Four supra­molecular isomers of di­chlorido­bis­(1,10-phenanthroline)cobalt(II): synthesis, structure characterization and isomerization

Crystal engineering can be described as the understanding of inter­molecular inter­­actions in the context of crystal packing and the utilization of such understanding to design new solids with desired physical and chemical properties. Free-energy differences between supra­molecular isomers are generally small and minor changes in the crystallization conditions may result in the occurrence of new isomers. The study of supra­molecular isomerism will help us to understand the mechanism of crystallization, a very central concept of crystal engineering. Two supra­molecular isomers of di­chlorido­bis­(1,10-phenanthroline-κ²N,N′)cobalt(II), [CoCl₂(C₁₂H₈N₂)₂], i.e. (IA) (ortho­rhom­bic) and (IB) (monoclinic), and two supra­molecular isomers of di­chlorido­bis­(1,10-phenanthroline-κ²N,N′)cobalt(II) N,N-di­methyl­formamide monosolvate, [CoCl₂(C₁₂H₈N₂)₂]·C₃H₇NO, i.e. (IIA) (ortho­rhom­bic) and (IIB) (monoclinic), were synthesized in di­methyl­formamide (DMF) and structurally characterized. Of these, (IA) and (IIA) have been prepared and structurally characterized previously [Li et al. (2007). Acta Cryst. E63, m1880–m1880; Cai et al. (2008). Acta Cryst. E64, m1328–m1329]. We found that the heating rate is a key factor for the crystallization of (IA) or (IB), while the temperature difference is responsible for the crystallization of (IIA) or (IIB). Based on the crystallization conditions, isomerization behaviour, the KPI (Kitajgorodskij packing index) values and the density data, (IB) and (IIA) are assigned as the thermodynamic and stable kinetic isomers, respectively, while (IA) and (IIB) are assigned as the metastable kinetic products. The 1,10-phenanthroline (phen) ligands inter­act with each other through offset face-to-face (OFF) π–π stacking in (IB) and (IIB), but by edge-to-face (EF) C—H...π inter­actions in (IA) and (IIA). Meanwhile, the DMF mol­ecules in (IIB) connect to neighbouring [CoCl₂(phen)₂] units through two C—H...Cl hydrogen bonds, whereas there are no obvious inter­actions between DMF mol­ecules and [CoCl₂(phen)₂] units in (IIA). Since OFF π–π stacking is generally stronger than EF C—H...π inter­actions for transition-metal complexes with nitro­gen-containing aromatic ligands, (IIA) is among the uncommon examples that are stable and densely packed but that do not following Etter's inter­molecular inter­action hierarchy.

S1. Introduction

Crystal engineering is the understanding of inter­molecular inter­actions in the context of crystal packing and the utilization of such understanding to design new solids with desired physical and chemical properties (Desiraju, 2010, 2013). Being an imperative and fascinating area of crystal engineering, supra­molecular isomerism refers to two or more supra­molecular systems (organic crystals or coordination polymers, for examples) that have the same molecular building blocks but different supra­molecular synthons and/or supra­molecular networks (Zhang et al., 2009; Moulton & Zaworotko, 2001). Inside crystals, the individual building blocks are packed together through weak noncovalent bonds, such as M—L coordinative bonds, hydrogen bonds, π–π, C—H···π, halogen–halogen inter­actions etc. Therefore, the free-energy differences between supra­molecular isomers are generally small, and minor changes in the crystallization conditions may result in the occurrence of new isomers. Efforts have been made to refine the synthetic procedures or assembly conditions to produce supra­molecular isomers, in order to better understand the factors that govern the formation of individual isomeric structures (Park et al., 2014; Biswas et al., 2014; Chen et al., 2013; Hu et al., 2012; Sang & Xu, 2010; Wu et al., 2014; Dabb & Fletcher, 2015; Han et al., 2015; Ren et al., 2015; Su et al., 2015; Moulton & Zaworotko, 2001; Zhang et al., 2009). Reaction/crystallization environments, such as solvent (Liu, Wang et al., 2014; Peng et al., 2008; Huang et al., 2006), temperature (Nagarkar et al., 2012; Kanoo et al., 2009; Sun et al., 2005; Masaoka et al., 2004), pH (Han et al., 2014; Orola et al., 2012; Thomas et al., 2010), molar ratio (Lee et al., 2013) and heating rate (Platero-Prats et al., 2012) have been found to affect the formation of particular supra­molecular isomers. Thus, the study of supra­molecular isomerism will help us to understand the mechanism of crystallization, a very central concept of crystal engineering.

Due to its rigidity, planarity, aromaticity, basicity and chelating capability, 1,10-phenanthroline (phen) has been a versatile reagent for analytical, synthetic organic, inorganic and supra­molecular chemistry for decades, and numerous phen coordination compounds have been reported (Ye et al., 2005; Accorsi et al., 2009; Moulton & Zaworotko, 2001; Dabb & Fletcher, 2015). Some phen– or modified phen–metal complexes can selectively bind and/or cleave DNA mainly due to the π-inter­action capability from phen ligands, which infers significant biological and pharmaceutical applications of the phen complexes (Barton, 1986; Mardanya et al., 2015; Shi et al., 2015; Thomas et al., 2010). Dichloridobis(1,10-phenanthroline)cobalt(II), with the capability to catalyze olefin polymerization (Liu, Zhang et al., 2014), can be prepared by mixing CoCl₂·6H₂O with two equivalents of phen in solvents, such as MeOH, EtOH, tetra­hydro­furan (THF), CH₃CN and di­methyl­formamide (DMF) etc. under ambient conditions. A few of its supra­molecular isomers have been obtained and structurally characterized: [CoCl₂(phen)₂], (IA) (orthorhombic; Li et al., 2007), [CoCl(phen)₂(H₂O)]Cl[CoCl₂(phen)₂].6H₂O (Rubin-Preminger et al., 2008), [CoCl₂(phen)₂].DMF, (IIA) (orthorhombic; Cai et al., 2008), [CoCl₂(phen)₂].1.5CH₃CN (Hazell et al., 1997), and [CoCl₂(phen)₂].0.5C₆H₁₄ (Liu, Zhang et al., 2014). Among these, (IA) and (IIA) were obtained by accident; (IA) was prepared in a water–methanol(1:2 v/v) solution at room temperature and crystalized by slow evaporation of the solution at room temperature (Li et al., 2007), while (IIA) was synthesized in a DMF–THF (1:1 v/v) solution at 363 K and crystalized at 269 K after rotary evaporation. There has been no systematic study on the supra­molecular isomerism of dichloridobis(1,10-phenanthroline)cobalt(II) so far. In this work, supra­molecular orthorhombic isomers (IA) and (IIA) were synthesized, together with the monoclinic isomers (IB) and (IIB). They were crystallized from DMF with exactly the same amounts of starting materials and the same concentrations, the only differences being the reaction temperatures and heating rates (Fig. 1).

S2. Experimental

S2.1. Synthesis and crystallization

CoCl₂·6H₂O (0.5 ml, 0.10 mol) in DMF and 1,10-phenanthroline (1.0 ml, 0.10 mol) in DMF were mixed at room temperature in a 5 ml vial with cap. When the reaction mixtures were placed directly into a 373 K oven, a ~269 K refrigerator or a 333 K oven for 12 h, red needle-like crystals of (IA), brown block-shaped crystals of (IIA) or red block-shaped crystals of (IIB) were obtained. If the reaction mixture was heated from room temperature (~298 K) to 373 K at a rate of 80 K h^-1 and kept at 373 K for 12 h, red plate-shaped crystals of (IB) formed.

S2.2. Refinement

Crystal data, data collection and structure refinement details of (IB) and (IIB) are summarized in Table 1. H atoms bonded to C atoms were treated as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic rings, or C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl groups.

S3. Results and discussion

As indicated in Fig. 1, with exactly the same starting materials, the heating rate is the determining factor for the formation of (IA) and (IB), while different reaction temperature leads to the crystallization of (IIA) and (IIB). Experiments showed that there is no indication that (IA) and (IB) would transfer to each other at 373 K by extending the reaction time to 24 h. Meanwhile, the crystals of (IB) were found to be stable at the room temperature. However, when (IA) and (IIB) were kept in their mother liquors at room temperature, block-shaped brown crystals of (IIA) started to appear within 24 h. In about one week, crystals of (IA) and (IIB) disappear and transform to (IIA) completely. We were expecting that (IIA) would lose the DMF solvent molecules and transfer to (IB) when being heated at 373 K, but no change was witnessed for the crystals after being heated for over 24 h. The isomerization behaviours of the four compounds imply that: (i) (IB), crystallized slowly at high temperature (373 K), is the thermodynamic product; (ii) (IA) and (IIB) are the metastable kinetic outcomes; (iii) (IIA) is a highly stable kinetic product. The results are consistent with the KPI (Kitajgorodskij packing index) values (Kitajgorodskij, 1973), calculated by using PLATON (Spek, 2009) [viz. 69.8, 70.4 and 68.8% for (IA), (IB) and (IIB), respectively], and calculated densities [1.567, 1.576, 1.503 and 1.476 Mg m^-3 for (IA), (IB), (IIA) and (IIB), respectively]. Unfortunately, no KPI data is available for (IIA) because the structure is disordered with the DMF molecules sitting on the twofold axes parallel to the b axis and PLATON is unable to calculate the KPI for a disordered structure. But, by considering the KPI value and density data of the four isomers together, we can easily conclude that the KPI value for (IIA) should be much higher than that of (IIB).

As reported by Li et al. (2007), (IA) crystallizes in the orthorhombic system with the Pna2₁ space group, while the new isomer (IB) crystallizes in monoclinic system with the P2₁/c space group. (IB) is an isomorphic structure of [FeCl₂(phen)₂] (Fu et al., 2005), [MnCl₂(phen)₂] (Pan & Xu, 2005) and [CoBr₂(phen)₂] (Yang et al., 2011). The asymmetric unit for both (IA) and (IB) has one [CoCl₂(phen)₂] unit. The molecular structure of (IB) is shown in Fig. 2, where the Co^II atom is coordinated by four N atoms from two phen molecules and two Cl atoms, forming a distorted o­cta­hedral geometry, with the apical N1—Co1—Cl1 and N3—Co1—Cl2 angles of 165.05 (6) and 169.92 (6)°, respectively. The Co—N and Co—Cl bond lengths for (IA) (Li et al., 2007) and (IB) are very similar, and in the ranges 2.127 (2)–2.201 (2) and 2.3733 (8)/2.4516 (8) Å, respectively, for (IB), and 2.1395 (14)–2.2043 (15) and 2.3928 (5)–2.4348 (6) Å, respectively, for (IA). A molecular overlay diagram for (IA) and (IB) with the Co^II atom and the two Cl atoms as the common basis is shown in Fig. 3. The two phen ligands in (IB) (green) are notably closer than those in (IA) (blue), but the dihedral angle between the two phen rings are similar: 73.04 (3) and 71.25 (3)° for (IA) and (IB), respectively.

The inter­molecular inter­actions of (IB) are shown in Fig. 4 and the geometry data are listed in Tables 2 and 3. In the structure, the π–π stacking (Fig. 4a, blue dashed lines) with an average centroid-to-centroid distance of 3.70 (7) Å (Table 2) and the hydrogen bond C10—H10A···Cl1ⁱ (Fig. 4a, green dashed lines), with C···Cl = 3.679 (3) Å (Table 3), co-operated to connect adjacent [CoCl₂(phen)₂] units, resulting in a chain with Co···Co = 8.7671 (10) Å. The chains inter­act with each other through van der Waals forces to form wave-shaped two-dimensional sheets parallel to the ac plane. The C3—H3A···Cl1ⁱⁱⁱ and C15—H15···Cl1^iv hydrogen bonds (Table 3) then join the undulating two-dimensional sheets into a layered architecture (Fig. 4b). In addition, there are two intra­molecular hydrogen bonds with moderate strength in (IB) (C12—H12A···Cl1 and C24—H24A···Cl2; Table 3), which in fact exist in all the isomers of dichloridobis(1,10-phenanthroline)cobalt(II).

For comparison, we analysed the inter­molecular inter­actions in (IA) using the data from Li et al. (2007). In (IA), neighbouring molecules along the b axis are stacked onto each other through C9—H9···Cl1ⁱⁱ hydrogen bonds to form columns (see Table S1 and Fig. S1 in the Supporting information). The C2—H2···Cl1ⁱ hydrogen bond and the edge-to-face (EF) C—H···π inter­actions from neighbouring columns work together to stabilize the columns and connect them into a three-dimensional architecture (see Table S1 and Fig. S1b in the Supporting information).

Thus, with rather similar molecular structures, (IB) is a layered structure and (IA) consists of parallel columns with significantly different supra­molecular networks: (i) the inter­actions between phen rings are EF C—H···π in (IA), but offset face-to-face (OFF) π–π in (IB); (ii) although in both (IA) and (IB) only one Cl atom from each of the [CoCl₂(phen)₂] units is involved in C—H···Cl hydrogen-bonding inter­actions, the Cl1 atom in (IA) bridges two H atoms from two neighbouring molecules to form bifurcated hydrogen bonds, while atom Cl1 in (IB) links three H atoms from the nearby molecules to form a trifurcated hydrogen bond. Theoretical calculations showed that for electron-deficient nitro­gen-containing aromatic compounds, lower total energy levels were achieved by adopting the OFF π–π mode, and the energy difference between OFF π–π and EF C—H···π for pyridine, pyrazine and triazine are 4.46, 3.50 and 2.65 kcal mol^-1, respectively (Geronimo et al., 2010). Janiak summarized the π-inter­actions in the metal complexes with nitro­gen-containing aromatic ligands. He indicated that the OFF π–π stacking of aromatic moieties shows increased stability when both partners are electron-poor, and a coordinated metal cation will decrease the electron density of the π-system and increase the tenancy of stacking (Janiak, 2000). This means that (IB) should have lower energy and be more stable that (IA), which is consistent with the results from our isomerization experiments.

The molecular and supra­molecular structures of (IIB) are shown in Figs. 5 and 6, and the supra­molecular structure of (IIA) is shown in Fig. S2 (see Supporting information) for comparison. As reported by Cai et al., (IIA) belongs to orthorhombic space group Pbcn, and only a half of the [CoCl₂(phen)₂].DMF is unique (Cai et al., 2008), while the new isomer (IIB) crystalizes in the monoclinic P2₁/c space group and the asymmetric unit consists of a complete [CoCl₂(phen)₂].DMF unit. Yet, similar to (IA) and (IB), the coordination geometry of the Co^II atom in (IIA) and (IIB) is distorted o­cta­hedral, with an apical N1—Co1—Cl1 angle of 162.67 (4)° for (IIA), and N1—Co1—Cl1 and N4—Co1—Cl2 angles in (IIB) of 167.55 (4) and 170.23 (4)°, respectively. In addition, the Co—Cl and Co—N bond lengths in (IIA) and (IIB) are very similar, i.e. 2.127 (2)–2.201 (2) and 2.3733 (8)/2.4516 (8) Å respectively, for (IIA), and 2.1444 (12)–2.1780 (13) and 2.3889 (4)/2.4075 (4) Å, respectively, for (IIB), with the latter range slightly narrower.

As we can see from Fig. 6(a), each [CoCl₂(phen)₂] unit in (IIB) links to four other [CoCl₂(phen)₂] units and four DMF molecules to form a two-dimensional sheet parallel to the ab plane. Each DMF molecule is bonded to a [CoCl₂(phen)₂] unit through two hydrogen bonds (C1A—H1AC···Cl1 and C2A—H2AB···Cl2; Table 5) and each [CoCl₂(phen)₂] unit inter­acts to its four [CoCl₂(phen)₂] neighbours through hydrogen bonds (C9—H9A···Cl2ⁱⁱⁱ and C15—H15A···Cl1^v; Table 5). The two-dimensional sheets are further connected through π–π stacking inter­actions (Cg1···Cg2ⁱ and Cg3···Cg3ⁱⁱ; Table 4) and hydrogen bonds (C14—H14A···Cl1^iv, C20—H20A···Cl1ⁱ and C24—H24A···Cl2^vi; Table 5) to form a three-dimensional supra­molecular network, where the DMF molecules sit in channels parallel to the c axis (Fig. 6b).

By analysing the data reported by Cai et al., we found that each [CoCl₂(phen)₂] unit in (IIA) is also surrounded by four other [CoCl₂(phen)₂] units and four DMF molecules to form a two-dimensional sheet parallel to the ac-plane (see Table S2 and Fig. S2a in the Supporting information). However, the [CoCl₂(phen)₂] unit inter­acts with its four [CoCl₂(phen)₂] neighbours through C6—H6A···Cl1ⁱ and EF C8—H8A···Cg2^iv, and there is no obvious inter­action between the [CoCl₂(phen)₂] unit and the DMF molecules. The two-dimensional sheets associate with each other through C5—H5A···Cl1ⁱⁱ and EF C2—H2A···Cg1ⁱⁱⁱ inter­actions (Fig. S2b in the Supporting information) to form a three-dimensional architecture, where each of the DMF molecules is locked in a separate cavity surrounded by six [CoCl₂(phen)₂] units. The overlay diagram of [CoCl₂(phen)₂] units for (IIA) and (IIB) (Fig. 7, with one Co^II atom and the two Cl atoms as the common basis) shows that there is less of a difference between (IIA) (yellow) and (IIB) (purple), than between(IA) and (IB). One pair of the phen ligands are almost completely overlapped, while the other pair are crossed with respect to each other. The dihedral angle between the two phen rings is 80.36 (2)° for (IIA) and 86.88 (2)° for (IIB), which are much larger than those for (IA) and (IB) of 73.04 (3) and 71.25 (3)°, respectively.

From the discussion above, we can see that, similar to (IA) and (IB), the supra­molecular structures of (IIA) and (IIB) are also quite different: (i) EF C—H···π and OFF π–π inter­actions are observed in (IIA) and (IIB), respectively; (ii) atoms Cl1 and Cl2 in (IIB) are involved in trifurcated and bifurcated hydrogen bonding, respectively, while both atoms Cl1 and Cl2 in (IIA) only form one C—H···Cl hydrogen bond; (iii) the DMF molecules in (IIB) are involved in hydrogen bonding, but the DMF molecules do not show any apparent hydrogen-bonding inter­actions. However, what makes the two isomers more inter­esting is that, compared to (IIB), (IIA) with a less stable EF C—H···π inter­action mode and fewer C—H···Cl hydrogen bonds has a much higher density (1.503 versus 1.476 Mg m^-3) and a higher thermostability. This means that here the best packing does not go together with the best inter­actions. Similar observations have been made for quite a few compounds, such as RSO₂NHN═CR₂ (R = p-tolyl), where the thermodynamic form does not contain the best hydrogen bond, i.e. N—H···O═S (Desiraju, 2007' Roy & Nangia, 2007).

In summary, two pairs of supra­molecular isomers of dichloridobis(1,10-phenanthroline)cobalt(II) were synthesized in DMF and structurally characterized. The heating rate and reaction temperature are the key factors for the crystallization of the four isomers. Of the isomers, (IB) and (IIA) are the thermodynamic and stable kinetic isomers, respectively, and (IA) and (IIB) are the two metastable kinetic products. Structural analysis reveals that the phen ligands inter­act with each other through OFF π–π stacking in (IB) and (IIB), but by EF C—H···π inter­actions in (IA) and (IIA). (IIA) is among the uncommon examples that are stable and densely packed but without best inter­molecular inter­actions. A study on the supra­molecular isomerization of the system and theory calculations are presently in progress by our group.

Structure description

Crystal engineering is the understanding of inter­molecular inter­actions in the context of crystal packing and the utilization of such understanding to design new solids with desired physical and chemical properties (Desiraju, 2010, 2013). Being an imperative and fascinating area of crystal engineering, supra­molecular isomerism refers to two or more supra­molecular systems (organic crystals or coordination polymers, for examples) that have the same molecular building blocks but different supra­molecular synthons and/or supra­molecular networks (Zhang et al., 2009; Moulton & Zaworotko, 2001). Inside crystals, the individual building blocks are packed together through weak noncovalent bonds, such as M—L coordinative bonds, hydrogen bonds, π–π, C—H···π, halogen–halogen inter­actions etc. Therefore, the free-energy differences between supra­molecular isomers are generally small, and minor changes in the crystallization conditions may result in the occurrence of new isomers. Efforts have been made to refine the synthetic procedures or assembly conditions to produce supra­molecular isomers, in order to better understand the factors that govern the formation of individual isomeric structures (Park et al., 2014; Biswas et al., 2014; Chen et al., 2013; Hu et al., 2012; Sang & Xu, 2010; Wu et al., 2014; Dabb & Fletcher, 2015; Han et al., 2015; Ren et al., 2015; Su et al., 2015; Moulton & Zaworotko, 2001; Zhang et al., 2009). Reaction/crystallization environments, such as solvent (Liu, Wang et al., 2014; Peng et al., 2008; Huang et al., 2006), temperature (Nagarkar et al., 2012; Kanoo et al., 2009; Sun et al., 2005; Masaoka et al., 2004), pH (Han et al., 2014; Orola et al., 2012; Thomas et al., 2010), molar ratio (Lee et al., 2013) and heating rate (Platero-Prats et al., 2012) have been found to affect the formation of particular supra­molecular isomers. Thus, the study of supra­molecular isomerism will help us to understand the mechanism of crystallization, a very central concept of crystal engineering.

Due to its rigidity, planarity, aromaticity, basicity and chelating capability, 1,10-phenanthroline (phen) has been a versatile reagent for analytical, synthetic organic, inorganic and supra­molecular chemistry for decades, and numerous phen coordination compounds have been reported (Ye et al., 2005; Accorsi et al., 2009; Moulton & Zaworotko, 2001; Dabb & Fletcher, 2015). Some phen– or modified phen–metal complexes can selectively bind and/or cleave DNA mainly due to the π-inter­action capability from phen ligands, which infers significant biological and pharmaceutical applications of the phen complexes (Barton, 1986; Mardanya et al., 2015; Shi et al., 2015; Thomas et al., 2010). Dichloridobis(1,10-phenanthroline)cobalt(II), with the capability to catalyze olefin polymerization (Liu, Zhang et al., 2014), can be prepared by mixing CoCl₂·6H₂O with two equivalents of phen in solvents, such as MeOH, EtOH, tetra­hydro­furan (THF), CH₃CN and di­methyl­formamide (DMF) etc. under ambient conditions. A few of its supra­molecular isomers have been obtained and structurally characterized: [CoCl₂(phen)₂], (IA) (orthorhombic; Li et al., 2007), [CoCl(phen)₂(H₂O)]Cl[CoCl₂(phen)₂].6H₂O (Rubin-Preminger et al., 2008), [CoCl₂(phen)₂].DMF, (IIA) (orthorhombic; Cai et al., 2008), [CoCl₂(phen)₂].1.5CH₃CN (Hazell et al., 1997), and [CoCl₂(phen)₂].0.5C₆H₁₄ (Liu, Zhang et al., 2014). Among these, (IA) and (IIA) were obtained by accident; (IA) was prepared in a water–methanol(1:2 v/v) solution at room temperature and crystalized by slow evaporation of the solution at room temperature (Li et al., 2007), while (IIA) was synthesized in a DMF–THF (1:1 v/v) solution at 363 K and crystalized at 269 K after rotary evaporation. There has been no systematic study on the supra­molecular isomerism of dichloridobis(1,10-phenanthroline)cobalt(II) so far. In this work, supra­molecular orthorhombic isomers (IA) and (IIA) were synthesized, together with the monoclinic isomers (IB) and (IIB). They were crystallized from DMF with exactly the same amounts of starting materials and the same concentrations, the only differences being the reaction temperatures and heating rates (Fig. 1).

As indicated in Fig. 1, with exactly the same starting materials, the heating rate is the determining factor for the formation of (IA) and (IB), while different reaction temperature leads to the crystallization of (IIA) and (IIB). Experiments showed that there is no indication that (IA) and (IB) would transfer to each other at 373 K by extending the reaction time to 24 h. Meanwhile, the crystals of (IB) were found to be stable at the room temperature. However, when (IA) and (IIB) were kept in their mother liquors at room temperature, block-shaped brown crystals of (IIA) started to appear within 24 h. In about one week, crystals of (IA) and (IIB) disappear and transform to (IIA) completely. We were expecting that (IIA) would lose the DMF solvent molecules and transfer to (IB) when being heated at 373 K, but no change was witnessed for the crystals after being heated for over 24 h. The isomerization behaviours of the four compounds imply that: (i) (IB), crystallized slowly at high temperature (373 K), is the thermodynamic product; (ii) (IA) and (IIB) are the metastable kinetic outcomes; (iii) (IIA) is a highly stable kinetic product. The results are consistent with the KPI (Kitajgorodskij packing index) values (Kitajgorodskij, 1973), calculated by using PLATON (Spek, 2009) [viz. 69.8, 70.4 and 68.8% for (IA), (IB) and (IIB), respectively], and calculated densities [1.567, 1.576, 1.503 and 1.476 Mg m^-3 for (IA), (IB), (IIA) and (IIB), respectively]. Unfortunately, no KPI data is available for (IIA) because the structure is disordered with the DMF molecules sitting on the twofold axes parallel to the b axis and PLATON is unable to calculate the KPI for a disordered structure. But, by considering the KPI value and density data of the four isomers together, we can easily conclude that the KPI value for (IIA) should be much higher than that of (IIB).

As reported by Li et al. (2007), (IA) crystallizes in the orthorhombic system with the Pna2₁ space group, while the new isomer (IB) crystallizes in monoclinic system with the P2₁/c space group. (IB) is an isomorphic structure of [FeCl₂(phen)₂] (Fu et al., 2005), [MnCl₂(phen)₂] (Pan & Xu, 2005) and [CoBr₂(phen)₂] (Yang et al., 2011). The asymmetric unit for both (IA) and (IB) has one [CoCl₂(phen)₂] unit. The molecular structure of (IB) is shown in Fig. 2, where the Co^II atom is coordinated by four N atoms from two phen molecules and two Cl atoms, forming a distorted o­cta­hedral geometry, with the apical N1—Co1—Cl1 and N3—Co1—Cl2 angles of 165.05 (6) and 169.92 (6)°, respectively. The Co—N and Co—Cl bond lengths for (IA) (Li et al., 2007) and (IB) are very similar, and in the ranges 2.127 (2)–2.201 (2) and 2.3733 (8)/2.4516 (8) Å, respectively, for (IB), and 2.1395 (14)–2.2043 (15) and 2.3928 (5)–2.4348 (6) Å, respectively, for (IA). A molecular overlay diagram for (IA) and (IB) with the Co^II atom and the two Cl atoms as the common basis is shown in Fig. 3. The two phen ligands in (IB) (green) are notably closer than those in (IA) (blue), but the dihedral angle between the two phen rings are similar: 73.04 (3) and 71.25 (3)° for (IA) and (IB), respectively.

The inter­molecular inter­actions of (IB) are shown in Fig. 4 and the geometry data are listed in Tables 2 and 3. In the structure, the π–π stacking (Fig. 4a, blue dashed lines) with an average centroid-to-centroid distance of 3.70 (7) Å (Table 2) and the hydrogen bond C10—H10A···Cl1ⁱ (Fig. 4a, green dashed lines), with C···Cl = 3.679 (3) Å (Table 3), co-operated to connect adjacent [CoCl₂(phen)₂] units, resulting in a chain with Co···Co = 8.7671 (10) Å. The chains inter­act with each other through van der Waals forces to form wave-shaped two-dimensional sheets parallel to the ac plane. The C3—H3A···Cl1ⁱⁱⁱ and C15—H15···Cl1^iv hydrogen bonds (Table 3) then join the undulating two-dimensional sheets into a layered architecture (Fig. 4b). In addition, there are two intra­molecular hydrogen bonds with moderate strength in (IB) (C12—H12A···Cl1 and C24—H24A···Cl2; Table 3), which in fact exist in all the isomers of dichloridobis(1,10-phenanthroline)cobalt(II).

For comparison, we analysed the inter­molecular inter­actions in (IA) using the data from Li et al. (2007). In (IA), neighbouring molecules along the b axis are stacked onto each other through C9—H9···Cl1ⁱⁱ hydrogen bonds to form columns (see Table S1 and Fig. S1 in the Supporting information). The C2—H2···Cl1ⁱ hydrogen bond and the edge-to-face (EF) C—H···π inter­actions from neighbouring columns work together to stabilize the columns and connect them into a three-dimensional architecture (see Table S1 and Fig. S1b in the Supporting information).

Thus, with rather similar molecular structures, (IB) is a layered structure and (IA) consists of parallel columns with significantly different supra­molecular networks: (i) the inter­actions between phen rings are EF C—H···π in (IA), but offset face-to-face (OFF) π–π in (IB); (ii) although in both (IA) and (IB) only one Cl atom from each of the [CoCl₂(phen)₂] units is involved in C—H···Cl hydrogen-bonding inter­actions, the Cl1 atom in (IA) bridges two H atoms from two neighbouring molecules to form bifurcated hydrogen bonds, while atom Cl1 in (IB) links three H atoms from the nearby molecules to form a trifurcated hydrogen bond. Theoretical calculations showed that for electron-deficient nitro­gen-containing aromatic compounds, lower total energy levels were achieved by adopting the OFF π–π mode, and the energy difference between OFF π–π and EF C—H···π for pyridine, pyrazine and triazine are 4.46, 3.50 and 2.65 kcal mol^-1, respectively (Geronimo et al., 2010). Janiak summarized the π-inter­actions in the metal complexes with nitro­gen-containing aromatic ligands. He indicated that the OFF π–π stacking of aromatic moieties shows increased stability when both partners are electron-poor, and a coordinated metal cation will decrease the electron density of the π-system and increase the tenancy of stacking (Janiak, 2000). This means that (IB) should have lower energy and be more stable that (IA), which is consistent with the results from our isomerization experiments.

The molecular and supra­molecular structures of (IIB) are shown in Figs. 5 and 6, and the supra­molecular structure of (IIA) is shown in Fig. S2 (see Supporting information) for comparison. As reported by Cai et al., (IIA) belongs to orthorhombic space group Pbcn, and only a half of the [CoCl₂(phen)₂].DMF is unique (Cai et al., 2008), while the new isomer (IIB) crystalizes in the monoclinic P2₁/c space group and the asymmetric unit consists of a complete [CoCl₂(phen)₂].DMF unit. Yet, similar to (IA) and (IB), the coordination geometry of the Co^II atom in (IIA) and (IIB) is distorted o­cta­hedral, with an apical N1—Co1—Cl1 angle of 162.67 (4)° for (IIA), and N1—Co1—Cl1 and N4—Co1—Cl2 angles in (IIB) of 167.55 (4) and 170.23 (4)°, respectively. In addition, the Co—Cl and Co—N bond lengths in (IIA) and (IIB) are very similar, i.e. 2.127 (2)–2.201 (2) and 2.3733 (8)/2.4516 (8) Å respectively, for (IIA), and 2.1444 (12)–2.1780 (13) and 2.3889 (4)/2.4075 (4) Å, respectively, for (IIB), with the latter range slightly narrower.

As we can see from Fig. 6(a), each [CoCl₂(phen)₂] unit in (IIB) links to four other [CoCl₂(phen)₂] units and four DMF molecules to form a two-dimensional sheet parallel to the ab plane. Each DMF molecule is bonded to a [CoCl₂(phen)₂] unit through two hydrogen bonds (C1A—H1AC···Cl1 and C2A—H2AB···Cl2; Table 5) and each [CoCl₂(phen)₂] unit inter­acts to its four [CoCl₂(phen)₂] neighbours through hydrogen bonds (C9—H9A···Cl2ⁱⁱⁱ and C15—H15A···Cl1^v; Table 5). The two-dimensional sheets are further connected through π–π stacking inter­actions (Cg1···Cg2ⁱ and Cg3···Cg3ⁱⁱ; Table 4) and hydrogen bonds (C14—H14A···Cl1^iv, C20—H20A···Cl1ⁱ and C24—H24A···Cl2^vi; Table 5) to form a three-dimensional supra­molecular network, where the DMF molecules sit in channels parallel to the c axis (Fig. 6b).

By analysing the data reported by Cai et al., we found that each [CoCl₂(phen)₂] unit in (IIA) is also surrounded by four other [CoCl₂(phen)₂] units and four DMF molecules to form a two-dimensional sheet parallel to the ac-plane (see Table S2 and Fig. S2a in the Supporting information). However, the [CoCl₂(phen)₂] unit inter­acts with its four [CoCl₂(phen)₂] neighbours through C6—H6A···Cl1ⁱ and EF C8—H8A···Cg2^iv, and there is no obvious inter­action between the [CoCl₂(phen)₂] unit and the DMF molecules. The two-dimensional sheets associate with each other through C5—H5A···Cl1ⁱⁱ and EF C2—H2A···Cg1ⁱⁱⁱ inter­actions (Fig. S2b in the Supporting information) to form a three-dimensional architecture, where each of the DMF molecules is locked in a separate cavity surrounded by six [CoCl₂(phen)₂] units. The overlay diagram of [CoCl₂(phen)₂] units for (IIA) and (IIB) (Fig. 7, with one Co^II atom and the two Cl atoms as the common basis) shows that there is less of a difference between (IIA) (yellow) and (IIB) (purple), than between(IA) and (IB). One pair of the phen ligands are almost completely overlapped, while the other pair are crossed with respect to each other. The dihedral angle between the two phen rings is 80.36 (2)° for (IIA) and 86.88 (2)° for (IIB), which are much larger than those for (IA) and (IB) of 73.04 (3) and 71.25 (3)°, respectively.

From the discussion above, we can see that, similar to (IA) and (IB), the supra­molecular structures of (IIA) and (IIB) are also quite different: (i) EF C—H···π and OFF π–π inter­actions are observed in (IIA) and (IIB), respectively; (ii) atoms Cl1 and Cl2 in (IIB) are involved in trifurcated and bifurcated hydrogen bonding, respectively, while both atoms Cl1 and Cl2 in (IIA) only form one C—H···Cl hydrogen bond; (iii) the DMF molecules in (IIB) are involved in hydrogen bonding, but the DMF molecules do not show any apparent hydrogen-bonding inter­actions. However, what makes the two isomers more inter­esting is that, compared to (IIB), (IIA) with a less stable EF C—H···π inter­action mode and fewer C—H···Cl hydrogen bonds has a much higher density (1.503 versus 1.476 Mg m^-3) and a higher thermostability. This means that here the best packing does not go together with the best inter­actions. Similar observations have been made for quite a few compounds, such as RSO₂NHN═CR₂ (R = p-tolyl), where the thermodynamic form does not contain the best hydrogen bond, i.e. N—H···O═S (Desiraju, 2007' Roy & Nangia, 2007).

In summary, two pairs of supra­molecular isomers of dichloridobis(1,10-phenanthroline)cobalt(II) were synthesized in DMF and structurally characterized. The heating rate and reaction temperature are the key factors for the crystallization of the four isomers. Of the isomers, (IB) and (IIA) are the thermodynamic and stable kinetic isomers, respectively, and (IA) and (IIB) are the two metastable kinetic products. Structural analysis reveals that the phen ligands inter­act with each other through OFF π–π stacking in (IB) and (IIB), but by EF C—H···π inter­actions in (IA) and (IIA). (IIA) is among the uncommon examples that are stable and densely packed but without best inter­molecular inter­actions. A study on the supra­molecular isomerization of the system and theory calculations are presently in progress by our group.

Synthesis and crystallization

CoCl₂·6H₂O (0.5 ml, 0.10 mol) in DMF and 1,10-phenanthroline (1.0 ml, 0.10 mol) in DMF were mixed at room temperature in a 5 ml vial with cap. When the reaction mixtures were placed directly into a 373 K oven, a ~269 K refrigerator or a 333 K oven for 12 h, red needle-like crystals of (IA), brown block-shaped crystals of (IIA) or red block-shaped crystals of (IIB) were obtained. If the reaction mixture was heated from room temperature (~298 K) to 373 K at a rate of 80 K h^-1 and kept at 373 K for 12 h, red plate-shaped crystals of (IB) formed.

Refinement details

Crystal data, data collection and structure refinement details of (IB) and (IIB) are summarized in Table 1. H atoms bonded to C atoms were treated as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic rings, or C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl groups.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2013); cell refinement: APEX2 (Bruker, 2013); data reduction: APEX2 (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006).

Figures

	Fig. 1. A summary of crystallization and isomerization conditions of (IA), (IB), (IIA) and (IIB).
	Fig. 2. The molecular structure of (IB), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A molecular overlay of the [CoCl2(phen)2] unit from (IA) (blue) and (IB) (green), with the Co^II atom and the two Cl atoms as the common basis.
	Fig. 4. The supramolecular structure of (IB), showing (a) the chain viewed parallel to theb axis and (b) the packing diagrams viewed parallel to the a axis. (Key: 1 = Cg1, 2 = Cg2, 3 = Cg3 and 4 = Cg4.) Blue dashed lines represent π–π interactions and green dash lines represent C—H···Cl hydrogen bonds. All H atoms, except those involved in hydrogen-bonding interactions, have been omitted for clarity. [Symmetry codes: (i) x-1, -y+3/2, z-1/2; (ii) x+1, -y+3/2, z+1/2; (iii) -x+1, y+1/2, -z+1/2; (iv) -x+2, y+1/2, -z+1/2.]
	Fig. 5. The molecular structure of (IIB), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 6. The supramolecular structure of (IIB), showing (a) the layer parallel to the ab plane and (b) the interactions between two neighbouring layers (blue and pink) viewed parallel to the c axis with the DMF molecules shown in the space-filling style. Green dashed lines represent C—H···Cl hydrogen bonds and dark dashed lines represent π–π stacking. All H atoms, except those involved in hydrogen-bonding interactions, have been omitted for clarity. [Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z; (iii) -x+2, y-1/2, -z+1/2; (iv) x, -y+3/2, z+1/2; (v) -x+1, y-1/2, -z+1/2; (vi) x, -y+3/2, z-1/2.]
	Fig. 7. A molecular overlay of the [CoCl2(phen)2] unit from (IIA) (yellow) and (IIB) (purple) with the Co^IIatom and the two Cl atoms as the common basis.

(IB) Dichloridobis(1,10-phenanthroline-κ²N,N')cobalt(II)

Crystal data

[CoCl2(C12H8N2)2]	F(000) = 996
Mr = 490.24	Dx = 1.576 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2035 (11) Å	Cell parameters from 3478 reflections
b = 16.6206 (16) Å	θ = 3.1–25.4°
c = 14.4854 (11) Å	µ = 1.11 mm^−1
β = 122.760 (5)°	T = 180 K
V = 2065.8 (4) Å^3	Plate, red
Z = 4	0.20 × 0.15 × 0.04 mm

Data collection

Bruker D8 VENTURE Photon 100 CMOS diffractometer	2735 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.073
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θmax = 26.0°, θmin = 3.1°
Tmin = 0.663, Tmax = 0.746	h = −12→12
18709 measured reflections	k = −20→19
4037 independent reflections	l = −17→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0259P)^2 + 0.6996P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4037 reflections	Δρmax = 0.45 e Å^−3
280 parameters	Δρmin = −0.35 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Co1	0.67640 (4)	0.73429 (2)	0.27648 (3)	0.01385 (12)
Cl1	0.80442 (8)	0.64824 (4)	0.21062 (6)	0.01950 (18)
Cl2	0.57463 (9)	0.63541 (4)	0.33936 (6)	0.0270 (2)
N1	0.5513 (3)	0.83059 (13)	0.29955 (17)	0.0150 (5)
N2	0.4696 (3)	0.74703 (12)	0.11806 (17)	0.0143 (5)
N3	0.7817 (3)	0.83745 (13)	0.24465 (17)	0.0155 (5)
N4	0.8786 (3)	0.76048 (13)	0.43387 (17)	0.0154 (5)
C1	0.5927 (3)	0.87187 (16)	0.3895 (2)	0.0179 (7)
H1A	0.6812	0.8543	0.4571	0.022*
C2	0.5130 (3)	0.93973 (17)	0.3899 (2)	0.0218 (7)
H2A	0.5485	0.9678	0.4566	0.026*
C3	0.3843 (3)	0.96578 (17)	0.2948 (2)	0.0228 (7)
H3A	0.3296	1.0123	0.2940	0.027*
C4	0.3336 (3)	0.92245 (16)	0.1975 (2)	0.0182 (7)
C5	0.4211 (3)	0.85557 (16)	0.2041 (2)	0.0150 (6)
C6	0.3768 (3)	0.81001 (16)	0.1068 (2)	0.0145 (6)
C7	0.2422 (3)	0.83162 (16)	0.0065 (2)	0.0164 (7)
C8	0.1525 (3)	0.89893 (17)	0.0029 (2)	0.0226 (7)
H8A	0.0594	0.9127	−0.0643	0.027*
C9	0.1979 (3)	0.94330 (17)	0.0935 (2)	0.0228 (7)
H9A	0.1386	0.9892	0.0882	0.027*
C10	0.2040 (3)	0.78495 (18)	−0.0860 (2)	0.0224 (7)
H10A	0.1140	0.7971	−0.1558	0.027*
C11	0.2977 (3)	0.72213 (19)	−0.0742 (2)	0.0252 (8)
H11A	0.2736	0.6903	−0.1360	0.030*
C12	0.4295 (3)	0.70459 (17)	0.0292 (2)	0.0199 (7)
H12A	0.4930	0.6603	0.0360	0.024*
C13	0.7342 (3)	0.87456 (17)	0.1507 (2)	0.0220 (7)
H13A	0.6481	0.8526	0.0852	0.026*
C14	0.8040 (4)	0.94407 (18)	0.1430 (3)	0.0312 (8)
H14A	0.7656	0.9689	0.0738	0.037*
C15	0.9287 (4)	0.97607 (18)	0.2365 (3)	0.0317 (8)
H15A	0.9768	1.0239	0.2330	0.038*
C16	0.9852 (3)	0.93793 (17)	0.3379 (2)	0.0244 (7)
C17	0.9074 (3)	0.86875 (16)	0.3378 (2)	0.0170 (7)
C20	1.1663 (4)	0.92701 (19)	0.5343 (3)	0.0303 (8)
H20A	1.2546	0.9468	0.6003	0.036*
C21	1.1166 (4)	0.96609 (19)	0.4392 (3)	0.0303 (8)
H21A	1.1698	1.0131	0.4396	0.036*
C18	0.9592 (3)	0.82703 (17)	0.4389 (2)	0.0175 (7)
C19	1.0889 (3)	0.85641 (17)	0.5378 (2)	0.0228 (7)
C22	1.1347 (4)	0.81314 (19)	0.6342 (2)	0.0271 (8)
H22A	1.2224	0.8299	0.7027	0.033*
C23	1.0519 (4)	0.74696 (18)	0.6281 (2)	0.0265 (8)
H23A	1.0809	0.7177	0.6928	0.032*
C24	0.9242 (3)	0.72188 (17)	0.5267 (2)	0.0203 (7)
H24A	0.8680	0.6755	0.5243	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0123 (2)	0.0142 (2)	0.01192 (19)	0.00049 (17)	0.00456 (16)	0.00012 (17)
Cl1	0.0160 (4)	0.0179 (4)	0.0237 (4)	0.0007 (3)	0.0102 (3)	−0.0027 (3)
Cl2	0.0279 (5)	0.0252 (4)	0.0273 (4)	−0.0037 (3)	0.0144 (4)	0.0044 (3)
N1	0.0149 (13)	0.0163 (13)	0.0137 (12)	−0.0008 (10)	0.0077 (11)	−0.0004 (10)
N2	0.0137 (13)	0.0153 (13)	0.0142 (12)	−0.0004 (10)	0.0078 (11)	−0.0013 (10)
N3	0.0150 (13)	0.0170 (13)	0.0131 (12)	0.0002 (10)	0.0066 (11)	−0.0011 (10)
N4	0.0141 (13)	0.0178 (13)	0.0137 (12)	0.0012 (10)	0.0070 (11)	−0.0009 (10)
C1	0.0144 (16)	0.0214 (17)	0.0189 (16)	−0.0032 (12)	0.0096 (14)	−0.0049 (13)
C2	0.0263 (18)	0.0204 (17)	0.0218 (16)	−0.0074 (14)	0.0151 (15)	−0.0094 (13)
C3	0.0282 (19)	0.0155 (16)	0.0336 (19)	0.0012 (13)	0.0224 (17)	−0.0019 (14)
C4	0.0196 (16)	0.0135 (15)	0.0247 (17)	0.0001 (12)	0.0141 (15)	0.0004 (13)
C5	0.0135 (15)	0.0154 (15)	0.0153 (15)	−0.0027 (12)	0.0074 (13)	0.0016 (12)
C6	0.0148 (16)	0.0144 (15)	0.0156 (15)	−0.0023 (12)	0.0091 (13)	0.0009 (12)
C7	0.0150 (16)	0.0172 (15)	0.0154 (15)	0.0020 (12)	0.0071 (13)	0.0051 (12)
C8	0.0168 (17)	0.0258 (18)	0.0202 (16)	0.0048 (13)	0.0066 (14)	0.0083 (14)
C9	0.0189 (17)	0.0181 (17)	0.0311 (18)	0.0097 (13)	0.0133 (15)	0.0084 (14)
C10	0.0138 (16)	0.0332 (19)	0.0140 (15)	0.0042 (13)	0.0035 (14)	0.0051 (13)
C11	0.0210 (18)	0.036 (2)	0.0150 (15)	0.0016 (15)	0.0075 (14)	−0.0066 (14)
C12	0.0153 (17)	0.0219 (17)	0.0174 (16)	0.0019 (13)	0.0055 (14)	−0.0048 (13)
C13	0.0219 (18)	0.0257 (18)	0.0178 (16)	−0.0021 (13)	0.0104 (14)	0.0009 (13)
C14	0.037 (2)	0.0283 (19)	0.0277 (18)	−0.0033 (15)	0.0173 (17)	0.0078 (15)
C15	0.035 (2)	0.0231 (18)	0.041 (2)	−0.0111 (15)	0.0229 (18)	0.0012 (16)
C16	0.0229 (18)	0.0210 (17)	0.0305 (18)	−0.0062 (13)	0.0153 (16)	−0.0051 (14)
C17	0.0166 (16)	0.0166 (16)	0.0190 (16)	−0.0007 (12)	0.0104 (14)	−0.0038 (12)
C20	0.0193 (18)	0.036 (2)	0.0283 (18)	−0.0099 (15)	0.0080 (16)	−0.0146 (16)
C21	0.0261 (19)	0.0265 (19)	0.0355 (19)	−0.0115 (14)	0.0148 (17)	−0.0113 (15)
C18	0.0131 (16)	0.0191 (16)	0.0192 (15)	0.0006 (12)	0.0081 (14)	−0.0057 (13)
C19	0.0177 (17)	0.0263 (18)	0.0206 (16)	−0.0014 (13)	0.0080 (14)	−0.0067 (14)
C22	0.0219 (18)	0.040 (2)	0.0152 (16)	−0.0008 (15)	0.0070 (15)	−0.0104 (14)
C23	0.0248 (18)	0.038 (2)	0.0103 (14)	0.0077 (15)	0.0052 (14)	0.0016 (14)
C24	0.0194 (17)	0.0234 (17)	0.0171 (15)	0.0017 (13)	0.0093 (14)	0.0005 (13)

Geometric parameters (Å, º)

Co1—N2	2.127 (2)	C8—H8A	0.9500
Co1—N4	2.134 (2)	C9—H9A	0.9500
Co1—N1	2.182 (2)	C10—C11	1.363 (4)
Co1—N3	2.201 (2)	C10—H10A	0.9500
Co1—Cl2	2.3733 (8)	C11—C12	1.399 (4)
Co1—Cl1	2.4516 (8)	C11—H11A	0.9500
N1—C1	1.323 (3)	C12—H12A	0.9500
N1—C5	1.364 (3)	C13—C14	1.393 (4)
N2—C12	1.323 (3)	C13—H13A	0.9500
N2—C6	1.361 (3)	C14—C15	1.369 (4)
N3—C13	1.325 (3)	C14—H14A	0.9500
N3—C17	1.365 (3)	C15—C16	1.405 (4)
N4—C24	1.326 (3)	C15—H15A	0.9500
N4—C18	1.357 (3)	C16—C17	1.397 (4)
C1—C2	1.392 (4)	C16—C21	1.428 (4)
C1—H1A	0.9500	C17—C18	1.438 (4)
C2—C3	1.361 (4)	C20—C21	1.349 (4)
C2—H2A	0.9500	C20—C19	1.430 (4)
C3—C4	1.408 (4)	C20—H20A	0.9500
C3—H3A	0.9500	C21—H21A	0.9500
C4—C5	1.396 (4)	C18—C19	1.411 (4)
C4—C9	1.431 (4)	C19—C22	1.407 (4)
C5—C6	1.440 (4)	C22—C23	1.360 (4)
C6—C7	1.402 (4)	C22—H22A	0.9500
C7—C10	1.409 (4)	C23—C24	1.399 (4)
C7—C8	1.428 (4)	C23—H23A	0.9500
C8—C9	1.351 (4)	C24—H24A	0.9500
N2—Co1—N4	162.50 (8)	C7—C8—H8A	119.5
N2—Co1—N1	76.77 (8)	C8—C9—C4	121.2 (3)
N4—Co1—N1	89.67 (8)	C8—C9—H9A	119.4
N2—Co1—N3	90.47 (8)	C4—C9—H9A	119.4
N4—Co1—N3	76.44 (8)	C11—C10—C7	119.2 (3)
N1—Co1—N3	81.54 (8)	C11—C10—H10A	120.4
N2—Co1—Cl2	95.64 (6)	C7—C10—H10A	120.4
N4—Co1—Cl2	95.86 (7)	C10—C11—C12	119.8 (3)
N1—Co1—Cl2	92.04 (6)	C10—C11—H11A	120.1
N3—Co1—Cl2	169.92 (6)	C12—C11—H11A	120.1
N2—Co1—Cl1	93.71 (6)	N2—C12—C11	122.8 (3)
N4—Co1—Cl1	97.13 (6)	N2—C12—H12A	118.6
N1—Co1—Cl1	165.05 (6)	C11—C12—H12A	118.6
N3—Co1—Cl1	87.11 (6)	N3—C13—C14	123.4 (3)
Cl2—Co1—Cl1	100.44 (3)	N3—C13—H13A	118.3
C1—N1—C5	117.1 (2)	C14—C13—H13A	118.3
C1—N1—Co1	129.02 (19)	C15—C14—C13	119.0 (3)
C5—N1—Co1	113.45 (17)	C15—C14—H14A	120.5
C12—N2—C6	117.7 (2)	C13—C14—H14A	120.5
C12—N2—Co1	126.87 (19)	C14—C15—C16	119.7 (3)
C6—N2—Co1	115.19 (17)	C14—C15—H15A	120.1
C13—N3—C17	117.6 (2)	C16—C15—H15A	120.1
C13—N3—Co1	129.01 (19)	C17—C16—C15	117.3 (3)
C17—N3—Co1	113.20 (17)	C17—C16—C21	119.2 (3)
C24—N4—C18	118.1 (2)	C15—C16—C21	123.5 (3)
C24—N4—Co1	126.19 (19)	N3—C17—C16	123.0 (3)
C18—N4—Co1	115.53 (17)	N3—C17—C18	117.0 (2)
N1—C1—C2	123.3 (3)	C16—C17—C18	120.0 (2)
N1—C1—H1A	118.4	C21—C20—C19	121.4 (3)
C2—C1—H1A	118.4	C21—C20—H20A	119.3
C3—C2—C1	119.9 (3)	C19—C20—H20A	119.3
C3—C2—H2A	120.0	C20—C21—C16	121.1 (3)
C1—C2—H2A	120.0	C20—C21—H21A	119.5
C2—C3—C4	118.8 (3)	C16—C21—H21A	119.5
C2—C3—H3A	120.6	N4—C18—C19	123.0 (3)
C4—C3—H3A	120.6	N4—C18—C17	117.4 (2)
C5—C4—C3	117.6 (3)	C19—C18—C17	119.5 (3)
C5—C4—C9	118.9 (3)	C22—C19—C18	117.1 (3)
C3—C4—C9	123.5 (3)	C22—C19—C20	124.1 (3)
N1—C5—C4	123.2 (2)	C18—C19—C20	118.7 (3)
N1—C5—C6	116.7 (2)	C23—C22—C19	119.2 (3)
C4—C5—C6	120.1 (2)	C23—C22—H22A	120.4
N2—C6—C7	123.3 (2)	C19—C22—H22A	120.4
N2—C6—C5	117.2 (2)	C22—C23—C24	120.2 (3)
C7—C6—C5	119.5 (3)	C22—C23—H23A	119.9
C6—C7—C10	117.2 (3)	C24—C23—H23A	119.9
C6—C7—C8	119.2 (3)	N4—C24—C23	122.4 (3)
C10—C7—C8	123.7 (2)	N4—C24—H24A	118.8
C9—C8—C7	121.1 (3)	C23—C24—H24A	118.8
C9—C8—H8A	119.5
C5—N1—C1—C2	−2.0 (4)	C17—N3—C13—C14	−1.2 (4)
Co1—N1—C1—C2	170.5 (2)	Co1—N3—C13—C14	174.1 (2)
N1—C1—C2—C3	1.1 (5)	N3—C13—C14—C15	0.4 (5)
C1—C2—C3—C4	0.6 (4)	C13—C14—C15—C16	0.9 (5)
C2—C3—C4—C5	−1.2 (4)	C14—C15—C16—C17	−1.2 (5)
C2—C3—C4—C9	178.5 (3)	C14—C15—C16—C21	178.6 (3)
C1—N1—C5—C4	1.3 (4)	C13—N3—C17—C16	0.9 (4)
Co1—N1—C5—C4	−172.3 (2)	Co1—N3—C17—C16	−175.2 (2)
C1—N1—C5—C6	−179.8 (2)	C13—N3—C17—C18	−179.0 (3)
Co1—N1—C5—C6	6.6 (3)	Co1—N3—C17—C18	5.0 (3)
C3—C4—C5—N1	0.2 (4)	C15—C16—C17—N3	0.3 (5)
C9—C4—C5—N1	−179.5 (3)	C21—C16—C17—N3	−179.5 (3)
C3—C4—C5—C6	−178.6 (3)	C15—C16—C17—C18	−179.9 (3)
C9—C4—C5—C6	1.6 (4)	C21—C16—C17—C18	0.3 (4)
C12—N2—C6—C7	0.0 (4)	C19—C20—C21—C16	−0.6 (5)
Co1—N2—C6—C7	174.9 (2)	C17—C16—C21—C20	0.0 (5)
C12—N2—C6—C5	179.7 (2)	C15—C16—C21—C20	−179.8 (3)
Co1—N2—C6—C5	−5.4 (3)	C24—N4—C18—C19	0.4 (4)
N1—C5—C6—N2	−1.0 (4)	Co1—N4—C18—C19	175.3 (2)
C4—C5—C6—N2	177.9 (3)	C24—N4—C18—C17	−179.3 (2)
N1—C5—C6—C7	178.7 (2)	Co1—N4—C18—C17	−4.4 (3)
C4—C5—C6—C7	−2.3 (4)	N3—C17—C18—N4	−0.5 (4)
N2—C6—C7—C10	−0.2 (4)	C16—C17—C18—N4	179.6 (3)
C5—C6—C7—C10	−179.9 (3)	N3—C17—C18—C19	179.8 (3)
N2—C6—C7—C8	−179.8 (3)	C16—C17—C18—C19	−0.1 (4)
C5—C6—C7—C8	0.5 (4)	N4—C18—C19—C22	0.4 (4)
C6—C7—C8—C9	2.1 (4)	C17—C18—C19—C22	−179.9 (3)
C10—C7—C8—C9	−177.5 (3)	N4—C18—C19—C20	179.8 (3)
C7—C8—C9—C4	−2.8 (5)	C17—C18—C19—C20	−0.5 (4)
C5—C4—C9—C8	0.9 (4)	C21—C20—C19—C22	−179.8 (3)
C3—C4—C9—C8	−178.8 (3)	C21—C20—C19—C18	0.8 (5)
C6—C7—C10—C11	0.0 (4)	C18—C19—C22—C23	−1.0 (5)
C8—C7—C10—C11	179.6 (3)	C20—C19—C22—C23	179.6 (3)
C7—C10—C11—C12	0.3 (5)	C19—C22—C23—C24	0.8 (5)
C6—N2—C12—C11	0.3 (4)	C18—N4—C24—C23	−0.6 (4)
Co1—N2—C12—C11	−173.9 (2)	Co1—N4—C24—C23	−174.9 (2)
C10—C11—C12—N2	−0.5 (5)	C22—C23—C24—N4	0.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Cl1^i	0.95	2.62	3.570 (3)	175
C10—H10A···Cl1^ii	0.95	2.82	3.679 (3)	152
C12—H12A···Cl1	0.95	2.80	3.396 (3)	122
C15—H15A···Cl1^iii	0.95	2.82	3.733 (3)	162
C24—H24A···Cl2	0.95	2.81	3.417 (3)	123

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

(IIB) Dichloridobis(1,10-phenanthroline-κ²N,N')cobalt(II) dimethylformamide monosolvate

Crystal data

[CoCl2(C12H8N2)2]·C3H7NO	F(000) = 1156
Mr = 563.33	Dx = 1.476 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.0920 (8) Å	Cell parameters from 9717 reflections
b = 11.1929 (6) Å	θ = 3.1–27.5°
c = 14.1149 (8) Å	µ = 0.92 mm^−1
β = 94.487 (2)°	T = 180 K
V = 2534.5 (2) Å^3	Block, red
Z = 4	0.40 × 0.25 × 0.20 mm

Data collection

Bruker D8 VENTURE Photon 100 CMOS diffractometer	4510 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.030
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θmax = 26.0°, θmin = 3.1°
Tmin = 0.643, Tmax = 0.746	h = −19→19
60743 measured reflections	k = −13→13
4975 independent reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0278P)^2 + 1.379P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
4975 reflections	Δρmax = 0.27 e Å^−3
327 parameters	Δρmin = −0.28 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Co1	0.74582 (2)	0.67173 (2)	0.16280 (2)	0.02039 (7)
Cl1	0.64088 (2)	0.80557 (4)	0.09341 (3)	0.03168 (10)
Cl2	0.79531 (3)	0.79678 (4)	0.29230 (3)	0.03357 (10)
N1	0.84522 (7)	0.54467 (11)	0.19338 (9)	0.0236 (3)
N2	0.84157 (7)	0.73422 (11)	0.07737 (8)	0.0222 (3)
N3	0.65880 (7)	0.57929 (11)	0.24406 (9)	0.0231 (3)
N4	0.69077 (8)	0.54009 (12)	0.06303 (9)	0.0274 (3)
C1	0.84666 (10)	0.45224 (15)	0.25214 (11)	0.0298 (3)
H1A	0.7979	0.4350	0.2835	0.036*
C2	0.91637 (11)	0.37886 (15)	0.27015 (12)	0.0344 (4)
H2A	0.9144	0.3133	0.3126	0.041*
C3	0.98735 (10)	0.40217 (15)	0.22617 (12)	0.0332 (4)
H3A	1.0352	0.3529	0.2376	0.040*
C4	0.98870 (9)	0.50017 (14)	0.16372 (11)	0.0259 (3)
C5	0.91558 (9)	0.56885 (13)	0.14965 (10)	0.0213 (3)
C6	0.91353 (9)	0.67085 (13)	0.08778 (10)	0.0203 (3)
C7	0.98536 (9)	0.70209 (14)	0.04261 (11)	0.0243 (3)
C8	1.05869 (9)	0.62939 (15)	0.05769 (11)	0.0288 (3)
H8A	1.1070	0.6495	0.0265	0.035*
C9	1.06034 (9)	0.53310 (15)	0.11527 (12)	0.0291 (3)
H9A	1.1097	0.4864	0.1238	0.035*
C10	0.98123 (10)	0.80611 (15)	−0.01322 (12)	0.0310 (4)
H10A	1.0284	0.8315	−0.0444	0.037*
C11	0.90897 (10)	0.87044 (16)	−0.02245 (12)	0.0333 (4)
H11A	0.9056	0.9413	−0.0596	0.040*
C12	0.83993 (10)	0.83091 (14)	0.02328 (11)	0.0277 (3)
H12A	0.7896	0.8755	0.0151	0.033*
C13	0.64532 (9)	0.59724 (14)	0.33454 (11)	0.0273 (3)
H13A	0.6791	0.6536	0.3701	0.033*
C14	0.58335 (10)	0.53668 (16)	0.37996 (13)	0.0356 (4)
H14A	0.5762	0.5511	0.4452	0.043*
C15	0.53344 (10)	0.45687 (16)	0.32967 (14)	0.0377 (4)
H15A	0.4909	0.4156	0.3594	0.045*
C16	0.54529 (10)	0.43606 (14)	0.23351 (14)	0.0338 (4)
C17	0.61009 (9)	0.49855 (13)	0.19390 (11)	0.0256 (3)
C18	0.62648 (10)	0.47878 (14)	0.09670 (12)	0.0284 (3)
C19	0.57559 (12)	0.39897 (15)	0.04095 (13)	0.0393 (4)
C20	0.50809 (12)	0.33968 (16)	0.08310 (17)	0.0498 (5)
H20A	0.4725	0.2878	0.0452	0.060*
C21	0.49445 (11)	0.35617 (17)	0.17450 (16)	0.0456 (5)
H21A	0.4503	0.3142	0.2007	0.055*
C22	0.59415 (15)	0.38387 (18)	−0.05361 (15)	0.0531 (6)
H22A	0.5618	0.3311	−0.0942	0.064*
C23	0.65879 (15)	0.44529 (19)	−0.08697 (14)	0.0529 (6)
H23A	0.6719	0.4350	−0.1509	0.063*
C24	0.70617 (12)	0.52398 (17)	−0.02677 (12)	0.0386 (4)
H24A	0.7506	0.5669	−0.0514	0.046*
C1A	0.66149 (14)	1.1200 (2)	0.14239 (16)	0.0558 (6)
H1AA	0.6539	1.0427	0.1732	0.084*
H1AB	0.6167	1.1322	0.0922	0.084*
H1AC	0.6600	1.1841	0.1895	0.084*
C2A	0.81413 (15)	1.0924 (2)	0.16403 (17)	0.0642 (6)
H2AA	0.8055	1.0153	0.1947	0.096*
H2AB	0.8229	1.1546	0.2126	0.096*
H2AC	0.8631	1.0875	0.1271	0.096*
C3A	0.74716 (12)	1.14191 (16)	0.00951 (14)	0.0391 (4)
H3AB	0.6966	1.1576	−0.0277	0.047*
N1A	0.74134 (9)	1.12154 (14)	0.10126 (11)	0.0382 (3)
O1A	0.81083 (9)	1.14260 (14)	−0.03188 (10)	0.0541 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01706 (10)	0.02157 (11)	0.02300 (11)	−0.00027 (7)	0.00456 (7)	−0.00015 (8)
Cl1	0.02409 (19)	0.0323 (2)	0.0387 (2)	0.00946 (15)	0.00319 (15)	−0.00089 (16)
Cl2	0.0350 (2)	0.0367 (2)	0.0294 (2)	−0.01539 (17)	0.00486 (16)	−0.00699 (16)
N1	0.0230 (6)	0.0239 (6)	0.0243 (6)	0.0014 (5)	0.0043 (5)	0.0022 (5)
N2	0.0195 (6)	0.0249 (6)	0.0225 (6)	0.0004 (5)	0.0028 (5)	0.0013 (5)
N3	0.0179 (6)	0.0234 (6)	0.0283 (7)	−0.0011 (5)	0.0038 (5)	−0.0001 (5)
N4	0.0310 (7)	0.0245 (7)	0.0268 (7)	0.0047 (5)	0.0024 (5)	−0.0035 (5)
C1	0.0303 (8)	0.0289 (8)	0.0306 (8)	0.0004 (7)	0.0054 (6)	0.0055 (7)
C2	0.0392 (9)	0.0285 (9)	0.0348 (9)	0.0042 (7)	−0.0009 (7)	0.0092 (7)
C3	0.0314 (8)	0.0286 (9)	0.0386 (9)	0.0091 (7)	−0.0044 (7)	0.0012 (7)
C4	0.0232 (7)	0.0272 (8)	0.0266 (8)	0.0040 (6)	−0.0015 (6)	−0.0051 (6)
C5	0.0198 (7)	0.0230 (7)	0.0211 (7)	0.0004 (6)	0.0015 (5)	−0.0037 (6)
C6	0.0200 (7)	0.0224 (7)	0.0185 (7)	−0.0006 (6)	0.0024 (5)	−0.0033 (6)
C7	0.0206 (7)	0.0289 (8)	0.0237 (7)	−0.0033 (6)	0.0033 (6)	−0.0063 (6)
C8	0.0183 (7)	0.0362 (9)	0.0325 (8)	−0.0018 (6)	0.0064 (6)	−0.0090 (7)
C9	0.0189 (7)	0.0328 (8)	0.0353 (8)	0.0053 (6)	0.0002 (6)	−0.0075 (7)
C10	0.0264 (8)	0.0379 (9)	0.0295 (8)	−0.0077 (7)	0.0082 (6)	0.0027 (7)
C11	0.0339 (9)	0.0338 (9)	0.0324 (9)	−0.0043 (7)	0.0040 (7)	0.0113 (7)
C12	0.0256 (8)	0.0289 (8)	0.0286 (8)	0.0023 (6)	0.0014 (6)	0.0050 (6)
C13	0.0252 (7)	0.0281 (8)	0.0293 (8)	−0.0002 (6)	0.0070 (6)	0.0009 (6)
C14	0.0339 (9)	0.0349 (9)	0.0403 (9)	0.0011 (7)	0.0173 (7)	0.0050 (8)
C15	0.0266 (8)	0.0334 (9)	0.0554 (11)	−0.0011 (7)	0.0180 (8)	0.0095 (8)
C16	0.0212 (8)	0.0230 (8)	0.0568 (11)	−0.0029 (6)	0.0015 (7)	0.0047 (7)
C17	0.0193 (7)	0.0209 (7)	0.0361 (8)	0.0000 (6)	−0.0001 (6)	0.0011 (6)
C18	0.0272 (8)	0.0212 (7)	0.0358 (9)	0.0025 (6)	−0.0038 (6)	−0.0013 (7)
C19	0.0450 (10)	0.0234 (8)	0.0467 (10)	0.0012 (7)	−0.0140 (8)	−0.0066 (8)
C20	0.0420 (11)	0.0274 (9)	0.0757 (15)	−0.0104 (8)	−0.0220 (10)	−0.0030 (9)
C21	0.0319 (9)	0.0316 (9)	0.0719 (14)	−0.0117 (8)	−0.0049 (9)	0.0025 (9)
C22	0.0735 (15)	0.0336 (10)	0.0482 (12)	0.0033 (10)	−0.0199 (11)	−0.0141 (9)
C23	0.0820 (16)	0.0446 (12)	0.0307 (10)	0.0147 (11)	−0.0049 (10)	−0.0130 (9)
C24	0.0492 (11)	0.0363 (9)	0.0307 (9)	0.0102 (8)	0.0059 (8)	−0.0031 (7)
C1A	0.0574 (13)	0.0542 (13)	0.0592 (13)	0.0012 (11)	0.0270 (11)	0.0003 (11)
C2A	0.0609 (14)	0.0720 (16)	0.0574 (14)	−0.0078 (12)	−0.0102 (11)	0.0136 (12)
C3A	0.0409 (10)	0.0332 (9)	0.0437 (10)	0.0001 (8)	0.0054 (8)	0.0039 (8)
N1A	0.0401 (8)	0.0345 (8)	0.0408 (8)	−0.0039 (7)	0.0081 (7)	0.0050 (7)
O1A	0.0510 (8)	0.0594 (9)	0.0547 (9)	−0.0021 (7)	0.0223 (7)	0.0073 (7)

Geometric parameters (Å, º)

Co1—N3	2.1444 (12)	C12—H12A	0.9500
Co1—N2	2.1466 (12)	C13—C14	1.402 (2)
Co1—N1	2.1586 (12)	C13—H13A	0.9500
Co1—N4	2.1780 (13)	C14—C15	1.363 (3)
Co1—Cl2	2.3889 (4)	C14—H14A	0.9500
Co1—Cl1	2.4075 (4)	C15—C16	1.405 (3)
N1—C1	1.325 (2)	C15—H15A	0.9500
N1—C5	1.3584 (19)	C16—C17	1.407 (2)
N2—C12	1.323 (2)	C16—C21	1.434 (3)
N2—C6	1.3562 (19)	C17—C18	1.434 (2)
N3—C13	1.327 (2)	C18—C19	1.410 (2)
N3—C17	1.3585 (19)	C19—C22	1.401 (3)
N4—C24	1.323 (2)	C19—C20	1.441 (3)
N4—C18	1.358 (2)	C20—C21	1.338 (3)
C1—C2	1.398 (2)	C20—H20A	0.9500
C1—H1A	0.9500	C21—H21A	0.9500
C2—C3	1.367 (2)	C22—C23	1.361 (3)
C2—H2A	0.9500	C22—H22A	0.9500
C3—C4	1.408 (2)	C23—C24	1.406 (3)
C3—H3A	0.9500	C23—H23A	0.9500
C4—C5	1.406 (2)	C24—H24A	0.9500
C4—C9	1.434 (2)	C1A—N1A	1.451 (2)
C5—C6	1.436 (2)	C1A—H1AA	0.9800
C6—C7	1.407 (2)	C1A—H1AB	0.9800
C7—C10	1.405 (2)	C1A—H1AC	0.9800
C7—C8	1.435 (2)	C2A—N1A	1.450 (3)
C8—C9	1.349 (2)	C2A—H2AA	0.9800
C8—H8A	0.9500	C2A—H2AB	0.9800
C9—H9A	0.9500	C2A—H2AC	0.9800
C10—C11	1.365 (2)	C3A—O1A	1.219 (2)
C10—H10A	0.9500	C3A—N1A	1.325 (2)
C11—C12	1.400 (2)	C3A—H3AB	0.9500
C11—H11A	0.9500
N3—Co1—N2	170.11 (5)	C12—C11—H11A	120.3
N3—Co1—N1	94.58 (5)	N2—C12—C11	122.95 (15)
N2—Co1—N1	76.92 (5)	N2—C12—H12A	118.5
N3—Co1—N4	76.69 (5)	C11—C12—H12A	118.5
N2—Co1—N4	97.51 (5)	N3—C13—C14	122.85 (15)
N1—Co1—N4	86.62 (5)	N3—C13—H13A	118.6
N3—Co1—Cl2	93.78 (4)	C14—C13—H13A	118.6
N2—Co1—Cl2	91.60 (3)	C15—C14—C13	119.34 (16)
N1—Co1—Cl2	92.04 (4)	C15—C14—H14A	120.3
N4—Co1—Cl2	170.23 (4)	C13—C14—H14A	120.3
N3—Co1—Cl1	92.94 (3)	C14—C15—C16	119.53 (15)
N2—Co1—Cl1	94.60 (3)	C14—C15—H15A	120.2
N1—Co1—Cl1	167.55 (4)	C16—C15—H15A	120.2
N4—Co1—Cl1	85.47 (4)	C15—C16—C17	117.53 (15)
Cl2—Co1—Cl1	97.355 (17)	C15—C16—C21	123.38 (16)
C1—N1—C5	117.75 (13)	C17—C16—C21	119.08 (17)
C1—N1—Co1	128.02 (10)	N3—C17—C16	122.60 (15)
C5—N1—Co1	114.13 (10)	N3—C17—C18	117.35 (13)
C12—N2—C6	117.93 (13)	C16—C17—C18	120.05 (15)
C12—N2—Co1	127.43 (10)	N4—C18—C19	123.38 (16)
C6—N2—Co1	114.40 (9)	N4—C18—C17	117.31 (14)
C13—N3—C17	118.11 (13)	C19—C18—C17	119.31 (16)
C13—N3—Co1	127.18 (10)	C22—C19—C18	116.78 (18)
C17—N3—Co1	114.61 (10)	C22—C19—C20	124.19 (18)
C24—N4—C18	118.12 (15)	C18—C19—C20	119.03 (18)
C24—N4—Co1	127.92 (12)	C21—C20—C19	121.36 (17)
C18—N4—Co1	113.46 (10)	C21—C20—H20A	119.3
N1—C1—C2	123.17 (15)	C19—C20—H20A	119.3
N1—C1—H1A	118.4	C20—C21—C16	121.12 (18)
C2—C1—H1A	118.4	C20—C21—H21A	119.4
C3—C2—C1	119.51 (15)	C16—C21—H21A	119.4
C3—C2—H2A	120.2	C23—C22—C19	119.63 (18)
C1—C2—H2A	120.2	C23—C22—H22A	120.2
C2—C3—C4	119.15 (15)	C19—C22—H22A	120.2
C2—C3—H3A	120.4	C22—C23—C24	120.01 (19)
C4—C3—H3A	120.4	C22—C23—H23A	120.0
C5—C4—C3	117.41 (14)	C24—C23—H23A	120.0
C5—C4—C9	119.15 (14)	N4—C24—C23	122.08 (19)
C3—C4—C9	123.44 (14)	N4—C24—H24A	119.0
N1—C5—C4	123.01 (14)	C23—C24—H24A	119.0
N1—C5—C6	117.02 (13)	N1A—C1A—H1AA	109.5
C4—C5—C6	119.96 (13)	N1A—C1A—H1AB	109.5
N2—C6—C7	123.07 (13)	H1AA—C1A—H1AB	109.5
N2—C6—C5	117.41 (12)	N1A—C1A—H1AC	109.5
C7—C6—C5	119.50 (13)	H1AA—C1A—H1AC	109.5
C10—C7—C6	117.11 (14)	H1AB—C1A—H1AC	109.5
C10—C7—C8	123.74 (14)	N1A—C2A—H2AA	109.5
C6—C7—C8	119.13 (14)	N1A—C2A—H2AB	109.5
C9—C8—C7	121.30 (14)	H2AA—C2A—H2AB	109.5
C9—C8—H8A	119.4	N1A—C2A—H2AC	109.5
C7—C8—H8A	119.4	H2AA—C2A—H2AC	109.5
C8—C9—C4	120.94 (14)	H2AB—C2A—H2AC	109.5
C8—C9—H9A	119.5	O1A—C3A—N1A	126.58 (19)
C4—C9—H9A	119.5	O1A—C3A—H3AB	116.7
C11—C10—C7	119.55 (15)	N1A—C3A—H3AB	116.7
C11—C10—H10A	120.2	C3A—N1A—C2A	121.36 (17)
C7—C10—H10A	120.2	C3A—N1A—C1A	121.70 (17)
C10—C11—C12	119.35 (15)	C2A—N1A—C1A	116.83 (18)
C10—C11—H11A	120.3
C5—N1—C1—C2	−0.6 (2)	Co1—N3—C13—C14	176.15 (12)
Co1—N1—C1—C2	−176.68 (12)	N3—C13—C14—C15	−1.0 (3)
N1—C1—C2—C3	0.3 (3)	C13—C14—C15—C16	0.4 (3)
C1—C2—C3—C4	0.2 (3)	C14—C15—C16—C17	1.0 (2)
C2—C3—C4—C5	−0.4 (2)	C14—C15—C16—C21	−178.32 (17)
C2—C3—C4—C9	179.06 (16)	C13—N3—C17—C16	1.5 (2)
C1—N1—C5—C4	0.4 (2)	Co1—N3—C17—C16	−175.11 (12)
Co1—N1—C5—C4	176.99 (11)	C13—N3—C17—C18	−178.95 (14)
C1—N1—C5—C6	−178.70 (13)	Co1—N3—C17—C18	4.43 (17)
Co1—N1—C5—C6	−2.08 (16)	C15—C16—C17—N3	−2.0 (2)
C3—C4—C5—N1	0.1 (2)	C21—C16—C17—N3	177.32 (15)
C9—C4—C5—N1	−179.36 (14)	C15—C16—C17—C18	178.48 (15)
C3—C4—C5—C6	179.16 (13)	C21—C16—C17—C18	−2.2 (2)
C9—C4—C5—C6	−0.3 (2)	C24—N4—C18—C19	0.1 (2)
C12—N2—C6—C7	−1.1 (2)	Co1—N4—C18—C19	172.68 (12)
Co1—N2—C6—C7	−175.90 (11)	C24—N4—C18—C17	−179.24 (14)
C12—N2—C6—C5	177.57 (13)	Co1—N4—C18—C17	−6.66 (17)
Co1—N2—C6—C5	2.80 (16)	N3—C17—C18—N4	1.6 (2)
N1—C5—C6—N2	−0.48 (19)	C16—C17—C18—N4	−178.83 (14)
C4—C5—C6—N2	−179.58 (13)	N3—C17—C18—C19	−177.76 (14)
N1—C5—C6—C7	178.27 (13)	C16—C17—C18—C19	1.8 (2)
C4—C5—C6—C7	−0.8 (2)	N4—C18—C19—C22	0.2 (3)
N2—C6—C7—C10	1.9 (2)	C17—C18—C19—C22	179.55 (16)
C5—C6—C7—C10	−176.81 (13)	N4—C18—C19—C20	−179.04 (15)
N2—C6—C7—C8	−179.85 (13)	C17—C18—C19—C20	0.3 (2)
C5—C6—C7—C8	1.5 (2)	C22—C19—C20—C21	178.76 (19)
C10—C7—C8—C9	177.16 (15)	C18—C19—C20—C21	−2.0 (3)
C6—C7—C8—C9	−1.0 (2)	C19—C20—C21—C16	1.6 (3)
C7—C8—C9—C4	−0.2 (2)	C15—C16—C21—C20	179.76 (18)
C5—C4—C9—C8	0.8 (2)	C17—C16—C21—C20	0.5 (3)
C3—C4—C9—C8	−178.63 (15)	C18—C19—C22—C23	−0.1 (3)
C6—C7—C10—C11	−0.9 (2)	C20—C19—C22—C23	179.18 (19)
C8—C7—C10—C11	−179.14 (16)	C19—C22—C23—C24	−0.4 (3)
C7—C10—C11—C12	−0.6 (3)	C18—N4—C24—C23	−0.6 (2)
C6—N2—C12—C11	−0.5 (2)	Co1—N4—C24—C23	−171.96 (13)
Co1—N2—C12—C11	173.46 (12)	C22—C23—C24—N4	0.8 (3)
C10—C11—C12—N2	1.4 (3)	O1A—C3A—N1A—C2A	−2.3 (3)
C17—N3—C13—C14	0.0 (2)	O1A—C3A—N1A—C1A	−178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H1AA···Cl1	0.98	2.89	3.597 (2)	130
C2A—H2AC···O1A	0.98	2.41	2.818 (3)	104
C2A—H2AA···Cl2	0.98	2.82	3.795 (3)	175
C9—H9A···Cl2^i	0.95	2.82	3.6906 (16)	153
C12—H12A···Cl1	0.95	2.82	3.4375 (16)	123
C13—H13A···Cl2	0.95	2.75	3.3755 (16)	124
C14—H14A···Cl1^ii	0.95	2.77	3.5518 (19)	140
C15—H15A···Cl1^iii	0.95	2.58	3.5203 (17)	168
C20—H20A···Cl1^iv	0.95	2.77	3.6962 (19)	164
C24—H24A···Cl2^v	0.95	2.82	3.630 (2)	144

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