(5,10,15,20-Tetra­phenyl­porphyrinato-κ4N)cobalt(II)–18-crown-6 (1/1)

Mansour, A.; Belkhiria, M.S.; Daran, J.-C.; Nasri, H.

doi:10.1107/S1600536810012080

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Pages m509-m510

https://doi.org/10.1107/S1600536810012080

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(5,10,15,20-Tetraphenylporphyrinato-κ⁴N)cobalt(II)–18-crown-6 (1/1)

Anissa Mansour,^a Mohamed Salah Belkhiria,^a Jean-Claude Daran ^b and Habib Nasri ^a ^*

^aDépartement de Chimie, Faculté des Sciences de Monastir, Avenue de l'environnement, 5019 Monastir, Tunisia, and ^bLaboratoire de Chimie de Coordination, CNRS UPR 8241, 205 route de Norbonne, 31077 Toulouse, Cedex 04, France
^*Correspondence e-mail: hnasri1@gmail.com

(Received 18 March 2010; accepted 30 March 2010; online 10 April 2010)

The asymmetric unit of the title compound, [Co(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆, contains one half of a Co^II(TPP) (TPP is tetraphenylporphyrin) complex and one half of an 18-crown-6 molecule of crystallization, both lying on inversion centers. The Co^II(TPP) complex exhibits a nearly planar conformation of the porphyrinate core [maximum deviation = 0.069 (2) Å] with an average Co—N distance of 1.971 (4) Å. The distance between the Co atom and the closest O atom of the 18-crown-6 molecule is 2.533 (2) Å, indicating a short non-bonded contact between the Co atom and the crown ether molecule. An ethylene group of the 18-crown-6 molecule is disordered over two sites with occupancies of 0.565 (7) and 0.435 (7).

Related literature

For general background to cobalt porphyrin species and their applications, see: Sanders et al. (2000 ). For the synthesis of Co(II) tetraphenylporphyrin, see: Madure & Scheidt (1976 ). For related structures, see: Konarev et al. (2003 , 2004 ); Nascimento et al. (2007 ); Smirnov et al. (1998 ); Lee et al. (2002 ); Iimura et al. (1988 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For the SIMU/ISOR restraints used in the refinement, see: McArdle (1995 ).

Experimental

Crystal data

[Co(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆
M_r = 935.95
Triclinic, $[P \overline 1]$
a = 10.1464 (4) Å
b = 11.0890 (6) Å
c = 11.7570 (5) Å
α = 104.327 (4)°
β = 105.842 (4)°
γ = 108.284 (4)°
V = 1125.12 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 180 K
0.25 × 0.24 × 0.21 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.927, T_max = 1.000
8862 measured reflections
4589 independent reflections
3977 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.100
S = 1.10
4589 reflections
323 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810012080/pv2268sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012080/pv2268Isup2.hkl

checkCIF report

Comment top

Cobalt atom in metalloporphyrines is commonly used as a qualitatively acceptable substitute for iron atom in high-spin five-coordinate hemes of deoxyhemoglobin and in the low-spin oxygenated hemes of oxyhemoglobin. The metalation of a porphyrin by cobalt (using CoCl₂^.6H₂O salt) yields the stable [Co^II(Porph)] (Porph = porphyrin) complex used as starting material in the preparation of five and six-coordinated Co(II) and Co(III) metalloporphyrines (Sanders et al., (2000). In the Cambridge Structural Database (CSD, version 5.31; Allen 2002) there are three structures of tetra-coordinated cobalt(II) tetraphenylporphyrin (TPP) complexes: IKUDOH (Konarev et al., 2003), IXIKIJ (Konarev et al., 2004) and TPORCP12 (Nascimento et al., 2007). Herein we report the struture of the title compound,(I), which has been prepared in our laboratory.

The asymmetric unit of (I), contains one half [Co^II(TPP)] complex and one half crystallographically independent 18-crown-6 molecule of crystallization both lying on inversion centers (Fig. 1).

The distance between the cobalt(II) ion and the symmetry related O1 and O1' atoms (Fig. 2) of the two closest crown ether molecules is 2.533 (2 ) Å. This distance is significantly longer than the Co^II—O(THF) bond length [2.204 (4) Å] in the [Co^II(F₈TPP)(THF)₂] derivative (where F₈TPP is the tetrakis(pentafluorophenylporphyrin)) (Smirnov et al., 1998) and the Co^II—O(H₂O) bond distance in the [Co^II(H₂O)₆]²⁺ species [ 2.062 (4)- 2.141 (4) Å] (Lee et al., 2002). This indicates that in (I) there is a short non-bonded contact between the cobalt ion and the crown ether molecule.

It has been noticed that there is a relationship between the ruffling of the porphyrinato core and the mean equatorial Co(II)—N_p distance (N_p = pyrrol N atom); the porphyrinato core is ruffled as the Co—N_p distance decreases, (Iimura et al., 1988). Thus, the average distance Co—N_p in (I), 1.971 (4) Å, is longer than those of the three other reported [Co^II(TPP)] structures quoted above [1.923 (3) – 1.969 (6) Å]. The porphyrin core in (I) presents a planar conformation with maximum and minimum deviations from the C₂₀N₄ least-squares plane of 0.069 (2) and -0.068 (2) Å for C6 and C8 atoms, respectively, while the Co²⁺ cation is basically in the porphyrin plane with a Co—C_t distance of 0.004 (1) Å (where C_t is the center of the C₂₀N₄plane).

Related literature top

For general background to cobalt porphyrin species and their applications, see: Sanders et al. (2000). For the synthesis of Co(II) tetraphenylporphyrin, see: Madure & Scheidt (1976). For related structures, see: Konarev et al. (2003, 2004); Nascimento et al. (2007); Smirnov et al. (1998); Lee et al. (2002); Iimura et al. (1988). For a description of the Cambridge Structural Database, see: Allen (2002). For the SIMU/ISOR restraints used in the refinement, see: McArdle (1995).

Experimental top

To a solution of [Co^II(TPP)] (Madure & Scheidt 1976) (100 mg, 0.067 mmol) in chlorobenzene (10 ml) was added an excess of 18-crown-6 (150 mg, 0.567 mmol) and sodium methanolate (100 mg, 3.225 mmol). The reaction mixture was stirred at room temperature until reddisd-green solution was formed. The resulting material was crystallized by diffusion of hexanes through the chlorobenzene solution which yielded [Co^II(TPP)]^.(18-C-6) crystals as an impurity.

Structure description top

The asymmetric unit of (I), contains one half [Co^II(TPP)] complex and one half crystallographically independent 18-crown-6 molecule of crystallization both lying on inversion centers (Fig. 1).

For general background to cobalt porphyrin species and their applications, see: Sanders et al. (2000). For the synthesis of Co(II) tetraphenylporphyrin, see: Madure & Scheidt (1976). For related structures, see: Konarev et al. (2003, 2004); Nascimento et al. (2007); Smirnov et al. (1998); Lee et al. (2002); Iimura et al. (1988). For a description of the Cambridge Structural Database, see: Allen (2002). For the SIMU/ISOR restraints used in the refinement, see: McArdle (1995).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, m1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of (I), with the atom-numbering scheme. Unlabeled atoms are related by an inversion center to the labeled atoms. Displacement ellipsoids are drawn at 50%. The H atoms and the minor positions of the disordered C24 and C25 atoms have been omitted for clarity.
	Fig. 2. A unit-cell packing of (I). The short non-bonded contacts between the cobalt and the symmetry related O1 and O1' atoms of the two closest crown ether molecues, are drawn by dashed lines. The H atoms and the minor positions of the disordered C24 and C25 atoms have been omitted for clarity.

(5,10,15,20-Tetraphenylporphyrinato-κ⁴N)cobalt(II)–18-crown-6 (1/1) top

Crystal data top

[Co(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆	Z = 1
M_r = 935.95	F(000) = 491
Triclinic, P1	D_x = 1.381 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.1464 (4) Å	Cell parameters from 6796 reflections
b = 11.0890 (6) Å	θ = 3.1–32.2°
c = 11.7570 (5) Å	µ = 0.44 mm⁻¹
α = 104.327 (4)°	T = 180 K
β = 105.842 (4)°	Prism, dark purple
γ = 108.284 (4)°	0.25 × 0.24 × 0.21 mm
V = 1125.12 (9) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer	4589 independent reflections
Radiation source: fine-focus sealed tube	3977 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 8.2632 pixels mm^-1	θ_max = 26.4°, θ_min = 3.3°
ω and φ scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −13→9
T_min = 0.927, T_max = 1.000	l = −14→14
8862 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.05322P)² + 0.3421P] where P = (F_o² + 2F_c²)/3
4589 reflections	(Δ/σ)_max < 0.001
323 parameters	Δρ_max = 0.79 e Å⁻³
30 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Co(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆	γ = 108.284 (4)°
M_r = 935.95	V = 1125.12 (9) Å³
Triclinic, P1	Z = 1
a = 10.1464 (4) Å	Mo Kα radiation
b = 11.0890 (6) Å	µ = 0.44 mm⁻¹
c = 11.7570 (5) Å	T = 180 K
α = 104.327 (4)°	0.25 × 0.24 × 0.21 mm
β = 105.842 (4)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	4589 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	3977 reflections with I > 2σ(I)
T_min = 0.927, T_max = 1.000	R_int = 0.019
8862 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	30 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.10	Δρ_max = 0.79 e Å⁻³
4589 reflections	Δρ_min = −0.44 e Å⁻³
323 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 F\^2\^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F\^2\^, conventional R-factors R are based on F, with F set to zero for negative F\^2\^. The threshold expression of F\^2\^ > σ(F\^2\^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F\^2\^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co	0.0000	0.5000	0.5000	0.01992 (11)
N1	−0.10600 (16)	0.51602 (15)	0.34011 (13)	0.0205 (3)
N2	−0.19511 (16)	0.39511 (15)	0.50211 (13)	0.0202 (3)
C1	−0.04208 (19)	0.58671 (18)	0.27400 (16)	0.0207 (4)
C2	−0.1554 (2)	0.57948 (19)	0.16553 (17)	0.0250 (4)
H2	−0.1398	0.6187	0.1064	0.030*
C3	−0.2885 (2)	0.50553 (19)	0.16529 (17)	0.0256 (4)
H3	−0.3826	0.4838	0.1059	0.031*
C4	−0.25852 (19)	0.46615 (18)	0.27385 (16)	0.0213 (4)
C5	−0.36903 (19)	0.39375 (18)	0.30882 (16)	0.0217 (4)
C6	−0.33699 (19)	0.36035 (18)	0.41648 (16)	0.0216 (4)
C7	−0.4490 (2)	0.2741 (2)	0.44746 (18)	0.0268 (4)
H7	−0.5525	0.2383	0.4042	0.032*
C8	−0.3764 (2)	0.2551 (2)	0.55053 (18)	0.0276 (4)
H8	−0.4199	0.2024	0.5917	0.033*
C9	−0.21943 (19)	0.33090 (18)	0.58552 (16)	0.0217 (4)
C10	0.1099 (2)	0.66163 (18)	0.30894 (16)	0.0213 (4)
C11	0.15851 (19)	0.74003 (18)	0.23032 (16)	0.0224 (4)
C12	0.1820 (2)	0.6798 (2)	0.12439 (18)	0.0293 (4)
H12	0.1656	0.5883	0.1003	0.035*
C13	0.2294 (2)	0.7541 (2)	0.05387 (19)	0.0339 (5)
H13	0.2456	0.7125	−0.0169	0.041*
C14	0.2529 (2)	0.8891 (2)	0.08771 (19)	0.0322 (4)
H14	0.2848	0.9390	0.0401	0.039*
C15	0.2289 (3)	0.9494 (2)	0.1922 (2)	0.0387 (5)
H15	0.2439	1.0406	0.2153	0.046*
C16	0.1824 (3)	0.8759 (2)	0.26378 (19)	0.0347 (5)
H16	0.1672	0.9181	0.3349	0.042*
C17	−0.52953 (19)	0.34897 (18)	0.22752 (17)	0.0229 (4)
C18	−0.5921 (2)	0.2539 (2)	0.10469 (18)	0.0277 (4)
H18	−0.5327	0.2183	0.0722	0.033*
C19	−0.7417 (2)	0.2114 (2)	0.03001 (19)	0.0346 (5)
H19	−0.7823	0.1476	−0.0522	0.042*
C20	−0.8304 (2)	0.2635 (2)	0.0775 (2)	0.0371 (5)
H20	−0.9312	0.2343	0.0279	0.045*
C21	−0.7694 (2)	0.3590 (2)	0.1985 (2)	0.0372 (5)
H21	−0.8289	0.3949	0.2304	0.045*
C22	−0.6198 (2)	0.4018 (2)	0.27297 (19)	0.0308 (4)
H22	−0.5793	0.4668	0.3545	0.037*
O1	1.00507 (17)	0.72687 (17)	0.61845 (14)	0.0415 (4)
O2	0.7723 (2)	0.8744 (2)	0.46275 (19)	0.0633 (5)
O3	0.75479 (18)	0.98421 (16)	0.26483 (16)	0.0438 (4)
C23	1.1145 (3)	0.8022 (2)	0.7438 (2)	0.0399 (5)
H23A	1.1340	0.7388	0.7828	0.048*
H23B	1.0739	0.8534	0.7930	0.048*
C24A	0.8779 (5)	0.7518 (5)	0.5733 (4)	0.0333 (11)	0.565 (7)
H24A	0.8463	0.7817	0.6419	0.040*	0.565 (7)
H24B	0.7962	0.6691	0.5084	0.040*	0.565 (7)
C25A	0.9181 (5)	0.8618 (5)	0.5181 (5)	0.0465 (14)	0.565 (7)
H25A	0.9936	0.9474	0.5837	0.056*	0.565 (7)
H25B	0.9557	0.8353	0.4528	0.056*	0.565 (7)
C24B	0.9331 (11)	0.8256 (10)	0.5946 (9)	0.071 (2)	0.435 (7)
H24C	0.9026	0.8563	0.6639	0.085*	0.435 (7)
H24D	1.0063	0.9049	0.5921	0.085*	0.435 (7)
C25B	0.8162 (10)	0.7669 (8)	0.4875 (8)	0.075 (3)	0.435 (7)
H25C	0.7347	0.6982	0.4942	0.089*	0.435 (7)
H25D	0.8415	0.7234	0.4193	0.089*	0.435 (7)
C26	0.6814 (3)	0.8027 (2)	0.3354 (3)	0.0493 (6)
H26A	0.5947	0.7262	0.3264	0.059*
H26B	0.7366	0.7676	0.2905	0.059*
C27	0.6318 (3)	0.8965 (3)	0.2809 (2)	0.0465 (6)
H27A	0.5481	0.8445	0.1998	0.056*
H27B	0.5997	0.9493	0.3378	0.056*
C28	0.7410 (3)	1.1016 (2)	0.2499 (2)	0.0396 (5)
H28A	0.7135	1.1454	0.3164	0.048*
H28B	0.6623	1.0768	0.1687	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.01575 (17)	0.0281 (2)	0.01649 (18)	0.00707 (14)	0.00525 (13)	0.01245 (14)
N1	0.0169 (7)	0.0242 (8)	0.0186 (7)	0.0062 (6)	0.0053 (6)	0.0095 (6)
N2	0.0202 (7)	0.0235 (8)	0.0168 (7)	0.0083 (6)	0.0053 (6)	0.0097 (6)
C1	0.0227 (9)	0.0237 (9)	0.0171 (8)	0.0096 (7)	0.0075 (7)	0.0100 (7)
C2	0.0272 (9)	0.0296 (10)	0.0191 (9)	0.0111 (8)	0.0067 (7)	0.0136 (8)
C3	0.0230 (9)	0.0310 (10)	0.0207 (9)	0.0104 (8)	0.0037 (7)	0.0120 (8)
C4	0.0204 (8)	0.0243 (9)	0.0177 (8)	0.0092 (7)	0.0043 (7)	0.0086 (7)
C5	0.0185 (8)	0.0234 (9)	0.0194 (8)	0.0072 (7)	0.0039 (7)	0.0073 (7)
C6	0.0173 (8)	0.0242 (9)	0.0199 (9)	0.0063 (7)	0.0050 (7)	0.0077 (7)
C7	0.0176 (8)	0.0329 (10)	0.0262 (9)	0.0054 (8)	0.0068 (7)	0.0132 (8)
C8	0.0220 (9)	0.0337 (10)	0.0260 (9)	0.0057 (8)	0.0097 (8)	0.0161 (8)
C9	0.0201 (8)	0.0248 (9)	0.0199 (9)	0.0070 (7)	0.0084 (7)	0.0098 (7)
C10	0.0244 (9)	0.0231 (9)	0.0187 (8)	0.0094 (7)	0.0095 (7)	0.0100 (7)
C11	0.0193 (8)	0.0274 (9)	0.0194 (8)	0.0066 (7)	0.0056 (7)	0.0124 (7)
C12	0.0378 (11)	0.0312 (10)	0.0279 (10)	0.0178 (9)	0.0161 (8)	0.0163 (8)
C13	0.0407 (12)	0.0461 (13)	0.0285 (10)	0.0223 (10)	0.0206 (9)	0.0215 (10)
C14	0.0288 (10)	0.0374 (11)	0.0275 (10)	0.0053 (9)	0.0080 (8)	0.0211 (9)
C15	0.0509 (13)	0.0244 (10)	0.0315 (11)	0.0065 (9)	0.0108 (10)	0.0123 (9)
C16	0.0486 (12)	0.0299 (11)	0.0245 (10)	0.0126 (9)	0.0159 (9)	0.0103 (8)
C17	0.0196 (8)	0.0249 (9)	0.0233 (9)	0.0071 (7)	0.0049 (7)	0.0138 (8)
C18	0.0258 (9)	0.0305 (10)	0.0242 (9)	0.0102 (8)	0.0063 (8)	0.0113 (8)
C19	0.0292 (10)	0.0346 (11)	0.0259 (10)	0.0033 (9)	−0.0010 (8)	0.0139 (9)
C20	0.0183 (9)	0.0468 (13)	0.0425 (12)	0.0075 (9)	0.0014 (8)	0.0290 (11)
C21	0.0258 (10)	0.0482 (13)	0.0492 (13)	0.0203 (10)	0.0163 (9)	0.0272 (11)
C22	0.0269 (10)	0.0347 (11)	0.0297 (10)	0.0121 (8)	0.0093 (8)	0.0122 (9)
O1	0.0360 (8)	0.0523 (10)	0.0342 (8)	0.0179 (7)	0.0067 (7)	0.0202 (7)
O2	0.0793 (12)	0.0724 (11)	0.0566 (10)	0.0555 (10)	0.0198 (9)	0.0282 (9)
O3	0.0461 (9)	0.0420 (9)	0.0594 (11)	0.0225 (8)	0.0307 (8)	0.0269 (8)
C23	0.0528 (14)	0.0367 (12)	0.0284 (11)	0.0177 (11)	0.0121 (10)	0.0137 (9)
C24A	0.032 (2)	0.036 (2)	0.035 (2)	0.0101 (18)	0.0153 (17)	0.0186 (18)
C25A	0.034 (2)	0.042 (3)	0.051 (3)	0.0053 (19)	0.0043 (19)	0.024 (2)
C24B	0.070 (3)	0.066 (3)	0.075 (3)	0.030 (2)	0.0147 (19)	0.035 (2)
C25B	0.074 (3)	0.068 (3)	0.080 (3)	0.035 (2)	0.0159 (19)	0.032 (2)
C26	0.0573 (15)	0.0349 (13)	0.0629 (17)	0.0176 (11)	0.0343 (13)	0.0181 (12)
C27	0.0293 (11)	0.0565 (15)	0.0486 (14)	0.0107 (10)	0.0121 (10)	0.0230 (12)
C28	0.0430 (13)	0.0389 (12)	0.0328 (11)	0.0201 (10)	0.0071 (10)	0.0104 (10)

Geometric parameters (Å, º) top

Co—N2	1.9669 (14)	C18—C19	1.385 (3)
Co—N2ⁱ	1.9669 (14)	C18—H18	0.9300
Co—N1ⁱ	1.9757 (14)	C19—C20	1.377 (3)
Co—N1	1.9757 (14)	C19—H19	0.9300
N1—C1	1.377 (2)	C20—C21	1.375 (3)
N1—C4	1.378 (2)	C20—H20	0.9300
N2—C9	1.377 (2)	C21—C22	1.383 (3)
N2—C6	1.379 (2)	C21—H21	0.9300
C1—C10	1.385 (2)	C22—H22	0.9300
C1—C2	1.430 (2)	O1—C24A	1.394 (4)
C2—C3	1.341 (3)	O1—C23	1.420 (3)
C2—H2	0.9300	O1—C24B	1.534 (8)
C3—C4	1.435 (2)	O2—C26	1.385 (3)
C3—H3	0.9300	O2—C25B	1.462 (7)
C4—C5	1.386 (2)	O2—C25A	1.510 (5)
C5—C6	1.388 (2)	O3—C28	1.399 (3)
C5—C17	1.490 (2)	O3—C27	1.413 (3)
C6—C7	1.434 (2)	C23—C28ⁱⁱ	1.488 (3)
C7—C8	1.339 (3)	C23—H23A	0.9700
C7—H7	0.9300	C23—H23B	0.9700
C8—C9	1.429 (2)	C24A—C25A	1.517 (6)
C8—H8	0.9300	C24A—H24A	0.9700
C9—C10ⁱ	1.386 (2)	C24A—H24B	0.9700
C10—C9ⁱ	1.386 (2)	C25A—H25A	0.9700
C10—C11	1.494 (2)	C25A—H25B	0.9700
C11—C12	1.380 (3)	C24B—C25B	1.308 (12)
C11—C16	1.381 (3)	C24B—H24C	0.9700
C12—C13	1.380 (3)	C24B—H24D	0.9700
C12—H12	0.9300	C25B—H25C	0.9700
C13—C14	1.373 (3)	C25B—H25D	0.9700
C13—H13	0.9300	C26—C27	1.493 (3)
C14—C15	1.370 (3)	C26—H26A	0.9700
C14—H14	0.9300	C26—H26B	0.9700
C15—C16	1.382 (3)	C27—H27A	0.9700
C15—H15	0.9300	C27—H27B	0.9700
C16—H16	0.9300	C28—C23ⁱⁱ	1.488 (3)
C17—C22	1.384 (3)	C28—H28A	0.9700
C17—C18	1.388 (3)	C28—H28B	0.9700

N2—Co—N2ⁱ	180.0	C20—C19—C18	119.9 (2)
N2—Co—N1ⁱ	90.63 (6)	C20—C19—H19	120.0
N2ⁱ—Co—N1ⁱ	89.37 (6)	C18—C19—H19	120.0
N2—Co—N1	89.37 (6)	C21—C20—C19	119.82 (18)
N2ⁱ—Co—N1	90.63 (6)	C21—C20—H20	120.1
N1ⁱ—Co—N1	180.0	C19—C20—H20	120.1
C1—N1—C4	104.78 (14)	C20—C21—C22	120.2 (2)
C1—N1—Co	126.92 (12)	C20—C21—H21	119.9
C4—N1—Co	128.22 (12)	C22—C21—H21	119.9
C9—N2—C6	104.48 (14)	C21—C22—C17	120.75 (19)
C9—N2—Co	126.91 (12)	C21—C22—H22	119.6
C6—N2—Co	128.44 (12)	C17—C22—H22	119.6
N1—C1—C10	125.90 (16)	C24A—O1—C23	122.1 (2)
N1—C1—C2	110.67 (15)	C23—O1—C24B	102.2 (4)
C10—C1—C2	123.35 (16)	C26—O2—C25B	97.5 (4)
C3—C2—C1	107.06 (16)	C26—O2—C25A	120.3 (3)
C3—C2—H2	126.5	C28—O3—C27	114.26 (18)
C1—C2—H2	126.5	O1—C23—C28ⁱⁱ	113.86 (18)
C2—C3—C4	107.11 (16)	O1—C23—H23A	108.8
C2—C3—H3	126.4	C28ⁱⁱ—C23—H23A	108.8
C4—C3—H3	126.4	O1—C23—H23B	108.8
N1—C4—C5	125.58 (16)	C28ⁱⁱ—C23—H23B	108.8
N1—C4—C3	110.38 (15)	H23A—C23—H23B	107.7
C5—C4—C3	123.97 (16)	O1—C24A—C25A	107.9 (3)
C4—C5—C6	122.88 (16)	O1—C24A—H24A	110.1
C4—C5—C17	118.89 (16)	C25A—C24A—H24A	110.1
C6—C5—C17	118.23 (16)	O1—C24A—H24B	110.1
N2—C6—C5	125.50 (16)	C25A—C24A—H24B	110.1
N2—C6—C7	110.62 (15)	H24A—C24A—H24B	108.4
C5—C6—C7	123.69 (16)	O2—C25A—C24A	104.3 (3)
C8—C7—C6	106.93 (16)	O2—C25A—H25A	110.9
C8—C7—H7	126.5	C24A—C25A—H25A	110.9
C6—C7—H7	126.5	O2—C25A—H25B	110.9
C7—C8—C9	107.22 (16)	C24A—C25A—H25B	110.9
C7—C8—H8	126.4	H25A—C25A—H25B	108.9
C9—C8—H8	126.4	C25B—C24B—O1	111.0 (8)
N2—C9—C10ⁱ	126.03 (16)	C25B—C24B—H24C	109.4
N2—C9—C8	110.74 (15)	O1—C24B—H24C	109.4
C10ⁱ—C9—C8	123.23 (16)	C25B—C24B—H24D	109.4
C1—C10—C9ⁱ	123.25 (16)	O1—C24B—H24D	109.4
C1—C10—C11	118.58 (15)	H24C—C24B—H24D	108.0
C9ⁱ—C10—C11	118.16 (16)	C24B—C25B—O2	106.7 (7)
C12—C11—C16	118.63 (17)	C24B—C25B—H25C	110.4
C12—C11—C10	121.28 (17)	O2—C25B—H25C	110.4
C16—C11—C10	120.09 (17)	C24B—C25B—H25D	110.4
C11—C12—C13	120.67 (18)	O2—C25B—H25D	110.4
C11—C12—H12	119.7	H25C—C25B—H25D	108.6
C13—C12—H12	119.7	O2—C26—C27	108.8 (2)
C14—C13—C12	120.34 (19)	O2—C26—H26A	109.9
C14—C13—H13	119.8	C27—C26—H26A	109.9
C12—C13—H13	119.8	O2—C26—H26B	109.9
C15—C14—C13	119.39 (18)	C27—C26—H26B	109.9
C15—C14—H14	120.3	H26A—C26—H26B	108.3
C13—C14—H14	120.3	O3—C27—C26	107.81 (19)
C14—C15—C16	120.54 (19)	O3—C27—H27A	110.1
C14—C15—H15	119.7	C26—C27—H27A	110.1
C16—C15—H15	119.7	O3—C27—H27B	110.1
C11—C16—C15	120.43 (19)	C26—C27—H27B	110.1
C11—C16—H16	119.8	H27A—C27—H27B	108.5
C15—C16—H16	119.8	O3—C28—C23ⁱⁱ	110.08 (18)
C22—C17—C18	118.42 (17)	O3—C28—H28A	109.6
C22—C17—C5	120.57 (17)	C23ⁱⁱ—C28—H28A	109.6
C18—C17—C5	121.01 (17)	O3—C28—H28B	109.6
C19—C18—C17	120.81 (19)	C23ⁱⁱ—C28—H28B	109.6
C19—C18—H18	119.6	H28A—C28—H28B	108.2
C17—C18—H18	119.6

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

Experimental details

Crystal data
Chemical formula	[Co(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆
M_r	935.95
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	10.1464 (4), 11.0890 (6), 11.7570 (5)
α, β, γ (°)	104.327 (4), 105.842 (4), 108.284 (4)
V (Å³)	1125.12 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.25 × 0.24 × 0.21

Data collection
Diffractometer	Oxford Diffraction Xcalibur
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.927, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8862, 4589, 3977
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 1.10
No. of reflections	4589
No. of parameters	323
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.44

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, m1997).

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Higher Education, Scientific Research and Technology of Tunisia.

References

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