(R)-2-[(Dimethyl­amino)­meth­yl]-1,1′-bis­(diphenyl­phosphinothio­yl)ferrocene dichloromethane monsolvate

Philippe, E.; Manoury, E.; Daran, J.-C.

doi:10.1107/S1600536812022301

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m799-m800

doi:10.1107/S1600536812022301

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(R)-2-[(Dimethylamino)methyl]-1,1′-bis(diphenylphosphinothioyl)ferrocene dichloromethane monsolvate

Elisabeth Philippe,^a Eric Manoury ^a and Jean-Claude Daran ^a ^*

^aLaboratoire de Chimie de Coordination, CNRS UPR8241, 205 route de Narbonne, Toulouse 31077, France
^*Correspondence e-mail: daran@lcc-toulouse.fr

(Received 11 May 2012; accepted 16 May 2012; online 26 May 2012)

In the title compound, [Fe(C₂₀H₂₁NPS)(C₁₇H₁₄PS)]·CH₂Cl₂, both cyclopentadienyl (Cp) rings constituting the ferrocene unit are substituted by a sulfur-protected diphenylphosphine. One of the Cp ligands is additionally substituted by a dimethylaminomethyl group causing the chirality of the molecule. Surprisingly, although the synthetic procedure yielded the title compound as a racemic mixture, the reported crystal is enantiomerically pure with the R absolute configuration. The dimethylamino group is exo with respect to the Cp ring. Both diphenylthiophosphine groups are trans with respect to the centroid–Fe–centroid direction. Weak intramolecular C—H⋯S and C—H⋯π interactions between symmetry-related molecules are observed. The contribution of the disordered solvent was removed from the refinement using SQUEEZE in PLATON [Spek (2009 ). Acta Cryst. D65, 148–155].

Related literature

For related 1,1′-bis(diphenylthiophosphino)ferrocene structures, see: Fang et al. (1995 ); Pilloni et al. (1997 ) and for a related dimethylethylaminoferrocene structure, see: Mateus et al. (2006 ). For the chemistry of related ferrocenyl compounds, see: Audin et al. (2010 ); Debono et al. (2010 ); Diab et al. (2008 ); Le Roux et al. (2007 ); Malacea et al. (2006a ,b ); Routaboul et al. (2005 , 2007 ).

Experimental

Crystal data

[Fe(C₂₀H₂₁NPS)(C₁₇H₁₄PS)]·CH₂Cl₂
M_r = 760.50
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.9493 (3) Å
b = 16.8206 (7) Å
c = 23.7697 (9) Å
V = 3578.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 180 K
0.48 × 0.11 × 0.08 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.841, T_max = 1.0
61147 measured reflections
7854 independent reflections
7097 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.102
S = 1.09
7854 reflections
393 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 3441 Friedel pairs
Flack parameter: 0.043 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C612—H612⋯S6	0.95	2.87	3.367 (3)	114
C113—H113⋯CT3ⁱ	0.95	2.84	3.678 (4)	148
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022301/im2377sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022301/im2377Isup2.hkl

checkCIF report

Comment top

Our group has extensively studied the coordination chemistry (Malacea et al., 2006a, 2006b) and the catalytic properties (Le Roux et al., 2007; Diab et al., 2008; Debono et al., 2010) of various ferrocenyl ligands which can be efficiently synthesized from racemic or enantiomerically pure 2-(diphenylthiophosphino)(hydroxymethyl)ferrocene (Routaboul et al., 2005; Mateus et al., 2006; Routaboul et al., 2007; Le Roux et al., 2007; Audin et al., 2010). The latter may be obtained from 2-(diphenylthiophosphino)(dimethylaminomethyl)ferrocene. This last compound can be efficiently obtained by a one-pot procedure from commercially available dimethylaminomethylferrocene (Mateus et al., 2006). During this synthesis, small amounts of 1,1'-bis(diphenylthiophosphino) 2-dimethylaminomethylferrocene can be observed in the crude materials and isolated by flash chromatography on silicagel. Single crystals suitable for X-ray diffraction analysis could be grown from a dichloromethane solution by slow diffusion of hexane.

In the title compound, both Cp rings constituting the ferrocene unit are substituted by a sulfur protected diphenylphosphine. One of the Cp ligands is additionally substituted by a dimethylaminomethyl group causing the chirality of the molecule. Surprisingly, although the synthetic procedure yielded the title compound as a racemic mixture, the reported crystal is enantiomerically pure with the R absolute configuration (Fig. 1). The dimethylamino moiety is exo with respect to the Cp ring as already observed for the related 2-(diphenylthiophophino)-dimethylaminomethylferrocene (Mateus et al., 2006). The C2—C21—N2 group is bent with respect to the Cp ring making a dihedral angle of 73.8 (3)° and the two methyl groups have rotated around the C21—N2 bond from the idealized bisecting position to minimize the interactions with the corresponding C111—C116 phenyl ring. The two diphenylthiophosphine moieties are trans with respect to the Ct1—Fe—Ct2 centroid direction (Ct1 and Ct2 being the centroids of the C1—C5 and C6—C10 Cp rings, respectively) as it was also observed in the molecular structure of related 1,1-(bisdiphenylthiophosphino)ferrocene (Fang et al.,1995; Pilloni et al., 1997). The P1—Ct1—Ct2—P6 torsion angle is 146.75 (2)°.

The two Cp rings are eclipsed with a twist angle of 0.8 (2)°. There is a weak intramolecular C—H···S interaction (Table 1). Weak intramolecular C—H···S and C—H···π interactions between symmetry related molecules are observed (Table 1).

Related literature top

For related 1,1'-bis(diphenylthiophosphino)ferrocene structures, see: Fang et al. (1995); Pilloni et al. (1997) and for a related dimethylethylaminoferrocene structure, see: Mateus et al. (2006). For the chemistry of related ferrocenyl compounds, see: Audin et al. (2010); Debono et al. (2010); Diab et al. (2008); Le Roux et al. (2007); Malacea et al. (2006a,b); Routaboul et al. (2005, 2007).

Experimental top

In a Schlenk tube, were dissolved, under argon, 13.5 g (55.6 mmol) of N,N-dimethylaminomethylferrocene in 80 ml of dry diethylether. The solution was cooled down to -78°C and 42 ml (67.1 mmol) of a 1.65M n-BuLi solution in hexane were added dropwise. The solution was then stirred 3 h at RT. After cooling back to -78°C again, 27 ml (150 mmol) of freshly distilled chlorodiphenylphosphine were added dropwise. After stirring overnight at RT, water was added slowly under argon. The aqueous phase was then extracted by three fractions of dichloromethane under argon. The organic solutions were dried with sodium sulfate. After evaporation of the solvents, the crude material was dissolved, under argon, in 400 ml of dry dichloromethane in a Schlenk tube. 10.2 g of sulfur (318 mmol) was then added and the solution was kept at reflux for 2 h. The crude material was purified by flash chromatography on silica with pentane then ether as eluent to yield two yellow fractions (first fraction: 0.45 g of 1,1'-bis(diphenylthiophosphino) 2-dimethylaminomethylferrocene (1.2%); second fraction: 23.2 g of 2- (diphenylthiophosphino)dimethylaminomethylferrocene (91%)).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. ; Molecular view of the title compound with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

(R)-2-[(Dimethylamino)methyl]-1,1'-bis(diphenylphosphinothioyl)ferrocene dichloromethane monosolvate top

Crystal data top

[Fe(C₂₀H₂₁NPS)(C₁₇H₁₄PS)]·CH₂Cl₂	F(000) = 1576
M_r = 760.50	D_x = 1.412 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9878 reflections
a = 8.9493 (3) Å	θ = 2.4–26.6°
b = 16.8206 (7) Å	µ = 0.81 mm⁻¹
c = 23.7697 (9) Å	T = 180 K
V = 3578.1 (2) Å³	Needle, yellow
Z = 4	0.48 × 0.11 × 0.08 mm

Data collection top

Bruker APEXII diffractometer	7854 independent reflections
Radiation source: fine-focus sealed tube	7097 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω and ϕ scans	θ_max = 27.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
T_min = 0.841, T_max = 1.0	k = −21→20
61147 measured reflections	l = −29→30

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0472P)² + 2.2997P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
7854 reflections	Δρ_max = 0.63 e Å⁻³
393 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 3441 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.043 (16)

Crystal data top

[Fe(C₂₀H₂₁NPS)(C₁₇H₁₄PS)]·CH₂Cl₂	V = 3578.1 (2) Å³
M_r = 760.50	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.9493 (3) Å	µ = 0.81 mm⁻¹
b = 16.8206 (7) Å	T = 180 K
c = 23.7697 (9) Å	0.48 × 0.11 × 0.08 mm

Data collection top

Bruker APEXII diffractometer	7854 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	7097 reflections with I > 2σ(I)
T_min = 0.841, T_max = 1.0	R_int = 0.040
61147 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.102	Δρ_max = 0.63 e Å⁻³
S = 1.09	Δρ_min = −0.36 e Å⁻³
7854 reflections	Absolute structure: Flack (1983), 3441 Friedel pairs
393 parameters	Absolute structure parameter: 0.043 (16)
0 restraints

Special details top

Experimental. NMR of 1,1'-bis(diphenylthiophosphino) 2-dimethylaminomethylferrocene 1H NMR ((p.p.m.), δ CDCl3): 7.7 (2H, m: Ph); 7.72–7.60 (6H, m: Ph); 7.55–7.40 (8H, m: Ph); 7.40–7.30 (4H, m: Ph); 4.97 (1H, br s: Cp); 4.89 (1H, br s: Cp); 4.78 (1H, br s: Cp); 4.54 (1H, br s: Cp); 4.48 (1H, br s: Cp); 4.25 (1H, br s: Cp); 3.97 (1H, br d(AB), J=10 Hz: CH2); 3.70 (1H, br s: Cp); 2.91 (1H, br d(AB), J=10 Hz: CH2); 1.88 (6H, s: CH3). 13 C NMR (δ (p.p.m.), CDCl3): 134.26 (d, JP—C=87.0 Hz: quat. Ph); 134.22 (d, JP—C=88.3 Hz: quat. Ph); 134.0 (d, JP—C=87.0 Hz: quat. Ph); 133.3 (d, JP—C=85.9 Hz: quat. Ph); 132.0 (d, JP—C=10.7 Hz: Ph); 131.9 (d, JP—C=10.5 Hz: Ph);131.7 (d, JP—C=10.8 Hz: Ph); 131.41 (s, Ph); 131.37 (d, JP—C=12.5 Hz: Ph); 131.3 (s, Ph); 131.2 (d, JP—C=2.9 Hz: Ph); 131.03 (d, JP—C=2.5 Hz: Ph); 128.4 (d, JP—C=12.5 Hz: Ph); 128.2 (d, JP—C=12.5 Hz: Ph); 128.0 (d, JP—C=12.4 Hz: Ph); 127.9 (d, JP—C=12.7 Hz: Ph); 77.9 (br s: Cp); 76.8 (d, JP—C=10.1 Hz: Cp); 76.0 (d, JP—C=12.4 Hz: Cp); 75.8 (d, JP—C=94 Hz: quat Cp); 75.6 (d, JP—C= 9.9 Hz: Cp); 75.3 (d, JP—C=12.3 Hz: Cp); 73.9 (d, JP—C=12.1 Hz: Cp); 72.5 (br d, JP—C=8 Hz: Cp); 56.0 (CH2); 44.5 (N—CH3). 31P NMR (δ (p.p.m.), CDCl3): 40.95; 40,56.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.48389 (4)	0.00564 (3)	0.606968 (17)	0.03074 (11)
P1	0.23725 (8)	0.02734 (5)	0.71861 (3)	0.02852 (17)
P6	0.73306 (8)	0.07876 (5)	0.50958 (3)	0.02409 (16)
S1	0.13593 (10)	0.12190 (5)	0.68974 (4)	0.0406 (2)
S6	0.89329 (9)	0.00330 (5)	0.52544 (3)	0.03778 (19)
N2	0.5450 (5)	0.1520 (2)	0.75679 (14)	0.0686 (11)
C1	0.4171 (3)	0.0049 (2)	0.68857 (12)	0.0325 (7)
C2	0.5410 (3)	0.0577 (2)	0.68079 (13)	0.0362 (8)
C3	0.6606 (3)	0.0106 (3)	0.66053 (13)	0.0494 (10)
H3	0.7580	0.0300	0.6525	0.059*
C4	0.6152 (4)	−0.0689 (2)	0.65397 (15)	0.0462 (9)
H4	0.6740	−0.1116	0.6400	0.055*
C5	0.4652 (4)	−0.0730 (2)	0.67230 (14)	0.0417 (8)
H5	0.4059	−0.1198	0.6736	0.050*
C6	0.5518 (3)	0.04440 (19)	0.52950 (12)	0.0287 (7)
C7	0.4279 (3)	0.0909 (2)	0.54986 (13)	0.0335 (7)
H7	0.4281	0.1465	0.5567	0.040*
C8	0.3061 (3)	0.0388 (2)	0.55776 (14)	0.0419 (9)
H8	0.2093	0.0541	0.5702	0.050*
C9	0.3500 (4)	−0.0390 (2)	0.54446 (15)	0.0464 (9)
H9	0.2893	−0.0852	0.5468	0.056*
C10	0.5022 (4)	−0.0362 (2)	0.52682 (13)	0.0400 (7)
H10	0.5607	−0.0804	0.5153	0.048*
C21	0.5416 (4)	0.1420 (2)	0.69626 (16)	0.0479 (9)
H21A	0.6301	0.1681	0.6795	0.057*
H21B	0.4511	0.1680	0.6809	0.057*
C22	0.6886 (8)	0.1248 (4)	0.7806 (3)	0.119 (3)
H22A	0.7709	0.1537	0.7626	0.178*
H22B	0.7003	0.0677	0.7738	0.178*
H22C	0.6899	0.1350	0.8212	0.178*
C23	0.5062 (9)	0.2326 (3)	0.7734 (2)	0.111 (3)
H23A	0.5025	0.2360	0.8146	0.166*
H23B	0.4082	0.2465	0.7578	0.166*
H23C	0.5816	0.2697	0.7591	0.166*
C111	0.2708 (3)	0.03238 (19)	0.79388 (12)	0.0310 (6)
C112	0.3919 (3)	−0.0059 (2)	0.81862 (13)	0.0402 (7)
H112	0.4579	−0.0366	0.7961	0.048*
C113	0.4166 (4)	0.0005 (3)	0.87580 (14)	0.0468 (8)
H113	0.5002	−0.0254	0.8923	0.056*
C114	0.3207 (4)	0.0441 (2)	0.90904 (15)	0.0482 (9)
H114	0.3378	0.0483	0.9484	0.058*
C115	0.1988 (4)	0.0818 (2)	0.88471 (14)	0.0446 (8)
H115	0.1323	0.1119	0.9074	0.053*
C116	0.1741 (4)	0.0757 (2)	0.82769 (13)	0.0362 (7)
H116	0.0901	0.1015	0.8114	0.043*
C121	0.1326 (3)	−0.06366 (19)	0.70677 (13)	0.0327 (7)
C122	0.0559 (4)	−0.0718 (2)	0.65611 (15)	0.0382 (8)
H122	0.0545	−0.0291	0.6300	0.046*
C123	−0.0181 (4)	−0.1416 (2)	0.64376 (17)	0.0473 (9)
H123	−0.0661	−0.1477	0.6084	0.057*
C124	−0.0227 (5)	−0.2024 (2)	0.68224 (19)	0.0554 (10)
H124	−0.0775	−0.2494	0.6742	0.067*
C125	0.0515 (5)	−0.1951 (2)	0.73201 (18)	0.0531 (10)
H125	0.0490	−0.2376	0.7583	0.064*
C126	0.1312 (4)	−0.1260 (2)	0.74514 (15)	0.0437 (8)
H126	0.1836	−0.1218	0.7798	0.052*
C611	0.7596 (3)	0.17580 (17)	0.54128 (11)	0.0254 (6)
C612	0.8712 (3)	0.18721 (19)	0.58077 (12)	0.0294 (6)
H612	0.9324	0.1439	0.5920	0.035*
C613	0.8938 (3)	0.2616 (2)	0.60395 (14)	0.0384 (7)
H613	0.9703	0.2691	0.6312	0.046*
C614	0.8055 (4)	0.3256 (2)	0.58777 (13)	0.0386 (8)
H614	0.8216	0.3767	0.6037	0.046*
C615	0.6936 (4)	0.3142 (2)	0.54805 (14)	0.0362 (7)
H615	0.6327	0.3578	0.5370	0.043*
C616	0.6703 (3)	0.24041 (18)	0.52467 (12)	0.0302 (6)
H616	0.5940	0.2331	0.4974	0.036*
C621	0.7209 (3)	0.09785 (17)	0.43468 (11)	0.0251 (6)
C622	0.8041 (4)	0.1585 (2)	0.41042 (13)	0.0357 (7)
H622	0.8578	0.1947	0.4335	0.043*
C623	0.8085 (4)	0.1661 (2)	0.35233 (14)	0.0438 (9)
H623	0.8661	0.2075	0.3359	0.053*
C624	0.7316 (4)	0.1151 (2)	0.31833 (13)	0.0414 (8)
H624	0.7366	0.1206	0.2786	0.050*
C625	0.6461 (4)	0.0553 (2)	0.34214 (14)	0.0427 (8)
H625	0.5918	0.0198	0.3187	0.051*
C626	0.6398 (3)	0.0471 (2)	0.39988 (13)	0.0359 (7)
H626	0.5796	0.0065	0.4160	0.043*
CT1	0.5398	−0.0138	0.6712	0.010*	0.00
CT2	0.4276	0.0198	0.5417	0.010*	0.00
CT3	0.7251	0.1066	0.3763	0.010*	0.00

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0273 (2)	0.0402 (3)	0.0247 (2)	0.00255 (18)	0.00526 (16)	0.01199 (19)
P1	0.0269 (3)	0.0326 (4)	0.0260 (4)	0.0068 (3)	0.0028 (3)	0.0074 (3)
P6	0.0225 (3)	0.0311 (4)	0.0186 (3)	0.0000 (3)	0.0010 (3)	0.0037 (3)
S1	0.0450 (5)	0.0375 (5)	0.0393 (5)	0.0162 (4)	−0.0074 (4)	0.0079 (4)
S6	0.0392 (4)	0.0435 (5)	0.0306 (4)	0.0150 (4)	0.0001 (3)	0.0075 (4)
N2	0.111 (3)	0.052 (2)	0.0427 (19)	−0.009 (2)	−0.021 (2)	0.0029 (16)
C1	0.0314 (14)	0.0435 (18)	0.0228 (14)	0.0099 (14)	0.0040 (11)	0.0127 (15)
C2	0.0288 (15)	0.056 (2)	0.0233 (15)	−0.0050 (14)	−0.0038 (12)	0.0097 (14)
C3	0.0232 (14)	0.096 (3)	0.0294 (16)	0.0046 (18)	0.0022 (12)	0.014 (2)
C4	0.0409 (19)	0.055 (2)	0.042 (2)	0.0176 (18)	0.0139 (16)	0.0223 (17)
C5	0.0449 (19)	0.0435 (19)	0.0366 (18)	0.0204 (16)	0.0156 (15)	0.0192 (15)
C6	0.0274 (14)	0.0397 (18)	0.0190 (14)	−0.0062 (12)	0.0039 (11)	0.0055 (13)
C7	0.0269 (14)	0.047 (2)	0.0269 (15)	0.0016 (13)	−0.0022 (12)	0.0104 (14)
C8	0.0242 (14)	0.070 (3)	0.0315 (18)	−0.0044 (15)	−0.0011 (13)	0.0151 (17)
C9	0.0457 (19)	0.058 (2)	0.0356 (19)	−0.0232 (18)	0.0044 (15)	0.0052 (17)
C10	0.0461 (19)	0.0458 (19)	0.0281 (16)	−0.0050 (16)	0.0030 (14)	−0.0014 (14)
C21	0.053 (2)	0.049 (2)	0.042 (2)	−0.0101 (17)	−0.0031 (17)	0.0139 (17)
C22	0.142 (6)	0.097 (4)	0.117 (5)	−0.001 (4)	−0.085 (5)	0.003 (4)
C23	0.211 (8)	0.043 (3)	0.078 (4)	−0.018 (4)	−0.048 (5)	−0.009 (2)
C111	0.0295 (14)	0.0384 (17)	0.0251 (14)	0.0022 (13)	0.0053 (11)	0.0100 (12)
C112	0.0368 (15)	0.056 (2)	0.0275 (15)	0.0090 (17)	0.0019 (12)	0.0102 (16)
C113	0.0436 (17)	0.063 (2)	0.0338 (17)	0.0012 (18)	−0.0049 (14)	0.0122 (18)
C114	0.053 (2)	0.065 (2)	0.0275 (17)	−0.0119 (19)	0.0057 (15)	0.0090 (16)
C115	0.0446 (18)	0.056 (2)	0.0331 (18)	0.0014 (16)	0.0114 (15)	−0.0032 (16)
C116	0.0375 (16)	0.0403 (18)	0.0307 (16)	0.0070 (14)	0.0034 (13)	0.0024 (14)
C121	0.0307 (15)	0.0344 (17)	0.0331 (16)	0.0113 (13)	0.0077 (12)	0.0060 (13)
C122	0.0312 (16)	0.043 (2)	0.0400 (19)	0.0041 (14)	−0.0006 (13)	0.0139 (16)
C123	0.043 (2)	0.046 (2)	0.053 (2)	0.0045 (17)	−0.0012 (17)	−0.0062 (17)
C124	0.056 (2)	0.042 (2)	0.068 (3)	−0.0078 (18)	0.016 (2)	−0.0063 (19)
C125	0.072 (3)	0.032 (2)	0.055 (2)	0.0017 (18)	0.024 (2)	0.0088 (17)
C126	0.058 (2)	0.0350 (18)	0.0384 (19)	0.0098 (17)	0.0115 (16)	0.0066 (15)
C611	0.0224 (13)	0.0321 (15)	0.0216 (13)	−0.0020 (12)	0.0030 (11)	0.0028 (11)
C612	0.0263 (14)	0.0411 (18)	0.0207 (14)	−0.0001 (13)	0.0015 (11)	0.0030 (12)
C613	0.0309 (15)	0.058 (2)	0.0269 (16)	−0.0094 (15)	−0.0011 (13)	−0.0027 (15)
C614	0.0397 (18)	0.045 (2)	0.0312 (17)	−0.0076 (15)	0.0041 (13)	−0.0086 (15)
C615	0.0323 (16)	0.0357 (18)	0.0404 (18)	−0.0003 (13)	0.0070 (13)	0.0062 (15)
C616	0.0286 (14)	0.0381 (17)	0.0239 (14)	0.0016 (13)	−0.0012 (12)	0.0007 (13)
C621	0.0233 (13)	0.0324 (16)	0.0197 (13)	0.0063 (11)	0.0023 (10)	0.0007 (11)
C622	0.0410 (18)	0.0376 (18)	0.0285 (16)	−0.0057 (14)	0.0035 (13)	0.0043 (14)
C623	0.050 (2)	0.050 (2)	0.0310 (17)	0.0018 (17)	0.0107 (15)	0.0144 (16)
C624	0.0448 (18)	0.056 (2)	0.0234 (15)	0.0127 (17)	0.0026 (14)	0.0063 (15)
C625	0.0418 (19)	0.059 (2)	0.0277 (17)	−0.0059 (16)	−0.0037 (14)	−0.0033 (15)
C626	0.0334 (15)	0.0462 (19)	0.0281 (16)	−0.0073 (14)	0.0018 (13)	−0.0036 (14)

Geometric parameters (Å, º) top

Fe1—CT1	1.6401 (4)	C23—H23B	0.9800
Fe1—CT2	1.6488 (4)	C23—H23C	0.9800
Fe1—C2	2.027 (3)	C111—C116	1.388 (4)
Fe1—C1	2.030 (3)	C111—C112	1.391 (4)
Fe1—C3	2.032 (3)	C112—C113	1.381 (4)
Fe1—C7	2.037 (3)	C112—H112	0.9500
Fe1—C10	2.038 (3)	C113—C114	1.378 (5)
Fe1—C6	2.046 (3)	C113—H113	0.9500
Fe1—C5	2.046 (3)	C114—C115	1.388 (5)
Fe1—C4	2.050 (3)	C114—H114	0.9500
Fe1—C9	2.051 (4)	C115—C116	1.377 (5)
Fe1—C8	2.052 (3)	C115—H115	0.9500
P1—C1	1.800 (3)	C116—H116	0.9500
P1—C111	1.816 (3)	C121—C126	1.390 (5)
P1—C121	1.816 (3)	C121—C122	1.393 (5)
P1—S1	1.9551 (11)	C122—C123	1.379 (5)
P6—C6	1.786 (3)	C122—H122	0.9500
P6—C621	1.812 (3)	C123—C124	1.373 (6)
P6—C611	1.813 (3)	C123—H123	0.9500
P6—S6	1.9519 (11)	C124—C125	1.362 (6)
N2—C21	1.449 (5)	C124—H124	0.9500
N2—C23	1.454 (6)	C125—C126	1.399 (6)
N2—C22	1.477 (7)	C125—H125	0.9500
C1—C2	1.432 (4)	C126—H126	0.9500
C1—C5	1.433 (5)	C611—C612	1.384 (4)
C2—C3	1.417 (5)	C611—C616	1.406 (4)
C2—C21	1.464 (5)	C612—C613	1.382 (5)
C3—C4	1.406 (6)	C612—H612	0.9500
C3—H3	0.9500	C613—C614	1.389 (5)
C4—C5	1.413 (5)	C613—H613	0.9500
C4—H4	0.9500	C614—C615	1.389 (5)
C5—H5	0.9500	C614—H614	0.9500
C6—C10	1.428 (5)	C615—C616	1.377 (5)
C6—C7	1.440 (4)	C615—H615	0.9500
C7—C8	1.411 (5)	C616—H616	0.9500
C7—H7	0.9500	C621—C622	1.388 (4)
C8—C9	1.403 (6)	C621—C626	1.393 (4)
C8—H8	0.9500	C622—C623	1.387 (5)
C9—C10	1.426 (5)	C622—H622	0.9500
C9—H9	0.9500	C623—C624	1.364 (5)
C10—H10	0.9500	C623—H623	0.9500
C21—H21A	0.9900	C624—C625	1.385 (5)
C21—H21B	0.9900	C624—H624	0.9500
C22—H22A	0.9800	C625—C626	1.381 (5)
C22—H22B	0.9800	C625—H625	0.9500
C22—H22C	0.9800	C626—H626	0.9500
C23—H23A	0.9800

CT1—Fe1—CT2	176.82 (3)	P6—C6—Fe1	127.72 (16)
CT1—Fe1—C2	37.12 (10)	C8—C7—C6	107.6 (3)
CT2—Fe1—C2	146.06 (10)	C8—C7—Fe1	70.39 (18)
CT1—Fe1—C1	36.75 (8)	C6—C7—Fe1	69.67 (17)
CT2—Fe1—C1	144.12 (8)	C8—C7—H7	126.2
C2—Fe1—C1	41.36 (13)	C6—C7—H7	126.2
CT1—Fe1—C3	35.63 (9)	Fe1—C7—H7	125.3
CT2—Fe1—C3	145.24 (9)	C9—C8—C7	109.4 (3)
C2—Fe1—C3	40.86 (14)	C9—C8—Fe1	70.0 (2)
C1—Fe1—C3	68.34 (12)	C7—C8—Fe1	69.24 (17)
CT1—Fe1—C7	146.69 (10)	C9—C8—H8	125.3
CT2—Fe1—C7	36.50 (10)	C7—C8—H8	125.3
C2—Fe1—C7	109.57 (14)	Fe1—C8—H8	127.1
C1—Fe1—C7	124.64 (13)	C8—C9—C10	107.6 (3)
C3—Fe1—C7	125.46 (16)	C8—C9—Fe1	70.0 (2)
CT1—Fe1—C10	141.04 (11)	C10—C9—Fe1	69.07 (19)
CT2—Fe1—C10	36.33 (10)	C8—C9—H9	126.2
C2—Fe1—C10	159.80 (13)	C10—C9—H9	126.2
C1—Fe1—C10	156.23 (14)	Fe1—C9—H9	126.3
C3—Fe1—C10	122.50 (14)	C9—C10—C6	108.4 (3)
C7—Fe1—C10	68.88 (14)	C9—C10—Fe1	70.1 (2)
CT1—Fe1—C6	144.19 (8)	C6—C10—Fe1	69.84 (19)
CT2—Fe1—C6	36.65 (8)	C9—C10—H10	125.8
C2—Fe1—C6	124.52 (12)	C6—C10—H10	125.8
C1—Fe1—C6	161.71 (14)	Fe1—C10—H10	125.8
C3—Fe1—C6	108.63 (12)	N2—C21—C2	111.3 (3)
C7—Fe1—C6	41.32 (12)	N2—C21—H21A	109.4
C10—Fe1—C6	40.94 (13)	C2—C21—H21A	109.4
CT1—Fe1—C5	35.88 (12)	N2—C21—H21B	109.4
CT2—Fe1—C5	141.48 (12)	C2—C21—H21B	109.4
C2—Fe1—C5	69.07 (15)	H21A—C21—H21B	108.0
C1—Fe1—C5	41.15 (14)	N2—C22—H22A	109.5
C3—Fe1—C5	67.34 (16)	N2—C22—H22B	109.5
C7—Fe1—C5	160.11 (13)	H22A—C22—H22B	109.5
C10—Fe1—C5	119.54 (15)	N2—C22—H22C	109.5
C6—Fe1—C5	155.96 (13)	H22A—C22—H22C	109.5
CT1—Fe1—C4	36.47 (11)	H22B—C22—H22C	109.5
CT2—Fe1—C4	140.93 (11)	N2—C23—H23A	109.5
C2—Fe1—C4	69.38 (15)	N2—C23—H23B	109.5
C1—Fe1—C4	69.18 (13)	H23A—C23—H23B	109.5
C3—Fe1—C4	40.30 (17)	N2—C23—H23C	109.5
C7—Fe1—C4	159.20 (13)	H23A—C23—H23C	109.5
C10—Fe1—C4	104.61 (15)	H23B—C23—H23C	109.5
C6—Fe1—C4	121.01 (13)	C116—C111—C112	118.9 (3)
C5—Fe1—C4	40.36 (13)	C116—C111—P1	119.5 (2)
CT1—Fe1—C9	141.26 (10)	C112—C111—P1	121.6 (2)
CT2—Fe1—C9	36.16 (10)	C113—C112—C111	120.3 (3)
C2—Fe1—C9	158.85 (14)	C113—C112—H112	119.8
C1—Fe1—C9	121.19 (13)	C111—C112—H112	119.8
C3—Fe1—C9	157.44 (17)	C114—C113—C112	120.4 (3)
C7—Fe1—C9	68.37 (15)	C114—C113—H113	119.8
C10—Fe1—C9	40.83 (14)	C112—C113—H113	119.8
C6—Fe1—C9	68.80 (12)	C113—C114—C115	119.6 (3)
C5—Fe1—C9	105.38 (16)	C113—C114—H114	120.2
C4—Fe1—C9	120.38 (17)	C115—C114—H114	120.2
CT1—Fe1—C8	145.23 (9)	C116—C115—C114	120.2 (3)
CT2—Fe1—C8	35.66 (9)	C116—C115—H115	119.9
C2—Fe1—C8	124.85 (15)	C114—C115—H115	119.9
C1—Fe1—C8	108.53 (12)	C115—C116—C111	120.6 (3)
C3—Fe1—C8	161.71 (18)	C115—C116—H116	119.7
C7—Fe1—C8	40.37 (13)	C111—C116—H116	119.7
C10—Fe1—C8	67.88 (15)	C126—C121—C122	119.2 (3)
C6—Fe1—C8	68.33 (12)	C126—C121—P1	122.6 (3)
C5—Fe1—C8	123.01 (14)	C122—C121—P1	118.1 (2)
C4—Fe1—C8	157.15 (16)	C123—C122—C121	120.3 (3)
C9—Fe1—C8	39.98 (15)	C123—C122—H122	119.9
C1—P1—C111	104.65 (13)	C121—C122—H122	119.9
C1—P1—C121	102.87 (15)	C124—C123—C122	120.4 (4)
C111—P1—C121	106.09 (14)	C124—C123—H123	119.8
C1—P1—S1	116.46 (11)	C122—C123—H123	119.8
C111—P1—S1	112.61 (11)	C125—C124—C123	119.8 (4)
C121—P1—S1	113.08 (10)	C125—C124—H124	120.1
C6—P6—C621	105.26 (14)	C123—C124—H124	120.1
C6—P6—C611	107.47 (14)	C124—C125—C126	121.2 (4)
C621—P6—C611	104.87 (13)	C124—C125—H125	119.4
C6—P6—S6	113.92 (11)	C126—C125—H125	119.4
C621—P6—S6	110.44 (9)	C121—C126—C125	119.0 (4)
C611—P6—S6	114.13 (10)	C121—C126—H126	120.5
C21—N2—C23	112.0 (4)	C125—C126—H126	120.5
C21—N2—C22	111.3 (5)	C612—C611—C616	119.6 (3)
C23—N2—C22	113.1 (5)	C612—C611—P6	120.1 (2)
C2—C1—C5	107.4 (3)	C616—C611—P6	120.3 (2)
C2—C1—P1	127.8 (3)	C613—C612—C611	120.1 (3)
C5—C1—P1	124.6 (3)	C613—C612—H612	120.0
C2—C1—Fe1	69.20 (17)	C611—C612—H612	120.0
C5—C1—Fe1	70.05 (17)	C612—C613—C614	120.5 (3)
P1—C1—Fe1	129.88 (15)	C612—C613—H613	119.7
C3—C2—C1	106.4 (3)	C614—C613—H613	119.7
C3—C2—C21	128.6 (3)	C613—C614—C615	119.5 (3)
C1—C2—C21	124.8 (3)	C613—C614—H614	120.3
C3—C2—Fe1	69.78 (19)	C615—C614—H614	120.3
C1—C2—Fe1	69.44 (17)	C616—C615—C614	120.5 (3)
C21—C2—Fe1	129.5 (2)	C616—C615—H615	119.8
C4—C3—C2	110.6 (3)	C614—C615—H615	119.8
C4—C3—Fe1	70.5 (2)	C615—C616—C611	119.9 (3)
C2—C3—Fe1	69.36 (17)	C615—C616—H616	120.1
C4—C3—H3	124.7	C611—C616—H616	120.1
C2—C3—H3	124.7	C622—C621—C626	118.9 (3)
Fe1—C3—H3	127.0	C622—C621—P6	120.4 (2)
C3—C4—C5	106.6 (3)	C626—C621—P6	120.4 (2)
C3—C4—Fe1	69.17 (19)	C623—C622—C621	119.7 (3)
C5—C4—Fe1	69.69 (19)	C623—C622—H622	120.1
C3—C4—H4	126.7	C621—C622—H622	120.1
C5—C4—H4	126.7	C624—C623—C622	121.2 (3)
Fe1—C4—H4	126.0	C624—C623—H623	119.4
C4—C5—C1	108.9 (3)	C622—C623—H623	119.4
C4—C5—Fe1	69.95 (19)	C623—C624—C625	119.6 (3)
C1—C5—Fe1	68.80 (17)	C623—C624—H624	120.2
C4—C5—H5	125.5	C625—C624—H624	120.2
C1—C5—H5	125.5	C626—C625—C624	120.1 (3)
Fe1—C5—H5	127.3	C626—C625—H625	120.0
C10—C6—C7	106.9 (3)	C624—C625—H625	120.0
C10—C6—P6	125.3 (2)	C625—C626—C621	120.5 (3)
C7—C6—P6	127.8 (2)	C625—C626—H626	119.7
C10—C6—Fe1	69.22 (18)	C621—C626—H626	119.7
C7—C6—Fe1	69.01 (17)

C1—CT1—CT2—C8	0.3 (3)	C5—CT1—CT2—C9	1.8 (2)
C2—CT1—CT2—C7	0.1 (2)	C1—C2—C21—N2	71.2 (4)
C3—CT1—CT2—C6	0.6 (3)	C3—C2—C21—N2	−102.8 (4)
C4—CT1—CT2—C10	1.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C612—H612···S6	0.95	2.87	3.367 (3)	114
C113—H113···CT3ⁱ	0.95	2.84	3.678 (4)	148

Symmetry code: (i) −x+3/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	[Fe(C₂₀H₂₁NPS)(C₁₇H₁₄PS)]·CH₂Cl₂
M_r	760.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	180
a, b, c (Å)	8.9493 (3), 16.8206 (7), 23.7697 (9)
V (Å³)	3578.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.48 × 0.11 × 0.08

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.841, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	61147, 7854, 7097
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.102, 1.09
No. of reflections	7854
No. of parameters	393
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.36
Absolute structure	Flack (1983), 3441 Friedel pairs
Absolute structure parameter	0.043 (16)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C612—H612···S6	0.95	2.87	3.367 (3)	114.1
C113—H113···CT3ⁱ	0.95	2.84	3.678 (4)	147.9

Symmetry code: (i) −x+3/2, −y, z+1/2.

References

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Volume 68| Part 6| June 2012| Pages m799-m800

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(R)-2-[(Di­methyl­amino)­meth­yl]-1,1′-bis­­(di­phenyl­phosphino­thio­yl)ferrocene di­chloro­methane monsolvate

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metal-organic compounds

(R)-2-[(Dimethylamino)methyl]-1,1′-bis(diphenylphosphinothioyl)ferrocene dichloromethane monsolvate