catena-Poly[[bis­(4-chloro­methyl­pyridine-κN)cobalt(II)]-di-μ-dicyanamido-κ²N¹:κ²N⁵]

The title compound, [Co(C₂N₃)(C₆H₆ClN)₂]_n, is a polymeric cobalt(II) complex with the metal ion located on an inversion centre. The Co^II ion is six-coordinated by two N atoms of two 4-chloro­methyl­pyridine ligands and four N atoms from four dicyanamide ligands, forming a slightly distorted octa­hedral configuration. In the crystal structure, neighbouring Co atoms are linked together by double dicyanamide bridges to form a polymeric cobalt(II) complex.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• R factor = 0.068
• wR factor = 0.160
• Data-to-parameter ratio = 12.9

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S1. Comment

To date, the dicyanamide ligand has frequently been used to bridge polynuclear transition metal complexes in the study of multidimensional molecule-based magnetic materials and other areas. Many such compounds have been reported. Most of them are focused on low-oxidation state systems, such as M^I (Britton, 1990; Batten et al., 2000; Bessler et al., 2000) and M^II (Manson et al., 1998; Claramunt et al., 2000; Dasna, et al., 2000; Jensen et al., 2000; Sun, Gao, Ma, Niu et al., 2000; Triki et al., 2001; Shi et al., 2002) (M^I = Cu or Ag; M^II = Cd, Cu, Co, Ni, Zn, Mn or Fe). Cobalt complexes have been synthesized previously but the different kinds of interactions observed for Co^II are still not clear and deserve the attention of magnetochemists (Marshall et al., 2000; Sun, Gao, Ma, Niu et al., 2000; Sun, Gao, Ma & Wang, 2000; Jäger et al., 2001; Jensen et al., 2001). Here, we report the structure of the title Co^II compound, (I).

The molecular structure of (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. [No values have been flagged for publication in the CIF so there is no Table 1 - do you wish to add one?] The Co^II ion, which lies on an inversion centre, is in a octahedral geometry and is six-coordinated by six N atoms, from four dicyanamide ligands and two 4-chloromethylpyridine ligands in a trans arrangement. The resulting coordination geometry is very close to that expected for an ideal octahedral complex.

In the crystal structure, each Co^II ion is bridged to form a one-dimensional chain along the [010] axis by dicyanamide ligands, through single end-to-end coordination, i.e. the dicyanamide ligand acts as a bidentate bridging ligand by coordinating to adjacent Co^II centres through its two terminal nitrile N atoms. No significant contacts are observed between adjacent chains in the crystal structure. Neighbouring benzene rings of the 4-chloromethylpyridine ligands along a chain to do not display π–π interactions, the distance between the centroids of the rings being 7.4810 (9) Å (Fig. 2).

S2. Experimental

All chemicals were of reagent grade quality obtained from commercial sources and used without further purification. A mixture of CoCl₂·6H₂O (120 mg, 0.504 mmol) and 4-chloromethylpyridine (90 mg, 0.549 mmol) was dissolved in methanol (10 ml) with stirring. To this solution was added an aqueous solution (5 ml) of dicyanamide (90 mg, 1.01 mmol), with stirring. The solution was refluxed for 30 min and then filtered. After allowing the filtrate to evaporate in air for 24 h, well shaped red needles of (I) were obtained (70% yield). Analysis, found: C 43.85, H 2.61, N 26.09%; calculated for C₁₆H₁₂Cl₂CoN₈: C 43.03, H 2.69, N, 25.10%.

S3. Refinement

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances constrained to 0.93 (aromatic CH) or 0.97 Å (methylene CH₂) and with U_iso(H) = 1.2U_eq(carrier C atom).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) 1 − x, 1 − y, 1 − z.]
	Fig. 2. The crystal packing of (I), viewed along the [100] axis.

catena-Poly[[bis(4-chloromethylpyridine-κN)cobalt(II)]-di-µ- dicyanamido-κN¹:κN⁵]

Crystal data

[Co(C2N3)(C6H6ClN)2]	Z = 1
Mr = 446.17	F(000) = 225
Triclinic, P1	Dx = 1.624 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2910 (9) Å	Cell parameters from 668 reflections
b = 7.4810 (9) Å	θ = 2.3–25.1°
c = 9.0070 (13) Å	µ = 1.25 mm^−1
α = 104.444 (2)°	T = 295 K
β = 96.971 (2)°	Needle, red
γ = 102.618 (2)°	0.44 × 0.14 × 0.10 mm
V = 456.15 (10) Å^3

Data collection

Bruker APEX area-detector diffractometer	1601 independent reflections
Radiation source: fine-focus sealed tube	1368 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scans	θmax = 25.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→6
Tmin = 0.805, Tmax = 0.885	k = −8→8
2408 measured reflections	l = −9→10

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0336P)^2 + 2.6609P] where P = (Fo^2 + 2Fc^2)/3
1601 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.78 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	0.5000	0.5000	0.5000	0.0306 (3)
Cl1	−0.3261 (3)	0.1451 (4)	−0.1605 (3)	0.0869 (8)
N1	0.6712 (7)	0.7140 (7)	0.4213 (6)	0.0393 (12)
N2	0.8059 (7)	1.0352 (7)	0.4023 (7)	0.0500 (15)
N3	0.6629 (7)	1.3038 (6)	0.4231 (6)	0.0371 (11)
N4	0.3064 (7)	0.3950 (6)	0.2785 (5)	0.0336 (11)
C1	0.7272 (8)	0.8680 (8)	0.4160 (6)	0.0321 (12)
C2	0.7201 (8)	1.1707 (8)	0.4149 (6)	0.0312 (12)
C3	0.3662 (9)	0.3585 (10)	0.1426 (7)	0.0458 (15)
H3	0.4970	0.3800	0.1440	0.055*
C4	0.2438 (9)	0.2905 (10)	0.0001 (8)	0.0520 (17)
H4	0.2925	0.2675	−0.0916	0.062*
C5	0.0485 (9)	0.2565 (8)	−0.0061 (7)	0.0406 (14)
C6	−0.0159 (9)	0.2922 (10)	0.1332 (8)	0.0486 (16)
H6	−0.1461	0.2704	0.1345	0.058*
C7	0.1168 (9)	0.3611 (10)	0.2712 (8)	0.0474 (16)
H7	0.0716	0.3852	0.3645	0.057*
C8	−0.0827 (10)	0.1803 (11)	−0.1655 (8)	0.0575 (19)
H8A	−0.0606	0.0597	−0.2196	0.069*
H8B	−0.0480	0.2692	−0.2258	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0321 (6)	0.0224 (6)	0.0304 (6)	0.0031 (4)	−0.0023 (4)	0.0027 (4)
Cl1	0.0536 (12)	0.1073 (18)	0.0700 (14)	0.0161 (12)	−0.0248 (10)	−0.0065 (12)
N1	0.042 (3)	0.031 (3)	0.043 (3)	0.005 (2)	0.003 (2)	0.013 (2)
N2	0.037 (3)	0.028 (3)	0.093 (4)	0.010 (2)	0.022 (3)	0.026 (3)
N3	0.042 (3)	0.022 (2)	0.042 (3)	0.007 (2)	0.003 (2)	0.003 (2)
N4	0.034 (3)	0.025 (2)	0.035 (3)	0.0016 (19)	0.003 (2)	0.004 (2)
C1	0.033 (3)	0.029 (3)	0.034 (3)	0.009 (2)	0.001 (2)	0.008 (2)
C2	0.034 (3)	0.025 (3)	0.029 (3)	0.000 (2)	0.004 (2)	0.004 (2)
C3	0.039 (3)	0.059 (4)	0.034 (3)	0.009 (3)	0.009 (3)	0.005 (3)
C4	0.046 (4)	0.067 (5)	0.036 (3)	0.009 (3)	0.005 (3)	0.007 (3)
C5	0.037 (3)	0.035 (3)	0.043 (4)	0.006 (3)	−0.003 (3)	0.007 (3)
C6	0.031 (3)	0.065 (4)	0.043 (4)	0.006 (3)	−0.002 (3)	0.011 (3)
C7	0.037 (3)	0.057 (4)	0.042 (4)	0.004 (3)	0.006 (3)	0.009 (3)
C8	0.060 (4)	0.058 (4)	0.042 (4)	0.015 (3)	−0.012 (3)	0.003 (3)

Geometric parameters (Å, º)

Co1—N3^i	2.121 (5)	N4—C7	1.340 (8)
Co1—N3^ii	2.121 (5)	C3—C4	1.378 (9)
Co1—N1	2.129 (5)	C3—H3	0.9300
Co1—N1^iii	2.129 (5)	C4—C5	1.382 (9)
Co1—N4	2.154 (4)	C4—H4	0.9300
Co1—N4^iii	2.154 (4)	C5—C6	1.377 (9)
Cl1—C8	1.744 (8)	C5—C8	1.524 (8)
N1—C1	1.150 (7)	C6—C7	1.385 (9)
N2—C2	1.292 (7)	C6—H6	0.9300
N2—C1	1.300 (7)	C7—H7	0.9300
N3—C2	1.150 (7)	C8—H8A	0.9700
N3—Co1^iv	2.121 (5)	C8—H8B	0.9700
N4—C3	1.334 (7)
N3^i—Co1—N3^ii	180.0 (3)	N3—C2—N2	172.0 (6)
N3^i—Co1—N1	92.10 (19)	N4—C3—C4	123.3 (6)
N3^ii—Co1—N1	87.90 (19)	N4—C3—H3	118.4
N3^i—Co1—N1^iii	87.90 (19)	C4—C3—H3	118.4
N3^ii—Co1—N1^iii	92.10 (19)	C3—C4—C5	119.8 (6)
N1—Co1—N1^iii	180.000 (1)	C3—C4—H4	120.1
N3^i—Co1—N4	91.10 (18)	C5—C4—H4	120.1
N3^ii—Co1—N4	88.90 (18)	C6—C5—C4	117.7 (6)
N1—Co1—N4	90.74 (18)	C6—C5—C8	123.9 (6)
N1^iii—Co1—N4	89.26 (18)	C4—C5—C8	118.5 (6)
N3^i—Co1—N4^iii	88.90 (18)	C5—C6—C7	118.8 (6)
N3^ii—Co1—N4^iii	91.10 (18)	C5—C6—H6	120.6
N1—Co1—N4^iii	89.26 (18)	C7—C6—H6	120.6
N1^iii—Co1—N4^iii	90.74 (18)	N4—C7—C6	124.0 (6)
N4—Co1—N4^iii	180.000 (1)	N4—C7—H7	118.0
C1—N1—Co1	153.7 (5)	C6—C7—H7	118.0
C2—N2—C1	123.1 (5)	C5—C8—Cl1	114.8 (5)
C2—N3—Co1^iv	157.0 (5)	C5—C8—H8A	108.6
C3—N4—C7	116.4 (5)	Cl1—C8—H8A	108.6
C3—N4—Co1	122.7 (4)	C5—C8—H8B	108.6
C7—N4—Co1	120.9 (4)	Cl1—C8—H8B	108.6
N1—C1—N2	173.3 (6)	H8A—C8—H8B	107.5
N3^i—Co1—N1—C1	−164.2 (10)	C7—N4—C3—C4	0.3 (10)
N3^ii—Co1—N1—C1	15.8 (10)	Co1—N4—C3—C4	179.7 (5)
N4—Co1—N1—C1	104.7 (10)	N4—C3—C4—C5	−0.2 (11)
N4^iii—Co1—N1—C1	−75.3 (10)	C3—C4—C5—C6	−0.3 (10)
N3^i—Co1—N4—C3	−43.6 (5)	C3—C4—C5—C8	−179.7 (6)
N3^ii—Co1—N4—C3	136.4 (5)	C4—C5—C6—C7	0.5 (10)
N1—Co1—N4—C3	48.5 (5)	C8—C5—C6—C7	179.9 (6)
N1^iii—Co1—N4—C3	−131.5 (5)	C3—N4—C7—C6	−0.1 (10)
N3^i—Co1—N4—C7	135.8 (5)	Co1—N4—C7—C6	−179.5 (5)
N3^ii—Co1—N4—C7	−44.2 (5)	C5—C6—C7—N4	−0.3 (11)
N1—Co1—N4—C7	−132.1 (5)	C6—C5—C8—Cl1	1.4 (9)
N1^iii—Co1—N4—C7	47.9 (5)	C4—C5—C8—Cl1	−179.3 (5)

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