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In the crystal structure of the title compound, [Co(NO2)(C44H28N4)(C2H6O)], a distorted octahedral CoIII complex shows orientational disorder such that the positions of the nitro and ethanol ligands are exchanged. As a result, the averaged structure has an inversion center at the Co atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006049/na6153sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006049/na6153Isup2.hkl
Contains datablock I

CCDC reference: 185742

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](C-C) = 0.004 Å
  • H-atom completeness 83%
  • R factor = 0.039
  • wR factor = 0.112
  • Data-to-parameter ratio = 15.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C46 H34 Co1 N5 O3 Atom count from the _atom_site data: C46 H28 Co1 N5 O3 CELLZ_01 From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C46 H34 Co N5 O3 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 46.00 46.00 0.00 H 34.00 28.00 6.00 Co 1.00 1.00 0.00 N 5.00 5.00 0.00 O 3.00 3.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?

Comment top

The nitro-to-nitrito photoisomerization of the title complex, [Co(tpp)(NO2)], where tpp is α,β,γ,δ-tetraphenylporphyrinate, was investigated in a benzene solution using the laser flash technique (Seki et al., 1997). The compound obtained from a benzene solution was determined to be [Co(tpp)(NO2)].benzene, which has an distorted square-pyramidal coordination with the nitro ligand at the apical position (Ohba & Seki, 2002a). The crystals grown from dimethylformamide (DMF) and dichloromethane solutions were determined to be [Co(tpp)(NO2)(H2O)]·2DMF (Ohba et al., 2000) and [Co(tpp)(NO2)(H2O)]·CH2Cl2 (Ohba & Seki, 2002b), respectively, which show a distorted octahedral coordination with the water molecule trans to the nitro ligand. The present paper reports the structure of the title crystal, [Co(tpp)(NO2)(EtOH)], (I), which was grown from a CH2Cl2/EtOH solution.

The Co complex has an ethanol molecule trans to the nitro ligand (Fig. 1), indicating that polar solvent molecule such as ethanol easily coordinates to the Co instead of a water molecule. The Co atom lies on a center of symmetry, and there is an orientational disorder such that the positions of the nitro and ethanol ligands are exchanged. Similar disorder was observed in the crystals of [Co(tpp)(NO2)(H2O)]·2DMF, where the positions of the nitro and aqua ligands are exchanged (Ohba et al., 2000). In (I), the cobalt complexes are stacked along the a axis to form one-dimensional columns (Fig. 2). The orientation of the cobalt complexes in a column may be ordered to avoid the close contact between the ethanol molecules.

Experimental top

The preparation of the title complex has been described previously (Seki et al., 1997). Crystals were grown from a dichloromethane–EtOH (3:2) solution.

Refinement top

The crystal specimen was sealed in a capillary with the mother liquor to avoid efflorescence. A split-site model was not applicable for positional disorder of the nitro N5 and ethanol O4 atoms. It was assumed that the N5 and O4 atoms share the same positional and atomic displacement parameters. Furthermore, the ethanol molecule show a disorder, which leads the largely elongated displacement ellipsoid of C31 and the abnormal bond angle O4—C30—C31 of 179.0 (6)°. However, a split-site model of the C30 and C31 atoms was unsuccessful. All H-atom positional parameters, except for those of ethanol, were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom). The H atoms of the ethanol were not introduced.

Computing details top

Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids plotted at the 50% probability level. The disordered nitro and ethanol ligands are shown only one of two possible positions for clarity.
[Figure 2] Fig. 2. The projection of the crystal structure of (I) along b. The disordered nitro and ethanol ligands are shown only one of two possible positions for clarity.
(I) top
Crystal data top
[Co(NO2)(C44H28N4)(C2H6O)]Z = 1
Mr = 763.73F(000) = 396
Triclinic, P1Dx = 1.374 Mg m3
a = 10.071 (2) ÅMo Kα radiation, λ = 0.7107 Å
b = 11.653 (2) ÅCell parameters from 25 reflections
c = 9.184 (2) Åθ = 10.0–14.0°
α = 92.65 (2)°µ = 0.52 mm1
β = 108.81 (2)°T = 297 K
γ = 65.45 (1)°Plate, purple
V = 923.2 (4) Å30.55 × 0.30 × 0.10 mm
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.008
θ–2θ scansθmax = 27.5°, θmin = 2.5°
Absorption correction: integration
(Coppens et al., 1965)
h = 1313
Tmin = 0.861, Tmax = 0.951k = 1515
4686 measured reflectionsl = 011
4233 independent reflections3 standard reflections every 150 reflections
3748 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2H-atom parameters not refined
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.050P)2 + 0.5469P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.113(Δ/σ)max = 0.001
S = 1.11Δρmax = 0.34 e Å3
4233 reflectionsΔρmin = 0.39 e Å3
269 parameters
Crystal data top
[Co(NO2)(C44H28N4)(C2H6O)]γ = 65.45 (1)°
Mr = 763.73V = 923.2 (4) Å3
Triclinic, P1Z = 1
a = 10.071 (2) ÅMo Kα radiation
b = 11.653 (2) ŵ = 0.52 mm1
c = 9.184 (2) ÅT = 297 K
α = 92.65 (2)°0.55 × 0.30 × 0.10 mm
β = 108.81 (2)°
Data collection top
Rigaku AFC-7R
diffractometer
3748 reflections with I > 2σ(I)
Absorption correction: integration
(Coppens et al., 1965)
Rint = 0.008
Tmin = 0.861, Tmax = 0.9513 standard reflections every 150 reflections
4686 measured reflections intensity decay: none
4233 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039269 parameters
wR(F2) = 0.113H-atom parameters not refined
S = 1.11Δρmax = 0.34 e Å3
4233 reflectionsΔρmin = 0.39 e Å3
Special details top

Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.00000.00000.00000.0263 (1)
O20.1509 (5)0.0616 (4)0.1576 (5)0.066 (1)0.50
O30.2952 (5)0.0319 (6)0.0675 (6)0.079 (1)0.50
O40.1768 (2)0.0111 (2)0.0314 (2)0.0471 (4)0.50
N50.1768 (2)0.0111 (2)0.0314 (2)0.0471 (4)0.50
N60.1379 (2)0.1728 (2)0.1079 (2)0.0326 (3)
N70.0454 (2)0.0758 (2)0.1975 (2)0.0307 (3)
C80.1676 (2)0.2871 (2)0.0454 (3)0.0359 (4)
C90.2735 (3)0.3896 (2)0.1640 (3)0.0472 (6)
C100.3110 (3)0.3379 (2)0.2964 (3)0.0480 (6)
C110.2263 (2)0.2028 (2)0.2618 (2)0.0355 (4)
C120.2347 (2)0.1176 (2)0.3713 (2)0.0355 (4)
C130.1448 (2)0.0116 (2)0.3393 (2)0.0344 (4)
C140.1468 (3)0.0996 (2)0.4546 (3)0.0438 (5)
C150.0514 (3)0.2163 (2)0.3820 (3)0.0431 (5)
C160.0101 (2)0.2025 (2)0.2210 (2)0.0332 (4)
C170.1085 (2)0.3033 (2)0.1086 (2)0.0352 (4)
C180.3538 (3)0.1678 (2)0.5290 (2)0.0371 (4)
C190.5009 (3)0.1771 (3)0.5542 (3)0.0620 (7)
C200.6145 (3)0.2245 (4)0.6984 (4)0.0753 (9)
C210.5819 (3)0.2624 (3)0.8154 (3)0.0586 (7)
C220.4360 (4)0.2511 (3)0.7925 (3)0.0600 (7)
C230.3218 (3)0.2035 (3)0.6491 (3)0.0532 (6)
C240.1509 (3)0.4358 (2)0.1568 (2)0.0389 (5)
C250.0516 (3)0.4925 (3)0.1766 (4)0.0590 (7)
C260.0892 (4)0.6139 (3)0.2248 (4)0.0719 (9)
C270.2228 (4)0.6770 (3)0.2531 (4)0.0677 (9)
C280.3266 (4)0.6241 (3)0.2294 (4)0.0730 (9)
C290.2905 (4)0.5035 (3)0.1808 (4)0.0605 (7)
C300.2993 (6)0.0097 (5)0.0227 (8)0.050 (1)0.50
C310.4501 (8)0.0054 (7)0.011 (1)0.103 (3)0.50
H90.31020.47750.15120.0566*
H100.38050.38240.39430.0576*
H140.20470.07900.56180.0526*
H150.02860.29360.42850.0517*
H190.52460.15120.47280.0744*
H200.71550.23050.71520.0903*
H210.66060.29660.91290.0703*
H220.41270.27580.87490.0721*
H230.22040.19560.63410.0639*
H250.04340.44860.15740.0708*
H260.01990.65220.23760.0863*
H270.24570.75840.28960.0812*
H280.42260.67000.24610.0876*
H290.36230.46720.16410.0726*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0244 (2)0.0242 (2)0.0289 (2)0.0107 (1)0.0072 (1)0.0070 (1)
O20.069 (3)0.075 (3)0.066 (2)0.032 (2)0.033 (2)0.008 (2)
O30.037 (2)0.135 (5)0.067 (3)0.046 (3)0.005 (2)0.004 (3)
O40.050 (1)0.0420 (10)0.052 (1)0.0205 (8)0.0203 (9)0.0129 (8)
N50.050 (1)0.0420 (10)0.052 (1)0.0205 (8)0.0203 (9)0.0129 (8)
N60.0336 (8)0.0253 (8)0.0324 (8)0.0104 (7)0.0061 (7)0.0066 (6)
N70.0309 (8)0.0268 (8)0.0308 (8)0.0119 (6)0.0067 (6)0.0070 (6)
C80.037 (1)0.0249 (9)0.039 (1)0.0109 (8)0.0079 (8)0.0071 (8)
C90.053 (1)0.0252 (10)0.045 (1)0.0085 (9)0.004 (1)0.0055 (9)
C100.053 (1)0.029 (1)0.040 (1)0.0084 (10)0.000 (1)0.0014 (9)
C110.036 (1)0.0293 (9)0.0325 (10)0.0106 (8)0.0047 (8)0.0041 (8)
C120.035 (1)0.0336 (10)0.0308 (10)0.0131 (8)0.0045 (8)0.0043 (8)
C130.037 (1)0.0322 (10)0.0301 (9)0.0148 (8)0.0064 (8)0.0074 (8)
C140.053 (1)0.037 (1)0.031 (1)0.0162 (10)0.0047 (9)0.0108 (8)
C150.052 (1)0.034 (1)0.036 (1)0.0167 (10)0.0091 (10)0.0140 (9)
C160.0346 (10)0.0289 (9)0.0341 (10)0.0139 (8)0.0096 (8)0.0104 (8)
C170.037 (1)0.0258 (9)0.039 (1)0.0124 (8)0.0098 (8)0.0095 (8)
C180.040 (1)0.0299 (9)0.0303 (10)0.0110 (8)0.0031 (8)0.0049 (7)
C190.041 (1)0.089 (2)0.045 (1)0.020 (1)0.009 (1)0.002 (1)
C200.038 (1)0.105 (3)0.059 (2)0.019 (2)0.000 (1)0.003 (2)
C210.059 (2)0.043 (1)0.040 (1)0.008 (1)0.008 (1)0.002 (1)
C220.085 (2)0.055 (2)0.038 (1)0.037 (1)0.008 (1)0.003 (1)
C230.056 (1)0.064 (2)0.043 (1)0.035 (1)0.008 (1)0.001 (1)
C240.047 (1)0.0261 (9)0.034 (1)0.0130 (9)0.0065 (9)0.0082 (8)
C250.046 (1)0.040 (1)0.081 (2)0.019 (1)0.010 (1)0.017 (1)
C260.068 (2)0.044 (1)0.092 (2)0.033 (1)0.002 (2)0.019 (1)
C270.090 (2)0.036 (1)0.058 (2)0.022 (1)0.010 (2)0.022 (1)
C280.088 (2)0.045 (2)0.093 (2)0.022 (2)0.051 (2)0.033 (2)
C290.070 (2)0.041 (1)0.083 (2)0.026 (1)0.041 (2)0.025 (1)
C300.039 (3)0.044 (3)0.085 (4)0.025 (2)0.035 (3)0.025 (3)
C310.062 (4)0.080 (5)0.21 (1)0.051 (4)0.081 (6)0.073 (6)
Geometric parameters (Å, º) top
Co1—N51.949 (3)C15—H150.950
Co1—O4i1.949 (3)C16—C171.383 (3)
Co1—N61.984 (1)C17—C241.507 (3)
Co1—N6i1.984 (1)C18—C191.382 (4)
Co1—N71.982 (2)C18—C231.370 (4)
Co1—N7i1.982 (2)C19—C201.390 (4)
O2—N51.223 (5)C19—H190.950
O3—N51.160 (4)C20—C211.360 (6)
O4—C301.202 (7)C20—H200.950
N6—C81.379 (3)C21—C221.365 (5)
N6—C111.375 (2)C21—H210.950
N7—C131.373 (2)C22—C231.388 (3)
N7—C161.380 (3)C22—H220.950
C8—C91.436 (3)C23—H230.950
C8—C17i1.385 (3)C24—C251.375 (5)
C9—C101.345 (3)C24—C291.382 (4)
C9—H90.950C25—C261.395 (4)
C10—C111.436 (3)C25—H250.950
C10—H100.950C26—C271.343 (6)
C11—C121.389 (3)C26—H260.950
C12—C131.382 (3)C27—C281.377 (6)
C12—C181.501 (3)C27—H270.950
C13—C141.441 (3)C28—C291.389 (4)
C14—C151.342 (3)C28—H280.950
C14—H140.950C29—H290.950
C15—C161.437 (3)C30—C311.47 (1)
N5—Co1—N5i180.0C14—C15—C16107.3 (2)
N5—Co1—N689.42 (8)C14—C15—H15126.3
N5—Co1—N6i90.58 (8)C16—C15—H15126.4
N5—Co1—N788.74 (9)N7—C16—C15109.9 (2)
N5—Co1—N7i91.26 (9)N7—C16—C17126.2 (2)
N5i—Co1—N690.58 (8)C15—C16—C17123.9 (2)
N5i—Co1—N6i89.42 (8)C8i—C17—C16122.7 (2)
N5i—Co1—N791.26 (9)C8i—C17—C24119.1 (2)
N5i—Co1—N7i88.74 (9)C16—C17—C24118.2 (2)
N6—Co1—N6i180.0C12—C18—C19118.6 (2)
N6—Co1—N790.71 (6)C12—C18—C23122.6 (2)
N6—Co1—N7i89.29 (6)C19—C18—C23118.8 (2)
N6i—Co1—N789.29 (6)C18—C19—C20120.1 (3)
N6i—Co1—N7i90.71 (6)C18—C19—H19119.9
N7—Co1—N7i180.0C20—C19—H19119.9
Co1—N5—O2115.4 (3)C19—C20—C21120.3 (3)
Co1—N5—O3118.1 (4)C19—C20—H20119.8
Co1—O4—C30168.0 (4)C21—C20—H20119.8
O2—N5—O3126.5 (5)C20—C21—C22119.9 (2)
Co1—N6—C8127.9 (1)C20—C21—H21120.0
Co1—N6—C11126.6 (1)C22—C21—H21120.0
C8—N6—C11105.6 (1)C21—C22—C23120.1 (3)
Co1—N7—C13126.5 (1)C21—C22—H22119.9
Co1—N7—C16127.9 (1)C23—C22—H22120.0
C13—N7—C16105.6 (2)C18—C23—C22120.6 (3)
N6—C8—C9109.9 (2)C18—C23—H23119.7
N6—C8—C17i126.1 (2)C22—C23—H23119.7
C9—C8—C17i124.0 (2)C17—C24—C25120.5 (2)
C8—C9—C10107.3 (2)C17—C24—C29121.0 (3)
C8—C9—H9126.4C25—C24—C29118.4 (2)
C10—C9—H9126.4C24—C25—C26120.5 (3)
C9—C10—C11107.0 (2)C24—C25—H25119.7
C9—C10—H10126.5C26—C25—H25119.7
C11—C10—H10126.5C25—C26—C27120.5 (4)
N6—C11—C10110.2 (2)C25—C26—H26119.7
N6—C11—C12126.2 (2)C27—C26—H26119.7
C10—C11—C12123.6 (2)C26—C27—C28120.1 (3)
C11—C12—C13123.1 (2)C26—C27—H27119.9
C11—C12—C18118.1 (2)C28—C27—H27119.9
C13—C12—C18118.7 (2)C27—C28—C29119.7 (4)
N7—C13—C12126.6 (2)C27—C28—H28120.1
N7—C13—C14110.0 (2)C29—C28—H28120.1
C12—C13—C14123.3 (2)C24—C29—C28120.6 (4)
C13—C14—C15107.1 (2)C24—C29—H29119.7
C13—C14—H14126.5C28—C29—H29119.7
C15—C14—H14126.4O4—C30—C31179.0 (6)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formula[Co(NO2)(C44H28N4)(C2H6O)]
Mr763.73
Crystal system, space groupTriclinic, P1
Temperature (K)297
a, b, c (Å)10.071 (2), 11.653 (2), 9.184 (2)
α, β, γ (°)92.65 (2), 108.81 (2), 65.45 (1)
V3)923.2 (4)
Z1
Radiation typeMo Kα
µ (mm1)0.52
Crystal size (mm)0.55 × 0.30 × 0.10
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correctionIntegration
(Coppens et al., 1965)
Tmin, Tmax0.861, 0.951
No. of measured, independent and
observed [I > 2σ(I)] reflections
4686, 4233, 3748
Rint0.008
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.113, 1.11
No. of reflections4233
No. of parameters269
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.34, 0.39

Computer programs: WinAFC Diffractometer Control Software (Rigaku, 1999), WinAFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 2001), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.

Selected geometric parameters (Å, º) top
Co1—N51.949 (3)Co1—N61.984 (1)
Co1—O4i1.949 (3)Co1—N71.982 (2)
N5—Co1—N689.42 (8)N6—Co1—N790.71 (6)
N5—Co1—N788.74 (9)
Symmetry code: (i) x, y, z.
 

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