Di-μ-cyanido-1:2κ2C:N,2:3κ2N:C-hexa­cyanido-1κ3C,3κ3C-tetra­kis(1,10-phenanthroline)-1κ2N,N′;2κ4N,N′;3κ2N,N′-1,3-dicobalt(III)-2-iron(II) tetra­hydrate

Zhang, Y.; Yuan, A.-H.; Zhou, H.; Guo, J.-X.; Liu, L.

doi:10.1107/S1600536809030165

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Pages m1033-m1034

doi:10.1107/S1600536809030165

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Di-μ-cyanido-1:2κ²C:N,2:3κ²N:C-hexacyanido-1κ³C,3κ³C-tetrakis(1,10-phenanthroline)-1κ²N,N′;2κ⁴N,N′;3κ²N,N′-1,3-dicobalt(III)-2-iron(II) tetrahydrate

Ying Zhang,^a Ai-Hua Yuan,^a ^* Hu Zhou,^a Ji-Xi Guo ^b and Lang Liu ^b

^aSchool of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China, and ^bInstitute of Applied Chemistry, Xinjiang University, Urumqi 830046, Xinjiang, People's Republic of China
^*Correspondence e-mail: aihuayuan@163.com

(Received 26 June 2009; accepted 29 July 2009; online 8 August 2009)

The hydrothermal reaction of CoCl₂·6H₂O, 1,10-phenanthroline (phen) and K₃[Fe(CN)₆] in deionized water yielded the title cyanide-bridged trinuclear cluster, [Co₂Fe(CN)₈(C₁₂H₈N₂)₄]·4H₂O or [{Co^III(phen)(CN)₄}₂{Fe^II(phen)₂}]·4H₂O, which contains two Co^III centers and one Fe^II center linked by cyanide bridges. The combination of coordinative bonds, O—H⋯N and O—H⋯O hydrogen bonds and π–π stacking interactions [centroid–centroid distance = 3.630 (2) Å] results in the stabilization of a supramolecular structure. All uncoordinated water molecules are disordered. Thermogravimetric analysis reveals that the title complex loses the four crystal water molecules at about 333 K, then the anhydrous phase loses no further mass up to about 573 K, above which decomposition occurs.

Related literature

For background to cyanide-bridged complexes, see: Rodríguez-Diéguez et al. (2007 ); Colacio et al. (2003 , 2005 ); Chen et al. (2006 ); Ferlay et al. (1995 ); Fernández-Armas et al. (2007 ); Goodwin et al. (2008 ); He et al. (2005 ); Kosaka et al. (2009 ); Mao et al. (2005 ); Overgaard et al. (2004 ); Paredes-García et al. (2006 ); Phillips et al. (2008 ); Reguera Balmaseda, del Castillo et al. (2008 ); Reguera, Balmaseda, Krap et al. (2008 ); Rodriguez et al. (2005 ); Xie et al. (2007 ); Yu et al. (2003 ). For related structures, see: Halbauer et al. (2008 ); Guo et al. (2007 ); Zhao et al. (2008 ); Brewer et al. (2007 ).

Experimental

Crystal data

[Co₂Fe(CN)₈(C₁₂H₈N₂)₄]·4H₂O
M_r = 1174.75
Triclinic, $[P \overline 1]$
a = 12.855 (3) Å
b = 14.006 (3) Å
c = 16.334 (3) Å
α = 72.68 (3)°
β = 82.54 (3)°
γ = 65.99 (3)°
V = 2564.5 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 173 K
0.74 × 0.56 × 0.33 mm

Data collection

Rigaku R-AXIS Spider diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.555, T_max = 0.755
41118 measured reflections
11723 independent reflections
10898 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 1.03
11723 reflections
726 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—C6	1.8747 (16)
Co1—C7	1.8779 (18)
Co1—C2	1.8960 (16)
Co1—C8	1.9076 (17)
Co1—N15	1.9693 (13)
Co1—N16	1.9762 (15)
Co2—C3	1.8744 (17)
Co2—C4	1.8822 (17)
Co2—C5	1.8975 (17)
Co2—C1	1.9044 (16)
Co2—N13	1.9652 (15)
Co2—N14	1.9665 (14)
Fe1—N2	2.0365 (14)
Fe1—N1	2.0464 (15)
Fe1—N12	2.0821 (15)
Fe1—N10	2.0845 (16)
Fe1—N11	2.0960 (16)
Fe1—N9	2.1067 (16)
N1—C1	1.144 (2)
N2—C2	1.144 (2)
N3—C3	1.147 (2)
N4—C4	1.147 (2)
N5—C5	1.149 (2)
N6—C6	1.148 (2)
N7—C7	1.156 (2)
N8—C8	1.146 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N7	0.82	2.34	3.143 (2)	167
O1—H1B⋯N3	0.82	2.12	2.939 (2)	172
O2—H2A⋯N8ⁱ	0.82	2.33	3.118 (3)	163
O2—H2B⋯N4	0.82	2.16	2.970 (2)	170
O3A—H3A⋯O2ⁱⁱ	0.82	2.22	2.971 (3)	153
O3A—H3B⋯O1	0.82	2.12	2.930 (3)	169
O3B—H3C⋯O1	0.85	1.97	2.823 (16)	179
O3B—H3D⋯O2ⁱⁱ	0.90	2.11	2.889 (18)	144
O4A—H4A⋯N6ⁱⁱⁱ	0.84	2.11	2.930 (6)	165
O4A—H4B⋯N5	0.82	2.13	2.870 (4)	151
O4B—H4D⋯N5	0.82	2.09	2.848 (4)	153
Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y+2, -z; (iii) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030165/at2833sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030165/at2833Isup2.hkl

checkCIF report

Comment top

Cyanide-bridged complexes have been investigated extensively over the past few years due to their excellent properties and potential applications, such as, high T_c molecular-based magnets (Ferlay et al., 1995; Kosaka et al., 2009), hydrogen storages (Reguera, Balmaseda & Krap et al., 2008; Reguera, Balmaseda & del Castillo et al., 2008), negative thermal expansion materials (Goodwin et al., 2008; Phillips et al., 2008), and so on. Increasing studies have shown that the hydrothermal reaction is a versatile and useful technique to prepare cyanide-bridged complexes, though the majority of synthetic procedures of cyanide-based systems still follow conventional solution routes. Recently, Colacio (Colacio et al., 2003; Rodriguez et al., 2005; Colacio et al., 2005; Rodríguez-Diéguez et al., 2007) and others (Yu et al., 2003; He et al., 2005; Mao et al., 2005; Chen et al., 2006) have shown that cyanide-bridged bimetallic complexes can also be assembled through hydrothermal reactions by using either [M(CN)₆]^3- (M = Fe^III, Co^III) anions as a source of cyanide groups, which act as both reducing agents and bridging ligands.

Bearing this in mind, we introduced CoCl₂.6H₂O, 1,10-phenanthroline (phen), and K₃[Fe(CN)₆] (or Na₂[Fe(CN)₅NO].2H₂O) into the reaction in order to obtain a Co—Fe bimetallic monometallic complex. It is interesting that a novel cyanide-bridged trinuclear cluster [{Co^III(phen)(CN)₄}₂{Fe^II(phen)₂}].4H₂O, was obtained. It should be noted here that, to the best of our knowledge, the title complex is the first example of a trinuclear cluster prepared by hydrothermal method in the cyanide-based system.

The asymmetric unit of the structure of the title complex is given in Fig. 1. Selected bond lengths and angles are listed in Table 1. Within the neutral [{Co^III(phen)(CN)₄}₂{Fe^II(phen)₂}] unit, there are one Fe^II center and two Co^III centers, with {FeN6} and {CoN2C4} coordination environments, respectively. The Fe center is six-coordinate and adopts a distorted slightly octahedral geometry. Each Fe center is coordinated with two coordinated phen ligands and two bridging cyanide groups in a cis arrangement with the angle N1—Fe1—N2 = 89.63 (6)°. The dihedral angle between the planes of chelating phen ligands with the Fe1 atom is ca 85°. The mean basal plane is constructed by three N atoms (N9, N11, and N12) from two phen ligands and N1 atom from one bridging cyanide group, while the axial positions are occupied by N10 atom from one phen ligand and N2 atom of the other bridging cyanide group. The geometrical data of the [Fe^II(phen)₂(CN)₂] unit in the title complex are similar to those found for the [Fe^II(phen)₂(CN)₂] unit in the one-dimensional complex [Cu₂Fe^II(CN)₄(phen)₃]_n.0.5nH₂O (He et al., 2005), the [Fe^II(bipy)₂(CN)₂] unit in the two-dimensional complex [Fe^II(bipy)₂(CN)₄Cu₂] (Colacio et al., 2003), and three-dimensional complex [Fe^II(CN)₄(phen)₂Cu₂] (Colacio et al., 2005).

The Co^III centers (Co1 and Co2) are both coordinated by two N atoms from one phen ligand, one C atom from one bridging cyanide ligand, and three C atoms from three terminal cyanide ligands. For the Co^III centers, the basal plane is formed by two N atoms of one phen ligand and two C atoms of two terminal cyanide groups, while the axial sites are occupied by two C atoms of the other two cyanide groups. As in all other cyanide-bridged complexes, the M—C bond is much shorter than the M—N bond (Table 1). Furthermore, the Co—C—N angles are closed to be linear with the angles spanning from 171° to 179°, which are comparable with those observed for the complexes obtained by hydrothermal methods (Colacio et al., 2003; He et al., 2005; Mao et al., 2005; Colacio et al., 2005), based on [Fe(CN)₆]^3- as the building block.

Thus, cyanide bridges connect one Fe^II atom to two Co^III atoms in cis arrangement, giving rise to a Co^III₂Fe^II trinuclear cluster with a Fe1 ··· Co1 distance of 5.052 Å and a Fe1 ··· Co2 distance of 5.056 Å. It is noteworthy that the structure of the title complex is distinguished from that of cyanide-based mixed-valence Co^II/Co^III complexes (Halbauer et al., 2008; Guo et al., 2007), and mixed-valence Fe^II/Fe^III (Zhao et al., 2008; Overgaard et al., 2004; Brewer et al., 2007; Xie et al., 2007; Fernández-Armas et al., 2007; Paredes-García et al., 2006) complexes belonging to other systems.

The crystallized water molecules are hydrogen-bonded to each other and terminal cyanide groups. The probable hydrogen bonding interactions are given in Table 2. In addition, weak face-to-face π-π interactions between the aromatic rings of adjacent phen ligands from neighboring trinuclear clusters also play important roles in the formation and stabilization of the three-dimensional supramolecular structure (Fig. 2). The distance between two adjacent aromatic ring center is ca 3.63 Å.

The IR spectrum (Fig. 3) of the title complex exhibits two strong peaks at 2080 cm^-1 and 2133 cm^-1, and one weak peak at 2171 cm^-1, which indicates the existence of different types of cyanide bridges in the structure. The lower frequencies at 2080 cm^-1 and 2133 cm^-1 are reasonably assigned to the terminal cyanide stretching vibrations, while the higher one of 2171 cm^-1 confirms the presence of bridging cyanide groups.

There is a broad band at the wavenumber range of 3700–2900 cm^-1 ascribed to the O—H stretching absorption (ν_O—H) in H₂O molecules. The IR spectrum exhibits characteristic strong bands of the coordinated phen ligands at 1638, 1521, 1425, 844, and 722 cm^-1 (δ_C—H benzene ring). The bands at 1521, 1425 and 722 cm^-1 are shifted from their positions for the free phen ligands (1503, 1420 and 737 cm^-1), indicating nitrogen coordination. The IR feature has been confirmed by single-crystal X-ray crystallographic analysis.

Thermogravimetric analysis (Fig. 4) is performed to study the thermal stability of the title complex, which shows the title complex loses four crystallized water molecules at above 333 K with a weight loss of 6.29% (Calc. 6.17%). The anhydrous phase loses no further mass up to about 573 K, above which thermal decomposition occurs.

Related literature top

For background to cyanide-bridged complexes, see: Rodríguez-Diéguez et al. (2007); Colacio et al. (2003, 2005); Chen et al. (2006); Ferlay et al. (1995); Fernández-Armas et al. (2007); Goodwin et al. (2008); He et al. (2005); Kosaka et al. (2009); Mao et al. (2005); Overgaard et al. (2004); Paredes-García et al. (2006); Phillips et al. (2008); Reguera Balmaseda, del Castillo et al. (2008); Reguera, Balmaseda, Krap et al. (2008); Rodriguez et al. (2005); Xie et al. (2007); Yu et al. (2003). For related structures, see: Halbauer et al. (2008); Guo et al. (2007); Zhao et al. (2008); Brewer et al. (2007).

Experimental top

All starting reagents were of analytical grade quality, obtained from commercial sources and used without further purification. A mixture of CoCl₂.6H₂O (0.1071 g, 0.45 mmol), 1,10-phenanthroline (phen, 0.0892 g, 0.45 mmol), K₃[Fe(CN)₆] (0.1482 g, 0.45 mmol) in a molar ratio of 1:1:1 combined with 10 ml deionized water was stirred for 20 min at room temperature and then transferred into a 25 ml Teflon-lined stainless-steel vessel. The mixture was heated hydrothermally at 413 K for two days under autogenous pressure. Slow cooling of the resulting solution to room temperature afforded dark red, prism-shaped crystals suitable for single-crystal X-ray structure analysis. Yield: 30% (based on Fe). These crystals were separated, washed thoroughly with deionized water and finally with ethanol, and dried. Analysis calculated for C₅₆H₄₀N₁₆O₄Co₂Fe: C 57.51, H 3.42, N 19.17%. Found: C 57.46, H 3.35, N 19.12%. EDS (energy dispersive spectrometer): Fe 32.33, Co 67.67. It is of interest that when working under the same hydrothermal conditions, except for using Na₂[Fe(CN)₅NO] instead of K₃[Fe(CN)₆] as the cyanide source, the same product was obtained (CCDC-732054). From the viewpoint of the mechanism of the formation of the title complex, it is reasonable that free cyanide groups from the dissociation of [Fe(CN)₆]^3- or [Fe(CN)₅NO]^2- might be responsible for the oxidation of the Co center from the original reduction state +II in the precursor CoCl₂.6H₂O to the oxidation state +III in the title complex.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the structure of the title complex showing 50% probability displacement ellipsoids. Water molecules have been omitted for clarity.
	Fig. 2. Hydrogen-bonded supramolecular structure of the complex.
	Fig. 3. IR spectrum of the title complex.
	Fig. 4. Thermogravimetric curve of the title complex.

Di-µ-cyanido-1:2κ²C:N,2:3κ²N:C- hexacyanido-1κ³C,3κ³C-tetrakis(1,10-phenanthroline)- 1κ²N,N';2κ⁴N,N';3κ²N,N'- 1,3-dicobalt(III)-2-iron(II) tetrahydrate top

Crystal data top

[Co₂Fe(CN)₈(C₁₂H₈N₂)₄]·4H₂O	Z = 2
M_r = 1174.75	F(000) = 1200
Triclinic, P1	D_x = 1.521 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.855 (3) Å	Cell parameters from 7618 reflections
b = 14.006 (3) Å	θ = 3.2–27.0°
c = 16.334 (3) Å	µ = 0.98 mm⁻¹
α = 72.68 (3)°	T = 173 K
β = 82.54 (3)°	Block, dark red
γ = 65.99 (3)°	0.74 × 0.56 × 0.33 mm
V = 2564.5 (12) Å³

Data collection top

Rigaku R-AXIS Spider diffractometer	11723 independent reflections
Radiation source: fine-focus sealed tube	10898 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −16→16
T_min = 0.555, T_max = 0.755	k = −18→17
41118 measured reflections	l = −21→21

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0331P)² + 1.5388P] where P = (F_o² + 2F_c²)/3
11723 reflections	(Δ/σ)_max = 0.001
726 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

[Co₂Fe(CN)₈(C₁₂H₈N₂)₄]·4H₂O	γ = 65.99 (3)°
M_r = 1174.75	V = 2564.5 (12) Å³
Triclinic, P1	Z = 2
a = 12.855 (3) Å	Mo Kα radiation
b = 14.006 (3) Å	µ = 0.98 mm⁻¹
c = 16.334 (3) Å	T = 173 K
α = 72.68 (3)°	0.74 × 0.56 × 0.33 mm
β = 82.54 (3)°

Data collection top

Rigaku R-AXIS Spider diffractometer	11723 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	10898 reflections with I > 2σ(I)
T_min = 0.555, T_max = 0.755	R_int = 0.040
41118 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.03	Δρ_max = 0.44 e Å⁻³
11723 reflections	Δρ_min = −0.70 e Å⁻³
726 parameters

Special details top

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

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	−0.124533 (16)	0.330081 (16)	0.192167 (12)	0.01867 (6)
Co2	0.211367 (16)	0.613907 (16)	0.329103 (12)	0.01846 (5)
Fe1	0.272543 (16)	0.259948 (16)	0.270557 (12)	0.01544 (5)
N1	0.22567 (11)	0.40567 (11)	0.29752 (8)	0.0231 (3)
N2	0.11105 (11)	0.30592 (11)	0.23131 (8)	0.0225 (3)
N3	−0.03701 (12)	0.73776 (12)	0.28215 (9)	0.0272 (3)
N4	0.27633 (15)	0.69837 (14)	0.14501 (10)	0.0416 (4)
N5	0.22982 (14)	0.80318 (13)	0.37282 (11)	0.0354 (3)
N6	−0.15698 (12)	0.26931 (14)	0.38441 (9)	0.0357 (4)
N7	−0.22187 (13)	0.57067 (12)	0.18027 (10)	0.0329 (3)
N8	−0.35730 (13)	0.34691 (15)	0.15092 (10)	0.0377 (4)
N9	0.23205 (12)	0.19390 (12)	0.39825 (9)	0.0275 (3)
N10	0.42921 (12)	0.19929 (12)	0.33001 (10)	0.0288 (3)
N11	0.31060 (11)	0.13043 (11)	0.21731 (9)	0.0267 (3)
N12	0.33409 (11)	0.31894 (11)	0.15018 (8)	0.0235 (3)
N13	0.36947 (11)	0.52399 (10)	0.36591 (8)	0.0204 (2)
N14	0.17586 (10)	0.55913 (10)	0.45039 (8)	0.0184 (2)
N15	−0.08549 (10)	0.35289 (10)	0.06914 (8)	0.0191 (2)
N16	−0.05795 (11)	0.17536 (11)	0.19295 (8)	0.0213 (3)
C1	0.21160 (12)	0.48801 (13)	0.30657 (9)	0.0204 (3)
C2	0.02146 (13)	0.31837 (12)	0.21564 (9)	0.0203 (3)
C3	0.05769 (13)	0.69236 (12)	0.29917 (9)	0.0214 (3)
C4	0.25134 (14)	0.66576 (14)	0.21445 (10)	0.0269 (3)
C5	0.22034 (13)	0.73388 (13)	0.35471 (10)	0.0239 (3)
C6	−0.14966 (13)	0.29636 (14)	0.31107 (10)	0.0250 (3)
C7	−0.18567 (13)	0.47879 (14)	0.18580 (10)	0.0239 (3)
C8	−0.27138 (14)	0.34141 (14)	0.16896 (10)	0.0253 (3)
C9	0.52910 (15)	0.19642 (15)	0.29379 (15)	0.0383 (4)
H9	0.5351	0.2178	0.2330	0.046*
C10	0.62613 (16)	0.16242 (16)	0.34347 (19)	0.0520 (6)
H10	0.6962	0.1614	0.3159	0.062*
C11	0.62013 (18)	0.13123 (15)	0.43026 (18)	0.0507 (6)
H11	0.6855	0.1089	0.4635	0.061*
C12	0.51653 (17)	0.13222 (14)	0.47063 (15)	0.0401 (5)
C13	0.4999 (2)	0.09982 (15)	0.56160 (15)	0.0511 (6)
H13	0.5622	0.0768	0.5982	0.061*
C14	0.3988 (2)	0.10091 (16)	0.59683 (14)	0.0493 (6)
H14	0.3906	0.0802	0.6574	0.059*
C15	0.30395 (18)	0.13297 (14)	0.54370 (12)	0.0373 (4)
C16	0.1974 (2)	0.13174 (15)	0.57587 (12)	0.0439 (5)
H16	0.1844	0.1117	0.6360	0.053*
C17	0.11322 (19)	0.15941 (16)	0.52032 (13)	0.0427 (5)
H17	0.0413	0.1579	0.5414	0.051*
C18	0.13308 (15)	0.19032 (15)	0.43129 (12)	0.0341 (4)
H18	0.0734	0.2094	0.3933	0.041*
C19	0.31693 (15)	0.16514 (13)	0.45389 (11)	0.0280 (3)
C20	0.42345 (15)	0.16639 (13)	0.41689 (12)	0.0287 (4)
C21	0.35029 (14)	0.41126 (14)	0.11906 (11)	0.0280 (3)
H21	0.3371	0.4564	0.1559	0.034*
C22	0.38586 (15)	0.44472 (15)	0.03462 (11)	0.0317 (4)
H22	0.3970	0.5110	0.0151	0.038*
C23	0.40454 (15)	0.38120 (15)	−0.01973 (11)	0.0328 (4)
H23	0.4278	0.4034	−0.0774	0.039*
C24	0.38890 (14)	0.28262 (15)	0.01076 (11)	0.0299 (4)
C25	0.40323 (17)	0.21135 (17)	−0.04085 (12)	0.0396 (4)
H25	0.4252	0.2300	−0.0993	0.048*
C26	0.38619 (17)	0.11833 (17)	−0.00829 (13)	0.0414 (5)
H26	0.3947	0.0736	−0.0445	0.050*
C27	0.35531 (15)	0.08576 (15)	0.08027 (13)	0.0344 (4)
C28	0.33953 (17)	−0.01117 (16)	0.11841 (16)	0.0444 (5)
H28	0.3493	−0.0600	0.0855	0.053*
C29	0.30996 (17)	−0.03515 (16)	0.20326 (16)	0.0462 (5)
H29	0.2996	−0.1009	0.2299	0.055*
C30	0.29509 (15)	0.03833 (15)	0.25071 (14)	0.0374 (4)
H30	0.2730	0.0214	0.3093	0.045*
C31	0.34010 (13)	0.15426 (13)	0.13257 (11)	0.0260 (3)
C32	0.35473 (13)	0.25445 (13)	0.09695 (10)	0.0245 (3)
C33	0.46540 (14)	0.50782 (14)	0.32018 (11)	0.0265 (3)
H33	0.4621	0.5467	0.2613	0.032*
C34	0.57127 (14)	0.43506 (14)	0.35623 (12)	0.0291 (3)
H34	0.6384	0.4255	0.3218	0.035*
C35	0.57866 (13)	0.37764 (13)	0.44087 (11)	0.0263 (3)
H35	0.6505	0.3285	0.4654	0.032*
C36	0.47828 (13)	0.39246 (12)	0.49103 (10)	0.0225 (3)
C37	0.47374 (14)	0.33739 (13)	0.57997 (11)	0.0272 (3)
H37	0.5424	0.2867	0.6088	0.033*
C38	0.37353 (15)	0.35609 (13)	0.62381 (11)	0.0276 (3)
H38	0.3733	0.3181	0.6826	0.033*
C39	0.26799 (13)	0.43218 (12)	0.58304 (10)	0.0219 (3)
C40	0.16036 (14)	0.45744 (13)	0.62392 (10)	0.0252 (3)
H40	0.1536	0.4225	0.6827	0.030*
C41	0.06563 (14)	0.53278 (14)	0.57807 (10)	0.0250 (3)
H41	−0.0070	0.5516	0.6055	0.030*
C42	0.07574 (13)	0.58191 (13)	0.49106 (10)	0.0213 (3)
H42	0.0091	0.6332	0.4600	0.026*
C43	0.27068 (12)	0.48641 (12)	0.49617 (9)	0.0188 (3)
C44	0.37582 (12)	0.46686 (12)	0.45018 (10)	0.0194 (3)
C45	−0.10336 (13)	0.44500 (13)	0.00828 (10)	0.0226 (3)
H45	−0.1422	0.5119	0.0226	0.027*
C46	−0.06668 (14)	0.44644 (14)	−0.07650 (10)	0.0269 (3)
H46	−0.0813	0.5137	−0.1188	0.032*
C47	−0.00973 (15)	0.35077 (15)	−0.09852 (10)	0.0277 (3)
H47	0.0158	0.3514	−0.1558	0.033*
C48	0.01046 (14)	0.25187 (14)	−0.03546 (10)	0.0243 (3)
C49	0.06927 (15)	0.14634 (15)	−0.04983 (11)	0.0304 (4)
H49	0.0983	0.1408	−0.1055	0.037*
C50	0.08422 (15)	0.05469 (14)	0.01403 (11)	0.0303 (4)
H50	0.1245	−0.0139	0.0026	0.036*
C51	0.04031 (13)	0.05916 (13)	0.09894 (11)	0.0253 (3)
C52	0.04915 (15)	−0.03224 (14)	0.16798 (12)	0.0307 (4)
H52	0.0855	−0.1033	0.1605	0.037*
C53	0.00447 (15)	−0.01708 (14)	0.24631 (11)	0.0316 (4)
H53	0.0090	−0.0780	0.2933	0.038*
C54	−0.04757 (14)	0.08730 (14)	0.25723 (10)	0.0276 (3)
H54	−0.0765	0.0959	0.3123	0.033*
C55	−0.01538 (13)	0.16124 (13)	0.11473 (10)	0.0209 (3)
C56	−0.03016 (12)	0.25769 (12)	0.04762 (9)	0.0200 (3)
O1	−0.25835 (11)	0.79447 (12)	0.20885 (9)	0.0415 (3)
H1A	−0.2471	0.7410	0.1926	0.062*
H1B	−0.1948	0.7814	0.2246	0.062*
O2	0.28189 (17)	0.81586 (13)	−0.03875 (10)	0.0616 (5)
H2A	0.2985	0.7640	−0.0584	0.092*
H2B	0.2886	0.7776	0.0108	0.092*
O3A	−0.3779 (2)	1.03096 (19)	0.15433 (19)	0.0758 (9)	0.866 (5)
H3A	−0.3618	1.0695	0.1103	0.114*	0.866 (5)
H3B	−0.3378	0.9660	0.1644	0.114*	0.866 (5)
O3B	−0.3120 (16)	1.0178 (13)	0.1828 (13)	0.0758 (9)	0.134 (5)
H3C	−0.2948	0.9503	0.1908	0.114*	0.134 (5)
H3D	−0.3271	1.0645	0.1299	0.114*	0.134 (5)
O4A	0.0980 (4)	0.9375 (4)	0.4824 (3)	0.0666 (17)	0.546 (10)
H4A	0.1018	0.8821	0.5226	0.100*	0.546 (10)
H4B	0.1402	0.9193	0.4430	0.100*	0.546 (10)
O4B	0.1348 (4)	0.9808 (4)	0.4474 (4)	0.0616 (18)	0.454 (10)
H4C	0.0512	1.0005	0.4678	0.092*	0.454 (10)
H4D	0.1514	0.9206	0.4402	0.092*	0.454 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01406 (10)	0.02221 (11)	0.01562 (10)	−0.00363 (8)	−0.00056 (7)	−0.00400 (8)
Co2	0.01609 (10)	0.01932 (10)	0.01740 (10)	−0.00382 (8)	0.00002 (7)	−0.00580 (8)
Fe1	0.01103 (9)	0.01723 (10)	0.01583 (10)	−0.00423 (8)	−0.00069 (7)	−0.00288 (8)
N1	0.0201 (6)	0.0255 (7)	0.0227 (6)	−0.0078 (5)	−0.0019 (5)	−0.0061 (5)
N2	0.0178 (6)	0.0213 (6)	0.0221 (6)	−0.0030 (5)	−0.0008 (5)	−0.0032 (5)
N3	0.0231 (7)	0.0308 (7)	0.0236 (7)	−0.0049 (6)	−0.0026 (5)	−0.0084 (6)
N4	0.0442 (10)	0.0446 (10)	0.0260 (8)	−0.0130 (8)	0.0058 (7)	−0.0044 (7)
N5	0.0332 (8)	0.0305 (8)	0.0433 (9)	−0.0082 (7)	−0.0060 (7)	−0.0144 (7)
N6	0.0211 (7)	0.0528 (10)	0.0221 (7)	−0.0059 (7)	0.0024 (5)	−0.0075 (7)
N7	0.0334 (8)	0.0305 (8)	0.0283 (7)	−0.0022 (6)	−0.0074 (6)	−0.0107 (6)
N8	0.0261 (8)	0.0523 (10)	0.0325 (8)	−0.0189 (7)	−0.0042 (6)	−0.0016 (7)
N9	0.0227 (7)	0.0257 (7)	0.0286 (7)	−0.0032 (6)	0.0009 (5)	−0.0089 (6)
N10	0.0185 (6)	0.0246 (7)	0.0447 (8)	−0.0071 (6)	0.0010 (6)	−0.0139 (6)
N11	0.0176 (6)	0.0250 (7)	0.0333 (7)	−0.0084 (6)	−0.0059 (5)	0.0005 (6)
N12	0.0231 (6)	0.0239 (7)	0.0219 (6)	−0.0096 (6)	−0.0034 (5)	−0.0020 (5)
N13	0.0165 (6)	0.0202 (6)	0.0237 (6)	−0.0044 (5)	0.0004 (5)	−0.0090 (5)
N14	0.0176 (6)	0.0186 (6)	0.0194 (6)	−0.0058 (5)	−0.0002 (5)	−0.0075 (5)
N15	0.0160 (6)	0.0218 (6)	0.0177 (6)	−0.0062 (5)	−0.0008 (5)	−0.0043 (5)
N16	0.0187 (6)	0.0221 (6)	0.0202 (6)	−0.0071 (5)	−0.0008 (5)	−0.0024 (5)
C1	0.0153 (7)	0.0261 (8)	0.0169 (6)	−0.0051 (6)	0.0001 (5)	−0.0062 (6)
C2	0.0198 (7)	0.0193 (7)	0.0161 (6)	−0.0027 (6)	0.0010 (5)	−0.0039 (5)
C3	0.0233 (8)	0.0221 (7)	0.0175 (7)	−0.0065 (6)	0.0002 (6)	−0.0070 (6)
C4	0.0241 (8)	0.0267 (8)	0.0250 (8)	−0.0055 (7)	0.0008 (6)	−0.0070 (6)
C5	0.0189 (7)	0.0232 (8)	0.0239 (7)	−0.0033 (6)	−0.0020 (6)	−0.0045 (6)
C6	0.0129 (7)	0.0332 (9)	0.0233 (8)	−0.0035 (6)	0.0009 (5)	−0.0079 (6)
C7	0.0184 (7)	0.0301 (8)	0.0188 (7)	−0.0037 (6)	−0.0032 (6)	−0.0073 (6)
C8	0.0231 (8)	0.0298 (8)	0.0187 (7)	−0.0087 (7)	0.0011 (6)	−0.0032 (6)
C9	0.0210 (8)	0.0286 (9)	0.0652 (13)	−0.0103 (7)	0.0039 (8)	−0.0133 (9)
C10	0.0198 (9)	0.0264 (10)	0.107 (2)	−0.0088 (8)	−0.0075 (10)	−0.0107 (11)
C11	0.0358 (11)	0.0200 (9)	0.0948 (19)	−0.0052 (8)	−0.0312 (11)	−0.0087 (10)
C12	0.0379 (10)	0.0169 (8)	0.0654 (13)	−0.0018 (7)	−0.0244 (9)	−0.0138 (8)
C13	0.0695 (16)	0.0226 (9)	0.0585 (13)	−0.0035 (10)	−0.0400 (12)	−0.0112 (9)
C14	0.0746 (17)	0.0268 (9)	0.0397 (11)	−0.0047 (10)	−0.0236 (11)	−0.0110 (8)
C15	0.0548 (12)	0.0189 (8)	0.0304 (9)	−0.0014 (8)	−0.0074 (8)	−0.0111 (7)
C16	0.0616 (13)	0.0251 (9)	0.0284 (9)	−0.0016 (9)	0.0082 (9)	−0.0090 (7)
C17	0.0432 (11)	0.0311 (10)	0.0373 (10)	−0.0035 (9)	0.0147 (9)	−0.0079 (8)
C18	0.0261 (8)	0.0315 (9)	0.0342 (9)	−0.0045 (7)	0.0066 (7)	−0.0067 (7)
C19	0.0314 (9)	0.0178 (7)	0.0298 (8)	−0.0005 (7)	−0.0057 (7)	−0.0102 (6)
C20	0.0275 (8)	0.0171 (7)	0.0405 (9)	−0.0021 (6)	−0.0099 (7)	−0.0121 (7)
C21	0.0263 (8)	0.0274 (8)	0.0289 (8)	−0.0123 (7)	−0.0026 (6)	−0.0022 (7)
C22	0.0270 (8)	0.0313 (9)	0.0316 (9)	−0.0136 (7)	−0.0022 (7)	0.0029 (7)
C23	0.0247 (8)	0.0381 (10)	0.0242 (8)	−0.0077 (7)	−0.0001 (6)	0.0012 (7)
C24	0.0233 (8)	0.0318 (9)	0.0246 (8)	−0.0024 (7)	−0.0041 (6)	−0.0039 (7)
C25	0.0357 (10)	0.0425 (11)	0.0285 (9)	−0.0012 (9)	−0.0042 (7)	−0.0110 (8)
C26	0.0370 (10)	0.0386 (10)	0.0425 (11)	0.0007 (8)	−0.0117 (8)	−0.0196 (9)
C27	0.0243 (8)	0.0283 (9)	0.0472 (11)	−0.0017 (7)	−0.0107 (7)	−0.0130 (8)
C28	0.0294 (10)	0.0294 (10)	0.0745 (15)	−0.0053 (8)	−0.0110 (10)	−0.0186 (10)
C29	0.0294 (10)	0.0227 (9)	0.0813 (16)	−0.0101 (8)	−0.0108 (10)	−0.0027 (9)
C30	0.0225 (8)	0.0299 (9)	0.0506 (11)	−0.0104 (7)	−0.0086 (8)	0.0056 (8)
C31	0.0183 (7)	0.0248 (8)	0.0305 (8)	−0.0043 (6)	−0.0073 (6)	−0.0043 (6)
C32	0.0187 (7)	0.0253 (8)	0.0245 (7)	−0.0047 (6)	−0.0050 (6)	−0.0035 (6)
C33	0.0217 (8)	0.0288 (8)	0.0276 (8)	−0.0077 (7)	0.0037 (6)	−0.0103 (7)
C34	0.0177 (7)	0.0310 (9)	0.0387 (9)	−0.0051 (7)	0.0043 (7)	−0.0176 (7)
C35	0.0166 (7)	0.0224 (8)	0.0400 (9)	−0.0022 (6)	−0.0036 (6)	−0.0147 (7)
C36	0.0200 (7)	0.0170 (7)	0.0315 (8)	−0.0047 (6)	−0.0044 (6)	−0.0097 (6)
C37	0.0256 (8)	0.0193 (7)	0.0338 (8)	−0.0050 (6)	−0.0110 (7)	−0.0040 (6)
C38	0.0316 (9)	0.0240 (8)	0.0259 (8)	−0.0112 (7)	−0.0083 (7)	−0.0007 (6)
C39	0.0252 (8)	0.0207 (7)	0.0228 (7)	−0.0108 (6)	−0.0033 (6)	−0.0061 (6)
C40	0.0308 (8)	0.0286 (8)	0.0196 (7)	−0.0157 (7)	0.0010 (6)	−0.0060 (6)
C41	0.0237 (8)	0.0302 (8)	0.0239 (7)	−0.0123 (7)	0.0052 (6)	−0.0111 (6)
C42	0.0182 (7)	0.0231 (7)	0.0228 (7)	−0.0063 (6)	0.0010 (6)	−0.0095 (6)
C43	0.0183 (7)	0.0172 (7)	0.0225 (7)	−0.0063 (6)	−0.0018 (5)	−0.0080 (6)
C44	0.0183 (7)	0.0172 (7)	0.0239 (7)	−0.0057 (6)	−0.0016 (6)	−0.0085 (6)
C45	0.0206 (7)	0.0217 (7)	0.0228 (7)	−0.0073 (6)	−0.0028 (6)	−0.0025 (6)
C46	0.0291 (8)	0.0288 (8)	0.0199 (7)	−0.0133 (7)	−0.0021 (6)	0.0013 (6)
C47	0.0306 (8)	0.0367 (9)	0.0178 (7)	−0.0166 (7)	0.0026 (6)	−0.0062 (6)
C48	0.0228 (7)	0.0297 (8)	0.0221 (7)	−0.0113 (7)	0.0019 (6)	−0.0085 (6)
C49	0.0312 (9)	0.0359 (9)	0.0285 (8)	−0.0142 (8)	0.0084 (7)	−0.0167 (7)
C50	0.0279 (8)	0.0287 (8)	0.0360 (9)	−0.0090 (7)	0.0045 (7)	−0.0158 (7)
C51	0.0206 (7)	0.0246 (8)	0.0297 (8)	−0.0076 (6)	−0.0010 (6)	−0.0075 (6)
C52	0.0263 (8)	0.0213 (8)	0.0403 (9)	−0.0064 (7)	−0.0043 (7)	−0.0048 (7)
C53	0.0308 (9)	0.0243 (8)	0.0322 (9)	−0.0098 (7)	−0.0051 (7)	0.0038 (7)
C54	0.0266 (8)	0.0283 (8)	0.0225 (7)	−0.0103 (7)	−0.0014 (6)	0.0009 (6)
C55	0.0176 (7)	0.0226 (7)	0.0210 (7)	−0.0072 (6)	−0.0009 (5)	−0.0044 (6)
C56	0.0169 (7)	0.0220 (7)	0.0206 (7)	−0.0071 (6)	−0.0009 (5)	−0.0053 (6)
O1	0.0304 (7)	0.0427 (8)	0.0432 (8)	−0.0101 (6)	−0.0054 (6)	−0.0036 (6)
O2	0.0890 (13)	0.0424 (9)	0.0356 (8)	−0.0130 (9)	0.0044 (8)	−0.0055 (7)
O3A	0.0557 (17)	0.0548 (12)	0.113 (2)	−0.0134 (12)	0.0160 (14)	−0.0362 (13)
O3B	0.0557 (17)	0.0548 (12)	0.113 (2)	−0.0134 (12)	0.0160 (14)	−0.0362 (13)
O4A	0.074 (3)	0.041 (2)	0.073 (3)	−0.0097 (19)	0.011 (2)	−0.021 (2)
O4B	0.080 (3)	0.034 (2)	0.074 (3)	−0.022 (2)	0.023 (2)	−0.028 (2)

Geometric parameters (Å, º) top

Co1—C6	1.8747 (16)	C23—H23	0.9500
Co1—C7	1.8779 (18)	C24—C32	1.407 (2)
Co1—C2	1.8960 (16)	C24—C25	1.432 (3)
Co1—C8	1.9076 (17)	C25—C26	1.348 (3)
Co1—N15	1.9693 (13)	C25—H25	0.9500
Co1—N16	1.9762 (15)	C26—C27	1.437 (3)
Co2—C3	1.8744 (17)	C26—H26	0.9500
Co2—C4	1.8822 (17)	C27—C28	1.400 (3)
Co2—C5	1.8975 (17)	C27—C31	1.407 (2)
Co2—C1	1.9044 (16)	C28—C29	1.367 (3)
Co2—N13	1.9652 (15)	C28—H28	0.9500
Co2—N14	1.9665 (14)	C29—C30	1.405 (3)
Fe1—N2	2.0365 (14)	C29—H29	0.9500
Fe1—N1	2.0464 (15)	C30—H30	0.9500
Fe1—N12	2.0821 (15)	C31—C32	1.429 (2)
Fe1—N10	2.0845 (16)	C33—C34	1.400 (2)
Fe1—N11	2.0960 (16)	C33—H33	0.9500
Fe1—N9	2.1067 (16)	C34—C35	1.370 (3)
N1—C1	1.144 (2)	C34—H34	0.9500
N2—C2	1.144 (2)	C35—C36	1.410 (2)
N3—C3	1.147 (2)	C35—H35	0.9500
N4—C4	1.147 (2)	C36—C44	1.401 (2)
N5—C5	1.149 (2)	C36—C37	1.434 (2)
N6—C6	1.148 (2)	C37—C38	1.356 (2)
N7—C7	1.156 (2)	C37—H37	0.9500
N8—C8	1.146 (2)	C38—C39	1.434 (2)
N9—C18	1.330 (2)	C38—H38	0.9500
N9—C19	1.364 (2)	C39—C43	1.399 (2)
N10—C9	1.332 (2)	C39—C40	1.410 (2)
N10—C20	1.358 (2)	C40—C41	1.370 (2)
N11—C30	1.328 (2)	C40—H40	0.9500
N11—C31	1.365 (2)	C41—C42	1.397 (2)
N12—C21	1.332 (2)	C41—H41	0.9500
N12—C32	1.362 (2)	C42—H42	0.9500
N13—C33	1.328 (2)	C43—C44	1.423 (2)
N13—C44	1.365 (2)	C45—C46	1.401 (2)
N14—C42	1.3302 (19)	C45—H45	0.9500
N14—C43	1.362 (2)	C46—C47	1.372 (3)
N15—C45	1.327 (2)	C46—H46	0.9500
N15—C56	1.360 (2)	C47—C48	1.405 (2)
N16—C54	1.331 (2)	C47—H47	0.9500
N16—C55	1.361 (2)	C48—C56	1.403 (2)
C9—C10	1.411 (3)	C48—C49	1.436 (2)
C9—H9	0.9500	C49—C50	1.352 (3)
C10—C11	1.355 (4)	C49—H49	0.9500
C10—H10	0.9500	C50—C51	1.437 (2)
C11—C12	1.404 (3)	C50—H50	0.9500
C11—H11	0.9500	C51—C55	1.401 (2)
C12—C20	1.410 (2)	C51—C52	1.407 (2)
C12—C13	1.433 (3)	C52—C53	1.373 (3)
C13—C14	1.347 (4)	C52—H52	0.9500
C13—H13	0.9500	C53—C54	1.395 (3)
C14—C15	1.428 (3)	C53—H53	0.9500
C14—H14	0.9500	C54—H54	0.9500
C15—C16	1.407 (3)	C55—C56	1.423 (2)
C15—C19	1.410 (2)	O1—H1A	0.8200
C16—C17	1.360 (3)	O1—H1B	0.8200
C16—H16	0.9500	O2—H2A	0.8200
C17—C18	1.409 (3)	O2—H2B	0.8200
C17—H17	0.9500	O3A—H3A	0.8199
C18—H18	0.9500	O3A—H3B	0.8199
C19—C20	1.428 (3)	O3B—H3C	0.8505
C21—C22	1.399 (2)	O3B—H3D	0.9027
C21—H21	0.9500	O4A—H4A	0.8422
C22—C23	1.371 (3)	O4A—H4B	0.8174
C22—H22	0.9500	O4B—H4C	1.0307
C23—C24	1.409 (3)	O4B—H4D	0.8225

C6—Co1—C7	90.48 (8)	N12—C21—C22	122.94 (17)
C6—Co1—C2	87.01 (7)	N12—C21—H21	118.5
C7—Co1—C2	90.57 (7)	C22—C21—H21	118.5
C6—Co1—C8	92.80 (7)	C23—C22—C21	119.48 (17)
C7—Co1—C8	89.57 (8)	C23—C22—H22	120.3
C2—Co1—C8	179.77 (7)	C21—C22—H22	120.3
C6—Co1—N15	174.69 (6)	C22—C23—C24	119.38 (16)
C7—Co1—N15	93.95 (7)	C22—C23—H23	120.3
C2—Co1—N15	90.01 (6)	C24—C23—H23	120.3
C8—Co1—N15	90.17 (7)	C32—C24—C23	117.35 (16)
C6—Co1—N16	92.28 (7)	C32—C24—C25	118.53 (17)
C7—Co1—N16	177.21 (6)	C23—C24—C25	124.11 (17)
C2—Co1—N16	89.20 (7)	C26—C25—C24	121.49 (18)
C8—Co1—N16	90.68 (7)	C26—C25—H25	119.3
N15—Co1—N16	83.28 (6)	C24—C25—H25	119.3
C3—Co2—C4	88.80 (8)	C25—C26—C27	121.08 (18)
C3—Co2—C5	91.73 (7)	C25—C26—H26	119.5
C4—Co2—C5	89.44 (8)	C27—C26—H26	119.5
C3—Co2—C1	91.83 (7)	C28—C27—C31	117.43 (19)
C4—Co2—C1	91.26 (7)	C28—C27—C26	123.79 (19)
C5—Co2—C1	176.38 (6)	C31—C27—C26	118.78 (17)
C3—Co2—N13	176.12 (6)	C29—C28—C27	119.58 (19)
C4—Co2—N13	94.35 (7)	C29—C28—H28	120.2
C5—Co2—N13	90.56 (7)	C27—C28—H28	120.2
C1—Co2—N13	85.85 (6)	C28—C29—C30	119.40 (18)
C3—Co2—N14	93.37 (7)	C28—C29—H29	120.3
C4—Co2—N14	177.57 (6)	C30—C29—H29	120.3
C5—Co2—N14	89.40 (6)	N11—C30—C29	122.93 (19)
C1—Co2—N14	89.76 (6)	N11—C30—H30	118.5
N13—Co2—N14	83.52 (6)	C29—C30—H30	118.5
N2—Fe1—N1	89.63 (6)	N11—C31—C27	123.07 (16)
N2—Fe1—N12	95.57 (6)	N11—C31—C32	117.09 (15)
N1—Fe1—N12	91.20 (6)	C27—C31—C32	119.84 (16)
N2—Fe1—N10	170.46 (6)	N12—C32—C24	123.00 (15)
N1—Fe1—N10	91.63 (6)	N12—C32—C31	116.79 (14)
N12—Fe1—N10	93.86 (6)	C24—C32—C31	120.21 (16)
N2—Fe1—N11	84.52 (6)	N13—C33—C34	121.87 (16)
N1—Fe1—N11	168.24 (5)	N13—C33—H33	119.1
N12—Fe1—N11	79.27 (6)	C34—C33—H33	119.1
N10—Fe1—N11	95.84 (6)	C35—C34—C33	120.36 (15)
N2—Fe1—N9	92.00 (6)	C35—C34—H34	119.8
N1—Fe1—N9	88.78 (6)	C33—C34—H34	119.8
N12—Fe1—N9	172.44 (5)	C34—C35—C36	119.16 (15)
N10—Fe1—N9	78.58 (7)	C34—C35—H35	120.4
N11—Fe1—N9	101.58 (6)	C36—C35—H35	120.4
C1—N1—Fe1	171.17 (13)	C44—C36—C35	116.95 (15)
C2—N2—Fe1	170.94 (13)	C44—C36—C37	118.12 (15)
C18—N9—C19	117.69 (16)	C35—C36—C37	124.93 (15)
C18—N9—Fe1	128.98 (13)	C38—C37—C36	121.37 (15)
C19—N9—Fe1	112.69 (12)	C38—C37—H37	119.3
C9—N10—C20	118.00 (16)	C36—C37—H37	119.3
C9—N10—Fe1	128.11 (14)	C37—C38—C39	121.21 (15)
C20—N10—Fe1	113.72 (11)	C37—C38—H38	119.4
C30—N11—C31	117.58 (16)	C39—C38—H38	119.4
C30—N11—Fe1	129.09 (14)	C43—C39—C40	116.81 (14)
C31—N11—Fe1	112.63 (11)	C43—C39—C38	118.24 (15)
C21—N12—C32	117.82 (14)	C40—C39—C38	124.95 (15)
C21—N12—Fe1	128.64 (12)	C41—C40—C39	119.40 (14)
C32—N12—Fe1	113.47 (11)	C41—C40—H40	120.3
C33—N13—C44	118.25 (14)	C39—C40—H40	120.3
C33—N13—Co2	129.55 (11)	C40—C41—C42	120.06 (15)
C44—N13—Co2	112.08 (10)	C40—C41—H41	120.0
C42—N14—C43	118.18 (13)	C42—C41—H41	120.0
C42—N14—Co2	129.60 (11)	N14—C42—C41	122.02 (15)
C43—N14—Co2	112.22 (10)	N14—C42—H42	119.0
C45—N15—C56	118.39 (13)	C41—C42—H42	119.0
C45—N15—Co1	129.36 (11)	N14—C43—C39	123.49 (14)
C56—N15—Co1	112.23 (10)	N14—C43—C44	115.95 (13)
C54—N16—C55	117.99 (14)	C39—C43—C44	120.55 (14)
C54—N16—Co1	129.90 (12)	N13—C44—C36	123.41 (14)
C55—N16—Co1	112.10 (11)	N13—C44—C43	116.08 (13)
N1—C1—Co2	171.05 (13)	C36—C44—C43	120.51 (14)
N2—C2—Co1	176.64 (14)	N15—C45—C46	121.92 (15)
N3—C3—Co2	178.00 (15)	N15—C45—H45	119.0
N4—C4—Co2	178.90 (17)	C46—C45—H45	119.0
N5—C5—Co2	176.80 (15)	C47—C46—C45	120.05 (15)
N6—C6—Co1	174.75 (15)	C47—C46—H46	120.0
N7—C7—Co1	178.49 (16)	C45—C46—H46	120.0
N8—C8—Co1	176.31 (15)	C46—C47—C48	119.35 (15)
N10—C9—C10	121.6 (2)	C46—C47—H47	120.3
N10—C9—H9	119.2	C48—C47—H47	120.3
C10—C9—H9	119.2	C56—C48—C47	116.96 (15)
C11—C10—C9	120.5 (2)	C56—C48—C49	118.09 (15)
C11—C10—H10	119.8	C47—C48—C49	124.96 (15)
C9—C10—H10	119.8	C50—C49—C48	121.51 (15)
C10—C11—C12	119.47 (19)	C50—C49—H49	119.2
C10—C11—H11	120.3	C48—C49—H49	119.2
C12—C11—H11	120.3	C49—C50—C51	121.16 (16)
C11—C12—C20	116.9 (2)	C49—C50—H50	119.4
C11—C12—C13	124.7 (2)	C51—C50—H50	119.4
C20—C12—C13	118.4 (2)	C55—C51—C52	117.22 (15)
C14—C13—C12	122.14 (19)	C55—C51—C50	118.22 (15)
C14—C13—H13	118.9	C52—C51—C50	124.56 (16)
C12—C13—H13	118.9	C53—C52—C51	118.91 (16)
C13—C14—C15	120.5 (2)	C53—C52—H52	120.5
C13—C14—H14	119.8	C51—C52—H52	120.5
C15—C14—H14	119.8	C52—C53—C54	120.35 (16)
C16—C15—C19	117.28 (18)	C52—C53—H53	119.8
C16—C15—C14	123.6 (2)	C54—C53—H53	119.8
C19—C15—C14	119.1 (2)	N16—C54—C53	122.09 (16)
C17—C16—C15	119.55 (18)	N16—C54—H54	119.0
C17—C16—H16	120.2	C53—C54—H54	119.0
C15—C16—H16	120.2	N16—C55—C51	123.43 (15)
C16—C17—C18	119.7 (2)	N16—C55—C56	116.02 (14)
C16—C17—H17	120.1	C51—C55—C56	120.55 (14)
C18—C17—H17	120.1	N15—C56—C48	123.33 (14)
N9—C18—C17	122.64 (19)	N15—C56—C55	116.23 (13)
N9—C18—H18	118.7	C48—C56—C55	120.44 (14)
C17—C18—H18	118.7	H1A—O1—H1B	101.9
N9—C19—C15	123.11 (17)	H2A—O2—H2B	92.6
N9—C19—C20	116.68 (15)	H3A—O3A—H3B	115.5
C15—C19—C20	120.20 (17)	H3C—O3B—H3D	121.5
N10—C20—C12	123.52 (18)	H4A—O4A—H4B	109.9
N10—C20—C19	116.86 (15)	H4C—O4B—H4D	102.0
C12—C20—C19	119.60 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N7	0.82	2.34	3.143 (2)	167
O1—H1B···N3	0.82	2.12	2.939 (2)	172
O2—H2A···N8ⁱ	0.82	2.33	3.118 (3)	163
O2—H2B···N4	0.82	2.16	2.970 (2)	170
O3A—H3A···O2ⁱⁱ	0.82	2.22	2.971 (3)	153
O3A—H3B···O1	0.82	2.12	2.930 (3)	169
O3B—H3C···O1	0.85	1.97	2.823 (16)	179
O3B—H3D···O2ⁱⁱ	0.90	2.11	2.889 (18)	144
O4A—H4A···N6ⁱⁱⁱ	0.84	2.11	2.930 (6)	165
O4A—H4B···N5	0.82	2.13	2.870 (4)	151
O4B—H4D···N5	0.82	2.09	2.848 (4)	153

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

Experimental details

Crystal data
Chemical formula	[Co₂Fe(CN)₈(C₁₂H₈N₂)₄]·4H₂O
M_r	1174.75
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	12.855 (3), 14.006 (3), 16.334 (3)
α, β, γ (°)	72.68 (3), 82.54 (3), 65.99 (3)
V (Å³)	2564.5 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.74 × 0.56 × 0.33

Data collection
Diffractometer	Rigaku R-AXIS Spider diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.555, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	41118, 11723, 10898
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.03
No. of reflections	11723
No. of parameters	726
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.70

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006).

Selected geometric parameters (Å, º) top

Co1—C6	1.8747 (16)	Fe1—N1	2.0464 (15)
Co1—C7	1.8779 (18)	Fe1—N12	2.0821 (15)
Co1—C2	1.8960 (16)	Fe1—N10	2.0845 (16)
Co1—C8	1.9076 (17)	Fe1—N11	2.0960 (16)
Co1—N15	1.9693 (13)	Fe1—N9	2.1067 (16)
Co1—N16	1.9762 (15)	N1—C1	1.144 (2)
Co2—C3	1.8744 (17)	N2—C2	1.144 (2)
Co2—C4	1.8822 (17)	N3—C3	1.147 (2)
Co2—C5	1.8975 (17)	N4—C4	1.147 (2)
Co2—C1	1.9044 (16)	N5—C5	1.149 (2)
Co2—N13	1.9652 (15)	N6—C6	1.148 (2)
Co2—N14	1.9665 (14)	N7—C7	1.156 (2)
Fe1—N2	2.0365 (14)	N8—C8	1.146 (2)

C1—N1—Fe1	171.17 (13)	N4—C4—Co2	178.90 (17)
C2—N2—Fe1	170.94 (13)	N5—C5—Co2	176.80 (15)
N1—C1—Co2	171.05 (13)	N6—C6—Co1	174.75 (15)
N2—C2—Co1	176.64 (14)	N7—C7—Co1	178.49 (16)
N3—C3—Co2	178.00 (15)	N8—C8—Co1	176.31 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N7	0.82	2.34	3.143 (2)	166.6
O1—H1B···N3	0.82	2.12	2.939 (2)	172.2
O2—H2A···N8ⁱ	0.82	2.33	3.118 (3)	162.6
O2—H2B···N4	0.82	2.16	2.970 (2)	169.6
O3A—H3A···O2ⁱⁱ	0.82	2.22	2.971 (3)	153.3
O3A—H3B···O1	0.82	2.12	2.930 (3)	168.9
O3B—H3C···O1	0.85	1.97	2.823 (16)	178.8
O3B—H3D···O2ⁱⁱ	0.90	2.11	2.889 (18)	144.2
O4A—H4A···N6ⁱⁱⁱ	0.84	2.11	2.930 (6)	165.0
O4A—H4B···N5	0.82	2.13	2.870 (4)	150.8
O4B—H4D···N5	0.82	2.09	2.848 (4)	153.0

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

Acknowledgements

The work was supported by the University Natural Science Foundation of China Jiangsu Province (No. 07KJB150030).

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brewer, C. T., Brewer, G., Butcher, R. J., Carpenter, E. E., Schmiedekamp, A. M. & Viragh, C. (2007). Dalton Trans. pp. 295–298. Web of Science CSD CrossRef Google Scholar
Chen, X. B., Li, Y. Z. & You, X. Z. (2006). Appl. Organomet. Chem. 20, 305–309. Web of Science CSD CrossRef CAS Google Scholar
Colacio, E., Debdoubi, A., Kivekäs, R. & Rodríguez, A. (2005). Eur. J. Inorg. Chem. pp. 2860–2868. Web of Science CSD CrossRef Google Scholar
Colacio, E., Domínguez-Vera, J. M., Lloret, F., Moreno Sánchez, J. M., Kivekäs, R., Rodríguez, A. & Sillanpää, R. (2003). Inorg. Chem. 42, 4209–4214. Web of Science CSD CrossRef PubMed CAS Google Scholar
Ferlay, S., Malleh, T., Ouakès, R., Veillet, P. & Verdaguer, M. (1995). Nature (London), 378, 701–703. CrossRef CAS Web of Science Google Scholar
Fernández-Armas, S., Mesa, J. L., Pizarro, J. L., Arriortua, M. I. & Roji, T. (2007). Mater. Res. Bull. 42, 544–552. Google Scholar
Goodwin, A. L., Calleja, M., Conterio, M. J., Dove, M. T., Evans, J. S. O., Keen, D. A., Peters, L. & Tucker, M. G. (2008). Science, 319, 794–797. Web of Science CrossRef PubMed CAS Google Scholar
Guo, Y., Feng, Y. H., Liu, Z. Q. & Liao, D. Z. (2007). J. Coord. Chem. 60, 2713–2720. Web of Science CSD CrossRef CAS Google Scholar
Halbauer, K., Görls, H. & Imhof, W. (2008). Inorg. Chem. Commun. 11, 1177–1180. Web of Science CSD CrossRef CAS Google Scholar
He, X., Lu, C. Z., Yuan, D. Q., Chen, S. M. & Chen, J. T. (2005). Eur. J. Inorg. Chem. pp. 2181–2188. Web of Science CSD CrossRef Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Kosaka, W., Imoto, K., Tsunobuchi, Y. & Ohkoshi, S. I. (2009). Inorg. Chem. 48, 4604–4606. Web of Science CrossRef PubMed CAS Google Scholar
Mao, H., Zhang, C., Xu, C., Zhang, H., Shen, X., Wu, B., Zhu, Y., Wu, Q. & Wang, H. (2005). Inorg. Chim. Acta, 358, 1934–1942. Web of Science CSD CrossRef CAS Google Scholar
Overgaard, J., Rentschler, E., Timco, G. A. & Larsen, F. K. (2004). ChemPhysChem, 5, 1755–1761. Web of Science CSD CrossRef PubMed CAS Google Scholar
Paredes-García, V., Venegas-Yazigi, D., Latorre, R. O. & Spodine, E. (2006). Polyhedron, 25, 2026–2032. Google Scholar
Phillips, A. E., Goodwin, A. L., Halder, G. J., Southon, P. D. & Kepert, C. J. (2008). Angew. Chem. Int. Ed. 47, 1396–1399. Web of Science CSD CrossRef CAS Google Scholar
Reguera, L., Balmaseda, J., del Castillo, L. F. & Reguera, E. (2008). J. Phys. Chem. C, 112, 5589–5597. Web of Science CrossRef CAS Google Scholar
Reguera, L., Balmaseda, J., Krap, C. P. & Reguera, E. (2008). J. Phys. Chem. C, 112, 10490–10501. Web of Science CrossRef CAS Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rodriguez, A., Sakiyama, H., Masciocchi, N., Galli, S., Gálvez, N., Lloret, F. & Colacio, E. (2005). Inorg. Chem. 44, 8399–8406. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rodríguez-Diéguez, A., Kivekäs, R., Sakiyama, H., Debdoubi, A. & Colacio, E. (2007). Dalton Trans. pp. 2145–2149. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, L. H., Liu, S. X., Gao, C. Y., Cao, R., Cao, J. F., Sun, C. Y. & Su, Z. M. (2007). Inorg. Chem. 46, 7782–7788. Web of Science CSD CrossRef PubMed CAS Google Scholar
Yu, J. H., Xu, J. Q., Yang, Q. X., Pan, L. Y., Wang, T. G., Lü, C. H. & Ma, T. H. (2003). J. Mol. Struct. 658, 1–7. Web of Science CSD CrossRef CAS Google Scholar
Zhao, Y. G., Guo, D., Liu, Y., He, C. & Duan, C. Y. (2008). Chem. Commun. pp. 5725–5727. Web of Science CSD CrossRef Google Scholar

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