Crystal structure of catena-poly[[aqua­bis­(4-cyano­benzoato-κO)copper(II)]-μ-N,N-di­ethyl­nicotinamide-κ2N1:O]

Akduran, N.; Necefoğlu, H.; Aydoğdu, Ö.; Hökelek, T.

doi:10.1107/S205698901601183X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 8| August 2016| Pages 1183-1186

https://doi.org/10.1107/S205698901601183X

Open

access

Crystal structure of catena-poly[[aquabis(4-cyanobenzoato-κO)copper(II)]-μ-N,N-diethylnicotinamide-κ²N¹:O]

Nurcan Akduran,^a Hacali Necefoğlu,^b,^c Ömer Aydoğdu ^b and Tuncer Hökelek ^d ^*

^aSANAEM, Saray Mahallesi, Atom Caddesi, No. 27, 06980 Saray-Kazan, Ankara, Turkey, ^bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^cInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan, and ^dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 7 June 2016; accepted 20 July 2016; online 22 July 2016)

The asymmetric unit of the title polymeric compound, [Cu(C₈H₄NO₂)₂(C₁₀H₁₄N₂O)(H₂O)]_n, contains one Cu^II atom, one coordinating water molecule, two 4-cyanobenzoate (CB) ligands and one coordinating N,N-diethylnicotinamide (DENA) molecule. The DENA ligand acts as a bis-monodentate ligand, while the CB anions are monodentate. Two O atoms of the CB ligands, one O atom of the water molecule and the pyridine N atom of the DENA ligand form a slightly distorted square-planar arrangement around the Cu^II atom which is completed to a square-pyramidal coordination by the apically placed O atom of the DENA ligand, with a Cu—O distance of 2.4303 (15) Å. In the two CB anions, the carboxylate groups are twisted relative to the attached benzene rings by 2.19 (12) and 3.87 (15)°, while the benzene rings are oriented at a dihedral angle of 5.52 (8)°. The DENA ligands bridge adjacent Cu²⁺ ions, forming polymeric coordination chains running along the b axis. In the crystal, strong water–carboxylate O—H⋯O hydrogen bonds link adjacent chains into layers parallel to (10-1) and weak C—H⋯O hydrogen bonds further stabilize the crystal structure. The cyano group C and N atoms of one of the CB ligands are disordered over two sets of sites with equal occupancies.

Keywords: crystal structure; coordination polymers; copper(II) benzoates; nicotinamide ligands.

CCDC reference: 1494903

1. Chemical context

Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974 ). The nicotinic acid derivative N,N-diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972 ). The structures of some complexes obtained from the reactions of transition metal(II) ions with NA and DENA as ligands, e.g. [Ni(NA)₂(C₇H₄ClO₂)₂(H₂O)₂] (Hökelek et al., 2009a ) and [Ni(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Hökelek et al., 2009b ), have been the subject of much interest in our laboratory. Aqua complexes of Cu^II benzoates containing nicotinamide or N-methylnicotinamide ligands have been studied e.g. [Cu(4-NO₂bz)₂(mna)₂(H₂O)] and [Cu(3,5-(NO₂)₂bz)₂(NA)₂(H₂O)] (4-NO₂bz = 4-nitrobenzoate, mna = N-methylnicotinamide, 3,5-(NO₂)₂bz = 3,5-dinitrobenzoate) (Vasková et al., 2014 ) and [Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2010 ). To the best of our knowledge, the title compound is the first polymeric copper compound with a similar set of ligands.

Transition metal complexes with biochemical molecules show interesting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982 ). Some benzoic acid derivatives, such as 4-aminobenzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002 ; Amiraslanov et al., 1979 ; Hauptmann et al., 2000 ).

The structure–function–coordination relationships of the arylcarboxylate ion in Cu^II complexes of benzoic acid derivatives may change depending on the nature and position of the substituent on the benzene ring, the nature of the additional ligand molecule or solvent, and the pH and temperature of synthesis (Shnulin et al., 1981 ; Nadzhafov et al., 1981 ; Antsyshkina et al., 1980 ; Adiwidjaja et al., 1978 ). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974 ). In this context, we synthesized a Cu^II-containing compound with 4-cyanobenzoate (CB) and DENA ligands, namely catena-poly[[aquabis(4-cyanobenzoato-κO)copper(II)]-μ-N,N-diethylnicotinamide-κ²N¹:O], [Cu(DENA)(CB)₂(H₂O)]_n, and report herein its crystal structure.

2. Structural commentary

The asymmetric unit of the title polymeric compound contains one Cu^II atom, one coordinating water molecule, two 4-cyanobenzoate (CB) anions and one N,N-diethylnicotinamide (DENA) ligand; the DENA ligand acts as a bis-monodentate ligand, while the CB anions are monodentate (Fig. 1). The DENA ligands bridge adjacent Cu^II ions, forming polymeric chains (Fig. 2) running along the b axis.

Figure 1
The asymmetric unit of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Part of the polymeric chain in the title compound. One part of the disordered CN group and H atoms have been omitted for clarity.

The two carboxylate O atoms (O2 and O4) of the CB anions, the coordinating water O atom (O6) and the N atom (N3) of the DENA ligand form a slightly distorted square-planar arrangement around the Cu atom, while the distorted square-pyramidal coordination is completed by the O atom (O5) of the DENA ligand at a distance of 2.4303 (15) Å (Table 1 and Fig. 2). A more remote O atom at 2.8500 (15) Å defines a tetragonally distorted CuNO₃₊₂ octahedron.

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	2.8500 (15)	Cu1—O5ⁱ	2.4303 (15)
Cu1—O2	1.9595 (14)	Cu1—N3	1.9999 (16)
Cu1—O4	1.9400 (14)	O6—Cu1	1.9503 (15)

O2—Cu1—O5ⁱ	90.12 (6)	O6—Cu1—O2	88.67 (6)
O2—Cu1—N3	89.16 (6)	O6—Cu1—O5ⁱ	93.94 (6)
O4—Cu1—O5ⁱ	90.54 (6)	O6—Cu1—N3	175.09 (7)
O4—Cu1—O6	91.40 (7)	N3—Cu1—O5ⁱ	90.47 (6)
O4—Cu1—N3	90.73 (6)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

In the carboxylate groups, the C—O bonds for coordinating O atoms are 0.028 (3) Å {for C1—O1 [1.244 (3) Å] and C1—O2 [1.272 (3) Å]} and 0.041 (3) Å {for C9—O3 [1.232 (3) Å] and C9—O4 [1.273 (3) Å]} longer than those of the non-coordinating ones, in which they indicate delocalized bonding arrangements rather than localized single and double bonds.

The Cu1 atom lies −0.0054 (2) and −0.1184 (2) Å, respectively, out of the planes of the O1/O2/C1 and O3/O4/C9 carboxylate groups. The O1—Cu1—O2 angle is 51.12 (6)°. The corresponding O—M—O (where M is a metal) angles are 59.76 (5) and 55.08 (5)° in [Cu(C₇H₄O₂Cl)₂(C₆H₆N₂O)₂] (Bozkurt et al., 2013 ), 53.50 (14)° in [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄] (Sertçelik et al., 2013 ), 57.75 (2)° in [Cu(C₇H₄FO₂)₂(C₇H₅FO₂)(C₆H₆N₂O)₂] (Necefoğlu et al., 2011 ) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) (Greenaway et al., 1984 ).

The dihedral angles between the carboxylate groups [(O1/O2/C1) and (O3/O4/C9)] and the adjacent benzene rings [A (C2–C7) and B (C10–C15)] are 2.19 (12) and 3.87 (15)°, respectively, while the benzene and pyridine [C (N3/C17–C21)] rings are oriented at dihedral angles of A/B = 5.52 (8), A/C = 88.66 (7) and B/C = 85.85 (7)°.

3. Supramolecular features

In the crystal, strong O—H_water ⋯ O_carboxylate hydrogen bonds (Table 2) link adjacent chains into layers parallel to (10 $[\overline{1}]$ ). Weak intermolecular C—H_DENA ⋯ O_carboxylate, C—H_DENA ⋯ O_DENA and C—H_DENA ⋯ O_water hydrogen bonds (Table 2) may further stabilize the crystal structure.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H61⋯O3ⁱⁱ	0.81 (2)	1.83 (2)	2.630 (2)	171 (3)
O6—H62⋯O1ⁱⁱ	0.79 (2)	1.90 (2)	2.673 (2)	166 (3)
C18—H18⋯O2ⁱⁱⁱ	0.93	2.55	3.460 (3)	166
C21—H21⋯O5ⁱ	0.93	2.45	3.054 (3)	123
C23—H23B⋯O6^iv	0.97	2.32	3.208 (3)	152
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (iii) x, y+1, z; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

4. Synthesis and crystallization

The title compound was prepared by the reaction of CuSO₄·5H₂O (1.24 g, 5 mmol) in H₂O (50 ml) and diethylnicotinamide (1.78 g, 10 mmol) in H₂O (10 ml) with sodium 4-cyanobenzoate (1.69 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving translucent dark-blue single crystals.

5. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 3. Atoms H61 and H62 (for H₂O) were located in a difference Fourier map and were refined by applying restrains [O—H = 0.85 (2) Å]. The C-bound H atoms were positioned geometrically with C—H = 0.93, 0.97 and 0.96 Å, for aromatic, methylene and methyl H-atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = k × U_eq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic and methylene H atoms. The CN substituents of one of the benzoate ligands are disordered over two sets of sites with equal occupancies.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₈H₄NO₂)₂(C₁₀H₁₄N₂O)(H₂O)]
M_r	552.04
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	14.6207 (4), 8.0160 (3), 22.2892 (5)
β (°)	101.725 (3)
V (Å³)	2557.78 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.90
Crystal size (mm)	0.45 × 0.36 × 0.11

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.671, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	42530, 6403, 4871
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.103, 1.05
No. of reflections	6403
No. of parameters	362
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)	0.44, −0.47
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1494903

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698901601183X/gk2662sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901601183X/gk2662Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); 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, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

catena-Poly[[aquabis(4-cyanobenzoato-κO)copper(II)]-µ-N,N-diethylnicotinamide-κ²N¹:O] top

Crystal data top

[Cu(C₈H₄NO₂)₂(C₁₀H₁₄N₂O)(H₂O)]	F(000) = 1140
M_r = 552.04	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9911 reflections
a = 14.6207 (4) Å	θ = 2.7–28.3°
b = 8.0160 (3) Å	µ = 0.90 mm⁻¹
c = 22.2892 (5) Å	T = 296 K
β = 101.725 (3)°	Prism, translucent dark blue
V = 2557.78 (13) Å³	0.45 × 0.36 × 0.11 mm
Z = 4

Data collection top

Bruker SMART BREEZE CCD diffractometer	6403 independent reflections
Radiation source: fine-focus sealed tube	4871 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
φ and ω scans	θ_max = 28.4°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −19→19
T_min = 0.671, T_max = 0.912	k = −10→10
42530 measured reflections	l = −29→29

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0489P)² + 0.8094P] where P = (F_o² + 2F_c²)/3
6403 reflections	(Δ/σ)_max < 0.001
362 parameters	Δρ_max = 0.44 e Å⁻³
2 restraints	Δρ_min = −0.47 e Å⁻³

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	Occ. (<1)
Cu1	0.090509 (15)	0.08013 (3)	0.097687 (11)	0.03134 (9)
O1	0.16527 (10)	0.1123 (2)	−0.01029 (8)	0.0518 (4)
O2	0.20187 (9)	−0.02498 (18)	0.07812 (7)	0.0381 (3)
O3	−0.07154 (12)	0.2958 (2)	0.02356 (8)	0.0556 (4)
O4	−0.01992 (9)	0.18571 (19)	0.11618 (7)	0.0444 (4)
O5	0.37494 (11)	0.45382 (19)	0.30110 (7)	0.0472 (4)
O6	0.01725 (10)	−0.10957 (19)	0.05986 (7)	0.0365 (3)
H61	0.0397 (17)	−0.162 (3)	0.0354 (11)	0.063 (9)*
H62	−0.0380 (12)	−0.108 (3)	0.0510 (12)	0.060 (8)*
N1	0.5925 (2)	−0.3371 (4)	−0.06545 (14)	0.0950 (10)
N2A	−0.4017 (6)	0.7313 (12)	0.1822 (4)	0.109 (3)	0.50
N2B	−0.4394 (6)	0.6248 (14)	0.1870 (5)	0.116 (3)	0.50
N3	0.16793 (10)	0.2791 (2)	0.12940 (7)	0.0314 (4)
N4	0.43627 (11)	0.2351 (2)	0.25951 (7)	0.0358 (4)
C1	0.21593 (13)	0.0157 (3)	0.02560 (10)	0.0376 (5)
C2	0.29915 (14)	−0.0606 (3)	0.00607 (10)	0.0374 (5)
C3	0.35893 (15)	−0.1668 (3)	0.04427 (11)	0.0451 (5)
H3	0.3480	−0.1906	0.0830	0.054*
C4	0.43431 (16)	−0.2378 (3)	0.02588 (12)	0.0532 (6)
H4	0.4739	−0.3092	0.0520	0.064*
C5	0.45085 (16)	−0.2027 (3)	−0.03156 (12)	0.0506 (6)
C6	0.39130 (18)	−0.0968 (3)	−0.07040 (12)	0.0572 (7)
H6	0.4022	−0.0733	−0.1092	0.069*
C7	0.31624 (16)	−0.0267 (3)	−0.05161 (11)	0.0501 (6)
H7	0.2765	0.0443	−0.0778	0.060*
C8	0.5301 (2)	−0.2783 (4)	−0.05100 (13)	0.0676 (8)
C9	−0.07600 (14)	0.2734 (3)	0.07759 (11)	0.0385 (5)
C10	−0.15334 (13)	0.3569 (3)	0.10182 (10)	0.0371 (5)
C11	−0.16399 (15)	0.3308 (3)	0.16119 (11)	0.0476 (6)
H11	−0.1239	0.2585	0.1866	0.057*
C12	−0.23369 (18)	0.4116 (4)	0.18294 (13)	0.0642 (8)
H12	−0.2405	0.3949	0.2231	0.077*
C13	−0.29347 (19)	0.5176 (4)	0.14476 (13)	0.0706 (9)
C14	−0.2838 (2)	0.5436 (4)	0.08554 (13)	0.0692 (9)
H14	−0.3245	0.6149	0.0600	0.083*
C15	−0.21392 (17)	0.4638 (3)	0.06426 (11)	0.0521 (6)
H15	−0.2070	0.4817	0.0242	0.062*
C16A	−0.3521 (8)	0.6441 (15)	0.1651 (6)	0.073 (3)	0.50
C16B	−0.3782 (8)	0.5688 (14)	0.1706 (6)	0.081 (3)	0.50
C17	0.15321 (14)	0.4322 (3)	0.10551 (10)	0.0382 (5)
H17	0.1037	0.4486	0.0725	0.046*
C18	0.20800 (16)	0.5653 (3)	0.12768 (11)	0.0440 (5)
H18	0.1959	0.6703	0.1101	0.053*
C19	0.28183 (15)	0.5417 (3)	0.17672 (11)	0.0401 (5)
H19	0.3193	0.6312	0.1930	0.048*
C20	0.29939 (13)	0.3835 (2)	0.20134 (9)	0.0297 (4)
C21	0.24061 (12)	0.2563 (2)	0.17641 (9)	0.0308 (4)
H21	0.2516	0.1497	0.1928	0.037*
C22	0.37445 (13)	0.3587 (3)	0.25778 (9)	0.0316 (4)
C23	0.50883 (16)	0.2147 (3)	0.31541 (11)	0.0538 (6)
H23A	0.5285	0.0990	0.3190	0.065*
H23B	0.4825	0.2417	0.3508	0.065*
C24	0.59187 (19)	0.3226 (5)	0.31558 (17)	0.0892 (11)
H24A	0.6363	0.3072	0.3533	0.134*
H24B	0.5727	0.4373	0.3118	0.134*
H24C	0.6201	0.2927	0.2818	0.134*
C25	0.44567 (16)	0.1255 (3)	0.20873 (11)	0.0484 (6)
H25A	0.5103	0.1255	0.2042	0.058*
H25B	0.4079	0.1690	0.1711	0.058*
C26	0.4156 (2)	−0.0535 (3)	0.21815 (15)	0.0693 (8)
H26A	0.4343	−0.1249	0.1882	0.104*
H26B	0.3490	−0.0578	0.2137	0.104*
H26C	0.4447	−0.0905	0.2585	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02943 (12)	0.03170 (15)	0.03000 (15)	0.00186 (9)	−0.00075 (9)	−0.00126 (10)
O1	0.0366 (8)	0.0593 (11)	0.0556 (11)	0.0051 (7)	0.0006 (7)	0.0137 (8)
O2	0.0365 (7)	0.0379 (8)	0.0394 (9)	0.0017 (6)	0.0066 (6)	−0.0021 (7)
O3	0.0702 (11)	0.0561 (11)	0.0428 (10)	0.0174 (9)	0.0170 (8)	−0.0003 (8)
O4	0.0369 (7)	0.0483 (9)	0.0470 (9)	0.0091 (7)	0.0059 (6)	−0.0029 (8)
O5	0.0543 (9)	0.0412 (9)	0.0399 (9)	0.0110 (7)	−0.0054 (7)	−0.0162 (7)
O6	0.0322 (7)	0.0422 (9)	0.0322 (9)	−0.0014 (6)	−0.0004 (6)	−0.0043 (7)
N1	0.103 (2)	0.105 (2)	0.091 (2)	0.0460 (19)	0.0533 (17)	0.0233 (18)
N2A	0.093 (6)	0.148 (9)	0.090 (5)	0.064 (6)	0.032 (4)	−0.015 (6)
N2B	0.099 (7)	0.158 (9)	0.098 (6)	0.068 (6)	0.036 (5)	−0.006 (7)
N3	0.0340 (8)	0.0276 (9)	0.0306 (9)	0.0021 (6)	0.0018 (6)	0.0009 (7)
N4	0.0389 (8)	0.0356 (10)	0.0299 (9)	0.0041 (7)	0.0001 (7)	−0.0068 (8)
C1	0.0310 (9)	0.0347 (11)	0.0432 (13)	−0.0045 (8)	−0.0015 (8)	−0.0038 (10)
C2	0.0353 (10)	0.0383 (12)	0.0367 (12)	−0.0047 (8)	0.0030 (8)	−0.0025 (9)
C3	0.0458 (11)	0.0527 (14)	0.0372 (13)	0.0051 (10)	0.0095 (9)	0.0072 (11)
C4	0.0512 (12)	0.0591 (16)	0.0498 (15)	0.0164 (12)	0.0118 (11)	0.0128 (13)
C5	0.0551 (13)	0.0514 (15)	0.0488 (15)	0.0079 (11)	0.0189 (11)	0.0030 (12)
C6	0.0656 (15)	0.0691 (18)	0.0408 (15)	0.0088 (13)	0.0203 (12)	0.0098 (13)
C7	0.0529 (13)	0.0542 (15)	0.0424 (14)	0.0090 (11)	0.0078 (10)	0.0116 (12)
C8	0.0784 (18)	0.070 (2)	0.0616 (18)	0.0225 (15)	0.0322 (15)	0.0129 (15)
C9	0.0379 (10)	0.0317 (11)	0.0443 (14)	−0.0021 (9)	0.0044 (9)	−0.0083 (10)
C10	0.0354 (10)	0.0354 (11)	0.0379 (13)	0.0013 (8)	0.0011 (8)	−0.0082 (10)
C11	0.0433 (11)	0.0529 (15)	0.0442 (14)	0.0105 (10)	0.0030 (9)	0.0005 (12)
C12	0.0574 (15)	0.094 (2)	0.0420 (15)	0.0211 (14)	0.0116 (11)	−0.0047 (14)
C13	0.0578 (15)	0.098 (2)	0.0520 (18)	0.0357 (16)	0.0013 (12)	−0.0187 (16)
C14	0.0707 (17)	0.075 (2)	0.0542 (18)	0.0394 (15)	−0.0058 (13)	−0.0091 (15)
C15	0.0583 (14)	0.0550 (15)	0.0394 (14)	0.0155 (12)	0.0017 (10)	−0.0026 (12)
C16A	0.063 (5)	0.107 (9)	0.051 (4)	0.027 (5)	0.015 (4)	−0.001 (6)
C16B	0.070 (7)	0.099 (9)	0.075 (6)	0.045 (5)	0.018 (5)	−0.006 (6)
C17	0.0398 (10)	0.0375 (12)	0.0346 (12)	0.0057 (9)	0.0011 (8)	0.0067 (9)
C18	0.0517 (12)	0.0284 (11)	0.0502 (15)	0.0034 (9)	0.0063 (10)	0.0109 (10)
C19	0.0459 (11)	0.0265 (11)	0.0460 (13)	−0.0051 (9)	0.0052 (9)	0.0006 (9)
C20	0.0341 (9)	0.0281 (10)	0.0271 (10)	−0.0003 (8)	0.0067 (7)	−0.0008 (8)
C21	0.0342 (9)	0.0256 (10)	0.0311 (11)	0.0018 (8)	0.0028 (7)	0.0029 (8)
C22	0.0350 (9)	0.0281 (10)	0.0305 (11)	−0.0035 (8)	0.0038 (8)	−0.0024 (9)
C23	0.0525 (13)	0.0561 (16)	0.0438 (14)	0.0200 (11)	−0.0113 (10)	−0.0138 (12)
C24	0.0473 (15)	0.101 (3)	0.108 (3)	−0.0012 (16)	−0.0109 (15)	−0.035 (2)
C25	0.0451 (12)	0.0628 (16)	0.0362 (13)	0.0142 (11)	0.0057 (9)	−0.0108 (11)
C26	0.0722 (18)	0.0439 (16)	0.083 (2)	0.0149 (13)	−0.0048 (15)	−0.0242 (14)

Geometric parameters (Å, º) top

Cu1—O1	2.8500 (15)	C11—C12	1.376 (3)
Cu1—O2	1.9595 (14)	C11—H11	0.9300
Cu1—O4	1.9400 (14)	C12—H12	0.9300
Cu1—O5ⁱ	2.4303 (15)	C13—C14	1.372 (4)
Cu1—N3	1.9999 (16)	C13—C12	1.381 (4)
O1—C1	1.244 (3)	C14—C15	1.370 (4)
O2—C1	1.272 (3)	C14—H14	0.9300
O3—C9	1.232 (3)	C15—H15	0.9300
O4—C9	1.273 (3)	C16A—N2A	1.128 (14)
O5—Cu1ⁱⁱ	2.4303 (15)	C16A—N2B	1.464 (13)
O5—C22	1.229 (2)	C16A—C13	1.458 (13)
O6—Cu1	1.9503 (15)	C16A—C16B	0.737 (13)
O6—H61	0.810 (17)	C16B—N2A	1.385 (15)
O6—H62	0.791 (17)	C16B—N2B	1.126 (13)
N2A—N2B	1.034 (11)	C16B—C13	1.525 (11)
N3—C17	1.338 (2)	C17—C18	1.365 (3)
N3—C21	1.345 (2)	C17—H17	0.9300
N4—C22	1.336 (2)	C18—C19	1.384 (3)
N4—C23	1.472 (3)	C18—H18	0.9300
N4—C25	1.461 (3)	C19—H19	0.9300
C1—C2	1.503 (3)	C20—C19	1.385 (3)
C2—C3	1.383 (3)	C21—C20	1.376 (3)
C2—C7	1.386 (3)	C21—H21	0.9300
C3—H3	0.9300	C22—C20	1.505 (3)
C4—C3	1.375 (3)	C23—C24	1.490 (4)
C4—C5	1.379 (3)	C23—H23A	0.9700
C4—H4	0.9300	C23—H23B	0.9700
C5—C6	1.387 (3)	C24—H24A	0.9600
C5—C8	1.449 (3)	C24—H24B	0.9600
C6—H6	0.9300	C24—H24C	0.9600
C7—C6	1.372 (3)	C25—C26	1.528 (4)
C7—H7	0.9300	C25—H25A	0.9700
C8—N1	1.130 (3)	C25—H25B	0.9700
C9—C10	1.506 (3)	C26—H26A	0.9600
C10—C11	1.379 (3)	C26—H26B	0.9600
C10—C15	1.385 (3)	C26—H26C	0.9600

O1—Cu1—O2	51.12 (6)	C14—C13—C12	120.7 (2)
O2—Cu1—O5ⁱ	90.12 (6)	C14—C13—C16A	112.0 (5)
O2—Cu1—N3	89.16 (6)	C14—C13—C16B	124.9 (6)
O4—Cu1—O2	179.33 (7)	C13—C14—H14	120.3
O4—Cu1—O5ⁱ	90.54 (6)	C15—C14—C13	119.5 (2)
O4—Cu1—O6	91.40 (7)	C15—C14—H14	120.3
O4—Cu1—N3	90.73 (6)	C10—C15—H15	119.7
O6—Cu1—O2	88.67 (6)	C14—C15—C10	120.7 (2)
O6—Cu1—O5ⁱ	93.94 (6)	C14—C15—H15	119.7
O6—Cu1—N3	175.09 (7)	N2A—C16A—C13	174.3 (11)
N3—Cu1—O5ⁱ	90.47 (6)	C13—C16A—N2B	129.6 (10)
C1—O2—Cu1	113.07 (13)	C16B—C16A—N2A	93.5 (18)
C9—O4—Cu1	123.16 (14)	C16B—C16A—N2B	48.9 (14)
C22—O5—Cu1ⁱⁱ	162.66 (14)	C16B—C16A—C13	80.8 (18)
Cu1—O6—H61	116 (2)	N2A—C16B—C13	125.1 (9)
Cu1—O6—H62	123 (2)	N2B—C16B—N2A	47.3 (7)
H61—O6—H62	112 (3)	N2B—C16B—C13	171.9 (12)
N2B—N2A—C16A	85.2 (11)	C16A—C16B—N2A	54.4 (16)
N2B—N2A—C16B	53.1 (8)	C16A—C16B—N2B	102 (2)
N2A—N2B—C16A	50.1 (8)	C16A—C16B—C13	70.7 (16)
N2A—N2B—C16B	79.6 (10)	N3—C17—C18	122.52 (19)
C17—N3—Cu1	123.86 (13)	N3—C17—H17	118.7
C17—N3—C21	118.21 (17)	C18—C17—H17	118.7
C21—N3—Cu1	117.90 (13)	C17—C18—C19	119.05 (19)
C22—N4—C23	118.27 (17)	C17—C18—H18	120.5
C22—N4—C25	126.36 (17)	C19—C18—H18	120.5
C25—N4—C23	115.08 (17)	C18—C19—C20	119.32 (19)
O1—C1—O2	124.4 (2)	C18—C19—H19	120.3
O1—C1—C2	118.6 (2)	C20—C19—H19	120.3
O2—C1—C2	117.02 (18)	C19—C20—C22	119.78 (18)
C3—C2—C7	118.8 (2)	C21—C20—C19	117.93 (18)
C3—C2—C1	121.3 (2)	C21—C20—C22	121.97 (17)
C7—C2—C1	119.89 (19)	N3—C21—C20	122.95 (18)
C2—C3—H3	119.5	N3—C21—H21	118.5
C4—C3—C2	121.1 (2)	C20—C21—H21	118.5
C4—C3—H3	119.5	O5—C22—N4	122.77 (18)
C3—C4—C5	119.6 (2)	O5—C22—C20	117.50 (17)
C3—C4—H4	120.2	N4—C22—C20	119.73 (17)
C5—C4—H4	120.2	N4—C23—C24	112.6 (2)
C4—C5—C6	119.9 (2)	N4—C23—H23A	109.1
C4—C5—C8	119.6 (2)	N4—C23—H23B	109.1
C6—C5—C8	120.5 (2)	C24—C23—H23A	109.1
C5—C6—H6	120.0	C24—C23—H23B	109.1
C7—C6—C5	120.0 (2)	H23A—C23—H23B	107.8
C7—C6—H6	120.0	C23—C24—H24A	109.5
C2—C7—H7	119.7	C23—C24—H24B	109.5
C6—C7—C2	120.6 (2)	C23—C24—H24C	109.5
C6—C7—H7	119.7	H24A—C24—H24B	109.5
N1—C8—C5	179.2 (4)	H24A—C24—H24C	109.5
O3—C9—O4	125.9 (2)	H24B—C24—H24C	109.5
O3—C9—C10	118.58 (19)	N4—C25—C26	112.5 (2)
O4—C9—C10	115.5 (2)	N4—C25—H25A	109.1
C11—C10—C9	121.09 (19)	N4—C25—H25B	109.1
C11—C10—C15	119.4 (2)	C26—C25—H25A	109.1
C15—C10—C9	119.5 (2)	C26—C25—H25B	109.1
C10—C11—H11	119.9	H25A—C25—H25B	107.8
C12—C11—C10	120.2 (2)	C25—C26—H26A	109.5
C12—C11—H11	119.9	C25—C26—H26B	109.5
C11—C12—C13	119.6 (2)	C25—C26—H26C	109.5
C11—C12—H12	120.2	H26A—C26—H26B	109.5
C13—C12—H12	120.2	H26A—C26—H26C	109.5
C12—C13—C16A	125.1 (5)	H26B—C26—H26C	109.5
C12—C13—C16B	113.2 (5)

O5ⁱ—Cu1—O2—C1	−176.78 (14)	C9—C10—C11—C12	178.4 (2)
O6—Cu1—O2—C1	89.28 (14)	C15—C10—C11—C12	−0.5 (4)
N3—Cu1—O2—C1	−86.32 (14)	C11—C10—C15—C14	0.1 (4)
O5ⁱ—Cu1—O4—C9	−177.31 (16)	C9—C10—C15—C14	−178.9 (2)
O6—Cu1—O4—C9	−83.35 (16)	C10—C11—C12—C13	0.6 (4)
N3—Cu1—O4—C9	92.22 (16)	C14—C13—C12—C11	−0.2 (5)
O2—Cu1—N3—C17	117.84 (16)	C16A—C13—C12—C11	−162.1 (6)
O2—Cu1—N3—C21	−60.21 (14)	C16B—C13—C12—C11	168.1 (6)
O4—Cu1—N3—C17	−61.50 (16)	C12—C13—C14—C15	−0.2 (5)
O4—Cu1—N3—C21	120.45 (14)	C16A—C13—C14—C15	163.8 (5)
O5ⁱ—Cu1—N3—C17	−152.04 (16)	C16B—C13—C14—C15	−167.1 (6)
O5ⁱ—Cu1—N3—C21	29.90 (14)	C13—C14—C15—C10	0.3 (5)
Cu1—O2—C1—O1	0.2 (3)	N2B—C16A—N2A—C16B	3 (2)
Cu1—O2—C1—C2	−179.20 (13)	C16B—C16A—N2A—N2B	−3 (2)
Cu1—O4—C9—O3	4.2 (3)	N2A—C16A—N2B—C16B	−176 (3)
Cu1—O4—C9—C10	−175.13 (13)	C13—C16A—N2B—N2A	179.0 (17)
Cu1ⁱⁱ—O5—C22—N4	−10.6 (6)	C13—C16A—N2B—C16B	3.5 (15)
Cu1ⁱⁱ—O5—C22—C20	168.3 (4)	C16B—C16A—N2B—N2A	176 (3)
C16A—N2A—N2B—C16B	2.2 (15)	N2B—C16A—C13—C12	−76.1 (13)
C16B—N2A—N2B—C16A	−2.2 (15)	N2B—C16A—C13—C14	120.7 (11)
Cu1—N3—C17—C18	−179.16 (17)	N2B—C16A—C13—C16B	−2.6 (11)
C21—N3—C17—C18	−1.1 (3)	C16B—C16A—C13—C12	−73 (2)
Cu1—N3—C21—C20	179.03 (14)	C16B—C16A—C13—C14	123.4 (18)
C17—N3—C21—C20	0.9 (3)	N2A—C16A—C16B—N2B	3 (2)
C23—N4—C22—O5	−1.1 (3)	N2A—C16A—C16B—C13	−179.5 (11)
C23—N4—C22—C20	179.90 (19)	N2B—C16A—C16B—N2A	−3 (2)
C25—N4—C22—O5	−174.6 (2)	N2B—C16A—C16B—C13	177.3 (12)
C25—N4—C22—C20	6.5 (3)	C13—C16A—C16B—N2A	179.5 (11)
C22—N4—C23—C24	−85.3 (3)	C13—C16A—C16B—N2B	−177.3 (12)
C25—N4—C23—C24	88.8 (3)	N2B—C16B—N2A—C16A	−176 (3)
C22—N4—C25—C26	−110.6 (2)	C13—C16B—N2A—C16A	0.5 (13)
C23—N4—C25—C26	75.8 (3)	C13—C16B—N2A—N2B	176.3 (17)
O1—C1—C2—C3	179.0 (2)	C16A—C16B—N2A—N2B	176 (3)
O1—C1—C2—C7	−2.0 (3)	N2A—C16B—N2B—C16A	3 (2)
O2—C1—C2—C3	−1.6 (3)	C16A—C16B—N2B—N2A	−3 (2)
O2—C1—C2—C7	177.4 (2)	N2A—C16B—C13—C12	121.0 (11)
C1—C2—C3—C4	179.2 (2)	N2A—C16B—C13—C14	−71.3 (14)
C7—C2—C3—C4	0.2 (4)	N2A—C16B—C13—C16A	−0.4 (11)
C1—C2—C7—C6	−179.3 (2)	C16A—C16B—C13—C12	121.4 (18)
C3—C2—C7—C6	−0.2 (4)	C16A—C16B—C13—C14	−71 (2)
C5—C4—C3—C2	0.1 (4)	N3—C17—C18—C19	0.1 (3)
C3—C4—C5—C6	−0.3 (4)	C17—C18—C19—C20	1.2 (3)
C3—C4—C5—C8	−179.7 (3)	C21—C20—C19—C18	−1.4 (3)
C4—C5—C6—C7	0.2 (4)	C22—C20—C19—C18	−175.1 (2)
C8—C5—C6—C7	179.7 (3)	N3—C21—C20—C19	0.4 (3)
C2—C7—C6—C5	0.0 (4)	N3—C21—C20—C22	173.90 (17)
O3—C9—C10—C11	177.3 (2)	O5—C22—C20—C19	48.0 (3)
O3—C9—C10—C15	−3.7 (3)	O5—C22—C20—C21	−125.4 (2)
O4—C9—C10—C11	−3.3 (3)	N4—C22—C20—C19	−133.0 (2)
O4—C9—C10—C15	175.6 (2)	N4—C22—C20—C21	53.6 (3)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H61···O3ⁱⁱⁱ	0.81 (2)	1.83 (2)	2.630 (2)	171 (3)
O6—H62···O1ⁱⁱⁱ	0.79 (2)	1.90 (2)	2.673 (2)	166 (3)
C18—H18···O2^iv	0.93	2.55	3.460 (3)	166
C21—H21···O5ⁱ	0.93	2.45	3.054 (3)	123
C23—H23B···O6ⁱⁱ	0.97	2.32	3.208 (3)	152

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y, −z; (iv) x, y+1, z.

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization).

References

Adiwidjaja, G., Rossmanith, E. & Küppers, H. (1978). Acta Cryst. B34, 3079–3083. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Amiraslanov, I. R., Mamedov, Kh. S., Movsumov, E. M., Musaev, F. N. & Nadzhafov, G. N. (1979). Zh. Strukt. Khim. 20, 1075–1080. CAS Google Scholar
Antolini, L., Battaglia, L. P., Corradi, A. B., Marcotrigiano, G., Menabue, L., Pellacani, G. C. & Saladini, M. (1982). Inorg. Chem. 21, 1391–1395. CSD CrossRef CAS Web of Science Google Scholar
Antsyshkina, A. S., Chiragov, F. M. & Poray-Koshits, M. A. (1980). Koord. Khim. 15, 1098–1103. Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1972). Acta Cryst. B28, 962–966. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bozkurt, N., Dilek, N., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2013). Acta Cryst. E69, m356–m357. CSD CrossRef IUCr Journals Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Catterick (neé Drew), J., Hursthouse, M. B., New, D. B. & Thornton, P. (1974). J. Chem. Soc. Chem. Commun. pp. 843–844. Google Scholar
Chen, H. J. & Chen, X. M. (2002). Inorg. Chim. Acta, 329, 13–21. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Greenaway, F. T., Pezeshk, A., Cordes, A. W., Noble, M. C. & Sorenson, J. R. J. (1984). Inorg. Chim. Acta, 93, 67–71. CSD CrossRef CAS Web of Science Google Scholar
Hauptmann, R., Kondo, M. & Kitagawa, S. (2000). Z. Kristallogr. New Cryst. Struct. 215, 169–172. CAS Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009a). Acta Cryst. E65, m466–m467. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009b). Acta Cryst. E65, m545–m546. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Süzen, Y., Tercan, B., Tenlik, E. & Necefoğlu, H. (2010). Acta Cryst. E66, m807–m808. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CAS PubMed Web of Science Google Scholar
Nadzhafov, G. N., Shnulin, A. N. & Mamedov, Kh. S. (1981). Zh. Strukt. Khim. 22, 124–128. CAS Google Scholar
Necefoğlu, H., Özbek, F. E., Öztürk, V., Tercan, B. & Hökelek, T. (2011). Acta Cryst. E67, m887–m888. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sertçelik, M., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2013). Acta Cryst. E69, m290–m291. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shnulin, A. N., Nadzhafov, G. N., Amiraslanov, I. R., Usubaliev, B. T. & Mamedov, Kh. S. (1981). Koord. Khim. 7, 1409–1416. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vasková, Z., Kitanovski, N., Jagličić, Z., Strauch, P., Růžičková, Z., Valigura, D., Koman, M., Kozlevčar, B. & Moncol, J. (2014). Polyhedron, 81, 555–563. 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.