Crystal structure of hexa­kis­(dimethyl sulfoxide-κO)cobalt(II) bis­[tri­chlorido­(quinoline-κN)cobaltate(II)]

Brescia, T.K.; Mulosmani, K.; Gulati, S.; Athanasopoulos, D.; Upmacis, R.K.

doi:10.1107/S2056989018001652

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ISSN: 2056-9890

Volume 74| Part 3| March 2018| Pages 309-312

https://doi.org/10.1107/S2056989018001652

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Crystal structure of hexakis(dimethyl sulfoxide-κO)cobalt(II) bis[trichlorido(quinoline-κN)cobaltate(II)]

Tyler K. Brescia,^a Kaltrina Mulosmani,^a Shivani Gulati,^b Demosthenes Athanasopoulos ^a and Rita K. Upmacis ^a ^*

^aDepartment of Chemistry and Physical Sciences, Pace, University, New York, NY 10038, USA, and ^bDepartment of Chemistry, Columbia University, New York, NY 10027, USA
^*Correspondence e-mail: rupmacis@pace.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 18 January 2018; accepted 28 January 2018; online 7 February 2018)

There are few reports that describe crystal structures of compounds containing cobalt complexed to either dimethyl sulfoxide (Me₂SO) or quinoline (C₉H₇N). The title compound, [Co(C₂H₆OS)₆][CoCl₃(C₉H₇N)]₂, is a cobalt salt in which the metal ion is complexed to both Me₂SO and quinoline. In particular, we observed that anhydrous cobalt(II) chloride reacts with quinoline in Me₂SO to form a salt that is to be formulated as [Co^II(Me₂SO)₆]²⁺{[Co^IICl₃quinoline]₂⁻}. The Co^II atom in the cation portion of this molecule lies on a inversion center and is bound to the O atoms of six Me₂SO moieties in an octahedral configuration, while the Co^II atom in the anion is attached to three chloride ligands and one quinoline moiety in a tetrahedral arrangement.

Keywords: crystal; cobalt; quinoline; dimethyl sulfoxide.

CCDC reference: 1820336

1. Chemical context

Quinoline-based molecules have shown significant promise in the development of clinically viable anti-cancer drugs (Afzal et al., 2015 ). Metal complexes containing quinoline include: (i) square-planar palladium- and platinum-quinoline compounds, such as trans-[Pd(II)Cl₂(quinoline)₂], cis-[Pt(II)Cl₂(quinoline)₂] and trans-[Pd(II)(N₃)₂(quinoline)₂] (Ha, 2012 ; Klapötke et al., 2000 ; Raven et al., 2012 ; Davies et al., 2001 ), as well as (ii) tetrahedral cobalt-, nickel- and zinc-quinoline compounds, of the form [M^IICl₂(quinoline)₂] (Golic & Mirceva, 1988 ). Interestingly, despite the fact that the interaction of dimethyl sulfoxide (Me₂SO) with metal ions has been studied for many years (Cotton & Francis, 1960 ), metal compounds that incorporate both coordinated quinoline and Me₂SO are rare, as illustrated by the fact that only one structurally characterized example is listed in the Cambridge Structural Database (Groom et al., 2016 ), Zn(O₂CC₆H₄C₂HN₃CO₂CH₃)₂·(quinoline)·Me₂SO (Ma et al., 2012 ). Herein, we describe the structure of the complex salt [Co^II(Me₂SO)₆][Co^IICl₃quinoline]₂, which can be obtained by the reaction of anhydrous cobalt(II) chloride with quinoline in Me₂SO.

2. Structural commentary

The molecular structures of the cation and anion portions of the title complex are shown in Fig. 1a and 1b, respectively. In the cation portion of this compound, the cobalt atom lies on a crystallographic inversion center and is coordinated to oxygen atoms of six Me₂SO groups in an octahedral configuration. The cation is not rigorously octahedral, as the Co—O bond distances are slightly elongated in the axial positions [2.1258 (17) Å] compared to the equatorial positions [2.0606 (17)–2.0819 (18) Å], giving an average Co—O distance of 2.089 Å. A closely related complex, [Co(Me₂SO)₆][CoCl₄], contains a cobalt cation that is similarly surrounded by six oxygen atoms in a slightly distorted octahedral configuration with Co—O distances between 2.06 (1) and 2.10 (1) Å, with a mean Co—O distance of 2.08Å (Ciccarese et al., 1993 ). The O—Co—O (cis) bond angles in the title complex are close to 90°, ranging from 86.29 (7) to 93.71 (7)°, compared to 87.9 (5) to 90.8 (4)° in [Co(Me₂SO)₆][CoCl₄] (Ciccarese et al., 1993).

Figure 1
The molecular structure of the complex salt [Co^II(Me₂SO)₆][Co^IICl₃quinoline]₂, showing (a) the [Co^II(Me₂SO)₆]²⁺ cation (primed labels are related by the symmetry code: −x, −y, −z + 2), and (b) the symmetry-unique [Co^IICl₃quinoline]⁻ anion.

The cobalt atom in the anion portion of the title complex is attached to three chloro ligands and one quinoline moiety in a tetrahedral arrangement. The Co—Cl bond distances range from 2.2517 (10) to 2.2534 (10) Å, with an average Co—Cl distance of 2.252 Å, while the Co—N distance is 2.054 (3) Å. The Cl—Co—Cl angles range from 108.21 (5) to 114.26 (4)°, giving an average of 110.98°, and the average N—Co—Cl angle is 107.88° [range 107.09 (9) to 108.80 (8)°], indicating that while the anion is close to tetrahedral, there is some distortion. Interestingly, the [CoCl₄]²⁻ anion in [Co(Me₂SO)₆][CoCl₄] also showed some distortion with Co—Cl distances ranging from 2.265 (6) to 2.305 (7) Å, giving an average Co—Cl distance of 2.284 (6) Å, and the Cl—Co—Cl angles ranging from 107.1 (2) to 112.4 (2)° (Ciccarese et al., 1993). The deviations from 109.5° in [Co(Me₂SO)₆][CoCl₄] were ascribed to disorder, as indicated by the high anisotropic motion (Ciccarese et al., 1993).

The degree of distortion from a tetrahedral arrangement can be readily quantified by the τ₄ index that is reported and discussed elsewhere (Yang et al., 2007 , Palmer et al., 2015 ). Briefly, τ₄ is obtained from the expression, τ₄ = [360 − (α + β)]/141, where α and β represent the two largest angles; a τ₄ value of 1.00 indicates an idealized tetrahedral geometry, whereas a value of 0.00 indicates an idealized square-planar geometry. In the title complex, α = 114.26 (4)° and β = 110.46 (4)°, such that τ₄ is 0.96, which indicates very little deviation from a tetrahedral geometry. For comparison, τ₄ for the [CoCl₄]²⁻ anion in [Co(Me₂SO)₆][CoCl₄] is 0.98 (where α = 112.38° and β = 108.81°; Ciccarese et al., 1993).

3. Supramolecular features

Fig. 2 shows the packing in the unit cell. There are no significant intermolecular interactions between the [Co^II(Me₂SO)₆]²⁺ and [Co^IICl₃quinoline]⁻ ions, with the exception of very weak C—H⋯Cl interactions. The distances between the Cl and the carbon atoms of the methyl groups of the Me₂SO ligands are, for example, Cl1⋯C32—S3 (symmetry code: x, y, z) [3.525 (3) Å], Cl1⋯C31—S3 (symmetry code: x, y, z) [3.736 (4) Å], Cl2⋯C22—S2 (symmetry code: 1 + x, 1 + y, z) [3.633 (4) Å], Cl2⋯C21—S2 (symmetry code: 1 + x, 1 + y, z) [3.770 (4) Å], Cl3⋯C12—S1 (symmetry code: 1 + x, y, z) [3.638 (4) Å] and Cl3⋯C32—S3 (symmetry code: x, 1 + y, z) [3.819 (4) Å] and are comparable to the sum of the van der Waals radii of Cl and CH₃ of 3.80 Å (Pauling, 1986 ).

Figure 2
The packing of [Co^II(Me₂SO)₆][Co^IICl₃quinoline]₂. H atoms have been omitted for clarity.

4. Database survey

The structure reported herein is closely related to the previously reported [Co(Me₂SO)₆][CoCl₄] complex as discussed above (Ciccarese et al., 1993). Interestingly, as long ago as 1960, and based on spectral and magnetic evidence only, Cotton & Francis reported that a complex having the empirical formula CoCl₂·3Me₂SO is more correctly formulated as [Co(Me₂SO)₆][CoCl₄] (Cotton & Francis, 1960).

In addition to [Co(Me₂SO)₆][CoCl₄], there are a few other examples of cobalt complexes solvated by Me₂SO that are listed in the Cambridge Database (CSD Version 5.38; Groom et al., 2016). For example, there are two reports for [Co(Me₂SO)₆][ClO₄]₂, one of which possesses Co—O distances in the range 2.0833 (17)–2.0934 (15) Å, giving a mean Co—O distance of 2.088 (5) Å, with O—Co—O (cis) angles between 90.11 (6) and 92.31 (6)° (Comuzzi et al., 2002 ), while a subsequent report lists Co—O distances in the range 2.088 (2)–2.110 (2) Å, with O—Co—O (cis) angles between 85.26 (7) and 93.67 (8)° (Chan et al., 2004 ). In [Co(Me₂SO)₆][SnCl₆], both the cobalt and tin metal ions display an octahedral environments, with the Co—O bond lengths reported between 2.093 (4) and 2.113 (5) Å (White et al., 2007 ). The O—Co—O (cis) angles vary between 89.0 (2) and 90.0 (2)° (White et al., 2007).

In addition to the above Co^II compounds, the octahedral Co^III complex [Co(Me₂SO)₆][NO₃]₃ is also known and possesses six equivalent Co—O bond lengths of 2.005 (2) Å, which are shorter than the values in the Co^II complexes (Li & Ng, 2010 ).

Although Me₂SO is typically coordinated to a metal via the oxygen atom (Sipos et al., 2015 ; Calligaris, 2004 ; Calligaris & Carugo, 1996 ), there are examples in which Me₂SO serves as an S-donor, as illustrated by the ruthenium complex [mer-RuCl₃(acv)(Me₂SO-S)(C₂H₅OH)]·C₂H₅OH (acv = acyclovir) (Turel et al., 2004 ). With regard to cobalt, it has been noted that Co^II is a hard acceptor preferring hard-donor atoms like oxygen in Me₂SO, the bonds being mainly electrostatic in nature (Comuzzi et al., 2002). Nevertheless, while Me₂SO coordination to cobalt through the soft-donor sulfur atom (rather than the oxygen atom) is rare, there are some notable examples. For example, the compound bis(dimethyl sulfoxide)hydridobis(triphenylphosphane)cobalt(I), [CoH(C₁₈H₁₅P)₂(Me₂SO)₂], contains Co^I coordinating a hydride anion, two phosphine ligands and two Me₂SO moieties that are bound through the sulfur atom in a distorted trigonal–bipyramidal structure (Hapke et al., 2010 ). Interestingly, there is an example of a cobalt(III) porphyrin complex that contains both oxygen- and sulfur-bound Me₂SO moieties, i.e. bis(dimethyl sulfoxide-κO)-(5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato)-cobalt(III) bis(dimethyl sulfoxide-κS)-(5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato)cobalt(III) bis(hexafluoroantimonate) dimethyl sulfoxide solvate (Venkatasubbaiah et al., 2011 ). The existence of both forms of Me₂SO bonding to Co^III in this latter complex cannot be predicted readily by the application of traditional hard/soft-acid/base theory.

The Co—N bond length in the anion [Co^IICl₃(quinoline)₂]⁻ of the title compound is 2.037 (5) Å while the Co–Cl bond lengths are 2.2517 (10)–2.2534 (10) Å, and the Cl—Co—Cl and Cl—Co—N angles range between 108.21 (5) and 114.26 (4)°, and 107.09 (9) and 108.80 (8)°, respectively. For comparison, the Co—N bond lengths in the Co^IICl₂(quinoline)₂ complex are 2.061 (3) and 2.037 (5) Å and the Co—Cl bond lengths are 2.246 (2) and 2.241 (1) Å (Golic & Mirceva, 1988), while the Cl—Co—Cl angle is 114.5 (1)° and the Cl—Co—N angles range between 106.2 (1) and 108.9 (1)°.

5. Synthesis and crystallization

Anhydrous cobalt(II) chloride (97%; 0.1301 g, 0.0010 mol) was mixed with quinoline, C₉H₇N, (99%; 0.2595 g, 0.0020 mol) in Me₂SO (20 mL) and refluxed for one h. After cooling down, the mixture was transferred to a beaker and placed in a desiccator containing anhydrous calcium chloride pellets (4–20 mesh) to crystallize over a period of four months. Deep-blue crystals of [Co(Me₂SO)₆]²⁺{[CoCl₃quinoline]₂}⁻ suitable for X-ray diffraction were obtained from this process of slow evaporation. Notably, when the reaction between anhydrous cobalt(II) chloride and quinoline is conducted in EtOH, rather than Me₂SO, the previously reported [Co^IICl₂(quinoline)₂] complex is obtained (Golic & Mirceva, 1988).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Hydrogen atoms on carbon were placed in calculated positions (C—H = 0.95–1.00 Å) and included as riding contributions with isotropic displacement parameters U_iso(H) = 1.2U_eq(Csp²) or 1.5U_eq(Csp³).

Table 1
Experimental details

Crystal data
Chemical formula	[Co(C₂H₆OS)₆][CoCl₃(C₉H₇N)]₂
M_r	1116.57
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	230
a, b, c (Å)	8.3182 (13), 9.6130 (15), 15.595 (2)
α, β, γ (°)	81.767 (2), 82.776 (2), 87.183 (2)
V (Å³)	1223.7 (3)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.63
Crystal size (mm)	0.39 × 0.12 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.626, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	19375, 7447, 4839
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.116, 1.02
No. of reflections	7447
No. of parameters	247
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.47
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 and SHELXTL (Sheldrick 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1820336

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018001652/lh5868sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018001652/lh5868Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Hexakis(dimethyl sulfoxide-κO)cobalt(II) bis[trichlorido(quinoline-κN)cobaltate(II)] top

Crystal data top

[Co(C₂H₆OS)₆][CoCl₃(C₉H₇N)]₂	Z = 1
M_r = 1116.57	F(000) = 571
Triclinic, P1	D_x = 1.515 Mg m⁻³
a = 8.3182 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6130 (15) Å	Cell parameters from 7471 reflections
c = 15.595 (2) Å	θ = 2.4–30.1°
α = 81.767 (2)°	µ = 1.63 mm⁻¹
β = 82.776 (2)°	T = 230 K
γ = 87.183 (2)°	Block, blue
V = 1223.7 (3) Å³	0.39 × 0.12 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	4839 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 30.5°, θ_min = 1.3°
T_min = 0.626, T_max = 0.746	h = −11→11
19375 measured reflections	k = −13→13
7447 independent reflections	l = −22→22

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0457P)² + 0.7087P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
7447 reflections	Δρ_max = 0.77 e Å⁻³
247 parameters	Δρ_min = −0.46 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
Co1	0.56334 (6)	0.57989 (4)	0.70199 (3)	0.04816 (13)
Co2	0.0000	0.0000	1.0000	0.02575 (11)
Cl1	0.56412 (18)	0.34385 (10)	0.71205 (7)	0.0874 (4)
Cl2	0.81055 (11)	0.65246 (10)	0.64138 (7)	0.0647 (2)
Cl3	0.48261 (13)	0.64884 (10)	0.83322 (6)	0.0659 (3)
N	0.3997 (3)	0.6584 (3)	0.61758 (17)	0.0502 (6)
S1	−0.13554 (8)	0.28530 (7)	0.90892 (5)	0.04024 (17)
S2	−0.09070 (8)	−0.10708 (7)	0.82809 (5)	0.03584 (16)
S3	0.31946 (7)	0.11911 (7)	0.89997 (4)	0.03205 (15)
O1	−0.0198 (2)	0.22294 (17)	0.97373 (12)	0.0334 (4)
O2	−0.0073 (2)	0.00114 (19)	0.86695 (12)	0.0366 (4)
O3	0.2483 (2)	0.01632 (18)	0.97778 (12)	0.0340 (4)
C1	0.3345 (5)	0.5732 (4)	0.5722 (3)	0.0657 (10)
H1A	0.3652	0.4773	0.5809	0.079*
C2	0.2274 (6)	0.6144 (7)	0.5145 (3)	0.0948 (17)
H2A	0.1791	0.5472	0.4885	0.114*
C3	0.1909 (5)	0.7490 (7)	0.4948 (3)	0.0865 (15)
H3A	0.1210	0.7776	0.4522	0.104*
C4	0.2547 (4)	0.8511 (5)	0.5364 (2)	0.0667 (11)
C5	0.2245 (6)	1.0016 (6)	0.5210 (3)	0.0875 (15)
H5A	0.1511	1.0396	0.4821	0.105*
C6	0.2971 (4)	1.0822 (5)	0.5601 (2)	0.0621 (10)
H6A	0.2807	1.1796	0.5447	0.074*
C7	0.3967 (5)	1.0394 (4)	0.6224 (3)	0.0706 (11)
H7A	0.4403	1.1045	0.6519	0.085*
C8	0.4309 (4)	0.8990 (4)	0.6405 (2)	0.0610 (9)
H8A	0.5021	0.8674	0.6820	0.073*
C9	0.3626 (4)	0.8004 (4)	0.5987 (2)	0.0534 (8)
C11	−0.0084 (5)	0.3546 (4)	0.8131 (2)	0.0638 (10)
H11A	−0.0742	0.4082	0.7720	0.096*
H11B	0.0482	0.2779	0.7866	0.096*
H11C	0.0699	0.4154	0.8286	0.096*
C12	−0.2066 (4)	0.4461 (3)	0.9459 (3)	0.0588 (9)
H12A	−0.2738	0.4975	0.9047	0.088*
H12B	−0.1149	0.5020	0.9504	0.088*
H12C	−0.2699	0.4266	1.0026	0.088*
C21	0.0638 (5)	−0.2325 (4)	0.8012 (2)	0.0618 (9)
H21A	0.0252	−0.2929	0.7638	0.093*
H21B	0.0920	−0.2890	0.8542	0.093*
H21C	0.1587	−0.1844	0.7708	0.093*
C22	−0.1126 (5)	−0.0229 (4)	0.7210 (2)	0.0601 (9)
H22A	−0.1599	−0.0871	0.6892	0.090*
H22B	−0.0071	0.0041	0.6910	0.090*
H22C	−0.1828	0.0602	0.7242	0.090*
C31	0.3992 (4)	0.2550 (3)	0.9467 (2)	0.0536 (8)
H31A	0.4504	0.3230	0.9006	0.080*
H31B	0.4788	0.2149	0.9844	0.080*
H31C	0.3121	0.3012	0.9805	0.080*
C32	0.5044 (3)	0.0349 (3)	0.8624 (2)	0.0442 (7)
H32A	0.5610	0.0958	0.8142	0.066*
H32B	0.4817	−0.0527	0.8429	0.066*
H32C	0.5715	0.0156	0.9095	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0638 (3)	0.0365 (2)	0.0456 (3)	−0.00097 (19)	−0.0139 (2)	−0.00423 (18)
Co2	0.0226 (2)	0.0228 (2)	0.0314 (3)	−0.00025 (17)	−0.00292 (18)	−0.00259 (18)
Cl1	0.1588 (12)	0.0370 (5)	0.0626 (6)	−0.0162 (6)	−0.0005 (6)	−0.0004 (4)
Cl2	0.0591 (5)	0.0601 (5)	0.0769 (6)	−0.0037 (4)	−0.0140 (4)	−0.0104 (4)
Cl3	0.0886 (7)	0.0612 (5)	0.0506 (5)	0.0280 (5)	−0.0216 (4)	−0.0151 (4)
N	0.0579 (16)	0.0548 (17)	0.0405 (14)	−0.0099 (13)	−0.0111 (12)	−0.0073 (12)
S1	0.0376 (4)	0.0294 (3)	0.0545 (4)	0.0028 (3)	−0.0158 (3)	−0.0006 (3)
S2	0.0322 (3)	0.0401 (4)	0.0366 (4)	−0.0029 (3)	−0.0049 (3)	−0.0090 (3)
S3	0.0250 (3)	0.0296 (3)	0.0396 (4)	−0.0002 (2)	−0.0032 (3)	0.0012 (3)
O1	0.0318 (9)	0.0231 (8)	0.0447 (11)	0.0014 (7)	−0.0088 (8)	0.0001 (7)
O2	0.0448 (11)	0.0338 (10)	0.0317 (10)	−0.0067 (8)	−0.0041 (8)	−0.0049 (8)
O3	0.0232 (8)	0.0339 (10)	0.0420 (10)	−0.0012 (7)	−0.0027 (7)	0.0039 (8)
C1	0.061 (2)	0.066 (2)	0.079 (3)	−0.0140 (18)	−0.024 (2)	−0.022 (2)
C2	0.082 (3)	0.143 (5)	0.074 (3)	−0.030 (3)	−0.008 (2)	−0.056 (3)
C3	0.069 (3)	0.147 (5)	0.050 (2)	−0.008 (3)	−0.023 (2)	−0.023 (3)
C4	0.051 (2)	0.112 (3)	0.0344 (18)	−0.003 (2)	−0.0007 (15)	−0.0031 (19)
C5	0.078 (3)	0.110 (4)	0.059 (3)	0.031 (3)	−0.009 (2)	0.030 (3)
C6	0.056 (2)	0.083 (3)	0.0409 (19)	−0.0063 (19)	−0.0049 (16)	0.0146 (18)
C7	0.074 (3)	0.057 (2)	0.077 (3)	−0.0079 (19)	−0.005 (2)	0.000 (2)
C8	0.062 (2)	0.061 (2)	0.059 (2)	−0.0091 (17)	−0.0185 (17)	0.0077 (17)
C9	0.0495 (18)	0.073 (2)	0.0360 (17)	−0.0071 (16)	−0.0040 (14)	−0.0008 (16)
C11	0.078 (2)	0.053 (2)	0.054 (2)	0.0094 (18)	−0.0079 (18)	0.0151 (16)
C12	0.0554 (19)	0.0396 (17)	0.083 (3)	0.0199 (15)	−0.0223 (18)	−0.0105 (17)
C21	0.074 (2)	0.0475 (19)	0.068 (2)	0.0225 (17)	−0.0182 (19)	−0.0216 (17)
C22	0.082 (3)	0.060 (2)	0.0423 (18)	0.0125 (18)	−0.0244 (17)	−0.0116 (16)
C31	0.065 (2)	0.0356 (16)	0.060 (2)	−0.0148 (15)	0.0069 (16)	−0.0121 (15)
C32	0.0398 (15)	0.0405 (16)	0.0468 (17)	0.0067 (12)	0.0089 (13)	−0.0023 (13)

Geometric parameters (Å, º) top

Co1—N	2.054 (3)	C4—C5	1.446 (6)
Co1—Cl1	2.2517 (10)	C5—C6	1.269 (6)
Co1—Cl2	2.2521 (11)	C5—H5A	0.9400
Co1—Cl3	2.2534 (10)	C6—C7	1.362 (5)
Co2—O3	2.0606 (17)	C6—H6A	0.9400
Co2—O3ⁱ	2.0607 (17)	C7—C8	1.362 (5)
Co2—O2ⁱ	2.0818 (18)	C7—H7A	0.9400
Co2—O2	2.0819 (18)	C8—C9	1.404 (5)
Co2—O1ⁱ	2.1258 (17)	C8—H8A	0.9400
Co2—O1	2.1258 (17)	C11—H11A	0.9700
N—C1	1.331 (4)	C11—H11B	0.9700
N—C9	1.383 (4)	C11—H11C	0.9700
S1—O1	1.5236 (18)	C12—H12A	0.9700
S1—C12	1.775 (3)	C12—H12B	0.9700
S1—C11	1.784 (4)	C12—H12C	0.9700
S2—O2	1.5127 (19)	C21—H21A	0.9700
S2—C21	1.772 (3)	C21—H21B	0.9700
S2—C22	1.776 (3)	C21—H21C	0.9700
S3—O3	1.5273 (19)	C22—H22A	0.9700
S3—C32	1.775 (3)	C22—H22B	0.9700
S3—C31	1.776 (3)	C22—H22C	0.9700
C1—C2	1.351 (6)	C31—H31A	0.9700
C1—H1A	0.9400	C31—H31B	0.9700
C2—C3	1.316 (7)	C31—H31C	0.9700
C2—H2A	0.9400	C32—H32A	0.9700
C3—C4	1.410 (6)	C32—H32B	0.9700
C3—H3A	0.9400	C32—H32C	0.9700
C4—C9	1.424 (5)

N—Co1—Cl1	107.09 (9)	C4—C5—H5A	120.0
N—Co1—Cl2	107.76 (8)	C5—C6—C7	125.4 (4)
Cl1—Co1—Cl2	108.21 (5)	C5—C6—H6A	117.3
N—Co1—Cl3	108.80 (8)	C7—C6—H6A	117.3
Cl1—Co1—Cl3	110.46 (4)	C6—C7—C8	117.8 (4)
Cl2—Co1—Cl3	114.26 (4)	C6—C7—H7A	121.1
O3—Co2—O3ⁱ	180.0	C8—C7—H7A	121.1
O3—Co2—O2ⁱ	90.17 (7)	C7—C8—C9	121.6 (4)
O3ⁱ—Co2—O2ⁱ	89.83 (7)	C7—C8—H8A	119.2
O3—Co2—O2	89.83 (7)	C9—C8—H8A	119.2
O3ⁱ—Co2—O2	90.17 (7)	N—C9—C8	120.7 (3)
O2ⁱ—Co2—O2	180.00 (10)	N—C9—C4	121.2 (3)
O3—Co2—O1ⁱ	91.82 (7)	C8—C9—C4	118.0 (4)
O3ⁱ—Co2—O1ⁱ	88.19 (7)	S1—C11—H11A	109.5
O2ⁱ—Co2—O1ⁱ	86.29 (7)	S1—C11—H11B	109.5
O2—Co2—O1ⁱ	93.71 (7)	H11A—C11—H11B	109.5
O3—Co2—O1	88.18 (7)	S1—C11—H11C	109.5
O3ⁱ—Co2—O1	91.81 (7)	H11A—C11—H11C	109.5
O2ⁱ—Co2—O1	93.71 (7)	H11B—C11—H11C	109.5
O2—Co2—O1	86.29 (7)	S1—C12—H12A	109.5
O1ⁱ—Co2—O1	180.000 (19)	S1—C12—H12B	109.5
C1—N—C9	116.5 (3)	H12A—C12—H12B	109.5
C1—N—Co1	120.2 (3)	S1—C12—H12C	109.5
C9—N—Co1	123.0 (2)	H12A—C12—H12C	109.5
O1—S1—C12	103.99 (14)	H12B—C12—H12C	109.5
O1—S1—C11	105.22 (15)	S2—C21—H21A	109.5
C12—S1—C11	98.78 (18)	S2—C21—H21B	109.5
O2—S2—C21	105.12 (15)	H21A—C21—H21B	109.5
O2—S2—C22	103.28 (15)	S2—C21—H21C	109.5
C21—S2—C22	98.54 (18)	H21A—C21—H21C	109.5
O3—S3—C32	103.92 (12)	H21B—C21—H21C	109.5
O3—S3—C31	104.93 (13)	S2—C22—H22A	109.5
C32—S3—C31	98.99 (16)	S2—C22—H22B	109.5
S1—O1—Co2	117.12 (10)	H22A—C22—H22B	109.5
S2—O2—Co2	124.52 (11)	S2—C22—H22C	109.5
S3—O3—Co2	118.17 (10)	H22A—C22—H22C	109.5
N—C1—C2	124.9 (4)	H22B—C22—H22C	109.5
N—C1—H1A	117.6	S3—C31—H31A	109.5
C2—C1—H1A	117.6	S3—C31—H31B	109.5
C3—C2—C1	119.7 (4)	H31A—C31—H31B	109.5
C3—C2—H2A	120.2	S3—C31—H31C	109.5
C1—C2—H2A	120.2	H31A—C31—H31C	109.5
C2—C3—C4	121.2 (4)	H31B—C31—H31C	109.5
C2—C3—H3A	119.4	S3—C32—H32A	109.5
C4—C3—H3A	119.4	S3—C32—H32B	109.5
C3—C4—C9	116.3 (4)	H32A—C32—H32B	109.5
C3—C4—C5	126.7 (4)	S3—C32—H32C	109.5
C9—C4—C5	117.0 (4)	H32A—C32—H32C	109.5
C6—C5—C4	120.0 (4)	H32B—C32—H32C	109.5
C6—C5—H5A	120.0

C12—S1—O1—Co2	148.84 (16)	C4—C5—C6—C7	−5.0 (7)
C11—S1—O1—Co2	−107.81 (16)	C5—C6—C7—C8	4.8 (6)
C21—S2—O2—Co2	−95.18 (18)	C6—C7—C8—C9	−1.9 (6)
C22—S2—O2—Co2	162.00 (16)	C1—N—C9—C8	−177.3 (3)
C32—S3—O3—Co2	−145.35 (14)	Co1—N—C9—C8	−3.1 (4)
C31—S3—O3—Co2	111.19 (15)	C1—N—C9—C4	2.5 (5)
C9—N—C1—C2	−4.9 (6)	Co1—N—C9—C4	176.7 (2)
Co1—N—C1—C2	−179.3 (4)	C7—C8—C9—N	179.6 (3)
N—C1—C2—C3	5.5 (7)	C7—C8—C9—C4	−0.3 (5)
C1—C2—C3—C4	−3.5 (8)	C3—C4—C9—N	−0.9 (5)
C2—C3—C4—C9	1.4 (6)	C5—C4—C9—N	−179.7 (3)
C2—C3—C4—C5	−180.0 (4)	C3—C4—C9—C8	178.9 (3)
C3—C4—C5—C6	−176.3 (4)	C5—C4—C9—C8	0.2 (5)
C9—C4—C5—C6	2.3 (6)

Symmetry code: (i) −x, −y, −z+2.

Acknowledgements

Gerard Parkin (Columbia University) is thanked for helpful discussions.

Funding information

RKU and KM would like to thank Pace University for research support (Pace Undergraduate Student & Faculty Research Award). SG thanks the University Grants Commission, New Delhi, India, for a Raman Fellowship for postdoctoral research.

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