[(4-Bromo­phen­yl)(2-pyridyl­methyl­idene)amine-κ2N,N′]bis­(1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dionato-κ2O,O′)cobalt(II)

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

doi:10.1107/S1600536810032757

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Pages m1138-m1139

https://doi.org/10.1107/S1600536810032757

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[(4-Bromophenyl)(2-pyridylmethylidene)amine-κ²N,N′]bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ²O,O′)cobalt(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 14 August 2010; online 21 August 2010)

In the title complex, [Co(C₅HF₆O₂)₂(C₁₂H₉BrN₂)], the Co^II atom exhibits a pseudo-octahedral coordination geometry, comprising two N-donor atoms from a bidentate chelate (4-bromophenyl)(2-pyridylmethylidene)amine (ppa^Br) ligand [Co—N = 2.098 (2) and 2.209 (2) Å] and four O-donor atoms from two bidentate chelate 1,1,1,5,5,5-hexafluoropentane-2,4-dionate (hfac) ligands [Co—O range = 2.0452 (19)–2.0796 (19) Å]. The packing of the structure involves weak π–π interactions between the pyridyl and benzene rings of neighbouring ppa^Br ligands [centroid–centroid distance = 3.928 (2) Å] and interactions between the Br atom on the ppa^Br ligand and the hfac ligand [Br⋯C = 3.531 (2) Å].

Related literature

For a review of halogen bonding, see: Corradi et al. (2000 ); Walsh et al. (2001 ); Liantonio et al. (2003 ). For an introduction to crystal engineering, see: Braga et al. (2002 ). For related structures, see: Harding, Harding, Sophonrat & Adams (2010 ); Harding, Harding, Tinpun et al. (2010 ); Aäkeroy et al. (2004 , 2007 ). For a description of the Cambridge Structural database, see: Allen et al. (2002 ).

Experimental

Crystal data

[Co(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]
M_r = 734.17
Triclinic, $[P \overline 1]$
a = 8.3568 (2) Å
b = 10.9420 (2) Å
c = 14.8151 (3) Å
α = 74.042 (1)°
β = 86.510 (1)°
γ = 77.080 (1)°
V = 1269.51 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.37 mm⁻¹
T = 150 K
0.60 × 0.30 × 0.03 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.330, T_max = 0.932
21525 measured reflections
5176 independent reflections
4508 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.08
5176 reflections
379 parameters
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −0.91 e Å⁻³

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810032757/zs2056sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032757/zs2056Isup2.hkl

checkCIF report

Comment top

The construction of supramolecular networks with designed architectures still remains the goal of crystal engineering and represents a significant challenge (Braga et al., 2002). Although complementary hydrogen-bonding ligands have been successfully used (Aäkeroy et al., 2004) in the construction of a number of networks, halogen-bonding (Walsh et al., 2001; Liantonio et al., 2003) and halogen···halogen interactions remain less well represented despite the fact that these interactions can be as strong as hydrogen-bonding interactions (Corradi et al., 2000). In this paper we report the synthesis and structure of [Co(hfac)₂(ppa^Br)] [hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionato; ppa^Br = (4-bromo-phenyl)pyridin-2-ylmethyleneamine].

The reaction of [Co(hfac)₂(H₂O)₂] with ppa^Br in CH₂Cl₂ yields [Co(hfac)₂(ppa^Br)] (I) (Fig. 1) which crystallizes from CH₂Cl₂/hexane. In (I) the cobalt metal centre is six-coordinate with a distorted octahedral geometry, the hfac ligands adopting a cis arrangement enforced by the chelating ppa^Br ligand. The CF₃ groups of the hfac ligand in some cases exhibit large thermal ellipsoids due to thermal motion of these groups. The Co—N and Co—O bond lengths are comparable with related cobalt hfac and diimine complexes reported in the CSD (Allen, 2002) (mean Co—O distance = 2.01 Å, Co—N distance = 2.11 Å). The β-diketonate ligands exhibit a bent coordination mode in which the angles between the planes defined by the Co and oxygen atoms and the carbon and oxygen atoms of the β-diketonate ligand are 18.9° and 24.7°. 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 respect to the pyridylimine unit by 17.6° and is similar to 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 of (I) involves a weak π–π interaction between the pyridyl and phenyl rings of neighbouring ppa^Br ligands as shown in Fig. 2 (Cg1···Cg2 = 3.928 (2) Å where Cg1 and Cg2 are the centroids of the rings C1—C6 and C8—C12—N2). A further weak interaction occurs between the Br atom on the ppa^Br ligand and the β-diketonate ligand creating discrete dimers within the structure [Br···C20, 3.531 (2) Å, see Fig. 3]. These dimers are then connected via the π–π interaction mentioned above resulting in one-dimensional chains. A similar interaction is also observed in the structure of trans-[M(hfac)₂(py-CH=CH—C₆F₄Br)₂] (Aäkeroy et al., 2007). Interestingly, the corresponding Ni analogue, [Ni(hfac)₂(ppa^Br)] has a completely different set of interactions with Br···CH interactions clearly evident (Harding, Harding, Sophonrat & Adams, 2010), once again highlighting the difficulties involved in attempting to use specific interactions in the design of supramolecular networks.

Related literature top

For a review of halogen bonding, see: Corradi et al. (2000); Walsh et al. (2001); Liantonio et al. (2003). For an introduction to crystal engineering, see: Braga et al. (2002). For related structures, see: Harding, Harding, Sophonrat & Adams (2010); Harding, Harding, Tinpun et al. (2010); Aäkeroy et al. (2004, 2007). For a description of the Cambridge Structural database, see: Allen et al. (2002).

Experimental top

To an orange red solution of [Co(hfac)₂(H₂O)₂] (0.127 g, 0.25 mmol) in CH₂Cl₂ (5 cm³) was added a solution of ppa^Br (0.065 g, 0.25 mmol) in CH₂Cl₂ (3 cm³). The deep orange solution was stirred for 1 h and then concentrated in vacuo. n-Hexane (15 cm³) was added to precipitate an orange solid which was washed with n-hexane (2 x 5 cm³) and dried in vacuo: yield 0.142 g (77%). IR in KBr disc ν_C=O 1647 cm^-1. UV-Vis (in CH₂Cl₂, log ε mol.dm^-3cm^-1) 243 (4.24), 309 (4.42). C₂₂H₁₁O₄N₂F₁₂BrCo; calc. C 36.0, H 1.5, N 3.8%; found C 36.5, H 1.5, N 3.8%.

Structure description top

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (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).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular packing in (I) showing the π–π interactions between the phenyl and pyridyl rings of the ppa^Br ligand. Only selected atoms are labelled for clarity. [Symmetry code: (i) -x + 2, -y, -z + 2].
	Fig. 3. The molecular packing in (I) showing the Br···β-diketonate interactions of the discrete dimers. Only selected atoms are labelled for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z + 2].

[(4-Bromophenyl)(2-pyridylmethylidene)amine- κ²N,N']bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato- κ²O,O')cobalt(II) top

Crystal data top

[Co(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]	Z = 2
M_r = 734.17	F(000) = 718
Triclinic, P1	D_x = 1.921 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3568 (2) Å	Cell parameters from 9953 reflections
b = 10.9420 (2) Å	θ = 2.9–32.8°
c = 14.8151 (3) Å	µ = 2.37 mm⁻¹
α = 74.042 (1)°	T = 150 K
β = 86.510 (1)°	Plate, orange
γ = 77.080 (1)°	0.60 × 0.30 × 0.03 mm
V = 1269.51 (5) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	5176 independent reflections
Radiation source: fine-focus sealed tube	4508 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
φ and ω scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −10→10
T_min = 0.330, T_max = 0.932	k = −13→13
21525 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0399P)² + 2.417P] where P = (F_o² + 2F_c²)/3
5176 reflections	(Δ/σ)_max = 0.001
379 parameters	Δρ_max = 1.23 e Å⁻³
0 restraints	Δρ_min = −0.91 e Å⁻³

Crystal data top

[Co(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]	γ = 77.080 (1)°
M_r = 734.17	V = 1269.51 (5) Å³
Triclinic, P1	Z = 2
a = 8.3568 (2) Å	Mo Kα radiation
b = 10.9420 (2) Å	µ = 2.37 mm⁻¹
c = 14.8151 (3) Å	T = 150 K
α = 74.042 (1)°	0.60 × 0.30 × 0.03 mm
β = 86.510 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5176 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	4508 reflections with I > 2σ(I)
T_min = 0.330, T_max = 0.932	R_int = 0.021
21525 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	Δρ_max = 1.23 e Å⁻³
5176 reflections	Δρ_min = −0.91 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
Br1	0.24966 (4)	0.40512 (3)	1.12788 (2)	0.02627 (10)
C1	0.4059 (3)	0.3017 (3)	1.0652 (2)	0.0190 (6)
C2	0.4540 (4)	0.1698 (3)	1.1069 (2)	0.0234 (6)
H2	0.4096	0.1318	1.1659	0.028*
C3	0.5671 (4)	0.0937 (3)	1.0621 (2)	0.0220 (6)
H3	0.6002	0.0028	1.0903	0.026*
C4	0.6331 (3)	0.1491 (3)	0.97587 (19)	0.0165 (5)
C5	0.5813 (3)	0.2824 (3)	0.93439 (19)	0.0198 (6)
H5	0.6237	0.3208	0.8750	0.024*
C6	0.4680 (4)	0.3591 (3)	0.9796 (2)	0.0218 (6)
H6	0.4337	0.4500	0.9519	0.026*
C7	0.8328 (3)	−0.0354 (3)	0.96759 (19)	0.0182 (5)
H7	0.8186	−0.0694	1.0331	0.022*
C8	0.9486 (3)	−0.1115 (3)	0.91526 (19)	0.0172 (5)
C9	1.0341 (4)	−0.2363 (3)	0.9576 (2)	0.0221 (6)
H9	1.0201	−0.2753	1.0225	0.027*
C10	1.1404 (4)	−0.3031 (3)	0.9032 (2)	0.0240 (6)
H10	1.1991	−0.3896	0.9301	0.029*
C11	1.1601 (4)	−0.2431 (3)	0.8099 (2)	0.0242 (6)
H11	1.2336	−0.2869	0.7718	0.029*
C12	1.0707 (4)	−0.1171 (3)	0.7723 (2)	0.0217 (6)
H12	1.0847	−0.0757	0.7078	0.026*
C13	0.8228 (4)	0.1729 (3)	0.5708 (2)	0.0215 (6)
C14	0.9068 (4)	0.2216 (3)	0.4767 (2)	0.0322 (7)
C15	0.6657 (4)	0.1503 (3)	0.5689 (2)	0.0258 (6)
H15	0.6125	0.1698	0.5102	0.031*
C16	0.5849 (4)	0.0998 (3)	0.6508 (2)	0.0246 (6)
C17	0.4252 (4)	0.0581 (4)	0.6393 (2)	0.0361 (8)
C18	0.7556 (4)	0.4215 (3)	0.6922 (2)	0.0223 (6)
C19	0.6383 (5)	0.5432 (3)	0.6348 (3)	0.0414 (9)
C20	0.9177 (4)	0.4284 (3)	0.7033 (2)	0.0231 (6)
H20	0.9542	0.5051	0.6707	0.028*
C21	1.0267 (4)	0.3261 (3)	0.7608 (2)	0.0203 (6)
C22	1.1961 (4)	0.3521 (3)	0.7732 (3)	0.0330 (8)
Co1	0.82077 (4)	0.13568 (3)	0.77538 (2)	0.01482 (10)
F1	0.3604 (3)	0.1057 (3)	0.55597 (18)	0.0696 (8)
F2	0.4576 (3)	−0.0730 (2)	0.65283 (19)	0.0578 (7)
F3	0.3172 (3)	0.0779 (3)	0.70502 (19)	0.0578 (7)
F4	0.9544 (4)	0.3293 (3)	0.47281 (18)	0.0768 (10)
F5	0.8123 (3)	0.2441 (3)	0.40289 (14)	0.0636 (8)
F6	1.0401 (3)	0.1358 (2)	0.46507 (15)	0.0508 (6)
F7	0.5963 (6)	0.5260 (3)	0.5585 (3)	0.130 (2)
F8	0.5029 (3)	0.5703 (2)	0.6848 (3)	0.0862 (11)
F9	0.6978 (3)	0.64976 (19)	0.61453 (18)	0.0505 (6)
F10	1.2729 (3)	0.3815 (4)	0.6912 (2)	0.0974 (13)
F11	1.1845 (4)	0.4500 (3)	0.8083 (3)	0.1054 (15)
F12	1.2953 (2)	0.25146 (19)	0.82617 (16)	0.0406 (5)
N1	0.7503 (3)	0.0775 (2)	0.92465 (16)	0.0159 (5)
N2	0.9660 (3)	−0.0524 (2)	0.82359 (16)	0.0171 (5)
O1	0.9099 (2)	0.15687 (19)	0.64017 (13)	0.0195 (4)
O2	0.6285 (2)	0.07571 (19)	0.73472 (14)	0.0207 (4)
O3	0.6895 (2)	0.32603 (18)	0.72450 (13)	0.0194 (4)
O4	1.0045 (2)	0.21558 (18)	0.80721 (13)	0.0192 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02487 (16)	0.02549 (16)	0.02822 (17)	−0.00312 (12)	0.00920 (12)	−0.01065 (12)
C1	0.0152 (13)	0.0234 (14)	0.0211 (14)	−0.0036 (11)	0.0022 (11)	−0.0116 (11)
C2	0.0295 (16)	0.0212 (14)	0.0213 (14)	−0.0111 (12)	0.0086 (12)	−0.0061 (12)
C3	0.0280 (15)	0.0158 (13)	0.0219 (14)	−0.0066 (12)	0.0031 (12)	−0.0036 (11)
C4	0.0159 (13)	0.0189 (13)	0.0166 (13)	−0.0056 (11)	−0.0007 (10)	−0.0061 (10)
C5	0.0201 (14)	0.0212 (14)	0.0152 (13)	−0.0026 (11)	0.0008 (11)	−0.0021 (11)
C6	0.0222 (14)	0.0179 (13)	0.0214 (14)	0.0010 (11)	−0.0018 (11)	−0.0026 (11)
C7	0.0207 (14)	0.0194 (13)	0.0140 (13)	−0.0048 (11)	−0.0011 (11)	−0.0032 (10)
C8	0.0172 (13)	0.0169 (13)	0.0179 (13)	−0.0040 (11)	−0.0035 (10)	−0.0044 (10)
C9	0.0240 (15)	0.0202 (14)	0.0192 (14)	−0.0010 (12)	−0.0058 (11)	−0.0026 (11)
C10	0.0232 (15)	0.0190 (13)	0.0269 (15)	0.0036 (12)	−0.0074 (12)	−0.0063 (12)
C11	0.0207 (14)	0.0244 (14)	0.0270 (15)	0.0004 (12)	−0.0010 (12)	−0.0102 (12)
C12	0.0224 (14)	0.0227 (14)	0.0195 (14)	−0.0036 (12)	−0.0001 (11)	−0.0057 (11)
C13	0.0279 (15)	0.0176 (13)	0.0181 (14)	−0.0028 (12)	0.0005 (12)	−0.0050 (11)
C14	0.0380 (19)	0.0381 (18)	0.0193 (15)	−0.0089 (15)	0.0039 (13)	−0.0058 (13)
C15	0.0278 (16)	0.0287 (15)	0.0206 (15)	−0.0050 (13)	−0.0044 (12)	−0.0060 (12)
C16	0.0245 (15)	0.0239 (14)	0.0269 (16)	−0.0075 (12)	−0.0044 (12)	−0.0065 (12)
C17	0.0330 (18)	0.050 (2)	0.0322 (18)	−0.0197 (16)	−0.0029 (15)	−0.0127 (16)
C18	0.0281 (16)	0.0191 (14)	0.0175 (14)	−0.0024 (12)	−0.0025 (12)	−0.0030 (11)
C19	0.041 (2)	0.0228 (16)	0.054 (2)	−0.0067 (15)	−0.0224 (18)	0.0045 (16)
C20	0.0279 (15)	0.0195 (14)	0.0218 (14)	−0.0095 (12)	0.0018 (12)	−0.0025 (11)
C21	0.0216 (14)	0.0208 (14)	0.0206 (14)	−0.0074 (11)	0.0005 (11)	−0.0069 (11)
C22	0.0295 (17)	0.0220 (15)	0.048 (2)	−0.0120 (14)	−0.0081 (15)	−0.0028 (14)
Co1	0.01588 (19)	0.01408 (18)	0.01382 (18)	−0.00367 (14)	−0.00033 (14)	−0.00219 (14)
F1	0.0544 (16)	0.104 (2)	0.0513 (15)	−0.0445 (16)	−0.0281 (12)	0.0049 (14)
F2	0.0614 (16)	0.0504 (14)	0.0774 (18)	−0.0309 (12)	0.0001 (13)	−0.0281 (13)
F3	0.0297 (11)	0.0890 (19)	0.0739 (17)	−0.0283 (12)	0.0120 (11)	−0.0436 (15)
F4	0.141 (3)	0.0613 (16)	0.0414 (14)	−0.0620 (18)	0.0404 (16)	−0.0119 (12)
F5	0.0408 (13)	0.118 (2)	0.0176 (10)	−0.0071 (14)	−0.0015 (9)	−0.0019 (12)
F6	0.0361 (12)	0.0704 (16)	0.0345 (12)	0.0019 (11)	0.0130 (9)	−0.0088 (11)
F7	0.238 (5)	0.0398 (15)	0.102 (3)	0.010 (2)	−0.137 (3)	−0.0037 (16)
F8	0.0272 (13)	0.0385 (14)	0.159 (3)	0.0060 (11)	0.0007 (16)	0.0188 (17)
F9	0.0464 (13)	0.0239 (10)	0.0674 (16)	−0.0076 (9)	−0.0113 (11)	0.0128 (10)
F10	0.0476 (16)	0.158 (3)	0.0688 (19)	−0.062 (2)	−0.0036 (14)	0.031 (2)
F11	0.0547 (17)	0.0586 (17)	0.230 (4)	0.0108 (14)	−0.065 (2)	−0.088 (2)
F12	0.0260 (10)	0.0309 (10)	0.0644 (14)	−0.0070 (8)	−0.0163 (10)	−0.0077 (10)
N1	0.0160 (11)	0.0154 (11)	0.0174 (11)	−0.0043 (9)	−0.0008 (9)	−0.0055 (9)
N2	0.0179 (11)	0.0164 (11)	0.0174 (11)	−0.0047 (9)	−0.0002 (9)	−0.0040 (9)
O1	0.0210 (10)	0.0214 (10)	0.0155 (9)	−0.0057 (8)	0.0001 (8)	−0.0031 (8)
O2	0.0224 (10)	0.0206 (10)	0.0195 (10)	−0.0090 (8)	−0.0007 (8)	−0.0025 (8)
O3	0.0192 (10)	0.0179 (9)	0.0194 (10)	−0.0035 (8)	−0.0010 (8)	−0.0026 (8)
O4	0.0209 (10)	0.0181 (9)	0.0190 (10)	−0.0064 (8)	−0.0022 (8)	−0.0031 (8)

Geometric parameters (Å, º) top

Br1—C1	1.902 (3)	C14—F6	1.322 (4)
C1—C6	1.378 (4)	C14—F5	1.322 (4)
C1—C2	1.382 (4)	C15—C16	1.391 (4)
C2—C3	1.379 (4)	C15—H15	0.9500
C2—H2	0.9500	C16—O2	1.256 (4)
C3—C4	1.394 (4)	C16—C17	1.537 (4)
C3—H3	0.9500	C17—F1	1.300 (4)
C4—C5	1.397 (4)	C17—F3	1.316 (4)
C4—N1	1.429 (3)	C17—F2	1.358 (4)
C5—C6	1.388 (4)	C18—O3	1.255 (4)
C5—H5	0.9500	C18—C20	1.396 (4)
C6—H6	0.9500	C18—C19	1.534 (4)
C7—N1	1.284 (4)	C19—F7	1.278 (5)
C7—C8	1.461 (4)	C19—F9	1.321 (4)
C7—H7	0.9500	C19—F8	1.336 (5)
C8—N2	1.349 (4)	C20—C21	1.387 (4)
C8—C9	1.384 (4)	C20—H20	0.9500
C9—C10	1.385 (4)	C21—O4	1.264 (3)
C9—H9	0.9500	C21—C22	1.537 (4)
C10—C11	1.375 (4)	C22—F11	1.296 (4)
C10—H10	0.9500	C22—F12	1.308 (4)
C11—C12	1.392 (4)	C22—F10	1.332 (5)
C11—H11	0.9500	Co1—O2	2.0452 (19)
C12—N2	1.335 (4)	Co1—O4	2.0639 (19)
C12—H12	0.9500	Co1—O1	2.0644 (19)
C13—O1	1.246 (3)	Co1—O3	2.0796 (19)
C13—C15	1.392 (4)	Co1—N2	2.098 (2)
C13—C14	1.537 (4)	Co1—N1	2.209 (2)
C14—F4	1.312 (4)

C6—C1—C2	121.5 (3)	F1—C17—F2	104.7 (3)
C6—C1—Br1	119.8 (2)	F3—C17—F2	103.7 (3)
C2—C1—Br1	118.7 (2)	F1—C17—C16	114.6 (3)
C3—C2—C1	119.3 (3)	F3—C17—C16	112.2 (3)
C3—C2—H2	120.4	F2—C17—C16	109.1 (3)
C1—C2—H2	120.4	O3—C18—C20	128.0 (3)
C2—C3—C4	120.5 (3)	O3—C18—C19	113.7 (3)
C2—C3—H3	119.7	C20—C18—C19	118.3 (3)
C4—C3—H3	119.7	F7—C19—F9	108.7 (4)
C3—C4—C5	119.2 (3)	F7—C19—F8	108.4 (4)
C3—C4—N1	124.2 (2)	F9—C19—F8	104.6 (3)
C5—C4—N1	116.6 (2)	F7—C19—C18	111.1 (3)
C6—C5—C4	120.3 (3)	F9—C19—C18	114.0 (3)
C6—C5—H5	119.9	F8—C19—C18	109.6 (3)
C4—C5—H5	119.9	C21—C20—C18	121.5 (3)
C1—C6—C5	119.2 (3)	C21—C20—H20	119.3
C1—C6—H6	120.4	C18—C20—H20	119.3
C5—C6—H6	120.4	O4—C21—C20	129.1 (3)
N1—C7—C8	119.7 (2)	O4—C21—C22	115.2 (3)
N1—C7—H7	120.1	C20—C21—C22	115.7 (3)
C8—C7—H7	120.1	F11—C22—F12	108.3 (3)
N2—C8—C9	122.5 (3)	F11—C22—F10	106.4 (4)
N2—C8—C7	115.7 (2)	F12—C22—F10	105.6 (3)
C9—C8—C7	121.7 (3)	F11—C22—C21	111.6 (3)
C10—C9—C8	118.5 (3)	F12—C22—C21	113.1 (3)
C10—C9—H9	120.7	F10—C22—C21	111.3 (3)
C8—C9—H9	120.7	O2—Co1—O4	173.89 (8)
C11—C10—C9	119.3 (3)	O2—Co1—O1	87.88 (8)
C11—C10—H10	120.3	O4—Co1—O1	89.87 (8)
C9—C10—H10	120.3	O2—Co1—O3	87.74 (8)
C10—C11—C12	119.0 (3)	O4—Co1—O3	86.41 (8)
C10—C11—H11	120.5	O1—Co1—O3	85.05 (8)
C12—C11—H11	120.5	O2—Co1—N2	94.96 (8)
N2—C12—C11	122.3 (3)	O4—Co1—N2	90.82 (8)
N2—C12—H12	118.9	O1—Co1—N2	92.91 (8)
C11—C12—H12	118.9	O3—Co1—N2	176.56 (8)
O1—C13—C15	128.6 (3)	O2—Co1—N1	91.80 (8)
O1—C13—C14	113.3 (3)	O4—Co1—N1	91.41 (8)
C15—C13—C14	118.1 (3)	O1—Co1—N1	169.94 (8)
F4—C14—F6	106.5 (3)	O3—Co1—N1	104.98 (8)
F4—C14—F5	107.8 (3)	N2—Co1—N1	77.10 (9)
F6—C14—F5	106.3 (3)	C7—N1—C4	119.2 (2)
F4—C14—C13	111.0 (3)	C7—N1—Co1	111.94 (18)
F6—C14—C13	111.4 (3)	C4—N1—Co1	128.79 (17)
F5—C14—C13	113.5 (3)	C12—N2—C8	118.4 (2)
C16—C15—C13	121.6 (3)	C12—N2—Co1	126.20 (19)
C16—C15—H15	119.2	C8—N2—Co1	115.41 (18)
C13—C15—H15	119.2	C13—O1—Co1	123.71 (19)
O2—C16—C15	129.1 (3)	C16—O2—Co1	123.95 (19)
O2—C16—C17	114.0 (3)	C18—O3—Co1	123.68 (19)
C15—C16—C17	116.7 (3)	C21—O4—Co1	122.51 (18)
F1—C17—F3	111.6 (3)

C6—C1—C2—C3	0.2 (4)	C5—C4—N1—C7	162.6 (3)
Br1—C1—C2—C3	179.9 (2)	C3—C4—N1—Co1	163.1 (2)
C1—C2—C3—C4	0.4 (4)	C5—C4—N1—Co1	−15.6 (3)
C2—C3—C4—C5	−1.1 (4)	O2—Co1—N1—C7	97.18 (19)
C2—C3—C4—N1	−179.8 (3)	O4—Co1—N1—C7	−88.02 (19)
C3—C4—C5—C6	1.4 (4)	O1—Co1—N1—C7	9.2 (6)
N1—C4—C5—C6	−179.8 (2)	O3—Co1—N1—C7	−174.68 (18)
C2—C1—C6—C5	0.1 (4)	N2—Co1—N1—C7	2.50 (18)
Br1—C1—C6—C5	−179.7 (2)	O2—Co1—N1—C4	−84.5 (2)
C4—C5—C6—C1	−0.9 (4)	O4—Co1—N1—C4	90.3 (2)
N1—C7—C8—N2	3.1 (4)	O1—Co1—N1—C4	−172.5 (4)
N1—C7—C8—C9	−176.7 (3)	O3—Co1—N1—C4	3.6 (2)
N2—C8—C9—C10	−0.5 (4)	N2—Co1—N1—C4	−179.2 (2)
C7—C8—C9—C10	179.2 (3)	C11—C12—N2—C8	0.8 (4)
C8—C9—C10—C11	1.2 (4)	C11—C12—N2—Co1	−178.8 (2)
C9—C10—C11—C12	−0.9 (4)	C9—C8—N2—C12	−0.5 (4)
C10—C11—C12—N2	−0.2 (4)	C7—C8—N2—C12	179.8 (2)
O1—C13—C14—F4	−55.7 (4)	C9—C8—N2—Co1	179.2 (2)
C15—C13—C14—F4	125.5 (3)	C7—C8—N2—Co1	−0.6 (3)
O1—C13—C14—F6	62.7 (4)	O2—Co1—N2—C12	88.0 (2)
C15—C13—C14—F6	−116.0 (3)	O4—Co1—N2—C12	−90.1 (2)
O1—C13—C14—F5	−177.3 (3)	O1—Co1—N2—C12	−0.2 (2)
C15—C13—C14—F5	3.9 (4)	N1—Co1—N2—C12	178.7 (2)
O1—C13—C15—C16	−2.0 (5)	O2—Co1—N2—C8	−91.62 (19)
C14—C13—C15—C16	176.6 (3)	O4—Co1—N2—C8	90.35 (19)
C13—C15—C16—O2	5.1 (5)	O1—Co1—N2—C8	−179.74 (19)
C13—C15—C16—C17	−170.3 (3)	N1—Co1—N2—C8	−0.91 (18)
O2—C16—C17—F1	166.4 (3)	C15—C13—O1—Co1	−16.6 (4)
C15—C16—C17—F1	−17.5 (5)	C14—C13—O1—Co1	164.79 (19)
O2—C16—C17—F3	37.7 (4)	O2—Co1—O1—C13	23.0 (2)
C15—C16—C17—F3	−146.2 (3)	O4—Co1—O1—C13	−151.3 (2)
O2—C16—C17—F2	−76.6 (4)	O3—Co1—O1—C13	−64.9 (2)
C15—C16—C17—F2	99.4 (3)	N2—Co1—O1—C13	117.9 (2)
O3—C18—C19—F7	−67.9 (5)	N1—Co1—O1—C13	111.4 (5)
C20—C18—C19—F7	112.6 (4)	C15—C16—O2—Co1	11.3 (4)
O3—C18—C19—F9	168.8 (3)	C17—C16—O2—Co1	−173.2 (2)
C20—C18—C19—F9	−10.7 (5)	O1—Co1—O2—C16	−20.5 (2)
O3—C18—C19—F8	51.9 (4)	O3—Co1—O2—C16	64.7 (2)
C20—C18—C19—F8	−127.5 (3)	N2—Co1—O2—C16	−113.2 (2)
O3—C18—C20—C21	−5.0 (5)	N1—Co1—O2—C16	169.6 (2)
C19—C18—C20—C21	174.4 (3)	C20—C18—O3—Co1	−16.7 (4)
C18—C20—C21—O4	2.5 (5)	C19—C18—O3—Co1	163.9 (2)
C18—C20—C21—C22	−174.7 (3)	O2—Co1—O3—C18	−150.4 (2)
O4—C21—C22—F11	−118.6 (4)	O4—Co1—O3—C18	27.8 (2)
C20—C21—C22—F11	59.0 (4)	O1—Co1—O3—C18	−62.3 (2)
O4—C21—C22—F12	3.9 (4)	N1—Co1—O3—C18	118.3 (2)
C20—C21—C22—F12	−178.4 (3)	C20—C21—O4—Co1	21.0 (4)
O4—C21—C22—F10	122.6 (3)	C22—C21—O4—Co1	−161.8 (2)
C20—C21—C22—F10	−59.7 (4)	O1—Co1—O4—C21	55.7 (2)
C8—C7—N1—C4	177.8 (2)	O3—Co1—O4—C21	−29.4 (2)
C8—C7—N1—Co1	−3.7 (3)	N2—Co1—O4—C21	148.6 (2)
C3—C4—N1—C7	−18.7 (4)	N1—Co1—O4—C21	−134.3 (2)

Experimental details

Crystal data
Chemical formula	[Co(C₅HF₆O₂)₂(C₁₂H₉BrN₂)]
M_r	734.17
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	8.3568 (2), 10.9420 (2), 14.8151 (3)
α, β, γ (°)	74.042 (1), 86.510 (1), 77.080 (1)
V (Å³)	1269.51 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.37
Crystal size (mm)	0.60 × 0.30 × 0.03

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.330, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	21525, 5176, 4508
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.08
No. of reflections	5176
No. of parameters	379
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −0.91

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

Acknowledgements

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

References

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