Acta Cryst. (2012). E68, m935 [ doi:10.1107/S1600536812024944 ]
The asymmetric unit of the title compound, [Ni(C19H16I4N2O2)], comprises half of a Schiff base complex. The NiII atom is located on a twofold rotation axis which also bisects the central C atom of the 2,2-dimethylpropane group of the ligand. The geometry around the NiII atom is distorted square-planar, with a dihedral angle of 21.7 (3)° between the symmetry-related N/Ni/O coordination planes. The dihedral angle between the symmetry-related benzene rings is 27.9 (3)°. In the crystal, short intermolecular I
I [3.8178 (9) and 3.9013 (10) Å] interactions are present.
The title compound was synthesized by adding 2 mmol of 6,6'-(((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene)) bis(2,4-diiodophenol) to a solution of NiCl2. 6H2O (2.1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Dark-red block-like crystals of the title compound, suitable for X-ray structure analysis, were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.
The H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.93, 0.96 and 0.97 Å for CH, CH3 and CH2 H-atoms, respectively, with Uiso (H) = k x Ueq(C), where k = 1.5 for CH3 H-atoms, and = 1.2 for other H-atoms.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008)'; software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./su2444fig1thm.gif)
| Fig. 1. A view of the molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering [symmetry code for suffix A: -x + 1, y, -z+ 1/2]. |
![[Figure 2]](./su2444fig2thm.gif)
| Fig. 2. A view along the c axis of crystal packing of the title compound, showing the intermolecular I···I interactions (dashed lines). |
| [Ni(C19H16I4N2O2)] | F(000) = 1600 |
| Mr = 870.65 | Dx = 2.465 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 2540 reflections |
| a = 16.682 (2) Å | θ = 2.5–27.4° |
| b = 15.9978 (19) Å | µ = 6.11 mm−1 |
| c = 8.7920 (9) Å | T = 291 K |
| V = 2346.4 (5) Å3 | Block, dark-red |
| Z = 4 | 0.21 × 0.15 × 0.11 mm |
| Bruker SMART APEXII CCD area-detector diffractometer | 2582 independent reflections |
| Radiation source: fine-focus sealed tube | 1615 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.078 |
| φ and ω scans | θmax = 27.1°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −21→21 |
| Tmin = 0.360, Tmax = 0.553 | k = −20→18 |
| 10345 measured reflections | l = −11→9 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.096 | H-atom parameters constrained |
| S = 0.96 | w = 1/[σ2(Fo2) + (0.0314P)2] where P = (Fo2 + 2Fc2)/3 |
| 2582 reflections | (Δ/σ)max = 0.001 |
| 129 parameters | Δρmax = 1.07 e Å−3 |
| 0 restraints | Δρmin = −0.73 e Å−3 |
| [Ni(C19H16I4N2O2)] | V = 2346.4 (5) Å3 |
| Mr = 870.65 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 16.682 (2) Å | µ = 6.11 mm−1 |
| b = 15.9978 (19) Å | T = 291 K |
| c = 8.7920 (9) Å | 0.21 × 0.15 × 0.11 mm |
| Bruker SMART APEXII CCD area-detector diffractometer | 2582 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1615 reflections with I > 2σ(I) |
| Tmin = 0.360, Tmax = 0.553 | Rint = 0.078 |
| 10345 measured reflections | θmax = 27.1° |
| R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.096 | Δρmax = 1.07 e Å−3 |
| S = 0.96 | Δρmin = −0.73 e Å−3 |
| 2582 reflections | Absolute structure: ? |
| 129 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.6358 (4) | −0.0602 (4) | 0.1174 (7) | 0.0299 (16) | |
| C2 | 0.6886 (4) | −0.1295 (4) | 0.1037 (7) | 0.0362 (17) | |
| C3 | 0.7615 (4) | −0.1247 (5) | 0.0316 (7) | 0.0397 (18) | |
| H3 | 0.7938 | −0.1719 | 0.0252 | 0.048* | |
| C4 | 0.7876 (5) | −0.0496 (4) | −0.0323 (8) | 0.0416 (18) | |
| C5 | 0.7398 (5) | 0.0202 (5) | −0.0212 (8) | 0.0445 (19) | |
| H5 | 0.7569 | 0.0706 | −0.0629 | 0.053* | |
| C6 | 0.6647 (4) | 0.0157 (4) | 0.0534 (7) | 0.0319 (16) | |
| C7 | 0.6152 (4) | 0.0890 (4) | 0.0576 (7) | 0.0356 (17) | |
| H7 | 0.6320 | 0.1342 | −0.0009 | 0.043* | |
| C8 | 0.5034 (5) | 0.1751 (4) | 0.1100 (7) | 0.0389 (17) | |
| H8A | 0.4493 | 0.1598 | 0.0813 | 0.047* | |
| H8B | 0.5265 | 0.2066 | 0.0265 | 0.047* | |
| C9 | 0.5000 | 0.2309 (5) | 0.2500 | 0.038 (2) | |
| C10 | 0.4250 (5) | 0.2865 (5) | 0.2380 (10) | 0.062 (2) | |
| H10A | 0.3778 | 0.2522 | 0.2412 | 0.093* | |
| H10B | 0.4263 | 0.3168 | 0.1438 | 0.093* | |
| H10C | 0.4240 | 0.3252 | 0.3214 | 0.093* | |
| I1 | 0.65256 (3) | −0.24569 (3) | 0.19386 (5) | 0.04569 (18) | |
| I2 | 0.89983 (4) | −0.04176 (4) | −0.13554 (7) | 0.0658 (2) | |
| Ni1 | 0.5000 | 0.01657 (7) | 0.2500 | 0.0310 (3) | |
| N1 | 0.5506 (3) | 0.0986 (3) | 0.1332 (6) | 0.0339 (13) | |
| O1 | 0.5668 (3) | −0.0689 (3) | 0.1835 (5) | 0.0363 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.031 (4) | 0.027 (4) | 0.032 (4) | 0.006 (3) | 0.002 (3) | 0.000 (3) |
| C2 | 0.041 (4) | 0.028 (4) | 0.039 (4) | 0.007 (4) | 0.002 (3) | 0.002 (3) |
| C3 | 0.042 (5) | 0.035 (4) | 0.042 (4) | 0.009 (4) | −0.008 (4) | −0.006 (3) |
| C4 | 0.044 (5) | 0.032 (4) | 0.049 (4) | 0.003 (4) | 0.006 (4) | −0.005 (3) |
| C5 | 0.053 (5) | 0.042 (5) | 0.039 (4) | −0.006 (4) | 0.005 (4) | 0.001 (3) |
| C6 | 0.035 (4) | 0.023 (4) | 0.038 (4) | −0.002 (3) | −0.001 (3) | 0.007 (3) |
| C7 | 0.043 (5) | 0.023 (4) | 0.041 (4) | −0.002 (4) | 0.004 (4) | 0.007 (3) |
| C8 | 0.046 (5) | 0.026 (4) | 0.045 (4) | 0.005 (4) | 0.000 (4) | 0.006 (3) |
| C9 | 0.054 (7) | 0.012 (5) | 0.049 (6) | 0.000 | 0.006 (5) | 0.000 |
| C10 | 0.068 (6) | 0.053 (5) | 0.066 (5) | 0.019 (5) | 0.009 (5) | −0.004 (4) |
| I1 | 0.0588 (4) | 0.0285 (3) | 0.0498 (3) | 0.0072 (3) | 0.0027 (3) | 0.0056 (2) |
| I2 | 0.0448 (4) | 0.0558 (4) | 0.0967 (5) | −0.0031 (3) | 0.0273 (3) | −0.0059 (3) |
| Ni1 | 0.0323 (7) | 0.0229 (7) | 0.0378 (7) | 0.000 | 0.0032 (6) | 0.000 |
| N1 | 0.038 (4) | 0.021 (3) | 0.043 (3) | 0.008 (3) | 0.005 (3) | −0.001 (2) |
| O1 | 0.035 (3) | 0.025 (2) | 0.049 (3) | 0.005 (2) | 0.013 (2) | 0.002 (2) |
| C1—O1 | 1.297 (8) | C8—N1 | 1.469 (8) |
| C1—C2 | 1.422 (9) | C8—C9 | 1.521 (8) |
| C1—C6 | 1.423 (8) | C8—H8A | 0.9700 |
| C2—C3 | 1.374 (9) | C8—H8B | 0.9700 |
| C2—I1 | 2.108 (7) | C9—C8i | 1.521 (8) |
| C3—C4 | 1.396 (9) | C9—C10i | 1.540 (9) |
| C3—H3 | 0.9300 | C9—C10 | 1.540 (9) |
| C4—C5 | 1.376 (10) | C10—H10A | 0.9600 |
| C4—I2 | 2.085 (8) | C10—H10B | 0.9600 |
| C5—C6 | 1.417 (10) | C10—H10C | 0.9600 |
| C5—H5 | 0.9300 | Ni1—O1i | 1.858 (4) |
| C6—C7 | 1.434 (9) | Ni1—O1 | 1.858 (4) |
| C7—N1 | 1.275 (8) | Ni1—N1 | 1.868 (5) |
| C7—H7 | 0.9300 | Ni1—N1i | 1.868 (5) |
| O1—C1—C2 | 120.3 (6) | C9—C8—H8B | 108.9 |
| O1—C1—C6 | 124.7 (6) | H8A—C8—H8B | 107.7 |
| C2—C1—C6 | 115.0 (6) | C8i—C9—C8 | 108.2 (7) |
| C3—C2—C1 | 123.0 (6) | C8i—C9—C10i | 108.3 (4) |
| C3—C2—I1 | 118.4 (5) | C8—C9—C10i | 111.3 (4) |
| C1—C2—I1 | 118.6 (5) | C8i—C9—C10 | 111.3 (4) |
| C2—C3—C4 | 120.7 (7) | C8—C9—C10 | 108.3 (4) |
| C2—C3—H3 | 119.7 | C10i—C9—C10 | 109.4 (9) |
| C4—C3—H3 | 119.7 | C9—C10—H10A | 109.5 |
| C5—C4—C3 | 119.4 (7) | C9—C10—H10B | 109.5 |
| C5—C4—I2 | 120.2 (5) | H10A—C10—H10B | 109.5 |
| C3—C4—I2 | 120.4 (5) | C9—C10—H10C | 109.5 |
| C4—C5—C6 | 120.3 (7) | H10A—C10—H10C | 109.5 |
| C4—C5—H5 | 119.9 | H10B—C10—H10C | 109.5 |
| C6—C5—H5 | 119.9 | O1i—Ni1—O1 | 85.2 (3) |
| C5—C6—C1 | 121.8 (6) | O1i—Ni1—N1 | 163.9 (2) |
| C5—C6—C7 | 118.6 (6) | O1—Ni1—N1 | 94.2 (2) |
| C1—C6—C7 | 119.5 (6) | O1i—Ni1—N1i | 94.2 (2) |
| N1—C7—C6 | 126.7 (6) | O1—Ni1—N1i | 163.9 (2) |
| N1—C7—H7 | 116.6 | N1—Ni1—N1i | 90.7 (3) |
| C6—C7—H7 | 116.6 | C7—N1—C8 | 118.7 (6) |
| N1—C8—C9 | 113.3 (5) | C7—N1—Ni1 | 125.7 (5) |
| N1—C8—H8A | 108.9 | C8—N1—Ni1 | 114.8 (4) |
| C9—C8—H8A | 108.9 | C1—O1—Ni1 | 126.5 (4) |
| N1—C8—H8B | 108.9 | ||
| O1—C1—C2—C3 | 178.3 (6) | N1—C8—C9—C8i | −36.1 (4) |
| C6—C1—C2—C3 | −1.2 (10) | N1—C8—C9—C10i | 82.8 (7) |
| O1—C1—C2—I1 | −0.4 (8) | N1—C8—C9—C10 | −157.0 (6) |
| C6—C1—C2—I1 | −179.9 (5) | C6—C7—N1—C8 | −173.4 (6) |
| C1—C2—C3—C4 | 0.3 (11) | C6—C7—N1—Ni1 | −4.0 (10) |
| I1—C2—C3—C4 | 178.9 (5) | C9—C8—N1—C7 | −114.5 (7) |
| C2—C3—C4—C5 | 0.6 (11) | C9—C8—N1—Ni1 | 75.0 (6) |
| C2—C3—C4—I2 | 178.1 (5) | O1i—Ni1—N1—C7 | −95.4 (9) |
| C3—C4—C5—C6 | −0.4 (11) | O1—Ni1—N1—C7 | −8.0 (6) |
| I2—C4—C5—C6 | −177.9 (5) | N1i—Ni1—N1—C7 | 156.7 (7) |
| C4—C5—C6—C1 | −0.7 (11) | O1i—Ni1—N1—C8 | 74.4 (9) |
| C4—C5—C6—C7 | −177.7 (6) | O1—Ni1—N1—C8 | 161.7 (4) |
| O1—C1—C6—C5 | −178.1 (6) | N1i—Ni1—N1—C8 | −33.6 (3) |
| C2—C1—C6—C5 | 1.4 (9) | C2—C1—O1—Ni1 | 165.6 (5) |
| O1—C1—C6—C7 | −1.1 (10) | C6—C1—O1—Ni1 | −14.9 (9) |
| C2—C1—C6—C7 | 178.4 (6) | O1i—Ni1—O1—C1 | −178.8 (6) |
| C5—C6—C7—N1 | −171.8 (7) | N1—Ni1—O1—C1 | 17.2 (6) |
| C1—C6—C7—N1 | 11.1 (11) | N1i—Ni1—O1—C1 | −90.2 (9) |
| Symmetry code: (i) −x+1, y, −z+1/2. |
HK and TS thank PNU for financial support. MNT thanks GC University of Sargodha, Pakistan for the research facility.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Blower, P. J. (1998). Transition Met. Chem. 23, 109–112.
Bondi, A. (1964). J. Phys. Chem. 68, 441–452.
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Granovski, A. D., Nivorozhkin, A. L. & Minkin, V. I. (1993). Coord. Chem. Rev. 126, 1–69.
Kargar, H., Kia, R., Abbasian, S. & Tahir, M. N. (2012a). Acta Cryst. E68, m193.
Kargar, H., Kia, R., Shakarami, T. & Tahir, M. N. (2012c). Acta Cryst. E68, o564.
Kargar, H., Kia, R., Sharafi, Z. & Tahir, M. N. (2012b). Acta Cryst. E68, m82.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Schiff base complexes are one of the most important stereochemical models in transition metal coordination chemistry, with the ease of preparation and structural variations (Granovski et al., 1993; Blower et al., (1998). In continuation of our work on the crystal structure of Schiff base metal complexes (Kargar et al., 2012a,b), we report herein on the crystal structure of the title compound, the nickel(II) complex of the Schiff base ligand 6,6'-(((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2,4-diiodophenol). The structure of the Zwitterion form of this ligand has been reported by us (Kargar et al., 2012c).
The asymmetric unit of the title compound, Fig. 1, comprises half of a Schiff base complex. The NiII atom is located on a 2-fold rotation axis which also bisects the central C atom, C9, of the 2,2-dimethylpropane group in the ligand. The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to those reported for the ligand (Kargar et al., 2012c) and related structures (Kargar et al., 2012a,b). The geometry around atom Ni1 is distorted square-planar which is supported by the N2O2 donor atoms of the coordinated Schiff base ligand. The dihedral angle between the benzene rings (C1-C6 and C1i-C6i; symmetry code: (i) -x+1, y, -z+1/2) is 27.9 (3)°, while that between the symmetry-related coordination planes, N1,Ni1,O1 and N1i,Ni1i,O1i is 21.7 (3)°.
In the crystal, short intermolecular I1···I2i [3.8178 (9)Å; symmetry code: (i) -x+3/2, -y-1/2, z+1/2] and I2···I2ii [3.9013 (10)Å; symmetry code: (ii) -x+2, y, -z-1/2] interactions are present (Fig. 2). These interactions are shorter than the sum of the van der Waals radius of I atoms [3.96Å; Bondi, 1964].