(Acetato-κ2O,O′)bis­(1,10-phenanthroline-κ2N,N′)copper(II) trifluoro­acetate tetra­hydrate

Wang, J.; Jin, Z.

doi:10.1107/S1600536810024359

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m865

doi:10.1107/S1600536810024359

Open

access

(Acetato-κ²O,O′)bis(1,10-phenanthroline-κ²N,N′)copper(II) trifluoroacetate tetrahydrate

Jinxia Wang ^a ^* and Zhuping Jin ^b

^aSchool of Science, North University of China, Taiyuan 030051, People's Republic of China, and ^bSchool of Chemical Engineering and Environment, North University of China, Taiyuan 030051, People's Republic of China
^*Correspondence e-mail: kxin_2010@163.com

(Received 17 May 2010; accepted 23 June 2010; online 30 June 2010)

In the title compound, [Cu(CH₃CO₂)(C₁₂H₈N₂)₂](CF₃CO₂)·4H₂O, the Cu^II atom shows a distorted octahedral coordination with four N atoms [Cu—N = 2.015 (3)–2.244 (3) Å] from the two phenanthroline ligands and two O atoms from the acetate [Cu—O = 1.953 (3) and 2.764 (3) Å]. Strong intermolecular O—H⋯O hydrogen-bonding interactions consolidate the crystal packing. The F atoms of the anion are disordered over two positions in a 0.5233 (3):0.4767 (3) ratio.

Related literature

For metal–1,10-phenanthroline complexes with carboxylates, see: Sun et al. (2007 ); Liu et al. (2009 ).

Experimental

Crystal data

[Cu(C₂H₃O₂)(C₁₂H₈N₂)₂](C₂F₃O₂)·4H₂O
M_r = 668.08
Triclinic, $[P \overline 1]$
a = 8.9019 (7) Å
b = 11.6662 (9) Å
c = 15.698 (1) Å
α = 101.619 (1)°
β = 101.512 (1)°
γ = 108.514 (1)°
V = 1451.98 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 K
0.28 × 0.25 × 0.19 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.801, T_max = 0.859
7689 measured reflections
5112 independent reflections
4389 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.159
S = 1.02
5112 reflections
425 parameters
103 restraints
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.953 (3)
Cu1—N1	2.015 (3)
Cu1—N4	2.022 (3)
Cu1—N2	2.037 (3)
Cu1—N3	2.244 (3)

O1—Cu1—N1	91.55 (13)
O1—Cu1—N4	93.66 (13)
N1—Cu1—N4	169.21 (13)
O1—Cu1—N2	171.51 (12)
N1—Cu1—N2	81.21 (14)
N4—Cu1—N2	92.78 (14)
O1—Cu1—N3	93.94 (12)
N1—Cu1—N3	110.64 (13)
N4—Cu1—N3	78.44 (13)
N2—Cu1—N3	92.75 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O5	0.85	1.95	2.787 (8)	168
O7—H7B⋯O4	0.85	2.11	2.854 (8)	145
O6—H6A⋯O1	0.85	2.00	2.844 (5)	170
O6—H6B⋯O4ⁱ	0.85	2.03	2.881 (7)	175
O8—H8B⋯O3ⁱⁱ	0.85	2.03	2.868 (10)	171
O8—H8A⋯O6ⁱⁱⁱ	0.85	2.17	2.809 (9)	132
Symmetry codes: (i) x, y-1, z; (ii) x+1, y, z; (iii) x, y+1, z.

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024359/ez2212sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024359/ez2212Isup2.hkl

checkCIF report

Comment top

Metal complexes with carboxylates are among the most investigated complexes in the field of coordination chemistry, in which metal-1,10-phenanthroline complexes and their derivatives have also attracted much attention during recent decades because of their interesting features (Sun et al., 2007; Liu et al., 2009). In this work, the title compound was obtained by the reaction of trifluoroacetic acid and cupric acetate in the presence of 1,10-phenanthroline as co-ligand.

The molecular structure of the title complex is shown in Fig. 1. The Cu^II atom exhibits a six-coordinate distorted octahedral geometry with four N atoms [Cu—N 2.015 (3) Å–2.244 (3) Å] from two phenanthroline ligands and two O atoms from the acetate ligand [Cu—O 1.953 (3), 2.764 (3) Å]. Three N atoms and one O atom occupy the equatorial positions with a slight departure from the ideal plane by 0.0563 (2) Å, while one O atom and one N atom lie in the apical positions with an axis angle of 140.63 (10)°, showing a large deviation from the expected 180°. Strong intermolecular O—H···O hydrogen bonding interactions exist.

Related literature top

For metal–1,10-phenanthroline complexes with carboxylates, see: Sun et al. (2007); Liu et al. (2009).

Experimental top

The reaction was carried out by the solvothermal method. Trifluoroacetic acid (0.114 g,1 mmol) and cupric acetate (0.199 g, 1 mmol) and 1,10-phenanthroline (0.312 g, 2 mmol) were added to an airtight vessel with the 21 ml of a 2:1 ethanol-water mixture. The resulting blue solution was filtered. Upon standing, the filtrate yielded blue block-shaped crystals after several days.

The yield is 76% and elemental analysis: calc. for C₂₈H₂₇CuF₃N₄O₈: C 50.34, H 4.07, N 8.39; found: C 50.52, H 4.29, N 8.53. The elemental analyses were performed with PERKIN ELMER MODEL 2400 SERIES II.

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.

(Acetato-κ²O,O')bis(1,10-phenanthroline- κ²N,N')copper(II) trifluoroacetate tetrahydrate top

Crystal data top

[Cu(C₂H₃O₂)(C₁₂H₈N₂)₂](C₂F₃O₂)·4H₂O	Z = 2
M_r = 668.08	F(000) = 686
Triclinic, P1	D_x = 1.528 Mg m⁻³
a = 8.9019 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6662 (9) Å	Cell parameters from 4430 reflections
c = 15.698 (1) Å	θ = 2.5–27.8°
α = 101.619 (1)°	µ = 0.83 mm⁻¹
β = 101.512 (1)°	T = 293 K
γ = 108.514 (1)°	Block, blue
V = 1451.98 (19) Å³	0.28 × 0.25 × 0.19 mm

Data collection top

Bruker SMART APEX diffractometer	5112 independent reflections
Radiation source: fine-focus sealed tube	4389 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
phi and ω scans	θ_max = 25.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
T_min = 0.801, T_max = 0.859	k = −13→13
7689 measured reflections	l = −18→17

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.108P)² + 0.7243P] where P = (F_o² + 2F_c²)/3
5112 reflections	(Δ/σ)_max = 0.002
425 parameters	Δρ_max = 1.04 e Å⁻³
103 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

[Cu(C₂H₃O₂)(C₁₂H₈N₂)₂](C₂F₃O₂)·4H₂O	γ = 108.514 (1)°
M_r = 668.08	V = 1451.98 (19) Å³
Triclinic, P1	Z = 2
a = 8.9019 (7) Å	Mo Kα radiation
b = 11.6662 (9) Å	µ = 0.83 mm⁻¹
c = 15.698 (1) Å	T = 293 K
α = 101.619 (1)°	0.28 × 0.25 × 0.19 mm
β = 101.512 (1)°

Data collection top

Bruker SMART APEX diffractometer	5112 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4389 reflections with I > 2σ(I)
T_min = 0.801, T_max = 0.859	R_int = 0.043
7689 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	103 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.02	Δρ_max = 1.04 e Å⁻³
5112 reflections	Δρ_min = −0.87 e Å⁻³
425 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	Occ. (<1)
Cu1	0.70769 (5)	0.42710 (4)	0.71713 (3)	0.0397 (2)
F1	0.083 (2)	0.9968 (17)	0.6171 (10)	0.133 (4)	0.52 (2)
F2	0.138 (2)	0.8377 (11)	0.5566 (10)	0.118 (4)	0.52 (2)
F3	0.3252 (15)	1.0243 (15)	0.6021 (9)	0.121 (4)	0.52 (2)
F1'	0.0317 (13)	0.9385 (17)	0.5837 (12)	0.120 (4)	0.48 (2)
F2'	0.206 (2)	0.8680 (17)	0.5546 (10)	0.117 (4)	0.48 (2)
F3'	0.263 (2)	1.0720 (11)	0.6148 (9)	0.116 (4)	0.48 (2)
N1	0.5545 (4)	0.3202 (3)	0.5937 (2)	0.0432 (8)
N2	0.5668 (4)	0.5324 (3)	0.6982 (2)	0.0440 (8)
N3	0.6031 (4)	0.3667 (3)	0.8268 (2)	0.0439 (8)
N4	0.8712 (4)	0.5606 (3)	0.8296 (2)	0.0428 (8)
O1	0.8368 (4)	0.3195 (3)	0.7158 (2)	0.0491 (7)
O2	0.9846 (4)	0.4555 (4)	0.6563 (2)	0.0676 (9)
O3	0.1324 (9)	0.8811 (7)	0.7380 (5)	0.146 (2)
O4	0.3983 (7)	0.9689 (5)	0.7462 (4)	0.1105 (16)
O5	0.7803 (6)	0.8614 (5)	0.9518 (4)	0.1055 (15)
H5A	0.8130	0.8679	0.9051	0.127*
H5B	0.8480	0.9207	0.9978	0.127*
O6	0.7421 (6)	0.0847 (4)	0.7568 (4)	0.0954 (14)
H6A	0.7587	0.1508	0.7392	0.115*
H6B	0.6419	0.0542	0.7570	0.115*
O7	0.5361 (8)	0.9627 (7)	0.9249 (4)	0.139 (2)
H7A	0.6116	0.9327	0.9256	0.166*
H7B	0.5276	0.9963	0.8818	0.166*
O8	0.9949 (10)	1.0217 (8)	0.8494 (5)	0.176 (3)
H8A	0.8909	0.9997	0.8294	0.211*
H8B	1.0276	0.9799	0.8113	0.211*
C1	0.9569 (5)	0.3597 (5)	0.6812 (3)	0.0505 (10)
C2	1.0606 (7)	0.2817 (6)	0.6725 (4)	0.0720 (15)
H2A	1.0192	0.2109	0.6951	0.108*
H2B	1.1731	0.3315	0.7071	0.108*
H2C	1.0556	0.2522	0.6099	0.108*
C3	1.0023 (6)	0.6569 (4)	0.8305 (3)	0.0539 (11)
H3	1.0226	0.6644	0.7757	0.065*
C4	1.1096 (6)	0.7466 (4)	0.9102 (4)	0.0624 (13)
H4	1.1998	0.8126	0.9082	0.075*
C5	1.0821 (6)	0.7371 (4)	0.9907 (3)	0.0583 (12)
H5	1.1533	0.7966	1.0444	0.070*
C6	0.9449 (5)	0.6366 (4)	0.9928 (3)	0.0497 (10)
C7	0.8417 (5)	0.5507 (4)	0.9101 (3)	0.0402 (9)
C8	0.6997 (5)	0.4478 (4)	0.9087 (3)	0.0401 (9)
C9	0.6667 (6)	0.4339 (4)	0.9899 (3)	0.0511 (11)
C10	0.5254 (7)	0.3300 (5)	0.9842 (4)	0.0659 (14)
H10	0.4985	0.3174	1.0368	0.079*
C11	0.4303 (7)	0.2496 (5)	0.9031 (4)	0.0676 (14)
H11	0.3378	0.1809	0.8992	0.081*
C12	0.4720 (6)	0.2712 (4)	0.8253 (3)	0.0544 (11)
H12	0.4047	0.2153	0.7694	0.065*
C13	0.7751 (7)	0.5228 (5)	1.0731 (3)	0.0633 (13)
H13	0.7536	0.5136	1.1274	0.076*
C14	0.9071 (7)	0.6189 (5)	1.0746 (3)	0.0627 (13)
H14	0.9755	0.6753	1.1301	0.075*
C15	0.5530 (6)	0.2158 (4)	0.5418 (3)	0.0566 (11)
H15	0.6303	0.1826	0.5631	0.068*
C16	0.4407 (7)	0.1531 (5)	0.4566 (3)	0.0685 (14)
H16	0.4453	0.0806	0.4214	0.082*
C17	0.3246 (7)	0.1982 (6)	0.4250 (3)	0.0719 (16)
H17	0.2476	0.1556	0.3687	0.086*
C18	0.3210 (5)	0.3089 (5)	0.4771 (3)	0.0568 (12)
C19	0.4408 (5)	0.3674 (4)	0.5617 (3)	0.0446 (9)
C20	0.4465 (5)	0.4808 (4)	0.6192 (3)	0.0435 (9)
C21	0.3284 (5)	0.5328 (5)	0.5919 (3)	0.0549 (11)
C22	0.3376 (7)	0.6413 (6)	0.6535 (4)	0.0709 (15)
H22	0.2617	0.6788	0.6392	0.085*
C23	0.4577 (8)	0.6925 (5)	0.7343 (4)	0.0720 (15)
H23	0.4622	0.7637	0.7757	0.086*
C24	0.5729 (6)	0.6375 (5)	0.7545 (3)	0.0585 (12)
H24	0.6565	0.6751	0.8090	0.070*
C25	0.2096 (6)	0.4726 (6)	0.5058 (4)	0.0689 (16)
H25	0.1326	0.5073	0.4870	0.083*
C26	0.2068 (6)	0.3658 (7)	0.4505 (4)	0.0698 (16)
H26	0.1285	0.3295	0.3941	0.084*
C27	0.2466 (9)	0.9333 (5)	0.7120 (4)	0.0738 (16)
C28	0.1951 (7)	0.9529 (5)	0.6193 (4)	0.0709 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0400 (3)	0.0424 (3)	0.0318 (3)	0.0131 (2)	0.0061 (2)	0.0079 (2)
F1	0.127 (8)	0.135 (8)	0.138 (8)	0.076 (6)	−0.004 (6)	0.033 (6)
F2	0.108 (8)	0.122 (6)	0.075 (5)	−0.001 (6)	0.009 (6)	0.010 (5)
F3	0.109 (7)	0.130 (7)	0.119 (6)	0.005 (6)	0.049 (5)	0.070 (6)
F1'	0.071 (6)	0.127 (8)	0.130 (8)	0.013 (6)	0.004 (5)	0.032 (6)
F2'	0.118 (8)	0.148 (8)	0.071 (5)	0.060 (7)	0.024 (6)	−0.015 (6)
F3'	0.127 (8)	0.102 (7)	0.094 (6)	0.006 (6)	0.018 (6)	0.050 (5)
N1	0.0406 (18)	0.0477 (19)	0.0347 (17)	0.0091 (15)	0.0117 (14)	0.0089 (15)
N2	0.0454 (19)	0.0455 (19)	0.0408 (18)	0.0165 (15)	0.0121 (15)	0.0125 (15)
N3	0.0445 (19)	0.0401 (18)	0.0436 (19)	0.0126 (15)	0.0115 (15)	0.0108 (15)
N4	0.0416 (18)	0.0445 (18)	0.0366 (17)	0.0123 (15)	0.0057 (14)	0.0110 (15)
O1	0.0505 (17)	0.0550 (17)	0.0462 (16)	0.0231 (14)	0.0162 (13)	0.0159 (14)
O2	0.072 (2)	0.080 (2)	0.066 (2)	0.0317 (19)	0.0306 (18)	0.038 (2)
O3	0.175 (6)	0.155 (6)	0.132 (5)	0.042 (5)	0.091 (5)	0.077 (5)
O4	0.098 (4)	0.090 (3)	0.113 (4)	0.023 (3)	−0.004 (3)	0.020 (3)
O5	0.093 (3)	0.131 (4)	0.099 (3)	0.045 (3)	0.031 (3)	0.038 (3)
O6	0.090 (3)	0.075 (3)	0.127 (4)	0.027 (2)	0.034 (3)	0.044 (3)
O7	0.136 (5)	0.190 (6)	0.109 (4)	0.102 (5)	0.023 (4)	0.029 (4)
O8	0.203 (8)	0.259 (9)	0.161 (7)	0.159 (7)	0.096 (6)	0.099 (7)
C1	0.051 (2)	0.068 (3)	0.034 (2)	0.025 (2)	0.0098 (18)	0.016 (2)
C2	0.076 (3)	0.102 (4)	0.062 (3)	0.053 (3)	0.032 (3)	0.030 (3)
C3	0.051 (3)	0.051 (2)	0.051 (3)	0.009 (2)	0.008 (2)	0.018 (2)
C4	0.047 (3)	0.045 (3)	0.074 (3)	0.004 (2)	0.001 (2)	0.012 (2)
C5	0.053 (3)	0.048 (3)	0.052 (3)	0.015 (2)	−0.007 (2)	−0.003 (2)
C6	0.052 (2)	0.052 (2)	0.042 (2)	0.026 (2)	0.0027 (19)	0.0063 (19)
C7	0.044 (2)	0.043 (2)	0.0327 (19)	0.0205 (18)	0.0040 (16)	0.0087 (16)
C8	0.045 (2)	0.044 (2)	0.038 (2)	0.0233 (18)	0.0126 (17)	0.0132 (17)
C9	0.062 (3)	0.062 (3)	0.046 (2)	0.036 (2)	0.023 (2)	0.021 (2)
C10	0.075 (3)	0.078 (4)	0.068 (3)	0.035 (3)	0.041 (3)	0.037 (3)
C11	0.066 (3)	0.060 (3)	0.083 (4)	0.019 (3)	0.036 (3)	0.029 (3)
C12	0.054 (3)	0.044 (2)	0.061 (3)	0.012 (2)	0.020 (2)	0.014 (2)
C13	0.086 (4)	0.079 (4)	0.036 (2)	0.043 (3)	0.022 (2)	0.017 (2)
C14	0.075 (3)	0.078 (3)	0.033 (2)	0.039 (3)	0.005 (2)	0.004 (2)
C15	0.058 (3)	0.053 (3)	0.048 (3)	0.010 (2)	0.018 (2)	0.004 (2)
C16	0.070 (3)	0.063 (3)	0.049 (3)	0.005 (3)	0.020 (2)	−0.003 (2)
C17	0.056 (3)	0.086 (4)	0.034 (2)	−0.008 (3)	0.005 (2)	−0.002 (2)
C18	0.041 (2)	0.078 (3)	0.037 (2)	0.001 (2)	0.0096 (18)	0.019 (2)
C19	0.034 (2)	0.056 (2)	0.038 (2)	0.0049 (18)	0.0116 (16)	0.0184 (19)
C20	0.036 (2)	0.055 (2)	0.042 (2)	0.0124 (18)	0.0152 (17)	0.0231 (19)
C21	0.043 (2)	0.071 (3)	0.064 (3)	0.022 (2)	0.022 (2)	0.039 (3)
C22	0.066 (3)	0.079 (4)	0.096 (4)	0.043 (3)	0.035 (3)	0.050 (3)
C23	0.086 (4)	0.062 (3)	0.083 (4)	0.041 (3)	0.032 (3)	0.022 (3)
C24	0.068 (3)	0.056 (3)	0.055 (3)	0.029 (2)	0.017 (2)	0.013 (2)
C25	0.039 (2)	0.108 (5)	0.071 (3)	0.024 (3)	0.015 (2)	0.056 (4)
C26	0.037 (2)	0.115 (5)	0.047 (3)	0.010 (3)	0.005 (2)	0.038 (3)
C27	0.094 (4)	0.050 (3)	0.073 (4)	0.018 (3)	0.036 (3)	0.010 (3)
C28	0.069 (3)	0.065 (3)	0.074 (4)	0.015 (3)	0.028 (3)	0.020 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.953 (3)	C4—H4	0.9300
Cu1—N1	2.015 (3)	C5—C6	1.410 (7)
Cu1—N4	2.022 (3)	C5—H5	0.9300
Cu1—N2	2.037 (3)	C6—C7	1.397 (6)
Cu1—N3	2.244 (3)	C6—C14	1.428 (7)
F1—C28	1.256 (11)	C7—C8	1.433 (6)
F2—C28	1.367 (12)	C8—C9	1.392 (6)
F3—C28	1.308 (10)	C9—C10	1.415 (7)
F1'—C28	1.393 (12)	C9—C13	1.425 (7)
F2'—C28	1.311 (12)	C10—C11	1.343 (8)
F3'—C28	1.351 (11)	C10—H10	0.9301
N1—C15	1.317 (6)	C11—C12	1.392 (7)
N1—C19	1.357 (5)	C11—H11	0.9300
N2—C24	1.337 (6)	C12—H12	0.9300
N2—C20	1.344 (5)	C13—C14	1.334 (8)
N3—C12	1.326 (6)	C13—H13	0.9300
N3—C8	1.357 (5)	C14—H14	0.9300
N4—C3	1.333 (6)	C15—C16	1.389 (7)
N4—C7	1.361 (5)	C15—H15	0.9300
O1—C1	1.294 (5)	C16—C17	1.355 (8)
O2—C1	1.226 (6)	C16—H16	0.9300
O3—C27	1.202 (8)	C17—C18	1.396 (8)
O4—C27	1.245 (8)	C17—H17	0.9300
O5—H5A	0.8500	C18—C19	1.406 (6)
O5—H5B	0.8500	C18—C26	1.422 (8)
O6—H6A	0.8501	C19—C20	1.423 (6)
O6—H6B	0.8500	C20—C21	1.410 (6)
O7—H7A	0.8500	C21—C22	1.397 (8)
O7—H7B	0.8501	C21—C25	1.419 (7)
O8—H8A	0.8500	C22—C23	1.363 (8)
O8—H8B	0.8500	C22—H22	0.9300
C1—C2	1.494 (7)	C23—C24	1.391 (7)
C2—H2A	0.9600	C23—H23	0.9300
C2—H2B	0.9600	C24—H24	0.9300
C2—H2C	0.9600	C25—C26	1.356 (8)
C3—C4	1.390 (7)	C25—H25	0.9300
C3—H3	0.9300	C26—H26	0.9300
C4—C5	1.353 (8)	C27—C28	1.521 (9)

O1—Cu1—N1	91.55 (13)	C14—C13—C9	121.3 (4)
O1—Cu1—N4	93.66 (13)	C14—C13—H13	119.3
N1—Cu1—N4	169.21 (13)	C9—C13—H13	119.4
O1—Cu1—N2	171.51 (12)	C13—C14—C6	121.3 (4)
N1—Cu1—N2	81.21 (14)	C13—C14—H14	119.2
N4—Cu1—N2	92.78 (14)	C6—C14—H14	119.6
O1—Cu1—N3	93.94 (12)	N1—C15—C16	122.8 (5)
N1—Cu1—N3	110.64 (13)	N1—C15—H15	118.5
N4—Cu1—N3	78.44 (13)	C16—C15—H15	118.7
N2—Cu1—N3	92.75 (13)	C17—C16—C15	119.6 (5)
C15—N1—C19	117.9 (4)	C17—C16—H16	120.2
C15—N1—Cu1	129.2 (3)	C15—C16—H16	120.2
C19—N1—Cu1	112.9 (3)	C16—C17—C18	120.0 (4)
C24—N2—C20	118.2 (4)	C16—C17—H17	120.1
C24—N2—Cu1	129.2 (3)	C18—C17—H17	120.0
C20—N2—Cu1	112.5 (3)	C17—C18—C19	116.7 (5)
C12—N3—C8	117.7 (4)	C17—C18—C26	124.9 (5)
C12—N3—Cu1	132.8 (3)	C19—C18—C26	118.4 (5)
C8—N3—Cu1	109.5 (2)	N1—C19—C18	123.0 (4)
C3—N4—C7	118.3 (4)	N1—C19—C20	116.5 (4)
C3—N4—Cu1	125.3 (3)	C18—C19—C20	120.5 (4)
C7—N4—Cu1	116.4 (3)	N2—C20—C21	123.5 (4)
C1—O1—Cu1	110.9 (3)	N2—C20—C19	116.9 (4)
H5A—O5—H5B	109.6	C21—C20—C19	119.6 (4)
H6A—O6—H6B	109.6	C22—C21—C20	116.4 (4)
H7A—O7—H7B	109.8	C22—C21—C25	124.8 (5)
H8A—O8—H8B	108.6	C20—C21—C25	118.8 (5)
O2—C1—O1	122.5 (4)	C23—C22—C21	120.3 (5)
O2—C1—C2	121.4 (4)	C23—C22—H22	119.8
O1—C1—C2	116.0 (4)	C21—C22—H22	119.9
C1—C2—H2A	109.0	C22—C23—C24	119.6 (5)
C1—C2—H2B	109.7	C22—C23—H23	120.1
H2A—C2—H2B	109.5	C24—C23—H23	120.3
C1—C2—H2C	109.8	N2—C24—C23	122.0 (5)
H2A—C2—H2C	109.5	N2—C24—H24	119.3
H2B—C2—H2C	109.5	C23—C24—H24	118.7
N4—C3—C4	122.7 (4)	C26—C25—C21	121.3 (5)
N4—C3—H3	118.7	C26—C25—H25	119.6
C4—C3—H3	118.7	C21—C25—H25	119.2
C5—C4—C3	119.5 (5)	C25—C26—C18	121.4 (5)
C5—C4—H4	120.3	C25—C26—H26	119.1
C3—C4—H4	120.2	C18—C26—H26	119.5
C4—C5—C6	119.7 (4)	O3—C27—O4	130.9 (7)
C4—C5—H5	120.2	O3—C27—C28	113.8 (7)
C6—C5—H5	120.1	O4—C27—C28	115.2 (6)
C7—C6—C5	117.6 (4)	F1—C28—F3	113.6 (9)
C7—C6—C14	118.9 (4)	F1—C28—F2'	127.6 (11)
C5—C6—C14	123.5 (4)	F3—C28—F2'	81.4 (9)
N4—C7—C6	122.2 (4)	F1—C28—F3'	74.3 (9)
N4—C7—C8	118.1 (3)	F3—C28—F3'	40.5 (6)
C6—C7—C8	119.6 (4)	F2'—C28—F3'	113.5 (10)
N3—C8—C9	122.7 (4)	F1—C28—F2	110.5 (9)
N3—C8—C7	117.6 (3)	F3—C28—F2	106.9 (8)
C9—C8—C7	119.7 (4)	F2'—C28—F2	26.1 (8)
C8—C9—C10	117.2 (4)	F3'—C28—F2	132.9 (10)
C8—C9—C13	119.1 (4)	F1—C28—F1'	30.7 (7)
C10—C9—C13	123.7 (4)	F3—C28—F1'	126.8 (10)
C11—C10—C9	120.0 (5)	F2'—C28—F1'	99.2 (9)
C11—C10—H10	120.0	F3'—C28—F1'	96.1 (9)
C9—C10—H10	120.0	F2—C28—F1'	79.8 (9)
C10—C11—C12	119.0 (5)	F1—C28—C27	109.3 (8)
C10—C11—H11	120.3	F3—C28—C27	109.3 (8)
C12—C11—H11	120.7	F2'—C28—C27	112.0 (9)
N3—C12—C11	123.4 (5)	F3'—C28—C27	115.4 (7)
N3—C12—H12	118.3	F2—C28—C27	107.1 (8)
C11—C12—H12	118.3	F1'—C28—C27	119.0 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O5	0.85	1.95	2.787 (8)	168
O7—H7B···O4	0.85	2.11	2.854 (8)	145
O6—H6A···O1	0.85	2.00	2.844 (5)	170
O6—H6B···O4ⁱ	0.85	2.03	2.881 (7)	175
O8—H8B···O3ⁱⁱ	0.85	2.03	2.868 (10)	171
O8—H8A···O6ⁱⁱⁱ	0.85	2.17	2.809 (9)	132

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

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₃O₂)(C₁₂H₈N₂)₂](C₂F₃O₂)·4H₂O
M_r	668.08
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.9019 (7), 11.6662 (9), 15.698 (1)
α, β, γ (°)	101.619 (1), 101.512 (1), 108.514 (1)
V (Å³)	1451.98 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.28 × 0.25 × 0.19

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.801, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	7689, 5112, 4389
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.159, 1.02
No. of reflections	5112
No. of parameters	425
No. of restraints	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.04, −0.87

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O1	1.953 (3)	Cu1—N2	2.037 (3)
Cu1—N1	2.015 (3)	Cu1—N3	2.244 (3)
Cu1—N4	2.022 (3)

O1—Cu1—N1	91.55 (13)	N4—Cu1—N2	92.78 (14)
O1—Cu1—N4	93.66 (13)	O1—Cu1—N3	93.94 (12)
N1—Cu1—N4	169.21 (13)	N1—Cu1—N3	110.64 (13)
O1—Cu1—N2	171.51 (12)	N4—Cu1—N3	78.44 (13)
N1—Cu1—N2	81.21 (14)	N2—Cu1—N3	92.75 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O5	0.85	1.95	2.787 (8)	168.1
O7—H7B···O4	0.85	2.11	2.854 (8)	145.1
O6—H6A···O1	0.85	2.00	2.844 (5)	169.5
O6—H6B···O4ⁱ	0.85	2.03	2.881 (7)	174.6
O8—H8B···O3ⁱⁱ	0.85	2.03	2.868 (10)	170.9
O8—H8A···O6ⁱⁱⁱ	0.85	2.17	2.809 (9)	131.5

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

Acknowledgements

The authors thank the Young Foundation of Shanxi Province for financial support (grant No. 2010021022-1).

References

Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, Y., Ning, J., Sun, J. & Zhang, C. (2009). Acta Cryst. E65, m113. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, J., Ma, C. & Zhang, R. (2007). Acta Cryst. E63, m2691–m2692. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.