The reaction of 2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetic acid (NBTA) and triethanolamine (TEA) with Co(NO3)2 results in the formation of the title complex. In the complex cation, the CoII ion is octahedrally coordinated by two N,O,O′-tridentate TEA molecules with a facial distribution and the N atoms in a trans arrangement.
Keywords: crystal structure, triethanolamine, α-(N-benzothiazolin-2-one) acetic acid, hydrogen bonding
Abstract
The reaction of 2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetic acid (NBTA) and triethanolamine (TEA) with Co(NO3)2 results in the formation of the title complex, [Co(C6H15NO3)2](C9H6NO3S)2, which is formed as a result of the association of bis(triethanolamine)cobalt(II) and 2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate units. It crystallizes in the monoclinic centrosymmetric space group P21/c, with the CoII ion situated on an inversion centre. In the complex cation, the CoII ion is octahedrally coordinated by two N,O,O′-tridentate TEA molecules with a facial distribution and the N atoms in a trans arrangement. Two ethanol groups of each TEA molecule form two five-membered chelate rings around the CoII ion, while the third ethanol group does not coordinate to the metal. The free and coordinating hydroxy groups of the TEA molecules are involved in hydrogen bonding with the O atoms of NBTA anions, forming an infinite two-dimensional network extending parallel to the bc plane.
Chemical context
Triethanolamine (TEA) is used as a corrosion inhibitor in metal-cutting fluids, as a curing agent for epoxy and rubber polymers, adhesives and antistatic agents and as a pharmaceutical intermediate and an ointment emulsifier etc. However, TEA is not a substance possessing a specific physiological action (Beyer et al., 1983 ▸; Knaak et al., 1997 ▸) with exception of its low antibacterial activity. Benzothiazole is a precursor for rubber accelerators, a component of cyanine dyes, a slimicide in the paper and pulp industry, and is used in the production of certain fungicides, herbicides, antifungal agents and pharmaceuticals (Bellavia et al., 2000 ▸; Seo et al., 2000 ▸). The interaction of metal ions with TEA results in the formation of complexes in which TEA demonstrates monodentate (Kumar et al., 2014 ▸), bidentate (Kapteijn et al., 1997 ▸), tridentate (Gao et al., 2004 ▸; Ucar et al., 2004 ▸; Topcu et al., 2001 ▸; Krabbes et al., 1999 ▸; Haukka et al., 2005 ▸; Yeşilel et al., 2004 ▸; Mirskova et al., 2013 ▸) and tetradentate binding (Zaitsev et al., 2014 ▸; Kazak et al., 2003 ▸; Yilmaz et al., 2004 ▸; Langley et al., 2011 ▸; Rickard et al., 1999 ▸; Maestri & Brown, 2004 ▸; Kovbasyuk et al., 2001 ▸; Tudor et al., 2001 ▸). In some complexes, TEA can show bridging properties (Atria et al., 2015 ▸; Wittick et al., 2006 ▸; Sharma et al., 2014 ▸; Yang et al., 2014 ▸; Funes et al., 2014 ▸). Here, we report the synthesis and structure of the title compound, [Co(C6H15NO3)2](C9H6NO3S)2, (I). 
Structural commentary
The molecular structure of compound (I) is shown in Fig. 1 ▸. The structure consists of a complex cation and one 2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate anion. The asymmetric unit contains a half of the cationic moiety because the CoII ion is located on an inversion centre. The cation and anion are linked by an O6—H6⋯O2 hydrogen bond (Table 1 ▸). In the cationic complex, the CoII ion is coordinated by four oxygen and two nitrogen atoms of two ligands. The nitrogen atoms occupy trans positions of the coordination polyhedron. The Co—N bond lengths [2.151 (3) Å] are equal as a result of symmetry, and the N—Co—N bond angle is 180°. The Co—O distances are 2.097 (2) Å and 2.101 (3) Å. One hydroxy group of each ethanol substituent is not involved in the coordination and is directed away from the coordination centre. The N—Co—O bond angles range from 81.60 (10) to 98.40 (10)° and the O—Co—O angles are 89.79 (10) and 90.21 (10)°. Thus, the coordination polyhedron of the central atom is a slightly distorted octahedron of the CoN2O4-type. The thiazoline ring (C1/C6/N1/C7/S1) and the bicyclic benzothiazole unit (N1/S1/C1–C7) are close to planar, the largest deviations from the least-squares planes being 0.019 (2) and 0.028 (4) Å, respectively. The dihedral angle between the plane of the carboxylate group and the benzothiazole ring system is 85.6 (2)°.
Figure 1.
The molecular structure of (I), showing the atom-labelling scheme. Unlabelled atoms are generated by the inversion centre.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O4—H4⋯O2i | 0.88 (3) | 1.71 (3) | 2.572 (4) | 166 (3) |
| O5—H5⋯O3ii | 0.86 (1) | 1.75 (2) | 2.577 (4) | 159 (3) |
| O6—H6⋯O2 | 0.82 | 1.88 | 2.697 (4) | 173 |
| C8—H8A⋯O1iii | 0.97 | 2.48 | 3.432 (6) | 167 |
| C12—H12B⋯O6iv | 0.97 | 2.53 | 3.455 (6) | 159 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
.
Supramolecular features
The crystal structure of (I) contains an intricate network of intermolecular O—H⋯O and C—H⋯O hydrogen bonds (Table 1 ▸). The [Co(TEA)2]2+ cations play an important role in the supramolecular architecture. Each cation is surrounded by four 2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate anions. The H atoms of the free hydroxy group of the TEA ligand form a hydrogen bond with the carboxylate O atom of the NBTA ion while the coordinating hydroxy H atoms are involved in intermolecular hydrogen bonding with the carboxylate O atoms of the NBTA ions [H4⋯O2i = 1.71 (3) Å and H5⋯O3ii = 1.752 (17)Å; symmetry codes: (i) x, −1 + y, z; (ii) 2 − x, 1 − y, 2 − z]. In addition, there is weak hydrogen bond between the –CH2 group and the non-coordinating hydroxy-O atoms of the TEA ligand, with a C⋯O distance of 3.455 (6) Å. The above-mentioned hydrogen bonds give rise to 
(22) and 
(22) graph-set motifs. The crystal structure contains layers of hydrogen-bonded cations that are sandwiched between layers of hydrogen-bonded anions. Each layer extends in the bc plane. There is hydrogen bonding within and between these layers. These are arranged along [100] in the sequence ACA·ACA·ACA (where A = anion layer and C = cation layer; Fig. 2 ▸) The NBTA anion layers are not linked by hydrogen bonds, but there are π–π stacking interactions between benzene (centroid Cg1) and thiazolin (centroid Cg2) rings [Cg1⋯Cg2(-x, −y, −z) = 3.71 Å] of adjacent inversion-related molecules (Fig. 3 ▸).
Figure 2.
Part of the crystal structure with hydrogen bonds shown as dashed lines. For clarity, H atoms not involved in hydrogen bonding are not shown.
Figure 3.
The crystal structure packing of (I). Hydrogen bonds are indicated by black dashed lines and π–π stacking interactions by red dashed lines.
Database survey
A survey of the Cambridge Structural Database (CSD; Groom & Allen, 2014 ▸) showed that coordination complexes of TEA with many metals including those of the s-, d-, p-, and f-blocks have been reported. Structures containing the bis(triethanolamine)cobalt(II) cation are described in the CSD entries with refcodes ASUGEA, IGALOR, WEPLIN.
Synthesis and crystallization
To an aqueous solution (2.5 ml) of Co(NO3)2 (0.091 g, 0.5 mmol) was added slowly an ethanol solution (5 ml) containing TEA (132 µl) and NBTA (0.209 g, 1 mmol) with constant stirring. A light-brown crystalline product was obtained at room temperature by solvent evaporation after four weeks (yield 70%). Elemental analysis calculated for C30H42CoN4O12S2: C, 46.57; H, 5.47; N, 7.24. Found: C, 46.62; H, 5.41; N, 7.19.
Refinement details
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The coordinating hydroxy H atoms of the TEA ligand were located in a difference Fourier map and freely refined. C-bound H atoms were placed in calculated positions and refined as riding atoms: C—H = 0.93 and 0.97 Å for aromatic and methylene H, with U iso(H) = 1.2U eq(C).
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [Co(C6H15NO3)2](C9H6NO3S)2 |
| M r | 773.73 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 14.6953 (6), 9.7043 (3), 12.1311 (4) |
| β (°) | 98.513 (4) |
| V (Å3) | 1710.94 (11) |
| Z | 2 |
| Radiation type | Cu Kα |
| μ (mm−1) | 5.66 |
| Crystal size (mm) | 0.28 × 0.24 × 0.18 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur Ruby |
| Absorption correction | Multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Oxford Diffraction, 2009 ▸) |
| T min, T max | 0.280, 0.797 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7096, 3487, 2693 |
| R int | 0.048 |
| (sin θ/λ)max (Å−1) | 0.629 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.061, 0.175, 1.03 |
| No. of reflections | 3487 |
| No. of parameters | 230 |
| No. of restraints | 6 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.47, −0.53 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016002930/pj2027sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016002930/pj2027Isup2.hkl
CCDC reference: 1454443
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
This work was supported by a Grant for Fundamental Research from the Center of Science and Technology, Uzbekistan (No. FPFI T.3-14).
supplementary crystallographic information
Crystal data
| [Co(C6H15NO3)2](C9H6NO3S)2 | F(000) = 810 |
| Mr = 773.73 | Dx = 1.502 Mg m−3 |
| Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1414 reflections |
| a = 14.6953 (6) Å | θ = 3.7–75.3° |
| b = 9.7043 (3) Å | µ = 5.66 mm−1 |
| c = 12.1311 (4) Å | T = 293 K |
| β = 98.513 (4)° | Block, dark orange |
| V = 1710.94 (11) Å3 | 0.28 × 0.24 × 0.18 mm |
| Z = 2 |
Data collection
| Oxford Diffraction Xcalibur Ruby diffractometer | 3487 independent reflections |
| Radiation source: fine-focus sealed tube | 2693 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.048 |
| Detector resolution: 10.2576 pixels mm-1 | θmax = 75.8°, θmin = 5.5° |
| ω scans | h = −18→17 |
| Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Oxford Diffraction, 2009) | k = −10→12 |
| Tmin = 0.280, Tmax = 0.797 | l = −12→15 |
| 7096 measured reflections |
Refinement
| 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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.175 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0899P)2 + 0.4878P] where P = (Fo2 + 2Fc2)/3 |
| 3487 reflections | (Δ/σ)max < 0.001 |
| 230 parameters | Δρmax = 0.47 e Å−3 |
| 6 restraints | Δρmin = −0.53 e Å−3 |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| Co1 | 1.0000 | 0.0000 | 1.0000 | 0.0321 (2) | |
| S1 | 1.42643 (10) | 0.51313 (12) | 1.23063 (9) | 0.0613 (3) | |
| O4 | 1.09939 (16) | −0.1150 (3) | 1.1029 (2) | 0.0405 (6) | |
| H4 | 1.1359 (16) | −0.175 (3) | 1.078 (2) | 0.061* | |
| O2 | 1.21319 (18) | 0.7409 (3) | 1.0090 (3) | 0.0511 (7) | |
| O5 | 0.92168 (17) | 0.0172 (2) | 1.1309 (2) | 0.0397 (6) | |
| H5 | 0.8630 (7) | 0.025 (4) | 1.130 (2) | 0.060* | |
| C4 | 1.3618 (3) | 0.3107 (6) | 0.8983 (4) | 0.0640 (12) | |
| H4A | 1.3469 | 0.2728 | 0.8275 | 0.077* | |
| N2 | 1.07355 (19) | 0.1681 (3) | 1.0879 (2) | 0.0354 (6) | |
| O6 | 1.1297 (3) | 0.4967 (3) | 0.9585 (3) | 0.0719 (11) | |
| H6 | 1.1537 | 0.5703 | 0.9793 | 0.108* | |
| O3 | 1.25064 (18) | 0.9228 (3) | 0.9142 (3) | 0.0593 (8) | |
| O1 | 1.4058 (3) | 0.7837 (3) | 1.1993 (3) | 0.0715 (9) | |
| N1 | 1.3885 (2) | 0.6444 (3) | 1.0445 (3) | 0.0432 (7) | |
| C11 | 1.0861 (3) | 0.2771 (4) | 1.0053 (3) | 0.0455 (9) | |
| H11A | 1.0256 | 0.3054 | 0.9693 | 0.055* | |
| H11B | 1.1176 | 0.2363 | 0.9484 | 0.055* | |
| C1 | 1.4051 (2) | 0.4195 (4) | 1.1068 (3) | 0.0441 (8) | |
| C9 | 1.2684 (2) | 0.8119 (4) | 0.9634 (3) | 0.0437 (8) | |
| C10 | 1.1382 (3) | 0.4043 (4) | 1.0483 (3) | 0.0507 (9) | |
| H10A | 1.1122 | 0.4435 | 1.1102 | 0.061* | |
| H10B | 1.2024 | 0.3826 | 1.0731 | 0.061* | |
| C6 | 1.3850 (2) | 0.5060 (4) | 1.0156 (3) | 0.0405 (8) | |
| C13 | 1.1640 (3) | 0.1118 (4) | 1.1391 (4) | 0.0535 (10) | |
| H13A | 1.1899 | 0.1712 | 1.2002 | 0.064* | |
| H13B | 1.2056 | 0.1126 | 1.0841 | 0.064* | |
| C15 | 1.0160 (3) | 0.2213 (4) | 1.1688 (3) | 0.0464 (9) | |
| H15A | 0.9732 | 0.2890 | 1.1321 | 0.056* | |
| H15B | 1.0551 | 0.2672 | 1.2292 | 0.056* | |
| C8 | 1.3671 (3) | 0.7592 (4) | 0.9693 (4) | 0.0500 (10) | |
| H8A | 1.3771 | 0.7314 | 0.8952 | 0.060* | |
| H8B | 1.4092 | 0.8341 | 0.9928 | 0.060* | |
| C7 | 1.4049 (3) | 0.6711 (5) | 1.1570 (4) | 0.0520 (10) | |
| C12 | 1.1576 (3) | −0.0320 (5) | 1.1821 (4) | 0.0542 (11) | |
| H12A | 1.2186 | −0.0725 | 1.1962 | 0.065* | |
| H12B | 1.1329 | −0.0298 | 1.2520 | 0.065* | |
| C3 | 1.3811 (3) | 0.2232 (5) | 0.9886 (4) | 0.0628 (12) | |
| H3 | 1.3783 | 0.1283 | 0.9781 | 0.075* | |
| C5 | 1.3638 (3) | 0.4522 (5) | 0.9094 (3) | 0.0522 (10) | |
| H5A | 1.3512 | 0.5095 | 0.8475 | 0.063* | |
| C2 | 1.4045 (3) | 0.2764 (4) | 1.0941 (4) | 0.0540 (10) | |
| H2 | 1.4195 | 0.2186 | 1.1552 | 0.065* | |
| C14 | 0.9626 (3) | 0.1087 (4) | 1.2162 (3) | 0.0480 (9) | |
| H14A | 1.0035 | 0.0572 | 1.2714 | 0.058* | |
| H14B | 0.9148 | 0.1495 | 1.2530 | 0.058* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0309 (4) | 0.0303 (4) | 0.0344 (4) | 0.0010 (3) | 0.0022 (3) | 0.0001 (3) |
| S1 | 0.0879 (9) | 0.0538 (7) | 0.0408 (5) | 0.0058 (5) | 0.0049 (5) | 0.0012 (4) |
| O4 | 0.0378 (12) | 0.0369 (14) | 0.0464 (13) | 0.0066 (10) | 0.0050 (10) | 0.0020 (11) |
| O2 | 0.0412 (13) | 0.0348 (14) | 0.0799 (19) | 0.0011 (11) | 0.0180 (13) | 0.0036 (13) |
| O5 | 0.0371 (12) | 0.0378 (14) | 0.0445 (14) | −0.0006 (10) | 0.0072 (10) | −0.0045 (10) |
| C4 | 0.056 (2) | 0.075 (3) | 0.058 (3) | 0.007 (2) | −0.001 (2) | −0.025 (2) |
| N2 | 0.0368 (14) | 0.0308 (15) | 0.0384 (14) | −0.0032 (11) | 0.0050 (11) | −0.0025 (12) |
| O6 | 0.090 (3) | 0.048 (2) | 0.072 (2) | −0.0219 (16) | −0.007 (2) | 0.0152 (16) |
| O3 | 0.0405 (14) | 0.0499 (18) | 0.089 (2) | 0.0076 (13) | 0.0143 (14) | 0.0197 (16) |
| O1 | 0.094 (3) | 0.0485 (19) | 0.069 (2) | 0.0017 (17) | 0.0040 (18) | −0.0165 (16) |
| N1 | 0.0388 (15) | 0.0467 (19) | 0.0439 (16) | 0.0064 (13) | 0.0056 (12) | 0.0039 (14) |
| C11 | 0.052 (2) | 0.039 (2) | 0.0442 (19) | −0.0072 (17) | 0.0051 (16) | −0.0020 (16) |
| C1 | 0.0381 (17) | 0.048 (2) | 0.046 (2) | 0.0000 (16) | 0.0090 (15) | −0.0006 (17) |
| C9 | 0.0375 (17) | 0.041 (2) | 0.052 (2) | 0.0019 (15) | 0.0066 (15) | −0.0002 (17) |
| C10 | 0.057 (2) | 0.043 (2) | 0.051 (2) | −0.0116 (18) | 0.0041 (18) | −0.0016 (18) |
| C6 | 0.0294 (15) | 0.050 (2) | 0.0422 (19) | 0.0057 (14) | 0.0044 (14) | −0.0037 (16) |
| C13 | 0.041 (2) | 0.049 (2) | 0.066 (2) | −0.0023 (17) | −0.0108 (18) | −0.012 (2) |
| C15 | 0.055 (2) | 0.040 (2) | 0.045 (2) | −0.0034 (17) | 0.0101 (17) | −0.0086 (17) |
| C8 | 0.0390 (18) | 0.051 (2) | 0.062 (2) | 0.0061 (17) | 0.0114 (17) | 0.011 (2) |
| C7 | 0.054 (2) | 0.047 (2) | 0.054 (2) | 0.0028 (18) | 0.0059 (18) | −0.003 (2) |
| C12 | 0.055 (2) | 0.048 (2) | 0.053 (2) | 0.0105 (18) | −0.0121 (19) | −0.0029 (19) |
| C3 | 0.052 (2) | 0.051 (3) | 0.086 (3) | 0.000 (2) | 0.014 (2) | −0.017 (2) |
| C5 | 0.046 (2) | 0.066 (3) | 0.043 (2) | 0.013 (2) | 0.0007 (17) | −0.009 (2) |
| C2 | 0.053 (2) | 0.044 (2) | 0.067 (3) | 0.0011 (18) | 0.014 (2) | 0.003 (2) |
| C14 | 0.056 (2) | 0.048 (2) | 0.0405 (19) | −0.0068 (18) | 0.0112 (16) | −0.0064 (17) |
Geometric parameters (Å, º)
| Co1—O4 | 2.097 (2) | C11—C10 | 1.505 (5) |
| Co1—O4i | 2.097 (2) | C11—H11A | 0.9700 |
| Co1—O5i | 2.101 (3) | C11—H11B | 0.9700 |
| Co1—O5 | 2.101 (3) | C1—C6 | 1.386 (5) |
| Co1—N2i | 2.151 (3) | C1—C2 | 1.398 (6) |
| Co1—N2 | 2.151 (3) | C9—C8 | 1.529 (5) |
| S1—C1 | 1.744 (4) | C10—H10A | 0.9700 |
| S1—C7 | 1.779 (5) | C10—H10B | 0.9700 |
| O4—C12 | 1.436 (5) | C6—C5 | 1.382 (5) |
| O4—H4 | 0.875 (9) | C13—C12 | 1.498 (6) |
| O2—C9 | 1.254 (4) | C13—H13A | 0.9700 |
| O5—C14 | 1.427 (4) | C13—H13B | 0.9700 |
| O5—H5 | 0.863 (9) | C15—C14 | 1.509 (5) |
| C4—C5 | 1.380 (7) | C15—H15A | 0.9700 |
| C4—C3 | 1.382 (7) | C15—H15B | 0.9700 |
| C4—H4A | 0.9300 | C8—H8A | 0.9700 |
| N2—C15 | 1.480 (4) | C8—H8B | 0.9700 |
| N2—C13 | 1.486 (5) | C12—H12A | 0.9700 |
| N2—C11 | 1.487 (5) | C12—H12B | 0.9700 |
| O6—C10 | 1.401 (5) | C3—C2 | 1.374 (6) |
| O6—H6 | 0.8200 | C3—H3 | 0.9300 |
| O3—C9 | 1.239 (5) | C5—H5A | 0.9300 |
| O1—C7 | 1.207 (5) | C2—H2 | 0.9300 |
| N1—C7 | 1.374 (5) | C14—H14A | 0.9700 |
| N1—C6 | 1.387 (5) | C14—H14B | 0.9700 |
| N1—C8 | 1.445 (5) | ||
| O4—Co1—O4i | 179.999 (1) | C11—C10—H10A | 110.6 |
| O4—Co1—O5i | 89.79 (10) | O6—C10—H10B | 110.6 |
| O4i—Co1—O5i | 90.21 (10) | C11—C10—H10B | 110.6 |
| O4—Co1—O5 | 90.21 (10) | H10A—C10—H10B | 108.7 |
| O4i—Co1—O5 | 89.79 (10) | C5—C6—C1 | 120.5 (4) |
| O5i—Co1—O5 | 180.00 (14) | C5—C6—N1 | 126.6 (4) |
| O4—Co1—N2i | 98.40 (10) | C1—C6—N1 | 112.9 (3) |
| O4i—Co1—N2i | 81.60 (10) | N2—C13—C12 | 112.9 (3) |
| O5i—Co1—N2i | 81.74 (10) | N2—C13—H13A | 109.0 |
| O5—Co1—N2i | 98.26 (10) | C12—C13—H13A | 109.0 |
| O4—Co1—N2 | 81.60 (10) | N2—C13—H13B | 109.0 |
| O4i—Co1—N2 | 98.40 (10) | C12—C13—H13B | 109.0 |
| O5i—Co1—N2 | 98.26 (10) | H13A—C13—H13B | 107.8 |
| O5—Co1—N2 | 81.74 (10) | N2—C15—C14 | 112.4 (3) |
| N2i—Co1—N2 | 180.0 | N2—C15—H15A | 109.1 |
| C1—S1—C7 | 91.15 (19) | C14—C15—H15A | 109.1 |
| C12—O4—Co1 | 113.2 (2) | N2—C15—H15B | 109.1 |
| C12—O4—H4 | 105.5 (16) | C14—C15—H15B | 109.1 |
| Co1—O4—H4 | 124.2 (16) | H15A—C15—H15B | 107.9 |
| C14—O5—Co1 | 112.2 (2) | N1—C8—C9 | 113.8 (3) |
| C14—O5—H5 | 105.9 (15) | N1—C8—H8A | 108.8 |
| Co1—O5—H5 | 130.5 (18) | C9—C8—H8A | 108.8 |
| C5—C4—C3 | 122.3 (4) | N1—C8—H8B | 108.8 |
| C5—C4—H4A | 118.8 | C9—C8—H8B | 108.8 |
| C3—C4—H4A | 118.8 | H8A—C8—H8B | 107.7 |
| C15—N2—C13 | 114.6 (3) | O1—C7—N1 | 125.6 (4) |
| C15—N2—C11 | 109.8 (3) | O1—C7—S1 | 125.2 (3) |
| C13—N2—C11 | 110.5 (3) | N1—C7—S1 | 109.2 (3) |
| C15—N2—Co1 | 107.4 (2) | O4—C12—C13 | 110.6 (3) |
| C13—N2—Co1 | 106.3 (2) | O4—C12—H12A | 109.5 |
| C11—N2—Co1 | 108.0 (2) | C13—C12—H12A | 109.5 |
| C10—O6—H6 | 109.5 | O4—C12—H12B | 109.5 |
| C7—N1—C6 | 115.3 (3) | C13—C12—H12B | 109.5 |
| C7—N1—C8 | 118.2 (3) | H12A—C12—H12B | 108.1 |
| C6—N1—C8 | 126.1 (3) | C2—C3—C4 | 120.1 (5) |
| N2—C11—C10 | 117.2 (3) | C2—C3—H3 | 120.0 |
| N2—C11—H11A | 108.0 | C4—C3—H3 | 120.0 |
| C10—C11—H11A | 108.0 | C4—C5—C6 | 117.7 (4) |
| N2—C11—H11B | 108.0 | C4—C5—H5A | 121.1 |
| C10—C11—H11B | 108.0 | C6—C5—H5A | 121.1 |
| H11A—C11—H11B | 107.2 | C3—C2—C1 | 118.2 (4) |
| C6—C1—C2 | 121.1 (4) | C3—C2—H2 | 120.9 |
| C6—C1—S1 | 111.2 (3) | C1—C2—H2 | 120.9 |
| C2—C1—S1 | 127.6 (3) | O5—C14—C15 | 111.2 (3) |
| O3—C9—O2 | 125.8 (3) | O5—C14—H14A | 109.4 |
| O3—C9—C8 | 116.4 (3) | C15—C14—H14A | 109.4 |
| O2—C9—C8 | 117.8 (3) | O5—C14—H14B | 109.4 |
| O6—C10—C11 | 105.9 (3) | C15—C14—H14B | 109.4 |
| O6—C10—H10A | 110.6 | H14A—C14—H14B | 108.0 |
| O4i—Co1—O4—C12 | −139 (11) | C2—C1—C6—N1 | 179.6 (3) |
| O5i—Co1—O4—C12 | 103.4 (3) | S1—C1—C6—N1 | 1.1 (4) |
| O5—Co1—O4—C12 | −76.6 (3) | C7—N1—C6—C5 | 175.5 (4) |
| N2i—Co1—O4—C12 | −175.0 (3) | C8—N1—C6—C5 | 2.5 (6) |
| N2—Co1—O4—C12 | 5.0 (3) | C7—N1—C6—C1 | −4.1 (5) |
| O4—Co1—O5—C14 | 72.2 (2) | C8—N1—C6—C1 | −177.1 (3) |
| O4i—Co1—O5—C14 | −107.8 (2) | C15—N2—C13—C12 | 80.4 (4) |
| O5i—Co1—O5—C14 | −141.4 (8) | C11—N2—C13—C12 | −154.9 (3) |
| N2i—Co1—O5—C14 | 170.7 (2) | Co1—N2—C13—C12 | −38.0 (4) |
| N2—Co1—O5—C14 | −9.3 (2) | C13—N2—C15—C14 | −83.1 (4) |
| O4—Co1—N2—C15 | −105.4 (2) | C11—N2—C15—C14 | 151.8 (3) |
| O4i—Co1—N2—C15 | 74.6 (2) | Co1—N2—C15—C14 | 34.7 (4) |
| O5i—Co1—N2—C15 | 166.0 (2) | C7—N1—C8—C9 | −77.0 (5) |
| O5—Co1—N2—C15 | −14.0 (2) | C6—N1—C8—C9 | 95.8 (4) |
| N2i—Co1—N2—C15 | −5 (14) | O3—C9—C8—N1 | 169.0 (4) |
| O4—Co1—N2—C13 | 17.6 (2) | O2—C9—C8—N1 | −10.3 (5) |
| O4i—Co1—N2—C13 | −162.4 (2) | C6—N1—C7—O1 | −176.0 (4) |
| O5i—Co1—N2—C13 | −70.9 (3) | C8—N1—C7—O1 | −2.4 (6) |
| O5—Co1—N2—C13 | 109.1 (3) | C6—N1—C7—S1 | 4.9 (4) |
| N2i—Co1—N2—C13 | 118 (14) | C8—N1—C7—S1 | 178.5 (3) |
| O4—Co1—N2—C11 | 136.3 (2) | C1—S1—C7—O1 | 177.4 (4) |
| O4i—Co1—N2—C11 | −43.7 (2) | C1—S1—C7—N1 | −3.5 (3) |
| O5i—Co1—N2—C11 | 47.7 (2) | Co1—O4—C12—C13 | −26.9 (4) |
| O5—Co1—N2—C11 | −132.3 (2) | N2—C13—C12—O4 | 44.2 (5) |
| N2i—Co1—N2—C11 | −123 (13) | C5—C4—C3—C2 | −0.9 (7) |
| C15—N2—C11—C10 | 64.6 (4) | C3—C4—C5—C6 | −0.7 (7) |
| C13—N2—C11—C10 | −62.7 (4) | C1—C6—C5—C4 | 1.1 (6) |
| Co1—N2—C11—C10 | −178.6 (3) | N1—C6—C5—C4 | −178.4 (4) |
| C7—S1—C1—C6 | 1.4 (3) | C4—C3—C2—C1 | 2.0 (6) |
| C7—S1—C1—C2 | −177.0 (4) | C6—C1—C2—C3 | −1.6 (6) |
| N2—C11—C10—O6 | −172.3 (4) | S1—C1—C2—C3 | 176.6 (3) |
| C2—C1—C6—C5 | 0.1 (6) | Co1—O5—C14—C15 | 30.8 (4) |
| S1—C1—C6—C5 | −178.4 (3) | N2—C15—C14—O5 | −44.5 (4) |
Symmetry code: (i) −x+2, −y, −z+2.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O2ii | 0.88 (3) | 1.71 (3) | 2.572 (4) | 166 (3) |
| O5—H5···O3iii | 0.86 (1) | 1.75 (2) | 2.577 (4) | 159 (3) |
| O6—H6···O2 | 0.82 | 1.88 | 2.697 (4) | 173 |
| C8—H8A···O1iv | 0.97 | 2.48 | 3.432 (6) | 167 |
| C12—H12B···O6v | 0.97 | 2.53 | 3.455 (6) | 159 |
Symmetry codes: (ii) x, y−1, z; (iii) −x+2, −y+1, −z+2; (iv) x, −y+3/2, z−1/2; (v) x, −y+1/2, z+1/2.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016002930/pj2027sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016002930/pj2027Isup2.hkl
CCDC reference: 1454443
Additional supporting information: crystallographic information; 3D view; checkCIF report