Synthesis and crystal structure of catena-poly[[bis­(pyridine-4-carbo­nitrile-κN¹)cobalt(II)]-di-μ-thio­cyanato-κ²N:S;κ²S:N]

The asymmetric unit of the title compound, [Co(NCS)₂(C₆H₄N₂)₂]_n (C₆H₄N₂ = pyri­dine-4-car­bo­ni­trile), consists of two crystallographically independent cobalt cations that are located on centers of inversion as well as two independent thio­cyanate anions and two independent pyri­dine-4-car­bo­ni­trile coligands that occupy general positions. Each of the cobalt cations is sixfold coordinated by two N- and two S-bonding thio­cyanate anions and two pyri­dine-4-car­bo­ni­trile coligands in an slightly distorted CoN₄S₂ octa­hedral geometry with an all-trans coordination. The cobalt cations are linked by pairs of μ-1,3-bridging anionic ligands into linear chains. Powder X-ray diffraction (PXRD) experiments indicate that the title compound was obtained as a pure phase. Moreover, comparison of the experimental X-ray powder pattern of the residue obtained after water removal from [Co(NCS)₂(C₆H₄N₂)₂(H₂O)₂] reported recently [Näther (2026).Acta Cryst. E82, 441–445] with the calculated powder pattern of the title compound proves that the latter crystalline phase has formed and indicates that a second modification with the same composition as that of the title compound might exist.

1. Chemical context

For many years, we and others have been inter­ested in the synthesis, crystal structures and magnetic properties of transition-metal thio­cyanate and seleno­cyanate coordination polymers in which the metal cations are linked by μ-1,3-bridging anionic ligands into one-dimensional or two-dimensional networks (Näther & Greve, 2003; Wöhlert et al., 2013; Neumann et al., 2018). In this context compounds based on Co^II are of special inter­est, because they can show one-dimensional or three-dimensional ferromagnetic ordering (Lescouëzec et al., 2005; Mautner et al., 2018; Wöhlert et al., 2012; 2013; Rams et al., 2020). In some cases such compounds are difficult to prepare and we therefore developed an alternative strategy in which precursor compounds with only terminally N-bonding thio­cyanate anions and weakly bound coligands are heated. This frequently leads to the formation of compounds in which the metal cations are linked by bridging anionic ligands (Näther & Greve, 2003; Wriedt & Näther, 2010).

In this context, we have recently reported on a discrete aqua complex with the composition Co(NCS)₂(C₆H₄N₂)₂(H₂O)₂ (C₆H₄N₂ = pyri­dine-4-car­bo­ni­trile) in which the metal cations are octa­hedrally coordinated by two N-bonding thio­cyanate anions, two pyri­dine-4-car­bo­ni­trile ligands and two water mol­ecules. Thermogravimetric measurements reveal, that this complex decomposes in separate steps, in which compounds with the composition Co(NCS)₂(C₆H₄N₂)₂ and Co(NCS)₂(C₆H₄N₂) are formed as inter­mediates. PXRD measurements of these residues reveal that crystalline phases have formed and that the residue obtained after the first mass loss consists of a mixture of two different crystalline phases, of which one might be isotypic to the corresponding Mn compound Mn(NCS)₂(C₆H₄N₂)₂ (Wellm et al., 2020).

Starting from these results we tried to prepare single crystals of the two pyri­dine-4-car­bo­ni­trile-deficient coordination compounds, which led to the formation of crystals of the title compound, Co(NCS)₂(C₆H₄N₂)₂ (I), which were characterized by single crystal X-ray diffraction.

2. Structural commentary

The asymmetric unit of (I) consists of two crystallographically independent cobalt cations that occupy centers of inversion as well as two crystallographically independent thio­cyanate anions and two crystallographically independent pyri­dine-4-car­bo­ni­trile coligands that are located in general positions in space group P2₁/c. Each cobalt cation is sixfold coordinated by pairs of N- and S-bonding thio­cyanate anions and two pyri­dine-4-car­bo­ni­trile coligands that coordinate with the pyridine atom to the metal centers in an all-trans CoN₄S₂ octa­hedral coordination environment (Fig. 1). Bond lengths and angles are comparable for both cobalt cations and deviate only slightly from the ideal values, which shows that the octa­hedra are slightly distorted (Table 1). The cobalt cations are linked by pairs of μ-1,3-bridging anionic ligands into linear chains that propagate along the [101] direction (Fig. 2).

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.068 (2)	Co2—S1^i	2.6178 (6)
Co1—S2	2.5836 (7)	Co2—N2	2.0462 (19)
Co1—N11	2.181 (2)	Co2—N21	2.185 (2)
N1—Co1—S2	86.30 (6)	N2—Co2—S1^ii	92.99 (6)
N1^ii—Co1—S2	93.70 (6)	N2—Co2—S1^i	87.01 (6)
N1^ii—Co1—N11	89.37 (8)	N2—Co2—N21^iii	89.60 (8)
N1—Co1—N11	90.63 (8)	N2—Co2—N21	90.40 (8)
N11^ii—Co1—S2	92.18 (6)	N21—Co2—S1^i	88.87 (6)
N11—Co1—S2	87.81 (6)	N21—Co2—S1^ii	91.13 (6)
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 1 Crystal structure of (I) with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) x − 1, y, z - 1; (ii) −x + 2, −y + 1, −z + 1; (iii) −x + 1, −y + 1, −z.

Figure 2 Fragment of the crystal structure of (I) with a view of part of a chain.

It is noted that the title compound is not isotypic to the corresponding Mn compound already reported in the literature, which crystallizes in the monoclinic space group P2₁/n with a = 5.7311 (4) Å, b =17.86665 (15) Å, c = 8.5822 (5) Å and β = 107.624° [V = 837.5 (3) ų at 195 K] (Wellm et al., 2020). Surprisingly, a similar unit cell with the same space group can also be found for the title compound if some of the weak reflections are omitted. However, if the structure is refined in this smaller unit cell, the six-membered rings of the pyri­dine-4-car­bo­ni­trile are disordered over two orientations, which clearly shows that the larger unit cell is correct. In contrast, in the Mn compound with half of the unit-cell volume no disorder is observed, which shows that this unit cell is correct and that this modification is different from that of the title compound.

3. Supra­molecular features

In the extended structure of (I), the [101] chains are packed in a way that is reminiscent of a sandwich-herringbone arrangement (Fig. 3). There are a number of C—H⋯N and C—H⋯S contacts (Table 2) but with long H⋯N and H⋯S distances and with angles far from linearity, indicating that these are very weak inter­actions.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯N1	0.93	2.63	3.126 (4)	114
C15—H15⋯N1^ii	0.93	2.59	3.106 (3)	115
C21—H21⋯N2	0.93	2.61	3.134 (3)	116
C22—H22⋯N12^iv	0.93	2.67	3.287 (4)	124
C24—H24⋯S2^v	0.93	2.98	3.813 (3)	150
C25—H25⋯N2^iii	0.93	2.55	3.065 (4)	115
Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .

Figure 3 Crystal structure of (I) in a view along the [101] direction.

4. Database survey

It is noted that several coordination compounds with pyri­dine-4-car­bo­ni­trile and transition metal thio­cyanates are already reported in the CSD [version 5.43, last update January 2026 (Groom et al., 2016) searched using CONQUEST (Bruno et al., 2002)]. Most of them are combined with Mn(NCS)₂. This includes discrete complexes with the composition Mn(NCS)₂(C₆H₄N₂)₄ (CSD refcode: OJEDOZ; Wellm et al., 2020) and Mn(NCS)₂(C₆H₄N₂)₂(H₂O)₂ (OJEFAN and OJEFAN01; Wellm et al., 2020), which crystallizes in two different modifications. Discrete aqua complexes with the composition Mn(NCS)₂(C₆H₄N₂)₂(H₂O)₂ and additional pyri­dine-4-car­bo­ni­trile as solvate mol­ecules are also known (OJEFER and OJEFUH; Wellm et al., 2020). Compounds with bridging anionic ligands with the composition Mn(NCS)₂(C₆H₄N₂)₂ (OJEFIV; Wellm et al., 2020) and two isomers of Mn(NCS)₂(C₆H₄N₂) (OJEDUF and OJEDUF01; Wellm et al., 2020) are also known.

With nickel, two compounds built up of discrete complexes are reported, viz. Ni(NCS)₂(C₆H₄N₂)₄ (UBUBOL; Clegg & Harrington, 2016) and Ni(NCS)₂(C₆H₄N₂)₂(H₂O)₂ (Näther, 2026). Fe(NCS)₂(C₆H₄N₂)₂(H₂O)₂·(C₆H₄N₂)₂ (KAPQEA; Jochim et al., 2017) also consists of discrete complexes with additional pyri­dine-4-car­bo­ni­trile mol­ecules located in cavities of this structure.

Moreover, compounds with the composition Cd(NCS)₂(C₆H₄N₂)₂ (WUCLUB; Chen et al., 2002) and Cu(NCS)₂(C₆H₄N₂)₂ (ABOVOF; Handy et al., 2017) are known which exhibit the same ratio between metal thio­cyanate and pyri­dine-4-car­bo­ni­trile as observed in the title compound. In both compounds the metal cations are linked by the anionic ligands into chains, but none of these compounds is isotypic to the title compound. The cadmium compound is isotypic to the corresponding manganese compound mentioned above (OJEFIV; Wellm et al., 2020). Finally, in Cd(NCS)₂(C₆H₄N₂) (WUCMAI; Chen et al., 2002) the pyri­dine-4-car­bo­ni­trile ligand acts as a bridging ligand. This compound is isotypic to one of the two modifications of Mn(NCS)₂(C₆H₄N₂) (OJEDUF01; Wellm et al., 2020).

5. Synthesis and crystallization

Co(NCS)₂ and pyri­dine-4-car­bo­ni­trile were purchased from Sigma-Aldrich. 1.00 mmol (175.2 mg) Co(NCS)₂ and 2.00 mmol (208.2 mg) pyri­dine-4-car­bo­ni­trile were stirred in 1 ml of ethanol for 1 d. The precipitate was filtered off and dried in air. Single crystals of (I) in the form of light-red blocks were obtained using the same amount of reactants without stirring.

The asymmetric CN stretching vibration of the thio­cyanate anions is observed at 2102 cm⁻¹ in the IR spectrum, in agreement with the bridging coordination of the anionic ligands (Fig. 4). Powder X-ray diffraction (PXRD) experiments show that the title compound was obtained as a pure phase (Fig. 5). Moreover, comparison of the experimental X-ray powder pattern of the residue obtained after water removal from Co(NCS)₂(C₆H₄N₂)₂(H₂O)₂ reported recently (Näther, 2026) with the calculated powder pattern of the title compound indicate that the title compound has formed in a mixture with a second and unknown modification of Co(NCS)₂(C₆H₄N₂)₂ (Fig. 6).

Figure 4 IR spectrum of (I) with the CN stretching vibration of the thio­cyanate anion shown.

Figure 5 Experimental (top) and calculated (bottom) PXRD patterns for (I).

Figure 6 Experimental (top) PXRD pattern of Co(NCS)2(C6H4N2)2 obtained by water removal from Co(NCS)2(C6H4N2)2(H2O)2 (Wellm et al., 2020) and calculated (bottom) powder pattern for (I).

Powder X-ray diffraction measurements were performed using a Stoe STADI P transmission powder diffractometer with Cu Kα₁ radiation (λ = 1.540598 Å), a Johann-type Ge(111) monochromator and a MYTHEN 1K detector from Dectris.

IR spectroscopy was done using an ATI Mattson Genesis Series FTIR Spectrometer, control software: WINFIRST, from ATI Mattson in ATR mode.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound hydrogen atoms were positioned with idealized geometry and were refined with U_iso(H) = 1.2U_eq(C) using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NCS)2(C6H4N2)2]
Mr	383.31
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	300
a, b, c (Å)	11.1023 (4), 18.2814 (8), 8.9315 (5)
β (°)	112.436 (3)
V (Å^3)	1675.57 (14)
Z	4
Radiation type	Mo Kα
μ (mm^−1)	1.28
Crystal size (mm)	0.17 × 0.12 × 0.09
Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe, 2008)
Tmin, Tmax	0.710, 0.845
No. of measured, independent and observed [I > 4u(I)] reflections	16251, 3288, 2401
Rint	0.043
(sin θ/λ)max (Å^−1)	0.617
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.036, 0.088, 1.07
No. of reflections	3288
No. of parameters	211
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å^−3)	0.38, −0.25
Computer programs: X-AREA and X-RED32 (Stoe, 2008), SHELXT (Sheldrick, 2015a), SHELXL2016/6 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and publCIF (Westrip, 2010).

Supporting information

Computing details

catena-Poly[[bis(pyridine-4-carbonitrile-κN¹)cobalt(II)]-di-µ-thiocyanato-κ²N:S;κ²S:N]

Crystal data

[Co(NCS)2(C6H4N2)2]	F(000) = 772
Mr = 383.31	Dx = 1.520 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.1023 (4) Å	Cell parameters from 13003 reflections
b = 18.2814 (8) Å	θ = 2.0–28.4°
c = 8.9315 (5) Å	µ = 1.28 mm^−1
β = 112.436 (3)°	T = 300 K
V = 1675.57 (14) Å^3	Block, light red
Z = 4	0.17 × 0.12 × 0.09 mm

Data collection

Stoe IPDS 2 diffractometer	3288 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2401 reflections with I > 4u(I)
Plane graphite monochromator	Rint = 0.043
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.0°
ω scans	h = −13→13
Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008)	k = −21→22
Tmin = 0.710, Tmax = 0.845	l = −11→11
16251 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 0.2371P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3288 reflections	Δρmax = 0.38 e Å^−3
211 parameters	Δρmin = −0.25 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	1.000000	0.500000	0.500000	0.04672 (14)
Co2	0.500000	0.500000	0.000000	0.04134 (13)
N1	1.17221 (19)	0.44202 (12)	0.6006 (2)	0.0515 (5)
C1	1.2795 (2)	0.42552 (13)	0.6692 (3)	0.0416 (5)
S1	1.43258 (5)	0.40342 (4)	0.76597 (8)	0.05299 (18)
N2	0.67531 (18)	0.44698 (11)	0.0948 (2)	0.0480 (5)
C2	0.7798 (2)	0.42780 (13)	0.1701 (3)	0.0429 (5)
S2	0.92796 (6)	0.40021 (4)	0.27846 (8)	0.0588 (2)
N11	0.91226 (18)	0.43418 (12)	0.6354 (2)	0.0515 (5)
C11	0.9848 (3)	0.40288 (19)	0.7757 (4)	0.0703 (8)
H11	1.074005	0.411988	0.818576	0.084*
C12	0.9339 (3)	0.35758 (19)	0.8603 (4)	0.0702 (8)
H12	0.987944	0.336118	0.957045	0.084*
C13	0.8022 (3)	0.34469 (14)	0.7996 (3)	0.0543 (6)
C14	0.7265 (2)	0.37688 (15)	0.6556 (3)	0.0563 (6)
H14	0.636912	0.369148	0.611322	0.068*
C15	0.7847 (2)	0.42066 (16)	0.5777 (3)	0.0548 (6)
H15	0.732429	0.441945	0.479851	0.066*
C16	0.7433 (3)	0.29886 (17)	0.8840 (4)	0.0660 (7)
N12	0.6942 (3)	0.26440 (17)	0.9497 (4)	0.0947 (9)
N21	0.42045 (19)	0.42792 (10)	0.1347 (3)	0.0486 (5)
C21	0.4642 (3)	0.35993 (15)	0.1750 (4)	0.0633 (7)
H21	0.534751	0.344242	0.151511	0.076*
C22	0.4097 (3)	0.31194 (17)	0.2500 (4)	0.0708 (8)
H22	0.443326	0.264979	0.276604	0.085*
C23	0.3053 (3)	0.33407 (15)	0.2850 (3)	0.0593 (7)
C24	0.2607 (3)	0.40443 (17)	0.2465 (4)	0.0672 (8)
H24	0.191268	0.421650	0.270553	0.081*
C25	0.3206 (3)	0.44875 (15)	0.1719 (4)	0.0624 (7)
H25	0.289582	0.496223	0.145920	0.075*
C26	0.2421 (3)	0.28496 (19)	0.3578 (4)	0.0767 (9)
N22	0.1929 (3)	0.2449 (2)	0.4133 (4)	0.1074 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0261 (2)	0.0694 (3)	0.0399 (3)	0.0037 (2)	0.00720 (19)	−0.0001 (2)
Co2	0.0275 (2)	0.0449 (2)	0.0449 (3)	0.00325 (17)	0.00625 (18)	0.0008 (2)
N1	0.0356 (11)	0.0663 (13)	0.0450 (12)	0.0026 (10)	0.0068 (9)	−0.0043 (10)
C1	0.0342 (12)	0.0482 (13)	0.0390 (12)	0.0004 (9)	0.0102 (10)	−0.0044 (10)
S1	0.0308 (3)	0.0583 (4)	0.0597 (4)	0.0074 (3)	0.0059 (3)	−0.0112 (3)
N2	0.0322 (10)	0.0524 (11)	0.0503 (12)	0.0033 (9)	0.0058 (9)	−0.0041 (10)
C2	0.0347 (12)	0.0513 (13)	0.0409 (13)	−0.0002 (10)	0.0123 (10)	−0.0039 (11)
S2	0.0333 (3)	0.0803 (5)	0.0525 (4)	0.0156 (3)	0.0050 (3)	−0.0081 (3)
N11	0.0355 (10)	0.0697 (14)	0.0470 (12)	0.0025 (9)	0.0132 (9)	−0.0003 (10)
C11	0.0405 (14)	0.103 (2)	0.0613 (17)	0.0044 (15)	0.0129 (12)	0.0164 (17)
C12	0.0526 (16)	0.092 (2)	0.0625 (18)	0.0084 (15)	0.0186 (14)	0.0204 (16)
C13	0.0560 (16)	0.0497 (14)	0.0602 (16)	−0.0005 (12)	0.0255 (13)	−0.0054 (12)
C14	0.0417 (13)	0.0624 (15)	0.0628 (17)	−0.0056 (12)	0.0177 (12)	−0.0051 (14)
C15	0.0381 (12)	0.0686 (16)	0.0517 (15)	0.0015 (12)	0.0105 (11)	0.0002 (13)
C16	0.0625 (17)	0.0579 (16)	0.075 (2)	−0.0046 (14)	0.0229 (15)	0.0040 (15)
N12	0.085 (2)	0.087 (2)	0.106 (2)	−0.0131 (17)	0.0302 (18)	0.0300 (19)
N21	0.0444 (11)	0.0464 (11)	0.0539 (12)	−0.0002 (9)	0.0174 (10)	−0.0003 (9)
C21	0.0505 (15)	0.0551 (15)	0.086 (2)	0.0088 (12)	0.0282 (14)	0.0146 (15)
C22	0.0577 (16)	0.0540 (16)	0.097 (2)	0.0047 (13)	0.0255 (16)	0.0192 (16)
C23	0.0545 (16)	0.0630 (16)	0.0567 (17)	−0.0097 (13)	0.0171 (13)	0.0045 (14)
C24	0.0701 (19)	0.0651 (17)	0.080 (2)	0.0045 (15)	0.0438 (17)	0.0037 (15)
C25	0.0720 (18)	0.0513 (14)	0.0772 (19)	0.0079 (13)	0.0433 (16)	0.0034 (14)
C26	0.0657 (19)	0.081 (2)	0.081 (2)	−0.0086 (16)	0.0247 (17)	0.0157 (18)
N22	0.087 (2)	0.118 (3)	0.117 (3)	−0.019 (2)	0.038 (2)	0.039 (2)

Geometric parameters (Å, º)

Co1—N1^i	2.068 (2)	C12—H12	0.9300
Co1—N1	2.068 (2)	C12—C13	1.371 (4)
Co1—S2	2.5836 (7)	C13—C14	1.372 (4)
Co1—S2^i	2.5836 (7)	C13—C16	1.440 (4)
Co1—N11^i	2.181 (2)	C14—H14	0.9300
Co1—N11	2.181 (2)	C14—C15	1.373 (4)
Co2—S1^ii	2.6178 (6)	C15—H15	0.9300
Co2—S1^i	2.6178 (6)	C16—N12	1.132 (4)
Co2—N2^iii	2.0462 (19)	N21—C21	1.333 (3)
Co2—N2	2.0462 (19)	N21—C25	1.329 (3)
Co2—N21	2.185 (2)	C21—H21	0.9300
Co2—N21^iii	2.185 (2)	C21—C22	1.376 (4)
N1—C1	1.153 (3)	C22—H22	0.9300
C1—S1	1.636 (2)	C22—C23	1.372 (4)
N2—C2	1.151 (3)	C23—C24	1.374 (4)
C2—S2	1.638 (2)	C23—C26	1.438 (4)
N11—C11	1.333 (3)	C24—H24	0.9300
N11—C15	1.333 (3)	C24—C25	1.372 (4)
C11—H11	0.9300	C25—H25	0.9300
C11—C12	1.380 (4)	C26—N22	1.135 (4)
N1^i—Co1—N1	180.0	C15—N11—Co1	121.45 (17)
N1—Co1—S2	86.30 (6)	C15—N11—C11	117.1 (2)
N1^i—Co1—S2^i	86.29 (6)	N11—C11—H11	118.5
N1^i—Co1—S2	93.70 (6)	N11—C11—C12	123.1 (3)
N1—Co1—S2^i	93.71 (6)	C12—C11—H11	118.5
N1^i—Co1—N11^i	90.63 (8)	C11—C12—H12	120.5
N1^i—Co1—N11	89.37 (8)	C13—C12—C11	119.0 (3)
N1—Co1—N11	90.63 (8)	C13—C12—H12	120.5
N1—Co1—N11^i	89.37 (8)	C12—C13—C14	118.5 (3)
S2—Co1—S2^i	180.00 (2)	C12—C13—C16	121.4 (3)
N11^i—Co1—S2^i	87.82 (6)	C14—C13—C16	120.1 (3)
N11^i—Co1—S2	92.18 (6)	C13—C14—H14	120.5
N11—Co1—S2^i	92.18 (6)	C13—C14—C15	119.1 (2)
N11—Co1—S2	87.81 (6)	C15—C14—H14	120.5
N11^i—Co1—N11	180.0	N11—C15—C14	123.3 (2)
S1^ii—Co2—S1^i	180.00 (3)	N11—C15—H15	118.4
N2—Co2—S1^i	92.99 (6)	C14—C15—H15	118.4
N2—Co2—S1^ii	87.01 (6)	N12—C16—C13	177.9 (4)
N2^iii—Co2—S1^ii	92.99 (6)	C21—N21—Co2	121.93 (18)
N2^iii—Co2—S1^i	87.01 (6)	C25—N21—Co2	121.07 (17)
N2^iii—Co2—N2	180.00 (10)	C25—N21—C21	116.9 (2)
N2—Co2—N21^iii	89.60 (8)	N21—C21—H21	118.5
N2—Co2—N21	90.40 (8)	N21—C21—C22	122.9 (3)
N2^iii—Co2—N21^iii	90.40 (8)	C22—C21—H21	118.5
N2^iii—Co2—N21	89.60 (8)	C21—C22—H22	120.3
N21^iii—Co2—S1^i	88.87 (6)	C23—C22—C21	119.3 (3)
N21^iii—Co2—S1^ii	91.13 (6)	C23—C22—H22	120.3
N21—Co2—S1^ii	88.87 (6)	C22—C23—C24	118.3 (3)
N21—Co2—S1^i	91.13 (6)	C22—C23—C26	121.3 (3)
N21^iii—Co2—N21	180.0	C24—C23—C26	120.4 (3)
C1—N1—Co1	164.1 (2)	C23—C24—H24	120.7
N1—C1—S1	179.0 (2)	C25—C24—C23	118.6 (3)
C1—S1—Co2^iv	100.25 (8)	C25—C24—H24	120.7
C2—N2—Co2	166.71 (19)	N21—C25—C24	123.9 (3)
N2—C2—S2	179.5 (2)	N21—C25—H25	118.0
C2—S2—Co1	100.52 (9)	C24—C25—H25	118.0
C11—N11—Co1	121.36 (17)	N22—C26—C23	178.4 (4)
Co1—N11—C11—C12	−176.3 (2)	C15—N11—C11—C12	0.6 (5)
Co1—N11—C15—C14	177.0 (2)	C16—C13—C14—C15	179.6 (3)
Co2—N21—C21—C22	−175.4 (2)	N21—C21—C22—C23	0.3 (5)
Co2—N21—C25—C24	175.5 (2)	C21—N21—C25—C24	−0.8 (5)
N11—C11—C12—C13	−1.0 (5)	C21—C22—C23—C24	−1.4 (5)
C11—N11—C15—C14	0.1 (4)	C21—C22—C23—C26	177.7 (3)
C11—C12—C13—C14	0.7 (5)	C22—C23—C24—C25	1.4 (4)
C11—C12—C13—C16	−179.0 (3)	C23—C24—C25—N21	−0.3 (5)
C12—C13—C14—C15	0.0 (4)	C25—N21—C21—C22	0.8 (4)
C13—C14—C15—N11	−0.4 (4)	C26—C23—C24—C25	−177.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N1	0.93	2.63	3.126 (4)	114
C15—H15···N1^i	0.93	2.59	3.106 (3)	115
C21—H21···N2	0.93	2.61	3.134 (3)	116
C22—H22···N12^v	0.93	2.67	3.287 (4)	124
C24—H24···S2^vi	0.93	2.98	3.813 (3)	150
C25—H25···N2^iii	0.93	2.55	3.065 (4)	115

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