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

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); 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

Crystal data

• [CoCl₂(C₁₃H₁₄N₂)]

• M_r = 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) ų

• 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) 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[F² > 2σ(F²)] = 0.043

• wR(F²) = 0.098

• S = 1.03

• 1678 reflections

• 88 parameters

• H-atom parameters constrained

• Δρ_max = 0.56 e Å⁻³

• Δρ_min = −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); cell refinement: RAPID-AUTO; 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.

Supporting information

S1. 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.

Related literature

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).

S2. 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).

S3. 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 U_iso(H) = 1.2 U_eq(C).

Computing details

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

	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).

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

Crystal data

[CoCl2(C13H14N2)]	F(000) = 334
Mr = 328.09	Dx = 1.544 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 4916 reflections
a = 5.1899 (10) Å	θ = 3.1–27.5°
b = 12.989 (3) Å	µ = 1.58 mm^−1
c = 10.490 (2) Å	T = 295 K
β = 93.58 (3)°	Palte, purple
V = 705.8 (3) Å^3	0.36 × 0.25 × 0.13 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	1678 independent reflections
Radiation source: fine-focus sealed tube	1307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 0 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −6→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
Tmin = 0.628, Tmax = 0.813	l = −13→13
6891 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 0.5699P] where P = (Fo^2 + 2Fc^2)/3
1678 reflections	(Δ/σ)max < 0.001
88 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.45224 (11)	0.2500	0.72216 (5)	0.0469 (2)
Cl1	0.5449 (2)	0.2500	0.51643 (11)	0.0644 (3)
Cl2	0.7429 (2)	0.2500	0.89105 (11)	0.0563 (3)
N1	0.2438 (5)	0.38105 (17)	0.7418 (2)	0.0456 (5)
C1	−0.1030 (6)	0.4919 (2)	0.6704 (3)	0.0541 (8)
H1A	−0.2369	0.5056	0.6097	0.065*
C2	0.0502 (6)	0.4066 (2)	0.6576 (3)	0.0543 (8)
H2A	0.0175	0.3645	0.5867	0.065*
C3	0.2864 (6)	0.4443 (2)	0.8422 (3)	0.0515 (7)
H3A	0.4195	0.4283	0.9025	0.062*
C4	0.1436 (6)	0.5310 (2)	0.8601 (3)	0.0528 (7)
H4A	0.1821	0.5727	0.9309	0.063*
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	−0.2666	0.6554	0.8784	0.063*
H6B	−0.3688	0.6506	0.7346	0.063*
C7	−0.0613 (8)	0.7500	0.7639 (4)	0.0476 (9)
H7A	−0.0195	0.7500	0.6750	0.057*
H7B	0.0993	0.7500	0.8163	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0569 (4)	0.0384 (3)	0.0452 (3)	0.000	0.0009 (3)	0.000
Cl1	0.0673 (7)	0.0813 (8)	0.0442 (6)	0.000	0.0004 (5)	0.000
Cl2	0.0634 (7)	0.0500 (6)	0.0539 (6)	0.000	−0.0076 (5)	0.000
N1	0.0506 (13)	0.0385 (11)	0.0474 (14)	−0.0043 (11)	0.0002 (11)	0.0027 (10)
C1	0.0570 (17)	0.0463 (16)	0.0573 (19)	−0.0023 (15)	−0.0108 (15)	0.0018 (13)
C2	0.0651 (19)	0.0453 (16)	0.0514 (18)	−0.0055 (15)	−0.0057 (15)	−0.0044 (13)
C3	0.0586 (18)	0.0419 (15)	0.0528 (18)	0.0007 (14)	−0.0070 (14)	−0.0038 (12)
C4	0.0604 (18)	0.0430 (15)	0.0541 (18)	−0.0034 (15)	−0.0029 (14)	−0.0070 (13)
C5	0.0475 (15)	0.0373 (14)	0.0545 (17)	−0.0088 (12)	0.0053 (13)	0.0040 (12)
C6	0.0515 (16)	0.0409 (15)	0.065 (2)	−0.0007 (14)	0.0092 (15)	0.0043 (13)
C7	0.050 (2)	0.0363 (19)	0.057 (3)	0.000	0.0068 (19)	0.000

Geometric parameters (Å, º)

Co1—N1^i	2.034 (2)	C3—H3A	0.9300
Co1—N1	2.034 (2)	C4—C5	1.385 (4)
Co1—Cl1	2.2400 (14)	C4—H4A	0.9300
Co1—Cl2	2.2539 (14)	C5—C6	1.501 (4)
N1—C2	1.338 (4)	C6—C7	1.526 (4)
N1—C3	1.343 (4)	C6—H6A	0.9700
C1—C2	1.375 (4)	C6—H6B	0.9700
C1—C5	1.383 (4)	C7—C6^ii	1.526 (4)
C1—H1A	0.9300	C7—H7A	0.9700
C2—H2A	0.9300	C7—H7B	0.9700
C3—C4	1.368 (4)
N1^i—Co1—N1	113.61 (13)	C3—C4—C5	120.4 (3)
N1^i—Co1—Cl1	104.19 (7)	C3—C4—H4A	119.8
N1—Co1—Cl1	104.19 (7)	C5—C4—H4A	119.8
N1^i—Co1—Cl2	104.73 (7)	C1—C5—C4	116.5 (3)
N1—Co1—Cl2	104.73 (7)	C1—C5—C6	122.6 (3)
Cl1—Co1—Cl2	125.73 (5)	C4—C5—C6	120.9 (3)
C2—N1—C3	116.5 (3)	C5—C6—C7	111.7 (3)
C2—N1—Co1	121.5 (2)	C5—C6—H6A	109.3
C3—N1—Co1	121.9 (2)	C7—C6—H6A	109.3
C2—C1—C5	120.0 (3)	C5—C6—H6B	109.3
C2—C1—H1A	120.0	C7—C6—H6B	109.3
C5—C1—H1A	120.0	H6A—C6—H6B	107.9
N1—C2—C1	123.4 (3)	C6—C7—C6^ii	111.4 (3)
N1—C2—H2A	118.3	C6—C7—H7A	109.3
C1—C2—H2A	118.3	C6^ii—C7—H7A	109.3
N1—C3—C4	123.2 (3)	C6—C7—H7B	109.3
N1—C3—H3A	118.4	C6^ii—C7—H7B	109.3
C4—C3—H3A	118.4	H7A—C7—H7B	108.0
C5—C6—C7—C6^ii	−176.0 (2)

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