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

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catena-Poly[[di­chloridocobalt(II)]-μ-1,3-di-4-pyridylpropane-κ2N:N′]

aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 29 May 2008; accepted 6 July 2008; online 12 July 2008)

In the title compound, [CoCl2(C13H14N2)]n, 1,3-bis­(4-pyrid­yl)propane (bpp) ligands bridge four-coordinate Co atoms, generating an extended one-dimensional zigzag chain. Both the Co and two Cl atoms in the tetrahedral coordination polyhedron lie on a mirror plane, while the bbp ligand is bis­ected through the central C atom in the chain by a second mirror plane. There are some ππ stacking inter­ations in the crystal structure, with inter­planar distances of 3.449 Å, which are responsible for the supra­molecular assembly.

Related literature

For related literature, see: Batten et al. (1999[Batten, S. R., Jeffey, J. C. & Ward, M. D. (1999). Inorg. Chim. Acta, 292, 231-237.]); Chen et al. (2004[Chen, Y.-B., Kang, Y., Qin, Y.-Y., Li, Z.-J., Cheng, J.-K., Hu, R.-F., Wen, Y.-H. & Yao, Y.-G. (2004). Acta Cryst. C60, m168-m169.]); Grosshans et al. (2004[Grosshans, P., Jouaiti, A., Bulach, V., Planeix, J. M., Hosseini, M. W. & Kyritsakas, N. (2004). Eur. J. Inorg. Chem. pp. 453-458.]); Lee et al. (2004[Lee, T. W., Lau, J. P. K. & Wong, W. T. (2004). Polyhedron, 23, 999-1002.]); Maji et al. (2005[Maji, T. K., Mostafa, G., Matsuda, R. & Kitagawa, S. (2005). J. Am. Chem. Soc. 127, 17152-17153.]); Niu et al. (2003[Niu, Y. Y., Song, Y. L., Hou, H. W. & Zhu, Y. (2003). Inorg. Chim. Acta, 355, 151-156.]); Paz & Klinowski (2004[Paz, F. A. A. & Klinowski, J. (2004). Inorg. Chem. 43, 3882-3893.]); Carlucci et al. (1997[Carlucci, L., Ciani, G. W., Gudenberg, D. & Proserpio, D. M. (1997). Inorg. Chem. 36, 3812-3813.]); Pan et al. (2001[Pan, L., Woodlock, W. B., Wang, X. T., Lam, K. C. & Rheingold, A. L. (2001). Chem. Commun. pp. 1762-1763.]).

[Scheme 1]

Experimental

Crystal data
  • [CoCl2(C13H14N2)]

  • Mr = 328.09

  • Monoclinic, P 21 /m

  • a = 5.1899 (10) Å

  • b = 12.989 (3) Å

  • c = 10.490 (2) Å

  • β = 93.58 (3)°

  • V = 705.8 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.58 mm−1

  • T = 295 (2) K

  • 0.36 × 0.25 × 0.13 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.628, Tmax = 0.813

  • 6891 measured reflections

  • 1678 independent reflections

  • 1307 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.098

  • S = 1.03

  • 1678 reflections

  • 88 parameters

  • H-atom parameters constrained

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.32 e Å−3

Table 1
Selected bond lengths (Å)

Co1—N1 2.034 (2)
Co1—Cl1 2.2400 (14)
Co1—Cl2 2.2539 (14)

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004[Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); 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: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Transition metal complexes with the flexible ligand 1,3-bis(4-pyridyl)propane (bpp) have been investigated extensively (Pan, et al., 2001; Batten, et al., 1999; Carlucci, et al., 1997; Lee, et al., 2004), and some of these compounds have potential application in nonlinear optical (NLO), magnetic, gas adsorption and microporous materials (Maji, et al., 2005; Niu, et al., 2003; Paz, et al., 2004). Our interest in transition metal-bpp complexes prompted us to report a new bpp-containing complex, [Co(bpp)Cl2]n, (I), obtained by self-assembly from CoCl2 and bpp in DMF solution. It is isostructural with the previously reported complex [Zn(bpp)Cl2]n (Chen, et al., 2004).

In the title compound, the Co atom is coordinated by two N atoms of two bpp ligands and two Cl anions, forming a distorted tetrahedron (Figure 1 and Table 1.) Both the cation and two chlorine atoms in the coordination polyhedra lie on a mirror plane, while the bbp ligand is bisected through the central carbon in the chain by a second mirror. The angles around Co(II) ions span the range 104.2° to 125. 7°. The Co—N bond distance is 2.034 (2) Å, and the Co—Cl distances are 2.240 (1) and 2.254 (1) Å, similar to those found in other related structures (Grosshans, et al., 2004). The bpp ligand is in a TT conformation, with a dihedral angle between two pyridine rings of 64.9°, and a C5—C6—C7—C6i (i = -x, 1.5 - y, z) torsion angle of 176.0°. Each bpp ligand bridges two cobalt(II) ions together via nitrogen atoms to form one-dimensional zigzag chains; there are π-π interations between pyridine rings, which are arranged in a face-to-face fashion with interplanar distances of 3.449 Å.

Related literature top

For related literature, see: Batten et al. (1999); Chen et al. (2004); Grosshans et al. (2004); Lee et al. (2004); Maji et al. (2005); Niu et al. (2003); Paz & Klinowski (2004); Carlucci et al. (1997); Pan et al. (2001).

Experimental top

Addition of 1,3-bis(4-pyridyl)propane (bpp) (0.198 g, 1.0 mmol) to a stirred DMF solution (30 ml) of CoCl2.6H2O (0.207 g 1.0 mmol) yielded a purple precipitate, which was refluxed for 30 min at 423 K followed by filtration after cooling. The resulting blue filtrate was maintained at room temperature; slow evaporation afforded a small amount of purple platelet cystals 15 days later (yield: 42% based on the initial CoCl2.6H2O input).

Refinement top

All H atoms werer located theoretically and refined as riding atoms, with C—H distances in the range 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title compound. The dispalcement ellipsoids are drawn at 40% probability level.
[Figure 2] Fig. 2. The crystal packing of the title complex, view pallel to (001).
catena-Poly[[dichloridocobalt(II)]-µ-1,3-di-4-pyridylpropane- κ2N:N'] top
Crystal data top
[CoCl2(C13H14N2)]F(000) = 334
Mr = 328.09Dx = 1.544 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 4916 reflections
a = 5.1899 (10) Åθ = 3.1–27.5°
b = 12.989 (3) ŵ = 1.58 mm1
c = 10.490 (2) ÅT = 295 K
β = 93.58 (3)°Palte, purple
V = 705.8 (3) Å30.36 × 0.25 × 0.13 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1678 independent reflections
Radiation source: fine-focus sealed tube1307 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 0 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = 66
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1616
Tmin = 0.628, Tmax = 0.813l = 1313
6891 measured reflections
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0331P)2 + 0.5699P]
where P = (Fo2 + 2Fc2)/3
1678 reflections(Δ/σ)max < 0.001
88 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
[CoCl2(C13H14N2)]V = 705.8 (3) Å3
Mr = 328.09Z = 2
Monoclinic, P21/mMo Kα radiation
a = 5.1899 (10) ŵ = 1.58 mm1
b = 12.989 (3) ÅT = 295 K
c = 10.490 (2) Å0.36 × 0.25 × 0.13 mm
β = 93.58 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1678 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1307 reflections with I > 2σ(I)
Tmin = 0.628, Tmax = 0.813Rint = 0.057
6891 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.03Δρmax = 0.56 e Å3
1678 reflectionsΔρmin = 0.32 e Å3
88 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
xyzUiso*/Ueq
Co10.45224 (11)0.25000.72216 (5)0.0469 (2)
Cl10.5449 (2)0.25000.51643 (11)0.0644 (3)
Cl20.7429 (2)0.25000.89105 (11)0.0563 (3)
N10.2438 (5)0.38105 (17)0.7418 (2)0.0456 (5)
C10.1030 (6)0.4919 (2)0.6704 (3)0.0541 (8)
H1A0.23690.50560.60970.065*
C20.0502 (6)0.4066 (2)0.6576 (3)0.0543 (8)
H2A0.01750.36450.58670.065*
C30.2864 (6)0.4443 (2)0.8422 (3)0.0515 (7)
H3A0.41950.42830.90250.062*
C40.1436 (6)0.5310 (2)0.8601 (3)0.0528 (7)
H4A0.18210.57270.93090.063*
C50.0580 (6)0.5572 (2)0.7735 (3)0.0463 (7)
C60.2140 (6)0.6529 (2)0.7913 (3)0.0523 (7)
H6A0.26660.65540.87840.063*
H6B0.36880.65060.73460.063*
C70.0613 (8)0.75000.7639 (4)0.0476 (9)
H7A0.01950.75000.67500.057*
H7B0.09930.75000.81630.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0569 (4)0.0384 (3)0.0452 (3)0.0000.0009 (3)0.000
Cl10.0673 (7)0.0813 (8)0.0442 (6)0.0000.0004 (5)0.000
Cl20.0634 (7)0.0500 (6)0.0539 (6)0.0000.0076 (5)0.000
N10.0506 (13)0.0385 (11)0.0474 (14)0.0043 (11)0.0002 (11)0.0027 (10)
C10.0570 (17)0.0463 (16)0.0573 (19)0.0023 (15)0.0108 (15)0.0018 (13)
C20.0651 (19)0.0453 (16)0.0514 (18)0.0055 (15)0.0057 (15)0.0044 (13)
C30.0586 (18)0.0419 (15)0.0528 (18)0.0007 (14)0.0070 (14)0.0038 (12)
C40.0604 (18)0.0430 (15)0.0541 (18)0.0034 (15)0.0029 (14)0.0070 (13)
C50.0475 (15)0.0373 (14)0.0545 (17)0.0088 (12)0.0053 (13)0.0040 (12)
C60.0515 (16)0.0409 (15)0.065 (2)0.0007 (14)0.0092 (15)0.0043 (13)
C70.050 (2)0.0363 (19)0.057 (3)0.0000.0068 (19)0.000
Geometric parameters (Å, º) top
Co1—N1i2.034 (2)C3—H3A0.9300
Co1—N12.034 (2)C4—C51.385 (4)
Co1—Cl12.2400 (14)C4—H4A0.9300
Co1—Cl22.2539 (14)C5—C61.501 (4)
N1—C21.338 (4)C6—C71.526 (4)
N1—C31.343 (4)C6—H6A0.9700
C1—C21.375 (4)C6—H6B0.9700
C1—C51.383 (4)C7—C6ii1.526 (4)
C1—H1A0.9300C7—H7A0.9700
C2—H2A0.9300C7—H7B0.9700
C3—C41.368 (4)
N1i—Co1—N1113.61 (13)C3—C4—C5120.4 (3)
N1i—Co1—Cl1104.19 (7)C3—C4—H4A119.8
N1—Co1—Cl1104.19 (7)C5—C4—H4A119.8
N1i—Co1—Cl2104.73 (7)C1—C5—C4116.5 (3)
N1—Co1—Cl2104.73 (7)C1—C5—C6122.6 (3)
Cl1—Co1—Cl2125.73 (5)C4—C5—C6120.9 (3)
C2—N1—C3116.5 (3)C5—C6—C7111.7 (3)
C2—N1—Co1121.5 (2)C5—C6—H6A109.3
C3—N1—Co1121.9 (2)C7—C6—H6A109.3
C2—C1—C5120.0 (3)C5—C6—H6B109.3
C2—C1—H1A120.0C7—C6—H6B109.3
C5—C1—H1A120.0H6A—C6—H6B107.9
N1—C2—C1123.4 (3)C6—C7—C6ii111.4 (3)
N1—C2—H2A118.3C6—C7—H7A109.3
C1—C2—H2A118.3C6ii—C7—H7A109.3
N1—C3—C4123.2 (3)C6—C7—H7B109.3
N1—C3—H3A118.4C6ii—C7—H7B109.3
C4—C3—H3A118.4H7A—C7—H7B108.0
C5—C6—C7—C6ii176.0 (2)
Symmetry codes: (i) x, y+1/2, z; (ii) x, y+3/2, z.

Experimental details

Crystal data
Chemical formula[CoCl2(C13H14N2)]
Mr328.09
Crystal system, space groupMonoclinic, P21/m
Temperature (K)295
a, b, c (Å)5.1899 (10), 12.989 (3), 10.490 (2)
β (°) 93.58 (3)
V3)705.8 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.58
Crystal size (mm)0.36 × 0.25 × 0.13
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.628, 0.813
No. of measured, independent and
observed [I > 2σ(I)] reflections
6891, 1678, 1307
Rint0.057
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.098, 1.03
No. of reflections1678
No. of parameters88
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.32

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Selected bond lengths (Å) top
Co1—N12.034 (2)Co1—Cl22.2539 (14)
Co1—Cl12.2400 (14)
 

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund in Ningbo University, the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061) and the Newer Training Program Foundation for Talents of the Science and Technology Department of Zhejiang Province (grant No. 2007R40G2070020). The authors also express sincere thanks to Dr Y. Q. Zheng for providing the study environment and for helpful comments.

References

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