Acta Cryst. (2009). E65, m566 [ doi:10.1107/S1600536809013920 ]
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2N,O]nickel(II)In the crystal structure of the title compound, [Ni(C14H13N2O)2], the NiII ion is located on an inversion center and is coordinated by two 4-methyl-2-(4-methylphenyldiazenyl)phenolate anions in a slightly distorted square-planar geometry. Within the anion, the two benzene rings are twisted from each other with a dihedral angle of 45.97 (12)°. No hydrogen bonding is found in the crystal structure.
Ni(H)(ortho-S-C6H4PPh2)(PMe3)2 (1.19 g, 2.35 mmol) and 2-(4'-methylphenylazo)-4-methylphenol (0.54 g, 2.38 mmol) was mixed in -80 °C. The mixture was stirred between -20 °C to 0 °C for 18 h and a red solution was formed. Green residue was filtered off, Then the solvent was removed in vacuum. The residue was extracted with pentane, and then diethyl ether. The extractions were kept in -20°C. The title compound was obtained from the pentane extractions as green crystals for X-ray diffraction.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2508fig1thm.gif)
| Fig. 1. View of the title compound, showing 25% displacement ellipsoids. H atoms were omitted. Symmetry code: (A) 2 - x, 2 - y, -z. |
| [Ni(C14H13N2O)2] | F(000) = 532 |
| Mr = 509.24 | Dx = 1.389 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1666 reflections |
| a = 9.5211 (10) Å | θ = 2.6–23.4° |
| b = 10.8162 (11) Å | µ = 0.83 mm−1 |
| c = 12.2647 (13) Å | T = 293 K |
| β = 105.367 (2)° | Block, green |
| V = 1217.9 (2) Å3 | 0.15 × 0.15 × 0.10 mm |
| Z = 2 |
| Bruker SMART APEX diffractometer | 2775 independent reflections |
| Radiation source: fine-focus sealed tube | 1890 reflections with I > 2σ(I) |
| graphite | Rint = 0.032 |
| ω scans | θmax = 27.6°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→11 |
| Tmin = 0.885, Tmax = 0.920 | k = −13→13 |
| 7063 measured reflections | l = −9→15 |
| 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.099 | All H-atom parameters refined |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0451P)2 + 0.1292P] where P = (Fo2 + 2Fc2)/3 |
| 2775 reflections | (Δ/σ)max < 0.001 |
| 212 parameters | Δρmax = 0.24 e Å−3 |
| 0 restraints | Δρmin = −0.19 e Å−3 |
| [Ni(C14H13N2O)2] | V = 1217.9 (2) Å3 |
| Mr = 509.24 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 9.5211 (10) Å | µ = 0.83 mm−1 |
| b = 10.8162 (11) Å | T = 293 K |
| c = 12.2647 (13) Å | 0.15 × 0.15 × 0.10 mm |
| β = 105.367 (2)° |
| Bruker SMART APEX diffractometer | 2775 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1890 reflections with I > 2σ(I) |
| Tmin = 0.885, Tmax = 0.920 | Rint = 0.032 |
| 7063 measured reflections | θmax = 27.6° |
| R[F2 > 2σ(F2)] = 0.038 | All H-atom parameters refined |
| wR(F2) = 0.099 | Δρmax = 0.24 e Å−3 |
| S = 1.02 | Δρmin = −0.19 e Å−3 |
| 2775 reflections | Absolute structure: ? |
| 212 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Ni | 1.0000 | 1.0000 | 0.0000 | 0.04172 (15) | |
| N1 | 0.96662 (19) | 0.83618 (16) | 0.04286 (15) | 0.0412 (4) | |
| N2 | 1.02859 (19) | 0.77982 (17) | 0.13462 (15) | 0.0448 (5) | |
| O | 1.0688 (2) | 1.04670 (16) | 0.14634 (14) | 0.0552 (5) | |
| C7 | 1.1204 (2) | 0.8429 (2) | 0.22272 (18) | 0.0428 (5) | |
| C1 | 0.8685 (2) | 0.75494 (19) | −0.03615 (18) | 0.0402 (5) | |
| C6 | 0.9169 (3) | 0.6442 (2) | −0.0673 (2) | 0.0440 (5) | |
| C4 | 0.6804 (3) | 0.6040 (2) | −0.1919 (2) | 0.0474 (6) | |
| C5 | 0.8231 (3) | 0.5700 (2) | −0.1455 (2) | 0.0480 (6) | |
| C2 | 0.7255 (3) | 0.7908 (2) | −0.0813 (2) | 0.0527 (6) | |
| C12 | 1.1914 (3) | 0.7700 (3) | 0.3162 (2) | 0.0524 (6) | |
| C8 | 1.1345 (3) | 0.9729 (2) | 0.2279 (2) | 0.0462 (6) | |
| C3 | 0.6333 (3) | 0.7146 (2) | −0.1575 (2) | 0.0559 (7) | |
| C9 | 1.2225 (3) | 1.0238 (3) | 0.3292 (2) | 0.0571 (7) | |
| C11 | 1.2798 (3) | 0.8206 (3) | 0.4119 (2) | 0.0560 (7) | |
| C10 | 1.2937 (3) | 0.9492 (3) | 0.4156 (2) | 0.0595 (7) | |
| C13 | 0.5765 (5) | 0.5215 (4) | −0.2756 (4) | 0.0741 (10) | |
| C14 | 1.3546 (5) | 0.7421 (5) | 0.5127 (3) | 0.0827 (11) | |
| H10 | 1.347 (3) | 0.987 (2) | 0.479 (2) | 0.050 (7)* | |
| H5 | 0.862 (3) | 0.494 (2) | −0.165 (2) | 0.048 (7)* | |
| H6 | 1.014 (2) | 0.624 (2) | −0.0350 (18) | 0.047 (6)* | |
| H12 | 1.173 (3) | 0.686 (2) | 0.311 (2) | 0.061 (8)* | |
| H3 | 0.541 (3) | 0.737 (2) | −0.185 (2) | 0.066 (8)* | |
| H9 | 1.232 (3) | 1.111 (3) | 0.333 (2) | 0.066 (8)* | |
| H13B | 0.594 (4) | 0.440 (4) | −0.253 (3) | 0.127 (16)* | |
| H13A | 0.603 (5) | 0.522 (4) | −0.338 (4) | 0.127 (19)* | |
| H2 | 0.689 (3) | 0.867 (3) | −0.057 (2) | 0.076 (8)* | |
| H13C | 0.491 (5) | 0.541 (3) | −0.290 (3) | 0.106 (15)* | |
| H14C | 1.454 (4) | 0.752 (4) | 0.527 (3) | 0.111 (13)* | |
| H14A | 1.318 (4) | 0.761 (4) | 0.576 (3) | 0.119 (14)* | |
| H14B | 1.341 (5) | 0.663 (5) | 0.504 (4) | 0.16 (2)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni | 0.0496 (3) | 0.0325 (2) | 0.0400 (2) | −0.00195 (18) | 0.00673 (18) | −0.00217 (18) |
| N1 | 0.0429 (10) | 0.0346 (10) | 0.0423 (10) | −0.0008 (8) | 0.0046 (8) | −0.0015 (8) |
| N2 | 0.0455 (11) | 0.0419 (11) | 0.0439 (11) | 0.0006 (8) | 0.0062 (9) | 0.0001 (9) |
| O | 0.0800 (13) | 0.0372 (8) | 0.0422 (9) | −0.0034 (8) | 0.0052 (9) | −0.0025 (8) |
| C7 | 0.0422 (12) | 0.0466 (13) | 0.0379 (12) | 0.0001 (10) | 0.0076 (10) | −0.0020 (10) |
| C1 | 0.0418 (13) | 0.0339 (11) | 0.0414 (12) | −0.0036 (9) | 0.0047 (10) | 0.0028 (9) |
| C6 | 0.0388 (13) | 0.0380 (12) | 0.0513 (14) | 0.0008 (10) | 0.0050 (10) | 0.0000 (11) |
| C4 | 0.0496 (14) | 0.0398 (13) | 0.0466 (13) | −0.0069 (10) | 0.0020 (11) | 0.0021 (11) |
| C5 | 0.0507 (14) | 0.0354 (13) | 0.0547 (15) | 0.0018 (11) | 0.0085 (12) | −0.0051 (11) |
| C2 | 0.0449 (14) | 0.0416 (14) | 0.0648 (16) | 0.0060 (11) | 0.0029 (12) | −0.0021 (12) |
| C12 | 0.0568 (16) | 0.0512 (16) | 0.0472 (14) | 0.0059 (13) | 0.0103 (12) | 0.0003 (12) |
| C8 | 0.0476 (14) | 0.0508 (15) | 0.0414 (13) | −0.0060 (10) | 0.0142 (11) | −0.0070 (10) |
| C3 | 0.0388 (14) | 0.0512 (15) | 0.0672 (17) | 0.0062 (12) | −0.0045 (12) | 0.0028 (13) |
| C9 | 0.0657 (17) | 0.0606 (18) | 0.0435 (14) | −0.0125 (13) | 0.0119 (13) | −0.0114 (12) |
| C11 | 0.0481 (14) | 0.0743 (19) | 0.0431 (14) | 0.0056 (13) | 0.0077 (11) | −0.0004 (13) |
| C10 | 0.0530 (16) | 0.083 (2) | 0.0392 (14) | −0.0108 (15) | 0.0070 (12) | −0.0122 (14) |
| C13 | 0.067 (2) | 0.061 (2) | 0.075 (2) | −0.0100 (17) | −0.0148 (19) | −0.0089 (17) |
| C14 | 0.074 (3) | 0.112 (4) | 0.0518 (19) | 0.013 (2) | −0.0005 (17) | 0.013 (2) |
| Ni—Oi | 1.8118 (16) | C2—C3 | 1.374 (3) |
| Ni—O | 1.8118 (16) | C2—H2 | 0.98 (3) |
| Ni—N1 | 1.8988 (18) | C12—C11 | 1.364 (3) |
| Ni—N1i | 1.8988 (18) | C12—H12 | 0.92 (2) |
| N1—N2 | 1.278 (2) | C8—C9 | 1.413 (3) |
| N1—C1 | 1.451 (3) | C3—H3 | 0.89 (2) |
| N2—C7 | 1.377 (3) | C9—C10 | 1.361 (4) |
| O—C8 | 1.303 (3) | C9—H9 | 0.95 (3) |
| C7—C12 | 1.408 (3) | C11—C10 | 1.397 (4) |
| C7—C8 | 1.412 (3) | C11—C14 | 1.513 (4) |
| C1—C6 | 1.373 (3) | C10—H10 | 0.91 (3) |
| C1—C2 | 1.382 (3) | C13—H13B | 0.92 (4) |
| C6—C5 | 1.381 (3) | C13—H13A | 0.87 (5) |
| C6—H6 | 0.93 (2) | C13—H13C | 0.81 (4) |
| C4—C5 | 1.377 (3) | C14—H14C | 0.92 (4) |
| C4—C3 | 1.382 (3) | C14—H14A | 0.95 (4) |
| C4—C13 | 1.514 (4) | C14—H14B | 0.86 (5) |
| C5—H5 | 0.95 (2) | ||
| Oi—Ni—O | 180.000 (1) | C11—C12—H12 | 121.2 (16) |
| Oi—Ni—N1 | 88.33 (8) | C7—C12—H12 | 116.8 (16) |
| O—Ni—N1 | 91.67 (8) | O—C8—C7 | 123.7 (2) |
| Oi—Ni—N1i | 91.67 (8) | O—C8—C9 | 119.2 (2) |
| O—Ni—N1i | 88.33 (8) | C7—C8—C9 | 117.0 (2) |
| N1—Ni—N1i | 180.0 | C2—C3—C4 | 121.8 (2) |
| N2—N1—C1 | 111.38 (17) | C2—C3—H3 | 119.1 (17) |
| N2—N1—Ni | 128.07 (14) | C4—C3—H3 | 119.2 (17) |
| C1—N1—Ni | 120.38 (13) | C10—C9—C8 | 120.7 (3) |
| N1—N2—C7 | 120.24 (19) | C10—C9—H9 | 122.2 (16) |
| C8—O—Ni | 124.29 (15) | C8—C9—H9 | 117.0 (16) |
| N2—C7—C12 | 115.5 (2) | C12—C11—C10 | 117.3 (2) |
| N2—C7—C8 | 124.1 (2) | C12—C11—C14 | 121.8 (3) |
| C12—C7—C8 | 120.1 (2) | C10—C11—C14 | 120.8 (3) |
| C6—C1—C2 | 120.0 (2) | C9—C10—C11 | 122.8 (3) |
| C6—C1—N1 | 120.67 (19) | C9—C10—H10 | 117.0 (15) |
| C2—C1—N1 | 119.3 (2) | C11—C10—H10 | 120.2 (14) |
| C1—C6—C5 | 119.8 (2) | C4—C13—H13B | 109 (2) |
| C1—C6—H6 | 117.3 (15) | C4—C13—H13A | 108 (3) |
| C5—C6—H6 | 122.9 (15) | H13B—C13—H13A | 101 (3) |
| C5—C4—C3 | 118.0 (2) | C4—C13—H13C | 115 (3) |
| C5—C4—C13 | 121.3 (3) | H13B—C13—H13C | 114 (3) |
| C3—C4—C13 | 120.8 (3) | H13A—C13—H13C | 108 (4) |
| C4—C5—C6 | 121.2 (2) | C11—C14—H14C | 109 (2) |
| C4—C5—H5 | 121.9 (15) | C11—C14—H14A | 111 (2) |
| C6—C5—H5 | 116.9 (15) | H14C—C14—H14A | 113 (3) |
| C3—C2—C1 | 119.2 (2) | C11—C14—H14B | 115 (3) |
| C3—C2—H2 | 120.0 (15) | H14C—C14—H14B | 104 (4) |
| C1—C2—H2 | 120.8 (15) | H14A—C14—H14B | 104 (4) |
| C11—C12—C7 | 122.0 (3) |
| Symmetry codes: (i) −x+2, −y+2, −z. |
Financial support from the Natural Science Foundation of China (grant Nos. 20872080 and 20772072) is gratefully acknowledged.
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Frey, M. (2005). PhD thesis, Darmstadt University of Technology, Germany.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Nickel hydride complexes are one of the most valuable catalysts and intermediates. Frey (2005) has successfully synthesized a new type of nickel hydride Ni(H)(ortho-S—C6H4PPh2)(PMe3)2. In the previous work in our lab, we have reported similar reactions between nickel or cobalt hydrides and phenol derivates. So the reaction between Ni(H)(ortho-S—C6H4PPh2)(PMe3)2 and phenol derivates was carried out to explore the acidity of the hydrogen ligand. The title compound, as an unexpected compound, was synthesized.
The molecular structure is shown in Fig. 1. The NiII ion is located in an inversion center and coordinated by two 2-(4'-methylphenylazo)-4-methylphenol anions in a square-planar geometry (Table 1). No hydrogen bonding is found in the crystal structure.