supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m1305    [ doi:10.1107/S1600536809039257 ]

Bis{2-(5-hydroxy-2-[1-(hydroxyimino)ethyl]phenolato-[kappa]2O1,N}nickel(II) N,N-dimethylformamide disolvate

Y.-Q. Dang

Abstract top

The Ni atom of the title complex, [Ni(C8H8NO3)2]·2C3H7NO, lies on a center of inversion in a square-planar N2O2 coordination environment. An intramolecular O-H...O hydrogen bond exists between the oximic hydroxy group of one ligand and the metal-coordinated O atom of the symmetry-related ligand. The dimethylformamide solvent molecules are connected to the phenolate groups of the complex via O-H...O hydrogen bonds.

Comment top

2-Hydroxyaryloximes are important organic ligands and their complexes found to have many applications, especially in extractive metallurgy and biology (Chaudhuri, 2003; Elo & Lumme, 1985; Keeney et al., 1984; Milios et al., 2007). Structures of nickel complexes based on the hydroxyoxime ligands 2-[1-(hydroxyimino)ethyl]phenol, bis[2-(1-(hydroxyimino)ethyl)phenolato]nickel (Hatzidimitriou et al., 1997), and bis[2-(5-methyl-1-(hydroxyimino)ethyl)phenolato]nickel (Voutsas et al., 1999), have been reported. As a continuation of these studies, the structure of the title complex, (I), is described herein.

The Ni atom in (I), Fig. 1, is four-coordinate and lies on a center of inversion in a square-planar coordination geometry with the O2—Ni1—N1 angle = 91.84 (6)° and O2—Ni1—N1i = 88.16 (6)°; i: -x, -y, -z. The distances of the Ni1—O2 and Ni1—N1 bonds is similar to those observed in the Ni complexes cited above. The deprotonated phenolato oxygen atom O2 is intramolecularly hydrogen bonded to the oximic hydroxyl group of the opposite ligand, Table 1. The complex and the solvent N,N-dimethylformamide molecules are linked by the O—H···O hydrogen bonds, Table 1.

Related literature top

For general background to the applications of 2-hydroxyaryloxime complexes in extractive metallurgy and biology, see: Keeney et al. (1984); Elo & Lumme (1985); Chaudhuri (2003); Milios et al. (2007). For related structures, see: Hatzidimitriou et al. (1997); Voutsas et al. (1999).

Experimental top

Nickel perchlorate hexahydrate (0.36 g, 1 mmol), 1-(2,4-dihydroxyphenyl)ethanone oxime (0.17 g, 1 mmol), H2O (6 ml) and DMF (6 ml) were placed in a 20 ml Teflon-lined autoclave. The autoclave was heated at 393 K for 2 days. The autoclave was cooled over a period of 5 h at a rate of 20 K per hour. Green crystals were collected by filtration, washed with methanol, and dried in air; yield 38% based on Ni.

Refinement top

H atoms were placed at calculated positions (C—H = 0.93–0.96 Å and O—H = 0.82 Å) and refined in the riding model approximation with Uiso(H) = 1.2–1.5Ueq(C or O).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I) with displacement ellipsoids are drawn at the 50% probability level. The dashed lines denote hydrogen bonds. The complex is located on a center of inversion; i: -x, -y, -z.
Bis{2-(5-hydroxy-2-[1-(hydroxyimino)ethyl]phenolato- κ2O1,N}nickel(II) N,N-dimethylformamide disolvate top
Crystal data top
[Ni(C8H8NO3)2]·2C3H7NOF(000) = 564
Mr = 537.21Dx = 1.455 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5624 reflections
a = 13.2905 (10) Åθ = 2.2–26.5°
b = 5.8649 (4) ŵ = 0.85 mm−1
c = 15.9345 (12) ÅT = 295 K
β = 99.129 (1)°Block, brown
V = 1226.32 (16) Å30.50 × 0.40 × 0.30 mm
Z = 2
Data collection top
Bruker SMART APEX area-detector
diffractometer		2398 independent reflections
Radiation source: fine-focus sealed tube2067 reflections with I > 2σ(I)
graphiteRint = 0.017
φ and ω scansθmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS, Bruker, 2002)		h = −16→14
Tmin = 0.677, Tmax = 0.786k = −7→6
6243 measured reflectionsl = −19→13
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0436P)2 + 0.4293P]
where P = (Fo2 + 2Fc2)/3
2398 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
[Ni(C8H8NO3)2]·2C3H7NOV = 1226.32 (16) Å3
Mr = 537.21Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.2905 (10) ŵ = 0.85 mm−1
b = 5.8649 (4) ÅT = 295 K
c = 15.9345 (12) Å0.50 × 0.40 × 0.30 mm
β = 99.129 (1)°
Data collection top
Bruker SMART APEX area-detector
diffractometer		2398 independent reflections
Absorption correction: multi-scan
(SADABS, Bruker, 2002)		2067 reflections with I > 2σ(I)
Tmin = 0.677, Tmax = 0.786Rint = 0.017
6243 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.083Δρmax = 0.25 e Å−3
S = 1.04Δρmin = −0.20 e Å−3
2398 reflectionsAbsolute structure: ?
160 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
Ni10.00000.00000.00000.03529 (12)
O10.36927 (11)0.3031 (3)0.28775 (9)0.0573 (4)
H10.38310.40800.32170.086*
O20.11298 (11)0.0218 (2)0.08068 (10)0.0512 (4)
O3−0.16273 (10)0.2912 (3)0.00960 (10)0.0600 (4)
H3−0.18060.1977−0.02810.090*
O40.45924 (14)0.6291 (3)0.38447 (11)0.0733 (5)
N1−0.06182 (11)0.2487 (3)0.04612 (10)0.0401 (4)
N20.57279 (13)0.9128 (3)0.41807 (11)0.0477 (4)
C10.14012 (14)0.1839 (3)0.13806 (11)0.0370 (4)
C20.23725 (14)0.1673 (3)0.18586 (11)0.0412 (4)
H20.27860.04440.17730.049*
C30.27296 (14)0.3301 (3)0.24559 (12)0.0412 (4)
C40.21144 (16)0.5124 (3)0.26013 (14)0.0472 (5)
H40.23500.62250.30050.057*
C50.11510 (16)0.5279 (3)0.21400 (13)0.0444 (4)
H50.07440.65070.22410.053*
C60.07536 (14)0.3672 (3)0.15236 (11)0.0359 (4)
C7−0.02770 (14)0.3901 (3)0.10657 (11)0.0371 (4)
C8−0.09685 (17)0.5748 (4)0.12913 (15)0.0539 (5)
H8A−0.16640.52470.11640.081*
H8B−0.08800.70940.09680.081*
H8C−0.08040.60850.18870.081*
C90.62892 (19)0.7952 (4)0.49118 (15)0.0622 (6)
H9A0.63810.89580.53930.093*
H9B0.69430.74920.47870.093*
H9C0.59140.66310.50380.093*
C100.60887 (19)1.1364 (4)0.39838 (18)0.0678 (7)
H10A0.60671.23680.44560.102*
H10B0.56621.19570.34900.102*
H10C0.67771.12480.38750.102*
C110.49409 (16)0.8175 (4)0.37059 (14)0.0533 (5)
H110.46260.89770.32330.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.03338 (19)0.0364 (2)0.03341 (19)0.00408 (13)−0.00300 (12)−0.00579 (13)
O10.0471 (8)0.0590 (9)0.0575 (9)0.0005 (7)−0.0175 (7)−0.0137 (7)
O20.0461 (8)0.0486 (8)0.0520 (8)0.0128 (6)−0.0136 (6)−0.0206 (6)
O30.0393 (8)0.0685 (10)0.0646 (10)0.0185 (7)−0.0148 (7)−0.0263 (8)
O40.0707 (11)0.0620 (11)0.0790 (12)−0.0240 (9)−0.0133 (9)−0.0079 (9)
N10.0331 (8)0.0433 (8)0.0408 (8)0.0070 (6)−0.0033 (6)−0.0046 (7)
N20.0420 (9)0.0450 (9)0.0548 (10)−0.0038 (7)0.0031 (7)−0.0094 (8)
C10.0397 (9)0.0376 (9)0.0319 (9)−0.0009 (8)0.0000 (7)−0.0030 (7)
C20.0403 (10)0.0417 (10)0.0394 (10)0.0037 (8)−0.0005 (8)−0.0039 (8)
C30.0404 (10)0.0440 (10)0.0364 (9)−0.0059 (8)−0.0018 (8)0.0010 (8)
C40.0500 (11)0.0434 (11)0.0453 (11)−0.0072 (9)−0.0013 (9)−0.0120 (8)
C50.0466 (11)0.0396 (10)0.0460 (11)0.0014 (8)0.0041 (9)−0.0084 (8)
C60.0391 (9)0.0363 (9)0.0319 (9)−0.0004 (7)0.0046 (7)−0.0007 (7)
C70.0415 (10)0.0370 (10)0.0330 (9)0.0036 (8)0.0069 (7)−0.0004 (7)
C80.0506 (12)0.0528 (12)0.0563 (13)0.0135 (10)0.0025 (10)−0.0134 (10)
C90.0567 (13)0.0743 (16)0.0517 (13)−0.0062 (12)−0.0034 (10)−0.0073 (11)
C100.0595 (14)0.0498 (13)0.0917 (19)−0.0088 (11)0.0048 (13)−0.0066 (12)
C110.0470 (11)0.0536 (12)0.0553 (12)−0.0024 (10)−0.0046 (9)−0.0093 (10)
Geometric parameters (Å, °) top
Ni1—O2i1.8197 (14)C3—C41.387 (3)
Ni1—O21.8197 (14)C4—C51.375 (3)
Ni1—N1i1.8801 (15)C4—H40.9300
Ni1—N11.8801 (15)C5—C61.403 (3)
O1—C31.357 (2)C5—H50.9300
O1—H10.8200C6—C71.452 (2)
O2—C11.328 (2)C7—C81.501 (3)
O3—N11.3970 (19)C8—H8A0.9600
O3—H30.8200C8—H8B0.9600
O4—C111.232 (3)C8—H8C0.9600
N1—C71.297 (2)C9—H9A0.9600
N2—C111.315 (3)C9—H9B0.9600
N2—C101.447 (3)C9—H9C0.9600
N2—C91.454 (3)C10—H10A0.9600
C1—C21.394 (2)C10—H10B0.9600
C1—C61.418 (2)C10—H10C0.9600
C2—C31.378 (3)C11—H110.9300
C2—H20.9300
O2i—Ni1—O2180.00 (14)C6—C5—H5118.5
O2i—Ni1—N1i91.84 (6)C5—C6—C1116.83 (17)
O2—Ni1—N1i88.16 (6)C5—C6—C7120.64 (16)
O2i—Ni1—N188.16 (6)C1—C6—C7122.52 (16)
O2—Ni1—N191.84 (6)N1—C7—C6120.30 (16)
N1i—Ni1—N1180.00 (11)N1—C7—C8118.96 (17)
C3—O1—H1109.5C6—C7—C8120.74 (16)
C1—O2—Ni1129.80 (12)C7—C8—H8A109.5
N1—O3—H3109.5C7—C8—H8B109.5
C7—N1—O3113.25 (14)H8A—C8—H8B109.5
C7—N1—Ni1131.56 (13)C7—C8—H8C109.5
O3—N1—Ni1115.19 (11)H8A—C8—H8C109.5
C11—N2—C10121.4 (2)H8B—C8—H8C109.5
C11—N2—C9121.3 (2)N2—C9—H9A109.5
C10—N2—C9117.25 (18)N2—C9—H9B109.5
O2—C1—C2116.94 (16)H9A—C9—H9B109.5
O2—C1—C6123.20 (16)N2—C9—H9C109.5
C2—C1—C6119.86 (16)H9A—C9—H9C109.5
C3—C2—C1121.11 (17)H9B—C9—H9C109.5
C3—C2—H2119.4N2—C10—H10A109.5
C1—C2—H2119.4N2—C10—H10B109.5
O1—C3—C2117.08 (17)H10A—C10—H10B109.5
O1—C3—C4122.81 (17)N2—C10—H10C109.5
C2—C3—C4120.11 (17)H10A—C10—H10C109.5
C5—C4—C3119.03 (17)H10B—C10—H10C109.5
C5—C4—H4120.5O4—C11—N2124.5 (2)
C3—C4—H4120.5O4—C11—H11117.8
C4—C5—C6123.04 (18)N2—C11—H11117.8
C4—C5—H5118.5
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.821.842.622 (2)159
O3—H3···O2i0.821.852.4857 (19)134
Symmetry codes: (i) −x, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.821.842.622 (2)159
O3—H3···O2i0.821.852.4857 (19)134
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

The author thanks the Science Foundation of Binzhou University for supporting this work (BZXYG0901 and BZXYQNLG200820).

references
References top

Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Chaudhuri, P. (2003). Coord. Chem. Rev. 243, 143–190.

Elo, H. & Lumme, P. (1985). Cancer Treat. Rep. 69, 1021–1022.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Hatzidimitriou, A. G., Uddin, M. & Lalia-Kantouri, M. (1997). Z. Anorg. Allg. Chem. 623, 627–632.

Keeney, M. E., Osseo-Asare, K. & Woode, K. A. (1984). Coord. Chem. Rev. 59, 141–201.

Milios, C. J., Inglis, R., Vinslava, A., Bagai, R., Wernsdorfer, W., Parsons, S., Perlepes, S. P., Christou, G. & Brechin, E. K. (2007). J. Am. Chem. Soc. 129, 12505–12511.

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

Voutsas, G. P., Keramidas, K. G., Dova, E., Lalia-Kantouri, M. & Hartophylles, M. (1999). Z. Kristallogr. New Cryst. Struct. 214, 33–34.