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Acta Cryst. (2008). E64, m194    [ doi:10.1107/S1600536807066226 ]

Bis(acetato-[kappa]2O,O')bis(2-aminopyridine-[kappa]N)nickel(II)

Q. Wang and D.-Q. Wang

Abstract top

The title complex, [Ni(C2H3O2)2(C5H6N2)2], has a distorted octahedral geometry around the Ni atom. Intermolecular and intramolecular N-H...O hydrogen bonds exist in the crystal structure.

Comment top

A lot of work has been devoted to the study of mixed–ligand complexes because of their key role in biological progress and their properties in areas such as analytical chemistry, catalysis and magnetochemistry (Roman et al., 1995). In this paper, we report the synthesis and crystal structure of the new title nickel complex.

The molecular structure of the title complex, (I), is shown on Fig.1. The Ni atom is in a distorted octahedral geometry [Ni—N = 2.069 (2)–2.079 (2) Å, Ni—O = 2.092 (2)–2.164 (2) Å], coordinated by two N atoms from two 2–aminopyridine ligands and four O atoms from two acetate groups. The intermolecular and intramolecular N—H···O hydrogen bonds are exist in the crystal structure.

Related literature top

For general background, see: Roman et al. (1995).

Experimental top

Nickel acetate tetrahydrate (2 mmol, 497.7 mg) in absolute ethanol (20 ml) was added dropwise to a absolute ethanol solution (20 ml) of 2–aminopyridine (4 mmol, 376.5 mg). The mixture was heated under reflux with stirring for 4 h. The solution was kept at room temperature for 20 days, after which large green block–shaped crystals of the title complex suitable for X–ray diffraction analysis were obtained.

Refinement top

All H–atoms were positioned geometrically and refined using a riding model, with C—H (methyl) 0.96 Å, C—H (aromatic) 0.93 Å, N—H(amino) 0.86 Å, with Uiso(H) = 1.2Ueq(C, N) and Uiso(H) = 1.5Ueq(C) for CH3.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex with the atom numbering scheme. Displacement ellipsoids are shown at 30% probability level. H atoms are presented as a spheres of arbitrary radius.
Bis(acetato-κ2O,O')bis(2-aminopyridine-κN)nickel(II) top
Crystal data top
[Ni(C2H3O2)2(C5H6N2)2]F000 = 1520
Mr = 365.01Dx = 1.486 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4718 reflections
a = 14.281 (4) Åθ = 2.4–27.7º
b = 14.989 (5) ŵ = 1.21 mm−1
c = 15.241 (5) ÅT = 298 (2) K
V = 3262.5 (18) Å3Block, green
Z = 80.48 × 0.36 × 0.30 mm
Data collection top
Siemens SMART CCD area–detector
diffractometer		2875 independent reflections
Radiation source: fine–focus sealed tube2173 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.039
T = 298(2) Kθmax = 25.0º
φ– and ω–scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.593, Tmax = 0.712k = −17→17
15953 measured reflectionsl = −14→18
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)] = 0.031H-atom parameters constrained
wR(F2) = 0.093  w = 1/[σ2(Fo2) + (0.039P)2 + 4.6901P]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max = 0.001
2875 reflectionsΔρmax = 0.38 e Å−3
202 parametersΔρmin = −0.25 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C2H3O2)2(C5H6N2)2]V = 3262.5 (18) Å3
Mr = 365.01Z = 8
Orthorhombic, PbcaMo Kα
a = 14.281 (4) ŵ = 1.21 mm−1
b = 14.989 (5) ÅT = 298 (2) K
c = 15.241 (5) Å0.48 × 0.36 × 0.30 mm
Data collection top
Siemens SMART CCD area–detector
diffractometer		2875 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2173 reflections with I > 2σ(I)
Tmin = 0.593, Tmax = 0.712Rint = 0.039
15953 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.093H-atom parameters constrained
S = 0.95Δρmax = 0.38 e Å−3
2875 reflectionsΔρmin = −0.25 e Å−3
202 parameters
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
Ni10.65501 (2)0.18431 (2)0.30692 (2)0.03492 (14)
N10.74523 (16)0.17626 (15)0.41287 (15)0.0353 (6)
N20.88178 (18)0.17679 (18)0.33118 (18)0.0475 (7)
H2A0.84850.17890.28420.057*
H2B0.94190.17590.32770.057*
N30.58868 (17)0.06682 (16)0.34427 (17)0.0405 (6)
N40.44625 (19)0.1315 (2)0.3738 (2)0.0654 (9)
H4A0.47030.18280.36260.079*
H4B0.38840.12740.38890.079*
O10.73266 (14)0.12566 (15)0.20530 (14)0.0469 (5)
O20.59071 (15)0.17241 (14)0.17892 (14)0.0470 (5)
O30.68659 (16)0.32137 (14)0.28166 (15)0.0484 (6)
O40.56826 (15)0.28132 (14)0.36282 (15)0.0472 (5)
C10.6643 (2)0.1341 (2)0.1533 (2)0.0470 (5)
C20.6716 (3)0.0967 (3)0.0625 (3)0.0723 (12)
H2C0.65470.03480.06320.108*
H2D0.73480.10290.04180.108*
H2E0.63010.12860.02410.108*
C30.6159 (2)0.3419 (2)0.3261 (2)0.0445 (8)
C40.5880 (3)0.4383 (2)0.3375 (3)0.0667 (11)
H4C0.60840.45910.39390.100*
H4D0.52120.44350.33340.100*
H4E0.61670.47360.29240.100*
C50.83976 (19)0.17483 (18)0.4102 (2)0.0364 (7)
C60.8921 (2)0.1720 (2)0.4878 (2)0.0500 (8)
H60.95720.17240.48540.060*
C70.8480 (3)0.1687 (2)0.5667 (2)0.0541 (9)
H70.88260.16630.61840.065*
C80.7511 (3)0.1690 (2)0.5695 (2)0.0526 (9)
H80.71930.16650.62270.063*
C90.7040 (2)0.1731 (2)0.4926 (2)0.0458 (8)
H90.63890.17380.49470.055*
C100.4988 (2)0.0580 (2)0.3679 (2)0.0416 (7)
C110.4604 (3)−0.0261 (2)0.3863 (3)0.0609 (10)
H110.3981−0.03120.40330.073*
C120.5143 (3)−0.0994 (3)0.3793 (3)0.0698 (11)
H120.4891−0.15530.39100.084*
C130.6068 (3)−0.0916 (3)0.3546 (3)0.0719 (12)
H130.6451−0.14150.34970.086*
C140.6401 (2)−0.0087 (2)0.3377 (3)0.0608 (10)
H140.7023−0.00340.32060.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0245 (2)0.0418 (2)0.0384 (2)−0.00038 (16)0.00112 (16)−0.00062 (17)
N10.0281 (12)0.0422 (14)0.0355 (13)−0.0029 (10)0.0029 (10)−0.0001 (11)
N20.0247 (13)0.0668 (19)0.0508 (17)−0.0029 (12)0.0040 (12)−0.0038 (14)
N30.0295 (13)0.0412 (14)0.0508 (15)−0.0025 (11)0.0000 (12)0.0003 (12)
N40.0373 (16)0.0581 (18)0.101 (3)0.0006 (14)0.0157 (17)0.0063 (18)
O10.0317 (11)0.0616 (14)0.0475 (13)0.0035 (10)−0.0040 (10)−0.0073 (11)
O20.0348 (10)0.0558 (11)0.0503 (11)0.0000 (8)−0.0056 (8)−0.0050 (9)
O30.0461 (13)0.0532 (13)0.0457 (13)−0.0089 (11)0.0034 (11)0.0038 (10)
O40.0402 (12)0.0437 (12)0.0577 (14)0.0018 (10)0.0092 (11)0.0022 (11)
C10.0348 (10)0.0558 (11)0.0503 (11)0.0000 (8)−0.0056 (8)−0.0050 (9)
C20.078 (3)0.086 (3)0.053 (2)0.013 (2)−0.012 (2)−0.023 (2)
C30.0465 (19)0.0452 (18)0.0419 (18)0.0012 (15)−0.0081 (16)0.0012 (15)
C40.091 (3)0.0416 (19)0.067 (2)0.008 (2)−0.005 (2)0.0021 (18)
C50.0308 (15)0.0315 (15)0.0468 (18)−0.0041 (12)0.0014 (14)−0.0025 (13)
C60.0346 (18)0.056 (2)0.059 (2)−0.0048 (15)−0.0110 (16)−0.0002 (17)
C70.059 (2)0.056 (2)0.047 (2)−0.0094 (17)−0.0172 (18)0.0030 (16)
C80.061 (2)0.059 (2)0.0378 (18)−0.0087 (17)0.0031 (17)0.0000 (16)
C90.0367 (17)0.059 (2)0.0412 (18)−0.0040 (15)0.0053 (15)−0.0003 (15)
C100.0330 (16)0.0505 (18)0.0414 (17)−0.0034 (14)0.0036 (14)−0.0015 (15)
C110.045 (2)0.063 (2)0.075 (3)−0.0148 (18)0.0148 (19)0.003 (2)
C120.076 (3)0.048 (2)0.085 (3)−0.014 (2)0.014 (2)0.005 (2)
C130.071 (3)0.044 (2)0.101 (3)0.0033 (19)0.013 (2)0.008 (2)
C140.043 (2)0.048 (2)0.092 (3)0.0030 (16)0.0131 (19)0.011 (2)
Geometric parameters (Å, °) top
Ni1—N12.069 (2)C2—H2D0.9600
Ni1—N32.079 (2)C2—H2E0.9600
Ni1—O42.092 (2)C3—C41.509 (5)
Ni1—O12.098 (2)C4—H4C0.9600
Ni1—O32.138 (2)C4—H4D0.9600
Ni1—O22.164 (2)C4—H4E0.9600
N1—C91.351 (4)C5—C61.400 (4)
N1—C51.351 (4)C6—C71.358 (5)
N2—C51.346 (4)C6—H60.9300
N2—H2A0.8600C7—C81.384 (5)
N2—H2B0.8600C7—H70.9300
N3—C101.339 (4)C8—C91.354 (5)
N3—C141.353 (4)C8—H80.9300
N4—C101.336 (4)C9—H90.9300
N4—H4A0.8600C10—C111.403 (5)
N4—H4B0.8600C11—C121.345 (5)
O1—C11.264 (4)C11—H110.9300
O2—C11.259 (4)C12—C131.379 (6)
O3—C31.254 (4)C12—H120.9300
O4—C31.264 (4)C13—C141.354 (5)
C1—C21.497 (5)C13—H130.9300
C2—H2C0.9600C14—H140.9300
N1—Ni1—N391.18 (10)O3—C3—O4119.7 (3)
N1—Ni1—O495.25 (9)O3—C3—C4120.6 (3)
N3—Ni1—O4101.98 (9)O4—C3—C4119.7 (3)
N1—Ni1—O1102.86 (9)C3—C4—H4C109.5
N3—Ni1—O195.05 (10)C3—C4—H4D109.5
O4—Ni1—O1154.83 (9)H4C—C4—H4D109.5
N1—Ni1—O393.74 (9)C3—C4—H4E109.5
N3—Ni1—O3163.58 (9)H4C—C4—H4E109.5
O4—Ni1—O361.99 (9)H4D—C4—H4E109.5
O1—Ni1—O399.10 (9)N2—C5—N1118.2 (3)
N1—Ni1—O2164.38 (9)N2—C5—C6121.3 (3)
N3—Ni1—O289.06 (9)N1—C5—C6120.6 (3)
O4—Ni1—O299.98 (9)C7—C6—C5120.1 (3)
O1—Ni1—O261.58 (8)C7—C6—H6119.9
O3—Ni1—O290.37 (8)C5—C6—H6119.9
C9—N1—C5117.5 (3)C6—C7—C8119.4 (3)
C9—N1—Ni1115.6 (2)C6—C7—H7120.3
C5—N1—Ni1126.8 (2)C8—C7—H7120.3
C5—N2—H2A120.0C9—C8—C7118.1 (3)
C5—N2—H2B120.0C9—C8—H8121.0
H2A—N2—H2B120.0C7—C8—H8121.0
C10—N3—C14117.2 (3)N1—C9—C8124.3 (3)
C10—N3—Ni1126.4 (2)N1—C9—H9117.8
C14—N3—Ni1116.2 (2)C8—C9—H9117.8
C10—N4—H4A120.0N4—C10—N3118.4 (3)
C10—N4—H4B120.0N4—C10—C11120.5 (3)
H4A—N4—H4B120.0N3—C10—C11121.1 (3)
C1—O1—Ni190.71 (19)C12—C11—C10119.6 (3)
C1—O2—Ni187.88 (19)C12—C11—H11120.2
C3—O3—Ni188.18 (19)C10—C11—H11120.2
C3—O4—Ni190.01 (19)C11—C12—C13120.0 (4)
O2—C1—O1119.7 (3)C11—C12—H12120.0
O2—C1—C2121.1 (3)C13—C12—H12120.0
O1—C1—C2119.2 (3)C14—C13—C12117.8 (4)
C1—C2—H2C109.5C14—C13—H13121.1
C1—C2—H2D109.5C12—C13—H13121.1
H2C—C2—H2D109.5C13—C14—N3124.3 (3)
C1—C2—H2E109.5C13—C14—H14117.9
H2C—C2—H2E109.5N3—C14—H14117.9
H2D—C2—H2E109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O2i0.862.132.988 (3)179
N2—H2A···O10.862.202.967 (3)149
N4—H4A···O40.862.032.848 (4)158
Symmetry codes: (i) x+1/2, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O2i0.862.132.988 (3)179
N2—H2A···O10.862.202.967 (3)149
N4—H4A···O40.862.032.848 (4)158
Symmetry codes: (i) x+1/2, y, −z+1/2.
Acknowledgements top

The authors acknowledge the financial support of the Shandong Province Science Foundation and the State Key Laboratory of Crystal Materials, Shandong University, People's Republic of China.

references
References top

Roman, P., Luque, A., Guzman-Miralles, C. & Beitia, J. I. (1995). Polyhedron, 14, 2863–2869.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X–ray Instruments Inc., Madison, Wisconsin, USA.