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Acta Cryst. (2007). E63, m2304    [ doi:10.1107/S1600536807038482 ]

[N,N'-Bis(6-methoxysalicylidene)-1,3-diaminopropane]nickel(II)

M. H. Habibi, R. Mokhtari, R. W. Harrington and W. Clegg

Abstract top

The title compound (systematic name: {3,3'-dimethoxy-2,2'-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato}nickel(II)), [Ni(C19H20N2O4)], is isostructural with its CuII analogue. The NiII ion is coordinated within a distorted square-planar N2O2 environment. The dihedral angle between the two NiNC3O chelate rings is 22.38 (12)°.

Comment top

Nickel(II) complexes with N2O2 Schiff-base ligands derived from salicylaldehyde have long been used as homogenous catalysts (Gosden et al., 1981; Healy & Pletcher, 1978). Recently we reported the structure of a copper(II) complex with the N,N'-bis(6-methoxysalicylidene)-1,3-diaminopropane ligand (Habibi et al., 2007). The title compound is isostructural with its CuII analogue.

In the title compound (Figure 1), the Ni—O and Ni—N distances are larger than the comparable mean distances of 1.829 and 1.859 Å, respectively, in N,N'-ethylenebis(salicylideneiminato)nickel(II) (Shkol'nikova et al., 1970) and 1.849 (2) and 1.840 (2) Å, respectively, in N,N'-ethylenebis[(2-hydroxy-1-naphthyl)methaniminato]nickel(II) (Akhtar, 1981).

Related literature top

For the isostructural CuII compound, see: Habibi et al. (2007). For related literature, see: Gosden et al. (1981); Healy & Pletcher (1978); Shkol'nikova et al. (1970); Akhtar (1981).

Experimental top

A mixture of 6-methoxysalicylaldehyde (2.0 mmol, 304 mg) and 1,3-diaminopropane (1.0 mmol, 74 mg) was dissolved in methanol (10 ml) with stirring for 10 min at room temperature, to give a clear yellow solution. A methanol solution (10 ml) of Ni(OAc)2·4H2O (1.0 mmol, 249 mg) was then added. The mixture was refluxed for a further 50 min and then filtered. After keeping the filtrate in air for 5 d, red block-shaped crystals were formed at the bottom of the vessel on slow evaporation of the solvent, in about 70% yield.

Refinement top

All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2 or 1.5 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2005); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure with atom labels and 50% probability displacement ellipsoids for non-H atoms.
{3,3'-dimethoxy-2,2'-[propane-1,3- diylbis(nitrilomethylidyne)]diphenolato}nickel(II) top
Crystal data top
[Ni(C19H20N2O4)]F000 = 832
Mr = 399.08Dx = 1.544 Mg m−3
Orthorhombic, Pca21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 7044 reflections
a = 13.677 (2) Åθ = 2.2–28.3º
b = 12.7319 (18) ŵ = 1.16 mm−1
c = 9.8561 (14) ÅT = 150 (2) K
V = 1716.3 (4) Å3Block, red
Z = 40.34 × 0.30 × 0.30 mm
Data collection top
Bruker SMART 1K CCD
diffractometer		4083 independent reflections
Radiation source: sealed tube3384 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
T = 150(2) Kθmax = 28.4º
thin–slice ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		h = −17→17
Tmin = 0.690, Tmax = 0.725k = −16→17
13065 measured reflectionsl = −13→12
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.0578P)2 + 0.6306P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.68 e Å−3
4083 reflectionsΔρmin = −0.53 e Å−3
238 parametersExtinction correction: SHELXTL (Sheldrick, 2005), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0025 (7)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 1870 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.00 (2)
Crystal data top
[Ni(C19H20N2O4)]V = 1716.3 (4) Å3
Mr = 399.08Z = 4
Orthorhombic, Pca21Mo Kα
a = 13.677 (2) ŵ = 1.16 mm−1
b = 12.7319 (18) ÅT = 150 (2) K
c = 9.8561 (14) Å0.34 × 0.30 × 0.30 mm
Data collection top
Bruker SMART 1K CCD
diffractometer		4083 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		3384 reflections with I > 2σ(I)
Tmin = 0.690, Tmax = 0.725Rint = 0.040
13065 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.101Δρmax = 0.68 e Å−3
S = 1.06Δρmin = −0.53 e Å−3
4083 reflectionsAbsolute structure: Flack (1983), with 1870 Friedel pairs
238 parametersFlack parameter: 0.00 (2)
1 restraint
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni0.82396 (2)0.25163 (3)0.10277 (8)0.01355 (10)
O10.8627 (2)−0.12162 (17)−0.1557 (3)0.0282 (6)
O20.93677 (17)0.21919 (17)0.0070 (2)0.0190 (5)
O30.90841 (15)0.34683 (16)0.1831 (2)0.0176 (5)
O40.69303 (16)0.5363 (2)0.4694 (3)0.0254 (5)
N10.76069 (19)0.12822 (18)0.0450 (3)0.0163 (5)
N20.71214 (18)0.31603 (19)0.1800 (3)0.0147 (5)
C10.8822 (3)−0.2066 (3)−0.2485 (4)0.0347 (9)
H1A0.8303−0.2593−0.24110.052*
H1B0.9452−0.2389−0.22590.052*
H1C0.8844−0.1794−0.34140.052*
C20.9282 (3)−0.0402 (2)−0.1530 (3)0.0208 (7)
C31.0159 (3)−0.0395 (3)−0.2224 (3)0.0244 (7)
H3A1.0353−0.0979−0.27610.029*
C41.0754 (3)0.0490 (3)−0.2116 (4)0.0254 (7)
H4A1.13560.0501−0.25970.031*
C51.0507 (2)0.1349 (3)−0.1343 (3)0.0222 (7)
H5A1.09420.1928−0.12780.027*
C60.9602 (2)0.1368 (2)−0.0644 (3)0.0178 (6)
C70.8979 (2)0.0481 (3)−0.0745 (3)0.0179 (6)
C80.8006 (2)0.0511 (2)−0.0200 (3)0.0185 (6)
H8A0.7615−0.0098−0.03310.022*
C90.6564 (2)0.1131 (2)0.0811 (3)0.0195 (7)
H9A0.64970.10510.18060.023*
H9B0.63100.04870.03730.023*
C100.5990 (2)0.2076 (3)0.0335 (4)0.0199 (7)
H10A0.52920.18850.02430.024*
H10B0.62320.2299−0.05670.024*
C110.6092 (2)0.2977 (3)0.1331 (3)0.0174 (7)
H11A0.58450.36270.08990.021*
H11B0.56760.28320.21320.021*
C120.7151 (2)0.3884 (2)0.2731 (3)0.0154 (6)
H12A0.65370.41130.30690.018*
C130.7990 (2)0.4375 (2)0.3308 (3)0.0153 (6)
C140.8929 (2)0.4154 (2)0.2787 (3)0.0154 (6)
C150.9741 (2)0.4713 (2)0.3329 (3)0.0200 (7)
H15A1.03820.45650.30090.024*
C160.9607 (2)0.5459 (2)0.4306 (4)0.0209 (7)
H16A1.01600.58190.46570.025*
C170.8673 (2)0.5711 (2)0.4810 (3)0.0194 (6)
H17A0.85940.62370.54850.023*
C180.7876 (2)0.5181 (2)0.4304 (3)0.0173 (6)
C190.6746 (3)0.6213 (3)0.5603 (4)0.0255 (8)
H19A0.60410.62680.57690.038*
H19B0.69840.68680.52010.038*
H19C0.70850.60850.64630.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.01077 (16)0.01476 (16)0.01513 (17)−0.00103 (14)0.0011 (2)−0.00126 (15)
O10.0344 (14)0.0200 (11)0.0301 (14)0.0000 (10)0.0024 (11)−0.0091 (10)
O20.0152 (11)0.0200 (10)0.0218 (12)0.0006 (9)0.0038 (9)−0.0030 (9)
O30.0112 (10)0.0186 (11)0.0229 (12)−0.0027 (8)0.0008 (9)−0.0038 (9)
O40.0096 (10)0.0312 (12)0.0354 (15)0.0022 (9)0.0021 (10)−0.0172 (11)
N10.0155 (13)0.0165 (12)0.0168 (13)−0.0028 (10)0.0004 (10)−0.0001 (10)
N20.0085 (12)0.0175 (12)0.0182 (14)−0.0014 (10)−0.0017 (10)−0.0001 (10)
C10.043 (2)0.0250 (18)0.036 (2)0.0011 (17)0.0013 (19)−0.0158 (16)
C20.0258 (18)0.0209 (15)0.0156 (16)0.0046 (13)−0.0049 (13)−0.0009 (13)
C30.0289 (19)0.0268 (16)0.0176 (16)0.0100 (15)−0.0004 (14)−0.0048 (13)
C40.0206 (17)0.0349 (18)0.0209 (17)0.0083 (14)0.0014 (14)−0.0011 (15)
C50.0205 (16)0.0258 (16)0.0203 (17)0.0023 (13)0.0010 (13)−0.0003 (13)
C60.0177 (15)0.0201 (14)0.0155 (15)0.0026 (12)−0.0014 (12)0.0002 (12)
C70.0185 (16)0.0205 (16)0.0146 (15)0.0045 (12)−0.0015 (12)−0.0004 (12)
C80.0210 (16)0.0168 (14)0.0177 (16)0.0005 (12)−0.0017 (12)0.0017 (12)
C90.0159 (14)0.0216 (14)0.0212 (19)−0.0053 (11)0.0027 (13)−0.0013 (12)
C100.0150 (15)0.0225 (15)0.0223 (17)−0.0036 (13)−0.0014 (13)−0.0048 (13)
C110.0059 (13)0.0240 (15)0.0222 (19)−0.0016 (11)−0.0026 (11)−0.0030 (12)
C120.0076 (13)0.0209 (14)0.0176 (15)0.0027 (11)0.0009 (11)−0.0012 (12)
C130.0098 (14)0.0164 (14)0.0196 (16)−0.0005 (11)−0.0004 (12)−0.0007 (12)
C140.0125 (15)0.0167 (14)0.0170 (16)0.0010 (12)0.0022 (12)0.0018 (12)
C150.0101 (15)0.0234 (15)0.0266 (18)−0.0019 (12)0.0022 (13)−0.0025 (13)
C160.0146 (15)0.0210 (15)0.0270 (18)−0.0041 (12)−0.0040 (14)−0.0034 (14)
C170.0163 (15)0.0201 (14)0.0218 (16)−0.0012 (12)−0.0002 (13)−0.0060 (12)
C180.0100 (14)0.0204 (15)0.0214 (16)0.0028 (11)0.0004 (12)−0.0034 (12)
C190.0202 (16)0.0280 (17)0.028 (2)0.0039 (13)0.0039 (13)−0.0105 (13)
Geometric parameters (Å, °) top
Ni—O21.855 (2)C6—C71.418 (4)
Ni—O31.852 (2)C7—C81.436 (5)
Ni—N11.882 (2)C8—H8A0.950
Ni—N21.895 (3)C9—H9A0.990
O1—C11.441 (4)C9—H9B0.990
O1—C21.370 (4)C9—C101.512 (5)
O2—C61.303 (4)C10—H10A0.990
O3—C141.302 (4)C10—H10B0.990
O4—C181.369 (4)C10—C111.516 (4)
O4—C191.427 (4)C11—H11A0.990
N1—C81.294 (4)C11—H11B0.990
N1—C91.482 (4)C12—H12A0.950
N2—C111.500 (4)C12—C131.425 (4)
N2—C121.301 (4)C13—C141.411 (4)
C1—H1A0.980C13—C181.428 (4)
C1—H1B0.980C14—C151.424 (4)
C1—H1C0.980C15—H15A0.950
C2—C31.381 (5)C15—C161.365 (4)
C2—C71.427 (4)C16—H16A0.950
C3—H3A0.950C16—C171.408 (4)
C3—C41.394 (5)C17—H17A0.950
C4—H4A0.950C17—C181.376 (4)
C4—C51.375 (5)C19—H19A0.980
C5—H5A0.950C19—H19B0.980
C5—C61.416 (4)C19—H19C0.980
O2—Ni—O381.06 (10)N1—C9—H9B109.9
O2—Ni—N192.44 (11)N1—C9—C10108.8 (2)
O2—Ni—N2166.39 (10)H9A—C9—H9B108.3
O3—Ni—N1164.26 (10)H9A—C9—C10109.9
O3—Ni—N292.77 (10)H9B—C9—C10109.9
N1—Ni—N296.42 (11)C9—C10—H10A109.5
C1—O1—C2117.4 (3)C9—C10—H10B109.5
Ni—O2—C6131.2 (2)C9—C10—C11110.7 (3)
Ni—O3—C14130.3 (2)H10A—C10—H10B108.1
C18—O4—C19118.2 (2)H10A—C10—C11109.5
Ni—N1—C8126.2 (2)H10B—C10—C11109.5
Ni—N1—C9118.56 (19)N2—C11—C10113.8 (3)
C8—N1—C9115.2 (3)N2—C11—H11A108.8
Ni—N2—C11124.5 (2)N2—C11—H11B108.8
Ni—N2—C12124.4 (2)C10—C11—H11A108.8
C11—N2—C12110.9 (3)C10—C11—H11B108.8
O1—C1—H1A109.5H11A—C11—H11B107.7
O1—C1—H1B109.5N2—C12—H12A115.9
O1—C1—H1C109.5N2—C12—C13128.1 (3)
H1A—C1—H1B109.5H12A—C12—C13115.9
H1A—C1—H1C109.5C12—C13—C14120.0 (3)
H1B—C1—H1C109.5C12—C13—C18120.1 (3)
O1—C2—C3124.2 (3)C14—C13—C18119.6 (3)
O1—C2—C7114.7 (3)O3—C14—C13123.1 (3)
C3—C2—C7121.1 (3)O3—C14—C15118.7 (3)
C2—C3—H3A120.9C13—C14—C15118.3 (3)
C2—C3—C4118.3 (3)C14—C15—H15A119.7
H3A—C3—C4120.9C14—C15—C16120.5 (3)
C3—C4—H4A118.6H15A—C15—C16119.7
C3—C4—C5122.8 (3)C15—C16—H16A119.0
H4A—C4—C5118.6C15—C16—C17122.0 (3)
C4—C5—H5A120.1H16A—C16—C17119.0
C4—C5—C6119.9 (3)C16—C17—H17A120.7
H5A—C5—C6120.1C16—C17—C18118.6 (3)
O2—C6—C5119.4 (3)H17A—C17—C18120.7
O2—C6—C7122.1 (3)O4—C18—C13114.7 (3)
C5—C6—C7118.5 (3)O4—C18—C17124.3 (3)
C2—C7—C6119.4 (3)C13—C18—C17121.0 (3)
C2—C7—C8119.5 (3)O4—C19—H19A109.5
C6—C7—C8120.7 (3)O4—C19—H19B109.5
N1—C8—C7126.6 (3)O4—C19—H19C109.5
N1—C8—H8A116.7H19A—C19—H19B109.5
C7—C8—H8A116.7H19A—C19—H19C109.5
N1—C9—H9A109.9H19B—C19—H19C109.5
O3—Ni—O2—C6161.9 (3)C3—C2—C7—C6−1.8 (5)
N1—Ni—O2—C6−3.7 (3)C3—C2—C7—C8171.0 (3)
N2—Ni—O2—C6−134.3 (5)Ni—N1—C8—C7−7.3 (5)
O2—Ni—O3—C14−179.7 (3)C9—N1—C8—C7175.7 (3)
N1—Ni—O3—C14−113.2 (4)C2—C7—C8—N1−175.1 (3)
N2—Ni—O3—C1412.5 (3)C6—C7—C8—N1−2.4 (5)
O2—Ni—N1—C88.9 (3)Ni—N1—C9—C1054.3 (3)
O2—Ni—N1—C9−174.2 (2)C8—N1—C9—C10−128.4 (3)
O3—Ni—N1—C8−56.2 (6)N1—C9—C10—C11−80.6 (3)
O3—Ni—N1—C9120.8 (4)Ni—N2—C11—C1010.4 (4)
N2—Ni—N1—C8178.5 (3)C12—N2—C11—C10−174.9 (3)
N2—Ni—N1—C9−4.5 (2)C9—C10—C11—N245.3 (4)
O2—Ni—N2—C11101.5 (5)Ni—N2—C12—C133.4 (5)
O2—Ni—N2—C12−72.5 (6)C11—N2—C12—C13−171.3 (3)
O3—Ni—N2—C11164.0 (2)N2—C12—C13—C145.6 (5)
O3—Ni—N2—C12−10.0 (3)N2—C12—C13—C18178.4 (3)
N1—Ni—N2—C11−28.8 (2)Ni—O3—C14—C13−7.5 (4)
N1—Ni—N2—C12157.2 (3)Ni—O3—C14—C15172.9 (2)
C1—O1—C2—C3−7.0 (5)C12—C13—C14—O3−3.7 (4)
C1—O1—C2—C7171.3 (3)C12—C13—C14—C15175.9 (3)
O1—C2—C3—C4179.5 (3)C18—C13—C14—O3−176.5 (3)
C7—C2—C3—C41.3 (5)C18—C13—C14—C153.0 (4)
C2—C3—C4—C50.5 (5)O3—C14—C15—C16178.2 (3)
C3—C4—C5—C6−1.7 (5)C13—C14—C15—C16−1.4 (5)
Ni—O2—C6—C5176.4 (2)C14—C15—C16—C17−0.4 (5)
Ni—O2—C6—C7−3.7 (5)C15—C16—C17—C180.5 (5)
C4—C5—C6—O2−179.0 (3)C19—O4—C18—C13−175.0 (3)
C4—C5—C6—C71.1 (5)C19—O4—C18—C175.2 (5)
O2—C6—C7—C2−179.3 (3)C16—C17—C18—O4−179.0 (3)
O2—C6—C7—C88.0 (5)C16—C17—C18—C131.2 (5)
C5—C6—C7—C20.6 (5)C12—C13—C18—O44.4 (4)
C5—C6—C7—C8−172.1 (3)C12—C13—C18—C17−175.8 (3)
O1—C2—C7—C6179.8 (3)C14—C13—C18—O4177.2 (3)
O1—C2—C7—C8−7.4 (4)C14—C13—C18—C17−3.0 (5)
Selected geometric parameters (Å, °) top
Ni—O21.855 (2)Ni—N11.882 (2)
Ni—O31.852 (2)Ni—N21.895 (3)
O2—Ni—O381.06 (10)O3—Ni—N1164.26 (10)
O2—Ni—N192.44 (11)O3—Ni—N292.77 (10)
O2—Ni—N2166.39 (10)N1—Ni—N296.42 (11)
Acknowledgements top

The authors thank the EPSRC (UK) and Isfahan University Centre of Excellence (Catalysis and Fuel Cells) for financial support.

references
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