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Acta Cryst. (2008). E64, m1253    [ doi:10.1107/S1600536808028171 ]

(2-{[2-(4-Chlorophenoxy)-1-oxidoethylidene-[kappa]O1]hydrazonomethyl}phenolato-[kappa]2N1,O)(1H-imidazole-[kappa]N3)nickel(II)

X.-H. Chen

Abstract top

In the title complex, [Ni(C15H11ClN2O3)(C3H4N2)], the NiII ion is coordinated by a phenolate O, hydrazine N and carbonyl O atom from the hydrazone ligand and by an N atom from the imidazole molecule, forming a distorted square-planar geometry. Intermolecular N-H...N hydrogen bonds link neighboring molecules into extended chains parallel to [100].

Comment top

Hydrazones are of interest owing to their capacity for chelating to transition (Sur et al., 1993; Sun et al., 2005), lanthanide (Ma et al., 1989) and main group (Liu & Gao 1998) metals. Here we report the crystal structure of the title complex, (I) (Fig. 1). The Ni(II) ion exists in a square-planar N2O2 coordination geometry defined by the phenolate O1, hydrazine N1, and carbonyl O2 atom of the hydrazone ligand, and N3 atom from the 1H-imidazole molecule. The hydrazone ligand in the title complex is distorted, the dihedral angle between the two phenyl rings being 50.56 (9)°. The corresponding dihedral angle is about 87° in the complex [Co(C15H12N2O3)(C5H7O2)(C3H7NO)] (Chen & Liu, 2006) with the ligand of salicylaldehyde phenoxyacylhydrazone. In the title complex, an extended one-dimensional chain structure is formed via intermolecular hydrogen bonds between the 1H-imidazole N—H groups and the uncoordinated N-atom of the hydrazone ligand (Fig. 2). The N4···N2(A) distance and the N4—H···N2(A) angle are 2.916 (3) Å and 171.92°, respectively [Symmetry code: (A) x - 1/2, y, -z + 1/2].

Related literature top

For general background, see: Liu & Gao (1998); Ma et al. (1989); (Sur et al. (1993); Sun et al. (2005). For related structures, see: Chen & Liu (2006).

Experimental top

The hydrazone ligand was prepared by the reaction of salicylaldehyde and 4-chloro-phenoxyacetylhydrazine in a molar ratio of 1:1 under reflux in ethanol for 2 h. The yellow product obtained on cooling was recrystallized from methanol. Salicylaldehyde 4-chloro-phenoxyacetylhydrazone (1 mmol), [Ni(OAc)2].4H2O (1 mmol), imidazole (1 mmol), N,N-dimethylformamide (5 ml), and methanol (10 ml) were stirred for 2 h. The solution was filtered and allowed to stand at room temperature for one week, and red crystals of complex (I) were obtained.

Refinement top

All H atoms were placed in idealized positions and treated as riding with N—H = 0.86 Å, C—H = 0.93–0.97Å and Uiso(H) = 1.2Ueq(C/N).

Computing details top

Data collection: TEXRAY (Molecular Structure Corporation,1999); cell refinement: TEXRAY (Molecular Structure Corporation,1999); data reduction: TEXSAN (Molecular Structure Corporation,1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEX (McArdle,1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Extended chain structure of (I).
(2-{[2-(4-Chlorophenoxy)-1-oxidoethylidene-κO1]hydrazonomethyl}phenolato- κ2N1,O)(1H-imidazole-κN3)nickel(II) top
Crystal data top
[Ni(C15H11ClN2O3)(C3H4N2)]F(000) = 1760
Mr = 429.50Dx = 1.576 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2947 reflections
a = 18.745 (5) Åθ = 3.0–27.5°
b = 6.6054 (14) ŵ = 1.25 mm−1
c = 29.230 (8) ÅT = 293 K
V = 3619.2 (16) Å3Prism, red
Z = 80.65 × 0.21 × 0.15 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4146 independent reflections
Radiation source: fine-focus sealed tube2947 reflections with I > 2σ(I)
graphiteRint = 0.058
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(TEXRAY; Molecular Structure Corporation, 1999)		h = −24→24
Tmin = 0.498, Tmax = 0.835k = −8→8
29384 measured reflectionsl = −37→37
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0475P)2]
where P = (Fo2 + 2Fc2)/3
4146 reflections(Δ/σ)max = 0.001
244 parametersΔρmax = 0.40 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
[Ni(C15H11ClN2O3)(C3H4N2)]V = 3619.2 (16) Å3
Mr = 429.50Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 18.745 (5) ŵ = 1.25 mm−1
b = 6.6054 (14) ÅT = 293 K
c = 29.230 (8) Å0.65 × 0.21 × 0.15 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4146 independent reflections
Absorption correction: multi-scan
(TEXRAY; Molecular Structure Corporation, 1999)		2947 reflections with I > 2σ(I)
Tmin = 0.498, Tmax = 0.835Rint = 0.058
29384 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.087Δρmax = 0.40 e Å−3
S = 0.96Δρmin = −0.30 e Å−3
4146 reflectionsAbsolute structure: ?
244 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
Ni10.160819 (13)0.65045 (4)0.262178 (8)0.03514 (10)
O10.11416 (8)0.6681 (2)0.31655 (5)0.0519 (4)
O20.20944 (7)0.63914 (19)0.20727 (4)0.0397 (3)
O30.30335 (9)0.7513 (2)0.14068 (5)0.0524 (4)
N10.25009 (9)0.6404 (2)0.28711 (5)0.0344 (3)
N20.30584 (9)0.6336 (2)0.25500 (6)0.0381 (4)
N30.07133 (9)0.6479 (2)0.23119 (6)0.0403 (4)
N4−0.04380 (10)0.6469 (3)0.21963 (6)0.0489 (4)
H4A−0.08890.65190.22500.059*
Cl10.44937 (4)0.82246 (10)−0.03563 (2)0.0718 (2)
C10.14251 (12)0.6600 (3)0.35761 (7)0.0433 (5)
C20.21615 (12)0.6403 (3)0.36618 (7)0.0393 (4)
C30.24043 (14)0.6287 (3)0.41153 (7)0.0508 (6)
H3A0.28900.61430.41710.061*
C40.19446 (16)0.6382 (3)0.44779 (8)0.0580 (6)
H4B0.21140.62850.47760.070*
C50.12234 (16)0.6625 (4)0.43930 (8)0.0589 (6)
H5A0.09080.67130.46380.071*
C60.09647 (14)0.6737 (4)0.39544 (8)0.0575 (6)
H6A0.04780.69060.39070.069*
C70.26712 (11)0.6330 (3)0.32997 (7)0.0396 (4)
H7A0.31510.62240.33760.048*
C80.27699 (11)0.6312 (3)0.21432 (7)0.0376 (4)
C90.32487 (11)0.6078 (3)0.17375 (7)0.0430 (5)
H9A0.37410.63120.18250.052*
H9B0.32100.47190.16140.052*
C100.33961 (11)0.7564 (3)0.10033 (7)0.0432 (5)
C110.32289 (16)0.9148 (4)0.07150 (9)0.0694 (8)
H11A0.28901.00990.08040.083*
C120.35588 (16)0.9335 (4)0.02962 (9)0.0709 (8)
H12A0.34401.03990.01020.085*
C130.40604 (13)0.7950 (3)0.01670 (7)0.0505 (5)
C140.42323 (14)0.6372 (3)0.04485 (7)0.0533 (6)
H14A0.45730.54310.03570.064*
C150.39005 (13)0.6170 (3)0.08685 (7)0.0481 (5)
H15A0.40180.50940.10600.058*
C160.05887 (13)0.6245 (4)0.18536 (8)0.0545 (6)
H16A0.09380.61070.16300.065*
C17−0.01198 (13)0.6245 (4)0.17777 (8)0.0619 (7)
H17A−0.03480.61170.14970.074*
C180.00820 (11)0.6595 (3)0.25023 (8)0.0418 (5)
H18A0.00080.67480.28150.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02247 (14)0.04455 (16)0.03838 (15)−0.00093 (10)0.00212 (10)0.00103 (11)
O10.0303 (8)0.0837 (11)0.0416 (8)0.0012 (8)0.0047 (6)0.0011 (7)
O20.0259 (7)0.0523 (8)0.0408 (7)−0.0004 (6)0.0013 (6)0.0006 (6)
O30.0488 (10)0.0576 (9)0.0507 (8)0.0156 (8)0.0168 (7)0.0097 (7)
N10.0259 (8)0.0354 (8)0.0419 (9)0.0007 (7)0.0018 (7)0.0000 (7)
N20.0249 (8)0.0471 (9)0.0422 (9)0.0004 (7)0.0043 (7)0.0010 (7)
N30.0268 (9)0.0488 (9)0.0453 (9)−0.0028 (7)0.0023 (7)−0.0002 (8)
N40.0238 (9)0.0643 (11)0.0585 (11)0.0004 (8)−0.0006 (8)0.0004 (9)
Cl10.0848 (5)0.0815 (4)0.0491 (3)0.0023 (4)0.0225 (3)0.0045 (3)
C10.0442 (13)0.0457 (11)0.0400 (10)−0.0037 (10)0.0040 (9)0.0005 (9)
C20.0423 (12)0.0345 (9)0.0413 (10)0.0001 (9)0.0003 (9)0.0005 (8)
C30.0533 (15)0.0526 (13)0.0467 (12)0.0052 (11)−0.0053 (11)−0.0010 (10)
C40.0749 (19)0.0589 (14)0.0401 (11)0.0025 (14)0.0010 (12)0.0006 (10)
C50.0646 (18)0.0688 (15)0.0433 (12)−0.0019 (13)0.0152 (12)−0.0017 (11)
C60.0441 (14)0.0787 (16)0.0497 (12)−0.0033 (12)0.0116 (11)0.0007 (12)
C70.0305 (11)0.0434 (10)0.0448 (11)0.0030 (9)−0.0038 (9)0.0021 (9)
C80.0282 (10)0.0399 (10)0.0448 (11)0.0005 (8)0.0034 (9)0.0026 (9)
C90.0302 (11)0.0569 (12)0.0418 (11)0.0031 (9)0.0044 (9)0.0037 (10)
C100.0353 (12)0.0492 (11)0.0450 (11)−0.0007 (9)0.0067 (9)0.0012 (10)
C110.0705 (19)0.0652 (15)0.0725 (17)0.0248 (14)0.0267 (15)0.0204 (14)
C120.076 (2)0.0674 (15)0.0692 (16)0.0195 (15)0.0218 (15)0.0269 (14)
C130.0502 (14)0.0613 (13)0.0400 (10)−0.0037 (11)0.0074 (10)0.0007 (10)
C140.0522 (14)0.0614 (14)0.0463 (12)0.0104 (12)0.0085 (11)−0.0039 (10)
C150.0456 (13)0.0551 (13)0.0436 (11)0.0105 (11)0.0018 (10)0.0046 (10)
C160.0335 (12)0.0849 (17)0.0452 (11)−0.0035 (12)0.0035 (10)−0.0045 (11)
C170.0363 (13)0.100 (2)0.0490 (13)−0.0063 (13)−0.0056 (10)−0.0039 (13)
C180.0267 (10)0.0506 (11)0.0480 (11)0.0006 (9)0.0016 (9)−0.0035 (10)
Geometric parameters (Å, °) top
Ni1—O11.8178 (14)C4—C51.384 (4)
Ni1—N11.8264 (17)C4—H4B0.9300
Ni1—O21.8473 (14)C5—C61.373 (3)
Ni1—N31.9064 (18)C5—H5A0.9300
O1—C11.314 (3)C6—H6A0.9300
O2—C81.284 (2)C7—H7A0.9300
O3—C101.362 (2)C8—C91.495 (3)
O3—C91.413 (2)C9—H9A0.9700
N1—C71.294 (3)C9—H9B0.9700
N1—N21.405 (2)C10—C151.377 (3)
N2—C81.307 (3)C10—C111.380 (3)
N3—C181.310 (3)C11—C121.377 (3)
N3—C161.368 (3)C11—H11A0.9300
N4—C181.326 (3)C12—C131.365 (4)
N4—C171.369 (3)C12—H12A0.9300
N4—H4A0.8600C13—C141.367 (3)
Cl1—C131.741 (2)C14—C151.383 (3)
C1—C61.406 (3)C14—H14A0.9300
C1—C21.409 (3)C15—H15A0.9300
C2—C31.404 (3)C16—C171.347 (3)
C2—C71.427 (3)C16—H16A0.9300
C3—C41.367 (3)C17—H17A0.9300
C3—H3A0.9300C18—H18A0.9300
O1—Ni1—N195.41 (7)N1—C7—H7A118.3
O1—Ni1—O2178.45 (7)C2—C7—H7A118.3
N1—Ni1—O283.87 (7)O2—C8—N2123.63 (19)
O1—Ni1—N389.58 (7)O2—C8—C9117.97 (18)
N1—Ni1—N3174.52 (7)N2—C8—C9118.34 (18)
O2—Ni1—N391.20 (7)O3—C9—C8107.58 (16)
C1—O1—Ni1126.98 (15)O3—C9—H9A110.2
C8—O2—Ni1110.41 (13)C8—C9—H9A110.2
C10—O3—C9117.83 (16)O3—C9—H9B110.2
C7—N1—N2117.51 (17)C8—C9—H9B110.2
C7—N1—Ni1127.87 (14)H9A—C9—H9B108.5
N2—N1—Ni1114.59 (12)O3—C10—C15125.01 (19)
C8—N2—N1107.48 (16)O3—C10—C11115.7 (2)
C18—N3—C16105.56 (19)C15—C10—C11119.2 (2)
C18—N3—Ni1126.33 (15)C12—C11—C10120.6 (2)
C16—N3—Ni1128.04 (15)C12—C11—H11A119.7
C18—N4—C17106.83 (19)C10—C11—H11A119.7
C18—N4—H4A126.6C13—C12—C11119.7 (2)
C17—N4—H4A126.6C13—C12—H12A120.1
O1—C1—C6117.9 (2)C11—C12—H12A120.1
O1—C1—C2124.22 (19)C12—C13—C14120.5 (2)
C6—C1—C2117.9 (2)C12—C13—Cl1119.65 (18)
C3—C2—C1119.4 (2)C14—C13—Cl1119.89 (19)
C3—C2—C7118.8 (2)C13—C14—C15120.1 (2)
C1—C2—C7121.83 (19)C13—C14—H14A119.9
C4—C3—C2121.7 (2)C15—C14—H14A119.9
C4—C3—H3A119.2C10—C15—C14119.9 (2)
C2—C3—H3A119.2C10—C15—H15A120.1
C3—C4—C5118.8 (2)C14—C15—H15A120.1
C3—C4—H4B120.6C17—C16—N3109.2 (2)
C5—C4—H4B120.6C17—C16—H16A125.4
C6—C5—C4121.3 (2)N3—C16—H16A125.4
C6—C5—H5A119.4C16—C17—N4106.4 (2)
C4—C5—H5A119.4C16—C17—H17A126.8
C5—C6—C1121.0 (2)N4—C17—H17A126.8
C5—C6—H6A119.5N3—C18—N4112.0 (2)
C1—C6—H6A119.5N3—C18—H18A124.0
N1—C7—C2123.49 (19)N4—C18—H18A124.0
N1—Ni1—O1—C1−3.95 (18)C2—C1—C6—C5−1.8 (3)
O2—Ni1—O1—C1−66 (2)N2—N1—C7—C2179.46 (15)
N3—Ni1—O1—C1173.78 (18)Ni1—N1—C7—C2−2.8 (3)
O1—Ni1—O2—C862 (2)C3—C2—C7—N1179.26 (18)
N1—Ni1—O2—C8−0.19 (13)C1—C2—C7—N1−1.2 (3)
N3—Ni1—O2—C8−177.80 (13)Ni1—O2—C8—N2−0.8 (2)
O1—Ni1—N1—C74.62 (17)Ni1—O2—C8—C9176.13 (13)
O2—Ni1—N1—C7−176.76 (16)N1—N2—C8—O21.6 (3)
N3—Ni1—N1—C7−150.9 (7)N1—N2—C8—C9−175.36 (16)
O1—Ni1—N1—N2−177.59 (11)C10—O3—C9—C8−179.55 (18)
O2—Ni1—N1—N21.03 (11)O2—C8—C9—O348.3 (2)
N3—Ni1—N1—N226.9 (8)N2—C8—C9—O3−134.64 (19)
C7—N1—N2—C8176.44 (17)C9—O3—C10—C158.3 (3)
Ni1—N1—N2—C8−1.59 (17)C9—O3—C10—C11−172.1 (2)
O1—Ni1—N3—C180.86 (18)O3—C10—C11—C12−179.4 (3)
N1—Ni1—N3—C18156.5 (6)C15—C10—C11—C120.3 (4)
O2—Ni1—N3—C18−177.80 (17)C10—C11—C12—C13−0.6 (5)
O1—Ni1—N3—C16−175.8 (2)C11—C12—C13—C140.6 (4)
N1—Ni1—N3—C16−20.2 (8)C11—C12—C13—Cl1−178.4 (2)
O2—Ni1—N3—C165.55 (19)C12—C13—C14—C15−0.3 (4)
Ni1—O1—C1—C6−179.05 (14)Cl1—C13—C14—C15178.68 (19)
Ni1—O1—C1—C21.5 (3)O3—C10—C15—C14179.7 (2)
O1—C1—C2—C3−178.61 (18)C11—C10—C15—C140.0 (4)
C6—C1—C2—C32.0 (3)C13—C14—C15—C100.0 (4)
O1—C1—C2—C71.8 (3)C18—N3—C16—C170.6 (3)
C6—C1—C2—C7−177.61 (18)Ni1—N3—C16—C17177.80 (16)
C1—C2—C3—C4−0.7 (3)N3—C16—C17—N4−0.4 (3)
C7—C2—C3—C4178.91 (19)C18—N4—C17—C160.1 (3)
C2—C3—C4—C5−0.9 (3)C16—N3—C18—N4−0.6 (2)
C3—C4—C5—C61.1 (4)Ni1—N3—C18—N4−177.83 (13)
C4—C5—C6—C10.3 (4)C17—N4—C18—N30.3 (2)
O1—C1—C6—C5178.8 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N2i0.862.062.916 (3)172
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
N4—H4A···N2i0.862.062.916 (3)172
Symmetry codes: (i) x−1/2, y, −z+1/2.
references
References top

Chen, X.-H. & Liu, S.-X. (2006). Acta Cryst. E62, m2869–m2871.

Liu, S.-X. & Gao, S. (1998). Polyhedron, 17, 81–84.

Ma, Y.-X., Ma, Z.-Q., Zhao, G., Ma, -Y. & Yang, M. (1989). Polyhedron, 8, 2105–2108.

McArdle, P. (1995). J. Appl. Cryst. 28, 65.

Molecular Structure Corporation (1999). TEXRAY and TEXSAN. MSC, The Woodlands, Texas, USA.

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

Sun, M.-M., Li, W.-P. & Liu, S.-X. (2005). Acta Cryst. E61, m1818–m1820.

Sur, H., Roychowdhuri, S. & Seth, S. (1993). Acta Cryst. C49, 870–873.