rac-{[2-(Diphenyl­thio­phosphor­yl)ferrocen­yl]meth­yl}dimethyl­ammonium diphenyl­dithio­phosphinate

Mouas, N.; Merazig, H.; Daran, J.-C.; Manoury, E.

doi:10.1107/S1600536812009129

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m381-m382

doi:10.1107/S1600536812009129

Open

access

ADDENDA AND ERRATA

A correction has been published for this article. To view the correction, click here.

rac-{[2-(Diphenylthiophosphoryl)ferrocenyl]methyl}dimethylammonium diphenyldithiophosphinate

Nardjes Mouas,^a,^b Hocine Merazig,^a Jean-Claude Daran ^b ^* and Eric Manoury ^b

^aUnité de Recherche de Chimie Moléculaire et Structurale CHEMS, Université Mentouri, Constantine, Algeria, and ^bCNRS, LCC, 205 route de Narbonne, BP 44099, F-31077, Toulouse cedex 4, France
^*Correspondence e-mail: daran@lcc-toulouse.fr

(Received 27 February 2012; accepted 29 February 2012; online 7 March 2012)

2-(Diphenylthiophosphino)dimethylaminomethylferrocene is a key intermediate in the synthesis of various ferrocenyl ligands. During one such synthesis, the title compound, [Fe(C₅H₅)(C₂₀H₂₂NPS)](C₁₂H₁₀PS₂), was isolated as a by-product. It is built up by association of (2-(diphenylphosphino)ferrocenyl)methyl)dimethylammonium cations and diphenylphosphino dithioate anions. N—H⋯S, C—H⋯S and C—H⋯π interactions link the anions and cations. Each anion–cation pair is linked two by two through C—H⋯π interactions, forming pseudo dimers.

Related literature

For the synthesis of various ferrocenyl ligands, see: Audin et al. (2010 ); Le Roux et al. (2007 ); Routaboul et al. (2005 , 2007 ). For related structures containing the C₁₂H₁₀PS₂ anion, see: Alison et al. (1971 ); Fackler et al. (1982 ); Silvestru et al. (1995 ). For related ferrocenyl ammonium structures, see: Štěpnička & Císařová, (2003 ). For a related ferrocenylamine structure, see: Mateus et al. (2006 ).

Experimental

Crystal data

[Fe(C₅H₅)(C₂₀H₂₂NPS)](C₁₂H₁₀PS₂)
M_r = 709.65
Monoclinic, P 2₁ /c
a = 14.7800 (3) Å
b = 18.3770 (3) Å
c = 13.6318 (3) Å
β = 112.557 (2)°
V = 3419.31 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 180 K
0.38 × 0.13 × 0.06 mm

Data collection

Agilent Xcalibur Eos Gemini ultra diffractometer
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Agilent, 2011 ) T_min = 0.815, T_max = 1.000
37299 measured reflections
7498 independent reflections
6435 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 1.05
7498 reflections
402 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C111–C116 and C221–C226 phenyl rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S21	0.85 (2)	2.34 (2)	3.1516 (15)	160.3 (19)
C21—H21B⋯S1	0.99	2.87	3.664 (2)	137
C22—H22C⋯Cg2ⁱ	0.99	2.75	3.621 (3)	149
C23—H23A⋯Cg1	0.99	2.75	3.483 (2)	132
Symmetry code: (i) -x+2, -y+1, -z+2.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009129/hp2031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009129/hp2031Isup2.hkl

checkCIF report

Comment top

2-(diphenylthiophosphino)dimethylaminomethylferrocene is a key intermediate in the synthesis of various ferrocenyl ligands (Routaboul et al., 2005; Mateus et al., 2006; Routaboul et al., 2007; Le Roux et al., 2007; Audin et al., 2010;), in our laboratories. The last step of the synthesis of 2-(diphenylthiophosphino)dimethylaminomethylferrocene is a sulfurization of 2-(diphenylphosphino)dimethylaminomethylferrocene without any purification with an excess of elemental sulfur (Mateus et al., 2006). During this synthesis, small amounts of dimethyl-(2-(diphenylthiophosphino)ferrocenyl)methylammonium diphenylphosphinodithioato can be observed in the crude materials. We were able to obtain pure salt fractions by flash chromatography on silicagel. Monocrystals suitable for X-ray diffraction analysis could be grown from a dichloromethane solution by slow diffusion of hexane.

The asymmetric unit of the title compound contains a (2-(diphenylphosphino)ferrocenyl)methyl)dimethylammonium cation and a diphenylphosphino dithioate anion which are linked through N—H···S hydrogen bond (Fig. 1; Table 1). Besides this rather strong hydrogen bond, there are weaker C—H···S and C—H···π hydrogen interactions. The anion-cation couple are linked two by two through intermolecular C—H···π interactions (Fig. 2; Table 1).

In the cation, the two Cp rings have roughly a staggered conformation with a twist angle of 20.6 (2)° and they are slightly bent with respect to each other making a dihedral angle of 4.72 (12)°. As observed in the related 2-(diphenylthiophosphino)-dimethylaminomethylferrocene (Mateus et al., 2006), the S atom is displaced undo towards the Fe atom by 1.149 (4) Å from the Cp ring. The C2—C21—N1 plane is making a dihedral angle of 58.9 (1)° with the corresponding Cp ring whereas in the above ferrocenylamine (Mateus et al., 2006) the corresponding angle was roughly 90°. The C21—N1 distance of 1.502 (2) Å is similar to the 1.526 (2) Å observed in the reported ferrocenylammonium cation, [FeCp₂PPh₂(CH₂NMe₂CH₂Ph)]⁺ (Štěpnička & Císařová, 2003).

The geometry of the anion fully agrees with related structures containing the same anion (Alison et al., 1971; Fackler et al., 1982; Silvestru et al., 1995).

Related literature top

For the synthesis of various ferrocenyl ligands, see: Audin et al. (2010); Le Roux et al. (2007); Routaboul et al. (2005, 2007). For related structures containing the C₁₂H₁₀PS₂ anion, see: Alison et al. (1971); Fackler et al. (1982); Silvestru et al. (1995). For related ferrocenyl ammonium structures, see: Štěpnička & Císařová, (2003). For a related ferrocenylamine structure, see: Mateus et al. (2006).

Experimental top

In a schlenk tube under argon 4gr of crude (2-diphenylphosphino) dimethylaminomethyl ferrocene (0,47 mmol) were dissolved in 100 ml of dichloromethane, 1,7gr of sulfur (53 mmol) were then added and the solution was heated to reflux for 2 h. The crude product was purified and crystallized at RT. Several days later, orange crystals suitable for X-ray analyses, were obtained.

Structure description top

The geometry of the anion fully agrees with related structures containing the same anion (Alison et al., 1971; Fackler et al., 1982; Silvestru et al., 1995).

For the synthesis of various ferrocenyl ligands, see: Audin et al. (2010); Le Roux et al. (2007); Routaboul et al. (2005, 2007). For related structures containing the C₁₂H₁₀PS₂ anion, see: Alison et al. (1971); Fackler et al. (1982); Silvestru et al. (1995). For related ferrocenyl ammonium structures, see: Štěpnička & Císařová, (2003). For a related ferrocenylamine structure, see: Mateus et al. (2006).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The asymmetric unit of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atom is represented as small sphere of arbitrary radii. Hydrogen bond is shown as dashed lines. H atoms not involved in hydrogen bondings within the Figure have been omitted for clarity.

Fig. 2. View showing the formation of pseudo dimer resulting from C—H···π interaction. H atoms are represented as small sphere of arbitrary radii and the H bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Cg1 and Cg2 are respectively the centroids of the C111 to C116 and C221 to C226 phenyl ring]. [Symmetry code: (i) -x + 2, -y + 1, -z + 2]

rac-{[2-(Diphenylthiophosphoryl)ferrocenyl]methyl}dimethylammonium diphenyldithiophosphinate top

Crystal data top

[Fe(C₅H₅)(C₂₀H₂₂NPS)](C₁₂H₁₀PS₂)	F(000) = 1480
M_r = 709.65	D_x = 1.379 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11690 reflections
a = 14.7800 (3) Å	θ = 3.0–29.1°
b = 18.3770 (3) Å	µ = 0.75 mm⁻¹
c = 13.6318 (3) Å	T = 180 K
β = 112.557 (2)°	Box, brown
V = 3419.31 (12) Å³	0.38 × 0.13 × 0.06 mm
Z = 4

Data collection top

Agilent Xcalibur Eos Gemini ultra diffractometer	7498 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6435 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.1978 pixels mm^-1	θ_max = 27.1°, θ_min = 3.0°
ω scans	h = −18→18
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Agilent, 2011)	k = −23→23
T_min = 0.815, T_max = 1.000	l = −17→16
37299 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0316P)² + 2.1534P] where P = (F_o² + 2F_c²)/3
7498 reflections	(Δ/σ)_max = 0.001
402 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Fe(C₅H₅)(C₂₀H₂₂NPS)](C₁₂H₁₀PS₂)	V = 3419.31 (12) Å³
M_r = 709.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.7800 (3) Å	µ = 0.75 mm⁻¹
b = 18.3770 (3) Å	T = 180 K
c = 13.6318 (3) Å	0.38 × 0.13 × 0.06 mm
β = 112.557 (2)°

Data collection top

Agilent Xcalibur Eos Gemini ultra diffractometer	7498 independent reflections
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Agilent, 2011)	6435 reflections with I > 2σ(I)
T_min = 0.815, T_max = 1.000	R_int = 0.032
37299 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.49 e Å⁻³
7498 reflections	Δρ_min = −0.27 e Å⁻³
402 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.

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
Fe1	0.892126 (18)	0.295821 (13)	0.56329 (2)	0.02385 (7)
S1	0.62046 (3)	0.37182 (3)	0.53349 (4)	0.03057 (11)
P1	0.69099 (3)	0.40945 (2)	0.44871 (3)	0.02035 (10)
N1	0.92524 (11)	0.49481 (8)	0.74750 (11)	0.0221 (3)
H1	0.9858 (16)	0.4861 (11)	0.7672 (16)	0.027*
C1	0.81988 (12)	0.38914 (9)	0.49855 (13)	0.0199 (3)
C2	0.89066 (12)	0.40119 (9)	0.60503 (13)	0.0203 (3)
C3	0.98477 (12)	0.38249 (10)	0.60566 (14)	0.0251 (4)
H3	1.0451	0.3854	0.6653	0.030*
C4	0.97303 (13)	0.35884 (10)	0.50256 (15)	0.0278 (4)
H4	1.0241	0.3430	0.4815	0.033*
C5	0.87217 (12)	0.36281 (10)	0.43610 (14)	0.0251 (4)
H5	0.8441	0.3502	0.3630	0.030*
C6	0.83827 (17)	0.23364 (11)	0.65368 (19)	0.0417 (5)
H6	0.8017	0.2508	0.6931	0.050*
C7	0.79979 (18)	0.20995 (12)	0.5482 (2)	0.0491 (6)
H7	0.7323	0.2083	0.5030	0.059*
C8	0.8793 (2)	0.18870 (12)	0.5202 (2)	0.0552 (7)
H8	0.8744	0.1700	0.4534	0.066*
C9	0.96609 (18)	0.20020 (12)	0.6086 (2)	0.0491 (6)
H9	1.0306	0.1911	0.6124	0.059*
C10	0.94077 (17)	0.22754 (12)	0.69090 (19)	0.0445 (5)
H10	0.9855	0.2399	0.7602	0.053*
C21	0.87113 (13)	0.42619 (9)	0.69984 (13)	0.0233 (4)
H21A	0.8908	0.3873	0.7543	0.028*
H21B	0.7999	0.4345	0.6784	0.028*
C22	0.90524 (15)	0.51676 (12)	0.84249 (15)	0.0342 (4)
H22A	0.9459	0.5588	0.8764	0.051*
H22B	0.9207	0.4762	0.8929	0.051*
H22C	0.8359	0.5297	0.8206	0.051*
C23	0.90543 (15)	0.55545 (10)	0.67055 (15)	0.0333 (4)
H23A	0.8359	0.5685	0.6448	0.050*
H23B	0.9219	0.5403	0.6105	0.050*
H23C	0.9454	0.5976	0.7054	0.050*
C111	0.69061 (12)	0.50804 (9)	0.44182 (12)	0.0207 (3)
C112	0.63090 (13)	0.54821 (10)	0.48002 (14)	0.0269 (4)
H112	0.5868	0.5238	0.5045	0.032*
C113	0.63565 (14)	0.62385 (11)	0.48240 (15)	0.0330 (4)
H113	0.5949	0.6510	0.5084	0.040*
C114	0.69980 (15)	0.65936 (11)	0.44694 (15)	0.0336 (4)
H114	0.7040	0.7110	0.4500	0.040*
C115	0.75816 (13)	0.61995 (10)	0.40692 (14)	0.0288 (4)
H115	0.8008	0.6447	0.3809	0.035*
C116	0.75428 (12)	0.54460 (10)	0.40491 (13)	0.0243 (4)
H116	0.7950	0.5177	0.3784	0.029*
C121	0.64309 (12)	0.37339 (10)	0.31452 (13)	0.0240 (4)
C122	0.63419 (15)	0.41465 (12)	0.22647 (15)	0.0356 (5)
H122	0.6536	0.4643	0.2346	0.043*
C123	0.59665 (17)	0.38328 (13)	0.12585 (16)	0.0437 (5)
H123	0.5905	0.4117	0.0654	0.052*
C124	0.56839 (15)	0.31161 (13)	0.11324 (16)	0.0390 (5)
H124	0.5427	0.2907	0.0443	0.047*
C125	0.57726 (16)	0.27025 (12)	0.20011 (16)	0.0410 (5)
H125	0.5582	0.2205	0.1914	0.049*
C126	0.61405 (15)	0.30098 (11)	0.30073 (15)	0.0350 (4)
H126	0.6194	0.2723	0.3607	0.042*
P2	1.19253 (3)	0.42161 (3)	0.91598 (3)	0.02193 (10)
S21	1.15395 (3)	0.50508 (3)	0.81403 (4)	0.02754 (10)
S22	1.08593 (3)	0.36503 (3)	0.93493 (4)	0.03142 (11)
C211	1.26918 (13)	0.36027 (10)	0.87503 (13)	0.0263 (4)
C212	1.35891 (14)	0.38428 (12)	0.87664 (15)	0.0333 (4)
H212	1.3819	0.4316	0.9022	0.040*
C213	1.41491 (15)	0.33888 (14)	0.84076 (16)	0.0422 (5)
H213	1.4762	0.3553	0.8417	0.051*
C214	1.38169 (17)	0.26997 (13)	0.80366 (17)	0.0452 (6)
H214	1.4204	0.2390	0.7795	0.054*
C215	1.29285 (18)	0.24609 (12)	0.80160 (18)	0.0445 (5)
H215	1.2699	0.1988	0.7755	0.053*
C216	1.23679 (16)	0.29114 (11)	0.83768 (16)	0.0346 (4)
H216	1.1757	0.2744	0.8367	0.042*
C221	1.27607 (12)	0.45558 (10)	1.04489 (13)	0.0227 (3)
C222	1.32713 (14)	0.40705 (11)	1.12579 (15)	0.0310 (4)
H222	1.3217	0.3562	1.1124	0.037*
C223	1.38586 (15)	0.43272 (12)	1.22579 (15)	0.0369 (5)
H223	1.4207	0.3994	1.2806	0.044*
C224	1.39368 (15)	0.50654 (13)	1.24572 (16)	0.0392 (5)
H224	1.4336	0.5240	1.3143	0.047*
C225	1.34355 (16)	0.55488 (12)	1.16604 (17)	0.0411 (5)
H225	1.3486	0.6057	1.1800	0.049*
C226	1.28564 (14)	0.52961 (11)	1.06545 (15)	0.0324 (4)
H226	1.2524	0.5632	1.0105	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02534 (13)	0.01906 (13)	0.02753 (14)	0.00148 (10)	0.01055 (10)	−0.00295 (10)
S1	0.0301 (2)	0.0363 (3)	0.0316 (2)	−0.00764 (19)	0.0189 (2)	−0.0016 (2)
P1	0.0183 (2)	0.0243 (2)	0.0188 (2)	−0.00269 (16)	0.00753 (16)	−0.00222 (17)
N1	0.0195 (7)	0.0237 (8)	0.0208 (7)	0.0004 (6)	0.0052 (6)	−0.0052 (6)
C1	0.0196 (8)	0.0202 (8)	0.0193 (8)	−0.0019 (6)	0.0066 (6)	−0.0009 (6)
C2	0.0205 (8)	0.0175 (8)	0.0216 (8)	−0.0003 (6)	0.0065 (6)	−0.0012 (6)
C3	0.0207 (8)	0.0263 (9)	0.0261 (9)	−0.0017 (7)	0.0065 (7)	−0.0037 (7)
C4	0.0232 (9)	0.0320 (10)	0.0320 (9)	−0.0003 (7)	0.0147 (7)	−0.0034 (8)
C5	0.0242 (8)	0.0298 (10)	0.0228 (8)	−0.0024 (7)	0.0105 (7)	−0.0039 (7)
C6	0.0528 (13)	0.0252 (10)	0.0573 (14)	0.0024 (9)	0.0323 (11)	0.0078 (10)
C7	0.0445 (13)	0.0244 (11)	0.0664 (16)	−0.0087 (9)	0.0081 (11)	0.0080 (10)
C8	0.095 (2)	0.0198 (11)	0.0596 (15)	−0.0031 (11)	0.0390 (15)	−0.0102 (10)
C9	0.0495 (13)	0.0270 (11)	0.0766 (17)	0.0154 (10)	0.0308 (13)	0.0101 (11)
C10	0.0504 (13)	0.0305 (11)	0.0454 (13)	0.0038 (10)	0.0104 (10)	0.0131 (10)
C21	0.0243 (8)	0.0238 (9)	0.0216 (8)	−0.0033 (7)	0.0086 (7)	−0.0035 (7)
C22	0.0364 (10)	0.0397 (12)	0.0281 (10)	0.0009 (9)	0.0141 (8)	−0.0110 (8)
C23	0.0406 (11)	0.0225 (9)	0.0299 (10)	−0.0012 (8)	0.0059 (8)	−0.0013 (8)
C111	0.0172 (7)	0.0249 (9)	0.0168 (8)	−0.0005 (6)	0.0028 (6)	−0.0013 (6)
C112	0.0204 (8)	0.0344 (10)	0.0260 (9)	0.0007 (7)	0.0089 (7)	−0.0031 (8)
C113	0.0310 (10)	0.0329 (11)	0.0337 (10)	0.0072 (8)	0.0110 (8)	−0.0047 (8)
C114	0.0400 (11)	0.0246 (10)	0.0298 (10)	0.0038 (8)	0.0063 (8)	0.0006 (8)
C115	0.0294 (9)	0.0301 (10)	0.0239 (9)	−0.0017 (8)	0.0070 (7)	0.0051 (8)
C116	0.0225 (8)	0.0294 (10)	0.0198 (8)	0.0017 (7)	0.0069 (7)	0.0016 (7)
C121	0.0175 (8)	0.0314 (10)	0.0222 (8)	−0.0013 (7)	0.0066 (7)	−0.0038 (7)
C122	0.0423 (11)	0.0375 (11)	0.0255 (9)	−0.0113 (9)	0.0113 (8)	−0.0036 (8)
C123	0.0531 (13)	0.0522 (14)	0.0232 (10)	−0.0094 (11)	0.0116 (9)	−0.0021 (9)
C124	0.0370 (11)	0.0500 (13)	0.0253 (10)	−0.0004 (9)	0.0067 (8)	−0.0122 (9)
C125	0.0469 (12)	0.0334 (11)	0.0346 (11)	−0.0028 (9)	0.0065 (9)	−0.0112 (9)
C126	0.0419 (11)	0.0319 (11)	0.0253 (9)	−0.0036 (9)	0.0062 (8)	−0.0035 (8)
P2	0.0210 (2)	0.0259 (2)	0.0184 (2)	0.00091 (17)	0.00710 (17)	−0.00071 (17)
S21	0.0231 (2)	0.0321 (2)	0.0252 (2)	0.00201 (17)	0.00693 (17)	0.00576 (18)
S22	0.0290 (2)	0.0373 (3)	0.0304 (2)	−0.00756 (19)	0.01418 (19)	−0.0032 (2)
C211	0.0293 (9)	0.0309 (10)	0.0186 (8)	0.0077 (7)	0.0092 (7)	0.0034 (7)
C212	0.0287 (9)	0.0449 (12)	0.0258 (9)	0.0048 (8)	0.0099 (8)	−0.0001 (8)
C213	0.0302 (10)	0.0665 (16)	0.0306 (10)	0.0127 (10)	0.0125 (8)	0.0051 (10)
C214	0.0535 (14)	0.0518 (14)	0.0335 (11)	0.0283 (11)	0.0203 (10)	0.0081 (10)
C215	0.0653 (15)	0.0314 (11)	0.0420 (12)	0.0142 (10)	0.0262 (11)	0.0040 (10)
C216	0.0433 (11)	0.0297 (10)	0.0348 (10)	0.0054 (8)	0.0194 (9)	0.0023 (8)
C221	0.0208 (8)	0.0279 (9)	0.0208 (8)	0.0004 (7)	0.0094 (7)	−0.0005 (7)
C222	0.0329 (10)	0.0311 (10)	0.0261 (9)	0.0041 (8)	0.0083 (8)	0.0011 (8)
C223	0.0311 (10)	0.0492 (13)	0.0233 (9)	0.0060 (9)	0.0025 (8)	0.0026 (9)
C224	0.0309 (10)	0.0545 (14)	0.0273 (10)	−0.0090 (9)	0.0056 (8)	−0.0116 (9)
C225	0.0453 (12)	0.0336 (11)	0.0393 (12)	−0.0096 (9)	0.0105 (10)	−0.0101 (9)
C226	0.0347 (10)	0.0292 (10)	0.0297 (10)	−0.0028 (8)	0.0083 (8)	−0.0005 (8)

Geometric parameters (Å, º) top

Fe1—C2	2.0208 (17)	C112—C113	1.391 (3)
Fe1—C1	2.0340 (17)	C112—H112	0.9500
Fe1—C3	2.0344 (18)	C113—C114	1.382 (3)
Fe1—C9	2.036 (2)	C113—H113	0.9500
Fe1—C10	2.039 (2)	C114—C115	1.388 (3)
Fe1—C8	2.042 (2)	C114—H114	0.9500
Fe1—C7	2.044 (2)	C115—C116	1.386 (3)
Fe1—C6	2.052 (2)	C115—H115	0.9500
Fe1—C5	2.0533 (18)	C116—H116	0.9500
Fe1—C4	2.0532 (18)	C121—C122	1.383 (3)
S1—P1	1.9557 (6)	C121—C126	1.389 (3)
P1—C1	1.7992 (17)	C122—C123	1.392 (3)
P1—C111	1.8141 (18)	C122—H122	0.9500
P1—C121	1.8146 (17)	C123—C124	1.372 (3)
N1—C23	1.481 (2)	C123—H123	0.9500
N1—C22	1.490 (2)	C124—C125	1.370 (3)
N1—C21	1.501 (2)	C124—H124	0.9500
N1—H1	0.85 (2)	C125—C126	1.387 (3)
C1—C5	1.436 (2)	C125—H125	0.9500
C1—C2	1.444 (2)	C126—H126	0.9500
C2—C3	1.430 (2)	P2—C221	1.8270 (17)
C2—C21	1.500 (2)	P2—C211	1.8305 (18)
C3—C4	1.417 (2)	P2—S22	1.9856 (6)
C3—H3	0.9500	P2—S21	2.0004 (6)
C4—C5	1.419 (2)	C211—C216	1.384 (3)
C4—H4	0.9500	C211—C212	1.390 (3)
C5—H5	0.9500	C212—C213	1.390 (3)
C6—C7	1.398 (3)	C212—H212	0.9500
C6—C10	1.405 (3)	C213—C214	1.382 (3)
C6—H6	0.9500	C213—H213	0.9500
C7—C8	1.422 (4)	C214—C215	1.374 (3)
C7—H7	0.9500	C214—H214	0.9500
C8—C9	1.399 (4)	C215—C216	1.388 (3)
C8—H8	0.9500	C215—H215	0.9500
C9—C10	1.404 (3)	C216—H216	0.9500
C9—H9	0.9500	C221—C226	1.385 (3)
C10—H10	0.9500	C221—C222	1.394 (3)
C21—H21A	0.9900	C222—C223	1.388 (3)
C21—H21B	0.9900	C222—H222	0.9500
C22—H22A	0.9800	C223—C224	1.380 (3)
C22—H22B	0.9800	C223—H223	0.9500
C22—H22C	0.9800	C224—C225	1.379 (3)
C23—H23A	0.9800	C224—H224	0.9500
C23—H23B	0.9800	C225—C226	1.388 (3)
C23—H23C	0.9800	C225—H225	0.9500
C111—C112	1.396 (2)	C226—H226	0.9500
C111—C116	1.398 (2)

C2—Fe1—C1	41.73 (6)	C10—C9—Fe1	69.96 (12)
C2—Fe1—C3	41.28 (7)	C8—C9—H9	126.1
C1—Fe1—C3	69.34 (7)	C10—C9—H9	126.1
C2—Fe1—C9	143.50 (9)	Fe1—C9—H9	125.3
C1—Fe1—C9	172.17 (9)	C9—C10—C6	108.7 (2)
C3—Fe1—C9	111.40 (9)	C9—C10—Fe1	69.74 (13)
C2—Fe1—C10	112.82 (8)	C6—C10—Fe1	70.40 (12)
C1—Fe1—C10	147.52 (8)	C9—C10—H10	125.6
C3—Fe1—C10	105.12 (9)	C6—C10—H10	125.6
C9—Fe1—C10	40.31 (10)	Fe1—C10—H10	125.8
C2—Fe1—C8	174.18 (10)	C2—C21—N1	112.54 (14)
C1—Fe1—C8	135.46 (10)	C2—C21—H21A	109.1
C3—Fe1—C8	144.53 (10)	N1—C21—H21A	109.1
C9—Fe1—C8	40.11 (11)	C2—C21—H21B	109.1
C10—Fe1—C8	67.38 (10)	N1—C21—H21B	109.1
C2—Fe1—C7	133.57 (9)	H21A—C21—H21B	107.8
C1—Fe1—C7	112.83 (8)	N1—C22—H22A	109.5
C3—Fe1—C7	169.60 (9)	N1—C22—H22B	109.5
C9—Fe1—C7	67.94 (10)	H22A—C22—H22B	109.5
C10—Fe1—C7	67.32 (10)	N1—C22—H22C	109.5
C8—Fe1—C7	40.72 (11)	H22A—C22—H22C	109.5
C2—Fe1—C6	108.42 (8)	H22B—C22—H22C	109.5
C1—Fe1—C6	118.04 (8)	N1—C23—H23A	109.5
C3—Fe1—C6	129.75 (9)	N1—C23—H23B	109.5
C9—Fe1—C6	67.90 (9)	H23A—C23—H23B	109.5
C10—Fe1—C6	40.19 (9)	N1—C23—H23C	109.5
C8—Fe1—C6	67.73 (10)	H23A—C23—H23C	109.5
C7—Fe1—C6	39.91 (10)	H23B—C23—H23C	109.5
C2—Fe1—C5	69.49 (7)	C112—C111—C116	119.31 (17)
C1—Fe1—C5	41.12 (7)	C112—C111—P1	119.92 (13)
C3—Fe1—C5	68.49 (7)	C116—C111—P1	120.64 (13)
C9—Fe1—C5	131.32 (9)	C113—C112—C111	120.24 (17)
C10—Fe1—C5	168.16 (8)	C113—C112—H112	119.9
C8—Fe1—C5	111.59 (9)	C111—C112—H112	119.9
C7—Fe1—C5	120.23 (9)	C114—C113—C112	119.92 (18)
C6—Fe1—C5	151.38 (8)	C114—C113—H113	120.0
C2—Fe1—C4	69.14 (7)	C112—C113—H113	120.0
C1—Fe1—C4	68.87 (7)	C113—C114—C115	120.27 (18)
C3—Fe1—C4	40.56 (7)	C113—C114—H114	119.9
C9—Fe1—C4	106.34 (9)	C115—C114—H114	119.9
C10—Fe1—C4	128.44 (9)	C116—C115—C114	120.12 (18)
C8—Fe1—C4	115.60 (9)	C116—C115—H115	119.9
C7—Fe1—C4	149.79 (9)	C114—C115—H115	119.9
C6—Fe1—C4	167.51 (9)	C115—C116—C111	120.11 (17)
C5—Fe1—C4	40.42 (7)	C115—C116—H116	119.9
C1—P1—C111	102.03 (8)	C111—C116—H116	119.9
C1—P1—C121	104.60 (8)	C122—C121—C126	119.11 (17)
C111—P1—C121	108.68 (8)	C122—C121—P1	123.04 (14)
C1—P1—S1	115.51 (6)	C126—C121—P1	117.85 (14)
C111—P1—S1	113.07 (6)	C121—C122—C123	119.84 (19)
C121—P1—S1	112.11 (6)	C121—C122—H122	120.1
C23—N1—C22	111.15 (15)	C123—C122—H122	120.1
C23—N1—C21	113.45 (13)	C124—C123—C122	120.5 (2)
C22—N1—C21	110.67 (14)	C124—C123—H123	119.7
C23—N1—H1	105.4 (14)	C122—C123—H123	119.7
C22—N1—H1	108.3 (14)	C125—C124—C123	120.03 (19)
C21—N1—H1	107.5 (14)	C125—C124—H124	120.0
C5—C1—C2	107.49 (14)	C123—C124—H124	120.0
C5—C1—P1	125.37 (13)	C124—C125—C126	120.0 (2)
C2—C1—P1	126.99 (12)	C124—C125—H125	120.0
C5—C1—Fe1	70.16 (10)	C126—C125—H125	120.0
C2—C1—Fe1	68.65 (9)	C125—C126—C121	120.50 (19)
P1—C1—Fe1	129.96 (9)	C125—C126—H126	119.7
C3—C2—C1	107.29 (14)	C121—C126—H126	119.7
C3—C2—C21	125.22 (15)	C221—P2—C211	103.57 (8)
C1—C2—C21	127.46 (15)	C221—P2—S22	109.33 (6)
C3—C2—Fe1	69.87 (10)	C211—P2—S22	109.40 (7)
C1—C2—Fe1	69.63 (9)	C221—P2—S21	108.27 (6)
C21—C2—Fe1	124.22 (12)	C211—P2—S21	107.77 (6)
C4—C3—C2	108.61 (15)	S22—P2—S21	117.58 (3)
C4—C3—Fe1	70.43 (10)	C216—C211—C212	119.37 (18)
C2—C3—Fe1	68.85 (10)	C216—C211—P2	120.67 (15)
C4—C3—H3	125.7	C212—C211—P2	119.88 (15)
C2—C3—H3	125.7	C213—C212—C211	119.8 (2)
Fe1—C3—H3	126.6	C213—C212—H212	120.1
C3—C4—C5	108.46 (15)	C211—C212—H212	120.1
C3—C4—Fe1	69.01 (10)	C214—C213—C212	120.2 (2)
C5—C4—Fe1	69.80 (10)	C214—C213—H213	119.9
C3—C4—H4	125.8	C212—C213—H213	119.9
C5—C4—H4	125.8	C215—C214—C213	120.2 (2)
Fe1—C4—H4	127.0	C215—C214—H214	119.9
C4—C5—C1	108.15 (15)	C213—C214—H214	119.9
C4—C5—Fe1	69.79 (11)	C214—C215—C216	119.8 (2)
C1—C5—Fe1	68.72 (10)	C214—C215—H215	120.1
C4—C5—H5	125.9	C216—C215—H215	120.1
C1—C5—H5	125.9	C211—C216—C215	120.6 (2)
Fe1—C5—H5	127.1	C211—C216—H216	119.7
C7—C6—C10	107.7 (2)	C215—C216—H216	119.7
C7—C6—Fe1	69.75 (13)	C226—C221—C222	119.09 (17)
C10—C6—Fe1	69.42 (12)	C226—C221—P2	120.61 (14)
C7—C6—H6	126.2	C222—C221—P2	120.22 (14)
C10—C6—H6	126.2	C223—C222—C221	120.29 (19)
Fe1—C6—H6	126.2	C223—C222—H222	119.9
C6—C7—C8	108.0 (2)	C221—C222—H222	119.9
C6—C7—Fe1	70.33 (12)	C224—C223—C222	120.08 (19)
C8—C7—Fe1	69.55 (13)	C224—C223—H223	120.0
C6—C7—H7	126.0	C222—C223—H223	120.0
C8—C7—H7	126.0	C225—C224—C223	119.96 (19)
Fe1—C7—H7	125.7	C225—C224—H224	120.0
C9—C8—C7	107.9 (2)	C223—C224—H224	120.0
C9—C8—Fe1	69.72 (13)	C224—C225—C226	120.3 (2)
C7—C8—Fe1	69.73 (12)	C224—C225—H225	119.9
C9—C8—H8	126.1	C226—C225—H225	119.9
C7—C8—H8	126.1	C221—C226—C225	120.31 (19)
Fe1—C8—H8	126.1	C221—C226—H226	119.8
C8—C9—C10	107.8 (2)	C225—C226—H226	119.8
C8—C9—Fe1	70.17 (13)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C111–C116 and C221–C226 phenyl rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S21	0.85 (2)	2.34 (2)	3.1516 (15)	160.3 (19)
C21—H21B···S1	0.99	2.87	3.664 (2)	137
C22—H22C···Cg2ⁱ	0.99	2.75	3.621 (3)	149
C23—H23A···Cg1	0.99	2.75	3.483 (2)	132

Symmetry code: (i) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₂₀H₂₂NPS)](C₁₂H₁₀PS₂)
M_r	709.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	180
a, b, c (Å)	14.7800 (3), 18.3770 (3), 13.6318 (3)
β (°)	112.557 (2)
V (Å³)	3419.31 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.38 × 0.13 × 0.06

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini ultra
Absorption correction	Multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.815, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	37299, 7498, 6435
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.05
No. of reflections	7498
No. of parameters	402
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.27

Computer programs: CrysAlis PRO (Agilent, 2011), SIR97 (Altomare et al., 1999), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C111–C116 and C221–C226 phenyl rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S21	0.85 (2)	2.34 (2)	3.1516 (15)	160.3 (19)
C21—H21B···S1	0.9900	2.8700	3.664 (2)	137.00
C22—H22C···Cg2ⁱ	0.99	2.75	3.621 (3)	149
C23—H23A···Cg1	0.99	2.75	3.483 (2)	132

Symmetry code: (i) −x+2, −y+1, −z+2.

Acknowledgements

The CNRS is acknowledged for financial support and NM acknowledges the Department of Chemistry of the University of Mentouri for funding her stay in the LCC.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Alison, J. M. C., Stephenson, T. A. & Gould, R. O. (1971). J. Chem. Soc. A, pp. 3690–3696. CrossRef Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Audin, C., Daran, J.-C., Deydier, E., Manoury, E. & Poli, R. (2010). C. R. Chimie, 13, 890–899. CrossRef CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII, Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Google Scholar
Fackler, J. P. Jr, Thompson, L. D., Lin, I. J. B., Stephenson, T. A., Gould, R. O., Alison, J. M. C. & Fraser, A. J. F. (1982). Inorg. Chem. 21, 2397–2403. CSD CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Le Roux, E., Malacea, R., Manoury, E., Poli, R., Gonsalvi, L. & Peruzzini, M. (2007). Adv. Synth. Catal. 349, 1064–1073. Web of Science CrossRef Google Scholar
Mateus, N., Routaboul, L., Daran, J.-C. & Manoury, E. (2006). J. Organomet. Chem. 691, 2297–2310. Web of Science CSD CrossRef CAS Google Scholar
Routaboul, L., Vincendeau, S., Daran, J.-C. & Manoury, E. (2005). Tetrahedron Asymmetry, 16, 2685–2690. Web of Science CrossRef CAS Google Scholar
Routaboul, L., Vincendeau, S., Turrin, C.-O., Caminade, A.-M., Majoral, J.-P., Daran, J.-C. & Manoury, E. (2007). J. Organomet. Chem. 692, 1064–1073. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Silvestru, A., Haiduc, I., Toscano, R. A. & Breunig, H. J. (1995). Polyhedron, 14, 2047–2033. CSD CrossRef CAS Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Štěpnička, P. & Císařová, I. (2003). Organometallics, 22, 1728–1740. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m381-m382

doi:10.1107/S1600536812009129

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

rac-{[2-(Di­phenyl­thio­phosphor­yl)ferrocen­yl]meth­yl}di­methyl­ammonium di­phenyl­di­thio­phosphinate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

rac-{[2-(Diphenylthiophosphoryl)ferrocenyl]methyl}dimethylammonium diphenyldithiophosphinate