PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1570.
Published online 2010 November 13. doi:  10.1107/S1600536810046118
PMCID: PMC3011804

Diaqua­bis­{2-hy­droxy-5-[(pyridin-2-yl)methyl­idene­amino]­benzoato-κ2 N,N′}nickel(II) dihydrate

Abstract

In the title complex, [Ni(C13H9N2O3)2(H2O)2]·2H2O, the NiII atom, located on a twofold rotation axis, is in a distorted octa­hedral geometry, defined by four N atoms from two 2-hy­droxy-5-[(pyridin-2-yl)methyl­idene­amino]­benzoate ligands and two O atoms from two water mol­ecules. In the crystal, inter­molecular O—H(...)O hydrogen bonds link the complex mol­ecules and uncoordinated water mol­ecules into a three-dimensional network. Intra­molecular O—H(...)O hydrogen bonds are present between the hy­droxy and carboxyl­ate groups.

Related literature

For the biological activity of Schiff base compounds, see: Ali et al. (2002 [triangle]); Cukurovali et al. (2002 [triangle]); Tarafder et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1570-scheme1.jpg

Experimental

Crystal data

  • [Ni(C13H9N2O3)2(H2O)2]·2H2O
  • M r = 613.22
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1570-efi1.jpg
  • a = 15.7628 (6) Å
  • b = 10.5672 (3) Å
  • c = 15.6178 (6) Å
  • V = 2601.44 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.81 mm−1
  • T = 173 K
  • 0.41 × 0.34 × 0.12 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.725, T max = 0.907
  • 14975 measured reflections
  • 2294 independent reflections
  • 1599 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.074
  • S = 0.89
  • 2294 reflections
  • 202 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [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
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046118/hy2372sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046118/hy2372Isup2.hkl

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

Acknowledgments

This work was supported by the Ningbo Natural Science Foundation (grant No. 2010 A610060), the ‘Qianjiang Talent’ Projects of Zhejiang Province (grant No. 2009R10032), the Ningbo University Foundation (grant No. XK1066), the Program for Innovative Research Team of Ningbo Novel Photoelectric Materials and Devices (grant No. 2009B21007) and the K. C. Wong Magna Fund in Ningbo University.

supplementary crystallographic information

Comment

Schiff base compounds have been of great interest for many years. These compounds play an important role in antitumor, antimicrobial and antiviral activities (Ali et al., 2002; Cukurovali et al., 2002; Tarafder et al., 2002). As an extension of the work on the structural characterization of Schiff base compounds, the crystal structure of the title compound is reported here.

The title compound is a mononuclear nickel(II) complex, as shown in Fig. 1. The NiII atom, lying on a twofold rotation axis, is six-coordinated in a distorted octahedral geometry, defined by four N donors from two Schiff base ligands, two O atoms from two coordinated water molecules. The molecular formula contains two uncoordinated water molecules. The Ni—N bond lengths are 2.0754 (18) and 2.1347 (17) Å, and the Ni—O distance is 2.0380 (17) Å. Intramolecular O—H···O hydrogen bonds between the hydroxy and carboxylate groups are observed (Table 1). In the crystal, intermolecular O—H···O hydrogen bonds link the complex molecules and uncoordinated water molecules into a three-dimensional network (Fig. 2).

Experimental

5-Aminosalicylic acid (1.53 g, 10 mmol), 2-pyridinecarboxaldehyde (1 ml, 10 mmol) and triethylamine (1 ml, 10 mmol) were mixed in 50 ml ethanol in a round flask. The mixture was refluxed with agitation for 4 h at 323 K to give a yellow precipitate. After filtration and washing the precipitate with ethanol, a pure Schiff base ligand, 5-[(pyridin-2-yl)methyleneamino]-2-hydroxybenzoic acid (yield: 2.02 g, 84%) was obtained.

A mixture of 5-[(pyridin-2-yl)methyleneamino]-2-hydroxybenzoic acid (0.024 g, 0.1 mmol), Ni(CH3CO2)2.2H2O (0.025 g, 0.1 mmol) and ethanol (20 ml) was heated at 273 K for 30 min to give a red solution. After evaporating the solution at room temperature for one week, red crystals were obtained (yield: 65%).

Refinement

H atoms attached to C atoms and O3 were placed in calculated positions and treated using a riding model, with C—H = 0.95 and O—H = 0.84 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). H atoms attached to water molecules (O4 and O5) were located in a difference Fourier map and refined isotropically.

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) -x+1, y, -z+1/2.]
Fig. 2.
Three-dimensional supramolecular network in the title compound. Dashed lines denote hydrogen bonds.

Crystal data

[Ni(C13H9N2O3)2(H2O)2]·2H2OF(000) = 1272
Mr = 613.22Dx = 1.566 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 14975 reflections
a = 15.7628 (6) Åθ = 3.9–25.0°
b = 10.5672 (3) ŵ = 0.81 mm1
c = 15.6178 (6) ÅT = 173 K
V = 2601.44 (16) Å3Platelet, red
Z = 40.41 × 0.34 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer2294 independent reflections
Radiation source: fine-focus sealed tube1599 reflections with I > 2σ(I)
graphiteRint = 0.044
[var phi] and ω scansθmax = 25.0°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −18→18
Tmin = 0.725, Tmax = 0.907k = −12→12
14975 measured reflectionsl = −18→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 0.89w = 1/[σ2(Fo2) + (0.045P)2] where P = (Fo2 + 2Fc2)/3
2294 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.20 e Å3
4 restraintsΔρmin = −0.40 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Ni10.50000.40233 (3)0.25000.02879 (13)
C10.42670 (16)−0.1813 (2)0.09408 (16)0.0418 (6)
C20.42072 (13)−0.04024 (19)0.08275 (14)0.0314 (5)
C30.35591 (14)0.0140 (2)0.03319 (15)0.0371 (6)
C40.34858 (15)0.1436 (2)0.02799 (15)0.0422 (6)
H4A0.30490.1798−0.00610.051*
C50.40373 (14)0.2213 (2)0.07156 (14)0.0376 (5)
H5A0.39750.31060.06850.045*
C60.47632 (13)0.03895 (19)0.12562 (13)0.0306 (5)
H6A0.52040.00320.15930.037*
C70.46889 (13)0.16841 (18)0.12030 (13)0.0281 (5)
C80.60516 (14)0.2224 (2)0.16257 (13)0.0340 (5)
H8A0.62370.14790.13430.041*
C90.66617 (13)0.3041 (2)0.20555 (14)0.0333 (5)
C100.75249 (14)0.2905 (2)0.19473 (15)0.0463 (6)
H10A0.77470.22140.16290.056*
C110.80586 (17)0.3784 (3)0.23054 (17)0.0543 (7)
H11A0.86560.37110.22420.065*
C120.77113 (16)0.4765 (3)0.27551 (17)0.0529 (7)
H12A0.80670.54040.29890.064*
C130.68392 (16)0.4830 (2)0.28702 (16)0.0445 (6)
H13A0.66080.55000.32020.053*
N10.52662 (11)0.25156 (15)0.16309 (11)0.0290 (4)
N20.63159 (11)0.39730 (16)0.25264 (11)0.0347 (4)
O10.37216 (11)−0.24708 (15)0.05397 (12)0.0591 (5)
O20.48289 (12)−0.22398 (14)0.14171 (12)0.0561 (5)
O30.29873 (10)−0.06080 (16)−0.00716 (11)0.0531 (5)
H3A0.3095−0.13700.00350.080*
O40.50698 (13)0.53118 (16)0.15316 (12)0.0501 (5)
O50.62630 (14)0.48046 (19)0.02994 (14)0.0614 (5)
H4B0.4935 (15)0.6066 (17)0.1536 (18)0.062 (9)*
H4C0.5432 (14)0.522 (2)0.1140 (13)0.055 (9)*
H5C0.618 (2)0.419 (2)−0.0026 (18)0.084 (11)*
H5B0.6754 (14)0.505 (3)0.024 (2)0.109 (15)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0350 (2)0.0170 (2)0.0344 (2)0.0000.00107 (18)0.000
C10.0476 (16)0.0267 (13)0.0512 (15)−0.0005 (11)0.0112 (13)−0.0075 (12)
C20.0363 (13)0.0238 (12)0.0340 (12)0.0022 (9)0.0041 (10)−0.0050 (10)
C30.0412 (14)0.0343 (14)0.0359 (12)0.0005 (10)0.0030 (11)−0.0131 (10)
C40.0479 (15)0.0378 (14)0.0409 (13)0.0117 (11)−0.0143 (11)−0.0048 (11)
C50.0493 (14)0.0233 (12)0.0402 (13)0.0051 (10)−0.0040 (11)−0.0003 (10)
C60.0308 (13)0.0253 (11)0.0357 (13)0.0038 (9)0.0029 (10)0.0004 (10)
C70.0325 (12)0.0212 (11)0.0306 (12)0.0003 (9)0.0036 (10)−0.0048 (9)
C80.0411 (15)0.0244 (12)0.0364 (13)0.0011 (10)0.0046 (11)0.0001 (10)
C90.0329 (13)0.0308 (13)0.0362 (13)−0.0016 (9)−0.0001 (11)0.0065 (11)
C100.0385 (15)0.0470 (16)0.0534 (16)−0.0012 (11)0.0037 (12)0.0096 (13)
C110.0358 (14)0.0617 (19)0.0654 (19)−0.0079 (13)−0.0070 (13)0.0216 (15)
C120.0469 (17)0.0557 (18)0.0563 (17)−0.0195 (14)−0.0180 (13)0.0137 (14)
C130.0522 (16)0.0393 (15)0.0419 (14)−0.0103 (12)−0.0117 (12)0.0048 (12)
N10.0346 (11)0.0211 (9)0.0313 (10)0.0009 (7)−0.0002 (8)0.0019 (8)
N20.0387 (10)0.0290 (10)0.0365 (10)−0.0064 (8)−0.0045 (9)0.0039 (9)
O10.0604 (12)0.0302 (10)0.0869 (13)−0.0087 (8)−0.0029 (10)−0.0191 (9)
O20.0731 (13)0.0220 (9)0.0731 (12)0.0054 (8)−0.0089 (10)0.0025 (9)
O30.0497 (11)0.0443 (10)0.0654 (12)−0.0009 (8)−0.0160 (9)−0.0216 (9)
O40.0730 (13)0.0260 (10)0.0512 (11)0.0140 (9)0.0232 (10)0.0116 (8)
O50.0665 (15)0.0488 (13)0.0688 (14)−0.0066 (11)0.0228 (12)−0.0147 (11)

Geometric parameters (Å, °)

Ni1—O42.0380 (17)C8—C91.456 (3)
Ni1—N22.0754 (18)C8—H8A0.9500
Ni1—N12.1347 (17)C9—N21.345 (3)
C1—O21.241 (3)C9—C101.378 (3)
C1—O11.271 (3)C10—C111.372 (3)
C1—C21.504 (3)C10—H10A0.9500
C2—C61.384 (3)C11—C121.367 (4)
C2—C31.404 (3)C11—H11A0.9500
C3—O31.354 (3)C12—C131.388 (3)
C3—C41.377 (3)C12—H12A0.9500
C4—C51.376 (3)C13—N21.337 (3)
C4—H4A0.9500C13—H13A0.9500
C5—C71.395 (3)O3—H3A0.8400
C5—H5A0.9500O4—H4B0.825 (16)
C6—C71.376 (3)O4—H4C0.843 (16)
C6—H6A0.9500O5—H5C0.837 (17)
C7—N11.431 (3)O5—H5B0.823 (18)
C8—N11.276 (3)
O4i—Ni1—O496.16 (11)C6—C7—C5119.61 (19)
O4i—Ni1—N293.23 (8)C6—C7—N1121.90 (19)
O4—Ni1—N288.74 (7)C5—C7—N1118.48 (18)
O4i—Ni1—N2i88.74 (7)N1—C8—C9119.7 (2)
O4—Ni1—N2i93.23 (8)N1—C8—H8A120.2
N2—Ni1—N2i177.06 (9)C9—C8—H8A120.2
O4i—Ni1—N1168.85 (7)N2—C9—C10122.9 (2)
O4—Ni1—N190.93 (7)N2—C9—C8114.73 (19)
N2—Ni1—N178.29 (7)C10—C9—C8122.3 (2)
N2i—Ni1—N199.48 (7)C11—C10—C9119.0 (2)
O4i—Ni1—N1i90.93 (7)C11—C10—H10A120.5
O4—Ni1—N1i168.85 (7)C9—C10—H10A120.5
N2—Ni1—N1i99.48 (6)C12—C11—C10118.5 (2)
N2i—Ni1—N1i78.29 (7)C12—C11—H11A120.7
N1—Ni1—N1i83.45 (9)C10—C11—H11A120.7
O2—C1—O1125.4 (2)C11—C12—C13120.0 (2)
O2—C1—C2118.4 (2)C11—C12—H12A120.0
O1—C1—C2116.2 (2)C13—C12—H12A120.0
C6—C2—C3118.72 (19)N2—C13—C12121.7 (2)
C6—C2—C1120.2 (2)N2—C13—H13A119.1
C3—C2—C1121.0 (2)C12—C13—H13A119.1
O3—C3—C4119.8 (2)C8—N1—C7117.79 (18)
O3—C3—C2120.2 (2)C8—N1—Ni1112.01 (14)
C4—C3—C2120.0 (2)C7—N1—Ni1129.08 (13)
C5—C4—C3120.8 (2)C13—N2—C9117.7 (2)
C5—C4—H4A119.6C13—N2—Ni1127.38 (16)
C3—C4—H4A119.6C9—N2—Ni1114.39 (14)
C4—C5—C7119.7 (2)C3—O3—H3A109.5
C4—C5—H5A120.2Ni1—O4—H4B129 (2)
C7—C5—H5A120.2Ni1—O4—H4C120.0 (17)
C7—C6—C2121.2 (2)H4B—O4—H4C107 (3)
C7—C6—H6A119.4H5C—O5—H5B109 (3)
C2—C6—H6A119.4

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O10.841.722.475 (2)149
O4—H4B···O2ii0.83 (2)1.81 (2)2.621 (2)168 (3)
O4—H4C···O50.84 (2)1.91 (2)2.744 (3)173 (2)
O5—H5B···O3iii0.82 (2)2.05 (2)2.870 (3)178 (3)
O5—H5C···O1iv0.84 (2)1.99 (2)2.793 (3)160 (3)

Symmetry codes: (ii) x, y+1, z; (iii) x+1/2, −y+1/2, −z; (iv) −x+1, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2372).

References

  • Ali, M. A., Mirza, A. H., Butcher, R. J. & Tarafder, M. T. H. (2002). Inorg. Biochem.92, 141–148. [PubMed]
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cukurovali, A., Yilmaz, I., Ozmen, H. & Ahmedzade, M. (2002). Transition Met. Chem.27, 171–176.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tarafder, M. T. H., Jin, K. T., Crouse, K. A., Ali, A. M. & Yamin, B. M. (2002). Polyhedron, 21, 2547–2554.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography