Di-μ-nicotinamide-κ2O:N1;κ2N1:O-bis­[aqua­bis­(4-meth­oxy­benzoato-κO)copper(II)]

Hökelek, T.; Süzen, Y.; Tercan, B.; Tenlik, E.; Necefoğlu, H.

doi:10.1107/S1600536810022415

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m807-m808

doi:10.1107/S1600536810022415

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Di-μ-nicotinamide-κ²O:N¹;κ²N¹:O-bis[aquabis(4-methoxybenzoato-κO)copper(II)]

Tuncer Hökelek,^a ^* Yasemin Süzen,^b Barış Tercan,^c Erdinç Tenlik ^d and Hacali Necefoğlu ^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Faculty of Science, Anadolu University, 26470 Yenibağlar, Eskişehir, Turkey, ^cDepartment of Physics, Karabük University, 78050 Karabük, Turkey, and ^dDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 8 June 2010; accepted 11 June 2010; online 16 June 2010)

The asymmetric unit of the centrosymmetric dinuclear title compound, [Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂], contains one half of the complex molecule. Each Cu^II atom is five-coordinated by one N atom from one bridging nicotinamide ligand and one O atom from another symmetry-related bridging nicotinamide ligand, two O atoms from two 4-methoxybenzoate ligands, and one water molecule, forming a distorted square-pyramidal geometry. Intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into layers parallel to ( $[\overline{1}]$ 01). π–π interactions, indicated by short intermolecular distances of 3.801 (1) Å between the centroids of the benzene rings and 3.653 (1) Å between the centroids of the pyridine rings, further stabilize the structure.

Related literature

For related structures, see: Hökelek & Necefoğlu (1996 ); Hökelek et al. (2009a ,b ,c ,d ).

Experimental

Crystal data

[Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r = 1011.93
Monoclinic, P 2₁ /n
a = 14.1707 (3) Å
b = 8.4319 (2) Å
c = 18.0225 (3) Å
β = 95.847 (2)°
V = 2142.23 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 100 K
0.37 × 0.37 × 0.23 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.678, T_max = 0.781
20329 measured reflections
5403 independent reflections
4813 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.072
S = 1.05
5403 reflections
316 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.86 (2)	2.03 (2)	2.8407 (18)	158 (2)
N2—H2B⋯O4ⁱⁱ	0.83 (2)	2.29 (2)	2.9897 (17)	141.4 (18)
O8—H81⋯O1ⁱⁱⁱ	0.79 (3)	1.97 (3)	2.7236 (15)	159 (3)
O8—H82⋯O4ⁱⁱⁱ	0.825 (18)	1.803 (18)	2.6052 (16)	163.9 (18)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: Mercury (Macrae et al., 2006 ); 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/S1600536810022415/cv2731sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022415/cv2731Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing study of transition metal complexes of nicotinamide (Hökelek & Necefoğlu, 1996; Hökelek et al., 2009a, b, c, d), herein we report the crystal structure of the title dinuclear complex.

The title compound, (I), consists of dimeric units located around a crystallographic symmetry centre and made up of two Cu cations, four 4-methoxybenzoate (MB) anions, two nicotinamide (NA) ligands and two water molecules (Fig. 1). Both of the Cu^II centres are five-coordinated with distorted square-pyramidal environments, and the two monomeric units are bridged through the two nicotinamide (NA) ligands about an inversion center. The Cu1···Cu1ⁱ (symmetry code: (i) 2 - x, -y, 1 - z) distance is 7.1368 (3) Å. The average Cu—O bond length is 2.0626 (10) Å, and the Cu atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O4/C9/O5) by 0.0015 (2) and -0.2589 (2) Å, respectively.

The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C10—C15) are 1.85 (5) and 10.16 (7) °, respectively, while those between rings A, B and C (N1/C17—C21) are A/B = 28.50 (4), A/C = 81.64 (4), B/C = 58.50 (4) °.

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into layers. The π–π contacts between the benzene rings and between the pyridine rings, Cg2—Cg2ⁱ and Cg3—Cg3ⁱⁱ [symmetry codes: (i) 2 - x, 2 - y, -z; (ii) 1 - x, 2 - y, -z, where Cg2 and Cg3 are the centroids of the rings B (C10—C15) and C (N1/C17—C21)] may further stabilize the structure, with centroid-centroid distances of 3.801 (1) and 3.653 (1) Å, respectively.

Related literature top

For related structures, see: Hökelek & Necefoğlu (1996); Hökelek et al. (2009a,b,c,d).

Experimental top

The title compound was prepared by the reaction of CuSO₄.5H₂O (2.50 g, 10 mmol) in H₂O (50 ml) and NA (2.44 g, 20 mmol) in H₂O (50 ml) with sodium 4-methoxybenzoate (3.48 g, 20 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving blue single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (') 2 - x, -y, 1 - z].

Di-µ-nicotinamide-κ²O:N¹;κ²N¹:O- bis[aquabis(4-methoxybenzoato-κO)copper(II)] top

Crystal data top

[Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂]	F(000) = 1044
M_r = 1011.93	D_x = 1.569 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9977 reflections
a = 14.1707 (3) Å	θ = 2.7–28.5°
b = 8.4319 (2) Å	µ = 1.07 mm⁻¹
c = 18.0225 (3) Å	T = 100 K
β = 95.847 (2)°	Block, blue
V = 2142.23 (8) Å³	0.37 × 0.37 × 0.23 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5403 independent reflections
Radiation source: fine-focus sealed tube	4813 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 28.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→18
T_min = 0.678, T_max = 0.781	k = −10→11
20329 measured reflections	l = −24→24

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0384P)² + 1.1134P] where P = (F_o² + 2F_c²)/3
5403 reflections	(Δ/σ)_max = 0.001
316 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂]	V = 2142.23 (8) Å³
M_r = 1011.93	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.1707 (3) Å	µ = 1.07 mm⁻¹
b = 8.4319 (2) Å	T = 100 K
c = 18.0225 (3) Å	0.37 × 0.37 × 0.23 mm
β = 95.847 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5403 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4813 reflections with I > 2σ(I)
T_min = 0.678, T_max = 0.781	R_int = 0.021
20329 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.47 e Å⁻³
5403 reflections	Δρ_min = −0.29 e Å⁻³
316 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
Cu1	0.832076 (11)	0.152692 (19)	0.356751 (8)	0.00986 (6)
O1	0.89942 (7)	0.40998 (13)	0.27780 (5)	0.0155 (2)
O2	0.94951 (7)	0.16598 (12)	0.30792 (5)	0.01368 (19)
O3	1.28693 (8)	0.39532 (15)	0.12796 (7)	0.0251 (2)
O4	0.66614 (8)	0.34649 (13)	0.32513 (6)	0.0181 (2)
O5	0.71138 (7)	0.14541 (12)	0.40038 (5)	0.01317 (19)
O6	0.32798 (7)	0.34252 (13)	0.52920 (6)	0.0170 (2)
O7	1.10015 (7)	0.07805 (12)	0.58526 (5)	0.0153 (2)
O8	0.77027 (8)	0.04960 (14)	0.26669 (6)	0.0167 (2)
H81	0.7200 (18)	0.008 (3)	0.2652 (13)	0.047 (7)*
H82	0.7977 (13)	−0.001 (2)	0.2360 (10)	0.017 (4)*
N1	0.88593 (8)	0.27822 (14)	0.44653 (6)	0.0118 (2)
N2	1.09767 (9)	0.27022 (17)	0.67244 (7)	0.0171 (3)
H2A	1.0823 (15)	0.365 (3)	0.6840 (12)	0.029 (5)*
H2B	1.1375 (14)	0.224 (2)	0.7019 (11)	0.022 (5)*
C1	0.95896 (9)	0.30016 (17)	0.27686 (7)	0.0125 (3)
C2	1.04648 (9)	0.32640 (17)	0.23831 (7)	0.0125 (3)
C3	1.11660 (10)	0.20966 (18)	0.23693 (8)	0.0152 (3)
H3	1.1096	0.1132	0.2608	0.018*
C4	1.19625 (10)	0.23685 (19)	0.20030 (8)	0.0187 (3)
H4	1.2429	0.1594	0.2003	0.022*
C5	1.20666 (10)	0.38071 (19)	0.16333 (8)	0.0173 (3)
C6	1.13758 (10)	0.49779 (18)	0.16412 (8)	0.0166 (3)
H6	1.1442	0.5936	0.1396	0.020*
C7	1.05849 (10)	0.46977 (18)	0.20197 (7)	0.0153 (3)
H7	1.0126	0.5484	0.2031	0.018*
C8	1.29541 (12)	0.5321 (2)	0.08255 (9)	0.0254 (3)
H8A	1.3544	0.5279	0.0607	0.038*
H8B	1.2938	0.6258	0.1126	0.038*
H8C	1.2437	0.5346	0.0437	0.038*
C9	0.65288 (9)	0.25480 (17)	0.37733 (7)	0.0123 (3)
C10	0.56660 (9)	0.27358 (16)	0.41748 (7)	0.0121 (2)
C11	0.55839 (10)	0.19292 (18)	0.48349 (8)	0.0148 (3)
H11	0.6064	0.1240	0.5019	0.018*
C12	0.47980 (10)	0.21312 (18)	0.52268 (8)	0.0159 (3)
H12	0.4753	0.1586	0.5670	0.019*
C13	0.40798 (10)	0.31546 (17)	0.49503 (8)	0.0134 (3)
C14	0.41505 (10)	0.39815 (18)	0.42856 (8)	0.0156 (3)
H14	0.3669	0.4669	0.4102	0.019*
C15	0.49373 (10)	0.37730 (17)	0.39027 (8)	0.0142 (3)
H15	0.4985	0.4324	0.3461	0.017*
C16	0.32415 (10)	0.26991 (19)	0.60087 (8)	0.0190 (3)
H16A	0.2661	0.2992	0.6205	0.028*
H16B	0.3771	0.3052	0.6343	0.028*
H16C	0.3267	0.1567	0.5958	0.028*
C17	0.83872 (10)	0.40389 (17)	0.47003 (8)	0.0152 (3)
H17	0.7874	0.4437	0.4394	0.018*
C18	0.86367 (10)	0.47614 (18)	0.53812 (8)	0.0169 (3)
H18	0.8306	0.5645	0.5524	0.020*
C19	0.93883 (10)	0.41469 (17)	0.58490 (8)	0.0153 (3)
H19	0.9555	0.4591	0.6316	0.018*
C20	0.98863 (9)	0.28598 (16)	0.56074 (7)	0.0114 (2)
C21	0.96065 (9)	0.22322 (16)	0.49060 (7)	0.0117 (2)
H21	0.9953	0.1395	0.4735	0.014*
C22	1.06782 (9)	0.20324 (17)	0.60760 (7)	0.0120 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00880 (8)	0.01102 (9)	0.00963 (8)	0.00027 (6)	0.00037 (6)	−0.00144 (6)
O1	0.0127 (4)	0.0164 (5)	0.0175 (5)	0.0029 (4)	0.0014 (4)	−0.0019 (4)
O2	0.0120 (4)	0.0141 (5)	0.0153 (4)	−0.0002 (4)	0.0033 (4)	−0.0005 (4)
O3	0.0202 (5)	0.0259 (6)	0.0315 (6)	−0.0008 (5)	0.0141 (5)	0.0034 (5)
O4	0.0195 (5)	0.0198 (6)	0.0158 (5)	−0.0003 (4)	0.0055 (4)	0.0042 (4)
O5	0.0114 (4)	0.0150 (5)	0.0133 (4)	0.0011 (4)	0.0024 (3)	−0.0006 (4)
O6	0.0133 (5)	0.0200 (5)	0.0183 (5)	0.0049 (4)	0.0049 (4)	0.0030 (4)
O7	0.0165 (5)	0.0120 (5)	0.0168 (5)	0.0028 (4)	−0.0017 (4)	−0.0015 (4)
O8	0.0116 (5)	0.0229 (6)	0.0154 (5)	−0.0010 (4)	0.0013 (4)	−0.0084 (4)
N1	0.0112 (5)	0.0113 (6)	0.0128 (5)	0.0002 (4)	0.0002 (4)	−0.0008 (4)
N2	0.0184 (6)	0.0162 (7)	0.0155 (6)	0.0042 (5)	−0.0048 (5)	−0.0034 (5)
C1	0.0118 (6)	0.0150 (6)	0.0102 (5)	−0.0009 (5)	−0.0017 (5)	−0.0029 (5)
C2	0.0113 (6)	0.0147 (7)	0.0113 (6)	−0.0004 (5)	0.0001 (5)	−0.0018 (5)
C3	0.0154 (6)	0.0133 (7)	0.0171 (6)	0.0007 (5)	0.0025 (5)	0.0006 (5)
C4	0.0154 (6)	0.0186 (7)	0.0224 (7)	0.0039 (6)	0.0042 (5)	0.0005 (6)
C5	0.0139 (6)	0.0213 (7)	0.0172 (6)	−0.0031 (6)	0.0046 (5)	−0.0014 (6)
C6	0.0191 (7)	0.0153 (7)	0.0155 (6)	−0.0014 (5)	0.0025 (5)	0.0012 (5)
C7	0.0156 (6)	0.0156 (7)	0.0147 (6)	0.0013 (5)	0.0010 (5)	−0.0008 (5)
C8	0.0256 (8)	0.0279 (9)	0.0243 (7)	−0.0082 (7)	0.0101 (6)	0.0011 (7)
C9	0.0124 (6)	0.0130 (6)	0.0112 (6)	−0.0021 (5)	0.0001 (5)	−0.0027 (5)
C10	0.0117 (6)	0.0118 (6)	0.0128 (6)	−0.0004 (5)	0.0009 (5)	−0.0007 (5)
C11	0.0139 (6)	0.0156 (7)	0.0149 (6)	0.0048 (5)	0.0021 (5)	0.0026 (5)
C12	0.0175 (7)	0.0165 (7)	0.0141 (6)	0.0036 (5)	0.0037 (5)	0.0038 (5)
C13	0.0117 (6)	0.0136 (7)	0.0153 (6)	0.0005 (5)	0.0028 (5)	−0.0015 (5)
C14	0.0140 (6)	0.0141 (7)	0.0184 (6)	0.0033 (5)	−0.0005 (5)	0.0024 (5)
C15	0.0149 (6)	0.0137 (7)	0.0138 (6)	0.0005 (5)	0.0002 (5)	0.0031 (5)
C16	0.0178 (7)	0.0209 (8)	0.0194 (7)	0.0025 (6)	0.0079 (5)	0.0020 (6)
C17	0.0131 (6)	0.0132 (7)	0.0186 (6)	0.0019 (5)	−0.0024 (5)	−0.0015 (5)
C18	0.0151 (6)	0.0146 (7)	0.0205 (7)	0.0045 (5)	−0.0013 (5)	−0.0051 (5)
C19	0.0146 (6)	0.0155 (7)	0.0153 (6)	0.0000 (5)	−0.0011 (5)	−0.0053 (5)
C20	0.0100 (6)	0.0110 (6)	0.0132 (6)	−0.0010 (5)	0.0006 (5)	0.0001 (5)
C21	0.0106 (6)	0.0111 (6)	0.0136 (6)	−0.0005 (5)	0.0019 (5)	−0.0002 (5)
C22	0.0108 (6)	0.0121 (6)	0.0131 (6)	−0.0005 (5)	0.0006 (5)	0.0018 (5)

Geometric parameters (Å, º) top

Cu1—O2	1.9634 (10)	C6—H6	0.9300
Cu1—O5	1.9548 (10)	C7—H7	0.9300
Cu1—O7ⁱ	2.3655 (10)	C8—H8A	0.9600
Cu1—O8	1.9667 (10)	C8—H8B	0.9600
Cu1—N1	2.0171 (11)	C8—H8C	0.9600
O1—C1	1.2540 (17)	C9—C10	1.4912 (18)
O2—C1	1.2754 (17)	C10—C15	1.4030 (19)
O3—C8	1.426 (2)	C11—C10	1.3856 (19)
O4—C9	1.2466 (17)	C11—C12	1.3886 (19)
O5—C9	1.2808 (17)	C11—H11	0.9300
O6—C13	1.3634 (17)	C12—C13	1.3876 (19)
O6—C16	1.4355 (17)	C12—H12	0.9300
O7—Cu1ⁱ	2.3655 (10)	C13—C14	1.399 (2)
O8—H81	0.79 (3)	C14—C15	1.381 (2)
O8—H82	0.83 (2)	C14—H14	0.9300
N1—C17	1.3444 (18)	C15—H15	0.9300
N1—C21	1.3401 (17)	C16—H16A	0.9600
N2—C22	1.3278 (18)	C16—H16B	0.9600
N2—H2A	0.86 (2)	C16—H16C	0.9600
N2—H2B	0.83 (2)	C17—H17	0.9300
C1—C2	1.4985 (19)	C18—C17	1.3833 (19)
C2—C7	1.394 (2)	C18—C19	1.3895 (19)
C3—C2	1.4007 (19)	C18—H18	0.9300
C3—C4	1.383 (2)	C19—H19	0.9300
C3—H3	0.9300	C20—C19	1.3886 (19)
C4—H4	0.9300	C20—C21	1.3903 (18)
C5—O3	1.3650 (17)	C21—H21	0.9300
C5—C4	1.399 (2)	C22—O7	1.2345 (17)
C5—C6	1.391 (2)	C22—C20	1.5053 (18)
C6—C7	1.390 (2)

O2—Cu1—O7ⁱ	85.44 (4)	H8A—C8—H8B	109.5
O2—Cu1—O8	88.96 (4)	H8A—C8—H8C	109.5
O2—Cu1—N1	93.49 (4)	H8B—C8—H8C	109.5
O5—Cu1—O2	176.73 (4)	O4—C9—O5	123.30 (13)
O5—Cu1—O7ⁱ	97.41 (4)	O4—C9—C10	119.63 (12)
O5—Cu1—O8	89.07 (4)	O5—C9—C10	117.05 (12)
O5—Cu1—N1	88.22 (4)	C11—C10—C9	120.61 (12)
O8—Cu1—O7ⁱ	97.34 (4)	C11—C10—C15	118.88 (13)
O8—Cu1—N1	173.84 (5)	C15—C10—C9	120.48 (12)
N1—Cu1—O7ⁱ	88.50 (4)	C10—C11—C12	121.22 (13)
C1—O2—Cu1	112.27 (9)	C10—C11—H11	119.4
C5—O3—C8	117.64 (13)	C12—C11—H11	119.4
C9—O5—Cu1	114.26 (9)	C11—C12—H12	120.3
C13—O6—C16	116.39 (11)	C13—C12—C11	119.38 (13)
C22—O7—Cu1ⁱ	134.96 (9)	C13—C12—H12	120.3
Cu1—O8—H82	125.4 (12)	O6—C13—C12	123.72 (13)
Cu1—O8—H81	123.2 (18)	O6—C13—C14	116.04 (12)
H82—O8—H81	103 (2)	C12—C13—C14	120.24 (13)
C17—N1—Cu1	120.44 (9)	C13—C14—H14	120.1
C21—N1—Cu1	120.36 (9)	C15—C14—C13	119.77 (13)
C21—N1—C17	118.32 (12)	C15—C14—H14	120.1
C22—N2—H2A	122.8 (14)	C10—C15—H15	119.7
C22—N2—H2B	120.0 (14)	C14—C15—C10	120.51 (13)
H2B—N2—H2A	116.8 (19)	C14—C15—H15	119.7
O1—C1—O2	123.25 (13)	O6—C16—H16A	109.5
O1—C1—C2	119.15 (13)	O6—C16—H16B	109.5
O2—C1—C2	117.60 (12)	O6—C16—H16C	109.5
C3—C2—C1	121.78 (13)	H16A—C16—H16B	109.5
C7—C2—C1	119.50 (12)	H16A—C16—H16C	109.5
C7—C2—C3	118.72 (13)	H16B—C16—H16C	109.5
C2—C3—H3	119.8	N1—C17—C18	122.43 (12)
C4—C3—C2	120.44 (14)	N1—C17—H17	118.8
C4—C3—H3	119.8	C18—C17—H17	118.8
C3—C4—C5	120.11 (14)	C17—C18—C19	119.00 (13)
C3—C4—H4	119.9	C17—C18—H18	120.5
C5—C4—H4	119.9	C19—C18—H18	120.5
O3—C5—C4	115.72 (14)	C18—C19—H19	120.5
O3—C5—C6	124.15 (14)	C20—C19—C18	118.94 (12)
C6—C5—C4	120.13 (13)	C20—C19—H19	120.5
C5—C6—H6	120.4	C19—C20—C21	118.40 (12)
C7—C6—C5	119.18 (14)	C19—C20—C22	124.05 (12)
C7—C6—H6	120.4	C21—C20—C22	117.45 (12)
C2—C7—H7	119.3	N1—C21—C20	122.83 (13)
C6—C7—C2	121.41 (13)	N1—C21—H21	118.6
C6—C7—H7	119.3	C20—C21—H21	118.6
O3—C8—H8A	109.5	O7—C22—N2	123.72 (13)
O3—C8—H8B	109.5	O7—C22—C20	119.57 (12)
O3—C8—H8C	109.5	N2—C22—C20	116.69 (12)

O7ⁱ—Cu1—O2—C1	−166.69 (9)	C6—C5—O3—C8	−6.9 (2)
O8—Cu1—O2—C1	95.87 (9)	O3—C5—C4—C3	−179.07 (13)
N1—Cu1—O2—C1	−78.48 (9)	C6—C5—C4—C3	0.9 (2)
O7ⁱ—Cu1—O5—C9	−177.06 (9)	O3—C5—C6—C7	179.92 (13)
O8—Cu1—O5—C9	−79.78 (9)	C4—C5—C6—C7	0.0 (2)
N1—Cu1—O5—C9	94.69 (9)	C5—C6—C7—C2	−0.8 (2)
O2—Cu1—N1—C17	128.61 (11)	O4—C9—C10—C11	−168.45 (13)
O2—Cu1—N1—C21	−62.33 (11)	O4—C9—C10—C15	9.4 (2)
O5—Cu1—N1—C17	−48.59 (11)	O5—C9—C10—C11	9.80 (19)
O5—Cu1—N1—C21	120.47 (11)	O5—C9—C10—C15	−172.30 (12)
O7ⁱ—Cu1—N1—C17	−146.05 (11)	C9—C10—C15—C14	−178.15 (13)
O7ⁱ—Cu1—N1—C21	23.01 (10)	C11—C10—C15—C14	−0.2 (2)
Cu1—O2—C1—O1	−0.05 (16)	C12—C11—C10—C9	177.95 (13)
Cu1—O2—C1—C2	179.28 (9)	C12—C11—C10—C15	0.0 (2)
Cu1—O5—C9—O4	8.36 (17)	C10—C11—C12—C13	0.3 (2)
Cu1—O5—C9—C10	−169.82 (9)	C11—C12—C13—O6	179.65 (13)
C16—O6—C13—C12	5.6 (2)	C11—C12—C13—C14	−0.4 (2)
C16—O6—C13—C14	−174.33 (13)	O6—C13—C14—C15	−179.84 (13)
Cu1—N1—C17—C18	168.29 (11)	C12—C13—C14—C15	0.2 (2)
C21—N1—C17—C18	−1.0 (2)	C13—C14—C15—C10	0.1 (2)
Cu1—N1—C21—C20	−166.33 (10)	C19—C18—C17—N1	−1.6 (2)
C17—N1—C21—C20	3.0 (2)	C17—C18—C19—C20	2.2 (2)
O1—C1—C2—C3	178.44 (12)	C21—C20—C19—C18	−0.4 (2)
O1—C1—C2—C7	−2.31 (19)	C22—C20—C19—C18	−176.58 (13)
O2—C1—C2—C3	−0.91 (19)	C19—C20—C21—N1	−2.3 (2)
O2—C1—C2—C7	178.33 (12)	C22—C20—C21—N1	174.18 (12)
C1—C2—C7—C6	−178.58 (12)	O7—C22—C20—C19	170.96 (14)
C3—C2—C7—C6	0.7 (2)	O7—C22—C20—C21	−5.28 (19)
C4—C3—C2—C1	179.42 (13)	N2—C22—O7—Cu1ⁱ	29.9 (2)
C4—C3—C2—C7	0.2 (2)	N2—C22—C20—C19	−7.8 (2)
C2—C3—C4—C5	−0.9 (2)	N2—C22—C20—C21	175.94 (13)
C4—C5—O3—C8	173.01 (14)	C20—C22—O7—Cu1ⁱ	−148.77 (10)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱⁱ	0.86 (2)	2.03 (2)	2.8407 (18)	158 (2)
N2—H2B···O4ⁱⁱⁱ	0.83 (2)	2.29 (2)	2.9897 (17)	141.4 (18)
O8—H81···O1^iv	0.79 (3)	1.97 (3)	2.7236 (15)	159 (3)
O8—H82···O4^iv	0.825 (18)	1.803 (18)	2.6052 (16)	163.9 (18)

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r	1011.93
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	14.1707 (3), 8.4319 (2), 18.0225 (3)
β (°)	95.847 (2)
V (Å³)	2142.23 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.37 × 0.37 × 0.23

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.678, 0.781
No. of measured, independent and observed [I > 2σ(I)] reflections	20329, 5403, 4813
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.072, 1.05
No. of reflections	5403
No. of parameters	316
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86 (2)	2.03 (2)	2.8407 (18)	158 (2)
N2—H2B···O4ⁱⁱ	0.83 (2)	2.29 (2)	2.9897 (17)	141.4 (18)
O8—H81···O1ⁱⁱⁱ	0.79 (3)	1.97 (3)	2.7236 (15)	159 (3)
O8—H82···O4ⁱⁱⁱ	0.825 (18)	1.803 (18)	2.6052 (16)	163.9 (18)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y−1/2, −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 the diffractometer. This work was supported financially by Kafkas University Research Fund (grant No. 2009-FEF-03).

References

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