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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1357.
Published online 2009 October 13. doi:  10.1107/S160053680904063X
PMCID: PMC2971377

A new Schiff base nickel(II) complex: {5,5′-dihydr­oxy-2,2′-[o-phenyl­enebis(nitrilo­methyl­idyne)]diphenolato}nickel(II) methanol disolvate

Abstract

The monomeric title nickel(II) complex of a salicylaldimine, [Ni(C20H14N2O4)]·2CH3OH, was obtained by the reaction of 2,4-dihydroxy­benzaldehyde and 1,2-phenyl­enediamine with nickel(II) acetate. The NiII atom is coordinated by two N atoms [Ni—N = 1.839 (2) Å] and two O atoms [Ni—O = 1.8253 (19) Å] in an approximately square-planar geometry. In the crystal structure, inter­molecular O—H(...)O hydrogen bonds link the mol­ecules into a chain along [001].

Related literature

For related structures, see: Amirnasr et al. (2006 [triangle]); Shi et al. (2004 [triangle]); Chen et al. (2009 [triangle]); Hermindez-Molina et al. (1997 [triangle]); Zhang et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1357-scheme1.jpg

Experimental

Crystal data

  • [Ni(C20H14N2O4)]·2CH4O
  • M r = 469.13
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1357-efi1.jpg
  • a = 15.673 (3) Å
  • b = 15.090 (2) Å
  • c = 8.8680 (2) Å
  • β = 104.593 (3)°
  • V = 2029.7 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.00 mm−1
  • T = 298 K
  • 0.31 × 0.14 × 0.13 mm

Data collection

  • Siemens SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.747, T max = 0.881
  • 5206 measured reflections
  • 1788 independent reflections
  • 1333 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.081
  • S = 1.00
  • 1788 reflections
  • 141 parameters
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680904063X/ds2006sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904063X/ds2006Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We acknowledge the financial support of the National Natural Science Foundation of China (20671048).

supplementary crystallographic information

Comment

Nickel complexes have attracted intensive interest in the past decade because they play important roles in bioinorganic chemistry and redox enzyme systems (Amirnasr et al., 2006). In a continuation of a study of Schiff base ligands and their nickel(II) complexes, we report here the title complex (Fig. 1), in which the main plane being formed by the three phenyl and the N2O2. The angles O1—Ni1—N1A and O1A—Ni1—N1 (177.30 (10)°) indicate that the coordination geometry of the nickel atom is four-coordinate in an approximately square planar, which acts as a tetradentate ligand through its o-phenylenediamine N atoms and its deprotonated phenol O atoms. This square planar geometry is the most usual for NiII complexes (Shi et al., 2004) in the N202 donor set with Schiff base ligands. The Ni—O distances of 1.8253 (19)Å are very close to the corresponding values in related structures(1.820 Å, Chen et al., 2009). However, the Ni—N distances of 1.8392 (2)Å are significantly shorter than that for a related complex (1.859 Å, Hemindez-Molina et al., 1997). As shown in Fig. 2, intermolecular O—H···O hydrogen bonds (Table 1) link the molecules into a one-dimensional chain along [0 0 1] direction (Zhang et al., 2009).

Experimental

o-Phenylenediamine(1 mmol, 108.22 mg) was dissolved in hot methanol (20 ml) and added dropwise to a methanol solution (10 ml) of 2,4-dihydroxybenzaldehyde (2 mmol, 276.2 mg). The mixture was then stirred at 323 K for 4 h. The triethylamine solution (3 ml) of nickel (II) acetate (1.5 mmol, 292.2 mg) was then added dropwise and the mixture stirred for another 4 h, at which point a red precipitate collected by suction filtration and washed with ethanol and ether. Crystals of the title compound suitable for X-ray analysis were from the methanol and dimethylsulfoxide solution after about one week.

Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H = 0.96 Å (methylene) or 0.93 Å (aromatic), 0.82 Å (hydroxyl) and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
Fig. 2.
Crystal packing of the compound, showing a one-dimensional chain linked by O—H···O hydrogen bonds (dashed lines).

Crystal data

[Ni(C20H14N2O4)]·2CH4OF(000) = 976
Mr = 469.13Dx = 1.535 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1287 reflections
a = 15.673 (3) Åθ = 2.7–23.9°
b = 15.090 (2) ŵ = 1.00 mm1
c = 8.8680 (2) ÅT = 298 K
β = 104.593 (3)°Block, red
V = 2029.7 (5) Å30.31 × 0.14 × 0.13 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer1788 independent reflections
Radiation source: fine-focus sealed tube1333 reflections with I > 2σ(I)
graphiteRint = 0.049
[var phi] and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→18
Tmin = 0.747, Tmax = 0.881k = −17→16
5206 measured reflectionsl = −9→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0294P)2] where P = (Fo2 + 2Fc2)/3
1788 reflections(Δ/σ)max < 0.001
141 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = −0.35 e Å3

Special details

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)

xyzUiso*/Ueq
Ni10.00000.21153 (3)−0.25000.03428 (19)
N10.06329 (15)0.12289 (14)−0.1294 (3)0.0322 (6)
O10.06161 (13)0.30290 (12)−0.1384 (2)0.0407 (5)
O20.23991 (13)0.45598 (13)0.2855 (2)0.0538 (6)
H20.21360.49760.23480.081*
O30.11150 (15)0.42336 (14)0.6598 (3)0.0615 (7)
H30.09210.38950.71540.092*
C10.03571 (17)0.03697 (17)−0.1846 (3)0.0340 (7)
C20.0716 (2)−0.04279 (19)−0.1201 (4)0.0438 (8)
H2A0.1194−0.0433−0.03320.053*
C30.0357 (2)−0.12082 (19)−0.1861 (4)0.0476 (9)
H3A0.0598−0.1744−0.14410.057*
C40.12589 (19)0.1350 (2)−0.0019 (4)0.0384 (8)
H40.15290.08470.04940.046*
C50.15581 (18)0.21777 (19)0.0639 (3)0.0330 (7)
C60.12162 (18)0.2986 (2)−0.0053 (3)0.0352 (7)
C70.1515 (2)0.3782 (2)0.0694 (4)0.0417 (8)
H70.12920.43150.02350.050*
C80.21309 (19)0.3788 (2)0.2092 (4)0.0385 (7)
C90.2494 (2)0.3000 (2)0.2786 (4)0.0461 (8)
H90.29250.30070.37230.055*
C100.22071 (19)0.2219 (2)0.2066 (4)0.0434 (8)
H100.24480.16930.25330.052*
C110.0943 (3)0.3892 (2)0.5095 (5)0.0717 (11)
H11A0.04310.41760.44540.107*
H11B0.08390.32660.51230.107*
H11C0.14400.39970.46710.107*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0358 (3)0.0298 (3)0.0330 (3)0.0000.0007 (2)0.000
N10.0334 (14)0.0260 (13)0.0370 (15)0.0003 (11)0.0083 (12)0.0010 (12)
O10.0474 (13)0.0288 (11)0.0357 (12)−0.0001 (10)−0.0088 (10)0.0008 (10)
O20.0578 (14)0.0451 (13)0.0460 (15)−0.0056 (11)−0.0101 (11)−0.0067 (12)
O30.0716 (17)0.0518 (15)0.0575 (17)−0.0104 (12)0.0094 (13)0.0108 (13)
C10.0379 (18)0.0288 (16)0.0376 (19)0.0023 (13)0.0138 (13)−0.0020 (14)
C20.047 (2)0.0360 (18)0.046 (2)0.0054 (16)0.0088 (16)0.0085 (16)
C30.061 (2)0.0294 (16)0.054 (2)0.0048 (15)0.0172 (16)0.0030 (15)
C40.0375 (18)0.0372 (18)0.040 (2)0.0054 (15)0.0081 (15)0.0062 (16)
C50.0325 (16)0.0320 (16)0.0330 (16)0.0017 (15)0.0053 (13)−0.0008 (15)
C60.0319 (16)0.0385 (18)0.0326 (17)−0.0002 (15)0.0035 (13)−0.0006 (15)
C70.046 (2)0.0350 (17)0.038 (2)−0.0007 (15)−0.0007 (15)−0.0017 (15)
C80.0373 (18)0.0395 (18)0.0364 (19)−0.0043 (15)0.0051 (15)−0.0070 (16)
C90.0395 (18)0.054 (2)0.0352 (19)0.0037 (17)−0.0088 (14)−0.0008 (17)
C100.0420 (19)0.0410 (19)0.0409 (19)0.0068 (16)−0.0014 (15)0.0055 (17)
C110.081 (3)0.064 (3)0.072 (3)−0.010 (2)0.025 (2)0.000 (2)

Geometric parameters (Å, °)

Ni1—O11.8253 (19)C3—H3A0.9300
Ni1—O1i1.8253 (19)C4—C51.408 (4)
Ni1—N1i1.839 (2)C4—H40.9300
Ni1—N11.839 (2)C5—C61.409 (4)
N1—C41.310 (4)C5—C101.411 (4)
N1—C11.414 (3)C6—C71.395 (4)
O1—C61.312 (3)C7—C81.366 (4)
O2—C81.360 (3)C7—H70.9300
O2—H20.8200C8—C91.393 (4)
O3—C111.391 (4)C9—C101.361 (4)
O3—H30.8200C9—H90.9300
C1—C21.389 (3)C10—H100.9300
C1—C1i1.394 (6)C11—H11A0.9600
C2—C31.371 (4)C11—H11B0.9600
C2—H2A0.9300C11—H11C0.9600
C3—C3i1.377 (6)
O1—Ni1—O1i81.88 (12)C4—C5—C6122.5 (3)
O1—Ni1—N1i177.30 (10)C4—C5—C10120.1 (3)
O1i—Ni1—N1i95.74 (9)C6—C5—C10117.5 (3)
O1—Ni1—N195.74 (9)O1—C6—C7117.6 (3)
O1i—Ni1—N1177.30 (10)O1—C6—C5122.9 (3)
N1i—Ni1—N186.67 (15)C7—C6—C5119.6 (3)
C4—N1—C1121.6 (3)C8—C7—C6120.8 (3)
C4—N1—Ni1125.3 (2)C8—C7—H7119.6
C1—N1—Ni1113.11 (19)C6—C7—H7119.6
C6—O1—Ni1127.69 (19)O2—C8—C7121.1 (3)
C8—O2—H2109.5O2—C8—C9118.1 (3)
C11—O3—H3109.5C7—C8—C9120.8 (3)
C2—C1—C1i119.95 (18)C10—C9—C8118.8 (3)
C2—C1—N1126.5 (3)C10—C9—H9120.6
C1i—C1—N1113.53 (15)C8—C9—H9120.6
C3—C2—C1119.2 (3)C9—C10—C5122.5 (3)
C3—C2—H2A120.4C9—C10—H10118.7
C1—C2—H2A120.4C5—C10—H10118.7
C2—C3—C3i120.81 (18)O3—C11—H11A109.5
C2—C3—H3A119.6O3—C11—H11B109.5
C3i—C3—H3A119.6H11A—C11—H11B109.5
N1—C4—C5125.5 (3)O3—C11—H11C109.5
N1—C4—H4117.2H11A—C11—H11C109.5
C5—C4—H4117.2H11B—C11—H11C109.5

Symmetry codes: (i) −x, y, −z−1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O3ii0.821.972.734 (3)154
O3—H3···O1iii0.821.982.797 (3)172

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2006).

References

  • Amirnasr, M., Schenk, K. J., Meghdadi, S. & Morshedi, M. (2006). Polyhedron, 25, 671–677.
  • Chen, X. H., Liang, Z. Y., Zhan, C. R. & Yang, M. X. (2009). J. Fuqing Branch Fujian Normal Univ.2, 7–11.
  • Hermindez-Molina, R., Mederos, A., Gill, P., Domfnguez, S., Ndfiez, P., Germain, G. & Debaerdemaeker, T. (1997). Inorg. Chim. Acta, 256, 319–325.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shi, Y. C., Shen, W. B., Yang, H. M., Song, H. B. & Hu, X. Y. (2004). Polyhedron, 23, 749–754.
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Zhang, Q. F., Jiang, F. L., Huang, Y. G., Wei, W., Gao, Q., Yang, M., Xiong, K. C. & Hong, M. C. (2009). Dalton Trans. pp. 2673–2676. [PubMed]

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