Acta Cryst. (2009). E65, m11 [ doi:10.1107/S1600536808040385 ]
In the title compound, [Ni(C8H7O3)(C10H8N2)]ClO4, the NiII atom is in a slightly distorted square-planar coordination by two N atoms from the 2,2'-bipyridine (bipy) ligand and two O atoms from the deprotonated 2-formyl-6-methoxyphenolate (mbd) ligand. The bipy ligand is nearly coplanar with the NiII square plane, the Ni atom being only 0.042 (2) Å from the mean plane, whereas the benzaldehyde plane is folded with respect to the square plane, making a dihedral angle of 19.17 (8)°. One of the O atoms of the perchlorate anion is involved in a weak interaction with the Ni atom, with an Ni-O distance of 2.5732 (18) Å. The packing is stabilized by weak C-H
O interactions.
Bipy (0.023 g, 0.12 mmol), Ni(ClO4)2 (0.028 g, 0.13 mmol) and Hmbd (0.020 g, 0.16 mmol), were added in a solvent of ethanol, the mixture was stirring were required. The resultant solution was kept at room temperature for three weeks yielding green crystals of (I)
All H atoms attached were fixed geometrically and treated as riding on their parent C atoms with C—H = 0.96 Å (methyl) or 0.93 Å (aromatic) with Uiso(H) = 1.2Ueq(aromatic) or Uiso(H) = 1.5Ueq(methyl).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2410fig1thm.gif)
| Fig. 1. Molecular view of compound (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. |
| [Ni(C8H7O3)(C10H8N2)]ClO4 | Z = 2 |
| Mr = 465.48 | F(000) = 476 |
| Triclinic, P1 | Dx = 1.647 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.460 (1) Å | Cell parameters from 3381 reflections |
| b = 9.580 (1) Å | θ = 1.7–25.2° |
| c = 11.956 (2) Å | µ = 1.22 mm−1 |
| α = 84.45 (1)° | T = 298 K |
| β = 80.05 (1)° | Block, green |
| γ = 80.25 (1)° | 0.32 × 0.26 × 0.19 mm |
| V = 938.4 (2) Å3 |
| Bruker APEXII area-detector diffractometer | 3381 independent reflections |
| Radiation source: fine-focus sealed tube | 2838 reflections with I > 2σ(I) |
| graphite | Rint = 0.009 |
| φ and ω scans | θmax = 25.2°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = 0→10 |
| Tmin = 0.696, Tmax = 0.801 | k = −11→11 |
| 3644 measured reflections | l = −14→14 |
| 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.077 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.049P)2] where P = (Fo2 + 2Fc2)/3 |
| 3381 reflections | (Δ/σ)max = 0.001 |
| 263 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.49 e Å−3 |
| [Ni(C8H7O3)(C10H8N2)]ClO4 | γ = 80.25 (1)° |
| Mr = 465.48 | V = 938.4 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.460 (1) Å | Mo Kα radiation |
| b = 9.580 (1) Å | µ = 1.22 mm−1 |
| c = 11.956 (2) Å | T = 298 K |
| α = 84.45 (1)° | 0.32 × 0.26 × 0.19 mm |
| β = 80.05 (1)° |
| Bruker APEXII area-detector diffractometer | 3381 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2838 reflections with I > 2σ(I) |
| Tmin = 0.696, Tmax = 0.801 | Rint = 0.009 |
| 3644 measured reflections | θmax = 25.2° |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.077 | Δρmax = 0.25 e Å−3 |
| S = 1.04 | Δρmin = −0.49 e Å−3 |
| 3381 reflections | Absolute structure: ? |
| 263 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 > 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 | ||
| Ni1 | 0.62596 (3) | 0.46273 (3) | 0.37323 (2) | 0.03207 (11) | |
| O1 | 0.8230 (2) | 0.46228 (19) | 0.43851 (14) | 0.0491 (4) | |
| O2 | 0.54224 (18) | 0.33979 (16) | 0.49436 (13) | 0.0397 (4) | |
| O3 | 0.4083 (2) | 0.12543 (17) | 0.59302 (15) | 0.0531 (5) | |
| N1 | 0.4407 (2) | 0.45896 (19) | 0.29274 (15) | 0.0356 (4) | |
| N2 | 0.6801 (2) | 0.6028 (2) | 0.24547 (15) | 0.0384 (4) | |
| C1 | 0.8713 (3) | 0.3669 (3) | 0.5099 (2) | 0.0539 (7) | |
| H1 | 0.9750 | 0.3677 | 0.5258 | 0.065* | |
| C2 | 0.7895 (3) | 0.2585 (3) | 0.5693 (2) | 0.0490 (6) | |
| C3 | 0.8710 (4) | 0.1578 (3) | 0.6437 (3) | 0.0797 (10) | |
| H3 | 0.9760 | 0.1654 | 0.6530 | 0.096* | |
| C4 | 0.7985 (5) | 0.0514 (3) | 0.7010 (3) | 0.0935 (13) | |
| H4 | 0.8532 | −0.0131 | 0.7499 | 0.112* | |
| C5 | 0.6424 (4) | 0.0376 (3) | 0.6871 (2) | 0.0711 (9) | |
| H5 | 0.5940 | −0.0367 | 0.7267 | 0.085* | |
| C6 | 0.5578 (3) | 0.1319 (2) | 0.6157 (2) | 0.0462 (6) | |
| C7 | 0.6294 (3) | 0.2479 (2) | 0.55657 (18) | 0.0390 (5) | |
| C8 | 0.3359 (4) | 0.0033 (3) | 0.6415 (2) | 0.0662 (8) | |
| H8A | 0.4119 | −0.0814 | 0.6251 | 0.099* | |
| H8B | 0.2399 | 0.0015 | 0.6094 | 0.099* | |
| H8C | 0.3075 | 0.0084 | 0.7225 | 0.099* | |
| C9 | 0.3265 (3) | 0.3750 (3) | 0.3212 (2) | 0.0416 (5) | |
| H9 | 0.3278 | 0.3148 | 0.3870 | 0.050* | |
| C10 | 0.2074 (3) | 0.3751 (3) | 0.2563 (2) | 0.0503 (6) | |
| H10 | 0.1300 | 0.3151 | 0.2774 | 0.060* | |
| C11 | 0.2044 (3) | 0.4647 (3) | 0.1599 (2) | 0.0544 (7) | |
| H11 | 0.1239 | 0.4668 | 0.1154 | 0.065* | |
| C12 | 0.3211 (3) | 0.5518 (3) | 0.1291 (2) | 0.0512 (6) | |
| H12 | 0.3208 | 0.6129 | 0.0637 | 0.061* | |
| C13 | 0.4388 (3) | 0.5464 (2) | 0.19728 (18) | 0.0380 (5) | |
| C14 | 0.5734 (3) | 0.6303 (2) | 0.17170 (18) | 0.0393 (5) | |
| C15 | 0.5939 (4) | 0.7291 (3) | 0.0798 (2) | 0.0557 (7) | |
| H15 | 0.5181 | 0.7493 | 0.0304 | 0.067* | |
| C16 | 0.7279 (4) | 0.7967 (3) | 0.0627 (2) | 0.0634 (8) | |
| H16 | 0.7435 | 0.8629 | 0.0011 | 0.076* | |
| C17 | 0.8374 (4) | 0.7669 (3) | 0.1357 (2) | 0.0594 (7) | |
| H17 | 0.9291 | 0.8113 | 0.1244 | 0.071* | |
| C18 | 0.8102 (3) | 0.6699 (3) | 0.2267 (2) | 0.0484 (6) | |
| H18 | 0.8848 | 0.6500 | 0.2770 | 0.058* | |
| Cl | 0.82646 (7) | 0.24175 (6) | 0.14548 (5) | 0.04118 (15) | |
| O4 | 0.8132 (2) | 0.2621 (2) | 0.26486 (14) | 0.0597 (5) | |
| O5 | 0.6696 (2) | 0.2285 (2) | 0.12270 (17) | 0.0753 (6) | |
| O6 | 0.8814 (3) | 0.3620 (2) | 0.07874 (16) | 0.0652 (5) | |
| O7 | 0.9370 (3) | 0.1160 (2) | 0.11921 (17) | 0.0757 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.03248 (17) | 0.03601 (17) | 0.03033 (16) | −0.01101 (12) | −0.01119 (11) | 0.00581 (11) |
| O1 | 0.0452 (10) | 0.0571 (11) | 0.0506 (10) | −0.0154 (8) | −0.0172 (8) | −0.0019 (9) |
| O2 | 0.0396 (9) | 0.0392 (9) | 0.0400 (9) | −0.0051 (7) | −0.0130 (7) | 0.0092 (7) |
| O3 | 0.0633 (12) | 0.0395 (10) | 0.0524 (10) | −0.0135 (9) | 0.0016 (9) | 0.0073 (8) |
| N1 | 0.0376 (10) | 0.0365 (10) | 0.0333 (9) | −0.0057 (8) | −0.0090 (8) | 0.0003 (8) |
| N2 | 0.0423 (11) | 0.0382 (11) | 0.0351 (10) | −0.0104 (9) | −0.0028 (8) | −0.0029 (8) |
| C1 | 0.0450 (15) | 0.0599 (17) | 0.0627 (17) | −0.0026 (13) | −0.0254 (13) | −0.0138 (14) |
| C2 | 0.0554 (16) | 0.0417 (14) | 0.0545 (15) | 0.0006 (12) | −0.0293 (13) | −0.0036 (12) |
| C3 | 0.087 (2) | 0.059 (2) | 0.104 (3) | 0.0030 (18) | −0.065 (2) | 0.0011 (19) |
| C4 | 0.133 (3) | 0.053 (2) | 0.109 (3) | −0.004 (2) | −0.084 (3) | 0.0223 (19) |
| C5 | 0.116 (3) | 0.0403 (16) | 0.0610 (18) | −0.0093 (17) | −0.0372 (18) | 0.0122 (13) |
| C6 | 0.0663 (17) | 0.0351 (13) | 0.0367 (12) | −0.0047 (12) | −0.0126 (12) | 0.0014 (10) |
| C7 | 0.0525 (14) | 0.0325 (12) | 0.0317 (11) | 0.0029 (11) | −0.0144 (10) | −0.0039 (9) |
| C8 | 0.090 (2) | 0.0397 (15) | 0.0617 (18) | −0.0221 (15) | 0.0168 (16) | 0.0003 (13) |
| C9 | 0.0405 (13) | 0.0436 (14) | 0.0427 (13) | −0.0110 (11) | −0.0101 (10) | 0.0012 (11) |
| C10 | 0.0427 (14) | 0.0594 (17) | 0.0530 (15) | −0.0150 (13) | −0.0107 (12) | −0.0059 (13) |
| C11 | 0.0469 (15) | 0.0707 (19) | 0.0503 (15) | −0.0073 (14) | −0.0226 (12) | −0.0046 (14) |
| C12 | 0.0531 (15) | 0.0616 (17) | 0.0414 (14) | −0.0082 (13) | −0.0201 (12) | 0.0045 (12) |
| C13 | 0.0421 (13) | 0.0389 (12) | 0.0320 (11) | −0.0016 (10) | −0.0085 (10) | −0.0009 (10) |
| C14 | 0.0454 (14) | 0.0381 (13) | 0.0330 (11) | −0.0040 (11) | −0.0050 (10) | −0.0019 (10) |
| C15 | 0.0692 (18) | 0.0561 (17) | 0.0394 (14) | −0.0127 (14) | −0.0074 (13) | 0.0109 (12) |
| C16 | 0.082 (2) | 0.0588 (18) | 0.0454 (15) | −0.0230 (16) | 0.0032 (15) | 0.0125 (13) |
| C17 | 0.0655 (19) | 0.0593 (18) | 0.0523 (16) | −0.0256 (15) | 0.0086 (14) | −0.0028 (14) |
| C18 | 0.0479 (14) | 0.0509 (15) | 0.0484 (14) | −0.0199 (12) | −0.0002 (11) | −0.0046 (12) |
| Cl | 0.0437 (3) | 0.0428 (3) | 0.0378 (3) | −0.0086 (3) | −0.0106 (2) | 0.0041 (2) |
| O4 | 0.0798 (13) | 0.0620 (12) | 0.0386 (9) | −0.0123 (10) | −0.0148 (9) | 0.0014 (9) |
| O5 | 0.0592 (12) | 0.1022 (17) | 0.0741 (14) | −0.0325 (12) | −0.0310 (10) | 0.0178 (12) |
| O6 | 0.0829 (14) | 0.0616 (12) | 0.0546 (11) | −0.0305 (11) | −0.0136 (10) | 0.0177 (9) |
| O7 | 0.0816 (15) | 0.0588 (13) | 0.0725 (14) | 0.0163 (11) | 0.0001 (11) | −0.0044 (11) |
| Ni1—O2 | 1.8932 (15) | C8—H8B | 0.9600 |
| Ni1—O1 | 1.9580 (16) | C8—H8C | 0.9600 |
| Ni1—N2 | 1.9783 (19) | C9—C10 | 1.374 (3) |
| Ni1—N1 | 1.9828 (18) | C9—H9 | 0.9300 |
| O1—C1 | 1.255 (3) | C10—C11 | 1.370 (3) |
| O2—C7 | 1.310 (3) | C10—H10 | 0.9300 |
| O3—C6 | 1.351 (3) | C11—C12 | 1.379 (4) |
| O3—C8 | 1.439 (3) | C11—H11 | 0.9300 |
| N1—C9 | 1.339 (3) | C12—C13 | 1.384 (3) |
| N1—C13 | 1.349 (3) | C12—H12 | 0.9300 |
| N2—C18 | 1.343 (3) | C13—C14 | 1.476 (3) |
| N2—C14 | 1.346 (3) | C14—C15 | 1.386 (3) |
| C1—C2 | 1.412 (4) | C15—C16 | 1.374 (4) |
| C1—H1 | 0.9300 | C15—H15 | 0.9300 |
| C2—C7 | 1.410 (3) | C16—C17 | 1.359 (4) |
| C2—C3 | 1.421 (4) | C16—H16 | 0.9300 |
| C3—C4 | 1.348 (5) | C17—C18 | 1.374 (3) |
| C3—H3 | 0.9300 | C17—H17 | 0.9300 |
| C4—C5 | 1.388 (5) | C18—H18 | 0.9300 |
| C4—H4 | 0.9300 | Cl—O7 | 1.4194 (19) |
| C5—C6 | 1.378 (4) | Cl—O5 | 1.4284 (19) |
| C5—H5 | 0.9300 | Cl—O6 | 1.4336 (18) |
| C6—C7 | 1.425 (3) | Cl—O4 | 1.4418 (17) |
| C8—H8A | 0.9600 | ||
| O2—Ni1—O1 | 92.24 (7) | O3—C8—H8C | 109.5 |
| O2—Ni1—N2 | 171.66 (7) | H8A—C8—H8C | 109.5 |
| O1—Ni1—N2 | 94.93 (7) | H8B—C8—H8C | 109.5 |
| O2—Ni1—N1 | 91.43 (7) | N1—C9—C10 | 122.1 (2) |
| O1—Ni1—N1 | 174.35 (7) | N1—C9—H9 | 119.0 |
| N2—Ni1—N1 | 81.75 (8) | C10—C9—H9 | 119.0 |
| C1—O1—Ni1 | 122.66 (17) | C11—C10—C9 | 119.0 (2) |
| C7—O2—Ni1 | 125.39 (15) | C11—C10—H10 | 120.5 |
| C6—O3—C8 | 116.8 (2) | C9—C10—H10 | 120.5 |
| C9—N1—C13 | 119.0 (2) | C10—C11—C12 | 119.7 (2) |
| C9—N1—Ni1 | 126.47 (15) | C10—C11—H11 | 120.1 |
| C13—N1—Ni1 | 114.47 (15) | C12—C11—H11 | 120.1 |
| C18—N2—C14 | 118.7 (2) | C11—C12—C13 | 118.7 (2) |
| C18—N2—Ni1 | 126.43 (17) | C11—C12—H12 | 120.7 |
| C14—N2—Ni1 | 114.84 (15) | C13—C12—H12 | 120.7 |
| O1—C1—C2 | 128.7 (2) | N1—C13—C12 | 121.5 (2) |
| O1—C1—H1 | 115.7 | N1—C13—C14 | 114.52 (19) |
| C2—C1—H1 | 115.7 | C12—C13—C14 | 124.0 (2) |
| C7—C2—C1 | 121.7 (2) | N2—C14—C15 | 121.0 (2) |
| C7—C2—C3 | 119.4 (3) | N2—C14—C13 | 114.38 (19) |
| C1—C2—C3 | 119.0 (3) | C15—C14—C13 | 124.6 (2) |
| C4—C3—C2 | 121.0 (3) | C16—C15—C14 | 119.1 (3) |
| C4—C3—H3 | 119.5 | C16—C15—H15 | 120.4 |
| C2—C3—H3 | 119.5 | C14—C15—H15 | 120.4 |
| C3—C4—C5 | 120.2 (3) | C17—C16—C15 | 119.9 (3) |
| C3—C4—H4 | 119.9 | C17—C16—H16 | 120.0 |
| C5—C4—H4 | 119.9 | C15—C16—H16 | 120.0 |
| C6—C5—C4 | 121.3 (3) | C16—C17—C18 | 118.8 (3) |
| C6—C5—H5 | 119.4 | C16—C17—H17 | 120.6 |
| C4—C5—H5 | 119.4 | C18—C17—H17 | 120.6 |
| O3—C6—C5 | 126.1 (3) | N2—C18—C17 | 122.4 (3) |
| O3—C6—C7 | 114.1 (2) | N2—C18—H18 | 118.8 |
| C5—C6—C7 | 119.8 (3) | C17—C18—H18 | 118.8 |
| O2—C7—C2 | 123.6 (2) | O7—Cl—O5 | 109.87 (14) |
| O2—C7—C6 | 118.2 (2) | O7—Cl—O6 | 110.45 (13) |
| C2—C7—C6 | 118.3 (2) | O5—Cl—O6 | 109.20 (12) |
| O3—C8—H8A | 109.5 | O7—Cl—O4 | 109.12 (12) |
| O3—C8—H8B | 109.5 | O5—Cl—O4 | 108.41 (12) |
| H8A—C8—H8B | 109.5 | O6—Cl—O4 | 109.75 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···O7i | 0.93 | 2.58 | 3.461 (4) | 159 |
| C12—H12···O5ii | 0.93 | 2.57 | 3.499 (3) | 177 |
| C15—H15···O5ii | 0.93 | 2.59 | 3.517 (3) | 171 |
| Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···O7i | 0.93 | 2.58 | 3.461 (4) | 159 |
| C12—H12···O5ii | 0.93 | 2.57 | 3.499 (3) | 177 |
| C15—H15···O5ii | 0.93 | 2.59 | 3.517 (3) | 171 |
| Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z. |
The authors are grateful to the Young Teacher Underway Science Foundation of Southwest JiaoTong University for financial support.
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2,2'-Bipyridyl ligand is bidentate chelating ligand, which can commonly act as terminal ligands, and may also provide molecular interaction sites for molecular recognition or assembly (Minuti et al., 1999; Hamblin et al., 2002). On the other hand, aldehyde ligands have significant importance in chemistry, specially in the development of its complexes, because this type ligands are potentially capable of forming stable complexes with metal ions (Alizadeh et al., 1999). Herein we report the synthesis and characterization of the title complex with mixed co-ligand.
The NiII atom in the title complex, has a square coordination formed by two N atoms from Bipy ligand and two O atoms from protonated mbd ligand (Fig. 1). One of the O atom of the perchlorate anion is in weak interaction with the Ni atom with a Ni—O distance of 2.5732 (18) Å. The average Ni—N bond length of 1.98 Å is close to the values observed in related complexes (Liu et al., 2008). The occurrence of C—H···O hydrogen bonding stabilizes the packing (Table 1).