Crystal structure of penta­carbon­yl(2,2-di­fluoro­propane­thio­ato-κS)manganese(I)

Daran, J.-C.; Morales-Cerrada, R.; Fliedel, C.; Gayet, F.; Ladmiral, V.; Ameduri, B.; Poli, R.

doi:10.1107/S2056989019004134

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 529-532

https://doi.org/10.1107/S2056989019004134

Open

access

Crystal structure of pentacarbonyl(2,2-difluoropropanethioato-κS)manganese(I)

Jean-Claude Daran,^a ^* Roberto Morales-Cerrada,^a,^b Christophe Fliedel,^a Florence Gayet,^a Vincent Ladmiral,^b Bruno Ameduri ^b and Rinaldo Poli ^a

^aLCC-CNRS, Université de Toulouse, CNRS, INPT, Toulouse, France, and ^bICGM CNRS, Univ Montpellier, ENSCM, Montpellier, France
^*Correspondence e-mail: daran@lcc-toulouse.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 13 March 2019; accepted 27 March 2019; online 2 April 2019)

The title compound, [Mn{SC(O)CF₂CH₃}(CO)₅], has been isolated as a by-product during the reaction of K[Mn(CO)₅] with CH₃CF₂COCl. It is built up from a difluoromethylpropanethioate bonded to an Mn(CO)₅ moiety through the S atom. The Mn atom has an almost perfect octahedral coordination sphere. It is one of the rare examples of compounds containing the (CO)₅MnS—C fragment. In the crystal, the methyl group occupies a pocket surrounded by the O atoms of three carbonyl groups of the Mn(CO)₅ moiety; however, the H⋯O distances are rather long. These interactions lead to the formation of layers lying parallel to (101), which enclose R₄⁴(15) and R₄⁴(16) ring motifs. The CF₂ group is disordered over two sets of sites with occupancies of 0.849 (3) and 0.151 (3).

Keywords: crystal structure; Mn(CO)₅ derivatives; Mn-S bond; intermolecular contacts.

CCDC reference: 1906042

1. Chemical context

Alkylpentacarbonylmanganese(I) complexes containing fluorinated alkyl groups, [MnR_F(CO)₅], have been known since 1960 (Kaesz et al., 1960 ; Beck et al., 1961 ) but X-ray structures have been scarcely investigated until recently (Morales-Cerrada, Fliedel, Daran et al., 2019 ). Our interest in these compounds is related to a study of the homolytic Mn—C bond strength and how this is affected by the F substitution at the α and β positions of the alkyl chain (Morales-Cerrada, Fliedel, Gayet et al., 2019 ). The compounds where R_F stands for CH₂CF₃ and CF₂CH₃ may be considered as models for the role of [Mn(CO)₅] as a radical-trapping species in the polymerization of vinylidene fluoride, where the Mn—C bonds may be formed and cleaved reversibly. While the synthesis of the CH₂CF₃ derivative could be accomplished as planned and the product could be obtained in a pure form and crystallized (Morales-Cerrada, Fliedel, Daran et al., 2019), the synthesis of the CF₂CH₃ derivative led to the unexpected compound, [Mn{SC(O)CH₃CF₂}(CO)₅] (1), reported here.

2. Structural commentary

The title compound (1), is built up from a difluoromethylpropanethioate bonded to an Mn(CO)₅ moiety through the S atom (Fig. 1). Selected bond distances and bond angles involving atom Mn1 are given in Table 1, and it can be seen that this atom has a nearly perfect octahedral coordination sphere. As expected, the Mn1—S1—C1—C2 fragment is almost planar, as shown by the value of the torsion angle of −177.98 (11)°. This plane roughly bisects the dihedral angle formed by the C11/Mn1/C12/S1 and C11/Mn1/C13/S1 planes with values of 50.06 (7) and 39.9 (1)°, respectively, placing the O2 atom relatively close to the O atoms of the two carbonyl groups C12=O12 and C13=O13 with distances O2⋯O12 = 3.058 (2) Å and O2⋯O13 = 3.257 (2) Å. The smallest bond angles, 86.01 (5)° for C14—Mn1—S1 and 86.14 (5)° for C15—Mn1—S1, are certainly related to steric hindrance resulting from these relatively short intramolecular O⋯O contacts. These short interactions might force the Mn1—S1 bond to bend slightly towards the equatorial plane [C12/C13/C14/C15]. The shortest Mn—C(O) distance is observed for the carbonyl group trans to the S atom; Mn1—C11 = 1.8376 (17) Å

Table 1
Selected geometric parameters (Å, °)

Mn1—C11	1.8376 (17)	Mn1—C14	1.8631 (17)
Mn1—C12	1.8807 (17)	Mn1—C15	1.8849 (17)
Mn1—C13	1.8720 (17)

C11—Mn1—C12	91.08 (7)	C13—Mn1—C15	174.92 (7)
C11—Mn1—C13	90.69 (7)	C13—Mn1—S1	88.91 (5)
C11—Mn1—C14	90.47 (7)	C14—Mn1—C12	177.58 (7)
C11—Mn1—C15	94.32 (7)	C14—Mn1—C13	90.77 (7)
C11—Mn1—S1	176.45 (5)	C14—Mn1—C15	90.07 (7)
C12—Mn1—C15	87.96 (7)	C14—Mn1—S1	86.01 (5)
C12—Mn1—S1	92.46 (5)	C15—Mn1—S1	86.14 (5)
C13—Mn1—C12	91.07 (7)

Figure 1
A view of the molecular structure of compound (1), with the atom labelling. For clarity, only the major disordered component of the –CF₂ group is shown. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, the methyl group occupies a pocket surrounded by O atoms of three carbonyl groups, C11=O11, C12=O12 and C14=O14, forming a two-dimensional network that develops parallel to (101); see Table 2 and Fig. 2. These rather weak C—H⋯O interactions result in the formation of two graph-set motifs, R₄⁴(15) and R₄⁴(16), as shown in Fig. 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3A—H3A1⋯O14ⁱ	0.98	2.81	3.732 (3)	158
C3A—H3A2⋯O12ⁱⁱ	0.98	2.79	3.753 (3)	166
C3A—H3A3⋯O11ⁱⁱⁱ	0.98	2.79	3.564 (3)	136
C3B—H3B2⋯O12ⁱⁱ	0.98	2.81	3.777 (19)	168
C3B—H3B3⋯O11ⁱⁱⁱ	0.98	2.37	3.165 (15)	138
C3B—H3B3⋯O11ⁱⁱⁱ	0.98	2.37	3.165 (15)	138
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view of the crystal packing of compound (1). The C—H⋯O interactions (Table 2

) involving the major component of the disordered –CF₂ group, are shown as dashed lines.

4. Database survey

A search in the Cambridge Structural Database (CSD, V5.40, update February 2019; Groom et al., 2016 ) using a (CO)₅MnS—C fragment revealed only three hits. These include, [μ₂-1,2-bis(p-fluorophenyl)-ethylene-1,2-dithiolato-S,S′]decacarbonyldi-manganese (CSD refcode CECCES; Lindner et al., 1983 ), pentacarbonyl-[(N-pentafluorothio)fluorothioformimido-S]manganese (JEBNOT; Damerius et al., 1989 ) and μ-1,2-dithiooxalatobis(pentacarbonyl)manganese (TOXCMN; Weber & Mattes, 1979 ). The Mn—S, S—C, Mn—C bond distances and Mn—S—C bond angles are compared to those for compound (1) in Table 3. As in compound (1), the Mn—C bond trans to the S atom is significantly shorter than the four other Mn—C bonds. The longest Mn—S bond, 2.405 Å in CECCES, may be related to the presence of the bulky fluorophenyl group attached to the C(S) atom. For compound (1) and TOXCMN, both having an oxo group attached to the C(S) atom, the Mn—S—C angle is nearly identical, 106.26 (6) and ca 105.64°, respectively (Table 3). In contrast, this angle is slightly larger for CECCES and for JEBNOT, ca 108.8 and 108.1°, respectively.

Table 3
Comparison of selected bond lengths (Å) and bond angle (°) in the title compound (1) and related compounds having an Mn(CO)₅SC fragment

Parameter	(1)	CECCES^a	JEBNOT^b	TOXCMN^c
Mn—S	2.3768 (5)	2.405	2.384	2.379
C—S	1.725 (2)	1.741	1.723	1.737
Mn—S—C	106.26 (6)	108.84	108.12	105.64
Mn—C11	1.838 (2)	1.803	1.835	1.840
Mn—C12	1.881 (2)	1.867	1.871	1.883
Mn—C13	1.872 (2)	1.861	1.891	1.857
Mn—C14	1.863 (3)	1.864	1.871	1.880
Mn—C15	1.885 (2)	1.878	1.891	1.857
Notes: (a) Lindner et al. (1983); (b) Damerius et al. (1989); (b) Weber & Mattes (1979).

5. Synthesis and crystallization

The synthesis of the target compound, [Mn(CF₂CH₃)(CO)₅], requires transit through the corresponding acyl derivative, [Mn(COCF₂CH₃)(CO)₅], because direct alkylation of CH₃CF₂-X (X = Cl, Br) reagents by the powerful [Mn(CO)₅]⁻ nucleophile suffers from the inverted polarity of the C—X bond, leading to [MnX(CO)₅] instead (Beck et al., 1961). The corresponding acylation using CH₃CF₂COCl as acylating agent was successful (Morales-Cerrada, Fliedel, Daran et al., 2019). However, the pure product could only be obtained when the 2,2-difluoropropanoyl chloride was synthesized by the action of oxalyl chloride on 2,2-difluoropropionic acid. In a first synthetic study, 2,2-difluoropropionic acid was chlorinated by the more common thionyl chloride reagent, SOCl₂. When the resulting acyl chloride was used to acylate [Mn(CO)₅]⁻, the title compound crystallized as colourless single crystals. The sulfur atom must have been provided by the thionyl chloride remaining as a contaminant in the acyl chloride reagent.

2,2-Difluoropropanoyl chloride was freshly prepared as follows. To a 50 ml round flask equipped with a reflux condenser, was introduced 5.28 g of 2,2-difluoropropionic acid (47.97 mmol) and 10.05 g of thionyl chloride (84.48 mmol; previously purified by reflux in the presence of sulfur powder and then distilled) was added dropwise. The mixture was then heated up to 363 K over 2 h (reflux). The product was purified by distillation (b.p. 308–313 K), giving 4.85 g of a colourless liquid. The amount of thionyl chloride contaminant in the distilled product could not be estimated by NMR spectroscopy.

Synthesis of the title compound (1): To a Schlenk tube were introduced 390 mg (9.97 mmol) of metallic potassium and 358 mg (15.57 mmol) of metallic sodium under argon. They were crushed together to generate a liquid NaK alloy. A solution of dimanganese decacarbonyl (2.00 g, 5.13 mmol) in 30 ml of dry THF was added and the resulting mixture was stirred for 3 h at room temperature, leading to the formation of K⁺[Mn(CO)₅]⁻. The mixture was filtered through Celite to yield a greenish brown solution, rinsing the Celite with 10 ml of dry THF. Then, 2,2-trifluoropropanoyl chloride (1.31 g, 10.19 mmol), made as described above, was added dropwise at room temperature. The resulting solution was further stirred at room temperature for 3 h, followed by evaporation of the solvents under reduced pressure. The product was purified by column chromatography through a silica gel column, using n-pentane as the mobile phase. After elimination of a first yellow fraction corresponding to [Mn₂(CO)₁₀], the mobile phase polarity was increased using a mixture of n-pentane and diethyl ether (2:1). An orange band was collected, followed by evaporation to dryness under reduced pressure to afford the product as an orange–brown liquid. The product was stored in the fridge (276–277 K), leading to the growth of thin colourless plate-like crystals of the title compound which were collected after two days.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The methyl H atoms were fixed geometrically and treated as riding: C—H = 0.98 Å with U_iso(H) = 1.5U_eq(CH₃). The two fluorine atoms presented elongated ellipsoids, which could be related to disorder. To consider a realistic chemical disorder, we defined a model by rotation around the C1—C2 bond. Initially, the model could be refined isotropically to define the occupancy factors using a free variable. The result showed a major component with an occupancy factor of 85% and a minor one at 15%. As a result, it was impossible to freely refine the thermal ellipsoids for the disordered CF₂ group. The anisotropic refinement has been realized using severe EADP restraints for the C and F atoms.

Table 4
Experimental details

Crystal data
Chemical formula	[Mn(C₃H₃F₂OS)(CO)₅]
M_r	320.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.3503 (4), 14.9583 (9), 12.3127 (9)
β (°)	97.149 (3)
V (Å³)	1160.49 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.36
Crystal size (mm)	0.40 × 0.26 × 0.04

Data collection
Diffractometer	Nonius CAD-4 with APEXII CCD
Absorption correction	Multi-scan (Blessing, 1995 )
T_min, T_max	0.621, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	43723, 2554, 2261
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.062, 1.04
No. of reflections	2554
No. of parameters	175
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.28
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SIR97 (Altomare et al., 1999 ), SHELXL2014 (Sheldrick, 2015 ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1906042

Crystal structure: contains datablocks 1, global. DOI: https://doi.org/10.1107/S2056989019004134/su5491sup1.cif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); 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: SHELXL2014 (Sheldrick, 2015).

Pentacarbonyl(2,2-difluoropropanethioato-κS)manganese(I) top

Crystal data top

[Mn(C₃H₃F₂OS)(CO)₅]	F(000) = 632
M_r = 320.10	D_x = 1.832 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.3503 (4) Å	Cell parameters from 9996 reflections
b = 14.9583 (9) Å	θ = 2.2–28.9°
c = 12.3127 (9) Å	µ = 1.36 mm⁻¹
β = 97.149 (3)°	T = 173 K
V = 1160.49 (13) Å³	Thin_plate, colourless
Z = 4	0.40 × 0.26 × 0.04 mm

Data collection top

Nonius CAD-4 with APEXII CCD diffractometer	2554 independent reflections
Radiation source: fine-focus sealed tube	2261 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 27.1°, θ_min = 2.7°
Absorption correction: multi-scan (Blessing, 1995)	h = −8→8
T_min = 0.621, T_max = 0.746	k = −19→19
43723 measured reflections	l = −15→15

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.033P)² + 0.5266P] where P = (F_o² + 2F_c²)/3
2554 reflections	(Δ/σ)_max = 0.001
175 parameters	Δρ_max = 0.55 e Å⁻³
6 restraints	Δρ_min = −0.28 e Å⁻³

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.43292 (4)	0.29392 (2)	0.45193 (2)	0.01827 (8)
S1	0.53795 (7)	0.42961 (3)	0.37381 (4)	0.02705 (11)
O2	0.6662 (2)	0.32546 (9)	0.22242 (11)	0.0380 (3)
O11	0.2678 (2)	0.13030 (8)	0.54815 (10)	0.0335 (3)
O12	0.8262 (2)	0.19606 (9)	0.40668 (12)	0.0386 (3)
O13	0.1947 (2)	0.24358 (10)	0.23502 (10)	0.0374 (3)
O14	0.0554 (2)	0.39501 (10)	0.50870 (13)	0.0429 (3)
O15	0.6894 (2)	0.35866 (9)	0.65865 (11)	0.0361 (3)
C1	0.6470 (3)	0.40015 (11)	0.25739 (14)	0.0258 (3)
C11	0.3361 (3)	0.19238 (11)	0.51356 (13)	0.0231 (3)
C12	0.6773 (3)	0.23362 (11)	0.41940 (14)	0.0249 (3)
C13	0.2873 (3)	0.26287 (11)	0.31555 (14)	0.0246 (3)
C14	0.1982 (3)	0.35751 (11)	0.48685 (14)	0.0264 (3)
C15	0.5915 (3)	0.33322 (10)	0.58282 (14)	0.0238 (3)
C2	0.7351 (3)	0.47775 (12)	0.19361 (16)	0.0348 (4)
C3A	0.9645 (4)	0.4925 (2)	0.2222 (2)	0.0413 (6)	0.849 (3)
H3A1	0.993454	0.510299	0.299223	0.062*	0.849 (3)
H3A2	1.011515	0.539893	0.175822	0.062*	0.849 (3)
H3A3	1.041157	0.437149	0.210635	0.062*	0.849 (3)
F1A	0.6207 (3)	0.55205 (11)	0.2005 (2)	0.0672 (7)	0.849 (3)
F2A	0.6999 (3)	0.45454 (13)	0.08233 (12)	0.0604 (6)	0.849 (3)
C3B	0.952 (2)	0.4766 (13)	0.1799 (15)	0.0413 (6)	0.151 (3)
H3B1	1.037235	0.468084	0.251102	0.062*	0.151 (3)
H3B2	0.990454	0.533469	0.148047	0.062*	0.151 (3)
H3B3	0.979264	0.427449	0.130863	0.062*	0.151 (3)
F1B	0.7158 (19)	0.5589 (6)	0.2621 (11)	0.0672 (7)	0.151 (3)
F2B	0.5979 (18)	0.4975 (8)	0.1138 (8)	0.0604 (6)	0.151 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01945 (13)	0.01603 (13)	0.01948 (13)	0.00083 (8)	0.00298 (9)	0.00078 (9)
S1	0.0315 (2)	0.01629 (19)	0.0345 (2)	0.00001 (15)	0.00874 (18)	0.00293 (16)
O2	0.0568 (9)	0.0261 (7)	0.0341 (7)	−0.0052 (6)	0.0176 (6)	0.0000 (5)
O11	0.0430 (7)	0.0257 (6)	0.0326 (7)	−0.0076 (5)	0.0081 (6)	0.0041 (5)
O12	0.0318 (7)	0.0426 (8)	0.0422 (8)	0.0146 (6)	0.0076 (6)	0.0002 (6)
O13	0.0402 (7)	0.0454 (8)	0.0250 (7)	−0.0088 (6)	−0.0029 (6)	0.0005 (6)
O14	0.0294 (7)	0.0434 (8)	0.0570 (9)	0.0104 (6)	0.0106 (6)	−0.0062 (7)
O15	0.0456 (8)	0.0279 (7)	0.0319 (7)	−0.0035 (6)	−0.0072 (6)	−0.0033 (5)
C1	0.0239 (8)	0.0256 (8)	0.0276 (8)	−0.0028 (6)	0.0021 (6)	0.0077 (7)
C11	0.0254 (8)	0.0241 (8)	0.0197 (8)	0.0009 (6)	0.0028 (6)	−0.0022 (6)
C12	0.0285 (9)	0.0223 (8)	0.0238 (8)	−0.0002 (7)	0.0025 (6)	0.0010 (6)
C13	0.0263 (8)	0.0217 (8)	0.0266 (9)	−0.0010 (6)	0.0069 (7)	0.0047 (6)
C14	0.0265 (8)	0.0247 (8)	0.0279 (9)	−0.0010 (7)	0.0026 (7)	0.0008 (7)
C15	0.0270 (8)	0.0163 (8)	0.0286 (8)	0.0014 (6)	0.0053 (7)	0.0018 (6)
C2	0.0370 (10)	0.0293 (9)	0.0384 (10)	−0.0031 (8)	0.0065 (8)	0.0118 (8)
C3A	0.0401 (12)	0.0418 (16)	0.0438 (18)	−0.0138 (10)	0.0117 (13)	0.0001 (13)
F1A	0.0639 (12)	0.0365 (8)	0.1106 (19)	0.0244 (9)	0.0482 (12)	0.0455 (11)
F2A	0.0864 (14)	0.0664 (12)	0.0267 (8)	−0.0336 (10)	0.0003 (8)	0.0110 (7)
C3B	0.0401 (12)	0.0418 (16)	0.0438 (18)	−0.0138 (10)	0.0117 (13)	0.0001 (13)
F1B	0.0639 (12)	0.0365 (8)	0.1106 (19)	0.0244 (9)	0.0482 (12)	0.0455 (11)
F2B	0.0864 (14)	0.0664 (12)	0.0267 (8)	−0.0336 (10)	0.0003 (8)	0.0110 (7)

Geometric parameters (Å, º) top

Mn1—C11	1.8376 (17)	C1—C2	1.545 (2)
Mn1—C12	1.8807 (17)	C2—F2B	1.264 (9)
Mn1—C13	1.8720 (17)	C2—F1A	1.336 (2)
Mn1—C14	1.8631 (17)	C2—F2A	1.404 (3)
Mn1—C15	1.8849 (17)	C2—C3B	1.409 (13)
Mn1—S1	2.3768 (5)	C2—C3A	1.472 (3)
S1—C1	1.7250 (18)	C2—F1B	1.492 (11)
O2—C1	1.209 (2)	C3A—H3A1	0.9800
O11—C11	1.131 (2)	C3A—H3A2	0.9800
O12—C12	1.127 (2)	C3A—H3A3	0.9800
O13—C13	1.126 (2)	C3B—H3B1	0.9800
O14—C14	1.127 (2)	C3B—H3B2	0.9800
O15—C15	1.122 (2)	C3B—H3B3	0.9800

C11—Mn1—C12	91.08 (7)	F1A—C2—F2A	104.25 (18)
C11—Mn1—C13	90.69 (7)	F2B—C2—C3B	119.9 (9)
C11—Mn1—C14	90.47 (7)	F1A—C2—C3A	112.9 (2)
C11—Mn1—C15	94.32 (7)	F2A—C2—C3A	107.65 (19)
C11—Mn1—S1	176.45 (5)	F2B—C2—F1B	98.7 (7)
C12—Mn1—C15	87.96 (7)	C3B—C2—F1B	103.2 (8)
C12—Mn1—S1	92.46 (5)	F2B—C2—C1	108.2 (4)
C13—Mn1—C12	91.07 (7)	F1A—C2—C1	110.99 (16)
C13—Mn1—C15	174.92 (7)	F2A—C2—C1	106.65 (15)
C13—Mn1—S1	88.91 (5)	C3B—C2—C1	118.3 (8)
C14—Mn1—C12	177.58 (7)	C3A—C2—C1	113.66 (18)
C14—Mn1—C13	90.77 (7)	F1B—C2—C1	105.3 (4)
C14—Mn1—C15	90.07 (7)	C2—C3A—H3A1	109.5
C14—Mn1—S1	86.01 (5)	C2—C3A—H3A2	109.5
C15—Mn1—S1	86.14 (5)	H3A1—C3A—H3A2	109.5
C1—S1—Mn1	106.26 (6)	C2—C3A—H3A3	109.5
O2—C1—C2	117.03 (16)	H3A1—C3A—H3A3	109.5
O2—C1—S1	126.92 (13)	H3A2—C3A—H3A3	109.5
C2—C1—S1	116.02 (13)	C2—C3B—H3B1	109.5
O11—C11—Mn1	176.70 (15)	C2—C3B—H3B2	109.5
O12—C12—Mn1	175.65 (15)	H3B1—C3B—H3B2	109.5
O13—C13—Mn1	177.98 (15)	C2—C3B—H3B3	109.5
O14—C14—Mn1	179.09 (17)	H3B1—C3B—H3B3	109.5
O15—C15—Mn1	177.59 (15)	H3B2—C3B—H3B3	109.5

Mn1—S1—C1—C2	−177.98 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A1···O14ⁱ	0.98	2.81	3.732 (3)	158
C3A—H3A2···O12ⁱⁱ	0.98	2.79	3.753 (3)	166
C3A—H3A3···O11ⁱⁱⁱ	0.98	2.79	3.564 (3)	136
C3B—H3B2···O12ⁱⁱ	0.98	2.81	3.777 (19)	168
C3B—H3B3···O11ⁱⁱⁱ	0.98	2.37	3.165 (15)	138
C3B—H3B3···O11ⁱⁱⁱ	0.98	2.37	3.165 (15)	138

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y+1/2, −z+1/2; (iii) x+1, −y+1/2, z−1/2.

Comparison of selected bond lengths (Å) and bond angle (°) in the title compound (1) and related compounds having an Mn(CO)₅SC fragment top

Parameter	(1)	CECCES^a	JEBNOT^b	TOXCMN^c
Mn—S	2.3768 (5)	2.405	2.384	2.379
C—S	1.725 (2)	1.741	1.723	1.737
Mn—S—C	106.26 (6)	108.84	108.12	105.64
Mn—C11	1.838 (2)	1.803	1.835	1.840
Mn—C12	1.881 (2)	1.867	1.871	1.883
Mn—C13	1.872 (2)	1.861	1.891	1.857
Mn—C14	1.863 (3)	1.864	1.871	1.880
Mn—C15	1.885 (2)	1.878	1.891	1.857

Notes: (a) Lindner et al. (1983); (b) Damerius et al. (1989); (b) Weber & Mattes (1979).

Funding information

Funding for this research was provided by: Centre National de la Recherche Scientifique and Agence Nationale de la Recherche (ANR, French National Agency) through the project FLUPOL (grant No. ANR-14-CE07-0012).

References

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
Beck, W., Hieber, W. & Tengler, H. (1961). Chem. Ber. 94, 862–872. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Damerius, R., Leopold, D., Schulze, W. & Seppelt, K. (1989). Z. Anorg. Allg. Chem. 578, 110–118. CSD CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Kaesz, H. D., King, R. B. & Stone, F. G. A. (1960). Z. Naturforsch. Teil B, 15, 763–764. CrossRef Google Scholar
Lindner, E., Butz, I. P., Hiller, W., Fawzi, R. & Hoehne, S. (1983). Angew. Chem. Int. Ed. 22, 996–997. CrossRef Web of Science Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Morales-Cerrada, R., Fliedel, C., Daran, J.-C., Gayet, F., Ladmiral, V., Améduri, B. & Poli, R. (2019). Chem. Eur. J. 25, 296–308. CAS PubMed Google Scholar
Morales-Cerrada, R., Fliedel, C., Gayet, F., Ladmiral, V., Améduri, B. & Poli, R. (2019). Organometallics, 38, 1021–1030. . CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Weber, H. & Mattes, R. (1979). Chem. Ber. 112, 95–98. CSD CrossRef CAS Web of Science 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.