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Acta Cryst. (2007). E63, m1980    [ doi:10.1107/S1600536807029649 ]

Dipyridinebis[4,4,4-trifluoro-1-(4-nitrophenyl)butane-1,3-dionato]copper(II)

L. Fan, D.-J. Wang and J. Zheng

Abstract top

In the centrosymmetric title compound, [Cu(C10H5F3NO4)2(C5H5N)2], the CuII atom is hexacoordinate and lies in a square plane formed by four O atoms. Two pyridine molecules complete the coordination in trans positions. In the crystal structure there are intramolecular C-H...F and intermolecular C-H...O hydrogen bonds.

Comment top

1,3-Diketones are invaluable chelating ligand for various lanthanide and transition metals in material chemistry (Shavaleev et al., 2003). In this paper, we report the crystallography structure of the title compound, Cu(C10H5O4F3N)2(C5H5N)2. In the title molecular structure (I), CuII is coordinated by two 4,4,4-trifluoro-1-(4-nitrophenyl)butane-1,3-dione oxygen atoms and two nitrogen atoms of pyridines, forming a distorted octahedron coordination geometry (Fig. 1).

Related literature top

For related literature, see: Shavaleev et al. (2003); Sloopa et al. (2002).

Experimental top

The ligand 4,4,4-trifluoro-1-(4-nitrophenyl)butane-1,3-dione was synthesized from reported literature(Sloopa et al., 2002). The coordination compounds were prepared according to the following procedure: The ligand (0.52 g, 2.0 mmol) and pyridine (0.16 g, 2.0 mmol) in 20 ml hot acetone was added slowly to the CuCl2·2H2O (0.17 g, 1.0 mmol) solution of 10 ml water. The mixture was stirred for 3 h. After filtration, the green solution was allowed to stand at room temperature. Green block-shaped crystals suitable for X-ray analysis were obtained after several days in 55% yield.

Refinement top

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 Uiso(H) = 1.2Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. View of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Dipyridinebis[4,4,4-trifluoro-1-(4-nitrophenyl)butane-1,3-dionato]copper(II) top
Crystal data top
[Cu(C10H5F3NO4)2(C5H5N)2]F000 = 750
Mr = 742.04Dx = 1.643 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P2ybcCell parameters from 2698 reflections
a = 12.5939 (9) Åθ = 2.8–22.9º
b = 8.7423 (6) ŵ = 0.83 mm−1
c = 14.1918 (10) ÅT = 292 (2) K
β = 106.2450 (10)ºBlock, green
V = 1500.13 (18) Å30.20 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker APEX CCD area-detector
diffractometer		3278 independent reflections
Radiation source: fine-focus sealed tube2298 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.080
T = 292(2) Kθmax = 27.0º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001a)		h = −15→16
Tmin = 0.852, Tmax = 0.922k = −11→11
12289 measured reflectionsl = −16→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.108  w = 1/[σ2(Fo2) + (0.0497P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max < 0.001
3278 reflectionsΔρmax = 0.38 e Å−3
223 parametersΔρmin = −0.61 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C10H5F3NO4)2(C5H5N)2]V = 1500.13 (18) Å3
Mr = 742.04Z = 2
Monoclinic, P21/cMo Kα
a = 12.5939 (9) ŵ = 0.83 mm−1
b = 8.7423 (6) ÅT = 292 (2) K
c = 14.1918 (10) Å0.20 × 0.10 × 0.10 mm
β = 106.2450 (10)º
Data collection top
Bruker APEX CCD area-detector
diffractometer		3278 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001a)		2298 reflections with I > 2σ(I)
Tmin = 0.852, Tmax = 0.922Rint = 0.080
12289 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047223 parameters
wR(F2) = 0.108H-atom parameters constrained
S = 0.97Δρmax = 0.38 e Å−3
3278 reflectionsΔρmin = −0.61 e Å−3
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 > 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
Cu10.50001.00000.00000.03413 (15)
C110.5305 (2)0.7430 (3)0.13701 (19)0.0436 (6)
H110.49320.80760.16900.052*
C140.6375 (2)0.5529 (3)0.0444 (2)0.0535 (8)
H140.67380.48930.01100.064*
C120.5706 (3)0.6059 (4)0.1804 (2)0.0565 (8)
H120.56080.57840.24070.068*
C130.6253 (3)0.5107 (3)0.1328 (3)0.0597 (8)
H130.65380.41790.16090.072*
C150.5954 (2)0.6912 (3)0.0050 (2)0.0426 (6)
H150.60350.7195−0.05580.051*
C90.3050 (2)0.9483 (3)−0.16549 (19)0.0391 (6)
C100.2652 (3)0.9380 (3)−0.2776 (2)0.0497 (7)
C70.2538 (2)1.0169 (3)−0.0145 (2)0.0391 (6)
C40.1679 (2)1.0904 (3)0.02552 (18)0.0367 (6)
C50.0934 (2)1.1942 (3)−0.0283 (2)0.0511 (8)
H50.09221.2145−0.09290.061*
C60.0200 (2)1.2689 (4)0.0128 (2)0.0546 (8)
H6−0.03011.3396−0.02360.065*
C10.0226 (2)1.2369 (3)0.10764 (19)0.0428 (7)
C20.0945 (2)1.1325 (3)0.1627 (2)0.0503 (7)
H20.09461.11160.22700.060*
C30.1663 (2)1.0594 (3)0.1210 (2)0.0469 (7)
H30.21510.98740.15760.056*
C80.2297 (2)0.9966 (3)−0.1179 (2)0.0432 (6)
H80.15821.0175−0.15600.052*
F10.31560 (18)1.0415 (2)−0.31809 (13)0.0820 (6)
F20.15767 (15)0.9595 (2)−0.31617 (13)0.0709 (5)
F30.28914 (16)0.8027 (2)−0.30905 (13)0.0776 (6)
N20.54337 (16)0.7864 (2)0.05053 (15)0.0355 (5)
N1−0.0522 (2)1.3223 (3)0.1521 (2)0.0583 (7)
O40.40646 (14)0.9163 (2)−0.13156 (13)0.0436 (5)
O30.34342 (15)0.9824 (2)0.04590 (14)0.0462 (5)
O1−0.0459 (2)1.2980 (3)0.23779 (17)0.0787 (7)
O2−0.1149 (2)1.4130 (4)0.1026 (2)0.1013 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0334 (3)0.0330 (2)0.0349 (3)0.00422 (19)0.0077 (2)0.00201 (19)
C110.0448 (16)0.0424 (15)0.0437 (16)0.0004 (12)0.0124 (14)0.0023 (13)
C140.0515 (19)0.0434 (16)0.060 (2)0.0106 (14)0.0055 (16)−0.0050 (15)
C120.065 (2)0.0530 (19)0.0460 (18)−0.0076 (16)0.0066 (16)0.0139 (15)
C130.062 (2)0.0375 (16)0.066 (2)0.0076 (15)−0.0041 (18)0.0094 (16)
C150.0391 (15)0.0410 (15)0.0460 (17)0.0018 (12)0.0093 (13)−0.0018 (13)
C90.0403 (16)0.0327 (13)0.0424 (17)−0.0009 (11)0.0084 (14)0.0016 (12)
C100.0504 (19)0.0483 (16)0.0490 (19)0.0025 (14)0.0118 (16)−0.0075 (15)
C70.0368 (15)0.0344 (14)0.0438 (16)−0.0056 (11)0.0076 (13)0.0008 (12)
C40.0318 (14)0.0381 (14)0.0363 (15)−0.0022 (11)0.0033 (12)−0.0016 (12)
C50.0516 (18)0.068 (2)0.0329 (16)0.0151 (15)0.0096 (14)0.0078 (14)
C60.0487 (19)0.065 (2)0.0448 (18)0.0191 (15)0.0050 (15)0.0042 (15)
C10.0384 (16)0.0453 (16)0.0439 (17)−0.0041 (12)0.0103 (14)−0.0059 (13)
C20.062 (2)0.0518 (17)0.0394 (16)0.0014 (15)0.0190 (15)0.0049 (14)
C30.0523 (18)0.0455 (15)0.0394 (16)0.0096 (13)0.0071 (14)0.0091 (13)
C80.0361 (15)0.0489 (16)0.0414 (16)0.0013 (12)0.0053 (13)−0.0034 (13)
F10.1064 (17)0.0922 (15)0.0497 (12)−0.0276 (12)0.0255 (12)0.0104 (10)
F20.0570 (12)0.1016 (15)0.0449 (10)0.0159 (10)−0.0007 (9)−0.0109 (10)
F30.0984 (15)0.0669 (12)0.0623 (12)0.0208 (11)0.0139 (11)−0.0242 (10)
N20.0330 (12)0.0333 (11)0.0376 (12)0.0026 (9)0.0057 (10)0.0032 (10)
N10.0515 (17)0.0661 (18)0.0602 (19)0.0030 (14)0.0202 (15)−0.0093 (15)
O40.0390 (11)0.0445 (11)0.0465 (12)0.0073 (8)0.0106 (9)0.0032 (9)
O30.0411 (11)0.0515 (12)0.0426 (11)0.0077 (9)0.0061 (10)0.0037 (9)
O10.0898 (18)0.0966 (19)0.0572 (15)0.0128 (14)0.0331 (14)−0.0094 (13)
O20.091 (2)0.132 (3)0.086 (2)0.064 (2)0.0332 (17)0.0184 (19)
Geometric parameters (Å, °) top
Cu1—N2i2.0197 (19)C10—F21.324 (3)
Cu1—N22.0197 (19)C10—F11.326 (3)
Cu1—O4i2.0443 (18)C10—F31.328 (3)
Cu1—O42.0443 (18)C7—O31.249 (3)
Cu1—O32.2483 (18)C7—C81.424 (4)
Cu1—O3i2.2483 (18)C7—C41.500 (3)
C11—N21.337 (3)C4—C51.373 (4)
C11—C121.377 (4)C4—C31.388 (3)
C11—H110.9300C5—C61.387 (4)
C14—C131.357 (4)C5—H50.9300
C14—C151.375 (4)C6—C11.366 (4)
C14—H140.9300C6—H60.9300
C12—C131.372 (4)C1—C21.366 (4)
C12—H120.9300C1—N11.475 (3)
C13—H130.9300C2—C31.369 (4)
C15—N21.332 (3)C2—H20.9300
C15—H150.9300C3—H30.9300
C9—O41.264 (3)C8—H80.9300
C9—C81.375 (4)N1—O21.198 (3)
C9—C101.531 (4)N1—O11.215 (3)
N2i—Cu1—N2180.0F2—C10—C9114.9 (2)
N2i—Cu1—O4i91.30 (8)F1—C10—C9110.7 (2)
N2—Cu1—O4i88.70 (8)F3—C10—C9111.3 (2)
N2i—Cu1—O488.70 (8)O3—C7—C8124.6 (2)
N2—Cu1—O491.30 (8)O3—C7—C4116.9 (2)
O4i—Cu1—O4180.0C8—C7—C4118.4 (2)
N2i—Cu1—O389.66 (7)C5—C4—C3118.5 (2)
N2—Cu1—O390.34 (7)C5—C4—C7121.7 (2)
O4i—Cu1—O395.04 (7)C3—C4—C7119.7 (2)
O4—Cu1—O384.96 (7)C4—C5—C6120.6 (3)
N2i—Cu1—O3i90.34 (7)C4—C5—H5119.7
N2—Cu1—O3i89.66 (7)C6—C5—H5119.7
O4i—Cu1—O3i84.96 (7)C1—C6—C5118.8 (3)
O4—Cu1—O3i95.04 (7)C1—C6—H6120.6
O3—Cu1—O3i180.0C5—C6—H6120.6
N2—C11—C12122.3 (3)C2—C1—C6122.0 (3)
N2—C11—H11118.9C2—C1—N1119.6 (2)
C12—C11—H11118.9C6—C1—N1118.4 (3)
C13—C14—C15119.0 (3)C1—C2—C3118.5 (3)
C13—C14—H14120.5C1—C2—H2120.8
C15—C14—H14120.5C3—C2—H2120.8
C13—C12—C11118.7 (3)C2—C3—C4121.5 (3)
C13—C12—H12120.6C2—C3—H3119.2
C11—C12—H12120.6C4—C3—H3119.2
C14—C13—C12119.4 (3)C9—C8—C7124.6 (3)
C14—C13—H13120.3C9—C8—H8117.7
C12—C13—H13120.3C7—C8—H8117.7
N2—C15—C14122.6 (3)C15—N2—C11118.0 (2)
N2—C15—H15118.7C15—N2—Cu1121.74 (17)
C14—C15—H15118.7C11—N2—Cu1119.88 (17)
O4—C9—C8130.0 (3)O2—N1—O1123.4 (3)
O4—C9—C10112.7 (2)O2—N1—C1118.7 (3)
C8—C9—C10117.2 (2)O1—N1—C1118.0 (3)
F2—C10—F1106.4 (3)C9—O4—Cu1122.10 (16)
F2—C10—F3106.9 (2)C7—O3—Cu1118.85 (16)
F1—C10—F3106.3 (2)
N2—C11—C12—C13−0.2 (4)C14—C15—N2—C11−1.2 (4)
C15—C14—C13—C120.6 (5)C14—C15—N2—Cu1171.9 (2)
C11—C12—C13—C14−0.6 (5)C12—C11—N2—C151.2 (4)
C13—C14—C15—N20.4 (4)C12—C11—N2—Cu1−172.1 (2)
O4—C9—C10—F2175.3 (2)O4i—Cu1—N2—C15−121.37 (19)
C8—C9—C10—F2−7.8 (4)O4—Cu1—N2—C1558.63 (19)
O4—C9—C10—F1−64.2 (3)O3—Cu1—N2—C15143.59 (19)
C8—C9—C10—F1112.7 (3)O3i—Cu1—N2—C15−36.41 (19)
O4—C9—C10—F353.7 (3)O4i—Cu1—N2—C1151.61 (19)
C8—C9—C10—F3−129.4 (3)O4—Cu1—N2—C11−128.39 (19)
O3—C7—C4—C5148.8 (3)O3—Cu1—N2—C11−43.43 (19)
C8—C7—C4—C5−28.8 (4)O3i—Cu1—N2—C11136.57 (19)
O3—C7—C4—C3−27.9 (3)C2—C1—N1—O2−179.7 (3)
C8—C7—C4—C3154.5 (2)C6—C1—N1—O22.3 (4)
C3—C4—C5—C61.5 (4)C2—C1—N1—O11.1 (4)
C7—C4—C5—C6−175.3 (3)C6—C1—N1—O1−176.8 (3)
C4—C5—C6—C1−0.4 (5)C8—C9—O4—Cu1−22.4 (4)
C5—C6—C1—C2−0.7 (5)C10—C9—O4—Cu1154.05 (17)
C5—C6—C1—N1177.2 (3)N2i—Cu1—O4—C9−56.13 (19)
C6—C1—C2—C30.5 (4)N2—Cu1—O4—C9123.87 (19)
N1—C1—C2—C3−177.3 (3)O3—Cu1—O4—C933.64 (19)
C1—C2—C3—C40.6 (4)O3i—Cu1—O4—C9−146.36 (19)
C5—C4—C3—C2−1.6 (4)C8—C7—O3—Cu131.7 (3)
C7—C4—C3—C2175.2 (3)C4—C7—O3—Cu1−145.79 (17)
O4—C9—C8—C7−1.8 (5)N2i—Cu1—O3—C749.69 (18)
C10—C9—C8—C7−178.1 (2)N2—Cu1—O3—C7−130.31 (18)
O3—C7—C8—C9−5.6 (4)O4i—Cu1—O3—C7140.97 (18)
C4—C7—C8—C9171.8 (2)O4—Cu1—O3—C7−39.03 (18)
Symmetry codes: (i) −x+1, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C8—H8···F20.932.332.723 (3)105
C5—H5···O1ii0.932.543.293 (4)138
Symmetry codes: (ii) x, −y+5/2, z−1/2.
Selected geometric parameters (Å, °) top
Cu1—N2i2.0197 (19)Cu1—O42.0443 (18)
Cu1—N22.0197 (19)Cu1—O32.2483 (18)
Cu1—O4i2.0443 (18)Cu1—O3i2.2483 (18)
N2i—Cu1—N2180.0O4i—Cu1—O395.04 (7)
N2i—Cu1—O4i91.30 (8)O4—Cu1—O384.96 (7)
N2—Cu1—O4i88.70 (8)N2i—Cu1—O3i90.34 (7)
N2i—Cu1—O488.70 (8)N2—Cu1—O3i89.66 (7)
N2—Cu1—O491.30 (8)O4i—Cu1—O3i84.96 (7)
O4i—Cu1—O4180.0O4—Cu1—O3i95.04 (7)
N2i—Cu1—O389.66 (7)O3—Cu1—O3i180.0
N2—Cu1—O390.34 (7)
Symmetry codes: (i) −x+1, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C8—H8···F20.932.332.723 (3)105
C5—H5···O1ii0.932.543.293 (4)138
Symmetry codes: (ii) x, −y+5/2, z−1/2.
Acknowledgements top

The authors are grateful to the Hubei Normal University and the Natural Science Foundation of the Educational Commission of Hubei Province (Nos. J200522002 and Z200622001) for financial support.

references
References top

Bruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS Inc., Madison, Wisconsin, USA.

Shavaleev, N. M., Moorcraft, L. P., Pope, S. J. A., Bell, Z. R., Faulkner, S. & Ward, M. D. (2003). Chem. Eur. J. 9, 5283–5291.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2001a). SADABS (Version 2.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2001b). SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.

Sloopa, J. C., Bumgardnerb, C. L. & Loehle, W. D. (2002). J. Fluorine Chem. 118, 135–147.