Tetra­kis(μ-3-chloro­benzoato-κ2O:O′)bis­[(N,N-di­ethyl­nicotinamide-κN1)copper(II)]

Bozkurt, N.; Tunç, T.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536813017881

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m431-m432

doi:10.1107/S1600536813017881

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Tetrakis(μ-3-chlorobenzoato-κ²O:O′)bis[(N,N-diethylnicotinamide-κN¹)copper(II)]

Nihat Bozkurt,^a Tuncay Tunç,^b Nagihan Çaylak Delibaş,^c Hacali Necefoğlu ^a and Tuncer Hökelek ^d ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bAksaray University, Science Education Department, 68100, Aksaray, Turkey, ^cDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 27 June 2013; accepted 28 June 2013; online 3 July 2013)

In the title centrosymmetric binuclear Cu^II complex, [Cu₂(C₇H₄ClO₂)₄(C₁₀H₁₄N₂O)₂], the two Cu^II cations [Cu⋯Cu = 2.6314 (4) Å] are bridged by four 3-chlorobenzoate (CB) anions. The four carboxylate O atoms around each Cu^II cation form a distorted square-planar arrangement, the distorted square-pyramidal coordination geometry being completed by the pyridine N atom of the N,N-diethylnicotinamide (DENA) molecule. The dihedral angle between the benzene ring and the carboxylate group is 4.49 (11)° in one of the independent CB ligands and 12.00 (10)° in the other. The benzene rings of the independent CB ligands are oriented at a dihedral angle of 84.13 (6)°. In the crystal, weak C—H⋯O hydrogen bonds link the binuclear complex molecules into supramolecular chains running along [101].

Related literature

For niacin, see: Krishnamachari (1974 ). For N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Speier & Fulop (1989 ); Usubaliev et al. (1980 ); Hökelek et al. (1995 ); Hökelek et al. (2009a ,b ,c , 2011 ); Necefoğlu et al. (2010a ,b ); Aydın et al. (2012 ).

Experimental

Crystal data

[Cu₂(C₇H₄ClO₂)₄(C₁₀H₁₄N₂O)₂]
M_r = 1105.75
Monoclinic, P 2₁ /c
a = 12.6077 (4) Å
b = 16.7569 (5) Å
c = 12.1402 (4) Å
β = 99.647 (2)°
V = 2528.54 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 296 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker SMART BREEZE CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.711, T_max = 0.724
78293 measured reflections
5166 independent reflections
4702 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.083
S = 1.04
5166 reflections
309 parameters
85 restraints
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9791 (13)
Cu1—O2ⁱ	1.9688 (13)
Cu1—O3	1.9755 (13)
Cu1—O4ⁱ	1.9703 (13)
Cu1—N1	2.1454 (14)
Symmetry code: (i) -x+1, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O5ⁱⁱ	0.93	2.45	3.221 (3)	140
Symmetry code: (ii) -x+2, -y+2, -z+2.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813017881/xu5716sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813017881/xu5716Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigation on 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 and its crystal structure is reported herein.

The title compound is a binuclear compound, consisting of four chlorobenzoate (CB) ligands. The structures of similar complexes of the Cu²⁺, Zn²⁺ and Co²⁺ ions, [Cu(C₆H₅COO)₂(C₅H₅N)]₂ (Usubaliev et al., 1980); [Cu(C₆H₅CO₂)₂(Py)]₂ (Speier & Fulop, 1989); [Cu₂(C₆H₅COO)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1995); [Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂] (Necefoğlu et al., 2010a); [Cu₂(C₇H₄IO₂)₄(H₂O)₂] (Aydın et al., 2012); [Zn₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009a); [Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂].2H₂O (Hökelek et al., 2009b); [Zn₂(C₉H₁₀NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009c); [Zn₂(C₈H₇O₂)₄(C₁₀H₁₄N₂O)₂] (Necefoğlu et al., 2010b) and [Co₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2011) have also been determined. In these structures, the benzoate ion acts as a bidentate ligand.

The title dimeric complex, [Cu₂(CB)₄(DENA)₂], has a centre of symmetry and two Cu^II atoms are surrounded by four CB groups and two DENA molecules. The CB groups act as bridging ligands. The Cu1···Cu1a [symmetry code: (a) 1 - x, - y, 1 - z] distance is 2.6314 (4) Å. The average Cu-O distance is 1.9734 (13) Å (Table 1), and four O atoms of the bridging CB ligands around each Cu atom form a distorted square plane. The Cu atom lies 1.3997 (2) Å below the least-squares plane. The average O-Cu-O bond angle is 89.41 (6)°. A distorted square-pyramidal arrangement around each Cu atom is completed by the DENA N atom at 2.1454 (14) Å from the Cu atom (Table 1). The N1-Cu1···Cu1a angle is 173.85 (4)° and the dihedral angle between plane through Cu1, O1, O2, C1, Cu1a, O1a, O2a, C1a and the plane through Cu1, O3, O4, C8, Cu1a, O3a, O4a, C8a is 89.76(1.45)°. The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O3/O4/C8)] and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 4.49 (11) and 12.00 (10) °, respectively, while that between rings A, B and C (N1/C15–C19) are A/B = 84.13 (6), A/C = 57.94 (6) and B/C = 37.95 (7) °.

In the crystal structure, weak intermolecular C—H···O interactions (Table 2) link the molecules into infinite chains through the centrosymmetric dimers running along the [1 0 1] direction.

Related literature top

For niacin, see: Krishnamachari (1974). For N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Speier & Fulop (1989); Usubaliev et al. (1980); Hökelek et al. (1995, Hökelek et al. (2009a,b,c, 2011); Necefoğlu et al. (2010a,b); Aydın et al. (2012).

Experimental top

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.25 g, 5 mmol) in H₂O (100 ml) and diethylnicotinamide (1.78 g, 10 mmol) in H₂O (20 ml) with sodium 3-chlorobenzoate (1.79 g, 10 mmol) in H₂O (100 ml). The mixture was set aside to crystallize at ambient temperature for five days, giving green single crystals.

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).

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: (a) 1 - x, - y, 1 - z]. Hydrogen atoms have been omitted for clarity.
	Fig. 2. A view of the packing of the title compound. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Tetrakis(µ-3-chlorobenzoato-κ²O:O')bis[(N,N-diethylnicotinamide-κN¹)copper(II)] top

Crystal data top

[Cu₂(C₇H₄ClO₂)₄(C₁₀H₁₄N₂O)₂]	F(000) = 1132
M_r = 1105.75	D_x = 1.452 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9380 reflections
a = 12.6077 (4) Å	θ = 2.5–29.9°
b = 16.7569 (5) Å	µ = 1.11 mm⁻¹
c = 12.1402 (4) Å	T = 296 K
β = 99.647 (2)°	Block, green
V = 2528.54 (14) Å³	0.35 × 0.25 × 0.20 mm
Z = 2

Data collection top

Bruker SMART BREEZE CCD diffractometer	5166 independent reflections
Radiation source: fine-focus sealed tube	4702 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −15→15
T_min = 0.711, T_max = 0.724	k = −20→20
78293 measured reflections	l = −15→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0449P)² + 1.301P] where P = (F_o² + 2F_c²)/3
5166 reflections	(Δ/σ)_max = 0.002
309 parameters	Δρ_max = 0.70 e Å⁻³
85 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu₂(C₇H₄ClO₂)₄(C₁₀H₁₄N₂O)₂]	V = 2528.54 (14) Å³
M_r = 1105.75	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6077 (4) Å	µ = 1.11 mm⁻¹
b = 16.7569 (5) Å	T = 296 K
c = 12.1402 (4) Å	0.35 × 0.25 × 0.20 mm
β = 99.647 (2)°

Data collection top

Bruker SMART BREEZE CCD diffractometer	5166 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	4702 reflections with I > 2σ(I)
T_min = 0.711, T_max = 0.724	R_int = 0.026
78293 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	85 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.04	Δρ_max = 0.70 e Å⁻³
5166 reflections	Δρ_min = −0.45 e Å⁻³
309 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	0.580773 (15)	0.980853 (12)	0.578926 (15)	0.02838 (8)
Cl1	0.53514 (7)	0.79998 (5)	−0.03442 (5)	0.0761 (2)
Cl2	0.92843 (7)	1.31020 (5)	0.55213 (9)	0.1053 (3)
O1	0.63814 (10)	0.91758 (8)	0.46442 (10)	0.0409 (3)
O2	0.49984 (11)	0.95064 (9)	0.33241 (11)	0.0458 (3)
O3	0.64805 (10)	1.07718 (8)	0.52693 (11)	0.0422 (3)
O4	0.51122 (10)	1.10927 (8)	0.39242 (11)	0.0405 (3)
O5	1.04739 (13)	1.05214 (11)	0.83585 (15)	0.0658 (5)
N1	0.70894 (11)	0.96124 (10)	0.71646 (12)	0.0347 (3)
N2	1.06037 (13)	0.95243 (12)	0.71450 (16)	0.0502 (4)
C1	0.58602 (14)	0.91427 (10)	0.36697 (15)	0.0343 (4)
C2	0.62814 (15)	0.86185 (11)	0.28384 (15)	0.0373 (4)
C3	0.57253 (17)	0.85814 (12)	0.17511 (16)	0.0433 (4)
H3	0.5123	0.8900	0.1529	0.052*
C4	0.6080 (2)	0.80633 (14)	0.10029 (17)	0.0518 (5)
C5	0.6965 (2)	0.75909 (16)	0.1303 (2)	0.0661 (7)
H5	0.7186	0.7242	0.0790	0.079*
C6	0.7521 (2)	0.76385 (16)	0.2371 (2)	0.0678 (7)
H6	0.8127	0.7322	0.2581	0.081*
C7	0.71904 (18)	0.81551 (13)	0.31447 (19)	0.0493 (5)
H7	0.7579	0.8188	0.3865	0.059*
C8	0.60290 (14)	1.12046 (10)	0.44801 (14)	0.0319 (3)
C9	0.66516 (15)	1.19115 (11)	0.41815 (16)	0.0368 (4)
C10	0.75758 (17)	1.21469 (12)	0.48927 (19)	0.0463 (5)
H10	0.7814	1.1867	0.5549	0.056*
C11	0.81362 (19)	1.28015 (14)	0.4613 (2)	0.0620 (6)
C12	0.7809 (2)	1.32217 (15)	0.3639 (3)	0.0749 (8)
H12	0.8202	1.3659	0.3461	0.090*
C13	0.6896 (2)	1.29872 (15)	0.2938 (3)	0.0700 (7)
H13	0.6668	1.3267	0.2280	0.084*
C14	0.63081 (19)	1.23348 (13)	0.32036 (19)	0.0506 (5)
H14	0.5685	1.2182	0.2727	0.061*
C15	0.81050 (14)	0.97600 (11)	0.70628 (15)	0.0361 (4)
H15	0.8250	0.9911	0.6366	0.043*
C16	0.89570 (14)	0.97002 (11)	0.79394 (15)	0.0353 (4)
C17	0.87265 (15)	0.94853 (12)	0.89783 (15)	0.0412 (4)
H17	0.9273	0.9452	0.9595	0.049*
C18	0.76805 (17)	0.93223 (14)	0.90842 (16)	0.0468 (5)
H18	0.7512	0.9167	0.9770	0.056*
C19	0.68845 (15)	0.93925 (13)	0.81604 (16)	0.0425 (4)
H19	0.6178	0.9282	0.8237	0.051*
C20	1.00821 (15)	0.99464 (13)	0.78250 (17)	0.0429 (4)
C21	1.02241 (19)	0.87796 (16)	0.6595 (2)	0.0649 (7)
H211	0.9638	0.8574	0.6937	0.078*
H212	1.0803	0.8391	0.6717	0.078*
C22	0.9840 (3)	0.8867 (3)	0.5347 (3)	0.1069 (13)
H221	0.9232	0.9220	0.5219	0.160*
H222	0.9635	0.8354	0.5030	0.160*
H223	1.0410	0.9083	0.5003	0.160*
C23	1.17124 (19)	0.97631 (17)	0.7067 (2)	0.0660 (7)
H231	1.1878	0.9589	0.6353	0.079*
H232	1.1761	1.0341	0.7092	0.079*
C24	1.25301 (19)	0.9423 (2)	0.7983 (3)	0.0759 (8)
H241	1.2468	0.8852	0.7983	0.114*
H242	1.3238	0.9570	0.7864	0.114*
H243	1.2409	0.9630	0.8689	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02465 (11)	0.03345 (13)	0.02565 (12)	−0.00047 (7)	0.00020 (8)	−0.00112 (8)
Cl1	0.1050 (5)	0.0886 (5)	0.0378 (3)	−0.0216 (4)	0.0206 (3)	−0.0159 (3)
Cl2	0.0775 (5)	0.0876 (5)	0.1497 (8)	−0.0475 (4)	0.0157 (5)	−0.0400 (6)
O1	0.0411 (7)	0.0475 (8)	0.0346 (7)	0.0051 (6)	0.0077 (5)	−0.0066 (6)
O2	0.0428 (7)	0.0565 (8)	0.0370 (7)	0.0102 (6)	0.0033 (6)	−0.0131 (6)
O3	0.0388 (7)	0.0412 (7)	0.0432 (7)	−0.0097 (6)	−0.0030 (5)	0.0079 (6)
O4	0.0352 (7)	0.0427 (7)	0.0420 (7)	−0.0059 (5)	0.0018 (5)	0.0078 (6)
O5	0.0505 (9)	0.0705 (11)	0.0739 (11)	−0.0157 (8)	0.0032 (8)	−0.0230 (9)
N1	0.0292 (7)	0.0439 (8)	0.0293 (7)	0.0024 (6)	0.0000 (6)	0.0020 (6)
N2	0.0353 (8)	0.0583 (11)	0.0583 (11)	−0.0018 (8)	0.0114 (7)	−0.0050 (9)
C1	0.0339 (9)	0.0340 (9)	0.0370 (9)	−0.0054 (7)	0.0115 (7)	−0.0037 (7)
C2	0.0426 (10)	0.0342 (9)	0.0386 (9)	−0.0065 (7)	0.0175 (8)	−0.0034 (7)
C3	0.0485 (11)	0.0447 (11)	0.0396 (10)	−0.0073 (9)	0.0152 (8)	−0.0041 (8)
C4	0.0713 (14)	0.0516 (12)	0.0372 (10)	−0.0171 (11)	0.0227 (10)	−0.0097 (9)
C5	0.0912 (19)	0.0568 (14)	0.0586 (14)	0.0074 (13)	0.0371 (13)	−0.0140 (12)
C6	0.0772 (17)	0.0645 (16)	0.0668 (15)	0.0230 (13)	0.0275 (13)	−0.0051 (13)
C7	0.0532 (12)	0.0502 (12)	0.0475 (11)	0.0052 (9)	0.0175 (9)	−0.0023 (9)
C8	0.0336 (8)	0.0320 (8)	0.0313 (8)	−0.0012 (7)	0.0089 (7)	−0.0025 (7)
C9	0.0388 (9)	0.0325 (9)	0.0422 (10)	−0.0010 (7)	0.0160 (7)	−0.0024 (7)
C10	0.0464 (11)	0.0413 (10)	0.0532 (12)	−0.0095 (9)	0.0141 (9)	−0.0081 (9)
C11	0.0547 (13)	0.0458 (12)	0.0905 (18)	−0.0178 (10)	0.0269 (12)	−0.0182 (12)
C12	0.0827 (19)	0.0418 (12)	0.112 (2)	−0.0138 (12)	0.0507 (17)	0.0072 (14)
C13	0.0880 (19)	0.0502 (14)	0.0798 (18)	0.0066 (13)	0.0367 (15)	0.0238 (13)
C14	0.0570 (13)	0.0455 (11)	0.0523 (12)	0.0032 (9)	0.0178 (10)	0.0091 (9)
C15	0.0328 (9)	0.0463 (10)	0.0284 (8)	0.0019 (7)	0.0030 (7)	0.0019 (7)
C16	0.0298 (8)	0.0374 (9)	0.0368 (9)	0.0048 (7)	−0.0002 (7)	−0.0041 (7)
C17	0.0390 (10)	0.0477 (11)	0.0323 (9)	0.0063 (8)	−0.0071 (7)	0.0005 (8)
C18	0.0478 (11)	0.0610 (13)	0.0305 (9)	0.0047 (9)	0.0032 (8)	0.0074 (9)
C19	0.0341 (9)	0.0564 (12)	0.0366 (9)	−0.0003 (8)	0.0053 (7)	0.0065 (9)
C20	0.0325 (9)	0.0496 (11)	0.0430 (10)	0.0018 (8)	−0.0034 (8)	−0.0001 (9)
C21	0.0471 (12)	0.0638 (15)	0.0857 (17)	0.0030 (11)	0.0162 (12)	−0.0228 (13)
C22	0.087 (2)	0.141 (3)	0.086 (2)	0.022 (2)	−0.0043 (18)	−0.052 (2)
C23	0.0429 (12)	0.0784 (18)	0.0805 (18)	−0.0069 (11)	0.0214 (12)	0.0006 (14)
C24	0.0368 (12)	0.092 (2)	0.100 (2)	0.0002 (12)	0.0133 (12)	−0.0083 (17)

Geometric parameters (Å, º) top

Cu1—Cu1ⁱ	2.6314 (4)	C9—C10	1.386 (3)
Cu1—O1	1.9791 (13)	C9—C14	1.388 (3)
Cu1—O2ⁱ	1.9688 (13)	C10—C11	1.378 (3)
Cu1—O3	1.9755 (13)	C10—H10	0.9300
Cu1—O4ⁱ	1.9703 (13)	C11—C12	1.378 (4)
Cu1—N1	2.1454 (14)	C12—H12	0.9300
Cl1—C4	1.740 (2)	C13—C12	1.369 (4)
Cl2—C11	1.741 (3)	C13—H13	0.9300
O1—C1	1.255 (2)	C14—C13	1.388 (3)
O2—C1	1.255 (2)	C14—H14	0.9300
O2—Cu1ⁱ	1.9688 (13)	C15—H15	0.9300
O3—C8	1.259 (2)	C16—C15	1.383 (2)
O4—Cu1ⁱ	1.9703 (13)	C16—C20	1.506 (3)
O4—C8	1.251 (2)	C17—C16	1.388 (3)
O5—C20	1.218 (3)	C17—C18	1.374 (3)
N1—C15	1.330 (2)	C17—H17	0.9300
N1—C19	1.330 (2)	C18—H18	0.9300
N2—C20	1.340 (3)	C19—C18	1.379 (3)
N2—C21	1.458 (3)	C19—H19	0.9300
N2—C23	1.472 (3)	C21—C22	1.519 (4)
C1—C2	1.500 (2)	C21—H211	0.9700
C2—C3	1.388 (3)	C21—H212	0.9700
C2—C7	1.383 (3)	C22—H221	0.9600
C3—C4	1.384 (3)	C22—H222	0.9600
C3—H3	0.9300	C22—H223	0.9600
C4—C5	1.367 (4)	C23—C24	1.496 (4)
C5—C6	1.369 (4)	C23—H232	0.9700
C5—H5	0.9300	C23—H231	0.9700
C6—H6	0.9300	C24—H241	0.9600
C7—C6	1.392 (3)	C24—H242	0.9600
C7—H7	0.9300	C24—H243	0.9600
C8—C9	1.499 (2)

O1—Cu1—Cu1ⁱ	87.05 (4)	C10—C11—Cl2	118.7 (2)
O1—Cu1—N1	98.53 (6)	C10—C11—C12	121.7 (2)
O2ⁱ—Cu1—Cu1ⁱ	81.29 (4)	C12—C11—Cl2	119.57 (19)
O2ⁱ—Cu1—O1	168.33 (6)	C11—C12—H12	120.5
O2ⁱ—Cu1—O3	89.25 (6)	C13—C12—C11	119.1 (2)
O2ⁱ—Cu1—O4ⁱ	88.70 (6)	C13—C12—H12	120.5
O2ⁱ—Cu1—N1	93.11 (6)	C12—C13—C14	120.5 (3)
O3—Cu1—Cu1ⁱ	83.65 (4)	C12—C13—H13	119.8
O3—Cu1—O1	89.21 (6)	C14—C13—H13	119.8
O3—Cu1—N1	93.79 (6)	C9—C14—C13	119.9 (2)
O4ⁱ—Cu1—Cu1ⁱ	84.77 (4)	C9—C14—H14	120.0
O4ⁱ—Cu1—O1	90.49 (6)	C13—C14—H14	120.0
O4ⁱ—Cu1—O3	168.41 (5)	N1—C15—C16	123.41 (17)
O4ⁱ—Cu1—N1	97.71 (6)	N1—C15—H15	118.3
N1—Cu1—Cu1ⁱ	173.85 (4)	C16—C15—H15	118.3
C1—O1—Cu1	119.39 (12)	C15—C16—C17	117.64 (17)
C1—O2—Cu1ⁱ	126.70 (12)	C15—C16—C20	122.09 (17)
C8—O3—Cu1	123.38 (11)	C17—C16—C20	119.91 (16)
C8—O4—Cu1ⁱ	122.52 (12)	C16—C17—H17	120.4
C15—N1—Cu1	120.69 (12)	C18—C17—C16	119.14 (16)
C19—N1—Cu1	120.94 (12)	C18—C17—H17	120.4
C19—N1—C15	118.21 (15)	C17—C18—C19	119.09 (18)
C20—N2—C21	125.21 (18)	C17—C18—H18	120.5
C20—N2—C23	117.7 (2)	C19—C18—H18	120.5
C21—N2—C23	116.48 (19)	N1—C19—C18	122.49 (18)
O1—C1—O2	125.52 (16)	N1—C19—H19	118.8
O1—C1—C2	118.14 (16)	C18—C19—H19	118.8
O2—C1—C2	116.33 (16)	O5—C20—N2	123.2 (2)
C3—C2—C1	119.11 (17)	O5—C20—C16	118.15 (19)
C7—C2—C1	121.25 (17)	N2—C20—C16	118.64 (18)
C7—C2—C3	119.61 (18)	N2—C21—C22	113.6 (3)
C2—C3—H3	120.5	N2—C21—H211	108.9
C4—C3—C2	119.0 (2)	N2—C21—H212	108.9
C4—C3—H3	120.5	C22—C21—H211	108.9
C3—C4—Cl1	118.5 (2)	C22—C21—H212	108.9
C5—C4—Cl1	119.61 (17)	H211—C21—H212	107.7
C5—C4—C3	121.8 (2)	C21—C22—H221	109.5
C4—C5—C6	119.0 (2)	C21—C22—H222	109.5
C4—C5—H5	120.5	C21—C22—H223	109.5
C6—C5—H5	120.5	H221—C22—H222	109.5
C5—C6—C7	120.8 (2)	H221—C22—H223	109.5
C5—C6—H6	119.6	H222—C22—H223	109.5
C7—C6—H6	119.6	N2—C23—C24	113.1 (2)
C2—C7—C6	119.8 (2)	N2—C23—H232	109.0
C2—C7—H7	120.1	N2—C23—H231	109.0
C6—C7—H7	120.1	C24—C23—H232	109.0
O3—C8—C9	116.81 (15)	C24—C23—H231	109.0
O4—C8—O3	125.68 (16)	H232—C23—H231	107.8
O4—C8—C9	117.52 (16)	C23—C24—H243	109.5
C10—C9—C8	119.60 (18)	C23—C24—H242	109.5
C10—C9—C14	119.75 (19)	C23—C24—H241	109.5
C14—C9—C8	120.64 (18)	H243—C24—H242	109.5
C9—C10—H10	120.5	H243—C24—H241	109.5
C11—C10—C9	119.0 (2)	H242—C24—H241	109.5
C11—C10—H10	120.5

Cu1ⁱ—Cu1—O1—C1	−1.49 (13)	O1—C1—C2—C3	−179.12 (17)
O2ⁱ—Cu1—O1—C1	−2.7 (4)	O1—C1—C2—C7	2.9 (3)
O3—Cu1—O1—C1	−85.17 (14)	O2—C1—C2—C3	1.7 (3)
O4ⁱ—Cu1—O1—C1	83.25 (14)	O2—C1—C2—C7	−176.27 (18)
N1—Cu1—O1—C1	−178.88 (13)	C1—C2—C3—C4	−176.33 (17)
Cu1ⁱ—Cu1—O3—C8	−0.31 (14)	C7—C2—C3—C4	1.7 (3)
O1—Cu1—O3—C8	86.81 (15)	C3—C2—C7—C6	−1.9 (3)
O2ⁱ—Cu1—O3—C8	−81.63 (15)	C1—C2—C7—C6	176.0 (2)
O4ⁱ—Cu1—O3—C8	−1.8 (4)	C2—C3—C4—Cl1	178.00 (15)
N1—Cu1—O3—C8	−174.70 (14)	C2—C3—C4—C5	−0.4 (3)
O1—Cu1—N1—C15	52.96 (15)	Cl1—C4—C5—C6	−179.0 (2)
O1—Cu1—N1—C19	−131.61 (16)	C3—C4—C5—C6	−0.7 (4)
O2ⁱ—Cu1—N1—C15	−126.27 (15)	C4—C5—C6—C7	0.4 (4)
O2ⁱ—Cu1—N1—C19	49.16 (16)	C2—C7—C6—C5	0.9 (4)
O3—Cu1—N1—C15	−36.82 (15)	O3—C8—C9—C10	−12.2 (2)
O3—Cu1—N1—C19	138.61 (16)	O3—C8—C9—C14	168.16 (18)
O4ⁱ—Cu1—N1—C15	144.62 (14)	O4—C8—C9—C10	168.11 (17)
O4ⁱ—Cu1—N1—C19	−39.95 (16)	O4—C8—C9—C14	−11.5 (3)
Cu1—O1—C1—O2	2.8 (3)	C8—C9—C10—C11	−179.51 (18)
Cu1—O1—C1—C2	−176.35 (11)	C14—C9—C10—C11	0.1 (3)
Cu1ⁱ—O2—C1—O1	−2.6 (3)	C8—C9—C14—C13	−179.86 (19)
Cu1ⁱ—O2—C1—C2	176.52 (12)	C10—C9—C14—C13	0.5 (3)
Cu1—O3—C8—O4	0.1 (3)	C9—C10—C11—Cl2	179.02 (16)
Cu1—O3—C8—C9	−179.54 (11)	C9—C10—C11—C12	−0.7 (3)
Cu1ⁱ—O4—C8—O3	0.3 (3)	C10—C11—C12—C13	0.7 (4)
Cu1ⁱ—O4—C8—C9	179.96 (11)	Cl2—C11—C12—C13	−179.1 (2)
Cu1—N1—C15—C16	175.23 (14)	C14—C13—C12—C11	0.0 (4)
C19—N1—C15—C16	−0.3 (3)	C9—C14—C13—C12	−0.6 (4)
Cu1—N1—C19—C18	−174.76 (16)	C17—C16—C15—N1	−0.9 (3)
C15—N1—C19—C18	0.8 (3)	C20—C16—C15—N1	−174.04 (18)
C21—N2—C20—O5	172.2 (2)	C15—C16—C20—O5	113.2 (2)
C21—N2—C20—C16	−7.7 (3)	C15—C16—C20—N2	−66.8 (3)
C23—N2—C20—O5	1.4 (3)	C17—C16—C20—O5	−59.7 (3)
C23—N2—C20—C16	−178.50 (19)	C17—C16—C20—N2	120.2 (2)
C20—N2—C21—C22	107.6 (3)	C18—C17—C16—C15	1.7 (3)
C23—N2—C21—C22	−81.5 (3)	C18—C17—C16—C20	174.99 (19)
C20—N2—C23—C24	83.6 (3)	C16—C17—C18—C19	−1.3 (3)
C21—N2—C23—C24	−88.0 (3)	N1—C19—C18—C17	0.0 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O5ⁱⁱ	0.93	2.45	3.221 (3)	140

Symmetry code: (ii) −x+2, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₇H₄ClO₂)₄(C₁₀H₁₄N₂O)₂]
M_r	1105.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.6077 (4), 16.7569 (5), 12.1402 (4)
β (°)	99.647 (2)
V (Å³)	2528.54 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART BREEZE CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.711, 0.724
No. of measured, independent and observed [I > 2σ(I)] reflections	78293, 5166, 4702
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.04
No. of reflections	5166
No. of parameters	309
No. of restraints	85
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.45

Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cu1—O1	1.9791 (13)	Cu1—O4ⁱ	1.9703 (13)
Cu1—O2ⁱ	1.9688 (13)	Cu1—N1	2.1454 (14)
Cu1—O3	1.9755 (13)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O5ⁱⁱ	0.93	2.45	3.221 (3)	140

Symmetry code: (ii) −x+2, −y+2, −z+2.

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 Planning Organization).

References

Aydın, Ö., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012). Acta Cryst. E68, m409–m410. CSD CrossRef IUCr Journals 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
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009c). Acta Cryst. E65, m1582–m1583. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Necefoğlu, H. & Balcı, M. (1995). Acta Cryst. C51, 2020–2023. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T., Sağlam, E. G., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2011). Acta Cryst. E67, m28–m29. Web of Science CrossRef IUCr Journals Google Scholar
Hökelek, T., Yılmaz, F., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009a). Acta Cryst. E65, m955–m956. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Yılmaz, F., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009b). Acta Cryst. E65, m1328–m1329. 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
Necefoğlu, H., Çimen, E., Tercan, B., Dal, H. & Hökelek, T. (2010a). Acta Cryst. E66, m334–m335. Web of Science CSD CrossRef IUCr Journals Google Scholar
Necefoğlu, H., Çimen, E., Tercan, B., Dal, H. & Hökelek, T. (2010b). Acta Cryst. E66, m485–m486. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Speier, G. & Fulop, V. (1989). J. Chem. Soc. Dalton Trans. pp. 2331–2333. CSD CrossRef Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Usubaliev, B. T., Movsumov, E. M., Musaev, F. N., Nadzhafov, G. N., Amiraslanov, I. R. & Mamedov, Kh. S. (1980). Koord. Khim. 6, 1091–1096. CAS Google Scholar

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