A new monoclinic polymorph of 1,1′-bis­(di­phenyl­thio­phosphor­yl)ferrocene

Tan, Y.S.; Yeo, C.I.; Tiekink, E.R.T.

doi:10.1107/S2056989015012682

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Volume 71| Part 8| August 2015| Pages 886-889

https://doi.org/10.1107/S2056989015012682

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A new monoclinic polymorph of 1,1′-bis(diphenylthiophosphoryl)ferrocene

Yee Seng Tan,^a Chien Ing Yeo ^a and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: Edward.Tiekink@gmail.com

Edited by P. C. Healy, Griffith University, Australia (Received 30 June 2015; accepted 1 July 2015; online 4 July 2015)

The title compound, [Fe(C₁₇H₁₄PS)₂], is a second monoclinic polymorph (P2₁/c, with Z′ = 1) of the previously reported monoclinic (C2/c, with Z′ = 1/2) form [Fang et al. (1995 ). Polyhedron, 14, 2403–2409]. In the new form, the S atoms lie to the same side of the molecule with the pseudo S—P⋯P—S torsion angle being −53.09 (3)°. By contrast to this almost syn disposition, in the C2/c polymorph, the Fe atom lies on a centre of inversion so that the S atoms are strictly anti, with a pseudo-S—P⋯P—S torsion angle of 180°. The significant difference in molecular conformation between the two forms does not result in major perturbations in the P=S bond lengths nor in the distorted tetrahedral geometries about the P atoms. The crystal packing of the new monoclinic polymorph features weak Cp—C—H⋯π(phenyl) interactions consolidating linear supramolecular chains along the a axis. These pack with no directional interactions between them.

Keywords: crystals structure; ferrocene derivative; polymorph; conformation.

CCDC reference: 1409866

1. Chemical context

Phosphanegold(I) dithiocarbamates, R₃PAu(S₂CNR′₂), attract on-going interest owing to impressive biological activities against both cancer (Jamaludin et al., 2013 ) and microbes (Sim et al., 2014 ). It was in the course of these studies that crystals of the title compound, dppfS₂, an oxidation product of 1,1′-bis(diphenylphosphane)ferrocene (dppf), were isolated as orange needles, being a side-product of a reaction, see Synthesis and crystallization for details. Crystallography shows the title compound to be a new monoclinic polymorph of a previously described C2/c form (Fang et al., 1995). Herein, details of the new polymorph are described along with a comparison with the original polymorph. A discussion of the key structural characteristics of related dppfY₂, Y = 0, O, S and Se, structures ensues.

2. Structural commentary

The molecular structure of dppfS₂ is shown in Fig. 1 and comprises two Ph₂P=S units linked via the P atoms through a C₅H₄FeC₅H₄ link. The S atoms lie to the same side of the molecule and might be described as having a syn conformation. When viewed down the P⋯P axis, the S atoms are gauche with the pseudo S—P⋯P—S torsion angle being −53.09 (3)°. This represents the major difference between dppfS₂ and its C2/c–dppfS₂ polymorph (Fang et al., 1995). In the latter the Fe atom lies on a crystallographic centre of inversion, implying the S atoms are anti and that the pseudo S—P⋯P—S torsion angle is 180°.

Figure 1
The molecular structure of the new P2₁/c polymorph of dppfS₂, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

The conformational differences in the polymorphs are highlighted in the overlay diagram shown in Fig. 2. The Fe atom is equally disposed from the centroids of the very nearly eclipsed Cp rings: Fe⋯Cg(C1–C5) and Cg(C6–C10) are 1.6487 (8) and 1.6451 (8) Å, respectively, and the Cg(C1–C5)⋯Fe⋯Cg(C6–C10) angle is 178.92 (5)°. The comparable parameters for the C2/c–dppfS₂ polymorph are 1.650 (3) Å and 180°, and the Cp rings are strictly staggered when viewed down the Cg(C1–C5)⋯Fe⋯Cg(C1–C5)ⁱ axis. In dppfS₂, the P=S bond lengths are experimentally distinct, i.e. P1=S1 of 1.9449 (6) Å is shorter than P2=S2 of 1.9530 (6) Å, with the former being equivalent to P1=S1 of 1.9384 (18) Å in C2/c–dppfS₂. Finally, the P1 and P2 atoms have distorted tetrahedral environments with the range of angles subtended at P1 of 103.94 (7)–113.78 (6)° being comparable to those subtended at P2, i.e. 105.55 (7)–114.92 (5)°; the equivalent range of angles in C2/c–dppfS₂ is 104.8 (2)–114.28 (15)°. In each case, the angles involving the S atom are wider than those involving C atoms only, and the narrowest angle always involves the two ipso-C atoms.

Figure 2
Overlay diagram of the P2₁/c (red image) and C2/c (green) polymorphs overlapped so that one Cp ring of each molecule is coincident.

3. Supramolecular features

Globally, the crystal packing features columns of molecules aligned along the a axis. Based on the distance criteria employed in PLATON (Spek, 2009 ), the most notable intermolecular contact operating in the crystal structure is a Cp-C2—H2⋯π(C31–C36) interaction, Table 1, that connects translationally related molecules into a supramolecular chain along the a axis, Fig. 3. Chains pack with no specific directional interactions between them, Fig. 4. In the C2/c–dppfS₂ polymorph, the most prominent directional interaction is a weak C—H⋯S contact. The crystal packing efficiencies calculated by PLATON (Spek, 2009) are 69.3 and 67.2%, respectively, indicating the more symmetric structure packs less efficiently.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C31–C36 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg1ⁱ	0.95	2.92	3.6111 (18)	130
Symmetry code: (i) x-1, y, z.

Figure 3
Supramolecular chain along the a axis sustained by C—H⋯π interactions shown as purple dashed lines.

Figure 4
Unit-cell contents shown in projection down the a axis. The C—H⋯π contacts are shown purple dashed lines. One of the supramolecular chains shown in Fig. 3

has been highlighted in space-filling mode.

4. Database survey

Subsequent to the report of the C2/c form by Fang et al. (1995), a second report appeared (Pilloni et al., 1997 ). In the latter analysis, the authors suggested that Cc was the correct space group. The assignment of C2/c was later confirmed as being correct (Clemente & Marzotto, 2004 ).

The structures of several oxidation products of dppf, Ph₂P(=Y)C₅H₄FeC₅H₄P(=Y)Ph₂, Y = 0, O, S and Se, have been described in the crystallographic literature. The parent compound, i.e. with Y = lone pair, has the Fe atom situated on a centre of inversion (Casellato et al., 1988 ). When Y = O, an unsolvated form has been reported with the Fe atom again located on a centre of inversion (Pilloni et al., 1993 ). A monohydrate (Bar et al., 2008 ; Bolte et al., 1997 ) as well as a dihydrate (Munyejabo et al., 1994 ; Fang et al., 1995) have also been described. In the former, the O atoms are approximately syn while the latter is centrosymmetric, i.e. resembling the situation with the Y = S polymorphs. Finally, when Y = Se, centrosymmetric structures are found in the unsolvated form (Arsenyan et al., 2012 ) as well as in the CH₂Cl₂ monosolvate (Pilloni et al., 1997). Clearly, there is significant conformational flexibility in the Ph₂P(=Y)C₅H₄FeC₅H₄P(=Y)Ph₂, Y = 0, O, S and Se, compounds suggesting a low energy barrier for the interchange from one conformation to another. The structural data for Ph₂P(=Y)C₅H₄FeC₅H₄P(=Y)Ph₂ are summarized in Table 2.

Table 2
Summary of structural data (Å) for Ph₂P(=Y)C₅H₄FeC₅H₄P(=Y)Ph₂

Y	Symmetry	Y—P⋯P—Y	Solvent	CSD refcode^a	Reference
O	$[\overline{1}]$	180	–	KADXAO	Casellato et al. (1988)
O	$[\overline{1}]$	180	–	WARMUX	Pilloni et al. (1993)
O	–	155.57 (18)	H₂O	RUVJEX01	Bar et al. (2008)
O	$[\overline{1}]$	180	2H₂O	HATTUR	Munyejabo et al. (1994)
S	$[\overline{1}]$	180	–	ZEQSOD	Fang et al. (1995)
S	–	−53.09 (3)	–	–	This work
Se	$[\overline{1}]$	180	–	KIHWAB	Arsenyan et al. (2012)
Se	$[\overline{1}]$	180	CH₂Cl₂	RIPTIT	Pilloni et al. (1997)
Note: (a) Cambridge Structural Database (Groom & Allen, 2014 ), Version 5.35.

The dppfS₂ molecule can function as a ligand in metal complexes, often forming zero-dimensional mononuclear species (e.g. Gimeno et al., 1995 , 2000 ; Pilloni et al., 1997) but sometimes binuclear species (Pilloni et al., 1998 ). Two examples exist whereby dppfS₂ bridges metal toms to form one-dimensional coordination polymers (Gimeno et al., 1998 , 2000).

5. Synthesis and crystallization

Two solutions were prepared. Firstly, a solution sodium salt of piperazine dithiocarbamate (0.7 mmol) was prepared by dissolving piperazine (0.0582 g) in acetonitrile (50 ml). NaOH (112 µl of 50% w/w) and CS₂ (84.6 µl) were added. Chloroform (150 ml) was then added and the reaction mixture was stirred for 2 h. A second solution containing [1,1′-bis(diphenylphosphane)ferrocene]bis[chloridogold(I)] (1.4 mmol) was prepared by dissolving potassium tetrachloridoaurate(III) (1.06 g) in a solvent mixture of acetone and water (1:2, 45 ml). Drop-wise addition of sodium sulfite (0.71 g) in water (10 ml) followed. Upon discolouration, bis(diphenylphosphane)ferrocene (dppf, 0.78 g) in chloroform (25 ml) was added. After stirring for 15 mins, the resulting gold precursor was extracted with chloroform (150 ml). Acetonitrile (50 ml) was added to this to form solvent mixture of chloroform and acetonitrile (3:1). The solution containing the dithiocarbamate was added to that containing the gold precursor. The resulting mixture was stirred for 3 h. and then filtered. After three weeks, orange needles appeared, along with the precipitate, and these were subjected to the crystallographic study. Yield: 0.0890 g, 10.3% (based on dppf). M.p.: 519.5–519.9 K. IR: ν(P=S) 628 (m).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_equiv(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(C₁₇H₁₄PS)₂]
M_r	618.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.7451 (3), 21.2453 (6), 15.4537 (5)
β (°)	95.631 (3)
V (Å³)	2857.32 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.81
Crystal size (mm)	0.25 × 0.25 × 0.25

Data collection
Diffractometer	Agilent Technologies SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.751, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	31395, 6509, 5701
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.05
No. of reflections	6509
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.24
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), QMol (Gans & Shalloway, 2001 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1409866

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015012682/hg5450sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012682/hg5450Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

1,1'-Bis(diphenylthiophosphoryl)ferrocene top

Crystal data top

[Fe(C₁₇H₁₄PS)₂]	F(000) = 1280
M_r = 618.47	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.7451 (3) Å	Cell parameters from 11974 reflections
b = 21.2453 (6) Å	θ = 3.9–29.3°
c = 15.4537 (5) Å	µ = 0.81 mm⁻¹
β = 95.631 (3)°	T = 100 K
V = 2857.32 (16) Å³	Prism, orange
Z = 4	0.25 × 0.25 × 0.25 mm

Data collection top

Agilent Technologies SuperNova Dual diffractometer with an Atlas detector	6509 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5701 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.036
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ω scan	h = −10→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −23→27
T_min = 0.751, T_max = 1.000	l = −19→20
31395 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0304P)² + 1.6529P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
6509 reflections	Δρ_max = 0.40 e Å⁻³
352 parameters	Δρ_min = −0.24 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Fe	0.34255 (2)	0.23085 (2)	0.17509 (2)	0.01395 (7)
S1	0.24914 (5)	0.41754 (2)	0.09257 (3)	0.02424 (10)
S2	0.69563 (5)	0.15111 (2)	0.05280 (3)	0.02111 (10)
P1	0.10320 (5)	0.35615 (2)	0.12875 (3)	0.01579 (9)
P2	0.65005 (5)	0.13323 (2)	0.17155 (3)	0.01496 (9)
C1	0.16059 (18)	0.27653 (7)	0.11083 (10)	0.0166 (3)
C2	0.11134 (18)	0.21919 (7)	0.14866 (11)	0.0182 (3)
H2	0.0388	0.2156	0.1903	0.022*
C3	0.19051 (18)	0.16874 (8)	0.11258 (11)	0.0210 (3)
H3	0.1802	0.1254	0.1262	0.025*
C4	0.28756 (19)	0.19377 (8)	0.05290 (10)	0.0203 (3)
H4	0.3530	0.1702	0.0196	0.024*
C5	0.27019 (18)	0.26013 (8)	0.05146 (10)	0.0179 (3)
H5	0.3221	0.2887	0.0172	0.021*
C6	0.54850 (18)	0.19445 (7)	0.22183 (10)	0.0156 (3)
C7	0.56320 (18)	0.26062 (7)	0.20595 (10)	0.0165 (3)
H7	0.6280	0.2795	0.1674	0.020*
C8	0.46383 (19)	0.29294 (8)	0.25808 (11)	0.0200 (3)
H8	0.4509	0.3373	0.2604	0.024*
C9	0.38708 (19)	0.24804 (8)	0.30613 (10)	0.0202 (3)
H9	0.3140	0.2571	0.3460	0.024*
C10	0.43834 (18)	0.18708 (8)	0.28431 (10)	0.0185 (3)
H10	0.4056	0.1483	0.3070	0.022*
C11	0.07025 (18)	0.36206 (7)	0.24275 (10)	0.0172 (3)
C12	0.1599 (2)	0.40242 (8)	0.29758 (11)	0.0219 (3)
H12	0.2401	0.4260	0.2759	0.026*
C13	0.1318 (2)	0.40811 (9)	0.38407 (12)	0.0266 (4)
H13	0.1934	0.4355	0.4215	0.032*
C14	0.0144 (2)	0.37407 (9)	0.41629 (11)	0.0264 (4)
H14	−0.0051	0.3786	0.4754	0.032*
C15	−0.0743 (2)	0.33340 (8)	0.36210 (11)	0.0237 (4)
H15	−0.1535	0.3095	0.3843	0.028*
C16	−0.04748 (19)	0.32759 (8)	0.27542 (11)	0.0204 (3)
H16	−0.1093	0.3001	0.2382	0.025*
C21	−0.08745 (18)	0.36448 (7)	0.07138 (10)	0.0176 (3)
C22	−0.1447 (2)	0.42511 (8)	0.05516 (11)	0.0220 (3)
H22	−0.0829	0.4607	0.0717	0.026*
C23	−0.2922 (2)	0.43325 (8)	0.01480 (11)	0.0254 (4)
H23	−0.3320	0.4745	0.0049	0.030*
C24	−0.3816 (2)	0.38158 (9)	−0.01103 (11)	0.0234 (4)
H24	−0.4826	0.3874	−0.0385	0.028*
C25	−0.32411 (19)	0.32144 (8)	0.00299 (11)	0.0227 (3)
H25	−0.3850	0.2860	−0.0158	0.027*
C26	−0.17703 (19)	0.31268 (8)	0.04459 (10)	0.0196 (3)
H26	−0.1380	0.2713	0.0547	0.023*
C31	0.82272 (18)	0.11941 (7)	0.24346 (10)	0.0177 (3)
C32	0.9158 (2)	0.06866 (8)	0.22515 (13)	0.0268 (4)
H32	0.8863	0.0421	0.1769	0.032*
C33	1.0508 (2)	0.05695 (9)	0.27696 (13)	0.0328 (4)
H33	1.1126	0.0218	0.2650	0.039*
C34	1.0959 (2)	0.09614 (10)	0.34592 (13)	0.0314 (4)
H34	1.1889	0.0880	0.3812	0.038*
C35	1.0063 (2)	0.14718 (9)	0.36387 (11)	0.0267 (4)
H35	1.0390	0.1746	0.4106	0.032*
C36	0.86822 (19)	0.15844 (8)	0.31345 (11)	0.0201 (3)
H36	0.8051	0.1928	0.3269	0.024*
C41	0.53591 (18)	0.06263 (7)	0.18021 (11)	0.0176 (3)
C42	0.53090 (19)	0.03306 (8)	0.26044 (11)	0.0205 (3)
H42	0.5890	0.0493	0.3107	0.025*
C43	0.4402 (2)	−0.02033 (8)	0.26646 (12)	0.0254 (4)
H43	0.4356	−0.0404	0.3211	0.031*
C44	0.3569 (2)	−0.04412 (8)	0.19325 (13)	0.0279 (4)
H44	0.2945	−0.0803	0.1979	0.033*
C45	0.3636 (2)	−0.01573 (8)	0.11305 (13)	0.0285 (4)
H45	0.3070	−0.0327	0.0628	0.034*
C46	0.4534 (2)	0.03775 (8)	0.10640 (11)	0.0230 (4)
H46	0.4584	0.0573	0.0515	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.01307 (12)	0.01394 (11)	0.01483 (12)	−0.00055 (8)	0.00125 (9)	−0.00082 (8)
S1	0.0231 (2)	0.0228 (2)	0.0270 (2)	−0.00807 (17)	0.00339 (18)	0.00380 (17)
S2	0.0243 (2)	0.0204 (2)	0.0197 (2)	−0.00123 (16)	0.00761 (17)	−0.00035 (15)
P1	0.0150 (2)	0.01549 (19)	0.0169 (2)	−0.00153 (15)	0.00182 (15)	0.00147 (15)
P2	0.0147 (2)	0.01333 (18)	0.0172 (2)	−0.00070 (15)	0.00332 (16)	−0.00081 (15)
C1	0.0142 (7)	0.0186 (7)	0.0168 (8)	−0.0006 (6)	0.0000 (6)	0.0003 (6)
C2	0.0128 (7)	0.0204 (8)	0.0213 (8)	−0.0018 (6)	0.0010 (6)	0.0006 (6)
C3	0.0172 (8)	0.0185 (8)	0.0262 (9)	−0.0025 (6)	−0.0038 (7)	−0.0035 (6)
C4	0.0187 (8)	0.0240 (8)	0.0175 (8)	0.0008 (7)	−0.0019 (6)	−0.0068 (6)
C5	0.0153 (8)	0.0237 (8)	0.0144 (7)	−0.0005 (6)	0.0004 (6)	0.0001 (6)
C6	0.0145 (7)	0.0158 (7)	0.0161 (7)	0.0008 (6)	0.0002 (6)	−0.0009 (6)
C7	0.0134 (7)	0.0159 (7)	0.0195 (8)	−0.0021 (6)	−0.0014 (6)	−0.0006 (6)
C8	0.0193 (8)	0.0171 (8)	0.0226 (8)	0.0010 (6)	−0.0031 (7)	−0.0045 (6)
C9	0.0204 (8)	0.0254 (8)	0.0144 (7)	0.0039 (7)	0.0002 (6)	−0.0033 (6)
C10	0.0189 (8)	0.0198 (8)	0.0167 (8)	0.0011 (6)	0.0010 (6)	0.0017 (6)
C11	0.0171 (8)	0.0169 (7)	0.0175 (8)	0.0045 (6)	0.0009 (6)	0.0013 (6)
C12	0.0216 (8)	0.0196 (8)	0.0241 (9)	0.0020 (6)	0.0004 (7)	0.0009 (7)
C13	0.0279 (9)	0.0282 (9)	0.0225 (9)	0.0042 (7)	−0.0042 (7)	−0.0047 (7)
C14	0.0282 (9)	0.0328 (10)	0.0181 (8)	0.0119 (8)	0.0015 (7)	0.0017 (7)
C15	0.0214 (8)	0.0275 (9)	0.0229 (9)	0.0069 (7)	0.0063 (7)	0.0063 (7)
C16	0.0188 (8)	0.0211 (8)	0.0215 (8)	0.0028 (6)	0.0021 (7)	0.0008 (6)
C21	0.0170 (8)	0.0201 (8)	0.0157 (7)	0.0000 (6)	0.0024 (6)	0.0026 (6)
C22	0.0245 (9)	0.0190 (8)	0.0223 (8)	0.0011 (7)	0.0016 (7)	0.0013 (6)
C23	0.0271 (9)	0.0235 (8)	0.0257 (9)	0.0075 (7)	0.0030 (7)	0.0059 (7)
C24	0.0182 (8)	0.0338 (9)	0.0182 (8)	0.0023 (7)	0.0012 (7)	0.0066 (7)
C25	0.0188 (8)	0.0270 (9)	0.0220 (8)	−0.0049 (7)	0.0016 (7)	0.0033 (7)
C26	0.0186 (8)	0.0196 (8)	0.0208 (8)	0.0000 (6)	0.0036 (7)	0.0040 (6)
C31	0.0148 (7)	0.0173 (7)	0.0215 (8)	−0.0014 (6)	0.0039 (6)	0.0040 (6)
C32	0.0230 (9)	0.0218 (8)	0.0360 (10)	0.0026 (7)	0.0050 (8)	0.0002 (7)
C33	0.0226 (9)	0.0322 (10)	0.0444 (12)	0.0097 (8)	0.0064 (8)	0.0096 (9)
C34	0.0148 (8)	0.0469 (12)	0.0324 (10)	0.0004 (8)	0.0018 (7)	0.0179 (9)
C35	0.0211 (9)	0.0397 (10)	0.0194 (8)	−0.0078 (8)	0.0023 (7)	0.0066 (7)
C36	0.0167 (8)	0.0247 (8)	0.0195 (8)	−0.0018 (6)	0.0049 (6)	0.0031 (6)
C41	0.0163 (8)	0.0131 (7)	0.0239 (8)	0.0005 (6)	0.0041 (6)	−0.0022 (6)
C42	0.0169 (8)	0.0178 (8)	0.0269 (9)	0.0005 (6)	0.0028 (7)	0.0016 (7)
C43	0.0202 (9)	0.0201 (8)	0.0367 (10)	0.0017 (7)	0.0063 (8)	0.0074 (7)
C44	0.0203 (9)	0.0150 (8)	0.0489 (11)	−0.0025 (7)	0.0062 (8)	−0.0010 (8)
C45	0.0250 (9)	0.0218 (9)	0.0384 (10)	−0.0036 (7)	0.0008 (8)	−0.0094 (8)
C46	0.0244 (9)	0.0199 (8)	0.0250 (9)	−0.0006 (7)	0.0045 (7)	−0.0049 (7)

Geometric parameters (Å, º) top

Fe—C6	2.0269 (15)	C13—C14	1.387 (3)
Fe—C10	2.0341 (16)	C13—H13	0.9500
Fe—C1	2.0372 (16)	C14—C15	1.387 (3)
Fe—C2	2.0383 (16)	C14—H14	0.9500
Fe—C7	2.0421 (15)	C15—C16	1.388 (2)
Fe—C3	2.0470 (16)	C15—H15	0.9500
Fe—C5	2.0495 (16)	C16—H16	0.9500
Fe—C9	2.0569 (16)	C21—C26	1.390 (2)
Fe—C4	2.0589 (16)	C21—C22	1.396 (2)
Fe—C8	2.0597 (16)	C22—C23	1.387 (2)
S1—P1	1.9449 (6)	C22—H22	0.9500
S2—P2	1.9530 (6)	C23—C24	1.383 (3)
P1—C1	1.7936 (16)	C23—H23	0.9500
P1—C11	1.8171 (16)	C24—C25	1.382 (2)
P1—C21	1.8184 (16)	C24—H24	0.9500
P2—C6	1.7943 (16)	C25—C26	1.393 (2)
P2—C31	1.8089 (16)	C25—H25	0.9500
P2—C41	1.8139 (16)	C26—H26	0.9500
C1—C5	1.433 (2)	C31—C36	1.390 (2)
C1—C2	1.436 (2)	C31—C32	1.397 (2)
C2—C3	1.419 (2)	C32—C33	1.382 (3)
C2—H2	0.9500	C32—H32	0.9500
C3—C4	1.417 (2)	C33—C34	1.379 (3)
C3—H3	0.9500	C33—H33	0.9500
C4—C5	1.418 (2)	C34—C35	1.382 (3)
C4—H4	0.9500	C34—H34	0.9500
C5—H5	0.9500	C35—C36	1.392 (2)
C6—C7	1.435 (2)	C35—H35	0.9500
C6—C10	1.438 (2)	C36—H36	0.9500
C7—C8	1.419 (2)	C41—C46	1.393 (2)
C7—H7	0.9500	C41—C42	1.394 (2)
C8—C9	1.418 (2)	C42—C43	1.392 (2)
C8—H8	0.9500	C42—H42	0.9500
C9—C10	1.422 (2)	C43—C44	1.380 (3)
C9—H9	0.9500	C43—H43	0.9500
C10—H10	0.9500	C44—C45	1.385 (3)
C11—C12	1.392 (2)	C44—H44	0.9500
C11—C16	1.398 (2)	C45—C46	1.391 (2)
C12—C13	1.388 (3)	C45—H45	0.9500
C12—H12	0.9500	C46—H46	0.9500

C6—Fe—C10	41.47 (6)	C6—C7—Fe	68.78 (9)
C6—Fe—C1	168.45 (6)	C8—C7—H7	126.1
C10—Fe—C1	149.39 (7)	C6—C7—H7	126.1
C6—Fe—C2	148.69 (6)	Fe—C7—H7	126.3
C10—Fe—C2	115.49 (7)	C9—C8—C7	108.65 (14)
C1—Fe—C2	41.25 (6)	C9—C8—Fe	69.75 (9)
C6—Fe—C7	41.30 (6)	C7—C8—Fe	69.10 (9)
C10—Fe—C7	69.21 (6)	C9—C8—H8	125.7
C1—Fe—C7	129.88 (6)	C7—C8—H8	125.7
C2—Fe—C7	168.66 (6)	Fe—C8—H8	127.1
C6—Fe—C3	115.82 (6)	C8—C9—C10	108.19 (14)
C10—Fe—C3	107.00 (7)	C8—C9—Fe	69.96 (9)
C1—Fe—C3	68.71 (6)	C10—C9—Fe	68.80 (9)
C2—Fe—C3	40.66 (6)	C8—C9—H9	125.9
C7—Fe—C3	149.88 (7)	C10—C9—H9	125.9
C6—Fe—C5	129.07 (6)	Fe—C9—H9	126.9
C10—Fe—C5	167.58 (6)	C9—C10—C6	107.92 (14)
C1—Fe—C5	41.06 (6)	C9—C10—Fe	70.53 (9)
C2—Fe—C5	68.94 (7)	C6—C10—Fe	69.00 (9)
C7—Fe—C5	108.78 (6)	C9—C10—H10	126.0
C3—Fe—C5	68.22 (7)	C6—C10—H10	126.0
C6—Fe—C9	68.97 (6)	Fe—C10—H10	126.0
C10—Fe—C9	40.67 (6)	C12—C11—C16	119.58 (15)
C1—Fe—C9	117.30 (7)	C12—C11—P1	119.96 (13)
C2—Fe—C9	107.89 (7)	C16—C11—P1	120.43 (12)
C7—Fe—C9	68.40 (7)	C13—C12—C11	119.85 (16)
C3—Fe—C9	129.09 (7)	C13—C12—H12	120.1
C5—Fe—C9	151.07 (7)	C11—C12—H12	120.1
C6—Fe—C4	107.48 (6)	C14—C13—C12	120.49 (17)
C10—Fe—C4	128.77 (7)	C14—C13—H13	119.8
C1—Fe—C4	68.55 (6)	C12—C13—H13	119.8
C2—Fe—C4	68.40 (7)	C15—C14—C13	119.86 (16)
C7—Fe—C4	117.58 (7)	C15—C14—H14	120.1
C3—Fe—C4	40.37 (7)	C13—C14—H14	120.1
C5—Fe—C4	40.38 (6)	C14—C15—C16	120.05 (17)
C9—Fe—C4	167.28 (7)	C14—C15—H15	120.0
C6—Fe—C8	68.73 (6)	C16—C15—H15	120.0
C10—Fe—C8	68.36 (7)	C15—C16—C11	120.15 (16)
C1—Fe—C8	109.16 (6)	C15—C16—H16	119.9
C2—Fe—C8	129.99 (7)	C11—C16—H16	119.9
C7—Fe—C8	40.47 (6)	C26—C21—C22	119.68 (15)
C3—Fe—C8	167.84 (7)	C26—C21—P1	122.07 (12)
C5—Fe—C8	118.62 (7)	C22—C21—P1	118.24 (12)
C9—Fe—C8	40.28 (7)	C23—C22—C21	119.82 (16)
C4—Fe—C8	151.13 (7)	C23—C22—H22	120.1
C1—P1—C11	106.75 (7)	C21—C22—H22	120.1
C1—P1—C21	105.88 (7)	C24—C23—C22	120.32 (16)
C11—P1—C21	103.94 (7)	C24—C23—H23	119.8
C1—P1—S1	112.74 (6)	C22—C23—H23	119.8
C11—P1—S1	113.78 (6)	C25—C24—C23	120.12 (16)
C21—P1—S1	113.00 (5)	C25—C24—H24	119.9
C6—P2—C31	105.69 (7)	C23—C24—H24	119.9
C6—P2—C41	105.55 (7)	C24—C25—C26	120.06 (16)
C31—P2—C41	104.63 (7)	C24—C25—H25	120.0
C6—P2—S2	114.92 (5)	C26—C25—H25	120.0
C31—P2—S2	111.95 (6)	C21—C26—C25	119.97 (15)
C41—P2—S2	113.24 (6)	C21—C26—H26	120.0
C5—C1—C2	107.49 (14)	C25—C26—H26	120.0
C5—C1—P1	122.88 (12)	C36—C31—C32	119.35 (15)
C2—C1—P1	129.63 (12)	C36—C31—P2	122.64 (12)
C5—C1—Fe	69.93 (9)	C32—C31—P2	117.97 (13)
C2—C1—Fe	69.42 (9)	C33—C32—C31	120.22 (18)
P1—C1—Fe	126.24 (8)	C33—C32—H32	119.9
C3—C2—C1	107.67 (14)	C31—C32—H32	119.9
C3—C2—Fe	70.00 (9)	C34—C33—C32	120.14 (18)
C1—C2—Fe	69.33 (9)	C34—C33—H33	119.9
C3—C2—H2	126.2	C32—C33—H33	119.9
C1—C2—H2	126.2	C33—C34—C35	120.27 (17)
Fe—C2—H2	126.1	C33—C34—H34	119.9
C4—C3—C2	108.58 (14)	C35—C34—H34	119.9
C4—C3—Fe	70.27 (9)	C34—C35—C36	120.01 (17)
C2—C3—Fe	69.34 (9)	C34—C35—H35	120.0
C4—C3—H3	125.7	C36—C35—H35	120.0
C2—C3—H3	125.7	C31—C36—C35	119.97 (16)
Fe—C3—H3	126.3	C31—C36—H36	120.0
C3—C4—C5	108.26 (14)	C35—C36—H36	120.0
C3—C4—Fe	69.36 (9)	C46—C41—C42	119.88 (15)
C5—C4—Fe	69.45 (9)	C46—C41—P2	119.87 (13)
C3—C4—H4	125.9	C42—C41—P2	120.25 (12)
C5—C4—H4	125.9	C43—C42—C41	119.62 (16)
Fe—C4—H4	126.9	C43—C42—H42	120.2
C4—C5—C1	108.00 (14)	C41—C42—H42	120.2
C4—C5—Fe	70.17 (9)	C44—C43—C42	120.12 (17)
C1—C5—Fe	69.01 (9)	C44—C43—H43	119.9
C4—C5—H5	126.0	C42—C43—H43	119.9
C1—C5—H5	126.0	C43—C44—C45	120.61 (16)
Fe—C5—H5	126.4	C43—C44—H44	119.7
C7—C6—C10	107.38 (14)	C45—C44—H44	119.7
C7—C6—P2	125.42 (12)	C44—C45—C46	119.71 (17)
C10—C6—P2	127.20 (12)	C44—C45—H45	120.1
C7—C6—Fe	69.92 (9)	C46—C45—H45	120.1
C10—C6—Fe	69.53 (9)	C45—C46—C41	120.03 (17)
P2—C6—Fe	125.62 (8)	C45—C46—H46	120.0
C8—C7—C6	107.86 (14)	C41—C46—H46	120.0
C8—C7—Fe	70.43 (9)

C11—P1—C1—C5	−145.23 (13)	C1—P1—C11—C12	117.38 (13)
C21—P1—C1—C5	104.46 (14)	C21—P1—C11—C12	−130.95 (13)
S1—P1—C1—C5	−19.57 (15)	S1—P1—C11—C12	−7.64 (15)
C11—P1—C1—C2	35.24 (17)	C1—P1—C11—C16	−64.36 (14)
C21—P1—C1—C2	−75.08 (16)	C21—P1—C11—C16	47.30 (14)
S1—P1—C1—C2	160.89 (13)	S1—P1—C11—C16	170.61 (11)
C11—P1—C1—Fe	−57.11 (12)	C16—C11—C12—C13	0.0 (2)
C21—P1—C1—Fe	−167.42 (9)	P1—C11—C12—C13	178.28 (13)
S1—P1—C1—Fe	68.54 (11)	C11—C12—C13—C14	−0.3 (3)
C5—C1—C2—C3	0.08 (17)	C12—C13—C14—C15	0.9 (3)
P1—C1—C2—C3	179.67 (12)	C13—C14—C15—C16	−1.1 (3)
Fe—C1—C2—C3	−59.75 (11)	C14—C15—C16—C11	0.8 (2)
C5—C1—C2—Fe	59.82 (11)	C12—C11—C16—C15	−0.3 (2)
P1—C1—C2—Fe	−120.58 (14)	P1—C11—C16—C15	−178.54 (12)
C1—C2—C3—C4	−0.18 (18)	C1—P1—C21—C26	16.91 (16)
Fe—C2—C3—C4	−59.51 (11)	C11—P1—C21—C26	−95.38 (14)
C1—C2—C3—Fe	59.33 (11)	S1—P1—C21—C26	140.79 (12)
C2—C3—C4—C5	0.21 (18)	C1—P1—C21—C22	−163.87 (13)
Fe—C3—C4—C5	−58.72 (11)	C11—P1—C21—C22	83.84 (14)
C2—C3—C4—Fe	58.93 (11)	S1—P1—C21—C22	−39.99 (15)
C3—C4—C5—C1	−0.16 (18)	C26—C21—C22—C23	1.9 (3)
Fe—C4—C5—C1	−58.83 (11)	P1—C21—C22—C23	−177.31 (13)
C3—C4—C5—Fe	58.66 (11)	C21—C22—C23—C24	−1.3 (3)
C2—C1—C5—C4	0.05 (17)	C22—C23—C24—C25	−0.2 (3)
P1—C1—C5—C4	−179.57 (11)	C23—C24—C25—C26	1.2 (3)
Fe—C1—C5—C4	59.55 (11)	C22—C21—C26—C25	−1.0 (2)
C2—C1—C5—Fe	−59.50 (11)	P1—C21—C26—C25	178.21 (13)
P1—C1—C5—Fe	120.88 (12)	C24—C25—C26—C21	−0.6 (3)
C31—P2—C6—C7	91.76 (14)	C6—P2—C31—C36	−9.64 (15)
C41—P2—C6—C7	−157.72 (13)	C41—P2—C31—C36	−120.81 (14)
S2—P2—C6—C7	−32.20 (15)	S2—P2—C31—C36	116.17 (13)
C31—P2—C6—C10	−88.52 (15)	C6—P2—C31—C32	172.81 (13)
C41—P2—C6—C10	21.99 (16)	C41—P2—C31—C32	61.64 (15)
S2—P2—C6—C10	147.51 (12)	S2—P2—C31—C32	−61.38 (14)
C31—P2—C6—Fe	−178.74 (9)	C36—C31—C32—C33	0.9 (3)
C41—P2—C6—Fe	−68.22 (11)	P2—C31—C32—C33	178.53 (14)
S2—P2—C6—Fe	57.30 (11)	C31—C32—C33—C34	−1.4 (3)
C10—C6—C7—C8	0.13 (17)	C32—C33—C34—C35	0.2 (3)
P2—C6—C7—C8	179.89 (11)	C33—C34—C35—C36	1.4 (3)
Fe—C6—C7—C8	59.83 (11)	C32—C31—C36—C35	0.8 (2)
C10—C6—C7—Fe	−59.70 (11)	P2—C31—C36—C35	−176.76 (13)
P2—C6—C7—Fe	120.06 (12)	C34—C35—C36—C31	−1.9 (2)
C6—C7—C8—C9	−0.11 (18)	C6—P2—C41—C46	107.95 (14)
Fe—C7—C8—C9	58.68 (11)	C31—P2—C41—C46	−140.78 (13)
C6—C7—C8—Fe	−58.79 (10)	S2—P2—C41—C46	−18.60 (15)
C7—C8—C9—C10	0.06 (18)	C6—P2—C41—C42	−72.25 (14)
Fe—C8—C9—C10	58.34 (11)	C31—P2—C41—C42	39.01 (15)
C7—C8—C9—Fe	−58.28 (11)	S2—P2—C41—C42	161.20 (11)
C8—C9—C10—C6	0.02 (18)	C46—C41—C42—C43	−1.6 (2)
Fe—C9—C10—C6	59.08 (11)	P2—C41—C42—C43	178.63 (13)
C8—C9—C10—Fe	−59.05 (11)	C41—C42—C43—C44	0.6 (3)
C7—C6—C10—C9	−0.09 (17)	C42—C43—C44—C45	0.6 (3)
P2—C6—C10—C9	−179.85 (12)	C43—C44—C45—C46	−0.9 (3)
Fe—C6—C10—C9	−60.04 (11)	C44—C45—C46—C41	−0.1 (3)
C7—C6—C10—Fe	59.94 (10)	C42—C41—C46—C45	1.3 (3)
P2—C6—C10—Fe	−119.81 (13)	P2—C41—C46—C45	−178.86 (13)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C31–C36 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg1ⁱ	0.95	2.92	3.6111 (18)	130

Symmetry code: (i) x−1, y, z.

Summary of structural data (Å) for Ph₂P(═Y)C₅H₄FeC₅H₄P(═Y)Ph₂. top

Y	Symmetry	Y—P···P—Y	Solvent	CSD refcode^a	Reference
O	1	180	–	KADXAO	Casellato et al. (1988)
O	1	180	–	WARMUX	Pilloni et al. (1993)
O	–	155.57 (18)	H₂O	RUVJEX01	Bar et al. (2008)
O	1	180	2H₂O	HATTUR	Munyejabo et al. (1994)
S	1	180	–	ZEQSOD	Fang et al. (1995)
S	–	-53.09 (3)	–	–	This work
Se	1	180	–	KIHWAB	Arsenyan et al. (2012)
Se	1	180	CH₂Cl₂	RIPTIT	Pilloni et al. (1997)

Note: (a) Cambridge Structural Database (Groom & Allen, 2014), Version 5.35.

Acknowledgements

This research is supported by the Trans-disciplinary Research Grant Scheme (TR002–2014 A) provided by the Ministry of Education, Malaysia.

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