supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

bv2085 scheme

Acta Cryst. (2008). E64, m298    [ doi:10.1107/S1600536807068183 ]

Aquabis(o-vanillinato-[kappa]2O,O')nickel(II)

Q. Wang and D.-Q. Wang

Abstract top

The NiII atom in the title complex, aquabis(2-formyl-6-methoxyphenolato-[kappa]2O,O')nickel(II), [Ni(C8H7O3)2(H2O)], is five-coordinated by four O atoms from two o-vanillinate ligands and one water molecule in a slightly distorted square-pyramidal geometry ([tau] = 0.06). In the crystal structure, the molecules are linked into dimers by intermolecular O-H...O hydrogen bonds.

Comment top

The structural and magnetic properties of binuclear and polymetallic nickel(II) complexes with various bridging ligands have received considerable attention in the past three decades (Meyer et al., 1982; Soules et al., 1988; Edwards et al., 1992; Asokan et al., 1998). In this paper, we report here the synthesis and crystal structure of the title complex, a new nickel complex.

The molecular structure of the title complex, (I), is shown in Fig.1. The NiII atom is five-coordinated in which four oxygen O(1), O(2), O(4), O(5) atoms from two o-vanillin ligands and one water molecule in a slightly distorted square pyramidal geometry, the tau value is 0.06 (Addison et al., 1984). NI(1), O(1), C(1), C(2), C(3), O(2) and Ni(1),O(4), C(9), C(10), C(11), O(5) form two six-membered chelating rings, which are essentially coplanar with a dihedral angle of 6.7 (0.19)°.

As seen in Fig. 2, the molecules are linked into dimers by intermolecular O—H···O hydrogen bonds (Table 1).

Related literature top

For general background, see: Meyer et al. (1982); Soules et al. (1988); Edwards et al. (1992); Asokan et al. (1998). For calculation of τ parameter, see: Addison et al. 1984.

Experimental top

Amounts of 304.3 mg (2 mmol) of o-vanillin and 80.00 mg (2 mmol) of NaOH were stirred into 30 ml absolute ethanol under room room temperature for 20 minutes, nickel chloride hexahydrate in the amount of 237.7 mg (1 mmol) was added, and the mixture was heated with stirring for 7 h and then filtered. The well shaped green polyhedral crystals of [Ni (C8H7O3)2H2O] for structure determination and characterization were separated from the mother liquor by slow evaporation at room temperature after two weeks.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model, with C—H (methyl) 0.96, C—H (aromatic) 0.93, C—H 0.93 Å (methylene), O—H 0.85 Å (water), withUiso(H) =1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed approximately along the bc plane.
aquabis(2-formyl-6-methoxyphenolato-κ2O,O')nickel(II) top
Crystal data top
[Ni(C8H7O3)2(H2O)]F000 = 784
Mr = 379.00Dx = 1.524 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1614 reflections
a = 9.4569 (14) Åθ = 2.5–27.7º
b = 15.8320 (19) ŵ = 1.21 mm−1
c = 11.1372 (18) ÅT = 298 (2) K
β = 97.729 (2)ºBlock, green
V = 1652.3 (4) Å30.43 × 0.40 × 0.15 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer		2909 independent reflections
Radiation source: fine-focus sealed tube1462 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.083
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.625, Tmax = 0.840k = −10→18
8178 measured reflectionsl = −13→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.157  w = 1/[σ2(Fo2) + (0.0683P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2909 reflectionsΔρmax = 0.54 e Å−3
199 parametersΔρmin = −1.08 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C8H7O3)2(H2O)]V = 1652.3 (4) Å3
Mr = 379.00Z = 4
Monoclinic, P21/cMo Kα
a = 9.4569 (14) ŵ = 1.21 mm−1
b = 15.8320 (19) ÅT = 298 (2) K
c = 11.1372 (18) Å0.43 × 0.40 × 0.15 mm
β = 97.729 (2)º
Data collection top
Siemens SMART CCD area-detector
diffractometer		2909 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1462 reflections with I > 2σ(I)
Tmin = 0.625, Tmax = 0.840Rint = 0.083
8178 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0623 restraints
wR(F2) = 0.157H-atom parameters constrained
S = 1.00Δρmax = 0.54 e Å−3
2909 reflectionsΔρmin = −1.08 e Å−3
199 parameters
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
Ni10.67982 (8)0.96568 (5)0.38774 (6)0.0453 (3)
O10.8808 (4)0.9428 (2)0.4415 (3)0.0453 (3)
O20.6193 (4)0.8834 (2)0.4980 (3)0.0513 (11)
O30.4899 (6)0.7887 (3)0.6400 (4)0.0692 (14)
O40.7481 (4)1.0350 (2)0.2593 (3)0.0453 (3)
O50.4873 (4)0.9690 (2)0.3093 (3)0.0496 (11)
O60.2167 (5)0.9542 (3)0.2415 (4)0.0608 (12)
O70.6836 (4)1.0859 (2)0.5067 (3)0.0453 (3)
H20.60501.10430.46990.068*
H30.66191.08210.57820.068*
C10.9283 (7)0.8990 (4)0.5329 (6)0.0616 (19)
H11.02700.89760.55280.074*
C20.8499 (7)0.8524 (4)0.6073 (6)0.0543 (18)
C30.7005 (7)0.8465 (4)0.5862 (6)0.0475 (16)
C40.6359 (9)0.7939 (4)0.6677 (6)0.0586 (19)
C50.7127 (11)0.7527 (5)0.7618 (7)0.082 (3)
H50.66640.71880.81260.098*
C60.8604 (11)0.7610 (5)0.7822 (8)0.090 (3)
H60.91230.73330.84740.108*
C70.9297 (9)0.8095 (5)0.7074 (7)0.075 (2)
H71.02850.81470.72140.090*
C80.4138 (9)0.7343 (4)0.7120 (7)0.093 (3)
H8A0.45310.67840.71230.139*
H8B0.31490.73270.67830.139*
H8C0.42250.75540.79350.139*
C90.6688 (7)1.0686 (4)0.1745 (5)0.0551 (17)
H90.71421.10250.12310.066*
C100.5204 (7)1.0624 (4)0.1462 (5)0.0465 (16)
C110.4375 (7)1.0112 (3)0.2125 (5)0.0419 (15)
C120.2881 (7)1.0062 (4)0.1720 (6)0.0490 (16)
C130.2275 (8)1.0497 (4)0.0718 (6)0.0614 (19)
H130.13021.04440.04620.074*
C140.3087 (9)1.1010 (4)0.0087 (6)0.071 (2)
H140.26591.1308−0.05850.086*
C150.4511 (9)1.1083 (4)0.0442 (6)0.064 (2)
H150.50471.14380.00140.077*
C160.0696 (7)0.9382 (5)0.2025 (7)0.088 (3)
H16A0.01910.99090.19180.132*
H16B0.03090.90500.26250.132*
H16C0.05940.90810.12710.132*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0487 (5)0.0459 (5)0.0406 (5)−0.0023 (4)0.0037 (3)0.0054 (4)
O10.0487 (5)0.0459 (5)0.0406 (5)−0.0023 (4)0.0037 (3)0.0054 (4)
O20.058 (3)0.050 (2)0.044 (3)0.012 (2)−0.001 (2)0.014 (2)
O30.092 (4)0.050 (3)0.069 (3)−0.006 (3)0.026 (3)0.013 (2)
O40.0487 (5)0.0459 (5)0.0406 (5)−0.0023 (4)0.0037 (3)0.0054 (4)
O50.055 (3)0.048 (2)0.045 (2)−0.005 (2)0.003 (2)0.012 (2)
O60.051 (3)0.074 (3)0.055 (3)−0.011 (3)0.001 (2)0.005 (2)
O70.0487 (5)0.0459 (5)0.0406 (5)−0.0023 (4)0.0037 (3)0.0054 (4)
C10.054 (5)0.065 (5)0.060 (5)0.010 (4)−0.013 (4)0.001 (4)
C20.062 (5)0.048 (4)0.052 (4)0.018 (4)0.002 (4)0.002 (3)
C30.063 (5)0.039 (4)0.041 (4)0.010 (3)0.010 (4)−0.007 (3)
C40.091 (6)0.040 (4)0.046 (4)0.008 (4)0.014 (4)0.001 (3)
C50.135 (8)0.061 (5)0.052 (5)0.020 (5)0.017 (5)0.013 (4)
C60.113 (8)0.075 (6)0.080 (6)0.036 (6)0.008 (6)0.004 (5)
C70.075 (6)0.083 (6)0.063 (5)0.023 (5)−0.008 (4)0.007 (5)
C80.137 (8)0.058 (5)0.094 (6)−0.015 (5)0.051 (6)0.007 (4)
C90.059 (5)0.057 (4)0.049 (4)−0.004 (4)0.007 (4)0.006 (3)
C100.059 (5)0.040 (3)0.039 (4)0.004 (3)0.001 (3)0.005 (3)
C110.056 (5)0.034 (3)0.034 (4)0.002 (3)0.000 (3)−0.003 (3)
C120.056 (5)0.045 (4)0.046 (4)0.000 (3)0.003 (4)−0.002 (3)
C130.068 (5)0.068 (5)0.045 (4)0.009 (4)−0.005 (4)0.009 (4)
C140.090 (6)0.063 (5)0.055 (5)0.007 (5)−0.015 (4)0.011 (4)
C150.092 (6)0.052 (4)0.047 (4)−0.008 (4)0.008 (4)0.004 (3)
C160.047 (5)0.122 (7)0.092 (6)−0.008 (5)0.001 (4)0.012 (5)
Geometric parameters (Å, °) top
Ni1—O51.912 (4)C5—H50.9300
Ni1—O21.929 (4)C6—C71.364 (10)
Ni1—O11.949 (4)C6—H60.9300
Ni1—O41.978 (4)C7—H70.9300
Ni1—O72.316 (3)C8—H8A0.9600
O1—C11.263 (7)C8—H8B0.9600
O2—C31.301 (7)C8—H8C0.9600
O3—C41.377 (8)C9—C101.400 (8)
O3—C81.434 (7)C9—H90.9300
O4—C91.244 (6)C10—C111.405 (8)
O5—C111.302 (6)C10—C151.431 (8)
O6—C121.369 (7)C11—C121.426 (8)
O6—C161.423 (7)C12—C131.370 (8)
O7—H20.8502C13—C141.375 (9)
O7—H30.8502C13—H130.9300
C1—C21.395 (9)C14—C151.357 (9)
C1—H10.9300C14—H140.9300
C2—C31.404 (8)C15—H150.9300
C2—C71.431 (9)C16—H16A0.9600
C3—C41.428 (8)C16—H16B0.9600
C4—C51.359 (9)C16—H16C0.9600
C5—C61.391 (10)
O5—Ni1—O287.93 (16)C6—C7—C2119.8 (8)
O5—Ni1—O1167.31 (16)C6—C7—H7120.1
O2—Ni1—O192.25 (16)C2—C7—H7120.1
O5—Ni1—O492.17 (16)O3—C8—H8A109.5
O2—Ni1—O4171.17 (16)O3—C8—H8B109.5
O1—Ni1—O485.73 (16)H8A—C8—H8B109.5
O5—Ni1—O7100.30 (15)O3—C8—H8C109.5
O2—Ni1—O799.99 (14)H8A—C8—H8C109.5
O1—Ni1—O792.17 (14)H8B—C8—H8C109.5
O4—Ni1—O788.68 (14)O4—C9—C10128.7 (6)
C1—O1—Ni1125.2 (4)O4—C9—H9115.7
C3—O2—Ni1126.1 (4)C10—C9—H9115.7
C4—O3—C8118.3 (6)C9—C10—C11122.4 (6)
C9—O4—Ni1124.3 (4)C9—C10—C15118.8 (6)
C11—O5—Ni1127.5 (4)C11—C10—C15118.8 (6)
C12—O6—C16118.1 (5)O5—C11—C10124.5 (6)
Ni1—O7—H293.5O5—C11—C12117.7 (5)
Ni1—O7—H3119.4C10—C11—C12117.8 (6)
H2—O7—H399.8O6—C12—C13125.4 (6)
O1—C1—C2127.6 (6)O6—C12—C11113.5 (5)
O1—C1—H1116.2C13—C12—C11121.2 (6)
C2—C1—H1116.2C12—C13—C14120.8 (7)
C1—C2—C3122.6 (6)C12—C13—H13119.6
C1—C2—C7116.6 (7)C14—C13—H13119.6
C3—C2—C7120.8 (7)C15—C14—C13120.2 (7)
O2—C3—C2125.1 (6)C15—C14—H14119.9
O2—C3—C4118.8 (6)C13—C14—H14119.9
C2—C3—C4116.1 (6)C14—C15—C10121.2 (6)
C5—C4—O3124.0 (7)C14—C15—H15119.4
C5—C4—C3122.7 (8)C10—C15—H15119.4
O3—C4—C3113.2 (6)O6—C16—H16A109.5
C4—C5—C6120.0 (8)O6—C16—H16B109.5
C4—C5—H5120.0H16A—C16—H16B109.5
C6—C5—H5120.0O6—C16—H16C109.5
C7—C6—C5120.6 (8)H16A—C16—H16C109.5
C7—C6—H6119.7H16B—C16—H16C109.5
C5—C6—H6119.7
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H2···O2i0.852.212.899 (5)139
O7—H2···O3i0.852.212.929 (6)143
O7—H3···O5i0.852.172.907 (5)146
O7—H3···O6i0.852.252.906 (5)134
Symmetry codes: (i) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H2···O2i0.852.212.899 (5)139
O7—H2···O3i0.852.212.929 (6)143
O7—H3···O5i0.852.172.907 (5)146
O7—H3···O6i0.852.252.906 (5)134
Symmetry codes: (i) −x+1, −y+2, −z+1.
Acknowledgements top

The authors acknowledge the financial support of the Shandong Province Science Foundation, and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

references
References top

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.

Asokan, A., Varghese, B., Caneschi, A. & Manoharan, P. T. (1998). Inorg. Chem. 37, 228–232.

Edwards, A. J., Hoskins, B. F., Kachab, E. H., Markiewicz, A., Murray, K. S. & Robson, R. (1992). Inorg. Chem. 31, 3585–3591.

Meyer, A., Gleizes, A., Girerd, J. J., Verdaguer, M. & Kahn, O. (1982). Inorg. Chem. 21, 1729–1739.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Soules, R., Dahan, F., Laurent, J. P. & Castan, P. (1988). J. Chem. Soc. Dalton Trans. pp. 587–590.