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As part of our inter­est in the synthesis and catalytic applications of chiral (di­phenyl­phosphanyl)­ferrocene ligands, we designed a number of P,N-containing ligands for use in asymmetric transfer hydrogenation (ATH). During the synthetic procedure to obtain rac-1-[(N,4-di­methyl­benzene­sulfonamido)­methyl]-2-(di­phenyl­phosphanyl)­ferrocene, the title compound, [Fe(C5H5)(C26H25NO2PS)]0.55·[Fe(C5H5)(C26H25NO3PS)]0.45, was obtained as a by-product. It is composed of a ferrocene group disubstituted by a partially oxidized di­phenyl­phosphanyl group, as confirmed by 31P NMR analysis, and an (N,4-di­­methyl­benzene­sulfonamido)­methyl substituent. Owing to the partially oxidized di­phenyl­phosphanyl group, it is best to view the crystal as being composed of a mixture of non-oxidized and oxidized phosphane, so it can be regarded as a cocrystal. It is also a racemate. To the best of our knowledge, the P=O distance [1.344 (4) Å] is the shortest observed for related (di­phenyl­phosphoryl)­ferrocene compounds. The packing is sta­bilized by weak C—H...O inter­actions, forming R22(10) hydrogen-bonding motifs, which build up a chain along the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614002988/ku3123sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614002988/ku3123Isup2.hkl
Contains datablock I

CCDC reference: 985993

Introduction top

In asymmetric transfer hydrogenation (ATH), most of the more efficient ligands present an NH group which is involved in a hydrogen-transfer step. In the mechanism proposed by Noyori (2003), the nature of the coordinated ligand switches between amine (RR'HN-MLn) and amide (RR'N-MLn) (MLn is what? Please define; Wu et al., 2010). However, some `non-NH' P,N-containing ferrocenylphosphanes have recently demonstrated good activity and selectivity in ATH. The lack of an N—H bond suggested a new mechanism and attracted our attention. To address this issue, we synthesized a new family of chiral P,N-containing ferrocenylphosphanes (planar chirality) bearing a mono­tosyl­ated amine fragment (TosNR, with R = H, Me) to study their coordination chemistry with Rh, Ir and Ru precursors by NMR analysis and density functional theory (DFT) calculations, to investigate their efficiency in ATH and to better understand the mechanisms involved (Wei et al., 2013). Unprotected rac-1-[(N,4-di­methyl­benzene­sulfonamido)­methyl]-2-(di­phenyl­phosphanyl)ferrocene, (3), is partially oxidized to rac-1-[(N,4-di­methyl­benzene­sulfonamido)­methyl]-2-(di­phenyl­phospho­ryl)ferrocene, (4), in air after a few days to give the title cocrystal, (3)0.55.(4)0.45, denoted (I).

Experimental top

Synthesis and crystallization top

The title compound was prepared in a two-step synthesis from 1-di­phenyl­phosphino­thioyl-2-(hy­droxy­methyl)­ferrocene, (1) (see scheme; Wei et al., 2013). This compound can be prepared in multigram qu­anti­ties and isolated as a racemic mixture or in a pure enanti­omeric form, making direct access to chiral ligands possible. Its functionalization can be performed in a one-pot process by successive addition of a strong acid (HBF4), probably generating a ferrocenyl carbocation and then the amine nucleophile. The phosphanyl function, protected from oxidation by an S atom, allowing working in air, was recovered by refluxing in toluene with P(NMe3)3. In the presence of air, compound (3) is partially oxidized to compound (4), giving the title cocrystal, (I).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were fixed geometrically and treated as riding, with C—H = 0.99 (methyl­ene), 0.98 (methyl) or 0.95 Å (methine), and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) otherwise.

Initially, the occupancy of atom O1 was freely refined with a fixed isotropic displacement parameter, the value of which was taken from the other O atoms. In a second step, the occupancy and the isotropic displacement parameter were freely refined. The refinement converged smoothly with no change to the occupancy factor. In the final step of the refinement, the occupancy was fixed and the displacement parameter refined anisotropically. There was no residual density in the vicinity of this O atom in a chemically reasonable position.

Results and discussion top

A view of the molecule of (I) is represented in Fig. 1. It is built up from a ferrocene group disubstituted by a partially oxidized di­phenyl­phosphanyl [occupancy factor 0.43 (1)] and an (N,4-di­methyl­benzene­sulfonamido)­methyl substituent. Owing to the partially oxidized phosphanyl group, it is best to consider the crystal as built up of a mixture of non-oxidized and oxidized phosphane, so it can be regarded as a cocrystal. Previously, we collected data at 180 K on a crystal resulting from the same synthesis route and obtained the same structure with an occupancy factor of 0.49 (1) and a short PO bond. Puzzled by such a result, we later collected data for a second crystal at 100 K. The second crystal was of better quality and, as the data were collected at 100 K, the final refinement was better, so we have used the second set of data for this report.

An inter­esting feature of the structure of (I) is the rather short PO distance of 1.344 (4) Å. A search of the Cambridge Structural Database (CSD; Version 5.33, update of June 2013; Allen, 2002) for related ferrocenylphosphine oxide compounds revealed 33 hits with PO distances ranging from 1.43 to 1.53 Å. So, as far as we know, the distance observed in cocrystal (I) is the shortest reported up now (Fig. 2). This short distance might be related to the partial occupancy of atom O1 (0.45) and to the influence of the electron density of the P-atom lone pair, which inter­feres with the weak electron density of atom O1 (roughly four electrons). Although this result is surprising, there is no chemical evidence for considering another atom having about four electrons attached to the phosphane. A protecting –BH3 group would lead to a longer P—B distance of about 1.9 Å, and a residual S atom on the P atom would result in a P—S bond of about 1.9 Å. So, chemically and structurally, there is no other choice than considering an O atom with partial occupancy. Such a hypothesis is confirmed by a 31P NMR analysis carried out in CDCl3 (Fig. 3b). The NMR spectrum clearly shows two resonances; that at δ = -25.41 p.p.m. can be attributed to a free phosphane group and that at δ = 28.75 p.p.m. corresponds to an oxidized phosphane group (Štěpnička & Cisařovà, 2002; Chernyshev & Krivdin, 2010).

The two cyclo­penta­dienyl (Cp) rings are nearly eclipsed, with a rotation angle between the rings of τ = 4.20 (17)°. The phosphane P atom is slightly exo from the Cp ring with a deviation from the plane of -0.374 (2) Å, whereas atom O1 is endo, with a deviation of 0.418 (2) Å from the plane. Atom N1 is exo from the Cp ring by -0.644 (2) Å.

The packing of (I) is stabilized by C—H···O inter­actions involving atom O11 of the SO2 group, as well as the partially occupied O1 atom. A C28···O11 inter­action results in a ten-membered ring around the 1,1,1 inversion centre, forming a pseudo-dimer (Fig. 4 and Table 2) (Etter, 1990; Bernstein et al., 1995). An inter­action between atom C126 of one of the phenyl rings of the di­phenyl­phosphanyl group and partially occupied atom O1 is the result and this, combined with an inter­action between atom C6 of the uncoordinated Cp ring and partially occupied atom O1, link the pseudo-dimeric units to build up a chain along the c axis (Fig. 4 and Table 2). Weak C—H···π inter­actions occur between atom C9 and the centroid (Cg3) of the C23–C28 ring, between atom C4 and the centroid (Cg5) of the C121–C126 ring, between atom C29 and the centroid (Cg4) of the C111–C116 ring, and between atom C113 and the centroid (Cg1?) of the substituted Cp ring (Table 2). Such weak inter­actions assure the cohesion of the crystal.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Chernyshev & Krivdin (2010); Etter (1990); Noyori (2003); Wei et al. (2013); Wu et al. (2010); Štěpnička & Cisařovà (2002).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: APEX2 (Bruker, 2013); data reduction: APEX2 (Bruker, 2013); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Frequency of occurrence of PO distances observed in the literature.
[Figure 3] Fig. 3. Comparison of the 31P NMR spectra for (a) the free phosphine ferrocenyl compound, (3) (C31H30FeNO2), and (b) the partially oxidized phosphine, (4) (C31H30FeNO2.45PS), of the title compound.
[Figure 4] Fig. 4. A partial packing view for (I), showing the chain formed by the C(8)R22(10) and C(9)R22(12) motifs. [Symmetry codes: (i) -x + 2, -y + 2, -z + 2; (ii) -x + 2, -y + 2, -z + 1.]
rac-1-[(N,4-Dimethylbenzenesulfonamido)methyl]-2-(diphenylphosphoryl)ferrocene–rac-1-[(N,4-dimethylbenzenesulfonamido)methyl]-2-(diphenylphosphanyl)ferrocene (0.45/0.55) top
Crystal data top
[Fe(C5H5)(C26H5NO2PS)]0.55·[Fe(C5H5)(C26H25NO3PS)]0.45Z = 2
Mr = 574.65F(000) = 592
Triclinic, P1Dx = 1.422 Mg m3
a = 10.4675 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.5147 (6) ÅCell parameters from 7259 reflections
c = 13.1941 (8) Åθ = 2.3–28.2°
α = 108.426 (3)°µ = 0.74 mm1
β = 101.310 (4)°T = 173 K
γ = 96.791 (3)°Flattened, yellow
V = 1325.38 (14) Å30.25 × 0.13 × 0.01 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5366 independent reflections
Radiation source: sealed tube4443 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
φ and ω scansθmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
h = 1213
Tmin = 0.614, Tmax = 0.746k = 1310
15594 measured reflectionsl = 1616
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0355P)2 + 1.2324P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
5366 reflectionsΔρmax = 0.49 e Å3
345 parametersΔρmin = 0.42 e Å3
Crystal data top
[Fe(C5H5)(C26H5NO2PS)]0.55·[Fe(C5H5)(C26H25NO3PS)]0.45γ = 96.791 (3)°
Mr = 574.65V = 1325.38 (14) Å3
Triclinic, P1Z = 2
a = 10.4675 (7) ÅMo Kα radiation
b = 10.5147 (6) ŵ = 0.74 mm1
c = 13.1941 (8) ÅT = 173 K
α = 108.426 (3)°0.25 × 0.13 × 0.01 mm
β = 101.310 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5366 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
4443 reflections with I > 2σ(I)
Tmin = 0.614, Tmax = 0.746Rint = 0.042
15594 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.03Δρmax = 0.49 e Å3
5366 reflectionsΔρmin = 0.42 e Å3
345 parameters
Special details top

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*/UeqOcc. (<1)
Fe10.72539 (3)1.05475 (3)0.67363 (3)0.01766 (10)
S10.88951 (7)0.73412 (6)0.92831 (5)0.03030 (16)
P10.81825 (6)0.79165 (6)0.49587 (5)0.02320 (15)
O110.9022 (2)0.86950 (18)1.00423 (14)0.0370 (5)
O120.8203 (2)0.62042 (19)0.94604 (16)0.0432 (5)
N10.8120 (2)0.7321 (2)0.80718 (16)0.0284 (5)
C10.7116 (2)0.8522 (2)0.58505 (18)0.0183 (5)
C20.7394 (2)0.8768 (2)0.70240 (18)0.0190 (5)
C30.6332 (2)0.9326 (2)0.74144 (19)0.0232 (5)
H30.62490.95740.81530.028*
C40.5419 (2)0.9449 (2)0.65185 (19)0.0230 (5)
H40.46280.98020.65560.028*
C50.5889 (2)0.8955 (2)0.55586 (19)0.0205 (5)
H50.54640.89180.48410.025*
C60.8821 (3)1.1717 (2)0.6514 (2)0.0299 (6)
H60.94251.13880.60880.036*
C70.7610 (3)1.2086 (2)0.6123 (2)0.0297 (6)
H70.72591.20480.53910.036*
C80.7019 (3)1.2518 (2)0.7017 (2)0.0302 (6)
H80.61971.28200.69910.036*
C90.7860 (3)1.2423 (2)0.7957 (2)0.0299 (6)
H90.77051.26540.86730.036*
C100.8974 (3)1.1925 (2)0.7646 (2)0.0295 (6)
H100.96981.17590.81150.035*
C210.8554 (2)0.8481 (2)0.77312 (19)0.0245 (5)
H21A0.92360.82610.73140.029*
H21B0.89550.93030.83930.029*
C220.7796 (3)0.5984 (3)0.7185 (2)0.0404 (7)
H22A0.71260.60070.65610.061*
H22B0.74480.52820.74550.061*
H22C0.85990.57720.69450.061*
C231.0501 (3)0.7055 (2)0.92053 (19)0.0299 (6)
C241.0774 (3)0.5739 (3)0.8981 (2)0.0364 (7)
H241.00930.49930.88770.044*
C251.2030 (3)0.5525 (3)0.8911 (2)0.0390 (7)
H251.22100.46290.87700.047*
C261.3039 (3)0.6587 (3)0.9040 (2)0.0377 (7)
C271.2745 (3)0.7896 (3)0.9266 (2)0.0360 (6)
H271.34250.86410.93660.043*
C281.1496 (3)0.8137 (3)0.9347 (2)0.0343 (6)
H281.13180.90340.94980.041*
C291.4398 (3)0.6340 (3)0.8928 (2)0.0471 (8)
H29A1.43780.59260.81460.071*
H29B1.46690.57230.93160.071*
H29C1.50330.72110.92490.071*
C1110.7688 (2)0.6059 (2)0.44556 (18)0.0210 (5)
C1120.6431 (3)0.5362 (2)0.4364 (2)0.0262 (5)
H1120.57680.58600.45750.031*
C1130.6140 (3)0.3947 (3)0.3965 (2)0.0303 (6)
H1130.52810.34770.39060.036*
C1140.7099 (3)0.3218 (2)0.3653 (2)0.0318 (6)
H1140.68960.22480.33750.038*
C1150.8345 (3)0.3894 (3)0.3743 (2)0.0343 (6)
H1150.90030.33890.35330.041*
C1160.8644 (3)0.5311 (3)0.4140 (2)0.0285 (5)
H1160.95060.57730.41970.034*
C1210.7525 (2)0.8307 (2)0.37231 (19)0.0216 (5)
C1220.6474 (3)0.7456 (3)0.2867 (2)0.0304 (6)
H1220.60110.66700.29400.036*
C1230.6092 (3)0.7739 (3)0.1905 (2)0.0400 (7)
H1230.53570.71600.13330.048*
C1240.6777 (3)0.8860 (3)0.1778 (2)0.0403 (7)
H1240.65350.90360.11100.048*
C1250.7808 (3)0.9718 (3)0.2617 (2)0.0363 (7)
H1250.82701.04970.25330.044*
C1260.8183 (3)0.9458 (3)0.3592 (2)0.0293 (6)
H1260.88921.00680.41730.035*
O10.9500 (4)0.8276 (4)0.5403 (3)0.0330 (9)0.45
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.02552 (19)0.00944 (16)0.01767 (17)0.00291 (13)0.00327 (13)0.00566 (12)
S10.0546 (4)0.0182 (3)0.0220 (3)0.0101 (3)0.0072 (3)0.0126 (2)
P10.0338 (4)0.0172 (3)0.0221 (3)0.0105 (3)0.0088 (3)0.0084 (2)
O110.0651 (13)0.0239 (9)0.0234 (9)0.0155 (9)0.0095 (9)0.0087 (8)
O120.0712 (14)0.0290 (10)0.0420 (11)0.0110 (10)0.0181 (10)0.0268 (9)
N10.0451 (13)0.0152 (10)0.0239 (11)0.0022 (9)0.0010 (9)0.0112 (8)
C10.0260 (12)0.0083 (10)0.0197 (11)0.0023 (8)0.0042 (9)0.0052 (8)
C20.0276 (12)0.0087 (10)0.0202 (11)0.0014 (9)0.0028 (9)0.0069 (8)
C30.0360 (14)0.0117 (10)0.0225 (12)0.0004 (10)0.0100 (10)0.0067 (9)
C40.0246 (12)0.0138 (11)0.0288 (13)0.0018 (9)0.0070 (10)0.0054 (9)
C50.0240 (12)0.0104 (10)0.0233 (12)0.0011 (9)0.0002 (9)0.0048 (9)
C60.0324 (14)0.0183 (12)0.0373 (15)0.0036 (10)0.0112 (12)0.0087 (11)
C70.0407 (15)0.0170 (12)0.0283 (13)0.0053 (11)0.0023 (11)0.0141 (10)
C80.0349 (14)0.0102 (11)0.0438 (16)0.0054 (10)0.0057 (12)0.0093 (11)
C90.0458 (16)0.0148 (12)0.0221 (13)0.0029 (11)0.0072 (11)0.0008 (10)
C100.0296 (13)0.0187 (12)0.0313 (14)0.0041 (10)0.0058 (11)0.0081 (10)
C210.0356 (14)0.0152 (11)0.0230 (12)0.0025 (10)0.0011 (10)0.0114 (10)
C220.064 (2)0.0162 (13)0.0320 (15)0.0008 (13)0.0039 (14)0.0087 (11)
C230.0553 (17)0.0188 (12)0.0161 (12)0.0115 (12)0.0017 (11)0.0094 (10)
C240.066 (2)0.0179 (13)0.0256 (13)0.0110 (13)0.0061 (13)0.0099 (11)
C250.072 (2)0.0220 (14)0.0263 (14)0.0221 (14)0.0091 (14)0.0099 (11)
C260.0617 (19)0.0330 (15)0.0167 (12)0.0174 (14)0.0037 (12)0.0072 (11)
C270.0516 (18)0.0256 (14)0.0266 (14)0.0083 (13)0.0022 (12)0.0076 (11)
C280.0606 (19)0.0167 (12)0.0231 (13)0.0107 (12)0.0027 (12)0.0068 (10)
C290.065 (2)0.0449 (18)0.0294 (15)0.0254 (16)0.0056 (14)0.0090 (13)
C1110.0330 (13)0.0161 (11)0.0154 (11)0.0094 (10)0.0043 (9)0.0066 (9)
C1120.0366 (14)0.0209 (12)0.0253 (13)0.0106 (10)0.0149 (11)0.0077 (10)
C1130.0441 (15)0.0211 (13)0.0283 (13)0.0019 (11)0.0148 (12)0.0101 (10)
C1140.0530 (17)0.0147 (12)0.0286 (13)0.0092 (11)0.0129 (12)0.0062 (10)
C1150.0425 (16)0.0221 (13)0.0375 (15)0.0172 (12)0.0099 (12)0.0052 (11)
C1160.0318 (14)0.0234 (13)0.0293 (13)0.0088 (11)0.0050 (11)0.0079 (10)
C1210.0307 (13)0.0158 (11)0.0226 (12)0.0100 (10)0.0109 (10)0.0078 (9)
C1220.0464 (16)0.0197 (12)0.0229 (13)0.0044 (11)0.0059 (11)0.0068 (10)
C1230.0598 (19)0.0299 (15)0.0246 (14)0.0096 (14)0.0028 (13)0.0062 (11)
C1240.071 (2)0.0390 (16)0.0243 (14)0.0250 (15)0.0189 (14)0.0189 (12)
C1250.0528 (18)0.0309 (15)0.0418 (16)0.0154 (13)0.0258 (14)0.0241 (13)
C1260.0357 (14)0.0237 (13)0.0327 (14)0.0075 (11)0.0135 (11)0.0120 (11)
O10.033 (2)0.022 (2)0.044 (2)0.0003 (17)0.0090 (19)0.0128 (18)
Geometric parameters (Å, º) top
Fe1—C32.038 (2)C21—H21B0.9900
Fe1—C42.038 (2)C22—H22A0.9800
Fe1—C22.039 (2)C22—H22B0.9800
Fe1—C82.040 (2)C22—H22C0.9800
Fe1—C52.044 (2)C23—C281.387 (4)
Fe1—C92.045 (2)C23—C241.397 (3)
Fe1—C12.052 (2)C24—C251.376 (4)
Fe1—C72.052 (2)C24—H240.9500
Fe1—C102.054 (2)C25—C261.386 (4)
Fe1—C62.056 (2)C25—H250.9500
S1—O121.4308 (19)C26—C271.399 (4)
S1—O111.4315 (19)C26—C291.503 (4)
S1—N11.637 (2)C27—C281.379 (4)
S1—C231.759 (3)C27—H270.9500
P1—O11.344 (4)C28—H280.9500
P1—C11.802 (2)C29—H29A0.9800
P1—C1111.825 (2)C29—H29B0.9800
P1—C1211.830 (2)C29—H29C0.9800
N1—C221.467 (3)C111—C1121.391 (3)
N1—C211.480 (3)C111—C1161.391 (3)
C1—C51.435 (3)C112—C1131.385 (3)
C1—C21.449 (3)C112—H1120.9500
C2—C31.426 (3)C113—C1141.381 (4)
C2—C211.502 (3)C113—H1130.9500
C3—C41.418 (3)C114—C1151.373 (4)
C3—H30.9500C114—H1140.9500
C4—C51.416 (3)C115—C1161.388 (3)
C4—H40.9500C115—H1150.9500
C5—H50.9500C116—H1160.9500
C6—C101.413 (4)C121—C1221.388 (3)
C6—C71.417 (4)C121—C1261.397 (3)
C6—H60.9500C122—C1231.388 (4)
C7—C81.412 (4)C122—H1220.9500
C7—H70.9500C123—C1241.380 (4)
C8—C91.412 (4)C123—H1230.9500
C8—H80.9500C124—C1251.368 (4)
C9—C101.414 (4)C124—H1240.9500
C9—H90.9500C125—C1261.390 (4)
C10—H100.9500C125—H1250.9500
C21—H21A0.9900C126—H1260.9500
C3—Fe1—C440.70 (10)C8—C7—C6107.7 (2)
C3—Fe1—C240.95 (9)C8—C7—Fe169.33 (13)
C4—Fe1—C269.07 (9)C6—C7—Fe169.98 (14)
C3—Fe1—C8122.18 (10)C8—C7—H7126.1
C4—Fe1—C8105.91 (10)C6—C7—H7126.1
C2—Fe1—C8159.02 (10)Fe1—C7—H7126.1
C3—Fe1—C568.46 (9)C9—C8—C7108.2 (2)
C4—Fe1—C540.60 (9)C9—C8—Fe169.98 (14)
C2—Fe1—C569.22 (9)C7—C8—Fe170.29 (13)
C8—Fe1—C5121.03 (10)C9—C8—H8125.9
C3—Fe1—C9105.22 (10)C7—C8—H8125.9
C4—Fe1—C9118.92 (10)Fe1—C8—H8125.4
C2—Fe1—C9122.78 (10)C8—C9—C10108.0 (2)
C8—Fe1—C940.44 (10)C8—C9—Fe169.58 (14)
C5—Fe1—C9154.98 (10)C10—C9—Fe170.15 (14)
C3—Fe1—C169.04 (9)C8—C9—H9126.0
C4—Fe1—C168.97 (9)C10—C9—H9126.0
C2—Fe1—C141.50 (8)Fe1—C9—H9125.9
C8—Fe1—C1157.52 (10)C6—C10—C9107.9 (2)
C5—Fe1—C141.03 (9)C6—C10—Fe170.01 (14)
C9—Fe1—C1161.41 (10)C9—C10—Fe169.49 (14)
C3—Fe1—C7159.73 (10)C6—C10—H10126.1
C4—Fe1—C7124.42 (10)C9—C10—H10126.1
C2—Fe1—C7158.77 (10)Fe1—C10—H10126.0
C8—Fe1—C740.38 (11)N1—C21—C2110.37 (19)
C5—Fe1—C7109.24 (9)N1—C21—H21A109.6
C9—Fe1—C767.89 (10)C2—C21—H21A109.6
C1—Fe1—C7123.37 (10)N1—C21—H21B109.6
C3—Fe1—C10120.07 (10)C2—C21—H21B109.6
C4—Fe1—C10154.51 (10)H21A—C21—H21B108.1
C2—Fe1—C10107.35 (10)N1—C22—H22A109.5
C8—Fe1—C1067.93 (10)N1—C22—H22B109.5
C5—Fe1—C10163.73 (10)H22A—C22—H22B109.5
C9—Fe1—C1040.36 (11)N1—C22—H22C109.5
C1—Fe1—C10126.04 (10)H22A—C22—H22C109.5
C7—Fe1—C1067.85 (10)H22B—C22—H22C109.5
C3—Fe1—C6156.60 (10)C28—C23—C24119.8 (3)
C4—Fe1—C6162.45 (10)C28—C23—S1119.8 (2)
C2—Fe1—C6122.70 (10)C24—C23—S1120.4 (2)
C8—Fe1—C667.80 (11)C25—C24—C23119.9 (3)
C5—Fe1—C6127.30 (10)C25—C24—H24120.1
C9—Fe1—C667.71 (10)C23—C24—H24120.1
C1—Fe1—C6110.17 (10)C24—C25—C26121.5 (2)
C7—Fe1—C640.36 (10)C24—C25—H25119.2
C10—Fe1—C640.20 (10)C26—C25—H25119.2
O12—S1—O11119.66 (12)C25—C26—C27117.7 (3)
O12—S1—N1106.61 (12)C25—C26—C29121.3 (3)
O11—S1—N1106.73 (11)C27—C26—C29121.0 (3)
O12—S1—C23108.00 (12)C28—C27—C26121.8 (3)
O11—S1—C23107.88 (12)C28—C27—H27119.1
N1—S1—C23107.40 (11)C26—C27—H27119.1
O1—P1—C1117.33 (19)C27—C28—C23119.3 (2)
O1—P1—C111109.51 (18)C27—C28—H28120.3
C1—P1—C111104.64 (10)C23—C28—H28120.3
O1—P1—C121117.76 (19)C26—C29—H29A109.5
C1—P1—C121104.13 (10)C26—C29—H29B109.5
C111—P1—C121101.63 (10)H29A—C29—H29B109.5
C22—N1—C21114.2 (2)C26—C29—H29C109.5
C22—N1—S1115.35 (16)H29A—C29—H29C109.5
C21—N1—S1117.69 (16)H29B—C29—H29C109.5
C5—C1—C2106.99 (19)C112—C111—C116118.9 (2)
C5—C1—P1126.75 (17)C112—C111—P1124.32 (18)
C2—C1—P1126.08 (17)C116—C111—P1116.75 (18)
C5—C1—Fe169.17 (12)C113—C112—C111120.4 (2)
C2—C1—Fe168.77 (12)C113—C112—H112119.8
P1—C1—Fe1123.40 (11)C111—C112—H112119.8
C3—C2—C1107.4 (2)C114—C113—C112120.1 (2)
C3—C2—C21124.5 (2)C114—C113—H113120.0
C1—C2—C21128.1 (2)C112—C113—H113120.0
C3—C2—Fe169.48 (12)C115—C114—C113120.1 (2)
C1—C2—Fe169.73 (12)C115—C114—H114119.9
C21—C2—Fe1126.98 (15)C113—C114—H114119.9
C4—C3—C2108.7 (2)C114—C115—C116120.2 (2)
C4—C3—Fe169.66 (13)C114—C115—H115119.9
C2—C3—Fe169.56 (12)C116—C115—H115119.9
C4—C3—H3125.6C115—C116—C111120.3 (2)
C2—C3—H3125.6C115—C116—H116119.9
Fe1—C3—H3126.7C111—C116—H116119.9
C5—C4—C3108.2 (2)C122—C121—C126118.2 (2)
C5—C4—Fe169.90 (13)C122—C121—P1123.25 (18)
C3—C4—Fe169.64 (13)C126—C121—P1118.33 (19)
C5—C4—H4125.9C123—C122—C121120.9 (2)
C3—C4—H4125.9C123—C122—H122119.6
Fe1—C4—H4126.1C121—C122—H122119.6
C4—C5—C1108.6 (2)C124—C123—C122120.1 (3)
C4—C5—Fe169.50 (13)C124—C123—H123120.0
C1—C5—Fe169.80 (12)C122—C123—H123120.0
C4—C5—H5125.7C125—C124—C123119.9 (2)
C1—C5—H5125.7C125—C124—H124120.1
Fe1—C5—H5126.6C123—C124—H124120.1
C10—C6—C7108.2 (2)C124—C125—C126120.5 (3)
C10—C6—Fe169.79 (14)C124—C125—H125119.7
C7—C6—Fe169.66 (14)C126—C125—H125119.7
C10—C6—H6125.9C125—C126—C121120.4 (3)
C7—C6—H6125.9C125—C126—H126119.8
Fe1—C6—H6126.2C121—C126—H126119.8
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C5 ring?, Cg3 is that of the C23–C28 ring, Cg4 that of the C111–C116 ring and Cg5 that of the C121–C126 ring.
D—H···AD—HH···AD···AD—H···A
C28—H28···O11i0.952.363.308 (3)177
C126—H126···O1ii0.952.122.948 (5)145
C6—H6···O1ii0.952.553.352 (5)143
C4—H4···Cg5iii0.952.753.667 (2)162
C9—H9···Cg3i0.952.713.607 (2)158
C29—H29A···Cg4iv0.982.963.761 (3)140
C113—H113···Cg1v0.952.833.672 (3)149
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+2, y+2, z+1; (iii) x+1, y+2, z+1; (iv) x+2, y+1, z+1; (v) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Fe(C5H5)(C26H5NO2PS)]0.55·[Fe(C5H5)(C26H25NO3PS)]0.45
Mr574.65
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)10.4675 (7), 10.5147 (6), 13.1941 (8)
α, β, γ (°)108.426 (3), 101.310 (4), 96.791 (3)
V3)1325.38 (14)
Z2
Radiation typeMo Kα
µ (mm1)0.74
Crystal size (mm)0.25 × 0.13 × 0.01
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.614, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
15594, 5366, 4443
Rint0.042
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.097, 1.03
No. of reflections5366
No. of parameters345
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.42

Computer programs: APEX2 (Bruker, 2013), SIR97 (Altomare et al., 1999), SHELXL2013 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C5 ring?, Cg3 is that of the C23–C28 ring, Cg4 that of the C111–C116 ring and Cg5 that of the C121–C126 ring.
D—H···AD—HH···AD···AD—H···A
C28—H28···O11i0.952.363.308 (3)176.9
C126—H126···O1ii0.952.122.948 (5)144.7
C6—H6···O1ii0.952.553.352 (5)142.9
C4—H4···Cg5iii0.952.753.667 (2)162.1
C9—H9···Cg3i0.952.713.607 (2)158.0
C29—H29A···Cg4iv0.982.963.761 (3)139.7
C113—H113···Cg1v0.952.833.672 (3)148.9
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+2, y+2, z+1; (iii) x+1, y+2, z+1; (iv) x+2, y+1, z+1; (v) x+1, y+1, z+1.
 

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