metal-organic compounds
A triclinic polymorph of catena-poly[[bis(N,N-dimethylformamide-κO)cobalt(II)]-di-μ-1,5-dicyanamido-κ4N1:N5]
aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
*Correspondence e-mail: mengsc@ujs.edu.cn
The title compound, [Co(C2N3)2(C3H7NO)2]n, is a triclinic polymorph of the previously reported monoclinic structure [Tong et al. (2003). Acta Cryst. E59, m405–m407]. The CoII ion lies on an inversion centre and adopts an almost regular octahedral N4O2 coordination geometry. Adjacent CoII atoms are connected by two bridging dicyanamide ligands, resulting in the formation of neutral chains parallel to the b axis. The title complex is isotypic with the MnII analogue but not with the NiII analogue.
Related literature
For the design and synthesis of metal-organic compounds, see: Long & Yaghi (2009). For the structures of the MnII and NiII analogues, see: Batten et al. (1999); Shen & Yuan (2005). For the structure of the monoclinic polymorph, see: Tong et al. (2003).
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812043310/rz5015sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043310/rz5015Isup2.hkl
Co(NO3)2.6H2O (116.6 mg, 0.4 mmol) was added into 1 ml dmf with thorough stir for 5 minutes. After filtration, the purple filtrate was carefully laid on the surface with a solution of NaN(CN)2 (89.1 mg, 1 mmol) in 1 ml dmf and 4 ml i-PrOH. Purple block crystals were obtained after five days.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.96 Å, and with Uiso(H) = 1.5Ueq(C) or 1.2Ueq(C) for methyl and formyl H atoms, respectively.
Data collection: CrystalClear (Rigaku, 2008); cell
CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The polymeric structure of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted. Symmetry code: (i) 1 - x, -y, 1 - z. |
[Co(C2N3)2(C3H7NO)2] | Z = 1 |
Mr = 337.22 | F(000) = 173 |
Triclinic, P1 | Dx = 1.526 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4315 (13) Å | Cell parameters from 1585 reflections |
b = 7.3879 (15) Å | θ = 4.5–29.1° |
c = 8.6210 (17) Å | µ = 1.19 mm−1 |
α = 105.69 (3)° | T = 150 K |
β = 107.94 (3)° | Block, purple |
γ = 96.19 (3)° | 0.22 × 0.18 × 0.15 mm |
V = 366.93 (17) Å3 |
Rigaku Saturn724+ diffractometer | 1319 independent reflections |
Radiation source: fine-focus sealed tube | 1242 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 25.3°, θmin = 4.0° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008) | h = −7→7 |
Tmin = 0.845, Tmax = 1.000 | k = −8→7 |
2514 measured reflections | l = −10→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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0266P)2 + 0.119P] where P = (Fo2 + 2Fc2)/3 |
1319 reflections | (Δ/σ)max < 0.001 |
97 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Co(C2N3)2(C3H7NO)2] | γ = 96.19 (3)° |
Mr = 337.22 | V = 366.93 (17) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.4315 (13) Å | Mo Kα radiation |
b = 7.3879 (15) Å | µ = 1.19 mm−1 |
c = 8.6210 (17) Å | T = 150 K |
α = 105.69 (3)° | 0.22 × 0.18 × 0.15 mm |
β = 107.94 (3)° |
Rigaku Saturn724+ diffractometer | 1319 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008) | 1242 reflections with I > 2σ(I) |
Tmin = 0.845, Tmax = 1.000 | Rint = 0.015 |
2514 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.22 e Å−3 |
1319 reflections | Δρmin = −0.24 e Å−3 |
97 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 | 0.0000 | 0.5000 | 0.03475 (14) | |
O1 | 0.7337 (2) | 0.1252 (2) | 0.75360 (17) | 0.0458 (3) | |
N1 | 0.3153 (3) | −0.1843 (2) | 0.5846 (2) | 0.0450 (4) | |
N2 | 0.3184 (3) | 0.2157 (2) | 0.5512 (2) | 0.0461 (4) | |
N3 | 0.2307 (3) | −0.4729 (2) | 0.6597 (2) | 0.0540 (5) | |
N4 | 1.0908 (3) | 0.2096 (2) | 0.9389 (2) | 0.0429 (4) | |
C1 | 0.2790 (3) | −0.3244 (3) | 0.6133 (2) | 0.0361 (4) | |
C2 | 0.2822 (3) | 0.3654 (3) | 0.5966 (2) | 0.0335 (4) | |
C3 | 0.9359 (3) | 0.1312 (3) | 0.7855 (2) | 0.0397 (4) | |
H3C | 0.9817 | 0.0763 | 0.6944 | 0.048* | |
C4 | 1.0358 (5) | 0.3018 (4) | 1.0885 (3) | 0.0620 (6) | |
H4A | 0.8777 | 0.2958 | 1.0544 | 0.093* | |
H4B | 1.1137 | 0.4337 | 1.1379 | 0.093* | |
H4C | 1.0796 | 0.2367 | 1.1720 | 0.093* | |
C5 | 1.3232 (4) | 0.2040 (4) | 0.9659 (3) | 0.0666 (7) | |
H5A | 1.3381 | 0.1399 | 0.8582 | 0.100* | |
H5B | 1.3753 | 0.1357 | 1.0456 | 0.100* | |
H5C | 1.4105 | 0.3329 | 1.0117 | 0.100* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0364 (2) | 0.02626 (19) | 0.0418 (2) | 0.00779 (14) | 0.01291 (16) | 0.01186 (15) |
O1 | 0.0401 (8) | 0.0490 (8) | 0.0434 (8) | 0.0089 (6) | 0.0120 (7) | 0.0100 (7) |
N1 | 0.0503 (10) | 0.0333 (9) | 0.0546 (11) | 0.0081 (7) | 0.0214 (9) | 0.0163 (8) |
N2 | 0.0510 (10) | 0.0356 (9) | 0.0582 (11) | 0.0160 (8) | 0.0235 (9) | 0.0177 (8) |
N3 | 0.0846 (14) | 0.0345 (9) | 0.0629 (12) | 0.0196 (9) | 0.0489 (11) | 0.0178 (9) |
N4 | 0.0446 (10) | 0.0461 (9) | 0.0336 (9) | 0.0087 (8) | 0.0104 (8) | 0.0102 (7) |
C1 | 0.0374 (10) | 0.0322 (10) | 0.0381 (10) | 0.0096 (8) | 0.0155 (9) | 0.0070 (8) |
C2 | 0.0331 (9) | 0.0331 (10) | 0.0348 (10) | 0.0050 (8) | 0.0114 (8) | 0.0127 (8) |
C3 | 0.0451 (12) | 0.0366 (10) | 0.0370 (11) | 0.0083 (9) | 0.0145 (9) | 0.0110 (8) |
C4 | 0.0828 (18) | 0.0611 (14) | 0.0381 (12) | 0.0177 (13) | 0.0210 (12) | 0.0087 (11) |
C5 | 0.0450 (13) | 0.0853 (18) | 0.0556 (15) | 0.0097 (12) | 0.0047 (11) | 0.0174 (13) |
Co1—N2i | 2.1061 (17) | N4—C3 | 1.313 (3) |
Co1—N2 | 2.1061 (17) | N4—C5 | 1.448 (3) |
Co1—O1 | 2.1157 (17) | N4—C4 | 1.452 (3) |
Co1—O1i | 2.1157 (17) | C2—N3iii | 1.295 (2) |
Co1—N1 | 2.1254 (17) | C3—H3C | 0.9300 |
Co1—N1i | 2.1254 (17) | C4—H4A | 0.9600 |
O1—C3 | 1.237 (2) | C4—H4B | 0.9600 |
N1—C1 | 1.145 (2) | C4—H4C | 0.9600 |
N2—C2 | 1.144 (2) | C5—H5A | 0.9600 |
N3—C2ii | 1.295 (2) | C5—H5B | 0.9600 |
N3—C1 | 1.304 (2) | C5—H5C | 0.9600 |
N2i—Co1—N2 | 180.00 (11) | C3—N4—C4 | 121.59 (19) |
N2i—Co1—O1 | 90.92 (7) | C5—N4—C4 | 117.31 (19) |
N2—Co1—O1 | 89.08 (7) | N1—C1—N3 | 173.5 (2) |
N2i—Co1—O1i | 89.08 (7) | N2—C2—N3iii | 173.04 (19) |
N2—Co1—O1i | 90.92 (7) | O1—C3—N4 | 124.73 (18) |
O1—Co1—O1i | 180.0 | O1—C3—H3C | 117.6 |
N2i—Co1—N1 | 88.01 (7) | N4—C3—H3C | 117.6 |
N2—Co1—N1 | 91.99 (7) | N4—C4—H4A | 109.5 |
O1—Co1—N1 | 90.34 (7) | N4—C4—H4B | 109.5 |
O1i—Co1—N1 | 89.66 (7) | H4A—C4—H4B | 109.5 |
N2i—Co1—N1i | 91.99 (7) | N4—C4—H4C | 109.5 |
N2—Co1—N1i | 88.01 (7) | H4A—C4—H4C | 109.5 |
O1—Co1—N1i | 89.66 (7) | H4B—C4—H4C | 109.5 |
O1i—Co1—N1i | 90.34 (7) | N4—C5—H5A | 109.5 |
N1—Co1—N1i | 180.00 (8) | N4—C5—H5B | 109.5 |
C3—O1—Co1 | 121.36 (13) | H5A—C5—H5B | 109.5 |
C1—N1—Co1 | 151.54 (16) | N4—C5—H5C | 109.5 |
C2—N2—Co1 | 159.60 (16) | H5A—C5—H5C | 109.5 |
C2ii—N3—C1 | 120.72 (16) | H5B—C5—H5C | 109.5 |
C3—N4—C5 | 121.09 (18) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y−1, z; (iii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C2N3)2(C3H7NO)2] |
Mr | 337.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 6.4315 (13), 7.3879 (15), 8.6210 (17) |
α, β, γ (°) | 105.69 (3), 107.94 (3), 96.19 (3) |
V (Å3) | 366.93 (17) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.22 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Rigaku Saturn724+ diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2008) |
Tmin, Tmax | 0.845, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2514, 1319, 1242 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.061, 1.04 |
No. of reflections | 1319 |
No. of parameters | 97 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.24 |
Computer programs: CrystalClear (Rigaku, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the Foundation of Jiangsu University (08JDG037).
References
Batten, S. R., Jensen, P., Kepert, C. J., Kurmoo, M., Moubaraki, B., Murray, K. S. & Price, D. J. (1999). J. Chem. Soc. Dalton Trans. pp. 2987–2997 CrossRef Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The design and synthesis of metal-organic compounds have attracted great attention in recent years (Long & Yaghi, 2009), in particular focusing on the properties of flexible bridging ligands able to construct metal-organic compounds with various structures. The title compound is constructed by the flexible dicyanamide bridging ligand through diffusion reaction.
As illustrated in Fig. 1, the cobalt(II) ion lies on an inversion centre and adopts an octahedral coordination geometry. Metal atoms are connected by two dicyanamide bridging ligands, resulting in the formation of neutral chains parallel the b axis. The title complex is isotypic with the Mn analogue (Batten et al., 1999) but not with the Ni analogue (Shen & Yuan, 2005). A monoclinic polymorph of the title compound was previously reported (Tong et al., 2003).