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Acta Cryst. (2012). E68, m11    [ doi:10.1107/S1600536811051476 ]

Bis[2-(1-iminoethyl)phenolato-[kappa]2N,O]nickel(II)

N. Wang

Abstract top

There are one and a half independent molecules in the asymmetric unit of the title compound, [Ni(C8H8NO)2], one of which is situated on an inversion center. In both molecules, the NiII ion is coordinated by two O and two N atoms from two Schiff base ligands in an approximate square-planar geometry. Intermolecular N-H...O hydrogen bonds link three molecules into centrosymmetric trimer. The crystal packing exhibits weak intermolecular C-H...O hydrogen bonds and voids of 37 Å3.

Comment top

The Schiff bases are a kind of versatile ligands used in coordination chemistry (Haikarainen et al., 2001; Miyasaka et al., 2002). The complexes derived from Schiff bases have proved to be of significant interest in the areas of catalysis, magnetism, medicinal and material chemistry. In the present paper, the title compound (I) - a new Schiff base nickel(II) complex - is reported.

The molecule of (I) is mononuclear nickel(II) complex. The asymmetric unit of (I) contains two crystallographically independent molecules, one of which is situated on inversion center. The Ni atom is coordinated by two O and two N atoms from two Schiff base ligands, forming a square planar geometry. The bond lengths related to the Ni atoms are comparable to those observed in other nickel(II) complexes with Schiff bases (Liu et al., 2006; Wang, 2010), but shorter than the Cu–N and Cu–O bonds observed in a structurally similar copper(II) complex (Marongiu & Lingafelter, 1971).

Intermolecular N—H···O hydrogen bonds link three molecules in (I) into centrosymmetric trimer (Fig. 1). The crystal packing exhibits weak intermolecular C—H···O hydrogen bonds and voids of 37 Å3.

Related literature top

For general background to the use of Schiff bases in coordination chemistry, see: Haikarainen et al. (2001); Miyasaka et al. (2002). For nickel complexes with Schiff base ligands, see: Liu et al. (2006); Wang (2010). For the crystal structure of a similar copper(II) complex, see: Marongiu & Lingafelter (1971).

Experimental top

To a stirred ethanolic solution (30 ml) of 2-acetylphenol (0.136 g, 1 mmol) was added a few drops of 30% ammonia and an ethanolic solution (20 ml) of nickel(II) nitrate hexahydrate (0.291 g, 1 mmol). The final mixture was further stirred at room temperature for 1 h. The clear solution was set aside for a week, yielding red small block-shaped single crystals.

Refinement top

The amino H atoms were located in a difference Fourier map and were refined with distance restraints of N—H = 0.90 (1) Å. All other H atoms were positioned geometrically and were constrained as riding atoms, with C—H distances of 0.93–0.96 Å, and Uiso(H) set to 1.2 or 1.5Ueq(C) of the parent atom. Rotating group models were used for the methyl groups. The structure contains voids of 37 Å3.

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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The hydrogen-bonded (dashed lines) trimer in (I), showing the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level. Unlabeled atoms are related to the labeled ones by the symmetry operation (1 - x, 1 - y, 1 - z).
Bis[2-(1-iminoethyl)phenolato-κ2N,O]nickel(II) top
Crystal data top
[Ni(C8H8NO)2]Z = 3
Mr = 327.02F(000) = 510
Triclinic, P1Dx = 1.453 Mg m−3
a = 9.1084 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.3612 (16) ÅCell parameters from 772 reflections
c = 11.8249 (18) Åθ = 2.3–24.5°
α = 101.006 (3)°µ = 1.30 mm−1
β = 93.049 (3)°T = 298 K
γ = 109.777 (3)°Block, red
V = 1121.1 (3) Å30.20 × 0.20 × 0.18 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4190 independent reflections
Radiation source: fine-focus sealed tube2297 reflections with I > 2σ(I)
graphiteRint = 0.044
ω scansθmax = 25.7°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −11→11
Tmin = 0.781, Tmax = 0.799k = −13→13
6121 measured reflectionsl = −13→14
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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0585P)2]
where P = (Fo2 + 2Fc2)/3
4190 reflections(Δ/σ)max < 0.001
298 parametersΔρmax = 0.48 e Å−3
3 restraintsΔρmin = −0.39 e Å−3
Crystal data top
[Ni(C8H8NO)2]γ = 109.777 (3)°
Mr = 327.02V = 1121.1 (3) Å3
Triclinic, P1Z = 3
a = 9.1084 (10) ÅMo Kα radiation
b = 11.3612 (16) ŵ = 1.30 mm−1
c = 11.8249 (18) ÅT = 298 K
α = 101.006 (3)°0.20 × 0.20 × 0.18 mm
β = 93.049 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4190 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2297 reflections with I > 2σ(I)
Tmin = 0.781, Tmax = 0.799Rint = 0.044
6121 measured reflectionsθmax = 25.7°
Refinement top
R[F2 > 2σ(F2)] = 0.062H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146Δρmax = 0.48 e Å−3
S = 0.99Δρmin = −0.39 e Å−3
4190 reflectionsAbsolute structure: ?
298 parametersFlack parameter: ?
3 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
Ni10.50000.50000.50000.0392 (3)
Ni20.35993 (9)0.05065 (7)0.23238 (6)0.0385 (3)
O10.1878 (5)−0.0945 (3)0.2135 (3)0.0472 (11)
O20.5346 (5)0.1953 (3)0.2545 (3)0.0473 (11)
O30.4558 (5)0.4475 (3)0.3430 (3)0.0477 (11)
N10.2586 (6)0.1539 (4)0.3058 (4)0.0423 (12)
N20.4618 (6)−0.0507 (4)0.1545 (4)0.0423 (12)
N30.4211 (6)0.6312 (4)0.5050 (4)0.0416 (12)
C10.0143 (7)−0.0061 (6)0.3199 (5)0.0451 (15)
C20.0540 (7)−0.1072 (6)0.2547 (5)0.0445 (16)
C3−0.0595 (8)−0.2330 (6)0.2351 (6)0.0571 (18)
H3−0.0379−0.30090.19130.069*
C4−0.1993 (8)−0.2566 (7)0.2789 (6)0.067 (2)
H4−0.2708−0.34030.26510.080*
C5−0.2365 (9)−0.1581 (8)0.3436 (6)0.070 (2)
H5−0.3316−0.17520.37410.084*
C6−0.1317 (8)−0.0350 (7)0.3621 (6)0.0594 (19)
H6−0.15810.03140.40390.071*
C70.1213 (7)0.1262 (6)0.3398 (5)0.0423 (15)
C80.0716 (8)0.2323 (6)0.4004 (6)0.065 (2)
H8A0.15360.31330.40470.098*
H8B0.05190.22160.47750.098*
H8C−0.02260.22980.35790.098*
C90.7050 (7)0.1099 (6)0.1411 (5)0.0419 (15)
C100.6652 (7)0.2101 (6)0.2071 (5)0.0433 (15)
C110.7740 (8)0.3369 (6)0.2241 (6)0.0563 (18)
H110.75120.40470.26720.068*
C120.9132 (9)0.3605 (7)0.1774 (6)0.066 (2)
H120.98390.44440.19080.080*
C130.9520 (9)0.2637 (9)0.1111 (7)0.075 (2)
H131.04580.28160.07870.090*
C140.8479 (8)0.1411 (7)0.0948 (6)0.0613 (19)
H140.87300.07520.05080.074*
C150.5979 (7)−0.0231 (5)0.1195 (5)0.0396 (15)
C160.6453 (8)−0.1295 (6)0.0558 (5)0.0563 (18)
H16A0.5654−0.21060.05510.084*
H16B0.7430−0.12540.09410.084*
H16C0.6577−0.1204−0.02260.084*
C170.3474 (6)0.6042 (5)0.3019 (5)0.0354 (14)
C180.3980 (7)0.4986 (5)0.2679 (5)0.0412 (15)
C190.3859 (7)0.4450 (6)0.1502 (5)0.0491 (16)
H190.42050.37700.12710.059*
C200.3235 (8)0.4911 (6)0.0672 (6)0.0562 (18)
H200.31550.4532−0.01090.067*
C210.2730 (8)0.5925 (6)0.0987 (6)0.0567 (18)
H210.23140.62340.04220.068*
C220.2843 (7)0.6477 (6)0.2141 (6)0.0474 (16)
H220.24940.71590.23480.057*
C230.3618 (6)0.6684 (5)0.4228 (5)0.0368 (14)
C240.3106 (9)0.7818 (6)0.4540 (5)0.066 (2)
H24A0.33090.81430.53660.099*
H24B0.20000.75590.42910.099*
H24C0.36800.84770.41610.099*
H10.306 (7)0.2400 (13)0.325 (5)0.080*
H20.399 (6)−0.134 (2)0.139 (5)0.080*
H3A0.434 (8)0.676 (5)0.578 (2)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0459 (7)0.0321 (6)0.0439 (7)0.0225 (6)0.0028 (6)0.0035 (5)
Ni20.0378 (5)0.0330 (5)0.0473 (5)0.0168 (4)0.0084 (4)0.0063 (4)
O10.038 (2)0.038 (2)0.067 (3)0.018 (2)0.012 (2)0.006 (2)
O20.045 (3)0.037 (2)0.057 (3)0.016 (2)0.016 (2)−0.001 (2)
O30.069 (3)0.041 (2)0.041 (3)0.034 (2)−0.001 (2)0.003 (2)
N10.047 (3)0.035 (3)0.044 (3)0.017 (3)0.003 (3)0.004 (3)
N20.043 (3)0.036 (3)0.049 (3)0.015 (3)0.015 (3)0.006 (3)
N30.046 (3)0.038 (3)0.044 (3)0.024 (3)0.000 (3)0.003 (3)
C10.036 (4)0.054 (4)0.050 (4)0.022 (3)0.004 (3)0.014 (3)
C20.036 (4)0.046 (4)0.058 (4)0.018 (3)0.005 (3)0.023 (3)
C30.044 (4)0.053 (4)0.076 (5)0.016 (4)0.003 (4)0.020 (4)
C40.044 (5)0.069 (5)0.079 (6)0.001 (4)0.001 (4)0.033 (4)
C50.048 (5)0.088 (6)0.078 (6)0.024 (5)0.020 (4)0.025 (5)
C60.045 (4)0.073 (5)0.067 (5)0.026 (4)0.014 (4)0.021 (4)
C70.049 (4)0.053 (4)0.032 (4)0.031 (4)0.004 (3)0.005 (3)
C80.058 (5)0.069 (5)0.077 (5)0.038 (4)0.015 (4)0.004 (4)
C90.039 (4)0.047 (4)0.042 (4)0.019 (3)0.004 (3)0.008 (3)
C100.043 (4)0.045 (4)0.039 (4)0.012 (3)−0.002 (3)0.010 (3)
C110.047 (4)0.049 (4)0.067 (5)0.012 (4)0.003 (4)0.012 (4)
C120.054 (5)0.065 (5)0.068 (5)0.001 (4)0.005 (4)0.023 (4)
C130.044 (5)0.102 (7)0.069 (6)0.010 (5)0.011 (4)0.020 (5)
C140.042 (4)0.080 (5)0.062 (5)0.024 (4)0.013 (4)0.011 (4)
C150.045 (4)0.045 (4)0.036 (4)0.024 (3)0.002 (3)0.013 (3)
C160.066 (5)0.056 (4)0.059 (4)0.038 (4)0.020 (4)0.010 (4)
C170.028 (3)0.032 (3)0.046 (4)0.012 (3)0.004 (3)0.006 (3)
C180.036 (4)0.038 (3)0.051 (4)0.015 (3)0.011 (3)0.011 (3)
C190.056 (4)0.047 (4)0.043 (4)0.021 (3)0.006 (3)0.004 (3)
C200.058 (4)0.059 (4)0.040 (4)0.010 (4)−0.001 (4)0.006 (4)
C210.058 (5)0.059 (5)0.056 (5)0.019 (4)0.001 (4)0.026 (4)
C220.046 (4)0.045 (4)0.056 (5)0.018 (3)0.006 (3)0.019 (3)
C230.032 (3)0.030 (3)0.050 (4)0.013 (3)0.010 (3)0.007 (3)
C240.102 (6)0.063 (4)0.059 (5)0.062 (5)0.017 (4)0.013 (4)
Geometric parameters (Å, °) top
Ni1—O3i1.816 (4)C8—H8C0.9600
Ni1—O31.816 (4)C9—C141.398 (8)
Ni1—N31.853 (5)C9—C101.417 (8)
Ni1—N3i1.853 (5)C9—C151.459 (8)
Ni2—O11.817 (4)C10—C111.414 (8)
Ni2—O21.822 (4)C11—C121.374 (9)
Ni2—N11.847 (5)C11—H110.9300
Ni2—N21.856 (5)C12—C131.382 (10)
O1—C21.310 (7)C12—H120.9300
O2—C101.315 (7)C13—C141.364 (9)
O3—C181.326 (6)C13—H130.9300
N1—C71.289 (7)C14—H140.9300
N1—H10.902 (10)C15—C161.501 (7)
N2—C151.283 (7)C16—H16A0.9600
N2—H20.899 (10)C16—H16B0.9600
N3—C231.294 (7)C16—H16C0.9600
N3—H3A0.897 (10)C17—C221.406 (7)
C1—C61.400 (8)C17—C181.422 (7)
C1—C21.420 (8)C17—C231.453 (7)
C1—C71.454 (8)C18—C191.391 (8)
C2—C31.418 (8)C19—C201.378 (8)
C3—C41.361 (9)C19—H190.9300
C3—H30.9300C20—C211.375 (8)
C4—C51.383 (9)C20—H200.9300
C4—H40.9300C21—C221.371 (8)
C5—C61.369 (9)C21—H210.9300
C5—H50.9300C22—H220.9300
C6—H60.9300C23—C241.502 (7)
C7—C81.498 (8)C24—H24A0.9600
C8—H8A0.9600C24—H24B0.9600
C8—H8B0.9600C24—H24C0.9600
O3i—Ni1—O3180.000 (1)C10—C9—C15120.8 (5)
O3i—Ni1—N386.81 (18)O2—C10—C11116.8 (6)
O3—Ni1—N393.19 (18)O2—C10—C9125.4 (5)
O3i—Ni1—N3i93.19 (18)C11—C10—C9117.9 (6)
O3—Ni1—N3i86.81 (18)C12—C11—C10120.3 (7)
N3—Ni1—N3i180.000 (2)C12—C11—H11119.8
O1—Ni2—O2178.57 (18)C10—C11—H11119.8
O1—Ni2—N193.24 (19)C11—C12—C13122.3 (7)
O2—Ni2—N187.0 (2)C11—C12—H12118.9
O1—Ni2—N287.43 (19)C13—C12—H12118.9
O2—Ni2—N292.39 (19)C14—C13—C12117.7 (7)
N1—Ni2—N2178.2 (2)C14—C13—H13121.2
C2—O1—Ni2127.8 (4)C12—C13—H13121.2
C10—O2—Ni2127.8 (4)C13—C14—C9123.1 (7)
C18—O3—Ni1129.2 (4)C13—C14—H14118.4
C7—N1—Ni2131.3 (4)C9—C14—H14118.4
C7—N1—H1108 (4)N2—C15—C9120.5 (5)
Ni2—N1—H1121 (4)N2—C15—C16119.1 (5)
C15—N2—Ni2132.2 (4)C9—C15—C16120.4 (5)
C15—N2—H2118 (4)C15—C16—H16A109.5
Ni2—N2—H2110 (4)C15—C16—H16B109.5
C23—N3—Ni1131.0 (4)H16A—C16—H16B109.5
C23—N3—H3A119 (4)C15—C16—H16C109.5
Ni1—N3—H3A110 (4)H16A—C16—H16C109.5
C6—C1—C2119.1 (6)H16B—C16—H16C109.5
C6—C1—C7120.2 (6)C22—C17—C18118.0 (5)
C2—C1—C7120.6 (5)C22—C17—C23119.9 (5)
O1—C2—C3117.3 (6)C18—C17—C23122.1 (5)
O1—C2—C1125.5 (5)O3—C18—C19117.8 (5)
C3—C2—C1117.2 (6)O3—C18—C17123.3 (5)
C4—C3—C2121.7 (7)C19—C18—C17118.9 (5)
C4—C3—H3119.2C20—C19—C18121.1 (6)
C2—C3—H3119.2C20—C19—H19119.5
C3—C4—C5121.0 (7)C18—C19—H19119.5
C3—C4—H4119.5C21—C20—C19120.8 (6)
C5—C4—H4119.5C21—C20—H20119.6
C6—C5—C4119.2 (7)C19—C20—H20119.6
C6—C5—H5120.4C22—C21—C20119.4 (6)
C4—C5—H5120.4C22—C21—H21120.3
C5—C6—C1121.9 (7)C20—C21—H21120.3
C5—C6—H6119.0C21—C22—C17121.9 (6)
C1—C6—H6119.0C21—C22—H22119.1
N1—C7—C1121.0 (5)C17—C22—H22119.1
N1—C7—C8119.3 (6)N3—C23—C17121.1 (5)
C1—C7—C8119.7 (6)N3—C23—C24118.8 (5)
C7—C8—H8A109.5C17—C23—C24120.1 (5)
C7—C8—H8B109.5C23—C24—H24A109.5
H8A—C8—H8B109.5C23—C24—H24B109.5
C7—C8—H8C109.5H24A—C24—H24B109.5
H8A—C8—H8C109.5C23—C24—H24C109.5
H8B—C8—H8C109.5H24A—C24—H24C109.5
C14—C9—C10118.7 (6)H24B—C24—H24C109.5
C14—C9—C15120.5 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O2i0.90 (1)2.16 (2)3.055 (6)172 (6)
N1—H1···O30.90 (1)2.25 (2)3.138 (6)168 (6)
C22—H22···O1ii0.932.463.332 (6)157 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O2i0.90 (1)2.16 (2)3.055 (6)172 (6)
N1—H1···O30.90 (1)2.25 (2)3.138 (6)168 (6)
C22—H22···O1ii0.932.463.332 (6)157 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z.
Acknowledgements top

No acknowledgements.

references
References top

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