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The title compound, [Fe3(C5H5)3(C15H12OP)]·H2O or Fc3PO·H2O, was obtained as red crystals from the Friedel–Crafts alkyl­ation reaction of PCl3 and ferrocene. Torsion angles (O=P—C—Fe/C) range from −45.39 (9) to −56.11 (14)°. The structure is stabilized by intermolecular hydrogen bonds [H...O = 2.10 (3) and 2.00 (4) Å], forming dimeric structures between pairs of O=PFc3 and water mol­ecules. A theoretical Tolman cone angle of 211° was calculated.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104014908/jz1629sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014908/jz1629Isup2.hkl
Contains datablock I

CCDC reference: 248131

Comment top

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 (PFc3O), (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 OPFc3 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 OPFc2Et·H2O (Durfey et al., 2002).

The conformation of the ferrocene substituents in (I) can be described by the torsion angles between the OP 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 H2CPFc3 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.

Experimental top

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(OPFc3) = 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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and with displacement ellipsoids at the 30% probability level. H atoms have been omitted for clarity. For the C atoms, the first digit indicates the ring number and the second digit indicates the number of the atom in the ring.
[Figure 2] Fig. 2. A packing diagram for (I), illustrating the interaction between pairs of OPFc3 and water molecules.
(I) top
Crystal data top
[Fe3(C5H5)3(C15H12OP)]·H2OZ = 2
Mr = 620.05F(000) = 636
Triclinic, P1Dx = 1.60 Mg m3
Dm = 1.585 Mg m3
Dm measured by flotation in aqueous NaI
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.010 (2) ÅCell parameters from 966 reflections
b = 11.900 (2) Åθ = 3–28°
c = 11.920 (2) ŵ = 1.76 mm1
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
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
5233 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
ω scansθmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1013
Tmin = 0.583, Tmax = 0.728k = 1515
8973 measured reflectionsl = 1515
6181 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH 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 = 1.03Δρmax = 0.39 e Å3
6181 reflectionsΔρmin = 0.47 e Å3
333 parameters
Crystal data top
[Fe3(C5H5)3(C15H12OP)]·H2Oγ = 78.13 (3)°
Mr = 620.05V = 1286.8 (5) Å3
Triclinic, P1Z = 2
a = 10.010 (2) ÅMo Kα radiation
b = 11.900 (2) ŵ = 1.76 mm1
c = 11.920 (2) ÅT = 293 K
α = 76.51 (3)°0.4 × 0.24 × 0.18 mm
β = 70.23 (3)°
Data collection top
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 = 0.728Rint = 0.015
8973 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.39 e Å3
6181 reflectionsΔρmin = 0.47 e Å3
333 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe20.09336 (3)0.58435 (2)0.75437 (2)0.03328 (7)
Fe30.21413 (3)0.11026 (2)0.63929 (3)0.03791 (8)
Fe10.54383 (3)0.23521 (2)0.90588 (3)0.03445 (7)
P0.31181 (5)0.31827 (4)0.74038 (4)0.02688 (9)
O10.42564 (14)0.35459 (12)0.62545 (12)0.0394 (3)
C310.14271 (19)0.40881 (14)0.75791 (16)0.0304 (3)
C510.27151 (19)0.17459 (14)0.75733 (16)0.0312 (4)
C110.35639 (18)0.31478 (15)0.87439 (16)0.0303 (3)
C520.1338 (2)0.13758 (17)0.81366 (18)0.0397 (4)
H520.04920.18450.84640.048*
C150.4289 (2)0.39738 (16)0.89415 (19)0.0382 (4)
H150.45940.46390.840.046*
C120.3289 (2)0.22699 (17)0.98143 (17)0.0368 (4)
H120.2830.16260.99390.044*
C350.0772 (2)0.46366 (16)0.66451 (18)0.0380 (4)
H350.11830.46290.5820.046*
C220.6494 (2)0.0830 (2)0.8469 (2)0.0522 (5)
H220.6080.01970.84750.063*
C130.3839 (2)0.25528 (19)1.06515 (19)0.0453 (5)
H130.37980.21271.1420.054*
C210.6773 (2)0.1789 (2)0.7518 (2)0.0513 (5)
H210.65720.18990.6790.062*
C330.0830 (2)0.50057 (17)0.8468 (2)0.0451 (5)
H330.16510.52790.90440.054*
C550.3707 (2)0.07452 (17)0.7209 (2)0.0441 (5)
H550.46870.07270.68230.053*
C610.2301 (3)0.2289 (2)0.4823 (2)0.0561 (6)
H610.26780.29870.46230.067*
C320.0423 (2)0.43285 (15)0.87065 (17)0.0352 (4)
H320.05650.40850.94630.042*
C420.1984 (3)0.67139 (18)0.8204 (2)0.0524 (6)
H420.22960.64330.88830.063*
C530.1477 (3)0.01709 (19)0.8113 (2)0.0521 (6)
H530.07380.02860.84230.063*
C540.2925 (3)0.02151 (18)0.7542 (2)0.0537 (6)
H540.33060.0970.74040.064*
C620.0854 (3)0.2142 (2)0.5430 (2)0.0600 (6)
H620.01120.27250.56970.072*
C230.6947 (3)0.0991 (2)0.9411 (3)0.0660 (7)
H230.68820.04891.01470.079*
C450.1910 (3)0.7133 (2)0.6254 (2)0.0620 (7)
H450.21690.71760.54210.074*
C140.4455 (2)0.35869 (18)1.0121 (2)0.0456 (5)
H140.48960.39571.04790.055*
C440.0585 (3)0.76071 (17)0.6992 (2)0.0553 (6)
H440.01850.80170.67320.066*
C650.3082 (4)0.1200 (2)0.4572 (2)0.0700 (8)
H650.40590.10490.41810.084*
C640.2091 (4)0.0375 (2)0.5031 (3)0.0801 (10)
H640.23090.04150.49870.096*
C630.0727 (4)0.0960 (3)0.5560 (3)0.0725 (8)
H630.01110.06240.59320.087*
C340.0618 (2)0.51928 (18)0.7212 (2)0.0462 (5)
H340.12760.5610.6820.055*
C430.0633 (3)0.73506 (17)0.8194 (2)0.0510 (5)
H430.010.75640.88660.061*
C410.2778 (3)0.6578 (2)0.7010 (2)0.0579 (6)
H410.37070.61930.67580.069*
C250.7410 (3)0.2554 (3)0.7858 (3)0.0693 (8)
H250.77050.32560.73970.083*
C240.7519 (3)0.2058 (3)0.9031 (3)0.0754 (9)
H240.79010.23790.94750.09*
O20.6279 (2)0.5060 (2)0.58941 (19)0.0680 (5)
H10.583 (4)0.458 (3)0.603 (3)0.082 (11)*
H20.612 (4)0.550 (3)0.525 (4)0.106 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe20.04236 (15)0.02183 (12)0.03498 (14)0.00229 (10)0.01289 (11)0.00402 (10)
Fe30.04915 (17)0.03017 (14)0.04302 (16)0.00990 (12)0.01976 (13)0.01058 (11)
Fe10.03312 (14)0.03203 (14)0.04300 (16)0.00251 (10)0.01755 (11)0.00868 (11)
P0.0296 (2)0.0223 (2)0.0307 (2)0.00468 (16)0.01033 (17)0.00577 (16)
O10.0390 (7)0.0404 (7)0.0360 (7)0.0115 (6)0.0066 (6)0.0038 (6)
C310.0360 (9)0.0229 (8)0.0351 (9)0.0026 (7)0.0148 (7)0.0057 (7)
C510.0365 (9)0.0252 (8)0.0374 (9)0.0042 (7)0.0166 (7)0.0081 (7)
C110.0311 (8)0.0263 (8)0.0366 (9)0.0015 (7)0.0142 (7)0.0081 (7)
C520.0430 (11)0.0391 (10)0.0398 (10)0.0140 (8)0.0112 (8)0.0070 (8)
C150.0457 (11)0.0276 (9)0.0496 (11)0.0035 (8)0.0231 (9)0.0109 (8)
C120.0358 (9)0.0358 (10)0.0380 (10)0.0057 (8)0.0116 (8)0.0042 (8)
C350.0485 (11)0.0316 (9)0.0400 (10)0.0020 (8)0.0222 (9)0.0081 (8)
C220.0514 (13)0.0407 (11)0.0666 (15)0.0105 (10)0.0246 (11)0.0186 (11)
C130.0508 (12)0.0503 (12)0.0370 (10)0.0011 (9)0.0193 (9)0.0079 (9)
C210.0414 (11)0.0564 (14)0.0519 (13)0.0016 (10)0.0093 (10)0.0162 (11)
C330.0357 (10)0.0327 (10)0.0598 (13)0.0004 (8)0.0080 (9)0.0082 (9)
C550.0441 (11)0.0315 (10)0.0647 (13)0.0045 (8)0.0260 (10)0.0185 (9)
C610.0883 (18)0.0469 (13)0.0430 (12)0.0210 (12)0.0292 (12)0.0030 (10)
C320.0391 (10)0.0263 (8)0.0368 (9)0.0043 (7)0.0089 (8)0.0033 (7)
C420.0730 (16)0.0340 (11)0.0607 (14)0.0154 (10)0.0305 (12)0.0066 (10)
C530.0733 (16)0.0394 (11)0.0539 (13)0.0285 (11)0.0270 (12)0.0016 (9)
C540.0797 (17)0.0246 (9)0.0694 (15)0.0038 (10)0.0405 (13)0.0089 (9)
C620.0728 (17)0.0604 (15)0.0622 (15)0.0089 (13)0.0429 (13)0.0073 (12)
C230.0616 (15)0.0694 (17)0.0720 (17)0.0272 (13)0.0407 (14)0.0234 (14)
C450.100 (2)0.0374 (12)0.0418 (12)0.0271 (13)0.0076 (13)0.0014 (9)
C140.0557 (12)0.0427 (11)0.0516 (12)0.0002 (9)0.0303 (10)0.0189 (9)
C440.0775 (17)0.0241 (10)0.0638 (15)0.0034 (10)0.0292 (13)0.0017 (9)
C650.100 (2)0.0636 (16)0.0459 (13)0.0097 (15)0.0137 (14)0.0218 (12)
C640.151 (3)0.0518 (15)0.0626 (17)0.0298 (18)0.050 (2)0.0189 (13)
C630.098 (2)0.0794 (19)0.0689 (18)0.0397 (18)0.0489 (17)0.0081 (15)
C340.0445 (11)0.0346 (10)0.0661 (14)0.0017 (8)0.0302 (10)0.0080 (9)
C430.0679 (15)0.0276 (10)0.0542 (13)0.0067 (9)0.0096 (11)0.0144 (9)
C410.0517 (13)0.0376 (12)0.0773 (17)0.0160 (10)0.0040 (12)0.0115 (11)
C250.0346 (12)0.0679 (17)0.098 (2)0.0134 (11)0.0009 (13)0.0262 (16)
C240.0376 (12)0.101 (2)0.111 (2)0.0105 (13)0.0372 (15)0.059 (2)
O20.0701 (12)0.0823 (14)0.0552 (11)0.0402 (11)0.0202 (9)0.0083 (10)
Geometric parameters (Å, º) top
Fe2—C312.0391 (17)C61—C651.409 (4)
Fe3—C512.0311 (17)C61—C621.411 (4)
Fe1—C112.0340 (18)C61—H610.93
P—O11.4941 (15)C32—H320.93
P—C311.7846 (19)C42—C411.405 (4)
P—C511.7872 (17)C42—C431.410 (3)
P—C111.7879 (18)C42—H420.93
C31—C321.430 (3)C53—C541.407 (4)
C31—C351.440 (2)C53—H530.93
C51—C521.425 (3)C54—H540.93
C51—C551.434 (3)C62—C631.406 (4)
C11—C121.433 (3)C62—H620.93
C11—C151.437 (2)C23—C241.414 (4)
C52—C531.418 (3)C23—H230.93
C52—H520.93C45—C441.409 (4)
C15—C141.429 (3)C45—C411.421 (4)
C15—H150.93C45—H450.93
C12—C131.420 (3)C14—H140.93
C12—H120.93C44—C431.409 (3)
C35—C341.423 (3)C44—H440.93
C35—H350.93C65—C641.425 (4)
C22—C211.406 (3)C65—H650.93
C22—C231.409 (3)C64—C631.406 (5)
C22—H220.93C64—H640.93
C13—C141.407 (3)C63—H630.93
C13—H130.93C34—H340.93
C21—C251.410 (4)C43—H430.93
C21—H210.93C41—H410.93
C33—C341.409 (3)C25—C241.416 (4)
C33—C321.422 (3)C25—H250.93
C33—H330.93C24—H240.93
C55—C541.422 (3)O2—H10.75 (3)
C55—H550.93O2—H20.86 (4)
O1—P—C31114.50 (9)C62—C61—H61125.7
O1—P—C51113.87 (9)C33—C32—C31108.01 (17)
C31—P—C51104.30 (8)C33—C32—H32126
O1—P—C11113.96 (8)C31—C32—H32126
C31—P—C11105.20 (9)C41—C42—C43108.1 (2)
C51—P—C11103.87 (8)C41—C42—H42126
C32—C31—C35107.33 (16)C43—C42—H42126
C32—C31—P125.41 (14)C54—C53—C52108.20 (19)
C35—C31—P127.11 (14)C54—C53—H53125.9
C32—C31—Fe269.56 (10)C52—C53—H53125.9
C35—C31—Fe269.41 (10)C53—C54—C55108.43 (18)
P—C31—Fe2129.64 (10)C53—C54—H54125.8
C52—C51—C55107.14 (16)C55—C54—H54125.8
C52—C51—P125.86 (14)C63—C62—C61108.1 (3)
C55—C51—P126.98 (15)C63—C62—H62126
C52—C51—Fe369.72 (11)C61—C62—H62126
C55—C51—Fe369.55 (11)C22—C23—C24107.4 (3)
P—C51—Fe3127.29 (10)C22—C23—H23126.3
C12—C11—C15107.26 (16)C24—C23—H23126.3
C12—C11—P126.05 (13)C44—C45—C41107.9 (2)
C15—C11—P126.68 (14)C44—C45—H45126.1
C12—C11—Fe169.85 (11)C41—C45—H45126.1
C15—C11—Fe169.32 (10)C13—C14—C15108.54 (17)
P—C11—Fe1125.03 (10)C13—C14—H14125.7
C53—C52—C51108.42 (19)C15—C14—H14125.7
C53—C52—H52125.8C45—C44—C43107.9 (2)
C51—C52—H52125.8C45—C44—H44126
C14—C15—C11107.57 (17)C43—C44—H44126
C14—C15—H15126.2C61—C65—C64107.1 (3)
C11—C15—H15126.2C61—C65—H65126.5
C13—C12—C11108.18 (17)C64—C65—H65126.5
C13—C12—H12125.9C63—C64—C65108.3 (2)
C11—C12—H12125.9C63—C64—H64125.9
C34—C35—C31107.64 (18)C65—C64—H64125.9
C34—C35—H35126.2C62—C63—C64108.0 (3)
C31—C35—H35126.2C62—C63—H63126
C21—C22—C23108.6 (2)C64—C63—H63126
C21—C22—H22125.7C33—C34—C35108.53 (18)
C23—C22—H22125.7C33—C34—H34125.7
C14—C13—C12108.45 (18)C35—C34—H34125.7
C14—C13—H13125.8C44—C43—C42108.3 (2)
C12—C13—H13125.8C44—C43—H43125.9
C22—C21—C25108.2 (2)C42—C43—H43125.9
C22—C21—H21125.9C42—C41—C45107.9 (2)
C25—C21—H21125.9C42—C41—H41126.1
C34—C33—C32108.49 (18)C45—C41—H41126.1
C34—C33—H33125.8C21—C25—C24107.5 (3)
C32—C33—H33125.8C21—C25—H25126.3
C54—C55—C51107.80 (19)C24—C25—H25126.3
C54—C55—H55126.1C23—C24—C25108.4 (2)
C51—C55—H55126.1C23—C24—H24125.8
C65—C61—C62108.5 (2)C25—C24—H24125.8
C65—C61—H61125.7H1—O2—H2103 (3)
C21—C11—P—O145.39 (9)Fe1—C11—P—O149.29 (13)
C41—C31—P—O151.27 (10)Fe2—C31—P—O156.11 (14)
C61—C51—P—O150.69 (10)Fe3—C51—P—O154.49 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1···O10.75 (3)2.10 (3)2.843 (3)167 (3)
O2—H2···O1i0.86 (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
Mr620.05
Crystal system, space groupTriclinic, 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)
V3)1286.8 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.76
Crystal size (mm)0.4 × 0.24 × 0.18
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.583, 0.728
No. of measured, independent and
observed [I > 2σ(I)] reflections
8973, 6181, 5233
Rint0.015
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.073, 1.03
No. of reflections6181
No. of parameters333
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
P—O11.4941 (15)P—C511.7872 (17)
P—C311.7846 (19)P—C111.7879 (18)
O1—P—C31114.50 (9)O1—P—C11113.96 (8)
O1—P—C51113.87 (9)
C21—C11—P—O145.39 (9)Fe1—C11—P—O149.29 (13)
C41—C31—P—O151.27 (10)Fe2—C31—P—O156.11 (14)
C61—C51—P—O150.69 (10)Fe3—C51—P—O154.49 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1···O10.75 (3)2.10 (3)2.843 (3)167 (3)
O2—H2···O1i0.86 (4)2.00 (4)2.860 (3)178 (4)
Symmetry code: (i) x+1, y+1, z+1.
Comparative geometrical data for XPFc3 (°, Å) top
Fe(X)Fe-Xθtor1θtor2θtor3θTFootnote
O1.4941 (15)-47.6-49.3-45.4211(TW)
-55.2-56.2-51.3
-54.6-54.4-50.6
I2.426 (12)-46.3-47.3-45.4198(i)
-162.0-161.2-167.6
-49.2-49.3-52.0
CH21.63056.357.251.5200(ii)
63.562.758.8
64.564.361.3
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).
 

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