metal-organic compounds
trans-Bis[8-(benzylsulfanyl)quinoline-κ2N,S]dichloridocobalt(II)
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
The title dichlorocobalt(II) complex, trans-[CoCl2(1)2] [1 = 8-(benzylsulfanyl)quinoline, C16H13NS], has a central CoII atom (site symmetry ) 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 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 CoII 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).
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 .
details are summarized in Table 2Structural data
CCDC reference: 2111388
https://doi.org/10.1107/S2414314621009925/zl4046sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009925/zl4046Isup2.hkl
Data collection: RAPID-AUTO (Rigaku, 1995); cell
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).[CoCl2(C16H13NS)2] | F(000) = 650 |
Mr = 632.50 | Dx = 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 |
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 | Rint = 0.034 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ω scans | h = −9→10 |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | k = −17→17 |
Tmin = 0.780, Tmax = 1.000 | l = −17→17 |
22957 measured reflections |
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(Fo2) + (0.0232P)2 + 1.8429P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | (Δ/σ)max < 0.001 |
3191 reflections | Δρmax = 0.44 e Å−3 |
178 parameters | Δρmin = −0.23 e Å−3 |
0 restraints |
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. Uiso(H) values were set to 1.2 Ueq(C). |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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).
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