Di­chloro­bis(1-propyl­imidazolidine-2-thione-[kappa]S)­cobalt(II)

The crystal structure of the title compound, [CoCl₂(C₆H₁₂N₂S)₂], consists of monomer units of a Co^II atom coordinated to two 1-propyl­imidazolidine-2-thione ligands and to two chloride ions. The heterocyclic thione ligand is monodentate and coordinated to the metal through the thione S atom. The environment around the Co^II atom is a slightly distorted tetrahedron. The Co-S bond lengths are 2.341 (2) and 2.330 (2) Å, and the Co-Cl bond lengths are 2.234 (2) and 2.238 (2) Å. The most important point of distortion is the S-Co-S bond angle of only 97.83 (8)°. Intramolecular classical hydrogen bonds are found between the chloride ions and the N-H groups. Additionally, intra- and intermolecular non-classical hydrogen bonds are found.

S1. Comment

Heterocyclic thiones, and especially heterocyclic molecules containing the thioamide group [–C(S)–NH–], form a class of coordination compounds which are interesting because of the thione–thiol equilibrium and the study of this equilibrium has been one of our objectives (García-Vázquez et al., 1999). In addition, these compounds have a wide range of applications as analytical reagents, metal corrosion inhibitors and in the pharmaceutical field (Hussain et al., 1990).

Furthermore, heterocyclic thione complexes of cobalt have been used to analyse the redox properties of the metal, studies which could be relevant to understanding the interaction of the cobalt ion with DNA (Tran Qui & Bagieu, 1990), but there have been relatively few reports of its complexation behaviour with this kind of ligand.

We have therefore synthesized a cobalt(II) complex incorporating a heterocyclic thionate ligand, namely dichlorobis(1-propylimidazolidine-2-thione-κS)cobalt(II), (I), the structure of which consists of monomeric units, although weak interactions between molecules through non-classical hydrogen bonds are found (Table 2). The heterocyclic thione ligand is monodentate and bonded to the metal through the S atom (Fig. 1). The environment around the Co^II atom is that of a slightly distorted tetrahedron, where the dihedral angle between the Co(Cl)₂ and Co(S)₂ moieties is 88.35 (6)°. The main point of distortion is the S—Co—S angle of only 97.83 (8)°, which deviated greatly from the ideal tetrahedral value (within experimental error) seen for Cl—Co—Cl in (I). Intramolecular hydrogen bonds between the N—H groups and the Cl atoms are also found (see Table 2), where the two amine H atoms coordinate to different Cl atoms (clinal geometry, see below). Hence, the dihedral angle between the mean planes of the two five-membered rings in (I) is 52.5 (2)°.

Looking to explain the value of the S—Co—S angle, a search was made for CoCl₂S₂ complexes in the Cambridge Structural Database (CSD; Version 5.22 of October 2001; Allen & Kennard, 1993) which returned only 9 hits and 7 compounds, one being trinuclear and therefore not considered further. There are three thiourea derivatives, one of them, dichlorobis(N,N'-di-o-tolylthiourea-S)cobalt(II) (Prisyazhnyuk et al., 1986), has a very distorted tetrahedral core, with a Cl—Co—Cl angle close to 120° and an S—Co—S angle close to 111°. The remaining thiourea (Hall & Horrocks, 1969; Domiano & Tiripicchio, 1972) and N,N'-diethylthiourea (Bonamico et al., 1973; Abbati et al., 1999) derivatives both appear twice and both compounds are geometrically similar to (I). Hydrogen bonds are also found in these two compounds. It is noteworthy that there are two possibilities for intramolecular interactions involving the Cl atoms. The first is a periplanar geometry where the two amine H atoms coordinate to the same Cl atom and the second is a clinal geometry, where the two amine H atoms coordinate to different Cl atoms. It is interesting to note that both geometries are found in dichlorobis(N,N'-diethylthiourea)cobalt(II), as there are two molecules in the asymmetric unit (Abbati et al., 1999). Still, the geometrical parameters around the Co atom are quite similar, the S—Co—S angles being 97.27 (5) and 98.57 (4)°, respectively.

In the other three compounds found in the in the CSD search, the S atom is connected to a ring and, in two of them, connects to a five-membered ring as in (I). In the first of the latter two, dinuclear bis{[µ²-N,N'-ethylenebis(pyrrolidine-2-thione-S,S')]dichlorocobalt(II)} (Atherton et al., 1998), the dithione ligands bridge the two Co^II atoms and the larger S—Co—S angle of 121.38 (8)° can be understood as a being a result of this bridging. The second compound, dichlorobis(2-mercaptobenzimidazole)cobalt(II) (Ravikumar et al. 1995), is the most chemically similar to (I), and as for the title compound, a clinal geometry is found. Still, the S—Co—S angle is 108.9 (1)° compared with 97.38 (8)° in (I). Classical intramolecular hydrogen bonds between the amine H and the Cl atoms are found in both complexes, but the N-propyl groups in (I) prevent the occurrence of intermolecular hydrogen bonds and this is probably one of the reasons for the differences found between the two complexes.

The hybridization of the S atom has been discussed extensively by Raper & Nowell (1979) on the basis of the Co—S—C angle and the dihedral angle between the Co—S—C plane and the mean plane of the ligand. When the Co—S—C angle is close to 104°, an sp³ hybridization is proposed, and values of about 108–110° are consistent with an sp² character. The corresponding values in (I), 106.7 (2) and 107.1 (3)°, do not allow us to distinguish between the two possibilities. The dihedral angles between the Co—S—C and SC(N)₂ planes found in (I) are 15.2 (3) and 10.2 (3)°, which are consistent with sp² hybridization.

Furthermore, the ring bond lengths are consistent with a considerable delocalization of the charge in the SC(N)₂ moiety, with the values for the C—N bond [average 1.318 (8) Å] being shorter than those expected for a single bond (Allen et al., 1987). The C—S bonds [average 1.696 (7) Å] are only slightly longer than in the uncoordinated N,N'-dimethyl-1,3-imidazolidine-2-thione ligand [1.673 (5) Å; Chieh & Cheung, 1983], suggesting that the ligand is coordinated in the thione rather than the thionate form. The Co—S distances of 2.330 (2) and 2.341 (2) Å are slightly longer than in other complexes where a thionate form is suggested (Raper & Nowell, 1979). The Co—Cl bond lengths agree with the corresponding lengths of other tetrahedral cobalt(II) complexes (Tran Qui & Bagieu, 1990; Abbati et al., 1999).

The geometrical parameters found in dichlorobis(2-mercaptobenzimidazole)cobalt(II) (Ravikumar et al., 1995) are also consistent with a thione rather than a thionate form [C—S bond lengths of 1.701 (6) and 1.724 (7) Å, and Co—S—C bond angles of 105.6 (2) and 108.4 (2)°]. The C—S bond lengths found in dichlorobis(N,N'-diethylthiourea)cobalt(II) (Abbati et al., 1999) are longer, whereas the average S—Co—S angle is 97.92 (5)°, similar to that found in (I). Hence, the value of the S—Co—S angle does not depend on the sp character of the S atom.

Thus, the value of the S—Co—S angle, together with the differences found in the Co—S and Co—Cl bond lengths, are probably a consequence of the different properties of the donor atoms. The Cl- and S-atom covalent radii differ only by 0.03 Å (Huheey et al., 1993). However, the Co—S and Co—Cl bond lengths differ by about 0.1 Å in all the compounds found in the CSD search, except in dichlorobis(2-mercaptobenzimidazole)cobalt(II) (Ravikumar et al., 1995), which again deviates by an average of 0.07 Å (maximum 0.098 Å and minimum 0.037 Å). This, together with the intermolecular hydrogen bonds and the crystal packing, results in the differences found for this compound, where the orientation of the ligands allows similar bond lengths and a regular geometry around the Co^II atom. The different orientation present in (I) (Fig. 3) is probably due to the propyl groups and the lack of classical intermolecular hydrogen bonds between the N atom and the Cl atoms of neighbouring molecules.

The thione ligands (excluding the n-propyl group) are essentially planar, with a maximum deviation from the least-squares mean planes of 0.053 (5) Å for atom C13. The Co^II atom deviates by 0.508 (9) and 0.363 (9) Å from these planes.

S2. Experimental

The ligand 1-propylimidazolidine-2-thione was prepared and characterized following a modification of the procedure of Allen et al. (1959) (see reaction Scheme in Comment). N-Propylethylenediamine (3.64 g, 0.36 mmol) was dissolved in EtOH/H₂O (10 + 10 ml) and cooled in an ice bath. An excess of carbon disulfide (0.6 ml 9.9 mmol) was added dropwise (0.01 ml min^-1) and the temperature raised to 333 K. A second portion of carbon disulfide (3.0 ml, 49.7 mmol) was added dropwise (0.02 ml min^-1). When the addition was complete, the temperature was raised to 383 K and reflux continued for 1 h. Thereafter, 0.5 ml of hydrochloride acid was added and the reflux continued for a further 10 h. The mixture was cooled and the 2.78 g of solid which was collected was washed with chilled acetone. The solid was identified as 1-propylimidazolidine-2-thione. Elemental analysis, found: C 49.8, H 8.1, N 19.3, S 22.0%; calculated for C₆H₁₂N₂S: C 50.0, H 8.4, N 19.4, S 22.2%. Relevant spectroscopic data, IR spectrum (KBr mulls, cm^-1): 3192 ν(N—H), 1498 ν(C—N)+ δ(N—H), 612 Δ(N—H), 510 ν(C—S); ¹H NMR (300 MHz, CDCl₃, p.p.m.): δ 6.57 (bs, 3H, N–H), 3.65–3.44 (m, 8H, CH₂), 1.65 (m, 3H, CH₃); ¹³C NMR (75 MHz, CDCl₃, p.p.m.): δ 183.6, 48.9, 48.8, 41.8, 20.81, 11.5. For the preparation of (I), CoCl₂ hexahydrate (2 g, 8.4 mmol) was dried with refluxing Cl₂SO. After 2 h, the excess Cl₂SO was removed under vacuum. After this, all further reactions were carried out under an argon atmosphere. Anhydrous CoCl₂ (0.13 g, 1.0 mmol) was dissolved in 20 ml of dry MeOH and an excess of 1-propylimidazolidine-2-thione (0.43 g, 3.0 mmol) was added. After 12 h of reaction, the MeOH was removed under vacuum and the oily product obtained was recrystallized from toluene. Elemental analysis, found: C 35.3, H 5.7, N 13.6, S 15.6%; calculated for C₁₂H₂₄Cl₂CoN₄S₂: C 34.5, H 5.8, N 13.4, S 15.3%.

S3. Refinement

H atoms of CH₂ and CH₃ groups were placed in calculated positions and refined with a riding model (C—H 0.97 and 0.96 Å, and 1.00 Å for CH₃ groups C15 and C16) and U_iso values 1.2U_eq and 1.5U_eq, respectively, of the C atoms to which they are attached. H atoms of the N—H groups were also placed in calculated positions and refined with a riding model (N—H 0.86 Å) and U_iso values 1.2U_eq of the N atoms to which they are attached.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1998); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary radii.
	Fig. 2. The hydrogen bonding in (I). [Symmetry codes: (i) x, 2 - y, z - 1/2; (ii) x, 1 - y, z + 1/2.]
	Fig. 3. The crystal packing in (I) viewed along the b axis.

Dichlorobis(N-propylimidazolidine-S)cobalt(II)

Crystal data

[CoCl2(C6H12N2S)2]	F(000) = 868
Mr = 418.30	Dx = 1.420 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 926 reflections
a = 15.684 (4) Å	θ = 2.7–24.0°
b = 8.640 (2) Å	µ = 1.36 mm^−1
c = 14.916 (4) Å	T = 293 K
β = 104.528 (5)°	Prism, blue
V = 1956.7 (9) Å^3	0.39 × 0.20 × 0.09 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer	4015 independent reflections
Radiation source: fine-focus sealed tube	1464 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 26.4°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→18
Tmin = 0.619, Tmax = 0.887	k = −8→10
11320 measured reflections	l = −18→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0728P)^2] where P = (Fo^2 + 2Fc^2)/3
4015 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

Experimental. The poor quality of the best crystal give values for R(int) of 0.0921 and for R(sigma) of 0.1566.

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co	0.83515 (6)	0.75187 (12)	0.09041 (6)	0.0510 (3)
Cl1	0.91702 (12)	0.9632 (2)	0.13422 (11)	0.0625 (5)
Cl2	0.92298 (13)	0.5482 (2)	0.08917 (12)	0.0674 (6)
S1	0.73292 (12)	0.7807 (2)	−0.05288 (12)	0.0619 (6)
S2	0.73526 (13)	0.7148 (2)	0.18065 (12)	0.0638 (6)
N11	0.7566 (4)	0.7720 (7)	−0.2239 (4)	0.0608 (17)
N12	0.8628 (4)	0.6662 (8)	−0.1219 (4)	0.0654 (18)
H12	0.8909	0.6286	−0.0694	0.078*
N21	0.7554 (4)	0.7323 (7)	0.3636 (4)	0.0638 (17)
N22	0.8646 (4)	0.8288 (8)	0.3198 (4)	0.0676 (18)
H22	0.8961	0.8583	0.2833	0.081*
C11	0.7869 (5)	0.7397 (8)	−0.1352 (4)	0.0516 (17)
C12	0.8153 (5)	0.7135 (9)	−0.2785 (5)	0.068 (2)
H12A	0.8319	0.7952	−0.3154	0.081*
H12B	0.7876	0.6303	−0.3192	0.081*
C13	0.8938 (5)	0.6558 (10)	−0.2064 (5)	0.078 (2)
H13A	0.9082	0.5500	−0.2187	0.093*
H13B	0.9449	0.7210	−0.2028	0.093*
C14	0.6783 (6)	0.8612 (10)	−0.2665 (6)	0.084 (3)
H14A	0.6571	0.9106	−0.2178	0.101*
H14B	0.6949	0.9426	−0.3036	0.101*
C15	0.6080 (7)	0.7756 (12)	−0.3234 (7)	0.119 (4)
H15A	0.5852	0.7007	−0.2839	0.143*
H15B	0.6311	0.7144	−0.3691	0.143*
C16	0.5326 (7)	0.8755 (14)	−0.3753 (6)	0.136 (4)
H16A	0.5141	0.9470	−0.3310	0.204*
H16B	0.4819	0.8082	−0.4061	0.204*
H16C	0.5520	0.9375	−0.4233	0.204*
C21	0.7880 (5)	0.7616 (8)	0.2912 (4)	0.0509 (17)
C22	0.8126 (5)	0.7877 (9)	0.4503 (5)	0.067 (2)
H22A	0.8296	0.7043	0.4948	0.080*
H22B	0.7846	0.8692	0.4773	0.080*
C23	0.8906 (5)	0.8481 (10)	0.4189 (4)	0.071 (2)
H23A	0.9016	0.9562	0.4354	0.086*
H23B	0.9433	0.7887	0.4460	0.086*
C24	0.6752 (6)	0.6456 (11)	0.3628 (6)	0.092 (3)
H24A	0.6540	0.5978	0.3025	0.111*
H24B	0.6897	0.5632	0.4083	0.111*
C25	0.6055 (7)	0.7367 (13)	0.3822 (9)	0.128 (4)
H25A	0.5842	0.8093	0.3320	0.153*
H25B	0.6280	0.7956	0.4385	0.153*
C26	0.5297 (7)	0.6344 (14)	0.3935 (8)	0.147 (5)
H26A	0.5334	0.5355	0.3654	0.220*
H26B	0.4747	0.6828	0.3640	0.220*
H26C	0.5333	0.6205	0.4582	0.220*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0537 (6)	0.0644 (6)	0.0376 (5)	0.0045 (5)	0.0162 (4)	−0.0026 (5)
Cl1	0.0676 (14)	0.0712 (13)	0.0483 (9)	−0.0032 (10)	0.0139 (9)	0.0017 (10)
Cl2	0.0775 (15)	0.0736 (14)	0.0557 (10)	0.0198 (11)	0.0253 (10)	0.0101 (10)
S1	0.0526 (12)	0.0893 (16)	0.0435 (9)	0.0071 (11)	0.0112 (9)	−0.0095 (10)
S2	0.0557 (12)	0.0906 (17)	0.0504 (10)	−0.0050 (11)	0.0231 (9)	−0.0137 (10)
N11	0.069 (4)	0.079 (5)	0.035 (3)	0.011 (4)	0.013 (3)	−0.005 (3)
N12	0.051 (4)	0.106 (5)	0.040 (3)	0.013 (4)	0.014 (3)	−0.003 (3)
N21	0.070 (4)	0.084 (5)	0.050 (3)	−0.011 (4)	0.039 (3)	−0.009 (4)
N22	0.057 (4)	0.107 (5)	0.044 (3)	−0.007 (4)	0.021 (3)	−0.001 (4)
C11	0.048 (4)	0.059 (5)	0.046 (4)	−0.009 (4)	0.008 (3)	0.001 (4)
C12	0.090 (6)	0.078 (6)	0.043 (4)	−0.004 (5)	0.033 (4)	0.011 (4)
C13	0.079 (6)	0.110 (7)	0.053 (5)	0.014 (5)	0.030 (5)	0.000 (5)
C14	0.101 (8)	0.084 (7)	0.061 (5)	0.017 (6)	0.005 (5)	−0.002 (5)
C15	0.096 (8)	0.127 (9)	0.111 (8)	0.018 (7)	−0.014 (7)	−0.020 (7)
C16	0.091 (8)	0.188 (12)	0.103 (8)	0.048 (8)	−0.024 (6)	0.014 (8)
C21	0.052 (5)	0.058 (5)	0.048 (4)	0.008 (4)	0.022 (3)	0.003 (4)
C22	0.074 (6)	0.087 (6)	0.041 (4)	0.003 (5)	0.020 (4)	0.007 (4)
C23	0.068 (6)	0.105 (7)	0.044 (4)	0.009 (5)	0.019 (4)	−0.009 (4)
C24	0.108 (8)	0.098 (8)	0.082 (6)	−0.028 (6)	0.044 (6)	−0.012 (5)
C25	0.081 (7)	0.144 (10)	0.177 (11)	0.007 (7)	0.068 (8)	−0.036 (9)
C26	0.099 (9)	0.203 (14)	0.156 (10)	−0.057 (9)	0.064 (8)	−0.013 (10)

Geometric parameters (Å, º)

Co—Cl1	2.234 (2)	C14—C15	1.420 (11)
Co—Cl2	2.238 (2)	C14—H14A	0.9700
Co—S1	2.341 (2)	C14—H14B	0.9700
Co—S2	2.330 (2)	C15—C16	1.511 (12)
S1—C11	1.696 (7)	C15—H15A	1.0000
S2—C21	1.697 (7)	C15—H15B	1.0000
N11—C11	1.318 (8)	C16—H16A	1.0001
N11—C12	1.464 (9)	C16—H16B	1.0001
N11—C14	1.454 (9)	C16—H16C	1.0001
N12—C11	1.319 (8)	C22—C23	1.510 (10)
N12—C13	1.464 (8)	C22—H22A	0.9700
N12—H12	0.8600	C22—H22B	0.9700
N21—C21	1.329 (8)	C23—H23A	0.9700
N21—C22	1.458 (9)	C23—H23B	0.9700
N21—C24	1.462 (9)	C24—C25	1.433 (11)
N22—C21	1.306 (8)	C24—H24A	0.9700
N22—C23	1.441 (8)	C24—H24B	0.9700
N22—H22	0.8600	C25—C26	1.524 (12)
C12—C13	1.502 (9)	C25—H25A	0.9700
C12—H12A	0.9700	C25—H25B	0.9700
C12—H12B	0.9700	C26—H26A	0.9600
C13—H13A	0.9700	C26—H26B	0.9600
C13—H13B	0.9700	C26—H26C	0.9600
Cl1—Co—Cl2	109.59 (9)	C16—C15—H15A	108.9
Cl1—Co—S2	111.34 (8)	C14—C15—H15B	108.9
Cl2—Co—S2	113.67 (8)	C16—C15—H15B	108.9
Cl1—Co—S1	113.07 (8)	H15A—C15—H15B	107.7
Cl2—Co—S1	110.99 (8)	C15—C16—H16A	109.5
S2—Co—S1	97.83 (8)	C15—C16—H16B	109.5
C11—S1—Co	106.7 (2)	H16A—C16—H16B	109.5
C21—S2—Co	107.1 (3)	C15—C16—H16C	109.5
C11—N11—C14	127.2 (6)	H16A—C16—H16C	109.5
C11—N11—C12	111.4 (6)	H16B—C16—H16C	109.5
C14—N11—C12	121.3 (6)	N22—C21—N21	109.2 (6)
C11—N12—C13	112.4 (6)	N22—C21—S2	127.4 (5)
C11—N12—H12	123.8	N21—C21—S2	123.4 (6)
C13—N12—H12	123.8	N21—C22—C23	101.7 (5)
C21—N21—C22	112.5 (6)	N21—C22—H22A	111.4
C21—N21—C24	126.6 (7)	C23—C22—H22A	111.4
C22—N21—C24	120.8 (6)	N21—C22—H22B	111.4
C21—N22—C23	112.8 (6)	C23—C22—H22B	111.4
C21—N22—H22	123.6	H22A—C22—H22B	109.3
C23—N22—H22	123.6	N22—C23—C22	103.6 (6)
N11—C11—N12	109.8 (6)	N22—C23—H23A	111.0
N11—C11—S1	124.2 (6)	C22—C23—H23A	111.0
N12—C11—S1	125.9 (5)	N22—C23—H23B	111.0
N11—C12—C13	103.5 (5)	C22—C23—H23B	111.0
N11—C12—H12A	111.1	H23A—C23—H23B	109.0
C13—C12—H12A	111.1	C25—C24—N21	114.6 (8)
N11—C12—H12B	111.1	C25—C24—H24A	108.6
C13—C12—H12B	111.1	N21—C24—H24A	108.6
H12A—C12—H12B	109.0	C25—C24—H24B	108.6
N12—C13—C12	101.9 (6)	N21—C24—H24B	108.6
N12—C13—H13A	111.4	H24A—C24—H24B	107.6
C12—C13—H13A	111.4	C24—C25—C26	111.1 (9)
N12—C13—H13B	111.4	C24—C25—H25A	109.4
C12—C13—H13B	111.4	C26—C25—H25A	109.4
H13A—C13—H13B	109.3	C24—C25—H25B	109.4
C15—C14—N11	115.4 (8)	C26—C25—H25B	109.4
C15—C14—H14A	108.4	H25A—C25—H25B	108.0
N11—C14—H14A	108.4	C25—C26—H26A	109.5
C15—C14—H14B	108.4	C25—C26—H26B	109.5
N11—C14—H14B	108.4	H26A—C26—H26B	109.5
H14A—C14—H14B	107.5	C25—C26—H26C	109.5
C14—C15—C16	113.5 (9)	H26A—C26—H26C	109.5
C14—C15—H15A	108.9	H26B—C26—H26C	109.5
Cl1—Co—S1—C11	84.5 (3)	C11—N11—C14—C15	−111.3 (10)
Cl2—Co—S1—C11	−39.1 (3)	C12—N11—C14—C15	72.4 (11)
S2—Co—S1—C11	−158.3 (3)	N11—C14—C15—C16	−173.0 (8)
Cl1—Co—S2—C21	−39.2 (3)	C23—N22—C21—N21	0.9 (9)
Cl2—Co—S2—C21	85.2 (3)	C23—N22—C21—S2	−178.6 (6)
S1—Co—S2—C21	−157.8 (3)	C22—N21—C21—N22	2.0 (9)
C14—N11—C11—N12	−175.4 (7)	C24—N21—C21—N22	−174.0 (7)
C12—N11—C11—N12	1.2 (9)	C22—N21—C21—S2	−178.5 (5)
C14—N11—C11—S1	7.2 (11)	C24—N21—C21—S2	5.6 (12)
C12—N11—C11—S1	−176.2 (5)	Co—S2—C21—N22	9.9 (8)
C13—N12—C11—N11	5.3 (9)	Co—S2—C21—N21	−169.5 (6)
C13—N12—C11—S1	−177.3 (6)	C21—N21—C22—C23	−3.7 (8)
Co—S1—C11—N11	−166.2 (6)	C24—N21—C22—C23	172.5 (7)
Co—S1—C11—N12	16.7 (7)	C21—N22—C23—C22	−3.1 (9)
C11—N11—C12—C13	−6.8 (9)	N21—C22—C23—N22	3.8 (8)
C14—N11—C12—C13	170.0 (7)	C21—N21—C24—C25	−112.4 (10)
C11—N12—C13—C12	−9.1 (9)	C22—N21—C24—C25	72.0 (11)
N11—C12—C13—N12	8.9 (8)	N21—C24—C25—C26	−172.0 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···Cl2	0.86	2.39	3.217 (6)	160
N22—H22···Cl1	0.86	2.50	3.291 (6)	154
C14—H14A···S1	0.97	2.69	3.163 (8)	110
C24—H24A···S2	0.97	2.67	3.148 (9)	111
C12—H12A···Cl1^i	0.97	2.68	3.618 (8)	161
C22—H22A···Cl2^ii	0.97	2.80	3.729 (8)	160

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