Tetra­kis(μ-4-methyl­benzoato-κ2O:O′)bis­[(isonicotinamide-κN)copper(II)]

Necefoğlu, H.; Çimen, E.; Tercan, B.; Dal, H.; Hökelek, T.

doi:10.1107/S1600536810006513

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m334-m335

doi:10.1107/S1600536810006513

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Tetrakis(μ-4-methylbenzoato-κ²O:O′)bis[(isonicotinamide-κN)copper(II)]

Hacali Necefoğlu,^a Efdal Çimen,^a Barış Tercan,^b Hakan Dal ^c and Tuncer Hökelek ^d ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bDepartment of Physics, Karabük University, 78050 Karabük, Turkey, ^cDepartment of Chemistry, Faculty of Science, Anadolu University, 26470 Yenibağlar, Eskişehir, Turkey, and ^dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 18 February 2010; accepted 19 February 2010; online 27 February 2010)

In the title centrosymmetric binuclear complex, [Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂], the Cu atoms [Cu⋯Cu = 2.6375 (6) Å] are bridged by four 4-methylbenzoate (PMB) ligands. The four nearest O atoms around each Cu^II ion form a distorted square-planar arrangement, and the distorted square-pyramidal coordination is completed by the pyridine N atom of the isonicotinamide (INA) ligand. Each Cu^II ion is displaced by 0.2633 (1) Å from the plane of the four O atoms, with an average Cu—O distance of 1.974 (2) Å. The dihedral angles between carboxylate groups and the adjacent benzene rings are 7.88 (19) and 9.68 (10)°, while the benzene rings are oriented at a dihedral angle of 85.90 (9)°. The pyridine ring is oriented at dihedral angles of 8.59 (7) and 83.89 (9)° with respect to the benzene rings. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π contacts between the benzene rings and between the pyridine and benzene rings, [centroid–centroid distances = 3.563 (2) and 3.484 (2) Å, respectively] may further stabilize the crystal structure.

Related literature

For niacin, see: Krishnamachari (1974 ), and for the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1995 , 2009a ,b ,c ); Speier & Fulop (1989 ); Usubaliev et al. (1980 ).

Experimental

Crystal data

[Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂]
M_r = 911.88
Monoclinic, P 2₁ /c
a = 11.2305 (2) Å
b = 23.4691 (4) Å
c = 8.0087 (1) Å
β = 102.128 (1)°
V = 2063.74 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 101 K
0.30 × 0.24 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.735, T_max = 0.862
20056 measured reflections
5101 independent reflections
3629 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.087
S = 1.01
5101 reflections
281 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9733 (18)
Cu1—O2ⁱ	1.9703 (18)
Cu1—O3	1.9687 (18)
Cu1—O4	1.9836 (18)
Cu1—N1	2.161 (2)
Symmetry code: (i) -x+2, -y+2, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5ⁱⁱ	0.89 (3)	2.11 (3)	2.984 (3)	169 (3)
Symmetry code: (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536810006513/xu2729sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006513/xu2729Isup2.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 two INA and four 4-methylbenzoate (PMB) ligands. The crystal structures of similar complexes of Cu²⁺ and Zn²⁺ 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), [Zn₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009a), [Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂].2H₂O (Hökelek et al., 2009b) and [Zn₂(C₉H₁₀NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009c) have also been reported. In these structures, the benzoate ion acts as a bidentate ligand.

The title dimeric complex, [Cu₂(PMB)₄(INA)₂], has a centre of symmetry and two Cu^II ions are surrounded by four PMB groups and two INA ligands (Fig. 1). The INA ligands are coordinated to Cu^II ions through pyridine N atoms only. The PMB groups act as bridging ligands. The Cu···Cu' distance is 2.6375 (6) Å. The average Cu—O distance is 1.9740 (18) Å (Table 1), and four O atoms of the bridging PMB ligands around each Cu^II ion form a distorted square plane. The Cu^II ion lies 0.2633 (1) Å below the least-squares plane. The average O—Cu—O bond angle is 89.39 (8)°. A distorted square-pyramidal arrangement around each Cu^II ion is completed by the pyridine N atom of INA ligand at 2.162 (2) Å (Table 1) from the Cu atom. The N1—Cu1···Cu1' angle is 171.10 (6)° and the dihedral angle between plane through atoms Cu1, O1, O2, C1, Cu1', O1', O2', C1' and the plane through Cu1, O3, O4, C9, Cu1', O3', O4' and C9' atoms is 89.91 (9)°. The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O3/O4/C9)] and the adjacent benzene rings A (C2—C7) and B (C10—C15) are 7.88 (19) and 9.68 (10) °, respectively, while that between rings A and B is A/B = 85.90 (9)°. Ring C (N1/C17—C21) is oriented with respect to rings A and B at dihedral angles A/C = 8.59 (7) and B/C = 83.89 (9) °.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 2) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. The π–π contacts between the benzene rings and benzene and pyridine rings, Cg1—Cg1ⁱ and Cg3—Cg1ⁱⁱ, [symmetry codes (i): 1 - x, -y, 1 - z; (ii) x, y, z - 1, where Cg1 and Cg3 are centroids of the rings A (C2—C7) and C (N1/C17—C21)] may further stabilize the structure, with centroid-centroid distances of 3.563 (2) and 3.484 (2) Å, respectively.

Related literature top

For niacin, see: Krishnamachari (1974), and for the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1995, 2009a,b,c); Speier & Fulop (1989); Usubaliev et al. (1980).

Experimental top

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.25 g, 5 mmol) in H₂O (50 ml) and isonicotinamide (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 4-methylbenzoate (1.58 g, 10 mmol) in H₂O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving green 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 20% probability level. Primed atoms are generated by the symmetry operator: (') 2-x, 2-y, 2-z.

Tetrakis(µ-4-methylbenzoato-κ²O:O')bis[(isonicotinamide- κN)copper(II)] top

Crystal data top

[Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂]	F(000) = 940
M_r = 911.88	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3119 reflections
a = 11.2305 (2) Å	θ = 2.5–25.4°
b = 23.4691 (4) Å	µ = 1.10 mm⁻¹
c = 8.0087 (1) Å	T = 101 K
β = 102.128 (1)°	Block, green
V = 2063.74 (6) Å³	0.30 × 0.24 × 0.14 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5101 independent reflections
Radiation source: fine-focus sealed tube	3629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→11
T_min = 0.735, T_max = 0.862	k = −31→31
20056 measured reflections	l = −10→10

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0224P)² + 2.5778P] where P = (F_o² + 2F_c²)/3
5101 reflections	(Δ/σ)_max = 0.001
281 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

[Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂]	V = 2063.74 (6) Å³
M_r = 911.88	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.2305 (2) Å	µ = 1.10 mm⁻¹
b = 23.4691 (4) Å	T = 101 K
c = 8.0087 (1) Å	0.30 × 0.24 × 0.14 mm
β = 102.128 (1)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5101 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3629 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.862	R_int = 0.062
20056 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.47 e Å⁻³
5101 reflections	Δρ_min = −0.70 e Å⁻³
281 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 > 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
Cu1	0.95060 (3)	0.966319 (13)	1.09852 (4)	0.01099 (9)
O1	0.81764 (18)	0.95045 (8)	0.9002 (2)	0.0191 (4)
O2	0.90275 (17)	1.00855 (8)	0.7371 (2)	0.0168 (4)
O3	1.04702 (19)	0.90818 (8)	1.0089 (2)	0.0203 (4)
O4	0.86037 (17)	1.03478 (8)	1.1481 (2)	0.0180 (4)
O5	0.70039 (18)	0.75397 (8)	1.5592 (2)	0.0183 (4)
N1	0.8976 (2)	0.90548 (9)	1.2719 (3)	0.0139 (5)
N2	0.7819 (3)	0.81071 (11)	1.7825 (3)	0.0200 (6)
H2A	0.752 (3)	0.7887 (13)	1.854 (4)	0.022 (8)*
H2B	0.818 (3)	0.8419 (16)	1.818 (4)	0.047 (12)*
C1	0.8203 (3)	0.97549 (10)	0.7606 (3)	0.0130 (5)
C2	0.7165 (2)	0.96483 (11)	0.6131 (3)	0.0122 (5)
C3	0.6147 (2)	0.93399 (11)	0.6322 (3)	0.0138 (6)
H3	0.6095	0.9196	0.7413	0.017*
C4	0.5205 (3)	0.92415 (11)	0.4928 (3)	0.0148 (6)
H4	0.4508	0.9034	0.5077	0.018*
C5	0.5265 (3)	0.94428 (11)	0.3308 (3)	0.0147 (6)
C6	0.6286 (3)	0.97476 (11)	0.3131 (3)	0.0159 (6)
H6	0.6344	0.9885	0.2035	0.019*
C7	0.7225 (2)	0.98563 (10)	0.4518 (3)	0.0128 (5)
H7	0.7911	1.0072	0.4371	0.015*
C8	0.4259 (3)	0.93213 (12)	0.1789 (3)	0.0221 (6)
H8A	0.3516	0.9219	0.2179	0.033*
H8B	0.4498	0.9005	0.1132	0.033*
H8C	0.4106	0.9661	0.1064	0.033*
C9	1.1213 (2)	0.91754 (11)	0.9141 (3)	0.0133 (5)
C10	1.1926 (3)	0.86716 (11)	0.8745 (3)	0.0142 (6)
C11	1.1638 (3)	0.81263 (11)	0.9227 (3)	0.0188 (6)
H11	1.0971	0.8075	0.9770	0.023*
C12	1.2313 (3)	0.76602 (12)	0.8923 (3)	0.0224 (7)
H12	1.2090	0.7291	0.9232	0.027*
C13	1.3314 (3)	0.77232 (12)	0.8172 (3)	0.0206 (6)
C14	1.3589 (3)	0.82663 (12)	0.7674 (3)	0.0203 (6)
H14	1.4264	0.8318	0.7146	0.024*
C15	1.2897 (3)	0.87351 (11)	0.7932 (3)	0.0176 (6)
H15	1.3087	0.9101	0.7552	0.021*
C16	1.4105 (3)	0.72204 (13)	0.7957 (4)	0.0284 (7)
H16A	1.3606	0.6874	0.7780	0.043*
H16B	1.4748	0.7177	0.8985	0.043*
H16C	1.4473	0.7283	0.6967	0.043*
C17	0.7944 (2)	0.87572 (10)	1.2239 (3)	0.0134 (5)
H17	0.7501	0.8796	1.1096	0.016*
C18	0.7487 (2)	0.83964 (11)	1.3316 (3)	0.0124 (5)
H18	0.6757	0.8188	1.2916	0.015*
C19	0.8121 (2)	0.83446 (10)	1.4999 (3)	0.0127 (5)
C20	0.9206 (3)	0.86403 (11)	1.5496 (3)	0.0170 (6)
H20	0.9674	0.8604	1.6626	0.020*
C21	0.9600 (3)	0.89878 (11)	1.4330 (3)	0.0152 (6)
H21	1.0346	0.9188	1.4683	0.018*
C22	0.7601 (3)	0.79620 (11)	1.6172 (3)	0.0142 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01279 (18)	0.01089 (15)	0.00968 (13)	−0.00136 (15)	0.00323 (11)	0.00055 (13)
O1	0.0192 (11)	0.0233 (11)	0.0133 (9)	−0.0080 (9)	0.0000 (8)	0.0042 (7)
O2	0.0154 (11)	0.0202 (10)	0.0137 (8)	−0.0071 (8)	0.0003 (7)	0.0035 (7)
O3	0.0299 (13)	0.0129 (9)	0.0236 (10)	0.0023 (9)	0.0177 (9)	0.0009 (8)
O4	0.0208 (11)	0.0142 (9)	0.0221 (9)	0.0023 (9)	0.0116 (8)	0.0033 (8)
O5	0.0255 (12)	0.0147 (10)	0.0160 (9)	−0.0046 (9)	0.0077 (8)	0.0016 (7)
N1	0.0156 (13)	0.0140 (11)	0.0130 (10)	0.0012 (10)	0.0050 (9)	0.0011 (8)
N2	0.0348 (17)	0.0132 (12)	0.0140 (11)	−0.0057 (12)	0.0094 (11)	0.0010 (9)
C1	0.0174 (15)	0.0085 (13)	0.0143 (11)	0.0016 (11)	0.0058 (10)	−0.0026 (9)
C2	0.0137 (14)	0.0096 (11)	0.0128 (11)	0.0027 (11)	0.0018 (9)	−0.0023 (10)
C3	0.0153 (16)	0.0133 (13)	0.0141 (12)	0.0024 (11)	0.0061 (10)	0.0007 (10)
C4	0.0127 (15)	0.0136 (13)	0.0179 (12)	−0.0008 (11)	0.0028 (11)	−0.0016 (10)
C5	0.0161 (16)	0.0110 (12)	0.0162 (12)	0.0039 (11)	0.0011 (10)	−0.0026 (10)
C6	0.0218 (16)	0.0124 (13)	0.0138 (11)	0.0015 (11)	0.0045 (11)	0.0006 (10)
C7	0.0144 (15)	0.0103 (12)	0.0150 (12)	0.0002 (11)	0.0062 (10)	0.0001 (9)
C8	0.0226 (18)	0.0209 (15)	0.0198 (13)	−0.0015 (13)	−0.0026 (12)	−0.0029 (11)
C9	0.0125 (15)	0.0159 (13)	0.0099 (11)	−0.0029 (11)	−0.0013 (10)	−0.0023 (9)
C10	0.0161 (16)	0.0154 (13)	0.0104 (11)	0.0002 (11)	0.0013 (10)	−0.0003 (10)
C11	0.0192 (17)	0.0180 (14)	0.0195 (13)	−0.0011 (12)	0.0049 (11)	0.0025 (11)
C12	0.0265 (19)	0.0149 (14)	0.0241 (14)	0.0034 (13)	0.0017 (12)	0.0022 (11)
C13	0.0245 (18)	0.0209 (15)	0.0149 (13)	0.0078 (13)	0.0009 (11)	−0.0017 (11)
C14	0.0202 (17)	0.0247 (16)	0.0171 (13)	0.0041 (13)	0.0063 (11)	−0.0008 (11)
C15	0.0222 (17)	0.0136 (13)	0.0160 (12)	0.0004 (12)	0.0016 (11)	0.0003 (10)
C16	0.036 (2)	0.0219 (16)	0.0264 (15)	0.0131 (14)	0.0043 (14)	0.0000 (12)
C17	0.0183 (16)	0.0113 (12)	0.0110 (11)	0.0004 (11)	0.0036 (10)	−0.0014 (9)
C18	0.0138 (15)	0.0112 (12)	0.0130 (11)	−0.0006 (11)	0.0049 (10)	−0.0026 (10)
C19	0.0177 (16)	0.0093 (12)	0.0127 (11)	0.0007 (11)	0.0065 (10)	−0.0005 (9)
C20	0.0202 (17)	0.0189 (14)	0.0108 (11)	−0.0003 (12)	0.0003 (10)	0.0026 (10)
C21	0.0140 (15)	0.0152 (13)	0.0160 (12)	−0.0036 (11)	0.0026 (10)	0.0002 (10)
C22	0.0186 (16)	0.0134 (13)	0.0118 (12)	0.0009 (12)	0.0060 (11)	0.0033 (10)

Geometric parameters (Å, º) top

Cu1—Cu1ⁱ	2.6375 (6)	C8—H8A	0.9800
Cu1—O1	1.9733 (18)	C8—H8B	0.9800
Cu1—O2ⁱ	1.9703 (18)	C8—H8C	0.9800
Cu1—O3	1.9687 (18)	C9—O4ⁱ	1.259 (3)
Cu1—O4	1.9836 (18)	C9—C10	1.499 (4)
Cu1—N1	2.161 (2)	C10—C11	1.394 (4)
O1—C1	1.269 (3)	C10—C15	1.390 (4)
O2—Cu1ⁱ	1.9703 (18)	C11—C12	1.381 (4)
O2—C1	1.252 (3)	C11—H11	0.9500
O3—C9	1.259 (3)	C12—C13	1.389 (4)
O4—C9ⁱ	1.259 (3)	C12—H12	0.9500
O5—C22	1.232 (3)	C13—C14	1.389 (4)
N1—C17	1.338 (3)	C13—C16	1.508 (4)
N1—C21	1.342 (3)	C14—C15	1.387 (4)
N2—C22	1.339 (3)	C14—H14	0.9500
N2—H2A	0.89 (3)	C15—H15	0.9500
N2—H2B	0.85 (4)	C16—H16A	0.9800
C1—C2	1.497 (3)	C16—H16B	0.9800
C2—C3	1.388 (4)	C16—H16C	0.9800
C2—C7	1.397 (3)	C17—C18	1.382 (3)
C3—C4	1.387 (4)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.391 (3)
C4—C5	1.395 (3)	C18—H18	0.9500
C4—H4	0.9500	C19—C20	1.387 (4)
C5—C6	1.384 (4)	C19—C22	1.503 (3)
C5—C8	1.503 (4)	C20—C21	1.381 (3)
C6—C7	1.385 (4)	C20—H20	0.9500
C6—H6	0.9500	C21—H21	0.9500
C7—H7	0.9500

O1—Cu1—Cu1ⁱ	88.51 (5)	H8A—C8—H8B	109.5
O1—Cu1—O4	88.96 (8)	H8A—C8—H8C	109.5
O1—Cu1—N1	97.37 (8)	H8B—C8—H8C	109.5
O2ⁱ—Cu1—Cu1ⁱ	79.79 (5)	O3—C9—O4ⁱ	125.3 (2)
O2ⁱ—Cu1—O1	168.28 (7)	O3—C9—C10	116.2 (2)
O2ⁱ—Cu1—O4	90.82 (8)	O4ⁱ—C9—C10	118.6 (2)
O2ⁱ—Cu1—N1	94.19 (8)	C11—C10—C9	120.0 (2)
O3—Cu1—Cu1ⁱ	82.21 (5)	C15—C10—C9	121.4 (2)
O3—Cu1—O1	87.53 (8)	C15—C10—C11	118.6 (3)
O3—Cu1—O2ⁱ	90.25 (8)	C10—C11—H11	119.6
O3—Cu1—O4	167.82 (7)	C12—C11—C10	120.7 (3)
O3—Cu1—N1	91.34 (8)	C12—C11—H11	119.6
O4—Cu1—Cu1ⁱ	86.04 (5)	C11—C12—C13	121.1 (3)
O4—Cu1—N1	100.68 (8)	C11—C12—H12	119.5
N1—Cu1—Cu1ⁱ	171.10 (6)	C13—C12—H12	119.5
C1—O1—Cu1	117.87 (17)	C12—C13—C16	121.0 (3)
C1—O2—Cu1ⁱ	128.72 (16)	C14—C13—C12	118.1 (3)
C9—O3—Cu1	125.69 (17)	C14—C13—C16	120.9 (3)
C9ⁱ—O4—Cu1	120.50 (17)	C13—C14—H14	119.3
C17—N1—Cu1	119.94 (16)	C15—C14—C13	121.3 (3)
C17—N1—C21	117.5 (2)	C15—C14—H14	119.3
C21—N1—Cu1	122.42 (18)	C10—C15—H15	119.9
C22—N2—H2A	118 (2)	C14—C15—C10	120.2 (3)
C22—N2—H2B	121 (2)	C14—C15—H15	119.9
H2A—N2—H2B	120 (3)	C13—C16—H16A	109.5
O1—C1—C2	117.3 (2)	C13—C16—H16B	109.5
O2—C1—O1	125.1 (2)	C13—C16—H16C	109.5
O2—C1—C2	117.6 (2)	H16A—C16—H16B	109.5
C3—C2—C1	121.6 (2)	H16A—C16—H16C	109.5
C3—C2—C7	119.1 (2)	H16B—C16—H16C	109.5
C7—C2—C1	119.4 (2)	N1—C17—C18	123.6 (2)
C2—C3—H3	119.9	N1—C17—H17	118.2
C4—C3—C2	120.3 (2)	C18—C17—H17	118.2
C4—C3—H3	119.9	C17—C18—C19	118.5 (2)
C3—C4—C5	121.0 (3)	C17—C18—H18	120.7
C3—C4—H4	119.5	C19—C18—H18	120.7
C5—C4—H4	119.5	C18—C19—C22	118.1 (2)
C4—C5—C8	120.9 (3)	C20—C19—C18	118.3 (2)
C6—C5—C4	118.2 (2)	C20—C19—C22	123.6 (2)
C6—C5—C8	120.9 (2)	C19—C20—H20	120.4
C5—C6—C7	121.4 (2)	C21—C20—C19	119.3 (2)
C5—C6—H6	119.3	C21—C20—H20	120.4
C7—C6—H6	119.3	N1—C21—C20	122.8 (3)
C2—C7—H7	120.0	N1—C21—H21	118.6
C6—C7—C2	120.0 (2)	C20—C21—H21	118.6
C6—C7—H7	120.0	O5—C22—N2	123.4 (2)
C5—C8—H8A	109.5	O5—C22—C19	119.8 (2)
C5—C8—H8B	109.5	N2—C22—C19	116.9 (2)
C5—C8—H8C	109.5

Cu1ⁱ—Cu1—O1—C1	−1.45 (18)	O2—C1—C2—C7	8.2 (4)
O2ⁱ—Cu1—O1—C1	−4.4 (5)	C1—C2—C3—C4	−179.2 (2)
O3—Cu1—O1—C1	−83.72 (19)	C7—C2—C3—C4	−0.1 (4)
O4—Cu1—O1—C1	84.61 (19)	C1—C2—C7—C6	178.2 (2)
N1—Cu1—O1—C1	−174.75 (19)	C3—C2—C7—C6	−0.9 (4)
Cu1ⁱ—Cu1—O3—C9	5.3 (2)	C2—C3—C4—C5	0.8 (4)
O1—Cu1—O3—C9	94.1 (2)	C3—C4—C5—C6	−0.5 (4)
O2ⁱ—Cu1—O3—C9	−74.4 (2)	C3—C4—C5—C8	178.2 (2)
O4—Cu1—O3—C9	20.7 (5)	C4—C5—C6—C7	−0.5 (4)
N1—Cu1—O3—C9	−168.6 (2)	C8—C5—C6—C7	−179.2 (2)
Cu1ⁱ—Cu1—O4—C9ⁱ	−2.61 (18)	C5—C6—C7—C2	1.2 (4)
O1—Cu1—O4—C9ⁱ	−91.19 (19)	O3—C9—C10—C11	8.4 (4)
O2ⁱ—Cu1—O4—C9ⁱ	77.09 (19)	O3—C9—C10—C15	−170.2 (2)
O3—Cu1—O4—C9ⁱ	−17.9 (5)	O4ⁱ—C9—C10—C11	−171.8 (2)
N1—Cu1—O4—C9ⁱ	171.51 (19)	O4ⁱ—C9—C10—C15	9.6 (4)
O1—Cu1—N1—C17	−4.4 (2)	C9—C10—C11—C12	−177.8 (2)
O1—Cu1—N1—C21	−179.6 (2)	C15—C10—C11—C12	0.8 (4)
O2ⁱ—Cu1—N1—C17	177.58 (19)	C9—C10—C15—C14	176.1 (2)
O2ⁱ—Cu1—N1—C21	2.4 (2)	C11—C10—C15—C14	−2.6 (4)
O3—Cu1—N1—C17	−92.1 (2)	C10—C11—C12—C13	1.7 (4)
O3—Cu1—N1—C21	92.7 (2)	C11—C12—C13—C14	−2.5 (4)
O4—Cu1—N1—C17	85.95 (19)	C11—C12—C13—C16	175.5 (3)
O4—Cu1—N1—C21	−89.3 (2)	C12—C13—C14—C15	0.8 (4)
Cu1—O1—C1—O2	2.0 (3)	C16—C13—C14—C15	−177.3 (3)
Cu1—O1—C1—C2	−177.69 (16)	C13—C14—C15—C10	1.8 (4)
Cu1ⁱ—O2—C1—O1	−1.3 (4)	N1—C17—C18—C19	1.0 (4)
Cu1ⁱ—O2—C1—C2	178.39 (16)	C17—C18—C19—C20	−2.6 (4)
Cu1—O3—C9—O4ⁱ	−5.1 (4)	C17—C18—C19—C22	178.6 (2)
Cu1—O3—C9—C10	174.71 (16)	C18—C19—C20—C21	2.1 (4)
Cu1—N1—C17—C18	−174.35 (19)	C22—C19—C20—C21	−179.1 (2)
C21—N1—C17—C18	1.1 (4)	C18—C19—C22—O5	30.9 (4)
Cu1—N1—C21—C20	173.7 (2)	C18—C19—C22—N2	−148.8 (3)
C17—N1—C21—C20	−1.6 (4)	C20—C19—C22—O5	−147.9 (3)
O1—C1—C2—C3	7.0 (4)	C20—C19—C22—N2	32.4 (4)
O1—C1—C2—C7	−172.1 (2)	C19—C20—C21—N1	0.1 (4)
O2—C1—C2—C3	−172.7 (2)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5ⁱⁱ	0.89 (3)	2.11 (3)	2.984 (3)	169 (3)

Symmetry code: (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂]
M_r	911.88
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	101
a, b, c (Å)	11.2305 (2), 23.4691 (4), 8.0087 (1)
β (°)	102.128 (1)
V (Å³)	2063.74 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.30 × 0.24 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.735, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	20056, 5101, 3629
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.087, 1.01
No. of reflections	5101
No. of parameters	281
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.70

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).

Selected bond lengths (Å) top

Cu1—O1	1.9733 (18)	Cu1—O4	1.9836 (18)
Cu1—O2ⁱ	1.9703 (18)	Cu1—N1	2.161 (2)
Cu1—O3	1.9687 (18)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5ⁱⁱ	0.89 (3)	2.11 (3)	2.984 (3)	169 (3)

Symmetry code: (ii) x, −y+3/2, z+1/2.

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 X-ray diffractometer. This work was supported financially by the Scientific and Technological Research Council of Turkey (grant No. 108 T657).

References

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 (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. 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., 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
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