Cobaltoceniumsulfonate

Vanicek, S.; Wurst, K.; Bildstein, B.

doi:10.1107/S2414314617017035

metal-organic compounds

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ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171703

https://doi.org/10.1107/S2414314617017035

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Cobaltoceniumsulfonate

Stefan Vanicek,^a Klaus Wurst ^a and Benno Bildstein ^a ^*

^aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80–82, 6020 Innsbruck, Austria
^*Correspondence e-mail: benno.bildstein@uibk.ac.at

Edited by R. J. Butcher, Howard University, USA (Received 25 October 2017; accepted 27 November 2017; online 30 November 2017)

The title compound, [Co(C₅H₅)(C₅H₄O₃S)], was synthesized by dediazoniation of cobaltoceniumdiazonium bis(hexafluoridophosphate) with CuCl and SO₂, crystallizing as yellow platelets. Structurally, a regular cobaltocenium sandwich moiety is observed containing coplanar cyclopentadienyl rings and displaying unexceptional carbon–cobalt [2.0230 (16)–2.0452 (14) Å] and carbon–carbon [1.410 (3)–1.431 (3) Å] bond distances. In this mesoionic molecule, the cationic cobaltoceniumyl part is connected to its anionic sulfonate part by a carbon–sulfur single bond of 1.7717 (15) Å.

Keywords: crystal structure; cobaltoceniumsulfonate; zwitterion; dediazoniation.

CCDC reference: 1562754

Structure description

The title compound (Fig. 1) is the first and only sulfonic acid derivative in the compound class of cobaltocenium salts. As a result of the strongly electron-withdrawing cationic cobaltocenium moiety, the corresponding sulfonic acid is fully dissociated, thereby stabilizing the title compound as its zwitterionic cobaltoceniumsulfonate.

Figure 1
The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms.

Structurally, a regular cobaltocenium sandwich moiety is observed containing coplanar cyclopentadienyl rings and displaying unexceptional carbon–cobalt [2.0230 (16)–2.0452 (14) Å] and carbon–carbon [1.410 (3)–1.431 (3) Å] bond distances. The structural properties of the sulfonate group are also unexceptional, showing a tetrahedral sulfonate functional group with sulfur–oxygen bond distances [1.4402 (12)–1.4499 (14) Å] and oxygen–sulfur–oxygen angles [113.04 (9)–114.09 (9)°] in line with expectations. In this mesoionic molecule, the cationic cobaltoceniumyl part is connected to its anionic sulfonate part by a carbon–sulfur single bond of 1.7717 (15) Å. The arrangement of molecular entities in the unit cell is shown in Fig. 2.

Figure 2
The arrangement of molecular entities of the zwitterionic title compound in the unit cell. [Symmetry codes: (A) x, y, z; (B) 1 − x, 1 − y, 1 − z; (C) $[{3\over 2}]$ − x, y − $[{1\over 2}]$ , $[{1\over 2}]$ − z; (D) x − $[{1\over 2}]$ , $[{3\over 2}]$ − y, $[{1\over 2}]$ + z.]

Synthesis and crystallization

Cobaltoceniumsulfonate was obtained by a Sandmeyer-type chlorosulfo-dediazoniation reaction of cobaltoceniumdiazonium bis(hexafluoridophosphate) (Vanicek et al., 2016 ) with sulfur dioxide in the presence of cupric chloride in hydrochloric acid according to literature (Hoffman, 1981 ), followed by aqueous workup. From the resulting product mixture containing various cobaltocenium compounds according to ¹H and ¹³C NMR analysis, single crystals of the title compound were obtained at room temperature from a mixture of acetonitrile and water.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[Co(C₅H₅)(C₅H₄O₃S)]
M_r	268.16
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	193
a, b, c (Å)	7.6234 (4), 13.1489 (6), 9.6785 (5)
β (°)	94.206 (1)
V (Å³)	967.55 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.97
Crystal size (mm)	0.18 × 0.14 × 0.14

Data collection
Diffractometer	Bruker D8 QUEST PHOTON 100
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.676, 0.790
No. of measured, independent and observed [I > 2σ(I)] reflections	22746, 2116, 2032
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.054, 1.08
No. of reflections	2116
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.43
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1562754

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617017035/bv4013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017035/bv4013Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617017035/bv4013Isup3.cdx

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: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008).

Cobaltoceniumsulfonate top

Crystal data top

[Co(C₅H₅)(C₅H₄O₃S)]	F(000) = 544
M_r = 268.16	D_x = 1.841 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6234 (4) Å	Cell parameters from 9062 reflections
b = 13.1489 (6) Å	θ = 2.6–27.5°
c = 9.6785 (5) Å	µ = 1.97 mm⁻¹
β = 94.206 (1)°	T = 193 K
V = 967.55 (8) Å³	Platelet, yellow
Z = 4	0.18 × 0.14 × 0.14 mm

Data collection top

Bruker D8 QUEST PHOTON 100 diffractometer	2116 independent reflections
Radiation source: Incoatec Microfocus	2032 reflections with I > 2σ(I)
Multi layered optics monochromator	R_int = 0.025
Detector resolution: 10.4 pixels mm^-1	θ_max = 27.0°, θ_min = 2.6°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (DIFABS; Walker & Stuart, 1983)	k = −16→16
T_min = 0.676, T_max = 0.790	l = −12→12
22746 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.020	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0286P)² + 0.5214P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2116 reflections	Δρ_max = 0.24 e Å⁻³
136 parameters	Δρ_min = −0.43 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.

Refinement. Hydrogen atoms were located in the difference Fourier syntheses and included and refined as riding atoms in their calculated positions.

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

	x	y	z	U_iso*/U_eq
Co1	0.72231 (2)	0.58762 (2)	0.24293 (2)	0.01743 (8)
S1	0.83395 (5)	0.69190 (3)	0.55827 (4)	0.02232 (10)
O1	0.76626 (18)	0.67652 (11)	0.69286 (13)	0.0405 (3)
O2	1.00545 (15)	0.64785 (10)	0.54789 (15)	0.0381 (3)
O3	0.81863 (18)	0.79505 (9)	0.50811 (15)	0.0398 (3)
C1	0.8206 (2)	0.68857 (14)	0.10960 (19)	0.0355 (4)
H1	0.7914	0.7586	0.1010	0.043*
C2	0.7347 (2)	0.60824 (16)	0.03566 (17)	0.0367 (4)
H2	0.6381	0.6148	−0.0315	0.044*
C3	0.8179 (2)	0.51592 (14)	0.07925 (18)	0.0357 (4)
H3	0.7868	0.4497	0.0466	0.043*
C4	0.9564 (2)	0.54022 (14)	0.18074 (18)	0.0323 (4)
H4	1.0340	0.4931	0.2279	0.039*
C5	0.9578 (2)	0.64712 (14)	0.19881 (18)	0.0322 (4)
H5	1.0368	0.6844	0.2600	0.039*
C6	0.54570 (19)	0.66101 (12)	0.35710 (15)	0.0222 (3)
H6	0.5113	0.7304	0.3503	0.027*
C7	0.4639 (2)	0.57829 (13)	0.28320 (16)	0.0260 (3)
H7	0.3653	0.5829	0.2176	0.031*
C8	0.5545 (2)	0.48737 (12)	0.32406 (15)	0.0252 (3)
H8	0.5264	0.4209	0.2908	0.030*
C9	0.69493 (19)	0.51320 (11)	0.42370 (15)	0.0209 (3)
H9	0.7769	0.4673	0.4684	0.025*
C10	0.68939 (18)	0.62079 (11)	0.44371 (14)	0.0187 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01734 (12)	0.01810 (12)	0.01726 (11)	−0.00121 (7)	0.00411 (7)	−0.00056 (6)
S1	0.02178 (18)	0.01959 (18)	0.02482 (18)	0.00203 (13)	−0.00344 (14)	−0.00436 (13)
O1	0.0459 (8)	0.0523 (8)	0.0231 (6)	−0.0119 (6)	0.0008 (5)	−0.0104 (5)
O2	0.0212 (6)	0.0373 (7)	0.0541 (8)	0.0067 (5)	−0.0086 (5)	−0.0140 (6)
O3	0.0454 (8)	0.0187 (6)	0.0526 (8)	−0.0002 (5)	−0.0145 (6)	−0.0005 (5)
C1	0.0388 (10)	0.0295 (8)	0.0406 (10)	0.0021 (7)	0.0199 (8)	0.0123 (7)
C2	0.0333 (9)	0.0581 (11)	0.0195 (7)	−0.0007 (8)	0.0080 (7)	0.0048 (7)
C3	0.0426 (10)	0.0357 (9)	0.0314 (8)	−0.0064 (8)	0.0200 (7)	−0.0119 (7)
C4	0.0258 (8)	0.0370 (9)	0.0360 (9)	0.0071 (7)	0.0153 (7)	0.0050 (7)
C5	0.0247 (8)	0.0383 (9)	0.0352 (9)	−0.0103 (7)	0.0120 (6)	−0.0022 (7)
C6	0.0177 (7)	0.0285 (8)	0.0208 (7)	0.0049 (6)	0.0036 (5)	0.0003 (5)
C7	0.0163 (7)	0.0404 (9)	0.0213 (7)	−0.0040 (6)	0.0026 (5)	0.0017 (6)
C8	0.0267 (8)	0.0261 (7)	0.0233 (7)	−0.0102 (6)	0.0055 (6)	−0.0005 (6)
C9	0.0231 (7)	0.0207 (7)	0.0192 (6)	−0.0007 (5)	0.0035 (5)	0.0017 (5)
C10	0.0182 (7)	0.0205 (7)	0.0176 (6)	0.0021 (5)	0.0028 (5)	−0.0003 (5)

Geometric parameters (Å, º) top

Co1—C4	2.0230 (16)	C2—C3	1.419 (3)
Co1—C3	2.0245 (16)	C2—H2	0.9500
Co1—C10	2.0251 (14)	C3—C4	1.425 (3)
Co1—C9	2.0288 (14)	C3—H3	0.9500
Co1—C5	2.0320 (16)	C4—C5	1.416 (3)
Co1—C1	2.0323 (16)	C4—H4	0.9500
Co1—C2	2.0333 (16)	C5—H5	0.9500
Co1—C8	2.0345 (15)	C6—C7	1.421 (2)
Co1—C7	2.0399 (15)	C6—C10	1.431 (2)
Co1—C6	2.0452 (14)	C6—H6	0.9500
S1—O2	1.4402 (12)	C7—C8	1.422 (2)
S1—O3	1.4425 (12)	C7—H7	0.9500
S1—O1	1.4499 (14)	C8—C9	1.429 (2)
S1—C10	1.7717 (15)	C8—H8	0.9500
C1—C2	1.410 (3)	C9—C10	1.4289 (19)
C1—C5	1.416 (3)	C9—H9	0.9500
C1—H1	0.9500

C4—Co1—C3	41.22 (8)	Co1—C1—H1	126.4
C4—Co1—C10	121.73 (7)	C1—C2—C3	108.00 (16)
C3—Co1—C10	158.16 (7)	C1—C2—Co1	69.67 (10)
C4—Co1—C9	104.88 (7)	C3—C2—Co1	69.20 (10)
C3—Co1—C9	121.06 (7)	C1—C2—H2	126.0
C10—Co1—C9	41.28 (5)	C3—C2—H2	126.0
C4—Co1—C5	40.89 (7)	Co1—C2—H2	126.7
C3—Co1—C5	68.94 (7)	C2—C3—C4	107.79 (16)
C10—Co1—C5	106.99 (7)	C2—C3—Co1	69.86 (10)
C9—Co1—C5	121.02 (7)	C4—C3—Co1	69.33 (9)
C4—Co1—C1	68.77 (7)	C2—C3—H3	126.1
C3—Co1—C1	68.70 (7)	C4—C3—H3	126.1
C10—Co1—C1	123.10 (7)	Co1—C3—H3	126.3
C9—Co1—C1	158.23 (7)	C5—C4—C3	107.83 (16)
C5—Co1—C1	40.76 (8)	C5—C4—Co1	69.90 (9)
C4—Co1—C2	69.01 (7)	C3—C4—Co1	69.45 (10)
C3—Co1—C2	40.95 (8)	C5—C4—H4	126.1
C10—Co1—C2	159.39 (7)	C3—C4—H4	126.1
C9—Co1—C2	158.48 (7)	Co1—C4—H4	126.1
C5—Co1—C2	68.64 (7)	C1—C5—C4	107.95 (16)
C1—Co1—C2	40.58 (8)	C1—C5—Co1	69.63 (9)
C4—Co1—C8	120.58 (7)	C4—C5—Co1	69.22 (9)
C3—Co1—C8	105.84 (7)	C1—C5—H5	126.0
C10—Co1—C8	69.11 (6)	C4—C5—H5	126.0
C9—Co1—C8	41.17 (6)	Co1—C5—H5	126.7
C5—Co1—C8	157.06 (7)	C7—C6—C10	107.52 (13)
C1—Co1—C8	160.03 (7)	C7—C6—Co1	69.45 (9)
C2—Co1—C8	122.90 (7)	C10—C6—Co1	68.66 (8)
C4—Co1—C7	157.47 (7)	C7—C6—H6	126.2
C3—Co1—C7	121.97 (7)	C10—C6—H6	126.2
C10—Co1—C7	68.91 (6)	Co1—C6—H6	127.2
C9—Co1—C7	69.16 (6)	C6—C7—C8	108.50 (13)
C5—Co1—C7	160.70 (7)	C6—C7—Co1	69.85 (8)
C1—Co1—C7	124.53 (7)	C8—C7—Co1	69.37 (9)
C2—Co1—C7	108.17 (7)	C6—C7—H7	125.8
C8—Co1—C7	40.85 (7)	C8—C7—H7	125.8
C4—Co1—C6	159.40 (7)	Co1—C7—H7	126.6
C3—Co1—C6	158.66 (7)	C7—C8—C9	108.21 (13)
C10—Co1—C6	41.16 (6)	C7—C8—Co1	69.78 (9)
C9—Co1—C6	69.40 (6)	C9—C8—Co1	69.20 (8)
C5—Co1—C6	123.96 (7)	C7—C8—H8	125.9
C1—Co1—C6	108.84 (7)	C9—C8—H8	125.9
C2—Co1—C6	123.38 (7)	Co1—C8—H8	126.7
C8—Co1—C6	68.87 (6)	C8—C9—C10	107.38 (13)
C7—Co1—C6	40.70 (6)	C8—C9—Co1	69.63 (8)
O2—S1—O3	113.96 (9)	C10—C9—Co1	69.22 (8)
O2—S1—O1	113.04 (9)	C8—C9—H9	126.3
O3—S1—O1	114.09 (9)	C10—C9—H9	126.3
O2—S1—C10	105.68 (7)	Co1—C9—H9	126.4
O3—S1—C10	104.73 (7)	C9—C10—C6	108.39 (13)
O1—S1—C10	104.05 (7)	C9—C10—S1	125.74 (11)
C2—C1—C5	108.43 (16)	C6—C10—S1	125.87 (11)
C2—C1—Co1	69.75 (10)	C9—C10—Co1	69.50 (8)
C5—C1—Co1	69.61 (9)	C6—C10—Co1	70.17 (8)
C2—C1—H1	125.8	S1—C10—Co1	126.80 (8)
C5—C1—H1	125.8

C5—C1—C2—C3	0.29 (19)	Co1—C8—C9—C10	59.15 (10)
Co1—C1—C2—C3	−58.76 (12)	C7—C8—C9—Co1	−59.05 (10)
C5—C1—C2—Co1	59.04 (12)	C8—C9—C10—C6	0.20 (16)
C1—C2—C3—C4	−0.12 (19)	Co1—C9—C10—C6	59.61 (10)
Co1—C2—C3—C4	−59.17 (11)	C8—C9—C10—S1	179.33 (11)
C1—C2—C3—Co1	59.05 (12)	Co1—C9—C10—S1	−121.26 (11)
C2—C3—C4—C5	−0.09 (18)	C8—C9—C10—Co1	−59.41 (10)
Co1—C3—C4—C5	−59.59 (11)	C7—C6—C10—C9	−0.42 (16)
C2—C3—C4—Co1	59.50 (12)	Co1—C6—C10—C9	−59.19 (10)
C2—C1—C5—C4	−0.34 (18)	C7—C6—C10—S1	−179.55 (11)
Co1—C1—C5—C4	58.79 (11)	Co1—C6—C10—S1	121.68 (12)
C2—C1—C5—Co1	−59.13 (12)	C7—C6—C10—Co1	58.77 (10)
C3—C4—C5—C1	0.26 (18)	O2—S1—C10—C9	39.68 (15)
Co1—C4—C5—C1	−59.05 (11)	O3—S1—C10—C9	160.34 (13)
C3—C4—C5—Co1	59.31 (11)	O1—S1—C10—C9	−79.61 (14)
C10—C6—C7—C8	0.49 (17)	O2—S1—C10—C6	−141.34 (13)
Co1—C6—C7—C8	58.77 (11)	O3—S1—C10—C6	−20.68 (15)
C10—C6—C7—Co1	−58.28 (10)	O1—S1—C10—C6	99.37 (14)
C6—C7—C8—C9	−0.37 (17)	O2—S1—C10—Co1	−50.30 (11)
Co1—C7—C8—C9	58.69 (10)	O3—S1—C10—Co1	70.37 (11)
C6—C7—C8—Co1	−59.06 (11)	O1—S1—C10—Co1	−169.58 (10)
C7—C8—C9—C10	0.10 (17)

Funding information

The presented work was supported by the Austrian Science Fund (FWF), P 30221-NBL.

References

Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hoffman, R. V. (1981). Org. Synth. 60, 121–126. CAS 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 CSD CrossRef CAS IUCr Journals Google Scholar
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Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Vanicek, S., Kopacka, H., Wurst, K., Müller, T., Hassenrück, C., Winter, R. F. & Bildstein, B. (2016). Organometallics, 35, 2101–2109. CrossRef CAS Google Scholar

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

Cobaltoceniumsulfonate

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

metal-organic compounds