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

In the centrosymmetric title compound, [Cu(C₁₀H₅F₃NO₄)₂(C₅H₅N)₂], the Cu^II 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.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.108
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   O3      ..      10.23 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   O4      ..      10.12 su

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.14

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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), Cu^II 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

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

S2. Experimental

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.

S3. 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).

Computing details

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

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)

Crystal data

[Cu(C10H5F3NO4)2(C5H5N)2]	F(000) = 750
Mr = 742.04	Dx = 1.643 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 2698 reflections
a = 12.5939 (9) Å	θ = 2.8–22.9°
b = 8.7423 (6) Å	µ = 0.83 mm^−1
c = 14.1918 (10) Å	T = 292 K
β = 106.245 (1)°	Block, green
V = 1500.13 (18) Å^3	0.20 × 0.10 × 0.10 mm
Z = 2

Data collection

Bruker APEX CCD area-detector diffractometer	3278 independent reflections
Radiation source: fine-focus sealed tube	2298 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
φ and ω scans	θmax = 27.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001a)	h = −15→16
Tmin = 0.852, Tmax = 0.922	k = −11→11
12289 measured reflections	l = −16→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0497P)^2] where P = (Fo^2 + 2Fc^2)/3
3278 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

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
Cu1	0.5000	1.0000	0.0000	0.03413 (15)
C11	0.5305 (2)	0.7430 (3)	0.13701 (19)	0.0436 (6)
H11	0.4932	0.8076	0.1690	0.052*
C14	0.6375 (2)	0.5529 (3)	0.0444 (2)	0.0535 (8)
H14	0.6738	0.4893	0.0110	0.064*
C12	0.5706 (3)	0.6059 (4)	0.1804 (2)	0.0565 (8)
H12	0.5608	0.5784	0.2407	0.068*
C13	0.6253 (3)	0.5107 (3)	0.1328 (3)	0.0597 (8)
H13	0.6538	0.4179	0.1609	0.072*
C15	0.5954 (2)	0.6912 (3)	0.0050 (2)	0.0426 (6)
H15	0.6035	0.7195	−0.0558	0.051*
C9	0.3050 (2)	0.9483 (3)	−0.16549 (19)	0.0391 (6)
C10	0.2652 (3)	0.9380 (3)	−0.2776 (2)	0.0497 (7)
C7	0.2538 (2)	1.0169 (3)	−0.0145 (2)	0.0391 (6)
C4	0.1679 (2)	1.0904 (3)	0.02552 (18)	0.0367 (6)
C5	0.0934 (2)	1.1942 (3)	−0.0283 (2)	0.0511 (8)
H5	0.0922	1.2145	−0.0929	0.061*
C6	0.0200 (2)	1.2689 (4)	0.0128 (2)	0.0546 (8)
H6	−0.0301	1.3396	−0.0236	0.065*
C1	0.0226 (2)	1.2369 (3)	0.10764 (19)	0.0428 (7)
C2	0.0945 (2)	1.1325 (3)	0.1627 (2)	0.0503 (7)
H2	0.0946	1.1116	0.2270	0.060*
C3	0.1663 (2)	1.0594 (3)	0.1210 (2)	0.0469 (7)
H3	0.2151	0.9874	0.1576	0.056*
C8	0.2297 (2)	0.9966 (3)	−0.1179 (2)	0.0432 (6)
H8	0.1582	1.0175	−0.1560	0.052*
F1	0.31560 (18)	1.0415 (2)	−0.31809 (13)	0.0820 (6)
F2	0.15767 (15)	0.9595 (2)	−0.31617 (13)	0.0709 (5)
F3	0.28914 (16)	0.8027 (2)	−0.30905 (13)	0.0776 (6)
N2	0.54337 (16)	0.7864 (2)	0.05053 (15)	0.0355 (5)
N1	−0.0522 (2)	1.3223 (3)	0.1521 (2)	0.0583 (7)
O4	0.40646 (14)	0.9163 (2)	−0.13156 (13)	0.0436 (5)
O3	0.34342 (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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0334 (3)	0.0330 (2)	0.0349 (3)	0.00422 (19)	0.0077 (2)	0.00201 (19)
C11	0.0448 (16)	0.0424 (15)	0.0437 (16)	0.0004 (12)	0.0124 (14)	0.0023 (13)
C14	0.0515 (19)	0.0434 (16)	0.060 (2)	0.0106 (14)	0.0055 (16)	−0.0050 (15)
C12	0.065 (2)	0.0530 (19)	0.0460 (18)	−0.0076 (16)	0.0066 (16)	0.0139 (15)
C13	0.062 (2)	0.0375 (16)	0.066 (2)	0.0076 (15)	−0.0041 (18)	0.0094 (16)
C15	0.0391 (15)	0.0410 (15)	0.0460 (17)	0.0018 (12)	0.0093 (13)	−0.0018 (13)
C9	0.0403 (16)	0.0327 (13)	0.0424 (17)	−0.0009 (11)	0.0084 (14)	0.0016 (12)
C10	0.0504 (19)	0.0483 (16)	0.0490 (19)	0.0025 (14)	0.0118 (16)	−0.0075 (15)
C7	0.0368 (15)	0.0344 (14)	0.0438 (16)	−0.0056 (11)	0.0076 (13)	0.0008 (12)
C4	0.0318 (14)	0.0381 (14)	0.0363 (15)	−0.0022 (11)	0.0033 (12)	−0.0016 (12)
C5	0.0516 (18)	0.068 (2)	0.0329 (16)	0.0151 (15)	0.0096 (14)	0.0078 (14)
C6	0.0487 (19)	0.065 (2)	0.0448 (18)	0.0191 (15)	0.0050 (15)	0.0042 (15)
C1	0.0384 (16)	0.0453 (16)	0.0439 (17)	−0.0041 (12)	0.0103 (14)	−0.0059 (13)
C2	0.062 (2)	0.0518 (17)	0.0394 (16)	0.0014 (15)	0.0190 (15)	0.0049 (14)
C3	0.0523 (18)	0.0455 (15)	0.0394 (16)	0.0096 (13)	0.0071 (14)	0.0091 (13)
C8	0.0361 (15)	0.0489 (16)	0.0414 (16)	0.0013 (12)	0.0053 (13)	−0.0034 (13)
F1	0.1064 (17)	0.0922 (15)	0.0497 (12)	−0.0276 (12)	0.0255 (12)	0.0104 (10)
F2	0.0570 (12)	0.1016 (15)	0.0449 (10)	0.0159 (10)	−0.0007 (9)	−0.0109 (10)
F3	0.0984 (15)	0.0669 (12)	0.0623 (12)	0.0208 (11)	0.0139 (11)	−0.0242 (10)
N2	0.0330 (12)	0.0333 (11)	0.0376 (12)	0.0026 (9)	0.0057 (10)	0.0032 (10)
N1	0.0515 (17)	0.0661 (18)	0.0602 (19)	0.0030 (14)	0.0202 (15)	−0.0093 (15)
O4	0.0390 (11)	0.0445 (11)	0.0465 (12)	0.0073 (8)	0.0106 (9)	0.0032 (9)
O3	0.0411 (11)	0.0515 (12)	0.0426 (11)	0.0077 (9)	0.0061 (10)	0.0037 (9)
O1	0.0898 (18)	0.0966 (19)	0.0572 (15)	0.0128 (14)	0.0331 (14)	−0.0094 (13)
O2	0.091 (2)	0.132 (3)	0.086 (2)	0.064 (2)	0.0332 (17)	0.0184 (19)

Geometric parameters (Å, º)

Cu1—N2^i	2.0197 (19)	C10—F2	1.324 (3)
Cu1—N2	2.0197 (19)	C10—F1	1.326 (3)
Cu1—O4^i	2.0443 (18)	C10—F3	1.328 (3)
Cu1—O4	2.0443 (18)	C7—O3	1.249 (3)
Cu1—O3	2.2483 (18)	C7—C8	1.424 (4)
Cu1—O3^i	2.2483 (18)	C7—C4	1.500 (3)
C11—N2	1.337 (3)	C4—C5	1.373 (4)
C11—C12	1.377 (4)	C4—C3	1.388 (3)
C11—H11	0.9300	C5—C6	1.387 (4)
C14—C13	1.357 (4)	C5—H5	0.9300
C14—C15	1.375 (4)	C6—C1	1.366 (4)
C14—H14	0.9300	C6—H6	0.9300
C12—C13	1.372 (4)	C1—C2	1.366 (4)
C12—H12	0.9300	C1—N1	1.475 (3)
C13—H13	0.9300	C2—C3	1.369 (4)
C15—N2	1.332 (3)	C2—H2	0.9300
C15—H15	0.9300	C3—H3	0.9300
C9—O4	1.264 (3)	C8—H8	0.9300
C9—C8	1.375 (4)	N1—O2	1.198 (3)
C9—C10	1.531 (4)	N1—O1	1.215 (3)
N2^i—Cu1—N2	180.0	F2—C10—C9	114.9 (2)
N2^i—Cu1—O4^i	91.30 (8)	F1—C10—C9	110.7 (2)
N2—Cu1—O4^i	88.70 (8)	F3—C10—C9	111.3 (2)
N2^i—Cu1—O4	88.70 (8)	O3—C7—C8	124.6 (2)
N2—Cu1—O4	91.30 (8)	O3—C7—C4	116.9 (2)
O4^i—Cu1—O4	180.0	C8—C7—C4	118.4 (2)
N2^i—Cu1—O3	89.66 (7)	C5—C4—C3	118.5 (2)
N2—Cu1—O3	90.34 (7)	C5—C4—C7	121.7 (2)
O4^i—Cu1—O3	95.04 (7)	C3—C4—C7	119.7 (2)
O4—Cu1—O3	84.96 (7)	C4—C5—C6	120.6 (3)
N2^i—Cu1—O3^i	90.34 (7)	C4—C5—H5	119.7
N2—Cu1—O3^i	89.66 (7)	C6—C5—H5	119.7
O4^i—Cu1—O3^i	84.96 (7)	C1—C6—C5	118.8 (3)
O4—Cu1—O3^i	95.04 (7)	C1—C6—H6	120.6
O3—Cu1—O3^i	180.0	C5—C6—H6	120.6
N2—C11—C12	122.3 (3)	C2—C1—C6	122.0 (3)
N2—C11—H11	118.9	C2—C1—N1	119.6 (2)
C12—C11—H11	118.9	C6—C1—N1	118.4 (3)
C13—C14—C15	119.0 (3)	C1—C2—C3	118.5 (3)
C13—C14—H14	120.5	C1—C2—H2	120.8
C15—C14—H14	120.5	C3—C2—H2	120.8
C13—C12—C11	118.7 (3)	C2—C3—C4	121.5 (3)
C13—C12—H12	120.6	C2—C3—H3	119.2
C11—C12—H12	120.6	C4—C3—H3	119.2
C14—C13—C12	119.4 (3)	C9—C8—C7	124.6 (3)
C14—C13—H13	120.3	C9—C8—H8	117.7
C12—C13—H13	120.3	C7—C8—H8	117.7
N2—C15—C14	122.6 (3)	C15—N2—C11	118.0 (2)
N2—C15—H15	118.7	C15—N2—Cu1	121.74 (17)
C14—C15—H15	118.7	C11—N2—Cu1	119.88 (17)
O4—C9—C8	130.0 (3)	O2—N1—O1	123.4 (3)
O4—C9—C10	112.7 (2)	O2—N1—C1	118.7 (3)
C8—C9—C10	117.2 (2)	O1—N1—C1	118.0 (3)
F2—C10—F1	106.4 (3)	C9—O4—Cu1	122.10 (16)
F2—C10—F3	106.9 (2)	C7—O3—Cu1	118.85 (16)
F1—C10—F3	106.3 (2)
N2—C11—C12—C13	−0.2 (4)	C14—C15—N2—C11	−1.2 (4)
C15—C14—C13—C12	0.6 (5)	C14—C15—N2—Cu1	171.9 (2)
C11—C12—C13—C14	−0.6 (5)	C12—C11—N2—C15	1.2 (4)
C13—C14—C15—N2	0.4 (4)	C12—C11—N2—Cu1	−172.1 (2)
O4—C9—C10—F2	175.3 (2)	O4^i—Cu1—N2—C15	−121.37 (19)
C8—C9—C10—F2	−7.8 (4)	O4—Cu1—N2—C15	58.63 (19)
O4—C9—C10—F1	−64.2 (3)	O3—Cu1—N2—C15	143.59 (19)
C8—C9—C10—F1	112.7 (3)	O3^i—Cu1—N2—C15	−36.41 (19)
O4—C9—C10—F3	53.7 (3)	O4^i—Cu1—N2—C11	51.61 (19)
C8—C9—C10—F3	−129.4 (3)	O4—Cu1—N2—C11	−128.39 (19)
O3—C7—C4—C5	148.8 (3)	O3—Cu1—N2—C11	−43.43 (19)
C8—C7—C4—C5	−28.8 (4)	O3^i—Cu1—N2—C11	136.57 (19)
O3—C7—C4—C3	−27.9 (3)	C2—C1—N1—O2	−179.7 (3)
C8—C7—C4—C3	154.5 (2)	C6—C1—N1—O2	2.3 (4)
C3—C4—C5—C6	1.5 (4)	C2—C1—N1—O1	1.1 (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—Cu1	154.05 (17)
C5—C6—C1—N1	177.2 (3)	N2^i—Cu1—O4—C9	−56.13 (19)
C6—C1—C2—C3	0.5 (4)	N2—Cu1—O4—C9	123.87 (19)
N1—C1—C2—C3	−177.3 (3)	O3—Cu1—O4—C9	33.64 (19)
C1—C2—C3—C4	0.6 (4)	O3^i—Cu1—O4—C9	−146.36 (19)
C5—C4—C3—C2	−1.6 (4)	C8—C7—O3—Cu1	31.7 (3)
C7—C4—C3—C2	175.2 (3)	C4—C7—O3—Cu1	−145.79 (17)
O4—C9—C8—C7	−1.8 (5)	N2^i—Cu1—O3—C7	49.69 (18)
C10—C9—C8—C7	−178.1 (2)	N2—Cu1—O3—C7	−130.31 (18)
O3—C7—C8—C9	−5.6 (4)	O4^i—Cu1—O3—C7	140.97 (18)
C4—C7—C8—C9	171.8 (2)	O4—Cu1—O3—C7	−39.03 (18)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···F2	0.93	2.33	2.723 (3)	105
C5—H5···O1^ii	0.93	2.54	3.293 (4)	138

Symmetry code: (ii) x, −y+5/2, z−1/2.