Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006049/na6153sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006049/na6153Isup2.hkl |
CCDC reference: 185742
Key indicators
- Single-crystal X-ray study
- T = 297 K
- Mean (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?
The preparation of the title complex has been described previously (Seki et al., 1997). Crystals were grown from a dichloromethane–EtOH (3:2) solution.
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.
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.
[Co(NO2)(C44H28N4)(C2H6O)] | Z = 1 |
Mr = 763.73 | F(000) = 396 |
Triclinic, P1 | Dx = 1.374 Mg m−3 |
a = 10.071 (2) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 11.653 (2) Å | Cell parameters from 25 reflections |
c = 9.184 (2) Å | θ = 10.0–14.0° |
α = 92.65 (2)° | µ = 0.52 mm−1 |
β = 108.81 (2)° | T = 297 K |
γ = 65.45 (1)° | Plate, purple |
V = 923.2 (4) Å3 | 0.55 × 0.30 × 0.10 mm |
Rigaku AFC-7R diffractometer | Rint = 0.008 |
θ–2θ scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = −13→13 |
Tmin = 0.861, Tmax = 0.951 | k = −15→15 |
4686 measured reflections | l = 0→11 |
4233 independent reflections | 3 standard reflections every 150 reflections |
3748 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | H-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 = 1.11 | Δρmax = 0.34 e Å−3 |
4233 reflections | Δρmin = −0.39 e Å−3 |
269 parameters |
[Co(NO2)(C44H28N4)(C2H6O)] | γ = 65.45 (1)° |
Mr = 763.73 | V = 923.2 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.071 (2) Å | Mo Kα radiation |
b = 11.653 (2) Å | µ = 0.52 mm−1 |
c = 9.184 (2) Å | T = 297 K |
α = 92.65 (2)° | 0.55 × 0.30 × 0.10 mm |
β = 108.81 (2)° |
Rigaku AFC-7R diffractometer | 3748 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.008 |
Tmin = 0.861, Tmax = 0.951 | 3 standard reflections every 150 reflections |
4686 measured reflections | intensity decay: none |
4233 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 269 parameters |
wR(F2) = 0.113 | H-atom parameters not refined |
S = 1.11 | Δρmax = 0.34 e Å−3 |
4233 reflections | Δρmin = −0.39 e Å−3 |
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). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.0263 (1) | |
O2 | 0.1509 (5) | 0.0616 (4) | −0.1576 (5) | 0.066 (1) | 0.50 |
O3 | 0.2952 (5) | −0.0319 (6) | 0.0675 (6) | 0.079 (1) | 0.50 |
O4 | 0.1768 (2) | 0.0111 (2) | −0.0314 (2) | 0.0471 (4) | 0.50 |
N5 | 0.1768 (2) | 0.0111 (2) | −0.0314 (2) | 0.0471 (4) | 0.50 |
N6 | 0.1379 (2) | −0.1728 (2) | 0.1079 (2) | 0.0326 (3) | |
N7 | 0.0454 (2) | 0.0758 (2) | 0.1975 (2) | 0.0307 (3) | |
C8 | 0.1676 (2) | −0.2871 (2) | 0.0454 (3) | 0.0359 (4) | |
C9 | 0.2735 (3) | −0.3896 (2) | 0.1640 (3) | 0.0472 (6) | |
C10 | 0.3110 (3) | −0.3379 (2) | 0.2964 (3) | 0.0480 (6) | |
C11 | 0.2263 (2) | −0.2028 (2) | 0.2618 (2) | 0.0355 (4) | |
C12 | 0.2347 (2) | −0.1176 (2) | 0.3713 (2) | 0.0355 (4) | |
C13 | 0.1448 (2) | 0.0116 (2) | 0.3393 (2) | 0.0344 (4) | |
C14 | 0.1468 (3) | 0.0996 (2) | 0.4546 (3) | 0.0438 (5) | |
C15 | 0.0514 (3) | 0.2163 (2) | 0.3820 (3) | 0.0431 (5) | |
C16 | −0.0101 (2) | 0.2025 (2) | 0.2210 (2) | 0.0332 (4) | |
C17 | −0.1085 (2) | 0.3033 (2) | 0.1086 (2) | 0.0352 (4) | |
C18 | 0.3538 (3) | −0.1678 (2) | 0.5290 (2) | 0.0371 (4) | |
C19 | 0.5009 (3) | −0.1771 (3) | 0.5542 (3) | 0.0620 (7) | |
C20 | 0.6145 (3) | −0.2245 (4) | 0.6984 (4) | 0.0753 (9) | |
C21 | 0.5819 (3) | −0.2624 (3) | 0.8154 (3) | 0.0586 (7) | |
C22 | 0.4360 (4) | −0.2511 (3) | 0.7925 (3) | 0.0600 (7) | |
C23 | 0.3218 (3) | −0.2035 (3) | 0.6491 (3) | 0.0532 (6) | |
C24 | −0.1509 (3) | 0.4358 (2) | 0.1568 (2) | 0.0389 (5) | |
C25 | −0.0516 (3) | 0.4925 (3) | 0.1766 (4) | 0.0590 (7) | |
C26 | −0.0892 (4) | 0.6139 (3) | 0.2248 (4) | 0.0719 (9) | |
C27 | −0.2228 (4) | 0.6770 (3) | 0.2531 (4) | 0.0677 (9) | |
C28 | −0.3266 (4) | 0.6241 (3) | 0.2294 (4) | 0.0730 (9) | |
C29 | −0.2905 (4) | 0.5035 (3) | 0.1808 (4) | 0.0605 (7) | |
C30 | 0.2993 (6) | 0.0097 (5) | −0.0227 (8) | 0.050 (1) | 0.50 |
C31 | 0.4501 (8) | 0.0054 (7) | −0.011 (1) | 0.103 (3) | 0.50 |
H9 | 0.3102 | −0.4775 | 0.1512 | 0.0566* | |
H10 | 0.3805 | −0.3824 | 0.3943 | 0.0576* | |
H14 | 0.2047 | 0.0790 | 0.5618 | 0.0526* | |
H15 | 0.0286 | 0.2936 | 0.4285 | 0.0517* | |
H19 | 0.5246 | −0.1512 | 0.4728 | 0.0744* | |
H20 | 0.7155 | −0.2305 | 0.7152 | 0.0903* | |
H21 | 0.6606 | −0.2966 | 0.9129 | 0.0703* | |
H22 | 0.4127 | −0.2758 | 0.8749 | 0.0721* | |
H23 | 0.2204 | −0.1956 | 0.6341 | 0.0639* | |
H25 | 0.0434 | 0.4486 | 0.1574 | 0.0708* | |
H26 | −0.0199 | 0.6522 | 0.2376 | 0.0863* | |
H27 | −0.2457 | 0.7584 | 0.2896 | 0.0812* | |
H28 | −0.4226 | 0.6700 | 0.2461 | 0.0876* | |
H29 | −0.3623 | 0.4672 | 0.1641 | 0.0726* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0244 (2) | 0.0242 (2) | 0.0289 (2) | −0.0107 (1) | 0.0072 (1) | −0.0070 (1) |
O2 | 0.069 (3) | 0.075 (3) | 0.066 (2) | −0.032 (2) | 0.033 (2) | 0.008 (2) |
O3 | 0.037 (2) | 0.135 (5) | 0.067 (3) | −0.046 (3) | 0.005 (2) | 0.004 (3) |
O4 | 0.050 (1) | 0.0420 (10) | 0.052 (1) | −0.0205 (8) | 0.0203 (9) | −0.0129 (8) |
N5 | 0.050 (1) | 0.0420 (10) | 0.052 (1) | −0.0205 (8) | 0.0203 (9) | −0.0129 (8) |
N6 | 0.0336 (8) | 0.0253 (8) | 0.0324 (8) | −0.0104 (7) | 0.0061 (7) | −0.0066 (6) |
N7 | 0.0309 (8) | 0.0268 (8) | 0.0308 (8) | −0.0119 (6) | 0.0067 (6) | −0.0070 (6) |
C8 | 0.037 (1) | 0.0249 (9) | 0.039 (1) | −0.0109 (8) | 0.0079 (8) | −0.0071 (8) |
C9 | 0.053 (1) | 0.0252 (10) | 0.045 (1) | −0.0085 (9) | 0.004 (1) | −0.0055 (9) |
C10 | 0.053 (1) | 0.029 (1) | 0.040 (1) | −0.0084 (10) | 0.000 (1) | −0.0014 (9) |
C11 | 0.036 (1) | 0.0293 (9) | 0.0325 (10) | −0.0106 (8) | 0.0047 (8) | −0.0041 (8) |
C12 | 0.035 (1) | 0.0336 (10) | 0.0308 (10) | −0.0131 (8) | 0.0045 (8) | −0.0043 (8) |
C13 | 0.037 (1) | 0.0322 (10) | 0.0301 (9) | −0.0148 (8) | 0.0064 (8) | −0.0074 (8) |
C14 | 0.053 (1) | 0.037 (1) | 0.031 (1) | −0.0162 (10) | 0.0047 (9) | −0.0108 (8) |
C15 | 0.052 (1) | 0.034 (1) | 0.036 (1) | −0.0167 (10) | 0.0091 (10) | −0.0140 (9) |
C16 | 0.0346 (10) | 0.0289 (9) | 0.0341 (10) | −0.0139 (8) | 0.0096 (8) | −0.0104 (8) |
C17 | 0.037 (1) | 0.0258 (9) | 0.039 (1) | −0.0124 (8) | 0.0098 (8) | −0.0095 (8) |
C18 | 0.040 (1) | 0.0299 (9) | 0.0303 (10) | −0.0110 (8) | 0.0031 (8) | −0.0049 (7) |
C19 | 0.041 (1) | 0.089 (2) | 0.045 (1) | −0.020 (1) | 0.009 (1) | 0.002 (1) |
C20 | 0.038 (1) | 0.105 (3) | 0.059 (2) | −0.019 (2) | 0.000 (1) | 0.003 (2) |
C21 | 0.059 (2) | 0.043 (1) | 0.040 (1) | −0.008 (1) | −0.008 (1) | −0.002 (1) |
C22 | 0.085 (2) | 0.055 (2) | 0.038 (1) | −0.037 (1) | 0.008 (1) | 0.003 (1) |
C23 | 0.056 (1) | 0.064 (2) | 0.043 (1) | −0.035 (1) | 0.008 (1) | −0.001 (1) |
C24 | 0.047 (1) | 0.0261 (9) | 0.034 (1) | −0.0130 (9) | 0.0065 (9) | −0.0082 (8) |
C25 | 0.046 (1) | 0.040 (1) | 0.081 (2) | −0.019 (1) | 0.010 (1) | −0.017 (1) |
C26 | 0.068 (2) | 0.044 (1) | 0.092 (2) | −0.033 (1) | 0.002 (2) | −0.019 (1) |
C27 | 0.090 (2) | 0.036 (1) | 0.058 (2) | −0.022 (1) | 0.010 (2) | −0.022 (1) |
C28 | 0.088 (2) | 0.045 (2) | 0.093 (2) | −0.022 (2) | 0.051 (2) | −0.033 (2) |
C29 | 0.070 (2) | 0.041 (1) | 0.083 (2) | −0.026 (1) | 0.041 (2) | −0.025 (1) |
C30 | 0.039 (3) | 0.044 (3) | 0.085 (4) | −0.025 (2) | 0.035 (3) | −0.025 (3) |
C31 | 0.062 (4) | 0.080 (5) | 0.21 (1) | −0.051 (4) | 0.081 (6) | −0.073 (6) |
Co1—N5 | 1.949 (3) | C15—H15 | 0.950 |
Co1—O4i | 1.949 (3) | C16—C17 | 1.383 (3) |
Co1—N6 | 1.984 (1) | C17—C24 | 1.507 (3) |
Co1—N6i | 1.984 (1) | C18—C19 | 1.382 (4) |
Co1—N7 | 1.982 (2) | C18—C23 | 1.370 (4) |
Co1—N7i | 1.982 (2) | C19—C20 | 1.390 (4) |
O2—N5 | 1.223 (5) | C19—H19 | 0.950 |
O3—N5 | 1.160 (4) | C20—C21 | 1.360 (6) |
O4—C30 | 1.202 (7) | C20—H20 | 0.950 |
N6—C8 | 1.379 (3) | C21—C22 | 1.365 (5) |
N6—C11 | 1.375 (2) | C21—H21 | 0.950 |
N7—C13 | 1.373 (2) | C22—C23 | 1.388 (3) |
N7—C16 | 1.380 (3) | C22—H22 | 0.950 |
C8—C9 | 1.436 (3) | C23—H23 | 0.950 |
C8—C17i | 1.385 (3) | C24—C25 | 1.375 (5) |
C9—C10 | 1.345 (3) | C24—C29 | 1.382 (4) |
C9—H9 | 0.950 | C25—C26 | 1.395 (4) |
C10—C11 | 1.436 (3) | C25—H25 | 0.950 |
C10—H10 | 0.950 | C26—C27 | 1.343 (6) |
C11—C12 | 1.389 (3) | C26—H26 | 0.950 |
C12—C13 | 1.382 (3) | C27—C28 | 1.377 (6) |
C12—C18 | 1.501 (3) | C27—H27 | 0.950 |
C13—C14 | 1.441 (3) | C28—C29 | 1.389 (4) |
C14—C15 | 1.342 (3) | C28—H28 | 0.950 |
C14—H14 | 0.950 | C29—H29 | 0.950 |
C15—C16 | 1.437 (3) | C30—C31 | 1.47 (1) |
N5—Co1—N5i | 180.0 | C14—C15—C16 | 107.3 (2) |
N5—Co1—N6 | 89.42 (8) | C14—C15—H15 | 126.3 |
N5—Co1—N6i | 90.58 (8) | C16—C15—H15 | 126.4 |
N5—Co1—N7 | 88.74 (9) | N7—C16—C15 | 109.9 (2) |
N5—Co1—N7i | 91.26 (9) | N7—C16—C17 | 126.2 (2) |
N5i—Co1—N6 | 90.58 (8) | C15—C16—C17 | 123.9 (2) |
N5i—Co1—N6i | 89.42 (8) | C8i—C17—C16 | 122.7 (2) |
N5i—Co1—N7 | 91.26 (9) | C8i—C17—C24 | 119.1 (2) |
N5i—Co1—N7i | 88.74 (9) | C16—C17—C24 | 118.2 (2) |
N6—Co1—N6i | 180.0 | C12—C18—C19 | 118.6 (2) |
N6—Co1—N7 | 90.71 (6) | C12—C18—C23 | 122.6 (2) |
N6—Co1—N7i | 89.29 (6) | C19—C18—C23 | 118.8 (2) |
N6i—Co1—N7 | 89.29 (6) | C18—C19—C20 | 120.1 (3) |
N6i—Co1—N7i | 90.71 (6) | C18—C19—H19 | 119.9 |
N7—Co1—N7i | 180.0 | C20—C19—H19 | 119.9 |
Co1—N5—O2 | 115.4 (3) | C19—C20—C21 | 120.3 (3) |
Co1—N5—O3 | 118.1 (4) | C19—C20—H20 | 119.8 |
Co1—O4—C30 | 168.0 (4) | C21—C20—H20 | 119.8 |
O2—N5—O3 | 126.5 (5) | C20—C21—C22 | 119.9 (2) |
Co1—N6—C8 | 127.9 (1) | C20—C21—H21 | 120.0 |
Co1—N6—C11 | 126.6 (1) | C22—C21—H21 | 120.0 |
C8—N6—C11 | 105.6 (1) | C21—C22—C23 | 120.1 (3) |
Co1—N7—C13 | 126.5 (1) | C21—C22—H22 | 119.9 |
Co1—N7—C16 | 127.9 (1) | C23—C22—H22 | 120.0 |
C13—N7—C16 | 105.6 (2) | C18—C23—C22 | 120.6 (3) |
N6—C8—C9 | 109.9 (2) | C18—C23—H23 | 119.7 |
N6—C8—C17i | 126.1 (2) | C22—C23—H23 | 119.7 |
C9—C8—C17i | 124.0 (2) | C17—C24—C25 | 120.5 (2) |
C8—C9—C10 | 107.3 (2) | C17—C24—C29 | 121.0 (3) |
C8—C9—H9 | 126.4 | C25—C24—C29 | 118.4 (2) |
C10—C9—H9 | 126.4 | C24—C25—C26 | 120.5 (3) |
C9—C10—C11 | 107.0 (2) | C24—C25—H25 | 119.7 |
C9—C10—H10 | 126.5 | C26—C25—H25 | 119.7 |
C11—C10—H10 | 126.5 | C25—C26—C27 | 120.5 (4) |
N6—C11—C10 | 110.2 (2) | C25—C26—H26 | 119.7 |
N6—C11—C12 | 126.2 (2) | C27—C26—H26 | 119.7 |
C10—C11—C12 | 123.6 (2) | C26—C27—C28 | 120.1 (3) |
C11—C12—C13 | 123.1 (2) | C26—C27—H27 | 119.9 |
C11—C12—C18 | 118.1 (2) | C28—C27—H27 | 119.9 |
C13—C12—C18 | 118.7 (2) | C27—C28—C29 | 119.7 (4) |
N7—C13—C12 | 126.6 (2) | C27—C28—H28 | 120.1 |
N7—C13—C14 | 110.0 (2) | C29—C28—H28 | 120.1 |
C12—C13—C14 | 123.3 (2) | C24—C29—C28 | 120.6 (4) |
C13—C14—C15 | 107.1 (2) | C24—C29—H29 | 119.7 |
C13—C14—H14 | 126.5 | C28—C29—H29 | 119.7 |
C15—C14—H14 | 126.4 | O4—C30—C31 | 179.0 (6) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co(NO2)(C44H28N4)(C2H6O)] |
Mr | 763.73 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 923.2 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.52 |
Crystal size (mm) | 0.55 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.861, 0.951 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4686, 4233, 3748 |
Rint | 0.008 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.113, 1.11 |
No. of reflections | 4233 |
No. of parameters | 269 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 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.
Co1—N5 | 1.949 (3) | Co1—N6 | 1.984 (1) |
Co1—O4i | 1.949 (3) | Co1—N7 | 1.982 (2) |
N5—Co1—N6 | 89.42 (8) | N6—Co1—N7 | 90.71 (6) |
N5—Co1—N7 | 88.74 (9) |
Symmetry code: (i) −x, −y, −z. |
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.