Crystal structure of the salt bis-(tri-ethano-lamine-κ(3) N,O,O')cobalt(II) bis-[2-(2-oxo-2,3-di-hydro-1,3-benzo-thia-zol-3-yl)acetate].

The reaction of 2-(2-oxo-2,3-di-hydro-1,3-benzo-thia-zol-3-yl)acetic acid (NBTA) and tri-ethano-lamine (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-(tri-ethano-lamine)-cobalt(II) and 2-(2-oxo-2,3-di-hydro-1,3-benzo-thia-zol-3-yl)acetate units. It crystallizes in the monoclinic centrosymmetric space group P21/c, with the Co(II) ion situated on an inversion centre. In the complex cation, the Co(II) ion is octa-hedrally coordinated by two N,O,O'-tridentate TEA mol-ecules with a facial distribution and the N atoms in a trans arrangement. Two ethanol groups of each TEA mol-ecule form two five-membered chelate rings around the Co(II) ion, while the third ethanol group does not coordinate to the metal. The free and coordinating hy-droxy groups of the TEA mol-ecules 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, n class="Chemical">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 n class="Chemical">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 [n class="Chemical">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 class="Chemical">N.

Synthesis and crystallization

To an aqueous solution (2.5 ml) of Co(NO3)2 (0.091 g, 0.5 mmol) was added slowly an n class="Chemical">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

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009 ▸), SHELXS97, SHELXL97 XP and SHELXTL (Sheldrick, 2008 ▸).

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

[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

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 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

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.

	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*

	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)

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)

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