The coordination geometry around the central CoII ion is unexpectedly different from that for the co-crystal of the title molecule with anthranilic acid.
Keywords: crystal structure, CoII complex, Schiff base ligand, pyridine-2-carbaldehyde, anthranilic acid, hydrogen bonding
Abstract
The title compound, [Co(C13H9N2O2)2]·1.5C3H7NO, is formed as a neutral CoII complex with dimethylformamide (DMF) solvent molecules. The CoII atom has a distorted O2N4 octahedral coordination sphere defined by two tridentate anionic Schiff base ligands with the O atoms being cis. The coordination sphere around the CoII atom is geometrically different from that reported for the co-crystal [Co(C13H9N2O2)2]·AA·H2O (AA is anthranilic acid). One of the DMF solvent molecules was modelled as being disordered about a crystallographic inversion centre with half-occupancy. The crystal structure is made up from alternating layers of complex molecules and DMF molecules parallel to (010). C—H⋯O hydrogen-bonding interactions between the complex molecules and the solvent molecules consolidate the crystal packing.
Chemical context
Metal complexes containing Schiff bases are the most fundamental chelating systems in coordination chemistry. Their interesting chemical and physical properties and their wide-ranging applications in numerous scientific areas have been explored widely (Vigato et al., 2012 ▶). During the last few years, we have investigated the chemistry of 3d metal complexes of Schiff base ligands with the aim of preparing mono- and heterometallic polynuclear compounds.
Recently, we have investigated the coordination behaviour of the tridentate carboxylate Schiff base ligand 2-N-(2′-pyridylimine)benzoic acid (HL), which results from the condensation between pyridine-2-carbaldehyde and anthranilic acid (AA) and reported the cation–anion complex CrL 2NO3·H2O (Buvaylo et al., 2014a ▶) and co-crystals of ML 2 (M = Co, Ni, Zn) and anthranilic acid (Buvaylo et al., 2014b ▶). The respective compounds were prepared by in situ Schiff base synthesis. ML 2 molecules of the isotypic CoL 2·AA·H2O and NiL 2·AA·H2O co-crystals retained the intramolecular distances M—(N,O) as found in the structure of the ‘native’ Schiff base metal complex NiL 2·H2O (Mukhopadhyay & Pal, 2005 ▶). The crystal packing of the co-crystals was described as an insertion of the organic molecules between the layers of ML 2 complexes as they occur in the reported NiL 2·H2O structure.
The title compound, [Co(C13H9N2O2)2]·1.5C3H7NO, was prepared similarly to the co-crystals (Buvaylo et al., 2014b ▶) but using additional [Cd(CH3COO)2]·2H2O in an attempt to prepare a heterometallic compound with HL. The obtained crystals, however, did not appear to contain anthranilic acid molecules or cadmium.
Structural commentary
The asymmetric unit of the title compound consists of one neutral CoL 2 molecule and 1.5 dimethylformamide (DMF) solvent molecules, of which one is fully ordered, the other being disordered about a crystallographic inversion centre. The CoL 2 molecule has no crystallographically imposed symmetry. The ligand molecules are deprotonated at the carboxylato oxygen atom and coordinate to the CoII atom through the azomethine, pyridine-N and carboxylato-O atoms in such a way that the metal atom is octahedrally surrounded by two anionic ligands with cis O atoms (Fig. 1 ▶, Table 1 ▶). The octahedral geometry is severely distorted: the Co—(N,O) distances fall in the range 2.0072 (12)–2.1498 (14) Å, the trans angles at the CoII ion lie in the range 161.53 (6)–177.35 (5), the cis angles vary from 77.91 (5) to 103.70 (5)°. Surprisingly, the coordination geometry around the CoII ion is markedly different from that of CoL 2·AA·H2O (Buvaylo et al., 2014b ▶) where the Co—(N,O) distances range from 1.990 (2) to 2.088 (18) Å, and the trans and cis angles at the CoII ion vary from 167.96 (6) to 176.95 (7) and from 80.93 (7) to 98.81 (7)°, respectively. The reason for such a discrepancy could be the absence of classical hydrogen bonds in the title compound in contrast to the co-crystal CoL 2·AA·H2O. A metal site with mixed (Co/Cd) occupancy for the title compound was ruled out by the refinement.
Figure 1.
The molecular structure of the title complex, showing the atom-numbering scheme. Non-H atoms are shown as displacement ellipsoids at the 50% probability level.
Table 1. Selected bond lengths (Å).
| Co1—O41 | 2.0072 (12) | Co1—N10 | 2.1189 (13) |
| Co1—O21 | 2.0181 (13) | Co1—N31 | 2.1358 (14) |
| Co1—N30 | 2.1057 (13) | Co1—N11 | 2.1498 (14) |
Supramolecular features
The crystal lattice is built of alternating layers of complex CoL 2 molecules and DMF molecules parallel to (010) (Fig. 2 ▶). Neighbouring CoL 2 molecules within a layer are related by an inversion centre with Co⋯Co separations of 6.8713 (6) and 6.9985 (6) Å. Weak C—H⋯O hydrogen-bonding interactions between the complex molecules and the solvent molecules lead to a consolidation of the crystal packing.
Figure 2.
Packing diagram showing alternating layers of [CoL 2] and DMF molecules. CH hydrogens have been omitted for clarity.
Synthesis and crystallization
The Schiff base ligand HL was prepared by refluxing pyridine-2-carbaldehyde (0.38 ml, 4 mmol) with anthranilic acid (0.55 g, 4 mmol) in 20 ml methanol for half an hour. The resultant yellow solution was left in open air overnight and used without further purification.
To a stirred DMF solution (5 ml) of Cd(CH3COO)2·2H2O (0.53 g, 2 mmol) in a 50 ml conic flask, HL (0.21 g, 4 mmol) in methanol from the previous preparation was added. The solution was magnetically stirred at 323 K for 20 minutes and a yellow precipitate of a Cd complex formed. Co(CH3COO)2·4H2O (0.25 g, 1 mmol) in DMF (10 ml) was added to the reaction mixture after a week. The mixture was stirred magnetically at 323 K for an hour, however, the yellow precipitate did not dissolve and was filtered off. The resulting red–brown solution was left to evaporate at room temperature. Red–brown block-like crystals of the title compound formed the next day. They were collected by filter-suction, washed with dry isopropanol and finally dried in vacuo (yield: 23% based on cobalt salt). Analysis for C26H18CoN4O4·1.5C3H7NO calculated (%) C: 59.18 H: 4.64 N: 12.45 Co: 9.52. Found (%) C: 59.33 H: 4.49 N: 12.41 Co: 9.76. Spectroscopic data (IR, KBr) are available as an additional Figure in the supporting information.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▶. The refinement of the metal occupancy as part Co and part Cd gave 100% Co. One solvent DMF molecule was modelled as being disordered about a crystallographic inversion centre with resulting half-occupancy and with geometries restrained to ideal values. All hydrogen atoms were placed at calculated positions and refined by use of the riding-model approximation, with U iso(H) = 1.2U eq of the parent C atom.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | [Co(C13H9N2O2)2]·1.5C3H7NO |
| M r | 619.02 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 100 |
| a, b, c (Å) | 8.4361 (6), 13.2603 (10), 13.8664 (10) |
| α, β, γ (°) | 110.061 (7), 103.559 (6), 101.430 (6) |
| V (Å3) | 1348.9 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.69 |
| Crystal size (mm) | 0.40 × 0.30 × 0.18 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur |
| Absorption correction | Analytical [CrysAlis PRO (Agilent, 2011 ▶) using an expression derived by Clark & Reid (1995 ▶)] |
| T min, T max | 0.821, 0.898 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 33209, 10748, 8599 |
| R int | 0.036 |
| (sin θ/λ)max (Å−1) | 0.787 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.048, 0.127, 1.05 |
| No. of reflections | 10748 |
| No. of parameters | 410 |
| No. of restraints | 35 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.74, −0.54 |
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814019485/wm5044sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019485/wm5044Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814019485/wm5044Isup3.jpg
CCDC reference: 1021534
Additional supporting information: crystallographic information; 3D view; checkCIF report
Table 2. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C10—H10⋯O42i | 0.95 | 2.46 | 3.393 (2) | 169 |
| C102—H10E⋯O42ii | 0.98 | 2.46 | 3.369 (3) | 154 |
| C16—H16⋯O101 | 0.95 | 2.41 | 3.326 (3) | 163 |
| C201—H20C⋯O22iii | 0.98 | 1.97 | 2.819 (10) | 143 |
| C23—H23⋯O42i | 0.95 | 2.60 | 3.454 (2) | 150 |
| C30—H30⋯O22iv | 0.95 | 2.42 | 3.344 (3) | 163 |
| C36—H36⋯O201v | 0.95 | 2.54 | 3.235 (13) | 130 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
.
Acknowledgments
This work was partly supported by the State Fund for Fundamental Researches of Ukraine (project 54.3/005). The authors acknowledge the facilities, scientific and technical assistance of the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy, Characterization & Analysis, the University of Western Australia, a facility funded by the University, State and Commonwealth Governments.
supplementary crystallographic information
Crystal data
| [Co(C13H9N2O2)2]·1.5C3H7NO | Z = 2 |
| Mr = 619.02 | F(000) = 642 |
| Triclinic, P1 | Dx = 1.524 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.4361 (6) Å | Cell parameters from 10672 reflections |
| b = 13.2603 (10) Å | θ = 2.8–34.5° |
| c = 13.8664 (10) Å | µ = 0.69 mm−1 |
| α = 110.061 (7)° | T = 100 K |
| β = 103.559 (6)° | Block, red-brown |
| γ = 101.430 (6)° | 0.40 × 0.30 × 0.18 mm |
| V = 1348.9 (2) Å3 |
Data collection
| Oxford Diffraction Xcalibur diffractometer | 10748 independent reflections |
| Graphite monochromator | 8599 reflections with I > 2σ(I) |
| Detector resolution: 16.0009 pixels mm-1 | Rint = 0.036 |
| ω scans | θmax = 34°, θmin = 2.8° |
| Absorption correction: analytical [CrysAlis PRO (Agilent, 2011) using an expression derived by Clark & Reid (1995)] | h = −12→13 |
| Tmin = 0.821, Tmax = 0.898 | k = −20→19 |
| 33209 measured reflections | l = −21→21 |
Refinement
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.127 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.4745P] where P = (Fo2 + 2Fc2)/3 |
| 10748 reflections | (Δ/σ)max = 0.006 |
| 410 parameters | Δρmax = 0.74 e Å−3 |
| 35 restraints | Δρmin = −0.54 e Å−3 |
Special details
| Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.One solvent dmf molecule was modelled as being disordered about a crystallographic inversion centre. The geometries were restrained to ideal values. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Co1 | 0.50566 (3) | 0.996180 (17) | 0.747260 (16) | 0.01696 (6) | |
| N11 | 0.28320 (17) | 0.91486 (12) | 0.60369 (11) | 0.0197 (2) | |
| C12 | 0.2706 (2) | 0.97508 (14) | 0.54251 (12) | 0.0194 (3) | |
| C13 | 0.1383 (2) | 0.93697 (15) | 0.44446 (14) | 0.0255 (3) | |
| H13 | 0.1345 | 0.9792 | 0.4012 | 0.031* | |
| C14 | 0.0121 (2) | 0.83562 (17) | 0.41152 (15) | 0.0307 (4) | |
| H14 | −0.0801 | 0.8077 | 0.3453 | 0.037* | |
| C15 | 0.0221 (2) | 0.77579 (16) | 0.47596 (15) | 0.0289 (4) | |
| H15 | −0.0645 | 0.7073 | 0.4556 | 0.035* | |
| C16 | 0.1607 (2) | 0.81754 (15) | 0.57109 (14) | 0.0245 (3) | |
| H16 | 0.1687 | 0.7755 | 0.6144 | 0.029* | |
| C10 | 0.4017 (2) | 1.08481 (13) | 0.58651 (12) | 0.0192 (3) | |
| H10 | 0.4017 | 1.131 | 0.5472 | 0.023* | |
| N10 | 0.51714 (16) | 1.11742 (11) | 0.67961 (10) | 0.0170 (2) | |
| C21 | 0.7536 (2) | 1.26504 (14) | 0.83458 (12) | 0.0205 (3) | |
| C22 | 0.65025 (19) | 1.22222 (13) | 0.72478 (12) | 0.0174 (3) | |
| C23 | 0.6816 (2) | 1.28292 (14) | 0.66229 (13) | 0.0240 (3) | |
| H23 | 0.6106 | 1.2552 | 0.5888 | 0.029* | |
| C24 | 0.8144 (2) | 1.38261 (15) | 0.70634 (14) | 0.0277 (3) | |
| H24 | 0.833 | 1.4234 | 0.6634 | 0.033* | |
| C25 | 0.9208 (2) | 1.42328 (16) | 0.81350 (15) | 0.0285 (4) | |
| H25 | 1.0149 | 1.4901 | 0.8431 | 0.034* | |
| C26 | 0.8883 (2) | 1.36573 (15) | 0.87639 (14) | 0.0269 (3) | |
| H26 | 0.9591 | 1.3952 | 0.9501 | 0.032* | |
| C20 | 0.7319 (2) | 1.21453 (15) | 0.91605 (13) | 0.0240 (3) | |
| O21 | 0.69029 (16) | 1.10880 (10) | 0.88645 (9) | 0.0232 (2) | |
| O22 | 0.7636 (3) | 1.28251 (13) | 1.01092 (11) | 0.0475 (4) | |
| N31 | 0.31332 (17) | 1.02612 (12) | 0.82016 (11) | 0.0203 (2) | |
| C32 | 0.2642 (2) | 0.94913 (14) | 0.85884 (12) | 0.0197 (3) | |
| C33 | 0.1204 (2) | 0.93994 (16) | 0.89184 (13) | 0.0257 (3) | |
| H33 | 0.0913 | 0.8875 | 0.9222 | 0.031* | |
| C34 | 0.0202 (2) | 1.00887 (17) | 0.87943 (13) | 0.0284 (4) | |
| H34 | −0.0811 | 1.0023 | 0.8986 | 0.034* | |
| C35 | 0.0694 (2) | 1.08726 (17) | 0.83884 (13) | 0.0270 (3) | |
| H35 | 0.0025 | 1.1352 | 0.8296 | 0.032* | |
| C36 | 0.2188 (2) | 1.09467 (16) | 0.81177 (13) | 0.0245 (3) | |
| H36 | 0.255 | 1.1504 | 0.7864 | 0.029* | |
| C30 | 0.3667 (2) | 0.87175 (14) | 0.85948 (12) | 0.0205 (3) | |
| H30 | 0.3484 | 0.821 | 0.8931 | 0.025* | |
| N30 | 0.48205 (17) | 0.87471 (11) | 0.81309 (10) | 0.0181 (2) | |
| C41 | 0.6719 (2) | 0.78101 (13) | 0.73476 (12) | 0.0207 (3) | |
| C42 | 0.5915 (2) | 0.80600 (13) | 0.81452 (12) | 0.0199 (3) | |
| C43 | 0.6270 (2) | 0.76728 (15) | 0.89722 (14) | 0.0271 (3) | |
| H43 | 0.5707 | 0.7825 | 0.9501 | 0.033* | |
| C44 | 0.7429 (3) | 0.70727 (16) | 0.90256 (15) | 0.0329 (4) | |
| H44 | 0.7668 | 0.6823 | 0.9594 | 0.039* | |
| C45 | 0.8246 (3) | 0.68328 (15) | 0.82488 (15) | 0.0313 (4) | |
| H45 | 0.9061 | 0.6434 | 0.8293 | 0.038* | |
| C46 | 0.7858 (2) | 0.71809 (14) | 0.74084 (14) | 0.0261 (3) | |
| H46 | 0.838 | 0.6987 | 0.6861 | 0.031* | |
| C40 | 0.6515 (2) | 0.81957 (14) | 0.64211 (13) | 0.0214 (3) | |
| O41 | 0.63573 (16) | 0.91724 (11) | 0.65820 (10) | 0.0244 (2) | |
| O42 | 0.6581 (2) | 0.75447 (12) | 0.55549 (10) | 0.0344 (3) | |
| C101 | 0.2797 (3) | 0.5260 (2) | 0.53693 (17) | 0.0462 (6) | |
| H10A | 0.1781 | 0.5472 | 0.5112 | 0.069* | |
| H10B | 0.2719 | 0.4523 | 0.4839 | 0.069* | |
| H10C | 0.3825 | 0.5826 | 0.5457 | 0.069* | |
| C102 | 0.4048 (3) | 0.4635 (2) | 0.6791 (2) | 0.0492 (6) | |
| H10D | 0.5229 | 0.5046 | 0.6912 | 0.074* | |
| H10E | 0.3748 | 0.3864 | 0.6245 | 0.074* | |
| H10F | 0.3947 | 0.4615 | 0.7475 | 0.074* | |
| N101 | 0.2892 (2) | 0.52022 (14) | 0.64083 (13) | 0.0314 (3) | |
| C103 | 0.2097 (2) | 0.57619 (16) | 0.70349 (15) | 0.0292 (4) | |
| H103 | 0.2267 | 0.5737 | 0.7728 | 0.035* | |
| O101 | 0.1172 (2) | 0.63017 (13) | 0.68000 (13) | 0.0384 (3) | |
| C201 | 0.6583 (8) | 0.4774 (8) | 1.0471 (4) | 0.074 (2) | 0.5 |
| H20A | 0.6872 | 0.5372 | 1.1196 | 0.11* | 0.5 |
| H20B | 0.7402 | 0.4981 | 1.0122 | 0.11* | 0.5 |
| H20C | 0.6635 | 0.4067 | 1.0537 | 0.11* | 0.5 |
| C202 | 0.4086 (11) | 0.5472 (7) | 1.0070 (9) | 0.094 (3) | 0.5 |
| H20D | 0.4843 | 0.62 | 1.0193 | 0.141* | 0.5 |
| H20E | 0.3758 | 0.5541 | 1.0718 | 0.141* | 0.5 |
| H20F | 0.3056 | 0.5245 | 0.9445 | 0.141* | 0.5 |
| N201 | 0.4968 (10) | 0.4635 (6) | 0.9856 (6) | 0.0754 (17) | 0.5 |
| C203 | 0.4235 (7) | 0.3681 (6) | 0.9046 (5) | 0.0535 (12) | 0.5 |
| H203 | 0.4778 | 0.312 | 0.8829 | 0.064* | 0.5 |
| O201 | 0.2772 (15) | 0.3581 (9) | 0.8592 (9) | 0.211 (4) | 0.5 |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.01868 (10) | 0.01863 (11) | 0.01563 (10) | 0.00464 (7) | 0.00591 (7) | 0.00978 (8) |
| N11 | 0.0208 (6) | 0.0218 (6) | 0.0165 (5) | 0.0045 (5) | 0.0054 (5) | 0.0092 (5) |
| C12 | 0.0192 (6) | 0.0232 (7) | 0.0163 (6) | 0.0063 (5) | 0.0056 (5) | 0.0091 (5) |
| C13 | 0.0258 (8) | 0.0286 (8) | 0.0208 (7) | 0.0062 (6) | 0.0038 (6) | 0.0123 (6) |
| C14 | 0.0247 (8) | 0.0347 (10) | 0.0249 (8) | 0.0029 (7) | −0.0012 (6) | 0.0127 (7) |
| C15 | 0.0231 (8) | 0.0294 (9) | 0.0267 (8) | −0.0005 (6) | 0.0024 (6) | 0.0112 (7) |
| C16 | 0.0243 (7) | 0.0252 (8) | 0.0224 (7) | 0.0019 (6) | 0.0055 (6) | 0.0124 (6) |
| C10 | 0.0223 (7) | 0.0213 (7) | 0.0171 (6) | 0.0071 (5) | 0.0075 (5) | 0.0107 (5) |
| N10 | 0.0191 (6) | 0.0183 (6) | 0.0157 (5) | 0.0061 (5) | 0.0067 (4) | 0.0084 (5) |
| C21 | 0.0247 (7) | 0.0207 (7) | 0.0176 (6) | 0.0041 (6) | 0.0087 (5) | 0.0102 (5) |
| C22 | 0.0207 (6) | 0.0172 (6) | 0.0170 (6) | 0.0059 (5) | 0.0082 (5) | 0.0087 (5) |
| C23 | 0.0317 (8) | 0.0237 (8) | 0.0182 (7) | 0.0058 (6) | 0.0082 (6) | 0.0120 (6) |
| C24 | 0.0372 (9) | 0.0241 (8) | 0.0243 (8) | 0.0040 (7) | 0.0110 (7) | 0.0149 (7) |
| C25 | 0.0335 (9) | 0.0239 (8) | 0.0271 (8) | 0.0017 (7) | 0.0096 (7) | 0.0133 (7) |
| C26 | 0.0305 (8) | 0.0235 (8) | 0.0213 (7) | −0.0004 (6) | 0.0046 (6) | 0.0102 (6) |
| C20 | 0.0273 (8) | 0.0249 (8) | 0.0182 (7) | 0.0017 (6) | 0.0070 (6) | 0.0108 (6) |
| O21 | 0.0260 (6) | 0.0228 (6) | 0.0201 (5) | 0.0040 (4) | 0.0039 (4) | 0.0123 (4) |
| O22 | 0.0860 (13) | 0.0276 (7) | 0.0186 (6) | −0.0018 (8) | 0.0160 (7) | 0.0088 (5) |
| N31 | 0.0203 (6) | 0.0258 (7) | 0.0176 (6) | 0.0068 (5) | 0.0067 (5) | 0.0118 (5) |
| C32 | 0.0200 (7) | 0.0224 (7) | 0.0140 (6) | 0.0021 (5) | 0.0055 (5) | 0.0068 (5) |
| C33 | 0.0246 (8) | 0.0298 (8) | 0.0192 (7) | 0.0005 (6) | 0.0102 (6) | 0.0082 (6) |
| C34 | 0.0200 (7) | 0.0399 (10) | 0.0181 (7) | 0.0039 (7) | 0.0076 (6) | 0.0056 (7) |
| C35 | 0.0238 (8) | 0.0385 (10) | 0.0179 (7) | 0.0132 (7) | 0.0063 (6) | 0.0089 (7) |
| C36 | 0.0252 (8) | 0.0333 (9) | 0.0208 (7) | 0.0130 (7) | 0.0092 (6) | 0.0143 (7) |
| C30 | 0.0245 (7) | 0.0208 (7) | 0.0145 (6) | 0.0023 (6) | 0.0056 (5) | 0.0086 (5) |
| N30 | 0.0202 (6) | 0.0179 (6) | 0.0139 (5) | 0.0025 (5) | 0.0033 (4) | 0.0071 (4) |
| C41 | 0.0233 (7) | 0.0172 (7) | 0.0171 (6) | 0.0034 (5) | 0.0027 (5) | 0.0060 (5) |
| C42 | 0.0233 (7) | 0.0165 (6) | 0.0158 (6) | 0.0035 (5) | 0.0019 (5) | 0.0063 (5) |
| C43 | 0.0380 (9) | 0.0236 (8) | 0.0184 (7) | 0.0082 (7) | 0.0044 (6) | 0.0108 (6) |
| C44 | 0.0454 (11) | 0.0269 (9) | 0.0228 (8) | 0.0134 (8) | 0.0002 (7) | 0.0121 (7) |
| C45 | 0.0380 (10) | 0.0210 (8) | 0.0285 (8) | 0.0120 (7) | 0.0002 (7) | 0.0082 (7) |
| C46 | 0.0278 (8) | 0.0207 (7) | 0.0236 (7) | 0.0071 (6) | 0.0033 (6) | 0.0056 (6) |
| C40 | 0.0207 (7) | 0.0247 (8) | 0.0191 (7) | 0.0066 (6) | 0.0062 (5) | 0.0098 (6) |
| O41 | 0.0304 (6) | 0.0269 (6) | 0.0244 (6) | 0.0114 (5) | 0.0145 (5) | 0.0153 (5) |
| O42 | 0.0531 (9) | 0.0341 (7) | 0.0206 (6) | 0.0208 (7) | 0.0145 (6) | 0.0107 (5) |
| C101 | 0.0517 (13) | 0.0484 (13) | 0.0279 (9) | 0.0014 (11) | 0.0207 (10) | 0.0063 (9) |
| C102 | 0.0334 (11) | 0.0434 (13) | 0.0490 (13) | 0.0134 (10) | 0.0020 (10) | 0.0004 (11) |
| N101 | 0.0294 (8) | 0.0303 (8) | 0.0251 (7) | 0.0033 (6) | 0.0089 (6) | 0.0035 (6) |
| C103 | 0.0306 (9) | 0.0291 (9) | 0.0251 (8) | 0.0031 (7) | 0.0119 (7) | 0.0094 (7) |
| O101 | 0.0432 (8) | 0.0358 (8) | 0.0400 (8) | 0.0142 (7) | 0.0170 (7) | 0.0165 (7) |
| C201 | 0.036 (3) | 0.148 (6) | 0.030 (2) | 0.033 (3) | 0.004 (2) | 0.031 (3) |
| C202 | 0.055 (4) | 0.078 (5) | 0.136 (6) | 0.025 (4) | 0.035 (5) | 0.024 (5) |
| N201 | 0.049 (2) | 0.115 (4) | 0.071 (3) | 0.016 (4) | 0.020 (3) | 0.053 (4) |
| C203 | 0.043 (3) | 0.079 (4) | 0.056 (3) | 0.033 (3) | 0.019 (2) | 0.039 (3) |
| O201 | 0.227 (7) | 0.144 (6) | 0.183 (7) | 0.017 (6) | 0.015 (6) | 0.032 (6) |
Geometric parameters (Å, º)
| Co1—O41 | 2.0072 (12) | C35—C36 | 1.392 (2) |
| Co1—O21 | 2.0181 (13) | C35—H35 | 0.9500 |
| Co1—N30 | 2.1057 (13) | C36—H36 | 0.9500 |
| Co1—N10 | 2.1189 (13) | C30—N30 | 1.288 (2) |
| Co1—N31 | 2.1358 (14) | C30—H30 | 0.9500 |
| Co1—N11 | 2.1498 (14) | N30—C42 | 1.421 (2) |
| N11—C16 | 1.338 (2) | C41—C46 | 1.398 (2) |
| N11—C16 | 1.338 (2) | C41—C42 | 1.409 (2) |
| N11—C12 | 1.351 (2) | C41—C40 | 1.524 (2) |
| C12—C13 | 1.394 (2) | C42—C43 | 1.404 (2) |
| C12—C10 | 1.466 (2) | C43—C44 | 1.382 (3) |
| C13—C14 | 1.390 (3) | C43—H43 | 0.9500 |
| C13—H13 | 0.9500 | C44—C45 | 1.392 (3) |
| C14—C15 | 1.383 (3) | C44—H44 | 0.9500 |
| C14—H14 | 0.9500 | C45—C46 | 1.389 (3) |
| C15—C16 | 1.390 (2) | C45—H45 | 0.9500 |
| C15—H15 | 0.9500 | C46—H46 | 0.9500 |
| C16—H16 | 0.9500 | C40—O42 | 1.237 (2) |
| C10—N10 | 1.289 (2) | C40—O41 | 1.276 (2) |
| C10—H10 | 0.9500 | C101—N101 | 1.453 (3) |
| N10—C22 | 1.428 (2) | C101—H10A | 0.9800 |
| C21—C26 | 1.403 (2) | C101—H10B | 0.9800 |
| C21—C22 | 1.410 (2) | C101—H10C | 0.9800 |
| C21—C20 | 1.525 (2) | C102—N101 | 1.456 (3) |
| C22—C23 | 1.404 (2) | C102—H10D | 0.9800 |
| C23—C24 | 1.384 (2) | C102—H10E | 0.9800 |
| C23—H23 | 0.9500 | C102—H10F | 0.9800 |
| C24—C25 | 1.392 (3) | N101—C103 | 1.336 (2) |
| C24—H24 | 0.9500 | C103—O101 | 1.221 (2) |
| C25—C26 | 1.380 (2) | C103—H103 | 0.9500 |
| C25—H25 | 0.9500 | C201—N201 | 1.366 (9) |
| C26—H26 | 0.9500 | C201—H20A | 0.9800 |
| C20—O22 | 1.241 (2) | C201—H20B | 0.9800 |
| C20—O21 | 1.265 (2) | C201—H20C | 0.9800 |
| N31—C36 | 1.339 (2) | C202—N201 | 1.442 (10) |
| N31—C32 | 1.347 (2) | C202—H20D | 0.9800 |
| C32—C33 | 1.391 (2) | C202—H20E | 0.9800 |
| C32—C30 | 1.468 (2) | C202—H20F | 0.9800 |
| C33—C34 | 1.387 (3) | N201—C203 | 1.278 (9) |
| C33—H33 | 0.9500 | C203—O201 | 1.204 (11) |
| C34—C35 | 1.382 (3) | C203—H203 | 0.9500 |
| C34—H34 | 0.9500 | ||
| O41—Co1—O21 | 103.70 (5) | C33—C32—C30 | 121.74 (15) |
| O41—Co1—N30 | 89.97 (5) | C34—C33—C32 | 118.64 (16) |
| O21—Co1—N30 | 90.57 (5) | C34—C33—H33 | 120.7 |
| O41—Co1—N10 | 91.81 (5) | C32—C33—H33 | 120.7 |
| O21—Co1—N10 | 90.92 (5) | C35—C34—C33 | 119.31 (15) |
| N30—Co1—N10 | 177.35 (5) | C35—C34—H34 | 120.3 |
| O41—Co1—N31 | 161.53 (6) | C33—C34—H34 | 120.3 |
| O21—Co1—N31 | 90.55 (5) | C34—C35—C36 | 118.72 (17) |
| N30—Co1—N31 | 78.03 (5) | C34—C35—H35 | 120.6 |
| N10—Co1—N31 | 99.76 (5) | C36—C35—H35 | 120.6 |
| O41—Co1—N11 | 87.74 (5) | N31—C36—C35 | 122.40 (16) |
| O21—Co1—N11 | 164.36 (5) | N31—C36—H36 | 118.8 |
| N30—Co1—N11 | 100.20 (5) | C35—C36—H36 | 118.8 |
| N10—Co1—N11 | 77.91 (5) | N30—C30—C32 | 118.03 (14) |
| N31—Co1—N11 | 80.75 (5) | N30—C30—H30 | 121.0 |
| C16—N11—C12 | 118.76 (14) | C32—C30—H30 | 121.0 |
| C16—N11—Co1 | 128.75 (11) | C30—N30—C42 | 121.33 (14) |
| C12—N11—Co1 | 112.47 (10) | C30—N30—Co1 | 114.82 (11) |
| N11—C12—C13 | 122.22 (15) | C42—N30—Co1 | 123.70 (10) |
| N11—C12—C10 | 116.19 (13) | C46—C41—C42 | 118.51 (15) |
| C13—C12—C10 | 121.57 (15) | C46—C41—C40 | 115.46 (15) |
| C14—C13—C12 | 118.33 (16) | C42—C41—C40 | 126.01 (15) |
| C14—C13—H13 | 120.8 | C43—C42—C41 | 119.54 (16) |
| C12—C13—H13 | 120.8 | C43—C42—N30 | 120.99 (15) |
| C15—C14—C13 | 119.39 (16) | C41—C42—N30 | 119.40 (14) |
| C15—C14—H14 | 120.3 | C44—C43—C42 | 120.71 (17) |
| C13—C14—H14 | 120.3 | C44—C43—H43 | 119.6 |
| C14—C15—C16 | 118.94 (17) | C42—C43—H43 | 119.6 |
| C14—C15—H15 | 120.5 | C43—C44—C45 | 120.18 (17) |
| C16—C15—H15 | 120.5 | C43—C44—H44 | 119.9 |
| N11—C16—C15 | 122.28 (16) | C45—C44—H44 | 119.9 |
| N11—C16—H16 | 118.9 | C46—C45—C44 | 119.41 (17) |
| C15—C16—H16 | 118.9 | C46—C45—H45 | 120.3 |
| N10—C10—C12 | 118.75 (14) | C44—C45—H45 | 120.3 |
| N10—C10—H10 | 120.6 | C45—C46—C41 | 121.60 (17) |
| C12—C10—H10 | 120.6 | C45—C46—H46 | 119.2 |
| C10—N10—C22 | 120.97 (13) | C41—C46—H46 | 119.2 |
| C10—N10—Co1 | 114.38 (11) | O42—C40—O41 | 123.49 (15) |
| C22—N10—Co1 | 124.31 (10) | O42—C40—C41 | 116.99 (15) |
| C26—C21—C22 | 118.32 (14) | O41—C40—C41 | 119.46 (14) |
| C26—C21—C20 | 115.13 (14) | C40—O41—Co1 | 127.35 (11) |
| C22—C21—C20 | 126.52 (14) | N101—C101—H10A | 109.5 |
| C23—C22—C21 | 119.32 (14) | N101—C101—H10B | 109.5 |
| C23—C22—N10 | 121.59 (14) | H10A—C101—H10B | 109.5 |
| C21—C22—N10 | 119.08 (13) | N101—C101—H10C | 109.5 |
| C24—C23—C22 | 120.89 (15) | H10A—C101—H10C | 109.5 |
| C24—C23—H23 | 119.6 | H10B—C101—H10C | 109.5 |
| C22—C23—H23 | 119.6 | N101—C102—H10D | 109.5 |
| C23—C24—C25 | 120.10 (15) | N101—C102—H10E | 109.5 |
| C23—C24—H24 | 120.0 | H10D—C102—H10E | 109.5 |
| C25—C24—H24 | 120.0 | N101—C102—H10F | 109.5 |
| C26—C25—C24 | 119.40 (17) | H10D—C102—H10F | 109.5 |
| C26—C25—H25 | 120.3 | H10E—C102—H10F | 109.5 |
| C24—C25—H25 | 120.3 | C103—N101—C101 | 120.47 (19) |
| C25—C26—C21 | 121.91 (16) | C103—N101—C102 | 121.65 (18) |
| C25—C26—H26 | 119.0 | C101—N101—C102 | 117.44 (19) |
| C21—C26—H26 | 119.0 | O101—C103—N101 | 126.04 (18) |
| O22—C20—O21 | 123.53 (15) | O101—C103—H103 | 117.0 |
| O22—C20—C21 | 116.35 (15) | N101—C103—H103 | 117.0 |
| O21—C20—C21 | 120.06 (14) | C203—N201—C201 | 115.3 (7) |
| C20—O21—Co1 | 124.57 (11) | C203—N201—C202 | 120.1 (8) |
| C36—N31—C32 | 118.68 (14) | C201—N201—C202 | 124.6 (7) |
| C36—N31—Co1 | 127.42 (11) | O201—C203—N201 | 111.9 (8) |
| C32—N31—Co1 | 112.43 (11) | O201—C203—H203 | 124.1 |
| N31—C32—C33 | 122.15 (16) | N201—C203—H203 | 124.1 |
| N31—C32—C30 | 116.05 (13) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10···O42i | 0.95 | 2.46 | 3.393 (2) | 169 |
| C102—H10E···O42ii | 0.98 | 2.46 | 3.369 (3) | 154 |
| C16—H16···O101 | 0.95 | 2.41 | 3.326 (3) | 163 |
| C201—H20C···O22iii | 0.98 | 1.97 | 2.819 (10) | 143 |
| C23—H23···O42i | 0.95 | 2.60 | 3.454 (2) | 150 |
| C30—H30···O22iv | 0.95 | 2.42 | 3.344 (3) | 163 |
| C36—H36···O201v | 0.95 | 2.54 | 3.235 (13) | 130 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+2, −z+2; (v) x, y+1, z.
References
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- Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
- Buvaylo, E. A., Kokozay, V. N., Rubini, K., Vassilyeva, O. Yu. & Skelton, B. W. (2014b). J. Mol. Struct. 1072, 129–136.
- Buvaylo, E. A., Kokozay, V. N., Vassilyeva, O. Y. & Skelton, B. W. (2014a). Acta Cryst. E70, m136. [DOI] [PMC free article] [PubMed]
- Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.
- Johnson, C. K. (1976). ORTEPII Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
- Mukhopadhyay, A. & Pal, S. (2005). J. Chem. Crystallogr. 35, 737–744.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Vigato, P. A., Peruzzo, V. & Tamburini, S. (2012). Coord. Chem. Rev. 256, 953–1114.
- Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814019485/wm5044sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019485/wm5044Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814019485/wm5044Isup3.jpg
CCDC reference: 1021534
Additional supporting information: crystallographic information; 3D view; checkCIF report