catena-Poly[[diaqua­bis­(formato-κO)cobalt(II)]-μ2-2,6-bis­(pyridin-4-yl)-4,4′-bipyridine-κ2N2:N6]

Ma, D.-Y.; Sun, D.-E.; Li, G.-Q.

doi:10.1107/S1600536811021118

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m913

doi:10.1107/S1600536811021118

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catena-Poly[[diaquabis(formato-κO)cobalt(II)]-μ₂-2,6-bis(pyridin-4-yl)-4,4′-bipyridine-κ²N²:N⁶]

De-Yun Ma,^a De-En Sun ^a and Guo-Qing Li ^a ^*

^aSchool of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, People's Republic of China
^*Correspondence e-mail: gqli1@scut.edu.cn

(Received 19 April 2011; accepted 1 June 2011; online 11 June 2011)

In the title complex, [Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]_n, the Co^II ion, lying on an inversion center, is six-coordinated by two O atoms from two monodentate formate ligands, two N atoms from two 2,6-bis(pyridin-4-yl)-4,4′-bipyridine (4-pybpy) ligands and two water molecules, displaying an octahedral geometry. The 4-pybpy ligand, having a twofold rotation axis, functions in a bridging coordination mode, connecting the Co^II ions into a corrugated chain along [ $[\overline{1}]$ 01]. The chains are further linked into a three-dimensional supramolecular network by O—H⋯O, C—H⋯N and C—H⋯O hydrogen bonds and π–π stacking interactions between the pyridine rings [centroid-to-centroid distance = 3.743 (2) Å].

Related literature

For general background to complexes with 2,6-bis(4-pyridyl)-4,4′-bipyridine, see: Liu et al. (2009 ); Yoshida et al. (2007 ).

Experimental

Crystal data

[Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]
M_r = 495.35
Monoclinic, C 2/c
a = 24.412 (5) Å
b = 11.073 (2) Å
c = 7.4117 (15) Å
β = 91.28 (3)°
V = 2003.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 293 K
0.30 × 0.26 × 0.21 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalStructure; Rigaku/MSC, 2002 ) T_min = 0.075, T_max = 0.126
9417 measured reflections
2303 independent reflections
1544 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.112
S = 1.11
2303 reflections
160 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2ⁱ	0.82 (1)	1.97 (1)	2.775 (3)	166 (4)
O1W—H2W⋯O2ⁱⁱ	0.82 (1)	1.99 (1)	2.814 (3)	174 (3)
C2—H2⋯N3ⁱⁱⁱ	0.93	2.62	3.458 (3)	150
C5—H5⋯O2ⁱⁱ	0.93	2.53	3.429 (4)	164
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z.

Data collection: CrystalStructure (Rigaku/MSC, 2002); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021118/hy2424sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021118/hy2424Isup2.hkl

checkCIF report

Comment top

In the structural investigation of 2,6-bis(4-pyridyl)-4,4'-bipyridine (4-pybpy) complexes, it has been found that 4-pybpy functions as a multidentate ligand (Liu et al., 2009; Yoshida et al., 2007), with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, a new Co^II complex obtained by the reaction of 4-pybpy, cobaltous nitrate hexahydrate in DMF solution.

As depicted in Fig. 1, the Co^II atom, lying on an inversion center, is coordinated by two O atoms from two formate anions, two N atoms from two 4-pybpy ligands and two water molecules. The coordination environment of the Co^II atom can be described as octahedral. The 4-pybpy ligands link Co^II ions, forming infinite chains, with a Co···Co separation of 12.835 (2) Å (Fig. 2). These chains are further self-assembled into a three-dimensional supramolecular network via intermolecular O—H···O and C—H···O hydrogen bonds (Table 1) involving the water molecules as donors and O atoms of the formate groups as acceptors, and π–π stacking interactions between the pyridyl rings of neighboring 4-pybpy ligands (Fig. 3). The centroid–centroid distance is 3.743 (2) Å.

Related literature top

For general background to complexes with 2,6-bis(4-pyridyl)-4,4'-bipyridine, see: Liu et al. (2009); Yoshida et al. (2007).

Experimental top

A mixture of 4-pybpy (0.155 g, 0.5 mmol), cobalt nitrate hexahydrate (0.145 g, 0.5 mmol) and DMF (15 ml) was placed in a 23 ml Teflon-lined reactor, which was heated at 358 K for 2 d, and then cooled to room temperature at a rate of 10 K h^-1. Block purple crystals obtained were washed with water and dried in air (yield: 45% based on Co).

Computing details top

Data collection: CrystalStructure (Rigaku/MSC, 2002); cell refinement: CrystalStructure (Rigaku/MSC, 2002); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids. H atoms were omitted for clarity. [Symmetry codes: (i) 1/2 - x, 5/2 - y, -z; (ii) -x, y, 1/2 - z.]
	Fig. 2. View of the corrugated chain. H atoms were omitted for clarity.
	Fig. 3. Crystal packing of the title compound. Hydrogen bonds and π–π stacking interactions are shown as dashed lines.

catena-Poly[[diaquabis(formato-κO)cobalt(II)]-µ₂- 2,6-bis(pyridin-4-yl)-4,4'-bipyridine-κ²N²:N⁶] top

Crystal data top

[Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]	F(000) = 1020
M_r = 495.35	D_x = 1.643 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2895 reflections
a = 24.412 (5) Å	θ = 2.4–27.9°
b = 11.073 (2) Å	µ = 0.91 mm⁻¹
c = 7.4117 (15) Å	T = 293 K
β = 91.28 (3)°	Block, purple
V = 2003.0 (7) Å³	0.30 × 0.26 × 0.21 mm
Z = 4

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2303 independent reflections
Radiation source: fine-focus sealed tube	1544 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalStructure; Rigaku/MSC, 2002)	h = −31→31
T_min = 0.075, T_max = 0.126	k = −14→14
9417 measured reflections	l = −9→8

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.040P)² + 3.P] where P = (F_o² + 2F_c²)/3
2303 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.76 e Å⁻³
3 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]	V = 2003.0 (7) Å³
M_r = 495.35	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.412 (5) Å	µ = 0.91 mm⁻¹
b = 11.073 (2) Å	T = 293 K
c = 7.4117 (15) Å	0.30 × 0.26 × 0.21 mm
β = 91.28 (3)°

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2303 independent reflections
Absorption correction: multi-scan (CrystalStructure; Rigaku/MSC, 2002)	1544 reflections with I > 2σ(I)
T_min = 0.075, T_max = 0.126	R_int = 0.063
9417 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	3 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.76 e Å⁻³
2303 reflections	Δρ_min = −0.57 e Å⁻³
160 parameters

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

	x	y	z	U_iso*/U_eq
Co1	0.2500	1.2500	0.0000	0.02543 (18)
O1W	0.30131 (10)	1.13065 (19)	0.1536 (3)	0.0321 (5)
H1W	0.2998 (17)	1.132 (3)	0.2643 (14)	0.048*
H2W	0.3056 (16)	1.0629 (15)	0.110 (4)	0.048*
O1	0.22769 (10)	1.35749 (18)	0.2125 (3)	0.0329 (5)
O2	0.18853 (10)	1.3927 (2)	0.4744 (3)	0.0384 (6)
N1	0.17914 (11)	1.1358 (2)	0.0338 (3)	0.0271 (6)
N2	0.0000	0.9831 (3)	0.2500	0.0285 (8)
N3	0.0000	0.3497 (4)	0.2500	0.0466 (11)
C1	0.13056 (14)	1.1840 (3)	0.0711 (4)	0.0308 (7)
H1	0.1269	1.2675	0.0632	0.037*
C2	0.08571 (14)	1.1183 (3)	0.1202 (4)	0.0300 (7)
H2	0.0528	1.1564	0.1458	0.036*
C3	0.09050 (13)	0.9933 (3)	0.1310 (4)	0.0255 (7)
C4	0.13993 (14)	0.9416 (3)	0.0889 (4)	0.0303 (7)
H4	0.1444	0.8583	0.0929	0.036*
C5	0.18262 (14)	1.0151 (3)	0.0409 (4)	0.0290 (7)
H5	0.2157	0.9791	0.0117	0.035*
C6	0.04323 (13)	0.9200 (3)	0.1906 (4)	0.0266 (7)
C7	0.04429 (12)	0.7978 (2)	0.1879 (4)	0.0221 (6)
H7	0.0744	0.7564	0.1447	0.027*
C8	0.0000	0.7374 (4)	0.2500	0.0286 (9)
C9	0.0000	0.6031 (4)	0.2500	0.0325 (10)
C10	−0.04717 (16)	0.5383 (3)	0.2075 (5)	0.0386 (8)
H10	−0.0800	0.5778	0.1805	0.046*
C11	−0.04431 (18)	0.4138 (3)	0.2061 (5)	0.0466 (10)
H11	−0.0758	0.3716	0.1719	0.056*
C12	0.20695 (14)	1.3244 (3)	0.3573 (4)	0.0297 (7)
H12A	0.2052	1.2418	0.3790	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0309 (3)	0.0234 (3)	0.0222 (3)	−0.0028 (3)	0.0045 (2)	−0.0005 (2)
O1W	0.0425 (15)	0.0286 (11)	0.0252 (11)	−0.0011 (10)	0.0021 (10)	0.0004 (9)
O1	0.0438 (15)	0.0292 (11)	0.0259 (11)	−0.0069 (10)	0.0077 (10)	−0.0032 (9)
O2	0.0456 (16)	0.0435 (13)	0.0265 (11)	0.0001 (11)	0.0083 (10)	−0.0030 (11)
N1	0.0292 (15)	0.0256 (12)	0.0267 (13)	−0.0016 (11)	0.0015 (11)	−0.0010 (11)
N2	0.027 (2)	0.0286 (18)	0.0300 (18)	0.000	0.0020 (16)	0.000
N3	0.061 (3)	0.031 (2)	0.048 (3)	0.000	0.008 (2)	0.000
C1	0.032 (2)	0.0239 (15)	0.0368 (17)	0.0017 (13)	0.0008 (14)	0.0000 (13)
C2	0.0281 (19)	0.0259 (15)	0.0361 (17)	0.0022 (13)	−0.0003 (13)	−0.0048 (13)
C3	0.0302 (18)	0.0239 (14)	0.0222 (14)	0.0012 (12)	−0.0013 (12)	−0.0034 (12)
C4	0.035 (2)	0.0271 (15)	0.0286 (15)	0.0027 (14)	0.0045 (13)	−0.0003 (13)
C5	0.0306 (19)	0.0278 (15)	0.0289 (15)	0.0000 (13)	0.0050 (13)	−0.0024 (13)
C6	0.0289 (18)	0.0274 (15)	0.0234 (14)	−0.0002 (13)	0.0010 (12)	−0.0017 (13)
C7	0.0202 (16)	0.0197 (12)	0.0267 (14)	0.0008 (11)	0.0039 (12)	−0.0011 (12)
C8	0.027 (2)	0.029 (2)	0.030 (2)	0.000	0.0002 (17)	0.000
C9	0.037 (3)	0.029 (2)	0.031 (2)	0.000	0.003 (2)	0.000
C10	0.040 (2)	0.0339 (17)	0.0419 (19)	−0.0055 (15)	−0.0007 (16)	0.0043 (15)
C11	0.057 (3)	0.0375 (19)	0.046 (2)	−0.0155 (18)	0.0002 (18)	0.0001 (17)
C12	0.0324 (19)	0.0323 (16)	0.0245 (14)	−0.0036 (14)	0.0025 (13)	−0.0002 (14)

Geometric parameters (Å, º) top

Co1—O1	2.057 (2)	C2—C3	1.392 (4)
Co1—O1ⁱ	2.057 (2)	C2—H2	0.9300
Co1—O1Wⁱ	2.133 (2)	C3—C4	1.377 (4)
Co1—O1W	2.133 (2)	C3—C6	1.486 (4)
Co1—N1ⁱ	2.162 (3)	C4—C5	1.375 (4)
Co1—N1	2.162 (3)	C4—H4	0.9300
O1W—H1W	0.82 (1)	C5—H5	0.9300
O1W—H2W	0.82 (1)	C6—C7	1.353 (4)
O1—C12	1.251 (3)	C7—C8	1.361 (3)
O2—C12	1.243 (4)	C7—H7	0.9300
N1—C1	1.335 (4)	C8—C7ⁱⁱ	1.361 (3)
N1—C5	1.341 (4)	C8—C9	1.487 (6)
N2—C6	1.348 (4)	C9—C10	1.387 (4)
N2—C6ⁱⁱ	1.348 (4)	C9—C10ⁱⁱ	1.387 (4)
N3—C11ⁱⁱ	1.328 (5)	C10—C11	1.381 (5)
N3—C11	1.328 (5)	C10—H10	0.9300
C1—C2	1.371 (4)	C11—H11	0.9300
C1—H1	0.9300	C12—H12A	0.9300

O1—Co1—O1ⁱ	180.0	C4—C3—C2	118.2 (3)
O1—Co1—O1Wⁱ	83.56 (9)	C4—C3—C6	122.1 (3)
O1ⁱ—Co1—O1Wⁱ	96.44 (9)	C2—C3—C6	119.7 (3)
O1—Co1—O1W	96.44 (9)	C5—C4—C3	119.1 (3)
O1ⁱ—Co1—O1W	83.56 (9)	C5—C4—H4	120.5
O1Wⁱ—Co1—O1W	180.0	C3—C4—H4	120.5
O1—Co1—N1ⁱ	88.67 (9)	N1—C5—C4	123.5 (3)
O1ⁱ—Co1—N1ⁱ	91.33 (9)	N1—C5—H5	118.2
O1Wⁱ—Co1—N1ⁱ	92.16 (9)	C4—C5—H5	118.2
O1W—Co1—N1ⁱ	87.84 (9)	N2—C6—C7	122.6 (3)
O1—Co1—N1	91.33 (9)	N2—C6—C3	115.6 (3)
O1ⁱ—Co1—N1	88.67 (9)	C7—C6—C3	121.7 (3)
O1Wⁱ—Co1—N1	87.84 (9)	C6—C7—C8	118.1 (3)
O1W—Co1—N1	92.16 (9)	C6—C7—H7	121.0
N1ⁱ—Co1—N1	180.0	C8—C7—H7	121.0
Co1—O1W—H1W	119 (2)	C7—C8—C7ⁱⁱ	121.1 (4)
Co1—O1W—H2W	116 (2)	C7—C8—C9	119.5 (2)
H1W—O1W—H2W	114.8 (18)	C7ⁱⁱ—C8—C9	119.5 (2)
C12—O1—Co1	127.3 (2)	C10—C9—C10ⁱⁱ	117.7 (4)
C1—N1—C5	116.5 (3)	C10—C9—C8	121.2 (2)
C1—N1—Co1	120.5 (2)	C10ⁱⁱ—C9—C8	121.2 (2)
C5—N1—Co1	122.5 (2)	C11—C10—C9	118.4 (4)
C6—N2—C6ⁱⁱ	117.5 (4)	C11—C10—H10	120.8
C11ⁱⁱ—N3—C11	115.4 (4)	C9—C10—H10	120.8
N1—C1—C2	124.1 (3)	N3—C11—C10	125.0 (4)
N1—C1—H1	117.9	N3—C11—H11	117.5
C2—C1—H1	117.9	C10—C11—H11	117.5
C1—C2—C3	118.5 (3)	O2—C12—O1	125.5 (3)
C1—C2—H2	120.8	O2—C12—H12A	117.2
C3—C2—H2	120.8	O1—C12—H12A	117.2

Symmetry codes: (i) −x+1/2, −y+5/2, −z; (ii) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2ⁱⁱⁱ	0.82 (1)	1.97 (1)	2.775 (3)	166 (4)
O1W—H2W···O2^iv	0.82 (1)	1.99 (1)	2.814 (3)	174 (3)
C2—H2···N3^v	0.93	2.62	3.458 (3)	150
C5—H5···O2^iv	0.93	2.53	3.429 (4)	164

Symmetry codes: (iii) −x+1/2, −y+5/2, −z+1; (iv) −x+1/2, y−1/2, −z+1/2; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]
M_r	495.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	24.412 (5), 11.073 (2), 7.4117 (15)
β (°)	91.28 (3)
V (Å³)	2003.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.30 × 0.26 × 0.21

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalStructure; Rigaku/MSC, 2002)
T_min, T_max	0.075, 0.126
No. of measured, independent and observed [I > 2σ(I)] reflections	9417, 2303, 1544
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.112, 1.11
No. of reflections	2303
No. of parameters	160
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.57

Computer programs: CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2ⁱ	0.82 (1)	1.97 (1)	2.775 (3)	166 (4)
O1W—H2W···O2ⁱⁱ	0.82 (1)	1.99 (1)	2.814 (3)	174 (3)
C2—H2···N3ⁱⁱⁱ	0.93	2.62	3.458 (3)	150
C5—H5···O2ⁱⁱ	0.93	2.53	3.429 (4)	164

Symmetry codes: (i) −x+1/2, −y+5/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y+1, z.

Acknowledgements

The authors acknowledge South China University of Technology for supporting this work.

References

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