Crystal structure of the salt bis­(tri­ethano­lamine-κ3N,O,O′)cobalt(II) bis­[2-(2-oxo-2,3-di­hydro-1,3-benzo­thia­zol-3-yl)acetate]

Ashurov, J.M.; Obidova, N.J.; Abdireymov, H.B.; Ibragimov, B.T.

doi:10.1107/S2056989016002930

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ISSN: 2056-9890

Volume 72| Part 3| March 2016| Pages 420-423

doi:10.1107/S2056989016002930

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Crystal structure of the salt bis(triethanolamine-κ³N,O,O′)cobalt(II) bis[2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate]

Jamshid M. Ashurov,^a ^* Nodira J. Obidova,^a Hudaybergen B. Abdireymov ^b and Bakhtiyar T. Ibragimov ^a

^aInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek Str. 83, Tashkent 700125, Uzbekistan, and ^bKarakalpak State University, Nukus str. Abdirova 1, Karakalpakstan 742012, Uzbekistan
^*Correspondence e-mail: atom.uz@mail.ru

Edited by T. J. Prior, University of Hull, England (Received 7 February 2016; accepted 18 February 2016; online 24 February 2016)

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 Co^II ion situated on an inversion centre. In the complex cation, the Co^II 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 Co^II 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.

Keywords: crystal structure; triethanolamine; α-(N-benzothiazolin-2-one) acetic acid; hydrogen bonding.

CCDC reference: 1454443

1. 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).

2. 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 Co^II 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 Co^II 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)°.

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⋯O6^iv	0.97	2.53	3.455 (6)	159
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+1, -z+2; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of (I), showing the atom-labelling scheme. Unlabelled atoms are generated by the inversion centre.

3. 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 R₄⁴(22) and C₄⁴(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.

4. 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.

5. 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.

6. 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 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ )
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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.53
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97, SHELXL97 XP and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1454443

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016002930/pj2027sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016002930/pj2027Isup2.hkl

checkCIF report

Chemical context top

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; Yesilel 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 et al., 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.

Structural commentary top

The molecular structure of compound (I) is shown in Fig. 1. The structure consists of a complex cation and two 2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate anions. The asymmetric unit contains a half of the cationic moiety because the Co^II 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 Co^II ion is coordinated by four oxygen and two nitrogen atoms of the ligand. 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 thiazolin 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 0.0187 (su?) and 0.0279 (su?) Å, respectively. The dihedral angle between the plane of the carboxylate group and the benzothiazole ring system is 85.61 (su?)°.

Supramolecular features top

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 R⁴₄(22) and C⁴₄(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 (su?) Å;] of adjacent inversion-related molecules (Fig. 3).

Database survey top

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 top

Refinement details top

Structure description top

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; Yesilel 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 et al., 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.

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 top

Refinement details top

Computing details top

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Unlabelled atoms are generated by the inversion centre.
	Fig. 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.
	Fig. 3. The crystal structure packing of (I). Hydrogen bonds are indicated by black dashed lines and π–π stacking interactions by red dashed lines.

Bis(triethanolamine-κ³N,O,O')cobalt(II) bis[2-(2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate] top

Crystal data top

[Co(C₆H₁₅NO₃)₂](C₉H₆NO₃S)₂	F(000) = 810
M_r = 773.73	D_x = 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 top

Oxford Diffraction Xcalibur Ruby diffractometer	3487 independent reflections
Radiation source: fine-focus sealed tube	2693 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 10.2576 pixels mm^-1	θ_max = 75.8°, θ_min = 5.5°
ω scans	h = −18→17
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Oxford Diffraction, 2009)	k = −10→12
T_min = 0.280, T_max = 0.797	l = −12→15
7096 measured reflections

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)] = 0.061	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(F_o²) + (0.0899P)² + 0.4878P] where P = (F_o² + 2F_c²)/3
3487 reflections	(Δ/σ)_max < 0.001
230 parameters	Δρ_max = 0.47 e Å⁻³
6 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Co(C₆H₁₅NO₃)₂](C₉H₆NO₃S)₂	V = 1710.94 (11) Å³
M_r = 773.73	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 14.6953 (6) Å	µ = 5.66 mm⁻¹
b = 9.7043 (3) Å	T = 293 K
c = 12.1311 (4) Å	0.28 × 0.24 × 0.18 mm
β = 98.513 (4)°

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	3487 independent reflections
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Oxford Diffraction, 2009)	2693 reflections with I > 2σ(I)
T_min = 0.280, T_max = 0.797	R_int = 0.048
7096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	6 restraints
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.47 e Å⁻³
3487 reflections	Δρ_min = −0.53 e Å⁻³
230 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	U_iso*/U_eq
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) top

	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) top

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) top

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···O1^iv	0.97	2.48	3.432 (6)	167
C12—H12B···O6^v	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.

Hydrogen-bond geometry (Å, º) top

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	0.864 (12)	1.752 (17)	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···O6^iv	0.97	2.53	3.455 (6)	159

Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+1/2, z+1/2.

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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.53

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

Acknowledgements

This work was supported by a Grant for Fundamental Research from the Center of Science and Technology, Uzbekistan (No. FPFI T.3-14).

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