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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1025.
Published online 2008 July 12. doi:  10.1107/S1600536808020862
PMCID: PMC2961947

catena-Poly[[dichloridocobalt(II)]-μ-1,3-di-4-pyridylpropane-κ2 N:N′]

Abstract

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 π–π 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 [triangle]); Chen et al. (2004 [triangle]); Grosshans et al. (2004 [triangle]); Lee et al. (2004 [triangle]); Maji et al. (2005 [triangle]); Niu et al. (2003 [triangle]); Paz & Klinowski (2004 [triangle]); Carlucci et al. (1997 [triangle]); Pan et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1025-scheme1.jpg

Experimental

Crystal data

  • [CoCl2(C13H14N2)]
  • M r = 328.09
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1025-efi1.jpg
  • 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 [triangle]) T min = 0.628, T max = 0.813
  • 6891 measured reflections
  • 1678 independent reflections
  • 1307 reflections with I > 2σ(I)
  • R int = 0.057

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 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

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

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020862/bg2192sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020862/bg2192Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

Fig. 1.
ORTEP view of the title compound. The dispalcement ellipsoids are drawn at 40% probability level.
Fig. 2.
The crystal packing of the title complex, view pallel to (001).

Crystal data

[CoCl2(C13H14N2)]F000 = 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 = 3.1–27.5º
b = 12.989 (3) ŵ = 1.58 mm1
c = 10.490 (2) ÅT = 295 (2) K
β = 93.58 (3)ºPalte, purple
V = 705.8 (3) Å30.36 × 0.25 × 0.13 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer1678 independent reflections
Radiation source: fine-focus sealed tube1307 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.057
Detector resolution: 0 pixels mm-1θmax = 27.5º
T = 295(2) Kθmin = 3.1º
ω scansh = −6→6
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)k = −16→16
Tmin = 0.628, Tmax = 0.813l = −13→13
6891 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0331P)2 + 0.5699P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1678 reflectionsΔρmax = 0.56 e Å3
88 parametersΔρmin = −0.32 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

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)
C1−0.1030 (6)0.4919 (2)0.6704 (3)0.0541 (8)
H1A−0.23690.50560.60970.065*
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*
C5−0.0580 (6)0.5572 (2)0.7735 (3)0.0463 (7)
C6−0.2140 (6)0.6529 (2)0.7913 (3)0.0523 (7)
H6A−0.26660.65540.87840.063*
H6B−0.36880.65060.73460.063*
C7−0.0613 (8)0.75000.7639 (4)0.0476 (9)
H7A−0.01950.75000.67500.057*
H7B0.09930.75000.81630.057*

Atomic displacement parameters (Å2)

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)0.000−0.0076 (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, °)

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—C6ii−176.0 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2192).

References

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