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Acta Cryst. (2007). E63, m2950    [ doi:10.1107/S1600536807055353 ]

catena-Poly[[tetra-[mu]-acetato-[kappa]8O:O'-dinickel(II)]-[mu]-2,3'-dipyridylamine-[kappa]2N:N']

L. Zhang

Abstract top

The title complex, [Ni2(C2H3O2)4(C10H7N3)]n or [Ni2(dbp)(C2O2H3)4]n (dbp = 2,3'-dipyridylamine), forms a polymeric linear chain. The repeat unit of the chain is the dinuclear [Ni2(C10H7N3)(C2O2H3)4] of the paddle-wheel type. The two Ni atoms are related by symmetry through an inversion center. Each Ni atom has a square-pyramidal coordination environment, with four O atoms from four acetate groups forming the basal plane, and a pyridyl N atom occupying the apex. The bridging dbp ligand is disordered over an inversion center, involving two alternative positions for the NH group.

Comment top

The chemical structure of the organic ligands including the molecular angle, length, and relative orientation of the donor groups plays an extremely important role in dictating polymer topology. So far, much of the research has been concentrated on the exploitation of angular ligands with a molecular angle, such as ligands with a Tshape,V-shape etc, in the construction of versatile coordination polymer architectures (Su et al., 2003; Gudbjartson et al., 1999). In this paper, we report the synthesis and crystal structure of the title complex,(I).

The structure of (I) consists of one-dimensional polymeric [Ni2(dbp)2(Ac)4]n chains built up from dinuclear Ni(II) subunit of the paddle-wheel type. The two nickel atoms are related by symmetry through inversion center (Fig. 1). Each nickel atom has a square pyramid coordination environment, with four oxygen atoms from four acetyl groups, forming the equatorial plane, and the pyridyl nitrogen atom, occupying the apex. This big paddle-wheel type arrangement prevents further torsion of the two pyridine rings of the bridging ligand, and then results in the formation of a neutral one-dimensional linear chain rather than a helical chain. The occurrence of intramolecular (N—H···O) hydrogen bond stabilize the architecture(Table 1).

Related literature top

For related literature, see: Gudbjartson et al. (1999); Su et al. (2003).

Experimental top

Ni(AC)2(0.036 g, 0.028 mmol), dbp (0.018 g, 0.013 mmol) a mixed solvent of acetonitrile, the mixture was heated for eight hours under reflux. During the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, weeks later some single crystals of the size suitable for X-Ray diffraction analysis.

Refinement top

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(Caromatic or N) and Uiso(H) = 1.5Ueq(Cmethyl).

Some of the C atoms of the pyridyl group display very elongated ellipsoids, however no correct disordered models could be defined.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. ORTEP view of (I) showing the formation of the polymeric chain, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 2 − x, 2 − y, 2 − z; ii: −x + 2, y, −z + 3/2; (iii) x, −y + 2, 1/2 + z]
Poly[(tetraacetyl-κ2N:N')dinickel(II)-µ-2,3'-dipyridylamine-κ2O:O'] top
Crystal data top
[Ni2(C2H3O2)4(C10H7N3)]F000 = 1072
Mr = 522.78Dx = 1.581 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1973 reflections
a = 13.4008 (13) Åθ = 2.9–25.2º
b = 8.4880 (9) ŵ = 1.76 mm−1
c = 20.112 (2) ÅT = 298 (2) K
β = 106.191 (7)ºBlock, green
V = 2196.9 (4) Å30.27 × 0.21 × 0.16 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		1973 independent reflections
Radiation source: fine-focus sealed tube1098 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.095
Detector resolution: 0 pixels mm-1θmax = 25.2º
T = 298(2) Kθmin = 2.9º
φ and ω scanh = −14→16
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		k = −10→8
Tmin = 0.648, Tmax = 0.766l = −24→18
5441 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.132  w = 1/[σ2(Fo2) + (0.0465P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
1973 reflectionsΔρmax = 0.57 e Å−3
147 parametersΔρmin = −0.45 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni2(C2H3O2)4(C10H7N3)]V = 2196.9 (4) Å3
Mr = 522.78Z = 4
Monoclinic, C2/cMo Kα
a = 13.4008 (13) ŵ = 1.76 mm−1
b = 8.4880 (9) ÅT = 298 (2) K
c = 20.112 (2) Å0.27 × 0.21 × 0.16 mm
β = 106.191 (7)º
Data collection top
Bruker APEXII area-detector
diffractometer		1973 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1098 reflections with I > 2σ(I)
Tmin = 0.648, Tmax = 0.766Rint = 0.095
5441 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054147 parameters
wR(F2) = 0.132H-atom parameters constrained
S = 1.00Δρmax = 0.57 e Å−3
1973 reflectionsΔρmin = −0.45 e Å−3
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*/UeqOcc. (<1)
Ni10.95385 (5)0.92235 (8)0.94293 (4)0.0423 (3)
N10.8818 (4)0.7990 (6)0.8453 (3)0.0577 (14)
N21.0307 (9)0.7655 (13)0.8155 (5)0.061 (3)0.50
H21.06130.78450.85840.074*0.50
O11.0991 (3)0.8984 (5)0.9401 (2)0.0644 (12)
O21.1772 (3)1.0270 (5)1.0372 (3)0.0688 (13)
O30.9695 (3)0.7416 (5)1.0053 (2)0.0603 (12)
O41.0480 (3)0.8712 (5)1.1020 (2)0.0654 (13)
C10.7828 (6)0.7539 (8)0.8293 (4)0.077 (2)
H10.74450.76580.86110.092*
C20.7364 (8)0.6873 (11)0.7633 (6)0.121 (4)
H210.66770.65350.75160.145*
C30.7940 (15)0.6729 (14)0.7163 (7)0.165 (8)
H30.76320.63230.67240.198*
C40.8911 (11)0.7158 (18)0.7332 (5)0.170 (8)
C50.9334 (7)0.7787 (12)0.7980 (4)0.098 (3)
C61.1793 (5)0.9576 (7)0.9823 (4)0.0533 (17)
C71.2802 (5)0.9406 (8)0.9663 (4)0.079 (2)
H7A1.31011.04280.96470.118*
H7B1.26950.88970.92220.118*
H7C1.32650.87821.00150.118*
C81.0076 (5)0.7494 (8)1.0691 (4)0.0573 (17)
C91.0085 (6)0.6030 (8)1.1110 (4)0.074 (2)
H9A0.94870.60241.12840.111*
H9B1.07040.60091.14910.111*
H9C1.00690.51201.08240.111*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0396 (5)0.0408 (5)0.0436 (5)−0.0011 (4)0.0069 (3)−0.0036 (4)
N10.054 (4)0.054 (4)0.062 (4)0.002 (3)0.011 (3)−0.003 (3)
N20.074 (9)0.085 (8)0.022 (5)−0.016 (7)0.008 (5)0.004 (5)
O10.051 (3)0.068 (3)0.072 (3)0.003 (2)0.014 (2)−0.009 (2)
O20.050 (3)0.077 (3)0.078 (3)−0.003 (2)0.015 (2)−0.019 (3)
O30.074 (3)0.049 (3)0.053 (3)−0.008 (2)0.011 (2)−0.003 (2)
O40.082 (3)0.043 (3)0.062 (3)−0.003 (2)0.006 (2)0.005 (2)
C10.057 (5)0.064 (5)0.098 (6)−0.007 (4)0.001 (4)0.016 (4)
C20.090 (8)0.082 (7)0.138 (10)−0.040 (6)−0.053 (7)0.006 (7)
C30.25 (2)0.111 (9)0.082 (9)0.083 (11)−0.048 (10)−0.036 (7)
C40.167 (12)0.259 (16)0.044 (6)0.143 (12)−0.038 (7)−0.032 (8)
C50.067 (6)0.163 (9)0.053 (5)0.029 (6)−0.002 (4)0.005 (5)
C60.042 (4)0.050 (4)0.070 (5)0.003 (3)0.019 (4)0.006 (4)
C70.063 (5)0.072 (5)0.112 (6)−0.006 (4)0.041 (4)−0.003 (4)
C80.050 (4)0.053 (5)0.072 (5)0.009 (3)0.022 (4)0.001 (4)
C90.095 (6)0.056 (5)0.072 (5)−0.005 (4)0.027 (4)0.013 (4)
Geometric parameters (Å, °) top
Ni1—O2i1.955 (5)C1—C21.418 (12)
Ni1—O31.956 (4)C1—H10.9300
Ni1—O4i1.968 (4)C2—C31.381 (16)
Ni1—O11.974 (4)C2—H210.9300
Ni1—N12.197 (5)C3—C41.30 (2)
Ni1—Ni1i2.6371 (14)C3—H30.9300
N1—C11.332 (8)C4—C51.376 (13)
N1—C51.333 (10)C4—N2ii1.675 (18)
N2—C51.258 (12)C6—C71.482 (9)
N2—C4ii1.675 (18)C7—H7A0.9600
N2—H20.8600C7—H7B0.9600
O1—C61.273 (7)C7—H7C0.9600
O2—C61.258 (7)C8—C91.501 (9)
O2—Ni1i1.955 (5)C9—H9A0.9600
O3—C81.242 (7)C9—H9B0.9600
O4—C81.265 (8)C9—H9C0.9600
O4—Ni1i1.968 (4)
O2i—Ni1—O389.00 (19)C3—C2—H21120.2
O2i—Ni1—O4i90.07 (19)C1—C2—H21120.2
O3—Ni1—O4i167.99 (17)C4—C3—C2120.3 (12)
O2i—Ni1—O1168.00 (18)C4—C3—H3119.9
O3—Ni1—O190.45 (18)C2—C3—H3119.8
O4i—Ni1—O187.97 (19)C3—C4—C5118.2 (14)
O2i—Ni1—N195.3 (2)C3—C4—N2ii131.3 (11)
O3—Ni1—N198.13 (18)C5—C4—N2ii107.3 (13)
O4i—Ni1—N193.87 (18)N2—C5—N1121.0 (8)
O1—Ni1—N196.7 (2)N2—C5—C4110.5 (10)
O2i—Ni1—Ni1i86.66 (14)N1—C5—C4124.6 (11)
O3—Ni1—Ni1i83.87 (13)O2—C6—O1123.3 (6)
O4i—Ni1—Ni1i84.13 (13)O2—C6—C7118.8 (6)
O1—Ni1—Ni1i81.36 (13)O1—C6—C7118.0 (7)
N1—Ni1—Ni1i177.22 (17)C6—C7—H7A109.5
C1—N1—C5118.1 (7)C6—C7—H7B109.5
C1—N1—Ni1120.8 (5)H7A—C7—H7B109.5
C5—N1—Ni1120.9 (5)C6—C7—H7C109.5
C5—N2—C4ii128.9 (9)H7A—C7—H7C109.5
C5—N2—H2115.6H7B—C7—H7C109.5
C4ii—N2—H2115.6O3—C8—O4125.2 (6)
C6—O1—Ni1126.6 (4)O3—C8—C9118.2 (6)
C6—O2—Ni1i121.6 (4)O4—C8—C9116.6 (6)
C8—O3—Ni1124.0 (4)C8—C9—H9A109.5
C8—O4—Ni1i122.5 (4)C8—C9—H9B109.5
N1—C1—C2119.1 (8)H9A—C9—H9B109.5
N1—C1—H1120.4C8—C9—H9C109.5
C2—C1—H1120.4H9A—C9—H9C109.5
C3—C2—C1119.6 (10)H9B—C9—H9C109.5
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.861.852.666 (10)157
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.861.852.666 (10)157
Acknowledgements top

The author is grateful to Lishui University for financial support.

references
References top

Bruker (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2 (Version 6.12) and SAINT (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA. Same version for both programs?

Gudbjartson, H., Biradha, K., Poirier, K. M. & Zaworotko, M. J. (1999). J. Am. Chem. Soc. 121, 2599–2600.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Su, C. Y., Cai, Y. P., Chen, C. L., Smith, M. D., Kaim, W. & Loye, H. C. (2003). J. Am. Chem. Soc. 125, 8595–8613.