The reaction of cobalt(II) nitrate hexahydrate with dimethylglyoxime (DMGH
2) and 1,10-phenanthroline (phen) in a 1:1:2 molar ratio results in two Co
III mono-dimethylglyoximates having two chelating phen ligands in
cis positions and the Co
III atom coordinated by six N atoms in a distorted octahedral coordination geometry. The isolated products differ in the deprotonation state of the DMGH
2 ligand. In [μ-hydrogen bis(
N,
N′-dioxidobutane-2,3-diimine)]tetrakis(1,10-phenanthroline)cobalt(III) trinitrate ethanol disolvate 1.87-hydrate, [Co
2(C
4H
6N
2O
2)(C
4H
7N
2O
2)(C
12H
8N
2)
4](NO
3)
3·2C
2H
6O·1.87H
2O, (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(C
4H
7N
2O
2)(C
12H
8N
2)
2](NO
3)
2·C
2H
6O·0.40H
2O, (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
CCDC references: 796065; 796066
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.
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.
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).
(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·1.87H2O | F(000) = 2859 |
Mr = 1379.76 | Dx = 1.548 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 9535 reflections |
a = 19.0680 (8) Å | θ = 2.8–24.9° |
b = 16.0170 (5) Å | µ = 0.65 mm−1 |
c = 20.0130 (8) Å | T = 130 K |
β = 104.353 (4)° | Needle, red |
V = 5921.4 (4) Å3 | 0.50 × 0.40 × 0.40 mm |
Z = 4 | |
Data collection top
Oxford XcaliburE CCD diffractometer | 5211 independent reflections |
Radiation source: fine-focus sealed tube | 3075 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω scans | θmax = 25.0°, θmin = 4.2° |
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009) | h = −22→22 |
Tmin = 0.720, Tmax = 0.804 | k = −18→19 |
25463 measured reflections | l = −23→23 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-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 parameters | Δρmax = 0.34 e Å−3 |
183 restraints | Δρmin = −0.46 e Å−3 |
Crystal data top
[Co2(C4H6N2O2)(C4H7N2O2)(C12H8N2)4]·(NO3)3·2C2H6O·1.87H2O | V = 5921.4 (4) Å3 |
Mr = 1379.76 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.0680 (8) Å | µ = 0.65 mm−1 |
b = 16.0170 (5) Å | T = 130 K |
c = 20.0130 (8) Å | 0.50 × 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 = 0.804 | Rint = 0.053 |
25463 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 183 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.34 e Å−3 |
5211 reflections | Δρmin = −0.46 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.55990 (2) | 0.21717 (2) | 0.10577 (2) | 0.03478 (15) | |
N11 | 0.57067 (14) | 0.17428 (16) | 0.19555 (13) | 0.0354 (7) | |
N12 | 0.59389 (13) | 0.10858 (15) | 0.08974 (13) | 0.0305 (6) | |
O11 | 0.56294 (12) | 0.22055 (14) | 0.24915 (11) | 0.0473 (6) | |
H1O | 0.5000 | 0.2140 | 0.2500 | 0.071* | |
O12 | 0.59934 (11) | 0.08509 (12) | 0.02976 (10) | 0.0377 (5) | |
C11 | 0.59519 (17) | 0.0986 (2) | 0.20504 (16) | 0.0368 (8) | |
C12 | 0.60775 (17) | 0.06000 (19) | 0.14341 (16) | 0.0333 (8) | |
C13 | 0.6104 (2) | 0.0549 (2) | 0.27320 (16) | 0.0501 (10) | |
H13C | 0.6618 | 0.0608 | 0.2965 | 0.075* | |
H13B | 0.5985 | −0.0045 | 0.2659 | 0.075* | |
H13A | 0.5810 | 0.0797 | 0.3018 | 0.075* | |
C14 | 0.6334 (2) | −0.0271 (2) | 0.13888 (17) | 0.0491 (10) | |
H14B | 0.5932 | −0.0615 | 0.1133 | 0.074* | |
H14A | 0.6515 | −0.0498 | 0.1855 | 0.074* | |
H14C | 0.6725 | −0.0272 | 0.1150 | 0.074* | |
N21 | 0.51604 (16) | 0.32337 (16) | 0.12822 (13) | 0.0412 (7) | |
N210 | 0.45986 (14) | 0.17976 (16) | 0.07948 (12) | 0.0327 (6) | |
C22 | 0.5466 (2) | 0.3956 (2) | 0.15209 (19) | 0.0542 (10) | |
H22 | 0.5974 | 0.4018 | 0.1586 | 0.065* | |
C23 | 0.5068 (2) | 0.4624 (2) | 0.1680 (2) | 0.0624 (12) | |
H23 | 0.5300 | 0.5138 | 0.1835 | 0.075* | |
C24 | 0.4341 (2) | 0.4535 (2) | 0.16102 (19) | 0.0599 (11) | |
H24 | 0.4067 | 0.4984 | 0.1725 | 0.072* | |
C25 | 0.3241 (2) | 0.3602 (3) | 0.12752 (19) | 0.0544 (11) | |
H25 | 0.2937 | 0.4016 | 0.1395 | 0.065* | |
C26 | 0.2952 (2) | 0.2867 (3) | 0.10224 (18) | 0.0510 (10) | |
H26 | 0.2449 | 0.2773 | 0.0968 | 0.061* | |
C27 | 0.3129 (2) | 0.1444 (2) | 0.05552 (16) | 0.0463 (9) | |
H27 | 0.2629 | 0.1311 | 0.0477 | 0.056* | |
C28 | 0.35988 (19) | 0.0882 (2) | 0.03984 (15) | 0.0426 (9) | |
H28 | 0.3425 | 0.0360 | 0.0198 | 0.051* | |
C29 | 0.43328 (18) | 0.1067 (2) | 0.05305 (15) | 0.0360 (8) | |
H29 | 0.4654 | 0.0660 | 0.0429 | 0.043* | |
C211 | 0.41307 (18) | 0.23714 (19) | 0.09395 (15) | 0.0350 (8) | |
C212 | 0.33884 (18) | 0.2222 (2) | 0.08329 (16) | 0.0399 (8) | |
C213 | 0.4434 (2) | 0.3146 (2) | 0.12002 (17) | 0.0389 (9) | |
C214 | 0.3998 (2) | 0.3778 (2) | 0.13687 (18) | 0.0483 (10) | |
N31 | 0.6636 (6) | 0.2582 (7) | 0.1407 (6) | 0.031 (2) | 0.564 (7) |
N310 | 0.5705 (5) | 0.2612 (7) | 0.0210 (5) | 0.035 (3) | 0.564 (7) |
C32 | 0.7087 (5) | 0.2574 (5) | 0.2032 (5) | 0.033 (2) | 0.564 (7) |
H32 | 0.6933 | 0.2324 | 0.2401 | 0.040* | 0.564 (7) |
C33 | 0.7776 (4) | 0.2919 (4) | 0.2163 (5) | 0.044 (2) | 0.564 (7) |
H33 | 0.8085 | 0.2913 | 0.2615 | 0.053* | 0.564 (7) |
C34 | 0.8004 (5) | 0.3272 (5) | 0.1617 (5) | 0.047 (2) | 0.564 (7) |
H34 | 0.8476 | 0.3504 | 0.1701 | 0.057* | 0.564 (7) |
C35 | 0.7737 (5) | 0.3618 (5) | 0.0367 (5) | 0.055 (2) | 0.564 (7) |
H35 | 0.8204 | 0.3850 | 0.0409 | 0.066* | 0.564 (7) |
C36 | 0.7251 (6) | 0.3612 (6) | −0.0275 (6) | 0.039 (3) | 0.564 (7) |
H36 | 0.7385 | 0.3839 | −0.0664 | 0.047* | 0.564 (7) |
C37 | 0.6025 (6) | 0.3233 (5) | −0.0955 (6) | 0.040 (3) | 0.564 (7) |
H37 | 0.6133 | 0.3454 | −0.1359 | 0.049* | 0.564 (7) |
C38 | 0.5362 (6) | 0.2908 (6) | −0.1014 (5) | 0.044 (3) | 0.564 (7) |
H38 | 0.5009 | 0.2891 | −0.1442 | 0.053* | 0.564 (7) |
C39 | 0.5221 (6) | 0.2586 (6) | −0.0387 (7) | 0.040 (3) | 0.564 (7) |
H39 | 0.4761 | 0.2346 | −0.0405 | 0.048* | 0.564 (7) |
C311 | 0.6369 (6) | 0.2943 (6) | 0.0240 (6) | 0.031 (2) | 0.564 (7) |
C312 | 0.6559 (5) | 0.3268 (5) | −0.0347 (5) | 0.043 (2) | 0.564 (7) |
C313 | 0.6864 (5) | 0.2935 (5) | 0.0882 (5) | 0.030 (2) | 0.564 (7) |
C314 | 0.7563 (6) | 0.3295 (6) | 0.0956 (7) | 0.044 (3) | 0.564 (7) |
N41 | 0.6498 (7) | 0.2667 (8) | 0.1181 (6) | 0.028 (3) | 0.436 (7) |
N410 | 0.5493 (6) | 0.2525 (7) | 0.0028 (7) | 0.018 (3) | 0.436 (7) |
C42 | 0.6982 (8) | 0.2744 (8) | 0.1776 (8) | 0.035 (3) | 0.436 (7) |
H42 | 0.6870 | 0.2526 | 0.2179 | 0.042* | 0.436 (7) |
C43 | 0.7660 (7) | 0.3137 (7) | 0.1840 (6) | 0.050 (3) | 0.436 (7) |
H43 | 0.7997 | 0.3188 | 0.2275 | 0.059* | 0.436 (7) |
C44 | 0.7813 (8) | 0.3439 (8) | 0.1257 (8) | 0.045 (4) | 0.436 (7) |
H44 | 0.8265 | 0.3705 | 0.1288 | 0.054* | 0.436 (7) |
C45 | 0.7465 (8) | 0.3656 (8) | −0.0006 (7) | 0.032 (3) | 0.436 (7) |
H45 | 0.7916 | 0.3908 | −0.0007 | 0.039* | 0.436 (7) |
C46 | 0.6920 (6) | 0.3563 (6) | −0.0629 (6) | 0.043 (3) | 0.436 (7) |
H46 | 0.7007 | 0.3760 | −0.1049 | 0.051* | 0.436 (7) |
C47 | 0.5692 (6) | 0.3078 (5) | −0.1235 (5) | 0.028 (2) | 0.436 (7) |
H47 | 0.5749 | 0.3263 | −0.1670 | 0.033* | 0.436 (7) |
C48 | 0.5031 (6) | 0.2692 (5) | −0.1197 (5) | 0.030 (3) | 0.436 (7) |
H48 | 0.4646 | 0.2613 | −0.1596 | 0.036* | 0.436 (7) |
C49 | 0.4970 (6) | 0.2433 (7) | −0.0544 (6) | 0.024 (3) | 0.436 (7) |
H49 | 0.4531 | 0.2178 | −0.0510 | 0.028* | 0.436 (7) |
C411 | 0.6122 (6) | 0.2902 (7) | −0.0022 (5) | 0.022 (3) | 0.436 (7) |
C412 | 0.6271 (7) | 0.3193 (7) | −0.0634 (7) | 0.026 (3) | 0.436 (7) |
C413 | 0.6660 (7) | 0.2989 (7) | 0.0601 (7) | 0.022 (3) | 0.436 (7) |
C414 | 0.7325 (6) | 0.3367 (6) | 0.0621 (6) | 0.039 (3) | 0.436 (7) |
O1W | 0.6457 (4) | 0.7548 (4) | 0.1543 (4) | 0.100 (3) | 0.436 (7) |
H1W1 | 0.6124 | 0.7788 | 0.1722 | 0.151* | 0.436 (7) |
H2W1 | 0.6747 | 0.7172 | 0.1801 | 0.151* | 0.436 (7) |
O2W | 0.5591 (3) | 0.9356 (3) | 0.3840 (2) | 0.0523 (13) | 0.50 |
H1W2 | 0.5316 | 0.9036 | 0.3515 | 0.078* | 0.50 |
H2W2 | 0.5766 | 0.9053 | 0.4218 | 0.078* | 0.50 |
N1A | 0.5016 (3) | 0.8621 (2) | 0.2198 (3) | 0.049 (3) | 0.50 |
O1A | 0.4785 (3) | 0.8913 (3) | 0.1606 (3) | 0.0614 (14) | 0.50 |
O3A | 0.5622 (3) | 0.8284 (4) | 0.2365 (4) | 0.068 (2) | 0.50 |
O2A | 0.4628 (4) | 0.8674 (4) | 0.2614 (4) | 0.057 (2) | 0.50 |
N1B | 0.6857 (2) | 0.59657 (18) | 0.2473 (2) | 0.048 (2) | 0.638 (5) |
O1B | 0.7153 (2) | 0.5660 (3) | 0.3032 (2) | 0.0703 (16) | 0.638 (5) |
O2B | 0.7167 (2) | 0.6131 (3) | 0.2001 (2) | 0.0760 (19) | 0.638 (5) |
O3B | 0.61938 (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 |
O1C | 0.63865 (16) | 0.65745 (17) | 0.06206 (18) | 0.0926 (12) | 0.638 (5) |
H1C | 0.6402 | 0.6763 | 0.1005 | 0.139* | |
C1C | 0.5942 (5) | 0.5902 (3) | 0.0510 (4) | 0.0423 (18) | 0.638 (5) |
H1CA | 0.5725 | 0.5822 | 0.0890 | 0.051* | 0.638 (5) |
H1CB | 0.5559 | 0.6005 | 0.0105 | 0.051* | 0.638 (5) |
C2C | 0.6330 (5) | 0.5106 (4) | 0.0399 (5) | 0.071 (3) | 0.638 (5) |
H2CC | 0.5994 | 0.4649 | 0.0311 | 0.085* | 0.638 (5) |
H2CB | 0.6706 | 0.4991 | 0.0805 | 0.085* | 0.638 (5) |
H2CA | 0.6538 | 0.5177 | 0.0012 | 0.085* | 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) |
H1CD | 0.6654 | 0.5455 | 0.0218 | 0.138* | 0.362 (5) |
H1CC | 0.6462 | 0.5327 | 0.0925 | 0.138* | 0.362 (5) |
C2C' | 0.5692 (10) | 0.5325 (16) | 0.0177 (9) | 0.115 (5) | 0.362 (5) |
H2CF | 0.5727 | 0.4730 | 0.0135 | 0.172* | 0.362 (5) |
H2CD | 0.5542 | 0.5570 | −0.0274 | 0.172* | 0.362 (5) |
H2CE | 0.5344 | 0.5454 | 0.0436 | 0.172* | 0.362 (5) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0364 (3) | 0.0351 (2) | 0.0411 (3) | −0.0070 (2) | 0.0251 (2) | 0.0013 (2) |
N11 | 0.0336 (17) | 0.0393 (16) | 0.0356 (17) | −0.0139 (13) | 0.0133 (13) | −0.0100 (13) |
N12 | 0.0311 (16) | 0.0375 (15) | 0.0263 (16) | −0.0080 (12) | 0.0133 (13) | 0.0003 (13) |
O11 | 0.0492 (15) | 0.0568 (14) | 0.0415 (14) | −0.0212 (12) | 0.0218 (12) | −0.0197 (12) |
O12 | 0.0439 (14) | 0.0445 (13) | 0.0302 (13) | −0.0005 (11) | 0.0195 (11) | 0.0028 (10) |
C11 | 0.035 (2) | 0.049 (2) | 0.026 (2) | −0.0155 (17) | 0.0073 (16) | −0.0045 (16) |
C12 | 0.033 (2) | 0.0381 (18) | 0.028 (2) | −0.0082 (15) | 0.0060 (16) | 0.0001 (15) |
C13 | 0.065 (3) | 0.060 (2) | 0.022 (2) | −0.007 (2) | 0.0046 (18) | −0.0025 (16) |
C14 | 0.059 (3) | 0.054 (2) | 0.035 (2) | 0.0009 (19) | 0.0118 (19) | 0.0067 (16) |
N21 | 0.050 (2) | 0.0347 (16) | 0.0487 (19) | −0.0058 (14) | 0.0314 (15) | 0.0030 (13) |
N210 | 0.0374 (17) | 0.0419 (16) | 0.0222 (15) | −0.0032 (14) | 0.0138 (13) | 0.0072 (12) |
C22 | 0.066 (3) | 0.042 (2) | 0.070 (3) | −0.010 (2) | 0.047 (2) | −0.0005 (19) |
C23 | 0.092 (3) | 0.034 (2) | 0.084 (3) | −0.009 (2) | 0.066 (3) | 0.0019 (19) |
C24 | 0.081 (3) | 0.042 (2) | 0.077 (3) | 0.011 (2) | 0.058 (3) | 0.015 (2) |
C25 | 0.059 (3) | 0.060 (3) | 0.058 (3) | 0.022 (2) | 0.038 (2) | 0.027 (2) |
C26 | 0.044 (2) | 0.067 (3) | 0.047 (2) | 0.012 (2) | 0.0193 (18) | 0.026 (2) |
C27 | 0.036 (2) | 0.079 (3) | 0.024 (2) | −0.010 (2) | 0.0059 (17) | 0.0112 (18) |
C28 | 0.040 (2) | 0.065 (2) | 0.0214 (19) | −0.010 (2) | 0.0041 (17) | −0.0013 (16) |
C29 | 0.039 (2) | 0.049 (2) | 0.0212 (18) | −0.0067 (17) | 0.0093 (16) | 0.0012 (15) |
C211 | 0.040 (2) | 0.043 (2) | 0.0258 (19) | 0.0025 (17) | 0.0155 (16) | 0.0119 (15) |
C212 | 0.034 (2) | 0.062 (2) | 0.0235 (18) | 0.007 (2) | 0.0076 (16) | 0.0194 (17) |
C213 | 0.046 (2) | 0.042 (2) | 0.037 (2) | 0.0039 (18) | 0.0263 (18) | 0.0137 (16) |
C214 | 0.060 (3) | 0.043 (2) | 0.055 (2) | 0.009 (2) | 0.039 (2) | 0.0180 (17) |
N31 | 0.027 (4) | 0.035 (3) | 0.036 (5) | −0.002 (3) | 0.013 (4) | 0.009 (4) |
N310 | 0.031 (5) | 0.042 (4) | 0.030 (5) | 0.003 (3) | 0.007 (3) | 0.001 (3) |
C32 | 0.033 (4) | 0.028 (3) | 0.039 (4) | −0.004 (3) | 0.008 (4) | 0.005 (3) |
C33 | 0.037 (4) | 0.038 (3) | 0.054 (4) | −0.005 (3) | 0.008 (3) | 0.001 (3) |
C34 | 0.042 (4) | 0.039 (3) | 0.060 (5) | −0.009 (3) | 0.011 (4) | −0.003 (3) |
C35 | 0.057 (4) | 0.052 (4) | 0.067 (5) | −0.007 (3) | 0.034 (4) | 0.012 (4) |
C36 | 0.038 (5) | 0.049 (4) | 0.037 (5) | −0.012 (4) | 0.021 (4) | 0.012 (4) |
C37 | 0.044 (5) | 0.040 (4) | 0.040 (5) | 0.006 (4) | 0.016 (4) | 0.007 (4) |
C38 | 0.051 (5) | 0.047 (4) | 0.039 (4) | 0.005 (4) | 0.018 (4) | 0.008 (3) |
C39 | 0.041 (5) | 0.045 (4) | 0.039 (5) | −0.001 (4) | 0.018 (4) | 0.008 (4) |
C311 | 0.028 (5) | 0.036 (4) | 0.031 (5) | 0.000 (3) | 0.014 (4) | 0.007 (4) |
C312 | 0.049 (5) | 0.041 (3) | 0.043 (4) | −0.001 (3) | 0.020 (4) | 0.009 (3) |
C313 | 0.030 (4) | 0.029 (3) | 0.034 (4) | −0.002 (3) | 0.011 (3) | 0.004 (3) |
C314 | 0.046 (5) | 0.046 (4) | 0.045 (5) | −0.001 (4) | 0.019 (4) | 0.001 (4) |
N41 | 0.027 (5) | 0.033 (4) | 0.021 (5) | −0.009 (3) | 0.002 (4) | −0.006 (4) |
N410 | 0.018 (5) | 0.022 (3) | 0.016 (5) | −0.006 (3) | 0.009 (4) | 0.001 (4) |
C42 | 0.033 (5) | 0.039 (5) | 0.032 (5) | −0.008 (4) | 0.007 (4) | 0.002 (4) |
C43 | 0.048 (5) | 0.058 (5) | 0.045 (5) | −0.013 (4) | 0.015 (4) | −0.006 (4) |
C44 | 0.040 (5) | 0.052 (5) | 0.042 (6) | −0.011 (4) | 0.011 (4) | −0.003 (4) |
C45 | 0.027 (5) | 0.041 (4) | 0.027 (6) | −0.016 (4) | 0.005 (4) | 0.004 (4) |
C46 | 0.047 (5) | 0.044 (4) | 0.044 (5) | −0.010 (4) | 0.024 (4) | 0.004 (4) |
C47 | 0.031 (4) | 0.031 (4) | 0.025 (4) | −0.001 (3) | 0.015 (4) | 0.003 (3) |
C48 | 0.046 (7) | 0.024 (5) | 0.026 (6) | 0.000 (4) | 0.020 (5) | 0.006 (4) |
C49 | 0.022 (4) | 0.026 (4) | 0.021 (5) | 0.000 (3) | 0.002 (4) | −0.005 (3) |
C411 | 0.022 (5) | 0.026 (4) | 0.022 (5) | −0.006 (3) | 0.012 (4) | 0.002 (4) |
C412 | 0.019 (5) | 0.034 (4) | 0.023 (5) | −0.003 (4) | 0.003 (4) | −0.003 (4) |
C413 | 0.018 (5) | 0.029 (4) | 0.018 (5) | −0.011 (4) | 0.005 (4) | 0.001 (4) |
C414 | 0.031 (5) | 0.042 (4) | 0.043 (5) | −0.015 (4) | 0.011 (4) | −0.003 (4) |
O1W | 0.110 (7) | 0.082 (5) | 0.130 (7) | −0.011 (4) | 0.069 (5) | −0.026 (4) |
O2W | 0.065 (4) | 0.050 (3) | 0.035 (3) | −0.001 (3) | 0.000 (3) | −0.006 (2) |
N1A | 0.061 (7) | 0.045 (4) | 0.039 (6) | −0.008 (4) | 0.008 (5) | −0.004 (4) |
O1A | 0.057 (4) | 0.071 (4) | 0.053 (4) | −0.005 (3) | 0.009 (3) | 0.007 (3) |
O3A | 0.055 (5) | 0.086 (6) | 0.063 (4) | 0.027 (4) | 0.014 (3) | −0.002 (4) |
O2A | 0.060 (7) | 0.066 (6) | 0.044 (5) | 0.005 (4) | 0.015 (5) | 0.008 (4) |
N1B | 0.028 (4) | 0.064 (4) | 0.059 (5) | −0.019 (3) | 0.025 (4) | −0.033 (3) |
O1B | 0.063 (3) | 0.080 (4) | 0.062 (3) | 0.003 (3) | 0.006 (3) | 0.014 (3) |
O2B | 0.058 (3) | 0.146 (5) | 0.034 (3) | −0.029 (3) | 0.030 (2) | −0.030 (3) |
O3B | 0.071 (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) |
O1C | 0.067 (2) | 0.064 (2) | 0.158 (3) | −0.0086 (17) | 0.049 (2) | −0.0126 (19) |
C1C | 0.054 (5) | 0.022 (3) | 0.065 (4) | −0.012 (3) | 0.042 (4) | −0.017 (3) |
C2C | 0.090 (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—N11 | 1.887 (3) | C37—C312 | 1.382 (13) |
Co1—N12 | 1.911 (2) | C37—H37 | 0.9500 |
Co1—N21 | 1.995 (3) | C38—C39 | 1.442 (15) |
Co1—N31 | 2.036 (12) | C38—H38 | 0.9500 |
Co1—N41 | 1.848 (14) | C39—H39 | 0.9500 |
Co1—N210 | 1.943 (3) | C311—C313 | 1.393 (13) |
Co1—N310 | 1.894 (11) | C311—C312 | 1.412 (12) |
Co1—N410 | 2.097 (13) | C313—C314 | 1.425 (14) |
N11—C11 | 1.296 (4) | N41—C42 | 1.319 (19) |
N11—O11 | 1.342 (3) | N41—C413 | 1.375 (17) |
N12—O12 | 1.287 (3) | N410—C49 | 1.327 (18) |
N12—C12 | 1.299 (4) | N410—C411 | 1.369 (16) |
O11—H1O | 1.2087 | C42—C43 | 1.415 (18) |
C11—C12 | 1.452 (4) | C42—H42 | 0.9500 |
C11—C13 | 1.496 (4) | C43—C44 | 1.359 (16) |
C12—C14 | 1.488 (4) | C43—H43 | 0.9500 |
C13—H13C | 0.9800 | C44—C414 | 1.383 (17) |
C13—H13B | 0.9800 | C44—H44 | 0.9500 |
C13—H13A | 0.9800 | C45—C414 | 1.424 (16) |
C14—H14B | 0.9800 | C45—C46 | 1.420 (16) |
C14—H14A | 0.9800 | C45—H45 | 0.9500 |
C14—H14C | 0.9800 | C46—C412 | 1.370 (15) |
N21—C22 | 1.329 (4) | C46—H46 | 0.9500 |
N21—C213 | 1.361 (4) | C47—C48 | 1.423 (14) |
N210—C29 | 1.332 (4) | C47—C412 | 1.429 (16) |
N210—C211 | 1.361 (4) | C47—H47 | 0.9500 |
C22—C23 | 1.395 (5) | C48—C49 | 1.402 (15) |
C22—H22 | 0.9500 | C48—H48 | 0.9500 |
C23—C24 | 1.365 (5) | C49—H49 | 0.9500 |
C23—H23 | 0.9500 | C411—C412 | 1.404 (16) |
C24—C214 | 1.404 (5) | C411—C413 | 1.412 (16) |
C24—H24 | 0.9500 | C413—C414 | 1.395 (15) |
C25—C26 | 1.344 (5) | O1W—H1W1 | 0.8900 |
C25—C214 | 1.436 (5) | O1W—H2W1 | 0.8900 |
C25—H25 | 0.9500 | O2W—O1Ai | 1.223 (6) |
C26—C212 | 1.435 (5) | O2W—H1W2 | 0.8900 |
C26—H26 | 0.9500 | O2W—H2W2 | 0.8900 |
C27—C28 | 1.361 (5) | N1A—O3A | 1.243 (5) |
C27—C212 | 1.404 (5) | N1A—O2A | 1.247 (5) |
C27—H27 | 0.9500 | N1A—O1A | 1.248 (5) |
C28—C29 | 1.390 (4) | N1B—O1B | 1.223 (4) |
C28—H28 | 0.9500 | N1B—O3B | 1.255 (4) |
C29—H29 | 0.9500 | N1B—O2B | 1.260 (4) |
C211—C212 | 1.399 (4) | O1B—N1B' | 1.245 (6) |
C211—C213 | 1.413 (4) | O3B—N1B' | 1.252 (5) |
C213—C214 | 1.403 (4) | N1B'—O1B' | 1.241 (5) |
N31—C32 | 1.330 (14) | N1B'—O2B' | 1.246 (5) |
N31—C313 | 1.357 (13) | O1C—C1C | 1.354 (7) |
N310—C39 | 1.316 (15) | O1C—H1C | 0.8200 |
N310—C311 | 1.360 (13) | C1C—C2C | 1.518 (10) |
C32—C33 | 1.389 (12) | C1C—H1CA | 0.9600 |
C32—H32 | 0.9500 | C1C—H1CB | 0.9606 |
C33—C34 | 1.392 (12) | C2C—H2CC | 0.9600 |
C33—H33 | 0.9500 | C2C—H2CB | 0.9603 |
C34—C314 | 1.381 (14) | C2C—H2CA | 0.9599 |
C34—H34 | 0.9500 | C2C—H1CD | 0.9674 |
C35—C36 | 1.386 (13) | C1C'—C2C' | 1.27 (3) |
C35—C314 | 1.400 (12) | C1C'—H1CD | 0.9700 |
C35—H35 | 0.9500 | C1C'—H1CC | 0.9700 |
C36—C312 | 1.403 (13) | C2C'—H2CF | 0.9600 |
C36—H36 | 0.9500 | C2C'—H2CD | 0.9600 |
C37—C38 | 1.345 (12) | C2C'—H2CE | 0.9600 |
| | | |
N11—Co1—N12 | 82.36 (11) | C36—C35—C314 | 122.3 (10) |
N11—Co1—N21 | 92.80 (11) | C36—C35—H35 | 118.9 |
N11—Co1—N31 | 85.6 (3) | C314—C35—H35 | 118.9 |
N11—Co1—N41 | 98.6 (4) | C35—C36—C312 | 119.5 (8) |
N11—Co1—N210 | 90.77 (10) | C35—C36—H36 | 120.2 |
N11—Co1—N310 | 168.0 (3) | C312—C36—H36 | 120.2 |
N11—Co1—N410 | 174.2 (3) | C38—C37—C312 | 124.3 (10) |
N12—Co1—N21 | 172.92 (10) | C38—C37—H37 | 117.9 |
N12—Co1—N31 | 90.6 (3) | C312—C37—H37 | 117.9 |
N12—Co1—N41 | 94.1 (4) | C37—C38—C39 | 115.9 (9) |
N12—Co1—N210 | 91.43 (11) | C37—C38—H38 | 122.1 |
N12—Co1—N410 | 92.0 (3) | C39—C38—H38 | 122.1 |
N21—Co1—N31 | 94.2 (3) | N310—C39—C38 | 122.6 (10) |
N21—Co1—N41 | 91.8 (4) | N310—C39—H39 | 118.7 |
N21—Co1—N410 | 92.7 (3) | C38—C39—H39 | 118.7 |
N41—Co1—N210 | 169.7 (4) | N310—C311—C313 | 116.6 (9) |
N41—Co1—N410 | 82.9 (5) | N310—C311—C312 | 122.4 (11) |
N310—Co1—N12 | 94.2 (3) | C313—C311—C312 | 121.0 (9) |
N310—Co1—N210 | 100.8 (3) | C37—C312—C36 | 125.0 (9) |
N310—Co1—N21 | 91.6 (3) | C37—C312—C311 | 115.7 (9) |
N210—Co1—N21 | 83.44 (11) | C36—C312—C311 | 119.3 (9) |
N310—Co1—N31 | 83.0 (4) | N31—C313—C311 | 116.3 (9) |
N210—Co1—N31 | 175.5 (3) | N31—C313—C314 | 124.0 (9) |
N210—Co1—N410 | 88.2 (3) | C311—C313—C314 | 119.7 (9) |
C11—N11—O11 | 120.4 (3) | C34—C314—C35 | 126.9 (11) |
C11—N11—Co1 | 115.5 (2) | C34—C314—C313 | 114.9 (8) |
O11—N11—Co1 | 123.6 (2) | C35—C314—C313 | 118.2 (11) |
O12—N12—C12 | 123.3 (2) | C42—N41—C413 | 118.2 (13) |
O12—N12—Co1 | 122.14 (18) | C42—N41—Co1 | 125.4 (10) |
C12—N12—Co1 | 114.5 (2) | C413—N41—Co1 | 116.4 (9) |
N11—O11—H1O | 105.6 | C49—N410—C411 | 118.0 (11) |
N11—C11—C12 | 113.8 (3) | C49—N410—Co1 | 133.4 (8) |
N11—C11—C13 | 123.6 (3) | C411—N410—Co1 | 108.6 (8) |
C12—C11—C13 | 122.7 (3) | N41—C42—C43 | 122.8 (12) |
N12—C12—C11 | 113.9 (3) | N41—C42—H42 | 118.6 |
N12—C12—C14 | 120.9 (3) | C43—C42—H42 | 118.6 |
C11—C12—C14 | 125.2 (3) | C44—C43—C42 | 117.8 (12) |
C11—C13—H13C | 109.5 | C44—C43—H43 | 121.1 |
C11—C13—H13B | 109.5 | C42—C43—H43 | 121.1 |
H13C—C13—H13B | 109.5 | C43—C44—C414 | 121.4 (13) |
C11—C13—H13A | 109.5 | C43—C44—H44 | 119.3 |
H13C—C13—H13A | 109.5 | C414—C44—H44 | 119.3 |
H13B—C13—H13A | 109.5 | C414—C45—C46 | 118.9 (11) |
C12—C14—H14B | 109.5 | C414—C45—H45 | 120.5 |
C12—C14—H14A | 109.5 | C46—C45—H45 | 120.5 |
H14B—C14—H14A | 109.5 | C412—C46—C45 | 121.0 (11) |
C12—C14—H14C | 109.5 | C412—C46—H46 | 119.5 |
H14B—C14—H14C | 109.5 | C45—C46—H46 | 119.5 |
H14A—C14—H14C | 109.5 | C48—C47—C412 | 121.3 (9) |
C22—N21—C213 | 118.4 (3) | C48—C47—H47 | 119.3 |
C22—N21—Co1 | 130.7 (3) | C412—C47—H47 | 119.3 |
C213—N21—Co1 | 110.8 (2) | C49—C48—C47 | 117.2 (9) |
C29—N210—C211 | 118.2 (3) | C49—C48—H48 | 121.4 |
C29—N210—Co1 | 129.0 (2) | C47—C48—H48 | 121.4 |
C211—N210—Co1 | 112.7 (2) | N410—C49—C48 | 123.6 (11) |
N21—C22—C23 | 122.3 (4) | N410—C49—H49 | 118.2 |
N21—C22—H22 | 118.8 | C48—C49—H49 | 118.2 |
C23—C22—H22 | 118.8 | N410—C411—C412 | 125.5 (10) |
C24—C23—C22 | 119.5 (4) | N410—C411—C413 | 115.9 (10) |
C24—C23—H23 | 120.3 | C412—C411—C413 | 118.6 (11) |
C22—C23—H23 | 120.3 | C46—C412—C411 | 121.0 (12) |
C23—C24—C214 | 120.0 (3) | C46—C412—C47 | 124.7 (12) |
C23—C24—H24 | 120.0 | C411—C412—C47 | 114.3 (10) |
C214—C24—H24 | 120.0 | N41—C413—C414 | 122.1 (13) |
C26—C25—C214 | 121.7 (3) | N41—C413—C411 | 116.2 (11) |
C26—C25—H25 | 119.1 | C414—C413—C411 | 121.6 (11) |
C214—C25—H25 | 119.1 | C44—C414—C413 | 117.5 (11) |
C25—C26—C212 | 121.3 (3) | C44—C414—C45 | 123.6 (11) |
C25—C26—H26 | 119.3 | C413—C414—C45 | 118.9 (11) |
C212—C26—H26 | 119.3 | H1W1—O1W—H2W1 | 117.4 |
C28—C27—C212 | 119.4 (3) | O3A—N1A—O2A | 121.0 (7) |
C28—C27—H27 | 120.3 | O3A—N1A—O1A | 120.3 (6) |
C212—C27—H27 | 120.3 | O2A—N1A—O1A | 118.7 (6) |
C27—C28—C29 | 120.3 (3) | O1B—N1B—O3B | 116.3 (4) |
C27—C28—H28 | 119.8 | O1B—N1B—O2B | 125.0 (5) |
C29—C28—H28 | 119.8 | O3B—N1B—O2B | 118.7 (5) |
N210—C29—C28 | 121.9 (3) | O1B'—N1B'—O2B' | 117.9 (6) |
N210—C29—H29 | 119.0 | O1B'—N1B'—O3B | 126.9 (7) |
C28—C29—H29 | 119.0 | O2B'—N1B'—O3B | 115.3 (7) |
N210—C211—C212 | 122.9 (3) | C1C—O1C—H1C | 108.7 |
N210—C211—C213 | 116.2 (3) | O1C—C1C—C2C | 112.6 (8) |
C212—C211—C213 | 120.9 (3) | O1C—C1C—H1CA | 110.6 |
C211—C212—C27 | 117.2 (3) | C2C—C1C—H1CA | 108.9 |
C211—C212—C26 | 117.8 (3) | O1C—C1C—H1CB | 108.4 |
C27—C212—C26 | 125.0 (3) | C2C—C1C—H1CB | 108.5 |
N21—C213—C214 | 122.8 (3) | H1CA—C1C—H1CB | 107.7 |
N21—C213—C211 | 116.5 (3) | O1C—C1C—H1CC | 95.7 |
C214—C213—C211 | 120.7 (3) | C1C—C2C—H2CC | 109.9 |
C213—C214—C24 | 116.9 (3) | C1C—C2C—H2CB | 109.1 |
C213—C214—C25 | 117.6 (3) | H2CC—C2C—H2CB | 109.5 |
C24—C214—C25 | 125.6 (3) | C1C—C2C—H2CA | 109.5 |
C32—N31—C313 | 118.3 (10) | H2CC—C2C—H2CA | 109.5 |
C32—N31—Co1 | 131.8 (7) | H2CB—C2C—H2CA | 109.5 |
C313—N31—Co1 | 109.8 (7) | C2C'—C1C'—H2CB | 108.5 |
C39—N310—C311 | 119.2 (11) | H1CA—C1C'—H2CB | 107.7 |
C39—N310—Co1 | 126.5 (8) | H1CB—C1C'—H2CA | 106.6 |
C311—N310—Co1 | 114.2 (7) | C2C'—C1C'—H1CD | 108.4 |
N31—C32—C33 | 122.4 (9) | C2C'—C1C'—H1CC | 107.6 |
N31—C32—H32 | 118.8 | H2CA—C1C'—H1CC | 109.2 |
C33—C32—H32 | 118.8 | H1CD—C1C'—H1CC | 107.0 |
C32—C33—C34 | 118.6 (8) | C1C'—C2C'—H2CF | 108.8 |
C32—C33—H33 | 120.7 | C1C'—C2C'—H2CD | 109.4 |
C34—C33—H33 | 120.7 | H2CF—C2C'—H2CD | 109.5 |
C314—C34—C33 | 121.8 (9) | C1C'—C2C'—H2CE | 110.2 |
C314—C34—H34 | 119.1 | H2CF—C2C'—H2CE | 109.5 |
C33—C34—H34 | 119.1 | H2CD—C2C'—H2CE | 109.5 |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H1O···O11i | 1.21 | 1.21 | 2.409 (4) | 170 |
O1W—H1W1···O3A | 0.89 | 1.95 | 2.816 (9) | 163 |
O1W—H2W1···O2B | 0.89 | 1.85 | 2.684 (9) | 155 |
O1W—H2W1···O2B′ | 0.89 | 2.04 | 2.921 (13) | 173 |
O1W—H2W1···O3B | 0.89 | 2.42 | 2.940 (8) | 118 |
O2W—H1W2···O2A | 0.89 | 2.03 | 2.890 (9) | 161 |
O2W—H2W2···O12ii | 0.89 | 2.10 | 2.845 (5) | 140 |
O1C—H1C···O1W | 0.82 | 1.64 | 2.395 (7) | 151 |
O1C—H1C···O2B | 0.82 | 2.38 | 2.884 (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·0.40H2O | F(000) = 1472 |
Mr = 711.79 | Dx = 1.587 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 8290 reflections |
a = 13.7587 (1) Å | θ = 4.6–65.2° |
b = 11.9763 (1) Å | µ = 5.15 mm−1 |
c = 18.2055 (2) Å | T = 130 K |
β = 96.744 (1)° | Block, dark-red |
V = 2979.11 (5) Å3 | 0.10 × 0.10 × 0.05 mm |
Z = 4 | |
Data collection top
Oxford SuperNova diffractometer | 5254 independent reflections |
Radiation source: Nova Cu X-ray Source | 4545 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.021 |
ω scans | θmax = 66.6°, θmin = 6.5° |
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009) | h = −16→15 |
Tmin = 0.611, Tmax = 0.810 | k = −14→11 |
14572 measured reflections | l = −21→18 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-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 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
Crystal data top
[Co(C4H7N2O2)(C12H8N2)2](NO3)2·C2H6O·0.40H2O | V = 2979.11 (5) Å3 |
Mr = 711.79 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 13.7587 (1) Å | µ = 5.15 mm−1 |
b = 11.9763 (1) Å | T = 130 K |
c = 18.2055 (2) Å | 0.10 × 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 = 0.810 | Rint = 0.021 |
14572 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.79 e Å−3 |
5254 reflections | Δρmin = −0.49 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.27764 (2) | 0.25578 (3) | 0.538389 (18) | 0.01733 (12) | |
N11 | 0.33983 (12) | 0.20189 (16) | 0.63104 (10) | 0.0230 (4) | |
N12 | 0.32710 (13) | 0.39383 (15) | 0.57754 (10) | 0.0219 (4) | |
O11 | 0.33595 (12) | 0.09908 (13) | 0.64919 (9) | 0.0298 (4) | |
O12 | 0.30142 (11) | 0.49779 (13) | 0.54848 (9) | 0.0273 (3) | |
H1O | 0.3309 | 0.4967 | 0.5031 | 0.041* | |
C11 | 0.38522 (15) | 0.2794 (2) | 0.67364 (12) | 0.0246 (5) | |
C12 | 0.37376 (15) | 0.3909 (2) | 0.64370 (12) | 0.0239 (5) | |
C13 | 0.43912 (19) | 0.2514 (2) | 0.74724 (14) | 0.0341 (6) | |
H13A | 0.4273 | 0.1731 | 0.7590 | 0.051* | |
H13B | 0.4162 | 0.2995 | 0.7852 | 0.051* | |
H13C | 0.5094 | 0.2632 | 0.7459 | 0.051* | |
C14 | 0.40974 (18) | 0.4922 (2) | 0.68611 (14) | 0.0329 (5) | |
H14A | 0.4146 | 0.5546 | 0.6518 | 0.049* | |
H14B | 0.4743 | 0.4770 | 0.7130 | 0.049* | |
H14C | 0.3639 | 0.5118 | 0.7214 | 0.049* | |
N21 | 0.23646 (12) | 0.10583 (15) | 0.50447 (10) | 0.0212 (4) | |
N210 | 0.39475 (13) | 0.22169 (15) | 0.49223 (10) | 0.0194 (4) | |
C22 | 0.15771 (16) | 0.0475 (2) | 0.51613 (13) | 0.0268 (5) | |
H22 | 0.1117 | 0.0794 | 0.5451 | 0.032* | |
C23 | 0.14067 (17) | −0.0595 (2) | 0.48700 (14) | 0.0322 (5) | |
H23 | 0.0837 | −0.0993 | 0.4965 | 0.039* | |
C24 | 0.20560 (17) | −0.1073 (2) | 0.44483 (14) | 0.0308 (5) | |
H24 | 0.1931 | −0.1793 | 0.4238 | 0.037* | |
C25 | 0.36629 (17) | −0.0910 (2) | 0.39240 (12) | 0.0268 (5) | |
H25 | 0.3582 | −0.1618 | 0.3689 | 0.032* | |
C26 | 0.44866 (16) | −0.0315 (2) | 0.38706 (12) | 0.0259 (5) | |
H26 | 0.4979 | −0.0618 | 0.3604 | 0.031* | |
C27 | 0.54796 (15) | 0.1425 (2) | 0.41856 (12) | 0.0245 (5) | |
H27 | 0.6007 | 0.1165 | 0.3938 | 0.029* | |
C28 | 0.55299 (16) | 0.24435 (19) | 0.45255 (13) | 0.0259 (5) | |
H28 | 0.6096 | 0.2895 | 0.4514 | 0.031* | |
C29 | 0.47513 (15) | 0.2829 (2) | 0.48922 (12) | 0.0229 (5) | |
H29 | 0.4798 | 0.3541 | 0.5123 | 0.028* | |
C211 | 0.38910 (15) | 0.12048 (18) | 0.45852 (11) | 0.0202 (4) | |
C212 | 0.46322 (15) | 0.07603 (19) | 0.42064 (11) | 0.0220 (4) | |
C213 | 0.30284 (15) | 0.05768 (18) | 0.46455 (11) | 0.0201 (4) | |
C214 | 0.29085 (16) | −0.04875 (19) | 0.43308 (12) | 0.0243 (5) | |
N31 | 0.15500 (13) | 0.28273 (15) | 0.57786 (10) | 0.0208 (4) | |
N310 | 0.20755 (12) | 0.31986 (15) | 0.44583 (10) | 0.0201 (4) | |
C32 | 0.13286 (17) | 0.26652 (19) | 0.64601 (13) | 0.0259 (5) | |
H32 | 0.1822 | 0.2404 | 0.6829 | 0.031* | |
C33 | 0.03914 (17) | 0.2868 (2) | 0.66512 (14) | 0.0289 (5) | |
H33 | 0.0258 | 0.2752 | 0.7146 | 0.035* | |
C34 | −0.03353 (16) | 0.32310 (19) | 0.61295 (13) | 0.0271 (5) | |
H34 | −0.0975 | 0.3363 | 0.6257 | 0.032* | |
C35 | −0.08169 (16) | 0.3810 (2) | 0.48076 (14) | 0.0293 (5) | |
H35 | −0.1477 | 0.3933 | 0.4892 | 0.035* | |
C36 | −0.05421 (17) | 0.4018 (2) | 0.41285 (14) | 0.0309 (5) | |
H36 | −0.1013 | 0.4289 | 0.3747 | 0.037* | |
C37 | 0.07954 (18) | 0.40794 (19) | 0.32944 (13) | 0.0293 (5) | |
H37 | 0.0369 | 0.4376 | 0.2894 | 0.035* | |
C38 | 0.17582 (18) | 0.38799 (19) | 0.32209 (13) | 0.0284 (5) | |
H38 | 0.2008 | 0.4055 | 0.2770 | 0.034* | |
C39 | 0.23787 (16) | 0.34177 (18) | 0.38096 (12) | 0.0232 (5) | |
H39 | 0.3038 | 0.3257 | 0.3740 | 0.028* | |
C311 | 0.11197 (15) | 0.34096 (17) | 0.45414 (12) | 0.0215 (4) | |
C312 | 0.04459 (16) | 0.38378 (18) | 0.39748 (13) | 0.0261 (5) | |
C313 | 0.08333 (15) | 0.32022 (18) | 0.52499 (12) | 0.0207 (4) | |
C314 | −0.01234 (16) | 0.34068 (18) | 0.54007 (13) | 0.0240 (5) | |
O1W | 0.0446 (5) | 1.0163 (6) | 0.6486 (3) | 0.0556 (17) | 0.403 (6) |
H1W1 | −0.0218 | 0.9745 | 0.6548 | 0.28 (11)* | 0.403 (6) |
N1A | 0.34885 (14) | 0.59349 (18) | 0.39045 (11) | 0.0302 (5) | |
O1A | 0.39449 (12) | 0.51624 (14) | 0.42903 (9) | 0.0309 (4) | |
O3A | 0.38139 (19) | 0.6285 (2) | 0.33571 (14) | 0.0762 (9) | |
O2A | 0.27349 (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) |
N1B | 0.17301 (10) | 0.42181 (11) | 0.79453 (7) | 0.0351 (8) | 0.864 (4) |
O1B | 0.14750 (18) | 0.50887 (17) | 0.75804 (13) | 0.0660 (11) | 0.864 (4) |
O2B | 0.11786 (12) | 0.38301 (17) | 0.83768 (10) | 0.0386 (6) | 0.864 (4) |
O3B | 0.25240 (11) | 0.37478 (17) | 0.78825 (11) | 0.0436 (6) | 0.864 (4) |
O1C | 0.1722 (5) | 0.8724 (5) | 0.7456 (4) | 0.068 (2) | 0.403 (6) |
H1C | 0.1305 | 0.9095 | 0.7035 | 0.082* | 0.403 (6) |
C1C | 0.1745 (6) | 0.7630 (6) | 0.7228 (5) | 0.046 (2) | 0.403 (6) |
H1CA | 0.1089 | 0.7416 | 0.6987 | 0.056* | 0.403 (6) |
H1CB | 0.1903 | 0.7143 | 0.7666 | 0.056* | 0.403 (6) |
C2C | 0.2476 (6) | 0.7448 (9) | 0.6706 (7) | 0.075 (3) | 0.403 (6) |
H2CA | 0.2199 | 0.7676 | 0.6208 | 0.112* | 0.403 (6) |
H2CC | 0.2652 | 0.6655 | 0.6702 | 0.112* | 0.403 (6) |
H2CB | 0.3062 | 0.7893 | 0.6861 | 0.112* | 0.403 (6) |
O1D | 0.0780 (4) | 0.9518 (6) | 0.6599 (3) | 0.0727 (15) | 0.597 (6) |
H1D | 0.0089 | 0.9434 | 0.6563 | 0.073* | 0.597 (6) |
C2D | 0.2263 (4) | 0.8467 (7) | 0.6737 (4) | 0.070 (2) | 0.597 (6) |
H2DA | 0.2550 | 0.9216 | 0.6744 | 0.104* | 0.597 (6) |
H2DB | 0.2221 | 0.8162 | 0.6234 | 0.104* | 0.597 (6) |
H2DC | 0.2674 | 0.7980 | 0.7076 | 0.104* | 0.597 (6) |
C1D | 0.1272 (5) | 0.8531 (7) | 0.6970 (4) | 0.074 (2) | 0.597 (6) |
H1DA | 0.1314 | 0.8612 | 0.7514 | 0.089* | 0.597 (6) |
H1DB | 0.0900 | 0.7843 | 0.6825 | 0.089* | 0.597 (6) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01491 (18) | 0.01660 (19) | 0.02036 (19) | 0.00083 (13) | 0.00165 (13) | −0.00134 (13) |
N11 | 0.0171 (8) | 0.0251 (10) | 0.0271 (9) | 0.0033 (7) | 0.0040 (7) | 0.0019 (8) |
N12 | 0.0197 (8) | 0.0195 (9) | 0.0263 (9) | 0.0019 (7) | 0.0023 (7) | −0.0023 (7) |
O11 | 0.0287 (8) | 0.0246 (9) | 0.0357 (9) | 0.0019 (7) | 0.0017 (7) | 0.0069 (7) |
O12 | 0.0313 (8) | 0.0186 (8) | 0.0319 (8) | 0.0029 (6) | 0.0034 (6) | −0.0011 (7) |
C11 | 0.0191 (10) | 0.0305 (12) | 0.0242 (11) | 0.0025 (9) | 0.0027 (8) | −0.0022 (10) |
C12 | 0.0173 (10) | 0.0302 (12) | 0.0245 (11) | −0.0002 (9) | 0.0045 (8) | −0.0053 (9) |
C13 | 0.0307 (13) | 0.0455 (16) | 0.0251 (12) | 0.0029 (11) | −0.0012 (10) | 0.0018 (11) |
C14 | 0.0333 (13) | 0.0322 (13) | 0.0324 (12) | −0.0037 (10) | 0.0006 (10) | −0.0091 (11) |
N21 | 0.0189 (8) | 0.0190 (9) | 0.0254 (9) | 0.0011 (7) | 0.0009 (7) | 0.0008 (7) |
N210 | 0.0180 (8) | 0.0186 (9) | 0.0212 (9) | 0.0018 (7) | 0.0008 (7) | 0.0009 (7) |
C22 | 0.0197 (10) | 0.0256 (12) | 0.0358 (12) | −0.0021 (9) | 0.0062 (9) | −0.0001 (10) |
C23 | 0.0252 (12) | 0.0243 (12) | 0.0474 (15) | −0.0052 (10) | 0.0056 (10) | −0.0009 (11) |
C24 | 0.0303 (12) | 0.0204 (12) | 0.0411 (13) | −0.0040 (9) | 0.0014 (10) | −0.0033 (10) |
C25 | 0.0320 (12) | 0.0219 (11) | 0.0258 (11) | 0.0040 (9) | 0.0004 (9) | −0.0030 (9) |
C26 | 0.0285 (11) | 0.0277 (12) | 0.0214 (11) | 0.0111 (9) | 0.0029 (8) | −0.0006 (9) |
C27 | 0.0207 (10) | 0.0306 (12) | 0.0226 (10) | 0.0060 (9) | 0.0043 (8) | 0.0033 (9) |
C28 | 0.0188 (11) | 0.0310 (13) | 0.0278 (12) | −0.0020 (9) | 0.0021 (9) | 0.0052 (9) |
C29 | 0.0187 (10) | 0.0236 (11) | 0.0257 (11) | −0.0018 (9) | −0.0003 (8) | 0.0000 (9) |
C211 | 0.0194 (10) | 0.0209 (11) | 0.0197 (10) | 0.0020 (8) | 0.0003 (8) | 0.0023 (8) |
C212 | 0.0214 (10) | 0.0250 (11) | 0.0192 (10) | 0.0054 (9) | 0.0014 (8) | 0.0038 (9) |
C213 | 0.0205 (10) | 0.0182 (10) | 0.0208 (10) | 0.0024 (8) | −0.0001 (8) | 0.0014 (8) |
C214 | 0.0268 (11) | 0.0192 (11) | 0.0258 (11) | 0.0028 (9) | −0.0015 (8) | 0.0004 (9) |
N31 | 0.0185 (8) | 0.0192 (9) | 0.0245 (9) | 0.0003 (7) | 0.0014 (7) | −0.0017 (7) |
N310 | 0.0213 (9) | 0.0157 (8) | 0.0229 (9) | −0.0004 (7) | 0.0004 (7) | −0.0032 (7) |
C32 | 0.0231 (11) | 0.0295 (12) | 0.0251 (11) | −0.0002 (9) | 0.0028 (9) | −0.0014 (9) |
C33 | 0.0262 (11) | 0.0323 (13) | 0.0297 (12) | −0.0032 (10) | 0.0095 (9) | −0.0019 (10) |
C34 | 0.0200 (10) | 0.0242 (11) | 0.0377 (13) | −0.0003 (9) | 0.0063 (9) | −0.0048 (10) |
C35 | 0.0195 (11) | 0.0259 (12) | 0.0414 (14) | 0.0030 (9) | −0.0008 (9) | −0.0021 (11) |
C36 | 0.0275 (12) | 0.0256 (12) | 0.0374 (13) | 0.0049 (10) | −0.0059 (10) | 0.0014 (10) |
C37 | 0.0350 (12) | 0.0222 (11) | 0.0286 (12) | 0.0018 (10) | −0.0046 (9) | −0.0002 (10) |
C38 | 0.0403 (13) | 0.0224 (11) | 0.0219 (11) | 0.0014 (10) | 0.0006 (9) | −0.0006 (9) |
C39 | 0.0274 (11) | 0.0192 (11) | 0.0233 (11) | −0.0015 (9) | 0.0040 (8) | −0.0046 (9) |
C311 | 0.0223 (10) | 0.0139 (10) | 0.0275 (11) | −0.0008 (8) | −0.0001 (8) | −0.0035 (9) |
C312 | 0.0283 (11) | 0.0191 (11) | 0.0294 (12) | 0.0013 (9) | −0.0030 (9) | −0.0017 (9) |
C313 | 0.0184 (10) | 0.0159 (10) | 0.0271 (11) | −0.0009 (8) | 0.0001 (8) | −0.0024 (9) |
C314 | 0.0218 (10) | 0.0160 (10) | 0.0340 (12) | −0.0011 (8) | 0.0025 (9) | −0.0035 (9) |
O1W | 0.052 (4) | 0.058 (4) | 0.057 (4) | −0.004 (3) | 0.008 (3) | 0.012 (3) |
N1A | 0.0259 (10) | 0.0297 (11) | 0.0349 (11) | −0.0019 (8) | 0.0032 (8) | 0.0019 (9) |
O1A | 0.0294 (8) | 0.0237 (8) | 0.0392 (9) | 0.0029 (7) | 0.0023 (7) | 0.0038 (7) |
O3A | 0.0806 (17) | 0.091 (2) | 0.0658 (16) | 0.0421 (15) | 0.0441 (14) | 0.0435 (14) |
O2A | 0.0299 (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) |
N1B | 0.0439 (16) | 0.0327 (18) | 0.0258 (14) | 0.0008 (13) | −0.0074 (12) | 0.0020 (13) |
O1B | 0.074 (3) | 0.058 (2) | 0.061 (2) | 0.0059 (17) | −0.0137 (18) | 0.0288 (16) |
O2B | 0.0402 (11) | 0.0410 (13) | 0.0347 (11) | 0.0039 (10) | 0.0043 (9) | 0.0033 (9) |
O3B | 0.0363 (12) | 0.0502 (14) | 0.0458 (13) | −0.0008 (11) | 0.0114 (9) | −0.0107 (11) |
O1C | 0.058 (4) | 0.065 (4) | 0.078 (5) | 0.003 (3) | −0.010 (3) | −0.019 (4) |
C1C | 0.056 (5) | 0.031 (4) | 0.054 (5) | 0.002 (3) | 0.014 (4) | −0.009 (3) |
C2C | 0.032 (4) | 0.077 (7) | 0.113 (9) | −0.002 (4) | −0.002 (5) | −0.022 (6) |
O1D | 0.054 (3) | 0.097 (4) | 0.071 (3) | 0.002 (3) | 0.027 (2) | 0.025 (3) |
C2D | 0.052 (3) | 0.087 (5) | 0.071 (4) | −0.011 (3) | 0.015 (3) | −0.001 (4) |
C1D | 0.075 (4) | 0.089 (5) | 0.060 (4) | −0.023 (4) | 0.022 (4) | −0.014 (4) |
Geometric parameters (Å, º) top
Co1—N11 | 1.9118 (18) | N310—C311 | 1.365 (3) |
Co1—N12 | 1.8949 (18) | C32—C33 | 1.396 (3) |
Co1—N21 | 1.9609 (18) | C32—H32 | 0.9500 |
Co1—N31 | 1.9371 (18) | C33—C34 | 1.367 (3) |
Co1—N210 | 1.9460 (18) | C33—H33 | 0.9500 |
Co1—N310 | 1.9942 (18) | C34—C314 | 1.407 (3) |
N11—O11 | 1.278 (2) | C34—H34 | 0.9500 |
N11—C11 | 1.319 (3) | C35—C36 | 1.358 (4) |
N12—C12 | 1.297 (3) | C35—C314 | 1.438 (3) |
N12—O12 | 1.382 (2) | C35—H35 | 0.9500 |
O12—H1O | 0.9631 | C36—C312 | 1.436 (3) |
C11—C12 | 1.444 (3) | C36—H36 | 0.9500 |
C11—C13 | 1.491 (3) | C37—C38 | 1.368 (3) |
C12—C14 | 1.491 (3) | C37—C312 | 1.410 (3) |
C13—H13A | 0.9800 | C37—H37 | 0.9500 |
C13—H13B | 0.9800 | C38—C39 | 1.403 (3) |
C13—H13C | 0.9800 | C38—H38 | 0.9500 |
C14—H14A | 0.9800 | C39—H39 | 0.9500 |
C14—H14B | 0.9800 | C311—C312 | 1.401 (3) |
C14—H14C | 0.9800 | C311—C313 | 1.414 (3) |
N21—C22 | 1.327 (3) | C313—C314 | 1.397 (3) |
N21—C213 | 1.360 (3) | O1W—H1W1 | 1.0597 |
N210—C29 | 1.334 (3) | N1A—O3A | 1.214 (3) |
N210—C211 | 1.357 (3) | N1A—O2A | 1.235 (3) |
C22—C23 | 1.396 (3) | N1A—O1A | 1.281 (3) |
C22—H22 | 0.9500 | N1B'—O2B' | 1.2228 |
C23—C24 | 1.370 (3) | N1B'—O3B' | 1.2274 |
C23—H23 | 0.9500 | N1B'—O1B' | 1.2635 |
C24—C214 | 1.405 (3) | N1B—O2B | 1.2445 |
C24—H24 | 0.9500 | N1B—O3B | 1.2461 |
C25—C26 | 1.352 (3) | N1B—O1B | 1.2637 |
C25—C214 | 1.436 (3) | O1C—C1C | 1.375 (9) |
C25—H25 | 0.9500 | O1C—H1C | 1.0056 |
C26—C212 | 1.430 (3) | C1C—C2C | 1.480 (14) |
C26—H26 | 0.9500 | C1C—H1CA | 0.9900 |
C27—C28 | 1.366 (3) | C1C—H1CB | 0.9900 |
C27—C212 | 1.416 (3) | C2C—H2CA | 0.9800 |
C27—H27 | 0.9500 | C2C—H2CC | 0.9800 |
C28—C29 | 1.405 (3) | C2C—H2CB | 0.9800 |
C28—H28 | 0.9500 | O1D—C1D | 1.486 (11) |
C29—H29 | 0.9500 | O1D—H1D | 0.9499 |
C211—C212 | 1.402 (3) | C2D—C1D | 1.477 (8) |
C211—C213 | 1.420 (3) | C2D—H2DA | 0.9800 |
C213—C214 | 1.399 (3) | C2D—H2DB | 0.9800 |
N31—C32 | 1.326 (3) | C2D—H2DC | 0.9800 |
N31—C313 | 1.370 (3) | C1D—H1DA | 0.9900 |
N310—C39 | 1.324 (3) | C1D—H1DB | 0.9900 |
| | | |
N12—Co1—N11 | 81.89 (8) | N21—C213—C211 | 115.87 (19) |
N12—Co1—N31 | 90.29 (8) | C214—C213—C211 | 120.7 (2) |
N11—Co1—N31 | 92.76 (8) | C213—C214—C24 | 116.9 (2) |
N12—Co1—N210 | 93.81 (8) | C213—C214—C25 | 118.3 (2) |
N11—Co1—N210 | 90.16 (7) | C24—C214—C25 | 124.7 (2) |
N31—Co1—N210 | 175.27 (7) | C32—N31—C313 | 118.67 (19) |
N12—Co1—N21 | 174.40 (7) | C32—N31—Co1 | 128.94 (15) |
N11—Co1—N21 | 92.95 (8) | C313—N31—Co1 | 112.36 (14) |
N31—Co1—N21 | 92.14 (8) | C39—N310—C311 | 118.08 (19) |
N210—Co1—N21 | 83.98 (8) | C39—N310—Co1 | 131.15 (15) |
N12—Co1—N310 | 95.67 (8) | C311—N310—Co1 | 110.75 (14) |
N11—Co1—N310 | 175.85 (8) | N31—C32—C33 | 121.9 (2) |
N31—Co1—N310 | 83.88 (7) | N31—C32—H32 | 119.1 |
N210—Co1—N310 | 93.36 (7) | C33—C32—H32 | 119.1 |
N21—Co1—N310 | 89.61 (7) | C34—C33—C32 | 120.3 (2) |
O11—N11—C11 | 123.90 (19) | C34—C33—H33 | 119.9 |
O11—N11—Co1 | 121.71 (15) | C32—C33—H33 | 119.9 |
C11—N11—Co1 | 114.39 (16) | C33—C34—C314 | 119.2 (2) |
C12—N12—O12 | 117.11 (18) | C33—C34—H34 | 120.4 |
C12—N12—Co1 | 116.28 (16) | C314—C34—H34 | 120.4 |
O12—N12—Co1 | 125.28 (13) | C36—C35—C314 | 120.9 (2) |
N12—O12—H1O | 101.7 | C36—C35—H35 | 119.5 |
N11—C11—C12 | 113.96 (19) | C314—C35—H35 | 119.5 |
N11—C11—C13 | 121.4 (2) | C35—C36—C312 | 121.4 (2) |
C12—C11—C13 | 124.6 (2) | C35—C36—H36 | 119.3 |
N12—C12—C11 | 113.3 (2) | C312—C36—H36 | 119.3 |
N12—C12—C14 | 123.9 (2) | C38—C37—C312 | 118.9 (2) |
C11—C12—C14 | 122.8 (2) | C38—C37—H37 | 120.5 |
C11—C13—H13A | 109.5 | C312—C37—H37 | 120.5 |
C11—C13—H13B | 109.5 | C37—C38—C39 | 120.2 (2) |
H13A—C13—H13B | 109.5 | C37—C38—H38 | 119.9 |
C11—C13—H13C | 109.5 | C39—C38—H38 | 119.9 |
H13A—C13—H13C | 109.5 | N310—C39—C38 | 122.2 (2) |
H13B—C13—H13C | 109.5 | N310—C39—H39 | 118.9 |
C12—C14—H14A | 109.5 | C38—C39—H39 | 118.9 |
C12—C14—H14B | 109.5 | N310—C311—C312 | 123.3 (2) |
H14A—C14—H14B | 109.5 | N310—C311—C313 | 116.34 (19) |
C12—C14—H14C | 109.5 | C312—C311—C313 | 120.3 (2) |
H14A—C14—H14C | 109.5 | C311—C312—C37 | 117.2 (2) |
H14B—C14—H14C | 109.5 | C311—C312—C36 | 118.1 (2) |
C22—N21—C213 | 118.31 (19) | C37—C312—C36 | 124.6 (2) |
C22—N21—Co1 | 130.01 (16) | N31—C313—C314 | 122.4 (2) |
C213—N21—Co1 | 111.66 (14) | N31—C313—C311 | 116.34 (18) |
C29—N210—C211 | 118.46 (19) | C314—C313—C311 | 121.2 (2) |
C29—N210—Co1 | 129.42 (16) | C313—C314—C34 | 117.6 (2) |
C211—N210—Co1 | 112.11 (14) | C313—C314—C35 | 118.0 (2) |
N21—C22—C23 | 121.8 (2) | C34—C314—C35 | 124.4 (2) |
N21—C22—H22 | 119.1 | O3A—N1A—O2A | 120.5 (2) |
C23—C22—H22 | 119.1 | O3A—N1A—O1A | 119.7 (2) |
C24—C23—C22 | 120.4 (2) | O2A—N1A—O1A | 119.7 (2) |
C24—C23—H23 | 119.8 | O2B'—N1B'—O3B' | 123.0 |
C22—C23—H23 | 119.8 | O2B'—N1B'—O1B' | 118.9 |
C23—C24—C214 | 119.2 (2) | O3B'—N1B'—O1B' | 118.1 |
C23—C24—H24 | 120.4 | O2B—N1B—O3B | 119.7 |
C214—C24—H24 | 120.4 | O2B—N1B—O1B | 119.2 |
C26—C25—C214 | 120.9 (2) | O3B—N1B—O1B | 121.1 |
C26—C25—H25 | 119.5 | C1C—O1C—H1C | 102.9 |
C214—C25—H25 | 119.5 | O1C—C1C—C2C | 112.0 (7) |
C25—C26—C212 | 121.4 (2) | O1C—C1C—H1CA | 109.2 |
C25—C26—H26 | 119.3 | C2C—C1C—H1CA | 109.2 |
C212—C26—H26 | 119.3 | O1C—C1C—H1CB | 109.2 |
C28—C27—C212 | 119.2 (2) | C2C—C1C—H1CB | 109.2 |
C28—C27—H27 | 120.4 | H1CA—C1C—H1CB | 107.9 |
C212—C27—H27 | 120.4 | C1D—O1D—H1D | 110.2 |
C27—C28—C29 | 120.5 (2) | C1D—C2D—H2DA | 109.5 |
C27—C28—H28 | 119.7 | C1D—C2D—H2DB | 109.5 |
C29—C28—H28 | 119.7 | H2DA—C2D—H2DB | 109.5 |
N210—C29—C28 | 121.4 (2) | C1D—C2D—H2DC | 109.5 |
N210—C29—H29 | 119.3 | H2DA—C2D—H2DC | 109.5 |
C28—C29—H29 | 119.3 | H2DB—C2D—H2DC | 109.5 |
N210—C211—C212 | 123.7 (2) | C2D—C1D—O1D | 107.3 (5) |
N210—C211—C213 | 116.24 (19) | C2D—C1D—H1DA | 110.3 |
C212—C211—C213 | 120.0 (2) | O1D—C1D—H1DA | 110.3 |
C211—C212—C27 | 116.7 (2) | C2D—C1D—H1DB | 110.3 |
C211—C212—C26 | 118.6 (2) | O1D—C1D—H1DB | 110.3 |
C27—C212—C26 | 124.7 (2) | H1DA—C1D—H1DB | 108.5 |
N21—C213—C214 | 123.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H1O···O1A | 0.96 | 1.71 | 2.659 (2) | 169 |
O12—H1O···O2A | 0.96 | 2.42 | 2.984 (2) | 117 |
O1W—H1W1···O2B′i | 1.06 | 1.71 | 2.464 (13) | 124 |
O1W—H1W1···O2Bi | 1.06 | 1.73 | 2.782 (8) | 169 |
O1C—H1C···O1W | 1.01 | 1.94 | 2.905 (11) | 161 |
O1D—H1D···O2Bi | 0.95 | 1.90 | 2.824 (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 |
Mr | 1379.76 | 711.79 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 130 | 130 |
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) |
V (Å3) | 5921.4 (4) | 2979.11 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Cu Kα |
µ (mm−1) | 0.65 | 5.15 |
Crystal size (mm) | 0.50 × 0.40 × 0.40 | 0.10 × 0.10 × 0.05 |
|
Data collection |
Diffractometer | Oxford XcaliburE CCD diffractometer | Oxford SuperNova diffractometer |
Absorption correction | Multi-scan CrysAlis PRO (Oxford Diffraction, 2009) | Multi-scan CrysAlis PRO (Oxford Diffraction, 2009) |
Tmin, Tmax | 0.720, 0.804 | 0.611, 0.810 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25463, 5211, 3075 | 14572, 5254, 4545 |
Rint | 0.053 | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.095, 0.89 | 0.038, 0.109, 1.06 |
No. of reflections | 5211 | 5254 |
No. of parameters | 614 | 488 |
No. of restraints | 183 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.46 | 0.79, −0.49 |
Selected geometric parameters (Å, º) for (I) topCo1—N11 | 1.887 (3) | Co1—N210 | 1.943 (3) |
Co1—N12 | 1.911 (2) | Co1—N310 | 1.894 (11) |
Co1—N21 | 1.995 (3) | Co1—N410 | 2.097 (13) |
Co1—N31 | 2.036 (12) | N11—O11 | 1.342 (3) |
Co1—N41 | 1.848 (14) | N12—O12 | 1.287 (3) |
| | | |
N11—Co1—N310 | 168.0 (3) | N41—Co1—N210 | 169.7 (4) |
N11—Co1—N410 | 174.2 (3) | N210—Co1—N31 | 175.5 (3) |
N12—Co1—N21 | 172.92 (10) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H1O···O11i | 1.209 | 1.209 | 2.409 (4) | 170 |
O1W—H1W1···O3A | 0.89 | 1.95 | 2.816 (9) | 163 |
O1W—H2W1···O2B | 0.89 | 1.85 | 2.684 (9) | 155 |
O1W—H2W1···O2B' | 0.89 | 2.04 | 2.921 (13) | 173 |
O1W—H2W1···O3B | 0.89 | 2.42 | 2.940 (8) | 118 |
O2W—H1W2···O2A | 0.89 | 2.03 | 2.890 (9) | 161 |
O2W—H2W2···O12ii | 0.89 | 2.10 | 2.845 (5) | 140 |
O1C—H1C···O1W | 0.82 | 1.64 | 2.395 (7) | 151 |
O1C—H1C···O2B | 0.82 | 2.38 | 2.884 (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) topCo1—N11 | 1.9118 (18) | Co1—N210 | 1.9460 (18) |
Co1—N12 | 1.8949 (18) | Co1—N310 | 1.9942 (18) |
Co1—N21 | 1.9609 (18) | N11—O11 | 1.278 (2) |
Co1—N31 | 1.9371 (18) | N12—O12 | 1.382 (2) |
| | | |
N31—Co1—N210 | 175.27 (7) | N11—Co1—N310 | 175.85 (8) |
N12—Co1—N21 | 174.40 (7) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H1O···O1A | 0.96 | 1.71 | 2.659 (2) | 169 |
O12—H1O···O2A | 0.96 | 2.42 | 2.984 (2) | 117 |
O1W—H1W1···O2B'i | 1.06 | 1.71 | 2.464 (13) | 124 |
O1W—H1W1···O2Bi | 1.06 | 1.73 | 2.782 (8) | 169 |
O1C—H1C···O1W | 1.01 | 1.94 | 2.905 (11) | 161 |
O1D—H1D···O2Bi | 0.95 | 1.90 | 2.824 (8) | 162 |
Symmetry code: (i) −x, y+1/2, −z+3/2. |
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 π–π 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 π–π 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).