Diaqua­bis­(N,N′-diethyl­nicotinamide-κN1)bis­(4-fluoro­benzoato-κO)copper(II)

Necefoğlu, H.; Özbek, F.E.; Öztürk, V.; Adıgüzel, V.; Hökelek, T.

doi:10.1107/S1600536811029941

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1164-m1165

doi:10.1107/S1600536811029941

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Diaquabis(N,N′-diethylnicotinamide-κN¹)bis(4-fluorobenzoato-κO)copper(II)

Hacali Necefoğlu,^a Füreya Elif Özbek,^a Vijdan Öztürk,^a Vedat Adıgüzel ^a and Tuncer Hökelek ^b ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and ^bDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 18 July 2011; accepted 25 July 2011; online 30 July 2011)

The asymmetric unit of the title mononuclear Cu^II complex, [Cu(C₇H₄FO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], contains one-half of the molecule. The Cu^II ion is located on an inversion centre, and is coordinated by two N atoms from two diethylnicotinamide ligands, two O atoms from two 4-fluorobenzoate (PFB) ligands and two water molecules in a distorted octahedral geometry. In the PFB ligand, the carboxylate group is twisted at an angle of 2.10 (14)° from the attached benzene ring. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link molecules related by translation along the a axis into chains. Weak intermolecular C—H⋯O hydrogen bonds and π–π interactions between the pyridine rings of neighbouring molecules [centroid-to-centroid distance = 3.571 (2) Å] further consolidate the crystal packing.

Related literature

For background to niacin, see: Krishnamachari (1974 ). For infomation on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1996 , 2009a ,b ); Hökelek & Necefoğlu (1998 , 2007 ); Necefoğlu et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Cu(C₇H₄FO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r = 734.25
Triclinic, $[P \overline 1]$
a = 7.4802 (2) Å
b = 8.6753 (2) Å
c = 14.6695 (4) Å
α = 77.164 (3)°
β = 84.723 (4)°
γ = 65.151 (2)°
V = 842.23 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 100 K
0.48 × 0.32 × 0.21 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.759, T_max = 0.860
13620 measured reflections
4109 independent reflections
3714 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.099
S = 1.15
4109 reflections
233 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2ⁱ	0.83 (2)	1.90 (2)	2.7050 (19)	163 (3)
O4—H42⋯O3ⁱⁱ	0.83 (2)	2.01 (2)	2.834 (2)	172 (2)
C6—H6⋯O2ⁱⁱ	0.93	2.32	3.211 (2)	162
C10—H10⋯O2ⁱⁱⁱ	0.93	2.48	3.394 (2)	170
Symmetry codes: (i) -x, -y, -z; (ii) x+1, y, z; (iii) -x, -y-1, -z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811029941/cv6646sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029941/cv6646Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized. Herewith we report its crystal structure (Fig. 1).

The asymmetric unit of the title mononuclear Cu^II complex contains one-half molecule, the Cu^II atom being located on an inversion center. The unit cell of the title compound contains also two N,N-diethylnicotinamide (DENA) ligands, two 4-fluorobenzoato (PFB) ligands and two coordinated water molecules. All ligands coordinate the Cu in a monodentate manner. The crystal structures of similar omplexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) have also been reported. In the copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, four O atoms (O1, O1', O4 and O4', see Fig. 1) in the equatorial plane around the Cu^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the DENA ligands (N1 and N1') in the axial positions. The near equalities of the C1—O1 [1.2716 (19) Å] and C1—O2 [1.247 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Cu—O bond lengths are 1.9833 (11) Å (for benzoate oxygen) and 2.4192 (12) Å (for water oxygen), and the Cu—N bond length is 2.0192 (14) Å, close to standard values (Allen et al., 1987). The Cu atom is displaced out of the mean plane of the carboxylate group (O1/C1/O2) by 0.7971 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2–C7) is 2.10 (14)°. The benzene A (C2–C7) and the pyridine B (N1/C8–C12) rings are oriented at a dihedral angle of A/B = 76.11 (6)°.

In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 1) link the molecules related by translation along axis a into chains. Weak intermolecular C—H···O hydrogen bonds (Table 1) and π–π interactions between the pyridine rings from the neighbouring molecules [Cg1···Cg1ⁱ = 3.571 (2) Å; symmetry code: (i) 2 - x, 1 - y, -z; Cg1 is the centroid of N1/C8—C12] consolidate further the crystal packing.

Related literature top

For background to niacin, see: Krishnamachari (1974). For infomation on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1996, 2009a,b); Hökelek & Necefoğlu (1998, 2007); Necefoğlu et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.23 g, 5 mmol) in H₂O (20 ml) and DENA (1.78 g, 10 mmol) in H₂O (20 ml) with sodium 4-fluorobenzoate (1.62 g, 10 mmol) in H₂O (50 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for a week, giving blue single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code ('): -x, -y, -z].

Diaquabis(N,N'-diethylnicotinamide-κN¹)bis(4- fluorobenzoato-κO)copper(II) top

Crystal data top

[Cu(C₇H₄FO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	Z = 1
M_r = 734.25	F(000) = 383
Triclinic, P1	D_x = 1.448 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4802 (2) Å	Cell parameters from 9044 reflections
b = 8.6753 (2) Å	θ = 2.9–28.4°
c = 14.6695 (4) Å	µ = 0.72 mm⁻¹
α = 77.164 (3)°	T = 100 K
β = 84.723 (4)°	Block, blue
γ = 65.151 (2)°	0.48 × 0.32 × 0.21 mm
V = 842.23 (4) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4109 independent reflections
Radiation source: fine-focus sealed tube	3714 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 28.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.759, T_max = 0.860	k = −11→11
13620 measured reflections	l = −19→19

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0524P)² + 0.2704P] where P = (F_o² + 2F_c²)/3
4109 reflections	(Δ/σ)_max < 0.001
233 parameters	Δρ_max = 0.57 e Å⁻³
2 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu(C₇H₄FO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	γ = 65.151 (2)°
M_r = 734.25	V = 842.23 (4) Å³
Triclinic, P1	Z = 1
a = 7.4802 (2) Å	Mo Kα radiation
b = 8.6753 (2) Å	µ = 0.72 mm⁻¹
c = 14.6695 (4) Å	T = 100 K
α = 77.164 (3)°	0.48 × 0.32 × 0.21 mm
β = 84.723 (4)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4109 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3714 reflections with I > 2σ(I)
T_min = 0.759, T_max = 0.860	R_int = 0.025
13620 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	2 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.57 e Å⁻³
4109 reflections	Δρ_min = −0.45 e Å⁻³
233 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.0000	0.0000	0.01357 (9)
O1	0.16849 (16)	−0.15368 (15)	0.10899 (8)	0.0158 (2)
O2	−0.04849 (17)	−0.19328 (17)	0.21759 (8)	0.0203 (3)
O3	−0.43885 (17)	−0.29279 (17)	−0.12427 (8)	0.0201 (3)
O4	0.29700 (18)	0.01961 (18)	−0.07056 (9)	0.0209 (3)
H41	0.242 (4)	0.068 (3)	−0.1223 (13)	0.047 (8)*
H42	0.382 (3)	−0.074 (2)	−0.0817 (16)	0.032 (6)*
N1	0.03309 (19)	−0.20678 (18)	−0.05247 (9)	0.0140 (3)
N2	−0.2966 (2)	−0.34165 (19)	−0.26337 (10)	0.0170 (3)
F1	0.65236 (17)	−0.32105 (18)	0.47171 (7)	0.0329 (3)
C1	0.1133 (2)	−0.1884 (2)	0.19273 (11)	0.0144 (3)
C2	0.2588 (2)	−0.2244 (2)	0.26753 (11)	0.0149 (3)
C3	0.2080 (2)	−0.2568 (2)	0.36158 (11)	0.0177 (3)
H3	0.0846	−0.2564	0.3777	0.021*
C4	0.3405 (3)	−0.2895 (2)	0.43123 (12)	0.0209 (4)
H4	0.3080	−0.3110	0.4941	0.025*
C5	0.5214 (3)	−0.2892 (2)	0.40410 (12)	0.0212 (4)
C6	0.5773 (2)	−0.2567 (2)	0.31234 (12)	0.0197 (3)
H6	0.7008	−0.2568	0.2970	0.024*
C7	0.4429 (2)	−0.2236 (2)	0.24351 (11)	0.0159 (3)
H7	0.4761	−0.2006	0.1808	0.019*
C8	0.2015 (2)	−0.3509 (2)	−0.04352 (11)	0.0158 (3)
H8	0.3068	−0.3555	−0.0122	0.019*
C9	0.2241 (2)	−0.4928 (2)	−0.07912 (11)	0.0170 (3)
H9	0.3423	−0.5912	−0.0711	0.020*
C10	0.0693 (2)	−0.4873 (2)	−0.12681 (11)	0.0159 (3)
H10	0.0819	−0.5808	−0.1519	0.019*
C11	−0.1058 (2)	−0.3376 (2)	−0.13609 (10)	0.0141 (3)
C12	−0.1186 (2)	−0.2029 (2)	−0.09675 (11)	0.0141 (3)
H12	−0.2374	−0.1052	−0.1011	0.017*
C13	−0.2925 (2)	−0.3226 (2)	−0.17555 (11)	0.0148 (3)
C14	−0.1364 (3)	−0.3544 (3)	−0.33111 (12)	0.0215 (4)
H14A	−0.1352	−0.4266	−0.3732	0.026*
H14B	−0.0117	−0.4107	−0.2979	0.026*
C15	−0.1552 (3)	−0.1797 (3)	−0.38791 (16)	0.0354 (5)
H15A	−0.0445	−0.1953	−0.4293	0.053*
H15B	−0.1584	−0.1069	−0.3466	0.053*
H15C	−0.2747	−0.1262	−0.4239	0.053*
C16	−0.4830 (2)	−0.3304 (2)	−0.29629 (13)	0.0211 (4)
H16A	−0.5377	−0.3920	−0.2465	0.025*
H16B	−0.4550	−0.3885	−0.3486	0.025*
C17	−0.6367 (3)	−0.1461 (3)	−0.32646 (15)	0.0288 (4)
H17A	−0.7545	−0.1488	−0.3455	0.043*
H17B	−0.5866	−0.0855	−0.3778	0.043*
H17C	−0.6660	−0.0874	−0.2751	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01438 (14)	0.01390 (16)	0.01479 (14)	−0.00694 (11)	−0.00242 (9)	−0.00428 (10)
O1	0.0159 (5)	0.0163 (6)	0.0160 (5)	−0.0067 (5)	−0.0017 (4)	−0.0041 (4)
O2	0.0151 (6)	0.0250 (7)	0.0224 (6)	−0.0102 (5)	−0.0015 (4)	−0.0035 (5)
O3	0.0144 (5)	0.0262 (7)	0.0218 (6)	−0.0087 (5)	0.0012 (4)	−0.0092 (5)
O4	0.0163 (6)	0.0227 (7)	0.0216 (6)	−0.0052 (5)	0.0000 (5)	−0.0063 (5)
N1	0.0131 (6)	0.0153 (7)	0.0159 (6)	−0.0077 (5)	0.0011 (5)	−0.0044 (5)
N2	0.0141 (6)	0.0198 (7)	0.0189 (6)	−0.0069 (5)	−0.0020 (5)	−0.0063 (5)
F1	0.0312 (6)	0.0496 (8)	0.0231 (5)	−0.0225 (6)	−0.0122 (4)	−0.0007 (5)
C1	0.0147 (7)	0.0100 (7)	0.0197 (7)	−0.0047 (6)	−0.0021 (6)	−0.0052 (6)
C2	0.0156 (7)	0.0122 (8)	0.0176 (7)	−0.0056 (6)	−0.0011 (6)	−0.0045 (6)
C3	0.0167 (7)	0.0172 (8)	0.0206 (8)	−0.0080 (6)	0.0000 (6)	−0.0047 (6)
C4	0.0250 (9)	0.0235 (9)	0.0157 (7)	−0.0116 (7)	−0.0011 (6)	−0.0029 (7)
C5	0.0227 (8)	0.0231 (9)	0.0204 (8)	−0.0109 (7)	−0.0082 (6)	−0.0033 (7)
C6	0.0160 (8)	0.0209 (9)	0.0240 (8)	−0.0091 (7)	−0.0024 (6)	−0.0039 (7)
C7	0.0170 (7)	0.0148 (8)	0.0168 (7)	−0.0073 (6)	−0.0007 (6)	−0.0034 (6)
C8	0.0135 (7)	0.0177 (8)	0.0166 (7)	−0.0064 (6)	−0.0002 (5)	−0.0044 (6)
C9	0.0129 (7)	0.0174 (8)	0.0193 (7)	−0.0041 (6)	−0.0006 (6)	−0.0051 (6)
C10	0.0164 (7)	0.0144 (8)	0.0183 (7)	−0.0064 (6)	0.0011 (6)	−0.0065 (6)
C11	0.0141 (7)	0.0158 (8)	0.0149 (7)	−0.0082 (6)	−0.0002 (5)	−0.0037 (6)
C12	0.0126 (7)	0.0143 (8)	0.0162 (7)	−0.0059 (6)	−0.0008 (5)	−0.0036 (6)
C13	0.0145 (7)	0.0121 (8)	0.0188 (7)	−0.0055 (6)	−0.0020 (6)	−0.0037 (6)
C14	0.0196 (8)	0.0264 (10)	0.0183 (8)	−0.0075 (7)	0.0001 (6)	−0.0081 (7)
C15	0.0334 (11)	0.0348 (12)	0.0418 (11)	−0.0194 (9)	0.0083 (9)	−0.0077 (10)
C16	0.0186 (8)	0.0229 (9)	0.0255 (8)	−0.0082 (7)	−0.0068 (6)	−0.0099 (7)
C17	0.0203 (9)	0.0243 (10)	0.0397 (10)	−0.0036 (7)	−0.0097 (7)	−0.0097 (8)

Geometric parameters (Å, º) top

Cu1—O1	1.9833 (11)	C6—H6	0.9300
Cu1—O1ⁱ	1.9833 (11)	C7—C6	1.388 (2)
Cu1—O4	2.4192 (12)	C7—H7	0.9300
Cu1—O4ⁱ	2.4192 (12)	C8—H8	0.9300
Cu1—N1	2.0192 (14)	C9—C8	1.382 (2)
Cu1—N1ⁱ	2.0192 (14)	C9—C10	1.385 (2)
O1—C1	1.2716 (19)	C9—H9	0.9300
O2—C1	1.247 (2)	C10—H10	0.9300
O3—C13	1.2363 (19)	C11—C10	1.395 (2)
O4—H41	0.831 (17)	C11—C13	1.505 (2)
O4—H42	0.833 (16)	C12—C11	1.379 (2)
N1—C8	1.342 (2)	C12—H12	0.9300
N1—C12	1.343 (2)	C14—C15	1.514 (3)
N2—C13	1.339 (2)	C14—H14A	0.9700
N2—C14	1.467 (2)	C14—H14B	0.9700
N2—C16	1.475 (2)	C15—H15A	0.9600
F1—C5	1.3601 (19)	C15—H15B	0.9600
C1—C2	1.505 (2)	C15—H15C	0.9600
C2—C3	1.395 (2)	C16—C17	1.519 (3)
C2—C7	1.393 (2)	C16—H16A	0.9700
C3—C4	1.388 (2)	C16—H16B	0.9700
C3—H3	0.9300	C17—H17A	0.9600
C4—C5	1.376 (3)	C17—H17B	0.9600
C4—H4	0.9300	C17—H17C	0.9600
C6—C5	1.376 (2)

O1—Cu1—O1ⁱ	180.00 (9)	C6—C7—C2	120.55 (15)
O1—Cu1—O4	85.97 (4)	C6—C7—H7	119.7
O1ⁱ—Cu1—O4	94.03 (4)	N1—C8—C9	122.39 (15)
O1—Cu1—O4ⁱ	94.03 (4)	N1—C8—H8	118.8
O1ⁱ—Cu1—O4ⁱ	85.97 (4)	C9—C8—H8	118.8
O4ⁱ—Cu1—O4	180.00 (9)	C8—C9—C10	119.52 (15)
N1—Cu1—O4	94.85 (5)	C8—C9—H9	120.2
N1ⁱ—Cu1—O4	85.15 (5)	C10—C9—H9	120.2
N1—Cu1—O4ⁱ	85.15 (5)	C9—C10—C11	118.13 (16)
N1ⁱ—Cu1—O4ⁱ	94.85 (5)	C9—C10—H10	120.9
O1—Cu1—N1	91.11 (5)	C11—C10—H10	120.9
O1ⁱ—Cu1—N1	88.89 (5)	C10—C11—C13	123.54 (15)
O1—Cu1—N1ⁱ	88.89 (5)	C12—C11—C10	118.98 (15)
O1ⁱ—Cu1—N1ⁱ	91.11 (5)	C12—C11—C13	116.96 (14)
N1ⁱ—Cu1—N1	180.00 (6)	N1—C12—C11	122.80 (15)
C1—O1—Cu1	127.30 (10)	N1—C12—H12	118.6
Cu1—O4—H41	91.8 (19)	C11—C12—H12	118.6
Cu1—O4—H42	114.0 (17)	O3—C13—N2	122.08 (15)
H41—O4—H42	102 (2)	O3—C13—C11	117.74 (14)
C8—N1—Cu1	122.34 (11)	N2—C13—C11	120.18 (14)
C8—N1—C12	118.14 (15)	N2—C14—C15	113.02 (15)
C12—N1—Cu1	119.51 (11)	N2—C14—H14A	109.0
C13—N2—C14	124.35 (14)	N2—C14—H14B	109.0
C13—N2—C16	117.12 (14)	C15—C14—H14A	109.0
C14—N2—C16	118.20 (14)	C15—C14—H14B	109.0
O1—C1—C2	115.78 (14)	H14A—C14—H14B	107.8
O2—C1—O1	126.09 (14)	C14—C15—H15A	109.5
O2—C1—C2	118.12 (14)	C14—C15—H15B	109.5
C3—C2—C1	119.85 (14)	C14—C15—H15C	109.5
C7—C2—C1	120.43 (14)	H15A—C15—H15B	109.5
C7—C2—C3	119.72 (15)	H15A—C15—H15C	109.5
C2—C3—H3	119.8	H15B—C15—H15C	109.5
C4—C3—C2	120.43 (16)	N2—C16—C17	114.09 (15)
C4—C3—H3	119.8	N2—C16—H16A	108.7
C3—C4—H4	121.1	N2—C16—H16B	108.7
C5—C4—C3	117.76 (15)	C17—C16—H16A	108.7
C5—C4—H4	121.1	C17—C16—H16B	108.7
F1—C5—C4	118.30 (15)	H16A—C16—H16B	107.6
F1—C5—C6	117.84 (16)	C16—C17—H17A	109.5
C6—C5—C4	123.86 (15)	C16—C17—H17B	109.5
C5—C6—C7	117.68 (16)	C16—C17—H17C	109.5
C5—C6—H6	121.2	H17A—C17—H17B	109.5
C7—C6—H6	121.2	H17A—C17—H17C	109.5
C2—C7—H7	119.7	H17B—C17—H17C	109.5

O4ⁱ—Cu1—O1—C1	−21.24 (14)	C14—N2—C16—C17	−93.55 (19)
O4—Cu1—O1—C1	158.76 (14)	O1—C1—C2—C3	177.38 (15)
N1ⁱ—Cu1—O1—C1	73.55 (14)	O1—C1—C2—C7	−1.8 (2)
N1—Cu1—O1—C1	−106.45 (14)	O2—C1—C2—C3	−1.9 (2)
O1—Cu1—N1—C8	−35.00 (12)	O2—C1—C2—C7	178.89 (15)
O1ⁱ—Cu1—N1—C8	145.00 (12)	C1—C2—C3—C4	−179.76 (16)
O1—Cu1—N1—C12	143.87 (12)	C7—C2—C3—C4	−0.6 (3)
O1ⁱ—Cu1—N1—C12	−36.13 (12)	C1—C2—C7—C6	179.96 (16)
O4ⁱ—Cu1—N1—C8	−128.95 (12)	C3—C2—C7—C6	0.8 (3)
O4—Cu1—N1—C8	51.05 (12)	C2—C3—C4—C5	−0.1 (3)
O4ⁱ—Cu1—N1—C12	49.92 (12)	C3—C4—C5—F1	179.97 (16)
O4—Cu1—N1—C12	−130.08 (12)	C3—C4—C5—C6	0.7 (3)
Cu1—O1—C1—O2	30.3 (2)	C7—C6—C5—F1	−179.76 (16)
Cu1—O1—C1—C2	−148.91 (11)	C7—C6—C5—C4	−0.5 (3)
Cu1—N1—C8—C9	179.77 (12)	C2—C7—C6—C5	−0.3 (3)
C12—N1—C8—C9	0.9 (2)	C10—C9—C8—N1	0.7 (2)
Cu1—N1—C12—C11	178.59 (11)	C8—C9—C10—C11	−0.7 (2)
C8—N1—C12—C11	−2.5 (2)	C12—C11—C10—C9	−0.8 (2)
C14—N2—C13—O3	171.65 (16)	C13—C11—C10—C9	−172.22 (15)
C14—N2—C13—C11	−8.5 (2)	C10—C11—C13—O3	118.97 (18)
C16—N2—C13—O3	−1.6 (2)	C10—C11—C13—N2	−60.9 (2)
C16—N2—C13—C11	178.22 (14)	C12—C11—C13—O3	−52.6 (2)
C13—N2—C14—C15	−89.5 (2)	C12—C11—C13—N2	127.53 (17)
C16—N2—C14—C15	83.7 (2)	N1—C12—C11—C10	2.5 (2)
C13—N2—C16—C17	80.1 (2)	N1—C12—C11—C13	174.46 (14)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.83 (2)	1.90 (2)	2.7050 (19)	163 (3)
O4—H42···O3ⁱⁱ	0.83 (2)	2.01 (2)	2.834 (2)	172 (2)
C6—H6···O2ⁱⁱ	0.93	2.32	3.211 (2)	162
C10—H10···O2ⁱⁱⁱ	0.93	2.48	3.394 (2)	170

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄FO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	734.25
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.4802 (2), 8.6753 (2), 14.6695 (4)
α, β, γ (°)	77.164 (3), 84.723 (4), 65.151 (2)
V (Å³)	842.23 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.48 × 0.32 × 0.21

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.759, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	13620, 4109, 3714
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.099, 1.15
No. of reflections	4109
No. of parameters	233
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.45

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.83 (2)	1.90 (2)	2.7050 (19)	163 (3)
O4—H42···O3ⁱⁱ	0.834 (18)	2.007 (18)	2.834 (2)	172 (2)
C6—H6···O2ⁱⁱ	0.93	2.32	3.211 (2)	162
C10—H10···O2ⁱⁱⁱ	0.93	2.48	3.394 (2)	170

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

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer. This work was financially supported by the Scientific and Technological Research Council of Turkey (grant No. 106 T472).

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