in different packing effects. \sch
Compound (I) (Fig. 1) is one of the few structures characterized to date containing the PFc3 moiety [Cambridge Structural Database (CSD), version 5.25, 2004; Allen, 2002). Usually, ferrocenyl fragments possess geometric parameters similar to those of ferrocene and its derivatives. In the case of (I), all the Cp rings are planar to within 0.003 Å and the interplanar angles are 3.53 (19), 2.37 (12) and 2.19 (12)° for the Fe1, Fe2 and Fe3 moieties, respectively. Furthermore, the Cp rings in each ferrocenyl moiety have an almost eclipsed conformation.
Pairs of O═PFc3 molecules are linked via O—H···O hydrogen bonds to water molecules, forming a dimeric structure around an inversion centre (Table 2 and Fig. 2). This interaction creates channels along the c axis (Fig. 2). The use of water as a hydrogen bridge in the solid state in phosphine oxide compounds is not uncommon, but few form dimeric structures in the unit cell (ca 10%; CSD, version 5.25, 2004). These compounds mostly consist of either ferrocene or electron-donating (Krauss et al., 2001) functionalized variations thereof. Thus, electron-rich phosphorus(V) oxides might assist in the formation of dimeric structures. The same hydrogen-bonding pattern is observed for the structure O═PFc2Et·H2O (Durfey et al., 2002).
The conformation of the ferrocene substituents in (I) can be described by the torsion angles between the O═P moiety and ferrocene, which are compared in Table 3 with those of other compounds containing PFc3 fragments. It is important to note that none of the compounds has torsion angles close to 0°, illustrating few or no intramolecular interactions between X—P and ferrocene, which was postulated as an option for a possible geometrical conformation of (I) (Sollot & Howard, 1962). The ferrocenyl moieties are staggered in such a way that both atoms O1 and P are above the plane formed by the three Fe atoms [1.8424 (16) and 0.3499 (5) Å for O1 and P, respectively].
Three different methods have been investigated to estimate the torsion angles of the ferrocenyl moiety for comparison with reported torsion angles in the literature (Steyl et al., 2001). These include O—P—Cg1—Cg2, O—P—C—Fe and O—P—C—C (Cg is the centroid of ring 1 or 2). The torsion angles O—P—Cg1—Cg2 and O—P—C—Fe yield similar values, while the other method gives ~5° difference, because of the almost eclipsed conformation of the Cp rings.
The most widely used parameter to define the steric demand of tertiary phosphines is the Tolman cone angle (θT), which was calculated as described previously (Tolman, 1977; Otto et al., 2000). A modified structure of (I) was used to calculate a reasonable value for the expected Tolman cone angle, by incorporating a dummy atom 2.28 Å from the P atom. A somewhat larger value of 211° was obtained for (I) compared with the other known PFc3 structures (Table 3). This value may not necessarily be a true reflection of the steric influence on a given metal centre, since the flexibility of ferrocenyl moieties around the P—C bond can significantly affect this value. This was found previously with similar flexible phosphines, e.g. tribenzylphosphine (Muller et al., 2002) and ferrocenyldiphenylphosphine (Otto et al., 2000). The structures of I-PFc3 and H2C═PFc3 are examples where the ferrocenyl fragments have different orientations with respect to the X—P moieties (torsion angles in Table 3) but still possess similar cone angles.