research communications
κN)bis(methylene)]bis(4-butyl-4,5-dihydro-1H-1,2,4-triazole-5-thione-κN2)}cobalt(II)
and spectroscopic properties of aquadichlorido{1,1′-[(pyridine-2,6-diyl-aDepartment of Chemistry and Biochemistry, Fairfield University, 1073 North Benson Road, Fairfield, CT 06824, USA, and bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435, USA
*Correspondence e-mail: jmiecznikowski@fairfield.edu, jjasinski@keene.edu
The structure of the title compound, [CoCl2(C19H27N7S2)(H2O)], at 173 K has monoclinic (C2/c) symmetry. We report here the synthesis, single-crystal structure, electrospray and NMR spectroscopy of a new six-coordinate cobalt(II) pincer complex. The pincer ligand, in this complex, which is novel, coordinates via three nitrogen atoms (two triazole and one pyridine). The ligand is ambidentate and can coordinate via three nitrogen atoms or two sulfur and one nitrogen atoms. The cobalt(II) metal center has pseudo-octahedral geometry and based on the single-crystal structure, the pincer ligand coordinates in a meridional fashion with the metal and adjacent six-membered ring ligands all in a similar plane and forming two slightly distorted boat configurations. The other two coordinated monodentate ligands are one water molecule and two chloride ions with four cobalt(II) complexes in the The of the complex is comprised of half the pyridine ring and water molecule with the CoII atom at the center of the pincer situated about a twofold axis. The Co—N, Co—O, and Co—Cl bond lengths are consistent with single bonds. In the crystal, the complex forms a three-centre bifurcated weak hydrogen-bonding interaction with a chlorine ion, forming one intermolecular interaction with the pincer group and a water molecule and a second intramolecular interaction with a C—H group within the pincer group. Crystal packing is also highlighted with C22(6)>a<a infinite chains forming along [001] supported by R22(8)>a>a ring motifs, forming a three-dimensional supramolecular network structure. While some stacking of the pyridine rings in the is observed, there are no relevant π–π interactions in the crystal packing. The 1H and 13C{1H} NMR spectra of the complex are consistent with a plane of symmetry being present. The electrospray which was collected in positive ion mode, showed the loss of one water molecule and one chloride ligand from the complex. In the future, we plan to screen this cobalt(II) complex for electrocatalysis reactivity.
Keywords: crystal structure; electrospray mass spectrum; NMR; cobalt(II); pincer complex.
CCDC reference: 2036378
1. Chemical context
Pincer ligands are tridentate ligands that coordinate to metal centers either in a meridional or facial manner (Peris & Crabtree, 2018; Gunanathan & Milstein, 2014). The resulting pincer complexes are robust and have been utilized as catalysts in a variety of reactions (Szabó & Wendt, 2014). Pincer complexes can be prepared using a wide range of metal centers. The donor atoms of the pincer ligand to the metal can be carbon, oxygen, nitrogen, phosphorous, or sulfur (Peris & Crabtree, 2018). Pincer ligand precursors can be tuned electronically by including electron-withdrawing or electron-donating groups, and sterically by including bulky substituents (van Koten & Milstein, 2013; van Koten & Gossage, 2015). Previously, Miecznikowski and co-workers prepared tridentate pincer ligand precursors with sulfur, nitrogen and sulfur donor atoms (Miecznikowski et al., 2011, 2012) (Fig. 1). The pincer ligand precursors were metallated with zinc(II)chloride in order to prepare zinc(II) model complexes of liver alcohol dehydrogenase (Miecznikowski et al., 2011, 2012) (see reaction scheme below). In 2012, Miecznikowski and co-workers reported the preparation of a pincer ligand precursor based on a bis-triazole starting material that could coordinate via sulfur, nitrogen, and sulfur donor atoms or via three nitrogen donor atoms (Miecznikowski et al., 2012). It was reported that the novel ambidentate tridentate pincer ligand precursor was metallated with ZnCl2 to give a new tridentate NNN-bound pincer zinc(II) pincer complex: dichloro(η3-N,N,N)-[2,6-bis(3-[N-butyl]triazol-5-thione-1-yl)]pyridinezinc(II), [(NNN)ZnCl2] (Fig. 1).
In this study, our aim was to prepare a cobalt(II) pincer complex that contained a pincer ligand precursor with methylene moieties connecting each triazole substituent to the pyridine in the pincer ligand precursor (Fig. 2). We wondered if the cobalt(II) metal center would coordinate to the pincer ligand via three nitrogen atoms as observed for the zinc(II) complex or via sulfur, nitrogen, and sulfur donor atoms. In this communication, we report the preparation, spectroscopic characterization, electrospray and single of a cobalt(II) pincer complex that contains an ambidentate ligand (Fig. 2).
2. Structural commentary
We report here the synthesis, single 19H29Cl2CoN7OS2, at 173 K whose structure has monoclinic (C2/c) symmetry (Fig. 3). The pincer ligand, in this complex, which is novel, coordinates via three nitrogen atoms (two triazole and one pyridine). The ligand is ambidentate and can coordinate via three nitrogen atoms or two sulfur and one nitrogen atom. The cobalt(II) metal center has a pseudo-octahedral geometry and based on the single the pincer ligand coordinates in a meridional fashion with the metal and adjacent six-membered ring ligands all in a similar plane and forming two slightly distorted boat configurations [Co1/N2/N2/C3/C4/N4: Q1 = 0.743 (6) Å, θ = 89.9°, φ = 345.8 (5)°; Co1/N4/C4A/C3A/N2A/N1A (atoms with the suffix A are generated by the 1 − x, y, −z + ): Q2 = 0.743 (6) Å, θ = 90.1(5°, φ = 185.3 (5)°} (Cremer & Pople, 1975). The other two coordinated monodentate ligands are one water molecule and two chloride ions with four cobalt(II) complexes in the The of the complex is comprised of half the pyridine ring and water molecule with the CoII atom at the center of the pincer situated about a twofold axis. The Co—N, Co—O, and Co—Cl bond lengths are consistent with single bonds. The cobalt–nitrogen (triazole) and cobalt–nitrogen (pyridine) bond lengths are comparable to those previously reported [triazole Co—N = 2.127 (2) and 2.093 (2) Å; pyridine Co—N= 2.187 (3) Å (Fang et al., 2019)]. The Co—O(water) bond length is comparable to previously reported values [2.09 (3) Å; See et al., 1998]. The cobalt–chloride bond lengths are longer than previously reported (2.31 Å; Di Vaira & Orioli, 1965). The C=S bond length of 1.655 (7) Å is more consistent with a carbon–sulfur double bond (1.61 Å; Trzhtsinskaya & Abramova, 1991).
electrospray and NMR spectroscopy of a new six-coordinate cobalt(II) pincer complex, C3. Supramolecular features
In the crystal, the complex forms a three-centre bifurcated weak hydrogen-bonding interaction (Table 1) with a chlorine ion, forming one intermolecular interaction with the pincer group and a water molecule and a second intramolecular interaction with a C—H group within the pincer group. The crystal packing is also highly supported by R22(8)>a>a ring motifs, forming a three-dimensional supramolecular network structure (Fig. 4). While some stacking of the pyridine rings in the is observed, there are no relevant π–π interactions or classical hydrogen bonds in the crystal packing. The 1H and 13C{1H} NMR spectra of the complex are consistent with a plane of symmetry being present. The electrospray which was collected in positive ion mode, showed the loss of one water molecule and one chloride ligand from the complex (see Fig. S1 in the supporting information). In the future, we plan to screen this cobalt(II) complex for electrocatalysis reactivity.
4. Database survey
The NNN pincer ligand precursor used in this study is novel. A related NNN pincer ligand, 4, has only been metallated with ZnCl2 to afford a five-coordinate zinc(II) complex (Miecznikowski et al., 2013). To the best of our knowledge (following a search using Sci-Finder Scholar) no other metal complexes that contain this ligand precursor have been reported in the literature.
5. Synthesis and crystallization
The preparation of the title complex, 8, and the corresponding ligand precursors 6 and 7 were accomplished according to the scheme below. The precursor for complex 6 has been reported previously (Guino-o et al., 2015).
2,6-Bis[(4-butyl-4H-1,2,4-triazol-1-yl)methyl]pyridine diiodide (Miecznikowski et al., 2011): In a 100 ml round-bottom flask, 3.0501 g (0.0126 mol) of 2,6-bis[(1H-1,2,4-triazol-1-yl)methyl]pyridine was dissolved in 25 ml of 1,4 dioxane. To this solution 13.958 g (0.0759 mol) of iodobutane were added. This solution was heated at reflux for 18 h. After allowing the solution to cool, the mother liquor was decanted off. The precipitate was dissolved in minimal methanol and transferred to a round-bottom flask. The solvent was then removed under reduced pressure. Yield: 3.85 g (0.00748 mol) (59.4% yield).
The product was characterized using 1H and 13C{1H} NMR spectroscopy.
1H NMR (DMSO-d6, 400 Mhz): δ 10.32 (s, 2H, triazole, CH), 9.30 (s, 2H, triazole, CH), 7.97 (m, 1H, pyridine CH), 7.52 (m, (2H, pyridine CH), 5.75 (s, 4H, CH2 linker), 4.32 (m, 4H, n-butyl CH2), 1.85 (m, 4H, n-butyl CH2), 1.32 (m, 4H, n-butyl CH2), 0.92 (m, 6H, n-butyl CH3). 13C {1H} NMR (DMSO-d6, 100 Mhz), δ 152.59 (pyridine C), 144.91 (triazole CH), 143.51 (triazole CH), 138.95 (pyridine CH), 122.85 (pyridine CH), 55.74 (CH2 linker), 47.42 (n-butyl CH2), 30.82 (n-butyl CH2), 18.79 (n-butyl CH2), 13.34 (n-butyl CH3).
2,2′-[Pyridine-2,6-diylbis(methylene)]bis(4-butyl-1,2,4-triazole-3-thione) (Miecznikowski, 2012): In a 35 mL microwave reactor vessel, 0.2694 g (5.228 × 10 −4 mol) of 6 were dissolved in 15 mL of MeCN. To this solution, 0.800 g (0.0249 mol) of sulfur and 0.2162 g (0.001564 mol) of potassium carbonate were added. This mixture was heated at 398 K for 6 h in the microwave reactor. After the reaction was complete, the undissolved solids were removed by vacuum filtration and the remaining solvent was removed under reduced pressure. The product was purified by dissolving the product in CH2Cl2 and filtering it through an alumina column to removed undissolved sulfur. Mass product = 0.0934 g (2.24 x 10 −4 mol) (42.8% yield).
The product was characterized using 1H and 13C{1H} NMR spectroscopy. The key feature of the NMR is that one of the acidic protons of the triazole, δ 10.32 in 6 was absent in the product and was presumably replaced with the thione moiety. There was also considerable shifting, to lower ppm values, of the aromatic, methylene and n-butyl CH2 proton resonances in 7 compared to the starting material 6.
1H NMR (DMSO-d6, 400 MHz): δ 8.65 (s, 2H, triazole, CH), 7.75 (m, 1H, pyridine CH), 7.02 (s, 2H, pyridine CH), 5.41 (s, 4H, CH2 linker), 3.98 (m, 4H, n-butyl CH2), 1.72 (m, 4H, n-butyl CH2), 1.29 (m, 4H, n-butyl CH2), 0.92 (m, 6H, n-butyl CH3). 13C {1H} NMR (DMSO-d6, 100 MHz), δ 166.03 (C=S), 155.02 (pyridine C), 141.41 (triazole CH), 137.92 (pyridine CH), 120.23 (pyridine CH), 53.03 (CH2 linker), 45.14 (n-butyl CH2), 29.91 (n-butyl CH2), 19.04 (n-butyl CH2), 13.47 (n-butyl CH3).
Aquadichloro-(n3-N,N,N)-[2,6-diylbis(methylene)bis(4-[N-butyl]triazol-5-thione-1-yl)]pyridinecobalt(II) [C19H29Cl2N7OS2Co]: In a 100mL round-bottom flask, 0.0934 g (2.24 × 10−4 mol) of (C19H27N7S2) were combined with 0.076 g (2.2 × 10−4 mol) of cobalt(II)tetrafluoroborate [Co(BF4)2·6H2O] and combined with 0.0333 g (4.43 × 10−4 moles) of potassium chloride (KCl) and dissolved in 10 mL of acetonitrile. The solution was refluxed for 20 h. The following day, the solution was filtered to remove undissolved material and the solvent was removed under reduced pressure. Yield: 0.162 grams (quantitative). Purple needle-shaped crystals suitable for X-ray diffraction were grown by a slow vapor diffusion of diethyl ether in to an acetonitrile solution containing the cobalt complex.
Analysis calculated for [C19H29Cl2CoN7S2]·H2O: (583.46): C, 39.11; H, 5.36; N, 16.80. Found: C, 39.33; H, 5.07; N, 17.11.
1H NMR (DMSO-d6, 400 MHz) δ 8.61 (s, 2H, triazole, CH), 7.71 (t, 1H, pyridine CH), 6.91 (d, 2H pyridine CH), 5.37 (s, 4H, CH2 linker), 3.95 (m, 4H, n-butyl CH2), 1.70 (m, 4H, n-butyl CH2), 1.26 (m, 4H, n-butyl CH2), 0.88 (t, 6H, n-butyl CH3). 13C {1H} NMR (DMSO-d6, 100 MHz), δ 164.95 (C=S), 153.93 (pyridine C), 140.47 (triazole CH), 136.91 (pyridine CH), 119.19 (pyridine CH), 51.98 (CH2 linker), 44.13 (n-butyl CH2), 28.87 (n-butyl CH2), 18.01 (n-butyl CH2), 12.47 (n-butyl CH3).
The 1H NMR and 13C{1H} spectrum of the complex was acquired in DMSO-d6. The NMR spectrum was consistent with the title complex. There was not considerable shifting of the proton resonances compared to the starting bis-thione precursor. In the 13C{1H} NMR spectrum, the C=S resonance shifted about δ 1 ppm to a lower value.
The cyclic voltammograms of 7 and 8 are given in Figs. S1 and S2, respectively, in the supporting information. In both 7 and 8 the is 0.2 M tetrabutylammonium tetrafluoroborate. The is Ag wire, the is glassy carbon and the counter electrode is a platinum wire. The scan rate is 100 mV s-1.
Electronic absorption spectrum of 8 in acetonitrile (1.89 mM) (see Fig. S4 in the supporting information): UV–Visible data: λ (nm), (∊ (M−1cm−1) (1.89 mM in MeCN) 234.00 (2480); 244.00 (2480); 368.00 (158); 574.00 nm (sh) (386); 589.00 (428); 682.00 (648).
6. Refinement
Crystal data, data collection and structure . H atoms were positioned geometrically (O—H = 0.84, C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O, C-methyl).
details are summarized in Table 2Supporting information
CCDC reference: 2036378
https://doi.org/10.1107/S2056989020013547/jy2002sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020013547/jy2002Isup2.hkl
Supplementary figures. DOI: https://doi.org/10.1107/S2056989020013547/jy2002sup2.pdf
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: ShelXT (Sheldrick, 2015b); program(s) used to refine structure: SHELXL (Sheldrick, 2015a); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[CoCl2(C19H27N7S2)(H2O)] | F(000) = 1172 |
Mr = 565.44 | Dx = 1.447 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54184 Å |
a = 26.3412 (8) Å | Cell parameters from 3680 reflections |
b = 11.4270 (3) Å | θ = 5.1–71.4° |
c = 8.6226 (3) Å | µ = 8.80 mm−1 |
β = 90.465 (3)° | T = 173 K |
V = 2595.31 (13) Å3 | Plate, violet |
Z = 4 | 0.32 × 0.24 × 0.1 mm |
Rigaku Oxford Diffraction Gemini Eos diffractometer | 1935 reflections with I > 2σ(I) |
Detector resolution: 16.0416 pixels mm-1 | Rint = 0.077 |
ω scans | θmax = 71.3°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015) | h = −31→32 |
Tmin = 0.050, Tmax = 1.000 | k = −14→13 |
7187 measured reflections | l = −10→5 |
2483 independent reflections |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.082 | w = 1/[σ2(Fo2) + (0.0964P)2 + 26.3272P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.235 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 1.40 e Å−3 |
2483 reflections | Δρmin = −0.65 e Å−3 |
149 parameters | Extinction correction: SHELXL2018/1 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0012 (2) |
Primary atom site location: dual |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.500000 | 0.67881 (12) | 0.250000 | 0.0337 (5) | |
Cl1 | 0.54526 (6) | 0.66425 (15) | 0.00348 (19) | 0.0453 (5) | |
S1 | 0.67541 (8) | 0.8989 (2) | 0.5267 (3) | 0.0709 (7) | |
O1 | 0.500000 | 0.4946 (6) | 0.250000 | 0.0528 (18) | |
H1 | 0.490570 | 0.453156 | 0.174640 | 0.079* | |
N1 | 0.5694 (2) | 0.6878 (5) | 0.3822 (6) | 0.0404 (13) | |
N2 | 0.5993 (2) | 0.7856 (5) | 0.3730 (7) | 0.0400 (13) | |
N3 | 0.6244 (2) | 0.6944 (6) | 0.5757 (7) | 0.0439 (14) | |
N4 | 0.500000 | 0.8712 (7) | 0.250000 | 0.0396 (17) | |
C1 | 0.5856 (3) | 0.6350 (7) | 0.5066 (8) | 0.0451 (16) | |
H1A | 0.571981 | 0.563686 | 0.544692 | 0.054* | |
C2 | 0.6333 (3) | 0.7948 (7) | 0.4898 (9) | 0.0472 (17) | |
C3 | 0.5931 (3) | 0.8675 (6) | 0.2452 (9) | 0.0454 (16) | |
H3A | 0.594825 | 0.824119 | 0.145975 | 0.054* | |
H3B | 0.621543 | 0.924266 | 0.247439 | 0.054* | |
C4 | 0.5441 (3) | 0.9327 (6) | 0.2516 (8) | 0.0456 (16) | |
C5 | 0.5448 (4) | 1.0553 (7) | 0.2553 (11) | 0.065 (2) | |
H5 | 0.576185 | 1.096191 | 0.261514 | 0.078* | |
C6 | 0.500000 | 1.1154 (10) | 0.250000 | 0.076 (4) | |
H6 | 0.500000 | 1.198536 | 0.250002 | 0.092* | |
C7 | 0.6532 (3) | 0.6589 (9) | 0.7150 (10) | 0.065 (2) | |
H7A | 0.629478 | 0.621798 | 0.788644 | 0.078* | |
H7B | 0.666974 | 0.730085 | 0.765450 | 0.078* | |
C8 | 0.6957 (4) | 0.5769 (11) | 0.6865 (13) | 0.083 (3) | |
H8A | 0.717687 | 0.573444 | 0.780111 | 0.100* | |
H8B | 0.716444 | 0.606952 | 0.599897 | 0.100* | |
C9 | 0.6777 (5) | 0.4566 (15) | 0.6479 (17) | 0.116 (5) | |
H9A | 0.661282 | 0.459438 | 0.544311 | 0.139* | |
H9B | 0.651149 | 0.435140 | 0.723408 | 0.139* | |
C10 | 0.7162 (6) | 0.3608 (15) | 0.6464 (19) | 0.125 (5) | |
H10A | 0.743434 | 0.381083 | 0.574431 | 0.188* | |
H10B | 0.700015 | 0.287769 | 0.612867 | 0.188* | |
H10C | 0.730446 | 0.350724 | 0.750896 | 0.188* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0320 (7) | 0.0305 (8) | 0.0387 (8) | 0.000 | −0.0011 (6) | 0.000 |
Cl1 | 0.0447 (9) | 0.0495 (10) | 0.0417 (9) | 0.0014 (7) | 0.0047 (7) | −0.0035 (7) |
S1 | 0.0442 (10) | 0.0749 (15) | 0.0934 (17) | −0.0210 (10) | −0.0088 (10) | −0.0141 (12) |
O1 | 0.079 (5) | 0.038 (4) | 0.041 (4) | 0.000 | −0.007 (3) | 0.000 |
N1 | 0.035 (3) | 0.041 (3) | 0.045 (3) | −0.008 (2) | 0.003 (2) | 0.005 (2) |
N2 | 0.032 (3) | 0.037 (3) | 0.052 (3) | −0.013 (2) | −0.002 (2) | 0.004 (2) |
N3 | 0.028 (3) | 0.058 (4) | 0.046 (3) | −0.002 (2) | −0.001 (2) | −0.001 (3) |
N4 | 0.041 (4) | 0.037 (4) | 0.041 (4) | 0.000 | −0.001 (3) | 0.000 |
C1 | 0.037 (3) | 0.047 (4) | 0.052 (4) | 0.000 (3) | 0.009 (3) | 0.010 (3) |
C2 | 0.031 (3) | 0.053 (4) | 0.058 (4) | −0.002 (3) | 0.003 (3) | −0.002 (3) |
C3 | 0.041 (4) | 0.043 (4) | 0.052 (4) | −0.010 (3) | 0.005 (3) | 0.008 (3) |
C4 | 0.052 (4) | 0.040 (4) | 0.045 (4) | −0.003 (3) | −0.002 (3) | 0.001 (3) |
C5 | 0.072 (5) | 0.038 (4) | 0.086 (6) | −0.008 (4) | −0.014 (5) | 0.006 (4) |
C6 | 0.080 (9) | 0.030 (6) | 0.119 (12) | 0.000 | −0.035 (8) | 0.000 |
C7 | 0.043 (4) | 0.096 (7) | 0.055 (5) | −0.001 (4) | −0.004 (4) | 0.006 (5) |
C8 | 0.057 (5) | 0.117 (10) | 0.075 (6) | 0.012 (6) | −0.011 (5) | 0.012 (6) |
C9 | 0.089 (8) | 0.154 (14) | 0.104 (10) | 0.022 (9) | −0.028 (7) | −0.035 (9) |
C10 | 0.106 (10) | 0.141 (13) | 0.129 (12) | 0.026 (10) | −0.028 (9) | 0.008 (10) |
Co1—Cl1 | 2.4512 (16) | C3—H3A | 0.9900 |
Co1—Cl1i | 2.4512 (16) | C3—H3B | 0.9900 |
Co1—O1 | 2.104 (7) | C3—C4 | 1.493 (10) |
Co1—N1 | 2.149 (6) | C4—C5 | 1.401 (11) |
Co1—N1i | 2.148 (6) | C5—H5 | 0.9500 |
Co1—N4 | 2.198 (8) | C5—C6 | 1.367 (11) |
S1—C2 | 1.655 (7) | C6—H6 | 0.9500 |
O1—H1 | 0.8403 | C7—H7A | 0.9900 |
O1—H1i | 0.8403 | C7—H7B | 0.9900 |
N1—N2 | 1.370 (7) | C7—C8 | 1.482 (14) |
N1—C1 | 1.300 (9) | C8—H8A | 0.9900 |
N2—C2 | 1.346 (9) | C8—H8B | 0.9900 |
N2—C3 | 1.454 (9) | C8—C9 | 1.491 (18) |
N3—C1 | 1.360 (9) | C9—H9A | 0.9900 |
N3—C2 | 1.387 (10) | C9—H9B | 0.9900 |
N3—C7 | 1.472 (10) | C9—C10 | 1.493 (19) |
N4—C4i | 1.357 (8) | C10—H10A | 0.9800 |
N4—C4 | 1.357 (8) | C10—H10B | 0.9800 |
C1—H1A | 0.9500 | C10—H10C | 0.9800 |
Cl1i—Co1—Cl1 | 172.22 (10) | N2—C3—C4 | 112.6 (6) |
O1—Co1—Cl1i | 86.11 (5) | H3A—C3—H3B | 107.8 |
O1—Co1—Cl1 | 86.11 (5) | C4—C3—H3A | 109.1 |
O1—Co1—N1i | 92.74 (16) | C4—C3—H3B | 109.1 |
O1—Co1—N1 | 92.74 (16) | N4—C4—C3 | 118.8 (6) |
O1—Co1—N4 | 180.0 | N4—C4—C5 | 122.0 (8) |
N1i—Co1—Cl1i | 92.61 (15) | C5—C4—C3 | 119.2 (7) |
N1—Co1—Cl1 | 92.61 (15) | C4—C5—H5 | 120.3 |
N1—Co1—Cl1i | 87.76 (15) | C6—C5—C4 | 119.3 (9) |
N1i—Co1—Cl1 | 87.76 (15) | C6—C5—H5 | 120.3 |
N1i—Co1—N1 | 174.5 (3) | C5—C6—C5i | 119.7 (11) |
N1i—Co1—N4 | 87.26 (16) | C5—C6—H6 | 120.2 |
N1—Co1—N4 | 87.26 (16) | C5i—C6—H6 | 120.2 |
N4—Co1—Cl1 | 93.89 (5) | N3—C7—H7A | 108.5 |
N4—Co1—Cl1i | 93.89 (5) | N3—C7—H7B | 108.5 |
Co1—O1—H1 | 124.3 | N3—C7—C8 | 115.1 (8) |
Co1—O1—H1i | 124.346 (2) | H7A—C7—H7B | 107.5 |
H1—O1—H1i | 111.3 | C8—C7—H7A | 108.5 |
N2—N1—Co1 | 119.7 (4) | C8—C7—H7B | 108.5 |
C1—N1—Co1 | 133.5 (5) | C7—C8—H8A | 109.1 |
C1—N1—N2 | 103.9 (6) | C7—C8—H8B | 109.1 |
N1—N2—C3 | 120.5 (5) | C7—C8—C9 | 112.3 (9) |
C2—N2—N1 | 113.6 (6) | H8A—C8—H8B | 107.9 |
C2—N2—C3 | 125.9 (6) | C9—C8—H8A | 109.1 |
C1—N3—C2 | 108.0 (6) | C9—C8—H8B | 109.1 |
C1—N3—C7 | 126.9 (7) | C8—C9—H9A | 107.9 |
C2—N3—C7 | 125.1 (6) | C8—C9—H9B | 107.9 |
C4i—N4—Co1 | 121.2 (4) | C8—C9—C10 | 117.6 (11) |
C4—N4—Co1 | 121.2 (4) | H9A—C9—H9B | 107.2 |
C4i—N4—C4 | 117.6 (8) | C10—C9—H9A | 107.9 |
N1—C1—N3 | 111.8 (6) | C10—C9—H9B | 107.9 |
N1—C1—H1A | 124.1 | C9—C10—H10A | 109.5 |
N3—C1—H1A | 124.1 | C9—C10—H10B | 109.5 |
N2—C2—S1 | 129.8 (6) | C9—C10—H10C | 109.5 |
N2—C2—N3 | 102.7 (6) | H10A—C10—H10B | 109.5 |
N3—C2—S1 | 127.5 (6) | H10A—C10—H10C | 109.5 |
N2—C3—H3A | 109.1 | H10B—C10—H10C | 109.5 |
N2—C3—H3B | 109.1 | ||
Co1—N1—N2—C2 | 162.7 (5) | C1—N3—C2—N2 | −1.2 (8) |
Co1—N1—N2—C3 | −17.8 (8) | C1—N3—C7—C8 | 83.9 (10) |
Co1—N1—C1—N3 | −160.2 (5) | C2—N2—C3—C4 | −111.9 (8) |
Co1—N4—C4—C3 | 3.1 (7) | C2—N3—C1—N1 | 1.0 (8) |
Co1—N4—C4—C5 | −178.5 (6) | C2—N3—C7—C8 | −94.5 (11) |
N1—N2—C2—S1 | −178.3 (6) | C3—N2—C2—S1 | 2.3 (11) |
N1—N2—C2—N3 | 1.1 (8) | C3—N2—C2—N3 | −178.4 (6) |
N1—N2—C3—C4 | 68.7 (8) | C3—C4—C5—C6 | 175.3 (6) |
N2—N1—C1—N3 | −0.3 (8) | C4i—N4—C4—C3 | −176.9 (7) |
N2—C3—C4—N4 | −58.7 (8) | C4i—N4—C4—C5 | 1.5 (6) |
N2—C3—C4—C5 | 122.8 (8) | C4—C5—C6—C5i | 1.5 (6) |
N3—C7—C8—C9 | −72.6 (12) | C7—N3—C1—N1 | −177.6 (7) |
N4—C4—C5—C6 | −3.1 (12) | C7—N3—C2—S1 | −3.1 (11) |
C1—N1—N2—C2 | −0.5 (8) | C7—N3—C2—N2 | 177.5 (7) |
C1—N1—N2—C3 | 179.0 (6) | C7—C8—C9—C10 | −168.6 (12) |
C1—N3—C2—S1 | 178.2 (6) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl1ii | 0.84 | 2.24 | 3.075 (4) | 171 |
C1—H1A···O1iii | 0.95 | 2.69 | 3.429 (7) | 135 |
C3—H3A···Cl1 | 0.99 | 2.55 | 3.360 (8) | 138 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1. |
Acknowledgements
JRM is grateful for all of the financial support he received for this project: the Connecticut NASA Space Grant Alliance (award No. P-1168), the National Science Foundation–Major Research Instrumentation Program (grant No. CHE-1827854) for funds to acquire a 400 MHz NMR spectrometer. JRM acknowledges support from The Science Institute of the College of Arts and Sciences at Fairfield University for this work. JRM thanks Terence Wu (Yale University) for assistance in acquiring electrospray mass spectra. JP expresses thanks to the National Science Foundation–Major Research Instrumentation Program (grant No. CHE-1039027) for funds to purchase an X-ray diffractometer. ANS and NRB acknowledge financial support from the Klimas Fund to support their summer research at Fairfield University. SCB acknowledges financial support from the Department of Chemistry and Biochemistry Kuck Fund to support her summer laboratory research.
Funding information
Funding for this research was provided by: National Science Foundation (award No. CHE-1827854 to John R. Miecznikowski; award No. CHE-1039027 to Jerry P. Jasinski); Connecticut Space Grant College Consortium (award No. P-1168 to John R. Miecznikowski); Fairfield University Science Institute of the College of Arts and Sciences (award to John R. Miecznikowski); Fairfield University Kuck Fund (award to Sheila C. Bonitatibus); Fairfield Univesity Klimas Fund (award to Allison N. Smolinsky, Natalia R. Bertolotti).
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