metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 CoII 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 CoII 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 ππ 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[Liu, C., Ding, Y.-B., Shi, X.-H., Zhang, D., Hu, M.-H., Yin, Y.-G. & Li, D. (2009). Cryst. Growth Des. 9, 1275-1277.]); Yoshida et al. (2007[Yoshida, J., Nishikiori, S. & Kuroda, R. (2007). Chem. Lett. 36, 678-679.]).

[Scheme 1]

Experimental

Crystal data
  • [Co(CHO2)2(C20H14N4)(H2O)2]

  • Mr = 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[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]) Tmin = 0.075, Tmax = 0.126

  • 9417 measured reflections

  • 2303 independent reflections

  • 1544 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.76 e Å−3

  • Δρmin = −0.57 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 CoII complex obtained by the reaction of 4-pybpy, cobaltous nitrate hexahydrate in DMF solution.

As depicted in Fig. 1, the CoII 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 CoII atom can be described as octahedral. The 4-pybpy ligands link CoII 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 ππ 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).

Refinement top

H atoms on C atoms were placed at calculated positions and treated as riding atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O—H = 0.82 (1) and H···H = 1.39 (1) Å and with Uiso(H) = 1.5Ueq(O). The highest peak is located 0.28 Å from H12A and the deepest hole is located 0.90 Å from Co1.

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
[Figure 1] 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.]
[Figure 2] Fig. 2. View of the corrugated chain. H atoms were omitted for clarity.
[Figure 3] Fig. 3. Crystal packing of the title compound. Hydrogen bonds and ππ 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
Mr = 495.35Dx = 1.643 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2895 reflections
a = 24.412 (5) Åθ = 2.4–27.9°
b = 11.073 (2) ŵ = 0.91 mm1
c = 7.4117 (15) ÅT = 293 K
β = 91.28 (3)°Block, purple
V = 2003.0 (7) Å30.30 × 0.26 × 0.21 mm
Z = 4
Data collection top
Rigaku/MSC Mercury CCD
diffractometer
2303 independent reflections
Radiation source: fine-focus sealed tube1544 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(CrystalStructure; Rigaku/MSC, 2002)
h = 3131
Tmin = 0.075, Tmax = 0.126k = 1414
9417 measured reflectionsl = 98
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.040P)2 + 3.P]
where P = (Fo2 + 2Fc2)/3
2303 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.76 e Å3
3 restraintsΔρmin = 0.57 e Å3
Crystal data top
[Co(CHO2)2(C20H14N4)(H2O)2]V = 2003.0 (7) Å3
Mr = 495.35Z = 4
Monoclinic, C2/cMo Kα radiation
a = 24.412 (5) ŵ = 0.91 mm1
b = 11.073 (2) ÅT = 293 K
c = 7.4117 (15) Å0.30 × 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)
Tmin = 0.075, Tmax = 0.126Rint = 0.063
9417 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0443 restraints
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.76 e Å3
2303 reflectionsΔρmin = 0.57 e Å3
160 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.25001.25000.00000.02543 (18)
O1W0.30131 (10)1.13065 (19)0.1536 (3)0.0321 (5)
H1W0.2998 (17)1.132 (3)0.2643 (14)0.048*
H2W0.3056 (16)1.0629 (15)0.110 (4)0.048*
O10.22769 (10)1.35749 (18)0.2125 (3)0.0329 (5)
O20.18853 (10)1.3927 (2)0.4744 (3)0.0384 (6)
N10.17914 (11)1.1358 (2)0.0338 (3)0.0271 (6)
N20.00000.9831 (3)0.25000.0285 (8)
N30.00000.3497 (4)0.25000.0466 (11)
C10.13056 (14)1.1840 (3)0.0711 (4)0.0308 (7)
H10.12691.26750.06320.037*
C20.08571 (14)1.1183 (3)0.1202 (4)0.0300 (7)
H20.05281.15640.14580.036*
C30.09050 (13)0.9933 (3)0.1310 (4)0.0255 (7)
C40.13993 (14)0.9416 (3)0.0889 (4)0.0303 (7)
H40.14440.85830.09290.036*
C50.18262 (14)1.0151 (3)0.0409 (4)0.0290 (7)
H50.21570.97910.01170.035*
C60.04323 (13)0.9200 (3)0.1906 (4)0.0266 (7)
C70.04429 (12)0.7978 (2)0.1879 (4)0.0221 (6)
H70.07440.75640.14470.027*
C80.00000.7374 (4)0.25000.0286 (9)
C90.00000.6031 (4)0.25000.0325 (10)
C100.04717 (16)0.5383 (3)0.2075 (5)0.0386 (8)
H100.08000.57780.18050.046*
C110.04431 (18)0.4138 (3)0.2061 (5)0.0466 (10)
H110.07580.37160.17190.056*
C120.20695 (14)1.3244 (3)0.3573 (4)0.0297 (7)
H12A0.20521.24180.37900.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0309 (3)0.0234 (3)0.0222 (3)0.0028 (3)0.0045 (2)0.0005 (2)
O1W0.0425 (15)0.0286 (11)0.0252 (11)0.0011 (10)0.0021 (10)0.0004 (9)
O10.0438 (15)0.0292 (11)0.0259 (11)0.0069 (10)0.0077 (10)0.0032 (9)
O20.0456 (16)0.0435 (13)0.0265 (11)0.0001 (11)0.0083 (10)0.0030 (11)
N10.0292 (15)0.0256 (12)0.0267 (13)0.0016 (11)0.0015 (11)0.0010 (11)
N20.027 (2)0.0286 (18)0.0300 (18)0.0000.0020 (16)0.000
N30.061 (3)0.031 (2)0.048 (3)0.0000.008 (2)0.000
C10.032 (2)0.0239 (15)0.0368 (17)0.0017 (13)0.0008 (14)0.0000 (13)
C20.0281 (19)0.0259 (15)0.0361 (17)0.0022 (13)0.0003 (13)0.0048 (13)
C30.0302 (18)0.0239 (14)0.0222 (14)0.0012 (12)0.0013 (12)0.0034 (12)
C40.035 (2)0.0271 (15)0.0286 (15)0.0027 (14)0.0045 (13)0.0003 (13)
C50.0306 (19)0.0278 (15)0.0289 (15)0.0000 (13)0.0050 (13)0.0024 (13)
C60.0289 (18)0.0274 (15)0.0234 (14)0.0002 (13)0.0010 (12)0.0017 (13)
C70.0202 (16)0.0197 (12)0.0267 (14)0.0008 (11)0.0039 (12)0.0011 (12)
C80.027 (2)0.029 (2)0.030 (2)0.0000.0002 (17)0.000
C90.037 (3)0.029 (2)0.031 (2)0.0000.003 (2)0.000
C100.040 (2)0.0339 (17)0.0419 (19)0.0055 (15)0.0007 (16)0.0043 (15)
C110.057 (3)0.0375 (19)0.046 (2)0.0155 (18)0.0002 (18)0.0001 (17)
C120.0324 (19)0.0323 (16)0.0245 (14)0.0036 (14)0.0025 (13)0.0002 (14)
Geometric parameters (Å, º) top
Co1—O12.057 (2)C2—C31.392 (4)
Co1—O1i2.057 (2)C2—H20.9300
Co1—O1Wi2.133 (2)C3—C41.377 (4)
Co1—O1W2.133 (2)C3—C61.486 (4)
Co1—N1i2.162 (3)C4—C51.375 (4)
Co1—N12.162 (3)C4—H40.9300
O1W—H1W0.82 (1)C5—H50.9300
O1W—H2W0.82 (1)C6—C71.353 (4)
O1—C121.251 (3)C7—C81.361 (3)
O2—C121.243 (4)C7—H70.9300
N1—C11.335 (4)C8—C7ii1.361 (3)
N1—C51.341 (4)C8—C91.487 (6)
N2—C61.348 (4)C9—C101.387 (4)
N2—C6ii1.348 (4)C9—C10ii1.387 (4)
N3—C11ii1.328 (5)C10—C111.381 (5)
N3—C111.328 (5)C10—H100.9300
C1—C21.371 (4)C11—H110.9300
C1—H10.9300C12—H12A0.9300
O1—Co1—O1i180.0C4—C3—C2118.2 (3)
O1—Co1—O1Wi83.56 (9)C4—C3—C6122.1 (3)
O1i—Co1—O1Wi96.44 (9)C2—C3—C6119.7 (3)
O1—Co1—O1W96.44 (9)C5—C4—C3119.1 (3)
O1i—Co1—O1W83.56 (9)C5—C4—H4120.5
O1Wi—Co1—O1W180.0C3—C4—H4120.5
O1—Co1—N1i88.67 (9)N1—C5—C4123.5 (3)
O1i—Co1—N1i91.33 (9)N1—C5—H5118.2
O1Wi—Co1—N1i92.16 (9)C4—C5—H5118.2
O1W—Co1—N1i87.84 (9)N2—C6—C7122.6 (3)
O1—Co1—N191.33 (9)N2—C6—C3115.6 (3)
O1i—Co1—N188.67 (9)C7—C6—C3121.7 (3)
O1Wi—Co1—N187.84 (9)C6—C7—C8118.1 (3)
O1W—Co1—N192.16 (9)C6—C7—H7121.0
N1i—Co1—N1180.0C8—C7—H7121.0
Co1—O1W—H1W119 (2)C7—C8—C7ii121.1 (4)
Co1—O1W—H2W116 (2)C7—C8—C9119.5 (2)
H1W—O1W—H2W114.8 (18)C7ii—C8—C9119.5 (2)
C12—O1—Co1127.3 (2)C10—C9—C10ii117.7 (4)
C1—N1—C5116.5 (3)C10—C9—C8121.2 (2)
C1—N1—Co1120.5 (2)C10ii—C9—C8121.2 (2)
C5—N1—Co1122.5 (2)C11—C10—C9118.4 (4)
C6—N2—C6ii117.5 (4)C11—C10—H10120.8
C11ii—N3—C11115.4 (4)C9—C10—H10120.8
N1—C1—C2124.1 (3)N3—C11—C10125.0 (4)
N1—C1—H1117.9N3—C11—H11117.5
C2—C1—H1117.9C10—C11—H11117.5
C1—C2—C3118.5 (3)O2—C12—O1125.5 (3)
C1—C2—H2120.8O2—C12—H12A117.2
C3—C2—H2120.8O1—C12—H12A117.2
Symmetry codes: (i) x+1/2, y+5/2, z; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2iii0.82 (1)1.97 (1)2.775 (3)166 (4)
O1W—H2W···O2iv0.82 (1)1.99 (1)2.814 (3)174 (3)
C2—H2···N3v0.932.623.458 (3)150
C5—H5···O2iv0.932.533.429 (4)164
Symmetry codes: (iii) x+1/2, y+5/2, z+1; (iv) x+1/2, y1/2, z+1/2; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Co(CHO2)2(C20H14N4)(H2O)2]
Mr495.35
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)24.412 (5), 11.073 (2), 7.4117 (15)
β (°) 91.28 (3)
V3)2003.0 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.91
Crystal size (mm)0.30 × 0.26 × 0.21
Data collection
DiffractometerRigaku/MSC Mercury CCD
diffractometer
Absorption correctionMulti-scan
(CrystalStructure; Rigaku/MSC, 2002)
Tmin, Tmax0.075, 0.126
No. of measured, independent and
observed [I > 2σ(I)] reflections
9417, 2303, 1544
Rint0.063
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.112, 1.11
No. of reflections2303
No. of parameters160
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1W—H1W···O2i0.82 (1)1.97 (1)2.775 (3)166 (4)
O1W—H2W···O2ii0.82 (1)1.99 (1)2.814 (3)174 (3)
C2—H2···N3iii0.932.623.458 (3)150
C5—H5···O2ii0.932.533.429 (4)164
Symmetry codes: (i) x+1/2, y+5/2, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x, y+1, z.
 

Acknowledgements

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

References

First citationLiu, C., Ding, Y.-B., Shi, X.-H., Zhang, D., Hu, M.-H., Yin, Y.-G. & Li, D. (2009). Cryst. Growth Des. 9, 1275–1277.  CrossRef CAS Google Scholar
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYoshida, J., Nishikiori, S. & Kuroda, R. (2007). Chem. Lett. 36, 678–679.  CrossRef CAS Google Scholar

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