supplementary materials


rz5015 scheme

Acta Cryst. (2012). E68, m1404    [ doi:10.1107/S1600536812043310 ]

A triclinic polymorph of catena-poly[[bis(N,N-dimethylformamide-[kappa]O)cobalt(II)]-di-[mu]-1,5-dicyanamido-[kappa]4N1:N5]

S. C. Meng

Abstract top

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.

Comment top

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).

Related literature top

For the design and synthesis of metal-organic compounds, see: Long & Yaghi (2009). For the structures of the Mn and Ni analogues, see: Batten et al. (1999); Shen & Yuan (2005). For the structure of the monoclinic polymorph, see: Tong et al. (2003).

Experimental top

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.

Refinement top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: 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).

Figures top
[Figure 1] 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.
catena-poly[[bis(N,N-dimethylformamide- κO)cobalt(II)]-di-µ-1,5-dicyanamido-κ4N1:N5] top
Crystal data top
[Co(C2N3)2(C3H7NO)2]Z = 1
Mr = 337.22F(000) = 173
Triclinic, P1Dx = 1.526 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.4315 (13) ÅCell parameters from 1585 reflections
b = 7.3879 (15) Åθ = 4.5–29.1°
c = 8.6210 (17) ŵ = 1.19 mm1
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
Data collection top
Rigaku Saturn724+
diffractometer
1319 independent reflections
Radiation source: fine-focus sealed tube1242 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 25.3°, θmin = 4.0°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
h = 77
Tmin = 0.845, Tmax = 1.000k = 87
2514 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-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 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
[Co(C2N3)2(C3H7NO)2]γ = 96.19 (3)°
Mr = 337.22V = 366.93 (17) Å3
Triclinic, P1Z = 1
a = 6.4315 (13) ÅMo Kα radiation
b = 7.3879 (15) ŵ = 1.19 mm1
c = 8.6210 (17) ÅT = 150 K
α = 105.69 (3)°0.22 × 0.18 × 0.15 mm
β = 107.94 (3)°
Data collection top
Rigaku Saturn724+
diffractometer
1242 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
Rint = 0.015
Tmin = 0.845, Tmax = 1.000θmax = 25.3°
2514 measured reflectionsStandard reflections: 0
1319 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.22 e Å3
S = 1.04Δρmin = 0.24 e Å3
1319 reflectionsAbsolute structure: ?
97 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
Co10.50000.00000.50000.03475 (14)
O10.7337 (2)0.1252 (2)0.75360 (17)0.0458 (3)
N10.3153 (3)0.1843 (2)0.5846 (2)0.0450 (4)
N20.3184 (3)0.2157 (2)0.5512 (2)0.0461 (4)
N30.2307 (3)0.4729 (2)0.6597 (2)0.0540 (5)
N41.0908 (3)0.2096 (2)0.9389 (2)0.0429 (4)
C10.2790 (3)0.3244 (3)0.6133 (2)0.0361 (4)
C20.2822 (3)0.3654 (3)0.5966 (2)0.0335 (4)
C30.9359 (3)0.1312 (3)0.7855 (2)0.0397 (4)
H3C0.98170.07630.69440.048*
C41.0358 (5)0.3018 (4)1.0885 (3)0.0620 (6)
H4A0.87770.29581.05440.093*
H4B1.11370.43371.13790.093*
H4C1.07960.23671.17200.093*
C51.3232 (4)0.2040 (4)0.9659 (3)0.0666 (7)
H5A1.33810.13990.85820.100*
H5B1.37530.13571.04560.100*
H5C1.41050.33291.01170.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0364 (2)0.02626 (19)0.0418 (2)0.00779 (14)0.01291 (16)0.01186 (15)
O10.0401 (8)0.0490 (8)0.0434 (8)0.0089 (6)0.0120 (7)0.0100 (7)
N10.0503 (10)0.0333 (9)0.0546 (11)0.0081 (7)0.0214 (9)0.0163 (8)
N20.0510 (10)0.0356 (9)0.0582 (11)0.0160 (8)0.0235 (9)0.0177 (8)
N30.0846 (14)0.0345 (9)0.0629 (12)0.0196 (9)0.0489 (11)0.0178 (9)
N40.0446 (10)0.0461 (9)0.0336 (9)0.0087 (8)0.0104 (8)0.0102 (7)
C10.0374 (10)0.0322 (10)0.0381 (10)0.0096 (8)0.0155 (9)0.0070 (8)
C20.0331 (9)0.0331 (10)0.0348 (10)0.0050 (8)0.0114 (8)0.0127 (8)
C30.0451 (12)0.0366 (10)0.0370 (11)0.0083 (9)0.0145 (9)0.0110 (8)
C40.0828 (18)0.0611 (14)0.0381 (12)0.0177 (13)0.0210 (12)0.0087 (11)
C50.0450 (13)0.0853 (18)0.0556 (15)0.0097 (12)0.0047 (11)0.0174 (13)
Geometric parameters (Å, º) top
Co1—N2i2.1061 (17)N4—C31.313 (3)
Co1—N22.1061 (17)N4—C51.448 (3)
Co1—O12.1157 (17)N4—C41.452 (3)
Co1—O1i2.1157 (17)C2—N3iii1.295 (2)
Co1—N12.1254 (17)C3—H3C0.9300
Co1—N1i2.1254 (17)C4—H4A0.9600
O1—C31.237 (2)C4—H4B0.9600
N1—C11.145 (2)C4—H4C0.9600
N2—C21.144 (2)C5—H5A0.9600
N3—C2ii1.295 (2)C5—H5B0.9600
N3—C11.304 (2)C5—H5C0.9600
N2i—Co1—N2180.00 (11)C3—N4—C4121.59 (19)
N2i—Co1—O190.92 (7)C5—N4—C4117.31 (19)
N2—Co1—O189.08 (7)N1—C1—N3173.5 (2)
N2i—Co1—O1i89.08 (7)N2—C2—N3iii173.04 (19)
N2—Co1—O1i90.92 (7)O1—C3—N4124.73 (18)
O1—Co1—O1i180.0O1—C3—H3C117.6
N2i—Co1—N188.01 (7)N4—C3—H3C117.6
N2—Co1—N191.99 (7)N4—C4—H4A109.5
O1—Co1—N190.34 (7)N4—C4—H4B109.5
O1i—Co1—N189.66 (7)H4A—C4—H4B109.5
N2i—Co1—N1i91.99 (7)N4—C4—H4C109.5
N2—Co1—N1i88.01 (7)H4A—C4—H4C109.5
O1—Co1—N1i89.66 (7)H4B—C4—H4C109.5
O1i—Co1—N1i90.34 (7)N4—C5—H5A109.5
N1—Co1—N1i180.00 (8)N4—C5—H5B109.5
C3—O1—Co1121.36 (13)H5A—C5—H5B109.5
C1—N1—Co1151.54 (16)N4—C5—H5C109.5
C2—N2—Co1159.60 (16)H5A—C5—H5C109.5
C2ii—N3—C1120.72 (16)H5B—C5—H5C109.5
C3—N4—C5121.09 (18)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y1, z; (iii) x, y+1, z.
Acknowledgements top

This work was supported by the Foundation of Jiangsu University (08JDG037).

references
References top

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.

Long, J. R. & Yaghi, O. M. (2009). Chem. Soc. Rev. 38, 1213–1214.

Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shen, X.-P. & Yuan, A.-H. (2005). Acta Cryst. E61, m1937–m1939.

Tong, M.-L., Zhou, A.-J., Hu, S., Chen, X.-M. & Ng, S. W. (2003). Acta Cryst. E59, m405–m407.