[4-Bromo-N-(pyridin-2-yl­methyl­idene)aniline-κ2N,N′]bis­(1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dionato-κ2O,O′)nickel(II)

Harding, P.; Harding, D.J.; Soponrat, N.; Adams, H.

doi:10.1107/S1600536811005599

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages m404-m405

doi:10.1107/S1600536811005599

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[4-Bromo-N-(pyridin-2-ylmethylidene)aniline-κ²N,N′]bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ²O,O′)nickel(II)

Phimphaka Harding,^a ^* David J. Harding,^a Nitisastr Soponrat ^b and Harry Adams ^c

^aMolecular Technology Research Unit, Department of Chemistry, Walailak University, Thasala, Nakhon Si Thammarat 80161, Thailand, ^bDepartment of Chemistry, Faculty of Science, Taksin University, Songkhla 90000, Thailand, and ^cDepartment of Chemistry, Faculty of Science, University of Sheffield, Brook Hill, Sheffield S3 7HF, England
^*Correspondence e-mail: kphimpha@wu.ac.th

(Received 3 August 2010; accepted 15 February 2011; online 9 March 2011)

The title compound, [Ni(C₅HF₆O₂)₂(C₁₂H₉BrN₂)], the Ni^II atom exhibits a pseudo-octahedral coordination geometry. The structure packs through C—H⋯Br interactions, forming a hydrogen-bonded ladder. There are also strong hydrogen-bonding interactions between two of the O atoms of the β-diketonate ligands and two H atoms on the pyridine ring of the Schiff base ligand.

Related literature

For related structures, see: Harding, Harding, Sophonrat & Adams (2010 ); Harding, Harding, Tinpun et al. (2010 ); Aakeröy et al. (2004 , 2005 , 2007 ). For an introduction to crystal engineering, see: Braga et al. (2002 ). For details concerning the coordination of additional ligands to β-diketonate complexes, see: Chassot & Emmenegger (1996 ); Emmenegger et al. (2001 ). For a description of the Cambridge Structural database, see: Allen et al. (2002 ).

Experimental

Crystal data

[Ni(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]
M_r = 733.95
Monoclinic, C 2/c
a = 31.251 (8) Å
b = 10.006 (3) Å
c = 17.653 (5) Å
β = 103.952 (5)°
V = 5358 (2) Å³
Z = 8
Mo Kα radiation
μ = 2.33 mm⁻¹
T = 150 K
0.22 × 0.12 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.628, T_max = 0.784
27645 measured reflections
5988 independent reflections
3422 reflections with I > 2σ(I)
R_int = 0.145

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.132
S = 0.91
5988 reflections
379 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −1.12 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O3	2.020 (3)
Ni1—O4	2.044 (3)
Ni1—O2	2.045 (3)
Ni1—N2	2.063 (3)
Ni1—O1	2.066 (3)
Ni1—N1	2.113 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Br1ⁱ	0.95	3.02	3.870 (3)	151
C2—H2⋯Br1ⁱⁱ	0.95	3.02	3.833 (3)	145
C12—H12⋯O1ⁱⁱⁱ	0.95	2.53	3.320 (4)	140
C11—H11⋯O4ⁱⁱⁱ	0.95	2.61	3.470 (3)	151
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005599/zb2010sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005599/zb2010Isup2.hkl

checkCIF report

Comment top

Metal β-diketonates represent an important class of complexes and are much studied owing to their ease of synthesis, ready modification and multiple applications. In the case of divalent metal ions, the [M(β-diketonate)₂] complexes are able to coordinate additional ligands forming either cis- or trans-octahedral metal complexes (Chassot & Emmenegger, 1996; Emmenegger et al., 2001). Of particular relevence to this paper is the use metal β-diketonates complexes in the preparation of crystal engineered networks (Braga et al., 2002) and while hydrogen bonded trans-isomers are well represented few compounds containing cis-isomers are described (Aäkeroy et al., 2004, 2005, 2007). In this paper we describe the synthesis and structure of [Ni(hfac)₂(ppa^Br)] (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionato; ppa^Br = (4-bromo-phenyl)pyridin-2-ylmethylene amine).

[Ni(hfac)₂(H₂O)₂] reacts readily with ppa^Br to give [Ni(hfac)₂(ppa^Br)] 1 which recrystallizes from CH₂Cl₂/n-hexane to give yellow crystals in the space group C2/c (Figure 1). This contrasts markedly with the analogous cobalt compound which crystallizes in P1 (Harding, Harding, Sophonrat and Adams, 2010). The nickel metal centre is pseudo-octahedral with a cis-arrangement enforced by the chelating ppa^Br ligand. The Ni—O and Ni—N bond lengths are typical of values reported for other nickel hfac and diimine complexes reported in the CSD (mean Ni—O distance = 2.01 Å, Ni—N distance = 2.11 Å, Allen, 2002). The β-diketonate ligands exhibit a bent coordination mode in which the angles between the planes defined by the Ni and oxygen atoms and the carbon and oxygen atoms of the β-diketonate ligand are 11.0° and 26.8°. In contrast, in trans-[M(hfac)₂(py-CH=CH—C₆F₄Br)₂] (M = Co, Cu) the β-diketonate ligands exhibit a planar coordination mode (Aäkeroy et al., 2007). In addition, the phenyl ring is twisted with to the pyridylimine unit by 30.0° a little greater than the angle observed in [Ni(dbm)₂(ppa^X)] (X = Me 22.9°, Cl 24.0°, Harding, Harding, Tinpun et al., 2010).

The packing in the structure is composed of two sets of interactions. The first set is involves a series of C—H···Br interactions (H6···Br 3.015 (3) Å, H2···Br 3.017 (3) Å) forming a hydrogen bonding ladder (Figure 2). The second interaction involves a strong hydrogen bonding interactions between two of the oxygen atoms of the β-diketonate ligands and two hydrogen atoms on the pyridyl ring of the ppa^Br ligand (O1···H12 2.532 (4) Å, O4···H11 2.610 (3) Å) forming a dimer (Figure 3). In contrast, the cobalt analogue has extensive π···π interactions and interactions between the Br atom on the ppa^Br ligand and the β-diketonate ligand (Harding, Harding, Sophonrat and Adams, 2010).

Related literature top

For related structures, see: Harding, Harding, Sophonrat & Adams (2010); Harding, Harding, Tinpun et al. (2010); Aäkeroy et al. (2004, 2005, 2007). For an introduction to crystal engineering, see: Braga et al. (2002). For details concerning the coordination of additional ligand to β-diketonates complexes, see: Chassot & Emmenegger (1996); Emmenegger et al. (2001). For a description of the Cambridge Structural database, see: Allen et al. (2002).

Experimental top

To a green solution of [Ni(hfac)₂(H₂O)₂] (0.128 g, 0.25 mmol) in CH₂Cl₂ (10 ml) was added a solution of ppa^Br (0.065 g, 0.25 mmol) in CH₂Cl₂ (3 ml). The orange solution was stirred overnight then concentrated in vacuo. n-Hexane (10 ml) was added to precipitate a yellow brown solid which was washed with n-hexane (2 x 5 ml) and dried in vacuo yielding a deep yellow solid (0.096 g, 52%). Found: C 36.2, H 1.7, N 3.9. Calc. for C₂₂H₁₁BrF₁₂N₂NiO₄: C 36.0, H 1.5, N 3.8%. m/z (ESI) 527 [M-hfac^-]⁺. n_max(KBr)/cm^-1 1651 (n_C=O). l_max(CH₂Cl₂)/nm (log e/M^-1cm^-1) 319 (4.46), 342 (4.34). Mpt. 156 °C.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (1) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular packing in (1) showing the C—H···Br interactions between neighbouring ppa^Br ligands. Only selected atoms are labelled for clairty. [Symmetry codes: (i) x, -1 + y, z; (ii) x, 1 + y, z; (iii) 1/2 - x, 1/2 - y, -z; (iv) 1/2 - x, 3/2 - y, -z; (v) 1/2 - x, 5/2 - y, -z].
	Fig. 3. The molecular packing in (1) showing the O···H interactions between the oxygen atoms of the β-diketonate ligands and the two hydrogen of the ppa^Br ligand. Only selected atoms are labelled for clairty. [Symmetry codes: (i) -x, y, 1/2 - z].

[4-Bromo-N-(pyridin-2-ylmethylidene)aniline- κ²N,N']bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato- κ²O,O')nickel(II) top

Crystal data top

[Ni(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]	F(000) = 2880
M_r = 733.95	D_x = 1.820 Mg m⁻³
Monoclinic, C2/c	Melting point: 429 K
Hall symbol: -C2yc	Mo Kα radiation, λ = 0.71073 Å
a = 31.251 (8) Å	Cell parameters from 3767 reflections
b = 10.006 (3) Å	θ = 2.4–24.9°
c = 17.653 (5) Å	µ = 2.33 mm⁻¹
β = 103.952 (5)°	T = 150 K
V = 5358 (2) Å³	Block, brown
Z = 8	0.22 × 0.12 × 0.11 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5988 independent reflections
Radiation source: fine-focus sealed tube	3422 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.145
Detector resolution: 100 pixels mm^-1	θ_max = 27.5°, θ_min = 1.3°
ϕ and ω scans	h = −39→40
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −12→12
T_min = 0.628, T_max = 0.784	l = −22→22
27645 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0546P)²] where P = (F_o² + 2F_c²)/3
5988 reflections	(Δ/σ)_max < 0.001
379 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −1.12 e Å⁻³

Crystal data top

[Ni(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]	V = 5358 (2) Å³
M_r = 733.95	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 31.251 (8) Å	µ = 2.33 mm⁻¹
b = 10.006 (3) Å	T = 150 K
c = 17.653 (5) Å	0.22 × 0.12 × 0.11 mm
β = 103.952 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5988 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	3422 reflections with I > 2σ(I)
T_min = 0.628, T_max = 0.784	R_int = 0.145
27645 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 0.91	Δρ_max = 1.24 e Å⁻³
5988 reflections	Δρ_min = −1.12 e Å⁻³
379 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

	x	y	z	U_iso*/U_eq
Ni1	0.089498 (18)	0.60018 (5)	0.17271 (3)	0.01947 (16)
Br1	0.279804 (16)	0.50379 (5)	−0.01356 (3)	0.03493 (16)
N1	0.10544 (11)	0.4874 (3)	0.0821 (2)	0.0180 (8)
N2	0.03045 (12)	0.5037 (3)	0.1283 (2)	0.0193 (8)
O1	0.06741 (10)	0.7013 (3)	0.25796 (16)	0.0227 (7)
O2	0.07571 (10)	0.7678 (3)	0.10485 (16)	0.0206 (7)
O3	0.14882 (9)	0.6873 (3)	0.21444 (17)	0.0253 (7)
O4	0.10989 (9)	0.4413 (3)	0.24516 (16)	0.0215 (7)
C1	0.22491 (15)	0.4979 (4)	0.0144 (3)	0.0268 (11)
C2	0.20348 (15)	0.3757 (5)	0.0139 (3)	0.0318 (12)
H2	0.2157	0.2965	−0.0018	0.038*
C3	0.16424 (15)	0.3716 (4)	0.0365 (3)	0.0269 (11)
H3	0.1497	0.2885	0.0375	0.032*
C4	0.14579 (14)	0.4876 (4)	0.0578 (3)	0.0197 (10)
C5	0.16748 (15)	0.6093 (4)	0.0566 (3)	0.0257 (11)
H5	0.1549	0.6892	0.0707	0.031*
C6	0.20726 (14)	0.6144 (4)	0.0351 (3)	0.0236 (10)
H6	0.2221	0.6971	0.0347	0.028*
C7	0.07464 (14)	0.4036 (4)	0.0519 (3)	0.0222 (10)
H7	0.0788	0.3410	0.0139	0.027*
C8	0.03340 (13)	0.4058 (4)	0.0765 (2)	0.0168 (9)
C9	−0.00087 (15)	0.3178 (4)	0.0481 (3)	0.0255 (11)
H9	0.0019	0.2505	0.0116	0.031*
C10	−0.03943 (15)	0.3295 (4)	0.0736 (3)	0.0261 (11)
H10	−0.0632	0.2691	0.0560	0.031*
C11	−0.04250 (15)	0.4301 (5)	0.1249 (3)	0.0265 (11)
H11	−0.0687	0.4407	0.1426	0.032*
C12	−0.00710 (14)	0.5167 (4)	0.1508 (3)	0.0223 (10)
H12	−0.0098	0.5870	0.1855	0.027*
C13	0.07108 (15)	0.8261 (4)	0.2653 (2)	0.0236 (10)
C14	0.06750 (18)	0.8781 (5)	0.3451 (3)	0.0326 (12)
C15	0.07746 (15)	0.9195 (4)	0.2105 (3)	0.0249 (11)
H15	0.0810	1.0110	0.2250	0.030*
C16	0.07882 (15)	0.8822 (4)	0.1348 (3)	0.0241 (11)
C17	0.08415 (17)	0.9929 (4)	0.0773 (3)	0.0278 (11)
C18	0.18236 (15)	0.6331 (4)	0.2566 (3)	0.0227 (10)
C19	0.22211 (17)	0.7250 (6)	0.2750 (3)	0.0410 (14)
C20	0.18587 (15)	0.5046 (4)	0.2881 (3)	0.0281 (11)
H20	0.2140	0.4740	0.3162	0.034*
C21	0.14966 (15)	0.4192 (4)	0.2797 (3)	0.0232 (10)
C22	0.15671 (15)	0.2806 (5)	0.3172 (3)	0.0286 (11)
F1	0.11909 (12)	0.9686 (3)	0.0484 (2)	0.0590 (10)
F2	0.04965 (11)	0.9967 (3)	0.01655 (16)	0.0474 (9)
F3	0.08890 (12)	1.1150 (3)	0.10758 (16)	0.0516 (9)
F4	0.03084 (12)	0.8339 (3)	0.3627 (2)	0.0651 (10)
F5	0.06729 (15)	1.0080 (3)	0.35147 (18)	0.0703 (12)
F6	0.09967 (13)	0.8311 (4)	0.40128 (18)	0.0775 (13)
F7	0.22453 (10)	0.8019 (3)	0.2159 (2)	0.0584 (10)
F8	0.21997 (13)	0.8058 (4)	0.3339 (2)	0.0789 (13)
F9	0.26008 (10)	0.6604 (4)	0.2971 (3)	0.0827 (14)
F10	0.13059 (10)	0.2608 (3)	0.3655 (2)	0.0540 (9)
F11	0.19792 (9)	0.2582 (3)	0.35786 (17)	0.0395 (8)
F12	0.14753 (11)	0.1857 (3)	0.26264 (18)	0.0522 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0209 (3)	0.0193 (3)	0.0168 (3)	−0.0020 (2)	0.0019 (2)	−0.0002 (2)
Br1	0.0284 (3)	0.0261 (3)	0.0550 (4)	−0.0007 (2)	0.0192 (3)	−0.0007 (2)
N1	0.0176 (19)	0.0186 (19)	0.020 (2)	0.0011 (15)	0.0087 (16)	0.0019 (15)
N2	0.019 (2)	0.0198 (18)	0.0171 (19)	0.0022 (15)	0.0002 (16)	0.0014 (15)
O1	0.0265 (17)	0.0234 (17)	0.0181 (16)	−0.0041 (13)	0.0051 (14)	−0.0022 (13)
O2	0.0269 (17)	0.0229 (16)	0.0123 (15)	−0.0012 (13)	0.0052 (14)	0.0002 (12)
O3	0.0202 (17)	0.0289 (17)	0.0248 (17)	−0.0049 (14)	0.0014 (15)	−0.0015 (14)
O4	0.0239 (17)	0.0250 (16)	0.0134 (15)	−0.0003 (13)	0.0001 (14)	0.0030 (13)
C1	0.023 (3)	0.026 (2)	0.028 (3)	0.003 (2)	0.000 (2)	0.001 (2)
C2	0.021 (3)	0.025 (3)	0.055 (4)	0.002 (2)	0.019 (2)	0.000 (2)
C3	0.024 (3)	0.018 (2)	0.041 (3)	−0.0019 (18)	0.013 (2)	0.000 (2)
C4	0.020 (2)	0.020 (2)	0.019 (2)	−0.0013 (18)	0.005 (2)	0.0001 (18)
C5	0.031 (3)	0.023 (2)	0.024 (2)	0.000 (2)	0.008 (2)	−0.002 (2)
C6	0.019 (2)	0.025 (2)	0.032 (3)	−0.0018 (19)	0.016 (2)	0.002 (2)
C7	0.028 (3)	0.016 (2)	0.019 (2)	0.0015 (19)	0.000 (2)	0.0013 (18)
C8	0.016 (2)	0.021 (2)	0.014 (2)	0.0027 (18)	0.0062 (18)	0.0056 (18)
C9	0.030 (3)	0.019 (2)	0.023 (2)	−0.0042 (19)	−0.001 (2)	−0.0012 (19)
C10	0.020 (3)	0.035 (3)	0.023 (3)	−0.008 (2)	0.005 (2)	−0.001 (2)
C11	0.023 (3)	0.038 (3)	0.020 (2)	−0.001 (2)	0.007 (2)	0.002 (2)
C12	0.022 (3)	0.027 (2)	0.017 (2)	0.0056 (19)	0.003 (2)	0.0011 (18)
C13	0.029 (3)	0.024 (2)	0.017 (2)	−0.005 (2)	0.003 (2)	−0.0033 (19)
C14	0.049 (3)	0.027 (3)	0.024 (3)	−0.012 (2)	0.012 (3)	−0.005 (2)
C15	0.031 (3)	0.020 (2)	0.025 (3)	−0.0018 (19)	0.009 (2)	−0.0032 (19)
C16	0.025 (3)	0.019 (2)	0.023 (2)	−0.0035 (18)	−0.003 (2)	0.0025 (19)
C17	0.034 (3)	0.024 (2)	0.026 (3)	−0.001 (2)	0.009 (2)	0.001 (2)
C18	0.025 (3)	0.029 (3)	0.015 (2)	−0.005 (2)	0.007 (2)	−0.0012 (19)
C19	0.030 (3)	0.044 (3)	0.046 (4)	−0.011 (3)	0.003 (3)	0.005 (3)
C20	0.020 (2)	0.034 (3)	0.027 (3)	0.001 (2)	0.000 (2)	0.002 (2)
C21	0.026 (3)	0.026 (2)	0.016 (2)	0.002 (2)	0.002 (2)	−0.0045 (19)
C22	0.023 (3)	0.033 (3)	0.030 (3)	0.001 (2)	0.008 (2)	0.003 (2)
F1	0.064 (2)	0.051 (2)	0.075 (3)	0.0070 (17)	0.042 (2)	0.0280 (18)
F2	0.059 (2)	0.0475 (19)	0.0271 (16)	−0.0053 (15)	−0.0060 (16)	0.0152 (14)
F3	0.100 (3)	0.0219 (15)	0.0304 (17)	−0.0123 (16)	0.0116 (18)	0.0018 (13)
F4	0.077 (3)	0.076 (2)	0.058 (2)	−0.030 (2)	0.045 (2)	−0.0352 (19)
F5	0.158 (4)	0.0290 (18)	0.0383 (19)	−0.0167 (19)	0.052 (2)	−0.0129 (14)
F6	0.086 (3)	0.113 (3)	0.0216 (17)	0.031 (2)	−0.0094 (19)	−0.0215 (19)
F7	0.050 (2)	0.066 (2)	0.056 (2)	−0.0321 (17)	0.0068 (18)	0.0199 (18)
F8	0.081 (3)	0.090 (3)	0.069 (3)	−0.051 (2)	0.022 (2)	−0.045 (2)
F9	0.0247 (18)	0.076 (3)	0.136 (4)	−0.0113 (18)	−0.004 (2)	0.041 (3)
F10	0.046 (2)	0.054 (2)	0.072 (2)	0.0198 (15)	0.0331 (19)	0.0345 (17)
F11	0.0330 (16)	0.0378 (16)	0.0419 (18)	0.0070 (13)	−0.0021 (15)	0.0108 (13)
F12	0.068 (2)	0.0274 (16)	0.050 (2)	0.0015 (15)	−0.0074 (18)	−0.0033 (15)

Geometric parameters (Å, º) top

Ni1—O3	2.020 (3)	C9—H9	0.9500
Ni1—O4	2.044 (3)	C10—C11	1.372 (6)
Ni1—O2	2.045 (3)	C10—H10	0.9500
Ni1—N2	2.063 (3)	C11—C12	1.393 (6)
Ni1—O1	2.066 (3)	C11—H11	0.9500
Ni1—N1	2.113 (4)	C12—H12	0.9500
Br1—C1	1.897 (5)	C13—C15	1.394 (6)
N1—C7	1.291 (5)	C13—C14	1.531 (7)
N1—C4	1.426 (6)	C14—F5	1.304 (5)
N2—C12	1.332 (6)	C14—F6	1.317 (6)
N2—C8	1.358 (5)	C14—F4	1.332 (6)
O1—C13	1.258 (5)	C15—C16	1.399 (6)
O2—C16	1.255 (5)	C15—H15	0.9500
O3—C18	1.253 (5)	C16—C17	1.538 (6)
O4—C21	1.265 (5)	C17—F2	1.326 (5)
C1—C6	1.376 (6)	C17—F3	1.327 (5)
C1—C2	1.393 (6)	C17—F1	1.334 (6)
C2—C3	1.379 (6)	C18—C20	1.394 (6)
C2—H2	0.9500	C18—C19	1.517 (7)
C3—C4	1.388 (6)	C19—F7	1.313 (6)
C3—H3	0.9500	C19—F9	1.325 (6)
C4—C5	1.396 (6)	C19—F8	1.331 (7)
C5—C6	1.386 (6)	C20—C21	1.397 (6)
C5—H5	0.9500	C20—H20	0.9500
C6—H6	0.9500	C21—C22	1.529 (6)
C7—C8	1.456 (6)	C22—F10	1.330 (6)
C7—H7	0.9500	C22—F12	1.333 (5)
C8—C9	1.384 (6)	C22—F11	1.333 (5)
C9—C10	1.390 (7)

O3—Ni1—O4	89.27 (12)	C11—C10—C9	118.7 (4)
O3—Ni1—O2	84.55 (12)	C11—C10—H10	120.7
O4—Ni1—O2	173.82 (12)	C9—C10—H10	120.7
O3—Ni1—N2	177.27 (13)	C10—C11—C12	119.8 (5)
O4—Ni1—N2	89.36 (12)	C10—C11—H11	120.1
O2—Ni1—N2	96.80 (12)	C12—C11—H11	120.1
O3—Ni1—O1	87.79 (12)	N2—C12—C11	121.9 (4)
O4—Ni1—O1	91.93 (12)	N2—C12—H12	119.1
O2—Ni1—O1	87.99 (12)	C11—C12—H12	119.1
N2—Ni1—O1	94.62 (13)	O1—C13—C15	128.3 (4)
O3—Ni1—N1	98.24 (13)	O1—C13—C14	114.1 (4)
O4—Ni1—N1	87.91 (12)	C15—C13—C14	117.7 (4)
O2—Ni1—N1	92.82 (12)	F5—C14—F6	108.1 (4)
N2—Ni1—N1	79.35 (14)	F5—C14—F4	106.8 (5)
O1—Ni1—N1	173.97 (13)	F6—C14—F4	104.4 (4)
C7—N1—C4	120.1 (4)	F5—C14—C13	114.9 (4)
C7—N1—Ni1	111.8 (3)	F6—C14—C13	111.0 (4)
C4—N1—Ni1	127.9 (3)	F4—C14—C13	111.0 (4)
C12—N2—C8	118.6 (4)	C13—C15—C16	121.8 (4)
C12—N2—Ni1	127.8 (3)	C13—C15—H15	119.1
C8—N2—Ni1	113.2 (3)	C16—C15—H15	119.1
C13—O1—Ni1	121.6 (3)	O2—C16—C15	129.0 (4)
C16—O2—Ni1	121.2 (3)	O2—C16—C17	112.9 (4)
C18—O3—Ni1	126.3 (3)	C15—C16—C17	118.1 (4)
C21—O4—Ni1	124.0 (3)	F2—C17—F3	106.8 (4)
C6—C1—C2	121.5 (5)	F2—C17—F1	106.0 (4)
C6—C1—Br1	119.2 (3)	F3—C17—F1	107.4 (4)
C2—C1—Br1	119.2 (3)	F2—C17—C16	111.0 (4)
C3—C2—C1	118.9 (4)	F3—C17—C16	114.7 (4)
C3—C2—H2	120.5	F1—C17—C16	110.5 (4)
C1—C2—H2	120.5	O3—C18—C20	127.6 (4)
C2—C3—C4	120.7 (4)	O3—C18—C19	112.9 (4)
C2—C3—H3	119.7	C20—C18—C19	119.5 (4)
C4—C3—H3	119.7	F7—C19—F9	107.5 (5)
C3—C4—C5	119.4 (4)	F7—C19—F8	106.8 (5)
C3—C4—N1	122.4 (4)	F9—C19—F8	106.1 (5)
C5—C4—N1	118.2 (4)	F7—C19—C18	112.7 (4)
C6—C5—C4	120.5 (4)	F9—C19—C18	113.3 (4)
C6—C5—H5	119.8	F8—C19—C18	110.0 (5)
C4—C5—H5	119.8	C18—C20—C21	122.6 (4)
C1—C6—C5	119.0 (4)	C18—C20—H20	118.7
C1—C6—H6	120.5	C21—C20—H20	118.7
C5—C6—H6	120.5	O4—C21—C20	128.4 (4)
N1—C7—C8	119.5 (4)	O4—C21—C22	112.9 (4)
N1—C7—H7	120.3	C20—C21—C22	118.7 (4)
C8—C7—H7	120.3	F10—C22—F12	107.4 (4)
N2—C8—C9	122.1 (4)	F10—C22—F11	107.0 (4)
N2—C8—C7	114.9 (4)	F12—C22—F11	106.3 (4)
C9—C8—C7	123.0 (4)	F10—C22—C21	111.5 (4)
C8—C9—C10	119.0 (4)	F12—C22—C21	110.5 (4)
C8—C9—H9	120.5	F11—C22—C21	113.9 (4)
C10—C9—H9	120.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Br1ⁱ	0.95	3.02	3.870 (3)	151
C2—H2···Br1ⁱⁱ	0.95	3.02	3.833 (3)	145
C12—H12···O1ⁱⁱⁱ	0.95	2.53	3.320 (4)	140
C11—H11···O4ⁱⁱⁱ	0.95	2.61	3.470 (3)	151

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

Experimental details

Crystal data
Chemical formula	[Ni(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]
M_r	733.95
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	31.251 (8), 10.006 (3), 17.653 (5)
β (°)	103.952 (5)
V (Å³)	5358 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.33
Crystal size (mm)	0.22 × 0.12 × 0.11

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.628, 0.784
No. of measured, independent and observed [I > 2σ(I)] reflections	27645, 5988, 3422
R_int	0.145
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.132, 0.91
No. of reflections	5988
No. of parameters	379
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −1.12

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Ni1—O3	2.020 (3)	Ni1—N2	2.063 (3)
Ni1—O4	2.044 (3)	Ni1—O1	2.066 (3)
Ni1—O2	2.045 (3)	Ni1—N1	2.113 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Br1ⁱ	0.95	3.015	3.870 (3)	151
C2—H2···Br1ⁱⁱ	0.95	3.017	3.833 (3)	145
C12—H12···O1ⁱⁱⁱ	0.95	2.532	3.320 (4)	140
C11—H11···O4ⁱⁱⁱ	0.95	2.610	3.470 (3)	151

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

Acknowledgements

We thank the Thailand Research Fund (grant No. RSA5080007) for funding this research.

References

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