trans-Bis[8-(benzyl­sulfan­yl)quinoline-κ2N,S]di­chlorido­cobalt(II)

Kodama, S.; Bunno, K.; Nomoto, A.; Ogawa, A.

doi:10.1107/S2414314621009925

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 10| October 2021| x210992

https://doi.org/10.1107/S2414314621009925

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trans-Bis[8-(benzylsulfanyl)quinoline-κ²N,S]dichloridocobalt(II)

Shintaro Kodama,^a ^* Kazuki Bunno,^a Akihiro Nomoto ^a and Akiya Ogawa ^a

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka, Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan
^*Correspondence e-mail: skodama@chem.osakafu-u.ac.jp

Edited by M. Zeller, Purdue University, USA (Received 21 September 2021; accepted 23 September 2021; online 4 October 2021)

The title dichlorocobalt(II) complex, trans-[CoCl₂(1)₂] [1 = 8-(benzylsulfanyl)quinoline, C₁₆H₁₃NS], has a central Co^II atom (site symmetry $[\overline1]$ ) that exhibits a distorted octahedral coordination geometry and is coordinated by two N and two S atoms from the bidentate N,S-ligand (1) situated in an equatorial plane and two Cl atoms in the axial positions. Complexes are linked by weak intermolecular C—H⋯π interactions between the 8-(benzylsulfanyl)quinoline ligands, forming a chain extending along the a-axis direction.

Keywords: crystal structure; cobalt(II) complex; bidentate N,S-ligand.

CCDC reference: 2111388

Structure description

Dichloridocobalt(II) complexes with homo donor ligands (e.g., multidentate nitrogen ligands) have been widely used in catalytic applications (Ma et al., 2014 ; Ai et al., 2019 ; Guo et al., 2021 ). Dichloridocobalt(II) complexes with hetero donor ligands (e.g., nitrogen- and sulfur-containing multidentate ligands) also exhibit interesting catalytic activities, e.g. in the oxidation reaction of n-octane (Soobramoney et al., 2014 ) and in the photochemical-driven hydrogen evolution from water (Lei et al., 2018 ); however, they are still limited in number. Herein, we report the structure determination of a new dichloridocobalt(II) complex 2 with 8-(benzylsulfanyl)quinoline (1) as an N,S-ligand (Kita et al., 2002 ) by single-crystal X-ray analysis.

As presented in Fig. 1, complex 2 exhibits a distorted octahedral coordination geometry. The central Co^II atom, located on a crystallographic center of inversion, is coordinated by two N and two S atoms from two symmetry-equivalent ligands 1 situated in the equatorial plane and two Cl atoms in the axial positions. The Co—N [2.1543 (17) Å] and Co—S [2.4856 (5) Å] bond lengths are within the range of those found in dichloridocobalt(II) complexes with a nitrogen- and sulfur-containing multidentate ligand (Soobramoney et al., 2014; Lei et al., 2018). In addition, weak intermolecular C—H⋯π interactions between the 8-(benzylsulfanyl)quinoline ligands are observed in the crystal packing of 2 (Karle et al., 2007 ), forming a chain along the a-axis direction (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯Cg2ⁱ	0.95	2.89	3.575 (2)	131
Symmetry code: (i) .

Figure 1
The molecular structure of 2 with atom numbering. Dispacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]

Figure 2
Crystal packing of 2 viewed along the c axis.

Synthesis and crystallization

CoCl₂·6H₂O (18.5 mg, 0.078 mmol) and 8-(benzylsulfanyl)quinoline (1; 45.5 mg, 0.18 mmol) in EtOH (20 mL) were heated at reflux overnight. The solvents were evaporated from the resulting suspension, and the residue was suspended in Et₂O followed by filtration to obtain a yellow–green powder. The powder was dissolved in EtOH, and Et₂O was diffused into the resulting solution to give 2 (4.5 mg, 9% yield) as yellow crystals. M.p. 150.2–150.8°C; IR (KBr, cm⁻¹) 3045, 2998, 1595, 1493, 1452, 1371, 1312, 1240, 994, 833.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₆H₁₃NS)₂]
M_r	632.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	103
a, b, c (Å)	8.00610 (17), 13.5141 (3), 13.3349 (3)
β (°)	105.714 (7)
V (Å³)	1388.85 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.99
Crystal size (mm)	0.09 × 0.04 × 0.02

Data collection
Diffractometer	Rigaku VariMax RAPID
Absorption correction	Multi-scan (ABSCOR; Rigaku, 1995 )
T_min, T_max	0.780, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22957, 3191, 2814
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 1.18
No. of reflections	3191
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.23
Computer programs: RAPID-AUTO (Rigaku, 1995); SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2111388

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009925/zl4046sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009925/zl4046Isup2.hkl

checkCIF report

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1995); cell refinement: RAPID-AUTO (Rigaku, 1995); data reduction: RAPID-AUTO (Rigaku, 1995); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

trans-Bis[8-(benzylsulfanyl)quinoline-κ²N,S]dichloridocobalt(II) top

Crystal data top

[CoCl₂(C₁₆H₁₃NS)₂]	F(000) = 650
M_r = 632.50	D_x = 1.512 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 8.00610 (17) Å	Cell parameters from 18593 reflections
b = 13.5141 (3) Å	θ = 2.2–27.5°
c = 13.3349 (3) Å	µ = 0.99 mm⁻¹
β = 105.714 (7)°	T = 103 K
V = 1388.85 (7) Å³	Prism, colourless
Z = 2	0.09 × 0.04 × 0.02 mm

Data collection top

Rigaku VariMax RAPID diffractometer	3191 independent reflections
Radiation source: rotating anode X-ray generator, MicroMax 007	2814 reflections with I > 2σ(I)
Multi-layer mirror optics monochromator	R_int = 0.034
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −9→10
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	k = −17→17
T_min = 0.780, T_max = 1.000	l = −17→17
22957 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0232P)² + 1.8429P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
3191 reflections	Δρ_max = 0.44 e Å⁻³
178 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

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. H atoms were positioned geometrically and constrained to ride on their parent atoms with C—H and CH₂ bond distances of 0.95 and 0.99 Å. U_iso(H) values were set to 1.2 U_eq(C).

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

	x	y	z	U_iso*/U_eq
Co1	0.500000	0.500000	0.500000	0.01456 (10)
Cl1	0.75883 (6)	0.50541 (4)	0.64296 (4)	0.01844 (12)
S1	0.64306 (7)	0.43574 (4)	0.36942 (4)	0.01617 (12)
N1	0.5642 (2)	0.63898 (13)	0.44057 (13)	0.0157 (3)
C1	0.5280 (3)	0.72466 (16)	0.47761 (17)	0.0182 (4)
H1	0.479481	0.723445	0.535214	0.022*
C2	0.5564 (3)	0.81773 (16)	0.43738 (18)	0.0203 (4)
H2	0.527515	0.876968	0.467243	0.024*
C3	0.6260 (3)	0.82107 (16)	0.35484 (17)	0.0205 (4)
H3	0.646246	0.882891	0.326311	0.025*
C4	0.6677 (3)	0.73190 (16)	0.31209 (16)	0.0172 (4)
C5	0.7444 (3)	0.73145 (17)	0.22805 (17)	0.0211 (4)
H5	0.765834	0.792080	0.197652	0.025*
C6	0.7877 (3)	0.64363 (17)	0.19073 (17)	0.0227 (5)
H6	0.841301	0.643561	0.135286	0.027*
C7	0.7535 (3)	0.55343 (17)	0.23382 (17)	0.0219 (5)
H7	0.781298	0.492970	0.205753	0.026*
C8	0.6802 (3)	0.55136 (15)	0.31611 (16)	0.0173 (4)
C9	0.6357 (3)	0.64133 (15)	0.35748 (16)	0.0159 (4)
C10	0.8657 (3)	0.39310 (16)	0.42715 (18)	0.0196 (4)
H10A	0.936644	0.403595	0.377737	0.023*
H10B	0.918744	0.430657	0.491654	0.023*
C11	0.8590 (3)	0.28453 (16)	0.45155 (17)	0.0183 (4)
C12	0.8020 (3)	0.21507 (17)	0.37238 (19)	0.0231 (5)
H12	0.769255	0.235779	0.301657	0.028*
C13	0.7929 (3)	0.11537 (17)	0.3968 (2)	0.0271 (5)
H13	0.752454	0.068236	0.342799	0.033*
C14	0.8429 (3)	0.08496 (17)	0.4998 (2)	0.0280 (5)
H14	0.836682	0.016931	0.516390	0.034*
C15	0.9017 (3)	0.15333 (18)	0.5785 (2)	0.0277 (5)
H15	0.938461	0.132049	0.649012	0.033*
C16	0.9073 (3)	0.25348 (17)	0.55467 (19)	0.0230 (5)
H16	0.944155	0.300590	0.609058	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0166 (2)	0.01190 (19)	0.01521 (19)	−0.00096 (15)	0.00437 (15)	0.00003 (15)
Cl1	0.0184 (2)	0.0177 (2)	0.0182 (2)	−0.00075 (19)	0.00324 (19)	−0.00025 (19)
S1	0.0184 (2)	0.0127 (2)	0.0175 (2)	0.00018 (19)	0.00518 (19)	0.00035 (19)
N1	0.0154 (8)	0.0149 (8)	0.0161 (8)	−0.0004 (7)	0.0030 (7)	0.0004 (7)
C1	0.0182 (10)	0.0162 (10)	0.0196 (10)	−0.0017 (8)	0.0044 (8)	−0.0016 (8)
C2	0.0204 (10)	0.0139 (10)	0.0251 (11)	0.0007 (8)	0.0034 (9)	−0.0012 (8)
C3	0.0194 (10)	0.0151 (10)	0.0235 (11)	−0.0016 (8)	0.0001 (9)	0.0039 (8)
C4	0.0161 (10)	0.0166 (10)	0.0164 (10)	−0.0009 (8)	0.0001 (8)	0.0034 (8)
C5	0.0235 (11)	0.0207 (11)	0.0175 (10)	−0.0022 (9)	0.0028 (8)	0.0064 (8)
C6	0.0270 (11)	0.0242 (11)	0.0184 (11)	0.0002 (9)	0.0088 (9)	0.0045 (9)
C7	0.0262 (11)	0.0206 (11)	0.0203 (10)	0.0032 (9)	0.0084 (9)	0.0014 (9)
C8	0.0192 (10)	0.0161 (10)	0.0159 (10)	−0.0006 (8)	0.0035 (8)	0.0018 (8)
C9	0.0154 (9)	0.0151 (9)	0.0157 (10)	0.0000 (8)	0.0014 (8)	0.0020 (8)
C10	0.0168 (10)	0.0161 (10)	0.0260 (11)	−0.0003 (8)	0.0061 (9)	0.0018 (9)
C11	0.0151 (10)	0.0155 (10)	0.0255 (11)	0.0022 (8)	0.0075 (8)	0.0014 (8)
C12	0.0289 (12)	0.0191 (11)	0.0244 (11)	0.0021 (9)	0.0127 (9)	−0.0006 (9)
C13	0.0325 (13)	0.0173 (11)	0.0356 (13)	0.0002 (9)	0.0164 (11)	−0.0045 (10)
C14	0.0271 (12)	0.0156 (11)	0.0441 (15)	0.0024 (9)	0.0142 (11)	0.0061 (10)
C15	0.0226 (11)	0.0262 (12)	0.0321 (13)	0.0004 (10)	0.0038 (10)	0.0108 (10)
C16	0.0190 (10)	0.0216 (11)	0.0265 (12)	−0.0010 (9)	0.0032 (9)	0.0029 (9)

Geometric parameters (Å, º) top

Co1—Cl1ⁱ	2.4070 (5)	C6—C7	1.406 (3)
Co1—Cl1	2.4070 (5)	C7—H7	0.9500
Co1—S1	2.4856 (5)	C7—C8	1.378 (3)
Co1—S1ⁱ	2.4856 (5)	C9—C4	1.419 (3)
Co1—N1ⁱ	2.1542 (17)	C9—C8	1.420 (3)
Co1—N1	2.1543 (17)	C10—H10A	0.9900
S1—C8	1.775 (2)	C10—H10B	0.9900
S1—C10	1.832 (2)	C11—C10	1.507 (3)
N1—C1	1.322 (3)	C11—C12	1.394 (3)
N1—C9	1.378 (3)	C11—C16	1.389 (3)
C1—H1	0.9500	C12—H12	0.9500
C2—C1	1.410 (3)	C13—C12	1.393 (3)
C2—H2	0.9500	C13—H13	0.9500
C2—C3	1.362 (3)	C14—C13	1.385 (4)
C3—H3	0.9500	C14—H14	0.9500
C4—C3	1.411 (3)	C14—C15	1.382 (4)
C4—C5	1.417 (3)	C15—H15	0.9500
C5—H5	0.9500	C16—C15	1.394 (3)
C5—C6	1.367 (3)	C16—H16	0.9500
C6—H6	0.9500

Cl1ⁱ—Co1—Cl1	180.0	C5—C6—H6	119.8
Cl1—Co1—S1ⁱ	84.016 (17)	C5—C6—C7	120.5 (2)
Cl1—Co1—S1	95.984 (17)	C7—C6—H6	119.8
Cl1ⁱ—Co1—S1	84.015 (17)	C6—C7—H7	119.5
Cl1ⁱ—Co1—S1ⁱ	95.984 (17)	C8—C7—C6	121.0 (2)
S1ⁱ—Co1—S1	180.0	C8—C7—H7	119.5
N1—Co1—Cl1ⁱ	88.58 (5)	C7—C8—S1	119.38 (17)
N1ⁱ—Co1—Cl1ⁱ	91.42 (5)	C7—C8—C9	119.84 (19)
N1ⁱ—Co1—Cl1	88.58 (5)	C9—C8—S1	120.78 (16)
N1—Co1—Cl1	91.42 (5)	N1—C9—C4	121.66 (19)
N1—Co1—S1	81.12 (5)	N1—C9—C8	119.66 (18)
N1ⁱ—Co1—S1ⁱ	81.12 (5)	C4—C9—C8	118.68 (19)
N1ⁱ—Co1—S1	98.88 (5)	S1—C10—H10A	110.1
N1—Co1—S1ⁱ	98.88 (5)	S1—C10—H10B	110.1
N1ⁱ—Co1—N1	180.00 (9)	H10A—C10—H10B	108.4
C8—S1—Co1	97.58 (7)	C11—C10—S1	108.03 (15)
C8—S1—C10	101.30 (10)	C11—C10—H10A	110.1
C10—S1—Co1	113.32 (8)	C11—C10—H10B	110.1
C1—N1—Co1	121.86 (14)	C12—C11—C10	121.0 (2)
C1—N1—C9	117.47 (18)	C16—C11—C10	119.4 (2)
C9—N1—Co1	120.55 (13)	C16—C11—C12	119.5 (2)
N1—C1—H1	117.8	C11—C12—H12	119.9
N1—C1—C2	124.4 (2)	C13—C12—C11	120.1 (2)
C2—C1—H1	117.8	C13—C12—H12	119.9
C1—C2—H2	120.6	C12—C13—H13	120.0
C3—C2—C1	118.7 (2)	C14—C13—C12	120.0 (2)
C3—C2—H2	120.6	C14—C13—H13	120.0
C2—C3—H3	120.3	C13—C14—H14	119.9
C2—C3—C4	119.4 (2)	C15—C14—C13	120.2 (2)
C4—C3—H3	120.3	C15—C14—H14	119.9
C3—C4—C5	121.6 (2)	C14—C15—H15	120.0
C3—C4—C9	118.32 (19)	C14—C15—C16	120.1 (2)
C5—C4—C9	120.0 (2)	C16—C15—H15	120.0
C4—C5—H5	120.0	C11—C16—C15	120.1 (2)
C6—C5—C4	119.9 (2)	C11—C16—H16	119.9
C6—C5—H5	120.0	C15—C16—H16	119.9

Co1—S1—C8—C7	−177.06 (17)	C6—C7—C8—S1	−178.85 (18)
Co1—S1—C8—C9	3.13 (18)	C6—C7—C8—C9	1.0 (3)
Co1—S1—C10—C11	91.07 (15)	C8—S1—C10—C11	−165.48 (15)
Co1—N1—C1—C2	−175.63 (16)	C8—C9—C4—C3	−178.91 (19)
Co1—N1—C9—C4	175.41 (15)	C8—C9—C4—C5	−0.8 (3)
Co1—N1—C9—C8	−5.1 (3)	C9—N1—C1—C2	0.5 (3)
N1—C9—C4—C3	0.6 (3)	C9—C4—C3—C2	−0.2 (3)
N1—C9—C4—C5	178.78 (19)	C9—C4—C5—C6	0.0 (3)
N1—C9—C8—S1	0.5 (3)	C10—S1—C8—C7	67.23 (19)
N1—C9—C8—C7	−179.27 (19)	C10—S1—C8—C9	−112.57 (18)
C1—N1—C9—C4	−0.7 (3)	C10—C11—C12—C13	−178.5 (2)
C1—N1—C9—C8	178.79 (19)	C10—C11—C16—C15	180.0 (2)
C1—C2—C3—C4	−0.1 (3)	C11—C16—C15—C14	−2.1 (4)
C3—C2—C1—N1	−0.1 (3)	C12—C11—C10—S1	64.7 (2)
C3—C4—C5—C6	178.1 (2)	C12—C11—C16—C15	1.2 (3)
C4—C5—C6—C7	1.3 (3)	C13—C14—C15—C16	1.5 (4)
C4—C9—C8—S1	−179.91 (16)	C14—C13—C12—C11	−0.9 (4)
C4—C9—C8—C7	0.3 (3)	C15—C14—C13—C12	0.0 (4)
C5—C4—C3—C2	−178.3 (2)	C16—C11—C10—S1	−114.0 (2)
C5—C6—C7—C8	−1.8 (4)	C16—C11—C12—C13	0.3 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···Cg2ⁱⁱ	0.95	2.89	3.575 (2)	131

Symmetry code: (ii) −x, −y, −z.

Acknowledgements

A part of this work was conducted at the Nara Institute of Science and Technology (NAIST), supported by the Nanotechnology Platform Program (Synthesis of Molecules and Materials) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (grant No. 21H01977; grant No. 19H02791; grant No. 19H02756); Iketani Science and Technology Foundation (grant No. 0331022-A).

References

Ai, W., Zhong, R., Liu, X. & Liu, Q. (2019). Chem. Rev. 119, 2876–2953. Web of Science CrossRef CAS PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Guo, J., Cheng, Z., Chen, J., Chen, X. & Lu, Z. (2021). Acc. Chem. Res. 54, 2701–2716. Web of Science CrossRef CAS PubMed Google Scholar
Karle, I. L., Butcher, R. J., Wolak, M. A., da Silva Filho, D. A., Uchida, M., Brédas, J.-L. & Kafafi, Z. H. (2007). J. Phys. Chem. C, 111, 9543–9547. Web of Science CSD CrossRef CAS Google Scholar
Kita, M., Abiko, S., Fuyuhiro, A., Yamanari, K., Murata, K. & Yamashita, S. (2002). Polyhedron, 21, 843–848. Web of Science CSD CrossRef CAS Google Scholar
Lei, J.-M., Luo, S.-P. & Zhan, S.-Z. (2018). J. Photochem. Photobiol. Chem. 364, 650–656. Web of Science CSD CrossRef CAS Google Scholar
Ma, J., Feng, C., Wang, S., Zhao, K.-Q., Sun, W.-H., Redshaw, C. & Solan, G. A. (2014). Inorg. Chem. Front. 1, 14–34. Web of Science CrossRef CAS Google Scholar
Rigaku (1995). ABSCOR and RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Soobramoney, L., Bala, M. D. & Friedrich, H. B. (2014). Dalton Trans. 43, 15968–15978. Web of Science CSD CrossRef CAS PubMed Google Scholar