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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): m675–m676.
Published online 2008 April 16. doi:  10.1107/S1600536808009872
PMCID: PMC2961190

Tetra­kis(μ3-2-{[1,1-bis­(hydroxy­meth­yl)-2-oxidoeth­yl]imino­meth­yl}-6-methoxy­phenol­ato)tetra­nickel(II) tetra­hydrate

Abstract

The title complex, [Ni4(C12H15NO4)4]·4H2O, has crystal­lographic fourfold inversion symmetry, with each NiII ion coordinated in a slightly distorted square-pyramidal coordination environment and forming an Ni4O4 cubane-like core. In the crystal structure, inter­molecular O—H(...)O hydrogen bonds connect complex and water mol­ecules to form a three-dimensional network. The O atom of one of the unique hydroxy­methyl groups is disordered over two sites, with the ratio of occupancies being approximately 0.79:0.21.

Related literature

For related literature, see: Dong, Li, Xu & Wang (2007 [triangle]); Dong, Li, Xu, Cui & Wang (2007 [triangle]); Koikawa et al. (2005 [triangle]); Mishtu et al. (2002 [triangle]); Nihei et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m675-scheme1.jpg

Experimental

Crystal data

  • [Ni4(C12H15NO4)4]·4H2O
  • M r = 1319.90
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-64-0m675-efi1.jpg
  • a = 18.754 (2) Å
  • c = 15.4395 (15) Å
  • V = 5430.3 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.45 mm−1
  • T = 298 (2) K
  • 0.30 × 0.29 × 0.28 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.670, T max = 0.686
  • 11110 measured reflections
  • 2399 independent reflections
  • 1840 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.194
  • S = 1.08
  • 2399 reflections
  • 186 parameters
  • H-atom parameters constrained
  • Δρmax = 1.23 e Å−3
  • Δρmin = −0.70 e Å−3

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

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009872/lh2612sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009872/lh2612Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2004B02) for a research grant.

supplementary crystallographic information

Comment

The chemistry of transition metal ion complexes of hydroxy (aryl-OH and alkyl-OH) rich molecules containing imine/amine group is important in the biomimetic studies of metalloproteins (Mishtu et al., 2002). Polynuclear metal complexes with tridentate ligand containing hydroxyl groups as terminal coordinating atoms have been reported and have attracted much attention (Nihei et al., 2003).

A few structurally characterized multinuclear complexes containing Schiff base ligands has been reported( e.g. Dong, Li, Xu & Wang (2007); Dong, Li, Xu, Cui & Wang (2007); Nihei et al., 2003). Herein, we report the synthesis and crystal structure of a novel tetranickel(II) complex with a tridentate Schiff base ligand derived from the condensation of o-vanillin and trihydroxymethylaminomethane.

The title compound contains a tetranuclear cubane core based on an approximately cubic array of alternating nickel and oxygen atoms (Fig.1). Each NiII ion is in a distorted square-pyramidal coordination environment with one nitrogen and two oxygen atoms from one Schiff base ligand and two oxygen atoms from the symmetry related units of the cubane core. The Ni atom deviates from the basal plane (formed by O1, N1, O3 and O3i, symmetry code (i) y - 7/4, -x + 3/4, -z + 7/4) by 0.1299 (33) Å, with a significantly longer Ni—Oapical bond distance (Table 1). In the molecular structure, the Ni—Ni distances (3.472 (4) Å, 3.182 (3) Å) are longer than some reported values (Koikawa et al., 2005). In addition, there are four H2O solvent molecules, which are involved in intermolecular O-H···O hydrogen bonds (Fig. 2, Table 2) which stabilize the crystal atructure along with van der Waals forces.

Experimental

Trihydroxymethylaminomethane(1 mmol, 121.14 mg) was dissolved in hot methanol (10 ml) and added successively to a methanol solution(3 ml) of o-vanillin (1 mmol, 152.15 mg). The mixture was then stirred at 323 K for 2 h. Subsequently, an aqueous solution(2 ml) of nickel chlorate hexahydrate(1 mmol, 237.66 mg) was added dropwise and stirred for another 5 h. The solution was held at room temperature for ten days, whereupon green blocky crystals suitable for X-ray diffraction were obtained.

Refinement

Difference Fourier maps revealed that one of the hydroxymethyl group is distorted over two sites. The subsequent refinement of their occupancies gave the value of 0.791 (3) and 0.209 (3), respectively. All the H atoms were placed in geometrically calculated positions (C—H = 0.93 - 0.97 Å, O—H = 0.82 Å) and allowed to ride on their respective parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. The water solvent molecules are not shown. Open bonds indicate disordered atoms and only the assymetric unit is labelled.
Fig. 2.
Part of the crystal structure with hydrogen bonds shown as dashed lines. The disorder is not shown.

Crystal data

[Ni4(C12H15NO4)4]·4H2OZ = 4
Mr = 1319.90F000 = 2752
Tetragonal, I41/aDx = 1.614 Mg m3
Hall symbol: -I 4adMo Kα radiation λ = 0.71073 Å
a = 18.754 (2) ÅCell parameters from 3768 reflections
b = 18.754 (2) Åθ = 2.2–25.2º
c = 15.4395 (15) ŵ = 1.45 mm1
α = 90ºT = 298 (2) K
β = 90ºBlock, green
γ = 90º0.30 × 0.29 × 0.28 mm
V = 5430.3 (10) Å3

Data collection

Bruker SMART CCD area-detector diffractometer2399 independent reflections
Radiation source: fine-focus sealed tube1840 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.7º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −22→22
Tmin = 0.670, Tmax = 0.686k = −22→15
11110 measured reflectionsl = −9→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.194  w = 1/[σ2(Fo2) + (0.0801P)2 + 60.7787P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2399 reflectionsΔρmax = 1.23 e Å3
186 parametersΔρmin = −0.70 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/UeqOcc. (<1)
Ni10.40964 (4)0.72996 (4)1.05945 (5)0.0374 (3)
N10.3971 (4)0.6819 (3)0.9486 (4)0.0575 (16)
O10.3327 (2)0.7952 (2)1.0412 (3)0.0480 (11)
O20.2316 (3)0.8868 (4)1.0480 (5)0.097 (2)
O30.4952 (2)0.6720 (2)1.0675 (3)0.0435 (10)
O40.3704 (5)0.5372 (4)0.9346 (5)0.079 (2)0.791 (10)
H40.35330.50230.91030.119*0.791 (10)
O4'0.3587 (16)0.5547 (15)0.836 (2)0.079 (2)0.209 (10)
H4'0.35620.51340.81900.119*0.209 (10)
O50.4819 (5)0.6865 (5)0.7848 (5)0.120 (3)
H50.43830.68530.78930.181*
O60.3380 (3)0.6042 (3)0.0986 (4)0.0729 (16)
H6A0.37330.59780.13220.088*
H6B0.34720.58460.05030.088*
C10.3427 (4)0.6889 (4)0.9010 (5)0.061 (2)
H10.33920.65860.85350.073*
C20.2852 (4)0.7394 (4)0.9132 (5)0.0529 (18)
C30.2839 (3)0.7900 (4)0.9815 (4)0.0476 (16)
C40.2269 (4)0.8386 (5)0.9823 (5)0.067 (2)
C50.1712 (5)0.8344 (6)0.9218 (6)0.078 (3)
H5A0.13340.86640.92450.094*
C60.1727 (5)0.7834 (6)0.8595 (6)0.078 (3)
H60.13540.78000.82010.094*
C70.2279 (4)0.7377 (5)0.8544 (6)0.068 (2)
H70.22810.70380.81040.081*
C80.1829 (7)0.9466 (7)1.0493 (9)0.130 (5)
H8A0.17970.96680.99230.195*
H8B0.20010.98201.08910.195*
H8C0.13660.93061.06750.195*
C90.4572 (5)0.6290 (5)0.9262 (6)0.075 (3)
C100.4932 (4)0.6144 (4)1.0099 (4)0.0523 (17)
H10A0.46910.57491.03800.063*
H10B0.54180.59950.99810.063*
C110.4273 (5)0.5654 (5)0.8832 (6)0.073 (2)
H11A0.40960.57810.82620.088*0.791 (10)
H11B0.46420.52960.87620.088*0.791 (10)
H11C0.46350.55090.84200.088*0.209 (10)
H11D0.42760.52900.92790.088*0.209 (10)
C120.5136 (5)0.6631 (6)0.8640 (6)0.085 (3)
H12A0.53590.70330.89270.101*
H12B0.55040.62830.85140.101*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0427 (5)0.0358 (5)0.0337 (5)0.0002 (3)−0.0072 (3)−0.0007 (3)
N10.080 (4)0.046 (3)0.046 (3)0.015 (3)−0.022 (3)−0.009 (3)
O10.045 (3)0.055 (3)0.043 (2)0.008 (2)−0.009 (2)−0.005 (2)
O20.070 (4)0.125 (6)0.095 (5)0.048 (4)−0.010 (4)−0.019 (4)
O30.056 (3)0.039 (2)0.036 (2)0.010 (2)−0.008 (2)−0.0013 (19)
O40.094 (6)0.059 (4)0.086 (5)0.007 (4)−0.005 (5)−0.030 (4)
O4'0.094 (6)0.059 (4)0.086 (5)0.007 (4)−0.005 (5)−0.030 (4)
O50.111 (6)0.189 (8)0.061 (4)0.038 (6)0.005 (4)0.011 (5)
O60.053 (3)0.096 (4)0.070 (4)−0.001 (3)0.011 (3)−0.003 (3)
C10.079 (5)0.056 (4)0.048 (4)0.006 (4)−0.022 (4)−0.007 (3)
C20.055 (4)0.059 (4)0.045 (4)−0.010 (3)−0.013 (3)0.007 (3)
C30.039 (4)0.059 (4)0.044 (4)−0.001 (3)−0.002 (3)0.014 (3)
C40.049 (4)0.093 (6)0.058 (5)0.010 (4)−0.001 (4)0.002 (5)
C50.050 (5)0.110 (8)0.075 (6)0.014 (5)−0.004 (4)0.010 (6)
C60.060 (5)0.106 (7)0.069 (6)−0.008 (5)−0.018 (4)0.007 (5)
C70.064 (5)0.081 (6)0.058 (5)−0.011 (4)−0.025 (4)0.005 (4)
C80.105 (9)0.148 (12)0.137 (12)0.064 (9)−0.013 (8)−0.026 (9)
C90.088 (6)0.076 (6)0.061 (5)0.035 (5)−0.005 (5)−0.016 (4)
C100.054 (4)0.060 (4)0.043 (4)0.010 (3)−0.001 (3)−0.013 (3)
C110.081 (6)0.076 (6)0.061 (5)0.016 (5)−0.007 (5)−0.031 (5)
C120.085 (7)0.104 (8)0.065 (6)0.024 (6)0.001 (5)−0.002 (5)

Geometric parameters (Å, °)

Ni1—O11.912 (4)C2—C71.408 (10)
Ni1—O31.941 (4)C2—C31.419 (10)
Ni1—N11.949 (6)C3—C41.405 (11)
Ni1—O3i1.970 (4)C4—C51.403 (12)
Ni1—O3ii2.565 (5)C5—C61.357 (13)
N1—C11.265 (9)C5—H5A0.9300
N1—C91.541 (10)C6—C71.345 (13)
O1—C31.303 (8)C6—H60.9300
O2—C41.362 (11)C7—H70.9300
O2—C81.446 (12)C8—H8A0.9600
O3—C101.400 (8)C8—H8B0.9600
O3—Ni1iii1.970 (4)C8—H8C0.9600
O4—C111.430 (12)C9—C111.475 (13)
O4—H40.8200C9—C101.484 (11)
O4—H11D1.0883C9—C121.565 (14)
O4'—C111.49 (3)C10—H10A0.9700
O4'—H4'0.8200C10—H10B0.9700
O5—C121.429 (12)C11—H11A0.9700
O5—H50.8200C11—H11B0.9700
O6—H6A0.8500C11—H11C0.9698
O6—H6B0.8499C11—H11D0.9699
C1—C21.447 (11)C12—H12A0.9700
C1—H10.9300C12—H12B0.9700
O1—Ni1—O3172.2 (2)O2—C8—H8A109.5
O1—Ni1—N194.3 (2)O2—C8—H8B109.5
O3—Ni1—N184.1 (2)H8A—C8—H8B109.5
O1—Ni1—O3i94.57 (19)O2—C8—H8C109.5
O3—Ni1—O3i88.47 (19)H8A—C8—H8C109.5
N1—Ni1—O3i166.1 (2)H8B—C8—H8C109.5
O1—Ni1—O3ii94.23 (17)C11—C9—C10114.6 (8)
O3—Ni1—O3ii79.80 (17)C11—C9—N1110.2 (8)
N1—Ni1—O3ii117.2 (2)C10—C9—N1104.9 (6)
O3i—Ni1—O3ii72.63 (17)C11—C9—C12108.1 (8)
C1—N1—C9121.7 (6)C10—C9—C12107.5 (8)
C1—N1—Ni1124.1 (6)N1—C9—C12111.6 (7)
C9—N1—Ni1114.0 (5)O3—C10—C9115.0 (6)
C3—O1—Ni1125.9 (4)O3—C10—H10A108.5
C4—O2—C8119.0 (8)C9—C10—H10A108.5
C10—O3—Ni1111.7 (4)O3—C10—H10B108.5
C10—O3—Ni1iii121.9 (4)C9—C10—H10B108.5
Ni1—O3—Ni1iii108.9 (2)H10A—C10—H10B107.5
C11—O4—H4109.5O4—C11—C9109.4 (7)
H4—O4—H11D103.2O4—C11—O4'65.0 (13)
C11—O4'—H4'109.5C9—C11—O4'130.9 (13)
C12—O5—H5109.5O4—C11—H11A109.8
H6A—O6—H6B108.4C9—C11—H11A109.8
N1—C1—C2126.4 (7)O4'—C11—H11A45.3
N1—C1—H1116.8O4—C11—H11B109.8
C2—C1—H1116.8C9—C11—H11B109.8
C7—C2—C3118.8 (7)O4'—C11—H11B117.9
C7—C2—C1118.0 (7)H11A—C11—H11B108.2
C3—C2—C1123.1 (6)O4—C11—H11C141.6
O1—C3—C4118.7 (7)C9—C11—H11C104.8
O1—C3—C2124.4 (6)O4'—C11—H11C104.3
C4—C3—C2116.9 (7)H11A—C11—H11C73.3
O2—C4—C5125.6 (8)O4—C11—H11D49.5
O2—C4—C3112.8 (7)C9—C11—H11D104.3
C5—C4—C3121.6 (9)O4'—C11—H11D104.9
C6—C5—C4119.7 (9)H11A—C11—H11D145.1
C6—C5—H5A120.1H11B—C11—H11D65.7
C4—C5—H5A120.1H11C—C11—H11D105.4
C7—C6—C5120.5 (8)O5—C12—C9111.7 (8)
C7—C6—H6119.8O5—C12—H12A109.3
C5—C6—H6119.8C9—C12—H12A109.3
C6—C7—C2122.3 (9)O5—C12—H12B109.3
C6—C7—H7118.9C9—C12—H12B109.3
C2—C7—H7118.9H12A—C12—H12B107.9
C1—C2—C3—C4176.2 (7)

Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z; (iii) −y+5/4, x+1/4, −z+9/4.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5···N10.822.582.988 (9)112
O4—H4···O6iv0.821.942.714 (8)157
O4'—H4'···O6iv0.821.962.68 (3)148
O6—H6A···O1v0.851.952.803 (7)180
O6—H6B···O4vi0.852.042.892 (9)180

Symmetry codes: (iv) y−1/4, −x+3/4, z+3/4; (v) −y+5/4, x+1/4, −z+5/4; (vi) x, y, z−1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2612).

References

  • Dong, J.-F., Li, L.-Z., Xu, T., Cui, H. & Wang, D.-Q. (2007). Acta Cryst. E63, m1501–m1502.
  • Dong, J.-F., Li, L.-Z., Xu, H.-Y. & Wang, D.-Q. (2007). Acta Cryst. E63, m2300.
  • Koikawa, M., Ohba, M. & Tokii, T. (2005). Polyhedron, 24, 2257–2262.
  • Mishtu, D., Chebrolu, P. R., Pauli, K. S. & Kari, R. (2002). Inorg. Chem. Commun.5, 380–383.
  • Nihei, M., Hoshino, N., Ito, T. & Oshio, H. (2003). Polyhedron, 22, 2359–2362.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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