Di-μ-cyanido-1:2κC:N,2:3κN:C-hexa-cyanido-1κC,3κC-tetra-kis(1,10-phenanthroline)-1κN,N';2κN,N';3κN,N'-1,3-dicobalt(III)-2-iron(II) tetra-hydrate.

The hydro-thermal reaction of CoCl(2)·6H(2)O, 1,10-phenanthroline (phen) and K(3)[Fe(CN)(6)] in deionized water yielded the title cyanide-bridged trinuclear cluster, [Co(2)Fe(CN)(8)(C(12)H(8)N(2))(4)]·4H(2)O or [{Co(III)(phen)(CN)(4)}(2){Fe(II)(phen)(2)}]·4H(2)O, 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 inter-actions [centroid-centroid distance = 3.630 (2) Å] results in the stabilization of a supra-molecular structure. All uncoordinated water molecules are disordered. Thermogravimetric analysis reveals that the title complex loses the four crystal water mol-ecules 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 = 1174.75

Triclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.03

11723 reflections

726 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.70 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co2Fe(CN)8(C12H8N2)4]·4H2O	Z = 2
Mr = 1174.75	F(000) = 1200
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0331P)2 + 1.5388P] where P = (Fo2 + 2Fc2)/3
11723 reflections	(Δ/σ)max = 0.001
726 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.70 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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

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) ; (ii) ; (iii) .