Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027662/bh6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027662/bh6025Isup2.hkl |
CCDC reference: 226248
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%.
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 Uiso(H) = 1.2Ueq(carrier C atom).
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.
[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) Å3 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0336P)2 + 2.6609P] where P = (Fo2 + 2Fc2)/3 |
1601 reflections | (Δ/σ)max < 0.001 |
124 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.78 e Å−3 |
[Co(C2N3)(C6H6ClN)2] | γ = 102.618 (2)° |
Mr = 446.17 | V = 456.15 (10) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.2910 (9) Å | Mo Kα radiation |
b = 7.4810 (9) Å | µ = 1.25 mm−1 |
c = 9.0070 (13) Å | T = 295 K |
α = 104.444 (2)° | 0.44 × 0.14 × 0.10 mm |
β = 96.971 (2)° |
Bruker APEX area-detector diffractometer | 1601 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1368 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 0.885 | Rint = 0.040 |
2408 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.49 e Å−3 |
1601 reflections | Δρmin = −0.78 e Å−3 |
124 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Co1—N3i | 2.121 (5) | N4—C7 | 1.340 (8) |
Co1—N3ii | 2.121 (5) | C3—C4 | 1.378 (9) |
Co1—N1 | 2.129 (5) | C3—H3 | 0.9300 |
Co1—N1iii | 2.129 (5) | C4—C5 | 1.382 (9) |
Co1—N4 | 2.154 (4) | C4—H4 | 0.9300 |
Co1—N4iii | 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—Co1iv | 2.121 (5) | C8—H8B | 0.9700 |
N4—C3 | 1.334 (7) | ||
N3i—Co1—N3ii | 180.0 (3) | N3—C2—N2 | 172.0 (6) |
N3i—Co1—N1 | 92.10 (19) | N4—C3—C4 | 123.3 (6) |
N3ii—Co1—N1 | 87.90 (19) | N4—C3—H3 | 118.4 |
N3i—Co1—N1iii | 87.90 (19) | C4—C3—H3 | 118.4 |
N3ii—Co1—N1iii | 92.10 (19) | C3—C4—C5 | 119.8 (6) |
N1—Co1—N1iii | 180.000 (1) | C3—C4—H4 | 120.1 |
N3i—Co1—N4 | 91.10 (18) | C5—C4—H4 | 120.1 |
N3ii—Co1—N4 | 88.90 (18) | C6—C5—C4 | 117.7 (6) |
N1—Co1—N4 | 90.74 (18) | C6—C5—C8 | 123.9 (6) |
N1iii—Co1—N4 | 89.26 (18) | C4—C5—C8 | 118.5 (6) |
N3i—Co1—N4iii | 88.90 (18) | C5—C6—C7 | 118.8 (6) |
N3ii—Co1—N4iii | 91.10 (18) | C5—C6—H6 | 120.6 |
N1—Co1—N4iii | 89.26 (18) | C7—C6—H6 | 120.6 |
N1iii—Co1—N4iii | 90.74 (18) | N4—C7—C6 | 124.0 (6) |
N4—Co1—N4iii | 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—Co1iv | 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 |
N3i—Co1—N1—C1 | −164.2 (10) | C7—N4—C3—C4 | 0.3 (10) |
N3ii—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) |
N4iii—Co1—N1—C1 | −75.3 (10) | C3—C4—C5—C6 | −0.3 (10) |
N3i—Co1—N4—C3 | −43.6 (5) | C3—C4—C5—C8 | −179.7 (6) |
N3ii—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) |
N1iii—Co1—N4—C3 | −131.5 (5) | C3—N4—C7—C6 | −0.1 (10) |
N3i—Co1—N4—C7 | 135.8 (5) | Co1—N4—C7—C6 | −179.5 (5) |
N3ii—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) |
N1iii—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. |
Experimental details
Crystal data | |
Chemical formula | [Co(C2N3)(C6H6ClN)2] |
Mr | 446.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 7.2910 (9), 7.4810 (9), 9.0070 (13) |
α, β, γ (°) | 104.444 (2), 96.971 (2), 102.618 (2) |
V (Å3) | 456.15 (10) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.44 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.805, 0.885 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2408, 1601, 1368 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.160, 1.09 |
No. of reflections | 1601 |
No. of parameters | 124 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.78 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXTL.
Co1—N3i | 2.121 (5) | Co1—N4 | 2.154 (4) |
Co1—N1 | 2.129 (5) | ||
N3i—Co1—N1 | 92.10 (19) | N3ii—Co1—N4 | 88.90 (18) |
N3ii—Co1—N1 | 87.90 (19) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+2, −z+1. |
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 MI (Britton, 1990; Batten et al., 2000; Bessler et al., 2000) and MII (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) (MI = Cu or Ag; MII = Cd, Cu, Co, Ni, Zn, Mn or Fe). Cobalt complexes have been synthesized previously but the different kinds of interactions observed for CoII 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 CoII 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 CoII 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 CoII 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 CoII 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).