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Acta Cryst. (2008). E64, m173    [ doi:10.1107/S1600536807065506 ]

Bis{[mu]-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}dinickel(II)

Y. Ding, Z. Ku, L. Wang, Y. Hu and Y. Zhou

Abstract top

The asymmetric unit of the title compound, [Ni2(C16H14N2O2)2], contains an NiII cation which is coordinated by two imine N atoms and by two phenolate O atoms of the salen ligand {salen = N,N'-bis(salicylidene)ethane-1,2-diamine or 2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenol}, leading to a distorted square-planar conformation. When a secondary Ni-O interaction > 2.41 Å to the neighbouring phenolate O atom is considered, two molecules are linked into a centrosymmetric dimer with an overall square-pyramidal coordination for the NiII cation. Weak [pi]-[pi] interactions with a shortest interplanar distance of 3.704 Å help to stabilize the crystal structure.

Comment top

A review on metal-salen complexes in catalysis was given recently by Cozzi (2004). Herein, we report on synthesis and crystal structure of [Ni(salen)]2, (I).

As shown in Fig. 1, the molecular structure of (I) is made up of a centrosymmetric dimer. The NiII cation is surrounded by two N atoms and two O atoms from the salen ligands leading to a distorted square coordination with mean Ni—O distances of 1.927 Å, and somewhat longer mean Ni—N distances of 1.952 Å. Secondary Ni1—O1(-x, y, 1/2 - z) interactions of 2.4106 (11) Å of one salen ligand to the neighbouring NiII center link two molecules to a centrosymmetric dimer with an Ni1···Ni1(-x, y, 1/2 - z) separation of 3.1946 (4) Å. The resulting overall coordination sphere of the NiII cation can thus be described as a distorted square pyramid.

As shown in Fig. 2, there are weak π-π interactions, with plane-to-plane distances and displacement angles for the planes Cg4···Cg5 and Cg5···Cg6 of 3.704 Å and 11.85 °, and 4.022 Å and 6.72 °, respectively. The planes Cg4, Cg5 and Cg6 consist of atoms C3—O2/N1, C1—C6 and C7—C12.

Related literature top

For a review on metal–salen complexes used in catalysis, see: Cozzi (2004).

Experimental top

Compound (I) was prepared by adding Ni(Ac)2.2H2O (0.110 g, 0.5 mmol) to a solution of H2(salen) 0.122 mg (0.5 mmol) in methanol (20 mL) and DMF (20 ml). After stirring the mixture for 2 h, the solution was filtered and kept for several days at ambient temperature to evaporate. Brown block-like crystals were obtained.

Refinement top

H atoms were placed in geometrically idealized positions and were refined in the riding mode with C–H = 0.97Å and Uiso(H)=1.5Ueq(C) for C14 and C15. All other H atoms were refined with C–H = 0.93Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL ((Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level [symmetry code: (i) -x, y, 1/2 - z].
[Figure 2] Fig. 2. The packing diagram of (I).
Bis{µ-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}dinickel(II) top
Crystal data top
[Ni2(C16H14N2O2)2]F000 = 1344
Mr = 650.00Dx = 1.593 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3127 reflections
a = 26.639 (2) Åθ = 2.8–26.6º
b = 6.9775 (6) ŵ = 1.44 mm−1
c = 14.7094 (12) ÅT = 273 (2) K
β = 97.501 (1)ºBlock, brown
V = 2710.7 (4) Å30.34 × 0.21 × 0.07 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3090 independent reflections
Radiation source: fine-focus sealed tube2607 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 273(2) Kθmax = 27.5º
φ– and ω– scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −34→32
Tmin = 0.641, Tmax = 0.906k = −7→9
8437 measured reflectionsl = −16→19
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.0243P)2 + 0.8084P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.39 e Å−3
3090 reflectionsΔρmin = −0.18 e Å−3
191 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00018 (7)
Secondary atom site location: difference Fourier map
Crystal data top
[Ni2(C16H14N2O2)2]V = 2710.7 (4) Å3
Mr = 650.00Z = 4
Monoclinic, C2/cMo Kα
a = 26.639 (2) ŵ = 1.44 mm−1
b = 6.9775 (6) ÅT = 273 (2) K
c = 14.7094 (12) Å0.34 × 0.21 × 0.07 mm
β = 97.501 (1)º
Data collection top
Bruker SMART CCD
diffractometer		3090 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2607 reflections with I > 2σ(I)
Tmin = 0.641, Tmax = 0.906Rint = 0.023
8437 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024191 parameters
wR(F2) = 0.056H-atom parameters constrained
S = 1.03Δρmax = 0.39 e Å−3
3090 reflectionsΔρmin = −0.18 e Å−3
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
Ni10.267171 (7)0.20529 (3)0.402119 (12)0.02626 (7)
C10.13571 (6)0.5214 (3)0.42203 (12)0.0431 (4)
H10.15050.63160.44920.052*
O10.21557 (4)0.37606 (15)0.43757 (7)0.0331 (2)
C30.14245 (6)0.1972 (2)0.36791 (11)0.0381 (4)
C20.16650 (6)0.3629 (2)0.40947 (10)0.0333 (3)
C60.08435 (7)0.5180 (3)0.39534 (14)0.0560 (5)
H60.06500.62530.40500.067*
C40.08991 (7)0.1999 (3)0.34122 (14)0.0520 (5)
H40.07430.09140.31380.062*
C50.06105 (7)0.3565 (3)0.35422 (15)0.0611 (6)
H50.02630.35510.33580.073*
C70.36315 (6)0.3962 (2)0.39857 (10)0.0341 (4)
C120.38590 (6)0.2332 (2)0.36206 (12)0.0383 (4)
C90.44526 (7)0.5552 (3)0.40933 (14)0.0560 (5)
H90.46510.66240.42610.067*
C80.39502 (7)0.5555 (3)0.42134 (13)0.0459 (4)
H80.38150.66440.44530.055*
C110.43741 (7)0.2396 (3)0.34965 (15)0.0538 (5)
H110.45180.13310.32510.065*
N10.31197 (5)0.03112 (18)0.34648 (9)0.0342 (3)
O20.31572 (4)0.40839 (15)0.41080 (8)0.0386 (3)
N20.21745 (5)0.00240 (18)0.37265 (9)0.0360 (3)
C130.35815 (6)0.0617 (2)0.33554 (11)0.0392 (4)
H130.3750−0.03490.30820.047*
C140.28630 (7)−0.1438 (2)0.30878 (12)0.0430 (4)
H14A0.3096−0.25130.31580.052*
H14B0.2747−0.12700.24400.052*
C150.24182 (7)−0.1823 (2)0.35987 (13)0.0443 (4)
H15A0.2181−0.26880.32500.053*
H15B0.2532−0.24070.41880.053*
C100.46695 (7)0.3965 (3)0.37237 (16)0.0618 (6)
H100.50090.39740.36340.074*
C160.16935 (7)0.0228 (2)0.35544 (11)0.0402 (4)
H160.1504−0.08320.33320.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02833 (11)0.02401 (11)0.02671 (11)0.00003 (8)0.00461 (7)−0.00381 (8)
C10.0403 (9)0.0467 (10)0.0431 (10)0.0081 (8)0.0082 (8)0.0044 (8)
O10.0303 (6)0.0334 (6)0.0356 (6)0.0004 (5)0.0048 (4)−0.0036 (5)
C30.0359 (9)0.0435 (10)0.0343 (9)−0.0052 (7)0.0030 (7)0.0054 (7)
C20.0326 (8)0.0405 (9)0.0271 (8)0.0013 (7)0.0056 (6)0.0068 (7)
C60.0404 (10)0.0672 (14)0.0615 (13)0.0172 (10)0.0112 (9)0.0118 (11)
C40.0390 (10)0.0646 (13)0.0510 (12)−0.0112 (9)0.0007 (8)0.0094 (10)
C50.0288 (9)0.0842 (16)0.0691 (14)0.0010 (10)0.0019 (9)0.0164 (12)
C70.0328 (8)0.0386 (9)0.0309 (8)−0.0011 (7)0.0037 (7)0.0026 (7)
C120.0357 (9)0.0395 (9)0.0403 (10)0.0041 (7)0.0066 (7)0.0034 (7)
C90.0434 (11)0.0600 (13)0.0637 (13)−0.0162 (9)0.0043 (9)0.0022 (10)
C80.0433 (10)0.0445 (10)0.0505 (11)−0.0054 (8)0.0082 (8)−0.0047 (8)
C110.0390 (10)0.0576 (12)0.0667 (13)0.0083 (9)0.0143 (9)0.0018 (10)
N10.0396 (7)0.0309 (7)0.0323 (7)0.0024 (6)0.0052 (6)−0.0032 (6)
O20.0349 (6)0.0327 (6)0.0499 (7)−0.0017 (5)0.0119 (5)−0.0051 (5)
N20.0425 (8)0.0318 (7)0.0342 (7)−0.0048 (6)0.0071 (6)−0.0026 (6)
C130.0438 (10)0.0365 (9)0.0387 (9)0.0109 (7)0.0110 (7)−0.0005 (7)
C140.0542 (11)0.0333 (9)0.0419 (10)0.0018 (8)0.0083 (8)−0.0087 (7)
C150.0583 (12)0.0301 (9)0.0455 (10)−0.0035 (8)0.0102 (9)−0.0035 (7)
C100.0330 (10)0.0720 (14)0.0817 (16)−0.0024 (10)0.0124 (10)0.0065 (12)
C160.0447 (10)0.0394 (9)0.0361 (9)−0.0142 (8)0.0037 (7)−0.0004 (7)
Geometric parameters (Å, °) top
Ni1—O21.9115 (11)C12—C131.433 (2)
Ni1—O11.9412 (10)C9—C81.373 (3)
Ni1—N21.9484 (13)C9—C101.392 (3)
Ni1—N11.9560 (13)C9—H90.9300
C1—C61.373 (2)C8—H80.9300
C1—C21.403 (2)C11—C101.364 (3)
C1—H10.9300C11—H110.9300
O1—C21.3217 (18)N1—C131.279 (2)
C3—C41.403 (2)N1—C141.472 (2)
C3—C21.421 (2)N2—C161.281 (2)
C3—C161.436 (2)N2—C151.466 (2)
C6—C51.387 (3)C13—H130.9300
C6—H60.9300C14—C151.508 (3)
C4—C51.364 (3)C14—H14A0.9700
C4—H40.9300C14—H14B0.9700
C5—H50.9300C15—H15A0.9700
C7—O21.3021 (18)C15—H15B0.9700
C7—C81.412 (2)C10—H100.9300
C7—C121.426 (2)C16—H160.9300
C12—C111.409 (2)
O2—Ni1—O191.35 (5)C9—C8—C7122.30 (18)
O2—Ni1—N2171.05 (5)C9—C8—H8118.9
O1—Ni1—N291.21 (5)C7—C8—H8118.9
O2—Ni1—N192.53 (5)C10—C11—C12122.30 (19)
O1—Ni1—N1170.36 (5)C10—C11—H11118.8
N2—Ni1—N183.67 (6)C12—C11—H11118.8
C6—C1—C2121.78 (18)C13—N1—C14119.87 (14)
C6—C1—H1119.1C13—N1—Ni1126.75 (11)
C2—C1—H1119.1C14—N1—Ni1113.21 (10)
C2—O1—Ni1125.41 (10)C7—O2—Ni1127.05 (10)
C4—C3—C2119.15 (16)C16—N2—C15121.38 (14)
C4—C3—C16118.13 (16)C16—N2—Ni1126.61 (12)
C2—C3—C16122.67 (15)C15—N2—Ni1111.57 (11)
O1—C2—C1118.39 (15)N1—C13—C12125.11 (15)
O1—C2—C3124.28 (15)N1—C13—H13117.4
C1—C2—C3117.33 (15)C12—C13—H13117.4
C1—C6—C5120.74 (18)N1—C14—C15108.46 (14)
C1—C6—H6119.6N1—C14—H14A110.0
C5—C6—H6119.6C15—C14—H14A110.0
C5—C4—C3122.08 (19)N1—C14—H14B110.0
C5—C4—H4119.0C15—C14—H14B110.0
C3—C4—H4119.0H14A—C14—H14B108.4
C4—C5—C6118.93 (17)N2—C15—C14107.30 (13)
C4—C5—H5120.5N2—C15—H15A110.3
C6—C5—H5120.5C14—C15—H15A110.3
O2—C7—C8118.69 (15)N2—C15—H15B110.3
O2—C7—C12124.88 (15)C14—C15—H15B110.3
C8—C7—C12116.43 (15)H15A—C15—H15B108.5
C11—C12—C7119.51 (16)C11—C10—C9118.58 (18)
C11—C12—C13117.88 (16)C11—C10—H10120.7
C7—C12—C13122.60 (15)C9—C10—H10120.7
C8—C9—C10120.87 (19)N2—C16—C3124.89 (15)
C8—C9—H9119.6N2—C16—H16117.6
C10—C9—H9119.6C3—C16—H16117.6
O2—Ni1—O1—C2148.07 (12)O1—Ni1—N1—C14−54.8 (3)
N2—Ni1—O1—C2−23.36 (12)N2—Ni1—N1—C143.41 (11)
N1—Ni1—O1—C234.3 (4)C8—C7—O2—Ni1−170.58 (11)
Ni1—O1—C2—C1−164.26 (11)C12—C7—O2—Ni110.4 (2)
Ni1—O1—C2—C316.4 (2)O1—Ni1—O2—C7177.25 (13)
C6—C1—C2—O1−179.44 (16)N2—Ni1—O2—C7−76.1 (4)
C6—C1—C2—C3−0.1 (3)N1—Ni1—O2—C7−11.58 (13)
C4—C3—C2—O1179.69 (15)O2—Ni1—N2—C16−86.3 (4)
C16—C3—C2—O12.5 (3)O1—Ni1—N2—C1620.29 (14)
C4—C3—C2—C10.4 (2)N1—Ni1—N2—C16−151.53 (15)
C16—C3—C2—C1−176.84 (15)O2—Ni1—N2—C1586.0 (3)
C2—C1—C6—C5−0.4 (3)O1—Ni1—N2—C15−167.35 (11)
C2—C3—C4—C5−0.3 (3)N1—Ni1—N2—C1520.84 (11)
C16—C3—C4—C5177.11 (18)C14—N1—C13—C12174.47 (15)
C3—C4—C5—C6−0.2 (3)Ni1—N1—C13—C12−0.4 (2)
C1—C6—C5—C40.5 (3)C11—C12—C13—N1176.60 (17)
O2—C7—C12—C11178.16 (16)C7—C12—C13—N1−4.5 (3)
C8—C7—C12—C11−0.8 (2)C13—N1—C14—C15158.62 (15)
O2—C7—C12—C13−0.7 (3)Ni1—N1—C14—C15−25.82 (17)
C8—C7—C12—C13−179.72 (15)C16—N2—C15—C14133.16 (16)
C10—C9—C8—C71.0 (3)Ni1—N2—C15—C14−39.67 (16)
O2—C7—C8—C9−179.08 (17)N1—C14—C15—N241.36 (18)
C12—C7—C8—C90.0 (3)C12—C11—C10—C90.2 (3)
C7—C12—C11—C100.8 (3)C8—C9—C10—C11−1.1 (3)
C13—C12—C11—C10179.71 (19)C15—N2—C16—C3178.62 (15)
O2—Ni1—N1—C136.72 (14)Ni1—N2—C16—C3−9.7 (2)
O1—Ni1—N1—C13120.4 (3)C4—C3—C16—N2176.60 (17)
N2—Ni1—N1—C13178.60 (14)C2—C3—C16—N2−6.1 (3)
O2—Ni1—N1—C14−168.47 (11)
Table 1
Selected geometric parameters (Å, °) top
Ni1—O21.9115 (11)Ni1—N21.9484 (13)
Ni1—O11.9412 (10)Ni1—N11.9560 (13)
O2—Ni1—O191.35 (5)O2—Ni1—N192.53 (5)
O2—Ni1—N2171.05 (5)O1—Ni1—N1170.36 (5)
O1—Ni1—N291.21 (5)N2—Ni1—N183.67 (6)
Acknowledgements top

This work was supported by the Natural Science Foundation of Xiaogan University (Z2008012).

references
References top

Bruker (2001). SAINT (Version 6.45), SMART (Version 5.628), SHELXTL (Version 6.12), and SADABS (Version 2.03). Bruker AXS, Inc., Madison, Wisconsin, USA.

Cozzi, P. G. (2004). Chem. Soc. Rev. 33, 410–421.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.