supplementary materials


rz5034 scheme

Acta Cryst. (2013). E69, m90    [ doi:10.1107/S1600536812051252 ]

catena-Poly[[bis(4-methylpyridine-[kappa]N)cobalt(II)]-di-[mu]-dicyanamido-[kappa]2N1:N5]

W. Huang, J. Zhang and C. Zhang

Abstract top

Cobalt(II) nitrate hexahydrate and sodium dicyanamide self-assembled in dimethylformamide (DMF) and 4-methylpyridine solutions to form the title compound, [Co(C2N3)2(C6H7N)2]n. The Co2+ ion lies on an inversion center and adopts an octahedral coordination geometry in which four N atoms from four different dicyanamide ligands lie in the equatorial plane and two 4-methylpyridine N atoms occupy the axial positions. The CoII atoms are connected by two bridging dicyanamide ligands, resulting in a chain parallel to the c axis. The chains are connected into a three-dimensional network by C-H...N hydrogen bonds.

Comment top

The design and syntheses of metal-organic compounds have attracted great attention in recent years because of not only their intriguing architectures and topologies (Eddaoudi et al., 2001) but also their potential applications (Banerjee et al., 2008). The title compound {Co[N(CN)2]2(NC6H7)2}n is constructed by the flexible dicyanamide bridging ligands through diffusion reaction.

As illustrated in Fig. 1, Co2+ ion lies on an inversion center and adopts an octahedral coordination geometry, where four N atoms from four different dicyanamide ligands lie in the equatorial plane and two 4-methylpyridine N atoms occupy the axial positions. The Co atoms are connected by two dicyanamide ligands, resulting in a neutral chain along the c-axis. In the crystal, the chains are linked by C—H···N hydrogen bonds (Table 1) into a three-dimensional network.

Related literature top

The design and syntheses of metal-organic compounds has attracted great attention not only as a result of their intriguing architectures and topologies (Eddaoudi et al., 2001) but also because of their potential applications (Banerjee et al., 2008).

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 the solution of NaN(CN)2 (89.1 mg, 1 mmol) in 1 ml dmf, 1 ml 4-methylpyridine and 5 ml i-PrOH. Pink block crystals were obtained after two weeks.

Refinement top

H atoms were positioned geometrically and refined with riding model, with Uiso = 1.5Ueq and 1.2Ueq for methyl and pyridyl H atoms, respectively. The C—H bonds are 0.96 Å in methyl and 0.93 Å in pyridyl.

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. Portion of the polymeric chain of the title compound, with 30% probability displacement ellipsoids. All H atoms have been omitted. Symmetry code: (i) 2-x, -y, 1-z.
catena-Poly[[bis(4-methylpyridine-κN)cobalt(II)]- di-µ-dicyanamido-κ2N1:N5] top
Crystal data top
[Co(C2N3)2(C6H7N)2]F(000) = 386
Mr = 377.28Dx = 1.463 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3521 reflections
a = 9.3686 (19) Åθ = 3.1–28.7°
b = 13.080 (3) ŵ = 1.02 mm1
c = 7.3048 (15) ÅT = 150 K
β = 106.86 (3)°Block, pink
V = 856.7 (3) Å30.21 × 0.17 × 0.15 mm
Z = 2
Data collection top
Rigaku Saturn724+
diffractometer
1549 independent reflections
Radiation source: fine-focus sealed tube1419 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 25.4°, θmin = 3.3°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
h = 1011
Tmin = 0.815, Tmax = 1.000k = 1215
4994 measured reflectionsl = 88
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0483P)2 + 0.6117P]
where P = (Fo2 + 2Fc2)/3
1549 reflections(Δ/σ)max < 0.001
115 parametersΔρmax = 0.94 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
[Co(C2N3)2(C6H7N)2]V = 856.7 (3) Å3
Mr = 377.28Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.3686 (19) ŵ = 1.02 mm1
b = 13.080 (3) ÅT = 150 K
c = 7.3048 (15) Å0.21 × 0.17 × 0.15 mm
β = 106.86 (3)°
Data collection top
Rigaku Saturn724+
diffractometer
1419 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2008)
Rint = 0.016
Tmin = 0.815, Tmax = 1.000θmax = 25.4°
4994 measured reflectionsStandard reflections: 0
1549 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.94 e Å3
S = 1.07Δρmin = 0.26 e Å3
1549 reflectionsAbsolute structure: ?
115 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
Co11.00000.00000.50000.01854 (16)
N10.86523 (19)0.07208 (14)0.6510 (3)0.0262 (4)
N20.87457 (19)0.07142 (14)1.2428 (2)0.0249 (4)
N30.76592 (19)0.12944 (15)0.9113 (2)0.0275 (4)
N40.85008 (18)0.12713 (13)0.4394 (2)0.0213 (4)
C10.8228 (2)0.09665 (15)0.7775 (3)0.0203 (4)
C20.8276 (2)0.09642 (15)1.0853 (3)0.0194 (4)
C30.7023 (2)0.11338 (17)0.3732 (3)0.0274 (5)
H3B0.66560.04690.35620.033*
C40.6022 (2)0.19299 (18)0.3293 (3)0.0315 (5)
H4A0.50060.17960.28280.038*
C50.6525 (2)0.29340 (17)0.3544 (3)0.0287 (5)
C60.5461 (3)0.3821 (2)0.3074 (4)0.0420 (6)
H6A0.44580.35700.26150.063*
H6B0.56820.42350.21050.063*
H6C0.55660.42250.42030.063*
C70.8053 (2)0.30713 (17)0.4229 (3)0.0301 (5)
H7A0.84480.37280.44200.036*
C80.8989 (2)0.22389 (16)0.4628 (3)0.0261 (5)
H8A1.00100.23530.50830.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0207 (2)0.0195 (2)0.0153 (2)0.00038 (14)0.00501 (16)0.00061 (14)
N10.0278 (9)0.0278 (10)0.0236 (9)0.0027 (7)0.0086 (8)0.0009 (8)
N20.0263 (9)0.0267 (9)0.0206 (10)0.0019 (7)0.0053 (7)0.0036 (7)
N30.0242 (9)0.0401 (11)0.0181 (9)0.0131 (8)0.0059 (7)0.0038 (8)
N40.0218 (8)0.0219 (9)0.0198 (9)0.0009 (7)0.0053 (7)0.0008 (7)
C10.0169 (9)0.0205 (10)0.0201 (10)0.0007 (7)0.0001 (8)0.0034 (8)
C20.0167 (9)0.0191 (9)0.0227 (11)0.0006 (7)0.0064 (8)0.0021 (8)
C30.0241 (10)0.0258 (11)0.0309 (12)0.0044 (8)0.0056 (9)0.0032 (9)
C40.0193 (10)0.0349 (12)0.0386 (13)0.0010 (9)0.0055 (9)0.0012 (10)
C50.0285 (11)0.0283 (12)0.0285 (11)0.0055 (9)0.0072 (9)0.0017 (9)
C60.0370 (13)0.0372 (14)0.0511 (16)0.0127 (11)0.0118 (12)0.0034 (12)
C70.0309 (11)0.0213 (11)0.0382 (13)0.0014 (9)0.0102 (10)0.0010 (9)
C80.0217 (10)0.0250 (11)0.0306 (12)0.0024 (8)0.0062 (9)0.0005 (9)
Geometric parameters (Å, º) top
Co1—N2i2.1219 (18)C3—C41.376 (3)
Co1—N2ii2.1219 (18)C3—H3B0.9300
Co1—N1iii2.1229 (18)C4—C51.389 (3)
Co1—N12.1229 (18)C4—H4A0.9300
Co1—N42.1385 (17)C5—C71.384 (3)
Co1—N4iii2.1385 (17)C5—C61.503 (3)
N1—C11.152 (3)C6—H6A0.9600
N2—C21.153 (3)C6—H6B0.9600
N2—Co1iv2.1219 (18)C6—H6C0.9600
N3—C21.308 (3)C7—C81.375 (3)
N3—C11.314 (3)C7—H7A0.9300
N4—C81.340 (3)C8—H8A0.9300
N4—C31.340 (3)
N2i—Co1—N2ii180.00 (7)N2—C2—N3175.1 (2)
N2i—Co1—N1iii89.76 (7)N4—C3—C4123.1 (2)
N2ii—Co1—N1iii90.24 (7)N4—C3—H3B118.5
N2i—Co1—N190.24 (7)C4—C3—H3B118.5
N2ii—Co1—N189.76 (7)C3—C4—C5120.2 (2)
N1iii—Co1—N1180.00 (9)C3—C4—H4A119.9
N2i—Co1—N489.84 (7)C5—C4—H4A119.9
N2ii—Co1—N490.16 (7)C7—C5—C4116.5 (2)
N1iii—Co1—N490.06 (7)C7—C5—C6122.0 (2)
N1—Co1—N489.94 (7)C4—C5—C6121.5 (2)
N2i—Co1—N4iii90.16 (7)C5—C6—H6A109.5
N2ii—Co1—N4iii89.84 (7)C5—C6—H6B109.5
N1iii—Co1—N4iii89.94 (7)H6A—C6—H6B109.5
N1—Co1—N4iii90.06 (7)C5—C6—H6C109.5
N4—Co1—N4iii180.0H6A—C6—H6C109.5
C1—N1—Co1159.33 (16)H6B—C6—H6C109.5
C2—N2—Co1iv163.96 (16)C8—C7—C5120.2 (2)
C2—N3—C1117.09 (17)C8—C7—H7A119.9
C8—N4—C3116.84 (18)C5—C7—H7A119.9
C8—N4—Co1121.94 (13)N4—C8—C7123.2 (2)
C3—N4—Co1121.22 (14)N4—C8—H8A118.4
N1—C1—N3175.1 (2)C7—C8—H8A118.4
Symmetry codes: (i) x, y, z1; (ii) x+2, y, z+2; (iii) x+2, y, z+1; (iv) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···N3v0.932.573.487 (3)168
Symmetry code: (v) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···N3i0.932.573.487 (3)167.5
Symmetry code: (i) x+1, y, z+1.
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (No. 50472048) and the Program for New Century Excellent Talents in Universities (NCET-05–0499).

references
References top

Banerjee, R., Phan, A., Wang, B., Knobler, C., Furukawa, H., O'Keeffe, M. & Yaghi, O. M. (2008). Science, 319, 939–943.

Eddaoudi, M., Moler, D. B., Li, H. L., Chen, B. L., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.

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

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