Study of the crystal structures of the title compounds reveals that the solid-state photochemical nitro–nitrito linkage isomerization is restricted by intermolecular C—H⋯O,O contacts in the 3-hydroxypyridine phase.
Keywords: crystal structure, nitro-nitrito photo linkage-isomerization, reaction cavity
Abstract
The reaction cavities of the nitro groups in the title compounds, trans-bis(acetylacetonato-κ2 O,O′)(nitro)(pyridine-κN)cobalt(III), [Co(C5H7O2)2(NO2)(C5H5N)], (I), trans-bis(acetylacetonato-κ2 O,O′)(4-methylpyridine-κN)(nitro)cobalt(III), [Co(C5H7O2)2(NO2)(C6H7N)], (II), and trans-bis(acetylacetonato-κ2 O,O′)(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate, [Co(C5H7O2)2(NO2)(C5H5NO)]·H2O, (III), have been investigated to reveal that bifurcated intermolecular C(py)—H⋯O,O contacts in (III) are unfeasible for the nitro–nitrito photochemical linkage isomerization process. In each structure, the pyridine ring and the Co atom lie on a crystallographic mirror plane; in (I) and (II) the nitro group lies in the same plane, whereas in (III), which crystallizes as a monohydrate, the nitro group is disordered over three orientations in a 0.672 (16):0.164 (8):0.164 (8) ratio; the water molecule of crystallization is statistically disordered over two sites adjacent to the mirror plane. In the crystals of (I) and (II), the molecules are linked into [100] chains by C—H⋯O hydrogen bonds, whereas the extended structure of (III) features (010) layers linked by O—H⋯O and C—H⋯O hydrogen bonds. Compounds (I) and (II) were refined as inversion twins.
Chemical context
Solid-state reactions are restricted by the cage effect, which is helpful for stereo-selectivity, but it sometimes interrupts the reaction. The photochemical nitro–nitrito linkage isomerization in crystals was investigated for the salts of [Co(NH3)5(NO2)]+, and indicated that insufficient free space around the nitro ligand prevents the isomerization from occurring (Boldyreva, 2001 ▸). For the salts of trans-[Co(en)2(NO2)(NCS)]+, a certain geometry of the intermolecular N—H⋯O hydrogen bonds restricts the photoisomerization (Ohba et al., 2018 ▸). In the present study, we investigated another type of nitrocobalt complex, trans-[Co(acac)2(NO2)(X-py)], where acac stands for acetylacetonate ion, and X-py = pyridine (I) or pyridine derivative; 4-Me-py (II), 3-OH-py (III), and 3-Me-py (IV). The photoactivity of (I) in the solid state had been reported based on the infrared spectra while irradiated with a high-pressure mercury arc, a remarkable increase in absorption in the region 1000–1050 cm−1 being detected (Johnson & Martin, 1969 ▸). This is due to the symmetric N—O stretching mode of the nitrito form, and it corresponds to 1055 cm−1 for [Co(NH3)5ONO]Cl2 (Heyns & de Waal, 1989 ▸).
When the IR spectra were measured after irradiation for 30 min to the KBr disks containing each complex by a 150 W Xe lamp without filtering, those of py (I) and 4-Me-py (II) showed an apparent increase of an absorption peak at 1051 and 1025 cm−1, respectively (see the figure in the supporting information), and the spectra reverted to those before irradiation on standing at room temperature for ca 16 h. The changing color of the KBr disks by photoirradiation was ambiguous, which might be due to the dark-red color of the crystals. On the other hand, the 3-OH-py (III) and 3-Me-py (IV) complexes were photo-stable and did not show the change in IR spectra by irradiation. In the present study, the crystal structures of (I)–(III) have been determined to reveal the differences in the circumstances of the nitro ligand. The structure of (IV) was reported previously (Miyazaki et al., 1998 ▸).
Structural commentary
The molecular structures of (I)–(III) are shown in Figs. 1 ▸–3 ▸ ▸, respectively. In these crystals, the complex has crystallographic mirror symmetry, and the py/4-Me-py/3-OH-py ligands and the cobalt atom lie on a mirror plane. The nitro group also lies on the mirror plane in (I) and (II). However, in (III) the nitro group shows positional disorder, and the major component [O4—N8—O4i, 67.2 (16)%] is oriented perpendicular to the mirror plane. The minor component [O5A—N8—O5B, 16.4 (8)%] and the water molecule (O7) are disordered near the mirror. The Co—N(nitro) bond distances are 1.923 (9) Å in (I), 1.949 (10) Å in (II) and 1.915 (3) Å in (III). In each case, a distorted trans-CoN2O4 octahedral coordination polyhedron arises.
Figure 1.
The molecular structure of (I), showing displacement ellipsoids at the 30% probability level. Symmetry code: (i) x, −y + 1, z.
Figure 2.
The molecular structure of (II), showing displacement ellipsoids at the 30% probability level. Symmetry code: (i) x, −y + 1, z. One of the two set of H-atom positions of the C18 methyl group is omitted for clarity.
Figure 3.
The molecular structure of (III), showing displacement ellipsoids at the 30% probability level. Symmetry code: (i) x, −y + 
, z. The minor occupancy O5A/O5B atoms of the nitro group and one of two possible positions of the water molecule O7 are omitted for clarity.
Supramolecular features
The crystal structures of (I)–(III) are shown in Figs. 4 ▸–6 ▸ ▸, respectively. In (I) and (II), the molecules are connected by C—H⋯O hydrogen bonds (Tables 1–3 ▸ ▸ ▸), forming chains propagating along the a-axis direction. In (III), the complex molecules are connected via O—H⋯O hydrogen bonds involving the water molecules, forming layers lying parallel to (010).
Figure 4.
The crystal structure of (I), projected along c. The C—H⋯O hydrogen bonds are shown as blue dashed lines.
Figure 5.
The crystal structure of (II), projected along c. The C—H⋯O hydrogen bonds are shown as blue dashed lines.
Figure 6.
The crystal structure of (III), projected along c. The O—H⋯O hydrogen bonds are shown as blue dashed lines. The minor occupancy O5A/O5B atoms of the nitro group and one of two possible positions of the water molecule O7 are omitted for clarity.
Table 1. Hydrogen-bond geometry (Å, °) for (I) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C14—H14⋯O4ii | 0.93 | 2.47 | 3.150 (11) | 130 |
Symmetry code: (ii) 
.
Table 2. Hydrogen-bond geometry (Å, °) for (II) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C14—H14⋯O4ii | 0.93 | 2.39 | 3.104 (10) | 133 |
Symmetry code: (ii) .
Table 3. Hydrogen-bond geometry (Å, °) for (III) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O6—H6⋯O7 | 0.84 (2) | 1.77 (2) | 2.593 (4) | 166 (3) |
| O6—H6⋯O7i | 0.84 (2) | 1.77 (2) | 2.593 (4) | 166 (3) |
| O7—H7A⋯O2ii | 0.83 (2) | 2.15 (3) | 2.962 (4) | 165 (8) |
| O7—H7B⋯O3iii | 0.83 (2) | 2.23 (3) | 3.030 (5) | 164 (8) |
| C10—H10C⋯O4iv | 0.96 | 2.53 | 3.446 (5) | 161 |
| C19—H19⋯O5A iv | 0.93 | 2.49 | 3.413 (11) | 171 |
| C19—H19⋯O5A v | 0.93 | 2.49 | 3.413 (11) | 171 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
.
Slices of the reaction cavities around the nitro group near its plane in (I)–(IV) are compared in Fig. 7 ▸, where the radii of the neighboring atoms are assumed to be 1.0 Å greater than the corresponding van der Waals radii (Bondi, 1964 ▸) except for Co, its radius being set to 1.90 Å. The intermolecular contacts that define the shape of cavity of NO2 − in its place in (I)–(IV) are shown in Figs. 8 ▸–11 ▸ ▸ ▸, respectively, where the C—H⋯O hydrogen bonds are shown as blue dashed lines (the O⋯H distances being in the range from 2.39 to 2.53 Å), and other O⋯H contacts of less than 2.8 Å are shown as green dashed lines. The cavities in the photo-stable crystals of (III) and (IV) are thinner than those in the photo-active ones (I) and (II), where it seems that there are no close contacts that prevents the linkage isomerization (Figs. 8 ▸ and 9 ▸). The narrow cavities in (III) and (IV) are due to the bifurcated intermolecular C—H(py)⋯O,O(nitro) contacts as seen in Figs. 10 ▸ and 11 ▸. On the extension of the Co–N(nitro) bond axis, there is a neighboring pyridine ring perpendicular to the nitro plane, suggesting that this ring will block the rotation of NO2 − to become a nitrito form.
Figure 7.
Comparison of the slices of the cavity around the nitro group within 0.1 Å from the plane in (I)–(IV). Symmetry code for (III) (i) x, −y + , z; for (IV): (i) x, −y + 
, z.
Figure 8.
The steric circumstance of the nitro group in (I). Only parts of the complex are shown for clarity. The C—H⋯O hydrogen bonds are shown as blue dashed lines. The green dashed lines indicate other O⋯H contacts shorter than 2.8 Å, O5⋯H15iv=2.73 Å. Symmetry codes: (i) x, −y + 1, z; (ii) x + 1, y, z; (iii) x − 1, y, z; (iv) x − 1, y, z − 1; (v) x − 1, −y + 1, z.
Figure 9.
The steric circumstance of the nitro group in (II). Only parts of the complex are shown for clarity. The C—H⋯O hydrogen bonds are shown as blue dashed lines. The green dashed lines indicate other O⋯H contacts shorter than 2.8 Å. Symmetry codes: (i) x, −y + 1, z; (ii) x + 1, y, z; (iii) x − 1, y, z; (iv) x, y, z + 1; (v) x − 1, y, z + 1; (vi) x − 1, −y + 1, z.
Figure 10.
The steric circumstance of the nitro group in (III). Only parts of the complex are shown for clarity. The C—H⋯O hydrogen bonds are shown as blue dashed lines, O4⋯H10C
vii = 2.53 Å. The green dashed lines indicate the other O⋯H contacts, O4⋯H19vi = 2.71 Å. Symmetry codes: (i) x, −y + , z; (ii) x, −y + , z + 1; (iii) x + , −y + , −z + ; (iv) x + , y, −z + ; (v) x + , −y + , −z + ; (vi) x − , −y + , −z + ; (vii) x − , y, − z.
Figure 11.
The steric circumstance of the nitro group in (IV). Only parts of the complexes are shown for clarity. The C—H⋯O hydrogen bonds are shown as blue dashed lines, O4⋯H11A
iv = 2.41 Å. The green dashed lines indicate the other O⋯H contacts, O4⋯H16iii = 2.69 Å. Symmetry codes: (i) x, −y + , z; (ii) −x + , −y, z + ; (iii) x + , y, −z + ; (iv) −x + , y − , z + .
Database survey
There are two entries of trans-[Co(acac)2(NO2)(X-py)] in the Cambridge Structural Database (CSD Version 5.39; Groom et al., 2016 ▸), the pyridine derivative being 3-methylpyridine (Miyazaki et al., 1998 ▸), and 4,4,5,5-tetramethyl-2-(3-pyridyl)imidazolin-1-oxyl radical (Ogita et al., 2002 ▸). Entries for the other related compounds include trans-[Co(acac)2(NO2)(2-aminopyrimidine)] (Kistenmacher et al., 1978 ▸), trans-[Co(acac)2(NO2)(H2O)] (Englert & Strähle, 1987 ▸), and trans-[Co(acac)2(4-methylpyridine)2]PF6 (Tayyari et al., 2015 ▸), for which theoretical assignments of the IR bands were presented.
Synthesis and crystallization
The title compounds were prepared according to the method of Boucher & Bailar (1965 ▸) from Na[Co(acac)2(NO2)2] and the appropriate pyridine derivative. Dark-red plates of (I), dark-red prisms of (II) and dark-red needles of (III) were grown from acetonitrile, nitromethane and methanol solutions, respectively.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. The H atoms bound to C were positioned geometrically, the methyl H atoms being introduced by an HFIX 137 command. They were refined as riding, with C—H = 0.93–0.96 Å, and U iso(H) = 1.2U eq(C) or 1.5U eq(Cmethyl). (I): two reflections showing poor agreement with I obs much smaller than I calc were omitted from the final refinement. (II): one reflection showing poor agreement was omitted. The DELU instruction was applied to C15 and C18 to avoid the 10 s.u. of the Hirshfeld test difference. (III): six reflections showing poor agreement were omitted. The minor occupancy nitro atoms O5A and O5B were refined anisotropically with an ISOR instruction. The H atoms bound to O were positioned from difference density maps, and their positional parameters were refined with the geometry restrained and with U iso(H) = 1.5U eq(O). Compounds (I) and (II) were refined as inversion twins.
Table 4. Experimental details.
| (I) | (II) | (III) | |
|---|---|---|---|
| Crystal data | |||
| Chemical formula | [Co(C5H7O2)2(NO2)(C5H5N)] | [Co(C5H7O2)2(NO2)(C6H7N)] | [Co(C5H7O2)2(NO2)(C5H5NO)]·H2O |
| M r | 382.25 | 396.28 | 416.27 |
| Crystal system, space group | Monoclinic, C m | Monoclinic, C m | Orthorhombic, P n m a |
| Temperature (K) | 301 | 301 | 301 |
| a, b, c (Å) | 8.1971 (14), 13.942 (2), 7.4148 (11) | 8.2459 (9), 13.9603 (14), 7.9222 (8) | 12.3811 (4), 14.0483 (5), 10.6443 (3) |
| α, β, γ (°) | 90, 91.588 (6), 90 | 90, 96.997 (4), 90 | 90, 90, 90 |
| V (Å3) | 847.1 (2) | 905.17 (16) | 1851.40 (10) |
| Z | 2 | 2 | 4 |
| Radiation type | Mo Kα | Mo Kα | Mo Kα |
| μ (mm−1) | 1.05 | 0.98 | 0.97 |
| Crystal size (mm) | 0.31 × 0.27 × 0.13 | 0.35 × 0.15 × 0.15 | 0.35 × 0.11 × 0.08 |
| Data collection | |||
| Diffractometer | Bruker D8 VENTURE | Bruker D8 VENTURE | Bruker D8 VENTURE |
| Absorption correction | Integration (SADABS; Bruker, 2016 ▸) | Integration (SADABS; Bruker, 2016 ▸) | Integration (SADABS; Bruker, 2016 ▸) |
| T min, T max | 0.731, 0.886 | 0.749, 0.895 | 0.780, 0.938 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3958, 1529, 1449 | 4495, 1810, 1754 | 19560, 2292, 1887 |
| R int | 0.024 | 0.021 | 0.032 |
| (sin θ/λ)max (Å−1) | 0.659 | 0.660 | 0.660 |
| Refinement | |||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.040, 0.083, 1.12 | 0.031, 0.074, 1.13 | 0.032, 0.087, 1.10 |
| No. of reflections | 1529 | 1810 | 2292 |
| No. of parameters | 128 | 134 | 165 |
| No. of restraints | 2 | 3 | 16 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.32, −0.34 | 0.35, −0.37 | 0.46, −0.46 |
| Absolute structure | Refined as an inversion twin | Refined as an inversion twin | – |
| Absolute structure parameter | 0.41 (3) | 0.37 (3) | – |
Supplementary Material
Crystal structure: contains datablock(s) I, II, III, general. DOI: 10.1107/S2056989018014731/hb7778sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018014731/hb7778Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018014731/hb7778Isup5.cdx
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989018014731/hb7778IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989018014731/hb7778IIsup6.cdx
Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989018014731/hb7778IIIsup4.hkl
Supporting information file. DOI: 10.1107/S2056989018014731/hb7778IIIsup8.cdx
The IR spectra of py (I) and 4-Me-py (II) compounds before and after photoirradiation for 30 min by a 150 W Xe lamp to the KBr disks.. DOI: 10.1107/S2056989018014731/hb7778sup9.tif
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank Dr Takashi Nemoto, Kyoto University, for making the program CAVITY available to the public.
supplementary crystallographic information
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Crystal data
| [Co(C5H7O2)2(NO2)(C5H5N)] | F(000) = 396 |
| Mr = 382.25 | Dx = 1.499 Mg m−3 |
| Monoclinic, Cm | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.1971 (14) Å | Cell parameters from 2813 reflections |
| b = 13.942 (2) Å | θ = 2.8–27.4° |
| c = 7.4148 (11) Å | µ = 1.05 mm−1 |
| β = 91.588 (6)° | T = 301 K |
| V = 847.1 (2) Å3 | Plate, dark red |
| Z = 2 | 0.31 × 0.27 × 0.13 mm |
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Data collection
| Bruker D8 VENTURE diffractometer | 1449 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.024 |
| Absorption correction: integration (SADABS; Bruker, 2016) | θmax = 27.9°, θmin = 2.8° |
| Tmin = 0.731, Tmax = 0.886 | h = −8→10 |
| 3958 measured reflections | k = −17→18 |
| 1529 independent reflections | l = −8→9 |
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Refinement
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0237P)2 + 1.1288P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.040 | (Δ/σ)max = 0.013 |
| wR(F2) = 0.083 | Δρmax = 0.32 e Å−3 |
| S = 1.12 | Δρmin = −0.34 e Å−3 |
| 1529 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 128 parameters | Extinction coefficient: 0.0076 (16) |
| 2 restraints | Absolute structure: Refined as an inversion twin |
| Hydrogen site location: inferred from neighbouring sites | Absolute structure parameter: 0.41 (3) |
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
| Refinement. Refined as a 2-component inversion twin. |
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Co1 | 0.42186 (18) | 0.5000 | 0.42933 (17) | 0.0438 (3) | |
| O2 | 0.3213 (6) | 0.5899 (5) | 0.5783 (6) | 0.0519 (15) | |
| O3 | 0.5237 (6) | 0.5919 (5) | 0.2843 (6) | 0.0510 (15) | |
| O4 | 0.1030 (10) | 0.5000 | 0.3107 (12) | 0.109 (4) | |
| O5 | 0.2595 (11) | 0.5000 | 0.1013 (12) | 0.124 (4) | |
| N6 | 0.2370 (11) | 0.5000 | 0.2638 (11) | 0.052 (2) | |
| N7 | 0.6127 (10) | 0.5000 | 0.6056 (11) | 0.046 (2) | |
| C8 | 0.2472 (10) | 0.7342 (6) | 0.7050 (8) | 0.068 (2) | |
| H8A | 0.1347 | 0.7153 | 0.7085 | 0.103* | |
| H8B | 0.2537 | 0.8018 | 0.6813 | 0.103* | |
| H8C | 0.3003 | 0.7203 | 0.8191 | 0.103* | |
| C9 | 0.3290 (9) | 0.6804 (7) | 0.5596 (9) | 0.050 (2) | |
| C10 | 0.4051 (12) | 0.7261 (3) | 0.4179 (11) | 0.0578 (14) | |
| H10 | 0.3946 | 0.7924 | 0.4090 | 0.069* | |
| C11 | 0.4946 (9) | 0.6800 (7) | 0.2902 (9) | 0.0476 (19) | |
| C12 | 0.5655 (11) | 0.7380 (7) | 0.1361 (9) | 0.072 (2) | |
| H12A | 0.6120 | 0.6952 | 0.0502 | 0.107* | |
| H12B | 0.6485 | 0.7803 | 0.1834 | 0.107* | |
| H12C | 0.4803 | 0.7750 | 0.0780 | 0.107* | |
| C13 | 0.7701 (12) | 0.5000 | 0.5474 (12) | 0.0441 (18) | |
| H13 | 0.7884 | 0.5000 | 0.4242 | 0.053* | |
| C14 | 0.8993 (9) | 0.5000 | 0.6648 (10) | 0.0560 (17) | |
| H14 | 1.0050 | 0.5000 | 0.6224 | 0.067* | |
| C15 | 0.8733 (10) | 0.5000 | 0.8481 (10) | 0.0607 (18) | |
| H15 | 0.9607 | 0.5000 | 0.9308 | 0.073* | |
| C16 | 0.7142 (10) | 0.5000 | 0.9055 (9) | 0.0577 (18) | |
| H16 | 0.6931 | 0.5000 | 1.0281 | 0.069* | |
| C17 | 0.5893 (11) | 0.5000 | 0.7818 (11) | 0.049 (2) | |
| H17 | 0.4829 | 0.5000 | 0.8222 | 0.059* |
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0433 (4) | 0.0486 (4) | 0.0404 (4) | 0.000 | 0.0172 (3) | 0.000 |
| O2 | 0.054 (4) | 0.058 (4) | 0.044 (3) | 0.006 (3) | 0.017 (3) | −0.001 (3) |
| O3 | 0.056 (4) | 0.052 (4) | 0.046 (3) | −0.004 (3) | 0.021 (3) | 0.008 (3) |
| O4 | 0.040 (4) | 0.212 (10) | 0.076 (5) | 0.000 | 0.012 (4) | 0.000 |
| O5 | 0.075 (6) | 0.242 (12) | 0.056 (5) | 0.000 | −0.006 (4) | 0.000 |
| N6 | 0.055 (6) | 0.066 (6) | 0.035 (4) | 0.000 | 0.017 (4) | 0.000 |
| N7 | 0.043 (5) | 0.051 (5) | 0.045 (4) | 0.000 | 0.010 (3) | 0.000 |
| C8 | 0.083 (5) | 0.072 (5) | 0.050 (4) | 0.021 (4) | −0.008 (3) | −0.020 (4) |
| C9 | 0.040 (4) | 0.062 (5) | 0.047 (4) | 0.009 (3) | −0.006 (3) | −0.004 (3) |
| C10 | 0.071 (4) | 0.048 (2) | 0.054 (3) | −0.002 (4) | −0.002 (3) | 0.005 (4) |
| C11 | 0.051 (4) | 0.051 (4) | 0.040 (3) | −0.013 (3) | −0.005 (3) | 0.013 (3) |
| C12 | 0.070 (5) | 0.083 (6) | 0.062 (4) | −0.020 (4) | 0.007 (4) | 0.019 (4) |
| C13 | 0.048 (5) | 0.044 (4) | 0.041 (4) | 0.000 | 0.021 (3) | 0.000 |
| C14 | 0.044 (4) | 0.064 (4) | 0.061 (4) | 0.000 | 0.012 (3) | 0.000 |
| C15 | 0.065 (5) | 0.061 (4) | 0.055 (4) | 0.000 | −0.004 (4) | 0.000 |
| C16 | 0.070 (5) | 0.068 (5) | 0.035 (3) | 0.000 | 0.009 (3) | 0.000 |
| C17 | 0.055 (5) | 0.056 (4) | 0.039 (4) | 0.000 | 0.029 (4) | 0.000 |
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Geometric parameters (Å, º)
| Co1—O2i | 1.877 (5) | C9—C10 | 1.392 (11) |
| Co1—O2 | 1.877 (5) | C10—C11 | 1.374 (12) |
| Co1—O3 | 1.883 (6) | C10—H10 | 0.9300 |
| Co1—O3i | 1.883 (6) | C11—C12 | 1.527 (9) |
| Co1—N6 | 1.923 (9) | C12—H12A | 0.9600 |
| Co1—N7 | 2.010 (8) | C12—H12B | 0.9600 |
| O2—C9 | 1.270 (10) | C12—H12C | 0.9600 |
| O3—C11 | 1.252 (10) | C13—C14 | 1.352 (12) |
| O4—N6 | 1.162 (11) | C13—H13 | 0.9300 |
| O5—N6 | 1.224 (12) | C14—C15 | 1.381 (10) |
| N7—C17 | 1.325 (11) | C14—H14 | 0.9300 |
| N7—C13 | 1.372 (12) | C15—C16 | 1.383 (10) |
| C8—C9 | 1.489 (10) | C15—H15 | 0.9300 |
| C8—H8A | 0.9600 | C16—C17 | 1.356 (12) |
| C8—H8B | 0.9600 | C16—H16 | 0.9300 |
| C8—H8C | 0.9600 | C17—H17 | 0.9300 |
| O2i—Co1—O2 | 83.8 (4) | O2—C9—C8 | 113.4 (8) |
| O2i—Co1—O3 | 178.7 (3) | C10—C9—C8 | 122.4 (9) |
| O2—Co1—O3 | 95.18 (10) | C11—C10—C9 | 124.4 (4) |
| O2i—Co1—O3i | 95.18 (10) | C11—C10—H10 | 117.8 |
| O2—Co1—O3i | 178.7 (3) | C9—C10—H10 | 117.8 |
| O3—Co1—O3i | 85.8 (4) | O3—C11—C10 | 126.1 (7) |
| O2i—Co1—N6 | 91.4 (3) | O3—C11—C12 | 114.6 (8) |
| O2—Co1—N6 | 91.4 (3) | C10—C11—C12 | 119.3 (8) |
| O3—Co1—N6 | 89.4 (2) | C11—C12—H12A | 109.5 |
| O3i—Co1—N6 | 89.4 (2) | C11—C12—H12B | 109.5 |
| O2i—Co1—N7 | 87.9 (2) | H12A—C12—H12B | 109.5 |
| O2—Co1—N7 | 87.9 (2) | C11—C12—H12C | 109.5 |
| O3—Co1—N7 | 91.3 (3) | H12A—C12—H12C | 109.5 |
| O3i—Co1—N7 | 91.3 (3) | H12B—C12—H12C | 109.5 |
| N6—Co1—N7 | 179.1 (5) | C14—C13—N7 | 121.6 (8) |
| C9—O2—Co1 | 125.1 (6) | C14—C13—H13 | 119.2 |
| C11—O3—Co1 | 124.1 (6) | N7—C13—H13 | 119.2 |
| O4—N6—O5 | 117.7 (10) | C13—C14—C15 | 119.6 (7) |
| O4—N6—Co1 | 122.9 (8) | C13—C14—H14 | 120.2 |
| O5—N6—Co1 | 119.4 (8) | C15—C14—H14 | 120.2 |
| C17—N7—C13 | 118.2 (8) | C16—C15—C14 | 118.4 (7) |
| C17—N7—Co1 | 120.7 (7) | C16—C15—H15 | 120.8 |
| C13—N7—Co1 | 121.1 (7) | C14—C15—H15 | 120.8 |
| C9—C8—H8A | 109.5 | C17—C16—C15 | 119.5 (6) |
| C9—C8—H8B | 109.5 | C17—C16—H16 | 120.2 |
| H8A—C8—H8B | 109.5 | C15—C16—H16 | 120.2 |
| C9—C8—H8C | 109.5 | N7—C17—C16 | 122.7 (8) |
| H8A—C8—H8C | 109.5 | N7—C17—H17 | 118.7 |
| H8B—C8—H8C | 109.5 | C16—C17—H17 | 118.7 |
| O2—C9—C10 | 124.2 (8) | ||
| O2i—Co1—O2—C9 | −178.3 (4) | Co1—O3—C11—C10 | 10.4 (11) |
| O3—Co1—O2—C9 | 2.5 (6) | Co1—O3—C11—C12 | −168.5 (5) |
| N6—Co1—O2—C9 | −87.0 (6) | C9—C10—C11—O3 | −1.6 (15) |
| N7—Co1—O2—C9 | 93.6 (6) | C9—C10—C11—C12 | 177.2 (7) |
| O2—Co1—O3—C11 | −9.7 (6) | C17—N7—C13—C14 | 0.000 (2) |
| O3i—Co1—O3—C11 | 171.1 (4) | Co1—N7—C13—C14 | 180.000 (1) |
| N6—Co1—O3—C11 | 81.7 (6) | N7—C13—C14—C15 | 0.000 (2) |
| N7—Co1—O3—C11 | −97.7 (6) | C13—C14—C15—C16 | 0.000 (2) |
| Co1—O2—C9—C10 | 4.4 (10) | C14—C15—C16—C17 | 0.000 (2) |
| Co1—O2—C9—C8 | −175.9 (4) | C13—N7—C17—C16 | 0.000 (2) |
| O2—C9—C10—C11 | −6.6 (14) | Co1—N7—C17—C16 | 180.000 (2) |
| C8—C9—C10—C11 | 173.8 (7) | C15—C16—C17—N7 | 0.000 (3) |
Symmetry code: (i) x, −y+1, z.
trans-Bis(acetylacetonato-κ2O,O')(nitro)(pyridine-κN)cobalt(III) (I) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C14—H14···O4ii | 0.93 | 2.47 | 3.150 (11) | 130 |
Symmetry code: (ii) x+1, y, z.
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Crystal data
| [Co(C5H7O2)2(NO2)(C6H7N)] | F(000) = 412 |
| Mr = 396.28 | Dx = 1.454 Mg m−3 |
| Monoclinic, Cm | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.2459 (9) Å | Cell parameters from 4544 reflections |
| b = 13.9603 (14) Å | θ = 2.5–27.8° |
| c = 7.9222 (8) Å | µ = 0.98 mm−1 |
| β = 96.997 (4)° | T = 301 K |
| V = 905.17 (16) Å3 | Prism, dark red |
| Z = 2 | 0.35 × 0.15 × 0.15 mm |
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Data collection
| Bruker D8 VENTURE diffractometer | 1754 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.021 |
| Absorption correction: integration (SADABS; Bruker, 2016) | θmax = 28.0°, θmin = 2.9° |
| Tmin = 0.749, Tmax = 0.895 | h = −10→8 |
| 4495 measured reflections | k = −17→18 |
| 1810 independent reflections | l = −9→10 |
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0113P)2 + 1.2247P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
| S = 1.13 | Δρmax = 0.35 e Å−3 |
| 1810 reflections | Δρmin = −0.37 e Å−3 |
| 134 parameters | Absolute structure: Refined as an inversion twin |
| 3 restraints | Absolute structure parameter: 0.37 (3) |
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
| Refinement. Refined as a 2-component inversion twin. |
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Co1 | 0.42176 (19) | 0.5000 | 0.52127 (18) | 0.03463 (18) | |
| O2 | 0.3036 (5) | 0.5901 (4) | 0.3806 (5) | 0.0400 (12) | |
| O3 | 0.5407 (5) | 0.5913 (4) | 0.6616 (5) | 0.0439 (13) | |
| O4 | 0.1207 (11) | 0.5000 | 0.6291 (11) | 0.125 (4) | |
| O5 | 0.2965 (10) | 0.5000 | 0.8253 (10) | 0.125 (4) | |
| N6 | 0.2587 (12) | 0.5000 | 0.6799 (11) | 0.048 (2) | |
| N7 | 0.5891 (9) | 0.5000 | 0.3642 (10) | 0.0330 (18) | |
| C8 | 0.2352 (11) | 0.7359 (5) | 0.2501 (9) | 0.065 (3) | |
| H8A | 0.3087 | 0.7499 | 0.1683 | 0.097* | |
| H8B | 0.1957 | 0.7946 | 0.2930 | 0.097* | |
| H8C | 0.1447 | 0.6991 | 0.1968 | 0.097* | |
| C9 | 0.3220 (9) | 0.6804 (6) | 0.3917 (9) | 0.043 (2) | |
| C10 | 0.4208 (15) | 0.7268 (2) | 0.5206 (12) | 0.0577 (10) | |
| H10 | 0.4215 | 0.7934 | 0.5206 | 0.069* | |
| C11 | 0.5191 (9) | 0.6796 (6) | 0.6500 (9) | 0.046 (2) | |
| C12 | 0.6150 (13) | 0.7373 (6) | 0.7949 (8) | 0.072 (3) | |
| H12A | 0.5936 | 0.7117 | 0.9024 | 0.108* | |
| H12B | 0.5813 | 0.8032 | 0.7868 | 0.108* | |
| H12C | 0.7298 | 0.7331 | 0.7857 | 0.108* | |
| C13 | 0.7505 (10) | 0.5000 | 0.4153 (10) | 0.0363 (16) | |
| H13 | 0.7851 | 0.5000 | 0.5315 | 0.044* | |
| C14 | 0.8686 (8) | 0.5000 | 0.3045 (8) | 0.0468 (14) | |
| H14 | 0.9787 | 0.5000 | 0.3475 | 0.056* | |
| C15 | 0.8232 (8) | 0.5000 | 0.1291 (8) | 0.0463 (14) | |
| C16 | 0.6569 (8) | 0.5000 | 0.0745 (7) | 0.0450 (14) | |
| H16 | 0.6209 | 0.5000 | −0.0414 | 0.054* | |
| C17 | 0.5439 (10) | 0.5000 | 0.1900 (10) | 0.0393 (17) | |
| H17 | 0.4333 | 0.5000 | 0.1491 | 0.047* | |
| C18 | 0.9477 (16) | 0.5000 | 0.0121 (19) | 0.078 (3) | |
| H18A | 0.9079 | 0.5349 | −0.0889 | 0.117* | 0.5 |
| H18B | 0.9714 | 0.4352 | −0.0174 | 0.117* | 0.5 |
| H18C | 1.0454 | 0.5299 | 0.0660 | 0.117* | 0.5 |
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0384 (4) | 0.0391 (3) | 0.0248 (3) | 0.000 | −0.0026 (2) | 0.000 |
| O2 | 0.045 (3) | 0.041 (3) | 0.033 (3) | 0.005 (2) | −0.001 (2) | 0.001 (3) |
| O3 | 0.047 (3) | 0.049 (3) | 0.032 (3) | −0.002 (3) | −0.010 (2) | −0.007 (3) |
| O4 | 0.059 (5) | 0.261 (12) | 0.056 (5) | 0.000 | 0.015 (4) | 0.000 |
| O5 | 0.066 (6) | 0.271 (12) | 0.039 (4) | 0.000 | 0.009 (4) | 0.000 |
| N6 | 0.056 (6) | 0.057 (6) | 0.029 (5) | 0.000 | −0.002 (4) | 0.000 |
| N7 | 0.021 (4) | 0.044 (4) | 0.033 (5) | 0.000 | −0.001 (3) | 0.000 |
| C8 | 0.072 (6) | 0.053 (5) | 0.065 (5) | 0.009 (4) | −0.015 (5) | 0.013 (5) |
| C9 | 0.052 (5) | 0.044 (5) | 0.034 (4) | 0.009 (3) | 0.005 (4) | 0.001 (3) |
| C10 | 0.080 (3) | 0.0389 (17) | 0.051 (2) | −0.007 (6) | −0.0049 (18) | 0.005 (6) |
| C11 | 0.053 (5) | 0.049 (5) | 0.037 (4) | −0.008 (3) | 0.008 (4) | −0.013 (3) |
| C12 | 0.104 (7) | 0.068 (5) | 0.042 (5) | −0.021 (6) | 0.002 (5) | −0.023 (5) |
| C13 | 0.026 (3) | 0.047 (3) | 0.031 (4) | 0.000 | −0.014 (3) | 0.000 |
| C14 | 0.043 (4) | 0.050 (3) | 0.047 (4) | 0.000 | 0.002 (3) | 0.000 |
| C15 | 0.055 (4) | 0.043 (3) | 0.041 (4) | 0.000 | 0.007 (3) | 0.000 |
| C16 | 0.055 (4) | 0.055 (3) | 0.026 (3) | 0.000 | 0.004 (3) | 0.000 |
| C17 | 0.040 (4) | 0.052 (4) | 0.024 (3) | 0.000 | −0.007 (3) | 0.000 |
| C18 | 0.073 (8) | 0.098 (5) | 0.064 (5) | 0.000 | 0.012 (4) | 0.000 |
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Geometric parameters (Å, º)
| Co1—O2 | 1.874 (5) | C10—H10 | 0.9300 |
| Co1—O2i | 1.874 (5) | C11—C12 | 1.539 (9) |
| Co1—O3 | 1.886 (5) | C12—H12A | 0.9600 |
| Co1—O3i | 1.886 (5) | C12—H12B | 0.9600 |
| Co1—N6 | 1.949 (10) | C12—H12C | 0.9600 |
| Co1—N7 | 1.968 (8) | C13—C14 | 1.388 (11) |
| O2—C9 | 1.271 (8) | C13—H13 | 0.9300 |
| O3—C11 | 1.248 (9) | C14—C15 | 1.394 (9) |
| O4—N6 | 1.160 (12) | C14—H14 | 0.9300 |
| O5—N6 | 1.156 (11) | C15—C16 | 1.387 (9) |
| N7—C13 | 1.343 (10) | C15—C18 | 1.464 (14) |
| N7—C17 | 1.385 (10) | C16—C17 | 1.383 (11) |
| C8—C9 | 1.475 (10) | C16—H16 | 0.9300 |
| C8—H8A | 0.9600 | C17—H17 | 0.9300 |
| C8—H8B | 0.9600 | C18—H18A | 0.9600 |
| C8—H8C | 0.9600 | C18—H18B | 0.9600 |
| C9—C10 | 1.387 (11) | C18—H18C | 0.9600 |
| C10—C11 | 1.392 (11) | ||
| O2—Co1—O2i | 84.4 (3) | C9—C10—H10 | 118.0 |
| O2—Co1—O3 | 95.28 (9) | C11—C10—H10 | 118.0 |
| O2i—Co1—O3 | 179.6 (3) | O3—C11—C10 | 125.9 (7) |
| O2—Co1—O3i | 179.6 (3) | O3—C11—C12 | 114.0 (7) |
| O2i—Co1—O3i | 95.29 (9) | C10—C11—C12 | 120.1 (8) |
| O3—Co1—O3i | 85.0 (3) | C11—C12—H12A | 109.5 |
| O2—Co1—N6 | 91.9 (3) | C11—C12—H12B | 109.5 |
| O2i—Co1—N6 | 91.9 (3) | H12A—C12—H12B | 109.5 |
| O3—Co1—N6 | 88.3 (2) | C11—C12—H12C | 109.5 |
| O3i—Co1—N6 | 88.3 (2) | H12A—C12—H12C | 109.5 |
| O2—Co1—N7 | 88.7 (2) | H12B—C12—H12C | 109.5 |
| O2i—Co1—N7 | 88.7 (2) | N7—C13—C14 | 123.7 (7) |
| O3—Co1—N7 | 91.1 (2) | N7—C13—H13 | 118.1 |
| O3i—Co1—N7 | 91.1 (2) | C14—C13—H13 | 118.1 |
| N6—Co1—N7 | 179.1 (5) | C13—C14—C15 | 120.4 (6) |
| C9—O2—Co1 | 125.1 (5) | C13—C14—H14 | 119.8 |
| C11—O3—Co1 | 124.4 (5) | C15—C14—H14 | 119.8 |
| O5—N6—O4 | 118.7 (11) | C16—C15—C14 | 116.5 (6) |
| O5—N6—Co1 | 121.2 (9) | C16—C15—C18 | 123.1 (8) |
| O4—N6—Co1 | 120.1 (8) | C14—C15—C18 | 120.5 (8) |
| C13—N7—C17 | 115.9 (8) | C17—C16—C15 | 120.9 (6) |
| C13—N7—Co1 | 123.7 (7) | C17—C16—H16 | 119.5 |
| C17—N7—Co1 | 120.4 (6) | C15—C16—H16 | 119.5 |
| C9—C8—H8A | 109.5 | C16—C17—N7 | 122.5 (7) |
| C9—C8—H8B | 109.5 | C16—C17—H17 | 118.7 |
| H8A—C8—H8B | 109.5 | N7—C17—H17 | 118.7 |
| C9—C8—H8C | 109.5 | C15—C18—H18A | 109.5 |
| H8A—C8—H8C | 109.5 | C15—C18—H18B | 109.5 |
| H8B—C8—H8C | 109.5 | H18A—C18—H18B | 109.5 |
| O2—C9—C10 | 124.7 (7) | C15—C18—H18C | 109.5 |
| O2—C9—C8 | 115.1 (7) | H18A—C18—H18C | 109.5 |
| C10—C9—C8 | 120.2 (7) | H18B—C18—H18C | 109.5 |
| C9—C10—C11 | 123.9 (3) | ||
| O2i—Co1—O2—C9 | −176.7 (5) | Co1—O3—C11—C12 | 172.0 (5) |
| O3—Co1—O2—C9 | 3.1 (7) | C9—C10—C11—O3 | 5.3 (18) |
| N6—Co1—O2—C9 | 91.5 (6) | C9—C10—C11—C12 | −175.5 (9) |
| N7—Co1—O2—C9 | −87.9 (6) | C17—N7—C13—C14 | 0.000 (1) |
| O2—Co1—O3—C11 | 4.5 (7) | Co1—N7—C13—C14 | 180.000 (1) |
| O3i—Co1—O3—C11 | −175.7 (5) | N7—C13—C14—C15 | 0.000 (1) |
| N6—Co1—O3—C11 | −87.3 (6) | C13—C14—C15—C16 | 0.000 (1) |
| N7—Co1—O3—C11 | 93.3 (6) | C13—C14—C15—C18 | 180.000 (1) |
| Co1—O2—C9—C10 | −6.9 (12) | C14—C15—C16—C17 | 0.000 (1) |
| Co1—O2—C9—C8 | 170.3 (5) | C18—C15—C16—C17 | 180.000 (1) |
| O2—C9—C10—C11 | 3.4 (18) | C15—C16—C17—N7 | 0.000 (1) |
| C8—C9—C10—C11 | −173.6 (8) | C13—N7—C17—C16 | 0.000 (1) |
| Co1—O3—C11—C10 | −8.8 (12) | Co1—N7—C17—C16 | 180.000 (1) |
Symmetry code: (i) x, −y+1, z.
trans-Bis(acetylacetonato-κ2O,O')(4-methylpyridine-κN)(nitro)cobalt(III) (II) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C14—H14···O4ii | 0.93 | 2.39 | 3.104 (10) | 133 |
Symmetry code: (ii) x+1, y, z.
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Crystal data
| [Co(C5H7O2)2(NO2)(C5H5NO)]·H2O | Dx = 1.493 Mg m−3 |
| Mr = 416.27 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pnma | Cell parameters from 9558 reflections |
| a = 12.3811 (4) Å | θ = 2.4–27.9° |
| b = 14.0483 (5) Å | µ = 0.97 mm−1 |
| c = 10.6443 (3) Å | T = 301 K |
| V = 1851.40 (10) Å3 | Needle, dark red |
| Z = 4 | 0.35 × 0.11 × 0.08 mm |
| F(000) = 864 |
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Data collection
| Bruker D8 VENTURE diffractometer | 1887 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.032 |
| Absorption correction: integration (SADABS; Bruker, 2016) | θmax = 28.0°, θmin = 2.5° |
| Tmin = 0.780, Tmax = 0.938 | h = −16→15 |
| 19560 measured reflections | k = −18→17 |
| 2292 independent reflections | l = −14→14 |
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Refinement
| Refinement on F2 | 16 restraints |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0204P)2 + 2.0145P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 2292 reflections | Δρmax = 0.46 e Å−3 |
| 165 parameters | Δρmin = −0.46 e Å−3 |
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Co1 | 0.35185 (3) | 0.7500 | 0.39108 (4) | 0.03386 (13) | |
| O2 | 0.44528 (12) | 0.66083 (11) | 0.31791 (14) | 0.0410 (3) | |
| O3 | 0.25897 (12) | 0.66025 (12) | 0.46516 (14) | 0.0439 (4) | |
| O4 | 0.2376 (4) | 0.6750 (2) | 0.1940 (3) | 0.076 (3) | 0.672 (16) |
| O5A | 0.1771 (13) | 0.7215 (16) | 0.2462 (12) | 0.078 (12) | 0.164 (8) |
| O5B | 0.3040 (13) | 0.7736 (15) | 0.1426 (10) | 0.076 (13) | 0.164 (8) |
| O6 | 0.4018 (2) | 0.7500 | 0.8767 (2) | 0.0756 (10) | |
| H6 | 0.446 (3) | 0.7500 | 0.936 (4) | 0.113* | |
| O7 | 0.5265 (3) | 0.7776 (6) | 1.0691 (3) | 0.088 (4) | 0.5 |
| H7A | 0.502 (5) | 0.784 (6) | 1.141 (3) | 0.132* | 0.5 |
| H7B | 0.5927 (18) | 0.785 (6) | 1.068 (6) | 0.132* | 0.5 |
| N8 | 0.2659 (2) | 0.7500 | 0.2415 (3) | 0.0440 (6) | |
| N9 | 0.44358 (19) | 0.7500 | 0.5455 (2) | 0.0359 (5) | |
| C10 | 0.5278 (2) | 0.5157 (2) | 0.2729 (3) | 0.0669 (8) | |
| H10A | 0.5146 | 0.5128 | 0.1841 | 0.100* | |
| H10B | 0.5295 | 0.4523 | 0.3067 | 0.100* | |
| H10C | 0.5960 | 0.5462 | 0.2880 | 0.100* | |
| C11 | 0.43951 (19) | 0.57141 (17) | 0.3353 (2) | 0.0454 (5) | |
| C12 | 0.3602 (2) | 0.52607 (18) | 0.4046 (3) | 0.0581 (7) | |
| H12 | 0.3649 | 0.4603 | 0.4123 | 0.070* | |
| C13 | 0.2749 (2) | 0.57064 (18) | 0.4630 (2) | 0.0493 (6) | |
| C14 | 0.1918 (3) | 0.5134 (2) | 0.5334 (3) | 0.0771 (9) | |
| H14A | 0.2089 | 0.5138 | 0.6214 | 0.116* | |
| H14B | 0.1920 | 0.4491 | 0.5030 | 0.116* | |
| H14C | 0.1217 | 0.5409 | 0.5208 | 0.116* | |
| C15 | 0.3987 (2) | 0.7500 | 0.6592 (3) | 0.0416 (7) | |
| H15 | 0.3237 | 0.7500 | 0.6647 | 0.050* | |
| C16 | 0.4571 (3) | 0.7500 | 0.7686 (3) | 0.0440 (7) | |
| C17 | 0.5695 (3) | 0.7500 | 0.7601 (3) | 0.0449 (7) | |
| H17 | 0.6122 | 0.7500 | 0.8320 | 0.054* | |
| C18 | 0.6153 (3) | 0.7500 | 0.6424 (3) | 0.0449 (7) | |
| H18 | 0.6901 | 0.7500 | 0.6343 | 0.054* | |
| C19 | 0.5519 (2) | 0.7500 | 0.5370 (3) | 0.0404 (7) | |
| H19 | 0.5843 | 0.7500 | 0.4581 | 0.048* |
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0317 (2) | 0.0381 (2) | 0.0318 (2) | 0.000 | 0.00176 (15) | 0.000 |
| O2 | 0.0397 (8) | 0.0418 (8) | 0.0415 (8) | 0.0026 (7) | 0.0031 (6) | −0.0036 (7) |
| O3 | 0.0383 (8) | 0.0528 (9) | 0.0407 (8) | −0.0074 (7) | 0.0028 (7) | 0.0044 (7) |
| O4 | 0.106 (6) | 0.0559 (19) | 0.066 (4) | −0.003 (2) | −0.039 (4) | −0.0118 (16) |
| O5A | 0.053 (7) | 0.15 (3) | 0.036 (5) | −0.045 (13) | −0.016 (5) | 0.009 (9) |
| O5B | 0.069 (8) | 0.12 (4) | 0.035 (5) | −0.040 (15) | 0.009 (5) | 0.023 (9) |
| O6 | 0.0423 (14) | 0.152 (3) | 0.0329 (13) | 0.000 | −0.0008 (11) | 0.000 |
| O7 | 0.0508 (19) | 0.175 (12) | 0.0375 (16) | −0.014 (3) | −0.0008 (14) | −0.015 (3) |
| N8 | 0.0380 (14) | 0.0506 (16) | 0.0434 (15) | 0.000 | −0.0011 (12) | 0.000 |
| N9 | 0.0311 (12) | 0.0414 (13) | 0.0352 (13) | 0.000 | −0.0007 (10) | 0.000 |
| C10 | 0.0668 (18) | 0.0595 (16) | 0.0743 (19) | 0.0186 (14) | −0.0060 (15) | −0.0180 (15) |
| C11 | 0.0503 (13) | 0.0424 (12) | 0.0435 (12) | 0.0061 (10) | −0.0125 (10) | −0.0060 (10) |
| C12 | 0.0725 (18) | 0.0372 (12) | 0.0645 (16) | −0.0016 (12) | −0.0020 (14) | 0.0066 (12) |
| C13 | 0.0523 (14) | 0.0518 (14) | 0.0437 (12) | −0.0124 (11) | −0.0083 (11) | 0.0127 (11) |
| C14 | 0.078 (2) | 0.079 (2) | 0.075 (2) | −0.0267 (17) | 0.0003 (17) | 0.0309 (17) |
| C15 | 0.0322 (14) | 0.0586 (19) | 0.0339 (15) | 0.000 | 0.0036 (12) | 0.000 |
| C16 | 0.0418 (17) | 0.060 (2) | 0.0299 (15) | 0.000 | 0.0006 (13) | 0.000 |
| C17 | 0.0380 (16) | 0.0575 (19) | 0.0391 (16) | 0.000 | −0.0096 (13) | 0.000 |
| C18 | 0.0296 (14) | 0.0544 (19) | 0.0507 (19) | 0.000 | −0.0025 (13) | 0.000 |
| C19 | 0.0332 (15) | 0.0466 (17) | 0.0414 (16) | 0.000 | 0.0032 (13) | 0.000 |
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Geometric parameters (Å, º)
| Co1—O2i | 1.8745 (15) | C10—H10A | 0.9600 |
| Co1—O2 | 1.8745 (15) | C10—H10B | 0.9600 |
| Co1—O3 | 1.8799 (15) | C10—H10C | 0.9600 |
| Co1—O3i | 1.8800 (15) | C11—C12 | 1.384 (4) |
| Co1—N8 | 1.915 (3) | C12—C13 | 1.376 (4) |
| Co1—N9 | 1.998 (2) | C12—H12 | 0.9300 |
| O2—C11 | 1.272 (3) | C13—C14 | 1.505 (3) |
| O3—C13 | 1.274 (3) | C14—H14A | 0.9600 |
| O4—N8 | 1.220 (3) | C14—H14B | 0.9600 |
| O5A—N8 | 1.172 (13) | C14—H14C | 0.9600 |
| O5B—N8 | 1.200 (13) | C15—C16 | 1.371 (4) |
| O6—C16 | 1.340 (4) | C15—H15 | 0.9300 |
| O6—H6 | 0.84 (2) | C16—C17 | 1.394 (4) |
| O7—H7A | 0.83 (2) | C17—C18 | 1.376 (5) |
| O7—H7B | 0.83 (2) | C17—H17 | 0.9300 |
| N8—O4i | 1.220 (3) | C18—C19 | 1.370 (4) |
| N9—C15 | 1.332 (4) | C18—H18 | 0.9300 |
| N9—C19 | 1.344 (4) | C19—H19 | 0.9300 |
| C10—C11 | 1.500 (3) | ||
| O2i—Co1—O2 | 83.87 (9) | H10A—C10—H10C | 109.5 |
| O2i—Co1—O3 | 179.59 (7) | H10B—C10—H10C | 109.5 |
| O2—Co1—O3 | 95.94 (7) | O2—C11—C12 | 124.9 (2) |
| O2i—Co1—O3i | 95.94 (7) | O2—C11—C10 | 114.2 (2) |
| O2—Co1—O3i | 179.59 (7) | C12—C11—C10 | 120.9 (2) |
| O3—Co1—O3i | 84.24 (10) | C13—C12—C11 | 125.2 (2) |
| O2i—Co1—N8 | 89.85 (8) | C13—C12—H12 | 117.4 |
| O2—Co1—N8 | 89.85 (8) | C11—C12—H12 | 117.4 |
| O3—Co1—N8 | 90.51 (8) | O3—C13—C12 | 125.2 (2) |
| O3i—Co1—N8 | 90.51 (8) | O3—C13—C14 | 114.4 (3) |
| O2i—Co1—N9 | 89.49 (7) | C12—C13—C14 | 120.4 (3) |
| O2—Co1—N9 | 89.49 (7) | C13—C14—H14A | 109.5 |
| O3—Co1—N9 | 90.14 (7) | C13—C14—H14B | 109.5 |
| O3i—Co1—N9 | 90.14 (7) | H14A—C14—H14B | 109.5 |
| N8—Co1—N9 | 179.12 (11) | C13—C14—H14C | 109.5 |
| C11—O2—Co1 | 124.40 (16) | H14A—C14—H14C | 109.5 |
| C13—O3—Co1 | 124.08 (16) | H14B—C14—H14C | 109.5 |
| C16—O6—H6 | 108 (4) | N9—C15—C16 | 123.4 (3) |
| H7A—O7—H7B | 111 (5) | N9—C15—H15 | 118.3 |
| O5A—N8—O5B | 120.1 (9) | C16—C15—H15 | 118.3 |
| O4—N8—O4i | 119.5 (4) | O6—C16—C15 | 117.4 (3) |
| O5A—N8—Co1 | 119.1 (6) | O6—C16—C17 | 124.4 (3) |
| O5B—N8—Co1 | 120.7 (7) | C15—C16—C17 | 118.2 (3) |
| O4—N8—Co1 | 120.26 (19) | C18—C17—C16 | 118.1 (3) |
| O4i—N8—Co1 | 120.26 (19) | C18—C17—H17 | 121.0 |
| C15—N9—C19 | 118.6 (3) | C16—C17—H17 | 121.0 |
| C15—N9—Co1 | 120.7 (2) | C19—C18—C17 | 120.6 (3) |
| C19—N9—Co1 | 120.7 (2) | C19—C18—H18 | 119.7 |
| C11—C10—H10A | 109.5 | C17—C18—H18 | 119.7 |
| C11—C10—H10B | 109.5 | N9—C19—C18 | 121.1 (3) |
| H10A—C10—H10B | 109.5 | N9—C19—H19 | 119.5 |
| C11—C10—H10C | 109.5 | C18—C19—H19 | 119.5 |
| O2i—Co1—O2—C11 | 173.79 (14) | Co1—O3—C13—C14 | 177.53 (16) |
| O3—Co1—O2—C11 | −5.84 (18) | C11—C12—C13—O3 | −2.6 (4) |
| N8—Co1—O2—C11 | −96.34 (18) | C11—C12—C13—C14 | 178.5 (2) |
| N9—Co1—O2—C11 | 84.25 (18) | C19—N9—C15—C16 | 0.000 (1) |
| O2—Co1—O3—C13 | 4.64 (19) | Co1—N9—C15—C16 | 180.000 (1) |
| O3i—Co1—O3—C13 | −174.99 (15) | N9—C15—C16—O6 | 180.000 (1) |
| N8—Co1—O3—C13 | 94.55 (19) | N9—C15—C16—C17 | 0.000 (1) |
| N9—Co1—O3—C13 | −84.86 (18) | O6—C16—C17—C18 | 180.000 (1) |
| Co1—O2—C11—C12 | 3.9 (3) | C15—C16—C17—C18 | 0.000 (1) |
| Co1—O2—C11—C10 | −176.26 (16) | C16—C17—C18—C19 | 0.000 (1) |
| O2—C11—C12—C13 | 1.3 (4) | C15—N9—C19—C18 | 0.000 (1) |
| C10—C11—C12—C13 | −178.6 (2) | Co1—N9—C19—C18 | 180.000 (1) |
| Co1—O3—C13—C12 | −1.4 (3) | C17—C18—C19—N9 | 0.000 (1) |
Symmetry code: (i) x, −y+3/2, z.
trans-Bis(acetylacetonato-κ2O,O')(3-hydroxypyridine-κN)(nitro)cobalt(III) monohydrate (III) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O6—H6···O7 | 0.84 (2) | 1.77 (2) | 2.593 (4) | 166 (3) |
| O6—H6···O7i | 0.84 (2) | 1.77 (2) | 2.593 (4) | 166 (3) |
| O7—H7A···O2ii | 0.83 (2) | 2.15 (3) | 2.962 (4) | 165 (8) |
| O7—H7B···O3iii | 0.83 (2) | 2.23 (3) | 3.030 (5) | 164 (8) |
| C10—H10C···O4iv | 0.96 | 2.53 | 3.446 (5) | 161 |
| C19—H19···O5Aiv | 0.93 | 2.49 | 3.413 (11) | 171 |
| C19—H19···O5Av | 0.93 | 2.49 | 3.413 (11) | 171 |
Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+3/2, z+1; (iii) x+1/2, −y+3/2, −z+3/2; (iv) x+1/2, y, −z+1/2; (v) x+1/2, −y+3/2, −z+1/2.
References
- Boldyreva, E. V. (2001). Russ. J. Coord. Chem. 27, 297–323.
- Bondi, A. (1964). J. Phys. Chem. 68, 441–451.
- Boucher, L. J. & Bailar, J. C. Jr (1965). J. Inorg. Nucl. Chem. 27, 1093–1099.
- Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
- Englert, U. & Strähle, J. (1987). Z. Naturforsch. Teil B, 42, 959–966.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Heyns, A. M. & de Waal, D. (1989). Spectrochim. Acta A, 45, 905–909.
- Johnson, D. A. & Martin, J. E. (1969). Inorg. Chem. 8, 2509–2510.
- Kistenmacher, T. J., Sorrell, T., Rossi, M., Chiang, C. C. & Marzilli, L. G. (1978). Inorg. Chem. 17, 479–481.
- Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.
- Miyazaki, H., Tsuchimoto, M. & Ohba, S. (1998). Acta Cryst. C54, 46–47.
- Ogita, M., Yamamoto, Y., Suzuki, T. & Kaizaki, S. (2002). Eur. J. Inorg. Chem. pp. 886–894.
- Ohashi, Y., Yanagi, K., Kurihara, T., Sasada, Y. & Ohgo, Y. (1981). J. Am. Chem. Soc. 103, 5805–5812.
- Ohba, S., Tsuchimoto, M. & Kurachi, S. (2018). Acta Cryst. E74, 1526–1531. [DOI] [PMC free article] [PubMed]
- Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
- Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
- Tayyari, S. F., Habibi, M. H., Shojaee, E., Jamialahmadi, M., Sammelson, R. E., Wada, K. & Suzuki, T. (2015). Spectrochim. Acta A,139, 94–101. [DOI] [PubMed]
- 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, II, III, general. DOI: 10.1107/S2056989018014731/hb7778sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018014731/hb7778Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018014731/hb7778Isup5.cdx
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989018014731/hb7778IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989018014731/hb7778IIsup6.cdx
Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989018014731/hb7778IIIsup4.hkl
Supporting information file. DOI: 10.1107/S2056989018014731/hb7778IIIsup8.cdx
The IR spectra of py (I) and 4-Me-py (II) compounds before and after photoirradiation for 30 min by a 150 W Xe lamp to the KBr disks.. DOI: 10.1107/S2056989018014731/hb7778sup9.tif
Additional supporting information: crystallographic information; 3D view; checkCIF report