metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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{4,4′-Di­bromo-2,2′-[2,2-di­methyl­propane-1,3-diylbis(nitrilo­methanylyl­­idene)]diphenolato-κ4O,N,N′,O′}nickel(II)

aDepartment of Chemistry, K. N. Toosi University of Technology, PO Box 16315-1618, Tehran, Iran, bDepartment of Chemistry, Islamic Azad University, Saveh Branch, PO Box 39187-366, Saveh, Iran, and cDepartment of Chemistry, Shahid Beheshti University, G. C. Evin, Tehran 1983963113, Iran
*Correspondence e-mail: rayati@kntu.ac.ir

(Received 6 March 2011; accepted 9 March 2011; online 15 March 2011)

In the title compound, [Ni(C19H18Br2N2O2)], the NiII ion, lying on a twofold rotation axis, is coordinated by two N atoms and two O atoms from the Schiff base ligand in a distorted square-planar geometry. Weak inter­molecular C—H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For the catalytic properties of Schiff base complexes, see: Cozzi (2004[Cozzi, P. G. (2004). Chem. Soc. Rev. 33, 410-421.]). For related structures see: Fun et al. (2008[Fun, H.-K., Kia, R. & Kargar, H. (2008). Acta Cryst. E64, o1895-o1896.]); Kargar et al. (2008[Kargar, H., Fun, H.-K. & Kia, R. (2008). Acta Cryst. E64, m1541-m1542.]). For the synthesis of the ligand, see: Fairhurst et al. (1995[Fairhurst, S. A., Hughes, D. L., Kleinkes, U., Leigh, G. J., Sanders, J. R. & Weisner, J. (1995). J. Chem. Soc. Dalton Trans. pp. 321-326.]).

[Scheme 1]

Experimental

Crystal data
  • [Ni(C19H18Br2N2O2)]

  • Mr = 524.84

  • Monoclinic, C 2/c

  • a = 24.227 (6) Å

  • b = 11.030 (3) Å

  • c = 7.535 (2) Å

  • β = 107.939 (19)°

  • V = 1915.6 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 5.20 mm−1

  • T = 298 K

  • 0.30 × 0.20 × 0.15 mm

Data collection
  • Stoe IPDS-2 diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005[Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.289, Tmax = 0.449

  • 7514 measured reflections

  • 2575 independent reflections

  • 1892 reflections with I > 2σ(I)

  • Rint = 0.142

Refinement
  • R[F2 > 2σ(F2)] = 0.073

  • wR(F2) = 0.211

  • S = 1.16

  • 2575 reflections

  • 119 parameters

  • H-atom parameters constrained

  • Δρmax = 0.74 e Å−3

  • Δρmin = −0.99 e Å−3

Table 1
Selected bond lengths (Å)

Ni1—N1 1.874 (4)
Ni1—O1 1.856 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3B⋯O1i 0.97 2.40 3.210 (6) 141
Symmetry code: (i) -x, -y, -z.

Data collection: X-AREA (Stoe & Cie, 2005[Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

Schiff base complexes are found to exhibit large applications such as catalytic properties (Cozzi, 2004). N,N'-Bis(5-bromo-2-hydroxybenzylidene)- 2,2-dimethylpropane-1,3-diamine ligand has been previously synthesized and structurally characterized by X-ray diffraction (Fun et al., 2008). The structure of a copper(II) complex of this Schiff base ligand has been also reported by Fun's group (Kargar et al., 2008).

Herein, we report the synthesis and crystal structure of an Ni(II) complex with this Schiff base ligand. The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit of the title compound contains half of the molecule. The NiII ion, lying on a twofold rotation axis, is coordinated by two N atoms and two O atoms from a Schiff base ligand (Table 1). The coordination environment around the NiII ion can be described as distorted squar-planar. In the crystal, weak intermolecular C—H···O hydrogen bonds stabilize the structure (Table 2, Fig. 2).

Related literature top

For the catalytic properties of Schiff base complexes, see: Cozzi (2004). For related structures see: Fun et al. (2008); Kargar et al. (2008). For the synthesis of the ligand, see: Fairhurst et al. (1995).

Experimental top

N,N'-Bis(5-bromo-2-hydroxybenzylidene)- 2,2-dimethylpropane-1,3-diamine was prepared according to the described procedure (Fairhurst et al., 1995). To a stirred ethanolic solution (30 ml) of 2,2-dimethylpropylenediamine (0.102 g, 1 mmol), 5-bromo-2-hydroxybenzaldehyde (0.402 g, 2 mmol) was added. The bright yellow solution was stirred and heated to reflux for 1 h. A yellow precipitate was obtained that was filtered off, washed with diethyl ether (yield: 70%; m.p.: 140 °C).

The title complex was prepared by the following procedure. The Schiff base ligand (0.467 g, 1 mmol) was dissolved in 20 ml ethanol. A solution of nickel(II) acetate (0.248 g, 1 mmol) in ethanol was added to the solution of ligand and the reaction mixture was refluxed for 1 h. The colored solution was concentrated to yield brown powders. The product washed with ethanol and air dried (yield: 95%; decomposition temperature: 242°C).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic), 0.97 (CH2) and 0.96 (CH3) Å and with Uiso(H) = 1.2 or 1.5Ueq(C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x, y, -z+1/2].
[Figure 2] Fig. 2. The packing diagram of the title compound. Hydrogen bonds are shown as blue dashed lines.
{4,4'-Dibromo-2,2'-[2,2-dimethylpropane-1,3- diylbis(nitrilomethanylylidene)]diphenolato- κ4O,N,N',O'}nickel(II) top
Crystal data top
[Ni(C19H18Br2N2O2)]F(000) = 1040.0
Mr = 524.84Dx = 1.820 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2575 reflections
a = 24.227 (6) Åθ = 3.2–29.2°
b = 11.030 (3) ŵ = 5.20 mm1
c = 7.535 (2) ÅT = 298 K
β = 107.939 (19)°Plate, brown
V = 1915.6 (9) Å30.30 × 0.20 × 0.15 mm
Z = 4
Data collection top
Stoe IPDS-2
diffractometer
2575 independent reflections
Radiation source: fine-focus sealed tube1892 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.142
ω scansθmax = 29.2°, θmin = 3.2°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
h = 3324
Tmin = 0.289, Tmax = 0.449k = 1513
7514 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.073Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0955P)2 + 1.9321P]
where P = (Fo2 + 2Fc2)/3
2575 reflections(Δ/σ)max < 0.001
119 parametersΔρmax = 0.74 e Å3
0 restraintsΔρmin = 0.99 e Å3
Crystal data top
[Ni(C19H18Br2N2O2)]V = 1915.6 (9) Å3
Mr = 524.84Z = 4
Monoclinic, C2/cMo Kα radiation
a = 24.227 (6) ŵ = 5.20 mm1
b = 11.030 (3) ÅT = 298 K
c = 7.535 (2) Å0.30 × 0.20 × 0.15 mm
β = 107.939 (19)°
Data collection top
Stoe IPDS-2
diffractometer
2575 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
1892 reflections with I > 2σ(I)
Tmin = 0.289, Tmax = 0.449Rint = 0.142
7514 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0730 restraints
wR(F2) = 0.211H-atom parameters constrained
S = 1.16Δρmax = 0.74 e Å3
2575 reflectionsΔρmin = 0.99 e Å3
119 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0516 (4)0.4164 (6)0.2433 (9)0.0606 (17)
H1A0.04070.46470.13190.073*
H1B0.08360.36500.24320.073*
H1C0.06290.46850.35050.073*
C20.00000.3381 (7)0.25000.0386 (14)
C30.0173 (2)0.2567 (5)0.0764 (6)0.0376 (10)
H3A0.04280.30230.02680.045*
H3B0.01730.23640.04380.045*
C40.0989 (2)0.1277 (5)0.0094 (7)0.0411 (11)
H40.11720.19460.07800.049*
C50.1317 (2)0.0172 (5)0.0337 (7)0.0425 (11)
C60.1902 (3)0.0171 (7)0.1506 (8)0.0546 (14)
H60.20780.08940.20180.065*
C70.2206 (3)0.0880 (7)0.1878 (9)0.0591 (17)
C80.1955 (3)0.1976 (7)0.1126 (9)0.0587 (16)
H80.21720.26870.13810.070*
C90.1388 (3)0.2006 (6)0.0009 (8)0.0518 (14)
H90.12230.27460.04620.062*
C100.1048 (2)0.0934 (5)0.0447 (7)0.0404 (11)
N10.04685 (19)0.1431 (4)0.0982 (5)0.0357 (9)
O10.05103 (17)0.1011 (3)0.1491 (5)0.0427 (8)
Ni10.00000.02440 (9)0.25000.0336 (3)
Br10.29838 (4)0.08575 (11)0.35030 (14)0.0979 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.074 (5)0.048 (4)0.053 (3)0.013 (3)0.010 (3)0.002 (3)
C20.037 (3)0.038 (4)0.036 (3)0.0000.004 (3)0.000
C30.041 (3)0.035 (3)0.036 (2)0.000 (2)0.0104 (19)0.0032 (18)
C40.046 (3)0.040 (3)0.036 (2)0.004 (2)0.0100 (19)0.0043 (19)
C50.038 (2)0.046 (3)0.039 (2)0.005 (2)0.0036 (19)0.001 (2)
C60.040 (3)0.058 (4)0.054 (3)0.000 (3)0.003 (2)0.008 (3)
C70.031 (3)0.073 (5)0.060 (3)0.014 (3)0.007 (2)0.003 (3)
C80.045 (3)0.060 (4)0.064 (3)0.018 (3)0.007 (3)0.005 (3)
C90.057 (4)0.039 (3)0.055 (3)0.007 (3)0.011 (3)0.003 (2)
C100.040 (3)0.044 (3)0.036 (2)0.005 (2)0.0105 (19)0.0033 (19)
N10.040 (2)0.036 (2)0.0277 (15)0.0035 (18)0.0057 (14)0.0005 (14)
O10.0371 (19)0.0349 (19)0.0495 (19)0.0004 (15)0.0035 (15)0.0030 (14)
Ni10.0339 (5)0.0315 (5)0.0325 (4)0.0000.0060 (3)0.000
Br10.0519 (5)0.1002 (8)0.1070 (7)0.0251 (5)0.0265 (4)0.0188 (5)
Geometric parameters (Å, º) top
C1—C21.533 (8)C5—C61.421 (8)
C1—H1A0.9600C5—C101.423 (8)
C1—H1B0.9600C6—C71.354 (10)
C1—H1C0.9600C6—H60.9300
C2—C1i1.533 (8)C7—C81.393 (11)
C2—C31.535 (7)C7—Br11.906 (6)
C2—C3i1.535 (7)C8—C91.372 (9)
C3—N11.476 (7)C8—H80.9300
C3—H3A0.9700C9—C101.423 (8)
C3—H3B0.9700C9—H90.9300
C4—N11.284 (7)C10—O11.300 (7)
C4—C51.435 (8)Ni1—N11.874 (4)
C4—H40.9300Ni1—O11.856 (4)
C2—C1—H1A109.5C7—C6—H6119.9
C2—C1—H1B109.5C5—C6—H6119.9
H1A—C1—H1B109.5C6—C7—C8121.2 (6)
C2—C1—H1C109.5C6—C7—Br1119.2 (5)
H1A—C1—H1C109.5C8—C7—Br1119.5 (5)
H1B—C1—H1C109.5C9—C8—C7119.9 (6)
C1—C2—C1i111.4 (8)C9—C8—H8120.0
C1—C2—C3108.3 (3)C7—C8—H8120.0
C1i—C2—C3110.2 (3)C8—C9—C10121.7 (6)
C1—C2—C3i110.2 (3)C8—C9—H9119.2
C1i—C2—C3i108.3 (3)C10—C9—H9119.2
C3—C2—C3i108.4 (6)O1—C10—C5123.6 (5)
N1—C3—C2114.6 (4)O1—C10—C9119.4 (5)
N1—C3—H3A108.6C5—C10—C9117.0 (5)
C2—C3—H3A108.6C4—N1—C3117.2 (4)
N1—C3—H3B108.6C4—N1—Ni1125.9 (4)
C2—C3—H3B108.6C3—N1—Ni1116.0 (3)
H3A—C3—H3B107.6C10—O1—Ni1128.0 (4)
N1—C4—C5126.2 (5)O1—Ni1—O1i83.5 (2)
N1—C4—H4116.9O1—Ni1—N1i166.70 (17)
C5—C4—H4116.9O1i—Ni1—N1i93.97 (18)
C6—C5—C10119.9 (6)O1—Ni1—N193.97 (18)
C6—C5—C4119.1 (6)O1i—Ni1—N1166.70 (17)
C10—C5—C4120.7 (5)N1i—Ni1—N191.3 (3)
C7—C6—C5120.2 (6)
C1—C2—C3—N1154.4 (5)C8—C9—C10—C51.2 (9)
C1i—C2—C3—N183.4 (6)C5—C4—N1—C3168.8 (5)
C3i—C2—C3—N134.9 (3)C5—C4—N1—Ni10.5 (7)
N1—C4—C5—C6176.4 (5)C2—C3—N1—C4118.2 (5)
N1—C4—C5—C108.9 (8)C2—C3—N1—Ni172.3 (5)
C10—C5—C6—C70.0 (9)C5—C10—O1—Ni19.6 (7)
C4—C5—C6—C7174.6 (6)C9—C10—O1—Ni1172.6 (4)
C5—C6—C7—C80.3 (11)C10—O1—Ni1—O1i179.3 (5)
C5—C6—C7—Br1178.4 (5)C10—O1—Ni1—N1i99.5 (8)
C6—C7—C8—C91.0 (11)C10—O1—Ni1—N113.9 (4)
Br1—C7—C8—C9177.7 (5)C4—N1—Ni1—O18.7 (4)
C7—C8—C9—C101.5 (10)C3—N1—Ni1—O1159.7 (3)
C6—C5—C10—O1178.3 (5)C4—N1—Ni1—O1i87.3 (9)
C4—C5—C10—O13.7 (8)C3—N1—Ni1—O1i81.1 (9)
C6—C5—C10—C90.4 (8)C4—N1—Ni1—N1i159.1 (5)
C4—C5—C10—C9174.1 (5)C3—N1—Ni1—N1i32.5 (3)
C8—C9—C10—O1179.1 (6)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3B···O1ii0.972.403.210 (6)141
Symmetry code: (ii) x, y, z.

Experimental details

Crystal data
Chemical formula[Ni(C19H18Br2N2O2)]
Mr524.84
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)24.227 (6), 11.030 (3), 7.535 (2)
β (°) 107.939 (19)
V3)1915.6 (9)
Z4
Radiation typeMo Kα
µ (mm1)5.20
Crystal size (mm)0.30 × 0.20 × 0.15
Data collection
DiffractometerStoe IPDS2
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
Tmin, Tmax0.289, 0.449
No. of measured, independent and
observed [I > 2σ(I)] reflections
7514, 2575, 1892
Rint0.142
(sin θ/λ)max1)0.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.073, 0.211, 1.16
No. of reflections2575
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.74, 0.99

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Ni1—N11.874 (4)Ni1—O11.856 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3B···O1i0.972.403.210 (6)141
Symmetry code: (i) x, y, z.
 

Acknowledgements

We gratefully acknowledge financial support of this study from K. N. Toosi University of Technology.

References

First citationCozzi, P. G. (2004). Chem. Soc. Rev. 33, 410–421.  Web of Science CrossRef PubMed CAS Google Scholar
First citationFairhurst, S. A., Hughes, D. L., Kleinkes, U., Leigh, G. J., Sanders, J. R. & Weisner, J. (1995). J. Chem. Soc. Dalton Trans. pp. 321–326.  CSD CrossRef Web of Science Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationFun, H.-K., Kia, R. & Kargar, H. (2008). Acta Cryst. E64, o1895–o1896.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKargar, H., Fun, H.-K. & Kia, R. (2008). Acta Cryst. E64, m1541–m1542.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.  Google Scholar

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