research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 164-166

Crystal structure of bis­­(2-{[(pyridin-2-yl)methyl­­idene]amino}­benzoato-κ3N,N′,O)cobalt(II) N,N-di­methyl­formamide sesquisolvate

aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine, and bCentre for Microscopy, Characterisation and Analysis, M313, University of Western Australia, Perth, WA 6009, Australia
*Correspondence e-mail: vassilyeva@univ.kiev.ua

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 August 2014; accepted 28 August 2014; online 6 September 2014)

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.

1. 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[Vigato, P. A., Peruzzo, V. & Tamburini, S. (2012). Coord. Chem. Rev. 256, 953-1114.]). 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.

[Scheme 1]

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 CrL2NO3·H2O (Buvaylo et al., 2014a[Buvaylo, E. A., Kokozay, V. N., Vassilyeva, O. Y. & Skelton, B. W. (2014a). Acta Cryst. E70, m136.]) and co-crystals of ML2 (M = Co, Ni, Zn) and anthranilic acid (Buvaylo et al., 2014b[Buvaylo, E. A., Kokozay, V. N., Rubini, K., Vassilyeva, O. Yu. & Skelton, B. W. (2014b). J. Mol. Struct. 1072, 129-136.]). The respective compounds were prepared by in situ Schiff base synthesis. ML2 mol­ecules of the isotypic CoL2·AA·H2O and NiL2·AA·H2O co-crystals retained the intra­molecular distances M—(N,O) as found in the structure of the `native' Schiff base metal complex NiL2·H2O (Mukhopadhyay & Pal, 2005[Mukhopadhyay, A. & Pal, S. (2005). J. Chem. Crystallogr. 35, 737-744.]). The crystal packing of the co-crystals was described as an insertion of the organic mol­ecules between the layers of ML2 complexes as they occur in the reported NiL2·H2O structure.

The title compound, [Co(C13H9N2O2)2]·1.5C3H7NO, was prepared similarly to the co-crystals (Buvaylo et al., 2014b[Buvaylo, E. A., Kokozay, V. N., Rubini, K., Vassilyeva, O. Yu. & Skelton, B. W. (2014b). J. Mol. Struct. 1072, 129-136.]) 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.

2. Structural commentary

The asymmetric unit of the title compound consists of one neutral CoL2 mol­ecule and 1.5 di­methyl­formamide (DMF) solvent mol­ecules, of which one is fully ordered, the other being disordered about a crystallographic inversion centre. The CoL2 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[link], Table 1[link]). 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 CoL2·AA·H2O (Buvaylo et al., 2014b[Buvaylo, E. A., Kokozay, V. N., Rubini, K., Vassilyeva, O. Yu. & Skelton, B. W. (2014b). J. Mol. Struct. 1072, 129-136.]) 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 CoL2·AA·H2O. A metal site with mixed (Co/Cd) occupancy for the title compound was ruled out by the refinement.

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)
[Figure 1]
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.

3. Supra­molecular features

The crystal lattice is built of alternating layers of complex CoL2 mol­ecules and DMF mol­ecules parallel to (010) (Fig. 2[link]). Neighbouring CoL2 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 Table 2[link] between the complex mol­ecules and the solvent mol­ecules lead to a consolidation of the crystal packing.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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.
[Figure 2]
Figure 2
Packing diagram showing alternating layers of [CoL2] and DMF mol­ecules. CH hydrogens have been omitted for clarity.

4. 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.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. 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 Uiso(H) = 1.2Ueq of the parent C atom.

Table 3
Experimental details

Crystal data
Chemical formula [Co(C13H9N2O2)2]·1.5C3H7NO
Mr 619.02
Crystal system, space group Triclinic, P[\overline{1}]
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)
V3) 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[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) using an expression derived by Clark & Reid (1995[Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.])]
Tmin, Tmax 0.821, 0.898
No. of measured, independent and observed [I > 2σ(I)] reflections 33209, 10748, 8599
Rint 0.036
(sin θ/λ)max−1) 0.787
 
Refinement
R[F2 > 2σ(F2)], wR(F2), 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
Computer programs: CrysAlis PRO (Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]), DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

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 CrL2NO3.H2O (Buvaylo et al., 2014a) and co-crystals of ML2 (M = Co, Ni, Zn) and anthranilic acid (Buvaylo et al., 2014b). The respective compounds were prepared by in situ Schiff base synthesis. ML2 molecules of the isotypic CoL2·AA·H2O and NiL2·AA·H2O co-crystals retained the intra­molecular distances M—(N,O) as found in the structure of the `native' Schiff base metal complex NiL2·H2O (Mukhopadhyay & Pal, 2005). The crystal packing of the co-crystals was described as an insertion of the organic molecules between the layers of ML2 complexes as they occur in the reported NiL2·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.

Structural commentary top

The asymmetric unit of the title compound consists of one neutral CoL2 molecule and 1.5 di­methyl­formamide (DMF) solvent molecules, of which one is fully ordered, the other being disordered about a crystallographic inversion centre. The CoL2 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 CoL2·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 CoL2·AA·H2O. A metal site with mixed (Co/Cd) occupancy for the title compound was ruled out by the refinement.

Supra­molecular features top

The crystal lattice is built of alternating layers of complex CoL2 molecules and DMF molecules parallel to (010) (Fig. 2). Neighbouring CoL2 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.

Synthesis and crystallization top

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 C26H18CoN4O4.3/2C3H7NO 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 top

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 Uiso(H) = 1.2Ueq of the parent C atom.

Related literature top

For related literature, see: Buvaylo et al. (2014a, 2014b); Mukhopadhyay & Pal (2005); Vigato et al. (2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, showing the atom-numbering scheme. Non-H atoms are shown as 50% atomic displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram showing alternating layers of [CoL2] and DMF molecules. CH hydrogens have been omitted for clarity.
Bis(2-{[(pyridin-2-yl)methylidene]amino}benzoato-κ3N,N',O)cobalt(II) N,N-dimethylformamide sesquisolvate top
Crystal data top
[Co(C13H9N2O2)2]·1.5C3H7NOZ = 2
Mr = 619.02F(000) = 642
Triclinic, P1Dx = 1.524 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4361 (6) ÅCell parameters from 10672 reflections
b = 13.2603 (10) Åθ = 2.8–34.5°
c = 13.8664 (10) ŵ = 0.69 mm1
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 top
Oxford Diffraction Xcalibur
diffractometer
10748 independent reflections
Graphite monochromator8599 reflections with I > 2σ(I)
Detector resolution: 16.0009 pixels mm-1Rint = 0.036
ω scansθmax = 34°, θmin = 2.8°
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2011) using an expression derived by Clark & Reid (1995)]
h = 1213
Tmin = 0.821, Tmax = 0.898k = 2019
33209 measured reflectionsl = 2121
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-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 parametersΔρmax = 0.74 e Å3
35 restraintsΔρmin = 0.54 e Å3
Crystal data top
[Co(C13H9N2O2)2]·1.5C3H7NOγ = 101.430 (6)°
Mr = 619.02V = 1348.9 (2) Å3
Triclinic, P1Z = 2
a = 8.4361 (6) ÅMo Kα radiation
b = 13.2603 (10) ŵ = 0.69 mm1
c = 13.8664 (10) ÅT = 100 K
α = 110.061 (7)°0.40 × 0.30 × 0.18 mm
β = 103.559 (6)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer
10748 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2011) using an expression derived by Clark & Reid (1995)]
8599 reflections with I > 2σ(I)
Tmin = 0.821, Tmax = 0.898Rint = 0.036
33209 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04835 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.05Δρmax = 0.74 e Å3
10748 reflectionsΔρmin = 0.54 e Å3
410 parameters
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
Co10.50566 (3)0.996180 (17)0.747260 (16)0.01696 (6)
N110.28320 (17)0.91486 (12)0.60369 (11)0.0197 (2)
C120.2706 (2)0.97508 (14)0.54251 (12)0.0194 (3)
C130.1383 (2)0.93697 (15)0.44446 (14)0.0255 (3)
H130.13450.97920.40120.031*
C140.0121 (2)0.83562 (17)0.41152 (15)0.0307 (4)
H140.08010.80770.34530.037*
C150.0221 (2)0.77579 (16)0.47596 (15)0.0289 (4)
H150.06450.70730.45560.035*
C160.1607 (2)0.81754 (15)0.57109 (14)0.0245 (3)
H160.16870.77550.61440.029*
C100.4017 (2)1.08481 (13)0.58651 (12)0.0192 (3)
H100.40171.1310.54720.023*
N100.51714 (16)1.11742 (11)0.67961 (10)0.0170 (2)
C210.7536 (2)1.26504 (14)0.83458 (12)0.0205 (3)
C220.65025 (19)1.22222 (13)0.72478 (12)0.0174 (3)
C230.6816 (2)1.28292 (14)0.66229 (13)0.0240 (3)
H230.61061.25520.58880.029*
C240.8144 (2)1.38261 (15)0.70634 (14)0.0277 (3)
H240.8331.42340.66340.033*
C250.9208 (2)1.42328 (16)0.81350 (15)0.0285 (4)
H251.01491.49010.84310.034*
C260.8883 (2)1.36573 (15)0.87639 (14)0.0269 (3)
H260.95911.39520.95010.032*
C200.7319 (2)1.21453 (15)0.91605 (13)0.0240 (3)
O210.69029 (16)1.10880 (10)0.88645 (9)0.0232 (2)
O220.7636 (3)1.28251 (13)1.01092 (11)0.0475 (4)
N310.31332 (17)1.02612 (12)0.82016 (11)0.0203 (2)
C320.2642 (2)0.94913 (14)0.85884 (12)0.0197 (3)
C330.1204 (2)0.93994 (16)0.89184 (13)0.0257 (3)
H330.09130.88750.92220.031*
C340.0202 (2)1.00887 (17)0.87943 (13)0.0284 (4)
H340.08111.00230.89860.034*
C350.0694 (2)1.08726 (17)0.83884 (13)0.0270 (3)
H350.00251.13520.82960.032*
C360.2188 (2)1.09467 (16)0.81177 (13)0.0245 (3)
H360.2551.15040.78640.029*
C300.3667 (2)0.87175 (14)0.85948 (12)0.0205 (3)
H300.34840.8210.89310.025*
N300.48205 (17)0.87471 (11)0.81309 (10)0.0181 (2)
C410.6719 (2)0.78101 (13)0.73476 (12)0.0207 (3)
C420.5915 (2)0.80600 (13)0.81452 (12)0.0199 (3)
C430.6270 (2)0.76728 (15)0.89722 (14)0.0271 (3)
H430.57070.78250.95010.033*
C440.7429 (3)0.70727 (16)0.90256 (15)0.0329 (4)
H440.76680.68230.95940.039*
C450.8246 (3)0.68328 (15)0.82488 (15)0.0313 (4)
H450.90610.64340.82930.038*
C460.7858 (2)0.71809 (14)0.74084 (14)0.0261 (3)
H460.8380.69870.68610.031*
C400.6515 (2)0.81957 (14)0.64211 (13)0.0214 (3)
O410.63573 (16)0.91724 (11)0.65820 (10)0.0244 (2)
O420.6581 (2)0.75447 (12)0.55549 (10)0.0344 (3)
C1010.2797 (3)0.5260 (2)0.53693 (17)0.0462 (6)
H10A0.17810.54720.51120.069*
H10B0.27190.45230.48390.069*
H10C0.38250.58260.54570.069*
C1020.4048 (3)0.4635 (2)0.6791 (2)0.0492 (6)
H10D0.52290.50460.69120.074*
H10E0.37480.38640.62450.074*
H10F0.39470.46150.74750.074*
N1010.2892 (2)0.52022 (14)0.64083 (13)0.0314 (3)
C1030.2097 (2)0.57619 (16)0.70349 (15)0.0292 (4)
H1030.22670.57370.77280.035*
O1010.1172 (2)0.63017 (13)0.68000 (13)0.0384 (3)
C2010.6583 (8)0.4774 (8)1.0471 (4)0.074 (2)0.5
H20A0.68720.53721.11960.11*0.5
H20B0.74020.49811.01220.11*0.5
H20C0.66350.40671.05370.11*0.5
C2020.4086 (11)0.5472 (7)1.0070 (9)0.094 (3)0.5
H20D0.48430.621.01930.141*0.5
H20E0.37580.55411.07180.141*0.5
H20F0.30560.52450.94450.141*0.5
N2010.4968 (10)0.4635 (6)0.9856 (6)0.0754 (17)0.5
C2030.4235 (7)0.3681 (6)0.9046 (5)0.0535 (12)0.5
H2030.47780.3120.88290.064*0.5
O2010.2772 (15)0.3581 (9)0.8592 (9)0.211 (4)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01868 (10)0.01863 (11)0.01563 (10)0.00464 (7)0.00591 (7)0.00978 (8)
N110.0208 (6)0.0218 (6)0.0165 (5)0.0045 (5)0.0054 (5)0.0092 (5)
C120.0192 (6)0.0232 (7)0.0163 (6)0.0063 (5)0.0056 (5)0.0091 (5)
C130.0258 (8)0.0286 (8)0.0208 (7)0.0062 (6)0.0038 (6)0.0123 (6)
C140.0247 (8)0.0347 (10)0.0249 (8)0.0029 (7)0.0012 (6)0.0127 (7)
C150.0231 (8)0.0294 (9)0.0267 (8)0.0005 (6)0.0024 (6)0.0112 (7)
C160.0243 (7)0.0252 (8)0.0224 (7)0.0019 (6)0.0055 (6)0.0124 (6)
C100.0223 (7)0.0213 (7)0.0171 (6)0.0071 (5)0.0075 (5)0.0107 (5)
N100.0191 (6)0.0183 (6)0.0157 (5)0.0061 (5)0.0067 (4)0.0084 (5)
C210.0247 (7)0.0207 (7)0.0176 (6)0.0041 (6)0.0087 (5)0.0102 (5)
C220.0207 (6)0.0172 (6)0.0170 (6)0.0059 (5)0.0082 (5)0.0087 (5)
C230.0317 (8)0.0237 (8)0.0182 (7)0.0058 (6)0.0082 (6)0.0120 (6)
C240.0372 (9)0.0241 (8)0.0243 (8)0.0040 (7)0.0110 (7)0.0149 (7)
C250.0335 (9)0.0239 (8)0.0271 (8)0.0017 (7)0.0096 (7)0.0133 (7)
C260.0305 (8)0.0235 (8)0.0213 (7)0.0004 (6)0.0046 (6)0.0102 (6)
C200.0273 (8)0.0249 (8)0.0182 (7)0.0017 (6)0.0070 (6)0.0108 (6)
O210.0260 (6)0.0228 (6)0.0201 (5)0.0040 (4)0.0039 (4)0.0123 (4)
O220.0860 (13)0.0276 (7)0.0186 (6)0.0018 (8)0.0160 (7)0.0088 (5)
N310.0203 (6)0.0258 (7)0.0176 (6)0.0068 (5)0.0067 (5)0.0118 (5)
C320.0200 (7)0.0224 (7)0.0140 (6)0.0021 (5)0.0055 (5)0.0068 (5)
C330.0246 (8)0.0298 (8)0.0192 (7)0.0005 (6)0.0102 (6)0.0082 (6)
C340.0200 (7)0.0399 (10)0.0181 (7)0.0039 (7)0.0076 (6)0.0056 (7)
C350.0238 (8)0.0385 (10)0.0179 (7)0.0132 (7)0.0063 (6)0.0089 (7)
C360.0252 (8)0.0333 (9)0.0208 (7)0.0130 (7)0.0092 (6)0.0143 (7)
C300.0245 (7)0.0208 (7)0.0145 (6)0.0023 (6)0.0056 (5)0.0086 (5)
N300.0202 (6)0.0179 (6)0.0139 (5)0.0025 (5)0.0033 (4)0.0071 (4)
C410.0233 (7)0.0172 (7)0.0171 (6)0.0034 (5)0.0027 (5)0.0060 (5)
C420.0233 (7)0.0165 (6)0.0158 (6)0.0035 (5)0.0019 (5)0.0063 (5)
C430.0380 (9)0.0236 (8)0.0184 (7)0.0082 (7)0.0044 (6)0.0108 (6)
C440.0454 (11)0.0269 (9)0.0228 (8)0.0134 (8)0.0002 (7)0.0121 (7)
C450.0380 (10)0.0210 (8)0.0285 (8)0.0120 (7)0.0002 (7)0.0082 (7)
C460.0278 (8)0.0207 (7)0.0236 (7)0.0071 (6)0.0033 (6)0.0056 (6)
C400.0207 (7)0.0247 (8)0.0191 (7)0.0066 (6)0.0062 (5)0.0098 (6)
O410.0304 (6)0.0269 (6)0.0244 (6)0.0114 (5)0.0145 (5)0.0153 (5)
O420.0531 (9)0.0341 (7)0.0206 (6)0.0208 (7)0.0145 (6)0.0107 (5)
C1010.0517 (13)0.0484 (13)0.0279 (9)0.0014 (11)0.0207 (10)0.0063 (9)
C1020.0334 (11)0.0434 (13)0.0490 (13)0.0134 (10)0.0020 (10)0.0004 (11)
N1010.0294 (8)0.0303 (8)0.0251 (7)0.0033 (6)0.0089 (6)0.0035 (6)
C1030.0306 (9)0.0291 (9)0.0251 (8)0.0031 (7)0.0119 (7)0.0094 (7)
O1010.0432 (8)0.0358 (8)0.0400 (8)0.0142 (7)0.0170 (7)0.0165 (7)
C2010.036 (3)0.148 (6)0.030 (2)0.033 (3)0.004 (2)0.031 (3)
C2020.055 (4)0.078 (5)0.136 (6)0.025 (4)0.035 (5)0.024 (5)
N2010.049 (2)0.115 (4)0.071 (3)0.016 (4)0.020 (3)0.053 (4)
C2030.043 (3)0.079 (4)0.056 (3)0.033 (3)0.019 (2)0.039 (3)
O2010.227 (7)0.144 (6)0.183 (7)0.017 (6)0.015 (6)0.032 (6)
Geometric parameters (Å, º) top
Co1—O412.0072 (12)C35—C361.392 (2)
Co1—O212.0181 (13)C35—H350.9500
Co1—N302.1057 (13)C36—H360.9500
Co1—N102.1189 (13)C30—N301.288 (2)
Co1—N312.1358 (14)C30—H300.9500
Co1—N112.1498 (14)N30—C421.421 (2)
N11—C161.338 (2)C41—C461.398 (2)
N11—C161.338 (2)C41—C421.409 (2)
N11—C121.351 (2)C41—C401.524 (2)
C12—C131.394 (2)C42—C431.404 (2)
C12—C101.466 (2)C43—C441.382 (3)
C13—C141.390 (3)C43—H430.9500
C13—H130.9500C44—C451.392 (3)
C14—C151.383 (3)C44—H440.9500
C14—H140.9500C45—C461.389 (3)
C15—C161.390 (2)C45—H450.9500
C15—H150.9500C46—H460.9500
C16—H160.9500C40—O421.237 (2)
C10—N101.289 (2)C40—O411.276 (2)
C10—H100.9500C101—N1011.453 (3)
N10—C221.428 (2)C101—H10A0.9800
C21—C261.403 (2)C101—H10B0.9800
C21—C221.410 (2)C101—H10C0.9800
C21—C201.525 (2)C102—N1011.456 (3)
C22—C231.404 (2)C102—H10D0.9800
C23—C241.384 (2)C102—H10E0.9800
C23—H230.9500C102—H10F0.9800
C24—C251.392 (3)N101—C1031.336 (2)
C24—H240.9500C103—O1011.221 (2)
C25—C261.380 (2)C103—H1030.9500
C25—H250.9500C201—N2011.366 (9)
C26—H260.9500C201—H20A0.9800
C20—O221.241 (2)C201—H20B0.9800
C20—O211.265 (2)C201—H20C0.9800
N31—C361.339 (2)C202—N2011.442 (10)
N31—C321.347 (2)C202—H20D0.9800
C32—C331.391 (2)C202—H20E0.9800
C32—C301.468 (2)C202—H20F0.9800
C33—C341.387 (3)N201—C2031.278 (9)
C33—H330.9500C203—O2011.204 (11)
C34—C351.382 (3)C203—H2030.9500
C34—H340.9500
O41—Co1—O21103.70 (5)C33—C32—C30121.74 (15)
O41—Co1—N3089.97 (5)C34—C33—C32118.64 (16)
O21—Co1—N3090.57 (5)C34—C33—H33120.7
O41—Co1—N1091.81 (5)C32—C33—H33120.7
O21—Co1—N1090.92 (5)C35—C34—C33119.31 (15)
N30—Co1—N10177.35 (5)C35—C34—H34120.3
O41—Co1—N31161.53 (6)C33—C34—H34120.3
O21—Co1—N3190.55 (5)C34—C35—C36118.72 (17)
N30—Co1—N3178.03 (5)C34—C35—H35120.6
N10—Co1—N3199.76 (5)C36—C35—H35120.6
O41—Co1—N1187.74 (5)N31—C36—C35122.40 (16)
O21—Co1—N11164.36 (5)N31—C36—H36118.8
N30—Co1—N11100.20 (5)C35—C36—H36118.8
N10—Co1—N1177.91 (5)N30—C30—C32118.03 (14)
N31—Co1—N1180.75 (5)N30—C30—H30121.0
C16—N11—C12118.76 (14)C32—C30—H30121.0
C16—N11—Co1128.75 (11)C30—N30—C42121.33 (14)
C12—N11—Co1112.47 (10)C30—N30—Co1114.82 (11)
N11—C12—C13122.22 (15)C42—N30—Co1123.70 (10)
N11—C12—C10116.19 (13)C46—C41—C42118.51 (15)
C13—C12—C10121.57 (15)C46—C41—C40115.46 (15)
C14—C13—C12118.33 (16)C42—C41—C40126.01 (15)
C14—C13—H13120.8C43—C42—C41119.54 (16)
C12—C13—H13120.8C43—C42—N30120.99 (15)
C15—C14—C13119.39 (16)C41—C42—N30119.40 (14)
C15—C14—H14120.3C44—C43—C42120.71 (17)
C13—C14—H14120.3C44—C43—H43119.6
C14—C15—C16118.94 (17)C42—C43—H43119.6
C14—C15—H15120.5C43—C44—C45120.18 (17)
C16—C15—H15120.5C43—C44—H44119.9
N11—C16—C15122.28 (16)C45—C44—H44119.9
N11—C16—H16118.9C46—C45—C44119.41 (17)
C15—C16—H16118.9C46—C45—H45120.3
N10—C10—C12118.75 (14)C44—C45—H45120.3
N10—C10—H10120.6C45—C46—C41121.60 (17)
C12—C10—H10120.6C45—C46—H46119.2
C10—N10—C22120.97 (13)C41—C46—H46119.2
C10—N10—Co1114.38 (11)O42—C40—O41123.49 (15)
C22—N10—Co1124.31 (10)O42—C40—C41116.99 (15)
C26—C21—C22118.32 (14)O41—C40—C41119.46 (14)
C26—C21—C20115.13 (14)C40—O41—Co1127.35 (11)
C22—C21—C20126.52 (14)N101—C101—H10A109.5
C23—C22—C21119.32 (14)N101—C101—H10B109.5
C23—C22—N10121.59 (14)H10A—C101—H10B109.5
C21—C22—N10119.08 (13)N101—C101—H10C109.5
C24—C23—C22120.89 (15)H10A—C101—H10C109.5
C24—C23—H23119.6H10B—C101—H10C109.5
C22—C23—H23119.6N101—C102—H10D109.5
C23—C24—C25120.10 (15)N101—C102—H10E109.5
C23—C24—H24120.0H10D—C102—H10E109.5
C25—C24—H24120.0N101—C102—H10F109.5
C26—C25—C24119.40 (17)H10D—C102—H10F109.5
C26—C25—H25120.3H10E—C102—H10F109.5
C24—C25—H25120.3C103—N101—C101120.47 (19)
C25—C26—C21121.91 (16)C103—N101—C102121.65 (18)
C25—C26—H26119.0C101—N101—C102117.44 (19)
C21—C26—H26119.0O101—C103—N101126.04 (18)
O22—C20—O21123.53 (15)O101—C103—H103117.0
O22—C20—C21116.35 (15)N101—C103—H103117.0
O21—C20—C21120.06 (14)C203—N201—C201115.3 (7)
C20—O21—Co1124.57 (11)C203—N201—C202120.1 (8)
C36—N31—C32118.68 (14)C201—N201—C202124.6 (7)
C36—N31—Co1127.42 (11)O201—C203—N201111.9 (8)
C32—N31—Co1112.43 (11)O201—C203—H203124.1
N31—C32—C33122.15 (16)N201—C203—H203124.1
N31—C32—C30116.05 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O42i0.952.463.393 (2)169
C102—H10E···O42ii0.982.463.369 (3)154
C16—H16···O1010.952.413.326 (3)163
C201—H20C···O22iii0.981.972.819 (10)143
C23—H23···O42i0.952.603.454 (2)150
C30—H30···O22iv0.952.423.344 (3)163
C36—H36···O201v0.952.543.235 (13)130
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x, y1, z; (iv) x+1, y+2, z+2; (v) x, y+1, z.
Selected bond lengths (Å) top
Co1—O412.0072 (12)Co1—N102.1189 (13)
Co1—O212.0181 (13)Co1—N312.1358 (14)
Co1—N302.1057 (13)Co1—N112.1498 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O42i0.952.463.393 (2)169
C102—H10E···O42ii0.982.463.369 (3)154
C16—H16···O1010.952.413.326 (3)163
C201—H20C···O22iii0.981.972.819 (10)143
C23—H23···O42i0.952.603.454 (2)150
C30—H30···O22iv0.952.423.344 (3)163
C36—H36···O201v0.952.543.235 (13)130
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x, y1, z; (iv) x+1, y+2, z+2; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Co(C13H9N2O2)2]·1.5C3H7NO
Mr619.02
Crystal system, space groupTriclinic, P1
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)
V3)1348.9 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.69
Crystal size (mm)0.40 × 0.30 × 0.18
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer
Absorption correctionAnalytical
[CrysAlis PRO (Agilent, 2011) using an expression derived by Clark & Reid (1995)]
Tmin, Tmax0.821, 0.898
No. of measured, independent and
observed [I > 2σ(I)] reflections
33209, 10748, 8599
Rint0.036
(sin θ/λ)max1)0.787
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.127, 1.05
No. of reflections10748
No. of parameters410
No. of restraints35
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.74, 0.54

Computer programs: CrysAlis PRO (Agilent, 2011), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

 

Acknowledgements

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.

References

First citationAgilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.  Google Scholar
First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals Google Scholar
First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBuvaylo, E. A., Kokozay, V. N., Rubini, K., Vassilyeva, O. Yu. & Skelton, B. W. (2014b). J. Mol. Struct. 1072, 129–136.  Web of Science CSD CrossRef CAS Google Scholar
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First citationMukhopadhyay, A. & Pal, S. (2005). J. Chem. Crystallogr. 35, 737–744.  Web of Science CSD CrossRef CAS Google Scholar
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First citationVigato, P. A., Peruzzo, V. & Tamburini, S. (2012). Coord. Chem. Rev. 256, 953–1114.  Web of Science CrossRef CAS Google Scholar
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Volume 70| Part 10| October 2014| Pages 164-166
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