Poly[bis(μ-4-amino­benzene­sulfonato-κ2N:O)di­aquacobalt(II)]

Kama, A.B.; Sidibe, M.; Diop, C.A.K.; Blanchard, F.

doi:10.1107/S241431461801204X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 8| August 2018| x181204

https://doi.org/10.1107/S241431461801204X

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Poly[bis(μ-4-aminobenzenesulfonato-κ²N:O)diaquacobalt(II)]

Antoine Blaise Kama,^a ^* Mamadou Sidibe,^a Cheikh Abdoul Khadre Diop ^a and Florent Blanchard ^b

^aLaboratoire de Chimie Minérale et Analytique (LACHIMIA), Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^bService de Cristallochimie – ICSN, Bat. 27, Avenue de la Terrasse, 91198 Gif sur Yvette Cedex, France
^*Correspondence e-mail: kama.antoineblaise@yahoo.fr

Edited by T. J. Prior, University of Hull, England (Received 31 July 2018; accepted 24 August 2018; online 31 August 2018)

The title compound, [Co(C₆H₆NO₃S)₂(H₂O)₂]_n, was obtained from a mixture of Co(NO₃)₂·6H₂O and a previously synthesized salt, namely CyNH₃·NH₂PhSO₃, in a 1:1 ratio (Cy = cyclohexyl; Ph = phenyl). The crystal structure consists of a three-dimensional supramolecular framework, in which polymeric layers are interconnected via N—H⋯O and O—H⋯O hydrogen bonding. The polymeric layers are formed by an interconnection of neighbouring cobalt(II) cations via NH₂PhSO₃⁻ bridges. Each cobalt(II) cation is surrounded by four NH₂PhSO₃⁻ moieties and two water molecules, leading to a distorted octahedral environment.

Keywords: crystal structure; cobalt sufanilate; polymeric layers; hydrogen bonds; three-dimensional framework.

CCDC reference: 1863810

Structure description

Mononuclear or polynuclear cobalt complexes formed by electron-donating groups have been widely studied (Liu et al., 2017 ; Leung et al., 2012 ; McCool et al., 2011 ; Nakazono et al., 2013 ; Pizzolato et al., 2013 ; Wang et al., 2014 ; Xu et al., 2017 ) owing to their capacities for water oxidation. Indeed, it has been frequently observed that ligand dissociation of cobalt complexes occurs, generating CoO_x nanoparticles that act as water oxidation catalysts (Wasylenko et al., 2011 ; Hong et al., 2012 ). For the design of new cobalt complexes, we target the synthesis of a new material from Co(NO₃)₂·6H₂O and a previously synthesized ligand. In this case, CyNH₃·NH₂PhSO₃ (Cy = cyclohexyl; Ph = phenyl) yielded the title compound [Co(NH₂PhSO₃)₂(H₂O)₂]_n via the elimination of the NO₃⁻ group and the substitution of four water molecules by NH₂PhSO₃⁻. If we consider the reagents and the resulting material, a notable fact is the elimination of some water molecules and the nitrate, probably in the form of CyNH₃·NO₃, leading to the substitution complex [Co(NH₂PhSO₃)₂(H₂O)₂]_n. The crystal structure is reported herein. A similar tetrahydrate cobalt complex has been previously reported (Shakeri & Haussühl, 1992 ).

The asymmetric unit comprises of a cobalt(II) cation (situated at an inversion centre), one NH₂PhSO₃⁻ anion and one water molecule (Fig. 1). The trans coordination of the ligands around the Co^II ion leads to a distorted octahedral coordination sphere with O—Co—N and O—Co—O angles in the range 88.42 (5)–91.58 (5)°. The Co—N [2.2424 (14) Å] and Co—O [in the range 2.0800 (12)–2.1049 (10) Å] bond length are similar to those found in the literature (Co—N = 2.256 and Co—O = 2.118 Å; Li et al., 2007 ]. The three S—O bond lengths are different [S1—O2 = 1.4652 (12), S1—O3 = 1.4512 (13) and S1—O4 = 1.4463 (15) Å] because O2 is involved in covalent bonding while O3 and O4 are involved in hydrogen bonding (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—HO1A⋯O4ⁱ	0.84 (3)	1.85 (3)	2.660 (2)	161 (3)
O1—HO1B⋯O3ⁱⁱ	0.80 (3)	1.97 (3)	2.7647 (18)	176 (3)
N1—HN1A⋯O3ⁱⁱⁱ	0.85 (2)	2.21 (2)	3.008 (2)	156 (2)
N1—HN1B⋯O1^iv	0.84 (2)	2.48 (2)	3.309 (2)	171 (2)
C3—H3⋯O3ⁱⁱⁱ	0.93	2.59	3.2123 (19)	124
C5—H5⋯O2^v	0.93	2.60	3.501 (2)	163
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at 50% probability level.

Figure 2
Hydrogen bonds (shown as light-blue dashed lines) between water molecules and SO₃⁻ groups in the title compound.

In the crystal structure, the cobalt(II) cation is surrounded by four NH₂PhSO₃⁻ moieties. Each NH₂PhSO₃⁻ unit is a bridge connecting two neighboring cobalt(II) cations through the NH₂ groups on the one hand and the SO₃⁻ group on the other, leading to polymeric layers (Fig. 3). The layers are connected via N—H⋯O (sulfanilate–sulfanilate interaction through SO₃⁻ and NH₂ groups) and O—H⋯O (sulfanilate–water interaction) hydrogen bonding. The resulting structure can be described as a three-dimensional supramolecular framework built from layers (Fig. 4).

Figure 3
Polymeric layers formed by interconection of neighbouring cobalt(II) cations.

Figure 4
Three-dimensional supramolecular framework built from polymeric layers connected via hydrogen bonds.

Synthesis and crystallization

The title compound was obtained by mixing cyclohexylammonium sulfanilate (0.78 g, 3 mmol) and cobalt nitrate hexahydrate, Co(NO₃)₂·6H₂O (0.6 g, 3 mmol) in ethanol as solvent. The solution was stirred for about two h and filtered. Slow evaporation of the filtrate at room temperature afforded red crystals suitable for single-crystal X-ray diffraction analysis.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₆H₆NO₃S)₂(H₂O)₂]
M_r	439.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.0768 (3), 5.9601 (3), 18.6738 (8)
β (°)	100.494 (4)
V (Å³)	774.46 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.43
Crystal size (mm)	0.7 × 0.5 × 0.1

Data collection
Diffractometer	Rigaku Pilatus 200K
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.837, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7932, 1931, 1780
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.065, 1.07
No. of reflections	1931
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.48
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1863810

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461801204X/pj4007sup1.cif

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[bis(µ-4-aminobenzenesulfonato-κ²N:O)diaquacobalt(II)] top

Crystal data top

[Co(C₆H₆NO₃S)₂(H₂O)₂]	F(000) = 450
M_r = 439.32	D_x = 1.884 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0768 (3) Å	Cell parameters from 5404 reflections
b = 5.9601 (3) Å	θ = 4.5–29.6°
c = 18.6738 (8) Å	µ = 1.43 mm⁻¹
β = 100.494 (4)°	T = 293 K
V = 774.46 (6) Å³	Block, red
Z = 2	0.7 × 0.5 × 0.1 mm

Data collection top

Rigaku Pilatus 200K diffractometer	1780 reflections with I > 2σ(I)
Detector resolution: 5.8140 pixels mm^-1	R_int = 0.024
profile data from ω–scans	θ_max = 29.7°, θ_min = 4.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −9→8
T_min = 0.837, T_max = 1.000	k = −8→7
7932 measured reflections	l = −25→22
1931 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0326P)² + 0.403P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1931 reflections	Δρ_max = 0.30 e Å⁻³
131 parameters	Δρ_min = −0.47 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	1.000000	0.500000	0.500000	0.01583 (9)
S1	0.61895 (5)	0.27748 (7)	0.39481 (2)	0.01899 (10)
O1	0.81064 (18)	0.7558 (2)	0.51451 (7)	0.0250 (3)
HO1A	0.761 (3)	0.833 (5)	0.4782 (14)	0.052 (7)*
HO1B	0.727 (4)	0.711 (5)	0.5342 (16)	0.062 (9)*
O2	0.81062 (15)	0.3792 (2)	0.40793 (6)	0.0285 (3)
O3	0.48036 (17)	0.4192 (3)	0.42166 (6)	0.0349 (3)
N1	0.3584 (2)	0.2190 (3)	0.07238 (7)	0.0201 (3)
HN1A	0.245 (3)	0.166 (4)	0.0662 (12)	0.036 (6)*
HN1B	0.359 (3)	0.351 (4)	0.0570 (12)	0.034 (6)*
O4	0.6175 (2)	0.0504 (3)	0.42203 (7)	0.0429 (4)
C1	0.5497 (2)	0.2593 (2)	0.29930 (7)	0.0167 (3)
C2	0.4574 (2)	0.0664 (3)	0.26903 (8)	0.0204 (3)
H2	0.436669	−0.052910	0.298746	0.024*
C3	0.3963 (2)	0.0531 (3)	0.19415 (8)	0.0212 (3)
H3	0.336171	−0.076396	0.173539	0.025*
C5	0.5176 (2)	0.4255 (3)	0.18059 (8)	0.0205 (3)
C4	0.4249 (2)	0.2329 (2)	0.14997 (7)	0.0169 (3)
H5	0.537318	0.545480	0.150979	0.025*
C6	0.5808 (2)	0.4383 (3)	0.25555 (8)	0.0205 (3)
H6	0.643504	0.566272	0.276156	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01436 (15)	0.02289 (16)	0.00953 (14)	0.00224 (10)	0.00027 (10)	−0.00099 (9)
S1	0.01725 (19)	0.0298 (2)	0.00910 (16)	0.00209 (13)	0.00034 (12)	0.00003 (13)
O1	0.0220 (6)	0.0298 (6)	0.0232 (6)	0.0067 (5)	0.0040 (5)	0.0020 (5)
O2	0.0173 (5)	0.0521 (8)	0.0147 (5)	−0.0029 (5)	−0.0010 (4)	−0.0078 (5)
O3	0.0242 (6)	0.0608 (9)	0.0204 (6)	0.0104 (6)	0.0062 (5)	−0.0093 (6)
N1	0.0209 (7)	0.0273 (7)	0.0110 (6)	−0.0005 (5)	−0.0001 (5)	−0.0003 (5)
O4	0.0648 (10)	0.0370 (7)	0.0220 (6)	−0.0013 (7)	−0.0051 (6)	0.0121 (5)
C4	0.0161 (7)	0.0243 (7)	0.0104 (6)	0.0012 (5)	0.0023 (5)	−0.0012 (5)
C1	0.0146 (6)	0.0245 (7)	0.0106 (6)	0.0009 (5)	0.0010 (5)	−0.0005 (5)
C6	0.0224 (7)	0.0213 (7)	0.0168 (7)	−0.0048 (6)	0.0012 (5)	−0.0023 (6)
C2	0.0226 (7)	0.0233 (7)	0.0151 (6)	−0.0039 (6)	0.0031 (5)	0.0028 (6)
C5	0.0238 (7)	0.0224 (7)	0.0151 (6)	−0.0035 (6)	0.0035 (5)	0.0026 (6)
C3	0.0226 (7)	0.0231 (7)	0.0165 (7)	−0.0060 (6)	−0.0002 (5)	−0.0021 (6)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.0800 (12)	N1—C4	1.4420 (17)
Co1—O1	2.0800 (12)	N1—HN1A	0.85 (2)
Co1—O2ⁱ	2.1048 (10)	N1—HN1B	0.84 (2)
Co1—O2	2.1049 (10)	C4—C5	1.392 (2)
Co1—N1ⁱⁱ	2.2424 (14)	C4—C3	1.390 (2)
Co1—N1ⁱⁱⁱ	2.2424 (14)	C1—C6	1.385 (2)
S1—O2	1.4652 (12)	C1—C2	1.391 (2)
S1—O3	1.4512 (13)	C6—H6	0.9300
S1—O4	1.4463 (15)	C6—C5	1.392 (2)
S1—C1	1.7648 (14)	C2—H2	0.9300
O1—HO1A	0.84 (3)	C2—C3	1.389 (2)
O1—HO1B	0.80 (3)	C5—H5	0.9300
N1—Co1^iv	2.2424 (13)	C3—H3	0.9300

O1ⁱ—Co1—O1	180.0	Co1^iv—N1—HN1A	102.4 (15)
O1ⁱ—Co1—O2	88.42 (5)	Co1^iv—N1—HN1B	108.0 (15)
O1ⁱ—Co1—O2ⁱ	91.58 (5)	C4—N1—Co1^iv	122.62 (10)
O1—Co1—O2	91.58 (5)	C4—N1—HN1A	106.6 (15)
O1—Co1—O2ⁱ	88.42 (5)	C4—N1—HN1B	105.6 (15)
O1ⁱ—Co1—N1ⁱⁱ	91.20 (6)	HN1A—N1—HN1B	111 (2)
O1ⁱ—Co1—N1ⁱⁱⁱ	88.80 (6)	C5—C4—N1	120.19 (13)
O1—Co1—N1ⁱⁱ	88.80 (6)	C3—C4—N1	119.75 (13)
O1—Co1—N1ⁱⁱⁱ	91.20 (6)	C3—C4—C5	120.05 (13)
O2ⁱ—Co1—O2	180.0	C6—C1—S1	120.28 (11)
O2—Co1—N1ⁱⁱⁱ	89.70 (5)	C6—C1—C2	120.67 (13)
O2—Co1—N1ⁱⁱ	90.30 (5)	C2—C1—S1	119.01 (11)
O2ⁱ—Co1—N1ⁱⁱ	89.70 (5)	C1—C6—H6	120.2
O2ⁱ—Co1—N1ⁱⁱⁱ	90.30 (5)	C1—C6—C5	119.64 (14)
N1ⁱⁱ—Co1—N1ⁱⁱⁱ	180.0	C5—C6—H6	120.2
O2—S1—C1	105.81 (7)	C1—C2—H2	120.2
O3—S1—O2	111.38 (8)	C3—C2—C1	119.59 (14)
O3—S1—C1	107.71 (7)	C3—C2—H2	120.2
O4—S1—O2	113.22 (9)	C4—C5—H5	120.0
O4—S1—O3	112.01 (10)	C6—C5—C4	119.95 (14)
O4—S1—C1	106.22 (8)	C6—C5—H5	120.0
Co1—O1—HO1A	118.7 (17)	C4—C3—H3	120.0
Co1—O1—HO1B	111 (2)	C2—C3—C4	120.09 (14)
HO1A—O1—HO1B	108 (2)	C2—C3—H3	120.0
S1—O2—Co1	135.27 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1A···O4^v	0.84 (3)	1.85 (3)	2.660 (2)	161 (3)
O1—HO1B···O3^vi	0.80 (3)	1.97 (3)	2.7647 (18)	176 (3)
N1—HN1A···O3^vii	0.85 (2)	2.21 (2)	3.008 (2)	156 (2)
N1—HN1B···O1^viii	0.84 (2)	2.48 (2)	3.309 (2)	171 (2)
C3—H3···O3^vii	0.93	2.59	3.2123 (19)	124
C5—H5···O2ⁱⁱⁱ	0.93	2.60	3.501 (2)	163

Symmetry codes: (iii) −x+3/2, y+1/2, −z+1/2; (v) x, y+1, z; (vi) −x+1, −y+1, −z+1; (vii) −x+1/2, y−1/2, −z+1/2; (viii) x−1/2, −y+3/2, z−1/2.

Acknowledgements

The authors thank the ICSN cristallochimie service (France) for instrumentation use.

Funding information

The authors acknowledge the Cheikh Anta Diop University of Dakar (Senegal) for financial support.

References

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