research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 252-255

Crystal structure of bis­­{2-[(E)-(4-fluoro­benz­yl)imino­meth­yl]phenolato-κ2N,O}nickel(II)

aFaculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, bDDH CoRe, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, cSchool of Biosciences and Biotechnology, Faculty of Science and Technology, Universiti Kebangsaan, 43600 Bangi, Selangor, Malaysia, dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, eDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia, and fDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
*Correspondence e-mail: hkfun@usm.my

Edited by J. Simpson, University of Otago, New Zealand (Received 9 September 2014; accepted 13 September 2014; online 24 September 2014)

The asymmetric unit of the title complex, [Ni(C14H11FNO)2], contains one-half of the mol­ecule with the NiII cation lying on an inversion centre coordinated by a bidentate Schiff base anion. The cationic NiII center is in a distorted square-planar coordination environment chelated by the imine N and phenolate O donor atoms of the two Schiff base ligands. The N and O donor atoms of the two ligands are mutually trans with Ni—N and Ni—O bond lengths of 1.9242 (10) and 1.8336 (9) Å, respectively. The fluoro­phenyl ring is almost orthogonal to the coordination plane and makes a dihedral angle of 82.98 (7)° with the phenolate ring. In the crystal, mol­ecules are linked into screw chains by weak C—H⋯F hydrogen bonds. Additional C—H⋯π contacts arrange the mol­ecules into sheets parallel to the ac plane.

1. Chemical context

Schiff base ligands are well-known and important compounds because of their wide range of biological activities and uses in industrial systems (Feng et al., 2013[Feng, Z.-Q., Yang, X.-L. & Ye, Y. F. (2013). Scientific World Journal, Article ID 956840, 9 pages.]; Kumar et al., 2010[Kumar, S., Niranjan, M. S., Chaluvaraju, K. C., Jamakhandi, C. M. & Kadadevar, D. J. (2010). J. Current Pharm. Res. 1, 39-42.]; Liu et al., 2005[Liu, W.-L., Zou, Y., Ni, C.-L., Li, Y.-Z. & Meng, Q.-J. (2005). J. Mol. Struct. 751, 1-6.]) as well as being versatile ligands for transition metals. Transition metal complexes with Schiff base ligands, especially those of PdII and NiII, have been shown to display a variety of structural features and, in some cases, exhibit inter­esting reactivity. In particular they can be photoluminescent (Guo et al., 2013a[Guo, H. F., Zhao, X., Ma, D. Y., Xie, A. P. & Shen, W. B. (2013a). Transition Met. Chem. 38, 299-305.]) and are used as catalysts for many organic reactions such as Heck and Suzuki cross-coupling reactions (Kumari et al., 2012[Kumari, N., Yadav, V. K., Zalis, S. & Mishra, L. (2012). Indian J. Chem. Section A, 51, 554-563.]; Teo et al., 2011[Teo, S., Weng, Z. & Andy Hor, T. S. (2011). J. Organomet. Chem. 696, 2928-2934.]).

[Scheme 1]

In our previous studies, we reported the syntheses and crystal structures of two related Schiff base complexes, bis­{2-[(E)-(4-fluoro­benz­yl)imino­meth­yl]-6-meth­oxy­phenolato-κ2N,O1}nickel(II) (Bahron et al., 2011[Bahron, H., Tajuddin, A. M., Ibrahim, W. N. W., Hemamalini, M. & Fun, H.-K. (2011). Acta Cryst. E67, m1010-m1011.]) and bis­{2-[(E)-(4-meth­oxy­benz­yl)imino­meth­yl]phenolato-κ2N,O1}nickel(II) (Bahron et al., 2014[Bahron, H., Tajuddin, A. M., Ibrahim, W. N. W., Fun, H.-K. & Chantrapromma, S. (2014). Acta Cryst. E70, 104-106.]). In this article, we report the successful synthesis of another Schiff base–NiII complex, [Ni(C14H11FNO)2] (1), and its characterization by spectros­copy and elemental analysis. Crystal structure determination confirms the binding mode of the [(4-fluoro­benz­yl)imino­meth­yl]phenolate ligand to the NiII cation (Fig. 1[link]). The title complex was also tested for anti­bacterial activity, and found to be only weakly active.

[Figure 1]
Figure 1
The mol­ecular structure of (1), showing 50% probability displacement ellipsoids and the atom-numbering scheme. The labelled atoms are related to the unlabelled atoms of the Schiff base ligands by the symmetry code: 1 − x, −y, 1 − z.

2. Structural commentary

The asymmetric unit of (1) contains one-half of the mol­ecule with the NiII cation lying on an inversion centre and the Schiff base anion acting as an N,O-bidentate chelate ligand (Fig. 1[link]). The cation binds to the N and the O atoms of two symmetry-related Schiff base ligand such that the N and O atoms are mutually trans. The N2O2 donor sets of the two chelating Schiff base ligands in the equatorial plane around Ni1 adopt a slightly distorted square planar coordination geometry with the angles O1—Ni1—N1 = 92.56 (4)° and O1—Ni1—N1i = 87.44 (4)° [symmetry code: (i) 1 − x, −y, 1 − z]. As expected under inversion symmetry, the trans angles (N11—Ni1—N1i and O1—Ni1—O1i) are found to be linear. The Ni1—N1 and Ni1—O1 distances in the N2O2 coordination plane are 1.9242 (10) Å and 1.8336 (9) Å, respectively. These compare well with those observed in the two other closely related NiII complexes with N2O2 coordinating Schiff base ligands (Bahron et al., 2011[Bahron, H., Tajuddin, A. M., Ibrahim, W. N. W., Hemamalini, M. & Fun, H.-K. (2011). Acta Cryst. E67, m1010-m1011.]; 2014[Bahron, H., Tajuddin, A. M., Ibrahim, W. N. W., Fun, H.-K. & Chantrapromma, S. (2014). Acta Cryst. E70, 104-106.]). The Ni1/O1/C1/C6/C7/N1 ring adopts an envelope conformation with the Ni1 atom displaced by 0.3885 (5) Å from the O1/C1/C6/C7/N1 plane, with the puckering parameters Q = 0.2429 (10) Å, θ = 65.3 (3) and φ = 4.0 (3)°. Other bond lengths and angles observed in the structure are also normal. The fluoro­phenyl ring (C9–C14) makes a dihedral angle of 82.98 (7)° with the phenolate ring (C1–C6).

3. Supra­molecular features

In the crystal packing, the mol­ecules are linked into screw chains by weak C2—H2A⋯F1 inter­actions (Fig. 2[link], Table 1[link]). C—H⋯π inter­actions involving both the fluoro­phenyl and the phenolate rings, C5—H5ACg1 and C13—H13ACg2, connect the mol­ecules into chains along the c-axis direction (Fig. 3[link], Table 1[link]). They also contribute to the formation of sheets parallel to the ac plane, which are further stacked along the b axis as shown in Fig. 4[link].

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C8—H8A⋯O1i 0.99 2.19 2.7300 (18) 113
C14—H14A⋯O1i 0.95 2.52 3.212 (2) 130
C2—H2A⋯F1ii 0.95 2.65 3.5312 (19) 155
C5—H5ACg1iii 0.95 2.69 3.4010 (18) 133
C13—H13ACg2iv 0.95 2.69 3.4252 (13) 134
Symmetry codes: (i) -x+1, -y, -z+1; (ii) [x-1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]; (iii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].
[Figure 2]
Figure 2
Screw chains of mol­ecules of (1) linked by C—H⋯F contacts drawn as dashed lines.
[Figure 3]
Figure 3
C—H⋯π contacts for (1) drawn as dotted lines with ring centroids shown as coloured spheres. Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively.
[Figure 4]
Figure 4
The packing of (1) viewed along the b axis showing mol­ecular sheets of the NiII complex.

4. Database survey

A search of the Cambridge Database (Version 5.35, November 2013 with 3 updates) revealed a total of 1191 NiII complexes with an NiN2O2 coordination sphere. No fewer than 333 of these had the Ni atom chelated by two 3-(imino­meth­yl)phenolate residues. No corresponding structures with a benzyl or substituted benzyl unit bound to the imino N atom were found. However extending the search to allow additional substitution on the phenolate ring resulted in eight discrete structures including the two closely related structures mentioned previously (Bahron et al., 2011[Bahron, H., Tajuddin, A. M., Ibrahim, W. N. W., Hemamalini, M. & Fun, H.-K. (2011). Acta Cryst. E67, m1010-m1011.], 2014[Bahron, H., Tajuddin, A. M., Ibrahim, W. N. W., Fun, H.-K. & Chantrapromma, S. (2014). Acta Cryst. E70, 104-106.]), and several other related complexes (see, for example Guo et al. 2013a[Guo, H. F., Zhao, X., Ma, D. Y., Xie, A. P. & Shen, W. B. (2013a). Transition Met. Chem. 38, 299-305.],b[Guo, Y., Liu, Y., Zhao, X. H., Li, Y. G. & Chen, W. (2013b). Russ. J. Coord. Chem. 39, 134—140.]; Senol et al. 2011[Senol, C., Hayvali, Z., Dal, H. & Hökelek, T. (2011). J. Mol. Struct. 997, 53—59.]; Chen et al. 2010[Chen, W., Li, Y., Cui, Y., Zhang, X., Zhu, H.-L. & Zeng, Q. (2010). Eur. J. Med. Chem. 45, 4473—4478.]).

5. Synthesis and crystallization

An ethano­lic solution of 4-fluoro­benzyl­amine (4 mmol, 0.5010 g) was added to salicyl­aldehyde (4 mmol, 0.4970 g), dissolved in absolute ethanol (2 ml), forming a bright-yellow solution. The mixture was heated under reflux for an hour to produce the ligand, (E)-2-[(4-fluoro­benzyl­imino)­meth­yl]phenol. Nickel(II) acetate tetra­hydrate (2 mmol, 0.4983 g) was dissolved separately in absolute ethanol (10 ml) and added to a flask containing the cooled ligand solution. The mixture was stirred and refluxed for 3 h upon which a dark-green solid formed. This was filtered off, washed with ice-cold ethanol and air-dried at room temperature. The solid product was recrystallized from chloro­form, yielding green crystals. Yield 68.6%; m.p. 471–473 K. Analytical data for C28H22F2N2O2Ni: C, 65.28; H, 4.30; N, 5.44. Found: C, 65.87; H, 4.39; N, 5.55. IR (KBr, cm−1): ν(C=N) 1612 (s), ν(C—N) 1390 (w), ν(C—O) 1221 (s), ν(Ni—N) 597 (w), ν(Ni—O) 451 (w). The infrared spectra of the title complex revealed a strong band of 1612 cm−1 in the spectrum assignable to C=N stretching frequency upon complexation (Nair et al., 2012[Nair, M. S., Arish, D. & Joseyphus, R. S. (2012). J. Saudi Chem. Soc. 16, 83-88.]). The appearance of new bands at 451 and 597 cm−1 in the spectrum of the title complex attributable to Ni—O and Ni—N vibrations, respectively, supports the suggestion above of the participation of the N atom of the imine group and O atom of the phenolic group of the ligand in the complexation with NiII cation (Ouf et al., 2010[Ouf, A. E., Ali, M. S., Saad, E. M. & Mostafa, S. I. (2010). J. Mol. Struct. 973, 69-75.]). Accordingly, it can be deduced that the ligand binds to the NiII cation in an N,O-bidentate fashion in 2:1 ratio.

An anti­bacterial activity investigation of the title complex against B. subtilis, S. aureus and E. coli showed very mild or no inhibition with clear inhibition diameters of 7–8 mm at the highest concentration of 50 μM. The negative control of a 9:1 mixture of DMSO:acetone and the positive control of 30 U of chloramphenicol showed inhibition diameters of 6 mm and 20 mm, respectively.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.95 Å for aromatic and 0.99 Å for CH2 hydrogen atoms. The Uiso values were constrained to be 1.2Ueq of the carrier atoms.

Table 2
Experimental details

Crystal data
Chemical formula [Ni(C14H11FNO)2]
Mr 515.17
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 13.8611 (3), 5.83340 (1), 16.9942 (3)
β (°) 125.998 (1)
V3) 1111.70 (4)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.92
Crystal size (mm) 0.47 × 0.19 × 0.11
 
Data collection
Diffractometer Bruker APEXII CCD area detector
Absorption correction Multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.674, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections 13419, 3235, 2896
Rint 0.024
(sin θ/λ)max−1) 0.703
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.072, 1.05
No. of reflections 3235
No. of parameters 160
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.45, −0.49
Computer programs: APEX2 and SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

Schiff base ligands are well-known and important compounds because of their wide range of biological activities and uses in industrial systems (Feng et al., 2013; Kumar et al., 2010; Liu et al., 2005) as well as being versatile ligands for transition metals. Transition metal complexes with Schiff base ligands, especially those of PdII and NiII, have been shown to display a variety of structural features and, in some cases, exhibit inter­esting reactivity. In particular they can be photoluminescent (Guo et al., 2013a) and are used as catalysts for many organic reactions such as Heck and Suzuki cross-coupling reactions (Kumari et al., 2012; Teo et al., 2011). In our previous studies, we reported the syntheses and crystal structures of two related Schiff base complexes, bis­{2-[(E)-(4-fluoro­benzyl)­imino­methyl]-6-meth­oxy­phenolato-κ2N,O1}nickel(II) (Bahron et al., 2011) and bis­{2-[(E)-(4-meth­oxy­benzyl)­imino­methyl]­phenolato-κ2N,O1}nickel(II) (Bahron et al., 2014). In this article, we report the successful synthesis of another Schiff base–NiII complex, [Ni(C14H11FNO)2] (1), and its characterization by spectroscopy and elemental analysis. The X-ray structure (Fig. 1) confirms the binding mode of the 4-fluoro­benzyl)­imino­methyl]­phenolate ligand to the NiII cation. The title complex was also tested for anti­bacterial activity, and found to be only weakly active.

Structural commentary top

The asymmetric unit of (1) contains one-half of the molecule with the NiII cation lying on an inversion centre and the Schiff base anion acting as an N,O-bidentate chelate ligand (Fig. 1). The Ni1 cation binds to the N and the O atoms of two symmetry-related Schiff base ligand such that the N and O atoms are mutually trans. The N2O2 donor sets of the two chelating Schiff base ligands in the equatorial plane around Ni1 adopt a slightly distorted square planar coordination geometry with the angles O1—Ni1—N1 = 92.56 (4)° and O1—Ni1—N1i = 87.44 (4)° [symmetry code: (i) 1 - x, -y, 1 - z]. As expected under inversion symmetry, the trans angles are found to be N11—Ni1—N1i = 180.00 (6)° and O1—Ni1—O1i = 180.0°. The Ni1—N1 and Ni1—O1 distances in the N2O2 coordination plane are 1.9242 (10) Å and 1.8336 (9) Å, respectively. These compare well with those observed in the two other closely related NiII complexes with N2O2 coordinating Schiff base ligands (Bahron et al., 2011; 2014). The Ni1/O1/C1/C6/C7/N1 ring adopts an envelope conformation with the Ni1 atom displaced by 0.3885 (5) Å from the plane of the phenolate ring atoms, with the puckering parameters Q = 0.2429 (10) Å, θ = 65.3 (3) and ϕ = 4.0 (3)°. Other bond lengths and angles observed in the structure are also normal. The fluoro­phenyl ring (C9–C14) makes a dihedral angle of 82.98 (7)° with the phenolate ring (C1–C6).

Supra­molecular features top

In the crystal packing, the molecules are linked into screw chains by weak C2–H2A···F1 inter­actions (Fig. 2, Table 1). C—H···π inter­actions involving both the fluoro­phenyl and the phenolate rings, C5—H5A···Cg1 and C13—H13A···Cg2, connect the molecules into chains along the c-axis direction (Fig. 3, Table 1). They also contribute to the formation of sheets parallel to the ac plane, which are further stacked along the b axis as shown in Fig. 4.

Database survey top

A search of the Cambridge Database (Version 5.35, November 2013 with 3 updates) revealed a total of 1191 NiII complexes with an NiN2O2 coordination sphere. No fewer than 333 of these had the Ni atom chelated by two 3-(imino­methyl)­phenolate residues. No corresponding structures with a benzyl or substituted benzyl unit bound to the imino N atom were found. However extending the search to allow additional substitution on the phenolate ring resulted in eight discrete structures including the two closely related structures mentioned previously (Bahron et al., 2011, 2014), and several other related complexes (see for example Guo et al. 2013a,b; Senol et al. 2011; Chen et al. 2010).

Synthesis and crystallization top

An ethano­lic solution of 4-fluoro­benzyl­amine (4 mmol, 0.5010 g) was added to salicyl­aldehyde (4 mmol, 0.4970 g), dissolved in absolute ethanol (2 ml), forming a bright-yellow solution. The mixture was heated under reflux for an hour to produce the ligand, (E)-2-[(4-fluoro­benzyl­imino)­methyl]­phenol. Nickel(II) acetate tetra­hydrate (2 mmol, 0.4983 g) was dissolved separately in absolute ethanol (10 ml) and added to a flask containing the cooled ligand solution. The mixture was stirred and refluxed for 3 hours upon which a dark-green solid formed. This was filtered off, washed with ice-cold ethanol and air dried at room temperature. The solid product was recrystallized from chloro­form, yielding green crystals. Yield 68.6%. Melting point 471–473 K. Analytical data for C28H22F2N2O2Ni: C, 65.28; H, 4.30; N, 5.44. Found: C, 65.87; H, 4.39; N, 5.55. IR (KBr, cm-1): ν(C=N) 1612 (s), ν(C—N) 1390 (w), ν(C—O) 1221 (s), ν(Ni—N) 597 (w), ν(Ni—O) 451 (w). The infrared spectra of the title complex revealed a strong band of 1612 cm-1 in the spectrum assignable to C=N stretching frequency upon complexation (Nair et al., 2012). The appearance of new bands at 451 and 597 cm-1 in the spectrum of the title complex attributable to Ni—O and Ni—N vibrations, respectively, supports the suggestion above of the participation of the N atom of the imine group and O atom of the phenolic group of the ligand in the complexation with NiII cation (Ouf et al., 2010). Accordingly, it can be deduced that the ligand binds to the NiII cation in an N,O-bidentate fashion in 2:1 ratio.

An anti­bacterial activity investigation of the title complex against B. subtilis, S. aureus and E. coli showed very mild or no inhibition with clear inhibition diameters of 7–8 mm at the highest concentration of 50 υM. The negative control of a 9:1 mixture of DMSO:acetone and the positive control of 30 U of chloramphenicol showed inhibition diameters of 6 mm and 20 mm, respectively.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.95 Å for aromatic and 0.99 Å for CH2 hydrogen atoms. The Uiso values were constrained to be 1.2Ueq of the carrier atoms.

Related literature top

For related literature, see: Bahron et al. (2011, 2014); Chen et al. (2010); Feng et al. (2013); Guo et al. (2013a, 2013b); Kumar et al. (2010); Kumari et al. (2012); Liu et al. (2005); Nair et al. (2012); Ouf et al. (2010); Senol et al. (2011); Teo et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2006) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (1), showing 50% probability displacement ellipsoids and the atom-numbering scheme. The labelled atoms are related to the unlabelled atoms of the Schiff base ligands by the symmetry code: 1 - x, -y, 1 - z.
[Figure 2] Fig. 2. Screw chains of molecules of (1) linked by C—H···F contacts drawn as dashed lines.
[Figure 3] Fig. 3. C—H···π contacts for (1) drawn as dotted lines with ring centroids shown as coloured spheres. Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively.
[Figure 4] Fig. 4. The packing of (1) viewed along the b axis showing molecular sheets of the NiII complex.
Bis{2-[(E)-(4-fluorobenzyl)iminomethyl]phenolato- K2N,O1}nickel(II) top
Crystal data top
[Ni(C14H11FNO)2]F(000) = 532
Mr = 515.17Dx = 1.539 Mg m3
Monoclinic, P21/cMelting point = 471–476 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.8611 (3) ÅCell parameters from 3235 reflections
b = 5.83340 (1) Åθ = 1.8–30.0°
c = 16.9942 (3) ŵ = 0.92 mm1
β = 125.998 (1)°T = 100 K
V = 1111.70 (4) Å3Plate, green
Z = 20.47 × 0.19 × 0.11 mm
Data collection top
Bruker APEXII CCD area detector
diffractometer
3235 independent reflections
Radiation source: sealed tube2896 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ϕ and ω scansθmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1919
Tmin = 0.674, Tmax = 0.906k = 88
13419 measured reflectionsl = 2323
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0322P)2 + 0.7123P]
where P = (Fo2 + 2Fc2)/3
3235 reflections(Δ/σ)max = 0.001
160 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
[Ni(C14H11FNO)2]V = 1111.70 (4) Å3
Mr = 515.17Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.8611 (3) ŵ = 0.92 mm1
b = 5.83340 (1) ÅT = 100 K
c = 16.9942 (3) Å0.47 × 0.19 × 0.11 mm
β = 125.998 (1)°
Data collection top
Bruker APEXII CCD area detector
diffractometer
3235 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
2896 reflections with I > 2σ(I)
Tmin = 0.674, Tmax = 0.906Rint = 0.024
13419 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.05Δρmax = 0.45 e Å3
3235 reflectionsΔρmin = 0.49 e Å3
160 parameters
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 2sigma(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
Ni10.50000.00000.50000.01062 (7)
F11.07321 (8)0.19874 (17)0.63754 (7)0.0297 (2)
N10.58764 (8)0.26207 (18)0.50481 (7)0.01200 (19)
O10.41017 (8)0.01507 (15)0.36693 (7)0.01520 (18)
C10.38843 (10)0.1456 (2)0.30461 (9)0.0133 (2)
C20.29659 (11)0.1091 (2)0.20455 (9)0.0160 (2)
H2A0.25280.03030.18400.019*
C30.27066 (11)0.2756 (2)0.13703 (9)0.0174 (2)
H3A0.20850.24900.07040.021*
C40.33373 (12)0.4832 (2)0.16425 (10)0.0175 (2)
H4A0.31470.59590.11680.021*
C50.42385 (11)0.5206 (2)0.26118 (9)0.0151 (2)
H5A0.46760.66000.28040.018*
C60.45190 (10)0.3546 (2)0.33205 (8)0.0125 (2)
C70.55207 (10)0.3936 (2)0.43090 (9)0.0125 (2)
H7A0.59680.52940.44340.015*
C80.70465 (10)0.3283 (2)0.59589 (9)0.0134 (2)
H8A0.70240.30420.65240.016*
H8B0.71980.49300.59330.016*
C90.80423 (10)0.1869 (2)0.60823 (8)0.0133 (2)
C100.86635 (11)0.2669 (2)0.57233 (9)0.0166 (2)
H10A0.84560.41100.54020.020*
C110.95823 (11)0.1396 (3)0.58258 (10)0.0202 (3)
H11A1.00100.19570.55880.024*
C120.98511 (11)0.0701 (3)0.62825 (10)0.0196 (3)
C130.92625 (11)0.1569 (2)0.66508 (9)0.0174 (2)
H13A0.94710.30190.69650.021*
C140.83553 (11)0.0255 (2)0.65471 (9)0.0152 (2)
H14A0.79420.08160.67980.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01005 (10)0.01029 (11)0.01063 (11)0.00089 (7)0.00557 (8)0.00019 (7)
F10.0240 (4)0.0360 (5)0.0340 (5)0.0125 (4)0.0197 (4)0.0035 (4)
N10.0105 (4)0.0115 (5)0.0129 (4)0.0003 (3)0.0063 (4)0.0010 (4)
O10.0168 (4)0.0142 (4)0.0122 (4)0.0036 (3)0.0072 (3)0.0005 (3)
C10.0123 (5)0.0149 (5)0.0138 (5)0.0010 (4)0.0084 (4)0.0009 (4)
C20.0141 (5)0.0177 (6)0.0148 (5)0.0015 (4)0.0077 (5)0.0003 (4)
C30.0141 (5)0.0218 (6)0.0136 (5)0.0016 (4)0.0066 (4)0.0010 (5)
C40.0176 (6)0.0188 (6)0.0157 (6)0.0029 (4)0.0096 (5)0.0049 (5)
C50.0153 (5)0.0144 (6)0.0167 (6)0.0012 (4)0.0100 (5)0.0022 (4)
C60.0115 (5)0.0133 (5)0.0135 (5)0.0014 (4)0.0077 (4)0.0010 (4)
C70.0122 (5)0.0115 (5)0.0158 (5)0.0002 (4)0.0093 (4)0.0005 (4)
C80.0119 (5)0.0116 (5)0.0140 (5)0.0017 (4)0.0062 (4)0.0020 (4)
C90.0103 (5)0.0149 (5)0.0114 (5)0.0012 (4)0.0045 (4)0.0015 (4)
C100.0154 (5)0.0179 (6)0.0156 (5)0.0010 (4)0.0086 (5)0.0007 (4)
C110.0174 (6)0.0271 (7)0.0192 (6)0.0004 (5)0.0126 (5)0.0003 (5)
C120.0139 (5)0.0249 (7)0.0182 (6)0.0039 (5)0.0085 (5)0.0020 (5)
C130.0139 (5)0.0162 (6)0.0161 (6)0.0013 (4)0.0054 (5)0.0002 (4)
C140.0123 (5)0.0152 (6)0.0155 (5)0.0018 (4)0.0068 (4)0.0008 (4)
Geometric parameters (Å, º) top
Ni1—O1i1.8336 (9)C5—H5A0.9500
Ni1—O11.8336 (9)C6—C71.4351 (16)
Ni1—N1i1.9242 (10)C7—H7A0.9500
Ni1—N11.9242 (10)C8—C91.5133 (16)
F1—C121.3613 (15)C8—H8A0.9900
N1—C71.2967 (16)C8—H8B0.9900
N1—C81.4915 (15)C9—C141.3943 (17)
O1—C11.3097 (15)C9—C101.3960 (17)
C1—C61.4130 (17)C10—C111.3937 (18)
C1—C21.4187 (17)C10—H10A0.9500
C2—C31.3801 (18)C11—C121.378 (2)
C2—H2A0.9500C11—H11A0.9500
C3—C41.4031 (19)C12—C131.3834 (19)
C3—H3A0.9500C13—C141.3926 (17)
C4—C51.3794 (18)C13—H13A0.9500
C4—H4A0.9500C14—H14A0.9500
C5—C61.4100 (17)
O1i—Ni1—O1180.0N1—C7—C6126.56 (11)
O1i—Ni1—N1i92.56 (4)N1—C7—H7A116.7
O1—Ni1—N1i87.44 (4)C6—C7—H7A116.7
O1i—Ni1—N187.44 (4)N1—C8—C9110.45 (9)
O1—Ni1—N192.56 (4)N1—C8—H8A109.6
N1i—Ni1—N1180.00 (6)C9—C8—H8A109.6
C7—N1—C8114.48 (10)N1—C8—H8B109.6
C7—N1—Ni1123.90 (8)C9—C8—H8B109.6
C8—N1—Ni1121.62 (8)H8A—C8—H8B108.1
C1—O1—Ni1129.03 (8)C14—C9—C10118.57 (11)
O1—C1—C6123.23 (11)C14—C9—C8121.18 (11)
O1—C1—C2118.67 (11)C10—C9—C8120.25 (11)
C6—C1—C2118.10 (11)C11—C10—C9121.36 (12)
C3—C2—C1120.18 (12)C11—C10—H10A119.3
C3—C2—H2A119.9C9—C10—H10A119.3
C1—C2—H2A119.9C12—C11—C10117.89 (12)
C2—C3—C4121.73 (12)C12—C11—H11A121.1
C2—C3—H3A119.1C10—C11—H11A121.1
C4—C3—H3A119.1F1—C12—C11118.81 (12)
C5—C4—C3118.79 (12)F1—C12—C13118.24 (13)
C5—C4—H4A120.6C11—C12—C13122.95 (12)
C3—C4—H4A120.6C12—C13—C14118.04 (12)
C4—C5—C6120.87 (12)C12—C13—H13A121.0
C4—C5—H5A119.6C14—C13—H13A121.0
C6—C5—H5A119.6C13—C14—C9121.18 (12)
C5—C6—C1120.33 (11)C13—C14—H14A119.4
C5—C6—C7118.85 (11)C9—C14—H14A119.4
C1—C6—C7120.62 (11)
O1i—Ni1—N1—C7161.69 (10)C8—N1—C7—C6171.36 (11)
O1—Ni1—N1—C718.31 (10)Ni1—N1—C7—C68.09 (17)
O1i—Ni1—N1—C818.90 (9)C5—C6—C7—N1177.97 (11)
O1—Ni1—N1—C8161.10 (9)C1—C6—C7—N17.20 (18)
N1i—Ni1—O1—C1158.63 (10)C7—N1—C8—C997.31 (12)
N1—Ni1—O1—C121.37 (10)Ni1—N1—C8—C982.15 (11)
Ni1—O1—C1—C612.98 (17)N1—C8—C9—C1487.37 (13)
Ni1—O1—C1—C2166.89 (9)N1—C8—C9—C1092.19 (13)
O1—C1—C2—C3179.45 (11)C14—C9—C10—C110.29 (18)
C6—C1—C2—C30.42 (17)C8—C9—C10—C11179.86 (12)
C1—C2—C3—C40.48 (19)C9—C10—C11—C120.9 (2)
C2—C3—C4—C50.03 (19)C10—C11—C12—F1178.90 (12)
C3—C4—C5—C60.47 (19)C10—C11—C12—C130.9 (2)
C4—C5—C6—C10.52 (18)F1—C12—C13—C14179.49 (11)
C4—C5—C6—C7175.37 (11)C11—C12—C13—C140.3 (2)
O1—C1—C6—C5179.94 (11)C12—C13—C14—C90.31 (19)
C2—C1—C6—C50.07 (17)C10—C9—C14—C130.32 (18)
O1—C1—C6—C75.30 (18)C8—C9—C14—C13179.25 (11)
C2—C1—C6—C7174.83 (11)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C8—H8A···O1i0.992.192.7300 (18)113
C14—H14A···O1i0.952.523.212 (2)130
C2—H2A···F1ii0.952.653.5312 (19)155
C5—H5A···Cg1iii0.952.693.4010 (18)133
C13—H13A···Cg2iv0.952.693.4252 (13)134
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y1/2, z1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+2, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C8—H8A···O1i0.992.192.7300 (18)113
C14—H14A···O1i0.952.523.212 (2)130
C2—H2A···F1ii0.952.653.5312 (19)155
C5—H5A···Cg1iii0.952.6853.4010 (18)133
C13—H13A···Cg2iv0.952.6933.4252 (13)134
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y1/2, z1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Ni(C14H11FNO)2]
Mr515.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)13.8611 (3), 5.83340 (1), 16.9942 (3)
β (°) 125.998 (1)
V3)1111.70 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.92
Crystal size (mm)0.47 × 0.19 × 0.11
Data collection
DiffractometerBruker APEXII CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.674, 0.906
No. of measured, independent and
observed [I > 2σ(I)] reflections
13419, 3235, 2896
Rint0.024
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.072, 1.05
No. of reflections3235
No. of parameters160
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.49

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2006) and publCIF (Westrip, 2010).

 

Footnotes

Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

The authors would like to acknowledge the Ministry of Education of Malaysia for research grants No. 600-RMI/FRGS 5/3 (51/2013) and (52/2013), Universiti Teknologi MARA for research grant No. 600-RMI/DANA 5/3/CG (15/2012) and Universiti Sains Malaysia for the use of the X-ray diffraction facilities. The authors would also like to acknowledge Universiti Kebangsaan Malaysia for the usage of its research facility for biological activity investigation.

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Volume 70| Part 10| October 2014| Pages 252-255
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