Influence of ligand positional isomerism on the molecular and supramolecular structures of cobalt(II)-phenyl­imidazole complexes

Duros, V.; Papatriantafyllopoulou, C.; Kitos, A.A.; Tasiopoulos, A.J.; Nastopoulos, V.

doi:10.1107/S205252061900636X

Influence of ligand positional isomerism on the molecular and supramolecular structures of cobalt(II)-phenylimidazole complexes

V. Duros, C. Papatriantafyllopoulou, A. A. Kitos, A. J. Tasiopoulos and V. Nastopoulos

In a study to evaluate the impact of flexible positional isomeric ligands on the coordination geometry and self-assembly process of 3d metal complexes, the synthesis of eight new cobalt(II) complexes with the 2-phenylimidazole (LH) and 5-phenylimidazole (L′H) ligands has been carried out. A variety of parameters/conditions have been probed using the general Co^II/X⁻/LH or L′H (X⁻ = Cl⁻, Br⁻, I⁻, NO₃⁻, NCS⁻, ClO₄⁻, SO₄²⁻) reaction system. Interestingly, X-ray analyses reveal two distinct groups of complexes: reactions with LH only lead to tetrahedral or quasi-tetrahedral complexes {i.e. [CoCl₂(LH)₂] (1), [CoI₂(LH)₂] (2), [Co(NO₃)₂(LH)₂] (3), [Co(NCS)₂(LH)₂] (4)}, whereas L′H favours octahedral coordination {i.e. [Co(L′H)₄(MeCN)(H₂O)]I₂ (5), [Co(L′H)₄(MeCN)(H₂O)](NO₃)₂ (6) and [Co(NCS)₂(L′H)₄)]·2MeOH (7·2MeOH)}. A tetrahedral [Co(NCS)₂(L′H)₂)] (8) complex was also concurrently isolated with complex 7. The effects of the positional isomeric ligands LH and L′H and of the coordinated inorganic anions on the stoichiometry and packing arrangements of the complexes are thoroughly discussed. The supramolecular assembly is firmly directed, in all types of complexes, by robust N—H

X (X = Cl, I, O or S) motifs, leading to varying dimensionalities (1D, 2D or 3D) and packing arrangements. The formation of these motifs has been activated by choosing appropriate anions X, acting as terminal ligands or counterions. At a second level of organization, additional subordinate C—H

X (X = Cl, I, O or S), C—H

π and π

π intermolecular interactions complement the rigidity of the complexes' packing towards compact 3D assemblies. Hirshfeld surface analyses provided insight into the intermolecular interactions, allowed quantification of the individual contact types and comparison between the complexes.

Keywords: positional isomerism; crystal engineering; intermolecular synthons; phenylimidazoles; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205252061900636X/aw5026sup1.cif Contains datablocks global, 1, 2, 3, 4, 5, 6, 7, 8
	Portable Document Format (PDF) file https://doi.org/10.1107/S205252061900636X/aw5026sup10.pdf Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50261sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50262sup3.hkl Contains datablock 2
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50263sup4.hkl Contains datablock 3
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50264sup5.hkl Contains datablock 4
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50265sup6.hkl Contains datablock 5
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50266sup7.hkl Contains datablock 6
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50267sup8.hkl Contains datablock 7
	Structure factor file (CIF format) https://doi.org/10.1107/S205252061900636X/aw50268sup9.hkl Contains datablock 8

CCDC references: 1914027; 1914028; 1914029; 1914030; 1914031; 1914032; 1914033; 1914034

Computing details top

For all structures, data collection: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); cell refinement: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: PLATON (Spek, 2011); Mercury (Bruno et al. 2002); DIAMOND (Brandenburg, 2014); X-SEED (Barbour, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

(1) top

Crystal data top

C₁₈H₁₆Cl₂CoN₄	D_x = 1.551 Mg m⁻³
M_r = 418.18	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 6008 reflections
a = 14.8764 (9) Å	θ = 3.0–29.0°
b = 8.9742 (4) Å	µ = 1.26 mm⁻¹
c = 26.8271 (9) Å	T = 100 K
V = 3581.5 (3) Å³	Prism, blue
Z = 8	0.32 × 0.15 × 0.15 mm
F(000) = 1704

Data collection top

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	6080 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5795 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	R_int = 0.030
ω scans	θ_max = 27.0°, θ_min = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→19
T_min = 0.667, T_max = 1.000	k = −9→11
11547 measured reflections	l = −31→34

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0333P)² + 0.5291P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
6080 reflections	Δρ_max = 0.41 e Å⁻³
464 parameters	Δρ_min = −0.28 e Å⁻³
5 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.495 (15)

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. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
C2A	0.4731 (3)	0.4790 (4)	0.68182 (15)	0.0143 (8)
C2B	0.3825 (2)	0.2020 (4)	0.55021 (14)	0.0146 (7)
C2C	0.6418 (3)	0.2780 (4)	0.46363 (14)	0.0159 (8)
C2D	0.7237 (3)	0.0203 (4)	0.33211 (15)	0.0150 (8)
C4A	0.3852 (3)	0.6551 (4)	0.65507 (14)	0.0173 (8)
H4A	0.3348	0.7052	0.6432	0.021*
C4B	0.3486 (3)	0.0478 (4)	0.60959 (13)	0.0174 (8)
H4B	0.3314	0.0103	0.6405	0.021*
C4C	0.6262 (3)	0.4257 (4)	0.40016 (14)	0.0181 (8)
H4C	0.6128	0.4607	0.3684	0.022*
C4D	0.6410 (3)	−0.1637 (4)	0.35724 (15)	0.0190 (8)
H4D	0.5921	−0.2187	0.3687	0.023*
C5A	0.4648 (3)	0.7178 (4)	0.66531 (15)	0.0218 (8)
H5A	0.4801	0.8177	0.6616	0.026*
C5B	0.3706 (3)	−0.0347 (4)	0.56942 (14)	0.0183 (8)
H5B	0.3714	−0.1381	0.5674	0.022*
C5C	0.6597 (3)	0.5074 (4)	0.43737 (14)	0.0207 (8)
H5C	0.6739	0.6083	0.4363	0.025*
C5D	0.7228 (3)	−0.2188 (4)	0.34705 (15)	0.0215 (9)
H5D	0.7410	−0.3175	0.3501	0.026*
C6A	0.5075 (3)	0.3337 (4)	0.69759 (13)	0.0138 (7)
C6B	0.3999 (3)	0.3350 (4)	0.52053 (14)	0.0178 (8)
C6C	0.6414 (3)	0.1499 (4)	0.49703 (14)	0.0159 (8)
C6D	0.7552 (3)	0.1684 (4)	0.31749 (13)	0.0154 (7)
C7A	0.4515 (3)	0.2365 (4)	0.72295 (15)	0.0176 (8)
H7A	0.3928	0.2642	0.7305	0.021*
C7B	0.4404 (3)	0.4582 (4)	0.54174 (16)	0.0230 (9)
H7B	0.4569	0.4564	0.5752	0.028*
C7C	0.6708 (3)	0.0114 (4)	0.48021 (16)	0.0222 (9)
H7C	0.6929	0.0009	0.4480	0.027*
C7D	0.6998 (3)	0.2604 (4)	0.28959 (14)	0.0175 (8)
H7D	0.6428	0.2281	0.2802	0.021*
C8A	0.4831 (3)	0.0989 (4)	0.73688 (13)	0.0188 (8)
H8A	0.4456	0.0327	0.7536	0.023*
C8B	0.4562 (3)	0.5834 (4)	0.51360 (17)	0.0291 (10)
H8B	0.4831	0.6663	0.5281	0.035*
C8C	0.6672 (3)	−0.1097 (4)	0.51159 (16)	0.0255 (9)
H8C	0.6865	−0.2023	0.5004	0.031*
C8D	0.7296 (3)	0.4011 (4)	0.27574 (14)	0.0191 (8)
H8D	0.6924	0.4635	0.2573	0.023*
C9A	0.5704 (3)	0.0588 (4)	0.72612 (14)	0.0210 (8)
H9A	0.5914	−0.0349	0.7352	0.025*
C9B	0.4321 (3)	0.5869 (5)	0.46344 (16)	0.0318 (11)
H9B	0.4419	0.6722	0.4445	0.038*
C9C	0.6349 (3)	−0.0945 (4)	0.55966 (15)	0.0231 (9)
H9C	0.6318	−0.1771	0.5806	0.028*
C9D	0.8142 (3)	0.4483 (4)	0.28920 (13)	0.0195 (8)
H9D	0.8341	0.5422	0.2796	0.023*
C10A	0.6266 (3)	0.1567 (4)	0.70200 (14)	0.0201 (8)
H10A	0.6858	0.1296	0.6954	0.024*
C10B	0.3936 (3)	0.4627 (5)	0.44212 (16)	0.0282 (10)
H10B	0.3784	0.4633	0.4085	0.034*
C10C	0.6074 (3)	0.0426 (4)	0.57647 (15)	0.0230 (8)
H10C	0.5860	0.0528	0.6089	0.028*
C10D	0.8694 (3)	0.3576 (4)	0.31670 (14)	0.0203 (9)
H10D	0.9262	0.3905	0.3260	0.024*
C11A	0.5956 (3)	0.2948 (4)	0.68754 (14)	0.0184 (8)
H11A	0.6335	0.3612	0.6712	0.022*
C11B	0.3775 (3)	0.3374 (4)	0.47050 (15)	0.0208 (8)
H11B	0.3514	0.2540	0.4559	0.025*
C11C	0.6111 (3)	0.1647 (4)	0.54578 (14)	0.0179 (8)
H11C	0.5934	0.2575	0.5576	0.021*
C11D	0.8405 (3)	0.2165 (4)	0.33060 (14)	0.0192 (8)
H11D	0.8783	0.1543	0.3487	0.023*
N1A	0.5190 (2)	0.6066 (3)	0.68212 (12)	0.0181 (7)
H1A	0.5733 (13)	0.613 (5)	0.6920 (17)	0.027*
N1B	0.3914 (2)	0.0634 (3)	0.53248 (12)	0.0174 (7)
H1B	0.409 (3)	0.043 (5)	0.5028 (8)	0.026*
N1C	0.6691 (2)	0.4142 (3)	0.47731 (12)	0.0202 (7)
H1C	0.692 (3)	0.433 (5)	0.5058 (9)	0.030*
N1D	0.7739 (2)	−0.1022 (3)	0.33140 (12)	0.0186 (7)
H1D	0.8288 (13)	−0.113 (5)	0.3229 (18)	0.028*
N3A	0.3898 (2)	0.5047 (3)	0.66493 (13)	0.0147 (7)
N3B	0.3556 (2)	0.1972 (3)	0.59755 (11)	0.0146 (6)
N3C	0.6147 (2)	0.2811 (3)	0.41633 (12)	0.0151 (6)
N3D	0.6411 (2)	−0.0118 (3)	0.34801 (13)	0.0144 (7)
Cl1	0.20519 (7)	0.48821 (10)	0.58987 (4)	0.0201 (2)
Cl2	0.21558 (6)	0.24886 (9)	0.69847 (3)	0.01686 (19)
Cl3	0.46731 (6)	0.24859 (10)	0.31794 (3)	0.01758 (19)
Cl4	0.45880 (7)	−0.01587 (10)	0.42304 (4)	0.0191 (2)
Co1	0.29988 (3)	0.35776 (5)	0.63889 (2)	0.01224 (11)
Co2	0.54962 (3)	0.12868 (5)	0.37588 (2)	0.01262 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2A	0.0143 (19)	0.0161 (17)	0.0126 (18)	−0.0029 (16)	0.0003 (18)	−0.0015 (13)
C2B	0.0127 (18)	0.0132 (16)	0.0178 (16)	0.0021 (15)	0.0032 (15)	0.0001 (13)
C2C	0.0113 (18)	0.0183 (18)	0.0181 (17)	−0.0027 (15)	0.0024 (15)	−0.0047 (14)
C2D	0.019 (2)	0.0153 (17)	0.0110 (18)	0.0030 (16)	−0.0016 (18)	−0.0017 (13)
C4A	0.020 (2)	0.0126 (16)	0.0192 (17)	0.0007 (15)	−0.0004 (16)	0.0022 (13)
C4B	0.020 (2)	0.0147 (16)	0.0173 (17)	0.0036 (16)	0.0018 (16)	0.0038 (13)
C4C	0.020 (2)	0.0180 (17)	0.0164 (16)	−0.0022 (16)	0.0020 (16)	0.0024 (14)
C4D	0.022 (2)	0.0120 (16)	0.0231 (18)	−0.0024 (16)	0.0029 (17)	−0.0030 (14)
C5A	0.029 (2)	0.0112 (16)	0.025 (2)	−0.0029 (17)	0.0005 (18)	0.0017 (15)
C5B	0.024 (2)	0.0126 (16)	0.0187 (17)	0.0030 (16)	0.0003 (16)	0.0029 (13)
C5C	0.027 (2)	0.0168 (18)	0.0180 (18)	−0.0057 (17)	0.0024 (18)	−0.0001 (14)
C5D	0.026 (2)	0.0132 (17)	0.025 (2)	0.0025 (17)	0.0042 (19)	−0.0008 (14)
C6A	0.0142 (19)	0.0151 (16)	0.0121 (16)	−0.0016 (16)	−0.0028 (15)	−0.0030 (13)
C6B	0.016 (2)	0.0177 (17)	0.0198 (18)	0.0041 (16)	0.0066 (17)	0.0016 (14)
C6C	0.0125 (19)	0.0191 (17)	0.0161 (17)	−0.0004 (15)	−0.0030 (15)	−0.0015 (13)
C6D	0.0152 (19)	0.0183 (17)	0.0128 (17)	0.0003 (16)	0.0021 (15)	−0.0006 (14)
C7A	0.0143 (19)	0.0206 (18)	0.0178 (18)	0.0010 (16)	−0.0001 (15)	0.0000 (14)
C7B	0.026 (2)	0.0190 (18)	0.024 (2)	−0.0003 (18)	0.0101 (18)	−0.0023 (16)
C7C	0.026 (2)	0.0216 (19)	0.0187 (19)	0.0037 (17)	−0.0051 (18)	−0.0067 (15)
C7D	0.0141 (19)	0.0223 (19)	0.0161 (18)	−0.0019 (16)	0.0006 (15)	−0.0005 (14)
C8A	0.022 (2)	0.0186 (17)	0.0158 (18)	−0.0036 (17)	−0.0014 (17)	0.0030 (14)
C8B	0.032 (3)	0.0183 (19)	0.037 (2)	−0.0032 (18)	0.013 (2)	−0.0042 (17)
C8C	0.031 (2)	0.0163 (17)	0.030 (2)	0.0072 (18)	−0.010 (2)	−0.0052 (16)
C8D	0.020 (2)	0.0176 (17)	0.0197 (18)	0.0057 (17)	0.0000 (17)	0.0047 (15)
C9A	0.026 (2)	0.0180 (18)	0.0193 (18)	0.0050 (18)	−0.0046 (18)	−0.0018 (14)
C9B	0.038 (3)	0.022 (2)	0.035 (2)	0.003 (2)	0.017 (2)	0.0139 (17)
C9C	0.026 (2)	0.0185 (18)	0.025 (2)	−0.0029 (18)	−0.0084 (18)	0.0061 (15)
C9D	0.028 (2)	0.0143 (17)	0.0165 (18)	−0.0034 (18)	0.0028 (17)	−0.0014 (14)
C10A	0.015 (2)	0.0263 (19)	0.0188 (18)	0.0061 (16)	−0.0007 (16)	−0.0022 (15)
C10B	0.029 (2)	0.031 (2)	0.024 (2)	0.007 (2)	0.0067 (19)	0.0114 (17)
C10C	0.023 (2)	0.0251 (19)	0.0206 (19)	−0.0042 (18)	−0.0024 (18)	0.0007 (15)
C10D	0.018 (2)	0.025 (2)	0.0173 (18)	−0.0071 (16)	−0.0015 (17)	−0.0053 (14)
C11A	0.0157 (19)	0.0234 (19)	0.0161 (17)	−0.0025 (17)	0.0012 (16)	0.0007 (14)
C11B	0.020 (2)	0.0209 (18)	0.0213 (19)	0.0024 (17)	0.0019 (17)	0.0038 (15)
C11C	0.020 (2)	0.0160 (17)	0.0179 (18)	0.0002 (16)	−0.0031 (16)	−0.0019 (13)
C11D	0.017 (2)	0.0221 (19)	0.0186 (18)	0.0029 (17)	−0.0016 (16)	−0.0003 (14)
N1A	0.0162 (17)	0.0173 (15)	0.0209 (16)	−0.0036 (15)	−0.0041 (15)	0.0004 (13)
N1B	0.0211 (17)	0.0153 (14)	0.0158 (14)	0.0022 (14)	0.0030 (14)	−0.0019 (12)
N1C	0.028 (2)	0.0178 (15)	0.0148 (15)	−0.0074 (15)	−0.0028 (15)	−0.0026 (12)
N1D	0.0160 (17)	0.0169 (15)	0.0230 (17)	0.0068 (14)	0.0042 (15)	0.0036 (13)
N3A	0.0179 (18)	0.0108 (14)	0.0154 (17)	−0.0021 (12)	0.0005 (15)	0.0008 (11)
N3B	0.0161 (16)	0.0118 (14)	0.0161 (15)	0.0029 (13)	0.0010 (13)	0.0020 (11)
N3C	0.0131 (16)	0.0140 (14)	0.0184 (14)	−0.0019 (13)	0.0005 (13)	−0.0028 (11)
N3D	0.0149 (18)	0.0139 (15)	0.0145 (17)	−0.0005 (13)	0.0011 (15)	0.0004 (11)
Cl1	0.0230 (5)	0.0216 (4)	0.0157 (5)	0.0087 (4)	−0.0023 (4)	0.0014 (3)
Cl2	0.0137 (4)	0.0177 (4)	0.0192 (4)	−0.0005 (4)	0.0019 (4)	0.0033 (3)
Cl3	0.0139 (4)	0.0182 (4)	0.0207 (4)	0.0013 (4)	−0.0021 (4)	0.0031 (3)
Cl4	0.0231 (5)	0.0178 (4)	0.0164 (5)	−0.0053 (4)	0.0039 (4)	−0.0017 (3)
Co1	0.0128 (2)	0.0113 (2)	0.0126 (2)	0.00102 (18)	0.0001 (2)	0.00035 (18)
Co2	0.0127 (2)	0.0116 (2)	0.0136 (2)	0.00019 (18)	0.0001 (2)	−0.00131 (18)

Geometric parameters (Å, º) top

C2A—N1A	1.333 (5)	C7C—C8C	1.376 (6)
C2A—N3A	1.340 (5)	C7C—H7C	0.9300
C2A—C6A	1.463 (5)	C7D—C8D	1.389 (5)
C2B—N3B	1.332 (5)	C7D—H7D	0.9300
C2B—N1B	1.338 (5)	C8A—C9A	1.378 (6)
C2B—C6B	1.458 (5)	C8A—H8A	0.9300
C2C—N3C	1.331 (5)	C8B—C9B	1.393 (6)
C2C—N1C	1.340 (5)	C8B—H8B	0.9300
C2C—C6C	1.457 (5)	C8C—C9C	1.383 (6)
C2D—N1D	1.329 (5)	C8C—H8C	0.9300
C2D—N3D	1.333 (5)	C8D—C9D	1.376 (6)
C2D—C6D	1.463 (5)	C8D—H8D	0.9300
C4A—C5A	1.340 (6)	C9A—C10A	1.374 (6)
C4A—N3A	1.377 (4)	C9A—H9A	0.9300
C4A—H4A	0.9300	C9B—C10B	1.378 (6)
C4B—C5B	1.348 (5)	C9B—H9B	0.9300
C4B—N3B	1.382 (4)	C9C—C10C	1.373 (6)
C4B—H4B	0.9300	C9C—H9C	0.9300
C4C—C5C	1.336 (5)	C9D—C10D	1.371 (6)
C4C—N3C	1.379 (4)	C9D—H9D	0.9300
C4C—H4C	0.9300	C10A—C11A	1.378 (5)
C4D—C5D	1.341 (6)	C10A—H10A	0.9300
C4D—N3D	1.386 (4)	C10B—C11B	1.378 (5)
C4D—H4D	0.9300	C10B—H10B	0.9300
C5A—N1A	1.359 (5)	C10C—C11C	1.371 (5)
C5A—H5A	0.9300	C10C—H10C	0.9300
C5B—N1B	1.361 (5)	C10D—C11D	1.388 (5)
C5B—H5B	0.9300	C10D—H10D	0.9300
C5C—N1C	1.367 (5)	C11A—H11A	0.9300
C5C—H5C	0.9300	C11B—H11B	0.9300
C5D—N1D	1.360 (5)	C11C—H11C	0.9300
C5D—H5D	0.9300	C11D—H11D	0.9300
C6A—C11A	1.383 (5)	N1A—H1A	0.852 (13)
C6A—C7A	1.385 (5)	N1B—H1B	0.858 (13)
C6B—C7B	1.382 (6)	N1C—H1C	0.855 (13)
C6B—C11B	1.383 (6)	N1D—H1D	0.852 (13)
C6C—C11C	1.389 (5)	N3A—Co1	2.004 (3)
C6C—C7C	1.393 (5)	N3B—Co1	1.999 (3)
C6D—C7D	1.386 (5)	N3C—Co2	1.997 (3)
C6D—C11D	1.385 (6)	N3D—Co2	2.000 (3)
C7A—C8A	1.373 (5)	Cl1—Co1	2.2548 (11)
C7A—H7A	0.9300	Cl2—Co1	2.2544 (10)
C7B—C8B	1.374 (6)	Cl3—Co2	2.2524 (10)
C7B—H7B	0.9300	Cl4—Co2	2.2603 (11)

N1A—C2A—N3A	109.1 (3)	C10A—C9A—C8A	120.3 (4)
N1A—C2A—C6A	125.8 (4)	C10A—C9A—H9A	119.8
N3A—C2A—C6A	125.0 (3)	C8A—C9A—H9A	119.8
N3B—C2B—N1B	109.8 (3)	C10B—C9B—C8B	119.4 (4)
N3B—C2B—C6B	126.9 (3)	C10B—C9B—H9B	120.3
N1B—C2B—C6B	123.3 (3)	C8B—C9B—H9B	120.3
N3C—C2C—N1C	109.5 (3)	C10C—C9C—C8C	119.8 (4)
N3C—C2C—C6C	127.0 (3)	C10C—C9C—H9C	120.1
N1C—C2C—C6C	123.5 (3)	C8C—C9C—H9C	120.1
N1D—C2D—N3D	110.1 (3)	C10D—C9D—C8D	120.4 (3)
N1D—C2D—C6D	124.7 (4)	C10D—C9D—H9D	119.8
N3D—C2D—C6D	125.3 (3)	C8D—C9D—H9D	119.8
C5A—C4A—N3A	109.2 (3)	C9A—C10A—C11A	120.3 (4)
C5A—C4A—H4A	125.4	C9A—C10A—H10A	119.9
N3A—C4A—H4A	125.4	C11A—C10A—H10A	119.9
C5B—C4B—N3B	109.1 (3)	C9B—C10B—C11B	120.2 (4)
C5B—C4B—H4B	125.4	C9B—C10B—H10B	119.9
N3B—C4B—H4B	125.4	C11B—C10B—H10B	119.9
C5C—C4C—N3C	109.2 (3)	C11C—C10C—C9C	120.4 (4)
C5C—C4C—H4C	125.4	C11C—C10C—H10C	119.8
N3C—C4C—H4C	125.4	C9C—C10C—H10C	119.8
C5D—C4D—N3D	109.0 (4)	C9D—C10D—C11D	120.0 (4)
C5D—C4D—H4D	125.5	C9D—C10D—H10D	120.0
N3D—C4D—H4D	125.5	C11D—C10D—H10D	120.0
C4A—C5A—N1A	106.5 (3)	C10A—C11A—C6A	119.3 (4)
C4A—C5A—H5A	126.8	C10A—C11A—H11A	120.4
N1A—C5A—H5A	126.8	C6A—C11A—H11A	120.4
C4B—C5B—N1B	106.4 (3)	C10B—C11B—C6B	120.5 (4)
C4B—C5B—H5B	126.8	C10B—C11B—H11B	119.8
N1B—C5B—H5B	126.8	C6B—C11B—H11B	119.8
C4C—C5C—N1C	106.7 (3)	C10C—C11C—C6C	120.1 (4)
C4C—C5C—H5C	126.6	C10C—C11C—H11C	119.9
N1C—C5C—H5C	126.6	C6C—C11C—H11C	119.9
C4D—C5D—N1D	106.7 (3)	C6D—C11D—C10D	120.0 (4)
C4D—C5D—H5D	126.7	C6D—C11D—H11D	120.0
N1D—C5D—H5D	126.7	C10D—C11D—H11D	120.0
C11A—C6A—C7A	120.4 (3)	C2A—N1A—C5A	109.0 (3)
C11A—C6A—C2A	120.0 (3)	C2A—N1A—H1A	123 (3)
C7A—C6A—C2A	119.6 (3)	C5A—N1A—H1A	128 (3)
C7B—C6B—C11B	119.5 (4)	C2B—N1B—C5B	108.7 (3)
C7B—C6B—C2B	120.5 (4)	C2B—N1B—H1B	124 (3)
C11B—C6B—C2B	120.0 (3)	C5B—N1B—H1B	128 (3)
C11C—C6C—C7C	119.5 (3)	C2C—N1C—C5C	108.2 (3)
C11C—C6C—C2C	120.3 (3)	C2C—N1C—H1C	123 (3)
C7C—C6C—C2C	120.2 (4)	C5C—N1C—H1C	128 (3)
C7D—C6D—C11D	119.7 (3)	C2D—N1D—C5D	108.6 (3)
C7D—C6D—C2D	119.7 (3)	C2D—N1D—H1D	129 (3)
C11D—C6D—C2D	120.5 (4)	C5D—N1D—H1D	122 (3)
C8A—C7A—C6A	119.6 (4)	C2A—N3A—C4A	106.2 (3)
C8A—C7A—H7A	120.2	C2A—N3A—Co1	128.5 (2)
C6A—C7A—H7A	120.2	C4A—N3A—Co1	123.0 (3)
C8B—C7B—C6B	120.2 (4)	C2B—N3B—C4B	106.1 (3)
C8B—C7B—H7B	119.9	C2B—N3B—Co1	129.1 (2)
C6B—C7B—H7B	119.9	C4B—N3B—Co1	122.5 (2)
C8C—C7C—C6C	119.6 (4)	C2C—N3C—C4C	106.4 (3)
C8C—C7C—H7C	120.2	C2C—N3C—Co2	130.5 (3)
C6C—C7C—H7C	120.2	C4C—N3C—Co2	122.3 (2)
C6D—C7D—C8D	119.7 (3)	C2D—N3D—C4D	105.7 (3)
C6D—C7D—H7D	120.1	C2D—N3D—Co2	127.7 (2)
C8D—C7D—H7D	120.1	C4D—N3D—Co2	123.6 (3)
C7A—C8A—C9A	120.1 (4)	N3B—Co1—N3A	113.02 (13)
C7A—C8A—H8A	120.0	N3B—Co1—Cl2	108.16 (9)
C9A—C8A—H8A	120.0	N3A—Co1—Cl2	114.16 (10)
C7B—C8B—C9B	120.3 (4)	N3B—Co1—Cl1	108.05 (9)
C7B—C8B—H8B	119.8	N3A—Co1—Cl1	106.18 (9)
C9B—C8B—H8B	119.8	Cl2—Co1—Cl1	106.93 (4)
C7C—C8C—C9C	120.5 (4)	N3C—Co2—N3D	107.77 (13)
C7C—C8C—H8C	119.8	N3C—Co2—Cl3	108.14 (9)
C9C—C8C—H8C	119.8	N3D—Co2—Cl3	114.40 (10)
C9D—C8D—C7D	120.1 (3)	N3C—Co2—Cl4	112.26 (9)
C9D—C8D—H8D	119.9	N3D—Co2—Cl4	104.73 (9)
C7D—C8D—H8D	119.9	Cl3—Co2—Cl4	109.60 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···Cl2ⁱ	0.85 (2)	2.46 (3)	3.229 (3)	151 (4)
N1B—H1B···Cl4	0.86 (3)	2.33 (3)	3.183 (3)	179 (6)
N1C—H1C···Cl1ⁱ	0.85 (3)	2.37 (3)	3.190 (3)	161 (4)
N1D—H1D···Cl3ⁱⁱ	0.85 (2)	2.40 (3)	3.184 (3)	154 (4)

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

(2) top

Crystal data top

C₁₈H₁₆CoI₂N₄	F(000) = 1140
M_r = 601.08	D_x = 2.020 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.5817 (4) Å	Cell parameters from 2244 reflections
b = 18.625 (1) Å	θ = 2.9–28.6°
c = 14.2346 (11) Å	µ = 4.00 mm⁻¹
β = 100.448 (7)°	T = 100 K
V = 1976.7 (2) Å³	Plate, blue
Z = 4	0.21 × 0.14 × 0.07 mm

Data collection top

Agilent Technologies SuperNova with Atlas detector diffractometer	2136 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1949 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.022
Detector resolution: 10.4223 pixels mm^-1	θ_max = 27.0°, θ_min = 2.9°
ω scans	h = −9→9
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −21→23
T_min = 0.605, T_max = 1.000	l = −18→8
4313 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	Hydrogen site location: mixed
wR(F²) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0312P)² + 0.5775P] where P = (F_o² + 2F_c²)/3
2136 reflections	(Δ/σ)_max < 0.001
117 parameters	Δρ_max = 0.57 e Å⁻³
1 restraint	Δρ_min = −0.62 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I	0.64585 (2)	0.10658 (2)	0.13296 (2)	0.01864 (8)
Co	0.5000	0.18344 (2)	0.2500	0.01323 (12)
N1	0.1429 (3)	0.31000 (12)	0.06410 (16)	0.0180 (5)
H1	0.114 (4)	0.3442 (12)	0.0256 (18)	0.027*
N3	0.3093 (3)	0.23837 (11)	0.16429 (15)	0.0137 (4)
C7	0.6293 (3)	0.33201 (15)	0.14263 (18)	0.0168 (5)
H7	0.6579	0.2834	0.1480	0.020*
C6	0.4513 (3)	0.35340 (14)	0.12489 (19)	0.0167 (5)
C2	0.3065 (3)	0.30033 (13)	0.11763 (18)	0.0149 (5)
C4	0.1401 (3)	0.20807 (16)	0.13807 (19)	0.0180 (6)
H4	0.1036	0.1645	0.1600	0.022*
C11	0.4104 (4)	0.42593 (15)	0.1160 (2)	0.0259 (6)
H11	0.2913	0.4407	0.1039	0.031*
C9	0.7235 (4)	0.45505 (15)	0.1442 (2)	0.0299 (7)
H9	0.8145	0.4892	0.1514	0.036*
C5	0.0375 (3)	0.25212 (15)	0.0757 (2)	0.0206 (6)
H5	−0.0810	0.2447	0.0464	0.025*
C8	0.7648 (4)	0.38288 (15)	0.1525 (2)	0.0222 (6)
H8	0.8841	0.3683	0.1647	0.027*
C10	0.5460 (4)	0.47631 (16)	0.1250 (3)	0.0356 (8)
H10	0.5176	0.5248	0.1182	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I	0.01936 (11)	0.01558 (12)	0.02040 (12)	0.00516 (6)	0.00205 (8)	−0.00084 (6)
Co	0.0117 (2)	0.0111 (2)	0.0157 (2)	0.000	−0.00068 (18)	0.000
N1	0.0149 (10)	0.0222 (11)	0.0161 (11)	0.0067 (9)	0.0007 (9)	0.0012 (9)
N3	0.0100 (9)	0.0138 (10)	0.0168 (11)	0.0008 (8)	0.0005 (8)	−0.0018 (9)
C7	0.0208 (12)	0.0146 (13)	0.0150 (13)	0.0005 (10)	0.0028 (10)	0.0005 (10)
C6	0.0203 (12)	0.0165 (12)	0.0139 (13)	0.0001 (10)	0.0047 (10)	−0.0010 (10)
C2	0.0150 (11)	0.0160 (12)	0.0131 (12)	0.0041 (9)	0.0008 (10)	−0.0026 (10)
C4	0.0120 (12)	0.0196 (14)	0.0217 (14)	−0.0003 (9)	0.0012 (11)	−0.0046 (11)
C11	0.0236 (13)	0.0193 (14)	0.0359 (17)	0.0063 (11)	0.0086 (13)	0.0033 (13)
C9	0.0302 (16)	0.0206 (14)	0.043 (2)	−0.0093 (12)	0.0178 (14)	−0.0078 (14)
C5	0.0119 (11)	0.0287 (14)	0.0202 (14)	0.0030 (10)	0.0001 (10)	−0.0068 (12)
C8	0.0182 (13)	0.0273 (14)	0.0221 (15)	−0.0025 (11)	0.0064 (11)	−0.0042 (12)
C10	0.0389 (18)	0.0142 (14)	0.058 (2)	−0.0007 (12)	0.0218 (17)	0.0013 (14)

Geometric parameters (Å, º) top

I—Co	2.5915 (3)	C6—C11	1.386 (4)
Co—N3	1.997 (2)	C6—C2	1.467 (3)
Co—N3ⁱ	1.997 (2)	C4—C5	1.348 (4)
Co—Iⁱ	2.5916 (3)	C4—H4	0.9300
N1—C2	1.345 (3)	C11—C10	1.380 (4)
N1—C5	1.369 (4)	C11—H11	0.9300
N1—H1	0.843 (10)	C9—C8	1.381 (4)
N3—C2	1.330 (3)	C9—C10	1.382 (5)
N3—C4	1.389 (3)	C9—H9	0.9300
C7—C6	1.386 (3)	C5—H5	0.9300
C7—C8	1.386 (4)	C8—H8	0.9300
C7—H7	0.9300	C10—H10	0.9300

N3—Co—N3ⁱ	118.35 (11)	N1—C2—C6	123.5 (2)
N3—Co—I	103.67 (6)	C5—C4—N3	108.9 (2)
N3ⁱ—Co—I	109.25 (6)	C5—C4—H4	125.5
N3—Co—Iⁱ	109.25 (6)	N3—C4—H4	125.5
N3ⁱ—Co—Iⁱ	103.67 (6)	C10—C11—C6	120.2 (2)
I—Co—Iⁱ	112.933 (18)	C10—C11—H11	119.9
C2—N1—C5	109.0 (2)	C6—C11—H11	119.9
C2—N1—H1	125 (2)	C8—C9—C10	119.6 (3)
C5—N1—H1	126 (2)	C8—C9—H9	120.2
C2—N3—C4	106.8 (2)	C10—C9—H9	120.2
C2—N3—Co	133.94 (16)	C4—C5—N1	106.2 (2)
C4—N3—Co	119.15 (17)	C4—C5—H5	126.9
C6—C7—C8	120.1 (3)	N1—C5—H5	126.9
C6—C7—H7	120.0	C9—C8—C7	120.3 (3)
C8—C7—H7	120.0	C9—C8—H8	119.9
C7—C6—C11	119.4 (2)	C7—C8—H8	119.9
C7—C6—C2	120.7 (2)	C11—C10—C9	120.4 (3)
C11—C6—C2	119.9 (2)	C11—C10—H10	119.8
N3—C2—N1	109.2 (2)	C9—C10—H10	119.8
N3—C2—C6	127.3 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Iⁱⁱ	0.84 (2)	2.86 (3)	3.584 (2)	144 (2)

Symmetry code: (ii) −x+1/2, −y+1/2, −z.

(3) top

Crystal data top

C₁₈H₁₆CoN₆O₆	F(000) = 964
M_r = 471.30	D_x = 1.596 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.4982 (9) Å	Cell parameters from 2592 reflections
b = 14.9627 (11) Å	θ = 3.2–72.3°
c = 14.5081 (14) Å	µ = 7.32 mm⁻¹
β = 107.938 (10)°	T = 100 K
V = 1961.6 (3) Å³	Prism, purple
Z = 4	0.18 × 0.13 × 0.09 mm

Data collection top

Agilent Technologies SuperNova with Atlas detector diffractometer	3563 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2849 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.041
Detector resolution: 10.4223 pixels mm^-1	θ_max = 68.5°, θ_min = 4.4°
ω scans	h = −11→10
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −18→17
T_min = 0.671, T_max = 1.000	l = −12→17
7276 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: mixed
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0392P)² + 1.633P] where P = (F_o² + 2F_c²)/3
3563 reflections	(Δ/σ)_max = 0.001
286 parameters	Δρ_max = 0.27 e Å⁻³
2 restraints	Δρ_min = −0.45 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Co	0.94789 (5)	0.27868 (3)	0.58536 (3)	0.02162 (14)
N1A	1.3875 (3)	0.33670 (19)	0.60016 (19)	0.0252 (6)
H1A	1.4778 (16)	0.326 (2)	0.606 (3)	0.038*
C2A	1.2830 (3)	0.2755 (2)	0.6001 (2)	0.0228 (6)
N3A	1.1525 (3)	0.31661 (17)	0.58262 (18)	0.0223 (5)
C4A	1.1774 (3)	0.4063 (2)	0.5701 (2)	0.0258 (7)
H4A	1.1056	0.4508	0.5562	0.031*
C5A	1.3229 (3)	0.4190 (2)	0.5812 (2)	0.0270 (7)
H5A	1.3693	0.4729	0.5768	0.032*
C6A	1.3145 (3)	0.1803 (2)	0.6187 (2)	0.0255 (7)
C7A	1.2024 (4)	0.1165 (2)	0.5868 (2)	0.0303 (7)
H7A	1.1078	0.1343	0.5503	0.036*
C8A	1.2313 (4)	0.0269 (2)	0.6094 (3)	0.0392 (9)
H8A	1.1560	−0.0152	0.5885	0.047*
C9A	1.3724 (4)	0.0000 (3)	0.6631 (3)	0.0428 (9)
H9A	1.3914	−0.0597	0.6802	0.051*
C10A	1.4845 (4)	0.0624 (3)	0.6910 (3)	0.0398 (9)
H10A	1.5801	0.0437	0.7243	0.048*
C11A	1.4571 (3)	0.1521 (2)	0.6703 (2)	0.0325 (8)
H11A	1.5334	0.1935	0.6908	0.039*
N1B	1.0491 (3)	0.08421 (19)	0.7992 (2)	0.0283 (6)
H1B	1.102 (4)	0.055 (2)	0.8468 (18)	0.042*
C2B	1.0705 (3)	0.1665 (2)	0.7693 (2)	0.0236 (7)
N3B	0.9615 (3)	0.18704 (17)	0.68944 (18)	0.0230 (6)
C4B	0.8672 (3)	0.1141 (2)	0.6705 (3)	0.0298 (7)
H4B	0.7803	0.1098	0.6190	0.036*
C5B	0.9204 (3)	0.0501 (2)	0.7383 (3)	0.0328 (8)
H5B	0.8784	−0.0053	0.7425	0.039*
C6B	1.1979 (3)	0.2220 (2)	0.8192 (2)	0.0255 (7)
C7B	1.1813 (4)	0.3129 (2)	0.8327 (2)	0.0335 (8)
H7B	1.0884	0.3394	0.8102	0.040*
C8B	1.3046 (4)	0.3640 (3)	0.8800 (3)	0.0439 (10)
H8B	1.2943	0.4249	0.8891	0.053*
C9B	1.4426 (4)	0.3245 (3)	0.9136 (2)	0.0479 (11)
H9B	1.5249	0.3588	0.9454	0.058*
C10B	1.4587 (4)	0.2343 (3)	0.9002 (3)	0.0435 (10)
H10B	1.5519	0.2081	0.9223	0.052*
C11B	1.3374 (3)	0.1829 (3)	0.8542 (2)	0.0332 (8)
H11B	1.3484	0.1219	0.8464	0.040*
N1	0.8206 (3)	0.2518 (2)	0.3997 (2)	0.0318 (7)
O1	0.8483 (2)	0.19681 (15)	0.47246 (15)	0.0282 (5)
O2	0.8512 (2)	0.33213 (17)	0.42164 (18)	0.0376 (6)
O3	0.7668 (3)	0.22440 (19)	0.31765 (17)	0.0450 (7)
N2	0.7467 (3)	0.38976 (18)	0.61369 (18)	0.0249 (6)
O4	0.8840 (2)	0.40133 (15)	0.61863 (16)	0.0281 (5)
O5	0.6984 (2)	0.31153 (14)	0.59877 (15)	0.0251 (5)
O6	0.6716 (2)	0.45384 (16)	0.62207 (18)	0.0362 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0153 (2)	0.0250 (3)	0.0237 (3)	−0.0015 (2)	0.00489 (19)	0.0002 (2)
N1A	0.0148 (11)	0.0335 (15)	0.0290 (15)	0.0004 (11)	0.0091 (11)	−0.0030 (11)
C2A	0.0167 (13)	0.0300 (17)	0.0224 (16)	−0.0009 (12)	0.0072 (12)	−0.0018 (13)
N3A	0.0165 (11)	0.0283 (14)	0.0223 (14)	−0.0009 (10)	0.0059 (10)	−0.0008 (10)
C4A	0.0188 (14)	0.0298 (17)	0.0295 (18)	0.0004 (13)	0.0084 (13)	−0.0006 (13)
C5A	0.0226 (15)	0.0291 (18)	0.0304 (18)	−0.0030 (13)	0.0097 (13)	−0.0014 (13)
C6A	0.0242 (15)	0.0307 (17)	0.0248 (17)	0.0031 (13)	0.0123 (13)	0.0004 (13)
C7A	0.0287 (16)	0.0328 (18)	0.0332 (19)	0.0007 (14)	0.0150 (14)	−0.0055 (14)
C8A	0.042 (2)	0.034 (2)	0.050 (2)	0.0010 (16)	0.0269 (18)	−0.0046 (17)
C9A	0.052 (2)	0.034 (2)	0.054 (2)	0.0158 (18)	0.035 (2)	0.0080 (18)
C10A	0.0361 (19)	0.050 (2)	0.037 (2)	0.0189 (18)	0.0176 (16)	0.0095 (17)
C11A	0.0250 (16)	0.042 (2)	0.0332 (19)	0.0065 (15)	0.0123 (14)	0.0023 (15)
N1B	0.0236 (14)	0.0298 (15)	0.0299 (16)	0.0021 (11)	0.0059 (12)	0.0095 (12)
C2B	0.0192 (14)	0.0277 (17)	0.0257 (17)	0.0023 (12)	0.0097 (13)	0.0017 (13)
N3B	0.0166 (11)	0.0252 (14)	0.0266 (14)	0.0011 (10)	0.0056 (11)	0.0015 (11)
C4B	0.0207 (15)	0.0279 (18)	0.038 (2)	−0.0036 (13)	0.0040 (13)	0.0006 (14)
C5B	0.0256 (16)	0.0264 (18)	0.043 (2)	−0.0018 (14)	0.0062 (15)	0.0043 (15)
C6B	0.0215 (14)	0.0381 (19)	0.0178 (16)	−0.0044 (13)	0.0070 (12)	0.0038 (14)
C7B	0.0283 (16)	0.041 (2)	0.0283 (19)	−0.0076 (15)	0.0049 (14)	0.0046 (15)
C8B	0.052 (2)	0.047 (2)	0.028 (2)	−0.0228 (19)	0.0062 (17)	0.0012 (16)
C9B	0.036 (2)	0.082 (3)	0.0169 (19)	−0.029 (2)	−0.0048 (15)	0.0108 (18)
C10B	0.0231 (17)	0.077 (3)	0.026 (2)	−0.0086 (18)	0.0022 (14)	0.0209 (19)
C11B	0.0221 (15)	0.054 (2)	0.0243 (18)	0.0003 (15)	0.0080 (14)	0.0123 (15)
N1	0.0197 (12)	0.0466 (19)	0.0295 (17)	−0.0027 (12)	0.0082 (12)	0.0008 (13)
O1	0.0253 (11)	0.0360 (13)	0.0213 (12)	−0.0012 (10)	0.0043 (9)	−0.0026 (9)
O2	0.0315 (12)	0.0377 (15)	0.0427 (15)	−0.0051 (11)	0.0102 (11)	0.0076 (11)
O3	0.0389 (14)	0.073 (2)	0.0201 (14)	−0.0050 (13)	0.0050 (11)	−0.0065 (13)
N2	0.0167 (12)	0.0312 (15)	0.0257 (15)	−0.0032 (11)	0.0046 (11)	−0.0016 (11)
O4	0.0135 (9)	0.0312 (12)	0.0397 (13)	−0.0034 (9)	0.0082 (9)	−0.0039 (10)
O5	0.0188 (10)	0.0270 (12)	0.0274 (12)	−0.0042 (9)	0.0041 (9)	−0.0021 (9)
O6	0.0216 (11)	0.0308 (13)	0.0575 (17)	0.0043 (10)	0.0143 (11)	−0.0088 (12)

Geometric parameters (Å, º) top

Co—N3B	2.014 (3)	N1B—C5B	1.368 (4)
Co—O1	2.031 (2)	N1B—H1B	0.838 (10)
Co—N3A	2.037 (2)	C2B—N3B	1.330 (4)
Co—O4	2.037 (2)	C2B—C6B	1.463 (4)
Co—O2	2.404 (2)	N3B—C4B	1.385 (4)
N1A—C2A	1.351 (4)	C4B—C5B	1.353 (5)
N1A—C5A	1.366 (4)	C4B—H4B	0.9300
N1A—H1A	0.852 (10)	C5B—H5B	0.9300
C2A—N3A	1.336 (4)	C6B—C7B	1.390 (5)
C2A—C6A	1.463 (4)	C6B—C11B	1.393 (4)
N3A—C4A	1.384 (4)	C7B—C8B	1.390 (5)
C4A—C5A	1.354 (4)	C7B—H7B	0.9300
C4A—H4A	0.9300	C8B—C9B	1.383 (6)
C5A—H5A	0.9300	C8B—H8B	0.9300
C6A—C11A	1.396 (4)	C9B—C10B	1.378 (6)
C6A—C7A	1.398 (4)	C9B—H9B	0.9300
C7A—C8A	1.388 (5)	C10B—C11B	1.375 (5)
C7A—H7A	0.9300	C10B—H10B	0.9300
C8A—C9A	1.386 (5)	C11B—H11B	0.9300
C8A—H8A	0.9300	N1—O3	1.213 (4)
C9A—C10A	1.379 (5)	N1—O2	1.254 (4)
C9A—H9A	0.9300	N1—O1	1.300 (4)
C10A—C11A	1.383 (5)	N2—O6	1.223 (3)
C10A—H10A	0.9300	N2—O5	1.252 (3)
C11A—H11A	0.9300	N2—O4	1.295 (3)
N1B—C2B	1.341 (4)

N3B—Co—O1	95.77 (10)	C2B—N1B—C5B	109.1 (3)
N3B—Co—N3A	111.28 (10)	C2B—N1B—H1B	129 (3)
O1—Co—N3A	111.25 (9)	C5B—N1B—H1B	122 (3)
N3B—Co—O4	113.00 (10)	N3B—C2B—N1B	109.8 (3)
O1—Co—O4	129.47 (9)	N3B—C2B—C6B	127.0 (3)
N3A—Co—O4	96.29 (9)	N1B—C2B—C6B	123.1 (3)
N3B—Co—O2	152.12 (9)	C2B—N3B—C4B	105.8 (3)
O1—Co—O2	57.49 (9)	C2B—N3B—Co	131.6 (2)
N3A—Co—O2	87.96 (9)	C4B—N3B—Co	120.0 (2)
O4—Co—O2	83.30 (9)	C5B—C4B—N3B	109.8 (3)
C2A—N1A—C5A	109.1 (2)	C5B—C4B—H4B	125.1
C2A—N1A—H1A	126 (3)	N3B—C4B—H4B	125.1
C5A—N1A—H1A	125 (3)	C4B—C5B—N1B	105.4 (3)
N3A—C2A—N1A	109.0 (3)	C4B—C5B—H5B	127.3
N3A—C2A—C6A	127.5 (3)	N1B—C5B—H5B	127.3
N1A—C2A—C6A	123.5 (3)	C7B—C6B—C11B	119.8 (3)
C2A—N3A—C4A	106.6 (2)	C7B—C6B—C2B	120.9 (3)
C2A—N3A—Co	134.7 (2)	C11B—C6B—C2B	119.4 (3)
C4A—N3A—Co	118.38 (19)	C6B—C7B—C8B	119.5 (3)
C5A—C4A—N3A	109.3 (3)	C6B—C7B—H7B	120.2
C5A—C4A—H4A	125.3	C8B—C7B—H7B	120.2
N3A—C4A—H4A	125.3	C9B—C8B—C7B	120.1 (4)
C4A—C5A—N1A	106.0 (3)	C9B—C8B—H8B	119.9
C4A—C5A—H5A	127.0	C7B—C8B—H8B	119.9
N1A—C5A—H5A	127.0	C10B—C9B—C8B	120.2 (3)
C11A—C6A—C7A	119.1 (3)	C10B—C9B—H9B	119.9
C11A—C6A—C2A	120.2 (3)	C8B—C9B—H9B	119.9
C7A—C6A—C2A	120.7 (3)	C11B—C10B—C9B	120.2 (3)
C8A—C7A—C6A	120.4 (3)	C11B—C10B—H10B	119.9
C8A—C7A—H7A	119.8	C9B—C10B—H10B	119.9
C6A—C7A—H7A	119.8	C10B—C11B—C6B	120.2 (4)
C9A—C8A—C7A	120.0 (4)	C10B—C11B—H11B	119.9
C9A—C8A—H8A	120.0	C6B—C11B—H11B	119.9
C7A—C8A—H8A	120.0	O3—N1—O2	124.6 (3)
C10A—C9A—C8A	119.6 (4)	O3—N1—O1	120.1 (3)
C10A—C9A—H9A	120.2	O2—N1—O1	115.3 (3)
C8A—C9A—H9A	120.2	N1—O1—Co	101.58 (18)
C9A—C10A—C11A	121.1 (3)	N1—O2—Co	85.42 (18)
C9A—C10A—H10A	119.4	O6—N2—O5	123.8 (2)
C11A—C10A—H10A	119.4	O6—N2—O4	119.8 (3)
C10A—C11A—C6A	119.7 (3)	O5—N2—O4	116.3 (2)
C10A—C11A—H11A	120.1	N2—O4—Co	103.59 (18)
C6A—C11A—H11A	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O5ⁱ	0.85 (2)	2.14 (2)	2.983 (4)	171 (4)
N1B—H1B···O4ⁱⁱ	0.84 (3)	2.35 (3)	2.974 (4)	132 (3)
N1B—H1B···O6ⁱⁱ	0.84 (3)	2.55 (4)	3.206 (4)	135 (3)

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y−1/2, −z+3/2.

(4) top

Crystal data top

C₂₀H₁₆CoN₆S₂	F(000) = 1896
M_r = 463.44	D_x = 1.482 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 17.5108 (14) Å	Cell parameters from 2206 reflections
b = 13.8088 (13) Å	θ = 4.6–28.3°
c = 18.9150 (16) Å	µ = 1.05 mm⁻¹
β = 114.745 (9)°	T = 100 K
V = 4153.7 (7) Å³	Prism, blue
Z = 8	0.15 × 0.10 × 0.09 mm

Data collection top

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4413 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3003 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	R_int = 0.065
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −22→17
T_min = 0.665, T_max = 1.000	k = −15→17
9606 measured reflections	l = −24→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: mixed
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0617P)²] where P = (F_o² + 2F_c²)/3
4413 reflections	(Δ/σ)_max = 0.001
268 parameters	Δρ_max = 0.90 e Å⁻³
1 restraint	Δρ_min = −0.84 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Co	0.62170 (2)	0.56587 (4)	0.24871 (2)	0.02358 (17)
C2A	0.51801 (18)	0.4464 (2)	0.31250 (18)	0.0227 (7)
C2B	0.71798 (19)	0.4339 (2)	0.18356 (19)	0.0224 (7)
C4A	0.6213 (2)	0.5236 (3)	0.40307 (18)	0.0292 (8)
H4A	0.6694	0.5611	0.4280	0.035*
C4B	0.61548 (19)	0.5123 (3)	0.09384 (18)	0.0275 (8)
H4B	0.5686	0.5517	0.0696	0.033*
C5A	0.5751 (2)	0.4832 (3)	0.4376 (2)	0.0320 (9)
H5A	0.5851	0.4874	0.4898	0.038*
C5B	0.6564 (2)	0.4655 (3)	0.0573 (2)	0.0320 (9)
H5B	0.6434	0.4666	0.0043	0.038*
C6A	0.46063 (18)	0.4052 (2)	0.23887 (19)	0.0239 (8)
C6B	0.77741 (19)	0.3920 (2)	0.25700 (18)	0.0215 (7)
C7A	0.4883 (2)	0.3823 (3)	0.18236 (19)	0.0281 (8)
H7A	0.5448	0.3901	0.1929	0.034*
C7B	0.7523 (2)	0.3711 (3)	0.31584 (18)	0.0254 (8)
H7B	0.6969	0.3819	0.3081	0.030*
C8A	0.4331 (2)	0.3479 (3)	0.1105 (2)	0.0392 (10)
H8A	0.4525	0.3329	0.0729	0.047*
C8B	0.8094 (2)	0.3342 (3)	0.38565 (19)	0.0286 (8)
H8B	0.7922	0.3199	0.4248	0.034*
C9A	0.3495 (2)	0.3357 (3)	0.0945 (2)	0.0475 (12)
H9A	0.3122	0.3132	0.0460	0.057*
C9B	0.8926 (2)	0.3182 (3)	0.3982 (2)	0.0304 (9)
H9B	0.9310	0.2940	0.4457	0.036*
C10A	0.3208 (2)	0.3570 (3)	0.1506 (3)	0.0458 (11)
H10A	0.2645	0.3474	0.1398	0.055*
C10B	0.9176 (2)	0.3383 (3)	0.3397 (2)	0.0296 (8)
H10B	0.9727	0.3264	0.3473	0.036*
C11A	0.37491 (19)	0.3923 (3)	0.2226 (2)	0.0320 (9)
H11A	0.3551	0.4075	0.2598	0.038*
C11B	0.86089 (19)	0.3761 (2)	0.26988 (19)	0.0238 (8)
H11B	0.8785	0.3911	0.2311	0.029*
N1A	0.51046 (17)	0.4350 (2)	0.38003 (17)	0.0283 (7)
H1A	0.4761 (19)	0.397 (2)	0.387 (2)	0.042*
N1B	0.72080 (17)	0.4162 (2)	0.11392 (16)	0.0275 (7)
H1B	0.757 (2)	0.378 (3)	0.110 (2)	0.041*
N3A	0.58572 (15)	0.5002 (2)	0.32495 (15)	0.0252 (6)
N3B	0.65360 (15)	0.4930 (2)	0.17253 (15)	0.0231 (6)
N1	0.52229 (17)	0.6411 (2)	0.18263 (16)	0.0279 (7)
C1	0.4587 (2)	0.6756 (3)	0.14190 (19)	0.0241 (8)
S1	0.36848 (5)	0.72505 (7)	0.08600 (5)	0.0304 (3)
N2	0.72600 (17)	0.6298 (2)	0.31726 (17)	0.0327 (7)
C2	0.7899 (2)	0.6578 (3)	0.36301 (19)	0.0270 (8)
S2	0.87915 (5)	0.69905 (8)	0.42763 (6)	0.0376 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0172 (2)	0.0267 (3)	0.0263 (3)	−0.00093 (17)	0.00859 (18)	−0.0028 (2)
C2A	0.0191 (15)	0.025 (2)	0.0233 (18)	0.0036 (13)	0.0077 (12)	0.0017 (15)
C2B	0.0211 (16)	0.023 (2)	0.0246 (18)	−0.0027 (13)	0.0108 (13)	−0.0010 (15)
C4A	0.0274 (17)	0.036 (2)	0.0211 (19)	0.0004 (16)	0.0073 (13)	−0.0044 (17)
C4B	0.0214 (16)	0.033 (2)	0.0253 (19)	0.0028 (15)	0.0072 (13)	0.0028 (16)
C5A	0.0346 (19)	0.036 (2)	0.024 (2)	0.0059 (17)	0.0110 (14)	0.0002 (17)
C5B	0.0350 (19)	0.038 (2)	0.0205 (19)	0.0004 (17)	0.0086 (14)	−0.0025 (17)
C6A	0.0167 (15)	0.021 (2)	0.0293 (19)	0.0016 (13)	0.0050 (13)	0.0051 (15)
C6B	0.0221 (15)	0.0202 (19)	0.0221 (18)	−0.0007 (13)	0.0092 (13)	−0.0026 (15)
C7A	0.0241 (17)	0.025 (2)	0.028 (2)	−0.0026 (14)	0.0040 (13)	−0.0031 (16)
C7B	0.0199 (15)	0.029 (2)	0.0250 (19)	−0.0001 (14)	0.0076 (13)	0.0012 (16)
C8A	0.039 (2)	0.033 (2)	0.032 (2)	0.0036 (17)	0.0014 (16)	−0.0065 (18)
C8B	0.0295 (18)	0.032 (2)	0.0235 (19)	−0.0010 (15)	0.0101 (14)	0.0029 (16)
C9A	0.029 (2)	0.040 (3)	0.046 (3)	0.0070 (17)	−0.0118 (17)	−0.013 (2)
C9B	0.0238 (17)	0.033 (2)	0.028 (2)	−0.0011 (15)	0.0036 (14)	0.0042 (17)
C10A	0.0164 (17)	0.029 (2)	0.074 (3)	−0.0035 (16)	0.0008 (17)	−0.002 (2)
C10B	0.0207 (16)	0.027 (2)	0.038 (2)	0.0002 (14)	0.0098 (14)	−0.0005 (17)
C11A	0.0204 (17)	0.021 (2)	0.054 (2)	−0.0016 (14)	0.0150 (15)	0.0014 (18)
C11B	0.0263 (17)	0.018 (2)	0.0295 (19)	−0.0005 (13)	0.0144 (14)	−0.0016 (15)
N1A	0.0258 (15)	0.030 (2)	0.0301 (17)	0.0037 (12)	0.0130 (12)	0.0059 (14)
N1B	0.0264 (15)	0.031 (2)	0.0270 (17)	0.0017 (13)	0.0129 (12)	−0.0026 (14)
N3A	0.0187 (13)	0.0319 (18)	0.0231 (15)	0.0006 (12)	0.0067 (10)	−0.0005 (13)
N3B	0.0198 (13)	0.0273 (18)	0.0213 (15)	0.0000 (12)	0.0078 (10)	−0.0008 (13)
N1	0.0270 (15)	0.0261 (18)	0.0360 (18)	0.0025 (13)	0.0185 (13)	0.0038 (14)
C1	0.0290 (18)	0.021 (2)	0.0274 (19)	−0.0037 (14)	0.0171 (14)	−0.0025 (15)
S1	0.0239 (4)	0.0340 (6)	0.0324 (5)	0.0037 (4)	0.0109 (3)	0.0099 (4)
N2	0.0221 (14)	0.037 (2)	0.0411 (19)	−0.0026 (13)	0.0156 (13)	−0.0092 (15)
C2	0.0250 (17)	0.026 (2)	0.034 (2)	0.0021 (15)	0.0168 (15)	−0.0055 (16)
S2	0.0217 (4)	0.0442 (7)	0.0399 (6)	−0.0005 (4)	0.0058 (4)	−0.0176 (5)

Geometric parameters (Å, º) top

Co—N2	1.953 (3)	C7A—C8A	1.381 (4)
Co—N1	1.962 (3)	C7A—H7A	0.9300
Co—N3A	2.015 (3)	C7B—C8B	1.377 (4)
Co—N3B	2.019 (3)	C7B—H7B	0.9300
C2A—N3A	1.334 (4)	C8A—C9A	1.376 (5)
C2A—N1A	1.347 (4)	C8A—H8A	0.9300
C2A—C6A	1.450 (4)	C8B—C9B	1.393 (4)
C2B—N3B	1.335 (4)	C8B—H8B	0.9300
C2B—N1B	1.361 (4)	C9A—C10A	1.382 (6)
C2B—C6B	1.462 (4)	C9A—H9A	0.9300
C4A—C5A	1.355 (5)	C9B—C10B	1.378 (4)
C4A—N3A	1.381 (4)	C9B—H9B	0.9300
C4A—H4A	0.9300	C10A—C11A	1.381 (5)
C4B—C5B	1.350 (4)	C10A—H10A	0.9300
C4B—N3B	1.379 (4)	C10B—C11B	1.380 (4)
C4B—H4B	0.9300	C10B—H10B	0.9300
C5A—N1A	1.370 (4)	C11A—H11A	0.9300
C5A—H5A	0.9300	C11B—H11B	0.9300
C5B—N1B	1.368 (4)	N1A—H1A	0.851 (10)
C5B—H5B	0.9300	N1B—H1B	0.84 (4)
C6A—C7A	1.382 (5)	N1—C1	1.158 (4)
C6A—C11A	1.412 (4)	C1—S1	1.638 (3)
C6B—C7B	1.388 (4)	N2—C2	1.158 (4)
C6B—C11B	1.395 (4)	C2—S2	1.631 (3)

N2—Co—N1	121.15 (13)	C7A—C8A—H8A	120.0
N2—Co—N3A	102.35 (12)	C7B—C8B—C9B	120.7 (3)
N1—Co—N3A	103.56 (11)	C7B—C8B—H8B	119.7
N2—Co—N3B	103.78 (11)	C9B—C8B—H8B	119.7
N1—Co—N3B	104.25 (11)	C8A—C9A—C10A	120.0 (4)
N3A—Co—N3B	123.31 (12)	C8A—C9A—H9A	120.0
N3A—C2A—N1A	109.3 (3)	C10A—C9A—H9A	120.0
N3A—C2A—C6A	126.6 (3)	C10B—C9B—C8B	119.5 (3)
N1A—C2A—C6A	124.1 (3)	C10B—C9B—H9B	120.3
N3B—C2B—N1B	109.2 (3)	C8B—C9B—H9B	120.3
N3B—C2B—C6B	127.5 (3)	C11A—C10A—C9A	120.8 (3)
N1B—C2B—C6B	123.3 (3)	C11A—C10A—H10A	119.6
C5A—C4A—N3A	109.0 (3)	C9A—C10A—H10A	119.6
C5A—C4A—H4A	125.5	C9B—C10B—C11B	120.1 (3)
N3A—C4A—H4A	125.5	C9B—C10B—H10B	119.9
C5B—C4B—N3B	109.8 (3)	C11B—C10B—H10B	119.9
C5B—C4B—H4B	125.1	C10A—C11A—C6A	119.2 (4)
N3B—C4B—H4B	125.1	C10A—C11A—H11A	120.4
C4A—C5A—N1A	106.2 (3)	C6A—C11A—H11A	120.4
C4A—C5A—H5A	126.9	C10B—C11B—C6B	120.5 (3)
N1A—C5A—H5A	126.9	C10B—C11B—H11B	119.7
C4B—C5B—N1B	106.1 (3)	C6B—C11B—H11B	119.7
C4B—C5B—H5B	126.9	C2A—N1A—C5A	108.6 (3)
N1B—C5B—H5B	126.9	C2A—N1A—H1A	126 (2)
C7A—C6A—C11A	119.1 (3)	C5A—N1A—H1A	125 (2)
C7A—C6A—C2A	120.4 (3)	C2B—N1B—C5B	108.4 (3)
C11A—C6A—C2A	120.3 (3)	C2B—N1B—H1B	122 (2)
C7B—C6B—C11B	119.2 (3)	C5B—N1B—H1B	130 (2)
C7B—C6B—C2B	120.4 (3)	C2A—N3A—C4A	106.8 (3)
C11B—C6B—C2B	120.4 (3)	C2A—N3A—Co	130.2 (2)
C8A—C7A—C6A	120.9 (3)	C4A—N3A—Co	121.6 (2)
C8A—C7A—H7A	119.6	C2B—N3B—C4B	106.4 (3)
C6A—C7A—H7A	119.6	C2B—N3B—Co	131.4 (2)
C8B—C7B—C6B	119.9 (3)	C4B—N3B—Co	121.4 (2)
C8B—C7B—H7B	120.0	C1—N1—Co	172.1 (3)
C6B—C7B—H7B	120.0	N1—C1—S1	178.7 (3)
C9A—C8A—C7A	119.9 (4)	C2—N2—Co	172.0 (3)
C9A—C8A—H8A	120.0	N2—C2—S2	179.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S2ⁱ	0.85 (3)	2.51 (3)	3.355 (3)	171 (3)
N1B—H1B···S1ⁱⁱ	0.84 (4)	2.61 (4)	3.451 (3)	173 (3)

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

(5) top

Crystal data top

C₃₈H₃₇CoN₉O·2(I)	D_x = 1.626 Mg m⁻³
M_r = 948.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnn2	Cell parameters from 3415 reflections
a = 11.3550 (12) Å	θ = 3.2–28.7°
b = 12.680 (3) Å	µ = 2.08 mm⁻¹
c = 13.4516 (14) Å	T = 100 K
V = 1936.8 (5) Å³	Prism, red
Z = 2	0.20 × 0.11 × 0.10 mm
F(000) = 938

Data collection top

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	3201 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3101 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	R_int = 0.033
ω scans	θ_max = 27.0°, θ_min = 3.2°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→14
T_min = 0.859, T_max = 1.000	k = −9→16
6159 measured reflections	l = −16→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0352P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3201 reflections	Δρ_max = 0.72 e Å⁻³
251 parameters	Δρ_min = −0.68 e Å⁻³
16 restraints	Absolute structure: Flack x determined using 964 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co	0.5000	0.5000	0.54738 (7)	0.0145 (2)
I	0.52089 (2)	0.68918 (2)	0.88794 (3)	0.02375 (10)
C2A	0.3291 (4)	0.6733 (4)	0.4875 (4)	0.0194 (10)
H2A	0.2967	0.6276	0.4409	0.023*
C2B	0.7337 (4)	0.6137 (4)	0.4862 (4)	0.0198 (10)
H2B	0.7100	0.6226	0.4206	0.024*
C4A	0.4361 (4)	0.7380 (4)	0.6031 (3)	0.0180 (9)
H4A	0.4942	0.7443	0.6515	0.022*
C4B	0.7356 (4)	0.5735 (4)	0.6418 (3)	0.0188 (9)
H4B	0.7118	0.5480	0.7034	0.023*
C5A	0.3564 (4)	0.8138 (4)	0.5806 (4)	0.0186 (10)
C5B	0.8416 (4)	0.6185 (4)	0.6228 (3)	0.0180 (10)
C6A	0.3348 (4)	0.9197 (4)	0.6201 (4)	0.0203 (10)
C6B	0.9423 (4)	0.6363 (4)	0.6870 (3)	0.0193 (10)
C7A	0.2883 (4)	0.9995 (4)	0.5620 (4)	0.0280 (12)
H7A	0.2696	0.9858	0.4959	0.034*
C7B	1.0549 (4)	0.6521 (5)	0.6494 (4)	0.0268 (11)
H7B	1.0666	0.6546	0.5811	0.032*
C8A	0.2689 (5)	1.0991 (4)	0.6000 (4)	0.0334 (13)
H8A	0.2373	1.1518	0.5600	0.040*
C8B	1.1496 (4)	0.6640 (5)	0.7132 (4)	0.0291 (12)
H8B	1.2250	0.6726	0.6873	0.035*
C9A	0.2971 (4)	1.1200 (4)	0.6990 (4)	0.0298 (12)
H9A	0.2849	1.1869	0.7254	0.036*
C9B	1.1331 (4)	0.6633 (5)	0.8147 (4)	0.0298 (12)
H9B	1.1967	0.6733	0.8573	0.036*
C10A	0.3432 (4)	1.0411 (5)	0.7571 (4)	0.0296 (12)
H10A	0.3622	1.0552	0.8230	0.035*
C10B	1.0223 (4)	0.6479 (6)	0.8525 (5)	0.0403 (17)
H10B	1.0112	0.6455	0.9209	0.048*
C11A	0.3616 (4)	0.9410 (4)	0.7195 (4)	0.0255 (11)
H11A	0.3918	0.8881	0.7601	0.031*
C11B	0.9274 (4)	0.6357 (5)	0.7897 (4)	0.0343 (14)
H11B	0.8524	0.6270	0.8162	0.041*
N1A	0.2893 (3)	0.7714 (3)	0.5050 (3)	0.0208 (8)
H1A	0.229 (4)	0.798 (4)	0.476 (4)	0.031*
N1B	0.8393 (3)	0.6425 (3)	0.5223 (3)	0.0196 (8)
H1B	0.896 (3)	0.674 (4)	0.493 (4)	0.029*
N3A	0.4192 (3)	0.6500 (3)	0.5445 (3)	0.0174 (8)
N3B	0.6680 (3)	0.5710 (3)	0.5566 (3)	0.0175 (8)
O1	0.5000	0.5000	0.7070 (4)	0.0183 (10)
H1	0.498 (5)	0.552 (3)	0.744 (4)	0.027*
N1	0.5000	0.5000	0.3865 (6)	0.0240 (12)
C12	0.506 (2)	0.5201 (10)	0.3025 (7)	0.020 (4)	0.5
C13	0.5101 (13)	0.5390 (14)	0.1980 (10)	0.046 (4)	0.5
H13A	0.5907	0.5405	0.1764	0.069*	0.5
H13B	0.4736	0.6055	0.1835	0.069*	0.5
H13C	0.4690	0.4837	0.1637	0.069*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0139 (3)	0.0158 (5)	0.0137 (4)	−0.0006 (4)	0.000	0.000
I	0.02090 (14)	0.03002 (19)	0.02032 (16)	0.00471 (11)	−0.00410 (17)	−0.00928 (17)
C2A	0.019 (2)	0.020 (2)	0.020 (2)	0.001 (2)	−0.0031 (18)	−0.001 (2)
C2B	0.018 (2)	0.020 (2)	0.021 (2)	−0.001 (2)	0.0017 (17)	−0.001 (2)
C4A	0.0156 (18)	0.022 (2)	0.017 (2)	−0.002 (2)	−0.0007 (17)	0.001 (2)
C4B	0.0167 (19)	0.023 (2)	0.016 (2)	−0.002 (2)	−0.0013 (16)	0.001 (2)
C5A	0.0149 (19)	0.022 (2)	0.019 (2)	−0.0009 (19)	0.0020 (17)	0.0035 (19)
C5B	0.0141 (19)	0.018 (2)	0.022 (2)	0.000 (2)	0.0014 (18)	−0.001 (2)
C6A	0.0147 (19)	0.020 (2)	0.026 (3)	0.003 (2)	0.0022 (18)	0.000 (2)
C6B	0.0138 (18)	0.022 (2)	0.022 (2)	−0.003 (2)	0.0004 (18)	−0.002 (2)
C7A	0.034 (2)	0.023 (3)	0.026 (3)	0.005 (2)	0.003 (2)	0.003 (2)
C7B	0.020 (2)	0.034 (3)	0.026 (3)	−0.004 (2)	0.003 (2)	0.006 (2)
C8A	0.038 (3)	0.023 (3)	0.039 (3)	0.007 (3)	0.008 (3)	0.007 (3)
C8B	0.016 (2)	0.039 (3)	0.032 (3)	−0.006 (2)	−0.001 (2)	0.010 (3)
C9A	0.026 (2)	0.021 (3)	0.042 (3)	0.001 (2)	0.010 (2)	−0.007 (3)
C9B	0.020 (2)	0.038 (3)	0.031 (3)	−0.001 (2)	−0.006 (2)	−0.005 (3)
C10A	0.020 (2)	0.034 (3)	0.035 (3)	−0.001 (2)	0.002 (2)	−0.007 (3)
C10B	0.023 (3)	0.078 (5)	0.021 (3)	−0.003 (3)	0.0000 (19)	−0.014 (3)
C11A	0.019 (2)	0.028 (3)	0.030 (3)	0.001 (2)	−0.001 (2)	−0.001 (2)
C11B	0.017 (2)	0.062 (4)	0.025 (3)	−0.003 (3)	0.005 (2)	−0.008 (3)
N1A	0.0156 (17)	0.025 (2)	0.021 (2)	0.0019 (18)	−0.0049 (15)	0.0039 (19)
N1B	0.0159 (16)	0.024 (2)	0.0185 (19)	−0.0032 (17)	0.0018 (14)	0.0021 (18)
N3A	0.0147 (14)	0.0175 (19)	0.0200 (19)	−0.0017 (16)	0.0002 (15)	0.0026 (17)
N3B	0.0139 (14)	0.021 (2)	0.0178 (18)	0.0008 (16)	−0.0013 (14)	0.0009 (18)
O1	0.025 (2)	0.015 (3)	0.015 (3)	−0.004 (2)	0.000	0.000
N1	0.023 (2)	0.028 (3)	0.021 (3)	0.001 (2)	0.000	0.000
C12	0.014 (5)	0.020 (11)	0.024 (5)	−0.001 (9)	0.003 (5)	−0.002 (4)
C13	0.030 (5)	0.068 (10)	0.039 (7)	0.015 (7)	0.001 (5)	−0.004 (7)

Geometric parameters (Å, º) top

Co—N3Aⁱ	2.112 (4)	C7B—C8B	1.384 (7)
Co—N3A	2.113 (4)	C7B—H7B	0.9300
Co—N3B	2.113 (3)	C8A—C9A	1.395 (8)
Co—N3Bⁱ	2.113 (3)	C8A—H8A	0.9300
Co—O1	2.148 (5)	C8B—C9B	1.379 (7)
Co—N1	2.163 (9)	C8B—H8B	0.9300
C2A—N3A	1.312 (6)	C9A—C10A	1.373 (8)
C2A—N1A	1.344 (6)	C9A—H9A	0.9300
C2A—H2A	0.9300	C9B—C10B	1.371 (7)
C2B—N3B	1.322 (6)	C9B—H9B	0.9300
C2B—N1B	1.344 (6)	C10A—C11A	1.383 (8)
C2B—H2B	0.9300	C10A—H10A	0.9300
C4A—C5A	1.355 (6)	C10B—C11B	1.379 (7)
C4A—N3A	1.378 (6)	C10B—H10B	0.9300
C4A—H4A	0.9300	C11A—H11A	0.9300
C4B—C5B	1.356 (6)	C11B—H11B	0.9300
C4B—N3B	1.379 (5)	N1A—H1A	0.85 (2)
C4B—H4B	0.9300	N1B—H1B	0.853 (13)
C5A—N1A	1.379 (6)	O1—H1	0.829 (13)
C5A—C6A	1.465 (6)	N1—C12ⁱ	1.161 (12)
C5B—N1B	1.386 (6)	N1—C12	1.161 (12)
C5B—C6B	1.451 (6)	C12—C12ⁱ	0.53 (2)
C6A—C7A	1.383 (7)	C12—C13	1.427 (16)
C6A—C11A	1.397 (7)	C12—C13ⁱ	1.603 (17)
C6B—C7B	1.389 (6)	C13—H13A	0.9600
C6B—C11B	1.391 (7)	C13—H13B	0.9600
C7A—C8A	1.380 (7)	C13—H13C	0.9600
C7A—H7A	0.9300

N3Aⁱ—Co—N3A	177.9 (2)	C9B—C8B—C7B	120.5 (5)
N3Aⁱ—Co—N3B	89.57 (13)	C9B—C8B—H8B	119.8
N3A—Co—N3B	90.55 (13)	C7B—C8B—H8B	119.8
N3Aⁱ—Co—N3Bⁱ	90.55 (13)	C10A—C9A—C8A	119.5 (5)
N3A—Co—N3Bⁱ	89.57 (13)	C10A—C9A—H9A	120.3
N3B—Co—N3Bⁱ	173.2 (2)	C8A—C9A—H9A	120.3
N3Aⁱ—Co—O1	91.03 (11)	C10B—C9B—C8B	119.5 (5)
N3A—Co—O1	91.03 (11)	C10B—C9B—H9B	120.2
N3B—Co—O1	86.62 (11)	C8B—C9B—H9B	120.2
N3Bⁱ—Co—O1	86.62 (11)	C9A—C10A—C11A	121.2 (5)
N3Aⁱ—Co—N1	88.97 (11)	C9A—C10A—H10A	119.4
N3A—Co—N1	88.97 (11)	C11A—C10A—H10A	119.4
N3B—Co—N1	93.38 (11)	C9B—C10B—C11B	120.4 (6)
N3Bⁱ—Co—N1	93.38 (11)	C9B—C10B—H10B	119.8
O1—Co—N1	180.0	C11B—C10B—H10B	119.8
N3A—C2A—N1A	111.6 (4)	C10A—C11A—C6A	119.7 (5)
N3A—C2A—H2A	124.2	C10A—C11A—H11A	120.2
N1A—C2A—H2A	124.2	C6A—C11A—H11A	120.2
N3B—C2B—N1B	110.9 (4)	C10B—C11B—C6B	120.8 (5)
N3B—C2B—H2B	124.6	C10B—C11B—H11B	119.6
N1B—C2B—H2B	124.6	C6B—C11B—H11B	119.6
C5A—C4A—N3A	110.7 (4)	C2A—N1A—C5A	107.7 (4)
C5A—C4A—H4A	124.6	C2A—N1A—H1A	123 (4)
N3A—C4A—H4A	124.6	C5A—N1A—H1A	129 (4)
C5B—C4B—N3B	110.3 (4)	C2B—N1B—C5B	108.0 (4)
C5B—C4B—H4B	124.8	C2B—N1B—H1B	130 (4)
N3B—C4B—H4B	124.8	C5B—N1B—H1B	122 (4)
C4A—C5A—N1A	104.9 (4)	C2A—N3A—C4A	105.1 (4)
C4A—C5A—C6A	133.0 (5)	C2A—N3A—Co	123.5 (3)
N1A—C5A—C6A	122.1 (4)	C4A—N3A—Co	131.1 (3)
C4B—C5B—N1B	105.0 (4)	C2B—N3B—C4B	105.8 (4)
C4B—C5B—C6B	130.8 (4)	C2B—N3B—Co	129.9 (3)
N1B—C5B—C6B	124.1 (4)	C4B—N3B—Co	124.1 (3)
C7A—C6A—C11A	118.8 (5)	Co—O1—H1	127 (5)
C7A—C6A—C5A	122.0 (5)	C12ⁱ—N1—Co	166.9 (6)
C11A—C6A—C5A	119.2 (5)	C12—N1—Co	166.9 (6)
C7B—C6B—C11B	118.3 (4)	C12ⁱ—C12—N1	76.9 (6)
C7B—C6B—C5B	122.1 (4)	C12ⁱ—C12—C13	99.9 (8)
C11B—C6B—C5B	119.6 (4)	N1—C12—C13	176.7 (13)
C8A—C7A—C6A	121.4 (6)	C12ⁱ—C12—C13ⁱ	61.3 (7)
C8A—C7A—H7A	119.3	N1—C12—C13ⁱ	138.2 (11)
C6A—C7A—H7A	119.3	C12—C13—H13A	109.5
C8B—C7B—C6B	120.4 (5)	C12—C13—H13B	109.5
C8B—C7B—H7B	119.8	H13A—C13—H13B	109.5
C6B—C7B—H7B	119.8	C12—C13—H13C	109.5
C7A—C8A—C9A	119.4 (5)	H13A—C13—H13C	109.5
C7A—C8A—H8A	120.3	H13B—C13—H13C	109.5
C9A—C8A—H8A	120.3

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···Iⁱⁱ	0.86 (5)	2.65 (5)	3.467 (4)	160 (4)
N1B—H1B···Iⁱⁱ	0.85 (4)	2.65 (5)	3.475 (4)	163 (4)
O1—H1···I	0.83 (5)	2.62 (5)	3.426 (4)	167 (4)

Symmetry code: (ii) x−1/2, −y+3/2, z−1/2.

(6) top

Crystal data top

C₃₈H₃₇CoN₉O·2(NO₃)	D_x = 1.403 Mg m⁻³
M_r = 818.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnn2	Cell parameters from 3240 reflections
a = 11.3655 (6) Å	θ = 4.4–28.9°
b = 12.5153 (7) Å	µ = 0.51 mm⁻¹
c = 13.6247 (6) Å	T = 100 K
V = 1938.01 (17) Å³	Prism, purple
Z = 2	0.20 × 0.12 × 0.12 mm
F(000) = 850

Data collection top

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	3470 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3354 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	R_int = 0.026
ω scans	θ_max = 27.0°, θ_min = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→14
T_min = 0.853, T_max = 1.000	k = −15→14
6658 measured reflections	l = −17→17

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.033P)² + 0.7309P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.072	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.32 e Å⁻³
3470 reflections	Δρ_min = −0.23 e Å⁻³
279 parameters	Absolute structure: Refined as an inversion twin.
10 restraints	Absolute structure parameter: 0.178 (17)

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co	0.5000	0.0000	0.29392 (4)	0.01557 (12)
N1A	0.1533 (2)	0.13514 (19)	0.32243 (16)	0.0197 (5)
H1A	0.102 (3)	0.163 (3)	0.359 (2)	0.029*
C2A	0.2608 (3)	0.1076 (2)	0.3574 (2)	0.0221 (6)
H2A	0.2824	0.1116	0.4231	0.026*
N3A	0.33061 (17)	0.07466 (15)	0.28666 (18)	0.0190 (4)
C4A	0.2646 (2)	0.0826 (2)	0.2022 (2)	0.0213 (6)
H4A	0.2919	0.0650	0.1399	0.026*
C5A	0.1546 (2)	0.1193 (2)	0.2215 (2)	0.0194 (5)
C6A	0.0544 (2)	0.1385 (2)	0.1565 (2)	0.0208 (5)
C7A	−0.0603 (3)	0.1499 (3)	0.1911 (2)	0.0340 (7)
H7A	−0.0747	0.1480	0.2582	0.041*
C8A	−0.1534 (3)	0.1640 (3)	0.1262 (3)	0.0344 (7)
H8A	−0.2294	0.1722	0.1503	0.041*
C9A	−0.1337 (3)	0.1660 (3)	0.0267 (3)	0.0317 (7)
H9A	−0.1960	0.1755	−0.0167	0.038*
C10A	−0.0210 (3)	0.1539 (4)	−0.0079 (2)	0.0461 (10)
H10A	−0.0073	0.1549	−0.0752	0.055*
C11A	0.0718 (3)	0.1402 (3)	0.0558 (2)	0.0383 (8)
H11A	0.1475	0.1320	0.0308	0.046*
N1B	0.7095 (2)	0.27619 (19)	0.33912 (18)	0.0224 (5)
H1B	0.766 (2)	0.303 (3)	0.370 (2)	0.034*
C2B	0.6716 (2)	0.1766 (2)	0.3566 (2)	0.0222 (6)
H2B	0.7032	0.1315	0.4041	0.027*
N3B	0.58371 (17)	0.15045 (15)	0.29784 (19)	0.0182 (4)
C4B	0.5650 (2)	0.2393 (2)	0.2396 (2)	0.0196 (5)
H4B	0.5077	0.2447	0.1911	0.023*
C5B	0.6429 (2)	0.3178 (2)	0.26387 (19)	0.0192 (5)
C6B	0.6633 (2)	0.4243 (2)	0.2216 (2)	0.0227 (5)
C7B	0.7044 (3)	0.5090 (2)	0.2783 (2)	0.0317 (7)
H7B	0.7198	0.4988	0.3447	0.038*
C8B	0.7224 (3)	0.6087 (2)	0.2360 (3)	0.0399 (8)
H8B	0.7501	0.6649	0.2742	0.048*
C9B	0.6995 (3)	0.6247 (3)	0.1378 (3)	0.0355 (8)
H9B	0.7116	0.6915	0.1098	0.043*
C10B	0.6586 (3)	0.5410 (3)	0.0809 (3)	0.0341 (7)
H10B	0.6424	0.5519	0.0147	0.041*
C11B	0.6416 (3)	0.4409 (2)	0.1225 (2)	0.0280 (6)
H11B	0.6155	0.3846	0.0837	0.034*
O1	0.5000	0.0000	0.1352 (3)	0.0223 (8)
H1	0.480 (3)	−0.050 (2)	0.100 (3)	0.034*
N1	0.5000	0.0000	0.4543 (3)	0.0248 (10)
C12	0.496 (2)	0.0187 (9)	0.5362 (4)	0.027 (3)	0.5
C13	0.4917 (9)	0.0380 (7)	0.6421 (5)	0.051 (3)	0.5
H13A	0.4173	0.0140	0.6673	0.076*	0.5
H13B	0.5005	0.1130	0.6547	0.076*	0.5
H13C	0.5541	−0.0005	0.6737	0.076*	0.5
N2	0.4680 (2)	0.1961 (2)	−0.03418 (18)	0.0248 (5)
O2	0.56214 (19)	0.1728 (2)	0.00745 (17)	0.0369 (5)
O3	0.45595 (19)	0.28495 (17)	−0.07561 (16)	0.0319 (5)
O4	0.38331 (19)	0.13228 (18)	−0.03354 (19)	0.0400 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0135 (2)	0.0151 (2)	0.0180 (2)	0.00016 (18)	0.000	0.000
N1A	0.0153 (10)	0.0233 (11)	0.0204 (11)	0.0044 (9)	0.0015 (9)	−0.0025 (9)
C2A	0.0223 (13)	0.0236 (14)	0.0202 (12)	0.0010 (11)	−0.0004 (12)	−0.0015 (10)
N3A	0.0167 (9)	0.0180 (9)	0.0222 (10)	0.0003 (8)	−0.0009 (12)	−0.0007 (10)
C4A	0.0170 (13)	0.0256 (14)	0.0215 (12)	0.0008 (11)	0.0000 (12)	0.0001 (10)
C5A	0.0187 (13)	0.0180 (12)	0.0215 (12)	−0.0002 (10)	0.0000 (12)	0.0010 (11)
C6A	0.0160 (13)	0.0200 (13)	0.0263 (13)	−0.0004 (11)	−0.0007 (12)	−0.0011 (10)
C7A	0.0214 (15)	0.051 (2)	0.0291 (15)	0.0078 (15)	0.0011 (13)	−0.0082 (14)
C8A	0.0199 (14)	0.0449 (18)	0.0385 (16)	0.0089 (14)	−0.0013 (14)	−0.0102 (15)
C9A	0.0209 (14)	0.0388 (17)	0.0354 (15)	0.0005 (13)	−0.0076 (14)	0.0069 (14)
C10A	0.0256 (15)	0.087 (3)	0.0260 (16)	−0.0017 (19)	−0.0013 (15)	0.0146 (18)
C11A	0.0170 (14)	0.070 (2)	0.0283 (15)	0.0013 (15)	0.0053 (14)	0.0074 (16)
N1B	0.0182 (10)	0.0216 (11)	0.0274 (11)	−0.0035 (9)	−0.0036 (10)	−0.0031 (9)
C2B	0.0201 (13)	0.0199 (13)	0.0268 (13)	0.0013 (11)	−0.0028 (12)	0.0018 (11)
N3B	0.0147 (9)	0.0180 (9)	0.0217 (10)	−0.0007 (8)	−0.0015 (11)	0.0011 (10)
C4B	0.0173 (11)	0.0187 (12)	0.0227 (12)	0.0018 (10)	0.0003 (11)	−0.0005 (10)
C5B	0.0164 (12)	0.0186 (12)	0.0225 (12)	0.0013 (10)	0.0017 (11)	−0.0006 (10)
C6B	0.0191 (12)	0.0172 (12)	0.0317 (13)	0.0001 (10)	0.0067 (13)	−0.0008 (11)
C7B	0.0402 (16)	0.0226 (13)	0.0322 (19)	−0.0054 (12)	0.0054 (15)	−0.0030 (12)
C8B	0.048 (2)	0.0204 (14)	0.051 (2)	−0.0072 (14)	0.0115 (19)	−0.0090 (14)
C9B	0.0349 (17)	0.0237 (15)	0.0480 (19)	−0.0002 (13)	0.0133 (16)	0.0089 (13)
C10B	0.0307 (16)	0.0326 (16)	0.0391 (17)	0.0001 (13)	0.0063 (15)	0.0101 (14)
C11B	0.0247 (14)	0.0248 (14)	0.0345 (15)	−0.0016 (12)	0.0018 (14)	0.0025 (12)
O1	0.0227 (18)	0.024 (2)	0.0201 (17)	0.0036 (12)	0.000	0.000
N1	0.024 (2)	0.028 (2)	0.022 (2)	−0.0036 (14)	0.000	0.000
C12	0.021 (4)	0.032 (10)	0.027 (2)	−0.010 (9)	−0.001 (4)	−0.003 (3)
C13	0.044 (4)	0.083 (7)	0.024 (3)	−0.020 (6)	−0.002 (4)	−0.009 (3)
N2	0.0223 (11)	0.0323 (13)	0.0198 (10)	−0.0005 (11)	−0.0003 (11)	0.0024 (10)
O2	0.0235 (11)	0.0487 (14)	0.0384 (12)	−0.0037 (10)	−0.0136 (10)	0.0098 (10)
O3	0.0290 (10)	0.0324 (12)	0.0344 (11)	−0.0022 (9)	0.0029 (10)	0.0121 (10)
O4	0.0254 (10)	0.0401 (13)	0.0543 (14)	−0.0111 (10)	−0.0127 (12)	0.0207 (11)

Geometric parameters (Å, º) top

Co—N3Bⁱ	2.1103 (19)	N1B—H1B	0.84 (2)
Co—N3B	2.1103 (19)	C2B—N3B	1.321 (3)
Co—N3A	2.1423 (19)	C2B—H2B	0.9300
Co—N3Aⁱ	2.1423 (19)	N3B—C4B	1.382 (3)
Co—O1	2.163 (3)	C4B—C5B	1.363 (4)
Co—N1	2.186 (4)	C4B—H4B	0.9300
N1A—C2A	1.356 (4)	C5B—C6B	1.471 (4)
N1A—C5A	1.390 (4)	C6B—C11B	1.388 (4)
N1A—H1A	0.84 (2)	C6B—C7B	1.393 (4)
C2A—N3A	1.315 (4)	C7B—C8B	1.390 (4)
C2A—H2A	0.9300	C7B—H7B	0.9300
N3A—C4A	1.378 (4)	C8B—C9B	1.378 (5)
C4A—C5A	1.358 (4)	C8B—H8B	0.9300
C4A—H4A	0.9300	C9B—C10B	1.383 (5)
C5A—C6A	1.462 (4)	C9B—H9B	0.9300
C6A—C11A	1.386 (4)	C10B—C11B	1.389 (4)
C6A—C7A	1.394 (4)	C10B—H10B	0.9300
C7A—C8A	1.390 (5)	C11B—H11B	0.9300
C7A—H7A	0.9300	O1—H1	0.82 (2)
C8A—C9A	1.374 (5)	N1—C12	1.140 (8)
C8A—H8A	0.9300	C12—C13	1.464 (9)
C9A—C10A	1.373 (4)	C13—H13A	0.9600
C9A—H9A	0.9300	C13—H13B	0.9600
C10A—C11A	1.377 (5)	C13—H13C	0.9600
C10A—H10A	0.9300	N2—O2	1.246 (3)
C11A—H11A	0.9300	N2—O4	1.251 (3)
N1B—C2B	1.340 (4)	N2—O3	1.254 (3)
N1B—C5B	1.377 (3)

N3Bⁱ—Co—N3B	177.10 (15)	C6A—C11A—H11A	119.5
N3Bⁱ—Co—N3A	89.15 (7)	C2B—N1B—C5B	107.9 (2)
N3B—Co—N3A	90.99 (7)	C2B—N1B—H1B	122 (2)
N3Bⁱ—Co—N3Aⁱ	90.99 (7)	C5B—N1B—H1B	130 (2)
N3B—Co—N3Aⁱ	89.15 (7)	N3B—C2B—N1B	111.4 (2)
N3A—Co—N3Aⁱ	174.71 (14)	N3B—C2B—H2B	124.3
N3Bⁱ—Co—O1	91.45 (7)	N1B—C2B—H2B	124.3
N3B—Co—O1	91.45 (7)	C2B—N3B—C4B	105.4 (2)
N3A—Co—O1	87.35 (7)	C2B—N3B—Co	125.24 (18)
N3Aⁱ—Co—O1	87.35 (7)	C4B—N3B—Co	129.32 (18)
N3Bⁱ—Co—N1	88.55 (7)	C5B—C4B—N3B	109.9 (2)
N3B—Co—N1	88.55 (7)	C5B—C4B—H4B	125.0
N3A—Co—N1	92.65 (7)	N3B—C4B—H4B	125.0
N3Aⁱ—Co—N1	92.65 (7)	C4B—C5B—N1B	105.4 (2)
O1—Co—N1	180.0	C4B—C5B—C6B	131.4 (3)
C2A—N1A—C5A	107.6 (2)	N1B—C5B—C6B	123.2 (2)
C2A—N1A—H1A	121 (2)	C11B—C6B—C7B	119.0 (3)
C5A—N1A—H1A	131 (2)	C11B—C6B—C5B	119.3 (3)
N3A—C2A—N1A	111.5 (2)	C7B—C6B—C5B	121.7 (3)
N3A—C2A—H2A	124.3	C8B—C7B—C6B	120.1 (3)
N1A—C2A—H2A	124.3	C8B—C7B—H7B	119.9
C2A—N3A—C4A	105.1 (2)	C6B—C7B—H7B	119.9
C2A—N3A—Co	130.2 (2)	C9B—C8B—C7B	120.4 (3)
C4A—N3A—Co	124.01 (18)	C9B—C8B—H8B	119.8
C5A—C4A—N3A	111.4 (2)	C7B—C8B—H8B	119.8
C5A—C4A—H4A	124.3	C8B—C9B—C10B	119.9 (3)
N3A—C4A—H4A	124.3	C8B—C9B—H9B	120.1
C4A—C5A—N1A	104.5 (2)	C10B—C9B—H9B	120.1
C4A—C5A—C6A	131.0 (3)	C9B—C10B—C11B	120.0 (3)
N1A—C5A—C6A	124.6 (3)	C9B—C10B—H10B	120.0
C11A—C6A—C7A	117.8 (3)	C11B—C10B—H10B	120.0
C11A—C6A—C5A	119.4 (3)	C6B—C11B—C10B	120.5 (3)
C7A—C6A—C5A	122.7 (3)	C6B—C11B—H11B	119.7
C8A—C7A—C6A	120.7 (3)	C10B—C11B—H11B	119.7
C8A—C7A—H7A	119.7	Co—O1—H1	125 (3)
C6A—C7A—H7A	119.7	C12—N1—Co	168.0 (6)
C9A—C8A—C7A	120.3 (3)	N1—C12—C13	177.6 (10)
C9A—C8A—H8A	119.8	C12—C13—H13A	109.5
C7A—C8A—H8A	119.8	C12—C13—H13B	109.5
C10A—C9A—C8A	119.3 (3)	H13A—C13—H13B	109.5
C10A—C9A—H9A	120.4	C12—C13—H13C	109.5
C8A—C9A—H9A	120.4	H13A—C13—H13C	109.5
C9A—C10A—C11A	120.8 (3)	H13B—C13—H13C	109.5
C9A—C10A—H10A	119.6	O2—N2—O4	120.5 (2)
C11A—C10A—H10A	119.6	O2—N2—O3	120.4 (2)
C10A—C11A—C6A	121.1 (3)	O4—N2—O3	119.0 (2)
C10A—C11A—H11A	119.5

Symmetry code: (i) −x+1, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O3ⁱⁱ	0.84 (3)	2.00 (3)	2.821 (3)	167 (3)
N1B—H1B···O3ⁱⁱⁱ	0.84 (3)	2.53 (3)	3.127 (3)	128 (3)
N1B—H1B···O4ⁱⁱⁱ	0.84 (3)	2.03 (3)	2.868 (3)	170 (3)
O1—H1···O2ⁱ	0.82 (3)	2.05 (3)	2.865 (3)	177 (3)

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

(7) top

Crystal data top

C₃₈H₃₂CoN₁₀S₂·2(CH₄O)	Z = 1
M_r = 815.87	F(000) = 425
Triclinic, P1	D_x = 1.320 Mg m⁻³
a = 8.6822 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4570 (9) Å	Cell parameters from 3225 reflections
c = 13.6578 (12) Å	θ = 4.3–29.6°
α = 103.023 (8)°	µ = 0.57 mm⁻¹
β = 95.901 (7)°	T = 100 K
γ = 107.217 (8)°	Prism, orange
V = 1026.15 (17) Å³	0.24 × 0.15 × 0.14 mm

Data collection top

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4241 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3549 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	R_int = 0.032
ω scans	θ_max = 26.5°, θ_min = 2.8°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→10
T_min = 0.780, T_max = 1.000	k = −11→9
8705 measured reflections	l = −16→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: mixed
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0309P)² + 0.5771P] where P = (F_o² + 2F_c²)/3
4241 reflections	(Δ/σ)_max < 0.001
260 parameters	Δρ_max = 0.28 e Å⁻³
3 restraints	Δρ_min = −0.38 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Co	0.5000	0.0000	0.0000	0.01496 (11)
N1A	0.8245 (2)	0.1512 (2)	0.28699 (13)	0.0206 (4)
H1A	0.9216 (16)	0.186 (3)	0.3232 (16)	0.031*
C2A	0.7864 (2)	0.1130 (2)	0.18446 (15)	0.0186 (4)
H2A	0.8630	0.1182	0.1414	0.022*
N3A	0.62656 (19)	0.06713 (18)	0.15296 (12)	0.0175 (4)
C4A	0.5598 (2)	0.0779 (2)	0.24040 (15)	0.0190 (4)
H4A	0.4483	0.0530	0.2418	0.023*
C5A	0.6804 (2)	0.1303 (2)	0.32429 (15)	0.0192 (4)
C6A	0.6744 (3)	0.1620 (2)	0.43391 (16)	0.0238 (5)
C7A	0.8039 (3)	0.1675 (3)	0.50515 (17)	0.0322 (6)
H7A	0.8972	0.1516	0.4838	0.039*
C8A	0.7939 (3)	0.1967 (3)	0.60824 (18)	0.0416 (7)
H8A	0.8815	0.2019	0.6559	0.050*
C9A	0.6552 (3)	0.2181 (3)	0.64033 (18)	0.0413 (7)
H9A	0.6493	0.2375	0.7094	0.050*
C10A	0.5255 (3)	0.2106 (3)	0.57024 (18)	0.0354 (6)
H10A	0.4315	0.2241	0.5920	0.042*
C11A	0.5343 (3)	0.1830 (3)	0.46733 (16)	0.0275 (5)
H11A	0.4464	0.1786	0.4203	0.033*
N1B	0.7994 (2)	0.3840 (2)	−0.08532 (13)	0.0202 (4)
H1B	0.809 (3)	0.4694 (17)	−0.0993 (18)	0.030*
C2B	0.6720 (2)	0.3065 (2)	−0.04877 (15)	0.0203 (4)
H2B	0.5855	0.3410	−0.0328	0.024*
N3B	0.68554 (19)	0.17517 (19)	−0.03846 (12)	0.0179 (4)
C4B	0.8302 (2)	0.1702 (2)	−0.07021 (15)	0.0185 (4)
H4B	0.8724	0.0904	−0.0712	0.022*
C5B	0.9025 (2)	0.2985 (2)	−0.09994 (14)	0.0173 (4)
C6B	1.0529 (2)	0.3429 (2)	−0.14259 (14)	0.0176 (4)
C7B	1.1047 (3)	0.4777 (2)	−0.17281 (17)	0.0257 (5)
H7B	1.0442	0.5445	−0.1650	0.031*
C8B	1.2461 (3)	0.5135 (2)	−0.21452 (17)	0.0267 (5)
H8B	1.2794	0.6040	−0.2344	0.032*
C9B	1.3368 (2)	0.4163 (2)	−0.22663 (16)	0.0237 (5)
H9B	1.4312	0.4405	−0.2547	0.028*
C10B	1.2868 (3)	0.2819 (3)	−0.19674 (19)	0.0301 (5)
H10B	1.3475	0.2152	−0.2050	0.036*
C11B	1.1465 (3)	0.2465 (3)	−0.15450 (18)	0.0275 (5)
H11B	1.1147	0.1566	−0.1338	0.033*
N2	0.63040 (19)	−0.15390 (19)	−0.04664 (13)	0.0195 (4)
C12	0.6937 (2)	−0.2233 (2)	−0.09897 (15)	0.0176 (4)
S	0.78707 (7)	−0.31891 (7)	−0.17439 (4)	0.02719 (15)
C13	0.2128 (4)	0.4090 (3)	0.4679 (2)	0.0525 (8)
H13A	0.1614	0.4020	0.5264	0.079*
H13B	0.1868	0.4845	0.4389	0.079*
H13C	0.3295	0.4386	0.4883	0.079*
O1	0.15494 (19)	0.2647 (2)	0.39439 (13)	0.0382 (4)
H1	0.199 (3)	0.274 (4)	0.3431 (15)	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.01664 (19)	0.0152 (2)	0.01317 (19)	0.00462 (14)	0.00512 (15)	0.00379 (14)
N1A	0.0180 (8)	0.0248 (10)	0.0176 (9)	0.0057 (7)	0.0020 (7)	0.0050 (7)
C2A	0.0191 (9)	0.0197 (11)	0.0170 (10)	0.0062 (8)	0.0049 (8)	0.0043 (8)
N3A	0.0192 (8)	0.0168 (9)	0.0164 (8)	0.0054 (7)	0.0055 (7)	0.0043 (7)
C4A	0.0201 (9)	0.0200 (11)	0.0181 (10)	0.0062 (8)	0.0078 (8)	0.0061 (8)
C5A	0.0220 (10)	0.0181 (10)	0.0179 (10)	0.0065 (8)	0.0058 (8)	0.0050 (8)
C6A	0.0280 (11)	0.0214 (11)	0.0170 (10)	0.0017 (9)	0.0042 (9)	0.0040 (8)
C7A	0.0285 (11)	0.0378 (14)	0.0229 (11)	0.0014 (10)	0.0020 (10)	0.0078 (10)
C8A	0.0446 (15)	0.0470 (16)	0.0181 (11)	−0.0040 (12)	−0.0054 (11)	0.0097 (11)
C9A	0.0544 (16)	0.0383 (15)	0.0168 (11)	−0.0031 (12)	0.0103 (12)	0.0022 (10)
C10A	0.0447 (14)	0.0310 (14)	0.0252 (12)	0.0057 (11)	0.0162 (11)	0.0022 (10)
C11A	0.0323 (11)	0.0256 (12)	0.0199 (11)	0.0049 (9)	0.0061 (9)	0.0023 (9)
N1B	0.0243 (8)	0.0172 (9)	0.0227 (9)	0.0080 (7)	0.0101 (7)	0.0079 (7)
C2B	0.0216 (10)	0.0193 (11)	0.0200 (10)	0.0056 (8)	0.0080 (8)	0.0045 (8)
N3B	0.0180 (8)	0.0167 (9)	0.0172 (8)	0.0036 (7)	0.0038 (7)	0.0036 (7)
C4B	0.0187 (9)	0.0186 (10)	0.0195 (10)	0.0071 (8)	0.0047 (8)	0.0055 (8)
C5B	0.0186 (9)	0.0164 (10)	0.0145 (9)	0.0054 (8)	0.0017 (8)	0.0008 (8)
C6B	0.0168 (9)	0.0187 (10)	0.0127 (9)	0.0023 (8)	0.0003 (8)	0.0011 (8)
C7B	0.0283 (11)	0.0198 (11)	0.0336 (12)	0.0111 (9)	0.0151 (10)	0.0076 (9)
C8B	0.0300 (11)	0.0160 (11)	0.0341 (12)	0.0044 (9)	0.0146 (10)	0.0074 (9)
C9B	0.0196 (10)	0.0245 (12)	0.0253 (11)	0.0045 (8)	0.0100 (9)	0.0044 (9)
C10B	0.0272 (11)	0.0315 (13)	0.0421 (14)	0.0170 (10)	0.0159 (10)	0.0161 (11)
C11B	0.0266 (11)	0.0266 (12)	0.0367 (13)	0.0114 (9)	0.0119 (10)	0.0170 (10)
N2	0.0209 (8)	0.0192 (9)	0.0199 (9)	0.0070 (7)	0.0060 (7)	0.0068 (7)
C12	0.0140 (9)	0.0176 (10)	0.0207 (10)	0.0018 (8)	0.0027 (8)	0.0091 (8)
S	0.0298 (3)	0.0282 (3)	0.0332 (3)	0.0158 (2)	0.0186 (2)	0.0128 (2)
C13	0.0496 (16)	0.0419 (17)	0.0497 (17)	−0.0032 (13)	0.0053 (14)	0.0066 (14)
O1	0.0300 (9)	0.0495 (11)	0.0311 (9)	0.0059 (8)	0.0042 (7)	0.0130 (8)

Geometric parameters (Å, º) top

Co—N3Aⁱ	2.1194 (16)	N1B—C5B	1.374 (3)
Co—N3A	2.1195 (16)	N1B—H1B	0.854 (10)
Co—N2ⁱ	2.1241 (17)	C2B—N3B	1.318 (3)
Co—N2	2.1241 (17)	C2B—H2B	0.9300
Co—N3B	2.1452 (16)	N3B—C4B	1.380 (2)
Co—N3Bⁱ	2.1452 (16)	C4B—C5B	1.362 (3)
N1A—C2A	1.344 (3)	C4B—H4B	0.9300
N1A—C5A	1.376 (3)	C5B—C6B	1.471 (3)
N1A—H1A	0.861 (10)	C6B—C11B	1.385 (3)
C2A—N3A	1.318 (2)	C6B—C7B	1.390 (3)
C2A—H2A	0.9300	C7B—C8B	1.389 (3)
N3A—C4A	1.377 (2)	C7B—H7B	0.9300
C4A—C5A	1.358 (3)	C8B—C9B	1.371 (3)
C4A—H4A	0.9300	C8B—H8B	0.9300
C5A—C6A	1.469 (3)	C9B—C10B	1.384 (3)
C6A—C7A	1.390 (3)	C9B—H9B	0.9300
C6A—C11A	1.394 (3)	C10B—C11B	1.385 (3)
C7A—C8A	1.389 (3)	C10B—H10B	0.9300
C7A—H7A	0.9300	C11B—H11B	0.9300
C8A—C9A	1.377 (4)	N2—C12	1.152 (3)
C8A—H8A	0.9300	C12—S	1.650 (2)
C9A—C10A	1.375 (4)	C13—O1	1.413 (3)
C9A—H9A	0.9300	C13—H13A	0.9600
C10A—C11A	1.385 (3)	C13—H13B	0.9600
C10A—H10A	0.9300	C13—H13C	0.9600
C11A—H11A	0.9300	O1—H1	0.840 (10)
N1B—C2B	1.345 (3)

N3Aⁱ—Co—N3A	180.0	C10A—C11A—C6A	120.3 (2)
N3Aⁱ—Co—N2ⁱ	91.85 (6)	C10A—C11A—H11A	119.9
N3A—Co—N2ⁱ	88.15 (6)	C6A—C11A—H11A	119.9
N3Aⁱ—Co—N2	88.15 (6)	C2B—N1B—C5B	108.22 (18)
N3A—Co—N2	91.85 (6)	C2B—N1B—H1B	124.0 (16)
N2ⁱ—Co—N2	180.0	C5B—N1B—H1B	127.7 (16)
N3Aⁱ—Co—N3B	88.63 (6)	N3B—C2B—N1B	111.28 (18)
N3A—Co—N3B	91.37 (6)	N3B—C2B—H2B	124.4
N2ⁱ—Co—N3B	91.49 (6)	N1B—C2B—H2B	124.4
N2—Co—N3B	88.51 (6)	C2B—N3B—C4B	105.14 (17)
N3Aⁱ—Co—N3Bⁱ	91.37 (6)	C2B—N3B—Co	125.05 (13)
N3A—Co—N3Bⁱ	88.63 (6)	C4B—N3B—Co	129.30 (14)
N2ⁱ—Co—N3Bⁱ	88.51 (6)	C5B—C4B—N3B	110.55 (18)
N2—Co—N3Bⁱ	91.49 (6)	C5B—C4B—H4B	124.7
N3B—Co—N3Bⁱ	180.0	N3B—C4B—H4B	124.7
C2A—N1A—C5A	107.82 (16)	C4B—C5B—N1B	104.81 (17)
C2A—N1A—H1A	126.3 (16)	C4B—C5B—C6B	130.81 (19)
C5A—N1A—H1A	125.9 (16)	N1B—C5B—C6B	124.34 (18)
N3A—C2A—N1A	111.18 (18)	C11B—C6B—C7B	118.20 (19)
N3A—C2A—H2A	124.4	C11B—C6B—C5B	119.11 (19)
N1A—C2A—H2A	124.4	C7B—C6B—C5B	122.69 (19)
C2A—N3A—C4A	105.52 (16)	C6B—C7B—C8B	120.6 (2)
C2A—N3A—Co	127.11 (13)	C6B—C7B—H7B	119.7
C4A—N3A—Co	127.33 (13)	C8B—C7B—H7B	119.7
C5A—C4A—N3A	110.20 (17)	C9B—C8B—C7B	120.5 (2)
C5A—C4A—H4A	124.9	C9B—C8B—H8B	119.7
N3A—C4A—H4A	124.9	C7B—C8B—H8B	119.7
C4A—C5A—N1A	105.28 (17)	C8B—C9B—C10B	119.50 (19)
C4A—C5A—C6A	131.59 (18)	C8B—C9B—H9B	120.3
N1A—C5A—C6A	123.13 (18)	C10B—C9B—H9B	120.3
C7A—C6A—C11A	119.0 (2)	C9B—C10B—C11B	120.1 (2)
C7A—C6A—C5A	121.4 (2)	C9B—C10B—H10B	120.0
C11A—C6A—C5A	119.5 (2)	C11B—C10B—H10B	120.0
C8A—C7A—C6A	120.0 (2)	C6B—C11B—C10B	121.1 (2)
C8A—C7A—H7A	120.0	C6B—C11B—H11B	119.5
C6A—C7A—H7A	120.0	C10B—C11B—H11B	119.5
C9A—C8A—C7A	120.4 (2)	C12—N2—Co	158.73 (17)
C9A—C8A—H8A	119.8	N2—C12—S	178.69 (19)
C7A—C8A—H8A	119.8	O1—C13—H13A	109.5
C10A—C9A—C8A	120.0 (2)	O1—C13—H13B	109.5
C10A—C9A—H9A	120.0	H13A—C13—H13B	109.5
C8A—C9A—H9A	120.0	O1—C13—H13C	109.5
C9A—C10A—C11A	120.2 (2)	H13A—C13—H13C	109.5
C9A—C10A—H10A	119.9	H13B—C13—H13C	109.5
C11A—C10A—H10A	119.9	C13—O1—H1	108 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1ⁱⁱ	0.86 (2)	2.00 (2)	2.853 (3)	174 (2)
N1B—H1B···Sⁱⁱⁱ	0.85 (2)	2.49 (2)	3.328 (2)	167 (2)
O1—H1···Sⁱ	0.84 (2)	2.44 (2)	3.224 (2)	155 (2)

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

(8) top

Crystal data top

C₂₀H₁₆CoN₆S₂	F(000) = 948
M_r = 463.44	D_x = 1.517 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.4747 (19) Å	Cell parameters from 1570 reflections
b = 5.5932 (5) Å	θ = 4.6–29.3°
c = 14.8644 (16) Å	µ = 1.07 mm⁻¹
β = 94.172 (8)°	T = 100 K
V = 2029.4 (3) Å³	Prism, blue
Z = 4	0.15 × 0.09 × 0.09 mm

Data collection top

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	2176 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1794 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	R_int = 0.030
ω scans	θ_max = 27.0°, θ_min = 3.3°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −30→24
T_min = 0.935, T_max = 1.000	k = −5→7
4333 measured reflections	l = −18→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: mixed
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0224P)² + 3.0766P] where P = (F_o² + 2F_c²)/3
2176 reflections	(Δ/σ)_max = 0.001
135 parameters	Δρ_max = 0.43 e Å⁻³
1 restraint	Δρ_min = −0.27 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Co	0.5000	0.71417 (8)	0.7500	0.01835 (13)
N1	0.39936 (7)	0.2486 (3)	0.59807 (12)	0.0183 (4)
H1	0.3954 (10)	0.129 (3)	0.5626 (14)	0.027*
C2	0.44728 (8)	0.3524 (4)	0.62177 (14)	0.0208 (5)
H2	0.4801	0.3141	0.5974	0.025*
N3	0.44203 (7)	0.5165 (3)	0.68420 (11)	0.0183 (4)
C4	0.38688 (8)	0.5172 (4)	0.70008 (14)	0.0182 (5)
H4	0.3709	0.6166	0.7409	0.022*
C5	0.35966 (8)	0.3511 (4)	0.64724 (13)	0.0157 (4)
C6	0.30160 (8)	0.2847 (4)	0.63634 (13)	0.0150 (4)
C7	0.28427 (8)	0.0706 (4)	0.59538 (13)	0.0173 (4)
H7	0.3099	−0.0377	0.5766	0.021*
C8	0.22878 (8)	0.0193 (4)	0.58257 (13)	0.0182 (4)
H8	0.2175	−0.1234	0.5551	0.022*
C9	0.19019 (8)	0.1782 (4)	0.61027 (13)	0.0173 (4)
H9	0.1531	0.1438	0.6004	0.021*
C10	0.20690 (8)	0.3885 (4)	0.65270 (13)	0.0163 (4)
H10	0.1810	0.4944	0.6724	0.020*
C11	0.26228 (8)	0.4416 (4)	0.66587 (13)	0.0148 (4)
H11	0.2733	0.5831	0.6946	0.018*
N2	0.45765 (7)	0.9051 (4)	0.83063 (13)	0.0243 (4)
C12	0.43880 (8)	1.0272 (4)	0.88384 (15)	0.0185 (5)
S	0.41467 (2)	1.20455 (10)	0.95819 (4)	0.02081 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0102 (2)	0.0229 (2)	0.0220 (2)	0.000	0.00118 (15)	0.000
N1	0.0168 (8)	0.0183 (10)	0.0201 (10)	0.0038 (8)	0.0032 (7)	−0.0032 (7)
C2	0.0146 (10)	0.0251 (12)	0.0230 (11)	0.0059 (9)	0.0036 (8)	0.0024 (10)
N3	0.0127 (8)	0.0214 (10)	0.0207 (9)	0.0006 (8)	0.0020 (7)	0.0004 (8)
C4	0.0127 (9)	0.0234 (12)	0.0187 (10)	0.0004 (9)	0.0027 (8)	−0.0017 (9)
C5	0.0146 (9)	0.0177 (11)	0.0149 (10)	0.0043 (9)	0.0020 (8)	0.0033 (8)
C6	0.0157 (10)	0.0180 (11)	0.0112 (10)	−0.0001 (9)	−0.0001 (7)	0.0025 (8)
C7	0.0208 (10)	0.0153 (11)	0.0160 (10)	0.0027 (9)	0.0020 (8)	0.0006 (9)
C8	0.0239 (11)	0.0152 (11)	0.0150 (10)	−0.0029 (9)	−0.0018 (8)	0.0024 (9)
C9	0.0157 (9)	0.0237 (11)	0.0121 (10)	−0.0038 (9)	−0.0012 (8)	0.0023 (9)
C10	0.0161 (10)	0.0200 (11)	0.0129 (10)	0.0020 (9)	0.0014 (8)	0.0014 (8)
C11	0.0162 (9)	0.0147 (10)	0.0131 (10)	−0.0009 (8)	−0.0005 (7)	−0.0005 (8)
N2	0.0164 (9)	0.0268 (11)	0.0296 (11)	−0.0013 (8)	0.0012 (8)	−0.0043 (9)
C12	0.0112 (9)	0.0191 (11)	0.0246 (11)	−0.0029 (9)	−0.0028 (8)	0.0036 (9)
S	0.0190 (3)	0.0190 (3)	0.0249 (3)	−0.0007 (2)	0.0054 (2)	−0.0006 (2)

Geometric parameters (Å, º) top

Co—N2	1.9576 (19)	C6—C11	1.397 (3)
Co—N2ⁱ	1.9576 (19)	C6—C7	1.395 (3)
Co—N3ⁱ	1.9974 (18)	C7—C8	1.388 (3)
Co—N3	1.9974 (18)	C7—H7	0.9300
N1—C2	1.333 (3)	C8—C9	1.381 (3)
N1—C5	1.382 (3)	C8—H8	0.9300
N1—H1	0.852 (10)	C9—C10	1.383 (3)
C2—N3	1.318 (3)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.388 (3)
N3—C4	1.387 (2)	C10—H10	0.9300
C4—C5	1.359 (3)	C11—H11	0.9300
C4—H4	0.9300	N2—C12	1.165 (3)
C5—C6	1.466 (3)	C12—S	1.628 (2)

N2—Co—N2ⁱ	113.88 (12)	C11—C6—C7	118.83 (19)
N2—Co—N3ⁱ	113.01 (7)	C11—C6—C5	119.36 (19)
N2ⁱ—Co—N3ⁱ	102.29 (7)	C7—C6—C5	121.80 (19)
N2—Co—N3	102.29 (7)	C8—C7—C6	120.05 (19)
N2ⁱ—Co—N3	113.02 (7)	C8—C7—H7	120.0
N3ⁱ—Co—N3	112.80 (10)	C6—C7—H7	120.0
C2—N1—C5	108.56 (18)	C9—C8—C7	120.6 (2)
C2—N1—H1	124.4 (16)	C9—C8—H8	119.7
C5—N1—H1	126.8 (16)	C7—C8—H8	119.7
N3—C2—N1	111.13 (18)	C8—C9—C10	119.83 (19)
N3—C2—H2	124.4	C8—C9—H9	120.1
N1—C2—H2	124.4	C10—C9—H9	120.1
C2—N3—C4	105.52 (18)	C9—C10—C11	120.00 (19)
C2—N3—Co	128.89 (14)	C9—C10—H10	120.0
C4—N3—Co	125.49 (14)	C11—C10—H10	120.0
C5—C4—N3	109.99 (18)	C10—C11—C6	120.62 (19)
C5—C4—H4	125.0	C10—C11—H11	119.7
N3—C4—H4	125.0	C6—C11—H11	119.7
C4—C5—N1	104.79 (17)	C12—N2—Co	171.38 (17)
C4—C5—C6	131.85 (19)	N2—C12—S	177.68 (19)
N1—C5—C6	123.34 (19)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Sⁱⁱ	0.85 (2)	2.49 (2)	3.317 (2)	162 (2)

Symmetry code: (ii) x, −y+1, z−1/2.

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Format		BIBTeX
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		CIF
		SGML
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		Plain Text

Influence of ligand positional isomerism on the molecular and supramolecular structures of cobalt(II)-phenyl­imidazole complexes

Supporting information

Influence of ligand positional isomerism on the molecular and supramolecular structures of cobalt(II)-phenylimidazole complexes