Bis[2-(2-pyridylmethyl­eneamino)benzene­sulfonato-κ3N,N′,O]cobalt(II) dihydrate

Huang, X.-R.; Ou-Yang, M.; Yang, G.-G.; Meng, X.-J.; Jiang, Y.-M.

doi:10.1107/S1600536809043918

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1465

https://doi.org/10.1107/S1600536809043918

Open

access

Bis[2-(2-pyridylmethyleneamino)benzenesulfonato-κ³N,N′,O]cobalt(II) dihydrate

Xue-Ren Huang,^a Miao Ou-Yang,^a Ge-Ge Yang,^a Xiu-Jin Meng ^a and Yi-Min Jiang ^a,^b ^*

^aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, People's Republic of China, and ^bKey Laboratory of New Processing Technology for Nonferrous Metals & Materials, Ministry of Education, Guilin University of Technology, Guilin 541004, People's Republic of China
^*Correspondence e-mail: 499122835@qq.com

(Received 15 October 2009; accepted 23 October 2009; online 31 October 2009)

The title complex, [Co(C₁₂H₉N₂O₃S)₂]·2H₂O, has site symmetry 2 with the Co^II cation located on a twofold rotation axis. Two tridentate 2-(2-pyridylmethyleneamino)benzenesulfonate (paba) ligands chelate to the Co^II cation in a distorted octahedral geometry. The pyridine and benzene rings in the paba ligand are oriented at a dihedral angle of 42.86 (13)°. Intermolecular O—H⋯O and C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For general background to the coordination chemistry of the sulfonate ligands, see: Jiang et al. (2006 ). For the isostructural Zn and Cd complexes, see: Cai et al. (2008 ); Ou-Yang et al. (2008 ). For the synthesis, see: Casella & Gullotti (1986 ).

Experimental

Crystal data

[Co(C₁₂H₉N₂O₃S)₂]·2H₂O
M_r = 617.53
Orthorhombic, P b c n
a = 19.636 (2) Å
b = 8.0973 (8) Å
c = 16.2819 (16) Å
V = 2588.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 291 K
0.31 × 0.25 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.771, T_max = 0.939
17970 measured reflections
2410 independent reflections
1960 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.02
2410 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O3	2.1029 (16)
Co1—N1	2.1863 (18)
Co1—N2	2.147 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O4ⁱ	0.85	2.16	3.009 (3)	179
O1—H2W⋯O2	0.84	2.15	2.867 (3)	143
C7—H7⋯O1ⁱⁱ	0.93	2.56	3.425 (3)	154
C11—H11⋯O4ⁱⁱⁱ	0.93	2.46	3.389 (3)	172
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+2, y-1, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809043918/xu2642sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043918/xu2642Isup2.hkl

checkCIF report

Comment top

The design of supermolecular coordination complexes in which both coordination bonds and hydrogen bonds take part in the self-assembly chemistry have recently generated increasing interest. Our group have focused on the exploration of the coordination chemistry of the sulfonate ligands (Jiang et al.., 2006). We report here the structure of the title complex (Fig. 1).

The Co^II complex is isostructural with [Zn(Paba)₂].2H₂O and [Cd(Paba)₂].2H₂O whose structure has been described in detail (Cai et al.., 2008; Ou-Yang et al.., 2008). The Co(II) atom lies on the twofold rotation axis and is coordinated by pyridine N, imine N and sulfonate O atoms from two paba^- ligands with a distorted octahedral geometry (Table 1). This structure is similar to complexes with N,N',O-tridentate donor ligands (Casella et al.., 1986). The O—H···O and C—H···O hydrogen bonding (Table 2) is present in the crystal structure.

Related literature top

For general background to the coordination chemistry of the sulfonate ligands, see: Jiang, et al. (2006). For the isostructural Zn and Cd complexes, see: Cai et al. (2008); Ou-Yang et al. (2008). For the synthesis, see: Casella & Gullotti (1986).

Experimental top

The potassium salt of 2-(pyridylmethyl)imine-2-benzenesulfonic acid (pabaK) was synthesized according to the literature method (Casella & Gullotti, 1986). To prepare the title complex, pabaK (1 mmol, 0.30 g) was dissolved in methanol (10 ml) at 333 k and an aqueous solution (10 ml) containing Co(AcO)₂.4H₂O (0.5 mmol, 0.125 g) was added. The mixture was stirred at 333 K for 4 h, then cooled to room temperature and filtered. Red crystals suitable for X-ray diffraction were obtained by slowly evaporation over several days, with a yield of 60%. Elemental analysis, found (%): C: 46.59; H: 4.04; N: 9.11; S: 10.25, calc (%): C: 46.64; H: 3.56; N: 9.07; S: 10.36.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the complex, showing the atom-numbering scheme. Symmetry code: -x + 2, y, -z + 1/2.

Bis[2-(2-pyridylmethyleneamino)benzenesulfonato- κ³N,N',O]cobalt(II) dihydrate top

Crystal data top

[Co(C₁₂H₉N₂O₃S)₂]·2H₂O	F(000) = 1268
M_r = 617.53	D_x = 1.584 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4317 reflections
a = 19.636 (2) Å	θ = 2.5–24.7°
b = 8.0973 (8) Å	µ = 0.88 mm⁻¹
c = 16.2819 (16) Å	T = 291 K
V = 2588.8 (4) Å³	Block, red
Z = 4	0.31 × 0.25 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2410 independent reflections
Radiation source: fine-focus sealed tube	1960 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→23
T_min = 0.771, T_max = 0.939	k = −9→9
17970 measured reflections	l = −19→19

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0467P)² + 1.5384P] where P = (F_o² + 2F_c²)/3
2410 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Co(C₁₂H₉N₂O₃S)₂]·2H₂O	V = 2588.8 (4) Å³
M_r = 617.53	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 19.636 (2) Å	µ = 0.88 mm⁻¹
b = 8.0973 (8) Å	T = 291 K
c = 16.2819 (16) Å	0.31 × 0.25 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2410 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1960 reflections with I > 2σ(I)
T_min = 0.771, T_max = 0.939	R_int = 0.039
17970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.02	Δρ_max = 0.44 e Å⁻³
2410 reflections	Δρ_min = −0.46 e Å⁻³
177 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	0.68407 (5)	0.2500	0.02746 (14)
S1	0.87615 (3)	0.82456 (8)	0.34750 (3)	0.03191 (17)
O1	0.79780 (13)	0.4090 (4)	0.44814 (16)	0.1166 (13)
H1W	0.7550	0.4121	0.4400	0.175*
H2W	0.8188	0.4425	0.4064	0.175*
O2	0.84711 (9)	0.6617 (2)	0.34011 (11)	0.0477 (5)
O3	0.95125 (8)	0.8220 (2)	0.34231 (9)	0.0350 (4)
O4	0.85336 (9)	0.9170 (2)	0.41814 (10)	0.0438 (4)
N1	0.90902 (9)	0.7307 (2)	0.17616 (11)	0.0297 (4)
N2	0.99827 (10)	0.4858 (3)	0.16249 (12)	0.0335 (5)
C1	0.85084 (11)	0.9367 (3)	0.25933 (13)	0.0310 (5)
C2	0.81355 (13)	1.0800 (3)	0.26678 (15)	0.0413 (6)
H2	0.8016	1.1189	0.3186	0.050*
C3	0.79387 (15)	1.1660 (4)	0.19754 (18)	0.0534 (8)
H3	0.7691	1.2634	0.2027	0.064*
C4	0.81090 (14)	1.1074 (4)	0.12064 (16)	0.0538 (8)
H4	0.7974	1.1653	0.0741	0.065*
C5	0.84796 (13)	0.9631 (4)	0.11249 (15)	0.0444 (7)
H5	0.8593	0.9246	0.0604	0.053*
C6	0.86829 (11)	0.8756 (3)	0.18134 (14)	0.0309 (5)
C7	0.89905 (12)	0.6270 (3)	0.11848 (14)	0.0362 (6)
H7	0.8624	0.6399	0.0828	0.043*
C8	0.94554 (12)	0.4883 (3)	0.10895 (13)	0.0330 (5)
C9	0.93760 (15)	0.3705 (3)	0.04869 (16)	0.0469 (7)
H9	0.9008	0.3749	0.0128	0.056*
C10	0.98533 (16)	0.2455 (4)	0.04253 (18)	0.0534 (7)
H10	0.9808	0.1639	0.0027	0.064*
C11	1.03915 (16)	0.2432 (3)	0.09565 (18)	0.0503 (7)
H11	1.0722	0.1612	0.0919	0.060*
C12	1.04376 (14)	0.3648 (3)	0.15512 (16)	0.0428 (6)
H12	1.0802	0.3618	0.1915	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0260 (2)	0.0333 (3)	0.0231 (2)	0.000	−0.00434 (16)	0.000
S1	0.0305 (3)	0.0415 (4)	0.0238 (3)	−0.0001 (3)	0.0004 (2)	0.0016 (2)
O1	0.0579 (15)	0.193 (3)	0.099 (2)	−0.0322 (18)	−0.0192 (14)	0.079 (2)
O2	0.0511 (11)	0.0469 (11)	0.0452 (11)	−0.0111 (9)	−0.0011 (9)	0.0076 (9)
O3	0.0292 (8)	0.0485 (10)	0.0272 (8)	0.0047 (7)	−0.0040 (7)	−0.0038 (7)
O4	0.0425 (10)	0.0625 (12)	0.0263 (9)	0.0069 (9)	0.0045 (7)	−0.0037 (8)
N1	0.0253 (9)	0.0408 (11)	0.0231 (10)	0.0000 (8)	−0.0006 (7)	−0.0016 (9)
N2	0.0383 (11)	0.0336 (11)	0.0287 (10)	0.0019 (9)	−0.0042 (8)	−0.0010 (8)
C1	0.0238 (11)	0.0400 (13)	0.0293 (12)	−0.0001 (10)	−0.0006 (9)	0.0029 (10)
C2	0.0354 (14)	0.0526 (16)	0.0357 (13)	0.0096 (12)	0.0024 (11)	−0.0009 (12)
C3	0.0490 (16)	0.0553 (18)	0.0560 (18)	0.0229 (14)	0.0011 (14)	0.0072 (14)
C4	0.0512 (17)	0.072 (2)	0.0377 (15)	0.0214 (15)	−0.0016 (12)	0.0139 (14)
C5	0.0389 (14)	0.0639 (19)	0.0305 (13)	0.0118 (13)	0.0013 (11)	0.0054 (12)
C6	0.0229 (11)	0.0433 (13)	0.0266 (11)	0.0005 (10)	−0.0010 (9)	0.0015 (11)
C7	0.0301 (12)	0.0503 (15)	0.0282 (12)	−0.0005 (11)	−0.0073 (10)	−0.0023 (11)
C8	0.0342 (12)	0.0382 (13)	0.0265 (12)	−0.0024 (11)	−0.0032 (10)	−0.0016 (10)
C9	0.0526 (16)	0.0487 (16)	0.0395 (15)	−0.0023 (13)	−0.0109 (12)	−0.0098 (13)
C10	0.073 (2)	0.0435 (16)	0.0433 (17)	0.0039 (15)	−0.0087 (15)	−0.0127 (13)
C11	0.0646 (19)	0.0376 (15)	0.0488 (17)	0.0134 (14)	−0.0012 (14)	−0.0036 (13)
C12	0.0492 (16)	0.0410 (15)	0.0381 (14)	0.0070 (12)	−0.0085 (12)	−0.0004 (12)

Geometric parameters (Å, º) top

Co1—O3	2.1029 (16)	C2—C3	1.380 (4)
Co1—O3ⁱ	2.1029 (16)	C2—H2	0.9300
Co1—N1ⁱ	2.1862 (18)	C3—C4	1.380 (4)
Co1—N1	2.1863 (18)	C3—H3	0.9300
Co1—N2	2.147 (2)	C4—C5	1.383 (4)
Co1—N2ⁱ	2.147 (2)	C4—H4	0.9300
S1—O2	1.4421 (18)	C5—C6	1.385 (3)
S1—O4	1.4433 (17)	C5—H5	0.9300
S1—O3	1.4773 (17)	C7—C8	1.456 (3)
S1—C1	1.770 (2)	C7—H7	0.9300
O1—H1W	0.8502	C8—C9	1.378 (3)
O1—H2W	0.8402	C9—C10	1.383 (4)
N1—C7	1.275 (3)	C9—H9	0.9300
N1—C6	1.422 (3)	C10—C11	1.366 (4)
N2—C12	1.331 (3)	C10—H10	0.9300
N2—C8	1.354 (3)	C11—C12	1.384 (4)
C1—C2	1.377 (3)	C11—H11	0.9300
C1—C6	1.406 (3)	C12—H12	0.9300

O3—Co1—O3ⁱ	115.85 (9)	C1—C2—H2	119.9
O3—Co1—N2	149.80 (7)	C3—C2—H2	119.9
O3ⁱ—Co1—N2	85.98 (7)	C2—C3—C4	120.0 (3)
O3—Co1—N2ⁱ	85.98 (7)	C2—C3—H3	120.0
O3ⁱ—Co1—N2ⁱ	149.80 (7)	C4—C3—H3	120.0
N2—Co1—N2ⁱ	83.20 (11)	C3—C4—C5	120.3 (2)
O3—Co1—N1ⁱ	83.51 (6)	C3—C4—H4	119.8
O3ⁱ—Co1—N1ⁱ	85.95 (6)	C5—C4—H4	119.8
N2—Co1—N1ⁱ	120.48 (7)	C4—C5—C6	120.4 (2)
N2ⁱ—Co1—N1ⁱ	75.60 (7)	C4—C5—H5	119.8
O3—Co1—N1	85.95 (6)	C6—C5—H5	119.8
O3ⁱ—Co1—N1	83.51 (6)	C5—C6—C1	118.7 (2)
N2—Co1—N1	75.60 (7)	C5—C6—N1	122.4 (2)
N2ⁱ—Co1—N1	120.48 (7)	C1—C6—N1	118.78 (19)
N1ⁱ—Co1—N1	160.09 (11)	N1—C7—C8	119.4 (2)
O2—S1—O4	114.72 (11)	N1—C7—H7	120.3
O2—S1—O3	112.14 (11)	C8—C7—H7	120.3
O4—S1—O3	111.25 (10)	N2—C8—C9	122.3 (2)
O2—S1—C1	106.90 (11)	N2—C8—C7	115.0 (2)
O4—S1—C1	107.06 (11)	C9—C8—C7	122.6 (2)
O3—S1—C1	103.96 (10)	C8—C9—C10	118.8 (2)
H1W—O1—H2W	110.5	C8—C9—H9	120.6
S1—O3—Co1	120.19 (9)	C10—C9—H9	120.6
C7—N1—C6	120.03 (19)	C11—C10—C9	119.2 (3)
C7—N1—Co1	114.63 (16)	C11—C10—H10	120.4
C6—N1—Co1	124.72 (14)	C9—C10—H10	120.4
C12—N2—C8	117.8 (2)	C10—C11—C12	118.9 (3)
C12—N2—Co1	126.85 (16)	C10—C11—H11	120.5
C8—N2—Co1	115.36 (16)	C12—C11—H11	120.5
C2—C1—C6	120.4 (2)	N2—C12—C11	122.9 (2)
C2—C1—S1	120.67 (18)	N2—C12—H12	118.6
C6—C1—S1	118.91 (18)	C11—C12—H12	118.6
C1—C2—C3	120.1 (2)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O4ⁱⁱ	0.85	2.16	3.009 (3)	179
O1—H2W···O2	0.84	2.15	2.867 (3)	143
C7—H7···O1ⁱⁱⁱ	0.93	2.56	3.425 (3)	154
C11—H11···O4^iv	0.93	2.46	3.389 (3)	172

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₉N₂O₃S)₂]·2H₂O
M_r	617.53
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	291
a, b, c (Å)	19.636 (2), 8.0973 (8), 16.2819 (16)
V (Å³)	2588.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.31 × 0.25 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.771, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	17970, 2410, 1960
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.02
No. of reflections	2410
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.46

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O3	2.1029 (16)	Co1—N2	2.147 (2)
Co1—N1	2.1863 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O4ⁱ	0.85	2.16	3.009 (3)	179.2
O1—H2W···O2	0.84	2.15	2.867 (3)	143.1
C7—H7···O1ⁱⁱ	0.93	2.56	3.425 (3)	154
C11—H11···O4ⁱⁱⁱ	0.93	2.46	3.389 (3)	172

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

Acknowledgements

This work was supported by the Science Foundation of the Guangxi Zhuang Autonomous Region of China (grant No. 0731053).

References

Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cai, C.-X., Ou-Yang, M., Zhao, Z.-Y. & Jiang, Y.-M. (2008). Acta Cryst. E64, m1195. Web of Science CSD CrossRef IUCr Journals Google Scholar
Casella, L. & Gullotti, M. (1986). Inorg. Chem. 25, 1293–1303. CrossRef CAS Web of Science Google Scholar
Jiang, Y.-M., Li, J.-M., Xie, F.-Q. & Wang, Y.-F. (2006). Chin. J. Struct. Chem. 25, 767–770. CAS Google Scholar
Ou-Yang, M., Huang, X.-R., Zhang, Y.-L. & Jiang, Y.-M. (2008). Acta Cryst. E64, m1461. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.