Bis(pyridine-κN)bis­[4,4,4-trifluoro-1-(4-fluoro­phen­yl)butane-1,3-dionato-κ² O,O′]cobalt(II)

Abstract

In the structure of the title compound, [Co(C₁₀H₅F₄O₂)₂(C₅H₅N)₂], cobalt(II) forms a complex with two 4,4,4-trifluoro-1-(4-fluoro­phen­yl)butane-1,3-dionate anions and two pyridine mol­ecules in an octa­hedral coordination environment, where the two dionate ligands are in equatorial positions and the two pyridine mol­ecules in axial positions. The complex is located on a crystallographic inversion centre.

Related literature

For related literature, see: Fan et al. (2007 ▶); Feng (2002 ▶); Lu et al. (2003 ▶); Sloopa et al. (2002 ▶).

Experimental

Crystal data

• [Co(C₁₀H₅F₄O₂)₂(C₅H₅N)₂]

• M _r = 683.41

• Monoclinic,

• a = 8.5181 (6) Å

• b = 17.0379 (13) Å

• c = 10.0150 (7) Å

• β = 90.374 (2)°

• V = 1453.45 (18) ų

• Z = 2

• Mo Kα radiation

• μ = 0.68 mm⁻¹

• T = 293 (2) K

• 0.40 × 0.10 × 0.10 mm

Data collection

• Bruker SMART 4K CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.772, T _max = 0.935

• 16450 measured reflections

• 3299 independent reflections

• 2136 reflections with I > 2σ(I)

• R _int = 0.063

Refinement

• R[F ² > 2σ(F ²)] = 0.059

• wR(F ²) = 0.138

• S = 1.09

• 3299 reflections

• 205 parameters

• H-atom parameters constrained

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2001 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected geometric parameters (Å, °).

Co1—O1	2.055 (2)
Co1—O2	2.033 (2)
Co1—N1	2.195 (3)

O1—Co1—O2	88.35 (8)
O1—Co1—N1	93.58 (9)
O2—Co1—N1	90.24 (9)

supplementary crystallographic information

Comment

The chelating group 1,3-diketone, widely used in coordination chemistry for a long time (Fan et al., 2007; Lu et al., 2003; Feng, 2002), has been increasingly encountered as a constituent of polydentate ligands in the context of metallo-supramolecular chemistry. In this paper, we report the crystal structure of the title compound, Co(C₁₀H₅O₂F₄)₂(C₅H₅N)₂. The Co(II) ion is located on a crystallographic inversion centre and is coordinated by two 4,4,4-trifluoro-1-(4-fluorophenyl)butane-1,3-dione oxygen atoms and two nitrogen atoms of pyridines, forming a distorted octahedron coordination geometry (Fig. 1). The chelate fragment is planar and the both lengths imply strong conjugation in chelate rings (Table 1).

Experimental

The ligand 4,4,4-trifluoro-1-(4-fluorophenyl)butane-1,3-dione was synthesized according to the reported literature (Sloopa et al., 2002). The coordination compound was prepared according to the following procedure: a mixture of ligand (0.328 g, 1.4 mmol) and pyridine (0.111 g, 1.4 mmol), dissolved in hot acetone (20 ml) was added slowly to a solution of Co(CH₃COO)₂ ˙4H₂O (0.174 g, 0.7 mmol) in water (10 ml). The mixture was stirred for 3 h. After filtration, the red solution was allowed to stand at room temperature. Brown block-shaped crystals suitable for X-ray analysis were obtained in several days. C, H and N content analyses were performed on a Perkin Elmer 2400 analytical instrument. Anal. Calcd. (%) for C₃₀H₂₀CoF₈N₂O₄: C, 52.72; H, 2.95; N, 4.10. Found (%): C, 53.01; H, 2.72; N, 4.20.

Refinement

All the H atoms were placed at their idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

View of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H-atoms are represented by circles of arbitrary size. Symmetry codes: a: (2 - x, 2 - y, 2 - z).

Crystal data

[Co(C10H5F4O2)2(C5H5N)2]	F000 = 690
Mr = 683.41	Dx = 1.562 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 1950 reflections
a = 8.5181 (6) Å	θ = 2.4–20.8º
b = 17.0379 (13) Å	µ = 0.68 mm−1
c = 10.0150 (7) Å	T = 293 (2) K
β = 90.374 (2)º	Block, brown
V = 1453.45 (18) Å3	0.40 × 0.10 × 0.10 mm
Z = 2

Data collection

Bruker SMART 4K CCD area-detector diffractometer	3299 independent reflections
Radiation source: fine-focus sealed tube	2136 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.063
T = 293(2) K	θmax = 27.5º
φ and ω scans	θmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 2001)	h = −11→11
Tmin = 0.772, Tmax = 0.935	k = −22→21
16450 measured reflections	l = −12→13

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059	H-atom parameters constrained
wR(F2) = 0.138	w = 1/[σ2(Fo2) + (0.059P)2 + 0.1443P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
3299 reflections	Δρmax = 0.44 e Å−3
205 parameters	Δρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	1.0000	1.0000	1.0000	0.0428 (2)
C1	1.1943 (3)	0.9984 (2)	0.6036 (3)	0.0479 (8)
C2	1.2093 (4)	0.9561 (3)	0.4859 (3)	0.0659 (10)
H2	1.1591	0.9079	0.4765	0.079*
C3	1.2988 (5)	0.9855 (3)	0.3824 (4)	0.0766 (12)
H3	1.3085	0.9574	0.3033	0.092*
C4	1.3713 (4)	1.0548 (3)	0.3971 (4)	0.0754 (12)
C5	1.3597 (4)	1.0991 (2)	0.5103 (4)	0.0732 (11)
H5	1.4099	1.1474	0.5178	0.088*
C6	1.2700 (4)	1.0691 (2)	0.6137 (3)	0.0599 (9)
H6	1.2611	1.0978	0.6922	0.072*
C7	1.0984 (3)	0.97134 (18)	0.7195 (3)	0.0432 (7)
C8	1.0258 (4)	0.89683 (18)	0.7204 (3)	0.0495 (8)
H8	1.0478	0.8627	0.6506	0.059*
C9	0.9242 (3)	0.87138 (17)	0.8183 (3)	0.0442 (7)
C10	0.8602 (4)	0.7887 (2)	0.8059 (3)	0.0568 (9)
C11	0.8337 (4)	1.1450 (2)	0.8834 (4)	0.0673 (10)
H11	0.9344	1.1531	0.8509	0.081*
C12	0.7186 (5)	1.1979 (2)	0.8505 (5)	0.0860 (13)
H12	0.7422	1.2414	0.7983	0.103*
C13	0.5687 (5)	1.1862 (3)	0.8949 (5)	0.0824 (12)
H13	0.4883	1.2206	0.8716	0.099*
C14	0.5405 (4)	1.1228 (3)	0.9741 (4)	0.0757 (11)
H14	0.4404	1.1136	1.0073	0.091*
C15	0.6617 (4)	1.0729 (2)	1.0041 (3)	0.0601 (9)
H15	0.6411	1.0299	1.0584	0.072*
F1	1.4601 (3)	1.08363 (17)	0.2953 (2)	0.1107 (9)
F3	0.8525 (3)	0.76125 (12)	0.6819 (2)	0.0869 (7)
F4	0.7189 (3)	0.78070 (13)	0.8566 (3)	0.1041 (9)
F5	0.9517 (3)	0.73792 (12)	0.8714 (2)	0.0910 (7)
N1	0.8080 (3)	1.08270 (15)	0.9594 (2)	0.0481 (6)
O1	0.8796 (2)	0.90574 (12)	0.9225 (2)	0.0506 (5)
O2	1.0882 (2)	1.01973 (12)	0.8149 (2)	0.0505 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0456 (3)	0.0427 (4)	0.0403 (3)	−0.0036 (3)	0.0131 (2)	−0.0079 (3)
C1	0.0444 (17)	0.062 (2)	0.0373 (17)	0.0143 (16)	0.0035 (13)	0.0043 (15)
C2	0.057 (2)	0.097 (3)	0.043 (2)	0.004 (2)	0.0051 (17)	−0.0090 (19)
C3	0.065 (2)	0.127 (4)	0.037 (2)	0.014 (2)	0.0073 (17)	−0.003 (2)
C4	0.059 (2)	0.115 (4)	0.053 (2)	0.023 (2)	0.0165 (19)	0.035 (2)
C5	0.077 (3)	0.073 (3)	0.070 (3)	0.011 (2)	0.026 (2)	0.022 (2)
C6	0.069 (2)	0.060 (2)	0.051 (2)	0.0100 (18)	0.0191 (17)	0.0066 (17)
C7	0.0398 (16)	0.0505 (18)	0.0393 (18)	0.0114 (14)	0.0037 (13)	−0.0001 (14)
C8	0.0566 (19)	0.0513 (19)	0.0408 (18)	0.0110 (15)	0.0085 (15)	−0.0100 (14)
C9	0.0413 (17)	0.0419 (17)	0.0494 (19)	0.0061 (14)	0.0017 (14)	−0.0087 (14)
C10	0.060 (2)	0.049 (2)	0.061 (2)	−0.0014 (17)	0.0095 (17)	−0.0132 (17)
C11	0.059 (2)	0.056 (2)	0.088 (3)	−0.0057 (18)	0.0111 (19)	0.011 (2)
C12	0.086 (3)	0.055 (2)	0.117 (4)	0.007 (2)	−0.001 (3)	0.019 (2)
C13	0.072 (3)	0.071 (3)	0.105 (3)	0.023 (2)	−0.005 (2)	−0.013 (3)
C14	0.051 (2)	0.091 (3)	0.084 (3)	0.016 (2)	0.0119 (19)	−0.013 (2)
C15	0.056 (2)	0.067 (2)	0.057 (2)	0.0000 (18)	0.0144 (17)	−0.0027 (18)
F1	0.0994 (17)	0.166 (3)	0.0678 (15)	0.0212 (17)	0.0392 (13)	0.0496 (15)
F3	0.1210 (19)	0.0674 (14)	0.0721 (15)	−0.0174 (13)	−0.0008 (13)	−0.0267 (11)
F4	0.0790 (16)	0.0701 (15)	0.164 (2)	−0.0272 (12)	0.0479 (16)	−0.0429 (15)
F5	0.1182 (19)	0.0515 (13)	0.1031 (19)	0.0003 (12)	−0.0169 (15)	0.0079 (12)
N1	0.0459 (15)	0.0505 (16)	0.0479 (15)	−0.0032 (12)	0.0095 (12)	−0.0060 (12)
O1	0.0502 (12)	0.0512 (13)	0.0506 (13)	−0.0053 (10)	0.0154 (10)	−0.0114 (10)
O2	0.0610 (13)	0.0467 (13)	0.0440 (13)	−0.0027 (10)	0.0178 (10)	−0.0046 (9)

Geometric parameters (Å, °)

Co1—O1	2.055 (2)	C7—C8	1.412 (4)
Co1—O1i	2.055 (2)	C8—H8	0.9300
Co1—O2	2.033 (2)	C8—C9	1.382 (4)
Co1—O2i	2.033 (2)	C9—O1	1.257 (3)
Co1—N1i	2.195 (3)	C9—C10	1.516 (4)
Co1—N1	2.195 (3)	C10—F3	1.328 (4)
C1—C2	1.388 (4)	C10—F4	1.316 (4)
C1—C6	1.370 (4)	C10—F5	1.334 (4)
C1—C7	1.496 (4)	C11—N1	1.325 (4)
C2—H2	0.9300	C11—H11	0.9300
C2—C3	1.385 (5)	C11—C12	1.370 (5)
C3—H3	0.9300	C12—H12	0.9300
C3—C4	1.339 (6)	C12—C13	1.370 (5)
C4—F1	1.365 (4)	C13—H13	0.9300
C4—C5	1.366 (5)	C13—C14	1.362 (6)
C5—H5	0.9300	C14—H14	0.9300
C5—C6	1.389 (5)	C14—C15	1.370 (5)
C6—H6	0.9300	C15—N1	1.338 (4)
C7—O2	1.266 (3)	C15—H15	0.9300
O1—Co1—N1i	86.43 (9)	C9—C8—C7	124.3 (3)
O1i—Co1—N1i	93.58 (9)	C9—C8—H8	117.9
O1—Co1—O1i	180	C9—O1—Co1	121.66 (19)
O1—Co1—O2	88.35 (8)	C11—C12—H12	120.2
O1—Co1—N1	93.58 (9)	C11—N1—C15	116.7 (3)
O2i—Co1—O1	91.65 (8)	C11—N1—Co1	119.7 (2)
O2i—Co1—O1i	88.35 (8)	C12—C11—H11	118.5
O2—Co1—N1	90.24 (9)	C12—C13—H13	120.9
O2—Co1—N1i	89.76 (9)	C13—C12—C11	119.6 (4)
O2i—Co1—N1i	90.24 (9)	C13—C12—H12	120.2
O2—Co1—O2i	180	C13—C14—H14	120.5
N1i—Co1—N1	180	C13—C14—C15	119.0 (4)
C1—C2—H2	119.9	C14—C13—C12	118.2 (4)
C1—C6—C5	122.0 (3)	C14—C13—H13	120.9
C1—C6—H6	119.0	C14—C15—H15	118.3
C2—C1—C7	123.6 (3)	C15—C14—H14	120.5
C2—C3—H3	120.2	C15—N1—Co1	123.6 (2)
C3—C2—C1	120.1 (4)	O1—C9—C8	129.5 (3)
C3—C2—H2	119.9	O1—C9—C10	113.0 (3)
C3—C4—F1	119.5 (4)	O2—C7—C1	115.2 (3)
C3—C4—C5	122.9 (4)	O2—C7—C8	123.2 (3)
C4—C3—C2	119.5 (4)	F1—C4—C5	117.6 (4)
C4—C3—H3	120.3	F3—C10—C9	114.8 (3)
C4—C5—H5	121.4	F3—C10—F5	104.9 (3)
C4—C5—C6	117.2 (4)	F4—C10—F3	106.5 (3)
C5—C6—H6	119.0	F4—C10—F5	106.1 (3)
C6—C1—C2	118.2 (3)	F4—C10—C9	113.2 (3)
C6—C1—C7	118.2 (3)	F5—C10—C9	110.7 (3)
C6—C5—H5	121.4	N1—C11—H11	118.5
C7—C8—H8	117.9	N1—C11—C12	123.0 (4)
C7—O2—Co1	127.5 (2)	N1—C15—C14	123.5 (4)
C8—C7—C1	121.5 (3)	N1—C15—H15	118.3
C8—C9—C10	117.4 (3)
C6—C1—C2—C3	−0.1 (5)	C12—C13—C14—C15	−1.1 (6)
C7—C1—C2—C3	179.3 (3)	C13—C14—C15—N1	−0.1 (6)
C1—C2—C3—C4	0.4 (5)	C12—C11—N1—C15	0.1 (5)
C2—C3—C4—F1	179.7 (3)	C12—C11—N1—Co1	178.0 (3)
C2—C3—C4—C5	−0.9 (6)	C14—C15—N1—C11	0.7 (5)
C3—C4—C5—C6	1.0 (6)	C14—C15—N1—Co1	−177.2 (3)
F1—C4—C5—C6	−179.6 (3)	O2—Co1—N1—C11	−33.8 (3)
C2—C1—C6—C5	0.2 (5)	O2i—Co1—N1—C11	146.2 (3)
C7—C1—C6—C5	−179.1 (3)	O1—Co1—N1—C11	−122.2 (3)
C4—C5—C6—C1	−0.6 (5)	O1i—Co1—N1—C11	57.8 (3)
C6—C1—C7—O2	4.3 (4)	O2—Co1—N1—C15	144.0 (3)
C2—C1—C7—O2	−175.0 (3)	O2i—Co1—N1—C15	−36.0 (3)
C6—C1—C7—C8	−175.6 (3)	O1—Co1—N1—C15	55.6 (3)
C2—C1—C7—C8	5.1 (5)	O1i—Co1—N1—C15	−124.4 (3)
O2—C7—C8—C9	6.5 (5)	C8—C9—O1—Co1	−17.9 (4)
C1—C7—C8—C9	−173.6 (3)	C10—C9—O1—Co1	158.9 (2)
C7—C8—C9—O1	−1.7 (5)	O2—Co1—O1—C9	23.5 (2)
C7—C8—C9—C10	−178.3 (3)	O2i—Co1—O1—C9	−156.5 (2)
O1—C9—C10—F4	33.3 (4)	N1i—Co1—O1—C9	−66.3 (2)
C8—C9—C10—F4	−149.5 (3)	N1—Co1—O1—C9	113.7 (2)
O1—C9—C10—F3	155.9 (3)	C8—C7—O2—Co1	10.3 (4)
C8—C9—C10—F3	−26.9 (4)	C1—C7—O2—Co1	−169.56 (18)
O1—C9—C10—F5	−85.6 (3)	O1—Co1—O2—C7	−21.1 (2)
C8—C9—C10—F5	91.5 (3)	O1i—Co1—O2—C7	158.9 (2)
N1—C11—C12—C13	−1.3 (7)	N1i—Co1—O2—C7	65.4 (2)
C11—C12—C13—C14	1.8 (7)	N1—Co1—O2—C7	−114.6 (2)

Symmetry codes: (i) −x+2, −y+2, −z+2.