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The reaction of cobalt(II) nitrate hexa­hydrate with dimethyl­glyoxime (DMGH2) and 1,10-phenanthroline (phen) in a 1:1:2 molar ratio results in two CoIII mono-dimethyl­glyoximates having two chelating phen ligands in cis positions and the CoIII atom coordinated by six N atoms in a distorted octa­hedral coordination geometry. The isolated products differ in the deprotonation state of the DMGH2 ligand. In [μ-hydrogen bis­(N,N′-dioxidobutane-2,3-diimine)]tetra­kis­(1,10-phenanthroline)cobalt(III) trinitrate ethanol disolvate 1.87-hydrate, [Co2(C4H6N2O2)(C4H7N2O2)(C12H8N2)4](NO3)3·2C2H6O·1.87H2O, (I), the C2-symmetric cation is formed with the coordination [Co(DMG)(phen)2]+ cations aggregating via a very strong O...H+...O hydrogen bond with an O...O distance of 2.409 (4) Å. Crystals of (I) exhibit extensive disorder of the solvent mol­ecules, the nitrate anions and one of the phen ligands. Compound (I) is a kinetic product, not isolated previously from similar systems, that transforms slowly into (N-hy­droxy-N′-oxidobutane-2,3-diimine)bis­(1,10-phenanthroline)cobalt(III) dinitrate ethanol monosolvate 0.4-hydrate, [Co(C4H7N2O2)(C12H8N2)2](NO3)2·C2H6O·0.40H2O, (II), with the DMGH ligand hydrogen bonded to one of the nitrate anions. In (II), the solvent mol­ecules and one of the nitrate anions are disordered.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110032968/gg3237sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110032968/gg3237Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110032968/gg3237IIsup3.hkl
Contains datablock II

CCDC references: 796065; 796066

Comment top

The coordination chemistry of the cobalt–dimethylglyoxime (DMGH2) system has long been the subject of research that is mostly related to the study of coenzyme B12 models, but synthetic, analytical, catalytic and structural aspects have also been widely addressed. In general, depending on the synthetic procedure applied (Gradinaru et al., 2006), CoIII can form mono-, bis- and tris-dimethylglyoximates, with the most extensively studied system being CoIII bis-dimethylglyoximates with trans geometry. The fact that CoIII can form mixed-ligand complexes containing one dimethylglyoxime ligand and two chelating bidentate ligands, such as thiosemicarbazide, glycine, 2,2'-bipyridine and 1,10-phenanthroline (phen), has been known for nearly 50 years (Ablov et al., 1963). These complexes are generally formed when a CoII salt, DMGH2 and a chelating ligand are reacted in a 1:1:2 molar ratio in air to allow easy oxidation of CoII to CoIII. To date, crystal structures have been reported for four complexes in this series: [CoIII(DMGH)(phen)2](SCN)2.2H2O (Botoshanskii et al., 1979), [CoIII(DMGH)(phen)2](BF4)2.2H2O (Malinovskii et al., 2004), [CoIII(DMGH)(Hthsc)2](NO3)2.2H2O (Hthsc = thiosemicarbazide; Malinovskii et al., 1977) and [CoIII(DMGH)(Hthsc)2](SiF6).2.3H2O (Bourosh et al., 2006), in which dimethylglyoxime is monodeprotonated and the inorganic counterions are in the outer coordination sphere.

Among the papers retracted recently from Acta Crystallographica Section E due to a series of uncovered scientific frauds (Harrison et al., 2010), three papers reported the structures of complexes formed by divalent transition metal nitrates with phen and DMGH2 of the general formula [MII(DMGH2)(phen)2](NO3)2.2H2O, where M = Zn, Ni and Cu (Zhong et al., 2007a,b; Zhong et al., 2007). The fact that these three structures were incorrect became obvious to us at the beginning of 2009 when we had analysed the geometry of the dimethylglyoxime ligand using the Cambridge Structural Database (CSD; Allen, 2002). Refinement of the crystal structures with the deposited diffraction data showed that, in all three cases, the studied compound was most probably [CoIII(DMGH)(phen)2](NO3)2.EtOH, i.e. it belonged to the known series of CoIII mono-dimethylglyoximates. The structure of this compound has not been previously reported, and therefore we assumed incompetence in correctly identifying the analysed chemical sample that encompassed the incorrect identification of the protonation state of the dimethylglyoxime ligand, the incorrect identification of the cation and its oxidation state and the incorrect identification of the solvent molecules. To make sure that the compound was really what we had expected, we decided to repeat the synthesis using Co(NO3)2.6H2O as a substrate. There were some doubts concerning the identification of the solvent molecules due to their severe disorder and therefore collection of new diffraction data at low temperature seemed neccessary. However, as often happens, the studied system appeared to be more complicated, and at the same time more interesting, than we initially expected.

The first reaction was carried out under anaerobic conditions and resulted in the CoII complex [CoII(phen)2(H2O)2](NO3)2, with an interesting uncommensurately modulated crystal structure that will be reported elsewhere. This reaction showed that under the applied conditions the DMGH2 is not reacting with CoII. The second reaction was carried out in aerobic conditions to allow easy oxidation of CoII to CoIII. As the reaction proceeded, precipitation of small red needle-shaped crystals was observed, followed by the appearance of dark-red block crystals. A few crystals of both types were isolated from the solution and the reaction mixture was left aside for a period of 3 d, during which the majority of the needle-shaped crystals transformed to dark-red blocks.

The diffraction quality of the crystals was checked, revealing in the case of the needles monoclinic symmetry and poor diffraction with a large amount of diffuse scattering, signaling extensive crystal disorder, whereas the dark-red block crystals gave good diffraction patterns and the unit-cell parameters agreed reasonably well with those reported for the three retracted structures (Zhong et al., 2010; CSD refcodes: YEYGOZ, YEYGUF, YIQNUI). Both types of crystal, when left in air, decomposed slowly to a powder. In order to obtain larger needle-shaped crystals, the reaction was repeated a few more times, but the less-stable and apparently kinetic product (I) appeared only once, forming a few larger crystals, one of which was used for the X-ray structural analysis at 130 K.

Structure solution revealed that (I) has the formula {[CoIIIDMG(phen)2]2H}(NO3)3.1.87H2O.2EtOH and consists of crystallographically C2-symmetric {[CoIIIDMG(phen)2]2H}+ cations in which two identical [CoIIIDMG(phen)2]+ units are connected by a very strong O-···H+···O- hydrogen bond, with the H atom located on a twofold axis passing through the middle of the O···O distance [2.4098 (4) Å] (Fig. 1a, Table 2). This distance is ca 0.1 Å shorter than the O···O distances of strong intramolecular hydrogen bonds formed in typical CoIII trans bis-dimethylglyoximates. In the dimethylglyoximate ligand, the N12—O12 bond length of 1.287 (3) Å clearly shows that one oxime group is fully deprotonated, whereas the N11—O11 bond length of 1.342 (3) Å in the second oxime group has a value intermediate between fully deprotonated and fully protonated states, which is in accord with the observed formation of [DMG···H···DMG]3- anionic species coordinated by two Co centres. To balance the positive charge of the Co cations, which was assumed to be 3+, one and a half of the nitrate anions had to be located in the asymmetric unit. One anion, designated B in Fig. 1(b) and disordered over two overlapping positions, was easily identified. The missing half of the anion was sought among a difficult to interprete cluster of electron-density peaks found around the twofold axis. Closer examination showed that this C2-symmetric cluster results from the superposition of a disordered group of atoms, having half occupancy, that belong to a nitrate anion (designated A) and a water molecule (O2W) (Fig. 1b). In addition to the components indicated above, the asymmetric unit of (I) also contains another water molecule (O1W), with an occupancy of 0.436 (7), and an ethanol sovent molecule disordered over two positions with a common hydroxy group.

The main component of (I), the {[CoIIIDMG(phen)2]2H}+ cation, has the CoIII atom in a distorted octahedral coordination geometry, with two chelating phen ligands in cis positions. The dihedral angles between the best planes of the chelating ligands are in the range 83.42 (8)–88.00 (10)° and the bite angles of the chelate rings are 82.37 (11)–83.45 (11)°. One of the phen ligands is disordered over two coplanar positions related by ca 13° rotation around the N12···N21 vector. The coordination geometry around the CoIII centre in (I) is given in Table 1.

The disordered phen ligand shows a large number of short C—H···O contacts with the surrounding disordered nitrate anions and disordered solvent molecules, some of which are most probably repulsive. The occupancy of the water molecule O1W is correlated with the minor position of the disordered phen ligand, whereas the occupancies of the alternative positions of the ethanol molecule are correlated with the disorder of the B nitrate anion. In contrast, the well ordered phen and DMG ligands do not form any unusually short contacts with the disordered part of the structure, with the shortest C13—H13B··· O2A(1 - x, -1 + y, 1/2 - z) distance of 2.36 Å occurring between the DMG methyl group and the nitrate A anion.

In the {[CoIIIDMG(phen)2]2H}+ cation, the atoms connected by a strong O-···H+···O- hydrogen bond are buried within a niche formed inside the cation by the ordered phen ligands and dimethylglyoximate units. In the crystal structure, the cations form extended chains along [101] via ππ stacking interactions between the disordered phen units, which are additionally supported by C—H···O interactions between phen H atoms and atom O12i [symmetry code: (i) 3/2 - x, 1/2 - y, -z] from the deprotonated oxime group. The packing arrangement in (I) is illustrated in Fig. 2.

The asymmetric unit of the second reaction product, the dark-red block crystals of (II), consists of the [CoIII(DMGH)(phen)2]2+ cation, one ordered and one disordered nitrate anion, and disordered ethanol and water solvent molecules (Fig. 3). Taking into account the occupancies of the solvent molecules derived from the structure refinement, the formula of (II) is [CoIII(DMGH)(phen)2]NO3)2. 0.40H2O.EtOH. The dimethylglyoxime ligand is monodeprotonated, as evidenced by the oxime-group N—O bond lengths [N11—O11 = 1.278 (2) Å and N12—O12 = 1.382 (2) Å], which are similar to those reported earlier for [CoIII(DMGH)(phen)]2+ cations (Botoshanskii et al., 1979; Malinovskii et al., 2004). The oxime group N12—O12—H1O interacts via a hydrogen bond with the ordered nitrate anion A (Table 4).

The coordination geometry around the CoIII centre in (II) is very similar to that in (I) (Fig. 3a, Table 3), with the dihedral angles between the best planes of the chelating ligands in the range 84.46 (4)–89.97 (4)° and the bite angles of the three chelate rings in the range 81.89 (8)–83.98 (8)°. The volume in the crystal structure which is occupied by the solvent molecules is either occupied by a single ethanol molecule, which forms a hydrogen bond with a disordered B nitrate anion, or by an ethanol and a water molecule, with the water molecule serving as a bridge between ethanol and the B nitrate anion. The crystal structure of (II) can be seen as composed of chains of [CoIII(DMGH)(phen)]2+ formed via ππ stacking interactions between inversion-centre-related phen ligands and C—H···O interactions between phen and DMGH- ligands. These chains extend along the [110] and [110] directions (Fig. 4). Similar packing motifs were observed in two other compounds containing [CoIII(DMGH)(phen)]2+ cations (Botoshanskii et al., 1979; Malinovskii et al., 2004).

In summary, the two CoIII nitrate compounds isolated from one reaction contain coordination cations that differ in the deprotonation state of the dimethylglyoximate ligand. In (I), there is one H atom per two DMG2- anions, and a very strong O-···H+···O- hydrogen bond connects two coordination cations into the {[CoIIIDMG(phen)2]2H}+ species, although this cannot pack efficiently, as reflected in the extensive crystal structure disorder. Compound (I), which is a kinetic product, transforms in solution to compound (II), with a structure similar to those of the previously reported mono-dimethylglyoximates. Moreover, (II) represents the revised structure of the three DMGH2 complexes recently retracted from Acta Crystallographica Section E (Zhong et al., 2010; CSD refcodes: YEYGOZ, YEYGUF, YIQNUI).

Related literature top

For related literature, see: Ablov et al. (1963); Allen (2002); Botoshanskii et al. (1979); Bourosh et al. (2006); Gradinaru et al. (2006); Harrison et al. (2010); Malinovskii et al. (1977, 2004); Sheldrick (2008); Zhong et al. (2007, 2007a, 2007b, 2010).

Experimental top

Dimethylglyoxime (60 mg, 0.5 mmol), 1,10-phenanthroline (190 mg, 1 mmol) and Co(NO3)2.6H2O (140 mg, 0.5 mmol) were dissolved in ethanol (10 ml) in a round-bottomed flask. The mixture was heated for 5 h under reflux with stirring, filtered, and the filrate placed in a vial in a closed vessel containing diethyl ether. Within 1 d, red needle-shaped crystals of (I) and dark-red block crystals of (II) appeared. A few crystals of each type were isolated from the solution and used for X-ray analyses.

Refinement top

Due to the severe disorder of the crystal structure of (I), the structure refinement was also attempted in the Cc space group, but the disorder persisted in this lower symmetry group too, with only a minor reduction in the R factor. For the refinement, restraints and constraints were imposed on the geometry of the disordered groups (DFIX, FLAT and EXYZ commands in SHELXL97; Sheldrick, 2008) and on the displacement parameters of some atoms (ISOR and EADP commands in SHELXL97). The sum of the occupancy factors for the disordered phen ligands (atom labels starting with 3 and 4) was constrained to 1.00 and for the major position the occupancy factor refined to 0.564 (7). A common occupancy factor was assumed for the major positions of the B nitrate anion and the ethanol C molecule and it refined to 0.638 (5). All C-bound H atoms were placed in calculated positions, with C—H = 0.95–98 Å, and were refined as riding on their carrier atoms, with Uiso(H) = 1.2Ueq(C). The H atoms of the OH groups were either identified in difference Fourier maps or placed in calculated positions and refined as riding on their carrier atoms, with Uiso(H) = 1.5Ueq(O).

In (II), disorder was observed for the B nitrate anion and the solvent molecules. The nitrate anions in disordered positions were refined as rigid groups. The sum of the occupancy factors for the disordered nitrate anions B and B' was constrained to 1.00. Water and ethanol C molecules had a common occupancy factor 1 - p, where p is the occupancy factor of the ethanol D molecule. The occupancy factors for the ethanol D molecule and nitrate B anion refined to 0.597 (6) and 0.864 (4), respectively. All C-bound H atoms were placed in calculated positions, with C—H = 0.95–99 Å, and were refined as riding on their carrier atoms, with Uiso(H) = 1.2Ueq(C). The H atoms of the OH groups were either identified in difference Fourier maps or placed in calculated positions and refined as riding on their carrier atoms, with Uiso(H) = 1.5Ueq(O). One of the H atoms of the disordered water molecule is missing.

Computing details top

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (a) The C2-symmetric coordination cation {[CoDMG(phen)2]2H}+ with the very strong O-···H+···O- hydrogen bond (dashed lines). The atoms of the phen ligand in the minor position are represented by ellipsoids with boundaries. Only the H atom in the very strong hydrogen bond is shown. (b) The nitrate anions and the solvent molecules of (I). Hydrogen bonds are shown as dashed lines and the disordered positions are differentiated by the displacement ellipsoid type.
[Figure 2] Fig. 2. The crystal packing of (I), showing chains of {[CoDMG(phen)2]2H}+ coordination cations formed via ππ stacking interactions between phen ligands. Disorder is only shown for the nitrate anion and the water molecule located around a twofold axis. Hydrogen bonds are shown as dashed lines. [Please check added text] H atoms not involved in hydrogen bonding have been omitted.
[Figure 3] Fig. 3. The structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (a) The coordination cation [CoDMGH(phen)2]2+. Only the H atom from the oxime group is shown. (b) The nitrate anions and the solvent molecules. The hydrogen bond is shown as a dashed line and the disordered positions are differentiated by the displacement ellipsoid type.
[Figure 4] Fig. 4. (a) Chains formed via ππ stacking interactions between phen ligands and C—H···O interactions (dashed lines) in (II). (b) A view of the crystal structure of (II). The chains at c = 0.5 are parallel to the viewing direction, and the chains at c = 0.0 or c = 1.0 are approximately perpendicular to the viewing direction. Hydrogen bonds are shown as dashed lines. [Please check added text]
(I) [µ-hydrogen bis(N,N'-dioxidobutane-2,3-diimine)]tetrakis(1,10- phenanthroline)cobalt(III) trinitrate ethanol disolvate 1.87-hydrate top
Crystal data top
[Co2(C4H6N2O2)(C4H7N2O2)(C12H8N2)4]·(NO3)3·2C2H6O·1.87H2OF(000) = 2859
Mr = 1379.76Dx = 1.548 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9535 reflections
a = 19.0680 (8) Åθ = 2.8–24.9°
b = 16.0170 (5) ŵ = 0.65 mm1
c = 20.0130 (8) ÅT = 130 K
β = 104.353 (4)°Needle, red
V = 5921.4 (4) Å30.50 × 0.40 × 0.40 mm
Z = 4
Data collection top
Oxford XcaliburE CCD
diffractometer
5211 independent reflections
Radiation source: fine-focus sealed tube3075 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω scansθmax = 25.0°, θmin = 4.2°
Absorption correction: multi-scan
CrysAlis PRO (Oxford Diffraction, 2009)
h = 2222
Tmin = 0.720, Tmax = 0.804k = 1819
25463 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 0.89 w = 1/[σ2(Fo2) + (0.0512P)2]
where P = (Fo2 + 2Fc2)/3
5211 reflections(Δ/σ)max = 0.002
614 parametersΔρmax = 0.34 e Å3
183 restraintsΔρmin = 0.46 e Å3
Crystal data top
[Co2(C4H6N2O2)(C4H7N2O2)(C12H8N2)4]·(NO3)3·2C2H6O·1.87H2OV = 5921.4 (4) Å3
Mr = 1379.76Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.0680 (8) ŵ = 0.65 mm1
b = 16.0170 (5) ÅT = 130 K
c = 20.0130 (8) Å0.50 × 0.40 × 0.40 mm
β = 104.353 (4)°
Data collection top
Oxford XcaliburE CCD
diffractometer
5211 independent reflections
Absorption correction: multi-scan
CrysAlis PRO (Oxford Diffraction, 2009)
3075 reflections with I > 2σ(I)
Tmin = 0.720, Tmax = 0.804Rint = 0.053
25463 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043183 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 0.89Δρmax = 0.34 e Å3
5211 reflectionsΔρmin = 0.46 e Å3
614 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.55990 (2)0.21717 (2)0.10577 (2)0.03478 (15)
N110.57067 (14)0.17428 (16)0.19555 (13)0.0354 (7)
N120.59389 (13)0.10858 (15)0.08974 (13)0.0305 (6)
O110.56294 (12)0.22055 (14)0.24915 (11)0.0473 (6)
H1O0.50000.21400.25000.071*
O120.59934 (11)0.08509 (12)0.02976 (10)0.0377 (5)
C110.59519 (17)0.0986 (2)0.20504 (16)0.0368 (8)
C120.60775 (17)0.06000 (19)0.14341 (16)0.0333 (8)
C130.6104 (2)0.0549 (2)0.27320 (16)0.0501 (10)
H13C0.66180.06080.29650.075*
H13B0.59850.00450.26590.075*
H13A0.58100.07970.30180.075*
C140.6334 (2)0.0271 (2)0.13888 (17)0.0491 (10)
H14B0.59320.06150.11330.074*
H14A0.65150.04980.18550.074*
H14C0.67250.02720.11500.074*
N210.51604 (16)0.32337 (16)0.12822 (13)0.0412 (7)
N2100.45986 (14)0.17976 (16)0.07948 (12)0.0327 (6)
C220.5466 (2)0.3956 (2)0.15209 (19)0.0542 (10)
H220.59740.40180.15860.065*
C230.5068 (2)0.4624 (2)0.1680 (2)0.0624 (12)
H230.53000.51380.18350.075*
C240.4341 (2)0.4535 (2)0.16102 (19)0.0599 (11)
H240.40670.49840.17250.072*
C250.3241 (2)0.3602 (3)0.12752 (19)0.0544 (11)
H250.29370.40160.13950.065*
C260.2952 (2)0.2867 (3)0.10224 (18)0.0510 (10)
H260.24490.27730.09680.061*
C270.3129 (2)0.1444 (2)0.05552 (16)0.0463 (9)
H270.26290.13110.04770.056*
C280.35988 (19)0.0882 (2)0.03984 (15)0.0426 (9)
H280.34250.03600.01980.051*
C290.43328 (18)0.1067 (2)0.05305 (15)0.0360 (8)
H290.46540.06600.04290.043*
C2110.41307 (18)0.23714 (19)0.09395 (15)0.0350 (8)
C2120.33884 (18)0.2222 (2)0.08329 (16)0.0399 (8)
C2130.4434 (2)0.3146 (2)0.12002 (17)0.0389 (9)
C2140.3998 (2)0.3778 (2)0.13687 (18)0.0483 (10)
N310.6636 (6)0.2582 (7)0.1407 (6)0.031 (2)0.564 (7)
N3100.5705 (5)0.2612 (7)0.0210 (5)0.035 (3)0.564 (7)
C320.7087 (5)0.2574 (5)0.2032 (5)0.033 (2)0.564 (7)
H320.69330.23240.24010.040*0.564 (7)
C330.7776 (4)0.2919 (4)0.2163 (5)0.044 (2)0.564 (7)
H330.80850.29130.26150.053*0.564 (7)
C340.8004 (5)0.3272 (5)0.1617 (5)0.047 (2)0.564 (7)
H340.84760.35040.17010.057*0.564 (7)
C350.7737 (5)0.3618 (5)0.0367 (5)0.055 (2)0.564 (7)
H350.82040.38500.04090.066*0.564 (7)
C360.7251 (6)0.3612 (6)0.0275 (6)0.039 (3)0.564 (7)
H360.73850.38390.06640.047*0.564 (7)
C370.6025 (6)0.3233 (5)0.0955 (6)0.040 (3)0.564 (7)
H370.61330.34540.13590.049*0.564 (7)
C380.5362 (6)0.2908 (6)0.1014 (5)0.044 (3)0.564 (7)
H380.50090.28910.14420.053*0.564 (7)
C390.5221 (6)0.2586 (6)0.0387 (7)0.040 (3)0.564 (7)
H390.47610.23460.04050.048*0.564 (7)
C3110.6369 (6)0.2943 (6)0.0240 (6)0.031 (2)0.564 (7)
C3120.6559 (5)0.3268 (5)0.0347 (5)0.043 (2)0.564 (7)
C3130.6864 (5)0.2935 (5)0.0882 (5)0.030 (2)0.564 (7)
C3140.7563 (6)0.3295 (6)0.0956 (7)0.044 (3)0.564 (7)
N410.6498 (7)0.2667 (8)0.1181 (6)0.028 (3)0.436 (7)
N4100.5493 (6)0.2525 (7)0.0028 (7)0.018 (3)0.436 (7)
C420.6982 (8)0.2744 (8)0.1776 (8)0.035 (3)0.436 (7)
H420.68700.25260.21790.042*0.436 (7)
C430.7660 (7)0.3137 (7)0.1840 (6)0.050 (3)0.436 (7)
H430.79970.31880.22750.059*0.436 (7)
C440.7813 (8)0.3439 (8)0.1257 (8)0.045 (4)0.436 (7)
H440.82650.37050.12880.054*0.436 (7)
C450.7465 (8)0.3656 (8)0.0006 (7)0.032 (3)0.436 (7)
H450.79160.39080.00070.039*0.436 (7)
C460.6920 (6)0.3563 (6)0.0629 (6)0.043 (3)0.436 (7)
H460.70070.37600.10490.051*0.436 (7)
C470.5692 (6)0.3078 (5)0.1235 (5)0.028 (2)0.436 (7)
H470.57490.32630.16700.033*0.436 (7)
C480.5031 (6)0.2692 (5)0.1197 (5)0.030 (3)0.436 (7)
H480.46460.26130.15960.036*0.436 (7)
C490.4970 (6)0.2433 (7)0.0544 (6)0.024 (3)0.436 (7)
H490.45310.21780.05100.028*0.436 (7)
C4110.6122 (6)0.2902 (7)0.0022 (5)0.022 (3)0.436 (7)
C4120.6271 (7)0.3193 (7)0.0634 (7)0.026 (3)0.436 (7)
C4130.6660 (7)0.2989 (7)0.0601 (7)0.022 (3)0.436 (7)
C4140.7325 (6)0.3367 (6)0.0621 (6)0.039 (3)0.436 (7)
O1W0.6457 (4)0.7548 (4)0.1543 (4)0.100 (3)0.436 (7)
H1W10.61240.77880.17220.151*0.436 (7)
H2W10.67470.71720.18010.151*0.436 (7)
O2W0.5591 (3)0.9356 (3)0.3840 (2)0.0523 (13)0.50
H1W20.53160.90360.35150.078*0.50
H2W20.57660.90530.42180.078*0.50
N1A0.5016 (3)0.8621 (2)0.2198 (3)0.049 (3)0.50
O1A0.4785 (3)0.8913 (3)0.1606 (3)0.0614 (14)0.50
O3A0.5622 (3)0.8284 (4)0.2365 (4)0.068 (2)0.50
O2A0.4628 (4)0.8674 (4)0.2614 (4)0.057 (2)0.50
N1B0.6857 (2)0.59657 (18)0.2473 (2)0.048 (2)0.638 (5)
O1B0.7153 (2)0.5660 (3)0.3032 (2)0.0703 (16)0.638 (5)
O2B0.7167 (2)0.6131 (3)0.2001 (2)0.0760 (19)0.638 (5)
O3B0.61938 (16)0.61223 (18)0.23738 (16)0.0812 (9)
N1B'0.6789 (3)0.5763 (5)0.2429 (3)0.094 (7)0.362 (5)
O1B'0.6916 (5)0.5007 (5)0.2524 (6)0.109 (4)0.362 (5)
O2B'0.7299 (4)0.6227 (5)0.2381 (6)0.0812 (9)0.36
O1C0.63865 (16)0.65745 (17)0.06206 (18)0.0926 (12)0.638 (5)
H1C0.64020.67630.10050.139*
C1C0.5942 (5)0.5902 (3)0.0510 (4)0.0423 (18)0.638 (5)
H1CA0.57250.58220.08900.051*0.638 (5)
H1CB0.55590.60050.01050.051*0.638 (5)
C2C0.6330 (5)0.5106 (4)0.0399 (5)0.071 (3)0.638 (5)
H2CC0.59940.46490.03110.085*0.638 (5)
H2CB0.67060.49910.08050.085*0.638 (5)
H2CA0.65380.51770.00120.085*0.638 (5)
O1C'0.63865 (16)0.65745 (17)0.06206 (18)0.0926 (12)0.36
C1C'0.6312 (13)0.5609 (18)0.0484 (13)0.115 (5)0.362 (5)
H1CD0.66540.54550.02180.138*0.362 (5)
H1CC0.64620.53270.09250.138*0.362 (5)
C2C'0.5692 (10)0.5325 (16)0.0177 (9)0.115 (5)0.362 (5)
H2CF0.57270.47300.01350.172*0.362 (5)
H2CD0.55420.55700.02740.172*0.362 (5)
H2CE0.53440.54540.04360.172*0.362 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0364 (3)0.0351 (2)0.0411 (3)0.0070 (2)0.0251 (2)0.0013 (2)
N110.0336 (17)0.0393 (16)0.0356 (17)0.0139 (13)0.0133 (13)0.0100 (13)
N120.0311 (16)0.0375 (15)0.0263 (16)0.0080 (12)0.0133 (13)0.0003 (13)
O110.0492 (15)0.0568 (14)0.0415 (14)0.0212 (12)0.0218 (12)0.0197 (12)
O120.0439 (14)0.0445 (13)0.0302 (13)0.0005 (11)0.0195 (11)0.0028 (10)
C110.035 (2)0.049 (2)0.026 (2)0.0155 (17)0.0073 (16)0.0045 (16)
C120.033 (2)0.0381 (18)0.028 (2)0.0082 (15)0.0060 (16)0.0001 (15)
C130.065 (3)0.060 (2)0.022 (2)0.007 (2)0.0046 (18)0.0025 (16)
C140.059 (3)0.054 (2)0.035 (2)0.0009 (19)0.0118 (19)0.0067 (16)
N210.050 (2)0.0347 (16)0.0487 (19)0.0058 (14)0.0314 (15)0.0030 (13)
N2100.0374 (17)0.0419 (16)0.0222 (15)0.0032 (14)0.0138 (13)0.0072 (12)
C220.066 (3)0.042 (2)0.070 (3)0.010 (2)0.047 (2)0.0005 (19)
C230.092 (3)0.034 (2)0.084 (3)0.009 (2)0.066 (3)0.0019 (19)
C240.081 (3)0.042 (2)0.077 (3)0.011 (2)0.058 (3)0.015 (2)
C250.059 (3)0.060 (3)0.058 (3)0.022 (2)0.038 (2)0.027 (2)
C260.044 (2)0.067 (3)0.047 (2)0.012 (2)0.0193 (18)0.026 (2)
C270.036 (2)0.079 (3)0.024 (2)0.010 (2)0.0059 (17)0.0112 (18)
C280.040 (2)0.065 (2)0.0214 (19)0.010 (2)0.0041 (17)0.0013 (16)
C290.039 (2)0.049 (2)0.0212 (18)0.0067 (17)0.0093 (16)0.0012 (15)
C2110.040 (2)0.043 (2)0.0258 (19)0.0025 (17)0.0155 (16)0.0119 (15)
C2120.034 (2)0.062 (2)0.0235 (18)0.007 (2)0.0076 (16)0.0194 (17)
C2130.046 (2)0.042 (2)0.037 (2)0.0039 (18)0.0263 (18)0.0137 (16)
C2140.060 (3)0.043 (2)0.055 (2)0.009 (2)0.039 (2)0.0180 (17)
N310.027 (4)0.035 (3)0.036 (5)0.002 (3)0.013 (4)0.009 (4)
N3100.031 (5)0.042 (4)0.030 (5)0.003 (3)0.007 (3)0.001 (3)
C320.033 (4)0.028 (3)0.039 (4)0.004 (3)0.008 (4)0.005 (3)
C330.037 (4)0.038 (3)0.054 (4)0.005 (3)0.008 (3)0.001 (3)
C340.042 (4)0.039 (3)0.060 (5)0.009 (3)0.011 (4)0.003 (3)
C350.057 (4)0.052 (4)0.067 (5)0.007 (3)0.034 (4)0.012 (4)
C360.038 (5)0.049 (4)0.037 (5)0.012 (4)0.021 (4)0.012 (4)
C370.044 (5)0.040 (4)0.040 (5)0.006 (4)0.016 (4)0.007 (4)
C380.051 (5)0.047 (4)0.039 (4)0.005 (4)0.018 (4)0.008 (3)
C390.041 (5)0.045 (4)0.039 (5)0.001 (4)0.018 (4)0.008 (4)
C3110.028 (5)0.036 (4)0.031 (5)0.000 (3)0.014 (4)0.007 (4)
C3120.049 (5)0.041 (3)0.043 (4)0.001 (3)0.020 (4)0.009 (3)
C3130.030 (4)0.029 (3)0.034 (4)0.002 (3)0.011 (3)0.004 (3)
C3140.046 (5)0.046 (4)0.045 (5)0.001 (4)0.019 (4)0.001 (4)
N410.027 (5)0.033 (4)0.021 (5)0.009 (3)0.002 (4)0.006 (4)
N4100.018 (5)0.022 (3)0.016 (5)0.006 (3)0.009 (4)0.001 (4)
C420.033 (5)0.039 (5)0.032 (5)0.008 (4)0.007 (4)0.002 (4)
C430.048 (5)0.058 (5)0.045 (5)0.013 (4)0.015 (4)0.006 (4)
C440.040 (5)0.052 (5)0.042 (6)0.011 (4)0.011 (4)0.003 (4)
C450.027 (5)0.041 (4)0.027 (6)0.016 (4)0.005 (4)0.004 (4)
C460.047 (5)0.044 (4)0.044 (5)0.010 (4)0.024 (4)0.004 (4)
C470.031 (4)0.031 (4)0.025 (4)0.001 (3)0.015 (4)0.003 (3)
C480.046 (7)0.024 (5)0.026 (6)0.000 (4)0.020 (5)0.006 (4)
C490.022 (4)0.026 (4)0.021 (5)0.000 (3)0.002 (4)0.005 (3)
C4110.022 (5)0.026 (4)0.022 (5)0.006 (3)0.012 (4)0.002 (4)
C4120.019 (5)0.034 (4)0.023 (5)0.003 (4)0.003 (4)0.003 (4)
C4130.018 (5)0.029 (4)0.018 (5)0.011 (4)0.005 (4)0.001 (4)
C4140.031 (5)0.042 (4)0.043 (5)0.015 (4)0.011 (4)0.003 (4)
O1W0.110 (7)0.082 (5)0.130 (7)0.011 (4)0.069 (5)0.026 (4)
O2W0.065 (4)0.050 (3)0.035 (3)0.001 (3)0.000 (3)0.006 (2)
N1A0.061 (7)0.045 (4)0.039 (6)0.008 (4)0.008 (5)0.004 (4)
O1A0.057 (4)0.071 (4)0.053 (4)0.005 (3)0.009 (3)0.007 (3)
O3A0.055 (5)0.086 (6)0.063 (4)0.027 (4)0.014 (3)0.002 (4)
O2A0.060 (7)0.066 (6)0.044 (5)0.005 (4)0.015 (5)0.008 (4)
N1B0.028 (4)0.064 (4)0.059 (5)0.019 (3)0.025 (4)0.033 (3)
O1B0.063 (3)0.080 (4)0.062 (3)0.003 (3)0.006 (3)0.014 (3)
O2B0.058 (3)0.146 (5)0.034 (3)0.029 (3)0.030 (2)0.030 (3)
O3B0.071 (2)0.0761 (19)0.106 (2)0.0038 (17)0.0406 (19)0.0112 (17)
N1B'0.084 (15)0.040 (7)0.178 (19)0.011 (8)0.068 (13)0.026 (9)
O1B'0.071 (7)0.090 (8)0.166 (11)0.008 (6)0.032 (7)0.030 (8)
O2B'0.071 (2)0.0761 (19)0.106 (2)0.0038 (17)0.0406 (19)0.0112 (17)
O1C0.067 (2)0.064 (2)0.158 (3)0.0086 (17)0.049 (2)0.0126 (19)
C1C0.054 (5)0.022 (3)0.065 (4)0.012 (3)0.042 (4)0.017 (3)
C2C0.090 (8)0.033 (4)0.115 (6)0.003 (4)0.075 (6)0.008 (4)
O1C'0.067 (2)0.064 (2)0.158 (3)0.0086 (17)0.049 (2)0.0126 (19)
C1C'0.096 (13)0.124 (14)0.132 (13)0.011 (12)0.040 (10)0.043 (12)
C2C'0.096 (13)0.124 (14)0.132 (13)0.011 (12)0.040 (10)0.043 (12)
Geometric parameters (Å, º) top
Co1—N111.887 (3)C37—C3121.382 (13)
Co1—N121.911 (2)C37—H370.9500
Co1—N211.995 (3)C38—C391.442 (15)
Co1—N312.036 (12)C38—H380.9500
Co1—N411.848 (14)C39—H390.9500
Co1—N2101.943 (3)C311—C3131.393 (13)
Co1—N3101.894 (11)C311—C3121.412 (12)
Co1—N4102.097 (13)C313—C3141.425 (14)
N11—C111.296 (4)N41—C421.319 (19)
N11—O111.342 (3)N41—C4131.375 (17)
N12—O121.287 (3)N410—C491.327 (18)
N12—C121.299 (4)N410—C4111.369 (16)
O11—H1O1.2087C42—C431.415 (18)
C11—C121.452 (4)C42—H420.9500
C11—C131.496 (4)C43—C441.359 (16)
C12—C141.488 (4)C43—H430.9500
C13—H13C0.9800C44—C4141.383 (17)
C13—H13B0.9800C44—H440.9500
C13—H13A0.9800C45—C4141.424 (16)
C14—H14B0.9800C45—C461.420 (16)
C14—H14A0.9800C45—H450.9500
C14—H14C0.9800C46—C4121.370 (15)
N21—C221.329 (4)C46—H460.9500
N21—C2131.361 (4)C47—C481.423 (14)
N210—C291.332 (4)C47—C4121.429 (16)
N210—C2111.361 (4)C47—H470.9500
C22—C231.395 (5)C48—C491.402 (15)
C22—H220.9500C48—H480.9500
C23—C241.365 (5)C49—H490.9500
C23—H230.9500C411—C4121.404 (16)
C24—C2141.404 (5)C411—C4131.412 (16)
C24—H240.9500C413—C4141.395 (15)
C25—C261.344 (5)O1W—H1W10.8900
C25—C2141.436 (5)O1W—H2W10.8900
C25—H250.9500O2W—O1Ai1.223 (6)
C26—C2121.435 (5)O2W—H1W20.8900
C26—H260.9500O2W—H2W20.8900
C27—C281.361 (5)N1A—O3A1.243 (5)
C27—C2121.404 (5)N1A—O2A1.247 (5)
C27—H270.9500N1A—O1A1.248 (5)
C28—C291.390 (4)N1B—O1B1.223 (4)
C28—H280.9500N1B—O3B1.255 (4)
C29—H290.9500N1B—O2B1.260 (4)
C211—C2121.399 (4)O1B—N1B'1.245 (6)
C211—C2131.413 (4)O3B—N1B'1.252 (5)
C213—C2141.403 (4)N1B'—O1B'1.241 (5)
N31—C321.330 (14)N1B'—O2B'1.246 (5)
N31—C3131.357 (13)O1C—C1C1.354 (7)
N310—C391.316 (15)O1C—H1C0.8200
N310—C3111.360 (13)C1C—C2C1.518 (10)
C32—C331.389 (12)C1C—H1CA0.9600
C32—H320.9500C1C—H1CB0.9606
C33—C341.392 (12)C2C—H2CC0.9600
C33—H330.9500C2C—H2CB0.9603
C34—C3141.381 (14)C2C—H2CA0.9599
C34—H340.9500C2C—H1CD0.9674
C35—C361.386 (13)C1C'—C2C'1.27 (3)
C35—C3141.400 (12)C1C'—H1CD0.9700
C35—H350.9500C1C'—H1CC0.9700
C36—C3121.403 (13)C2C'—H2CF0.9600
C36—H360.9500C2C'—H2CD0.9600
C37—C381.345 (12)C2C'—H2CE0.9600
N11—Co1—N1282.36 (11)C36—C35—C314122.3 (10)
N11—Co1—N2192.80 (11)C36—C35—H35118.9
N11—Co1—N3185.6 (3)C314—C35—H35118.9
N11—Co1—N4198.6 (4)C35—C36—C312119.5 (8)
N11—Co1—N21090.77 (10)C35—C36—H36120.2
N11—Co1—N310168.0 (3)C312—C36—H36120.2
N11—Co1—N410174.2 (3)C38—C37—C312124.3 (10)
N12—Co1—N21172.92 (10)C38—C37—H37117.9
N12—Co1—N3190.6 (3)C312—C37—H37117.9
N12—Co1—N4194.1 (4)C37—C38—C39115.9 (9)
N12—Co1—N21091.43 (11)C37—C38—H38122.1
N12—Co1—N41092.0 (3)C39—C38—H38122.1
N21—Co1—N3194.2 (3)N310—C39—C38122.6 (10)
N21—Co1—N4191.8 (4)N310—C39—H39118.7
N21—Co1—N41092.7 (3)C38—C39—H39118.7
N41—Co1—N210169.7 (4)N310—C311—C313116.6 (9)
N41—Co1—N41082.9 (5)N310—C311—C312122.4 (11)
N310—Co1—N1294.2 (3)C313—C311—C312121.0 (9)
N310—Co1—N210100.8 (3)C37—C312—C36125.0 (9)
N310—Co1—N2191.6 (3)C37—C312—C311115.7 (9)
N210—Co1—N2183.44 (11)C36—C312—C311119.3 (9)
N310—Co1—N3183.0 (4)N31—C313—C311116.3 (9)
N210—Co1—N31175.5 (3)N31—C313—C314124.0 (9)
N210—Co1—N41088.2 (3)C311—C313—C314119.7 (9)
C11—N11—O11120.4 (3)C34—C314—C35126.9 (11)
C11—N11—Co1115.5 (2)C34—C314—C313114.9 (8)
O11—N11—Co1123.6 (2)C35—C314—C313118.2 (11)
O12—N12—C12123.3 (2)C42—N41—C413118.2 (13)
O12—N12—Co1122.14 (18)C42—N41—Co1125.4 (10)
C12—N12—Co1114.5 (2)C413—N41—Co1116.4 (9)
N11—O11—H1O105.6C49—N410—C411118.0 (11)
N11—C11—C12113.8 (3)C49—N410—Co1133.4 (8)
N11—C11—C13123.6 (3)C411—N410—Co1108.6 (8)
C12—C11—C13122.7 (3)N41—C42—C43122.8 (12)
N12—C12—C11113.9 (3)N41—C42—H42118.6
N12—C12—C14120.9 (3)C43—C42—H42118.6
C11—C12—C14125.2 (3)C44—C43—C42117.8 (12)
C11—C13—H13C109.5C44—C43—H43121.1
C11—C13—H13B109.5C42—C43—H43121.1
H13C—C13—H13B109.5C43—C44—C414121.4 (13)
C11—C13—H13A109.5C43—C44—H44119.3
H13C—C13—H13A109.5C414—C44—H44119.3
H13B—C13—H13A109.5C414—C45—C46118.9 (11)
C12—C14—H14B109.5C414—C45—H45120.5
C12—C14—H14A109.5C46—C45—H45120.5
H14B—C14—H14A109.5C412—C46—C45121.0 (11)
C12—C14—H14C109.5C412—C46—H46119.5
H14B—C14—H14C109.5C45—C46—H46119.5
H14A—C14—H14C109.5C48—C47—C412121.3 (9)
C22—N21—C213118.4 (3)C48—C47—H47119.3
C22—N21—Co1130.7 (3)C412—C47—H47119.3
C213—N21—Co1110.8 (2)C49—C48—C47117.2 (9)
C29—N210—C211118.2 (3)C49—C48—H48121.4
C29—N210—Co1129.0 (2)C47—C48—H48121.4
C211—N210—Co1112.7 (2)N410—C49—C48123.6 (11)
N21—C22—C23122.3 (4)N410—C49—H49118.2
N21—C22—H22118.8C48—C49—H49118.2
C23—C22—H22118.8N410—C411—C412125.5 (10)
C24—C23—C22119.5 (4)N410—C411—C413115.9 (10)
C24—C23—H23120.3C412—C411—C413118.6 (11)
C22—C23—H23120.3C46—C412—C411121.0 (12)
C23—C24—C214120.0 (3)C46—C412—C47124.7 (12)
C23—C24—H24120.0C411—C412—C47114.3 (10)
C214—C24—H24120.0N41—C413—C414122.1 (13)
C26—C25—C214121.7 (3)N41—C413—C411116.2 (11)
C26—C25—H25119.1C414—C413—C411121.6 (11)
C214—C25—H25119.1C44—C414—C413117.5 (11)
C25—C26—C212121.3 (3)C44—C414—C45123.6 (11)
C25—C26—H26119.3C413—C414—C45118.9 (11)
C212—C26—H26119.3H1W1—O1W—H2W1117.4
C28—C27—C212119.4 (3)O3A—N1A—O2A121.0 (7)
C28—C27—H27120.3O3A—N1A—O1A120.3 (6)
C212—C27—H27120.3O2A—N1A—O1A118.7 (6)
C27—C28—C29120.3 (3)O1B—N1B—O3B116.3 (4)
C27—C28—H28119.8O1B—N1B—O2B125.0 (5)
C29—C28—H28119.8O3B—N1B—O2B118.7 (5)
N210—C29—C28121.9 (3)O1B'—N1B'—O2B'117.9 (6)
N210—C29—H29119.0O1B'—N1B'—O3B126.9 (7)
C28—C29—H29119.0O2B'—N1B'—O3B115.3 (7)
N210—C211—C212122.9 (3)C1C—O1C—H1C108.7
N210—C211—C213116.2 (3)O1C—C1C—C2C112.6 (8)
C212—C211—C213120.9 (3)O1C—C1C—H1CA110.6
C211—C212—C27117.2 (3)C2C—C1C—H1CA108.9
C211—C212—C26117.8 (3)O1C—C1C—H1CB108.4
C27—C212—C26125.0 (3)C2C—C1C—H1CB108.5
N21—C213—C214122.8 (3)H1CA—C1C—H1CB107.7
N21—C213—C211116.5 (3)O1C—C1C—H1CC95.7
C214—C213—C211120.7 (3)C1C—C2C—H2CC109.9
C213—C214—C24116.9 (3)C1C—C2C—H2CB109.1
C213—C214—C25117.6 (3)H2CC—C2C—H2CB109.5
C24—C214—C25125.6 (3)C1C—C2C—H2CA109.5
C32—N31—C313118.3 (10)H2CC—C2C—H2CA109.5
C32—N31—Co1131.8 (7)H2CB—C2C—H2CA109.5
C313—N31—Co1109.8 (7)C2C'—C1C'—H2CB108.5
C39—N310—C311119.2 (11)H1CA—C1C'—H2CB107.7
C39—N310—Co1126.5 (8)H1CB—C1C'—H2CA106.6
C311—N310—Co1114.2 (7)C2C'—C1C'—H1CD108.4
N31—C32—C33122.4 (9)C2C'—C1C'—H1CC107.6
N31—C32—H32118.8H2CA—C1C'—H1CC109.2
C33—C32—H32118.8H1CD—C1C'—H1CC107.0
C32—C33—C34118.6 (8)C1C'—C2C'—H2CF108.8
C32—C33—H33120.7C1C'—C2C'—H2CD109.4
C34—C33—H33120.7H2CF—C2C'—H2CD109.5
C314—C34—C33121.8 (9)C1C'—C2C'—H2CE110.2
C314—C34—H34119.1H2CF—C2C'—H2CE109.5
C33—C34—H34119.1H2CD—C2C'—H2CE109.5
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H1O···O11i1.211.212.409 (4)170
O1W—H1W1···O3A0.891.952.816 (9)163
O1W—H2W1···O2B0.891.852.684 (9)155
O1W—H2W1···O2B0.892.042.921 (13)173
O1W—H2W1···O3B0.892.422.940 (8)118
O2W—H1W2···O2A0.892.032.890 (9)161
O2W—H2W2···O12ii0.892.102.845 (5)140
O1C—H1C···O1W0.821.642.395 (7)151
O1C—H1C···O2B0.822.382.884 (6)120
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y+1, z+1/2.
(II) [N-hydroxy-N'-oxidobutane-2,3-diimine(1-)- κ2N,N']bis(1,10-phenanthroline- κ2N,N)cobalt(III) dinitrate ethanol monosolvate 0.4-hydrate top
Crystal data top
[Co(C4H7N2O2)(C12H8N2)2](NO3)2·C2H6O·0.40H2OF(000) = 1472
Mr = 711.79Dx = 1.587 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 8290 reflections
a = 13.7587 (1) Åθ = 4.6–65.2°
b = 11.9763 (1) ŵ = 5.15 mm1
c = 18.2055 (2) ÅT = 130 K
β = 96.744 (1)°Block, dark-red
V = 2979.11 (5) Å30.10 × 0.10 × 0.05 mm
Z = 4
Data collection top
Oxford SuperNova
diffractometer
5254 independent reflections
Radiation source: Nova Cu X-ray Source4545 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.021
ω scansθmax = 66.6°, θmin = 6.5°
Absorption correction: multi-scan
CrysAlis PRO (Oxford Diffraction, 2009)
h = 1615
Tmin = 0.611, Tmax = 0.810k = 1411
14572 measured reflectionsl = 2118
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0786P)2]
where P = (Fo2 + 2Fc2)/3
5254 reflections(Δ/σ)max < 0.001
488 parametersΔρmax = 0.79 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
[Co(C4H7N2O2)(C12H8N2)2](NO3)2·C2H6O·0.40H2OV = 2979.11 (5) Å3
Mr = 711.79Z = 4
Monoclinic, P21/cCu Kα radiation
a = 13.7587 (1) ŵ = 5.15 mm1
b = 11.9763 (1) ÅT = 130 K
c = 18.2055 (2) Å0.10 × 0.10 × 0.05 mm
β = 96.744 (1)°
Data collection top
Oxford SuperNova
diffractometer
5254 independent reflections
Absorption correction: multi-scan
CrysAlis PRO (Oxford Diffraction, 2009)
4545 reflections with I > 2σ(I)
Tmin = 0.611, Tmax = 0.810Rint = 0.021
14572 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.06Δρmax = 0.79 e Å3
5254 reflectionsΔρmin = 0.49 e Å3
488 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.27764 (2)0.25578 (3)0.538389 (18)0.01733 (12)
N110.33983 (12)0.20189 (16)0.63104 (10)0.0230 (4)
N120.32710 (13)0.39383 (15)0.57754 (10)0.0219 (4)
O110.33595 (12)0.09908 (13)0.64919 (9)0.0298 (4)
O120.30142 (11)0.49779 (13)0.54848 (9)0.0273 (3)
H1O0.33090.49670.50310.041*
C110.38522 (15)0.2794 (2)0.67364 (12)0.0246 (5)
C120.37376 (15)0.3909 (2)0.64370 (12)0.0239 (5)
C130.43912 (19)0.2514 (2)0.74724 (14)0.0341 (6)
H13A0.42730.17310.75900.051*
H13B0.41620.29950.78520.051*
H13C0.50940.26320.74590.051*
C140.40974 (18)0.4922 (2)0.68611 (14)0.0329 (5)
H14A0.41460.55460.65180.049*
H14B0.47430.47700.71300.049*
H14C0.36390.51180.72140.049*
N210.23646 (12)0.10583 (15)0.50447 (10)0.0212 (4)
N2100.39475 (13)0.22169 (15)0.49223 (10)0.0194 (4)
C220.15771 (16)0.0475 (2)0.51613 (13)0.0268 (5)
H220.11170.07940.54510.032*
C230.14067 (17)0.0595 (2)0.48700 (14)0.0322 (5)
H230.08370.09930.49650.039*
C240.20560 (17)0.1073 (2)0.44483 (14)0.0308 (5)
H240.19310.17930.42380.037*
C250.36629 (17)0.0910 (2)0.39240 (12)0.0268 (5)
H250.35820.16180.36890.032*
C260.44866 (16)0.0315 (2)0.38706 (12)0.0259 (5)
H260.49790.06180.36040.031*
C270.54796 (15)0.1425 (2)0.41856 (12)0.0245 (5)
H270.60070.11650.39380.029*
C280.55299 (16)0.24435 (19)0.45255 (13)0.0259 (5)
H280.60960.28950.45140.031*
C290.47513 (15)0.2829 (2)0.48922 (12)0.0229 (5)
H290.47980.35410.51230.028*
C2110.38910 (15)0.12048 (18)0.45852 (11)0.0202 (4)
C2120.46322 (15)0.07603 (19)0.42064 (11)0.0220 (4)
C2130.30284 (15)0.05768 (18)0.46455 (11)0.0201 (4)
C2140.29085 (16)0.04875 (19)0.43308 (12)0.0243 (5)
N310.15500 (13)0.28273 (15)0.57786 (10)0.0208 (4)
N3100.20755 (12)0.31986 (15)0.44583 (10)0.0201 (4)
C320.13286 (17)0.26652 (19)0.64601 (13)0.0259 (5)
H320.18220.24040.68290.031*
C330.03914 (17)0.2868 (2)0.66512 (14)0.0289 (5)
H330.02580.27520.71460.035*
C340.03353 (16)0.32310 (19)0.61295 (13)0.0271 (5)
H340.09750.33630.62570.032*
C350.08169 (16)0.3810 (2)0.48076 (14)0.0293 (5)
H350.14770.39330.48920.035*
C360.05421 (17)0.4018 (2)0.41285 (14)0.0309 (5)
H360.10130.42890.37470.037*
C370.07954 (18)0.40794 (19)0.32944 (13)0.0293 (5)
H370.03690.43760.28940.035*
C380.17582 (18)0.38799 (19)0.32209 (13)0.0284 (5)
H380.20080.40550.27700.034*
C390.23787 (16)0.34177 (18)0.38096 (12)0.0232 (5)
H390.30380.32570.37400.028*
C3110.11197 (15)0.34096 (17)0.45414 (12)0.0215 (4)
C3120.04459 (16)0.38378 (18)0.39748 (13)0.0261 (5)
C3130.08333 (15)0.32022 (18)0.52499 (12)0.0207 (4)
C3140.01234 (16)0.34068 (18)0.54007 (13)0.0240 (5)
O1W0.0446 (5)1.0163 (6)0.6486 (3)0.0556 (17)0.403 (6)
H1W10.02180.97450.65480.28 (11)*0.403 (6)
N1A0.34885 (14)0.59349 (18)0.39045 (11)0.0302 (5)
O1A0.39449 (12)0.51624 (14)0.42903 (9)0.0309 (4)
O3A0.38139 (19)0.6285 (2)0.33571 (14)0.0762 (9)
O2A0.27349 (12)0.63370 (15)0.41027 (11)0.0381 (4)
N1B'0.17408 (13)0.46618 (13)0.77274 (9)0.024 (5)0.136 (4)
O1B'0.20339 (10)0.38169 (13)0.81061 (8)0.0386 (6)0.136 (4)
O2B'0.10747 (18)0.52230 (15)0.79232 (16)0.070 (6)0.136 (4)
O3B'0.2151 (2)0.4890 (2)0.71829 (12)0.077 (7)0.136 (4)
N1B0.17301 (10)0.42181 (11)0.79453 (7)0.0351 (8)0.864 (4)
O1B0.14750 (18)0.50887 (17)0.75804 (13)0.0660 (11)0.864 (4)
O2B0.11786 (12)0.38301 (17)0.83768 (10)0.0386 (6)0.864 (4)
O3B0.25240 (11)0.37478 (17)0.78825 (11)0.0436 (6)0.864 (4)
O1C0.1722 (5)0.8724 (5)0.7456 (4)0.068 (2)0.403 (6)
H1C0.13050.90950.70350.082*0.403 (6)
C1C0.1745 (6)0.7630 (6)0.7228 (5)0.046 (2)0.403 (6)
H1CA0.10890.74160.69870.056*0.403 (6)
H1CB0.19030.71430.76660.056*0.403 (6)
C2C0.2476 (6)0.7448 (9)0.6706 (7)0.075 (3)0.403 (6)
H2CA0.21990.76760.62080.112*0.403 (6)
H2CC0.26520.66550.67020.112*0.403 (6)
H2CB0.30620.78930.68610.112*0.403 (6)
O1D0.0780 (4)0.9518 (6)0.6599 (3)0.0727 (15)0.597 (6)
H1D0.00890.94340.65630.073*0.597 (6)
C2D0.2263 (4)0.8467 (7)0.6737 (4)0.070 (2)0.597 (6)
H2DA0.25500.92160.67440.104*0.597 (6)
H2DB0.22210.81620.62340.104*0.597 (6)
H2DC0.26740.79800.70760.104*0.597 (6)
C1D0.1272 (5)0.8531 (7)0.6970 (4)0.074 (2)0.597 (6)
H1DA0.13140.86120.75140.089*0.597 (6)
H1DB0.09000.78430.68250.089*0.597 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01491 (18)0.01660 (19)0.02036 (19)0.00083 (13)0.00165 (13)0.00134 (13)
N110.0171 (8)0.0251 (10)0.0271 (9)0.0033 (7)0.0040 (7)0.0019 (8)
N120.0197 (8)0.0195 (9)0.0263 (9)0.0019 (7)0.0023 (7)0.0023 (7)
O110.0287 (8)0.0246 (9)0.0357 (9)0.0019 (7)0.0017 (7)0.0069 (7)
O120.0313 (8)0.0186 (8)0.0319 (8)0.0029 (6)0.0034 (6)0.0011 (7)
C110.0191 (10)0.0305 (12)0.0242 (11)0.0025 (9)0.0027 (8)0.0022 (10)
C120.0173 (10)0.0302 (12)0.0245 (11)0.0002 (9)0.0045 (8)0.0053 (9)
C130.0307 (13)0.0455 (16)0.0251 (12)0.0029 (11)0.0012 (10)0.0018 (11)
C140.0333 (13)0.0322 (13)0.0324 (12)0.0037 (10)0.0006 (10)0.0091 (11)
N210.0189 (8)0.0190 (9)0.0254 (9)0.0011 (7)0.0009 (7)0.0008 (7)
N2100.0180 (8)0.0186 (9)0.0212 (9)0.0018 (7)0.0008 (7)0.0009 (7)
C220.0197 (10)0.0256 (12)0.0358 (12)0.0021 (9)0.0062 (9)0.0001 (10)
C230.0252 (12)0.0243 (12)0.0474 (15)0.0052 (10)0.0056 (10)0.0009 (11)
C240.0303 (12)0.0204 (12)0.0411 (13)0.0040 (9)0.0014 (10)0.0033 (10)
C250.0320 (12)0.0219 (11)0.0258 (11)0.0040 (9)0.0004 (9)0.0030 (9)
C260.0285 (11)0.0277 (12)0.0214 (11)0.0111 (9)0.0029 (8)0.0006 (9)
C270.0207 (10)0.0306 (12)0.0226 (10)0.0060 (9)0.0043 (8)0.0033 (9)
C280.0188 (11)0.0310 (13)0.0278 (12)0.0020 (9)0.0021 (9)0.0052 (9)
C290.0187 (10)0.0236 (11)0.0257 (11)0.0018 (9)0.0003 (8)0.0000 (9)
C2110.0194 (10)0.0209 (11)0.0197 (10)0.0020 (8)0.0003 (8)0.0023 (8)
C2120.0214 (10)0.0250 (11)0.0192 (10)0.0054 (9)0.0014 (8)0.0038 (9)
C2130.0205 (10)0.0182 (10)0.0208 (10)0.0024 (8)0.0001 (8)0.0014 (8)
C2140.0268 (11)0.0192 (11)0.0258 (11)0.0028 (9)0.0015 (8)0.0004 (9)
N310.0185 (8)0.0192 (9)0.0245 (9)0.0003 (7)0.0014 (7)0.0017 (7)
N3100.0213 (9)0.0157 (8)0.0229 (9)0.0004 (7)0.0004 (7)0.0032 (7)
C320.0231 (11)0.0295 (12)0.0251 (11)0.0002 (9)0.0028 (9)0.0014 (9)
C330.0262 (11)0.0323 (13)0.0297 (12)0.0032 (10)0.0095 (9)0.0019 (10)
C340.0200 (10)0.0242 (11)0.0377 (13)0.0003 (9)0.0063 (9)0.0048 (10)
C350.0195 (11)0.0259 (12)0.0414 (14)0.0030 (9)0.0008 (9)0.0021 (11)
C360.0275 (12)0.0256 (12)0.0374 (13)0.0049 (10)0.0059 (10)0.0014 (10)
C370.0350 (12)0.0222 (11)0.0286 (12)0.0018 (10)0.0046 (9)0.0002 (10)
C380.0403 (13)0.0224 (11)0.0219 (11)0.0014 (10)0.0006 (9)0.0006 (9)
C390.0274 (11)0.0192 (11)0.0233 (11)0.0015 (9)0.0040 (8)0.0046 (9)
C3110.0223 (10)0.0139 (10)0.0275 (11)0.0008 (8)0.0001 (8)0.0035 (9)
C3120.0283 (11)0.0191 (11)0.0294 (12)0.0013 (9)0.0030 (9)0.0017 (9)
C3130.0184 (10)0.0159 (10)0.0271 (11)0.0009 (8)0.0001 (8)0.0024 (9)
C3140.0218 (10)0.0160 (10)0.0340 (12)0.0011 (8)0.0025 (9)0.0035 (9)
O1W0.052 (4)0.058 (4)0.057 (4)0.004 (3)0.008 (3)0.012 (3)
N1A0.0259 (10)0.0297 (11)0.0349 (11)0.0019 (8)0.0032 (8)0.0019 (9)
O1A0.0294 (8)0.0237 (8)0.0392 (9)0.0029 (7)0.0023 (7)0.0038 (7)
O3A0.0806 (17)0.091 (2)0.0658 (16)0.0421 (15)0.0441 (14)0.0435 (14)
O2A0.0299 (9)0.0339 (10)0.0519 (11)0.0070 (8)0.0105 (8)0.0020 (8)
N1B'0.008 (7)0.034 (13)0.030 (10)0.011 (7)0.003 (7)0.014 (10)
O1B'0.0402 (11)0.0410 (13)0.0347 (11)0.0039 (10)0.0043 (9)0.0033 (9)
O2B'0.074 (13)0.105 (17)0.029 (9)0.019 (12)0.004 (8)0.013 (10)
O3B'0.052 (11)0.103 (17)0.079 (13)0.013 (10)0.025 (10)0.009 (12)
N1B0.0439 (16)0.0327 (18)0.0258 (14)0.0008 (13)0.0074 (12)0.0020 (13)
O1B0.074 (3)0.058 (2)0.061 (2)0.0059 (17)0.0137 (18)0.0288 (16)
O2B0.0402 (11)0.0410 (13)0.0347 (11)0.0039 (10)0.0043 (9)0.0033 (9)
O3B0.0363 (12)0.0502 (14)0.0458 (13)0.0008 (11)0.0114 (9)0.0107 (11)
O1C0.058 (4)0.065 (4)0.078 (5)0.003 (3)0.010 (3)0.019 (4)
C1C0.056 (5)0.031 (4)0.054 (5)0.002 (3)0.014 (4)0.009 (3)
C2C0.032 (4)0.077 (7)0.113 (9)0.002 (4)0.002 (5)0.022 (6)
O1D0.054 (3)0.097 (4)0.071 (3)0.002 (3)0.027 (2)0.025 (3)
C2D0.052 (3)0.087 (5)0.071 (4)0.011 (3)0.015 (3)0.001 (4)
C1D0.075 (4)0.089 (5)0.060 (4)0.023 (4)0.022 (4)0.014 (4)
Geometric parameters (Å, º) top
Co1—N111.9118 (18)N310—C3111.365 (3)
Co1—N121.8949 (18)C32—C331.396 (3)
Co1—N211.9609 (18)C32—H320.9500
Co1—N311.9371 (18)C33—C341.367 (3)
Co1—N2101.9460 (18)C33—H330.9500
Co1—N3101.9942 (18)C34—C3141.407 (3)
N11—O111.278 (2)C34—H340.9500
N11—C111.319 (3)C35—C361.358 (4)
N12—C121.297 (3)C35—C3141.438 (3)
N12—O121.382 (2)C35—H350.9500
O12—H1O0.9631C36—C3121.436 (3)
C11—C121.444 (3)C36—H360.9500
C11—C131.491 (3)C37—C381.368 (3)
C12—C141.491 (3)C37—C3121.410 (3)
C13—H13A0.9800C37—H370.9500
C13—H13B0.9800C38—C391.403 (3)
C13—H13C0.9800C38—H380.9500
C14—H14A0.9800C39—H390.9500
C14—H14B0.9800C311—C3121.401 (3)
C14—H14C0.9800C311—C3131.414 (3)
N21—C221.327 (3)C313—C3141.397 (3)
N21—C2131.360 (3)O1W—H1W11.0597
N210—C291.334 (3)N1A—O3A1.214 (3)
N210—C2111.357 (3)N1A—O2A1.235 (3)
C22—C231.396 (3)N1A—O1A1.281 (3)
C22—H220.9500N1B'—O2B'1.2228
C23—C241.370 (3)N1B'—O3B'1.2274
C23—H230.9500N1B'—O1B'1.2635
C24—C2141.405 (3)N1B—O2B1.2445
C24—H240.9500N1B—O3B1.2461
C25—C261.352 (3)N1B—O1B1.2637
C25—C2141.436 (3)O1C—C1C1.375 (9)
C25—H250.9500O1C—H1C1.0056
C26—C2121.430 (3)C1C—C2C1.480 (14)
C26—H260.9500C1C—H1CA0.9900
C27—C281.366 (3)C1C—H1CB0.9900
C27—C2121.416 (3)C2C—H2CA0.9800
C27—H270.9500C2C—H2CC0.9800
C28—C291.405 (3)C2C—H2CB0.9800
C28—H280.9500O1D—C1D1.486 (11)
C29—H290.9500O1D—H1D0.9499
C211—C2121.402 (3)C2D—C1D1.477 (8)
C211—C2131.420 (3)C2D—H2DA0.9800
C213—C2141.399 (3)C2D—H2DB0.9800
N31—C321.326 (3)C2D—H2DC0.9800
N31—C3131.370 (3)C1D—H1DA0.9900
N310—C391.324 (3)C1D—H1DB0.9900
N12—Co1—N1181.89 (8)N21—C213—C211115.87 (19)
N12—Co1—N3190.29 (8)C214—C213—C211120.7 (2)
N11—Co1—N3192.76 (8)C213—C214—C24116.9 (2)
N12—Co1—N21093.81 (8)C213—C214—C25118.3 (2)
N11—Co1—N21090.16 (7)C24—C214—C25124.7 (2)
N31—Co1—N210175.27 (7)C32—N31—C313118.67 (19)
N12—Co1—N21174.40 (7)C32—N31—Co1128.94 (15)
N11—Co1—N2192.95 (8)C313—N31—Co1112.36 (14)
N31—Co1—N2192.14 (8)C39—N310—C311118.08 (19)
N210—Co1—N2183.98 (8)C39—N310—Co1131.15 (15)
N12—Co1—N31095.67 (8)C311—N310—Co1110.75 (14)
N11—Co1—N310175.85 (8)N31—C32—C33121.9 (2)
N31—Co1—N31083.88 (7)N31—C32—H32119.1
N210—Co1—N31093.36 (7)C33—C32—H32119.1
N21—Co1—N31089.61 (7)C34—C33—C32120.3 (2)
O11—N11—C11123.90 (19)C34—C33—H33119.9
O11—N11—Co1121.71 (15)C32—C33—H33119.9
C11—N11—Co1114.39 (16)C33—C34—C314119.2 (2)
C12—N12—O12117.11 (18)C33—C34—H34120.4
C12—N12—Co1116.28 (16)C314—C34—H34120.4
O12—N12—Co1125.28 (13)C36—C35—C314120.9 (2)
N12—O12—H1O101.7C36—C35—H35119.5
N11—C11—C12113.96 (19)C314—C35—H35119.5
N11—C11—C13121.4 (2)C35—C36—C312121.4 (2)
C12—C11—C13124.6 (2)C35—C36—H36119.3
N12—C12—C11113.3 (2)C312—C36—H36119.3
N12—C12—C14123.9 (2)C38—C37—C312118.9 (2)
C11—C12—C14122.8 (2)C38—C37—H37120.5
C11—C13—H13A109.5C312—C37—H37120.5
C11—C13—H13B109.5C37—C38—C39120.2 (2)
H13A—C13—H13B109.5C37—C38—H38119.9
C11—C13—H13C109.5C39—C38—H38119.9
H13A—C13—H13C109.5N310—C39—C38122.2 (2)
H13B—C13—H13C109.5N310—C39—H39118.9
C12—C14—H14A109.5C38—C39—H39118.9
C12—C14—H14B109.5N310—C311—C312123.3 (2)
H14A—C14—H14B109.5N310—C311—C313116.34 (19)
C12—C14—H14C109.5C312—C311—C313120.3 (2)
H14A—C14—H14C109.5C311—C312—C37117.2 (2)
H14B—C14—H14C109.5C311—C312—C36118.1 (2)
C22—N21—C213118.31 (19)C37—C312—C36124.6 (2)
C22—N21—Co1130.01 (16)N31—C313—C314122.4 (2)
C213—N21—Co1111.66 (14)N31—C313—C311116.34 (18)
C29—N210—C211118.46 (19)C314—C313—C311121.2 (2)
C29—N210—Co1129.42 (16)C313—C314—C34117.6 (2)
C211—N210—Co1112.11 (14)C313—C314—C35118.0 (2)
N21—C22—C23121.8 (2)C34—C314—C35124.4 (2)
N21—C22—H22119.1O3A—N1A—O2A120.5 (2)
C23—C22—H22119.1O3A—N1A—O1A119.7 (2)
C24—C23—C22120.4 (2)O2A—N1A—O1A119.7 (2)
C24—C23—H23119.8O2B'—N1B'—O3B'123.0
C22—C23—H23119.8O2B'—N1B'—O1B'118.9
C23—C24—C214119.2 (2)O3B'—N1B'—O1B'118.1
C23—C24—H24120.4O2B—N1B—O3B119.7
C214—C24—H24120.4O2B—N1B—O1B119.2
C26—C25—C214120.9 (2)O3B—N1B—O1B121.1
C26—C25—H25119.5C1C—O1C—H1C102.9
C214—C25—H25119.5O1C—C1C—C2C112.0 (7)
C25—C26—C212121.4 (2)O1C—C1C—H1CA109.2
C25—C26—H26119.3C2C—C1C—H1CA109.2
C212—C26—H26119.3O1C—C1C—H1CB109.2
C28—C27—C212119.2 (2)C2C—C1C—H1CB109.2
C28—C27—H27120.4H1CA—C1C—H1CB107.9
C212—C27—H27120.4C1D—O1D—H1D110.2
C27—C28—C29120.5 (2)C1D—C2D—H2DA109.5
C27—C28—H28119.7C1D—C2D—H2DB109.5
C29—C28—H28119.7H2DA—C2D—H2DB109.5
N210—C29—C28121.4 (2)C1D—C2D—H2DC109.5
N210—C29—H29119.3H2DA—C2D—H2DC109.5
C28—C29—H29119.3H2DB—C2D—H2DC109.5
N210—C211—C212123.7 (2)C2D—C1D—O1D107.3 (5)
N210—C211—C213116.24 (19)C2D—C1D—H1DA110.3
C212—C211—C213120.0 (2)O1D—C1D—H1DA110.3
C211—C212—C27116.7 (2)C2D—C1D—H1DB110.3
C211—C212—C26118.6 (2)O1D—C1D—H1DB110.3
C27—C212—C26124.7 (2)H1DA—C1D—H1DB108.5
N21—C213—C214123.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H1O···O1A0.961.712.659 (2)169
O12—H1O···O2A0.962.422.984 (2)117
O1W—H1W1···O2Bi1.061.712.464 (13)124
O1W—H1W1···O2Bi1.061.732.782 (8)169
O1C—H1C···O1W1.011.942.905 (11)161
O1D—H1D···O2Bi0.951.902.824 (8)162
Symmetry code: (i) x, y+1/2, z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Co2(C4H6N2O2)(C4H7N2O2)(C12H8N2)4]·(NO3)3·2C2H6O·1.87H2O[Co(C4H7N2O2)(C12H8N2)2](NO3)2·C2H6O·0.40H2O
Mr1379.76711.79
Crystal system, space groupMonoclinic, C2/cMonoclinic, P21/c
Temperature (K)130130
a, b, c (Å)19.0680 (8), 16.0170 (5), 20.0130 (8)13.7587 (1), 11.9763 (1), 18.2055 (2)
β (°) 104.353 (4) 96.744 (1)
V3)5921.4 (4)2979.11 (5)
Z44
Radiation typeMo KαCu Kα
µ (mm1)0.655.15
Crystal size (mm)0.50 × 0.40 × 0.400.10 × 0.10 × 0.05
Data collection
DiffractometerOxford XcaliburE CCD
diffractometer
Oxford SuperNova
diffractometer
Absorption correctionMulti-scan
CrysAlis PRO (Oxford Diffraction, 2009)
Multi-scan
CrysAlis PRO (Oxford Diffraction, 2009)
Tmin, Tmax0.720, 0.8040.611, 0.810
No. of measured, independent and
observed [I > 2σ(I)] reflections
25463, 5211, 3075 14572, 5254, 4545
Rint0.0530.021
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.095, 0.89 0.038, 0.109, 1.06
No. of reflections52115254
No. of parameters614488
No. of restraints1830
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.460.79, 0.49

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Selected geometric parameters (Å, º) for (I) top
Co1—N111.887 (3)Co1—N2101.943 (3)
Co1—N121.911 (2)Co1—N3101.894 (11)
Co1—N211.995 (3)Co1—N4102.097 (13)
Co1—N312.036 (12)N11—O111.342 (3)
Co1—N411.848 (14)N12—O121.287 (3)
N11—Co1—N310168.0 (3)N41—Co1—N210169.7 (4)
N11—Co1—N410174.2 (3)N210—Co1—N31175.5 (3)
N12—Co1—N21172.92 (10)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O11—H1O···O11i1.2091.2092.409 (4)170
O1W—H1W1···O3A0.891.952.816 (9)163
O1W—H2W1···O2B0.891.852.684 (9)155
O1W—H2W1···O2B'0.892.042.921 (13)173
O1W—H2W1···O3B0.892.422.940 (8)118
O2W—H1W2···O2A0.892.032.890 (9)161
O2W—H2W2···O12ii0.892.102.845 (5)140
O1C—H1C···O1W0.821.642.395 (7)151
O1C—H1C···O2B0.822.382.884 (6)120
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y+1, z+1/2.
Selected geometric parameters (Å, º) for (II) top
Co1—N111.9118 (18)Co1—N2101.9460 (18)
Co1—N121.8949 (18)Co1—N3101.9942 (18)
Co1—N211.9609 (18)N11—O111.278 (2)
Co1—N311.9371 (18)N12—O121.382 (2)
N31—Co1—N210175.27 (7)N11—Co1—N310175.85 (8)
N12—Co1—N21174.40 (7)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O12—H1O···O1A0.961.712.659 (2)169
O12—H1O···O2A0.962.422.984 (2)117
O1W—H1W1···O2B'i1.061.712.464 (13)124
O1W—H1W1···O2Bi1.061.732.782 (8)169
O1C—H1C···O1W1.011.942.905 (11)161
O1D—H1D···O2Bi0.951.902.824 (8)162
Symmetry code: (i) x, y+1/2, z+3/2.
 

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