Bis(μ-4-formyl­benzoato-κ2O:O′)bis­[(4-formyl­benzoato-κ2O,O′)bis­(iso­nicotin­amide-κN1)copper(II)]

Sertçelik, M.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536813010908

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages m290-m291

https://doi.org/10.1107/S1600536813010908

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Bis(μ-4-formylbenzoato-κ²O:O′)bis[(4-formylbenzoato-κ²O,O′)bis(isonicotinamide-κN¹)copper(II)]

Mustafa Sertçelik,^a Nagihan Çaylak Delibaş,^b Hacali Necefoğlu ^a and Tuncer Hökelek ^c ^*

^aDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey, ^bDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 29 March 2013; accepted 22 April 2013; online 27 April 2013)

The asymmetric unit of the centrosymmetric dinuclear title compound, [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄], contains one half of the complex molecule. The Cu^II atoms are bridged by the carboxylate groups of two 4-formylbenzoate (FOB) anions. Besides the two bridging FOB anions, one additional chelating FOB anion and two isonicotinamide (INA) ligands complete the distorted CuN₂O₄ octahedral coordination of each Cu²⁺ cation. Within the asymmetric unit, the benzene and pyridine rings are oriented at dihedral angles of 25.1 (3) and 12.6 (3)°, respectively. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π contacts between the pyridine rings [shortest centroid–centroid distance = 3.821 (3) Å] may further stabilize the crystal structure. One of the formyl groups of the two FOB anions is disordered over two sets of sites with an occupancy ratio of 0.65:0.35.

Related literature

For general background, see: Bigoli et al. (1972 ); Krishnamachari (1974 ). For related structures, see: Hökelek (1996 , 2009a ,b ,c )); Greenaway et al. (1984 ); Necefoğlu et al. (2011 ).

Experimental

Crystal data

[Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄]
M_r = 1212.09
Triclinic, $[P \overline 1]$
a = 8.6462 (2) Å
b = 11.6709 (3) Å
c = 13.4339 (4) Å
α = 87.876 (3)°
β = 83.483 (3)°
γ = 74.566 (2)°
V = 1298.24 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 100 K
0.17 × 0.07 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.927, T_max = 0.947
19200 measured reflections
6198 independent reflections
4412 reflections with I > 2σ(I)
R_int = 0.189

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.204
S = 1.11
6198 reflections
389 parameters
119 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.05 e Å⁻³
Δρ_min = −1.51 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.994 (3)
Cu1—O2	2.736 (4)
Cu1—O3	1.949 (4)
Cu1—O4ⁱ	2.242 (3)
Cu1—N1	2.033 (4)
Cu1—N2	2.013 (4)
Symmetry code: (i) -x+1, -y+1, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2ⁱⁱ	0.86	2.17	2.997 (6)	160
N3—H3B⋯O5Aⁱⁱⁱ	0.86	2.27	3.044 (9)	149
N4—H4A⋯O7^iv	0.86	2.06	2.878 (6)	158
N4—H4B⋯O2^v	0.86	2.10	2.890 (6)	152
C3—H3⋯O7^vi	0.93	2.52	3.391 (7)	155
C6—H6⋯O8^vii	0.93	2.44	3.336 (9)	162
C18—H18⋯O5Aⁱⁱⁱ	0.93	2.35	3.274 (9)	169
C23—H23⋯O2^v	0.93	2.54	3.432 (7)	162
C24—H24⋯O6^viii	0.93	2.50	3.217 (7)	134
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z; (iv) x+1, y, z+1; (v) -x+2, -y+1, -z+2; (vi) x+1, y, z; (vii) -x+1, -y+2, -z+2; (viii) -x+2, -y, -z+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, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813010908/wm2735sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813010908/wm2735Isup2.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 , [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄], was synthesized and its crystal structure is reported herein.

The asymmetric unit of the centrosymmetric dinuclear title compound contains one half of the complex molecule. The structures of some DENA and/or NA complexes with Zn^II, viz. [Zn₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009a), [Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂]^.2H₂O (Hökelek et al., 2009b) and [Zn₂(C₇H₄FO₂)₄(C₆H₆N₂O)₂].C₇H₅FO₂ (Hökelek et al., 2009c) have also been determined.

In the title dinuclear compound the Cu²⁺ cations are bridged by two carboxylate groups of two 4-formylbenzoate (FOB) anions. The two bridging FOB anions, one chelating FOB anion and two isonicotinamide (INA) ligands coordinate to each Cu²⁺ cation in a distorted octahedral geometry. Each Cu^II atom is surrounded by three FOB anions and two INA ligands. The INA ligands are coordinated to the Cu^II ion through pyridine N atoms only. Two FOB anions act as bridging ligands, while the other FOB anion is coordinated to the Cu^II ion bidentately. The Cu1···Cu1a distance is 4.1554 (8) Å. The four O atoms around the Cu1 atom form a distorted square-planar arrangement with an average Cu1—O bond length of 2.23 Å (Table 1). The distorted octahedral coordination is completed by the pyridine atoms, N1 and N2 of the INA ligands at distances of 2.033 (4) and 2.013 (4) Å, respectively (Table 1, Fig. 1). The N1—Cu1···Cu1a and N2—Cu1···Cu1a angles (a = x, - y, - z) are 97.62 (12) and 77.27 (12) °, respectively. The dihedral angles between the planar carboxylate groups (O1/O2/C1), (O3/O4/C8) and the adjacent benzene rings A (C2—C7), B (C9—C14) are 11.3 (6)° and 2.1 (6)°, respectively, while that between rings A and B is A/B = 25.1 (3)°. The pyridine rings C (N1/C15—C19) and D (N2/C20—C24) are oriented at a dihedral angle of 12.6 (3)°. The O1—Cu1—O2 angle involving the chelating FOB anion is 53.50 (14)°.

The corresponding O—Cu—O angles are 57.75 (2)° in [Cu(C₇H₄FO₂)₂(C₇H₅FO₂)(C₆H₆N₂O)₂] (Necefoğlu et al., 2011), 58.3 (3)° in [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) (Greenaway et al., 1984).

In the crystal structure, N—H···O and C–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 shortest π–π contact between the pyridine rings, Cg3—Cg4ⁱ [symmetry code: (i) 1 - x, 1 - y, - z, where Cg3 and Cg4 are the centroids of the rings C (N1/C15—C19) and D (N2/C20—C24), respectively] may further stabilize the structure, with a centroid-centroid distance of 3.821 (3) Å.

Related literature top

For general background, see: Bigoli et al. (1972); Krishnamachari (1974). For related structures, see: Hökelek (1996, 2009a,b,c)); Greenaway et al. (1984); Necefoğlu et al. (2011).

Experimental top

The title compound was prepared by the reaction of CuSO₄^.5H₂O (1.25 g, 5 mmol) in H₂O (50 ml) and INA (1.22 g, 10 mmol) in H₂O (100 ml) with sodium 4-formylbenzoate (1.72 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving blue single crystals.

Structure description top

For general background, see: Bigoli et al. (1972); Krishnamachari (1974). For related structures, see: Hökelek (1996, 2009a,b,c)); Greenaway et al. (1984); Necefoğlu et al. (2011).

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, 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. Hydrogen atoms have been omitted for clarity [symmetry operator: (a) - x, - y, - z].

Bis(µ-4-formylbenzoato-κ²O:O')bis[(4-formylbenzoato-κ²O,O')bis(isonicotinamide-κN¹)copper(II)] top

Crystal data top

[Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄]	Z = 1
M_r = 1212.09	F(000) = 622
Triclinic, P1	D_x = 1.550 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6462 (2) Å	Cell parameters from 6407 reflections
b = 11.6709 (3) Å	θ = 2.4–27.8°
c = 13.4339 (4) Å	µ = 0.90 mm⁻¹
α = 87.876 (3)°	T = 100 K
β = 83.483 (3)°	Rod, blue
γ = 74.566 (2)°	0.17 × 0.07 × 0.06 mm
V = 1298.24 (6) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6198 independent reflections
Radiation source: fine-focus sealed tube	4412 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.189
φ and ω scans	θ_max = 28.2°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
T_min = 0.927, T_max = 0.947	k = −15→15
19200 measured reflections	l = −16→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.204	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.076P)² + 1.153P] where P = (F_o² + 2F_c²)/3
6198 reflections	(Δ/σ)_max < 0.001
389 parameters	Δρ_max = 1.05 e Å⁻³
119 restraints	Δρ_min = −1.51 e Å⁻³

Crystal data top

[Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄]	γ = 74.566 (2)°
M_r = 1212.09	V = 1298.24 (6) Å³
Triclinic, P1	Z = 1
a = 8.6462 (2) Å	Mo Kα radiation
b = 11.6709 (3) Å	µ = 0.90 mm⁻¹
c = 13.4339 (4) Å	T = 100 K
α = 87.876 (3)°	0.17 × 0.07 × 0.06 mm
β = 83.483 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6198 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4412 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.947	R_int = 0.189
19200 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	119 restraints
wR(F²) = 0.204	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 1.05 e Å⁻³
6198 reflections	Δρ_min = −1.51 e Å⁻³
389 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.62806 (7)	0.56954 (5)	0.88371 (4)	0.0185 (2)
O1	0.6218 (4)	0.7313 (3)	0.8280 (2)	0.0219 (8)
O2	0.8235 (4)	0.6237 (3)	0.7243 (3)	0.0242 (8)
O3	0.7284 (4)	0.3990 (3)	0.8858 (2)	0.0236 (8)
O4	0.6139 (4)	0.3497 (3)	1.0325 (3)	0.0234 (8)
O5A	0.5585 (8)	1.2043 (6)	0.4824 (4)	0.0358 (16)	0.65
O5B	0.7922 (16)	1.1019 (11)	0.3972 (9)	0.036 (3)	0.35
O6	0.9826 (6)	−0.2505 (4)	0.9067 (4)	0.0539 (13)
O7	0.1544 (5)	0.6109 (4)	0.4944 (3)	0.0413 (11)
O8	0.7785 (6)	0.7769 (5)	1.3297 (4)	0.075 (2)
N1	0.5025 (5)	0.5434 (4)	0.7713 (3)	0.0192 (8)
N2	0.7236 (5)	0.6046 (4)	1.0053 (3)	0.0205 (9)
N3	0.2635 (6)	0.4147 (4)	0.4793 (3)	0.0273 (10)
H3A	0.2147	0.4101	0.4278	0.033*
H3B	0.3264	0.3518	0.5024	0.033*
N4	0.9885 (5)	0.6171 (4)	1.3195 (3)	0.0250 (9)
H4A	1.0185	0.6325	1.3753	0.030*
H4B	1.0426	0.5553	1.2859	0.030*
C1	0.7234 (6)	0.7203 (4)	0.7504 (4)	0.0206 (10)
C2	0.7188 (6)	0.8266 (4)	0.6842 (4)	0.0222 (10)
C3	0.8351 (7)	0.8206 (5)	0.6028 (4)	0.0259 (11)
H3	0.9212	0.7530	0.5934	0.031*
C4	0.8234 (7)	0.9140 (5)	0.5363 (4)	0.0299 (12)
H4	0.9015	0.9094	0.4819	0.036*
C5	0.6953 (8)	1.0154 (5)	0.5500 (4)	0.0325 (13)
C6	0.5786 (7)	1.0235 (5)	0.6324 (4)	0.0339 (13)
H6	0.4930	1.0913	0.6421	0.041*
C7	0.5923 (7)	0.9294 (5)	0.6992 (4)	0.0286 (12)
H7	0.5163	0.9346	0.7548	0.034*
C8	0.6975 (5)	0.3243 (4)	0.9504 (3)	0.0172 (9)
C9	0.7701 (6)	0.1950 (4)	0.9257 (4)	0.0217 (10)
C10	0.7451 (7)	0.1082 (5)	0.9932 (4)	0.0269 (11)
H10	0.6821	0.1294	1.0539	0.032*
C11	0.8139 (7)	−0.0111 (5)	0.9706 (5)	0.0319 (12)
H11	0.7989	−0.0695	1.0168	0.038*
C12	0.9055 (7)	−0.0432 (5)	0.8787 (5)	0.0330 (13)
C13	0.9269 (7)	0.0436 (5)	0.8116 (4)	0.0322 (13)
H13	0.9874	0.0222	0.7502	0.039*
C14	0.8600 (7)	0.1626 (5)	0.8333 (4)	0.0283 (12)
H14	0.8749	0.2207	0.7866	0.034*
C15	0.3770 (6)	0.6306 (5)	0.7469 (4)	0.0233 (10)
H15	0.3460	0.6994	0.7850	0.028*
C16	0.2918 (6)	0.6235 (4)	0.6686 (4)	0.0233 (10)
H16	0.2064	0.6869	0.6537	0.028*
C17	0.3337 (6)	0.5212 (4)	0.6115 (3)	0.0211 (10)
C18	0.4627 (7)	0.4294 (5)	0.6364 (4)	0.0259 (11)
H18	0.4936	0.3591	0.6002	0.031*
C19	0.5449 (6)	0.4434 (4)	0.7153 (4)	0.0223 (10)
H19	0.6324	0.3820	0.7308	0.027*
C20	0.6678 (6)	0.7138 (4)	1.0458 (4)	0.0202 (10)
H20	0.5980	0.7726	1.0117	0.024*
C21	0.7102 (6)	0.7416 (5)	1.1354 (4)	0.0237 (11)
H21	0.6680	0.8175	1.1618	0.028*
C22	0.8170 (6)	0.6553 (5)	1.1866 (4)	0.0215 (10)
C23	0.8753 (6)	0.5437 (4)	1.1446 (4)	0.0206 (10)
H23	0.9476	0.4840	1.1763	0.025*
C24	0.8253 (6)	0.5224 (4)	1.0555 (4)	0.0204 (10)
H24	0.8643	0.4466	1.0285	0.024*
C25	0.6803 (9)	1.1107 (6)	0.4732 (4)	0.0406 (15)
H25A	0.748 (11)	1.094 (8)	0.410 (4)	0.035*	0.65
H25B	0.622 (17)	1.188 (4)	0.500 (10)	0.035*	0.35
C26	0.9852 (8)	−0.1697 (6)	0.8536 (5)	0.0397 (15)
H26	1.042 (5)	−0.189 (4)	0.793 (2)	0.016 (14)*
C27	0.2415 (6)	0.5188 (5)	0.5231 (4)	0.0241 (11)
C28	0.8602 (7)	0.6880 (5)	1.2856 (4)	0.0268 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0193 (4)	0.0219 (3)	0.0121 (3)	−0.0046 (2)	0.0078 (2)	−0.0045 (2)
O1	0.029 (2)	0.0195 (16)	0.0144 (17)	−0.0054 (15)	0.0067 (14)	−0.0028 (13)
O2	0.025 (2)	0.0264 (17)	0.0173 (18)	−0.0027 (15)	0.0065 (15)	−0.0011 (14)
O3	0.033 (2)	0.0251 (17)	0.0121 (17)	−0.0100 (16)	0.0039 (15)	−0.0005 (14)
O4	0.0201 (19)	0.0293 (18)	0.0181 (18)	−0.0055 (15)	0.0093 (14)	−0.0068 (14)
O5A	0.048 (4)	0.034 (3)	0.023 (3)	−0.011 (3)	0.004 (3)	0.000 (3)
O5B	0.050 (9)	0.027 (5)	0.027 (6)	−0.009 (5)	0.014 (5)	0.008 (5)
O6	0.046 (3)	0.037 (2)	0.079 (4)	−0.008 (2)	−0.008 (3)	−0.009 (2)
O7	0.046 (3)	0.038 (2)	0.033 (2)	0.006 (2)	−0.015 (2)	−0.0141 (19)
O8	0.062 (3)	0.083 (4)	0.053 (3)	0.043 (3)	−0.034 (3)	−0.053 (3)
N1	0.015 (2)	0.026 (2)	0.015 (2)	−0.0069 (16)	0.0081 (16)	−0.0036 (16)
N2	0.023 (2)	0.024 (2)	0.014 (2)	−0.0075 (17)	0.0065 (16)	−0.0044 (15)
N3	0.038 (3)	0.029 (2)	0.015 (2)	−0.008 (2)	0.0000 (19)	−0.0048 (17)
N4	0.025 (2)	0.031 (2)	0.015 (2)	−0.0040 (19)	0.0050 (18)	−0.0084 (18)
C1	0.023 (3)	0.025 (2)	0.013 (2)	−0.006 (2)	0.0030 (19)	−0.0040 (18)
C2	0.025 (3)	0.024 (2)	0.016 (2)	−0.007 (2)	0.006 (2)	−0.0051 (19)
C3	0.028 (3)	0.029 (2)	0.019 (3)	−0.007 (2)	0.006 (2)	−0.003 (2)
C4	0.039 (3)	0.033 (3)	0.018 (3)	−0.014 (2)	0.010 (2)	−0.003 (2)
C5	0.050 (4)	0.029 (3)	0.019 (3)	−0.014 (2)	0.006 (2)	0.001 (2)
C6	0.039 (4)	0.027 (3)	0.031 (3)	−0.003 (2)	0.002 (2)	0.000 (2)
C7	0.032 (3)	0.029 (2)	0.021 (3)	−0.005 (2)	0.011 (2)	−0.003 (2)
C8	0.005 (2)	0.024 (2)	0.019 (2)	−0.0007 (18)	0.0043 (18)	−0.0035 (18)
C9	0.015 (3)	0.024 (2)	0.023 (3)	−0.0026 (19)	0.006 (2)	−0.0065 (19)
C10	0.022 (3)	0.029 (2)	0.027 (3)	−0.006 (2)	0.006 (2)	−0.003 (2)
C11	0.030 (3)	0.026 (2)	0.041 (3)	−0.010 (2)	−0.006 (2)	0.004 (2)
C12	0.027 (3)	0.030 (3)	0.042 (3)	−0.005 (2)	−0.004 (3)	−0.011 (2)
C13	0.026 (3)	0.034 (3)	0.031 (3)	0.000 (2)	0.008 (2)	−0.016 (2)
C14	0.027 (3)	0.028 (3)	0.026 (3)	−0.005 (2)	0.008 (2)	−0.006 (2)
C15	0.020 (3)	0.027 (2)	0.018 (3)	−0.002 (2)	0.009 (2)	−0.007 (2)
C16	0.021 (3)	0.025 (2)	0.020 (3)	−0.002 (2)	0.006 (2)	−0.005 (2)
C17	0.022 (3)	0.029 (2)	0.011 (2)	−0.008 (2)	0.0121 (19)	−0.0041 (19)
C18	0.030 (3)	0.029 (2)	0.016 (2)	−0.007 (2)	0.010 (2)	−0.010 (2)
C19	0.022 (3)	0.024 (2)	0.016 (2)	−0.001 (2)	0.010 (2)	−0.0061 (19)
C20	0.017 (3)	0.022 (2)	0.016 (2)	−0.0008 (19)	0.0081 (19)	−0.0033 (18)
C21	0.024 (3)	0.025 (2)	0.018 (2)	−0.002 (2)	0.007 (2)	−0.0076 (19)
C22	0.019 (3)	0.030 (2)	0.013 (2)	−0.006 (2)	0.0054 (19)	−0.0025 (19)
C23	0.021 (3)	0.023 (2)	0.014 (2)	−0.0026 (19)	0.0085 (19)	−0.0035 (18)
C24	0.016 (3)	0.026 (2)	0.015 (2)	−0.0045 (19)	0.0124 (19)	−0.0042 (19)
C25	0.063 (5)	0.034 (3)	0.024 (3)	−0.013 (3)	0.002 (3)	0.001 (2)
C26	0.035 (4)	0.034 (3)	0.052 (4)	−0.009 (3)	−0.016 (3)	−0.003 (3)
C27	0.025 (3)	0.034 (3)	0.012 (2)	−0.010 (2)	0.011 (2)	−0.007 (2)
C28	0.024 (3)	0.035 (3)	0.018 (3)	−0.001 (2)	0.005 (2)	−0.010 (2)

Geometric parameters (Å, º) top

Cu1—O1	1.994 (3)	C7—C6	1.382 (8)
Cu1—O2	2.736 (4)	C7—H7	0.9300
Cu1—O3	1.949 (4)	C8—C9	1.506 (7)
Cu1—O4ⁱ	2.242 (3)	C9—C10	1.378 (7)
Cu1—N1	2.033 (4)	C9—C14	1.395 (7)
Cu1—N2	2.013 (4)	C10—H10	0.9300
O1—C1	1.271 (6)	C11—C10	1.390 (7)
O2—C1	1.259 (6)	C11—C12	1.395 (8)
O3—C8	1.264 (6)	C11—H11	0.9300
O4—C8	1.248 (6)	C12—C13	1.366 (9)
O4—Cu1ⁱ	2.242 (3)	C13—H13	0.9300
O5A—C25	1.299 (9)	C14—C13	1.384 (7)
O5A—H25B	0.61 (19)	C14—H14	0.9300
O5B—C25	1.311 (11)	C15—C16	1.367 (7)
O5B—H25A	0.43 (10)	C15—H15	0.9300
O6—C26	1.165 (8)	C16—H16	0.9300
O7—C27	1.215 (7)	C17—C16	1.385 (6)
N1—C15	1.338 (7)	C17—C27	1.508 (7)
N1—C19	1.356 (6)	C18—C17	1.388 (8)
N2—C20	1.349 (6)	C18—H18	0.9300
N2—C24	1.336 (7)	C19—C18	1.379 (7)
N3—C27	1.328 (6)	C19—H19	0.9300
N3—H3A	0.8600	C20—C21	1.371 (7)
N3—H3B	0.8600	C20—H20	0.9300
N4—C28	1.312 (7)	C21—C22	1.392 (7)
N4—H4A	0.8600	C21—H21	0.9300
N4—H4B	0.8600	C22—C28	1.511 (7)
C1—C2	1.494 (7)	C23—C22	1.381 (7)
C3—C4	1.374 (7)	C23—C24	1.370 (7)
C3—C2	1.389 (7)	C23—H23	0.9300
C3—H3	0.9300	C24—H24	0.9300
C4—H4	0.9300	C25—H25A	0.97 (2)
C5—C4	1.391 (8)	C25—H25B	0.97 (2)
C5—C25	1.479 (8)	C26—C12	1.487 (8)
C6—C5	1.398 (8)	C26—H26	0.90 (2)
C6—H6	0.9300	C28—O8	1.220 (6)
C7—C2	1.395 (7)

O1—Cu1—O4ⁱ	87.34 (13)	C12—C11—H11	120.0
O1—Cu1—N1	88.89 (15)	C11—C12—C26	121.4 (6)
O1—Cu1—N2	90.93 (15)	C13—C12—C11	119.4 (5)
O3—Cu1—O1	150.35 (14)	C13—C12—C26	119.2 (5)
O3—Cu1—O4ⁱ	121.93 (13)	C12—C13—C14	121.2 (5)
O3—Cu1—N1	88.74 (16)	C12—C13—H13	119.4
O3—Cu1—N2	95.15 (16)	C14—C13—H13	119.4
N1—Cu1—O4ⁱ	85.80 (14)	C9—C14—H14	120.3
N2—Cu1—O4ⁱ	86.58 (15)	C13—C14—C9	119.5 (5)
N2—Cu1—N1	172.37 (16)	C13—C14—H14	120.3
C1—O1—Cu1	108.3 (3)	N1—C15—C16	123.3 (4)
C8—O3—Cu1	127.1 (3)	N1—C15—H15	118.4
C8—O4—Cu1ⁱ	148.5 (3)	C16—C15—H15	118.4
C15—N1—Cu1	119.3 (3)	C15—C16—C17	119.6 (5)
C15—N1—C19	117.5 (4)	C15—C16—H16	120.2
C19—N1—Cu1	123.1 (4)	C17—C16—H16	120.2
C20—N2—Cu1	118.3 (4)	C16—C17—C18	117.9 (5)
C24—N2—Cu1	123.9 (3)	C16—C17—C27	118.0 (5)
C24—N2—C20	117.3 (4)	C18—C17—C27	124.1 (4)
C27—N3—H3A	120.0	C17—C18—H18	120.3
C27—N3—H3B	120.0	C19—C18—C17	119.4 (4)
H3A—N3—H3B	120.0	C19—C18—H18	120.3
C28—N4—H4A	120.0	N1—C19—C18	122.3 (5)
C28—N4—H4B	120.0	N1—C19—H19	118.8
H4A—N4—H4B	120.0	C18—C19—H19	118.8
O1—C1—C2	118.2 (4)	N2—C20—C21	122.5 (5)
O2—C1—O1	123.6 (5)	N2—C20—H20	118.7
O2—C1—C2	118.2 (4)	C21—C20—H20	118.7
C3—C2—C7	119.5 (5)	C20—C21—C22	119.4 (5)
C3—C2—C1	119.9 (5)	C20—C21—H21	120.3
C7—C2—C1	120.5 (4)	C22—C21—H21	120.3
C2—C3—H3	119.9	C21—C22—C28	118.3 (5)
C4—C3—C2	120.2 (5)	C23—C22—C21	118.0 (5)
C4—C3—H3	119.9	C23—C22—C28	123.7 (5)
C4—C5—C6	120.2 (5)	C22—C23—H23	120.5
C4—C5—C25	118.8 (5)	C24—C23—C22	119.0 (5)
C6—C5—C25	121.0 (6)	C24—C23—H23	120.5
C3—C4—C5	120.3 (5)	N2—C24—C23	123.6 (5)
C3—C4—H4	119.9	N2—C24—H24	118.2
C5—C4—H4	119.9	C23—C24—H24	118.2
C5—C6—H6	120.5	O5A—C25—O5B	120.1 (8)
C7—C6—C5	119.0 (5)	O5A—C25—C5	119.9 (6)
C7—C6—H6	120.5	O5B—C25—C5	119.9 (8)
C2—C7—H7	119.6	O5A—C25—H25A	120 (5)
C6—C7—C2	120.8 (5)	C5—C25—H25A	118 (5)
C6—C7—H7	119.6	O5B—C25—H25B	120 (5)
O3—C8—C9	116.7 (4)	C5—C25—H25B	113 (7)
O4—C8—O3	125.1 (5)	H25A—C25—H25B	127 (8)
O4—C8—C9	118.2 (4)	O6—C26—C12	125.3 (7)
C10—C9—C8	120.2 (4)	O6—C26—H26	114 (3)
C10—C9—C14	119.8 (5)	C12—C26—H26	120 (3)
C14—C9—C8	120.0 (5)	O7—C27—N3	123.4 (5)
C9—C10—C11	120.0 (5)	O7—C27—C17	119.3 (5)
C9—C10—H10	120.0	N3—C27—C17	117.3 (5)
C11—C10—H10	120.0	O8—C28—N4	123.1 (5)
C10—C11—C12	120.1 (5)	O8—C28—C22	120.3 (5)
C10—C11—H11	120.0	N4—C28—C22	116.6 (4)

O3—Cu1—O1—C1	9.8 (5)	C6—C5—C25—O5A	0.9 (9)
O4ⁱ—Cu1—O1—C1	−161.5 (3)	C6—C5—C25—O5B	179.1 (9)
N1—Cu1—O1—C1	−75.7 (3)	C7—C6—C5—C4	−0.4 (9)
N2—Cu1—O1—C1	111.9 (3)	C7—C6—C5—C25	176.2 (6)
O1—Cu1—O3—C8	169.2 (4)	C6—C7—C2—C1	−173.4 (5)
O4ⁱ—Cu1—O3—C8	−21.0 (4)	C6—C7—C2—C3	2.1 (8)
N1—Cu1—O3—C8	−105.2 (4)	C2—C7—C6—C5	−1.1 (9)
N2—Cu1—O3—C8	68.2 (4)	O3—C8—C9—C10	178.6 (5)
O1—Cu1—N1—C19	132.7 (4)	O3—C8—C9—C14	−2.8 (7)
O3—Cu1—N1—C15	165.9 (4)	O4—C8—C9—C10	−0.7 (7)
O3—Cu1—N1—C19	−17.7 (4)	O4—C8—C9—C14	177.9 (5)
O4ⁱ—Cu1—N1—C15	43.8 (4)	C8—C9—C10—C11	−179.2 (5)
O4ⁱ—Cu1—N1—C19	−139.9 (4)	C14—C9—C10—C11	2.2 (8)
O1—Cu1—N2—C20	39.5 (3)	C8—C9—C14—C13	179.6 (5)
O1—Cu1—N2—C24	−148.6 (4)	C10—C9—C14—C13	−1.7 (8)
O3—Cu1—N2—C20	−169.5 (3)	C12—C11—C10—C9	−1.4 (8)
O3—Cu1—N2—C24	2.4 (4)	C10—C11—C12—C13	0.1 (9)
O4ⁱ—Cu1—N2—C20	−47.7 (3)	C10—C11—C12—C26	178.0 (5)
O4ⁱ—Cu1—N2—C24	124.1 (4)	C11—C12—C13—C14	0.3 (9)
Cu1—O1—C1—O2	−8.7 (6)	C26—C12—C13—C14	−177.6 (5)
Cu1—O1—C1—C2	168.4 (3)	C9—C14—C13—C12	0.5 (9)
Cu1—O3—C8—O4	−11.3 (7)	N1—C15—C16—C17	1.0 (8)
Cu1—O3—C8—C9	169.5 (3)	C18—C17—C16—C15	−0.4 (7)
Cu1ⁱ—O4—C8—O3	65.4 (8)	C27—C17—C16—C15	−177.4 (4)
Cu1ⁱ—O4—C8—C9	−115.4 (6)	C16—C17—C27—O7	12.4 (7)
Cu1—N1—C15—C16	176.0 (4)	C16—C17—C27—N3	−169.0 (4)
C19—N1—C15—C16	−0.6 (7)	C18—C17—C27—O7	−164.4 (5)
Cu1—N1—C19—C18	−177.0 (4)	C18—C17—C27—N3	14.2 (7)
C15—N1—C19—C18	−0.5 (7)	C19—C18—C17—C16	−0.6 (7)
Cu1—N2—C20—C21	171.6 (4)	C19—C18—C17—C27	176.2 (4)
C24—N2—C20—C21	−0.8 (7)	N1—C19—C18—C17	1.1 (7)
Cu1—N2—C24—C23	−172.2 (3)	N2—C20—C21—C22	1.2 (7)
C20—N2—C24—C23	−0.2 (7)	C20—C21—C22—C23	−0.5 (7)
O1—C1—C2—C3	175.4 (5)	C20—C21—C22—C28	−179.4 (4)
O1—C1—C2—C7	−9.1 (7)	C21—C22—C28—O8	15.8 (8)
O2—C1—C2—C3	−7.3 (7)	C21—C22—C28—N4	−163.5 (5)
O2—C1—C2—C7	168.2 (5)	C23—C22—C28—O8	−163.0 (6)
C4—C3—C2—C1	174.0 (5)	C23—C22—C28—N4	17.6 (7)
C4—C3—C2—C7	−1.6 (8)	C24—C23—C22—C21	−0.5 (7)
C2—C3—C4—C5	0.1 (8)	C24—C23—C22—C28	178.3 (4)
C6—C5—C4—C3	0.9 (9)	C22—C23—C24—N2	0.9 (7)
C25—C5—C4—C3	−175.8 (5)	O6—C26—C12—C11	−2.0 (10)
C4—C5—C25—O5A	177.5 (6)	O6—C26—C12—C13	175.9 (6)
C4—C5—C25—O5B	−4.2 (11)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱⁱ	0.86	2.17	2.997 (6)	160
N3—H3B···O5Aⁱⁱⁱ	0.86	2.27	3.044 (9)	149
N4—H4A···O7^iv	0.86	2.06	2.878 (6)	158
N4—H4B···O2^v	0.86	2.10	2.890 (6)	152
C3—H3···O7^vi	0.93	2.52	3.391 (7)	155
C6—H6···O8^vii	0.93	2.44	3.336 (9)	162
C18—H18···O5Aⁱⁱⁱ	0.93	2.35	3.274 (9)	169
C23—H23···O2^v	0.93	2.54	3.432 (7)	162
C24—H24···O6^viii	0.93	2.50	3.217 (7)	134

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x+1, y, z+1; (v) −x+2, −y+1, −z+2; (vi) x+1, y, z; (vii) −x+1, −y+2, −z+2; (viii) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄]
M_r	1212.09
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.6462 (2), 11.6709 (3), 13.4339 (4)
α, β, γ (°)	87.876 (3), 83.483 (3), 74.566 (2)
V (Å³)	1298.24 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.17 × 0.07 × 0.06

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.927, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	19200, 6198, 4412
R_int	0.189
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.204, 1.11
No. of reflections	6198
No. of parameters	389
No. of restraints	119
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.05, −1.51

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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	1.994 (3)	Cu1—O4ⁱ	2.242 (3)
Cu1—O2	2.736 (4)	Cu1—N1	2.033 (4)
Cu1—O3	1.949 (4)	Cu1—N2	2.013 (4)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱⁱ	0.86	2.17	2.997 (6)	160
N3—H3B···O5Aⁱⁱⁱ	0.86	2.27	3.044 (9)	149
N4—H4A···O7^iv	0.86	2.06	2.878 (6)	158
N4—H4B···O2^v	0.86	2.10	2.890 (6)	152
C3—H3···O7^vi	0.93	2.52	3.391 (7)	155
C6—H6···O8^vii	0.93	2.44	3.336 (9)	162
C18—H18···O5Aⁱⁱⁱ	0.93	2.35	3.274 (9)	169
C23—H23···O2^v	0.93	2.54	3.432 (7)	162
C24—H24···O6^viii	0.93	2.50	3.217 (7)	134

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x+1, y, z+1; (v) −x+2, −y+1, −z+2; (vi) x+1, y, z; (vii) −x+1, −y+2, −z+2; (viii) −x+2, −y, −z+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 the X-ray diffractometer. This work was supported financially by Kafkas University Research Fund (grant No. 2012-FEF-12).

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