supplementary materials


mw2119 scheme

Acta Cryst. (2014). E70, m21-m22    [ doi:10.1107/S1600536813033357 ]

Bis([mu]2-benzoato-[kappa]2O:O')bis­[(benzoato-[kappa]2O,O')bis(4,4'-bi­pyridine-[kappa]N)cobalt(II)]-benzoic acid (1/6)

R. Peña-Rodríguez, J. M. Rivera, R. Colorado-Peralta, A. M. Duarte-Hernández and A. Flores-Parra

Abstract top

In the title compound, [Co2(C7H5O2)4(C10H8N2)4]·6C6H5COOH, the centrosymmetric cobalt dimer co-crystallizes with six mol­ecules of benzoic acid. Each CoII atom is coordinated by four O atoms in a distorted square-planar arrangement while the N atoms are located in apical positions. The dihedral angles between the rings comprising each of the 4,4'-bipyridyl ligands are 25.2 (2) and 22.8 (2)°. In the crystal, the three-dimensional network is assembled by O-H...O and C-H...O hydrogen bonds.

Comment top

The design of metal-organic coordination compounds is of current interest in the fields of supramolecular chemistry and crystal engineering. This interest stems from their potential applications as functional materials, such as in gas storage, ion-exchange, catalysis, magnetism and molecular sensing (Song et al., 2009; Zhang et al., 2007). 4,4'-Bipyridine is an excellent, rigid bridging ligand for the construction of novel metal-organic coordination compounds due to its various coordinative modes with metal ions (Wu et al., 2007; Murugesapandian & Roesky, 2011a, 2011b). Currently all the metal-organic coordination compounds obtained with benzoic acid and 4,4'-bipyridine are polymeric. The title compound is the first example of a dimeric species with these two ligands.

The title compound is a cobalt(II) dimer having crystallographically-imposed centrosymmetry (Fig. 1) together with six molecules of benzoic acid in the lattice. Each cobalt(II) ion displays a distorted octahedral coordination geometry being surrounded by four oxygen atoms of one chelating and two bridging benzoate anions and two trans-disposed, monodentate 4,4'-bipyridine ligands. In the central portion of the dimer, the two metal ions and the two bidentate bridging benzoate ions form an eight-membered ring. The dihedral angles between the rings of the 4,4'-bipyridine ligands are 25.2 (2)° (ligand containing N1 and N2) and 22.8 (2)° (ligand containing N3 and N5). In the crystal structure weak O—H···O and C—H···O hydrogen bonds link the molecules into an infinite one-dimensional chain extending along the b axis [O7—H7a···O1,1.859 Å, 164.10°; C6—H6···O2, 2.366 Å, 167.54°]. (Fig. 2).

Related literature top

For polymer structures with benzoate and 4,4'-bipyridyl ligands coordinated to cobalt(II), see: Song et al. (2009), Zhang et al. (2007); to copper(II), see: Wu et al. (2007); to cadmium(II) and zinc(II), see: Murugesapandian & Roesky (2011a,b).

Experimental top

A solution of cobalt(II) nitrate hexahydrate (93.1 mg 0.32 mmol) in 5 mL of deionized water was added dropwise to 5 mL of a methanol solution of benzoic anhydride (72.4 mg 0.32 mmol). The reaction mixture was refluxed at 80 °C without stirring after which a solution of 4,4'-bipyridine (50 mg 0.32 mmol) in 10 mL of methanol was slowly added at room temperature. The solid was crystallized from solution giving red crystals of the title compound which were suitablefor X-ray crystal structure analysis and fully characterized by standard analytical methods. M.p. > 350°C.

Refinement top

H atoms were positioned geometrically and refined using a riding model approximation with distance O—H = 0.82 Å and C—H = 0.93 Å, with Uiso(H) = 1.2Ueq(C,O).

Computing details top

Data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012), enCIFer (Allen, 2004) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, three benzoic acid molecules are represented by sticks and H atoms are omitted for clarity.
[Figure 2] Fig. 2. Crystal packing of the title compound viewed along b axis. Intermolecular hydrogen bonds are shown as blue dashed lines.
Bis(µ2-benzoato-κ2O:O')bis[(benzoato-κ2O,O')bis(4,4'-bipyridine-κN)cobalt(II)]–benzoic acid (1/6) top
Crystal data top
[Co2(C7H5O2)4(C10H8N2)4]·6C7H6O2Z = 1
Mr = 1959.74F(000) = 1018
Triclinic, P1Dx = 1.329 Mg m3
Hall symbol: -P 1Melting point: 350 K
a = 10.4977 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 15.8329 (7) ÅCell parameters from 28061 reflections
c = 16.3994 (8) Åθ = 1.0–27.5°
α = 64.222 (3)°µ = 0.41 mm1
β = 87.792 (3)°T = 293 K
γ = 86.469 (3)°Prism, red
V = 2449.6 (2) Å30.2 × 0.1 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer
11064 independent reflections
Radiation source: Enraf–Nonius FR5905118 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
Detector resolution: 9 pixels mm-1θmax = 27.4°, θmin = 2.4°
CCD rotation images, thick slices scansh = 1312
Absorption correction: multi-scan
(SORTAV; Blessing, 1987, 1989, 1995)
k = 2020
Tmin = 0.925, Tmax = 0.980l = 2021
28546 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.076Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0388P)2 + 1.8382P]
where P = (Fo2 + 2Fc2)/3
11064 reflections(Δ/σ)max = 0.001
631 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Co2(C7H5O2)4(C10H8N2)4]·6C7H6O2γ = 86.469 (3)°
Mr = 1959.74V = 2449.6 (2) Å3
Triclinic, P1Z = 1
a = 10.4977 (6) ÅMo Kα radiation
b = 15.8329 (7) ŵ = 0.41 mm1
c = 16.3994 (8) ÅT = 293 K
α = 64.222 (3)°0.2 × 0.1 × 0.05 mm
β = 87.792 (3)°
Data collection top
Nonius KappaCCD
diffractometer
11064 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1987, 1989, 1995)
5118 reflections with I > 2σ(I)
Tmin = 0.925, Tmax = 0.980Rint = 0.082
28546 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.076H-atom parameters constrained
wR(F2) = 0.157Δρmax = 0.32 e Å3
S = 1.03Δρmin = 0.31 e Å3
11064 reflectionsAbsolute structure: ?
631 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Co10.13907 (4)0.09130 (3)0.51110 (3)0.04482 (16)
O10.1879 (2)0.16963 (17)0.58558 (17)0.0566 (7)
O20.3130 (2)0.17380 (17)0.47431 (17)0.0573 (7)
O30.0072 (2)0.02611 (18)0.59081 (16)0.0605 (7)
O40.1804 (2)0.04234 (18)0.41807 (16)0.0563 (7)
N10.0204 (3)0.2073 (2)0.4218 (2)0.0511 (8)
N20.3787 (5)0.6089 (3)0.1719 (3)0.0927 (13)
N30.2633 (3)0.0192 (2)0.60462 (19)0.0477 (7)
N50.6503 (5)0.3951 (3)0.9135 (3)0.0887 (12)
C10.4254 (3)0.1614 (2)0.7278 (2)0.0517 (9)
C20.5065 (4)0.2405 (3)0.7921 (3)0.0583 (10)
C30.3224 (4)0.1222 (3)0.7567 (3)0.0636 (11)
H30.30520.14270.81820.076*
C40.2452 (4)0.0522 (3)0.6933 (3)0.0602 (10)
H40.17650.02680.71430.072*
C50.3647 (3)0.0556 (2)0.5767 (2)0.0490 (9)
H50.38060.03270.51480.059*
C60.4468 (3)0.1251 (2)0.6347 (2)0.0516 (9)
H60.51620.14780.61180.062*
C70.4598 (5)0.2980 (3)0.8773 (3)0.0776 (13)
H70.37860.28560.89560.093*
C80.5339 (6)0.3730 (3)0.9344 (3)0.0919 (16)
H80.50070.41060.99130.11*
C90.6958 (5)0.3408 (4)0.8324 (4)0.0938 (16)
H90.7770.35560.81610.113*
C100.6279 (4)0.2627 (3)0.7704 (3)0.0837 (14)
H100.66420.22540.71450.1*
C110.1404 (4)0.3636 (3)0.3194 (2)0.0538 (10)
C120.2251 (4)0.4474 (3)0.2685 (3)0.0605 (10)
C130.1842 (4)0.2761 (3)0.3651 (3)0.0786 (14)
H130.27050.26680.36340.094*
C140.1030 (4)0.2013 (3)0.4138 (3)0.0778 (14)
H140.13680.14240.44310.093*
C150.0627 (4)0.2928 (3)0.3749 (3)0.0853 (15)
H150.14940.30050.3770.102*
C160.0126 (4)0.3702 (3)0.3238 (3)0.0846 (15)
H160.02390.42780.29180.101*
C170.1911 (5)0.5364 (3)0.2540 (3)0.0911 (16)
H170.11450.54370.27630.109*
C180.2705 (6)0.6136 (4)0.2066 (4)0.1049 (18)
H180.24620.67220.19880.126*
C190.4141 (5)0.5272 (5)0.1853 (3)0.0924 (16)
H190.49160.52310.16190.111*
C200.3392 (5)0.4428 (4)0.2345 (3)0.0889 (15)
H200.36820.38510.24330.107*
C210.2930 (3)0.1908 (2)0.5415 (3)0.0523 (9)
C220.3932 (4)0.2327 (3)0.5724 (3)0.0592 (10)
C230.3760 (4)0.2431 (3)0.6515 (3)0.0746 (12)
H230.30060.22580.68490.089*
C240.4712 (5)0.2794 (4)0.6811 (4)0.1020 (17)
H240.45950.28660.73420.122*
C250.5817 (6)0.3044 (4)0.6327 (5)0.116 (2)
H250.64540.32890.65270.14*
C260.5993 (5)0.2940 (5)0.5558 (5)0.124 (2)
H260.67530.31120.52310.149*
C270.5054 (4)0.2580 (4)0.5248 (4)0.0937 (16)
H270.51860.25090.47160.112*
C280.1194 (3)0.0033 (2)0.6124 (2)0.0420 (8)
C290.1875 (3)0.0308 (2)0.6794 (2)0.0431 (8)
C300.3148 (4)0.0119 (3)0.7003 (3)0.0595 (10)
H300.35780.01710.67160.071*
C310.3783 (4)0.0354 (4)0.7630 (3)0.0842 (14)
H310.4640.0230.77630.101*
C320.3144 (6)0.0772 (4)0.8054 (3)0.0948 (16)
H320.35690.09230.84840.114*
C330.1893 (5)0.0970 (3)0.7856 (3)0.0824 (14)
H330.14720.12570.8150.099*
C340.1249 (4)0.0747 (3)0.7221 (3)0.0609 (10)
H340.03990.08910.70790.073*
O50.3391 (4)0.6953 (3)0.0736 (3)0.1194 (14)
O60.5022 (4)0.7786 (2)0.0694 (2)0.1021 (11)
H6A0.53580.72650.09940.153*
C420.3856 (6)0.7699 (4)0.0509 (3)0.0842 (14)
C430.3183 (4)0.8629 (3)0.0038 (3)0.0627 (11)
C440.1891 (5)0.8649 (4)0.0154 (3)0.0866 (14)
H440.1460.80940.01060.104*
C450.1230 (5)0.9484 (5)0.0651 (4)0.1014 (17)
H450.03550.94950.07250.122*
C460.1856 (6)1.0296 (4)0.1035 (4)0.1030 (18)
H460.14081.08630.13650.124*
C470.3141 (6)1.0277 (3)0.0935 (3)0.0933 (16)
H470.35711.08310.12080.112*
C480.3802 (5)0.9451 (3)0.0436 (3)0.0749 (12)
H480.46780.94460.03660.09*
O70.0189 (3)0.6991 (2)0.4128 (2)0.0877 (9)
H7A0.07350.74150.40320.132*
O80.0534 (3)0.7343 (2)0.2686 (3)0.0932 (10)
C490.0020 (4)0.6876 (3)0.3376 (4)0.0683 (12)
C500.1003 (4)0.6121 (3)0.3495 (3)0.0649 (11)
C510.1503 (4)0.6056 (3)0.2726 (4)0.0782 (13)
H510.12150.64780.21560.094*
C520.2422 (5)0.5369 (4)0.2805 (5)0.0965 (16)
H520.27540.53260.2290.116*
C530.2843 (6)0.4755 (4)0.3636 (6)0.1079 (19)
H530.34670.42920.36850.129*
C540.2367 (5)0.4804 (4)0.4403 (5)0.1045 (18)
H540.26610.43770.49690.125*
C550.1436 (5)0.5500 (3)0.4328 (4)0.0834 (14)
H550.11090.55410.48460.1*
O90.2055 (3)0.4497 (2)0.0229 (2)0.0972 (10)
H9A0.24730.49770.00880.146*
O100.0947 (3)0.4821 (2)0.1046 (2)0.1078 (12)
C350.1129 (5)0.4338 (3)0.0259 (4)0.0774 (13)
C360.0322 (4)0.3462 (3)0.0283 (3)0.0711 (12)
C370.0617 (5)0.3194 (4)0.0164 (4)0.1078 (19)
H370.07450.35560.07810.129*
C380.1384 (6)0.2389 (4)0.0287 (4)0.118 (2)
H380.20140.22050.00260.141*
C390.1209 (6)0.1874 (4)0.1187 (4)0.1061 (18)
H390.1730.13390.14980.127*
C400.0265 (6)0.2138 (4)0.1645 (4)0.1014 (17)
H400.01380.1780.22620.122*
C410.0491 (5)0.2937 (3)0.1181 (3)0.0863 (14)
H410.11280.31190.14910.104*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0362 (3)0.0504 (3)0.0510 (3)0.0013 (2)0.0021 (2)0.0252 (2)
O10.0409 (15)0.0625 (16)0.0784 (18)0.0047 (12)0.0067 (13)0.0421 (14)
O20.0486 (16)0.0696 (17)0.0632 (17)0.0057 (13)0.0042 (13)0.0378 (15)
O30.0380 (15)0.0825 (18)0.0580 (16)0.0074 (13)0.0108 (12)0.0280 (14)
O40.0479 (16)0.0741 (17)0.0585 (16)0.0023 (13)0.0033 (12)0.0400 (14)
N10.0431 (19)0.0514 (19)0.0581 (19)0.0026 (15)0.0005 (15)0.0230 (16)
N20.089 (3)0.100 (3)0.078 (3)0.026 (3)0.013 (2)0.031 (3)
N30.0403 (18)0.0574 (18)0.0470 (19)0.0008 (14)0.0029 (14)0.0246 (15)
N50.101 (3)0.070 (3)0.077 (3)0.016 (2)0.021 (3)0.017 (2)
C10.043 (2)0.055 (2)0.055 (2)0.0056 (18)0.0011 (18)0.0213 (19)
C20.055 (3)0.051 (2)0.063 (3)0.0023 (19)0.008 (2)0.019 (2)
C30.061 (3)0.077 (3)0.048 (2)0.011 (2)0.002 (2)0.025 (2)
C40.049 (2)0.075 (3)0.060 (3)0.008 (2)0.005 (2)0.034 (2)
C50.037 (2)0.058 (2)0.048 (2)0.0008 (17)0.0086 (17)0.0211 (19)
C60.033 (2)0.057 (2)0.062 (2)0.0048 (17)0.0045 (18)0.024 (2)
C70.084 (3)0.073 (3)0.063 (3)0.014 (3)0.000 (2)0.019 (2)
C80.108 (5)0.081 (3)0.068 (3)0.018 (3)0.001 (3)0.018 (3)
C90.059 (3)0.088 (3)0.109 (4)0.018 (3)0.005 (3)0.022 (3)
C100.061 (3)0.079 (3)0.085 (3)0.014 (2)0.005 (3)0.014 (3)
C110.046 (2)0.059 (2)0.053 (2)0.0037 (19)0.0004 (18)0.021 (2)
C120.051 (3)0.067 (3)0.061 (3)0.009 (2)0.002 (2)0.026 (2)
C130.046 (3)0.076 (3)0.088 (3)0.010 (2)0.021 (2)0.009 (3)
C140.060 (3)0.060 (3)0.091 (3)0.016 (2)0.020 (2)0.008 (2)
C150.047 (3)0.062 (3)0.115 (4)0.002 (2)0.004 (3)0.009 (3)
C160.054 (3)0.055 (3)0.115 (4)0.003 (2)0.012 (3)0.009 (3)
C170.067 (3)0.067 (3)0.114 (4)0.012 (3)0.010 (3)0.016 (3)
C180.099 (5)0.079 (4)0.115 (5)0.019 (3)0.006 (4)0.025 (3)
C190.072 (4)0.125 (5)0.089 (4)0.013 (3)0.025 (3)0.056 (4)
C200.079 (4)0.087 (3)0.105 (4)0.020 (3)0.036 (3)0.046 (3)
C210.041 (2)0.045 (2)0.069 (3)0.0019 (17)0.003 (2)0.024 (2)
C220.047 (2)0.064 (2)0.076 (3)0.0024 (19)0.007 (2)0.038 (2)
C230.055 (3)0.094 (3)0.087 (3)0.008 (2)0.008 (2)0.050 (3)
C240.075 (4)0.151 (5)0.121 (4)0.015 (4)0.005 (3)0.096 (4)
C250.078 (4)0.158 (6)0.155 (6)0.038 (4)0.005 (4)0.103 (5)
C260.077 (4)0.186 (6)0.151 (6)0.068 (4)0.023 (4)0.105 (5)
C270.063 (3)0.129 (4)0.116 (4)0.042 (3)0.024 (3)0.076 (4)
C280.034 (2)0.0437 (19)0.0396 (19)0.0041 (16)0.0016 (16)0.0107 (16)
C290.041 (2)0.0428 (19)0.043 (2)0.0038 (16)0.0002 (16)0.0167 (16)
C300.047 (2)0.075 (3)0.064 (3)0.005 (2)0.012 (2)0.038 (2)
C310.058 (3)0.124 (4)0.091 (3)0.010 (3)0.025 (3)0.067 (3)
C320.096 (4)0.122 (4)0.091 (4)0.001 (3)0.024 (3)0.072 (3)
C330.093 (4)0.096 (4)0.082 (3)0.007 (3)0.001 (3)0.061 (3)
C340.055 (3)0.070 (3)0.065 (3)0.004 (2)0.001 (2)0.036 (2)
O50.145 (4)0.067 (2)0.124 (3)0.001 (2)0.011 (3)0.022 (2)
O60.107 (3)0.089 (2)0.102 (3)0.032 (2)0.035 (2)0.035 (2)
C420.100 (4)0.090 (4)0.067 (3)0.016 (3)0.004 (3)0.040 (3)
C430.070 (3)0.067 (3)0.050 (2)0.017 (2)0.004 (2)0.027 (2)
C440.087 (4)0.085 (3)0.092 (4)0.003 (3)0.001 (3)0.041 (3)
C450.065 (4)0.125 (5)0.124 (5)0.015 (4)0.012 (3)0.065 (4)
C460.107 (5)0.097 (4)0.094 (4)0.036 (4)0.027 (4)0.033 (3)
C470.101 (4)0.073 (3)0.092 (4)0.001 (3)0.008 (3)0.023 (3)
C480.071 (3)0.077 (3)0.066 (3)0.010 (3)0.008 (2)0.022 (2)
O70.084 (2)0.082 (2)0.095 (2)0.0141 (17)0.0120 (18)0.0397 (19)
O80.075 (2)0.102 (2)0.107 (3)0.0221 (19)0.018 (2)0.050 (2)
C490.053 (3)0.064 (3)0.092 (4)0.006 (2)0.009 (3)0.038 (3)
C500.047 (3)0.056 (3)0.091 (3)0.009 (2)0.008 (2)0.031 (3)
C510.058 (3)0.083 (3)0.102 (4)0.003 (3)0.005 (3)0.048 (3)
C520.071 (4)0.101 (4)0.143 (5)0.001 (3)0.013 (3)0.079 (4)
C530.087 (4)0.075 (4)0.163 (6)0.008 (3)0.014 (4)0.056 (4)
C540.093 (4)0.067 (3)0.124 (5)0.006 (3)0.003 (4)0.015 (3)
C550.075 (3)0.062 (3)0.100 (4)0.001 (3)0.017 (3)0.025 (3)
O90.095 (3)0.089 (2)0.091 (2)0.0281 (19)0.011 (2)0.0262 (19)
O100.103 (3)0.089 (2)0.085 (3)0.017 (2)0.000 (2)0.002 (2)
C350.072 (3)0.073 (3)0.076 (3)0.005 (3)0.011 (3)0.022 (3)
C360.066 (3)0.061 (3)0.072 (3)0.001 (2)0.009 (2)0.015 (2)
C370.095 (4)0.099 (4)0.087 (4)0.018 (3)0.011 (3)0.004 (3)
C380.099 (4)0.104 (4)0.113 (5)0.033 (4)0.011 (4)0.018 (4)
C390.093 (4)0.080 (4)0.109 (5)0.016 (3)0.019 (4)0.008 (3)
C400.108 (5)0.091 (4)0.076 (3)0.006 (3)0.016 (3)0.009 (3)
C410.092 (4)0.082 (3)0.077 (3)0.008 (3)0.013 (3)0.028 (3)
Geometric parameters (Å, º) top
Co1—O31.999 (2)C26—C271.384 (6)
Co1—O42.013 (2)C26—H260.93
Co1—N12.142 (3)C27—H270.93
Co1—N32.157 (3)C28—O4i1.257 (4)
Co1—O12.176 (2)C28—C291.491 (5)
Co1—O22.220 (2)C29—C301.385 (5)
O1—C211.275 (4)C29—C341.385 (5)
O2—C211.250 (4)C30—C311.374 (5)
O3—C281.247 (4)C30—H300.93
O4—C28i1.257 (4)C31—C321.364 (6)
N1—C141.321 (5)C31—H310.93
N1—C151.327 (5)C32—C331.363 (6)
N2—C191.290 (6)C32—H320.93
N2—C181.311 (6)C33—C341.380 (6)
N3—C41.324 (4)C33—H330.93
N3—C51.338 (4)C34—H340.93
N5—C91.320 (6)O5—C421.204 (6)
N5—C81.324 (6)O6—C421.302 (6)
C1—C31.383 (5)O6—H6A0.82
C1—C61.392 (5)C42—C431.497 (6)
C1—C21.482 (5)C43—C481.370 (6)
C2—C101.375 (6)C43—C441.374 (6)
C2—C71.385 (5)C44—C451.374 (7)
C3—C41.385 (5)C44—H440.93
C3—H30.93C45—C461.359 (7)
C4—H40.93C45—H450.93
C5—C61.376 (5)C46—C471.362 (7)
C5—H50.93C46—H460.93
C6—H60.93C47—C481.365 (6)
C7—C81.367 (6)C47—H470.93
C7—H70.93C48—H480.93
C8—H80.93O7—C491.330 (5)
C9—C101.388 (6)O7—H7A0.82
C9—H90.93O8—C491.198 (5)
C10—H100.93C49—C501.482 (6)
C11—C131.358 (5)C50—C551.366 (6)
C11—C161.359 (5)C50—C511.390 (6)
C11—C121.482 (5)C51—C521.373 (6)
C12—C201.359 (6)C51—H510.93
C12—C171.391 (6)C52—C531.356 (8)
C13—C141.368 (6)C52—H520.93
C13—H130.93C53—C541.368 (8)
C14—H140.93C53—H530.93
C15—C161.367 (6)C54—C551.394 (7)
C15—H150.93C54—H540.93
C16—H160.93C55—H550.93
C17—C181.375 (6)O9—C351.316 (5)
C17—H170.93O9—H9A0.82
C18—H180.93O10—C351.196 (5)
C19—C201.427 (7)C35—C361.507 (6)
C19—H190.93C36—C411.350 (6)
C20—H200.93C36—C371.362 (6)
C21—C221.491 (5)C37—C381.385 (7)
C22—C271.368 (5)C37—H370.93
C22—C231.382 (5)C38—C391.352 (7)
C23—C241.383 (6)C38—H380.93
C23—H230.93C39—C401.372 (7)
C24—C251.358 (7)C39—H390.93
C24—H240.93C40—C411.377 (7)
C25—C261.346 (7)C40—H400.93
C25—H250.93C41—H410.93
O3—Co1—O4111.24 (10)C23—C24—H24119.9
O3—Co1—N193.58 (11)C26—C25—C24120.2 (5)
O4—Co1—N193.96 (11)C26—C25—H25119.9
O3—Co1—N387.57 (11)C24—C25—H25119.9
O4—Co1—N389.12 (11)C25—C26—C27120.7 (5)
N1—Co1—N3176.07 (11)C25—C26—H26119.7
O3—Co1—O196.72 (10)C27—C26—H26119.7
O4—Co1—O1151.17 (10)C22—C27—C26120.0 (5)
N1—Co1—O191.07 (10)C22—C27—H27120
N3—Co1—O185.06 (10)C26—C27—H27120
O3—Co1—O2155.49 (10)O3—C28—O4i124.4 (3)
O4—Co1—O291.70 (10)O3—C28—C29118.8 (3)
N1—Co1—O293.29 (10)O4i—C28—C29116.8 (3)
N3—Co1—O284.17 (10)C30—C29—C34119.0 (3)
O1—Co1—O259.65 (9)C30—C29—C28120.1 (3)
C21—O1—Co190.4 (2)C34—C29—C28120.9 (3)
C21—O2—Co189.0 (2)C31—C30—C29120.8 (4)
C28—O3—Co1157.9 (2)C31—C30—H30119.6
C28i—O4—Co1133.3 (2)C29—C30—H30119.6
C14—N1—C15114.3 (3)C32—C31—C30119.3 (4)
C14—N1—Co1122.7 (3)C32—C31—H31120.3
C15—N1—Co1122.8 (3)C30—C31—H31120.3
C19—N2—C18118.2 (5)C33—C32—C31121.1 (4)
C4—N3—C5116.6 (3)C33—C32—H32119.5
C4—N3—Co1121.2 (2)C31—C32—H32119.5
C5—N3—Co1122.2 (2)C32—C33—C34120.1 (4)
C9—N5—C8117.2 (4)C32—C33—H33119.9
C3—C1—C6116.7 (3)C34—C33—H33119.9
C3—C1—C2121.9 (3)C33—C34—C29119.7 (4)
C6—C1—C2121.3 (3)C33—C34—H34120.2
C10—C2—C7116.9 (4)C29—C34—H34120.2
C10—C2—C1122.8 (4)C42—O6—H6A109.6
C7—C2—C1120.3 (4)O5—C42—O6123.4 (5)
C1—C3—C4119.5 (4)O5—C42—C43124.3 (6)
C1—C3—H3120.2O6—C42—C43112.3 (5)
C4—C3—H3120.2C48—C43—C44119.0 (4)
N3—C4—C3123.9 (4)C48—C43—C42122.9 (5)
N3—C4—H4118C44—C43—C42118.1 (5)
C3—C4—H4118C43—C44—C45120.3 (5)
N3—C5—C6123.6 (3)C43—C44—H44119.9
N3—C5—H5118.2C45—C44—H44119.9
C6—C5—H5118.2C46—C45—C44120.1 (5)
C5—C6—C1119.7 (3)C46—C45—H45120
C5—C6—H6120.2C44—C45—H45120
C1—C6—H6120.2C45—C46—C47119.8 (5)
C8—C7—C2119.5 (5)C45—C46—H46120.1
C8—C7—H7120.3C47—C46—H46120.1
C2—C7—H7120.3C46—C47—C48120.5 (5)
N5—C8—C7123.8 (5)C46—C47—H47119.8
N5—C8—H8118.1C48—C47—H47119.8
C7—C8—H8118.1C47—C48—C43120.3 (5)
N5—C9—C10122.9 (5)C47—C48—H48119.8
N5—C9—H9118.5C43—C48—H48119.8
C10—C9—H9118.5C49—O7—H7A109.3
C2—C10—C9119.7 (4)O8—C49—O7122.7 (4)
C2—C10—H10120.2O8—C49—C50124.7 (5)
C9—C10—H10120.2O7—C49—C50112.5 (5)
C13—C11—C16115.6 (4)C55—C50—C51119.5 (4)
C13—C11—C12122.9 (4)C55—C50—C49122.2 (5)
C16—C11—C12121.5 (4)C51—C50—C49118.3 (4)
C20—C12—C17116.1 (4)C52—C51—C50120.2 (5)
C20—C12—C11123.2 (4)C52—C51—H51119.9
C17—C12—C11120.7 (4)C50—C51—H51119.9
C11—C13—C14120.8 (4)C53—C52—C51119.9 (5)
C11—C13—H13119.6C53—C52—H52120.1
C14—C13—H13119.6C51—C52—H52120.1
N1—C14—C13124.3 (4)C52—C53—C54121.1 (5)
N1—C14—H14117.9C52—C53—H53119.5
C13—C14—H14117.9C54—C53—H53119.5
N1—C15—C16124.5 (4)C53—C54—C55119.4 (6)
N1—C15—H15117.8C53—C54—H54120.3
C16—C15—H15117.8C55—C54—H54120.3
C11—C16—C15120.4 (4)C50—C55—C54119.9 (5)
C11—C16—H16119.8C50—C55—H55120
C15—C16—H16119.8C54—C55—H55120
C18—C17—C12120.1 (5)C35—O9—H9A109.7
C18—C17—H17119.9O10—C35—O9124.4 (5)
C12—C17—H17119.9O10—C35—C36123.1 (5)
N2—C18—C17123.3 (5)O9—C35—C36112.5 (4)
N2—C18—H18118.3C41—C36—C37119.1 (4)
C17—C18—H18118.3C41—C36—C35123.2 (5)
N2—C19—C20122.6 (5)C37—C36—C35117.7 (4)
N2—C19—H19118.7C36—C37—C38120.9 (5)
C20—C19—H19118.7C36—C37—H37119.5
C12—C20—C19119.6 (5)C38—C37—H37119.5
C12—C20—H20120.2C39—C38—C37119.3 (6)
C19—C20—H20120.2C39—C38—H38120.3
O2—C21—O1120.0 (3)C37—C38—H38120.3
O2—C21—C22120.3 (3)C38—C39—C40120.2 (5)
O1—C21—C22119.7 (4)C38—C39—H39119.9
C27—C22—C23119.0 (4)C40—C39—H39119.9
C27—C22—C21120.6 (4)C39—C40—C41119.4 (5)
C23—C22—C21120.3 (4)C39—C40—H40120.3
C22—C23—C24119.9 (4)C41—C40—H40120.3
C22—C23—H23120C36—C41—C40121.0 (5)
C24—C23—H23120C36—C41—H41119.5
C25—C24—C23120.2 (5)C40—C41—H41119.5
C25—C24—H24119.9
O3—Co1—O1—C21167.4 (2)C11—C12—C17—C18179.9 (4)
O4—Co1—O1—C211.4 (3)C19—N2—C18—C172.2 (9)
N1—Co1—O1—C2198.8 (2)C12—C17—C18—N21.2 (9)
N3—Co1—O1—C2180.5 (2)C18—N2—C19—C201.3 (8)
O2—Co1—O1—C215.7 (2)C17—C12—C20—C191.6 (7)
O3—Co1—O2—C2111.0 (4)C11—C12—C20—C19179.1 (4)
O4—Co1—O2—C21170.8 (2)N2—C19—C20—C120.6 (8)
N1—Co1—O2—C2195.1 (2)Co1—O2—C21—O19.8 (3)
N3—Co1—O2—C2181.9 (2)Co1—O2—C21—C22168.1 (3)
O1—Co1—O2—C215.8 (2)Co1—O1—C21—O210.0 (3)
O4—Co1—O3—C2869.3 (7)Co1—O1—C21—C22167.9 (3)
N1—Co1—O3—C2826.4 (7)O2—C21—C22—C273.6 (6)
N3—Co1—O3—C28157.4 (7)O1—C21—C22—C27178.4 (4)
O1—Co1—O3—C28117.9 (7)O2—C21—C22—C23173.8 (4)
O2—Co1—O3—C28132.4 (6)O1—C21—C22—C234.2 (6)
O3—Co1—O4—C28i18.2 (3)C27—C22—C23—C240.5 (7)
N1—Co1—O4—C28i77.2 (3)C21—C22—C23—C24177.9 (4)
N3—Co1—O4—C28i105.2 (3)C22—C23—C24—C250.2 (8)
O1—Co1—O4—C28i176.7 (3)C23—C24—C25—C260.1 (10)
O2—Co1—O4—C28i170.6 (3)C24—C25—C26—C270.2 (11)
O3—Co1—N1—C1423.0 (3)C23—C22—C27—C260.5 (8)
O4—Co1—N1—C1488.6 (3)C21—C22—C27—C26177.9 (5)
O1—Co1—N1—C14119.8 (3)C25—C26—C27—C220.2 (10)
O2—Co1—N1—C14179.4 (3)Co1—O3—C28—O4i65.7 (8)
O3—Co1—N1—C15152.1 (3)Co1—O3—C28—C29114.8 (6)
O4—Co1—N1—C1596.3 (3)O3—C28—C29—C30175.8 (3)
O1—Co1—N1—C1555.3 (3)O4i—C28—C29—C304.7 (5)
O2—Co1—N1—C154.3 (3)O3—C28—C29—C344.7 (5)
O3—Co1—N3—C441.7 (3)O4i—C28—C29—C34174.9 (3)
O4—Co1—N3—C4153.0 (3)C34—C29—C30—C310.6 (6)
O1—Co1—N3—C455.3 (3)C28—C29—C30—C31179.0 (4)
O2—Co1—N3—C4115.2 (3)C29—C30—C31—C320.6 (7)
O3—Co1—N3—C5140.8 (3)C30—C31—C32—C330.9 (8)
O4—Co1—N3—C529.5 (3)C31—C32—C33—C340.2 (8)
O1—Co1—N3—C5122.3 (3)C32—C33—C34—C291.0 (7)
O2—Co1—N3—C562.3 (3)C30—C29—C34—C331.3 (6)
C3—C1—C2—C10160.3 (4)C28—C29—C34—C33178.2 (4)
C6—C1—C2—C1022.2 (6)O5—C42—C43—C48166.7 (5)
C3—C1—C2—C721.8 (6)O6—C42—C43—C4811.4 (6)
C6—C1—C2—C7155.8 (4)O5—C42—C43—C4412.2 (7)
C6—C1—C3—C41.6 (6)O6—C42—C43—C44169.6 (4)
C2—C1—C3—C4176.0 (4)C48—C43—C44—C450.9 (7)
C5—N3—C4—C31.5 (6)C42—C43—C44—C45179.9 (4)
Co1—N3—C4—C3179.2 (3)C43—C44—C45—C460.3 (8)
C1—C3—C4—N30.0 (6)C44—C45—C46—C470.8 (9)
C4—N3—C5—C61.4 (5)C45—C46—C47—C481.3 (9)
Co1—N3—C5—C6179.0 (3)C46—C47—C48—C430.7 (8)
N3—C5—C6—C10.3 (5)C44—C43—C48—C470.4 (7)
C3—C1—C6—C51.8 (5)C42—C43—C48—C47179.3 (4)
C2—C1—C6—C5175.9 (3)O8—C49—C50—C55167.8 (4)
C10—C2—C7—C80.8 (7)O7—C49—C50—C5512.5 (6)
C1—C2—C7—C8177.3 (4)O8—C49—C50—C5112.8 (6)
C9—N5—C8—C70.0 (8)O7—C49—C50—C51166.9 (4)
C2—C7—C8—N50.1 (8)C55—C50—C51—C520.2 (6)
C8—N5—C9—C100.7 (8)C49—C50—C51—C52179.7 (4)
C7—C2—C10—C91.4 (7)C50—C51—C52—C530.1 (7)
C1—C2—C10—C9176.6 (4)C51—C52—C53—C540.2 (9)
N5—C9—C10—C21.5 (8)C52—C53—C54—C550.3 (9)
C13—C11—C12—C2025.2 (6)C51—C50—C55—C540.4 (7)
C16—C11—C12—C20155.5 (5)C49—C50—C55—C54179.8 (4)
C13—C11—C12—C17154.0 (5)C53—C54—C55—C500.4 (8)
C16—C11—C12—C1725.2 (6)O10—C35—C36—C41177.0 (5)
C16—C11—C13—C141.6 (7)O9—C35—C36—C413.8 (7)
C12—C11—C13—C14177.7 (4)O10—C35—C36—C373.2 (7)
C15—N1—C14—C132.8 (7)O9—C35—C36—C37176.0 (5)
Co1—N1—C14—C13172.6 (4)C41—C36—C37—C380.8 (9)
C11—C13—C14—N11.3 (8)C35—C36—C37—C38179.1 (5)
C14—N1—C15—C161.7 (7)C36—C37—C38—C391.1 (10)
Co1—N1—C15—C16173.8 (4)C37—C38—C39—C401.1 (10)
C13—C11—C16—C152.7 (7)C38—C39—C40—C410.8 (9)
C12—C11—C16—C15176.6 (4)C37—C36—C41—C400.4 (8)
N1—C15—C16—C111.1 (8)C35—C36—C41—C40179.5 (5)
C20—C12—C17—C180.8 (7)C39—C40—C41—C360.4 (8)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···N2ii0.821.912.726 (5)177
O7—H7A···O1iii0.821.862.656 (4)164
O9—H9A···N5iv0.821.912.732 (5)176
Symmetry codes: (ii) x+1, y, z; (iii) x, y+1, z+1; (iv) x1, y+1, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···N2i0.821.912.726 (5)177
O7—H7A···O1ii0.821.862.656 (4)164
O9—H9A···N5iii0.821.912.732 (5)176
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z+1; (iii) x1, y+1, z1.
Acknowledgements top

The authors acknowledge financial support from the Consejo Nacional de Ciencia y Tecnología (CONACyT), Fondo Mixto Veracruz (127835).

references
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