Di­aqua­bis­[2-(2-hy­droxy­eth­yl)pyridine-κ2N,O]cobalt(II) dichloride

Zeghouan, O.; Guenifa, F.; Hadjadj, N.; Bendjeddou, L.; Merazig, H.

doi:10.1107/S1600536813018321

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m439-m440

doi:10.1107/S1600536813018321

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Diaquabis[2-(2-hydroxyethyl)pyridine-κ²N,O]cobalt(II) dichloride

Ouahida Zeghouan,^a Fatiha Guenifa,^a Nasreddine Hadjadj,^a Lamia Bendjeddou ^a ^* and Hocine Merazig ^a

^aUnité de Recherche Chimie de l'Environnement et Moléculaire Structurale 'CHEMS', Faculté des Sciences Exactes, Campus Chaabet Ersas, Université Constantine I, 25000 Constantine, Algeria
^*Correspondence e-mail: Lamiabendjeddou@yahoo.fr

(Received 29 June 2013; accepted 2 July 2013; online 6 July 2013)

In the title salt, [Co(C₇H₉NO)₂(H₂O)₂]Cl₂, the Co^II cation, located on an inversion center, is N,O-chelated by two hydroxyethylpyridine ligands and coordinated by two water molecules in a distorted O₄N₂ octahedral geometry. In the crystal, the Cl⁻ anions link with the complex cations via O—H⋯Cl hydrogen bonds, forming a three-dimensional supramolecular architecture. π–π stacking is observed between the pyridine rings of adjacent molecules [centroid–centroid distance = 3.5810 (11) Å].

Related literature

For applications of pyridine derivatives in the synthesis of coordination polymers, see: Sanudo et al. (2003 ); Boskovic et al. (2002 ). For related complexes containing a 2(2-hydroxyethyl)pyridine ligand, see: Kong et al. (2009 ); Mobin et al. (2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

[Co(C₇H₉NO)₂(H₂O)₂]Cl₂
M_r = 412.17
Orthorhombic, P b c n
a = 12.8911 (3) Å
b = 8.0049 (2) Å
c = 16.8757 (4) Å
V = 1741.44 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Bruker APEXII diffractometer
9407 measured reflections
1535 independent reflections
1419 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.056
S = 1.04
1535 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.1210 (13)
Co1—O1W	2.0715 (13)
Co1—N1	2.1537 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Clⁱ	0.84 (2)	2.26 (2)	3.0625 (13)	162 (2)
O1W—H1W⋯Clⁱⁱ	0.932 (11)	2.145 (12)	3.0738 (13)	174.6 (19)
O1W—H2W⋯Clⁱⁱⁱ	0.835 (16)	2.285 (16)	3.1121 (14)	170.4 (15)
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012), Mercury (Macrae et al., 2006 ) and POV-RAY (Persistence of Vision Team, 2004 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813018321/xu5717sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018321/xu5717Isup2.hkl

checkCIF report

Comment top

Pyridine derivatives ligands have the potential to be used in the synthesis of supramolecular materials, particularly transition metal coordination polymers (Sanudo et al., 2003; Boskovic et al., 2002). A few complexes containing L (L =2 (2-hydroxyethyl)pyridine) have been studied for years, because this ligand has a versatile coordination activities and bridging function (Kong et al., 2009; Mobin et al., 2010). We report here the synthesis and crystal structure of the title compound.

The complex comprises two L (L = 2-(2-hydroxyethyl)pyridine) ligands, one Co^II ion, two aqua ligands and uncoordinated Cl anions (Fig. 1). The coordination geometry around the Co center is octahedral with a CoN₂O₄ ligand set (Table 1). The bis L ligands coordinate to the Co(II) ions through the nitrogen atom of pyridine ring and the oxygen atom of hydroxyl group, creating a chelate ring. The octahedral geometries are completed by two trans aqua ligands at axial positions.

The complex cations are connected via O—H···Cl hydrogen bonds (Fig. 2), forming a centrosymmetric and a noncentrosymmetric rings, in two domensionel network, which can be described by the graph set R²₄(12) and R²₄(10), respectively (Bernstein et al.,1995). π-π stacking between the pyridine rings [centroid-centroid distance = 3.5810 (11) Å] is also present (Fig. 3).

Related literature top

For applications of pyridine derivatives in the synthesis of coordination polymers, see: Sanudo et al. (2003); Boskovic et al. (2002). For related complexes containing a 2(2-hydroxyethyl)pyridine ligand, see: Kong et al. (2009); Mobin et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by reaction of 2 (2-hydroxyethyl)pyridine (10.0 mmol, 1.67 g) in a mixture of ethanol–water (V/V = 1:1) and CoCl₂.6H₂O (10.0 mmol, 2.50 g), the solution was maintained at 313 K under agitation during 24 h at room temperature. Pink crystals were obtained by slow evaporation of the solvents within 3 weeks.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012), Mercury (Macrae et al., 2006) and POV-RAY (Persistence of Vision Team, 2004).

Figures top

	Fig. 1. The asymmetric unit of the title structure with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure, showing the aggregation of R²₄(12) and R²₄(10) hydrogen-bonding motifs.
	Fig. 3. A part of the crystal packing showing π–π stacking interactions between the pyridine rings (dashed lines).

Diaquabis[2-(2-hydroxyethyl)pyridine-κ²N,O]cobalt(II) dichloride top

Crystal data top

[Co(C₇H₉NO)₂(H₂O)₂]Cl₂	F(000) = 852
M_r = 412.17	D_x = 1.572 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1536 reflections
a = 12.8911 (3) Å	θ = 3.2–25.1°
b = 8.0049 (2) Å	µ = 1.31 mm⁻¹
c = 16.8757 (4) Å	T = 293 K
V = 1741.44 (7) Å³	Prism, pink
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Bruker APEXII diffractometer	1419 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
Graphite monochromator	θ_max = 25.1°, θ_min = 3.9°
ϕ scans	h = −14→15
9407 measured reflections	k = −9→9
1535 independent reflections	l = −19→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.0293P)² + 0.7255P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.056	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.21 e Å⁻³
1535 reflections	Δρ_min = −0.22 e Å⁻³
115 parameters

Crystal data top

[Co(C₇H₉NO)₂(H₂O)₂]Cl₂	V = 1741.44 (7) Å³
M_r = 412.17	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 12.8911 (3) Å	µ = 1.31 mm⁻¹
b = 8.0049 (2) Å	T = 293 K
c = 16.8757 (4) Å	0.3 × 0.2 × 0.2 mm

Data collection top

Bruker APEXII diffractometer	1419 reflections with I > 2σ(I)
9407 measured reflections	R_int = 0.015
1535 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.21 e Å⁻³
1535 reflections	Δρ_min = −0.22 e Å⁻³
115 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.50000	0.50000	0.00000	0.0229 (1)
O1	0.41357 (11)	0.27513 (16)	0.00777 (7)	0.0360 (4)
O1W	0.62402 (10)	0.39039 (16)	0.05822 (8)	0.0360 (4)
N1	0.43197 (11)	0.57142 (18)	0.11153 (8)	0.0272 (4)
C1	0.35447 (17)	0.2261 (3)	0.07500 (12)	0.0476 (7)
C2	0.40794 (17)	0.2792 (2)	0.15026 (11)	0.0413 (6)
C3	0.40051 (14)	0.4625 (2)	0.16765 (10)	0.0288 (5)
C4	0.36041 (17)	0.5176 (2)	0.23920 (11)	0.0367 (6)
C5	0.35342 (16)	0.6852 (3)	0.25479 (11)	0.0417 (6)
C6	0.38502 (15)	0.7962 (2)	0.19758 (12)	0.0404 (6)
C7	0.42246 (14)	0.7350 (2)	0.12727 (11)	0.0331 (6)
Cl	0.34635 (4)	0.01817 (5)	0.40317 (3)	0.0402 (2)
H1	0.3978 (18)	0.211 (3)	−0.0294 (11)	0.0540*
H1A	0.34570	0.10570	0.07490	0.0570*
H1B	0.28620	0.27680	0.07240	0.0570*
H1W	0.6327 (17)	0.2761 (13)	0.0664 (13)	0.0540*
H2A	0.48060	0.24860	0.14680	0.0500*
H2B	0.37800	0.21780	0.19420	0.0500*
H2W	0.6813 (12)	0.436 (2)	0.0664 (14)	0.0540*
H4	0.33820	0.44050	0.27680	0.0440*
H5	0.32780	0.72310	0.30310	0.0500*
H6	0.38110	0.91080	0.20640	0.0490*
H7	0.44230	0.81090	0.08840	0.0400*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0221 (2)	0.0221 (2)	0.0245 (2)	0.0002 (1)	0.0017 (1)	0.0009 (1)
O1	0.0429 (8)	0.0315 (7)	0.0337 (7)	−0.0128 (6)	0.0066 (6)	−0.0041 (5)
O1W	0.0293 (7)	0.0295 (7)	0.0491 (8)	0.0000 (5)	−0.0083 (6)	0.0071 (6)
N1	0.0259 (7)	0.0276 (7)	0.0280 (7)	0.0020 (6)	0.0025 (6)	−0.0007 (6)
C1	0.0534 (13)	0.0401 (11)	0.0492 (12)	−0.0200 (10)	0.0219 (10)	−0.0088 (9)
C2	0.0564 (13)	0.0310 (10)	0.0365 (10)	−0.0006 (9)	0.0159 (9)	0.0067 (8)
C3	0.0263 (9)	0.0336 (9)	0.0266 (9)	−0.0003 (7)	0.0004 (7)	0.0003 (7)
C4	0.0353 (11)	0.0479 (12)	0.0270 (9)	−0.0029 (8)	0.0034 (8)	−0.0003 (8)
C5	0.0381 (11)	0.0547 (12)	0.0324 (10)	0.0017 (10)	0.0038 (8)	−0.0152 (9)
C6	0.0395 (11)	0.0354 (10)	0.0463 (11)	0.0033 (9)	0.0010 (9)	−0.0134 (9)
C7	0.0306 (10)	0.0297 (9)	0.0389 (10)	0.0004 (7)	0.0022 (8)	−0.0013 (7)
Cl	0.0376 (3)	0.0269 (2)	0.0561 (3)	−0.0017 (2)	−0.0020 (2)	0.0015 (2)

Geometric parameters (Å, º) top

Co1—O1	2.1210 (13)	C2—C3	1.499 (2)
Co1—O1W	2.0715 (13)	C3—C4	1.386 (3)
Co1—N1	2.1537 (14)	C4—C5	1.370 (3)
Co1—O1ⁱ	2.1210 (13)	C5—C6	1.374 (3)
Co1—O1Wⁱ	2.0715 (13)	C6—C7	1.371 (3)
Co1—N1ⁱ	2.1537 (14)	C1—H1A	0.9704
O1—C1	1.422 (2)	C1—H1B	0.9701
O1—H1	0.84 (2)	C2—H2A	0.9699
O1W—H2W	0.835 (16)	C2—H2B	0.9697
O1W—H1W	0.932 (11)	C4—H4	0.9303
N1—C3	1.350 (2)	C5—H5	0.9305
N1—C7	1.342 (2)	C6—H6	0.9307
C1—C2	1.506 (3)	C7—H7	0.9300

O1—Co1—O1W	90.95 (5)	N1—C3—C4	121.20 (15)
O1—Co1—N1	87.56 (5)	C2—C3—C4	120.39 (15)
O1—Co1—O1ⁱ	180.00	N1—C3—C2	118.40 (15)
O1—Co1—O1Wⁱ	89.05 (5)	C3—C4—C5	120.24 (17)
O1—Co1—N1ⁱ	92.44 (5)	C4—C5—C6	118.61 (18)
O1W—Co1—N1	90.70 (5)	C5—C6—C7	118.77 (16)
O1ⁱ—Co1—O1W	89.05 (5)	N1—C7—C6	123.51 (16)
O1W—Co1—O1Wⁱ	180.00	O1—C1—H1A	109.58
O1W—Co1—N1ⁱ	89.30 (5)	O1—C1—H1B	109.54
O1ⁱ—Co1—N1	92.44 (5)	C2—C1—H1A	109.58
O1Wⁱ—Co1—N1	89.30 (5)	C2—C1—H1B	109.59
N1—Co1—N1ⁱ	180.00	H1A—C1—H1B	108.04
O1ⁱ—Co1—O1Wⁱ	90.95 (5)	C1—C2—H2A	108.66
O1ⁱ—Co1—N1ⁱ	87.56 (5)	C1—C2—H2B	108.64
O1Wⁱ—Co1—N1ⁱ	90.70 (5)	C3—C2—H2A	108.70
Co1—O1—C1	124.41 (12)	C3—C2—H2B	108.72
C1—O1—H1	107.4 (15)	H2A—C2—H2B	107.60
Co1—O1—H1	127.1 (15)	C3—C4—H4	119.87
H1W—O1W—H2W	107.4 (17)	C5—C4—H4	119.89
Co1—O1W—H2W	125.1 (12)	C4—C5—H5	120.72
Co1—O1W—H1W	125.4 (13)	C6—C5—H5	120.67
C3—N1—C7	117.65 (14)	C5—C6—H6	120.60
Co1—N1—C7	117.99 (11)	C7—C6—H6	120.63
Co1—N1—C3	124.34 (11)	N1—C7—H7	118.22
O1—C1—C2	110.47 (17)	C6—C7—H7	118.27
C1—C2—C3	114.33 (16)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Clⁱⁱ	0.84 (2)	2.26 (2)	3.0625 (13)	162 (2)
O1W—H1W···Clⁱⁱⁱ	0.932 (11)	2.145 (12)	3.0738 (13)	174.6 (19)
O1W—H2W···Cl^iv	0.835 (16)	2.285 (16)	3.1121 (14)	170.4 (15)

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

Experimental details

Crystal data
Chemical formula	[Co(C₇H₉NO)₂(H₂O)₂]Cl₂
M_r	412.17
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	12.8911 (3), 8.0049 (2), 16.8757 (4)
V (Å³)	1741.44 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.31
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9407, 1535, 1419
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.056, 1.04
No. of reflections	1535
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012), Mercury (Macrae et al., 2006) and POV-RAY (Persistence of Vision Team, 2004).

Selected bond lengths (Å) top

Co1—O1	2.1210 (13)	Co1—N1	2.1537 (14)
Co1—O1W	2.0715 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Clⁱ	0.84 (2)	2.26 (2)	3.0625 (13)	162 (2)
O1W—H1W···Clⁱⁱ	0.932 (11)	2.145 (12)	3.0738 (13)	174.6 (19)
O1W—H2W···Clⁱⁱⁱ	0.835 (16)	2.285 (16)	3.1121 (14)	170.4 (15)

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

Acknowledgements

This work was supported by the Unité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université de Constantine 1, Algeria. Thanks are due to MESRS and ATRST (Ministère de l'Enseignement Supérieur et de la Recherche Scientifique et l'Agence Thématique de Recherche en Sciences et Technologie, Algeria) via the PNR program for financial support.

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