A pair of L-shaped dicyanamide anions link the bis(N,N-dimethylformamide)cobalt(II) units into a linear chain running along the b axis of the monoclinic crystal of (C2N3)2(DMF)2Co. The Co atom and the dicyanamido bridging ligand occupy special positions of symmetry 2/m and m, respectively. The coordination polyhedron of the Co atom is close to a regular octahedron.
Supporting information
CCDC reference: 217352
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (N-C) = 0.005 Å
- R factor = 0.029
- wR factor = 0.087
- Data-to-parameter ratio = 11.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.528 0.721
Tmin' and Tmax expected: 0.605 0.705
RR' = 0.853
Please check that your absorption correction is appropriate.
PLAT_702 Alert C Angle Calc 88.44(5), Rep 88.50(10), Dev.. 1.20 Sigma
O1 -CO1 -N1 1.555 1.555 2.656
PLAT_702 Alert C Angle Calc 88.44(5), Rep 88.50(10), Dev.. 1.20 Sigma
O1 -CO1 -N1 1.555 1.555 5.666
PLAT_702 Alert C Angle Calc 88.44(5), Rep 88.50(10), Dev.. 1.20 Sigma
O1 -CO1 -N1 5.666 1.555 1.555
PLAT_702 Alert C Angle Calc 88.44(5), Rep 88.50(10), Dev.. 1.20 Sigma
O1 -CO1 -N1 5.666 1.555 6.565
PLAT_731 Alert C Bond Calc 0.94(3), Rep 0.940(10) ...... 3.00 su-Rat
C2 -H2 1.555 1.555
PLAT_731 Alert C Bond Calc 0.94(3), Rep 0.940(10) ...... 3.00 su-Rat
C3 -H3A 1.555 1.555
PLAT_731 Alert C Bond Calc 0.95(3), Rep 0.950(10) ...... 3.00 su-Rat
C3 -H3B 1.555 1.555
PLAT_731 Alert C Bond Calc 0.93(4), Rep 0.940(10) ...... 4.00 su-Rat
C4 -H4A 1.555 1.555
PLAT_733 Alert C Torsion Calc -46.02(4), Rep -46.00(10) ...... 2.50 su-Rat
N1 -CO1 -O1 -C2 1.555 1.555 1.555 1.555
PLAT_733 Alert C Torsion Calc 133.98(4), Rep 134.00(10) ...... 2.50 su-Rat
N1 -CO1 -O1 -C2 5.666 1.555 1.555 1.555
PLAT_733 Alert C Torsion Calc 46.02(4), Rep 46.00(10) ...... 2.50 su-Rat
N1 -CO1 -O1 -C2 6.565 1.555 1.555 1.555
PLAT_733 Alert C Torsion Calc -133.98(4), Rep -134.00(10) ...... 2.50 su-Rat
N1 -CO1 -O1 -C2 2.656 1.555 1.555 1.555
PLAT_735 Alert C D-H Calc 0.94(3), Rep 0.940(10) ...... 3.00 su-Rat
C2 -H2 1.555 1.555
PLAT_736 Alert C H...A Calc 2.54(3), Rep 2.530(10) ...... 3.00 su-Rat
H2 -N2 1.555 7.666
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
15 Alert Level C = Please check
Cobalt(II) chloride (0.12 g, 0.5 mmol) and sodium dicyanamide (0.09 g, 1.0 mmol) were placed in a 10:1 v/v methanol/DMF mixture and the solution was heated until the reagents dissolved. Polyhedral crystals separated from the solution in about 80% yield after 10 d.
The diffraction data were of sufficiently high quality to allow for the refinement of the H atoms. These were refined subject to bond constraints of C—H = 0.95 (1) Å for the methyl groups, the H···H distance was restrained to 1.50 (1) Å.
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97.
catena-poly[bis(µ-1,5-dicyanamido)-bis(
N,
N-dimethylformamide)cobalt(II)]
top
Crystal data top
C10H14CoN8O2 | F(000) = 346 |
Mr = 337.22 | Dx = 1.499 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 13.525 (4) Å | Cell parameters from 282 reflections |
b = 7.383 (2) Å | θ = 3.3–27.5° |
c = 8.094 (3) Å | µ = 1.17 mm−1 |
β = 112.399 (5)° | T = 293 K |
V = 747.3 (4) Å3 | Block, pink |
Z = 2 | 0.42 × 0.36 × 0.30 mm |
Data collection top
Rigaku Mercury CCD diffractometer | 878 independent reflections |
Radiation source: rotating-anode generator | 847 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scan | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan CrystalClear (Rigaku, 2002) | h = −17→12 |
Tmin = 0.528, Tmax = 0.721 | k = −9→9 |
2432 measured reflections | l = −9→10 |
Refinement top
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0676P)2 + 0.0203P] where P = (Fo2 + 2Fc2)/3 |
878 reflections | (Δ/σ)max = 0.001 |
76 parameters | Δρmax = 0.36 e Å−3 |
5 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C10H14CoN8O2 | V = 747.3 (4) Å3 |
Mr = 337.22 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 13.525 (4) Å | µ = 1.17 mm−1 |
b = 7.383 (2) Å | T = 293 K |
c = 8.094 (3) Å | 0.42 × 0.36 × 0.30 mm |
β = 112.399 (5)° | |
Data collection top
Rigaku Mercury CCD diffractometer | 878 independent reflections |
Absorption correction: multi-scan CrystalClear (Rigaku, 2002) | 847 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.721 | Rint = 0.019 |
2432 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 5 restraints |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.36 e Å−3 |
878 reflections | Δρmin = −0.36 e Å−3 |
76 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.5000 | 0.5000 | 0.5000 | 0.0247 (2) | |
O1 | 0.5839 (1) | 0.5000 | 0.7776 (2) | 0.036 (1) | |
N1 | 0.5997 (1) | 0.7068 (2) | 0.4662 (2) | 0.036 (1) | |
N2 | 0.6333 (2) | 1.0000 | 0.3560 (3) | 0.041 (1) | |
N3 | 0.7372 (2) | 0.5000 | 1.0206 (3) | 0.039 (1) | |
C1 | 0.6142 (1) | 0.8476 (2) | 0.4199 (2) | 0.028 (1) | |
C2 | 0.6826 (2) | 0.5000 | 0.8466 (3) | 0.033 (1) | |
C3 | 0.6836 (3) | 0.5000 | 1.1447 (4) | 0.080 (1) | |
C4 | 0.8536 (2) | 0.5000 | 1.0963 (4) | 0.050 (1) | |
H2 | 0.726 (2) | 0.5000 | 0.780 (4) | 0.04 (1)* | |
H3a | 0.738 (3) | 0.5000 | 1.259 (4) | 0.12 (2)* | |
H3b | 0.646 (3) | 0.389 (3) | 1.131 (6) | 0.16 (2)* | |
H4a | 0.879 (3) | 0.5000 | 1.004 (4) | 0.06 (1)* | |
H4b | 0.886 (2) | 0.401 (2) | 1.171 (3) | 0.08 (1)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0297 (3) | 0.0196 (3) | 0.0242 (3) | 0.000 | 0.0097 (2) | 0.000 |
O1 | 0.035 (1) | 0.048 (1) | 0.024 (1) | 0.000 | 0.009 (1) | 0.000 |
N1 | 0.043 (1) | 0.026 (1) | 0.044 (1) | −0.004 (1) | 0.023 (1) | −0.002 (1) |
N2 | 0.062 (1) | 0.026 (1) | 0.052 (1) | 0.000 | 0.042 (1) | 0.000 |
N3 | 0.036 (1) | 0.050 (1) | 0.027 (1) | 0.000 | 0.008 (1) | 0.000 |
C1 | 0.027 (1) | 0.028 (1) | 0.031 (1) | 0.000 (1) | 0.015 (1) | −0.005 (1) |
C2 | 0.038 (1) | 0.035 (1) | 0.027 (1) | 0.000 | 0.013 (1) | 0.000 |
C3 | 0.057 (2) | 0.157 (5) | 0.029 (1) | 0.000 | 0.021 (1) | 0.000 |
C4 | 0.036 (1) | 0.061 (2) | 0.043 (1) | 0.000 | 0.004 (1) | 0.000 |
Geometric parameters (Å, º) top
Co1—O1 | 2.096 (2) | N2—C1 | 1.305 (2) |
Co1—O1i | 2.096 (2) | N3—C2 | 1.318 (3) |
Co1—N1 | 2.123 (2) | N3—C3 | 1.446 (4) |
Co1—N1ii | 2.123 (2) | N3—C4 | 1.455 (4) |
Co1—N1i | 2.123 (2) | C2—H2 | 0.94 (1) |
Co1—N1iii | 2.123 (2) | C3—H3a | 0.94 (1) |
O1—C2 | 1.235 (3) | C3—H3b | 0.95 (1) |
N1—C1 | 1.147 (2) | C4—H4a | 0.94 (1) |
N2—C1iv | 1.305 (2) | C4—H4b | 0.94 (1) |
| | | |
O1—Co1—O1i | 180 | C1—N1—Co1 | 152.9 (1) |
O1—Co1—N1 | 91.6 (1) | C1iv—N2—C1 | 119.2 (2) |
O1—Co1—N1ii | 88.5 (1) | C2—N3—C3 | 121.1 (2) |
O1—Co1—N1i | 88.5 (1) | C2—N3—C4 | 121.7 (2) |
O1—Co1—N1iii | 91.6 (1) | C3—N3—C4 | 117.1 (2) |
O1i—Co1—N1 | 88.5 (1) | N1—C1—N2 | 174.6 (2) |
O1i—Co1—N1ii | 91.6 (1) | O1—C2—N3 | 123.5 (2) |
O1i—Co1—N1i | 91.6 (1) | O1—C2—H2 | 123 (2) |
O1i—Co1—N1iii | 88.5 (1) | N3—C2—H2 | 113 (2) |
N1—Co1—N1ii | 88.0 (1) | N3—C3—H3a | 105 (4) |
N1—Co1—N1i | 180.0 (1) | N3—C3—H3b | 108 (3) |
N1—Co1—N1iii | 92.0 (1) | H3a—C3—H3b | 108 (3) |
N1i—Co1—N1ii | 92.0 (1) | N3—C4—H4a | 110 (2) |
N1i—Co1—N1iii | 88.0 (1) | N3—C4—H4b | 116 (2) |
N1ii—Co1—N1iii | 180.0 (1) | H4b—C4—H4b | 107 (2) |
C2—O1—Co1 | 122.3 (2) | | |
| | | |
N1—Co1—O1—C2 | −46.0 (1) | N1iii—Co1—N1—C1 | 147.2 (3) |
N1i—Co1—O1—C2 | 134.0 (1) | N1ii—Co1—N1—C1 | −32.8 (3) |
N1iii—Co1—O1—C2 | 46.0 (1) | Co1—O1—C2—N3 | 180.0 |
N1ii—Co1—O1—C2 | −134.0 (1) | C3—N3—C2—O1 | 0.0 |
O1i—Co1—N1—C1 | 58.8 (3) | C4—N3—C2—O1 | 180.0 |
O1—Co1—N1—C1 | −121.2 (3) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1; (iii) x, −y+1, z; (iv) x, −y+2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N2v | 0.94 (1) | 2.53 (1) | 3.464 (3) | 172 (3) |
Symmetry code: (v) −x+3/2, −y+3/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C10H14CoN8O2 |
Mr | 337.22 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 13.525 (4), 7.383 (2), 8.094 (3) |
β (°) | 112.399 (5) |
V (Å3) | 747.3 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.17 |
Crystal size (mm) | 0.42 × 0.36 × 0.30 |
|
Data collection |
Diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | Multi-scan CrystalClear (Rigaku, 2002) |
Tmin, Tmax | 0.528, 0.721 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2432, 878, 847 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.087, 1.06 |
No. of reflections | 878 |
No. of parameters | 76 |
No. of restraints | 5 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.36, −0.36 |
Selected geometric parameters (Å, º) topCo1—O1 | 2.096 (2) | N2—C1 | 1.305 (2) |
Co1—N1 | 2.123 (2) | N3—C2 | 1.318 (3) |
O1—C2 | 1.235 (3) | N3—C3 | 1.446 (4) |
N1—C1 | 1.147 (2) | N3—C4 | 1.455 (4) |
| | | |
O1—Co1—N1 | 91.6 (1) | N1—Co1—N1i | 88.0 (1) |
O1—Co1—N1i | 88.5 (1) | | |
Symmetry code: (i) −x+1, y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N2ii | 0.94 (1) | 2.53 (1) | 3.464 (3) | 172 (3) |
Symmetry code: (ii) −x+3/2, −y+3/2, −z+1. |
Owing to its capacity for binding to metal atoms in different modes, the dicyanamido anion, [N(CN)2]− (dca), is an excellent building block for the synthesis of a wide range of metal complexes. Polymeric dicyanamido complexes possess interesting magnetic properties and unusual coordination architectures (Miller & Manson, 2001). A number of one-, two- and three-dimensional coordination polymers featuring various structural motifs have been reported. The one-dimensional [M(dca)2L] chains (L = neutral terminal or chelating ligand) (Manson et al., 1999; Vangdal et al., 2002), two-dimensional β-M(dca)2 sheets and three-dimensional rutile-like α-M(dca)2 networks (Miller & Manson, 2001), along with other motifs (Gao et al., 2002; Shi et al., 2002; Yeung et al., 2002) may be mentioned as a few examples. The recently published structures of benzyltrialkylammonium tris(dicyanamido)metalates, [C6H5CH2NR3][M(dca)3] (R = n-C4H9, M = Mn, Co; R = C2H5, M = Mn, Fe) (Tong et al., 2003), exhibit a three-dimensional architecture based on a cubic network of [MN6] coordination octahedra, following the motif of the α-Po-like type, and bridged by the dca ligand.
In the title compound, (I), the bis-DMF adduct of Co(dca)2, forms one-dimensional chains in the crystal (Fig. 1). The Co atom lies at the 2c Wyckoff position (1/2,1/2,1/2) of site symmetry 2/m. The dca occupies a special position across the mirror plane (Wyckoff 4i). The Co atom has an octahedral environment, formed by four N atoms belonging to four different dca groups [Co1—N1 2.123 (2) Å] and two O atoms of two DMF ligands [Co1—O1 2.096 (2) Å]; the DMF ligands, in compliance with symmetry requirements, are trans to each other. Adjacent chains are held together by a weak C—H···N hydrogen bond, forming layers parallel to the ab plane (Fig. 2; Table 2).